CN104230647A - Preparation method of cis-1,4-dichloro-2-butylene - Google Patents
Preparation method of cis-1,4-dichloro-2-butylene Download PDFInfo
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- CN104230647A CN104230647A CN201410447859.7A CN201410447859A CN104230647A CN 104230647 A CN104230647 A CN 104230647A CN 201410447859 A CN201410447859 A CN 201410447859A CN 104230647 A CN104230647 A CN 104230647A
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Abstract
The invention relates to a method for preparing cis-1,4-dichloro-2-butylene from cis-1,4-butenediol as a raw material and triphosgene as a chlorination reagent. The method comprises the following concrete steps: dissolving triphosgene in a solvent, adding a catalyst for decomposing triphosgene, dropwise adding cis-1,4-butenediol into a triphosgene solution, and reacting to obtain cis-1,4-dichloro-2-butylene. The method is mild in process reaction condition, high in yield, good in repeatability and suitable for large-scale preparation; triphosgene completely takes part in reaction after the reaction is finished, and reaction byproducts are carbon dioxide and hydrogen chloride which can be very easily recycled.
Description
Technical field
The present invention relates to one with cis Isosorbide-5-Nitrae-butylene glycol for raw material, solid phosgene is the method that chlorination reagent prepares cis Isosorbide-5-Nitrae-dichloro-2-butene.
Background technology
Isosorbide-5-Nitrae-dichloro-2-butene is important industrial chemicals.Trans Isosorbide-5-Nitrae-dichloro-2-butene can be used to 2-vinylcyclopropane-1,1-dicarboxylic acid methylester [the C. E. Clark of synthesis of high purity, etal., US.Pat. 4781807], also can be used to synthesis 2,7-dimethyl-1,3,5-heptantriene-1,8-dialdehyde [H. Pommer, etal., Angew. Chem. 72,911-915 (1960)].Cis Isosorbide-5-Nitrae-dichloro-2-butene can be used to synthesize various heterocycle, as
n-Boc-3-pyrroline, a kind of novel antibacterial medicine fluoroquinolone key intermediate [T. Rajesh, etal., Organic Process Research & Development, 13,638-640 (2009)].Pi Shiqing etc. report that the bromo-succinimide of catalytic amount can high productivity convert cis Isosorbide-5-Nitrae-dichloro-2-butene be trans Isosorbide-5-Nitrae-dichloro-2-butene [Pi Shiqing, Chen Xinzhi, China Patent Publication No. CN1660729A].Therefore the synthesis of cis Isosorbide-5-Nitrae-dichloro-2-butene has more importantly meaning.
The existing method preparing cis Isosorbide-5-Nitrae-dichloro-2-butene mainly contains following several:
One, with cis Isosorbide-5-Nitrae-butylene glycol raw material, thionyl chloride is chlorinating agent, adds a small amount of pyridine or 1,2,3-benzotriazole catalyzed reaction prepares cis Isosorbide-5-Nitrae-dichloro-2-butene.[Amundsen，etal.,?J.?Am.?Chem.?Soc.,?73,?2118-2119(1951);?R.?Gleiter,?etal.,?J.?Am.?Chem.?Soc.,?114,?8921-8927(1992);?S.?S.?Chaudhari,?etal.,?Synlett,?11,?1763-1765(1999);?M.?Morimoto,?etal.,?Tetrahedron?Asymmetry,?19,?1464-1468(2008)]
Two, with cis Isosorbide-5-Nitrae-butylene glycol raw material, trichlorine phosphine oxide is chlorinating agent, adds a small amount of pyridine catalyzed reaction and prepares cis Isosorbide-5-Nitrae-dichloro-2-butene.(Mislow,?etal.,?J.?Am.?Chem.?Soc.,?73,?2118-2119(1951)
Three, with cis Isosorbide-5-Nitrae-butylene glycol raw material, hydrogen chloride gas is that chlorinating agent prepares cis Isosorbide-5-Nitrae-dichloro-2-butene.[BASF,?DE857369(1941)；Reppe，etal.,?Justus?Libigs?Annalen?der?Chemie,?596,?65(1955)]
Four, with cis Isosorbide-5-Nitrae-butylene glycol raw material, methylsulfonyl chloride is that chlorinating agent prepares cis Isosorbide-5-Nitrae-dichloro-2-butene.[M.?Altamura,?etal.,?J.?Org.?Chem.,?58,?272-274?(1993)]
Five, take DHF as raw material, titanium tetrachloride or thionyl chloride are that chlorinating agent prepares cis Isosorbide-5-Nitrae-dichloro-2-butene.[P.?A.?Delaney,?J.?Chem.?Soc.?Perkin?Transactions?1:?Organic?and?Bio-Organic?Chemistry?(1972-199),?1855(1986)；Reppe，etal.,?Justus?Libigs?Annalen?der?Chemie,?596,?65(1955)]
In above Lung biopsy, method two, method four and method five production cost are higher.Method three needs special pressure reaction still, and weight yield only has 50-60%, the pressure reaction still that production 100 kilograms of products just need 2000 liters is carried out with five times of solvents, its method does not obviously possess industrial value, current industrialization generates usual using method one, although thionyl chloride is more cheap, but sulfurous gas and the hydrogen chloride gas of two molar equivalents can be produced in reaction process, often produce sulfurous gas and 35.8 liters of hydrogen chloride gas that 100 kilograms of products can produce 35.8 liters, hydrogen chloride gas can be absorbed by water, and sulfurous gas needs a large amount of alkali lye classifications to absorb, process not thorough, sulfurous gas can overflow, in a word, a large amount of sulfurous gas can cause serious environmental pollution, and processing cost is high.
