WATER POLLUTION CONTROL RESEARCH SERIES
16020 EWC 04/71
Catalog of Pesticide
NMR Spectra
ENVIRONMENTAL PROTECTION AGENCY • RESEARCH AND MONITORING
-------
WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes
the results and progress in the control and abatement
of pollution in our Nation's waters. They provide a
central source of information on the research, develop-
ment, and demonstration activities in the Environmental
Protection Agency, through inhouse research and grants
and contracts with Federal, State, and local agencies,
research institutions, and industrial organizations,
Inquiries pertaining to Water Pollution Control Research
Reports should be directed to the Head, Project Reports
System, Office of Research and Monitoring, Environmental
Protection Agency, Room 801, Washington, D.C. 20242.
-------
CATALOG OF PESTICIDE
NMR SPECTRA
by
Enviroiiiiiental Protection Agency
Southeast Water Laboratory
Athens, Georgia 30601
Project #16020 EWC
April 1971
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price $1.50
-------
EPA Review Notice
This report has been reviewed by the Water Quality Office,
EPA, and approved for publication. Approval does not signify
that the contents necessarily reflect the views and policies
of the Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or
recommendation for use.
-------
ABSTRACT
This catalog contains the 100-MHz NMR spectra of 114 organo-
phosphorus, DDT, and carbamate pesticides and a brief discussion
of their most important features. Chemical shifts and coupling
constants are shown on each spectrum.
111
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CONTENTS
Section
Page
I Introduction 1
II Experimental 3
III Discussion
A. The Organophosphorus Pesticides 5
B. DDT and Related Compounds 61
C. The Carbamate Pesticides 93
IV Index to Spectra 137
V Acknowledgments 149
VI References 151
VII List of Publications Resulting from this Work 153
VIII Appendix: Chemical Names and Sources of the
Pesticides 155
-------
SECTION I
INTRODUCTION
Pesticides are inportant sources of water contamination. Individual
pesticides or their degradation products must often be identified if
the water quality is to be protected and improved. Nuclear magnetic
resonance (NMR) spectroscopy provides unique structural information (1)
that cannot be obtained from infrared spectroscopy, mass spectrometry,
and gas chromatography (the primary instrumental methods currently used
to identify water contaminants).
Interpretation of NMR spectra is enhanced when spectra of known similar
compounds are available for comparison. Since few pesticides have been
included in NMR spectral catalogs, we recorded and interpreted spectra
of three important classes of pesticides and some of their degradation
products. Spectral interpretations were discussed in previous publica-
tions (2-5), but only a few spectra were included.
This catalog contains spectra of 114 compounds arranged according to
molecular structures:
1. Organophosphorus pesticides
a. Phosphomethoxy [(CH30)2-P]
b. Phosphoethoxy [(C2H50)2-P]
c. Miscellaneous
2. DDT and related compounds — pesticides and several known or
proposed metabolites with the substitute diphenyl
methane skeleton.
3. Carbamate pesticides.
-------
Chemical names and sources of the compounds are listed in the Appendix
in the order they appear in this publication. Section IV is an
alphabetical index of the common names and trade names of all compounds
in this catalog.
-------
SECTION II
EXPERIMENTAL
The 100-MHz spectra were recorded with a Varian HA-100 NMR spectrometer
equipped with a variable-temperature probe and a homonuclear spin
decoupler. Solutions (300 mg/mlj were prepared in deuterochloroform,
except when other solvents or less concentrated solutions had to be used,
or when changing solvent or concentration produced a desirable chemical
shift. Each spectrum shows chemical shifts (T values with reference to
the internal standard, tetramethylsilane). Sweep widths of 1000 Hz or
500 Hz were used, but portions of some spectra were expanded for more
detailed analysis. In some cases homonuclear spin decoupling, inte-
gration, protonation with trifluoroacetic acid, D20 exchange, temperature,
solvent and concentration variations, and supplemental 60-Miz spectra
were needed for spectral interpretation.
-------
SECTION III
DISCUSSION
THE ORGANOPHOSPHORUS PESTICIDES
Signal splittings due to coupling of phosphorus with hydrogen complicate
these spectra. Coupling constants, inversely proportional to the P-H
distance, vary from 0.5 to 18 Hz. The aromatic proton signals of ronnel,
dicapthon, Ruelene, Zytron, methyl parathion, ethyl parathion and
paraoxon, have a small splitting due to P-H coupling through four and/or
five bonds. The phosphoethoxy methyl signals (T 8.59-8.67, J = 0.5-1.2 Hz)
also show P-H coupling through four bonds.
Each spectrum of the phosphomethoxy compounds exhibits a doublet
(J = 11-16 Hz, T 6.1-6.3) due to the CH,0-P protons coupled through oxygen
to phosphorus. In malathion, malaoxon, Dibrom, and Neguvon, each doublet
exhibits a smaller splitting (<2Hz). Two methoxyl groups are attached
to the phosphorus atom and an asymmetric carbon atom is present; therefore,
this splitting is actually a chemical shift difference due to a small
magnetic non-equivalence of the methoxyl groups. Similarly, methylene
groups of several phosphoethoxy compounds (Thimet, Di-Syston, Trithion
and ethion) produce 16, rather than the expected eight, peaks. Each non-
equivalent methylene group is coupled with methyl protons to produce a
quartet that is further split by phosphorus. The signals of the phospho-
ethoxy methylene protons appear at T5.65-5.91 with P-H coupling of 8-10 Hz.
-------
A-la
a 8.71 7
a' 8.75 7
b V93 ' 9 (»«
c>
d
d'
6.J9 li5(P-H>
&20 ISJ(P-H)
5.78 7
5.85 7
5.9
-------
A-lb
75'
50'
o 9.04 7
a' 9.08 7
b ^90
fa'
c 6.52 ISi5(P-H)
liS(P-H)
9 (vie)
17(g,m.)
*7.22 C 6 (vit)
c' 6.54
d 6.03
d' 6.10
• 5A7
175(P-H)
» (H-Hb)
6 (H-Hb.)
10
-------
7 Malooxon
'" <«' ft W ft. Wl (»>
50 CH7O-P-S-CH-C-OCHoCHi
CO
(a
o'l
A-2
a
a'
b
b'
c
e1
d
d'
8.71
8.75
'6.88
*715
6.17
6.18
5.78
5.85
5.9
7
8 (vie.)
6(vie.)
13
13
7
7
10
-------
A-3
4.5
IB
IS
-------
Dim«thoxon
40O
(d)
,«, O OH
11 ii ii i
eH3O-P-S-CH2-C-N-CH3
CH30 W
(c)
(d)
A-4
a
b
c
d
7.17
649
6.17
2.55
5
17
12J
2.35
7.35
-------
T
Mvta-Systox-lT0
O
ii
..,
(b)
rlVi
(«")
rh
A-5
a
b
8.65
7.21
6.8
6.18
7
7
13
10
-------
A-6
"° Dibrem
-
O
it
Br Br
i
CHoO-P-0-C-C-CI
J i ii
CH30 H Cl
(a-) (b)
to
(b)
a 6.08 12 (P-H)
.„, ^ 12 (P-H)
'
b 3.30
-------
A-7
f Ncguvon <0°
W
O OH
(o) H I
CH3O-P-CH-CCI3
CH0 (W
t
so
•xcKongvd
with DjO
(b)
a 6.09 11 (P-H)
a' 6.10 11 (P-H)
b 5.43 12(P-H)
c 3.69
-------
A-8
DDVP
f («) m (W
CH30-P-OCH=CCI2
CHoO
f
a
b
6.14
3.00
II
5.5
10
-------
A-9
M
Ul
a
b
c
d
848 7
7.63 08
6.20 ll(P-H)
4.14
4.10 7
270
-------
CTl
f Axodrln
w
o
II
(d)
H
H
CHoO-P-0-C=C-C-N-CH-
• i ii *
CH»O CH-, O
CH30
(d)
A-10
a
b
7.58
721
6.16
4.21
3.0
0.9
5
11 (P-H)
0.9
10
-------
A-n
a
b
b'
c
d
7.74
7.03
6.96
6.17
3.89
J
as
11
-------
A-12
I-1
oo
'CH-jO-P-O-CsCH-C*
1.0
OJ
11.5
11.5
%
tram C = C
-------
I-1
vo
A-13
a
a'
b Irani
b' cis
c
e'
d ci.
