EP0000059A1 - Process for the preparation of N-alkyl-substituted carboxamides. - Google Patents
Process for the preparation of N-alkyl-substituted carboxamides. Download PDFInfo
- Publication number
- EP0000059A1 EP0000059A1 EP78100102A EP78100102A EP0000059A1 EP 0000059 A1 EP0000059 A1 EP 0000059A1 EP 78100102 A EP78100102 A EP 78100102A EP 78100102 A EP78100102 A EP 78100102A EP 0000059 A1 EP0000059 A1 EP 0000059A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- reaction
- distillation
- acids
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 150000003857 carboxamides Chemical class 0.000 title abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 37
- -1 carbonium ions Chemical class 0.000 claims abstract description 37
- 238000004821 distillation Methods 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000011541 reaction mixture Substances 0.000 claims abstract description 16
- 150000007513 acids Chemical class 0.000 claims abstract description 14
- 150000002825 nitriles Chemical class 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 235000011007 phosphoric acid Nutrition 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- 150000003470 sulfuric acid monoesters Chemical class 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 5
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 35
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 22
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 125000003710 aryl alkyl group Chemical group 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- QQGNLKJAIVSNCO-UHFFFAOYSA-N N-butylformamide Chemical compound CCCCNC=O QQGNLKJAIVSNCO-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000000460 chlorine Chemical group 0.000 description 4
- 229910052801 chlorine Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 4
- SDLAKRCBYGZJRW-UHFFFAOYSA-N n-tert-butylformamide Chemical compound CC(C)(C)NC=O SDLAKRCBYGZJRW-UHFFFAOYSA-N 0.000 description 4
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
- 238000006434 Ritter amidation reaction Methods 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 3
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 3
- XFHJDMUEHUHAJW-UHFFFAOYSA-N n-tert-butylprop-2-enamide Chemical compound CC(C)(C)NC(=O)C=C XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- GRWFGVWFFZKLTI-IUCAKERBSA-N 1S,5S-(-)-alpha-Pinene Natural products CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical compound O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 description 2
- 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
- ZTHQBROSBNNGPU-UHFFFAOYSA-N Butyl hydrogen sulfate Chemical compound CCCCOS(O)(=O)=O ZTHQBROSBNNGPU-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 2
- 229940116229 borneol Drugs 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- QEMXXENZTVUGPT-UHFFFAOYSA-N butyl cyclohex-3-ene-1-carboxylate Chemical compound CCCCOC(=O)C1CCC=CC1 QEMXXENZTVUGPT-UHFFFAOYSA-N 0.000 description 2
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- 239000011552 falling film Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical compound CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940041616 menthol Drugs 0.000 description 2
- IPUNVLFESXFVFH-UHFFFAOYSA-N methyl cyclohex-3-ene-1-carboxylate Chemical compound COC(=O)C1CCC=CC1 IPUNVLFESXFVFH-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
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- 150000003254 radicals Chemical class 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
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- 150000003509 tertiary alcohols Chemical class 0.000 description 2
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- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
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- MTVIFDMVZHUZOV-UHFFFAOYSA-N 2,2,3,3,3-pentachloropropanoic acid Chemical compound OC(=O)C(Cl)(Cl)C(Cl)(Cl)Cl MTVIFDMVZHUZOV-UHFFFAOYSA-N 0.000 description 1
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- GAPYETXMWCTXDQ-UHFFFAOYSA-N 2-hydroxyethyl hydrogen sulfate Chemical compound OCCOS(O)(=O)=O GAPYETXMWCTXDQ-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
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- CJTZDYDOPZRFTF-UHFFFAOYSA-N 4-dodecan-2-ylbenzenesulfonic acid Chemical compound CCCCCCCCCCC(C)C1=CC=C(S(O)(=O)=O)C=C1 CJTZDYDOPZRFTF-UHFFFAOYSA-N 0.000 description 1
- KWXICGTUELOLSQ-UHFFFAOYSA-N 4-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 KWXICGTUELOLSQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- WRUAHXANJKHFIL-UHFFFAOYSA-N benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- NVZRFUCVCIVKJR-UHFFFAOYSA-N benzyl(methoxy)phosphinic acid Chemical compound COP(O)(=O)CC1=CC=CC=C1 NVZRFUCVCIVKJR-UHFFFAOYSA-N 0.000 description 1
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- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000005626 carbonium group Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- VRNCRGHDRGGBLW-UHFFFAOYSA-N cyclopenta-1,2-diene Chemical compound C1CC=C=C1 VRNCRGHDRGGBLW-UHFFFAOYSA-N 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- AFAXGSQYZLGZPG-UHFFFAOYSA-N ethanedisulfonic acid Chemical compound OS(=O)(=O)CCS(O)(=O)=O AFAXGSQYZLGZPG-UHFFFAOYSA-N 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- BYNLHLLOIZDKIC-UHFFFAOYSA-N ethyl cyclohex-3-ene-1-carboxylate Chemical compound CCOC(=O)C1CCC=CC1 BYNLHLLOIZDKIC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- PCIBVZXUNDZWRL-UHFFFAOYSA-N ethylene glycol monophosphate Chemical compound OCCOP(O)(O)=O PCIBVZXUNDZWRL-UHFFFAOYSA-N 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DWHMMGGJCLDORC-UHFFFAOYSA-N methoxy(methyl)phosphinic acid Chemical compound COP(C)(O)=O DWHMMGGJCLDORC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- UYJLDSDYCDMKBI-UHFFFAOYSA-N n-tert-butyl-2-phenylacetamide Chemical compound CC(C)(C)NC(=O)CC1=CC=CC=C1 UYJLDSDYCDMKBI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- CACRRXGTWZXOAU-UHFFFAOYSA-N octadecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCS(O)(=O)=O CACRRXGTWZXOAU-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 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
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- KAVGMUDTWQVPDF-UHFFFAOYSA-N perflubutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F KAVGMUDTWQVPDF-UHFFFAOYSA-N 0.000 description 1
- 229950003332 perflubutane Drugs 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
- NFBAXHOPROOJAW-UHFFFAOYSA-N phenindione Chemical class O=C1C2=CC=CC=C2C(=O)C1C1=CC=CC=C1 NFBAXHOPROOJAW-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-N phenylmethanesulfonic acid Chemical compound OS(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229940066528 trichloroacetate Drugs 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
Definitions
- the invention relates to a process for the preparation of N-alkyl-substituted carboxamides.
- a process has been found for the preparation of N-substituted carboxamides by reacting a component which forms carbonium ions with a nitrile in the presence of acids, in which the reaction mixture is separated by distillation, the reaction being carried out in the presence of an acid which is inert under the distillation conditions .
- the process according to the invention can be explained using the following reaction equation:
- the process according to the invention is carried out in the presence of acids which are inert under the distillation conditions.
- Acids which can be used for the process according to the invention should form carbonium ions with components which form carbonium ions and should not lead to decomposition of the reaction mixture or of the reaction product under the distillation conditions.
- Acids of the formula can preferably be used for the process according to the invention wherein Y represents an acyl radical of an acid from the series of phosphoric acids in oxidation state 5, a phosphoric acid mono- or diester and sulfuric acid monoester, an aliphatic or aromatic phosphonic acid, an aliphatic or aromatic sulfonic acid or an aliphatic carboxylic acid with a p K value is greater than 1, be used.
- acyl residues (Y) of an acid from the range of phosphoric acids with oxidation state 5 are the acyl residues of orthophosphoric acid and polyphosphoric acid.
- phosphoric acid and sulfuric acid esters may be mentioned: dimethyl phosphate, diethyl phosphate, monobutyl phosphate, di-2-ethylhexyl phosphate, mono-n-butyl phosphate, mono-n-butyl sulfurate, mono-2-sulfuric acid -hexyl) ester, sulfuric acid mono- (2-hydroxyethyl) ester, phosphoric acid mono- (2-hydroxyethyl) ester.
- acyl radicals of the phosphoric acid monoesters or diesters and sulfuric acid monoesters are those of polyols, such as ethane-1,2-diol, 1,2-propanediol, 1,3-2,2-dimethyl-propane-diol, trimethylolpropane and pentaerythritol.
- aliphatic or aromatic phosphonic acids may be mentioned: methanephosphonic acid, ethanephosphonic acid, methanephosphonic acid monomethyl ester, vinylphosphonic acid, ethane-1,2-phosphonic acid, phenylphosphonic acid, benzylphosphonic acid, benzylphosphonic acid mono-methyl ester.
- Examples include the following sulfonic acids: methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, benzenesulfonic acid, benzene-1,3-disulfonic acid, toluenesulfonic acid, ethane-disulfonic acid 1,2, butane disulfonic acid 1,4, benzyl sulfonic acid , 4- (2-dodecyl) phenyl sulfonic acid, hexadecyl and octadecyl sulfonic acid.
- sulfonic acids methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, benz
- carboxylic acids are: dichloroacetic acid, trichloroacetic acid, perchloropropionic acid, trifluoroacetic acid.
