US3857838A - Organophosphate ester derivatives of heterocyclic compounds and process - Google Patents
Organophosphate ester derivatives of heterocyclic compounds and process Download PDFInfo
- 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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- US
- United States
- Prior art keywords
- carbon atoms
- dihydro
- pyrimidine
- mixture
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000002148 esters Chemical class 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 title 1
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 PHOSPHATE ESTER Chemical class 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 54
- 125000000217 alkyl group Chemical group 0.000 abstract description 24
- 150000001875 compounds Chemical class 0.000 abstract description 18
- 125000002947 alkylene group Chemical group 0.000 abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 abstract description 9
- 230000000749 insecticidal effect Effects 0.000 abstract description 9
- 230000000895 acaricidal effect Effects 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 125000004414 alkyl thio group Chemical group 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 6
- 239000011593 sulfur Substances 0.000 abstract description 6
- 125000005083 alkoxyalkoxy group Chemical group 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 241000534944 Thia Species 0.000 abstract description 4
- 125000001475 halogen functional group Chemical group 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 49
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 35
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 229910052799 carbon Inorganic materials 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 18
- 238000004587 chromatography analysis Methods 0.000 description 18
- 238000001914 filtration Methods 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 17
- 229940126062 Compound A Drugs 0.000 description 15
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000010992 reflux Methods 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- 239000000741 silica gel Substances 0.000 description 10
- 229910002027 silica gel Inorganic materials 0.000 description 10
- 230000009102 absorption Effects 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 241000238631 Hexapoda Species 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000005947 Dimethoate Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 241001124076 Aphididae Species 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- DNCYBUMDUBHIJZ-UHFFFAOYSA-N 1h-pyrimidin-6-one Chemical compound O=C1C=CN=CN1 DNCYBUMDUBHIJZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 241000255925 Diptera Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241000257159 Musca domestica Species 0.000 description 3
- 244000046052 Phaseolus vulgaris Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 description 3
- 229960005286 carbaryl Drugs 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NOTFZGFABLVTIG-UHFFFAOYSA-N Cyclohexylethyl acetate Chemical compound CC(=O)OCCC1CCCCC1 NOTFZGFABLVTIG-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241000256248 Spodoptera Species 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- HPFKOFNYNQMWEF-UHFFFAOYSA-N chloro-dihydroxy-sulfanylidene-$l^{5}-phosphane Chemical compound OP(O)(Cl)=S HPFKOFNYNQMWEF-UHFFFAOYSA-N 0.000 description 2
- NLCIYDBRSJQKTO-UHFFFAOYSA-N chloroform;cyclohexane;propan-2-one Chemical compound CC(C)=O.ClC(Cl)Cl.C1CCCCC1 NLCIYDBRSJQKTO-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000019695 salad leaves Nutrition 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- NJBMZYSKLWQXLJ-UHFFFAOYSA-N 3,4-dihydro-2h-pyrrol-5-amine Chemical compound NC1=NCCC1 NJBMZYSKLWQXLJ-UHFFFAOYSA-N 0.000 description 1
- YIOSBVGXNFWVER-UHFFFAOYSA-N 7,8-dihydro-6h-pyrrolo[1,2-a]pyrimidin-4-one Chemical compound O=C1C=CN=C2CCCN12 YIOSBVGXNFWVER-UHFFFAOYSA-N 0.000 description 1
- 241001600407 Aphis <genus> Species 0.000 description 1
- 241001425390 Aphis fabae Species 0.000 description 1
- 241000238657 Blattella germanica Species 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 241001249699 Capitata Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000255580 Ceratitis <genus> Species 0.000 description 1
- 241000255579 Ceratitis capitata Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 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 1
