CN104030970B - A kind of novel method of synthesizing carbazole compounds - Google Patents
A kind of novel method of synthesizing carbazole compounds Download PDFInfo
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- CN104030970B CN104030970B CN201410294787.7A CN201410294787A CN104030970B CN 104030970 B CN104030970 B CN 104030970B CN 201410294787 A CN201410294787 A CN 201410294787A CN 104030970 B CN104030970 B CN 104030970B
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title 1
- -1 2,6-diisopropyl phenyl Chemical group 0.000 claims abstract description 136
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 150000001716 carbazoles Chemical class 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 38
- 239000002808 molecular sieve Substances 0.000 claims description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000013508 migration Methods 0.000 claims description 3
- 230000005012 migration Effects 0.000 claims description 3
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 147
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 50
- 229940093499 ethyl acetate Drugs 0.000 description 49
- 235000019439 ethyl acetate Nutrition 0.000 description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 48
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 238000001035 drying Methods 0.000 description 30
- 239000007787 solid Substances 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 0 *c(cc1*2N)c(*=C)c(N(*)CI)c1-c1c2ccc([N+])c1 Chemical compound *c(cc1*2N)c(*=C)c(N(*)CI)c1-c1c2ccc([N+])c1 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- FGJAUJJHGXCJIL-UHFFFAOYSA-N (1-butyl-9-ethyl-3,4-dimethylcarbazol-2-yl) benzoate Chemical compound CCCCc1c(OC(=O)c2ccccc2)c(C)c(C)c2c3ccccc3n(CC)c12 FGJAUJJHGXCJIL-UHFFFAOYSA-N 0.000 description 3
- YNEVPAACAPAFET-UHFFFAOYSA-N (9-ethyl-4-heptylcarbazol-2-yl) benzoate Chemical compound CCCCCCCc1cc(OC(=O)c2ccccc2)cc2n(CC)c3ccccc3c12 YNEVPAACAPAFET-UHFFFAOYSA-N 0.000 description 3
- DBDCPKPHHCECLZ-UHFFFAOYSA-N 1-chloro-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(Cl)=CC=C2 DBDCPKPHHCECLZ-UHFFFAOYSA-N 0.000 description 3
- VJBSZGJDFGLOOZ-UHFFFAOYSA-N CC1=C(C=C2C(=C1C)C3=CC=CC=C3N2C4=CC=CC=C4)OC(=O)C5=CC=CC=C5 Chemical compound CC1=C(C=C2C(=C1C)C3=CC=CC=C3N2C4=CC=CC=C4)OC(=O)C5=CC=CC=C5 VJBSZGJDFGLOOZ-UHFFFAOYSA-N 0.000 description 3
- XRCDFSNQQPEIBJ-UHFFFAOYSA-N CC1=C(C=C2C(=C1C)C3=CC=CC=C3N2CC4=CC=CC=C4)OC(=O)C5=CC=CC=C5 Chemical compound CC1=C(C=C2C(=C1C)C3=CC=CC=C3N2CC4=CC=CC=C4)OC(=O)C5=CC=CC=C5 XRCDFSNQQPEIBJ-UHFFFAOYSA-N 0.000 description 3
- HKNXSVZUKWCUNC-UHFFFAOYSA-N CCC1=C(C=C2C(=C1CC)C3=CC=CC=C3N2CC)OC(=O)C4=CC=CC=C4 Chemical compound CCC1=C(C=C2C(=C1CC)C3=CC=CC=C3N2CC)OC(=O)C4=CC=CC=C4 HKNXSVZUKWCUNC-UHFFFAOYSA-N 0.000 description 3
- ZBKQDNLJJAIBCF-UHFFFAOYSA-N CCCC1=C(C=C2C(=C1CCC)C3=CC=CC=C3N2CC)OC(=O)C4=CC=CC=C4 Chemical compound CCCC1=C(C=C2C(=C1CCC)C3=CC=CC=C3N2CC)OC(=O)C4=CC=CC=C4 ZBKQDNLJJAIBCF-UHFFFAOYSA-N 0.000 description 3
- NYMVFRSWIZKKGF-UHFFFAOYSA-N CCCCCCCC1=C2C(=CC(=C1)OC(=O)C3=CC=CC=C3)N(C4=C2C=C(C=C4)C)CC Chemical compound CCCCCCCC1=C2C(=CC(=C1)OC(=O)C3=CC=CC=C3)N(C4=C2C=C(C=C4)C)CC NYMVFRSWIZKKGF-UHFFFAOYSA-N 0.000 description 3
- UFOSFFZXADHCHJ-UHFFFAOYSA-N CCN1C2=CC=CC=C2C3=C(C(=C(C=C31)OC(=O)C4=CC=CC=C4)C5=CC=C(C=C5)C)C Chemical compound CCN1C2=CC=CC=C2C3=C(C(=C(C=C31)OC(=O)C4=CC=CC=C4)C5=CC=C(C=C5)C)C UFOSFFZXADHCHJ-UHFFFAOYSA-N 0.000 description 3
- BZYWMDMJZIEGDQ-UHFFFAOYSA-N CCN1C2=CC=CC=C2C3=C(C=C(C=C31)OC(=O)C4=CC=CC=C4)C5CCCCC5 Chemical compound CCN1C2=CC=CC=C2C3=C(C=C(C=C31)OC(=O)C4=CC=CC=C4)C5CCCCC5 BZYWMDMJZIEGDQ-UHFFFAOYSA-N 0.000 description 3
- VUSPYDNLCREHPM-UHFFFAOYSA-N CCN1C2=CC=CC=C2C3=C1C(=C(C(=C3C)C)OC(=O)C4=CC=CC=C4)C5=CC=CC=C5 Chemical compound CCN1C2=CC=CC=C2C3=C1C(=C(C(=C3C)C)OC(=O)C4=CC=CC=C4)C5=CC=CC=C5 VUSPYDNLCREHPM-UHFFFAOYSA-N 0.000 description 3
- SPQFTWHSEFLZRE-UHFFFAOYSA-N CCN1C2=CC=CC=C2C3=C1C=C(C=C3)OC(=O)C4=CC=CC=C4 Chemical compound CCN1C2=CC=CC=C2C3=C1C=C(C=C3)OC(=O)C4=CC=CC=C4 SPQFTWHSEFLZRE-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VCDOOGZTWDOHEB-UHFFFAOYSA-N 1-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(Br)=CC=C2 VCDOOGZTWDOHEB-UHFFFAOYSA-N 0.000 description 1
- YSBHLEVBYWIZKB-UHFFFAOYSA-N CCCCN1C2=CC=CC=C2C3=C(C(=C(C=C31)OC(=O)C4=CC=CC=C4)C)C Chemical compound CCCCN1C2=CC=CC=C2C3=C(C(=C(C=C31)OC(=O)C4=CC=CC=C4)C)C YSBHLEVBYWIZKB-UHFFFAOYSA-N 0.000 description 1
- WRDYABSTHCMFJS-UHFFFAOYSA-N COc(cc1)cc(CCCC2[O-](C)[N+]2=C)c1[NH+2]Cl Chemical compound COc(cc1)cc(CCCC2[O-](C)[N+]2=C)c1[NH+2]Cl WRDYABSTHCMFJS-UHFFFAOYSA-N 0.000 description 1
- NUZIHLUFIOKRSO-UHFFFAOYSA-N O=C(c1ccccc1)Oc1cc(-c2ccccc2)c(c(cc(cc2)Cl)c2[n]2Cc3ccccc3)c2c1 Chemical compound O=C(c1ccccc1)Oc1cc(-c2ccccc2)c(c(cc(cc2)Cl)c2[n]2Cc3ccccc3)c2c1 NUZIHLUFIOKRSO-UHFFFAOYSA-N 0.000 description 1
- OIOIKTBJFZYPCK-UHFFFAOYSA-N OC(c1cc2cc(Cl)ccc2[n]1Cc1ccccc1)C#CC(c1ccccc1)OC(c1ccccc1)=O Chemical compound OC(c1cc2cc(Cl)ccc2[n]1Cc1ccccc1)C#CC(c1ccccc1)OC(c1ccccc1)=O OIOIKTBJFZYPCK-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
The present invention relates to a kind of method of synthesizing carbazole compounds, 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides/silver hexafluoroantimonate catalysis under, react to 1-(indoles-2-base)-2-alkynes-1-alcohol high regioselectivity synthesis functionalization carbazole, the present invention has simple to operate, raw material and reagent are easy to get, mild condition, reaction has the advantages such as the regioselectivity of height, and multiple substituting group can be introduced, the easily separated purifying of product simultaneously, be applicable to the carbazole compound synthesizing various replacement.
