CN103772151A - Preparation method of 2-methyl-3-phenyl benzyl alcohol - Google Patents
Preparation method of 2-methyl-3-phenyl benzyl alcohol Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
Abstract
The invention relates to a preparation method of 2-methyl-3-phenyl benzyl alcohol. The preparation method comprises the steps of (1) under a lighting condition, enabling 2,3-dimethyl biphenyl to mix and react with chlorine gas at 40-120 DEGC; or, in the presence of an initiator, enabling the 2,3-dimethyl biphenyl to react with sulfuryl chloride or chlorine gas at 40-120 DEG C; (2) implementing an esterification reaction on 2-methyl-3-chloromethyl biphenyl prepared by the step (1) and an esterification reagent in a solvent in the presence of a catalyst; and (3) under an alkaline condition, hydrolyzing an esterification product prepared by the step (2), and controlling pH range within 9-14. The preparation method disclosed by the invention is simple and convenient to operate, relatively low in cost, not high in requirement on equipment and applicable to industrial production. (img file='DDA0000466672690000011. TIF'wi='1528'he='344'/).
Description
Technical field
The present invention relates to a kind of preparation method of 2-methyl-3-phenyl benzil alcohol.
Background technology
2-methyl-3-phenyl benzil alcohol is an important intermediate producing agricultural chemicals bifenthrin and other agricultural chemicals medicine.
The method of preparing at present 2-methyl-3-phenyl benzil alcohol mainly contains four kinds:
First method is with 2,6-toluene dichloride is raw material, THF is solvent, after a step grignard reaction, reacts make 3-chloro-2-methyl biphenyl with bromobenzene under catalyzer, then in THF, carries out obtaining target product with formaldehyde gas or paraformaldehyde direct reaction after second step grignard reaction.
Second method (CN1935761A, CN101130485A) be with 2,6-toluene dichloride is raw material, THF is solvent, after a step grignard reaction, react under catalyzer with bromobenzene and make 3-chloro-2-methyl biphenyl, then in THF, carry out directly reacting generation 2-methyl-3-phenyl phenyl aldehyde with DMF after second step grignard reaction, then obtain target product with NaBH4 or the reduction of other metallic reducing agent.
The third method (CN101704723A) is take 2-methyl-3-chloroaniline as raw material, under the existence of metal catalyst, acids promotor and nitrous acid ester, carrying out diazonium coupling with benzene reacts and makes 2-methyl-3-chlordiphenyl, carry out again grignard reaction, carbonyl addition makes 2-methyl-3-phenyl phenyl aldehyde, finally under metallic reducing agent reduction, obtain.
The 4th kind of method (CN102603485A) is take the bromo-2-tolyl acid of 3-as raw material, under palladium-containing catalyst catalysis, there is Suzuki linked reaction with phenyl substituted boracic acid/phenyl substituted boracic acid salt and make 3-phenyl-2-tolyl acid, then obtain target product through reduction.
But method one, method two and method three have all been applied to grignard reaction, need anhydrous and oxygen-free operation, and equipment cost is higher.Method two, three, four need use the carbonyl reduction agent that price is more expensive, and cost is higher.
Summary of the invention
Technical problem to be solved by this invention is, in order to overcome, preparation method's cost of 2-methyl-3-phenyl benzil alcohol in prior art is higher, complex operation, higher to equipment requirements, be unfavorable for the defects such as suitability for industrialized production, and a kind of preparation method of 2-methyl-3-phenyl benzil alcohol is provided.Preparation method of the present invention is easy and simple to handle, cost is lower, and less demanding for equipment is applicable to the needs of suitability for industrialized production.
The preparation method who the invention provides a kind of 2-methyl-3-phenyl benzil alcohol, it comprises the steps:
Step (1): under illumination condition, by 2,3-dimethyl diphenyl (DMBP) and chlorine hybrid reaction, temperature of reaction is 40 ℃～120 ℃;
Or, under initiator condition, by 2,3-dimethyl diphenyl (DMBP), to react with SULPHURYL CHLORIDE or chlorine, temperature of reaction is 40 ℃～120 ℃;
Step (2): in solvent, under catalyzer condition, 2-methyl-3-chloromethyl biphenyl (MCMBP) that step (1) is prepared carries out esterification with esterifying reagent;
Step (3): under alkaline condition, the esterification products that step (2) is prepared is hydrolyzed, controlling pH scope is 9～14;
In step (1), the reaction under illumination condition, preferably includes following steps: 2,3-dimethyl diphenyl is warming up to 40 ℃～120 ℃, opens illumination, pass into chlorine and react.
