CN100366603C - N-取代甲酰胺的制备方法 - Google Patents
N-取代甲酰胺的制备方法 Download PDFInfo
- Publication number
- CN100366603C CN100366603C CNB2004800045740A CN200480004574A CN100366603C CN 100366603 C CN100366603 C CN 100366603C CN B2004800045740 A CNB2004800045740 A CN B2004800045740A CN 200480004574 A CN200480004574 A CN 200480004574A CN 100366603 C CN100366603 C CN 100366603C
- Authority
- CN
- China
- Prior art keywords
- group
- structural formula
- aryl
- platinum
- 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.)
- Expired - Fee Related
Links
- -1 N-substituted formamides Chemical class 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000019253 formic acid Nutrition 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- 239000005078 molybdenum compound Substances 0.000 claims abstract description 6
- 150000002752 molybdenum compounds Chemical class 0.000 claims abstract description 6
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 37
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 7
- 239000002250 absorbent Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000003610 charcoal Substances 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 230000006353 environmental stress Effects 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000010948 rhodium Substances 0.000 claims 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 239000003426 co-catalyst Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 12
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical compound O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- HBEDSQVIWPRPAY-UHFFFAOYSA-N 2,3-dihydrobenzofuran Chemical compound C1=CC=C2OCCC2=C1 HBEDSQVIWPRPAY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RJKGJBPXVHTNJL-UHFFFAOYSA-N 1-nitronaphthalene Chemical compound C1=CC=C2C([N+](=O)[O-])=CC=CC2=C1 RJKGJBPXVHTNJL-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 1
- HYANHJNUAZZLRC-UHFFFAOYSA-N 5-amino-4-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(N)C=C(C(O)=O)C=C1C(O)=O HYANHJNUAZZLRC-UHFFFAOYSA-N 0.000 description 1