Description
Technical field
Synthesize the method for functionalization carbazole with the present invention relates to a kind of high regioselectivity, namely 1-(indoles-2-base)-2-alkynes-1-alcohol is 1, Reactive Synthesis carbazole compound is there is under the catalysis of 3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides/silver hexafluoroantimonate.
Background technology
Carbazole compound is widespread in nature, and is also simultaneously the basic framework of some medicines, due to carbazole alkaloid superior, the biological activity of wide spectrum, cause the very big concern of pharmaceutical chemists.In addition due to its special thermodynamics, electricity and optical property, make it in Materials science, also have larger application prospect.
1-2therefore, development structure novelty and polysubstituted carbazole compound gain great popularity, and have become the new direction that research and development carbazoles medicine is important.Although the investigation and application of recent domestic to carbazole and derivative thereof gos deep into just further,
3-4but simple, quick, the efficient and polysubstituted carbazole of synthesis of highly selective and the document of derivative thereof are but seldom reported.Limitation is raw material preparation not easily, severe reaction conditions, and reaction preference is poor, unfriendly to environment, and substrate diversity is bad etc.
Reference:
(1)Schmidt,A.W.；Reddy,K.R.；
H.-J.Chem.Rev.2012,112,3193.
(2)(a)Kapil,R.S.TheAlkaloids,ed.Manske,R.H.F.AcademicPress,NewYork,1971,13,273.(b)Husson,H.P.TheAlkaloids,ed.Brossi,A.AcademicPress,NewYork,1985,26,1.(c)Chakraborty,D.P.TheAlkaloids,ed.Bossi,A.AcademicPress,NewYork,1993,44,257.(d)
H.J.AdvancesinNitrogenHeterocycles,ed.Moody,C.J.J.AI,Greenwich,1995,1,173.(e)Maneerat,W.；Ritthiwigrom,T.；Cheenpracha,S.；Promgool,T.；Yossathera,K.；Deachathai,S.；Phakhodee,W.；Laphookhieo,S.J.Nat.Prod.2012,75,741.(f)Thongthoom,T.；Songsiang,U.；Phaosiri,C.；Yenjai,C.Arch.Pharm.Res.2010,33,675.(g)Lin,W.；Wang,Y.；Lin,S.；Li,C.；Zhou,C.；Wang,S.；Huang,H.；Liu,P.；Ye,G.；Shen.X.Eur.J.Medi.Chem.2012,47,214.(h)
M.；Liu,J.；Zheng,R.；Lam,J.W.Y.；Qin,A.；Tang,B.Z.Macromolecules2007,40,1914.(i)Sanda,F.；Nakai,T.；Kobayashi,N.；Masuda,T.Macromolecules2004,37,2703.
(3)Forreviewsonthesynthesisofcarbazoles,see:(a)
H.-J.；Reddy,K.R.Chem.Rev.2002,102,4303.(b)Bergman,J.；Pelcman,B.Pure&Appl.Chem.1990,62,1967.(c)Moody,C.J.Synlett1994,681.(d)
B.C.G.Curr.Org.Chem.2000,4,727.(e)
H.-J.Chem.Soc.Rev.1999,28,151.(f)
H.-J.Top.Curr.Chem.2005,244,115.
(4)Forselectedexamples,see:(a)Tsang,W.C.P.；Zheng,N.；Buchwald,S.L.J.Am.Chem.Soc.2005,127,14560.(b)Ackermann,L.；Althammer,A.Angew.Chem.,Int.Ed.2007,46,1627.(c)Forke,R.；
A.；
H.-J.Org.Biomol.Chem.2008,6,2481.(d)Gruner,K.K.；
H.-J.Org.Biomol.Chem.2008,6,3902.(e)Knott,K.E.；Auschill,S.；
A.；
H.-J.Chem.Commun.2009,1467.(f)Kong,W.；Fu,C.；Ma,S.Chem.Commun.2009,4572.(g)Lim,B.-Y.；Choi,M.-K.；Cho,C.-G.TetrahedronLett.2011,52,6015.(h)Kumar,V.P.；Gruner,K.K.；Kataeva,O.；
H.-J.Angew.Chem.,Int.Ed.2013,52,11073.(i)Hernandez-Perez,A.C.；Collins,S.K.Angew.Chem.,Int.Ed.2013,52,12696.
Summary of the invention
The object of the invention is just to provide a kind of simple, and efficiently, fast, the method for the polysubstituted carbazole compound of one-step synthesis of highly selective, is achieved through the following technical solutions:
A kind of method of synthesizing functionalization carbazole, 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides/silver hexafluoroantimonate catalysis under, 1-(indoles-2-the base)-2-alkynes-1-alcohol high regioselectivity ground synthesizing carbazole compounds that reacts, in the reaction, OBz and R of 4-position in raw material is in
4respectively selective migration is to the 2-position of product carbazole and 3-position, and react experienced by and optionally moves, its reaction formula is as follows:
R
1=methyl, methoxyl group, chlorine or bromine; R
2=ethyl, phenyl, benzyl, butyl or allyl group; R
3=alkyl; R
4=alkyl
Or aryl, wherein alkyl is C
nh
2n+1, n=1-3 in formula; R
5=methyl, butyl or phenyl; Concrete steps are as follows:
(1) in glove box, weighed silver hexafluoroantimonate and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides, then added successively
molecular sieve, 1-(indoles-2-base)-2-alkynes-1-alcohol, and 1,2-ethylene dichloride, then at room temperature stirring reaction 1-48 hour;
(2) too short silicagel column, concentrated, rapid column chromatography, obtains carbazole compound.
As improving further, R of the present invention
3the alkyl of=straight chain: n-propyl, n-heptyl, high benzyl, or the alkyl of side chain or ring-type: sec.-propyl and cyclohexyl.
As improving further, organic solvent of the present invention is 1,2-ethylene dichloride.
As improving further, 1-of the present invention (indoles-2-base)-2-alkynes-1-alcohol and 1, the mol ratio of 3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides and silver hexafluoroantimonate is 1: 0.05:0.05.
As improving further, the mol ratio of 1-of the present invention (indoles-2-base)-2-alkynes-1-alcohol and 1,2-ethylene dichloride is 0.1:1, and unit is mmol/mL.
The present invention relates to a kind of 1-(indoles-2-base)-2-alkynes-1-alcohol to react under the catalysis of gold/silver, the method for the polysubstituted carbazole compound of high regioselectivity ground synthesis.Present method is simple to operate, and raw material and reagent are easy to get, and reaction has the regioselectivity of height, and reaction conditions is gentle, is applicable to the carbazole synthesizing various replacement.
Instant invention overcomes the drawback of traditional method, have the following advantages:
1) reaction has the regioselectivity of height; 2) easy to operate, productive rate is higher; 3) diversity of substrate is enriched; 4) reaction conditions is gentle; 5) environmental friendliness.
Innovative point of the present invention is the methodology having developed a kind of high regioselectivity ground synthesizing carbazole compounds.
The productive rate of the corresponding carbazole compound of gained of the present invention is 31-91%.
Embodiment
The present invention synthesizes the method for functionalization carbazole, 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides/silver hexafluoroantimonate catalysis under, 1-(indoles-2-the base)-2-alkynes-1-alcohol high regioselectivity ground synthesizing carbazole compounds that reacts, in the reaction, OBz and R of 4-position in raw material is in
4respectively selective migration is to the 2-position of product carbazole and 3-position, and its reaction formula is as follows:
R
1=methyl, methoxyl group, chlorine, bromine; R
2=ethyl, phenyl, benzyl, butyl, allyl group; R
3=various alkyl, the alkyl as straight chain: n-propyl, n-heptyl, high benzyls etc. also can be the alkyl of side chain or ring-type: sec.-propyl and cyclohexyl; R
4=alkyl or aryl, wherein alkyl is C
nh
2n+1, n=1-3, R in formula
5=methyl, butyl, phenyl; The steps include:
(3) in glove box, weighed silver hexafluoroantimonate and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides, then added successively
molecular sieve, 1-(indoles-2-base)-2-alkynes-1-alcohol, and 1,2-ethylene dichloride, then at room temperature stirring reaction 1-48 hour;
(4) concentrated, rapid column chromatography, obtains carbazole compound.
Organic solvent of the present invention is 1,2-ethylene dichloride.The mol ratio of 1-(indoles-2-base)-2-alkynes-1-alcohol and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides and silver hexafluoroantimonate is: 1: 0.05:0.05.
The mol ratio of 1-of the present invention (indoles-2-base)-2-alkynes-1-alcohol and 1,2-ethylene dichloride is: 0.1mmol/mL.
Below by specific embodiment, technical scheme of the present invention is described in further detail:
(1) 2-benzoyloxy-9-ethyl-4-heptyl-9H-carbazole (3a) (qya-7-129)
Exemplary steps: add silver hexafluoroantimonate (18.0mg in the reaction tubes of drying, 0.05mmol) He 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (33.1mg, 0.05mmol, weigh in glove box), then add successively
molecular sieve (501.7mg), 2a (432.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 1 hour, too short silicagel column (ether: 20mL × 3), concentrated, rapid column chromatography (petrol ether/ethyl acetate=30/1), obtain product 3a (355.5mg, 86%): product is solid, fusing point: 93.0-93.8 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.26(d,J＝7.5Hz,2H,ArH),8.11(d,J＝8.1Hz,1H,ArH),7.59(t,J＝7.4Hz,1H,ArH),7.53-7.32(m,4H,ArH),7.25(t,J＝7.4Hz,1H,ArH),7.15(s,1H,ArH),6.90(s,1H,ArH),4.25(q,J＝7.1Hz,2H,NCH
2),3.21(t,J＝7.8Hz,2H,ArCH
2),1.94-1.76(m,2H,CH
2),1.59-1.43(m,2H,CH
2),1.42-1.21(m,9H,3×CH
2+CH
3),0.88(t,J＝6.3Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.7,149.2,140.7,140.5,139.6,133.5,130.2,129.9,128.6,124.8,122.7,122.5,119.1,118.8,113.2,108.3,99.4,37.6,34.4,31.8,29.8,29.5,29.3,22.7,14.2,13.7；IR(KBr)ν(cm
-1)3059,2953,2928,2855,1737,1620,1596,1459,1435,1378,1329,1261,1177,1127,1080,1063,1026,1000；MS(70ev,EI)m/z(％)414(M
++1,14.54),413(M
+,48.40),105(100)；ElementalanalysiscalcdforC
28H
31NO
2:C,81.32；H,7.56；N,3.39；Found:C,81.31,H,7.47；N,3.24.
The synthesis step of following compound 3b-3ac is as exemplary steps.
(2) 2-benzoyloxy-6-methyl-9-ethyl-4-heptyl-9H-carbazole (3b) (qya-7-179)
Silver hexafluoroantimonate (18.0mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (502.0mg), 2b (445.7mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 1.5 hours, obtain product 3b (365.2mg, 85%) (petrol ether/ethyl acetate=50/1): product is solid, fusing point: 99.5-100.7 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.25(d,J＝7.2Hz,2H,ArH),7.89(s,1H,ArH),7.57(t,J＝7.5Hz,1H,ArH),7.46(t,J＝7.7Hz,2H,ArH),7.24(s,2H,ArH),7.11(d,J＝1.5Hz,1H,ArH),6.87(d,J＝1.5Hz,1H,ArH),4.21(q,J＝7.2Hz,2H,NCH
2),3.20(t,J＝7.8Hz,2H,ArCH
2),2.55(s,3H,CH
3),1.96-1.76(m,2H,CH
2),1.62-1.44(m,2H,CH
2),1.43-1.21(m,9H,3×CH
2+CH
3),0.88(t,J＝6.6Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.5,149.0,140.8,139.4,138.6,133.4,130.1,129.8,128.5,128.1,126.0,122.7,122.5,118.5,112.9,107.9,99.2,37.5,34.3,31.8,29.7,29.4,29.2,22.6,21.6,14.1,13.6；IR(KBr)ν(cm
-1)3060,3029,2926,2855,1736,1623,1598,1476,1378,1331,1308,1264,1176,1126,1080,1063,1024；MS(70ev,EI)m/z(％)428(M
++1,22.34),427(M
+,70.91),105(100)；ElementalanalysiscalcdforC
29H
33NO
2:C,81.64；H,7.78；N,3.28；Found:C,81.74,H,7.83；N,3.02.
(3) 2-benzoyloxy-6-methyl-9-ethyl-4-propyl group-9H-carbazole (3c) (qya-7-180)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.6mg), 2c (389.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 1.5 hours, obtain product 3c (328.4mg, 88%) (petrol ether/ethyl acetate=20/1): product is solid, fusing point: 114.5-115.6 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.26(d,J＝7.2Hz,2H,ArH),7.89(s,1H,ArH),7.62(t,J＝7.4Hz,1H,ArH),7.50(t,J＝7.5Hz,2H,ArH),7.33-7.21(m,2H,ArH),7.12(d,J＝1.5Hz,1H,ArH),6.87(s,1H,ArH),4.26(q,J＝7.2Hz,2H,NCH
2),3.20(t,J＝7.8Hz,2H,ArCH
2),2.55(s,3H,CH
3),2.00-1.82(m,2H,CH
2),1.38(t,J＝7.2Hz,3H,CH
3),1.11(t,J＝7.5Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.6,149.0,140.8,139.2,138.7,133.4,130.1,129.8,128.5,128.2,126.0,122.8,122.5,118.6,113.0,107.9,99.3,37.5,36.3,22.5,21.6,14.2,13.6；IR(KBr)ν(cm
-1)2958,2869,1736,1599,1477,1451,1382,1331,1308,1261,1176,1127,1089,1059,1024；MS(70ev,EI)m/z(％)372(M
++1,18.05),371(M
+,65.82),105(100)；ElementalanalysiscalcdforC
25H
25NO
2:C,80.83；H,6.78；N,3.77；Found:C,80.75,H,6.79；N,3.56.
(4) 2-benzoyloxy-9-ethyl-4-styroyl-9H-carbazole (3d) (qya-8-021)
Silver hexafluoroantimonate (17.8mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.5mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.3mg), 2d (437.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 3 hours, obtain product 3d (318.4mg, 76%) (petrol ether/ethyl acetate=50/1 ~ 30/1): product is solid, fusing point: 124.9-126.1 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.26(d,J＝6.9Hz,2H,ArH),8.19(d,J＝8.1Hz,1H,ArH),7.63(t,J＝7.4Hz,1H,ArH),7.56-7.15(m,11H,ArH),6.93(s,1H,ArH),4.32(q,J＝7.1Hz,2H,NCH
2),3.63-3.42(m,2H,ArCH
2),3.28-3.03(m,2H,CH
2),1.42(t,J＝7.2Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.6,149.2,141.8,140.7,140.4,138.4,133.5,130.1,129.7,128.5,128.3,126.1,125.0,122.5,122.3,119.2,118.7,113.2,108.4,99.8,37.6,36.1,35.7,13.6；IR(KBr)ν(cm
-1)3060,3027,2976,2933,2869,1736,1620,1596,1452,1435,1378,1329,1261,1178,1123,1081,1064,1026,1000；MS(70ev,EI)m/z(％)420(M
++1,23.73),419(M
+,72.22),105(100)；ElementalanalysiscalcdforC
29H
25NO
2:C,83.03；H,6.01；N,3.34；Found:C,83.30,H,5.99；N,3.19.
(5) 2-benzoyloxy-9-ethyl-4-sec.-propyl-9H-carbazole (3e) (qya-8-122)
Silver hexafluoroantimonate (17.7mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.3mg), 2e (375.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 3 hours, obtain product 3e (268.1mg, 75%) (sherwood oil/methylene dichloride=5/1): product is solid, fusing point: 108.8-110.5 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.22-8.12(m,2H,ArH),8.08(d,J＝8.1Hz,1H,ArH),7.49(t,J＝7.4Hz,1H,ArH),7.43-7.24(m,4H,ArH),7.13(t,J＝7.4Hz,1H,ArH),7.08-7.03(m,1H,ArH),6.90(d,J＝1.5Hz,1H,ArH),4.17(q,J＝7.2Hz,2H,NCH
2),3.87(heptet,J＝6.7Hz,1H,ArCH),1.38(d,J＝6.6Hz,6H,2×CH
3),1.27(t,J＝7.2Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.5,149.6,145.7,140.55,140.46,133.4,130.1,129.9,128.5,124.8,122.8,122.4,119.1,118.2,109.0,108.3,99.4,37.5,30.4,22.5,13.6；IR(KBr)ν(cm
-1)3058,2967,2932,2871,1736,1619,1597,1585,1460,1450,1433,1379,1351,1327,1264,1177,1122,1085,1060,1025；MS(70ev,EI)m/z(％)358(M
++1,21.62),357(M
+,77.89),105(100)；ElementalanalysiscalcdforC
24H
23NO
2:C,80.64；H,6.49；N,3.92；Found:C,80.68,H,6.51；N,3.74.
(6) 2-benzoyloxy-9-ethyl-4-cyclohexyl-9H-carbazole (3f) (qya-8-123)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.1mg), 2f (413.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 3 hours, obtain product 3f (305.4mg, 77%) (sherwood oil/methylene dichloride=5/1): product is solid, fusing point: 172.8-174.0 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.32-8.18(m,2H,ArH),8.11(d,J＝7.8Hz,1H,ArH),7.63-7.53(m,1H,ArH),7.52-7.33(m,4H,ArH),7.28-7.21(m,1H,ArH),7.16(d,J＝1.8Hz,1H,ArH),6.98(d,J＝1.8Hz,1H,ArH),4.26(q,J＝7.2Hz,2H,NCH
2),3.63-3.44(m,1H,ArCH),2.31-2.11(m,2H,CH
2),2.02-1.80(m,3H,CH
2+oneprotonofCH
2),1.72-1.48(m,4H,2×CH
2),1.42-1.31(m,4H,CH
3+oneprotonofCH
2)；
13CNMR(75MHz,CDCl
3)δ165.5,149.6,144.8,140.5,140.4,133.4,130.1,129.9,128.5,124.7,122.5,122.4,119.1,118.2,109.4,108.3,99.3,40.9,37.5,32.9,27.1,26.4,13.6；IR(KBr)ν(cm
-1)3058,2975,2927,2852,1737,1620,1597,1585,1471,1450,1433,1379,1351,1329,1262,1173,1138,1122,1081,1063,1025；MS(70ev,EI)m/z(％)398(M
++1,28.21),397(M
+,92.52),105(100)；ElementalanalysiscalcdforC
27H
27NO
2:C,81.58；H,6.85；N,3.52；Found:C,81.59,H,6.86；N,3.33.
(7) 2-benzoyloxy-4-propyl group-9-phenyl-9H-carbazole (3g) (qya-8-187)
Silver hexafluoroantimonate (17.0mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (502.1mg), 2g (423.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtains product 3g (317.2mg, 78%) (petrol ether/ethyl acetate=50/1): Product liquid.
1HNMR(300MHz,CDCl
3)δ8.30-8.05(m,3H,ArH),7.57-7.23(m,11H,ArH),7.18(d,J＝1.8Hz,1H,ArH),6.96(d,J＝1.8Hz,1H,ArH),3.25(t,J＝7.7Hz,2H,ArCH
2),2.05-1.82(m,2H,CH
2),1.13(t,J＝7.4Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.4,149.2,141.7,141.5,139.1,137.2,133.4,130.0,129.8,129.6,128.4,127.7,127.3,125.1,122.9,122.3,120.1,119.1,114.5,109.6,100.7,36.3,22.6,14.2；IR(neat)ν(cm
-1)3060,2958,2931,2870,1737,1620,1597,1504,1455,1428,1366,1331,1262,1222,1197,1176,1135,1079,1063,1025,1001；MS(70ev,EI)m/z(％)406(M
++1,16.33),405(M
+,52.34),105(100)；HRMSCalcdforC
28H
23NO
2(M
+):405.1729,Found:405.1735.
(8) the chloro-9H-carbazole (3h) (qya-8-186) of 2-benzoyloxy-4-propyl group-9-benzyl-6-
Silver hexafluoroantimonate (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (502.6mg), 2h (463.9mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtain product 3h (377.0mg, 84%) (sherwood oil/methylene dichloride=5/1 ~ 2/1): product is solid, fusing point: 177.0-178.1 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.21(d,J＝7.5Hz,2H,ArH),8.05(d,J＝2.1Hz,1H,ArH),7.61(t,J＝7.4Hz,1H,ArH),7.48(t,J＝7.8Hz,2H,ArH),7.33(dd,J
1＝8.7HzandJ
2＝1.8Hz,1H,ArH),7.28-7.17(m,4H,ArH),7.14-7.03(m,3H,ArH),6.93(d,J＝1.2Hz,1H,ArH),5.39(s,2H,NCH
2),3.18(t,J＝7.7Hz,2H,CH
2),1.99-1.78(m,2H,CH
2),1.13(t,J＝7.5Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.4,149.8,141.9,139.5,139.4,136.3,133.5,130.1,129.6,128.8,128.5,127.6,126.2,125.0,124.9,123.8,121.9,118.0,114.1,109.7,100.1,46.6,36.0,22.4,14.2；IR(KBr)ν(cm
-1)2958,2929,2870,1735,1618,1596,1496,1452,1413,1329,1299,1263,1164,1136,1087,1059,1025；MS(70ev,EI)m/z(％)455(M
+(
37Cl),10.59),453(M
+(
35Cl),27.88),105(100)；ElementalanalysiscalcdforC
29H
24ClNO
2:C,76.73；H,5.33；N,3.09；Found:C,77.08,H,5.60；N,2.80.
(9) the bromo-9H-carbazole (3i) (qya-8-181) of 2-benzoyloxy-4-propyl group-9-benzyl-6-
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (502.1mg), 2i (516.2mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 2 hours, obtain product 3i (389.9mg, 78%) (sherwood oil/methylene dichloride=5/1 ~ 2/1): product is solid, fusing point: 179.8-180.6 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.25-8.13(m,3H,ArH),7.66-7.56(m,1H,ArH),7.54-7.41(m,3H,ArH),7.28-7.16(m,4H,ArH),7.13-7.03(m,3H,ArH),6.93(d,J＝1.5Hz,1H,ArH),5.40(s,2H,NCH
2),3.18(t,J＝7.7Hz,2H,CH
2),1.97-1.81(m,2H,CH
2),1.13(t,J＝7.4Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.4,149.8,141.7,139.7,139.5,136.3,133.5,130.1,129.6,128.8,128.5,127.7,127.6,126.2,124.9,124.4,117.9,114.2,112.4,110.2,100.1,46.6,36.0,22.3,14.1；IR(KBr)ν(cm
-1)3063,3032,2958,2929,2870,1735,1620,1597,1452,1414,1357,1330,1312,1263,1165,1136,1089,1067,1025；MS(70ev,EI)m/z(％)500(M
+(
81Br)+1,7.29),499(M
+(
81Br),21.41),498(M
+(
79Br)+1,7.47),497(M
+(
79Br),22.52),105(100)；ElementalanalysiscalcdforC
29H
24BrNO
2:C,69.88；H,4.85；N,2.81；Found:C,70.01,H,4.87；N,2.65.
(10) 2-benzoyloxy-4-propyl group-9-benzyl-7-methoxyl group-9H-carbazole (3j) (qya-8-146)
Silver hexafluoroantimonate (17.5mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.0mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (500.6mg), 2j (465.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 5 hours, obtain product 3j (236.6mg, 53%) (petrol ether/ethyl acetate=20/1): product is solid, fusing point: 204.2-205.6 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.21(d,J＝7.2Hz,2H,ArH),7.99(d,J＝8.7Hz,1H,ArH),7.61(t,J＝7.5Hz,1H,ArH),7.49(t,J＝7.7Hz,2H,ArH),7.32-7.18(m,5H,ArH),7.06(d,J＝1.8Hz,1H,ArH),6.94-6.76(m,3H,ArH),5.40(s,2H,NCH
2),3.85(s,3H,CH
3),3.18(t,J＝7.7Hz,2H,CH
2),1.99-1.82(m,2H,CH
2),1.12(t,J＝7.4Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.6,158.4,148.4,142.7,141.5,138.0,136.7,133.4,130.1,129.8,128.8,128.5,127.4,126.3,123.0,119.1,116.7,113.8,107.6,99.7,93.5,55.5,46.6,36.2,22.5,14.3；IR(KBr)ν(cm
-1)2958,2931,2871,2831,1732,1619,1584,1490,1470,1451,1435,1400,1378,1313,1265,1221,1142,1172,1142,1104,1066,1041,1026；MS(70ev,EI)m/z(％)450(M
++1,36.52),449(M
+,100)；ElementalanalysiscalcdforC
30H
27NO
3:C,80.15；H,6.05；N,3.12；Found:C,80.15,H,6.04；N,2.90.
(11) 2-benzoyloxy-9-ethyl-9H-carbazole (3k) (qya-8-150)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.1mg), 2k (330.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtain product 3k (318.4mg, 76%) (petrol ether/ethyl acetate=30/1): product is solid, fusing point: 122.6-123.6 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.20-8.11(m,2H,ArH),8.09-7.98(m,2H,ArH),7.62-7.53(m,1H,ArH),7.51-7.37(m,3H,ArH),7.32(d,J＝8.1Hz,1H,ArH),7.26(d,J＝1.5Hz,1H,ArH),7.24-7.16(m,1H,ArH),7.06(dd,J
1＝8.4HzandJ
2＝1.8Hz,1H,ArH),4.22(q,J＝7.2Hz,2H,NCH
2),1.35(t,J＝7.2Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.5,149.4,140.4,140.3,133.4,130.1,129.7,128.5,125.4,122.6,120.8,120.2,119.1,112.7,108.4,101.8,37.5,13.6；IR(KBr)ν(cm
-1)3060,2976,2933,1732,1631,1599,1494,1459,1380,1337,1261,1226,1169,1116,1079,1064,1025,1001；MS(70ev,EI)m/z(％)316(M
++1,5.92),315(M
+,25.87),105(100)；ElementalanalysiscalcdforC
21H
17NO
2:C,79.98；H,5.43；N,4.44；Found:C,80.19,H,5.44；N,4.29.
(12) 2-benzoyloxy-3,4-dimethyl-9-butyl-9H-carbazole (3l) (qya-8-156)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.3mg), 2l (389.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 2 hours, obtain product 3l (302.3mg, 81%) (petrol ether/ethyl acetate=50/1): product is solid, fusing point: 160.8-161.7 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.33-8.26(m,2H,ArH),8.23(d,J＝7.8Hz,1H,ArH),7.66-7.57(m,1H,ArH),7.50(t,J＝7.4Hz,2H,ArH),7.45-7.32(m,2H,ArH),7.25-7.17(m,1H,ArH),7.08(s,1H,ArH),4.18(t,J＝7.2Hz,2H,NCH
2),2.84(s,3H,ArCH
3),2.30(s,3H,ArCH
3),1.86-1.67(m,2H,CH
2),1.42-1.28(m,2H,CH
2),0.90(t,J＝7.4Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.4,147.9,141.0,138.8,133.5,133.0,130.2,129.7,128.6,124.7,123.3,122.6,119.9,119.1,118.7,108.3,99.7,42.7,30.9,20.5,16.9,13.8,12.3；IR(KBr)ν(cm
-1)2958,2930,2872,1736,1622,1598,1451,1355,1331,1313,1263,1171,1127,1091,1070,1025；MS(70ev,EI)m/z(％)372(M
++1,13.24),371(M
+,50.67),105(100)；ElementalanalysiscalcdforC
25H
25NO
2:C,80.83；H,6.78；N,3.77；Found:C,81.04,H,6.78；N,3.61.
(13) 2-benzoyloxy-3,4-dimethyl-9-allyl group-9H-carbazole (3m) (qya-8-172)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.3mg), 2m (373.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtain product 3m (184.8mg, 76%) (petrol ether/ethyl acetate=100/1 ~ 50/1): product is solid, fusing point: 142.6-143.7 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.26(d,J＝7.2Hz,2H,ArH),8.21(d,J＝8.1Hz,1H,ArH),7.56(t,J＝7.4Hz,1H,ArH),7.45(t,J＝7.4Hz,2H,ArH),7.38(t,J＝7.5Hz,1H,ArH),7.27(d,J＝8.1Hz,1H,ArH),7.20(t,J＝7.5Hz,1H,ArH),7.04(s,1H,ArH),5.98-5.75(m,1H,＝CH),5.08(d,J＝10.2Hz,1H,oneprotonof＝CH
2),4.95(d,J＝17.1Hz,1H,oneprotonof＝CH
2),4.77-4.61(m,2H,NCH
2),2.80(s,3H,ArCH
3),2.28(s,3H,ArCH
3)；
13CNMR(75MHz,CDCl
3)δ165.3,148.0,140.9,138.7,133.4,132.9,132.0,130.1,129.6,128.5,124.8,123.3,122.5,119.9,119.5,119.0,116.6,108.4,99.8,45.0,16.8,12.3；IR(KBr)ν(cm
-1)2924,1735,1623,1599,1482,1451,1359,1330,1313,1264,1169,1131,1092,1070,1024；MS(70ev,EI)m/z(％)356(M
++1,12.06),355(M
+,45.37),105(100)；ElementalanalysiscalcdforC
24H
21NO
2:C,81.10；H,5.96；N,3.94；Found:C,81.27,H,5.98；N,3.79.
(14) 2-benzoyloxy-3,4-dimethyl-9-phenyl-9H-carbazole (3n) (qya-8-175)
Silver hexafluoroantimonate (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (502.6mg), 2n (409.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 5 hours, obtain product 3n (119.8mg, 31%) (sherwood oil/methylene dichloride=10/1 ~ 5/1 ~ 3/1): product is solid, fusing point: 164.1-166.0 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.29(d,J＝7.8Hz,1H,ArH),8.22(d,J＝7.5Hz,2H,ArH),7.64-7.22(m,11H,ArH),7.05(s,1H,ArH),2.89(s,3H,ArCH
3),2.31(s,3H,ArCH
3)；
13CNMR(75MHz,CDCl
3)δ165.3,148.1,141.6,139.4,137.4,133.5,133.0,130.1,129.9,129.6,128.5,127.6,127.3,125.0,123.8,122.6,120.44,120.38,119.8,109.4,100.8,17.0,12.4；IR(KBr)ν(cm
-1)1736,1621,1598,1502,1453,1363,1312,1278,1261,1248,1204,1177,1133,1095；MS(70ev,EI)m/z(％)392(M
++1,11.49),391(M
+,39.48),105(100)；ElementalanalysiscalcdforC
27H
21NO
2:C,82.84；H,5.41；N,3.58；Found:C,82.86,H,5.41；N,3.40.
(15) 2-benzoyloxy-3,4-dimethyl-9-benzyl-9H-carbazole (3o) (qya-8-169)
Silver hexafluoroantimonate (17.8mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.2mg), 2o (423.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtain product 3o (201.4mg, 50%) (sherwood oil/methylene dichloride=10/1 ~ 5/1 ~ 2/1): product is solid, fusing point: 213.0-213.8 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.33-8.15(m,3H,ArH),7.67-7.58(m,1H,ArH),7.51(t,J＝7.7Hz,2H,ArH),7.43-7.36(m,1H,ArH),7.33(d,J＝8.1Hz,1H,ArH),7.28-7.17(m,4H,ArH),7.13-7.03(m,3H,ArH),5.44(s,2H,NCH
2),2.89(s,3H,ArCH
3),2.31(s,3H,ArCH
3)；
13CNMR(75MHz,CDCl
3)δ165.3,148.1,141.2,139.1,136.9,133.5,133.1,130.1,129.6,128.7,128.5,127.3,126.2,125.0,123.5,122.6,120.1,119.8,119.2,108.6,100.0,46.4,16.9,12.3；IR(KBr)ν(cm
-1)3060,2925,2869,1735,1621,1598,1502,1452,1363,1312,1278,1261,1204,1177,1133,1096,1063,1024；MS(70ev,EI)m/z(％)406(M
++1,13.83),405(M
+,44.99),105(100)；ElementalanalysiscalcdforC
28H
23NO
2:C,82.94；H,5.72；N,3.45；Found:C,82.92,H,5.74；N,3.27.
(16) 2-benzoyloxy-1,3,4-trimethylammonium-9-ethyl-9H-carbazole (3p) (qya-8-157)
Silver hexafluoroantimonate (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (502.1mg), 2p (375.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 2 hours, obtain product 3p (275.7mg, 77%) (petrol ether/ethyl acetate=50/1 ~ 30/1): product is solid, fusing point: 181.8-182.7 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.39-8.27(m,2H,ArH),8.25(d,J＝7.8Hz,1H,ArH),7.72-7.62(m,1H,ArH),7.55(t,J＝7.7Hz,2H,ArH),7.48-7.36(m,2H,ArH),7.26-7.16(m,1H,ArH),4.69-4.41(m,2H,NCH
2),2.83(s,3H,ArCH
3),2.60(s,3H,ArCH
3),2.28(s,3H,ArCH
3),1.42(t,J＝7.1Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ164.9,146.8,141.5,137.4,133.5,130.1,130.0,129.4,128.6,124.6,123.7,122.7,120.7,119.6,118.9,109.7,108.3,39.4,16.9,15.3,12.8,12.1；IR(KBr)ν(cm
-1)2974,2928,2871,1732,1583,1451,1399,1379,1340,1311,1269,1251,1169,1150,1092,1068,1025；MS(70ev,EI)m/z(％)358(M
++1,13.51),357(M
+,46.56),105(100)；ElementalanalysiscalcdforC
24H
23NO
2:C,80.64；H,6.49；N,3.92；Found:C,80.93,H,6.47；N,3.75.
(17) 2-benzoyloxy-3,4-dimethyl-9-ethyl-1-butyl-9H-carbazole (3q) (qya-9-013)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.2mg), 2q (418.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 2 hours, obtains product 3q (360.2mg, 90%) (petrol ether/ethyl acetate=100/1 ~ 50/1): product is liquid.
Thereactionof[IPrAuCl](31.2mg,0.05mmol),AgSbF
6(17.6mg,0.05mmol),
MS(501.2mg),and2q(418.1mg,1.0mmol)inDCE(10mL)atrtfor2hafforded3q(360.2mg,90％)(petroleumether/ethylacetate＝100/1～50/1):liquid；
1HNMR(300MHz,CDCl
3)δ8.36-8.27(m,2H,ArH),8.25(d,J＝7.8Hz,1H,ArH),7.66-7.57(m,1H,ArH),7.52(t,J＝7.5Hz,2H,ArH),7.47-7.33(m,2H,ArH),7.28-7.16(m,1H,ArH),4.46(q,J＝7.0Hz,2H,NCH
2),3.13-2.98(m,1H,oneprotonofCH
2),2.93-2.68(m,4H,CH
3+oneprotonofCH
2),2.26(s,3H,CH
3),1.83-1.53(m,2H,CH
2),1.47-1.27(m,5H,CH
3+CH
2),0.87(t,J＝7.4Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.3,146.7,141.4,136.6,133.5,130.2,130.1,129.5,128.6,124.7,123.8,122.8,121.2,119.9,118.9,114.9,108.3,39.1,33.5,25.9,22.7,17.0,14.9,13.7,12.9；IR(neat)ν(cm
-1)3050,2958,2929,2871,1732,1584,1487,1451,1404,1378,1339,1312,1267,1199,1169,1151,1091,1070,1025；MS(70ev,EI)m/z(％)400(M
++1,16.29),399(M
+,56.05),105(100)；HRMSCalcdforC
27H
29NO
2(M
+):399.2198,Found:399.2204.
(18) 2-benzoyloxy-3,4-dimethyl-9-ethyl-1-phenyl-9H-carbazole (3r) (qya-9-014)
Silver hexafluoroantimonate (17.0mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.9mg), 2r (436.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 2 hours, obtain product 3r (373.8mg, 89%) (petrol ether/ethyl acetate=50/1 ~ 30/1): product is solid, fusing point: 195.6-196.7 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.30(d,J＝7.5Hz,1H,ArH),7.82(d,J＝7.5Hz,2H,ArH),7.55-7.08(m,11H,ArH),3.73(q,J＝7.0Hz,2H,NCH
2),2.91(s,3H,CH
3),2.30(s,3H,CH
3),0.93(t,J＝6.9Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.4,146.1,141.3,136.1,135.5,133.0,132.0,130.3,130.2,129.7,129.4,128.2,128.0,127.8,127.6,124.8,123.5,122.8,120.9,119.7,119.0,116.0,108.6,38.3,17.1,13.8,12.8；IR(KBr)ν(cm
-1)3057,2927,1734,1602,1581,1471,1450,1399,1376,1343,1315,1259,1174,1091,1069,1026；MS(70ev,EI)m/z(％)420(M
++1,21.07),419(M
+,65.18),105(100)；ElementalanalysiscalcdforC
29H
25NO
2:C,83.03；H,6.01；N,3.34；Found:C,83.12,H,5.89；N,3.22.
(19) 2-benzoyloxy-3,4,6-trimethylammonium-9-ethyl-9H-carbazole (3s) (qya-7-171)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.1mg), 2s (376.2mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 3 hours, obtain product 3s (293.6mg, 82%) (petrol ether/ethyl acetate=20/1): product is solid, fusing point: 197.5-198.6 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.29(d,J＝7.2Hz,2H,ArH),8.03(s,1H,ArH),7.64(t,J＝7.4Hz,1H,ArH),7.52(t,J＝7.5Hz,2H,ArH),7.32-7.21(m,2H,ArH),7.06(s,1H,ArH),4.24(q,J＝7.1Hz,2H,NCH
2),2.84(s,3H,ArCH
3),2.55(s,3H,ArCH
3),2.30(s,3H,ArCH
3),1.35(t,J＝7.2Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.5,147.8,138.8,138.5,133.5,133.0,130.2,129.7,128.6,127.8,125.9,123.5,122.8,119.8,118.8,107.8,99.4,37.4,21.6,17.0,13.5,12.3；IR(KBr)ν(cm
-1)2972,2922,1731,1603,1486,1451,1379,1349,1309,1266,1185,1123,1092,1069；MS(70ev,EI)m/z(％)358(M
++1,13.90),357(M
+,54.39),105(100)；ElementalanalysiscalcdforC
24H
23NO
2:C,80.64；H,6.49；N,3.92；Found:C,80.50,H,6.38；N,3.68.
1 gram of scale reaction:
Silver hexafluoroantimonate (51.8mg, 0.15mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (93.9mg, 0.15mmol) is added successively in the reaction tubes of drying,
molecular sieve (1502.1mg), 2s (1126.0mg, 1.0mmol), and 1,2-ethylene dichloride (30mL), then at room temperature stirring reaction 3 hours, obtains product 3s (921.1mg, 86%) (petrol ether/ethyl acetate=50/1 ~ 30/1): product is solid.
1HNMR(300MHz,CDCl
3)δ8.34-8.21(m,2H,ArH),8.04(s,1H,ArH),7.68-7.58(m,1H,ArH),7.57-7.47(m,2H,ArH),7.30-7.21(m,2H,ArH),7.06(s,1H,ArH),4.25(q,J＝7.2Hz,2H,NCH
2),2.85(s,3H,ArCH
3),2.55(s,3H,ArCH
3),2.30(s,3H,ArCH
3),1.36(t,J＝7.1Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.4,147.9,138.8,138.6,133.5,133.0,130.1,129.8,128.6,127.8,126.0,123.6,122.8,119.9,118.9,107.8,99.4,37.4,21.6,17.0,13.5,12.3.
(20) 2-benzoyloxy-3,4,9-triethyl-9H-carbazole (3t) (qya-9-031)
Silver hexafluoroantimonate (17.5mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.3mg), 2t (389.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtain product 3t (259.7mg, 70%) (petrol ether/ethyl acetate=100/1 ~ 50/1): product is solid, fusing point: 143.0-143.9 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.29(d,J＝7.2Hz,2H,ArH),8.16(d,J＝7.8Hz,1H,ArH),7.60(t,J＝7.2Hz,1H,ArH),7.49(t,J＝7.5Hz,2H,ArH),7.42(t,J＝7.5Hz,1H,ArH),7.34(d,J＝8.1Hz,1H,ArH),7.23(t,J＝7.4Hz,1H,ArH),7.14(s,1H,ArH),4.23(q,J＝7.2Hz,2H,NCH
2),3.32(q,J＝7.5Hz,2H,CH
2),2.80(q,J＝7.4Hz,2H,CH
2),1.44(t,J＝7.5Hz,3H,CH
3),1.35(t,J＝7.1Hz,3H,CH
3),1.23(t,J＝7.5Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.6,147.9,140.4,138.63,138.61,133.5,130.0,129.8,128.6,124.7,124.6,122.5,122.4,119.1,118.8,108.2,100.2,37.3,23.1,19.7,15.7,14.2,13.6；IR(KBr)ν(cm
-1)3060,2969,2933,2873,1738,1732,1621,1598,1479,1451,1378,1350,1327,1269,1190,1174,1108,1064,1025；MS(70ev,EI)m/z(％)372(M
++1,12.03),371(M
+,43.81),105(100)；ElementalanalysiscalcdforC
25H
25NO
2:C,80.83；H,6.78；N,3.77；Found:C,81.06,H,6.81；N,3.58.
(21) 2-benzoyloxy-9-ethyl-3,4-dipropyl-9H-carbazole (3u) (qya-8-173)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.2mg), 2u (416.0mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 5 hours, obtains product 3u (179.6mg, 45%) (petrol ether/ethyl acetate=100/1 ~ 50/1): product is liquid.
1HNMR(300MHz,CDCl
3)δ8.33-8.21(m,2H,ArH),8.09(d,J＝8.1Hz,1H,ArH),7.65-7.57(m,1H,ArH),7.51(t,J＝7.4Hz,2H,ArH),7.45-7.33(m,2H,ArH),7.23(t,J＝7.5Hz,1H,ArH),7.14(s,1H,ArH),4.25(q,J＝7.1Hz,2H,NCH
2),3.34-3.11(m,2H,CH
2),2.83-2.62(m,2H,CH
2),1.93-1.72(m,2H,CH
2),1.72-1.54(m,2H,CH
2),1.37(t,J＝7.2Hz,3H,CH
3),1.19(t,J＝7.2Hz,3H,CH
3),0.97(t,J＝7.4Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.5,148.0,140.5,138.7,137.6,133.4,130.0,129.9,128.6,124.7,123.5,122.7,122.3,119.4,118.9,108.2,100.2,37.4,32.4,28.8,24.6,23.1,14.7,14.5,13.6；IR(neat)ν(cm
-1)3060,2958,2931,2871,1737,1621,1597,1478,1450,1378,1327,1263,1188,1173,1110,1065,1026；MS(70ev,EI)m/z(％)400(M
++1,14.42),399(M
+,47.72),105(100)；HRMSCalcdforC
27H
29NO
2(M
+):399.2198,Found:399.2196.
(22) 2-benzoyloxy-9-ethyl-3,4-trimethylene-9H-carbazole (3v) (qya-8-151)
Silver hexafluoroantimonate (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.8mg), 2v (374.3mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 3 hours, obtain product 3v (254.8mg, 72%) (petrol ether/ethyl acetate=50/1): product is solid, fusing point: 138.9-139.7 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.32-8.18(m,2H,ArH),8.01(d,J＝7.8Hz,1H,ArH),7.64-7.54(m,1H,ArH),7.53-7.29(m,4H,ArH),7.25-7.16(m,1H,ArH),7.10(s,1H,ArH),4.25(q,J＝7.1Hz,2H,NCH
2),3.44(t,J＝7.4Hz,2H,CH
2),2.98(t,J＝7.5Hz,2H,CH
2),2.27(quint,J＝7.5Hz,2H,CH
2),1.36(t,J＝7.2Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ164.9,145.8,140.5,139.9,139.5,133.4,130.1,129.8,128.5,127.2,124.9,122.7,121.6,118.8,117.4,108.1,99.3,37.7,32.5,.29.4,25.2,13.6；IR(KBr)ν(cm
-1)3060,2972,2934,2848,1735,1629,1601,1477,1449,1343,1313,1263,1188,1166,1115,1093,1065,1026；MS(70ev,EI)m/z(％)356(M
++1,14.23),355(M
+,51.80),105(100)；ElementalanalysiscalcdforC
24H
21NO
2:C,81.10；H,5.96；N,3.94；Found:C,81.42,H,5.97；N,3.79.
(23) 2-benzoyloxy-4-methyl-9-ethyl-3-propyl group-9H-carbazole (3w) (qya-10-125)
Silver hexafluoroantimonate (17.5mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.8mg), 2w (389.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 12 hours, obtain product 3w and 3w ' (337.5mg, 91%, 3w:3w '=97:3asdeterminedby
1hNMRanalysis) (petrol ether/ethyl acetate=50/1): product is solid, fusing point: 150.4-151.3 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.34-8.18(m,3H,ArH),7.70-7.62(m,1H,ArH),7.55(t,J＝7.5Hz,2H,ArH),7.47-7.35(m,2H,ArH),7.28-7.17(m,1H,ArH),7.13(s,1H,ArH),4.29(q,J＝7.1Hz,2H,NCH
2),2.89(s,3H,CH
3),2.81-2.70(m,2H,CH
2),1.72-1.52(m,2H,CH
2),1.40(t,J＝7.2Hz,3H,CH
3),0.96(t,J＝7.2Hz,3H,CH
3)；thefollowingsignalisdiscerniblefor3w’:8.12(d,J＝8.7Hz,1H,ArH),3.40-3.33(m,2H,ArCH
2),2.33(s,3H,ArCH
3)；
13CNMR(75MHz,CDCl
3)δ165.7,147.9,140.5,138.3,133.5,132.9,130.1,129.8,128.6,124.7,123.8,123.5,122.7,120.0,118.7,108.1,99.9,37.4,28.8,23.9,16.8,14.2,13.6；IR(KBr)ν(cm
-1)2959,2931,2871,1735,1622,1598,1473,1449,1378,1348,1326,1267,1189,1173,1105,1064；MS(70ev,EI)m/z(％)372(M
++1,18.21),371(M
+,62.35),105(100)；ElementalanalysiscalcdforC
25H
25NO
2:C,80.83；H,6.78；N,3.77；Found:C,81.01,H,6.85；N,3.56.
(24) 2-benzoyloxy-Isosorbide-5-Nitrae-dimethyl-9-ethyl-3-propyl group-9H-carbazole (3x) (qya-10-148)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.8mg), 2x (403.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtain product 3x and 3x ' (338.9mg, 88%, 3x:3x '=96:4asdeterminedby
1hNMRanalysis) (sherwood oil/methylene dichloride=10/1 ~ 5/1): product is solid, recrystallization obtains 3x (281.1mg, 73%), fusing point: 174.6-175.7 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.34-8.27(m,2H,ArH),8.24(d,J＝7.8Hz,1H,ArH),7.68-7.62(m,1H,ArH),7.58-7.50(m,2H,ArH),7.47-7.34(m,2H,ArH),7.27-7.17(m,1H,ArH),4.67-4.40(m,2H,NCH
2),2.89-2.72(m,4H,CH
3+oneprotonofCH
2),2.63-2.46(m,4H,CH
3+oneprotonofCH
2),1.72-1.46(m,2H,CH
2),1.42(t,J＝7.4Hz,3H,CH
3),0.93(t,J＝7.4Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.2,146.7,141.5,137.5,133.6,130.1,129.9,129.5,128.7,124.7,124.3,123.8,122.8,120.8,118.9,110.0,108.3,39.5,29.6,23.9,16.8,15.5,14.3,12.3；IR(KBr)ν(cm
-1)2958,2928,2868,1734,1585,1479,1450,1398,1376,1341,1312,1268,1222,1168,1150,1107,1090,1067,1026；MS(70ev,EI)m/z(％)386(M
++1,15.79),385(M
+,50.36),105(100)；ElementalanalysiscalcdforC
26H
27NO
2:C,81.01；H,7.06；N,3.63；Found:C,81.13,H,7.08；N,3.44.
(25) 2-benzoyloxy-4-methyl-9-ethyl-3-propyl group-1-butyl-9H-carbazole (3y) (qya-10-166)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.8mg), 2y (445.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 12 hours, obtain product 3y and 3y ' (382.1mg, 89%, 3y:3y '=96:4asdeterminedby
1hNMRanalysis) (petrol ether/ethyl acetate=50/1): product is liquid.
1HNMR(300MHz,CDCl
3)δ8.31(d,J＝8.1Hz,2H,ArH),8.25(d,J＝7.8Hz,1H,ArH),7.68-7.58(m,1H,ArH),7.53(t,J＝7.5Hz,2H,ArH),7.47-7.36(m,2H,ArH),7.26-7.18(m,1H,ArH),4.47(q,J＝7.1Hz,2H,NCH
2),3.12-2.94(m,1H,oneprotonofCH
2),2.90-2.67(m,5H,CH
3+CH
2),2.61-2.43(m,1H,oneprotonofCH
2),1.84-1.53(m,4H,2×CH
2),1.46-1.28(m,5H,CH
3+CH
2),0.91(t,J＝7.4Hz,3H,CH
3),0.86(t,J＝7.5Hz,3H,CH
3)；thefollowingsignalisdiscerniblefor3y’:8.12(d,J＝7.5Hz,1H,ArH),3.27-3.21(m,1H,oneprotonofCH
2),2.28(s,3H,ArCH
3)；
13CNMR(75MHz,CDCl
3)δ165.8,146.8,141.4,136.7,133.5,130.1,130.0,129.6,128.6,124.7,124.5,123.9,122.8,121.4,118.9,115.1,108.3,39.2,33.4,29.6,26.0,23.8,22.7,16.9,15.0,14.3,13.7；IR(neat)ν(cm
-1)2959,2930,2871,1732,1589,1574,1487,1451,1404,1378,1339,1312,1266,1221,1168,1151,1104,1066,1026；MS(70ev,EI)m/z(％)428(M
++1,32.39),427(M
+,100)；HRMSCalcdforC
29H
33NO
2(M
+):427.2511,Found:427.2517.
