JPH0772153B2 - Process for producing para-hydroxybenzaldehyde derivative - Google Patents
Process for producing para-hydroxybenzaldehyde derivativeInfo
- Publication number
- JPH0772153B2 JPH0772153B2 JP61251292A JP25129286A JPH0772153B2 JP H0772153 B2 JPH0772153 B2 JP H0772153B2 JP 61251292 A JP61251292 A JP 61251292A JP 25129286 A JP25129286 A JP 25129286A JP H0772153 B2 JPH0772153 B2 JP H0772153B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- para
- cresol
- general formula
- cerium
- 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 - Fee Related
Links
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical class OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 title claims description 23
- 238000000034 method Methods 0.000 title description 19
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical class CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZFBNNSOJNZBLLS-UHFFFAOYSA-N 2,6-Dimethoxy-4-methylphenol Chemical compound COC1=CC(C)=CC(OC)=C1O ZFBNNSOJNZBLLS-UHFFFAOYSA-N 0.000 description 2
- FIGPGTJKHFAYRK-UHFFFAOYSA-N 2,6-dibromo-4-methylphenol Chemical compound CC1=CC(Br)=C(O)C(Br)=C1 FIGPGTJKHFAYRK-UHFFFAOYSA-N 0.000 description 2
- PETRWTHZSKVLRE-UHFFFAOYSA-N 2-Methoxy-4-methylphenol Chemical compound COC1=CC(C)=CC=C1O PETRWTHZSKVLRE-UHFFFAOYSA-N 0.000 description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AERUOEZHIAYQQL-UHFFFAOYSA-K cerium(3+);triacetate;hydrate Chemical compound O.[Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O AERUOEZHIAYQQL-UHFFFAOYSA-K 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- YXEOEPYIBGTLML-UHFFFAOYSA-N 2,6-dichloro-4-methylphenol Chemical compound CC1=CC(Cl)=C(O)C(Cl)=C1 YXEOEPYIBGTLML-UHFFFAOYSA-N 0.000 description 1
- MTIDYGLTAOZOGU-UHFFFAOYSA-N 2-bromo-4-methylphenol Chemical compound CC1=CC=C(O)C(Br)=C1 MTIDYGLTAOZOGU-UHFFFAOYSA-N 0.000 description 1
- KEBGFIIPHINZFS-UHFFFAOYSA-N 2-methoxy-4,6-dimethylphenol Chemical compound COC1=CC(C)=CC(C)=C1O KEBGFIIPHINZFS-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- SOYWOKSOKVRZRZ-UHFFFAOYSA-N 3-methoxy-4-methylphenol Chemical compound COC1=CC(O)=CC=C1C SOYWOKSOKVRZRZ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 241000972773 Aulopiformes Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- -1 Para-hydroxybenzyl methyl ether Chemical compound 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 235000019515 salmon Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 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
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、パラヒドロキシベンズアルデヒド誘導体の製
造方法、更に詳しくは一般式 〔式中R1及びR2は、同一又は異なって水素原子、アルキ
ル基、アルコキシ基、アリール基又はハロゲン原子を示
す。〕 で表わされるパラヒドロキシベンズアルデヒド誘導体の
製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a parahydroxybenzaldehyde derivative, more specifically a general formula [In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom. ] It is related with the manufacturing method of the para hydroxy benzaldehyde derivative represented by these.
従来の技術及びその問題点 上記一般式（１）で表わされるパラヒドロキシベンズア
ルデヒド誘導体は、医薬、農薬等の有効成分を合成する
ための中間体として重要な化合物である。Conventional Technology and Problems Thereof The parahydroxybenzaldehyde derivative represented by the general formula (1) is an important compound as an intermediate for synthesizing active ingredients such as pharmaceuticals and agricultural chemicals.
