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Патент USA US3047618

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United States ,ate t Q?ice
3,047,605
Patented July 31, 1962
1
i)
These 13 - alkoxy - (or /3-alky1mercapto~.)-vinyl-phos-.
3,047,605
phonic acid alkyl ester chlorides or?-alkoXy-(or B-alkyl
mercapto-)-vinyl thionophosphonic acid alkyl ester chlo
PHOSPHONIC ACID ESTERSS AND THEIR
PRODUCTION
Gerhard Schrader, Wuppertal-Cronenberg, Germany, as
signor to Farbenfabriken Bayer Aktiengesellschaft,
Leverkusen, Germany, a corporation of Germany
No Drawing. Filed May 20, 1958, Ser. No. 736,465
Claims priority, application Germany June 5, 1957
11 Claims. (Cl. 260—461)
rides can be condensed with any alcohols or phenols to
form the hitherto unknown esters which distinguish
themselves by a very good contact-insecticidal action:
The present invention relates to and has as its objects 10
-In all these above shown formulae R and R1 and R2
new and useful insecticidal phosphonic acid esters and
have the ?rst menitoned signi?cance.
their production. Generally the new compounds may
The condensation of these phosphonic acid or thio
be represented by the following formula
phosphonic acid chlorides with alcohols or phenols may
be carried out in the presence of suitable acid-binding
agents. As acid-binding agents there are preferably used
tertiary amines in the presence of inert solvents, at room
temperature or slightly elevated temperature. When
condensing phenols, it is also possible to start ‘from the
alkali metal salts of the phenols or from the phenols
themselves and to bind the halogen with alkali metal car
in which R and R1 stand for alkyl radicals, R2 stands for
aliphatic, araliphatic or aromatic radicals which further
more may be substituted, and X, Y or Z stand for oxygen
or sulfur.
bonates. In the condensation of phenols with ?-alkoxy
(or ,B-alkylmercapto-)vinyl-phosphonic acid- or -thiono
pounds. Thus, if phosphonic or thionophosphonic acid
phosphonic acid ester chlorides, ketones have primarily
esters ‘are desired the following way may lead to that 25 proved to be particularly useful solvents (especially
part of the inventive compounds. Vinylalkyl ethers or
methyl ethyl ketone and methyl isobutyl ketone).
There are many ways of preparing the inventive com
mercaptans are known to add on phosphorus pentachlo
ride easily. The adducts thus formed may then be re
acted with sulfurous acid to form the corresponding di
chlorides:
If thiolphosphonic acid esters are desired B-alkoXy-(or
?-alkylmercapto-)vinylphosphonic acid ester chlorides
as described in the foregoing paragraph can be reacted
30 with any aliphatic, aliphatic~aromatic or aromatic mer
captans so as to form likewise new ,B-alkoXy-(or B-alkyl
mercapto-)-vinyl-phosphonic acid thiolesters of, the fol
lowing formula
wasp/m.
OR]
35
These {3 - alkoxy - (or ?-alkylmercapto-)-vinyl-pl1os
SR3
phonic acid dichlorides thus formed may be ‘further con
In another way the l3-alkoxy-(or B-alkylmercapto):
vinyl-thionophosphonic acid dichlorides also described‘ in
verted by known methods i.e. by reacting with convenient
alcohols to corresponding dialkyl esters of the following
general formula
0R2
These 5 - alkoxy - (or ?-alkylmercapto-)-vinyl-phos
the ?rst paragraph can be converted as described above
into the corresponding thionophosphonic acid mono
chlorides.
45
phonic acid dialkyl esters may be converted by known
methods with the aid of phosgene into the correspond
mercapto-)~vinyl-thionophosphonic acid.
These new thionophosphonic acids react, however, in
the tautomeric Form II:
ing 5 - alkoxy - (or ?-alkylmercapto-)-vinyl-phosphonic
acid ester chlorides:
When saponifying these ?-alkoXy-(or ?-alkylmer
capto-)-vinyl#thionophosphonic acid monochlorides with
alkaline reacting compounds chlorine is eliminated with
the formation of the corresponding ,B-alkoxy-(or ?-alkyl-r
50
0
(s)
CR1
l/OR‘
RO-—OH=CH—P
<s>
ii/OR’
2 RO—CH=CH—P\
OH
C1
SH
(I)
(II)
The above shown adducts of phosphorus pentachloride 55 It has now been found that aliphatic, ‘aliphatic-aromatic
and B-alkoxy-(or ?-alkylmercapto-)-vinyl-ethers may be
and in some cases also aromatic halides which may be
reduced with hydrogen sul?de so as to form ,B-alkoxy
substituted react with the Form II in such a manner that
(or B-alkylmercapto-)-vinyl-thionophosphonic acid di
,B-alkoxy-(or ?-alkylmercapto-)vinyl-thiolphosphonic acid
chlorides:
s
01
Cl
60
esters of the general formula
0
QR;
SR:
These easily obtainable dichlorides may also be con
are formed. These ?-alkoxy-(or ,8-alkylmercapto-)-vinyl
verted with appropriate alcohols by known methods into 65 thiolphosphonic ‘acid esters are identical with the com
the corresponding B-alkoxy-(or ,B-alkylmercapto-)-vinyl
pounds obtainable by the first mentioned process.
thionophosphonic acid alkyl ester chlorides:
When working according to the ?rst described method
for producing thiolphosphonic acid derivatives the reaction
70 usually should be carried out at slightly elevated tempera
tures say up to about 50 to 70° C. The mercaptans are
converted before reaction in their corresponding salts
3,047,605
4
3
either by reaction of alkali metals in suitable inert
(d)
O
OOH:
organic solvents such as benzene or toluene or by the
reaction of alkali metal alcoholates also in suitable inert
solvents; in this case especially lower ketones such as
acetone-or methyl ethyl ketone are most workable. If
Working according to the second described method for
producing thiolphosphonic acid esters the saponifying of
the thionoester chlorides should be carried out usually
with strong alkaline reactants such as e.g. potassium hy
droxide. Without isolating the intermediates then the
corresponding substituted halide is added. Reaction usu
ally is carried out also in this case at elevated tempera
tures say up to about 100° C. and using suitable inert
organic or aqueous organic solvents.
vAlso these new thiolphosphonic acid esters distinguish
themselves by an outstanding insecticidal action. The new
compounds have chiefly a systemic action.
If dithio-compounds are desired, the aforementioned )8
(h)
I
alkoxy-(or ?-alkylmercapto-) -vinyl~thionophosphonic acid
s
ll /
0 02115
02115s-0n=orr_1=
alkyl ester monochlorides are reacted with salts of any
aliphatic, aliphatic-aromatic or aromatic mercaptans so as
to form l8—alkoxy-(or ?-alkylmercapto-)-vinyl-dithiophos
phonic acid esters of the following general formula
OR;
25
SR2
have been prepared by mixing the active ingredient with
The condensation of the ?-alkoxy-(or ?-alkylmercap
to-)-vinyl-thionophosphonic acid monochlorides with
the same amount of dimethyl formarnide as an auxiliary
solvent adding thereafter 20% by weight referred to active
mercaptans is expediently carried out so that alkali metal 30 ingredient of a commercial emulsi?er consisting of a
benzyl hydroxy polyglycol ether containing about 10 to 15
alcoholates, especially sodium ethylate is used as an acid
glycol residues, and diluting at last this premixture with
binding agent. In this case most of the desired thiol
water to the desired concentration indicated in the follow
esters are obtained nearly quantitatively without the for
ing paragraphs. The tests have been carried out in the
mation of the corresponding oxygen esters as by-products.
following manner:
The condensation can expediently be carried out at
Against aphids (contact-insecticidal action) of the type
doralis fabae (with compounds (a), (c), (d), (f), (g),
(h), and (i) ). Heavily infested bean plants (Vitia faba)
a slightly elevated temperature, for example at 20—40° C.,
if desired also in ‘the presence of suitable inert solvents.
Also these dithio-products distinguish themselves by a
good contact-insecticidal action.
The new esters are es
pecially effective against red spiders and have chie?y an
acaricidal action.
have been sprayed drip wet with solutions as prepared
The effect has been determined by evaluation
after 24 hours by counting the dead pests either on the
surface of the soil or still remaining on the plants;
40 above.
