CN104892408A - Synthetic method of benzoate compound - Google Patents
Synthetic method of benzoate compound Download PDFInfo
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- CN104892408A CN104892408A CN201510260292.7A CN201510260292A CN104892408A CN 104892408 A CN104892408 A CN 104892408A CN 201510260292 A CN201510260292 A CN 201510260292A CN 104892408 A CN104892408 A CN 104892408A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/58—One oxygen atom, e.g. butenolide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D333/26—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/32—Oxygen atoms
Abstract
The invention provides a synthetic method of a benzoate compound. The benzoate compound is synthesized in high yield and in high conversion rate at a mild condition by taking a benzonitrile compound and an alcohol or phenolic compound as raw materials, by taking cheap and easily available copper as a catalyst, and by taking green and environment-friendly oxygen as an oxidizing agent. One of the raw materials in the method can not only result from the alcohol compound, but also from the phenolic compound, so that the range of substrates is greatly widened. The problems that most methods are not wildly suitable for functional groups and that specific reaction conditions, such as taking an expensive transition metal as the catalyst, and using a toxic reagent, are needed are overcome. The synthetic method has a certain industrial application value.
Description
[technical field]
The present invention relates to organic synthesis field, be specifically related to a kind of synthetic method of benzoate compounds.
[background technology]
Benzoate compounds is widely used in solvent, spices, synthesis material and softening agent.Therefore, the synthesis of benzoate compounds is the emphasis that chemical field is paid close attention to always, the heat subject of organic synthesis and other field of fine chemical research especially.
The synthetic method of benzoate compounds is a lot, and wherein the most frequently used one is in acid condition, by benzoic acid compounds and alcohol or halo hydrocarbons and their derivates direct esterification synthesizing benzoic acids ester compound.Also be the good method of synthesizing benzoic acids ester compound additionally by transesterify between simple benzoic ether and alcohol.Although adopt these methods can both synthesizing benzoic acids ester compound effectively, most method be wide to the adaptability of functional group, needs specific reaction conditions simultaneously, as: the transition metal by costliness makees catalyzer; Use toxic reagent etc.Therefore develop that a kind of cheaper starting materials is easy to get, reaction conditions is gentle, the synthetic method of the benzoate compounds of substrate wide adaptability is one of problem needing in organic synthesis to solve.(reference: Tetrahedron Lett.2003.44.6582; Cat.Lett.2003.3-4.143; Tetrahedron.2011,67,1640; Tetrahedron.2012,68,4701; Tetrahedron.2014,70,3887; Tetrahedron.2013,54,5064; Org.Lett.2014,16,236; J.Am.Chem.2013,135,10776; Green.Chem.2013,15,1646).
The present invention for raw material, with copper cheap and easy to get for catalyzer, with the oxygen of environmental protection for oxygenant, has synthesized benzoate compounds with benzonitrile compounds and alcohol or phenolic compound under mild conditions.One of raw material of the method not only can derive from alcohol compound, and can derive from phenolic compound, has greatly widened the scope of substrate, develops functional group's adaptability benzoate compounds widely, has certain industrial application value.
[summary of the invention]
The object of the invention is development one copper and make catalyzer, oxygen makees oxygenant, is raw material with benzonitrile compounds cheap and easy to get and alcohol or phenolic compound, the method for high conversion and high productivity synthesizing benzoic acids ester compound.
Goal of the invention of the present invention is achieved by the following technical solution:
A kind of structural formula is
the synthetic method of benzoate compounds, comprise following steps:
Get benzonitrile compounds, alcohol or phenolic compound, copper catalyst, organic solvent be placed in reaction vessel, mixing; Under oxygen atmosphere, at temperature of reaction is 80 ~ 120 DEG C, Keep agitation reaction 20 ~ 30h, be cooled to room temperature after reaction terminates, with saturated ammonium chloride solution washing, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains benzoate compounds.
In described general formula I, R is H, Cl, Br, methyl, nitro, methoxyl group, trifluoromethyl.
In described general formula II, R
1c
2~ C
8alkyl, benzyl, to methoxy-benzyl, to nitrobenzyl, to trifluoromethyl benzyl, 1-phenylethyl, 1-menaphthyl, 2-menaphthyl, furans-3-methyl, thiophene-3-methyl; Phenyl, p-methylphenyl, p-nitrophenyl, m-nitro base, m-methoxyphenyl, o-bromophenyl, 2-naphthyl.