In step (1), described illumination condition, without particular requirement, can be illumination condition conventional in this area, for example, adopts electricity-saving lamp, and ultraviolet lamp or high voltage mercury lamp carry out illumination.
In step (1), the reaction under illumination condition or the reaction under initiator condition can be carried out in solvent, also can under condition of no solvent, carry out, preferably condition of no solvent.Described solvent can be the conventional organic solvent in this area.One or more in the preferred benzene of described organic solvent, chlorobenzene, phenyl polychloride, tetracol phenixin and 1,2-ethylene dichloride.The consumption of described solvent is generally the carrying out that does not affect reaction, preferably 1.0mL/g2,3-dimethyl diphenyl.
In step (1), the reaction under illumination condition, can also add catalyzer and/or initiator.The preferred phosphorus trichloride of described catalyzer or phosphorus pentachloride.The mole dosage of described catalyzer is preferably 0.5%～3% of 2,3-dimethyl diphenyl.
In step (1), the preferred Diisopropyl azodicarboxylate of described initiator or benzoyl peroxide.The mole dosage of described initiator is preferably 0.3%～1% of 2,3-dimethyl diphenyl.
In step (1), in the time that catalyzer and/or initiator are also added in the reaction under illumination condition, described reaction preferably includes following steps: by 2,3-dimethyl diphenyl, mixes with catalyzer and/or initiator, in the time of 40 ℃～120 ℃, open illumination, pass into chlorine or drip SULPHURYL CHLORIDE and react.
In step (1), only the reaction under initiator condition preferably includes following steps: 2,3-dimethyl diphenyl is mixed with initiator, in the time of 40 ℃～120 ℃, drip SULPHURYL CHLORIDE or pass into chlorine reaction.Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; The mole dosage of described initiator is 0.3%～1% of 2,3-dimethyl diphenyl.
In step (1), preferably 80 ℃～100 ℃ of described temperature of reaction.
In step (1), the only reaction under initiator condition, the molar ratio of described SULPHURYL CHLORIDE and 2,3-dimethyl diphenyl preferably 0.7～0.9.
In step (1), the process of described reaction can be monitored by GC or HPLC, generally with vapor detection 2, the transformation efficiency of 3-dimethyl diphenyl reaches 70%(mass percent), or HPLC detects 2,3-dimethyl diphenyl transformation efficiency reaches 70%(mass percent) time, as the terminal of reaction, preferably 2 hours.
In step (1), the reaction under illumination condition, after reaction finishes, also can be further purified product by aftertreatment.Described aftertreatment preferably includes following steps: stop passing into chlorine, blast nitrogen, reaction solution rectification under vacuum, collects after cut.
In step (1), the only reaction under initiator condition, after reaction finishes, also can be further purified product by aftertreatment.Described aftertreatment preferably includes following steps: cooling reaction solution to 0 ℃, drips NaHCO under ice bath
3the aqueous solution, extraction, organic phase rectification under vacuum, collects after cut.Described NaHCO
3the NaHCO that aqueous solution preferred mass concentration is 20%
3the aqueous solution.
In step (1), the front-end volatiles that reclaim by rectification under vacuum in aftertreatment be unreacted complete 2,3-dimethyl diphenyl, recyclable applying mechanically; Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), can be used for reduction dechlorination, further prepares raw material 2,3-dimethyl diphenyl.
In step (2), described solvent can be solvent conventional in this area, preferably one or more in toluene, dimethylbenzene, dioxane and water, more preferably water.The consumption of described solvent does not generally affect the carrying out of reaction, preferably 1.0mL/g2-methyl-3-chloromethyl biphenyl.
In step (2), the preferred quaternary ammonium salt of described catalyzer.The preferred tetrabutylammonium chloride of described quaternary ammonium salt, Tetrabutyl amonium bromide, tetrabutyl ammonium fluoride or benzyl trimethyl ammonium chloride, preferably tetrabutylammonium chloride.The mole dosage of described catalyzer is preferably 0.5%～5% of 2-methyl-3-chloromethyl biphenyl.
In step (2), the preferred sodium acetate of described esterifying reagent, sodium formiate, trimethylacetic acid sodium or Sodium Benzoate, preferably sodium acetate.The molar ratio of described esterifying reagent and 2-methyl-3-chloromethyl biphenyl preferably 1.0～3.0, more preferably 1.3～1.8.
In step (2), preferably 60 ℃～120 ℃ of the temperature of reaction of described esterification, more preferably 80 ℃～100 ℃.
In step (2), institute's first is stated the reaction process of esterification and can be monitored by GC, HPLC or TLC, generally when in vapor detection reaction system, 2-base-3-chloromethyl biphenyl content is less than 1%, as the terminal of reaction, the present invention preferably 15 hours.
In the present invention, preferably, after the described esterification of step (2) finishes, directly under alkaline condition, carry out the described hydrolysis reaction of step (3) without aftertreatment; Preferably include following steps: under catalyzer condition, 2-methyl-3-chloromethyl biphenyl is mixed with esterifying reagent, carry out esterification, and then drip aqueous sodium hydroxide solution in reaction solution, be hydrolyzed, the scope of controlling pH value when hydrolysis is 9～14.
In step (3), described alkaline condition preferably adopts the NaOH aqueous solution.The mass concentration of the described NaOH aqueous solution preferably 30%.
In step (3), described pH scope preferably 10～12.
In step (3), preferably 80 ℃～100 ℃ of the temperature of reaction of described hydrolysis.
In step (3), the process of described hydrolysis can be monitored by GC, HPLC or TLC, while generally disappearance with esterification products, as the terminal of reaction, preferably 10～15 hours.
In step (3), after described hydrolysis finishes, can also further pass through aftertreatment purified product.Described aftertreatment preferably includes following steps: separatory, first alcohol and water recrystallization for organic layer, vacuum drying.The water layer that separatory obtains can recovery in the esterification of next batch.
In the preparation method of described 2-methyl-3-phenyl benzil alcohol, described 2,3-dimethyl diphenyl can make by the following method: in solvent, 2-chloromethyl-3-methyl diphenyl (CMMBP) and reductive agent are carried out to reduction dechlorination and react;
In preparation 2, in the method for 3-dimethyl diphenyl, described solvent can be the common solvent of this area, one or more in particular methanol, ethanol, tetrahydrofuran (THF), 2-methyltetrahydrofuran, dioxane, ethyl acetate and acetone, more preferably ethanol and/or tetrahydrofuran (THF).The consumption of described solvent does not generally affect the carrying out of reaction, preferably 1.0mL/g2-chloromethyl-3-methyl diphenyl.
In the method for preparation 2,3-dimethyl diphenyl, the preferred zinc powder of described reductive agent and acetic acid combination, iron powder and acetic acid combination, palladium carbon and H
2combination, platinum carbon and H
2combination, Raney's nickel and H
2combination, preferably palladium carbon and H
2combination.Hydrogen in described reductive agent or acetic acid, with the molar ratio of 2-chloromethyl-3-methyl diphenyl preferably 1.0～3.0, more preferably 1～2.0.Preferably 0.1%～5%2-chloromethyl-3-methyl diphenyl of the mole dosage of zinc powder, iron powder, palladium carbon, platinum carbon or Raney's nickel in described reductive agent, more preferably scope is 1%～5%2-chloromethyl-3-methyl diphenyl.
In the method for preparation 2,3-dimethyl diphenyl, in the time that reductive agent comprises hydrogen, preferably 0.1～0.6MPa of described hydrogen pressure, more preferably 0.1Mpa.
In the method for preparation 2,3-dimethyl diphenyl, preferably 25 ℃～80 ℃ of the temperature of described reduction dechlorination reaction, more preferably 30 ℃～70 ℃.
In the method for preparation 2,3-dimethyl diphenyl, can also further add acid binding agent.The preferred sodium carbonate of described acid binding agent.The consumption of described acid binding agent is preferably 1.1～2.0 times of 2-chloromethyl-3-methyl diphenyl molar weight.
In the method for preparation 2,3-dimethyl diphenyl, the process of described reduction dechlorination reaction can be monitored by GC, HPLC or TLC, while generally disappearance with 2-chloromethyl-3-methyl diphenyl, as the terminal of reaction, preferably 6～63 hours, more preferably 10～48 hours.
After described reduction dechlorination reaction finishes, also can be further purified product by aftertreatment.Described aftertreatment preferably includes following steps: filters, and except desolventizing, resistates underpressure distillation.
Above-mentioned preparation 2, in the method for 3-dimethyl diphenyl, raw material 2-chloromethyl-3-methyl diphenyl (CMMBP) used can be taken from the by product that 2,3-dimethyl diphenyl obtains after according to above-mentioned chlorination reaction.
Therefore,, in the present invention, an operational path of preferably preparing 2-methyl-3-phenyl benzil alcohol is:
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material be commercially available obtaining all.
Positive progressive effect of the present invention is: 2-methyl-3-phenyl benzil alcohol preparation method of the present invention, greatly reduce raw materials cost, and reduce the requirement to equipment, simple to operate, be suitable for suitability for industrialized production.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
Embodiment 1
In 500mL four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), is warming up to after 80 degree, open illumination, start to pass into chlorine, temperature is controlled in 100 ℃, after vapor detection transformation efficiency approximately 70%, stop logical chlorine and blast nitrogen, take away remaining chlorine and hydrogenchloride.Reaction solution underpressure distillation.Front-end volatiles 51.9g, for unreacted complete 2,3-dimethyl diphenyl, yield 28.5%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 82.6g, and yield 38.1%, can be used for preparing the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 62.8g, and yield 29.0%, can be used for follow-up preparation 2-methyl-3-phenyl benzil alcohol reaction.
Embodiment 2
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 4.2g phosphorus pentachloride, be warming up to after 80 ℃, open illumination, start to pass into chlorine, control temperature and be less than 100 ℃, after vapor detection transformation efficiency approximately 70%, under ice bath, slowly drip the NaHCO of 42.0g20%
3solution.Extracting and demixing, organic phase underpressure distillation.Front-end volatiles 53.8g, for unreacted complete 2,3-dimethyl diphenyl, yield 29.5%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 84.3g, and yield 38.9%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 64.1g, and yield 29.6%, can be used for follow-up preparation 2-methyl-3-phenyl benzil alcohol reaction.
Embodiment 3
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 4.2g phosphorus pentachloride, is warming up to after 40 ℃, opens illumination, starts to pass into chlorine, after vapor detection transformation efficiency approximately 70%, slowly drips the NaHCO3 solution of 42.0g20% under ice bath.Extracting and demixing, organic phase underpressure distillation.Front-end volatiles 56.5g, for unreacted complete 2,3-dimethyl diphenyl, yield 31.0%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 80.2g, and yield 37.0%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 57.2g, and yield 26.4%, can be used for follow-up preparation 2-methyl-3-phenyl benzil alcohol reaction.
Embodiment 4
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 1.6g Diisopropyl azodicarboxylate, is warming up to after 80 ℃, opens illumination, start to pass into chlorine, temperature is controlled in 100 ℃, after vapor detection transformation efficiency approximately 70%, stops logical chlorine, blast nitrogen, to take away remaining chlorine and hydrogenchloride.Reaction solution underpressure distillation.Front-end volatiles be unreacted complete 2,3-dimethyl diphenyl, 47.8g, yield 26.2%, recovery.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 81.3g, and yield 37.5%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is 2-methyl-3-chloromethyl biphenyl (MCMBP), 60.7g, and yield 28.0%, can be used for the reaction of 2-methyl-3-phenyl benzil alcohol.
Embodiment 5
In four-hole bottle, add 182.3g2,3-dimethyl diphenyl (DMBP), 3.3g Diisopropyl azodicarboxylate, be warming up to after 80 ℃, in 3 hours, slowly drip 108.0g SULPHURYL CHLORIDE, dropwise rear 80 ℃ of insulations 2 hours, after be cooled to 0 ℃, under ice bath, slowly drip the NaHCO of 84.0g20%
3solution.Extracting and demixing, organic phase underpressure distillation.Front-end volatiles 31.3g, for unreacted complete 2,3-dimethyl diphenyl, yield 17.2%.Middle cut is 2-chloromethyl-3-methyl diphenyl (CMMBP), 105.3g, and yield 48.6%, for the preparation of the reaction of 2,3-dimethyl diphenyl.After cut is mainly 2-methyl-3-chloromethyl biphenyl (MCMBP), 67.4g, and yield 31.1%, can be used for preparing the reaction of 2-methyl-3-phenyl benzil alcohol.
Embodiment 6
In four-hole bottle, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 110.6g ethanol, 48.0g acetic acid, is cooled to after 25 ℃, in 6 hours, adds 31.4g zinc powder in batches.After zinc powder adds, 25 ℃ are incubated 48 hours, steam ethanol and unreacted acetic acid, recovery after middle control is qualified.The residual water that adds of still, extraction, organic phase decompression precipitation, reclaims 2,3-dimethyl diphenyl 69.6g, and yield 95.5% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 7
In four-hole bottle, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 86.5g tetrahydrofuran (THF), 48.0g acetic acid, is cooled to after 25 ℃, in 6 hours, adds 31.4g zinc powder in batches.After zinc powder adds, 25 ℃ are incubated 63 hours, steam tetrahydrofuran (THF) and unreacted acetic acid, recovery after middle control is qualified.The residual water that adds of still, extraction, organic phase decompression precipitation, reclaims 2,3-dimethyl diphenyl 67.8g, and yield 93.0% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 8
In 500mL autoclave, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 92.1g ethanol, 2.6g5%Pd/C, 63.6g Na
2cO
3, with the hydrogen that is filled with 0.1MPa after hydrogen exchange three times, be warming up to 50 ℃ of insulation 6h.Filter, reclaim catalyzer, steam ethanol, recovery.Mother liquor underpressure distillation, obtains 2,3-dimethyl diphenyl 71.2g, and yield 97.6% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 9
In 500mL autoclave, add 2-chloromethyl-3-methyl diphenyl (CMMBP) 86.7g, 92.1g ethanol, 63.6g Na
2cO
3, 0.9g Raney's nickel, with the hydrogen that is filled with 0.6MPa after hydrogen exchange three times, is warming up to 70 ℃ of insulation 10h.Filter, mother liquor normal pressure steams ethanol, and rear underpressure distillation obtains 2,3-dimethyl diphenyl 66.6g, and yield 91.4% can return and apply mechanically preparation 2-methyl-3-chloromethyl biphenyl.
Embodiment 10
In four-hole bottle, add 65.0g2-methyl-3-chloromethyl biphenyl (MCMBP), 2.5g tetrabutylammonium chloride, 73.8g50% aqueous sodium acetate solution, be warming up to backflow, 100 ℃ of insulations 15 hours, after vapor detection raw material is less than 1%, to the NaOH aqueous solution that slowly drips 44.0g30% in reaction solution, control pH between 9-10,100 ℃ insulation 10 hours after, 60 ℃ of stratification, mother liquor recovery, toluene and mixed heptane recrystallization for organic layer, obtain BFA wet product.Crude product vacuum drying obtains the finished product BFA52.3g, and purity is greater than 99.8%(GC), yield 88.0%.
Embodiment 11
In four-hole bottle, add 65.0g2-methyl-3-chloromethyl biphenyl (MCMBP), 2.5g tetrabutylammonium chloride, 89.4g50% trimethylacetic acid sodium water solution, be warming up to backflow, 100 ℃ of insulations 15 hours, after vapor detection raw material is less than 1%, to the NaOH aqueous solution that slowly drips 44.0g30% in reaction solution, control pH between 9-10,100 ℃ insulation 15 hours after, 60 ℃ of stratification, mother liquor recovery, first alcohol and water recrystallization for organic layer, obtains BFA wet product.Crude product vacuum drying obtains the finished product BFA48.9g, and purity is greater than 99.0%(GC), yield 82.2%.
