JP2001192349A - Method for producing hydroxyphenylcyclohexanol - Google Patents
Method for producing hydroxyphenylcyclohexanolInfo
- Publication number
- JP2001192349A JP2001192349A JP35756399A JP35756399A JP2001192349A JP 2001192349 A JP2001192349 A JP 2001192349A JP 35756399 A JP35756399 A JP 35756399A JP 35756399 A JP35756399 A JP 35756399A JP 2001192349 A JP2001192349 A JP 2001192349A
- Authority
- JP
- Japan
- Prior art keywords
- treatment
- supported catalyst
- palladium
- subjected
- activity
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- QHNHEYDAIICUDL-UHFFFAOYSA-N 1-phenylcyclohexane-1,2-diol Chemical compound OC1CCCCC1(O)C1=CC=CC=C1 QHNHEYDAIICUDL-UHFFFAOYSA-N 0.000 title claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000011282 treatment Methods 0.000 claims abstract description 45
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 40
- 230000000694 effects Effects 0.000 claims abstract description 20
- -1 hydroxyphenylcyclohexanol compound Chemical class 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 159000000008 strontium salts Chemical class 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 208000005374 Poisoning Diseases 0.000 description 5
- 231100000572 poisoning Toxicity 0.000 description 5
- 230000000607 poisoning effect Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BZHMBWZPUJHVEE-UHFFFAOYSA-N 2,4-dimethylpentane Chemical compound CC(C)CC(C)C BZHMBWZPUJHVEE-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- LSVLMFBVUQQWOQ-UHFFFAOYSA-N 4-(4-hydroxycyclohexyl)phenol Chemical compound C1CC(O)CCC1C1=CC=C(O)C=C1 LSVLMFBVUQQWOQ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WGECXQBGLLYSFP-UHFFFAOYSA-N (+-)-2,3-dimethyl-pentane Natural products CCC(C)C(C)C WGECXQBGLLYSFP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OEQXBPJIRUTUAX-UHFFFAOYSA-N 2-amino-4-(4-hydroxyphenyl)phenol Chemical compound C1=C(O)C(N)=CC(C=2C=CC(O)=CC=2)=C1 OEQXBPJIRUTUAX-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical class OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- DCHOTFPTCDONQH-UHFFFAOYSA-N 2-hydroxy-2-phenylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C1(O)CCCCC1=O DCHOTFPTCDONQH-UHFFFAOYSA-N 0.000 description 1
- FAMUOIFJNGMNSN-UHFFFAOYSA-N 2-hydroxy-5-(4-hydroxyphenyl)benzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(C=2C=CC(O)=CC=2)=C1 FAMUOIFJNGMNSN-UHFFFAOYSA-N 0.000 description 1
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 1
- QJMYXHKGEGNLED-UHFFFAOYSA-N 5-(2-hydroxyethylamino)-1h-pyrimidine-2,4-dione Chemical compound OCCNC1=CNC(=O)NC1=O QJMYXHKGEGNLED-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- OCDXZFSOHJRGIL-UHFFFAOYSA-N cyclohexyloxycyclohexane Chemical compound C1CCCCC1OC1CCCCC1 OCDXZFSOHJRGIL-UHFFFAOYSA-N 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ビフェノール類を
還元してヒドロキシフェニルシクロヘキサノール類を製
造する方法に関する。ヒドロキシフェニルシクロヘキサ
ノール類は各種医薬、工業薬品などの原料として有用な
物質である。TECHNICAL FIELD The present invention relates to a method for producing hydroxyphenylcyclohexanols by reducing biphenols. Hydroxyphenylcyclohexanols are useful substances as raw materials for various medicines, industrial chemicals and the like.
