JPH0152A - Fluorobenzoic acid ester and its manufacturing method - Google Patents
Fluorobenzoic acid ester and its manufacturing methodInfo
- Publication number
- JPH0152A JPH0152A JP62-155039A JP15503987A JPH0152A JP H0152 A JPH0152 A JP H0152A JP 15503987 A JP15503987 A JP 15503987A JP H0152 A JPH0152 A JP H0152A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acid ester
- fluorobenzoic acid
- alkyl group
- general formula
- 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.)
- Granted
Links
- -1 Fluorobenzoic acid ester Chemical class 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 150000004714 phosphonium salts Chemical group 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000003983 crown ethers Chemical class 0.000 claims description 9
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 10
- 239000012948 isocyanate Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 235000003270 potassium fluoride Nutrition 0.000 description 5
- 239000011698 potassium fluoride Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- VENGGGZJFDLMED-UHFFFAOYSA-M 1-(2-ethylhexyl)-n,n-dimethylpyridin-1-ium-4-amine;chloride Chemical compound [Cl-].CCCCC(CC)C[N+]1=CC=C(N(C)C)C=C1 VENGGGZJFDLMED-UHFFFAOYSA-M 0.000 description 2
- QMCPTPOMEYEVJS-UHFFFAOYSA-N 2,2-dimethylpropyl 2-fluorobenzoate Chemical compound CC(C)(C)COC(=O)C1=CC=CC=C1F QMCPTPOMEYEVJS-UHFFFAOYSA-N 0.000 description 2
- JFATYAUAICAXNZ-UHFFFAOYSA-N 2,2-dimethylpropyl 3,5-dichloro-2,4-difluorobenzoate Chemical compound CC(C)(C)COC(=O)C1=CC(Cl)=C(F)C(Cl)=C1F JFATYAUAICAXNZ-UHFFFAOYSA-N 0.000 description 2
- NSTREUWFTAOOKS-UHFFFAOYSA-N 2-fluorobenzoic acid Chemical class OC(=O)C1=CC=CC=C1F NSTREUWFTAOOKS-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MQSFWQYRNBDUCO-UHFFFAOYSA-N ethyl 3,5-dichloro-4-fluorobenzoate Chemical compound CCOC(=O)C1=CC(Cl)=C(F)C(Cl)=C1 MQSFWQYRNBDUCO-UHFFFAOYSA-N 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- ITBPSZBIEAPMPR-UHFFFAOYSA-N 1,3-dichloro-2,4-difluoro-5-isocyanatobenzene Chemical compound FC1=C(Cl)C=C(N=C=O)C(F)=C1Cl ITBPSZBIEAPMPR-UHFFFAOYSA-N 0.000 description 1
- KBSGMGUUKUTGES-UHFFFAOYSA-M 1-(2,2-dimethylpropyl)-n,n-dihexylpyridin-1-ium-4-amine;bromide Chemical compound [Br-].CCCCCCN(CCCCCC)C1=CC=[N+](CC(C)(C)C)C=C1 KBSGMGUUKUTGES-UHFFFAOYSA-M 0.000 description 1
- AJQZWCXWWBADOK-UHFFFAOYSA-M 1-(2,2-dimethylpropyl)-n,n-dihexylpyridin-1-ium-4-amine;chloride Chemical compound [Cl-].CCCCCCN(CCCCCC)C1=CC=[N+](CC(C)(C)C)C=C1 AJQZWCXWWBADOK-UHFFFAOYSA-M 0.000 description 1
- BGCATFIAPJHHAF-UHFFFAOYSA-M 1-(2,2-dimethylpropyl)-n,n-dimethylpyridin-1-ium-4-amine;bromide Chemical compound [Br-].CN(C)C1=CC=[N+](CC(C)(C)C)C=C1 BGCATFIAPJHHAF-UHFFFAOYSA-M 0.000 description 1
- OTCQGJASYOVVCB-UHFFFAOYSA-M 1-(2,2-dimethylpropyl)-n,n-dimethylpyridin-1-ium-4-amine;chloride Chemical compound [Cl-].CN(C)C1=CC=[N+](CC(C)(C)C)C=C1 OTCQGJASYOVVCB-UHFFFAOYSA-M 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- OYGHNTBGRXACPB-UHFFFAOYSA-M 1-(2-ethylhexyl)-n,n-dihexylpyridin-1-ium-4-amine;bromide Chemical compound [Br-].CCCCCCN(CCCCCC)C1=CC=[N+](CC(CC)CCCC)C=C1 OYGHNTBGRXACPB-UHFFFAOYSA-M 0.000 description 1
- QYQDDZDSBBGSKN-UHFFFAOYSA-M 1-(2-ethylhexyl)-n,n-dihexylpyridin-1-ium-4-amine;chloride Chemical compound [Cl-].CCCCCCN(CCCCCC)C1=CC=[N+](CC(CC)CCCC)C=C1 QYQDDZDSBBGSKN-UHFFFAOYSA-M 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- JWLUXKDDQJWZAN-UHFFFAOYSA-N 2,2-dimethylpropyl 2,3,4,5-tetrachlorobenzoate Chemical compound CC(C)(C)COC(=O)C1=CC(Cl)=C(Cl)C(Cl)=C1Cl JWLUXKDDQJWZAN-UHFFFAOYSA-N 0.000 description 1
- WIUURYDOGGLACM-UHFFFAOYSA-N 2,2-dimethylpropyl 2-chlorobenzoate Chemical compound CC(C)(C)COC(=O)C1=CC=CC=C1Cl WIUURYDOGGLACM-UHFFFAOYSA-N 0.000 description 1
- QACVZTLSNLCYCB-UHFFFAOYSA-N 2,2-dimethylpropyl 3,5-dichloro-4-fluorobenzoate Chemical compound CC(C)(C)COC(=O)C1=CC(Cl)=C(F)C(Cl)=C1 QACVZTLSNLCYCB-UHFFFAOYSA-N 0.000 description 1
- IROWIXYGGPOJFJ-UHFFFAOYSA-N 2,3,4,5-tetrachlorobenzoyl chloride Chemical compound ClC(=O)C1=CC(Cl)=C(Cl)C(Cl)=C1Cl IROWIXYGGPOJFJ-UHFFFAOYSA-N 0.000 description 1
- QQEJNPVDHGNRMO-UHFFFAOYSA-N 2,6-dichloro-n-[(3,5-dichloro-2,4-difluorophenyl)carbamoyl]benzamide Chemical compound FC1=C(Cl)C(F)=C(Cl)C=C1NC(=O)NC(=O)C1=C(Cl)C=CC=C1Cl QQEJNPVDHGNRMO-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- VWNMVYACOKCDLR-UHFFFAOYSA-N 3,5-dichloro-2,4-difluorobenzoyl fluoride Chemical compound FC(=O)C1=CC(Cl)=C(F)C(Cl)=C1F VWNMVYACOKCDLR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- PJHUABJTDFXYRQ-UHFFFAOYSA-N benzoyl azide Chemical compound [N-]=[N+]=NC(=O)C1=CC=CC=C1 PJHUABJTDFXYRQ-UHFFFAOYSA-N 0.000 description 1
- WCHPXAFAEZGCMB-UHFFFAOYSA-M benzyl(tributyl)phosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CC1=CC=CC=C1 WCHPXAFAEZGCMB-UHFFFAOYSA-M 0.000 description 1
