NO771419L - NEW AMINOPHOSPHINES AND PROCEDURES FOR THEIR PREPARATION - Google Patents
NEW AMINOPHOSPHINES AND PROCEDURES FOR THEIR PREPARATIONInfo
- Publication number
- NO771419L NO771419L NO771419A NO771419A NO771419L NO 771419 L NO771419 L NO 771419L NO 771419 A NO771419 A NO 771419A NO 771419 A NO771419 A NO 771419A NO 771419 L NO771419 L NO 771419L
- Authority
- NO
- Norway
- Prior art keywords
- asymmetric
- reaction
- carried out
- benzene
- complex
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- 230000003287 optical effect Effects 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- -1 aminophosphino Chemical group 0.000 claims description 11
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical class PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- XZKIHKMTEMTJQX-UHFFFAOYSA-N 4-Nitrophenyl Phosphate Chemical compound OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XZKIHKMTEMTJQX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 229910052751 metal Chemical group 0.000 claims description 3
- 239000002184 metal Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims 3
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- 125000004414 alkyl thio group Chemical group 0.000 claims 2
- 125000004104 aryloxy group Chemical group 0.000 claims 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 2
- 230000007062 hydrolysis Effects 0.000 claims 2
- 238000006460 hydrolysis reaction Methods 0.000 claims 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 2
- JMSUNAQVHOHLMX-UHFFFAOYSA-N 1-cyclohexylethanol Chemical compound CC(O)C1CCCCC1 JMSUNAQVHOHLMX-UHFFFAOYSA-N 0.000 claims 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 229940116333 ethyl lactate Drugs 0.000 claims 1
- 229940117360 ethyl pyruvate Drugs 0.000 claims 1
- 238000004508 fractional distillation Methods 0.000 claims 1
- 239000012456 homogeneous solution Substances 0.000 claims 1
- LXZGVFCKZRHKMU-UHFFFAOYSA-N n-benzyl-n-methylaniline Chemical compound C=1C=CC=CC=1N(C)CC1=CC=CC=C1 LXZGVFCKZRHKMU-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003446 ligand Substances 0.000 description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- GHJZSQPLYYPZJI-UHFFFAOYSA-N n'-diphenylphosphanylethane-1,2-diamine Chemical compound C=1C=CC=CC=1P(NCCN)C1=CC=CC=C1 GHJZSQPLYYPZJI-UHFFFAOYSA-N 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 229940012017 ethylenediamine Drugs 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- CBQJSKKFNMDLON-JTQLQIEISA-N N-acetyl-L-phenylalanine Chemical compound CC(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 CBQJSKKFNMDLON-JTQLQIEISA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000003254 radicals Chemical group 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- KWGRBVOPPLSCSI-WPRPVWTQSA-N (-)-ephedrine Chemical class CN[C@@H](C)[C@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WPRPVWTQSA-N 0.000 description 2
- XODAOBAZOQSFDS-JXMROGBWSA-N (e)-2-acetamido-3-phenylprop-2-enoic acid Chemical compound CC(=O)N\C(C(O)=O)=C\C1=CC=CC=C1 XODAOBAZOQSFDS-JXMROGBWSA-N 0.000 description 2
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 2
- UFDFFEMHDKXMBG-UHFFFAOYSA-N 2-acetamidoprop-2-enoic acid Chemical compound CC(=O)NC(=C)C(O)=O UFDFFEMHDKXMBG-UHFFFAOYSA-N 0.000 description 2
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QNAYBMKLOCPYGJ-UWTATZPHSA-N D-alanine Chemical compound C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 description 2
- 125000003047 N-acetyl group Chemical group 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RQEUFEKYXDPUSK-SSDOTTSWSA-N (1R)-1-phenylethanamine Chemical compound C[C@@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-SSDOTTSWSA-N 0.000 description 1
- VFUFIIXSVCSRBQ-LLVKDONJSA-N (2R)-2-acetamido-3-(3-acetyloxy-4-methoxyphenyl)propanoic acid Chemical compound C(C)(=O)OC=1C=C(C[C@@H](NC(C)=O)C(=O)O)C=CC1OC VFUFIIXSVCSRBQ-LLVKDONJSA-N 0.000 description 1
- DNJSHXYKYRIMOH-SECBINFHSA-N (2r)-2-acetamido-3-(1,3-benzodioxol-5-yl)propanoic acid Chemical compound CC(=O)N[C@@H](C(O)=O)CC1=CC=C2OCOC2=C1 DNJSHXYKYRIMOH-SECBINFHSA-N 0.000 description 1
- NSMWYRLQHIXVAP-WDSKDSINSA-N (2s,5s)-2,5-dimethylpiperazine Chemical compound C[C@H]1CN[C@@H](C)CN1 NSMWYRLQHIXVAP-WDSKDSINSA-N 0.000 description 1
- XNCRUNXWPDJHGV-BQYQJAHWSA-N (e)-2-methyl-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(/C)=C/C1=CC=CC=C1 XNCRUNXWPDJHGV-BQYQJAHWSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RIFKADJTWUGDOV-UHFFFAOYSA-N 1-cyclohexylethanone Chemical compound CC(=O)C1CCCCC1 RIFKADJTWUGDOV-UHFFFAOYSA-N 0.000 description 1
- QTNHDDAPMUJZSZ-UHFFFAOYSA-N 2-acetamido-3-(1,3-benzodioxol-5-yl)prop-2-enoic acid Chemical compound CC(=O)NC(C(O)=O)=CC1=CC=C2OCOC2=C1 QTNHDDAPMUJZSZ-UHFFFAOYSA-N 0.000 description 1
- XODAOBAZOQSFDS-UHFFFAOYSA-N 2-acetamido-3-phenylprop-2-enoic acid Chemical compound CC(=O)NC(C(O)=O)=CC1=CC=CC=C1 XODAOBAZOQSFDS-UHFFFAOYSA-N 0.000 description 1
- MCIIDRLDHRQKPH-UHFFFAOYSA-N 2-methyl-3-phenylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=CC=C1 MCIIDRLDHRQKPH-UHFFFAOYSA-N 0.000 description 1
