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Патент USA US3076019

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United States Patent 0
C6
3,076,009
Patented Jan. 29, 1963
1
2
phosphoric acid esters. This reaction is preferably carried
3,076,009
out at‘. temperatures of. between 40 and 100° C. but lower
or higher temperatures may also be applied. It is ex
THIOPHOSPHORIC ACID ESTERS AND
PRODUCTION
pedient to work in a suitable solvent such as benzene or
Gerhard Schrader, Opladen, and August Diirken, Wupper
tal-Sonnborn, Germany, assignors t0 Farbenfabriken
toluene. However, ketones such as for example acetone
or methyl-ethyl ketone are also suitable for carrying out
Bayer Aktiengesellschaft, Leverkusen, Germany, a cor
poration of Germany
No Drawing. Filed Feb. 8, 1956, Ser. No. 564,108
Claims priority, application’ Germany Feb. 10, 1955
5 Claims. (Cl. 260—461)
the reaction. It is further possible to use an excess of the
corresponding a-halogen-carboxylic acid ester as solvent.
The reaction leading to this class‘ of compounds may be
10
This invention relates to thiophosphoric acid esters of
the general formula
15
R and R’ stand for aliphatic or aromatic radicals, R" 20 in which R, R’, R” and X have the meaning set forth in
stands for hydrogen, aliphatic or aromatic radicals, X
column 1.
stands for oxygen or sulfur whereby one X must be sulfur.
The invention is further illustrated by the following
examples without‘ being, restricted thereto.
Example I
An object of this invention is to provide new thiophos
phoric acid esters having good insecticidal properties.
Another object of this invention is to provide processes
’ for making these new thiophosphoric acid esters.
Further objects will become apparent as the following
S
description proceeds.
00139
The thiophosphoric acid esters according to the inven
correspond to the formula
30
OCH3
80 grams of the ammonium salt of dimethyl-thiol-phos
phoric acid are suspended in 200 grams of u-bromo-phenyl
acetic acid ethyl ester. The mixture is heated to 60° C.
35
and maintained at 60~70° C. for a half hour. The reac
tion is completedwith slight heat' evolution. The mix
ture is cooled to room temperature, diluted with 500 milli
wherein R, R’, R" and X have the abovesaid meaning.
For instance, R and R’ may be methyl, ethyl, propyl, butyl,
hexyl, phenyl, nitrophenyl chlorophenyl, tolyl, benzyl etc.;
40
R" may stand for the same radicals or may be hydrogen.
The new thiophosphoric acid esters wherein the chalco
genic X attached to CH and P is oxygen, can be regarded
litres of ether, the salts’ are ?ltered off by suction and the
ethereal layer is washed twice with 100 millilitre portions
of water. After drying over sodium sulphate the ether
is distilled oif. At a pressure of 0.01 mm. Hg there are
obtained 100 grams of ?rst runnings which come over at
50-60" C., chie?y consisting of unchanged a-bromo
phenyl-acetic acid ethyl-ester. By further distillation there
as phosphoric acid derivatives of a-hydroxy carboxylic
are obtained about 100 grams of the new ester coming over
at 122-125“ C./0.01 mm. Hg as a colourless sparingly
acid esters. These esters can be prepared by reaction of
u-hydroxy carboxylic acid esters with 0,0-dialkyl-thiono
water-soluble oil.
phosphoric acid monohalides in the presence of acid bind
ing agents such as tertiary amines, alkali alcoholates, alkali
hydroxides and alkali carbonates‘.
The reaction leading to this class of compounds may be 50
represented by the following equation:
Example 2
0113-03-0 o 0 (H55
(H) 0011,
S——P/
0011.
160 grams of the’ ammonium salt of dimethyl-thiol
55 phosphoric acid are suspended with 320 grams of a-bromo
propionic acid ethyl ester; The mixture is heated with
stirring to about 60° C. and maintained at this temperature
for an hour. It is then cooled down, 600 millilitres of
ether are added thereto, the salts thus formed are ?ltered
in which R, R' and R" have the meaning set‘ forth in
column 1.
