CN108046980B - Novel synthesis method of 5-bromo-1-pentene - Google Patents
Novel synthesis method of 5-bromo-1-pentene Download PDFInfo
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- CN108046980B CN108046980B CN201711395883.0A CN201711395883A CN108046980B CN 108046980 B CN108046980 B CN 108046980B CN 201711395883 A CN201711395883 A CN 201711395883A CN 108046980 B CN108046980 B CN 108046980B
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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Abstract
The invention relates to the technical field of organic synthesis methods, in particular to a novel chemical synthesis method of 5-bromo-1-pentene, which comprises the steps of heating 1, 5-dibromopentane serving as an initial raw material and N, N-dimethylformamide serving as a solvent; hexamethylphosphoric triamide is used as a catalyst for reaction, and the 5-bromine-1-pentene crude product is obtained by normal pressure distillation; the crude product is washed twice with brine and then rectified to obtain the high-purity 5-bromo-1-pentene. The method simplifies the existing synthesis process and post-treatment, improves the reaction yield, improves the production stability and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of organic synthesis methods, in particular to a novel chemical synthesis method of 5-bromo-1-pentene.
Background
5-bromo-1-pentene (5-bromo-1-pentene), molecular formula C5H9Br, molecular weight 149.03, colorless transparent liquid, molecular structural formula:
the molecular structure contains double bonds and bromine atoms, so the molecular structure has the properties of olefin and halogenated hydrocarbon, is a starting material for synthesizing DL-playfrog toxin (DL-thionocoxin) and a fatty acid containing benzol, is a basic chemical and medical intermediate, and has quite wide application in the fields of medicines, pesticides and material chemistry.
At present, the commonly used synthesis methods of 5-bromo-1-pentene mainly comprise the following steps:
1) U.S. Pat. No. 5,5563230 uses 1, 5-dibromopentane as raw material, and heating with hexamethylphosphoric triamide (HMPA) at high temperature to remove one molecule of hydrogen bromide to obtain the target compound, and the synthetic route is as follows:
however, this route has a significant amount of 1, 4-pentadiene, a by-product of two molecules of hydrogen bromide, appearing as follows:
in addition, the yield reported in the U.S. patent is only 61.5%, the solvent and the elimination catalyst used are hexamethylphosphoric triamide, the market price is high, the carcinogenic toxicity is high, and the reaction problem is over 195 ℃. The method is not suitable for production due to the disadvantages of high raw material price, harsh production conditions and the like.
2) 1, 5-dibromopentane and potassium tert-butoxide are used as raw materials, and a molecule of hydrogen bromide is removed in a solvent to obtain a target compound, wherein the synthetic route is as follows:
in the method, the used raw material potassium tert-butoxide has large molecular weight and large mass, so that the raw material has high price, the by-product 1, 5-pentadiene is also generated, the reaction of the raw material 1, 5-dibromopentane is incomplete in the reaction process, a plurality of impurities in the product are caused by various factors, and the yield is low.
3) The target compound is obtained by bromination by using 4-pentene-1-alcohol and phosphorus tribromide or other bromides as raw materials, and the synthetic route is as follows:
however, in the synthesis method, 4-penten-1-ol raw materials are not easy to obtain, customized synthesis is needed, the price is high, and the production amplification is meaningless.
By comprehensively analyzing the above synthetic methods, a novel 5-bromo-1-pentene synthetic method which can simplify the existing synthetic process and post-treatment, improve the reaction yield, improve the production stability and reduce the production cost is urgently needed.
Disclosure of Invention
In view of the above problems, the present invention provides a novel process for synthesizing 5-bromo-1-pentene, which can simplify the existing synthesis process and post-treatment, improve the reaction yield, improve the production stability and reduce the production cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention relates to a novel chemical synthesis method of 5-bromo-1-pentene, which comprises the steps of heating 1, 5-dibromopentane serving as an initial raw material and N, N-dimethylformamide serving as a solvent; hexamethylphosphoric triamide is used as a catalyst for reaction, and the 5-bromine-1-pentene crude product is obtained by normal pressure distillation; the crude product is washed twice with brine and then rectified to obtain a pure product, namely the high-purity 5-bromo-1-pentene, and the process route is as follows:
preferably, in the present synthesis method invention, the mass ratio of 1, 5-dibromopentane to N, N-dimethylformamide is 1: 1 to 5.
Preferably, in the present synthesis method invention, the mass ratio of 1, 5-dibromopentane to hexamethylphosphoric triamide is 1: 0.04-0.08.
Preferably, in the synthesis method, the reaction temperature in the process is in the range of 100-160 ℃.
Preferably, in the synthesis method, the reaction time in the process is controlled to be 2-12 h.
Preferably, in the present synthesis method invention, the reaction temperature in the process is 140 ℃.
Preferably, in the synthesis method, the reaction time in the process is 6 hours.
The invention has the advantages and beneficial effects that: provides a novel 5-bromo-1-pentene process synthesis method which can simplify the existing synthesis process and post-treatment, improve the reaction yield, improve the production stability and reduce the production cost. In the invention, after 1, 5-dibromopentane and DMF are mixed and heated, the mixture is heated at 100-160 ℃ to distill out fractions, and the process is simple; the adopted raw materials are low in price and easy to obtain, and are environment-friendly; the synthesis method is simple and convenient to operate, and the yield is more than 80%, and the purity is more than 99%; is suitable for large-scale industrial production.
Detailed Description
The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
A novel chemical synthesis method of 5-bromo-1-pentene is characterized in that 1, 5-dibromopentane is used as an initial raw material, N-dimethylformamide is used as a solvent, and heating is carried out; hexamethylphosphoric triamide is used as a catalyst for reaction, and the 5-bromine-1-pentene crude product is obtained by normal pressure distillation; washing the crude product with brine twice, and rectifying to obtain a pure product, namely the high-purity 5-bromo-1-pentene, wherein the specific implementation process refers to the following steps:
example 1
1, 5-dibromopentane 100KG, N-dimethylformamide 200KG, stirring and mixing, then heating for 6h at 150 ℃ in an oil bath, distilling and collecting fractions under normal pressure, washing the collected fractions twice with 100KG saturated saline, rectifying the upper organic liquid to obtain 32.6KG, wherein the yield is 50.2%, and the content: 99 percent.
The product was tested and confirmed to be 5-bromo-1-pentene with a purity of 99% (GC), wherein the product had a 1H NMR (400MHz, CDCl3) delta: 1.96(m,2H), 2.22(m,2H), 3.43(t,2H), 5.02-5.12 (m,2H), 5.80(m, 1H).
Example 2
1, 5-dibromopentane 100KG, N-dimethylformamide 100KG, hexamethylphosphoric triamide 6.2KG are stirred and mixed, then oil bath is heated for 4h at 140 ℃, distillation under normal pressure is carried out to collect the fraction, the collected fraction is washed twice by 100KG saline, the upper organic liquid is rectified to obtain 52.0KG, the yield is 80.1%, and the content: 99 percent.
The product was tested and confirmed to be 5-bromo-1-pentene with a purity of 99% (GC), wherein the product had a 1H NMR (400MHz, CDCl3) delta: 1.96(m,2H), 2.22(m,2H), 3.43(t,2H), 5.02-5.12 (m,2H), 5.80(m, 1H).
Example 3
1, 5-dibromopentane 100KG, N-dimethylformamide 200KG, hexamethylphosphoric triamide 3.1KG are stirred and mixed, then the oil bath is heated for 4h at 150 ℃, the fraction is collected by atmospheric distillation, the collected fraction is washed twice by 100KG brine, the upper organic liquid is rectified to obtain 46.7KG, the yield is 71.9%, and the content: 99 percent.
The product was tested and confirmed to be 5-bromo-1-pentene with a purity of 99% (GC), wherein the product had a 1H NMR (400MHz, CDCl3) delta: 1.96(m,2H), 2.22(m,2H), 3.43(t,2H), 5.02-5.12 (m,2H), 5.80(m, 1H).
Example 4
1, 5-dibromopentane 100KG, N-dimethylformamide 100KG, hexamethylphosphoric triamide 3.1KG stir and mix, then oil bath 140 ℃ heating 6h, atmospheric distillation collects the fraction, and the fraction of collecting is washed twice with 100KG water, and upper organic liquid obtains 49.3KG through the rectification, yield 76%, content: 99 percent.
The product was tested and confirmed to be 5-bromo-1-pentene with a purity of 99% (GC), wherein the product had a 1H NMR (400MHz, CDCl3) delta: 1.96(m,2H), 2.22(m,2H), 3.43(t,2H), 5.02-5.12 (m,2H), 5.80(m, 1H).
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A chemical synthesis method of 5-bromo-1-pentene is characterized in that 1, 5-dibromopentane is used as a starting material, N-dimethylformamide is used as a solvent, hexamethylphosphoric triamide is used as a catalyst, the three materials are mixed, heated and reacted, and a crude product of 5-bromo-1-pentene is obtained through normal pressure distillation; washing the crude product with brine twice, and rectifying to obtain a pure product, namely the high-purity 5-bromo-1-pentene; wherein the mass ratio of 1, 5-dibromopentane to N, N-dimethylformamide is 1: 1-5; mass ratio of 1, 5-dibromopentane to hexamethylphosphoric triamide ═ 1: 0.04 to 0.08; the reaction temperature range in the process is 100-160 ℃.
2. The chemical synthesis method of 5-bromo-1-pentene according to claim 1, wherein the reaction time in the process is controlled to be 2 to 12 hours.
3. The chemical synthesis method of 5-bromo-1-pentene according to claim 1, wherein the reaction temperature in the process is 140 ℃.
4. The chemical synthesis method of 5-bromo-1-pentene according to claim 1, wherein the reaction time in the process is 6 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5563230A (en) * | 1994-09-09 | 1996-10-08 | National Science Council | Chiral smectic liquid crystalline polymers |
| CN105837396A (en) * | 2016-04-28 | 2016-08-10 | 仪征市海帆化工有限公司 | 5-chloro-1-amylene synthesis method |
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- 2017-12-21 CN CN201711395883.0A patent/CN108046980B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5563230A (en) * | 1994-09-09 | 1996-10-08 | National Science Council | Chiral smectic liquid crystalline polymers |
| CN105837396A (en) * | 2016-04-28 | 2016-08-10 | 仪征市海帆化工有限公司 | 5-chloro-1-amylene synthesis method |
Non-Patent Citations (4)
| Title |
|---|
| A New Microwave Reactor for Batchwise Organic Synthesis;RANER, KD et al;《JOURNAL OF ORGANIC CHEMISTRY》;19950421;第60卷(第8期);第2456-2460页 * |
| A useful modification of the Kraus procedure for preparation of omega-bromo-1-alkenes by HMPA-promoted elimination of HBR from 1,omega-dibromoalkanes;Hoye, TR et al;《SYNTHETIC COMMUNICATIONS》;20011231;第31卷(第9期);第1367-1371页 * |
| Controlling Thread Assemblies of Pharmaceutical Compounds in Liquid Crystal Phase by Using Functionalized Nanotopography;Simon, Karen A et al;《CHEMISTRY OF MATERIALS》;20100427;第22卷(第8期);第2434-2441页 * |
| Synthesis of 1,10-Dimethylbicyclo[8.8.8]hexacosane and 1,10-Dihydroxybicyclo[8.8.8]hexacosane;Ian W. Jones et al;《ORGANIC LETTERS》;20050615;第7卷(第14期);第2841-2843页 * |
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