- MSIFHGPIEOZWQZ-UHFFFAOYSA-N 3-chlorobicyclo[2.2.1]hepta-1,3-diene;rhodium Chemical compound [Rh].C1CC2=CC(Cl)=C1C2 MSIFHGPIEOZWQZ-UHFFFAOYSA-N 0.000 description 1
- MDFWXZBEVCOVIO-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]heptan-3-amine Chemical compound C1CC2(C)C(N)CC1C2(C)C MDFWXZBEVCOVIO-UHFFFAOYSA-N 0.000 description 1
- RBMUAGDCCJDQLE-UHFFFAOYSA-N 5-methyl-2-propan-2-ylcyclohexan-1-amine Chemical compound CC(C)C1CCC(C)CC1N RBMUAGDCCJDQLE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KTIPEYSWPZOCIA-UHFFFAOYSA-N azanide dichloroazanide platinum(4+) Chemical compound ClN([Pt](N)(N)N)Cl KTIPEYSWPZOCIA-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006074 cyclodimerization reaction Methods 0.000 description 1
- KWGRBVOPPLSCSI-UHFFFAOYSA-N d-ephedrine Natural products CNC(C)C(O)C1=CC=CC=C1 KWGRBVOPPLSCSI-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- JVLAXAWYFGQTFP-UHFFFAOYSA-N diphenyl(piperazin-1-yl)phosphane Chemical compound C1CNCCN1P(C=1C=CC=CC=1)C1=CC=CC=C1 JVLAXAWYFGQTFP-UHFFFAOYSA-N 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 229960002179 ephedrine Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- IKGHIFGXPVLPFD-NSHDSACASA-N methyl (2s)-2-acetamido-3-phenylpropanoate Chemical compound COC(=O)[C@@H](NC(C)=O)CC1=CC=CC=C1 IKGHIFGXPVLPFD-NSHDSACASA-N 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- HZPZCHFYBJYZKQ-UHFFFAOYSA-N n,n'-bis(diphenylphosphanyl)ethane-1,2-diamine Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)NCCNP(C=1C=CC=CC=1)C1=CC=CC=C1 HZPZCHFYBJYZKQ-UHFFFAOYSA-N 0.000 description 1
- KTHDTJVBEPMMGL-GSVOUGTGSA-N n-acetylalanine Chemical compound OC(=O)[C@@H](C)NC(C)=O KTHDTJVBEPMMGL-GSVOUGTGSA-N 0.000 description 1
- MYWUZJCMWCOHBA-UHFFFAOYSA-N n-methyl-1-phenylpropan-2-amine Chemical compound CNC(C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical compound O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- OIWNHEPSSHYXTG-UHFFFAOYSA-L ruthenium(2+);triphenylphosphane;dichloride Chemical compound Cl[Ru]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 OIWNHEPSSHYXTG-UHFFFAOYSA-L 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
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Description
Nye aminofosfiner og fremgangsmåteNew aminophosphines and method
for deres fremstilling.for their production.
Foreliggende oppfinnelse vedrorer syntese av nye optisk aktive forbindelser som horer til klassen av aminofosfiner, og deres anvendelse sammen med passende derivater av overgangsmetaller, The present invention relates to the synthesis of new optically active compounds belonging to the class of aminophosphines, and their use together with suitable derivatives of transition metals,
ved asymmetrisk hydrogenering av en lang rekke forbindelser,by asymmetric hydrogenation of a wide variety of compounds,
valgt blant prochirale og racemiske olefiner og forbinbindelsene inneholdende Co- og/eller CN-grupper. selected from prochiral and racemic olefins and the compounds containing Co and/or CN groups.
Fremstilling av optisk aktive organiske forbindelser med hby optisk renhet på industriell basis, som f.eks. venstredreiende aminosyrer, er fremdeles nesten utelukkende avhengig av prosesser av biokjemisk eller mikrobiologisk type. Production of optically active organic compounds with hby optical purity on an industrial basis, such as e.g. left-handed amino acids, are still almost exclusively dependent on processes of a biochemical or microbiological type.
Inntil for noen år siden kjente man ikke til noen forsok av ren kjemisk type som på grunn av prosessokonomi og optisk utbytte var i stand' til å konkurrere med de ovennevnte metoder. Until a few years ago, no attempt of a purely chemical type was known which, due to process economy and optical yield, was able to compete with the above-mentioned methods.
Oppdagelsen av nye homogene katalytiske systemer med hby stereo-spesifikk virkning, som f.eks. tris(trifenyl-fosfin)kloro-rodium, og nye fremskritt i syntese av asymmetriske fosforbaserte fosfiner forte til fremstilling av chiral"komplekser av overgangsmetaller med hoy stéreoselektivitet ved hydrogenering av prochirale olefiner. The discovery of new homogeneous catalytic systems with hby stereo-specific action, such as e.g. tris(triphenyl-phosphine)chloro-rhodium, and new advances in the synthesis of asymmetric phosphorus-based phosphines for the preparation of chiral complexes of transition metals with high stereoselectivity by hydrogenation of prochiral olefins.
Det er nå funnet en ny klasse av optisk aktive forbindelser som kan oppnås lett og greit og som tillater fremstilling av et bredt område av aktive komplekser for asymmetrisk hydrogenering av umettede forbindelser, mer spesielt olefiner, med hoy omdannelse og optisk renhet. A new class of optically active compounds has now been found which can be easily obtained and which allows the preparation of a wide range of active complexes for the asymmetric hydrogenation of unsaturated compounds, more particularly olefins, with high conversion and optical purity.
