US3029270A - Phosphonic acid esters and process for their production - Google Patents
Phosphonic acid esters and process for their production Download PDFInfo
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- US3029270A US3029270A US5626A US562660A US3029270A US 3029270 A US3029270 A US 3029270A US 5626 A US5626 A US 5626A US 562660 A US562660 A US 562660A US 3029270 A US3029270 A US 3029270A
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- 238000000034 method Methods 0.000 title description 5
- 238000004519 manufacturing process Methods 0.000 title description 2
- 150000003008 phosphonic acid esters Chemical class 0.000 title description 2
- 239000002253 acid Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- -1 alkyl radical Chemical class 0.000 description 32
- 238000003756 stirring Methods 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 20
- 150000002148 esters Chemical class 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 241001124076 Aphididae Species 0.000 description 9
- 241001454295 Tetranychidae Species 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000005457 ice water Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical class OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- DTMAWRDZMPCAPO-UHFFFAOYSA-N ethenyl(ethoxy)phosphinic acid hydrochloride Chemical compound Cl.CCOP(O)(=O)C=C DTMAWRDZMPCAPO-UHFFFAOYSA-N 0.000 description 3
- RSXPIJKXIOZTFO-UHFFFAOYSA-N ethenyl-dihydroxy-sulfanylidene-lambda5-phosphane Chemical class C(=C)P(O)(O)=S RSXPIJKXIOZTFO-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- FSNDHQWTLNTNEA-UHFFFAOYSA-N (3-ethenyl-1-sulfanylidenethiophen-2-yl)phosphonic acid Chemical class C(=C)C1=C(S(C=C1)=S)P(O)(=O)O FSNDHQWTLNTNEA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 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 2
- 241000700159 Rattus Species 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- MLSZIADXWDYFKM-UHFFFAOYSA-N 1-dichlorophosphorylethene Chemical compound ClP(Cl)(=O)C=C MLSZIADXWDYFKM-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 1
- 241001425390 Aphis fabae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- DJUWOJJZRJZCOK-UHFFFAOYSA-N [Na].CC=1C=C(C=CC1SC)O Chemical compound [Na].CC=1C=C(C=CC1SC)O DJUWOJJZRJZCOK-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000332 continued effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- QDOPBBLWIUQTAW-UHFFFAOYSA-N dichloro-ethenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C=C QDOPBBLWIUQTAW-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005059 halophenyl group Chemical group 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- BYOIUZNBVLCMNV-UHFFFAOYSA-M sodium;2,4-dichlorophenolate Chemical compound [Na+].[O-]C1=CC=C(Cl)C=C1Cl BYOIUZNBVLCMNV-UHFFFAOYSA-M 0.000 description 1
- CURNJKLCYZZBNJ-UHFFFAOYSA-M sodium;4-nitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1 CURNJKLCYZZBNJ-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229940086542 triethylamine Drugs 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
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4015—Esters of acyclic unsaturated acids
-
- 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
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
Definitions
- the present invention relates to and has as its objects new and useful phosphonic acid derivatives with especially insecticidal or more broadly pesticidal properties.
- the new compounds of the present invention may be represented by the following formula ll CHFoH-P in which R stands for a lower alkyl radical up to 6 carbon atoms and R stands for substituted alkyl or possibly substituted aralkyl or aryl radicals.
- R stands for a lower alkyl radical up to 6 carbon atoms
- R stands for substituted alkyl or possibly substituted aralkyl or aryl radicals.
- the preparation of the new compounds of this invention may be carried out by methods known in principle, but should be described in more detail in the following description.
- Ester chlorides of vinyl-phosphonic acids and vinylthionophosphonic acids can be converted into vinyl-phosphonic, vinyl-fluonophosphonic acid esters or vinylthionothiolphosphonic acid esters by known methods.
- vinyl-phosphonic acid esters it is possible to produce esters with various alkyl radicals. Esters of this kind have hitherto not been known in the liaterature, nor have vinyl-thionophosphonic acid esters been described in literature.
