CN109369328A - A kind of preparation method of simple and safe synthesis propilolic alcohol - Google Patents
A kind of preparation method of simple and safe synthesis propilolic alcohol Download PDFInfo
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- CN109369328A CN109369328A CN201811500734.0A CN201811500734A CN109369328A CN 109369328 A CN109369328 A CN 109369328A CN 201811500734 A CN201811500734 A CN 201811500734A CN 109369328 A CN109369328 A CN 109369328A
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- catalyst
- propilolic alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
Abstract
A kind of preparation method of simple and safe synthesis propilolic alcohol, it is characterized in that, this method preparation section are as follows: reactor first is added in catalyst, metaformaldehyde and solvent, is passed through acetylene, reactor is heated to certain temperature and carries out activation of catalyst, activation process adjusts pH value by lye；After the completion of activation of catalyst, stopping is passed through acetylene gas, 1 is added into reactor again, 4- butynediols and organic solvent, continue for reactor to be heated to BYD decomposition temperature, Isosorbide-5-Nitrae-butynediols is under the effect of the catalyst, it decomposes generation propilolic alcohol and formaldehyde, propilolic alcohol is separated with reaction solution in gaseous form.Remarkable result of the invention are as follows: prepare propilolic alcohol by selecting BYD to decompose decomposition temperature, acetylene is not used during BYD decomposition reaction, atmospheric operation improves the stability of safety and system.
Description
Technical field
The invention belongs to the preparation method field of medication chemistry product, in particular to a kind of simple and safe synthesis propilolic alcohol
Preparation method.
Technical background
Propilolic alcohol is industrially a kind of important intermediate of organic synthesis.In pharmaceuticals industry, propilolic alcohol is synthesis phosphorus
Mycin sodium, fosfomycin calcium, the important intermediate of sulphadiazine are also used for the medicine such as production propenyl, methacrylaldehyde, vitamin A and produce
Product.In pesticide industry, for synthesizing propargite pesticide.It can be made by addition reaction of the terminal groups alkynes to aldehydes or ketones
Propilolic alcohol, reaction process is first reacted with terminal alkyne generally by active metal reagents such as zinc alkyl, butyl lithiums generates alkynyl
Zinc or alkynyl lithium reagent, then obtain propiolic alcohol compound to carbonyls addition.However, zinc alkyl and butyl lithium etc. are golden
Belonging to reagent is sensitivity to water electrode, needs the water content of strict control reaction system, is all needed to reagent and solvent, vessel needed for reacting
Stringent dried over anhydrous, therefore severe reaction conditions, it is inconvenient.Currently, the industrialized production of propilolic alcohol substantially uses
Reppe method technique, production technology are that German scholar Reppe was succeeded in developing with IG company of the state in 1937.Due to this
Technical process reaches 2MPa, safety problem one using a large amount of acetylene gas and inflammable and explosive acetylene copper catalyst, acetylene pressure
It is directly the main bugbear for perplexing the technical process.
Summary of the invention
The purpose of the present invention is directed to the shortcoming of existing propilolic alcohol technology of preparing safety, provides a kind of simple and safe conjunction
At the preparation method of propilolic alcohol.
Purpose technical solution is as follows to realize the present invention:
A kind of preparation method of simple and safe synthesis propilolic alcohol, is first added reactor for catalyst, metaformaldehyde and solvent, leads to
Enter acetylene, reactor is heated to certain temperature and carries out activation of catalyst, activation process adjusts pH value by lye.Catalyst is living
After the completion of change, stopping is passed through acetylene gas, then Isosorbide-5-Nitrae-butynediols and organic solvent are added into reactor, continues reactor
Be heated to BYD decomposition temperature, Isosorbide-5-Nitrae-butynediols under the effect of the catalyst, decomposes and generates propilolic alcohol and formaldehyde, propilolic alcohol with
Gas form is separated with reaction solution.The catalyst can be supported copper oxide catalyst, carrier-free copper oxide or contain
There is one of the basic copper carbonate powder of micro Bi element.Organic solvent can be ethylene glycol, gamma-butyrolacton, NMP etc. and ring
One or more of hexanone, including but not limited to these organic solvents.It is 25-80% that organic solvent, which accounts for liquid phase quality specific gravity, excellent
Select 60-70%.It is 10-40%, preferably 15-20% that catalyst, which accounts for liquid phase quality specific gravity,.The control of catalyst activation process solution ph exists
3-7, preferably 5.0-6.3, catalyst activation temperature are 60-100 DEG C, preferably 80-90 DEG C.Activation process addition lye can be first
It is one or more kinds of in the aqueous slkalis such as sodium alkoxide, sodium ethoxide, sodium bicarbonate, sodium carbonate.Catalyst activation process acetylene pressure is normal
Pressure.