- MEQASKDMJDLBRC-UHFFFAOYSA-N C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.N3CCNCC3 Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C34.N3CCNCC3 MEQASKDMJDLBRC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 241000344110 Erysimum rhodium Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000534944 Thia Species 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000384 adrenergic alpha-2 receptor agonist Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- KBAAVEBMJBZPCJ-UHFFFAOYSA-N anilino formate Chemical compound O=CONC1=CC=CC=C1 KBAAVEBMJBZPCJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002527 isonitriles Chemical class 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- MLYGFXBIHLNCKU-UHFFFAOYSA-N pyrene;1h-pyrrole Chemical class C=1C=CNC=1.C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 MLYGFXBIHLNCKU-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
- C07C233/14—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/08—Radicals containing only hydrogen and carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
在有至少一种基于贵金属的氢化催化剂和钒或钼化合物作为辅助催化剂的情况下，用甲酸和/或甲酸铵作为氢供体和甲酰化剂，通过氢化相应的硝基芳烃或硝基杂芳烃制备N-芳基或N-杂芳基甲酰胺。
Description
本发明涉及一种通过还原性甲酰化从硝基芳烃或硝基杂芳烃制备N-芳基或N-杂芳基甲酰胺的方法。
N-芳基或N-杂芳基甲酰胺是合成许多化合物的有用中间产品。例如，它们可以脱水生成异腈(US-A-3636036)。甲酰基也可作为氨基保护基团，其经强酸处理可裂解。N-芳基或N-杂芳基甲酰胺的其它应用还包括用作热记录材料(JP-A-09-193553)的显影剂或用作聚合作用催化剂(US-A-5153767)的助剂。
已知的生产N-芳基或N-杂芳基甲酰胺的方法是基于对应的芳基和芳香胺与甲酸的反应。生产芳香胺的常用方法包括通过氢化或用铁作为还原剂使对应的硝基芳烃还原。WO-A-96/36597公开了在存在微量钒化合物的条件下使用贵金属催化剂以气体氢使硝基芳烃氢化成芳香胺。在一个实施例中，当反应混合物中存在乙酸钠时，芳香胺被原位乙酰化。使用加压(高达20bar)气体氢和高压釜是该方法的一个缺陷。
本发明的一个目的是提供一种简便的、一步从硝基化合物生产N-芳基或N-杂芳基甲酰胺的方法。
本发明的另一目的是提供一种从在相邻环碳原子上含有硝基氨基集团的芳烃生产苯并咪唑的一步式方法。取代的苯并咪唑是合成具有药物活性化合物的有用中间产品。
人们业已发现，能够在有至少一种贵金属基氢化催化剂和一种作为辅助催化剂的钒或钼化合物的情况下，以甲酸和/或甲酸铵作为氢供体和甲酰化剂使对应的硝基芳烃或硝基杂芳烃氢化来生产N-芳基或N-杂芳基甲酰胺。这种方法的一个最大优点是可在环境压力下不使用气体氢就能进行反应。
这里以及下面所使用的术语“芳烃”和“芳基”应分别理解为表示诸如苯、联苯、萘、茚满、蒽、菲、芴、芘和二萘嵌苯的所有的单环、双环和多环芳烃以及衍生自各个上述碳氢化合物的单价基团(比如苯基、联二苯基、萘基等)。
相应地，这里以及下面所使用的术语“杂芳烃”和“杂芳基”应分别理解为表示所有的至少含有一个碳以外的环原子，特别是氮、氧或硫的单环、双环和多环芳烃及其所衍生的单价基团，杂芳烃的例子包括吡啶、嘧啶、芘嗪、哒嗪、吡咯、芘唑、咪唑、呋喃、噻吩、噻唑、吲哚、异吲哚、中氮茚、喹啉、异喹啉、喹喔啉、喹唑啉、邻二氮杂萘、萘啶、咔唑、氮杂蒽和吩嗪。
这里以及下面所使用的术语“贵金属”应理解为尤其表示铂系金属，即铑、钌、钯、锇、铱和铂。
在本发明的一个较佳实施例中，N-芳基或N-杂芳基甲酰胺具有下列结构式：
其中，取代基R1和R5独立地选自氢、卤素、C1-6-烷基、C1-6烷氧基、氰基、羧基、二(C1-6-烷基)氨基、C1-6-烷氧基羰基和芳基；
R2到R4独立地选自氢、卤素、C1-6烷基、C1-6-烷氧基、氰基、羧基、二(C1-6-烷基)氨基、C1-6-烷氧基羰基、芳基和-NHCHO；
和/或R1到R5中的两个或多个与所述苯基部分一起形成一个双环或多环的稠合碳环或杂环体系；
且对应的硝基芳烃或硝基杂芳烃具有下列结构式：
