CN101102997A - 磺酰化二苯基乙二胺、其制备方法和在转移氢化催化中的用途 - Google Patents
磺酰化二苯基乙二胺、其制备方法和在转移氢化催化中的用途 Download PDFInfo
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- CN101102997A CN101102997A CNA2005800467592A CN200580046759A CN101102997A CN 101102997 A CN101102997 A CN 101102997A CN A2005800467592 A CNA2005800467592 A CN A2005800467592A CN 200580046759 A CN200580046759 A CN 200580046759A CN 101102997 A CN101102997 A CN 101102997A
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- Prior art keywords
- diamines
- alkyl
- alkaryl
- catalyzer
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- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 5
- 238000005984 hydrogenation reaction Methods 0.000 title description 3
- 238000006555 catalytic reaction Methods 0.000 title description 2
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical class C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 title 1
- 150000004985 diamines Chemical class 0.000 claims abstract description 70
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 238000009901 transfer hydrogenation reaction Methods 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 14
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 10
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 8
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- -1 methoxyl group Chemical group 0.000 claims description 27
- 230000006103 sulfonylation Effects 0.000 claims description 19
- 238000005694 sulfonylation reaction Methods 0.000 claims description 19
- 150000002460 imidazoles Chemical class 0.000 claims description 11
- 125000005594 diketone group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 150000003997 cyclic ketones Chemical class 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 7
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 4
- PONXTPCRRASWKW-KBPBESRZSA-N diphenylethylenediamine Chemical compound C1([C@H](N)[C@@H](N)C=2C=CC=CC=2)=CC=CC=C1 PONXTPCRRASWKW-KBPBESRZSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 description 3
