FR2609712A1 - L-amino acids prepn. - from precursor mixt. of keto acid, maleic acid, and ammonia - Google Patents
L-amino acids prepn. - from precursor mixt. of keto acid, maleic acid, and ammonia Download PDFInfo
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- FR2609712A1 FR2609712A1 FR8700460A FR8700460A FR2609712A1 FR 2609712 A1 FR2609712 A1 FR 2609712A1 FR 8700460 A FR8700460 A FR 8700460A FR 8700460 A FR8700460 A FR 8700460A FR 2609712 A1 FR2609712 A1 FR 2609712A1
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- 239000002243 precursor Substances 0.000 title claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title abstract 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title abstract 2
- 229910021529 ammonia Inorganic materials 0.000 title abstract 2
- 150000004715 keto acids Chemical class 0.000 title abstract 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 title abstract 2
- 239000011976 maleic acid Substances 0.000 title abstract 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title abstract 2
- 150000008575 L-amino acids Chemical class 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkaline-earth Substances 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 150000005352 hydroxybiphenyls Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 4
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 claims description 3
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 150000001649 bromium compounds Chemical class 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000002222 fluorine compounds Chemical group 0.000 claims 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims 1
- 150000002898 organic sulfur compounds Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 150000001413 amino acids Chemical class 0.000 abstract 2
- 102000003929 Transaminases Human genes 0.000 abstract 1
- 108090000340 Transaminases Proteins 0.000 abstract 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000005891 transamination reaction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
- 229940112669 cuprous oxide Drugs 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000005297 pyrex Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- KQLZDIKWQFUGRI-UHFFFAOYSA-N 1,5-dibromo-5-phenylcyclohexa-1,3-diene Chemical group BrC1(CC(=CC=C1)Br)C1=CC=CC=C1 KQLZDIKWQFUGRI-UHFFFAOYSA-N 0.000 description 1
- JHOPNNNTBHXSHY-UHFFFAOYSA-N 2-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1O JHOPNNNTBHXSHY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VZHUBBUZNIULNM-UHFFFAOYSA-N Cyclohexyl butanoate Chemical compound CCCC(=O)OC1CCCCC1 VZHUBBUZNIULNM-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- UBXYXCRCOKCZIT-UHFFFAOYSA-N biphenyl-3-ol Chemical group OC1=CC=CC(C=2C=CC=CC=2)=C1 UBXYXCRCOKCZIT-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/04—Alpha- or beta- amino acids
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
Description
PROCèDE DE PREPARÂTION D'HYROXYBIPHENYLES
La présente invention concerne un procedé de fabrication d' hydroxybiphényles. Elle concerne plus particulièrement un procédé de préparation de dihydroxy-4, 4' biphényle. PROCESS FOR THE PREPARATION OF HYROXYBIPHENYLS
The present invention relates to a process for producing hydroxybiphenyls. It relates more particularly to a process for the preparation of 4,4'-dihydroxybiphenyl.
En effet le dihydroxy-4,4'biphényle est un intermédiaire recherché actuellement dans l'industrie des matériaux synthétiques tels que les polyesters, les polyépoxides, les polyuréthanes, comme antioxydant dans les résines ou dans l'industrie des matières colorantes. Indeed 4,4'-dihydroxybiphenyl is an intermediate currently sought in the industry of synthetic materials such as polyesters, polyepoxides, polyurethanes, as an antioxidant in resins or in the dyestuffs industry.
Il est connu de préparer les hydroxybiphényles par hydrolyse des halogènobiphényles à l'aide d'une catalyse au cuivre, telle que par exemple a l'aide de sulfate de cuivre (selon le brevet US 4 475 500) ou a l'aide d'oxyde de cuivre (selon le brevet US 4 340 748) en milieu basique aqueux. Les conditions de température et la pression autogène créée par des températures aussi élevées ainsi que la faible quantité de ratière première traitée à chaque opération ont incité l'homme de l'art a chercher une technique moins dangeureuse et surtout plus rentable. It is known to prepare the hydroxybiphenyls by hydrolysis of the halogenobiphenyls by means of a copper catalysis, such as, for example, with the aid of copper sulphate (according to US Pat. No. 4,475,500) or with the aid of copper oxide (according to US Pat. No. 4,340,748) in aqueous basic medium. The temperature conditions and the autogenous pressure created by such high temperatures as well as the small amount of dobby treated at each operation have prompted those skilled in the art to seek a less dangerous and above all more profitable.
