JP5930329B2 - 3‐(メチルチオ)プロパナール及びシアン化水素からの2‐ヒドロキシ‐4‐(メチルチオ)酪酸ニトリルの製法 - Google Patents
3‐(メチルチオ)プロパナール及びシアン化水素からの2‐ヒドロキシ‐4‐(メチルチオ)酪酸ニトリルの製法 Download PDFInfo
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- JP5930329B2 JP5930329B2 JP2013554846A JP2013554846A JP5930329B2 JP 5930329 B2 JP5930329 B2 JP 5930329B2 JP 2013554846 A JP2013554846 A JP 2013554846A JP 2013554846 A JP2013554846 A JP 2013554846A JP 5930329 B2 JP5930329 B2 JP 5930329B2
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims description 169
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 title claims description 55
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 59
- 239000007789 gas Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- ONFOSYPQQXJWGS-UHFFFAOYSA-N 2-hydroxy-4-(methylthio)butanoic acid Chemical compound CSCCC(O)C(O)=O ONFOSYPQQXJWGS-UHFFFAOYSA-N 0.000 claims description 12
- -1 amine inorganic bases Chemical class 0.000 claims description 11
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 2
- 125000006222 dimethylaminomethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920002717 polyvinylpyridine Polymers 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 150000003974 aralkylamines Chemical class 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 28
- 150000001299 aldehydes Chemical class 0.000 description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 description 17
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 14
- 125000004093 cyano group Chemical group *C#N 0.000 description 13
- 238000005259 measurement Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
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- 229960004452 methionine Drugs 0.000 description 10
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 239000000523 sample Substances 0.000 description 7
- PICCHNWCTUUCAQ-UHFFFAOYSA-N 2-hydroxypentanethioic s-acid Chemical compound CCCC(O)C(O)=S PICCHNWCTUUCAQ-UHFFFAOYSA-N 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006189 Andrussov oxidation reaction Methods 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000004255 ion exchange chromatography Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000010561 standard procedure Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
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- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- CQSQMXIROIYTLO-UHFFFAOYSA-N 2-methylpropanethial Chemical compound CC(C)C=S CQSQMXIROIYTLO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
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- 230000001143 conditioned effect Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- JPWPMBYFDCHLKL-UHFFFAOYSA-N 4-methylsulfanylbutanenitrile Chemical compound CSCCCC#N JPWPMBYFDCHLKL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003109 Karl Fischer titration Methods 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 2
