US2913367A - Some phosphorus containing derivatives of alkyl acetothiolacetate - Google Patents
Some phosphorus containing derivatives of alkyl acetothiolacetate Download PDFInfo
- Publication number
- US2913367A US2913367A US570644A US57064456A US2913367A US 2913367 A US2913367 A US 2913367A US 570644 A US570644 A US 570644A US 57064456 A US57064456 A US 57064456A US 2913367 A US2913367 A US 2913367A
- Authority
- US
- United States
- Prior art keywords
- carbonyl
- alkyl
- acetothiolacetate
- methylvinyl
- ethylthio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 125000000217 alkyl group Chemical group 0.000 title description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title description 3
- 229910052698 phosphorus Inorganic materials 0.000 title description 3
- 239000011574 phosphorus Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 21
- -1 e.g. Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 241000238631 Hexapoda Species 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 7
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005949 Malathion Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- JXSJBGJIGXNWCI-UHFFFAOYSA-N diethyl 2-[(dimethoxyphosphorothioyl)thio]succinate Chemical compound CCOC(=O)CC(SP(=S)(OC)OC)C(=O)OCC JXSJBGJIGXNWCI-UHFFFAOYSA-N 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229960000453 malathion Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Chemical group 0.000 description 2
- 239000011593 sulfur Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001674044 Blattodea Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 1
- QFNCJANBIZSTDM-UHFFFAOYSA-N [chloro(ethoxy)phosphoryl]benzene Chemical compound CCOP(Cl)(=O)C1=CC=CC=C1 QFNCJANBIZSTDM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical class OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 description 1
- FVIHUXZNJJCGPC-UHFFFAOYSA-N chloro-ethoxy-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)C1=CC=CC=C1 FVIHUXZNJJCGPC-UHFFFAOYSA-N 0.000 description 1
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 1
- NAKDJXIEBCHXIZ-UHFFFAOYSA-N dihydroxy-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(=S)C1=CC=CC=C1 NAKDJXIEBCHXIZ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100001225 mammalian toxicity Toxicity 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4078—Esters with unsaturated acyclic alcohols
Definitions
- This invention relates to new phosphorus-containing derivatives of alkyl acetothiolacetates, the process of manufacturing those compounds, and the use of the compounds as insecticides.
- R is alkyl group containing not more than 6 carbon atoms
- R" is an alkyl group containing not more than 10 carbon atoms
- X is oxygen or sulfur.
- the present invention also includes a process for the manufacture of the above compounds.
- 'We react an alkyl acetothiolacetate, e.g. ethyl acetothiolacetate I clzt -co-onri lsozm with a dialkyl phosphorohalidate, e.g. diethyl phosphorochloridate T QgHrO-P Cl OCaHs a dialkyl phosphorohalidothioate, e.g. 0,0-diethyl phosphorochloridothioate an alkyl arylphosphonohalidate, e. g.
- the reaction is carried out in the presence of an amine-type HCl acceptor, preferably triethylamine.
- an alkali metal derivative of the proper acetothiolacetate may be reacted with the proper dialkyl phosphorohalidate, dialkyl phosphorohalidothioate, alkyl arylphosphonohalidate, or alkyl arylphosphonohalidothioate.
- reaction is preferably conducted in an anhydrous inert solvent, e.g., benzene, xylene, hexane,
- the preferred halidates and halidothioates for the introduction of the phosphorous-containing radical are the chloridates and chloridothioates, respectively.
- Examples of preferred reagents of these classes are as follows:
- EXAMPLE II A 1% acetone solution of 0,0-diethyl O-[Z-(ethylthio) carbonyl-l-methylvinyl]phosphorothioate was prepared. One milliliter was placed in a one liter bottle and the acetone allowed to evaporate. In another bottle was placed one milliter of a 1% solution of malathion, from.
- the other compounds of our group may be prepared in the same manner (substituting the proper reagents), and used in the same manner, as the compound prepared and used in Examples 1 and 2.
- Numerous other solvents e.g. low-boiling hydrocarbons or water may be employed instead of acetone, and the compounds may also be employed in dusting powders and other insecticidal compositions.
