JPH04208250A - Production of aromatic carboxylic acid esters - Google Patents
Production of aromatic carboxylic acid estersInfo
- Publication number
- JPH04208250A JPH04208250A JP2293004A JP29300490A JPH04208250A JP H04208250 A JPH04208250 A JP H04208250A JP 2293004 A JP2293004 A JP 2293004A JP 29300490 A JP29300490 A JP 29300490A JP H04208250 A JPH04208250 A JP H04208250A
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- phosphine
- reaction
- catalyst
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 11
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 43
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 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
- 229910002090 carbon oxide Inorganic materials 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 11
- -1 aromatic halides Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000002194 synthesizing effect Effects 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
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 150000002941 palladium compounds Chemical class 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
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-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
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000004768 bromobenzenes 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000047 product Substances 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
- 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
- HFEFLNNDSLOUEM-UHFFFAOYSA-N 1-bromo-2-butoxybenzene Chemical group CCCCOC1=CC=CC=C1Br HFEFLNNDSLOUEM-UHFFFAOYSA-N 0.000 description 1
- JVEQWIQHHWNMQX-UHFFFAOYSA-N 1-bromo-2-ethoxybenzene Chemical group CCOC1=CC=CC=C1Br JVEQWIQHHWNMQX-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical group CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- RRWFUWRLNIZICP-UHFFFAOYSA-N 1-bromo-2-phenoxybenzene Chemical group BrC1=CC=CC=C1OC1=CC=CC=C1 RRWFUWRLNIZICP-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 group CC(C)C1=CC=CC=C1Br LECYCYNAEJDSIL-UHFFFAOYSA-N 0.000 description 1
- DSMRKVAAKZIVQL-UHFFFAOYSA-N 1-bromo-2-tert-butylbenzene Chemical group 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
- 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
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-UHFFFAOYSA-N 0.000 description 1
- KBTMGSMZIKLAHN-UHFFFAOYSA-N 4-bromo-1,2-dimethoxybenzene Chemical group COC1=CC=C(Br)C=C1OC KBTMGSMZIKLAHN-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical group COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-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
- 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- QARVLSVVCXYDNA-IDEBNGHGSA-N bromobenzene Chemical group Br[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 QARVLSVVCXYDNA-IDEBNGHGSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 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
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003814 drug Substances 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- VEAZEPMQWHPHAG-UHFFFAOYSA-N n,n,n',n'-tetramethylbutane-1,4-diamine Chemical compound CN(C)CCCCN(C)C VEAZEPMQWHPHAG-UHFFFAOYSA-N 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
- ILCQYORZHHFLNL-UHFFFAOYSA-N n-bromoaniline Chemical compound BrNC1=CC=CC=C1 ILCQYORZHHFLNL-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
- 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
- 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
- 150000003003 phosphines Chemical class 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
- 239000002244 precipitate Substances 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
- 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
- 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
- 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
- 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 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)
Abstract
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] [Industrial Application Field] The present invention provides a novel method for synthesizing aromatic carboxylic acid esters, which are important as organic fine chemicals and intermediates for pharmaceuticals, agricultural chemicals, etc. . Specifically, an aromatic product characterized by using a palladium-phosphine catalyst in which the ratio of phosphine and palladium is adjusted to 5 to 50 when reacting a brominated aromatic compound with carbon monoxide and alcohol in the presence of a basic substance. The present invention relates to a method for producing group carboxylic acid esters.
［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。[Prior Art] Conventionally, various methods have been proposed for carbonylating aromatic compounds. For example, a method for producing aromatic carboxylic acid esters by reacting an iodinated aromatic compound with carbon monoxide and alcohol in the presence of a palladium-phosphine catalyst (A).
Ｓｃｈｏｅｎｂｅｒｇ、 、 Ｉ 、 Ｂａｒｔｏｌｅ
ｔｔｉ 、 Ｒ、Ｆ 、 Ｈｅｃｋ 、 Ｊ、 Ｏｒｇ
、 ＣｈＣｍ 。Schoenberg, I., Bartole
tti, R.F., Heck, J., Org.
, ChCm.