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- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- 229940091173 hydantoin Drugs 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 235000010755 mineral Nutrition 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 2
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- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- MWLKEJXYXYRWIH-UHFFFAOYSA-N 2-amino-4-methylsulfanylbutanenitrile Chemical compound CSCCC(N)C#N MWLKEJXYXYRWIH-UHFFFAOYSA-N 0.000 description 1
- BHPAXKBSATVOQB-UHFFFAOYSA-N 2-methylbutanethioamide Chemical compound CCC(C)C(N)=S BHPAXKBSATVOQB-UHFFFAOYSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- FFEARJCKVFRZRR-UHFFFAOYSA-N methionine Chemical compound CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
- C07C255/12—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
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Description
MMPから、好適な触媒の使用下でのシアン化水素(青酸)との反応によって、MMP‐シアンヒドリン(2‐ヒドロキシ‐4‐(メチルチオ)酪酸ニトリル)を製造することができる。好適な触媒は、例えば、ピリジン又はトリエチルアミンである。MHAは、例えば、鉱酸を用いるMMP‐シアンヒドリンの加水分解によって得られる。メチオニンは、MMP‐シアンヒドリンと炭酸水素アンモニウムとの反応によって、ヒダントインの生成下に生じ、これは、塩基、例えば、炭酸カリウム又は水酸化ナトリウムで鹸化され得る。メチオニンの遊離は、二酸化炭素又は硫酸で行われる。
本発明の課題は、アルデヒド、殊にMMPとシアン化水素との反応を触媒するばかりでなく、貯蔵安定性のシアンヒドリンを製造する触媒的方法を得ることであり、この際、この方法は、同時に、収率又は使用アルデヒド及びシアン化水素に関する明らかな改善を有するべきであった。
この及び更なる課題は、2‐ヒドロキシ‐4‐(メチルチオ)酪酸ニトリルの製法によって解明され、この方法では、3‐(メチルメルカプト)‐プロピオンアルデヒドをシアン化水素と、触媒としての塩基の存在下で、主反応帯域でニトリルに反応させ、かつ主反応帯域を出るガス状のシアン化水素(HCN)の残留量を、3‐(メチルメルカプト)‐プロピオンアルデヒド及び触媒及び選択的に2‐ヒドロキシ‐4‐(メチルチオ)酪酸ニトリルからの混合物を含有する吸収帯域及び後反応帯域中で吸収させかつ更に反応させる。
R1は、R2と異なっていてよく、
Xは、0〜6の数であり、かつ
Aは、天然又は合成の樹脂、有利にポリスチレンである]の不均一系のアミン又はポリビニルピリジンを使用することもできる。これらの化合物及びそれと結び付く利点、例えば、より容易な分離可能性、次の反応段階への僅少なエントレインメントは、既にWO2006/015684に記載されている。
MMP-CN:86〜97質量%、
MMP:0〜1質量%、
HCN:0.05〜0.5質量%、
H2O:2〜14質量%、
オリゴマー:0.01〜0.1質量%。
MMP-CN中のH2Oの含量は、最終生成物の二電流測定的指示での滴定法により測定された(Karl-Fischer-Titration)。
例えば、図1に示した、2個の充填床(C)及び(E)を備え、かつ高さ各々2500及び1700mmを有する直径70mmのカラムを有する装置を使用した。充填床の間に、中間塔底部(D)があり、そこから塔頂部循環の操作のために、流れ(6)が引き出され得る。カラムの下に、4リットルの容量を有するカラム塔底部が存在した。この装置の図面は添付されている(図1参照)。
例1からの装置を使用した。
Claims (23)
- 2−ヒドロキシ−4−(メチルチオ)酪酸ニトリルの製造方法であって、3−メチルメルカプト−プロピオンアルデヒドをシアン化水素と、触媒としての塩基の存在下で、主反応帯域中で反応させてニトリルとし、かつ主反応帯域を出るガス状のシアン化水素の残留量を、ガスと液体とを接触させる装置を包含し、3−メチルメルカプトプロピオンアルデヒド及び触媒及び選択的に2−ヒドロキシ−4−(メチルチオ)酪酸ニトリルからの混合物を含有する吸収帯域及び後反応帯域中で吸収させかつ更に反応させ、ここで、吸収帯域及び後反応帯域中に含有される混合物は、少なくとも部分的に主反応帯域から由来する、前記2−ヒドロキシ−4−(メチルチオ)酪酸ニトリルの製造方法。
- 主反応帯域は、撹拌反応器又はループ型反応器を包含する、請求項1に記載の方法。
- 主反応帯域は、付加的に1個のジェットポンプを包含する、請求項2記載の方法。
- 前記ガスと液体とを接触させる装置は、カラム、トレーカラム、充填床カラム、バブルカラム反応器、液滴カラム又は選択的に機械的撹拌容器を有する反応器、浸漬ジェット反応器又はジェットポンプを包含する、請求項1から3までのいずれか1項に記載の方法。
- 吸収帯域及び後反応帯域は、ループ型反応器の一部である、請求項1から4までのいずれか1項に記載の方法。
- ガス状のシアン化水素を主反応帯域中に導入させる、請求項1から5までのいずれか1項に記載の方法。
- 使用されるガスのシアン化水素含量は、1〜99質量%である、請求項6に記載の方法。
- 触媒として、低分子又は不均一系のアミン、無機塩基の溶液又は酸及び低分子アミンからの混合物を使用する、請求項1から7までのいずれか1項に記載の方法。
- 低分子アミンとして、トリ−(C1〜C12アルキル)−アミン、ジアルキルアラルキルアミン、ジアルキルアリールアミン又は複素環系アミンが使用される、請求項8に記載の方法。
- 式Iによる触媒は、同族体のジアルキルアミノアルキルポリスチレン又はジアルキルアミノ巨大網状樹脂の群から選択されるポリマー結合塩基である、請求項10に記載の方法。
