CN101198593B - 制备甲酰胺的方法 - Google Patents
制备甲酰胺的方法 Download PDFInfo
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- CN101198593B CN101198593B CN2006800214752A CN200680021475A CN101198593B CN 101198593 B CN101198593 B CN 101198593B CN 2006800214752 A CN2006800214752 A CN 2006800214752A CN 200680021475 A CN200680021475 A CN 200680021475A CN 101198593 B CN101198593 B CN 101198593B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 150000003857 carboxamides Chemical class 0.000 title claims description 7
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000000370 acceptor Substances 0.000 claims abstract description 6
- -1 C1-C6Haloalkylsulfinyl radical Chemical class 0.000 claims description 106
- 238000000034 method Methods 0.000 claims description 17
- 150000001448 anilines Chemical class 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000004737 (C1-C6) haloalkoxy group Chemical group 0.000 claims description 4
- 125000006771 (C1-C6) haloalkylthio group Chemical group 0.000 claims description 4
- LPZZJKBLKQOBMZ-UHFFFAOYSA-N 2-(4-methylpentan-2-yl)aniline Chemical compound CC(C)CC(C)C1=CC=CC=C1N LPZZJKBLKQOBMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 2
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims description 2
- 125000006798 (C1-C6) haloalkylamino group Chemical group 0.000 claims description 2
- 125000004749 (C1-C6) haloalkylsulfinyl group Chemical group 0.000 claims description 2
- 125000004741 (C1-C6) haloalkylsulfonyl group Chemical group 0.000 claims description 2
- 125000006643 (C2-C6) haloalkenyl group Chemical group 0.000 claims description 2
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 2
- 125000004441 haloalkylsulfonyl group Chemical group 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- YBSBUXVXUOXKOR-UHFFFAOYSA-N 5-fluoro-1,3-dimethylpyrazole Chemical class CC=1C=C(F)N(C)N=1 YBSBUXVXUOXKOR-UHFFFAOYSA-N 0.000 claims 1
- IOGCHBMFOXWVLY-UHFFFAOYSA-N 5-fluoro-1,3-dimethylpyrazole-4-carboxamide Chemical class CC1=NN(C)C(F)=C1C(N)=O IOGCHBMFOXWVLY-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 3