- Examples include the following acids which are particularly preferred for the process according to the invention: trichloroacid and trifluoroacetic acid.
- Components that are known to be activated after the Ritter reaction with acids to form a carbonium ion may be mentioned as a component that forms carbonium ions for the process according to the invention.
- these are secondary or tertiary aliphatic alcohols, esters and olefins.
- radicals R 12 to R 15 may be linked to form cycloaliphatic or aromatic, carbocyclic rings.
- Alkyl radicals (R 8 to R 10 , R 12 to R 16 ) can be, for example, straight-chain or branched hydrocarbon radicals having 1 to 12 carbon atoms. The following may preferably be mentioned: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
- Aralkyl radicals can have a straight-chain or branched hydrocarbon radical with up to 6, preferably with up to 3, carbon atoms in the aliphatic part and a radical from the benzene series, preferably phenyl and naphthyl, in the aromatic part. Examples include: benzyl, phenethyl, benzhydryl and phenyl-dimethyl-methyl.
- Aryl radicals can be aromatic carbocyclic radicals having 5 to 8 carbon atoms, such as phenyl, naphthyl and diphenyl, preferably phenyl.
- Alkenyl residues (R 16 ) can be vinyl, propenyl and cyclopropenyl.
- Examples of acid residues (R 11 ) are the sulfate, phosphate, acetate, trichloroacetate and trifluoroacetate residue.
- the process according to the invention is generally in the temperature range from about 0 ° C to about 120 ° C, preferably from 10 ° C to 100 ° C, bev. moves from 25 ° to 90 o C, performed. At temperatures above 60 ° C., it can be advantageous to carry out the reaction under pressure in order to keep unreacted or excess, noble boiling reaction components, such as hydrocyanic acid, in the liquid reaction phase.
- nitrile at least stoichiometrically based on the arbonium ions b: .ldende component
- an excess of nitrile compared to components forming carbonium ions up to 10: 1 can be used, im it is generally advisable to use the nitrile in a molar ratio of 1 to 3 compared to the components which form carbonium ions.
- Favorable space-time yields are also obtained in that the molar amount of the acid reaches at least the value of the sum of the molar amounts of carboxamide already present in the reaction medium and the component which forms carbonium ions. An excess of the acid above this value increases the reaction rate; In general, it is advisable to use the acid in a ratio of 1 to 3 in relation to the sum of the component which forms carbonium ions and the carboxamide.
- catalytic amounts of perfluoroalkanesulfonic acids such as perfluorobutane or perfluorooctanesulfonic acid or perfluoroalkane carboxylic acids, are used in the reaction to increase the reaction rate.
- perfluoroalkanesulfonic acids such as perfluorobutane or perfluorooctanesulfonic acid or perfluoroalkane carboxylic acids.
- perfluoroalkanesulfonic acids such as perfluorobutane or perfluorooctanesulfonic acid or perfluoroalkane carboxylic acids
- the additions are between 1 and 10 mol% of the total amount of acid.
- the distillation according to the process of the invention can be carried out in a conventional manner.
- it can be carried out in the following distillation apparatus: thin-film evaporators, falling-film evaporators and coiled tube evaporators.
- the distillation according to the process according to the invention can generally be carried out at distillation bottoms from 90 ° to 180 ° C., preferably from 100 to 150 ° C., and at a pressure from 0.1 mbar to I bar, preferably from 0.1 mbar to 100 mbar. be performed.
- the N-alkyl-substituted carboxamide and the acid are obtained by the process according to the invention.
- An optionally obtained mixture of carboxamide and acid can optionally be partially recycled back into the reaction.
- the process according to the invention can be carried out batchwise or continuously.
- the method according to the invention can be carried out as follows:
- the carbonium ion-forming component and the nitrile are passed to a reactor, e.g. a boiler or a boiler cascade provided with cooling and stirring devices, in which there is a mixture of the acid used and, if appropriate, the reaction product.
- a reactor e.g. a boiler or a boiler cascade provided with cooling and stirring devices, in which there is a mixture of the acid used and, if appropriate, the reaction product.
- the reaction mixture is fed to a conveniently continuously operating distillation apparatus, preferably a thin-film evaporator, a falling film evaporator or a slit tube evaporator, and separated depending on the reaction conditions (e.g. Temperature, pressure, evaporator surface and residence time) the carboxylic acid am..d completely or partially.
- the distillation bottoms which in addition to the acid used according to the invention also contains residual carboxamide, can of course be completely separated by further distillation. However, it is also possible, particularly in the case of continuous operation, to fully or partially return the distillation bottoms to the reaction. In order to keep the proportion of by-products low, it is advantageous to separate 0.1 to 5% of the distillation bottoms and, if necessary, to carry this part out separately, e.g. residue combustion.
- the boiling point of the acid is lower than that of the carboxylic acid amide, it may be expedient to separate the acid from the remaining carboxylic acid amide by carrier gas or carrier steam distillation.
- Inert gases such as helium, argon and nitrogen, for example, are suitable as carrier gases, and the nitriles used, such as hydrocyanic acid, acetonitrile and acrylonitrile, are suitable as carrier vapor.
- Chlorine hydrocarbons, such as chlorobenzene and dichlorobenzene, can also be used for a carrier steam distillation, for example.
- the method according to the invention advantageously also saves an extraction step, without which work-up by distillation is not possible according to DT-AS 2 144 230.
- the process according to the invention has the advantage that no waste acids or waste salts are obtained in the isolation of the reaction product; it can therefore be carried out advantageously and without polluting the environment.
- N-substituted carboxamides which can be prepared by the process according to the invention can be used as printing aids or in the production of textile auxiliaries or can be converted to amines.
- Example 1 The bottom product obtained in each case as in Example 1 (36% tert-butylformamide, 64% methanesulfonic acid) is reacted and worked up in accordance with Example 1 with hydrocyanic acid and tert-butanol.
- the table shows the products used and received:
- tripropen 126 g of tripropen are added dropwise to a solution of 18 g of water in 170 g of trifluoroacetic acid at room temperature, the stirred mixture is heated to 65 ° C. and 40 g of hydrocyanic acid are metered in over the course of 45 minutes.
- the reaction mixture is kept one hour at 60 to 65 ° C and then worked up by distillation at a pressure of 12 to 15 torr, wherein the distillation bottom temperature of room temperature is increased to 149 0 C.
- the trifluoroacetic acid used and the excess hydrocyanic acid and small amounts of Ni-nonyl-formamide are obtained as distillate from the boiling range ⁇ 30 ° C.-139 ° C./15 torr, which can be used again for the reaction, and then 146 g of pure one Ni-nonyl-formamide with a boiling range of 142 to 146 ° C / 13 Torr.
- tert 55 g of tert are added dropwise at 50-55 ° C. to a mixture of 140 g of polyphosphoric acid (76% P 2 O 5 ) and 82 g of acetonitrile, which are placed in a reaction vessel provided with a stirrer, dropping funnel and reflux condenser. Butanol. The reaction mixture for 3 hours at 55 - 60 ° C g ehal- th and then eindo in a Dünnschichzverdampfer siert. 77 g of distillate are obtained, which is then fractionated, 47 g of acetonitrile and 30 g of tert. Butylacetamide ( bp 15 99-100 ° C, mp.
- the sump obtained in the thin-film distillation (185 g) contains 27% tert. Butylacetamide in addition to the polyphosphoric acid used (determined by nuclear magnetic resonance spectroscopy. This sump can be reused in the reaction with the same yield result.
- a stirred mixture of 880 g of a C 12 alkylbenzenesulfonic acid and 130 ml of hydrocyanic acid is heated to 50 ° C. under reflux. For this, 181 g are tert. Butanol and 70 ml of hydrocyanic acid were added dropwise. After 1.5 hours, the excess hydrocyanic acid is distilled off in vacuo. At an evaporator temperature of 135 C and a pressure of 0.5 Torr, the reaction mixture is subjected to thin-film distillation. 101 g of tert are obtained. Butylformamide and 950 g of distillation bottoms, which is used again for the reaction. Under the reaction conditions given above, 80 ml of hydrocyanic acid with 75 g of tert are tert in this bottom product. Butanol implemented. The subsequent thin film distillation gives 110 g of tert. Butylformamide.
- the distillation bottoms contain 35% tert. Butylformamide. Under the specified conditions, it is again tert with 75 g. Butanol and 80 ml HCN implemented. The subsequent thin-layer distillation (as stated above) gives 64 g (94% strength) of tert. Butylformamide and 555 distillation bottoms, which was used in the reaction with the same result.
- 660 g of p-dodecylbenzenesulfonic acid are placed in a stirred vessel equipped with a thermometer, dropping funnel, reflux condenser and drying tube. At 20 - 25 ° C, 160 ml of hydrocyanic acid are added. As soon as the hydrocyanic acid has been stirred in well, the mixture is heated to 30 ° to 35 ° C. and dripped within 30 minutes. 148 g tert. Butanol too. The temperature is kept at 40 - 42 ° C by gentle cooling. The mixture is then stirred for 3 h at this temperature, then the unreacted hydrocyanic acid is distilled off in vacuo. 75-80 ml of hydrocyanic acid are obtained.