其中，R1′到R5′各自具有与结构式(I)中对应的取代基R1、R2、R3、R4和R5相同的含义，或者，如果所述对应的取代基是-NHCHO，则为-NO2或NH2。这里以及在下文中，术语“C1-6-烷基”应理解为表示具有1-6个碳原子的直链或支链烷基，诸如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、叔戊基、新戊基、己基等。因此，术语“C1-6烷氧基”、“C1-6烷氧基羰基”、“二(C1-6-烷基)氨基”的含义应理解为分别表示由前述C1-6-烷基基团和氧、羰氧(-OC(＝O)-)或氮组成的任意部分。
含有苯基部分的双环或多环稠合碳环或杂环环系是例如作为碳环的萘、茚满、四氢化萘、芴、蒽、菲、苊、芘和二萘嵌苯以及作为杂环的吲哚、苯并咪唑、硫杂茚、喹啉、喹喔啉、苯并二氢呋喃、色烯、咔唑和氮杂蒽。
在本发明的另一个较佳实施例中，所形成的N-芳基或N-杂芳基甲酰胺在邻近具有硝基的碳原子那个碳上有一个氨基基团，它可原位与甲酰胺部分反发生应形成咪唑环，从而生成一个苯并咪唑体系。假若，例如，使用邻-硝基苯胺作为反应物，则产物将是苯并咪唑。
在本发明的一个更优选的实施例中，最终形成的N-杂芳基甲酰胺是具有下述结构式的苯并咪唑：
其中，取代基R1、R4和R5如上述定义，而对应的硝基芳烃具有下述结构式：
其中，R2′和R3′中的一个是-NO2，另一个是-NH2；
而R1、R4和R5如上面结构式(Ia)中的定义。
特别优选的硝基芳烃(IIa)是那些其中R2′为-NO2和R3′为-NH2的，尤其是哪些其中R1为甲基和R4为氰基的。对应的苯并咪唑(Ia)的甲酰氨基可以水解生成对应的胺，这种胺便是合成α-肾上腺素受体激动剂(WO-A-99/26942)的中间体。
苯并咪唑(Ia)可以以两种互变异构体形式(1H和3H型)之一存在或以这两种形式的混合物存在。为了简便起见，在此仅介绍其中一种形式。
较佳地，基于贵金属的氢化催化剂是铂，尤其是以诸如活性炭等为载体的铂。
更佳选地，铂是“中毒的”，尤其是经过硫化的。
为了获得高产率的理想的甲酰胺或苯并咪唑，而较少地生成副产品或未能完全还原的产物，比如羟胺或邻-甲酰基羟胺，必须加入诸如钒或钼化合物的辅助催化剂。而且这种钒或钼化合物最好是选自氧化钒(V2O5)、偏钒酸铵(NH4VO3)和诸如钼酸钠(Na2MoO4)的钼酸盐。
较佳地，氢化反应在环境压力下进行。
本发明将结合具体实施例进行详细说明。然而，必须注意，本发明决非仅限于此。
实施例1
甲酰苯胺(N-苯基甲酰胺)
在氩气氛下将硝基苯(12.31g，100mmol)、甲酸(80％；278mL，328.0g)、硫化的铂催化剂(活性炭载体上5％的铂，Engelhard号：43045，批号：08544；干重1.55g)和氧化钒(57mg)加入一个带有温度控制的0.3L的双壁搅拌容器中。停止氩气流，浆料加温到91-94℃，持续2小时。反应混合物HPLC分析表明：甲酰苯胺得率为79.9％，并伴有18.3％苯胺生成。
实施例2(比较例)
甲酰苯胺(N-苯基甲酰胺)
重复实施例1的步骤，但不加氧化钒。反应3小时后，甲酰胺得率为55％，并有30.6％的N-甲酸基苯胺和10.2％的苯胺副产品生成。
实施例3
1-氯-2，4-双(甲酰氨基)苯
用1-氯-2，4-二硝基苯(100mmol，20.26g)作为起始化合物，重复实施例1的步骤。反应温度为91-95℃，1-氯-2，4-双(甲酰氨基)苯得率为77.0％。部分还原的化合物1-氯-2(4)-甲酰氨基-4(2)-硝基苯的得率为20.5％。
实施例4
1-氯-2，4-双(甲酰氨基)苯
在氩气氛下将1-氯-2，4-二硝基苯(4mmol，0.81g)、甲酸水溶液(80％；11mL，13g)、硫化的铂催化剂(活性炭载体上5％的铂，Engelhard号：43045，批号：08544；干重62mg)和钼酸钠二水合物(2.3mg)加入一个小型搅拌容器中。停止氩气流，浆料加温到90-95℃，持续2.5小时。1-氯-2，4-双(甲酰氨基)苯得率为76.1％，部分还原的化合物1-氯-2(4)-甲酰氨基-4(2)-硝基苯的得率为20.5％。
实施例5
1-氯-2，4-双(甲酰氨基)苯
用偏钒酸铵(2mg)代替钼酸钠二水合物重复实施例4的步骤。在90-95℃温度下反应2.5小时后，1-氯-2，4-双(甲酰氨基)苯的得率为77.2％，部分还原的化合物1-氯-2(4)-甲酰氨基-4(2)-硝基苯的得率为20.5％。
实施例6
1-氯-2，4-双(甲酰氨基)苯
在氩气氛下将1-氯-2，4-二硝基苯(4mmol，0.81g)、甲酸铵(约40mmol，2.6g)、硫化的铂催化剂(活性炭载体上5％的铂，Engelhard号：43045，批号：08544；干重62mg)和乙腈(11mL)加入-个小型搅拌容器中。停止氩气流，浆料加温到80℃，持续2.5小时，1-氯-2，4-双(甲酰氨基)苯得率为88.5％。
实施例7
1-氯-2，4-双(甲酰氨基)苯
在添加氧化钒(2.3mg)的情况下重复实施例6的步骤。在80℃温度下反应2.5小时后，1-氯-2，4-双(甲酰氨基)苯的得率为95.7％。
实施例8
