CN102381941A - Preparation method of 2-methyl-3-biphenylmethanol - Google Patents

Abstract

The invention relates to a preparation method of 2-methyl-3-biphenylmethanol. The 2-methyl-3-biphenylmethanol is prepared by carrying out catalyst preparation, a first Grignard reaction, a coupling reaction, and a second Grignard reaction, and carrying out series of steps of filtration, recrystallization, drying and the like. According to the invention, the method which does not adopt tetrahydrofuran as a solvent adopts toluene as the solvent. The method of the invention, which well solves problems of the 2-methyl-3-biphenylmethanol catalyst preparation with toluene as the solvent and adopts pure benzene as a coupling agent, allows no byproducts to be generated.

Description

A kind of preparation method of 2-methyl-3-biphenylmethanol

Technical field

The present invention relates to the synthetic field of fine chemistry industry, be specifically related to the preparation method of a kind of Er Bugeshi reaction synthetic pesticide midbody 2-methyl-3-biphenylmethanol monomer (2-methyl diphenyl-3-methyl alcohol).

Background technology

2-methyl-3-biphenylmethanol has another name called 2-methyl-3-phenyl benzil alcohol; Be mainly used in the production of agricultural chemicals bifenthrin and the synthesis material of other pharmaceutical prods.2-methyl-3-biphenylmethanol is the white crystals body, and slightly the special odor of alcohol is dissolved in toluene, methyl alcohol, and ETHYLE ACETATE, acetone and other organic solvent, water insoluble; Present compound method mainly contains with 2, and the 6-toluene dichloride is a raw material, is solvent with the THF, through two step grignard reactions, generates 2-methyl-3-phenyl phenyl aldehyde with the N reaction, becomes product with potassium borohydride reduction then; Again or adopt " patent No. for the ZL200710130941.7 patent name is: 2-methyl-3-phenyl benzil alcohol process for cleanly preparing " said method to make 2-methyl-3-biphenylmethanol; Above-mentioned two kinds of methods are all used the solvent of THF as grignard reaction; Isolated tetrahydrofuran solvent generally contains the water about 5-15% in its production process; And be difficult to remove water purification with general rectificating method; So the THF that adopts aforesaid method to obtain reclaiming generally can only use it for anything else in addition, repeats to utilize and can not return native system again.

Summary of the invention

In view of above-mentioned weak point, the object of the present invention is to provide a kind of preparation method who does not adopt THF to make the 2-methyl-3-biphenylmethanol of solvent, this method technology is simple, and yield is high.

For, achieving the above object, the present invention has adopted following technical scheme: 1. the preparation method of a 2-methyl-3-biphenylmethanol, it is characterized in that: this preparation method comprises the steps:

(1) Preparation of Catalyst: count by weight ratio: with 238 parts of nickelous chlorides, 133 parts of aluminum chlorides, 270 parts of iron trichlorides, 170 parts of cupric chlorides are dissolved in 4055 parts of raw spirits of heat, and the raw spirit temperature is 60-80 ℃; The dissolving back that finishes adds 811 parts of coconut husk injection active carbons, stirs to pour in the furnace pot and put into vacuum drying oven, and under 120 ℃ of temperature, constant temperature baking 4-6 hour, the cooling fragmentation obtains catalyzer;

(2) grignard reaction for the first time, meter adds 780 parts of toluene, 11 parts in magnesium powder in reaction kettle by weight ratio; 2 parts of monobromethanes stir, and after reaction caused, refluxing dripped 2 down; 260 parts of 6-toluene dichloride with 70 ℃ of insulations 3 hours, get the grignard reaction solution A after grignard reaction is accomplished;

(3) linked reaction reaction: count by weight ratio, 400 parts of purified petroleum benzin and the prepared catalyzer of step (1) are stirred in reaction kettle for 1 part, and under 75-81 ℃ of backflow, drip the grignard reaction solution A that step (2) obtains; Dripped off in 8 hours, and got the coupling material, transfer to PH 2-3 with Hydrogen bromide; Hydrolysis reaction is warming up to 80-85 ℃ subsequently gradually, toluene that recovery steams and unnecessary purified petroleum benzin; The feed liquid cooling adds 300 parts of water, makes water and oil phase layering; Isolate oil reservoir, distill after washing three times and dewater, the biphenyl material;

(4) grignard reaction for the second time: meter by weight ratio, reaction kettle adds 866 parts of toluene, 70 parts in magnesium powder; 2 parts of monobromethanes stir, after grignard reaction causes; 500 parts in the biphenyl material that refluxes and to drip step (3) gained down, with 60 ℃ temperature insulations 4 hours, the grignard reaction solution B; And then drip 260 parts of Ns, and transfer PH to 2-3 with Hydrogen bromide, be warming up to 80-85 ℃ gradually; Toluene is steamed, and feed liquid is cooled to 50 ℃ then, adds 433 parts of toluene again and stirs 3 hours; Add 500 parts of water washings, extracting and demixing is taken out oil phase, adds 1000 parts of water and stirs the washing after-filtration; Recrystallization is at the 50-60 ℃ of dry 2-methyl-3-biphenylmethanol product that gets.

Beneficial effect of the present invention is: the present invention does not adopt THF to make solvent; Then take toluene to make the preparation technology of solvent; The present invention has also well solved toluene and has prepared the problem of the catalyzer of 2-methyl-3-biphenylmethanol as solvent, makees coupling agent with purified petroleum benzin simultaneously, does not produce by product.

Embodiment

Below we will further specify the present invention through embodiment.

A kind of preparation method of 2-methyl-3-biphenylmethanol, this preparation method comprises the steps:

(1) Preparation of Catalyst: count by weight ratio: with the 238kg nickelous chloride, 133kg aluminum chloride, 270kg iron trichloride, 170kg cupric chloride are dissolved in the 4055kg raw spirit of heat, and the raw spirit temperature is 70 ℃; The dissolving back that finishes adds 811kg coconut husk injection active carbon, stirs to pour in the furnace pot and put into vacuum drying oven, and under 120 ℃ of temperature, constant temperature baking 6 hours, the cooling fragmentation obtains catalyzer;

(2) grignard reaction for the first time, meter adds toluene 780kg, magnesium powder 11kg in reaction kettle by weight ratio; Monobromethane 2kg stirs, and after reaction caused, refluxing dripped 2 down; 6-toluene dichloride 260kg with 70 ℃ of insulations 3 hours, gets the grignard reaction solution A after grignard reaction is accomplished;

(3) linked reaction reaction: count by weight ratio, purified petroleum benzin 400 kg and the prepared catalyzer 1kg of step (1) are stirred in reaction kettle, and under 80 ℃ of backflows, drip the grignard reaction solution A that step (2) obtains; Dripped off in 8 hours, and got the coupling material, transfer to PH 2-3 with Hydrogen bromide; Hydrolysis reaction is warming up to 85 ℃ subsequently gradually, toluene that recovery steams and unnecessary purified petroleum benzin; The feed liquid cooling adds 300 kg water, makes water and oil phase layering; Isolate oil reservoir, distill after washing three times and dewater, the biphenyl material;

(4) grignard reaction for the second time: meter by weight ratio, reaction kettle adds toluene 866kg, magnesium powder 70 kg; Monobromethane 2kg stirs, after grignard reaction causes; Reflux and drip biphenyl material 500 kg of step (3) gained down,, get the grignard reaction solution B with 60 ℃ temperature insulations 4 hours; And then drip N 260kg, and transfer PH to 2-3 with Hydrogen bromide, be warming up to 85 ℃ gradually; Toluene is steamed, and feed liquid is cooled to 50 ℃ then, adds 433kg toluene again and stirs 3 hours; Add the washing of 500kg water, extracting and demixing is taken out oil phase, adds 1000kg water and stirs the washing after-filtration; Recrystallization is at 60 ℃ of dry 2-methyl-3-biphenylmethanol products that get.

Claims (1)

1. the preparation method of a 2-methyl-3-biphenylmethanol, it is characterized in that: this preparation method comprises the steps:

(1) Preparation of Catalyst: count by weight ratio: with 238 parts of nickelous chlorides, 133 parts of aluminum chlorides, 270 parts of iron trichlorides, 170 parts of cupric chlorides are dissolved in 4055 parts of raw spirits of heat, and the raw spirit temperature is 60-80 ℃; The dissolving back that finishes adds 811 parts of coconut husk injection active carbons, stirs to pour in the furnace pot and put into vacuum drying oven, and under 120 ℃ of temperature, constant temperature baking 4-6 hour, the cooling fragmentation obtains catalyzer;

(2) grignard reaction for the first time, meter adds 780 parts of toluene, 11 parts in magnesium powder in reaction kettle by weight ratio; 2 parts of monobromethanes stir, and after reaction caused, refluxing dripped 2 down; 260 parts of 6-toluene dichloride with 70 ℃ of insulations 3 hours, get the grignard reaction solution A after grignard reaction is accomplished;

(3) linked reaction reaction: count by weight ratio, 400 parts of purified petroleum benzin and the prepared catalyzer of step (1) are stirred in reaction kettle for 1 part, and under 75-81 ℃ of backflow, drip the grignard reaction solution A that step (2) obtains; Dripped off in 8 hours, and got the coupling material, transfer to PH 2-3 with Hydrogen bromide; Hydrolysis reaction is warming up to 80-85 ℃ subsequently gradually, toluene that recovery steams and unnecessary purified petroleum benzin; The feed liquid cooling adds 300 parts of water, makes water and oil phase layering; Isolate oil reservoir, distill after washing three times and dewater, the biphenyl material;

(4) grignard reaction for the second time: meter by weight ratio, reaction kettle adds 866 parts of toluene, 70 parts in magnesium powder; 2 parts of monobromethanes stir, after grignard reaction causes; 500 parts in the biphenyl material that refluxes and to drip step (3) gained down, with 60 ℃ temperature insulations 4 hours, the grignard reaction solution B; And then drip 260 parts of Ns, and transfer PH to 2-3 with Hydrogen bromide, be warming up to 80-85 ℃ gradually; Toluene is steamed, and feed liquid is cooled to 50 ℃ then, adds 433 parts of toluene again and stirs 3 hours; Add 500 parts of water washings, extracting and demixing is taken out oil phase, adds 1000 parts of water and stirs the washing after-filtration; Recrystallization is at the 50-60 ℃ of dry 2-methyl-3-biphenylmethanol product that gets.