They are ‘moreover also suitable for
killing caterpillars of various species.
a The new compounds of the present invention very ef
With compounds (a), (g), and (i): solutions of 0.01%
fectively kill insects like ?ies, mites, aphids, etc. They
kill aphids 100%,
distinguish themselves especially by a good contact-insecti 45 With
compounds (d) and (1‘): solutions of 0.001% kill
cidal activity and at the same time by an activity on eating
insects such as caterpillars.
aphids 100%,
With compounds (h): solutions of 0.1% kill aphids
100%;
Against caterpillars (with compound (b) ). White cab
Most surprisingly they are of
remarkable low toxicity against mammals. They may be
used in the same manner as other known phosphoric in
secticides, i.e. in a concentration from about 0.0000l% 50
bage has been sprayed drip wet with 0.1% aqueous
to about 1%, diluted or extended with suitable solid or
emulsions as prepared above. Caterpillars of the type
diamond back moth (10 each) have been placed on the
sprayed leaves of the white cabbage. The living status
liquid carriers or diluents. Examples of such solid carriers
are talc, chalk, bentonite, clay and the like, as liquid
carriers there may be mentioned, water (if necessary with
a commercial emulsi?er), alcohols, especially lower al
cohols such as methanol or ethanol, ketones, especially
has been determined after 24 and 48 hours, and com—
plete killing has been obtained;
Against spider mites (contact-insecticidal action) of
the type species Tetranychus telarius (two spotted spider)
(with compounds (0), (d), and (e)). Bean plants
lower ketones such as acetone or methyl ethyl ketone,
liquid hydrocarbons and the like. The new compounds
may furthermore be used in combination with each other
60 v(Phaseolus vulgaris) of about 15 inches height are
or with known insecticides, fertilizers etc.
The insecticidal activity of the inventive compounds
sprayed drip wet with solutions prepared as indicated
above. The bean plants have been infested heavily with
may be seen from the following test results.
the two spotted spider. Evaluation has been carried
Aqueousdilutions of the following compounds
out after 24 hours, 48 hours and 8 days;
65
(b)
ISl OCtHb
C2H50—GH=CH—P
SCzHs
(c)
.
O
ll/
OO1H5
70
With compounds (0) and>(e): solutions of 0.01% kill
spider mites 100%,
With compound (d): solutions of 0.001% kill spider
mites 90%;
Against flies (Musca domestica) (with compounds (g),
(h), and (i)). About 50 ?ies were placed under cov
ered Petri dishes in which drip wet ?lter paper has been
placed which is sprayed with an insecticidal solution as
prepared above. The living status of the ?ies has been
75 determined after 24 hours;
3,047,605
5
6
With compounds (g) and (i): solutions of 0.011% kill
per os of 5' milligrams per kilogram. 0.1 percent solu~
?ies 100%,
tions kill red spiders completely.
With compound (h): solutions of 0.1% kill ?ies 100%.
Example 4
Further activities of the inventive compounds are to
be found in the following examples, which are given by
way of illustration only without, however, limiting the
present invention thereto.
Example 1
S
OCgH5
24 grams of cyclohexylmercaptan are dissolved in 50
10
S.CH2.CHz.S 02115
25 grams of ,B-ethylmercaptoethylmercaptan (B.P.
67° C./ 12 mm. Hg) are dissolved in 100 millilitres of
millilitres of anhydrous alcohol. A sodium ethylate solu
tion containing 0.2 mol of dissolved sodium is added
dropwise thereto at 30° C. 45 grams of B-ethoxyvinyl
ethylthionophosphonic acid monochloride are added drop
wise with further stirring at 30° C. and the mixture is
heated to 35—40° C. for a further 2 hours. The product
is then worked up as described in Example 1, and 42
grams of the new ester of B.P. 120° C./0.01
Hg.
are thus obtained. Yield: 72 percent of the theoretical.
The new ester is a pale yellow water-insoluble oil which
shows a toxicity on rats per os of 250 milligrams per kilo
anhydrous alcohol. A sodium ethylate solution contain
ing 0.2 mol of sodium is added thereto at about 30° C.
The mixture is after-stirred at 30 C. for a half hour and
45 grams of ?-ethoxyvinylethylthionophosphonic acid
monochloride (B.P. 60° C./0.01
Hg) are then added
dropwise with further stirring "at 30° C. The mixture
gram. 0.1 percent solutions kill caterpillars completely.
Example 5
is after-stirred at 30° C. for an hour, then poured into
300 millilitres of water, the separated oil is taken up in
200 millilitres of benzene and the benzenic solution is
i OCgH5
washed twice with SO-millilitre portions of water. The 25
benzenic solution is then dried over sodium sulphate.
OQHJ0.0H:CH—P
After distilling off the solvent, the residue is fractionated.
46 grams of the new ester of B.P. 118° C./0.0l mm. Hg
22 grams of thiophenol are dissolved in 50 millilitres of
are thus obtained. Yield: 77 percent of the theoretical.
anhydrous alcohol. A sodium ethylate solution contain
30
The new ester is a pale yellow water-insoluble oil.
ing 0.2 mol of dissolved sodium is added thereto with
The new ester shows a toxicity on rats per os of
stirring at 30° C. 45 grams of ,B-ethoxyvinylethyl
about 25 milligrams per kilogram. Aphides are still
thionophosphonic acid monochloride are then added
killed completely at a concentration of 0.01 percent.
dropwise with further stirring at 30° C. and the mixture
Spider mites are completely killed even at a concentration
is after-stirred at 40° C. for an hour. After working up
of 0.001 percent. 0.1 percent solutions show a complete
as usual, 47 grams of the new ester are obtained which
systemic action. Moreover, 0.1 percent solutions kill cat
boils under av pressure of 0.01 mm. Hg. at 130 C. Yield:
erpillars with certainty. 0.1 percent solutions also have
82 percent of the theoretical.
a positive ovicidal action on the ovae of red spiders.
The new ester shows a toxicity on rats per es of 100
milligrams per kilogram. ‘0.1 percent solutions kill cater
pillars completely. Aphides and spider mites are still
Example 2
completely killed at a concentration of 0.01 percent.
Example 6
13 grams of ethylrnercaptan are dissolved in 60 milli
litres of anhydrous alcohol. A sodium ethylate solution
45
containing 0.2 mol of dissolved sodium is added thereto
dropwise with stirring at 30° C. 45 grams of ,B-ethoXy
37 grams of p-chlorophenylmercaptan are dissolved in
vinylethyl-thionophosphonic acid monochloride are then
added with further stirring at 30° C. The mixture is 50 50 millilitres of anhydrous alcohol. 0.2 mol of a sodium
ethylate solution is added thereto dropwise with stirring
after-stirred for an hour and then worked up as described
in Example 1. 43 grams of the new ester of RP. 90° C./
0.01 mm. Hg are thus obtained. Yield: 88 percent of
the theoretical. The new ester is a colourless water-in
soluble oil. The new ester shows a toxicity on rats
per os of 100 milligrams per kilogram. 0.1 percent solu
C. for a further 2 hours and then worked up as described
in Example 1'. 70- grams of the new ester are thus ob
tions kill caterpillars completely.
tained as a pale yellow water-insoluble oil. On prolonged
at 30° C. 45 grams of B-et-hoxyvinylethyl-thionophos
phonic acid monochloride are then added dropwise with
‘further stirring at 30° C. The mixture is stirred at 35°
standing the crude product crystallises in colourless crys
tals which have a distinct melting point of 50° C.
Example 3
60
S C aHra
24 grams of n-hexylmercaptan are dissolved in 50 milli
litres of anhydrous alcohol. A sodium ethylate solution
The ester kills rats per os at 50 milligrams per kilo
gram.- Spider mites are completely killed at a concentra
tion of 0.01 percent. Caterpillars are still killed with
certainty by a 0.1 percent aqueous solution.
Example 7
containing 0.2 mol of dissolved sodium are added thereto
at 30° C. 45 grams of ?-ethoxyvinylethyl-thionophos
phonic acid monochloride are added thereto dropwise
with stirring at 30° C. and the mixture is heated to 30—
35° C. for a further 2 hours. The product is then worked
up as described in Example 1, and 52 grams of the new
45 grams of 3,4-dichlorophenylmercaptan are dissolved
ester are thus obtained which distills under ‘a pressure of
in 120 millilitres of anhydrous alcohol. A sodium ethylate
Cl
0.01 mm. Hg at 105° C. without decomposition. Yield:
solution containing 0.3 mol of dissolved sodium is added
88 percent of the theoretical. The ester is a colourless
thereto dropwise with stirring at 30” C. To this solution
water-insoluble oil. The ester shows a toxicity on rats 75 there are added dropwise with further stirring at 30° C.
3,047,605
55 grams of B-ethoxyvinylethyl-thionoph0sphonic acid
55 grams of ?-ethoxyvinylethyl-thionophosphonic acid
monochloride and the temperature is maintained at 40°
C. for a further 2 hours. The product is then worked
monochloride. The mixture is after-stirred at 40° C. for
two hours and then worked up in usual manner. 69 grams
up as described in Example 1. 77 grams of the new ester
are thus obtained as a colourless crystalline powder of
of the new ester are thus obtained as a yellow water
melting point 68° C. Yield: 87 percent of the theoretical.
ester is not distillable even under high vacuum.
insoluble oil. Yield: 88 percent of the theoretical. The
The DL50 on rats per os is 100 milligrams per kilogram.
0.1 percent solutions kill caterpillars with certainty.
Example 8
S
Example 11
S
00113
C2H5O.CH=CH—~P
10
00211!
C2H5O.CH=CH——IIEL
38 grams of p-chlorothiophenol are dissolved in 100
millilitres of methanol. A sodium methylate solution con
S .CH2.S CzH5
22 grams of a-mercaptoimethylthio ethyl ether (B.P. 15 taining 14 mol of dissolved sodium are added at 30° C.