In above-mentioned synthetic method, described benzonitrile compounds be selected from benzonitrile, to benzyl chloride nitrile, to bromobenzyl nitrile, to methyl-benzonitrile, adjacent methyl-benzonitrile, p-Nitrobenzyl Cyanide, to HOMOVERATRONITRILE, to Trifluoromethylbenzonitrile.
In above-mentioned synthetic method, described alcohol compound be selected from ethanol, n-propyl alcohol, the trimethyl carbinol, primary isoamyl alcohol, n-Octanol, benzylalcohol, p-methoxybenzyl alcohol, to nitrobenzyl alcohol, to trifluoromethyl-benzyl-alcohol, 1-phenylethyl alcohol, 1-naphthalene methyl alcohol, 2-naphthalene methyl alcohol, furans-3-methyl alcohol, thiophene-3-methyl alcohol; Described phenolic compound is phenol, p-methyl phenol, p-NP, m-nitrophenol, meta-methoxy phenol, o-bromophenol, beta naphthal.
In above-mentioned synthetic method, described catalyzer is selected from Cu, CuO, Cu
2o, CuCl
2, CuCl, CuBr
2, CuBr, CuI, Cu (OAc)
2, Cu (NO
3)
2, CuSO
4in one or more.In above-mentioned synthetic method, described organic solvent be selected from methyl-sulphoxide, acetonitrile, normal hexane, hexanaphthene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), toluene, chlorobenzene, 1,2-dimethylbenzene or 1,2-ethylene dichloride one or more.
In above-mentioned synthetic method, the mol ratio between described benzonitrile compounds and copper catalyst is [10:1] ~ [2:1].
In above-mentioned synthetic method, the mol ratio between described benzonitrile compounds and alcohol or phenolic compound is [1:1] ~ [1:3].Temperature of reaction is 80 ~ 120 DEG C, and the reaction times is 20 ~ 30h.
In above-mentioned synthetic method, the organic solvent in described extraction step is the one in ethyl acetate, trichloromethane or methylene dichloride.
Experimentally result, provided by the present inventionly make catalyzer by copper, oxygen makees oxygenant, be the method that raw material carrys out synthesizing benzoic acids ester compound with benzonitrile compounds cheap and easy to get and alcohol or phenolic compound, the selectivity of product and yield are all very high, environmental protection, has good prospects for commercial application.
[Brief Description Of Drawings]
Fig. 1 is the synthesis path figure of benzoic acid ester compounds provided by the invention.
[embodiment]
Be described further synthetic method of the present invention below in conjunction with synthesis example of the present invention, it should be noted that, embodiment does not form the restriction to application claims protection domain:
As shown in Figure 1, the synthesis step of benzoate compounds provided by the invention is: benzonitrile compounds, alcohol or phenolic compound (mol ratio 100 ~ 300% is based on benzonitrile compounds), copper catalyst (mol ratio 10 ~ 50% is based on benzonitrile compounds), organic solvent (1mL) are placed in reaction vessel, mixing; Under oxygen atmosphere, at temperature of reaction is 80 ~ 120 DEG C, Keep agitation reaction 20 ~ 30 hours, be cooled to room temperature after reaction terminates, with saturated ammonium chloride solution washing, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains benzoate compounds.
Synthesis example 1
The synthesis of ethyl benzoate
0.2mmol benzonitrile, 30mol%CuCl, 0.6mmol ethanol, 1mL toluene is added, under oxygen atmosphere in reaction vessel, be heated to 90 DEG C, Keep agitation 20h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 90%.
1H NMR(400MHz,CDCl
3)δ8.06-8.04(m,2H),7.57-7.53(m,1H),7.45-7.42(m,2H),4.41-4.36(m,2H),1.40(t,J＝7.2Hz,3H).
Synthesis example 2
The synthesis of propyl benzoate
0.2mmol benzonitrile, 10mol%CuBr, 0.6mmol n-propyl alcohol, 1mL Isosorbide-5-Nitrae-dioxane is added in reaction vessel, under oxygen atmosphere, be heated to 90 DEG C, Keep agitation 26h, stopped reaction, be cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 81%.
