JP2775319B2 - Method for producing diarylethylene glycol - Google Patents
Method for producing diarylethylene glycolInfo
- Publication number
- JP2775319B2 JP2775319B2 JP1289299A JP28929989A JP2775319B2 JP 2775319 B2 JP2775319 B2 JP 2775319B2 JP 1289299 A JP1289299 A JP 1289299A JP 28929989 A JP28929989 A JP 28929989A JP 2775319 B2 JP2775319 B2 JP 2775319B2
- Authority
- JP
- Japan
- Prior art keywords
- diarylethylene
- glycol
- group
- reaction
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims description 35
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000012285 osmium tetroxide Substances 0.000 claims description 4
- 229910000489 osmium tetroxide Inorganic materials 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- ZUKDFIXDKRLHRB-UHFFFAOYSA-K cobalt(3+);triacetate Chemical compound [Co+3].CC([O-])=O.CC([O-])=O.CC([O-])=O ZUKDFIXDKRLHRB-UHFFFAOYSA-K 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000002994 raw material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- -1 lithium aluminum hydride Chemical compound 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- IHPDTPWNFBQHEB-UHFFFAOYSA-N hydrobenzoin Chemical compound C=1C=CC=CC=1C(O)C(O)C1=CC=CC=C1 IHPDTPWNFBQHEB-UHFFFAOYSA-N 0.000 description 5
- UBYFOQCYKRXTMK-UHFFFAOYSA-N 1,1-diphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(O)(CO)C1=CC=CC=C1 UBYFOQCYKRXTMK-UHFFFAOYSA-N 0.000 description 4
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- MUZMRKGPXHDTOF-UHFFFAOYSA-N 1-methyl-2-[1-(2-methylphenyl)ethenyl]benzene Chemical group CC1=CC=CC=C1C(=C)C1=CC=CC=C1C MUZMRKGPXHDTOF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 150000002832 nitroso derivatives Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ICZJKMUPTCBZPP-UHFFFAOYSA-N 1,1-bis(2-methylphenyl)ethane-1,2-diol Chemical compound CC1=CC=CC=C1C(O)(CO)C1=CC=CC=C1C ICZJKMUPTCBZPP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VAQAXKQRILVNEE-UHFFFAOYSA-N 2-ethenyl-1-phenyl-2H-pyridine Chemical group C1(=CC=CC=C1)N1C(C=CC=C1)C=C VAQAXKQRILVNEE-UHFFFAOYSA-N 0.000 description 1
- GKNPSSNBBWDAGH-UHFFFAOYSA-N 2-hydroxy-2,2-diphenylacetic acid (1,1-dimethyl-3-piperidin-1-iumyl) ester Chemical compound C1[N+](C)(C)CCCC1OC(=O)C(O)(C=1C=CC=CC=1)C1=CC=CC=C1 GKNPSSNBBWDAGH-UHFFFAOYSA-N 0.000 description 1
- LNCZPZFNQQFXPT-UHFFFAOYSA-N 2-phenyl-1,2-propanediol Chemical compound OCC(O)(C)C1=CC=CC=C1 LNCZPZFNQQFXPT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- QCQIKKRAIWBWLJ-UHFFFAOYSA-N C(C)(=O)O.I(=O)CC1=CC=CC=C1 Chemical compound C(C)(=O)O.I(=O)CC1=CC=CC=C1 QCQIKKRAIWBWLJ-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 1
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- WPUKUEMZZRVAKZ-NFBKMPQASA-N [(1r,3r)-1-ethyl-1-methylpiperidin-1-ium-3-yl] 2-hydroxy-2,2-diphenylacetate Chemical compound C1[N@@+](CC)(C)CCC[C@H]1OC(=O)C(O)(C=1C=CC=CC=1)C1=CC=CC=C1 WPUKUEMZZRVAKZ-NFBKMPQASA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- XREOXKSDMNASCB-UHFFFAOYSA-N acetic acid;iodosylbenzene Chemical compound CC(O)=O.O=IC1=CC=CC=C1 XREOXKSDMNASCB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical class CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229960003869 mepenzolate bromide Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZPBISILWWETTE-UHFFFAOYSA-N methyl bromite Chemical compound COBr=O UZPBISILWWETTE-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 230000001734 parasympathetic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229960001501 pipenzolate Drugs 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- IVNFTPCOZIGNAE-UHFFFAOYSA-N propan-2-yl hydrogen sulfate Chemical compound CC(C)OS(O)(=O)=O IVNFTPCOZIGNAE-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 [産業上の利用分野] 本発明は、ジアリールエチレンを特定の酸化剤で酸化
することにより、ジアリールエチレングリコールを得る
新規な方法に関するものである。Description: TECHNICAL FIELD The present invention relates to a novel method for obtaining diarylethylene glycol by oxidizing diarylethylene with a specific oxidizing agent.