Il est encore connu de nombreux procédés de préparation de composés hydroxyaryliques réalisés en phase vapeur, c'est à dire a une température supérieure a 3000C en présence de catalyseur a base de cuivre et d'un catalyseur a base de phosphates de terres rares. Il est ainsi décrit dans le brevet US 3 752 878 un procédé de préparation de composés hydroxyaryliques dont le groupe aryle contient un ou plusieurs noyaux benzèniques à partir de composés équivalents halogénés par hydrolyse en présence d'un catalyseur à base de phosphate de lanthane ou de cerium et de cuivre qui sont précipités conjointement sous forme de polyphosphate minéral. Cette réaction est réalisée sous forme biphasique.Le catalyseur se trouvant sous forme solide et le composé halogèné à hydrolyser sous forme gazeuse car la réaction est effectuée à 5000C. Le taux de conversion du composé de départ est faible et les conditions de réaction sont trop sévères pour être utilisables a l'échelle industrielle. Numerous processes are still known for the preparation of hydroxyaryl compounds produced in the vapor phase, that is to say at a temperature above 3000 ° C. in the presence of a copper-based catalyst and a rare earth phosphate catalyst. Thus, US Pat. No. 3,752,878 discloses a process for the preparation of hydroxyaryl compounds wherein the aryl group contains one or more benzene rings from equivalent halogenated compounds by hydrolysis in the presence of a lanthanum phosphate or cerium and copper which are precipitated together in the form of mineral polyphosphate. This reaction is carried out in biphasic form. The catalyst is in solid form and the halogenated compound to be hydrolyzed in gaseous form because the reaction is carried out at 5000 ° C. The conversion rate of the starting compound is low and the reaction conditions are too severe to be usable on an industrial scale.
Lorsque l'on désire réaliser l'hydrolyse å une température moins élevée, telle que par exemple selon le brevet japonais 69/17372 ou l'hydrolyse est réalisée é environ 2000C, en présence de dérivés du cuivre a l'état d'oxydation deux, comme le sulfate de cuivre, le dibromure de cuivre, le diacétate de cuivre ; la durée de la réaction d'hydrolyse est particulièrement longue et atteint parfois 10 heures pour un rendement ne dépassant pas 25 %. Cette méthode n'est donc pas transférable au niveau industriel. When it is desired to carry out the hydrolysis at a lower temperature, as for example according to Japanese Patent 69/17372 or the hydrolysis is carried out at about 2000C, in the presence of copper derivatives in the oxidation state two such as copper sulphate, copper dibromide, copper diacetate; the duration of the hydrolysis reaction is particularly long and sometimes reaches 10 hours for a yield not exceeding 25%. This method is therefore not transferable at the industrial level.
Ainsi depuis de nombreuses années l'industrie est à la recherche d'un procédé de préparation d'hydroxybiphényles économiquement rentable, non dangeureux à partir d'halogénobiphényles. For many years, the industry has been seeking a process for the preparation of economically profitable, non-hazardous hydroxybiphenyls from halobiphenyls.