- SXPOMOHAHKKGGA-UHFFFAOYSA-N 4-(2,3-dimethylbenzoyl)oxy-2,3-dihydroxy-4-oxobutanoic acid Chemical compound CC1=C(C(=CC=C1)C(=O)OC(=O)C(C(C(=O)O)O)O)C SXPOMOHAHKKGGA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- LAXRNWSASWOFOT-UHFFFAOYSA-J (cymene)ruthenium dichloride dimer Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ru+2].[Ru+2].CC(C)C1=CC=C(C)C=C1.CC(C)C1=CC=C(C)C=C1 LAXRNWSASWOFOT-UHFFFAOYSA-J 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- RJWUMFHQJJBBOD-UHFFFAOYSA-N 2-methylheptadecane Chemical compound CCCCCCCCCCCCCCCC(C)C RJWUMFHQJJBBOD-UHFFFAOYSA-N 0.000 description 2
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000007193 benzoin condensation reaction Methods 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
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- 239000003446 ligand Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VGKDLMBJGBXTGI-SJCJKPOMSA-N sertraline Chemical compound C1([C@@H]2CC[C@@H](C3=CC=CC=C32)NC)=CC=C(Cl)C(Cl)=C1 VGKDLMBJGBXTGI-SJCJKPOMSA-N 0.000 description 2
- 229960002073 sertraline Drugs 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- GUUDUUDWUWUTPD-UHFFFAOYSA-N 1-ethyl-4-propan-2-ylbenzene Chemical compound CCC1=CC=C(C(C)C)C=C1 GUUDUUDWUWUTPD-UHFFFAOYSA-N 0.000 description 1
- OCQAXYHNMWVLRH-UHFFFAOYSA-N 2,3-dibenzoyl-2,3-dihydroxybutanedioic acid Chemical group C=1C=CC=CC=1C(=O)C(O)(C(O)=O)C(O)(C(=O)O)C(=O)C1=CC=CC=C1 OCQAXYHNMWVLRH-UHFFFAOYSA-N 0.000 description 1
- YMHOBZXQZVXHBM-UHFFFAOYSA-N 2,5-dimethoxy-4-bromophenethylamine Chemical compound COC1=CC(CCN)=C(OC)C=C1Br YMHOBZXQZVXHBM-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- KMGUEILFFWDGFV-UHFFFAOYSA-N 2-benzoyl-2-benzoyloxy-3-hydroxybutanedioic acid Chemical compound C=1C=CC=CC=1C(=O)C(C(C(O)=O)O)(C(O)=O)OC(=O)C1=CC=CC=C1 KMGUEILFFWDGFV-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- BTKLMGGKCQZDNC-UHFFFAOYSA-N CC(C)CCCCCCC[O] Chemical compound CC(C)CCCCCCC[O] BTKLMGGKCQZDNC-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UVGSRARLWOYTNE-UHFFFAOYSA-N OC1=C2C=CC=CC2=NC2=CCCCC2=C1 Chemical class OC1=C2C=CC=CC2=NC2=CCCCC2=C1 UVGSRARLWOYTNE-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- YGXMUPKIEHNBNQ-UHFFFAOYSA-J benzene;ruthenium(2+);tetrachloride Chemical compound Cl[Ru]Cl.Cl[Ru]Cl.C1=CC=CC=C1.C1=CC=CC=C1 YGXMUPKIEHNBNQ-UHFFFAOYSA-J 0.000 description 1
