US3081330A - Thionophosphinic acid esters and process for their production - Google Patents
Thionophosphinic acid esters and process for their production Download PDFInfo
- Publication number
- US3081330A US3081330A US44537A US4453760A US3081330A US 3081330 A US3081330 A US 3081330A US 44537 A US44537 A US 44537A US 4453760 A US4453760 A US 4453760A US 3081330 A US3081330 A US 3081330A
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- United States
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- aryl
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- acid esters
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- Expired - Lifetime
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- 150000002148 esters Chemical class 0.000 title description 8
- 239000002253 acid Substances 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 3
- 238000000034 method Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 15
- -1 substituted alkyl radical Chemical class 0.000 description 19
- 239000000243 solution Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 7
- 241001454295 Tetranychidae Species 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- 235000019256 formaldehyde Nutrition 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 2
- 244000178937 Brassica oleracea var. capitata Species 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- KNIUHBNRWZGIQQ-UHFFFAOYSA-N 7-diethoxyphosphinothioyloxy-4-methylchromen-2-one Chemical compound CC1=CC(=O)OC2=CC(OP(=S)(OCC)OCC)=CC=C21 KNIUHBNRWZGIQQ-UHFFFAOYSA-N 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241000500437 Plutella xylostella Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
Definitions
- the present invention relates to and has as its objects new and useful insecticidal thiophosphinic acid esters and processes for their production.
- the new compounds of this invention may be represented by the following general formula R1 Aryl-P OR in which Aryl stands for an arylradical, R for an arbitrarily substituted alkyl radical and R for preferably low molecular weight alkyl radicals.
- aryl-thiolphosphonites of the following constitution (11) Aryl- P I (II) SH can be, easily obtained in known manner 'with hydrogen sulfide. These aryl-thiophosphonites react with alkali with the formation of the isomeric compounds of the following constitution (III) R s H Alkali ll Aryl-P Aryl-P V (II) p (III) 2 .
- the symbols have the same significance as given in the above said first formula.
- radical R may be a lower alkyl radiice
- white cabbage has been sprayed drip wet with aqueous emulsions as prepared above in a concentration as shown below. Caterpillars (10 each) have been placed on the sprayed leaves of the white cabbage. The living status has been determined after 24 and 48 hours. The following results have been obtained:
- Aqueous concentration in Killing rate Compound percent; active (in percent) ingredient/ water (I)--. (II) 0.1 100
- a sodium ethylate solution containing 0.25 mol of dissolved sodium is added thereto at 20 C. while stirring.
- 32 grams of chloro-acetic acid ethyl ester are added dropwis'e at 40 C.
- the mixture is further heated to 60 C. for an hour and then worked up as described in Example 1.
- 52 grams of the new ester of RP. 78 C./0.0l mm. Hg are thus obtained as a water-insoluble colorless oil. Yield: 76% of the theoretical. Spider mites are killed completely with 0.1% solutions.
- Example 5 47 grams (0.25 mol) of phenyl-ethyl-thiolphosphonite are dissolved in 50 ml. of methanol. A sodium methylate solution containing 0.25 mol of dissolved sodium is added thereto at 20 C. Subsequently 46 grams of OL-bI'OlIlO- propionic acid ethyl ester are added dropwise at 40 C. while stirring is continued. The mixture is heated to 60 C. for another hour and then worked up as described in Example 1. 35 grams of the new ester of BF. 78 C./0.0l mm. Hg are thus obtained as a colorless water-insoluble oil. Yield: 49% of the theoretical.
- R is a lower alkyl radical and R is a lower alkyl radical W OR having up to 4 carbon atoms.
- aryl is chloro-substituted phenyl
- R is a lower 5 R fe enc s Cited in the fil f i patent alkylene radical having up to 4 carbon atoms, R;, 1s a Kamai et a1: Zhun Obshchei Khim, 28, 939 941 lower alkyl radical and R is a lower alkyl radical having (1958) cited in Chem Abs 52 17162 (1958) up to 4 carbon atoms.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States-Patent O h 3,081,330 THIONOPHOSPHINIC ACID STERS AND PROCESS FOR THEIR PRODUCTION Gerhard Schrader, Wuppertal-C'ronenberg, Germany, as-
signor to Farbenfabriken Bayer Aktiengesellschaft,
Leverkusen, Germany, a corporation of Germany No Drawing. Filed July 22, 1960, Ser. No. 44,537 Claims priority, application Germany Aug. 21, 1959 5 Claims. (Cl. 260-461) The present invention relates to and has as its objects new and useful insecticidal thiophosphinic acid esters and processes for their production. Generally the new compounds of this invention may be represented by the following general formula R1 Aryl-P OR in which Aryl stands for an arylradical, R for an arbitrarily substituted alkyl radical and R for preferably low molecular weight alkyl radicals.