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Abstract
Verfahren zur Herstellung von N-alkylsubstituierten Carbonsäureamiden. Carbonium-lonen bildende Verbindungen werden mit einem Nitril in Gegenwart von Säuren zu N-alkylsubstituierten Carbonsäureamiden umgesetzt. Das Reaktionsgemisch wird durch Destillation aufgetrennt, wobei man die Umsetzung in Gegenwart einer Säure durchführt, die unter Destillationsbedingungen inert ist.Process for the preparation of N-alkyl substituted carboxamides. Compounds which form carbonium ions are reacted with a nitrile in the presence of acids to give N-alkyl-substituted carboxamides. The reaction mixture is separated by distillation, the reaction being carried out in the presence of an acid which is inert under distillation conditions.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von N-alkylsubstituierten Carbonsäureamiden.The invention relates to a process for the preparation of N-alkyl-substituted carboxamides.
Es ist bekannt, sekundäre und tertiäre Alkohole, Olefine und Wasser, oder Ester mit Nitrilen in Gegenwart von Säuren, beispielsweise Schwefelsäure, zu N-alkylsubstituierten Carbonsäureamiden umzusetzen (in der Literatur als Ritter-Reaktion bekannt). Zur Aufarbeitung wird das Reaktionsgemisch mit einem großen Überschuß an Wasser behandelt (Russian Chemical Review 29, 334 (196O)). Hierbei entstehen große Mengen an verdünnten Säuren, die nur mit großen Aufwendungen beseitigt werden können.It is known to convert secondary and tertiary alcohols, olefins and water, or esters with nitriles in the presence of acids, for example sulfuric acid, to give N-alkyl-substituted carboxamides (known in the literature as the Ritter reaction). For working up, the reaction mixture is treated with a large excess of water (Russian Chemical Review 29, 334 (196O)). This creates large amounts of dilute acids, which can only be removed with great effort.
Es ist außerdem bekannt (DT-AS 2 144 230), nach Durchführung der Umsetzung durch Extraktion das entstandene Säureamid mit säurestabilen, polaren trisubstituierten Phosphorsäureestern oder tetrasubstituierten Harnstoffderivaten zu extrahieren und damit von Säure zu trennen. Nach der Extraktion wird in bekannter Weise, z.B. durch Destillation, aufgearbeitet.It is also known (DT-AS 2 144 230), after carrying out the reaction by extraction, to extract the acid amide formed with acid-stable, polar trisubstituted phosphoric acid esters or tetrasubstituted urea derivatives and thus to separate them from acid. After the extraction, in a known manner, e.g. worked up by distillation.
Es wurde ein Verfahren zur Herstellung von N-substituierten Carbonsäureamiden durch Umsetzung einer Carbonium-Ionen bildenden Komponente mit einem Nitril in Gegenwart vor Säuren gefunden, bei dem man das Reaktionsgemisch durch Destillation auftrennt, wobei man die Umsetzung in Gegenwart einer unter den Destillationsbedinqunqen inerten Säure durchführt.A process has been found for the preparation of N-substituted carboxamides by reacting a component which forms carbonium ions with a nitrile in the presence of acids, in which the reaction mixture is separated by distillation, the reaction being carried out in the presence of an acid which is inert under the distillation conditions .
Das ertindungsgemäße Verfahren kann anhand der folgenden Reaktionsgleichung erläutert werden:
Vorzugsweise können für das erfindungsgemäße Verfahren Säuren der Formel
worin Y für einen Acylrest einer Säure aus der Reihe der Phos phorsäuren in der Oxidationsstufe 5, eines Phosphorsäure- mono- bzw. diesters und Schwefelsäuremonoesters, einer aliphatischen oder aromatischen Fhosphonsäure, einer aliphatischen oder aromatischen Sulfonsäure oder einer aliphatischen Carbonsäure mit einem pK-Wert von größer als 1 steht,
eingesetzt werden.Acids of the formula can preferably be used for the process according to the invention
wherein Y represents an acyl radical of an acid from the series of phosphoric acids in oxidation state 5, a phosphoric acid mono- or diester and sulfuric acid monoester, an aliphatic or aromatic phosphonic acid, an aliphatic or aromatic sulfonic acid or an aliphatic carboxylic acid with a p K value is greater than 1,
be used.
Als Acylreste (Y) einer Säure aus der Reihe der Phosphorsäuren mit der Oxidationsstufe 5 seien beispielsweise die Acylreste der Orthophosphorsäure und der Polyphosphorsäure genannt.Examples of acyl residues (Y) of an acid from the range of phosphoric acids with oxidation state 5 are the acyl residues of orthophosphoric acid and polyphosphoric acid.
Als Acylreste (Y) von Phosphorsäuremono- bzw. -diester und Schwefelsäuremoncester seien Reste der Formel
- R und R2 gleich oder verschieden sind und > für Wasserstoff oder einen Alkylrest mit 1 bis 12, bevorzugt 1 bis 8, Kohlenstoffatomen stehen,
angeführt.As acyl residues (Y) of phosphoric acid monoesters or diesters and sulfuric acid moncesters are residues of the formula
- R and R 2 are identical or different and> represent hydrogen or an alkyl radical having 1 to 12, preferably 1 to 8, carbon atoms,
cited.
Beispielsweise seien die folgenden Phosphorsäure- und Schwefelsäureester genannt: Phosphorsäuredimethylester, Phosphorsäurediäthylester, Phosphorsäuremonobutylester, Fhosphorsäure-di-2-äthylhexyl-ester, Phosphorsäure-mono-n-butylester, Schwefelsäure-mono-n-butylester, Schwefelsäure-mono-(2-äthyl-hexyl) ester, Schwefelsäure-mono-(2-hydroxväthyl)-ester, Phosphorsäure- mono-(2-hydroxyäthyl)-ester.For example, the following phosphoric acid and sulfuric acid esters may be mentioned: dimethyl phosphate, diethyl phosphate, monobutyl phosphate, di-2-ethylhexyl phosphate, mono-n-butyl phosphate, mono-n-butyl sulfurate, mono-2-sulfuric acid -hexyl) ester, sulfuric acid mono- (2-hydroxyethyl) ester, phosphoric acid mono- (2-hydroxyethyl) ester.
Außerdem seien als Acylreste der Phosphorsäuremono- bzw. diester und Schwefelsäuremonoester solche von Polyolen, wie Äthan-diol-1,2,Propandiol-1,2, 2,2-Dimethyl-propan-diol-1,3, Trimethylolpropan und Pentaerythrit angeführt.In addition, the acyl radicals of the phosphoric acid monoesters or diesters and sulfuric acid monoesters are those of polyols, such as ethane-1,2-diol, 1,2-propanediol, 1,3-2,2-dimethyl-propane-diol, trimethylolpropane and pentaerythritol.
Als Acylreste (Y) einer aliphatischen oder aromatischen Phosphorsäure seien Reste der Formel
- R3 für einen geradkettigen oder verzweigten Alkyl- oder Alkenylrest, bevorzugt mit 2 bis 4 Kohlenstoffatomen, Aryl, bevorzugt Phenyl, oder Aralkyl, bevorzugt Benzyl,
- R 4 für Wasserstoff oder einen geradkettigen oder verzweigten Alkylrest, bevorzugt mit 1 bis' 4 Kohlenstoffatomen und
- R5 für einen gegebenenfalls durch C1 bis C4-Alkyl substituierten Alkylen-, bevorzugt mit 2 bis 6 Kohlenstoffatomen, oder einen Arylenrest, bevorzugt Phenylen, steht,
angeführt.As acyl residues (Y) of an aliphatic or aromatic phosphoric acid are residues of the formula
- R 3 represents a straight-chain or branched alkyl or alkenyl radical, preferably having 2 to 4 carbon atoms, aryl, preferably phenyl, or aralkyl, preferably benzyl,
- R 4 represents hydrogen or a straight-chain or branched alkyl radical, preferably having 1 to 4 carbon atoms and
- R 5 represents an alkylene, preferably having 2 to 6 carbon atoms, optionally substituted by C 1 to C 4 alkyl, or an arylene radical, preferably phenylene,
cited.
Beispielsweise seien die tolgenden aliphatischen oder aromatischen Phosphonsäuren genannt: Methanphosphonsäure, Äthanphosphonsäure, Methanphosphonsäure-monomethylester, Vinylphosphonsäure, Äthan-di-phosphonsäure-1,2, Phenylphosphonsäure, Benzyl-phosphonsäure, Benzylphosphonsäure-mono-methylester.For example, the following aliphatic or aromatic phosphonic acids may be mentioned: methanephosphonic acid, ethanephosphonic acid, methanephosphonic acid monomethyl ester, vinylphosphonic acid, ethane-1,2-phosphonic acid, phenylphosphonic acid, benzylphosphonic acid, benzylphosphonic acid mono-methyl ester.