50° C./ 12 mm. Hg) are dissolved in 75 millilitres of an
The mixture is after-stirred at 30° C. for a half hour
hydrous alcohol. A sodium ethylate solution containing
and 53 grams of ?-ethoxyvinyl-thionophosphonic acid
0.2 mol of ‘dissolved sodium is added thereto. 45 grams
methyl ester chloride (B.P. 55° C./0.01 mm. Hg) are
of B-ethoxy-vinylethyl-thionophosphonic acid monochlo
then added with stirring at the aforesaid temperature.
ride are added thereto dropwise with further stirring at 20 The reaction product is heated at 30-35° C. for a further
35° C. and the temperature is kept at 30° C. for a further
hour and then poured into plenty of water. The sepa
hour. After working up as usual, 37 grams of the new
rated oil is taken up with benzene, washed neutral and
ester of B.P. 115° C./0.01 mm. Hg are obtained. Yield:
dried. After distilling sit the solvent, 45 grams of the
65 percent of the theoretical. The ester is a colourless
new ester are obtained as a pale yellow water-insoluble
water-insoluble oil.
25 oil. Yield: 59 percent of the theoretical.
DL50 ‘on rats per os: 10 milligrams per kilogram.
Example 12
0.01 percent solutions ‘kill aphids completely. Spider
mites are still killed’completely at a concentration of
0.001 percent. 0.1 percent solutions have a strong sys
temic action. Caterpillars are killed with certainty even 30
at a concentration of 0.1 percent. Spider mite ovae are
also killed with certainty by 0.1 percent solutions.
By the same way but using instead of ?-ethoxy-vinyl
ethyl-thionophosphonic acid monochloride B-ethoxy-vinyl
methyl-thionophosphonic acid monochloride or B-ethoxy
Il/
CH3
S CGH13
hour and 53 grams of (3-ethoXyvinyl-thionophosphonic
acid methyl ester chloride are then added at this tempera
ture. After working up as usual, 36 grams of the new
molecular amounts [there are obtained the following two
S
OOH:
30 grams of n-hexylmercaptan are dissolved in 100
millilitres of methanol. A sodium methylate solution con
taining 1A1. mol of dissolved sodium is added thereto at
35 30° C. The mixture is after-stirred at 30° C. for a half
vinylpropyl-thionophosphonic acid monochloride in equi
compounds:
S
ester are obtained as a colourless water-insoluble oil of
40 B.P. 98° C./0.0l mm. Hg. Yield: 51 percent of the
theoretical.
V 7
Example 13
S
03117
S
OCHa
‘s-oHt-s c2116
Example 9
s
ll/
30 grams of cyclohexylmercaptan are dissolved in 100
millilitres of methanol. A sodium methylate solution con
taining 1%: mol of dissolved sodium is added thereto. At
002115
30° C., 53 grams of ,B-ethoxyvinyl-thionophosphonic acid
methyl ester chloride are added dropwise with stirring.
32 grams of p-thiocresol are dissolved in 70 millilitres
of anhydrous alcohol. A sodium ethylate solution con
The mixture is stirred at 30—35° C. for an hour and then
worked up in uusual manner. 35 grams of the new ester of
taining 0.2 mol of dissolved sodium is added thereto, 45 55 B.P. 105° C./0.01 mm. Hg are thus obtained. Yield: 50
grams of B-ethoxyvinylethyl-thionophosphonic acid mono
percent of the theoretical.
’chloride are then added dropwise with stirring and the
Example 14
mixture is after-stirred at 40° C. for 2 hours. After
working up as usual, 63 grams of the new ester are ob
tained. Yield: 84 percent of the theoretical. The new 60
ester is not distillable even under high vacuum.
062115
S.CH2.CH2.SC2H5
The new ester kills rats per os at 250 milligrams per
kilogram. Flies are still killed with certainty at a con
32 grams of ?-ethylmercapto-thioethyl ether (B.P. 67°
centration of 0.001 percent. Aphides are destroyed with
certainty by 0.1 percent solutions.
S
CH3O.CH=CH-—i.l3
C./l2 mm. Hg) are dissolved in 120 millilitres of an
65
hydrous alcohol. A sodium ethylate solution containing
1%; mol of dissolved sodium is added thereto at 30° C.
52 grams of B-methoxyvinyl-thionophosphonic acid ethyl
ester chloride (B.P. 55° C./0.0l mm. Hg) are then added
dropwise with further stirring at 30° C. The mixture
70 is after-stirred at this temperature for another hour and
34 grams of ?-diethylaminoethylmercaptan (B.P. 54°
‘C./ 10 mm. Hg)v are dissolved in 100 millilitres of methyl
then Worked up in usual manner. 54 grams of the new
ester of B.P. 94° C./0.01 mm. Hg are thus obtained. The
ester is barely Water soluble. Yield: 76 percent of the
ethyl ketone. A sodium ethylate solution containing 0.25
theoreticaL. Aphides are completely killed by 0.001 per
mol of dissolved sodium is added thereto with stirring.
To the solution thus obtained there is added at 30° C. 75 cent suspensions of this ester.
3,047,605
9
10
Example 15
Example 19
28 grams of a-methylmercapto-thioethyl ether (B.P. 5
24 grams of p-thiocresol are dissolved in 100 millilitres
of ethylmethylketone. A sodium ethylate solution con
50° C./ 12 mm. Hg) are dissolved in 120 millilitres of
anhydrous alcohol. A sodium ethylate solution contain
ing 1%; mol of dissolved sodium is added thereto. The
mixture is after-stirred at 30° C. for 30 minutes and 53
taining 0.2 mol of dissolved sodium are added thereto at
grams of ?-methoxyvinvl-thionophosphonic acid ethyl es
ter chloride are added dropwise rat the said temperature.
The product is after~stirred for another hour and then
ester chloride are then added dropwise with stirring at
30° C. The mixture is heated at 30° C. ‘for another hour
worked up in usual manner. '49 grams of the new ester
of B.P. 90° C./ 00.1 mm. Hg are thus obtained as a colour
water-insoluble pale yellow oil are thus obtained. Yield:
82 percent of the theoretical.
30° C. 40 grams of ,B-ethoxyvinyl-phosphonic acid ethyl
and then worked up in usual manner.
less water-insoluble oil. Yield: 72 percent of the theo 15
retical. Spider mites are still completely killed by 0.0001
47 grams of a
Example 20
O OCQHU
percent solutions.
Example 16
S.CHg.CHg.SCgH5
43 ‘grams of ?-ethoxyv'inyl-thionophosphonic acid ethyl
s)
t
ester chloride (B.P. 60° C./ 0.01 mm. Hg) are dissolved
in 100 millilitres of anhydrous alcohol.
25 millilitres
6 grams of ?nely divided sodium are suspended in 200
of water are added thereto. 23 grams of potassium
millilitres of benzene. 31 grams of li-ethylmercapto 25 hydroxide dissolved in 50 millilitres of ‘water are then
ethylmercaptln (B.P. 67° C./l2 mm. Hg) are added
added with stirring and the reaction mixture is kept at
thereto with‘stirring. The mixture is heated to 50° C.
70° C. ‘for an hour. 25 grams of ?-ethylmercaptoethyl
for a further 4 hours. To the suspension of sodium
mercapt-an are thereupon added with ‘stirring and the mix
mercaptide thus obtained there are added with stirring
ture is heated to 75—80° C. for a further 2 hours. After
at 50—60° C. 50 grams of ?-ethoxyvinyl-phosphonic acid 30 cooling, the reaction mixture is poured into 300 millilitres
ethyl ester chloride (B.P. 70° C./0.05 mm. Hg). The
of Water, the separated oil is taken up with 200 millilitres
mixture is after-stirre ‘at 50° C. for 2 hours and then
of lbenzene and the benzene solution is shaken twice with
poured into 200 mil ilitres of ice-Water. The benzenic
50-millilitre-portions of a 4 percent sodium bicarbonate
solution is separated off, washed twice with SO-millilitre
solution; The benzene solution is dried over sodium sul
portions of water and dried over sodium sulphate. After 35 phate. The benzene is distilled off and the residue frac
distilling o?? the benzene under vacuum the residue is frac
tionated under rvacuum. 40 grams of the new ester of
tionated. 51 grams of the new ester of B.P. 110° C./0.01
mm. Hg are thus obtained. Yield: 72 percent of the
theoretical.
B.P. 110° C./0.01 mm. Hg are thus obtained. Yield: 70
percent of the theoretical.
The compound thus obtained is identical with the one
The ester is a pale yellow water-insoluble
oil.
obtained according to Example 1.
