JPH0753692B2 - Method for producing aromatic carboxylic acid esters - Google Patents
Method for producing aromatic carboxylic acid estersInfo
- Publication number
- JPH0753692B2 JPH0753692B2 JP2293004A JP29300490A JPH0753692B2 JP H0753692 B2 JPH0753692 B2 JP H0753692B2 JP 2293004 A JP2293004 A JP 2293004A JP 29300490 A JP29300490 A JP 29300490A JP H0753692 B2 JPH0753692 B2 JP H0753692B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- group
- palladium
- mmol
- phosphine
- 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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 31
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000003054 catalyst Substances 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims description 9
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 125000005087 alkynylcarbonyl group Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 52
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 39
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 26
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 22
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000010926 purge Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000002941 palladium compounds Chemical class 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- -1 aromatic halogen Chemical class 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 4
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl 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
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000004768 bromobenzenes Chemical class 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 2
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 2
- BEHBHYYPTOHUHX-UHFFFAOYSA-N (2-bromophenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1Br BEHBHYYPTOHUHX-UHFFFAOYSA-N 0.000 description 1
- UCIBNEZUFGXWJV-UHFFFAOYSA-N (2-bromophenyl) butanoate Chemical compound CCCC(=O)OC1=CC=CC=C1Br UCIBNEZUFGXWJV-UHFFFAOYSA-N 0.000 description 1
- CQOJLROYGSGCQQ-UHFFFAOYSA-N (2-bromophenyl) propanoate Chemical compound CCC(=O)OC1=CC=CC=C1Br CQOJLROYGSGCQQ-UHFFFAOYSA-N 0.000 description 1
- WLPXNBYWDDYJTN-UHFFFAOYSA-N 1-bromo-2,3-dimethylbenzene Chemical group CC1=CC=CC(Br)=C1C WLPXNBYWDDYJTN-UHFFFAOYSA-N 0.000 description 1
- JVEQWIQHHWNMQX-UHFFFAOYSA-N 1-bromo-2-ethoxybenzene Chemical compound CCOC1=CC=CC=C1Br JVEQWIQHHWNMQX-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- NBHAHMHUMMWFPJ-UHFFFAOYSA-N 1-bromo-2-phenylmethoxybenzene Chemical compound BrC1=CC=CC=C1OCC1=CC=CC=C1 NBHAHMHUMMWFPJ-UHFFFAOYSA-N 0.000 description 1
- LECYCYNAEJDSIL-UHFFFAOYSA-N 1-bromo-2-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC=C1Br LECYCYNAEJDSIL-UHFFFAOYSA-N 0.000 description 1
- DSMRKVAAKZIVQL-UHFFFAOYSA-N 1-bromo-2-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1Br DSMRKVAAKZIVQL-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- JSHASCFKOSDFHY-UHFFFAOYSA-N 1-butylpyrrolidine Chemical compound CCCCN1CCCC1 JSHASCFKOSDFHY-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- KBTMGSMZIKLAHN-UHFFFAOYSA-N 4-bromo-1,2-dimethoxybenzene Chemical compound COC1=CC=C(Br)C=C1OC KBTMGSMZIKLAHN-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- OCUTXRDBYHANJS-UHFFFAOYSA-N BrC1=C(C=CC=C1)O.[P] Chemical compound BrC1=C(C=CC=C1)O.[P] OCUTXRDBYHANJS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- BIHHBTVQFPVSTE-UHFFFAOYSA-N ethyl 2-bromobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1Br BIHHBTVQFPVSTE-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- SWGQITQOBPXVRC-UHFFFAOYSA-N methyl 2-bromobenzoate Chemical compound COC(=O)C1=CC=CC=C1Br SWGQITQOBPXVRC-UHFFFAOYSA-N 0.000 description 1
- IPIVTJSCIHXKOE-UHFFFAOYSA-N methyl 4-propan-2-ylbenzoate Chemical compound COC(=O)C1=CC=C(C(C)C)C=C1 IPIVTJSCIHXKOE-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- XRKQMIFKHDXFNQ-UHFFFAOYSA-N n-cyclohexyl-n-ethylcyclohexanamine Chemical compound C1CCCCC1N(CC)C1CCCCC1 XRKQMIFKHDXFNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PENAXHPKEVTBLF-UHFFFAOYSA-L palladium(2+);prop-1-ene;dichloride Chemical compound [Pd+]Cl.[Pd+]Cl.[CH2-]C=C.[CH2-]C=C PENAXHPKEVTBLF-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- SNOWYPDEJVKXAG-UHFFFAOYSA-N phenyl 2-bromobenzoate Chemical compound BrC1=CC=CC=C1C(=O)OC1=CC=CC=C1 SNOWYPDEJVKXAG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、有機精密化学品として、また、医薬、農薬等
の中間体として重要な芳香族カルボン酸エステル類の新
規な合成法に提供する。詳しくは、臭素化芳香族化合物
を塩基性物質の存在下で一酸化炭素とアルコールを反応
させる際にホスフィンとパラジウムの比を５〜50に調整
したパラジウム−ホスフィン触媒を用いることを特徴と
する芳香族カルボン酸エステル類の製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention provides a novel method for synthesizing aromatic carboxylic acid esters which are important as organic fine chemicals and as intermediates for medicines, agricultural chemicals and the like. . Specifically, when a brominated aromatic compound is reacted with carbon monoxide and an alcohol in the presence of a basic substance, a palladium-phosphine catalyst having a phosphine / palladium ratio adjusted to 5 to 50 is used. The present invention relates to a method for producing a group carboxylic acid ester.