- a compound of the formula X 0 T ll RPOC CH-CSR" R being selected from the class consisting of aryl groups containing from 6 to 9 carbon atoms and alkoxy groups containing not more than 6 carbon atoms, R is an alkyl group containing not more than 6 carbon atoms, R is an alkyl group containing not more than ten carbon atoms, and X is selected from the class consisting of sulphur and oxygen.
- a method of killing insects which comprises contacting them with a compound as defined in claim 1.
- a method of killing insects which comprises contacting them with a compound as defined in claim 2.
- a process of killing insects which comprises contacting them with a compound as defined in claim 3.
- a method of killing insects which comprises contacting them with a compound as defined in claim 4.
- a method of killing insects which comprises contacting them with a compound as defined in claim 5.
- a method of killing insects which comprises contacting them with a compound as defined in claim 6.
- a method of killing insects which comprises contacting them with a compound as defined inv claim 7.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
SOME PHOSPHORUS CONTAINING DERIVATIVES OF ALKYL ACETOTHIOLACETATE Thomas P. Dawson, Bel Air, Md., Elwyn R. Lovejoy,
Wilmington, Del., and Charles E. Williamson, Edgewood, and Benjamin Witten, Baltimore, Md.
No Drawing. Application March 9, 1956 Serial No. 570,644
14 Claims. (Cl. 167-22) (Granted under Title 35, US. Code (1952), see. 266) The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment to us of any royalty thereon.
This invention relates to new phosphorus-containing derivatives of alkyl acetothiolacetates, the process of manufacturing those compounds, and the use of the compounds as insecticides.
.More particularly it relates to O-[2-(alkylthio) carbonyl-l-methylvinyl] 0,0-dialkyl phosphates, O-[2-(alkylthio carbonyl-l-methylvinyl] 0,0-dialkyl phosphorothioates, O-[2-(alkylthio)carbonyl 1 methylvinyHO-alkyl i arylphosphonates and O-[2-(alkylthio)carbonyl-l-methylvinyl] O-alkyl arylphosphonothioates.
Our compounds may be represented by the following general formula 1 v 1 vitwi --o -o=oH ":sR"
a R CH3 'wherelR is anaryl'group containing 6 to 9 carbon atoms or an alkoxy-group containing not more than 6 carbon i .1
atoms,- R is alkyl group containing not more than 6 carbon atoms, R" is an alkyl group containing not more than 10 carbon atoms, and X is oxygen or sulfur.
These compounds are highly effective insecticides.
They combine extremely high toxicity toward insects with low mammalian toxicity.
The present invention also includes a process for the manufacture of the above compounds. 'We react an alkyl acetothiolacetate, e.g. ethyl acetothiolacetate I clzt -co-onri lsozm with a dialkyl phosphorohalidate, e.g. diethyl phosphorochloridate T QgHrO-P Cl OCaHs a dialkyl phosphorohalidothioate, e.g. 0,0-diethyl phosphorochloridothioate an alkyl arylphosphonohalidate, e. g. ethyl phenylphosphonochloridate 0 T 1|Cl or an alkyl arylphosphonohalidothiate, e.g., O-ethyl phenylphosphonochloridothioate 2,913,367 Patented Nov. 17, 1959 depending whether R is alkoxy or aryl and whether X is oxygen or sulfur. The reaction is carried out in the presence of an amine-type HCl acceptor, preferably triethylamine.
Alternatively, an alkali metal derivative of the proper acetothiolacetate may be reacted with the proper dialkyl phosphorohalidate, dialkyl phosphorohalidothioate, alkyl arylphosphonohalidate, or alkyl arylphosphonohalidothioate.
In either case the reaction is preferably conducted in an anhydrous inert solvent, e.g., benzene, xylene, hexane,
or other low-boiling hydrocarbon or hydrocarbon fraction.