- 230000000855 fungicidal effect Effects 0.000 abstract description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 35
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- FSLWXANTEMFPRQ-UHFFFAOYSA-N 5-fluoro-1,3-dimethylpyrazole-4-carbonyl fluoride Chemical compound CC1=NN(C)C(F)=C1C(F)=O FSLWXANTEMFPRQ-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- NFDXQGNDWIPXQL-UHFFFAOYSA-N 1-cyclooctyldiazocane Chemical compound C1CCCCCCC1N1NCCCCCC1 NFDXQGNDWIPXQL-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000012973 diazabicyclooctane Substances 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 2
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 description 2
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 125000006351 ethylthiomethyl group Chemical group [H]C([H])([H])C([H])([H])SC([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000004372 methylthioethyl group Chemical group [H]C([H])([H])SC([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- GOFJDXZZHFNFLV-UHFFFAOYSA-N 5-fluoro-1,3-dimethyl-N-[2-(4-methylpentan-2-yl)phenyl]pyrazole-4-carboxamide Chemical compound CC(C)CC(C)C1=CC=CC=C1NC(=O)C1=C(F)N(C)N=C1C GOFJDXZZHFNFLV-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000006125 ethylsulfonyl group Chemical group 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-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
- 125000006126 n-butyl sulfonyl group Chemical group 0.000 description 1
- JIKUXBYRTXDNIY-UHFFFAOYSA-N n-methyl-n-phenylformamide Chemical compound O=CN(C)C1=CC=CC=C1 JIKUXBYRTXDNIY-UHFFFAOYSA-N 0.000 description 1
- 125000006124 n-propyl sulfonyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005034 trifluormethylthio group Chemical group FC(S*)(F)F 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
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- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
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Abstract
本发明涉及一种在无酸受体存在的情况下由酰基氟及苯胺衍生物制备相应的已知的、具有杀菌活性的1，3-二甲基-5-氟-1H-吡唑-4-甲酰胺的新方法。
Description
本发明涉及一种在无酸受体存在的情况下由酰基氟及苯胺衍生物制备相应的已知的具有杀菌活性的1，3-二甲基-5-氟-1H-吡唑-4-甲酰胺的新方法。
已知1，3-二甲基-5-氟-1H-吡唑-4-甲酰胺可通过将相应的酰基氟与所需苯胺衍生物进行反应而制得(参见EP-A 0776889)。根据该说明书，优选使用双环叔胺例如二氮杂双环辛烷(DABCO)、二氮杂双环壬烯(DBN)或二氮杂双环十一碳烯(DBU)作为酸受体。与DABCO进行的反应仅提供80％的产率。而且，由于DABCO非常昂贵并且不能够再循环，因此该试剂不适于工业规模的实施。
现已发现式(I)的甲酰胺
其中，
R为C3-C12环烷基、C3-C12环烯基、C6-C12二环烷基、C2-C12氧杂环烷基、C4-C12氧杂环烯基、C3-C12硫杂环烷基、C4-C12硫杂环烯基、C2-C12氮杂环烷基，所述每个基团可被C1-C8烷基、C1-C8烷氧基、卤素和/或氰基相同或不同地任选单取代或多取代，
或者为被相同或不同地任选单取代至五取代的苯基，其中各取代基选自所列W1，
或者为未被取代的C2-C20烷基，
或者为被卤素、C1-C6烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷氧基、C1-C6烷氨基、二(C1-C6烷基)氨基、C1-C6卤代烷硫基、C1-C6卤代烷基亚磺酰基、C1-C6卤代烷基磺酰基、C1-C6卤代烷氧基、C1-C6卤代烷氨基、卤代二(C1-C6烷基)氨基、-SiR1R2R3和/或C3-C6环烷基相同或不同地单取代或多取代的C1-C20烷基，其中环烷基部分可又被卤素、C1-C4烷基和/或C1-C4卤代烷基相同或不同地任选单取代至四取代，
W1为卤素、氰基、硝基、氨基、羟基、C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷基亚磺酰基、C1-C8烷基磺酰基、C2-C6烯基、C2-C6烯氧基；各自具有1-13个相同或不同的卤原子的C1-C6卤代烷基、C1-C6卤代烷氧基、C1-C6卤代烷硫基、C1-C6卤代烷基亚磺酰基或C1-C6卤代烷基磺酰基；各自具有1-11个相同或不同的卤原子的C2-C6卤代烯基或C2-C6卤代烯氧基；C3-C6环烷基或C3-C6环烷氧基；
R1和R2各自独立地为氢、C1-C8烷基、C1-C8烷氧基、C1-C4烷氧基-C1-C4烷基、C1-C4烷硫基-C1-C4烷基或C1-C6卤代烷基，
R3为氢、C1-C8烷基、C1-C8烷氧基、C1-C4烷氧基-C1-C4烷基、C1-C4烷硫基-C1-C4烷基、C2-C8烯基、C2-C8炔基、C1-C6卤代烷基、C2-C6卤代烯基、C2-C6卤代炔基、C3-C6环烷基，或者各自任选被取代的苯基或苯基烷基，
其特征在于
在无酸受体存在的情况下，式(II)的5-氟-1，3-二甲基-1H-吡唑-4-碳酰氟与式(III)的苯胺衍生物反应
其中R如上定义。
令人惊讶的是，在本发明条件下可以良好的产率并以高纯度和高选择性制备式(I)的甲酰胺。由于无需使用酸受体，本发明方法的另一优点为后处理更简便。从而本发明方法也变得更经济可行。此外，可以缩短反应时间。
例如，当5-氟-1，3-二甲基-1H-吡唑-4-碳酰氟与2-(1，3-二甲基丁基)苯胺用作起始原料时，本发明方法可通过下列方案图进行说明：
在本发明方法的实施中，用作起始原料的式(II)的5-氟-1，3-二甲基-1H-吡唑-4-碳酰氟为已知的(参见EP-A 0776889)。
在本发明方法的实施中，也用作起始原料的苯胺衍生物由式(III)进行一般定义。
R优选为C3-C8环烷基、C3-C8环烯基、C6-C10二环烷基、C2-C7氧杂环烷基、C4-C7氧杂环烯基、C3-C7硫杂环烷基、C4-C7硫杂环烯基、C2-C7氮杂环烷基，所述每个基团可被C1-C4烷基、C1-C4烷氧基、氟、氯、溴和/或氰基相同或不同地任选单取代至四取代，
或者为被相同或不同地单取代至三取代的苯基，其中取代基选自所列W1，
或者为未被取代的C2-C12烷基(例如乙基和直链或带有支链的丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基和十二烷基)
或者为被氟、氯、溴、碘、C1-C6烷硫基、C1-C4烷基亚磺酰基、C1-C4烷基磺酰基、C1-C4烷氧基、C1-C4烷氨基、二(C1-C4烷基)氨基，各自具有1-9个氟、氯和/或溴原子的C1-C4卤代烷硫基、C1-C4卤代烷基亚磺酰基、C1-C4卤代烷基磺酰基、C1-C4卤代烷氧基、C1-C4卤代烷氨基、卤代二(C1-C4烷基)氨基，-SiR1R2R3、环丙基、二氯环丙基、环丁基、环戊基或环己基相同或不同地单取代或多取代的C1-C12烷基(例如甲基、乙基及直链或带有支链的丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基和十二烷基)。
R更优选为环戊基、环己基、环庚基、二环[2.2.1]庚基，
或者为在4位单取代的苯基，在3，4位、2，3位、2，4位或3，5位被相同或不同地二取代的苯基，或者在2，4，6位被相同或不同地三取代的苯基，其中各取代基选自所列W1，
或者为未被取代的C3-C10烷基(例如丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1，2-二甲基丙基、1，1-二甲基丙基、2，2-二甲基丙基、1-乙基丙基、正己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1，2-二甲基丁基、1，3-二甲基丁基、2，3-二甲基丁基、1，1-二甲基丁基、2，2-二甲基丁基、3，3-二甲基丁基、1，1，2-三甲基丙基、1，2，2-三甲基丙基、1-乙基丁基、2-乙基丁基、1-乙基-3-甲基丙基、正庚基、1-甲基己基、1-乙基戊基、2-乙基戊基、1-丙基丁基、辛基、1-甲基庚基、2-甲基庚基、1-乙基己基、2-乙基己基、1-丙基戊基、2-丙基戊基、壬基、1-甲基辛基、2-甲基辛基、1-乙基庚基、2-乙基庚基、1-丙基己基、2-丙基己基、癸基、1-甲基壬基、2-甲基壬基、1-乙基辛基、2-乙基辛基、1-丙基庚基和2-丙基庚基)
或者为，该烷基被氟、氯、甲硫基、乙硫基、正丙硫基或异丙硫基、正丁硫基、异丁硫基、仲丁硫基、叔丁硫基、戊硫基、己硫基、甲基磺酰基、乙基磺酰基、正丙基磺酰基或异丙基磺酰基、正丁基磺酰基、异丁基磺酰基、仲丁基磺酰基、叔丁基磺酰基、甲氧基、乙氧基、正丙氧基或异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、甲基氨基、乙基氨基、正丙基氨基或异丙基氨基、正丁基氨基、异丁基氨基、仲丁基氨基、叔丁基氨基、二甲基氨基、二异丙基氨基、三氟甲硫基、三氟甲氧基、-SiR1R2R3、环丙基、二氯环丙基、环丁基、环戊基或环己基相同地或不同地单取代或多取代的C1-C10烷基(例如甲基、乙基、丙基、1-甲基乙基、丁基、1-甲基丙基、2-甲基丙基、1，1-二甲基乙基、正戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1，2-二甲基丙基、1，1-二甲基丙基、2，2-二甲基丙基、1-乙基丙基、正己基、1-甲基戊基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1，2-二甲基丁基、1，3-二甲基丁基、2，3-二甲基丁基、1，1-二甲基丁基、2，2-二甲基丁基、3，3-二甲基丁基、1，1，2-三甲基丙基、1，2，2-三甲基丙基、1-乙基丁基、2-乙基丁基、1-乙基-3-甲基丙基、正庚基、1-甲基己基、1-乙基戊基、2-乙基戊基、1-丙基丁基、辛基、1-甲基庚基、2-甲基庚基、1-乙基己基、2-乙基己基、1-丙基戊基、2-丙基戊基、壬基、1-甲基辛基、2-甲基辛基、1-乙基庚基、2-乙基庚基、1-丙基己基、2-丙基己基、癸基、1-甲基壬基、2-甲基壬基、1-乙基辛基、2-乙基辛基、1-丙基庚基和2-丙基庚基)。
W1 优选为氟、氯、溴、甲基、乙基、正丙基或异丙基、正丁基、异丁基、仲丁基或叔丁基、甲氧基、乙氧基、正丙氧基或异丙氧基、三氟甲基、三氟乙基、二氟甲氧基、三氟甲氧基、二氟氯甲氧基、三氟乙氧基。
W1 更优选为氟、氯或溴。
R1和R2各自独立地优选为C1-C6烷基、C1-C6烷氧基、C1-C3烷氧基-C1-C3烷基或C1-C3烷硫基-C1-C3烷基。
R1和R2各自独立地更优选为甲基、乙基、甲氧基、乙氧基、甲氧基甲基、乙氧基甲基、甲氧基乙基、乙氧基乙基、甲硫基甲基、乙硫基甲基、甲硫基乙基或乙硫基乙基。
R1和R2各自独立地
为甲基、甲氧基、甲氧基甲基或甲硫基甲基。
R1和R2 
各自为甲基。
R3 优选为C1-C6烷基、C1-C6烷氧基、C1-C3烷氧基-C1-C3烷基、C1-C3烷硫基-C1-C3烷基、C3-C6环烷基、苯基或苯甲基。
R3 更优选为甲基、乙基、正丙基或异丙基、正丁基、仲丁基、异丁基或叔丁基、甲氧基、乙氧基、正丙氧基或异丙氧基、正丁氧基、仲丁氧基、异丁氧基或叔丁氧基、甲氧基甲基、乙氧基甲基、甲氧基乙基、乙氧基乙基、甲硫基甲基、乙硫基甲基、甲硫基乙基、乙硫基乙基、环丙基、苯基或苯甲基。
R3 
为甲基、乙基、正丙基或异丙基、异丁基或叔丁基、甲氧基、异丙氧基、异丁氧基或叔丁氧基。
R3 
为甲基。
在本发明方法中优选使用式(III-1)的苯胺衍生物
其中R如上定义。
在本发明方法中还优选使用式(III-2)的苯胺衍生物
其中R如上定义。
在本发明方法中还优选使用式(III-3)的苯胺衍生物
其中R如上定义。
特别优选使用式(III-1)的苯胺衍生物。
式(III)或式(III-1)、(III-2)及(III-3)的苯胺衍生物为已知的或可由已知方式制备(参见EP-A 0776889、WO 03/010149)。