- TVLWUEFMJYTXBV-UHFFFAOYSA-M benzyl(trihexyl)azanium;chloride Chemical compound [Cl-].CCCCCC[N+](CCCCCC)(CCCCCC)CC1=CC=CC=C1 TVLWUEFMJYTXBV-UHFFFAOYSA-M 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- GEHMWSIEKHOKJZ-UHFFFAOYSA-M benzyl(trioctyl)azanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CC1=CC=CC=C1 GEHMWSIEKHOKJZ-UHFFFAOYSA-M 0.000 description 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 description 1
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 description 1
- BMDRYIFEJILWIP-UHFFFAOYSA-M butyl(triethyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CC)(CC)CC BMDRYIFEJILWIP-UHFFFAOYSA-M 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical class C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OAGDQKIHYQTVMA-UHFFFAOYSA-N ethyl 3,5-dichloro-2,4-difluorobenzoate Chemical compound CCOC(=O)C1=CC(Cl)=C(F)C(Cl)=C1F OAGDQKIHYQTVMA-UHFFFAOYSA-N 0.000 description 1
- UXYBXUYUKHUNOM-UHFFFAOYSA-M ethyl(trimethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)C UXYBXUYUKHUNOM-UHFFFAOYSA-M 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000006332 fluoro benzoyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- SPJQBGGHUDNAIC-UHFFFAOYSA-N methyl 2,5-dichlorobenzoate Chemical compound COC(=O)C1=CC(Cl)=CC=C1Cl SPJQBGGHUDNAIC-UHFFFAOYSA-N 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MZVRZMXMVXWEQW-UHFFFAOYSA-M n,n-dibutyl-1-(2,2-dimethylpropyl)pyridin-1-ium-4-amine;chloride Chemical compound [Cl-].CCCCN(CCCC)C1=CC=[N+](CC(C)(C)C)C=C1 MZVRZMXMVXWEQW-UHFFFAOYSA-M 0.000 description 1
- DLZHYNRQTCHKKV-UHFFFAOYSA-M n,n-dibutyl-1-(2-ethylhexyl)pyridin-1-ium-4-amine;bromide Chemical compound [Br-].CCCCC(CC)C[N+]1=CC=C(N(CCCC)CCCC)C=C1 DLZHYNRQTCHKKV-UHFFFAOYSA-M 0.000 description 1
- MZEXOXBTROHQNO-UHFFFAOYSA-M n,n-dibutyl-1-(2-ethylhexyl)pyridin-1-ium-4-amine;chloride Chemical compound [Cl-].CCCCC(CC)C[N+]1=CC=C(N(CCCC)CCCC)C=C1 MZEXOXBTROHQNO-UHFFFAOYSA-M 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- DMDPGPKXQDIQQG-UHFFFAOYSA-N pentaglyme Chemical compound COCCOCCOCCOCCOCCOC DMDPGPKXQDIQQG-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LXOPGEOHQNURFP-UHFFFAOYSA-N propan-2-yl 3,5-dichloro-2,4-difluorobenzoate Chemical compound CC(C)OC(=O)C1=CC(Cl)=C(F)C(Cl)=C1F LXOPGEOHQNURFP-UHFFFAOYSA-N 0.000 description 1
- LJAGKXGWTPAVPD-UHFFFAOYSA-N propan-2-yl 3,5-dichloro-4-fluorobenzoate Chemical compound CC(C)OC(=O)C1=CC(Cl)=C(F)C(Cl)=C1 LJAGKXGWTPAVPD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- MRPDZPGNCPXKGT-UHFFFAOYSA-N tert-butyl 2,3-dichlorobenzoate Chemical compound CC(C)(C)OC(=O)C1=CC=CC(Cl)=C1Cl MRPDZPGNCPXKGT-UHFFFAOYSA-N 0.000 description 1
- YFXXVGXVKQQCAH-UHFFFAOYSA-N tert-butyl 3,5-dichloro-2,4-difluorobenzoate Chemical compound CC(C)(C)OC(=O)C1=CC(Cl)=C(F)C(Cl)=C1F YFXXVGXVKQQCAH-UHFFFAOYSA-N 0.000 description 1
- UEZFGZYRUYWVKK-UHFFFAOYSA-N tert-butyl 3,5-dichloro-4-fluorobenzoate Chemical compound CC(C)(C)OC(=O)C1=CC(Cl)=C(F)C(Cl)=C1 UEZFGZYRUYWVKK-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- SYZCZDCAEVUSPM-UHFFFAOYSA-M tetrahexylazanium;bromide Chemical compound [Br-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC SYZCZDCAEVUSPM-UHFFFAOYSA-M 0.000 description 1
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 description 1
- BALCYVFFDOBQPW-UHFFFAOYSA-M tetraphenylazanium;chloride Chemical compound [Cl-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BALCYVFFDOBQPW-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- VBFVWBMHOSXZOX-UHFFFAOYSA-M tributyl(2-methylpropyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC(C)C VBFVWBMHOSXZOX-UHFFFAOYSA-M 0.000 description 1
- FGQQGDVRJUAQLN-UHFFFAOYSA-M tributyl(dodecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](CCCC)(CCCC)CCCC FGQQGDVRJUAQLN-UHFFFAOYSA-M 0.000 description 1
- QTNZUCWMRAIYCB-UHFFFAOYSA-M tributyl(ethyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CC)(CCCC)CCCC QTNZUCWMRAIYCB-UHFFFAOYSA-M 0.000 description 1
- MGFDNLWKTJVEDZ-UHFFFAOYSA-M tributyl(hexyl)azanium;bromide Chemical compound [Br-].CCCCCC[N+](CCCC)(CCCC)CCCC MGFDNLWKTJVEDZ-UHFFFAOYSA-M 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- PPQRADLPLZYEKN-UHFFFAOYSA-N tritylphosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1C(C=1C=CC=CC=1)([PH3+])C1=CC=CC=C1 PPQRADLPLZYEKN-UHFFFAOYSA-N 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は新規なフルオロ安息香酸エステル及びその製造
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel fluorobenzoic acid ester and a method for producing the same.
(従来の技術)
近年フッ素を含有する農薬や医薬品は、優れた薬理活性
や生理活性などを有することから注目され、積極的に研
究がなされており、例えば含フツ素尿素系殺虫剤および
含フツ素キノリン系抗菌剤が提案されている。中でも特
開昭57−126460公報記載のN−(3,5−ジク
ロロ−2,4−ジフルオロフェニル)−N’−(2,6
−ジクロロベンゾイル)尿素が殺虫剤として高い活性を
示すことが知られている。またその製造方法として3.
