CN104230674A - Preparation method of dihydroxydibutylether - Google Patents
Preparation method of dihydroxydibutylether Download PDFInfo
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- CN104230674A CN104230674A CN201410429985.XA CN201410429985A CN104230674A CN 104230674 A CN104230674 A CN 104230674A CN 201410429985 A CN201410429985 A CN 201410429985A CN 104230674 A CN104230674 A CN 104230674A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/46—Use of additives, e.g. for stabilisation
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of dihydroxydibutylether. The method is characterized by comprising the following steps: A adopting disulfate as a catalyst, catalyzing 1,3-butanediol to carry out condensation reaction at the temperature of 80-190 DEG C within 1-10 hours, so as to obtain a crude product of dihydroxydibutylether; B cooling the obtained crude product of the dihydroxydibutylether, and alkalifying to adjust the pH value to be 6-10; and C carrying out vacuum distillation at the temperature of 100-300 DEG C, so as to obtain dihydroxydibutylether. The catalyst can be separated from a reactant and a product easily, and does not corrode equipment, and meanwhile, the production process has the characteristics of being simple in post-treatment, free of environmental pollution and the like.
Description
Technical field
The invention belongs to industrial chemicals preparation field, be specifically related to a kind of preparation method of dihydroxydibutylether.
Background technology
Dihydroxydibutylether (dihydroxydibutylether, DHBE) is a kind of colourless odorless flaxen oily liquids, is widely used in field of medicaments.At field of medicaments, it is market-oriented that dihydroxydibutylether (DHBE) capsule is used as treatment liver and gall diseases medicine, and in the listing of multiple countries.Medicine is called Dyskinebyl (Dyskinebyl), is first succeeded in developing by French Laphal pharmaceutical factory and is put on market, and this medicine belongs to the two-way promotor of choleresis, has cholagogic, anti-inflammatory, spasmolysis, protects courage, arranges masonry use, is a kind of choleretic efficiently.
Dihydroxydibutylether is isomer mixture, and it mainly contains three isomer: 4-(3-hydroxybutoxy)-2-butanols (I), 3-(3-hydroxybutoxy)-n-butyl alcohol (II) and 3-(3-hydroxyl-1-methyl propoxy-)-n-butyl alcohol (III).Structural formula is as follows:
Joulty A reports a kind of synthesis technique of dihydroxydibutylether at French Patent (1961) FR1267084A.In this route, 2,2-dicyano ether and the reaction of monobromethane Grignard reagent, then hydrolysis obtains 3,3-dioxo dibutyl ether, under the effect of catalyzer Raney Ni, be reduced into dihydroxydibutylether, productive rate is 15%.Synthetic route is as follows:
Monobromethane grignard reagent reaction method can obtain the product of higher degree, but there is following shortcoming: 1, raw material 2,2-dicyano ether is expensive, low conversion rate; 2, must carry out under the condition of absolute in grignard reagent preparation process, in use procedure, grignard reagent is unstable under having oxygen maybe can provide proton material existent condition, and this also causes its preservation more difficult, makes suitability for industrialized production difficulty.
Elso Manghisi is studied in the dehydrating step of United States Patent (USP) (1986) US4584321 to 1,3 butylene glycol, describes sulphuric acid catalysis reaction process.The intermolecular dehydrating condensation of sulphuric acid catalysis 1,3 butylene glycol becomes ether, then obtains dihydroxydibutylether through underpressure distillation, yield 18.9%.Synthetic route is as follows:
The production technique of existing dihydroxydibutylether is using 1,3 butylene glycol as raw material, obtains under high temperature, sulfuric acid catalysis condition.Although its technique is very ripe, there is following shortcoming:
1, more, the etching apparatus of by product, have the inevitably shortcoming such as discharging of waste liquid;
2, in reaction process, easily make 1,3 butylene glycol generate the unsaturated product of alkene, seriously limit its development and application.
Meng Qingwei adopts Zeo-karb as catalyzer in Chinese patent (2013) CN201310256987.9, and the intermolecular dehydrating condensation of catalysis 1,3 butylene glycol becomes ether, then obtains dihydroxydibutylether through underpressure distillation.Synthetic route is as follows:
Although Zeo-karb can avoid the vitriol oil as the shortcoming of catalyzer, still there is following shortcoming:
1, find in an experiment, after catalyzing cation exchange resin, product is reddish-brown liquid;
2, reaction more than two hours after, the resin catalyst in reaction solution breaks, and causes generating high boiling macromole and ethers product accumulation in the acid site of catalyst surface, have impact on reaction;
3, the olefin compound of reaction generation, reacts with the acidic-group of exchange resin and generates ester, reduce the selectivity of reaction;
4, swelling in reaction solution, the phenomenon of breaking of catalyzer, adds in product the possibility introducing impurity;
5, Zeo-karb is expensive, limits its prospects for commercial application.
