CN1037175C - 新的卤代甲基苯甲酰氰类化合物及其制备方法 - Google Patents
新的卤代甲基苯甲酰氰类化合物及其制备方法 Download PDFInfo
- Publication number
- CN1037175C CN1037175C CN94104064A CN94104064A CN1037175C CN 1037175 C CN1037175 C CN 1037175C CN 94104064 A CN94104064 A CN 94104064A CN 94104064 A CN94104064 A CN 94104064A CN 1037175 C CN1037175 C CN 1037175C
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- China
- Prior art keywords
- benzyl
- methyl
- butyl
- cyanides
- cyanide
- 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
- 238000002360 preparation method Methods 0.000 title claims description 13
- 150000002825 nitriles Chemical class 0.000 title abstract description 4
- -1 alkali metal cyanide Chemical class 0.000 claims abstract description 34
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WYXWANVHOUGOBI-UHFFFAOYSA-N 2-methylbenzoyl cyanide Chemical class CC1=CC=CC=C1C(=O)C#N WYXWANVHOUGOBI-UHFFFAOYSA-N 0.000 claims description 12
- GPZXFICWCMCQPF-UHFFFAOYSA-N 2-methylbenzoyl chloride Chemical class CC1=CC=CC=C1C(Cl)=O GPZXFICWCMCQPF-UHFFFAOYSA-N 0.000 claims description 7
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 5
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000005997 bromomethyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000005646 oximino group Chemical group 0.000 claims 2
- 125000006729 (C2-C5) alkenyl group Chemical group 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000001805 chlorine compounds Chemical class 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011814 protection agent Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 150000003053 piperidines Chemical class 0.000 description 13
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 11
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 230000031709 bromination Effects 0.000 description 9
- 238000005893 bromination reaction Methods 0.000 description 9
- 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 9
- 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 9
- ASUDFOJKTJLAIK-UHFFFAOYSA-N 2-methoxyethanamine Chemical compound COCCN ASUDFOJKTJLAIK-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- GJQBHOAJJGIPRH-UHFFFAOYSA-N benzoyl cyanide Chemical compound N#CC(=O)C1=CC=CC=C1 GJQBHOAJJGIPRH-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N anhydrous trimethylamine Natural products CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- TXZFBHYDQGYOIT-UHFFFAOYSA-N 2-(chloromethyl)benzoyl chloride Chemical compound ClCC1=CC=CC=C1C(Cl)=O TXZFBHYDQGYOIT-UHFFFAOYSA-N 0.000 description 4
- NNCLHQHIAYREGO-UHFFFAOYSA-N Cc1cccc(C(=O)C#N)c1Cl Chemical compound Cc1cccc(C(=O)C#N)c1Cl NNCLHQHIAYREGO-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AXWLKJWVMMAXBD-UHFFFAOYSA-N 1-butylpiperidine Chemical class CCCCN1CCCCC1 AXWLKJWVMMAXBD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 2
- ONQBOTKLCMXPOF-UHFFFAOYSA-N 1-ethylpyrrolidine Chemical compound CCN1CCCC1 ONQBOTKLCMXPOF-UHFFFAOYSA-N 0.000 description 2
- GPGKNEKFDGOXPO-UHFFFAOYSA-N 4-phenyl-1h-pyrazole Chemical class C1=NNC=C1C1=CC=CC=C1 GPGKNEKFDGOXPO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FNEQHKCQXDKYEO-UHFFFAOYSA-N N-Benzyl-Pyrrole Natural products C1=CC=CN1CC1=CC=CC=C1 FNEQHKCQXDKYEO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- FQGYCXFLEQVDJQ-UHFFFAOYSA-N mercury dicyanide Chemical compound N#C[Hg]C#N FQGYCXFLEQVDJQ-UHFFFAOYSA-N 0.000 description 2
- VGEMYWDUTPQWBN-UHFFFAOYSA-N n-ethyl-2-methoxyethanamine Chemical compound CCNCCOC VGEMYWDUTPQWBN-UHFFFAOYSA-N 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
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 2