5−ジクロロ−2,4−ジフルオロフェニルイソシアネ
ートと2.6−シフルオロベンズアミドとを反応させて
製造する方法が知られている。(Prior art) In recent years, fluorine-containing pesticides and pharmaceuticals have attracted attention due to their excellent pharmacological and physiological activities, and are being actively researched. Plain quinoline antibacterial agents have been proposed. Among them, N-(3,5-dichloro-2,4-difluorophenyl)-N'-(2,6
-dichlorobenzoyl) urea is known to exhibit high activity as an insecticide. In addition, as the manufacturing method, 3.
A method of producing it by reacting 5-dichloro-2,4-difluorophenyl isocyanate and 2,6-cyfluorobenzamide is known.
(発明が解決しようとする問題点)
しかし、前記公報記載の製造方法において使用する、フ
ルオロフェニルイソシアネート類は一般に対応するアニ
リンとホスゲンとを反応させることにより製造されてい
るが、このホスゲンは毒ガスでありその使用に際し規制
が定められている為、ホスゲンを使用せずに前記フェニ
ルイソシアネートを製造する方法が望まれていた。また
、最近ホスゲンを使用しないイソシアネートの製造方法
として2,3,4.5−テトラクロロベンゾイルクロリ
ドをフッ素化し3.5−ジクロロ−2,4−ジフルオロ
ベンゾイルフロリドを得、これにアジ化ナトリウムを反
応させて対応するベンゾイルアジドを製造しこれを加熱
することにより3.5−ジクロロ−2,4−ジフルオロ
フェニルイソシアネートを製造する方法が提案されてい
る。(国際特許出願公開WO36105487号公報参
照)しかしながらこの方法も、爆発性のあるアジ化ナト
リウムを使用するため工業的には満足できる方法ではな
かった。(Problems to be Solved by the Invention) However, the fluorophenyl isocyanates used in the production method described in the above publication are generally produced by reacting the corresponding aniline with phosgene, but this phosgene is a poisonous gas. Since there are regulations regarding the use of phenyl isocyanate, a method for producing the phenyl isocyanate without using phosgene has been desired. Recently, as a method for producing isocyanate without using phosgene, 2,3,4,5-tetrachlorobenzoyl chloride is fluorinated to obtain 3,5-dichloro-2,4-difluorobenzoyl fluoride, and sodium azide is added to this. A method has been proposed for producing 3,5-dichloro-2,4-difluorophenyl isocyanate by reacting to produce the corresponding benzoyl azide and heating the same. (See International Patent Application Publication No. WO 36105487) However, this method was also not industrially satisfactory because it used explosive sodium azide.
(問題点を解決するための手段)
本発明者らは、このような現状に鑑み、フルオロフェニ
ルイソシアネートを、他の方法で工業的に製造する方法
を提供すべ(鋭意研究を重ねた結果、対応するクロロ安
息香酸エステルと金属フルオリドとを、特定の触媒およ
び特定の溶媒の存在下もしくは無溶媒下で反応させるこ
とにより、エステル基の副反応を抑制し、新規なフルオ
ロ安息香酸エステルを製造することができ、さらにこの
フルオロ安息香酸エステルより前記フルオロフェニルイ
ソシアネートを製造できることを見出し、この知見に基
づき本発明を完成するに至った。(Means for Solving the Problems) In view of the current situation, the present inventors proposed a method for industrially producing fluorophenyl isocyanate using other methods (as a result of extensive research, they By reacting a chlorobenzoic acid ester and a metal fluoride in the presence of a specific catalyst and a specific solvent or in the absence of a solvent, side reactions of the ester group are suppressed and a new fluorobenzoic acid ester is produced. It was also discovered that the fluorophenyl isocyanate can be produced from this fluorobenzoic acid ester, and based on this knowledge, the present invention was completed.
すなわち本発明は、含フツ素尿素系殺虫剤、含フツ素キ
ノリン系殺菌剤製造中間体として有用な一般式
(式中、Xはフッ素原子または水素原子を示し、Rはア
ルキル基を示す。)
で表されるフルオロ安息香酸エステル、および(式中、
Yは水素原子または塩素原子を示し、Rはアルキル基を
示す。)
で表されるクロロ安息香酸エステルと金属フルオリドと
を、触媒として第四級ホスホニウム塩、第四級アンモニ
ウム塩およびピリジニウム塩の中から選ばれる少な(と
も1種の塩の存在下、非プロトン性極性溶媒中で、また
は、触媒として第四級ホスホニウム塩、第四級アンモニ
ウム塩およびピリジニウム塩の中から選ばれる少なくと
も1種の塩と、クラウンエーテル及びポリアルキレング
リコール類の中から選ばれる少なくとも1種の化合物と
の組み合わせの存在下反応させ、一般式(式中、Xおよ
びRは前記と同一の意味を有する。)で表されるフルオ
ロ安息香酸エステルを製造することを特徴とするフルオ
ロ安息香酸エステルの製造方法を提供するものである。That is, the present invention provides a general formula useful as an intermediate for producing a fluorine-containing urea insecticide or a fluorine-containing quinoline fungicide (wherein, X represents a fluorine atom or a hydrogen atom, and R represents an alkyl group). Fluorobenzoic acid ester represented by, and (in the formula,
Y represents a hydrogen atom or a chlorine atom, and R represents an alkyl group. ) A chlorobenzoic acid ester represented by In a polar solvent or as a catalyst, at least one salt selected from quaternary phosphonium salts, quaternary ammonium salts, and pyridinium salts, and at least one salt selected from crown ethers and polyalkylene glycols. A fluorobenzoic acid ester characterized by producing a fluorobenzoic acid ester represented by the general formula (wherein X and R have the same meanings as above) by reacting in the presence of a combination with a compound of The present invention provides a method for manufacturing.
本発明のフルオロ安息香酸エステルは、前記−般式(1
)で表される化合物であって該式中のXは水素原子また
はフッ素原子を示し、Rはメチル基、エチル基、プロピ
ル基、イソプロピル基、t−ブチル基、5ec−ブチル
基、ネオペンチル基などのアルキル基を示す。このよう
なフルオロ安息香酸エステルとしては例えば、3.5−
ジクロロ−4−フルオロ安息香酸メチル、3.5−ジク
ロロ−4−フルオロ安息香酸エチル、3.5−ジクロロ
−4−フルオロ安息香酸イソプロピル、3゜5−ジクロ
ロ−4−フルオロ安息香酸−t−ブチル、3,5−ジク
ロロ−4−フルオロ安息香酸−5ec−ブチル、3.5
−ジクロロ−4−フルオロ安息香酸−ネオペンチル、3
.5−ジクロロ−2,4−ジフルオロ安息香酸メチル、
3,5−ジクロロ−2,4−ジフルオロ安息香酸エチル
、3゜5−ジクロロ−2,4−ジフルオロ安息香酸イソ
プロピル、3.5−ジクロロ−2,4−ジフルオロ安息
香酸−t−ブチル、3.5−ジクロロ−2゜4−ジフル
オロ安息香酸−5ec−ブチルおよび3.5−ジクロロ
−2,4−ジフルオロ安息香酸−ネオペンチルなどが挙
げられる。The fluorobenzoic acid ester of the present invention has the above general formula (1
), in which X represents a hydrogen atom or a fluorine atom, and R represents a methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, 5ec-butyl group, neopentyl group, etc. represents an alkyl group. Examples of such fluorobenzoic acid esters include 3.5-
Methyl dichloro-4-fluorobenzoate, ethyl 3.5-dichloro-4-fluorobenzoate, isopropyl 3.5-dichloro-4-fluorobenzoate, t-butyl 3.5-dichloro-4-fluorobenzoate , 5ec-butyl 3,5-dichloro-4-fluorobenzoate, 3.5
-Dichloro-4-fluorobenzoic acid-neopentyl, 3
.. Methyl 5-dichloro-2,4-difluorobenzoate,
Ethyl 3,5-dichloro-2,4-difluorobenzoate, isopropyl 3.5-dichloro-2,4-difluorobenzoate, t-butyl 3.5-dichloro-2,4-difluorobenzoate, 3. Examples include 5ec-butyl 5-dichloro-2°4-difluorobenzoate and neopentyl 3,5-dichloro-2,4-difluorobenzoate.
