US3857838A - Organophosphate ester derivatives of heterocyclic compounds and process - Google Patents

Organophosphate ester derivatives of heterocyclic compounds and process Download PDF

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Publication number
US3857838A
US3857838A US00288393A US28839372A US3857838A US 3857838 A US3857838 A US 3857838A US 00288393 A US00288393 A US 00288393A US 28839372 A US28839372 A US 28839372A US 3857838 A US3857838 A US 3857838A
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United States
Prior art keywords
carbon atoms
dihydro
pyrimidine
mixture
group
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Expired - Lifetime
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US00288393A
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English (en)
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J Perronnet
A Poittevin
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Sanofi Aventis France
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Roussel Uclaf SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings

Definitions

  • A represents a divalent radical selected from the group consisting of alkylene having three to five carbon atoms, aza substitued alkylene having atoms, alkoxy having one to four carbon atoms, alkoxyalkoxy having'one to four carbon atoms in each alk, and
  • R, and R are members selected from the group consisting of hydrogen and alkyl having one to three carbon atoms; as well as the process of producing said organophosphate esters.
  • the compounds have insecticidal and acaricidal properties 4 Claims, N0 Drawings ORGANOPIIOSPIIATE ESTER DERIVATIVES OF IIETEROCYCLIC COMPOUNDS AND PROCESS OBJECTS OF THE INVENTION T N A wherein A represents a divalent radical selected from the group consisting of alkylene having three to five carbon atoms, aza substituted alkylene having three to five carbon atoms in the chain and thia substituted alkylene having three to five carbon atoms in the chain,
  • Y represents a member selected from the group consisting of hydrogen, alkyl having one to six carbon atom, cyano, halo and alkylthio having one to six carbon atoms,
  • X represents a member selected from the group consisting of sulfur and oxygen
  • R represents an alkyl having one to four carbon atoms
  • R represents a member selected from the group consisting of alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, al-
  • R, and R are members selected from the group consisting of hydrogen and alkyl having one to wherein A represents a divalent radical selected from the group consisting of alkylene having three to five carbon atoms, aza substituted alkylene having three to five carbon atoms in the chain and thia substituted al kylene having three to five carbon atoms in the chain and Y represents a member selected from the group consiting of hydrogen, alkyl having from one to six carbon atoms, cyano, halo and alkylthio having from one to six carbon atoms.
  • halophosphate having the formula wherein Hal represents a member selected from the group consisting of chloro and bromo, X represents a member selected from the group consisting of sulfur and oxygen, R represents an alkyl having one to four carbon atoms and R represents a member selected from the group consisting of alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, alkoxyalkoxy having one to four carbon atoms in eac alk, and
  • R, and R are members selected from the group consisting of hydrogen and alkyl having one to three carbon atoms, and recovering said organophosphate ester.
  • a further object ofthe present invention is the development of insecticidal and/or acaricidal compositions containing from 10 percent to percent of the above organophosphate esters and the remainder inert excipients.
  • a yet further object of the present invention is the development of a method for combatting insects and/or acarids which comprises contacting 'them with the above organophosphate esters.
  • A represents an alkylene chain having from three to five carbon atoms, possibly interrupted by a beteroatom chosen from sulfur and nitrogen, and more particularly A represents a divalent radical selected from the group consisting of alkylene having three to five carbon atoms, aza substituted alkylene having three to five carbon atoms in the chain and thia substituted alkylene having three to five carbon atoms in the chain;
