JPWO2016104332A1 - アルデヒド化合物の製造方法およびアセタール化合物 - Google Patents
アルデヒド化合物の製造方法およびアセタール化合物 Download PDFInfo
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- JPWO2016104332A1 JPWO2016104332A1 JP2016566176A JP2016566176A JPWO2016104332A1 JP WO2016104332 A1 JPWO2016104332 A1 JP WO2016104332A1 JP 2016566176 A JP2016566176 A JP 2016566176A JP 2016566176 A JP2016566176 A JP 2016566176A JP WO2016104332 A1 JPWO2016104332 A1 JP WO2016104332A1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- -1 aldehyde compound Chemical class 0.000 title abstract description 53
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- LUNMJPAJHJAGIS-UHFFFAOYSA-N 3-methylpentanedial Chemical compound O=CCC(C)CC=O LUNMJPAJHJAGIS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- VEEFADFWCHSFIU-UHFFFAOYSA-N 3-methylbut-3-enal Chemical compound CC(=C)CC=O VEEFADFWCHSFIU-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 36
- 125000001424 substituent group Chemical group 0.000 description 16
- 239000003446 ligand Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
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- 239000000243 solution Substances 0.000 description 7
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- 125000003118 aryl group Chemical group 0.000 description 6
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 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 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000003284 rhodium compounds Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 125000004815 1,2-dimethylethylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([*:2])C([H])([H])[H] 0.000 description 3
- 125000004807 2-methylethylene group Chemical group [H]C([H])([H])C([H])([*:2])C([H])([H])[*:1] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 C*CC1OC(CC(C)=C)OC1 Chemical compound C*CC1OC(CC(C)=C)OC1 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
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- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
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- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PXSBSBDNZRLRLK-UHFFFAOYSA-N 2-(2h-pyran-2-yloxy)-2h-pyran Chemical compound O1C=CC=CC1OC1OC=CC=C1 PXSBSBDNZRLRLK-UHFFFAOYSA-N 0.000 description 1
- QSVXMOKGHFNTEI-UHFFFAOYSA-N 2-bis[2-(dimethylamino)phenyl]phosphanyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1P(C=1C(=CC=CC=1)N(C)C)C1=CC=CC=C1N(C)C QSVXMOKGHFNTEI-UHFFFAOYSA-N 0.000 description 1