ジアリールエチレングリコールの中には有機合成の原
料の中間原料として有用な化合物が多い。例えば、ジフ
ェニルエチレングリコールは部分酸化してジフェニルグ
リコール酸(別名ベンジル酸)に変換することができ
る。ベンジル酸は副交感神経抑制作用のある医薬として
用いられる塩酸ジフェニン、塩酸ベナクチジン、臭化メ
ペンゾレート、ピペンゾレートメチルブロマイトなどを
製造するための中間体として利用される化合物である。Among the diarylethylene glycols, there are many compounds useful as intermediate raw materials for organic synthesis. For example, diphenylethylene glycol can be partially oxidized to diphenylglycolic acid (also known as benzylic acid). Benzic acid is a compound used as an intermediate for producing diphenine hydrochloride, benactidine hydrochloride, mepenzolate bromide, pipenzolate methyl bromite, etc., which are used as drugs having a parasympathetic nerve-suppressing action.
[従来の技術] これらの化合物の中からジフェニルエチレングリコー
ルを例にとり説明すると、例えば、ジフェニルエチレン
グリコールの製造方法としては、次のようなものが提案
されている。[Prior art] Diphenylethylene glycol will be described as an example among these compounds. For example, the following method has been proposed as a method for producing diphenylethylene glycol.
(イ)クロル酢酸とフェニルリチウムを反応させる方法
[J.A.C.S.、VoL.77、3634(1955)]。(A) A method of reacting chloroacetic acid with phenyllithium [JACS, VoL. 77, 3634 (1955)].
(ロ)ベンジル酸あるいはベンジル酸エチルエステルを
リチウムアルミニウムハイドライドで反応させる方法
[J.A.C.S.、VoL.76、1840(1954)]。(B) A method of reacting benzylic acid or benzylic acid ethyl ester with lithium aluminum hydride [JACS, VoL. 76, 1840 (1954)].
[発明が解決しようとする課題] 上記(イ)の方法ではフェニルリチウムが水を嫌う反
応原料であり、危険な上に、工業化するためには各種の
問題点が多い。また、(ロ)の方法では、原料となるベ
ンジル酸あるいはベンジル酸エステルが高価であり、や
はり工業的な製法としては未だ充分であるとは言えな
い。[Problems to be Solved by the Invention] In the method (a), phenyllithium is a reaction raw material that dislikes water, and is dangerous and has many problems in industrialization. In the method (b), benzyl acid or benzyl ester as a raw material is expensive, and it cannot be said that the method is still sufficient as an industrial production method.
ここで、α−メチルスチレンから酸化によりエチレン
グリコール類を製造する方法として、例えば相間移動触
媒を利用し、燐タングステン酸触媒により、過酸化水素
を酸化剤としてα−メチルスチレンを酸化することによ
り、PhC(Me)(OH)CH2OHである1−フェニル−1−メ
チルエチレングリコールを製造する例が知られている
(Chem.−Ztg.、110(7−8)、303−4)。Here, as a method for producing ethylene glycols by oxidation from α-methylstyrene, for example, using a phase transfer catalyst, by oxidizing α-methylstyrene with hydrogen peroxide as an oxidizing agent using a phosphotungstic acid catalyst, An example of producing 1-phenyl-1-methylethylene glycol which is PhC (Me) (OH) CH 2 OH is known (Chem.-Ztg., 110 (7-8), 303-4).
しかしながら、本発明者らの実験によれば、ジフェニ
ルエチレンを上記方法に準じて酸化すると、ジフェニル
エチレングリコールの生成は全く認められず、代わりに
ベンゾフェノンの生成が認められた。However, according to the experiments of the present inventors, when diphenylethylene was oxidized according to the above-mentioned method, no formation of diphenylethylene glycol was observed, and instead, formation of benzophenone was observed.
