CN109485542A - A kind of preparation method of the chloro- 6- iodohexane of 1- - Google Patents
A kind of preparation method of the chloro- 6- iodohexane of 1- Download PDFInfo
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- CN109485542A CN109485542A CN201811605943.1A CN201811605943A CN109485542A CN 109485542 A CN109485542 A CN 109485542A CN 201811605943 A CN201811605943 A CN 201811605943A CN 109485542 A CN109485542 A CN 109485542A
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- Prior art keywords
- chloro
- iodohexane
- preparation
- chlorine
- catalyst
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
Abstract
The invention discloses a kind of preparation methods of the chloro- 6- iodohexane of 1-, it is using the chloro- 1- hexanol of 6- and paratoluensulfonyl chloride as raw material, benzene or toluene are solvent, under phase transfer catalyst and acid binding agent effect, 2 ~ 5 hours own esters of preparation 4- toluenesulfonic acid -6- chlorine are reacted at -5 ~ 5 DEG C, then again with 0.5 ~ 3 hour chloro- 6- iodohexane of preparation 1- of sodium iodide back flow reaction.The method of the present invention has easy to operate, post-processing simplicity, the higher feature of yield.
Description
Technical field
The invention belongs to technical field of fine, and in particular to a kind of preparation method of the chloro- 6- iodohexane of 1-.
Background technique
The chloro- 6- iodohexane of 1- is a kind of colourless or lurid transparency liquid, is the important centre for preparing pesticide and medicine
Body, therefore have good market prospects.
The method that tradition prepares the chloro- 6- iodohexane of 1- is using acetone as solvent, is original with 1,6- dichloro hexane and sodium iodide
Material, by iodine exchange reaction (such as: Journal of the Chemical Society, 2100-3; 1950；
Australian Journal of Chemistry, 32(12),2777-81;1979).This scheme is easy to operate, but reacts
Time is long, and reaction is incomplete, and obtained product is the chloro- 6- iodohexane of 1- and 1, bis- iodohexane of 6-, it is more difficult to separate, after rectifying only
The about 50% chloro- 6- iodohexane of 1- is obtained, industrialized production is not particularly suited for.
In recent years, (Tetrahedron, 66 (35), 7161-7168 were had been reported that; 2010；) with chloro- 1 hexanol of 6- and right
Toluene sulfochloride be the own ester of Material synthesis 4- toluenesulfonic acid -6- chlorine, then with sodium iodide exchange reaction obtain the chloro- 6- iodine of 1- oneself
Alkane.This technical solution improves product yield, but existing preparation method uses a large amount of pyridines, and pyridine is soluble easily in water and has
Solvent, it is difficult to reach efficiently separating and recycling for solvent, therefore high expensive.
Summary of the invention
The present invention is intended to provide a kind of preparation method of the chloro- 6- iodohexane of improved 1-, existing at high cost, difficult to overcome
The technological deficiencies such as operation realize the chloro- 6- iodohexane industrial scale production of 1-.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of the chloro- 6- iodohexane of 1-, using the chloro- 1- hexanol of 6- and paratoluensulfonyl chloride as raw material, benzene or toluene
2 ~ 5 hours preparation 4- toluenesulfonic acids-are reacted under condition of ice bath under phase transfer catalyst and acid binding agent effect for solvent
The own ester of 6- chlorine, then again with 0.5 ~ 3 hour chloro- 6- iodohexane of preparation 1- of sodium iodide back flow reaction.
Specifically, phase transfer catalyst is quaternary ammonium salt catalyst during sulfonylation, optimal selection is benzyl three
The optimum molar ratio of ethyl ammonium chloride (TEBA), the chloro- 1- hexanol of 6- and paratoluensulfonyl chloride, catalyst are as follows: 1:1 ~ 1.2:0.02 ~
0.05, the amount of solvent is 2 ~ 3 times of substrate quality, the preferred sodium hydroxide of acid binding agent.