Als Acylreste (Y) einer aliphatischen oder aromatischen Sulfonsäure seien Reste der Formel
- R für einen gegebenenfalls durch Fluor oder Chlor substituierten Alkylrest oder Aralkylrest, bevorzugt mit 1 bis 18 Kohlenstoffatomen, oder einen gegebenenfalls durch Fluor, Chlor, C1-C4-Alkyl oder eine Sulfonsäuregruppe substituierten Arylrest, bevorzugt Phenyl, steht,
angeführt.As acyl residues (Y) of an aliphatic or aromatic sulfonic acid are residues of the formula
- R represents an alkyl radical or aralkyl radical, optionally substituted by fluorine or chlorine, preferably having 1 to 18 carbon atoms, or an aryl radical, preferably phenyl, optionally substituted by fluorine, chlorine, C 1 -C 4 -alkyl or a sulfonic acid group,
cited.
Beispielsweise seien die folgenden Sulfonsäuren genannt: Methansulfonsäure, Äthansulfonsäure, Propansulfonsäure, Butansulfonsäure, Trifluormethansulfonsäure, Perfluorbutansulfonsäure, Benzolsulfonsäure, Benzol-1,3-disulfonsäure, Toluolsulfonsäure, Äthan-di-sulfonsäure-1,2, Butandi-sulfonsäure-1,4, Benzylsulfonsäure, 4-(2-Dodecyl)-phenyl- sulfonsäure, Hexadecyl- und Octadecyl-sulfonsäure.Examples include the following sulfonic acids: methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, perfluorobutanesulfonic acid, benzenesulfonic acid, benzene-1,3-disulfonic acid, toluenesulfonic acid, ethane-disulfonic acid 1,2, butane disulfonic acid 1,4, benzyl sulfonic acid , 4- (2-dodecyl) phenyl sulfonic acid, hexadecyl and octadecyl sulfonic acid.
Als Acylreste (Y) einer aliphatischen Carbonsäure mit einem pH-Wert von größer als 1 seien Reste der Formel
- R7 für einen gegebenenfalls durch Fluor und Chlor substituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen steht,
angeführt.As acyl residues (Y) of an aliphatic carboxylic acid with a pH of greater than 1 are residues of the formula
- R 7 represents an alkyl radical with 1 to 4 carbon atoms optionally substituted by fluorine and chlorine,
cited.
Als Carbonsäuren seien beispielsweise genannt: Dichloressigsäure, Trichloressigsäure, Perchlorpropionsäure, Trifluoressigsäure.Examples of carboxylic acids are: dichloroacetic acid, trichloroacetic acid, perchloropropionic acid, trifluoroacetic acid.
Beispielsweise seien die folgenden für das erfindungsgemäße Verfahren besonders bevorzugten Säuren genannt: Trichlor- und Trifluoressigsäure.Examples include the following acids which are particularly preferred for the process according to the invention: trichloroacid and trifluoroacetic acid.
Es ist möglich, das erfindungsgemäße Verfahren in Gegenwart einer oder mehrerer Säuren durchzuführen.It is possible to carry out the process according to the invention in the presence of one or more acids.
Als Carboniumionen bildende Komponente für das erfindungsgemäße Verfahren seien die Komponenten genannt, die bekanntlich nach der Ritter-Reaktion mit Säuren zu einem Carboniumion aktiviert werden. Beispielsweise sind dies sekundäre oder tertiäre aliphatische Alkohole, Ester und Olefine.Components that are known to be activated after the Ritter reaction with acids to form a carbonium ion may be mentioned as a component that forms carbonium ions for the process according to the invention. For example, these are secondary or tertiary aliphatic alcohols, esters and olefins.
Als sekundäre und tertiäre Alkohole seien Verbindungen der Formel
- R Wasserstoff, Alkyl, Aralkyl oder Aryl und
- R 9 und R10 gleich oder verschieden sind und Alkyl oder Aralkyl bedeuten,
genannt.Compounds of the formula are secondary and tertiary alcohols
- R is hydrogen, alkyl, aralkyl or aryl and
- R 9 and R 10 are identical or different and are alkyl or aralkyl,
called.
Als Ester seien Verbindungen der Formel
- R , R9 und R10 die oben genannte Bedeutung haben und
- R11 einen Acylrest einer anorganischen oder organischen Säure bedeutet,
genanrt.Compounds of the formula are esters
- R, R 9 and R 10 have the meaning given above and
- R 11 denotes an acyl residue of an inorganic or organic acid,
mentioned.
Als Olefine seien Verbindungen der Formel
- R12, R13 und R14 gleich oder verschieden sind und Wasserstoff, Alkyl, Aralkyl oder Aryl und
- R15 Alkyl, Aralkyl oder Aryl bedeuten,
genannt.Compounds of the formula are olefins
- R 12 , R 13 and R 14 are the same or different and are hydrogen, alkyl, aralkyl or aryl and
- R 15 is alkyl, aralkyl or aryl,
called.
Es ist auch möglich, daß jeweils zwei der Reste R12 bis R15 zu cyclo-aliphatischen oder aromatischen, carbocyclischen Ringen verbunden sind.It is also possible for two of the radicals R 12 to R 15 to be linked to form cycloaliphatic or aromatic, carbocyclic rings.
Als Nitrile für das erfindungsgemäße Verfahren seien Verbindungen der Formel
- R 16 Wasserstoff, Alkyl, Alkenyl, Aralkyl oder Aryl bedeutet,
genannt.Compounds of the formula are nitriles for the process according to the invention
- R 16 denotes hydrogen, alkyl, alkenyl, aralkyl or aryl,
called.
Alkylreste (R8 bis R10,R12 bis R 16) können beispielsweise geradkettige oder verzweigte Kohlenwasserstoffreste mit 1 bis 12 Kohlenstoffatomen sein. Bevorzugt seien genannt: Methyl, Äthyl, Propyl, Isopropyl, Butyl, Isobutyl, Pentyl, Isopentyl, Hexyl und Isohexyl.Alkyl radicals (R 8 to R 10 , R 12 to R 16 ) can be, for example, straight-chain or branched hydrocarbon radicals having 1 to 12 carbon atoms. The following may preferably be mentioned: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
Aralkylreste (R8 bis R10 R12 bis R 16) können im aliphatischen Teil einen geradkettigen oder verzweigten Kohlenwasserstoffrest mit bis zu 6, bevorzugt mit bis zu 3 Kohlenstoffatomen, und im aromatischen Teil einen Rest aus der Benzolreihe, bevorzugt Phenyl und Naphthyl, haben. Beispielsweise seien genannt: Benzyl, Phenäthyl, Benzhydryl und Phenyl-dimethyl-methyl.Aralkyl radicals (R 8 to R 10 R12 to R 16 ) can have a straight-chain or branched hydrocarbon radical with up to 6, preferably with up to 3, carbon atoms in the aliphatic part and a radical from the benzene series, preferably phenyl and naphthyl, in the aromatic part. Examples include: benzyl, phenethyl, benzhydryl and phenyl-dimethyl-methyl.
Arylreste (R8 und R12 bis R16) können aromatische carbocyclische Reste mit 5 bis 8 Kohlenstoffatomen wie Phenyl, Naphthyl und Diphenyl, bevorzugt Phenyl, sein.Aryl radicals (R 8 and R 12 to R16) can be aromatic carbocyclic radicals having 5 to 8 carbon atoms, such as phenyl, naphthyl and diphenyl, preferably phenyl.
Alkenylreste (R16) können Vinyl, Propenyl und Cyclopropenyl sein.Alkenyl residues (R 16 ) can be vinyl, propenyl and cyclopropenyl.
Als Säurereste (R11) seien beispielsweise der Sulfat-, Phosphat-, Acetat-, Trichloracetat- und der Trifluoracetatrest genannt.Examples of acid residues (R 11 ) are the sulfate, phosphate, acetate, trichloroacetate and trifluoroacetate residue.
Die Herstellung der einzelnen Komponenten für das erfindungsgemäße Verfahren ist bekannt. Im einzelnen seien beispielhaft die folgenden Verbindungen angeführt:
- Als Alkohole: Isopropanol, tert.-Butanol, sek.-Butanol, iso-Amylalkohol, Cyclohexanol, Benzylalkohol, Borneol, Terpineol und Menthol.
- Als Ester: Schwefelsäure-mono-ester von Isopropanol, Cyclohexanol, die Trifluoracetate, die bei der Addition von Trifluoressigsäure an Mono- und Diolefine, wie Propen, Isobuten, Cyclopentadien-1,5 und Dicyclopentadien entstehen.
- Als Olefine: Propen, Isobuten, Buten-1, cis- und transbuten-2, 2-Methyl-buten-2, Diisobuten, Triisobuten, Tetraisobuten, Tri- und Tetrapropen, α- und ß-Pinen, Styrol,α-Methylstyrol, Cyclopenten, Cyclohexen, 1-Methyl-cyclohexen, Isopren, Dicyclopentadien, 2,5-Dimethylhexadien-1,5, Limonen, Methallylchlorid, Methallylcyanid, 3-Cyclohexen-1-carbonsäure- nitril, 4-Methylcyclohexen-1-carbonsäure- nitril, 3-Cyclohexen-1-carbonsäure-methylester, 3-Cyclohexen-1-carbonsäure-äthyl- ester, 3-Cyclohexen-1-carbonsäure-butylester und Abietinsäure-methylester.
