US3758645A - Cis thiophosphoric acid amide esters - Google Patents

Cis thiophosphoric acid amide esters Download PDF

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Publication number
US3758645A
US3758645A US00054837A US3758645DA US3758645A US 3758645 A US3758645 A US 3758645A US 00054837 A US00054837 A US 00054837A US 3758645D A US3758645D A US 3758645DA US 3758645 A US3758645 A US 3758645A
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compound
formula
cis
hydrogen
methyl
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US00054837A
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J Leber
K Lutz
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Sandoz AG
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Sandoz 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/24—Esteramides
    • C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/2412—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of unsaturated acyclic alcohols
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165—Esters of thiophosphoric acids
    • C07F9/20—Esters of thiophosphoric acids containing P-halide groups
    • 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
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/22—Amides of acids of phosphorus
    • C07F9/26—Amides of acids of phosphorus containing P-halide groups

Definitions

  • the present invention concerns new thiophosphoric acid amide esters of the formula wherein R is alkyl of one to four carbon atoms, R is alkyl of one to four carbon atoms,
  • R is alkyl of one to five carbon atoms
  • X is hydrogen, chlorine or bromine.
  • the compounds are useful pesticides.
  • -COOR radicals are cis to one another in the crotonic acid radical.
  • definitions forthe compounds I essentially contemplate compounds having said cis configuration, although compounds comprising a mixture of the cis form and a certain amount of the trans form are also contemplated.
  • the configuration of compounds I is dependent on the configuration of the starting materials employed in the processes described below, and the process for the production of the starting materials described below result in a predominant proportion of compounds having the cis configuration.
  • a process for the production of a compound of formula I comprises a. reacting a compound of formula V,
  • R R and X are as defined aboveg and Y is halogen
  • Z is hydrogen or an alkali metal, in the presence of an acid acceptor when Z is hydrogen, and optionally in the presence of an acid acceptor when Z is an alkali metal.
  • Y is chlorine or bromine
  • Z is hydrogen or sodium
  • a compound of formula [V and an acid acceptor such as triethylamine, trimethylamine, dimethyl aniline, diethyl aniline or sodium carbonate are added at a temperature of between 20 and +50C, preferably between l0 and 0C, to a compound of formula V in an inert solvent, e.g., an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chlorobenzene or chloroform, or an ether such as dioxane, over a period of between one-half hour and 2 hours.
  • an inert solvent e.g., an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chlorobenzene or chloroform, or an ether such as dioxane
  • an equivalent amount of the compound of formula IV with respect to the compound of formula V is employed, and the amount of the acid acceptor is preferably such as to be equivalent with respect to the compound of formula V, for taking up the hydrohalic acid produced in the reaction.
  • the amount of the compound of formula IV is preferably two equivalents with respect to the compound of formula V.
  • the reaction mixture is stirred at room temperature over a'period of between [0 and 20 hours.
  • the solvent is subsequentlyremoved in a vacuum at a bath temperature of between 20 and 50C.
  • the residue is distilled in a high vacuum.
  • the pure compound of formula I is obtained as a colourless oil which can be distilled without decomposition.
  • a compound of formula III and an acid acceptor such as triethylamine, trimethylamine, dimethyl aniline or diethyl aniline are added at a temperature of between -20 and +50C, preferably between 0 and 20C, to a compound of formula VI in an inert solvent,
  • an aromatic,hydrocarbon such as toluene or xylene
  • a halogenated hydrocarbon such as chlorobenm wherein R is as defined above
  • an equivalent amou'ntof the compound of formula II] with respect to the'compou'nd' of formula VI is'employed, and the amount of acid acceptor is preferably such as to be equivalent with respect to the compound of formula-Vl,"forthe acceptance of displaced Yradicals.
  • t t The reaction mixture is subsequently stirred at 20C over a period of between 20 and hours,and the reaction mixture is then worked up in the usualmanner, to yield the compound-of formula I.
  • the compound of formula V employed as starting material in process a) above may be produced by reacting a compound of formula ll,
  • the resulting reaction mixture may be employed directly for reaction with the compound of formula IV in accordance with process a) above without isolation of the compound of formula V.
  • One method of effecting process a) of the invention starting with the production of a compound of formula V and continuing through to the production of a compound of formula I, without isolation of the compound of formula V comprises adding preferably at least one equivalent of a compound of formula III, at a temperature of between -20 and +50C, preferably between -lC and room temperature, to a compound of formula II in an inert solvent, e.g., an aromatic hydrocarbon such as toluene or xylene, a halogenated hydrocarbon such as chlorobenzene or chloroform, or an ether such as dioxane, over a period of between one-half hour and 2 hours, in the presence of an acid acceptor such as triethylamine, trimethylamine, dimethyl aniline or diethyl aniline.