- Vinyl-thionophosphonic acid alkyl ester chlorides may also be saponified with alkali metal hydroxide and then reacted with optional alkyl halides, arakyl halides or if desired, with aryl halides. This reaction is illustrated by the following reaction scheme.
- Vinyl-thionothiolphosphonic acid esters can also be obtained e.g. via an alkali metal especially the potassium salt I, easily obtainable with potassium hydrogen sulfide, for example from vinyl-thionophosphonic acid alkyl ester chlorides, and subsequent alkylation:
- R stands for lower alkyl radicals, preferably with 1-6 carbon atoms, and R stands for a substituted alkyl radical or an optionally substituted aralky l or aryl radical; R thus may stand for the following radicals, given as examples but not intended to limit the scope of this invention in any way: CH3SC2H5
- the intermediate vinyl-phosphonic acid or vinyl-thiephosphonic acid ester chlorides are obtainable by a simple process discovered in the meantime.
- This process consists in reacting vinyl-phosphonic acid dihalides (chlorides) with about the stoichiometrical amount of alcohols in the presence of acid-binding agents especially of tertiary amines, or by reacting the corresponding vinyl-thionophosphonic acid dihalides (chlorides) with about stoichiometrical amounts of especially alkali metal alcoholates.
- the new compounds obtainable according to the invention are intended to be used in the first place as plant protective agents or insecticides. They are preferably used in combination with suitable solid or liquid extenders or diluents. Suitable solid extenders are, for example, talc, chalk, bentonite or kieselguhr, or in the case of liquid agents, water, preferably in combination with suitable emulsifiers and an organic solubilizer such as, for example, dimethyl formamide or acetone.
- Example I O OC Hs 145 grams of vinyl-phosphonic acid dichloride (1 mol) (B.P. 44/ 1 mm. Hg) are dissolved in 1000 ml. of petrol ether. While stirring there is added at 10 to 20 C. a mixture of 101 grams of triethyl amine and 48 grams of anhydrous ethanol. Stirring is continued for 1 further hour, and the triethyl amine salt which has been formed is filtrated with suction. The remaining solution is freed from solvent by distillation and the residue is distilled under high vacuum, the vinyl-phosphonic acid ethyl ester chloride distilling at 1 mm. Hg/49 C. is obtained. The yield amounts to 75% of the theoretical.
- Example 2 322 grams (2 mols) of vinyl-thionophosphonic acid dichloride (13.1. 46 C./1 mm. Hg) are dissolved in 1500 ml. of benzene whereupon While stirring there is added at 0 to C. a concentrated sodium ethylate solution containing 46 grams of sodium metal. Thereafter stirring is continued for further 10 minutes and the reaction mixture is poured into ice-water. The benzenic layer is separated, washed once with 100 ml. of water and then is dried over anhydrous sodium sulfate. After fractionated distillation there are obtained 232 grams of vinyl-thionophosphonic acid ethyl ester chloride (B.P. 48 C./l mm. Hg). The yield is 68% of the theoretical.
- Example 3 39 grams (0.25 mol) of vinyl phosphonic acid ethyl ester chloride (Bl 49 C./ l mm. Hg) is added dropwise with stirring at 3040 C. to 40 grams of p-nitrophenol sodium salt dissolved in 150 cc. of methyl ethyl ketone. Stirring is continued for an hour whereupon the reaction product is added to 300 cc. of ice water. The precipitated oil is taken up in 200 cc. of benzene and deacidified with a 4% solution of bicarbonate. After drying, the benzene solution is fractionated. 35 grams of the ester of HP. 119 C./0.0l mm. Hg is obtained. Yield 55% of the theoretical.
- the precipitated oil is taken up in 400 cc. of chloroform, washed neutral with Water and dried over sodium sulfate. Upon fractionating, 32 grams of the new ester of B.P. 79 C./0.01 mm. Hg are obtained. Yield 53% of the theoretical.