- Als Nitrile: Blausäure, Acetonitril, Acrylnitril., Propionitril, Pivalonitril, Laurinsäurenitril, Stearinsäurenitril, Benzylcyanid und Benzonitril.
- As alcohols: isopropanol, tert-butanol, sec-butanol, iso-amyl alcohol, cyclohexanol, benzyl alcohol, borneol, terpineol and menthol.
- As esters: sulfuric acid monoesters of isopropanol, cyclohexanol, the trifluoroacetates that result from the addition of trifluoroacetic acid to mono- and diolefins, such as propene, isobutene, 1,5-cyclopentadiene and dicyclopentadiene.
- As olefins: propene, isobutene, butene-1, cis and transbutene-2, 2-methyl-butene-2, diisobutene, triisobutene, tetraisobutene, tri- and tetrapropene, α- and β-pinene, styrene, α-methylstyrene, Cyclopentene, cyclohexene, 1-methyl-cyclohexene, isoprene, dicyclopentadiene, 2,5-dimethylhexadiene-1,5, limonene, methallyl chloride, methallyl cyanide, 3-cyclohexene-1-carboxylic acid nitrile, 4-methylcyclohexene-1-carboxylic acid nitrile, 3-cyclohexene-1-carboxylic acid methyl ester, 3-cyclohexene-1-carboxylic acid ethyl ester, 3-cyclohexene-1-carboxylic acid butyl ester and abietic acid methyl ester.
- As nitriles: hydrocyanic acid, acetonitrile, acrylonitrile, propionitrile, pivalonitrile, lauric acid nitrile, stearic acid nitrile, benzyl cyanide and benzonitrile.
Das erfindungsgemäße Verfahren wird im allgemeinen im Temperaturbereich von etwa 0°C bis etwa 120°C, bevorzugt von 10°C bis 100°C, besonders bev. zugt von 25°bis 90oC, durchgeführt. Bei Temperaturen die oberhalb 60°C liegen, kann es vorteilhaft sein, die Reaktion unter Druck auszuführen, um unumgesetzte oder überschüssige, edrig siedende Reaktionskomponenten, wie z.B. Blausäure, in der flüssigen Reaktionsphase zu halten.The process according to the invention is generally in the temperature range from about 0 ° C to about 120 ° C, preferably from 10 ° C to 100 ° C, bev. moves from 25 ° to 90 o C, performed. At temperatures above 60 ° C., it can be advantageous to carry out the reaction under pressure in order to keep unreacted or excess, noble boiling reaction components, such as hydrocyanic acid, in the liquid reaction phase.
Zur Erzielung hoher Raum-Zeit-Ausbeute kann es zweckmäßig sein, das Nitril mindestens stöchiometrisch bezogen auf die arbonium-Ionen b:.ldende Komponente einzusetzen, vorteilhaft kann ein Uberschuß von Nitril gegenüber Carbonium-Ionen bildenden Komponenten bis 10:1 eingesetzt werden, im allgemeinen empfiehlt es sich, das Nitril im molaren Verhältnis von 1 bis 3 gegenüber den Carbonium-Ionen bildenden Komponenten einzusetzen. Günstige Raum-Zeit-Ausbeuten erhält man weiterhin dadurch, daß die molare Menge der Säure mindestens den Wert der Summe der molaren Mengen von bereits im Reaktionsmedium befindlichem Carbonsäureamid und der Carbonium-Ionen bildenden Komponente erreicht. Ein Überschuß der Säure über diesen Wert hinaus erhöht die Reaktionsgeschwindigkeit; im allgemeinen empfiehlt es sich, die Säure gegenüber der Summe der Carbonium-Ionen bildenden Komponente und dem Carbonsäureamid im Verhältnis 1 bis 3 einzusetzen.To achieve a high space-time yield, it may be expedient to use the nitrile at least stoichiometrically based on the arbonium ions b: .ldende component, an excess of nitrile compared to components forming carbonium ions up to 10: 1 can be used, im it is generally advisable to use the nitrile in a molar ratio of 1 to 3 compared to the components which form carbonium ions. Favorable space-time yields are also obtained in that the molar amount of the acid reaches at least the value of the sum of the molar amounts of carboxamide already present in the reaction medium and the component which forms carbonium ions. An excess of the acid above this value increases the reaction rate; In general, it is advisable to use the acid in a ratio of 1 to 3 in relation to the sum of the component which forms carbonium ions and the carboxamide.
In einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens setzt man bei der Umsetzung zur Steigerung der Reaktionsgeschwindigkeit katalytische Mengen von Perfluoralkansulfonsäuren, wie die Perfluorbutan- oder Perfluoroctansulfonsäure oder Perfluoralkancarbonsäuren, wie Trifluoressigsäure zu. Im allgemeinen liegen die Zusätze zwischen 1 und 10 Mol-% der Gesamtsäuremenge.In a particular embodiment of the process according to the invention, catalytic amounts of perfluoroalkanesulfonic acids, such as perfluorobutane or perfluorooctanesulfonic acid or perfluoroalkane carboxylic acids, are used in the reaction to increase the reaction rate. such as trifluoroacetic acid. In general, the additions are between 1 and 10 mol% of the total amount of acid.
Die Destillation nach dem erfindungsgemäßen Verfahren kann in üblicher Weise durchgeführt werden. Beispielsweise kann sie in folgenden Destillationsapparatureh durchgeführt werden: Dünnschichtverdampfer, Fallfilmverdampfer und Schlangenrohrverdampfer.The distillation according to the process of the invention can be carried out in a conventional manner. For example, it can be carried out in the following distillation apparatus: thin-film evaporators, falling-film evaporators and coiled tube evaporators.
Die Destillation nach dem erfindungsgemäßen Verfahren kann im allgemeinen bei Destillationssumpftemperaturen von 90° bis 180°C, bevorzugt von 100 bis 150°C, und bei einem Druck von 0,1 mbar bis I bar, bevorzugt von 0,1 mbar bis 100 mbar, durchgeführt werden.The distillation according to the process according to the invention can generally be carried out at distillation bottoms from 90 ° to 180 ° C., preferably from 100 to 150 ° C., and at a pressure from 0.1 mbar to I bar, preferably from 0.1 mbar to 100 mbar. be performed.
Nach dem erfindurgsgemäßen Verfahren erhält man nach der Destillation das N-alkylsubstituierte Carbonsäureamid und die Säure. Ein gegebenenfalls anfallendes Gemisch aus Carbonsäureamid und Säure kann gegebenenfalls teilweise wieder in die Umsetzung zurückgeführt werden.After the distillation, the N-alkyl-substituted carboxamide and the acid are obtained by the process according to the invention. An optionally obtained mixture of carboxamide and acid can optionally be partially recycled back into the reaction.
Das erfindungsgemäße Verfahren kann sowohl diskontinuierlich als auch kontinuierlich durchgeführt werden.The process according to the invention can be carried out batchwise or continuously.
Das erfindungsgemäße Verfahren kann wie folgt ausgeführt werden:The method according to the invention can be carried out as follows:
Die Carbonium-Ionen bildende Komponente und das Nitril werden einem Reaktor, z.B. einen mit Kühl- und Rührvorrichtungen versehenen Kessel oder einer Kesselkaskade, zugeführt, in dem sich ein Gemisch aus der eingesetzten Säure und gegebenenfalls dem Reaktionsprodukt, befindet.The carbonium ion-forming component and the nitrile are passed to a reactor, e.g. a boiler or a boiler cascade provided with cooling and stirring devices, in which there is a mixture of the acid used and, if appropriate, the reaction product.
Für den Fall, daß der Siedepunkt des Carbonsäureamids niedriger ist als der der Säure führt man nach der Umsetzung das Reaktionsgemisch einer, zweckmäßigerweise kontinuierlich arbeitenden, Destillationsapparatur, vorzugsweise einem Dünnschichtverdampfer, einen Fallfilmverdampfer oder einem Schlanqenrohrverdampfer, zu und trennt in Abhängigkeit von den Reaktionsbedingungen (z.B. Temperatur, Druck, Verdampferfläche und Verweilzeit) das Carbonsäuream..d ganz oder teilweise ab. Der Destillationssumpf, der neben der erfindungsgemäß eingesetzten Säure noch restliches Carbonsäureamid enthält, kann selbstverständlich vollständig durch weitere Destillation aufgetrennt werden. Es ist aber auch möglich, insbesondere bei kontiuierlicher Arbeitsweise, den Destillationssumpf ganz oder teilweise in die Umsetzung zurückzuführen. Um den Anteil an Nebenprodukten gering zu halten, trennt man vorteilhafterweise 0,1 bis 5 % des Destillationssumpfes ab und führt diesen Teil gegebenenfalls einer gesonderten Aufarbeitung, z.B. einer Rückstandsverbrennung zu.In the event that the boiling point of the carboxylic acid amide is lower than that of the acid, after the reaction, the reaction mixture is fed to a conveniently continuously operating distillation apparatus, preferably a thin-film evaporator, a falling film evaporator or a slit tube evaporator, and separated depending on the reaction conditions (e.g. Temperature, pressure, evaporator surface and residence time) the carboxylic acid am..d completely or partially. The distillation bottoms, which in addition to the acid used according to the invention also contains residual carboxamide, can of course be completely separated by further distillation. However, it is also possible, particularly in the case of continuous operation, to fully or partially return the distillation bottoms to the reaction. In order to keep the proportion of by-products low, it is advantageous to separate 0.1 to 5% of the distillation bottoms and, if necessary, to carry this part out separately, e.g. residue combustion.