La présente invention a permis d'atteindre cet objectif et a pour objet un procédé industriel de préparation d'hydroxybiphényles caractérisé par le fait que l'on met en présence en phase liquide aqueuse à une température inférieure å 3000C un bromobiphényle de formule générale (I)
dans laquelle m et n sont des nombres entiers identiques ou différents, égal å 0,1, 2 ou 3 et dont la somme n+m est supérieure ou égale à 1 et inférieure ou égale à 4, avec une base de formule M(OH) dans laquelle M
p est un métal choisi parmi les métaux alcalins ou alcalino-terreux, p est un nombre entier égal à 1 ou 2 suivant la valence du M, en présence d'un catalyseur à base de cuivre et d'un co-catalyseur choisi parmi les halogénures (fluorures, bromures), les phosphates, les nitrates, les alcoolates alcalins ou alcalinoterreux, de cuivre ou d'argent, les silicates minéraux ou organiques ainsi que leurs précurseurs, les dérivés soufrés organiques et l'oxyde de carbone ou un de ses précurseurs. Les dérivés bromés sont préparés de manière connue par tout homme de l'art par action du brome sur un biphényle & température ambiante pendant quelques heures. La variation de température, de durée, le choix du solvant et le cboix de certains catalyseurs de bromation permettent de fixer un ou plusieurs atomes de brome. The present invention has made it possible to achieve this objective and relates to an industrial process for the preparation of hydroxybiphenyls, characterized in that a bromobiphenyl of general formula (I) is placed in the aqueous liquid phase at a temperature below 3000C. )
in which m and n are identical or different integers, equal to 0.1, 2 or 3 and whose sum n + m is greater than or equal to 1 and less than or equal to 4, with a base of formula M (OH ) in which M
p is a metal selected from alkali or alkaline earth metals, p is an integer equal to 1 or 2 depending on the valence of M, in the presence of a copper-based catalyst and a co-catalyst selected from the group consisting of halides (fluorides, bromides), phosphates, nitrates, alkali or alkaline earth metal alkoxides, copper or silver, inorganic or organic silicates and their precursors, organic sulfur derivatives and carbon monoxide or one of its precursors. The brominated derivatives are prepared in a manner known to those skilled in the art by the action of bromine on a biphenyl at room temperature for a few hours. The variation of temperature, of duration, the choice of the solvent and the coxix of certain bromination catalysts make it possible to fix one or more bromine atoms.
Parmi les dérivés de formule générale (I), on préfère les dérivés dans lesquels n+m est égal & 1 ou 2 et encore plus préférentiellement ceux pour lesquels n+m est égal å 2 et tout particulièrement le dibromo-4,4'biphényle. Among the derivatives of general formula (I), the derivatives in which n + m is equal to 1 or 2 and even more preferably those for which n + m is equal to 2 and especially 4,4'-dibromo biphenyl are preferred. .
Parmi les bases de formule N(OH) , on préfère utiliser les p bases fortes alcalines et tout particulièrement la soude ou la potasse. Among the bases of formula N (OH), it is preferred to use strong alkaline bases and especially soda or potassium hydroxide.
Parmi les catalyseurs a base de cuivre, on peut citer non limitativement le cuivre métallique, le cuivre a l'état d'oxydation un tel que l'oxyde cuivreux, les halogénures, acétate, cyanure, thiocyanate, triflate, sulfure cuivreux, ainsi. que les dérivés du cuivre à l'état d'oxydation deux tels que l'oxyde, les halogénures, acétates, acétylacétonates, métaborate, isobutyrate, citrate, cyclohexylbutyrate, diméthyldithiocarbamate, hexanoate, gluconate, hydroxyde, oxalate, propionate, stéarate, sulfate, trifluoroacétylacétonate cuivriques. Copper-based catalysts include, but are not limited to, copper metal, copper in the oxidation state such as cuprous oxide, halides, acetate, cyanide, thiocyanate, triflate, cuprous sulfide, as well. that two oxidation state copper derivatives such as oxide, halides, acetates, acetylacetonates, metaborate, isobutyrate, citrate, cyclohexylbutyrate, dimethyldithiocarbamate, hexanoate, gluconate, hydroxide, oxalate, propionate, stearate, sulfate, cupric trifluoroacetylacetonate.
On préfère cependant utiliser les oxydes ou halogénures de cuivre å l'état d'oxydation un ou deux. It is preferred, however, to use the oxides or halides of copper in the oxidation state one or two.