1-甲酰氨基-4-甲基苯(对-甲酰基甲苯胺(p-formtoluidide))用对-硝基甲苯(4mmol，0.55g)作为起始化合物重复实施例7的步骤。反应温度为80℃，反应时间2.5小时之后，1-甲酰氨基-4-甲基苯的得率为87.9％，生成的副产品是4-苯甲胺(11.2％)。
实施例9
1，3-双(甲酰氨基)-2-甲基苯
用2，6-二硝基甲苯(4mmol，0.81g)作为起始化合物，重复实施例4的步骤。1，3-双(甲酰氨基)-2-甲基苯和1-氨基-3-甲酰氨基-2-甲基苯的共同得率为97.2％。
实施例10
1，3-双(甲酰氨基)-2-甲基苯
在不加入钼酸钠的情况下重复实施例9的步骤。1，3-双(甲酰氨基)-2-甲基苯和1-氨基-3-甲酰氨基-2-甲基苯的共同得率为79.0％。
实施例11
1，3-双(甲酰氨基)-2-甲基苯
在加入氧化钒(2.3mg)代替钼酸钠二水合物的情况下重复实施例9的步骤。1，3-双(甲酰氨基)-2-甲基苯和1-氨基-3-甲酰氨基-2-甲基苯的共同得率为98.1％。
实施例12
2-氨基-4-甲基-3，5-二硝基苄腈
将4-甲基-3，5-二硝基苄腈(10.5kg；制备见US-A-3 162 675)、4-氨基-4H-1，2，4-三唑(17.0kg)和二甲亚砜(68.6kg)的溶液用约50分钟投配到叔-丁氧锂(12.2kg)和二甲亚砜(106.6kg)的混合物中，其间使每种溶液的温度保持在20-25℃。在20-25℃熟化2小时后，用约10分钟在20℃将醋酸(8.9g)投配到反应混合物中。在20℃左右用1.5小时时间将水(158L)投配到反应混合物中使产物结晶。产物浆料冷却到10-15℃并使其在此温度下保持约45分钟。过滤所得到的浆料，用水(106L)洗涤。将所得的湿饼放入真空盘式干燥器在约50℃和30托真空下干燥，2-氨基-4-甲基-3，5-二硝基苄腈为橙棕色固体。产量为9.8kg(87％)。
实施例13
5-甲酰氨基-4-甲基-1H-苯并咪唑-7-腈[N-(7-氰基-4-甲基-1H-苯并眯唑-5-基)-甲酰胺](Ia，R1＝Me，R4＝CN，R5＝H)
在氩气氛下将2-氨基-4-甲基-3，5-二硝基苯甲腈(IIa，R1＝Me，R2’＝NO2’，R3’＝NH2，R4＝CN，R5＝H，；22.2g，100mmol)、甲酸(80％的水溶液；328.0g)、硫化的铂催化剂(活性炭载体上5％的铂，水分57.8％，来自意大利的Engelhard，样品代码43045；2.44g)和铂/钒催化剂(活性炭载体上5％铂+1％钒，水分61.74％，Degussa CF 1082XBA/W；1.22g)加入带有温度控制的1L双壁搅拌容器中。停止氩气流，浆料在50分钟内加温到90℃，期间二氧化碳开始发气。反应混合物在剧烈发气情况下在90-93℃再保持2小时，同时用HPLC监控。反应完成后，混合物冷却到25℃，黑色悬浮液经1cm的Celite层过滤，随后用80％甲酸水溶液(50g)洗涤。在45℃/30毫巴的条件下，亮橙色滤液在旋转式蒸发器中浓缩成大约150g。加入甲醇(118.0g，150mL)，在45℃经过15分钟后，混合物在半小时内被冷却到0℃，再搅拌1小时。将沉淀的产物过滤出来，用甲醇(58.2g，74mL)洗涤产物滤饼。这样得到的产物(21.7g)在45℃/25毫巴干燥15小时。
产量：15.3g(75.9％，测定(HPLC)：99.3％)。
熔点＞310℃。
根据核磁共振数据，产品为构象异构体和/或互变异构体的混合物。以下仅给出了主要同分异构体(83％)的化学位移：
1H NMR(DMSO-d6)：δ＝13.2(br.s，1H)，9.87(br.s，1H)，8.47(s，1H)，8.35(d，J＝1.8Hz，1H)，7.91(s，1H)，2.48(s，2H)。
13C NMR(DMSO-d6)：δ＝160.1，144.6，140.5，134.0，129.9，123.0，121.6，117.1，97.8，13.1。
实施例14
5-氨基-4-甲基-1H-苯并眯唑-7-腈
5-(甲酰氨基)-4-甲基-1H-苯并咪唑-7-腈(4.8kg)、水(46L)和浓盐酸(17.8kg)的混合物在80℃左右搅拌约1.5小时。在混合物冷却到25℃后，加入50％的氢氧化钠水溶液(17.1kg)和水(64L)。混合物在约15分钟内冷却到25℃。然后过滤混合物，并用水(50L)洗涤产物。产物在真空盘式干燥器中在45-50℃和约40托真空下进行干燥。
产量：3.8kg(94％)。
实施例15
1-甲酰氨基-2-甲氧基苯(邻-甲酰基甲氧基苯胺(formoanisidide))用邻-硝基苯甲醚(4mmol，0.55g)作为原材料、并用氧化钒(2.3mg)替代钼酸钠二水合物重复实施例4的步骤。在90-95℃反应2.5小时后，邻-formoanisidide的得率为24.8％，邻-茴香胺为主要产物，得率为62.8％。
实施例16
1-甲酰氨基萘
用1-硝基萘(4mmol，0.61g)作为起始原料、并用氧化钒(2.3mg)替代钼酸钠二水合物重复实施例4的步骤。在90-95℃反应2.5小时后，1-甲酰氨基萘的得率为22.3％，α-萘胺为主要产物，得率为60.8％。
Claims (10)
1.一种制备具有下述结构式(I)的N-芳基或N-杂芳基甲酰胺的方法，