  • Y represents hydrogen, alkyl having one to six carbon atoms, linear or branched, cyano, halogen or alkylthio having one to six carbon atoms, and more praticularly Y represents a member selected from the group consisting of hydrogen, alkyl having from one to six carbon atoms, cyano, halo and alkylthio having from one to six carbon atoms;
  • X represents an atom of sulfur or oxygen
  • R represents an alkyl. linear or branched. having one to four carbon atoms
  • R represents an alkyl, linear or branched, having one to four carbon atoms, alkoxy having one to four carbon atoms and possibly substituted by alkoxy having one to four carbon atoms, or R represents an amino group in which R, and R the same or different, represent either hydrogen or an alkyl, linear or branched, having one to three carbon atoms, and more particularly R represents a member selected from the group consisting of alkyl having one to four carbon atoms, alkoxy having one to four carbon atoms, alkoxyalkoxy having one to four carbon atoms in each alk, and
  • R, and R are members selected from the group consisting of hydrogen and alkyl having one to three carbon atoms.
  • alkyl used here above designates particularly methyl, ethyl, propyl, isopropyl or n-butyl and the h. 2-diethoxythiophosphoryloxy-3-ethylthio-7 ,8-.
  • the compounds of formula I are endowed withpesti- I cidal properties particularly as insecticides and/or acaricides which make them suitable to control noxious organisms and particularly insects and acarids.
  • insecticidal properties of these compounds can be demonstrated particularly by tests on Prodenia lituru, Ceralin's capitata, Aphisfabl'ze, BIateIIa germanica or Musca domestica which are described later.
  • (III) such as acetone, acetonitrile, benzene, methanol or ethyl acetate, under, preferably, anhydrous conditions in the presence of a basic agent such as an alkali metal carbonate, an alkali metal lower alkanolate and/or a tertiary organic amine base such as triethylamine, trimethylamine or pyridine.
  • the basic agent may also be the alkali metal derivative of the compound of formula II as formed from the reaction of the compound of formula ll with an alkali metal lower alkanolate in a solvent such as a lower alkanol.
  • these compounds can be prepared by reacting a compound of the formula with a trialkyl phosphite. Preferably, this reaction is conducted with an excess of the trialkylphosphite and for example at temperatures of from 50C to 125C.
  • the invention also comprises the insecticidal and/or acaricidal compositions containing, as active material, at least one of the compounds of formula I.
  • These compositions can be presented in the form of powders, granules, suspensions, emulsions, solutions, containing the active principle, for example, in mixture with a vehicle and/or ananionic, cationic or nonionic surfaceactive agent assuring, among other things, a uniform dispersion of the substances of the composition.
  • the vehicle utilized can be a liquid such as water, alcohol, hydrocarbons or other organic solvents, mineral, vegetable or animal oil, or a powder such as talc, clays, silicates, Kieselguhr.
  • the insecticidal liquidsor powders for foliage applications contain preferably from 20 to percent by weight of the active material Formula I.
  • the acaricidal liquids or powders for foliage applications contain preferably from 20 percent to 80 percent by weight of the active material of formula I.
  • insects and/or acarids are contacted with the insects and/or acarids.
  • the compounds of formula 11. utilized as starting materials in the process of the invention. can be prepared accordingto a process analogous to that described by Le Berre et a1. Bull. Soc. Chim. 1969, 3137.
  • N OH 1 I A N Br can be prepared by the action ofN-bromo-succinimide on compounds of the formula
  • the following examples are illustrative of the practice ol the invention without being deemed limitative in any respect.
  • 1.6-dhydro-4-hydr0xy-5-isopropyl-azepino-[ 1 .2-a]- pyrimidine-6-one 45 gm of sodium ethylate were introduced into 450 cc of ethanol. 63 gm of ethyl isopropyl-malonate and 50 gm of the sulfate ofcaprolactamidine were added to the solution obtained. The reaction mixture was heated to reflux and maintained there for four hours. The solvent was then eliminated by distillation under reduced pressure. The residue was dissolved in water and acidified to a ph of 3 with an aqueous hydrochloric acid solution. The precipitate formed was isolated by vacuum filtration and dried.