、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、
Ｃａ５ｓａｒ、Ｍ、Ｆｏａ、Ａ、Ｇａｒｄａｎｏ、Ｊ
。, 39 (1974), 3318), carbonylation of aromatic halides using a palladium-triphenylphosphine catalyst in a benzene-water two-phase solvent in the presence of a phase transfer catalyst and excess sodium hydroxide. A method for synthesizing sodium salts of aromatic carboxylic acids (L,
Ca5sar, M., Foa, A., Gardano, J.
.
Ｏｒｇａｎｏｍｅｔ、Ｃｈｅｍ、 、 １２１ （１９
７６） 、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に対して２〜４モル等量存在させ
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、Ｃａ５ｓａｒ、Ｍ、Ｆｏａ、”
ＯｒｇａｎｊｃＳｙｎｔｈｅｓｅｓ ｖｉａ Ｍｅｔａ
ｌ Ｃａｒｂｏｎｙｌゲ’、ｅｄ、ＩＪｌｅｎｄｅｒ、
Ｐ。Organomet, Chem, , 121 (19
76), C55), etc. are known. However, these catalysts are carried out in the presence of 2 to 4 molar equivalents of phosphine such as triphenylphosphine as a ligand to palladium, but the reaction activity is low and the stability of the catalyst is low, so palladium The disadvantage is that metals often precipitate and the reaction stops midway. In addition to palladium catalysts, methods using nickel and cobalt catalysts have also been proposed (for example,
T, A, Weil, L, Ca5sar, M, Foa,”
OrganjcSyntheses via Meta
l Carbonylge', ed, IJlender,
P.
Ｐｉｎｏ、Ｖｏｌ、２．Ｊｏｈｎ Ｗｉｌｅｙ ＆ ５
ｏｎｓ、Ｎｅｗ Ｙｏｒｋ、Ｎ、Ｙ、。Pino, Vol. 2. John Wiley & 5
ons, New York, N.Y.
ｐｐ、５１７−５４３ （１９７７） ；Ｔ、Ｋａｓｈ
ｉｍｕｒａ、 Ｋ、 Ｋｕｄｏ、Ｓ、Ｍｏｒｉ、 Ｎ。pp, 517-543 (1977); Kash, T.
imura, K., Kudo, S., Mori, N.
Ｓｕｇｉｔａ、１９８６，２９９，４８３，８５１）
、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て芳香族カルボン酸
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。Sugita, 1986, 299, 483, 851)
However, these methods have problems in industrial implementation because the reaction rate is slow and high temperature and pressure, or light irradiation, etc. are required. Under these circumstances, there has been a demand for the development of stable catalysts that can efficiently synthesize 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。The present inventors have long conducted various studies on the carbonylation reaction of aromatic compounds, and in particular, conducted extensive and thorough research on the effects of raw materials, catalysts, reaction conditions, etc. on the yield and selectivity of the product. .
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。Conventionally, it has been thought that when phosphine is present in excess of palladium in the carbonylation reaction of brominated aromatic compounds using a palladium-phosphine complex as a catalyst, the reaction is inhibited because the phosphine coordinates to the reaction active site. I've been exposed to it. However, in the course of intensive research into the effects of phosphine in palladium-phosphine catalysts, the present inventor unexpectedly discovered that adding phosphine in large excess to palladium not only does not reduce the reaction rate, but actually increases it. , completed the present invention. A catalyst in which phosphine is present in large excess relative to palladium as in the present invention has the effect of increasing catalyst activity and significantly improving catalyst stability, so it is an efficient aromatic carboxylic acid ester that can be implemented industrially. We can provide a manufacturing method for
［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、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
る一般式（Ｉｌｌ）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 provides a method for treating a brominated aromatic compound represented by formula (I) with carbon monoxide and an alcohol having the general formula (II) R, -OH in the presence of a basic substance. The present invention relates to a method for efficiently synthesizing aromatic carboxylic acid esters represented by the general formula (Ill) using a palladium-phosphine catalyst in which the ratio of phosphine and palladium is adjusted to 5 to 50.
ここに一般式（１）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 (1), at least one of X and Y 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 a halogen. Also, the formula (]II
In (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] The present invention will be explained in detail below.
