CN111484420A - Method for synthesizing triarylmethane derivative and triarylmethane derivative obtained by same - Google Patents

Method for synthesizing triarylmethane derivative and triarylmethane derivative obtained by same Download PDF

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CN111484420A
CN111484420A CN201910088261.6A CN201910088261A CN111484420A CN 111484420 A CN111484420 A CN 111484420A CN 201910088261 A CN201910088261 A CN 201910088261A CN 111484420 A CN111484420 A CN 111484420A
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于雅琴
徐大振
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Tianjin Normal University
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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Abstract

The invention discloses a method for synthesizing triarylmethane derivatives, which is synthesized by using ferric trichloride as a catalyst and carrying out one-pot reaction on various substituted salicylaldehyde, aromatic boric acid and aromatic hydrocarbon. The three different aryls are introduced by salicylaldehyde, arylboronic acid and aromatic hydrocarbon which are low in price and easy to obtain in one step, the reaction has high chemical selectivity, triarylmethane derivatives with various completely asymmetric groups are provided, the method is simple and convenient to operate, the reaction time is short, the catalyst is low in price and easy to obtain, the production cost is low, the pollution is less, the post-treatment is simple, and the reaction has good yield.

Description

Method for synthesizing triarylmethane derivative and triarylmethane derivative obtained by same
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing triarylmethane derivatives and triarylmethane derivatives obtained by the method.
Background
Triarylmethane derivatives are widely used in pharmaceutical chemistry, dye industry and material science due to their structural particularity, and are a very important class of compounds. The methods used up to now for the synthesis of triarylmethane derivatives are mainly: diaryl methanol (ester, ether, imine, etc.) directly reacts with arene by a Friedel-crafts alkylation method, the synthesis method is generally easy to react for the arene containing electron-donating groups, a reaction substrate has certain limitation, and an isomer byproduct is easy to generate; the other synthetic method is synthesized by cross coupling reaction or carbon-hydrogen functionalization reaction catalyzed by transition metal; yet another method is to synthesize by 1, 6-addition arylation of p-benzoquinone derivatives. There are some obvious disadvantages in the above synthetic methods, such as: limited substrate range, poor regioselectivity, expensive transition metals often used in the reaction, multi-step reactions and harsh reaction conditions.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention provides a method for synthesizing triarylmethane derivatives, which is a one-pot reaction using cheap FeCl3The catalyst is used for preparing the triarylmethane derivative, and has the advantages of simple and convenient operation, short reaction time, cheap and easily-obtained catalyst, low production cost, less pollution, simple post-treatment and high reaction yield.
It is another object of the present invention to provide triarylmethane derivatives obtained by the above process.
The purpose of the invention is realized by the following technical scheme.
A method of synthesizing triarylmethane derivatives, comprising the steps of:
mixing a first reactant, a second reactant, a third reactant, piperidine and a catalyst, adding a solvent, reacting for 20-80 min at 40-120 ℃ under stirring, cooling to room temperature of 20-25 ℃ after the reaction is finished, adding ethyl acetate, washing to obtain an organic phase, drying the organic phase, evaporating the solvent to obtain a residue, separating the residue by column chromatography, evaporating the solvent again, and drying to obtain a triarylmethane derivative, wherein the ratio of the first reactant, the second reactant, the third reactant, the piperidine and the catalyst is 1 (1-1.5): (1-1.5): (1-1.5): (0.5-1), the catalyst is FeCl3；
The molecular formula of the first reactant is:
Figure BDA0001962473640000021
R1is one or more substituents on the phenyl ring to which it is attached, when R is1When it is a substituent, R1is-H or-Br, when R is1When there are more than one substituent, R1Is 3,5-Cl2Or 3,5-Br2；
The molecular formula of the second reactant is:
Figure BDA0001962473640000022
the R is2Is one or more substituents on the phenyl ring to which it is attached, when R is2When it is a substituent, R2is-H, -F, -Br, -MeO or-t-Bu, when R is2When there are more than one substituent, R2Is 3, 4-dimethoxy;
the molecular formula of the third reactant is:
Figure BDA0001962473640000023
the R is3is-H, -Me or-Et, said R4is-H, -Me or-Et, said R5Is a substituent on the phenyl ring to which it is attached, said R5is-H or-CH3。
In the technical scheme, a mixed solution of n-hexane and ethyl acetate is used as an eluent for column chromatography separation, and the ratio of the n-hexane to the ethyl acetate is 6:1 in parts by volume.
