CN101362772A - The preparation method of dibutylmagnesium - Google Patents

The preparation method of dibutylmagnesium Download PDF

Info

Publication number
CN101362772A
CN101362772A CNA2008101968974A CN200810196897A CN101362772A CN 101362772 A CN101362772 A CN 101362772A CN A2008101968974 A CNA2008101968974 A CN A2008101968974A CN 200810196897 A CN200810196897 A CN 200810196897A CN 101362772 A CN101362772 A CN 101362772A
Authority
CN
China
Prior art keywords
reaction
dibutylmagnesium
preparation
sec
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2008101968974A
Other languages
Chinese (zh)
Inventor
吴广文
陶凌云
吴元欣
黄艳刚
孙炜
朱少坤
宋刚
张春桂
杨峻
丁墩墩
刘旋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Institute of Technology
Original Assignee
Wuhan Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Institute of Technology filed Critical Wuhan Institute of Technology
Priority to CNA2008101968974A priority Critical patent/CN101362772A/en
Publication of CN101362772A publication Critical patent/CN101362772A/en
Pending legal-status Critical Current

Links

Abstract

本发明涉及一种以2-氯丁烷、镁粉、正丁基锂为原料合成二丁基镁的制备方法。以2-氯丁烷、镁粉、正丁基锂为原料,在无水、无氧溶剂条件下合成二丁基镁,其反应过程包括:在N2保护下,将镁粉、引发剂混合,置于反应釜中加热、搅拌,并缓慢加入少量2-氯丁烷溶液,引发反应后,在保温情况下,将2-氯丁烷溶液缓慢加入反应釜,反应生成格氏试剂;冷却降温,快速加入正丁基锂正己烷溶液,保温反应后,蒸馏分离出溶剂,冷却过滤,制备得到二丁基镁;制备过程中各原料的配比为:镁粉∶2-氯丁烷∶正丁基锂的摩尔比为1.0~1.2∶1∶1。本发明具有工艺简单易行、无污染、投资省、镁粉转化率和产品收率高等优点。The invention relates to a preparation method for synthesizing dibutyl magnesium by using 2-chlorobutane, magnesium powder and n-butyl lithium as raw materials. Using 2-chlorobutane, magnesium powder, and n-butyllithium as raw materials, dibutylmagnesium is synthesized under anhydrous and oxygen-free solvent conditions. The reaction process includes: under the protection of N2 , magnesium powder and initiator are mixed , placed in the reaction kettle to heat and stir, and slowly add a small amount of 2-chlorobutane solution, after the reaction is initiated, slowly add the 2-chlorobutane solution to the reaction kettle under the condition of heat preservation, and the reaction generates Grignard reagent; cooling down , quickly add n-butyllithium n-hexane solution, after heat preservation reaction, distill and separate the solvent, cool and filter, and prepare dibutylmagnesium; the ratio of each raw material in the preparation process is: magnesium powder: 2-chlorobutane: n- The molar ratio of butyllithium is 1.0˜1.2:1:1. The invention has the advantages of simple and easy process, no pollution, low investment, high conversion rate of magnesium powder and high product yield.

Description

The preparation method of dibutylmagnesium
Technical field
The present invention relates to a kind of is the preparation method of the synthetic dibutylmagnesium of raw material with Sec-Butyl Chloride, magnesium powder, n-Butyl Lithium.
Background technology
Organic halogenation magnesium is that Grignard reagent has application very widely in chemical reaction.Tong Geshi reagent is compared, and dialkyl magnesium reaction is similar and use and want much less with organic halogenation magnesium.Its major cause is also not have suitable method mass production dialkyl magnesium up to now.Dialkyl magnesium compare with Grignard reagent and lithium alkylide have that raw materials cost is low, transportation easily.Particularly dialkyl magnesium has the excellent in chemical performance, compares dialkyl magnesium with lithium alkylide and has better thermostability and weak igniting property (ethereal solution).Dialkyl magnesium even can be used for the stablizer of lithium alkylide hydrocarbon solution.Compare with organic halogenation magnesium, dialkyl magnesium stability in varsol is stronger, and reaction yield is higher.Dialkyl magnesium is similar to lithium alkylide, can be used as the metallization reagent of organic compound, as benzene, toluene etc., can also react with unsaturated organic compound.
Dibutylmagnesium, English name: Dibutylmagnesium (being called for short DBM) has multiple isomers.Be dissolved in ethers, pure dibutylmagnesium is nonvolatile solid, but since its solid very easily fire, so finished product is made 14% hexane solution or 17% n-heptane solution.
Dibutylmagnesium is because the defective on the preparation method never has the such widespread use of Grignard reagent.Preparation method is the earliest reduced and gets by the magnesium powder by mercury alkylide, and its reaction is as follows:
R 2Hg+Mg→R 2Mg+Hg
This preparation process be subjected to the great number price of mercury and when using injury two aspects to human body limit.In fact generally speaking, mercury alkylide is made by magnesium exactly.This reaction generally will be carried out in alkaline environment, must compare under the environment of alkali-free in the Grignard reagent combined reaction with it, and it can decompose more alkyl magnesium.
Secondly by adding diox itself and magnesium halide are separated out with the form of complex compound, react as follows:
2RMgX+C 4H 8O 2→R 2Mg+C 4H 8O 2·MgX 2
Make this reaction under alkali free environment, not finish because diox itself is alkalescence, therefore,, make its production be subjected to great restriction because dibutylmagnesium preparation difficulty has mercury pollution and must finish under alkaline environment.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that exists at above-mentioned prior art and a kind of dibutylmagnesium preparation method is provided, it have simple for process, pollution-free, cost is low, magnesium powder transformation efficiency and the high advantage of product yield.
The present invention for the technical scheme that problem adopted of the above-mentioned proposition of solution is:
With Sec-Butyl Chloride, magnesium powder, n-Butyl Lithium is raw material, synthetic dibutylmagnesium under anhydrous, anaerobic solvent condition, and its reaction process comprises: at N 2Protection mixes magnesium powder, initiator down, places the reactor heating, stirs, and slowly add a small amount of Sec-Butyl Chloride solution, after the initiation reaction, under the insulation situation, Sec-Butyl Chloride solution is slowly added reactor, and reaction generates Grignard reagent CH 3CH 2CH (CH 3) MgCl; Cool, add the n-Butyl Lithium hexane solution fast, after the insulation reaction, fractionation by distillation goes out solvent, and cold filtration prepares dibutylmagnesium; Each proportion of raw materials is in the preparation process: magnesium powder: Sec-Butyl Chloride: the mol ratio of n-Butyl Lithium is 1.0~1.2: 1: 1.
Press such scheme, described initiator is I 2, Br 2, methyl iodide, monobromethane or Grignard reagent; The add-on of described initiator is 0.1~0.5% of Sec-Butyl Chloride institute consumption by weight.
Press such scheme, described reactor is to have in the reactor of stirring, reflux exchanger, nitrogen ingress pipe, dropping funnel, and reaction process feeds nitrogen.
Press such scheme, after reaction causes, Sec-Butyl Chloride solution is slowly dropped in the reactor, temperature of reaction is controlled at 30 ℃~100 ℃; After dropwising, continue to stir insulation reaction 1.5~3 hours.
Press such scheme, after generating Grignard reagent, cool, under 0 ℃~60 ℃ temperature, add the n-Butyl Lithium hexane solution fast, insulation reaction 1~2 hour, holding temperature are controlled at 30 ℃~120 ℃.
Press such scheme, described Sec-Butyl Chloride solution is formulated by Sec-Butyl Chloride and solvent, and strength of solution is 0.6~1.05mol/L, and described solvent is an ether, or is in tetrahydrofuran (THF), benzene, toluene, the normal hexane any one.
Press such scheme, described n-Butyl Lithium hexane solution is formulated by n-Butyl Lithium and solvent normal hexane, and the volumetric molar concentration of solution is 2.5mol/L.
Press such scheme, fractionation by distillation goes out solvent, gets supernatant liquid after leaving standstill; The little metal lithium is cut into small pieces adds in the above-mentioned supernatant liquor, slowly stir, the inflated with nitrogen protection leaches the unreacted metal lithium, and the concentration with complexometry analysis dibutylmagnesium adds normal hexane, is made into certain density dibutylmagnesium solution.The solvent of collecting can be recycled.
The interior stirring velocity of reactor is 100~700 rev/mins in the above-mentioned reaction; Require anhydrous, anaerobic in the reactor, and the inflated with nitrogen protection.
Reaction formula of the present invention is:
CH 3CH 2CH(CH 3)Cl+Mg——CH 3CH 2CH(CH 3)MgCl
CH 3CH 2CH(CH 3)MgCl+CH 3CH 2CH 2CH 2Li——CH 3CH 2CH 2CH 2Mg(CH 3)CHCH 2CH 3
CH 3CH 2CH(CH 3)Cl+2Li——CH 3CH 2CH(CH 3)Li+LiCl
CH 3CH 2CH(CH 3)Li+CH 3CH 2CH(CH 3)MgCl——[CH 3CH 2CH(CH 3)] 2Mg+LiCl
The Grignard reagent synthetic causes slower, should carry out under heating and slow stirring condition.Reaction is reacted rapider, and is attended by a large amount of reaction heat after causing, and following side reaction easily takes place:
CH 3CH 2CH(CH 3)Cl+2Mg——CH 3CH 2CH(CH 3)CH(CH 3)CH 2CH 3+MgCl 2
The way that solves has: (1) cooling, the reactor of use should be equipped with the cooling heat transferring device, accelerates to stir, and makes the reaction mixture uniform mixing, avoids local superheating, guarantees to react and effectively carries out.(2) Sec-Butyl Chloride and solvent ether are hybridly prepared into the solution of lower concentration, slowly join in the reactor control speed of reaction.
The reaction of Grignard reagent and butyllithium reaction generation dibutylmagnesium is very fast, and reaction is very complete.In order to increase the LiCl particle grain size, be easy to separate, need to reduce temperature of reaction and stirring velocity.The LiCl that separates can recycle, and reduces production costs the enabling environment protection.
Beneficial effect of the present invention is: 1, adopt two-step approach to finish preparation process, preparation process is simple and effective; 2, preparation cost is low, and is pollution-free, the enabling environment protection; 3, magnesium powder transformation efficiency and product yield height, and the solvent of collecting can be recycled.
Embodiment
Further specify the present invention by the following examples.
Embodiment 1:
To agitator, dropping funnel, thermometer, nitrogen ingress pipe are housed, feed nitrogen in the 250ml four-hole boiling flask reactor of reflux exchanger (on adorn drying tube), water vapour is driven away in heating, removes thermal source after reaching 100 ℃.When treating that temperature drops to about 70 ℃, add 3.65g (0.15mol) magnesium powder, 2g2-chlorobutane, 30mL ether and an iodine, slowly stir, make that material is stable in the reactor refluxed 10~20 minutes, controlled temperature is about 34 ℃.In the reactor liquid become brown, treat that reddish-brown is taken off after, beginning slowly drips Sec-Butyl Chloride solution, Sec-Butyl Chloride solution is mixed by 15g2-chlorobutane and 110mL ether; Control reaction temperature after dropwising, continued stirring reaction 3 hours at 33 ℃~35 ℃, added the hexane solution that 60mL contains the 2.5mol/L n-Butyl Lithium then in reactor fast, reduced stirring velocity, and control reaction temperature is 0 ℃~5 ℃.React the filtering separation that finishes, filtrate is analyzed Mg content with EDTA (complexometry), and calculating product yield is 85%.
Embodiment 2:
To agitator, dropping funnel, thermometer, nitrogen ingress pipe are housed, feed nitrogen in the 250ml four-hole boiling flask reactor of reflux exchanger (on adorn drying tube), water vapour is driven away in heating, removes thermal source after reaching 100 ℃.When treating that temperature drops to about 70 ℃, add 3.65g (0.15mol) magnesium powder, 2g2-chlorobutane, 30mL normal hexane and an iodine, slowly stir, controlled temperature is about 65 ℃.Liquid becomes rose in the bottle, treats that rose takes off, and slowly drips Sec-Butyl Chloride solution, and Sec-Butyl Chloride solution is mixed by 15g2-chlorobutane and 110mL normal hexane; Temperature of reaction is controlled at 60 ℃~68 ℃, continues stirring reaction 3 hours, adds the hexane solution that 60mL contains the 2.5mol/L n-Butyl Lithium then in reactor fast, reduces stirring velocity, and control reaction temperature is 0 ℃~5 ℃.React the filtering separation that finishes, filtrate is analyzed Mg content with EDTA, and calculating product yield is 75%.
Embodiment 3:
To agitator, dropping funnel, thermometer, nitrogen ingress pipe are housed, feed nitrogen in the 250ml four-hole boiling flask reactor of reflux exchanger (on adorn drying tube), water vapour is driven away in heating, removes thermal source after reaching 100 ℃.When treating that temperature drops to about 70 ℃, add 4.4g (0.18mol) magnesium powder, 3g2-chlorobutane, 100mL ether and iodine, slowly stir, controlled temperature is about 33 ℃.Liquid becomes reddish-brown in the bottle, treats that reddish-brown takes off, and slowly drips Sec-Butyl Chloride solution, and Sec-Butyl Chloride solution is mixed by 14g2-chlorobutane and 160mL ether.Temperature of reaction is controlled at 33 ℃~35 ℃, continues stirring reaction 3 hours, adds the hexane solution that 60mL contains the 2.5mol/L n-Butyl Lithium then in reactor fast, reduces stirring velocity, and control reaction temperature is 0 ℃~5 ℃.React the filtering separation that finishes, filtrate is analyzed Mg content with EDTA, and calculating product yield is 76%.
Embodiment 4:
To agitator, dropping funnel, thermometer, nitrogen ingress pipe are housed, feed nitrogen in the 250ml four-hole boiling flask reactor of reflux exchanger (on adorn drying tube), water vapour is driven away in heating, removes thermal source after reaching 100 ℃.When treating that temperature drops to about 70 ℃, add 4.9g (0.2mol) magnesium powder, 2g2-chlorobutane, 30mL normal hexane and an iodine, slowly stir, controlled temperature is about 65 ℃.Liquid becomes rose in the bottle, treats that rose takes off, and slowly drips Sec-Butyl Chloride solution, and Sec-Butyl Chloride solution is mixed by 15g2-chlorobutane and 110mL normal hexane; Temperature of reaction is controlled at 60 ℃~68 ℃, continues stirring reaction 3 hours, adds the hexane solution that 60mL contains the 2.5mol/L n-Butyl Lithium then in reactor fast, reduces stirring velocity, and control reaction temperature is 0 ℃~5 ℃.React the filtering separation that finishes, filtrate is analyzed Mg content with EDTA, and calculating product yield is 76.6%.

Claims (7)

1, a kind of preparation method of dibutylmagnesium is characterized in that: with Sec-Butyl Chloride, magnesium powder, n-Butyl Lithium is raw material, synthetic dibutylmagnesium under anhydrous, anaerobic solvent condition, and its reaction process comprises: at N 2Protection mixes magnesium powder, initiator down, places the reactor heating, stirs, and slowly add a small amount of Sec-Butyl Chloride solution, after the initiation reaction, under the insulation situation, Sec-Butyl Chloride solution is slowly added reactor, and reaction generates Grignard reagent CH 3CH 2CH (CH 3) MgCl; Cool, add the n-Butyl Lithium hexane solution fast, after the insulation reaction, fractionation by distillation goes out solvent, and cold filtration prepares dibutylmagnesium; Each proportion of raw materials is in the preparation process: magnesium powder: Sec-Butyl Chloride: the mol ratio of n-Butyl Lithium is 1.0~1.2: 1: 1.
2, by the preparation method of the described dibutylmagnesium of claim 1, it is characterized in that described initiator is I 2, Br 2, methyl iodide, monobromethane or Grignard reagent; The add-on of described initiator is 0.1~0.5 ‰ of Sec-Butyl Chloride institute consumption by weight.
3, by the preparation method of the described dibutylmagnesium of claim 1, it is characterized in that described reactor is to have in the reactor of stirring, reflux exchanger, nitrogen ingress pipe, dropping funnel, reaction process feeds nitrogen.
4, by the preparation method of the described dibutylmagnesium of claim 1, it is characterized in that after reaction causes, Sec-Butyl Chloride solution slowly being dropped in the reactor, temperature of reaction is controlled at 30 ℃~100 ℃; After dropwising, continue to stir insulation reaction 1.5~3 hours.
5,, it is characterized in that after generating Grignard reagent, cooling by the preparation method of the described dibutylmagnesium of claim 1, under 0 ℃~60 ℃ temperature, add the n-Butyl Lithium hexane solution fast, insulation reaction 1~2 hour, holding temperature are controlled at 30 ℃~120 ℃.
6, press the preparation method of the described dibutylmagnesium of claim 1, it is characterized in that described Sec-Butyl Chloride solution is formulated by Sec-Butyl Chloride and solvent, strength of solution is 0.6~1.05mol/L, and described solvent is an ether, or is in tetrahydrofuran (THF), benzene, toluene, the normal hexane any one.
7, by the preparation method of the described dibutylmagnesium of claim 1, it is characterized in that described n-Butyl Lithium hexane solution is formulated by n-Butyl Lithium and solvent normal hexane, the volumetric molar concentration of solution is 2.5mol/L.
CNA2008101968974A 2008-09-09 2008-09-09 The preparation method of dibutylmagnesium Pending CN101362772A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2008101968974A CN101362772A (en) 2008-09-09 2008-09-09 The preparation method of dibutylmagnesium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2008101968974A CN101362772A (en) 2008-09-09 2008-09-09 The preparation method of dibutylmagnesium

Publications (1)

Publication Number Publication Date
CN101362772A true CN101362772A (en) 2009-02-11

Family

ID=40389398

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2008101968974A Pending CN101362772A (en) 2008-09-09 2008-09-09 The preparation method of dibutylmagnesium

Country Status (1)

Country Link
CN (1) CN101362772A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9499880B2 (en) * 2015-03-06 2016-11-22 Battelle Memorial Institute System and process for production of magnesium metal and magnesium hydride from magnesium-containing salts and brines

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9499880B2 (en) * 2015-03-06 2016-11-22 Battelle Memorial Institute System and process for production of magnesium metal and magnesium hydride from magnesium-containing salts and brines

Similar Documents

Publication Publication Date Title
CN106674257A (en) Continuous production method of Grignard reagent
CN101891621B (en) Compounding method for 3- ethyoxyl-4-ethoxycarbonyl phenylacetic acid
CN104072387B (en) Preparation method of 2-cyano-4' -methyl biphenyl
CN102532045A (en) Method for producing cyanuric acid from urea used as raw material
CN103242194A (en) Preparation method for 2,2-diisopropyl propionitrile
CN102718624B (en) Method for synthesizing triphenylchloromethane
CN114516780B (en) Preparation method of 3,4, 5-trifluoro-bromobenzene
CN112028752B (en) Synthetic method of 3',5' -dichloro-2, 2-trifluoroacetophenone
CN106831851A (en) A kind of preparation method of allyl silicane
CN106946224B (en) The method for preparing α-three aluminum hydride with lithium aluminium hydride reduction and lithium borohydride mixed catalytic
CN101362772A (en) The preparation method of dibutylmagnesium
CN103012288B (en) Preparation method of 6-chloro-1,3-dimethyluracil
CN105085158B (en) A kind of synthetic method of p-methylbenzotrifluoride
CN103058856B (en) Method for preparing 4-(2,4,5-trifluorophenyl)-5-oxobutyric acid
CN106349139A (en) Preparation method of high-purity benzoyl peroxide
CN105418399A (en) Synthesis method of 2-methoxy-4-hydroxypropiophenone
CN110776446B (en) Process for preparing diaryl dithioethers
CN105111039A (en) Preparation method of chloroisopentene
CN108409768A (en) A kind of preparation method of boron trifluoride benzylamine complex compound
CN112778109B (en) Preparation method of 1- [ 3-chloro-5- (trifluoromethyl) phenyl ] -2,2, 2-trifluoroacetone and derivatives thereof
CN112430197B (en) A kind of synthetic method of tert-butyl 3-oxo-5-hydroxyl-6-cyanohexanoate
CN102532038B (en) Method for preparing 2-methyl-1-pyrimidine-5-yl-1-(4-fluoroform methoxyl phenyl) allene-1-alcohol
CN105384612B (en) The preparation method of chloroethyl positive propyl ether
CN101210026A (en) Method for preparing sodium tetraphenylborate
CN116730813B (en) Method for preparing 4,4' -difluorobenzophenone from 4-chlorofluorobenzene

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Open date: 20090211