Für den Fall, daß der Siedepunkt der Säure niedriger ist als der des Carbonsäureamids, kann es zweckmäßig sein, die Säure durch eine Trägergas- bzw. Trägerdampfdestillation vom zurückbleibenden Carbonsäureamid zu trennen. Als Trägergase kommen hier beispielsweise Inertgase, wie Helium, Argon und Stickstoff, und als Trägerdampf die eingesetzten Nitrile, wie Blausäure, Acetonitril und Acrylnitril in Frage. Für eine Trägerdampfdestillation können beispielsweise auch Chlorkohlenwasserstoffe, wie Chlor- und Dichlorbenzol, verwendet werden.In the event that the boiling point of the acid is lower than that of the carboxylic acid amide, it may be expedient to separate the acid from the remaining carboxylic acid amide by carrier gas or carrier steam distillation. Inert gases such as helium, argon and nitrogen, for example, are suitable as carrier gases, and the nitriles used, such as hydrocyanic acid, acetonitrile and acrylonitrile, are suitable as carrier vapor. Chlorine hydrocarbons, such as chlorobenzene and dichlorobenzene, can also be used for a carrier steam distillation, for example.
Es war nicht zu erwarten, daß sich das bei der Umsetzung erhaltene Gemisch durch Destillation aufarbeiten läßt, da unter diesen Bedingungen eine Zersetzung des Reaktionsproduktes zu erwarten war. Eine solche Zersetzung tritt beispielsweise bei der für die Ritter-Reaktion als Reaktionsmedium besonders oft angewandten Schwefelsäure auf (DT-AS 2 144 230, Spalte 1, Zeile 41 bis Spalte 2, Zeile 20).It was not to be expected that the mixture obtained in the reaction could be worked up by distillation, since a decomposition of the reaction product was to be expected under these conditions. Such decomposition occurs, for example, with sulfuric acid, which is particularly often used as the reaction medium for the Ritter reaction (DT-AS 2 144 230, column 1, line 41 to column 2, line 20).
Diese Schwierigkeit macht es notwendig, das Reaktionsprodukt z.B. mit einem großen Überschuß an Wasser zu behandeln.This difficulty makes it necessary to e.g. treat with a large excess of water.
Durch das erfindungsgemäße Verfahren wird vorteilhafterweise auch ein Extra tionsschritt gespart, ohne den der DT-AS 2 144 230 zufolge eine Aufarbeitung durch Destillation nicht möglich ist.The method according to the invention advantageously also saves an extraction step, without which work-up by distillation is not possible according to DT-AS 2 144 230.
Das erfindungsgemäße Verfahren hat den Vorteil, daß bei der Isolierung des Reaktionsproduktes keine Abfallsäuren oder Abfallsalze anfallen; es läßt sich daher vorteilhaft und ohne Belastung der Umwelt durchführen.The process according to the invention has the advantage that no waste acids or waste salts are obtained in the isolation of the reaction product; it can therefore be carried out advantageously and without polluting the environment.
Die nach dem erfindungsgemäßen Verfahren herstellbaren N-substituierten Carbonsäureamide können als Druckereihilfsmittel bzw. bei der Herstellung von Textilhilfs-Mitteln eingesetzt oder zu Aminen umgesetzt werden.The N-substituted carboxamides which can be prepared by the process according to the invention can be used as printing aids or in the production of textile auxiliaries or can be converted to amines.
In eine Lösung von 150 q Blausäure in 420 g Methansulfonsäure, die sich in einem mit Rückflußkühler und Tropftrichter versehenen Rührgefäß befindet, werden unter Rühren und Kühlen 222 g tert.-Butanol innerhalb einer Stunde zudosiert. Die Reaktionstemperatur wird während des Eintropfens langsam ansteigend auf 20 bis 40°C gehalten. Das Reaktionsgemisch wird 4 Stunden bei 40°C gehalten. Dann wird die überschüssige Blausäure im Vakuum abdestilliert. Das zurückbleibende Reaktionsgemisch wird bei einer Verdampferwandtemperatur von 110 bis 115°C in einen Dünnschichtverdampfer eindosiert. Dabei destillieren 55 g eines Gemisches von 96 % tert.-Butylformamid und 4 % tert.-Butanol (gaschrcmatographisch ermittelt) ab und es werden 665 g eines Sumpfproduktes aus Methansulfonsäure und tert.-Butylformamid im Verhältnis 64:36 (nach Kernresonanzspektrum) erhalten.In a solution of 150 q hydrocyanic acid in 420 g of methanesulfonic acid, which is located in a stirred vessel provided with a reflux condenser and dropping funnel, 222 g of tert-butanol are metered in with stirring and cooling within one hour. The reaction temperature is kept slowly increasing to 20 to 40 ° C. during the dropping. The reaction mixture is kept at 40 ° C. for 4 hours. Then the excess hydrocyanic acid is distilled off in vacuo. The remaining reaction mixture is metered into a thin-film evaporator at an evaporator wall temperature of 110 to 115 ° C. 55 g of a mixture of 96% tert-butylformamide and 4% tert-butanol (determined by gas chromatography) distill off and 665 g of a bottom product of methanesulfonic acid and tert-butyl formamide are obtained in a ratio of 64:36 (according to the nuclear magnetic resonance spectrum).
In 200 g Methansulfonsäure,die 1 g Phenothiazin als Polymerisationsinhibitor enthält, wird innerhalb einer Stunde eine Lösung von 150 g tert.-Butanol in 159 g Acrylnitril bei einer Reaktionstemperatur von 30 bis 35°C zugetropft. Das Reaktionsgemisch verbleibt 6 Stunden bei dieser Temperatur im Reaktionsgefäß und wird nach Abdestillieren des überschüssigen Acrylnitril mit 900 g Äthanol vermischt und in einen Schlangenrohrverdampfer eindosiert. Bei 150°C und 25 bar destillieren mit dem Alkohol 100 g N-tert.-Butylacrylamid ab, die durch abdestillieren des Äthanols isoliert werden, Fp. 125°C. Der Sumpf kann mit gleichem Ausbeuteergebnis in die Reaktionsstufe zurückgeführt werden.In 200 g of methanesulfonic acid, which contains 1 g of phenothiazine as a polymerization inhibitor, a solution of 150 g of tert-butanol in 159 g of acrylonitrile is added dropwise at a reaction temperature of 30 to 35 ° C. within one hour. The reaction mixture remains in this reaction vessel at this temperature for 6 hours and, after the excess acrylonitrile has been distilled off, is mixed with 900 g of ethanol and metered into a snake tube evaporator. At 150 ° C. and 25 bar, 100 g of N-tert-butylacrylamide are distilled off with the alcohol and are isolated by distilling off the ethanol, mp. 125 ° C. The bottom can be returned to the reaction stage with the same yield.
Das wie in Beispiel 1 jeweils erhaltene Sumpfprodukt (36 % tert.-Butylformamid, 64 % Methansulfonsäure) wird entsprechend Beispiel 1 mit Blausäure und tert.-Butanol umgesetzt und aufgearbeitet. Die Tabelle gibt die eingesetzten und erhaltenen Produkte an:
In eine Mischung von 90 g Trifluoressigsäure und 185 g Benzylcyanid werden bei 20°C innerhalb von einer Stunde 44 g tert.-Butanol zugetropft. Das Reaktionsgemisch wird dann 6 Stunden bei 60°C gehalten. Dann wird die Hauptmenge der Trifluoressigsäure unter Normaldruck abdestilliert, ein kleiner Teil im Gemisch mit überschüssigem Benzylcyanid bei vermindertem Druck (Siedebereich bis 75°C/0,5 Torr). Der Destillationssumpf besteht aus nahezu reinem N-tert.-Butyl-phenyl-acetamid. Fp. 1140C (aus Alkohol umgelöst), Ausbeute 69 g.44 g of tert-butanol are added dropwise at 20 ° C. in a mixture of 90 g of trifluoroacetic acid and 185 g of benzyl cyanide. The reaction mixture is then kept at 60 ° C. for 6 hours. Then the main amount of trifluoroacetic acid is distilled off under normal pressure, a small part in a mixture with excess benzyl cyanide at reduced pressure (boiling range up to 75 ° C / 0.5 Torr). The distillation bottoms consist of almost pure N-tert-butyl-phenyl-acetamide. Mp 114 0 C (from alcohol recrystallized)., Yield 69 g.