- 229940098221 silver cyanide Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- VEPTXBCIDSFGBF-UHFFFAOYSA-M tetrabutylazanium;fluoride;trihydrate Chemical compound O.O.O.[F-].CCCC[N+](CCCC)(CCCC)CCCC VEPTXBCIDSFGBF-UHFFFAOYSA-M 0.000 description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 2
- 238000009333 weeding Methods 0.000 description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- JRUQXVDEQZLXLV-UHFFFAOYSA-N 1-benzyl-2H-quinoline Chemical compound C1C=CC2=CC=CC=C2N1CC1=CC=CC=C1 JRUQXVDEQZLXLV-UHFFFAOYSA-N 0.000 description 1
- WYANFTXHKVXPFJ-UHFFFAOYSA-N 1-cyclopentylpiperidine Chemical class C1CCCC1N1CCCCC1 WYANFTXHKVXPFJ-UHFFFAOYSA-N 0.000 description 1
- BDVKAMAALQXGLM-UHFFFAOYSA-N 1-ethylpiperidin-4-one Chemical compound CCN1CCC(=O)CC1 BDVKAMAALQXGLM-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- JEVCFPPYJUBGIO-UHFFFAOYSA-N 2-(phenoxymethyl)benzoyl chloride Chemical class ClC(=O)C1=CC=CC=C1COC1=CC=CC=C1 JEVCFPPYJUBGIO-UHFFFAOYSA-N 0.000 description 1
- MIGNJKDTMBBNFI-UHFFFAOYSA-N 2-(phenoxymethyl)benzoyl cyanide Chemical class N#CC(=O)C1=CC=CC=C1COC1=CC=CC=C1 MIGNJKDTMBBNFI-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- NYXWJYYYYZNYKD-UHFFFAOYSA-N 3-cyano-2-methylbenzoyl chloride Chemical compound CC1=C(C#N)C=CC=C1C(Cl)=O NYXWJYYYYZNYKD-UHFFFAOYSA-N 0.000 description 1
- LMRKVKPRHROQRR-UHFFFAOYSA-N 4-butylmorpholine Chemical compound CCCCN1CCOCC1 LMRKVKPRHROQRR-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 238000003482 Pinner synthesis reaction Methods 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 1
- SYLAQKBSMIRLCY-UHFFFAOYSA-N benzyl-butyl-cyclohexyl-ethylazanium Chemical compound C1CCCCC1[N+](CC)(CCCC)CC1=CC=CC=C1 SYLAQKBSMIRLCY-UHFFFAOYSA-N 0.000 description 1
- JARXMPNWSRDOGR-UHFFFAOYSA-N benzyl-dibutyl-ethylazanium Chemical compound CCCC[N+](CC)(CCCC)CC1=CC=CC=C1 JARXMPNWSRDOGR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BEVHTMLFDWFAQF-UHFFFAOYSA-N butyl(triphenyl)phosphanium Chemical class C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 BEVHTMLFDWFAQF-UHFFFAOYSA-N 0.000 description 1
- XTBPKISXEWSOFF-UHFFFAOYSA-N butyl-cyclohexyl-diethylazanium Chemical compound CCCC[N+](CC)(CC)C1CCCCC1 XTBPKISXEWSOFF-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229960002798 cetrimide Drugs 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HXEAALMXXABUTH-UHFFFAOYSA-N chloromethylbenzene oxalonitrile Chemical compound C(C1=CC=CC=C1)Cl.N#CC#N HXEAALMXXABUTH-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- DVJGEFVPCPNKOE-UHFFFAOYSA-N dibenzyl(dibutyl)azanium Chemical compound C=1C=CC=CC=1C[N+](CCCC)(CCCC)CC1=CC=CC=C1 DVJGEFVPCPNKOE-UHFFFAOYSA-N 0.000 description 1
- MPXRTHRNQMUDNH-UHFFFAOYSA-N dibenzyl-cyclohexyl-ethylazanium Chemical compound C=1C=CC=CC=1C[N+](C1CCCCC1)(CC)CC1=CC=CC=C1 MPXRTHRNQMUDNH-UHFFFAOYSA-N 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- VCAVAURZPNANDQ-UHFFFAOYSA-N ethyl-hexadecyl-dimethylazanium Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)CC VCAVAURZPNANDQ-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002367 halogens 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
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Abstract
式ⅠPh-CO-CN卤代甲基苯甲酰氰类化合物的制备方法以及新的卤代甲基苯甲酰氰Ⅰ′。所述方法是使式ⅡPh-CO-Cl的卤代甲基苯甲酰氯类化合物与碱金属氰化物或过渡金属氰化物反应，必要的话，在合适的有机稀释剂中反应。式Ⅰ的卤代甲基苯甲酰氰类化合物是合成植物保护剂的重要中间体。所述式Ⅰ′化合物如下，式中字母意义见说明书中所述。
Description
本发明涉及通式I的卤代甲基苯甲酰氰类化合物的制备方法，
Ph-CO-CN I其中Pb是被氯代甲基或溴代甲基取代的苯基，而且如果必要的话，苯基还可带有1至4个对反应惰性的基团。
苯甲酰氰是可按照公知的方法制备的，特别是通过苯甲酰氯与以下几种物质反应制备：——与氰化汞反应(F.Wler and J.Liebig，Annalen derChemie 3，(1832)249，267)，——与氰化银反应(Liebigs′Annalen der Chemie 287，(1895)，
307)，——与无水氰化铜(I)反应(Org.Synthesis 24，(1944)14)——或在吡啶存在下与无水氰化氢反应(Chem.Ber 31，(1898)
1023).