The preferred halidates and halidothioates for the introduction of the phosphorous-containing radical are the chloridates and chloridothioates, respectively. Examples of preferred reagents of these classes are as follows:
(A) Dialkyl phosphorochloridates:
Examples of preferred alkyl acetothiolacetates are:
Methyl acetothiolacetate Ethyl acetothiolacetate n-Propyl acetothiolacetate I Isopropyl acetothiolacetate n-Butyl acetothiolacetate The following is a representative example of the production of our compounds:
EXAMPLE I 0,0-diethyl O-[Z-(ethylthio)carbonyl-1 -methylvinyll v phosphorothioate 0,0-diethyl phosphorochloridothioate (9.4 g., 0.05 M), and ethyl acetothiolacetate (7.3 g., 0.05 M), and triethylamine (10 g., 0.1 M) were dissolved in ml. of benzene and the mixture was refluxed for one hour. It was removed and washed with water (4X50 ml.), and then the solvent was removed by distillation at reduced pressure. A yield of 7.2 g. (=48.3%) of product remained.
Other particularly preferred compounds of our inven tion that may be prepared by the same general method, utilizing the proper reactants are:
0,0-diethyl O-[2-(rnethylthio)carbonyl 1 methylvinyl] phosphorothioate O ethyl O [2 (ethylthio)carbonyl 1 methylvinyl] phenylphosphonothioate O ethyl 0 [2 (methylthio)carbonyl -1 methylvinyl] phenylphosphonothioate 0,0 diethyl O [2 (ethylthio)carbonyl l methylvinl] phosphate 0,0 diethyl O [2 (methylthio)carbonyl 1 methylvinyl] phosphate ethyl O [2 (ethylthio)carbonyl 1 methylvinyl] phenylphosphonate O ethyl O [2 (methylthio) carbonyl 1 methylvinyl] phenylphosphonate 0,0 dimethyl O [2 (ethylthio)carbonyl 1 methylvinyll phosphorothioate O methyl 0 [2 (ethylthio)carhonyl 1 methylvinyl] phenylphosphonothioate O methyl 0 [2 (methylthio)carbonyl 1 methylvinyllphenylphosphonothioate 0,0 dimethyl O [2 (ethylthio)carbonyl l methylvinyl] phosphate 0,0 dimethyl O [2 (methylthio)carbonyl 1 methylvinyl 1 phosphate 0 methyl 0 [2 (ethylthio)carbonyl 1 methylvinyl] phenylphosphonate 0 methyl 0 [2 (methylthio)carbonyl 1 methylvinyl] phenylphosphonate These particularly preferred compounds are those in which, referring to the general formula, R is methoxy, ethoxy or phenyl, R is methyl or ethyl, and R is methyl or ethyl.
The following example illustrates the insecticidal properties of one of our preferred compounds.
EXAMPLE II A 1% acetone solution of 0,0-diethyl O-[Z-(ethylthio) carbonyl-l-methylvinyl]phosphorothioate was prepared. One milliliter was placed in a one liter bottle and the acetone allowed to evaporate. In another bottle was placed one milliter of a 1% solution of malathion, from.
which the acetone was also allowed to evaporate. The same number of the same variety of cockroaches were then placed in each bottle and timed to death. Those in the bottle containing the phosphorothioate died considerably more quickly than those in the bottle containing malathion.
The other compounds of our group may be prepared in the same manner (substituting the proper reagents), and used in the same manner, as the compound prepared and used in Examples 1 and 2. Numerous other solvents, e.g. low-boiling hydrocarbons or water may be employed instead of acetone, and the compounds may also be employed in dusting powders and other insecticidal compositions.
We claim: 1. A compound of the formula X 0 T ll RPOC=CH-CSR" R being selected from the class consisting of aryl groups containing from 6 to 9 carbon atoms and alkoxy groups containing not more than 6 carbon atoms, R is an alkyl group containing not more than 6 carbon atoms, R is an alkyl group containing not more than ten carbon atoms, and X is selected from the class consisting of sulphur and oxygen.
2. 0,0 diethyl O [2 (ethylthio)carbonyl 1- methlvinyl] phosphorothioate.
3. 0,0 diethyl O [2 (ethylthio)carbonyl 1- methylvinyl phosphate.
4. 0,0 dimethyl O [2 (ethylthio)carbonyl lmethylvinyl]phosphorothioate.
5. 0,0 dimethyl O [2 (ethylthio)carbonyl 1- methylvinyllphosphate.