Summary of the invention
For the deficiencies in the prior art part, the invention provides a kind of simple to operate, cost low and there is no the cis Isosorbide-5-Nitrae-dichloro-2-butene preparation method of sulfur dioxide emissions.
The present invention is for reaching above object, be achieved through the following technical solutions: with cis 1,4-butylene glycol raw material, solid phosgene is chlorinating agent, and preparation method is specific as follows: be first dissolved in solvent by described solid phosgene, then adds the catalyzer for decomposing solid phosgene, then by cis 1,4-butylene glycol is added dropwise in solid phosgene solution and reacts, and reacts complete acquisition cis Isosorbide-5-Nitrae-dichloro-2-butene.
As preferably: the consumption of described catalyzer is 0.1-1.0g/100g solid phosgene, and the consumption of described solvent is 1 ~ 10 times of cis Isosorbide-5-Nitrae-butylene glycol and solid phosgene quality sum.
As preferably, the mole dosage of described solid phosgene is 0.69 ~ 0.8 times of cis Isosorbide-5-Nitrae-butylene glycol molar weight.
As preferably, described catalyzer is pyridine or 4-N, N dimethylamine yl pyridines (DMAP).
As preferably: described solvent is methylene dichloride, ethylene dichloride, toluene or tetracol phenixin.
As preferably, except the catalyzer of foregoing description, the present invention can also use triethylamine as catalyzer, 100-120 gram of triethylamine is added according to every 100 grams of solid phosgenes, temperature of reaction is 0-1000C, reaction times is 1-8 hour, and reaction terminates rear byproduct of reaction triethylamine hydrochloride as by-product recovery.
As preferably, the temperature of described reaction is 0-100 DEG C, and the reaction times is 1-8h.
The beneficial effect that the present invention realizes:
The present invention selects solid phosgene to be chlorination reagent, and solid phosgene is a kind of conventional industrial chemicals, easily buys and transport; In reaction process by catalyst decomposes be phosgene participate in reaction, reaction terminate rear solid phosgene participate in completely reaction, the by product of reaction is carbonic acid gas and hydrogen chloride gas, carbonic acid gas and hydrogen chloride gas are easy to recycle, there is larger industrial value, compare with method five
Method of the present invention is often produced 100kg product and is only had 35.8 liters of hydrogen chloride gas and 35.8 liters of Carbon emissions, and does not relate to the discharge of sulfurous gas.
Can add triethylamine is used for decomposing solid phosgene and absorption reaction generation hydrogenchloride as catalyzer in reaction system, the triethylamine hydrochloride purity of generation is high, arrives 99%GC purity.
Production operation condition of the present invention is simple, reaction conditions is gentle, adopt the cis 1 that method of the present invention finally obtains, 4-dichloro-2-butene purity is high, can more than 95% be reached, color is that micro-Huang is extremely light yellow, can directly use this solution, or straight run distillation can obtain the product (>99%GC purity) of high-content.
Embodiment
Below describe technical scheme of the present invention in detail.The embodiment of the present invention is only for concrete grammar is described, the scale of the method is not by the restriction of embodiment.
Embodiment 1
Prepare the there-necked flask with hydrogen chloride gas and carbon dioxide collection device, the solid phosgenes of 100 grams (0.34mol) are added reaction flask, adds 500 milliliters of methylene dichloride, then add 1 gram of pyridine, under reflux conditions drip 43 grams of cis Isosorbide-5-Nitrae-butylene glycols (0.49mol).Dropwise, continue backflow 8 hours, it is complete that GC detects raw material reaction, and cis Isosorbide-5-Nitrae-dichloro-2-butene reaches 95% GC purity.Liquid distillation obtains 56 grams of light yellow liquid cis Isosorbide-5-Nitrae-dichloro-2-butenes (92% productive rate), reaches 99% GC purity.Boiling point: 156-158
0c.
Embodiment 2
Prepare the there-necked flask with hydrogen chloride gas and carbon dioxide collection device, the solid phosgenes of 100 grams (0.34mol) are added reaction flask, adds 500 milliliters of methylene dichloride, then add 1 gram of 4-
n,
n-dimethylamino pyridine (DMAP), under reflux conditions drips 43 grams of cis Isosorbide-5-Nitrae-butylene glycols (0.49mol).Dropwise, continue backflow 8 hours, it is complete that GC detects raw material reaction, and cis Isosorbide-5-Nitrae-dichloro-2-butene reaches 95% GC purity.Liquid distillation obtains 56 grams of light yellow liquid cis Isosorbide-5-Nitrae-dichloro-2-butenes (92% productive rate), reaches 99% GC purity.Boiling point: 156-158
0c.
Embodiment 3
Prepare the there-necked flask with hydrogen chloride gas and carbon dioxide collection device, the solid phosgenes of 100 grams (0.34mol) are added reaction flask, adds 500 milliliters of ethylene dichloride, then add 1 gram of pyridine, under reflux conditions drip 43 grams of cis Isosorbide-5-Nitrae-butylene glycols (0.49mol).Dropwise, continue backflow 6 hours, it is complete that GC detects raw material reaction, and cis Isosorbide-5-Nitrae-dichloro-2-butene reaches 95% GC purity.Liquid distillation obtains 55 grams of light yellow liquid cis Isosorbide-5-Nitrae-dichloro-2-butenes (91% productive rate), reaches 99% GC purity.Boiling point: 156-158
0c.
Embodiment 4
Prepare the there-necked flask with hydrogen chloride gas and carbon dioxide collection device, the solid phosgenes of 100 grams (0.34mol) are added reaction flask, adds 500 milliliters of ethylene dichloride, then add 1 gram of 4-
n,
n-dimethylamino pyridine (DMAP), under reflux conditions drips 43 grams of cis Isosorbide-5-Nitrae-butylene glycols (0.49mol).Dropwise, continue backflow 8 hours, it is complete that GC detects raw material reaction, and cis Isosorbide-5-Nitrae-dichloro-2-butene reaches 95% GC purity.Liquid distillation obtains 56 grams of light yellow liquid cis Isosorbide-5-Nitrae-dichloro-2-butenes (92% productive rate), reaches 99% GC purity.Boiling point: 156-158
0c.
Embodiment 5
Prepare the there-necked flask with hydrogen chloride gas and carbon dioxide collection device, the solid phosgenes of 100 grams (0.34mol) are added reaction flask, adds 500 milliliters of toluene, then add 1 gram of pyridine, under reflux conditions drip 43 grams of cis Isosorbide-5-Nitrae-butylene glycols (0.49mol).Dropwise, continue backflow 4 hours, it is complete that GC detects raw material reaction, and cis Isosorbide-5-Nitrae-dichloro-2-butene reaches 95% GC purity.Liquid distillation obtains 54 grams of light yellow liquid cis Isosorbide-5-Nitrae-dichloro-2-butenes (89% productive rate), reaches 99% GC purity.Boiling point: 156-158
0c.
Embodiment 6
Prepare the there-necked flask with hydrogen chloride gas and carbon dioxide collection device, the solid phosgenes of 100 grams (0.34mol) are added reaction flask, add 500 milliliters of toluene, add 1 gram of 4-N again, N dimethylamine yl pyridines (DMAP), under reflux conditions drip 43 grams of cis Isosorbide-5-Nitrae-butylene glycols (0.49mol).Dropwise, continue backflow 4 hours, it is complete that GC detects raw material reaction, and cis Isosorbide-5-Nitrae-dichloro-2-butene reaches 95% GC purity.Liquid distillation obtains 54 grams of light yellow liquid cis Isosorbide-5-Nitrae-dichloro-2-butenes (89% productive rate), reaches 99% GC purity.Boiling point: 156-158
0c.
Embodiment 7
Prepare the there-necked flask with hydrogen chloride gas and carbon dioxide collection device, the solid phosgenes of 100 grams (0.34mol) are added reaction flask, adds 500 milliliters of methylene dichloride, then add 100 grams of triethylamines.Under reflux conditions drip 43 grams of cis Isosorbide-5-Nitrae-butylene glycols (0.49mol).Dropwise, continue backflow 8 hours, it is complete that GC detects raw material reaction.Concentrated solution, filter, solid methyl tertiary butyl ether washs.Liquid distillation obtains 56 grams of light yellow liquid cis Isosorbide-5-Nitrae-dichloro-2-butenes (92% productive rate), reaches 99% GC purity.Boiling point: 156-158
0c.130 grams of triethylamine hydrochlorides are obtained, 99%GC purity after solid drying.
Background technology lists five kinds of art methods, method two, method four and method five production cost are higher, the cost that the present invention produces 100kg product is compared compared with it, raw materials cost reduces 10-15%, energy consumption cost reduces 10-12%, and the discharge aqueous solution reclaims the byproduct obtained does not need extra process namely to have economic worth, in addition, method three needs special pressure reaction still, and weight yield only has 50-60%, as, the pressure reaction still that production 100 kilograms of products just need 2000 liters is carried out with five times of solvents, its method does not obviously possess industrial value, current industrialization generates usual using method one, although thionyl chloride is more cheap, but sulfurous gas and the hydrogen chloride gas of two molar equivalents can be produced in reaction process, often produce sulfurous gas and 35.8 liters of hydrogen chloride gas that 100 kilograms of products can produce 35.8 liters, hydrogen chloride gas can be absorbed by water, and sulfurous gas needs a large amount of alkali lye classifications to absorb, process not thorough, sulfurous gas can overflow, in a word, a large amount of sulfurous gas can cause serious environmental pollution, and processing cost is high, the present invention produces 100kg product and only produces 35.8 liters of hydrogenchloride and 35.8 liters of carbonic acid gas, hydrogenchloride is directly absorbed by water can obtain the higher hydrochloric acid soln of purity, do not pollute the environment in Carbon emission to air.
Finally, it is also to be noted that what enumerate above is only some specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also very many distortion.All distortion that the different technologies personnel of this area can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (7)
1. a cis 1, the synthetic method of 4-dichloro-2-butene, is characterized in that, with cis 1,4-butylene glycol raw material, solid phosgene is chlorinating agent, and preparation method is specific as follows: be first dissolved in solvent by described solid phosgene, then adds the catalyzer for decomposing solid phosgene, then by cis 1,4-butylene glycol is added dropwise in solid phosgene solution and reacts, and reacts complete acquisition cis Isosorbide-5-Nitrae-dichloro-2-butene.
2. cis 1 according to claim 1, the synthetic method of 4-dichloro-2-butene, is characterized in that, the consumption of described catalyzer is 0.1-1.0g/100g solid phosgene, the quality consumption of described solvent is 1 ~ 10 times of cis Isosorbide-5-Nitrae-butylene glycol and solid phosgene quality sum.
3. the synthetic method of cis Isosorbide-5-Nitrae-dichloro-2-butene according to claim 1, is characterized in that: the mole dosage of solid phosgene is 0.69 ~ 0.8 times of cis Isosorbide-5-Nitrae-butylene glycol molar weight.
4. the synthetic method of the cis Isosorbide-5-Nitrae-dichloro-2-butene according to claim 1 or 2 or 3, is characterized in that: described catalyzer is pyridine or 4-
n,
n-dimethylamino pyridine.
5. the synthetic method of the cis Isosorbide-5-Nitrae-dichloro-2-butene according to claim 1 or 2 or 3, is characterized in that: described solvent is methylene dichloride, ethylene dichloride, toluene or tetracol phenixin.
6. the synthetic method of the cis Isosorbide-5-Nitrae-dichloro-2-butene according to claim 1 or 2 or 3, is characterized in that, described catalyzer is triethylamine, and byproduct of reaction triethylamine hydrochloride is recycled.
7. the synthetic method of the cis Isosorbide-5-Nitrae-dichloro-2-butene according to claim 1 or 2 or 3, is characterized in that: temperature of reaction 0 ~ 100
0c, the reaction times is 1 ~ 8 hour.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671270A (en) * | 2008-09-11 | 2010-03-17 | 杭州澳赛诺化工有限公司 | Method for synthesizing cyanoacetylene derivatives |
| CN102617302A (en) * | 2012-02-27 | 2012-08-01 | 浙江新赛科药业有限公司 | Process for synthesizing trimethoxyphenyl stilbene |
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2014
- 2014-09-04 CN CN201410447859.7A patent/CN104230647A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671270A (en) * | 2008-09-11 | 2010-03-17 | 杭州澳赛诺化工有限公司 | Method for synthesizing cyanoacetylene derivatives |
| CN102617302A (en) * | 2012-02-27 | 2012-08-01 | 浙江新赛科药业有限公司 | Process for synthesizing trimethoxyphenyl stilbene |
Non-Patent Citations (1)
| Title |
|---|
| MISLOW ETAL: "Stereochemistry of 1,4-Addition.I.The Chlorination of Butadiene", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
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