CN100556871C - The synthetic method of triarylmethane derivatives - Google Patents
The synthetic method of triarylmethane derivatives Download PDFInfo
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- CN100556871C CN100556871C CNB2007100543258A CN200710054325A CN100556871C CN 100556871 C CN100556871 C CN 100556871C CN B2007100543258 A CNB2007100543258 A CN B2007100543258A CN 200710054325 A CN200710054325 A CN 200710054325A CN 100556871 C CN100556871 C CN 100556871C
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Abstract
The invention discloses the synthetic method of a kind of triarylmethane and derivative, preparation process is as follows: substituted benzaldehyde, acetic anhydride, catalyzer are joined in the organic solvent, add substituted benzene compound, be heated to 20～120 ℃, reacted 1～50 hour, reaction finishes, concentrate, purifying gets product; Described substituted benzaldehyde is phenyl aldehyde, halogeno-benzene formaldehyde, alkyl substituted benzene formaldehyde or nitro substituted benzaldehyde, described catalyzer is iron trichloride, Iron(III) chloride hexahydrate or Indium-111 chloride, described substituted benzene is halogeno-benzene, alkyl substituted benzene or methoxyl group substituted benzene, the present invention have reaction conditions gentleness, raw material range extensively and cheap, the reaction specificity is strong, productive rate is high, the advantage little to the influence of environment.
Description
Technical field
The invention belongs to the organic compound synthesis technical field, relate to a kind of synthetic method of triarylmethane derivatives.
Background technology
Trisubstituted benzene methylmethane and derivative thereof all have important effect in fields such as material, medicine, chemical industry, and triarylmethane derivatives is very useful blocking group, can also be as optical agents and dyestuff.At present, the method of synthetic trisubstituted benzene methylmethane needs complicated process and exacting terms mostly, and for example: the high pressure that needs that need in corrosive acid, the reaction to need the bigger organic solvent of toxicity, also has just can be finished the loaded down with trivial details operating process of reaction and needs etc.Recently, there is bibliographical information to be used as catalyzer and can obtains higher yield, [V ijay N, K.G.Abhilash, and N.Vidya Org.Lett., 2005,7,5857 with expensive Au (golden salt) or metal iridium-Xi (salt); Susmita P, Joyanta C, Ujjal K.R, SujitR.J.O.C 2007,72,3100-3103].But this catalyzer price is very high, and the reaction pair compound has certain selectivity, has only the group that has the stronger sub-ability of power supply on part of compounds such as the phenyl ring, for example, and methoxyl group, the yield that reactions such as hydroxyl just can obtain.In addition, also there is bibliographical information to need equivalent or excessive aluminum chloride as catalyzer [Xiao Wang, Yikai Wang, Da-Ming Du, Jiaxi XuJournal of Molecular Catalysis A:Chemical, 2006,255,31-35], the also same Au of this method (golden salt) or metal iridium-Xi (salt) are used that synthetic method as catalyzer is the same a significant limitation on material choice.
Summary of the invention
The purpose of this invention is to provide the synthetic method that a kind of applicable raw materials is extensive, react simple, react the triarylmethane derivatives that specificity is strong, productive rate is high.
The present invention realizes above-mentioned purpose by the following technical solutions: the synthetic method of triarylmethane derivatives, synthesis step is as follows: substituted benzaldehyde, acetic anhydride, catalyzer are joined in the organic solvent, add substituted benzene compound, be heated to 20～120 ℃, reacted 1～50 hour, reaction finishes, and concentrates, and purifying gets product; Described substituted benzaldehyde is phenyl aldehyde, halogeno-benzene formaldehyde, alkyl substituted benzene formaldehyde or nitro substituted benzaldehyde, described catalyzer is iron trichloride, Iron(III) chloride hexahydrate or Indium-111 chloride, and described substituted benzene is halogeno-benzene, alkyl substituted benzene or methoxyl group substituted benzene.
The synthesis step of the triarylmethane derivatives of different substituted aryls is as follows: with substituted benzaldehyde, acetic anhydride, catalyst dissolution in organic solvent, added a kind of substituted benzene stirring at room 1～4 hour, add another kind of substituted benzene then, be heated to 20～120 ℃, reacted 1～50 hour, reaction finishes, and concentrates, and purifying gets product.
