CN109180419A - The preparation process of the bromo- 1- amylene of 5- - Google Patents
The preparation process of the bromo- 1- amylene of 5- Download PDFInfo
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- CN109180419A CN109180419A CN201811060816.8A CN201811060816A CN109180419A CN 109180419 A CN109180419 A CN 109180419A CN 201811060816 A CN201811060816 A CN 201811060816A CN 109180419 A CN109180419 A CN 109180419A
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- amylene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation processes of the bromo- 1- amylene of 5-, comprising the following steps: step a, it is added 1 in reaction kettle, pentamethylene bromide and solid potassium hydroxide, and heating stirring, make to keep the temperature 1-3 hours after temperature reaches 100-120 DEG C in reaction kettle；Step b, vacuum distillation obtains fraction；Step c, the fraction for obtaining step b carries out rectifying, obtains target product；Step d, unreacted raw material is recycled.The invention has the advantages that raw material used in the synthetic method and alkali potassium hydroxide are all very cheap and easily-available, solvent is not used in reaction, is conducive to control production cost, is suitble to industrialized production；Unreacted raw materials recovery rate 26%, can apply, and sufficiently accomplish Resource recovery, save the cost, and reduce the pollution of environment.
Description
Technical field
The present invention relates to the preparation processes of the bromo- 1- amylene of 5-.
Background technique
In recent years, the research of the bromo- 1- amylene of 5- is widely paid close attention to and obtains biggish progress.The bromo- 1- amylene of 5- is
A kind of very widely used pharmaceutical intermediate such as can be used for synthesizing a series of α-monohydroxy cyclodextrine derivatives.The bromo- 1- of 5-
Amylene is also that air and water are stablized in synthesis, has the platinum organic precursor [Pt (C compared with low melting point (40-41 DEG C)5H9)2]
One of raw material, [Pt (C5H9)2] it is for regulating and controlling to prepare the platinum based catalyst of support type.Support type platinum based catalyst has
High activity, highly selective and good stability, thus it is widely used in electrode catalyst of fuel cell, in petrochemical industry
The fields such as the synthesis of catalytic reforming and various fine chemicals.
The existing synthetic route of reported in literature has:
(1), 2- chloromethyl tetrahydrofuran is that raw material open loop obtains the dilute -1- alcohol of 4- penta, then uses carbon tetrabromide and triphenylphosphine bromine
Change reaction and obtains the bromo- 1- amylene of 5-.The route raw material is very expensive, and raw material is rare, is not suitable for industrialized production；
(2), using dibromo pentane as raw material, potassium tert-butoxide is base catalyst, and tetrahydrofuran and toluene are that mixed solvent synthesis 5- is bromo-
1- amylene, yield 69% or hexamethylphosphoramide are that catalyst is reacted at 195-220 DEG C；This route raw material is cheap, preceding
Person's catalyst relative price is higher, and latter reaction's temperature is excessively high, so that industrialized higher cost.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the disadvantages mentioned above of the prior art, provide a kind of bromo- 1- amylene of 5-
Preparation process.
In order to solve the above technical problems, a kind of preparation process of the bromo- 1- amylene of 5- of the present invention, it is characterised in that including with
Lower step:
Step a, it is added 1 in reaction kettle, pentamethylene bromide and solid potassium hydroxide, and heating stirring, reach temperature in reaction kettle
1-3 hours are kept the temperature after 100-120 DEG C；
Step b, vacuum distillation obtains fraction；
Step c, the fraction for obtaining step b carries out rectifying, obtains target product.
Chemical equation of the invention are as follows:
The invention has the advantages that raw material used in the synthetic method and alkali potassium hydroxide are all very cheap and easily-available, than making in document
Cheap more of potassium tert-butoxide, in addition, not using solvent in reaction, are conducive to control production cost, suitable industrialized production；
Unreacted raw materials recovery rate 26%, can apply, and sufficiently accomplish Resource recovery, save the cost, and reduce the pollution of environment.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In technical solution of the present invention is clearly and completely described.
