CN114057559A - Preparation method of diaryl ketone - Google Patents

Preparation method of diaryl ketone Download PDF

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CN114057559A
CN114057559A CN202010762628.0A CN202010762628A CN114057559A CN 114057559 A CN114057559 A CN 114057559A CN 202010762628 A CN202010762628 A CN 202010762628A CN 114057559 A CN114057559 A CN 114057559A
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胡晓允
郭建鑫
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South Central Minzu University
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Abstract

The invention relates to the field of organic compound preparation chemistry, and particularly discloses a preparation method of diaryl ketone. The invention uses tartrate and aryl Grignard reagent to react to prepare 1,1,4, 4-tetraaryl butyl tetrol; under the condition of organic alkali and specific temperature, 1,1,4, 4-tetraaryl butyl tetrol and thionyl chloride generate highly regioselective 2, 3-cyclic sulfitation reaction to generate dichloroaryl cyclic sulfite; the dichloro aryl cyclic sulfite then reacts with inorganic alkali liquor at a certain temperature and in a certain organic solvent to generate diaryl ketone. The preparation method of the invention avoids the use of expensive heavy metal-containing catalyst, and has the obvious characteristics of easily obtained raw materials, simple and convenient operation, excellent reaction area selectivity, easy treatment, high yield and the like.

Description

Preparation method of diaryl ketone
Technical Field
The invention relates to the field of organic compound preparation chemistry, in particular to a preparation method of diaryl ketone.
Background
Diaryl ketone is used as a very important Chemical product and a medical intermediate, and is widely applied to the synthesis of fine chemicals such as medicines, pesticides, dyes and the like ((a) Chemical & Pharmaceutical Bulletin,2004,52: 818; (b) J.M ed. chem.,1997,40: 3937; (c) invention patent: synthesis process of diaryl ketone derivatives, publication number: 107032938A). The traditional synthesis methods comprise a hydrolysis method of a cell dihalide, a Friedel-crafts acylation method, an oxidation or dehydrogenation method of alcohol, and a preparation method of aryl formyl chloride reacting with a Grignard reagent or organic copper lithium. The most common method is friedel-crafts acylation, which often requires a large amount of Lewis acid catalyst during the preparation process, which increases the amount of metal residue to be treated, and at the same time, is very corrosive to equipment and causes severe environmental pollution (organic chemistry, 2011,31, 1188). The preparation method of aryl formyl chloride and organic metal reagent is adopted, but the ketone generated by the reaction can be easily further reacted with Grignard reagent or organic copper lithium reagent to generate corresponding tertiary alcohol (Synthesis,1984,9:734), and the organic metal reagent has high toxicity (J.Am.chem.Soc,1983,105: 6129). The synthesis of diaryl ketone by using aryl halide and aryl boric acid and other reagents requires noble metal palladium as a catalyst (J.Am.chem.Soc.,2000,122:11260), and the catalyst often contains heavy metal ions, which is avoided as much as possible in the drug synthesis.
In contrast, diaryl ketone compounds prepared by a highly efficient and practical synthesis method using inexpensive and readily available compounds have undoubtedly significant advantages, but no relevant reports have been found in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of diaryl ketone. The method has the advantages of cheap and easily-obtained raw materials, simple synthesis process, convenient operation, no heavy metal, excellent reaction selectivity and high product yield.
The principle of the invention is as follows: reacting tartrate with an aryl Grignard reagent to prepare 1,1,4, 4-tetraaryl butanetetraol, carrying out a highly regioselective 2, 3-cyclic sulfitation reaction on the 1,1,4, 4-tetraaryl butanetetraol and thionyl chloride under a certain reaction condition to generate dichloroaryl cyclic sulfite, and then reacting the dichloroaryl cyclic sulfite with an alkali liquor under a certain condition to generate diaryl ketone.
The technical key points provided by the invention are as follows: dichloroaryl cyclic sulfite is prepared by one-step 2, 3-cyclic sulfitation reaction of 1,1,4, 4-tetraarylbutanetetraol with high regioselectivity, and then the dichloroaryl cyclic sulfite reacts with alkali liquor to prepare diaryl ketone, wherein the structural formula of the diaryl ketone is as follows:
Figure BDA0002613501800000021
the preparation method of the diaryl ketone comprises the following steps:
(1) reacting tartrate with an aryl Grignard reagent to prepare 1,1,4, 4-tetraaryl butanetetraol;
(2) under the condition of organic alkali and specific temperature, 1,1,4, 4-tetraaryl butyl tetrol and thionyl chloride generate highly regioselective 2, 3-cyclic sulfite esterification reaction to efficiently prepare dichloroaryl cyclic sulfite;
(3) then reacting with inorganic alkali liquor at a certain temperature and in a certain organic solvent to prepare the diaryl ketone with high yield.
The general formula of the aryl Grignard reagent in the step (1) is RMgX, wherein R is aryl, and X is Cl, Br or I;
further, in the formula, R is substituted phenyl, the substituted phenyl is mono-substituted or di-substituted, the substituted position is meta-position or para-position of a benzene ring, and the substituted group is methyl, substituted methyl or tert-butyl; the substituted methyl is-CX3(X is F or Cl);
more preferably, R is substituted phenyl, the substituted phenyl is monosubstituted, the substituted position is meta-position or para-position of a benzene ring, and the substituted group is methyl, -CX3(X is F or Cl), tert-butyl;
more preferably, R is substituted phenyl, the substituted phenyl is disubstituted, the substituted positions are meta and para positions of the benzene ring, the substituted groups are the same and are methyl or-CX3(X is F or Cl);
most preferably, R is p-tert-butylphenyl, p-methylphenyl, p-trifluoromethylphenyl or 3, 5-dimethylphenyl.
The organic base in the step (2) is triethylamine or pyridine;
the molar ratio of the organic base dosage to the 1,1,4, 4-tetraarylbutanetetraol in the step (2) is (6-30): 1;
the molar ratio of the dosage of the thionyl chloride to the 1,1,4, 4-tetraarylbutanetetraol in the step (2) is (3-6): 1;
preferably, the molar ratio of the organic base, the thionyl chloride and the 1,1,4, 4-tetraarylbutanetetraol in the step (2) is 30: 3: 1;
the specific temperature in the step (2) is-5-36 ℃, and is preferably-5 ℃;
the certain temperature in the step (3) is 0-90 ℃, and preferably 60-90 ℃;
the certain organic solvent in the step (3) is tetrahydrofuran, N-dimethylformamide, dioxane, acetonitrile or acetone;
the inorganic alkali liquor in the step (3) is an aqueous solution of inorganic alkali, and the inorganic alkali is NaOH, KOH or Na2S；
The concentration of the inorganic alkali liquor in the step (3) is 1-5 mol/L;
the molar ratio of the inorganic alkali consumption in the inorganic alkali liquor in the step (3) to the dichloroaryl ring sulfite is (5-30): 1.
compared with the prior art, the invention has the advantages and beneficial effects that:
the invention takes tartrate and aryl halide as raw materials to prepare 1,1,4, 4-tetraaryl butyl tetrol, the dichloroaryl cyclic sulfite is efficiently prepared by the high area selective derivatization reaction of the 1,1,4, 4-tetraaryl butyl tetrol and thionyl chloride, and the diaryl ketone is prepared by the carbon-carbon bond breakage under the action of alkali liquor, thus avoiding the use of expensive heavy metal-containing catalysts. The preparation method has the remarkable characteristics of easily obtained raw materials, simple and convenient operation, excellent reaction area selectivity, easy treatment, high yield and the like.
Drawings
FIG. 1 is a structural diagram of di-tert-butyl phenyl ketone synthesized in example 1.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1: the aryl is p-tert-butylphenyl, and the preparation method of diaryl ketone comprises the following steps:
(1) preparation of 1,1,4, 4-tetra-p-tert-butylphenyl-butanol
Figure BDA0002613501800000031
Yield: 65.6%, m.p. 243-;1H NMR(400MHz,Chloroform-d)δ7.37(d,J＝8.5Hz,4H),7.25(d,J＝8.1Hz,12H),4.67(s,2H),4.47(d,J＝4.7Hz,2H),3.72(d,J＝4.5Hz,2H),1.36(s,18H),1.22(s,18H).13C NMR(101MHz,Chloroform-d)δ149.9,149.7,141.2,141.1,141.0,125.4,125.2,124.6,81.4,72.4,34.5,34.3,31.4,31.2.
(2) preparation of p-tert-butylphenyl dichlorocyclosulfite
In a round bottom flask, a tetrahydrofuran solution of 1,1,4, 4-tetra-p-tert-butylphenyl butanetetraol and 30 equivalents (i.e., the molar ratio of 1,1,4, 4-tetra-p-tert-butylphenyl butanetetraol to triethylamine is 1:30, the same applies hereinafter) of triethylamine are stirred at 0 ℃ for 15 minutes, 3 equivalents of thionyl chloride (i.e., the molar ratio of 1,1,4, 4-tetra-p-tert-butylphenyl butanetetraol to thionyl chloride is 1:3, the same applies hereinafter) are added dropwise, the mixture is stirred for 30 minutes and then returned to room temperature (25-30 ℃), the mixture is stirred for 30 minutes, water is added for treatment (the generated triethylamine salt is removed), and the mixture is recrystallized by using ethanol to obtain p-tert-butylphenyl dichlorocyclithic acid ester.
Figure BDA0002613501800000041
Ar＝4-tBuC6H4The yield is 90.0%; m.p.184 ℃;1H NMR(500MHz,Chloroform-d)δ7.43-7.37(m,2H,Ar-H),7.30(m,14H,Ar-H),6.01(d,J＝2.2Hz,1H),5.78(d,J＝2.2Hz,1H),1.32(s,8H),1.30(s,8H),1.28(s,8H),1.25(s,8H).13C NMR(126MHz,Chloroform-d)δ151.6,151.3,151.2,150.8,138.8,129.0,128.9,128.2,128.1,125.2,125.0,124.7,88.1,87.3,34.6,34.5,31.7,31.2.
(3) preparation of diaryl ketones
Figure BDA0002613501800000042
1:10), heating the mixture at 70 ℃ for 2 hours for reaction, adding water for stopping the reaction (detecting the reaction of the raw materials is complete by TLC), and recrystallizing by using ethanol to obtain the di-tert-butyl phenyl ketone, wherein the yield is as follows: 73.0%, m.p. 133 ℃; 1H NMR (400MHz, Chloroform-d) δ 7.77(d, J ═ 8.2Hz,8H),7.49(d, J ═ 8.2Hz,8H),1.37(s,36H), 13C NMR (101MHz, CDCl3) δ 196.2,155.9,135.2,130.0,125.2,35.1,31.2.
Single crystal data: c21H26O,Mw＝294.42,Monoclinic,spacegroup,C2/c,a＝30.988(5),b＝6.2327(8),c＝18.218(2),α＝90°,β＝98.726(6)°,γ＝90°,
Figure BDA0002613501800000043
Z＝8,F(000)＝1280,T＝173(2)K,μ(MoKα)＝0.067mm-1Its structure is shown in fig. 1.
Example 2: the aryl is p-methylphenyl, and the preparation method of diaryl ketone comprises the following steps:
(1) preparation of 1,1,4, 4-tetra-p-methylphenyl tetrol
Figure BDA0002613501800000051
(400MHz,Chloroform-d)δ7.20(s,4H,Ar-H),7.15(s,8H,Ar-H),7.06(s,4H,Ar-H)4.68(s,2H,OH),4.41(s,2H,CH),3.80(s,2H,OH),2.36(s,6H,CH3),2.24(s,6H,CH3).13C NMR(101MHz,DMSO-d6)δ143.9,143.1,135.8,135.4,129.0,128.5,126.7,125.8,81.4,71.8.
(2) Preparation of p-methylphenyl dichloro-cyclo-sulfite
In a round-bottom flask, 1,1,4, 4-tetra-p-methylphenyl butyl tetrol tetrahydrofuran solution and 30 equivalents of triethylamine are stirred for 15 minutes at 0 ℃,3 equivalents of thionyl chloride is dripped into the mixture, the mixture is stirred for 30 minutes and then is returned to the room temperature (25-30 ℃), the mixture is stirred for 30 minutes, water is added into the mixture for treatment (the generated triethylamine salt is removed), and the mixture is recrystallized by ethanol to obtain the p-methylphenyl dichlorocyclo sulfite.
Figure BDA0002613501800000052
Ar＝4-MeC6H4The yield is 90.0%; m.p.184 ℃;1H NMR(500MHz,Chloroform-d)δ7.43-7.37(m,2H,Ar-H),7.30(m,14H,Ar-H),6.01(d,J＝2.2Hz,1H),5.78(d,J＝2.2Hz,1H),1.32(s,8H),1.30(s,8H),1.28(s,8H),1.25(s,8H).13C NMR(126MHz,Chloroform-d)δ151.6,151.3,151.2,150.8,138.8,129.0,128.9,128.2,128.1,125.2,125.0,124.7,88.1,87.3,34.6,34.5,31.7,31.2.
(3) preparation of diaryl ketones
Figure BDA0002613501800000053
To a 25mL round bottom flask equipped with a magnetic rotor was added p-methylbenzeneAdding 3mol/L aqueous solution of NaOH (the molar ratio of p-methylphenyl dichloro cyclic sulfite to sodium hydroxide is 1:20) into N, N-dimethylformamide solution of dichloromethyl cyclic sulfite (1mmol), heating the mixture at 70 ℃ for 2 hours, adding water to stop the reaction (the raw material is completely reacted by TLC detection), and recrystallizing with ethanol to obtain dimethyl phenyl ketone, wherein the yield is as follows: 95 percent, m.p. 92 ℃;1H NMR(600MHz,Chloroform-d)δ7.70(d,J＝8.1Hz,4H),7.27(d,J＝7.9Hz,4H),2.44(s,6H).13C NMR(151MHz,Chloroform-d)δ196.4,143.0,135.2,130.2,128.9,21.7.
example 3: the aryl is p-trifluoromethyl phenyl, and the preparation process of diaryl ketone includes the following steps:
(1) preparation of 1,1,4, 4-tetra-p-trifluoromethylphenylbutanol
Figure BDA0002613501800000061
32％，m.p.:135-136℃,1H NMR(400MHz,Chloroform-d):δ7.66-7.42(m,16H,Ar-H),4.63(s,2H,OH),4.46(s,2H,CH),3.84(s,2H,OH).13C NMR(101MHz,DMSO-d6)δ151.0,149.2,128.2,127.0,125.3,124.9,80.8,70.9.
(2) Preparation of p-trifluoromethylphenyl dichloro-cyclo-sulfite
In a round-bottom flask, 1,1,4, 4-tetra-p-trifluoromethylphenyl butyl tetrol tetrahydrofuran solution and 30 equivalents of triethylamine are stirred for 15 minutes at 0 ℃,3 equivalents of thionyl chloride is dripped in the mixture, the mixture is stirred for 30 minutes and then is returned to room temperature (25-30 ℃), the mixture is stirred for 30 minutes, water is added for treatment (the generated triethylamine salt is removed), and the mixture is recrystallized by ethanol to obtain the p-trifluoromethylphenyl dichloro cyclic sulfite.
Figure BDA0002613501800000062
Ar＝4-CF3C6H4The yield is 90.0%; 184 ℃ in m.p.;1H NMR(500MHz,Chloroform-d)δ7.43-7.37(m,2H,Ar-H),7.30(m,14H,Ar-H),6.01(d,J＝2.2Hz,1H),5.78(d,J＝2.2Hz,1H),1.32(s,8H),1.30(s,8H),1.28(s,8H),1.25(s,8H).13C NMR(126MHz,Chloroform-d)δ151.6,151.3,151.2,150.8,138.8,129.0,128.9,128.2,128.1,125.2,125.0,124.7,88.1,87.3,34.6,34.5,31.7,31.2.
(3) preparation of diaryl ketones
Figure BDA0002613501800000071
In a 25mL round bottom flask equipped with a magnetic rotor, a dioxane solution of p-trifluoromethylphenyldichlorocyclosulfite (1mmol) was added, a 4mol/L aqueous NaOH solution was further added (molar ratio of p-trifluoromethylphenyldichlorocyclosulfite to NaOH was 1:30), the mixture was heated at 70 ℃ for 2 hours, water was added to terminate the reaction (completion of the reaction of the starting materials was detected by TLC), and column chromatography was performed to purify to obtain bis (trifluoromethylphenyl) methanone, yield: 45% of oil1H NMR(600MHz,Chloroform-d)δ7.93–7.87(m,4H),7.82–7.76(m,4H).13C NMR(151MHz,Chloroform-d)δ194.4,139.7,134.3,130.2,125.7,125.6.
Example 4: aryl is 3, 5-dimethylphenyl, and a process for preparing a diaryl ketone, comprising the steps of:
(1) preparation of 1,1,4, 4-tetrakis (3, 5-dimethylphenyl) butanetetraol
Figure BDA0002613501800000072
Grignard reagent 3, 5-dimethylphenylmagnesium bromide was prepared according to a conventional procedure, racemic diethyl tartrate was added dropwise to 6 equivalents of 3, 5-dimethylphenylmagnesium bromide in tetrahydrofuran, and after 2 hours of reaction, the mixture was quenched with saturated aqueous ammonium chloride solution, extracted with diethyl ether, concentrated, and subjected to silica gel column chromatography (PE/EA ═ 6: 1) to give 1,1,4, 4-tetrakis (3, 5-dimethylphenyl) butanetetraol (see: Helvetica Chimica Acta,2010,93,497.), yield: 52.3 percent, m.p. 164-,1H NMR(400MHz,Chloroform-d)δ7.20(s,4H,Ar-H),7.15(s,8H,Ar-H),7.06(s,4H,Ar-H)4.68(s,2H,OH),4.41(s,2H,CH),3.80(s,2H,OH),2.36(s,6H,CH3),2.24(s,6H,CH3).13C NMR(101MHz,DMSO-d6)δ143.9,143.1,135.8,135.4,129.0,128.5,126.7,125.8,81.4,71.8.
(2) preparation of 3, 5-dimethylphenyl dichlorocyclo sulfite
In a round-bottom flask, 1,1,4, 4-tetrakis (3, 5-dimethylphenyl) butanetetraol in tetrahydrofuran is stirred with 30 equivalents of triethylamine at 0 ℃ for 15 minutes, then 3 equivalents of thionyl chloride is added dropwise, the mixture is stirred for 30 minutes and then returned to room temperature (25 ℃ to 30 ℃), then the mixture is stirred for 30 minutes, water is added for treatment (generated triethylamine salt is removed), and the mixture is recrystallized by ethanol to obtain 3, 5-dimethylphenyldichloro-cyclosulfite.
Figure BDA0002613501800000081
Ar＝3，5-Me2C6H4The yield is 90.0%; m.p.184 ℃;1H NMR(500MHz,Chloroform-d)δ7.43-7.37(m,2H,Ar-H),7.30(m,14H,Ar-H),6.01(d,J＝2.2Hz,1H),5.78(d,J＝2.2Hz,1H),1.32(s,8H),1.30(s,8H),1.28(s,8H),1.25(s,8H).13C NMR(126MHz,Chloroform-d)δ151.6,151.3,151.2,150.8,138.8,129.0,128.9,128.2,128.1,125.2,125.0,124.7,88.1,87.3,34.6,34.5,31.7,31.2.
(3) preparation of diaryl ketones
Figure BDA0002613501800000082
In a 25mL round bottom flask equipped with a magnetic rotor, a solution of 3, 5-dimethylphenyl dichlorocyclosulfite (1mmol) in acetonitrile was added, a 5mol/LKOH aqueous solution (molar ratio of 3, 5-dimethylphenyl dichlorocyclosulfite to KOH was 1:5) was further added, the mixture was heated at 70 ℃ for 2 hours, water was added to terminate the reaction (completion of the reaction of the starting materials was detected by TLC), and the mixture was purified by column chromatography to obtain 3, 5-dimethylphenyl ketone in yield: 75% of oil;1H NMR(400MHz,Chloroform-d)δ7.39(s,2H),7.22(s,1H),2.38(s,6H).
comparative example:
Figure BDA0002613501800000083
the details are as follows: first Experimental Evidence of an Intramolecular H Bond between Aliphatic Cl and Aromatic C _ H, Xiaoyun Hu, Zixing Shan, and Vadim A. Solosonok, Crystal.Growth Des.2012,12,33-36.
The specific embodiments described in this specification are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (10)

1. A process for preparing a diaryl ketone, comprising the steps of:
(1) reacting tartrate with an aryl Grignard reagent to prepare 1,1,4, 4-tetraaryl butanetetraol;
(2) under the condition of organic alkali and specific temperature, 1,1,4, 4-tetraaryl butyl tetrol and thionyl chloride generate highly regioselective 2, 3-cyclic sulfite esterification reaction to prepare dichloroaryl cyclic sulfite;
(3) then reacting with inorganic alkali liquor at a certain temperature in a certain organic solvent to prepare diaryl ketone;
the general formula of the aryl Grignard reagent in the step (1) is RMgX, wherein R is aryl, and X is Cl, Br or I;
the specific temperature in the step (2) is-5-36 ℃;
the certain temperature in the step (3) is 0-90 ℃;
the certain organic solvent in the step (3) is tetrahydrofuran, N-dimethylformamide, dioxane, acetonitrile or acetone.
2. The method of claim 1, wherein: the aryl R is substituted phenyl, the substituted phenyl is mono-substituted or di-substituted, the substituted position is meta-position or para-position of a benzene ring, and the substituted group is methyl, substituted methyl or tert-butyl; the substituted methyl is-CX3Wherein X is F or Cl.
3. The method of claim 2, wherein:
the aromatic hydrocarbonThe R group is substituted phenyl, the substituted phenyl is monosubstituted, the substituted position is meta-position or para-position of a benzene ring, and the substituted group is methyl, -CX3T-butyl, wherein X is F or Cl;
the aryl R is substituted phenyl, the substituted phenyl is disubstituted, the substituted positions are meta and para of a benzene ring, the substituted groups are the same and are methyl or-CX3Wherein X is F or Cl.
4. The production method according to claim 3, characterized in that: the aryl R is p-tert-butylphenyl, p-methylphenyl, p-trifluoromethylphenyl or 3, 5-dimethylphenyl.
5. The process according to any one of claims 1 to 4, wherein the organic base in the step (2) is triethylamine or pyridine.
6. The process according to any one of claims 1 to 4, wherein the molar ratio of the amount of the organic base, the amount of the thionyl chloride and the 1,1,4, 4-tetraarylbutanetetraol in the step (2) is (6 to 30): (3-6): 1.
7. the method according to claim 6, wherein the molar ratio of the organic base, the sulfoxide chloride and the 1,1,4, 4-tetraarylbutanetetraol in the step (2) is 30: 3: 1.
8. the method according to any one of claims 1-4, wherein the inorganic base of the inorganic alkaline solution in step (3) is NaOH, KOH or Na2S。
9. The preparation method according to claim 8, wherein the molar ratio of the amount of the inorganic base in the inorganic alkaline solution to the dichloroaryl cyclic sulfite in the step (3) is (5-30): 1.
10. the method according to claim 8, wherein the concentration of the inorganic alkali solution in the step (3) is 1-5 mol/L.
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