US3029270A - Phosphonic acid esters and process for their production - Google Patents

Phosphonic acid esters and process for their production Download PDF

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Publication number
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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grams
vinyl
added
stirring
mol
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Schrader Gerhard
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Bayer AG
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Bayer AG
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    • 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)
US5626A 1959-02-04 1960-02-01 Phosphonic acid esters and process for their production Expired - Lifetime US3029270A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF27638A DE1151503B (de) 1959-02-04 1959-02-04 Verfahren zur Herstellung von Phosphon- bzw. Thio- oder Dithiophosphonsaeureestern

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US (1) US3029270A (ja)
BE (1) BE587271A (ja)
CH (1) CH399461A (ja)
DE (1) DE1151503B (ja)
DK (1) DK107849C (ja)
GB (1) GB882703A (ja)
NL (2) NL248000A (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
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

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918488A (en) * 1957-06-24 1959-12-22 Bayer Ag Phosphonic acid esters and a process for their production

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2765331A (en) * 1952-02-29 1956-10-02 Shell Dev Esters of phosphorus acids and process for the preparation of the same
DE1023034B (de) * 1956-05-24 1958-01-23 Hoechst Ag Verfahren zur Herstellung von Vinylphosphonsaeuredichlorid
BE569525A (ja) * 1957-07-17

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2918488A (en) * 1957-06-24 1959-12-22 Bayer Ag Phosphonic acid esters and a process for their production

Cited By (3)

* Cited by examiner, † Cited by third party
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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Publication number Publication date
GB882703A (en) 1961-11-15
CH399461A (de) 1965-09-30
NL248000A (ja) 1900-01-01
BE587271A (ja) 1900-01-01
NL124866C (ja) 1900-01-01
DK107849C (da) 1967-07-10
DE1151503B (de) 1963-07-18

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