Example 1
Prepare clean and dry 200L reaction kettle, is equipped with the pillar and glass condenser of glass filler.It is pumped into from reaction kettle bottom valve
150kg 1, pentamethylene bromide, then solid potassium hydroxide 60kg is put into from feed opening.Condenser opens chilled brine, opens reaction
Kettle mechanical stirring, opening jacket steam makes after temperature reaches 110 DEG C -120 DEG C in reaction kettle, keeps the temperature 2 hours.Open workshop three-level sieve
Thatch pumps (vacuum degree about 2mmHg), and decompression steams crude product, goes out to no fraction, continues heating in 120 DEG C and keeps the temperature 1 hour.It has kept the temperature
Finish, lobe pump decompression again steams crude product, to not go out fraction, keeps the temperature it again, and repetitive operation reacts knot to fraction is not gone out substantially
Beam.Merge the total 48.2kg of all qualified fractions.Fraction is detected, if 1, the content of pentamethylene bromide is greater than 20%, then
Fraction is rejoined in reaction kettle and continues to participate in reaction.
The fraction batch rectification that will be collected above.10L four-hole boiling flask configures 50cm rectifying pillar, and Rectification head, ice maker is cooling,
It is about that 2mmHg is distilled that oil pump, which is decompressed to vacuum degree, 60 DEG C of oil temperature, collects top 40 DEG C of product 37.6kg of temperature, yield 51%.
It recycles unreacted raw material: remaining a large amount of white solids in reaction kettle, 150kg water is added into kettle, stirs 2 at room temperature
Hour.Stratification, lower organic layer are fitted into 25L plastic barrel.It is pumped into 80kg methylene chloride in reaction kettle, stirs 2 hours, it is complete
At extraction, stratification, lower organic layer is separated.Reaction kettle is pumped into organic layer, 2 hours dry with 20kg anhydrous sodium sulfate, takes out
The mother liquor of filter returns in kettle, unlatching steam, 40-50 DEG C or so of interior temperature under normal pressure, takes off methylene chloride.Concentrate 46kg, puts
Enter in plastic barrel, keeps next raw material and apply.
Example 2
Prepare clean and dry 200L reaction kettle, is equipped with the pillar and glass condenser of glass filler.It is pumped into from reaction kettle bottom valve
150kg 1, pentamethylene bromide, then solid potassium hydroxide 70kg is put into from feed opening.Condenser opens chilled brine, opens reaction
Kettle mechanical stirring, opening jacket steam makes after temperature reaches 110-120 DEG C in reaction kettle, keeps the temperature 2 hours.Open workshop three-level Roots
It pumps (vacuum degree about 2mmHg), decompression steams crude product, goes out to no fraction, continues heating in 120 DEG C and keeps the temperature 1 hour.Heat preservation finishes,
Lobe pump decompression again steams crude product, to not go out fraction, keeps the temperature it again, and repetitive operation terminates to fraction, reaction is not gone out substantially.
Merge the total 46.3kg of all qualified fractions.Fraction is detected, if 1, the content of pentamethylene bromide is greater than 20%, then will evaporate
Divide to rejoin in reaction kettle and continues to participate in reaction.
The fraction batch rectification that will be collected above.10L four-hole boiling flask configures 50cm rectifying pillar, and Rectification head, ice maker is cooling,
It is about that 2mmHg is distilled that oil pump, which is decompressed to vacuum degree, 60 DEG C of oil temperature, collects top 40 DEG C of product 33.2kg of temperature, yield 45%.
Above-described embodiment is to have carried out production practices using 200L reaction kettle, considers the influence of industrialization amplification completely,
Therefore present invention process is suitable for industrial application.
In addition, in material addition step, the dosage of solid potassium hydroxide is 1,1.7-2.0 times of the molar equivalent of pentamethylene bromide
Production needs can be met.