Gjenstanden for den foreliggende oppfinnelse er en ny klasse av The object of the present invention is a new class of
12 3 1 aminderivater av fosfor av typen PR (NR R )_ , hvori R er alkyl, aryl-tio, alkyl-fosfino, aryl-fosfino, amino-fosfino og lignende, 2 3 x varierer fra 0 til 2, NR R representerer optisk aktive amino-grupper som avledes fra de aminoforbindelser som beskrives i det folgende, som utgjor en bred kategori av mono- og poly-dentate ligander, som er i stand til å koordinere overgangsmetaller, slik at det dannes komplekser egnet for asymmetrisk hydrogenering, med hoy omdannelsesgrad, av prochirale. og racemiske olefiner, for fremstilling av de tilsvarende mettede forbindelser med en god optisk renhet.. Fremstillingen av de amino-fosfo-organiske forbindelser gjennomfores ved å gå ut fra forbindelser med formel 12 3 1 amine derivatives of phosphorus of the type PR (NR R )_ , in which R is alkyl, aryl-thio, alkyl-phosphino, aryl-phosphino, amino-phosphino and the like, 2 3 x varies from 0 to 2, NR R represents optically active amino groups derived from the amino compounds described below, which constitute a broad category of mono- and poly-dentate ligands, capable of coordinating transition metals, such that complexes suitable for asymmetric hydrogenation, with a high degree of conversion, of prochirals are formed. and racemic olefins, for the production of the corresponding saturated compounds with a good optical purity. The production of the amino-phospho-organic compounds is carried out by starting from compounds of the formula
hvori, når n er 1, X representeres hydrogen, et alkalimetall eller PR^X, og når n er 2, er X et radikal av typen -Pr\idet R'*' er valgt.blant de ovennevnte radikaler, og når n er 3, står X for P, R 2 og R 3 er like eller forskjellige fra hverandre og står for et alkyl, alkylaryl, aryl-alkyl- eller cykloalkylradikal, idet minst en av de to radikaler inneholder ett eller flere ikke-racemiske chiralsentere. Den nevnte fremstilling av forbindelsene kan gjennomfores i henhold -til et av de folgende skjemaer: wherein, when n is 1, X represents hydrogen, an alkali metal or PR^X, and when n is 2, X is a radical of the type -Pr\where R'*' is selected from among the above-mentioned radicals, and when n is 3, X stands for P, R 2 and R 3 are the same or different from each other and stand for an alkyl, alkylaryl, aryl-alkyl or cycloalkyl radical, at least one of the two radicals containing one or more non-racemic chiral centers. The aforementioned preparation of the compounds can be carried out according to one of the following forms:
hvori gruppene R har de ovennevnte betydninger, B er en organisk base, eller fremstillingen kan gjennomfores i henhold til tidligere kjente prosesser og i samsvar med de tilsvarende achirale forbindelser. in which the groups R have the above meanings, B is an organic base, or the preparation can be carried out according to previously known processes and in accordance with the corresponding achiral compounds.
Blant de optisk aktive aminer (R*NH2) kan f.eks. nevnes alfa-metyl-benzylamin, bornylamin, sek.-butylamin, mentylamin eller et hvilket som helst primært amin inneholdende ett eller flere ikke-racemiske chirale sentere, eller sekundære aminer (R<*>RNH) hvori den ene eller begge grupper knyttet til nitrogenatornet inneholder ett eller flere ikke-racemiske chirale sentere. F.eks. usubstituert N alfa-metylbenzylamin, pipekolin, desoksyefedrin, o-substituert efedrin, N-monosubstituert og N,N<1->disubstituert etylendiamin med minst en ikke-racemisk chiral substituent, ipip^asiner inneholdende ett eller flere ikke-racemiske chirale sentere. Among the optically active amines (R*NH2) can e.g. mention is made of alpha-methyl-benzylamine, bornylamine, sec-butylamine, menthylamine or any primary amine containing one or more non-racemic chiral centers, or secondary amines (R<*>RNH) in which one or both groups attached to the nitrogen atom contains one or more non-racemic chiral centers. E.g. unsubstituted N alpha-methylbenzylamine, pipecoline, desoxyephedrine, o-substituted ephedrine, N-monosubstituted and N,N<1->disubstituted ethylenediamine with at least one non-racemic chiral substituent, ipip^azines containing one or more non-racemic chiral centers.
Det aktive katalytiske kompleks dannes ved den asymmetriske hydrogenering ved å omsette en eller flere av de ovenfor beskrevne ligander med en koordinasjonsforbindelse av et metall av overgangsrekken, foretrukket Cr Mo W Fe Co Ni Ru Rh Pd Pt Os Ir Cu Ag Au Ti V. The active catalytic complex is formed by the asymmetric hydrogenation by reacting one or more of the above-described ligands with a coordination compound of a metal of the transition series, preferably Cr Mo W Fe Co Ni Ru Rh Pd Pt Os Ir Cu Ag Au Ti V.
Ligandene i koordinasjonsforbindelsene kan være anioniske eller noytrale. Blant de anioniske ligander kan nevnes halogene, cyanidet, nitratet, acetatet, acetylacetonatet, sulfidet og lignende ioner. Blant.de noytrale ligander, kan nevnes vann, ammoniakk, aminer fosfiner, karbon-monoksyd, olefiner, diolefiner og lignende. The ligands in the coordination compounds can be anionic or neutral. Among the anionic ligands, halogen, cyanide, nitrate, acetate, acetylacetonate, sulfide and similar ions can be mentioned. Among the neutral ligands, mention may be made of water, ammonia, amines, phosphines, carbon monoxide, olefins, diolefins and the like.
Blant representative forbindelser kan nevnes rodium (III) hydratisert klorid, rutenium (III / klorid, dikloro-tetrakis (tri-fenylfosfin)rutenium(II), rodium (I hj.-dikloro-tetrakis (etylen), rodium(I ha-dikloro-bis(norbornadien), diklorotetraamino-platina (II),dibromo-tetrakis(trifenylfosfin)palladium. Among representative compounds can be mentioned rhodium (III) hydrated chloride, ruthenium (III / chloride, dichloro-tetrakis (tri-phenylphosphine) ruthenium (II), rhodium (I hj.-dichloro-tetrakis (ethylene), rhodium (I ha-dichloro -bis(norbornadiene), dichlorotetraamino-platinum (II), dibromo-tetrakis(triphenylphosphine) palladium.
Molforholdet mellom ligand og komplekset av overgangsmetallet, uttrykt som forholdet mellom antallet av fosforatomer i liganden og antallet av metallatomer i komplekset kan variere mellom 1 og 15, idet verdiene 2, 3 og 4 foretrekkes. The molar ratio between the ligand and the complex of the transition metal, expressed as the ratio between the number of phosphorus atoms in the ligand and the number of metal atoms in the complex can vary between 1 and 15, the values 2, 3 and 4 being preferred.