Example 21
Example 17
0 002m
13/0 (32H;
ll/
CzH50.CH=CH-P
45
55 grams of ‘B-CthOXYVlDYI-tthiOIlOPhOSPhOIllC acid ethyl
37 grams of p-chlorophenylmercaptan are dissolved in
ester chloride are dissolved in 125 grams of anhydrous
100 millilitres of ethylmethylketone. A sodium ethylate
alcohol. 30 millilitres of water are added thereto and
solution containing 0.25 mol of dissolved sodium is added
then a solution of 29 grams of potassium hydroxide in
50
dropwise with stirring at 30° C. 50 grams of ?-ethoxy
60 millilitres of water. The mixture is heated to 70° C.
vinyl-phosphonic acid ethyl ester chloride are then added
‘for a further 2 hours and 32 grams of monochloracetic
dropwise with stirring at 30° C. The mixture is after
acid ethyl ester are then added. The mixture is heated
stirred at 30° C. for an hour and then worked up as in
with ‘further stirring to 75° C. for a further l—2 hours.
dicated in Example 1. 70 grams of the new ester are
It is then cooled to room temperature and poured into
thus obtained as a water-insoluble oil which is not distilla
300 millilitres of ice water. The separated oil is taken
ble even under vacuum. Yield: 90 percent of the theo
up with 300 millilitres of benzene. The benzene solu
retical.
tion is washed twice with 50 millilitre-portions of a 4
Example 18
percent sodium bicarbonate solution. The benzenic solu
tion is then dried over sodium sulphate. By fractionating
38 grams of the new ester of B.P. 115° C./0.01 mm. Hg
are obtained. Yield: 54 percent of the theoretical. The
new ester is a water-insoluble colourless oil.
Example 22
Cl
65
46 grams of 3,4-dichlorophenylmeroaptan are dissolved
in 100 millilitres of ethylmethylketone. A sodium ethyl
ate solution containing 0.25' mol of dissolved sodium is
added dropwise with stirring at 30° C. 50 grams of ,8
ethoxyvinyl-phosphonic acid ethyl ester chloride are then 70
added with stirring at 30° C. The mixture is kept at 30°
C. for another hour and then Worked up as described in
Example 1. 70 grams of the‘new ester are thus obtained
as ‘a water-insoluble oil which is not distillable even un
der vacuum. Yield: 82 percent of the theoretical.
55 grams of B-ethoxyvinyl-thionophosphonic acid ethyl
ester chloride are dissolved in 125 millilitres of anhydrous
alcohol. 30 millilitres of water ‘are added thereto and
then‘ a solution of 29 grams of potassium hydroxide in
60 millilitres of water. The mixture is heated to 75 °' C.
75 for a further 2 hours and 47 grams of ?-bromopropionic
3,047,605
12
11
Example 27
acid ethyl ester are then added. The mixture is heated
O CgH5
with further stirring ‘at 75 ° C. for 2 hours and then
worked up as described in Example 6. 40 grams of the
new ester of B.P. 120° C./ 0.01 mm. Hg are thus obtained.
Yield: 54 percent of the theoretical. The ester is a col
S.CHz.CN
55 grams of [3-ethoxyvinyl-thionophosphonic acid ethyl
ourless Water-insoluble oil.
ester chloride are dissolved in 125 millilitres oi anhydrous
alcohol. 30 millilitres of water are added thereto and
Example 23
O
OOzH;
then a solution of 29 grams of potassium hydroxide in 60
1O millilitres of water. After having kept the reaction prod
CzH5O.CH=CH—P
uct at an internal temperature of 75° C. for 2 hours, 20
grams of chloracetonitrile are added. The mixture is kept
at 75° C. for a further 4 hours and then worked up in
SCaHnUIl)
55 grams of ?-ethoxy-vinyl-thionophosphonic acid ethyl
ester chloride are dissolved in 125 millilitres of anhydrous
usual manner. 45 grams of the new ester ‘are thus ob
alcohol. 30 millilitres of water are added thereto with
15 tained. Yield: 76 percent of the theoretical. The yellow
stirring and then a solution of 29 grams of potassium
water~insoluble ester is distillable only with decomposition
hydroxide in 60‘ millilitres of water. The mixture is
even under high vacuum.
heated to 75° C. for 2 hours and 55 grams of n-hexylio
Example 28
dide are then added. The temperature is kept at 75°
C. with stirring for a \further 3 hours and then worked
20
up as described in Example 6. 35 grams of the new ester
of B.P. ll0°/0.01 mm. Hg are thus obtained. Yield: 50
\
some-Q-m
percent of the theoretical.
Example 24
55 grams of ?-ethoxyvinyl-thionophosphonic acid ethyl
O OCzH;
25 ester chloride are dissolved in 125 millilitres of 98 percent
alcohol. 30 millilitres of water are added thereto and
then a solution of 29' grams of potassium hydroxide in 60
millilitres of Water. The mixture is stirred at an internal
C2H50.CH=OH—P
soizHzs
55 grams of B-ethoxyvinyl-thionophosphonic acid ethyl
temperature of 75 ° C. for a further 2 hours and 50 grams
ester chloride are dissolved in 125 millilitres of 98 per 30 of u-chloromethyl-(4-chlorophenyl)-thioether are then
cent alcohol. 30 millilitres of water are added thereto
added. The reaction product is kept at an internal tem
and then a solution of 30' grams of potassium hydroxide
perature of 75 ° C. for a further 2 hours and then worked
in 60 millilitres of water. The mixture is heated with
stirring to 75° C. for 2 hours and 74 grams of dodecylio
up in usual manner.
dide are then added. The mixture is heated at 75 ° C. for
percent of the theoretical.
a further 4 hours and then worked up as described in
Example 6. 55 grams of the new ester of B.P. 160°
C./ 0.01 mm. Hg are thus obtained. Yield: 60 percent of
Example 29
(H) OCZH5
the theoretical.
Example 25
78 grams of the new ester are thus
obtained as a pale yellow water-insoluble oil. Yield: 89
40
CzH5O.CH=CH—P
55 grams of ?-ethoxyvinyl-thionophosphonic acid ethyl
ester chloride are dissolved in 125 millilitres of 98 per
cent alcohol. 30 millilitres of water are added then and
55 ‘grams of B-ethoxyvinylthionophosphonic acid ethyl
45 then a solution of 29 grams of potassium hydroxide in 60
ester chloride are dissolved in 125 millilitres of 98 per
cent aleohol. 3O millilitres of Water are added thereto
millilitres of water. The mixture is stirred at an internal
temperature of 75° C. for a further 2 hours and 32 grams
of benzyl chloride are then added. The mixture is there
upon heated at 7 5° C. for a further 2 hours. After work
ing up as usual, 37 grams of the new ester of B.P. 130° C/
0.01 mm. Hg are obtained. Yield: 52 percent of the theo
retical. The new ester is a pale yellow Water-insoluble
and then a solution of 29 grams of potassium hyroxide
in 60 millilitres of water. The temperature is kept at
75 ° C. for a further 2 hours and 68 grams of B-diethyl
aminoethyl-mercaptan are then added. The reaction
product is then kept at an inside temperature of 75° C.
for a ‘further 4 hours. After working up as usual, 54
grams of the new ester are obtained. Yield: 73 percent
vBy the same way but using instead of ?-ethoxyvinyl
thionophosphonic acid ethyl ester chloride the equimolec
ular amount of the ?-n-butoxyvinylthionophosphonic
of the theoretical. The colourless barely water-soluble
oil is distillable under high vacuum only with decompo
sition.
acid ethyl ester chloride there is obtained the ester of the
Example 26
following formula
60
5 grams of y3-ethoxyvinylthionophosphonic ‘acid ethyl
ester chloride are dissolved in 125 millilitres of 98 percent 65
alcohol. 30 millilitres of water are added thereto and
then a solution of 29 grams of potassium hydroxide
in 60 millilitres of water. The temperature is kept at 75 °
C. for a [further 2 hours and 42 grams of p-chlorobenzyl
chloride are then added. The reaction mixture is kept 70
at an internal temperature of 75° C. for a further 4 hours
and then worked up in usual manner. 53 grams of the
new ester are thus obtained as a pale yellow water insolu
ble oil. Even under high vacuum the new compound is
distillable only with decomposition.
0
II/
002115
Example 30
O
OCHs
CgH50.CH=CH—P
-5 3 grams of B-ethoxyvinyl-thionophosphonic acid meth
yl ester chloride are dissolved in 130 milliliters of meth
anol. 30 millilitres of water are added thereto and then
a potassium hydroxide solution of 29‘ grams of potassium
hydroxide in 60 millilitres of water. The mixture is
75 heated to the boil for 2 hours and 25 grams of [.i-diethyl
3,047,605
13
14
aminoethy-l chloride are then added. The reaction prod
sulphate. After distilling 01f the solvent under vacuum,
uct is then further ‘heated to the boil for 2 hours. After
38 grams of the new ester remain behind as a colourless
working up as usual, 17 grams of the new ester are ob
tained as a yellowish brown-water-insoluble oil. Yield:
water-insoluble oil. B.P. 110° C./0.01 mm. Hg. Yield:
25 percent of the theoretical.
1DL50: 100 milligrams per kilogram.
Spider mites are killed completely with 0.01% solu
67 percent of the theoretical.
Example 31
Toxicity on rats per os
tions. 0.1% solutions have a systemic action on aphides.
