CN100494133C - Method of synthesizing 1-chloro-3-ethyl-benzene - Google Patents
Method of synthesizing 1-chloro-3-ethyl-benzene Download PDFInfo
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- CN100494133C CN100494133C CNB2007100213879A CN200710021387A CN100494133C CN 100494133 C CN100494133 C CN 100494133C CN B2007100213879 A CNB2007100213879 A CN B2007100213879A CN 200710021387 A CN200710021387 A CN 200710021387A CN 100494133 C CN100494133 C CN 100494133C
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Abstract
This invention relates to a synthesizing method for the chloroacetyl benzene including: A, taking Inter-chlorophenyl ethanone as the raw material to carry out refluence reaction with hydrazine hydrate to generate hydrazone to be cooled and delaminated to get the hydrazone, B, coheating the hydrazone in a de-glycol solution of KOH or NaOH to be reacted to generate a the chloroacetyl benzene rough product, C, distilling the rough product to get a product, which is advantaged that the technical process is simple, transforming rate is high, by-product is less and the rate of finished products gets 95-97%, and purity reaches to 98.6-99%.
Description
Technical field
The present invention relates to a kind of synthetic method of 1-chloro-3-ethyl-benzene, belong to the processing technique field of organism intermediate.
Background technology
1-chloro-3-ethyl-benzene is a kind of colourless liquid, mainly as the organic synthesis thing as ... intermediate.Bibliographical information about the 1-chloro-3-ethyl-benzene synthesis technique is very few, only have related in the U.S. Pat 2159370, this patent is to be raw material with chlorobenzene (1mol), under Lewis acid such as aluminum chloride (0.055mol) effect, and feed the excessive rare gas of second (1.44mol) at 80 ℃, make the 1-chloro-3-ethyl-benzene crude product, crude product obtains the finished product 1-chloro-3-ethyl-benzene through rectifying, the purity of resulting finished product 1-chloro-3-ethyl-benzene is 80%, wherein also contains 20% adjacent chloroethyl benzene.The synthetic method by product that this patent is recommended is many, for example contains 7.31% adjacent chloroethyl benzene, 12.90% diethyl chlorobenzene in the crude product, also has 24.73% high boiling material in addition; The yield of finished product 1-chloro-3-ethyl-benzene is lower, only is 29.25%; Transformation efficiency is low, because crude product contains 25.43% chlorobenzene, so transformation efficiency only is 74.57%.Based on these factors, if produce 1-chloro-3-ethyl-benzene, so owing to yield, all poor economy of losing finished product of purity with aforesaid method.
Summary of the invention
Task of the present invention is the synthetic method that a kind of 1-chloro-3-ethyl-benzene will be provided, and this method need not rectifying and technology is simple, yield and purity are high and have economy.
Task of the present invention is finished like this, a kind of synthetic method of 1-chloro-3-ethyl-benzene, and it may further comprise the steps:
A). with the m chloroacetophenone is raw material, generates hydrazone with the hydrazine hydrate back flow reaction, and cooling back layering obtains hydrazone;
B). hydrazone is total to thermal response in the Diethylene Glycol solution of potassium hydroxide or sodium hydroxide, generates the 1-chloro-3-ethyl-benzene crude product;
C). with the distillation of 1-chloro-3-ethyl-benzene crude product, obtain the finished product 1-chloro-3-ethyl-benzene, wherein: described back flow reaction is a back flow reaction under the normal pressure, reaction times is 120-180min, temperature of reaction is 107-119 ℃, and the described temperature of reaction of thermal response altogether is 110-148 ℃, and the reaction times is 90-180min.
In one embodiment of the invention, the mol ratio of described m chloroacetophenone and hydrazine hydrate is 1:1.5～3, and wherein, the concentration of hydrazine hydrate is 40-85%.
In another embodiment of the present invention, described be cooled to be cooled to≤40 ℃, the described standing demix that is layered as, the upper strata is for reclaiming hydrazine hydrate after the layering, and lower floor is a hydrazone.
In yet another embodiment of the present invention, the weight ratio of described m chloroacetophenone and Diethylene Glycol, potassium hydroxide or sodium hydroxide is 1: 2-4: 0.3-0.5.
More of the present invention and among embodiment, described distillation is for adding water normal pressure component distillation.
In of the present invention and then embodiment, described distillation is not for adding the water underpressure distillation.