Reaksjons-losningsmidlene kan være aromatiske eller alifatiske hydrokarboner, alkoholer, etere, ketoner, estere, amider og deres blandinger. The reaction solvents may be aromatic or aliphatic hydrocarbons, alcohols, ethers, ketones, esters, amides and their mixtures.
Reaksjonen med asymmetrisk hydrogenering gjennomfores ved et molforhold mellom substrat og katalysator varierende mellom 10.000 og 10. Reaksjonstemperaturen kan være mellom -70°C og +200°C, foretrukket mellom 0 og 50°C. Hydrogentrykket er i området 1 til 100 atmosfærer.. The reaction with asymmetric hydrogenation is carried out at a molar ratio between substrate and catalyst varying between 10,000 and 10. The reaction temperature can be between -70°C and +200°C, preferably between 0 and 50°C. The hydrogen pressure is in the range of 1 to 100 atmospheres.
De fblgende eksempler illustrerer oppfinnelsen.The following examples illustrate the invention.
Eksempel 1.Example 1.
N,N'-bis(S(-)alfametylbenzyl)etylendiamin separeres ved å gå ut fra S(-)alfametylbenzylamin og dietyl-oksalat. Reduksjonen av diamidet gjennomfores med litiumaluminium-hydrid i THF og det tilsvarende diamin isoleres som dihydrokloridet med smeltepunkt 250°C (utbytte : 80%). N,N'-bis(S(-)alphamethylbenzyl)ethylenediamine is separated by starting from S(-)alphamethylbenzylamine and diethyl oxalate. The reduction of the diamide is carried out with lithium aluminum hydride in THF and the corresponding diamine is isolated as the dihydrochloride with a melting point of 250°C (yield: 80%).
Etter at dihydrokloridet er blitt klaret med 10% NaOH, behandles 0,050 mol av diaminet med 0,100 mol difenylklorofosfin i 300 ml vannfri benzen, i nærvær av 0,200 mol trietylamin. After the dihydrochloride has been clarified with 10% NaOH, 0.050 mole of the diamine is treated with 0.100 mole of diphenylchlorophosphine in 300 ml of anhydrous benzene, in the presence of 0.200 mole of triethylamine.
Blandingen kokes under tilbakelop i 20 timer, hydrokloridet av trietylammonium frafiltreres og benzenlosningen konsentreres inntil N-N• bis (S(-)alfametylbenzyl) N-N' bis(difenylfosfino) etylendiamin separeres, smeltepunkt 138-140°C (utbytte 70% i forhold til utgangs-diaminet.). The mixture is refluxed for 20 hours, the triethylammonium hydrochloride is filtered off and the benzene solution is concentrated until N-N• bis (S(-)alphamethylbenzyl) N-N' bis(diphenylphosphino) ethylenediamine is separated, melting point 138-140°C (yield 70% in relation to starting the diamine.).
/a7<25>= - 91,5° (c = 1 i CHC1,) /a7<25>= - 91.5° (c = 1 in CHC1,)
D D
f (I) Katalysatoren fremstilles ved å behandle 5,5 mg rodium p-— 6 f (I) The catalyst is prepared by treating 5.5 mg of rhodium p-— 6
diklorotetrakis(etylen) (17,7 -,10 mol) med 22,5 mg N-N' bis (S(-)alfa-metylbenzyl) N-N * (difenylfosfino)etylendiamin dichlorotetrakis(ethylene) (17.7 -.10 mol) with 22.5 mg N-N' bis (S(-)alpha-methylbenzyl) N-N * (diphenylphosphino)ethylenediamine
— 6 — 6
(35,4 • 10 mol), idet 6 ml vannfri benzen anvendes som løsningsmiddel. (35.4 • 10 mol), 6 ml of anhydrous benzene being used as solvent.
Atomforhold P/Rh = 2Atomic ratio P/Rh = 2
Opplosningen overfores i en kolbe inneholdende 2,8 g alfa-acetamido-kanelsyre i 24 ml vannfri metanol, idet kolben forbindes _ til et hydrogeneringsapparat som arbeider ved atmosfæretrykk og ^ / som er termostatinnstilt til 25°C, og hvormed det gjennomfores en omhyggelig spyling med hydrogen av reaksjons-omgivelsene for / det katalytiske kompleks tilsettes. The solution is transferred to a flask containing 2.8 g of alpha-acetamido-cinnamic acid in 24 ml of anhydrous methanol, the flask being connected _ to a hydrogenation apparatus operating at atmospheric pressure and ^ / which is thermostatically set to 25°C, and with which a careful flushing is carried out with hydrogen of the reaction environment for / the catalytic complex is added.
Reaksjonsforlopet styres ved vanlig måleteknikk.The course of the reaction is controlled by standard measuring techniques.
Den initiale hastighet for hydrogenabsorpsjonen er omtrent 4 ml/ min., målt under arbeidsbetingelsene. \ The initial rate of hydrogen absorption is approximately 4 ml/min., measured under working conditions. \
/ Etter 3 timer er omdannelsen omtrent 85%. Reaksjonen avsluttes // / After 3 hours the conversion is approximately 85%. The reaction ends //
og reaksjonsproduktet separeres ved avdamping av losningsmidletyunder reduserte trykk. ^ and the reaction product is separated by evaporation of the solvent under reduced pressure. ^
Restproduktet behandles med en 0,5 N NaOH-losning og denThe residual product is treated with a 0.5 N NaOH solution and it
) uopploselige katalysator frafiltreres. // ) insoluble catalyst is filtered off. //
Den vandige losning gjores sur til pH 2-3 med fortynnet HC1, og f ~^den organiske fase ekstraheres fem ganger med etyleter. De kombinerte eterfraksjoner torkes over Na2SO^. Eteren avdampes så. Restproduktet, undersokt ved spektroskopi (NMR, IR) består av The aqueous solution is made acidic to pH 2-3 with dilute HCl, and the organic phase is extracted five times with ethyl ether. The combined ether fractions are dried over Na 2 SO 4 . The ether is then evaporated. The residual product, examined by spectroscopy (NMR, IR) consists of
R(-)N-acetylfenyl-alanin /q?<20>= -40 ( c = 1, EtOH 95%) med et ) J optisk utbytte . på. 84%^ Den spesifikke rotasjon for enantiomert<<>C Irent S( + ) N-acetylfenyl-alanin er /a7d° = + 47'5 ( c = 1, EtoH95%). , R(-)N-acetylphenyl-alanine /q?<20>= -40 ( c = 1, EtOH 95%) with a ) J optical yield . on. 84%^ The specific rotation for enantiomeric <<>C Irent S( + ) N-acetylphenyl-alanine is /a7d° = + 47'5 ( c = 1, EtoH95%). ,
Eksempel 2.Example 2.
