CN105461533B - The synthetic method of the pentanone of 3,5 dichloro 2 - Google Patents
The synthetic method of the pentanone of 3,5 dichloro 2 Download PDFInfo
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- CN105461533B CN105461533B CN201510820567.8A CN201510820567A CN105461533B CN 105461533 B CN105461533 B CN 105461533B CN 201510820567 A CN201510820567 A CN 201510820567A CN 105461533 B CN105461533 B CN 105461533B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/84—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by azeotropic distillation
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Abstract
The invention discloses a kind of synthetic method of the pentanone of 3,5 dichloro 2, using α chlorine α ' acetyl group gamma butyrolactones as raw material, under salt and phase transfer catalyst effect, is reacted with hydrochloric acid, the pentanone of 3,5 dichloro 2 is synthesized by the method for continuous steam distillation.The present invention differs the characteristics of larger according to raw material with product boiling point, the technical scheme separated using side border ring, not only increases the purity of product, more greatly improves yield, and the recyclable recycling of hydrochloric acid solution in reaction.Raw material reaction speed can be improved by adding phase transfer catalyst, reduces its accumulation in reaction system, addition salt can increase reaction distillation temperature, accelerate product separating rate, the overall residence time for reducing raw material and product in reaction system, so as to reduce side reaction, improve selectivity.
Description
Technical field
The invention belongs to the field of chemical synthesis, and in particular to the synthetic method of one kind 3,5- Dichloro-2-pentanones.
Background technology
3,5- Dichloro-2-pentanones are the important intermediates of medical pesticide synthesis.Its common synthetic method is in ice at present
In the presence of acetic acid, raw material α-chloro- α '-acetyl group-gamma-butyrolacton and hydrochloric acid reaction, then carried out by the method for extracting rectifying
Separating-purifying.The shortcomings that this method is that glacial acetic acid is difficult to reclaim, and reaction yield is low, poor selectivity, the necessary rectification and purification of product, warp
Ji property is poor.
The content of the invention
The present invention provides a kind of synthesis side for the 3,5- Dichloro-2-pentanones that cost is low, product yield is high regarding to the issue above
Method.
The present invention, the characteristics of larger, is differed with product boiling point according to raw material, the technical scheme separated using side border ring, no
But the purity of product is improved, more greatly improves yield, and the recyclable recycling of hydrochloric acid solution in reaction.By adding phase
Transfer catalyst can improve raw material reaction speed, reduce its accumulation in reaction system, and addition salt can increase reaction and steam
Temperature is evaporated, accelerates product separating rate, it is the overall residence time for reducing raw material and product in reaction system, secondary anti-so as to reduce
Should, improve selectivity.Specific technical scheme is as follows.
The synthetic method for 3, the 5- Dichloro-2-pentanones that the application provides, using α-chloro- α '-acetyl group-gamma-butyrolacton as original
Material, under salt and phase transfer catalyst effect, reacted with hydrochloric acid, by the synthesis of the method for continuous steam distillation separate 3,
5- Dichloro-2-pentanones.
The concentration of hydrochloric acid described in the application synthetic method is 20-35%, hydrochloric acid dosage be raw material α-chloro- α '-acetyl group-
1.5-5 times of gamma-butyrolacton molal quantity.
Preferably, the concentration of hydrochloric acid used in the application synthetic method is 25-30%, hydrochloric acid dosage be raw material α-chloro- α '-
2.0-2.5 times of acetyl group-gamma-butyrolacton molal quantity.
Salt described in the application synthetic method is one kind in sodium chloride, magnesium chloride or potassium chloride, and its dosage is rubbed for hydrochloric acid
0.1-0.5 times, preferably 0.2-0.25 times of that number
Phase transfer catalyst described in the application synthetic method is halogenation normal-butyl ammonium, benzyl halide trimethyl ammonium and halogenation
Any one or a few in benzyl triethyl ammonium ammonium.