【０００２】[0002]
【従来の技術】従来、かかるヒドロキシフェニルシクロ
ヘキサノールの製造法としては、たとえば、まず、ｐ−
ブロモフェノール誘導体とシクロヘキサンジオンのヘミ
ケタールをグリニアール反応させ、脱水、還元、ケター
ルの脱離工程を経てヒドロキシフェニルシクロヘキサノ
ンを製造する。これのフェノール性水酸基を保護した
後、シクロヘキサノン部を還元し、保護基をはずすこと
によって目的化合物を得る方法が挙げられる。しかしな
がら、このような方法は、工程数が多く、高価な原料を
用いる不利に加え、危険なグリニアール反応を用いなけ
ればならない不利がある。2. Description of the Related Art Conventionally, as a method for producing such hydroxyphenylcyclohexanol, for example, first, p-
The bromophenol derivative and the hemiketal of cyclohexanedione are subjected to a Grignard reaction to produce hydroxyphenylcyclohexanone through dehydration, reduction, and ketal elimination steps. After protecting the phenolic hydroxyl group, the cyclohexanone moiety is reduced and the protecting group is removed to obtain the desired compound. However, such a method has the disadvantage of having to use a dangerous Grignard reaction in addition to the disadvantage of having many steps and using expensive raw materials.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、簡潔な反応
系かつ温和な反応条件下に、ヒドロキシフェニルシクロ
ヘキサノール類を製造する方法を提供することを目的と
する。An object of the present invention is to provide a method for producing hydroxyphenylcyclohexanols in a simple reaction system under mild reaction conditions.
【０００４】[0004]
【課題を解決するための手段】本発明者は、前記従来技
術の課題を解決すべく、ビフェノール類をヒドロキシフ
ェニルシクロヘキサノール類に水素化還元しうる触媒に
ついて鋭意研究を重ねた。その結果、当該水素化還元触
媒として、パラジウム担体担持触媒にその活性を変化さ
せる処理を施した触媒を用いることにより、前記目的を
達成できることを見出し本発明を完成するに至った。Means for Solving the Problems In order to solve the above-mentioned problems of the prior art, the present inventors have made intensive studies on catalysts capable of hydrogenating biphenols to hydroxyphenylcyclohexanols. As a result, the present inventors have found that the object can be achieved by using a catalyst obtained by subjecting a palladium carrier-supported catalyst to a treatment for changing its activity as the hydrogenation reduction catalyst, and completed the present invention.
【０００５】すなわち本発明は、ビフェノール類を、活
性を変化させる処理を施したパラジウム担体担持触媒の
存在下に、水素化還元することを特徴とするヒドロキシ
フェニルシクロヘキサノール類の製造法；さらには前記
製造法に用いる、活性を変化させる処理を施したパラジ
ウム担体担持触媒、に関する。That is, the present invention provides a method for producing hydroxyphenylcyclohexanol, which comprises hydrogenating and reducing a biphenol in the presence of a palladium carrier-supported catalyst which has been subjected to a treatment for changing the activity. The present invention relates to a palladium carrier-supported catalyst which has been subjected to a treatment for changing the activity, which is used in the production method.
【０００６】[0006]
【発明の実施の形態】本発明の製造法の原料であるビフ
ェノール類としては、一般式（１）BEST MODE FOR CARRYING OUT THE INVENTION As a raw material of the production method of the present invention, biphenols represented by the general formula (1)
【０００７】[0007]
【化１】 Embedded image
【０００８】（式中、Ｒ１〜Ｒ８はそれぞれ同一または
異なっていてもよく、水素原子、アルキル基、水酸基、
アミノ基またはカルボキシル基を示す。）で表される化
合物があげられる。具体的には、４，４′−ビフェノー
ル、１，２，２′，３′−テトラヒドロキシ−４，４′
−ビフェノール、２−カルボキシ−４，４′−ビフェノ
ール、２−アミノ−４，４′−ビフェノール、２，２′
−ジメチルビフェノール等があげられる。(Wherein R 1 to R 8 may be the same or different and each represents a hydrogen atom, an alkyl group, a hydroxyl group,
Indicates an amino group or a carboxyl group. )). Specifically, 4,4'-biphenol, 1,2,2 ', 3'-tetrahydroxy-4,4'
-Biphenol, 2-carboxy-4,4'-biphenol, 2-amino-4,4'-biphenol, 2,2 '
-Dimethylbiphenol and the like.