Ved å gjenta fremgangsmåten beskrevet i eksempel 1 og ved anvende R(+) alfa-metylbenzylamin, fremstilles N-N'(R(+) alfametylbenzyl) N-N• (difenylfosfino) etylendiaminet, med to chiralitets-sentere med motsatt konfigurasjon i forhold til dem i difosfinet i eksempel 1. By repeating the procedure described in example 1 and using R(+) alpha-methylbenzylamine, N-N'(R(+) alphamethylbenzyl) N-N• (diphenylphosphino) ethylenediamine is prepared, with two chirality centers with the opposite configuration in relation to them in the diphosphine of Example 1.
Liganden omsettes med komplekset rodium (I) og det katalytiske kompleks anvendes ved hydrogeneringen av alfa-acetaminokanelsyre. Det hydrogenerte produkt, etter isolering og undersøkelse som i eksempel 1, består av S-£f) N-acetylf enyl-alanin, med en iakttatt The ligand is reacted with the complex rhodium (I) and the catalytic complex is used in the hydrogenation of alpha-acetaminocinnamic acid. The hydrogenated product, after isolation and examination as in example 1, consists of S-£f) N-acetylphenyl-alanine, with an observed
— 20 — 20
rotasjon /a7 d + 38'9 (c = 1, EtOH 95%) indikerende enrotation /a7 d + 38'9 (c = 1, EtOH 95%) indicating a
Eksempel 3.Example 3.
2(S),5(S) dimetylpiperazin fremstilles ved cyklodimerisering av S(-) alanin og reduksjon av det resulterende diketopiperazin med 1i tiumaluminiumhydr id. 2(S),5(S) dimethylpiperazine is prepared by cyclodimerization of S(-) alanine and reduction of the resulting diketopiperazine with 1ithium aluminum hydride.
Den etterfolgende reaksjon av det ovennevnte piperazin med difenylklorofosfin i nærvær av trietylamin forer til.dannelse av 2(S), The subsequent reaction of the above-mentioned piperazine with diphenylchlorophosphine in the presence of triethylamine leads to the formation of 2(S),
— 23 — 23
5(S) dimetylN,N" difenylfosfino (+) piperazin / a7 D = 78 (c = 1, THF). Utbytte : 60%. 5(S) dimethylN,N" diphenylphosphino (+) piperazine / a7 D = 78 (c = 1, THF). Yield: 60%.
Ved å arbeide i henhold til eksempel 1 omsettes den således fremstilte ligand (134 • 10~^ mol) med^rodium (I)^- diklcxotetra-,kjLsj|tyJLej^(6^^ dette katalytiske kompleks, anvendes c ved hydrogenering av alfa-acetamidokanelsyre (13 • 10~^ mol) ved 2 5°C og imder at mo sfæ retryKk^^ N^ a.cetyl ,(Sj_fÆnylj-ajLani n oppnås By working according to example 1, the thus prepared ligand (134 • 10~^ mol) is reacted with ^rhodium (I)^- diklcxotetra-,kjLsj|tyJLej^(6^^ this catalytic complex is used c in the hydrogenation of alpha -acetamidocinnamic acid (13 • 10~^ mol) at 2 5°C and while mo sfæ retryKk^^ N^ a.cetyl ,(Sj_fÆnylj-ajLani n is obtained
på_de nne måte med et utbytte på 80-85%, / oc7 ^ - + 0, 5 (c = l, EtOH 95%). Optig^e nhet : 1%. ~~~~-«-— in the same way with a yield of 80-85%, / oc7 ^ - + 0.5 (c = 1, EtOH 95%). Optimum unit: 1%. ~~~~-«-—
Eksempel 4.Example 4.
Det katalytiske kompleks fremstillet i henhold til fremgangsmåten i eksempel 1, ved å gå ut fra 47,9 mg rodium (I) ^i-diklorotetra-kiscykloten (66,8<*>IO"<6>mol) og "86 mg N-N' (S(-) metylbenzyl) N-N<*>(difenylfosfino) etylen-diamin (135 • 10" —6 mol) anvendes The catalytic complex prepared according to the procedure in Example 1, starting from 47.9 mg of rhodium (I) ^i-dichlorotetrakiscyclotone (66.8<*>IO"<6>mol) and "86 mg of N-N (S(-) methylbenzyl) N-N<*>(diphenylphosphino)ethylenediamine (135 • 10" -6 mol) is used
ved den kctalytiske hydrogenering av 3-acetoksy 4-metoksy alfa-acetamidokanelsyre (2g) under a tmos f æretrykk ved 25°C. Ved å arbeide _sorn beskr evet i eksem pel.!, isoleres 3- acetoksy 4-metoksy N-acety]^Rj_j^ejiyJL.alam på^ 85-90%, /«7<22>= -16,9 (c = 1, aceton). by the catalytic hydrogenation of 3-acetoxy 4-methoxy alpha-acetamidocinnamic acid (2g) under atmospheric pressure at 25°C. By working as described in the example, 3-acetoxy 4-methoxy N-acety]^Rj_j^ejiyJL.alam is isolated at^ 85-90%, /«7<22>= -16.9 (c = 1, acetone).
Det optiske utbyjbte^ er 77%, og det enantiomete rene 3-acetoksy 4-metoksy N-acetyl (R) f enyl-alanin har /op ^<2>-22 c The optical yield is 77%, and the enantiometrically pure 3-acetoxy 4-methoxy N-acetyl (R)phenylalanine has /op ^<2>-22 c
aceton)..acetone)..
Eksempel 5.Example 5.