  • an inert solvent e.g., an aromatic hydro
  • the acid acceptor is present in an amount such as to be equivalent with respect to the compound of formula II, for the acceptance of displayed Y radicals.
  • a mixture of an amine of formula IV preferably in an equivalent amount, with an acid acceptor, such as triethylamine, trimethylamine, dimethyl aniline or diethyl aniline, preferably tri-n-butyl amine, preferably also in an equivalent amount, is added at a temperature of between and +50C, preferably between l0C and room temperature, over a period of between one-half hour and 2 hours to the reaction mixture.
  • the reaction mixture is stirred at room temperature for about 20 hours.
  • the reaction mixture is then worked up in the usual manner to yield the compound of formula I.
  • a) of the invention commencing first with the production of a compound of formula V and then continuing through to the production of a compound of formula 1, without isolation of .the compound of formula V from the reaction mixture, a compound of formula II is reacted with a compound of formula III in a manner such as hereinbefore described, but in the absence of an acid acceptor.
  • Subsequent reaction of the resulting compound still contained in the reaction mixture with a compound of formula IV may be effected by employing at least three equivalents of the compound of formula IV, which compound in addition to reacting with the compound of formula V, also serves as acid acceptor, by reacting with the hydrohalic acid produced during the overall reaction, including the reaction between the compounds of formulae II and Ill.
  • the production of a compound of formula VI, employed as starting material in process b) above for the production of a compound of formula I may be effected by reacting a compound of formula II with a compound of formual IV, preferably in equivalent amounts, in the presence of an acid acceptor.
  • the compounds I of the invention essentially contemplate compounds wherein the -CH and -COOR radicals are cis to one another in the crotonic acid radical.
  • This configuration, or a predominant proportion of compounds of formula I having this configuration (more than 80 by weight) can be achieved by preparing the above compounds of formula II in a specific manner.
  • the compounds of formula Il may be produced by reacting a phosphoric oxxyor thiochloride or bromide with a compound of formula VI],
  • CI-I COCHXCOOR Vll wherein R and X are as defined above, or with a salt thereof, in the presence of an acid acceptor.
  • the compounds of formula II predominantly have a cis configuration in the crotonic acid radical (i.e. the -CH group is cis to the -COOR group) when an organic base, e.g., tri-n-butylamine or triethylamine, is used as acid acceptor.
  • an organic base e.g., tri-n-butylamine or triethylamine
  • the process may be effected by reacting a compound of formula VII with a phosphorus thiohalide, e.g., phosphorus thiochloride, in the presence of an acid acceptor, e.g., tri-n-butyl amine, and without isolating the resulting compoundof formula II from the reaction mixture adding thereto a compound of formula III together with an acid acceptor.
  • a phosphorus thiohalide e.g., phosphorus thiochloride
  • Thethiophosphoric acid amine esters of fonnula I obtained in accordance with the invention areoils which can be distilled in a high vacuum without decomposition. When they are produced in accordance with the processes a) and b) described above, the same ratio of the cis with respect to the trans isomer thereof in the crotonic acid radical is obtained as is present in the starting materials of formulae V and VI and'hence II respectively.
  • the compound I are soluble in organic solvents and may be readily emulsified with water.
  • the compounds of formula I are .useful pesticides. More particularly, the compounds possess insecticidal, acaricidal and nematocidal properties. They are effective against chewing and sucking insects, particularly against spider mites.
  • the compounds have a low level of toxicity in warm- 1 tection of plants and animals againstnoxious organisms, e.g., insects, mites and nematodes.
  • the combatting of noxious organisms may be carried out by conventional methods, e.g. by treating the subjects or locus to be protected with a composition containing a compound of formula I as active agent.
  • the compounds of formula I may be added to carrier materials to form dusting or spraying agents, e.g., solutions or dispersions, employing water or suitable organic solvents, e.g., alcohol, petroleum or tar distillates, optionally in combination with emulsifying agents, e.g., liquid polyglycol ethers derived from high molecular weight alcohols, mercaptans or alkyl phenols with an alkylene oxide.
  • suitable organic solvents such as ketones, aromatic, optionally halogenated hydrocarbons, or mineral oils, may also be added as solution aids.
  • Spraying and dusting agents may contain the usual inert carrier materials, e.g., talc, diatomaceous earth, bentonite, pumice, or other additives such as cellulose derivatives and the like, as well as conventional wetting agents and adhesives.