Parmi les co-catalyseurs permettant de réduire soit la température, soit la durée de la réaction et objet de la protection demandée pour la présente invention, on peut choisir les halogénures, les phosphates, les nitrates, les silicates, l'ensemble de ces composés sont pour leur mise en oeuvre associés à des protons ou & des cations alcalins, alcalino-terreux, métalliques par exemple de cuivre, d'argent ou organiques. Les silicates peuvent aussi être préparés in-situ dans le milieu réactionnel par action par exemple de la base forte sur de la silice ou du verre. Les phosphates peuvent également etre préparés in-situ & partir de phosphates organiques. Among the cocatalysts which make it possible to reduce either the temperature or the duration of the reaction and the object of the protection required for the present invention, it is possible to choose the halides, the phosphates, the nitrates, the silicates, all of these compounds. are for their implementation associated with protons or cations alkaline, alkaline earth metal, for example copper, silver or organic. The silicates can also be prepared in situ in the reaction medium by action, for example, of the strong base on silica or glass. Phosphates can also be prepared in situ from organic phosphates.
Parmi les co-catalyseurs entièrement organiques on peut également citer par exemple les alcoolates et les alcools contenant de préférence 1 a 12 atomes de carbone, les acides carboxyliques contenant 2 & 12 atomes de carbone, les dérivés soufrés ainsi que l'oxyde de carbone ou un de ses précurseurs organiques tels que les formiates. Among the fully organic cocatalysts, mention may also be made, for example, of alcoholates and alcohols containing preferably 1 to 12 carbon atoms, carboxylic acids containing 2 to 12 carbon atoms, sulfur derivatives and carbon monoxide or one of its organic precursors such as formates.
Ainsi, on peut citer pour exemplifier les co-catalyseurs de la présente invention, le diphénylsulfure, le dithiophène, le fluorure de potassium et/ou de sodium, l'acide phosphorique, l'acide nitrique, le méthylate de sodium, le formiate de méthyle, les verres, par exemple le
Pyrex, la silice...... Thus, exemplary co-catalysts of the present invention include diphenylsulfide, dithiophene, potassium fluoride and / or sodium, phosphoric acid, nitric acid, sodium methoxide, formate methyl, glasses, for example the
Pyrex, silica ......
On préfère utiliser les fluorures, les bromures, les phosphates, les nitrates, les silicates alcalins ou les formiates organiques. It is preferred to use fluorides, bromides, phosphates, nitrates, alkali silicates or organic formates.
Il est évident que lorque le catalyseur à base de cuivre et le co-catalyseur forment une seule entité chimique, cette dernière sera utilisée et jouera l'ensemble des deux rôles. It is obvious that when the copper catalyst and the cocatalyst form a single chemical entity, the latter will be used and will play both roles.
Parmi les conditions réactionnelles, la température est une condition essentielle du point de vue économique et elle fait l'objet du présent procédé, elle est limitée å 3000C et de préférence comprise entre 220 et 250 C. La pression utilisée est la pression autogene obtenue a la température de réaction par vaporisation des composés présents, elle peut étre accrue par tout solvant inerte tel que l'azote ou tout gaz non réactif avec les composés réactionnels. La réaction ayant lieu en milieu aqueux, on utilise de préférence un mono ou polybromobiphényle & une concentration supérieure å 0,15 mole par litre d'eau et de préférence comprise entre 0,15 et 2 moles par litre d'eau. Among the reaction conditions, the temperature is an essential condition from the economic point of view and is the subject of the present process, it is limited to 3000C and preferably between 220 and 250 C. The pressure used is the autogenous pressure obtained a the vaporization reaction temperature of the compounds present may be increased by any inert solvent such as nitrogen or any gas unreactive with the reaction compounds. Since the reaction takes place in an aqueous medium, a mono or polybromobiphenyl is preferably used at a concentration greater than 0.15 mole per liter of water and preferably between 0.15 and 2 moles per liter of water.
On utilise de préférence une quantité de base de formule M(OH) libérant p au moins 2 équivalents d'hydroxyle par atome de brome & hydrolyser et présentant une concentration dans l'eau comprise entre un équivalent molaire par litre et dix équivalent molaire par litre.A base amount of formula M (OH) liberating p at least 2 equivalents of hydroxyl per atom of bromine is preferably used for hydrolysis and has a concentration in water of between one molar equivalent per liter and ten molar equivalents per liter. .