One of advantage of the inventive method makes technology become simple owing to need not rectifying; Two, the reaction conversion ratio height, by product is few and can make the 1-chloro-3-ethyl-benzene product yield reach 95-97%; Three, purity can reach 98.6-99%; Four, can be put to suitability for industrialized production and have economy.
Embodiment
Embodiment 1:
A). in the 250ml four-hole reaction flask of band whipping appts, add the m chloroacetophenone 30.9g (0.27mol) of purity 99.0% and the hydrazine hydrate 23.6g (0.4mol) of adding concentration 85%, start mechanical stirring or claim and stir automatically, be warming up to 110-119 ℃ of reaction 120min, be cooled to normal temperature, static layering, get the layer oily matter hydrazone, and the upper strata is the hydrazine hydrate that is used to reclaim;
B). in the 250ml four-hole reaction flask of another band whipping appts, add Diethylene Glycol 100g and flaky sodium hydrate 10g (0.25mol) and by steps A) hydrazone of preparation is whole, start mechanical stirring, be warming up to 140-148 ℃ of reaction 120min, observation has or not bubble to overflow, promptly observe nitrogen effusion situation, till not having nitrogen and overflowing, promptly generate the 1-chloro-3-ethyl-benzene crude product;
C). to step B) the 1-chloro-3-ethyl-benzene crude product distillation that generated, specifically being at step B) reaction promptly reaches after finishing to end to having and becomes stream after nitrogen is overflowed again for not adding the underpressure distillation of water, collect 140 ℃/150mm with front-end volatiles, the distillate layering, layer oily matter washes with water once but is not limited only to once, and is dry, to filter by the colourless transparent liquid of purity shown in the following table and yield be the 1-chloro-3-ethyl-benzene finished product.
Embodiment 2:
A). in the 250ml four-hole reaction flask of band whipping appts, add the m chloroacetophenone 30.9g (0.2mol) of purity 99.0% and the hydrazine hydrate 17.7g (0.3mol) of adding concentration 85%, start mechanical stirring, be warming up to 111-117 ℃ of reaction 150min, be cooled to normal temperature, static layering, get the layer oily matter hydrazone, and the upper strata is the hydrazine hydrate that is used to reclaim;
B). in the 250ml four-hole reaction flask of another band whipping appts, add Diethylene Glycol 136g and potassium hydroxide 15.4g (0.27mol) and add by steps A) hydrazone that makes is whole, start mechanical stirring in 110-115 ℃ of reaction 90min, till not having nitrogen and overflowing, promptly generate the 1-chloro-3-ethyl-benzene crude product, be cooled to below 100 ℃;
C). to by step B) the 1-chloro-3-ethyl-benzene crude product that generated adds water and carries out vapor distillation, the overhead product layering, organic layer adds water washing once but need not be limited to once, layer oily matter drying, filtration, and the colourless transparent liquid that obtains by purity shown in the following table and yield is the 1-chloro-3-ethyl-benzene finished product.
Embodiment 3:
A). in the 250ml four-hole reaction flask of band whipping appts, add the m chloroacetophenone 30.9g (0.2mol) of purity 99.0% and the hydrazine hydrate 38.5g (0.6mol) of adding concentration 78%, start mechanical stirring, be warming up to 110-119 ℃ of reaction 120min, be cooled to normal temperature, static layering or title standing demix, get the layer oily matter hydrazone, and the upper strata is the hydrazine hydrate that is used to reclaim;
B). in the 250ml four-hole reaction flask of another band whipping appts, add Diethylene Glycol 60g and potassium hydroxide 12g (0.21mol) and add by steps A) hydrazone of preparation is whole, start mechanical stirring in 130-140 ℃ of reaction 180min, till not having nitrogen and overflowing, promptly generate the 1-chloro-3-ethyl-benzene crude product;
C). to by step B) the 1-chloro-3-ethyl-benzene crude product that generated do not add the water underpressure distillation, collect 140 ℃/150mm with front-end volatiles, the overhead product layering, wash with water once but be not limited only to once, layer oily matter drying, filtration, the colourless transparent liquid that obtains by purity shown in the following table and yield is the finished product 1-chloro-3-ethyl-benzene.