0 00113
Example 35
10
53 grams of l8-ethoxyvinyl-thionophosphonic acid meth
yl ester chloride (B.P. 55° C./ 0.01 mm. Hg) are dissolved
in 130 millilitres of methanol. 30 millilitres of water are
added thereto and then a solution of 29 grams of potas
sium hydroxide in 60 millilitres of water. The water is
heated to 70° C. for 2 hours and 33 grams of benzyl
chloride are then added‘. The reaction product is after
27 grams of p-nitrophenol are dissolved in 200 milli
litres of anhydrous ethyl alcohol. 45 grams of a sodium
ethylate solution containing 1/5 mol of sodium are added
thereto with stirring. The mixture is stirred at 25—30° C.
for half an hour and 43 grams of p-ethoxyvinyl‘thiono
st-irred at 70-75 ° C. for a further 2 hours and then poured
phosphonic acid ethyl ester chloride are then added at
into water. The separated oil is taken up with benzene, 20 30° C. with ‘further stirring. After a short time the re
washed neutral and dried. After distilling o? the solvent,
action product shows a neutral reaction. The reaction
38 grams ‘of the new ester are obtained as a pale yellow
product ‘is then poured into 300 millilitres of water and
water-insoluble oil. Yield: 56 percent of the theoretical.
the precipitated oil is taken up with benzene. The ben
zene solution is washed twice with 25 millilitre portions
Example 32
of water and then dried over sodium sulphate. On frac
O OCH3
tionating, 50 grams of the new ester of B.P. 85° C./ 0.01
mm‘. Hg are obtained.
53 grams of l3-ethoxyvinyl-thionophosphonic acid meth
tions.
ly ester chloride are dissolved in 130 millilitres of meth
anol. 30 millilitres of water are added thereto and then
a solution of 29 grams of potassium hydroxide in 60
millilitres of water. The mixture is heated to 70-—75° C.
for 2 hours and 32 grams of ?chlorethylthioethyl ether
are then added.
Toxicity on rats per os DL50:
25 milligrams per kilogram.
Aphides are destroyed with certainty with 0.001% solu
S .CH2.CH2. S CgHs
The new: ester kills spider mites completely at
a concentration of 0.001%.
Moreover, the new ester
has a strong ovicidal action on the eggs of red spiders.
Example 36
s
OC2H5
The reaction product is kept at 70
75° C. for a further 2 hours and then worked up in usual
manner.
32 grams of the new ester are thus obtained as
a yellow water-insoluble oil.
theoretical.
Yield: 48‘ percent of the
40
Example 33
Cl
43 grams: of 3-chloro-4-nitrophenol are dissolved in
150‘ millilitres of ethyl methyl ketone. 40 grams of dry
IS] OCzH5
ground potassium carbonate are added to this solution.
OEH5O.CH=OH—P
The mixture is heated with stirring to an internal tem
perature of 75° C. and 55 grams of ?-ethoxyvinyl-thiono
O.CHz.CC1a
45 phosphonic acid ethyl ester chloride are added at this
38 grams of trichlorethylalcohol are dissolved in 22
temperature. The mixture is heated at 75—80° C. for
grams of anhydrous pyridine. 5 5 grams of ?-ethoxyvinyl
a further 4 hours and then worked up in usual manner.
thionophosphonic acid ethyl' ester chloride (-B.P. 60° C./
After distilling off the solvent, 57 grams of the new ester
0.01 mm. Hg) are added thereto with stirring. The tem
perature is kept at 45-50° C. for 8 hours and the mix 50 are obtained as a pale yellow water-insoluble oil. The
ester is distill-able only with decomposition, even under
ture is then poured into 200 millilitres of ice-water to
high vacuum. Yield: 65 percent of the theoretical.
which 20 millilitres of dilute hydrochloric acid have been
added. The separated oil is taken up with benzene and
Example 37
neutralised with sodium bicarbonate. The benezene solu
sI OCzH5
tion is dried over sodium sulphate and then fractionated.
CzH5O.CH=CH—l>/
35 grams of the new ester of B.P. 105° C./0.01 mm. Hg
are then obtained. Yield: 43 percent of' the theoretical.
60
To a suspension of 30 grams of anhydrous ground
potassium carbonate in 130 grams of ethyl methyl ketone
there are added with stirring 22 grams of ,B-ethyl mer
capto ethanol.
chloride are added dropwise at an internal temperature
65 of 75° C. and the mixture is then heated at 75-80° C.
45 grams of B-ethoxyvinyl-thionophos~
phonic acid ethyl ester chloride are then added at an
internal temperature of 75° C. with’ further stirring. The
reaction product is heated to 75—80° C. for 3-4 hours
and then cooled to room temperature.
43 grams of 4-chloro-3-nitrophenyl are dissolved in
150 millilitres of ethyl methyl ketone. 40 grams of dry
and ground potassium carbonate are added thereto. 55
grams of ,8-ethoxyvinyl-thionophosphonic acid ethyl ester
The reaction
product is poured into 300 millilitres of water. The
‘precipitated oil is taken up with 200 millilitres of ben
zene. The benzene solution is washed twice with 50
millilitre portions of water and then dried over sodium 75
for a further 4 hours.
After working up as usual, 46
grams of the new ester are obtained as a yellow water
insoluble oil which is not distillable even under high
vacuum. Yield: 52 percent of the theoretical.
Example 38
i OC2H5
CgH50.CH=CH-'P
3,047,605
15
litres of benzene. 27 grams of cyclohexanol are added
thereto with stirring at 50° C. The mixture is heated
at 50° C. for an hour. The sodium has then dissolved.
55 grams of [i-ethoxyvinyl-thionophosphonic acid ethyl
ester chloride are then added with further stirring at
50—55° C. The reaction product is heated at 50—55° C.
for another hour and then worked up in usual manner.
50 grams of the new ester are thus obtained as a pale
yellow water-insoluble oil of RP. 105° C./0.0l mm. Hg.
Yield: 72 percent of the theoretical.
16
millilitres of benzene. 30 grams of benzyl alcohol are
added with stirring to this suspension at 50° C. The
mixture is stirred for a further 2' hours. The sodium is
then dissolved. 27 grams of ,B-methoxyvinyl-thionophos
phonic acid ethyl ester chloride (B.P. 55° C./0.01 mm.
Hg) are added at 50° C. to the solution thus obtained.
The mixture is heated at 50° C. for another hour, then
cooled to room temperature and poured into 300 millilitres
of ice-water. The separated oil is taken up with benzene,
separated from water and dried. On fractionating, 26
6 grams of powdered sodium are suspended in 50 milli
grams of the new ester are obtained as a pale yellow
‘
water-insoluble oil of RP. 115° C./0.01 mm. Hg. Yield:
76 percent of the theoretical.
By the same way but using the equimolecular amount
15
of [3-n-propoxyvinyl-thionophosphonic acid ethyl ester
chloride instead of ,B-methoxyvinyl-thionophosphonic acid
ethyl ester chloride there is obtained the following com
pound
S
52 grams of 3-chloro-4-methyl—7-hydroxycoumarin are
dissolved in 150 millilitres of ethyl methyl Vketone. 40
Example 43
grams of dry and screened potassium carbonate are added
therto. 55 grams of ,8-ethoxyvinyl-thionophosphonic acid 25
S
0.011161332502115
28 grams of ?-oxethyl-thioethy-lether are suspended in
150 millilitres of methyl ethyl ketone with the addition of
50 grams of the new ester are thus
obtained as colourless crystalline needles melting at 76°
C. Yield: 52 percent of the theoretical.
40 grams of anhydrous powdered potassium carbonate and
of 1 gram of powdered cooper. 53 grams of IS-methoxy
vinyl -thionophosphonic acid ethylester chloride ‘are added
Example 40
O
00211;
CHaO.CH=GH—lI’
ethyl ester chloride are added with stirring at 75° C. to
the suspension. The mixture is heated to an internal
temperature of 75—80° C. for 12 hours and then worked
up in usual manner.
002115
with stirring at 80° C. to this suspension there. The mix
35 ture is kept at 80° C. with stirring for a further 4 hours
and then Worked up in usual manner. 55 grams of the
OCaHu
new ester are thus obtained as a water-insoluble yellow
oil. Yield: 81 percent of the theoretical.
35 grams of p-nitrophenol are dissolved in 150 milli
litres of ethyl methyl ketone. 40 grams of dry and
screened potassium carbonate are then added with stir
In a concentration of 0.1 percent, the ester shows a
marked systemic action on aphids.
ring. 50 grams of B-ethoxyvinyl-phosphonic acid ethyl
ester chloride (B.P. 70° C./ 0.05 mm. Hg) are then added
dropwise ‘at an internal temperature of 75° C. The mix
ture is heated at 75—80‘’ C. for a further 4-5 hours and
then worked up in usual manner. 51 grams of the new
ester are thus obtained as a yellow water-insoluble oil.
Yield: 68 percent of the theoretical.