La quantité pondérale de catalyseur à base de cuivre est de préférence comprise entre 0,2 t et 5 t par rapport à la quantité du bromobiphényle introduite. The amount by weight of copper-based catalyst is preferably between 0.2 and 5 t relative to the amount of bromobiphenyl introduced.
La quantité molaire de co-catalyseur est de préférence comprise entre 0,1 et 100 fois la quantité molaire de catalyseur. Une quantité largement excédentaire ne nuerait pas au procédé de l'invention mais cela n'apporte aucun avantage supplémentaire. La quantité utile sera simplement adaptée par l'homme de l'art å l'économie du procédé. The molar amount of cocatalyst is preferably between 0.1 and 100 times the molar amount of catalyst. A large excess quantity would not be harmful to the process of the invention, but this provides no additional benefit. The useful amount will simply be adapted by those skilled in the art to the economics of the process.
L'invention permet de préparer des bydroxybiphényles et parmi ceux-ci on peut citer ; l'hydroxy-4 biphényle, l'hydroxy-2 biphényle, l'hydroxy-3 biphényle, le dihydroxy-4,4'biphényle, le dihydroxy-2,2'biphényle, le dihydroxy-2,4'biphényle, le trihydroxy-2,4,4'biphényle, les tétrahydroxybiphényles. The invention makes it possible to prepare bydroxybiphenyls and among these can be mentioned; 4-hydroxy-biphenyl, 2-hydroxy-biphenyl, 3-hydroxy-biphenyl, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, trihydroxy -2,4,4'biphenyl, tetrahydroxybiphenyls.
L'invention sera plus complètement décrite à l'aide des exemples suivants qui ne doivent en aucun cas être considérés comme limitatifs de l'invention. The invention will be more fully described with the aid of the following examples which should in no way be considered as limiting the invention.
EXEMPLES 1 A 16
Mode opératoire
On introduit dans un réacteur er. Hastelloy C 276 de 7t ml les composés suivants
2 g (6,4 mmoles)
- Cu2O 10 mg (0,07 mmoles)
- NaOH 5N 20 ml (100 mmoles
- Cocatalyseur 2 moles par mole de Ou2O
ou 20 mg dans le cas du pyrex
les gaz sont introduits par purge.EXAMPLES 1 TO 16
Operating mode
We introduce into a reactor er. Hastelloy C 276 of 7t ml the following compounds
2 g (6.4 mmol)
- Cu2O 10 mg (0.07 mmol)
5N NaOH (100 mmol)
- Cocatalyst 2 moles per mole of Ou2O
or 20 mg in the case of pyrex
the gases are introduced by purge.
Après une purge à l'argon, fermeture de l'autoclave puis introduction éventuelle de co-catalyseur gazeux, l'autoclave est placé dans un four agité et porté à 250oC. Après un temps T de réaction, le réacteur est ramené à température ambiante. Le mélange réactionnel est dilué par 20 ml d'eau (ripage du réacteur), acidifié par 25 ml d'acide sulfurique 4N et extrait à la méthylisobutylcétone (1x20 ml + 5x10 ml). After purging with argon, closing the autoclave and then optionally introducing gaseous cocatalyst, the autoclave is placed in a stirred oven and heated to 250oC. After a reaction time T, the reactor is brought back to ambient temperature. The reaction mixture is diluted with 20 ml of water (shifted from the reactor), acidified with 25 ml of 4N sulfuric acid and extracted with methyl isobutyl ketone (1 × 20 ml + 5 × 10 ml).
La phase organique est séchée sur sulfate de sodium. Les rendements sont déterminés par chromatographie liquide haute performance.The organic phase is dried over sodium sulphate. The yields are determined by high performance liquid chromatography.