  • inert carrier materials e.g., talc, diatomaceous earth, bentonite, pumice, or other additives such as cellulose derivatives and the like, as well as conventional wetting agents and adhesives.
  • the compounds of formula I may be present in compositions as mixtures with other known active materials.
  • the compositions may contain between 2 and 90 preferably between 5 and 50 by weight of active agent.
  • the compositions which may be in diluted form, may contain between 0.02 and 90 preferably between 0.1 and 20 by weight of the compound of formula I.
  • a. 25 parts by weight of a compound of formula I are mixed with 25 parts by weight of isooetylphenyldecaglycol ether and 50 parts by weight of xylene, whereby a clear solution is obtained, which can easily be emulsified in water.
  • the concentrate is diluted with water to the desired concentration before use.
  • the emulsion in the dishes is then dried for about 4 hours, and then Bruchidius images are placed in each 50 parts by weight of a compound of formula I are I dish which is covered with a lid of fine mesh brass wire grating. The animals are kept without food at room temperature.
  • the mortality rate is indicated as a precentage. means that all the bean weevils were killed, 0 means that no bean weevil was killed.
  • the evaluation is given in the following Table l.
  • the rate of mortality is determined by counting out the live and dead animals.
  • the mortality rate is indicated as a percentage. 100 means that all the rod locusts were killed, 0 means that no rod locust was killed.
  • the evaluation is indicated in the following Table 3.
  • ins cticidal ctlect against Aphis fabae black bean aphid
  • contact efiect Broad bean plants Vicia faba
  • the broad bean plants are strongly infected with all the forms of development of the black bean aphid (Aphis fabae).
  • the mortality rate is indicated as a percentage. 100 means that all the bean aphids were killed, 0 means that no bean aphid was killed.
  • the evaluation is indicated in the following Table 4.
  • Nematocidal effect against Panagrellus redivivus (paste nematode) 1 cc of an aqueous suspension of Panagrellus redivivus, containing about 120 nematodes, is placed in a small cup having a diameter of 5.5 cm and a height of 3.2 cm, and containing 7 g of Terralite. 1 cc of an emulsion containing a compound of formula I is then spread over the Terralite.
  • the contents of the cup are examined in accordance with Baermann's extraction method (G.Baermann, Meded.Geneesk.Lab.'- Weltefreden 1917, 41-47), and the live nematodes are counted out under a binocular magnifying glass.
  • the rate of mortality is indicated as a range of 0 to 9 (9 maximum effect, no live nematodes, 0 no effeccover live nematodes).
  • the evaluation is indicated in the following Table 5.
  • the solution which turns viscous is stirred at to 3 for a further half hour, whereby the solution is mixed as thoroughly as possible.
  • 20 cc of toluene are added.
  • the reaction mixture is extracted twice in a separatory funnel with 120 cc amounts of approximately hydrochloric acid (25 cc of concentrated hydrochloric acid with 100 g of crushed ice).
  • the separation of the phases during the first washing with aqueous hydrochloric acid is effected without the addition of petroleum ether; petroleum ether is preferably added during the second washing with aqueous hydrochloric acid in order to complete the separation.
  • the petroleum ether phase isagain washed with water and with hydrogen carbonate solution, is dried with sodium sulphate, and the solventis removed.
  • the resulting 0- 1 carboisopropoxyl propen-2-yl)-0-methyl-N-ethylphosphorothioamidate hasa B.'P. of 8789/5.10" mm of Hg. n 1.495.
  • O)P(S)OC(CH ) CHCOOCH(CH dissolved in 1 liter of toluene, are'added to a mixture of.59.1 g .(1 mol) of propylamine and 101.2 g (1 mol) of triethylamine at a reaction temperature of 20 with '2 hours.
  • the reaction mixture is stirred at 20 for'a further 36 hours, and the precipitated triethylamine hydrochloride is subsequently filtered off.
  • the filtrate is washed with water, dried, the solvent is removed by evaporation, and the resulting product is distilled in a vacuum.
  • the 0-ethyl-0-(1carboisopropoxy-1-propen-2-yl)- thioph sphorochloridate, required as starting material, may be produced as follows:
  • the reaction mixture is added to 200 cc of ice water, the organic phase is separated, is washed well with a sodium hydrogen carbonate solution and subsequently with water, is dried with magnesium sulphate, filtered and concentrated by evaporation in a vacuum at 40.
  • the resulting product may be purified by distillation in a high vacuum. It is also possible to use the crude product in the reaction for the production of the corresponding compound of formula I.
  • the resulting 0-( l-chlorolcarbethoxy-l propen-Z-yl )-0-methyl-Nn-propyl-phosphorothioamidate has a 8.1. of 107 at 0.01 mm of Hg.
  • the ratio of the cisztrans isomers in the crotonic acid radical amounts to 9:1.
  • the 0-( l-chloro-lcarbethoxy-1-propen-2-yl)-N-npropyl-phosphoroamidochloridothionate, required as starting material, may be produced in the following manner: a
  • R is alkyl of one to four carbon atoms
  • R is alkyl of one to four carbon atoms
  • R is alkyl of one to five carbon atoms
  • X is hydrogen, chlorine or bromine, in which -CH is cis to the -COOR in the crotonic acid moiety.
  • R is n-propyl, R is ethyl and X is chlorine.