すなわち、ジフェニルエチレンは2個のフェニル基が
結合しているので、上記のように過酸化水素による酸化
においては、エチレン部分の炭素−炭素結合が開裂し易
いものと考えられる。That is, since diphenylethylene has two phenyl groups bonded, it is considered that the carbon-carbon bond in the ethylene portion is easily cleaved in the oxidation with hydrogen peroxide as described above.
従って、ジフェニルエチレンからグリコール類を得る
ためには、酸化方法を慎重に選択しなければならない。Therefore, in order to obtain glycols from diphenylethylene, the oxidation method must be carefully selected.
本発明は、ジアリールエチレン類を酸化開裂すること
なく酸化して、各種の農薬、医薬品などの中間原料とし
て有用であるジアリールエチレングリコールを製造する
ことを目的とするものである。An object of the present invention is to oxidize diarylethylenes without oxidative cleavage to produce diarylethylene glycol which is useful as an intermediate material for various agricultural chemicals and pharmaceuticals.
[課題を解決するための手段] 本発明は、医薬品などの中間原料として有用であるジ
アリールエチレングリコールを、容易に入手できる安価
な原料から、高い収率をもって製造する方法に関するも
のである。[Means for Solving the Problems] The present invention relates to a method for producing diarylethylene glycol, which is useful as an intermediate material for pharmaceuticals or the like, from a readily available inexpensive material with a high yield.
即ち本発明は、1,1−ジアリールエチレンを、特定の
酸化剤の存在下に酸化することを特徴とするジアリール
エチレングリコールの製造方法に関するものである。That is, the present invention relates to a method for producing diarylethylene glycol, which comprises oxidizing 1,1-diarylethylene in the presence of a specific oxidizing agent.
次に本発明を詳しく説明する。 Next, the present invention will be described in detail.
本発明は、ジアリールエチレングリコールの製造を、
容易に入手することのできる1,1−ジアリールエチレン
を原料として、特定の酸化剤の存在下に酸化することに
より行なう。The present invention relates to the production of diarylethylene glycol,
This is carried out by oxidizing 1,1-diarylethylene which is easily available as a raw material in the presence of a specific oxidizing agent.
本発明の原料は、下記の式(I)で示す1,1−ジアリ
ールエチレンである。The raw material of the present invention is 1,1-diarylethylene represented by the following formula (I).
ここで上式のAr1あるいはAr2は、例えば、フェニル
基、ナフチル基、ビフェニリル基などの置換基を有する
ことのあるアリール基を表わし、同一または異なるもの
である。 Here, Ar 1 or Ar 2 in the above formula represents an aryl group which may have a substituent, such as a phenyl group, a naphthyl group, and a biphenylyl group, and may be the same or different.
前記アリール基は、塩素、弗素、臭素、沃素などのハ
ロゲン原子、ニトロ基、アミノ基、メチル基、エチル基
などの低級アルキル基、メトキシ基、エトキシ基などの
低級アルコキシ基からなる群より選ばれる1〜3個の置
換基で置換されたものでもよい。The aryl group is selected from the group consisting of halogen atoms such as chlorine, fluorine, bromine and iodine, lower alkyl groups such as nitro group, amino group, methyl group and ethyl group, and lower alkoxy groups such as methoxy group and ethoxy group. It may be substituted with 1 to 3 substituents.
具体的な1,1−ジアリールエチレンとしては、1,1−ジ
フェニルエチレン、1,1−フェニルトリルエチレン、1,1
−ジトリルエチレン、1,1−フェニルブロムフェニルエ
チレン、1,1−ビスブロムフェニルエチレン、1,1−ビス
クロロフェニルエチレン、1,1−ビスメトキシフェニル
エチレン、1,1−ビスフロロフェニルエチレン、1,1−フ
ェニルニトロフェニルエチレン、1,1−ビスニトロフェ
ニルエチレン、1,1−フェニル−(3−(1−カルボキ
シエチル)フェニル)エチレン、1,1−フェニルナフチ
ルエチレンなどが挙げられる。Specific 1,1-diarylethylenes include 1,1-diphenylethylene, 1,1-phenyltolylethylene, 1,1
-Ditolylethylene, 1,1-phenylbromophenylethylene, 1,1-bisbromophenylethylene, 1,1-bischlorophenylethylene, 1,1-bismethoxyphenylethylene, 1,1-bisfluorophenylethylene, 1 1,1-phenylnitrophenylethylene, 1,1-bisnitrophenylethylene, 1,1-phenyl- (3- (1-carboxyethyl) phenyl) ethylene, 1,1-phenylnaphthylethylene and the like.
