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Research on Organophosphorus Insecticides, Synthesis of O-Alkyl O-Substituted Phenyl Alkylphosphonothioates W U K I U N - H O U O , SUN Y U N G - M I N , and WANG S I N G - M I N Department o f Chemistry, F u d a n University, Shanghai, C h i n a
In order to obtain the organo-phosphorus insecticides needed for agriculture in China, we have prepared more than one hundred organo-phosphorus compounds. After screening for the efficiency of insecticides, we found that o-l,3,-dichlorophenyl o-alkyl ethylphosphonothioates showed high activities against a wide variety of insects as an efficient contact insecticide. We have synthesized fifteen compounds of the homologs by the following reactions:
For the last step of the preparation we used method 4A and 4B, and found that method 4B is better. For the synthesis of the alkyldichlorothiophosphine, we also used the aluminum chloride complex method: 0097-6156/81/0171-0341$05.00/0 ©
1981
American
Chemical Society
Quin and Verkade; Phosphorus Chemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
342
PHOSPHORUS CHEMISTRY
The molecular structural formulas, boiling points, melting points and the yields are listed in Table I. Table I
C H 2
y
5
RO
^OR
S t r u c t u r a l Formulas R CH
h
R
£
2
£
C H 2
4
n-C H
y
5
n-C H
7
3
3
Λ/
j6
C
7
H
2 5
C H
A*
8
C H
9
n-C H
10
CH
11
C H
12
n-C H
13
CH
14
C H
1 5
n-C H
2
6
7
2
3
?
3
7
bp 118-119°/0.9
4B 61.3 4A 80.0
o,£-Cl C H
3
bp 152-153°/0.8
4A 56.9
6
2
6
£
-ClC H
4
bp 128°/0.1
4A 78.6
£
-ClC H
4
bp 124-125°/0.6
4A 62.5
6
6
£-t-BuC H
4
bp 130-131°/0.3
4B 66.1
£-t-BuC H
4
bp 134.5°/0.7
4B 78.2
£-t-BuC H
4
bp 135-136°/0.2
4B 77.2
6
o,o, -Cl C H
2
mp 49°
4B 92.3
o,o,£,Cl C H
2
mp 43°
4B 90.0
o,o,£,Cl C H
2
mp 48°
4B 77.1
3
6
3
6
6
ci c
6
mp 66-67°
4A 58.6
ci c
6
mp 79°
4A 58.8
mp 64-65°
4A 44.3
5
5
4B 70.4
bp 130-131°/0.5
5
3
bp 128-129°/0.9
3
2
3
5
Method Y i e l d (%)
o, ,Cl C H
£
3
3
4
6
5
3
,
-ClC H
6
6
3
2
2
£
5
Boiling Point & Melting Point °C/mmHg
f
o, -Cl C H
3
1
C 1
5 6 C
Quin and Verkade; Phosphorus Chemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
71.
KIUN-Houo E T A L .
TABLE I I .
1 2 1 2 1 2 1 2 1 2 1 2 1 2 1
46
34
36
37
34
45
37
33
38
43
47
34
30
32 31 31 31 42 33 38 29 41 35 36 30 30 25 32
38
28
40
12
1 38 2 1 37 2 1 25
28 28 35 32 12
13
ζ 1
2 3 4 5 6 7 8
33
-
42
_
52
Ζ
9
1 ο Ζ
10 11
-
0
_
1 1
— 33 _ 30
-36 -30 -
22
-
-
42
43
42
35
44
43
34
41
71
60
59
Mortality % (17 h o u r s ) (3) (2)
100 100
100
55.0
100
100 100 100 100 34.2
-31 -24 21
Melanogaster
100 100
100 100 100
100
-
_
343
100 100 100 100 100 100 100 100 100 100 100 100 100 73.3 62.5
100
100
33
38
(1)
28
-
9 Ζ
15
(4)
22 _
9 Ζ
14
Insecticides
T o x i c i t y Test f o r Drosophila
Numbers o f insects f o r test (2) (3) (1)
Sample Number 1
Organophosphorus
100
-
100 73.5
100 100 _ 100
-
100 _ 100 100
(4)
-
100
- 3.3 100 33.3 14.3 83.9
-25.0 -
100
-81.8 -
7.9
0
0
0
0
0
0
0
0
100
100
85.7
-40.9 -
Δ.
Standard Sample 1 Rogor
-
3.4
-
N o t e s Α. (1) = 100 ppm (2) « 10 ppm (3) = 1 ppm (4) = 0.1 ppm Β. The t e s t s o l u t i o n made o f 1 0 % a b s o l u t e a l c o h o l i c i n s e c t i c i d e , was d i l u t e d g r a d u a l l y w i t h w a t e r . C. D e t e r m i n a t i o n 1by method1 o f a g a r - a g a r p o i s o n d i e t . *Rogor i s ; 0 , 0 - d i m e t h y l - S -- ( N - m e t h y l c a r b o m o y l met h y l ) d i t h i o p h o s phate.
Quin and Verkade; Phosphorus Chemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
344
PHOSPHORUS
Table I I I . Sample Number 1 3 6 10 Rogor *Notes:
R e s u l t s f o r Second Emulsion Concentration 47.1% 50.4% 48.9% 18.9% 25.0%
Screening Test
M o r t a l i t y o f I n s e c t s %* Tetranychus Agrotis Myzus Urticae Ipsilon Persicae 10.0 50.0 0 18.8
55.1 80.0 65.7 78.3 99.4
77.8 77.8 70.0 0
100 oThe e m u l s i o n c o n c e n t r a t i o n i np r a c t i c e was d i l u t e d w i t h 2000 v o l u m e s o f s o l u t i o n .
Table IV.
Insecticide Emulsion Concentran.
Test f o r F i r s t Generation of Tryporza I n c e r t u l a s , F i r s t I n s t a L a v a ( O u t d o o r s :i n P o t ) . Quantity of Insecticide Jin/Mou*
No. 1 (47.1%) No. 3 (50.4%) No. 5 (48.1%) No. 10 (18.9%) Suraithion (50 % Sample) *Notes:
CHEMISTRY
1 1 1 3 ^
No. o f Rice Plants
No. (Df I n s e c t s Dead Mortality P e r ]Pot H e a r t % %
58 49 26 28
60 60 60 60
1.7 2.0 30.7 32.1
100.0 98.7 95.5 89.5
45
60
0
100.0
J i n ; C h i n e s e m e a s u r e o f w e i g h t , 1 J i n = 500 gm. Mou; C h i n e s e m e a s u r e o f a r e a , 1 Mou = 6.67 a c r e s
Literature Cited
1. Hoffman, F.W.; Moore, T.R. J. Am. Chem. Soc. 1958, 80, 1151. 2. Fukuto, T.R. J. Am. Chem. Soc. 1959, 81, 372. 3. Schegk, E.; Schrader, G. Ger. 1, 078, 124, Chem. Abstr. 1963, 58, 1492. RECEIVED
June 30,
1981.
Quin and Verkade; Phosphorus Chemistry ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