In eine Mischung von 163 g Trichloressigsäure und 54 g Adipinsäuredinitril werden bei 80°C 100 g tert.-Butanol innerhalb von einer Stunde zugetropft. Die Reaktionsmischung wird 7 Stunden bei 80°C gehalten. Danach wird das Reaktionsprodukt durch Vakuumdestillation der eingesetzten Trichloressigsäure, die bei ca. 100°C/13 Torr abdestilliert wird, abgetrennt. Man erhält 90 g Adipinsäure-N-tert.-butyl-diamid, das als fester Rückstand im Reaktionsgefäß zurückbleibt. Fp. 213 bis 215°C (aus Äthanol umgelöst).In a mixture of 163 g of trichloroacetic acid and 54 g of adiponitrile, 100 g of tert-butanol are added dropwise at 80 ° C. over the course of one hour. The reaction mixture is kept at 80 ° C. for 7 hours. The reaction product is then separated off by vacuum distillation of the trichloroacetic acid used, which is distilled off at about 100 ° C./13 torr. 90 g of adipic acid-N-tert-butyl-diamide are obtained, which remains as a solid residue in the reaction vessel. Mp 213 to 215 ° C (redissolved from ethanol).
Unter Kühlung werden in eine Lösung- von 1 g Phenothiazin in 90 g Trifluoressigsäure 84 g Acrylnitril bei 20°C eingetropft. Bei 35°C werden danach 43 g tert.-Butanol zugetropft. Die Reaktionsmischung wird 6 Stunden bei 60 bis 70°C gehalten und anschließend destillativ aufgearbeitet. Acrylnitril, Trifluoressigsäure und ein Teil des entstandenen N-tert.-Butylacrylamids werden unter vermindertem Druck abdestilliert. Zurück bleiben als Destillationssumpf 36 g N-tert.-Butylacrylamid (Fp. 120 bis 1220C). Das Destillat kann mit gleichem Ergebnis wieder in die Reaktion eingesetzt werden.While cooling, 84 g of acrylonitrile are added dropwise at 20 ° C. to a solution of 1 g of phenothiazine in 90 g of trifluoroacetic acid. 43 g of tert-butanol are then added dropwise at 35 ° C. The reaction mixture is 6 hours at 60 kept up to 70 ° C and then worked up by distillation. Acrylonitrile, trifluoroacetic acid and part of the resulting N-tert-butylacrylamide are distilled off under reduced pressure. 36 g of N-tert-butylacrylamide (mp 120 to 122 ° C.) remain as the distillation bottoms. The distillate can be used again in the reaction with the same result.
In eine Lösung von 18 g Wasser in 170 g Trifluoressigsäure werden bei Raumtemperatur 126 g Tripropen eingetropft, die gerührte Mischung wird auf 65°C erwärmt und innerhalb von 45 Minuten werden 40 g Blausäure zudosiert. Die Reaktionsmischung wird eine Stunde bei 60 bis 65°C gehalten und anschließend bei einem Druck von 12 bis 15 Torr destillativ aufgearbeitet, wobei die Destillationssumpftemperatur von Raumtemperatur bis auf 1490C gesteigert wird. Man gewinnt auf diese Weise die eingesetzte Trifluoressigsäure und die überschüssige Blausäure und geringe Mengen an N-i-Nonyl-formamid als Destillat vom Siedebereich < 30°C - 139°C/ 15 Torr, das erneut zur Reaktion eingesetzt werden kann, und anschließend 146 g reines N-i-Nonyl-formamid vom Siedebereich 142 bis 146°C/13 Torr.126 g of tripropen are added dropwise to a solution of 18 g of water in 170 g of trifluoroacetic acid at room temperature, the stirred mixture is heated to 65 ° C. and 40 g of hydrocyanic acid are metered in over the course of 45 minutes. The reaction mixture is kept one hour at 60 to 65 ° C and then worked up by distillation at a pressure of 12 to 15 torr, wherein the distillation bottom temperature of room temperature is increased to 149 0 C. In this way, the trifluoroacetic acid used and the excess hydrocyanic acid and small amounts of Ni-nonyl-formamide are obtained as distillate from the boiling range <30 ° C.-139 ° C./15 torr, which can be used again for the reaction, and then 146 g of pure one Ni-nonyl-formamide with a boiling range of 142 to 146 ° C / 13 Torr.
In eine Mischung von 140 g Polyphosphorsäure (76 % P2O5) und 82 g Acetonitril, die in einem mit Rührer, Tropftrichter und Rückflußkühler versehenen Reaktionsgefäß vorgelegt werden, tropft man bei 50 - 55°C 55 g tert. Butanol ein. Die Reaktionsmischung wird 3 Stunden bei 55 - 60°C gehal- ten und anschließend in einem Dünnschichzverdampfer eindosiert. Man erhält 77 g Destillat, das anschließend fraktioniert wird, wobei 47 g Acetonitril und 30 g tert. Bu- tylacetamid (Kp 15 99 - 100°C, Fp. 93 - 94°C) erhalten werden. Der bei der Dünnschichtdestillation erhaltene Sumpf (185 g) enthält 27 % tert. Butylacetamid neben der eingesetzten Polyphosphorsäure, (bestimmt durch Kernresonanzspektroskopie. Dieser Sumpf läßt sich mit gleichem Ausbeuteergebnis in die Reaktion erneut einsetzen.55 g of tert are added dropwise at 50-55 ° C. to a mixture of 140 g of polyphosphoric acid (76% P 2 O 5 ) and 82 g of acetonitrile, which are placed in a reaction vessel provided with a stirrer, dropping funnel and reflux condenser. Butanol. The reaction mixture for 3 hours at 55 - 60 ° C g ehal- th and then eindo in a Dünnschichzverdampfer siert. 77 g of distillate are obtained, which is then fractionated, 47 g of acetonitrile and 30 g of tert. Butylacetamide ( bp 15 99-100 ° C, mp. 93-94 ° C) can be obtained. The sump obtained in the thin-film distillation (185 g) contains 27% tert. Butylacetamide in addition to the polyphosphoric acid used (determined by nuclear magnetic resonance spectroscopy. This sump can be reused in the reaction with the same yield result.
Eine gerührte Mischung von 880 g einer C12-Alkyl-benzolsulfonsäure und von 130 ml Blausäure wird unter Rückflußkühlung auf 50°C erwärmt. Dazu werden 181 g tert. Butanol und 70 ml Blausäure zugetropft. Nach 1,5 Stunden wird der Blausäureüberschuß im Vakuum abdestilliert. Bei einer Verdampfertemperatur von 135 C und einem Druck von 0,5 Torr wird das Reaktionsgemisch einer Dünnschichtdestillation unterworfen. Man erhält 101 g tert. Butylformamid und 950 g Destillationssumpf, der erneut zur Reaktion eingesetzt wird. Unter den oben angegebenen Reaktionsbedingungen werden in diesem Sumpfprodukt 80 ml Blausäure mit 75 g tert. Butanol umgesetzt. Die anschließende Dünnschichtdestillation ergibt 110 g tert. Butylformamid.A stirred mixture of 880 g of a C 12 alkylbenzenesulfonic acid and 130 ml of hydrocyanic acid is heated to 50 ° C. under reflux. For this, 181 g are tert. Butanol and 70 ml of hydrocyanic acid were added dropwise. After 1.5 hours, the excess hydrocyanic acid is distilled off in vacuo. At an evaporator temperature of 135 C and a pressure of 0.5 Torr, the reaction mixture is subjected to thin-film distillation. 101 g of tert are obtained. Butylformamide and 950 g of distillation bottoms, which is used again for the reaction. Under the reaction conditions given above, 80 ml of hydrocyanic acid with 75 g of tert are tert in this bottom product. Butanol implemented. The subsequent thin film distillation gives 110 g of tert. Butylformamide.
In eine Mischung von 435 g Schwefelsäuremono-n-butylester und 180 ml Blausäure werden bei 30 - 40cC 259 g tert. Butanol eingetropft, die Reaktion wird innerhalb von 3 Stunden bei 40°C zum Ende geführt. Das Reaktionsgemisch wird einer Dünnschichtdestillation unterworfen. Bei einer Verdampfertemperatur von 115°C und einem Druck von 0,5 Torr werden 90 g Destillat erhalten, das aus einem Gemisch von tert.-Butylformamid, n-Butanol und n-Butylameisensäureester besteht.In a mixture of 435 g of sulfuric acid mono-n-butyl ester and 180 ml of hydrocyanic acid at 30 - 40 C C 259 g tert. Dropped in butanol, the reaction is within 3 Hours at 40 ° C to the end. The reaction mixture is subjected to thin film distillation. At an evaporator temperature of 115 ° C. and a pressure of 0.5 torr, 90 g of distillate are obtained, which consists of a mixture of tert-butylformamide, n-butanol and n-butyl formic acid ester.