The dosage of phase transfer catalyst described in the application synthetic method is raw material α-chloro- α '-acetyl group-gamma-butyrolacton
The 0.3-10% of quality, preferable dosage are 1-1.5%.
Further, raw material α-chloro- α '-acetyl group-gamma-butyrolacton is to pass through drop in the synthetic method that the application provides
What the mode added was added, time for adding 3-12h, preferably 6-8h.
3,5- Dichloro-2-pentanones described in the application synthetic method are that the method distilled by azeotrope with water is separated,
Mode separates for side border ring.
Described in the application synthetic method react and distill carry out at the same temperature, reaction temperature according to salt dosage not
Together, it is maintained between 100-115 DEG C.And raw material time for adding is 3-12h, and reacts basis herein and continue to extend 1-3h, preferably
Time for adding be 6-8h, then the preferable reaction time is 7-9h.
Beneficial effect：
1）Present invention process safety and environmental protection, it is easy to industrialize；
2）Synthetic method of the present invention greatly improves yield, reduces cost；
3）Synthetic method products obtained therefrom purity of the present invention is high, without further separating-purifying.
Embodiment
The technical scheme provided with reference to specific embodiment the application is further explained.
Embodiment 1
30% concentrated hydrochloric acid 243g (2mol) and 23.4g sodium chloride is added into 1000ml four-hole bottles（0.4mol）.Stirring rises
Temperature to 105 DEG C of reflux states, start to be added dropwise 1.7g TBABs be dissolved in 162.6g (1mol) α-chloro- α '-acetyl group-γ-
The solution of butyrolactone, collects layer oily matter in water knockout drum.About 7h completion of dropwise addition, continue reaction backflow 1h, collect grease
Common 166g, with 100g washings once, oil reservoir product obtains 157g.It is 97% to detect normalization purity with GC, calculated yield 96.5%.
Embodiment 2
30% concentrated hydrochloric acid 243g (2mol) and 38g magnesium chlorides is added into 1000ml four-hole bottles（0.4mol）.Stirring heating
To 108 DEG C of reflux states, start dropwise addition 1.7g TBABs and be dissolved in 162.6g (1mol) α-chloro- α '-acetyl group-γ-fourth
The solution of lactone, collects layer oily matter in water knockout drum.About 7h completion of dropwise addition, continue reaction backflow 1h, collect grease and be total to
160g, with 100g washings once, oil reservoir product obtains 154g.It is 97% to detect normalization purity with GC, calculated yield 94.8%.
Embodiment 3
30% concentrated hydrochloric acid 243g (2mol) and 23.4g sodium chloride is added into 1000ml four-hole bottles（0.4mol）.Stirring rises
Temperature to 105 DEG C of reflux states, start to be added dropwise 4.8g tetrabutylammonium chlorides be dissolved in 162.6g (1mol) α-chloro- α '-acetyl group-γ-
The solution of butyrolactone, collects layer oily matter in water knockout drum.About 7h completion of dropwise addition, continue reaction backflow 1h, collect grease
Common 162g, with 100g washings once, oil reservoir product obtains 150g.It is 97% to detect normalization purity with GC, calculated yield 93.4%.
Comparative example 1
30% concentrated hydrochloric acid 243g (2mol) is added into 1000ml four-hole bottles.Stirring is warming up to 102 DEG C of reflux states, opens
Begin that 162.6g (1mol) α-chloro- α '-acetyl group-gamma-butyrolacton is added dropwise, layer oily matter is collected in water knockout drum.About 7h is added dropwise
Terminate, continue reaction backflow 1h, collect the common 135g of grease, with 100g washings once, oil reservoir product obtains 130g.Returned with GC detections
One change purity is 95%, calculated yield 81.7%.