Ester chlorides of arylphosphonous acids having the following constitution (I) V Aryl-P 01 are known in the literature. H
From these ester chlorides, aryl-thiolphosphonites of the following constitution (11) Aryl- P I (II) SH can be, easily obtained in known manner 'with hydrogen sulfide. These aryl-thiophosphonites react with alkali with the formation of the isomeric compounds of the following constitution (III) R s H Alkali ll Aryl-P Aryl-P V (II) p (III) 2 .In the foregoing formulae the symbols have the same significance as given in the above said first formula.
In accordance with the present invention it has now been found that the aforementioned 'aryl thiolphosphonites, when reacted with alkyl halides in the presence of acid-binding agents, easily form aryl-alkyl-thionophosphinic acid esters of the following general formulae:
R MRI- l Aryl-P SH OR In this reaction scheme the symbols again have the same significance as given in the above said first formula.
More specifically the radical R may be a lower alkyl radiice As examples for the special utility of the inventive compounds the esters of the following formulae ii CH2CHz-SC2H5 021150 on. i -cn-co-oonn cirno on:
have been tested against spider mites, flies and caterpillars. Aqueous solutions of the aforementioned compounds have been prepared by admixing them with the same amount of an auxiliary solvent (acetone). A commercial emulsifier (benZyl hydroxy diphenyl polyglycol ether) is added in an amount of 20% referred to active ingredient. This premixture then is diluted with water to the desired concentration. The tests have been carried out as follows:
(a) Against spider mites (contact-insecticidal action): bean plants (Phaseolus vulgaris) of about 15 inches height were sprayed drip wet with solutions as prepared above in a concentration as shown below. The bean plants have been infested heavily with the two-spotted spider (species Tetranychus telarius). Evaluation has been carried out after 24 hours, 48 hours and 8 days. -The following results have been obtained:
Aqueous concentration (in Killing rate Compound percent active (in percent) ingredient/ water (I) v e Aqueous concentration (in Killing rate Compound percent active (in percent) ingredient] water (I)--. (I1) O. 001 100 (c) Against caterpillars of the type diamond black moth (Plutella maculipennis): white cabbage has been sprayed drip wet with aqueous emulsions as prepared above in a concentration as shown below. Caterpillars (10 each) have been placed on the sprayed leaves of the white cabbage. The living status has been determined after 24 and 48 hours. The following results have been obtained:
Aqueous concentration (in Killing rate Compound percent; active (in percent) ingredient/ water (I)--. (II) 0.1 100 The following examples are given for the purpose of illustrating the present invention.
3 Example 1 @t l CH2-CH2SCzH CzHgO 47 grams (0.25 mol) of phenyl-ethyl-thiolphosphonite (BJP. 105 C./l mm. Hg.) are dissolved in 50 ml. of anhydrous alcohol. A sodium ethylate solution containing 0.25 mol of dissolved sodium is added thereto while stirring. Subsequently 32 grams of fi-chloroethyl-thioethyl ether are added at 75 C. while stirring is continued. The mixture is further heated to 80 C. for an hour, then cooled to room temperature and the reaction product is poured into 300 ml. of icewater. The precipitated oil is taken up with 200 ml. of benzene, washed with water until neutral and then dried over sodium sulfate. Upon fractionating 41 grams of the new ester of RP. 82 C./ 0.01 mm. Hg are obtained as a water-insoluble colorless oil. Yield: 60% of the theoretical. Caterpillars are killed completely with 0.1% solutions. Systematic action on spider mites with 0.1% solutions=100%.
Calculated for mol 274: S, 23.2%; -P, 11.3%. Found: S, 22.5%; P, 10.86%.
By exactly the same way there may be obtained the following compounds:
P-CHPCH -SCgHg CH3 Example 2 CzHgO 47 grams (0.25 mol) of phenyl-ethyl-thiolphosphonite are dissolved in 50 ml. of anhydrous alcohol. A sodium ethylate solution containing 0.25 mol of dissolved sodium is added thereto at 20 C. Subsequently 28 grams of achloro-methyl-thioethyl ether are added dropwise while stirring is continued. The mixture is heated to 60 C. for an hour and worked up as described in Example '1. 33 grams of the new ester of B.P. 76 C./0.01 mm. Hg are thus obtained as a colorless water-insoluble oil. Yield: 51% of the theoretical. Aphids and spider mites are killed completely with 0.01% solutions. Systemic action on spider mites with 0.1% solutions=100%.
By the same way there may be obtained the compounds of the following formulae:
CgHsO Example 3 CzHaO 47 grams (0.25 mol) of phenyl-ethyl-thiolphosphonite are dissolved in 50 ml. of anhydrous alcohol. A sodium ethylate solution containing 0.25 mol of dissolved sodium is added thereto at 20 ,C. While stirring. Subsequently 46 grams of B-chloro-propionic acid ethyl ester are added dropwise at 50 C. while stirring is continued. The mixbe obtained the following Example 4 CzHsO 47 grams (0.25 mol) of phenyl-ethyl-thiolphosphonite are dissolved in 50 ml. of anhydrous alcohol. A sodium ethylate solution containing 0.25 mol of dissolved sodium is added thereto at 20 C. while stirring. Subsequently 32 grams of chloro-acetic acid ethyl ester are added dropwis'e at 40 C. The mixture is further heated to 60 C. for an hour and then worked up as described in Example 1. 52 grams of the new ester of RP. 78 C./0.0l mm. Hg are thus obtained as a water-insoluble colorless oil. Yield: 76% of the theoretical. Spider mites are killed completely with 0.1% solutions.
Calculated for mol 272: S, 11.8%; P, 11.4%. Found: S, 11.7%; P, 11.3%.
Example 5 47 grams (0.25 mol) of phenyl-ethyl-thiolphosphonite are dissolved in 50 ml. of methanol. A sodium methylate solution containing 0.25 mol of dissolved sodium is added thereto at 20 C. Subsequently 46 grams of OL-bI'OlIlO- propionic acid ethyl ester are added dropwise at 40 C. while stirring is continued. The mixture is heated to 60 C. for another hour and then worked up as described in Example 1. 35 grams of the new ester of BF. 78 C./0.0l mm. Hg are thus obtained as a colorless water-insoluble oil. Yield: 49% of the theoretical.
Calculated for mol 286: S, 11.2%; P, 10.9%. Found: S, 12.1%; P, 11.7%.
I claim:
1. The compound of the following formula 2. The compound of the following formula 3. A compound of the following formula s Rg-SR3 Aryl-i wherein aryl is phenyl, R is a lower alkylene radical having up to 4 carbon atoms, R;, is a lower alkyl radical and R is a lower alkyl radical having up to 4 carbon atoms.
5 a 6 4. A compound of the following formula wherein aryl is lower alkyl-substituted phenyl, R is a s Rg-S-Ra lower alkylene radical having up to 4 carbon atoms, R
is a lower alkyl radical and R is a lower alkyl radical W OR having up to 4 carbon atoms. wherein aryl is chloro-substituted phenyl, R is a lower 5 R fe enc s Cited in the fil f i patent alkylene radical having up to 4 carbon atoms, R;, 1s a Kamai et a1: Zhun Obshchei Khim, 28, 939 941 lower alkyl radical and R is a lower alkyl radical having (1958) cited in Chem Abs 52 17162 (1958) up to 4 carbon atoms. P
udov1k et al.. Bull. Acad. Sci. U.S.S.R. D1v. Chem. 5. A compound of the following formula 10 Sci" English translation, 1952 802F806- fi/Bz-S-Ra Aryl-I
Claims (1)
- 3. A COMPOUND OF THE FOLLOWING FORMULA
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF29221A DE1115248B (en) | 1959-08-21 | 1959-08-21 | Process for the preparation of arylthionophosphinic acid-O-alkyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3081330A true US3081330A (en) | 1963-03-12 |
Family
ID=7093209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US44537A Expired - Lifetime US3081330A (en) | 1959-08-21 | 1960-07-22 | Thionophosphinic acid esters and process for their production |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3081330A (en) |
| BE (1) | BE594249A (en) |
| CH (1) | CH388956A (en) |
| DE (1) | DE1115248B (en) |
| GB (1) | GB879021A (en) |
| NL (2) | NL255650A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3376365A (en) * | 1964-12-28 | 1968-04-02 | Mobil Oil Corp | Phosphinothioate ester |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE23979E (en) * | 1948-05-10 | 1955-04-12 | Lubricant composition containing dialkyl | |
| BE568698A (en) | 1957-06-24 |
-
0
- BE BE594249D patent/BE594249A/xx unknown
- NL NL255050D patent/NL255050A/xx unknown
- NL NL255650D patent/NL255650A/xx unknown
-
1959
- 1959-08-21 DE DEF29221A patent/DE1115248B/en active Pending
-
1960
- 1960-07-19 CH CH824160A patent/CH388956A/en unknown
- 1960-07-22 US US44537A patent/US3081330A/en not_active Expired - Lifetime
- 1960-07-27 GB GB26176/60A patent/GB879021A/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3376365A (en) * | 1964-12-28 | 1968-04-02 | Mobil Oil Corp | Phosphinothioate ester |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1115248B (en) | 1961-10-19 |
| CH388956A (en) | 1965-03-15 |
| BE594249A (en) | |
| GB879021A (en) | 1961-10-04 |
| NL255650A (en) | |
| NL255050A (en) |
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