本発明のフルオロ安息香酸エステルの製造方法において
原料として用いられるクロロ安息香酸エステルは、前記
一般式(II)で示−される化合物であり、該式中のY
は水素原子または塩素原子を示し、Rはメチル基、エチ
ル基、プロピル基、イソプロピル基、t−ブチル基、5
ec−ブチル基、lネオペンチル基などのアルキル基を
示しなかでもネオペンチル基が好ましい。このようなり
ロロ安息香酸エステルとしては、例えば3,4.5−1
リクロロ安息香酸メチル、3.4.5−1−ジクロロ安
息香酸エチル、3.4.5−トリクロロ安息香酸イソプ
ロピル、3,4.5−)ジクロロ安息香酸−t−ブチル
、3,4.5−1−ジクロロ安息香酸−5ec−ブチル
、3.4.5−トリクロロ安息香酸−ネオペンチル、2
.3,4.5−テトラクロロ安息香酸メチル、2.3,
4.5−テトラクロロ安息香酸エチル、2,3.4.5
−テトラクロロ安息香酸イソプロピル、2.3.4.5
−テトラクロロ安息香酸−t−ブチル、2.3゜4.5
−テトラクロロ安息香酸−5ec−ブチルおよび2.3
.4.5−テトラクロロ安息香息香酸−ネオペンチルな
どが挙げられる。The chlorobenzoic acid ester used as a raw material in the method for producing a fluorobenzoic acid ester of the present invention is a compound represented by the general formula (II), in which Y
represents a hydrogen atom or a chlorine atom, R is a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, 5
Among the alkyl groups such as ec-butyl group and l-neopentyl group, neopentyl group is preferred. As such lolobenzoic acid ester, for example, 3,4.5-1
Methyl dichlorobenzoate, 3.4.5-ethyl dichlorobenzoate, 3.4.5-isopropyl trichlorobenzoate, 3,4.5-) tert-butyl dichlorobenzoate, 3,4.5- 5ec-butyl 1-dichlorobenzoate, 3.4.5-neopentyl trichlorobenzoate, 2
.. Methyl 3,4.5-tetrachlorobenzoate, 2.3,
4.5-Ethyl tetrachlorobenzoate, 2,3.4.5
-isopropyl tetrachlorobenzoate, 2.3.4.5
-t-butyl tetrachlorobenzoate, 2.3°4.5
-5ec-butyl tetrachlorobenzoate and 2.3
.. Examples include 4.5-tetrachlorobenzoic acid-neopentyl.
本発明の製造方法において触媒として用いる第四級ホス
ホニウム塩、第四級アンモニウム塩およびピリジニウム
塩としては、それぞれ一般式%式%()
(式中のR1,R1,R3およびR4はそれぞれアルキ
ル基、アリール基またはアラルキル基であり、それらは
同一であってもよいし、互いに異なっていてもよく、X
゛はハロゲン原子である。また、R’、R−およびR″
はそれぞれアルキル基であり、それらは同一であっても
よいし、互いに異なっていてもよく、X”はハロゲン原
子である。)で表される化合物を使用することができる
。このような化合物の具体例としては、テトラフェニル
ホスホニウムプロミド、テトラフェニルホスホニウムク
ロリド、ベンジルトリブチルホスホニウムクロリド、ベ
ンジルトリフェニルホスホニウムクロリド、トリフェニ
ルメチルホスホニウムクロリドなどの第四級ホスホニウ
ム塩、テトラメチルアンモニウムクロリド、テトラエチ
ルアンモニウムプロミド、テトラブチルアンモニウムプ
ロミド。The quaternary phosphonium salts, quaternary ammonium salts and pyridinium salts used as catalysts in the production method of the present invention have the general formula % () (R1, R1, R3 and R4 are each an alkyl group, an aryl group or an aralkyl group, which may be the same or different from each other,
゛ is a halogen atom. Also, R', R- and R''
are each an alkyl group, and they may be the same or different from each other, and X'' is a halogen atom. Specific examples include quaternary phosphonium salts such as tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, benzyltributylphosphonium chloride, benzyltriphenylphosphonium chloride, triphenylmethylphosphonium chloride, tetramethylammonium chloride, tetraethylammonium bromide, Tetrabutylammonium bromide.
テトラプチルアンモニウムヨージド、テトラヘキシルア
ンモニウムプロミド、テトラオクチルアンモニウムクロ
リド、エチルトリメチルアンモニウムクロリド、ブチル
トリエチルアンモニウムクロリド、ラウリルトリメチル
アンモニウムプロミド。Tetraptylammonium iodide, tetrahexylammonium bromide, tetraoctylammonium chloride, ethyltrimethylammonium chloride, butyltriethylammonium chloride, lauryltrimethylammonium bromide.
エチルトリブチルアンモニウムプロミド、イソブチルト
リブチルアンモニウムプロミド、ヘキシルトリブチルア
ンモニウムプロミド、オクチルトリブチルアンモニウム
プロミド、ラウリルトリブチルアンモニウムプロミド、
メチルトリオクチルアンモニウムプロミド、テトラフェ
ニルアンモニウムクロリド、ベンジルトリメチルアンモ
ニウムプロミド、ベンジルトリエチルアンモニウムクロ
リド、ベンジルトリプロピルアンモニウムクロリド。Ethyltributylammonium bromide, isobutyltributylammonium bromide, hexyltributylammonium bromide, octyltributylammonium bromide, lauryltributylammonium bromide,
Methyltrioctylammonium bromide, tetraphenylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltripropylammonium chloride.
ベンジルトリヘキシルアンモニウムクロリド、ベンジル
トリオクチルアンモニウムクロリドなどの第四級アンモ
ニウム塩、N−(2−エチルヘキシル)−4−ジメチル
アミノピリジニウムクロリド。Quaternary ammonium salts such as benzyltrihexylammonium chloride and benzyltrioctylammonium chloride, N-(2-ethylhexyl)-4-dimethylaminopyridinium chloride.