(26) 2-benzoyloxy-4-methyl-9-ethyl-3-propyl group-1-butyl-6-methoxyl group-9H-carbazole (3z) (qya-10-189)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.7mg), 2z (474.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 4 hours, obtain product 3zand3z ' (389.2mg, 85%, 3z:3z '=97:3asdeterminedby
1hNMRanalysis) (petrol ether/ethyl acetate=40/1): product is solid, recrystallization obtains 3z (319.2mg, 70%, 3z:3z '=99:1asdeterminedby
1hNMRanalysis): fusing point: 137.6-138.8 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.34-8.25(m,2H,ArH),7.78(d,J＝2.4Hz,1H,ArH),7.72-7.63(m,1H,ArH),7.62-7.52(m,2H,ArH),7.32(d,J＝9.0Hz,1H,ArH),7.10(dd,J
1＝8.7HzandJ
2＝2.4Hz,1H,ArH),4.44(q,J＝7.1Hz,2H,NCH
2),3.93(s,3H,CH
3),3.07-2.89(m,1H,oneprotonofCH
2),2.88-2.65(m,5H,CH
3+CH
2),2.56-2.42(m,1H,oneprotonofCH
2),1.78-1.47(m,4H,2×CH
2),1.44-1.27(m,5H,CH
3+CH
2),0.91(t,J＝7.4Hz,3H,CH
3),0.85(t,J＝7.4Hz,3H,CH
3)；thefollowingsignalisdiscerniblefor3z’:2.25(s,3H,ArCH
3)；
13CNMR(75MHz,CDCl
3)δ165.8,153.3,146.9,137.4,136.7,133.5,130.1,130.0,129.6,128.7,124.4,124.1,121.2,115.2,112.7,108.7,107.2,56.2,39.3,33.2,29.6,26.0,23.8,22.7,16.9,15.0,14.3,13.8；IR(KBr)ν(cm
-1)2958,2930,2871,2830,1734,1618,1584,1490,1468,1451,1435,1378,1313,1265,1221,1172,1142,1104,1065,1041,1025；MS(70ev,EI)m/z(％)458(M
++1,3.32),457(M
+,100)；ElementalanalysiscalcdforC
30H
35NO
3:C,78.74；H,7.71；N,3.06；Found:C,78.92,H,7.79；N,2.83.
(27) 2-benzoyloxy-4-methyl-9-ethyl-3-sec.-propyl-9H-carbazole (3aa) (qya-10-124)
Silver hexafluoroantimonate (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.6mg), 2aa (388.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 12 hours, obtain product 3aa (162.5mg, 44%) (petrol ether/ethyl acetate=50/1): product is solid, fusing point: 147.8-149.1 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.34-8.27(m,2H,ArH),8.26(d,J＝7.8Hz,1H,ArH),7.68-7.61(m,1H,ArH),7.58-7.49(m,2H,ArH),7.46-7.41(m,1H,ArH),7.37(d,J＝7.5Hz,1H,ArH),7.26-7.17(m,1H,ArH),7.05(s,1H,ArH),4.27(q,J＝7.2Hz,2H,NCH
2),3.59(heptet,J＝7.2Hz,1H,CH),2.95(s,3H,CH
3),1.44-1.30(m,9H,3×CH
3)；
13CNMR(75MHz,CDCl
3)δ165.9,148.1,140.6,138.1,133.5,132.6,130.3,129.9,128.64,128.62,124.7,123.6,122.9,120.3,118.7,108.1,101.0,37.4,27.4,21.9,17.4,13.6；IR(neat)ν(cm
-1)2975,2932,2873,1735,1622,1597,1475,1450,1379,1346,1313,1266,1184,1113,1067,1026；MS(70ev,EI)m/z(％)372(M
++1,10.78),371(M
+,36.39),105(100)；ElementalanalysiscalcdforC
25H
25NO
2:C,80.83；H,6.78；N,3.77；Found:C,81.04,H,6.86；N,3.60.
(28) 2-benzoyloxy-4-methyl-9-ethyl-3-(p-methylphenyl)-9H-carbazole (3ab) (qya-10-122)
Silver hexafluoroantimonate (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (501.8mg), 2ab (436.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 24 hours, obtain product 3ab (189.6mg, 45%) (petrol ether/ethyl acetate=50/1): product is solid, fusing point: 146.9-148.3 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.21(d,J＝8.1Hz,1H,ArH),7.89-7.79(m,2H,ArH),7.52-7.37(m,3H,ArH),7.36-7.28(m,2H,ArH),7.27-7.17(m,4H,ArH),7.12(d,J＝8.1Hz,2H,ArH),4.34(q,J＝7.1Hz,2H,NCH
2),2.68(s,3H,CH
3),2.29(s,3H,CH
3),1.41(t,J＝7.2Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.6,147.2,140.5,139.0,136.2,133.9,133.02,132.96,130.5,129.8,129.6,128.6,128.2,126.5,124.9,123.5,122.7,119.7,118.9,108.2,99.8,37.5,21.1,18.2,13.7；IR(KBr)ν(cm
-1)3052,2976,2922,2871,1734,1622,1597,1475,1450,1379,1349,1312,1293,1258,1189,1143,1089,1067,1026,1004；MS(70ev,EI)m/z(％)420(M
++1,16.56),419(M
+,55.11),105(100)；ElementalanalysiscalcdforC
29H
25NO
2:C,83.03；H,6.01；N,3.34；Found:C,83.16,H,6.05；N,3.21.
(29) 2-benzoyloxy-4-methyl-9-ethyl-3-(rubigan)-9H-carbazole (3ac) (qya-10-139)
Silver hexafluoroantimonate (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol) is added successively in the reaction tubes of drying,
molecular sieve (500.8mg), 2ac (459.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then at room temperature stirring reaction 3 hours, obtain product 3ac (242.7mg, 55%) (petrol ether/ethyl acetate=30/1): product is solid, fusing point: 190.1-191.0 DEG C (n-hexane/ethyl acetate).
1HNMR(300MHz,CDCl
3)δ8.22(d,J＝8.1Hz,1H,ArH),7.93-7.81(m,2H,ArH),7.62-7.33(m,5H,ArH),7.33-7.18(m,6H,ArH),4.36(q,J＝7.2Hz,2H,NCH
2),2.67(s,3H,CH
3),1.45(t,J＝7.2Hz,3H,CH
3)；
13CNMR(75MHz,CDCl
3)δ165.4,146.8,140.5,139.2,135.5,133.3,132.7,132.0,129.7,129.3,128.3,128.0,125.11,125.05,123.4,122.7,119.7,119.1,108.3,99.9,37.5,18.1,13.6；IR(KBr)ν(cm
-1)3060,2976,2932,1732,1622,1598,1475,1450,1379,1349,1311,1271,1258,1209,1189,1143,1089,1067,1019；MS(70ev,EI)m/z(％)442(M
+(
37Cl)+1,2.82),441(M
+(
37Cl),9.86),440(M
+(
35Cl)+1,7.68),439(M
+(
35Cl),27.11),105(100)；ElementalanalysiscalcdforC
28H
22ClNO
2:C,76.44；H,5.04；N,3.18；Found:C,76.38,H,5.01；N,2.97.
Finally, it is also to be noted that what enumerate above is only several specific embodiment of the present invention and comparative example.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1. one kind is synthesized the method for functionalization carbazole, it is characterized in that, 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides/silver hexafluoroantimonate catalysis under, the formula 2 chemical combination object height regioselectivity ground synthesizing carbazole compounds that reacts, in the reaction, is in OBz and R of 4-position in raw material
4respectively selective migration is to the 2-position of product carbazole and 3-position, and react and experienced by optionally transition process, its reaction formula is as follows:
R
1=methyl, methoxyl group, chlorine or bromine; R
2=ethyl, phenyl, benzyl, butyl or allyl group; R
3=alkyl; R
4=alkyl or aryl, wherein alkyl is C
nh
2n+1, n=1-3 in formula; R
5=methyl, butyl or phenyl; Concrete steps are as follows:
(1) in glove box, weighed silver hexafluoroantimonate and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides, then added successively
molecular sieve, formula 2 compound, and 1,2-ethylene dichloride, then at room temperature stirring reaction 1-48 hour;
(2) too short silicagel column, concentrated, rapid column chromatography, obtains carbazole compound.
2. the method for synthesis functionalization carbazole according to claim 1, is characterized in that, described R
3the alkyl of=straight chain: n-propyl, n-heptyl, or the alkyl of side chain: sec.-propyl.
3. the method for synthesis functionalization carbazole according to claim 1, it is characterized in that, the mol ratio of described formula 2 compound and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides and silver hexafluoroantimonate is 1: 0.05:0.05.
4. the method for synthesis functionalization carbazole according to claim 1, is characterized in that, the described molar weight of formula 2 compound and the amount ratio of 1,2-ethylene dichloride are 0.1:1, and unit is mmol/mL.
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| US7767841B1 (en) * | 2007-04-05 | 2010-08-03 | University Of New Orleans Research And Technology Foundation, Inc. | Gold complexes for catalysIS and preparation thereof |
| CN103044313A (en) * | 2012-12-06 | 2013-04-17 | 浙江大学 | Method for synthesising carbazole compounds |
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| CN101585803A (en) * | 2009-06-09 | 2009-11-25 | 浙江大学 | Method for synthesizing carbazole compounds |
| CN103044313A (en) * | 2012-12-06 | 2013-04-17 | 浙江大学 | Method for synthesising carbazole compounds |
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