CN112194555A - Preparation method of brominated alkanes - Google Patents
Preparation method of brominated alkanes Download PDFInfo
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- CN112194555A CN112194555A CN202010914763.2A CN202010914763A CN112194555A CN 112194555 A CN112194555 A CN 112194555A CN 202010914763 A CN202010914763 A CN 202010914763A CN 112194555 A CN112194555 A CN 112194555A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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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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Abstract
The application belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of brominated alkanes, which comprises the following steps: (1) adding excessive sulfur powder into fatty alcohol under stirring, heating to 30-60 deg.C, and adding excessive bromine dropwise into fatty alcohol; (2) after the bromine is dripped, reflux reaction is carried out for 1-3h until the content of fatty alcohol in the reaction system is less than 0.1 percent, and reaction liquid is obtained after the reaction is stopped; (3) standing and layering the reaction solution to obtain an organic phase; (4) distilling the organic phase at normal pressure or reduced pressure to obtain crude bromo-alkane; (5) washing the crude bromoalkane product with alkali, washing with water, and drying to obtain refined bromoalkane product; (6) and detecting the purity of the brominated alkane refined product, and calculating the yield of the brominated alkane refined product.
Description
Technical Field
The application belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of brominated alkanes.
Background
The existing process takes 48% hydrobromic acid and corresponding alcohol as raw materials and sulfuric acid as a catalyst to synthesize the bromoalkane, so that the yield is low, a large amount of acid water and wastewater are generated, and the subsequent treatment is complex.
Disclosure of Invention
In order to solve the problems of the prior art, the application provides a preparation method of brominated alkanes, and the application is realized by the following scheme:
a preparation method of brominated alkanes comprises the following steps: (1) adding excessive sulfur powder into fatty alcohol under stirring, heating to 30-60 deg.C, and adding excessive bromine dropwise into fatty alcohol; (2) after the bromine is dripped, reflux reaction is carried out for 1-3h until the content of fatty alcohol in the reaction system is less than 0.1 percent, and reaction liquid is obtained after the reaction is stopped; (3) standing and layering the reaction solution to obtain an organic phase; (4) distilling the organic phase at normal pressure or reduced pressure to obtain crude bromo-alkane; (5) washing the crude bromoalkane product with alkali, washing with water, and drying to obtain refined bromoalkane product; (6) and detecting the purity of the brominated alkane refined product, and calculating the yield of the brominated alkane refined product.
Preferably, the adding amount of the sulfur powder is 101-110% of the theoretical requirement.
Preferably, the temperature of the reaction system during the bromine dripping in the step (1) is controlled to be 40-100 ℃.
Preferably, the addition amount of the bromine is 101-110% of the theoretical requirement amount.
Preferably, the aliphatic alcohol is one of n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol and n-octanol.
Preferably, the sulfur powder is an industrial first-grade sulfur powder meeting GB/T2449.1-2014.
Has the advantages that: the method has the advantages of reasonable design and simple preparation method, and the prepared bromoalkane finished product has the yield as high as 90 percent and the purity as high as 99 percent.
The reaction equation of the present application is as follows:
6(R-OH)+S+3Br2=6(R-Br)+H2SO4+2H2O
(1) in the equation: R-OH represents a fatty alcohol including, but not limited to, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, n-octanol;
(2) R-Br represents alkyl bromide, including but not limited to 1-bromopropane, 2-bromopropane, 1-bromobutane, bromoisobutane, 1-bromopentane, bromoisopentane, 1-bromohexane, 1-bromooctane corresponding to the aliphatic alcohol of (1).
Drawings
FIG. 1 is a process flow diagram of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more clear, embodiments of the present application are described in further detail below.
Example 1
A preparation method of brominated alkanes comprises the following steps: (1) adding excessive sulfur powder into fatty alcohol under stirring, heating to 30-60 deg.C, and adding excessive bromine dropwise into fatty alcohol; (2) after the bromine is dripped, reflux reaction is carried out for 1-3h until the content of fatty alcohol in the reaction system is less than 0.1 percent, and reaction liquid is obtained after the reaction is stopped; (3) standing and layering the reaction solution to obtain an organic phase; (4) distilling the organic phase at normal pressure or reduced pressure to obtain crude bromo-alkane; (5) washing the crude bromoalkane product with alkali, washing with water, and drying to obtain refined bromoalkane product; (6) and detecting the purity of the brominated alkane refined product, and calculating the yield of the brominated alkane refined product.
Example 2
On the basis of the embodiment 1, the adding amount of the sulfur powder is 101-110% of the theoretical demand.
Example 3
On the basis of the example 2, the temperature of the reaction system in the bromine dripping process of the step (1) is controlled to be 40-100 ℃.
Example 4
On the basis of the embodiment 3, the addition amount of the bromine is 101-110% of the theoretical demand amount.
The theoretical requirement is the amount of bromine theoretically required to produce monobromide.
Example 5
The fatty alcohol is one of n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol and n-octanol on the basis of the embodiment 4.
Example 6
On the basis of example 5, the sulfur powder is a first-class industrial sulfur powder meeting GB/T2449.1-2014.
Example 7
A preparation method of brominated alkanes comprises the following steps: (1) adding 1600kg of n-propanol with the purity of 99.8% and 150kg of sulfur powder into a 3000L glass lining reaction kettle with a reflux condenser under the stirring state, and dropwise adding 2240kg of bromine into the reaction kettle when the temperature is raised to 40 ℃; (2) after the dropwise addition of the bromine is finished, carrying out reflux reaction for 2 hours, sampling and testing the content of the n-propanol to be 0.026%, and stopping the reaction to obtain a reaction solution; (3) standing and layering the reaction solution to obtain an organic phase; (4) distilling the organic phase at normal pressure, wherein the number of tower plates of a distillation tower is 75, and collecting fractions at 69-71 ℃ to obtain a crude product of 1-bromopropane; (5) washing the crude bromoalkane product with alkali, washing with water, and drying to obtain 3025kg of 1-bromopropane refined product; (6) the purity of the 1-bromopropane fine product is detected to be 99.61 percent, and the yield of the 1-bromopropane fine product is calculated to be 92.22 percent.
Preferably, the temperature of the reaction system during the bromine dripping in the step (1) is controlled to be not higher than 60 ℃.
Preferably, the sulfur powder is an industrial first-grade sulfur powder meeting GB/T2449.1-2014.
Example 8
A preparation method of brominated alkanes comprises the following steps: (1) adding 1200kg of n-butanol with the purity of 99.9 percent into a 2000L glass lining reaction kettle with a reflux condenser under the stirring state to neutralize 90kg of sulfur powder, and adding 1360kg of bromine into the reaction kettle when the temperature is raised to 40 ℃; (2) after the dropwise addition of the bromine is finished, carrying out reflux reaction for 2 hours, sampling to assay the content of n-butyl alcohol to be 0.051%, and stopping the reaction to obtain a reaction solution; (3) standing and layering the reaction solution to obtain an organic phase; (4) distilling the organic phase at normal pressure, wherein the number of the tower plates of the distillation tower is 30, and collecting the fraction at 100-102 ℃ to obtain a crude product of 1-bromobutane; (5) the crude product of the para-brominated alkane is washed by alkali, washed by water and dried to obtain 2026kg of refined 1-bromobutane; (6) the purity of the 1-bromobutane fine product was checked to be 99.73%, and the yield of the 1-bromobutane fine product was calculated to be 91.88%.
Preferably, the temperature of the reaction system during the bromine dripping in the step (1) is controlled to be not higher than 60 ℃.
Preferably, the sulfur powder is an industrial first-grade sulfur powder meeting GB/T2449.1-2014.
Example 9
A preparation method of brominated alkanes comprises the following steps: (1) 1200kg of isoamyl alcohol with the purity of 99.8 percent is added into a 2000L glass lining reaction kettle with a reflux condenser under the stirring state to neutralize 75kg of sulfur powder, and 1125kg of bromine is dripped into the reaction kettle when the temperature is raised to 40 ℃; (2) after the bromine is dripped, the reflux reaction is carried out for 2 hours, the content of isoamyl alcohol is sampled and assayed to be 0.072 percent, and the reaction is stopped to obtain reaction liquid; (3) standing and layering the reaction solution to obtain an organic phase; (4) distilling the organic phase at normal pressure, wherein the number of the tower plates of the distillation tower is 30, and collecting fractions at the temperature of 119 ℃ and 121 ℃ to obtain a bromo-isopentane crude product; (5) carrying out alkali washing, water washing and drying on the crude bromoisopentane product to obtain 1883kg of a refined bromoalkane product; (6) the purity of the refined bromoisopentane product is detected to be 99.26 percent, and the yield of the refined bromoisopentane product is calculated to be 91.45 percent.