其中，取代基R1和R5独立地选自氢、卤素、C1-6-烷基、C1-6-烷氧基、氰基、羧基、二(C1-6-烷基)氨基、C1-6-烷氧基羰基和芳基；
R2到R4独立地选自氢、卤素、C1-6-烷基、C1-6-烷氧基、氰基、羧基、二(C1-6-烷基)氨基、C1-6-烷氧基羰基、芳基和-NHCHO；
和/或R1到R5中的两个或多个与所述苯基部分形成双环或多环稠合碳环或杂环环系；
所述的方法包括在至少一种基于选自铑、钌、钯、锇、铱和铂的贵金属的氢化催化剂和钒或钼化合物为辅助催化剂的条件下，以甲酸和/或甲酸铵为氢供体和甲酰化剂，氢化下述结构式(II)的硝基芳烃或硝基杂芳烃
其中，R1’到R5’中的每一个具有和结构式(I)中相应取代基R1、R2、R3、R4和R5的相同含义，或者，如果所述相应取代基是-NHCHO，则为-NO2或NH2。
2.根据权利要求1所述的方法，其特征在于，所形成的N-芳基或N-杂芳基甲酰胺含有一个氨基基团，该基团可原位与甲酰胺部分反应生成一个咪唑环。
3.根据权利要求1或2所述的方法，其特征在于，所述N-杂芳基甲酰胺具有下述结构式：
其中，取代基R1、R4和R5如权利要求1所定义，而所述的硝基芳烃具有下述结构式：
其中：R2’和R3’中的一个是-NO2，另一个是-NH2；
而R1、R4和R5如上面结构式(Ia)中所定义。
4.根据权利要求3所述的方法，其特征在于，所述R2‘是-NO2而R3’是-NH2。
5.根据权利要求4所述的方法，其特征在于，所述R1是甲基而R4是氰基。
6.根据权利要求1所述的方法，其特征在于，所述贵金属是铂。
7.根据权利要求6所述的方法，其特征在于，所述基于贵金属的氢化催化剂是活性炭载体上的铂。
8.根据权利要求6或7所述的方法，其特征在于，所述铂是经过硫化的。
9.根据权利要求1所述的方法，其特征在于，所述钒或钼化合物选自氧化钒、偏钒酸铵和钼酸钠。
10.根据权利要求1所述的方法，其特征在于，所述氢化反应在环境压力下进行。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US44812303P | 2003-02-20 | 2003-02-20 | |
| US60/448,123 | 2003-02-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1751020A CN1751020A (zh) | 2006-03-22 |
| CN100366603C true CN100366603C (zh) | 2008-02-06 |
Family
ID=32908540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800045740A Expired - Fee Related CN100366603C (zh) | 2003-02-20 | 2004-02-19 | N-取代甲酰胺的制备方法 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7268255B2 (zh) |
| EP (1) | EP1597227A1 (zh) |
| JP (1) | JP4554591B2 (zh) |
| KR (1) | KR101053816B1 (zh) |
| CN (1) | CN100366603C (zh) |
| HK (1) | HK1088593A1 (zh) |
| IL (1) | IL170253A (zh) |
| WO (1) | WO2004074234A1 (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8680333B2 (en) * | 2009-12-04 | 2014-03-25 | Basf Se | Process for the preparation of aromatic formamides |
| CN102942500B (zh) * | 2012-11-16 | 2014-08-27 | 常州大学 | 一种n-甲酰胺类化合物的制备方法 |
| CN107715873B (zh) * | 2017-10-26 | 2020-11-24 | 湘潭大学 | 一种以金属有机骨架材料为载体负载La改性的Pt基催化剂的制备方法及应用 |
| CN111153825A (zh) * | 2019-06-19 | 2020-05-15 | 浙江大学 | 利用负载型金属氧化物催化材料制备酰胺类化合物的方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6096924A (en) * | 1995-05-19 | 2000-08-01 | Novartis Ag | Process for the catalytic hydrogeneration of aromatic nitro compounds |
| CN1284073A (zh) * | 1997-11-24 | 2001-02-14 | 宝洁公司 | 5－(2－咪唑啉基氨基)－苯并咪唑衍生物,其制备和作为具有改进的代谢稳定性的a－肾上腺素能受体激动剂的应用 |