一般式（１）のパラヒドロキシベンズアルデヒド誘導体
の製造方法としては、例えば一般式 〔式中R1及びR2は前記に同じ。）で表わされるパラクレ
ゾール誘導体を、触媒の存在下に酸化反応させる方法が
知られており、その代表的な方法として特開昭55−8183
2号公報に記載の方法、特開昭61−24535号公報に記載の
方法等が挙げられる。前者の方法は、触媒としてコバル
ト塩を用いる方法であり、後者の方法は触媒として銅塩
を用いる方法である。しかしながら、前者の方法は、目
的化合物を収率よく製造し得るものではない。また後者
の方法では、銅塩触媒を用いるために公害対策上の後処
理設備が必要である。更に上記方法は、いずれも反応に
要する時間が10〜60時間と長く、連続製造が困難である
という問題をも有している。このように従来公知の方法
は、工業的製造法として満足できるものではない。而し
て大規模製造上から考えて、公害対策設備を必要とせ
ず、反応を短時間で完了させることができ、しかも目的
化合物を高収率で収得し得る新規製法の開発が望まれて
いるのが現状である。Examples of the method for producing the parahydroxybenzaldehyde derivative represented by the general formula (1) include, for example, the general formula [In the formula, R 1 and R 2 are the same as defined above. ), A method of oxidizing a para-cresol derivative represented by the formula (1) in the presence of a catalyst is known, and a typical method thereof is JP-A-55-8183.
The method described in JP-A No. 2-24, the method described in JP-A No. 61-24535, and the like can be mentioned. The former method is a method using a cobalt salt as a catalyst, and the latter method is a method using a copper salt as a catalyst. However, the former method cannot produce the target compound in good yield. Further, in the latter method, since a copper salt catalyst is used, a post-treatment facility for pollution control is required. Further, each of the above methods has a problem that the time required for the reaction is as long as 10 to 60 hours and continuous production is difficult. As described above, the conventionally known method is not satisfactory as an industrial manufacturing method. Therefore, from the viewpoint of large-scale production, it is desired to develop a new production method capable of completing the reaction in a short time without requiring pollution control equipment and obtaining the target compound in a high yield. is the current situation.
問題点を解決するための手段 本発明者は、斯かる現状に鑑み、上記一般式（２）のパ
ラクレゾール誘導体から上記一般式（１）で表わされる
パラヒドロキシベンズアルデヒド誘導体を酸素酸化反応
により温和な反応条件下に短時間で、しかも高収率で製
造し得る方法を開発すべく鋭意研究を重ねてきた。その
結果、下記の反応条件下に酸素酸化反応を行なう場合
に、本発明の所期の目的を達成し得ることを見い出し
た。本発明は、斯かる知見に基づいて完成されたもので
ある。Means for Solving the Problems In view of the present situation, the present inventor has mildly oxidized a para-hydroxybenzaldehyde derivative represented by the general formula (1) from a para-cresol derivative represented by the general formula (2) by an oxygen oxidation reaction. We have earnestly conducted research to develop a method capable of producing in a high yield in a short time under reaction conditions. As a result, they have found that the intended purpose of the present invention can be achieved when the oxygen oxidation reaction is carried out under the following reaction conditions. The present invention has been completed based on such findings.
即ち、本発明は、可溶性コバルト塩触媒とセリウム塩及
びニッケル塩からなる群より選ばれた少なくとも１種の
助触媒との共存下、上記一般式（２）で表わされるパラ
クレゾール誘導体を液相酸素酸化反応させて上記一般式
（１）で表わされるパラヒドロキシベンズアルデヒド誘
導体を得ることを特徴とするパラヒドロキシベンズアル
デヒド誘導体の製造方法に係る。That is, according to the present invention, a paracresol derivative represented by the above general formula (2) is mixed with liquid phase oxygen in the presence of a soluble cobalt salt catalyst and at least one promoter selected from the group consisting of cerium salt and nickel salt. The present invention relates to a method for producing a para-hydroxybenzaldehyde derivative, which comprises subjecting the para-hydroxybenzaldehyde derivative represented by the general formula (1) to an oxidation reaction.