Tableau des résultats voir page suivante
Tableau I
Table of results see next page
Table I
N <SEP> Co-catalyseurs <SEP> Durée <SEP> RR <SEP> (%) <SEP> RR <SEP> (t) <SEP>
<tb> <SEP> 4-OH <SEP> 4,4' <SEP> diOH
<tb> <SEP> 1 <SEP> - <SEP> 3 <SEP> h <SEP> 0,4 <SEP> 52,9
<tb> <SEP> 2 <SEP> - <SEP> 5 <SEP> h <SEP> 1,5 <SEP> 85,2
<tb> <SEP> 3 <SEP> - <SEP> 7 <SEP> h <SEP> 1,3 <SEP> 90,5 <SEP>
<tb> <SEP> 4 <SEP> Ph2S <SEP> 3 <SEP> h <SEP> 0,5 <SEP> 6C,6
<tb> <SEP> 5 <SEP> dithiophène <SEP> 3 <SEP> h <SEP> 0,6 <SEP> 68,8 <SEP>
<tb> <SEP> 6 <SEP> XF <SEP> 3 <SEP> h <SEP> 1,7 <SEP> 88,8
<tb> <SEP> 7 <SEP> NaF <SEP> 3 <SEP> h <SEP> 1,4 <SEP> 93,3
<tb> <SEP> 8 <SEP> H3PO4 <SEP> 3 <SEP> h <SEP> 2,7 <SEP> 91,2
<tb> <SEP> 9 <SEP> HNO3 <SEP> 3 <SEP> h <SEP> 1,2 <SEP> 83,6
<tb> 10 <SEP> NaCN <SEP> 3 <SEP> h <SEP> 0,3 <SEP> 58,9
<tb> 11 <SEP> NaOMe <SEP> 3 <SEP> h <SEP> 4,2 <SEP> 83,0 <SEP>
<tb> 12 <SEP> NaBr <SEP> (1 <SEP> mole <SEP> par <SEP> mole <SEP> 3 <SEP> h <SEP> 1,2 <SEP> 84,5
<tb> <SEP> de <SEP> Br2 <SEP> (C6H4)2
<tb> 13 <SEP> HCO2Me <SEP> 3 <SEP> h <SEP> 1,7 <SEP> 90,4
<tb> 14 <SEP> CO <SEP> & <SEP> 6,4 <SEP> t <SEP> dans <SEP> N2 <SEP> 3 <SEP> h <SEP> 0,5 <SEP> 62,5
<tb> <SEP> 1 <SEP> purge
<tb> 15 <SEP> Pyrex <SEP> 3 <SEP> h <SEP> 1,7 <SEP> 86,9
<tb> 16 <SEP> SiO2 <SEP> 3 <SEP> h <SEP> 1,8 <SEP> 89,4
<tb>
EXEMPLE 17
On opère comme décrit â l'exemple 1, en introduisant - 2 9 de dibromo-4,4'biphényle (6,4 mmoles)
- 20 ml de NaOH 5 N (100 mmoles)
- 10 mg d'oxyde cuivreux (0,07 mmoles)
- 1,4 g de NaBr (14 mmoles)
Après 3 heures de réaction, on obtient un rendement en dihydro-4,4'biphényle de 84,7 t et un rendement en hydroxy-4 biphényle de :,2 %.N <SEP> Co-catalysts <SEP> Time <SEP> RR <SEP> (%) <SEP> RR <SEP> (t) <SEP>
<tb><SEP> 4-OH <SEP> 4,4 '<SEP> diOH
<tb><SEP> 1 <SEP> - <SEP> 3 <SEP> h <SEQ> 0.4 <SEP> 52.9
<tb><SEP> 2 <SEP> - <SEP> 5 <SEP> h <SEP> 1.5 <SEP> 85.2
<tb><SEP> 3 <SEP> - <SEP> 7 <SEP> h <SEP> 1.3 <SEP> 90.5 <SEP>
<tb><SEP> 4 <SEP> Ph2S <SEP> 3 <SEP> h <SEP> 0.5 <SEP> 6C, 6
<tb><SEP> 5 <SEP> dithiophene <SEP> 3 <SEP> h <SEP> 0.6 <SEP> 68.8 <SEP>
<tb><SEP> 6 <SEP> XF <SEP> 3 <SEP> h <SEP> 1.7 <SEP> 88.8
<tb><SEP> 7 <SEP> NaF <SEP> 3 <SEP> h <SEP> 1.4 <SEP> 93.3
<tb><SEP> 8 <SEP> H3PO4 <SEP> 3 <SEP> h <SEP> 2.7 <SEP> 91.2
<tb><SEP> 9 <SEP> HNO3 <SEP> 3 <SEP> h <SEP> 1.2 <SEP> 83.6