- Example 6 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added dropwise with stirring to a solution of 36 grams of 4-chlorophenyl-mercaptan dissolved in a solution of sodium ethylate containing 1/4 mol of sodium. The temperature is kept at 20 C. during the dropping in and stirred for an hour after the dropwise addition. The reaction product is then added to 300 cc. of ice-water and worked up in usual manner. 34 grams of the new ester of B.P. 126 Yield 49% 6 grams (0.25 mol) of powdered sodium are suspended in 100 cc. of benzene. 60 grams of diethyl aminoethanol are added with stirring at 50 C. to the suspension.
- Example 9 fi/OCJHE 0H3 CH-P
- Example 10 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 60 C. to a solution of 56 grams of 3,4,6-tn'chlorophenol sodium salt in 100 cc. of methyl ethyl ketone. Heating is con tinued at 50-60 C. for 10 hours, the reaction product taken up in 300 cc. of benzene and the benzene solution is washed several times with water. The resulting crude product is kept at a bath temperature of 70 C. in a vacuum of 1 mm. Hg for a short time. In this manner, 60 grams of the new ester are obtained as a water-insoluble pale yellow oil. Yield 72% of the theoretical.
- Example 11 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 60 C. to a solution of 48 grams or" 2,4-dichlorophenol sodium salt in 100 cc. of methyl ethyl ketone. The mixture is stirred for a further 10 hours and then worked up in conventional manner. 54 grams of the new ester are obtained as a water-insoluble pale yellow oil. Yield 73% of the theoretical.
- Example 16 In an analogous manner there are obtained from 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride, 36 grams of potassium hydrogen sulfide and 40 grams of a-chloromethyl-thiophenyl ether, 51 grams of the new ester. Yield 70% of the theoretical.
- Example 17 B O C2115 CHFCH-P C 2-C 2N (C 2 2 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 40 C. to 36 grams of potassium hydrogen sulfide in 100 cc. of anhydrous alcohol. The mixture is warmed at 40 C. for an hour and 50 cc. of acetonitrile are then added. 35 grams of fi-chioroethyl-diethylamine are then added dropwise at 70 C. to the mixture. The mixture i heated to 80 C. for an hour, then cooled to room temperature and the reaction product is added to 300 cc. of ice-Water. The separated oil is taken up in 200 cc. of benzene and dried with sodium sulfate. Upon fractionating, 30 grams of the new ester of BB. 84 C./0.01 mm. Hg are obtained. Yield 45% of the theoretical.
- Example 18 IS 0 C2115 0H OH-P 0 SCHa CH 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 30 C. to 45 grams of 3-methyl-4-methylmercapto-phenol sodium saltester of Bi. C./0.0l Hg are obtained. Yield 69% ot' the theoretical.
- Example 19 S-OH-CHZ-SCZH5 CIIa 52 grams (0.25 mol) of vinyl-thionophosphonic acid- O-ethyl ester-thiolic acid potassium salt (Ml 186 C.) are dissolved in cc. of acetonitrile. 35 grams of 2- chloro-isopropyl-thioethyl ether (Bi 56 C./ 13 mm. Hg) are added thereto with stirring at 80 C. The reaction product is heated at 80 C. for an hour, diluted with 300 cc. of benzene and then added to 200 cc. of ice- Water. After conventional working up there are obtained 40 grams of the new ester of 13.1. 94 C./ 0.01 mm. Hg. Yield 59% of the theoretical.
- the new ester shows on rats per os a toxicity of 25 trig/kg.
- X stands for a chalcogen having an atomic weight from 16 to 33
- R stands for an alkyl radical having up to 6 carbon atoms and R stands for a member selected from the group consisting of a lower alkyl radical substituted by a lower alkyl mercapto group, a lower alkyl radical substituted by a lower dialkyl amino group, a lower alkyl radical substituted by a phenyl mercapto group, a lower alkyl radical substituted by a halophenyl mercapto group, a lower alkyl radical substituted by a cyano group, and a lower alkyl radical substituted by a phenyl carbonyl group, nitro-substituted phenyl radical,
- R is a lower alkyl mercapto-substituted phenyl radical.
- R is a lower alkyl radical substituted by a lower alkyl mercapto group.