In addition to the implementation, the present invention can also have other embodiments.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Claims (8)
1. a kind of preparation process of the bromo- 1- amylene of 5-, it is characterised in that the following steps are included:
Step a, it is added 1 in reaction kettle, pentamethylene bromide and solid potassium hydroxide, and heating stirring, reach temperature in reaction kettle
1-3 hours are kept the temperature after 100-120 DEG C；
Step b, vacuum distillation obtains fraction；
Step c, the fraction for obtaining step b carries out rectifying, obtains target product.
2. the preparation process of the bromo- 1- amylene of 5- according to claim 1, it is characterised in that: in the step a, solid hydrogen
The dosage of potassium oxide is 1.7-2.0 times of the molar equivalent of pentamethylene bromide.
3. the preparation process of the bromo- 1- amylene of 5- according to claim 1, it is characterised in that: in step b, vacuum distillation is obtained
After taking fraction, heating reaction kettle makes interior temperature reach 100-120 DEG C and keeps the temperature 1 hour, and then vacuum distillation obtains fraction, weight again
Multiple aforesaid operations terminate until not going out fraction, reaction substantially.
4. the preparation process of the bromo- 1- amylene of 5- according to claim 1, it is characterised in that: in step b, carried out to fraction
Detection, if 1, the content of pentamethylene bromide is greater than 20%, then rejoins in reaction kettle fraction and continue to participate in reaction.
5. the preparation process of the bromo- 1- amylene of 5- according to claim 1, it is characterised in that: in step c, carried out to fraction
Batch rectification, it is about 2mmHg that oil pump, which is decompressed to vacuum degree, 60 DEG C of oil temperature, collects the product of 40 DEG C of top temperature, the bromo- 1- penta of as 5-
Alkene.
6. the preparation process of the bromo- 1- amylene of 5- according to claim 1, it is characterised in that: in step d, use anhydrous sulphur
Organic layer is dried in sour sodium, and drying time is 1-2 hours.
7. the preparation process of the bromo- 1- amylene of 5- according to claim 1, it is characterised in that: use multistage sieve in step b
It is about 2mmHg that thatch pump, which is decompressed to vacuum degree to reaction kettle,.
8. the preparation process of the bromo- 1- amylene of 5- according to claim 1-7, it is characterised in that: further include recycling
The step of unreacting material, specifically
Step d, water is added in reaction kettle and stirs, stratification, lower organic layer separates, and dichloromethane then is added to reaction kettle
Alkane completes extraction after stirring, stratification, lower organic layer separates, and takes out the moisture in aforementioned organic layer, and dichloro is taken off in heating
Methane completes unreacted 1, the recycling of pentamethylene bromide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811060816.8A CN109180419A (en) | 2018-09-12 | 2018-09-12 | The preparation process of the bromo- 1- amylene of 5- |
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| CN201811060816.8A CN109180419A (en) | 2018-09-12 | 2018-09-12 | The preparation process of the bromo- 1- amylene of 5- |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299151A (en) * | 2018-02-09 | 2018-07-20 | 浙江大学 | A method of 2- methallyl chlorides are prepared by bis- chlorolifarinas of 1,2- |
-
2018
- 2018-09-12 CN CN201811060816.8A patent/CN109180419A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299151A (en) * | 2018-02-09 | 2018-07-20 | 浙江大学 | A method of 2- methallyl chlorides are prepared by bis- chlorolifarinas of 1,2- |
Non-Patent Citations (4)
| Title |
|---|
| TRAVIS W. BAUGHMAN等: "The facile preparation of alkenyl metathesis synthons", 《TETRAHEDRON》 * |
| 任雪明等: "《高中化学教学疑难问题研析》", 31 August 2015, 浙江教育出版社 * |
| 刘知新等: "《化学教育史》", 31 March 1999, 广西教育出版社 * |
| 周年琛等: "《有机化学》", 31 October 2012, 苏州大学出版社 * |
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