N−(2−エチルヘキシル)−4−ジ−n−ブチルアミ
ノピリジニウムクロリド、N−(2−エチルヘキシル)
−4−ジーn−へキシルアミノピリジニウムクロリド、
N−ネオペンチル−4−ジメチルアミノビリジ互ウムク
ロリド、N−ネオペンチル−4−ジ−n−ブチルアミノ
ピリジニウムクロリド、N−ネオペンチル−4−ジーn
−へキシルアミノピリジニウムクロリド、N−(2−エ
チルヘキシル)−4−ジメチルアミノピリ、ジニウムク
ロリド、N−(2−エチルヘキシル)−4−ジ−n−ブ
チルアミノピリジニウムプロミド、N−(2−エチルヘ
キシル)−4−ジ−n−ヘキシルアミノピリジニウムプ
ロミド、N−ネオペンチル−4−ジ−メチルアミノピリ
ジニウムプロミド。N-(2-ethylhexyl)-4-di-n-butylaminopyridinium chloride, N-(2-ethylhexyl)
-4-di-n-hexylaminopyridinium chloride,
N-neopentyl-4-dimethylaminopyridinium chloride, N-neopentyl-4-di-n-butylaminopyridinium chloride, N-neopentyl-4-di-n
-hexylaminopyridinium chloride, N-(2-ethylhexyl)-4-dimethylaminopyri, dinium chloride, N-(2-ethylhexyl)-4-di-n-butylaminopyridinium bromide, N-(2- ethylhexyl)-4-di-n-hexylaminopyridinium bromide, N-neopentyl-4-di-methylaminopyridinium bromide.
N−ネオペンチル−4,−ジ−n−ブチルアミノピリジ
ニウムプロミド、N−ネオペンチル−4−ジ−n−ヘキ
シルアミノピリジニウムプロミドなどのピリジニウム塩
が挙げられる。Examples include pyridinium salts such as N-neopentyl-4,-di-n-butylaminopyridinium bromide and N-neopentyl-4-di-n-hexylaminopyridinium bromide.
さらに、本発明においては、触媒として、前記の第四級
ホスホニウム塩、第四級アンモニウム塩およびピリジニ
ウム塩の中から選ばれる少なくとも一種の塩とクラウン
エーテル及びポリアルキレングリコール類の中から選ば
れる少なくとも1種の化合物との組み合わせを用いるこ
ともできる。Furthermore, in the present invention, at least one salt selected from the above-mentioned quaternary phosphonium salts, quaternary ammonium salts and pyridinium salts and at least one salt selected from crown ethers and polyalkylene glycols are used as catalysts. Combinations with species compounds can also be used.
該クラウンエーテルとしては、例えば18−クラウン−
6、ジベンゾ−18−クラウン−6、ジシクロへキサノ
ー1B−クラウン−6,12−クラウン−4,15−ク
ラウン−5,およびジベンゾ−24−クラウン−8など
が挙げられるが、中でも18−クラウン−6、ジベンゾ
−18−クラウン−6、ジシクロへキサノー18−クラ
ウン−6が好適である。As the crown ether, for example, 18-crown-
6, dibenzo-18-crown-6, dicyclohexanone 1B-crown-6,12-crown-4,15-crown-5, and dibenzo-24-crown-8, among others, 18-crown- 6, dibenzo-18-crown-6, and dicyclohexano-18-crown-6 are preferred.
また、ポリアルキレングリコール類としては、一般式
%式%()
(式中のR1はアルキレン基、R9およびR”はそれぞ
れ水素原子、アルキル基、アリール基またはアラルキル
基であって、それらは同一であってもよいし、互いに異
なっていてもよく、Zは2以上の整数である。)
で表される化合物を用いることができる。このような化
合物としては、例えばジエチレングリコール、トリエチ
レングリコール、テトラエチレングリコール、ペンタエ
チレングリコール、ヘキサエチレングリコール、ジイソ
プロピレングリコール。In addition, as polyalkylene glycols, the general formula % () (in the formula, R1 is an alkylene group, R9 and R'' are each a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, and they are the same) or may be different from each other, and Z is an integer of 2 or more.) Examples of such compounds include diethylene glycol, triethylene glycol, and tetraethylene. Glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol.
ジプロピレングリコール、トリプロピレングリコール、
テトラプロピレングリコール、テトラメチレングリコー
ルなどのグリコール類、およびこれらグリコール類のモ
ノメチル−、モノエチル−。dipropylene glycol, tripropylene glycol,
Glycols such as tetrapropylene glycol and tetramethylene glycol, and monomethyl and monoethyl of these glycols.
モノプロとルー、モノブチルエーテルなどのモノアルキ
ルエーテル類、テトラエチレングリコールジメチルエー
テル、ペンタエチレングリコールジメチルエーテルなど
のジアルキルエーテル類、フェニルエーテル類、ベンジ
ルエーテル類、さらにポリエチレングリコールジメチル
エーテル(平均分子1300)、ポリエチレングリコー
ルジブチルエーテル(平均分子量300)、ポリエチレ
ングリコールジメチルエーテル(平均分子量400)な
どのポリアルキレングリコール類が挙げられるが、なか
でもR9とR1(lが共にアルキル基、アリール基又は
アラルキル基の化合物が好ましい。Monoalkyl ethers such as monopro and monobutyl ether, dialkyl ethers such as tetraethylene glycol dimethyl ether and pentaethylene glycol dimethyl ether, phenyl ethers, benzyl ethers, as well as polyethylene glycol dimethyl ether (average molecular weight 1300), polyethylene glycol dibutyl ether (average molecular weight: 300), polyethylene glycol dimethyl ether (average molecular weight: 400), etc. Among them, compounds in which R9 and R1 (l are both alkyl, aryl, or aralkyl groups) are preferred.
本発明においては、前記のクラウンエーテルやポリアル
キレングリコールは、1種用いてもよいし、2種以上組
み合わせて用いてもよく、またクラウンエーテルとポリ
アルキレングリコール類を併用してもよい。In the present invention, the above-mentioned crown ethers and polyalkylene glycols may be used alone or in combination of two or more, and crown ethers and polyalkylene glycols may be used in combination.
本発明においては、触媒の使用量は、前記一般式(If
)で示されるクロロ安息香酸エステル1モルに対し、通
常1〜50モル%、好ましくは5〜40モル%の範囲で
選ばれる。また触媒としてクラウンエーテルやポリアル
キレングリコール類と前記の第四級ホスホニウム塩、第
四級アンモニウム塩およびピリジニウム塩との組み合わ
せて用いる場合、両者の割合についてはクラウンエーテ
ル又はポリアルキレングリコールの量が第四級ホスホニ
ウム塩、第四級アンモニウム塩およびピリジニウム塩の
4倍モルを越えない割合で用いることが望ましい。第四
級ホスホニウム塩を用いずに、クラウンエーテルやポリ
アルキレングリコール類を単独で使用した場合には目的
のフルオロ安息香酸エステルはほとんど生成しない。In the present invention, the amount of catalyst used is determined by the general formula (If
) is usually selected in an amount of 1 to 50 mol %, preferably 5 to 40 mol %, based on 1 mol of the chlorobenzoic acid ester. In addition, when a crown ether or polyalkylene glycol is used in combination with the above-mentioned quaternary phosphonium salt, quaternary ammonium salt, or pyridinium salt as a catalyst, the amount of crown ether or polyalkylene glycol is It is desirable to use the compound in a molar ratio not exceeding four times that of the quaternary phosphonium salt, quaternary ammonium salt and pyridinium salt. When a crown ether or polyalkylene glycol is used alone without using a quaternary phosphonium salt, the desired fluorobenzoic acid ester is hardly produced.