- R is a phenyl mer- 10.
- the compound of the following formula capto lower alkyl radical.
- S OCQH4 6.
- R is a lower alkyl C Il/ radical susbtituted by a lower dialkyl amino group.
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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)
Description
United States Patent Ofilice 3,29,Z? Patented Apr. 10, 1982 The present invention relates to and has as its objects new and useful phosphonic acid derivatives with especially insecticidal or more broadly pesticidal properties. Generally the new compounds of the present invention may be represented by the following formula ll CHFoH-P in which R stands for a lower alkyl radical up to 6 carbon atoms and R stands for substituted alkyl or possibly substituted aralkyl or aryl radicals. The preparation of the new compounds of this invention may be carried out by methods known in principle, but should be described in more detail in the following description. Ester chlorides of vinyl-phosphonic acids and vinylthionophosphonic acids can be converted into vinyl-phosphonic, vinyl-fluonophosphonic acid esters or vinylthionothiolphosphonic acid esters by known methods. In the case of vinyl-phosphonic acid esters it is possible to produce esters with various alkyl radicals. Esters of this kind have hitherto not been known in the liaterature, nor have vinyl-thionophosphonic acid esters been described in literature.
Various ways can be used for the production of the new compoundsclaimed according to the invention. It is thus possible to react, for example, viny1-(thiono)- phosphonic acid alkyl ester chlorides with optional alcohols, phenols or mercaptans. The following reaction scheme illustrates this reaction:
Vinyl-thionophosphonic acid alkyl ester chlorides may also be saponified with alkali metal hydroxide and then reacted with optional alkyl halides, arakyl halides or if desired, with aryl halides. This reaction is illustrated by the following reaction scheme.
Vinyl-thionothiolphosphonic acid esters can also be obtained e.g. via an alkali metal especially the potassium salt I, easily obtainable with potassium hydrogen sulfide, for example from vinyl-thionophosphonic acid alkyl ester chlorides, and subsequent alkylation:
S OH] (ll-R1 CH2=C11- K01 In the above reaction scheme R stands in each case for a preferred lower alkyl radical whilst R may stand for optionally substituted alkyl, aralkyl or ary-l radicals as described in the beginning of the description.
The compounds obtainable according to the invention as said above have the following general composition:
wherein R stands for lower alkyl radicals, preferably with 1-6 carbon atoms, and R stands for a substituted alkyl radical or an optionally substituted aralky l or aryl radical; R thus may stand for the following radicals, given as examples but not intended to limit the scope of this invention in any way: CH3SC2H5 The intermediate vinyl-phosphonic acid or vinyl-thiephosphonic acid ester chlorides are obtainable by a simple process discovered in the meantime. This process consists in reacting vinyl-phosphonic acid dihalides (chlorides) with about the stoichiometrical amount of alcohols in the presence of acid-binding agents especially of tertiary amines, or by reacting the corresponding vinyl-thionophosphonic acid dihalides (chlorides) with about stoichiometrical amounts of especially alkali metal alcoholates.
The new compounds obtainable according to the invention are intended to be used in the first place as plant protective agents or insecticides. They are preferably used in combination with suitable solid or liquid extenders or diluents. Suitable solid extenders are, for example, talc, chalk, bentonite or kieselguhr, or in the case of liquid agents, water, preferably in combination with suitable emulsifiers and an organic solubilizer such as, for example, dimethyl formamide or acetone.