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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)
US00054837A 1969-07-18 1970-07-14 Cis thiophosphoric acid amide esters Expired - Lifetime US3758645A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1102869A CH526585A (de) 1969-07-18 1969-07-18 Verfahren zur Herstellung neuer Thiophosphorsäureamidester
CH79770 1970-01-21

Publications (1)

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US3758645A true US3758645A (en) 1973-09-11

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US (1) US3758645A (xx)
JP (2) JPS5016778B1 (xx)
BE (1) BE753579A (xx)
DK (1) DK133695B (xx)
EG (1) EG10369A (xx)
ES (2) ES381927A1 (xx)
FR (1) FR2102407A5 (xx)
GB (1) GB1315708A (xx)
IE (1) IE34387B1 (xx)
IL (1) IL34939A (xx)
NL (1) NL171161C (xx)
PL (1) PL81642B1 (xx)
RO (2) RO64797A (xx)
YU (3) YU36036B (xx)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263288A (en) * 1978-01-03 1981-04-21 Rohm And Haas Company Acaricidal, insecticidal, and nematocidal phosphoramidothioates
EP0253762A2 (en) * 1986-06-16 1988-01-20 Sandoz Ag Oil in water emulsion
US4999346A (en) * 1984-12-20 1991-03-12 Sandoz Ltd. Novel composition and process for control of cockroach population
CN105131033A (zh) * 2015-08-10 2015-12-09 河北工业大学 N-(1,2-二苯基-2-氨基)-硫代磷酰胺盐及其应用

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4263288A (en) * 1978-01-03 1981-04-21 Rohm And Haas Company Acaricidal, insecticidal, and nematocidal phosphoramidothioates
US4999346A (en) * 1984-12-20 1991-03-12 Sandoz Ltd. Novel composition and process for control of cockroach population
EP0253762A2 (en) * 1986-06-16 1988-01-20 Sandoz Ag Oil in water emulsion
EP0253762A3 (en) * 1986-06-16 1990-06-13 Sandoz Ag Oil in water emulsion
CN105131033A (zh) * 2015-08-10 2015-12-09 河北工业大学 N-(1,2-二苯基-2-氨基)-硫代磷酰胺盐及其应用
CN105131033B (zh) * 2015-08-10 2017-05-31 河北工业大学 N‑(1,2‑二苯基‑2‑氨基)‑硫代磷酰胺盐及其应用

Also Published As

Publication number Publication date
GB1315708A (en) 1973-05-02
YU9978A (en) 1985-12-31
IL34939A0 (en) 1970-09-17
PL81642B1 (xx) 1975-08-30
BE753579A (fr) 1971-01-18
DK133695C (xx) 1976-11-22
FR2102407A5 (xx) 1972-04-07
DE2035103B2 (de) 1975-06-12
EG10369A (en) 1976-02-29
ES381927A1 (es) 1973-04-16
JPS5637207B1 (xx) 1981-08-29
RO61454A (xx) 1977-01-15
YU9878A (en) 1985-12-31
IE34387L (en) 1971-01-18
RO64797A (ro) 1981-06-26
YU36036B (en) 1981-11-13
JPS5016778B1 (xx) 1975-06-16
DE2035103A1 (de) 1971-01-28
IL34939A (en) 1973-03-30
NL171161C (nl) 1983-02-16
DK133695B (da) 1976-07-05
ES410649A1 (es) 1976-06-01
NL7010066A (xx) 1971-01-20
IE34387B1 (en) 1975-04-30

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