CN101279903B - Synthetic method of o-hydroxyacetophenone - Google Patents

Synthetic method of o-hydroxyacetophenone Download PDF

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CN101279903B
CN101279903B CN2008100616198A CN200810061619A CN101279903B CN 101279903 B CN101279903 B CN 101279903B CN 2008100616198 A CN2008100616198 A CN 2008100616198A CN 200810061619 A CN200810061619 A CN 200810061619A CN 101279903 B CN101279903 B CN 101279903B
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hydroxyl
hydroxyacetophenone
organic solvent
synthetic method
anhydrous
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CN101279903A (en
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朱锦桃
宋光伟
陈刚
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Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
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Abstract

The invention discloses a method to synthesize 2-hydroxy-acetophenone, which takes low-cost paracetamol as material and prepares 2-hydroxy-acetophenone through acylation, Fries recomposition, acylation through hydrolyzation, and deaminization through diazotization. The material used in the method is easy to get and is low in cost; the process is simple, with mild condition and short period; the yield is high and the product is high in purity; therefore the method is of good prospect in industrial application.

Description

A kind of synthetic method of o-hydroxyacetophenone
Technical field
The present invention relates to a kind of synthetic method of pharmaceutical intermediate, specifically a kind of synthetic method of o-hydroxyacetophenone.
Background technology
O-hydroxyacetophenone (English name O-hydroxy-acetophenon) is a kind of important chemical material, have purposes widely in the development of fine chemical products such as medicine, agricultural chemicals and industrial production, it is the key intermediate of propafenone, Propafenone, choleretic.
About synthesizing of o-hydroxyacetophenone, relevant report was arranged once.Kingdom happiness (" Chinese Journal of Pharmaceuticals ", 1999,30 (5), 232-233) reported to be raw material with phenol, generate ester with acetic anhydride, carry out the Fries rearrangement then and obtain o-hydroxyacetophenone and parahydroxyacet-ophenone under the dithiocarbonic anhydride solvent, its ratio is 2: 3.The shortcoming of this method is to make solvent with dithiocarbonic anhydride, and it has irritating smell, and is volatile, and toxicity is bigger, handle inconvenience, and the yield of the o-hydroxyacetophenone that obtains has only 33%.
Qiao Yang Ding waits (" organic chemistry " in addition, 2002,22 (4), 275-278) reported that solvent-free reaction comes the method for synthesis of hydroxy methyl phenyl ketone, acetoxyphenyl heats under the aluminum trichloride (anhydrous) condition and carries out the hydroxy acetophenone that the Fries rearrangement obtains the adjacency pair position, and its ratio is about 1: 1, but the shortcoming of this method is a relatively thickness of reaction mixture, stir difficulty, make reaction be difficult to carry out, easily carbonization.
2005, and Sanjay Bhar etc. (" Synthetic Communications ", 2005,35 (9), 1183-1188) people has reported with the semicarbazone to be raw material, in the presence of phosphoric acid, obtains o-hydroxyacetophenone by hydrolysis reaction.This method expensive raw material price is difficult for preparation, is unfavorable for scale operation.
2007, and Ghiaci etc. (" Applied Catalysis A:General ", 2007,320,35-42) people has reported at H 3PO 4/ TiO 2-ZrO 2Under the catalyzer, be raw material with phenol, ethyl acetate is an acylating reagent, carries out vapor reaction in 200-400 ℃ and obtains o-hydroxyacetophenone, and yield is 96.8%.The difficult preparation of catalyzer that this method is used, and under very high temperature, react again, be difficult for controlling, be unsuitable for industrial applications.
Summary of the invention
Overcome the deficiency in the background technology, the purpose of this invention is to provide a kind of easy and simple to handlely, cost is low, and security is good, and yield is higher, is easy to the method for the synthesizing o-hydroxy ethyl ketone of suitability for industrialized production.
The method of synthesizing o-hydroxy ethyl ketone of the present invention may further comprise the steps:
1) 4-acetaminophenol acetic ester is synthetic
In reactor Paracetamol is dissolved in the organic solvent, adds weak base simultaneously, the mol ratio of weak base and Paracetamol is 1: 0.5～3, adds acylating reagent then, the consumption of acylating reagent be Paracetamol mole number 1-6 doubly; 0 ℃ to the reflux temperature reaction steam and remove organic solvent after 3-36 hour, add entry, suction filtration gets 4-acetaminophenol acetic ester solid product;
2) 2-hydroxyl-5-acetamido methyl phenyl ketone is synthetic
4-acetaminophenol acetic ester with step 1) in reactor is dissolved in the organic solvent, add lewis acid catalyst simultaneously, its consumption be 4-acetaminophenol acetic ester mole number 1-10 doubly, reacted 1-18 hour down at 20-180 ℃, cooling, filter, recrystallization obtains 2-hydroxyl-5-acetamido methyl phenyl ketone;
3) 2-hydroxyl-5-aminoacetophenone is synthetic
2-hydroxyl-5-acetamido methyl phenyl ketone and mineral acid were added in the reactor in 1: 5 in molar ratio～5: 1, to reflux temperature, reacted 10-200 minute in 20 ℃, cooling, with the weak base neutralization, suction filtration, recrystallization obtain 2-hydroxyl-5-aminoacetophenone;
4) o-hydroxyacetophenone is synthetic
2-hydroxyl-5-aminoacetophenone is dissolved in the lower alcohol, adds mantoquita, drip the vitriol oil down, drip and finish, stirred 5-60 minute in 0-100 ℃ as catalyzer; Splash into saturated sodium nitrite in aqueous solution again, reacted 0.5-5 hour down in 0-100 ℃; Mantoquita: the vitriol oil: Sodium Nitrite: the mol ratio of 2-hydroxyl-5-aminoacetophenone is (0.005～0.02): (2～3): (1～2): 1; Carry out wet distillation then, the cut organic solvent extraction, underpressure distillation obtains o-hydroxyacetophenone.
In the synthetic method of the present invention, said organic solvent can be benzene,toluene,xylene, chlorobenzene, bromobenzene, dichlorobenzene, methylene dichloride, trichloromethane, tetracol phenixin, 1 in the step 1), 2-ethylene dichloride, 1,1,2-trichloroethane, ethyl acetate, methyl acetate, ethyl formate, pentamethylene, hexanaphthene, acetone or butanone etc.Said weak base can be anhydrous K 2CO 3, Na 2CO 3, KHCO 3, NaHCO 3, triethylamine, Trimethylamine 99, pyridine, morpholine, di-isopropyl methylamine, diisopropyl ethyl amine or tri-n-butyl amine etc.Said acylating reagent can be diacetyl oxide, Acetyl Chloride 98Min. or acetyl bromide etc.The 4-acetaminophenol acetic ester of this reaction gained need not recrystallization purifying, and yield can reach 96.2%.
In the synthetic method of the present invention, step 2) said organic solvent can be oil of mirbane, chlorobenzene, bromobenzene, dichlorobenzene or trichlorobenzene etc. in.Described lewis acid catalyst can be aluminum trichloride (anhydrous), Zinc Chloride Anhydrous or anhydrous stannic chloride etc.The used solvent of recrystallization is dehydrated alcohol, anhydrous methanol or 1, the 2-ethylene dichloride.
In the synthetic method of the present invention, said mineral acid is that massfraction is hydrochloric acid or the sulfuric acid of 1-60% in step 3); Described weak base is that massfraction is the NH of 1-60% 3H 2O, KHCO 3Or NaHCO 3The used solvent of recrystallization is one or both in water, ethanol, methyl alcohol and the ethyl acetate.
In the synthetic method of the present invention, in step 4), said lower alcohol is industrial methanol, ethanol, Virahol or butanols; Said mantoquita is cupric sulfate pentahydrate, cupric chloride, cupric bromide, cupric iodide or cupric oxide.The organic solvent that the extraction cut is used can be ester class, ethers or a haloalkane commonly used, and said ester class is selected from ethyl acetate or butylacetate; Ethers is an ether; Haloalkane is selected from methylene dichloride or trichloromethane.
Reaction equation of the present invention is as follows:
Figure S2008100616198D00031
The present invention compares the beneficial effect that has with background technology:
1) the synthesizing o-hydroxy ethyl ketone of bibliographical information generally is to be raw material with phenol or semicarbazone, is raw material and the invention provides a kind of with Paracetamol (to acetaminophenol), through four-step reaction, can make things convenient for the economic o-hydroxyacetophenone that obtains.The industrial chemicals that Paracetamol has become a kind of cheapness, has been easy to get.
2) 4-acetaminophenol acetic ester and aluminum trichloride (anhydrous) direct heating have been avoided in the application of the inventive method, make to stir difficulty, and the reactant caking, and do not have the problem that adjacency pair position product is selected, and directly obtain o-hydroxyacetophenone.
3) the inventive method reaction conditions gentleness is easy and simple to handle, and product yield is higher, and good industrialized application prospect is arranged.
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
1) preparation of 4-acetaminophenol acetic ester
With Paracetamol (45.4g, 0.3mol), Acetyl Chloride 98Min. (33g, 0.42mol) and Anhydrous potassium carbonate (41.4g 0.3mol) is added in the ethyl acetate of 500ml, and stirring heating was in 78 ℃ of following back flow reaction 18 hours.Normal pressure steams to remove and reclaims solvent, and cooling adds 350ml water, separates out solid, and suction filtration also washes the solid 55.7g that repeatedly obtains white, yield 96.1% with water.Experimental data is as follows:
mp?158-159℃； 1HNMR(400MHz，CDCl 3)δ(ppm)：7.50-7.47(d，2H，ArH)，7.33(s，1H，NHCO)，7.04-7.02(d，2H，ArH)，2.29(s，3H，CH 3COO)，2.16(s，3H，CH 3CONH)。IR(KBr)cm -1：3369，3294，1751，1691，1608，1541，1507，1365，1241
2) preparation of 2-hydroxyl 5-acetamido methyl phenyl ketone
With 4-acetaminophenol acetic ester (19.3g, 0.1mol) be dissolved in orthodichlorobenzene (150ml), add aluminum trichloride (anhydrous) (33.3g, 0.25mol), stir, slowly heat up, controlled temperature reacted 4 hours about 140-145 ℃, and reaction finishes, cooling reactant to 60 ℃, remove by filter orthodichlorobenzene, filter cake is dissolved in 1, and the mixing solutions of 2-ethylene dichloride and water is told organic layer, water layer is with 1,2-ethylene dichloride (100ml * 3) extraction merges organic layer, anhydrous sodium sulfate drying, filter, filtrate is concentrated into dried, obtains powdery yellow solid 16.3g, yield 84.6% with the dehydrated alcohol recrystallization.
Experimental data is as follows:
mp?167-169℃； 1HNMR(400MHz，CDCl 3)δ(ppm)：12.09(s，1H，OH)，8.18(s，1H，ArH)，7.35-7.32(d，1H，ArH)，7.14(s，1H，NHCO)，6.95-6.93(d，1H，ArH)，2.63(s，3H，CH 3CONH)，2.18(s，3H，CH 3CO)。IR(KBr)cm -1：3252，3058，1656，1560，1487，1410，1368，1252，793，634，517
3) preparation of 2-hydroxyl 5-aminoacetophenone
With 2-hydroxyl 5-acetamido methyl phenyl ketone (19.3g, 0.1mol) and 15% dilute hydrochloric acid (28ml 0.12mol) heated in the 100ml there-necked flask, 105-115 ℃ of following back flow reaction 40 minutes; Reaction finishes, and is cooled to room temperature, the NH with 10% 3H 2O is adjusted to PH=7-8, suction filtration, and the aqueous ethanolic solution recrystallization with 10% obtains deep yellow needle-like solid 14.0g, yield 92.1%.
Experimental data is as follows:
mp?111-113℃； 1HNMR(400MHz，CDCl 3)δ(ppm)：11.72(s，1H，OH)，7.03-7.04(d，1H，ArH)，6.90-6.92(dd，1H，ArH)，6.82-6.84(d，1H，ArH)，3.46(bs，2H，NH 2)，2.58(s，3H，CH 3CO)。IR(KBr)cm -1：3460，2931，2865，1649，1134，976，941
4) preparation of o-hydroxyacetophenone
(45.7g 0.3mol) is dissolved in 95% the industrial alcohol (250ml), and (0.5g 2mmol), is warming up to 50 ℃ to add cupric sulfate pentahydrate with 2-hydroxyl 5-aminoacetophenone; (58.5g 0.6mol) joins in the ethanolic soln in 1 hour through dropping funnel, and temperature is controlled at 50-55 ℃, after dropwising, keeps 50 ℃ to stir 15 minutes with the vitriol oil; With NaNO 2(24.7g, 0.36mol) the solid saturated solution that is made into soluble in water through dropping funnel, splashed into this saturated solution in 2 hours in 50 ℃ the ethanolic soln, dripped and finished, in 50 ℃ of following stirring reactions 1 hour.Be warming up to back flow reaction then 2 hours; Reaction finishes, and normal pressure steams and removes 80% ethanol, carries out wet distillation, cut ethyl acetate extraction (50ml * 3), and anhydrous sodium sulfate drying, suction filtration, the cut of 128-130/8.0KPa is collected in decompression, is weak yellow liquid 38.5g, yield 94.4%.
Experimental data is as follows:
Gas-chromatography content: 〉=99.7% (analysis condition is: column length 30m, the ATSE-30 capillary column of diameter 0.25mm; Hydrogen flame detects: 140 ℃ of column temperatures, and detector temperature: 250 ℃, perfusor: 250 ℃; Carrier gas is N 2, flow velocity: 30ml/min, hydrogen flow rate: 15ml/min;
1HNMR(400MHz，CDCl 3)δ(ppm)：12.26(s，1H，OH)，7.72-7.75(dd，1H，ArH)，7.45-7.49(m，1H，ArH)，6.97-6.99(d，1H，ArH)，6.89-6.92(t，1H，ArH)，2.64(s，3H，CH 3CO)。IR(KBr)cm -1：3434，3000，2914，1642，1437，1407，1027，954，704，671，619
CI-MS：136(M +)
Embodiment 2:
1) preparation of 4-acetaminophenol acetic ester
According to the method for step 1) among the embodiment 1, the charging capacity of Acetyl Chloride 98Min. is 23.6g, gets 4-acetaminophenol acetic ester 53.5g, yield 92.3%.
2) preparation of 2-hydroxyl 5-acetamido methyl phenyl ketone
According to step 2 among the embodiment 1) method, the charging capacity of aluminum trichloride (anhydrous) is 13.4g, after the reaction 2-hydroxyl 5-acetamido methyl phenyl ketone 15.5g, yield 80.3%.
3) preparation of 2-hydroxyl 5-aminoacetophenone
According to the method for step 3) among the embodiment 1, the charging capacity of 15% dilute hydrochloric acid is 121.6ml, gets 2-hydroxyl 5-aminoacetophenone 13.7g, yield 90.1% after the reaction.
4) preparation of o-hydroxyacetophenone
According to the method for step 4) among the embodiment 1, the charging capacity of the vitriol oil is 49.0g, and reaction obtains o-hydroxyacetophenone 37.7g, yield 92.4%.
Embodiment 3:
1) preparation of 4-acetaminophenol acetic ester
According to the method for step 1) among the embodiment 1, the charging capacity of Acetyl Chloride 98Min. is 141.3g, gets 4-acetaminophenol acetic ester 54.8g, yield 94.5%.
2) preparation of 2-hydroxyl 5-acetamido methyl phenyl ketone
According to step 2 among the embodiment 1) method, the charging capacity of aluminum trichloride (anhydrous) is 133.5g, after the reaction 2-hydroxyl 5-acetamido methyl phenyl ketone 14.5g, yield 75.1%.
3) preparation of 2-hydroxyl 5-aminoacetophenone
According to the method for step 3) among the embodiment 1, the charging capacity of 10% dilute hydrochloric acid is 91.2ml, gets 2-hydroxyl 5-aminoacetophenone 13.8g, yield 91.4% after the reaction.
4) preparation of o-hydroxyacetophenone
According to the method for step 4) among the embodiment 1, NaNO 2Charging capacity be 20.7g, obtain o-hydroxyacetophenone 36.2g after the reaction, yield 88.7%.
Embodiment 4:
1) preparation of 4-acetaminophenol acetic ester
With the ingredient proportion of step 1) among the embodiment 1, reacted 36 hours down at 25 ℃, get 4-acetaminophenol acetic ester 49.2g, yield 85.0%.
2) preparation of 2-hydroxyl 5-acetamido methyl phenyl ketone
With step 2 among the embodiment 1) ingredient proportion, technological operation, about 150-155 ℃ the reaction 3 hours, 2-hydroxyl 5-acetamido methyl phenyl ketone 15.7g, yield 81.3%.
3) preparation of 2-hydroxyl 5-aminoacetophenone
With ingredient proportion, the technological process of step 3) among the embodiment 1, NH with 10% 3H 2O is adjusted to PH=5-6, and suction filtration gets 2-hydroxyl 5-aminoacetophenone 12.6g, yield 82.9%.
4) preparation of o-hydroxyacetophenone
According to the method for step 4) among the embodiment 1, the charging capacity of cupric sulfate pentahydrate is 2.0g, and reaction obtains o-hydroxyacetophenone 38.4g, yield 94.1%.
Embodiment 5:
1) preparation of 4-acetaminophenol acetic ester
With the ingredient proportion of step 1) among the embodiment 1, reacted 24 hours down at 50 ℃, obtain 4-acetaminophenol acetic ester 52.2g, yield 90.1%.
2) preparation of 2-hydroxyl 5-acetamido methyl phenyl ketone
With step 2 among the embodiment 1) ingredient proportion, technological process, about 170-175 ℃ the reaction 2 hours, obtain 2-hydroxyl 5-acetamido methyl phenyl ketone 14.9g, yield 77.4%.
3) preparation of 2-hydroxyl 5-aminoacetophenone
With ingredient proportion, the technological process of step 3) among the embodiment 1, NH with 15% 3H 2O is adjusted to PH=10-11, and suction filtration gets 2-hydroxyl 5-aminoacetophenone 13.1g, yield 86.2%.
4) preparation of o-hydroxyacetophenone
According to charging capacity, the technological process of step 4) among the embodiment 1, replace anhydrous cupric sulfate with equimolar cupric chloride, get o-hydroxyacetophenone 38.0g, yield 93.1% after the reaction.
Embodiment 6:
1) preparation of 4-acetaminophenol acetic ester
Replace Anhydrous potassium carbonate with equimolar triethylamine, remaining charging capacity, technological process are pressed the step 1) among the embodiment 1, get 4-acetaminophenol acetic ester 53.8g, and yield is 93.0%.
2) preparation of 2-hydroxyl 5-acetamido methyl phenyl ketone
Replace aluminum trichloride (anhydrous) with equimolar Zinc Chloride Anhydrous, all the other charging capacitys, technological process are all by the step 2 among the embodiment 1), get 2-hydroxyl 5-acetamido methyl phenyl ketone 14.1g, yield 73.1%.
3) preparation of 2-hydroxyl 5-aminoacetophenone
Sulfuric acid with equimolar 10% replaces 15% dilute hydrochloric acid, and remaining charging capacity, technological process get 2-hydroxyl 5-aminoacetophenone 13.9g, yield 91.4% with the step 3) among the embodiment 1.
4) preparation of o-hydroxyacetophenone
With the ingredient proportion of step 4) among the embodiment 1, drip the vitriol oil, NaNO down at 70 ℃ 2Saturated solution gets o-hydroxyacetophenone 36.9g, yield 90.4%.

Claims (7)

1. the synthetic method of an o-hydroxyacetophenone is characterized in that may further comprise the steps:
1) 4-acetaminophenol acetic ester is synthetic
In reactor acamol is dissolved in the organic solvent, adds weak base simultaneously, the mol ratio of weak base and acamol is 1: 0.5～3, adds acylating reagent then, the consumption of acylating reagent be acamol mole number 1-6 doubly; 0 ℃ of reaction after 3-36 hour to the reflux temperature, steam and remove organic solvent, add entry, suction filtration gets 4-acetaminophenol acetic ester solid product, said organic solvent is benzene,toluene,xylene, chlorobenzene, bromobenzene, dichlorobenzene, methylene dichloride, trichloromethane, tetracol phenixin, 1,2-ethylene dichloride, vinyl trichloride, ethyl acetate, methyl acetate, ethyl formate, pentamethylene, hexanaphthene, acetone or butanone;
2) 2-hydroxyl-5-acetamido methyl phenyl ketone is synthetic
4-acetaminophenol acetic ester with step 1) in reactor is dissolved in the organic solvent, add lewis acid catalyst simultaneously, its consumption be 4-acetaminophenol acetic ester mole number 1-10 doubly, reacted 1-18 hour down at 20-180 ℃, cooling, filter, recrystallization obtains 2-hydroxyl-5-acetamido methyl phenyl ketone, and said organic solvent is oil of mirbane, chlorobenzene, bromobenzene, dichlorobenzene or trichlorobenzene;
3) 2-hydroxyl-5-aminoacetophenone is synthetic
2-hydroxyl-5-acetamido methyl phenyl ketone and mineral acid were added in the reactor in 1: 5 in molar ratio～5: 1, to reflux temperature, reacted 10-200 minute in 20 ℃, cooling, with the weak base neutralization, suction filtration, recrystallization obtain 2-hydroxyl-5-aminoacetophenone;
4) o-hydroxyacetophenone is synthetic
2-hydroxyl-5-aminoacetophenone is dissolved in the lower alcohol, adds mantoquita, drip the vitriol oil down, drip and finish, stirred 5-60 minute in 0-100 ℃ as catalyzer; Splash into saturated sodium nitrite in aqueous solution again, reacted 0.5-5 hour down in 0-100 ℃; Mantoquita: the vitriol oil: Sodium Nitrite: the mol ratio of 2-hydroxyl-5-aminoacetophenone is (0.005～0.02): (2～3): (1～2): 1; Carry out wet distillation then, the cut organic solvent extraction, underpressure distillation obtains o-hydroxyacetophenone, and said organic solvent is ethyl acetate, butylacetate, ether, methylene dichloride or trichloromethane, and lower alcohol is industrial methanol, ethanol, Virahol or butanols.
2. the synthetic method of o-hydroxyacetophenone according to claim 1 is characterized in that said weak base is anhydrous K in the step 1) 2CO 3, Na 2CO 3, KHCO 3, NaHCO 3, triethylamine, Trimethylamine 99, pyridine, morpholine, di-isopropyl methylamine, diisopropyl ethyl amine or tri-n-butyl amine.
3. the synthetic method of o-hydroxyacetophenone according to claim 1 is characterized in that said acylating reagent is diacetyl oxide, Acetyl Chloride 98Min. or acetyl bromide in the step 1).
4. the synthetic method of o-hydroxyacetophenone according to claim 1 is characterized in that step 2) in said lewis acid catalyst be aluminum trichloride (anhydrous), Zinc Chloride Anhydrous or anhydrous stannic chloride; The used solvent of recrystallization is dehydrated alcohol, anhydrous methanol or 1, the 2-ethylene dichloride.
5. the synthetic method of o-hydroxyacetophenone according to claim 1 is characterized in that said mineral acid is that massfraction is hydrochloric acid or the sulfuric acid of 1-60% in the step 3); Said weak base is that massfraction is the NH of 1-60% 3H 2O, KHCO 3Or NaHCO 3
6. the synthetic method of o-hydroxyacetophenone according to claim 1 is characterized in that the used solvent of recrystallization in the step 3) is one or both in water, ethanol, methyl alcohol and the ethyl acetate.
7. the synthetic method of o-hydroxyacetophenone according to claim 1 is characterized in that said mantoquita is cupric sulfate pentahydrate, cupric chloride, cupric bromide or cupric iodide in the step 4).
CN2008100616198A 2008-05-23 2008-05-23 Synthetic method of o-hydroxyacetophenone Expired - Fee Related CN101279903B (en)

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