本発明は、一般式（１）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
、−ｍ化炭素及び一般式（ＩＩ） Ｒ−〇Ｈで表わされ
るアルコールと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一般式（ｍ）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（１）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。In the present invention, when a brominated aromatic compound represented by the general formula (1) is reacted with -m carbon and an alcohol represented by the general formula (II) R-○H in the presence of a basic substance, phosphine The present invention provides a method for synthesizing aromatic carboxylic acid esters represented by the general formula (m), which is characterized by using a palladium-phosphine catalyst in which the ratio of palladium and palladium is adjusted to 5 to 50. Here, in general formula (1), X and Y
represents a hydrocarbon group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, an acyl group, a hydroxyl group, an amino group, or a halogen, at least one of which has 1 to 20 carbon atoms.
また式（ＩＩ）及び（ｍ）においてＲは炭素数１〜２０
の炭化水素基を表わす。In formulas (II) and (m), R has 1 to 20 carbon atoms.
represents a hydrocarbon group.
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（１）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
ベンゼ匙、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 a raw material in the present invention is a group of compounds represented by the general formula (1), where at least one of X and Y is a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group, an acyloxy group, an alkoxy carbonyl group, acyl group, hydroxyl group,
Represents an amino group or halogen. Typical examples include bromobenzenes with hydrocarbon groups such as bromobenzene, bromotoluene, bromoxylene, isopropylbromobenzene, t-butylbromobenzene, anisyl bromide, ethoxybromobenzene, butyloxybromobenzene, phenoxy Bromobenzene, 3,4-dimethoxybromobenzene, alkoxybromobenzene such as 3,4-methyleneoxybromobenzene, acyloxybromobenzene such as acetoxybromobenzene, propioxybromobenzene, benzoxybromobenzene, methoxycarbonylbromobenzene, Bromobenzenes with an acyloxycarbonyl group such as ethoxycarbonylbromobenzene, propioxycarbonylbromobenzene, phenoxycarbonylbromobenzene, bromophenol,
Examples include bromoaniline and bromonaphthalene having the above-mentioned substituents.
本発明１で用いる触媒は、パラジウム−ホスフィン錯体
である。この際、ホスフィンとパラジウムの比は５〜５
０、好ましくは５〜２０に調整される。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、ド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。The catalyst used in the present invention 1 is a palladium-phosphine complex. At this time, the ratio of phosphine and palladium is 5 to 5.
0, preferably 5-20. Examples of phosphines with high reaction activity include aromatic phosphines such as triphenylphosphine, tritolylphosphine, and dorianisylphosphine, and alkylphosphines such as tributylphosphine and triisopropylphosphine. On the other hand, palladium compounds include inorganic salts such as palladium chloride, sodium palladate, and potassium palladate, as well as palladium acetate, palladium acetylacetonate, di(benzonitrile) palladium chloride, and π-chloride.
Organic complexes such as allyl palladium can be used.
パラジウム−ホスフィン錯体は、予め合成した錯体とし
て反応系に加ミ１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。この際、パラジウ
ム化合物の使用量は１／１０〜１／３０００モル等量、
好ましくは１１５０〜１／１０００モル等量である。The palladium-phosphine complex may be added to the reaction system as a pre-synthesized complex, or the palladium compound and phosphine may be charged into a reactor at a certain ratio and a palladium complex may be formed under the reaction conditions. . At this time, the amount of palladium compound used is 1/10 to 1/3000 molar equivalent,
Preferably it is 1150 to 1/1000 molar equivalent.
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、ジシクロへキシ
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７、Ｎ。The basic substance used in the present invention has the effect of significantly accelerating the reaction by capturing hydrogen bromide produced by the reaction, and by adding this basic substance, the target compound can be efficiently obtained. Typical basic substances include aliphatic amines such as triethylamine, tripropylamine, triisopropylamine, tributylamine, and dicyclohexylethylamine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, and N-methylpyrrolidine.