- YBDQLHBVNXARAU-UHFFFAOYSA-N 2-methyloxane Chemical compound CC1CCCCO1 YBDQLHBVNXARAU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- QZUPHAGRBBOLTB-UHFFFAOYSA-N NSC 244302 Chemical compound C=1C=CC=CC=1P(C(C)(C)C)C1=CC=CC=C1 QZUPHAGRBBOLTB-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- NLBJXFKIFPYQRB-UHFFFAOYSA-N bis(2-tert-butylphenyl) (2-methylphenyl) phosphite Chemical compound CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C NLBJXFKIFPYQRB-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- FMJNZRCLIZWWJP-UHFFFAOYSA-N carbon monoxide;ruthenium;triphenylphosphane Chemical compound [Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FMJNZRCLIZWWJP-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- ZXKWUYWWVSKKQZ-UHFFFAOYSA-N cyclohexyl(diphenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZXKWUYWWVSKKQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- MXIRHCBUSWBUKI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCC[CH2+] MXIRHCBUSWBUKI-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- VPLLTGLLUHLIHA-UHFFFAOYSA-N dicyclohexyl(phenyl)phosphane Chemical compound C1CCCCC1P(C=1C=CC=CC=1)C1CCCCC1 VPLLTGLLUHLIHA-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- WHNGQRQJGDUZPJ-UHFFFAOYSA-N hexyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCCCC)C1=CC=CC=C1 WHNGQRQJGDUZPJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FDJSESZWPWMLEC-UHFFFAOYSA-N nonane Chemical compound CCCCCCCC[CH2+] FDJSESZWPWMLEC-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000008300 phosphoramidites Chemical class 0.000 description 1
- UNQNIRQQBJCMQR-UHFFFAOYSA-N phosphorine Chemical compound C1=CC=PC=C1 UNQNIRQQBJCMQR-UHFFFAOYSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IFXORIIYQORRMJ-UHFFFAOYSA-N tribenzylphosphane Chemical compound C=1C=CC=CC=1CP(CC=1C=CC=CC=1)CC1=CC=CC=C1 IFXORIIYQORRMJ-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YJLVKRVGSARISS-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphite Chemical compound CC1=CC=CC(C)=C1OP(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C YJLVKRVGSARISS-UHFFFAOYSA-N 0.000 description 1
- BKHZQJRTFNFCTG-UHFFFAOYSA-N tris(2-methylphenyl) phosphite Chemical compound CC1=CC=CC=C1OP(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C BKHZQJRTFNFCTG-UHFFFAOYSA-N 0.000 description 1
- DAZUWKNHFLGZSN-UHFFFAOYSA-N tris(2-phenylphenyl) phosphite Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(OC=1C(=CC=CC=1)C=1C=CC=CC=1)OC1=CC=CC=C1C1=CC=CC=C1 DAZUWKNHFLGZSN-UHFFFAOYSA-N 0.000 description 1
- IJOFZIRWMBOMHP-UHFFFAOYSA-N tris(2-propan-2-ylphenyl) phosphite Chemical compound CC(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)C)OC1=CC=CC=C1C(C)C IJOFZIRWMBOMHP-UHFFFAOYSA-N 0.000 description 1
- IQKSLJOIKWOGIZ-UHFFFAOYSA-N tris(4-chlorophenyl)phosphane Chemical compound C1=CC(Cl)=CC=C1P(C=1C=CC(Cl)=CC=1)C1=CC=C(Cl)C=C1 IQKSLJOIKWOGIZ-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
- 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 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
- C07C47/12—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing more than one —CHO group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/26—Radicals substituted by doubly bound oxygen or sulfur atoms or by two such atoms singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