本発明で出発原料として用いられる一般式（２）のパラ
クレゾール誘導体としては、一般式（２）に該当する化
合物である限り従来公知のものを広く使用でき、具体的
にはパラクレゾール、２−メチル−ｐ−クレゾール、３
−メチル−ｐ−クレゾール、２−メトキシ−ｐ−クレゾ
ール、３−メトキシ−ｐ−クレゾール、2,6−ジメトキ
シ−ｐ−クレゾール、２−メトキシ−６−メチル−ｐ−
クレゾール、2,6−ジ−tert−ブチル−ｐ−クレゾー
ル、tert−ブチル−ｐ−クレゾール、２−クロロ−ｐ−
クレゾール、2,6−ジクロロ−ｐ−クレゾール、２−ブ
ロモ−ｐ−クレゾール、2,6−ジブロモ−ｐ−クレゾー
ル等を例示できる。As the para-cresol derivative of the general formula (2) used as a starting material in the present invention, conventionally known compounds can be widely used as long as they are compounds corresponding to the general formula (2). Methyl-p-cresol, 3
-Methyl-p-cresol, 2-methoxy-p-cresol, 3-methoxy-p-cresol, 2,6-dimethoxy-p-cresol, 2-methoxy-6-methyl-p-
Cresol, 2,6-di-tert-butyl-p-cresol, tert-butyl-p-cresol, 2-chloro-p-
Examples thereof include cresol, 2,6-dichloro-p-cresol, 2-bromo-p-cresol, and 2,6-dibromo-p-cresol.
本発明では、反応系内に可溶性コバルト塩とセリウム塩
及びニッケル塩からなる群より選ばれた少なくとも１種
の助触媒とを共存させることを必須とする。In the present invention, it is essential that a soluble cobalt salt and at least one promoter selected from the group consisting of cerium salt and nickel salt coexist in the reaction system.
用いられるコバルト塩としては、従来公知のものを広く
使用でき、例えばコバルトの酢酸塩、塩酸塩、硝酸塩、
硫酸塩、ナフテン酸塩、安息香酸塩、ステアリン酸塩、
アセチルアセトナート、酸化物等が挙げられる。斯かる
可溶性コバルト塩触媒の使用量としては、溶媒の種類、
助触媒の種類、その他の反応条件等により異なり一概に
は言えないが、原料とする一般式（２）のパラクレゾー
ル誘導体１モル当り、通常0.0005〜0.5モル程度、好ま
しくは0.001〜0.1モル程度とするのがよい。As the cobalt salt used, conventionally known ones can be widely used, for example, cobalt acetate, hydrochloride, nitrate,
Sulfate, naphthenate, benzoate, stearate,
Examples include acetylacetonate and oxides. The amount of such a soluble cobalt salt catalyst used, the type of solvent,
It depends on the type of cocatalyst, other reaction conditions, etc. and cannot be generally stated, but it is usually about 0.0005 to 0.5 mol, preferably about 0.001 to 0.1 mol, per mol of the para-cresol derivative of the general formula (2) used as a raw material. Good to do.