The mole dosage of described catalyzer is 1～50% of a substituted benzaldehyde mole dosage, and described substituted benzene consumption uses 4～20mmol substituted benzene for the 1mmol substituted benzaldehyde, and the consumption of described acetic anhydride uses 0～10mmol acetic anhydride for the 1mmol substituted benzaldehyde.
Described substituted benzaldehyde is phenyl aldehyde, chlorinated benzene formaldehyde, bromobenzene formaldehyde, alkyl substituted benzene formaldehyde or nitro substituted benzaldehyde.
Described substituted benzene is chlorinated benzene, bromobenzene, methyl substituted benzene or halogenated methoxy benzene.
Described organic solvent is a halohydrocarbon, and consumption uses 1～10ml organic solvent for the 1mmol substituted benzaldehyde.
The general formula of described reaction is:
Perhaps
The present invention is with substituted benzaldehyde, substituted benzene is a raw material, in the presence of acetic anhydride, use iron trichloride, Iron(III) chloride hexahydrate or Indium-111 chloride are as catalyzer, one-step synthesis trisubstituted benzene methylmethane analog derivative, reaction is simple, catalyzer asepsis environment-protecting wherein, and low price, synthetic method of the present invention has the reaction conditions gentleness, raw material range is extensive and cheap, the reaction specificity is strong, the productive rate height, to advantage such as the influence of environment is little, this reaction not only can be synthesized identical substituted-phenyl methane and derivative thereof, can also synthesize different substituted-phenyl methane of three molecules and derivative thereof.
1H NMR collection of illustrative plates,
13The DPX-400 type 400,000,000 superconduction nuclear magnetic resonance spectrometers that the CNMR collection of illustrative plates is produced with Bruker company, as solvent, TMS measures as interior mark with deuterochloroform.
Embodiment
Further describe the present invention below in conjunction with embodiment:
Embodiment 1,2,2 '-(phenmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol (0.103ml) phenyl aldehyde, the acetic anhydride of 3.2mmol, the iron trichloride of 0.1mmol, the 2ml p-Xylol is heated to 80 ℃ with oil bath then under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(phenmethyl) pure connection (1, the 4-dimethyl benzene) 237mg (purity＞99%, colorless solid).Separation yield 79%.The nmr analysis data of compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.27-7.23(m，2H)，7.20-7.19(m，1H)，7.05-7.01(m，4H)，6.94-6.92(d，J＝7.4Hz，2H)，6.54(s，2H)，5.63(s，1H)，2.18(s，6H)，2.11(s，6H)；
13CNMR(100MHz，CDCl
3)δ142.9，141.8，135.0，133.5，130.2，129.9，129.9，128.3，127.0，126.1，50.5，21.3，19.2.(M+Na)：323.2mp.92℃
Embodiment 2,2,2 '-(phenmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol (0.103ml) phenyl aldehyde, the iron trichloride of 0.1mmol, 2ml p-Xylol, under magnetic agitation, be heated to 70 ℃ then, reacted 30 hours with oil bath.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(phenmethyl) pure connection (1, the 4-dimethyl benzene) 15mg (purity＞99%, colorless solid).Separation yield 5%.Present embodiment
1The HNMR collection of illustrative plates,
13The CNMR collection of illustrative plates is with embodiment 1; The nmr analysis data of compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.27-7.23(m，2H)，7.20-7.19(m，1H)，7.05-7.01(m，4H)，6.94-6.92(d，J＝7.4Hz，2H)，6.54(s，2H)，5.63(s，1H)，2.18(s，6H)，2.11(s，6H)；
13CNMR(100MHz，CDCl
3)δ142.9，141.8，135.0，133.5，130.2，129.9，129.9，128.3，127.0，126.1，50.5，21.3，19.2.
Embodiment 3,2,2 '-(phenmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol (0.103ml) phenyl aldehyde, 3.2mmol acetic anhydride, the Iron(III) chloride hexahydrate of 0.1mmol, 2ml p-Xylol, under magnetic agitation, be heated to 120 ℃ then, reacted 1 hour with oil bath.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(phenmethyl) pure connection (1, the 4-dimethyl benzene) 216mg (purity＞99%, colorless solid).Separation yield 72%.Present embodiment
1H NMR collection of illustrative plates,
13The CNMR collection of illustrative plates is with embodiment 1; The nmr analysis data of compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.27-7.23(m，2H)，7.20-7.19(m，1H)，7.05-7.01(m，4H)，6.94-6.92(d，J＝7.4Hz，2H)，6.54(s，2H)，5.63(s，1H)，2.18(s，6H)，2.11(s，6H)；
13CNMR(100MHz，CDCl
3)δ142.9，141.8，135.0，133.5，130.2，129.9，129.9，128.3，127.0，126.1，50.5，21.3，19.2.
Embodiment 4,2,2 '-(phenmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol (0.103ml) phenyl aldehyde, the acetic anhydride of 3.2mmol, the Indium-111 chloride of 0.1mmol, the 2ml p-Xylol is heated to 90 ℃ with oil bath then under magnetic agitation, reacted 10 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(phenmethyl) pure connection (1, the 4-dimethyl benzene) 183mg (purity＞99%, colorless solid).Separation yield 60%, the nmr analysis data of compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.27-7.23(m，2H)，7.20-7.19(m，1H)，7.05-7.01(m，4H)，6.94-6.92(d，J＝7.4Hz，2H)，6.54(s，2H)，5.63(s，1H)，2.18(s，6H)，2.11(s，6H)；
13CNMR(100MHz，CDCl
3)δ142.9，141.8，135.0，133.5，130.2，129.9，129.9，128.3，127.0，126.1，50.5，21.3，19.2.
Embodiment 5,2,2 '-(phenmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol (0.103ml) phenyl aldehyde, the acetic anhydride of 10mmol, the iron trichloride of 0.01mmol, the 10ml p-Xylol is heated to 80 ℃ with oil bath then under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(phenmethyl) pure connection (1, the 4-dimethyl benzene) 183mg (purity＞99%, colorless solid).Separation yield 46%.Present embodiment
1The HNMR collection of illustrative plates,
13The CNMR collection of illustrative plates is with embodiment 1; The nmr analysis data of compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.27-7.23(m，2H)，7.20-7.19(m，1H)，7.05-7.01(m，4H)，6.94-6.92(d，J＝7.4Hz，2H)，6.54(s，2H)，5.63(s，1H)，2.18(s，6H)，2.11(s，6H)；
13CNMR(100MHz，CDCl
3)δ142.9，141.8，135.0，133.5，130.2，129.9，129.9，128.3，127.0，126.1，50.5，21.3，19.2.
Embodiment 6,2,2 '-(to the methylbenzene methyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol p-tolyl aldehyde, the acetic anhydride of 3.2mmol, the iron trichloride of 0.5mmol, the 2ml p-Xylol is heated to 80 ℃ with oil bath then under magnetic agitation, reacted 10 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(to the methylbenzene methyl) pure connection (1, the 4-dimethyl benzene) 267mg (purity＞99%, colorless solid).Separation yield 85%.The nmr analysis data of compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.06-7.01(m，4H)，6.93-6.89(t，J＝8.3Hz，4H)，6.55(s，2H)，5.58(s，1H)，2.31(s，3H)，2.18(s，6H)，2.10(s，6H).
13CNMR(100MHz，CDCl
3)δ142.5，140.2，135.9，135.4，133.9，130.6，130.3，130.2，129.4，127.3，50.5，21.7，21.5，19.7.
Embodiment 7,2,2 '-(o-methyl-benzene methyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol o-methyl-benzene formaldehyde, the acetic anhydride of 3.2mmol, the iron trichloride of 0.1mmol, the 2ml p-Xylol is heated to 90 ℃ with oil bath then under magnetic agitation, reacted 10 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(o-methyl-benzene methyl) pure connection (1, the 4-dimethyl benzene) 210mg (purity＞99%, colorless solid).Separation yield 67%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.13-7.12(m，2H)，7.07-7.02(m，3H)，6.94-6.92(d，J＝7.3Hz，2H)，6.72-6.70(d，J＝7.0Hz，1H)，6.51(s，2H)，5.63(s，1H)，2.18(s，6H)，2.13(s，3H)，2.08(s，6H).
13CNMR(100MHz，CDCl
3)δ141.6，141.2，136.6，135.1，133.5，130.2，130.1，129.8，129.2，127.0，126.2，125.8，47.2，21.3，19.5，19.0.
Embodiment 8,2,2 '-(m-nitro methyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol m-nitrobenzaldehyde, the acetic anhydride of 3.2mmol, the iron trichloride of 0.2mmol, the 8ml p-Xylol is heated to 50 ℃ with oil bath then under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(m-nitro methyl) pure connection (1, the 4-dimethyl benzene) 304mg (purity＞99%, colorless solid).Separation yield 88%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ8.10-8.08(d，J＝8.0Hz，1H)，7.91(s，1H)，7.46-7.42(t，J＝7.9Hz，1H)，7.37-7.35(d，J＝7.6Hz，1H)，7.08-7.06(d，J＝7.6Hz，2H)，6.99-6.97(d，J＝7.6Hz，2H)，6.47(s，2H)，5.74(s，1H)，2.20(s，6H)，2.11(s，6H).
13CNMR(100MHz，CDCl
3)δ148.5，145.5，140.3，135.9，135.5，133.3，130.6，129.8，129.2，127.6，124.6，121.6，50.1，21.3，19.2.
Embodiment 9,2,2 '-(p-nitrophenyl methyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add the 1mmol paranitrobenzaldehyde, 3.2mmol acetic anhydride, the iron trichloride of 0.05mmol, 5ml p-Xylol, under magnetic agitation, be heated to 20 ℃ then, reacted 50 hours with oil bath.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(p-nitrophenyl methyl) pure connection (1, the 4-dimethyl benzene) 242mg (purity＞99%, colorless solid).Separation yield 45%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ8.11-8.09(d，J＝8.7Hz，2H)，7.21-7.18(d，J＝8.6Hz，2H)，7.06-7.03(d，J＝7.1Hz，2H)，6.97-6.95(d，J＝7.5Hz，2H)，6.50(s，2H)，5.74(s，1H)，2.19(s，6H)，2.11(s，6H).
13CNMR(100MHz，CDCl
3)δ151.2，146.6，140.4，135.6，133.5，130.7，129.8，129.0，127.7，123.6，50.4，21.3，19.3.
Embodiment 10,2,2 '-(to chlorophenylmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol 4-chloro-benzaldehyde, the acetic anhydride of 3.2mmol, the iron trichloride of 0.1mmol, the 6ml p-Xylol is heated to 60 ℃ with oil bath then under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(to chlorophenylmethyl) pure connection (1, the 4-dimethyl benzene) 251mg (purity＞99%, colorless solid).Separation yield 75%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.23-7.21(d，J＝8.1Hz，2H)，7.04-7.02(d，J＝7.6Hz，2H)，7.00-6.93(d，J＝7.9Hz，4H)，6.50(s，2H)，5.59(s，1H)，2.19(s，6H)，2.09(s，6H).
13CNMR(100MHz，CDCl
3)δ141.6，141.3，135.2，133.4，132.0，131.2.130.4，129.8，128.5，127.2，49.9，21.3，19.2.
Embodiment 11,2,2 '-(chlorophenylmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol m chlorobenzaldehyde, the acetic anhydride of 3.2mmol, the iron trichloride of 0.1mmol, the 2ml p-Xylol is heated to 80 ℃ with oil bath then under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(chlorophenylmethyl) pure connection (1, the 4-dimethyl benzene) 294mg (purity＞99%, colorless solid).Separation yield 88%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.19-7.17(m，2H)，7.06-7.05(d，J＝2.8Hz，1H)，7.03-7.02(d，J＝4.7Hz，2H)，6.96-6.94(q，2H)，6.90(s，1H)，6.51(s，2H)，5.60(s，1H)，2.20(s，6H)，2.10(s，6H).
13CNMR(100MHz，CDCl
3)δ144.2，139.9，134.2，133.2，132.3，129.3，128.8，128.4，127.9，127.0，126.2，125.4，49.1，20.2，18.1.
Embodiment 12,2,2 '-(adjacent chlorophenylmethyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol o-chlorobenzaldehyde, the acetic anhydride of 3.2mmol, the iron trichloride of 0.3mmol, the 3ml p-Xylol is heated to 100 ℃ with oil bath then under magnetic agitation, reacted 15 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(adjacent chlorophenylmethyl) pure connection (1, the 4-dimethyl benzene) 267mg (purity＞99%, colorless solid).Separation yield 60%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.37-7.35(q，1H)，7.18-7.10(m，2H)，7.05-7.04(d，J＝7.6Hz，2H)，6.96-6.94(d，J＝7.6Hz，2H)，6.85-6.83(q，1H)，6.49(s，2H)，5.94(s，1H)，2.19(s，6H)，2.11(s，6H).
13CNMR(100MHz，CDCl
3)δ140.8，140.3，135.0，134.7，133.6，131.0，130.2，129.6，129.5，127.6，127.2，126.5，47.4，21.3，19.0.
Embodiment 13,2,2 '-(adjacent Brombenzyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add the adjacent bromobenzaldehyde of 1mmol, the acetic anhydride of 3.2mmol, the iron trichloride of 0.1mmol, the 2ml p-Xylol is heated to 80 ℃ with oil bath then under magnetic agitation, reacted 6 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(adjacent Brombenzyl) pure connection (1, the 4-dimethyl benzene) 291mg (purity＞99%, colorless solid).Separation yield 77%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.56-7.54(q，1H)，7.18-7.14(m，1H)，7.08-7.03(m，3H)，6.96-6.94(d，J＝7.6Hz，2H)，6.85-6.83(q，1H)，6.49(s，2H)，5.89(s，1H)，2.18(s，6H)，2.11(s，6H).
13CNMR(100MHz，CDCl
3)δ142.6，140.4，135.1，133.8，133.0，131.3，130.3，129.7，128.0，127.3，127.2，126.0，50.3，21.4，19.2.
Embodiment 14,2,2 '-(Brombenzyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol 3-bromobenzaldehyde, the acetic anhydride of 8mmol, the iron trichloride of 0.4mmol, the 2ml p-Xylol is heated to 80 ℃ with oil bath then under magnetic agitation, reacted 16 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(Brombenzyl) pure connection (1, the 4-dimethyl benzene) 340mg (purity＞99%, colorless solid).Separation yield 81%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.34-7.32(d，J＝7.9Hz，1H)，7.18(s，1H)，7.13-7.09(t，J＝7.8Hz，1H)，7.04-7.03(d，J＝7.6Hz，2H)，6.96-6.92(m，3H)，6.51(s，2H)，5.59(s，1H)，2.19(s，6H)，2.10(s，6H).
13CNMR(100MHz，CDCl
3)δ145.6，141.0，135.3，133.4，132.8，130.4，129.9，129.8，129.5.128.5，127.3，122.6，50.2，21.3，19.2.
Embodiment 15,2,2 '-(to Brombenzyl) connection (1, the synthesizing 4-dimethyl benzene): in round-bottomed flask, add 1mmol p-bromobenzaldehyde, the acetic anhydride of 1mmol, the iron trichloride of 0.3mmol, the 2ml p-Xylol is heated to 30 ℃ with oil bath then under magnetic agitation, reacted 40 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(to Brombenzyl) pure connection (1, the 4-dimethyl benzene) 295mg (purity＞99%, colorless solid).Separation yield 60%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.39-7.37(q，2H)，7.05-7.03(d，J＝7.6Hz，2H)，6.96-6.94(d，J＝8.5Hz，2H)，6.90-6.88(d，J＝8.3Hz，2H)，6.50(s，2H)，5.57(s，1H)，2.20(s，6H)，2.09(s，6H).
13CNMR(100MHz，CDCl
3)δ142.1，141.1，135.2，133.3，131.5，131.3，130.3，129.7，127.2，120.0，49.9，21.2，19.2.
Embodiment 16,2, synthesizing of 2 '-(phenyl methyl) connection (1-methoxyl group-4-methylbenzene): in round-bottomed flask, add the 1mmol phenyl aldehyde, 3.2mmol acetic anhydride, 0.1mmol iron trichloride, 4mmol is heated to 80 ℃ with oil bath then to methoxy toluene under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(phenyl methyl) pure connection (1-methoxyl group-4-methylbenzene) 262mg (purity＞99%, colorless solid).Separation yield 79%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.24-7.20(t，J＝7.3Hz，2H)，7.16-7.15(d，J＝7.1Hz，1H)，7.06-7.04(d，J＝7.3Hz，2H)，6.99-6.96(q，2H)，6.75-6.73(d，J＝8.2Hz，2H)，6.61-6.61(d，J＝1.7Hz，2H)，6.15(s，1H)，3.63(s，6H)，2.18(s，6H).
13CNMR(100MHz，CDCl
3)δ155.3，144.1，132.5，130.8，129.4，129.2，127.9，127.5，125.7，111.0，56.0，43.1，20.8.
Embodiment 17,5,5 '-(phenmethyl) connection (1,2, the synthesizing 4-Three methyl Benzene): in round-bottomed flask, add 1mmol phenyl aldehyde, the acetic anhydride of 5mmol, the iron trichloride of 0.1mmol, 4mmol1,2, the 4-trimethylbenzene is heated to 80 ℃ with oil bath then under magnetic agitation, reacts 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 5,5 '-(phenmethyl) pure connection (1) 243mg (purity＞99%, colorless solid).Separation yield 74%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.26-7.17(m，3H)，7.03-7.01(d，J＝7.3Hz，2H)，6.91(s，2H)，6.50(s，2H)，5.57(s，1H)，2.19(s，6H)，2.09(s，12H).
13CNMR(100MHz，CDCl
3)δ143.3，139.2，133.9，133.5，133.3，131.5，130.3，129.6，128.0，125.8，49.7，19.4，19.1，18.9.
Embodiment 18,2, synthesizing of 2 '-(to Brombenzyl) connection (1-methoxyl group-4-chlorobenzene): in round-bottomed flask, add the 1mmol p-bromobenzaldehyde, the acetic anhydride of 6mmol, 0.1mmol iron trichloride, 4mmol is heated to 80 ℃ with oil bath then to the methoxyl group chlorobenzene under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(to Brombenzyl) pure connection (1-methoxyl group-4-chlorobenzene) 401mg (purity＞99%, colorless solid).Separation yield 89%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.39-7.37(d，J＝8.4Hz，2H)，7.19-7.16(q，2H)，6.91-6.89(d，J＝8.4Hz，2H)，6.79-6.77(d，J＝8.7Hz，2H)，6.69-6.68(d，J＝2.5Hz，2H)，5.99(s，1H)，3.67(s，6H).
13CNMR(100MHz，CDCl
3)δ155.7，141.3，133.1，131.4，130.9，129.5，127.6，125.3，120.3，112.0，55.9，43.0.
Embodiment 19,2, synthesizing of 2 '-(adjacent Brombenzyl) connection (1-methoxyl group-4-chlorobenzene): in round-bottomed flask, add the adjacent bromobenzaldehyde of 1mmol, 3.2mmol acetic anhydride, 0.1mmol iron trichloride, 6mmol is heated to 80 ℃ with oil bath then to the methoxyl group chlorobenzene under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(adjacent Brombenzyl) pure connection (1-methoxyl group-4-chlorobenzene) 266mg (purity＞99%, colorless solid).Separation yield 59%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.57-7.55(q，1H)，7.20-7.16(m，3H)，7.11-7.07(m，1H)，6.83-6.78(m，3H)，6.63-6.62(d，J＝2.6Hz，2H)，6.31(s，1H)，3.68(s，6H).
13CNMR(100MHz，CDCl
3)δ155.9，141.8，133.2，132.5，130.2，129.4，128.2，127.7，127.2，125.5，125.3，112.0，56.1，43.6.
Embodiment 20,2, synthesizing of 2 '-(to Brombenzyl) connection (1-methoxyl group-4-bromobenzene): in round-bottomed flask, add the 1mmol p-bromobenzaldehyde, 3.2mmol acetic anhydride, 0.1mmol iron trichloride, 10mmol is heated to 80 ℃ with oil bath then to the methoxyl group bromobenzene under magnetic agitation, reacted 22 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain 2,2 '-(to Brombenzyl) pure connection (1-methoxyl group-4-bromobenzene) 430mg (purity＞99%, colorless solid).Separation yield 80%.The nmr analysis data of this compound are as follows:
1H?NMR(400MHz，CDCl
3)δ7.39-7.37(d，J＝8.4Hz，2H)，7.34-7.31(q，2H)，6.90-6.88(d，J＝8.4Hz，2H)，6.82-6.81(d，J＝2.4Hz，2H)，6.74-6.72(d，J＝8.7Hz，2H)，5.98(s，1H)，3.67(s，6H).
13CNMR(100MHz，CDCl
3)δ156.1，141.2，133.5，132.2，131.4，130.9，130.6，120.3，112.7，112.4，55.9，42.9.
The triphenyl methane 2-((3, the 4-dimethyl benzene) (phenyl) methyl)-1 that embodiment 21, three molecules are different, synthesizing of 3,5 Three methyl Benzenes: in round-bottomed flask, add 1mmol (0.103ml) phenyl aldehyde, the acetic anhydride of 2mmol, 0.1mmol iron trichloride, 1,3 of 1mmol, the 5-trimethylbenzene, the methylene dichloride of 1ml is room temperature reaction two hours under magnetic agitation then, the o-Xylol that adds 1ml then is heated to 80 ℃ with oil bath, reacts 24 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain pure 2-((3, the 4-dimethyl benzene) (phenyl) methyl)-1,3,5 Three methyl Benzene 276mg (purity＞99%, colorless solid).Separation yield 88%.The nmr analysis data of this compound are as follows:
1HNMR(400MHz，CDCl
3)δ7.25-7.16(m，3H)，7.08-7.07(d，J＝7.3Hz，2H)，7.02-7.00(d，J＝7.7Hz，2H)，6.9(s，1H)，6.84(s，1H)，6.79-6.77(d，J＝7.2Hz，1H)，5.92(s，1H)，2.27(s，3H)，2.23(s，3H)，2.18(s，3H)，2.00(s，6H).
13CNMR(100MHz，CDCl
3)δ143.0，139.4，137.4，137.1，136.0，135.6，133.9，130.5，129.9，129.2，129.1，127.9，126.5，125.5，50.4，21.8，20.6，19.7，19.2.
The triphenyl methane 2-((3, the 4-dimethyl benzene) (phenyl) methyl)-1 that embodiment 22, three molecules are different, synthesizing of 3,5 Three methyl Benzenes: in round-bottomed flask, add 1mmol (0.103ml) phenyl aldehyde, the acetic anhydride of 2mmol, 0.1mmol iron trichloride, 1,3 of 1mmol, the 5-trimethylbenzene, the trichloromethane of 10ml is room temperature reaction two hours under magnetic agitation then, the o-Xylol that adds 1ml then is heated to 80 ℃ with oil bath, reacts 24 hours.Remove oil bath, drop to room temperature; Rotatory evaporator concentrates, and raffinate is a developping agent with the sherwood oil, separates with silica gel thin-layer chromatography.Obtain pure 2-((3, the 4-dimethyl benzene) (phenyl) methyl)-1,3,5 Three methyl Benzene 276mg (purity＞99%, colorless solid).Separation yield 83%.The nmr analysis data of this compound are as follows:
1HNMR(400MHz，CDCl
3)δ7.25-7.16(m，3H)，7.08-7.07(d，J＝7.3Hz，2H)，7.02-7.00(d，J＝7.7Hz，2H)，6.9(s，1H)，6.84(s，1H)，6.79-6.77(d，J＝7.2Hz，1H)，5.92(s，1H)，2.27(s，3H)，2.23(s，3H)，2.18(s，3H)，2.00(s，6H).
13CNMR(100MHz，CDCl
3)δ143.0，139.4，137.4，137.1，136.0，135.6，133.9，130.5，129.9，129.2，129.1，127.9，126.5，125.5，50.4，21.8，20.6，19.7，19.2.
Claims (8)
1, the synthetic method of triarylmethane derivatives, it is characterized in that, synthesis step is as follows: phenyl aldehyde or substituted benzaldehyde, acetic anhydride, catalyzer are joined in the organic solvent, add substituted benzene compound, be heated to 20～120 ℃, reacted 1～50 hour, reaction finishes, concentrate, purifying gets product; Described substituted benzaldehyde is halogeno-benzene formaldehyde, alkyl substituted benzene formaldehyde or nitro substituted benzaldehyde, described catalyzer is iron trichloride, Iron(III) chloride hexahydrate or Indium-111 chloride, and described substituted benzene is halogeno-benzene, alkyl substituted benzene, methoxyl group substituted benzene or halogenated methoxy benzene.
2, the synthetic method of triarylmethane derivatives as claimed in claim 1, it is characterized in that, the synthesis step of the triarylmethane derivatives of different substituted aryls is as follows: with phenyl aldehyde or substituted benzaldehyde, acetic anhydride, catalyst dissolution in organic solvent, add a kind of substituted benzene stirring at room 1～4 hour, and added another kind of substituted benzene then, be heated to 20～120 ℃, reacted 1～50 hour, reaction finishes, and concentrates, and purifying gets product.
3, the synthetic method of triarylmethane derivatives, it is characterized in that, synthesis step is as follows: phenyl aldehyde or substituted benzaldehyde, acetic anhydride, catalyzer are joined in the organic solvent, add substituted benzene compound, be heated to 20～120 ℃, reacted 1～50 hour, reaction finishes, concentrate, purifying gets product; Described substituted benzaldehyde is a halogeno-benzene formaldehyde, alkyl substituted benzene formaldehyde or nitro substituted benzaldehyde, described catalyzer is an iron trichloride, Iron(III) chloride hexahydrate or Indium-111 chloride, described substituted benzene is a halogeno-benzene, alkyl substituted benzene, methoxyl group substituted benzene or halogenated methoxy benzene, the mole dosage of described catalyzer is 1～50% of phenyl aldehyde or a substituted benzaldehyde mole dosage, described substituted benzene consumption is that 1mmol phenyl aldehyde or substituted benzaldehyde use 4～20mmol substituted benzene, and the consumption of described acetic anhydride is that 1mmol phenyl aldehyde or substituted benzaldehyde use 0～10mmol acetic anhydride.
4, the synthetic method of triarylmethane derivatives as claimed in claim 3, it is characterized in that, the synthesis step of the triarylmethane derivatives of different substituted aryls is as follows: with phenyl aldehyde or substituted benzaldehyde, acetic anhydride, catalyst dissolution in organic solvent, add a kind of substituted benzene stirring at room 1～4 hour, and added another kind of substituted benzene then, be heated to 20～120 ℃, reacted 1～50 hour, reaction finishes, and concentrates, and purifying gets product.
As the synthetic method of claim 3 or 4 described triarylmethane derivatives, it is characterized in that 5, described substituted benzaldehyde is chlorinated benzene formaldehyde, bromobenzene formaldehyde, alkyl substituted benzene formaldehyde or nitro substituted benzaldehyde.
As the synthetic method of claim 3 or 4 described triarylmethane derivatives, it is characterized in that 6, described substituted benzene is chlorinated benzene, bromobenzene or methyl substituted benzene.
7, the synthetic method of triarylmethane derivatives as claimed in claim 5 is characterized in that, described organic solvent is a halohydrocarbon, and consumption is that 1mmol phenyl aldehyde or substituted benzaldehyde use 1～10ml organic solvent.
8, the synthetic method of triarylmethane derivatives as claimed in claim 6 is characterized in that, described organic solvent is a halohydrocarbon, and consumption is that 1mmol phenyl aldehyde or substituted benzaldehyde use 1～10ml organic solvent.
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