［従来技術］ 従来、芳香族化合物のカルボニル化に関しては各種の方
法が提案されている。例えば、パラジウム−ホスフィン
触媒の存在下でヨウ素化芳香族化合物を一酸化炭素及び
アルコールと反応させて芳香族カルボン酸エステル類を
製造する方法（A.Schoenberg,.I.Bartoletti,R.F.Heck,
J.Org.Chem,.39（1974）,3318）、ベンゼン−水二相系
溶媒中でパラジウム−トリフェニルホスフィン触媒を用
い、相間移動触媒及び過剰の水酸化ナトリウムの共存下
で、芳香族ハロゲン化物をカルボニル化することにより
芳香族カルボン酸のナトリウム塩を合成する方法（L.Ca
ssar,M.Foa,A.Gardano,J.Organomet.Chem.,121（197
6）,C55）等が知られている。しかし、これらの触媒に
は配位子としてトリフェニルホスフィン等のホスフィン
をパラジウム１モル当量に対して２〜４モル当量存在さ
せて行われるが、反応活性が低く、また触媒の安定性が
低いので、パラジウム金属がしばしば析出し、途中で反
応が停止する欠点がある。パラジウム触媒以外にニッケ
ル、コバルト触媒による方法も提案されている（例え
ば、T.A.Weil,L.Cassar,M.Foa,“Organic Syntheses vi
a Metal Carbonyls",ed.I.Wender,P.Pino,Vol.2,John W
iley ＆ Sons,New York,N.Y.,pp.517-543（1977）;T.Ka
shimura,K.Kudo,S.Mori,N.Sugita,1986,299,483,85
1）。しかし、これらの方法は、反応速度が遅く、高温
高圧、または光照射等が必要であり、工業的に実施する
には問題がある。このような状況のもとで芳香族カルボ
ン酸エステル類を効率的に合成できる安定な触媒の開発
が求められていた。[Prior Art] Conventionally, various methods have been proposed for carbonylation of aromatic compounds. For example, a method of producing an aromatic carboxylic acid ester by reacting an iodinated aromatic compound with carbon monoxide and an alcohol in the presence of a palladium-phosphine catalyst (A. Schoenberg, I. Bartoletti, RFHeck,
J.Org.Chem, .39 (1974), 3318), using a palladium-triphenylphosphine catalyst in a benzene-water two-phase solvent, in the presence of a phase transfer catalyst and an excess of sodium hydroxide, an aromatic halogen. Method for synthesizing sodium salt of aromatic carboxylic acid by carbonylation of compound (L.Ca
ssar, M.Foa, A.Gardano, J.Organomet.Chem., 121 (197
6), C55), etc. are known. However, in these catalysts, phosphine such as triphenylphosphine is present as a ligand in the presence of 2 to 4 molar equivalents relative to 1 molar equivalent of palladium, but the reaction activity is low and the stability of the catalyst is low. However, there is a drawback that palladium metal often precipitates and the reaction stops in the middle. In addition to palladium catalysts, nickel and cobalt catalysts have also been proposed (eg TAWeil, L. Cassar, M. Foa, “Organic Syntheses vi
a Metal Carbonyls ", ed.I.Wender, P.Pino, Vol.2, John W
iley & Sons, New York, NY, pp.517-543 (1977); T.Ka
shimura, K.Kudo, S.Mori, N.Sugita, 1986,299,483,85
1). However, these methods have a slow reaction rate, require high temperature and high pressure, or require light irradiation, and thus are problematic for industrial implementation. Under such circumstances, there has been a demand for the development of a stable catalyst capable of efficiently synthesizing aromatic carboxylic acid esters.