1H NMR(400MHz,CDCl
3)δ8.06-8.04(m,2H),7.57-7.53(m,1H),7.46-7.42(m,2H),4.28(t,J＝6.8Hz,2H),1.84-1.76(m,2H),1.04(t,J＝7.6Hz,3H).
Synthesis example 3
The synthesis of benzoic acid t-butyl ester
0.2mmol benzonitrile, 20mol%CuBr, the 0.6mmol trimethyl carbinol, 1mL1,4-dioxane is added in reaction vessel, 1mL acetonitrile, under oxygen atmosphere, is heated to 120 DEG C, Keep agitation 24h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with dichloromethane extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 68%.
1H NMR(400MHz,CDCl
3)δ8.00-7.98(m,2H),7.54-7.49(m,1H),7.43-7.39(m,2H),1.60(s,9H).
Synthesis example 4
The synthesis of isoamyl benzoate
0.2mmol benzonitrile, 10mol%CuCl, 0.6mmol primary isoamyl alcohol, 1mL1,2-dimethylbenzene is added in reaction vessel, under oxygen atmosphere, be heated to 100 DEG C, Keep agitation 24h, stopped reaction, be cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 72%.
1H NMR(400MHz,CDCl
3)δ8.05-8.03(m,2H),7.55(t,J＝7.6Hz,1H),7.44(t,J＝7.6Hz,2H),4.36(t,J＝6.8Hz,2H),1.86-1.74(m,1H),1.69-1.64(m,2H),0.99(s,3H),0.97(s,3H)
Synthesis example 5
The synthesis of phenylformic acid n-octyl
0.2mmol benzonitrile, 30mol%Cu (OAc) is added in reaction vessel
2, 0.2mmol n-Octanol, 1mL acetonitrile, under oxygen atmosphere, be heated to 100 DEG C, Keep agitation 28h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 66%.
1H NMR(400MHz,CDCl
3)δ8.04(t,J＝7.2Hz,2H),7.57-7.53(m,1H),7.46-7.42(m,2H),4.32(t,J＝6.8Hz,2H),1.80-1.73(m,2H),1.46-1.41(m,2H),1.34-1.28(m,8H),0.89(t,J＝7.2Hz,3H)
Synthesis example 6
The synthesis of peruscabin
0.2mmol benzonitrile, 50mol%Cu (OAc) is added in reaction vessel
2, 0.2mmol benzylalcohol, 1mL methyl-sulphoxide, under oxygen atmosphere, be heated to 100 DEG C, Keep agitation 22h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with extraction into ethyl acetate, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 72%.
1H NMR(400MHz,CDCl
3)δ8.08(d,J＝8.0Hz,2H),7.56(t,J＝7.2Hz,1H),7.46-7.32(m,7H),5.37(s,2H).
Synthesis example 7
The synthesis of phenylformic acid-4-methoxy benzyl ester
0.2mmol benzonitrile, 50mol%Cu (OAc) is added in reaction vessel
2, 0.24mmol p-methoxybenzyl alcohol, 1mL hexanaphthene, under oxygen atmosphere, be heated to 120 DEG C, Keep agitation 25h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 61%.
1H NMR(400MHz,CDCl
3)δ8.04(t,J＝7.2Hz,2H),7.54(t,J＝7.2Hz,1H),7.43-7.38(m,4H),6.91(d,J＝8.8Hz,2H),5.30(s,2H),3.81(s,3H).
Synthesis example 8
The synthesis of phenylformic acid-4-p-Nitrobenzyl
0.2mmol benzonitrile, 50mol%CuSO is added in reaction vessel
4, 0.4mmol to nitrobenzyl alcohol, 1mL acetonitrile, 1mL chlorobenzene, under oxygen atmosphere, be heated to 90 DEG C, Keep agitation 24h, stopped reaction, be cooled to room temperature, add saturated ammonium chloride solution washing, with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 70%.
1H NMR(400MHz,CDCl
3)δ8.23(t,J＝4.0Hz,2H),8.09(d,J＝7.6Hz,2H),7.61-7.58(m,3H),7.46(t,J＝8.0Hz,2H),5.46(s,2H).