Specifically, in iodine exchange reaction the optimum molar ratio of the own ester of 4- toluenesulfonic acid -6- chlorine and sodium iodide be 1:1 ~
1.2。
The reaction equation of the method for the present invention is as follows:
Compared to the prior art, the method for the present invention the utility model has the advantages that sulfonylation process uses toluene or benzene for solvent, in conjunction with
The use of phase transfer catalyst reduces reaction difficulty and operation difficulty, and production process is easy to control, and solvent is easy to be recycled, receives
Rate is higher.
Specific embodiment
Technical solution of the present invention is further discussed in detail with reference to embodiments, but protection scope of the present invention
It is not limited thereto.
Embodiment 1
The synthesis of the own ester of 4- toluenesulfonic acid -6- chlorine
50mL sodium hydrate aqueous solution (wherein sodium hydroxide is 4mol/L) is added in reaction kettle, 0.5gTEBA and 10.0g6- are chloro-
1- hexanol, ice water bath is cooling, and quickly under stirring, the 50mL benzole soln of the paratoluensulfonyl chloride containing 15.0g, reaction temperature is slowly added dropwise
Degree control drips, then react 2 hours for 2 hours at -5 ~ 0 DEG C, stands, liquid separation, dry, and benzene is recycled in air-distillation, obtains
The own ester crude product (content 90%) of 21.3g4- toluenesulfonic acid -6- chlorine.
The synthesis of the chloro- 6- iodohexane of 1-
Above-mentioned crude product and 10.88g sodium iodide are added in 50mL acetone, are vigorously stirred, it is back flow reaction 1 hour, cooling, it is quiet
It sets, filters, filtrate is distilled to recover acetone through normal pressure, then carries out rectifying, and the fraction for collecting 82 DEG C is the chloro- 6- iodohexane of product 1-,
Colourless liquid, yield 86.2%, purity 99%.
Embodiment 2
The synthesis of the own ester of 4- toluenesulfonic acid -6- chlorine
50mL sodium hydrate aqueous solution (wherein sodium hydroxide is 4mol/L) is added in reaction kettle, 0.6gTEBA and 10.0g6- are chloro-
1- hexanol, ice water bath is cooling, and quickly under stirring, the 50mL toluene solution of the paratoluensulfonyl chloride containing 16.5g is slowly added dropwise, reacts
Temperature is controlled at 0 ~ 5 DEG C, is dripped within 2 hours, then react 2 hours, is stood, liquid separation, dry, and toluene is recycled in air-distillation, is obtained
The own ester crude product (content 91%) of 21.6g4- toluenesulfonic acid -6- chlorine.
The synthesis of the chloro- 6- iodohexane of 1-
Above-mentioned crude product and 11.97g sodium iodide are added in 50mL acetone, are vigorously stirred, it is back flow reaction 1 hour, cooling, it stands,
Filtering, filtrate is distilled to recover acetone through normal pressure, then carries out rectifying, and the fraction for collecting 82 DEG C is the chloro- 6- iodohexane of product 1-, colourless
Liquid, yield 86.7%, purity 99%.
Above-described embodiment is the preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, others are included in protection model of the invention without departing from the substitute mode that should be equivalent is changed made by the present invention
Within enclosing.
Claims (3)
1. a kind of preparation method of the chloro- 6- iodohexane of 1-, which is characterized in that with the chloro- 1- hexanol of 6- and paratoluensulfonyl chloride be original
Material, benzene or toluene are solvent, and under phase transfer catalyst and acid binding agent effect, 2 ~ 5 hours preparation 4- first are reacted at -5 ~ 5 DEG C
The own ester of base benzene sulfonic acid -6- chlorine, then again with 0.5 ~ 3 hour chloro- 6- iodohexane of preparation 1- of sodium iodide back flow reaction.