本发明的方法可在稀释剂的存在下进行实施。可用于本发明目的的稀释剂包括所有惰性有机溶剂，优选脂族烃、脂环烃或芳香烃，例如石油醚、己烷、庚烷、环己烷、甲基环己烷、苯、甲苯、二甲苯或十氢化萘；卤代烃类，例如氯苯、二氯苯、二氯甲烷、三氯甲烷、四氯化碳、二氯乙烷或三氯乙烷；醚类，例如二乙醚、二异丙醚、甲基叔丁基醚、甲基·叔戊基醚、二噁烷、四氢呋喃、1，2-二甲氧基乙烷、1，2-二乙氧基乙烷或苯甲醚；酮类，例如丙酮、丁酮、甲基异丁基酮或环己酮；腈类，例如乙腈、丙腈、正丁腈或异丁腈或苄腈；酰胺类，例如N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基甲酰苯胺、N-甲基吡咯烷酮或六甲基磷酰胺，更优选氯苯或甲苯。
实施本发明方法的反应温度可以在一个相对宽泛的范围内变化。通常使用120℃-150℃的温度，优选130℃-140℃的温度。
在本发明方法的实施中，每摩尔式(II)的5-氟-1，3-二甲基-1H-吡唑-4-碳酰氟通常使用0.8-1.5mol、优选等摩尔量的式(III)的苯胺衍生物。
依据反应物的反应活性，反应时间可最高达10小时，但是在完全转化的情况下，反应也可提前终止。优选反应时间5小时。
本发明的所有方法通常在标准压力下实施。但是也可在升高或降低的压力下进行——通常在0.1巴至10巴之间。
可通过本发明方法制备的式(I)的甲酰胺为有价值的杀菌剂(参见例如WO 03/010149)。
本发明的式(I)甲酰胺的制备在以下实施例中进行了描述，该实施例对以上描述进行了进一步的说明。但是，这些实施例不应被理解为限制性的。
制备实施例
在保护气(氩气)下，首先加入溶于40ml氯苯的18.05g(100mmol)2-(1，3-二甲基丁基)苯胺的溶液。加入16.17g(100mmol)5-氟-1，3-二甲基-1H-吡唑-4-碳酰氟并且将该混合物在130℃下再搅拌5h。为进行后处理，将混合物冷却，加入100ml水并且将混合物每次用100ml乙酸乙酯萃取三次。合并的有机相用100ml水洗涤一次，用硫酸镁干燥并在减压下浓缩。将所得100ml悬浮液在室温下再搅拌2h。得到28.2g(理论产量的89％)晶体形式的N-[2-(1，3-二甲基丁基)苯基]-5-氟-1，3-二甲基-1H-吡唑-4-甲酰胺(熔点104-106℃)。
Claims (5)
1.制备式(I)的甲酰胺的方法，
其中
R为C3-C12环烷基、C3-C12环烯基、C6-C12二环烷基、C2-C12氧杂环烷基、C4-C12氧杂环烯基、C3-C12硫杂环烷基、C4-C12硫杂环烯基、C2-C12氮杂环烷基，所述每个基团可被C1-C8烷基、C1-C8烷氧基、卤素和/或氰基相同或不同地任选单取代或多取代，
或者为被相同或不同地任选单取代至五取代的苯基，其中各取代基选自所列W1，
或者为未被取代的C2-C20烷基，
或者为被卤素、C1-C6烷硫基、C1-C6烷基亚磺酰基、C1-C6烷基磺酰基、C1-C6烷氧基、C1-C6烷氨基、二(C1-C6烷基)氨基、C1-C6卤代烷硫基、C1-C6卤代烷基亚磺酰基、C1-C6卤代烷基磺酰基、C1-C6卤代烷氧基、C1-C6卤代烷氨基、卤代二(C1-C6烷基)氨基、-SiR1R2R3和/或C3-C6环烷基相同或不同地单取代或多取代的C1-C20烷基，其中环烷基部分可又被卤素、C1-C4烷基和/或C1-C4卤代烷基相同或不同地任选单取代至四取代，
W1为卤素、氰基、硝基、氨基、羟基、C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、C1-C8烷基亚磺酰基、C1-C8烷基磺酰基、C2-C6烯基、C2-C6烯氧基；各自具有1-13个相同或不同的卤原子的C1-C6卤代烷基、C1-C6卤代烷氧基、C1-C6卤代烷硫基、C1-C6卤代烷基亚磺酰基或C1-C6卤代烷基磺酰基；各自具有1-11个相同或不同的卤原子的C2-C6卤代烯基或C2-C6卤代烯氧基；C3-C6环烷基或C3-C6环烷氧基；
R1和R2各自独立地为氢、C1-C8烷基、C1-C8烷氧基、C1-C4烷氧基-C1-C4烷基、C1-C4烷硫基-C1-C4烷基或C1-C6卤代烷基，
R3为氢、C1-C8烷基、C1-C8烷氧基、C1-C4烷氧基-C1-C4烷基、C1-C4烷硫基-C1-C4烷基、C2-C8烯基、C2-C8炔基、C1-C6卤代烷基、C2-C6卤代烯基、C2-C6卤代炔基、C3-C6环烷基，或者各自任选被取代的苯基或苯基烷基，
其特征在于
在无酸受体存在的情况下，式(II)的5-氟-1，3-二甲基-1H-吡唑
-4-碳酰氟与式(III)的苯胺衍生物反应
其中R如上定义。
2.权利要求1的方法，其特征在于使用120℃-150℃的温度。
3.权利要求1或2的方法，其特征在于使用式(III-1)的苯胺衍生物
其中R如权利要求1中所定义。
4.权利要求3的方法，其特征在于使用2-(1，3-二甲基丁基)苯胺作为式(III)的苯胺衍生物。
5.权利要求1或2的方法，其特征在于使用2-(1，3-二甲基丁基)苯胺作为式(III)的苯胺衍生物。
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| DE102005028293.8 | 2005-06-18 | ||
| DE102005028293A DE102005028293A1 (de) | 2005-06-18 | 2005-06-18 | Verfahren zum Herstellen von Carboxamiden |
| PCT/EP2006/005435 WO2006136287A1 (de) | 2005-06-18 | 2006-06-07 | Verfahren zum herstellen von carboxamiden |
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| EP2920151B1 (en) * | 2012-11-13 | 2017-09-27 | Bayer Cropscience AG | Method for producing carboxamides |
| MX2016012936A (es) | 2014-04-01 | 2016-12-07 | Bayer Cropscience Ag | Proceso para la preparacion de n-[3-(bencilcarbamoil)fenil]-1h-pir azol-5-carboxamidas. |
| CN108358797A (zh) * | 2018-04-20 | 2018-08-03 | 南京农业大学 | 一种烷基甘氨酸的合成方法 |
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| CN1058584A (zh) * | 1990-08-03 | 1992-02-12 | 黑蒙特股份公司 | 有机酯与酰胺的制备方法及所用的催化剂系统 |
| CN1161329A (zh) * | 1995-12-01 | 1997-10-08 | 拜尔公司 | 1，3-二甲基-5-氟吡唑-4-(n-苯基)甲酰胺类化合物的制法 |
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| DE102005009457A1 (de) | 2005-03-02 | 2006-09-07 | Bayer Cropscience Ag | Verfahren zum Herstellen von Alkylaniliden |
| DE102005028294A1 (de) * | 2005-06-18 | 2006-12-21 | Bayer Cropscience Gmbh | Verfahren zum Herstellen von Carboxamiden |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1058584A (zh) * | 1990-08-03 | 1992-02-12 | 黑蒙特股份公司 | 有机酯与酰胺的制备方法及所用的催化剂系统 |
| CN1161329A (zh) * | 1995-12-01 | 1997-10-08 | 拜尔公司 | 1，3-二甲基-5-氟吡唑-4-(n-苯基)甲酰胺类化合物的制法 |
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| JP5007302B2 (ja) | 2012-08-22 |
| IL188174A0 (en) | 2008-03-20 |
| US20090054660A1 (en) | 2009-02-26 |
| KR101336731B1 (ko) | 2013-12-04 |
| EP1902033B1 (de) | 2009-08-12 |
| KR20080027846A (ko) | 2008-03-28 |
| DE102005028293A1 (de) | 2007-01-04 |
| DK1902033T3 (da) | 2009-11-09 |
| ATE439348T1 (de) | 2009-08-15 |
| WO2006136287A1 (de) | 2006-12-28 |
| EP1902033A1 (de) | 2008-03-26 |
| DE502006004527D1 (de) | 2009-09-24 |
| BRPI0612982B1 (pt) | 2015-01-06 |
| US7919632B2 (en) | 2011-04-05 |
| CN101198593A (zh) | 2008-06-11 |
| JP2008546655A (ja) | 2008-12-25 |
| IL188174A (en) | 2011-04-28 |
| BRPI0612982A2 (pt) | 2010-12-14 |
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