<tb> 10 <SEP> NaCN <SEP> 3 <SEP> h <SEP> 0.3 <SEP> 58.9
<tb> 11 <SEP> NaOMe <SEP> 3 <SEP> h <SEP> 4.2 <SEP> 83.0 <SEP>
<tb> 12 <SEP> NaBr <SEP> (1 <SEP> mole <SEP> with <SEP> mole <SEP> 3 <SEP> h <SEP> 1.2 <SEP> 84.5
<tb><SEP> of <SEP> Br2 <SEP> (C6H4) 2
<tb> 13 <SEP> HCO2Me <SEP> 3 <SEP> h <SEP> 1.7 <SEP> 90.4
<tb> 14 <SEP> CO <SEP>&<SEP> 6.4 <SEP> t <SEP> in <SEP> N2 <SEP> 3 <SEP> h <SEP> 0.5 <SEP> 62.5
<tb><SEP> 1 <SEP> purge
<tb> 15 <SEP> Pyrex <SEP> 3 <SEP> h <SEP> 1.7 <SEP> 86.9
<tb> 16 <SEP> SiO2 <SEP> 3 <SEP> h <SEP> 1.8 <SEP> 89.4
<Tb>
EXAMPLE 17
The procedure is as described in Example 1, with the introduction of 2,4-dibromo-4,4'-biphenyl (6.4 mmol).
20 ml of 5 N NaOH (100 mmol)
- 10 mg of cuprous oxide (0.07 mmol)
1.4 g of NaBr (14 mmol)
After 3 hours of reaction, a yield of 4,4'-dihydro-4,4'biphenyl of 84.7 t and a yield of 4-hydroxybiphenyl of: 2% is obtained.
EXEMPLE îe
On opère comme déprit a l'exemple 1, en hydrolysant un mélange de:
- bromo-2 biphényle
- dibromo-2,4 biphényle
- dibromo-2,4' biphényle
- dibromo-2,2' biphényle
- tribromo-2,4,4' biphényle obtenu par bromation du brome2 biphényle par le brome dans le dichloromèthane en présence de 1 t de chlorure ferrique pendant 48 heures.EXAMPLE
The reaction is carried out as in Example 1, by hydrolysing a mixture of:
- 2-bromo biphenyl
- 2,4-dibromo biphenyl
- 2,4-dibromo biphenyl
- 2,2'-dibromo biphenyl
tribromo-2,4,4 'biphenyl obtained by bromination bromine biphenyl bromine in dichloromethane in the presence of 1 t ferric chloride for 48 hours.
L'hydrolyse est conduite en présence de 0,07 mole d'oxyde cuivreux et de 2 moles de silice par mole de catalyseur, å 2500C dans la soude 5N. The hydrolysis is conducted in the presence of 0.07 mole of cuprous oxide and 2 moles of silica per mole of catalyst, at 2500C in 5N sodium hydroxide.
On obtient en 3 heures un mélange de
- hydroxy-2 biphényle
- dihydroxy-2,4 biphényle
- dihydroxy-2,4' biphényle
- dihydroxy-2,2' biphényle
- trihydroxy-2,4,4' biphényle
Les produits sont identifiés par résonance magnétique nucléaire après isolement par chromatographie phase gazeuse préparative.In 3 hours, a mixture of
- 2-hydroxybiphenyl
2,4-dihydroxybiphenyl
2,4-dihydroxybiphenyl
2,2-dihydroxybiphenyl
2,4,4-trihydroxybiphenyl
The products are identified by nuclear magnetic resonance after isolation by preparative gas chromatography.
