CN114181090A - 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 - Google Patents
由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 Download PDFInfo
- Publication number
- CN114181090A CN114181090A CN202010969949.8A CN202010969949A CN114181090A CN 114181090 A CN114181090 A CN 114181090A CN 202010969949 A CN202010969949 A CN 202010969949A CN 114181090 A CN114181090 A CN 114181090A
- Authority
- CN
- China
- Prior art keywords
- amide
- iridium
- boron
- hydrosilation
- synthesis
- 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
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 36
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 34
- 150000001408 amides Chemical class 0.000 title claims abstract description 32
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 30
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 19
- -1 amine compound Chemical class 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000000746 purification Methods 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical group CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001343 alkyl silanes Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 238000006722 reduction reaction Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FVNFBBAOMBJTST-UHFFFAOYSA-N 8-(2-phenylethyl)-1-oxa-3,8-diazaspiro[4.5]decan-2-one Chemical compound O1C(=O)NCC11CCN(CCC=2C=CC=CC=2)CC1 FVNFBBAOMBJTST-UHFFFAOYSA-N 0.000 description 2
- CEUORZQYGODEFX-UHFFFAOYSA-N Aripirazole Chemical compound ClC1=CC=CC(N2CCN(CCCCOC=3C=C4NC(=O)CCC4=CC=3)CC2)=C1Cl CEUORZQYGODEFX-UHFFFAOYSA-N 0.000 description 2
- GDLIGKIOYRNHDA-UHFFFAOYSA-N Clomipramine Chemical compound C1CC2=CC=C(Cl)C=C2N(CCCN(C)C)C2=CC=CC=C21 GDLIGKIOYRNHDA-UHFFFAOYSA-N 0.000 description 2
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 2
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229960004372 aripiprazole Drugs 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- APEJMQOBVMLION-UHFFFAOYSA-N cinnamamide Chemical compound NC(=O)C=CC1=CC=CC=C1 APEJMQOBVMLION-UHFFFAOYSA-N 0.000 description 2
- 229960004606 clomipramine Drugs 0.000 description 2
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- WSEQXVZVJXJVFP-FQEVSTJZSA-N escitalopram Chemical compound C1([C@]2(C3=CC=C(C=C3CO2)C#N)CCCN(C)C)=CC=C(F)C=C1 WSEQXVZVJXJVFP-FQEVSTJZSA-N 0.000 description 2
