CN101735042B - Synthesizing method of 2-alkyl-4,4-diaryl trans-2-ethyl crotonate - Google Patents

Synthesizing method of 2-alkyl-4,4-diaryl trans-2-ethyl crotonate Download PDF

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CN101735042B
CN101735042B CN 200910155479 CN200910155479A CN101735042B CN 101735042 B CN101735042 B CN 101735042B CN 200910155479 CN200910155479 CN 200910155479 CN 200910155479 A CN200910155479 A CN 200910155479A CN 101735042 B CN101735042 B CN 101735042B
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butenoate
diaryl
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CN101735042A (en
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麻生明
方昭
傅春玲
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention relates to a synthesizing method of 2-alkyl-4,4-diaryl trans-2-ethyl crotonate which is synthesized by using 2,3-allenyl acid ester and electron-rich aromatic compounds as raw materials and by using a palladium-catalyzed carbon-hydrogen bond functionalized reaction in a high regio-selective and stereo-selective way. The invention has simple operation, easy obtaining of reagents as raw materials, high regio-selectivity and stereo-selectivity of the reaction, easy separation and purification of products, and suitability for synthesizing various substituent groups of 2-alkyl-4,4-diaryl trans-2-ethyl crotonate compounds.

Description

2-alkyl-4, the synthetic method of 4-diaryl ethyl trans-2-butenoate
Technical field
The present invention relates to a kind of synthetic 2-alkyl-4, the method of 4-diaryl ethyl trans-2-butenoate, namely by 2 of palladium catalysis, the high zone of the reaction of 3-connection olefin(e) acid ester and electron rich aromatic ring and Stereoselective synthesize 2-alkyl-4, the method for 4-diaryl ethyl trans-2-butenoate.
Background technology
2-alkyl-4,4-diaryl ethyl trans-2-butenoate is one of intermediate important in the organic synthesis, also is one of structural unit common in the natural product, has certain physiologically active, at biological technical field, there is huge value of exploiting and utilizing aspects such as medicine and agricultural chemicals.But rarely seen this class 2-alkyl-4 in the document, the directly synthetic report of 4-diaryl ethyl trans-2-butenoate compound.
Summary of the invention
Purpose of the present invention just provides a kind of 2-alkyl-4, the direct synthetic method of 4-diaryl ethyl trans-2-butenoate compound.
The present invention is by electron rich aromatic compound and 2, the hydrocarbon functionalization reaction of the high zone of 3-connection olefin(e) acid ester and Stereoselective generates 2-alkyl-4,4-diaryl ethyl trans-2-butenoate, reaction can make up carbon bond with the direct functionalization of the hydrocarbon key of aromatic ring, and substrate adaptability is preferably arranged.
Synthetic 2-alkyl-4 provided by the invention, the method of 4-diaryl ethyl trans-2-butenoate, with 2,3-connection olefin(e) acid ester and electron rich aromatic compound are raw material, utilize the hydrocarbon key functionalization of palladium catalysis, high zone and Stereoselective generate 2-alkyl-4,4-diaryl ethyl trans-2-butenoate, and reaction formula is as follows:
Figure G2009101554795D00011
Ar 1Be equal trimethoxyphenyl, p-methoxyphenyl or p-hydroxybenzene; Ar 2Be aryl; R is methyl, ethyl, and allyl group or benzyl the steps include:
(1) electron rich aromatic compound and dichloro diacetonitrile palladium are dissolved in the N,N-dimethylacetamide, 2,3-connection olefin(e) acid ester is added with the trifluoroacetic acid flushing.Whole system is heated to 40 ℃ and stirred 15 hours.
(2) after step (1) reacts completely, use in the saturated sodium bicarbonate aqueous solution cancellation reaction and trifluoroacetic acid.
(3) use extracted with diethyl ether, anhydrous sodium sulfate drying filters, and concentrates, and rapid column chromatography obtains 2-alkyl-4,4-diaryl ethyl trans-2-butenoate.
The mol ratio of electron rich aromatic compound and 2,3-connection olefin(e) acid ester is 1: 1.19～1.27 among the present invention.
The mol ratio of dichloro diacetonitrile palladium and electron rich aromatic compound is 0.044-0.058 among the present invention: 1.
The volume ratio of N,N-dimethylacetamide and trifluoroacetic acid is 1: 4 among the present invention.
The present invention has introduced a kind of synthetic 2-alkyl-4, the method for 4-diaryl ethyl trans-2-butenoate has the following advantages: 1) raw material is simple and easy to, and is easy to prepare; 2) mild condition, strong operability; 3) certain substrate universality is arranged, can synthesize the 2-alkyl-4 of various replacements, 4-diaryl ethyl trans-2-butenoate; 4) the easily separated purifying of product.
Innovative point of the present invention is to have developed the direct hydrocarbon functionalization reaction of a kind of electron rich aromatic compound and 2,3-connection olefin(e) acid ester.
The corresponding 2-alkyl-4 of gained of the present invention, the productive rate of 4-diaryl ethyl trans-2-butenoate is 37-70%.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
Embodiment 1
With 1,3,5-trimethoxy-benzene (49.4mg, 0.29mmol) and dichloro diacetonitrile palladium (3.5mg 0.013mmol) is dissolved in 0.3mLN, in the N-N,N-DIMETHYLACETAMIDE, draw 2-methyl-4-phenyl-2 with dropper, (72.9mg 0.36mmol), adds system with trifluoroacetic acid 1.2mL rinse to 3 alkene ethyl butyrates.Kept 40 degree heated and stirred behind reinforced the finishing 15 hours.The system for the treatment of is a little behind the cool to room temperature, drip saturated sodium bicarbonate aqueous solution cancellation reaction and in and the trifluoroacetic acid solvent.Use extracted with diethyl ether, saturated sodium bicarbonate solution is washed organic phase to neutral, and anhydrous sodium sulfate drying filters, and concentrates, and rapid column chromatography gets product 2-methyl-4-phenyl-4-(2,4,6-trimethoxyphenyl) ethyl trans-2-butenoate, and productive rate is 64%.Product is white solid.
1H?NMR(300MHz，CDCl 3)δ7.50(d，J＝9.3Hz，1H)，7.27-7.18(m，2H)，7.18-7.09(m，3H)，6.14(s，2H)，5.59(d，J＝9.3Hz，1H)，4.18(q，J＝7.4Hz，2H)，3.79(s，3H)，3.71(s，6H)，1.88(s，3H)，1.28(t，J＝7.4Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.6，160.1，158.8，144.1，143.3，127.9，127.4，127.1，125.5，111.3，91.2，60.3，55.7，55.2，38.4，14.3，12.4；
MS(70eV，EI)m/z(％)370(M +，10.49)，324(100)；
IR(KBr)ν(cm -1)3059，2938，2838，1706，1642，1605，1493，1465，1455，1418，1367，1331，1280，1220，1205，1151，1112，1057，1037；
Anal.Calcd?for?C 22H 26O 5：C，71.33；H，7.07；Found：C，71.28；H，7.06.
Embodiment 2
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (51.0mg, 0.30mmol), (4.0mg is 0.015mmol) with 2-ethyl-4-phenyl-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (76.1mg, 0.35mmol), get product 2-ethyl-4-phenyl-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 46.9mg, productive rate are 41%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.46(d，J＝9.6Hz，1H)，7.26-7.19(m，2H)，7.18-7.10(m，3H)，6.15(s，2H)，5.62(d，J＝9.6Hz，1H)，4.19(q，J＝7.2Hz，2H)，3.81(s，3H)，3.71(s，6H)，2.49-2.30(m，2H)，1.28(t，J＝6.9Hz，3H)，0.93(t，J＝7.5Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.3，160.1，158.8，143.5，143.3，133.7，127.8，127.0，125.5，111.5，91.2，?60.2，55.7，55.2，37.9，20.2，14.3，13.8；
MS(70eV，EI)m/z(％)384(M +，8.13)，338(100)；
IR(neat)ν(cm -1)2973，2936，2838，1706，1605，1493，1465，1418，1294，1219，1203，1151，1115，1056，1039；
HRMS?Calcd?for?C 23H 28O 5(M +)：384.1937；Found：384.1952.
Embodiment 3
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (49.2mg, 0.29mmol), (4.2mg is 0.016mmol) with 2-benzyl-4-phenyl-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (101.5g, 0.37mmol), get product 2-benzyl-4-phenyl-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 65.8mg, productive rate are 50%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.68(d，J＝9.6Hz，1H)，7.28-7.04(m，10H)，6.13(s，2H)，5.75(d，J＝9.6Hz，1H)，4.12(q，J＝7.2Hz，2H)，3.80(s，3H)，3.76(s，2H)，3.65(s，6H)，1.19(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.1，160.2，158.7，145.1，143.1，139.9，130.7，128.4，128.0，127.9，127.1，125.6，111.0，91.1，60.3，55.6，55.2，38.3，32.4，14.1；
MS(70eV，EI)m/z(％)446(M +，0.23)，401(M +-OC 2H 5，5.98)，309(M +-OC 2H 5-C 7H 8)，205(100)；
IR(neat)ν(cm -1)3083，3060，3025，2938，2839，1708，1603，1493，1455，1418，1368，1330，1290，1218，1204，1150，1107，1078，1059；
Anal.Calcd?for?C 28H 30O 5：C，75.31；H，6.77；Found：C，75.32；H，6.81.
Embodiment 4
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (51.4mg, 0.31mmol), (4.2mg is 0.016mmol) with 2-allyl group-4-phenyl-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (83.9mg, 0.37mmol), get product 2-allyl group-4-phenyl-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 44.2mg, productive rate are 37%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.57(d，J＝9.9Hz，1H)，7.26-7.19(m，2H)，7.17-7.10(m，3H)，6.15(s，2H)，5.81-5.66(m，1H)，5.62(d，J＝9.3Hz，1H)，4.99(dq，J 1＝17.3Hz，J 2＝1.8Hz，1H)，4.94-4.86(m，1H)，4.18(q，J＝7.2Hz，2H)，3.81(s，3H)，3.72(s，6H)，3.17-3.06(m，2H)，1.27(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.0，160.1，158.7，145.3，143.2，135.7，129.5，127.9，127.1，125.6，115.0，111.2，91.2，60.3，55.7，55.2，38.1，31.0，14.2；
MS(70eV，EI)m/z(％)396(M +，9.02)，168(100)；
IR(neat)ν(cm -1)3082，2955，2936，2839，1707，1638，1606，1494，1465，1450，1418，1368，1331，1284，1218，1203，1151，1117，1059，1041；
HRMS?Calcd?for?C 24H 28O 5(M +)：396.1937；Found：396.1933.
Embodiment 5
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (51.8mg, 0.31mmol), (4.2mg is 0.016mmol) with 2-methyl-4-naphthyl-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (92.7mg, 0.37mmol), get product 2-methyl-4-naphthyl-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 89.8mg, productive rate are 69%.Product is white solid.
1H?NMR(300MHz，CDCl 3)δ8.13-8.01(m，1H)，7.91-7.80(m，1H)，7.72(dd，J 1＝7.2Hz，J 2＝1.5Hz，1?H)，7.55-7.33(m，5H)，6.18(s，2H)，6.13(d，J＝9.0Hz，1H)，4.30-4.07(m，2H)，3.81(s，3H)，3.73(s，6H)，1.93(s，3H)，1.27(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.6，160.1，158.8，146.1，138.5，133.7，132.0，128.6，126.6，126.0，125.6，125.4，125.1，125.0，124.0，111.3，91.3，60.2，55.7，55.1，36.6，14.2，12.4；
MS(70e?V，EI)m/z(％)420(M +，33.28)，374(100)；
IR?IR(KBr)ν(cm -1)3003，2971，2936，2838，1711，1641，1602，1508，1493，1466，1437，1417，1396，1332，1241，1224，1205，1152，1111，1057，1034；
Anal.Calcd?for?C 26H 28O 5：C，74.26；H，6.71；Found：C，74.08；H，6.77.
Embodiment 6
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (50.6mg, 0.30mmol), (3.6mg is 0.014mmol) with 2-methyl-4-p-methylphenyl-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (78.6mg, 0.36mmol), get product 2-methyl-4-p-methylphenyl-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 70.4mg, productive rate are 61%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.54(d，J＝9.2Hz，1H)，7.08(s，4H)，6.18(s，2H)，5.59(d，J＝9.0Hz，1H)，4.21(q，J＝7.2Hz，2H)，3.83(s，3H)，3.75(s，6H)，2.32(s，3H)，1.91(d，J＝0.9Hz，3H)，1.31(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.6，160.0，158.7，144.5，140.2，134.9，128.6，127.1，127.0，111.4，91.2，60.2，55.7，55.2，38.0，20.9，14.2，12.3；
MS(70eV，EI)m/z(％)384(M +，10.42)，338(100)；
IR(neat)ν(cm -1)2938，2838，1706，1641，1606，1586，1512，1493，1465，1418，1367，1329，1278，1220，1205，1151，1111，1079，1057，1038；
HRMS?Calcd?for?C 23H 28O 5(M +)：384.1937；Found：384.1955.
Embodiment 7
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (49.6mg, 0.30mmol), (4.1mg is 0.016mmol) with 2-methyl-4-p-methoxyphenyl-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (85.1mg, 0.37mmol), get product 2-methyl-4-p-methoxyphenyl-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 45.6mg, productive rate are 38%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.49(d，J＝9.3Hz，1H)，7.12-7.03(m，2H)，6.83-6.74(m，2H)，6.15(s，2H)，5.54(d，J＝9.3Hz，1H)，4.19(q，J＝7.2Hz，2H)，3.81(s，3H)，3.77(s，3H)，3.73(s，6H)，1.87(d，J＝0.9Hz，3H)，1.29(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.7，160.0，158.7，157.4，144.6，135.4，128.1，127.1，113.2，111.6，91.2，60.3，55.8，55.2，55.1，37.6，14.3，12.4；
MS(70eV，EI)m/z(％)400(M +，14.20)，354(100)；
IR(neat)ν(cm -1)2938，2837，1705，1642，1607，1510，1464，1417，1387，1367，1282，1247，1220，1205，1151，1111，1079，1057，1036；
HRMS?Calcd?for?C 23H 28O 6(M +)：400.1886；Found：400.1878.
Embodiment 8
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (50.3mg, 0.30mmol), (3.7mg is 0.014mmol) with 2-methyl-4-fluorophenyl-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (80.4mg, 0.37 mmol), get the fluorophenyl-4-(2,4 of product 2-methyl-4-, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 81.7mg, productive rate are 70%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.46(d，J＝9.3Hz，1H)，7.16-7.05(m，2H)，6.97-6.86(m，2H)，6.16(s，2H)，5.56(d，J＝9.0Hz，1H)，4.20(q，J＝7.2Hz，2H)，3.81(s，3H)，3.73(s，6H)，1.89(d，J＝1.2Hz，3H)，1.29(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.6，161.0(d，J＝241.1Hz)，160.2，158.6，143.7，138.8(d，J＝3.5Hz)，128.5(d，J＝7.8Hz)，127.6，114.5(d，J＝211Hz)，111.2，91.2，60.3，55.7，55.2，37.7，14.2，12.4；
19F?NMR(282MHz)δ-118.3；
MS(70eV，EI)m/z(％)388(M +，9.48)，342(100)；
IR(neat)ν(cm -1)2939，2839，1706，1642，1606，1506，1466，1438，1418，1367，1279，1220，1205，1151，1112，1078，1057，1038，1016；
HRMS?Calcd?for?C 22H 25O 5F(M +)：388.1686；Found：388.1681.
Embodiment 9
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (49.6mg, 0.30mmol), (4.1mg is 0.016mmol) with 2-methyl-4-rubigan-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (84.5mg, 0.036mmol), get product 2-methyl-4-rubigan-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 63.4mg, productive rate are 52%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.41(dq，J 1＝9.3Hz，J 2＝1.5Hz，1H)，7.21-7.15(m，2H)，7.11-7.03(m，2H)，6.14(s，2H)，5.53(d，J＝9.3Hz，1H)，4.19(q，J＝7.2Hz，2H)，3.80(s，3H)，3.72(s，6H)，1.86(d，J＝1.5Hz，3H)，1.28(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.5，160.2，158.6，143.3，141.9，131.1，128.5，127.9，110.8，91.1，60.3，55.7，55.2，37.8，14.2，12.4；
MS(70eV，EI)m/z(％)406(M +( 37Cl)，2.53)，404(M +( 35Cl)，8.04)，358(100)；
IR(neat)ν(cm -1)2939，2839，1708，1642，1606，1489，1465，1418，1367，1331，1287，1220，1205，1151，1113，1078，1057，1038，1014；
HRMS?Calcd?for?C 22H 25O 5Cl(M +( 35Cl))：404.1391；Found：404.1400.
Embodiment 10
Press embodiment 1 described method, different is that used substrate is: 1,3,5-trimethoxy-benzene (50.9mg, 0.30mmol), (3.7mg is 0.014mmol) with 2-methyl-4-rubigan-2 for dichloro diacetonitrile palladium, 3 alkene ethyl butyrate (106.3mg, 0.38mmol), get product 2-methyl-4-rubigan-4-(2,4, the 6-trimethoxyphenyl) ethyl trans-2-butenoate 69.5mg, productive rate are 51%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.42(d，J＝9.3Hz，1H)，7.37-7.29(m，2H)，7.07-6.98(m，2H)，6.15(s，2H)，5.52(d，J＝9.3Hz，1H)，4.20(q，J＝7.2Hz，2H)，3.81(s，3H)，3.72(s，6H)，1.88(d，J＝1.2Hz，3H)，1.29(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.5，160.2，158.6，143.2，142.4，130.8，128.9，127.9，119.2，110.8，91.2，60.4，55.7，55.2，37.8，14.2，12.4；
MS(70eV，EI)m/z(％)450(M +( 81Br)，7.67)，448(M +( 79Br)，7.78)，404(100)；
IR(neat)ν(cm -1)2937，2841，1706，1606，1588，1486，1465，1456，1418，1367，1219，1205，1151，1112，1038，1010；
HRMS?Calcd?for?C 22H 25O 5Br(M +( 79Br))：448.0885；Found：448.0878.
Embodiment 11
Press embodiment 1 described method, different is that used substrate is: methyl-phenoxide (0.30mmol, 33 μ L, d=0.993,32.8mg), dichloro diacetonitrile palladium (4.3mg, 0.017mmol) and 2-methyl-4-phenyl-2,3 alkene ethyl butyrate (73.4mg, 0.36mmol), get product 2-methyl-4-phenyl-4-p-methoxyphenyl ethyl trans-2-butenoate 47.9mg, productive rate is 52%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.34-7.24(m，2H)，7.24-7.16(m，3H)，7.16-7.07(m，2H)，6.89-6.78(m，2H)，6.33(d，J＝10.5Hz，1H)，5.79(d，J＝10.5Hz，1H)，4.20(q，J＝7.2Hz，2H)，3.77(s，3H)，1.98(d，J＝1.5Hz，3H)，1.28(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ167.7，158.0，144.0，143.2，135.8，129.2，128.4，128.2，126.9，126.3，113.8，60.3，55.2，48.3，21.0，14.2；
MS(70eV，EI)m/z(％)310(M +，34.42)，236(100)；
IR(neat)ν(cm -1)3028，2979，2835，1711，1643，1609，1584，1510，1494，1452，1371，1302，1250，1217，1178，1133，1108，1033；
HRMS?Calcd?for?C 20H 22O 3(M +)：310.1569；Found：310.1563.
Embodiment 12
Press embodiment 1 described method, different is that used substrate is: methyl-phenoxide (0.30mmol, 33 μ L, d=0.993,32.8mg), dichloro diacetonitrile palladium (4.2mg, 0.016mmol) and 2-methyl-4-naphthyl-2,3 alkene ethyl butyrate (91.9mg, 0.36mmol), get product 2-methyl-4-naphthyl-4-p-methoxyphenyl ethyl trans-2-butenoate 63.6mg, productive rate is 58%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ8.17-8.05(m，1H)，7.92-7.83(m，1H)，7.79(d，J＝8.1Hz，1H)，7.57-7.43(m，3H)，7.39(d，J＝6.6Hz，1H)，7.22-7.11(m，2H)，6.90-6.79(m，2H)，6.64(d，J＝9.9Hz，1H)，6.51(dd，J 1＝10.2Hz，J 2＝1.2Hz，1H)，4.21(q，J＝7.2Hz，2H)，3.78(s，3H)，2.05(d，J＝1.5Hz，3H)，1.23(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ167.7，157.9，143.8，140.0，136.1，134.0，131.7，129.1，128.7，127.2，127.0，125.9，125.4，125.34，125.27，124.2，113.8，60.4，55.1，44.8，21.0，14.1；
MS(70eV，EI)m/z(％)360(M +，40.59)，287(100)；
IR(neat)ν(cm -1)3047，2980，2835，1710，1642，1609，1582，1510，1462，1395，1372，1349，1301，1248，1219，1178，1132，1110，1033；
1467，1371，1314，1277，1236，1148，1084，1067，1045，1010；
HRMS?Calcd?for?C 24H 24O 3(M +)：360.1725；Found：360.1724.
Embodiment 13
Press embodiment 1 described method, different is that used substrate is: methyl-phenoxide (0.30mmol, 33 μ L, d=0.993,32.8mg), dichloro diacetonitrile palladium (3.8mg, 0.015mmol) and 2-methyl-4-fluorophenyl-2,3 alkene ethyl butyrate (79.1mg, 0.36mmol), get the fluorophenyl of product 2-methyl-4--4-p-methoxyphenyl ethyl trans-2-butenoate 49.6mg, productive rate is 50%.Product is liquid.
1H?NMR(300MHz，CDCl 3)δ7.19-7.06(m，4H)，7.03-6.93(m，2H)，6.88-6.80(m，2H)，6.27(dd，J 1＝10.2Hz，J 2＝1.2Hz，1H)，5.75(d，J＝10.2Hz，1H)，4.21(q，J＝7.2Hz，2H)，3.78(s，3H)，1.98(d，J＝1.2Hz，3H)，1.28(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ167.7，161.4(J＝242.2Hz)，158.2，142.9，139.7(J＝3.5Hz)，135.7，129.6(J＝7.7Hz)，129.2，127.2，115.2(J＝21.6Hz)，113.9，60.4，55.2，47.6，20.9，14.2；
19F?NMR(282MHz，CDCl 3)δ-116.9；
MS(70eV，EI)m/z(％)328(M +，35.21)，254(100)；
IR(neat)ν(cm -1)2980，2955，2925，2901，2835，1711，1639，1608，1573，1508，1459，1374，1299，1245，1217，1179，1132，1108，1034；
HRMS?Calcd?for?C 20H 21O 3F(M +)：328.1475；Found：328.1474.
Embodiment 14
Press embodiment 1 described method, different is that used substrate is: phenol (27.7mg, 0.29mmol), dichloro diacetonitrile palladium (4.4mg, 0.017mmol) and 2-methyl-4-phenyl-2,3 alkene ethyl butyrate (72.3mg, 0.36mmol), get product 2-methyl-4-phenyl-4-p-hydroxybenzene ethyl trans-2-butenoate 34.7mg, productive rate is 40%.Product is white solid.
1H?NMR(300MHz，CDCl 3)δ7.34-7.24(m，2H)，7.24-7.15(m，3H)，7.09-6.99(m，2H)，6.80-6.70(m，2H)，6.33(dd，J 1＝10.4Hz，J 2＝1.5Hz，1H)，5.75(d，J＝10.8Hz，1H)，5.46(s，1H)，4.21(q，J＝7.2Hz，2H)，1.98(d，J＝1.2Hz，3H)，1.28(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ168.1，154.1，143.9，143.4，135.7，129.4，128.4，128.2，126.9，126.3，115.3，60.6，48.4，21.0，14.2；
MS(70eV，EI)m/z(％)296(M +，30.77)，222(100)；
IR(KBr)ν(cm -1)3407，2980，2925，1708，1684，1613，1597，1512，1494，1450，1373，1219，1173，1134，1104，1023；
Anal.Calcd?for?C 19H 20O 3：C，77.00；H，6.80；Found：C，76.79；H，7.10.
Embodiment 15
Press embodiment 1 described method, different is that used substrate is: phenol (27.7mg, 0.29mmol), dichloro diacetonitrile palladium (4.3mg, 0.016mmol) and 2-methyl-4-naphthyl-2,3 alkene ethyl butyrate (91.7mg, 0.36mmol), get product 2-methyl-4-naphthyl-4-p-hydroxybenzene ethyl trans-2-butenoate 50.8mg, productive rate is 50%.Product is white solid.
1H?NMR(300MHz，CDCl 3)δ8.10-7.96(m，1H)，7.90-7.80(m，1H)，7.75(d，J＝7.8Hz，1H)，7.49-7.37(m，3H)，7.34(d，J＝7.2Hz，1H)，7.11-6.99(m，2H)，6.77-6.66(m，2H)，6.55(d，J＝9.9Hz，1H)，6.45(dd，J 1＝10.2Hz，J 2＝1.2Hz，1H)，5.03(bs，1H)，4.17(q，J＝7.2Hz，2H)，2.00(d，J＝0.9Hz，3H)，1.19(t，J＝7.2Hz，3H)；
13C?NMR(75MHz，CDCl 3)δ167.9，154.0，143.9，140.0，136.2，134.0，131.7，129.3，128.7，127.2，127.0，126.0，125.5，125.4，125.3，124.2，115.3，60.5，44.8，21.0，14.1；
MS(70eV，EI)m/z(％)346(M +，24.17)，273(100)；
IR(KBr)ν(cm -1)3399，3048，2927，1687，1641，1613，1596，1511，1440，1374，1221，1172，1134，1104，1022；
Anal.Calcd?for?C 23H 22O 3：C，79.74；H，6.40；Found：C，79.86；H，6.30。

Claims (4)

1. 2-alkyl-4, the synthetic method of 4-diaryl ethyl trans-2-butenoate, it is characterized in that: with 2,3-connection olefin(e) acid ester and electron rich aromatic compound are raw material, utilize the hydrocarbon key functionalization of dichloro diacetonitrile palladium catalysis, generate 2-alkyl-4,4-diaryl ethyl trans-2-butenoate, reaction formula is as follows:
Figure FSB00001054893600011
Ar 1Be equal trimethoxyphenyl, p-methoxyphenyl or p-hydroxybenzene; Ar 2Be aryl; R is methyl or ethyl, the steps include:
(1) electron rich aromatic compound and dichloro diacetonitrile palladium are dissolved in the N,N-dimethylacetamide, 2,3-connection olefin(e) acid ester is added with the trifluoroacetic acid flushing, whole system is heated to 40 ℃ and stirred 15 hours;
(2) after step (1) reacts completely, with saturated sodium bicarbonate aqueous solution cancellation reaction, in and trifluoroacetic acid;
(3) use extracted with diethyl ether, anhydrous sodium sulfate drying filters, and concentrates, and rapid column chromatography obtains 2-alkyl-4,4-diaryl ethyl trans-2-butenoate.
2. 2-alkyl-4 according to claim 1, the synthetic method of 4-diaryl ethyl trans-2-butenoate is characterized in that the mol ratio of described electron rich aromatic compound and 2,3-connection olefin(e) acid ester is 1: 1.19～1.27.
3. 2-alkyl-4 according to claim 1, the synthetic method of 4-diaryl ethyl trans-2-butenoate, the mol ratio that it is characterized in that described dichloro diacetonitrile palladium and electronics aromatic compound is 0.044～0.058: 1.
4. 2-alkyl-4 according to claim 1, the synthetic method of 4-diaryl ethyl trans-2-butenoate, the volume ratio that it is characterized in that described N,N-dimethylacetamide and trifluoroacetic acid is 1: 4.
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