EXEMPLE 19
Les essais suivants sont réalisés dans les mémes conditions que les exemples 1 a 16 avec
- 2 g de dibromo-4,4'biphényle
- 100 mg d'oxyde cuivreux
- 20 ml de NaOH 5N à 2300C en utilisant le cas échéant comme co-catalyseur du butanol.EXAMPLE 19
The following tests are carried out under the same conditions as Examples 1 to 16 with
-2 g of 4,4'-dibromobiphenyl
- 100 mg of cuprous oxide
20 ml of 5N NaOH at 2300 ° C., optionally using as butanol cocatalyst.
Tableau 2
Table 2
N <SEP> Cocatalyseurs <SEP> Durée <SEP> RR <SEP> (%) <SEP> RR <SEP> (%)
<tb> <SEP> 4-OH <SEP> 4,4' <SEP> diOH
<tb> <SEP> 7 <SEP> - <SEP> 7 <SEP> h <SEP> 30 <SEP> traces <SEP> 69,0
<tb> <SEP> 2 <SEP> 10 <SEP> ml <SEP> BuOH <SEP> 7 <SEP> h <SEP> 30 <SEP> 1,8 <SEP> 84,0
<tb> N <SEP> Cocatalysts <SEP> Time <SEP> RR <SEP> (%) <SEP> RR <SEP> (%)
<tb><SEP> 4-OH <SEP> 4,4 '<SEP> diOH
<tb><SEP> 7 <SEP> - <SEP> 7 <SEP> h <SEP> 30 <SEP> traces <SEP> 69.0
<tb><SEP> 2 <SEP> 10 <SEP> ml <SEP> BuOH <SEP> 7 <SEP> h <SEP> 30 <SEP> 1.8 <SEP> 84.0
<Tb>
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Publication number | Priority date | Publication date | Assignee | Title |
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EP0367145A2 (en) * | 1988-10-27 | 1990-05-09 | Meiji Seika Kaisha Ltd. | New process for the production of L-2-amino-4(hydroxymethyl-phospinyl)-butyric acid |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1248130A (en) * | 1959-11-18 | 1960-12-09 | Tanabe Seiyaku Co | Manufacturing process of l-aspartic acid |
EP0135846A2 (en) * | 1983-09-01 | 1985-04-03 | Genetics Institute, Inc. | Production of L-amino acids by transamination |
JPS61202695A (en) * | 1985-03-06 | 1986-09-08 | Showa Denko Kk | Production of l-phenylalanine |
EP0152275B1 (en) * | 1984-02-07 | 1991-06-19 | THE NUTRASWEET COMPANY (a Delaware corporation) | Production of amino acids via bioconversion |
-
1987
- 1987-01-16 FR FR8700460A patent/FR2609712A1/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1248130A (en) * | 1959-11-18 | 1960-12-09 | Tanabe Seiyaku Co | Manufacturing process of l-aspartic acid |
EP0135846A2 (en) * | 1983-09-01 | 1985-04-03 | Genetics Institute, Inc. | Production of L-amino acids by transamination |
EP0152275B1 (en) * | 1984-02-07 | 1991-06-19 | THE NUTRASWEET COMPANY (a Delaware corporation) | Production of amino acids via bioconversion |
JPS61202695A (en) * | 1985-03-06 | 1986-09-08 | Showa Denko Kk | Production of l-phenylalanine |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 106, no. 17, 27 avril 1987, page 570, résumé no. 137015k, Columbus, Ohio, US; & JP-A-61 202 695 (SHOWA DENKO K.K.) 08-09-1986 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0367145A2 (en) * | 1988-10-27 | 1990-05-09 | Meiji Seika Kaisha Ltd. | New process for the production of L-2-amino-4(hydroxymethyl-phospinyl)-butyric acid |
EP0367145A3 (en) * | 1988-10-27 | 1991-10-16 | Meiji Seika Kaisha Ltd. | New process for the production of l-2-amino-4(hydroxymethyl-phospinyl)-butyric acid |
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