6. 0,0 dimethyl 0 [2 methylvinyl] phosphorothioate.
7. 0,0 dimethyl 0 [2 (methylthio)carbonyl 1- methyl vinyl] phosphate.
8. A method of killing insects which comprises contacting them with a compound as defined in claim 1.
9. A method of killing insects which comprises contacting them with a compound as defined in claim 2.
10. A process of killing insects which comprises contacting them with a compound as defined in claim 3.
11. A method of killing insects which comprises contacting them with a compound as defined in claim 4.
12. A method of killing insects which comprises contacting them with a compound as defined in claim 5.
13. A method of killing insects which comprises contacting them with a compound as defined in claim 6.
14. A method of killing insects which comprises contacting them with a compound as defined inv claim 7.
(methylthio)carbonyl 1- References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES BIOS Final Report 714 (revised) (RB. 87, 923 R), p. 53 (1948).
Pudovik et al.:
Doklay Nauk S.S.S.R., vol. 105, pp. 735-7 (1955).
Claims (1)
1. A COMPOUND OF THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US570644A US2913367A (en) | 1956-03-09 | 1956-03-09 | Some phosphorus containing derivatives of alkyl acetothiolacetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US570644A US2913367A (en) | 1956-03-09 | 1956-03-09 | Some phosphorus containing derivatives of alkyl acetothiolacetate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2913367A true US2913367A (en) | 1959-11-17 |
Family
ID=24280473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US570644A Expired - Lifetime US2913367A (en) | 1956-03-09 | 1956-03-09 | Some phosphorus containing derivatives of alkyl acetothiolacetate |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2913367A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3053729A (en) * | 1959-10-26 | 1962-09-11 | Shell Oil Co | Insecticidal compositions |
| US3081220A (en) * | 1960-05-23 | 1963-03-12 | Shell Oil Co | Fungicidal process |
| US3093536A (en) * | 1961-04-05 | 1963-06-11 | Shell Oil Co | Stabilized halogenated enol ester pesticidal compositions |
| US3097128A (en) * | 1961-01-06 | 1963-07-09 | Shell Oil Co | Phenol stabilized organo-phosphorous insecticides |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2226420A (en) * | 1939-10-03 | 1940-12-24 | Socony Vacuum Oil Co Inc | Extreme pressure lubricant |
| AT167432B (en) * | 1946-10-12 | 1951-01-10 | Bertha Braendli-Schafroth | Pesticides |
| US2596076A (en) * | 1948-03-26 | 1952-05-06 | American Cyanamid Co | Dithiophosphate esters as insecticides |
| US2668828A (en) * | 1953-04-21 | 1954-02-09 | Dow Chemical Co | S, s-bis(ethylxanthoyl) o-ethyl trithiophosphate |
| US2685552A (en) * | 1952-02-29 | 1954-08-03 | Shell Dev | Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate |
-
1956
- 1956-03-09 US US570644A patent/US2913367A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2226420A (en) * | 1939-10-03 | 1940-12-24 | Socony Vacuum Oil Co Inc | Extreme pressure lubricant |
| AT167432B (en) * | 1946-10-12 | 1951-01-10 | Bertha Braendli-Schafroth | Pesticides |
| US2596076A (en) * | 1948-03-26 | 1952-05-06 | American Cyanamid Co | Dithiophosphate esters as insecticides |
| US2685552A (en) * | 1952-02-29 | 1954-08-03 | Shell Dev | Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate |
| US2668828A (en) * | 1953-04-21 | 1954-02-09 | Dow Chemical Co | S, s-bis(ethylxanthoyl) o-ethyl trithiophosphate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3053729A (en) * | 1959-10-26 | 1962-09-11 | Shell Oil Co | Insecticidal compositions |
| US3081220A (en) * | 1960-05-23 | 1963-03-12 | Shell Oil Co | Fungicidal process |
| US3097128A (en) * | 1961-01-06 | 1963-07-09 | Shell Oil Co | Phenol stabilized organo-phosphorous insecticides |
| US3093536A (en) * | 1961-04-05 | 1963-06-11 | Shell Oil Co | Stabilized halogenated enol ester pesticidal compositions |
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