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- WTWBUQJHJGUZCY-UHFFFAOYSA-N cuminaldehyde Chemical compound CC(C)C1=CC=C(C=O)C=C1 WTWBUQJHJGUZCY-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001295 dansyl group Chemical group [H]C1=C([H])C(N(C([H])([H])[H])C([H])([H])[H])=C2C([H])=C([H])C([H])=C(C2=C1[H])S(*)(=O)=O 0.000 description 1
- 239000008232 de-aerated water Substances 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
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- 125000006610 n-decyloxy group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001327 prunus amygdalus amara l. extract Substances 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 description 1
- 125000001680 trimethoxyphenyl group Chemical group 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
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Abstract
式(I)的二胺被描述,其中A是氢、或是饱和或不饱和的C1-C20烷基、或是芳基;B是取代的或未取代的C1-C20烷基、环烷基、烷芳基、烷芳基或芳基,或是烷氨基,并且至少X1、X2、Y1、Y2或Z之一是C1-C10烷基、环烷基、烷芳基、芳烷基或烷氧基取代基。手性二胺可以用来制备在转移氢化反应中适用的催化剂。
Description
二胺
本发明涉及二胺且尤其涉及取代的二苯基乙二胺和由其衍生的催化剂。这样的催化剂可用于加速不对称氢化反应,所述不对称氢化反应的产物可在精细化学品或药物中间体生产中用作例如化学中间体或试剂。
催化的不对称氢化包括利用手性金属络合物对分子氢的活化。但是,在通常所说的转移氢化过程中,在合适的手性催化剂存在的情况下,有机分子也可以被用作氢供体。氢供体例如异丙醇或甲酸通常与[(磺酰化二胺)RUCl(芳烃)]型催化剂一起用于还原羰基。这种技术给催化的不对称氢化提供了有力的补充。事实上转移氢化特别适用于对于氢化反应是困难基质的酮如炔酮和环酮的不对称还原。
迄今为止,转移氢化催化剂的磺酰化二胺组分被局限于磺酰化二苯基乙二胺(Dpen)和环烷基-1,2-二胺,如1,2-环己烷。例如已经用[(甲苯磺酰基-dpen)RuCl(芳烃)]催化剂将转移氢化应用于药用产物如10-羟基-二氢-二苯并-[b,f]-吖庚因的生产上(见WO2004/031155)。
在此以前所使用的磺酰化二胺组分,在有用的同时在所希望的基质范围不是同等有效的。所以,就需要扩展适用于转移氢化反应催化剂的二胺的范围从而提供具有增强的活性、选择性或稳定性的催化剂。我们已经认识到,通过向二苯基乙二胺的苯环引入一个或多个取代基和通过磺化烃性质的改变,二胺组分的空间和电子特征可以得到有用的适应。
所以本发明提供了一种式(I)的二胺:
其中A是氢、或是饱和的或不饱和的C1-C20烷基、或是芳基;B是取代的或未取代的C1-C20烷基、环烷基、烷芳基、烷芳基或芳基、或烷基氨基;且X1、X2、Y1、Y2或Z中的至少一个是C1-C10烷基、环烷基、烷芳基、芳烷基或烷氧基取代基。
本发明还提供一种制备式(I)的二胺的方法,其包括以下步骤:由式(II)的取代二酮形成取代的螺咪唑,其中X1、X2、Y1、Y2和Z与上文相同,还原取代的螺咪唑以形成取代二胺,任选得溶解取代二胺为对映体富集形式,并磺酰化该取代二胺。
本发明还提供一种催化剂,该催化剂包括式(I)的二胺与合适的催化活性金属的化合物的反应产物。
在式(I)中,A是氢或饱和的或不饱和的C1-C20烷基或芳基。C1-C20烷基可以是支链的或直链的,例如可以是甲基、乙基、正丙基,异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、己基、环己基、乙基己基、异辛基、正壬基、正癸基、异癸基、十三烷基、十八烷基和异十八烷基。芳基可以是未取代的或取代的苯基、萘基或蒽基苯基。合适的取代基是羟基、卤素(如F、Cl、Br、I)、C1-C20烷氧基、氨基、酰氨基、腈基和硫羟基。优选A是氢、甲基乙基、丙基、或苯基。最优选A是氢。