Embodiment 12
In four-hole bottle, add 65.0g2-methyl-3-chloromethyl biphenyl (MCMBP), 2.9g tetra-n-butyl ammonium bromide, 73.8g50% aqueous sodium acetate solution, be warming up to backflow, 100 ℃ of insulations 15 hours, after vapor detection raw material is less than 1%, to the NaOH aqueous solution that slowly drips 44.0g30% in reaction solution, control pH between 12-13,100 ℃ insulation 10 hours after, 60 ℃ of stratification, mother liquor recovery, toluene and mixed heptane recrystallization for organic layer, obtain BFA wet product.Crude product vacuum drying obtains the finished product BFA54.1g, and purity is greater than 99.5%(GC), yield 91.0%.
Claims (15)
1. a preparation method for 2-methyl-3-phenyl benzil alcohol, it comprises the steps:
Step (1): under illumination condition, by 2,3-dimethyl diphenyl and chlorine hybrid reaction, temperature of reaction is 40 ℃～120 ℃;
Or, under initiator condition, by 2,3-dimethyl diphenyl, to react with SULPHURYL CHLORIDE or chlorine, temperature of reaction is 40 ℃～120 ℃;
Step (2): in solvent, under catalyzer condition, 2-methyl-3-chloromethyl biphenyl and esterifying reagent that step (1) is prepared carry out esterification;
Step (3): under alkaline condition, the esterification products that step (2) is prepared is hydrolyzed, controlling pH scope is 9～14;
2. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), and the reaction under illumination condition, comprise the steps: 2,3-dimethyl diphenyl is warming up to 40 ℃～120 ℃, opens illumination, passes into chlorine and reacts.
3. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), the chlorination reaction under two kinds of conditions is carried out or carried out under condition of no solvent in solvent; Described solvent is organic solvent; Described organic solvent is one or more in benzene, chlorobenzene, phenyl polychloride, tetracol phenixin and 1,2-ethylene dichloride.
4. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), the reaction under illumination condition, further adds catalyzer and/or initiator; Described catalyzer is phosphorus trichloride or phosphorus pentachloride; The mole dosage of described catalyzer is 0.5%～3% of 2,3-dimethyl diphenyl; Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; The mole dosage of described initiator is 0.3%～1% of 2,3-dimethyl diphenyl.
5. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, it is characterized in that: in step (1), in the time that catalyzer and/or initiator are also added in the reaction under illumination condition, described reaction comprises the steps: 2,3-dimethyl diphenyl, mixes with catalyzer and/or initiator, in the time of 40 ℃～120 ℃, open illumination, pass into chlorine or drip SULPHURYL CHLORIDE and react.
6. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, it is characterized in that: in step (1), only the reaction under initiator condition comprises the steps: 2,3-dimethyl diphenyl mixes with initiator, in the time of 40 ℃～120 ℃, drip SULPHURYL CHLORIDE or pass into chlorine reaction; Described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide; The mole dosage of described initiator is 0.3%～1% of 2,3-dimethyl diphenyl.
7. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), described temperature of reaction is 80 ℃～100 ℃; In step (1), the described only reaction under initiator condition, the molar ratio of described SULPHURYL CHLORIDE and 2,3-dimethyl diphenyl is 0.7～0.9.
8. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (1), the only reaction under initiator condition, after reaction finishes, is further purified product by aftertreatment; Described aftertreatment comprises the steps: cooling reaction solution to 0 ℃, under ice bath, drips NaHCO
3the aqueous solution, extraction, organic phase rectification under vacuum, collects after cut;
In step (1), the front-end volatiles that reclaim by rectification under vacuum in aftertreatment be unreacted complete 2,3-dimethyl diphenyl, recovery; Middle cut is 2-chloromethyl-3-methyl diphenyl, and reduction dechlorination, further prepares raw material 2,3-dimethyl diphenyl.
9. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (2), described solvent is one or more in toluene, dimethylbenzene, dioxane and water; In step (2), described catalyzer is quaternary ammonium salt; Described quaternary ammonium salt is tetrabutylammonium chloride, Tetrabutyl amonium bromide, tetrabutyl ammonium fluoride or benzyl trimethyl ammonium chloride; The mole dosage of described catalyzer is 0.5%～5% of 2-methyl-3-chloromethyl biphenyl; In step (2), described esterifying reagent is sodium acetate, sodium formiate, trimethylacetic acid sodium or Sodium Benzoate; The molar ratio of described esterifying reagent and 2-methyl-3-chloromethyl biphenyl is 1.0～3.0.
10. the preparation method of 2-methyl-3-phenyl benzil alcohol as claimed in claim 1, is characterized in that: in step (2), the temperature of reaction of described esterification is 60 ℃～120 ℃;
After the described esterification of step (2) finishes, directly under alkaline condition, carry out the described hydrolysis reaction of step (3) without aftertreatment; Comprise the steps: under catalyzer condition, 2-methyl-3-chloromethyl biphenyl is mixed with esterifying reagent, carry out esterification, and then drip aqueous sodium hydroxide solution in reaction solution, be hydrolyzed, the scope of controlling pH value when hydrolysis is 9～14.
The preparation method of 11. 2-methyl-3-phenyl benzil alcohols as claimed in claim 10, is characterized in that: in step (2), the temperature of reaction of described esterification is 80 ℃～100 ℃.
The preparation method of 12. 2-methyl-3-phenyl benzil alcohols as claimed in claim 1, is characterized in that: in step (3), described alkaline condition adopts the NaOH aqueous solution; In step (3), described pH scope is 10～12; In step (3), the temperature of reaction of described hydrolysis is 80 ℃～100 ℃;
In step (3), after described hydrolysis finishes, also further pass through aftertreatment purified product; Described aftertreatment comprises the steps: separatory, first alcohol and water recrystallization for organic layer, vacuum drying; The water layer recovery that separatory obtains is in the esterification of next batch.
The preparation method of 13. 2-methyl-3-phenyl benzil alcohols as claimed in claim 1, is characterized in that: step (1): in solvent, 2-chloromethyl-3-methyl diphenyl is carried out to reduction dechlorination with reductive agent and react, prepare 2,3-dimethyl diphenyl;
Step (2): under illumination condition, step (1) is prepared 2,3-dimethyl diphenyl and chlorine hybrid reaction, temperature of reaction is 40 ℃～120 ℃;
Or, under initiator condition, step (1) is prepared 2,3-dimethyl diphenyl, reacts with SULPHURYL CHLORIDE or chlorine, temperature of reaction is 40 ℃～120 ℃;
Step (3): in solvent, under catalyzer condition, 2-methyl-3-chloromethyl biphenyl and esterifying reagent that step (2) is prepared carry out esterification;
Step (4): under alkaline condition, the esterification products that step (3) is prepared is hydrolyzed, controlling pH scope is 9～14;
The preparation method of 14. 2-methyl-3-phenyl benzil alcohols as claimed in claim 13, it is characterized in that: in preparation 2, in the step of 3-dimethyl diphenyl, described solvent is one or more in methyl alcohol, ethanol, tetrahydrofuran (THF), 2-methyltetrahydrofuran, dioxane, ethyl acetate and acetone;
In the step of preparation 2,3-dimethyl diphenyl, described reductive agent is zinc powder and acetic acid combination, iron powder and acetic acid combination, palladium carbon and H
2combination, platinum carbon and H
2combination, Raney's nickel and H
2combination; Hydrogen in described reductive agent or acetic acid, with the molar ratio of 2-chloromethyl-3-methyl diphenyl be 1.0～3.0; The mole dosage of zinc powder, iron powder, palladium carbon, platinum carbon or Raney's nickel in described reductive agent is 0.1%～10%2-chloromethyl-3-methyl diphenyl.
The preparation method of 15. 2-methyl-3-phenyl benzil alcohols as claimed in claim 14, is characterized in that: in the step of preparation 2,3-dimethyl diphenyl, in the time that reductive agent comprises hydrogen, described hydrogen pressure is 0.1～0.6Mpa;
In the step of preparation 2,3-dimethyl diphenyl, the temperature of described reduction dechlorination reaction is 25 ℃～80 ℃;
In the step of preparation 2,3-dimethyl diphenyl, further add acid binding agent; Described acid binding agent is sodium carbonate.
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| CN109734555A (en) * | 2019-02-01 | 2019-05-10 | 武汉格源精细化学有限公司 | Preparation method of the high-purity to methylbenzyl alcohol |
| CN110922297A (en) * | 2018-09-19 | 2020-03-27 | 张家港九力新材料科技有限公司 | Method for preparing biphenyl dichlorobenzyl through photocatalytic chlorination |
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