| US6326517B1 (en) * | 1998-12-10 | 2001-12-04 | Central Glass Company, Limited | Method of producing benzamides |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2647815A (en) * | 1951-05-03 | 1953-08-04 | Gen Aniline & Film Corp | Alkyl diformyl phenylenediamines |
| US3636036A (en) | 1970-02-11 | 1972-01-18 | Ivar Ugi | Alkyl substituted phenylene diisonitriles |
| FR2644161B1 (fr) | 1989-03-08 | 1991-05-10 | Rhone Poulenc Chimie | Procede de preparation d'amides n-arylsubstitues |
| JPH0792543B2 (ja) | 1990-03-01 | 1995-10-09 | キヤノン株式会社 | レーザ走査装置及びそれを用いた画像形成装置 |
| JP3562089B2 (ja) | 1996-01-18 | 2004-09-08 | 日本製紙株式会社 | 感熱記録体 |
| JP3463919B2 (ja) * | 1998-12-10 | 2003-11-05 | セントラル硝子株式会社 | 安息香酸アミド |
| US20040167194A1 (en) * | 2003-02-20 | 2004-08-26 | Randall Jared Lynn | Methods of making 6-[(4,5-Dihydro-1H-imidazol-2-yl)amino-]-7-methyl-1H-benzimidazole-4-carbonitrile and its preferred salt form |
-
2004
- 2004-02-19 JP JP2006501895A patent/JP4554591B2/ja not_active Expired - Fee Related
- 2004-02-19 EP EP04712501A patent/EP1597227A1/en not_active Withdrawn
- 2004-02-19 KR KR1020057015457A patent/KR101053816B1/ko not_active Expired - Fee Related
- 2004-02-19 CN CNB2004800045740A patent/CN100366603C/zh not_active Expired - Fee Related
- 2004-02-19 US US10/546,291 patent/US7268255B2/en not_active Expired - Fee Related
- 2004-02-19 WO PCT/EP2004/001593 patent/WO2004074234A1/en active Application Filing
-
2005
- 2005-08-11 IL IL170253A patent/IL170253A/en not_active IP Right Cessation
-
2006
- 2006-08-14 HK HK06108991A patent/HK1088593A1/xx not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6096924A (en) * | 1995-05-19 | 2000-08-01 | Novartis Ag | Process for the catalytic hydrogeneration of aromatic nitro compounds |
| CN1284073A (zh) * | 1997-11-24 | 2001-02-14 | 宝洁公司 | 5－(2－咪唑啉基氨基)－苯并咪唑衍生物,其制备和作为具有改进的代谢稳定性的a－肾上腺素能受体激动剂的应用 |
| US6326517B1 (en) * | 1998-12-10 | 2001-12-04 | Central Glass Company, Limited | Method of producing benzamides |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050101223A (ko) | 2005-10-20 |
| WO2004074234A1 (en) | 2004-09-02 |
| IL170253A (en) | 2011-05-31 |
| JP4554591B2 (ja) | 2010-09-29 |
| KR101053816B1 (ko) | 2011-08-03 |
| US20070037985A1 (en) | 2007-02-15 |