在式(I)中,B通过任选对映体富集的取代二胺的磺酰化引入。大范围的磺酰化化合物可以被用来改变式(I)中的磺酰化二胺的性质。因而,B可以是一个取代的或未取代的C1-C20烷基、环烷基、烷芳基、烷芳基或芳基,例如按上文所述,或是烷基氨基。对于烷基氨基,我们是指B可以是式-NR′2,其中R′,例如是甲基、环己基或异丙基或烷基环结构的氮形成部分。也可以使用氟烷基或氟芳基,例如,B可以是P-CF3-C6H4、C6F5或CF2CF2CF2CF3或CF3。优选B是芳基。该芳基可以是未取代的或取代的苯基、萘基或蒽基苯基或杂芳基化合物如吡啶基。合适的取代基是如上文所述的C1-C20烷基、三氟甲基、羟基、卤素(如F,Cl,Br,I)、C1-C20烷氧基(尤其是甲氧基)、氨基、酰氨基、腈基、硝基和硫羟基。因而B可以是例如邻硝基苯基、对硝基苯基、三氯苯基、三甲氧基苯基、三异丙基苯基、邻氨基苯基、苯甲基(-CH2C6H5)、2-苯基乙基(C2H4C6H5)、苯基(C6H5)、甲苯基(p-CH3-C6H4)、二甲苯基((CH3)2C6H3)、甲氧苯基(CH3O-C6H4)、萘基、或丹酰基(5-二甲氨基-1-萘)。优选地,B是甲苯基,且所述磺酰化是用甲苯磺酰氯(对甲苯磺酰氯)进行的。
本发明的二胺具有两个手性中心,每个手性中心都带有一个具有至少一个取代基X1、X2、Y1、Y2或Z的苯环。取代基X1、X2、Y1、Y2或Z是C1-C10烷基、环烷基、烷芳基、芳烷基或烷氧基。应当理解的是为了满足X1、X2、Y1、Y2或Z所连接的苯环中的碳原子的化合价,当其中的X1、X2、Y1、Y2或Z不是C1-C10烷基、环烷基、烷芳基、芳烷基或烷氧基取代基时,X1、X2、Y1、Y2或Z将是氢原子。
因而至少X1、X2、Y1、Y2或Z之一可以独立地是C1-C10烷基,例如甲基、三氟甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、环戊基、己基、环己基、乙基己基、异辛基、正壬基、正癸基或异癸基;烷芳基,例如苯甲基或苯乙基;芳基,例如苯基、甲苯基或二甲苯基;或者是C1-C10烷氧基,例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基、环戊氧基、戊氧基、己氧基、环己氧基、乙基己氧基、异辛氧基、正壬氧基、正癸氧基或异癸氧基。
优选每个苯环具有一个或更多的取代基。苯环可以在一个或多个位置被取代,如环可以是单取代的、二取代的、三取代的、四取代的、或五取代的。苯环上的取代基可以在邻位(X1,X2)、间位(Y1,Y2)或对位(Z)。但是,当取代基在苯环的间位时,它使氨基的电子效应最小化,这可以促进二胺的合成。因而一个实施方案就是取代二胺是1,2-二-(间取代苯基)乙二胺。当取代基为更多时,它们优选是相同的。例如在一个实施方案中,Y1、Y2可以是氢,且X1、X2和Z优选是相同的烷基、环烷基、烷芳基、芳烷基或烷氧基取代基。在另一个实施方案中,X1、X2和Z可以是氢,且Y1、Y2优选是相同的烷基、环烷基、烷芳基、芳烷基或烷氧基取代基。在优选的实施方案中,X1、X2、Y1和Y2是氢,且Z是C1-C10甲基、环烷基、烷芳基、芳烷基或烷氧基取代基。在尤其优选的实施方案中,X1、X2、Y1和Y2是氢,且Z是甲基。在另一个优选的实施方案中,X1、X2、Y1和Y2是氢,且Z是甲氧基。
本发明的取代二胺可以方便得由式(II)的取代二酮经过螺咪唑,然后被还原为二胺并被磺酰化而制得,在式(II)中X1、X2、Y1、Y2和Z如上所述。
式(II)取代二酮(苯偶酰)可以从市面获得,或可以由式(III)的取代苯甲醛、通过苯偶姻缩合接着将得到的苯偶姻氧化而容易地制得,式(III)中X1、X2、Y1、Y2和Z如上所述。取代的苯甲醛是市售的或可由公知的取代反应合成。苯偶姻缩合反应是熟知的,且通常通过在氰化钠存在下、在合适的溶剂中使取代的苯甲醛反应来进行(见例如lde et al,Org.React.1948,4,269-304)。取代苯偶姻氧化为二酮的反应可以利用乙酸铜和硝酸胺容易地进行(例如见Weiss et al,J.Am.Chem.Soc,1948,3666)。
螺咪唑可以通过用乙酸、乙酸胺和环己酮处理式(II)的取代二酮并加热回流而形成。由得到的取代苯偶姻还原为取代二胺的反应可以通过以下步骤进行:在低于-60℃温度下混合螺咪唑溶液和锂丝以及液氨,用乙醇和氯化铵处理所述混合物,并使该混合物升温到室温。磺酰化所述的取代二胺以提供本发明的取代二胺。
取代二胺可以随后通过在合适的溶剂中,用期望的磺酰氯如Cl-SO2-B和碱如三乙胺处理该取代二胺而被磺酰化。
取代二胺中的氮原子被键合到手性中心,从而取代二胺是手性的。该二胺可以是纯手性的,如(R,R)或(S,S),或者具有一个(R)和一个(S)中心。优选二胺是纯手性的。鉴于二胺可以被用作外消旋混合物,胺优选是对映体富集的。手性取代二胺的拆分可以用手性酸或通过任何其他本领域技术人员已知的方法进行。鉴于可以对式(I)的磺酰化二胺进行拆分,优选拆分在磺酰化步骤之前在取代二胺上进行。例如取代二胺可以在合适的溶剂中用手性羧酸如二甲苯酰酒石酸或二苯甲酰酒石酸处理。拆分的取代二胺优选具有高于70%的对映体过量(ee%),更优选高于90%。
