CN100430358C - Process for synthesizing 4-chlorobutyl methyl ether - Google Patents
Process for synthesizing 4-chlorobutyl methyl ether Download PDFInfo
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- CN100430358C CN100430358C CNB200610016412XA CN200610016412A CN100430358C CN 100430358 C CN100430358 C CN 100430358C CN B200610016412X A CNB200610016412X A CN B200610016412XA CN 200610016412 A CN200610016412 A CN 200610016412A CN 100430358 C CN100430358 C CN 100430358C
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Abstract
The present invention relates to saturated ether containing halogen, and is especially process of synthesizing 4-chlorobutyl methyl ether. The present invention features the reactant molar proportion of tetrahydrofuran, anhydrous methanol and sulfoxide chloride in 1.0 to 1.0-2.0 to 1.5-2.5; the catalyst selected from pyridine, N,N-dimethyl pyridine, N,N-dimethyl formamide, magnesium chloride, zinc chloride and ferric chloride hexahydrate in the amount of 0.5-5.0 mol% of tetrahydrofuran; the solvent selected from cyclohexane, tert-butyl alcohol and acetone and in the amount of 2.5-4.0 mol% of tetrahydrofuran; and optimized reaction conditions including reaction temperature of 80-120 deg.c and reaction time of 1.0-2.0 hr; and the product yield of 68-75 % and purity of 97-99 %. Compared with available technology, the present invention has the advantages of 1-4 hr shorted reaction time, 20-40 deg.c lowered reaction temperature and 13-25 % raised product yield.
Description
Technical field
Technical scheme of the present invention relates to halogen-containing saturated ethers, specifically the synthetic method of 4-chlorobutyl methyl ether.
Background technology
The 4-chlorobutyl methyl ether claims 1-chloro-4-methyl butyl ether again, is a kind of colourless, transparent, volatile, nontoxic and have the oily liquids of irritating smell, and its molecular formula is G
5H
11OCl, structural formula are ClCH
2CH
2CH
2CH
2OCH
3, relative molecular mass 122.59.The boiling point of 4-chlorobutyl methyl ether is 142.5 ℃～142.8 ℃, and refractive index is n
20 D=1.4244, be insoluble in water, be soluble in organic solvents such as pentane, hexane, methylene dichloride.
Contain in the 4-chlorobutyl methyl ether molecule-Cl and R-O-R group, so chlorobutyl methyl ether can be used as a kind of useful reaction intermediate, be used for synthetic other organic compound; Also can be used as initiator of polyreaction, pharmaceutical intermediate and Grignard reagent etc., in addition, the 4-chlorobutyl methyl ether also has important use in the synthetic field of medicine, and in new drug closes war research, occupy important one seat, for example the 4-chlorobutyl methyl ether can be used to synthetic be used for clinical treatment all kinds dysthymia disorders and compulsive medicine.
In view of the important application of 4-chlorobutyl methyl ether, its study on the synthesis is more and more paid close attention to by the people.US 5621149,1997 to disclose with tetrahydrofuran (THF), methyl alcohol and sulfur oxychloride be raw material, mol ratio such as press and add methyl alcohol, tetrahydrofuran (THF), then sulfur oxychloride is added drop-wise in the reaction mixture by constant pressure funnel, remain on below 15 ℃, after dripping off, reaction solution is heated to 120 ℃, reaction is 3 hours under the stirring and refluxing condition, and obtaining the product productive rate through the separation purification then is 59.8%.Robert C Elderfield, Burnett M Pitt, Iris Wempen.Synthesis of the branched chain5-isopropylaminoamyl and 4-isopropylaminobutyl ethers and of the bromidesderived from them[J] .J Am Chem Soc, 1950,72:1334-1345. introduced with 1,4-dichlorobutane and methyl alcohol are raw material, at first 1,4-dichlorobutane and 250ml methyl alcohol reaction mixture are heated to backflow, add the solution that sodium methylate and methyl alcohol were made into by dropping funnel then, the dropping time is 5 hours, then mixture heating up is arrived and reflux, can stop up to being neutrality with the test of wide pH value test paper, product yield was 36% method after separation was purified.William E.McEwen, A.Blair Janes, Jerome W.Knapczyk, el al.Role of throughspace 2p-3d overlap in the alkylation of phosphines[J] .J Am Chem Soc, 1978,100 (23): it is raw material that 7304-7311. has disclosed with the 4-butylene-chlorohydrin, under ice bath cooling and quick agitation condition, anhydrous tetrahydro furan and sodium hydride, the emulsion of methyl iodide is added drop-wise in the mixed solution of 4-butylene-chlorohydrin and anhydrous tetrahydro furan, the dropping time is 1.5 hours, after dropwising, mixed solution is risen to room temperature and continues stirring fast, reaction finishes and obtains the 4-chlorobutyl methyl ether after purification is separated in the back, and productive rate is 20% method.
Though used reaction raw materials, reaction conditions and the route of synthesis of aforesaid method has nothing in common with each other, all there is the long and lower shortcoming of product yield of reaction times.
Summary of the invention
Technical problem to be solved by this invention is: a kind of synthetic method of 4-chlorobutyl methyl ether is provided, and this method has overcome the long and lower shortcoming of product yield of reaction times.
The present invention solves this technical problem the technical scheme that is adopted: the synthetic method of 4-chlorobutyl methyl ether is as follows:
(1) preparation of raw material
Reactant: tetrahydrofuran (THF): anhydrous methanol: sulfur oxychloride molar ratio=1.0: 1.0～2.0: 1.5～2.5,
Catalyzer: pyridine, N, N dimethylamine yl pyridines, N, dinethylformamide, magnesium chloride, zinc chloride or ferric chloride (FeCl36H2O), catalyst levels are 0.5～5.0% of used tetrahydrofuran (THF) molar weight,
Solvent: hexanaphthene, the trimethyl carbinol or acetone, the mol ratio of solvent and tetrahydrofuran (THF) consumption is 1.0: 2.5～4.0;
(2) operation steps
(2.1) by (1) regulation measure tetrahydrofuran (THF) and anhydrous methanol joins in the reaction flask, with frozen water/methyl alcohol cooling bath this mixed solution is cooled to 0 ℃, in this mixed solution, add to press the catalyzer of (1) specified amount then, stir;
(2.2) get sulfur oxychloride, dropwise join in the reaction solution that (2.1) form, dropping temperature is maintained 6～10 ℃ by the rate of addition of regulating sulfur oxychloride by constant pressure funnel by (1) specified amount;
(2.3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2.2) form, add solvent by (1) specified amount, then this reaction solution is heated to 80～120 ℃ gradually, under stirring and refluxing, react and do not emit to there being gas, reaction times is 1.0～2.0 hours, stops heating, and this reaction solution is cooled to room temperature;
(2.4) reaction solution that (2.3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is to clean, is washed with distilled water to only again, and the last consumption that adds in the oily product that separatory obtains is that the anhydrous magnesium sulfate of tetrahydrofuran (THF) molar weight 24%～34% carries out drying.
(2.5) the oily product that (2.4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent, temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product, productive rate is 68～75%, and product purity is 97～99%.
The invention has the beneficial effects as follows: the present invention compares with existing 4-chlorobutyl methyl ether preparation method, and the reaction times shortened 1～4 hour, temperature of reaction has reduced by 20～40 ℃, product yield and improved 13～25%.In detail relatively lift related data in the prior art referring to the related data in the following example and background technology.
Embodiment
Embodiment 1
(1) gets the 0.50mol tetrahydrofuran (THF) and the 0.55mol anhydrous methanol joins in the reaction flask, mixed solution is cooled to 0 ℃, in mixed solution, add the 0.0084mol magnesium chloride then, stir with frozen water/methyl alcohol cooling bath;
(2) the 0.80mol sulfur oxychloride is dropwise joined by constant pressure funnel in the reaction solution of (1) formation, dropping temperature is maintained 6 ℃ by the rate of addition of regulating sulfur oxychloride;
(3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2) form, add hexanaphthene 0.15mol, then this reaction solution is heated to 96 ℃ gradually, under stirring and refluxing, reacts and do not emit 1.5 hours reaction times to there being gas, stop heating, this reaction solution is cooled to room temperature;
(4) reaction solution that (3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is washed with distilled water to only to clean again, and the last 0.12mol anhydrous magnesium sulfate that adds in the oily product that separatory obtains carries out drying.
(5) the oily product that (4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent etc., temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product 0.36mol, productive rate is 72.0%, and product purity is 98%.
Embodiment 2
(1) gets the 0.5mol tetrahydrofuran (THF) and the 0.63mol anhydrous methanol joins in the reaction flask, mixed solution is cooled to 0 ℃, in mixed solution, add the 0.0044mol ferric chloride (FeCl36H2O) then, stir with frozen water/methyl alcohol cooling bath;
(2) the 0.88mol sulfur oxychloride is dropwise joined by constant pressure funnel in the reaction solution of (1) formation, dropping temperature is maintained 7 ℃ by the rate of addition of regulating sulfur oxychloride;
(3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2) form, add trimethyl carbinol 0.14mol, then this reaction solution is heated to 101 ℃ gradually, under stirring and refluxing, reacts and do not emit 1.2 hours reaction times to there being gas, stop heating, this reaction solution is cooled to room temperature;
(4) reaction solution that (3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is washed with distilled water to only to clean again, and the last 0.14mol anhydrous magnesium sulfate that adds in the oily product that separatory obtains carries out drying.
(5) the oily product that (4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent etc., temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product 0.35mol, productive rate is 70.41%, and product purity is 98.5%.
Embodiment 3
(1) get the 0.5mol tetrahydrofuran (THF) and the 0.73mol anhydrous methanol joins in the reaction flask, with frozen water/methyl alcohol cooling bath mixed solution is cooled to 0 ℃, add 0.021mol N then in mixed solution, the N dimethylamine yl pyridines stirs;
(2) the 0.93mol sulfur oxychloride is dropwise joined by constant pressure funnel in the reaction solution of (1) formation, dropping temperature is maintained 8 ℃ by the rate of addition of regulating sulfur oxychloride;
(3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2) form, add acetone 0.16mol, then this reaction solution is heated to 104 ℃ gradually, under stirring and refluxing, reacts and do not emit 1.8 hours reaction times to there being gas, stop heating, this reaction solution is cooled to room temperature;
(4) reaction solution that (3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is washed with distilled water to only to clean again, and the last 0.15mol anhydrous magnesium sulfate that adds in the oily product that separatory obtains carries out drying.
(5) the oily product that (4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent etc., temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product 0.37mol, productive rate is 74.76%, and product purity is 97.5%.
Embodiment 4
(1) gets the 0.5mol tetrahydrofuran (THF) and the 1.00mol anhydrous methanol joins in the reaction flask, mixed solution is cooled to 0 ℃, in mixed solution, add the 0.0025mol pyridine then, stir with frozen water/methyl alcohol cooling bath;
(2) the 1.25mol sulfur oxychloride is dropwise joined by constant pressure funnel in the reaction solution of (1) formation, dropping temperature is maintained 9 ℃ by the rate of addition of regulating sulfur oxychloride;
(3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2) form, add acetone 0.20mol, then this reaction solution is heated to 80 ℃ gradually, under stirring and refluxing, reacts and do not emit 2 hours reaction times to there being gas, stop heating, this reaction solution is cooled to room temperature;
(4) reaction solution that (3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is washed with distilled water to only to clean again, and the last 0.17mol anhydrous magnesium sulfate that adds in the oily product that separatory obtains carries out drying.
(5) the oily product that (4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent etc., temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product 0.356mol, productive rate is 71.2%, and product purity is 98.2%.
Embodiment 5
(1) gets the 0.50mol tetrahydrofuran (THF) and the 0.50mol anhydrous methanol joins in the reaction flask, mixed solution is cooled to 0 ℃, in mixed solution, add the 0.0084mol zinc chloride then, stir with frozen water/methyl alcohol cooling bath;
(2) the 0.75mol sulfur oxychloride is dropwise joined by constant pressure funnel in the reaction solution of (1) formation, dropping temperature is maintained 10 ℃ by the rate of addition of regulating sulfur oxychloride;
(3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2) form, add hexanaphthene 0.125mol, then this reaction solution is heated to 120 ℃ gradually, under stirring and refluxing, reacts and do not emit 1 hour reaction times to there being gas, stop heating, this reaction solution is cooled to room temperature;
(4) reaction solution that (3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is washed with distilled water to only to clean again, and the last 0.12mol anhydrous magnesium sulfate that adds in the oily product that separatory obtains carries out drying.
(5) the oily product that (4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent etc., temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product 0.343mol, productive rate is 68.6%, and product purity is 97.0%.
Embodiment 6
(1) get the 0.5mol tetrahydrofuran (THF) and the 0.75mol anhydrous methanol joins in the reaction flask, with frozen water/methyl alcohol cooling bath mixed solution is cooled to 0 ℃, add 0.025mol N then in mixed solution, dinethylformamide stirs;
(2) the 1.00mol sulfur oxychloride is dropwise joined by constant pressure funnel in the reaction solution of (1) formation, dropping temperature is maintained 7 ℃ by the rate of addition of regulating sulfur oxychloride;
(3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2) form, add trimethyl carbinol 0.15mol, then this reaction solution is heated to 100 ℃ gradually, under stirring and refluxing, reacts and do not emit 1.5 hours reaction times to there being gas, stop heating, this reaction solution is cooled to room temperature;
(4) reaction solution that (3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is washed with distilled water to only to clean again, and the last 0.145mol anhydrous magnesium sulfate that adds in the oily product that separatory obtains carries out drying.
(5) the oily product that (4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent etc., temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product 0.347mol, productive rate is 69.4%, and product purity is 99.0%.
Claims (1)
1.4-the synthetic method of chlorobutyl methyl ether is characterized in that; Following technology is arranged:
(1) preparation of raw material
Reactant: tetrahydrofuran (THF): anhydrous methanol: sulfur oxychloride molar ratio=1.0: 1.0～2.0: 1.5～2.5,
Catalyzer: pyridine, N, N dimethylamine yl pyridines, N, dinethylformamide, magnesium chloride, zinc chloride or ferric chloride (FeCl36H2O), catalyst levels are 0.5～5.0% of used tetrahydrofuran (THF) molar weight,
Solvent: hexanaphthene, the trimethyl carbinol or acetone, the mol ratio of solvent and tetrahydrofuran (THF) consumption is 1.0: 2.5～4.0;
(2) operation steps
(2.1) by (1) regulation measure tetrahydrofuran (THF) and anhydrous methanol joins in the reaction flask, with frozen water/methyl alcohol cooling bath this mixed solution is cooled to 0 ℃, in this mixed solution, add to press the catalyzer of (1) specified amount then, stir;
(2.2) get sulfur oxychloride, dropwise join in the reaction solution that (2.1) form, dropping temperature is maintained 6～10 ℃ by the rate of addition of regulating sulfur oxychloride by constant pressure funnel by (1) specified amount;
(2.3) after sulfur oxychloride dropwises, remove cooling bath, in the reaction solution that (2.2) form, add solvent by (1) specified amount, then this reaction solution is heated to 80～120 ℃ gradually, under stirring and refluxing, react and do not emit to there being gas, reaction times is 1.0～2.0 hours, stops heating, and this reaction solution is cooled to room temperature;
(2.4) reaction solution that (2.3) are formed is transferred in the separating funnel, at first extracts whole products with pentane, is washed with distilled water to then only, adds saturated NaHCO again
3Solution washing is to clean, is washed with distilled water to only again, and the last consumption that adds in the oily product that separatory obtains is that the anhydrous magnesium sulfate of tetrahydrofuran (THF) molar weight 24%～34% carries out drying,
(2.5) the oily product that (2.4) are formed is transferred to and distills in the there-necked flask, at first collect extraction agent, solvent, temperature is increased to more than 130 ℃ gradually then, collect the cut in 140～146 ℃ of scopes, can obtain 4-chlorobutyl methyl ether product, productive rate is 68～75%, and product purity is 97～99%.
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| CN113999091A (en) * | 2021-11-30 | 2022-02-01 | 南通宝凯药业有限公司 | Preparation method of bis (4-chlorobutyl) ether |
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| US5621149A (en) * | 1994-02-18 | 1997-04-15 | Fmc Corporation | Process for preparing functionalized initiators for anionic polymerization |
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| US5621149A (en) * | 1994-02-18 | 1997-04-15 | Fmc Corporation | Process for preparing functionalized initiators for anionic polymerization |
Non-Patent Citations (2)
| Title |
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| 4_氯丁基甲醚的合成方法. 王丽华等.天津化工，第20卷第1期. 2006 |
| 4_氯丁基甲醚的合成方法. 王丽华等.天津化工，第20卷第1期. 2006 * |
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Assignee: Cangzhou Senary Chemical Technology Co., Ltd. Assignor: Hebei University of Technology Contract fulfillment period: 2009.9.23 to 2014.9.22 contract change Contract record no.: 2009130000165 Denomination of invention: Process for synthesizing 4-chlorobutyl methyl ether Granted publication date: 20081105 License type: Exclusive license Record date: 2009.9.27 |
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