36 grams of ?-ethylmercapto-ethylmercaptan (B.P. 67°
The ester boils
C./ 12 mm. Hg) are dissolved in 100 millilitres of anhy
under a pressure of 0.01 mm. Hg at 135° C. Toxicity
on rats per os DL50: 25 milligrams per kilogram. 0.01%
solutions kill Colorado beetles with certainty. 0.01% so
drous ethanol. At 30° C. there is added while stirring
a sodium ethylate solution in ethanol containing 1A mol
50 of sodium.
lutions destroy aphides.
Example 41
At the same temperature there are added
59 grams of B-ethylmercapto-vinyl-thionophosphonic acid
ethyl ester chloride. The temperature is kept for 1 futher
hour and the mixture is worked up in the usual manner.
There are obtained 62 grams of the new ester boiling
0 001115
55 at 0.01 mm. Hg at 118° C. The new ester is a colourless
and water-insoluble oil. The yield amounts 87 percent
of the theoretical. The toxicity on rats is 100 mg./kg.
O.CHz.CH2. S 03115
6 grams of powdered sodium are suspended in 100
millilitres of benzene. 60 grams of ,B-ethoxy ethanol are
added with stirring at 45° C. The sodium is then dis
solved. 50 grams of ,B-ethoxyvinylphosphonic acid ethyl
LD5U.
60
Example 45
S
OCgHs
ester chloride are then added with further stirring at 0 to
+10° C. The mixture is stirred at 10° C. for a further
hour and then poured in 200 millilitres of Water. After
34 grams of ?-diethylamino-ethylmercaptan (B.P. 54°
working up as usual, 47 grams of the new ester of B.P.
65 C./ 10 mm. Hg) are dissolved in 100 millilitres of anhy
108° C./0.01 mm. Hg are obtained. Yield: 70 percent
drous alcohol. There is added at 30° C. a sodium ethylate
of the theoretical. Toxicity on rats per os DL50: 1000
solution in anhydrous alcohol containing 1%: mol of
milligrams per kilogram.
sodium. At the same temperature there are added drop
Example 42
IS OCzHs
CH3O.CH=CH—P
Wise while stirring 59 grams of B-ethylmercapto-vinyl
70 thionophosphonic acid ethylester chloride. The same tem
perature is kept for 1 further hour and the mixture is
worked up in the usual manner. There are obtained 77
grams of the new ester of the above shown formula as
a slightly yellow water-insoluble oil. The yield is 94
30 grams of powdered sodium are suspended in 100 75 percent of the theoretical. The new ester is undistillable
3,047,605
17
18
even in high vacuum. The toxicity on rats orally is 25
29 grams of cyclohexyl mercaptan are dissolved in 100
mg./kg. LD95.
millilitres of anhydrous alcohol. There is added to this
solution a solution of sodium ethylate containing 1%; mol
Example 46
of sodium. Thereafter there are added while stirring
and at a temperature of 30° C. 59 grams of B-ethyl
merc-apto-vinyl-thionophosphonic acid ethyl ester chlo
SC EH13
ride. The temperature is kept for further 2 hours and‘
30 grams of n-hexylrnercaptanv are dissolved in 100 cc.
of anhydrous alcohol. There is added at 30° C. a sodium
the mixture then is worked up as usual. ‘There are ob‘
tained 65 grains of the new ester as a light brown water
ethylate solution containing 1A mol of anhydrous sodium.
insoluble oil. Yield 83 percent of the theoretical.
At the same temperature and while stirring there are added
59 grams of ?-ethylmercapto-vinyl-thionophosphonic acid
ethylester chloride. The temperature is kept for 1 further
Example 51
hour and the mixture is worked up in the usual manner.
There are obtained 5 7 grams of the new ester as a colour 15
less water-insoluble oil, boiling at 104° C./ 0.01 mm. Hg.
Yield 73 percent of the theoretical.
Example 47
S
OCZH5
30 grams of thioglycol acid ethyl ester are dissolved
At 30° C. there
is added a solution of sodium ethylate containing Mt mol
of sodium. Thereafter there are added dropwise 59 grams
20 in 100 millilitres of anhydrous alcohol.
of [i-ethylmercapto-vinyl-thionophosphonic acid ethyl ester
chloride. The temperature is kept for 2 further hours
28 grams of a-methylmercapto-thioethyl ether (B.P.
50° C./l2 mm. Hg) are dissolved in 100 millilitres of
at 30° C. and the mixture is worked up in a usual manner.
anhydrous alcohol. There is added while stirring and at 25 There are obtained 60 grams of the new ester as a yellow
a temperature of 30° C. a solution of sodium ethylate
water-insoluble oil. Yield 76 percent of the theoretical.
containing 14 mol of anhydrous sodium. Thereafter are
The toxicity on rats orally is 500 mg./kg. LDso.
added while stirring at the same temperature 60 grams
of [3-ethyl-mercapto-vinyl-thionophosphonic acid-ethyl
ester chloride. The temperature is kept for 11/2 hours
30
Example 52
at 30° C. and the mixture worked up as usual. There
are obtained 74 percent of the new ester as a water-in
soluble light brown oil. Yield 98 percent of the theo—
retical. The toxicity on rats orally is 100 rug/kg. LD95. 35
Example 48
38 grams of p-chloro phenol mercaptan are dissolved
in 120 millilitres of anhydrous alcohol. Thereto is added
while stirring a solution of sodium ethylate containing %
40 mol of sodium. Thereafter there are added dropwise
while stirring. and at a temperature of 30° C. 60 grains
51 grams of dodecyl mercaptan are dissolved in 100
of ,B-ethylmercapto-vinyl-thionophosphonic acid ethyl
millilitres of anhydrous alcohol. There is added at 30°
ester chloride. The temperature is kept‘for further 2
C. a solution of sodium ethylate containing 14 mol of
hours at 30° C. and the mixture is then worked up inVa
anhydrous sodium. Thereafter there are added dropwise
at the same temperature 59 grains of ?-ethyhnercapto 45 usual manner. There are obtained 68 grams of the new
ester as a yellow water-insoluble oil. Yield 80 percent
vinyl~thiono~pl1osphonic acid ethyl ester chloride. The
of the theoretical.
temperature is kept for 1 further hour while stirring and
Example 53
the mixture is worked up in the usual manner. There are
obtained 85 grams of the new ester as a yellow water
insoluble oil. Yield 86 percent of the theoretical.
50
Example 49
S~CH—COOOZH5
6 grams of sodium powder are suspended into 100
At 50° C. there are added
55 millilitres of dry benzene.
while stirring 60 grams'of diethyl amino ethanol. After
em
about 2 hours of stirring at said temperature the sodium
has been converted into a corresponding alcoholate.
While stirring there are added 60 grams of B-ethyl trier;
34 grams of a-sulfhydryl propionic acid ethyl ester
(B.P. 48° C./ll mm. Hg) are dissolved in_ 100 milli
litres of anhydrous alcohol. There is-added while stir
capto‘ vinyl-thionophosphonic acid ethyl ester chloride.
ring and at a temperature of 30° C. a solution of sodium
After stirring for 1 further hour at 60° C. the mixture‘ is'
poured into 400 millilitres o-f ice-water. The oil which
precipitates ‘is taken up in'200 millilitres of benzene. The
ethylate containing 1%; mol of anhydrous sodium.’ There
after there are added at the same temperature 59 grams
of ,B-ethyl mercapto-vinyl-thionophosphonic acid ethyl
ester chloride. The temperature is kept for‘ 2 further
benzenic layer is dried over" anhydrous sodium sulphate
and the benzene'then is distilled off. There are obtained
50 grams of the new ester as a colourless‘water-insoluble
hours and the mixture is ‘worked up in the usual manner.
There are obtained 66 grams of the new ester as a yellow
oil which distils'at 0.0l‘mm. Hg at 1'l8°‘C. The‘yield is
64 percent of the theoretical. The toxicity on-rats‘orally
is 10 mg./kg. LD50.
water-insoluble oil; Yield 80% of-thetheoretic'ali The
toxicity on rats orally is 500 mg./kg. LD95.
Example 50
S
70
O G 2H5
CiHaS—-OH=OH—P
75
3,047,605
19
20
'43' grams of 3-chloro-4-nitrophenol are dissolved in
100 millilitres of anhydrous alcohol. To this solution
there is added while stirring a solution of sodium ethylate
6 grams of sodium powder are suspended in 100 milli
iltres of benzene. At 50° C. there are added 40 grams
of cyclohexanol. After stirring for 2 hours at 50° C. the
sodium has been converted into a corresponding alco
holate. Thereafter there are added while stirring and at
a temperature of 50° C. 60‘ grams of ,B-ethylrnercapto
‘ containing 1%; mol of sodium. Thereby the temperature
rises to 45° C. Thereafter there are added dropwise while
stirring at 50°C. 60 grams of B-ethyl mercapto-vinyl
thionophosphonic acid ethyl ester chloride. The temper
vinyl-thionophosphonic acid ethyl ester chloride. The
temperature is kept at 60° C. for 1 further hour and the
ature is kept at 50° C. for further 2 hours and then the
mixture is worked up in usual manner. There are ob
mixture is worked up then as described in the foregoing
example. There are obtained 42 grams of the new ester 10 tained 55' grams of the new ester as a water-insoluble yel
lowish-brown oil, which is kept at a temperature of 80°
as a pale yellow water-insoluble oil (B.P. 108° C./0.01
C. for a short period under vacuum of 0.01 mm. Yield
mm. Hg). Yield 57 percent of the theoretical.