The reaction is preferably carried out in suitable sol
vents such as lower aliphatic alcohols, lower aliphatic
60 off by suction and the ethereal solution is washed three
ketones, lower aliphatic nitriles, hydrocarbons such’ as
benzene and toluene. It is advantageous to conduct the
reaction at a temperature of between 40 and 80° C. but
lower or higher temperatures may also be applied.
The new thio- or dithiophosphoric acid esters, wherein
the chalcogenic X attached to CH and P is sulfur, may be
prepared by reaction of u-halogen-carboxylic acid esters 70
with the salts of dialkyl-thiol or dialkyl-thiol-thiono
times with 100 millilitre portions of water. The ethereal
solution is dried and then fractionated. 100 grams of the
new ester, B.P. 76-7 8° C./ 0.01 mm. Hg, are thus obtained.
The excess u-bromo-propionic acid ethyl ester used is
recovered as ?rst runnings.
Example 3
CH3-CH-O 0-0 0.3,
s--P
002B)
3,076,009
4
3
Example 8
38 grams of diethyl-thiol-phosphoric acid ammonium
salt are dissolved in 125 millilitres of 99 percent ethyl
GH-C 0-0 02H;
alcohol. 38 grams of e-bromo-propionic acid ethyl-ester
H/OCzHg
are added with stirring at 75° C. and the temperature is
3
maintained for an hour. The salts are then ?ltered o? by 5
0-P
suction, the ?ltrate is diluted with water, the water-insolu
002115
ble residue is taken up with chloroform, dried over sodium
54 grams of mandelic acid ethyl ester are dissolved in
sulphate and distilled. 40 grams of the new ester, B.P.
25 grams of pyridine. 57 grams of diethyl-thiono-phos~
78-79° C./0.01 mm. Hg, are thus obtained.
10
phoric acid monochloride are added thereto with stirring
Example 4
at 40° C. and the mixture is heated to 60° C. for 2 hours.
The viscous reaction mixture is introduced into a mixture
of 300 millilitres of water and 30 millilitres of concen
trated hydrochloric acid.
46 grams of diethyl-thiol-phosphoric acid ammonium
salt are suspended in 100 millilitres of methyl-ethyl-ketone.
is distilled oif. 70 grams of the new ester are obtained as
viscous water-insoluble oil. The new ester can be distilled
61 grams of a-bromo-phenyl-acetic.acid ethyl ester are ,
in high vacuum only with decomposition. The new ester
kills red spiders at 0.01% concentration.
added with stirring at 60° C., and the mixture is heated to
60-65° C. for an hour. The salts are then ?ltered off by
suction, the bulk of the solvent is distilled off, the product
Example 9
taken up with ether, washed with water and the ethereal
solution is dried. By fractionating there are obtained 50
grams of the new ester, B.P. 127° C./0.01 mm. Hg. The
new ester is a colourless oil which is able to kill plant lice
at a concentration of 0.005 percent and red spiders at 0.01
CHg-OH-C 0-0 02115
S
H/
0 02115
0-1?
percent concentration.
Example 5
The water-insoluble part is
taken up in chloroform and the chloroform solution is
shaken with 100 millilitres of a 5% sodium bicarbonate
solution. After drying with sodium sulphate the solvent
30
002B;
24 grams of lactic acid ethyl ester are added to a
(Heron-o0 0 0,115
sodium ethylate solution (4.6 g. of sodium in 200 milli
litres of alcohol) at 20° C. 39 grams of diethyl-thiono
5
phosphoric acid monochloride are added drop by drop
00 H
u/
2 ‘
to the solution at 40° C. and the temperature is kept at
001B;
40° C. for 30 minutes. The reaction product is placed
in a large quantity of water, the water-insoluble por
tion taken up in chloroform, dried and fractionated. 35
8-?