因此这个路线提供了一种有效的和低成本的方法用来制备对映体富集的取代1,2-二苯基乙二胺。该路线在下面被描述用于一个优选实施例,其中A、X1、X2、Y1和Y2是氢,B是例如P-CH3-C6H5,且Z是C1-C10烷基、环烷基、烷芳基、芳烷基或烷氧基取代基;
适用于不对称转移氢化反应的催化剂可以通过将本发明的取代磺酰化二胺与合适的催化活性金属化合物反应来制备。金属化合物优选是选自Ru、Rh、Ir、Co、N、Fe、Pd或Rt的金属的化合物。优选的化合物是Ru、Rh和Ir的化合物,尤其是Ru或Rh的化合物。合适的Ru或Rh化合物是[MX2(芳烃)]2化合物,其中M=Rh或Ru且X=卤素,更优选[RuCl2(芳烃)]2。芳烃化合物是任意合适的芳族分子,包括苯和环戊二烯,例如苯、五甲基环戊二烯和对异丙基苯甲基(4-异丙基甲苯)。用于制备氢化催化剂的特别合适的金属化合物包括[RhCp*Cl2]2(其中Cp*是CpMe5)、[RuCl2(苯)]2和[RuCl2(对异丙基苯甲烷)]2。
催化剂可以通过在温和条件下(如在大约大气压下0-80℃)、在合适的溶剂中简单地将二胺和金属化合物结合来制得。合适的溶剂包括烃、芳烃、氯代烃、酯、醇、醚、DMF及类似物。如果希望,反应可以非原位进行并且如通过在真空下除去溶剂将得到的催化剂分离。或者,催化剂可以原位形成,即,在将被氢化的基质和氢源存在下再次通过将金属化合物和二胺在反应物中结合,所述的反应物可以用合适的溶剂稀释。
可以将本发明的手性催化剂用于转移氢化反应。通常,在催化剂存在下混合羰基化合物或亚胺、氢源、碱和溶剂,所述催化剂可以原位形成。优选氢源是异丙醇或甲酸(或甲酸盐)。可以用催化剂将多种羰基化合物和亚胺还原为相应的手性醇和相应的手性胺。所述反应可以在典型的转移氢化条件下、在多种所属领域技术人员公知的合适溶剂中进行。例如,反应可以在醚、酯或二甲基甲酰胺(DMF)中、在0-75℃温度下进行。水可以存在。与甲酸一起使用时,碱如三乙胺、DBU或其它叔胺是优选的。与异丙醇一起使用时,碱优选是t-BuOK、KOH或iPrOK。
本发明通过下面的实施例加以说明。
实施例1:二胺配体的制备
(I)螺咪唑的形成(1到2)
a)Z=甲基(CH3):将乙酸(70ml)加入装有市售的二酮1a(二甲基二苯基乙二酮11.9g,50mmol)和乙酸铵(27g,350mmol)的烧瓶中。加入环己酮(5.3ml,51.5mmol)并在回流下加热反应混合物1-4小时。冷却到室温之后,混合物被倒入水中并且放置过夜进行结晶。通过过滤收集晶体并减压下干燥。由乙酸乙酯/己烷中进行再结晶并且分两批得出8.22g和3.32g的2a。总产量为11.54g,73%。
b)Z=甲氧基(CH3O):将乙酸(100ml)加入装有市售的二酮1b(二甲氧基二苯基乙二酮,18.9g,70mmol)和乙酸铵(37.7g,490mmol)的烧瓶中,。加入环己酮(74.5ml,72.1mmol)并回流加热反应混合物1-4小时。冷却到室温之后,混合物被倒入水中并且放置过夜进行结晶。通过过滤收集晶体并在减压下干燥。咪唑2b的产量为19.22g,79%。进一步提纯可通过由乙酸乙酯/己烷中结晶来实现。
(II)还原(2到3)
a)Z=甲基(CH3):在氩气和-78℃温度下,将氨气慢慢冷凝入螺咪唑2a(6.95g,22mmol)的无水THF(50ml)溶液。一旦反应混合物的体积达到将近两倍,气流就停止。慢慢加入锂丝(0.62g,88mmol)以确保温度不超过-60℃。搅拌30-60分钟后加入乙醇(2.6ml),再过30-60分钟后加入氯化铵(6.2g)。使混合物升温到室温,加入水(约100ml)和MTBE(约100ml)。各层被分离并且将含水层用100ml MTBE萃取两次。用盐水清洗并且在真空下蒸发结合的有机层,在MTBE中溶解得到的油并加入10%的盐酸(2-3eq.)。搅拌两相混合物30-90分钟并用水稀释。各层被分离并且用水萃取有机层。用二氯甲烷清洗化合的含水层然后用KOH水溶液中和直到pH>10。将粗制的二胺萃取入二氯甲烷(3次)。结合的有机萃取物被干燥(Na2SO4)和蒸发以得到油或固体。作为非对映异构体的19∶1混合物的外消旋二胺3a的产量是4.96g,94%。进一步提纯可通过由乙酸乙酯/己烷中结晶来实现。
b)Z=甲氧基(CH3O):在氩气和-78℃温度下,将氨气慢慢冷凝入螺咪唑2b(6.96g,20mmol)的无水THF(40ml)溶液。一旦反应混合物的体积达到将近两倍,气流就停止。慢慢加入锂丝(0.56g,80mmol)以确保温度不超过-60℃。搅拌30-60分钟后加入乙醇(2.4ml),再过30-60分钟后加入氯化铵(2.8g)。使混合物升温到室温,加入水(约100ml)和MTBE(约100ml)。各层被分离并且用100ml的MTBE萃取水层两次。用盐水清洗并且在真空下蒸发结合的有机层,在MTBE中溶解得到的油并加入10%的盐酸(2-3eq.)。搅拌两相的混合物30-90分钟并用水稀释。用二氯甲烷清洗结合的水层然后用KOH水溶液中和直到pH>10。将粗制的二胺萃取入二氯甲烷(3次)。结合的有机萃取物被干燥(Na2SO4)和蒸发以得到油或固体。作为非对映异构体的19∶1混合物的外消旋二胺3b的产量是4.69g,86%。进一步的提纯可通过由乙酸乙酯/己烷中结晶来实现。