8.83
8.79
7.90
7.78
639
6.56
6.20
d'trans 6.12
trans
-O'
7
7
1.6
16
7
7
12
12
CI
c=c
-o' "ci
-------
A-14
"» M*»hyl Trithion
(») II (b)
CH3O-P-5-CH2-S-
(c) (c)
-Cl
(c)
a
b
c
6.28
5.74
2A7
IS
14
-------
(b)
W
L,
A-15
4
10
a 6.24 15
b 4.23 16
e 1.9
-------
Outhlan oxygen"0 analog
O (£)
I- o — p.
4 I
CH3O
(«)
<->/w
f\
fe)
Cb)
A-16
10
6.19
4M
2X>
13
IS
-------
1
Irnldan
CO
(c)
(•) g (V ,
CH30-P-S-CH2-I^
CHoO
(a)3
(b)
A-17
a
b
6.23
4.98
2.18
15
15
10
-------
to
W)
A-18
(b)
U/U
-'W
a
b
c
d
768
7.60
6.19
3.0
14
10
-------
A-19
Abat*
(a)
s
II
CH.,0 -P-O-
«* i
(b)
T J
6.17 14(P-H)
b 2.5
-------
Ronnvl
ISO
1 s
I (<•) II
CH3O-P-0-
Cl
\
Iv)
to
-Cl
(b)
A-20
i
10
6.10 14
2.55 1.8(P-H)
2.47 lO(P-H)
-------
rate
»°
to
Oardona
C
CH30-P-O-C-
CH30 CIHC />
Wfc)
A-21
V
a
b
J_
6.21
3.92
2.46
2.43
_J_
11 (P-H)
1.5 (P-H)
-------
IUW
Jo Methyl Parathion,
100
i
(O
00
(b) (c)
(W
~~s^~t
A-22
10
a 6.13 14
b Z70 9
c 1.78 9
-------
A-23
N>
500 Sumithion
(b) n
CH3O-P-O-
C3°
7.38
6.12
2.84
1.98
14(P-H)
10
-------
A-24
Dicapthon
w *
CH30-P-O-
(b) (c)
CHoO /
(a) Cl
-NO-
(d)
W W
(o)
a
b
c
d
6£>8
2.49
1.87
14
9 1
151P-H )
i8(H-Hm)
1.2JP-H1")
10
-------
10 P
I 1
1 9
4°
CHoO-P-N
CH3-C-CH3
(0) CH3(0)
(f)
A
A-25a
8.72
»« c 'in
6.2-6.7
6.19 I1(P-H>
2.62 2.5(H-Hm)
257
2'57
1.0(P-
10
-------
ro
1
w
Ru*l«n«
A-25B
u
SOmfl/O.Sml
75mg/0.5ml
100 mg/0.5 ml
10
-------
A-25c
CO
Co
10
-------
A-26
u>
8.81
6.8
6.3
6.20
2.81 :
6.5
14
9 (H-H0)
°
->w - Z5(H-Hm
2.59 ^ iflip-H1")
246 " 9 (H"Ho'
**° x 1.3 (P-H)
-------
A-27
CO
01
CH3CH20-P-S-CH2-S-CH2CH3
8.71
7.30
5.97
5.815
5.83
O8IP-H)
7
7
13(P-H)
10(P-H)
7 (H-H)
-------
A-28
(b) (•) .*j (d) (c)
CH3CH20-P-S-CH2CH2-S-CH2
CH3CH2O
(b) (•')
a 8.73 7.5
. _.- ^ 7(H-H)
b 8.65 ^ o.7(P-H)
c 7/40 7.5
d 63-7.5
. 5.83 10(P-H)
,' 5.85 ^ 7(H-H)
-------
A-29
Syitox
CO
•J
OHf**"****'!
« n (0 W)
CH3CH7O
a.)3 w2
(•)
W
S^»A(^N^«^f>^y«((by^W^
p-r+fr
rtrtvv'***^^*^^
nffii
>-«>
o ere
a
b
c
d
•
f
8. 73 7. 5
7 (H-H)
0.9 (P-H)
7.41 7.5
7.20 7
7 (H-H)
10 (P-H)
5.8
10
-------
A-30
I
I Uo-Systox
T
r
U>
00
(b) W I (d) (d)
(c) (a)
CHoCHoO
-------
A-31
OJ
o 8.64 7
b 6.3
« 5.83 10(P-H)
d 4.32 13
-------
A-32
CHoCHoO-P-S-CH^-S-
a
b
b
c
d
8.67
SM
5.91
5-72
2.68
7
10(P-H)
7(H-H)
13.5(P-H)
-------
A-33a
a
b
b'
8.62
5.82
5.80
5.74
7 (H-H)
0.8 (P-H)
7 (H-H)
10 (P-H)
7 (H-H)
10 (P-H)
17 (P-H)
10
,000
T Ethion
(«» (M
*
(c) j (W (a)
CH3CH2O-P-S-CH2-S-P-OCH2CH3
H3CH20 OCH2CH3
(a)
-------
to
A-33b
10
-------
U)
ICO
10
Ph«ncapton
t («) (b)
s
II
(«)
CH3CH2O-P-S-CH2-S-
CHoCHoO
A-34
a
b
b'
c
d
8.64 7
5.82 ^ 10(I>-H)
SM ' 7 (H-H)
5.66 14
2.8
10
-------
A-35
Dursbon
ib
*>.
Cl
Cl
w
(b').(b)
61 s
II (b) (a)
O-.p-OCH2CH3
W
>-H»
0 CPS
b 5.61
b' 5.60
c 2.16
\ 7 (H-
/ 10 (P-
7 (H-H)
H)
1.2 (P-H)
10
-------
A-36
Zinophoi
* (a) (b) * |
CH3CH20-P-<
CM3CH20
(a) (b)
(«)
en
(4
W
(b)
jJLJ[
1.72
1.67
10
-------
A-37
T
T W (•) it //"NV CH
CH3CH20-P-0-^(jN (,
>
a
b
c
d
e
7 (H-H)
W(P-H)
8.68
8.62
7.51
6.S8 7
,-,,-. 95(P-H)
5A6 - 7 (H-M)
3,34
10
-------
A-38
a
b
c
d
e
I
8.68
8.61
7.51
6.87
5.65
126
7 (H-H)
1.21P-H)
7 (H-H)
8IP-H)
-------
A-39
n i
> o
JO
HO
'00
Cthyl Outhion
H (b) f| (c) ,
CHoCHoO-P-S-CHo-N
32, 2^
00
(o) (bO
b'
c
d
5.84
5.80
4.19
1.9
O.S(P-H)
7 (H-H)
10.5(P-H>
7 (H-HI
T6 (P-H)
-------
A-40
Co-Rol
I ,„, ,., s
CH3CH20-P-O-
CH3CH20 W)
(a) («)
a
b
7^43
2.83
2-37
7.0(H-H>
as(p-H)
7.0(H-H)
- WJO(P-H)
9.5(H-H0)
0.8
-------
A-41
f Ethyl Porathion *
v W
« («) W *
50 CH3CH2O-P-O-
CH3CH2O
(0) (b)
(d)
-NOi
W)
863 ,, Q8(P-H)
a 8.63 ^ 7{H.H)
10 (P-H)
7 (H-H)
5.75
. 7 AT - '
-------
A-42
ISO
Porooxon
fa)
CH3CH20-P-0-
C»3CX!20
(d)
(c)
;w
I
a
b
c
d
7 (H-H1
0.9 (P-H)
240
.,«
1176
7 »Hfl
9 (H-H)
IfllP-H)
9 (H-H)
07 (P-H)
10
-------
A-43
(b) ft
CH3CH20-P-0-C
CIHC
(a)" (b)" W
b
b'
JL J.
8'74 \ 1.2 (P-H)
5.89 7
5.88
4.00
2.65
7
1.5 (P-H)
-------
A-44
8.64
5.73
2.64
1.96
7 (H-H)
0.5 (P-H)
7 (H-H)
10 (P-H)
-------
HO
10
"
Sulf otcpp
s s
(a) (b) || II (b) (a)
CH3CH2O -p-o-P- OCH2CH3
CH3CH2O OCH2CH3
(a) (b) (b) (a)
Ul
A-45
(o)
I I
(a)
8.65
7 (H-H)
0.5(P-H)
7 (H-H)
10 (P-H)
10
-------
A-46
01
en
CH3CH2CH2O OCH2CH2CH3
a
b
9.03
8.27
5.88
7
ftS(P-H)
7 (H-H)
10
-------
A-47
Falon*
750
T
tn
tb)
III
(b)
(bl (b)
a 5.4-6.7
b Z6-?.4
10
-------
A-48
Merphos
Jo
T
T H (b) (c) W
" (CH3CH2CH2CH2S)3-P
en
T J
a 9.08 7
b,c 8J-&8
d 7.2
10
-------
A-49
a
b
c
d
9.05
8.5
8JZ5
7.01
6.5
IS(P-H)
-------
(d),
W*p»yn
ui
CH3'
O
(a)
(b)
(d)
NH2
(b)
A-50
a
b
c
d
7.24 10.5
3.14
2.61
1.98
10
-------
THE DDT-TYPE COMPOUNDS
Most DET-type compounds contain para-disubstituted benzene rings whose
protons produce complex multiplets. Each benzene ring contains four
magnetically non-equivalent protons that form two pairs of equivalent
nuclei with a chemical shift difference approximately equal to the
coupling constants involved. This is defined as an AA'BB1 system (6).
