CN104030970A - New method for synthesizing carbazole compound - Google Patents

New method for synthesizing carbazole compound Download PDF

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CN104030970A
CN104030970A CN201410294787.7A CN201410294787A CN104030970A CN 104030970 A CN104030970 A CN 104030970A CN 201410294787 A CN201410294787 A CN 201410294787A CN 104030970 A CN104030970 A CN 104030970A
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carbazole
cdcl
gold
hexafluoro
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CN104030970B (en
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麻生明
仇友爱
周静
傅春玲
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Zhejiang University ZJU
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    • 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

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Abstract

The invention relates to a method for synthesizing a carbazole compound. The method comprises the following steps: under the catalysis of 1,3-Bis(2,6-di-isopropylphenyl)imidazol-2-ylidene gold(I)chloride/ silver hexafluoroantimonate, reacting with 1-(indole-2-group)-2-alkyne-1-alcohol and synthesizing into functionalized carbazole in a high regioselectivity manner. The method has the advantages of being simple to operate, mild in conditions, as well as high regioselectivity of the reaction and the like, the raw materials and reagents are easily available, a plurality of substituent groups can be simultaneously introduced, products are easily separated and purified, and the method is applicable to synthesis of various substituted carbazole compounds.

Description

A kind of novel method of synthesizing carbazole compounds
Technical field
A kind of method that the present invention relates to high regioselectivity and synthesize functionalization carbazole, be that 1-(indoles-2-yl)-2-alkynes-1-alcohol is 1, synthesizing carbazole compounds reacts under the catalysis of 3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides/hexafluoro-antimonic acid silver.
Background technology
Carbazole compound is widespread in nature, and is simultaneously also 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.Due to its special thermodynamics, electricity and optical property, make it in Materials science, also have larger application prospect in addition. 1-2therefore, development structure novelty and polysubstituted carbazole compound gain great popularity, and have become the important new direction of research and development carbazoles medicine.Although research and the application of recent domestic to carbazole and derivative thereof just further goed deep into, 3-4but simple, quick, the efficient and synthetic polysubstituted carbazole of highly selective and the document of derivative thereof are but seldom reported.Limitation is that raw material preparation is difficult for, 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.The?Alkaloids,ed.Manske,R.H.F.Academic?Press,New?York,1971,13,273.(b)Husson,H.P.The?Alkaloids,ed.Brossi,A.Academic?Press,New?York,1985,26,1.(c)Chakraborty,D.P.The?Alkaloids,ed.Bossi,A.Academic?Press,New?York,1993,44,257.(d) H.J.Advances?in?Nitrogen?Heterocycles,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.Macromolecules?2007,40,1914.(i)Sanda,F.；Nakai,T.；Kobayashi,N.；Masuda,T.Macromolecules2004,37,2703.
(3)For?reviews?on?the?synthesis?of?carbazoles,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)For?selected?examples,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.Tetrahedron?Lett.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, efficient, and quick, 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 synthetic functionalization carbazole, 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) under the catalysis of gold (I) acyl chlorides/hexafluoro-antimonic acid silver, the high regioselectivity of 1-(indoles-2-yl)-2-alkynes-1-alcohol the synthesizing carbazole compounds that reacts, in this reaction, the OBz of 4-position and R in raw material 4selective migration is to 2-position and the 3-position of product carbazole respectively, and optionally migration has been experienced in reaction, and 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 hexafluoro-antimonic acid silver and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides, then added successively molecular sieve, 1-(indoles-2-yl)-2-alkynes-1-alcohol, and 1,2-ethylene dichloride, then stirring reaction 1-48 hour at room temperature;
(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-yl)-2-alkynes-1-alcohol and 1, the mol ratio of 3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides and hexafluoro-antimonic acid silver is 1: 0.05:0.05.
As improving further, the mol ratio of 1-of the present invention (indoles-2-yl)-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-yl)-2-alkynes-1-alcohol and react under the catalysis of gold/silver, the method that high regioselectivity ground synthesizes polysubstituted carbazole compound.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 gentleness is applicable to synthesize the carbazole of various replacements.
The present invention has overcome the drawback of traditional method, has the following advantages:
1) reaction has the regioselectivity of height; 2) easy to operate, productive rate is higher; 3) diversity of substrate is abundant; 4) reaction conditions gentleness; 5) environmental friendliness.
Innovative point of the present invention has been to develop the methodology of 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 method of the synthetic functionalization carbazole of the present invention, 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) under the catalysis of gold (I) acyl chlorides/hexafluoro-antimonic acid silver, the high regioselectivity of 1-(indoles-2-yl)-2-alkynes-1-alcohol the synthesizing carbazole compounds that reacts, in this reaction, the OBz of 4-position and R in raw material 4selective migration is to 2-position and the 3-position of product carbazole respectively, 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., can be also 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 in formula, R 5=methyl, butyl, phenyl; The steps include:
(3) in glove box, weighed hexafluoro-antimonic acid silver and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides, then added successively molecular sieve, 1-(indoles-2-yl)-2-alkynes-1-alcohol, and 1,2-ethylene dichloride, then stirring reaction 1-48 hour at room temperature;
(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-yl)-2-alkynes-1-alcohol and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides and hexafluoro-antimonic acid silver is: 1: 0.05:0.05.
The mol ratio of 1-of the present invention (indoles-2-yl)-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 hexafluoro-antimonic acid silver (18.0mg in dry reaction tubes, 0.05mmol) He 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (33.1mg, 0.05mmol, in glove box, weigh), then add successively molecular sieve (501.7mg), 2a (432.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 1 hour at room temperature, 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (18.0mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (502.0mg), 2b (445.7mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 1.5 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (501.6mg), 2c (389.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 1.5 hours at room temperature, obtains 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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.8mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.5mg, 0.05mmol), molecular sieve (501.3mg), 2d (437.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 3 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.7mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol), molecular sieve (501.3mg), 2e (375.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 3 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol), molecular sieve (501.1mg), 2f (413.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 3 hours at room temperature, obtains 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+one?proton?of?CH 2),1.72-1.48(m,4H,2×CH 2),1.42-1.31(m,4H,CH 3+one?proton?of?CH 2)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.0mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol), molecular sieve (502.1mg), 2g (423.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, 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)； 13C?NMR(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) 2-benzoyloxy-4-propyl group-9-chloro-9H-carbazole of benzyl-6-(3h) (qya-8-186)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (502.6mg), 2h (463.9mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 29H 24ClNO 2:C,76.73；H,5.33；N,3.09；Found:C,77.08,H,5.60；N,2.80.
(9) 2-benzoyloxy-4-propyl group-9-bromo-9H-carbazole of benzyl-6-(3i) (qya-8-181)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol), molecular sieve (502.1mg), 2i (516.2mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 2 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.5mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.0mg, 0.05mmol), molecular sieve (500.6mg), 2j (465.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 5 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (501.1mg), 2k (330.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (501.3mg), 2l (389.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 2 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (501.3mg), 2m (373.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, obtains 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,one?proton?of＝CH 2),4.95(d,J＝17.1Hz,1H,one?proton?of＝CH 2),4.77-4.61(m,2H,NCH 2),2.80(s,3H,ArCH 3),2.28(s,3H,ArCH 3)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (502.6mg), 2n (409.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 5 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.8mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (501.2mg), 2o (423.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (502.1mg), 2p (375.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 2 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (501.2mg), 2q (418.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 2 hours at room temperature, obtains product 3q (360.2mg, 90%) (petrol ether/ethyl acetate=100/1～50/1): product is liquid.
The?reaction?of[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,one?proton?of?CH 2),2.93-2.68(m,4H,CH 3+one?proton?of?CH 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)； 13C?NMR(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)；HRMS?Calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.0mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (501.9mg), 2r (436.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 2 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (501.1mg), 2s (376.2mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 3 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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:
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (51.8mg, 0.15mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (93.9mg, 0.15mmol), molecular sieve (1502.1mg), 2s (1126.0mg, 1.0mmol), and 1,2-ethylene dichloride (30mL), then stirring reaction 3 hours at room temperature, 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)； 13C?NMR(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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.5mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (501.3mg), 2t (389.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol), molecular sieve (501.2mg), 2u (416.0mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 5 hours at room temperature, 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)； 13C?NMR(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)；HRMS?Calcd?for?C 27H 29NO 2(M +):399.2198,Found:399.2196.
(22) 2-benzoyloxy-9-ethyl-3,4-trimethylene-9H-carbazole (3v) (qya-8-151)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (501.8mg), 2v (374.3mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 3 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.5mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (501.8mg), 2w (389.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 12 hours at room temperature, obtain product 3w and 3w ' (337.5mg, 91%, 3w:3w '=97:3as determined by 1h NMR analysis) (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)；the?following?signal?is?discernible?for3w’:8.12(d,J＝8.7Hz,1H,ArH),3.40-3.33(m,2H,ArCH 2),2.33(s,3H,ArCH 3)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol), molecular sieve (501.8mg), 2x (403.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, obtain product 3x and 3x ' (338.9mg, 88%, 3x:3x '=96:4as determined by 1h NMR analysis) (sherwood oil/methylene dichloride=10/1～5/1): product is solid, and 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+one?proton?of?CH 2),2.63-2.46(m,4H,CH 3+one?proton?of?CH 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol), molecular sieve (501.8mg), 2y (445.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 12 hours at room temperature, obtain product 3y and 3y ' (382.1mg, 89%, 3y:3y '=96:4as determined by 1h NMR analysis) (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,one?proton?of?CH 2),2.90-2.67(m,5H,CH 3+CH 2),2.61-2.43(m,1H,one?proton?of?CH 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)；the?following?signal?isdiscernible?for3y’:8.12(d,J＝7.5Hz,1H,ArH),3.27-3.21(m,1H,one?proton?of?CH 2),2.28(s,3H,ArCH 3)； 13C?NMR(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)；HRMS?Calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.8mg, 0.05mmol), molecular sieve (501.7mg), 2z (474.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 4 hours at room temperature, obtain product 3zand3z ' (389.2mg, 85%, 3z:3z '=97:3as determined by 1h NMR analysis) (petrol ether/ethyl acetate=40/1): product is solid, and recrystallization obtains 3z (319.2mg, 70%, 3z:3z '=99:1as determined by 1h NMR analysis): 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,one?proton?of?CH 2),2.88-2.65(m,5H,CH 3+CH 2),2.56-2.42(m,1H,one?proton?of?CH 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)；the?following?signal?is?discernible?for3z’:2.25(s,3H,ArCH 3)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.6mg, 0.05mmol), molecular sieve (501.6mg), 2aa (388.8mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 12 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.6mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.3mg, 0.05mmol), molecular sieve (501.8mg), 2ab (436.6mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 24 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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)
In dry reaction tubes, add successively hexafluoro-antimonic acid silver (17.3mg, 0.05mmol) and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides (31.2mg, 0.05mmol), molecular sieve (500.8mg), 2ac (459.1mg, 1.0mmol), and 1,2-ethylene dichloride (10mL), then stirring reaction 3 hours at room temperature, obtains 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)； 13C?NMR(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)；Elemental?analysis?calcd?for?C 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 more than enumerate is only several specific embodiment of the present invention and comparative example.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.

Claims (5)

1. the method for a synthetic functionalization carbazole, it is characterized in that, 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) under the catalysis of gold (I) acyl chlorides/hexafluoro-antimonic acid silver, the high regioselectivity of 1-(indoles-2-yl)-2-alkynes-1-alcohol the synthesizing carbazole compounds that reacts, in this reaction, the OBz of 4-position and R in raw material 4selective migration is to 2-position and the 3-position of product carbazole respectively, and optionally transition process has been experienced in reaction, and 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 hexafluoro-antimonic acid silver and 1,3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides, then added successively molecular sieve, 1-(indoles-2-yl)-2-alkynes-1-alcohol, and 1,2-ethylene dichloride, then stirring reaction 1-48 hour at room temperature;
(2) too short silicagel column, concentrated, rapid column chromatography, obtains carbazole compound.
2. the method for synthetic functionalization carbazole according to claim 1, is characterized in that, described R 3the alkyl of=straight chain: n-propyl, n-heptyl, high benzyl, or the alkyl of side chain or ring-type: sec.-propyl and cyclohexyl.
3. the method for synthetic functionalization carbazole according to claim 1, is characterized in that, described organic solvent is 1,2-ethylene dichloride.
4. the method for synthetic functionalization carbazole according to claim 1, it is characterized in that, described 1-(indoles-2-yl)-2-alkynes-1-alcohol and 1, the mol ratio of 3-two (2,6-diisopropyl phenyl imidazoles-2-subunit) gold (I) acyl chlorides and hexafluoro-antimonic acid silver is 1: 0.05:0.05.
5. the method for synthetic functionalization carbazole according to claim 1, is characterized in that, described 1-(indoles-2-yl)-2-alkynes-1-alcohol and the mol ratio of 1,2-ethylene dichloride are 0.1:1, and unit is mmol/mL.
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