1-fenyl,2,5 S(-) alfa-metylbenzyl, 1-fosfa-2,5-azacyklopentan fremstilles ved å omsette N-N(S(-)-alfametylbenzyl) etylendiamin med fenyl-diklorofosfin i nærvær av trietylamin. 380 • 10~^ mol av forbindelsen omsettes med 95 • 10~ —6 mol rodium (I)^i-dikloro-tetrakis"(etylen) ( P/Rh =2). 1-Phenyl,2,5 S(-)alpha-methylbenzyl,1-phospha-2,5-azacyclopentane is prepared by reacting N-N(S(-)-alphamethylbenzyl)ethylenediamine with phenyl-dichlorophosphine in the presence of triethylamine. 380 • 10~^ mol of the compound is reacted with 95 • 10~ —6 mol of rhodium (I)^i-dichloro-tetrakis"(ethylene) ( P/Rh =2).
Ved å gå frem i samsvar med eksempel 3 anvendes ka ta lysatoren ved hydrogenering av acetaminoakrylsyre, under 15 atmosfærer hydrogen og ved romtemperatur. By proceeding in accordance with example 3, the ka ta lysator is used for the hydrogenation of acetaminoacrylic acid, under 15 atmospheres of hydrogen and at room temperature.
Det enantiomere rene N-acetyl S(-)-alanin oppnås med et utbytte på 85-90% og har /a/ 25 = -5 ( c = 1, H20). The enantiomerically pure N-acetyl S(-)-alanine is obtained with a yield of 85-90% and has /a/ 25 = -5 ( c = 1, H 2 O).
"s-°>c^t=—~ ~ ' • • —- -> "s-°>c^t=—~ ~ ' • • —- ->
Optisk utbytte^: 7,5Optical yield^: 7.5
25 25
Det enantiomere rene N-acetyl R(-)-alanin har /a7 D = rr66;>5The enantiomerically pure N-acetyl R(-)-alanine has /a7 D = rr66;>5
( c = 2, H20). ~~ ——____—_—_(c = 2, H 2 O). ~~ ——____—_—_
Eksempel 6.Example 6.
Det katalytiske kompleks fremstillet i henhold til eksempel 1,The catalytic complex prepared according to Example 1,
ved å gå ut fra rodium (I)^i-diklorotetrakis (éylen) (73 * 10~—6starting from rhodium (I)^i-dichlorotetrakis (éylene) (73 * 10~—6
mol) og N,N' (S(-)-alfa-metylbenzyi) N,N<*>(difenylfosfin) etylen-diamin (146 • 10~ —6 mol) anvendes ved katalytisk hydrogenering av 3,4 metylendioksy, alfa-acetamidokanelsyre (6,98 • 10 _3 mol) mol) and N,N' (S(-)-alpha-methylbenzyi) N,N<*>(diphenylphosphine) ethylene-diamine (146 • 10~ —6 mol) are used in the catalytic hydrogenation of 3,4 methylenedioxy, alpha- acetamidocinnamic acid (6.98 • 10 _3 mol)
ved 25°C og under atmosfæretrykk.at 25°C and under atmospheric pressure.
Ved å arbeide som beskrevet i eksempel 1, isoleres 3,4 metylendioksy, N-acetyl (R) fenyl-alanin med kvantitativt utbytte. By working as described in example 1, 3,4 methylenedioxy, N-acetyl (R) phenylalanine is isolated with quantitative yield.
//«7 ^ 8 ="40 ('c = 1/8, EtOH 95%). Optisk utbytte : 75%. N //«7 ^ 8 ="40 ('c = 1/8, EtOH 95%). Optical yield : 75%. N
Det enanjy^merjur ene-S.^^me^ylendipksy/ N-a ce ty 1 (R) f enyl-alanin ^har^a7 *8 = -53,4 ( c = 1,8, EtOH 95%). The enanjy^merjur ene-S.^^me^ylendipksy/ N-a ce ty 1 (R) f enyl-alanine ^har^a7 *8 = -53.4 ( c = 1.8, EtOH 95%).
Eksempel 7.Example 7.
Det katalytiske kompleks fremstillet i henhold til fremgangsmåten i eksempel 1, ved å gå ut fra rodium (I) ^i-diklorotetrakis (cyklookten) (13,9 • IO"<6>mol) og N,N<1>(S.(-)-alfa-metylbenzyl) N,N• (difenyl-fosfino) etylendaiamin (27,5 -10 mol) anvendes ^"Ved den katalytiske hydrogenering ved 25°Cag under atmosfære trykk av alfa-acetamidoakrylsyre"(15,5 . 10~<3>mol). The catalytic complex prepared according to the procedure in example 1, starting from rhodium (I) ^i-dichlorotetrakis (cyclooctene) (13.9 • IO"<6>mol) and N,N<1>(S. (-)-alpha-methylbenzyl) N,N• (diphenyl-phosphino) ethylenediamine (27.5 -10 mol) is used ^"In the catalytic hydrogenation at 25°Cag under atmospheric pressure of alpha-acetamidoacrylic acid"(15.5 . 10~<3>mol).
Det N-acetyl (R)-alanin som isoleres med kvantitativt utbytte har /a7 £5 = 48,5. Optisk utbytte : 73%. The N-acetyl (R)-alanine that is isolated in quantitative yield has /a7 £5 = 48.5. Optical yield: 73%.
Eksempel 8.Example 8.
Det katalytiske kompleks fremstillet som beskrevet i eksempel 1, ved å gå ut fra rodium (I)^i-diklorotetrakis (cyklookten) The catalytic complex prepared as described in example 1, starting from rhodium (I)^i-dichlorotetrakis (cyclooctene)
(146 • 10~<6>mol) og N,N<«>(S(-)-alfametylbenzyl)N,N• (difenyl-fosf ino) etylendiamin (278 • IO<-6>mol), anvendes ved den /^katalytiske hydrogenering av metylesterenav alfa-acetamidokanel^-—3 / syre (13,7 • 10 mol). R(-) N-acetylfenyl^alaninmetylesteren, — 25 I som isoleres ved kromatograf er ing på silikagel, har /cc7 D<=>-10 (c = 1,9, MeOH). (146 • 10~<6>mol) and N,N<«>(S(-)-alphamethylbenzyl)N,N• (diphenyl-phosphino)ethylenediamine (278 • IO<-6>mol), are used in the /^catalytic hydrogenation of the methyl ester of alpha-acetamidocinnamic^-—3 / acid (13.7 • 10 mol). The R(-) N-acetylphenyl^alanine methyl ester, — 25 I which is isolated by chromatograph is ing on silica gel, has /cc7 D<=>-10 (c = 1.9, MeOH).