In the above technical solution, the solvent is one or more of toluene, chlorobenzene, 1, 4-dioxane, acetonitrile, ethanol, water, dichloroethane and dimethylformamide, and is used to provide a uniformly dispersed atmosphere for the first reactant, the second reactant, the piperidine and the third reactant.
In the technical scheme, the solvent is toluene, chlorobenzene, 1, 4-dioxane, acetonitrile, ethanol, water, dichloroethane or dimethylformamide.
In the above technical solution, the ratio of the parts by volume of the ethyl acetate to the parts by weight of the first reactant is 50: 1.
in the technical scheme, the washing is sequentially washed by water and saturated saline solution.
In the technical scheme, the ratio of the parts by weight of the first reactant to the parts by volume of the solvent is 1 (1-2), and when the unit of the parts by weight of the first reactant is mmol, the unit of the parts by volume is m L.
In the technical scheme, the stirring reaction is preferably carried out at 100 ℃ for 20-80 min.
In the technical scheme, the reaction time under the stirring condition is detected and determined by adopting thin layer chromatography.
In the above technical solution, the operation steps of drying the organic phase are as follows: to the organic phase was added anhydrous sodium sulfate for drying, and the anhydrous sodium sulfate was filtered.
Triarylmethane derivatives obtained by the above process.
The method of the invention has the following beneficial effects:
1. the synthesis steps are simple, the reaction time is short, the yield is high, the reaction raw materials and the used catalyst are cheap and easy to obtain, and in addition, the reaction substrate of the method has wide application range.
2. The method has simple post-reaction treatment: after the reaction is finished, the product is obtained by simple filtration and column chromatography separation.
Detailed Description
In the specific implementation mode of the invention, the reagents and the medicines involved in the synthesis method are purchased from Tianjin reagent six factories, the purity of the medicines is analytically pure, and the reagents and the medicines are directly used without any pretreatment.
The synthesis method of the invention continuously stirs in the whole process, and the model of an electromagnetic heating stirrer used for stirring is NUOVAII (Temaran, USA); the rotary evaporator was model RE-2000A (Otsuwa instruments liability Co., Ltd., Otsu). Nuclear magnetic resonance instrument model: bruker AV-400spectrometer, 400 MHz.
In the following examples, the degree of progress of the reaction was checked by thin layer chromatography (T L C) during the reflux reaction under heating in which a silica gel plate of G254 type 15mm × 50mm in size was used, a ZF-I type three-way ultraviolet analyzer (Shanghai Ching Tang) was used, the drugs used were purchased from Tianjin reagent Seisakun, the purity of the drugs were all analytically pure and were all used directly without any pretreatment, and when the first reactant of the raw material or salicylaldehyde was found to disappear by T L C and only the target compound was present, it was indicated that the reaction of the synthesis method of the present invention was completed and the next separation operation was continued.
In the following examples, the room temperature is 20 to 25 ℃. When column chromatography is used for separation, the polarity of the developing solvent is as follows: n-hexane/ethyl acetate 6:1 (parts by volume).
The organic phase was dried over anhydrous sodium sulfate and filtered: the organic phase was dried by adding anhydrous sodium sulfate, and the anhydrous sodium sulfate was filtered.
In a particular embodiment of the invention, the amount of substance is in mmol and the volume is in ml.