在EP-A 352543中提到了取代的苯甲酰氰类化合物(见说明书第4页式II和权利要求5)，特别是作为用于除草的4-苯基吡唑类化合物的可能的起始物质(见说明书第10页反应路线(4))。但该专利未给出制备这些苯甲酰氰类化合物的方法，除了苯甲酰氰类化合物的通式外，甚至未公开一个具体的化合物。
DE-A 4042282公开了2-苯氧甲基苯甲酰氰类化合物的制备方法，通过2-苯氧甲基苯甲酰氯类化合物与碱金属氰化物或碱土金属氰化物反应，必要的话在氢氰酸存在下反应。但是该方法看来不适合用于制备卤代甲基苯甲酰氰类化合物(I)，因为按照Houben-Weyl，Methoden der Organischen Chemie(有机化学方法)，卷VIII，第4版，Georg Thieme Verlay，Stuttgart 1952，第294页，芳环上的α-卤代烷基侧链非常易于与碱金属氰化物反应。关于这一点通过实例给出了苄基氯与***的反应。还可以参见无水条件下，在150℃，苄基氯与氰化铜(I)的反应，见J.Am.Chem.Soc.68，(1946)2741。
按照类似于Houben-Weyl的方法，在卤代甲基苯甲酰氯II类化合物与碱金属氰化物或过渡金属氰化物的反应中，相应地可预期得到氰基甲基苯甲酰氯和卤代甲基苯甲酰氰产物的混合物。
本发明的一个目的是提供制备化合物I的可工业化应用的方法。
我们已发现该目的可通过本发明中制备卤代甲基苯甲酰氰类化合物的方法得以实现，该方法包括使式II的卤代甲基苯甲酰氯与碱金属氰化物或过渡金属氰化物反应。
所述式II为：
Ph-CO-Cl II
卤代甲基苯甲酰氯类化合物II可通过已知的卤化方法由相应的甲基取代的苯衍生物(参见例如DE-A2835440)或由相应的苯甲酸类化合物(参见例如DE-A 4042282)制得：
本发明方法通常推荐在大气压或轻微减压条件下进行，反应温度为(-20)至100℃，优选0至80℃，特别是20至80℃。
在碱金属氰化物中优选***和***。在过渡金属氰化物中，合适的有，例如氰化汞(I)、氰化银并优选氰化铜(I)。
通常使用大约化学计量量的卤代甲基苯甲酰氯II和碱金属氰化物或过渡金属氰化物。然而，基于II的量计算，氰化物最好过量不超过2倍，特别优选1.05至1.5倍。
如果使用的卤代甲基苯甲酰氯II不是以液态存在，则需要加入惰性有机溶剂或稀释剂，特别合适的是质子惰性偶极溶剂或非极性溶剂。
质子惰性偶极溶剂应理解为是指溶剂分子具有一定偶极矩，但不带有能够形成氢桥的氢原子的溶剂，该类溶剂的介电常数大于15。可参见A.J.Parker，Chem.Rev.69(1969)，第1-32页，特别是第2页关于质子惰性偶极溶剂的定义。
合适的质子惰性偶极溶剂是，例如：亚砜类例如二甲亚砜、二乙基亚砜，二甲基砜、二乙基砜、甲基乙基砜和环丁砜；腈类例如乙腈、苄腈、丁腈、异丁腈和间氯苄氰；N，N-二烷基取代的酰胺类例如二甲基甲酰胺、四甲基脲、N，N-二甲基苯甲酰胺、N，N-二甲基乙酰胺、N，N-二甲基苯乙酰胺、N，N-二甲基环己烷甲酰胺、N，N-二甲基丙酰胺及同系N-酰基哌啶(Carboxylic acid piperidide)、N-酰基吗啉(Carboxylic acid morpholide)、N-酰基吡咯烷(Carboxylic acidpyrrolidide)上述N，N-二甲基化合物相应的N，N-二乙基、N，N-二丙基、N，N-二异丙基、N，N-二异丁基、N，N-二苄基、N，N-二苯基、N-甲基-N-苯基-、N-环己基-N-甲基和N-乙基-N-叔丁基化合物，以及N-甲基甲酰胺、N-乙基吡咯烷酮、N-丁基吡咯烷酮、N-乙基-4-哌啶酮、N-甲基吡咯烷酮和六甲基磷酰胺。上述溶剂的混合物也是合适的。
优选二甲基乙酰胺、N-甲基吡咯烷酮、二甲基甲酰胺、二甲亚砜、环丁砜、丙酮和乙腈。
合适的非极性溶剂优选芳烃类，例如苯、甲苯、邻二甲苯、间二甲苯、对二甲苯，卤代烃类，例如二氯甲烷和醇类例如甲醇和乙醇。特别优选甲苯。
本方法过程通过加入催化剂可顺利地进行。基于II的量计算，0.005至2倍量，特别是0.01至0.5倍量的催化剂就足够了。
用于该目的的适合的催化剂通常是四级氮化合物的卤化物、氰化物、氢氧化物、硫酸氢盐、C1-C4烷基硫酸盐和四氟硼酸盐和卤化芳基鏻及卤化烷基鏻；例如：
卤化四(C1-C4烷基)铵，例如氯化四乙铵、溴化四乙铵、溴化四丙铵、氯化四丁铵、溴化四丁铵、碘化四丁铵、溴化四辛铵、氯化三丁基甲铵、溴化十六烷基三甲铵、氯化十六烷基三甲铵溶液、溴化乙基十六烷基二甲铵、氯化甲基三辛基铵，
下列铵、哌啶鎓和吗啉鎓离子，与乙基硫酸盐或溴反离子所形成的盐：
环己基二乙基正丁基铵，
氯化(C1-C6烷基)苄基二甲铵，
溴化苄基三丁基铵，
氯化苄基三丁基铵，
氯化苄基三乙基铵，
氯化苄基三甲基铵，
苄基环己基二乙基铵，
苄基-二正丙基乙基铵，
苄基-二正丁基乙基铵，
苄基丁基环己基乙基铵，
丁基二(甲氧乙基)乙基铵，
苄基二(甲氧乙基)乙基铵，
二苄基二正丙基铵，
二苄基二正丁基铵，
二正丁基二(甲氧乙基)铵，
苄基正丁基二(甲氧乙基)铵
二苄基二(甲氧乙基)铵，
N-(正丁基)-N-乙基哌啶鎓，
N-苄基-N-乙基哌啶鎓，
4-(正丁基)-4-乙基吗啉鎓，
4-苄基-4-乙基吗啉鎓，
N-二(正丁基)哌啶鎓，
N-苄基-N-(正丁基)哌啶鎓，
4-二(正丁基)吗啉鎓，
4-苄基-4-(正丁基)吗啉鎓，
环己基二苄基乙基铵，
N，N-二(正丁基)六亚甲基亚铵，
N-苄基-N-(正丁基)六亚甲基亚铵
N，N-二苄基六亚甲基亚铵
N，N-二苄基哌啶鎓
4，4-二甲基吗啉鎓，
N，N-二(正丁基)吡咯烷鎓
N-苄基-N-(正丁基)吡咯烷鎓
N，N-二苄基吡咯烷鎓
N-苄基-N-己基哌啶鎓
N-苄基-N-(2-甲基戊基)哌啶鎓，
N-苄基-N-(2-乙基己基)哌啶鎓，
1，1-二正丁基-2-乙基哌啶，
1-苄基-1-正丁基-2-乙基哌啶，
4-苄基-4-己基吗啉鎓，
4-(正丁基)-4-己基吗啉鎓，
4-苄基-4-(2-乙基己基)吗啉鎓，
N-(正丁基)-N-异丁基六亚甲基亚铵，
N-苄基-N-异丁基六亚甲基亚铵，
N-异戊基-N-苄基六亚甲基亚铵，
N-苄基-N-(正丁基)-3，3，5-三甲基六亚甲基亚铵，
N-苄基-N-(2-甲基丁基)哌啶鎓，
N-苄基-N-(3-甲基丁基)哌啶鎓，
N-苄基-N-(2-甲基-3-甲基丁基)哌啶鎓，
N-环戊基哌啶鎓，
N-苄基-N-(2-甲基-3-乙氧基丙基)哌啶鎓，
环己基二乙基-(正丁基)铵，
4-苄基-4-(2-甲戊基)吗啉鎓，
1-苄基-1-(正丁基)-2-(正丁基)-2-乙基哌啶鎓，
N-苄基-N-乙基六亚甲基亚铵，
N-苄基-N-(2-甲戊基)六亚甲基亚铵，
N-苄基-N-(3，5-二甲基-5-甲基己基)六亚甲基亚铵，
N-苄基-N-(2-甲基戊基)-3，3，5-三甲基六亚甲基亚铵，
N-苄基-N-(2-乙基己基)-3，3，5-三甲基六亚甲基亚铵，
N-苄基-N-环己基六亚甲基亚铵，
N-苄基-N-(2-甲基-2-甲氧基乙基)六亚甲基亚铵，
N-苄基-N-(2-甲基-2-正丁氧基乙基)六亚甲基亚铵，
N-苄基-N-[2-甲基-2-(2-甲氧基乙氧基)乙基]六亚甲基亚铵，
N-苄基-N-(2，5-二甲基-2-丙氧基乙基)六亚甲基亚铵，
N-苄基-N-(2-甲基-3-甲基丁基)-3，3，5-三甲基六亚甲基亚铵，
N-苄基-N-(四氢吡喃-2-基甲基)哌啶鎓，
N-苄基-N-(2-甲基-2-甲氧基乙基)哌啶鎓，
N-苄基-N-(2-甲基-2-正丁氧基乙基)哌啶鎓，
N-苄基-N-[2-甲基-2-(2-甲氧基乙氧基)乙基]哌啶鎓，
N-苄基-N-(4，4-二甲基戊基)哌啶鎓，
N-苄基-N-(四氢吡喃-2-基甲基)六亚甲基亚铵，
N-苄基-N-(2-甲基-3-甲基丁基)六亚甲基亚铵，
N-苄基-N-(2-甲基-3-甲基丁基)吡咯烷鎓，
4-苄基-4-(2-甲基-3-甲基丁基)吗啉鎓，
N-苄基-N-(正丙基)六亚甲基亚铵，
N-苄基-N-(异丙基)六亚甲基亚铵，
正丁基-(2-甲基丁基)-二(2-甲氧基乙基)铵，
苄基-(2-甲基丁基)-二(2-甲氧基乙基)铵，
(双-乙基丁基苄基铵)己烷，
正丁基-(3-甲基丁基)-二(2-甲氧基乙基)铵，
N-苄基-(3-甲基丁基)-二(2-甲氧基乙基)铵，
1，ω-二(N-乙基-六亚甲基亚铵)己基，
1，ω-二(N-苄基-六亚甲基亚铵)己基，
1，ω-二(N-正丁基-六亚甲基亚铵)己基，
1，ω-二(N-乙基六亚甲基亚铵)辛基，
1，ω-二(N-苄基六亚甲基亚铵)辛基，
1，ω-二(N-正丁基六亚甲基亚铵)辛基，
1，ω-二(N-乙基哌啶鎓)己基，
1，ω-二(N-苄基哌啶鎓)己基，
1，ω-二(N-正丁基哌啶鎓)己基，
1，ω-二(N-乙基哌啶鎓)辛基，
1，ω-二(N-苄基哌啶鎓)辛基，
1，ω-二(N-正丁基哌啶鎓)辛基，
1，ω-二(N-乙基吡咯烷鎓)己基，
1，ω-二(N-苄基吡咯烷鎓)己基，
1，ω-二(N-正丁基吡咯烷鎓)己基，
1，ω-二(N-乙基吡咯烷鎓)辛基，
1，ω-二(N-苄基吡咯烷鎓)辛基，
1，ω-二(N-正丁基吡咯烷鎓)辛基，
二丁基乙基苯乙基铵
正丁基-2-甲基丁基-二(2-甲氧基乙基)铵，
二(2-甲氧基乙基)-二(正丙基)铵，
二(2-甲氧基乙基)二戊基铵，
(-)-N-苄基喹宁盐酸盐
(-)-N-十二烷基-N-甲基麻黄素氢溴酸盐，
氰化四(C1-C4烷基)铵例如氰化四乙铵、氰化四丁铵，以及氢氧化四乙铵溶液、氢氧化四丁铵溶液、氢氧化苄基三乙铵溶液、氢氧化苄基三甲铵溶液、氢氧化苄基三乙铵溶液、氟化四丁铵三水合物、四丁铵硫酸氢盐、四丁铵四氟硼酸盐、四乙铵氟硼酸盐，
烷基或芳基取代的卤化鏻，例如溴化乙基三辛基鏻、溴化三丁基十六烷基鏻、溴化四丁基鏻、氯化四丁基鏻溶液、氯化丁基三苯基鏻、溴化四苯基鏻和氯化四苯基鏻。
按照近期发现，氯化四丁铵、溴化四丁铵和氰化四烷基铵是特别合适的，优选使用其50％重量浓度的水溶液。
如果碱金属氰化物在水溶液中，且卤代甲基苯甲酰氯II在有机相中，建议通过加入相转移催化剂来加速反应。
特别适合于此目的的相转移催化剂是诸如苯并-15-冠醚-5，三[2-(2-甲氧基乙氧基)乙基]胺、二环己基-18-冠醚-6和18-冠醚-6-四羧酸之类的冠醚。
所述相转移催化剂的用量以0.001至1mol％，特别是0.001至0.08mol％为宜(基于II的量计算)。
本发明方法可以间歇式或连续式进行。在连续性方法中，例如反应组分可通过一个管式反应器或搅拌的串联器。本发明产物I可按常规方法纯化，例如通过蒸馏方法。
按照本发明方法，卤代甲基苯甲酰氰类化合物I可以以高纯度和技术上简单易行的方法得到。在制备2-卤代甲基苯甲酰氰类化合物过程中作为副产物得到的2-卤代甲基苯甲酸可转化成2-苯并[C]呋喃酮，该化合物可再用于制备II。
对于目标产物I，Ph优选为下式基团：
在本发明方法产物I和式I′的新的卤代甲基苯甲酰氰类化合物中，
X为卤素特别是氟或氯，C1-C4烷基特别是甲基或乙基，C1-C4烷氧基特别是甲氧基、乙氧基或异丙氧基，C1-C4卤代烷基特别是三氟甲基，-C(C1-C5烷基)＝N-O-(C1-C5烷基)或-C(C1-C5烷基)＝N-O-(C2-C5链烯基)，特别是甲氧亚氨基和-C(CH3)＝N-OC3；
m是0至4，优选0。
Y是氯甲基或溴甲基，优选在2位，特别优选氯甲基。
卤代甲基苯甲酰氰类化合物I和I′是制备各种植物保护剂的有用的中间体，例如除草的4-苯基吡唑类化合物，见EP-A352543所述。
本方法产物I和I′还可用于合成芳基二羟乙酸酯，见DE-A4042271所述。其中所述的由Pinner反应获得的苯基二羟乙酸酯及其酮缩醇的粗产物混合物可按DE-A4042272所述不经进一步纯化转化成苯基二羟乙酸酯的E-肟醚，见下式：
其中Ar是取代的或未取代的苯基。式III化合物可用作植物保护中的杀真霉剂、杀螨剂或杀虫剂(例如参见EP-A253213和EP-A254426)
制备实施例实施例1：
在水/甲苯中相转移条件下制备2-氯代甲基苯甲酰氰
将1g(3mmol)溴化四丁铵加入到117.6g(2.4mol)***在400g水中的溶液中。然后将所得混合物用大约200g 1％重量浓度的盐酸调至pH10.5，然后加入1000g甲苯。用大约30分钟时间，将378g(2.0mol)2-氯代甲基苯甲酰氯在1000ml甲苯中的溶液量入该两相混合物中。
在25-35℃搅拌约2-3小时后，分相。有机相用200ml水和200ml1％重量浓度盐酸各洗涤一次，然后用硫酸镁干燥并浓缩。粗产物用分馏方法纯化(b.P.100℃，0.3毫巴)。产量：292.34g(82％)。实施例2：
在乙腈/水中制备2-氯代甲基苯甲酰氰
将9.45g(0.05mol)2-氯代甲基苯甲酰氯在100ml水润湿的乙腈中的溶液用4.9g(0.1mol)***处理，然后将反应混合物在大约25-30℃搅拌24小时。HPLC分析表明混合物中19％为2-苯并[C]呋喃酮和2-氯代甲基苯甲酸，76％为2-氯代甲基苯甲酰氰及5％为二聚苯甲酰氰。
可通过硅胶色谱或分馏(见实施例1)分离粗产物。
产量：6.3g(70.5％)，b.p.0.3＝100℃。实施例3：
使用CuCN制备2-氯代甲基苯甲酰氰
将9.5g(0.05mol)2-氯代甲基苯甲酰氯在100ml乙腈中的溶液用8.9g(0.1mol)氰化铜(I)处理，然后将反应混合物在约0℃搅拌24小时。HPLC分析表明24％为2-苯并[c]呋喃酮，62％为2-氯代甲基苯甲酰氯，约10％为二聚苯甲酰氰。
可通过硅胶色谱(洗脱剂∶己烷/甲苯＝1∶1)或分馏(见实施例1所述)分离反应混合物，(b.p.0.5＝106℃)。产量：5.27g(58％)。
Claims (6)
1.下式I′的卤代甲基苯甲酰氰，其中：
X为卤素、C1-C4烷基、C1-C4烷氧基、三氟甲基、C1-C5烷基-(C1-C5烷基)羟亚氨基或C1-C5烷基(C2-C5链烯基)羟亚氨基；
m是0至4；
Y为氯代甲基或溴代甲基。
2.权利要求1的式I′的卤代甲基苯甲酰氰，其中Y为2-氯代甲基，m为0。
3.权利要求1的式I′的卤代甲基苯甲酰氰的制备方法，其特征在于使下式II′的卤代甲基苯甲酰氯与碱金属氰化物或过渡金属氰化物反应
其中x、m和Y的定义同权利要求1。
4.权利要求3的方法，其中所述反应在有机稀释剂中进行。
5.权利要求3的方法，其中所述反应在催化剂存在下在有机稀释剂中进行。
6.权利要求3的方法，其中所述的式II′化合物在相转移催化剂存在下，在有机稀释剂中与***或***水溶液反应。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4311722.8 | 1993-04-08 | ||
| DE4311722A DE4311722C1 (de) | 1993-04-08 | 1993-04-08 | Verfahren zur Herstellung von Halogenmethyl-benzoylcyaniden und neue Halogenmethyl-benzoylcyanide |
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| CN1097412A CN1097412A (zh) | 1995-01-18 |
| CN1037175C true CN1037175C (zh) | 1998-01-28 |
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| US (2) | US5446199A (zh) |
| EP (1) | EP0619300B1 (zh) |
| JP (2) | JP3811507B2 (zh) |
| KR (1) | KR100310591B1 (zh) |
| CN (1) | CN1037175C (zh) |
| AT (1) | ATE146773T1 (zh) |
| CA (1) | CA2120081C (zh) |
| DE (2) | DE4311722C1 (zh) |
| DK (1) | DK0619300T3 (zh) |
| HU (1) | HU214952B (zh) |
| IL (1) | IL109077A (zh) |
| PL (1) | PL177244B1 (zh) |
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| DE4412316A1 (de) * | 1994-04-11 | 1995-10-12 | Basf Ag | Verfahren zur Herstellung von o-Chlormethylbenzoesäurechloriden |
| NZ296534A (en) * | 1994-11-24 | 1999-01-28 | Basf Ag | Preparation of halomethylbenzoyl cyanides |
| DE102005027149A1 (de) * | 2005-06-11 | 2006-12-14 | Lanxess Deutschland Gmbh | Verfahren zur Herstellung von substituierten Benzoylcyaniden |
| WO2007072679A1 (ja) * | 2005-12-20 | 2007-06-28 | Sumitomo Chemical Company, Limited | ２，４－ジフルオロニトロベンゼンの製造方法 |
| BRPI1005352A2 (pt) | 2009-02-05 | 2016-02-10 | Basf Se | processos para a produção de derivados do ácido 2-halogenometilfenil acético, processo para a produção de uma alquiloxima, processo para a produção de uma oxima, uso de 3-isocromanona e processo para a produção de um de um fungicida estrobilurina |
| CN113880729B (zh) * | 2021-10-29 | 2024-04-26 | 邯郸市瑞田农药有限公司 | 催化剂催化合成苯甲酰氰制备方法 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4238413A (en) * | 1979-11-07 | 1980-12-09 | Hooker Chemicals & Plastics Corp. | (3-Trifluoromethyl)-benzoyl cyanide and process for its production |
| EP0398783A1 (fr) * | 1989-05-19 | 1990-11-22 | Elf Atochem S.A. | Procédé de synthèse de cyanures d'acyle |
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| FR1563737A (zh) * | 1967-12-08 | 1969-04-18 | ||
| DE2614241C3 (de) * | 1976-04-02 | 1980-03-20 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Acylcyaniden |
| DE2717075A1 (de) * | 1977-04-18 | 1978-10-26 | Degussa | Verfahren zur herstellung von benzoylcyanid |
| DE2753656C2 (de) * | 1977-12-02 | 1982-11-25 | Degussa Ag, 6000 Frankfurt | Verfahren zur Herstellung von Benzoylcyanid |
| DE2835440A1 (de) * | 1978-08-12 | 1980-02-28 | Dynamit Nobel Ag | Verfahren zur herstellung von chlormethyl-benzoylchloriden |
| DE3226425A1 (de) * | 1981-11-11 | 1983-05-19 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von acylcyaniden |
| DE3340933A1 (de) * | 1983-11-11 | 1985-05-23 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von (alpha)-ketonitrilen |
| DE3341306A1 (de) * | 1983-11-15 | 1985-05-23 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von in 2-stellung aromatisch oder heterocyclisch substituierten acetonitrilen |
| USRE33989E (en) * | 1986-07-16 | 1992-07-07 | Basf Aktiengesellschaft | Oxime ethers and fungicides containing these compounds |
| GB8617648D0 (en) * | 1986-07-18 | 1986-08-28 | Ici Plc | Fungicides |
| FR2629080B1 (fr) * | 1988-03-25 | 1990-11-16 | Poudres & Explosifs Ste Nale | Procede de preparation d'isocyanates d'acyle |
| US4986845A (en) * | 1988-07-15 | 1991-01-22 | Nissan Chemical Industries Ltd. | Pyrazole derivatives and herbicides containing them |
| US5352827A (en) * | 1989-05-19 | 1994-10-04 | Atochem | Synthesis of acyl cyanides in a hydrous reaction medium |
| EP0718279B1 (de) * | 1990-12-31 | 1997-09-24 | Basf Aktiengesellschaft | Verfahren zur Herstellung von o-substituierten Benzoylcyaniden |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4238413A (en) * | 1979-11-07 | 1980-12-09 | Hooker Chemicals & Plastics Corp. | (3-Trifluoromethyl)-benzoyl cyanide and process for its production |
| EP0398783A1 (fr) * | 1989-05-19 | 1990-11-22 | Elf Atochem S.A. | Procédé de synthèse de cyanures d'acyle |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE146773T1 (de) | 1997-01-15 |
| EP0619300B1 (de) | 1996-12-27 |
| PL177244B1 (pl) | 1999-10-29 |
| HUT66608A (en) | 1994-12-28 |
| JPH06321886A (ja) | 1994-11-22 |
| EP0619300A3 (de) | 1995-03-29 |
| CA2120081A1 (en) | 1994-10-09 |
| IL109077A (en) | 1998-06-15 |
| HU214952B (hu) | 1998-08-28 |
| CA2120081C (en) | 2004-12-28 |
| US5510528A (en) | 1996-04-23 |
| JP2006188531A (ja) | 2006-07-20 |
| IL109077A0 (en) | 1994-06-24 |
| DE59401372D1 (de) | 1997-02-06 |
| US5446199A (en) | 1995-08-29 |
| DE4311722C1 (de) | 1994-04-07 |
| KR100310591B1 (ko) | 2002-07-27 |
| HU9400996D0 (en) | 1994-06-28 |
| CN1097412A (zh) | 1995-01-18 |
| EP0619300A2 (de) | 1994-10-12 |
| DK0619300T3 (zh) | 1997-02-24 |
| JP3811507B2 (ja) | 2006-08-23 |
| JP4096045B2 (ja) | 2008-06-04 |
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