CN102557943A - Method for synthesizing aromatic formic acid aryl ester derivative - Google Patents
Method for synthesizing aromatic formic acid aryl ester derivative Download PDFInfo
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Abstract
The invention discloses a method for synthesizing an aromatic formic acid aryl ester derivative shown as a formula (I). The method comprises the following steps of: fully reacting arylboronic acid shown as a formula (II) and acyl chloride shown as a formula (III) which are taken as raw materials in oxygen atmosphere in the presence of a copper catalyst, a ligand and an alkaline compound in an inert organic solvent, and after-treating a reaction solution after the reaction is finished to obtain the aromatic formic acid aryl ester derivative. The method for synthesizing the aromatic formic acid aryl ester derivative is reasonable, low in cost and high in reaction yield, and has relatively high implementation value as well as social and economic benefits; reaction conditions are mild; and the quality of products is high.
Description
(1) technical field
The present invention relates to a kind of chemical synthesis process of aromatic acid aryl ester verivate.
(2) background technology
Aromatic acid aryl ester verivate is to have the active compound with pharmacologically active of good biological, is widely used in synthesizing of organic, medicine and pharmaceutical-chemical intermediate.
In the prior art, comparatively commonly through the synthetic aromatic acid aryl ester verivate of the esterification of aromatic acid and phenol.Yet this method need be at the reaction conditions of harshness such as high temperature, use strong acid just can carry out as catalyzer, and functional group's compatibility of reaction yield and substrate is not fine.In addition; Adopt Bayer-Villiger oxidation rearrangement reaction also can synthesize and obtain aromatic acid aryl ester verivate; But the selectivity of this method depends on the substituent difference in carbonyl both sides and has high selectivity, yet for aromatic acid aryl ester compounds, the both sides substituting group all is that therefore aryl shows similar character; In the group migration, cause extremely low reaction preference, thereby made yield reduce greatly.
To the above unfavorable factor of considering, be necessary existing method is improved, develop a kind of cheapness, reaction conditions gentleness, catalystsystem aromatic acid aryl ester derivative synthesizing process efficiently, have very big economic benefit and social benefit.
(3) summary of the invention
The purpose of this invention is to provide a kind of technology rationally, low-cost, reaction conditions is gentle, reaction yield is high and the chemical synthesis process of the aromatic acid aryl ester verivate of good product quality.
For realizing the foregoing invention purpose, the present invention adopts following technical scheme:
The compound method of the aromatic acid aryl ester verivate shown in a kind of formula (I); Said compound method is: the acyl chlorides with shown in aryl boric acid shown in the formula (II) and the formula (III) is a raw material; In the oxygen atmosphere; Fully reaction in inert organic solvents in the presence of copper catalyst, part and basic cpd, reaction finishes afterreaction liquid and obtains the aromatic acid aryl ester verivate shown in the formula (I) through aftertreatment;
Formula (I), (II) or (III) in, R
1Be selected from one of following: the alkyl of hydrogen, C1～C8, the alkoxyl group of C1～C8, C2～C8 alkyl acyl, halogen, nitro, cyanic acid, phenyl or trifluoromethyl; R
2Be selected from one of following: thienyl, furyl, pyrryl, pyridyl, phenyl or substituted-phenyl, the substituting group of said substituted-phenyl are the alkyl of C1～C8, alkoxyl group, trifluoromethyl, cyanic acid, halogen or the nitro of C1～C8;
Described copper catalyst is selected from following a kind of or any several kinds combination: cuprous chloride, cuprous bromide, cuprous iodide, cuprous acetate, trifluoromethanesulfonic acid are cuprous, neutralized verdigris, acetylacetone copper, copper trifluoromethanesulfcomposite, cupric chloride, cupric oxide;
Described part is selected from following a kind of or any several kinds combination: tricyclohexyl phosphine, three (p-methoxyphenyl) phosphine, 1; Two (diphenylphosphine) ethane (dppe), 1 of 2-; Two (diphenylphosphine) propane (dppp) of 2-; Triphenylphosphine, three (1-naphthyl) phosphine, 1,4-diazabicylo [2.2.2] octane (DABCO), two (2-diphenylphosphine) phenylates (DPEphos);
Described basic cpd is selected from following a kind of or any several kinds combination: sodium-acetate, cesium acetate, cesium carbonate, sodium hydroxide, potassiumphosphate, cesium fluoride, lithium fluoride, yellow soda ash, salt of wormwood, triethylamine, pyridine, 1-methyl piperidine;
Said inert organic solvents is selected from following a kind of or any several kinds combination: the alkanes of C1～C8, halogenated hydrocarbon, chlorobenzene, toluene, YLENE, THF, 2-methyltetrahydrofuran, N; Dinethylformamide, DMAC N,N, ETHYLE ACETATE, acetonitrile.
Further, described R
1Be preferably one of following: the alkyl of hydrogen, C1～C8, the alkoxyl group of C1～C8, C2～C8 alkyl acyl, halogen, trifluoromethyl.
Further, described R
1Be preferably one of following: the alkyl of hydrogen, C1～C4, the alkoxyl group of C1～C4, C2～C4 alkyl acyl, halogen, trifluoromethyl.
Further again, described R
1Be preferably one of following: hydrogen, ethanoyl, methoxyl group, methyl, fluorine, trifluoromethyl.
Further, described R
2Be preferably one of following: phenyl, substituted-phenyl, thienyl, furyl, the substituting group of said substituted-phenyl are the alkyl of C1～C8, alkoxyl group or the halogen of C1～C8.
Further, the substituting group of said substituted-phenyl is positioned at the contraposition of chloroformyl, and said substituting group is the alkyl of C1～C4, alkoxyl group, F or the Cl of C1～C4.
Further again, described R
2For one of following: phenyl, p-methylphenyl, p-methoxyphenyl, to fluorophenyl, rubigan, thienyl, furyl.
It is one of following that copper catalyst of the present invention is preferably: acetylacetone copper, neutralized verdigris, more preferably neutralized verdigris.
It is one of following that part of the present invention is preferably: two (2-diphenylphosphine) phenylates (DPEphos), 1,4-diazabicylo [2.2.2] octane (DABCO), more preferably 1,4-diazabicylo [2.2.2] octane (DABCO).
It is one of following that basic cpd of the present invention is preferably: cesium fluoride, salt of wormwood, more preferably salt of wormwood.
It is one of following that inert organic solvents of the present invention is preferably: toluene, YLENE, more preferably toluene.
The molar ratio of acyl chlorides according to the invention, aryl boric acid, copper catalyst, part and basic cpd is 1.0: 1.0～3.0: 0.01～0.5: 0.01～0.5: 1.0～5.0; Be preferably 1.0: 1.5～2.0: 0.05～0.15: 0.1～0.3: 2.0～3.0, most preferably be 1: 1.5: 0.1: 0.2: 2.0.
Among the present invention, the add-on of said inert organic solvents is 5～30 times of acyl chlorides quality, is preferably 8～20 times, more preferably 8～15 times.
Among the present invention, temperature of reaction is 40～150 ℃, is preferably 70～130 ℃, more preferably 100～120 ℃; Reaction times is preferably 24h～36h generally at 10h～60h.
The present invention is after reacting completely; The gained reaction solution can obtain title product through conventional aftertreatment, for example adopts following post-treating method: the gained reaction solution steams earlier and desolventizes, and adds saturated aqueous common salt again; Separate and get organic layer, be aromatic acid aryl ester verivate behind the rotation evaporate to dryness.
The present invention compared with prior art, its beneficial effect is mainly reflected in: 1, reaction preference and yield are high, good product quality; 2, operational path is advanced rationally, reaction conditions is gentle; 3, use cheap copper catalyst and part; So the present invention has bigger implementary value and economic results in society.
(4) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 27.6g (0.2mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
In the oxygen atmosphere, with Benzoyl chloride 99min., phenyl-boron dihydroxide, neutralized verdigris, 1,4-diazabicylo [2.2.2] octane (DABCO), salt of wormwood drop in the reaction kettle under the room temperature, add the toluene dissolving, and temperature of reaction is 110 ℃, and afterreaction finished in 24 hours.
Reaction finishes the back underpressure distillation and reclaims organic solvent, adds saturated aqueous common salt again, separates and gets organic layer, promptly gets phenol benzoate 16.4g, yield 83%, purity 98.6% behind the rotation evaporate to dryness.
Nuclear magnetic resonance spectrum (Bruke):
1H NMR (500MHz, CDCl
3): δ=8.21 (d, J=7.9Hz, 2H), 7.63-7.66 (m, 1H), 7.51-7.54 (m, 2H), 7.43-7.46 (m, 2H), 7.27-7.30 (m, 1H), 7.22-7.24 (m, 2H);
13C NMR (125MHz, CDCl
3): δ=165.16,150.99,133.55,130.16,129.62,129.47,128.55,125.86,121.70.MS (70eV, EI): m/z (%)=198 (M
+, 7), 105 (100), 77 (36).
Embodiment 2:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is an acetylacetone copper, the quality that feeds intake 2.62g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 27.6g (0.2mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 14.5g, and, yield 73%, purity 98.5%.
Embodiment 3:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a cuprous acetate, the quality that feeds intake 1.23g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 27.6g (0.2mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 12.5g, and, yield 63%, purity 98.6%.
Embodiment 4:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a cesium fluoride, the quality that feeds intake 30.4g (0.2mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 15.4g, and, yield 78%, purity 98.8%.
Embodiment 5:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is two (2-diphenylphosphine) phenylates (DPEphos), the quality that feeds intake 10.77g (0.02mol); Basic cpd is a cesium fluoride, the quality that feeds intake 30.4g (0.2mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 15.6g, and, yield 79%, purity 98.4%.
Embodiment 6:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a cuprous acetate, the quality that feeds intake 1.23g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a cesium fluoride, the quality that feeds intake 30.4g (0.2mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 8.5g, and, yield 43%, purity 99.1%.
Embodiment 7:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 27.6g (0.2mol); Organic solvent is YLENE 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 13.3g, and, yield 67%, purity 98.5%.
Embodiment 8:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 27.6g (0.2mol); Organic solvent is toluene 211g, and its total consumption is 8 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 16.0g, and, yield 81%, purity 98.5%.
Embodiment 9:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 27.6g (0.2mol); Organic solvent is toluene 211g, and its total consumption is 15 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 16.2g, and, yield 82%, purity 98.3%.
Embodiment 10:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 2.0: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 24.4g (0.2mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 27.6g (0.2mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 15.8g, and, yield 80%, purity 98.7%.
Embodiment 11:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 3.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 41.3g (0.3mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom phenol benzoate 14.7g, and, yield 74%, purity 98.5%.
Embodiment 12:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a Benzoyl chloride 99min., the quality that feeds intake 14.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 41.3g (0.3mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
Temperature of reaction is 80 ℃, and the reaction times is 36 hours, and all the other are with embodiment 1, products obtained therefrom phenol benzoate 13.3g, and, yield 67%, purity 98.6%.
Embodiment 12:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a 2-thiophene acyl chlorides, the quality that feeds intake 14.7g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 41.3g (0.3mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom 2-thiophenic acid phenyl ester 18.6g, and, yield 91%, purity 98.2%.
Embodiment 13:
Mol ratio by acyl chlorides, aryl boric acid, copper catalyst, part, basic cpd is 1.0: 1.5: 0.1: feed intake at 0.2: 2.0; Acyl chlorides is a 2-furans acyl chlorides, the quality that feeds intake 13.1g (0.1mol); Aryl boric acid is a phenylo boric acid, the quality that feeds intake 18.3g (0.15mol); Copper catalyst is a neutralized verdigris, the quality that feeds intake 1.82g (0.01mol); Part is 1,4-diazabicylo [2.2.2] octane (DABCO), the quality that feeds intake 2.24g (0.02mol); Basic cpd is a salt of wormwood, the quality that feeds intake 41.3g (0.3mol); Organic solvent is toluene 169g, and its total consumption is 12 times of Benzoyl chloride 99min. quality.
All the other are with embodiment 1, products obtained therefrom 2-furancarboxylic acid phenyl ester 16.9g, and, yield 90%, purity 98.2%.
Embodiment 14～24:
Acyl chlorides, aryl boric acid, copper catalyst, part, salt of wormwood are 1.0: 1.5: 0.1 with the amount of substance ratio: after feeding intake at 0.2: 2.0; Add the toluene dissolving, temperature of reaction is 110 ℃, and the reaction times is 24 hours; All the other steps are with embodiment 1, and the result is as shown in the table:
Compound I
1:
1H NMR (500MHz, CDCl
3): δ=8.15 (d, J=9.0Hz, 2H), 7.39-7.42 (m, 2H), 7.23-7.26 (m, 1H), 7.18-7.20 (m, 2H), 6.96-6.98 (m, 2H), 3.87 (s, 3H);
13CNMR (125MHz, CDCl
3): δ=164.86,163.87,151.08,132.25,129.39,125.67,121.89,121.77,113.81,55.47.
Compound I
2:
1H NMR (500MHz, CDCl
3): δ=8.10 (d, J=8.1Hz, 2H), 7.40-7.44 (m, 2H), 7.30-7.31 (m, 2H), 7.24-7.28 (m, 1H), 7.20-7.22 (m, 2H), 2.45 (s, 3H);
13CNMR (125MHz, CDCl
3): δ=165.20,151.04,144.35,130.19,129.41,129.25,126.85,125.74,121.73,21.70.
Compound I
3:
1H NMR (500MHz, CDCl
3): δ=8.14-8.15 (m, 2H), 7.49-7.50 (m, 2H), 7.42-7.46 (m, 2H), 7.27-7.30 (m, 1H), 7.20-7.22 (m, 2H);
13C NMR (125MHz, CDCl
3): δ=164.32,150.80,140.13,131.53,129.53,128.94,128.07,126.02,121.60.
Compound I
4:
1H NMR (500MHz, CDCl
3): δ=8.22-8.25 (m, 2H), 7.43-7.46 (m, 2H), 7.28-7.31 (m, 1H), 7.18-7.23 (m, 4H);
13C NMR (125MHz, CDCl
3): δ=166.13 (d, J
C-F=253.5Hz), 164.16,150.84,132.75 (d, J
C-F=9.3Hz), 129.49,125.94,125.83 (d, J
C-F=3.0Hz), 121.62,115.75 (d, J
C-F=21.9Hz).
Compound I
5:
1H NMR (500MHz, CDCl
3): δ=8.19-8.21 (m, 2H), 7.62-7.65 (m, 1H), 7.49-7.53 (m, 2H), 7.13-7.15 (m, 2H), 6.94-6.95 (m, 2H), 3.83 (s, 3H);
13C NMR (125MHz, CDCl
3): δ=165.52,157.33,144.45,133.47,130.12,129.68,128.52,122.43,114.53,55.61.
Compound I
6:
1H NMR (500MHz, CDCl
3): δ=8.21 (d, J=7.7Hz, 2H), 7.63-7.66 (m, 1H), 7.50-7.53 (m, 2H), 7.31-7.35 (m, 1H), 6.81-6.84 (m, 1H), 6.78-6.79 (m, 1H), 3.83 (s, 3H);
13C NMR (125MHz, CDCl
3): δ=165.08,160.58,151.95,133.57, l30.17, l29.86,129.59, l28.56,113.91,111.86,107.69,55.44.
Compound I
7:
1H NMR (500MHz, CDCl
3): δ=8.22 (d, J=7.3Hz, 2H), 7.62-7.65 (m, 1H), 7.50-7.53 (m, 2H), 7.23-7.24 (m, 2H), 7.10-7.12 (m, 2H), 2.39 (s, 3H);
13CNMR (125MHz, CDCl
3): δ=165.34,148.73,135.47,133.45,130.12,129.97,129.71,128.50,121.34,20.86.
Compound I
8:
1H NMR (500MHz, CDCl
3): δ=8.22-8.24 (m, 2H), 7.63-7.66 (m, 1H), 7.51-7.54 (m, 2H), 7.32-7.35 (m, 1H), 7.10-7.11 (m, 1H), 7.04-7.06 (m, 2H), 2.41 (s, 3H);
13C NMR (125MHz, CDCl
3): δ=165.22,150.91,139.62,133.46,130.10,129.67,129.15,128.50,126.63,122.26,118.60,21.28.
Compound I
9:
1H NMR (500MHz, CDCl
3): δ=8.21-8.23 (m, 2H), 7.71-7.72 (m, 2H), 7.66-7.69 (m, 1H), 7.52-7.55 (m, 2H), 7.36-7.37 (m, 2H);
13C NMR (125MHz, CDCl
3): δ=164.64,153.49,133.95,130.26,128.99,128.69,128.19 (d, J
C-F=32.6Hz), 126.85 (q, J
C-F=3.7Hz), 123.90 (d, J
C-F=270.3Hz), 122.25.
Compound I
10:
1H NMR (500MHz, CDCl
3): δ=8.19-8.20 (m, 2H), 7.63-7.66 (m, 1H), 7.50-7.54 (m, 2H), 7.17-7.20 (m, 2H), 7.10-7.13 (m, 2H);
13C NMR (125MHz, CDCl
3): δ=165.20,160.30 (d, J
C-F=242.8Hz), 146.76 (d, J
C-F=2.9Hz), 133.70,130.16,129.30,128.60,123.09 (d, J
C-F=8.4Hz), 116.12 (d, J
C-F=23.4Hz).
Compound I
11:
1H NMR (500MHz, CDCl
3): δ=8.20-8.22 (m, 2H), 8.05 (d, J=8.7Hz, 2H), 7.65-7.68 (m, 1H), 7.52-7.55 (m, 2H), 7.33-7.35 (m, 2H);
13C NMR (125MHz, CDCl
3): δ=196.85,164.62,154.70,134.83,133.91,130.25,130.00,129.07,128.67,121.92,26.59.
Claims (10)
1. the compound method of the aromatic acid aryl ester verivate shown in the formula (I); Said method comprises the following steps: that with the acyl chlorides shown in aryl boric acid shown in the formula (II) and the formula (III) be raw material; In the oxygen atmosphere; Fully reaction in inert organic solvents in the presence of copper catalyst, part and basic cpd, reaction finishes afterreaction liquid and obtains the aromatic acid aryl ester verivate shown in the formula (I) through aftertreatment;
Formula (I), (II) or (III) in, R
1Be selected from one of following: the alkyl of hydrogen, C1～C8, the alkoxyl group of C1～C8, C2～C8 alkyl acyl, halogen, nitro, cyanic acid, phenyl, halogen or trifluoromethyl; R
2Be selected from one of following: thienyl, furyl, pyrryl, pyridyl, phenyl or substituted-phenyl, the substituting group of said substituted-phenyl are the alkyl of C1～C8, alkoxyl group, trifluoromethyl, cyanic acid, halogen or the nitro of C1～C8;
Described copper catalyst is selected from following a kind of or any several kinds combination: cuprous chloride, cuprous bromide, cuprous iodide, cuprous acetate, trifluoromethanesulfonic acid are cuprous, neutralized verdigris, acetylacetone copper, copper trifluoromethanesulfcomposite, cupric chloride, cupric oxide;
Described part is selected from following a kind of or any several kinds combination: tricyclohexyl phosphine, three (p-methoxyphenyl) phosphine, 1; Two (diphenylphosphine) ethane, 1 of 2-; Two (diphenylphosphine) propane of 2-; Triphenylphosphine, three (1-naphthyl) phosphine, 1,4-diazabicylo [2.2.2] octane, two (2-diphenylphosphine) phenylate;
Described basic cpd is selected from following a kind of or any several kinds combination: sodium-acetate, cesium acetate, cesium carbonate, sodium hydroxide, potassiumphosphate, cesium fluoride, lithium fluoride, yellow soda ash, salt of wormwood, triethylamine, pyridine, 1-methyl piperidine;
Said inert organic solvents is selected from following a kind of or any several kinds combination: the alkanes of C1～C8, halogenated hydrocarbon, chlorobenzene, toluene, YLENE, THF, 2-methyltetrahydrofuran, N; Dinethylformamide, DMAC N,N, ETHYLE ACETATE, acetonitrile.
2. the compound method of aromatic acid aryl ester verivate as claimed in claim 1; It is characterized in that: the molar ratio of said acyl chlorides and aryl boric acid, copper catalyst, part and basic cpd is 1.0: 1.0～3.0: 0.01～0.5: 0.01～0.5: 1.0～5.0, and the consumption of said inert organic solvents is 8～20 times of acyl chlorides quality.
3. the compound method of aromatic acid aryl ester verivate as claimed in claim 2; It is characterized in that: the molar ratio of said acyl chlorides and aryl boric acid, copper catalyst, part and basic cpd is 1.0: 1.5～2.0: 0.05～0.15: 0.1～0.3: 2.0～3.0, and the consumption of said inert organic solvents is 8～15 times of acyl chlorides quality.
4. like the compound method of the described aromatic acid aryl ester of one of claim 1～3 verivate, it is characterized in that: temperature of reaction is 40～150 ℃, and the reaction times is 10h～60h.
5. the compound method of aromatic acid aryl ester verivate as claimed in claim 4 is characterized in that: temperature of reaction is 100～120 ℃, and the reaction times is 24h～36h.
6. the compound method of aromatic acid aryl ester verivate as claimed in claim 1 is characterized in that: described copper catalyst is one of following: acetylacetone copper, neutralized verdigris.
7. the compound method of aromatic acid aryl ester verivate as claimed in claim 1 is characterized in that: described part is one of following: two (2-diphenylphosphine) phenylate, 1,4-diazabicylo [2.2.2] octane.
8. the compound method of aromatic acid aryl ester verivate as claimed in claim 1 is characterized in that: described basic cpd is one of following: cesium fluoride, salt of wormwood.
9. the compound method of aromatic acid aryl ester verivate as claimed in claim 1 is characterized in that: described inert organic solvents is one of following: toluene, YLENE.
10. the compound method of aromatic acid aryl ester verivate as claimed in claim 4; It is characterized in that: described copper catalyst is a neutralized verdigris, and described part is 1,4-diazabicylo [2.2.2] octane; Described basic cpd is a salt of wormwood; Described inert organic solvents toluene, the molar ratio of said acyl chlorides and aryl boric acid, copper catalyst, part and basic cpd are 1.0: 1.5: 0.1: 0.2: 2.0, the consumption of said inert organic solvents was 8～15 times of acyl chlorides quality.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628964A (en) * | 2017-09-07 | 2018-01-26 | 陕西科技大学 | A kind of synthetic method of N aryl Zhong Fang acid amides |
| CN114409538A (en) * | 2021-12-29 | 2022-04-29 | 湖北工业大学 | Allyl benzoate compound and preparation method thereof |
| WO2024045034A1 (en) * | 2022-08-31 | 2024-03-07 | 苏州大学 | Method for dehydrogenation esterification of aldehyde and aryl phenol by means of light/nickel dual-catalysis system |
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| 《Tetrahedron Letters》 20031231 Yoshio Urawa, et al A convenient method for preparing aromatic ketones from acyl chlorides and arylboronic acids via Suzuki-Miyaura type coupling reaction 第271-273页 1-10 第44卷, * |
| YOSHIO URAWA, ET AL: "A convenient method for preparing aromatic ketones from acyl chlorides and arylboronic acids via Suzuki–Miyaura type coupling reaction", 《TETRAHEDRON LETTERS》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107628964A (en) * | 2017-09-07 | 2018-01-26 | 陕西科技大学 | A kind of synthetic method of N aryl Zhong Fang acid amides |
| CN114409538A (en) * | 2021-12-29 | 2022-04-29 | 湖北工业大学 | Allyl benzoate compound and preparation method thereof |
| CN114409538B (en) * | 2021-12-29 | 2023-09-26 | 湖北工业大学 | Allyl benzoate compound and preparation method thereof |
| WO2024045034A1 (en) * | 2022-08-31 | 2024-03-07 | 苏州大学 | Method for dehydrogenation esterification of aldehyde and aryl phenol by means of light/nickel dual-catalysis system |
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