本発明方法において用いられる金属フルオリドとしては
、例えばフッ化カリウム、フッ化セシウムなどが挙げら
れるが、特にスプレー乾燥したフッ化カリウムが好適で
ある。これらの金属フルオリドは、前記一般式(U)で
示されるクロロ安息香酸エステルの置換可能な塩素原子
に対して1〜2倍当量の割合で用いることが好ましい、
また本反応は通常、反応を円滑に進める目的で溶媒の存
在下行うこともできるし、無溶媒で行うこともできる。Examples of the metal fluoride used in the method of the present invention include potassium fluoride and cesium fluoride, and spray-dried potassium fluoride is particularly preferred. These metal fluorides are preferably used in a ratio of 1 to 2 equivalents to the replaceable chlorine atom of the chlorobenzoic acid ester represented by the general formula (U),
Further, this reaction can usually be carried out in the presence of a solvent or without a solvent for the purpose of smoothly proceeding the reaction.
溶媒を使用する場合は、スルホラン、ジメチルスルホン
、1.3−ジメチルイミダシリン−2−オン、ジメチル
ホルムアミド、N−メチルピロリドン、テトラメチル尿
素、ジメチルスルホキシド等の非プロトン性極性溶媒の
使用が好ましい。When using a solvent, it is preferable to use an aprotic polar solvent such as sulfolane, dimethylsulfone, 1,3-dimethylimidacylin-2-one, dimethylformamide, N-methylpyrrolidone, tetramethylurea, dimethylsulfoxide, etc. .
さらに、触媒として前記第四級ホスホニウム塩。Furthermore, the quaternary phosphonium salt as a catalyst.
第四級アンモニウム塩およびピリジニウム塩の中から選
ばれる少なくとも一種を単独で使用する場合には非プロ
トン性極性溶媒中で反応を行うのが好ましい。またこの
非プロトン性極性溶媒の使用量は、前記一般式(II)
で示されるハロゲン化ベンズアルデヒド[1モルに対し
、通常100〜1000g、好ましくは150〜500
gの範囲で選ばれる。When at least one selected from quaternary ammonium salts and pyridinium salts is used alone, the reaction is preferably carried out in an aprotic polar solvent. Further, the amount of this aprotic polar solvent to be used is determined according to the above general formula (II).
[Usually 100 to 1000 g, preferably 150 to 500 g per mol of halogenated benzaldehyde represented by
selected within the range of g.
また、本反応は通常150〜300℃、好ましくは16
0〜240℃の範囲で選ばれる。反応圧については特に
制限はなく、常圧で反応させてもよいし、加圧下で反応
させてもよい。加圧下で反応させる場合は、10kg/
cm”以下の圧が好ましいが、工業的には常圧で反応さ
せるのが好ましい。In addition, this reaction is usually carried out at 150 to 300°C, preferably at 16°C.
The temperature is selected within the range of 0 to 240°C. There is no particular restriction on the reaction pressure, and the reaction may be carried out at normal pressure or under increased pressure. When reacting under pressure, 10 kg/
Although a pressure of 1.5 cm or less is preferable, industrially it is preferable to carry out the reaction at normal pressure.
さらに反応時間は1〜20時間程度で十分である。Further, a reaction time of about 1 to 20 hours is sufficient.
本発明方法によって得られる新規なフルオロ安息香酸エ
ステルは以下に示す様に、常法に従いヒドラジンと反応
させることにより対応するフルオロベンゾイルヒドラジ
ドを得、さらに亜硝酸ナトリウムと反応させることによ
り対応するフルオロベンゾイルアジドを得、これを加熱
することによす前記フルオロフェニルイソシアネートを
製造することができる。またこのフルオロフェニルイソ
シアネートとベンズアミドとを反応させることにより特
開昭57−126460号公報記載の含フツ素尿素系殺
菌剤を製造することができる。The novel fluorobenzoic acid ester obtained by the method of the present invention is obtained by reacting with hydrazine according to a conventional method to obtain the corresponding fluorobenzoyl hydrazide, and further reacting with sodium nitrite to obtain the corresponding fluorobenzoyl azide. The above-mentioned fluorophenyl isocyanate can be produced by obtaining and heating this. Furthermore, by reacting this fluorophenyl isocyanate with benzamide, the fluoride-containing urea fungicide described in JP-A-57-126460 can be produced.
(発明の効果)
本発明方法によると、一般式(II)で示されるクロロ
安息香酸エステルと金属フルオリドとを、特定の触媒、
特定の溶媒の存在下、反応させることにより、式中の−
OH基の核への転移、脱炭酸及び高沸物の生成等の副反
応を抑制し、工業的にフルオロ安息香酸エステルを製造
することができる。さらにこの方法により得られたフル
オロ安息香酸エステルは、フルオロフェニルイソシアネ
ートの製造中間体として有用な化合物である。(Effects of the Invention) According to the method of the present invention, a chlorobenzoic acid ester represented by general formula (II) and a metal fluoride are combined with a specific catalyst,
By reacting in the presence of a specific solvent, − in the formula
Fluorobenzoic acid esters can be produced industrially by suppressing side reactions such as transfer of OH groups to nuclei, decarboxylation, and generation of high-boiling substances. Further, the fluorobenzoic acid ester obtained by this method is a compound useful as an intermediate for producing fluorophenyl isocyanate.
実施例 次に実施例により本発明をさらに詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例1
水分離器、攪拌機を備えた50−1四つロフラスコに、
スプレー乾燥フン化カリウム(森田化学工業■製) 6
.0 g (104gm+ol) 、テトラフェニルホ
スホニウムプロミドl’、 7 g (4gmol)
、無水スルホラン12gおよびトルエン20−1を入
れ、油浴上で加熱攪拌しながらトルエンを留去させ、共
沸脱水を行った。液温か140℃になるまで加熱した後
45ssHgまで減圧にし、残りのトルエンをほぼ全量
留去した0反応容器内を100℃まで冷却し窒素ガスで
置換した後、2.3,4.5−テトラクロロ安息香酸ネ
オペンチル13.1g(40gaol)を加え、窒素ガ
ス雰囲気下190℃で攪拌を行い15時間反応を行った
。Example 1 In a 50-1 four-loaf flask equipped with a water separator and a stirrer,
Spray-dried potassium fluoride (manufactured by Morita Chemical Industries, Ltd.) 6
.. 0 g (104 gm+ol), tetraphenylphosphonium bromide l', 7 g (4 gmol)
, 12 g of anhydrous sulfolane, and 20-1 toluene were added, and toluene was distilled off while stirring while heating on an oil bath to perform azeotropic dehydration. After heating the liquid temperature to 140°C, the pressure was reduced to 45ssHg, and almost all of the remaining toluene was distilled off. The interior of the reaction vessel was cooled to 100°C, replaced with nitrogen gas, and 2.3,4.5-tetra 13.1 g (40 gaol) of neopentyl chlorobenzoate was added, and the mixture was stirred at 190° C. under a nitrogen gas atmosphere to conduct a reaction for 15 hours.