83 grams of powdered and screened potassium carbonate
grams of the new ester, B.P. 69° C./0.01 mm. Hg, are
are suspended in 150 millilitres of methyl-ethyl-ketone.
obtained. The new ester has a toxicity of about 1000
98 grams of diethyl-dithio-phosphoric acid are slowly
added with stirring at 40° C. 90 grams of w-brOmO 40 mg./kg. when applied to rats per os. The ester kills
red spiders at 0.05% concentration.
propionic acid ethyl ester are then added drop by drop
We claim:
at 65° C. and the temperature is maintained at 60° C. for
1. A thiophosphoric acid ester of the formula
four hours. By usual working up, 110 grams of the new
ester, B.P. 134° C./2 mm. Hg, are obtained.
Example 6
CH-CO 0 C231!
45
S
O OOH:
' OCH;
ll/
s-r
0033
OCH:
84V
CHg-CH——G 0 0 CeHil
50
2. A thiophosphoric acid ester of the formula
40 grams of dimethyl-thiol-phosphoric acid ammonium
salt are suspended in 100 millilitres of methyl-ethyl-ketone.
47 grams of u-bromo-propionic acid-n-hexyl ester (B.P.
65—67° C./1 mm. Hg) are added thereto with stirring at 55
65° C. The temperature is maintained for about an hour
and the product then worked up in usual manner. 35
grams of the new ester, B.P. 98-100° C./0._01 mm. Hg, are _
thus obtained.
3. A compound of the formula
The new ester shows with rats per 0s a '
R0
toxicity of LD 50:500 mg./kg. It kills plant-lice at a 60
concentration of 0.05 percent.
s
\ll
P-X-CHCOOR
R0
Example 7
'
wherein each R is lower alkyl, R’ is phenyl and X is a
0112-00-0 02B!
65 member selected from the group consisting of oxygen and
sulfur.‘
4. A compound of claim 3 wherein X is oxygen.
5. A compound of claim 3 wherein X is sulfur.
0 02115
50 grams of diethyl-dithio-phosphoric acid ammonium
salt are dissolved in 150 millilitres of methyl-ethyl-ketone. 70
25 grams of mono-chlor-acetic acid ethyl ester are added
with stirring thereto at 70° C. The temperature is main
tained at 65 ° C. for'two hours and the product is then
worked up in usual manner. 33 grams of the new ester,
B.P. 137° C./ 1.5 mm. Hg, are thus obtained.
75
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,266,514
2,494,126
Romieux et a1 _________ __ Dec. 16, 1941
Hoegberg ____________ __ Jan. 10, 1950
(Other references on following page)
3,076,009
5
6
UNITED STATES PATENTS
2,494,283
2,645,657
2,802,856
d
t
1. _______ __ J
. 10, 1950
142001) (1953)
£331? eatyai _a_________ __ 1:11; 14,1953
_________ __ A
Norman et a1
OTHER REFERENCES
‘
Melnikov et al.: “J. Gen. Chem. U.S.S.R.,” 23, 1417
Hg
. 1 , 1957
3
Bacon et 'aL: “J. Am. Chem. Soc.,” 76, 670.675
5
(1954).
Kosolapo?: “Chemical Abstracts,” v01. 48, pp. 6639..
6640, 9902—3 (1954).
Whitemore: “Organic Chemistry,” D. Van Nostrand
Mastryukova et al.: “Bull. Acad. Sci. U.S.S.R., Div.
Co., Inc., NY. (1937), pp. 37-39.
Chem. Sci,” p. 433 (1956).
Melnikov et a1.: “Doklady Akad. Nauk S.S.S.R.” 86,
Germany, application Ser. No. F 13502, IV b/ 12-0.
543-6 (1952).
10 Printed Jan. 26, 1956.
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