CN103044313B - Method for synthesising carbazole compounds - Google Patents
Method for synthesising carbazole compounds Download PDFInfo
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- CN103044313B CN103044313B CN201210516430.XA CN201210516430A CN103044313B CN 103044313 B CN103044313 B CN 103044313B CN 201210516430 A CN201210516430 A CN 201210516430A CN 103044313 B CN103044313 B CN 103044313B
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Abstract
The invention relates to a method for synthesising carbazole compounds, comprising the step of selectively reacting 1-(indol-2-yl)-3-alkyne-1-alcohol in the presence of gold trichloride in high region to synthesise functionalized carbazole. The method disclosed by the invention has the advantages that operation is simple, raw materials and reagents are available, conditions are moderate, the regioselectivity of the reaction is high, and the like; and moreover, a plurality of substituent groups can be introduced simultaneously, and the product is easily separated and purified. The method is suitable for synthesising various substituent carbazole compounds.
Description
Technical field
A kind of method that the present invention relates to high regioselectivity and synthesize functionalization carbazole, i.e. 1-(indoles-2-yl)-3-alkynes-1-alcohol synthesizing carbazole compounds that reacts under the catalysis of gold perchloride.
Background technology
Carbazole compound is extensively present in occurring in nature in a variety of forms.Carbazole is 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.The carbazole compound of the synthetic of development structure novelty gains great popularity, and has become the important new direction of research and development carbazoles medicine.Research and the application of recent domestic to carbazole and derivative thereof just further goed deep into, and the demand of carbazole also swashed to increase severely add.But simple, quick, the document of synthetic carbazole and derivative thereof is but seldom reported efficiently.Limitation is that raw material is difficult for, severe reaction conditions, and reaction preference is poor, unfriendly etc. to environment.
Summary of the invention
The object of the invention is just to provide a kind of simple, efficient, quick, the method for the one-step synthesis carbazole compound of highly selective.
Concrete technical scheme of the present invention is as follows:
The present invention be a kind of high regioselectivity synthesize the method for functionalization carbazole, 1-(indoles-2-yl)-3-alkynes-1-alcohol synthesizing carbazole compounds that reacts under the catalysis of gold perchloride, reaction formula is as follows:
R
1=ethyl, benzyl, to methoxy-benzyl; R
2=H, methyl, methoxyl group or bromine; R
3=alkyl, phenyl, wherein alkyl is C
n h
2n+1, in formula
n=1-2; R
4=alkyl or phenyl, wherein alkyl is C
n h
2n+1, in formula
n=1-4; Its step is as follows:
(1) successively 1-(indoles-2-yl)-3-alkynes-1-alcohol, gold perchloride are joined in toluene, then stirring reaction 3-19.5 hour at room temperature;
(2) concentrated, rapid column chromatography, obtains carbazole compound.
The mol ratio of 1-of the present invention (indoles-2-yl)-3-alkynes-1-alcohol and gold perchloride is 1: 0.05.
The mol ratio of 1-of the present invention (indoles-2-yl)-3-alkynes-1-alcohol and toluene is 0.1～0.2.
The present invention relates to a kind of 1-(indoles-2-yl)-3-alkynes-1-alcohol and react under the catalysis of gold perchloride, the method for high regioselectivity ground synthesizing carbazole compounds.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) the easily separated purifying of product; 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, and the productive rate of the corresponding carbazole compound of gained is 60-90%.
Embodiment
Embodiment 1
Under room temperature, add gold perchloride (3.1 mg, 0.01 mmol), 1-(1-ethyl-indoles-2-yl)-2-methyl 4-phenyl-3-butyne-1-ol (60.6 mg, 0.20 mmol) and toluene (1 mL), then within room temperature 3 hours, react completely, concentrated, rapid column chromatography, obtain product 9-Ethyl-2-Methyl-4-phenyl carbazole 51.3 mg, productive rate is 90%.Product is solid, fusing point 92-93
oc(ethyl acetate/normal hexane).
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.68-7.57?(m,?2H,?ArH),?7.56-7.43?(m,?4H,?ArH),?7.41-7.31?(m,?2H,?ArH),?7.21?(s,?1H,?ArH),?7.02-6.90?(m,?2H,?ArH),4.38?(q,?J?=?7.2?Hz,?2H,?NCH
2
),?2.59?(s,?3H,?ArCH
3
),?1.46?(t,?J?=?7.2?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?141.4,?140.6,?140.1,?137.5,?135.5,?129.1,?128.3,?127.3,?124.9,?122.5,?122.1,?122.0,?118.3,?118.0,?108.1,?107.5,?37.3,?22.1,?13.7;?IR?(KBr)?ν?(cm
-1
)?3052,?3025,?2974,?2914,?2865,?1621,?1599,?1571,?1470,?1460,?1418,?1348,?1324,?1282,?1190,?1121,?1084,?1028;MS?(70?ev,?EI)?m/z?(%)?286?(M
+
+1,?18.69),?285?(M
+
,?84.44),?270?(100);?Elemental?analysis?calcd?(%)?for?C
21
H
19
N:?C,?88.38;?H,?6.71;?N,?4.91;?Found:?C,?88.34,?H,?6.87;?N,?4.86.
Embodiment 2
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (3.5 mg, 0.012 mmol), 1-(1-ethyl-indoles-2-yl)-2-methyl-3-hexin-1-alcohol (51.1 mg, 0.20 mmol) and toluene (1 mL), then within room temperature 12 hours, react completely, concentrated, rapid column chromatography, obtains product 2-methyl-4,9-diethyl-carbazole 38.3mg, productive rate is 81%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?8.18?(d,?J?=?8.1?Hz,?1H,?ArH),?7.54-7.41?(m,?2H,?ArH),?7.37-7.23?(m,?1H,?ArH),?7.13?(s,?1H,?ArH),?6.94?(s,?1H,?ArH),?4.38?(q,?J?=?7.2?Hz,?2H,?NCH
2
),?3.29?(q,?J?=?7.5?Hz,?2H,?ArCH
2
),?2.61?(s,?3H,?ArCH
3
),?1.60-1.40?(m,?6H,?2×CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?140.6,?139.8,?139.4,?135.7,?124.4,?122.9,?122.3,?120.1,?118.6,?118.3,?108.1,?106.3,?37.3,?27.3,?22.2,?14.2,?13.7;?IR?(neat)?ν?(cm
-1
)?2970,?2943,?2877,?1618,?1599,?1570,?1468,?1458,?1432,?1374,?1350,?1327,?1258,?1189,?1156,?1080;MS?(70?ev,?EI)?m/z?(%)?238?(M
+
+1,?17.18),?237?(M
+
,?78.06),?222?(100);?HRMS?Calcd?for?C
17
H
19
N?(M
+
):?237.1517,?Found:?237.1519.
Embodiment 3
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (4.6 mg, 0.015 mmol), 1-(1-ethyl-indoles-2-yl)-2-methyl-3-octyne-1-alcohol (83.5 mg, 0.30 mmol) and toluene (2 mL), then react completely at room temperature 19.5 hours, concentrated, rapid column chromatography, obtains product 2-methyl-9-ethyl-4-butyl carbazole 57.8 mg, and productive rate is 74%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?8.08?(d,?J?=?7.8?Hz,?1H,?ArH),?7.47-7.31?(m,?2H,?ArH),?7.27-7.17?(m,?1H,?ArH),?7.05?(s,?1H,?ArH),?6.85?(s,?1H,?ArH),?4.31?(q,?J?=?7.4?Hz,?2H,?NCH
2
),?3.26-3.07?(m,?2H,?ArCH
2
),?2.53?(s,?3H,?ArCH
3
),?1.88-1.75?(m,?2H,?CH
2
),?1.61-1.45?(m,?2H,?CH
2
),?1.40?(t,?J?=?7.4?Hz,?3H,?ArCH
3
),?0.99?(t,?J?=?7.4?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?140.7,?139.9,?138.2,?135.5,?124.4,?123.0,?122.2,?121.2,?118.6,?118.5,?108.1,?106.3,?37.3,?34.1,?32.0,?23.0,?22.1,?14.1,?13.7;?IR?(neat)?ν?(cm
-1
)?3050,?3013,?2955,?2928,?2860,?1623,?1601,?1577,?1491,?1468,?1459,?1450,?1432,?1377,?1350,?1328,?1299,?1268,?1257,?1210,?1188,?1156,?1112,?1084,?1029;MS?(70?ev,?EI)?m/z?(%)?265?(M
+
,?100);?HRMS?Calcd?for?C
19
H
23
N?(M
+
):?265.1830,?Found:?265.1827.
Embodiment 4
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (4.7 mg, 0.015 mmol), 1-(5-methyl isophthalic acid-ethylindole-2-yl)-2-methyl-3-octyne-1-alcohol (89.0 mg, 0.30 mmol) and toluene (2 mL), then within room temperature 11.5 hours, react completely, concentrated, rapid column chromatography, obtains product 2,6-dimethyl-9-ethyl-4-butyl carbazole 60.5 mg, productive rate is 72%.Product is colourless liquid.
1
H?NMR?(400?MHz,?CDCl
3
)?δ?7.87?(s,?1H,?ArH),?7.36-7.19?(m,?2H,?ArH),?7.02?(s,?1H,?ArH),?6.81?(s,?1H,?ArH),?4.26?(q,?J?=?7.2?Hz,?2H,?NCH
2
),?3.24-3.11?(m,?2H,?ArCH
2
),?2.54?(s,?3H,?ArCH
3
),?2.52?(s,?3H,?ArCH
3
),?1.91-1.76?(m,?2H,?CH
2
),?1.62-1.48?(m,?2H,?CH
2
),?1.37?(t,?J?=?7.2?Hz,?3H,?ArCH
3
),?1.01?(t,?J?=?7.2?Hz,?3H,?CH
3
);?
13
C?NMR?(100?MHz,?CDCl
3
)?δ?141.0,?138.19,?138.17,?135.3,?127.7,?125.6,?123.1,?122.4,?120.9,?118.3,?107.8,?106.2,?37.3,?34.1,?32.0,?22.9,?22.1,?21.7,?14.1,?13.7;?IR?(neat)?ν?(cm
-1
)?2956,?2929,?2861,?1626,?1607,?1576,?1481,?1462,?1376,?1350,?1325,?1307,?1271,?1254,?1190,?1146,?1117;MS?(70?ev,?EI)?m/z?(%)?280?(M
+
+1,?21.93),?279?(M
+
,?100);?HRMS?Calcd?for?C
20
H
25
N?(M
+
):?279.1987,?Found:?279.1982.
Embodiment 5
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (4.6 mg, 0.015 mmol), 1-(5-methyl isophthalic acid-ethylindole-2-yl)-2-ethyl-4-phenyl-3-butyne-1-ol (97.5 mg, 0.30 mmol) and toluene (2 mL), then within room temperature 14 hours, react completely, concentrated, rapid column chromatography, obtains product 6-methyl-2,9-diethyl-4-phenyl carbazole 72.9 mg, productive rate is 79%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.68-7.60?(m,?2H,?ArH),?7.54-7.38?(m,?3H,?ArH),?7.28?(s,?1H,?ArH),?7.24-7.11?(m,?3H,?ArH),?6.94?(d,?J?=?1.2?Hz,?1H,?ArH),?4.28?(q,?J?=?7.1?Hz,?2H,?NCH
2
),?2.85?(q,?J?=?7.8?Hz,?2H,?ArCH
2
),?2.29?(s,?3H,?ArCH
3
),?1.42-1.31?(m,?6H,?2×CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?141.8,?141.6,?140.9,?138.5,?137.5,?129.2,?128.2,?127.3,?126.2,?122.7,?122.1,?120.8,?118.1,?107.8,?106.2,?37.3,?29.5,?21.4,?16.1,?13.7;?IR?(neat)?ν?(cm
-1
)?3055,?3027,?2966,?2931,?2870,?1622,?1603,?1568,?1499,?1486,?1470,?1462,?1409,?1378,?1350,?1334,?1307,?1292,?1282,?1227,?1192,?1176,?1146,?1126,?1085,?1073,?1062,?1028;MS?(70?ev,?EI)?m/z?(%)?314?(M
+
+1,?24.85);?313?(M
+
,?100);?HRMS?Calcd?for?C
23
H
23
N?(M
+
):?313.1830,?Found:?313.1824.
Embodiment 6
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (4.6 mg, 0.015 mmol), 1-(5-methyl isophthalic acid-ethylindole-2-yl)-2-phenyl-3-octyne-1-alcohol (102.5 mg, 0.29 mmol) and toluene (2.0 mL), then react completely at room temperature 11 hours, concentrated, rapid column chromatography, obtains product 6-methyl 9-ethyl 4-butyl-2-phenyl carbazole 62.5 mg, and productive rate is 64%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.99?(s,?1H,?ArH),?7.85-7.75?(m,?2H,?ArH),?7.60-7.46?(m,?3H,?ArH),?7.45-7.27?(m,?4H,?ArH),?4.42?(q,?J?=?7.2?Hz,?2H,?NCH
2
),?3.46-3.20?(m,?2H,?ArCH
2
),?2.63?(s,?3H,?ArCH
3
),?2.02-1.87?(m,?2H,?CH
2
),?1.72-1.56?(m,?2H,?CH
2
),?1.48?(t,?J?=?7.2?Hz,?3H,?CH
3
),?1.09?(t,?J?=?7.2?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?142.4,?141.1,?138.7,?138.64,?138.63,?128.7,?128.0,?127.6,?126.9,?126.2,?122.8,?122.7,?119.9,?119.1,?107.9,?104.6,?37.4,?34.3,?31.9,?22.9,?21.7,?14.1,?13.7;?IR?(neat)?ν?(cm
-1
)?3026,?2955,?2929,?2868,?1600,?1567,?1486,?1470,?1375,?1351,?1309,?1281,?1228,?1153,?1117,?1075;MS?(70?ev,?EI)?m/z?(%)?342?(M
+
+1,?27.48),?341?(M
+
,?100);?HRMS?Calcd?for?C
25
H
27
N?(M
+
):?341.2144,?Found:?341.2142.
Embodiment 7
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (3.2 mg, 0.01 mmol), 1-(1-ethyl-5-methoxy-Indole-2-yl)-2-methyl-3-octyne-1-alcohol (63.5 mg, 0.2 mmol) and toluene (1 mL), then react completely at room temperature 11.5 hours, concentrated, rapid column chromatography, obtains product 9-ethyl-4-butyl-6-methoxyl carbazole 36.0 mg, and productive rate is 60%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.63?(d,?J?=?2.4?Hz,?1H,?ArH),?7.30?(d,?J?=?9.0?Hz,?1H,?ArH),?7.11?(dd,?J?=?8.7?and?2.4?Hz,?1H,?ArH),?7.06?(s,?1H,?ArH),?6.84?(s,?1H,?ArH),?4.31?(q,?J?=?7.2?Hz,?2H,?NCH
2
),?3.95?(s,?3H,?OCH
3
),?3.30-2.97?(m,?2H,?ArCH
2
),?2.56?(s,?3H,?ArCH
3
),?1.94-1.78?(m,?2H,?CH
2
),?1.66-1.50?(m,?2H,?CH
2
),?1.42?(t,?J?=?7.2?Hz,?3H,?CH
3
),?1.04?(t,?J?=?7.2?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?153.2,?141.3,?138.2,?135.6,?135.0,?123.3,?120.8,?118.3,?112.7,?108.4,?106.35,?106.32,?56.2,?37.4,?34.1,?32.1,?23.1,?22.1,?14.1,?13.7;?IR?(neat)?ν?(cm
-1
)?2954,?2931,?2862,?2830,?1625,?1609,?1579,?1482,?1378,?1351,?1310,?1227,?1170,?1138,?1040;MS?(70?ev,?EI)?m/z?(%)?296?(M
+
+1,?21.91),?295?(M
+
,?100);?HRMS?Calcd?for?C
20
H
25
NO?(M
+
):?295.1936,?Found:?295.1936.
Embodiment 8
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (3.4 mg, 0.01 mmol), 1-(1-benzyl-5-bromo indole-2-yl)-2-ethyl-4-phenyl-3-butyne-1-ol (92.0 mg, 0.20 mmol) and toluene (2 mL), then react completely at room temperature 13 hours, concentrated, rapid column chromatography, obtains bromo-4-phenyl carbazole 63.6 mg of product 2-ethyl-9-benzyl-6-, and productive rate is 72%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.66-7.56?(m,?3H,?ArH),?7.55-7.41?(m,?3H,?ArH),?7.31?(dd,?J?=?8.7?and?1.8?Hz,?1H,?ArH),?7.26-7.16?(m,?3H,?ArH),?7.13?(s,?1H,?ArH),?7.10-7.02?(m,?3H,?ArH),?6.99?(d,?J?=?0.9?Hz,?1H,?ArH),?5.36?(s,?2H,?ArCH
2
),?2.78?(q,?J?=?7.5?Hz,?2H,?CH
2
),?1.28?(t,?J?=?7.5?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?143.1,?141.7,?140.7,?139.4,?137.7,?136.6,?129.0,?128.8,?128.5,?127.8,?127.7,?127.5,?126.2,?124.5,?124.4,?121.8,?117.4,?111.6,?110.0,?106.8,?46.4,?29.4,?15.9;?IR?(neat)?ν?(cm
-1
)?3087,?3049,?3012,?2955,?2928,?2862,?1645,?1495,?1574,?1502,?1463,?1392?,1327?1302,?1225,?1162,?1118,?1088,?1029;?MS?(70?ev,?EI)?m/z?(%)?442?(M
+?
(
81
Br)+1,?27.88),?441?(M
+?
(
81
Br),?100),?440?(M
+?
(
79
Br)+1,?29.53),439?(M
+?
(
79
Br),?96.50);?HRMS?Calcd?for?C
27
H
22
N
79
Br?(M
+
):?439.0936,?Found:?439.0932.
Embodiment 9
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (4.6 mg, 0.015 mmol), 1-(4-methyl isophthalic acid-ethylindole-2-yl)-2-methyl-3-octyne-1-alcohol (89.2 mg, 0.30 mmol) and toluene (2 mL), then within room temperature 3 hours, react completely, concentrated, rapid column chromatography, obtains product 2,5-dimethyl-9-ethyl-4 butyl carbazole 54.5 mg, productive rate is 65%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.46-7.36?(m,?1H,?ArH),?7.32?(d,?J?=?7.8?Hz,?1H,?ArH),?7.14?(s,?1H,?ArH),?7.09?(d,?J?=?7.2?Hz,?1H,?ArH),?6.97?(s,?1H,?ArH),?4.38?(q,?J?=?7.1?Hz,?2H,?NCH
2
),?3.48-3.30?(m,?2H,?ArCH
2
),?3.04?(s,?3H,?CH
3
),?2.60?(s,?3H,?CH
3
),?1.86-1.74?(m,?2H,?CH
2
),?1.60-1.40?(m,?5H,?CH
3
+CH
2
),?1.02?(t,?J?=?7.2?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?141.2,?140.6,?137.7,?135.1,?132.1,?124.6,?122.8,?122.4,?122.3,?119.4,?106.2,?106.0,?37.2,?36.8,?34.8,?25.3,?22.6,?21.7,?14.1,?13.3;?IR?(neat)?ν?(cm
-1
)?3048,?2956,?2926,?2870,?1619,?1597,?1570,?1451,?1377,?1349,?1317,?1274,?1216,?1148,?1078,?1044;MS?(70?ev,?EI)?m/z?(%)?280?(M
+
+1,?22.02),?279?(M
+
,?100);?HRMS?Calcd?for?C
20
H
25
N?(M
+
):?279.1987,?Found:?279.1994.
Embodiment 10
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (4.9 mg, 0.016 mmol), 1-(7-methyl isophthalic acid-ethylindole-2-yl)-2-methyl 4-phenyl-3-butyne-1-ol (96.2 mg, 0.30 mmol) and toluene (2 mL), then within room temperature 12 hours, react completely, concentrated, rapid column chromatography, obtains product 1,7-dimethyl-9 ethyl-5-phenyl carbazole 82.1mg, productive rate is 90%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.77-7.69?(m,?2H,?ArH),?7.67-7.52?(m,?3H,?ArH),?7.42?(d,?J?=?7.8?Hz,?1H,?ArH),?7.32?(s,?1H,?ArH),?7.20?(d,?J?=?7.2?Hz,?1H,?ArH),7.06?(d,?J?=?0.6?Hz,?1H,?ArH),?6.96?(t,?J?=?7.5?Hz,?1H,?ArH),?4.69?(q,?J?=?7.1?Hz,?2H,?NCH
2
),?2.91?(s,?3H,?ArCH
3
),?2.71?(s,?3H,?ArCH
3
),?1.56?(t,?J?=?7.2?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?141.5,?141.4,?138.8,?137.2,?135.2,?129.2,?128.3,?127.3,?123.5,?122.4,?120.0,?119.5,?118.4,?118.2,?107.8,?39.3,?22.1,?20.3,?15.6;?IR?(neat)?ν?(cm
-1
)?3027,?2959,?2927,?2855,?1622,?1603,?1569,?1486,?1463,?1409,?1332,?1306,?1227,?1192,?1146,?1084,?1028;MS?(70?ev,?EI)?m/z?(%)?300?(M
+
+1,?19.63),?299?(M
+
,?78.14),?284?(100);?HRMS?Calcd?for?C
22
H
21
N?(M
+
):?299.1674,?Found:?299.1678.
Embodiment 11
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (3.1 mg, 0.01 mmol), 1-(1-(4-methoxy-benzyl) indoles-2-yl)-2-methyl-3-octyne-1-alcohol (75.0 mg, 0.20 mmol) and toluene (1.5 mL), then within room temperature 12 hours, react completely, concentrated, rapid column chromatography, obtains product 2-methyl-4-butyl-9-(4-methoxy-benzyl) carbazole 41.7 mg, productive rate is 58%.Product is solid, fusing point 92-93
oc(ethyl acetate/normal hexane).
1
H?NMR?(300?MHz,?CDCl
3
)?δ?8.10?(q,?J?=?7.8?Hz,?1H,?ArH),?7.42-7.28?(m,?2H,?ArH),?7.27-7.18?(m,?1H,?ArH),?7.10-6.98?(m,?3H,?ArH),?6.86?(s,?1H,?ArH),?6.80-6.71?(m,?2H,?ArH),?5.38?(s,?2H,?ArCH
2
),?3.70?(s,?3H,?OCH
3
),?3.24-3.15?(m,?2H,?ArCH
2
),?2.47?(s,?3H,?ArCH
3
),?1.90-1.68?(m,?2H,?CH
2
),?1.62-1.43?(m,?2H,?CH
2
),?1.00?(t,?J?=?7.2?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?158.8,?141.5,?140.6,?138.1,?135.7,?129.3,?127.5,?124.6,?123.1,?122.2,?121.5,?119.0,?118.5,?114.1,?108.6,?106.7,?55.2,?45.8,?34.1,?32.0,?23.0,?22.1,?14.1;?IR?(KBr)?ν?(cm
-1
)?3052,?2954,?2928,?2860,?2835,?1613,?1601,?1586,?1575,?1513,?1481,?1463,?1446,?1353,?1327,?1295,?1248,?1175,?1034;MS?(70?ev,?EI)?m/z?(%)?358?(M
+
+1,?7.06),?357?(M
+
,?24.84),?121?(100);?Elemental?analysis?calcd?(%)?for?C
25
H
27
NO:?C,?83.99;?H,?7.61;?N,?3.92;?Found:?C,?83.57,?H,?7.66;?N,?4.02.
Embodiment 12
Press the method described in embodiment 1, different is that substrate used and reagent are: gold perchloride (3.2 mg, 0.01 mmol), 1-(1-benzylindole-2-yl)-2-ethyl-4-phenyl-3-butyne-1-ol (76.2 mg, 0.20 mmol) and toluene (1.0 mL), then react completely at room temperature 12 hours, concentrated, rapid column chromatography, obtains product 2-ethyl-9-benzyl-4-phenyl carbazole 45.0 mg, and productive rate is 62%.Product is colourless liquid.
1
H?NMR?(300?MHz,?CDCl
3
)?δ?7.71-7.63?(m,?2H,?ArH),?7.58-7.44?(m,?4H,?ArH),?7.35-7.22?(m,?5H,?ArH),?7.22-7.12?(m,?3H,?ArH),?7.03-6.92?(m,?2H,?ArH),?5.55?(s,?2H,?ArCH
2
),?2.83?(q,?J?=?7.7?Hz,?2H,?CH
2
),?1.32?(t,?J?=?7.7?Hz,?3H,?CH
3
);?
13
C?NMR?(75?MHz,?CDCl
3
)?δ?142.3,?141.5,?141.4,?140.9,?137.5,?137.2,?129.2,?128.7,?128.3,?127.40,?127.37,?126.4,?125.1,?122.7,?122.0,?121.4,?118.7,?118.4,?108.6,?106.7,?46.4,?29.4,?16.0;?IR?(neat)?ν?(cm
-1
)?3055,?3030,?2962,?2926,?2853,?1620,?1600,?1571,?1496,?1480,?1463,?1453,?1418,?1354,?1324,?1292,?1174;MS?(70?ev,?EI)?m/z?(%)?362?(M
+
+1,?29.50),?361?(M
+
,?100);?HRMS?Calcd?for?C
27
H
23
N?(M
+
):?361.1830,?Found:?361.1828.
Claims (2)
1. a method of synthesizing functionalization carbazole to high regioselectivity, is characterized in that 1-(indoles-2-yl)-3-alkynes-1-alcohol synthesizing carbazole compounds that reacts under the catalysis of gold perchloride, and reaction formula is as follows:
R
1=ethyl, benzyl, to methoxy-benzyl; R
2=H, methyl, methoxyl group or bromine; R
3=alkyl, phenyl, wherein alkyl is C
n h
2n+1, in formula
n=1-2; R
4=alkyl or phenyl, wherein alkyl is C
m h
2m+1, in formula
m=1-4; Its step is as follows:
(1) successively 1-(indoles-2-yl)-3-alkynes-1-alcohol, gold perchloride are joined in toluene, the mol ratio of 1-(indoles-2-yl)-3-alkynes-1-alcohol and gold perchloride is 1: 0.05, then stirring reaction 3-19.5 hour at room temperature;
(2) concentrated, rapid column chromatography, obtains carbazole compound.
2. the method for synthesizing carbazole compounds according to claim 1, is characterized in that described 1-(indoles-2-yl)-3-alkynes-1-alcohol and the mol ratio of toluene are 0.1～0.2.
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| Title |
|---|
| Gold(I)-Catalyzed Rearrangement of 3-Silyloxy-1,5-enynes: An Efficient Synthesis of Benzo[b]thiophenes, Dibenzothiophenes, Dibenzofurans, and Indole Derivatives;Hashmi,A. Stephen K.等;《Chemistry-A European Journal》;20120419;第18卷(第21期);第6577页表1、表2、结果与讨论左栏第2段第17-18行，第6578页表2续，支持信息化合物4a和4l的合成 * |
| Hashmi,A. Stephen K.等.Gold(I)-Catalyzed Rearrangement of 3-Silyloxy-1,5-enynes: An Efficient Synthesis of Benzo[b]thiophenes, Dibenzothiophenes, Dibenzofurans, and Indole Derivatives.《Chemistry-A European Journal》.2012,第18卷(第21期),第6577页表1、表2、结果与讨论左栏第2段第17-18行，第6578页表2续，支持信息化合物4a和4l的合成. |
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