Synthesis example 9
The synthesis of phenylformic acid-4-trifluoromethyl benzyl ester
0.2mmol benzonitrile, 20mol%Cu (OAc) is added in reaction vessel
2, 0.3mmol to trifluoromethyl-benzyl-alcohol, 1mL acetonitrile, under oxygen atmosphere, be heated to 100 DEG C, Keep agitation 28h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 73%.
1H NMR(400MHz,CDCl
3)δ8.10-8.07(m,2H),7.64(d,J＝8.0Hz,2H),7.59-7.54(m,3H),7.47-7.43(m,2H),5.41(s,2H).
Synthesis example 10
The synthesis of phenylformic acid-1-phenyl chlorocarbonate
0.2mmol benzonitrile, 25mol%CuBr, 0.2mmol 1-phenylethyl alcohol, 1mL chlorobenzene is added, under oxygen atmosphere in reaction vessel, be heated to 120 DEG C, Keep agitation 30h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 73%.
1H NMR(400MHz,CDCl
3)δ8.09-8.07(m,2H),7.57-7.53(m,1H),7.46-7.41(m,4H),7.38-7.35(m,2H),7.31-7.28(m,1H),6.16-6.11(m,1H),1.67(d,J＝6.4Hz,3H).
Synthesis example 11
The synthesis of phenylformic acid-1-naphthalene methyl esters
0.2mmol benzonitrile, 40mol%CuI, 0.24mmol 1-naphthalene methyl alcohol, 1mL 1,2-dimethylbenzene is added in reaction vessel, under oxygen atmosphere, be heated to 100 DEG C, Keep agitation 29h, stopped reaction, be cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 76%.
1H NMR(400MHz,CDCl
3)δ8.11(d,J＝8.4Hz,1H),8.05(d,J＝7.2Hz,2H),7.90-7.85(m,2H),7.63(d,J＝6.8Hz,1H),7.58-7.45(m,4H),7.39(t,J＝7.6Hz,2H),5.81(s,2H).
Synthesis example 12
The synthesis of phenylformic acid-2-naphthalene methyl esters
0.2mmol benzonitrile, 50mol%CuCl, 0.22mmol 2-naphthalene methyl alcohol, 1mL normal hexane is added, under oxygen atmosphere in reaction vessel, be heated to 120 DEG C, Keep agitation 20h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 73%.
1H NMR(400MHz,CDCl
3)δ8.11-8.09(m,2H),7.90(s,1H),7.87-7.83(m,3H),7.57-7.53(m,2H),7.51-7.46(m,2H),7.43(t,J＝8.0Hz,2H),5.52(s,2H).
Synthesis example 13
The synthesis of phenylformic acid-3-furans methyl esters
0.2mmol benzonitrile, 20mol%CuCl, 0.3mmol 3-furfuralcohol, 1mL 1,2-ethylene dichloride is added in reaction vessel, under oxygen atmosphere, be heated to 90 DEG C, Keep agitation 30h, stopped reaction, be cooled to room temperature, add saturated ammonium chloride solution washing, with extraction into ethyl acetate, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 59%.
1H NMR(400MHz, CDCl
3)δ8.05(d,J＝8.0Hz,2H),7.57-7.53(m,2H),7.45-7.42(m,3H),6.51(s,1H),5.24(s,2H).
Synthesis example 14
The synthesis of phenylformic acid-3-thiophene methyl esters
0.2mmol benzonitrile, 10mol%Cu is added in reaction vessel
2o, 0.2mmol 3-thiophen(e)alcohol, 1mL normal hexane, under oxygen atmosphere, be heated to 110 DEG C, Keep agitation 22h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 61%.
1H NMR(400MHz,CDCl
3)δ8.07-8.05(m,2H),7.57-7.53(m,1H),7.45-7.42(m,2H),7.37(s,1H),7.33-7.31(m,1H),7.18-7.16(m,1H),5.36(s,2H).
Synthesis example 15
The synthesis of Ethoforme
0.2mmol is added to benzyl chloride nitrile, 20mol%Cu in reaction vessel
2o, 0.6mmol ethanol, 1mL methyl-sulphoxide, under oxygen atmosphere, be heated to 110 DEG C, Keep agitation 24h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 63%.
1H NMR(400MHz,CDCl
3)δ8.00-7.96(m,2H),7.43-7.39(m,2H),4.40-4.35(m,2H),1.39(t,J＝7.2Hz,3H).
Synthesis example 16
The synthesis of parabromobenzoic acid ethyl ester
0.2mmol is added to bromobenzyl nitrile, 30mol%CuSO in reaction vessel
4, 0.26mmol ethanol, 1mL toluene, under oxygen atmosphere, be heated to 80 DEG C, Keep agitation 26h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 59%.
1H NMR(400MHz, CDCl
3)δ7.92-7.89(m,2H),7.59-7.56(m,2H),4.40-4.35(m,2H),1.39(t,J＝7.2Hz,3H).
Synthesis example 17
The synthesis of ethyl p-methyl benzoate
0.2mmol is added to methyl-benzonitrile, 50mol%CuBr in reaction vessel
2, 0.5mmol ethanol, 1mL normal hexane, under oxygen atmosphere, be heated to 120 DEG C, Keep agitation 23h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 70%.
1H NMR(400MHz,CDCl
3)δ7.93(d,J＝7.6Hz,2H),7.23(d,J＝8.0Hz,2H),4.39-4.33(m,2H),2.41(s,3H),1.39(t,J＝7.2Hz,3H).
Synthesis example 18
The synthesis of o-toluic acid ethyl ester
0.2mmol adjacent methyl-benzonitrile, 30mol%CuO, 0.3mmol ethanol, 1mL tetrahydrofuran (THF) is added, under oxygen atmosphere in reaction vessel, be heated to 110 DEG C, Keep agitation 24h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with dichloromethane extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 73%.
1H NMR(400MHz,CDCl
3)δ7.92-7.90(d,J＝7.6Hz,1H),7.39(t,J＝6.8Hz,1H),7.26-7.23(m,2H),4.26(t,J＝7.2Hz,2H),2.60(s,3H),1.84-1.75(m,2H),1.04(t,J＝7.2Hz,3H).
Synthesis example 19
The synthesis of ethyl p-nitrobenzoate
0.2mmol p-Nitrobenzyl Cyanide, 50mol%Cu is added in reaction vessel
2o, 0.6mmol ethanol, 1mL toluene, under oxygen atmosphere, be heated to 90 DEG C, Keep agitation 30h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 78%.
1H NMR(400MHz,CDCl
3)δ8.30-8.21(m,4H),4.47-4.42(m,2H),1.43(t,J＝7.2Hz,3H).
Synthesis example 20
The synthesis of ethyl anisate
0.2mmol is added to HOMOVERATRONITRILE, 10mol%CuCl, 0.4mmol ethanol, 1mL normal hexane, under oxygen atmosphere in reaction vessel, be heated to 110 DEG C, Keep agitation 23h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 67%.
1H NMR(400MHz,CDCl
3)δ8.01-7.98(m,2H),6.93-6.89(m,2H),4.37-4.32(m,2H),3.85(s,3H),1.38(t,J＝7.2Hz,3H).
Synthesis example 21
To the synthesis of trifluoromethylbenzoic acid propyl ester
0.2mmol is added to Trifluoromethylbenzonitrile, 20mol%CuI, 0.34mmol propyl alcohol, 1mL hexanaphthene, under oxygen atmosphere in reaction vessel, be heated to 110 DEG C, Keep agitation 24h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 82%.
1H NMR(400MHz,CDCl
3)δ8.16(d,J＝8.0Hz,2H),7.70(d,J＝8.0Hz,2H),4.45-4.39(m,2H),1.42(t,J＝7.2Hz,3H).
Synthesis example 22
The synthesis of phenol benzoate
0.2mmol benzonitrile, 20mol%CuI, 0.3mmol phenol, 1mL1,4-dioxane is added in reaction vessel, under oxygen atmosphere, be heated to 90 DEG C, Keep agitation 28h, stopped reaction, be cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 71%.
1H NMR(400MHz,CDCl
3)δ8.21(d,J＝7.2Hz,2H),7.64(t,J＝7.6Hz,1H),7.52(t,J＝7.6Hz,2H),7.46-7.42(m,2H),7.30-7.21(m,3H)；
Synthesis example 23
The synthesis of phenylformic acid-4-methyl phenyl ester
0.2mmol benzonitrile, 10mol%CuCl, 0.32mmol p-methyl phenol, 1mL toluene is added, under oxygen atmosphere in reaction vessel, be heated to 90 DEG C, Keep agitation 20h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 69%.
1H NMR(400MHz,CDCl
3)δ8.20(d,J＝7.2Hz,2H),7.63(t,J＝7.6Hz,1H),7.51(t,J＝7.6Hz,2H),7.23(d,J＝8.0Hz,2H),7.09(d,J＝7.6Hz,2H)；
Synthesis example 24
The synthesis of phenylformic acid-4-nitro phenyl ester
0.2mmol benzonitrile, 30mol%CuBr, 0.26mmol p-NP, 1mL acetonitrile is added, under oxygen atmosphere in reaction vessel, be heated to 100 DEG C, Keep agitation 25h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 86%.
1H NMR(400MHz,CDCl
3)δ8.34(d,J＝8.8Hz,2H),8.21(t,J＝7.6Hz,2H),7.69(t,J＝7.6Hz,1H),7.55(t,J＝7.6Hz,2H),7.43(d,J＝8.8Hz,2H)
Synthesis example 25
The synthesis of phenylformic acid-3-nitro phenyl ester
0.2mmol benzonitrile, 50mol%CuI, 0.24mmol m-nitrophenol, 1mL toluene is added, under oxygen atmosphere in reaction vessel, be heated to 120 DEG C, Keep agitation 27h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 84%.
1H NMR(400MHz,CDCl
3)δ8.21(d,J＝7.2Hz,2H),8.18-8.14(m,2H),7.71-7.53(m,5H)；
Synthesis example 26
The synthesis of phenylformic acid-3-methoxyl group phenyl ester
0.2mmol benzonitrile, 20mol%CuCl, 0.4mmol meta-methoxy phenol, 1mL THF is added, under oxygen atmosphere in reaction vessel, be heated to 110 DEG C, Keep agitation 21h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 91%.
1H NMR(400MHz,CDCl
3)δ8.20(d,J＝7.6Hz,2H),7.64(t,J＝7.6Hz,1H),7.55-7.49(m,2H),7.33(t,J＝8.0Hz,1H),6.84-6.77(m,3H),3.82(s,3H)；
Synthesis example 27
The synthesis of phenylformic acid-2-bromobenzene ester
0.2mmol benzonitrile, 20mol%CuCl, 0.4mmol o-bromophenol, 1mL toluene is added, under oxygen atmosphere in reaction vessel, be heated to 120 DEG C, Keep agitation 20h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 79%.
1H NMR(400MHz,CDCl
3)δ8.26(d,J＝7.2Hz,2H),7.68-7.65(m,2H),7.54(t,J＝7.6Hz,2H),7.41-7.37(m,1H),7.30-7.27(m,1H),7.19-7.15(m,1H)；
Synthesis example 28
The synthesis of Betanaphthyl Benzoate
0.2mmol benzonitrile, 30mol%CuCl, 0.3mmol beta naphthal, 1mL acetonitrile is added, under oxygen atmosphere in reaction vessel, be heated to 120 DEG C, Keep agitation 24h, stopped reaction, is cooled to room temperature, add saturated ammonium chloride solution washing, with chloroform extraction, dry, underpressure distillation is except desolventizing, namely thick product obtains target product through pillar layer separation, productive rate 80%.
1H NMR(400MHz,CDCl
3)δ8.26(d,J＝7.6Hz,2H),7.92-7.83(m,3H),7.70-7.64(m,2H),7.56-7.50(m,4H),7.38-7.35(m,1H)。
Claims (8)
1. a synthetic method for benzoate compounds, comprises following operation steps:
Get benzonitrile compounds, alcohol or phenolic compound, copper catalyst, organic solvent be placed in reaction vessel, mixing; Under oxygen atmosphere, at temperature of reaction is 80 ~ 120 DEG C, Keep agitation reaction 20 ~ 30h, be cooled to room temperature after reaction terminates, with saturated ammonium chloride solution washing, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains benzoate compounds.There is following structural formula:
In described general formula I, R is H, Cl, Br, methyl, nitro, methoxyl group, trifluoromethyl.