The complex spectrum prevents interpretation by visual inspection, but
an approximation of the ortho coupling constants and aromatic proton
chemical shifts was obtained as described in a previous publication (4).
The ortho protons of compounds with the CGI, moiety on the ct-carbon
resonate at a significantly lower field (r2.42-2.52) than ortho protons
of compounds with other functional groups on the a-carbon 02.72-2.90).
This large deshielding effect of the CC13 moiety may be explained by
considering the molecular stereochemistry as observed in Leybold models.
When three chlorines are substituted on the 8-carbon, the ortho aromatic
protons cannot escape the deshielding effect of the chlorine atoms.
However, if only one chlorine atom is removed, the ortho protons are no
longer forced into close proximity to the chlorine atoms. The deshielding
effect of the CC1 group is greatest when chlorine substitution on
one of the aromatic rings occurs in the ortho position. Examination
of a I^ybold model shows that a chlorine in the ortho position of a ring
causes rotation of that ring around the aromatic-aliphatic C-C bond to
be energetically unfavorable. The most favorable conformation places the
remaining ortho proton near the B-carbon chlorines and the ortho chlorine
as far as possible from the CCLj moiety.
The meta protons of the aromatic rings with para chlorine substi-
tuents resonate in a range from t2.68-2.76. As expected, the benzylic
61
-------
proton signals 05.06-6.0) are deshielded more by an ortho than a para
chlorine on an aromatic ring.
Technical DDT is a mixture of p_,p_f-DDT and o.p^-DDT. Peak area measure-
ments by electronic integration of the part of the spectrum containing
the signals of the benzylic protons (p_,p_'-DDT, iS.OO; p_,p_'-DDT, x4.25)
provide the isomeric composition of the sample (80% p_,p_'-DDT, 201 £,p_'-DDT)'
The spectrum of Dilan, a mixture of Bulan and ProIan, contains only one
benzylic peak but has two methyl signals with significantly different
chemical shifts (triplet, i9.ll; doublet, T8.54). The integration of these
methyl signals provides the percentage of each compound in the mixture
(62% Bulan, 381 Prolan).
62
-------
(a)
(b) (c)
CCI3(«) (W
B-l
a SJOQ
b 2.77 as
« W3 8.5
. 4
10
-------
B-2
(0 («) CCI3« (b)
a 4.25
b 2.74 8.5
c 2.6-2.9
d 2.52 8.5
• 1.88
10
-------
B-3
Technical DDT
Mixture of
o,p' DDT
and
-------
B-4
\r"iiuni1^T^rtn»)»ljmn>|i M. rv A or. 'i r
a 428
b 2.4-24
c L84H.96
10
-------
B-5
Mvthoxychlor
o\
-j
(b)
W W CCI3W) (c)
a
b
c
d
!. 1
6.29
5.06
3.18 9
2.52 9
10
-------
B-6
03
(b) (c) OH (e) (b)
(a)
a
b
c
6.48
2.76 9
2.42 9
1O
-------
sto _ _/
p,p'DDD
(d)
OV
(a)
B-7
(di (c)
(c) (d)
CI-C-CI
H
(b)
a 5.49
b 3.74
c 2.78
d 2.74
8
8
9
9
10
-------
B-8
a
b
c
4*2
3A4
-------
B-9
a 60S 8
b 5.75 8
c 2.88 8.5
d 2.74 &5
10
-------
B-10
P«rthan«
50
ro
(f)
J
W
<•) (f) H <«
{•) (OCI-C-CKO (e)
H
(d)
(d)
1
(b) (a)
a
b
c
d
e
I
8.84
Z43
5.50
3.68
2.92
230
9
9
10
-------
DDE
(b)
(a)
(b)
B-ll
T_ J
a ZA8 9
b 2.75 9
10
-------
B-12
a
b
c
d
_L .i
3.45
2.91 8^
2.77 8^
2.75 8.5
2.65 8.5
10
-------
B-13
a
b
c
3.62
3.28
2.5-3JO
-------
DDNU
(clb)
(a)
W (W
(b) (c)
Cl-
-Cl
B-14
x
a 4.59
b 2.80
e 2.74
9
9
10
-------
B-15
a
b
2J5
2.29
8.5
10
-------
B-16
DDA
00
(«),<«
(c) (b) H (b) (c)
a
b
c
d
5.03
2.77
2.71
as
9
9
10
-------
B-17
ite
i o
DDA Methyl Esl«r
(d)
(b)
(d) (0
Cl-
-Cl
T
a 6.29
b 5.06
c 279
d 2.73
9
9
10
-------
B-18
T
Diphcnamid
oo
o
(c)
J
(fa)
a
a'
b
c
7.12
7.08
4.82
2.79
10
-------
B-19
a
b
c
d
e
8.78
5.73
5.68
2.72
2.68
7
7
9
9
10
-------
B-20
00
to
o
1 '
(• Chloropropylat*"
L
A
,
(•)
U)
s
y
j
!
i
1 --,----,----
' "
- • • i • i
1
300 200
Cl-
,1, 1
0^3 added JW
• V
/-~^
JT — '
--•~^ rm
1 J
•L J
,
Y^
It, A
, i ...
.........I........
W W)
^\
•\C )/-
x^y
(•) W)
(a)
Hf>
3n^
......... I .........
i
i i i
(b) 1M «
OH(d) W |p-
' vP^ '
c-(( )Va
1 V±^ 1
C=OW) («)
1
1 2__— ^^^^
W tMo
1
H
I
........ .1 ......
Jk,
T IT *
P CTS
^1
, „ -^
....!....
T
T J
a 8.79 6
b &63
_ A fiO A
d 173 9
• 170 9
31 2 3456789 10
-------
B-21
a
b
c
d
8.54
542
4.70
2.78
6
12
-------
B-22a
a 9.11
b 8.23
b' 8.25
d 4^6
2.80
11.5
-------
B-22b
Bulon
00
U1
(d)
il
A H0*Hd d««wpl*d
from Hb*Hb-
B Hc,Hbftt^ decoupled
from Hj
C Hj decoupled
from Hc
Sw»p Width 500
-------
B-23
Mixture of
Prolcm and Bulan
-------
B-24a
DDOH
00
•vl
(e) (d) H (d) (•)
(a)
a 7.82
b,c 60
d 290 9
• Z75 9
10
-------
woo
4°
DDOH
inCCl4
CO
00
(a)
Ml
(d)
(b)
(c)
B-24b
Trichloroacctyl Isocyanot* added
(•) (d) <4 (d) (•)
(a)
J_ £
a 8.19
b,e 6.1
d 2.97 9
10
-------
B-25
(b) (b) H (b) (b)
DjO added
00
imp.
O 6.17
b 79-33
c
-------
B-26
T
a 6.24
b 5.82
e 4.57
d 2.77
-------
B-27
Isebutyl Triph«nftm*thylamin«
H3C-C-CH3
(a) « (a)
H
a 9.11 7
b 8.54
C 8.33
d 8.05 6
-------
THE CARBAMATE PESTICIDES
Thirteen carhamate pesticides included in this study have the general
structure:
0 H
II /
R-O-C-N
\
In all cases, the methyl protons resonate in a narrow range from
T?. 20-7. 29 and produce a doublet ( J = 5 Hz) due to coupling of the methyl
protons with the amide proton.
Although hindered rotation about the N-C-0 bond of amides is quite
common and produces both the cis and trans isomers, this phenomenon
is observed at ambient temperature in only one of the N-monosubstituted
carbamates, Azak. Other investigators (7,8) have also reported hindered
Station about the N-C^O bond in carbamates at low temperature but
essentially free rotation at higher temperatures. In Azak, the bulky
t-butyl groups substituted on the benzene ring in the ortho positions
sterically hinder rotation — a signal is observed for each isomeric
at ambient temperature. Both N,N-dimethyl carbamates included in this
study (Dimetilan and isolan) exhibit hindered rotation at ambient
temperature and produce signals for both rotomer forms.
chemical shifts of both the NH and NQI proton signals of Zectran
•?
are dependent on solvent and concentration. Various concentrations of
Zectran in three different solvents were used to study the effects of
solute-solute and solute -solvent association (5).