- 229960004341 escitalopram Drugs 0.000 description 2
- 229960002912 fenspiride Drugs 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 229960003376 levofloxacin Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 2
- UHFFQIFQGQFRKG-UHFFFAOYSA-N n,n-dibenzylhexadecan-1-amine Chemical compound C=1C=CC=CC=1CN(CCCCCCCCCCCCCCCC)CC1=CC=CC=C1 UHFFQIFQGQFRKG-UHFFFAOYSA-N 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 238000006268 reductive amination reaction Methods 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- PTIVSZNNOUZBKM-UHFFFAOYSA-N 1-benzylazepane Chemical compound C=1C=CC=CC=1CN1CCCCCC1 PTIVSZNNOUZBKM-UHFFFAOYSA-N 0.000 description 1
- 206010002383 Angina Pectoris Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 208000004756 Respiratory Insufficiency Diseases 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000935 antidepressant agent Substances 0.000 description 1
- 229940005513 antidepressants Drugs 0.000 description 1
- 239000003693 atypical antipsychotic agent Substances 0.000 description 1
- 229940127236 atypical antipsychotics Drugs 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- HSUGRBWQSSZJOP-RTWAWAEBSA-N diltiazem Chemical compound C1=CC(OC)=CC=C1[C@H]1[C@@H](OC(C)=O)C(=O)N(CCN(C)C)C2=CC=CC=C2S1 HSUGRBWQSSZJOP-RTWAWAEBSA-N 0.000 description 1
- 229960004166 diltiazem Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- VEQBFCHDNFXWFH-UHFFFAOYSA-N n,n-dibenzylbenzamide Chemical compound C=1C=CC=CC=1C(=O)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 VEQBFCHDNFXWFH-UHFFFAOYSA-N 0.000 description 1
- LKQUCICFTHBFAL-UHFFFAOYSA-N n-benzylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NCC1=CC=CC=C1 LKQUCICFTHBFAL-UHFFFAOYSA-N 0.000 description 1
- WXXHOQJPLCZXLB-UHFFFAOYSA-N n-methyl-n-phenylnaphthalen-2-amine Chemical compound C=1C=C2C=CC=CC2=CC=1N(C)C1=CC=CC=C1 WXXHOQJPLCZXLB-UHFFFAOYSA-N 0.000 description 1
- CICSJMNWCSOMDH-UHFFFAOYSA-N n-methyl-n-phenylnaphthalene-2-carboxamide Chemical compound C=1C=C2C=CC=CC2=CC=1C(=O)N(C)C1=CC=CC=C1 CICSJMNWCSOMDH-UHFFFAOYSA-N 0.000 description 1
- OZGNYLLQHRPOBR-DHZHZOJOSA-N naftifine Chemical compound C=1C=CC2=CC=CC=C2C=1CN(C)C\C=C\C1=CC=CC=C1 OZGNYLLQHRPOBR-DHZHZOJOSA-N 0.000 description 1
- 229960004313 naftifine Drugs 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 description 1
- 201000004193 respiratory failure Diseases 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/04—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with only hydrogen atoms, halogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/643—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of R2C=O or R2C=NR (R= C, H)
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，步骤如下：在有机溶剂中，将酰胺和硅烷在铱络合物和硼试剂的催化下反应，随后经浓缩、纯化得到胺；酰胺:铱络合物:硼试剂:硅烷的摩尔比为1:0.0001～0.001:0.01～0.05:2～4；本发明以稳定易得的酰胺为原料，以非常低的催化剂负载量铱络合物与硼试剂共催化硅氢化，高效率地合成胺类化合物。本发明各步骤操作、分离简单，反应速率快，反应条件温和，所用的试剂均为廉价易得的商品化试剂，产率高，官能团容忍性好。
Description
技术领域
本发明涉及胺类化合物的制备领域，尤其涉及由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法。
背景技术
胺作为一类重要的化合物，往往是具有生物活性的天然产物和药物分子中重要的结构单元，如新型抗抑郁药草酸艾斯西酞普兰(Escitalopram,2.1和氯米帕明(Clomipramine,2.5)、非典型抗精神病药物阿立哌唑(Aripiprazole 2.2和喹诺酮类抗菌药左氧氟沙星(Levofloxacin,2.3)、治疗慢性支气管炎和呼吸功能不全的芬司匹利(Fenspiride,2.4)和钙离子阻断剂的降血压及预防心绞痛药物地尔硫卓(Diltiazem,2.6)等。此外，胺类化合物在农药、矿物浮选、腐蚀抑制剂、润滑剂等领域亦具有广泛的用途。因此，发展一种高效合成胺的方法对于众多领域有着重要意义。
胺类化合物在医药、农药等领域具有广泛的用途，目前，已经有许多方法被发展用于胺的制备。胺的常规合成方法是指在催化剂存在下用常规加热器加热(或高压)合成胺类化合物的一般方法，下面介绍几种胺类合成的方法。
硝基化合物经化学还原或是催化氢化合成胺，化学还原又分金属还原和金属氢化物还原。
还原胺化反应是一种简便的把醛酮转换成胺的方法。醛酮的还原胺化可分为两步，先是将羰基跟胺脱水生成亚胺(西弗碱)，然后经硼氢化钠或者氰基硼氢化钠还原成胺。
将腈基还原成伯胺较为容易，利用氢化将氰基还原制备伯胺的方法在工艺上已经比较成熟，可以用来催化腈的氢化还原的催化剂有很多，如氧化铂、镍、钯、钴和硼化镍等。
叠氮化合物的还原，叠氮基可方便地通过无机叠氮化合物引入到有机分子中，主要是对分子中的卤素(通常是溴)进行亲核取代，然后通过合适的试剂将其还原成胺。此外还可以通过适当的试剂在温和的条件下，在叠氮基还原成氨基时对氨基进行保护。该方法还可用于制取采用其它方法不易合成的胺类化合物。
氮原子上无取代基的酰胺与次氯酸钠或次溴酸钠的碱溶液作用时，脱去羰基生成伯胺，在反应中碳链减少一个碳原子。这是霍夫曼所发现制胺的方法，通常称为霍夫曼降解反应。
酰胺还原是有机合成中的重要反应之一，也是合成胺的一种常用的方法。通过选择合适的反应条件，可以将酰胺(包括内酰胺)还原成醛、醇、亚胺或胺等不同的目标产物，其中以酰胺还原成胺最为重要。传统的酰胺还原为胺的方法需要多步骤。例如，首先用Lawesson试剂或P4S10把酰胺制成硫代酰胺，再用Ni试剂通过脱硫作用，经过两步将酰胺还原为胺。
近十年来，发展了许多金属如Mo,Ru,Co,Rh,Ir,Os,Pt,In,Ti,Mn,等催化直接还原法，但皆因催化剂不易得或反应条件苛刻而少有实际应用价值。
发明内容
本发明的目的在于解决现有技术中的上述问题，提供由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其是以稳定易得的酰胺为原料，经铱络合物与硼试剂共同催化硅氢化反应，高产率地合成胺类化合物。
为达到上述目的，本发明采用如下技术方案：
由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，步骤如下：在有机溶剂中，将酰胺和硅烷在铱络合物和硼试剂的催化下反应，随后经浓缩、纯化得到胺；合成路线如下：
其中，R1和R2选自氢、烷基或芳基；R3选自氢、烷基、芳基或烷氧基；[Ir]为铱络合物，[B]为硼试剂，Si-H为硅烷。
所述烷基选自C1～C20的烷基，所述芳基选自C6～C20的芳基，所述烷氧基选自C1～C7的烷氧基。
本发明中，酰胺:铱络合物:硼试剂:硅烷的摩尔比为1:0.0001～0.001:0.01～0.05:2～4。
所述铱络合物包括IrCl(CO)(PPh3)2。
所述硼试剂包括(C6F5)3B(三五氟苯基硼)。
所述硅烷选自烷氧基硅烷或烷基硅烷，例如(EtO)3SiH(三乙氧基硅烷)、Et3SiH(三乙基硅烷)、PMHS(聚甲基氢硅烷)、TMDS(1,1,3,3-四甲基二硅氧烷)、Et2SiH2(二乙基硅烷)或Ph2SiH2(二苯基硅烷)等。
所述有机溶剂选自醚、卤代烃或者芳香烃。所述醚选自C2～C6的醚，所述卤代烃选自C1～C6的卤代烃。优选地，所述有机溶剂选自四氢呋喃、2-甲基四氢呋喃、二氯甲烷、二氯乙烷、甲苯或二甲苯。
相对于现有技术，本发明技术方案取得的有益效果是：
本发明以稳定易得的酰胺为原料，以非常低的催化剂负载量铱络合物与硼试剂共催化硅氢化，高效率地合成胺类化合物。本发明各步骤操作、分离简单，反应速率快，反应条件温和，所用的试剂均为廉价易得的商品化试剂，产率高，官能团容忍性好。
具体实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚、明白，以下结合实施例，对本发明做进一步详细说明。
实施例1
合成N-甲基-N-(2-萘基)苯胺(a)
将N-甲基-N-苯基-2-萘甲酰胺(261mg)溶于甲苯中，于室温下依次加入铱络合物[IrCl(CO)(PPh3)2](8mg)，硅烷TMDS(1，1，3，3-四甲基二硅氧烷)(0.36mL)和B(C6F5)3(15mg)。搅拌反应后浓缩，纯化后得白色固体a(240mg,产率97％)。IR(film)vmax:3052,2962,2819,1598,1505,1367,1119,939,812,747cm-1；1H NMR(400MHz,CDCl3)δ3.02(s,3H),4.63(s,2H),6.66-6.83(m,2H),7.17-7.28(m,2H),7.30-7.50(m,3H),7.60-7.69(m,1H),7.71-7.85(m,3H)ppm；13C NMR(100MHz,CDCl3)δ38.6,57.1,112.5,112.6,116.8,125.2,125.3,125.6,126.2,127.7,128.4,129.3,132.8,133.6,136.7,149.9ppm；MS(ESI,m/z):247(M+H+)。
实施例2
合成1-苄基氮杂环庚烷(b)
1-苄基氮杂-2-酮(203mg)溶于四氢呋喃中，于室温下依次加入铱络合物[IrCl(CO)(PPh3)2](8mg，1mol％)，B(C6F5)3(15mg)和硅烷TMDS(1，1，3，3-四甲基二硅氧烷)(0.36mL)。搅拌反应后浓缩，得到无色液体b(168mg,产率89％)。IR(film)vmax:3021,2921,2847,2979,1490,1453,1353cm-1；1H NMR(400MHz,CDCl3)δ1.67(s,8H),2.68(s,4H),3.69(s,2H),7.21-7.49(m,5H)ppm；13C NMR(100MHz,CDCl3)δ27.0,28.2,55.6,62.7,126.6,128.0,128.7,140.0ppm；MS(ESI,m/z):189.4(M+H+)。
实施例3
合成萘替芬(c)
将N-甲基-N-(1-萘甲基)肉桂酰胺(301mg)溶于甲苯中，于室温下依次加入铱络合物[IrCl(CO)(PPh3)2](8mg，1mol％)，TMDS(0.36mL)和B(C6F5)3(15mg)。搅拌反应后浓缩，纯化后得浅黄色液体c(178mg,产率62％)。IR(film)vmax:3022,2985,2782,1494,1369,1065cm-1；1H NMR(400MHz,CDCl3)δ2.27(s,3H),3.27(dd,J＝6.6,1.1Hz,2H),3.94(s,2H),6.36(dt,J＝15.9,6.6Hz,1H),6.56(d,J＝15.9Hz,1H),7.24-7.17(m,1H),7.33-7.27(m,2H),7.55-7.35(m,6H),7.76(d,J＝8.0Hz,1H),7.83(dd,J＝8.3,1.0Hz,1H),8.30(d,J＝8.4Hz,1H)ppm；13C NMR(100MHz,CDCl3)δ42.4,60.0,60.4,124.6,125.1,125.5,125.9,126.3,127.3,127.4,127.5,127.9,128.4,128.5,132.4,132.6,133.8,134.8,137.1ppm；MS(ESI,m/z):287.1(M+H+)。
实施例4
合成三苄基胺(d)
将N,N-二苄基苯甲酰胺(301mg)溶于甲苯中，于室温下依次加入铱络合物[IrCl(CO)(PPh3)2](0.08mg，0.01mol％)，硅烷TMDS(0.36mL)和B(C6F5)3(15mg)。搅拌反应后浓缩，纯化后得浅黄色液体d(281mg,产率98％)。IR(film)vmax:3082,3062,3028,2925,2881,2837,2802,1603,1493,1452,1366,1247,1122,1028cm-1；1H NMR(400MHz,CDCl3)δ3.55(s,6H),7.18-7.26(m,3H),7.26-7.35(m,6H),7.37-7.43(m,6H)ppm；13C NMR(100MHz,CDCl3)δ57.9,126.9,128.2,128.8,139.7ppm；MS(ESI,m/z):288.3(M+H+).
实施例5
合成N,N-二苄基十六烷胺(e)
N,N-二苄基棕榈酰胺(435mg)溶于甲苯中，于室温下依次加入铱络合物[IrCl(CO)(PPh3)2](0.08mg,0.01mol％)，硅烷TMDS(0.36mL)和B(C6F5)3(15mg。搅拌反应后浓缩，纯化后得浅黄色液体e(391mg,产率93％)。IR(film)vmax:3085,3027,3026,2924,2793,1601,1453,1365,1259,1074,743,697cm-1；1H NMR(500MHz,CDCl3)δ0.87(t,J＝7.1Hz,3H),1.16-1.32(m,26H),1.45-1.53(m,2H),2.38(t,J＝7.2Hz,2H),3.53(s,4H),7.16-7.20(m,2H),7.26-7.29(m,4H),7.34-7.35(m,4H)ppm；13C NMR(125MHz,CDCl3)δ14.1,22.7,27.0,27.3,29.4,29.5,29.7(2C),29.70(2C),29.73(4C),31.95,53.42,58.3,126.7,128.1,128.7,140.1ppm；HRMS-ESI calcd for[C30H48N]+(M+H+):422.3781；found:422.3784.
实施例6
合成二苄胺(f)
N-苄基苯甲酰胺(211mg)溶于甲苯中，于室温下依次加入铱络合物[IrCl(CO)(PPh3)2](8mg,1mol％)、硅烷TMDS(0.36mL)和B(C6F5)3(30mg)。搅拌反应后浓缩，纯化后得浅黄色液体f(63mg,产率32％)。IR(film)νmax:3332,3083,3061,3024,2917,2817,1494,1452,1109,1027cm-1；1H NMR(400MHz,CDCl3)δ1.68(s,1H),3.80(s,4H),7.19-7.40(m,10H)ppm；13C NMR(100MHz,CDCl3)δ53.2,127.0,128.2,128.4,140.4ppm；MS(ESI,m/z):198(M+H+).
Claims (10)
1.由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于步骤如下：在有机溶剂中，将酰胺和硅烷在铱络合物和硼试剂的催化下反应，随后经浓缩、纯化得到胺；合成路线如下：
其中，R1和R2选自氢、烷基或芳基；R3选自氢、烷基、芳基或烷氧基；[Ir]为铱络合物，[B]为硼试剂，Si-H为硅烷。
2.如权利要求1所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述烷基选自C1～C20的烷基，所述芳基选自C6～C20的芳基，所述烷氧基选自C1～C7的烷氧基。
3.如权利要求1所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：酰胺:铱络合物:硼试剂:硅烷的摩尔比为1:0.0001～0.001:0.01～0.05:2～4。
4.如权利要求1所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述铱络合物包括IrCl(CO)(PPh3)2。
5.如权利要求1所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述硼试剂包括(C6F5)3B。
6.如权利要求1所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述硅烷选自烷氧基硅烷或烷基硅烷。
7.如权利要求6所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述硅烷选自(EtO)3SiH、Et3SiH、PMHS、TMDS，Et2SiH2或Ph2SiH2。
8.如权利要求1所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述有机溶剂选自醚、卤代烃或者芳香烃。
9.如权利要求8所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述醚选自C2～C6的醚，所述卤代烃选自C1～C6的卤代烃。
10.如权利要求8所述的由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法，其特征在于：所述有机溶剂选自四氢呋喃、2-甲基四氢呋喃、二氯甲烷、二氯乙烷、甲苯或二甲苯。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010969949.8A CN114181090B (zh) | 2020-09-15 | 2020-09-15 | 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010969949.8A CN114181090B (zh) | 2020-09-15 | 2020-09-15 | 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114181090A true CN114181090A (zh) | 2022-03-15 |
| CN114181090B CN114181090B (zh) | 2023-04-28 |
Family
ID=80601261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010969949.8A Active CN114181090B (zh) | 2020-09-15 | 2020-09-15 | 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114181090B (zh) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484385A (zh) * | 2019-01-28 | 2020-08-04 | 中国科学院上海有机化学研究所 | 一种有机硼和无机碱催化酰胺的硅氢化反应方法 |
-
2020
- 2020-09-15 CN CN202010969949.8A patent/CN114181090B/zh active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484385A (zh) * | 2019-01-28 | 2020-08-04 | 中国科学院上海有机化学研究所 | 一种有机硼和无机碱催化酰胺的硅氢化反应方法 |
Non-Patent Citations (3)
| Title |
|---|
| RYAN C. CHADWICK等: "Metal-Free Reduction of Secondary and Tertiary N‑Phenyl Amides by Tris(pentafluorophenyl)boron-Catalyzed Hydrosilylation", 《J. ORG. CHEM. 》 * |
| TATIANA ROGOVA等: "Reverse Polarity Reductive Functionalization of Tertiary Amides via a Dual Iridium-Catalyzed Hydrosilylation and Single Electron Transfer Strategy", 《ACS CATAL.》 * |
| YANN CORRE等: "Efficient and selective hydrosilylation of secondary and tertiary amides using an iridium(III) metallacycle catalyst: development and mechanistic investigation", 《CHEMCATCHEM》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114181090B (zh) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI540138B (zh) | 有機胺基矽烷及其製造方法 | |
| CN113877630B (zh) | 一种制备双[(3-二甲基氨基)丙基]胺的催化剂及其应用 | |
| EP1478651B1 (en) | Preparation of n-substituted aminoorganosilanes | |
| CN114181090B (zh) | 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 | |
| Shuai et al. | Metal-free chemoselective reduction of nitroaromatics to anilines via hydrogen transfer strategy | |
| CN1198790C (zh) | 制备4－氨基二苯胺的方法 | |
| CN104803835B (zh) | 一种制备苯甲醛及其衍生物的方法 | |
| CN107382741B (zh) | 催化炔烃和胺的分子间氢胺化反应的方法 | |
| CN109651159A (zh) | 一种氢转移选择性还原腈类制备伯胺的方法 | |
| CN113773206B (zh) | 一种二氧化碳参与的布替萘芬的制备方法 | |
| CN109651160A (zh) | 一种催化苯乙炔氢胺化反应制备烯胺类化合物的方法 | |
| CN114588929A (zh) | 一种负载型铜纳米团簇催化剂及其在aha偶联反应中的应用 | |
| US6689913B2 (en) | Process for preparing terbinafine and HCI salt thereof | |
| CN107556226B (zh) | 一种拉曲替尼中间体的制备方法 | |
| CN102950025B (zh) | 一种亚胺不对称加氢催化剂及其用途 | |
| CN109384681B (zh) | 一种合成盐酸美西律的方法 | |
| JP2014172847A (ja) | 芳香族アミン化合物の製造方法 | |
| WO2019053382A1 (fr) | Nouveau procede de stockage de l'hydrogene | |
| CN112521289B (zh) | 一种氧杂烯丙基胺类化合物及其制备方法和应用 | |
| JP4643566B2 (ja) | Ｎ−アシルヒドラゾンのアリル化方法 | |
| CN116253648A (zh) | 一种无金属参与的芳胺化合物合成方法 | |
| CN109912538B (zh) | 一种抗抑郁药沃替西汀的制备方法 | |
| CN110292948B (zh) | 含单亚胺功能化的咪唑氯盐作为催化剂在制备芳香杂环甲酸酯类化合物中的应用 | |
| CN107445879B (zh) | 拉曲替尼中间体的制备方法 | |
| CN107216255B (zh) | 一种硝基苯乙炔加氢制备氨基苯乙炔的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |