CN114057559B - Preparation method of diaryl ketone - Google Patents
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Abstract
The invention relates to the field of organic compound preparation chemistry, and in particular discloses a preparation method of diaryl ketone. The invention prepares 1, 4-tetraaryltetrol by the reaction of tartrate and aryl Grignard reagent; in the presence of organic base, under the condition of specific temperature, 1, 4-tetraarylbutyl tetraol and thionyl chloride are subjected to high regioselective 2, 3-cyclosulfite reaction to generate dichloro aryl cyclosulfite; the dichloro aryl cyclic sulfite is then reacted with inorganic alkali liquor in certain organic solvent at certain temperature to produce diaryl ketone. The preparation method avoids the use of expensive heavy metal-containing catalysts, and has the remarkable characteristics of easily available raw materials, simple and convenient operation, excellent reaction area selectivity, easy treatment, high yield and the like.
Description
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 widely used as a very important Chemical product and pharmaceutical intermediate in 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), and (c) invention patent: synthetic process of diaryl ketone derivative, publication No. 107032938A). The traditional synthesis method comprises a cell dihalide hydrolysis method, a Friedel-crafts acylation method, an alcohol oxidation or dehydrogenation method and a preparation method by reacting benzoyl chloride 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, which increases the throughput of metal residues and at the same time, is serious to equipment corrosion and environmental pollution (organic chemistry, 2011,31,1188). The preparation of the arylcarbonyl chloride with the organometallic reagent is employed, but the ketone formed by the reaction readily reacts further with either the Grignard reagent or the organocopper lithium reagent to form the corresponding tertiary alcohol (Synthesis, 1984, 9:734), and the organometallic reagent is more toxic (J.Am. Chem. Soc,1983, 105:6129). The synthesis of diaryl ketones from aryl halides and aryl borates requires noble metal palladium as a catalyst (j.am. Chem. Soc.,2000, 122:11260), and these catalysts often contain heavy metal ions, which are to be avoided as much as possible in the synthesis of pharmaceuticals.
In contrast, the diaryl ketone compound prepared by using the cheap and easily available compound and through the efficient and practical synthesis method has obvious advantages, but no related report is seen in the prior art.
Disclosure of Invention
Aiming at the defects existing 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: the tartaric acid ester reacts with an aryl Grignard reagent to prepare 1, 4-tetraarylbutyl tetraol, under certain reaction conditions, the 1, 4-tetraarylbutyl tetraol and thionyl chloride are subjected to high regioselectivity 2, 3-cyclosulfite reaction to generate dichloro aryl cyclosulfite, and then the dichloro aryl cyclosulfite reacts with alkali liquor under certain conditions to generate diaryl ketone.
The technical key points provided by the invention are as follows: the dichloro aryl cyclic sulfite is prepared through a high regioselectivity 2, 3-cyclic sulfite reaction of 1, 4-tetraarylbutyl tetraol, and then the dichloro aryl cyclic sulfite reacts with alkali liquor to prepare diaryl ketone, wherein the structural formula of the diaryl ketone is as follows:
the preparation method of the diaryl ketone comprises the following steps:
(1) Reacting tartaric acid ester with an aryl Grignard reagent to obtain 1, 4-tetraaryltetrol;
(2) Under the existence of organic alkali and specific temperature condition, 1, 4-tetraarylbutyl tetraol and thionyl chloride are subjected to high regioselective 2, 3-cyclosulfite reaction to efficiently prepare dichloro aryl cyclosulfite;
(3) Then reacts with inorganic alkali liquor in a certain organic solvent at a certain temperature to prepare the diaryl ketone with high yield.
The aryl Grignard reagent in the step (1) has a general formula of RMgX, wherein R is aryl, and X is Cl, br or I;
further, R is a substituted phenyl, the substituted phenyl is mono-substituted or di-substituted, the substituted position is meta-position or para-position of benzene ring, and the substituted group is methyl, substituted methyl or tert-butyl; the substituted methyl group is-CX 3 (X is F or Cl);
more preferably, R isSubstituted phenyl, the substituted phenyl is monosubstituted, the substituted position is meta-position or para-position of benzene ring, and the substituted group is methyl, -CX 3 (X is F or Cl), tert-butyl;
more preferably, R is a substituted phenyl group which is disubstituted, the substituted positions are meta and para to the phenyl ring, the substituted groups are the same and are methyl or-CX 3 (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 used in the step (2) to the 1, 4-tetraarylbutanetetrachol is (6-30): 1, a step of;
the molar ratio of the sulfoxide chloride to the 1, 4-tetraarylbutaneterol in the step (2) is (3-6): 1, a step of;
preferably, the molar ratio of the organic base, thionyl chloride and 1, 4-tetraaryltetrol in step (2) is 30:3:1, a step of;
the specific temperature in the step (2) is-5-36 ℃, preferably-5 ℃;
the certain temperature in the step (3) is 0-90 ℃, preferably 60-90 ℃;
the certain organic solvent in the step (3) is tetrahydrofuran, N-dimethylformamide, dioxane, acetonitrile or acetone;
the inorganic alkali liquid in the step (3) is an aqueous solution of inorganic alkali, and the inorganic alkali is NaOH, KOH or Na 2 S；
The concentration of the inorganic alkali liquor in the step (3) is 1-5mol/L;
the molar ratio of the inorganic alkali in the inorganic alkali liquor to the dichloroaryl cyclic sulfite in the step (3) is (5-30): 1.
compared with the prior art, the invention has the advantages and beneficial effects that:
according to the invention, tartaric acid ester and aryl halide are used as raw materials to prepare 1, 4-tetraarylbutanetetrachol, dichloroaryl cyclic sulfite is prepared efficiently through a highly regioselective derivatization reaction of the tetraarylbutanetetrachol and thionyl chloride, carbon-carbon bond breakage occurs under the action of alkali liquor, and diaryl ketone is prepared, so that the use of expensive heavy metal-containing catalysts is avoided. The preparation method has the remarkable characteristics of easily available raw materials, simplicity and convenience in operation, excellent reaction area selectivity, easiness in treatment, high yield and the like.
Drawings
FIG. 1 is a block diagram of the di-t-butylphenyl ketone synthesized in example 1.
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples.
Example 1: the aryl is p-tert-butylphenyl, and the method for preparing diaryl ketone comprises the following steps:
(1) Preparation of 1, 4-tetra-p-tert-butylphenyl-butanetetraol
Yield: 65.6%, m.p. 243-245 ℃; 1 H 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). 13 C 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-dichloro-cyclosulfite
In a round-bottomed flask, a solution of 1, 4-tetra-p-tert-butylphenyl-butanetetrachol in tetrahydrofuran was stirred with 30 equivalents (i.e., a molar ratio of 1, 4-tetra-p-tert-butylphenyl-butanetetrachol to triethylamine of 1:30, the same applies below) of triethylamine at 0℃for 15 minutes, 3 equivalents of thionyl chloride (namely, the mol ratio of 1, 4-tetra-p-tert-butylphenyl butyl tetrol to thionyl chloride is 1:3, the same applies below) are added dropwise, the mixture is stirred for 30 minutes and then returns to room temperature (25-30 ℃), water treatment is added after stirring is continued for 30 minutes (the generated triethylamine salt is removed), and p-tert-butylphenyl dichloro-cyclosulfite is obtained by recrystallization with ethanol.Ar＝4- t BuC 6 H 4 Yield 90.0%; m.p.184 ℃; 1 H 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). 13 C 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
1:10), the mixture was heated at 70℃for 2 hours, quenched by the addition of water (complete reaction of starting material detected by TLC), and recrystallized from ethanol to give di-tert-butylphenyl ketone, yield: 73.0%, m.p. 133 ℃;1H NMR (400 MHz, chloroform-d) δ7.77 (d, J=8.2 Hz, 8H), 7.49 (d, J=8.2 Hz, 8H), 1.37 (s, 36H). 13C NMR (101 MHz, CDCl 3) δ 196.2,155.9,135.2,130.0,125.2,35.1,31.2.
Single crystal data: c (C) 21 H 26 O,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°,Z＝8,F(000)＝1280,T＝173(2)K,μ(MoKα)＝0.067mm- 1 The structure is shown in figure 1.
Example 2: the aryl is p-methylphenyl, and the preparation method of the diaryl ketone comprises the following steps:
(1) Preparation of 1, 4-tetra-p-methylphenyl-butanetetraol
(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). 13 C NMR(101MHz,DMSO-d 6 )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-cyclosulfite
In a round bottom flask, a tetrahydrofuran solution of 1, 4-tetra-p-methylphenyl butyl tetraol and 30 equivalents of triethylamine are stirred at 0 ℃ for 15 minutes, 3 equivalents of thionyl chloride are added dropwise, the mixture is stirred for 30 minutes and then returns to room temperature (25-30 ℃) and then water is added for treatment (removal of generated triethylamine salt) after stirring is continued for 30 minutes, and p-methylphenyl dichloro-cyclosulfite is obtained by recrystallization with ethanol.Ar＝4-MeC 6 H 4 Yield 90.0%; m.p.184 ℃; 1 H 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). 13 C 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
In a 25mL round bottom flask equipped with a magnetic rotor, a solution of p-methylphenyl dichloro-cyclosulfite (1 mmol) in N, N-dimethylformamide was added, and a 3mol/LNaOH aqueous solution (molar ratio of p-methylphenyl dichloro-cyclosulfite to sodium hydroxide: 1:20) was further added, and the mixture was heated at 70℃for 2 hours, and the reaction was terminated by adding water (complete reaction of the starting materials was detected by TLC), and recrystallized with ethanol to give dimethylphenyl methanone, yield: 95, m.p. 92 ℃; 1 H NMR(600MHz,Chloroform-d)δ7.70(d,J＝8.1Hz,4H),7.27(d,J＝7.9Hz,4H),2.44(s,6H). 13 C 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 method of the diaryl ketone comprises the following steps:
(1) Preparation of 1, 4-tetra-p-trifluoromethyl-phenylbutanetetraol
32％，m.p.:135-136℃, 1 H 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). 13 C NMR(101MHz,DMSO-d 6 )δ151.0,149.2,128.2,127.0,125.3,124.9,80.8,70.9.
(2) Preparation of p-trifluoromethylphenyl dichloro-cyclosulfite
In a round bottom flask, a tetrahydrofuran solution of 1, 4-tetra-p-trifluoromethylphenyl tetrol and 30 equivalents of triethylamine are stirred at 0 ℃ for 15 minutes, 3 equivalents of thionyl chloride are added dropwise, the mixture is stirred for 30 minutes and then returns to room temperature (25-30 ℃) and is further stirred for 30 minutes, water is added for treatment (the generated triethylamine salt is removed), and the p-trifluoromethylphenyl dichloro-cyclosulfite is obtained by recrystallization with ethanol.Ar＝4-CF 3 C 6 H 4 Yield 90.0%; 184 ℃ in m.p.; 1 H 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). 13 C 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
In a 25mL round bottom flask equipped with a magnetic rotor, a dioxane solution of p-trifluoromethylphenyl dichloro-cyclosulfite (1 mmol) was added, and then a 4mol/LNaOH aqueous solution (molar ratio of p-trifluoromethylphenyl dichloro-cyclosulfite to NaOH was 1:30) was added, the mixture was heated at 70℃for 2 hours, the reaction was terminated by adding water (complete reaction of the starting materials was detected by TLC), and the bis (trifluoromethylphenyl) methanone was purified by column chromatography, yield: 45%, oily matter 1 H NMR(600MHz,Chloroform-d)δ7.93–7.87(m,4H),7.82–7.76(m,4H). 13 C NMR(151MHz,Chloroform-d)δ194.4,139.7,134.3,130.2,125.7,125.6.
Example 4: the aryl is 3, 5-dimethylphenyl, and the preparation method of the diaryl ketone comprises the following steps:
(1) Preparation of 1, 4-tetra (3, 5-dimethylphenyl) butanetetraol
Grignard reagent 3, 5-dimethylphenylmagnesium bromide was prepared according to a conventional procedure, diethyl racemic tartrate was added dropwise to 6 equivalents of a tetrahydrofuran solution of 3, 5-dimethylphenylmagnesium bromide, after 2 hours of reaction, quenched with saturated aqueous ammonium chloride, extracted with diethyl ether, concentrated, and purified by silica gel column chromatography (PE/EA=6:1) to give 1, 4-tetrakis (3, 5-dimethylphenyl) butantetrol (see: helvetica Chimica Acta,2010,93,497.), yield: 52.3%, m.p. 164-165 c, 1 H 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). 13 C NMR(101MHz,DMSO-d 6 )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 dichloro-cyclosulfite
In a round-bottomed flask, a solution of 1, 4-tetra (3, 5-dimethylphenyl) butanetetraol in tetrahydrofuran and 30 equivalents of triethylamine are stirred at 0 ℃ for 15 minutes, 3 equivalents of thionyl chloride are added dropwise, the mixture is stirred for 30 minutes and then returned to room temperature (25-30 ℃) and then stirred for 30 minutes again, water is added for treatment (removal of the generated triethylamine salt), and 3, 5-dimethylphenyl dichloro-cyclosulfite is obtained by recrystallization from ethanol.Ar＝3，5-Me 2 C 6 H 4 Yield 90.0%; m.p.184 ℃; 1 H 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). 13 C 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
In a 25mL round bottom flask equipped with a magnetic rotor, an acetonitrile solution of 3, 5-dimethylphenyl dichloro-cyclosulfite (1 mmol) was added, and then a 5mol/LKOH aqueous solution (the molar ratio of 3, 5-dimethylphenyl dichloro-cyclosulfite to KOH was 1:5) was added, the mixture was heated at 70℃for 2 hours, the reaction was terminated by adding water (the reaction of the starting materials was completed by TLC detection), and the 3, 5-dimethylphenyl methanone was purified by column chromatography, yield: 75% of oily matter; 1 H NMR(400MHz,Chloroform-d)δ7.39(s,2H),7.22(s,1H),2.38(s,6H).
comparative example:
the specific 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.Soloshonok, cryst.Growth Des.2012,12,33-36.
The specific embodiments described in this specification are merely illustrative of the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (8)
1. A process for the preparation of a diaryl ketone, characterized by the steps of:
(1) Reacting tartaric acid ester with an aryl Grignard reagent to obtain 1, 4-tetraaryltetrol;
(2) Under the existence of organic alkali and specific temperature condition, 1, 4-tetraarylbutyl tetraol and thionyl chloride are subjected to high regioselective 2, 3-cyclosulfite reaction to prepare dichloro aryl cyclosulfite;
(3) Then reacting with inorganic alkali liquor in a certain organic solvent at a certain temperature to prepare diaryl ketone;
the aryl Grignard reagent in the step (1) has a general formula of RMgX, wherein R is aryl, and X is Cl, br or I; the aryl R is substituted phenyl, the substituted phenyl is monosubstituted or disubstituted, the substituted position is meta-position or para-position of benzene ring, and the substituted group is methyl, -CF 3 A tert-butyl group;
the specific temperature in the step (2) is-5-36 ℃;
the certain temperature in the step (3) is 60-90 ℃;
the certain organic solvent in the step (3) is tetrahydrofuran, N-dimethylformamide, dioxane, acetonitrile or acetone.
2. The method of manufacturing according to claim 1, characterized in that: the aryl R is p-tert-butylphenyl, p-methylphenyl, p-trifluoromethylphenyl or 3, 5-dimethylphenyl.
3. The process according to any one of claims 1 to 2, wherein the organic base in step (2) is triethylamine or pyridine.
4. The process according to any one of claims 1 to 2, wherein the molar ratio of the amount of the organic base, the amount of thionyl chloride and 1, 4-tetraarylbutaneterol in step (2) is (6-30): (3-6): 1.
5. the process of claim 4, wherein the molar ratio of the organic base, thionyl chloride and 1, 4-tetraarylbutaneterol in step (2) is 30:3:1.
6. the process according to any one of claims 1 to 2, wherein the inorganic base of the inorganic alkaline solution in step (3) isNaOH, KOH or Na 2 S。
7. The process according to claim 6, wherein the molar ratio of the amount of the inorganic base used in the inorganic alkaline solution to the dichloroaryl cyclosulfite in the step (3) is (5-30): 1.
8. the process according to claim 6, wherein the concentration of the inorganic lye in the step (3) is 1 to 5 mol/L.
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| CN102603705A (en) * | 2012-03-27 | 2012-07-25 | 武汉大学 | Preparation method of chiral five-membered ring sulfite with active functional groups on alpha-carbon in substituent |
| CN103936703A (en) * | 2013-01-17 | 2014-07-23 | 上海朴颐化学科技有限公司 | Preparation method of 5-oxaspiro[2,4]heptane-6-one and intermediate thereof |
| CN108276256A (en) * | 2018-02-10 | 2018-07-13 | 中南民族大学 | The preparation method of (2R, 3R) -2,3- dimethoxy -1,1,4,4- tetraphenyl -1,4- butanediols |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603705A (en) * | 2012-03-27 | 2012-07-25 | 武汉大学 | Preparation method of chiral five-membered ring sulfite with active functional groups on alpha-carbon in substituent |
| CN103936703A (en) * | 2013-01-17 | 2014-07-23 | 上海朴颐化学科技有限公司 | Preparation method of 5-oxaspiro[2,4]heptane-6-one and intermediate thereof |
| CN108276256A (en) * | 2018-02-10 | 2018-07-13 | 中南民族大学 | The preparation method of (2R, 3R) -2,3- dimethoxy -1,1,4,4- tetraphenyl -1,4- butanediols |
Non-Patent Citations (1)
| Title |
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| First Experimental Evidence of an Intramolecular H Bond between Aliphatic Cl and Aromatic C-H;First Experimental Evidence of an Intramolecular H Bond between Aliphatic Cl and Aromatic C-H;《Cryst. Growth Des.》;第12卷;第33-36页 * |
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