In described general formula II, R
1c
2~ C
8alkyl, benzyl, to methoxy-benzyl, to nitrobenzyl, to trifluoromethyl benzyl, 1-phenylethyl, 1-menaphthyl, 2-menaphthyl, furans-3-methyl, thiophene-3-methyl; Phenyl, p-methylphenyl, p-nitrophenyl, m-nitro base, m-methoxyphenyl, o-bromophenyl, 2-naphthyl.
2. the synthetic method of benzoate compounds according to claim 1, it is characterized in that, described benzonitrile compounds be selected from benzonitrile, to benzyl chloride nitrile, to bromobenzyl nitrile, to methyl-benzonitrile, adjacent methyl-benzonitrile, p-Nitrobenzyl Cyanide, to HOMOVERATRONITRILE, to Trifluoromethylbenzonitrile.
3. the synthetic method of benzoate compounds according to claim 1, it is characterized in that, described alcohol compound be selected from ethanol, n-propyl alcohol, the trimethyl carbinol, primary isoamyl alcohol, n-Octanol, benzylalcohol, p-methoxybenzyl alcohol, to nitrobenzyl alcohol, to trifluoromethyl-benzyl-alcohol, 1-phenylethyl alcohol, 1-naphthalene methyl alcohol, 2-naphthalene methyl alcohol, furans-3-methyl alcohol, thiophene-3-methyl alcohol; Described phenolic compound is phenol, p-methyl phenol, p-NP, m-nitrophenol, meta-methoxy phenol, o-bromophenol, beta naphthal.
4. the synthetic method of benzoate compounds according to claim 1, is characterized in that, described catalyzer is selected from Cu, CuO, Cu
2o, CuCl
2, CuCl, CuBr
2, CuBr, CuI, Cu (OAc)
2, Cu (NO
3)
2, CuSO
4in one or more.
5. the synthetic method of benzoate compounds according to claim 1, it is characterized in that, described organic solvent is selected from methyl-sulphoxide, acetonitrile, normal hexane, hexanaphthene, 1,4-dioxane, tetrahydrofuran (THF), toluene, chlorobenzene, 1, one or more in 2-dimethylbenzene or 1,2-ethylene dichloride.
6. the synthetic method of benzoate compounds according to claim 1, is characterized in that, the mol ratio between described benzonitrile compounds and copper catalyst is [10:1] ~ [2:1].
7. the synthetic method of benzoate compounds according to claim 1, is characterized in that, the mol ratio between described benzonitrile compounds and alcohol or phenolic compound is [1:1] ~ [1:3].Temperature of reaction is 80 ~ 120 DEG C, and the reaction times is 20 ~ 30h.
8. the synthetic method of benzoate compounds according to claim 1, is characterized in that, the organic solvent in described extraction step is the one in ethyl acetate, trichloromethane or methylene dichloride.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820049A (en) * | 2016-05-13 | 2016-08-03 | 湖北科技学院 | Synthesis method for tert-butyl ester compound |
| CN109456185A (en) * | 2018-11-21 | 2019-03-12 | 上海大学 | Using N-Boc amide as the preparation method of Material synthesis ester type compound |
| CN113979955A (en) * | 2021-11-12 | 2022-01-28 | 河南农业大学 | Preparation method of heterocyclic ester compound |
| CN113979955B (en) * | 2021-11-12 | 2024-05-14 | 河南农业大学 | Preparation method of heterocyclic ester compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105820049A (en) * | 2016-05-13 | 2016-08-03 | 湖北科技学院 | Synthesis method for tert-butyl ester compound |
| CN109456185A (en) * | 2018-11-21 | 2019-03-12 | 上海大学 | Using N-Boc amide as the preparation method of Material synthesis ester type compound |
| CN113979955A (en) * | 2021-11-12 | 2022-01-28 | 河南农业大学 | Preparation method of heterocyclic ester compound |
| CN113979955B (en) * | 2021-11-12 | 2024-05-14 | 河南农业大学 | Preparation method of heterocyclic ester compound |
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