60 percent of the theoretical.
Example 55
Example 59
15
39 grams of 4-methyl mercapto-3-methylphenol (M.P.
s
20
pension of 6 grams of sodium powder in 150 millilitres
of benzene.
After conversion of the sodium into a cor
28 grams of ?-ethylmercapto ethanol are dissolved in
150 millilitres of methyl ethyl ketone. To this solution
there are added while stirring 40‘ grams of dried and ?nely
divided potassium carbonate and 1 gram of copper pow
der. Thereafter while stirring there are added dropwise
at 80° C. 60 grams of ethyl marcapto-vinyl-thionophos~
59° C.) are dissolved in 70 millilitres of benzene. This
solution is added at 50° C. and while stirring to a sus
responding alcoholate there are added while stirring at
00,115
25
phonic acid ethyl ester chloride. The temperature is kept
at 80° C. while stirring for further 4 hours, then the re
action product is diluted with 500 millilitres of chloroform
and the resulting salts are ?ltered off with suction. The
60° C. 60 grams of ,B-ethyl mercapto-vinyl-thionophos
phonic acid ethyl ester chloride. The temperature is kept
for 1 further hour at 60° C. and the mixture then is
mixture is worked up in a usual manner. There are ob
worked up as described in the foregoing examples. There 30 tained 45 grams of the new ester as a yellow water-insol
are obtained 70 grams of water-insoluble yellow oil.
uble oil, which is kept shortly at a temperature of 60° C.
Yield 81 percent of the theoretical. The new ester is
and under vacuum of 0.01 mm. Yield 60 percent of the
undistillable even in high vacuum.
theoretical.
Example 56
Example 60
35
ISI 005115
0
001m
ll/
C2H5S—-OH=GH—P
C1H5S—OH=CH—P
S-CHz-COOGQHB
\ O-<3--SCH3
60 grams of ?-ethylmercapto-vinyl-thionophosphonic
, 35 grams of p-methylmercapto phenol (M.P. 87° C.) 40 acid ethyl ester chloride are dissolved in 120 millilitres
of anhydrous alcohol. While stirring there are added 20
are dissolved in 70 millilitres of benzene. This solution is
millilitres of water. The temperature rises to 70° C. Then
added While stirring to a suspension of 6 grams of sodi
there is added dropwise at 70° C. a solution of 29 grams
um powder in 100 millilitres of benzene at 60° C. After
of potassium hydroxide and 60 millilitres of water. The
reaction of the sodium there are added While stirring at
. temperature is kept for further 2 hours at 70° C. and
the same temperature 60 grams of ,B-ethylmercapto-vinyl
thereafter there are added 32 grams of monochloro acetic
thionophosphonic acid ethyl ester chloride. The tem
acid ethyl ester. The temperature is kept for 2 further
perature is kept for 1 further hour at 60° C. and the mix
ture is worked up as usual. The product obtained is
kept at a temperature of 80° C. under vacuum of 0.01
mm.
hours at 70° C. and the mixture is worked up as usual.
There are obtained 40 grams of the new ester as a yellow
water-insoluble oil (B.P. 108° C./0.01 mm. Hg). Yield
54 percent of the theoretical.
There are obtained 53 grams of a yellow water- .
insoluble oil. Yield 64 percent of the theoretical.
Example 61
Example 57
S
0
002E);
OCQHE
S-CHg—GHz-—SG1H5
60 grams of IS-ethyl mercapto-vinyl-thionophosphonic
acid ethyl ester chloride together with 120 millilitres of
anhydrous alcohol, 20 millilitres of water and a solution of
29 grams of potassium hydroxide in 60 millilitres of water
40 grams of the sodium salt of nitrophenol are dissolved
in 150 millilitres of ethyl methyl ketone. There are add
ed while stirring at 40° C. 60 grams of ,B-ethylrnercapto
vinyl-thionophosphonic acid ethyl ester chloride. The
temperature is kept for 1 further hour at 40° C. and the
are saponi?ed exactly as described in the foregoing exam
ple. After saponi?cation there are ‘added while stirring
at 70° C. 32 grams of B-chloroethyl thioethyl ether. The
temperature is ‘kept for 2 hours at 70° C. and the mixture
mixture then is worked up as usual. The raw product
obtained is distilled o? at 80° C. under a pressure of 0.01
mm.
is worked up in a usual manner. There are obtained 44
grams of the new ester as a light yellow water-insoluble
There are obtained 59 grams of the new ester as
a yellowish brown water-insoluble oil.
of the theoretical.
Yield 71 percent '
oil (B.P. 114° C./0.01 mm. Hg).
The new ester is undistillable even in
LD50.
Example 58
V
8
70
002115
Example 62 i
O OCgHg
C:H5S—CH=CH—P
Cl
Yield 59 percent of
the theoretical. The toxicity on rats orally is 10 mg./kg.
high vacuum.
El
8,047,605
22
60 grams of B-ethylmercapto-vinyl-thionophosphonic
and the product is then Worked up in usual manner. 50
grams of the new ester of B.P. 90° C./ 0.01 mm. Hg are
thus obtained. Yield: 74 percent of the theoretical. The
ester is sparingly water-soluble.
acid ethyl ester chloride are saponi?ed as described in
the foregoing examples. To the saponi?cation product
there are added 47 grams of a-bromopropionic acid ethyl
ester chloride. The temperature is kept at 70° C. for
ifurther 2 hours, and the mixture is worked up as usual.
Spider mites are completely killed by 0.01% solutions
of this ester.
There are obtained 32 grams of the new ester as a yellow
water-insoluble oil. The new ester is undistillable even
Example 67
s’ OCzHs
in high vacuum. The toxicity on rats orally is 50 mg./ kg.
LD95.
Example 63
10
6 grams of sodium powder are suspended in 50 milli
litres of benzene. 60 grams of diethylamino-ethanol are
added with stirring at 50° C. After the sodium is dis
solved, 55 grams of ,B-ethoxyvinyl-phosphonic acid ethyl
60 grams of B-ethylmercapto-vinyl-thionophosphonic
ester chloride (B.P. 60° C./‘0.0l mm. Hg) are added drop
wise with stirring. The mixture is after-stirred for an
hour and then worked up in usual manner. 64 grams of
acid ethyl ester chloride are saponi?ed as described in
the foregoing examples. To the saponitication product
there are added while stirring and at a temperature of
the new ester of B.P. 114° C./0.01 mm. Hg are thus ob
70° C. 35 grams of ,B-chloroethyl'diethylamine. The tem~ 20 tained. Yield: 86 percent of the theoretical.
perature is kept for further 2 hours at 70° C. and the
0.01% solutions of the ester have a marked ovicidal
mixture is worked up in usual manner. After lower boil
action on the ovae of red spiders.
ing impurities have been distilled off under reduced pres
sure- there are obtained 30 grams of the new ester as a
yellow water-insoluble oil. Yield 39 percent of the theo
retical. The toxicity on rats orally is 10 mg./kg. LDM.
25
Example 68
Sr OCzHb
CgH50.CH=CH—
Example 64
iL/
O.CHr.CH2-N(CHa):
30
60‘ grams of B-ethylmercapto-vinyl-thionophosphonic
6 grams of sodium powder are suspended in 100 milli
litres of benzene. 50 grams of dimethylamino-ethanol
are added with stirring at 50° C. The mixture is heated at
50° C. for a ‘further hour and 55 grams of B-ethoxyvinyh
thiono-phosphonic acid ethyl ester chloride are added at
acid ethyl ester chloride are saponi?ed as described in 35 this temperature. The reaction product is kept at 60° C.
for a further hour and then poured into 300 millilitres of
the aforegoing examples. To the saponi?cation product
water. The separated‘ oil is taken up with plenty of ben
there are added while stirring at 70° C. 40 grams of
zene, the benzenic layer is separated and dried.
a-chloromethyl thiophenylether. The temperature is kept
The
for further 2 hours at 70° C. and the mixture is worked 40 solvent is removed under vacuum. 32 grams of the new
ester are thus obtained. Yield: 49 percent of the theo
up as usual. The water-insoluble yellow raw product ob
retical.
tained is kept shortly under pressure of 0.01 mm. at a
Example 69
temperature of 80° C. There are obtained 49 grams of
the new ester. Yield 59 percent of the theoretical. The
toxicity on rats orally is 25 mg./kg. LD50.
Example 65
O
0 02115
6 grams of sodium powder are suspended in 100 milli
litres of benzene. 50 grams of diethylamino-ethanol are
added thereto with stirring at 50° C. The mixture is after
stirred at 50° C. for half an hour. The sodium dissolves.
