CN101696153B - Preparation method of 3,3-dimethyl-1-butanol - Google Patents
Preparation method of 3,3-dimethyl-1-butanol Download PDFInfo
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- CN101696153B CN101696153B CN 200910229704 CN200910229704A CN101696153B CN 101696153 B CN101696153 B CN 101696153B CN 200910229704 CN200910229704 CN 200910229704 CN 200910229704 A CN200910229704 A CN 200910229704A CN 101696153 B CN101696153 B CN 101696153B
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Abstract
The invention relates to a preparation method of 3,3-dimethyl-1-butanol. General raw materials with low cost, such as tertiary butanol, concentrated hydrochloric acid, 1,2-dichloroethane, potassium hydroxide, and the like, are adopted; a Grignard reagent is prepared and then is reacted with the 1,2-dichloroethane to obtain a product; and the product is further hydrolyzed to synthesized and purified to prepare the 3,3-dimethyl-1-butanol. The invention simplifies the preparation method of the 3,3-dimethyl-1-butanol, improves the reaction yield of the 3,3-dimethyl-1-butanol, adopts general raw materials with low cost on the premise of avoiding using high-pressure equipment, shortens the reaction time, simplifies the aftertreatment procedures of products and greatly lowers the preparation cost of the 3,3-dimethyl-1-butanol.
Description
Technical field
The present invention relates to the preparation method of 3,3-dimethyl-1-butanol, belong to the foodstuff additive synthesis technical field.
Background technology
Foodstuff additive are being brought into play more and more important effect in modern food industry, play irreplaceable effect at aspects such as painted, seasonings, being subject to the practitioner pays close attention to widely, along with the research that it is deepened continuously, constantly there is novel product to come out, research to the update of old product also never stopped, and knob is sweet to be exactly one of them exemplary.Knob is sweet, and what its cost control is played very important impact in synthetic is 3,3-dimethyl-1-butanol, and its fancy price hampers the sweet further application of knob.
According to existing bibliographical information, the hydro-reduction reaction under high temperature, high pressure of 3,3-dimethyl-1-butanol, 3, the 3-of employing dimethyl-1-butyric acid prepares more, the shortcoming of the method is raw materials used 3,3-dimethyl-1-butyric acid price is more expensive, and severe reaction conditions in the reaction process, and equipment requirements is higher, so 3, the 3-dimethyl-1-butanol holds at high price, and has had a strong impact on the further application of 3,3-dimethyl-1-butanol.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind ofly 3, the preparation method of 3-dimethyl-1-butanol adopts low-cost raw material to realize 3,3-dimethyl-1-butanol cost degradation industrial production.
Summary of the invention
A kind of 3, the preparation method of 3-dimethyl-1-butanol, first with the trimethyl carbinol and haloid acid reaction preparation tertiary butyl halogen, take tetrahydrofuran (THF) as solvent tertiary butyl halogen is prepared into grignard reagent tertiary butyl magnesium halide again, obtains 3 with the reaction of 1,2-ethylene dichloride again, 3-dimethylbutyl halogen, gained 3,3-dimethylbutyl halogen are hydrolyzed in potassium hydroxide aqueous solution and obtain 3,3-dimethyl-1-butanol.
Take haloid acid as example as hydrochloric acid, reaction equation is as follows:
Above gained reaction product is further purified, and can make product 3, the 3-dimethyl-1-butanol.
Detailed Description Of The Invention
A kind of 3, the preparation method of 3-dimethyl-1-butanol, step is as follows:
(1) the raw material trimethyl carbinol, haloid acid are joined according to 1: 1～5 volume ratios reflux 0.5～8 hour in the reactor, cooling, separatory, gained oil reservoir are used respectively alkaline aqueous solution, water, saturated U-Ramin MC solution washing, and desiccant dryness gets tertiary butyl halogen; Keep 0-8 ℃ of temperature in this step in washing, the drying process.
(2) tertiary butyl halogen that step (1) is made is added drop-wise in the anhydrous reactor of tertiary butyl halogen anaerobic that tetrahydrofuran (THF), magnesium, iodine and initiation usefulness are housed, be warming up to boiling after dripping off, keep boiling 0.5-5 hour, get tertiary butyl magnesium halide (Grignard reagent).
In this step (2), the mol ratio of tertiary butyl halogen and magnesium is 1: 0.8-5, the volume ratio of tertiary butyl halogen total amount and tetrahydrofuran (THF) is 1: 1-10, and the tertiary butyl halogen that causes usefulness is the 5-30% volume ratio of tertiary butyl halogen total amount, the iodine consumption is the 0.1-1wt% (weight ratio) of tertiary butyl halogen total amount.
(3) under the anhydrous condition of anaerobic, gained tertiary butyl magnesium halide is splashed into 1 under the ice-water bath, in the 2-dihalo-ethane, Grignard reagent and 1, the mol ratio of 2-dihalo-ethane is 1: 1～5, reacts 20-24 hour, transfers pH to 4～6 with dilute hydrochloric acid, separatory, use the organic extractant aqueous phase extracted, be incorporated in the organic phase underpressure distillation, get 3,3-dimethyl-1-halogen butane.
(4) gained 3, and 3-dimethyl-1-halogen butane joins in the sodium hydroxide or potassium hydroxide aqueous solution of 0.1～5mol/L concentration, reflux 1～5 hour, transfer pH to neutral, separatory is used the organic extractant aqueous phase extracted, is incorporated in the organic phase, underpressure distillation gets 3,3-dimethyl-1-butanol product.
Above-mentioned steps (1) haloid acid is selected from concentration and is not less than 25% concentrated hydrochloric acid, concentration and is not less than 20% Hydrogen bromide or concentration and is not less than 15% hydroiodic acid HI.Be mass percent concentration.
Yellow soda ash, sodium bicarbonate, sodium hydroxide, potassium hydroxide or calcium hydroxide preparation can be selected in used alkaline aqueous solution pH=8～10 in above-mentioned steps (1) washing.
Preferably, used alkaline aqueous solution is saturated sodium bicarbonate aqueous solution in above-mentioned steps (1) washing.Prevent effectively that not only intermediate tertiary butyl halogen is soluble in water, the trimethyl carbinol soluble in water, unreacted acidic hydrogen hydracid and other impurity can also be transferred to aqueous phase and discard.
The described siccative of above-mentioned steps (1) is selected from U-Ramin MC, anhydrous magnesium sulfate or anhydrous sodium sulphate.
Preferably, adopt protection of inert gas in above-mentioned steps (2) the Grignard reagent preparation process, rare gas element generally is selected from nitrogen or argon gas.
Preferably, the magnesium described in the above-mentioned steps (2) is the activated magnesium with the hydrogen instant restoring, or the instant magnesium rod of shearing.Described " immediately " refer to the magnesium behind the hydrogen reducing or shear after magnesium rod at once with regard to usefulness, prevent from placing make magnesium the surface by airborne dioxygen oxidation, form fine and close oxide film, the generation of inhibited reaction.
Above-mentioned steps (3) is described 1, and 2-dihalo-ethane is selected from 1,2-ethylene dichloride, glycol dibromide or 1,2-ethylidene periodide.
Organic extractant is selected from ethyl acetate, methylene dichloride or chloroform described in above-mentioned steps (3), (4).
Technical characterstic and the excellent results of the inventive method are as follows:
1. in the process of preparation tertiary butyl halogen, when washing, keep low temperature as far as possible, preferred 0-8 ℃, can reduce the hydrolysis of tertiary butyl halogen, reduce the generation of the impurity trimethyl carbinol, side reaction occurs when avoiding next step Grignard reagent.
2. Grignard reagent is unstable in air and other wet environments, so the present invention preferably adopts protection of inert gas to keep dry in reaction process.
3. adopt the halogen of the tertiary butyl halogen when Grignard reagent prepares not simultaneously, active can the variation to some extent, but adopt activated magnesium or newly shear magnesium rod Effective Raise productive rate.
4.3, in 3-dimethyl-1-halogen butane preparation feedback, the reaction of saturated dihalide and bimolecular Grignard reagent might occur, produce alkane by-product, adopt described Grignard reagent to splash into 1 under the ice-water bath, but 2-dihalo-ethane Effective Raise productive rate.Though otherwise saturated dihalide is joined that Grignard reagent also can obtain product but productive rate can decrease.
The present invention adopts low-cost common chemical reagent, under the general chemistry reaction conditions, can high yield prepare target compound 3, the 3-dimethyl-1-butanol, avoid using under the prerequisite of high-tension apparatus and shortened the reaction times, the raw materials used trimethyl carbinol, concentrated hydrochloric acid, 1,2-ethylene dichloride, potassium hydroxide are cheap and easy to get, and preparation manipulation is simple, last handling process is simple, product yield is high, steady quality, and parameter is convenient to control, flow process is short, energy consumption is low, greatly reduces the preparation cost of 3,3-dimethyl-1-butanol.
Embodiment
The invention will be further described below in conjunction with embodiment, but be not limited to this.
Embodiment 1:
To be 30% concentrated hydrochloric acid according to 1: 3 volume ratio join in the reactor refluxed 5 hours for the raw material trimethyl carbinol, concentration, cooling, separatory, oil reservoir are used respectively 3-5 ℃ of cold sodium bicarbonate aqueous solution, water, saturated U-Ramin MC solution washing, anhydrous U-Ramin MC is dry, productive rate 91%.
Tertiary butyl chloride evenly slowly add (joining day is not less than 0.5 hour) to tetrahydrofuran (THF) is housed, with in the reactor under the anhydrous condition of tertiary butyl chloride anaerobic of the iodine of the magnesium of hydrogen instant restoring, tertiary butyl chloride total amount 0.5% and tertiary butyl chloride total amount 20%, the mol ratio of tertiary butyl chloride total amount and magnesium is 1: 1.2, the volume ratio of tertiary butyl chloride total amount and tetrahydrofuran (THF) is 1: 5, be warming up to boiling after dripping off, keep boiling 1 hour, get Grignard reagent tertiary butyl chlorination magnesium.
Under the anhydrous condition of anaerobic, gained tertiary butyl chlorination magnesium is splashed in the there-necked flask that 1,2-ethylene dichloride is housed under the ice-water bath, the mol ratio of Grignard reagent and 1,2-ethylene dichloride is 1: 3, reacts 24 hours, the beaker of distilled water is equipped with in impouring, and dilute hydrochloric acid transfers pH to neutral, separatory, the chloroform extraction water, be incorporated in the organic phase, underpressure distillation gets 3,3-dimethyl-1-chlorobutane, productive rate 82%.
Gained 3,3-dimethyl-1-chlorobutane join in the aqueous sodium hydroxide solution of 4mol/L concentration, reflux 4 hours, transfer pH to neutral, separatory, and the chloroform extraction water is incorporated in the organic phase, and underpressure distillation gets product, and productive rate is 85%.
Embodiment 2:
To be 38% concentrated hydrobromic acid according to 1: 3 volume ratio join in the reactor refluxed 5 hours for the raw material trimethyl carbinol, concentration, cooling, separatory, oil reservoir is used respectively 2-5 ℃ of cold sodium bicarbonate aqueous solution, water, saturated U-Ramin MC solution washing, anhydrous U-Ramin MC is dry, whole process keeps low temperature to be no more than 8 ℃, productive rate 95% as far as possible.
Tert.-butyl bromide evenly slowly (joining day is not less than 0.5 hour) joins in the reactor under the anhydrous condition of tert.-butyl bromide anaerobic of iodine that tetrahydrofuran (THF), the activated carbon of hydrogen instant restoring, the total consumption 0.5% of tert.-butyl bromide are housed and the total consumption 20% of tert.-butyl bromide, be warming up to boiling after dripping off, keep boiling 2 hours, get Grignard reagent tertiary butyl bromination magnesium.
Under the anhydrous condition of anaerobic, gained tertiary butyl bromination magnesium is splashed in the there-necked flask that 1,2-ethylene dichloride is housed under the ice-water bath, the mol ratio of Grignard reagent and 1,2-ethylene dichloride is 1: 3, reacts 24 hours, the beaker of distilled water is equipped with in impouring, and dilute hydrochloric acid transfers pH to neutral, separatory, the chloroform extraction water, be incorporated in the organic phase, underpressure distillation gets 3,3-dimethyl-1-chlorobutane, productive rate 82%.
Gained 3,3-dimethyl-1-chlorobutane join in the aqueous sodium hydroxide solution of 3mol/L concentration, reflux 5 hours, transfer pH to neutral, separatory, and the chloroform extraction water is incorporated in the organic phase, and underpressure distillation gets product, and productive rate is 85%.
Embodiment 3:
To be 30% concentrated hydrochloric acid according to 1: 3 volume ratio join in the reactor refluxed 6 hours for the raw material trimethyl carbinol, concentration, cooling, separatory, oil reservoir is used respectively sodium bicarbonate aqueous solution cold below 5 ℃, water, saturated U-Ramin MC solution washing, anhydrous U-Ramin MC is dry, whole process keeps low temperature to be no more than 8 ℃, productive rate 91% as far as possible.
Tertiary butyl chloride evenly slowly (joining day is not less than 0.5 hour) joins in the reactor under the anhydrous condition of tertiary butyl chloride anaerobic that tetrahydrofuran (THF), the activated carbon of hydrogen instant restoring, total consumption 0.5% iodine of tertiary butyl chloride and the total consumption 20% of tertiary butyl chloride are housed, the mol ratio of tertiary butyl chloride and magnesium is 1: 1.2, the volume ratio of tertiary butyl chloride and tetrahydrofuran (THF) is 1: 5, be warming up to boiling after dripping off, keep boiling 5 hours, get Grignard reagent tertiary butyl bromination magnesium.
Under the anhydrous condition of anaerobic, gained tertiary butyl bromination magnesium is splashed in the there-necked flask that glycol dibromide is housed under the ice-water bath, the mol ratio of Grignard reagent and glycol dibromide is 1: 2.2, reacts 24 hours, the beaker of distilled water is equipped with in impouring, and dilute hydrochloric acid transfers pH to neutral, separatory, the chloroform extraction water, be incorporated in the organic phase, underpressure distillation gets 3,3-dimethyl-1-n-butyl bromide, productive rate 92%.
Gained 3,3-dimethyl-1-n-butyl bromide joins in the aqueous sodium hydroxide solution of 2mol/L concentration, refluxes 6 hours, transfers pH to neutral, separatory, the chloroform extraction water is incorporated in the organic phase, and underpressure distillation gets product, and productive rate is 95%.
Claims (8)
1. one kind 3, the preparation method of 3-dimethyl-1-butanol, step is as follows:
(1) the raw material trimethyl carbinol, haloid acid are joined according to 1: 1～5 volume ratios reflux 0.5～8 hour in the reactor, cooling, separatory, gained oil reservoir are used respectively alkaline aqueous solution, water, saturated U-Ramin MC solution washing, and desiccant dryness gets tertiary butyl halogen; Keep 0-8 ℃ of temperature in this step in washing, the drying process.
(2) tertiary butyl halogen that step (1) is made is added drop-wise in the anhydrous reactor of tertiary butyl halogen anaerobic that tetrahydrofuran (THF), magnesium, iodine and initiation usefulness are housed, and is warming up to boiling after dripping off, and keeps boiling 0.5-5 hour, gets tertiary butyl magnesium halide;
In this step (2), the mol ratio of tertiary butyl halogen and magnesium is 1: 0.8-5, the volume ratio of tertiary butyl halogen total amount and tetrahydrofuran (THF) is 1: 1-10, and the tertiary butyl halogen that causes usefulness is the 5-30% volume ratio of tertiary butyl halogen total amount, the iodine consumption is the 0.1-1wt% of tertiary butyl halogen total amount;
(3) under the anhydrous condition of anaerobic, gained tertiary butyl magnesium halide is splashed into 1 under the ice-water bath, in the 2-dihalo-ethane, Grignard reagent and 1, the mol ratio of 2-dihalo-ethane is 1: 1～5, reacts 20-24 hour, transfers pH to 4～6 with dilute hydrochloric acid, separatory, use the organic extractant aqueous phase extracted, be incorporated in the organic phase underpressure distillation, get 3,3-dimethyl-1-halogen butane; Grignard reagent is described tertiary butyl magnesium halide;
(4) gained 3, and 3-dimethyl-1-halogen butane joins in the sodium hydroxide or potassium hydroxide aqueous solution of 0.1～5mol/L concentration, reflux 1～5 hour, transfer pH to neutral, separatory is used the organic extractant aqueous phase extracted, is incorporated in the organic phase, underpressure distillation gets 3,3-dimethyl-1-butanol product.
2. as claimed in claim 13, the preparation method of 3-dimethyl-1-butanol is characterized in that, step (1) haloid acid is selected from concentration and is not less than 25% concentrated hydrochloric acid, concentration and is not less than 20% Hydrogen bromide or concentration and is not less than 15% hydroiodic acid HI.
3. as claimed in claim 13, the preparation method of 3-dimethyl-1-butanol is characterized in that, yellow soda ash, sodium bicarbonate, sodium hydroxide, potassium hydroxide or calcium hydroxide preparation are selected in used alkaline aqueous solution pH=8～10 in step (1) washing.
4. as claimed in claim 13, the preparation method of 3-dimethyl-1-butanol is characterized in that, used alkaline aqueous solution is saturated sodium bicarbonate aqueous solution in step (1) washing.
5. as claimed in claim 13, the preparation method of 3-dimethyl-1-butanol is characterized in that, the described siccative of step (1) is selected from U-Ramin MC, anhydrous magnesium sulfate or anhydrous sodium sulphate.
6. as claimed in claim 13, the preparation method of 3-dimethyl-1-butanol is characterized in that, adopts protection of inert gas in step (2) the Grignard reagent preparation process, and rare gas element generally is selected from nitrogen or argon gas; Grignard reagent is described tertiary butyl magnesium halide.
7. as claimed in claim 13, the preparation method of 3-dimethyl-1-butanol is characterized in that, step (3) is described 1, and 2-dihalo-ethane is selected from 1,2-ethylene dichloride, glycol dibromide or 1,2-ethylidene periodide.
8. as claimed in claim 13, the preparation method of 3-dimethyl-1-butanol is characterized in that, organic extractant is selected from ethyl acetate, methylene dichloride or chloroform described in step (3), (4).
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| CN 200910229704 CN101696153B (en) | 2009-10-23 | 2009-10-23 | Preparation method of 3,3-dimethyl-1-butanol |
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| CN101696153B true CN101696153B (en) | 2013-04-03 |
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| CN102531838B (en) * | 2012-01-18 | 2014-05-28 | 常州市牛塘化工厂有限公司 | Method for preparing 3,3-dimethyl-1-butanol |
| CN102584530B (en) * | 2012-01-18 | 2014-02-12 | 常州市牛塘化工厂有限公司 | Method for preparing 3,3-dimethyl-1-butanol |
| CN104876791A (en) * | 2015-04-21 | 2015-09-02 | 苏州久王环保科技股份有限公司 | Preparation method of 1,1,1,2,2,3,3-heptafluoro-7-bromoheptane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1360563A (en) * | 1999-07-02 | 2002-07-24 | 纳特拉斯维特公司 | Process for preparation of 3,3-dimethylbutanal |
| CN1778789A (en) * | 2004-11-23 | 2006-05-31 | 王俊华 | Production of 3,3-dimethyl-butyrylchlorine |
| CN101508623A (en) * | 2009-03-19 | 2009-08-19 | 清华大学 | Plasma coal cracking reaction apparatus relating to flow screening component |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1360563A (en) * | 1999-07-02 | 2002-07-24 | 纳特拉斯维特公司 | Process for preparation of 3,3-dimethylbutanal |
| CN1778789A (en) * | 2004-11-23 | 2006-05-31 | 王俊华 | Production of 3,3-dimethyl-butyrylchlorine |
| CN101508623A (en) * | 2009-03-19 | 2009-08-19 | 清华大学 | Plasma coal cracking reaction apparatus relating to flow screening component |
Non-Patent Citations (1)
| Title |
|---|
| J.F.Normant,et al..Condensation des reactifs.......《Tetrahedron Letters》.1977,(第37期),3263-3266. * |
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