As an example for the special utility of the inventive compounds the compounds of the following formulae O 02 (II) have been tested against aphids and spider mites. 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 th desired concentrations. The tests have been carried out as follows:
(a) Against aphids of the type Doralis fabae: heavily infested bean plants (Vicia faba) have been sprayed drip wet with solutions as prepared above. The eifect has been determined after 24 hours by counting the dead pests either on the surface of the soil or still remaining on the plants. The following results have been obtained:
Compound aqueous concentration killing rate (in percent active (in percent) ingredient/water) (I) 0.01 100 (II) 0.01 100 Compound aqueous concentration killing rate (in percent active (in percent) ingredient/water) The following examples are given for illustrating the present invention:
Example I O OC Hs 145 grams of vinyl-phosphonic acid dichloride (1 mol) (B.P. 44/ 1 mm. Hg) are dissolved in 1000 ml. of petrol ether. While stirring there is added at 10 to 20 C. a mixture of 101 grams of triethyl amine and 48 grams of anhydrous ethanol. Stirring is continued for 1 further hour, and the triethyl amine salt which has been formed is filtrated with suction. The remaining solution is freed from solvent by distillation and the residue is distilled under high vacuum, the vinyl-phosphonic acid ethyl ester chloride distilling at 1 mm. Hg/49 C. is obtained. The yield amounts to 75% of the theoretical.
Calculated for mol 155: P=20.1%; Pound: P=19.7%; Cl=23.2%.
Example 2 322 grams (2 mols) of vinyl-thionophosphonic acid dichloride (13.1. 46 C./1 mm. Hg) are dissolved in 1500 ml. of benzene whereupon While stirring there is added at 0 to C. a concentrated sodium ethylate solution containing 46 grams of sodium metal. Thereafter stirring is continued for further 10 minutes and the reaction mixture is poured into ice-water. The benzenic layer is separated, washed once with 100 ml. of water and then is dried over anhydrous sodium sulfate. After fractionated distillation there are obtained 232 grams of vinyl-thionophosphonic acid ethyl ester chloride (B.P. 48 C./l mm. Hg). The yield is 68% of the theoretical.
Calculated for mol 171: Cl=20.8%; S=l8.3%; P=18.1%. Found: Cl=20.7%; S=17.8%; P=17.9%.
4 Example 3 39 grams (0.25 mol) of vinyl phosphonic acid ethyl ester chloride (Bl 49 C./ l mm. Hg) is added dropwise with stirring at 3040 C. to 40 grams of p-nitrophenol sodium salt dissolved in 150 cc. of methyl ethyl ketone. Stirring is continued for an hour whereupon the reaction product is added to 300 cc. of ice water. The precipitated oil is taken up in 200 cc. of benzene and deacidified with a 4% solution of bicarbonate. After drying, the benzene solution is fractionated. 35 grams of the ester of HP. 119 C./0.0l mm. Hg is obtained. Yield 55% of the theoretical.
Solutions of 0.01% kill aphids 100% and spider mites 65%.
Example 4 O O C2115 li/ CHz=CH-P 39 grams (0.25 mol) of vinyl-phosphonic acid ethyl ester chloride are added dropwise with stirring at 30 C. to 45 grams of 3-methyl-4-methyirnercapto-phenol sodium salt dissolved in 200 cc. of methyl ethyl ketone. Heating is continued at 30 C. for an hour and the reaction product is then added to 300 cc. of ice-Water. The precipitated oil is taken up in 300 cc. of benzene, deaciditied with a solution of sodium bicarbonate and dried with sodium sulfate. Upon fractionating, 40 grams of the new ester of B.P. 112 C./0.0l mm. Hg are obtained. Yield 59% of the theoretical.
0.01% solutions kill aphids 100% and spider mites 40%.
Example 5 S 0C2H5 CH2=CH-P O-CHrCHg-SCgHg 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride (B.P. 48 C./1 mm. Hg) are added dropwise with stirring to 28 grams of fl-hydroxyethylthioethyl ether dissolved in 150 cc. of methyl ethyl ketone. 40 grams of finely powdered and dry potassium carbonate are added to the suspension and the mixture is heated to C. for 2 hours. The reaction mixture is then cooled to room temperature. The precipitated salt is fitered off with suction. The filtrate is added to 300 cc. of water. The precipitated oil is taken up in 400 cc. of chloroform, washed neutral with Water and dried over sodium sulfate. Upon fractionating, 32 grams of the new ester of B.P. 79 C./0.01 mm. Hg are obtained. Yield 53% of the theoretical.
0.01% solutions kill aphids and spider mites 60%.