本発明で用いられるセリウム塩としては、具体的には酢
酸セリウム、硝酸セリウム、硫酸セリウム、塩化セリウ
ム、セリウムアセチルアセトナート、硝酸セリウムアン
モニウム、炭酸セリウム、水酸化セリウム、蓚酸セリウ
ム等を例示できる。また、ニッケル塩としては、具体的
には酢酸ニッケル、塩化ニッケル、臭化ニッケル、炭酸
ニッケル、硝酸ニッケル、蟻酸ニッケル、ナフテン酸ニ
ッケル、硫酸ニッケル、ニッケルアセチルアセトナー
ト、酸化ニッケル等を例示できる。これらは１種単独で
又は２種以上混合して使用され得る。上記可溶性コバル
ト塩と上記助触媒とを併用することにより、目的とする
一般式（１）のパラヒドロキシベンズアルデヒド誘導体
の収率を格段に高めることができる。斯かる助触媒の使
用量としては、原料とする一般式（２）のパラクレゾー
ル誘導体１モル当り、通常0.0005〜0.5モル程度、好ま
しくは0.001〜0.1モル程度とするのがよい。Specific examples of the cerium salt used in the present invention include cerium acetate, cerium nitrate, cerium sulfate, cerium chloride, cerium acetylacetonate, cerium ammonium nitrate, cerium carbonate, cerium hydroxide and cerium oxalate. Specific examples of the nickel salt include nickel acetate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel naphthenate, nickel sulfate, nickel acetylacetonate, and nickel oxide. These may be used alone or in combination of two or more. By using the soluble cobalt salt in combination with the cocatalyst, the yield of the desired para-hydroxybenzaldehyde derivative of the general formula (1) can be significantly increased. The amount of such a promoter to be used is usually about 0.0005 to 0.5 mol, preferably about 0.001 to 0.1 mol, per mol of the para-cresol derivative of the general formula (2) used as the raw material.
本発明の酸素酸化反応は、反応系内に酸化剤を存在させ
て行なわれる。用いられる酸化剤としては、分子状酸素
を与え得るものである限り従来公知のものを広く使用で
き、例えば酸素、空気、過酸化水素、過酸化ナトリウ
ム、過酸化酢酸、過酸化ベンゾイル等の過酸化物等を挙
げることができる。また、本発明の酸化反応の際の圧力
は、反応系を液層に維持できる圧力である限り特に限定
されるものではなく、常圧下及び加圧下のいずれでもよ
い。特に本発明では、酸素圧が0.1〜10kg/cm2程度とな
るように反応系内の圧力を調整するのが望ましい。The oxygen oxidation reaction of the present invention is carried out in the presence of an oxidizing agent in the reaction system. As the oxidizing agent to be used, conventionally known ones can be widely used as long as they can give molecular oxygen. The thing etc. can be mentioned. Further, the pressure during the oxidation reaction of the present invention is not particularly limited as long as it is a pressure capable of maintaining the reaction system in the liquid layer, and may be under normal pressure or under pressure. Particularly in the present invention, it is desirable to adjust the pressure in the reaction system so that the oxygen pressure is about 0.1 to 10 kg / cm 2 .
本発明の反応は、塩基性の溶液中で行なうのがよい。使
用される反応溶媒としては、例えばメタノール、エタノ
ール、イソプロパノール等のアルコール類、ベンゼン、
シクロヘキサン、シクロペンタン等の炭化水素類、クロ
ロホルム、四塩化炭素、クロロベンゼン等のハロゲン化
炭化水素類、ジブチルエーテル、ジフエニルエーテル、
ジオキサン等のエーテル類、ジメチルホルムアミド、ジ
メチルスルホキシド等の極性溶媒等やこれらの混合溶媒
等を挙げることができる。また塩基としては、従来公知
のものを広く使用でき、具体的には水酸化ナトリウム、
水酸化カリウム、ナトリウムメトキシド、カリウムメト
キシド、ナトリウムエトキシド、カリウムエトキシド、
ナトリウムブトキシド、カリウムブトキシド等が挙げら
れ、これらは１種単独で又は２種以上混合して使用され
る。斯かる塩基は、原料化合物を可溶性にし酸化反応に
おいて活性化するためと酸素酸化反応により生成する生
成水を捕捉するために使用される。該塩基の使用量とし
ては、一般式（１）のパラクレゾール誘導体対して通常
等モル〜10モル程度、好ましくは1.5〜６モル程度とす
るのがよい。The reaction of the present invention is preferably carried out in a basic solution. Examples of the reaction solvent used include alcohols such as methanol, ethanol and isopropanol, benzene,
Hydrocarbons such as cyclohexane and cyclopentane, halogenated hydrocarbons such as chloroform, carbon tetrachloride and chlorobenzene, dibutyl ether, diphenyl ether,
Examples thereof include ethers such as dioxane, polar solvents such as dimethylformamide and dimethylsulfoxide, and mixed solvents thereof. As the base, conventionally known ones can be widely used, specifically, sodium hydroxide,
Potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide,
Sodium butoxide, potassium butoxide, etc. are mentioned, and these are used individually by 1 type or in mixture of 2 or more types. Such a base is used for solubilizing the raw material compound and activating it in the oxidation reaction, and for capturing the produced water generated by the oxygen oxidation reaction. The amount of the base used is usually about equimolar to about 10 mol, preferably about 1.5 to 6 mol, based on the para-cresol derivative of the general formula (1).
本発明の反応は、通常25〜200℃程度、好ましくは50〜1
30℃程度にて行なわれる。本発明の反応によれば、約３
時間で目的化合物を高収率で得ることができ、その後24
時間までにわずかにその収率は上昇を続けるが、経済性
を考慮して該反応の反応時間は４時間程度とするのがよ
い。The reaction of the present invention is usually about 25 to 200 ° C., preferably 50 to 1
It is performed at about 30 ° C. According to the reaction of the present invention, about 3
The target compound can be obtained in high yield in a time, and then 24
Although the yield slightly increases by the time, the reaction time of the reaction is preferably about 4 hours in consideration of economic efficiency.
発明の効果 本発明の方法によれば、緩和な反応条件下に短時間で目
的とする上記一般式（１）で表わされるパラヒドロキシ
ベンズアルデヒド誘導体を高収率で製造し得る。また使
用される触媒は、公害上全く問題のない化合物であり、
反応後の後処理が容易である。従って、本発明の方法
は、上記一般式（１）で表わされるパラヒドロキシベン
ズアルデヒド誘導体の工業的製造方法として極めて有利
なものである。EFFECTS OF THE INVENTION According to the method of the present invention, the target para-hydroxybenzaldehyde derivative represented by the general formula (1) can be produced in a high yield in a short time under mild reaction conditions. Also, the catalyst used is a compound that has no problem in terms of pollution,
Post-treatment after reaction is easy. Therefore, the method of the present invention is extremely advantageous as a method for industrially producing the parahydroxybenzaldehyde derivative represented by the general formula (1).
実施例 以下に実施例を掲げて本発明をより一層明らかにする。Examples The present invention will be further clarified with reference to the following examples.
実施例１ 容量50mlのステンレス製オートクレーブにパラクレゾー
ル216mg（２ミリモル）、酢酸コバルト・４水和物5mg
（0.02ミリモル）、酢酸セリウム・１水和物6.7mg（0.0
2ミリモル）及び24.9％ナトリウムメトキシド・メタノ
ール液2g（9.2ミリモル）を入れ、酸素ガス1.5kg/cm2の
条件下に加圧密封し、油浴温度95℃にて攪拌して反応さ
せた。反応後の後処理は、次に示す２通りの方法のいず
れかで行なった。Example 1 216 mg (2 mmol) of para-cresol and 5 mg of cobalt acetate tetrahydrate in a stainless steel autoclave having a volume of 50 ml.
(0.02 mmol), cerium acetate monohydrate 6.7 mg (0.0
2 mmol) and 2 g (9.2 mmol) of 24.9% sodium methoxide / methanol solution were added, and the mixture was pressure-sealed under the condition of oxygen gas of 1.5 kg / cm 2 and stirred at an oil bath temperature of 95 ° C. for reaction. Post-treatment after the reaction was performed by either of the following two methods.
（ａ） 反応液を希塩酸で弱酸性（pH4）とし、これを
エタノールで100ml丸底フラスコに移し常温で減圧濃縮
する。残渣に少量のエタノールを加え、10分間攪拌し、
ガラスフィルターで過後、その液と洗液を内部標準
品と共にメスフラスコにて所定量に薄め、これを定量液
とした。(A) The reaction solution is made weakly acidic (pH 4) with dilute hydrochloric acid, transferred to a 100 ml round bottom flask with ethanol, and concentrated under reduced pressure at room temperature. Add a small amount of ethanol to the residue, stir for 10 minutes,
After passing through a glass filter, the solution and the washing solution were diluted with an internal standard product to a predetermined amount in a measuring flask, and this was used as a quantitative solution.
（ｂ） 反応液を希塩酸で弱酸製（pH4）とし、水20ml
と酢酸エチル80mlの混合溶媒で分液ロートに移し、振盪
後酢酸エチル層を硫酸ナトリウム無水物で乾燥し、減圧
濃縮した。残渣をエタノールで溶解し、内部標準品と共
にメスフラスコにて所定量に薄め、これを定量液とし
た。(B) Dilute hydrochloric acid to make the reaction solution a weak acid (pH 4) and add 20 ml of water.
The mixture was transferred to a separating funnel with a mixed solvent of 80 ml of ethyl acetate and ethyl acetate, and after shaking, the ethyl acetate layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was dissolved in ethanol and diluted with the internal standard to a predetermined amount in a volumetric flask, which was used as a quantitative solution.
定量は、クロモソルブＷに10重量％のサーモン3000を担
持させた充填剤を使用し、水素炎イオン化検出器を用い
たガスクロマトグラフ法にて分析した結果、生成したパ
ラヒドロキシベンズアルデヒドの収率は、理論生成量の
88％であった。尚、上記（ａ）及び（ｂ）の処理方法の
差は、許容誤差以内であった。Quantitative analysis was carried out by using a packing material in which 10% by weight of salmon 3000 was supported on Chromosolve W and analyzed by a gas chromatograph method using a flame ionization detector. As a result, the yield of parahydroxybenzaldehyde produced was theoretical. Amount of production
It was 88%. The difference between the processing methods (a) and (b) was within the allowable error.
また生成物をシリカゲルＣ−200のカラムクロマトグラ
フィーにてベンゼン：酢酸エチル（5:3）の混合溶媒で
展開し、分離精製した結晶のIRスペクトル、NMRスペク
トル、マススペクトル及び融点は、別途合成した標準品
及び市販品のそれらと一致した。Further, the product was developed by column chromatography on silica gel C-200 with a mixed solvent of benzene: ethyl acetate (5: 3), and the IR spectrum, NMR spectrum, mass spectrum and melting point of the separated and purified crystal were separately synthesized. Consistent with those of the standard and commercial products.
更に反応生成物中の各成分を調べたところ、原料のパラ
クレゾールは存在していないことから、完全に反応が進
行したことが判明し、また溶媒との反応生成物としてパ
ラメトキシベンジルアルコールが１％以内、パラヒドロ
キシベンジルメチルエーテルが約２％あり、完全酸化体
であるパラヒドロキシ安息香酸は１％以内であった。Furthermore, when each component in the reaction product was examined, it was found that the raw material para-cresol did not exist, and therefore the reaction proceeded completely, and para-methoxybenzyl alcohol was 1% as the reaction product with the solvent. %, Para-hydroxybenzyl methyl ether was about 2%, and para-hydroxybenzoic acid as a complete oxidant was within 1%.
実施例２〜６ 下記第１表に示すアルカリメトキシドを使用する以外
は、上記実施例１と同様にしてパラヒドロキシベンズア
ルデヒドを得た。Examples 2 to 6 Parahydroxybenzaldehyde was obtained in the same manner as in Example 1 except that the alkali methoxide shown in Table 1 below was used.
実施例７〜11 下記第２表に示す反応時間とする以外は、上記実施例１
と同様にしてパラヒドロキシベンズアルデヒドを得た。 Examples 7 to 11 Example 1 above except that the reaction times are shown in Table 2 below.
Parahydroxybenzaldehyde was obtained in the same manner as in.