【０００９】本発明の製造法に用いる触媒としては、パ
ラジウム担体担持触媒に、当該触媒の活性を変化させる
処理を施したものを用いる。As a catalyst used in the production method of the present invention, a palladium carrier-supported catalyst which has been subjected to a treatment for changing the activity of the catalyst is used.
【００１０】活性を変化させる処理を施されるパラジウ
ム担体担持触媒は、特に制限されないが、固体酸点によ
る官能基の分解性が少ないこと、および汎用性の点でパ
ラジウム活性炭担持触媒が好ましい。The palladium carrier-supported catalyst subjected to the activity changing treatment is not particularly limited. However, a palladium-activated carbon-supported catalyst is preferred from the viewpoints of low decomposability of functional groups due to solid acid sites and versatility.
【００１１】また、パラジウム担体担持触媒のパラジウ
ム金属担持率は特に制限はないが、反応速度や経済性を
勘案すると０．０１重量％から２５重量％程度が好まし
い。パラジウム金属担持率が少なくなると反応速度が低
下し反応時間が長くなる傾向があるため、パラジウム金
属担持率は０．１重量％以上とするのが好ましい。な
お、経済性を考慮すれば、パラジウム金属担持率は１０
重量％以下とするのが好ましい。The palladium metal loading of the palladium carrier-supported catalyst is not particularly limited, but is preferably about 0.01 to 25% by weight in consideration of the reaction rate and economy. When the palladium metal loading decreases, the reaction rate tends to decrease and the reaction time tends to increase. Therefore, the palladium metal loading is preferably 0.1% by weight or more. In consideration of economy, the palladium metal loading rate is 10%.
% By weight or less.
【００１２】パラジウム担体担持触媒に施す活性を変化
させる処理とは、パラジウム担体担持触媒に、各種化合
物を、物理吸着、化学吸着または固定化させることによ
り、パラジウム担体担持触媒の活性を変化させる処理で
あり、多くの工業触媒で一般的に行われている方法を用
いることができる。活性を変化させる当該処理として
は、アルカリ土類金属塩処理、アルカリ金属塩処理、硫
黄被毒処理、リン被毒処理、アミン被毒処理等があげら
れる。これらの処理はいずれかの処理を単独で行っても
よく、数種類の処理を組み合わせて行ってもよい。これ
らの処理のなかでも、アルカリ土類金属塩処理またはア
ルカリ金属塩処理を施したパラジウム担体担持触媒が、
ヒドロキシフェニルシクロヘキサノール類の収率が高く
なるため好ましい。特にリチウム塩処理、マグネシウム
塩処理、カルシウム塩処理、ストロンチウム塩処理およ
びバリウム塩処理からなる群より選ばれる少なくとも一
つの処理を施したパラジウム担体担持触媒がより好まし
い。なお、アルカリ土類金属塩処理に用いるアルカリ土
類金属塩としては、炭酸バリウム、炭酸カルシウム、炭
酸マグネシウム、硝酸バリウム、硝酸カルシウム、硝酸
マグネシウム等があげられ、硫黄被毒処理に用いる硫黄
化合物としては、硫化水素、チオフェン等があげられ、
アルカリ金属塩処理に用いるアルカリ金属塩としては、
炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、
炭酸水素カリウム、炭酸セシウム、硝酸ナトリウム、硝
酸カリウム、硝酸セシウム等があげられ、リン被毒処理
に用いるリン化合物としては、フォスフィン、トリフェ
ニルフォスフィン、黄燐等があげられ、アミン被毒処理
に用いるアミン類としては、トリメチルアミン、ジメチ
ルアミン等があげられる。The treatment for changing the activity applied to the palladium carrier-supported catalyst is a treatment for changing the activity of the palladium carrier-supported catalyst by physically adsorbing, chemically adsorbing, or immobilizing various compounds on the palladium carrier-supported catalyst. Yes, methods commonly used for many industrial catalysts can be used. Examples of the treatment for changing the activity include alkaline earth metal salt treatment, alkali metal salt treatment, sulfur poisoning treatment, phosphorus poisoning treatment, and amine poisoning treatment. Any of these processes may be performed alone, or a combination of several types of processes may be performed. Among these treatments, a palladium carrier-supported catalyst that has been subjected to an alkaline earth metal salt treatment or an alkali metal salt treatment,