  • EX/TMPILE 1 "M v 2-Diethoxytlfiophosfioryloxy g 'v 7 A -dihydro-6H-pyrrolo-[ l ,2-a]-pyrimidine-4-one 36 gm of 2-hydroxy-7,8-dihydro-6H-pyrrolo-[l,2-a]- pyrimidine-4-one were placed in suspension in 300 cc of acetone. After homogenization, 28 cc of triethylamine were added, then 35 cc of 0,0-diethy1 chlorothiophosphate were introduced drop by drop. The mixture was agitated at room temperature for forty-eight hours.
  • Step B 2-(o-ethyl NN dimethylthiophosphoramido-oxy)-7,8-dihydro-6H-pyrrolo- [l,2-a]-pyrimidine-4-one 88 gm of a sodium salt of 2-hydroxy-7,8-dihydro-6H- pyrrolo-[ l ,2al-pyrimidine-4-one and 63 cc of ethyl N- dimethyl-thiophosphoramido-chloridate were introduced into 700 cc of acetonitrile. The mixture was heated to reflux for 33 hours. The precipitate formed was eliminated by filtration. The filtrate evaporated to dryness and gm of red oil was obtained.
  • This oil was subjected to chromatography through silica eluting with a cyclohexane-acetone-chloroform mixture (1:1:1) in order to obtain some yellowish crystals which were purified by washing with essence G. 27.5 gm of 2-(O-ethyl-N,N-dimethyl-thiophosphoramido-0xy)- 7,8-dihydro-6H-pyrrolo-[1,2-a]-pyrimidine-4-one were thus obtained melting at 63 C.
  • Step A The sodium salt of 2-hydroxy3-methyl- 7 ,8-dihydro-6H-pyrrolo-[1 ,2-a]-pyrimidine-4-one.
  • Step B 2-Diethoxythiophosphoryloxy-3-methyl- 7,8-dihydro-6H-pyrrolo-[l ,2-a]-pyrimidine4-one.
  • EXAMPLE 8 l,6-Dihydro-4-dimethoxythiophosphoryloxy-azepino- [l,2-a]-pyrimidine-6-one
  • 35 gm of 1,6-dihydro*4-hydroxy-azepino-[l,2-a] pyrimidine-6-one and 27 gm of potassium carbonate were introduced into 350 cc of acetonitrile.
  • 32 gm of 0,0-dimethyl chloro-thiophosphate were then added, and the reaction mixture was agitated for 20 hours at room temperature.
  • the mineral salts were eliminated by filtration.
  • the filtrate was concentrated to dryness by distillation under reduced pressure.
  • EXAMPLE 9 l,6-Dihydro-4diethoxythiophosphoryloxy-azepinoll.2-al-pyrimidine-6-one
  • 35 gm of l,6-dihydro-4-hydroxy-azepino-l1.2-111- pyrimidine-6-one and 27 gm of potassium carbonate were introduced into 350 cc of acetonitrile.
  • 30 cc of .0,0-diethyl chloro-thiophosphate were added thereto.
  • the mixture was agitated for 56 hours at room temperature.
  • the mineral salts were eliminated by filtration.
  • the filtrate was concentrated to dryness by distillation under reduced pressure.
  • a]-pyrimidine-4-one and 27.6 gm of potassium carbonate were introduced into 300 cc of acetone. This mixture was heated to reflux and maintained there for 1 hour, then cooled to 20C. 34.8 gm of O-methyl-O- ethyl chlorothiophosphate were added. The reaction mixture was heated to 40C and maintained at this temperature for 4 hours. The insolubles formed were eliminated by filtration. The filtrate was concentrated to dryness under reduced pressure. The residue was subject to chromatography through silica gel with elution by a mixture of chloroform and acetone (111-). 6.5 gm of 2-(methoxy-ethoxythiophosphoryloxy)-7,8-dihydro- 6H-pyrrolo-[1,2-a]-pyrimidine-4-one were obtained having a melting point of 71C.
  • the first group ofplants was treated by Compound A, 1 ml of solution containing mg of Compound A 5 per liter was sprinkled on each leaf. Each leaf was infested with 20 plant lice and each leaf was encircled with gauze in order to hinder the departure ofthe plant lice.
  • a counting of living and dead insects as that of Carbaryl are expressed as a percentage of the a function of time was made. The results are expressed reduction of the number of living caterpillars. The re- 20 in a percentage of Abbott efficacy (taking into account sults are given in Table III below. the controlled test).
  • n represents an integer from 2 to 3
  • Y represents a member selected from the group consisting of hydrogen, alkyl having one to six carbon atoms, halo and alkylthio having one to six carbon atoms,
  • X represents a member selected from the group consisting of sulfur and oxygen
  • R represents an alkyl having one to four carbon atoms
  • R represents a member selected from the group consisting of alkoxy having one to four carbons atoms, alkoxyalkoxy having one to four carbon atoms alkoxyalkoxy having one to four carbon atoms in each alk, and

