CN1184463A - N-甲基-2-(3,4-二甲氧基苯基)乙胺的制备方法 - Google Patents
N-甲基-2-(3,4-二甲氧基苯基)乙胺的制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 20
- HNJWKRMESUMDQE-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-n-methylethanamine Chemical compound CNCCC1=CC=C(OC)C(OC)=C1 HNJWKRMESUMDQE-UHFFFAOYSA-N 0.000 title abstract 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 41
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 6
- 239000010948 rhodium Substances 0.000 claims abstract description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims abstract description 5
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 16
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 13
- -1 3,4-dimethoxyphenyl-methyl Chemical group 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- DIVNUTGTTIRPQA-UHFFFAOYSA-N (3,4-dimethoxyphenyl)methanamine Chemical compound COC1=CC=C(CN)C=C1OC DIVNUTGTTIRPQA-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 6
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000003956 methylamines Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- ASLSUMISAQDOOB-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)acetonitrile Chemical compound COC1=CC=C(CC#N)C=C1OC ASLSUMISAQDOOB-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical group CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- SGTNSNPWRIOYBX-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-{[2-(3,4-dimethoxyphenyl)ethyl](methyl)amino}-2-(propan-2-yl)pentanenitrile Chemical compound C1=C(OC)C(OC)=CC=C1CCN(C)CCCC(C#N)(C(C)C)C1=CC=C(OC)C(OC)=C1 SGTNSNPWRIOYBX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其包括在20~200℃的温度和1~300巴的压力下,在有水或无水存在下,在包含0.05~50重量%的亚铬酸铜、铜、银、金、铁、钴、镍、钌、铑、钯、锇、铱、铂或它们的混合物的催化剂的存在下,使用通式Ⅰ的甲胺和氢氢化3,4-二甲氧基苯基乙腈,其中,R1是氢、苄基或叔丁基。
Description
本发明涉及一种在升温下,在担载的包括亚铬酸铜、元素周期表IB族或VIII族的元素或它们的混合物的催化剂存在下,在有水或无水存在下通过3,4-二甲氧基苯基乙腈(藜芦基氰化物)与甲胺或取代的甲胺反应制备N-甲基-2-(3,4-二甲氧基苯基)乙胺(N-甲基高藜芦基胺)的方法,其中甲胺的取代基是在反应条件下可以被消去的基团。
DEA3338681公开了在镍催化剂上使用十倍摩尔过量的甲胺催化氢化藜芦基氰化物。作为副产物得到高藜芦基胺,其选择性大于3%,并且不得不通过加入苯甲醛以除去它。
Arch.Pharm.,271(1933)431-448公开了在甲胺和作为催化剂的钯黑的存在下将藜芦基氰化物氢化为N-甲基高藜芦基胺的氢化反应。然而,就所使用的钯而论,其产率不是令人满意的。
Ind.Eng.Chem.Prod.Res.Dev.,6(1967)142-144公开了在钯和铂催化剂上将腈催化氢化为伯、仲和叔胺的氢化反应,其主要生成叔胺。在这里甲醇被描述为催化毒物。铑被认为适合于制备仲胺。
相反,戊腈与丁胺在钯和铂上的氢化反应生成丁戊胺,但是转化率低,其分别是54%和23%。
有机反应的催化作用(Catalysis of Organic Reactions),1992,93-104)建议在由腈和伯胺制备仲胺时不要使用酸性催化剂(例如二氧化钛或氧化铝)和一般不要使用极性溶剂和尤其是不要使用甲醇。
本发明的目的是消除上述缺陷。