反応終了後、反応混合物を冷却し、トルエン100s+
1を加え無機物を濾過した後、濾液を水200m1で3
回洗浄した。トルエン層を取り出し無水硫酸ナトリウム
で乾燥後、ロータリーエバポレーターでトルエンを留去
し、褐色の油状物質11.0gを得た。得られた油状物
質を減圧蒸留し、無色油状物質の3,5−ジクロロ−2
,4−ジフルオロ安息香酸ネオペンチル7.2gを得た
。収率は61%であった。以下に本化合物の赤外線吸収
スペクトル分析(以下、IRと略す。)、核磁気共鳴ス
ペクトル分析(以下、NMRと略す。)。After the reaction is completed, the reaction mixture is cooled and heated with toluene for 100s+
After adding 1 and filtrating the inorganic matter, dilute the filtrate with 200ml of water.
Washed twice. The toluene layer was taken out and dried over anhydrous sodium sulfate, and the toluene was distilled off using a rotary evaporator to obtain 11.0 g of a brown oily substance. The obtained oily substance was distilled under reduced pressure to obtain 3,5-dichloro-2 as a colorless oily substance.
, 7.2 g of neopentyl 4-difluorobenzoate was obtained. The yield was 61%. Infrared absorption spectrum analysis (hereinafter abbreviated as IR) and nuclear magnetic resonance spectrum analysis (hereinafter abbreviated as NMR) of this compound will be described below.
質量スペクトル分析(以下、Massと略す。)の分析
結果を示す。The analysis results of mass spectrum analysis (hereinafter abbreviated as Mass) are shown.
沸点;115〜b
融点;38〜42℃
I R’(KBr); 1720(C=O)、1250
(C−F) cm−’Mass s+/e : 29
6(M” )、 209(M”−CHxC(CHs)s
)実施例2
実施例1における2、3.4.5−テトラクロロ安息香
酸ネオペンチルに代えて3,4.5−)ジクロロ安息香
酸ネオペンチル8.9g (30鋼−ol) 、スプレ
ー乾燥フン化カリウム2.6g(45vwol)、テト
ラフェニルホスホニウムプロミド1. 3g (31m
ol) 、無水スルホラン9gを用い、同様の操作で6
時間反応を行った。同様に後処理を行った後減圧蒸留に
より5.3gの3,5−ジクロロ−4−フルオロ安息香
酸ネオペンチルを得た。さらに蒸留残渣をシリカゲルに
よるカラムクロマトグラフィーに付し、ベンゼンで溶離
することにより淡黄色板状結晶の3.5−ジクロロ−4
−フルオロ安息香酸ネオペンチル2.0gを得た。収率
は87%であった。以下に物性を示す。Boiling point: 115-b Melting point: 38-42°C I R'(KBr); 1720 (C=O), 1250
(C-F) cm-'Mass s+/e: 29
6(M”), 209(M”-CHxC(CHs)s
) Example 2 Neopentyl 3,4.5-)dichlorobenzoate in place of neopentyl 2,3.4.5-tetrachlorobenzoate in Example 1 8.9 g (30 steel-ol), spray-dried potassium fluoride 2.6 g (45 vwol) of tetraphenylphosphonium bromide 1. 3g (31m
6 in the same manner using 9 g of anhydrous sulfolane.
A time reaction was performed. After post-treatment in the same manner, 5.3 g of neopentyl 3,5-dichloro-4-fluorobenzoate was obtained by distillation under reduced pressure. Furthermore, the distillation residue was subjected to column chromatography using silica gel and eluted with benzene to obtain pale yellow plate-like crystals of 3,5-dichloro-4.
-2.0 g of neopentyl fluorobenzoate was obtained. The yield was 87%. The physical properties are shown below.
沸点 ; 137〜140 ℃/ 7 mm1g融点;
96〜98℃
I R(KBr); 1730(C=O)、1240(
C−F) cm−’Mass m/e : 27B(
?I” )、 191 (M”−CHzC(CII+)
*)実施例3
実施例1において、2. 3. 4. 5−テトラクロ
ロ安息香酸ネオペンチル9.9 g (30+gnol
) 。Boiling point: 137-140°C/7 mm/g Melting point;
96-98℃ IR (KBr); 1730 (C=O), 1240 (
C-F) cm-'Mass m/e: 27B(
? I”), 191 (M”-CHzC(CII+)
*) Example 3 In Example 1, 2. 3. 4. Neopentyl 5-tetrachlorobenzoate 9.9 g (30+gnol
).
スプレー乾燥フン化カリウム4. 0 g (69o+
mol)スルホラン9gを用い、テトラフェニルホスホ
ニウムプロミドの代わりに、N−・(2−エチルヘキシ
ル)−4−ジメチルアミノピリジニウムクロリド0.8
g (3−sol)を用いた以外は実施例1と同様に反
応・後処理を行い、3,5−ジクロロ−2,4−ジフル
オロ安息香酸ネオペンチル5.7gを得た。収率は64
%であった。Spray dried potassium fluoride4. 0 g (69o+
mol) Using 9 g of sulfolane, 0.8 of N-.(2-ethylhexyl)-4-dimethylaminopyridinium chloride was added in place of tetraphenylphosphonium bromide.
The reaction and post-treatment were carried out in the same manner as in Example 1 except that g (3-sol) was used to obtain 5.7 g of neopentyl 3,5-dichloro-2,4-difluorobenzoate. Yield is 64
%Met.
実施例4
実施例2のテトラフェニルホスホニウムプロミドの代わ
りにN−(2−エチルヘキシル)−4−ジメチルアミノ
ピリジニウムクロリド0.8g(3v++ol)を用い
た以外は実施例2と同様に行い3.5−ジクロロ−4−
フルオロ安息香酸ネオペンチル7.6gを得た。収率は
91%であった。Example 4 The same procedure as in Example 2 was carried out except that 0.8 g (3v++ol) of N-(2-ethylhexyl)-4-dimethylaminopyridinium chloride was used instead of tetraphenylphosphonium bromide in Example 2. 3.5 -dichloro-4-
7.6 g of neopentyl fluorobenzoate was obtained. The yield was 91%.
