CN103193650B - Method for preparing carboxylic acid methyl ester catalyzed by metal copper salt - Google Patents
Method for preparing carboxylic acid methyl ester catalyzed by metal copper salt Download PDFInfo
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Abstract
The invention discloses a method for preparing carboxylic acid methyl ester catalyzed by metal copper salt. In an organic solvent, the metal copper salt is taken as a catalyst; and carboxylic acid is taken as a substrate to react under the effect of peroxide; and the carboxylic acid methyl ester is obtained by post-treatment after the reaction is finished. According to the method disclosed by the invention, the carboxylic acid is directly methylated to synthetize ester; the reaction material is cheap and easily available; the preparation method is simple; the metal copper salt is utilized as the catalyst, and is cheap and easily available; and the cost can be greatly reduced. The method disclosed by the invention can be used for synthetizing a series of carboxylic ester; and the synthetic product is an important organic synthetic midbody.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to a kind of preparation method by the carboxylate methyl ester of catalysis of copper salt.
Background technology
Ester is chemistry and one of most important organic structure in pharmacopedics, and is widely used in producing various valuable compounds therefrom as (Larock, R.C.ComprehensiVe Organic Transformation such as polymkeric substance, perfume and lipid acid; VCH:New York, 1999).So esterification is one of most important reaction in organic synthesis.
The method of conventional synthesis ester is as acyl chlorides, acid anhydrides etc. and alcohol generation substitution reaction with the carboxylic acid derivative activated.The shortcoming of the method is acyl chlorides.The compounds such as acid anhydrides are unstable, and unfriendly to environment.
Another method directly preparing ester generates corresponding ester with carboxylic acid to alcohol condensation.But this reaction is reversible reaction, so need excessive alcohol or carboxylic acid to make reaction carry out towards the direction generating ester, comparatively waste in the industrial production.
In recent years, organo-peroxide is widely used in carbon-hydrogen bond activation.2008 Li group (Y.H.Zhang, J.Q.Feng, C.J.Li, J.Am.Chem.Soc.2008,130,2900) report pyridine guiding C-H bond methylation reaction, this reaction provides methyl free radicals with organo-peroxide.
Summary of the invention
The invention provides a kind of preparation method by the carboxylate methyl ester of catalysis of copper salt, this preparation method's raw material is easy to get, simple to operate.
By a preparation method for the carboxylate methyl ester of catalysis of copper salt, comprising: in organic solvent, make catalyzer with copper salt, take carboxylic acid as substrate, react under the effect of superoxide, after reaction terminates, obtain described carboxylate methyl ester through aftertreatment;
The structure of described carboxylate methyl ester is as shown in formula I:
The structure of described carboxylic acid is as shown in formula II:
In formula I and formula II, R
1for aryl or carbonatoms are the saturated alkyl of 5 ~ 11;
Described superoxide is organo-peroxide, and described organo-peroxide can produce methyl free radicals in a heated condition.
The reaction equation of this preparation method is as follows:
The principle of this preparation method is: superoxide produces methyl free radicals under the catalysis of copper salt, and methyl free radicals generates carbon-oxygen bond with the oxygen hydrogen bond action in carboxylic acid again.
As preferably, described superoxide is peroxidized t-butyl perbenzoate, dicumyl peroxide (DCP) or the tertiary butyl ether of peroxidation (DTBP), and these superoxide easily produce methyl free radicals, and reaction efficiency is high.
As preferably, the R in described carboxylic acid
1for aryl, aryl can with carbonyl generation conjugation, improve the reactive behavior of atom N, thus improve the efficiency of reaction; As further preferred, described aryl is phenyl, 4-bromophenyl, 4-chloro-phenyl-, 2-chloro-phenyl-, 4-aminomethyl phenyl, 4-nitrophenyl, 2-nitrophenyl, 4-cyano-phenyl, 4-xenyl, 4-tert-butyl-phenyl or 1-naphthyl.
In actual mechanical process, strictly do not control the upper limit of amount of peroxide, generally can add excessive superoxide, the mol ratio of described carboxylic acid and described superoxide is preferably 1:1 ~ 1:3.
Compared with other noble metal catalysts, catalysis of copper salt agent is cheap and easy to get, preparation cost can be reduced, conventional cuprous salt or cupric salt can be used as described copper salt, as preferably, described copper salt is cuprous chloride, cuprous iodide, venus crystals, trifluoroacetic acid copper, Salzburg vitriol or Copper dichloride dihydrate, and these mantoquitas are easy to buy from the market; Described copper salt most preferably is cuprous chloride, and the catalytic effect of cuprous chloride to this reaction is best.As preferably, the mol ratio of described copper salt and described acid amides is 0.01 ~ 1:1.
The temperature of reaction is 80 ~ 140 DEG C; The time of reaction is 1 ~ 24h, extend the reaction times, raise temperature of reaction, catalyzed reaction can be made to carry out more thorough, the transformation efficiency of raw material can be improved, but temperature of reaction is too high, the reaction times is long, is unfavorable for the practical application of reacting, the temperature of reaction is preferably 100 ~ 140 DEG C, most preferably be 130 DEG C, the time of reaction is preferably 6 ~ 18h, is more preferably 12h.
Described organic solvent is aprotic solvent, and as preferably, described organic solvent is chlorine benzene,toluene,xylene, sym-trimethylbenzene, ethyl acetate, 1,2-ethylene dichloride or trichloroethane, most preferably is chlorobenzene, when carrying out in chlorobenzene, and reaction most effective.
The consumption of described organic solvent, can by abundant for raw material dispersing and dissolving without requirement strict especially, and the Materials Solvents consumption of general 100mg is about 1mL.
The aftertreatment of product of the present invention comprises: cross and filter insolubles, be spin-dried for solvent, then uses column chromatography to be separated.
Compared with prior art, the present invention has the following advantages:
The inventive method is originated using superoxide as methyl, and directly to make carboxylic acid methyl, reaction raw materials is cheap and easy to get, and preparation method is simple, makes catalyzer with copper salt, cheap and easy to get, can greatly reduce costs.Preparation method of the present invention can be used for synthesizing a series of ester, and the product of synthesis is important organic synthesis intermediate.
Embodiment
Describe the present invention in detail below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1
In the Shi Lanke test tube of drying, add the phenylformic acid of 61mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, joined in Shi Lanke test tube by the chlorobenzene of tertiary for the peroxidation of 146mg butyl ether and 1ml, the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product methyl benzoate (No. CAS: 93-58-3) 52mg, productive rate 76%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ8.05(d,J=7.2Hz,2H),7.56(t,J=7.6Hz,1H),7.44(t,J=7.8Hz,2H),3.92(s,3H).
13C?NMR(100MHz,CDCl
3):δ167.8,133.6,130.8,130.2,129.0,52.8.
Embodiment 2
In the Shi Lanke test tube of drying, add the Chlorodracylic acid of 78mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 4-chloro benzoic ether (No. CAS: 1126-46-1) 68mg, productive rate 80%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ7.96(d,J=8.8Hz,2H),7.40(d,J=8.8Hz,2H),3.91(s,3H).
13C?NMR(100MHz,CDCl
3):δ166.9,140.0,131.6,129.4,129.2,52.9.
Embodiment 3
In the Shi Lanke test tube of drying, add the parabromobenzoic acid of 101mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 4-methyl-bromobenzoate (No. CAS: 619-42-1) 82mg, productive rate 76%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ7.89(d,J=8.8Hz,2H),7.58(d,J=8.8Hz,2H),3.91(s,3H).
13C?NMR(100MHz,CDCl
3):δ167.0,132.4,131.8,129.7,128.7,53.0.
Embodiment 4
In the Shi Lanke test tube of drying, add the p-nitrobenzoic acid of 101mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 4-nitro methyl-formiate (No. CAS: 619-50-1) 27mg, productive rate 30%, reaction process is shown below:
The product that the present embodiment is prepared carry out nucleus magnetic resonance (
1h NMR) analyze:
1H?NMR(400MHz,CDCl
3):δ8.31(d,J=8.4Hz,2H),8.23(d,J=8.0Hz,2H),4.00(s,3H).
13C?NMR(100MHz,CDCl
3):δ165.8,151.2,136.1,131.4,124.2,53.5.
Embodiment 5
In the Shi Lanke test tube of drying, add the paracyanobenzoic acid of 73.5mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 4-cyano-benzoic acid methyl ester (No. CAS: 1129-35-7) 35mg, productive rate 44%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ8.14(d,J=8.4Hz,2H),7.74(d,J=8.0Hz,2H),3.96(s,3H).
13C?NMR(100MHz,CDCl
3):δ166.1,134.6,132.9,130.8,118.6,117.0,53.4.
Embodiment 6
In the Shi Lanke test tube of drying, add the 0-chloro-benzoic acid of 78mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 2-chloro benzoic ether (No. CAS: 610-96-8) 81mg, productive rate 95%, reaction process is shown below:
The product that the present embodiment is prepared carry out nucleus magnetic resonance (
1h NMR) analyze:
1H?NMR(400MHz,CDCl
3):δ7.84-7.82(m,1H),7.47-7.39(m,2H),7.33-7.29(m,1H),3.94(s,3H).
13C?NMR(100MHz,CDCl
3):δ166.8,134.3,133.2,132.0,131.7,130.7,127.2,53.1.
Embodiment 7
In the Shi Lanke test tube of drying, add the o-Carboxynitrobenzene of 101mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 2-nitrobenzene methyl (No. CAS: 606-27-9) 75mg, productive rate 83%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ7.92-7.90(m,1H),7.76-7.62(m,3H),3.92(s,3H).
13C?NMR(100MHz,CDCl
3):δ166.5,148.9,133.6,132.5,130.5,128.2,124.6,53.9.
Embodiment 8
In the Shi Lanke test tube of drying, add the p-methylbenzoic acid of 68mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product methyl 4 methylbenzoate (No. CAS: 99-75-2) 55mg, productive rate 73%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ7.86(d,J=8.0Hz,2H),7.16(d,J=7.6Hz,2H),3.83(s,3H),2.33(s,3H).
13C?NMR(100MHz,CDCl
3):δ167.9,144.2,130.3,129.7,128.1,52.6,22.3.
Embodiment 9
In the Shi Lanke test tube of drying, add the p-tert-butyl benzoic acid of 89mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 4-p t butylbenzoic acid methyl esters (No. CAS: 26537-19-9) 77mg, productive rate 80%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ7.94(d,J=8.0Hz,2H),7.42(d,J=7.6Hz,2H),3.86(s,3H),1.30(s,9H).
13C?NMR(100MHz,CDCl
3):δ167.8,157.2,130.1,128.0,126.0,52.6,35.7,31.8.
Embodiment 10
In the Shi Lanke test tube of drying, add the cuprous chloride to methoxy benzoic acid and 5.0mg of 76mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 4-methoxyl methyl benzoate (No. CAS: 121-98-2) 67mg, productive rate 81%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ7.99(dd,J
1=2.0Hz,J
2=8.8Hz,2H),6.91(dd,J
1=2.0Hz,J
2=8.8Hz,2H),3.88(d,J=2.8Hz,3H),3.85(d,J=4.0Hz,3H).
13C?NMR(100MHz,CDCl
3):δ167.5,164.0,132.2123.2,114.2,56.1,52.5.
Embodiment 11
In the Shi Lanke test tube of drying, add the 4-diphenic acid of 99mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 4-diphenic acid methyl esters (No. CAS: 720-75-2) 66mg, productive rate 62%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ8.13(d,J=8.8Hz,2H),7.69-7.64(m,4H),7.49(t,J=7.4Hz,2H),7.41(t,J=7.4Hz,1H),3.96(s,3H).