Example 6 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added dropwise with stirring to a solution of 36 grams of 4-chlorophenyl-mercaptan dissolved in a solution of sodium ethylate containing 1/4 mol of sodium. The temperature is kept at 20 C. during the dropping in and stirred for an hour after the dropwise addition. The reaction product is then added to 300 cc. of ice-water and worked up in usual manner. 34 grams of the new ester of B.P. 126 Yield 49% 6 grams (0.25 mol) of powdered sodium are suspended in 100 cc. of benzene. 60 grams of diethyl aminoethanol are added with stirring at 50 C. to the suspension. Heating is continued at 50 C. for an hour and 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added dropwise with further stirring at 30 C. The mixture is stirred at 30 C. for a further hour, the reaction product is taken up in 200 cc. of benzene and the mixture is added to 300 cc. of ice-water. After conventional Working up, 40 grams of the new ester of B.P. 88 C./0.01 mm. Hg are obtained. Yield 64% of the theoretical.
Example 8 S 11 ll/ CH2=CHP 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added dropwise with stirring at 20 C. to 41 grams of p-methylmercapto-phenol sodium salt dissolved in 200 cc. of methyl ethyl ketone. The mixture is stirred at 20 C. for a further hour and then worked up in usual manner. The resulting ester obtained as a water-insoluble oil is kept for a short time at a bath temperature of 70 C. and 1 mm. Hg pressure. 57 grams of the new ester are obtained in this manner. Yield 83% of the theoretical.
0.01% solutions kill aphids to 100% and spider mites to 90%.
Example 9 fi/OCJHE 0H3=CH-P Example 10 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 60 C. to a solution of 56 grams of 3,4,6-tn'chlorophenol sodium salt in 100 cc. of methyl ethyl ketone. Heating is con tinued at 50-60 C. for 10 hours, the reaction product taken up in 300 cc. of benzene and the benzene solution is washed several times with water. The resulting crude product is kept at a bath temperature of 70 C. in a vacuum of 1 mm. Hg for a short time. In this manner, 60 grams of the new ester are obtained as a water-insoluble pale yellow oil. Yield 72% of the theoretical.
Example 11 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 60 C. to a solution of 48 grams or" 2,4-dichlorophenol sodium salt in 100 cc. of methyl ethyl ketone. The mixture is stirred for a further 10 hours and then worked up in conventional manner. 54 grams of the new ester are obtained as a water-insoluble pale yellow oil. Yield 73% of the theoretical.
Example 12 O OC2H5 ll/ CHz=CH-P 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are heated with 30 grams of potassium hydroxide dissolved in 50 cc. of water with the addition of 20 cc. of anhydrous alcohol to C. for an hour. In this way the sodium salt of the following constitution is formed:
0 00211. ll/ e O Na SN a 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring to a solution of 36 grams of potassium hydrogen sulfide in cc. of anhydrous alcohol. The mixture is heated to 40 C. for an hour and 28 grams of e-chloromethyl-thioethyl ether are then added with stirring. The whole is kept at 50 C. for a further hour and then Worked up in conventional manner. 37 grams of the new ester of B.P. 70 C./0.0l mm. Hg are thus obtained. Yield 61% of the theoretical 0.01% solutions kill aphids to 100% and spider mites to 40 Example 14 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring to a solution of 36 grams of potassium hydrogen sulfide in 100 cc. of anhydrous alcohol. The mixture is heated to 40 C. for an hour and 32 grams of fl-chloroethyl-thioethyl other are then added with stirring at 80 C. Heating is continued at 80 C. for an hour and the mixture is worked up in conventional manner. 34 grams of the new ester of HP. 79 C./0.01 mm. Hg are obtained. Yield 53% of the theoretical.