- 206010061217 Infestation Diseases 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 102100029909 Peptide YY Human genes 0.000 description 1
- 108010088847 Peptide YY Proteins 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 241000985245 Spodoptera litura Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- BYHUURFQWCMINB-UHFFFAOYSA-N chloro-ethoxy-methoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCOP(Cl)(=S)OC BYHUURFQWCMINB-UHFFFAOYSA-N 0.000 description 1
- OAIVIYSBZFEOIU-UHFFFAOYSA-N chloroform;propan-2-one Chemical compound CC(C)=O.ClC(Cl)Cl OAIVIYSBZFEOIU-UHFFFAOYSA-N 0.000 description 1
- WACQKHWOTAEEFS-UHFFFAOYSA-N cyclohexane;ethyl acetate Chemical compound CCOC(C)=O.C1CCCCC1 WACQKHWOTAEEFS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- BYQFBFWERHXONI-UHFFFAOYSA-N diethyl 2-propan-2-ylpropanedioate Chemical compound CCOC(=O)C(C(C)C)C(=O)OCC BYQFBFWERHXONI-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- UKFXDFUAPNAMPJ-UHFFFAOYSA-N ethylmalonic acid Chemical compound CCC(C(O)=O)C(O)=O UKFXDFUAPNAMPJ-UHFFFAOYSA-N 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- QOLACWFHYSUXPZ-UHFFFAOYSA-N n-[chloro(ethoxy)phosphinothioyl]methanamine Chemical compound CCOP(Cl)(=S)NC QOLACWFHYSUXPZ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- HAOKKJHTFUZWIM-UHFFFAOYSA-N pyridin-1-ium-2-amine;chloride Chemical compound Cl.NC1=CC=CC=N1 HAOKKJHTFUZWIM-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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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- 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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR7133434A FR2152469B1 (de) | 1971-09-16 | 1971-09-16 |
Publications (1)
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US3857838A true US3857838A (en) | 1974-12-31 |
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ID=9083063
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Application Number | Title | Priority Date | Filing Date |
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US00288393A Expired - Lifetime US3857838A (en) | 1971-09-16 | 1972-09-12 | Organophosphate ester derivatives of heterocyclic compounds and process |
Country Status (13)
Country | Link |
---|---|
US (1) | US3857838A (de) |
JP (1) | JPS4836189A (de) |
AU (1) | AU466846B2 (de) |
BE (1) | BE788828A (de) |
CA (1) | CA981671A (de) |
DE (1) | DE2245386A1 (de) |
ES (1) | ES406728A1 (de) |
FR (1) | FR2152469B1 (de) |
GB (1) | GB1396169A (de) |
IL (1) | IL40323A (de) |
IT (1) | IT965384B (de) |
NL (1) | NL7212526A (de) |
ZA (1) | ZA726212B (de) |
Cited By (7)
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)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2198697B1 (de) * | 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)
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 |
-
0
- BE BE788828D patent/BE788828A/xx unknown
-
1971
- 1971-09-16 FR FR7133434A patent/FR2152469B1/fr not_active Expired
-
1972
- 1972-09-07 IL IL40323A patent/IL40323A/en unknown
- 1972-09-12 US US00288393A patent/US3857838A/en not_active Expired - Lifetime
- 1972-09-14 JP JP47091865A patent/JPS4836189A/ja active Pending
- 1972-09-15 CA CA151,877A patent/CA981671A/en not_active Expired
- 1972-09-15 ES ES406728A patent/ES406728A1/es not_active Expired
- 1972-09-15 DE DE2245386A patent/DE2245386A1/de active Pending
- 1972-09-15 NL NL7212526A patent/NL7212526A/xx not_active Application Discontinuation
- 1972-09-15 IT IT52790/72A patent/IT965384B/it active
- 1972-09-15 AU AU46740/72A patent/AU466846B2/en not_active Expired
- 1972-09-15 GB GB4282572A patent/GB1396169A/en not_active Expired
-
1973
- 1973-09-12 ZA ZA726212A patent/ZA726212B/xx unknown
Patent Citations (1)
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)
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 |
Also Published As
Publication number | Publication date |
---|---|
ZA726212B (en) | 1973-10-31 |
GB1396169A (en) | 1975-06-04 |
NL7212526A (de) | 1973-03-20 |
IL40323A0 (en) | 1972-11-28 |
CA981671A (en) | 1976-01-13 |
AU4674072A (en) | 1974-03-21 |
AU466846B2 (en) | 1975-11-13 |
FR2152469A1 (de) | 1973-04-27 |
DE2245386A1 (de) | 1973-03-22 |
BE788828A (fr) | 1973-03-14 |
IL40323A (en) | 1976-03-31 |
IT965384B (it) | 1974-01-31 |
FR2152469B1 (de) | 1974-03-29 |
ES406728A1 (es) | 1975-10-01 |
JPS4836189A (de) | 1973-05-28 |
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