CN110483261B - Method for catalytic dehydrogenation of aryl secondary alcohol into ketone - Google Patents
Method for catalytic dehydrogenation of aryl secondary alcohol into ketone Download PDFInfo
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- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
- C07D311/82—Xanthenes
- C07D311/84—Xanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
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Abstract
The invention discloses a method for catalytic dehydrogenation of aryl secondary alcohol into ketone, which comprises the steps of dissolving the aryl secondary alcohol in an organic solvent, and reacting at 40-120 ℃ in the presence of an acid catalyst and a cocatalyst to obtain substituted aryl ketone, wherein the acid is aryl sulfonic acid (ArSO)3H) Alkyl sulfonic acid (RSO)3H) Or boron trifluoride diethyl etherate, and the cocatalyst is tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon. The method does not use metal catalyst and oxidant, the used catalyst is cheap and nontoxic, can tolerate water and air, has mild reaction conditions, simple operation and high atom economy, and can be produced in large scale.
Description
Technical Field
The invention relates to a conversion reaction of secondary alcohol, in particular to a method for catalytic dehydrogenation of aryl secondary alcohol into ketone.
Background
The selective oxidation of secondary aryl alcohols to ketone compounds is a very important and fundamental organic conversion reaction. The product plays an important role in organic synthesis intermediates, medicine synthesis and the composition of pesticides, spices and pigments. For example, benzophenone is commonly used in the synthesis of diphenhydramine hydrochloride, benztropine hydrobromide and dicyclohexylpiperidine, and is a fixative.
Stoichiometric amounts of Chromium (VI), manganese oxidant, Jones reagent, PDC oxidation system, NaClO solution have been used to accomplish the oxidation of secondary alcohols (S.V.Ley, A.Madin, in: B.M.Trost, I.Fleming (Eds.), Comprehensive Organic Synthesis, vol.7,1991 (pp.305-327); G.Cainelli, G.Cardiolo, Chromium oxides in Organic Chemistry, Springer Verlag, Berlin, 1984). They are generally toxic, hazardous, and produce heavy metal waste or large quantities of undesirable compounds. Later, various non-metallic oxidizing agents including peracetic acid, t-butoxyphenyl peroxide, iodoxybenzene, TEMPO were used as the oxidizing agent under metal catalysis. For example, t-butyl hydroperoxide (TBHP) is used as an oxidant, and Pawel j.fig. provides a 2, 4-alkoxy-1, 3, 5-triaza-pentadienoic acid coordinated cu (ii) compound that catalyzes the oxidation of secondary alcohols to ketones under microwave heating (chem.commun.,2010,46, 2766-; bauer et al (chem. commun.2013,49,5889-5891) used iron complexes of bidentate and tridentate aminopyridine ligands to catalyze secondary alcohols to ketones with peroxyacetic acid as oxidant to obtain good chemoselectivity; sunwei by Lanzhou (org. Lett., 2015, 17,54-57) uses hydrogen peroxide as an oxidant, acetic acid as an additive, and the manganese complex Mn (S-PMB) - (CF)3SO3)2Catalytic oxidation of secondary alcohols gives the corresponding ketones. However, most non-metallic oxidizers produce large amounts of stoichiometric reagent waste and produce unwanted by-products that severely pollute the environment, and the catalysts used are typically in the form of expensive cobalt, copper, iron complexes, which are generally unstable and slowly disappear or decompose under oxidizing conditions.
In summary, there is an urgent need to develop a clean catalytic oxidation process using the theory and method of green chemistry from the viewpoint of atom economy and environmental protection.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the existing method for catalytically oxidizing aryl secondary alcohol into ketone, and provide a method for catalytically dehydrooxidizing aryl secondary alcohol into ketone, wherein the method does not use a metal catalyst or an oxidant, and the used catalyst is low in cost and non-toxic.
The invention is realized by the following technical scheme:
a method for catalytic dehydrogenation of aryl secondary alcohol into ketone adopts an acid catalyst and a cocatalyst to catalyze the reaction of the aryl secondary alcohol to generate aryl ketone, wherein the acid catalyst is aryl sulfonic acid, alkyl sulfonic acid or boron trifluoride diethyl etherate, and the cocatalyst is tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon.
Preferably, the method comprises the following specific steps: dissolving aryl secondary alcohol in an organic solvent, adding an acid catalyst and a cocatalyst, and carrying out catalytic reaction at 40-120 ℃ for 0.5-12 hours to obtain aryl ketone.
Further, the reaction time is 1-5 hours.
Preferably, the aryl secondary alcohol is xanthene alcohol or
In the formula, Ar1Represents phenyl, naphthyl, substituted phenyl or substituted naphthyl, Ar2Represents phenyl or substituted phenyl, Ar1And Ar2The substituents in the substituted phenyl group represented by (A) are each independently CH3、CH3O、F、CF3、Cl、Br、NO2or-CH2-OCH2-，Ar1The substituent in the substituted naphthyl group is CH3、CH3O、F、CF3Cl, Br or NO2。
Preferably, the arylsulfonic acid has the formula ArSO3H, Ar represents phenyl, naphthyl, substituted phenyl or substituted naphthyl, and substituents in the substituted phenyl and the substituted naphthyl represented by Ar are each independently CH3、CH3O、F、CF3Cl, Br or NO2。
Preferably, the alkylsulfonic acid has the formula RSO3H, wherein R represents C1～C3Alkyl, CHF2Or CF3。
Preferably, the cocatalyst is any one of tert-butyl chloride, tert-butyl bromide, benzyl chloride and benzyl bromide.
Preferably, the organic solvent is any one of dichloroethane, monochloromethane, chloroform, dichloromethane, dimethyl sulfoxide, carbon tetrachloride, acetonitrile, dioxane, acetone, tetrahydrofuran, ethyl acetate, cyclohexane, benzene, toluene, xylene, and nitromethane.
Preferably, the amount of the acid catalyst is 5 to 50 percent of the molar amount of the aryl secondary alcohol.
Preferably, the amount of the cocatalyst is 1-2 times of the molar amount of the aryl secondary alcohol.
Compared with the prior art, the invention has the following beneficial technical effects:
the present invention uses arylsulfonic acids (ArSO)3H) Alkyl sulfonic acid (RSO)3H) Or boron trifluoride diethyl etherate is used as a catalyst, tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon is used as a cocatalyst, and the aryl secondary alcohol is directly catalyzed to perform dehydrogenation reaction under the conditions of no metal catalyst and no oxidant to obtain the aryl ketone compound. In the reaction process, firstly, acid is catalyzed by tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon to form carbocation, and then the carbocation breaks the methine carbon-hydrogen bond of aryl secondary alcohol, captures the hydride of the carbon-hydrogen bond, and forms ketone product. The process used in the present invention, unlike the metal catalyzed free radical reactions described above, avoids the use of expensive metal complexes or the use of strong oxidants which are sensitive to water and air. The reaction condition is mild, the operation is easy, the price is low, the catalyst is nontoxic, and the large-scale production can be realized. The aryl ketone compound prepared by the method has great application potential in the preparation of medicines, natural products and organic synthesis intermediates.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The method for catalytic dehydrooxidation of aryl secondary alcohol into ketone comprises the steps of dissolving aryl secondary alcohol in an organic solvent, and reacting for 0.5-12 hours at 40-120 ℃ in the presence of an acid catalyst and a tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon cocatalyst to obtain aryl ketone, wherein the acid catalyst is aryl sulfonic acid (ArSO)3H) Alkyl sulfonic acid (RSO)3H) Or boron trifluoride diethyl etherate, and the addition amount of the acid catalyst is 5 to 50 percent of the molar amount of the aryl secondary alcohol.
The aryl secondary alcohol is xanthene alcohol or
In the formula, Ar1Represents phenyl, naphthyl, substituted phenyl or substituted naphthyl, Ar2Represents phenyl or substituted phenyl, Ar1And Ar2The substituents in the substituted phenyl group represented by (A) are each independently CH3、CH3O、F、CF3、Cl、Br、NO2or-CH2-OCH2-，Ar1The substituent in the substituted naphthyl group is CH3、CH3O、F、CF3Cl, Br or NO2。
The acid catalyst of the invention is ArSO3H or RSO3H, Ar represents phenyl, naphthyl, substituted phenyl or substituted naphthyl, R represents C1～C3Alkyl, CHF2Or CF3And the substituents in the substituted phenyl and substituted naphthyl represented by Ar are each independently CH3、CH3O、F、CF3Cl, Br or NO2。
The cocatalyst of the invention is tert-halohydrocarbon or benzyl halohydrocarbon, which is any one of tert-butyl chloride, tert-butyl bromide, benzyl chloride and benzyl bromide, and the dosage of the cocatalyst is 1-2 times of the molar weight of the aryl secondary alcohol. The organic solvent is any one of dichloroethane, methane chloride, chloroform, dichloromethane, dimethyl sulfoxide, carbon tetrachloride, acetonitrile, dioxane, acetone, tetrahydrofuran, ethyl acetate, cyclohexane, benzene, toluene, xylene and nitromethane.
The reaction time in the present invention is more preferably 1 to 5 hours.
Example 1
Taking benzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method thereof are as follows:
p-toluenesulfonic acid (0.3mmol, 0.50g), tert-butyl chloride (0.6mmol, 0.030mL), benzhydrol (0.6mmol, 0.11g) were added to dichloroethane (0.5mL) in this order, stirred at room temperature and then heated to 60 ℃ with stirring, the reaction was stopped after 2 hours of reaction, 2mL of saturated aqueous sodium bicarbonate solution was added to the system, extracted three times with 10mL of ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by column chromatography (hexane/EtOAc) to give the product as a white solid in an isolated yield of 83%. The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ196.5,137.6,132.4,130.0,128.3.
example 2
Taking 4-methylbenzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method are as follows:
in example 2, the benzhydrol used was replaced by an equimolar amount of 4-methylbenzophenone and the other procedure was the same as in example 1 to prepare 4-methylbenzophenone as a white solid in an isolated yield of 86%, characterized by:1H NMR(600MHz,CDCl3)δ7.82–7.77(m,2H),7.73(d,J＝8.1Hz,2H),7.57(d,J＝7.3Hz,1H),7.47(t,J＝7.7Hz,2H),7.30–7.25(m,2H),2.44(s,3H)；13C NMR(151MHz,CDCl3)δ196.5,143.2,138.0,134.9,132.1,130.3,1299,129.0,128.2,21.6 example 3
Example 3
Taking 4-nitrobenzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method are as follows:
in example 3, the benzhydrol used was replaced by an equimolar amount of 4-nitrobenzyl alcohol and the other procedure was the same as in example 1 to prepare 4-nitrobenzophenone as a white solid in an isolated yield of 72% characterized by the following data:1H NMR(600MHz,CDCl3)δ8.26(d,J＝8.2Hz,2H),7.92(d,J＝8.1Hz,2H),7.82–7.77(m,2H),7.57(d,J＝7.3Hz,1H),7.47(t,J＝7.7Hz,2H)；13C NMR(151MHz,CDCl3)δ194.8,149.1,142.9,136.3,133.5,130.7,130.2,128.7,123.6
example 4
Taking the preparation of 1-naphthyl benzophenone, which is a compound of the following formula, as an example, the raw materials and the preparation method thereof are as follows:
in example 4, the benzhydrol used was replaced by equimolar 1-naphthyl benzyl alcohol and the other steps were the same as in example 1 to prepare 1-naphthyl benzophenone as a pale yellow solid with an isolated yield of 82%, characterized by:1H NMR(600MHz,CDCl3)δ9.10(d,J＝8.1Hz,1H),8.00–7.96(m,2H),7.80(d,J＝7.9,Hz,1H),7.12–7.10(m,3H),6.90(d,J＝7.2Hz,1H),7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ198.3,143.7,140.6,138.9,138.5,136.0,134.3,133.4,132.4,131.5,130.1,124.4,128.6.
example 5
Taking 4-bromobenzophenone as an example for preparing the compound shown in the following formula, the raw materials and the preparation method thereof are as follows:
in example 5, the benzhydrol used was replaced with an equimolar amount of 4-bromobenzhydrol and the other procedure was the same as in example 1 to prepare a white solid with an isolated yield of 85% and the characterization data is:1H NMR(600MHz,CDCl3)δ7.79–7.76(m,2H),7.69-7.58(m,5H),7.49(dd,J＝7.4,8.0Hz,2H)；13C NMR(151MHz,CDCl3)δ195.6,137.1,136.3,132.6,131.6,131.5,129.9,128.2,127.5.
example 6
Taking the preparation of 2-methylbenzophenone of the following formula as an example, the raw materials and the preparation method are as follows:
in example 6, the benzhydrol used was replaced by an equimolar amount of 2-methylbenzyl alcohol and the other procedure was the same as in example 1 to prepare a white solid with an isolated yield of 80%, characterized by:1H NMR(600MHz,CDCl3)δ7.81–7.79(m,2H),7.60-7.56(m,1H),7.49–7.44(m,2H),7.41–7.38(m,1H),7.32–7.29(m,2H),7.26–7.23(m,1H),2.33(s,3H)；13C NMR(151MHz,CDCl3)δ198.6,138.6,137.7,136.7,133.1,132.4,131.0,130.1,128.5,128.4,125.2,20.0.
example 7
Taking the preparation of the compound 9H-heteroanthracen-9-one of the following formula as an example, the raw materials and the preparation method thereof are as follows:
in example 7, the benzhydrol used was replaced by an equimolar amount of xanthanol and the other procedure was the same as in example 1 to prepare 9H-heteroanthran-9-one as a white solid in an isolated yield of 79%, characterized by the following data:1H NMR(400MHz,CDCl3)δ8.25(dd,J＝8.0,1.5Hz,2H),7.63(ddd,J＝8.7,7.1,1.7Hz,2H),7.40(dd,J＝8.5,0.6Hz,2H),7.29(ddd,J＝8.1,7.2,1.0Hz,2H).13C NMR(101MHz,CDCl3)δ176.2,155.1,133.8,125.7,122.9,120.8,116.9.
example 8
Taking benzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method thereof are as follows:
in example 8, dichloroethane used as a solvent was replaced with an equal amount of toluene, tert-butyl chloride was replaced with an equal amount of benzyl chloride, the reaction temperature was replaced with 120 ℃, and the other steps were the same as in example 1 to prepare benzophenone as a white solid in an isolated yield of 80%. The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ196.5,137.6,132.4,130.0,128.3.
example 9
Taking benzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method thereof are as follows:
in example 9, p-toluenesulfonic acid used was replaced with an equimolar amount of boron trifluoride etherate, the amount of tert-butyl chloride was replaced with twice the amount used in example 1, the reaction time was replaced with 12 hours, the reaction temperature was replaced with 40 ℃, and other procedures were the same as in example 1 to prepare benzophenone as a white solid in an isolated yield of 80%. The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ196.5,137.6,132.4,130.0,128.3.
example 10
Taking benzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method thereof are as follows:
in example 10, the amount of p-toluenesulfonic acid used was replaced with 0.18mmol (0.31g), the reaction time was replaced with 1h, and the other steps were the same as in example 1 to prepare benzophenone as a white solid with an isolated yield of 86%. The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ196.5,137.6,132.4,130.0,128.3.
example 11
Taking benzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method thereof are as follows:
in example 11, using the amount of p-toluenesulfonic acid was replaced with 0.03mmol (0.11g), using the reaction time was replaced with 0.5 hour, using the reaction temperature was replaced with 120 ℃, and the other steps were the same as in example 1 to prepare benzophenone as a white solid with an isolated yield of 65%. The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ196.5,137.6,132.4,130.0,128.3.
example 12
Taking benzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method thereof are as follows:
in example 12, the amount of t-butyl chloride used was replaced with 0.9mmol (0.045mL), the reaction temperature was replaced with 80 ℃ and the reaction time was replaced with 5 hours, and the other steps were the same as in example 1 to prepare benzophenone as a white solid in an isolated yield of 82%. The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ196.5,137.6,132.4,130.0,128.3.
example 13
Taking benzophenone as an example for preparing the compound shown in the formula, the raw materials and the preparation method thereof are as follows:
in example 13, p-toluenesulfonic acid used was replaced with an equimolar amount of trifluoromethanesulfonic acid, and the other procedure was the same as in example 1, to prepare benzophenone as a white solid with an isolated yield of 85%. The obtained product is characterized by a Bruker Avance type superconducting Fourier digital nuclear magnetic resonance spectrometer, and the characterization data is as follows:1H NMR(600MHz,CDCl3)δ7.56(dd,J＝8.4,1.2Hz,2H),7.30(d,J＝7.5Hz,1H),7.25–7.17(m,2H).13C NMR(151MHz,CDCl3)δ196.5,137.6,132.4,130.0,128.3.
Claims (6)
1. a method for catalytic dehydrogenation of aryl secondary alcohol into ketone is characterized in that an acid catalyst and a cocatalyst are adopted to catalyze the reaction of aryl secondary alcohol to generate aryl ketone, wherein the acid catalyst is p-toluenesulfonic acid, trifluoromethanesulfonic acid or boron trifluoride diethyl etherate, and the cocatalyst is tertiary halogenated hydrocarbon or benzyl halogenated hydrocarbon;
the aryl secondary alcohol is xanthene alcoholOr
In the formula, Ar1Represents phenyl, naphthyl, substituted phenyl or substituted naphthyl, Ar2Represents phenyl or substituted phenyl, Ar1And Ar2The substituents in the substituted phenyl group represented by (A) are each independently CH3、CH3O、F、CF3、Cl、Br、NO2or-CH2-OCH2-，Ar1The substituent in the substituted naphthyl group is CH3、CH3O、F、CF3Cl, Br or NO2；
The cocatalyst is any one of tert-butyl chloride, tert-butyl bromide, benzyl chloride and benzyl bromide.
2. The process for the catalytic dehydrogenation of aryl secondary alcohols to ketones according to claim 1, characterized by the specific steps of: dissolving aryl secondary alcohol in an organic solvent, adding an acid catalyst and a cocatalyst, and carrying out catalytic reaction at 40-120 ℃ for 0.5-12 hours to obtain aryl ketone.
3. A process for the catalytic dehydrogenation of aryl secondary alcohols to ketones according to claim 2, wherein the reaction time is 1 to 5 hours.
4. A process for the catalytic dehydroxidation of secondary aryl alcohols to ketones according to any of claims 1-3 wherein the organic solvent is any of dichloroethane, methyl chloride, chloroform, dichloromethane, dimethyl sulfoxide, carbon tetrachloride, acetonitrile, dioxane, acetone, tetrahydrofuran, ethyl acetate, cyclohexane, benzene, toluene, xylene and nitromethane.
5. A process for the catalytic dehydrooxidation of secondary aryl alcohols to ketones as claimed in any one of claims 1 to 3 wherein the amount of acid catalyst is between 5% and 50% of the molar amount of secondary aryl alcohol.
6. A process for the catalytic dehydrooxidation of secondary aryl alcohols to ketones as claimed in any of claims 1 to 3 wherein the amount of co-catalyst is 1 to 2 times the molar amount of secondary aryl alcohol.
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