本発明者らはかねてより芳香族化合物のカルボニル化反
応について種々研究を重ね、特に原料、触媒、反応条件
等が生成物の収率や選択率に及ぼす影響について広範か
つ綿密な研究を行ってきた。従来、パラジウム−ホスフ
ィン錯体を触媒とする臭素化芳香族化合物のカルボニル
化反応においてホスフィンをパラジウムに対して過剰に
存在させると、反応活性サイトにホスフィンが配位する
ため、反応が阻害されると考えられてきた。しかし、本
発明者がパラジウム−ホスフィン触媒のホスフィンの効
果に関する研究を鋭意行う過程で、意外にもホスフィン
をパラジウムに対し大過剰に添加することにより反応速
度が低下しないばかりか却って増加することを見い出
し、本発明を完成させた。本発明のようにホスフィンを
パラジウムに対して大過剰に存在させる触媒は、触媒活
性の増加と共に触媒の安定性が著しく向上させる効果も
あるので、工業的に実施できる効率的な芳香族カルボン
酸エステルの製造法を提供できる。The present inventors have long conducted various studies on the carbonylation reaction of aromatic compounds, and in particular, have conducted extensive and detailed studies on the influence of raw materials, catalysts, reaction conditions, etc. on the yield and selectivity of products. . Conventionally, it is considered that when phosphine is excessively present with respect to palladium in the carbonylation reaction of a brominated aromatic compound using a palladium-phosphine complex as a catalyst, the reaction is inhibited because the phosphine is coordinated to the reaction active site. Has been. However, in the process in which the present inventor diligently studied the effect of phosphine on a palladium-phosphine catalyst, it was surprisingly found that the addition of phosphine in a large excess relative to palladium not only decreases the reaction rate but rather increases it. The present invention has been completed. A catalyst in which phosphine is present in a large excess relative to palladium as in the present invention has an effect of significantly improving the stability of the catalyst along with an increase in the catalytic activity, and therefore an efficient aromatic carboxylic acid ester that can be industrially implemented Can be provided.
［発明が解決しようとする問題点］ 本発明は、式（Ｉ）で 表わされる臭素化芳香族化合物を塩基性物質の存在下で
一酸化炭素及び一般式（II）R-OHを有するアルコールと
反応させる際、パラジウム化合物１モル当量とホスフィ
ン５〜20モル当量とを反応させることにより得られるパ
ラジウム−ホスフィン触媒を用いる一般式（III）で 表わされる芳香族カルボン酸エステル類を効率的に合成
する方法に関する。[Problems to be Solved by the Invention] The present invention is based on the formula (I). When reacting the represented brominated aromatic compound with carbon monoxide and an alcohol having the general formula (II) R-OH in the presence of a basic substance, 1 molar equivalent of a palladium compound and 5 to 20 molar equivalents of phosphine are reacted. In the general formula (III) using a palladium-phosphine catalyst obtained by It relates to a method for efficiently synthesizing the represented aromatic carboxylic acid esters.
ここに一般式（Ｉ）においてＸ及びＹは、少なくとも一
方が炭素数１〜20の炭化水素基、アルコキシ基、アシロ
キシ基、アルコキシカルボニル基、アシル基、水酸基、
アミノ基、またはハロゲンを表わす。また式（II）及び
（III）においてＲは炭素数１〜20の炭化水素基を表わ
す。In the general formula (I), X and Y are at least one of a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, an acyl group, a hydroxyl group,
Represents an amino group or halogen. In the formulas (II) and (III), R represents a hydrocarbon group having 1 to 20 carbon atoms.
［問題点を解決するための手段］ 以下、本発明について詳細に説明する。[Means for Solving Problems] Hereinafter, the present invention will be described in detail.
本発明は、一般式（Ｉ）で 表わされる臭素化芳香族化合物を塩基性物質の存在下
で、一酸化炭素及び一般式（II）のR-OHで表わされるア
ルコールと反応させる際にパラジウム化合物１モル当量
とホスフィン５〜20モル当量とを反応させることにより
得られるパラジウム−ホスフィン触媒を用いることを特
徴とする一般式（III）で 表わされる芳香族カルボン酸エステル類の合成法を提供
するものである。ここに一般式（Ｉ）においてＸ及びＹ
は少なくとも一方が炭素数１〜20の炭化水素基、アルコ
キシ基、アシロキシ基、アルコキシカルボニル基、アシ
ル基、水酸基、アミノ基、またはハロゲンを表わす。ま
た式（II）及び（III）においてＲは炭素数１〜20の炭
化水素基を表わす。The present invention has the general formula (I) When reacting the represented brominated aromatic compound with carbon monoxide and an alcohol represented by R-OH of the general formula (II) in the presence of a basic substance, 1 molar equivalent of a palladium compound and 5 to 20 molar equivalents of phosphine. In the general formula (III) characterized by using a palladium-phosphine catalyst obtained by reacting with It provides a method for synthesizing the represented aromatic carboxylic acid esters. Here, in the general formula (I), X and Y
At least one represents a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, an amino group, or halogen. In the formulas (II) and (III), R represents a hydrocarbon group having 1 to 20 carbon atoms.
本発明の原料として使用する臭素化芳香族化合物は一般
式（Ｉ）で 表わされる化合物群であり、Ｘ及びＹは少なくとも一方
が炭素数１〜20の炭化水素基、アルコキシ基、アシロキ
シ基、アルコキシカルボニル基、アシル基、水酸基、ア
ミノ基、またはハロゲンを表わす。代表的なものとして
は、ブロモベンゼン、ブロモトルエン、ブロモキシレ
ン、イソプロピルブロモベンゼン、ｔ−ブチルブロモベ
ンゼン等の炭化水素基をもつブロモベンゼン類、臭化ア
ニシル、エトキシブロモベンゼン、ブチロキシブロモベ
ンゼン、フェノキシブロモベンゼン、3,4−ジメトキシ
ブロモベンゼン、3,4−メチレンオキシブロモベンゼン
等のアルコキシブロモベンゼン、アセトキシブロモベン
ゼン、プロピオキシブロモベンゼン、ベンゾキシブロモ
ベンゼン等のアシロキシブロモベンゼン、メトキシカル
ボニルブロモベンゼン、エトキシカルボニルブロモベン
ゼン、プロピオキシカルボニルブロモベンゼン、フェノ
キシカルボニルブロモベンゼン等のアシロキシカルボニ
ル基をもつブロモベンゼン類、ブロモフェノール、ブロ
モアニリン、あるいは前述の置換基をもつブロモナフタ
レン等があげられる。The brominated aromatic compound used as the raw material of the present invention has the general formula (I) At least one of X and Y is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, an amino group, or halogen. Typical examples include bromobenzenes having a hydrocarbon group such as bromobenzene, bromotoluene, bromoxylene, isopropylbromobenzene, and t-butylbromobenzene, anisyl bromide, ethoxybromobenzene, butyroxybromobenzene, and phenoxy. Bromobenzene, 3,4-dimethoxybromobenzene, alkoxybromobenzene such as 3,4-methyleneoxybromobenzene, acetoxybromobenzene, propioxybromobenzene, acyloxybromobenzene such as benzoxybromobenzene, methoxycarbonylbromobenzene, and the like. Bromobenzenes having an acyloxycarbonyl group such as ethoxycarbonyl bromobenzene, propioxycarbonyl bromobenzene and phenoxycarbonyl bromobenzene, bromophenol, bromophenol Phosphorus, or bromonaphthalene like with aforementioned substituent.
本発明で用いる触媒は、前記したようにパラジウム化合
物１モル当量とホスフィン５〜20モル当量とを反応させ
ることにより得られるパラジウム−ホスフィン錯体であ
る。The catalyst used in the present invention is a palladium-phosphine complex obtained by reacting 1 molar equivalent of a palladium compound with 5 to 20 molar equivalents of phosphine as described above.
ホスフィンの使用量がパラジウム化合物１モル当量に対
して５モル当量未満であると、反応活性が低く、また触
媒の安定性が悪いので、パラジウム金属が析出したり、
塗中で反応が停止したりするので好ましくない。また、
ホスフィンをパラジウム化合物１モル当量に対して20モ
ル当量超用いても触媒活性や触媒の安定性が飽和状態と
なるので、ホスフィンの使用量はパラジウム化合物１モ
ル当量に対して20モル当量以下とするのが適当である。
反応活性の高いホスフィンとしてはトリフェニルホスフ
ィン、トリトリルホスフィン、トリアニシルホスフィン
等の芳香族ホスフィン類、トリブチルホスフィン、トリ
イソプロピルホスフィン等のアルキルホスフィン類等が
あげられる。一方、パラジウム化合物としては、塩化パ
ラジウム、パラジウム酸ナトリウム、パラジウム酸カリ
ウム等の無機塩のほか、酢酸パラジウム、パラジウムア
セチルアセトナート、塩化ジ（ベンゾニトリル）パラジ
ウム、塩化π−アリルパラジウム等の有機錯体を用いる
ことができる。パラジウム−ホスフィン錯体は、予め合
成した錯体として反応系に加えてもよいし、パラジウム
化合物とホスフィンを一定の割合で反応器中に充填し、
反応条件下でパラジウム錯体を形成させてもよい。If the amount of phosphine used is less than 5 molar equivalents relative to 1 molar equivalent of the palladium compound, the reaction activity will be low and the stability of the catalyst will be poor, so that palladium metal may precipitate,
This is not preferable because the reaction may stop during coating. Also,
Even if more than 20 molar equivalents of phosphine are used per 1 molar equivalent of the palladium compound, the catalytic activity and stability of the catalyst will be saturated, so the amount of phosphine used should be 20 molar equivalents or less relative to 1 molar equivalent of the palladium compound. Is appropriate.
Examples of the phosphine having high reaction activity include aromatic phosphines such as triphenylphosphine, tritolylphosphine and trianisylphosphine, and alkylphosphines such as tributylphosphine and triisopropylphosphine. On the other hand, as the palladium compound, in addition to inorganic salts such as palladium chloride, sodium palladate, and potassium palladate, palladium acetate, palladium acetylacetonate, di (benzonitrile) palladium chloride, organic complexes such as π-allylpalladium chloride, etc. Can be used. The palladium-phosphine complex may be added to the reaction system as a complex synthesized in advance, or a palladium compound and phosphine may be charged into the reactor at a constant ratio,
A palladium complex may be formed under the reaction conditions.
本発明で用いる塩基性物質は反応により生成する臭化水
素を捕捉することにより反応を著しく促進する効果を有
しており、これを添加することにより目的化合物を効率
的に得ることができる。塩基性物質の代表的なものとし
ては、トリエチルアミン、トリプロピルアミン、トリイ
ソプロピルアミン、トリブチルアミン、ジシクロヘキシ
ルエチルアミン等の脂肪族アミン、Ｎ−メチルピロリジ
ン、Ｎ−メチルピペリジン、Ｎ−メチルモルホリン、Ｎ
−ブチルピロリジン等の環状アミン、N,N,N′,N′−テ
トラメチルエチレンジアミン、N,N,N′,N′−テトラメ
チルプロピレンジアミン、N,N,N′,N′−テトラメチル
ブチレンジアミン、N,N,N′,N′−テトラメチルヘキサ
メチレンジアミン等のジアミン類、あるいはN,N−ジメ
チルアニリン、N,N−ジエチルアニリン、ピリジン、４
−ジメチルアミノピリジン等の芳香族アミン類、水酸化
テトラブチル等の水酸化第４級アンモニウム、またはこ
れらを高分子に結合させたものがあげられる。これらの
塩基性物質の使用量は、原料中の臭素１モル当量に対
し、0.1〜20モル当量、好ましくは１〜５モル当量であ
る。The basic substance used in the present invention has an effect of remarkably promoting the reaction by trapping hydrogen bromide generated by the reaction, and by adding this, the target compound can be efficiently obtained. Typical examples of the basic substance include aliphatic amines such as triethylamine, tripropylamine, triisopropylamine, tributylamine and dicyclohexylethylamine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine and N.
-Cyclic amines such as butylpyrrolidine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N'-tetramethylbutylene Diamines such as diamine, N, N, N ', N'-tetramethylhexamethylenediamine, or N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4
-Aromatic amines such as dimethylaminopyridine, quaternary ammonium hydroxide such as tetrabutyl hydroxide, or those obtained by binding these to a polymer. The amount of these basic substances used is 0.1 to 20 molar equivalents, preferably 1 to 5 molar equivalents, relative to 1 molar equivalent of bromine in the raw material.
一般式（II）R-OHで表わされるアルコール類としては、
Ｒが１〜20を有する炭化水素基を有するものがあげられ
る。例えば、メチル、エチル基等のアルキル基、シクロ
ペンチル、シクロヘキシル等のシクロアルキル基、フェ
ニル、ベンジル基等のアリール基を含む脂肪族、脂環
族、または芳香族の炭化水素基である。従って、一般式
（III）で表わされる化合物としては安息香酸エチル、
安息香酸メチル、ｐ−トリル酸メチル、ｐ−イソプロピ
ル安息香酸メチル等があげられる。Examples of alcohols represented by the general formula (II) R-OH include
Examples thereof include those having a hydrocarbon group in which R has 1 to 20. For example, it is an aliphatic, alicyclic, or aromatic hydrocarbon group containing an alkyl group such as a methyl or ethyl group, a cycloalkyl group such as cyclopentyl or cyclohexyl, or an aryl group such as a phenyl or benzyl group. Therefore, as the compound represented by the general formula (III), ethyl benzoate,
Examples thereof include methyl benzoate, p-methyl triphosphate, and methyl p-isopropyl benzoate.
反応装置としては通常用いられる流通式あるい回分式高
圧反応装置が適当である。反応は一酸化炭素加圧下で行
う。一酸化炭素の圧力はゲージ圧で１〜200kg/cm2、好
ましくは３〜100kg/cm2である。また反応温度は50〜200
℃、好ましくは100〜180℃である。As the reaction apparatus, a flow type or batch type high pressure reaction apparatus which is usually used is suitable. The reaction is carried out under pressure with carbon monoxide. The pressure of carbon monoxide is 1 to 200 kg / cm 2 , preferably 3 to 100 kg / cm 2 as a gauge pressure. The reaction temperature is 50 to 200.
C., preferably 100 to 180.degree.
［実施例］ 次に本発明を実施例により、更に詳細に説明する。EXAMPLES Next, the present invention will be described in more detail with reference to examples.
実施例１ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン131.1mg（0.5mmol）、エタノール
10ml及びベンゼン10mlを100mlオートクレーブに仕込
み、一酸化炭素で50kg/cm2に加圧した。次に140℃に昇
温させて２時間反応させた。反応後過剰の一酸化炭素を
パージした後、反応液を取り出し、ガスクロマトグラフ
ィーにより分析した。その結果、仕込んだブロモベンゼ
ンの17.15％が反応し、安息香酸エチル8.57mmol（触媒
活性85.7/h）が得られた。Example 1 7.85 g (50 mmol) of bromobenzene, 5.0 of triethylamine
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 131.1mg (0.5mmol), ethanol
10 ml and 10 ml of benzene were charged into a 100 ml autoclave and pressurized with carbon monoxide to 50 kg / cm 2 . Next, the temperature was raised to 140 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 17.15% of the charged bromobenzene was reacted, and 8.57 mmol of ethyl benzoate (catalytic activity 85.7 / h) was obtained.
実施例２ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン262.3mg（0.1mmol）、エタノール
10ml及びベンゼン10mlを100mlオートクレーブに仕込
み、一酸化炭素で50kg/cm2に加圧した。次に140℃に昇
温させて２時間反応させた。反応後過剰の一酸化炭素を
パージした後、反応液を取り出し、ガスクロマトグラフ
ィーにより分析した。その結果、仕込んだブロモベンゼ
ンの12.04％が反応し、安息香酸エチル6.02mmol（触媒
活性60.2/h）が得られた。Example 2 7.85 g (50 mmol) of bromobenzene, 5.0 of triethylamine
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 262.3mg (0.1mmol), ethanol
10 ml and 10 ml of benzene were charged into a 100 ml autoclave and pressurized with carbon monoxide to 50 kg / cm 2 . Next, the temperature was raised to 140 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 12.04% of the charged bromobenzene reacted and 6.02 mmol of ethyl benzoate (catalyst activity 60.2 / h) was obtained.
実施例３ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン262.3mg（0.1mmol）、エタノール
10ml及びベンゼン10mlを100mlオートクレーブに仕込
み、一酸化炭素で5kg/cm2に加圧した。次に120℃に昇温
させて２時間反応させた。反応後過剰の一酸化炭素をパ
ージした後、反応液を取り出し、ガスクロマトグラフィ
ーにより分析した。その結果、仕込んだブロモベンゼン
の10.35％が反応し、安息香酸エチル5.18mmol（触媒活
性51.8/h）が得られた。Example 3 7.85 g (50 mmol) of bromobenzene, 5.0 of triethylamine
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 262.3mg (0.1mmol), ethanol
10 ml and 10 ml of benzene were charged into a 100 ml autoclave and pressurized with carbon monoxide to 5 kg / cm 2 . Next, the temperature was raised to 120 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 10.35% of the charged bromobenzene reacted, and 5.18 mmol of ethyl benzoate (catalytic activity 51.8 / h) was obtained.
実施例４ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン262.3mg（0.1mmol）、エタノール
10ml及びベンゼン10mlを100mlオートクレーブに仕込
み、一酸化炭素で20kg/cm2に加圧した。次に120℃に昇
温させて２時間反応させた。反応後過剰の一酸化炭素を
パージした後、反応液を取り出し、ガスクロマトグラフ
ィーにより分析した。その結果、仕込んだブロモベンゼ
ンの6.60％が反応し、安息香酸エチル3.30mmol（触媒活
性33.0/h）が得られた。Example 4 7.85 g (50 mmol) of bromobenzene and 5.0 of triethylamine
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 262.3mg (0.1mmol), ethanol
10 ml and 10 ml of benzene were charged into a 100 ml autoclave and pressurized with carbon monoxide to 20 kg / cm 2 . Next, the temperature was raised to 120 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 6.60% of the charged bromobenzene reacted, and 3.30 mmol of ethyl benzoate (catalytic activity 33.0 / h) was obtained.
実施例５ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン262.3mg（0.1mmol）、エタノール
10ml及びベンゼン10mlを100mlオートクレーブに仕込
み、一酸化炭素で5kg/cm2に加圧した。次に120℃に昇温
させて２時間反応させた。反応後過剰の一酸化炭素をパ
ージした後、反応液を取り出し、ガスクロマトグラフィ
ーにより分析した。その結果、仕込んだブロモベンゼン
の10.35％が反応し、安息香酸エチル5.18mmol（触媒活
性51.8/h）が得られた。Example 5 7.85 g (50 mmol) of bromobenzene, 5.0 of triethylamine
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 262.3mg (0.1mmol), ethanol
10 ml and 10 ml of benzene were charged into a 100 ml autoclave and pressurized with carbon monoxide to 5 kg / cm 2 . Next, the temperature was raised to 120 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 10.35% of the charged bromobenzene reacted, and 5.18 mmol of ethyl benzoate (catalytic activity 51.8 / h) was obtained.
実施例６ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リス（ｐ−トリル）ホスフィン152.2mg（0.5mmol）、エ
タノール10ml及びベンゼン10mlを100mlオートクレーブ
に仕込み、一酸化炭素で50kg/cm2に加圧した。次に140
℃に昇温させて２時間反応させた。反応後過剰の一酸化
炭素をパージした後、反応液を取り出し、ガスクロマト
グラフィーにより分析した。その結果、仕込んだブロモ
ベンゼンの10.0％が反応し、安息香酸エチル4.98mmol
（触媒活性49.8/h）が得られた。Example 6 7.85 g (50 mmol) of bromobenzene, 5.0 of triethylamine
Charge 5 g (50 mmol), palladium chloride 8.9 mg (0.05 mmol), tris (p-tolyl) phosphine 152.2 mg (0.5 mmol), ethanol 10 ml and benzene 10 ml into a 100 ml autoclave and pressurize with carbon monoxide to 50 kg / cm 2 . did. Then 140
The temperature was raised to ℃ and reacted for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 10.0% of the charged bromobenzene reacted, and ethyl benzoate 4.98 mmol
(Catalytic activity 49.8 / h) was obtained.
実施例７ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リス（ｐ−アニシル）ホスフィン176.2mg（0.5mmol）、
エタノール10ml及びベンゼン10mlを100mlオートクレー
ブに仕込み、一酸化炭素で50kg/cm2に加圧した。次に14
0℃に昇温させて２時間反応させた。反応後過剰の一酸
化炭素をパージした後、反応液を取り出し、ガスクロマ
トグラフィーにより分析した。その結果、仕込んだブロ
モベンゼンの7.2％が反応し、安息香酸エチル3.62mmol
（触媒活性36.2/h）が得られた。Example 7 7.85 g (50 mmol) of bromobenzene and 5.0 of triethylamine
5 g (50 mmol), palladium chloride 8.9 mg (0.05 mmol), tris (p-anisyl) phosphine 176.2 mg (0.5 mmol),
10 ml of ethanol and 10 ml of benzene were charged into a 100 ml autoclave and pressurized with carbon monoxide to 50 kg / cm 2 . Then 14
The temperature was raised to 0 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 7.2% of the charged bromobenzene reacted, and ethyl benzoate 3.62 mmol
(Catalytic activity 36.2 / h) was obtained.
比較例１ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン26.2mg（0.1mmol）、エタノール1
0ml及びベンゼン10mlを100mlオートクレーブに仕込み、
一酸化炭素で5kg/cm2に加圧した。次に120℃に昇温させ
て２時間反応させた。反応後過剰の一酸化炭素をパージ
した後、反応液を取り出し、ガスクロマトグラフィーに
より分析した。その結果、仕込んだブロモベンゼンの1.
36％が反応し、安息香酸エチル0.68mmol（触媒活性6.8/
h）が得られた。Comparative Example 1 Bromobenzene 7.85 g (50 mmol), triethylamine 5.0
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 26.2mg (0.1mmol), ethanol 1
Charge 0 ml and benzene 10 ml into a 100 ml autoclave,
Pressurized with carbon monoxide to 5 kg / cm 2 . Next, the temperature was raised to 120 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 1.
36% reacted, ethyl benzoate 0.68mmol (catalyst activity 6.8 /
h) was obtained.
比較例２ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン26.2mg（0.1mmol）、エタノール1
0ml及びベンゼン10mlを100mlオートクレーブに仕込み、
一酸化炭素で50kg/cm2に加圧した。次に120℃に昇温さ
せて２時間反応させた。反応後過剰の一酸化炭素をパー
ジした後、反応液を取り出し、ガスクロマトグラフィー
により分析した。その結果、仕込んだブロモベンゼンの
1.36％が反応し、安息香酸エチル0.84mmol（触媒活性8.
4/h）が得られた。Comparative Example 2 Bromobenzene 7.85 g (50 mmol), triethylamine 5.0
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 26.2mg (0.1mmol), ethanol 1
Charge 0 ml and benzene 10 ml into a 100 ml autoclave,
Pressurized with carbon monoxide to 50 kg / cm 2 . Next, the temperature was raised to 120 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result,
1.36% reacted, 0.84 mmol of ethyl benzoate (catalytic activity 8.
4 / h) was obtained.
比較例３ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン26.2mg（0.1mmol）、エタノール1
0ml及びベンゼン10mlを100mlオートクレーブに仕込み、
一酸化炭素で50kg/cm2に加圧した。次に140℃に昇温さ
せて２時間反応させた。反応後過剰の一酸化炭素をパー
ジした後、反応液を取り出し、ガスクロマトグラフィー
により分析した。その結果、仕込んだブロモベンゼンの
0.48％が反応し、安息香酸エチル0.24mmol（触媒活性2.
4/h）が得られた。Comparative Example 3 Bromobenzene 7.85 g (50 mmol), triethylamine 5.0
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 26.2mg (0.1mmol), ethanol 1
Charge 0 ml and benzene 10 ml into a 100 ml autoclave,
Pressurized with carbon monoxide to 50 kg / cm 2 . Next, the temperature was raised to 140 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result,
0.48% reacted, 0.24 mmol of ethyl benzoate (catalytic activity 2.
4 / h) was obtained.
比較例４ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リフェニルホスフィン52.2mg（0.2mmol）、エタノール1
0ml及びベンゼン10mlを100mlオートクレーブに仕込み、
一酸化炭素で50kg/cm2に加圧した。次に140℃に昇温さ
せて２時間反応させた。反応後過剰の一酸化炭素をパー
ジした後、反応液を取り出し、ガスクロマトグラフィー
により分析した。その結果、仕込んだブロモベンゼンの
1.84％が反応し、安息香酸エチル0.92mmol（触媒活性9.
2/h）が得られた。Comparative Example 4 Bromobenzene 7.85 g (50 mmol), triethylamine 5.0
5g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 52.2mg (0.2mmol), ethanol 1
Charge 0 ml and benzene 10 ml into a 100 ml autoclave,
Pressurized with carbon monoxide to 50 kg / cm 2 . Next, the temperature was raised to 140 ° C. and the reaction was performed for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result,
1.84% reacted, 0.92 mmol of ethyl benzoate (catalytic activity 9.
2 / h) was obtained.