Remarkable result of the invention are as follows: 1) select BYD to decompose decomposition temperature and prepare propilolic alcohol, in BYD decomposition reaction process
In do not use acetylene, atmospheric operation, improve safety and system stability；
2) BYD decomposition prepares propine determining alcohol height, selects high boiling organic solvent, propilolic alcohol product is easily isolated；3) this hair
It is bright to prepare propilolic alcohol high income, improve economic benefit.
Specific embodiment
The specific embodiment of the invention is further illustrated below by embodiment.
Embodiment one
A kind of preparation method of simple and safe synthesis propilolic alcohol, decomposes system third with carrier-free basic copper carbonate catalyst BYD
Alkynol, preferred reaction conditions are reaction temperature 140, atmospheric operation, solvent gamma-butyrolacton/BYD mass ratio 2/1, catalyst concn
When (catalyst quality/(BYD+ solvent), similarly hereinafter) is 20wt%, reaction time 4h, propilolic alcohol yield is 22.38%.
Embodiment two
A kind of preparation method of simple and safe synthesis propilolic alcohol, decomposes propilolic alcohol processed with magnesium silicate loaded copper oxide catalysis BYD, excellent
Selecting reaction condition is 155 DEG C of reaction temperature, atmospheric operation, solvent ethylene glycol/BYD mass ratio 2/1,20 wt % of catalyst concn
, reaction time 4h when, propilolic alcohol yield 33.3%.
Embodiment three
A kind of preparation method of simple and safe synthesis propilolic alcohol, decomposes propilolic alcohol processed with magnesium silicate loaded copper oxide catalysis BYD and connects
Continuous experiment, preferred reaction conditions are that 146 DEG C of reaction temperature, acetylene gas are bubbled into, are atmospheric operation, not set rectifier unit, molten
Agent ethylene glycol/BYD mass ratio be 1, catalyst initial concentration 10% and periodically add, react obtain afterwards for 24 hours product contain propilolic alcohol
53.8%, propilolic alcohol yield 23.6%.
Claims (3)
1. a kind of preparation method of simple and safe synthesis propilolic alcohol, which is characterized in that this method preparation section are as follows: first will catalysis
Reactor is added in agent, metaformaldehyde and solvent, is passed through acetylene, and reactor is heated to certain temperature and carries out activation of catalyst, living
Change process adjusts pH value by lye；After the completion of activation of catalyst, stopping is passed through acetylene gas, then Isosorbide-5-Nitrae-is added into reactor
Butynediols and organic solvent continue for reactor to be heated to BYD decomposition temperature, effect of the Isosorbide-5-Nitrae-butynediols in catalyst
Under, it decomposes generation propilolic alcohol and formaldehyde, propilolic alcohol is separated with reaction solution in gaseous form.
2. the preparation method of propilolic alcohol according to claim 1, which is characterized in that the catalyst can be support type
One of copper oxide catalyst, carrier-free copper oxide or basic copper carbonate powder containing micro Bi element.Catalyst accounts for liquid
Phase quality specific gravity be 10-40%, preferably 15-20%, catalyst activation process solution ph control in 3-7, preferably 5.0-6.3, urge
Agent activation temperature is 60-100 DEG C, and preferably 80-90 DEG C, activation process addition lye can be sodium methoxide, sodium ethoxide, bicarbonate
One or more kinds of in the aqueous slkalis such as sodium, sodium carbonate, catalyst activation process acetylene pressure is normal pressure.