(III)二胺的手性拆分
a)二胺3a的拆分。用二甲苯酰酒石酸在甲醇中形成盐并从甲醇中结晶初步得出94%ee的(S,S)4a。通过进一步结晶可将ee提高到99%。
b)二胺3b的拆分。用二甲苯酰酒石酸在甲醇中形成盐并从甲醇中结晶初步得出74%ee的(S,S)4b。通过进一步结晶使提高ee成为可能。用二苯甲酰基酒石酸在甲醇中形成盐并从甲醇中结晶初步得出98%ee的4b。
(IV)单磺酰化二胺的合成
a)甲苯磺酰基-5a(Z=CH3,B=4-CH3-C6H4)。将三乙胺(210μl,1.5mmol)加入到二胺4a(180mg,0.75mmol)的无水二氯甲烷(8ml)溶液中,并将溶液冷却到0℃。缓慢加入甲苯磺酰氯(对甲苯磺酰氯,148mg,0.77mmol)的无水二氯甲烷(4ml)溶液。在0℃下搅拌该混合物30-120分钟并使其升温到室温保持1-24小时。加入水并分离各层。用二氯甲烷萃取水层两次,结合的有机层被用盐水清洗,并干燥(Na2SO4)和蒸发。可以用柱色谱提纯粗制的单磺化二胺。通过柱状色谱的提纯得到270mg(91%)的白色固体状的Ts-5a。
b)甲苯磺酰基-5b(Z=OCH3,B=4-CH3-C6H4)。将三乙胺(190μl,1.3mmol)加入到二胺4b(175mg,0.65mmol)的无水二氯甲烷(8ml)溶液中,并且将溶液冷却到0℃。缓慢加入甲苯磺酰氯(对甲苯磺酰氯,1428mg,0.67mmol)的无水二氯甲烷(5ml)溶液。在0℃下搅拌该混合物30-120分钟并使其升温到室温保持1-24小时。加入水并分离各层。用二氯甲烷萃取水层两次,结合的有机层被用盐水清洗,并干燥(Na2SO4)和蒸发。可以用柱状色谱提纯粗制的单磺酰化二胺。通过柱状色谱的提纯得到270mg(91%)的白色固体状的Ts-5b。
实施例2:转移氢化催化剂的制备
在惰性气氛下,在70-90℃加热[Ru(对异丙基苯甲烷)Cl2]2(0.5eq.)、三乙胺(2eq.)、单磺化二胺(1eq.)5b在无水异丙醇中的混合物1-4小时。冷却到室温之后,在减压下浓缩溶液,且通过过滤收集橙色固体。用脱气水和少量甲醇清洗该固体,然后在减压下进一步干燥。进一步的提纯可以通过从热的甲醇中沉淀/结晶来进行。
实施例3:单磺化二胺5在不对称转移氢化中的用途
转移氢化催化剂在酮混合物上的测试
带有二胺5的转移氢化催化剂在原位制备,并通过在DMF中预制成的酮混合物来进行测试。在惰性气氛(氩气)下,在40℃加热在无水DMF(2ml)中的[Ru(对异丙基苯甲烷)Cl2]2(0.0025mmol)或[RhCp*Cl2]2(0.0025mmol)、单磺化二胺(0.0055mmol)510分钟。加入五种酮(0.5mL,共1mmol,每种0.2mmol)的DMF溶液(相对于每种基质S/C 40),接着加入0.6ml甲酸/三乙胺的1/1混合物和1ml DMF。在60℃加热反应一个晚上(20小时)并通过CG进行分析(ChiraDex CB column,10psi He,100℃保持12分钟,然后以1.5℃/min的速率升温到180℃,然后以5℃/min的速率升温到200℃)。
所测二胺如下所示用于参考:
conv=转化率
ee对映体过量
结果显示环酮达到了尤其高的转化率和ee值,即,其中酮为部分环状结构,如α-四氢萘酮。
实施例4:TsDAEN和TsDPEN的活性比较
利用α-四氢萘酮作为基质测试(S,S)-TsDAEN和常规的(S,S)-TsDPEN在不对称转移氢化中的活性。在15mmol的规格上、S/C为500/1、用[RuCl2(对异丙基苯甲烷)]2作为金属前体、DMF作为溶剂的条件下,在60℃进行反应。在反应初始加入等量的甲酸三乙铵,在反应过程中加入更多的HCOOH以维持pH在8.2。下面所示的结果表明(S,S)-TsDAEN的活性大于(S,S)-TsDPEN。
二胺配体 | 时间(小时) | 转化率(%) | e.e(%) | |
实例4 | (S,S)-TsDAEN | 1.5522 | 367190 | 98 |
对比例 | (S,S)-TsDPEN | 1234622 | 112531364570 | 98 |
Claims (12)
2.根据权利要求1的二胺,其中A是氢。
3.根据权利要求1或2的二胺,其中B是取代的或未取代的芳基。
4.根据权利要求1-3之一的二胺,其中X1、X2、Y1和Y2是氢,且Z是C1-C10烷基、烷芳基、环烷基、芳烷基或烷氧基取代基。
5.根据权利要求4的二胺,其中Z是甲基。
6.根据权利要求4的二胺,其中Z是甲氧基。
7.根据权利要求1-6之一的二胺,其中该二胺是纯手性的。
9.一种催化剂,其包括如权利要求1-7之一所述的式(I)的二胺与选自Ru、Rh、Ir、Co、Ni、Fe、Pd或Pt的金属的化合物的反应产物。
10.根据权利要求9的催化剂,其中金属化合物是[MX2(芳烃)]2,其中M=Rh或Ru且X=卤素。