- Cyclic amines such as butylpyrrolidine 7,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’ −テトラメチルへキ
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、原料中の臭素に対し０．
１〜２０モル等量、好ましくは１〜５モル等量である。N, N', N'-tetramethylethylenediamine,
Diamines such as N, N, N', N'-tetramethylpropylene diamine, N, N, N', N'-tetramethylbutylene diamine, N, N, N', N'-tetramethylhexamethylene diamine, etc. , or N, N-
Aromatic amines such as dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine,
Examples include quaternary ammonium hydroxide such as tetrabutyl hydroxide, or those bonded to polymers. The amount of these basic substances used is 0.0% relative to the bromine in the raw materials.
1 to 20 molar equivalents, preferably 1 to 5 molar equivalents.
一般式（ｎ）Ｒ−○Ｈ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、−
数式（ｍ）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 the alcohols represented by the general formula (n) R-○H include those having a hydrocarbon group in which R has 1 to 20. For example, alkyl groups such as methyl and ethyl groups,
Aliphatic groups containing cycloalkyl groups such as cyclopentyl and cyclohexyl, and aryl groups such as phenyl and benzyl groups;
It is an alicyclic or aromatic hydrocarbon group. Therefore, −
Examples of the compound represented by formula (m) include ethyl benzoate, methyl benzoate, methyl p-tolylate, and methyl p-isopropylbenzoate.
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。−酸化炭素の圧力はゲージ圧て１−２００ ｋ ｇ
／ ｃ ｍ２、好ましくは３−１００ｋ ｇ ／ ｃ
ｒｄである。また反応温度は５ｏ〜２０００Ｃ１好ま
しくは１００〜１８０℃である。As the reactor, a commonly used flow type or batch type high pressure reactor is suitable. The reaction is carried out under pressure of carbon monoxide. -The pressure of carbon oxide is 1-200 kg by gauge pressure.
/cm2, preferably 3-100kg/c
It is rd. Further, the reaction temperature is 5°C to 2000°C, preferably 100°C to 180°C.
［実施例］ 次に本発明を実施例により、更に詳細に説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
実施例１
ブロモベンゼン７．８５ｇ （５０ｍｍｏｌ）、トリエ
チルアミン５．０５ｇ （５０ｍｍｏｌ）、塩化パラジ
ウム８．９ｍｇ （０，０５ｍｍｏ ｌ）、トリフェニ
ルホスフィン１３１．１ｍｇ （０，５ｍｍｏｌ）、エ
タノール１０ｍ１及びベンゼン１０ｍ１を１００ ｍ
ｌオートクレーブに仕込み、−酸化炭素で５０ ｋ ｇ
／ ｃ ｍに加圧した。次に１４０ ’Ｃ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。Example 1 Bromobenzene 7.85g (50mmol), triethylamine 5.05g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 131.1mg (0.5mmol), ethanol 10ml and benzene 10ml. 100m
l in an autoclave, -50 kg with carbon oxide
/ cm. Next, the temperature was raised to 140'C and the reaction was carried out for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography.
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。As a result, 17.15% of the charged bromobenzene 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 、０５ ｇ （５０ｍ ｍ ｏ １ ）
、塩化パラジウム８．９ｍｇ （０，０５ｍｍｏｌ）、
トリフェニルホスフィン２６２．３ｍｇ （０，１ｍｍ
ｏｌ）、エタノール１０ｍ１及びベンゼン１０ｍ１を１
００ｍ１オートクレーブに仕込み、−酸化炭素で５０
ｋ ｇ ／ ｃ ｍ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、ガスクロマドクラフィー
により分析した。Example 2 Bromobenzene 7.85g (50mmol), triethylamine 5.05g (50mmol)
, palladium chloride 8.9 mg (0.05 mmol),
Triphenylphosphine 262.3mg (0.1mm
ol), 10 ml of ethanol and 10 ml of benzene
00ml in an autoclave, - 50ml with carbon oxide
It was pressurized to kg/cm. Next, the temperature was raised to 140°C and a reaction was carried out for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography.
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６．０２ ｍ ｍ ｏ １（触媒
活性６０．２／ｈ）が得られた。As a result, 12.04% of the charged bromobenzene reacted, and 6.02 m m o 1 (catalytic activity 60.2/h) of ethyl benzoate was obtained.
実施例３
ブロモベンゼン７．８５ｇ （５０ｍｍｏ ｌ）、トリ
エチルアミン５．０５ｇ （５０ｍｍｏｌ）。Example 3 Bromobenzene 7.85 g (50 mmol), triethylamine 5.05 g (50 mmol).