[1]下記一般式(1)
で表される化合物(以下、アセタール化合物(1)と称する。)を加水分解する工程を含む、3−メチルグルタルアルデヒドの製造方法。
[2]下記一般式(2)
で表される化合物(以下、アセタール化合物(2)と称する。)をヒドロホルミル化してアセタール化合物(1)を得る工程をさらに含む、[1]の製造方法。
[3]下記一般式(3)で表される化合物(以下、アセタール化合物(3)と称する。)。
アセタール化合物(1)は、好適にはアセタール化合物(2)のヒドロホルミル化反応により製造できる。
また、R1とR2、R3とR4が互いに連結して形成するアルキレン基としては、例えばエチレン基、n−プロピレン基、n−ブチレン基、n−ペンチレン基、n−へキシレン基、2−メチルエチレン基、1,2−ジメチルエチレン基、2−メチル−n−プロピレン基、2,2−ジメチル−n−プロピレン基、3−メチル−n−ペンチレン基などが挙げられる。中でもエチレン基、n−プロピレン基、2−メチル−n−プロピレン基、2,2−ジメチル−n−プロピレン基、2−メチルエチレン基、1,2−ジメチルエチレン基が好ましく、エチレン基、n−プロピレン基、2−メチル−n−プロピレン基、2,2−ジメチル−n−プロピレン基がより好ましく、エチレン基、n−プロピレン基が特に好ましい。
アセタール化合物(2)の製造方法に制限はなく、例えば3−メチル−3−ブテン−1−アールを、上記したR1〜R4に対応するアルコールの存在下でアセタール化する方法が挙げられる。ここで、用いる3−メチル−3−ブテン−1−アールは、例えば特表2007−525522号や国際特許公開08/037693号記載の方法に従い、イソプレノールから合成できる。
上記した触媒の使用量は、使用する酸の種類や水の量により異なるが、塩酸を使用する場合の例を挙げれば、塩化水素分子換算で反応溶液の0.00001質量%〜10質量%の範囲で使用するのが好ましく、0.0001質量%〜5質量%の範囲がさらに好ましい。0.00001質量%未満では十分な反応速度が得られないことが多く、10質量%を超えて使用した場合は、中和する際の塩基の使用量が増えて後処理工程の負荷が増大する。
アセタール化合物(2)の中でも、製造が容易であることなどから、下記アセタール化合物(3)
が特に好ましい。なお、かかるアセタール化合物(3)は新規化合物である。
アセタール化合物(1)は、好適にはアセタール化合物(2)をヒドロホルミル化する方法により得られる。
ヒドロホルミル化反応は、アセタール化合物(2)を、第8〜10族金属化合物および必要に応じて配位子の存在下に、一酸化炭素および水素と反応させることによって行なう。
第8〜10族金属化合物の使用量は、反応混合液1リットルあたり、金属原子換算で0.0001〜100ミリモルの範囲であるのが好ましく、0.005〜10ミリモルの範囲であるのがより好ましい。第8〜10族金属化合物の使用量が、金属原子換算で反応混合液1リットルあたり0.0001ミリモル未満であると、反応速度が極めて遅くなる傾向にあり、また100ミリモルを超えてもそれに見合う効果が得られず、触媒コストが増大するのみである。
具体的には、例えば特表2007−506691号の9〜40頁に記載の化合物を用いることができる。
配位子はそれぞれ単独で用いてもよく、2種以上を併用してもよい。
上記フェニレン基としては、例えば1,2−フェニレン基、1,3−フェニレン基、1,4−フェニレン基などが挙げられる。
上記ナフチレン基としては、例えば1,2−ナフチレン基、1,8−ナフチレン基などが挙げられる。
反応は、攪拌型反応槽、循環型反応槽、気泡塔型反応槽などを用いて、バッチ方式または連続方式で行うことができる。必要ならば、未反応のアセタール化合物(2)を反応後の反応液から回収し、反応器へ再循環しながら実施してもよい。連続方式は、単一反応器または直列もしくは並列の複数の反応器で実施することができる。
次に、アセタール化合物(1)を加水分解することによりMGLを得る方法について説明する。MGLはアセタール化合物(1)と水を反応させることにより得ることができる。水との反応は無触媒でもよく、必要に応じて酸を触媒として用いてもよい。用いる酸としては特に限定されず、例えば、硫酸、燐酸、硝酸、塩酸、ホウ酸などの無機酸およびその塩;ギ酸、酢酸、プロピオン酸、シュウ酸、メタンスルホン酸、パラトルエンスルホン酸、パラトルエンスルホン酸ピリジニウムなどの有機酸およびその塩;陽イオン交換樹脂、シリカアルミナ、ゼオライト、活性白土などの固体酸などが挙げられる。
上記した酸の使用量は、使用する酸の種類や水の量により異なるが、塩酸を使用する場合の例を挙げれば、反応液の0.0001質量%〜10質量%の範囲で使用するのが好ましく、0.001質量%〜5質量%の範囲がさらに好ましい。0.0001質量%未満では十分な反応速度が得られないことが多く、10質量%を超えて使用した場合は、中和する際の塩基の使用量が増えて後処理工程の負荷が増大する。
1H−NMR(400MHz、CDCl3、TMS)δ:1.805(s,3H)、2.382 (d,2H)、3.843−4.008(m,4H)、4.828(q,1H)、4.868(t,1H)、4.982(t,1H)
ビスホスファイトAに代えてトリス(2,4−ジ−t−ブチルフェニル)ホスファイト3.56gを用いてロジウム原子:リン原子=1:100(モル比)にし、反応時間を2時間とした以外は、実施例2と同様にして反応を実施した。化合物Aの転化率は99.2%、化合物Bの選択率は94.3%であった。
ビスホスファイトAに代えてトリフェニルホスフィン1.44gを用いてロジウム原子:リン原子=1:100(モル比)にし、反応時間を3.5時間とした以外は、実施例2と同様にして反応を実施した。化合物Aの転化率は80.0%、化合物Bの選択率は94.1%であった。
3つ口フラスコに1mol/Lの塩酸636.4mg(塩酸0.64mmol、23.3mg)、蒸留水600mlおよび化合物B100.8g(636.9mmol)を仕込み、窒素雰囲気下、60℃で3.5時間攪拌した。得られた反応液をガスクロマトグラフィーで分析したところ、化合物Bの転化率は97.2%、MGLの選択率は99.8%であった。反応液を室温まで冷却した後、炭酸水素ナトリウムで中和し、酢酸エチル600mlで3回抽出した。得られた有機層を合わせて溶媒を減圧留去した後、蒸留精製することでMGL65.8g(576.4mmol、収率90.5%)を得た。
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