Optisk utbytte : 46,5% Optical yield: 46.5%
Den enantiomere rene S(-) N-acetylfenyl-alaninmetylester har<25>%+21,4 c 1,9, MeOH). The enantiomerically pure S(-) N-acetylphenyl-alanine methyl ester has<25>%+21.4 c 1.9, MeOH).
Eksempel 9.Example 9.
Det katalytiske kompleks som fremstillet i henhold til fremgangsmåten beskrevet i eksempel 1, ved å gå ut fra rodium (I) yu-diklorotetrakis (etylen) 77 •10 mol) og N,N• (S(-) alfametylbenzyl) N,N<1>(difenylfosfino) etylendiamin (154 • 10~<6>mol), anvendes ved den katalytiske hydrogenering av propan-2,3-dikarboksylsyre (15 • 10~<3>mol) ved 15,5 atmosfærer og 30°C. The catalytic complex prepared according to the method described in example 1, starting from rhodium (I) yu-dichlorotetrakis (ethylene) 77 •10 mol) and N,N• (S(-) alphamethylbenzyl) N,N< 1>(diphenylphosphino)ethylenediamine (154 • 10~<6>mol), is used in the catalytic hydrogenation of propane-2,3-dicarboxylic acid (15 • 10~<3>mol) at 15.5 atmospheres and 30°C.
r Propan 2,3-dikarboksylsyren (R) isolert med kvantitativt utbytte,] /a7 q<5>= 2* 1, 5 ( c = 1, H20). Optis k utbytte : 10%. j r The propane 2,3-dicarboxylic acid (R) isolated in quantitative yield,] /a7 q<5>= 2* 1, 5 ( c = 1, H2O). Optical yield: 10%. j
Eksempel 10.Example 10.
Det katalytiske kompleks som fremstillet i henhold til fremgangsmåten beskrevet i eksempel 1, ved å gå ut fra rodium (I) u-diklorotetrakis (etylen) (72 • IO"<6>mol) og N,N'(S(-) alfa-metylbenzyl N, N1 (difenylfosfino)etylendiamin (146 • 10 mol) The catalytic complex prepared according to the procedure described in Example 1, starting from rhodium (I) u-dichlorotetrakis(ethylene) (72 • 10"<6>mol) and N,N'(S(-) alpha -methylbenzyl N, N1 (diphenylphosphino)ethylenediamine (146 • 10 mol)
anvendes ved den katalytiske hydrogenering av alfa-metylkanelsyre I^^ B^^^ S^ S^^^ S^^^' 2-benzylpropionsyren (S) kvantitativt used in the catalytic hydrogenation of alpha-methylcinnamic acid I^^ B^^^ S^ S^^^ S^^^' 2-benzylpropionic acid (S) quantitatively
gj envunnet i he2jhoj.d„tilMfr.emgangsmåten^beskrøyet 1,gj enwonnet in he2jhoj.d„tilMfr.emgangsmoden^deskrøyet 1,
har / a7 c benzen). has / a7 c benzene).
Optisk utbytte : 4%.</>Optical yield : 4%.</>
Eksempel 11.Example 11.
7 ml vannfri metanol og 5 g acetofenon innfores i en autoklav under nitrogenatmosfære. En losning av 2 ml benzen inneholdende 18,7 mg rodiumkloro-norbornadien /RhClNBD72dimer<q>g 56,3 mg N-N<1>bis (S(-)alfa-metylbenzyl)-N-N' (difenylfosfino) etylendiamin (PNNP) tilsettes så. Etter at det er opprettet vakuumbetingelser fylles autoklaven med H2ved trykk 12 atmosfærer. Etter 12 timer ved romtemperatur var 4 atmosfærer hydrogen absorbert med en omdannelse på omtrent 80%. R^ ksjoneji__aybrytes på_dejfcbe^j;4gBa&kt. Benzen_og^metaho 1 fjernes unde r redusert trykk og deretter gjenvinnes ved fraksjonert vakuumdestillasjon 3,9 g av et produkt som etters pektroskopisk analyse (NMR), består av R(+)l-metyl-fenyl-karbinol /a/ D 47, ,4 regj^pjrodu kt). Optisk renhet : 17% 7 ml of anhydrous methanol and 5 g of acetophenone are introduced into an autoclave under a nitrogen atmosphere. A solution of 2 ml of benzene containing 18.7 mg of rhodium chloro-norbornadiene /RhClNBD72dimer<q>g 56.3 mg of N-N<1>bis (S(-)alpha-methylbenzyl)-N-N' (diphenylphosphino)ethylenediamine (PNNP) is then added . After vacuum conditions have been created, the autoclave is filled with H2 at a pressure of 12 atmospheres. After 12 hours at room temperature, 4 atmospheres of hydrogen had been absorbed with a conversion of approximately 80%. R^ ksionji__aybrytes on_dejfcbe^j;4gBa&kt. Benzene_and^metaho 1 is removed under reduced pressure and then recovered by fractional vacuum distillation 3.9 g of a product which, according to spectroscopic analysis (NMR), consists of R(+)l-methyl-phenyl-carbinol /a/ D 47, , 4 regj^pjrodu kt). Optical purity : 17%
(/a7 1° = +44,2)':" — ' (/a7 1° = +44.2)':" — '
Eksempel 12.Example 12.
Katalysatoren fremstillet fra 45 mg /R^C1NBD72 og 124 mg (PNNP)The catalyst prepared from 45 mg /R^C1NBD72 and 124 mg (PNNP)
i 3 ml benzen. En slik katalytisk losning innfores i en autoklav inneholdende 5 g cykloheksylmetylketon i 7 ml metanol. Autoklaven bringes til 12 atmosfærers trykk med hydrogen. Etter 48 timer ved romtemperatur var omtrent 3 atmosfærer H2absorbert. Reaksjonen avbrytes. Med en fremgangsmåte tilsvarende den i eksempel 1 ble det gjenvunnet 3,15 g av et produkt som er in 3 ml of benzene. Such a catalytic solution is introduced into an autoclave containing 5 g of cyclohexyl methyl ketone in 7 ml of methanol. The autoclave is brought to 12 atmospheres pressure with hydrogen. After 48 hours at room temperature, about 3 atmospheres of H2 had been absorbed. The reaction is interrupted. With a method similar to that in example 1, 3.15 g of a product which is recovered
Claims (12)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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IT2265376A IT1063212B (en) | 1976-04-26 | 1976-04-26 | Asymmetric hydrogenation of olefins, carbonyl cpds. or nitriles - using transition metal complex of asymmetric amino-phosphine |
IT2013977A IT1113753B (en) | 1977-02-10 | 1977-02-10 | Asymmetric hydrogenation of olefins, carbonyl cpds. or nitriles - using transition metal complex of asymmetric amino-phosphine |
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NO771419L true NO771419L (en) | 1977-10-27 |
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NO771419A NO771419L (en) | 1976-04-26 | 1977-04-25 | NEW AMINOPHOSPHINES AND PROCEDURES FOR THEIR PREPARATION |
NO773738A NO773738L (en) | 1976-04-26 | 1977-10-31 | PROCEDURES FOR ASYMMETRIC HYDROGENATION |
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NO773738A NO773738L (en) | 1976-04-26 | 1977-10-31 | PROCEDURES FOR ASYMMETRIC HYDROGENATION |
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JP (1) | JPS52151127A (en) |
AU (2) | AU523259B2 (en) |
CA (1) | CA1109074A (en) |
CH (1) | CH629166A5 (en) |
DD (2) | DD132487A5 (en) |
DE (3) | DE2759684C2 (en) |
DK (1) | DK180877A (en) |
FR (1) | FR2349555A1 (en) |
GB (1) | GB1580461A (en) |
HU (2) | HUT33991A (en) |
LU (1) | LU77197A1 (en) |
NL (1) | NL180096C (en) |
NO (2) | NO771419L (en) |
SE (2) | SE434918B (en) |
YU (1) | YU107577A (en) |
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IT1087963B (en) * | 1977-10-17 | 1985-06-04 | Snam Progetti | ASYMMETRICAL HYDROGENATION OF PROCHIRAL OLEFINS BY COMPLEX OF TRANSITION METALS IMMOBILIZED IN CLAY MINERALS. |
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-
1977
- 1977-04-06 CA CA275,775A patent/CA1109074A/en not_active Expired
- 1977-04-19 AU AU24407/77A patent/AU523259B2/en not_active Ceased
- 1977-04-21 GB GB16691/77A patent/GB1580461A/en not_active Expired
- 1977-04-22 DD DD7700198557A patent/DD132487A5/en unknown
- 1977-04-22 CH CH503677A patent/CH629166A5/en not_active IP Right Cessation
- 1977-04-22 DD DD77206208A patent/DD137233A5/en unknown
- 1977-04-25 FR FR7712435A patent/FR2349555A1/en active Granted
- 1977-04-25 HU HU82465A patent/HUT33991A/en unknown
- 1977-04-25 DK DK180877A patent/DK180877A/en not_active Application Discontinuation
- 1977-04-25 LU LU77197A patent/LU77197A1/xx unknown
- 1977-04-25 SE SE7704738A patent/SE434918B/en not_active IP Right Cessation
- 1977-04-25 YU YU01075/77A patent/YU107577A/en unknown
- 1977-04-25 NO NO771419A patent/NO771419L/en unknown
- 1977-04-25 HU HU82466A patent/HUT34037A/en unknown
- 1977-04-26 DE DE2759684A patent/DE2759684C2/en not_active Expired
- 1977-04-26 NL NLAANVRAGE7704570,A patent/NL180096C/en not_active IP Right Cessation
- 1977-04-26 DE DE2718533A patent/DE2718533C3/en not_active Expired
- 1977-04-26 DE DE2759683A patent/DE2759683C3/en not_active Expired
- 1977-04-26 JP JP4750177A patent/JPS52151127A/en active Granted
- 1977-10-31 NO NO773738A patent/NO773738L/en unknown
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1983
- 1983-09-09 SE SE8304837A patent/SE460066B/en not_active IP Right Cessation
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1984
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Also Published As
Publication number | Publication date |
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CH629166A5 (en) | 1982-04-15 |
DD132487A5 (en) | 1978-10-04 |
DE2759683B1 (en) | 1980-07-17 |
LU77197A1 (en) | 1977-08-17 |
DE2718533B2 (en) | 1979-12-20 |
AU572169B2 (en) | 1988-05-05 |
NL180096C (en) | 1987-01-02 |
SE460066B (en) | 1989-09-04 |
NO773738L (en) | 1977-10-27 |
SE434918B (en) | 1984-08-27 |
SE7704738L (en) | 1977-10-27 |
DE2718533C3 (en) | 1980-08-28 |
DD137233A5 (en) | 1979-08-22 |
HUT33991A (en) | 1985-01-28 |
CA1109074A (en) | 1981-09-15 |
FR2349555B1 (en) | 1980-12-26 |
YU107577A (en) | 1983-02-28 |
JPS633871B2 (en) | 1988-01-26 |
DK180877A (en) | 1977-10-27 |
AU2440777A (en) | 1979-03-08 |
DE2718533A1 (en) | 1977-11-24 |
JPS52151127A (en) | 1977-12-15 |
AU3054684A (en) | 1984-12-20 |
DE2759683C3 (en) | 1981-10-15 |
HUT34037A (en) | 1985-01-28 |
DE2759684C2 (en) | 1986-05-28 |
SE8304837L (en) | 1983-09-09 |
AU523259B2 (en) | 1982-07-22 |
SE8304837D0 (en) | 1983-09-09 |
NL7704570A (en) | 1977-10-28 |
NL180096B (en) | 1986-08-01 |
GB1580461A (en) | 1980-12-03 |
FR2349555A1 (en) | 1977-11-25 |
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