Meng Qingwei adopts solid super-strong acid or hydrogen type molecular sieve as catalyzer in Chinese patent (2013) CN201310251783.6, and the intermolecular dehydrating condensation of catalysis 1,3 butylene glycol becomes ether, then obtains dihydroxydibutylether through underpressure distillation.This patent adopts solid super-strong acid or hydrogen type molecular sieve to avoid above-mentioned shortcoming, but, still there is above-mentioned shortcoming:
1, its catalysis generates dihydroxydibutylether is dehydration reaction, due to the strong water absorbability of 1,3 butylene glycol, makes the transformation efficiency of reaction very low;
2, the by product occurred in reaction process is more, the olefines mainly generated by 1,3 butylene glycol intramolecular dehydration;
3, a part of product can continue etherificate occurs, and generates high boiling impurity;
4, solid super-strong acid or hydrogen type molecular sieve expensive, limit its prospects for commercial application.
Summary of the invention
The present invention, in order to overcome above-mentioned technical problem, provides a kind of preparation method of dihydroxydibutylether, adopts the condensation of heterogeneous catalyst catalysis 1,3 butylene glycol to prepare dihydroxydibutylether.Catalyzer of the present invention easily and reactant and product separation, not etching apparatus; Meanwhile, it is simple that production process has aftertreatment, the features such as nonpollution environment.
For achieving the above object, the present invention adopts following technical scheme:
A preparation method for dihydroxydibutylether, is characterized in that: the processing step of the method is as follows:
A, employing hydrosulfate are as catalyzer, and at the temperature of 80-190 DEG C, in 1-10 hour, catalysis 1,3 butylene glycol generation condensation reaction, obtains the crude product of dihydroxydibutylether;
B, the dihydroxydibutylether crude product cooling that will obtain, add alkali and regulate pH value to 6-10;
C, underpressure distillation at 100-300 DEG C of temperature, obtain dihydroxydibutylether.
Catalyst levels of the present invention is the 1.0%-50% of 1,3 butylene glycol quality, and reaction yield is high, and reaction product impurity is few.
In steps A of the present invention, the pressure of condensation reaction is 0.04-0.1Mpa, is conducive to the water of generation to distill out, reaction forward is moved, and is conducive to the generation of reacting.
Hydrosulfate catalyzer in steps A of the present invention is one or more in sodium pyrosulfate, sal enixum, TBuA hydrosulfate, monoammonium sulfate, magnesium hydrogen sulfate, is preferably sal enixum;
Be preferably sal enixum, the effect of reaction is better, and content is higher and impurity is less.
Alkali in step B of the present invention, is preferably sodium hydroxide or potassium hydroxide, and sodium hydroxide or potassium hydroxide are all as highly basic, and catalyzer-hydrosulfate residual in the effective neutralization reaction of energy is with stopped reaction.
Preferably, in described step B, regulate pH value to 7.0 ~ 8.0, all causing dihydroxy dibutyl ether in follow-up still-process, other reaction be produced, thus affect purity and yield under the condition of peracid or excessively alkali.
Preferably, in described step C, the vacuum tightness of underpressure distillation is-0.04--0.1MPa, is conducive to the boiling point reducing product and impurity, thus product can be made to be separated under lower temperature condition with impurity, be conducive to large production under this vacuum degree condition.
The dihydroxydibutylether yield of preparation method of the present invention and purity are all obviously better than existing Method and Technology, and beneficial effect is in particular in:
1, the present invention adopts economy to be easy to get, is easily separated with liquid-phase reaction system, the not hydrosulfate of etching apparatus, relative to sulfuric acid more environmental protection, meets the theory of Green Chemistry; More cheap relative to Zeo-karb, solid super-strong acid and hydrogen type molecular sieve, transformation efficiency is higher.Be applicable to large-scale production and continuous seepage, ensure quality product, production cost is low simultaneously.
2, traditional technology is too strong due to the acidity of reaction solution, makes the organism decarburization in reaction solution and occurs coked phenomenon, causes subsequent disposal difficulty, need to increase the operations such as filtration, but reaction solution is sticky causes filtration difficulty, is unsuitable for scale operation.The reaction solution acidity of present invention process is moderate, and subsequent processes is simple, the process that reaction product only needs a step underpressure distillation to purify, and can obtain the dihydroxydibutylether of purity more than 95%.
Embodiment
Below in conjunction with embodiment, essentiality content of the present invention is described in further detail.
Embodiment 1
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, use hydrosulfate are as catalyzer, and at the temperature of 80 DEG C, in 10 hours, catalysis 1,3 butylene glycol generation condensation reaction, obtains the crude product of dihydroxydibutylether, transformation efficiency 85%;
B, the dihydroxydibutylether crude product cooling that will obtain, add alkali adjust ph to 6;
C, at 100 DEG C of temperature, vacuum tightness is underpressure distillation under-0.1Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 98.1%.
In described steps A.Catalyst levels is 1.0% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.04Mpa.
Hydrosulfate catalyzer in described steps A is sal enixum.
Embodiment 2
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, use hydrosulfate are as catalyzer, and at the temperature of 190 DEG C, in 1 hour, catalysis 1,3 butylene glycol generation condensation reaction, obtains the crude product of dihydroxydibutylether, transformation efficiency 86%;
B, the dihydroxydibutylether crude product cooling that will obtain, add alkali adjust ph to 10;
C, at 300 DEG C of temperature, vacuum tightness is underpressure distillation under-0.04Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 97.4%.
In described steps A, catalyst levels is 1.0% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.04Mpa.
Hydrosulfate catalyzer in described steps A is sal enixum.
Embodiment 3
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, use hydrosulfate are as catalyzer, and at the temperature of 90 DEG C, in 3 hours, catalysis 1,3 butylene glycol generation condensation reaction, obtains the crude product of dihydroxydibutylether, transformation efficiency 85%;
B, the dihydroxydibutylether crude product cooling that will obtain, add alkali adjust ph to 7;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.01Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 98.5%.
In described steps A, catalyst levels is 50% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.1Mpa.
Hydrosulfate catalyzer in described steps A is sal enixum.
Embodiment 4
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, measure 200.0g(2.22mol) the round-bottomed flask that joins of 1,3 butylene glycol in, add hydrosulfate as catalyzer, stir, oil bath is heated, and is warming up to 145-150 DEG C, reacts after 1.5 hours, transformation efficiency 90%;
B, be cooled to after room temperature until product, add sodium hydroxide and be adjusted to pH to 6;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.02Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 97.1%.
In described steps A, catalyst levels is 5% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.04Mpa.
Hydrosulfate catalyzer in described steps A is sal enixum.
Embodiment 5
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, measure 200.0g(2.22mol) the round-bottomed flask that joins of 1,3 butylene glycol in, add hydrosulfate as catalyzer, stir, oil bath is heated, and is warming up to 155-175 DEG C, reacts after 3 hours, transformation efficiency 92%;
B, be cooled to after room temperature until product, add sodium hydroxide and be adjusted to pH to 10;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.04Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 98.2%.
In described steps A, catalyst levels is 10% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.07Mpa.
Hydrosulfate catalyzer in described steps A is sal enixum.
Embodiment 6
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, measure 200.0g(2.22mol) the round-bottomed flask that joins of 1,3 butylene glycol in, add TBuA hydrosulfate as catalyzer, stir, oil bath is heated, and is warming up to 175-190 DEG C, reacts after 3 hours, transformation efficiency 95%.
B, be cooled to after room temperature until product, add sodium hydroxide and be adjusted to pH to 7;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.04Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 97.8%.
In described steps A, catalyst levels is 30% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.04Mpa.
Embodiment 7
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, measure 200.0g(2.22mol) the round-bottomed flask that joins of 1,3 butylene glycol in, add hydrosulfate as catalyzer, stir, oil bath is heated, and is warming up to 130-150 DEG C, reacts after 5 hours, transformation efficiency 92%;
B, be cooled to after room temperature until product, add potassium hydroxide and be adjusted to pH to 8;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.04Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 96.8%.
In described steps A, catalyst levels is 50% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.1Mpa.
Hydrosulfate catalyzer in described steps A is sodium pyrosulfate.
Embodiment 8
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, measure 200.0g(2.22mol) the round-bottomed flask that joins of 1,3 butylene glycol in, together add hydrosulfate as catalyzer, stir, oil bath is heated, and is warming up to 100-130 DEG C, reacts after 4.5 hours, transformation efficiency 96%;
B, be cooled to after room temperature until product, add potassium hydroxide and be adjusted to pH to 7.5;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.03Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 96.9%.
In described steps A, catalyst levels is 40% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.06Mpa.
Hydrosulfate catalyzer in described steps A is magnesium hydrogen sulfate.
Embodiment 9
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, measure 200.0g(2.22mol) the round-bottomed flask that joins of 1,3 butylene glycol in, together add hydrosulfate as catalyzer, stir, oil bath is heated, and is warming up to 80 DEG C, reacts after 1 hour, transformation efficiency 91%.
B, be cooled to after room temperature until product, add potassium hydroxide and be adjusted to pH to 9;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.04Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 97.5%.
In described steps A, catalyst levels is 5% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.08Mpa.
Hydrosulfate catalyzer in described steps A is TBuA hydrosulfate.
Embodiment 10
A preparation method for dihydroxydibutylether, the processing step of the method is as follows:
A, measure 200.0g(2.22mol) the round-bottomed flask that joins of 1,3 butylene glycol in, together add hydrosulfate catalyzer as catalyzer, stir, oil bath is heated, and is warming up to 90 DEG C, reacts after 10 hours, transformation efficiency 92%.
B, be cooled to after room temperature until product, add sodium hydroxide and be adjusted to pH to 7;
C, at 150 DEG C of temperature, vacuum tightness is underpressure distillation under-0.04Mpa condition, obtains dihydroxydibutylether.Measure through GC, product content is 96.3%.
In described steps A, catalyst levels is 8% of 1,3 butylene glycol quality.
In described steps A, the pressure of condensation reaction is 0.07Mpa.
Hydrosulfate catalyzer in described steps A is monoammonium sulfate.
Embodiment 11
The preparation method of dihydroxydibutylether of the present invention is carried out method disclosed in process pilot scale-up and CN201310256987.9, CN201310251783.6, US4584321 and carry out process pilot scale-up, adopt vapor detection method to analyze the product obtained respectively, its content and impurity situation are described below:
Table 1 vapor detection method is to the analytical results of reaction product
As can be seen here, the dihydroxydibutylether product of the inventive method synthesis is adopted to have purity high, the feature that impurity is few.As everyone knows, the key factor affecting medicine safety in utilization is that foreign matter content is the least possible, and the impurity number of the inventive method product and foreign matter content are all far smaller than prior art, more safe and reliable.
Claims (8)
1. a preparation method for dihydroxydibutylether, is characterized in that: the processing step of the method is as follows:
A, employing hydrosulfate are as catalyzer, and at the temperature of 80-190 DEG C, in 1-10 hour, catalysis 1,3 butylene glycol generation condensation reaction, obtains the crude product of dihydroxydibutylether;
B, the dihydroxydibutylether crude product cool to room temperature that will obtain, add alkali and regulate its pH value to 6-10;
C, underpressure distillation at 100-300 DEG C of temperature, obtain dihydroxydibutylether.
2. the preparation method of a kind of dihydroxydibutylether according to claim 1, is characterized in that: described catalyst levels is the 1.0%-50% of 1,3 butylene glycol quality.
3. the preparation method of a kind of dihydroxydibutylether according to claim 1, it is characterized in that: in described steps A, the pressure of condensation reaction is 0.04-0.1Mpa.
4. the preparation method of a kind of dihydroxydibutylether according to claim 1, is characterized in that: the hydrosulfate catalyzer in described steps A is one or more in sodium pyrosulfate, sal enixum, TBuA hydrosulfate, monoammonium sulfate, magnesium hydrogen sulfate.
5. the preparation method of a kind of dihydroxydibutylether according to claim 4, is characterized in that: described hydrosulfate catalyzer is sal enixum.
6. the preparation method of a kind of dihydroxydibutylether according to claim 1, it is characterized in that, the alkali in described step B is sodium hydroxide or potassium hydroxide.
7. the preparation method of a kind of dihydroxydibutylether according to claim 1, is characterized in that, in described step B, regulates the value of PH to 7.0-8.0.
8. the preparation method of a kind of dihydroxydibutylether according to claim 1, it is characterized in that, in described step C, the vacuum tightness of underpressure distillation is-0.04--0.1Mpa.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4584321A (en) * | 1983-05-30 | 1986-04-22 | Istituto Luso Farmaco D'italia S.P.A. | 3-(3-Hydroxybutoxy)-1-butanol in pharmaceutical compositions |
| CN103319316A (en) * | 2013-06-24 | 2013-09-25 | 大连理工大学 | Green preparation method of dihydroxy dibutyl ether |
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2014
- 2014-08-28 CN CN201410429985.XA patent/CN104230674A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4584321A (en) * | 1983-05-30 | 1986-04-22 | Istituto Luso Farmaco D'italia S.P.A. | 3-(3-Hydroxybutoxy)-1-butanol in pharmaceutical compositions |
| CN103319316A (en) * | 2013-06-24 | 2013-09-25 | 大连理工大学 | Green preparation method of dihydroxy dibutyl ether |
Non-Patent Citations (1)
| Title |
|---|
| 陈单云等: "硫酸氢钠在催化反应中的应用", 《湖北化工》 * |
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