実施例12〜15 下記第３表に示すように酢酸コバルト・４水和物と酢酸
セリウム・１水和物との配合割合を代える以外は、上記
実施例１と同様にしてパラヒドロキシベンズアルデヒド
を得た。 Examples 12 to 15 Parahydroxybenzaldehydes were obtained in the same manner as in Example 1 except that the compounding ratios of cobalt acetate tetrahydrate and cerium acetate monohydrate were changed as shown in Table 3 below. It was
第３表には、比較のために酢酸コバルト・４水和物のみ
を使用した場合の結果を併せて示す。Table 3 also shows the results when only cobalt acetate tetrahydrate was used for comparison.
実施例16〜18 下記第４表に示すようにコバルト塩（0.02ミリモル）及
びセリウム塩（0.02ミリモル）の種類を代える以外は、
上記実施例１と同様にしてパラヒドロキシベンズアルデ
ヒドを得た。 Examples 16 to 18, except that the types of cobalt salt (0.02 mmol) and cerium salt (0.02 mmol) were changed as shown in Table 4 below.
Parahydroxybenzaldehyde was obtained in the same manner as in Example 1.
実施例19〜22 セリウム塩の代りに下記第５表に示すニッケル塩を用い
る以外は、上記実施例１と同様にしてパラヒドロキシベ
ンズアルデヒドを得た。 Examples 19 to 22 Parahydroxybenzaldehyde was obtained in the same manner as in Example 1 except that the nickel salt shown in Table 5 below was used instead of the cerium salt.
実施例23〜27 下記第６表に示す一般式（２）の化合物を使用する以外
は、上記実施例１と同様にして一般式（１）の目的化合
物を得た。 Examples 23 to 27 Target compounds of general formula (1) were obtained in the same manner as in Example 1 except that the compound of general formula (2) shown in Table 6 below was used.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 31/26 31/28 Ｃ０７Ｃ 45/28 47/575 // Ｃ０７Ｂ 61/00 ３００ Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location B01J 31/26 31/28 C07C 45/28 47/575 // C07B 61/00 300
Claims (1)
ッケル塩からなる群より選ばれた少なくとも１種の助触
媒との共存下、一般式 〔式中R1及びR2は、同一又は異なって水素原子、アルキ
ル基、アルコキシ基、アリール基又はハロゲン原子を示
す。〕 で表わされるパラクレゾール誘導体を液相酸素酸化反応
させて一般式 〔式中R1及びR2は前記に同じ。〕 で表わされるパラヒドロキシベンズアルデヒド誘導体を
得ることを特徴とするパラヒドロキシベンズアルデヒド
誘導体の製造方法。1. A general formula in the presence of a soluble cobalt salt catalyst and at least one cocatalyst selected from the group consisting of cerium salts and nickel salts. [In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a halogen atom. ] The paracresol derivative represented by [In the formula, R 1 and R 2 are the same as defined above. ] The parahydroxy benzaldehyde derivative represented by these is obtained, The manufacturing method of the para hydroxy benzaldehyde derivative characterized by the above-mentioned.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61251292A JPH0772153B2 (en) | 1986-10-21 | 1986-10-21 | Process for producing para-hydroxybenzaldehyde derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61251292A JPH0772153B2 (en) | 1986-10-21 | 1986-10-21 | Process for producing para-hydroxybenzaldehyde derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63104937A JPS63104937A (en) | 1988-05-10 |
| JPH0772153B2 true JPH0772153B2 (en) | 1995-08-02 |
Family
ID=17220636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61251292A Expired - Fee Related JPH0772153B2 (en) | 1986-10-21 | 1986-10-21 | Process for producing para-hydroxybenzaldehyde derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0772153B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119213B (en) * | 2014-06-30 | 2016-04-27 | 上海应用技术学院 | A kind of preparation method of vanillin food grade,1000.000000ine mesh |
-
1986
- 1986-10-21 JP JP61251292A patent/JPH0772153B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63104937A (en) | 1988-05-10 |
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