| JP2006519201A (ja) | 2006-08-24 |
| HK1088593A1 (en) | 2006-11-10 |
| US7268255B2 (en) | 2007-09-11 |
| EP1597227A1 (en) | 2005-11-23 |
| CN1751020A (zh) | 2006-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Uberman et al. | PVP-Pd nanoparticles as efficient catalyst for nitroarene reduction under mild conditions in aqueous media | |
| CN103058942A (zh) | 一种1,2,3-三氮唑化合物的一锅法合成方法 | |
| CN100366603C (zh) | N-取代甲酰胺的制备方法 | |
| CN114957090A (zh) | 稠合异吲哚衍生物的制备方法 | |
| Zhang et al. | Synthesis of unsymmetrical 2-pyridyl ureas via selenium-catalyzed oxidative carbonylation of 2-aminopyridine with aromatic amines | |
| Ou et al. | Synthesis and crystal structure of β-hexanitrohexaazaisowurtzitane | |
| CN104262166B (zh) | 一种邻苯二胺及其衍生物的制备方法 | |
| CN1187314C (zh) | 一种合成芳胺类化合物的方法 | |
| CN107245066A (zh) | 一种选择性制备糠胺或四氢糠胺的方法 | |
| CN114031557B (zh) | 一种2-（4-氨基苯基）-5-氨基苯并咪唑的合成方法 | |
| CN118103355A (zh) | 用于制备作为荧光示踪剂的吡嗪羧酸类衍生物的氢化合成方法 | |
| CN106349295A (zh) | 含有羟基的半夹心钌配位化合物、制备方法和将硝基苯类化合物还原成苯胺类化合物的方法 | |
| Arifuddin et al. | Zinc chloride promoted efficient and facile BOC protection of amines | |
| Liu et al. | Visible-Light-Photocatalyzed C5-H Nitration of 8-Aminoquinoline Amides | |
| KR102070020B1 (ko) | 정사면체 구조인 옥타아민 화합물 및 그 제조방법 | |
| GB1571742A (en) | Process for the preparation of isoindolinone derivatives | |
| CN116789613A (zh) | 一种5-羧基苯并三氮唑的制备方法 | |
| CN107383023A (zh) | 一种6‑(2‑亚甲基喹啉)色胺酮类化合物及其合成方法 | |
| CN101624323A (zh) | 一种伯胺和仲胺类化合物的制备方法 | |
| Huang et al. | Improved synthesis of 5, 5‐diamino BINAP and application to asymmetric hydrogenation | |
| CN115677708A (zh) | 一种吡咯并喹喔啉的制备方法 | |
| Park et al. | Urea-cavitands:[1+ 1] vs.[2+ 2] Binding of Anionic Guest | |
| CN117402083A (zh) | 一种亚氨基腙中间体的制备方法 | |
| KR20170093821A (ko) | 이달로피르딘의 제조 방법 | |
| Chavan et al. | Copper (I) complexes with N-(2-quinolinylmethylene)-1, 5-dimethyl-2-phenyl-1-pyrazole-3-(2H)-one and phosphine as ligands: Effective catalyst for Sonogashira cross-coupling reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1088593 Country of ref document: HK |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1088593 Country of ref document: HK |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080206 Termination date: 20130219 |