CN1923793A - Synthesis method of aryl phenyl ester like compound - Google Patents

Abstract

The invention discloses a synthesizing method of compound with structural formula as formula (I) based on aryl phenyl ester compound, which comprises the following steps: adding substituted benzene carbonic acid, substituted phenol, organic solvent and catalyst in the reacting bottle with mechanical stirring and diverting reflux device sequently; heating the reacting system to reflux state; separating the water; maintaining for 0.5h; stopping heating; terminating reacting; filtering reacting liquid; separating solid catalyst; decompressing to remove solvent; cooling to indoor temperature; evolving solid; filtering to obtain the product; recrystallizing to obtain the pure product.

Description

The synthetic method of aryl phenyl ester like compound

Technical field

The present invention relates to a kind of synthetic method of aryl phenyl ester like compound.

Background technology

Aryl phenyl ester like compound has very important purposes in liquid crystal material.Traditional vitriol oil is very low for the catalyzing esterification activity of substituted benzoic acid and substituted phenol.The synthetic general two-step approach that adopts of aryl phenyl ester like compound is prepared into acyl chlorides by substituted benzoic acid earlier, gets with corresponding phenol reaction again.

USP3923857 disclose 4-alkylbenzoic acid-4 '-synthetic method of cyanobenzene ester class liquid crystal monomer.Reaction was two steps, earlier prepared 4-alkylbenzene formyl chloride with the 4-alkylbenzoic acid, again with 4 '-cyanophenol in pyridine solution, react generation 4-alkylbenzoic acid-4 '-cyanobenzene ester.Wherein 4-heptyl benzene formic acid-4 '-the cyanobenzene ester product yield is 55%.

USP4198312 disclose with 4-alkylbenzoic acid and 3 '-chloro-4 '-cyanophenol be the synthetic 4-alkylbenzoic acid-3 of raw material '-chloro-4 '-method of cyanobenzene ester.Reaction in two steps, the first step is by the synthetic 4-alkylbenzene formyl chloride of 4-alkylbenzoic acid, at ambient temperature again with 3 '-chloro-4 '-cyanophenol reacts in the mixed solvent of ether and pyridine and makes corresponding ester.Esters product total recovery 68.8%～76.3%.

USP4340498 discloses the building-up process of halogenophenyl aryl nitrone derivative.Earlier prepare 4-alkylbenzene formyl chloride with the 4-alkylbenzoic acid, again with 4 '-fluorophenol in pyridine solution, react generation 4-alkylbenzoic acid-4 '-fluorine-based phenyl ester.Reaction formula is as follows:

Wherein R is C ₃H ₇, C ₄H ₉, C ₅H ₁₁, C ₇H ₁₅, C ₈H ₁₇, C ₅H ₁₁O etc.

In the present prior art, esterification adopts two-step approach: the first step prepares aroyl chloride, reacts with fortified phenol and then, obtain the purpose product, purpose product total recovery is lower than 76%, and because of reagent such as reaction process use sulfur oxychlorides, can cause problems such as environmental pollution and etching apparatus.

Summary of the invention

The objective of the invention is to overcome deficiency and the defective that prior art exists, propose a kind of reaction yield height, environment friendliness, the synthetic method of a step aryl phenyl ester like compound.

Building-up reactions formula of the present invention is as follows:

The present invention is the synthetic method with compound of general formula of molecular structure (I).

(I) R wherein ₁Be carbon number 1～6 straight chained alkyl, straight chain alkoxyl group or F, R ₂For F, Cl, Br, CN or carbon number 1～6 straight chain alkoxyl group, be raw material with substituted benzoic acid and fortified phenol, its general structure is respectively as (II) with (III):

R wherein ₁And R ₂With R in the general structure (I) ₁And R ₂Identical, this method may further comprise the steps:

1) in the reaction flask that has mechanical stirring, branch water reflux, adds substituted benzoic acid, fortified phenol, organic solvent, catalyzer successively.Add the mol ratio 1.0: 0.8～1.2 of substituted benzoic acid (II) and fortified phenol (III), catalyst levels is 2.0g～5.0g;

2) heating under agitation is warming up to reaction system and refluxes, and along with the carrying out of reaction, the water that separating reaction produces no longer includes water generates in reaction system, keeps reaction 0.5 hour, stops heating, and reaction finishes;

3) reacting liquor while hot is filtered, isolate solid catalyst after, decompression desolventizes.Be cooled to room temperature, separate out solid, filter the purpose product.

The organic solvent that the present invention adopts can be aromatic hydrocarbons, aryl alkyl ethers, chlorinated aromatic hydrocarbons, as benzene, toluene, ethylbenzene, propyl benzene, isopropyl benzene, butylbenzene, dimethylbenzene, trimethylbenzene, methyl-ethyl benzene, methyl-phenoxide, phenyl ethyl ether, diphenyl ether, chlorobenzene, dichlorobenzene, methyl chlorobenzene.Can select according to the temperature required solvent that carries out of reaction, preferred solvent is: toluene, dimethylbenzene, trimethylbenzene.

The synthetic method of preferred aryl groups benester compound of the present invention, this method may further comprise the steps:

1) have mechanical stirring, divide add successively in the reaction flask of water reflux 4-propylbenzoic acid, 4 '-fluorophenol, dimethylbenzene, catalyzer, 4-propylbenzoic acid and 4 '-mol ratio of fluorophenol is 1.0: 1.1, catalyzer is 3g;

2) stir heating down, be warming up to 144 ℃, reaction system refluxes, and the water that separating reaction produces no longer includes water generates in reaction system, keep reaction 0.5 hour again, stops heating, and reaction finishes;

3) reacting liquor while hot is filtered, isolate solid catalyst after, decompression desolventizes, and is cooled to room temperature, separates out solid, filter 4-propylbenzoic acid-4 '-the fluorobenzene ester.

The present invention has following advantage:

1) the present invention is a single stage method synthesizing aryl benester compound, has shortened reactions steps.

2) ester class product yield of the present invention is 80%.

3) the present invention has avoided the use sulfur oxychloride, and esterification is etching apparatus not, and is environmentally friendly, has excellent industrial application foreground.

Embodiment

Preparation of catalysts

The present invention requires catalyzer to have higher specific surface area and pore volume structure, and general specific surface area is 500～700 meters ²/ gram, 0.5～1.0 milliliter/gram of pore volume.Catalyst preparation step is as follows:

The preparation of a carrier

After 0.20mol phenyltrimethoxysila,e, 0.80mol tetrem oxosilane mixed, add 280mL ethanol, 60 ℃ of high degree of agitation 4 hours.In above-mentioned mixed solution, add the 135mL hexanaphthene again, 280mL water and 0.01mol lauryl amine, behind the thorough mixing, sealing system.The mixed solution that obtains is placed 80 ℃ of ageings 3 days, and white precipitate appears in reaction solution, filters, and leaches solid, and 80 ℃ of dryings are 10 hours under vacuum condition, 350 ℃ of roastings 4 hours, the silicone materials of bonding phenyl.

The sulfonic introducing of b

Solid support material is soaked overnight in tetrachloroethane solution, changes in the sulfonation reaction bottle, adds the tetrachloroethane solution of 15% sulphur trioxide, and 120 ℃ of maintenance system temperature stirred after 5 hours, naturally cooled to room temperature.Filter out solid catalyst, wash to pH be 6～7, in 120 ℃ of dryings 8 hours, solid acid catalyst.

The specific surface area and the pore volume of catalyzer are tested with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature, and specific surface area of catalyst is 680 meters ²/ gram, 0.96 milliliter/gram of pore volume.

Embodiment 1

In the 500mL reaction flask that mechanical stirring, thermometer, branch water reflux are housed, add the 3g catalyzer, 300mL dimethylbenzene, 20.5g (0.125mol) 4-propylbenzoic acid, 14.6g (0.130mol) 4 '-fluorophenol, under agitation, heat temperature raising to temperature of reaction is 144 ± 3 ℃.Along with esterification is carried out, the water that separating reaction produces no longer includes water generates in reaction system, keeps reaction 0.5 hour again, stops heating, and reaction finishes.Reacting liquor while hot is filtered, isolate solid catalyst after, decompression desolventizes, and is cooled to room temperature, separates out solid, filter the purpose product, yield is 86.3%.Get pure product through recrystallization, purity is 99.5%.

Structure is identified:

Ultimate analysis: theoretical value: C 74.40 H 5.85

Measured value: C 74.38 H 5.86

Infrared spectra: IR (KBr), ν/cm ^-1: 2963,2949,1739,1609,1484,1417,1400,827,807,756,699;

mp：48.0～49.4℃

Confirm the gained compound be 4-propylbenzoic acid-4 '-the fluorobenzene ester.

Embodiment 2

In the 500mL reaction flask that mechanical stirring, thermometer, branch water reflux are housed, add 2g, catalyzer, the 300mL sym-trimethylbenzene, 24.0g (0.125mol) 4-amylbenzene formic acid, 11.2g (0.100mol) 4 '-fluorophenol, under agitation, heat temperature raising to temperature of reaction is 164 ± 3 ℃.Other condition is with embodiment 1, obtain 4-amylbenzene formic acid-4 '-the fluorobenzene ester, yield is 80.5%.Thick product can get pure product through recrystallization, purity 99.0%.

Structure is identified

Ultimate analysis: theoretical value: C 75.50 H 6.69;

Measured value: C 75.53 H 6.71.

Infrared spectra: IR (KBr), ν/cm ^-1: 2969,2949,1740,1608,1484,1417,1400,827,806,756,699.

mp：32.9～33.8℃

Confirm the gained compound be 4-amylbenzene formic acid-4 '-the fluorobenzene ester.

Embodiment 3

In the 500mL reaction flask that mechanical stirring, thermometer, branch water reflux are housed, add the 2.5g catalyzer, toluene 300mL, 19.8g (0.110mol) 4-propoxy benzoic acid, 14.6g (0.130mol) 4 '-fluorophenol, heat temperature raising to temperature of reaction is 110 ± 2 ℃.Other condition is with embodiment 1, obtain 4-propoxy benzoic acid-4 '-the fluorobenzene ester, yield is 83.5%.Thick product can get pure product through recrystallization, purity 99.6%.

Structure is identified

Ultimate analysis: theoretical value: C 70.06 H 5.51;

Measured value: C 70.06 H 5.53.

Infrared spectra: IR (KBr), ν/cm ^-1: 2960,2949,1733,1604,1486,1417,1400,827,807,756,700.

mp：81.0～82.2℃

Confirm the gained compound be 4-propoxy benzoic acid-4 '-the fluorobenzene ester.

Embodiment 4

In the 500mL reaction flask that mechanical stirring, thermometer, branch water reflux are housed, add the 5g catalyzer, dimethylbenzene 300mL, 17.5g (0.125mol) 4-fluorobenzoic acid, 19.8g (0.130mol) 4 '-propoxy-phenol, heat temperature raising to temperature of reaction is 144 ± 2 ℃.Other condition is with embodiment 1, obtain 4-fluorobenzoic acid-4 '-the propoxy-phenyl ester, yield is 80.1%.Thick product can get pure product through recrystallization, purity 99.1%.

Structure is identified

Ultimate analysis: theoretical value: C 70.06 H 5.51;

Measured value: C 70.05 H 5.52.

Infrared spectra: IR (KBr), ν/cm ^-1: 2963,2950,1739,1609,1482,1417,1401,830,807,785,699.

mp：73.0～74.5℃

Confirm the gained compound be 4-fluorobenzoic acid-4 '-the propoxy-phenyl ester.

Embodiment 5

In the 500mL reaction flask that mechanical stirring, thermometer, branch water reflux are housed, add the 4g catalyzer, dimethylbenzene 300mL, 17.5g (0.125mol) 4-fluorobenzoic acid, 23.4g (0.130mol) 4 '-pentyloxy phenol, heat temperature raising to temperature of reaction is 144 ± 2 ℃.Other condition is with embodiment 1, obtain 4-fluorobenzoic acid-4 '-the pentyloxy phenyl ester, yield is 88.6%.Thick product can get pure product through recrystallization, purity 99.3%.

Structure is identified

Ultimate analysis: theoretical value: C 75.50 H 6.69;

Measured value: C 75.52 H 6.72.

Infrared spectra: IR (KBr), ν/cm ^-1: 2960,2943,1732,1609,1480,1417,1408,827,800,749,689.

mp：63.0～64.5℃

Confirm the gained compound be 4-fluorobenzoic acid-4 '-the pentyloxy phenyl ester.

Embodiment 6

In the 500mL reaction flask that mechanical stirring, thermometer, branch water reflux are housed, add the 5g catalyzer, dimethylbenzene 300mL, 22.3g (0.125mol) 4-butylbenzoic acid, 15.5g (0.130mol) 4 '-itrile group phenol, heat temperature raising to temperature of reaction is 144 ± 2 ℃.Other condition is with embodiment 1, obtain 4-butylbenzoic acid-4 '-the itrile group phenyl ester, yield is 81.2%.Thick product can get pure product through recrystallization, purity 98.6%.

Structure is identified

Ultimate analysis: theoretical value: C 77.40 H 6.13 N 5.01;

Measured value: C 77.42 H 6.11 N 5.02.

Infrared spectra: IR (KBr), ν/cm ^-1: 2958,2942,1730,1602,1481,1417,1397,827,805,756,699.

mp：67.0～68.3℃

Confirm the gained compound be 4-butylbenzoic acid-4 '-the itrile group phenyl ester.

Adopt different substituted benzoic acids and fortified phenol to obtain corresponding ester, the results are shown in Table 1.

Table 1

Compound	Yield/%
		4-propylbenzoic acid-4 '-the bromobenzene ester	86.1
4-propyl group oxybenzoic acid-4 '-the bromobenzene ester	91.0
		4-fluorobenzoic acid-4 '-the bromobenzene ester	80.1
4-fluorobenzoic acid-4 '-the itrile group phenyl ester	83.5

Claims (3)

1, a kind of synthetic method with compound of general formula of molecular structure (I),

R wherein ₁Be carbon number 1～6 straight chained alkyl, straight chain alkoxyl group or F, R ₂For F, Cl, Br, CN or carbon number 1～6 straight chain alkoxyl group, be raw material with substituted benzoic acid and fortified phenol, its general structure is respectively as (II) with (III):

R wherein ₁And R ₂With R in the general structure (I) ₁And R ₂Identical; This method may further comprise the steps:

1) in the reaction flask that has mechanical stirring, branch water reflux, adds substituted benzoic acid, fortified phenol, organic solvent, catalyzer successively, add the mol ratio 1.0: 0.8～1.2 of substituted benzoic acid (II) and fortified phenol (III), catalyzer is 2g～5g;

2) heating under agitation is warming up to reaction system and refluxes, and the water that separating reaction produces no longer includes water generates in reaction system, keep reaction 0.5 hour again, stops heating, and reaction finishes;

3) reacting liquor while hot is filtered, isolate solid catalyst after, decompression desolventizes, and is cooled to room temperature, separates out solid, filter the purpose product.

2, the synthetic method of general formula of molecular structure according to claim 1 (I) compound is characterized in that the organic solvent in the described step 1) is toluene, dimethylbenzene, trimethylbenzene.

3, the synthetic method of general formula of molecular structure according to claim 2 (I) compound, this method may further comprise the steps:

1) have mechanical stirring, divide add successively in the reaction flask of water reflux 4-propylbenzoic acid, 4 '-fluorophenol, dimethylbenzene, catalyzer, 4-propylbenzoic acid and 4 '-mol ratio of fluorophenol is 1.0: 1.1, catalyzer is 3g;

2) stir heating down, be warming up to 144 ℃, reaction system refluxes, and the water that separating reaction produces no longer includes water generates in reaction system, keep reaction 0.5 hour again, stops heating, and reaction finishes;

3) reacting liquor while hot is filtered, isolate solid catalyst after, decompression desolventizes, and is cooled to room temperature, separates out solid, filter 4-propylbenzoic acid-4 '-the fluorobenzene ester.