Preferably, the temperature of the reaction system during the bromine dripping in the step (1) is controlled to be not higher than 60 ℃.
Preferably, the sulfur powder is an industrial first-grade sulfur powder meeting GB/T2449.1-2014.
Example 10
A preparation method of brominated alkanes comprises the following steps: (1) adding 1600kg of n-octanol with the purity of 99.8 percent and 70kg of sulfur powder into a 3000L glass lining reaction kettle with a reflux condenser under the stirring state, and dripping 1050kg of bromine into the reaction kettle when the temperature is raised to 40 ℃; (2) after the bromine is dripped, the reflux reaction is carried out for 2 hours, the sampling and testing are carried out, the content of n-octanol is 0.057 percent, and the reaction is stopped to obtain reaction liquid; (3) standing and layering the reaction solution to obtain an organic phase, namely a 1-bromooctane crude product; (4) carrying out alkali washing, water washing and drying on the 1-bromooctane crude product to obtain 2269kg of 1-bromooctane refined product; (5) the purity of the 1-bromooctane refined product is detected to be 99.191%, and the yield of the 1-bromooctane refined product is calculated to be 95.53%.
Preferably, the temperature of the reaction system during the bromine dripping in the step (1) is controlled to be not higher than 60 ℃.
Preferably, the sulfur powder is an industrial first-grade sulfur powder meeting GB/T2449.1-2014.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. The preparation method of brominated alkanes is characterized by comprising the following preparation steps: (1) adding excessive sulfur powder into fatty alcohol under stirring, heating to 30-60 deg.C, and adding excessive bromine dropwise into fatty alcohol; (2) after the bromine is dripped, reflux reaction is carried out for 1-3h until the content of fatty alcohol in the reaction system is less than 0.1 percent, and reaction liquid is obtained after the reaction is stopped; (3) standing and layering the reaction solution to obtain an organic phase; (4) distilling the organic phase at normal pressure or reduced pressure to obtain crude bromo-alkane; (5) washing the crude bromoalkane product with alkali, washing with water, and drying to obtain refined bromoalkane product; (6) and detecting the purity of the brominated alkane refined product, and calculating the yield of the brominated alkane refined product.
2. The method according to claim 1, wherein the sulfur powder is added in an amount of 101-110% of the theoretical requirement.
3. The method for preparing bromoalkane according to claim 1, wherein the temperature of the reaction system during the dropwise addition of bromine in the step (1) is controlled to be 40-100 ℃.
4. The method according to claim 1, wherein the bromine is added in an amount of 101-110% of the theoretical requirement.
5. The method of claim 1, wherein the aliphatic alcohol is one of n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, and n-octanol.
6. The method for preparing brominated alkanes according to claim 1, wherein the sulfur powder is an industrial first-grade sulfur powder conforming to GB/T2449.1-2014.
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| CN202010914763.2A CN112194555A (en) | 2020-09-03 | 2020-09-03 | Preparation method of brominated alkanes |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433054A (en) * | 2022-09-28 | 2022-12-06 | 山东海王化工股份有限公司 | Preparation method of 1, 2-dibromoethane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2041189C1 (en) * | 1992-06-16 | 1995-08-09 | Славгородское производственное объединение "Алтайхимпром" им.Г.С.Верещагина | Method of ethyl bromide synthesis |
| CN103804121A (en) * | 2014-01-23 | 2014-05-21 | 安徽华润涂料有限公司 | Production process for synthesis of bromoethane |
| CN110903163A (en) * | 2019-09-17 | 2020-03-24 | 丛强 | Preparation method of tribromoneopentyl alcohol |
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2020
- 2020-09-03 CN CN202010914763.2A patent/CN112194555A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2041189C1 (en) * | 1992-06-16 | 1995-08-09 | Славгородское производственное объединение "Алтайхимпром" им.Г.С.Верещагина | Method of ethyl bromide synthesis |
| CN103804121A (en) * | 2014-01-23 | 2014-05-21 | 安徽华润涂料有限公司 | Production process for synthesis of bromoethane |
| CN110903163A (en) * | 2019-09-17 | 2020-03-24 | 丛强 | Preparation method of tribromoneopentyl alcohol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115433054A (en) * | 2022-09-28 | 2022-12-06 | 山东海王化工股份有限公司 | Preparation method of 1, 2-dibromoethane |
| CN115433054B (en) * | 2022-09-28 | 2024-05-03 | 山东海王化工股份有限公司 | Preparation method of 1, 2-dibromoethane |
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Application publication date: 20210108 |