Embodiment 4:
A). in the 250ml four-hole reaction flask of band whipping appts, add the m chloroacetophenone 30.9g (0.2mol) of purity 99.0% and the hydrazine hydrate 75.1g (0.6mol) of adding concentration 40%, start mechanical stirring or claim and stir automatically, be warming up to 107-116 ℃ of back flow reaction 180min, be cooled to normal temperature, static layering or title standing demix, get the layer oily matter hydrazone, and the upper strata is the hydrazine hydrate that is used to reclaim;
B). the Diethylene Glycol that in the 250ml four-hole reaction flask of another band whipping appts, adds the potassium hydroxide that embodiment 3 reclaims all and add by steps A) hydrazone of preparation is whole, start mechanical stirring in 130-140 ℃ of reaction 180min, till not having nitrogen and overflowing, promptly generate the 1-chloro-3-ethyl-benzene crude product;
C). to by step B) the 1-chloro-3-ethyl-benzene crude product that generated adds water and carries out vapor distillation, the overhead product layering, organic layer adds water washing once but need not be limited to once, layer oily matter drying, filtration, and the colourless transparent liquid that obtains by purity shown in the following table and yield is the 1-chloro-3-ethyl-benzene finished product.
The technique effect contrast table
Claims (6)
1, a kind of synthetic method of 1-chloro-3-ethyl-benzene is characterized in that it may further comprise the steps:
A). with the m chloroacetophenone is raw material, generates hydrazone with the hydrazine hydrate back flow reaction, and cooling back layering obtains hydrazone;
B). hydrazone is total to thermal response in the Diethylene Glycol solution of potassium hydroxide or sodium hydroxide, generates the 1-chloro-3-ethyl-benzene crude product;
C). with the distillation of 1-chloro-3-ethyl-benzene crude product, obtain the finished product 1-chloro-3-ethyl-benzene, wherein: described back flow reaction is a back flow reaction under the normal pressure, reaction times is 120-180min, temperature of reaction is 107-119 ℃, and the described temperature of reaction of thermal response altogether is 110-148 ℃, and the reaction times is 90-180min.
2, the synthetic method of 1-chloro-3-ethyl-benzene according to claim 1, the mol ratio that it is characterized in that described m chloroacetophenone and hydrazine hydrate is 1: 1.5～3, wherein, the concentration of hydrazine hydrate is 40-85%.
3, the synthetic method of 1-chloro-3-ethyl-benzene according to claim 1, it is characterized in that described be cooled to be cooled to≤40 ℃, the described standing demix that is layered as, the upper strata is for reclaiming hydrazine hydrate after the layering, and lower floor is a hydrazone.
4, the synthetic method of 1-chloro-3-ethyl-benzene according to claim 1, the weight ratio that it is characterized in that described m chloroacetophenone and Diethylene Glycol, potassium hydroxide or sodium hydroxide is 1: 2-4: 0.3-0.5.
5, the synthetic method of 1-chloro-3-ethyl-benzene according to claim 1 is characterized in that described distillation is for adding water normal pressure component distillation.
6, the synthetic method of 1-chloro-3-ethyl-benzene according to claim 1 is characterized in that described distillation is not for adding the water underpressure distillation.
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| CNB2007100213879A CN100494133C (en) | 2007-04-06 | 2007-04-06 | Method of synthesizing 1-chloro-3-ethyl-benzene |
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| CNB2007100213879A CN100494133C (en) | 2007-04-06 | 2007-04-06 | Method of synthesizing 1-chloro-3-ethyl-benzene |
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| CN100494133C true CN100494133C (en) | 2009-06-03 |
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Non-Patent Citations (8)
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| 4-苯基-1-丁醇的合成研究. 王晓琴等.广州化学，第30卷第1期. 2005 |
| 4-苯基-1-丁醇的合成研究. 王晓琴等.广州化学，第30卷第1期. 2005 * |
| 对氯乙基氯苯的合成. 张卫红等.化工进展，第24卷第12期. 2005 |
| 对氯乙基氯苯的合成. 张卫红等.化工进展，第24卷第12期. 2005 * |
| 对溴乙苯的合成研究. 吴英绵等.河北化工，第4期. 2004 |
| 对溴乙苯的合成研究. 吴英绵等.河北化工，第4期. 2004 * |
| 黄鸣龙改良还原法（上）. 韩广甸等.医药工业，第17卷第3期. 1986 |
| 黄鸣龙改良还原法（上）. 韩广甸等.医药工业，第17卷第3期. 1986 * |
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