本発明の方法により製造することのできるジアリール
エチレングリコールは、下記一般式(II)により表わす
ことができる。The diarylethylene glycol that can be produced by the method of the present invention can be represented by the following general formula (II).
ここでAr1およびAr2は、上記式(I)におけるものと
同様に定義される。 Here, Ar 1 and Ar 2 are defined in the same manner as in the above formula (I).
本発明の方法により製造されるジアリールエチレング
リコールとしては、上記式(I)の芳香族の置換基はそ
のまま保存される。In the diarylethylene glycol produced by the method of the present invention, the aromatic substituent of the above formula (I) is preserved as it is.
従って、具体的には、例えば、1,1−ジフェニルエチ
レンから1,1−ジフェニルエチレングリコールが得ら
れ、また、1,1−ビスクロロフェニルエチレンからは1,1
−ビスクロロフェニルエチレングリコールが、1,1−フ
ェニル−(3−(1−カルボキシエチル)フェニル)エ
チレンからは1,1−フェニル−(3−(1−カルボキシ
エチル)フェニル)エチレングリコールが、1,1−フェ
ニルピリジルエチレンからは1,1−フェニルピリジルエ
チレングリコールがそれぞれ得られる。Therefore, specifically, for example, 1,1-diphenylethylene glycol can be obtained from 1,1-diphenylethylene, and 1,1-diphenylethylene glycol can be obtained from 1,1-bischlorophenylethylene.
-Bischlorophenylethylene glycol is 1,1-phenyl- (3- (1-carboxyethyl) phenyl) ethylene from 1,1-phenyl- (3- (1-carboxyethyl) phenyl) ethylene glycol is 1,1-phenylpyridylethylene glycol is obtained from 1-phenylpyridylethylene, respectively.
本発明では、1,1−ジアリールエチレンは過マンガン
酸塩、四酸化オスミウム、三酢酸コバルトおよび一重項
酸素からなる群から選ばれる何れかの酸化剤により酸化
される。In the present invention, the 1,1-diarylethylene is oxidized by any oxidizing agent selected from the group consisting of permanganate, osmium tetroxide, cobalt triacetate and singlet oxygen.
具体的な過マンガン酸塩としては、過マンガン酸のカ
リウム塩、バリウム塩、カルシウム塩、マグネシウム
塩、鉛塩などの他に、セチルトリメチルアンモニウム塩
等のアンモニウム塩などが用いられる。Specific examples of permanganates include potassium salts, barium salts, calcium salts, magnesium salts, and lead salts of permanganate, and ammonium salts such as cetyltrimethylammonium salt.
また、四酸化オスミウムは、反応基質に対して等モル
以上加えて酸化する方法の他に、触媒量の四酸化オスミ
ウムをニトロソ化合物、ヨードシル化合物、過酸化物な
どの共酸化剤と共に酸化させる方法も採用することがで
きる。ここで用いる具体的なニトロソ化合物としてはメ
チルモルホリンN−オキシドなどがあり、ヨードシル化
合物としては酢酸ヨードシルトルエン、酢酸ヨードシル
ベンゼンなどがそれぞれ挙げられる。In addition to oxidizing osmium tetroxide by adding an equimolar amount or more to the reaction substrate, there is also a method of oxidizing a catalytic amount of osmium tetroxide with a co-oxidant such as a nitroso compound, an iodosyl compound, or a peroxide. Can be adopted. Specific examples of the nitroso compound used herein include methylmorpholine N-oxide, and examples of the iodosyl compound include iodosyltoluene acetate and iodosylbenzene acetate.
一重項酸素は、過酸化水素と次亜塩素酸ナトリウム、
次亜塩素酸カルシウム、次亜臭素酸ナトリウムなどの次
亜ハロゲン酸塩との反応による方法あるいは有機過酸化
物の熱分解による方法などによれば容易に発生するの
で、これを用いることができる。Singlet oxygen consists of hydrogen peroxide and sodium hypochlorite,
According to a method based on a reaction with a hypohalite such as calcium hypochlorite or sodium hypobromite, or a method based on thermal decomposition of an organic peroxide, etc., it can be easily used.
