CN111362796B - Method for reducing and hydrogenating tertiary alkyl alcohol - Google Patents
Method for reducing and hydrogenating tertiary alkyl alcohol Download PDFInfo
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- CN111362796B CN111362796B CN202010236807.0A CN202010236807A CN111362796B CN 111362796 B CN111362796 B CN 111362796B CN 202010236807 A CN202010236807 A CN 202010236807A CN 111362796 B CN111362796 B CN 111362796B
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- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention discloses a method for reducing and hydrogenating tertiary alkyl alcohol, which takes oxalate prepared in advance for tertiary alkyl alcohol as a raw material to react for 8 to 12 hours at a temperature of between 40 and 60 ℃ under the action of a nickel source, a ligand, a hydrogen donor, a reducing agent, an additive and a solvent to obtain a product of reducing and hydrogenating the tertiary alkyl alcohol. The invention utilizes tertiary alkyl alcohol to prepare tertiary alkyl oxalate as a reaction precursor, adopts zinc powder/magnesium chloride as a medium to catalyze and reduce the non-activated tertiary alkyl oxalate, promotes the C-O bond of the oxalate to be broken by nickel, and uses diphenylsilane as a hydrogen donor to prepare a reduction product. The method has the advantages of cheap catalyst metal, simple and easily-obtained raw materials, mild reaction, one-step reaction, simple steps, safe operation, high yield and low cost.
Description
Technical Field
The invention relates to a method for preparing a reduction hydrogenation product, in particular to a method for preparing a reduction hydrogenation product by taking an alcohol compound as a raw material, which is applied to the technical field of organic synthesis.
Background
The promotion of alkyl radicals by transition metal catalysis and their application in organic reactions have been one of the leading and popular research areas in organic chemistry.
Alcohol compounds are a very inexpensive class of compounds that are widely found in nature. At present, the methods for preparing corresponding alkanes by breaking C-O bonds mainly comprise the following steps:
(1) Alcohol compounds are used as raw materials, and C-O bonds are broken at high temperature under the action of a ruthenium or iridium catalyst and hydrazine hydrate to obtain corresponding alkane, but the method needs extremely toxic hydrazine hydrate, has high danger and has expensive catalyst price (J.Am.chem.Soc., 2016,138, 5433-5440.);
(2) P-toluenesulfonate and methanesulfonate are used as raw materials, and react with sodium borohydride to break a C-O bond to obtain corresponding alkane, and the method has the defects of narrow substrate range, poor selectivity and the like (ACS Med. Chem. Lett.2017.8 (4), 438-442.);
(3) The method takes ketone compounds as substrates and triethoxysilane or borane as reducing reagents to realize the fracture of C-O double bonds and obtain corresponding alkanes, but the method has large consumption of the reducing reagents and strict reaction conditions (Bio. & Med. Chemistry Letters,2009,19 (15): 4213-4216);
(4) Taking benzoate as a raw material, and realizing the homolytic cleavage of C-O bonds by using an electrochemical method to generate a corresponding reduction hydrogenation product. However, this method also has the disadvantages of complicated procedure, complicated operation, poor selectivity, etc. (chem.
Disclosure of Invention
In order to solve the problems of the prior art, the invention aims to overcome the defects in the prior art and provide a method for reducing and hydrogenating tertiary alkyl alcohol.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a method for reducing and hydrogenating tertiary alkyl alcohol comprises the following steps:
under inert atmosphere, taking oxalate prepared in advance by using tertiary alkyl alcohol as a raw material, dissolving oxalate, a hydrogen donor, a ligand, a nickel source, an additive and a reducing agent in a solvent according to the molar ratio of 1.0-2.0:
wherein R is 1 ,R 2 ,R 3 Is any one or more of hydrogen, methyl, phenethyl, benzoyl, cyclohexyl and 3-hydroxy-3-methylbutyl;
the structural formula of the oxalate is as follows:
wherein R is 1 ,R 2 ,R 3 Is hydrogen, methyl, phenethylAny one or more of phenyl, benzoyl, cyclohexyl and 3-hydroxy-3-methylbutyl;
the hydrogen donor is silane; the ligand is a nitrogen-containing ligand; the nickel source is a nickel catalyst; the additive is a magnesium salt; the reducing agent is zinc powder.
The amount of the nickel source is preferably 20 to 50% by mass of the oxalate.
The amount of the ligand is preferably 100 to 150% by mass of the oxalate.
The amount of the additive is preferably 200 to 250% of the mass of the oxalate.
Preferably, the solvent is N, N-dimethylacetamide, and the molar concentration of the N, N-dimethylacetamide in the mixed reactants is not less than 0.075M.
Preferably, the nickel source is NiCl 2 。
Preferably, 2- (2-pyridine) -benzimidazole is used as the ligand.
Preferably, diphenylsilane is used as the hydrogen donor.
Preferably, anhydrous magnesium chloride is used as the additive.
Preferably, zinc powder is used as the reducing agent.
Preferably, the solvent is anhydrous N, N-dimethylacetamide.
As a preferable technical scheme, the method for reducing and hydrogenating the tertiary alkyl alcohol takes (3-benzoyloxy-1, 1-dimethylpropyl) methyl oxalate as a raw material to synthesize the isoamyl benzoate, and the structural formula of the method is as follows:
the principle of the invention is as follows:
the reaction mechanism adopted by the invention is as follows: oxalate prepared in advance by using tertiary alkyl alcohol is taken as a raw material, and a C-O bond is broken under the combined action of a nickel source, a nitrogen-containing ligand, a reducing agent, an additive, a hydrogen donor and a solvent to generate a corresponding reduction hydrogenation product.
Wherein R is 1 ,R 2 ,R 3 Is any one or more of hydrogen, methyl, phenethyl, benzoyl, cyclohexyl and 3-hydroxy-3-methylbutyl.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the method provided by the invention has the advantages that a new way is provided for synthesizing complex compounds under relatively mild and simple conditions by a Ni/Zn reduction system and a method for generating alkyl free radicals by breaking C-O bonds; the reaction of the invention has the characteristics of simple steps, convenient operation, high yield, wide substrate adaptability and the like; the reaction of the invention has potential research value for asymmetric hydrogenation reaction, and has important significance in the field of biological medicine and synthesis of natural products;
2. the method adopts oxalate as raw material, is easy to prepare, simple and easily obtained, and is relatively stable and convenient to store; the nickel source is cheap and easy to obtain, and the method is green, environment-friendly, low in toxicity and high in efficiency; the reaction is mild, and the operation and the post-treatment are simpler; high reaction yield, good substrate adaptability, low cost and suitability for industrial application.
Detailed Description
The above-described embodiments are further illustrated below with reference to specific examples, in which preferred embodiments of the invention are detailed below:
example one
In this example, a method for reducing and hydrogenating tertiary alkyl alcohol, which uses (3-benzoyloxy-1, 1-dimethylpropyl) methyl oxalate as a raw material to synthesize isoamyl benzoate, the structural formula of which is:
the method for reducing and hydrogenating the tertiary alkyl alcohol comprises the following steps:
to a dried Schlenk tube were added 0.15mmol of (3-benzoyloxy-1, 1-dimethylpropyl) methyl oxalate, 0.15mmol of the ligand 2- (2-pyridine) -benzimidazole, 0.375mmol of zinc powder, 0.3mmol of anhydrous magnesium chloride, 0.03mmol of nickel chloride in that order, then the Schlenk tube was evacuated three times using a double-row tube to ensure the reaction under nitrogen atmosphere, 0.3mmol of diphenylsilane was added with a microinjector, finally 2mL of anhydrous N, N-dimethylacetamide was added with a syringe and stirred at 40 ℃ for 12h; after the reaction is finished, directly using ethyl acetate: the volume ratio of the petroleum ether is 10:90 was subjected to column chromatography to give isoamyl benzoate as a colorless liquid in 86% yield.
Experimental test analysis:
the isoamyl benzoate prepared in this example was subjected to structural identification.
1 H NMR(600MHz,Chloroform-d)δ8.07–8.02(m,2H),7.57–7.52(m,1H),7.43(t,J＝7.8Hz,2H),4.36(t,J＝6.8Hz,2H),1.87–1.77(m,1H),1.67(q,J＝6.8Hz,2H),0.98(d,J＝6.7Hz,6H)
13 C NMR(150MHz,Chloroform-d)δ166.78,132.89,130.65,129.64,128.42,63.73,37.54,25.33,22.63.
By combining the data and analysis, the compound is determined to be isoamyl benzoate, and the structural formula is as follows:
Example two
The present embodiment is substantially the same as the first embodiment, and the special points are that:
in this example, a method of reductive hydrogenation of tertiary alkyl alcohol was used toThe (3-benzoyloxy-1, 1-dimethylpropyl) methyl oxalate is used as a raw material to synthesize the isoamyl benzoate, and the structural formula is as follows:
the method for reducing and hydrogenating the tertiary alkyl alcohol comprises the following steps:
to a dried Schlenk tube were added 0.15mmol of (3-benzoyloxy-1, 1-dimethylpropyl) methyl oxalate, 0.225mmol of the ligand 2- (2-pyridine) -benzimidazole, 0.225mmol of zinc dust, 0.375mmol of anhydrous magnesium chloride, 0.075mmol of nickel chloride in that order, then the Schlenk tube was evacuated three times using a double-row tube to ensure the reaction under nitrogen atmosphere, 0.15mmol of diphenylsilane was added with a microinjector, finally 2mL of anhydrous N, N-dimethylacetamide was added with a syringe and stirred at 60 ℃ for 8h; after the reaction is finished, without post-treatment, ethyl acetate is directly used: the volume ratio of the petroleum ether is 10:90 was subjected to column chromatography to give isoamyl benzoate as a colorless liquid in a yield of 91%.
Experimental test analysis:
the isoamyl benzoate prepared in this example was subjected to structural identification.
In the method, oxalic ester prepared in advance by using the tertiary alkyl alcohol is used as a raw material, and the reaction is carried out under the action of a nickel source, a ligand, a hydrogen donor, a reducing agent, an additive and a solvent to obtain a product of the reduction hydrogenation of the tertiary alkyl alcohol. The method has the advantages of cheap catalyst metal, simple and easily-obtained raw materials, high reaction yield, good substrate adaptability, mild reaction, one-step reaction, simple steps, safety in operation, high yield, low cost and suitability for industrial application.
While the embodiments of the present invention have been described, the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications made according to the spirit and principles of the present invention should be made in an equivalent manner, so long as the objects of the present invention are met, and the present invention is within the protection scope of the present invention without departing from the technical principles and inventive concepts of the method for three-stage alkyl alcohol reduction hydrogenation of the present invention.
Claims (6)
1. A method for reducing and hydrogenating tertiary alkyl alcohol is characterized by comprising the following steps:
under an inert atmosphere, using oxalate prepared in advance by using a tertiary alkyl alcohol as a raw material, dissolving the oxalate, a hydrogen donor, a ligand, a nickel source, an additive and a reducing agent in a molar ratio of 1.0 to 2.0:
wherein R is 1 ,R 2 ,R 3 Is any one or more of methyl, phenethyl, benzoyl, cyclohexyl and 3-hydroxy-3-methylbutyl;
the structural formula of the oxalate is as follows:
wherein R is 1 ,R 2 ,R 3 Is any one or more of methyl, phenethyl, benzoyl, cyclohexyl and 3-hydroxy-3-methylbutyl;
the hydrogen donor is diphenylsilane, and the ligand adopts 2- (2-pyridine) -benzimidazole; the nickel source adopts NiCl 2 (ii) a The additive adopts anhydrous magnesium chloride; the reducing agent adopts zinc powder; the solvent adopts anhydrous N, N-dimethylacetamide.
2. The method of claim 1, comprising the step of reductively hydrogenating the tertiary alkyl alcohol, wherein: the using amount of the nickel source is 20 to 50 percent of the mass of the oxalate.
3. The process for the reductive hydrogenation of a tertiary alkyl alcohol according to claim 1, wherein: the dosage of the ligand is 100 to 150 percent of the mass of the oxalate.
4. The process for the reductive hydrogenation of a tertiary alkyl alcohol according to claim 1, wherein: the dosage of the additive is 200 to 250 percent of the mass of the oxalate.
5. The method of claim 1, comprising the step of reductively hydrogenating the tertiary alkyl alcohol, wherein: the solvent is N, N-dimethylacetamide, and the molar concentration of the N, N-dimethylacetamide in the mixed reactants is not less than 0.075M.
6. The method of claim 1, comprising the step of reductively hydrogenating the tertiary alkyl alcohol, wherein: taking (3-benzoyloxy-1, 1-dimethylpropyl) methyl oxalate as a raw material to synthesize isoamyl benzoate, wherein the structural formula is as follows:
。
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