53 grams of ?-ethoxyvinyl-thionophosphonic acid methyl
60 grams of ?-ethylmercapto-vinyl-thionophosphonic
ester chloride (B.P. 55° C./0.01 mm. Hg) are ‘then added
acidethyl ester chloride are saponi?ed as usual. To this
solution there are added dropwise while stirring and at
a temperature of‘7O‘80o C. 42 grams of p-chlorobenzyl
with stirring at the said temperature. The reaction prod
net is after-stirred for whom, then diluted with 300 milli
itres of benzene and poured into 300 millilitres of ice
water. The benzenic layer is separated, dried over sodium
sulphate and the ?ltrate is fractionated. 67 grams of the
chloride. The temperature is kept at 70° C. for further
2'hours and the mixture then is worked up as usual. The
raw product obtained is kept shortly under a pressure of
new ester of B.P. 80° C./0='.01 mm. Hg are thus obtained.
Yield 65 percent of the 60 Yield: 94 percent of the'theoretical.
0.01 mm. at a temperature of 75° C. There are obtained
55 grams of the new ester.
theoretical.
Example 70
Example 66
0
002E‘;
65
5 3 grams of ?-methoxyvinyl-thionophosphonic acid
83 grams of B-ethoxy-vinyl-phosphonic acid diethyl ester
(B.P. 70° C./0.01 mm. Hg) are reacted at 65° C. with
phosgene.
Reaction is carried out in such way that the
70
temperature is kept at 65 to 70° C. When the reaction
to and then a solution of 29 grams of potassium hydroxide
ethyl ester chloride are dissolved in 130 millilitres of an
hydrous alcohol. 30 millilitres of water are added there
in 60 millilitres of water. The mixture is kept at 75° C.
with stirring and 32 grams of ,d-chloroethyl thioethyl
ether are then added dropwise. The temperature is main
temperature no longer can be maintained by introducing
phosgene the reaction mixture is heated for 1 further hour
at 70° C. The reaction product is distilled in vacuum.
tained at 75 ° C. with further stirring for a further 3 hours 75 There are obtained 33 grams of the ester chloride distilling
3,047,605
24
23
I claim:
at 70° C./0:05 mm. Hg. Yield 45 percent of the theo-'
retical.
From the following table there is to be seen the activity
of some of the inventive compounds of the above shown
1. A phosphonic acid ester of the following formula
examples:
5
ZR:
OOMPOUN D
I
rat per 0s.-.
Example 17 _______ __ spider mites
LDos 50 mglkg.
0. 001%‘
40%
aphids. _ . _-
0. 01%
rat per os __
Example 18 ______ ._ spider m1tes._
aphids ______ ..
0. 1%
rat per 05...
Example 19 _______ ..
100%
LDos 100 mg /kg.
caterpillars ______ __
0. 1%
aphids (syst. act.)
rat per 05.....
Example 20 _______ __
100%
LDm 50 mg /kg.
10
0.1%
100%
00%
0.1%
100%
LDM 25 mg /kg.
'
%
100%
'
Example 21
spider mites
0. 01%
?ies _______________________ __
I
Example 22 ....... ._
,
. 001%
00%
100%
rat per os._
LD50 50 mg /kg.
?ies ____________ ._
0. 001%
aphids (syst act)
[rat per os ....... _.
laphids (syst
ct )
Example 24 _______ __
Example 25 _______ __
100%
0.1%
LD95
Example 23 _______ __ spider mites ____ _.
'
15
50%
100%
0 mgz/lrg.
0. 1%‘
0. 1%
20
100%
100%
LDw 1,000 rug/kg.
0. 1%‘
0%
0. 1%
0%
LDao 10 mg /kg.
‘
0 01%
100% 25
0. 01%
100%
LD50 250 mg /kg.
Example 26 _______ __
0 1%
0. 01%
100%
0. 01%
100%
0. 01%
100%
0.1%
100%
0.
a
100 0
Example 31 ....... .. {
O. 8:11;?
001%
100%
Example 32 _______ __ {
O_
.
LDso 50 mg /kg.
Example 28 _______ __
rat per os___._
Example 29 _______ __
aphiids (sytrst. act.)
sp1 er mi es ____ __
Example 30 """" " {caterpillars_____
0.00
0.1%
50%
100%
0.0.11%,0
100/0
aphids ____ __
0.1%
0.1%
0. 01g)
Example "5 """" " lspildeir mites.
0.156
.
,
ap
i
s ______ ._
ap 11 s ____ __
Exampl“ 55 ------- -- {?ies ..... -_
Example 56 _______ -- rat per os
rat per 0
Example 57 _______ __
10. A phosphonic acid ester of the following formula:
40
100379
100% 45
50g,
0.01 c
100 0
0.1 0
100%
100%
0. 01%
50%
LD50 10 mg. kg.
LDm 25 mg./ ‘g.
aphids__
0.01%
spider mites.
Example 58 _______ ._
0 50
0. 01%
50%
LDm 500 rug/kg.
0.1%
100%
0. 01%
70%
LD50 100 mg/kg.
Example 59 _______ __
0.1%
0. 01%
100%
100% 5 5
LDlM 100 mgJkg.
0.1%‘
100%
Example 60 _______ __
0. 1%
100%
0. 01%‘
100%
L 50 10 mgjkg.
Example 61 ....... ._
e
. 01%
75%
LDos 50 mg [kg.
0.1%‘
0% 6O
0. 1%
100%
Example 62 _______ __
0
CR1
OR:
100%
LLD-n 250 mg ,‘kg.
spildeir mites.
,..
9. A phosphonic acid ester of claim 1 wherein X and
Z are oxygen and Y is sulfur.
100
0. 01%
0.1%
Example 52 _______ __
7. A phosphonic acid ester of claim 1 wherein X is
8. A phosphonic acid ester of claim 1 wherein X and
Y are oxygen and Z is sulfur.
11'
Example 49 """" " lcaterpillars.
rat per os__
6. A phosphonic acid ester of claim 1 wherein X is
oxygen.
100% 35
1005;
_ eatercpiuars
apii s____
30
oxygen and Y and Z are sulfur.
0. 01%2
069%;
Example 51 ------- -- {caterpillars
5. A phosphonic acid ester of claim 1 wherein X and
Y are sulfur and Z is oxygen.
1005/;
Example 44 """"" " i h_d
Example 45 _______ __ { p l
Example "10
stand for a chalcogen which has an atomic weight from
16 to 33, at least one of the chalcogens Y and Z being
sulfur.
2. A phosphonic acid ester of claim 1 wherein X is
sulfur.
'3. A phosphonic acid ester of claim 1 wherein X, Y
4. A phosphonic acid ester of claim 1 wherein X and
90%
.
chlorophenyl mercapto substituted lower alkyl, cyclo
hexyl, phenyl, chloro substituted phenyl, nitro substituted
phenyl, lower alkyl mercapto substituted phenyl, lower
alkyl substituted phenyl, and chromanyl, and X, Y and Z
Z are sulfur and Y is oxygen.
LDQi 500 n1g./kg.
spider mites ____ _.
lower carbalkoxy" substituted lower alkyl, cyano sub
stituted lower alkyl, chlorine substituted lower alkyl,
phenyl substituted lower alkyl, chlorophenyl substituted
lower alkyl, phenyl mercapto substituted lower alkyl,
and Z are sulfur.
100%
0. 1%
100%,
LDao 2.5 mg /kg.
0. 001%|
00%
Example 27 _______ _.
in which R and R1 stand for lower alkyl radicals up to 4
carbon atoms, R2 stands for a member selected from the
group consisting of lower alkyl mercapto substituted
lower alkyl, lower dialkyl amino substituted lower alkyl,
in which R and R1 stand for lower alkyl radicals up to 4
carbon atoms, R2 stands for a member selected from the
group consisting of lower alkyl mercapto substituted lower
alkyl, lower dialkyl amino substituted lower alkyl, lower
carbalkoxy substituted lower alkyl, cyano substituted
lower alkyl, chlorine substituted lower alkyl, phenyl sub
stituted lower alkyl, chlorophenyl substituted lower alkyl,
phenyl mercapto substituted, lower alkyl, chlorophenyl
mercapto substituted lower alkyl, cyclohexyl, phenyl,
chloro substituted phenyl, nitro substituted phenyl, lower
alkyl mercapto substituted phenyl, lower alkyl substituted
phenyl, and chromanyl; and X is a chalcogen having an
atomic weight from 16 to 33.
11. A phosphonic acid ester of claim 10 wherein X is
sulfur.
References Cited in the ?le of this patent
LDso 10 mg /k .
Example 63 _______ __
p
0.01%
100%
0. 1%
100%
LDM, 500 mg [kg.
Example 65 _______ __
p
_
spider mites _______________ ._
0. 1%
.0l%
100%
60% 65
Anisimov et
Anisimov et
Anisimov et
Anisimov et
Anisimov et
al.:
al.:
al.:
al.:
al.:
Chem. Abst., 50, 32/17 (1956).
Chem. Abst., 50, 6297 (1956).
Chem. Abst., 50, 7077 (1956).
Chem. Abst., 50, 9319 (1956).
Chem. Abst., 50, 13,784-5 (1956).
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