Comparative example 2
30% concentrated hydrochloric acid 243g (2mol) and 23.4g sodium chloride is added into 1000ml four-hole bottles（0.4mol）.Stirring rises
Temperature starts that 162.6g (1mol) α-chloro- α '-acetyl group-gamma-butyrolacton is added dropwise, received in water knockout drum to 105 DEG C of reflux states
Collect layer oily matter.About 7h completion of dropwise addition, continue reaction backflow 1h, collect the common 145g of grease, with 100g washings once, oil reservoir
Product obtains 140g.It is 96% to detect normalization purity with GC, calculated yield 86.8%.
Comparative example 3
30% concentrated hydrochloric acid 243g (2mol) is added into 1000ml four-hole bottles.Stirring is warming up to 102 DEG C of reflux states, opens
Beginning is added dropwise 1.7g TBABs and is dissolved in 162.6g (1mol) α-chloro- α '-acetyl group-gamma-butyrolacton, is received in water knockout drum
Collect layer oily matter.About 7h completion of dropwise addition, continue reaction backflow 1h, collect the common 152g of grease, with 100g washings once, oil reservoir
Product obtains 140g.It is 96% to detect normalization purity with GC, calculated yield 90.2%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (9)
- The synthetic method of 1.3,5- Dichloro-2-pentanones, it is characterised in that using α-chloro- α '-acetyl group-gamma-butyrolacton as raw material, Under salt and phase transfer catalyst effect, reacted with hydrochloric acid, 3,5- is separated to obtain by the method synthesis of continuous steam distillation Dichloro-2-pentanone.
- 2. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that the concentration of the hydrochloric acid For 20-35%, hydrochloric acid dosage is 1.5-5 times of raw material α-chloro- α '-acetyl group-gamma-butyrolacton molal quantity.
- 3. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 2, it is characterised in that the concentration of hydrochloric acid used is 25-30%, hydrochloric acid dosage are 2.0-2.5 times of raw material α-chloro- α '-acetyl group-gamma-butyrolacton molal quantity.
- 4. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 2, it is characterised in that the salt be sodium chloride, One kind in magnesium chloride or potassium chloride, its dosage are 0.1-0.5 times of hydrochloric acid molal quantity.
- 5. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that the phase transfer catalysis (PTC) Agent is any one or a few in halogenation normal-butyl ammonium, benzyl halide trimethyl ammonium and benzyl halide triethyl ammonium.
- 6. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 5, it is characterised in that the phase transfer catalysis (PTC) The dosage of agent is the 0.3-10% of raw material α-chloro- α '-acetyl group-gamma-butyrolacton quality.
- 7. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that raw material α-chloro- α '-acetyl Base-gamma-butyrolacton is added by way of dropwise addition, time for adding 3-12h.
- 8. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that the chloro- 2- penta of 3,5- bis- Ketone is that the method distilled by azeotrope with water is separated, and mode separates for side border ring.
- 9. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that the reaction and distillation exist Carried out under same temperature, reaction temperature is maintained between 100-115 DEG C, reaction time 6-13h.
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| CN106278845B (en) * | 2016-05-19 | 2019-03-05 | 海正化工南通有限公司 | A kind of synthesis technology of 3,5- Dichloro-2-pentanone |
| CN106565441A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Synthesis method of 3,5-dichloro-2-pentanone |
| CN109534980B (en) * | 2018-12-25 | 2022-02-08 | 江苏兄弟维生素有限公司 | Method for synthesizing cyclopropyl methyl ketone from alpha-acetyl-gamma-butyrolactone high-boiling-point substance |
| CN111792987A (en) * | 2020-07-19 | 2020-10-20 | 江苏云帆化工有限公司 | Synthetic method for preparing 3, 5-dichloro-2-pentanone from methyl acetoacetate |
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| CN103709023B (en) * | 2013-12-24 | 2015-11-25 | 秦永其 | The synthetic method of 3,5-Dichloro-2-pentanone |
| CN104292089B (en) * | 2014-09-30 | 2016-01-13 | 大连九信生物化工科技有限公司 | The synthesis technique of the chloro-1 '-chloracetyl cyclopropane of a kind of 1- |
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