塩化パラジウム８．９ｍｇ （０，０５ｍｍｏ １）、
トリフェニルホスフィン２６２．３ｍｇ （０，１ｍｍ
ｏｌ）、エタノール１０ｍ１及びベンゼン１０ｍ１を１
００ｍ１オートクレーブに仕込み、二酸化炭素で５ ｋ
ｇ ／ ｃｉに加圧した。次に１２０ ’Ｃ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。Palladium chloride 8.9 mg (0.05 mmo 1),
Triphenylphosphine 262.3mg (0.1mm
ol), 10 ml of ethanol and 10 ml of benzene
Pour into a 00ml autoclave and boil with carbon dioxide for 5k.
Pressurized to g/ci. Next, the temperature was raised to 120'C and a reaction was carried out for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography.
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。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５．０５ｇ （５０ｍｍｏｌ）、塩化パラジ
ウム８．９ｍｇ （０，０５ｍｍｏ ｌ）、トリフェニ
ルホスフィン２６２．３ｍｇ （０，１ｍｍｏｌ）、エ
タノール１０ｍ１及びベンゼン１０ｍ１を１００ｍ１オ
ートクレーブに仕込み、−酸化炭素で２０ ｋ ｇ ／
ｃ ｒｄ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。Example 4 7.85 g (50 mmol) of bromobenzene, 5.05 g (50 mmol) of triethylamine, 8.9 mg (0.05 mmol) of palladium chloride, 262.3 mg (0.1 mmol) of triphenylphosphine, 10 ml of ethanol, and 10 ml of benzene. Pour into a 100ml autoclave, -20kg/carbon oxide
Pressure was applied to crd. Next, the temperature was raised to 120°C and a reaction was carried out for 2 hours. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography.
その結果、仕込んだブロモベンゼンの６．６ｏ％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。As a result, 6.6o% of the charged bromobenzene reacted, and 3.30mmol 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５．０５ｇ （５０ｍｍｏｌ）、塩化パラジ
ウム８．９ｍｇ （０，０５ｍｍｏ ｌ）、トリフェニ
ルホスフィン２６２．３ｍｇ （０，１ｍｍｏｌ）、エ
タノール１０ｍ１及びベンゼン１０ ｍ ｌを１００ｍ
１オートクレーブに仕込み、−酸化炭素で５ ｋ ｇ
／ ｃ ｍに加圧した。次に１２０’Ｃ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。Example 5 Bromobenzene 7.85 g (50 mmol), triethylamine 5.05 g (50 mmol), palladium chloride 8.9 mg (0.05 mmol), triphenylphosphine 262.3 mg (0.1 mmol), ethanol 10 ml and benzene 10 m l to 100m
1 autoclave, -5 kg with carbon oxide
/ cm. Next, raise the temperature to 120'C and
Allowed time to react. After purging excess carbon monoxide after the reaction, the reaction solution was taken out and analyzed by gas chromatography.
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。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５．０５ｇ （５０ｍｍｏ ｌ）、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（０，５ｍｍｏ
ｌ） 、エタノール１０ｍ１及びベンゼン１０ｍ１を１
００ｍ１オートクレーブに仕込み、−酸化炭素で５０
ｋ ｇ ／ ｃ ｍに加圧した。Example 6 Bromobenzene 7.85g (50mmol), triethylamine 5.05g (50mmol), palladium chloride 8.9mg (0.05mmol), Tris (p
-tolyl) phosphine 152.2 mg (0,5 mmo
l), 10 ml of ethanol and 10 ml of benzene
00ml in an autoclave, - 50ml with carbon oxide
It was pressurized to kg/cm.
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。Next, the temperature was raised to 140°C and a reaction was carried out 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 4.98 mmol of ethyl benzoate (catalytic activity: 49.8/h) was obtained.