In the following examples, the solvent was distilled off twice under reduced pressure, and the first distillation under reduced pressure was conducted so as to remove as much of the solvent as possible (possibly with a residue), and the remaining solvent was distilled off in the second distillation (the ratio of the volume of the solvent distilled off in the first distillation to the volume of the solvent distilled off in the second distillation did not affect the effect of obtaining the target compound in the following examples).
The technical scheme of the invention is further explained by combining specific examples.
Example 1
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000041
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.122g) phenylboronic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.145g) N, N-dimethylaniline and 1mmol FeCl were added in this order3(catalyst) (0.161g) was charged into a 10ml dry round-bottomed flask, 2ml of chlorobenzene was added as a solvent, and the reaction was heated under reflux at 100 ℃ and monitored by T L CReacting, cooling to room temperature after the reaction is completed, adding 50ml ethyl acetate into a reaction system, washing with 30ml water and saturated salt water in sequence, drying and filtering an organic phase through anhydrous sodium sulfate, evaporating under reduced pressure to remove a large amount of solvent, separating the residue through column chromatography, evaporating the solvent to remove the solvent again by adopting a mixed solution of normal hexane and ethyl acetate as an eluent, drying to obtain the target compound with the reaction yield of 95 percent,1HNMR(400MHz,DMSO-d6):＝2.83(s,6H,CH3),5.69(s,1H,CH),6.63-6.74(m,4H,ArH),6.79(d,J＝8.0Hz,1H,ArH),6.85(d,J＝8.8Hz,2H,ArH),6.99-7.04(m,3H,ArH),7.15(t,J＝7.2Hz,1H,ArH),7.25(t,J＝7.2Hz,2H,ArH),9.32(s,1H,OH).13C NMR(100MHz,DMSO-d6):＝40.7,48.6,112.8,115.5,119.0,126.1,127.4,128.4,129.4,130.0,130.2,131.2,131.8,145.1,149.2,155.1.
example 2
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (4-methoxyphenyl) (2-hydroxyphenyl) methane), comprising the steps of:
Figure BDA0001962473640000042
1.0mmol (0.122g) of salicylaldehyde, 1.0mmol (0.152g) of p-methoxyphenylboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered through anhydrous sodium sulfate, a large amount of solvent is removed through reduced pressure evaporation, residue is separated through column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is removed through evaporation again, and the target compound is obtained through drying, wherein the reaction yield is 88%.1H NMR(400MHz,CDCl3):＝2.91(s,6H,CH3),3.77(s,3H,CH3),5.52(s,1H,CH),6.68(d,J＝8.2Hz,2H,ArH),6.78-6.84(m,5H,ArH),6.99(d,J＝8.2Hz,2H,ArH),7.05(d,J＝8.2Hz,2H,ArH),7.12(t,J＝8.8Hz,1H,ArH)；13C NMR(100MHz,CDCl3):＝40.7,49.6,55.3,112.9,113.9,116.3,120.6,127.8,129.9,130.1,130.3,131.1,135.1,136.4,149.5,153.7,158.2.
Example 3
A method for synthesizing a triarylmethane derivative ((4-diethylaminophenyl) (2-hydroxyphenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000051
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.122g) phenylboronic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.179g) N, N-diethylaniline and 1mmol FeCl were added in this order3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, and the target compound is obtained after drying, wherein the reaction yield is 93%,1HNMR(400MHz,CDCl3):＝1.15(t,J＝7.2Hz,6H,CH3),3.28-3.33(m,4H,CH2),4.92(br,1H,OH),5.55(s,1H,CH),6.62(d,J＝8.0Hz,2H,ArH),6.82(t,J＝8.4Hz,3H,ArH),6.97(d,J＝8.8Hz,2H,ArH),7.12-7.16(m,3H,ArH),7.22(d,J＝7.2Hz,1H,ArH),7.29(t,J＝7.6Hz,2H,ArH).13C NMR(100MHz,CDCl3):＝12.6,44.4,50.4,112.0,116.3,120.6,126.5,127.3,127.8,128.5,129.4,130.2,130.4,131.0,134.6,143.1,153.7.