- 式Iの触媒は、ジエチルアミノエチルポリスチレン、ジエチルアミノメチルポリスチレン、ジメチルアミノメチルポリスチレン、ジエチルアミノメチル巨大網状樹脂又はジメチルアミノエチルポリスチレンである、請求項11に記載の方法。
- 無機塩基として、アルカリ金属水酸化物、アルカリ金属シアニド、アルカリ金属炭酸塩又はアルカリ金属炭酸水素塩を、単独で又は混合形で使用する、請求項8に記載の方法。
- 酸及び低分子アミンからの混合物中の酸として、有機酸又は有機スルホン酸又は鉱酸を使用する、請求項8に記載の方法。
- 主反応帯域及び吸収帯域及び後反応帯域中で、23℃及び水含量2〜14質量%で、pH電極で測定される、4.5〜6.0のpH値に調整される、請求項1から14までのいずれか1項に記載の方法。
- 主反応帯域は、20℃〜80℃の温度で操作される、請求項1から15までのいずれか1項に記載の方法。
- 吸収帯域及び後反応帯域は、0℃〜30℃の温度で操作される、請求項1から16までのいずれか1項に記載の方法。
- HCN及びMMPのMMP−シアンヒドリンへの反応の完全化のための、MMP−シアンヒドリンの生成物排出部位前のもう1つの後反応帯域は、20℃〜80℃の温度で操作される、請求項1から17までのいずれか1項に記載の方法。
- 0.9〜5バールの絶対圧下に作業される、請求項1から18までのいずれか1項に記載の方法。
- 青酸対3−(メチルチオ)プロパナールのモル比は、0.98〜1.03である、請求項1から19までのいずれか1項に記載の方法。
- 青酸対3−(メチルチオ)プロパナールのモル比は、0.99〜1.01である、請求項20に記載の方法。
- 触媒対3−(メチルチオ)プロパナールの0.00005〜0.002の質量比が使用される、請求項1から21までのいずれか1項に記載の方法。
- 方法は、バッチ法で、半連続又は連続的に実施される、請求項1から22までのいずれか1項に記載の方法。
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EP2468383A1 (de) | 2010-12-22 | 2012-06-27 | Evonik Degussa GmbH | Verfahren zur thermischen Nachverbrennung von Abgasen aus der Acrolein- und aus der Blausäureherstellung |
DE102010064250A1 (de) | 2010-12-28 | 2012-06-28 | Evonik Degussa Gmbh | Verfahren zur Herstellung von Methylmercaptopropionaldehyd |
SG192565A1 (en) | 2011-02-23 | 2013-09-30 | Evonik Degussa Gmbh | Method for producing 2-hydroxy-4-(methylthio)butanenitrile from 3-(methylthio)propanal and hydrogen cyanide |
BR112013020609B1 (pt) | 2011-02-23 | 2019-05-14 | Evonik Degussa Gmbh | Mistura contendo 2-hidróxi-4-(metiltio)butironitrila, seus usos e seu método de produção |
DE102011081828A1 (de) | 2011-08-30 | 2013-02-28 | Evonik Degussa Gmbh | Verfahren zur Umsetzung von Methylmercaptopropionaldehyd aus Roh-Acrolein und Roh-Methylmercaptan |
SG2014012819A (en) | 2011-08-30 | 2014-06-27 | Evonik Degussa Gmbh | Method for producing a methionine salt |
EP2641898A1 (de) | 2012-03-20 | 2013-09-25 | Evonik Industries AG | Verfahren zur Herstellung von Methionin |
EP2679579A1 (de) | 2012-06-27 | 2014-01-01 | Evonik Industries AG | Integriertes Verfahren zur Herstellung von Acrolein und 3-Methylmercaptopropionaldehyd |
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MX341595B (es) | 2016-08-26 |
CN103347854A (zh) | 2013-10-09 |
US9133113B2 (en) | 2015-09-15 |
US20140213819A1 (en) | 2014-07-31 |
CN103347854B (zh) | 2017-04-26 |
KR101911563B1 (ko) | 2018-10-24 |
EP2678312B1 (de) | 2017-10-11 |
US20150197489A1 (en) | 2015-07-16 |
BR112013018092A2 (pt) | 2020-10-27 |
JP2014513668A (ja) | 2014-06-05 |
MX341594B (es) | 2016-08-26 |
WO2012113664A1 (de) | 2012-08-30 |
KR20140007390A (ko) | 2014-01-17 |
US20120215022A1 (en) | 2012-08-23 |
MX2013009640A (es) | 2013-09-26 |
MY174539A (en) | 2020-04-24 |
EP2678312A1 (de) | 2014-01-01 |
RU2604534C2 (ru) | 2016-12-10 |
SG192565A1 (en) | 2013-09-30 |
BR112013018092B1 (pt) | 2021-04-27 |
MX337247B (es) | 2016-02-19 |
US9206121B2 (en) | 2015-12-08 |
US8729288B2 (en) | 2014-05-20 |
ES2649612T3 (es) | 2018-01-15 |
RU2013142825A (ru) | 2015-04-10 |
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