13C?NMR(100MHz,CDCl
3):δ167.7,146.3,140.7,130.8,129.6,129.5,128.8,127.9,127.7,52.8.
Embodiment 12
In the Shi Lanke test tube of drying, add the 1-naphthoic acid of 86mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product 1-2-methyl naphthoate (No. CAS: 2459-24-7) 71mg, productive rate 76%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ8.90(d,J=8.8Hz,1H),8.16(d,J=7.2Hz,1H),7.98(d,J=8.4Hz,1H),7.85(d,J=7.6Hz,1H),7.60(t,J=7.6Hz,1H),7.52-7.45(m,2H),3.98(s,3H).
13C?NMR(100MHz,CDCl
3):δ168.7,134.5,134.1,132.0,130.9,129.2,128.4,127.7,126.9,126.5,125.2,52.8.
Embodiment 13
In the Shi Lanke test tube of drying, add the styracin of 74mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product methyl cinnamate (No. CAS: 1754-62-7) 41mg, productive rate 51%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ7.71(d,J=16.0Hz,1H),7.54(t,J=3.2Hz,2H),7.41-7.40(m,3H),6.46(d,J=16.4Hz,1H),3.82(s,3H).
13C?NMR(100MHz,CDCl
3):δ168.1,145.6,135.0,131.0,129.6,128.7,118.4,52.4.
Embodiment 14
In the Shi Lanke test tube of drying, add the lauric acid of 100mg and the cuprous chloride of 5.0mg.Test tube first vacuumizes, then inflated with nitrogen, in triplicate.Then, the tertiary butyl ether of peroxidation of 146mg and the chlorobenzene of 1ml join in Shi Lanke test tube, and the reaction solution obtained stirs 12 hours in 130 DEG C.Be cooled to room temperature after reaction terminates, filter with glass funnel, concentrated, cross silicagel column (volume ratio of ethyl acetate and sherwood oil is 1:20), obtain product Laurate methyl (No. CAS: 111-82-0) 86mg, productive rate 80%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment prepares:
1H?NMR(400MHz,CDCl
3):δ3.66(s,3H),2.30(t,J=7.6Hz,2H),1.63-1.58(m,2H),1.28-1.25(m,16H),0.87(t,J=6.6Hz,3H);
13C?NMR(100MHz,CDCl
3):δ175.0,52.1,34.7,32.5,30.2,30.1,30.0,29.9,29.8,25.6,23.3,14.7。
Claims (5)
1. by a preparation method for the carboxylate methyl ester of catalysis of copper salt, it is characterized in that, comprising: in organic solvent, catalyzer is made with copper salt, take carboxylic acid as substrate, react under the effect of superoxide, after reaction terminates, obtain described carboxylate methyl ester through aftertreatment;
The structure of described carboxylate methyl ester is as shown in formula I:
The structure of described carboxylic acid is as shown in formula II:
In formula I and formula II, R
1for aryl or carbonatoms are the saturated alkyl of 5 ~ 11;
Described superoxide is the tertiary butyl ether of peroxidation;
The temperature of reaction is 130 ~ 140 DEG C; The time of reaction is 12 ~ 24h;
Described copper salt is cuprous chloride.
2. the preparation method of carboxylate methyl ester according to claim 1, is characterized in that, the R in described carboxylic acid
1for aryl.
3. the preparation method of carboxylate methyl ester according to claim 1, is characterized in that, the mol ratio of described carboxylic acid and described superoxide is 1:1 ~ 1:3.
4. the preparation method of carboxylate methyl ester according to claim 1, is characterized in that, the mol ratio of described copper salt and described carboxylic acid is 0.01 ~ 1:1.
5. the preparation method of carboxylate methyl ester according to claim 1, is characterized in that, described organic solvent is chlorine benzene,toluene,xylene, sym-trimethylbenzene, ethyl acetate, 1,2-ethylene dichloride or trichloroethane.
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