11.根据权利要求9或10的催化剂用于进行转移氢化反应的用途。
12.根据权利要求11的催化剂的用途,其中转移氢化反应在环酮上进行。
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- 2009-06-26 US US12/493,043 patent/US20090326274A1/en not_active Abandoned
-
2011
- 2011-12-07 US US13/313,889 patent/US8859815B2/en active Active
-
2012
- 2012-09-28 CY CY20121100907T patent/CY1113605T1/el unknown
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104030950A (zh) * | 2009-03-17 | 2014-09-10 | 约翰森·马瑟公开有限公司 | 在Ru(II)催化剂存在下氢化酮类的方法 |
US9416100B2 (en) | 2009-03-17 | 2016-08-16 | Johnson Matthey Public Limited Company | Process for hydrogenating ketones in the presence of Ru(II) catalysts |
CN104030950B (zh) * | 2009-03-17 | 2017-01-04 | 约翰森·马瑟公开有限公司 | 在Ru(II)催化剂存在下氢化酮类的方法 |
US10406514B2 (en) | 2009-03-17 | 2019-09-10 | Johnson Matthey Public Limited Company | Process for hydrogenating ketones in the presence of Ru(II) catalysts |
CN110066233A (zh) * | 2018-01-22 | 2019-07-30 | 广东东阳光药业有限公司 | 一种单取代胺化合物的制备方法 |
CN110066233B (zh) * | 2018-01-22 | 2021-05-11 | 广东东阳光药业有限公司 | 一种单取代胺化合物的制备方法 |
Also Published As
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US20120077973A1 (en) | 2012-03-29 |
US7667075B2 (en) | 2010-02-23 |
US20080081930A1 (en) | 2008-04-03 |
EP1812384A1 (en) | 2007-08-01 |
CN101102997B (zh) | 2012-10-31 |
CY1113605T1 (el) | 2016-06-22 |
MX2007005935A (es) | 2007-07-04 |
WO2006054115A1 (en) | 2006-05-26 |
RU2446154C2 (ru) | 2012-03-27 |
EP1935880A1 (en) | 2008-06-25 |
PL1812384T3 (pl) | 2012-12-31 |
RU2007122501A (ru) | 2008-12-27 |
ES2390590T3 (es) | 2012-11-14 |
AU2005305640B2 (en) | 2011-09-01 |
SI1812384T1 (sl) | 2012-12-31 |
PT1812384E (pt) | 2012-10-11 |
EP1812384B1 (en) | 2012-07-04 |
KR101287369B1 (ko) | 2013-07-18 |
JP2008520639A (ja) | 2008-06-19 |
GB0425320D0 (en) | 2004-12-22 |
CA2587726C (en) | 2016-04-19 |
US8859815B2 (en) | 2014-10-14 |
AU2005305640A1 (en) | 2006-05-26 |
KR20070091143A (ko) | 2007-09-07 |
US20090326274A1 (en) | 2009-12-31 |
JP5529380B2 (ja) | 2014-06-25 |
UA91527C2 (ru) | 2010-08-10 |
BRPI0516815B1 (pt) | 2015-03-10 |
DK1812384T3 (da) | 2012-10-08 |
BRPI0516815A (pt) | 2008-09-23 |
CA2587726A1 (en) | 2006-05-26 |
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