•*he signals of the protons near or adjacent to nitrogen in many of these
impounds show broadening due to the quadrupole moment of the nitrogen
93
-------
nucleus as well as some hindrance to rotation (7, 9). Increasing the
sample temperature sharpens peaks that are broadened due to one or both
effects (10, 11). Low temperature studies (5) confirmed that rotation
is hindered in both the thiolcarbamates (example: sutan) and the dithio-
carbamates (example: Vegadex).
94
-------
c-i
o
II W) (c)
O-C-NH-CH3
T J
a 7.91
b 7.76
e 7.26
d 4.7
e 3.25
10
-------
C-2
ft (d) (b)
O-C-NH-CH
a 8.77
b 7.26
c 7.12
d 4.6
e 2A-&2
7
S
7
-------
C-3
&64
7.65
7.22
7.06
d' 4.8
d 4.4
e 2J8
a
b
c
e'
5
5
W
C-N
C-N
/ v
0 H
(4
-------
C-4
Rf 5305
00
(b)
(c) (a)
-------
C-5
Baygon
vo
II (d) (b)
O-C-NH-CHo
(c) 3
O-CH-CHo
i (or
CH3
J
a a/0
b 7.22
c 5.52
d 4.6
e 2.7-12
6
5
6
-------
Carbanolot*
o
o
(e) (d)
C-6
(b)
(c)
a
b
d
e
7.83
7.20
4.70
3.07
2.87
10
-------
C-7
Bcnomyl
{} (8) (<) (b) (b) (a)
C-NH-CH2-CH2-CH2-CH3
X-NH-C-O-CHo
N' (h) JJ (d)
(d)
(c)
(b)
(a)
>-*<>
0 Q*
a 9.02
b 8.2-8.7
e 6.57
d 6.20
• 2.80
f 1.66
g -0.14
h - 1.4
7(Hb-Hc)
6(Mc-Hg)
10
-------
C-8
,.
Mvtabolit* o*400B«nomyl i«
.300
H(a)
M °
XNH-C-0-CH3
• if' (o) (b)
(•
10
T_ J_
a 6.30
b 6.19
e 3.40 8.5(HC-H«)
2.5(Hc-Hd)
d 3.12 2.5(He-Hj)
e 2.76 4.5(Hc-He)
-------
C-9
S«vin
o
OJ
O
II (b) (a)
O-C-NH-CH3
(b)
Imp.
Imp.
^
a 7.29
b 4.7
c 2.0-2.8
10
-------
C-10
a 8.24
b 7.38
< 7.2
d 7.24 5
e 4.7
f 19-3.2
-------
C-ll
a 8.52
b 7.20
c 7.00
d 4.7
e 3.0-33
-------
C-12
(b) (a)
O-C-NH-CHo
a 7.32
b 4.59
e 2.3-3.0
-------
C-13
Matacil
o-C-NH-CH
(e)
(d)
T J
a 7.71
b 7,37
c 726
d 4.6
e 3.1
10
-------
C-14a
1
SO
Z«ctran
O
00
O"C"NH"CH3
a
b
c
d
7.88
7.28
7.26
4.80
133
10
-------
C-14B
to
s
i
i
f-1
O
VO
C
•••••••• i ----,---- 1
n '
0 400
* Zectran 1% in CDCI3
1
t \
WH3C
. . . ^_ i . ^ . ,
»
\0)
H^C (e) Q
>-u^-o-c-i
H3C (•)
(a)
1
......... |
300
(d)
^H
1
....!....
^
,
1
200
(d)
A.
/ H^
(d)
, r^^. «run. f. .IKK
1
(c
1
1
i
.........
100
......... \ .....
Jk
,
j
L
0 CPS
1
T
a 7.75
b 7.1-7.15
c 7.22
d 5.14
e 3.28
1 23456789 10
-------
C-14c
1 ' ' • ' 1 ' ' ' ' 1
• • • i i • • • • 1
• • • ' i • • • • |
0 400
; ' • ' |
300
200
100
0 CPS
0 Z«clron 40% in CDCI3
0
— «. — -*— < —
*- ' j> ", ' — • —
1 . , . . i : • . •
^
V
- i • • . i_.
(d)
_I_I.J.. I.J-L-L.l-J.
.
.
(<
J
)
(a)
lu
\ ~
K
........
T J
a 7.78
b 7.33-7.38 5
e 7.25
d 4.39
e 3.31
10
-------
C-15
mo
9 B
1 0
I 0
50
Masurol
(b)
C"3(e) Q
(a) >^\ II » W
CH3-S-(( ))-0-C-NH-CH3
(d)
a 7.93
b 748
c 724
d 4.7
e 3.13
10
-------
*° Sirmat* 2,3-llomer
10
(d) (d)
/H(b)
(C)
(b)
(a)
J
C-16
T _J
a 7.18 5
b 5.10
C 4.78
d 2.55-2.92
10
-------
C-17
I _J
a 7.20 5
b 5.0
e 4.97
d 2.86 8.5
-------
C-17b
Commercial Sifmat*
Mixlur*
SO* 3,4 Isomer
2O* 2.3 Isomer
-------
c-18
(b) .00
(a)
"
(c)
10
a 7.77
b 7.61
c 7.13
d 3.80
M.thomyl
- (b)
jo U
(a)
(c)
(d)
-------
C-19
(b) | *(») || (d) (c)
CH3-S-OCH=N-O-C-NH-CH3
a 8.54
b 8.03
c 7.10 5
d 3.75
e 2.46
-------
C-20
o
o Isolon
:
L 0>)
£
*00 300
W
H
(c)
>O-C-N'
H3C-C-CH3
(or i w3
W
ll
H
d
J)
.:.:.;...
1 ....!..,.
.
/
(<
__ ^J
fh
1
>)
1 .... 1 .... 1
. "|:'|
i
':•;';';•.
200 lofb) II
(d)
rmtn
J
I
/_i\
«r
^
Jj
r
a>)
(c-
(
^
7
j^
r—
;
H
1 (<
i
\
1
ll
i ' • • • i ' • • '
0 CP5
1 1
T J
a 057 7
b 7.78 05
c 6.99
c' 6.91
d 5.66 7
« 4.23 as
K>
-------
C-21
ii / \ ii /
-C-,1 >0-C-N,
a
b
b'
c
d
I_ 1
7.60 OB
703
6.95
6.94
3.99 08
-------
022
I PC
(a)
0-CH
T J
a 8.76 6
b 5,00 6
c 3£
d 24-3.1
10
-------
C-23
CIPC
OW
1
L
(c)
NH-C
S0-CH
(b)
rffnti
(a)
a 8.75
b 5.03
c 3.0
d 25-3.1
6
6
10
-------
Barban
29W
f
o
II
(b)
(a)
NH-C-0-CH2-C=C-CH2CI
Cl
(d)
C-24
a
b
c
d
5.86
5.20
2.9
-------
C-25
T
150
1
to
(W (a)
NH-C-O-CH3
. V
a
b
6.25
3.05
2.4-2.9
10
-------
C-26
NI
u>
,t- - _, » «
W W <•) N-OS-CH2CH3
CH3CH2CH2
a
b
c
d
e
9.10
8.73
8.40
7.11
6.72
7
7.5
7-75
7.5
75
-------
NJ
- ~ X
CH3CH2-S-C-N
S
C-27
T J
a 9.09 &5
b ars 7
c 7.96
d 7.10 7
• &81 73
-------
028
(b) (d) (e) CH2CH3
CH3CH2CH2-S-C-N
"cHnCHoCHoCHo
z 3
a 9.08 6J5
b 9,03 7
c 8.86 7
d 8.2-8.7
• 7.15 7
f 6.70 7
g 6.M 7
-------
C-29
Vcrnam
r
tr>
300 (e)2°° (c) (a)
(W ft) (d) S XCH2CH2CH3
CH3CHoCH9-S-C-Nv
X
(e) (c) (a)
a 9.10 75
b *02 7
c &2-&6
d 7.12 7
e 6.71 75
10
-------
C-30
NJ
x
CH ° Cl
CHo N ii i
o N-C-S-CH2-C=CHCI
a
b 6.2
c 6.15 1-0
<' 5.96 OA
d 3.78 O6
d' X49 iJO
(c-) W1 W
-CH2 ,H -CHj Cl
c=c c=c
Cl Cl c'l H
10
-------
C-31
* Avod.x BW
CHo. (b)
CH
oo
,-,
N-C-S-CH0-C=C
(a)
Cl
' (b)
(b)
a
b
c
L i.