酸化剤の使用量については特に制限はないが、例え
ば、原料の1,1−ジアリールエチレンに対して、0.1〜20
モル倍、好ましくは1.0〜10モル倍が適当である。酸化
剤の使用量がこの範囲の下限より少ない場合には反応は
充分には進まず、また、酸化剤の使用量を上記範囲の上
限値より多くしても、反応速度の向上には殆ど寄与せ
ず、却って酸化剤の回収に手間取るようになり好ましく
ない。Although there is no particular limitation on the amount of the oxidizing agent, for example, 0.1 to 20 relative to the raw material 1,1-diarylethylene.
Molar times, preferably 1.0 to 10 times, are suitable. When the amount of the oxidizing agent is less than the lower limit of this range, the reaction does not proceed sufficiently, and even when the amount of the oxidizing agent is more than the upper limit of the above range, it hardly contributes to the improvement of the reaction rate. Instead, it takes much time to recover the oxidizing agent, which is not preferable.
反応温度は酸化剤により左右されるが、一般には−50
〜200℃、好ましくは−20〜100℃である。−50より低い
温度では、反応溶媒あるいは反応原料が凝固したり、反
応温度が低過ぎるために反応速度が遅くなるので好まし
くない。また、200℃を超えると反応生成物であるジア
リールエチレングリコールの熱分解などの副反応が生
じ、目的物の選択性が著しく低下するので何れも好まし
くない。また、反応時間は酸化剤あるいは反応温度など
の反応条件によっても異なるが、一般には10分〜10時間
の範囲から選ばれる。The reaction temperature depends on the oxidizing agent, but is generally -50.
~ 200 ° C, preferably -20-100 ° C. If the temperature is lower than −50, the reaction solvent or the reaction raw material is coagulated, or the reaction temperature is too low, so that the reaction rate is undesirably reduced. On the other hand, when the temperature exceeds 200 ° C., side reactions such as thermal decomposition of diarylethylene glycol, which is a reaction product, occur, and the selectivity of the target product is remarkably reduced. The reaction time varies depending on the reaction conditions such as the oxidizing agent and the reaction temperature, but is generally selected from the range of 10 minutes to 10 hours.
反応系の圧力は、何等本発明の反応には影響を与えな
いので、適宜に選択できるが、通常は常圧で充分であ
る。Since the pressure of the reaction system does not affect the reaction of the present invention at all, it can be appropriately selected, but usually normal pressure is sufficient.
1,1−ジアリールエチレンと酸化剤との接触効率を向
上させるために溶媒を用いてもよい。そのような溶媒と
しては、例えば、水、メタノールあるいはイソプロパノ
ールなどのアルコール、ジオキサン、アセトン、アセト
ニトリル、イソオクタン、ベンゼン、クロロホルムなど
の単一溶媒あるいはこれらの混合溶媒などが用いられ、
好ましくは水が用いられる。A solvent may be used to improve the contact efficiency between the 1,1-diarylethylene and the oxidizing agent. As such a solvent, for example, water, an alcohol such as methanol or isopropanol, dioxane, acetone, acetonitrile, isooctane, benzene, a single solvent such as chloroform or a mixed solvent thereof, and the like,
Preferably, water is used.
反応後においては、金属などの固形物を濾過などの手
段により分離した後、常法に従い、ベンゼン、酢酸エチ
ル、クロロホルムなどの有機溶媒で反応混合物を抽出し
た後、通常の蒸留あるいは再結晶などにより高純度のジ
アリールエチレングリコールが容易に得られる。After the reaction, solids such as metals are separated by means such as filtration, and then the reaction mixture is extracted with an organic solvent such as benzene, ethyl acetate, and chloroform according to a conventional method, and then subjected to ordinary distillation or recrystallization. Highly pure diarylethylene glycol is easily obtained.
[発明の効果] 以上に詳述したように、本発明の方法によれば、1,1
−ジアリールエチレンを、特定の酸化剤の存在下に酸化
し、医薬品などの中間原料として有用なジアリールエチ
レングリコールを高い収率で製造することができる。[Effects of the Invention] As described above in detail, according to the method of the present invention, 1,1,1
-Diarylethylene can be oxidized in the presence of a specific oxidizing agent to produce a high yield of diarylethylene glycol useful as an intermediate material for pharmaceuticals and the like.
[実施例] 以下に本発明を実施例により更に説明する。[Examples] Hereinafter, the present invention will be further described with reference to Examples.