Spider mites Example 15 8 002115 CH2=CHP 43 grams (0.25 mol) of vinyl-thionophosphonie acid ethyl ester chloride are added with stirring to 36 grams of potassium hydrogen sulfide in 100 cc. of anhydrous ethyl alcohol. The mixture is kept at 40 C. for 1 /2 hours and 52 grams of a-chloro-rnethyl-p-chlorophenylthioether are added. The reaction product is kept at 50 C. for a further 2 hours and then added to 300 cc. of ice-Water. The precipitated oil is taken up in 200 cc. of benzene and washed several times with water. After removing the solvent, a water-insoluble yellow oil is obtained which is kept for a short time at a bath temperature of 70 C. and a vacuum of 1 mm. Hg. 58 grams of the new ester are thus obtained. Yield 72% of the theoretical.
Example 16 In an analogous manner there are obtained from 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride, 36 grams of potassium hydrogen sulfide and 40 grams of a-chloromethyl-thiophenyl ether, 51 grams of the new ester. Yield 70% of the theoretical.
0.01% solutions kill aphids to 100% and spider mites to 75%.
Example 17 B O C2115 CHFCH-P C 2-C 2N (C 2 2 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 40 C. to 36 grams of potassium hydrogen sulfide in 100 cc. of anhydrous alcohol. The mixture is warmed at 40 C. for an hour and 50 cc. of acetonitrile are then added. 35 grams of fi-chioroethyl-diethylamine are then added dropwise at 70 C. to the mixture. The mixture i heated to 80 C. for an hour, then cooled to room temperature and the reaction product is added to 300 cc. of ice-Water. The separated oil is taken up in 200 cc. of benzene and dried with sodium sulfate. Upon fractionating, 30 grams of the new ester of BB. 84 C./0.01 mm. Hg are obtained. Yield 45% of the theoretical.
0.001% solutions kill aphids to 40% and spider mites to 80%.
Example 18 IS 0 C2115 0H OH-P 0 SCHa CH 43 grams (0.25 mol) of vinyl-thionophosphonic acid ethyl ester chloride are added with stirring at 30 C. to 45 grams of 3-methyl-4-methylmercapto-phenol sodium saltester of Bi. C./0.0l Hg are obtained. Yield 69% ot' the theoretical.
Example 19 S-OH-CHZ-SCZH5 CIIa 52 grams (0.25 mol) of vinyl-thionophosphonic acid- O-ethyl ester-thiolic acid potassium salt (Ml 186 C.) are dissolved in cc. of acetonitrile. 35 grams of 2- chloro-isopropyl-thioethyl ether (Bi 56 C./ 13 mm. Hg) are added thereto with stirring at 80 C. The reaction product is heated at 80 C. for an hour, diluted with 300 cc. of benzene and then added to 200 cc. of ice- Water. After conventional working up there are obtained 40 grams of the new ester of 13.1. 94 C./ 0.01 mm. Hg. Yield 59% of the theoretical.
The new ester shows on rats per os a toxicity of 25 trig/kg. LDSQ- Example 20 CH=CHP S-OH2-CN 52 grams (0.25 mol) of vinyl-thionophosphonic acid- O-ethyl-ester thiolic acid potassium salt are dissolved in 150 cc. of acetonitrile. 19 grams of chloro-acetonitrile are added with stirring at 40 C. for a further hour and then worked up in conventional manner. 30 grams of the new ester of 8.1. 86 C./ 0.01 mm. Hg are obtained. Yield 587% of the theoretical. The toxicity on rats per os is 50 rug/kg. L13
Example 21 s ooirr I claim: 1. A phosphonic acid ester of the general formula:
INC/0R1 onFoH-i XRZ wherein X stands for a chalcogen having an atomic weight from 16 to 33; R stands for an alkyl radical having up to 6 carbon atoms and R stands for a member selected from the group consisting of a lower alkyl radical substituted by a lower alkyl mercapto group, a lower alkyl radical substituted by a lower dialkyl amino group, a lower alkyl radical substituted by a phenyl mercapto group, a lower alkyl radical substituted by a halophenyl mercapto group, a lower alkyl radical substituted by a cyano group, and a lower alkyl radical substituted by a phenyl carbonyl group, nitro-substituted phenyl radical,
a lower alkyl mercapto-substituted phenyl radical and a halogen-substituted phenyl radical.