This is preferable because the yield of hydroxyphenylcyclohexanols increases. In particular, a palladium carrier-supported catalyst that has been subjected to at least one treatment selected from the group consisting of lithium salt treatment, magnesium salt treatment, calcium salt treatment, strontium salt treatment and barium salt treatment is more preferred. In addition, examples of the alkaline earth metal salt used in the alkaline earth metal salt treatment include barium carbonate, calcium carbonate, magnesium carbonate, barium nitrate, calcium nitrate, and magnesium nitrate. Examples of the sulfur compound used in the sulfur poisoning treatment include: , Hydrogen sulfide, thiophene, etc.,
As the alkali metal salt used in the alkali metal salt treatment,
Sodium carbonate, potassium carbonate, sodium bicarbonate,
Potassium hydrogen carbonate, cesium carbonate, sodium nitrate, potassium nitrate, cesium nitrate, etc. are mentioned. Phosphorus compounds used for phosphorus poisoning treatment include phosphine, triphenylphosphine, yellow phosphorus and the like. Examples include trimethylamine, dimethylamine and the like.
【００１３】パラジウム担体担持触媒に物理吸着、化学
吸着または固定化され、パラジウム担体担持触媒の活性
を変化させる化合物のパラジウム金属に対する割合は、
特に制限されないが、たとえば、当該化合物がアルカリ
土類金属塩の場合には、通常、アルカリ土類金属の重量
が、パラジウム金属に対して、５〜５００重量％程度と
するのが好ましく、２０〜２００重量％とするのがより
好ましい。また当該化合物がアルカリ金属塩の場合に
は、通常、アルカリ金属の重量が、パラジウム金属に対
して、５〜１００重量％程度とするのが好ましく、１０
〜６５重量％とするのがより好ましい。また当該化合物
が硫黄化合物の場合には、通常、硫黄原子の重量が、パ
ラジウム金属に対して、０．１〜３０重量％程度とする
のが好ましく、０．２〜２０重量％とするのがより好ま
しい。The ratio of the compound to the palladium metal which is physically adsorbed, chemisorbed or immobilized on the palladium carrier-supported catalyst and changes the activity of the palladium carrier-supported catalyst is as follows:
Although not particularly limited, for example, when the compound is an alkaline earth metal salt, usually, the weight of the alkaline earth metal is preferably about 5 to 500% by weight based on the palladium metal, and preferably 20 to 500% by weight. The content is more preferably 200% by weight. When the compound is an alkali metal salt, it is usually preferable that the weight of the alkali metal is about 5 to 100% by weight based on the palladium metal.
More preferably, it is set to 65% by weight. When the compound is a sulfur compound, the weight of the sulfur atom is usually preferably about 0.1 to 30% by weight, and more preferably 0.2 to 20% by weight, based on the palladium metal. More preferred.
【００１４】なお、パラジウム担体担持触媒に対し当該
活性を変化させる処理を施す時期は、特に制限されず、
パラジウム担体担持触媒を調製する前、パラジウム担体
担持触媒を調製中、パラジウム担体担持触媒を調製した
後のいずれのときに行ってもよい。There is no particular limitation on the timing of the treatment for changing the activity of the catalyst supported on the palladium carrier.
It may be performed at any time before preparing the palladium carrier-supported catalyst, during preparation of the palladium carrier-supported catalyst, or after preparing the palladium carrier-supported catalyst.
【００１５】かかるパラジウム担体担持触媒の使用量
は、特に制限されないが、反応速度や経済効果を勘案す
ると原料のビフェノール類に対し、０．０１重量％から
４０重量％程度が好ましい。触媒の使用量が少なくなる
と反応速度が低下し反応時間が長くなる傾向があるた
め、触媒の使用量は０．１重量％以上とするのが好まし
い。なお、経済性を考慮すれば触媒の使用量は１０重量
％以下とするのが好ましい。The amount of the catalyst supported on the palladium carrier is not particularly limited, but is preferably about 0.01% to 40% by weight based on the starting biphenol in consideration of the reaction rate and economic effect. When the amount of the catalyst used decreases, the reaction rate tends to decrease and the reaction time tends to increase. Therefore, the amount of the catalyst used is preferably 0.1% by weight or more. In consideration of economy, it is preferable to use the catalyst in an amount of 10% by weight or less.
【００１６】本反応は無溶媒条件でも実施できるが、溶
媒を使用する方が水素化反応の進行が速く制御が容易と
なるため好ましい。反応に用いる溶媒としてはテトラヒ
ドロフラン、１，４−ジオキサン、エチルイソプロピル
エーテル、ジイソプロピルエーテル、ジシクロヘキシル
エーテルなどで例示される各種エーテル類、メタノー
ル、エタノール、１−プロパノール、２−プロパノー
ル、１−ブタノール、２−ブタノール、３−ブタノー
ル、シクロペンタノール、シクロヘキサノール、エチレ
ングリコールなどで例示される各種アルコール類、デカ
リン、シクロヘキサンで例示される環状炭化水素類、ｎ
−ヘプタン、２−メチルヘキサン、２−エチルペンタ
ン、２，４−ジメチルペンタンなどで例示される各種鎖
状炭化水素類などを使用することができる。これらのな
かでもビフェノール類、ヒドロキシフェニルシクロヘキ
サノール類の溶解性の良さからエーテル類および／また
はアルコール類を使用するのが好ましい。なお、反応系
中の原料の濃度は１〜７５重量％程度とするのが好まし
い。This reaction can be carried out without solvent, but it is preferable to use a solvent because the hydrogenation reaction proceeds quickly and the control is easy. As the solvent used for the reaction, various ethers exemplified by tetrahydrofuran, 1,4-dioxane, ethyl isopropyl ether, diisopropyl ether, dicyclohexyl ether, etc., methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- Various alcohols exemplified by butanol, 3-butanol, cyclopentanol, cyclohexanol, ethylene glycol, etc., cyclic hydrocarbons exemplified by decalin and cyclohexane, n
Various chain hydrocarbons exemplified by -heptane, 2-methylhexane, 2-ethylpentane, 2,4-dimethylpentane and the like can be used. Of these, ethers and / or alcohols are preferably used from the viewpoint of good solubility of biphenols and hydroxyphenylcyclohexanols. Note that the concentration of the raw materials in the reaction system is preferably about 1 to 75% by weight.
【００１７】本発明のヒドロキシフェニルシクロヘキサ
ノール類の製造法は、前記ビフェノール類を、前記触媒
の存在下に、水素化還元するものである。In the method for producing hydroxyphenylcyclohexanols of the present invention, the biphenols are hydrogenated and reduced in the presence of the catalyst.
【００１８】水素化還元は、水素雰囲気下、水素流通下
もしくは水素圧力下で行う。反応時の水素圧力、反応器
中の水素の状態に特に制限はないが、反応効率と反応設
備面を考慮して圧力は０．１ＭＰａ〜１０ＭＰａ程度が
望ましく、さらに好ましくは０．１ＭＰａ〜８ＭＰａで
ある。なお、本記述は減圧条件を排除するものではない
が０．１ＭＰａ未満であると減圧水素を作り出す装置が
必要となるため不経済であり、１０ＭＰａを超えるとそ
れだけより高い加圧水素が必要であるため不経済であ
る。The hydrogenation reduction is carried out in a hydrogen atmosphere, under a hydrogen flow, or under a hydrogen pressure. The hydrogen pressure during the reaction and the state of hydrogen in the reactor are not particularly limited, but the pressure is preferably about 0.1 MPa to 10 MPa, more preferably 0.1 MPa to 8 MPa in consideration of reaction efficiency and reaction equipment. is there. This description does not exclude the reduced pressure condition, but if it is less than 0.1 MPa, a device for producing reduced pressure hydrogen is required, which is uneconomical. If it exceeds 10 MPa, higher pressurized hydrogen is required. It is uneconomical.
【００１９】水素化還元の反応温度は、反応速度、溶媒
の蒸気圧および反応圧力の関係を考慮して、１０℃〜３
００℃程度が好ましい。反応温度が低くなると反応速度
が低下し、反応完結にかかる時間が長くなるため、反応
温度は８０℃以上とするのがより好ましい。また、反応
温度が高くなると加熱に要する経費ならびに冷却に要す
る経費が多くなり不経済であるため反応温度は１８０℃
以下とするのがより好ましい。The reaction temperature of the hydrogenation reduction is from 10 ° C. to 3
About 00 ° C. is preferable. As the reaction temperature decreases, the reaction rate decreases, and the time required for completing the reaction increases, so that the reaction temperature is more preferably set to 80 ° C. or higher. When the reaction temperature is high, the cost required for heating and the cost required for cooling increase, which is uneconomical.
It is more preferable to set the following.
【００２０】水素化還元に用いる装置は、反応水素圧力
や反応温度に応じて適宜に選択すれば良い。例えば、加
圧条件では、オートクレーブなどの耐圧容器を用い、常
圧条件では、水素の流通が可能な装置を用いる。形状は
特に限定されない。The apparatus used for the hydrogenation reduction may be appropriately selected according to the reaction hydrogen pressure and the reaction temperature. For example, under pressure conditions, a pressure-resistant container such as an autoclave is used, and under normal pressure conditions, an apparatus through which hydrogen can flow is used. The shape is not particularly limited.
【００２１】かかる本発明の水素化還元によりビフェノ
ール類は、ヒドロキシフェニルシクロヘキサノール類に
還元される。前記一般式（１）で表されるビフェノール
類からは、一般式（２）：By the hydrogenation reduction of the present invention, biphenols are reduced to hydroxyphenylcyclohexanols. From the biphenols represented by the general formula (1), the general formula (2):
【００２２】[0022]
【化２】 Embedded image
【００２３】（式中、Ｒ１〜Ｒ８は化１のそれと同
じ。）で表されるヒドロキシフェニルシクロヘキサノー
ル類が生成する。なお、４，４′−ビフェノールから
は、４−（ｐ−ヒドロキシフェニル）シクロヘキサノー
ルが得られる。(Wherein, R 1 to R 8 are the same as those of Chemical formula 1) to form hydroxyphenylcyclohexanols. In addition, 4- (p-hydroxyphenyl) cyclohexanol is obtained from 4,4'-biphenol.
【００２４】かかる水素化還元によりビフェノール類か
らヒドロキシフェニルシクロヘキサノール類が得られる
が、生成したヒドロキシフェニルシクロヘキサノール類
は、さらに緩やかにビシクロヘキサンジオール類に水素
化還元される傾向がある。これを避けるために、水素化
還元は、水素吸収量を確認しながら行い、ビフェノール
類が、ヒドロキシフェニルシクロヘキサノール類に還元
される理論水素吸収量（原料ビフェノール類の３倍モル
水素量）の８０〜１００モル％程度で攪拌を停止させた
り、反応系の温度を低下させるなどの手段により、水素
化還元反応を停止させる処置を行い、ヒドロキシフェニ
ルシクロヘキサノール類がビシクロヘキサンジオール類
にまで過剰に水素化還元される前に反応を終了させるの
が好ましい。By such hydrogenation reduction, hydroxyphenylcyclohexanols can be obtained from biphenols, and the generated hydroxyphenylcyclohexanols tend to be more slowly hydrogenated to bicyclohexanediols. In order to avoid this, the hydrogenation reduction is carried out while confirming the hydrogen absorption, and the biphenol is reduced to 80% of the theoretical hydrogen absorption (3 times the molar amount of the starting biphenol) by which the biphenols are reduced to hydroxyphenylcyclohexanols. A treatment to stop the hydrogenation-reduction reaction is performed by stopping stirring at about 100 mol% or lowering the temperature of the reaction system, so that hydroxyphenylcyclohexanols are excessively hydrogenated to bicyclohexanediols. It is preferable to terminate the reaction before the reduction.
【００２５】[0025]
【発明の効果】本発明によれば、簡潔な反応系かつ温和
な反応条件下において、ヒドロキシフェニルシクロヘキ
サノールを製造することができる。しかも、活性を変化
させる処理を施したパラジウム担体担持触媒として、ア
ルカリ土類金属塩処理またはアルカリ金属塩処理を施し
たパラジウム担体担持触媒を用いた場合には、収率も非
常に高い。According to the present invention, hydroxyphenylcyclohexanol can be produced in a simple reaction system and under mild reaction conditions. Moreover, when a palladium carrier-supported catalyst that has been treated with an alkaline earth metal salt or an alkali metal salt is used as the palladium carrier-supported catalyst that has been subjected to the activity changing treatment, the yield is very high.
【００２６】[0026]
【実施例】以下に実施例および比較例をあげて本発明を
さらに具体的に説明するが、本発明はこれら実施例に限
定されるものではない。EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
【００２７】実施例1 ２００ｍｌのステンレス製オートクレーブ装置に４，
４′−ビフェノール２０ｇ、市販のバリウム処理を行っ
たパラジウム活性炭担持触媒（エヌ・イー ケムキャッ
ト社製）０．４ｇおよびテトラヒドロフラン２０ｍｌを
加え、容器内を水素ガスで十分置換した後、反応初期圧
力を０．６ＭＰａとし、１３５℃まで反応系内の温度を
上げた。この温度に達した時、水素圧力を０．８ＭＰａ
とし、適宜圧力減少分を補給、水素吸収量が理論水素吸
収量（原料の３倍モル水素量）の８５モル％なるまで４
時間反応させた。冷却後、ろ過した。このろ液をガスク
ロマトグラフ法にて分析した。目的の４−（ｐ−ヒドロ
キシフェニル）シクロヘキサノールの生成率は原料であ
る４，４′−ビフェノールに対して８０モル％であっ
た。Example 1 In a 200 ml stainless steel autoclave,
20 g of 4'-biphenol, 0.4 g of a commercially available barium-treated palladium-activated carbon-supported catalyst (manufactured by NE Chemcat) and 20 ml of tetrahydrofuran were added, and the inside of the vessel was sufficiently purged with hydrogen gas. The pressure in the reaction system was increased to 135 ° C. When this temperature is reached, the hydrogen pressure is increased to 0.8 MPa
Replenish the pressure reduction as appropriate, until the hydrogen absorption reaches 85 mol% of the theoretical hydrogen absorption (three times the amount of hydrogen of the raw material).
Allowed to react for hours. After cooling, the mixture was filtered. This filtrate was analyzed by gas chromatography. The production rate of the desired 4- (p-hydroxyphenyl) cyclohexanol was 80 mol% with respect to the raw material 4,4'-biphenol.
【００２８】実施例２〜１１ パラジウム活性炭担持触媒に施した活性を変化させる処
理、反応温度、反応圧力、反応時間を表１に示すように
変化させた以外は実施例１と同様に行った。結果を表１
に示す。Examples 2 to 11 The same procedures as in Example 1 were carried out except that the treatment applied to the palladium activated carbon-supported catalyst for changing the activity, the reaction temperature, the reaction pressure and the reaction time were changed as shown in Table 1. Table 1 shows the results
Shown in
【００２９】[0029]
【表１】 [Table 1]
フロントページの続き Ｆターム(参考） 4G069 AA03 AA08 AA15 BA08B BB12A BB16A BC01A BC01B BC01C BC04A BC04B BC04C BC08A BC08B BC08C BC09A BC09B BC09C BC10A BC10B BC10C BC12A BC12B BC12C BC13A BC13B BC13C BC72A BC72B BC72C CB02 FA02 FB13 4H006 AA02 AC11 BA25 BA55 BA81 BB14 BB15 BE20 FC22 FC52 FE12 FE13 4H039 CA40 CB10 Continued on the front page F-term (reference) 4G069 AA03 AA08 AA15 BA08B BB12A BB16A BC01A BC01B BC01C BC04A BC04B BC04C BC08A BC08B BC08C BC09A BC09B BC09C BC10A BC10B BC10C BC12A BC12B BC12C BC13ABC12ABC12C BC12ABC12A BB15 BE20 FC22 FC52 FE12 FE13 4H039 CA40 CB10
Claims (7)
理を施したパラジウム担体担持触媒の存在下に、水素化
還元することを特徴とするヒドロキシフェニルシクロヘ
キサノール類の製造法。1. A method for producing hydroxyphenylcyclohexanol, comprising hydrogenating and reducing a biphenol in the presence of a palladium carrier-supported catalyst subjected to a treatment for changing the activity.
ム担体担持触媒が、パラジウム活性炭担時触媒に、活性
を変化させる処理を施したものである請求項１記載の製
造法。2. The method according to claim 1, wherein the palladium carrier-supported catalyst which has been subjected to the activity changing treatment is obtained by subjecting a palladium activated carbon supported catalyst to a treatment for changing the activity.
ム担体担持触媒が、アルカリ土類金属塩処理またはアル
カリ金属塩処理を施したパラジウム担体担持触媒である
請求項１または２記載の製造法。3. The method according to claim 1, wherein the palladium carrier-supported catalyst subjected to the activity changing treatment is a palladium carrier-supported catalyst subjected to an alkaline earth metal salt treatment or an alkali metal salt treatment.
ム担体担持触媒が、リチウム塩処理、マグネシウム塩処
理、カルシウム塩処理、ストロンチウム塩処理およびバ
リウム塩処理からなる群から選ばれる少なくとも一つの
処理を施したパラジウム担体担持触媒である請求項１〜
３のいずれかに記載の製造法。4. The palladium carrier-supported catalyst which has been subjected to the activity changing treatment is subjected to at least one treatment selected from the group consisting of lithium salt treatment, magnesium salt treatment, calcium salt treatment, strontium salt treatment and barium salt treatment. The catalyst is a palladium carrier supported catalyst.
3. The production method according to any one of 3.
ール類である請求項１〜４のいずれかに記載の製造法。5. The method according to claim 1, wherein the solvent is an ether and / or an alcohol.
しながら行う請求項１〜５のいずれかに記載の製造法。6. The production method according to claim 1, wherein the termination of the hydrogenation reduction is performed while confirming the hydrogen absorption amount.
性を変化させる処理を施したパラジウム担体担持触媒。7. A catalyst supported on a palladium carrier, which has been subjected to a treatment for changing the activity, which is used in the production method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35756399A JP2001192349A (en) | 1999-10-29 | 1999-12-16 | Method for producing hydroxyphenylcyclohexanol |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11-308442 | 1999-10-29 | ||
| JP30844299 | 1999-10-29 | ||
| JP35756399A JP2001192349A (en) | 1999-10-29 | 1999-12-16 | Method for producing hydroxyphenylcyclohexanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001192349A true JP2001192349A (en) | 2001-07-17 |
Family
ID=26565549
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35756399A Pending JP2001192349A (en) | 1999-10-29 | 1999-12-16 | Method for producing hydroxyphenylcyclohexanol |
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| Country | Link |
|---|---|
| JP (1) | JP2001192349A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013161594A1 (en) | 2012-04-24 | 2013-10-31 | 住友化学株式会社 | Method for producing hydroxyphenylcyclohexanol compound |
-
1999
- 1999-12-16 JP JP35756399A patent/JP2001192349A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013161594A1 (en) | 2012-04-24 | 2013-10-31 | 住友化学株式会社 | Method for producing hydroxyphenylcyclohexanol compound |
| CN104220406A (en) * | 2012-04-24 | 2014-12-17 | 住友化学株式会社 | Method for producing hydroxyphenylcyclohexanol compound |
| JPWO2013161594A1 (en) * | 2012-04-24 | 2015-12-24 | 住友化学株式会社 | Method for producing hydroxyphenylcyclohexanol compound |
| US9315435B2 (en) | 2012-04-24 | 2016-04-19 | Sumitomo Chemical Company, Limited | Method for producing hydroxyphenylcyclohexanol compound |
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