&71 7
63
&90
1O
-------
C-32
Ro-N«*t
(b) (d) ]f xCH2CH3
CH3CH2-S-C-N
to
vo
a
b
c
d
e
I
8.82 7
8.72 7
8.1-8.9
7.10 7
6.68 7
6.2
10
-------
033
a
b
c
d
8.72 7.5
8-2-8J
7.09 Z5
6.5
-------
C-34a
O=C C-OCHo
0 \ // J
I
a 6.29
b 5.99
c 4.82
J.
IS
16
-------
2.0
3.0
4.0
5.0 PPM(T) 6.0
7.0
8.0
C-34b
9.0 lb
Jo Suprocide
U)
NJ
8.0
7.0
(9)
300
200
6.0
5.0 'PPM(i)' 4.0
3.0
0
* 6O MHz
_^_™__j
i i.i
(b
A
1
. . . 1 ......... 1 - ... . .... 1 ....
>
'U
L 1
^^^^l^^ffrtymMfW'^Jfr-t^'lj ttfot tyt&iffl^f^f^ j^f1 Vf^T^l^rf' ^^VMff^^V^W^^fl>^^lUu^^<
1 1 . 1 . . 1 .... 1 ,
. ... 1 .... 1 .... 1 . 1 1 ... - ^- i '-—'
2.0
1.0
-------
C-35
Thirom
n S
N-C-S-S-C-N
CH
U)
u>
10
6.40
-------
I
T V.gad.x
(b)
•5-C
25*C
amb*
,60'C
tt
60'C
C-36
S w , ,
«»> (b) N-C-S-CHo-CsC
X ^ V
a R72
b 6.12
c 5.72
d 4.73
-------
C-37
(b)
£
H2
W)
(o)
a
b
c
d
7.28
6.49
5.59
10
-------
SECTION IV
INDEX TO SPECTRA
AbateR - A-19
D
Acaralate - see Chloropropylate
Alkron - see Ethyl Parathion
D
Aileron - see Ethyl Parathion
R
Aminocarb - see Matacil
j^
Anofex - see p_,pJ-DDT
T>
Aprocarb - see Baygon
1^
Arpocarb - see Matacil
Aspon - A-46
R R
Asuntol - see Co-Ral
R
Avadex - C-30
Avadex BW - C-31
Azak - C-3
R
Azinphosethyl - see Ethyl Guthion
j^
Azinphosmethyl - see Guthion
AzodrinR - A-10
Banol - see Carbanolate
Barban - C-24
n
Basudin - see Diazinon
n
Baygon - C-5
n
Baytex - see Tiguvon
j^
Benlate - see Benomyl
Benonyl - C-7
Benonyl metabolite - C-8
137
-------
Bidrin - A-ll
Bladafume - see Sulfotepp
R
Bulan - B-22
Carbanolate - C-6
j^
Carbaryl - see Sevin
j^
Carbicron - see Bidrin
j^
Carbofuran - see Furadan
R
Carbophenothion - see Trithion
Carbophos - see Malathion
R
Carbyne - see Barban
j^
(DEC - see Vegadex
Chem-Hoe - see IPC
Chlorobenzilate - B-19
Chloro-IPC - see CIPC
Chloropham - See CIPC
£
Chloropropylate - B-20
CiodrinR - A-9
CIPC - C-23
Co-RalR - A-40
Corothion - see Ethyl Parathion
R
Coumaphos - see Co-Ral
R
Cygon - A-3
Cygon oxygen analog - see Dimethoxon
Cynem - see Zinophos
- see Methyl Parathion
DATC - see Avadex
Dazomet - see Myrlone
138
-------
DBF - B-15
j^
2,3 DCDT - see Avadex
DBA - B-16
DDA Methyl Ester - B-17
o,£'-DDD - B-8
£,2.'-ODD - B-7
DDE - B-ll
DBMS - B-9
o,£'-DDMU - B-13
£,£'-DDMU - B-12
DDNU - B-14
DDQH - B-24
o,£' -DDT - B-2
£,£'-DDT - B-l
DDT acetal - B-26
DDT, Techical - B-3
DDVP - A-8
DEFR - A-49
Dedevap - see DDVP
DeGreen - see DEF1*
Deleaf Defoliant - see Merphos
R
Delnav - A-31
j^
Demeton 0 - see Systox
Demetron S - see Iso-Systox
2,4-DEP - see Falone
j^
Diallate - see Avadex
Diazinon - A-37
139
-------
Diazinon oxygen analog - see Diazoxon
Diazoxon - A-38
R
Dibrom - A-6
R
Dicaptan - see Dicapthon
Dicapthon - A-24
n
Dichlorophen (e) - see Preventol GD
Dichlorvos - see DDVP
1^
Dicofol - see Kelthane
R
Dilan - B-23
p
Dimecron - see Phosphamidon
R
Dimethoate - see Cygon
Dimethoxon - A-4
Dimethoxy DET - see Methoxychlor
DimetilanR - C-21
j^
Dinocide - see p_,p_'-DDT
n
Dioxathion - see Delnav
Diphenamid - B-18
R
Dipteres - see Neguvon
j^
Dipterex - see Neguvon
R
Disulfoton - see Di-Syston
j^
Di-Syston - A-28
n
Dithiodemeton - see Di-Syston
j^
Dithione - see Sulfotepp
j^
Dithiosystox - see Di-Syston
DMDT - see Methoxychlor
R
DMPA - see Zytron
R
DMTT - see Mylone
R
DNB - see Bulan
140
-------
R
UNP - see Prolan
R R
Dowco-139 - see Zectran
R R
Dow 1329 - see Zytron
Dow ET-14 - see Ronnel (technical)
R
Dow ET-57 - see Ronnel (purified)
R
DTMC - see Kelthane
Dursban - A-35
Dupont Fungicide 1991 - see Benomyl
Dupont Fungicide 1991 metabolite - see Benomyl metabolite
Dylox - see Neguvon
Dymid - see Diphenamid
E-605 - see Ethyl Parathion
Easy Off-D - see Merphos
Enide - see Diphenamid
R
ENT 24, 969 - see Supona
R
Entex - see Tiguvon
EPN - A-44
EPN-300 - see EPN
R
Eptam - C-26
EPTC - see Eptam
Ethion - A-33
R
Ethyl Guthion - A-39
Ethyl Parathion - A-41
Etilon - see Ethyl Parathion
Falodin - see Falone
Falone - A-47
Far-Go - see Avadex Bto
141
-------
Fendilorphos - see Ronnel
Fenthion - see Tiguvon
R
Folex - see Merphos
R
Folidol - see Ethyl Parathion
Folidol M - see Methyl Parathion
R R
Folithion - see Sumithion
Forte - see Thiram
R R
Fostion MM - see Cygon
R R
Frumin AL - see Di-Syston
J* R
Frumin G - see Di-Syston
U
Furadan - C-ll
R R
G-4 - see Preventol GD
Gardentox - see Diazinon
P
Gardona - A-21
Garrathion - see Trithion
R
GC-4072 - see Supona
Genitox - see p_,p_'-DDT
R
Gesapon - see
Gesarex - see £,p_'-DDT
R
Gesarol - see p^pJ-DDT
R
Guesapon - see p^pJ
Guesarol - see p_,£'-DDT
R
Gusathion - see Guthion
R R
Gusathion A - see Ethyl Guthion
GuthionR - A- 15
Guthion oxygen analog - A- 16
j^
Gyron - see p_,p_'-DDT
142
-------
Herkol - see DDVP
R R
Hydram - see Ordram
R
Imidan - A-17
INPC - see IPC
IPC - C-22
Isobutyl Triphenylmethylamine - B-27
Isolan - C-20
R
Isomeric Chlorthion - see Dicapthon
Iso PPC - see IPC
Iso-SystoxR - A-30
R
Ixodex - see p_,£f-DDT
Karbofos - see Malathion
KelthaneR - B-6
R
Korlan - see Ronnel
Landrin - see SD-8530
j^
Lannate - see Methomyl
R
Lebaycid - see Tiguvon
Mafu - see DDVP
Malaoxon - A-2
Malaspray - see Malathion
Malathion - A-l
Malathion oxygen analog - see Malaoxon
Malathon - see Malathion
Marlate - see Methoxychlor
Matacil - C-13
MCA-600 - see Mobam
143
-------
o-MDT - B-4
Mercaptophos - see Tiguvon
R
Mercapto dimsthur - see Mesurol
Merphos - A-48
MesurolR - C-15
j^
Metaisosystoxsulfoxide - see Meta-Systox-R
R
Meta-Systox-R - A-5
Methomyl - C-18
Methoxychlor - B-5
Nfethoxy DDT - see Methoxychlor
K
Methyl demeton-0-sulfoxide - see Meta-Systox-R
R R
Methyl Guthion - see Guthion
Methyl Parathion - A-22
Methyl Trithion - A-14
R
Metmercapturon - see Mesurol
Matron - see Methyl Parathion
Mevinphos - see Phosdrin
j^
Microfume - see Mylone
j^
Mintacol - see Paraoxon
Mobara - C-12
R
Molinate - see Ordram
R R
Muscatox - see Co-Ral
R
Mylone - C-37
n
Naled - see Dibrom
Nankor - see Ronnel
R
Navadel - see Delnav
R
Neguvon - A-7
144
-------
Nemafos - see Zinophos
Nemaphos - see Zinophos
Neocid - see p_,p_'-DDT
Neocidol - see p_,pJ-DDT
Niagara 1240 - see Ethion
Nialate - see Ethion
Niran - see Ethyl Parathion
Nitrostigmine - see Ethyl Parathion
Nitrox • see Methyl Parathion
Nitrox 80 - see Methyl Parathion
Nogos - see DDVP
R
Nomersan - see Thiram
D
Nuvacren - see Azodrin
Oko - see DDVP
Ordram - C-33
Orthophos - see Ethyl Parathion
Oxydemetonmethyl - see Meta-Systox-R
Paraoxon - A-42
Parathion - see Ethyl Parathion
Parathion Methyl - see Methyl Parathion
Parathion oxygen analog - see Paraoxon
PEBC - see TillamR
n
Pebulate - see Tillam
Pentachlorin - see £,p_f-DDT
Perfekthion - see Cygon
Perthane - B-10
Phencapton - A-34
Phenkaptone - see Phencapton
145
-------
R
Phorate - see Thimet
Phosdrin - A-12
Phosphamidon - A-13
Polyram-Ultra - see Thiram
R
Pomasol - see Thiram
R
Preventol - see Preventol GD
R
Preventol GD - B-25
R
Preventol GDC - see Preventol GD
Primin - see Isolan
R
Prolan - B-21
R
Prolate - see Inddan
Propham - see IPC
R
Propoxur - see Baygon
R
Queletox - see Tiguvon
RE-5305 - C-4
Resitox - see Co-Ral
R
Rhodiatox - see Ethyl Parathion
R
Rhothane - p,p'-DDD
R R
Rogor - see Cygon
Ro-Neet - C-32
Ronnel - A-20
R
Rowmate - see Sirmate
Roxion - see Cygon
R
Ruelene - A-25
S-847 - see Barban
R
SB-7859 - see Supona
146
-------
SD-8530 - C-l
R
Sevin - C-9
Sirmate - mixture of 2,3-and 3,4-Sirmate
Sirmate,2,3,isomer - C-16
Sinuate,3^4 isomer - C-17
Sok - see Carbanolate
R R
Solvirex - see Di-Syston
Spectracide - see Diazinon
Sulfatepp - see Sulfotepp
Sulfotepp - A-45
R
Sumithion - A-23
R
Supona - A-4 3
R
Supracide - C-34
Sutan - C-27
Swep - C-25
R
Systox - A-29
IDE - see £,p_'-DDD
TEDTP - see Sulfotepp
R
Temik - C-19
Terbutol - see Azak
R
Thimet - A-2 7
£
Thiodemeton 0 - see Di-Syston
H
Thiol-Systox - see Iso-Systox
Thionazin - see Zinophos
n
Thiono-Systox - see Systox
R
Thiophos - see Ethyl Parathion
Thiotepp - see Sulfotepp
147
-------
Thiram - C-35
Tiguvon - A-18
R
Tillam - C-28
1MTD - see Thiram
TMTDS - see Thiram
Triallate - see Avadex BW
R
Trichlorofon - see Neguvon
R
Trithion - A-32
R
Trolene - see Ronnel
Tuads • see Thiram
R R
Tugon - see Neguvon
UC-8454 - C-10
UC-10854 - C-2
R R
Unden - see Baygon
R
Vapona - see DDVP
R
Vegadex - C-36
R
Vernam - C-29
R
Vernolate - See Vernam
R
Viozene - see Ronnel
R R
Wepsin - see Wepsyn
j^
Wepsyn - A- 50
Zectran - C-14
Zinophos - A- 36
R
Zytron - A-26
148
-------
SECTION V
ACKNOWLEDGMENTS
Ann L. Alford and Lawrence H. Keith performed the experimental work,
interpreted the spectra, and prepared the spectral catalog. Arthur
W. Garrison's advice and assistance with the organophosphorus and DDT
pesticide spectra are gratefully acknowledged.
The authors wish to express their appreciation to the suppliers of
the pesticide analytical standards, and in particular to James D.
McKinney, National Institute of Environmental Health Sciences, Research
Triangle Park, North Carolina; Candace Plato, Pesticide Reference
Standards Section, Food and Drug Administration, Washington, D. C.;
and John A. Gardiner, Agricultural Chemicals Research, Industrial
and Biochemicals Departments, E. I. DuPont de Nemours and Company,
Wilmington, Delaware, for the samples of several pesticides and metabolites
not commercially available.
149
-------
SECTION VI
REFERENCES
1. For a summarizing reference see:
L. H. Keith and A. L. Alford, J. Assoc. Offic. Anal. Ghenu, 53,
1018 (1970).
2. L. H. Keith, A. W. Garrison, and A. L. Alford, J. Assoc. Offic.
Anal. Chem., 5^, 1063 (1968).
3. L. H. Keith and A. L. Alford, Anal. Chim. Acta, 44, 447 (1969).
4. L. H. Keith, A. L. Alford, and A. W. Garrison, J. Assoc. Offic.
Anal. Chem., 5£, 1074 (1969).
5. L. H. Keith and A. L. Alford, J. Assoc. Offic. Anal. Chem., £3,
157 (1970).
6. J. W. Emsley, J. Feeney, and L. H. Sutcliffe, "High Resolution
Nuclear Magnetic Resonance Spectroscopy," Vol. 1, Pergamon Press,
London, 1965, p. 399ff.
7. T. M. Valega, J. Org. Chem., 31, 1150 (1966).
8. E. Lustig, W. R. Benson, and N. Duy, J. Org. Chem., 32_, 850 (1967).
9. J. L. Richards, D. S. Tarbell, and E. H. Hoffmeister, Tetrahedron 24,
6485 (1968).
10. J. D. Roberts, J. Amer. Chem. Soc., 78, 4495 (1956).
151
-------
11. J. W. Emsley, J. Feeney, and L. H. Sutcliffe, "High Resolution
Nuclear Magnetic Resonance Spectroscopy," Vol. 2, Pergamon Press,
London, 1966, p. 819.
152
-------
SECTION VII
PUBLICATIONS RESULTING FROM THIS WDRK
1. L. H. Keith, A. W. Garrison, and A. L. Alford, "The High
Resolution NMR Spectra of Pesticides. I. Organophosphorus Pesticides,"
J. Assoc. Offic. Anal. Chem., 51, (5), 1063 (1968).
2. L. H. Keith and A. L. Alford, "Supplementaiy Interpretations of the
NMR Spectra of Phosphorus Pesticides," Anal. (Mm. Act a, 44,
447 (1969).
3. L. H. Keith, A. L. Alford, and A. W. Garrison, "The High Resolution
NMR Spectra of Pesticides. II. The DDT Class," J. Assoc. Qffic.
Anal. Chem., 5£, 1074 (1969).
4. L. H. Keith and A. L. Alford, "The High Resolution NMR Spectra of
Pesticides. III. The Carbamates," J. Assoc. Offic. Anal. Chem., 53_,
157 (1970).
5. L. H. Keith and A. L. Alford, "Review of Nuclear Magnetic Resonance
Spectroscopy in Pesticide Analysis," J. Assoc. Offic. Anal. Chem.,
53, 1018 (1970).
153
-------
en
SECTION VIII
APPENDIX: CHEMICAL NAMES AND SOURCES OF THE PESTICIDES
Spectrum
No.
A-l
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
A-ll
Common or
Trade Name
Malathion
Malaoxon
Cygon
Dimethoxon
n
Meta-Systox-R
Dibrom
Neguvon
DDVP
Ciodrin
n
Azodrin
Bidrin
Chemical Name
0 ,0-Diirethyl S- (1 , 2-dicarboethoxyethyl)
phosphorodithioate
0,0-Dimethyl S-(l, 2-dicarboethoxyethyl)
phosphorothioate
0,0-Dimethyl S- (N-methylcarbamoylmethyl)
phosphorodithioate
0,0-Dimethyl S- (N-methylcarbamoylmethyl)
phosphorothioate
0,0-Dimethyl S- [2- (ethylsulfinyl) ethyl]
phosphorothioate
0,0-Dimethyl 0~l,2-dibromo-2,2-
dichloroethyl phosphate
0,0-Dimethyl (l-hydroxy-2,2,2-
trichloroethyl) phosphonate
0,0-Dimethyl 0-2,2-dichlorovinyl
phosphate
« -Methylbenzyl 3- (dimethoxyphosphinyloxy) t-
cis-crotonate
3- (Dimethoxyphosphinyloxy)-N-methyl-
cis-crotonamide
3- (Dimethoxylphosphinyloxy) -N,N-dimethyl-
Source
American Cyanamid
American Cyanamid
American Cyanamid
American Cyanamid
Chemagro Corp
Chevron Chem Co
Chemagro Corp
Shell Development Corp
Shell Development Corp
Shell Development Corp
Shell Development Corp
cis-crotonamide
-------
in
cn
Spectrum
No.
A-12
A-13
A-14
A-15
A-16
A-17
A-18
A-19
A-20
A-21
A-22
A-23
Common or
Trade Name
PhosdrinR
Phosphamidon
Methyl TrithionR
GuthionR
Guthion oxygen
analog
Imidan
R
Tiguvon
R
Abate
Ronnel
R
Gardona
Methyl parathion
R
Sumithion
Chemical Name
0 ,0-Dimethyl 0- (2 -carbomethoxy- 1-
methylvinyl) phosphate
0,0-Dimethyl 0- [2-chloro-2- (N,N-diethyl
carbamoyl) - 1-methyl vinyl ] phosphate
0 ,0-Dimethyl S- (p_-chlorophenylthio) methyl
phosphorodithioate
0,0-Dimethyl S- [4-oxo-l ,2 ,3-benzotriazin-
3(4H)-yl methyl] phosphorodithioate
0,0-Dimethyl S- [4-oxo-l ,2 ,3-benzotriazin-
3(4H)-yl methyl] phosphorothioate
0,0-Dimethyl S-phthalimidomethyl
phosphorodithioate
0,0-Dimethyl 0- [4- (methylthio-m-tolyl]
phosphorothioate
0,0,0' ,0' -Tetramethyl 0,0'-thiodi-p_-
phenylene phosphorothioate
0,0-Dimethyl 0-{2,4,5-trichlorophenyl)
phosphorothioate
vinyl dimethyl ester 2-chloro-l-(2,4,5-
trichlorophenyl) phosphoric acid
0,0-Dimethyl 0- (4-nitrophenyl)
phosphorothioate
0,0-dimethyl 0- (4-nitro-m-tolyl)
Source
FDA
Chevron Chem Co
Stauffer Chem Co
Chemagro Corp
Chemagro Corp
Stauffer Chem Co
Chemagro Corp
American Cyanamid
Dow Chem Co
Shell Development Corp
Monsanto Chem Co
Chemagro Corp
phosphorothioate
-------
tn
Spectrum
No.
A-24
A-25
A-26
A-27
A-28
A-29
A-30
A-31
A-32
A- 33
A-34
A-35
Common or
Trade Name
Dicapthon
Ruelene
R
Zytron
R
Thimet
Di-Syston
Systox
Iso-Systox
DelnavR
TrithionR
Ethion
Phenacapton
R
Dursban
Chemical Name
0 ,0-Dimethyl 0- (2- chloro- 4-nitrophenyl)
phosphorothioate
4-t-Butyl-2-chlorophenyl methyl
methylphosphoramidate
2,4-Dichlorophenyl methyl isopropyl-
phosphoramidothioate
0,0-Diethyl S- (ethylthio) methyl
phosphorodithioate
0,0-Diethyl S- 2- (ethylthio) ethyl
phosphorodithioate
0,0-Diethyl 0-2- (ethylthio) ethyl
phosphorothioate
0,0-Diethyl S-2- (ethylthio) ethyl
phosphorothioate
2 , 3-p-Dioxanedithiol S,S' -bis (0 ,0-
diethyl phosphorodithioate)
0 ,0-Diethyl S- (4- chloropheny Ithiomethy 1)
phosphorodithioate
0,0,0', O'-Tetraethyl S,Sf-methylene
bis-phosphorodithioate
0 ,0-Diethyl S- (2 , 5-dichloropheny Ithio)
methyl phosphorodithioate
0,0-Diethyl 0- (3 , 5 ,6- trichloro-2-pyridyl)
Source
American Cyanamid
Dow Chemical Co
Dow Chemical Co
American Cyanamid
Chemagro Corporation
Chemagro Corporation
Chemagro Corporation
Hercules Powder Company
Stauf fer Chemical Co
Niagara Chem Div, FMC Corp
Geigy Chemical Corporation
Dow Chemical Co
phosphorothioate
-------
en
oo
Spectrum
No.
A-36
A- 37
A- 38
A- 39
Common or
Trade Name
Zinophos
Diazinon
Diazoxon
Ethyl Guthion
Chemical Name
0,0-Diethyl 0-2-pyrazinyl
phosphorothioate
0,0-Diethyl 0- (2- isopropyl-4-methyl-6-
pyrimidyl) phosphorothioate
0,0-Diethyl 0- (2-isopropyl-4-msthyl-6-
pyrimidyl) phosphate
0,0-Diethyl S- [4-oxo-l,2,3-benzo-
Source
American Cyanamid
Geigy Chemical Corp
Geigy Chemical Corp
Chemagro Corporation
A-40
A-41
A-42
A-43
A-44
A-45
A-46
A-47
A-48
R
Co-Ral
Ethyl parathion
Paraoxon
R
Supona
EPN
Sulfotepp
Aspon
Falone
Merphos
triazin-3-(4H)yl methyl]
phosphorodithioate
0,0-Diethyl 0-(3-chloro-4-methyl-2-oxo-
2H-l-benzopyran-7-yl) phosphorothioate
0,0-Diethyl 0-4-nitrophenyl phosphoro-
thioate
0,0-Diethyl 0-4-nitrophenyl phosphate
0,0-Diethyl-1-(2,4-dichlorophenyl)-2-
chlorovinyl phosphate
0-Ethyl 0-4-nitrophenyl phenylphosphono-
thioate
0,0,0' jO'-Tetraethyl dithiopyrophosphate
0,0,0' ,0'-Tetrapropyl dithiopyrophosphate
Tris-(2,4-di chlorophenoxyethy1) phosphite
Tributyl phosphorotrithioite
Chemagro Corporation
Monsanto Chemical Co
American Cyanamid
Shell Development Corp
E. I, Dupont de Nemours
and Co
Chemagro Corporation
Stauffer Chemical Co
U S Rubber
V-C Chemical Co
-------
<£>
Spectrum
No,
A-49
A-SO
B-l
B-2
B-3
B-4
B-S
B-6
B-7
B-8
B-9
B-10
Common or
Trade Name
DEF11
WepsynR
I^'-DDT
o,E'-DDT
Tech DDT
o-MDT
Methoxychlor
Kelthane
p_,j>'-DDD
o,p'-DDD
DDMS
Perthane
Chemical Name
S,S,S-Tributyl phosphorotxithioate
5"AminO"l-bis(diethylamido)phosphoryl-
3-phenyl- 1,2 ,4-triazole
l,l,l-Trichloro-2 ,2-bis (p_- chlorophenyl) -
ethane
1 ,1 ,!-TrichlorO"2-jV'Chlorophenyl-2-o-
chlorophenylethane "
Mixture of o,E'-DDT and g^'-DDT
1 , 1 , l-Trichloro- 2-o- chlorophenyl- 2-
phenylethane ""
l,l,l-Trichloro-2,2-bis (^-methoxyphenyl)-
ethane
1,1-bis (^-Chlorophenyl) -2 ,2 ,2-trichloro-
ethanol
l,l-Dichloro-2 ,2-bis (£- chlorophenyl)
ethane
l,l-Dichloro-2-£-chlorophenyl-2-p_-
chlorophenylethane
1-Chloro- 2 , 2-bis (E- chlorophenyl)
ethane
l,l-Dichloro-2,2-bis(p-ethylphenyl)-
Source
Chemagro Corporation
Thompson-Hayward
FDA
FDA
Allied Chemical
CDC, PHS
Corp
Geigy Chemical Corp
Rohm § Haas Co
FDA
FDA
CDC, PHS
Rohm § Haas Co
ethane
-------
Spectrum
No.
Common or
Trade Name
Chemical Name
Source
H-
cn
o
B-ll
B-12
B-13
B-14
B-15
B-16
B-17
B-18
B-19
B-20
B-21
B-22
B-23
B-24
B-25
B-26
DDE
p^pJ-DDMLJ
o,pJ-DDMJ
DDNU
DBF
DDA
DDA methyl ester
Diphenamid
Chlorobenzilate
R
Chloropropylate
R
Prolan
R
Bulan
DilanR
DDOH
R
Preventol GD
DDT acetal
1,l-Dichloro-2,2-bis(£-chlorophenyl)-
ethylene
l-Chloro-2,2-bis(p_-chlorophenyl)ethylene
l-Chloro-2-£-chlorophenyl-2-p_-chlorophenyl-
ethylene
1,1-bis (p_-Chlorophenyl) ethylene
p_,£f -Dichlorobenzophenone
bis (p_-Chlorophenyl) acetic acid
Methyl bis (pj-chlorophenyl) acetate
N,N-Dimethyl-2,2-diphenylacetamide
Ethyl-p_,p_' -dichlorobenzilate
Isopropyl-p_fp_f -dichlorobenzilate
2-Nitro-l, 1-bis (p_-chlorophenyl)propane
2-Nitro-l, 1-bis (p_-chlorophenyl)butane
Mixture of Prolan and Bulan
2,2-bis (p_-Chlorophenyl)ethanol
bis (£-Hydroxy-£-chlorophenyl) methane
2-bis (p_-Chlorophenyl)methyl-1,3-
dioxolane
FDA
CDC, PHS
FDA
CDC, PHS
Eastman Org Chem
CDC, PHS
CDC, PHS
Upjohn Co
Geigy Chemical Corp
Geigy Chemical Corp
Commercial Solvents Corp
Commercial Solvents Corp
Commercial Solvents Corp
CDC, PHS
General Aniline § Film Corp
CDC, PHS
-------
Spectrum
No.
Common or
Trade Maine
Chemical Name
Source
B-27
C-l
C-2
C-3
C-4
C-5
C-6
C-7
C-8
C-9
C-10
C-ll
C-12
C-13
Isobutyl triphenyl-
methylamine
SD 8530
UC 10854
R
Azak
RE 5305
Baygon
Carbanolate
Benomyl
Benomyl metabolite
Sevin
UC 8454
Furadan
R
Mobam
R
R
Matacil
3,4,5 -Triraethy Ipheny 1-N-methylcarbamate
3-Isopropylphenyl-N-methylcarbamate
2,6-Di-tert-butyl-4-methylphenyl-N-
methylcarGainate
3-sec-Butylphenyl-N-methylcait>amate
2-Isopropoxyphenyl-N-methylcarbamate
3,4-Xylyl-6-chloro'N-methylcarbamate
Methyl l-(butylcarbamoyl)-2-benzimida-
zole carbamate
Methyl 5-hydroxy-2-benzimidazole carbamate
1-Naphthyl-N-methylcarbajnate
1- (5,6,7,8-Tetrahydro) -naphthyl-N-
methylcarbamate
7-(2,3-Dihydro-2,2-dimethyl)-
benzofuranyl-N-methylcarbamate
4-Benzothienyl-N-methylcarbamate
4-Dimethylamino- 3-methylphenyl-N"
methylcarbamate
Inperial Chem Industries LTD
Shell Development Corp
Union Carbide Corp
Hercules Powder Co
Chevron Chemical Co
Chemagro Corporation
Upjohn Company
E. I. DuPont de Nemours § Co
E. I. DuPont de Nemours § Co
Union Carbide Corporation
Union Carbide Corporation
Niagara Chemical Div, FMC Corp
Mobil Chemical Co
Chemagro Corporation
-------
01
NJ
Spectrum
No.
C-14
C-15
C-16
C-17
C-18
Common or
Trade Name
1^
Zectran
MesurolR
Six-mate, 2,3-
isomer
Sirmate, 3,4-isomer
Methomyl
Chemical Name
4-Dimethylamino- 3 ,5-dimethylphenyl-
N-methy Icarb amate
4 -Methy Ithio- 3 , S - dimethylpheny 1-
N-me thy Icarb amate
2 ,3-Dichlorobenzyl-N-me thy Icarb amate
3,4-Dichlorobenzyl-N-methylcarbamate
S-Methyl N-[(methy Icarb amoyl)oxy]
Source
Dow Chemical Co
Chemagro Corporation
FDA
FDA
E. I. DuPont
de Nemours
C-19
C-20
C-21
C-22
C-23
C-24
C-25
C-26
C-27
Temik
Isolan
Dimetilan
IPC
CIPC
Barban
R
Swep
Eptam
Sutan
R
thioacetimidate
2-Methyl-2-methylthiopropionaldehyde-
0-methylcarbamoyl oxime
5- (1- Isopropyl- 3-methyl) -pyrazolyl-N,
N-dimethylcarbamate
3- (l-N,N-Dinethylcarbamoyl-5-methyl) -
pyrazolyl-N,N-dimethylcarbamate
Isopropyl-N-phenylcarbamate
Isopropyl-N-(3-chlorophenyl)carbamate
4-Chloro-2-butynyl-N-(3-chlorophenyl)-
carbamate
Methyl-N-(3,4-dichlorophenyl)carbamate
S-Ethyl-N ,N-dipropylthiolcarbamate
S-Ethyl-N,N-diisobutylthiolcarb amate
IMion Carbide Corp
Geigy Chemical Corp
Geigy Chemical Corp
Pittsburgh Plate Glass Co
Pittsburgh Plate Glass Co
Gulf Res § Dev Co
Niagara Chem Div, FMC Corp
Stauffer Chemical Co
Stauffer Chemical Co
-------
Spectrum
No.
C-28
C-29
C-30
Common or
Trade Name
R
Tillam
Vernam
Avadex^
Chemical Name
S-Propyl-N-butyl-N-ethyl thiolcarbamate
S-Propyl-N,N-dipropyl thiolcarbamate
S- f 2 , 3-Dichloroallyl) -N tN-diisopropyl
Source
Stauffer Chemical Co
Stauffer Chemical Co
Monsanto Chemical Co
C-31
C-35
C-36
C-37
Avadex
BW11
C-32
C-33
C-34
Ro-Neet
Ordram
Supraci
R
Thiram
Vegadex
R
Mylone
R
thiolcarbamate
S-(2,3,3-Trichloroallyl)-N,N-diisopropy 1
thiolcarbamate
S-Ethyl-N-ethyl-N-cyclohexylthiolcarbamate
S-Ethyl -hexahydroazepine-1 - carbothioate
0,0-Dimethyl-S-[2-methoxy-1,3,4-
thiadiazol-5(4H)-onyl-4-methyl]-
dithiophosphate
bis (DimethyIthiocarbamoyl) disulf ide
2-Chloroallyl-N,N-diethyl dithiocarbamate
3,5-Diroethyl-l,3,5-tetrahydrothiadiazine-
2-thione
Monsanto Chemical Co
Stauffer Chemical Co
Stauffer Chemical Co
Geigy Chemical Corp
E. I. DuPont de Nemours
Monsanto Chemical Co
Union Carbide Corp
Co
-------
Ace fun ion Number
Subject Field & Group
010B
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
rganization
Water Quality Office, Environmental Protection Agency, Southeast Water
Laboratory, Athens, Georgia
Title
CATALOG OF PESTICIDE NMR SPECTRA
1Q I Authors)
' ALFORD, ANN L.
KEITH, LAWRENCE H.
16
21
Project Designation
PROJECT 116020 EWC
Note
22
Citation
WQO Project #16020
11 references
, p. 1-157, April, 1971, 114 figures, 2 tables,
23
Descriptors (Starred First)
*Pesticides, *Nuclear magnetic resonance, *0rganophosphorus pesticides,
*Carbamate pesticides, *DDT, data collections, spectroscopy
25
Identifiers (Starred First)
*Chemical shifts, *Coupling constants, spin decoupling
27
Abstract
This catalog contains the 100 MHz nuclear magnetic resonance
spectra of 114 organophosphorus, DDT, and carbamate pesticides and a
brief discussion of their most important features. Chemical shifts
and coupling constants are shown on each spectrum. (Alford - Southeast
Water Laboratory)
ANN L. ALFORD
Institution
SOUTHEAST WATER LABORATORY
WR-.102 (REV JULY I96»>
VVRSIC
SEND TO: WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. O. C. 20240
* CPO! 1988-359-339
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