2. A compound of claim 1 wherein R is intro-substituted phenyl.
3. A compound of claim 1 wherein R is a lower alkyl mercapto-substituted phenyl radical.
4. A compound of claim 1 wherein R is a lower alkyl radical substituted by a lower alkyl mercapto group.
1 l) 5. A compound of claim 1 wherein R is a phenyl mer- 10. The compound of the following formula capto lower alkyl radical. S OCQH4 6. A compound of claim 1 wherein R is a lower alkyl C Il/ radical susbtituted by a lower dialkyl amino group. H
7. The compound of the following formula 5 0 C i1 11. The compound of the following formula oH,=oH- P oolm Q on =oH-P 8. The compound of the following formula 10 S-C aS ii 12. The compound of the following formula CHFOH-P fi/O C2115 Q' 15 oHFoH-P (3H3 S-CH2-CH2N(C:1HU2 The compound of the following formula References Cited in the file of this patent S UNITED STATES PATENTS C H H/ 20 4 2,918,488 Schrader Dec. 22, 1959
Claims (1)
1. A PHOSPHONIS ACID ESTER OF THE GENERAL FORMULA:
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DEF27638A DE1151503B (en) | 1959-02-04 | 1959-02-04 | Process for the production of phosphonic or thio or dithiophosphonic acid esters |
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US3029270A true US3029270A (en) | 1962-04-10 |
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US5626A Expired - Lifetime US3029270A (en) | 1959-02-04 | 1960-02-01 | Phosphonic acid esters and process for their production |
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US (1) | US3029270A (en) |
BE (1) | BE587271A (en) |
CH (1) | CH399461A (en) |
DE (1) | DE1151503B (en) |
DK (1) | DK107849C (en) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US3361855A (en) * | 1960-02-13 | 1968-01-02 | Bayer Ag | Dithiophosphonic acid esters |
US3416912A (en) * | 1966-11-23 | 1968-12-17 | Chemagro Corp | Process of killing plants |
US3481731A (en) * | 1967-01-27 | 1969-12-02 | Chemagro Corp | Alkoxy vinyl phosphono dithioates as herbicides |
Citations (1)
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US2918488A (en) * | 1957-06-24 | 1959-12-22 | Bayer Ag | Phosphonic acid esters and a process for their production |
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US2765331A (en) * | 1952-02-29 | 1956-10-02 | Shell Dev | Esters of phosphorus acids and process for the preparation of the same |
DE1023034B (en) * | 1956-05-24 | 1958-01-23 | Hoechst Ag | Process for the production of vinylphosphonic acid dichloride |
NL100011C (en) * | 1957-07-17 |
-
0
- BE BE587271D patent/BE587271A/xx unknown
- NL NL248000D patent/NL248000A/xx unknown
- NL NL124866D patent/NL124866C/xx active
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- 1959-02-04 DE DEF27638A patent/DE1151503B/en active Pending
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1960
- 1960-01-27 CH CH94760A patent/CH399461A/en unknown
- 1960-02-01 US US5626A patent/US3029270A/en not_active Expired - Lifetime
- 1960-02-02 GB GB3735/60A patent/GB882703A/en not_active Expired
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US2918488A (en) * | 1957-06-24 | 1959-12-22 | Bayer Ag | Phosphonic acid esters and a process for their production |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3361855A (en) * | 1960-02-13 | 1968-01-02 | Bayer Ag | Dithiophosphonic acid esters |
US3416912A (en) * | 1966-11-23 | 1968-12-17 | Chemagro Corp | Process of killing plants |
US3481731A (en) * | 1967-01-27 | 1969-12-02 | Chemagro Corp | Alkoxy vinyl phosphono dithioates as herbicides |
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NL124866C (en) | 1900-01-01 |
DK107849C (en) | 1967-07-10 |
CH399461A (en) | 1965-09-30 |
DE1151503B (en) | 1963-07-18 |
NL248000A (en) | 1900-01-01 |
BE587271A (en) | 1900-01-01 |
GB882703A (en) | 1961-11-15 |
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