该目的是通过一种新的和改进的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法实现的,该方法包括在50~200℃的温度和1~300巴的压力下,在有水或无水存在下,在包括0.05~50重量%的亚铬酸铜、铜、银、金、铁、钴、镍、钌、铑、钯、锇、铱、铂或它们的混合物的催化剂的存在下,使用通式I的甲胺和氢氢化3,4-二甲氧基苯基乙腈,其中,R1是氢、苄基或叔丁基。
本发明的方法可以以下述方式进行
在20~200℃、优选50~180℃、特别优选70~160℃的温度下,在1~300巴,优选30~300巴,特别优选50~270巴的压力下,在添加或不加溶剂的情况下,在担载的包括亚铬酸铜、元素周期表IB族或VIII族的元素或它们的混合物的催化剂存在下,在有0~30,优选0.05~2.5,特别优选0.1~2重量%水的存在情况下,使3,4-二甲氧基苯基乙腈与甲胺I和氢间歇或连续地进行反应,该反应优选在压力容器或反应器(例如高压釜或管式反应器)中进行,特别优选连续地在管式反应器中进行。可以按照常规的方法(例如蒸馏)进行后处理。
合适的甲胺I特别是甲胺本身和那些被取代的甲胺,其取代基是在反应条件下可以被消除的基团,例如苄基和叔丁基,即苄基甲胺和叔丁基甲胺,优选是苄基甲胺。
苄基或叔丁基基团可优选在氢化反应条件、用加热的方法或在无机或有机酸例如硫酸、氢氯酸、甲磺酸或乙酸或在酸性催化剂例如离子交换剂或沸石的存在下被消去。
通常,甲胺与3,4-二甲氧基苯基乙腈的摩尔比是1∶1~15∶1,优选1.5∶1~10∶1,特别优选2∶1~5∶1。
合适的溶剂是具有1~8个碳原子的醇类,优选具有1~4个碳原子的醇类,N-取代的吡咯烷酮(例如N-甲基吡咯烷酮),醚类(例如四氢呋喃),芳族烃(例如苯、甲苯和二甲苯),或甲胺本身。甲醇、N-甲基吡咯烷酮、四氢呋喃、甲基苄胺和甲胺是特别优选的。
合适的包括亚铬酸铜、元素周期表IB族或VIII族的元素或它们的混合物的担载催化剂是那些在载体上的亚铬酸铜、铜、银、金、铁、钴、镍、钌、铑、钯、锇、铱、铂或它们的混合物,优选亚铬酸铜、铜、钯、铂或它们的混合物,特别优选钯、铂或它们的混合物,特别是铂的总含量是0.05~50重量%,优选0.1~10重量%,特别优选0.5~2重量%的催化剂,但是优选由它们自身组成的催化剂。
合适的载体的例子是活性炭、碳化硅或氧化物(例如氧化铝、氧化硅、二氧化钛、二氧化锆、氧化锌、氧化镁或它们的混合物),其中可以掺杂碱金属和/或碱土金属氧化物,优选γ-氧化铝、氧化硅或氧化铝/氧化硅混合物。例如载体可以以挤出物、丸状或片状的形式使用。
根据本发明的催化剂一般是通过工业上已知的方法制备的,优选是通过多孔浸渍法制备的。其包括将金属前体溶解在与载体的孔体积相当的水中,用该溶液浸渍载体,随后在例如80~170℃(优选100~150℃)的温度下干燥催化剂例如1~48小时(优选12~24小时)。干燥可以在搅拌或不搅拌的情况下进行。可以替代孔浸渍法的是使用其用量比载体的孔体积大的溶剂浸渍(使用上清液浸渍)。然后,通常在空气气流中在例如300~700℃(优选400~600℃)的温度下煅烧干燥的催化剂达0.5~10小时(优选1~3小时)。
合适的金属前体是金属盐类(例如硝酸盐、亚硝酰硝酸盐、卤化物、碳酸盐、羧酸盐、乙酰丙酮化物、氯配合物、亚硝酸配合物或胺配合物),优选硝酸盐、氯化物或氯配合物。
在含有多种金属作为活性组份的催化剂的情况下,可以同时或连续地浸渍金属前体。在分开浸渍的情况下,在每次浸渍步骤之后,在80~170℃(优选100~150℃)的温度下干燥催化剂1-48小时(优选12~24小时)。使用活性组份浸渍的顺序可以根据需要选择。
N-甲基-2-(3,4-二甲氧基苯基)乙胺[N-甲基高藜芦基胺]是药物戊脉安合成中的中间产物(US-A-3 261 859)。
实施例实施例1
在160℃和200巴下,每小时向上泵送205毫升的28%的藜芦基氰化物的甲基苄胺溶液(摩尔比是1∶3.7)以通过垂直的氢化反应器(直径:16毫米;填充高度:600毫米;油热套管),该反应器填充有511克(800毫升)催化剂(在氧化铝上0.5重量%的钯)。同时,100升(STP)/小时的氢气向上流过反应器。在降压到大气压之后,通过蒸馏除去过剩的甲基苄胺,并通过定量气相色谱法分析排出物。每小时得到40克(70%)的N-甲基高藜芦基胺。实施例2
将7克(40毫摩尔)的藜芦基氰化物和25克(200毫摩尔)的甲基苄胺与3克在氧化铝上含有4重量%钯的催化剂一起在300毫升的高压釜中加热到100℃,然后在200巴下用氢氢化10小时。降压得到6.2克(81%)的N-甲基高藜芦基胺,其转化率是100%。
实施例3
在140℃和200巴压力下,每小时向上泵送400毫升的37%的藜芦基氰化物的N-甲基吡咯烷酮溶液(含有3重量%的水)和280毫升液态甲胺(摩尔比是1∶10)以通过垂直的氢化反应器(直径:27毫米;填充高度:1500毫米;油热套管),该反应器填充有800毫升由γ-氧化铝(呈4毫米的丸状)上的0.5重量%的钯组成的催化剂。同时使200升(STP)/小时的氢气向上流过反应器。在降压到大气压之后,通过蒸馏除去过剩的甲胺,并通过定量气相色谱法分析排出物。
在经过1000多小时之后,伴随着3,4-二甲氧基苯基乙腈(藜芦基氰化物)的定量转化得到N-甲基-2-(3,4-二甲氧基苯基)乙胺(N-甲基高藜芦基胺),其产率是90%,高藜芦基胺的含量低于1%。催化剂的制备催化剂A:三氧化二铝上0.5重量%的钯
使用570毫升的硝酸钯(II)的硝酸溶液浸渍1000克氧化铝载体(该载体为2~4毫米的丸状,其表观密度是755克/升,孔体积是0.57立方厘米/克和表面积是238平方米/克),在120℃下,在不搅拌的情况下干燥18小时和在450℃下煅烧3小时。催化剂B:三氧化二铝上1重量%的铂
使用1097毫升的硝酸铂(II)的水溶液浸渍1613克氧化铝载体(该载体为4毫米的挤出物,其表观密度是560克/升,孔体积是0.68立方厘米/克和表面积是203平方米/克),在120℃下,在不搅拌的情况下干燥20小时和在450℃下煅烧3小时。催化剂C:氧化硅/三氧化二铝上0.8重量%的铂
使用970毫升的氯化铂(II)的盐酸溶液浸渍1032克由80重量%的氧化硅和20重量%的氧化铝组成的氧化硅/氧化铝载体(该载体为3毫米的挤出物,其表观密度是463克/升,孔体积是0.94立方厘米/克和表面积是167平方米/克);在120℃下,在不搅拌的情况下干燥20小时和在450℃下煅烧3小时。催化剂D:氧化硅/三氧化二铝上0.4重量%的铂/0.4重量%的钯
使用97 0毫升的包含氯化铂(II)和氯化钯(II)的盐酸溶液浸渍催化剂C中描述的氧化硅/氧化铝载体;在120℃下,在不搅拌的情况下干燥20小时和在450℃下煅烧3小时。催化剂E:氧化硅/三氧化二铝上0.8重量%的钯
使用970毫升的包含氯化钯(II)的盐酸溶液浸渍催化剂C中描述的氧化硅/氧化铝载体;在120℃下,在不搅拌的情况下干燥20小时和在450℃下煅烧3小时。催化剂F:氧化硅/三氧化二铝上0.8重量%的钯
制备方法与催化剂E的相同,除了被浸渍的催化剂在旋转管中搅拌的情况下在120℃下干燥1小时和在450℃下煅烧1小时。催化剂G:在氧化硅上的0.8重量%的钯
使用1398毫升的氯化钯(II)的盐酸溶液浸渍1520克氧化硅载体(该载体为3~5毫米的丸状,其表观密度是489克/升,孔体积是0.92立方厘米/克和表面积是336平方米/克);在120℃下,在旋转管中搅拌的情况下干燥1小时和在450℃下煅烧1小时。实施例4~11
在140℃和80巴下,每小时向上泵送27毫升的37%的藜芦基氰化物溶液和10毫升液态甲胺(摩尔比是1∶5)以通过垂直的氢化反应器(直径:16毫米;填充高度:400毫米;油热套管),该反应器填充有80毫升来自于下表的催化剂。同时使10升(STP)/小时的氢气向上流过反应器。在降压到大气压之后,通过蒸馏除去过剩的甲胺,并通过定量气相色谱法分析排出物。
表
实施例 | 催化剂 | 溶剂 | 转化率 | 选择性 | 产率 | HVA |
No. | [%] | [%] | [%] | [%] | ||
4 | A | 甲醇 | 95 | 65 | 60 | <1 |
5 | B | 甲醇 | 100 | 85 | 83 | <1 |
6 | C | 甲醇 | 99 | 94 | 91 | <1 |
7 | D | 甲醇 | 100 | 75 | 73 | <1 |
8 | E | 甲醇 | 100 | 80 | 78 | <1 |
9 | E | NMP | 99 | 95 | 88 | <1 |
10 | F | NMP | 99 | 93 | 84 | <1 |
11 | G | NMP | 99 | 99 | 94 | <1 |
转化率=藜芦基氰化物转化率 | ||||||
选择性=N-甲基高藜芦基胺选择性 | ||||||
NMP=N-甲基吡咯烷酮 | ||||||
HVA=高藜芦基胺 |
Claims (10)
1、一种制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其包括在20~200℃的温度和1~300巴的压力下,在有水或无水存在下,在包含0.05~50重量%的亚铬酸铜、铜、银、金、铁、钴、镍、钌、铑、钯、锇、铱、铂或它们的混合物的催化剂的存在下使用通式I的甲胺和氢氢化3,4-二甲氧基苯基乙腈,其中,R1是氢、苄基或叔丁基。
2、根据权利要求1的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中使用通式I的化合物作为甲胺,这里R1是氢或苄基。
3、根据权利要求1的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中使用通式I的化合物作为甲胺,这里R1是氢。
4、根据权利要求1~3任一项的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中担载的催化剂包括0.1~10重量%的亚铬酸铜、铜、银、金、铁、钴、镍、钌、铑、钯、锇、铱、铂或它们的混合物。
5、根据权利要求1~4任一项的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中担载的催化剂包括亚铬酸铜、铜、镍、钌、钯、铂或它们的混合物。
6、根据权利要求1~5任一项的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中担载的催化剂包括钌、钯、铂或它们的混合物。
7、根据权利要求1~6任一项的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中担载的催化剂包括钯。
8、根据权利要求1~7任一项的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中水与3,4-二甲氧基苯基乙腈的摩尔比是0.05∶1~2.5∶1。
9、根据权利要求1~8任一项的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中甲胺与3,4-二甲氧基苯基乙腈的摩尔比是1∶1~15∶1。
10、根据权利要求1~9任一项的制备N-甲基-2-(3,4-二甲氧基苯基)乙胺的方法,其中使用活性炭、氧化铝、氧化硅、二氧化钛、二氧化锆、氧化锌、氧化镁、碳化硅或它们的混合物作为载体。
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DE1995118038 DE19518038A1 (de) | 1995-05-17 | 1995-05-17 | Verfahren zur Herstellung von N-Methyl-2-(3,4-dimethoxyphenyl)-ethylamin |
DE19518018.6 | 1995-05-17 | ||
DE19518038.0 | 1995-05-17 | ||
DE1995118018 DE19518018A1 (de) | 1995-05-17 | 1995-05-17 | Verfahren zur Herstellung von N-Methyl-2-(3,4-dimethoxyphenyl)-ethylamin |
DE19606729.4 | 1996-02-23 | ||
DE1996106729 DE19606729A1 (de) | 1996-02-23 | 1996-02-23 | Verfahren zur Herstellung von N-Methyl-2-(3,4-dimethoxyphenyl)-ethylamin |
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CN114853728A (zh) * | 2022-05-07 | 2022-08-05 | 四川制药制剂有限公司 | 一种富马酸伏诺拉生片及其制备方法 |
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DE19756947A1 (de) * | 1997-12-22 | 1999-06-24 | Basf Ag | Verfahren zur Herstellung sekundärer Amine aus Nitrilen und primären Aminen |
DE19942300A1 (de) | 1999-09-04 | 2001-03-08 | Basf Ag | Verfahren zur Herstellung von Alkanolaminen mit verbesserter Farbqualität |
US20100019191A1 (en) * | 2006-12-15 | 2010-01-28 | Basf Se | Method for producing 1,2-ethylene glycol and 1,2-propylene glycol by means of the heterogeneously catalysed hydrogenolysis of a polyol |
US7538060B2 (en) * | 2007-02-14 | 2009-05-26 | Eastman Chemical Company | Palladium-copper chromite hydrogenation catalysts |
US20080194398A1 (en) * | 2007-02-14 | 2008-08-14 | Eastman Chemical Company | Ruthenium-copper chromite hydrogenation catalysts |
JP2010536913A (ja) * | 2007-08-29 | 2010-12-02 | ビーエーエスエフ ソシエタス・ヨーロピア | グリセリンからのアミンの製造方法 |
WO2009027249A2 (de) * | 2007-08-29 | 2009-03-05 | Basf Se | Verfahren zur herstellung von aminen aus zuckeralkoholen |
CN102203054B (zh) | 2008-11-05 | 2014-07-30 | 巴斯夫欧洲公司 | 生产n,n-取代的3-氨基丙-1-醇的方法 |
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IT1229214B (it) * | 1989-03-31 | 1991-07-25 | Alfa Wassermann S P A Contrada | Processo per la sintesi della n metil 3,4 dimetossifeniletilamina |
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CN114853728A (zh) * | 2022-05-07 | 2022-08-05 | 四川制药制剂有限公司 | 一种富马酸伏诺拉生片及其制备方法 |
CN114853728B (zh) * | 2022-05-07 | 2023-11-07 | 四川制药制剂有限公司 | 一种富马酸伏诺拉生片及其制备方法 |
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HUP9801069A3 (en) | 2000-06-28 |
AU5813496A (en) | 1996-11-29 |
SK281665B6 (sk) | 2001-06-11 |
CZ345597A3 (cs) | 1998-04-15 |
HUP9801069A2 (hu) | 1999-05-28 |
BR9608468A (pt) | 1998-12-29 |
TR199701373T1 (xx) | 1998-02-21 |
PL323359A1 (en) | 1998-03-30 |
US5840981A (en) | 1998-11-24 |
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WO1996036589A1 (de) | 1996-11-21 |
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