実施例5
冷却管、攪拌器を備えた50m1フラスコに、スプレー
乾燥フッ化カリウム(Laporte Chew、社製
)1、 9 g (33mmol) 、テトラフェニル
ホスホニウムプロミド1. 1 g (2,5mmol
) 、 18−クラウン−6を0. 7g (2,5
vwol) 、 3. 4゜5−トリクロロ安息香酸
エチル6.4g (25n+mol)を入れ、油浴上で
加熱し、窒素雰囲気下、210℃で2時間反応させた。Example 5 In a 50 ml flask equipped with a condenser and a stirrer, 1.9 g (33 mmol) of spray-dried potassium fluoride (manufactured by Laporte Chew) and 1.9 g (33 mmol) of tetraphenylphosphonium bromide were added. 1 g (2.5 mmol
), 18-crown-6 to 0. 7g (2,5
vwol), 3. 6.4 g (25 n+mol) of ethyl 4.5-trichlorobenzoate was added, heated on an oil bath, and reacted at 210° C. for 2 hours under a nitrogen atmosphere.
反応容器を冷却し、トルエン40a+1で希釈し無機塩
を濾過しトルエンを留去した。残渣を減圧蒸留すること
により、3゜5−ジクロロ−4−フルオロ安息香酸エチ
ル3.4gを得た。収率は57%であった。以下に物性
を示す。The reaction vessel was cooled, diluted with toluene 40a+1, inorganic salts were filtered, and toluene was distilled off. The residue was distilled under reduced pressure to obtain 3.4 g of ethyl 3.5-dichloro-4-fluorobenzoate. The yield was 57%. The physical properties are shown below.
Claims (1)
ルキル基を示す。) で表されるフルオロ安息香酸エステル。 2)一般式 ▲数式、化学式、表等があります▼ (式中、Yは水素原子または塩素原子を示し、Rはアル
キル基を示す。) で表されるクロロ安息香酸エステルと金属フルオリドと
を、触媒として第四級ホスホニウム塩、第四級アンモニ
ウム塩およびピリジニウム塩の中から選ばれる少なくと
も1種の塩の存在下、非プロトン性極性溶媒中で反応さ
せ、一般式 ▲数式、化学式、表等があります▼ (式中、Xはフッ素原子または水素原子を示し、Rはア
ルキル基を示す。) で表されるフルオロ安息香酸エステルを製造することを
特徴とするフルオロ安息香酸エステルの製造方法。 3)一般式 ▲数式、化学式、表等があります▼ (式中、Yは水素原子または塩素原子を示し、Rはアル
キル基を示す。) で表されるクロロ安息香酸エステルと金属フルオリドと
を、触媒として第四級ホスホニウム塩、第四級アンモニ
ウム塩およびピリジニウム塩の中から選ばれる少なくと
も1種の塩と、クラウンエーテル及びポリアルキレング
リコール類の中から選ばれる少なくとも1種の化合物と
の組み合わせの存在下反応させ、一般式 ▲数式、化学式、表等があります▼ (式中、Xはフッ素原子または水素原子を示し、Rはア
ルキル基を示す。) で表されるフルオロ安息香酸エステルを製造することを
特徴とするフルオロ安息香酸エステルの製造方法。[Claims] 1) Fluorobenzoic acid ester represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a fluorine atom or a hydrogen atom, and R represents an alkyl group.) . 2) A chlorobenzoic acid ester and a metal fluoride represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y represents a hydrogen atom or a chlorine atom, and R represents an alkyl group.) The reaction is carried out in an aprotic polar solvent in the presence of at least one salt selected from quaternary phosphonium salts, quaternary ammonium salts, and pyridinium salts as a catalyst, and the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the formula, X represents a fluorine atom or a hydrogen atom, and R represents an alkyl group.) A method for manufacturing a fluorobenzoic acid ester, which is characterized by manufacturing a fluorobenzoic acid ester represented by the following formula. 3) A chlorobenzoic acid ester and a metal fluoride represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Y represents a hydrogen atom or a chlorine atom, and R represents an alkyl group.) Presence of a combination of at least one salt selected from quaternary phosphonium salts, quaternary ammonium salts, and pyridinium salts as a catalyst and at least one compound selected from crown ethers and polyalkylene glycols. The following reaction is performed to produce a fluorobenzoic acid ester represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a fluorine atom or a hydrogen atom, and R represents an alkyl group.) A method for producing a fluorobenzoic acid ester, characterized by:
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62155039A JP2612708B2 (en) | 1987-06-22 | 1987-06-22 | Fluorobenzoic acid ester and method for producing the same |
EP88109547A EP0296479B1 (en) | 1987-06-22 | 1988-06-15 | Fluorobenzoates and process for their production |
DE3888733T DE3888733T2 (en) | 1987-06-22 | 1988-06-15 | Fluorobenzoates and their production. |
US07/207,230 US4916253A (en) | 1987-06-22 | 1988-06-16 | Fluorobenzoates and process for their production |
KR1019880007454A KR910003473B1 (en) | 1987-06-22 | 1988-06-21 | Fluoro benzoates and process for their production |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62155039A JP2612708B2 (en) | 1987-06-22 | 1987-06-22 | Fluorobenzoic acid ester and method for producing the same |
Publications (3)
Publication Number | Publication Date |
---|---|
JPS6452A JPS6452A (en) | 1989-01-05 |
JPH0152A true JPH0152A (en) | 1989-01-05 |
JP2612708B2 JP2612708B2 (en) | 1997-05-21 |
Family
ID=15597334
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62155039A Expired - Fee Related JP2612708B2 (en) | 1987-06-22 | 1987-06-22 | Fluorobenzoic acid ester and method for producing the same |
Country Status (5)
Country | Link |
---|---|
US (1) | US4916253A (en) |
EP (1) | EP0296479B1 (en) |
JP (1) | JP2612708B2 (en) |
KR (1) | KR910003473B1 (en) |
DE (1) | DE3888733T2 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2082310T3 (en) * | 1991-09-21 | 1996-03-16 | Hoechst Ag | PROCEDURE FOR THE PREPARATION OF CHLORINE AND FLUORINE BENZENE COMPOUNDS BY SELECTIVE NUCLEOPHYL FLUORODESNITRATION. |
JP2004149458A (en) * | 2002-10-30 | 2004-05-27 | Central Glass Co Ltd | Method for producing fluoro(trifluoromethyl)cinnamic acid |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3044055A1 (en) * | 1980-11-22 | 1982-07-01 | Celamerck Gmbh & Co Kg, 6507 Ingelheim | N-Halo:benzoyl-N'-tetra:halo-phenyl (thio)urea derivs. - prepd. e.g. by reaction of a tetra:halo-aniline with a halo-benzoyl isocyanate or isothiocyanate |
WO1986005487A1 (en) * | 1985-03-14 | 1986-09-25 | Celamerck Gmbh & Co. Kg | Process for the manufacture of benzoyl urea |
GB8621217D0 (en) * | 1986-09-03 | 1986-10-08 | Ici Plc | Chemical compounds |
-
1987
- 1987-06-22 JP JP62155039A patent/JP2612708B2/en not_active Expired - Fee Related
-
1988
- 1988-06-15 DE DE3888733T patent/DE3888733T2/en not_active Expired - Lifetime
- 1988-06-15 EP EP88109547A patent/EP0296479B1/en not_active Expired - Lifetime
- 1988-06-16 US US07/207,230 patent/US4916253A/en not_active Expired - Lifetime
- 1988-06-21 KR KR1019880007454A patent/KR910003473B1/en not_active IP Right Cessation
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