Der Destillationssumpf enthält 35 % tert. Butylformamid. Unter den angegebenen Bedingungen wird er erneut mit 75 g tert. Butanol und 80 ml HCN umgesetzt. Durch die (wie oben angegeben) anschließende Dünnschichtdestillation erhält man 64 g (94 %iges) tert. Butylformamid und 555 Destillationssumpf, der mit gleichem Ergebnis in die Reaktion eingesetzt wurde.The distillation bottoms contain 35% tert. Butylformamide. Under the specified conditions, it is again tert with 75 g. Butanol and 80 ml HCN implemented. The subsequent thin-layer distillation (as stated above) gives 64 g (94% strength) of tert. Butylformamide and 555 distillation bottoms, which was used in the reaction with the same result.
In einem Rührgefäß, versehen mit Thermometer, Tropftrichter, Rückflußkühler und Trockenrohr, legt man 660 g p-Dodecylbenzolsulfonsäure vor. Bei 20 - 25°C gibt man 160 ml Blausäure zu. Sobald die Blausäure gut eingerührt ist erwärmt man auf 30° bis 35°C und tropft innerhalb von 30 min. 148 g tert. Butanol zu. Durch leichtes Kühlen hält man die Temperatur bei 40 - 42°C. Anschließend wird 3 h bei dieser Temperatur nachgerührt, dann die unumgesetzte Blausäure im Vakuum abdestilliert. Man erhält 75 - 80 ml Blausäure zurück.660 g of p-dodecylbenzenesulfonic acid are placed in a stirred vessel equipped with a thermometer, dropping funnel, reflux condenser and drying tube. At 20 - 25 ° C, 160 ml of hydrocyanic acid are added. As soon as the hydrocyanic acid has been stirred in well, the mixture is heated to 30 ° to 35 ° C. and dripped within 30 minutes. 148 g tert. Butanol too. The temperature is kept at 40 - 42 ° C by gentle cooling. The mixture is then stirred for 3 h at this temperature, then the unreacted hydrocyanic acid is distilled off in vacuo. 75-80 ml of hydrocyanic acid are obtained.
Der verbleibende Rückstand wird bei einer Wandtemperratur von 1450C in einem Dünnschichtverdampfer eingespeist. Dabei destillieren 106 g eines Gemisches von 94 % tert. Butylformamid und 6 % tert. Butanol (gaschromatographisch ermittelt) ab. Es werden 750 g Sumpfprodukt erhalten, das die Sulfonsäure und tert. Butylformamid im Verhältnis 2: 1 (nach Kernresonanzspektroskopie) enthält.
Das Sumpfprodukt läßt sich mit gleichem Ergebnis erneut einsetzen.The remaining residue is fed in at a wall temperature of 145 ° C. in a thin-film evaporator. 106 g of a mixture of 94% tert distill. Butylformamide and 6% tert. Butanol (determined by gas chromatography). 750 g of bottom product are obtained which contain the sulfonic acid and tert. Contains butylformamide in a ratio of 2: 1 (according to nuclear magnetic resonance spectroscopy).
The bottom product can be used again with the same result.
Claims (4)
einsetzt.2) Method according to claim 1, characterized in that an acid of the formula
starts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2725889A DE2725889C3 (en) | 1977-06-08 | 1977-06-08 | Process for the preparation of N-alkyl-substituted carboxamides |
| DE2725889 | 1977-06-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000059A1 true EP0000059A1 (en) | 1978-12-20 |
| EP0000059B1 EP0000059B1 (en) | 1980-09-17 |
Family
ID=6011060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100102A Expired EP0000059B1 (en) | 1977-06-08 | 1978-06-06 | Process for the preparation of n-alkyl-substituted carboxamides. |
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| Country | Link |
|---|---|
| US (1) | US4246199A (en) |
| EP (1) | EP0000059B1 (en) |
| JP (1) | JPS5416401A (en) |
| BR (1) | BR7803654A (en) |
| DE (2) | DE2725889C3 (en) |
| ES (1) | ES470565A1 (en) |
| IN (1) | IN148189B (en) |
| IT (1) | IT1104726B (en) |
| ZA (1) | ZA783259B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100811043B1 (en) * | 2001-11-16 | 2008-03-06 | 엘지전자 주식회사 | Transmission Power Control Method for Shared Channel (SCH) and HI in Mobile Communication System |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4640384A (en) * | 1986-04-07 | 1987-02-03 | Alexander Kucher | Emergency evacuation system for high-rise buildings |
| EP0976451A1 (en) * | 1998-07-31 | 2000-02-02 | Haldor Topsoe A/S | Process for the recovery of perfluorinated sulphonic acids from spent acid |
| US6303817B1 (en) | 2000-08-10 | 2001-10-16 | International Flavors & Fragrances Inc. | Method for making amides |
| US6482983B1 (en) * | 2001-07-31 | 2002-11-19 | Millennium Specialty Chemicals | Process for obtaining N-monosubstituted amides |
| AT413101B (en) * | 2002-10-01 | 2005-11-15 | Dsm Fine Chem Austria Gmbh | IMPROVED METHOD FOR THE PRODUCTION OF N-SUBSTITUTED AMIDES FROM NITRILES |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2601387A (en) * | 1948-11-24 | 1952-06-24 | Du Pont | Preparation of amides having tertiary carbon attached to amido nitrogen |
| US3627830A (en) * | 1969-02-03 | 1971-12-14 | Basf Ag | Production of pure-n-dimethylacylamides |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1934485A (en) * | 1929-10-04 | 1933-11-07 | Du Pont | Treatment of formamide |
| US1950875A (en) * | 1931-07-09 | 1934-03-13 | Du Pont | Process for the vaporization of formamide |
| US2457660A (en) * | 1944-06-01 | 1948-12-28 | Du Pont | N-tertiary alkyl amides and method for preparing same |
| US2554846A (en) * | 1945-11-01 | 1951-05-29 | Armour & Co | Preparation of n,n' diacyldiaminoalkanes |
| US2628217A (en) * | 1949-01-25 | 1953-02-10 | Du Pont | Process for preparing amides |
| US2597446A (en) * | 1949-11-29 | 1952-05-20 | Wyeth Corp | Tertiary butyl secondary amines and method for preparing the same |
| US2573673A (en) * | 1950-05-27 | 1951-10-30 | John J Ritter | Method of producing n-mono substituted imidic compounds |
| ES257803A1 (en) * | 1959-06-06 | 1960-11-01 | Konink Ind Mij Voorheen Noury | Triacetyl- and tetraacetylmethylenediamine and process |
| US3008992A (en) * | 1959-12-02 | 1961-11-14 | Union Carbide Corp | Process for recovering n-methyl-n-vinylacetamide |
| IL27076A (en) * | 1966-12-18 | 1971-03-24 | Varshany E | Production of n-substituted amides |
| US3846492A (en) * | 1969-05-22 | 1974-11-05 | Phillips Petroleum Co | Amide production |
| DE2236040C2 (en) * | 1972-07-22 | 1974-06-27 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of carboxamides |
| US3976595A (en) * | 1975-03-17 | 1976-08-24 | Celanese Corporation | Sulfonic acid-type catalysts useful in, for example, esterification reactions |
-
1977
- 1977-06-08 DE DE2725889A patent/DE2725889C3/en not_active Expired
-
1978
- 1978-05-19 IN IN382/DEL/78A patent/IN148189B/en unknown
- 1978-05-30 US US05/911,009 patent/US4246199A/en not_active Expired - Lifetime
- 1978-06-06 EP EP78100102A patent/EP0000059B1/en not_active Expired
- 1978-06-06 IT IT49725/78A patent/IT1104726B/en active
- 1978-06-06 DE DE7878100102T patent/DE2860163D1/en not_active Expired
- 1978-06-06 JP JP6734878A patent/JPS5416401A/en active Pending
- 1978-06-07 BR BR787803654A patent/BR7803654A/en unknown
- 1978-06-07 ES ES470565A patent/ES470565A1/en not_active Expired
- 1978-06-07 ZA ZA00783259A patent/ZA783259B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2601387A (en) * | 1948-11-24 | 1952-06-24 | Du Pont | Preparation of amides having tertiary carbon attached to amido nitrogen |
| US3627830A (en) * | 1969-02-03 | 1971-12-14 | Basf Ag | Production of pure-n-dimethylacylamides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100811043B1 (en) * | 2001-11-16 | 2008-03-06 | 엘지전자 주식회사 | Transmission Power Control Method for Shared Channel (SCH) and HI in Mobile Communication System |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000059B1 (en) | 1980-09-17 |
| JPS5416401A (en) | 1979-02-07 |
| ZA783259B (en) | 1979-06-27 |
| IN148189B (en) | 1980-11-29 |
| BR7803654A (en) | 1979-01-16 |
| DE2725889B2 (en) | 1979-07-19 |
| DE2725889C3 (en) | 1980-04-17 |
| IT7849725A0 (en) | 1978-06-06 |
| IT1104726B (en) | 1985-10-28 |
| US4246199A (en) | 1981-01-20 |
| DE2860163D1 (en) | 1980-12-18 |
| ES470565A1 (en) | 1979-01-01 |
| DE2725889A1 (en) | 1978-12-14 |
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