example 4
A method of synthesizing a triarylmethane derivative ((4-pyrrolylphenyl) (2-hydroxyphenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000061
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.122g) phenylboronic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.176g) 1-phenylpyrrolidine and 1mmol FeCl were added sequentially3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, and the target compound is obtained after drying, wherein the reaction yield is 94%,1H NMR(400MHz,CDCl3):＝1.96(s,2H,CH2),3.24(s,2H,CH2),4.88(br,1H,OH),5.56(s,1H,CH),6.50(d,J＝8.4Hz,2H,ArH),6.80(t,J＝8.8Hz,3H,ArH),6.99(d,J＝8.4Hz,2H,ArH),7.09-7.15(m,3H,ArH),7.20(t,J＝7.2Hz,1H,ArH),7.28(t,J＝8.4Hz,1H,ArH).13C NMR(100MHz,CDCl3):＝25.5,47.7,50.5,111.9,116.3,120.6,126.5,127.8,128.3,128.5,129.4,130.1,130.4,131.0,143.2,146.9,153.8.
example 5
A method of synthesizing a triarylmethane derivative ((4-methylaminophenyl) (2-hydroxyphenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000062
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.122g) phenylboronic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.128g) N-methylaniline and 1mmol FeCl3(catalyst) (0.161g) adding into 10ml dry round bottom flask, adding 2ml chlorobenzene as solvent, heating reflux reacting at 100 deg.C, T L C monitoring reaction, cooling to room temperature after reaction, adding 50ml ethyl acetate into reaction system, washing with 30ml water and saturated salt water, drying organic phase with anhydrous sodium sulfate, filtering, distilling under reduced pressure to remove a large amount of solvent, separating residue by column chromatography, mixing n-hexane and ethyl acetateThe combined solution is used as eluent, the solvent is evaporated and removed again, the target compound is obtained after drying, the reaction yield is 80 percent,1H NMR(400MHz,CDCl3):＝2.77(s,3H,CH3),4.20(s,2H,OH,NH),5.58(s,1H,CH),6.54(d,J＝8.4Hz,2H,ArH),6.75-6.82(m,3H,ArH),6.95(d,J＝8.4Hz,2H,ArH),7.08-7.12(m,3H,ArH),7.21(t,J＝7.6Hz,1H,ArH),7.28(t,J＝7.6Hz,2H,ArH).13C NMR(100MHz,CDCl3):＝30.9,50.4,112.9,116.2,120.7,126.5,127.8,128.5,129.4,130.2,130.4,130.8,130.9,143.2,148.1,153.7.
example 6
A method of synthesizing a triarylmethane derivative ((2-methyl-4-dimethylaminophenyl) (2-hydroxyphenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000071
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.122g) phenylboronic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.145g) N, N-dimethylaniline and 1mmol FeCl were added in this order3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, the target compound is obtained by drying, the reaction yield is 83%,1HNMR(400MHz,CDCl3):＝2.18(s,3H,CH3),2.89(s,6H,CH3),5.68(s,1H,CH),6.47-6.50(m,1H,ArH),6.59(s,1H,ArH),6.71(t,J＝8.4Hz,2H,ArH),6.73-6.83(m,2H,ArH),7.11(t,J＝7.2Hz,3H,ArH),7.21(t,J＝7.6Hz,1H,ArH),7.28(t,J＝7.2Hz,2H,ArH).13C NMR(100MHz,CDCl3):＝20.3,40.8,47.2,110.5,115.3,116.1,120.6,126.4,127.7,128.5,129.6,129.7,130.3,130.7,137.7,142.7,149.4,153.7.
example 7
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (4-fluorophenyl) methane), comprising the steps of:
Figure BDA0001962473640000072
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.140g) p-fluorophenylboronic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.145g) N, N-dimethylaniline and 1mmol FeCl were added in this order3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, the target compound is obtained by drying, the reaction yield is 91%,1HNMR(400MHz,CDCl3):＝2.96(s,6H,CH3),5.63(s,1H,CH),6.72(d,J＝8.4Hz,2H,ArH),6.82-6.84(m,2H,ArH),6.87(d,J＝7.2Hz,1H,ArH),7.01(t,J＝8.4Hz,4H,ArH),7.11-7.17(m,3H,ArH).13C NMR(100MHz,CDCl3):＝40.6,49.4,112.9,115.1,115.3,116.2,120.7,127.9,129.9,130.3,130.8,138.9,149.5,153.6,160.3,162.7.
example 8
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (4-bromophenyl) methane), comprising the steps of:
Figure BDA0001962473640000081
1.0mmol (0.122g) of salicylaldehyde, 1.0mmol (0.200g) of p-bromophenylboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl were successively mixed3(catalyst) (0.161g) was charged into a 10ml dry round-bottom flask, 2ml chlorobenzene was added as a solvent, the reaction was heated under reflux at 100 ℃ and monitored by T L CCooling to room temperature, adding 50ml ethyl acetate into the reaction system, washing with 30ml water and saturated salt water in sequence, drying the organic phase with anhydrous sodium sulfate, filtering, evaporating under reduced pressure to remove a large amount of solvent, separating the residue by column chromatography, evaporating to remove the solvent again by using the mixed solution of n-hexane and ethyl acetate as eluent, drying to obtain the target compound with reaction yield of 89%,1HNMR(400MHz,CDCl3):＝2.88(s,6H,CH3),5.59(s,1H,CH),6.65-6.72(m,3H,ArH),6.78-6.82(m,2H,ArH),6.94-6.99(m,4H,ArH),7.08(t,J＝7.6Hz,1H,ArH),7.36-7.38(m,2H,ArH).13C NMR(100MHz,CDCl3):＝40.8,49.3,113.1,116.1,120.2,120.7,127.9,130.0,130.4,130.6,131.2,131.5,131.7,142.8,149.5,153.6.
example 9
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (p-tert-butylphenyl) methane), comprising the steps of:
Figure BDA0001962473640000091
1.0mmol (0.122g) of salicylaldehyde, 1.0mmol (0.178g) of p-tert-butylboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl were successively mixed3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, and the target compound is obtained after drying, wherein the reaction yield is 93%,1H NMR(400MHz,CDCl3):＝1.29(s,9H,CH3),2.88(s,6H,CH3),5.55(s,1H,CH),6.66(d,J＝8.4Hz,2H,ArH),6.74-6.83(m,3H,ArH),6.99-7.09(m,5H,ArH),7.29(d,J＝8.0Hz,2H,ArH).13C NMR(100MHz,CDCl3):＝31.5,34.5,40.8,50.0,113.0,116.3,120.6,125.5,127.8,129.0,130.0,130.3,130.5,131.2,139.9,149.3,149.5,153.8.
example 10
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (3-bromophenyl) methane), comprising the steps of:
Figure BDA0001962473640000092
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.200g) m-bromobenzeneboronic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.145g) N, N-dimethylaniline and 1mmol FeCl were added in this order3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, the target compound is obtained by drying, the reaction yield is 85%,1HNMR(400MHz,CDCl3):＝3.20(s,6H,CH3),5.86(s,1H,CH),6.95(d,J＝8.4Hz,2H,ArH),7.05(d,J＝8.0Hz,2H,ArH),7.11(d,J＝7.2Hz,1H,ArH),7.25(d,J＝8.8Hz,2H,ArH),7.33(d,J＝7.6Hz,1H,ArH),7.39-7.49(m,2H,ArH),7.56(s,1H,ArH),7.62(d,J＝7.6Hz,1H,ArH).13CNMR(100MHz,CDCl3):＝40.6,49.7,112.9,116.1,120.8,122.6,128.0,128.0,129.5,129.9,130.3,132.3,145.9,149.5,153.5.
example 11
A method for synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (3, 4-dimethoxyphenyl) methane), comprising the steps of:
Figure BDA0001962473640000101
sequentially adding 1.0mmol (0.122g) of salicylaldehyde and 1.0mmol (0.182g) of 3, 4-bisMethoxyphenylboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, and the target compound is obtained after drying, wherein the reaction yield is 94%,1H NMR(400MHz,CDCl3):＝2.88(s,6H,CH3),3.72(s,3H,CH3),3.80(s,3H,CH3),5.58(s,1H,CH),6.61(d,J＝8.0Hz,1H,ArH),6.68(t,J＝8.0Hz,3H,ArH),6.75(d,J＝8.4Hz,2H,ArH),6.82(s,2H,ArH),6.99(d,J＝8.4Hz,2H,ArH),7.06-7.10(m,1H,ArH).13CNMR(100MHz,CDCl3):＝40.8,49.7,55.9,77.4,111.0,112.7,113.0,116.1,120.5,121.3,127.7,129.9,130.3,130.7,131.2,136.0,147.5,148.9,149.4,153.8.
example 12
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (2-naphthyl) methane), comprising the steps of:
Figure BDA0001962473640000111
1.0mmol (0.122g) salicylaldehyde, 1.0mmol (0.173g) 2-naphthoic acid, 1.2mmol (0.102g) piperidine, 1.2mmol (0.145g) N, N-dimethylaniline and 1mmol FeCl were sequentially added3(catalyst) (0.161g) is added into 10ml dry round bottom flask, 2ml chlorobenzene is added as solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors reaction, cooling to room temperature after reaction is completed, 50ml ethyl acetate is added into reaction system, 30ml water and saturated salt water are used for washing in sequence, organic phase is dried and filtered by anhydrous sodium sulfate, residue is separated by column chromatography after a large amount of solvent is removed by reduced pressure evaporation, mixed solution of normal hexane and ethyl acetate is used as eluent, solvent is removed by evaporation againCleaning and drying to obtain the target compound with the reaction yield of 75 percent,1HNMR(400MHz,CDCl3):＝2.98(s,6H,CH3),5.82(s,1H,CH),6.75(d,J＝8.4Hz,2H,ArH),6.88-6.91(m,3H,ArH),7.10(d,J＝8.8Hz,2H,ArH),7.18-7.21(m,1H,ArH),7.39(d,J＝7.2Hz,1H,ArH),7.47-7.49(m,2H,ArH),7.57(s,1H,ArH),7.75-7.78(m,1H,ArH),7.81-7.86(m,2H,ArH).13C NMR(100MHz,CDCl3):＝40.7,50.4,112.9,116.3,120.7,125.7,126.0,127.5,127.6,127.9,128.0,128.1,129.6,130.1,130.6,130.7,132.3,133.5,140.8,149.5,153.8.
example 13
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxyphenyl) (2-thienyl) methane), comprising the steps of:
Figure BDA0001962473640000112
1.0mmol (0.122g) of salicylaldehyde, 1.0mmol (0.129g) of 2-thiopheneboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, and the target compound is obtained after drying, wherein the reaction yield is 80%,1HNMR(400MHz,CDCl3):＝3.05(s,6H,CH3),5.16(br,1H,OH),5.93(s,1H,CH),6.82(d,J＝8.4Hz,2H,ArH),6.87(s,1H,ArH),6.91(d,J＝8.0Hz,1H,ArH),6.99(t,J＝7.6Hz,1H,ArH),7.05-7.08(m,1H,ArH),7.12(d,J＝6.8Hz,1H,ArH),7.22-7.28(m,3H,ArH),7.33-7.35(m,1H,ArH).13C NMR(100MHz,CDCl3):＝40.7 45.4,112.8,116.3,120.8,124.8,126.3,126.8,128.1,129.5,129.8,130.1,130.9,147.6,149.6,153.4.
example 14
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxy-4-bromophenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000121
1.0mmol (0.200g) of 5-bromosalicylaldehyde, 1.0mmol (0.122g) of phenylboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl are successively mixed3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, the target compound is obtained by drying, the reaction yield is 76%,1HNMR(400MHz,CDCl3):＝3.18(s,6H,CH3),4.95(br,1H,OH),5.79(s,1H,CH),6.75-6.78(m,1H,ArH),6.94-7.02(m,3H,ArH),7.05-7.07(m,1H,ArH),7.25(d,J＝8.4Hz,2H,ArH),7.38(d,J＝7.2Hz,2H,ArH),7.49-7.51(m,1H,ArH),7.56(d,J＝7.6Hz,2H,ArH).13C NMR(100MHz,CDCl3):＝40.7,50.4,113.0,113.8,114.1,116.7,117.0,126.8,128.7,129.2,129.9,132.7,142.3,149.6,156.0,158.3.
example 15
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxy-3, 5-dichlorophenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000122
1.0mmol (0.122g) of 3, 5-dichlorosalicylaldehyde, 1.0mmol (0.122g) of phenylboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl are successively mixed3(catalyst) (0.161g) was charged into a 10ml dry round bottom flask,adding 2ml of chlorobenzene as a solvent, heating and refluxing at 100 ℃, monitoring the reaction at T L C, cooling to room temperature after the reaction is completed, adding 50ml of ethyl acetate into a reaction system, washing with 30ml of water and saturated saline solution in sequence, drying and filtering an organic phase by anhydrous sodium sulfate, evaporating under reduced pressure to remove a large amount of solvent, separating the residue by column chromatography, adopting a mixed solution of normal hexane and ethyl acetate as an eluent, evaporating the solvent to remove completely, drying to obtain the target compound with the reaction yield of 59 percent,1H NMR(400MHz,CDCl3):＝2.93(s,6H,CH3),5.42(s,1H,CH),6.68(d,J＝8.8Hz,2H,ArH),6.76(s,1H,ArH),6.95(d,J＝8.8Hz,2H,ArH),7.09(d,J＝7.2Hz,2H,ArH),7.21-7.25(m,2H,ArH),7.29(t,J＝6.8Hz,2H,ArH).13C NMR(100MHz,CDCl3):＝41.4,50.4,113.5,121.2,125.8,127.2,127.2,129.1,129.1,129.9,130.6,134.9,143.3,148.6,149.9.
example 16
A method of synthesizing a triarylmethane derivative ((4-dimethylaminophenyl) (2-hydroxy-3, 5-dibromophenyl) (phenyl) methane), comprising the steps of:
Figure BDA0001962473640000131
1.0mmol (0.280g) of 3, 5-dibromo salicylaldehyde, 1.0mmol (0.122g) of phenylboronic acid, 1.2mmol (0.102g) of piperidine, 1.2mmol (0.145g) of N, N-dimethylaniline and 1mmol of FeCl were sequentially added3(catalyst) (0.161g) is added into a 10ml dry round-bottom flask, 2ml chlorobenzene is added as a solvent, heating reflux reaction is carried out at 100 ℃, T L C monitors the reaction, after the reaction is completed, cooling to room temperature is carried out, 50ml ethyl acetate is added into a reaction system, 30ml water and saturated salt water are sequentially used for washing, an organic phase is dried and filtered by anhydrous sodium sulfate, a large amount of solvent is evaporated under reduced pressure, residue is separated by column chromatography, a mixed solution of normal hexane and ethyl acetate is used as an eluent, the solvent is evaporated and removed again, and the target compound is obtained after drying, wherein the reaction yield is 55%,1H NMR(400MHz,CDCl3):＝2.93(s,6H,CH3),5.74(s,1H,CH),6.68(t,J＝7.6Hz,2H,ArH),6.95(t,J＝8.0Hz,3H,ArH),7.09(t,J＝7.2Hz,2H,ArH),7.21-7.29(m,3H,ArH),7.48(d,J＝7.2Hz,2H,ArH).13C NMR(100MHz,CDCl3):＝40.7,50.0,111.2,112.5,112.8,113.5,126.6,128.5,129.2,129.6,130.0,132.1,132.7,134.6,142.7,149.4.
the accurate attribution of the hydrogen chemical shift results and the signal attribution of carbon atoms of carbon spectra of pure compounds obtained in each example in nuclear magnetic resonance hydrogen spectra are also attached to the operation steps of each example, and the synthesized products are proved to be triarylmethane derivatives.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. A method of synthesizing triarylmethane derivatives, comprising the steps of:
mixing a first reactant, a second reactant, a third reactant, piperidine and a catalyst, adding a solvent, reacting for 20-80 min at 40-120 ℃ under stirring, cooling to room temperature of 20-25 ℃ after the reaction is finished, adding ethyl acetate, washing to obtain an organic phase, drying the organic phase, evaporating the solvent to obtain a residue, separating the residue by column chromatography, evaporating the solvent again, and drying to obtain a triarylmethane derivative, wherein the ratio of the first reactant, the second reactant, the third reactant, the piperidine and the catalyst is 1 (1-1.5): (1-1.5): (1-1.5): (0.5-1), the catalyst is FeCl3；
The molecular formula of the first reactant is:
Figure FDA0001962473630000011
R1is one or more substituents on the phenyl ring to which it is attached, when R is1When it is a substituent, R1is-H or-Br, when R is1When there are more than one substituent, R1Is 3,5-Cl2Or 3,5-Br2；
The molecular formula of the second reactant is:
Figure FDA0001962473630000012
the R is2Is one or more substituents on the phenyl ring to which it is attached, when R is2When it is a substituent, R2is-H, -F, -Br, -MeO or-t-Bu, when R is2When there are more than one substituent, R2Is 3, 4-dimethoxy;
the molecular formula of the third reactant is:
Figure FDA0001962473630000013
the R is3is-H, -Me or-Et, said R4is-H, -Me or-Et, said R5Is a substituent on the phenyl ring to which it is attached, said R5is-H or-CH3。
2. The method according to claim 1, characterized in that a mixed solution of n-hexane and ethyl acetate is used as an eluent for column chromatography separation, and the ratio of n-hexane to ethyl acetate is 6:1 in parts by volume.
3. The method of claim 2, wherein the solvent is one or more of toluene, chlorobenzene, 1, 4-dioxane, acetonitrile, ethanol, water, dichloroethane, and dimethylformamide for providing a uniformly dispersed atmosphere for the first reactant, the second reactant, the piperidine, and the third reactant.
4. The method of claim 2, wherein the solvent is toluene, chlorobenzene, 1, 4-dioxane, acetonitrile, ethanol, water, dichloroethane, or dimethylformamide.
5. The process of claim 1, wherein the ratio of parts by volume of ethyl acetate to parts by weight of the material of the first reactant is 50: 1.
6. the method according to claim 5, wherein the washing is carried out by sequentially washing with water and saturated brine.
7. The method according to claim 6, wherein the ratio of the parts by weight of the first reactant to the parts by volume of the solvent is 1 (1-2), and when the parts by weight of the first reactant is mmol, the parts by volume is m L.
8. The method according to claim 7, wherein the reaction is preferably stirred at 100 ℃ for 20-80 min.
9. The method of claim 8, wherein the reaction time under stirring conditions is determined by thin layer chromatography detection; the operation steps for drying the organic phase are as follows: to the organic phase was added anhydrous sodium sulfate for drying, and the anhydrous sodium sulfate was filtered.
10. Triarylmethane derivatives obtainable by the process according to claims 1 to 9.
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