実施例７
ブロモベンゼン７．８５ｇ （５０ｍｍｏ １）、トリ
エチルアミン５．０５ｇ （５０ｍｍ’ｏｌ）、塩化パ
ラジウム８．９ｍｇ （０，０５ｍｍｏ ｌ）、トリス
（ｐ−アニシル）ホスフィン１７６．２ｍｇ （０，５
ｍｍｏ ｌ） 、エタノール１０ｍ１及びベンゼン１０
ｍ１を１００ ｍ ｌオートクレーブに仕込み、−酸化
炭素で５０ ｋ ｇ ／ ｃ ｒｒｒに加圧した。Example 7 Bromobenzene 7.85 g (50 mmol), triethylamine 5.05 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
ml was placed in a 100 ml autoclave and pressurized to 50 kg/crrr with -carbon oxide.
鴨１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。Duck 1 was heated to 140°C and reacted for 2 hours. After purging excess carbon monoxide after the reaction, take out the reaction solution,
Analyzed by gas chromatography. As a result, 7.2% of the charged bromobenzene was reacted, and 3.62 mmol of ethyl benzoate (catalytic activity: 36.2/h) was obtained.
比較例１
ブロモベンゼン７．８５ｇ （５０ｍｍｏ １）、トリ
エチルアミン５．０５ｇ （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１０ｍ１及びベンゼン１０ｍ１を１００ｍ１オー
トクレーブに仕込み、−酸化炭素で５ ｋ ｇ ／ ｃ
ｒｌ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 7.85 g (50 mmol) of bromobenzene, 5.05 g (50 mmol) of triethylamine, 8.9 mg (0.05 mmol) of palladium chloride, 26.2 mg (0.1 mmol) of triphenylphosphine, 10 ml of ethanol, and 10 ml of benzene. Filled in a 100ml autoclave, -5 kg/c with carbon oxide
Pressure was applied to rl. Next, the temperature was raised to 120°C and a reaction was carried out 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% of the charged bromobenzene reacted, and 0.68 mmol of ethyl benzoate (catalytic activity: 6°8/h) was obtained.
通に較例２
ブロモベンゼン７．８５ｇ （５０ｍｍｏ １）、トリ
エチルアミン５．０５ｇ （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 （０，１ｍｍｏ１）、エタ
ノール１０ｍ１及びベンゼン１０ｍ１を１００ｍ１オー
トクレーブに仕込み、−酸化炭素で５０ ｋ ｇ ／
ｃ ｍ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 7.85g (50mmol), triethylamine 5.05g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 26.2mg (0.1mmol), ethanol 10ml and benzene Pour 10ml into a 100ml autoclave and -50kg/carbon oxide.
Pressure was applied to cm. Next, the temperature was raised to 120°C and a reaction was carried out 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% of the charged bromobenzene reacted, and 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５．０５ｇ （５０ｍｍｏ ｌ）、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１０ ｍ ｌ及びベンゼン１０ｍｌを１００ｍ１
オートクレーブに仕込み、−酸化炭素で５０ ｋ ｇ
／ ｃ ｒｒ？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％力反応し、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 7.85g (50mmol), triethylamine 5.05g (50mmol), palladium chloride 8.9mg (0.05mmol), triphenylphosphine 26.2mg (0.1mmol), ethanol 10ml and benzene 10ml to 100ml
Place in autoclave, -50 kg with carbon oxide
/crr? Pressure was applied. Next, the temperature was raised to 140°C and a reaction was carried out 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, the amount of bromobenzene charged was 0.
48% force reaction, 0.24 mmol of ethyl benzoate (
A catalyst activity of 2.4/h) was obtained.
比較例４
ブロモベンゼン７．８５ｇ （５０ｍｍｏｌ）、）〜リ
エチルアミン５．０５ｇ （５０ｍｍｃｌ）、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１０ｍ１及びベンゼン１゜ｍｌを１００ｍ１オ
ートクレーブに仕込み、−ｍ化炭素で５０ ｋ ｇ ／
ｃ ｍ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０．９２ｍｍｏ １ （触媒
活性９．２／ｈ）が得ら九た。Comparative Example 4 Bromobenzene 7.85 g (50 mmol), ) to ethylamine 5.05 g (50 mmcl), palladium chloride 8. ．． 9 mg (0.05 mmol), triphenylphosphine 52.2 mg (0.2 mmol), 10 ml of ethanol and 1° ml of benzene were placed in a 100 ml autoclave, and 50 kg/ml of -merized carbon was added.