2. the preparation method of the chloro- 6- iodohexane of 1- as described in claim 1, which is characterized in that phase turns during sulfonylation
Shifting catalyst is quaternary ammonium salt catalyst, and optimal selection is benzyltriethylammoinium chloride, the chloro- 1- hexanol of 6- and tolysulfonyl
The optimum molar ratio of chlorine, catalyst are as follows: 1:1 ~ 1.2:0.02 ~ 0.05, the amount of solvent are 2 ~ 3 times of substrate quality, and acid binding agent is excellent
Select sodium hydroxide.
3. the preparation method of the chloro- 6- iodohexane of 1- as described in claim 1, which is characterized in that 4- methylbenzene in iodine exchange reaction
The optimum molar ratio of the own ester of sulfonic acid -6- chlorine and sodium iodide is 1:1 ~ 1.2.
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| CN201811605943.1A CN109485542A (en) | 2018-12-27 | 2018-12-27 | A kind of preparation method of the chloro- 6- iodohexane of 1- |
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| CN201811605943.1A CN109485542A (en) | 2018-12-27 | 2018-12-27 | A kind of preparation method of the chloro- 6- iodohexane of 1- |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003313159A (en) * | 2002-04-23 | 2003-11-06 | Mitsui Chemicals Inc | Method for producing sulfonate compound |
| WO2008059349A1 (en) * | 2006-11-14 | 2008-05-22 | Orphachem | Method of fluorine-18 labelling of tropane derivatives |
| CN103755602A (en) * | 2013-12-24 | 2014-04-30 | 江苏天容集团股份有限公司 | Synthetic method of L-p-toluenesulfonyl ethyl lactate |
| CN104311514A (en) * | 2014-10-14 | 2015-01-28 | 安徽扬子化工有限公司 | Method for synthesizing 3-hydroxymethyl tetrahydrofuran ester |
| CN107652162A (en) * | 2017-11-29 | 2018-02-02 | 常州沃腾化工科技有限公司 | A kind of preparation method of cyclohexyl bromide methane |
-
2018
- 2018-12-27 CN CN201811605943.1A patent/CN109485542A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003313159A (en) * | 2002-04-23 | 2003-11-06 | Mitsui Chemicals Inc | Method for producing sulfonate compound |
| WO2008059349A1 (en) * | 2006-11-14 | 2008-05-22 | Orphachem | Method of fluorine-18 labelling of tropane derivatives |
| CN103755602A (en) * | 2013-12-24 | 2014-04-30 | 江苏天容集团股份有限公司 | Synthetic method of L-p-toluenesulfonyl ethyl lactate |
| CN104311514A (en) * | 2014-10-14 | 2015-01-28 | 安徽扬子化工有限公司 | Method for synthesizing 3-hydroxymethyl tetrahydrofuran ester |
| CN107652162A (en) * | 2017-11-29 | 2018-02-02 | 常州沃腾化工科技有限公司 | A kind of preparation method of cyclohexyl bromide methane |
Non-Patent Citations (5)
| Title |
|---|
| （美）奈克（NECKERS，D.C.），（美）多伊尔（DOYLE，M.）著；: "《有机化学 下》", 30 November 1985, 化学工业出版社 * |
| KENJI MORI ET AL: ""Pheromone synthesis. Part 244: Synthesis of the racemate and enantiomers of (11Z,19Z)-CH503 (3-acetoxy-11,19-octacosadien-1-ol), a new sex pheromone of male Drosophila melanogaster to show its (S)-isomer and racemate as bioactive"", 《TETRAHEDRON》 * |
| XIAOLIN KANG ET AL: ""Synthesis of a main-chain liquid crystalline azo-polymer"", 《COLLOID POLYM SCI》 * |
| 段行信编: "《实用精细有机合成手册》", 31 January 2000, 北京：化学工业出版社 * |
| 江体乾等: "《化工工艺手册》", 28 February 1992, 上海科学技术出版社 * |
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Application publication date: 20190319 |