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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)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US00288393A 1971-09-16 1972-09-12 Organophosphate ester derivatives of heterocyclic compounds and process Expired - Lifetime US3857838A (en)

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US (1) US3857838A (fr)
JP (1) JPS4836189A (fr)
AU (1) AU466846B2 (fr)
BE (1) BE788828A (fr)
CA (1) CA981671A (fr)
DE (1) DE2245386A1 (fr)
ES (1) ES406728A1 (fr)
FR (1) FR2152469B1 (fr)
GB (1) GB1396169A (fr)
IL (1) IL40323A (fr)
IT (1) IT965384B (fr)
NL (1) NL7212526A (fr)
ZA (1) ZA726212B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3973009A (en) * 1974-05-06 1976-08-03 Stauffer Chemical Company Insecticidal and miticidal method
US4152427A (en) * 1977-01-29 1979-05-01 Bayer Aktiengesellschaft Combating pests with substituted pyrimidinone [(di)-thio]-phosphoric(phosphonic) acid esters and ester-amides
US4472389A (en) * 1981-12-10 1984-09-18 Uniroyal, Inc. Substituted pyrimidinyl organophosphorus insecticides
US4634690A (en) * 1981-12-10 1987-01-06 Uniroyal Chemical Company, Inc. Substituted pyrimidinyl organophosphorus insecticides
US5366969A (en) * 1989-09-09 1994-11-22 Boehringer Mannheim Gmbh Amidine group containing monocycloheteracyclic or bicycloheterocyclic diphosphonic acid derivatives and medicaments containing these compounds
US6228553B1 (en) * 1998-07-14 2001-05-08 Fuji Photo Film Co., Ltd. Pyrrolo [1,2-A] pyrimidine compound and heat-sensitive recording material using the same
US10562663B2 (en) * 2017-02-15 2020-02-18 Creative Impact Inc. Apparatus for housing and revealing a plurality of children's toys

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2198697B1 (fr) * 1972-09-11 1975-09-12 Roussel Uclaf
US4000267A (en) * 1972-09-11 1976-12-28 Roussel-Uclaf Insecticidal and acaricidal compositions employing pyrido[1,2a]pyrimidinone thiophosphates
US4395551A (en) * 1981-12-10 1983-07-26 Uniroyal, Inc. Pyridopyrimidinone compounds

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402176A (en) * 1964-12-24 1968-09-17 Bayer Ag O-pyrazolo-(1, 5-a)-pyrimidyl phosphorus-containing esters

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3402176A (en) * 1964-12-24 1968-09-17 Bayer Ag O-pyrazolo-(1, 5-a)-pyrimidyl phosphorus-containing esters

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3973009A (en) * 1974-05-06 1976-08-03 Stauffer Chemical Company Insecticidal and miticidal method
US4152427A (en) * 1977-01-29 1979-05-01 Bayer Aktiengesellschaft Combating pests with substituted pyrimidinone [(di)-thio]-phosphoric(phosphonic) acid esters and ester-amides
US4472389A (en) * 1981-12-10 1984-09-18 Uniroyal, Inc. Substituted pyrimidinyl organophosphorus insecticides
US4634690A (en) * 1981-12-10 1987-01-06 Uniroyal Chemical Company, Inc. Substituted pyrimidinyl organophosphorus insecticides
US5366969A (en) * 1989-09-09 1994-11-22 Boehringer Mannheim Gmbh Amidine group containing monocycloheteracyclic or bicycloheterocyclic diphosphonic acid derivatives and medicaments containing these compounds
US6228553B1 (en) * 1998-07-14 2001-05-08 Fuji Photo Film Co., Ltd. Pyrrolo [1,2-A] pyrimidine compound and heat-sensitive recording material using the same
US10562663B2 (en) * 2017-02-15 2020-02-18 Creative Impact Inc. Apparatus for housing and revealing a plurality of children's toys
US11192682B2 (en) 2017-02-15 2021-12-07 Zuru (Singapore) Pte. Ltd. Apparatus for housing and revealing a plurality of children's toys

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IL40323A0 (en) 1972-11-28
IT965384B (it) 1974-01-31
IL40323A (en) 1976-03-31
CA981671A (en) 1976-01-13
ZA726212B (en) 1973-10-31
JPS4836189A (fr) 1973-05-28
AU466846B2 (en) 1975-11-13
DE2245386A1 (de) 1973-03-22
ES406728A1 (es) 1975-10-01
AU4674072A (en) 1974-03-21
BE788828A (fr) 1973-03-14
NL7212526A (fr) 1973-03-20
FR2152469B1 (fr) 1974-03-29
GB1396169A (en) 1975-06-04
FR2152469A1 (fr) 1973-04-27

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