比較例５ ブロモベンゼン7.85g（50mmol）、トリエチルアミン5.0
5g（50mmol）、塩化パラジウム8.9mg（0.05mmol）、ト
リス（ｐ−トリル）ホスフィン30.4mg（0.1mmol）、エ
タノール10ml及びベンゼン10mlを100mlオートクレーブ
に仕込み、一酸化炭素で50kg/cm2に加圧した。次に140
℃に昇温させて２時間反応させた。反応後過剰の一酸化
炭素をパージした後、反応液を取り出し、ガスクロマト
グラフィーにより分析した。その結果、仕込んだブロモ
ベンゼンの1.7％が反応し、安息香酸エチル0.86mmol
（触媒活性8.6/h）が得られた。Comparative Example 5 Bromobenzene 7.85 g (50 mmol), triethylamine 5.0
Charge 5 g (50 mmol), palladium chloride 8.9 mg (0.05 mmol), tris (p-tolyl) phosphine 30.4 mg (0.1 mmol), ethanol 10 ml and benzene 10 ml into a 100 ml autoclave and pressurize with carbon monoxide to 50 kg / cm 2 . did. Then 140
The temperature was raised to ℃ and reacted for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography. As a result, 1.7% of the charged bromobenzene reacted, and ethyl benzoate 0.86 mmol
(Catalytic activity 8.6 / h) was obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 竹内 和彦 茨城県つくば市東１丁目１番地 工業技術 院化学技術研究所内 (56)参考文献 特開 昭61−12649（ＪＰ，Ａ) 特開 昭56−61322（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiko Takeuchi, 1-1, Higashi, Tsukuba-shi, Ibaraki Industrial Technology Institute, Institute of Chemical Research (56) References JP 61-12649 (JP, A) JP 56- 61322 (JP, A)
Claims (1)
なくとも一方が、水素、炭素数１〜10の炭化水素基、ア
ルコキシ基、アシロキン基、アルニキシカルボニル基、
アシル基、水酸基、アミノ基、またはハロゲンを表わ
す。）を塩基性物質の存在下で一酸化炭素及び一般式
（II）R-OH（式中、Ｒは炭素数１〜20を有する炭化水素
基を表わす。）を有するアルコールと反応させる際、パ
ラジウム化合物１モル当量とホスフィン５〜20モル当量
とを反応させることにより得られるパラジウム−ホスフ
ィン触媒を用いることを特徴とする一般式（III）で 表わされる芳香族カルボン酸エステル類（式中、Ｘ、Ｙ
及びＲは前記の通り。）を製造する方法。1. A formula (I) A brominated aromatic compound represented by the formula (wherein at least one of X and Y is hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group, an acylokin group, an alkynylcarbonyl group,
It represents an acyl group, a hydroxyl group, an amino group, or halogen. Is reacted with carbon monoxide and an alcohol having the general formula (II) R-OH (wherein R represents a hydrocarbon group having 1 to 20 carbon atoms) in the presence of a basic substance, palladium In the general formula (III), characterized by using a palladium-phosphine catalyst obtained by reacting 1 molar equivalent of a compound with 5 to 20 molar equivalents of phosphine. Aromatic carboxylic acid esters represented (wherein X, Y
And R are as described above. ) Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2293004A JPH0753692B2 (en) | 1990-10-30 | 1990-10-30 | Method for producing aromatic carboxylic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2293004A JPH0753692B2 (en) | 1990-10-30 | 1990-10-30 | Method for producing aromatic carboxylic acid esters |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04208250A JPH04208250A (en) | 1992-07-29 |
| JPH0753692B2 true JPH0753692B2 (en) | 1995-06-07 |
Family
ID=17789230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2293004A Expired - Lifetime JPH0753692B2 (en) | 1990-10-30 | 1990-10-30 | Method for producing aromatic carboxylic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0753692B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002167351A (en) * | 2000-11-30 | 2002-06-11 | Adchemco Corp | Method for producing 4,4'-dicarboxy diphenylether and it's derivative |
| FR2997696B1 (en) * | 2012-11-08 | 2014-12-05 | Servier Lab | NOVEL PROCESS FOR THE SYNTHESIS OF (2E) -3- (3,4-DIMETHOXYPHENYL) PROP-2-ENENITRILE, AND APPLICATION TO THE SYNTHESIS OF IVABRADINE AND ITS SALTS OF ADDITION TO A PHARMACEUTICALLY ACCEPTABLE ACID |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988358A (en) * | 1974-05-10 | 1976-10-26 | The University Of Delaware | Process for the preparation of carboxylic acid esters from organic halides |
| JPS5661322A (en) * | 1979-10-23 | 1981-05-26 | Mitsui Toatsu Chem Inc | Production of aromatic polycarboxylic acid or ester |
| JPS6112649A (en) * | 1984-06-29 | 1986-01-21 | Mitsui Toatsu Chem Inc | Preparation of aromatic carboxylic acid ester |
| US4668816A (en) * | 1985-11-12 | 1987-05-26 | Stauffer Chemical Company | High yield carbonylation of halo-hydrocarbons |
| US4713484A (en) * | 1985-11-12 | 1987-12-15 | Stauffer Chemical Company | Single phase carbonylation of aromatic halides to carboxylic acid salts |
| JPH0788341B2 (en) * | 1987-03-14 | 1995-09-27 | 日本農薬株式会社 | Method for producing carboxamides |
-
1990
- 1990-10-30 JP JP2293004A patent/JPH0753692B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04208250A (en) | 1992-07-29 |
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