3. the preparation method of propilolic alcohol according to claim 1, which is characterized in that organic solvent can be ethylene glycol, γ-
Butyrolactone, NMP etc. and one or more of cyclohexanone, including but not limited to these organic solvents, organic solvent account for liquid phase matter
Amount specific gravity is 25-80%, preferably 60-70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811500734.0A CN109369328A (en) | 2018-12-10 | 2018-12-10 | A kind of preparation method of simple and safe synthesis propilolic alcohol |
Applications Claiming Priority (1)
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| CN201811500734.0A CN109369328A (en) | 2018-12-10 | 2018-12-10 | A kind of preparation method of simple and safe synthesis propilolic alcohol |
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| CN109369328A true CN109369328A (en) | 2019-02-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717945A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for synthesizing 1, 4-butynediol and preparation method and application thereof |
| CN113666803A (en) * | 2021-08-30 | 2021-11-19 | 四川众邦制药有限公司 | Method for synthesizing propiolic alcohol |
| CN113698274A (en) * | 2021-09-27 | 2021-11-26 | 四川众邦制药有限公司 | Method for synthesizing 3-butyne-2-ol with high yield |
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| US4855516A (en) * | 1987-05-23 | 1989-08-08 | Gaff-Huels Chemie Gmbh | Method of manufacturing 2-propyn-1-ol |
| CN1826306A (en) * | 2003-07-24 | 2006-08-30 | 巴斯福股份公司 | Method for the production of propargyl alcohol |
| CN108069827A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of method for preparing 1,4- butynediols coproduction propilolic alcohols |
| CN108358749A (en) * | 2018-02-07 | 2018-08-03 | 重庆弛源化工有限公司 | A kind of production method of propargyl alcohol |
| CN108503505A (en) * | 2018-05-11 | 2018-09-07 | 中国石化长城能源化工（宁夏）有限公司 | A method of preparing propilolic alcohol using Isosorbide-5-Nitrae-butynediols |
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2018
- 2018-12-10 CN CN201811500734.0A patent/CN109369328A/en active Pending
Patent Citations (5)
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| US4855516A (en) * | 1987-05-23 | 1989-08-08 | Gaff-Huels Chemie Gmbh | Method of manufacturing 2-propyn-1-ol |
| CN1826306A (en) * | 2003-07-24 | 2006-08-30 | 巴斯福股份公司 | Method for the production of propargyl alcohol |
| CN108069827A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of method for preparing 1,4- butynediols coproduction propilolic alcohols |
| CN108358749A (en) * | 2018-02-07 | 2018-08-03 | 重庆弛源化工有限公司 | A kind of production method of propargyl alcohol |
| CN108503505A (en) * | 2018-05-11 | 2018-09-07 | 中国石化长城能源化工（宁夏）有限公司 | A method of preparing propilolic alcohol using Isosorbide-5-Nitrae-butynediols |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112717945A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst for synthesizing 1, 4-butynediol and preparation method and application thereof |
| CN112717945B (en) * | 2019-10-28 | 2023-05-26 | 中国石油化工股份有限公司 | Catalyst for synthesizing 1, 4-butynediol as well as preparation method and application thereof |
| CN113666803A (en) * | 2021-08-30 | 2021-11-19 | 四川众邦制药有限公司 | Method for synthesizing propiolic alcohol |
| CN113666803B (en) * | 2021-08-30 | 2023-09-01 | 四川众邦新材料股份有限公司 | Method for synthesizing propargyl alcohol |
| CN113698274A (en) * | 2021-09-27 | 2021-11-26 | 四川众邦制药有限公司 | Method for synthesizing 3-butyne-2-ol with high yield |
| CN113698274B (en) * | 2021-09-27 | 2024-04-12 | 四川众邦新材料股份有限公司 | Method for synthesizing 3-butyn-2-ol in high yield |
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Application publication date: 20190222 |
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