<実施例1> 1,1−ジアリールエチレンとして1,1−ジフェニルエチ
レン10.0g(50mmol)をエタノールで希釈して120mlにし
たものを−15℃に保ちながら、過マンガン酸カリウム1
2.0gと硫酸マグネシウム9.0gの160ml水溶液を滴下し、
混合液中に過マンガン酸カリウムによる紫色が現われる
まで滴下を続けた。Example 1 10.0 g (50 mmol) of 1,1-diphenylethylene as 1,1-diarylethylene was diluted to 120 ml with ethanol and kept at -15 ° C. while keeping potassium permanganate 1
A 160 ml aqueous solution of 2.0 g and 9.0 g of magnesium sulfate was added dropwise.
The dropwise addition was continued until a purple color due to potassium permanganate appeared in the mixture.
滴下後一時間撹拌した後、反応液から二酸化マンガン
を濾別し、更にエーテルで濾液を抽出した。エーテル層
を亜硫酸ナトリウムで失活した後、乾燥し更に溶媒を蒸
発させ、白色固体の粗生成物を得た。粗生成物をベンゼ
ン、n−ヘキセンで再結晶し、精製物5.2gを得た。精製
物をNMRおよびIRで分析したところ1,1−ジフェニルエチ
レングリーコールであることを確認した。After stirring for 1 hour after the dropwise addition, manganese dioxide was filtered off from the reaction solution, and the filtrate was extracted with ether. After quenching the ether layer with sodium sulfite, it was dried and the solvent was further evaporated to obtain a crude product as a white solid. The crude product was recrystallized from benzene and n-hexene to obtain 5.2 g of a purified product. Analysis of the purified product by NMR and IR confirmed that it was 1,1-diphenylethylene glycol.
粗生成物を液体クロマトグラフ(カラム:ERMAERC−10
00、溶離液:75%メタノール水溶液、検出器:UV−225n
m)で分離定量したところ、原料の転化率が85%で1,1−
ジフェニルエチレングリコールが72%の収率で得られ
た。The crude product was subjected to liquid chromatography (column: ERMAERC-10
00, eluent: 75% methanol aqueous solution, detector: UV-225n
m), the conversion of the raw material was 85% and 1,1-
Diphenylethylene glycol was obtained with a yield of 72%.
<実施例2> 1,1−ジアリールエチレンとして1,1−ジフェニルエチ
レン1.0g(5.6mmol)を三酢酸コバルト(13.9mmol)と
1.5mlの水と40mlの氷酢酸溶液に溶かし反応させた。<Example 2> 1.0 g (5.6 mmol) of 1,1-diphenylethylene as 1,1-diarylethylene was mixed with cobalt triacetate (13.9 mmol).
1.5 ml of water and 40 ml of glacial acetic acid solution were dissolved and reacted.
反応はアルゴン雰囲気下で70℃で撹拌せずに8時間行
なった。反応液をエーテルで抽出し、エーテル層を亜硫
酸ナトリウム水溶液で洗浄し、更に水洗した後、硫酸マ
グネシウムで乾燥した。エーテルを蒸留で除くと白色固
体の粗生成物が残った。The reaction was carried out at 70 ° C. for 8 hours without stirring under an argon atmosphere. The reaction solution was extracted with ether, and the ether layer was washed with an aqueous solution of sodium sulfite, further washed with water, and dried over magnesium sulfate. The ether was removed by distillation, leaving a crude product as a white solid.
その後の分析あるいは定量を実施例1と同様に行な
い、原料の転化率66%で、ジフェニルエチレングリコー
ル46%の収率で得た。Subsequent analysis or quantification was performed in the same manner as in Example 1. The conversion of the raw material was 66% and the yield of diphenylethylene glycol was 46%.
<実施例3> 1,1−ジアリールエチレンとして1,1−フェニル−(3
−(1−カルボキシエチル)フェニル)エチレン5.0g
(20mmol)のメタノール300ml溶液を10℃に冷却し、そ
の中に31%過酸化水素水溶液6.6g(60mmol)を加える。
この溶液に10.0%次亜塩素酸ナトリウム水溶液30.1g(5
0mmol)を、冷却と撹拌を続けながら2時間で滴下し
た。反応液はそのままの温度で一晩撹拌を続けた。反応
混合物を水で薄めた後、エーテルで抽出した。Example 3 1,1-phenyl- (3
-(1-carboxyethyl) phenyl) ethylene 5.0g
A solution of (20 mmol) in 300 ml of methanol is cooled to 10 ° C., and 6.6 g (60 mmol) of a 31% aqueous hydrogen peroxide solution are added thereto.
30.1 g of 10.0% aqueous sodium hypochlorite solution (5
0 mmol) was added dropwise over 2 hours with continued cooling and stirring. The reaction was stirred overnight at the same temperature. The reaction mixture was diluted with water and extracted with ether.
エーテル層を亜硫酸ナトリウム水溶液で洗浄し、更に
水で洗った後、硫酸マグネシウムで乾燥した。エーテル
を蒸留で除くと粘性のある液体が得られた。The ether layer was washed with an aqueous solution of sodium sulfite, further washed with water, and dried over magnesium sulfate. Removal of the ether by distillation gave a viscous liquid.
粗生成物1gに対して2.5%硫酸イソプロパノール溶液2
0mlを加え、還流温度で3時間反応させた。反応液を水
酸化ナトリウム水溶液で塩基性にした後、エーテルで抽
出し、エーテル層を乾燥した後濃縮し、残留液をGC−MA
SSで分析したところ、原料転化率は59.8%であり、1,1
−フェニル−(3−(1−イソプロポキシカルボニルエ
チル)フェニル)エチレングリコールは36%の収率で生
成した。2.5% isopropanol sulfate solution per 1 g of crude product 2
0 ml was added, and the mixture was reacted at a reflux temperature for 3 hours. The reaction solution was made basic with an aqueous sodium hydroxide solution, extracted with ether, the ether layer was dried and concentrated, and the remaining solution was subjected to GC-MA
When analyzed by SS, the raw material conversion was 59.8%,
-Phenyl- (3- (1-isopropoxycarbonylethyl) phenyl) ethylene glycol was produced in a yield of 36%.
<実施例4> 1,1−ジアリールエチレンとして1,1−ジトリルエチレ
ン、1,1−ビスクロロフェニルエチレンおよび1,1−ビス
メトキシフェニルエチレンを各々50mmol用い、実施例1
と同様な操作を行なったところ、1,1−ジトリルエチレ
ングリコール、1,1−ビスクロロフェニルエチレングリ
コール、および1,1−ビスメトキシフェニルエチレング
リコールが各々得られた。転化率と収率は、各々75%/6
1%、81%/70%および97%/80%であった。<Example 4> Example 1 was conducted using 50 mmol of 1,1-ditolylethylene, 1,1-bischlorophenylethylene, and 1,1-bismethoxyphenylethylene as 1,1-diarylethylene, respectively.
By performing the same operation as in 1, 1,1-ditolylethylene glycol, 1,1-bischlorophenylethylene glycol, and 1,1-bismethoxyphenylethylene glycol were obtained, respectively. Conversion and yield are 75% / 6 respectively
1%, 81% / 70% and 97% / 80%.
<比較例> 1,1−ジアリールエチレンとして、ジフェニルエチレ
ン10.0g(50mmol)を、t−ブタノールで希釈し50mlと
した後、珪タングステン酸(SiO2・12WO2・2H2O)3.35g
(1mmol)、31%過酸化水素水16.5g(150mmol)を加
え、還流させつつ16時間反応させた。<Comparative Example> 1,1 diaryl ethylene, diphenylethylene 10.0 g (50 mmol), after a 50ml diluted with t- butanol, silicotungstic acid (SiO 2 · 12WO 2 · 2H 2 O) 3.35g
(1 mmol) and 16.5 g (150 mmol) of 31% aqueous hydrogen peroxide were added, and the mixture was reacted for 16 hours under reflux.
反応終了後、水100mlを加えてエーテルで抽出した。
エーテル液を水洗した後、乾燥し蒸留によりエーテルを
除いた。After completion of the reaction, 100 ml of water was added, and the mixture was extracted with ether.
After washing the ether solution with water, it was dried and the ether was removed by distillation.
実施例1と同様にして分析したところ、原料の転化率
は32%であったが、ジフェニルエチレンは全く検出され
ず、その代わりにベンゾフェノンが23%の収率で得られ
た。When analyzed in the same manner as in Example 1, the conversion of the raw material was 32%, but no diphenylethylene was detected, and instead, benzophenone was obtained in a yield of 23%.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C07C 43/23 C07C 43/23 A 67/31 67/31 69/732 69/732 Z 205/19 205/19 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C07C 43/23 C07C 43/23 A 67/31 67/31 69/732 69/732 Z 205/19 205/19
Claims (2)
リールエチレンを、過マンガン酸塩、四酸化オスミウ
ム、三酢酸コバルトおよび一重項酸素からなる群から選
ばれる何れかの酸化剤の存在下に酸化することを特徴と
する、下記一般式(II)で表わされる1,1−ジアリール
エチレングリコールの製造方法、 式中、Ar1およびAr2は同一または異なるアリール基であ
る。1. The method according to claim 1, wherein the 1,1-diarylethylene represented by the following general formula (I) is an oxidizing agent selected from the group consisting of permanganate, osmium tetroxide, cobalt triacetate and singlet oxygen. A method for producing a 1,1-diarylethylene glycol represented by the following general formula (II), which comprises oxidizing in the presence of: In the formula, Ar 1 and Ar 2 are the same or different aryl groups.
トロ基、アミノ基、低級アルキル基および低級アルコキ
シ基からなる群より選ばれる1〜3個の置換基を有する
ことを特徴とする、請求項1記載の1,1−ジアリールエ
チレングリコールの製造方法。2. The aryl group of the above formula has one to three substituents selected from the group consisting of a halogen atom, a nitro group, an amino group, a lower alkyl group and a lower alkoxy group. Item 1. The method for producing a 1,1-diarylethylene glycol according to Item 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1289299A JP2775319B2 (en) | 1989-11-07 | 1989-11-07 | Method for producing diarylethylene glycol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1289299A JP2775319B2 (en) | 1989-11-07 | 1989-11-07 | Method for producing diarylethylene glycol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03151338A JPH03151338A (en) | 1991-06-27 |
JP2775319B2 true JP2775319B2 (en) | 1998-07-16 |
Family
ID=17741386
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1289299A Expired - Lifetime JP2775319B2 (en) | 1989-11-07 | 1989-11-07 | Method for producing diarylethylene glycol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2775319B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110181654A1 (en) * | 2010-01-27 | 2011-07-28 | Robert Radi | Customized writing instrument and method for manufacturing same |
-
1989
- 1989-11-07 JP JP1289299A patent/JP2775319B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH03151338A (en) | 1991-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0566468A2 (en) | Process for the preparation of a biphenyl derivative | |
JP2001199923A (en) | Method for selectively oxidizing alcohol using readily removable nitroxyl radical | |
JP2775319B2 (en) | Method for producing diarylethylene glycol | |
JP2740853B2 (en) | Method for producing 2,2-diaryl glycolic acid | |
JPH07145157A (en) | Production of optically active epoxide | |
JP2002179608A (en) | Method for producing phthalaldehyde | |
JPS58189133A (en) | Manufacture of 2,3,5-trimethyl-p-benzoquinone | |
JPH04149160A (en) | Production of 1-amino-4-alkoxybenzene compounds | |
JP3008296B2 (en) | Method for producing diaryl glycolic acid | |
JP4369240B2 (en) | Oxidation of unsaturated alcohol | |
US5214192A (en) | Process for preparing iodoarene compounds | |
JP3001626B2 (en) | 2-Chloropropionaldehyde trimer and method for producing the same | |
JPH0832647B2 (en) | Method for producing aldehyde from primary alcohol | |
JPS6137753A (en) | Method of oxidizing cinnamic aldehyde | |
JP3371544B2 (en) | Method for producing aromatic aldehyde | |
JPH03112940A (en) | Production of (+-)-4-formyl-alpha-alkylbenzyl alcohol | |
JPS6038343A (en) | Production of phenylacetic acid derivative | |
Dai et al. | Structural Effect on Eu (fod) 3‐Catalyzed Rearrangement of Allylic Esters | |
WO1990009975A1 (en) | Aldehyde oxidation | |
JPS6310706B2 (en) | ||
US4493799A (en) | Synthesis of succinonitriles | |
KR100278967B1 (en) | A preparing method of ortho-difluorobenzoic acid derivatives | |
JPH078827B2 (en) | Method for producing α, β-unsaturated aldehyde | |
JP2001233818A (en) | Method for producing biphenylylacetic acid | |
JPS6039061B2 (en) | Process for producing cyclopentadec-4-yn-1-one |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |