CN106861757B - A kind of organic boron of fluorescent marker/nitrogen lewis acid base bifunctional catalyst and preparation method thereof - Google Patents
A kind of organic boron of fluorescent marker/nitrogen lewis acid base bifunctional catalyst and preparation method thereof Download PDFInfo
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- CN106861757B CN106861757B CN201710133198.4A CN201710133198A CN106861757B CN 106861757 B CN106861757 B CN 106861757B CN 201710133198 A CN201710133198 A CN 201710133198A CN 106861757 B CN106861757 B CN 106861757B
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- -1 nitrogen lewis acid Chemical class 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 239000002841 Lewis acid Substances 0.000 title claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 7
- 230000001588 bifunctional effect Effects 0.000 title claims description 10
- 239000003550 marker Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 328
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011630 iodine Substances 0.000 claims abstract description 9
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000003385 sodium Chemical class 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 292
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 140
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 48
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 16
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000003248 quinolines Chemical class 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 229940111121 antirheumatic drug quinolines Drugs 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- ORQWTLCYLDRDHK-UHFFFAOYSA-N phenylselanylbenzene Chemical compound C=1C=CC=CC=1[Se]C1=CC=CC=C1 ORQWTLCYLDRDHK-UHFFFAOYSA-N 0.000 claims description 2
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 claims description 2
- 239000001230 potassium iodate Substances 0.000 claims description 2
- 229940093930 potassium iodate Drugs 0.000 claims description 2
- 235000006666 potassium iodate Nutrition 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 claims 1
- 125000005246 nonafluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 229910052714 tellurium Inorganic materials 0.000 claims 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000006683 Mannich reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 110
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 105
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 82
- KFDXGMWQQNKTOC-UHFFFAOYSA-N 2-[(2-anilinophenyl)methyl]cyclohexan-1-one Chemical compound N(C1=CC=CC=C1)C1=C(CC2C(CCCC2)=O)C=CC=C1 KFDXGMWQQNKTOC-UHFFFAOYSA-N 0.000 description 48
- 230000003197 catalytic effect Effects 0.000 description 45
- 239000012299 nitrogen atmosphere Substances 0.000 description 44
- 238000000926 separation method Methods 0.000 description 43
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 41
- 238000001514 detection method Methods 0.000 description 40
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 150000001299 aldehydes Chemical class 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- CUYLPYBYCYQGCE-UHFFFAOYSA-N 2-benzylcyclohexan-1-one Chemical compound O=C1CCCCC1CC1=CC=CC=C1 CUYLPYBYCYQGCE-UHFFFAOYSA-N 0.000 description 6
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- UXJMXERXJQAWSP-UHFFFAOYSA-N 2-pentylcyclohexan-1-one Chemical compound CCCCCC1CCCCC1=O UXJMXERXJQAWSP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VCDPHYIZVFJQCD-ZRDIBKRKSA-N (2e)-2-benzylidenecyclohexan-1-one Chemical compound O=C1CCCC\C1=C/C1=CC=CC=C1 VCDPHYIZVFJQCD-ZRDIBKRKSA-N 0.000 description 1
- JTLNYEGYOSBRDX-UHFFFAOYSA-N 1-nitroethyne Chemical group [O-][N+](=O)C#C JTLNYEGYOSBRDX-UHFFFAOYSA-N 0.000 description 1
- VCDPHYIZVFJQCD-UHFFFAOYSA-N 2-benzylidenecyclohexan-1-one Chemical compound O=C1CCCCC1=CC1=CC=CC=C1 VCDPHYIZVFJQCD-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- WDNOUBDSBVPCIT-UHFFFAOYSA-N CC1=CC=C(C=C1)C2CCCC(=O)C2(C)NC3=CC=CC=C3 Chemical compound CC1=CC=C(C=C1)C2CCCC(=O)C2(C)NC3=CC=CC=C3 WDNOUBDSBVPCIT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- GMDBEEZCZPKKOV-UHFFFAOYSA-N [O-][N+](C(C=C1)=CC=C1C(NC1=C(CC(CCCC2)C2=O)C=CC=C1)=O)=O Chemical compound [O-][N+](C(C=C1)=CC=C1C(NC1=C(CC(CCCC2)C2=O)C=CC=C1)=O)=O GMDBEEZCZPKKOV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- BFMYDTVEBKDAKJ-UHFFFAOYSA-L disodium;(2',7'-dibromo-3',6'-dioxido-3-oxospiro[2-benzofuran-1,9'-xanthene]-4'-yl)mercury;hydrate Chemical compound O.[Na+].[Na+].O1C(=O)C2=CC=CC=C2C21C1=CC(Br)=C([O-])C([Hg])=C1OC1=C2C=C(Br)C([O-])=C1 BFMYDTVEBKDAKJ-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4283—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using N nucleophiles, e.g. Buchwald-Hartwig amination
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- 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)
- Catalysts (AREA)
Abstract
The present invention is a kind of difunctional organic boron nitrogen fluorescence lewis acid base catalyst and preparation method thereof.It is characterized in that, using quinoline amides compound, cheap tetraphenylboron sodium analog derivative as raw material, using iodine that is cheap, being easy to get as catalyst, with there are commonly solvents to make reaction dissolvent, certain time is reacted in reaction at a certain temperature, and high yield obtains difunctional organic boron/nitrogen fluorescence lewis acid base catalyst with high selectivity.The catalyst stability is good, can be recycled, and have extraordinary non-corresponding stereoselectivity in Mannich reaction.This method has the advantages that cost is relatively low, and yield is high, easy to operate, pollution-free, for realizing that its industrialized production has certain feasibility.
Description
[technical field]
The invention belongs to be catalyzed organic synthesis field, a kind of novel quinoline ion organic boron nitrogen Louis is related in particular to
Acid catalyst and preparation method thereof.
[background technique]
Organic base bifunctional catalyst has higher due to that can cooperate with activation nucleopilic reagent and electrophilic reagent
Regio- and stereo-selectivity, therefore be widely used in organic synthesis field.But compare metallic catalyst, organic catalyst by
It is lower in its intrinsic physicochemical properties its catalytic activity similar with organic synthesis product, therefore usually additive amount reaches
The residual of catalyst caused by 5-10mol% is more, but for product, the catalyst of this low concentration (<
It is a problem that 1mol%) how residual comes out quickly through spectral detection, and for pharmaceutical chemistry, list is miscellaneous must not be big
Strict demand in 0.1% seriously limits application of the Organic base bifunctional catalyst inside pharmaceutical synthesis.Closely
Nian Lai, fluorochrome label chemistry unique luminous, lower detection limit, high sensitivity and good heat since material has
Stability and favor by chemist.Ionic organic quinolines boron compound fluorescence quantum efficiency with higher and stability
Concern [Chin.J.Org.Chem.2016,36,987 by analytical chemistry and technical field of material chemistry；Dalton Trans.,
2012,41,2131；Macromolecules 2012,45,3078；Energy Sources,Part A,2011,33,1035；
Inorg.Chem.2009,48,10466；J.Am.Chem.Soc.2009,131,3476；Macromolecules.2007,40,
6；J.Am.Chem.Soc.2004,126,7015；Macromolecules.2006,39,9041.J.Am.Chem.Soc.2004,
126,7015；Appl.Phys.Lett.2001,78,2300；Chem.Mater.2000,12,79；Antimicrob.Agents
Chemother.1980,17,549；Chem.Ber.1969,102,4025] still, the bifunctional catalyst based on fluorescent marker
It is reported for synthesizing chemistry never someone.And the such compound method of synthesis is single, predominantly using quinoline derivatives with
Triphenyl borine heating reflux reaction, but such method expensive starting materials, product structure are single, low yield, and live without catalysis
Property；So that using ionic organic quinolines boron/nitrogen fluorescent chemicals catalyst difunctional as soda acid in organic synthesis
Using not reporting.
The present invention is using quinolines, cheap tetraphenylboron sodium analog derivative as raw material, with iodine that is cheap, being easy to get
As catalyst, with there are commonly solvents to make reaction dissolvent, certain time, high yield, height are reacted in reaction at a certain temperature
Difunctional ionic organic boron nitrogen fluorescence lewis acid base catalyst is selectively obtained, the catalyst stability is good, it can be recycled,
And there is extraordinary non-corresponding stereoselectivity in Mannich reaction.
[summary of the invention]
The present invention is using existing 8- fluoro amide quinolines, tetraphenylboron sodium analog derivative as raw material, with cheap, easy
The iodine obtained is as catalyst, and with there are commonly solvents to make reaction dissolvent, certain time is reacted in reaction at a certain temperature,
High yield obtains difunctional ionic organic boron nitrogen fluorescence lewis acid base catalyst with high selectivity.The catalyst is in Manny
There is extraordinary non-corresponding stereoselectivity in uncommon reaction.
To achieve the above object of the invention, the present invention proposes technical solution below:
The present invention is using existing 8- fluoro amide quinolines, tetraphenylboron sodium analog derivative as raw material, with cheap, easy
The iodine obtained is as catalyst, and with there are commonly solvents to make reaction dissolvent, certain time is reacted in reaction at a certain temperature,
High yield obtains the organic boron-nitrogen compound of ionic 8- fluoro amide quinolines with high selectivity.After reaction, through preparing color
Spectrum separates to obtain ionic organic boron nitrogen fluorescent chemicals.The catalyst has extraordinary non-corresponding isomery to select in Mannich reaction
Selecting property.
The present invention is a kind of difunctional ionic organic boron nitrogen fluorescence lewis acid base catalyst and preparation method thereof the system
Preparation Method with quinolines (I), tetraphenylboron sodium analog derivative (II) be raw material, using iodine as catalyst, with organic
Solvent makees reaction dissolvent, and effecting reaction, obtained ionic 8- fluoro amide quinolines organic boron nitrogen are glimmering at a certain temperature for reaction
Optical compounds (III)；Its structural formula is as follows:
Wherein, the R1、R2、R3、R4、R5、R6Group is hydrogen, methyl, methoxyl group, tert-butyl, isopropyl, nitro, acetylene
One of base, vinyl, allyl, carbonyl, hydroxyl, aldehyde radical, trifluoromethyl, fluorine, chlorine, bromine, iodine, RfFor containing fluoro aryl or alkane
Base group.In above-mentioned preparation method, which is characterized in that be with 8- fluoro amide quinolines, tetraphenylboron sodium analog derivative
Raw material, with there are commonly solvents to make reaction dissolvent, is reacted in certain temperature using iodine that is cheap, being easy to get as catalyst
Lower reaction certain time, high yield obtain ionic organic boron nitrogen quinolines with high selectivity.The catalyst is in Manny
There is extraordinary non-corresponding stereoselectivity in uncommon reaction.
In above-mentioned preparation method, which is characterized in that the R3Group is hydrogen, phenyl, 4- chlorphenyl, 4- aminomethyl phenyl, 4-
Trifluoromethyl, 4- methoxyphenyl, 4- acetylphenyl, 4- hydroxy phenyl, 4- aldehyde radical phenyl, 4- styryl, chlorine,
Bromine, iodine, allyl, acetyl group, phenoxy group, thiophenyl, phenylseleno, benzene telluro, 2- thienyl, carbazyl, in 2- styryl
One kind.
In above-mentioned preparation method, which is characterized in that the RfGroup is trifluoromethyl, pentafluoropropyl group, seven fluorine butyl, perfluor
One of phenyl, nine fluorine amyl groups.
In above-mentioned preparation method, which is characterized in that the R1、R2、R6Group is hydrogen, methyl, methoxyl group, tert-butyl, isopropyl
One of base, nitro, cyano, acetenyl, trifluoromethyl, fluorine, chlorine, bromine, iodine.
In above-mentioned preparation method, it is characterised in that the R4、R5Group is respectively one of hydrogen, methyl ,-methoxyl group.
In above-mentioned preparation method, which is characterized in that the solvent is toluene, acetonitrile, tetrahydrofuran (THF), dimethyl sulfoxide
(DMSO), one of n,N-Dimethylformamide (DMF).
In above-mentioned preparation method, which is characterized in that catalyst is one of iodine, Potassiumiodate, potassium iodide.
In above-mentioned preparation method, which is characterized in that the dosage of catalyst is 1%-500%.
In above-mentioned preparation method, which is characterized in that highly-solid selectively of the catalyst in catalysis Mannich reaction.
[Detailed description of the invention]
It is a kind of novel organic boron nitrogen material quinolines synthesis path figure provided by the invention shown in attached drawing 1.It is attached
The catalytic applications of the difunctional organic boron nitrogen fluorescence lewis acid base catalyst of Fig. 2.
[specific embodiment]
A kind of ionic organic boron nitrogen fluorescence lewis acid base bifunctional catalyst of the present invention and preparation method thereof, refers to
Attached drawing 1: solvent, nitrogen atmosphere will be added as in raw material quinoline derivatives, tetraphenylboron sodium and catalyst merging reaction vessel
Under, it is reacted 10-60 hours in the environment of 20-200 DEG C, obtains target product for product through pillar layer separation after the reaction was completed
III is catalyzed Mannich reaction as catalyst
Below with reference to specific preparating example, the present invention will be further described:
Preparation example 1
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1、
R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C to be terminated
Afterwards, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1、R2、R3、R4、R5、R6=H), yield is 96%. detections
Catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph), 0.6mmol are added in 10mL reaction tube
Cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1、R2、R3、R4、R5、R6=H) and 1mL toluene, it reacts at 25 DEG C
Carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl cyclohexanone, yield 78%, along anti-
Selectivity is 1/99.
Preparation example 2
0.1mmol I (wherein R is added in 10mL reaction tubef=C2F5；R3、R4、R5=H), 0.2mmol II (wherein R1
=H, R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction knot at 150 DEG C
Shu Hou is filtered, and concentration obtains III (wherein R through pillar layer separationf=C2F5；R1、R2、R3、R4、R5、R6=H) yield be 73%. inspection
Survey catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1、R2、R3、R4、R5、R6=H) and 1mL toluene, reaction
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl cyclohexanone, yield are are carried out at 25 DEG C
83%, cri-trans selectivity 1/99.
Preparation example 3
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1、
R6=H；R2=OMe), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R2=OMe；R1、R3、R4、R5、R6=H), yield is
60%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R2=OMe；R1、R3、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 83%, cri-trans selectivity 1/99.
Preparation example 4
0.1mmol I (wherein R is added in 10mL reaction tubef=C3F7；R3、R4、R5=H), 0.2mmol II (wherein
R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction knot at 150 DEG C
Shu Hou is filtered, and concentration obtains III (wherein R through pillar layer separationf=C3F7；R1、R2、R3、R4、R5、R6=H), yield 61%.
Detect catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=C3F7；R1、R2、R3、R4、R5、R6=H) and 1mL toluene, reaction
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl cyclohexanone, yield are are carried out at 25 DEG C
84%, cri-trans selectivity 1/99.
Preparation example 5
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1
=-C (CH3)3；R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1=(- C (CH3)3)；R2、R3、R4、R5、R6
=H), yield is 83%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene being added in 10mL reaction tube
Formaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=(- C (CH3)3)；R2、R3、R4、R5、
R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2- benzene
Amido benzyl cyclohexanone, yield 86%, cri-trans selectivity 1/99.
Preparation example 6
0.1mmol I (wherein R is added in 10mL reaction tubef=C6F5；R3、R4、R5=H), 0.2mmol II (wherein
R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction knot at 150 DEG C
Shu Hou is filtered, and concentration obtains wherein III (wherein R through pillar layer separationf=C6F5；R1、R2、R3、R4、R5、R6=H), yield is
61%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=C6F5；R1、R2、R3、R4、R5、R6=H) and 1mL toluene,
Reaction carries out 12h, TLC tracking reaction to fully reacting reaction result at 25 DEG C are as follows: 2- anilino- benzyl cyclohexanone produces
Rate is 89%, cri-trans selectivity 1/99.
Preparation example 7
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R6
=H, R1=CH3、R2=OMe), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out at 150 DEG C
12h. after reaction, is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R1=CH3；R2=OMe；R3、R4、R5、
R6=H), yield is 72%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol being added in 10mL reaction tube
Benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=CH3；R2=OMe；R3、R4、R5、
R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2- benzene
Amido benzyl cyclohexanone, yield 83%, cri-trans selectivity 1/99.
Preparation example 8
0.1mmol I (wherein R is added in 10mL reaction tubef=C4F9；R3、R4、R5=H), 0.2mmol II (wherein R1
=H, R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction knot at 150 DEG C
Shu Hou is filtered, and concentration obtains III (wherein R through pillar layer separationf=C4F9；R1、R2、R3、R4、R5、R6=H), yield 65%.
Detect catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=C4F9；R1、R2、R3、R4、R5、R6=H) and 1mL toluene, reaction
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl cyclohexanone, yield are are carried out at 25 DEG C
88%, cri-trans selectivity 1/99.
Preparation example 9
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1、
R2=F；R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction knot at 150 DEG C
Shu Hou is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R1、R2=F；R3、R4、R5、R6=H), yield is
62%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1、R2=F；R3、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 83%, cri-trans selectivity 1/99.
Preparation example 10
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1
=NO2；R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1=NO2；R2、R3、R4、R5、R6=H), yield is
68%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=NO2、R2、R3、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 83%, the selectivity of 2- anilino- benzyl cyclohexanone are 89%, cri-trans selectivity 1/99.
Preparation example 11
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R6
=H, R1=(C2H-)、R2=Me), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out at 150 DEG C
12h. after reaction, is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R1=(C2H-)、R2=Me, R3、R4、
R5、R6=H), yield be 78%. detection catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph),
0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=(C2H-)、R2=
Me、R3、R4、R5、R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting is reacted
As a result are as follows: 2- anilino- benzyl cyclohexanone, yield 87%, the selectivity of 2- anilino- benzyl cyclohexanone is 83%, suitable
Counter-selection is 1/99.
Preparation example 12
I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1、R6=H；R2
=Cl), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. after reaction at 150 DEG C, mistake
Filter, concentration, obtains III (wherein R through pillar layer separationf=CF3；R2=Cl；R1、R3、R4、R5、R6=H), yield is 80%. detections
Catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph), 0.6mmol are added in 10mL reaction tube
Cyclohexanone, 0.002mmol III (wherein Rf=CF3；R2=Cl；R1、R3、R4、R5、R6=H) and 1mL toluene, it reacts 25
12h, TLC tracking reaction to fully reacting reaction result are carried out at DEG C are as follows: 2- anilino- benzyl cyclohexanone, yield 80%,
The selectivity of 2- anilino- benzyl cyclohexanone is 84%, cri-trans selectivity 1/99.
Preparation example 13
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R4=CH3、R3、R5=H), 0.2mmol II (its
Middle R1、R2、R6=H), 0.005mmol I2And 1mL
Toluene, under nitrogen atmosphere, reaction carries out 12h. after reaction at 150 DEG C, filters, concentration, through column chromatography
Separate to obtain III (wherein Rf=CF3；R4=CH3、R1、R2、R3、R5、R6=H), yield is 82%. detection catalytic activity: in 10mL
0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol are added in reaction tube
III (wherein Rf=CF3；R4=CH3；R1、R2、R3、R5、R6=H) and 1mL toluene, it reacts and carries out 12h, TLC at 25 DEG C
Tracking is reacted to fully reacting reaction result are as follows: 2- anilino- benzyl cyclohexanone, yield 78%, 2- anilino- benzyl
The selectivity of cyclohexanone is 84%, cri-trans selectivity 1/99.
Preparation example 14
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R6
=H；R1=I；R2=Cl), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, it is anti-that reaction carries out 12h. at 150 DEG C
It after answering, filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1=I, R2=Cl, R3、R4、R5、R6=H), it produces
Rate is 64%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar being added in 10mL reaction tube
=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=I；R2=C；R3、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 82%, the selectivity of 2- anilino- benzyl cyclohexanone are 83%, cri-trans selectivity 1/99.
Preparation example 15
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R5=OCH3；R3、R4=H), 0.2mmol II
(wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, it is anti-that reaction carries out 12h. at 150 DEG C
It after answering, filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R5=OCH3；R1、R2、R3、R4、R6=H), it produces
Rate is 78%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar being added in 10mL reaction tube
=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R5=OCH3；R1、R2、R3、R4、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 81%, the selectivity of 2- anilino- benzyl cyclohexanone are 86%, cri-trans selectivity 1/99.
Preparation example 16
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=Ph；R4、R5=H), 0.2mmol II (its
Middle R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=Ph；R1、R2、R4、R5、R6=H), yield is
90%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=Ph；R1、R2、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 81%, the selectivity of 2- anilino- benzyl cyclohexanone are 86%, cri-trans selectivity 1/99.
Preparation example 17
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-CH3-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-CH3-Ph；R1、R2、R4、R5、R6=
H), yield is 76%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene first being added in 10mL reaction tube
Aldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-CH3-Ph；R1、R2、R4、R5、R6=
H) and 1mL toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- at 25 DEG C
Benzyl cyclohexanone, yield 80%, the selectivity of 2- anilino- benzyl cyclohexanone are 82%, cri-trans selectivity 1/99.
Preparation example 18
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-CF3-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-CF3-Ph；R1、R2、R4、R5、R6=
H), yield is 70%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene first being added in 10mL reaction tube
Aldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-CF3-Ph；R1、R2、R4、R5、R6=
H) and 1mL toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- at 25 DEG C
Benzyl cyclohexanone, yield 85%, the selectivity of 2- anilino- benzyl cyclohexanone are 90%, cri-trans selectivity 1/99.
Preparation example 19
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-OCH3-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-OCH3-Ph；R1、R2、R4、R5、R6
=H), yield is 88%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene being added in 10mL reaction tube
Formaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-OCH3-Ph；R1、R2、R4、R5、
R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2- benzene
Amido benzyl cyclohexanone, yield 83%, the selectivity of 2- anilino- benzyl cyclohexanone are 82%, cri-trans selectivity 1/
99。
Preparation example 20
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-OH-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-OH-Ph；R1、R2、R4、R5、R6=
H), yield is 75%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene first being added in 10mL reaction tube
Aldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-OH-Ph；R1、R2、R4、R5、
R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2- benzene
Amido benzyl cyclohexanone, yield 84%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/
99。
Preparation example 21
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-COCH3-Ph；R4、R5=H),
0.2mmol II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, react at 150 DEG C
It carries out 12h. after reaction, filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-COCH3-Ph；R1、
R2、R4、R5、R6=H), yield be 67%. detection catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph),
0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-COCH3-Ph；
R1、R2、R4、R5、R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting is reacted
As a result are as follows: 2- anilino- benzyl cyclohexanone, yield 84%, the selectivity of 2- anilino- benzyl cyclohexanone is 100%, suitable
Counter-selection is 1/99.
Preparation example 22
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1
=Cl；R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1=Cl；R2、R3、R4、R5、R6=H), yield is
74%. detection catalytic activity: 0.5mm ol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=CF3；R1=Cl；R2、R3、R4、R5、R6=H) and
1mL toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzene first at 25 DEG C
Pentylcyclohexanone, yield 81%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 23
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=COCH3；R4、R5=H), 0.2mmol II
(wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, it is anti-that reaction carries out 12h. at 150 DEG C
It after answering, filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=COCH3；R1、R 2、R4、R5、R6=H),
Yield is 70%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde being added in 10mL reaction tube
(Ar=Ph), 0.6mm ol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=COCH3；R1、R2、R 4、R5、R6=H)
With 1mL toluene, reaction carries out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzene at 25 DEG C
Methyl cyclohexanone, yield 81%, the selectivity of 2-anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 24
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1
=CN；R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1=CN；R2、R3、R4、R5、R6=H), yield is
65%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=CN；R2、R3、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 83%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 25
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R6
=H；R1=F；R2=CF3)、0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1=F；R2=CF3；R3、R4、R5、R6=
H), yield is 82%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene first being added in 10mL reaction tube
Aldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=F；R2=CF3；R3、R4、R5、R6=H)
With 1mL toluene, reaction carries out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzene at 25 DEG C
Methyl cyclohexanone, yield 89%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 26
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-COH-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-COH-Ph；R1、R2、R4、R5、R6=
H), yield is 78%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene first being added in 10mL reaction tube
Aldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-COH-Ph；R1、R2、R4、R5、R6=
H) and 1mL toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- at 25 DEG C
Benzyl cyclohexanone, yield 89%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 27
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-C2H3-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-C2H3-Ph；R1、R2、R4、R5、R6
=H), yield is 82%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene being added in 10mL reaction tube
Formaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-COH-Ph；R1、R2、R4、R5、R6
=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2- aniline
Base benzyl cyclohexanone, yield 82%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/
99。
Preparation example 28
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=I；R4、R5=H), 0.2mmol II (wherein
R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction knot at 150 DEG C
Shu Hou is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R3=I；R1、R2、R4、R5、R6=H), yield is
71%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=I；R1、R2、R4、R5、R6=H) and 1mL tolue
Ne, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result at 25 DEG C are as follows: 2- anilino- benzyl cyclohexanone,
Yield is that the selectivity of 82%, 2- anilino- benzyl cyclohexanone is 99%, cri-trans selectivity 1/99.
Preparation example 29
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=o-C2H3-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=(2-C2H3)-Ph；R1、R2、R4、R5、
R6=H), yield is 84%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol being added in 10mL reaction tube
Benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=(2-C2H3)-Ph；R1、R2、R4、
R5、R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2-
The selectivity of anilino- benzyl cyclohexanone, yield 81%, 2- anilino- benzyl cyclohexanone is 99%, and cri-trans selectivity is
1/99。
Preparation example 30
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-O-Ph；R4、R5=H), 0.2mmol II
(wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, it is anti-that reaction carries out 12h. at 150 DEG C
It after answering, filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=O-Ph；R1、R2、R4、R5、R6=H), it produces
Rate is 80%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar being added in 10mL reaction tube
=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=OPh；R1、R2、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 82%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 31
I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1=((CH3)2CH-)；R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R1=((CH3)2CH-)；R2、R3、R4、R5、R6=
H), yield is 78%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene first being added in 10mL reaction tube
Aldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=((CH3)2CH-)；R2、R3、R4、R5、
R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2- benzene
Amido benzyl cyclohexanone, yield 82%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/
99。
Preparation example 32
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-S-Ph, R4、R5=H), 0.2mmol II
(wherein R1=H, R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out at 150 DEG C
12h. after reaction, is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-S-Ph；R1、R2、R4、R5、R6
=H), yield is 87%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene being added in 10mL reaction tube
Formaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-S-Ph；R1、R2、R4、R5、R6=
H) and 1mL toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- at 25 DEG C
Benzyl cyclohexanone, yield 82%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 33
I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1=OCH3；R2、
R6=H), 0.005mmol I2And 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. after reaction at 150 DEG C,
Filtering, concentration, obtains III (wherein R through pillar layer separationf=CF3；R1=OCH3；R2、R3、R4、R5、R6=H), yield 78%.
Detect catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=OCH3；R2、R3、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 80%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 34
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-Se-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2And 1mL toluene, under nitrogen atmosphere, reaction carries out at 150 DEG C
12h. after reaction, is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-Se-Ph；R1、R2、R4、R5、
R6=H), yield is 74%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol being added in 10mL reaction tube
Benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-Se-Ph；R1、R2、R4、R5、R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2-
The selectivity of anilino- benzyl cyclohexanone, yield 88%, 2- anilino- benzyl cyclohexanone is 99%, and cri-trans selectivity is
1/99。
Preparation example 35
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=p-Te-Ph；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2And 1mL toluene, under nitrogen atmosphere, reaction carries out at 150 DEG C
12h. after reaction, is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-Te-Ph；R1、R2、R 4、
R5、R6=H), yield be 78%. detection catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph),
0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-Te-Ph；R1、
R2、R4、R5、R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction is reacted to fully reacting ties
Fruit are as follows: 2- anilino- benzyl cyclohexanone, yield 88%, the selectivity of 2- anilino- benzyl cyclohexanone is 99%, along anti-
Selectivity is 1/99.
Preparation example 36
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=-H2C-CH=CH2；R4、R5=H),
0.2mmol II (wherein R1、R2、R6=H), 0.005mmol I2And 1mL toluene, under nitrogen atmosphere, react at 150 DEG C
Lower progress 12h. after reaction, is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R3=-H2C-CH=CH2；
R1、R2、R4、R5、R6=H), yield is 71%. detection catalytic activity: 0.5mmol aniline (Ar=being added in 10mL reaction tube
Ph), 0.5mmol benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=-H2C-CH
=CH2；R1、R2、R4、R5、R6=H) and 1mL toluene, reaction carries out 12h at 25 DEG C, and TLC tracking reaction is to having reacted
Full reaction result are as follows: the selectivity of 2- anilino- benzyl cyclohexanone, yield 85%, 2- anilino- benzyl cyclohexanone is
99%, cri-trans selectivity 1/99.
Preparation example 37
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R6
=H；R1=CF3；R2=CH3)、0.005mmol I2And 1 mL toluene, under nitrogen atmosphere, reaction carries out at 150 DEG C
12h. after reaction, is filtered, and concentration obtains III (wherein R through pillar layer separationf=CF3；R1=CF3；R2=CH3；R3、R4、R5、
R6=H), yield is 72%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol being added in 10mL reaction tube
Benzaldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R1=CF3；R2=CH3；R3、R4、R5、
R6=H) and 1mL toluene, it reacts and carries out 12h at 25 DEG C, TLC tracking reaction to fully reacting reaction result are as follows: 2- benzene
Amido benzyl cyclohexanone, yield 89%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/
99。
Preparation example 38
0.1I (wherein R is added in 10mL reaction tubef=CF3；R3=(C12H8N)；R4、R5=H), 0.2mmol II (its
Middle R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=C12H8N；R1、R2、R4、R5、R6=H), yield
For 71%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=being added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=C12H8N；R1、R2、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 81%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 39
0.1mmol I wherein R is added in 10mL reaction tubef=CF3；R3=p-Cl-Ph；R4、R5=H), 0.2mmol II
(wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, it is anti-that reaction carries out 12h. at 150 DEG C
It after answering, filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=p-Cl-Ph；R1、R2、R4、R5、R6=H),
Yield is 88%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde being added in 10mL reaction tube
(Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=p-Cl-Ph；R1、R2、R4、R5、R6=H)
With 1mL toluene, reaction carries out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzene at 25 DEG C
Methyl cyclohexanone, yield 83%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 40
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=(2-C4H3S；R4、R5=H), 0.2mmol
II (wherein R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. at 150 DEG C
After reaction, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=2-C4H3S；R1、R2、R4、R5、R6=
H), yield is 92%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzene first being added in 10mL reaction tube
Aldehyde (Ar=Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=2-C4H3S；R1、R2、R4、R5、R6=
H) and 1mL toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- at 25 DEG C
Benzyl cyclohexanone, yield 88%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 41
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=Cl；R4、R5=H), 0.2mmol II (its
Middle R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=Cl；R1、R2、R4、R5、R6=H), yield is
76%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=Cl；R1、R2、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 85%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 42
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3=Br；R4、R5=H), 0.2mmol II (its
Middle R1、R2、R6=H), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C
After, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3=Br；R1、R2、R4、R5、R6=H), yield is
78%. detection catalytic activity: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=are added in 10mL reaction tube
Ph), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3=Br；R1、R2、R4、R5、R6=H) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl ring at 25 DEG C
Hexanone, yield 88%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%, cri-trans selectivity 1/99.
Preparation example 43
0.1mmol I (wherein R is added in 10mL reaction tubef=CF3；R3、R4、R5=H), 0.2mmol II (wherein R1、
R2、R6=F), 0.005mmol I2With 1mL toluene, under nitrogen atmosphere, reaction carries out 12h. reaction at 150 DEG C to be terminated
Afterwards, it filters, concentration obtains III (wherein R through pillar layer separationf=CF3；R3、R4、R5=H；R1、R2、R6=F), yield 72%.
Detect catalytic activity: in 10mL reaction tube be added 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino- benzyl cyclohexanone, yield should be carried out at 25 DEG C
Selectivity for 100%, 2- anilino- benzyl cyclohexanone is 100%, cri-trans selectivity 1/99.
Preparation example 44
0.5mmol aniline (Ar=p-CH is added in 10mL reaction tube3C6H4), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- (4- toluidine) benzyl hexamethylene should be carried out at 25 DEG C
Ketone, yield 100%, the selectivity of 2- (4- toluidine) benzyl cyclohexanone are 100%, cri-trans selectivity 1/99.
Preparation example 45
0.5mmol aniline (Ar=p-OCH is added in 10mL reaction tube3C6H4), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- (4- methoxybenzene amido) benzyl ring should be carried out at 25 DEG C
Hexanone, yield 100%, the selectivity of 2- (4- methoxybenzene amido) benzyl cyclohexanone are 100%, cri-trans selectivity 1/
99。
Preparation example 46
0.5mmol aniline (Ar=p-NO is added in 10mL reaction tube2C6H4), 0.5mmol benzaldehyde (Ar=Ph),
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- (4- nitrobenzene amido) benzyl hexamethylene should be carried out at 25 DEG C
Ketone, yield 100%, the selectivity of 2- (4- nitrobenzene amido) benzyl cyclohexanone are 100%, cri-trans selectivity 1/99.
Preparation example 47
0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=p-CH are added in 10mL reaction tube3C6H4)、
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino--(4- tolyl) methyl ring should be carried out at 25 DEG C
Hexanone, yield 100%, the selectivity of 2- anilino--(4- tolyl) methyl cyclohexanone are 100%, cri-trans selectivity 1/
99。
Preparation example 48
0.5mmol aniline (Ar=Ph), 0.5mmol paranitrobenzaldehyde (Ar=p- are added in 10mL reaction tube
CH3C6H4), 0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL
Toluene, reaction carry out 12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino--(4- nitro at 25 DEG C
Phenyl) methyl cyclohexanone, yield 100%, the selectivity of 2- anilino--(4- nitrobenzophenone) methyl cyclohexanone is 100%, suitable
Counter-selection is 1/99.
Preparation example 49
0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=p-CH are added in 10mL reaction tube3C6H4)、
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino--(4- methoxyphenyl) first should be carried out at 25 DEG C
Pentylcyclohexanone, yield 100%, the selectivity of 2- anilino--(4- methoxyphenyl) methyl cyclohexanone are 100%, along anti-choosing
Selecting property is 1/99.
Preparation example 50
0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=p-FC are added in 10mL reaction tube6H4)、
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino--(4- fluorophenyl) methyl ring should be carried out at 25 DEG C
Hexanone, yield 100%, the selectivity of 2- anilino--(4- fluorophenyl) methyl cyclohexanone are 100%, cri-trans selectivity 1/
99。
Preparation example 51
0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar=p-ClC are added in 10mL reaction tube6H4)、
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: 2- anilino--(4- chlorphenyl) methyl ring should be carried out at 25 DEG C
Hexanone, yield 100%, the selectivity of 2- anilino--(4- chlorphenyl) methyl cyclohexanone are 100%, cri-trans selectivity 1/
99。
Preparation example 52
0.5mmol benzaldehyde (Ar=Ph) is added in 10mL reaction tube, 0.5mmol n-propylamine, 0.6mmol cyclohexanone,
0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, it reacts and is carried out at 25 DEG C
12h, TLC tracking are reacted to fully reacting reaction result are as follows: (E) -2- benzylidene cyclohexanone, yield 100%, (E) -2-
The selectivity of benzylidene cyclohexanone is 100%, cri-trans selectivity 1/99.
Preparation example 53
0.5mmol n-propylamine, 0.5mmol p-chlorobenzaldehyde (Ar=p-ClC are added in 10mL reaction tube6H4)、
0.6mmol cyclohexanone, 0.002mmol III (wherein Rf=CF3；R3、R4、R5=H；R1、R2、R6=F) and 1mL toluene, instead
12h, TLC tracking reaction to fully reacting reaction result are as follows: (E) -2- (4- chlorphenyl) methylenecyclohex should be carried out at 25 DEG C
Ketone, yield 100%, the selectivity of (E) -2- (4- chlorphenyl) methylene Cyclohexanone are 100%, cri-trans selectivity 1/99.
Reference examples 1:
Under no catalysts conditions: 0.5mmol aniline (Ar=Ph), 0.5mmol benzaldehyde (Ar being added in 10mL reaction tube
=Ph), 0.6mmol cyclohexanone and 1mL toluene, reaction carries out 12h at 25 DEG C, and TLC tracking reaction is anti-to fully reacting
Answer result are as follows: 2- anilino- benzyl cyclohexanone, yield 35%, the selectivity of 2- anilino- benzyl cyclohexanone are 99%,
Cri-trans selectivity is 45/55.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Cannot therefore and being interpreted as limitations on the scope of the patent of the present invention should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Protect range therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (2)
1. a kind of organic boron of fluorescent marker/nitrogen lewis acid base bifunctional catalyst, its structural formula of the bifunctional catalyst
(I) as follows:
Wherein substituent group shown in structure formula (I) is characterized in that, the R1、R2、R6Group is hydrogen, methyl, methoxyl group, tertiary fourth
One of base, isopropyl, nitro, cyano, acetenyl, trifluoromethyl, fluorine, chlorine, bromine, iodine；The wherein R3Group is hydrogen, benzene
Base, 4- chlorphenyl, 4- aminomethyl phenyl, 4- trifluoromethyl, 4- methoxyphenyl, 4- acetylphenyl, 4- hydroxy phenyl, 4-
Aldehyde radical phenyl, 4- ethenylphenyl, chlorine, bromine, iodine, methylacryloyl, acetyl group, phenoxy group, thiophenyl, phenylseleno, benzene tellurium
One of base, 2- thienyl, carbazyl, 2- styryl；The wherein R4、R5Group is respectively H ,-Me ,-OMe group
It is a kind of；The wherein RfGroup is one of trifluoromethyl, pentafluoroethyl group, heptafluoropropyl, perfluorophenyl, nona-fluoro butyl group.
2. the organic boron of fluorescent marker according to claim 1/nitrogen lewis acid base bifunctional catalyst, is characterized in that,
Using quinolines, tetraphenylboron sodium analog derivative as raw material, using elemental iodine that is cheap, being easy to get or iodine class compound as being catalyzed
Agent, with there are commonly solvents to make reaction dissolvent, reaction reacts 1-24h at 20-200 DEG C, organic boron/nitrogen can be prepared
Lewis acid base bifunctional catalyst (I)；The organic solvent is toluene, acetonitrile, tetrahydrofuran (THF), dimethyl sulfoxide
(DMSO), one of N,N-dimethylformamide (DMF)；The iodine class compound is one of Potassiumiodate, potassium iodide.
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| "Borchelate und Bormetallchelate 1. Mitt. Borchelate mit Chelatbildnern der Pyridin- und Chinolinreihe und ihren N-Oxiden";E.Hohaus et al.;《Chem.Ber.》;19700127(第102期);第3488-3492页 * |
| "Main-Chain-Type N,N′-Chelate Organoboron Aminoquinolate Polymers: Synthesis, Luminescence, and Energy Transfer Behavior";Yuuya Nagata et al.;《Macromolecules》;20080423(第41期);第4025-4031页 * |
| "Theoretical design study on photophysical property of the organoboron quinolate derivatives";Luyi Zou et al.;《Theor. Chem. Acc》;20110119(第129期);第63-71页 * |
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