United Stares	Industrial Environmental Research fcPA 600 ? 8t>- i,5£
Environmental Protection	laboratory	».,c. 1W-
Agency	Cincinnai- OH 46258
Reasarc*' and Development
Dioxins
Volume III.
Assessment of
Dioxin-Forming
Chemical Processes

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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1.	Environmental Health Effects Research
2.	Environmental Protection Technology
3.	Ecological Research
4.	Environmental Monitoring
5.	Socioeconomic Environmental Studies
6.	Scientific and Technical Assessment Reports (STAR)
7.	Interagency Energy-Environment Research and Development
8.	"Special" Reports
9.	Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution-sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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EPA—600/2—80-158
June 1980
DIOXINS:
VOLUME III.
ASSESSMENT OF DIOXIN-FORMING CHEMICAL PROCESSES
by
Forrest E. Dryden, Harry E. Ensley
Ronald J. Rossi, E. Jasper Westbrook
Walk, Haydel & Associates, Inc.
New Orleans, Louisiana 70130
Contract No. 68-03-2579
Project Officer
David R. Watkins
Industrial Pollution Control Division
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268

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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory Cincinnati (IERL-Ci), U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the U.S. Environmental Protec-
tion Agency, nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.

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FOREWORD
When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on our
health often require that new and increasingly more efficient pollution con-
trol methods be used. The Industrial Environmental Research Laboratory-
Cincinnati (IERL-Ci) assists in developing and demonstrating new and im-
proved methodologies that will meet these needs both efficiently and
economically.
This report is one of a three-volume series dealing with a group of
hazardous chemical compounds known as dioxins. The extreme toxicity of one
of these chemicals, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), has
been a concern of both scientific researchers and the public for many years.
The sheer mass of published information that has resulted from this concern
has created difficulties in assessing the overall scope of the dioxin
problem. In this report series the voluminous data on 2,3,7,8-TCDD and
other dioxins are summarized and assembled in a manner that allows compari-
son of related observations from many sources; thus, the series serves as a
comprehensive guide in evaluation of the environmental hazards of dioxins.
Volume I is a state-of-the-art review of dioxin literature. Detailed
information is presented on the chemistry, sources, degradation, transport,
disposal, and health effects of dioxins. Accounts of public and occupa-
tional exposure to dioxins are also included. Volume II details the devel-
opment of a new analytical method for detecting part-per-tri11 ion levels of
dioxins in industrial wastes. It also includes a review of the analytical
literature on methods of detecting dioxins in various types of environmental
samples. Volume III identifies various routes of formation of dioxins in
addition to the classical route of the hydrolysis of chlorophenols. The
possible presence of dioxins in basic organic chemicals and pesticides is
addressed, and production locations for these materials are identified.
For further information, contact Project Officer David R. Watkins,
Organic and Inorganic Chemicals Branch, IERL-Ci. Phone (513) 684-4481.
David G. Stephan
Di rector
Industrial Environmental Research Laboratory
Cincinnati
i i i

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PREFACE
This report is Volume III in a series of three reports dealing with a
group of hazardous chemical compounds known as dioxins. This volume details
the chemistry of dioxin formation, and identifies the types of organic
chemicals and pesticides which may have dioxins associated with them as
impurities or byproducts. Other volumes of this series examine the occur-
rence, environmental transport, toxicity, and disposal of this class of
compounds, analytical techniques used to identify dioxins, and commercial
products with potential for containing dioxin contaminants.
An extensive body of published literature has appeared during the past
25 years that has been concerned primarily with one extremely toxic member
of this class of compounds, 2,3,7,8-tetrachlorodibenzo-p-dioxin. Often
described in both popular and technical literature as "TCDD" or simply
"dioxin," this compound is one of the most toxic substances known to
science. This report series is concerned not only with this compound, but
also with all of its chemical relatives that contain the dioxin nucleus.
Throughout these reports, the term "TCDD's" is used to indicate the family
of 22 tetrachlorodibenzo-p-dioxin isomers, whereas the term "dioxin" is used
to indicate any compound with the basic dioxin nucleus. The most toxic
isomer among those that have been assessed is specifically designated as
"2,3,7,8-TCDD."
The objective in the use of these terms is to clarify a point of tech-
nical confusion that has occasionally hindered comparison of information
from various sources. In particular, early laboratory analyses often re-
ported the presence of "TCDD," which may have been the most-toxic
2,3,7,8-isomer or may have been a mixture of several of the tetrachloro
isomers, some of which are relatively nontoxic. Throughout this report
series, the specific term 2,3,7,8-TCDD is used when it was the intent of the
investigator to refer to this most-toxic isomer. Since early analytical
methods could not dependably isolate specific isomers from environmental
samples, the generic term "TCDD's" is used when this term appears to be most
appropriate in light of present technology.
i v

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ABSTRACT
Concern about potential contamination of products and wastes by
dibenzo-p-dioxins in the production of organic chemicals and pesticides is
the reason for this study of products and processes subject to such contam-
ination. In addition, speculative consideration is given to other possible
dioxin sources.
Chemical reaction mechanisms by which dioxins may be formed are
reviewed, particularly those likely to occur within commercially significant
processes. Various routes of formation are identified in addition to the
classical route of the hydrolysis of trichlorophenol. Basic organic
chemicals and pesticides with a reasonable potential for dioxin byproduct
contamination are surveyed as to current and past producers and production
locations.
Classifications are presented both for general organic chemicals and
for pesticides that indicate likelihood of dioxin formation. Conditions are
noted that are most likely to promote dioxin formation in various processes.
This report was submitted in fulfillment of Contract No. 68-03-2579, by
Walk, Haydel & Associates, Inc., under the sponsorship of the U.S. Environ-
mental Protection Agency. This report covers the period October 31, 1978,
to March 16, 1980, and work was completed as of March 16, 1980.
v

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CONTENTS
Page
Foreword	iii
Preface	iv
Abstract	v
List of Figures	viii
List of Tables	x
List of Abbreviations	X1-
Acknowledgment	x-jj
1.	Introduction	1
2.	Conclusions	3
3.	The Chemistry of Dibenzo-p-Dioxins	4
4.	Speculative Sources of Dioxins	39
5.	Organic Chemicals	43
6.	Pesticide Chemicals	64
7.	Chemicals, Producers, and Plant Locations	90
References
Bibliography
vii

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1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
ige
53
54
55
56
57
58
59
60
61
62
63
71
72
73
74
76
77
78
79
80
FIGURES
4-Bromo-2,5-dichlorophenol
2-Chioro-4-fluorophenol
Decabromophenoxybenzene
2,4-Di bromophenol
2.3-Dichlorophenol
2.4-Dichlorophenol
2.5-Dichlorophenol
2.6-Dichlorophenol
3,4-Dichlorophenol
Pentabromophenol
2,4,6-Tribromophenol
2,4,5-Trichlorophenol, 2,4,5-T and esters and salts
Si 1 vex and esters and salts
Ronnel
Erbon and Sesone
2,4-0 and esters and salts
2,4-DB
2,4-OP
Oicapthon and Dichlofenthion
Bi fenox
viii

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FIGURES (continued)
Number	Page
21	Nitrofen	81
22	Dicamba	82
23	Pentachlorophenol (PCP) via	phenol	83
24	Pentachlorophenol (PCP) via	hexachlorobenzene	84
25	Chloranil	85
26	Hexachlorophene and Isobac 20	87
27	2,3,4,6-Tetrachlorophenol	88
ix

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2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
6
10
25
29
45
65
70
89
91
92
93
94
95
96
97
98
TABLES
Perhalo Dibenzo-p-Dioxins via Free Radical Reactions
Ullman Condensation Reactions
Catechol-Based Reactions
Substitution Reactions
List of Organic Chemicals
List of Pesticide Chemicals
Higher Chlorinated Dioxins Found in Commercial Pesticides
Pesticide Raw Materials
Class I Organic Chemicals
Class II Organic Chemicals
Class III Organic Chemicals
Organic Chemical Producers
Former Organic Chemical Production Locations
Pesticide Chemicals - Classes I and II
Pesticide Chemical Producers
Former Pesticide Production Locations
X

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LIST OF ABBREVIATIONS
DBDCDD's
di bromodichlorodi benzo-p-di oxi ns
DBDD's
dibromodibenzo-p-dioxins
DCDD's
dichlorodibenzo-p-dioxins
Dioxins
dibenzo-p-dioxins
DFDD's
di f1uorodi benzo-p-di oxi ns
DMSO
dimethyl sulfoxide
DNDD's
dinitrodibenzo-p-dioxins
Hexa-CDD1s
hexachlorodi benzo-p-di oxi ns
Hepta-CDD1s
heptachlorodibenzo-p-dioxins
OBDD
octabromodi benzo-p-di oxi n
OCOD
octachlorodi benzo-p-di oxi n
PCP
pentachlorophenol
Penta-CDD's
pentachlorodibenzo-p-dioxins
TBDD's
tetrabromodibenzo-p-dioxins
TCDD's
tetrachlorodibenzo-p-dioxins
2,3,7,8-TCDD
2,3,7,8-tetrachlorodibenzo-p-dioxin
TCP
trichlorophenol
Tri-CDD's
trichlorodibenzo-p-dioxins
xi

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ACKNOWLEDGMENT
This report was prepared by Walk Haydel & Associates, Inc. under the
direction, contribution, and contract management of Forrest E. Dryden.
Contributing authors included Harry E. Ensley, Ronald J. Rossi, and E.
Jasper Westbrook.
Final compilation of this report for integration into the three-volume
dioxin series was done by PEDCo Environmental, Inc., Cincinnati, Ohio, with
Mr. R. W. Gerstle as Project Director and Ms. M. Pat Esposito as Project
Manager. Information on natural compounds as potential precursors of
dioxins was provided by PEDCo Environmental, Inc.
The cooperation of the many organizations and individuals who assisted
in the collection, editing, and critiquing of this material is appreciated.
Particular thanks to Robert J. Planchet, Jerome F. Pankow, and William J.
Kimsey, Jr. for their contributions.
xii

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SECTION 1
INTRODUCTION
A dioxin is any of a family of compounds known chemically as dibenzo-
para-dioxins. Each of these compounds has as a nucleus a triple-ring struc-
ture consisting of two benzene rings interconnected to each other through a
pair of oxygen atoms. Shown below are the structural formula of the dioxin
nucleus and also the abbreviated structural convention used throughout the
report series.
:x^;
6	4
Halogenated dibenzo-p-dioxins (dioxins), and in particular chlorinated
dioxins such as 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD), are
known to be toxic even at low concentrations. Such contaminants have been
found in a number of commercial organic chemical products, primarily pesti-
cides of the 2,4,5-T type. For this reason an analysis was undertaken of
the chemical products and processes likely to be conducive to the formation
of dioxins. This report reviews the chemical mechanisms by which commercial
organic processes might produce dioxins as byproducts and tabulates those
chemicals likely to be associated with dioxins as a consequence. In addi-
tion, it lists known producer locations for such chemicals, indicating
potential sources of current and past contaminated wastes.
In approaching this study, the investigators proceeded as follows.
1.	Reviewed current theories on mechanisms of the formation of
dioxins under various reaction conditions.
2.	Tabulated reported laboratory preparations of dibenzo-p-dioxins.
3.	Established criteria for structure and reaction conditions con-
ducive to dioxin formation in chemical processing.
4.	Postulated conditions under which dioxins might be formed other
than in commercial chemical production.
5.	Differentiated between pesticide chemicals and all other types of
organic chemicals for purposes of this study.
1

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6.	Reviewed commercially significant chemicals, using as primary
sources the Stanford Research Institute Directory of Chemical
Producers, the Merck Index, The Farm Chemicals Handbook, and other
reference materials.
7.	Designated those products in which the chemical structures might
indicate association with dioxins.
8.	Further screened the list by consideration of reaction conditions,
processing sequence, and intermediates.
9.	Categorized general organic chemical products in three classes.
Class I: strong likelihood of polyhalogenated dibenzo-p-dioxin
association
Class II: strong likelihood of other dioxin association
Class III: moderate probability of dioxin association
10.	Categorized the target pesticide chemicals as belonging in Class I
or Class II.
11.	Identified the dioxin compounds and formation mechanisms expected
to be related to each Class I compound.
12.	Listed known locations in the United States in which production
occurs or has occurred in the past 10 years. The primary source
was the Stanford Research Institute Directory of Chemical
Producers covering the years 1968 through 1978.
Some recent regulatory restrictions on the use of some herbicides, such
as 2,4,5-T and silvex, may result in curtailed production. This study does
not address the effects of any such curtailment (e.g., production shut-
downs).
Although there is a substantial range of toxicity among the various
substituted dibenzo-p-dioxins, processes indicating potential for generation
of the less-toxic forms are included for two reasons:
1.	Dioxins other than those that might be hypothesized by straight-
forward mechanisms have been found in a number of commercial
products (Fishbein 1973).
2.	Disproportionate and other composition changes may cause shifts
in content, possibly from lower to higher toxicity forms (Buser
1976).
Subjective judgement was exercised with respect to inclusion and clas-
sification of chemicals and processes. In addition, although every reason-
able effort was made to avoid omissions, some are inevitable in view of the
number of organic chemical compounds to be dealt with.
2

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SECTION 2
CONCLUSIONS
1.	Dibenzo-p-dioxins should be expected as byproduct trace contamination
in a number of commercially manufactured organic chemicals. These
include not only the frequently cited herbicides of the 2,4,5-T type,
but also numerous other ortho halogenated phenols and related struc-
tures commonly made or used in organic chemical processing.
2.	Processing conditions of elevated temperatures plus either alkalinity
or the presence of free halogen—conditions often nece-ssary for dioxin
formation—are frequently encountered in the manufacture of these
organic compounds.
3.	The particular dibenzo-p-dioxins found as trace byproduct materials are
often at variance with those anticipated on the basis of straightfor-
ward mechanisms. This variance is possibly due to mechanisms more
complex than those that have been proposed or to disproportionate
(shifting of halogens) of the initially produced halogenated dioxins.
4.	Dioxin contamination resulting from the manufacture of many organic
chemicals could follow either of two paths. First, it could appear as
trace contamination of the finished chemical product; second, it could
appear as a component of wastes from leakage, handling, purification,
neutralization, and "off-spec" production. This report does not con-
sider the formation of dioxins in subsequent consumptive uses.
5.	Plant locations of present and past commercial production of potential-
ly dioxin-associated chemicals are widespread over the United States.
6.	Sites of exposure or contamination are not necessarily defined by
production locations, because wastes are often dumped at sites remote
from the production facility. Exact locations of disposal sites would
require investigation of individual plant practices.
7.	There is a variety of potential dioxin sources other than commercial
production by syntheses of organic chemicals. Among these are labor-
atory preparation of dioxins in small quantities but high concentra-
tions, and the combustion of mixed wastes containing potential dioxin
precursors.
8.	Reaction conditions ranging from temperatures as low as 145°C, and the
presence of weak to strong bases acting on the organic and pesticide
products can result in production of trace quantities of dioxins.
3

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SECTION 3
THE CHEMISTRY OF DIBENZO-p-DIOXINS
Concern has recently arisen about the occurrence of trace quantities of
halogenated dibenzo-p-dioxins (hereafter referred to as halogenated dioxins)
and in particular 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) in the
environment. A study of the reported laboratory procedures for preparation
of dioxins can serve as a guide to the chemical conditions that are most
likely to lead to dioxin formation. This review of the literature is not
limited to methods for the preparation of halogenated dioxins; rather it
delineates the known procedures for the preparation of dioxins of any sub-
stitution pattern.
LABORATORY PREPARATIONS OF DIOXINS
The first report of intentional preparation* of this class of compounds
occurred in 1872, when Merz and Weith described the preparation of
"perchlorophenylenoxyd" by thermolysis of potassium pentachlorophenate (1).
Hugounenq (1890) reported that the treatment of pentachloroanisole (2)
with concentrated sulfuric acid also gives "perchlorophenylenoxyd."
0©
OK	OCH3
C,V^VCI
I]	—	 » PERCHLOROPHEWTLENOXTD «#—=	 l| I
CI	CI
W	(2)
* According to scientists of Dow Chemical (Rawls 1979), dioxins have been
prepared since "...Prometheus stole fire from the gods and brought it to
manki nd...".
4

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Soon after these reports Zinke (1894) and Blitz (1904) showed that
heating heptachlorohexenone (3) to 200°C gave "perchlorophenylenoxyd." Not
until 1960 was it shown that "perchlorophenylenoxyd" is octachlorodibenzo-
p-dioxin (0CDD)(4) (Denivelle 1960).
civA9|,
CI CI
(1)
00
The mechanism of the reactions reported by Zinke and Blitz remained
unknown for over a half-century. In 1961 Kulka showed- that heptachloro-
cyclohexenone (3) eliminates a molecule of hydrogen chloride at about 180°C
to give hexachlorocyclohexadienone (5). Kulka proposed that this compound,
on heating to 2Q0°C, loses a chlorine radical to give the pentachlorocyclo-
hexadienone radical (6) (or its resonance isomer, the pentachlorophenoxy
radical (7)), which then dimerizes to give (4) and a molecule of chlorine.
CI CI
(2)
180°C CI
—-HCI +
Cl
CI 200°C CI
	^ci* +
CI CI
(1)
U)
Cl2 +
The mechanism that Kulka proposed, supplemented with earlier work by
Denivelle (1959, 1960), initiated numerous reports on the preparation of
halogenated dibenzo-p-dioxins under neutral or acidic conditions. A number
of these reactions are listed in Table 1.
Bayer (1903) patented a process for the preparation of dibenzo-p-dioxin
(8) from sodium o-chlorophenylate (9). This procedure, which is an exten-
sion of the earlier work reported by Merz and Weith (1872), is based on
5

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TABLE 1. PERHALO DIBENZO-p-DIOXINS VIA FREE RADICAL REACTIONS
Item
Reactant
Conditions
Product	(Yield) Ref.
©
CI
CI
OH	O
ci+^yV01 25°o"3oo°c Cl
CI CI^^^CI 25 min	CI
CI CI
Cl
40 g
OH
©
Cl
Cl
Cl
Cl
Cl
25 g
O
©
Cl
Cl
Cl ci
OH
©
Cl
Cl
Cl
Cl
Cl
25 g
OH
Cl-
cr
XI
-ci
ci
ci
+
Cl	Cl
Cl	Cl
Cl
Cl
(83%)
10 g
+ Clr
REFLUXING Cl
1,2,4 TRICHLOROBENZENE
16 h
270°-280°C
30 min
Cl	Cl
o-
CI^V^O-
Cl ci
18g
Cl ci
Cl
Cl
Cl	Cl
llg
Cl
Cl
(83%)
(73%)
Cl
Cl
+ Br-;
I, 2,4 TRICHLOROSEi-iZENE Cl
REFLUX lb h Cl
2.4 TRICHLORODENZENE
REFLUX 16 h Cl
Cl	O-
Cl Cl
Cl
Cl
Cl
(52%)
CI
Cl
1

Cl
i


r°i
rS
c,
r

V
Cl
Cl

Cl

(23%)
(conti nued)
6

-------
TABLE 1 (continued)
Item
Reactant
Conditions	Product	(Yield) Ref.
OH	O
or cl2 | 320°-360°C
or Br2/ 35 min Br
Br
35 g
CI CI
0.2 g
Br
(52%) c
Br (15g)
©
Br
Br
OH	O
Br+ Clv]f^S|/CI f0r Cl2^ 300°-350°C 01
•Br CI^%Aci \°r Br2/ 30 min Br
CI	CI CI
30 g	0.2 g
OH
©
CI
CI
CI
CI
CI
300°C
(62%)
(15g)
CI (POOR)
(conti nued)
7

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TABLE 1 (continued)
Reactant
Conditions
Product

CI
CI

CI
CI

CI
CI
OH
CI
200 g
OH
CI
222 g
O
CI
CI
CI CI
75 g
O
CI
CI
CI CI
62 g
OH
CI
I20-200°C
120-200°C
270 C IN
CI
CI
CI
CI
CI
C| QUINOLINE C|
CI
CI
CI
CI
CI
CI
CI
CI
o-k^Aci
CI
CI
CI
CI
CI
CI
CI
CI
CI
(04%)
, If no yield is stated, no	value is reported in reference.
D Kulka 1965.	! Gribble 1974.
j Kulka 1961.	Sandermann, Stockmann, and Casten 1957.
Denivelle, Fort, and Pham	1959. ^ Kaupp and Klug 1962.

-------
0©
CC1^- cco
(9)	(8)
Ullmann's preparation of diphenylamines (Ullman 1903) and generally referred
to as a modified Ullman condensation (Aniline 1973). Although the yields of
the modified Ullmann reaction rarely exceed 30 percent, this procedure was
standard for the preparation of both substituted and unsubstituted dioxins
until the early 1970's. Examples of the utilization of this process are
given in Table 2, showing minor as well as major products of reaction, where
applicable.
As the reactions in Table 2 show, dioxins have been formed from the
alkali metal salts of ortho-halophenols through pyrolysis at temperatures of
200° to 300°C for several hours, usually in the presence of copper powder or
copper salts. Entries 23 and 24 in Table 2 show that much milder conditions
(pyridine as the base and a temperature of only 145°C for 2 to 3 hours) can
give significant concentrations of dibenzo-p-dioxins (Ueda 1963).
The mechanism for this type of reaction was generally believed to
involve a nucleophilic attack of the phenoxy ion on a second phenolate ring
(Buser 1975), followed by expulsion of the halide to give the o-halophen-
oxyphenate (10) (also known as predioxin). An intramolecular nucleophilic
aromatic substitution followed by expulsion of a halide gives the dibenzo-
p-dioxin (11).
©:ojm©

©
-x
1/	W
Q*'M©
(10)
X=leaving group
(e.g. CI, F, Br, I, NC^, SC>3R)
M=alkali metal cation
Y=any substituent group
9

-------
TABLE 2. liLLMAN CONDENSATION REACTIONS
Item
Reactant
Conditions
Product	(Yield) Ref.
©
©
©
ONa
CH
CH
CH
OK
CH
Br
CH
CH
CH
CH
CH
OK
190-200°C
Cu, Cu(OAc)
CH
CH
CH
OK
OK
CH
OK
CH
CH
(25%) b
® XX
©
3
CH-

OCH3
CH,
CH
ch3o
(conti nued)
10

-------
TABLE 2 (continued)
a
Item	Reoctant	Conditions	Product	(Yield) Ref.
©
OK
Br

ON a
ONa
OK
OK
® a
® U-
6 g
Br	O
OCH3
CH3O
110 min
O	OCH3
O^U
,0:0""'
® XX»	CM°U
I60°c
Cu
1 h	\^0
160°-220°C	ff^V0
Cu,
O
/V-OK	200°C,	rf^^V0
KAo- ('-28) 9
CI
(50S) f
(conti nued)
11

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Product	(Yield) Ref.

OK Br
Br KO
N.
4.5 g
®QC„
OCH3
OH
-	CH3(VW'Br
5.78 g
6.58 g
190°C
Cu
2 h
180°C
30 min
180cC
KOH, Cu
30 min
| (0.09 g) h,j
°Tf^|
0
(0.08 g)
CJ
(TRACE)
OCH3
•0
0
OCH3
(0.164 g) k
OCH,
O
:
och3
(0.287 g)
OCH3
(0.132 g)
(conti nued)
12

-------
TABLE 2 (continued)
Product
Yield Ref.
(20 mg) i
(40 mg) 1
(40 mg) i
Item Reactant
Conditions
CI
CI
CI
OK
CI
CI
3.25 g
200°C
Cu
2 h
3.15 g
200°C
Cu
2 h
18 5°C
Cu
1.5 h
3.25 g
(40 mg) 1
CI
1

/VONa
210°C
IJF
0.3g Cu
T
3 h
CI

3.7 g

(0.9 g)
(conti nued)
13

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Product
(Yield) Ref.

190°C
Cu
4 h
CC
(25%)
195°C
Cu POWDER
30 min
ch3
ch3
(60 mg)
ch3o
200 C
Cu POWDER,
1.5 h
(250 mg) n
och3
@
190°C
Cu POWDER
1 h
(3.1 g) o
©
I45°C
Cu POWDER, PYRIDINE
2.5 h
(10 mg)
(conti nued)
14

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Product
(Yield) Ref.
©
ch3
CH 3 y^>OH
CH3^s^Br
CH3
1.17 g
145°C
Cu POWDER, PYRIDINE
3 h
CH
CH
CH
CH
O-
CH3/v^^O-'\^^CH3
ch3 ch3
(8 mg) P
CI
CI
CI
CI
(conti nued)
15

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Product	(Yield) Ref.
(D
ci
CI
OK
CI
OK
CI
CI
290°C
1-4 h
CI
CI
CI
CI	CI
CI
CI
CI
CI
CI
CI
Cf "T ^ "T CI
CI	CI
@
OK
CI
CI
OK
CI
290°C
1-4 h
CI
CI
CI
Ov^VCI
CI
CI
CI
CI
CI
(conti nued)
16

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Product	(Yield) Ref.
OK

CI
CI
OK
XI CI^/^CI
XX'
CI
290°C
1-4 h
CI
CI
CI
CI	CI
Cl^ _0.
crx^O'
CI	CI
CI
CI
CI
CI
CI
CI	CI
• 0
•o-
Cl	CI
CI
CI	CI
(conti nued)
17

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Product	(Yield) Ref.
OK
® XX
CI
290°C
1-4 h
CI
OK
CI
CI
CI
290°C
1-4 h
OK
CI^A^CI
® x jc +
w CI-^s^CI CI
OK
CI
CI
CI
290°C
1-4 h
CI
CI
CI
CI
CI
(conti nued)
18

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Proauct	(Yield) Ref.
OK
CI
C!
CI
CI
290 C
1-4 h
Ci
CI
CI
CI
CI
L.CI CI^An^CI
Aa
f^CI CI
290°c
1-4 h
CI
(continued)
19

-------
TABLE 2 (continued)
a
Item	Reactant	Conditions	Product	(Yield) Ref.
(conti nued)
20

-------
TABLE 2 (continued)
Item
Reactant
Conditions
Product	(Yield) Ref.
OK
CI
CI
OK
vc
CI
290°C
1-4 h
CI	CI
CI
CI
CI
CI	CI
CI	CI
Cl^v^o
CI	CI
CI
(MINOR)
CI
CKVN°' "CI
CI	CI
CI
CI	CI
CI
CI	CI
dWe
CI	CI
ClAj^oA^A
b
c
d
e
f
g
h
i
If no yield is stated, no value is reported in reference.
Cull inane and Davies 1936.
Tomita 1933.
Tomita and Tani 1942.
Julia and Baillarge 1953.
Tomita, Nakano, and Hirai 1954.
Tomita and Yagi 1958.
Fujita and Gota 1955.
Fujita et al. 1956.
k
1
m
n
o
P
q
Inubushi et al. 1959.
Tomita, Ueda, and Narisada 1959.
Denivelle, Fort, and Hai 1960.
Ueda 1962.
Ueda and Akio 1963.
Ueda 1963.
Buser 1975.
21

-------
In 1974 Cadogan, Sharp, and Trattles proposed a more reasonable mech-
anism involving the a-ketocarbene (12), which is attacked by the phenoxide
to give (10).
0©
ONa
-NaBr


Br
Oi
©©
•n*Kio
rA^P.:Na
Br


©0
NaO Br
O
(10)
They also proposed that the conversion of the o-halophenoxyphenate to
dibenzo-p-dioxin occurs via a benzyne intermediate (13).
/
©
O Br
O
(/
O
o
(A
The evidence in favor of this mechanism is quite convincing since both
ortho- and meta-halophenoxyphenates are converted to the same dibenzodioxin,
as shown below.
22

-------
Cu POWER
As shown in Table 2 (items 5, 6, 11, 13, 25-28, and 31-35), complex
mixtures result from attempts to prepare unsymmetrical dibenzo-p-dioxins
using the modified Ullmann reaction. An early attempt to circumvent this
problem involved the synthesis of a protected form of the unsymmetrical
predioxin intermediate (14) (Tomita 1938) followed by its conversion to the
dioxin in a separate procedure as shown below (Tomita 1938; Kermatsu 1936).
JL J + KBr
O <3^
CH3 CH3 t j a
HBr ~~
HOAc
*1XJ*5-fL— C££T
This procedure has the advantage of giving a single dibenzo-p-dioxin
isomer; however, it is limited, in that yields of the dioxin rarely exceed
10 percent (Tomita 1938).
A newer and more general procedure for the preparation of unsymmetrical
(as well as symmetrical) dibenzo-p-dioxins involves the reaction of catechol
salts with ortho-dihalobenzenes in dimethyl sulfoxide (DMSO) (Pohland 1972;
Kende 1974).
0©
a™*
ci
. ^	DMSO
OK	CI	REFLUX
0©
This procedure is a modification of a much earlier approach to the
synthesis of dibenzo-p-dioxin, which suffered low yields (Tomita 1932) or no
dioxin formation (Fujita 1955). The improved process gives very high yields
of dibenzo-p-dioxins when dimethyl sulfoxide is used as the solvent. Whether
this result is simply a solvent effect or DMSO plays a chemical role in the
reaction has not been determined. Examples of the utilization of this
reaction for the preparation of dibenzo-p-dioxins are included in Table 3.
23

-------
TABLE 3. CATECHOL-BASED REACTIONS
Item
Reactant
Conditions
Product	(Yield) Ref.
©
©
OK
Br
Br
OK
©
©
©
>OK
2.75 g	5.9 g
OK

OH
OH CI
OH Br
OH Br
OH F
OH F
200°C
Ca POWDER
CuN03
3 h
190 0 C
Cu POWDER
2 h
KOH
DMSO,A
KOH
DMSO,A
KOH
DMSO,A
(NO REACTION)
(81%) d
(25%) e
(41%) e
©
©
CI
OH CI
OH CI
OH CI
OH CI
CI
CI
a OH CK^^/Cl
OH CI
CI
KOH
DMSO,A
KOH
DMSO,A
CI
(31%) e
CI
CI
-/CI
O" \^^ci
CI
(41%) e
(conti nued)
24

-------
TABLE 3 (continued)
Item
Reactant
Conditions
Product
(Yield) Ref.
a
OH ci
+
OH CI
CI
CI
DMSO,A
KOH
DMSO,A
(351 e
TOTAL)
CI
(40»
TOTAL)
CH3
ch3
CI
OH CI
+
OH CI
® CHXTH+BrXl
H Br*
+
OH Br
OH CI
+
OH CI
CI
CI
-Br
Br
CI
CI
CH3
KOH
DMSO, A q^3
KOH
DMSO, A CH,
KOH
DMSO, a CI
(501)
(continued)
25

-------
TABLE 3 (continued)
Item
Reactant
Conditions
Product	(Yield) Ref.
S>




OH
OH
CI^^^OH CI-
© " ^
KOH
OMSO,A
KOH
OMSO,A
KOH
OMSO,A
CI
CI
CI
CI
CI
CI
oAA CI
+ Evenly distributed carbons.
^ Preparation of uniformly labelled 14C TCDD isomers (148 mil 1icurie/mil1i
mole).
? If no yield is stated, no value is reported in reference.
Tomita 1932.
S Fujita and Gota 1955.
Pohland and Yang 1972.
* Kende et al. 1974.
Rose et al. 1976.
26

-------
Although no mechanistic studies of this reaction have been reported, it
is clear that the initial attack of the catechol dianion on the polyhalo-
benzene does not occur via a benzyne intermediate, since in item 3 of Table
3 one would expect two different dioxins, which is not the result. This
does not preclude the possibility that a benzyne intermediate is involved in
the conversion of the predioxin (15) to the 2,3-dichlorodibenzo-p-dioxin
(16), as has been proposed for similar predioxin cyclizations (Cadogan
1974).
Numerous approaches to the preparation of substituted dioxins are based
on elaboration of the dibenzo-p-dioxin skeleton via electrophilic aromatic
substitution reactions. These applications are summarized in Table 4.
As indicated in Table 4, electrophilic aromatic substitution occurs
first at position 2. (The dioxin numbering sequence is shown in item 1.)
If the newly introduced substituent is deactivating (halogen or nitro), the
next attack occurs at either position 7 or 8. Gilman (1957; 1958) found
that position 1 can be metalated by treatment of dibenzo-p-dioxin with alkyl
or phenyl 1ithium reagents allowing this position to be substituted.
MISCELLANEOUS DIOXIN PREPARATIONS
Buser (1976) has developed a method for the preparation of qualitative
standards of polychlorinated dioxins based on the photodechlorination of
octachlorodioxin (Crosby 1971; 1973). Irradiation of octachlorodibenzo-p-
dioxin yields a mixture of tri-, tetra-, penta-, hexa- and heptachloro-
dibenzo-p-dioxin that is useful for the analysis of materials suspected to
contain polychlorodioxins.
ONLY OBSERVED PRODUCT
NOT OBSERVED
27

-------
TABLE 4. SUBSTITUTION REACTIONS
Item
Reactant
Conditions
Product	(Yield) Ref.
+ Br„
©
+ Br2 Fe(Br)g, CAT.
©
+ CI,
©
+ Cl2 Fe(Cl)
3
•u'	-C|
+ PENT A-CDD AND TRI-CDO
(LOW)
©
+ cu
(4B)
©
©
+ Br,
+ Br2
(765)
(675)
(conti nued)
23

-------
TABLE 4 (continued)
Item
Reactant
Conditions	Product	(Yield) Ref.
+ Ci5
(2A%) c

+ TRITIUM
CUT
+ Cl2 FeC 13,12(CAT)

och3
+ Br,
och3
OCH
(905)
och3

NO 2
HOAc.O C
HNOi, A
NO-
29

-------
TABLE 4 (continued)
Item	Reactant	Conditions	Product	(Yield) Ref.

+ RCOCI aici
3
C-R
©
©
©
©
©
OoN
H2/Pd
HONO,CuC1
Cl2, HOAc
1.PHENYL 1THIUM
2.Br
2
KB r
(1 g) j.k
KB r O3,HOAc, 120UC
(1 g)
(40%) j,k
@
8 r 2,HOAc, 120°C
(0.6 g) j,k
(conti nued)
30

-------
TABLE 4 (continued)
Item
Reactant
Conditions
Product	(Yield) Ref.
®
@
@

O
26 g
o-
50 mg
o-
0.5 g
® a
Br
® DoO
«x
0.2 g
0.5 g
Br2,H0*c, m°Z
C121 Fg CI ^ * I2
Bf2» HOAc
® COO c'2, Fec'3,4
Br,
Br,
(20
j,k
(20 g) 1
CI
bBXX€C(6° 9) m
CI
CI
CI
CI
CI
XI
CI
Br
CI
Br
g)n
If no value is stated, no value reported in reference.
Gil man and Dietrich 1957.
Jj Kende et al. 1974.
Vinopal, Yamamoto, and Casida 1973.
! Ueda 1963.
Tomita 1935.
y Tomita 1937.
. Ueo 1941.
jj Gil man and Dietrich 1957.
, Gilman and Dietrich 1958.
Sanderman, Stockmann, and Casten 1957.
m
Tomita, Ueda, and Narisada 1959.
n Denivelle, Fort, and Hai 1960.
31

-------
Lester and Brennan (1972) have patented a process for the direct con-
version of substituted phenols to substituted dibenzo-p-dioxins with a
panadiurircopper catalyst.
IOOdmoI NaOAc
HOAc, REFLUX
OH
R
R ¦ HtCH3,CH2CH3, OCH3, N02
Although the mechanism of the reaction has not been studied, the reac-
tion is important in light of the widespread industrial uses of phenol and
phenol derivatives.
An interesting procedure for preparation of dihydroxydibenzo-p-dioxins
is based on the oxidative coupling of polyhalocatechols found by reduction
of the resulting quinone (Frejka 1937).
NaNO;
HOAc,H2Q
CI
CI
Sn.HCI or
S02
CI	CI
o^A^oh
CI CI
Although the yields from this process are modest (15 to 35 percent),
the reaction proceeds under very mild conditions.
DISCUSSION OF REACTION CHEMISTRY
On the basis of the data presented thus far, certain general izations
can be made about the conditions under which formation of dioxins (both
halogenated and nonhalogenated) is probable.
32

-------
First, and most likely, is the formation of dioxins on treatment of
o-halophenols with base at elevated temperatures. The strength of the base
required to effect this reaction depends on the particular phenol involved;
however, there is adequate precedent for the ability of relatively weak
organic bases such as pyridine or quinoline to effect dioxin formation. The
temperature range required for dioxin formation varies with the particular
o-halophenol; however, 1 percent yields of halogenated dioxins have been
formed at temperatures as low as 145°C. (See Table 2, item 23.)
The presence of an ortho-halogen on the phenolic starting material is
not an absolute requirement for dioxin formation. According to the mech-
anism proposed by Cadogan, Sharp, and Trattles (1974), all that is required
is a substituent ortho to the phenol that is capable of acting as a leaving
group.
Other substituents should be capable of elimination to give the
orketocarbene and thus dioxins. Among those in addition to the halogens are
A second possible source of dioxins is the treatement of halogenated
phenols with reagents conducive to the formation of the corresponding poly-
halogenated phenoxy radical (i.e., treatment with halogens or other mild
oxidizing agents). Although this reaction has been used only for the prep-
aration of perhalo dioxins (in yields of more than 80 percent and 200-gram
quantities), there is no reason why the reaction could not produce the lower
halogenated derivatives of dioxins. (See Table 1, item 2.)
A common practice in the preparation of polyhalobenzenes by electro-
phi lie halogenation is neutralization of the acid byproduct with alkali
hydroxides. This process (or simply a basic wash of product during the
isolation procedure) can lead (via nucleophilic substitution) to a halogen-
ated phenol, which upon distillation may produce dioxins.
Dioxins
Sulfonic acids
Sulfonate esters
Nitro groups
Carboxylate esters

Dioxins
33

-------
The treatment of catechol salts with o-dihalobenzenes is a particularly
efficient method for the formation of dioxins, both halogenated and nonhalo-
genated. Also, the treatment of polyhalocatechols with mild oxidants can
produce significant quantities of halogenated dihydroxy-dioxins.
Of particular concern is the treatment of aromatic compounds under
oxidizing conditions at elevated temperature. Several industrial processes
involve the oxidation of benzene, toluene, and naphthalene under "semicom-
bustion" conditions. In lic)ht of the studies such as that by Dow Chemical
(Rawls 1979) on combustion sources of dioxins, the "tars" from these pro-
cesses (which are often generated in considerable quantities) deserve
further study.
The mechanistic aspects of dioxin formation discussed in this section
represent the current understanding of these reactions; however, several
experimental observations about dioxin formation cannot be explained by the
current theories. The formation of four isomers of hexa-CDD on pyrolysis of
2,3,4,6-tetrachlorophenate (Higginbotham 1968; Langer 1973), including the
1,2,3,7,8,9 hexa-CDD (Buser 1975), can be explained in terms of the pre-
dioxin intermediates, (17) and (19), undergoing the Smiles rearrangement as
shown on the following page.
As the diagram shows, the initially formed predioxin intermediate can
proceed directly toward dioxin formation (path a) or can undergo the Smiles
rearrangement (path b), which leads to new predioxin intermediates 1JB and
20. The newly formed predioxins can then react further to give a different
dioxin or can undergo the Smiles rearrangement to regenerate the original
predioxin. This interconvertability of predioxins often leads to mixtures
of dioxin products which are otherwise difficult to understand.
An equally disturbing mechanistic point is the observation that
numerous pesticides are contaminated by polychlorodioxins, which would not
be anticipated on the basis of the feedstock materials and reaction condi-
tions. An example reported by Fishbein (1973) is the presence of signifi-
cantly higher concentrations of hepta- and octachlorodioxins than hexa-
chlorodioxin in commercial 2,3,4,6-tetrachlorophenol, also known as
Dowicide-6 (see Table 7).
The Dow Chemical Company (Rawls 1979) has proposed that	the polychloro-
dibenzo-p-dioxins undergo disproportionation and establish	an equilibrium
mixture of halogenated dioxins. No experimental evidence in	support of this
proposal has been published.
34

-------
CI
1 ©.©
CK ^Ci
CI	CI
1 ©S
+ NaCl
~ NaCl or
CI	ci
(is
PR ED I OX IN
(£)
PREOIOXIN
PATH b
PATH b
CI Na©
CI	CI +NaCI
1,2,4,6.7,9-HEXA-CDD
Na® ci
+ NaCl
1,2,3,6,7,8-HEXA-COD
PRE DIuXIN
(20) Ci
PREDIOXIN c,
i + NaCl
+ NaCl
1,2.3,7.8.9-HEXA-CDD
CI ci
,2,4,5,0,9-HEXA-CDD
35

-------
SECTION 4
SPECULATIVE SOURCES OF DIOXINS
Dioxins can enter the environment in a variety of ways:
1.	As contaminants in commercial chemical products whose normal
processing conditions generate the dioxins as byproducts.
Sections 5 and 6 detail the mechanisms by which this can occur in
some of these commercial chemicals.
2.	As contaminants in chemical processing under improperly controlled
reaction conditions (Rappe 1978). Thus, dioxins would be present
in the wastes from "bad batches." Chemical manufacture that might
lead to dioxin presence under such circumstances is also reviewed
in Sections 5 and 6.
3.	As products of intentional dioxin preparations in the laboratory.
Although the quantities involved from such sources probably would
not be large, the concentrations would be high. Therefore any
failure to practice proper disposal could be serious because of
the high toxicity and concentration potential. Reported labora-
tory dioxin preparations are noted in Section 3.
4.	As deliberate or unintentional products of reactions carried out
by uninformed or irresponsible persons. The hazards in such cases
would be enhanced because the dioxins formed would likely be
subject to improper use or disposal.
5.	As products of combustion of general municipal, commercial, and
industrial wastes. Such wastes are likely to contain materials
required for dioxin formation. The chlorine content of municipal
waste is relatively high because of the widespread use of poly-
vinyl chloride and other chlorinated polymers.
6.	As combustion products and residues from burning vegetation that
has been sprayed with chlorinated herbicides (and other pesti-
cides). This potential source is of two-fold interest. First,
chemicals such as 2,4,5-T, 2,4-D, and others noted in Section 6
might be degraded to dioxins under relatively mild combustion
conditions (Buu-Hoi 1971). Second, formation of dioxins might
occur under combustion conditions, even from chemicals not direct-
ly related to dioxins, such as many insecticides (DDT, aldrin,
dieldrin, etc.).
36

-------
7.	As incidental products of fires in facilities such as chemical and
pesticide warehouses, farm buildings in which pesticides are
stored, and facilities for storage of chemically treated wood
products such as lumber or poles (Buu-Hoi 1971).
8.	As waste disposal byproducts of materials such as polychlorinated
biphenyls (PCB). These materials have been used extensively in
electrical transformers, as heat transfer media, as lubricants,
and in carbonless paper.
9.	As derivative wastes from pentachlorophenol (PCP) and other wood-
treating agents. Agents used in the treatment of wood products
are likely to remain with the wood through its use cycle. Thus
they are subjected to the same extremes of exposure as the wood,
including ultimately combustion, which leads to dioxin formation
(Buu-Hoi 1971).
10.	As an unsuspected byproduct of the treatment of aromatic compounds
under oxidizing conditions at elevated temperature. Several
industrial processes involve the oxidation of benzene, toluene,
and naphthalene under "semicombustion" conditions. In light of
such studies as that by Dow Chemical (Rawls 1979) on combustion
sources of dioxins, the "tars" from these processes (often occur-
ring in considerable quantities) warrant further study.
11.	As byproducts of miscellaneous chemical syntheses that may not be
commercially significant at this time. An example might be the
detected presence of 2,3,7,8-TCDD in chlorinated polyphenylene
ethers (such as 21), which can be produced from 2,4,5-trichloro-
phenol (Cox 1965).
These polymers are not known to be of commercial significance, but
serve as a cautionary example.
12. As a result of the combustion of naturally occurring compounds.
Recent reports by chemists at the Dow Chemical Company maintain
that dioxin formation is a natural consequence of combustion (Dow
1978). There are numerous naturally occurring compounds that
could, during the complex process of combustion, serve as pre-
cursors of dioxins. Combustion of these compounds in the presence
of chlorine-containing compounds (e.g., DDT or polyvinyl chloride)
NaOH
37

-------
could lead to the formation of chlorinated dioxins. Examples of
such naturally occurring "potential" dioxin precursors are given
below.
OH
OH
OH
I
CH3NHCH2CH
OH
OH
OCH3
OH
(22)
CATECHOL
(23)
(24)
ADRENAL1NE
(EPINEPHRINE)
GU A1A CD L
Catechol (22) occurs in nature as the product of phenol
biodegradation and as a major product of tannin pyrolysis
(Wertheim 1939). Guaiacol (23) occurs as the major phenolic
component in several hardwood trees and is also prepared synthet-
ically for use as an ingredient in cough syrups (Merck 1978; U.S.
EPA Draft 1979). Adrenaline (24) is a naturally occurring mamma-
lian hormone and is also prepared synthetically for use in many
drug formulations (U.S. EPA Draft 1979). Other naturally occur-
ring compounds that contain the orthohydroxy or alkoxy groups
include vanillin (25), which is the flavoring ingredient in
vanilla extract; urushiol (26), a mixture of compounds that are
the toxic constituents of poison ivy; eugenol (27), the pungent
principle of cloves; capsaicin (28) the pungent principle of
various peppers; and safrole (29), the major volatile constituent
of sassafras.
CHO
OH
OH
(26)
R = C15H31
OH
(25)
ch2ch=ch2
(27)
VANILLIN
= C15H29
= C15H27
= C15H25
¦ Ci5H23
EUGENOL
OH
CH2NHC-(CH2)rCH = CHCH(CH3)2
(28)
CAPSAICIN
ORUSHIOL
CH2CH=CH2
(29)
¦ SAFROLE
38

-------
Among many plant alkaloids that include the structure are
reserpine (30), glaucine (31), and colchicine (32). Other
potential dioxin precursors are found in the fomecin (33) series
of antibiotics, produced by a fungus, and also in one of the
active ingredients of creosote.
A constituent of animal urine is 4-hydroxy-3-methoxymandelic
acid (Merck Index 1978). Since the structure is so common in
living organisms, it is also often used in synthetic medicinal
compounds, including phenisonone, isoproterenol, estil (an
anaesthetic), methocarbanol, and the high-volume drugs guaifenesin
and methyldopa (U.S. EPA 1979).
OCH,

OCH
OCH
(30)
ch3o
ch3o
(30)
RESERPINE
GLAUCINE
CHO
ch3o
NHCOCH,
'xbc
OCH,
(32)
COLCHICINE
OH
(33)
FOMECIN
At least one natural compound may be by itself a precursor
for a chlorinated dioxin. A microorganism species creates a
defensive chemical known as drosophyllin A (34), (p-methoxytetra-
chlorophenol) (Merck Index 1978). In theory it could, when
heated, form a substituted hydroxy or methoxy chlorinated dioxin,
one possibility of which is:
+ 2 HCI
OH
CI
(341
OROSOPHYLLIN »
39

-------
SECTION 5
ORGANIC CHEMICALS
Organic chemical products with the greatest potential for byproduct
formation of dioxins are considered in this section. Pesticides and pesti-
cide manufacture are covered separately in Section 6.
Toxicity of the many substituted dibenzo-p-dioxins varies widely. None
are excluded from consideration here since disproportionate and other
composition shifts may bring about changes from lower toxicity forms to
higher (Buser 1976).
Because of the very large number of organic compounds and their varying
proclivities to form dioxins, the compounds were screened initially on the
basis of:
Molecular structure
Process sequence
Commercial significance
As a means of focusing attention on those organic chemicals most likely
to be associated with the formation of dioxins, they were placed in the
following classifications:
Class I - Polyhalogenated phenols, primarily with a halogen ortho to
the hydroxyl group, with a high probability of dioxin formation.
Products with such compounds appearing as intermediates are also con-
sidered. Manufacture of these materials normally involves reaction
conditions of elevated temperature plus either alkalinity or free
halogen presence, either of which is conducive to formation of halogen-
ated dioxins.
Class II - Ortho-halophenols and ortho-halophenyl ethers where the
substituted groups are a mixture of halogens and nonhalogens. Process-
ing conditions are similar to those defined for Class I and produce
mixed substituted dioxins. The distinction between Classes I and II is
arbitrary and does not indicate necessarily a difference in likelihood
of dioxin formation.
Class III - Other chemicals having the possibility, but less likeli-
hood, of dioxin formation. These include i) ortho substituted aromatic
40

-------
compounds requiring an unusual combination of reaction steps to produce
dioxins, 2) aromatic compounds that might form dioxins because of their
production under semicombustion conditions, and 3) products that might
contain dioxins by way of contamination of their starting materials.
Since only commercially significant products are of interest in this
study, the listing is limited to those produced in quantities in excess of
1000 pounds per year and/or whose sales reach $1000 per year, as required
for listing in the SRI Directory of Chemical Producers. The product lists
are based on commercial production during the past 10 years.
Table 5 lists and classifies commercial organic chemicals selected as
having a relationship to dioxin formation or presence. Structures are shown
for Classes I and II, the chemicals of primary importance. Class III com-
pounds are listed by name only.
Most of the organic chemicals considered are used as manufacturing
intermediates or at least are subjected to subsequent formulation or fabri-
cation. Thus further processing may introduce additional possibilities for
dioxin formation, contamination, and exposure not contemplated within the
scope of this study.
The intended reaction mechanisms for each Class I organic chemical are
shown in Figures 1 through 11. The sequence is shown from left to right
across the top of each figure, and the possible dioxin side reaction mech-
anism diverges to typical dioxin byproducts at the bottom of the figure.
The specific dioxin products shown are those for which reasonably straight-
forward mechanisms can be postulated. In many cases more complex and
secondary mechanisms may produce dioxins in addition to those shown.
41

-------
TABLE 5. LIST OF ORGANIC CHEMICALS
Class I
4-BR0M0-2,5-DICHL0R0PHEN0L
OH
CI
CI
Br
2-CHL0R0-4-FLU0R0PHEN0L
OH
CI
DECABROMOPHENOXYBENZENE
2,4-DlBRQMOPHENOL
OH
Br
Br
2,3-D ICHLOROPHENOL
OH
CI
CI
(conti nued)
42

-------
TABLE 5 (continued)
Class I (continued)
2,4-01CHL0R0PHENQL
2,5-01 CHL0R0PHEN0L
2,G-DICHL0R0PHEM0L
OH
CI
CI
OH
CI
CI
CI
OH
tr"
3,4-DICHL0R0PHEN0L
PENTABROMOPHENOL
(conti nued)
OH
CI
CI
OH
Br\^ s^Br
Br
43

-------
TABLE 5 (continued)
Class I (continued)
2,4,6-TRI BROMOPHENOL
2,4,5-TRICHLOROPHENOL
Class II
BROMOPHENETOLE
OH
Br>V'W^'Br
Br
OH
CI
OC2H5
-Br
0-BR0M0PHEN0L
OH
Br
2-CHL0R0-1,4-DIETHOXY-5-NITROBENZENE
5-CHL0R0-2,4-DIMETHOXY-ANILINE
OC2H5
CI
o2n
OC2H5
NH,
VOCH3
CI
OCH,
| continued)
44

-------
TABLE 5 (continued)
Class II (continued)
OH
CI
CHLOROHYDROQUI NONE
OH
OH
, 	-CI
0-CHL0R0PHEN0L
2-CHL0R0-4-PHENYLPHEN0L
4-CHL0R0RES0RCINOL
2,6-01BR0M0-4-NITR0PHEN0L
3,5-01 CHL0R0SALICYLIC ACIO
OH
OH
CI
OH
Brv^A^Br
CI
N02
COOH
lie
(conti nued)
45

-------
TABLE 5 (continued)
Class II (Continued)
OH
2,6-011000-4-NITR0PHEN0L
no2
COOH
OH
3 ,5-DI I0D0SAL1CYLIC ACID
0-FLU0R0ANIS0LE
0-FLU0R0PHEN0L
TETRABR0M0B1SPHENOL -A
TETRACHL0R0BISPHENOL-A
(conti nued)
46
HO
OH
CH
Br
HO


CH

-------
TABLE 5 (continued)
Class III	
3-Amino-5-chloro-2-hydroxybenzenesulfonic acid
2-Amino-4-chloro-6-nilrophenol
o-Anisidine
Benzaldehyde
Bromobenzene
o-Bromofluorobenzene
o-Chlorofluorobenzene
3-Chloro-4-fluoro-nifrobenzene
3-Chloro-4-fluorophenol
4-Chloro-2-nih*ophenol
Chloropentafluorobenzene
2,4-Dibromof I uorobenz ene
3,4-Dichloroaniline
o-Dichlorobenzene
3,4-Dichlorobenzaldehyde
3,4-Dichlorobenzofri chloride
3,4-Dlchlorobenzotri Fluoride
1,2-Dichioro-4-niJrobenzene
(conti nued)
47

-------
TABLE 5 (continued)
Class 111 (continued)	
3,4-Dichlorophenylisocyanate
3.4-D	ifluoroan i I i ne
o-Difluorobenzene
1,2-Dihydroxybenzene-3,5-disulfonic acid, disodium salt
2.5-DihydroxybenzenesuIfonic	acid
2,5-Dihydroxybenzenesulfonic acid, potassium salt
2,4-Dinifrophenol
2.4-D	i n i Irophenoxye thanol
3.5-Dinitrosaiicylic	acid
Fumaric acid
Hexabromobenzene
Hexachlorobenzene
Hexaf I uorobenzene
Maleic acid
Maleic anhydride
o-Nitroanisole
2-N i tro-p-creso!
o-Nitrophenol
(conti nued)
48

-------
TABLE 5 (continued)
Class III (continued)	
Pentabromochlorocyclohexane
Pentabromoethylebenzene
Pentabromotoluene
Pen tachloroani line
Pentafluoroaniline
0-Phenetidine
Phenol (From chlorobenzene)
1-Phenol-2-sulfonic	acid, formaldehyde condensate
Phenyl ether
Phthalic anhydride
Picric acid
Sodium picrate
Tetrabromophthalic anhydride
1,2,4,5-Tetrachlorobenzene
Tetrachlorophthallc anhydride
Tetrafluoro-m-phenylenediamine
Tribromobenzene
1,2,4-Trichlorobenzene
2,4,6-Trinitroresorcinol
49

-------
4—BROMO—2,5-01CHLOROPHENOL

NaOH

+ OTHER
ISOMERS
J,2,4-TRICHLOROBENZENE
2,7-OCOO
2,8-DCOO
2,7—D B—3,8—DCOD
Figure 1. 4-Bromo-215-dichloropheno1
50

-------
2 - CHLORO - 4 - FLUOROPHENOL
OH
OH
NaOCI
NaOH
4 - FLUOROPHENOL

O CI
2,7 - DFOD
Figure 2. 2-Chloro-4-f1uorophenol.
51

-------
DECABROMOPHENOXYBENZENE
NaOH
PENTABROMOPHENOL
Figure 3.
Decabromophenoxybenzene.
52

-------
2,4 - DIBROMOPHENOL
+ OTHER BROMOPHENOLS
-f OTHER BRDMOPHENOXY RADICALS
+ OTHER SROMODIOXINS
2,7-OBDD
Figure 4. 2,4-Dibromophenol
53

-------
©
2, 3-D ICHLOROPHENOL
OH
OH
SO
,2,3-TRICHLOROBENZEHE
O CI
o
2,7 - DCDD
Figure 5. 2,3-Dichlorophenol
54
A

-------
2,4 - DICHIOROPHENQI
OH
PHENOL
CI
CATALYST
OH
CI
4- OTHER ISOMERS
CI
o
CI
CI
+ OTHER CHLOROPHENOXY RADICALS
+ OTHER CHLORODIOXIHS
2,7 - DCDO
Figure 6. 2,4-Dichlorophenol.
55

-------
1,2,4 - TRiCHLOROBENZENE
2,5 - DICHLOROPHENOL
200°C
2,7-DCDD
2,8-DCDD
Figure 7. 2,5-Dichlorophenol.
56

-------
2,6 - DICHLOROPHENOL
OH
CATALYST
PHENOL
+ OTHER ISOMERS
+ OTHER CHLOROPHENOXY RADICALS
CI
o
o
+ OTHER CHLORODI0XINS
CI
1,8 - DCDD
Figure 8. 2,6-Dichlorophenol
57

-------
CI
so3
CI	OH
S°3H JL 0 so3h
ci
h2so4
)e4^0 sc
3,4-DICHLOROPHENOL
OH
CI
1,3,4-TRICHLOROBENZENE
H3PO4
I <
qO
CI ^ § CI^\S03H
CI
so3h
CI
so3h
CI
so3h
CI
h3po4
t
o
o
2,1 - DCDD
CI
Figure 9. 3,4-Dichlorophenol
58

-------
PENUBRQMQPHENQL
OH
Br2 , CATALYST
PHENOL
OBDD
Figure 10. Pentabromophenol
59

-------
2,4,6 - TRIBROMOPHENOL
OH
PHENOL
+ OTHER BROMOPHENOLS
+ OTHER BROMOPHENOXY RADICALS
+ OTHER BROMODIOXINS
2,4,7,9-TB00
Figure 11. 2,4,6-Tribromophenol.
60

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SECTION 6
PESTICIDE CHEMICALS
Pesticides are the most significant group of organic chemicals in
relation to dioxin occurrence. This statement is based on the structure and
reaction mechanism analogy, reaction conditions, detected presence of
dioxins in a number of commercial pesticide products, and a history of
environmental contamination problems, particularly with trichlorophenol and
2,4,5-T.
Chlorinated dibenzo-p-dioxins are known to be present in at least trace
amounts in a number of pesticide chemicals. These include 2,4,5-T, silvex,
2,4-D, erbon, Sesone, DMPA, ronnel, tetradifon, and the various chloro-
phenols (Fishbein 1973). In addition, the chemical structures, reactions,
and process conditions for a number of others indicate dioxin content
potential.
This study deals with production of the basic pesticide chemicals.
Thus it does not address problems of dioxin formation possibly resulting
from formulation, storage, distribution, and utilization of the pesticides.
If exposure to alkaline formulation media or elevated temperatures is
encountered in any of the diverse procedures for handling and use of these
pesticides, dioxin formation could be a significant problem.
SELECTION AND CLASSIFICATION
The pesticide chemicals were selected for evaluation in this study on
the basis of molecular structure, from those listed as commercial pesticides
in the Farm Chemicals Handbook. The primary criterion was an ortho halo-
phenolic structure, or the derivative esters and salts thereof. Also con-
sidered were ortho dihalo aromatic structures, which conceivably could
convert to phenols upon exposure to alkaline conditions.
A second criterion was a minimum commercial production level of 1000
pounds or $1000 value per year. These correspond to the minimum levels
required for inclusion in the Stanford Research Institute Directory of
Chemical Producers, which was a primary reference. The lists are based on
production during the past 10 years.
The pesticide chemicals considered in this study are listed in Table 6.
They are grouped into classes representing likelihood of dioxin formation,
as follows:
61

-------
TABLE 6. LIST OF PESTICIDE CHEMICALS
General name
Chemical name
Class I

Bi fenox
Methyl-5-[2,4-dichloroephenoxy]-2-
ni trobenzoate
Chiorani1
2,3,5)6-Tetrachloro-255-cyclorhexadiene-
1,4-dione
2,4-D and esters and salts
(2,4-Dichlorophenoxy)acetic acid and
esters and salts
2,4-DB and salts
2,4-Dichlorophenoxybutyric acid and
sal ts
Dicamba
3,6-Dichloro-2-methoxybenzoic acid
Dicamba, dimethyl amine salt
3,6-Di chloro-2-methoxybenzoic ac id,
dimethylamine salt
Dicapthon
Phosphorothioic acid o-(2-chloro-4-
nitrophenyl) o,o-dimethyl ester
Dichlofenthion
Phosphorothioic acid o-2,4-dichloro-
phenyl o,o-diakyl ester
Disul sodium (Sesone)
2,4-Dichlorophenoxyethyl sulfate,
sodium salt
2,4-DP
2-[2,4-Dichlorophenoxy] propionic acid
Erbon
2,2-Dichloropropanoic acid 2-(2,4,5-
trichlorophenoxy) ethyl ester
Hexachlorophene
2,2'-Methylene bis (3,4,6-trichlorophenol)
Isobac 20
2,21-Methylene bis (3,4,6-trichlorophenol),
monosodium salt
Nitrofen
2,4-Dichlorophenyl-p-nitorphenyl ether
Pentachlorophenol (PCP)
and salts
Pentachlorophenol and salts
(conti nued)
62

-------
TABLE 6 (continued)
General name
Chemical name
Ronnel
Phosphorothioic acid, o,o-dimethyl
Q-(2,4,5-trichlorophenyl) ester
Silvex and esters and salts
2-(2,4,5-Trichlorophenoxy) propionic
acid and esters and salts
2,4,5-T and esters and salts
(2,4,5-Trichlorophenoxy) acetic acid
2,3,4,6-Tetrachlorophenol
2,4,5-Trichlorophenol
Class II
o-Benzyl-p-chlorophenol
Bromoxynil and esters
3,5-Dibromo-4-hydroxybenzonitri1e
Carbonphenothion
Phosphorodithioic acid s-[[(4-chlorophenyl)
thio]methyl] o,o-diethyl ester
DCPA
2,3,5,6-Tetrachloro-l,4-benzenedi-
carboxylic acid dimethyl ester
Dichlone
2,3-Dichloro-l,4-haphthalenedione
Dinitrobutylphenol,
ammonium salt
2,4-Dinitro-6~sec-butyl phenol,
ammonium salt
Loxyni1
3,5-Di i odo-4-hydroxybenzonitrile
Li ndane
1,2,3,4,5,6-Hexac h1orocyc1o hexane,
gamma isomer
MCPA
(4-Chloro-o-toloxy) acetic acid
MCPB
4-(2-Methyl-4-chlorophenoxy) butyric acid
Mecoprop
2-(4-Chioro-2-methylphenoxy) propionic
acid
Parathion
Phosphorothioic acid o,o-diethyl o-(4-
nitrophenyl) ester
PCNP
Pentachloronitrobenzene
(conti nued)
63

-------
TABLE 6 (continued)
General name
Chemical name
-
Pipecoli nopropy1-3,4-dichlorobenzoate
Piperalin
3-(2-methylpiperidino)propyl-3,4-
dichlorobenzoate
Propanil
3,4-Di chloropropionani1ide
Tetradifon
l,2)4-Trichloro-5-[(4-chlorophenyl)-
sulfonyl] benzene
2,3,6-Trichlorobenzoic acid
2,3,6-Trichlorophenylacetic acid and
sodium salt
Triiodobenzoic acid
64

-------
Class I - Highly likely to be associated with the presence of halogen-
ated dibenzo-p-dioxins because of the presence of an ortho-halogenated
phenol in the reaction sequence, with subjection to elevated tempera-
ture (>145°C+) plus either alkalinity or the presence of free halogen.
Class II - Reasonable but lesser probability of such dioxin association
because of the presence of phenolic or aromatic structures related to
dioxins; although not directly involving dioxin precursive conditions,
such chemicals might form dioxins under irregular operating conditions.
CHEMICAL REACTIONS
Higher chlorinated dioxins have been detected in samples of a number of
pesticides produced from 1950 to 1970. Data from these analyses were
summarized by Fishbein (1973), as shown in Table 7.
Many of the dioxins present differ from those expected on the basis of
the straightforward mechanisms hypothesized. Possible reasons for this may
be that other mechanisms are at work or that substantial disproportionate
is occurring among the dioxins initially formed, as has been suggested by
Dow Chemical (Rawls 1979) and others (Buser 1976).
Reaction mechanisms for the Class I pesticide products are shown in the
following figures. The intended product reaction sequence is from left to
right across the top of each figure, and the possible dioxin side reaction
mechanism diverges to typical dioxin byproducts at the bottom of the figure.
The specific dioxin products shown are those for which reasonably straight-
forward mechanisms can be postulated. In many cases, more complex and
secondary mechanisms may produce dioxins in addition to those shown, as
evidenced by their analytical detection in a number of products (Fishbein
1973).
The initial reaction steps in producing many of the Class I pesticides
are very similar and thus the pesticides are grouped by common mechanism.
Similarity is noted in 2,4,5-T, silvex, ronnel, 2,4-D, erbon, Sesone,
dichlofenthion, dicapthon, bifenox, and dicamba. The final substitution
pattern differs in each case, as does the precise halophenol or chloroben-
zene starting structure.
The first step in production of 2,4,5-T, silvex, ronnel, and erbon is
identical (Figures 12 through 15). Treatment of 1,2,4,5-tetrachlorobenzene
with caustic yields 2,4,5-trichlorophenol. The reaction conditions are
sufficiently drastic, including alkalinity and elevated temperature, to
cause formation of the orketocarbene, which reacts with the chlorophenylate
to give the predioxin, which then reacts to yield 2,3,7,8-TCDD. Continued
alkaline processing, which occurs with each of these product items, also
contributes to the same transient intermediates and consequently to forma-
tion of 2,3,7,8-TCDD.

-------
TABLE 7. HIGHER CHLORINATED DIOXINS FOUND IN COMMERCIAL PESTICIDES3
Pesticide
Chiorodibenzo-p-dioxi n
detected
Sample
Number
contami nated
Number
tested
Tetra-
Hexa-
Hepta-
Octa-
Phenoxyalkanoates






2,4,5-T
++
++
-
-
23
42
Si 1 vex
+
-
-
-
1
7
2,4-D
-
+
-
-
1
24
Erbon
-
-
-
++
1
1
Sesone
-
+
-
-
1
1
Chlorophenols






Tri-
-
+
+
+
4
6
Tetra-
-
++
++
++
3
3
Penta-(PCP)
-
++
++
++
10
11
Others0
-
++
++
+
5
22
* Fishbein, 1973.
concentration range: ++ = >10 ppm
+= 0.5 to 10 ppm
-=<0.5 ppm
DMPA, ronnel, and tetradifon were found to contain chlorodioxin contamination.
66

-------
2,4.5-T
.CI
NaOH
C!
1,2,4,5-TETRA-
CHLDRO BENZENE
COOH
NaOH
2,3,7,8-TCDD
ESTERS
MINE
SALTS
Figure 12, 2,4,5-Trichlorophenol, 2»4,5-T and esters and salts
67

-------
SILVEX
COOH
/M 1 A 1 I
Uri3 On
bo^ esters
2 AMINE
SALTS
NaOH
NaOH
cich2co2h
,2,4, 5-TETRA-
CHL0R08ENIEHE
2,4,5-TRiCHLOROPHENOL
G?Na©
CI
/~~\Na@
UOCI
o ^ -Cl
2,3,7,8-TC00
Figure 13, Silvex and esters and salts.
68

-------
2,4,5-TRl-
CHLOROPHENOL
RONNEL
OoNa©
S* ,CI	SNyOCH3
o'Pnci	o' soch3
CI	CI
NaOH
CI
1,2,4.5-TETRA-
CHLQROBENZENE
2,3,7,8-TCDD
Figure 14. Ronnel.
69

-------
(DiSUL SODIUM) SESONE
X=H O	O
OC2H4OS-OH OC2H4OS-ONa
CI 8 1 CI o
9 CH 2CH2O-C-CCI2CH3
CI
ERBON
1 /-V^v
CHS>
OONa© O
^ 1 CI / \
CH2-CH2
NaOH
X=H or CI
X=CI
2,3,7,8-TCDD
2,J-QCOD
Figure 15. Erbon and Sesone.
70

-------
The normal reaction sequences for 2,4-D, 2,4-DB, 2,4-DP, disul sodium
(Sesone), dichlofenthion, bifenox, and nitrofen (sequences shown in Figures
15 through 21) are analogous in their early steps to those of 2,4,5-T and
others in the group just described, but occur via 2,4-dichlorophenol rather
than 2,4,5-trichlorophenol. The dioxin formation sequence is likewise
analogous but typically would produce 2,7-DCDD.
Note that the reaction mechanism for disul sodium is presented in the
same figure (Figure 15) with that for erbon. This placement is not meant to
imply that they are co-products, but rather is intended to demonstrate the
analogous reaction patterns of typical pesticides differing as to halogena-
tion and substitutions. Similar analogies can be drawn among nearly all of
the pesticide chemicals studied.
Another point, important to dioxin formation, is demonstrated in Figure
16, showing the reaction for 2,4-D. The reaction sequence conventionally
cited is chlorination of phenol to 2,4-dichlorophenol, followed by reaction
with chloroacetic acid in the presence of caustic to produce 2,4-D. This
last step with the dichlorophenol under alkaline conditions can result in
dioxin formation. An alternative process sequence cited in the patent
literature (Manske 1949) reverses the order of chlorination, as shown in the
upper tier reaction of Figure 16. This sequence would be expected to reduce
the likelihood of dioxin formation. A commercially feasible yield in excess
of 80 percent is noted, but the extent of commercial utilization is not
known. This reaction sequence could possibly be adapted to other dihalogen-
ated phenoxyalkanoates, with an expected reduction in dioxin formation.
Dicamba (Figure 22) with its dimethylamine salt presents one of the
more complex dioxin derivation patterns because of the continued alkaline
conditions under which various substitutions are made. First, preparation
of 2,5-dichlorophenol and its subsequent further exposure to caustic results
in transient intermediates and predioxins that form 2,7-DCDD and 2,8-DCDD.
In addition, similar alkaline processing of the carboxyl and methyl substi-
tuted forms can result in variously substituted dioxins, only two of which,
for simplicity, are shown in Figure 22.
Pentachlorophenol (PCP), a commercially high-volume chemical, can be
manufactured by two basic methods. One involves direct chlorination of
phenol (Figure 23) in the presence of an A1C13 catalyst. The presence of
normal excess chlorine is conducive to formation of a free-radical interme-
diate, then of the predioxin, and ultimately of OCDD. The alternative
process based on caustic treatment of hexachlorobenzene (Figure 24) produces
chlorinated transient intermediates analogous to the 2,4,5-T series but
fully chlorine substituted. These in turn form the predioxin and finally
OCDD.
The complex free-radical mechanism by which chloranil is made (Figure
25) results in transient intermediates similar to those occurring as by-
product derivatives of PCP. Therefore, OCDD should be expected as a dioxin
contaminant.
71

-------
PHENOL
OH
PHENOXtACETIC AGIO
och2cooh
NaOH
CI CH2COOH
CI,
OH
ffl* NaOH
CICHaCOOH
OCH2COONa
¦Cl H©
CI
2,4-01CHL0R0PHEN0L
2,4- 0
OCH2COOH
CI	ESTERS
^^^AMINE
SALTS
0ONa©
CI
2.7-0COO
Figure 16. 2,4-D and esters and salts.
72

-------
2,4-DB
OH
ONa
PI
NaQH r
50-200°C
CI
2,4-OlCHlOROPHENOL
CH2CH2CH2COOH
? CI +^2^ ESTERS
~-2^amine
salts
0?Na©
r-)Na©
Uo ct
:crci
2,7 - OCDO
Figure 17. 2,4-DB.
73

-------
2,4 - DP
OH
CI
CI
I
H
I
CH3-C-C02H
O
NaOH , CH3CH - C02H
CI
2,4 - DICHLOROPHENOL
CI
2,7 - DCOD
Figure 18. 2,4-DP.
74

-------
CI
NaOH
OoNa©
CI
Sv OR
cr^oR
DICAPTHOK (X=N0,)
Of
DICHLOFENTHIGN (X=C!)
xO R
O vOR
G?Na©
CI


(X=N02)
2,7-ONDD
Figure 19. Dicapthon arid Dichlofenthion.
75

-------
BIFENOX
COOR
COOR
M = Na. K
X = CI. Br
R = H or MkvI
©
2,7-OCDD
Figure 20. Bifenox.
76

-------
NITROFEN
OH
CI
CI
+
©
OH,Cu
^ 200s?:
CI	no2
2,4-01CHLOROPHENOL CHL0R0-4-N1TROPHEHOL
»- cih^ Vo-^y
2,7-DCDO
Figure 21. Nitrofen.
77

-------
1,2,4-TRICHL0R0BEHZENE 2,5-OICHlOROPHEHOL
D1CAMBA
C02
140°C
200 C
COOH
COOH
CI ©
coT0
CI ' w
2,8-DCuu
2,7-DC00
Figure 22. Dicamba.
78

-------
PENTACHLOROPHENOL(PCP)
PCP, Na SALT

ONa
l


-~
f T
CI
Sf CI

CI
1 I
NaOH
PHENOL
OCDD
Figure 23. Pentachlorophenol (PCP) via phenol
79

-------
PENTACHLCROPHENOL (PCP)
0©

NaOH
HEXACHLOROBENZENE
(+)Na
CI QW CI
Figure 24. Pentachlorophenol (PCP) via hexachlorobenzene.
30

-------
(
CHLORANIL
REACTION VIA COMPLEX \
FREE RADICAL MECHANISM )
HCI , 02
220- 260°C
BENZENE
Clvvx^x^CI
~ TY
Cl-^Y^CI
ocoo
Figure 25. Chloranil.
81

-------
Hexachlorophene and its sodium salt, Isobac 20, (Figure 26), are pro-
duced from 2,4,5-trichlorophenol whose preliminary production from 1,2,4,5-
tetrachlorobenzene is carried out by reaction with caustic. This first step
potentially forms dioxin precursors similar to the equivalent step in the
manufacture of 2,4,5-T. Consequently, 2,3,7,8-TCDD is the anticipated
byproduct dioxin.
The production of 2,3,4,6-tetracnlorophenol (Figure 27) by chlorination
of phenol would be expected to yield trace byproducts of various isomeric
hexachlorodibenzo-p-dioxins via a free-radical mechanism.
Again, because of the analytical evidence of many dioxins other than
those hypothesized in these mechanisms, no specific dioxin presence should
be presumed or excluded.
As an indication of the critical processing that might precede the
reactions shown in this section, Table 8 summarizes the primary raw mate-
rials. Those materials potentially carrying trace dioxins are reviewed in
Section 5.
82

-------
HEXACHLOROPHENE
ISOBAC 20
NaOH
NaOH
CHLOROBEHZENE

2,3,7,8-TCDD
Figure 26. Hexachlorophene and Isobac 20.
83

-------
2,3,4,6 - TETRACHLOROPHENOL
Cl2 , CATALYST
+ OTHER CHLOROPHENOLS
+ OTHER CHLOROPHENOXY RADICALS
CI	CI	CI	CI	CI
?' cvWo
CI CI
o-^ci ciV~0
CI
CI
HEXA-CDD'S
Figure 27. 2,3,4,6-Tetrachlorophenol.
84

-------
2,4,5-TRl-
CHLORQPHENOL
ROHNEL
©ONa©
% /CI
o'KCl
S^OCH3
° OCHo
CI
NaQH
Na OCH3
»
CI
1,2,4,5-TETRA
CHLuRQBENZENE
2,3,1,8-TCDO
Figure 14. Ronnel.
69

-------
(QISUL SODIUM) SESONE
X=H O	O
H	H
OC2H4OS-OH OC2H4OS-ONa
O CH2CH2O-C-CCI2CH3
NaOH
OiONa© O
CI/ \
CH2-CH2
NaOH
X = CI
X =H or CI
X = H
2.7-0C00
X=CI
2,3,7,8-TCOD
Figure 15. Erbon and Sesone.
70

-------
The normal reaction sequences for 2,4-D, 2,4-DB, 2,4-DP, disul sodium
(Sesone), dichlofenthion, bifenox, and nitrofen (sequences shown in Figures
15 through 21) are analogous in their early steps to those of 2,4,5-T and
others in the group just described, but occur via 2,4-dichlorophenol rather
than 2,4,5-trichlorophenol. The dioxin formation sequence is likewise
analogous but typically would produce 2,7-DCDD.
Note that the reaction mechanism for disul sodium is presented in the
same figure (Figure 15) with that for erbon. This placement is not meant to
imply that they are co-products, but rather is intended to demonstrate the
analogous reaction patterns of typical pesticides differing as to halogena-
tion and substitutions. Similar analogies can be drawn among nearly all of
the pesticide chemicals studied.
Another point, important to dioxin formation, is demonstrated in Figure
16, showing the reaction for 2,4-D. The reaction sequence conventionally
cited is chlorination of phenol to 2,4-dichlorophenol, followed by reaction
with chloroacetic acid in the presence of caustic to produce 2,4-D. This
last step with the dichlorophenol under alkaline conditions can result in
dioxin formation. An alternative process sequence cited in the patent
literature (Manske 1949) reverses the order of chlorination, as shown in the
upper tier reaction of Figure 16. This sequence would be expected to reduce
the likelihood of dioxin formation. A commercially feasible yield in excess
of 80 percent is noted, but the extent of commercial utilization is not
known. This reaction sequence could possibly be adapted to other dihalogen-
ated phenoxyalkanoates, with an expected reduction in dioxin formation.
Dicamba (Figure 22) with its dimethyl amine salt presents one of the
more complex dioxin derivation patterns because of the continued alkaline
conditions under which various substitutions are made. First, preparation
of 2,5-dichlorophenol and its subsequent further exposure to caustic results
in transient intermediates and predioxins that form 2,7-DCDD and 2,8-DCDD.
In addition, similar alkaline processing of the carboxyl and methyl substi-
tuted forms can result in variously substituted dioxins, only two of which,
for simplicity, are shown in Figure 22.
Pentachlorophenol (PCP), a commercially high-volume chemical, can be
manufactured by two basic methods. One involves direct chlorination of
phenol (Figure 23) in the presence of an A1C13 catalyst. The presence of
normal excess chlorine is conducive to formation of a free-radical interme-
diate, then of the predioxin, and ultimately of OCDD. The alternative
process based on caustic treatment of hexachlorobenzene (Figure 24) produces
chlorinated transient intermediates analogous to the 2,4,5-T series but
fully chlorine substituted. These in turn form the predioxin and finally
OCDD.
The complex free-radical mechanism by which chloranil is made (Figure
25) results in transient intermediates similar to those occurring as by-
product derivatives of PCP. Therefore, OCDD should be expected as a dioxin
contami nant.
71

-------
och2cooh
CI ch2cooh
2,4- B

\ J i5^tk^AWiN|
o\
tsjaOH
cicfficoon
Cl
CHlOROPHtHOl
, i-OCOO
c?ci ~ -cl
Figure
16. 2,
4-0 and esters
and salts.
72

-------
2,4-OB
CH2CH2CH2 COOH
Ci
2,4-DICHLOROPHENOL
ESTERS
2 AMINE
SALTS
NaOH
50-200 C
0?Na©
©Na©
OCI
CI
CI
2,7 - ocoo
Figure 17. 2,4-DB.
73

-------
2,4 - DP
H
I
CH3-C-C02H
NaOH , CH3 CH
2,4 - QICHLOROPHENOL
2,7 - DCDO
Figure 18. 2,4-DP.
74

-------
OH
,CI
NaOH
©ONa© -
D1CAFTH0N (X=N02)
DICHLOFEHTHI ON (X=C1)
~ ~OR
° 0?Na©
Ci
(x=no2j
0,N-^S^ O
2,7-DNDD
Figure 19. Dicapthon and Diehlofenthion.
75

-------
BIFENOX
COOR
COOR
M = Na, K
X = CI, Br
R = H or Mkvl
©
2,7-DCDD
Figure 20. Bifenox.
76

-------
NtTROFEN
CI	no2
2,4-DICHtOROPHENOL CHL0R0-4-NITROPHENOL
OH.Cu
200 C
2,7-DCDD
Figure 21. Nitrofen.
77

-------
1,2, 4-TRICHLOROBENZENE 2,5-01CHLOROPHENOL
0ICAMBA
C!
. x ci (3)
OH
200 C
COOH
COOH
140°C
2,8-OCDD
2,7-DCuD
XX
Figure 22. Dicamba.
78

-------
PENTACHLOROPHENOL(PCP)
PCP, Na SALT

OH
*
ck
A
~

CI
y

CI

ONa
°s


o
CI


CI
NaOH
PHENOL
OCDD
Figure 23. Pentachloropheriol (PCP) via phenol
79

-------
PENTACHLOROPHBUL (PCP)
0©
ONa
OH
01 NaOH Cl
HEXICHLORQBENZENE
©Na
Cl© CI
ck^A^ oci^X .ci
ci ci
OGOD
Figure 24. Pentachlorophenol (PCP) via hexachlorobenzene.

-------
(
REACTION VIA COMPLEX \
FREE RADICAL MECHANISM /
HCI , 02
220- 260°C
CHLORANIL
o
ivV
BENZENE
V
OCDD
Figure 25. Chloranil.
81

-------
Hexachlorophene and its sodium salt, Isobac 20, (Figure 26), are pro-
duced from 2,4,5-trichlorophenol whose preliminary production from 1,2,4,5-
tetrachlorobenzene is carried out by reaction with caustic. This first step
potentially forms dioxin precursors similar to the equivalent step in the
manufacture of 2,4,5-T. Consequently, 2,3,7,8-TCDD is the anticipated
byproduct dioxin.
The production of 2,3,4,6-tetrachlorophenol (Figure 27) by chlorination
of phenol would be expected to yield trace byproducts of various isomeric
hexachlorodibenzo-p-dioxins via a free-radical mechanism.
Again, because of the analytical evidence of many dioxins other than
those hypothesized in these mechanisms, no specific dioxin presence should
be presumed or excluded.
As an indication of the critical processing that might precede the
reactions shown in this section, Table 8 summarizes the primary raw mate-
rials. Those materials potentially carrying trace dioxins are reviewed in
Section 5.
82

-------
HEXACHLOROPHENE
ISOBAC 20
©Na©
OH
OH
OH
OH
NaOH
NaOH
CI CI
1,2,4,5-TETRA-
CHLOROBENZENE
O CI
2,3,7,8-TC00
Figure 26. Hexachlorophene and Isobac 20.
83

-------
2,3,4,6 - TETRACHLOROPHENOL
+ OTHER CHLOROPHEHOLS
CI
CI
Cl2 , CATALYST
PHENOL
+ OTHER CHLOROPHENOXY RADICALS
CI CI
CI
HEXA-CDD'S
Figure 27. 2,3,4,6-Tetrachlorophenol
84

-------
TABLE 8. PESTICIDE RAW MATERIALS
Pesticide product
Raw materials
Bi fenox
2,4-Dichlorophenol
3-Halo-o-nitrobenzoic acid ester
NaOH
Chiorani1
Benzene
Hydrogen chloride
Oxygen
2,4-D and esters and salts
Phenol
Chloroacetic acid
NaOH
Cl2
Alcohols (for esters)
Amines (for amine salts)
2,4-DB and salts
Phenol
Cl2
NaOH
Butyrolactone
Alcohols (for esters)
Amines (for amine salts)
Di camba
1,2,4-Trichlorobenzene
NaOH
C02
Dimethyl sulfate
Di capthon
2-Chloro-4-nitorphenol
NaOH
Chlorodimethylthi ophosphonate
Dichlofention
2,4-Di chlorophenol
NaOH
Chlorodimethylthi ophosphonate
Disul Dodium (Sesone)
2,4-Di chlorophenol
NaOH
Ethylene oxide
Chlorosulfonic acid
2,4-DP
2,4-Di chlorophenol
2-Chloropropionic acid
NaOH
(continued)
85

-------
TABLE 8 (continued)
Pesticide product
Raw materials
Erbon
1,2,4,5-Tetrachlorobenzene
NaOH
Ethylene oxide
2,2-Dichloropropionic acid
Hexachlorophene arid Isobac 20
1,2,4,5-Tetrachlorobenzene
NaOH
Ethylene oxide
Ni trofen
2,4-Dichlorophenol
Chloro-4~ni trobenzene
KOH
Pentachlorophenol PCP
Phenol
Cl2 (Phenol route)
or
Benzene
CI 2 (Hexachlorobenzene
NaOH route)
Ronnel
1,2,4,5-Tetrachlorobenzene
NaOH
Phosphorus sulfochloride
NaOCH3
Si 1 vex and esters and salts
1,2,4,5-Tetrachlorobenzene
NaOH
Chloropropionic acid
Alcohols (for esters)
Amines (for amine and salts)
2,4,5-T and esters and salts
1,2,4,5-Tetrachlorobenzene
NaOH
Chloracetic acid
Alcohols (for esters)
Amines (for amine salts)
2,3,4,6-Tetrachlorophenol
Phenol
Cl2
2,4,5-Tri chlorophenol
1,2,4,5-Tetrachlorobenzene
NaOH
86

-------
SECTION 7
CHEMICALS, PRODUCERS, AND PLANT LOCATIONS
The tables that follow list organic chemicals and pesticides selected
for study on the basis of potential dioxin contamination, with known produc-
ers and production locations, present and past. The primary source of
producer information is the SRI Directory of Chemical Producers. The tabu-
lations are by chemical, with producers and locations; and by producer and
location, with chemicals. The tabulations by chemical (Tables 9, 10, 11,
and 14) are segregated according to the classifications based on dioxin
concern as defined in Section 5 (Organic Chemicals) and Section 6 (Pesticide
Chemicals), respectively. The classification information is also noted in
the producer location tables by means of Roman numerals following the chemi-
cal names.
The tabulations by producer and location (Tables 12 and 15) group all
of the critical chemicals involved at each manufacturer location. These
lists do not necessarily define the site subject to exposure, because many
dumps are remote from the plants; they do provide a starting point for such
definition. Abandoned production of a chemical or abandoned facilities may
present special problems. Therefore, the production facilities noted since
1968 but no longer active in 1978 are footnoted and are also extracted in
separate tables (Tables 13 and 16). Some of these sites remain active in
other production, and some may retain production capability and/or minor
production of the subject chemical. Other plant sites may be totally
deactivated or abandoned. The producer listed is the last known operator.
Some of the company names of producers designate subsidiary or divi-
sional names, with notation of the parent company. The underlined portion
of the name indicates the short-form name used in other tables. Company
addresses, from the SRI Directory and from the Thomas Register, are for the
last known producer at a given location and are subject to the uncertainties
introduced by acquisitions and name changes.
87

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TABLE 9. PRODUCERS OF CLASS I ORGANIC CHEMICALS
Chemical
Producer
Location
4-Bromo-2,5-dichlorphenol
Velsicol
Beaumont, Tex.
2-Chloro-4-f1uorophenol
01 in
Rochester, N. Y.
Decabromophenoxybenzene
Great Lakes Chem.
El Dorado, Ark.
2,4-Dibromophenol
Dow
White Chem.
Midland, Mich.
Bayonne, N. J.
2,3-D ichlorophenol
Specialty Organics
A1drich
Diamond Shamrock
Irwindale, Cal.
* ^
Milwaukee, Wis.
Neward, N, J.3
2 ,4-Dichlorophenol
Dow
Monsanto
Rhodia
Transvaal
Midland, Mich.
Sauget, 111.
Freeport, Tex.
Jacksonville, Ark.
2,5-D ichlorophenol
Velsicol
Beaumont, Tex.
2,6-Dichlorophenol
A1dri ch
Specialty Organics
Milwaukee, Wis.
Irwindale, Cal.
3,4-Dichlorophenol
Aldrich
Milwaukee, Wis.
Pentabromophenol
Michigan Chem.
R. S. A.
White Chem.
St. Louis, Mich.3
Ardsley, N. Y.3
Bayonne, N. J.
2,4,6-Tribromophenol
Dow
Eastern Chem.
Guardi an
Velsicol
R.S.A.
White Chem.
Midland, Mich.3
3
Pequannock, N. J.
Hauppauge, N. Y.
Pequannock, N. J.
St. Louis, Mich.3
Ardsley, N. Y.a
Bayonne, N. J.
a No longer produced at this location.
88

-------
TABLE 10. PRODUCERS OF CLASS II ORGANIC CHEMICALS
Chemical
Producer
Location
Bromophenetole
R.S.A.
Ardsley, N. Y.
o-Bromophenol
Eastman Kodak
R.S.A.
Rochester, N. Y.
Ardsley, N. Y.
2-Chloro~l,4-diethoxy-
5-nitrobenzene
Fairmount Chem.
GAF
Pfister
Newark, N. J.
Rensselaer, N. Y.
Newark, N. J.
5-Ch1oro-2,4-dimethoxy-
ani1i ne
GAF
Pfister
Rensselaer, N. Y.
Ri'dgefield, N. J.
Newark, N. J.
Chiorohydroqui none
Eastman Kodak
Eastern Chem.
Guardian
Rochester, N. Y.
Pequannock, N.
Hauppauge, N. Y.
Pequannock, N. J.
o-Chlorophenol
Dow
Monsanto
Midland, Mich.
Sauget, 111.
2-Chloro-4-phenylphenol
Dow
Midland, Mich.
4-Chlororesorci nol
Am. Color & Chem.
GAF
Lock Haven, Pa.
Rensselaer, N. Y.
2,6-Dibromo-4-nitro-pheno1
Martin Marietta
Maumee
Sherwin Williams
Sodyeco, N. C.a
St. Bernard, Ohio
St. Bernard, Ohio3
3,5-Dichlorosalicy!ic acid
Aceto
Inmont Corp.
Carlstadt, N. J.
Carlstadt, N. J.
2,6-Di iodo-4-ni trophenol
R.S.A.
Ardsley, N. Y.
3,5-Diiodosalicy!ic acid
Morton Chem.
R.S.A.
Ringwood, 111.3
Ardsley, N. Y.a
o-Fluoroani sole
01 in
Rochester, N. Y.
o-Fluorophenol
01 in
Rochester, N. Y.
Tetrabromobisphenol-A
Dow
Great Lakes
Velsicol
Midland, Mich.
El Dorado, Ark.
St. Louis, Mich.
Tetrachlorobi sphenol-A
Dover
Dover, Ohio3
a No longer produced at this location.

-------
TABLE 11. PRODUCERS OF CLASS III ORGANIC CHEMICALS
Chemical
Producer
Location
3-Amino-5-chloro-2-
hydroxybenzenesulfonic
acid
Allied
Nyanza
Toms River Chem.
Buffalo, N. Y.a
Ashland, Mass.
Toms River, N. J.
2-Ami no-4-chloro-6-
nitrophenol
Nyanza
Ashland, Mass.
o-Am'sidi ne
Am. Color and Chem.
Am. Aniline
du Pont
Monsanto
Lock Haven, Pa.
Lock Haven, Pa.
Deepwater, N. J.
St. Louis, Mo.
Benzaldehyde
Crompton and Knowles
Dow
Fritzsche
Kalama Chem.
Monroe Chem.
F. Ritter
Stauffer
Tenneco
UOP
Velsicol
Fair Lawn, N. J.
Kalama, Wash.3
Clifton, N. J.3
Kalama, Wash.
Eddystone, Pa.
Los Angeles, Cal.
Edison, N. J.
Nixon, N. J.
Fords, N. J.3
Garfield, N. J.
East Rutherford, N. J.
r?
Chattanooga, Tenn.
Bromobenzene
Dow
Velsi col
Midland, Mich.
St. Louis, Mich.
o-Bromof1uorobenzene
Olin
Rochester, N. Y.
o-Chlorof1urobenzene
01 in
Rochester, N. Y.
3-Chloro-4~f1uoro-nitro-
benzene
Olin
Rochester, N. Y.
3-Chloro-4-f1uorophenol
Olin
Rochester, N. Y.
4-Chloro-2-nitorphenol
du Pont
Maumee
Sherwin Williams
Deepwater, N. J.a
St. Bernard, Ohio
St. Bernard, Ohio
Chioropentafluorobenzene
Whi ttaker
g
San Diego, Cal.
2,4-Dibromofluorobenzene
Olin
Rochester, N. Y.
(continued)
90

-------
TABLE 11 (continued)
Chemi cal
Producer
Location
3,4-Dichloroani1i ne
Blue Spruce
Bound Brook, N. J.


3
Edison, N. J.

Chem. Insecticide
Metuchen, N. J.

du Pont
Deepwater, N. J.

Martin Marietta
Sodyeco, N. C.a

Monsanto
Luling, La.


Sauget, 111.3
o-Dichlorobenzene
A11i ed
Syracuse, N. Y.a

Chem. Products
Cartersvi11e, Ga.

Dover
Dover, Ohio

Dow
Midland, Mich.

du Pont
Deepwater, N. J.

Hooker
Niagara Falls, N. Y.3

Monsanto
Sauget, 111.

Montrose Chem.
Henderson, Nev.

Neville Chem.
Sante Fe Springs, Cal.c

01 in
Mcintosh, Ala.

PPG
Natrium, W. Va.

Solvent Chem.
Niagara Falls^ N. Y.


Maiden, Mass.

Speciality Organics
Irwindale, Cal.

Standard Chlorine
Delaware City, Del.


Kearny, N. J.
3,4-Dichlorobenzaldehyde
Tenneco
Fords, N. J.
3,4-Dichlorobenzotrichloride
Tenneco
Fords, N. J.
3,4-Dichlorobenzotri f1uoride
Tenneco
Fords, N. J.a
1,2-Di chloro-4-nitrobenzene
Blue Spruce
Bound Brook, N. J.
a


Edison, N. J.

Chem. Insecticide
Metuchen, N. J.

Martin Marietta
Sodyeco, N. C.a

Monsanto
Sauget, 1113

PIasti fax
Gulfport, Miss.
3,4-Dichlorophenylisocyanate
Mobay Chem.
New Martinsville, S. C
^ *

Ott Chem.
Muskegon, Mich.
3,4-Di f1uoroani1i ne
01 i n
Rochester, N. Y.
(conti nued)
91

-------
TABLE 11 (continued)
Chemi cal
Producer
Locati on
o-Di f1uorobenzene
01 in
Rochester, N. Y.
1,2-Di hydroxybenzene-3,5-
Sterling Drug
New York, N. Y.a
disulfonic acid,


disodium salt


2,5-Di hydroxybenzenesulfonic
Eastman Kodak
Rochester, N. Y.a
aci d
Nease Chem.
State Col 1ege, Pa.
2,5-Dihydroxybenzenesulfonic
Nease Chem.
State College, Pa.a
acid, potassium salt


2,4-Dini trophenol
Martin Marietta
Sodyeco, N. C.

Mobay
Bushy Park, S. C.
2,4-Di nitrophenoxyethanol
Hummel Chem.
Neward, N. J. 3


South Plainfield, N. J.
3,5-Dinitrosalicy! ic acid
Eastman Kodak
Rochester, N. Y.

Hummel Chem.
Newark, N. J.3


South Plainfield, N. J.

Salsbury Labs
Charles City, Iowa
Fumaric acid
AT 1ied
Buffalo, N. Y.a


Moundsville, W. Va.

Alberta Gas
Duluth, Minn.

Hooker
Arecibo, P. R.

Monsanto
St. Louis, Mo.

Petro-Tex
d
Houston, Tex.

Pfi zer
Terre Haute, Ind.

Rei chhold
' ^
Morris, 111.

Stepan Chem.
Fieldsboro, N. J.

Tenneco
Garfield, N. J.

U. S. Steel
Neville Island, Pa.
Hexabromobenzene
Vels icol
St. Louis, Mich.

Dover
Dover, Ohio
Hexachlorobenzene
Hummel Chem.
Neward, N. J.3


South Plainfield, N. J.

Stauffer
^ '
Louisville, Ky.
(conti nued)
92

-------
TABLE 11 (continued)
Chemical
Producer
Locati on
Hexaf1uorobenzene
PCR
Whittaker
Gainesville, Fla.
San Diego, Cal.
Louisville, Ky.
Maleic acid
A1 1ied
Eastman Kodak
Pfanstiehl Labs
Buffalo, N. Y.a
Marcus Hook, Pa.
Moundsville, W. Va.a
Rochester, N. Y.
Waukegan, 111.
Maleic anhydride
Allied
Amoco
As 1 and
Chevron
Koppers
Petro-Tex
Monsanto
Rei chhold
Standard Oil of Ind.
(see Amoco above)
Tenneco
U.S. Steel
Moundsville, W. Va.a
Joilet, 111.
Neal , W. Va.
Richmond, Cal.
Bridgeville, Pa.
Cicero, 111.
Houston, Tex.
St. Louis, Mo.
Elizabeth, N. J.
Morris, 111.
Fords, N. J.
Neville Island, Pa.
o-Nitroani sole
du Pont
Monsanto
Deepwater, J.
Sauget, 111.
St. Louis, Mo.
2-Nitro-p-cresol
Sherwi n Wi11iams
du Pont
Chicago, 111.
Deepwater, N. J.
o-Ni trophenol
Monsanto
du Pont
Sauget, 111.
Deepwater, N. J.
Pentabromochloro-
cyclohexane
Dow
Midland, Mich.
Pentabromoethyle-
benzene
Hexcel
Sayreville, N. J.
Pentabromotoluene
White Chem.
Bayonne, N. J.
(conti nued)
93

-------
TABLE 11 (continued)
Chemi cal
Producer
Location
Pentachloroani1i ne
01 i n
Rochester, N. Y.
Pentaf1uoroani1i ne
Whi ttaker
San Diego, Cal.a
o-Phenetidi ne
Am. Aniline
Lock Haven, Pa.a

Monsanto
cl
St. Louis, Mo.
Phenol (from chlorobenzene)
Dow
Midland, Mich.3

Hooker
North Tonawanda, N. Y.c
' a


South Shore, K^.

Union Carbide
Marietta, Ohio
l-Phenol-2-sulfonic acid,
A11i ed
Buffalo, N. Y.
formaldehyde condensate
Diamond Shamrock
Cedartown, Ga.

Rohm and Haas
Philadelphia, Pa.
Phenyl ether
Dow
Midland, Mich.

Fri tzsche
Clifton, N. J.

Monsanto
Chocolate Bayou, Tex.
Phthalic anhydride
A11i ed
Buffalo, N. Y.a


3
Chicago, 111.


El Segundo, Cal.


Frankford, Pa.


Ironton, Ohio

BASF Wyandotte
Kearny, N. J.

Chevron
Perth Amboy, N. J.


Richmond, Cal.
» 3

Commonwealth Oil
Penuelas, P. R.

Conoco
Hebronville, Mass.

Exxon
Baton Rouge, La.

W. R. Grace
Fords, N. J.a

Hooker
Arecibo, P. R.

Koppers
Bridgeville, Pa.


Chicago, 111.


Ci cero, 111.

Monsanto
Bridgeport, N. J.


Chocolate Bayou, Tex.


St. Louis, Mo.


Texas City, Tex.

Reichhold
Azusa, Cal.


Elizabeth, N. J.


Morris, 111.3

Sherwi n Wi11i ams
Chicago, 111.3
(conti nued)
94

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TABLE 11 (continued)
Chemi cal
Producer
Location
Phthalic anhydride
(conti nued)
Picric acid
Sodium pi crate
Tetrabromophthalic
anhydride
1,2,4,5-Tetrachlorobenzene
Tetrachlorophthali c
anhydri de
Tetraf1uoro-m-phenylene-
diami ne
Tri bromobenzene
1,2,4-Trichlorobenzene
Stand. Oil Co. Cal
(see Chevron)
Stepan Chem.
Union Carbide
U.S. Steel
Witco Chem.
Allied
du Pont
Hummel Chem.
Martin Marietta
Hummel Chem.
Martin Marietta
Northrop
Velsicol
Dover
Dow
Hooker
Solvent Chem.
Standard Chlorine
Hooker
Monsanto
Whittaker
Velsi col
Northrop
Chris Craft
Dover
Dow
Hooker
Neville Chem.
Sobin Chems.
Solvent Chem.
Standard Chlorine
Sun Chem.
Elwood, 111.
Millsdale, 1113
Institute, W. Va.a
South Charleston, S. C.'
Neville Island, Pa.
Chicago, 111.
Perth Amboy, N. J.a
Buffalo, N. Ya
*	a
Deepwater, N. J.
South Plainfield, N. J.
Sodyeco, N. C.
South Plainfield, N. J.
Sodyeco, N. C.a
Asheville, N. C.
St. Louis, Mich.
Dover, Ohio
Midland, Mich.
Niagara Falls^ N. Y.
Maiden, Mass.
Delaware City, Del.
Niagara Falls, N. Y.
Bridgeport, N. J.
San Diego, Cal. a
St. Louis, Mich.'
Asheville, N. C.
Newark, N. J.
Dover, Ohio
Midland, Mich.
Niagara Falls, N. Y.3
Sante Fe Springs, Cal.
Neward, N. J.a
Maiden, Mass.
Delaware City. Del.
Kearny, N. J.
Chester, S. C.a
(conti nued)
95

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TABLE 11 (continued)
Chemi cal
Producer
Locati on
2,4,6-Tri ni troresorci nol
Northrop
Asheville, N. C.

01 in
East A1ton, 111.
^ No longer produced at this
location.

Possibly two plants.


96

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TABLE 12. ALPHABETICAL LIST OF ORGANIC CHEMICAL PRODUCERS
Producer
Locati on
Chemical (class)
Aceto Chem. Co., Inc.
126-02 Northern Blvd.
Flushing, N. Y. 11368
Arsynco, Inc. Subsid.
Carlstadt, N. J.
3,5-Dichlorosalicyl ic
acid (II)
Alberta Gas Chems. Inc.
Address not available
Duluth, Minn.
Fumaric acid (III)
Aldrich Chem. Co., Inc.
940 West St. Paul Ave.
Milwaukee, Wis. 53233
Milwaukee, Wis.
2,4-Dichlorophenol (I)a
2,6-Dichlorophenol (I)
3,4-Dichlorophenol (I)
A11ied Chem. Corp.
Columbian Rd. and Park Ave.
Morristown, N. J. 07960
Buffalo, N. Y.
Chicago, 111.
El Segundo, Cal.
Frankford, Pa.
I ronton, Ohio
Marcus Hook, Pa.
Moundsville, W. Va.
Syracuse, N. Y.
3-Amino-5-chloro-2-
hydroxybenzene-
sulfonic acid (III)3
Fumaric acid (III)
Maleic acid (III)
l-Phenol-2-sulfonic acid,
formaldehyde condensate (III)
Phthalic anhydride (III)3
Picric acid (III)3
Phthalic anhydride (III)3
Phthalic anhdyride (III)
Phthalic anhydride (III)3
Phthalic anhydride (III)3
Maleic acid (III)
Fumaric acid (III)
Maleic acid (III)
Maleic anhydride (III)
o-Dichlorobenzene (III)
American Aniline
Products, Inc.
25 McLean Blvd.
P.O. Box 3063
Paterson, N. J. 07509
Owned by Pepi, Inc. 52%
and Kopper Co., Inc., 48%
Lock Haven, Pa.
o-Anisidine (111)a
American Color and Chem.
Corp.
11400 Westinghouse Blvd.
P.O. Box 1688
Charlotte, N. C. 28201
Lock Haven, Pa.
o-Anisidine (III)
4-Chlororesorcinol (II)
(conti nued)
97

-------
TABLE 12 (Continued)
Producer
Locati on
Chemical (class)
Amoco Chems. Corp.
200 E. Randolph Dr.
Chicago, 111. 60601
Affiliate of Standard
Oil Co., Ind.
Joilet, 111.

Maleic anhydride (III)
Arsynco
See Aceto


Ashland Oil, Inc .
1409 Winchester Ave.
P.O. Box 391
Ashland, Ky. 41101
Neal, W. Va.

Maleic anhdyride (III)
BASF Wyandotte Corp.
100 Cherry Hill Road
Parisppany, N. J. 07054
Kearny, N. J.

Phthalic anhydride (III)
Blue Spruce Co.
1390 Valley Road
Stirling, N. J. 07980
Bound Brook,
Edi son, N. J.
N. J.
3,4-Dichloroaniline (III)
l,2-Dichloro-4-nitro-
benzene (III)
3,4-Dichloroaniline (III)
l,2-Dichloro-4-nitro-
phenol (III)3
Chemical Insecticide Corp.
30 Whitman Ave.
Metuchen, N. J. 08840
No current address
Metuchen, N.
J.
3,4-Dichloroaniline (III)3
l,2-Dichloro-4-nitro-
benzene (III)
Chemical Products Corp.
48 Atlanta Road
Cartersvi11e, Ga. 30120
Cartersvilie,
Ga.
o-Dichlorobenzene (III)a
Chevron Chem. Co.
575 Market Street
San Francisco, Cal. 94105
Subsid. Standard Oil Co.
of Cal.
Richmond, Cal
Perth Amboy,
N. J.
Maleic anhydride (III)3
Phthalic anhydride (III)
Phthalic anhydride (III)3
Chris Craft Industry, Inc.
600 Madison Avenue
New York, N. Y.
See Montrose Chem.
Newark, N. J.

1,2,4-Trichlorobenzene (III)3
(conti nued)
98

-------
TABLE 12 (Continued)
Producer
Locati on
Chemical (class)
Commonwealth Oil Refining
Co., Inc.
245 Park Avenue
New York, N. V. 10017
Penuelas, P. R.
Phthalic anhydride (III)3
Continental Oil Co.
(Conoco)
Petrochemicals Dept.
Saddle Brook, N. J. 07662
Hebronville, Mass.
Phthalic anhydride (III)3
Crompton and Knowles Corp.
345 Park Ave.
New York, N. Y. 10022
Fair Lawn, N. J.
Benzaldehyde (III)
Diamond Shamrock Corp.
1100 Superior Ave.
Cleveland, Ohio 44114
Cedartown, Ga.
Newark, N. J.
1-Phenol-2-sulfonic acid,
formaldehyde condensate (III)
2,4-Dichlorophenol (I)
Dover Chem. Corp.
West 15th Street
Dover, Ohio 44622
Affiliate of ICC Indus-
tries, Inc.
Dover, Ohio
o-Dichlorobenzene (III)3
Hexachlorobenzene (III)
1,2,4,5-Tetrachioro-
benzene (III)
Tetrachlorobisphenol-A (II)
1,2,4-Trichlorobenzene (III)
Dow Chem. U.S.A.
2020 Dow Center
Midland, Mich.
Kalama, Wash.
Midland, Mich.
Benzaldehyde (III)3
o-Chlorophenol (II)
2-Chloro-4-phenylphenol (II)
2,4-Dibromophenol (I)
o-Dichlorobenzene (III)
2,4-Dichlorophenol (I)
Pentabromochloro-
cyclohexane (III)
Phenol (III)3*
Phenyl either (III)
Tetrabromobisphenol-A (II)
1,2,4,5-Tetrachioro-
benzene (III)
2,4,6-Tribromophenol (I)
1,2,4-Trichlorobenzene (III)
(conti nued)
99

-------
TABLE 12 (Continued)
Producer
Locati on
Chemical (class)
E.I. du Pont de Nemours
and Co., Inc.
1007 Market Street
Wilmington, Del. 19898
Eastern Chem. Corp.
Now Eastern Chem. Div.
of Guardian Chem. Corp.
Eastman Kodak Co.
343 State Street
Rochester, N. Y. 14650
Exxon Corp.
1251 Ave. of the Americas
New York, N. Y. 10020
Fairmount Chem. Co., Inc.
117 Blanchard Street
Newark, N. J. 07105
Fritzsche Dodge and Olcott,
I nc.
76 Ninth Ave.
New York, N. Y. 10011
GAF Corp.
140 West 51st St.
New York, N. Y. 10020
W. R. Grace and Co.
7 Hanover Square
New York, N. Y. 10005
Deepwater, N. J.
Pequannock, N. J.
Rochester, N. Y.
Baton Rouge, La.
Newark, N. J.
CIi fton. N. J.
Rensselaer, N. Y.
Fords, N. J.
o-Anisidine (III)
4-Ch1oro-2-nitropheno1 (111)=
3,4-Dichloroani1ine (III)
o-Dichlorobenzene (III)
2-Nitro-p-cresol (III)
o-Nitrophenol (III)
o-Nitroanisole (III)
Chlorohydroquinone (II)3
2,4,6-Tribromopheno1 (I)
o-Bromophenol (II)
Chlorohydroquinone (II)
2,5-Dihydroxybenzene-
sulfonic acid (III)
2,5-Di ni trosa1i cy1ic
acid (III)
Maiei c acid (111)a
Phthalic anhydride (III)
2-Chloro-1,4-di ethoxy-5-
nitrobenzene (II)
Benzaldehyde (III).
Phenyl ether (III)C
2-Chloro-l,4-diethoxy-5~
nitrobenzene (II)
5-Chloro-2,4-dimethoxy-
ani1i ne (II)
4-Chlororesorc i nol
(II)
Phthalic anhydride (III)C
(conti nued)
100

-------
TABLE 12 (Continued)
Producer
location
Chemical (class)
Great Lakes Chem. Corp.
Hwy. 52, Northwest
West Lafayette, Ind. 47906
Guardian Chem, Corp.
230 Marcus Blvd.
Hauppauge, N. V. 11787
Hexeel Corp.
11711 Dublin Blvd.
Dublin, Cal. 94566
Hooker Chem. Corp.
1900 St. James PI.
Houston, Tex. 77027
Subsid. Occidental
Petroleum Corp.
Hummel Chem. Co. , Inc.
P.O. Box 250
South Plaintield, N.
07080
ICC Industries
See Solvent Chem.
Inmont Corp.
1133 Ave. of the Americas
New York, N. V. 10036
(Subsid. of Carrier Corp.)
El Dorado, Ark.
Hauppauge, N. Y,
Sayreville, N. 0.
Arecibo, P. R,
Niagara Falls, N. Y.
North Tonawanda, N. Y.
South Shore, Ky.
Newark, N. J.
South Plainfield, N. J.
Oecabromophenoxy-
benzene (I)
Tetrabromobisphenol-A (II)
Chlorohydropuinone (II)3
2,4,6-Tribromophenol (I)
Pentabromoethylbenzene (III)
Carlstadt, N. J.
NOTE: Carlstadt Plant
listed under Inter-
chemical Corp. which
was acquired by Inmont
Corp.
acid (III)
anhydride C331^
Furmari c
Phthalic
o-Dichlorobenzene (III)
Tetrachlorophthalic
anhydride
1,2,4
(III)
Tetrachloro-
benzene (III)
1,2,4-Trichlgrpbenzene (III)C
Phenol (111 )f *
Phenol (III)
a,b
4-Di nitrophenoxyethanol
3,5-Dini trosalicylic
acid
a
(in)!
cIII)c
Hexachlorobenzene (III)
Picric acid (III)3
2.4-Di	nitrophenoxy-
ethanol (III)
3.5-Dinitrosalicylic
acid (111)a	a
Hexachlorobenzene (III)
Picric acid (111)a
Sodium picrate (III)
3,5-Dichlorosalicylic
acid (III)
(continued)
101

-------
TABLE 12 (Continued)
Producer
Locati on
Chemical (class)
International Minerals
and Chem. Corp.
IMC Plaza
Libertyvi11e, 111. 60048
Ka1ama Chem., Inc.
The Bank of Cal. Center
Suite 1110
Kalama, Wash. 98164
Kopper Co., Inc.
Koppers Bldg.
Pittsburgh, Pa. 15219
Martin Marietta Corp.
6801 Rock!edge Dr.
Bethesda, Md. 20034
Maumee Chem. Co.
Presumed to be acquired
by Sherwin Williams
Address not available
Mobay Chem. Co.
Penn Lincoln Parkway West
Pittsburgh, Pa. 15205
Monroe Chem. Co.
Saville Ave. at 4th St.
Eddystone, Pa.
Subsid. of Kalama Chem.,
Inc. (see Kalama)
Monsanto Co.
800 North Lindbergh Blvd.
St. Louis, Mo. 63166
Newark, N. J.
Kalama, Wash.
Bri dgevilie, Pa.
Chicago, 111.
Cicero, 111.
Sodyeco, N. C.
St. Bernard, Ohio
New Martinsville, W. Va.
Eddystone, Pa.
Bridgeport, N. J.
Chocolate Bayou, Tex.
Luling, La.
1,2 ,4-Trichlorobenzene (III)
Benzaldehyde (III)
Maleic anhydride (III)
Phthalic anhydride (III)
Phthalic anhydride (III)3
Maleic anhydride (III)3
Phthalic anhdyride (III)
2,6-Dibromo-4-nitrophenol (II)C
3,4-Dichloroani1ine (III)3
l,2-Dichloro-4-nitro-
3
benzene (III)
2,4-Dinitrophenol (III)
Picric acid (III)
Sodium picrate (III)
2,6-Debromo-4-nitrophenol (II)
4-Chloro-2-nitrophenol (III)
3,4-Dichlorophenyli-
socyanate (III)
2,4-Dinitrophenol (III)
Benzaldehyde (III)
Phthalic anhydride (III)
Tetrachlorophthalic anhydride (III)
Phenyl ether (III)
Phthalic anhydride (111)a
3 ,4-Dichloroani1ine (III)
(conti nued)
102

-------
TABLE 12 (Continued)
Producer
Location
Chemical (class)
Monsanto (continued)
Sauget, 111.
St. Louis, Mo.
Texas City, Tex.
o-Chlorophenol (II)
3,4-Dichloroani1ine (III)a
o-Dichlorobenzene (III)
l,2-Dichlor-4-nitrobenzene (III)
2,4-Dichlorophenol (I)
o-Nitroanisole (III)
o-Nitrophenol (HI)
o-Anisidine (III)
Fumaric acid (III)
Maleic anhydride (III)
o-Nitroanisole (III^
o-Phenetidine (III)
Phthalic anhydride (111)a
Phthalic anhydride (III)
Montrose Chem. Corp. of
Cal.
2401 Morris Ave.
P.O. Box E
Union, N. J. 07083
(Jointly owned by Chris
Craft Industries, Inc.
and Stauffer Chem. Co.)
Henderson, Nev.
o-Dichlorobenzene (III)
Morton Chem. Co., Div.
Morton-Norwich Products,
Inc.
110 North Wacker Dr.
Chicago, 111. 60606
Ringwood, 111.
3,5-Diiodosalicylic acid (II)a
Nease Chem. Co., Inc.
P.O. Box 221
State College, Pa. 16801
State Col lege, Pa.
2,5-Dihydroxybenzene-
sulfonic acid (III )a
2,5-Di hydroxybenzene-
sulfonic acid,
' g
potassium salt (III)
Neville Chem. Co.
Neville Island
Pittsburgh, Pa. 15225
Sante Fe Springs, Cal.
o-Dichlorobenzene (III)3
1,2,4-Trichlorobenzene (III)
Northrop Corp.
1800 Centruy Park, East
Los Angeles, Cal. 90067
Ashevilie, N. C.
Sodium picrate (III)
Tribromobenzene (III)
2,4,6-Trinitroresorcinol (III)
(conti nued)
103

-------
TABLE 12 (Continued)
Producer
Locati on
Chemical (class)
Northwest Industries
(See Velsicol)
G 300 Sears Tower
Chicago, 111. 60606


Nyanza, Inc.
200 Sutton St.
North Andover, Mass. 01721
Ashland, Mass
3-Ami no-5-chloro-2-
hydroxybenzene-
sulfonic acid (III)
2-Ami no-4-chloro-6-
nitrophenol (III)
Occidental Petroleum Corp.
(See Hooker)
10889 Wilshire Blvd. ,
Suite 1500
Los Angeles, Cal. 90024


01 in Corp.
120 Long Ridge Road
Stamford, Conn. 06904
East A1ton, 111.
Mcintosh, Ala.
Rochester, N. Y.
2,4,6-Trinitroresorcinol (III)a
o-Dichlorobenzene (III)
o-Bromof1uorobenzene (III)
o-Chlorofluorobenzene (III)
3-Chloro-4-f1uoronitro-
benzene (III)
2-Chloro-4-f1uorophenol	(I)
3-Chloro-4-f1uorophenol	(III)
2,4-Dibromofluorobenzene (III)
3,4-Dif1uoroani1ine (III)
o-Difluorobenzene (III)
o-Fluoroanisole (II)
Pentachloroani1ine (III)
Ott Chem. Co.
See Story Chem.


PCR, Inc.
P.O. Box 1466
Gainesville, Fla. 32602
Gainesville, Fla.
Hexafluorobenzene (III)
Petro-Tex Chem. Corp.
8600 Park Place
Houston, Tex. 77017
Jointly owned by FMC Corp.
and Tenneco, Inc.
Houston, Tex.
Fumaric acid (III)3
Maleic anhydride (III)
(conti nued)
104

-------
TABLE 12 (Continued)
Producer
Location
Chemical (class)
Pfister Chem., Inc.
Linden Avenue
Ridgefield, N. J. 07657
Newark, N. J.
Ridgefield, N. J.
2-Chloro-l,4-diethoxy-5-
nitrobenzene (II)
5-Chloro-2,4-dimethoxyani1ine (II
5-Chloro-2,4-dimethoxy-
aniline (II)
Pfizer, Inc.
235 East 42nd St.
New York, N. Y. 10017
Terre Haute, Ind.
Fumaric acid (III)
Plastifax, Inc.
Indust. Seaway Blvd.
P.O. Box 1056
Gulfport, Miss. 39501
Gulf Port, Miss.
l,2-Dichloro-4-
nitrobenzene (III)
PPG Industries, Inc.
One Gateway Center
Pittsburgh, Pa. 15222
Natrium, W. Va.
o-Dichlorobenzene (III)
Reichhold Chems., Inc.
RCI Bldg.
White Plains, N. Y. 10603
Azusa, Cal.
Elizabeth, N. J.
Morris, 111.
Phthalic anhydride (III)3
Maleic anhydride (III)
Phthalic anhydride (III)
Fumaric acid (III)
Maleic anhydride (III)
Phthalic anhydride (III)
Rhodia, Inc.
600 Madison Ave.
New York, N. Y. 10022
Freeport, Tex.
2,4-Dichlorophenol (I)
F. Ritter and Co.
4001 Goodwin Ave.
Los Angeles, Cal. 90039
Los Angeles, Cal.
Benzaldehyde (111 )a
Rohm and Haas Co.
Independence Mall West
Philadephia, Pa. 19105
Philadelphia, Pa.
1-Phenol-2-sulfoni c
acid, formaldehyde
condensate (III)
R.S.A. Corp.
690 Saw Mill River Road
Ardsley, N. Y. 10502
Ardsley, N. Y.
Bromophenetole (II)
o-Bromophenol (II)
2,6-Di iodo-4-nitrophenol (H)a
3,5-Diiodosalicylic acid (II)
Pentabromophenol (I)
2,4,6-Tribromophenol (I)
(continued)
105

-------
TABLE 12 (Continued)
Producer
Location
Chemical (class)
Salsbury Labs
2000 Rockford Road
Charles City, Iowa
50616
Sherwin Williams Co.
101 Prospect Ave.
Cleveland. Ohio 44101
Sobin Chems. Inc.
See International
Minerals and Chems. Corp.
Solvent Chem. Co., Inc.
720 Fifth Avenue
New York, N. Y. 10011
Affiliate if ICC Industries
Specialty Organics, Inc.
5263 North Fourth St.
Irwindale, Cal. 91706
Standard Chlorine Chem.
Co., Inc.
1035 Belleville Turnpike
Kearny, N. J. 07032
Charles City, Iowa
Chi cago, 111.
St. Bernard, Ohio
Maiden, Mass.
Niagara FalIs, N. Y.
Irwindale, Cal.
Del aware Ci ty, Del.
Kearny, N. J.
3,5-Di ni trosali eye 1i c
acid (III)
2-Nitro-p-cresol (III)
Phthalic anhydride (111 )a
2,6-Dibromo-4-nitrophenol (II)'
4-Chloro-2-nitrophenol (III)3
o-Dichlorobenzene (III)
1,2,4,5-Tetrachloro-
benzene (III)
1,2,4-Trichlorobenzene (III)'
o-Dichlorobenzene (III)
2,3-Dichlorophenol (I)
2,6-Dichlorophenol (I)
o-Dichlorobenzene (III)
o-Dichlorobenzene (III)
1,2,4,5-Tetrachioro-
benzene (III)
1,2,4-Trichlorobenzene (III)
o-Dichlorobenzene (III)
1,2,4-Trichlorobenzene (111)c
Standard Oil Co.(Cal.)
(See Chevron)
575 Market St.
San Francisco, Cal. 94105
Standard Oil Co. (Ind.)
(See Amoco)
910 South Michigan Ave.
Chi cago, 111. 60605
Standard Oil Co. (N.J.)
(See Exxon)
(conti nued)
106

-------
TABLE 12 (Continued)
Producer
Location
Chemical (class)
Stauffer Chem. Co.
Westport, Conn. 06880
Edison, N. J.
Nixon, N. J.
Louisville, Ky.
Benzaldehyde (111 )a
Banzaldehyde (111 )a
Hexachlorobenzene (III)
Stepan Chem. Co.
Edens and Winnetka Rd.
Northfield, 111. 60093
El wood, 111.
Fieldsboro, N. J.
Mi 11sdale, 111.
Phthalic anhydride (III)
Fumaric acid (III)
Phthalic anhydride (III)a
Stering Drug Inc.
90 Park Avenue
New York, N. Y. 10016
New York, N. Y.
1,2-Di hydroxy-3,5-disulfonic
acid, disodium salt (III)
Story Chem. Corp.
500 Agard Road
Muskegon, Mich. 49445
Ott Chem. Co. , Di v.
Muskegan, Mich.
3,4-Dichloropheny 11" -
socyanate (III)
Sun Chem. Corp.
Box 70
Chester, S. C. 29706
Chester, S. C.
1,2,4-Trichlorobenzene (III)3
Tenneco Chems. Co.
Park 80 Plaza, West
Saddle Brook, N. J. 07662
(Part of Tenneco, Inc.)
Fords, N. J.
Garfield, N. J.
Benzaldehyde (III)3
3,4-Dichlorobenzal-
dehyde (III)
3,4-Di chlorobenzotri-
chloride (III)
3,4-Dichlorobenzotri-
fluoride (III)3
Maleic anhydride (III)
Fumaric acid (III)
Benzaldehyde (III)
Toms River Chem. Corp.
P.O. Box 71
Toms River, N. J. 08753
(80% Ciba-Geigy and
20% Sandoz AG)
Toms River, N. J.
3-Ami no-5-chloro-2-
hydroxybenzene-
sulfonic acid (III)
Transvaal, Inc.
Marshall Road
P.O. Box 69
Jacksonville, Ark. 72076
(Subsid. of Vertac)
Jacksonville, Ark.
2,4-Dichlorophenol (I)
Union Carbide Corp.
270 Park Avenue
New York, N. Y. 10017
Marietta, Ohio
Phenol (III)a,b
(conti nued)
107

-------
TABLE 12 (Continued)
Producer
Location
Chemical (class)
UOP, Inc.
Ten UOP P]aza
Algonquin and Mt.
Prospect Roads
Des Plaines, 111. 60016
East Rutherford, N. J.
Benzaldehyde (III)
U.S. Steel Corp.
Sixth and Grant
Pittsburgh, Pa. 15230
Neville Island, Pa.
Fumaric acid (III)
Maleic anhydride (III)
Phthalic anhydride (III)
Velsicol Chem. Corp.
341 East Ohio St.
Chicago, 111. 60611
(Subsid. of Northwest
Industries, Inc.)
Beaumont, Tex.
Chattanooga, Tenn.
St. Louis, Mich.
4-Bromo-2,5-dichlorphenol (I)
2,5-Dichlorophenol (I)
Benzaldehyde (III)a
Hexabromobenzene (III)
Pentabromophenol (I)
Tetrabromobisphenol-A (II)
Tetrabromophthalic anhydride (III
Tribromobenzene (III)
2,4,6-Tribromophenol (I)
Vertac, Inc. (See Transvaal)
2414 Clark Tower
Memphis, Tenn. 38137


White Chem. Corp.
P.O. Box 278
Bayonne, N. J. 07002
Bayonne, N. J.
2,4-Dibromophenol (I)
Pentabromophenol (I)
Pentabromotoluene (III)
2,4,6-Tribromophenol (I)
Whittaker Corp.
10880 Wilshire Blvd.
Los Angeles, Cal. 90024
San Diego, Cal.
Hexaf1uorobenzene (III)ag
Pentaf1uoroani1ine (III)
Chloropentaf1uoro-
benzene (III)
Tetraf1uoro-m-phenylene-
diamine (III)
Witco Chem. Corp.
277 Park Avenue
New York, N. Y. 10017
Chicago, 111.
Perth Amboy, N. J.
Phthalic anhydride (III)®
Phthalic anhydride (III)
* No longer produced at this location.
From chlorobenzene.
108

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TABLE 13. FORMER LOCATIONS OF ORGANIC CHEMICAL PRODUCTION
Producer
Locati on
Chemical (class)
Aldri ch
Milwaukee, Wise.
2,4-Dichlorophenol (I)
Allied
Buffalo, N. Y.
Chi cago, 111.
Frankford, Pa.
I ronton, Ohio
Moundsville, W. Va.
Syracuse, N. Y.
3-Ami no-5-chloro-2-hydroxy-
benzenesulfonic acid (III)
Fumaric acid (III)
Maleic acid (III)
l-Phenol-2-sulfonic acid,
formaldehyde condensate (III)
Phthalic anhydride (III)
Phthalic anhydride (III)
Phthalic anhydride (III)
Phthalic anhydride (III)
Fumaric acid (III)
Maleic acid (III)
Maleic anhydride (III)
o-Dichlorobenzene (III)
Am. Aniline
Lock Haven, Pa.
o-Anisidine (III)
Blue Spruce
Edison, N. J.
3,4-Dichloroani1ine (III)
1,2-Dichloro-4-nitrobenzene (III)
Chem. Insecticide
Metuchen, N. J.
3,4-Dichloroani1ine (III)
1,2-Dichloro-4-nitrobenzene (III)
Chem. Products
Cartersvi11e, Ga.
o-Dichlorobenzene (III)
Chevron
Richmond, Cal.
Perth Ambay, N. J.
Maleic anhydride (III)
Phthalic anhydride (III)
Chris Craft
Newark, N. J.
1,2,4-Trichlorobenzene (III)
Commonwealth Oil
Penuelas, P. R.
Phthalic anhydride (III)
Conoco
Hebronville, Mass.
Phthalic anhydride (III)
Dover
Dover, Ohio
o-Dichlorobenzene (III)
Hexachlorobenzene (III)
1,2,4,5-Tetrachlorobenzene (III)
Tetrachlorobisphenol-A (II)
1,2,4-Trichlorobenzene (III)
Diamond Shamrock
Cedartown, Ga.
l-Phenol-2-sulfonic acid,
formaldehyde condensate (III)
Dow
Midland, Mich.
Phenol3 (III)
2,4,6-Tribromophenol (I)
(continued)
109

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TABLE 13 (Continued)
Producer
Locati on
Chemical (class)
Oow (continued)
Kalama, Wash.
Benzaldehyde (III)
du Pont
Deepwater, N. J.
4-Chloro-2-nitrophenol (III)
o-Dichlorobenzene (III)
2-Nitro-p-creso 1 (III)
o-Nitrophenol (III)
Eastern Chem.
(currently Eastern
Chem. Div. of
Guardian)
Pequannock, N. J.
Chiorohydroquinone (II)
2,4,6-Tribromophenol (I)
Eastman Kodak
Rochester, N. Y.
2,5-Di hydroxybenzenesulfoni c
acid (III)
Maleic acid (III)
Fri tzsche
Clifton, N. J.
Benzaldehyde (III)
Phenyl ether (III)
W. R. Grace
Fords, N. J.
Phthalic anhydride (III)
Guardian
Hauppauge, N. Y.
Pequannock, N. J.
Chiorohydroquinone (II)
Chlorohydroquinone (II)
2,4,6-Tribromophenol (I)
Hooker
Ni agara Falls, N. Y.
North Tonawanda, N. Y.
South Shore, Ky.
o-Dichlorobenzene (III)
Tetrachlorophthalic anhydride (III)
1,2,4,5-Tetrachlorobenzene (III)
1,2,4-Trichlorobenzene (III)
Phenol3 (III)
Phenol3 (III)
Hummel Chem.
Newark, N. J.
South Plainfield, N. J.
2.4-Dinitrophenoxyethanol	(III)
3.5-Dinitrosalicy1ic	acid (III)
Hexachlorobenzene (III)
Picric acid (III)
3,5-Dinitrosalicylic acid (III)
Hexachlorobenzene (III)
Picric acid (III)
Inmont
(formerly Inter-
chemical Corp. )
Carlstadt, N. J.
3,5-Dichlorosalicy 1ic acid (III)
(continued)
110

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TABLE 13 (Continued)
Producer
Location
Chemical (class)
Koppers
Chicago, 111.
Cicero, 111.
Phthalic anhydride (III)
Maleic anhydride (III)
Martin Marietta
Sodyeco, N. C.
2,6-0ibromo-4-nitropheno1 (II)
3,4-Dichloroani1ine (III)
l,2-D1chloro-4-nitrobenzene (III)
Sodium picrate (III)
Monsanto
Chocolate Bayou, Tex.
Saugett, 111.
St. Louis, Mo.
Phthalic anhydride (III)
3,4-Dichloroani1ine (III)
l,2-Dichloro-4-nitrobenzene (III)
o-Nitroanisole (III)
o-Anisidine (III)
o-Phenetidine (III)
Phthalic anhydride (III)
Morton Chem.
Ringwood, 111.
3,5-0iiodosalicy 1ic acid (II)
Nease Chem.
State Col lege, Pa.
2,5-Dihydroxybenzenesulfonic
acid (III)
2,5-Di hydroxybenzenesul foni c
acid and potassium salt (III)
Neville Chem.
Santa Fe Springs, Cal.
o-Dichlorobenzene (III)
1,2,4-Trichlorobenzene (III)
01 in
East Alton, 111.
Mcintosh, Ala.
2,4,6-Trinitroresorcinol (III)
o-Dichlorobenzene (III)
Petro-Tex
Houston, Tex.
Fumaric acid (III)
Maleic anhydride (III)
Pf ister
Newark, N. J.
2-Chloro-1,4-d i ethoxy-5-
nitrobenzene (II)
5-Chloro-2,4-dimethoxyani1ine (II]
Reichhold
Azusa, Cal.
Elizabeth, N. J.
Morris, 111.
Phthalic anhydride (III)
Phthalic anhydride (III)
Fumaric acid (III)
Phthalic anhydride (III)
F. Ritter
Los Angeles, Cal.
Benzaldehyde (III)
(continued)
HI

-------
TABLE 13 (Continued)
Producer
Locati on
Chemicals (class)
R.S.A.
Ardsley, N. Y.
3,5-Diiodosalicyclic acid (II)
Pentabrompphenol (I)
2,4,6-Tribromophenol (I)
Sherwin Williams
St. Bernard, Ohio
2,6-0ibromo-4-nitrophenol (II)
4-Chloro-2-nitrophenol (III)
Phthalic anhydride (III)
Sobin Chems.
(currently Inter-
national Minerals
and Chems. Corp. )
Newark, N. J.
1,2,4-Trichlorobenzene (III)
Solvent Chem.
Maiden, Mass.
o-Dichlorobenzene (III)
1,2,4,5-Tetrachlorobenzene (III)
1,2,4-Trichlorobenzene (III)
Standard Chlorine
Kearny, N. J.
1,2,4-Trichlorobenzene (III)
Stauffer
Edison, N. J.
Louisvi 11 e, Ky.
Nixon, N. J.
Benzaldehyde (III)
Hexachlorobenzene (III)
Benzaldehyde (III)
Stepan Chem.
Fieldsboro, N. J.
Mi 11 sdale, 111.
Fumaric acid (III)
Phthalic anhydride (III)
Sterli ng Drug
New York, N. Y.
1,2"Dihydroxy-3,5-di sulfonic
acid, disodium salt (III)
Story Chem.
Muskegon, Mich.
3,4-Di chlorophenyli socyanate (III)
Sun Chem.
Chester, S. C.
1,2,4-Trichlorobenzene (III)
Tenneco
Fords, N. J.
3,4-Dichlorobenzotrifluoride (III)
Union Carbide
Marietta, Ohio
Phenola (III)
Vels icol
Chattanooga, Tenn.
St. Louis, Mich.
Benzaldehyde (III)
Hexabromobenzene (III)
Pentabromophenol (I)
Tribromobenzene (III)
2,4,6-Tribromophenol (I)
(conti nued)
112

-------
TABLE 13 (Continued)
Producer
Location
Chemicals (class)
Whi ttaker
San Diego, Cal.
Hexafluorobenzene (III)


Pentaf1uoroani1ine (III)


Chioropentaf1uorobenzene (III)


Tetrafluoro-m-phenylenedfamine (III)
Wi tco
Chicago, 111.
Phthalic anhydride (III)

Perth Amboy, N. J.
Phthalic anhydride (III)
a From chlorobenzene.
113

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TABLE 14. PRODUCERS OF PESTICIDE CHEMICALS, CLASSES I AND II
Chemical
Producer
Location
Class I


Bi fenox
Mobi 1
Mt. Pleasant, Tenn.
Cblorani 1
Arapahoe
Uni royal
Boulder, Colo.a
Naugatuck, Conn.
2,4-D and esters and salts
Amchem
Chemical Insecticide
Corp.
Chempar
Diamond Shamrock
Dow
Fallek-Lankro
Guth Chem.
Imperial
Miller Chem.
Monsanto
PBI-Gordon
Rhodi a
Riverdale
Thompson Chem.
Thornpson-Hayward
Transvaal
Woodbury
Ambler, Pa.
Fremont, Cal.
St. Joseph, Mo.
Metuchen, N. J.3
Portland, Ore.3
Newark, N. J.3
Midland, Mich.
Tuscaloosa, Ala.
Hillside, 111.
Shenandoah, Iowa
Whiteford, Md.3
Sauget, 111.3
Kansas City, Kans.
N. Kansas City, Mo.
Portland, Ore.
St. Joseph, Mo.
St. Paul, Minn.3
Chicago Hgts. , 111.
St. Louis, Mo.3
Kansas City, Kans.
Jacksonville, Ark.
Orlando, Fla.3
2,4-DB and salts
Amchem
Rhodi a
Ambler, Pa.
N. Kansas City, Mo.
Portland, Ore.
St. Joseph, Mo.
St. Paul, Mi nn.3
Dicamba
Velsicol
Beaumont, Tex.
Chattanooga, Tenn.
Di capthon
American Cyanamid
Warners, N. J.3
Dichlofenthion
Mobile
Charleston, S. C.3
Mt. Pleasant, Tenn.
(conti riued)
114

-------
TABLE 14 (continued)
Chemical
Producer
Location
Dimethyl amine salt of
dicamba
PBI-Gordon
Kansas City, Kans.
Disul Sodium (Sesone)
Amchem
GAF
Union Carbide
Ambler, Pa.a
Fremont, Cal.
Linden, N. J.a
d
St. Joseph, Mo.
Linden, N. J.a
Institue and S.
Charleston, W. Va.
2,4-DP
Rhodi a
Transvaal
Portland, Ore.
Jacksonville, Ark.
Erbon
Dow
Midland, Mich.3
Hexachlorophene
Gi vaudan
Clifton, N. J.
Isobac 20
Gi vaudan
Clifton, N. J.
Nitrofen
Rohm and Haas
Philadelphia, Pa.
Pentachlorophenol (PCP)
and salts
Dow
Merck
Monsanto
Reichhold
Sonford Chemical
Vulcan Matls.
Midland, Mich.
d
Hawthorne, N. J.
Sauget, 111.
Tacoma, Wash.
d
Port Neches, Tex.
Wichita, Kans.
Ronnel
Dow
Midland, Mich.
Si 1 vex and esters and salts
Dow
Guth Chemical
Mi 11 master Onyx
Riverdale
Thompson-Hayward
Transvaal
Midland, Mich.
Hillside, 111.3
Berkeley Hgts., N. J.3
Chicago Hgts., 111.
Kansas City, Kans.
Jacksonville, Ark.
2,4,5-T and esters and salts
Amchem
Chemical Insecticide
Corp.
Chempar
Ambler, Pa.
Fremont, Cal.
St. Joseph, Mo.
Metuchen, N. J.3
Portland, Ore.3
(conti nued)
115

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TABLE 14 (continued)
Chemi cal
Producer
Location
2,4,5-T and esters and
salts (continued)
Diamond Shamrock
Dow
Guth Chemical
Hercules
Mi 11 master Onyx
PBI-Gordan
Ri verdale
Thompson Chemical
Thompson-Hayward
Transvaal
Newark, N. J.a
Midland, Mich.
Hillside, 111.3
Brunswick, Ga.
Berkeley Hgts., N. J.
Kansas City, Kans.
Chicago Hgts., 111.
St. Louis, Mo.a
Kansas City, Kans.
Jacksonville, Ark.
2,3,4,6-Tetrachlorophenol
Dow
Sonford
Midland, Mich.
Port Neches, Tex.
2,4,5-Trichlorophenol
and salts
Chemical Insecticide
Corp.
Diamond Shamrock
Dow
GAF
Hercules
Hooker
N. Eastern Pharmacy
Transvaal
Metuchen, N. J.3
Newark, N. J.a
Midland, Mich.
Linden, N. *J.aa
Brunswick, Ga.
Niagara Falls, N. Y.
Verona, Mo.
Jacksonville, Ark.
2,4,6-Trichlorophenol
Dow
Midland, Mich.
Class II


o-Benzyl-p-chlorophenol
Monsanto
Reichhold
Sauget, 111.
Tacoma, Wash.
Bromoxynil and esters
Amchem
Rhodi a
Ambler, Pa.
Portland, Ore.
St. Joseph, Mo.
Carbophenothion
Stauffer
Cold Creek, Ala.3
Henderson, Nev.
Chi orothal oni1
Diamond Shamrock
Greens Bayou, Tex.
DCPA
Diamond Shamrock
Greens Bayou, Tex.
Dichlone
Aceto
FMC
Uni royal
Flushing, N. Y.3
Middleport, N. Y^
Nangatuck, Conn.
(conti nued)
116

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TABLE 14 (continued)
Chemical
Producer
Location
Dinitrobutylphenol,
ammonium salt
Dow
Midland, Mich.
4,6-Dini tro-o-cresol
and sodium salt
Blue Spruce
Bound Brook, N. J.
Ioxyni1
Amchem
Rhodia
Fremont, Cal.a
Portland, Ore.3
Li ndane
Hooker
Prenti ss
Niagara Falls, N. Y.
Newark, N. J.
MCPA and derivatives
Diamond Shamrock
Dow
Fallek-Lankro
Guth Chemical
Monsanto
Rhodia
Newark, N. J.a
Midland, Mich.
Tuscaloosa, Ala.
Hillside, 111.3
Nitro, W. Va.a
Portland, Ore.
MCPB
Amchem
Dow
Monsanto
Rhodi a
Ambler, Pa.
Fremont, Cal.
St. Joseph, Mo.
Midland, Mich.3
Sauget, 111.
Portland, Ore.
St. Joseph, Mo.
Mecoprop
CIeary
Fallek-Lankro
Morton Chem.
PBI-Gordon
Rhodia
Somerset, N. J.
Tuscaloosa, Ala.
3
Ringwood, 111.
Kansas City, Kans.
Portland, Ore.
St. Joseph, Mo.
Parathion
American Cyanamid
American Potash
Monsanto
Stauffer
Velsicol
Warners, N. J.3
3
Hamilton, Miss.
Los Angeles, Cal.
Anniston, Ala.
Mt. Pleasant, Tenn.
Bayport, Tex.
PCNB
Monsanto
01 in
Sauget, 111.3
Leland, Miss.
Mcintosh, Ala.
Rochester, N. Y.
(continued)
117

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TABLE 14 (continued)
Chemical
Producer
Location
Pipecolinopropyl-3,4-
di chlorobenzoate
Eli Lilly
Lafayette, Ind.
Piperalin
Eli Lilly
Indianapolis, Ind.3
Lafayette, Ind.
Propani1
Blue Spruce
Eagle River
Monsanto
Sobin Chemical
Bound Brook, N. J.
Helena, Ark.
Luling, La.
Newark, N. J.
Tetradi fon
FMC
Baltimore, Md.a
2,3,6-Trichlorobenzoic
acid
Amchem
du Pont
Tenneco
Ambler, Pa.
Fremont, Cal.
St. Joseph, Mo.
Deepwater, N. J.
Fords, N. J.a
2,3,6-Trichlorophenyl
acetic acid and
sodium salt
Amchem
Tenneco
Ambler, Pa.
Fremont, Cal.
St. Joseph, Mo.
Fords, N. J.a
Triiodobenzoic acid
Amchem
Mai 1i nckrodt
Ambler, Pa.
Raleigh, N. C.
No longer produced at this location.
118

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TABLE 15. ALPHABETICAL LIST OF PESTICIDE CHEMICAL PRODUCERS
Producer
Location
Chemical (class)
Aceto Chemical Co., Inc.
Alco Standard Corp.
(See Miller Chem.)
Amchem Products, Inc.
Brookside Ave.
P.O. Box 33
Ambler, Pa. 19002
(Subsid. of Union Carbide)
Flushing, N. Y.
Ambler, Pa.
Fremont, Cal.
Li nden, N. J.
St. Joseph, Mo.
American Cyanamid Co.
Berdan Ave.
Wayne, N. J. 07470
American Potash and Chem.
Corp.
Kerr-McGee Chem. Corp.
Kerr-McGee Center
Oklahoma City, Okla. 73125
Warners, N. J.
Hamilton, Miss.
Los Angeles, Cal.
Oichlone (II)
2,4-D and esters and salts (I)
2,4-DB and salts (I)
Disul sodium (I)
2.4.5-T	and esters and salts (I)
Bromoxynil and esters (II)
MCPB (II)
2.3.6-Trichlorobenzoic
acid and salt (II)
Triiodobenzoic acid (II)
2,4-D and esters and salts (I)
Disul sodium (I)
2.4.5-T	and esters and salts (I)
Ioxynil (II)
MCPB (II)a
2.3.6-Trichlorobenzoic
acid (II)
2,3,6-Trichlorophenyl
acetic acid, sodium
salt (II)
Disul sodium (I)
2,4-D and esters and salts (I)
Disul sodium (I)
2.4.5-T	and esters and salts (1)
MCPB (II)
2.3.6-Tri	ch1orobenzo i c
acid (II)
2,3,6-Trichlorophenyl
acetic acid, sodium
salt (II)
Dicapthon (I)
Parathion (II)
Parathion (II)
Parathion (ll)a
(conti nued)
119

-------
TABLE 15 (Continued)
Producer
Locati on
Chemical (class)
Arapahoe Chem. Div.
Syntex Corp.
3401 Hi 11view Ave.
Palo Alto, Cal . 94304
Boulder, Col.
Chloranil (I)a
Blue Spruce Co.
Stirling, N. J. 07980
Bound Brook, N. J.
4,6-Di ni tro-o-cresol
and sodium salt (II)
Propani1 (II)
Chemical Insecticide Corp.
30 Whitman Ave.
Metuchen, N. J. 08840
(1971 address)
Metuchen, N. J.
2,4-D and esters and salts (I)a
2,4,5-T and esters and salts (I)°
2,4,5-Trichlorophenol (I)
Chempar Chem. Co., Inc.
(Address not available)
Portland, Ore.
2,4-D and esters and salts (I)a
2,4,5-T and esters and salts (1)"
W. A. C 1 eary
1049 Somerset St.
Somerset, N. J. 08873
Somerset, N. J.
Mecoprop (II)
Diamond Shamrock Corp.
1100 Superior Ave.
Cleveland, Ohio 44114
Greens Bayou, Tex.
Newark, N. J.
Chiorothaloni1 (II)
DCPA (II)
2,4-D and esters and salts (I)
2,4,5-T and esters and salts (I)
2,4,5-Trichloroghenol
and salts (I)
MCPA (II)
Dow Chemical U.S.A.
Midland, Mich.
2,4-D and esters and salts (I)
Dinitrobuty1pheno1 ammonium
salt (II)
Erbon (I)
MCPA and derivatives (II)
MCPB (II)a
Pentachlorophenol and
salts (I)
Ronnel (I)
Silvex and esters and salts (I)
2,4,5-T and esters and salts (I)
2.4.5-Trichlorophenol	(I)
2.4.6-Trichlorophenol	(I)
(conti nued)
120

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TABLE 15 (Continued)
Producer
Location
Chemical (class)
E.I. du Pont de Nemours
and Co. , Inc.
1007 Market Street
Wilmington, Del. 19898
Deepwater, N. J.
2,3,6-Trichlorobenzoic
acid and salts (II)
Eagle River Chemicals, Co.
Helena, Ark. 72342
(Subsid. of Vertac, Inc.)
Helena, Ark.
Propanil (II)
Eli Lilly and Co.
740 S. Alabama St.
Indianapolis, Ind. 96206
Indianapolis, Ind.
Lafayette, Ind.
Piperalin (II)a
Pipecolinopropyl-3,4-
dichlorobenzoate (II)
Piperalin (II)
FMC Corp.
One 111inois Center
200 East Randolph Dr.
Chicago, 111. 60601
Baltimore, Md.
Middleport, N. Y.
Tetradifon (II)3
Dichlone (I)
Fal1ek-Lankro Corp.
P.O. Box H
Tuscaloosa, Ala. 35401
(Joint venture of Fallek
Chem. Corp. and Lankro
Chem. Group Ltd. [UK])
Tuscaloosa, Ala.
2,4-D and esters and salts (I]
MCPA and derivatives (II)
Mecoprop (II)
GAF Corp.
140 West 51st St.
New York, N. Y. 10020
Linden, N. J.
Disul sodium (I)a
2,4,5-Trichlorophenol
and salts (I)
Givaudan Corp.
100 Delawanna Ave.
Clifton, N. J. 07014
(Affiliate of L. Givaudan
and Cie [Switz.])
Clifton, N. J.
Hexachlorophene (I)
Isobac 20 (I)
Guth Chemical Co.
P.O. Box 302
Napervilie, 111.
Hi 11 side, 111.
2,4-D and esters and
and salts (I)
Silvex and esters and
salts (I)
2,4,5-T and esters and
salts (I)a
MCPA (II)
Gulf Oi1 Corp.
(See Millmaster Onyx)


(conti nued)
121

-------
TABLE 15 (Continued)
Producer
Locati on
Chemical (class)
Hercules, Inc.
910 Market St.
Wilmington, Del. 19899
Brunswick, Ga

2,4,5-T and esters and
salts (I)a
2,4,5-Trichlorophenol and
salts (I)a
Hooker Chemical Corp.
1900 St. James PI.
Houston, Tex. 77027
(Subsid. of Occidental
Petroleum Corp. )
Niagara Falls
N. V.
2 ,4 ,5-Trichlorophenol and
salts (I)a
Lindane (II)
Imperial, Inc.
West 6th and Grass Sts.
Shenandoah, Iowa
Shenandoah, Iowa
2,4-D and esters and
salts (I)
Ma 11inckrodt, Inc.
675 Brown Road
P.O. Box 5840
St. Louis, Mo. 63134
Raleigh, N. C

Triiodobenzoic acid (II)a
Merck and Co. , Inc.
126 East Lincoln Ave.
Rahway, N. J. 07065
Hawthorne, N.
J.
Pentachlorophenol
and salts (I)3
Miller Chem. and Fertz.
Corp.
Subsid of
Alco Standard Corp.
Valley Forge, Pa. 19481
Whiteford, Md

2,4-D and esters and
salts (I)a
Millmaster Onyx Group
99 Park Ave.
New York, N. V. 10016
(Part of Gulf Oil Corp.)
Berkeley Hgts.
, N. J.
Si 1 vex and esters and
and salts (I)a
2,4,5-T and esters and
salts (I)a
Mobil Chem. Co.
Phosphorus Div.
P.O. Box 26638
Richmond, Va. 23261
(Div. of Mobi1 Corp.)
Charleston, S.
Mt. Pleasant,
C.
Tenn.
Dichlofenthion (I)a
Bifenox (I)
Di chlofention (I)
Monsanto Co.
800 North Lindbergh Blvd.
St. Louis, Mo. 63166
Anniston, Ala.
Luling, La.
Nitro, W. Va.
Sauget, 111.

Parathion (II)
Propani1 (II)
MCPA (II)
2,4-D and esters and
salts (I)
(conti nued)
122

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TABLE 15 (Continued)
Producer
Location
Chemical (class)
Monsanto Co. (continued)
Morton Chem. Co.
Div. of
Morton-Norwich Products,
Inc.
110 North Wacker Dr.
Chicago, 111. 60606
North Eastern Pharmaceutical
and Chem. Co.
P.O. Box 270
Stamford, Conn. 06904
Occidental Petroleum Corp
(See Hooker)
01 in Corp.
120 Long Ridge Rd.
Stanford, Conn. 06904
PBI-Gordon Corp.
300 South Third St.
Kansas City, Kans. 66118
Prentiss Drug and Chem.
Co., Inc.
363 Seventh Ave.
New York, N. V. 10001
Reichhold Chemicals, Inc.
RCI Building
White Plains, N. Y. 10603
Rhodia, Inc.
600 Madison Ave.
New York, N. Y. 10022
(Subsid. of Rhone-
Poulenc SA [France])
Ri ngwood, 111.
Verona, Mo.
Lei and, Miss.
Mcintosh, Ala.
Rochester, N. Y.
Kansas City, Kans.
Newark, N. J.
Tacoma, Wash.
N. Kansas City, Mo.
Portland, Ore.
Pentachlorophenol and
salts (I)
o-Benzyl-p-chlorophenol (II)
MCPB (II)
PCNB (II)a
Mecoprop (II)a
2,4,5-Trichlorophenol and
salts (I)a
PCNB (II)
PCNB (II)
PCNB (II)3
Dimethylamine salt of
dicamba (I)
2,4,5-T and esters and
salts (10
Mecoprop (II)
Lindone (II)
Pentachlorophenol and
and salts (I)
o-Benzyl~P""Chlorophenol (II)
2,4-D (I)a
2,4-OB (I)a
Ioxynil (II)
2,4-D (I)
2,4-DB (I)
(conti nued)
123

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TABLE 15 (Continued)
Producer
Locati on
Chemical (class)
Rhodia, Inc. (cont.)
Riverdale Chemicals, Inc.
220 E. 17th St.
Chicago Hgts., 111. 60411
Sob in Chemicals, Inc.
International Minerals
and Chem. Corp.
IMC Plaza
Libertyville, 111. 60048
Sonford Chem. Co.
Pure-Atlantic Hwy.
Port Neches, Tex. 77651
Stauffer Chemical Co.
Westport, Conn. 06880
Syntex Corp.
(See Arapahoe)
Tenneco Chemicals Co.
Park 80 Plaza West
Saddle Brook, N. J. 07662
(Part of Tenneco, Inc.)
Thompson Chemicals Corp.
3028 Locust St.
St. Louis, Mo. 63103
St. Joseph, Mo.
St. Paul , Minn.
Chicago Hgts., 111.
Newark, N. J.
Port Neches , Tex.
Cold Creek, Ala.
Henderson, Nev.
Mt. Pleasant, Tenn.
Fords, N. J.
St. Louis, Mo.
2,4-DP (I)
Bromoxynil and esters (II)
MCPA and derivatives (II)
MCPB (II)
Mecoprop (II)
2,4-D and esters and
salts (I)
2,4-OB and salts (I)
Bromoxynil and esters (II)
MCPA and derivatives (II)
MCPB (II)
Mecoprop (II)
2,4-D and esters and salts
2,4-DB (I)3
(I)'
2,4-D and esters and salts (I)
Silvex and esters and salts (I)
2,4,5-T and esters and salts (I)
Propanil (11)a
Pentachlorophenol and
salts (I)a	.
2,3,4,6-Tetrachlorophenol (I)c
Carbophenothion (II)3
Carbophenothion (II)
Parathion (II)a
2,3,6-Trichlorobenzoic
acid and salts (II)
(2,3,6-Trichlorophenyl)
acetic acid and sodium
salt (II)a
2,4-D and esters and salts (I)a
2,4,5-T and esters and salts (I)c
(conti nued)
124

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TABLE 15 (Continued)
Producer
Locati on
Chemical (class)
Thompson-Hayward Chem. Co.
5200 Speaker Rd.
P.O. Box 2383
Kansas City, Kans. 66110
(Subsid of North American
Phi 1ips Corp.)
Kansas City, Kans.
2,4-D and esters and salts (I)
Silvex and esters and salts (I)
2,4,5-T and esters and salts (I)
Transvaal, Inc.
Marshall Rd.
P.O. Box 69
Jacksonville, Ark. 72076
(Subsid. Vertac, Inc.)
Jacksonvilie,
Ark.
2,4-D and esters and salts (I)
2,4-DP (I)
Silvex and esters and salts (I)
2,4,5-T and esters and salts (I)
2,3,4,6-Tetrachlorophenol (I)
2,4,5-Trichlorophenol and salts (
Union Carbide Corp.
270 Park Ave.
New York, N. Y. 10017
(See also Amchem)
Institute and
Charleston, W
South
V a.
Disul sodium (I)a
Uniroyal, Inc.
1230 Ave. of the Americas
New York, N, Y. 10020
Naugatuck, Conn.
Chloranil (I)a
Dichlone (II)3
Velsicol Chemical Corp.
341 East Ohio St.
Chicago, 111. 60611
(Subsid. of Northwest
Industries, Inc.)
Bayport, Tex.
Beaumont, Tex

Parathion (II)a
Dicamba (I)
Vertac, Inc.
(See Transvaal and Eagle
River)



Vulcan Materials Co.
P.O. Box
Birmingham, Ala. 35223
Wichita, Kans

Pentachlorophenol and
salts (I)
Woodbury Chemicals
Subsid. of
Comutrix Corp.
8373 N. E. 2nd Ave.
Miami , Fla. 33138
Orlando, Fla.

2,4-D and esters and salts (I)
a No longer produced at this
location.


125

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TABLE 16. FORMER PESTICIDE PRODUCTION LOCATIONS
Producer
Locati on
Chemical (class)
Aceto
Flushing, N. Y.
Dichlone (II)

Amchem
Ambler, Pa.
Fremont, Cal.
Linden, N. J.
St. Joseph, Mo.
Disul Sodium (I)
2,3,6-Trichlorobenzoic
acid and salts (II)
Disul Sodium (I)
loxynil (11)
MCPB (II)
Disul Sodium (I)
Disul Sodium (I)
American Cyanamid
Warners, N. J.
Dicapthon (I)
Parathion (II)

American Potash
Hamilton, Miss.
Parathion (II)

Arapahoe
Boulder, Col.
Chloranil (I)

Chem. Insecticide Corp.
Metuchen, N. J.
2,4-D and esters and salts (I)
2,4,5-T and esters and salts (I)
2,4,5-Trichlorophenol and
salts (I)
Chempar
Portland, Ore.
2,4-D and esters and salts (I)
2,4,5-T and esters and salts (I)
Diamond Shamrock
Newark, N. J.
2,4,5-T and esters and salts (I)
2,4,5-Trichlorophenol and
salts (I)
MCPA (II)
Dow
Midland, Mich.
Erbon (I)
MCPB (II)

du Pont
Deepwater, N. J.
2,3,6-Trichlorobenzoic
acid and salts (II)
Eli Lilly
Indianapolis, Ind.
Piperalin (II)

FMC
Baltimore, Md.
Tetradifon (II)

GAF
Linden, N. J.
Disul Sodium (I)
2,4,5-Trichlorophenol
and salts (I)
(conti nued)
126

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TABLE 16 (Continued)
Producer
Location
Chemical (class)
Guth Chem.
Hi 11 side, 111.
2,4-D and esters and salts (I)
Silvex and esters and salts (I)
2,4,5-T and esters and salts (I)
MCPA (II)
Hercules
Brunswick, Ga.
2,4,5-T and esters and salts (I)
2,4,5-Trichlorophenol and salts (
Hooker
Niagara FalIs, N. Y.
2,4,5-Trichlorophenol and
salts (I)
Mai 1i nckrodt
Raleigh, N. C.
Triiodobenzoic acid (II)
Merck
Hawthorne, N. J.
Pentachlorophenol and salts (I)
Mi 11er Chem.
Whiteford, Md.
2,4-D and esters and salts (I)
Millmaster Onyx
Berkeley Hgts., N. J.
Silvex and esters and
salts (I)
2,4,5-T and esters and
salts (I)
Mobi 1
Charleston, S. C.
Dichlorofenthion (I)
Monsanto
Luling, La.
Nitro, W. Va.
Sauget, 111.
Propanil (II)
MCPA (II)
2,4-D and esters and
salts (I)
MCPB (II)
PCNB (II)
Morton
Ringwood, 111.
Mecoprop (I)
N. Eastern Pharm.
Verona, Mo.
2,4,5-Trichlorophenol and
salts (I)
01 i n
Rochester, N. Y.
PCNB (II)
Rhodi a
N. Kansas City, Mo.
Portland, Ore.
St. Paul , Mi nn.
2,4-D and esters and
salts (I)
2,4-DB and salts (I)
Ioxynil (II)
2,4-D and esters and salts (I)
2,4-DB and salts (I)
(conti nued)
127

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TABLE 16 (Continued)
Producer
Locati on
Chemical (class)
Sobin Chem.
Newark, N. J.
Propanil (II)
Sonford
Port Neches, Tex.
Pentachlorophenol and
salts (I)
2,3,4,6-Tetrachlorophenol (I)
Stauffer
Cold Creek, Ala.
Carbophenothion (II)
Tenneco
Fords, N. J.
2,3,6-Trichlorobenzoic acid
and salts (II)
(2,3,6-Trichlorophenyl)
acetic acid (II)
Thompson Chem.
St. Louis, Mo.
2,4-D and esters and salts (I)
2,4,5-T and esters and salts (I)
Union Carbide
Institute and South
Charleston, W. Va.
Disul Sodium (I)
Uni royal
Naugatuck, Conn.
Chloranil (I)
Dichlone (II)
Velsi col
Bayport, Tex.
Chattanooga, Tenn.
Parathion (II)
Dicamba (I)
Woodbury
Orlando, Fla.
2,4-D and esters and
salts (I)
128

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VOLUME III
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Kaupp, J., and H. Klug. 1962. Perchlorodiphenylene dioxide. German Patent
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131

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132

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Vinopal, J. H. , I. Yamamoto, and J. E. Casida. 1973. Preparation of
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133

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VOLUME III
BIBLIOGRAPHY
Berg, Gordon L. , ed. 1975. Farm Chemicals Handbook. Meister Publ. Co.,
Willoughby, Ohio.
Cattabeni, F. , A. Cavallaro, and G. Galli, eds. 1978. Dioxin - Toxicolog-
ical and Chemical Aspects. Spectrum Publications, Inc., New York.
Hawley, G. , 1977. Condensed Chemical Dictionary. 9th Ed. , Van Nostrand-
Reinhold, New York.
Monsanto Research Corp. and Research Triangle Institute. 1976. Chapter 6:
The Industrial Organic Chemicals Industry - Part I. In: Industrial
Process Profiles for Environmental Use. EPA-68-02-1302 and 1325,
Research Triangle Park, North Carolina.
Parsons, T. , ed. 1977. Chapter 8: Pesticides Industry. In: Industrial
Process Profiles for Environmental Use. Radian Corp. EPA-68-02-1319,
Research Triangle Park, North Carolina.
Rawls, L. 1979. Dow Finds Support, Doubt for Dioxin Ideas. Chem. and Eng.
News, 57(7): 23-29.
Sittig, M. , ed. 1977. Pesticide Process Encyclopedia. Noyes Data Corp.,
New Jersey.
Stanford Research Institute. 1968, 1969, 1971, 1972, 1973, and 1978.
Directory of Chemical Producers - USA. Menlo Park, California.
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Publishing Co.
Windholz, M. , ed. 1976. Merck Index, 9th Ed., Merck and Co., Inc., Rahway,
New Jersey.
134

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-600/2-80-158
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Dioxins: Volume III. Assessment of Dioxin-Forming
Chemical Processes
5. REPORT DATE
JUNE 1980 ISSUING DATE.
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
F.E. Dryden, H.E. Ensley. R.J. Rossi, and
E.J. Westbrook
8. PE-RFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Walk, Haydel, & Associates, Inc.
600 Carondelet St.
New Orleans, LA 70130
10. PROGRAM ELEMENT NO.
1BB610
11. CONTRACT/GRANT NO.
Contract Mo.
68-03-2579
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati. Ohio 45268
13. TYPE OF RE PORT AN D PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
Volume III of a three-volume series on dioxins
16. ABSTRACT
Chemical reaction mechanisms by which dioxins may be formed, are
reviewed, particularly those likely to occur within commercially significant
processes. Various routes of formation are identified in addition to the
classical route of the hydrolysis of trichlorophenol. Basic organic chemicals
and resticides with a reasonable potential for dioxin byproduct contamination
are surveyed as to current and past producers and production locations.
Classifications are presented both for general organic chemicals and
for pesticides that indicate likelihood of dioxin formation. Conditions
are noted that are most likely to promote dioxin formation in various
processes.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
e. cosati f ield/Group
Organic chemicals
Pesti ci des
Chemical reactions
Chemical plants
Dioxins
2,3,7,8 - TCDD
Environmental biology
Hydrolysi s
Chemical manufacturing
07C
06F
07C
07A
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report/
Unclassi fied
21. NO. OF PAGES
147
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) previous edition is obsolete	~	=
135

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