Pressure was applied to cm. Next, the temperature was raised to 140°C and a reaction was carried out 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% of the charged bromobenzene
was reacted, and 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 （５０ｍｍｏ１．）、トリ
エチルアミン５．０５ｇ （５０ｍｍｏｌ）、塩化パラ
ジウム８．９ｍｇ （０，０５ｍｍｏ ｌ）、トリス（
ｐ−トリル）ホスフィン３０．４ｍｇ（０，１ｍｍｏｌ
） 、エタノール１０ｍ１及びベンゼン１０ｍ１を１０
０ｍ１オー１−クレープに仕込み、−酸化炭素で５０
ｋ ｇ ／ ｃ ｒｌに加圧した。Comparative Example 5 Bromobenzene 7.85g (50mmol), triethylamine 5.05g (50mmol), palladium chloride 8.9mg (0.05mmol), Tris (
p-tolyl) phosphine 30.4 mg (0.1 mmol
), 10 ml of ethanol and 10 ml of benzene
0ml 1-Pour into a crepe, -50 with carbon oxide
It was pressurized to kg/crl.
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０．８６ｍｍｏ］（触媒活性８．６／ｈ）が得られた
。Next, the temperature was raised to 140°C and a reaction was carried out 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 0.86 mmol of ethyl benzoate (catalytic activity: 8.6/h) was obtained.
Claims (1)
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、ホスフィンとパラジウムの比を５〜 ５０に調製したパラジウム−ホスフィン触 媒を用いることを特徴とする一般式（III） で ▲数式、化学式、表等があります▼ 表わされる芳香族カルボン酸エステル類 （式中、Ｒは前記の通り。）を製造する方 法。(1) Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ A brominated aromatic compound represented by group, acyloxy group, alkoxycarbonyl group, acyl group, hydroxyl group, amino group, or halogen) in the presence of a basic substance and carbon monoxide and the general formula (II) R-OH (wherein R is carbon (representing a hydrocarbon group having a number of 1 to 20), a palladium-phosphine catalyst having a phosphine to palladium ratio of 5 to 50 is used. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ A method for producing the aromatic carboxylic acid esters (in the formula, R is as described above).
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 true JPH04208250A (en) | 1992-07-29 |
| JPH0753692B2 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) |
Cited By (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 |
| JP2014114275A (en) * | 2012-11-08 | 2014-06-26 | Lab Servier | New process for synthesizing (2e)-3-(3,4-dimethoxyphenyl)prop-2-en nitrile and application in synthesis of ivabradine and addition salt with pharmaceutically acceptable acid |
Citations (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 |
| JPS62114930A (en) * | 1985-11-12 | 1987-05-26 | ストウフア− ケミカル カンパニ− | High yield carbonyl reaction of halo- hydrocarbon |
| JPS63166845A (en) * | 1986-12-22 | 1988-07-11 | ストウファー ケミカル カンパニー | Single phase carbonization of aromatic halaide to carboxylate |
| JPS63227547A (en) * | 1987-03-14 | 1988-09-21 | Nippon Nohyaku Co Ltd | Production of carboxylic acid amides or esters |
-
1990
- 1990-10-30 JP JP2293004A patent/JPH0753692B2/en not_active Expired - Lifetime
Patent Citations (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 |
| JPS62114930A (en) * | 1985-11-12 | 1987-05-26 | ストウフア− ケミカル カンパニ− | High yield carbonyl reaction of halo- hydrocarbon |
| JPS63166845A (en) * | 1986-12-22 | 1988-07-11 | ストウファー ケミカル カンパニー | Single phase carbonization of aromatic halaide to carboxylate |
| JPS63227547A (en) * | 1987-03-14 | 1988-09-21 | Nippon Nohyaku Co Ltd | Production of carboxylic acid amides or esters |
Cited By (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 |
| JP2014114275A (en) * | 2012-11-08 | 2014-06-26 | Lab Servier | New process for synthesizing (2e)-3-(3,4-dimethoxyphenyl)prop-2-en nitrile and application in synthesis of ivabradine and addition salt with pharmaceutically acceptable acid |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0753692B2 (en) | 1995-06-07 |
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