CN106565441A - Synthesis method of 3,5-dichloro-2-pentanone - Google Patents
Synthesis method of 3,5-dichloro-2-pentanone Download PDFInfo
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- CN106565441A CN106565441A CN201610991250.5A CN201610991250A CN106565441A CN 106565441 A CN106565441 A CN 106565441A CN 201610991250 A CN201610991250 A CN 201610991250A CN 106565441 A CN106565441 A CN 106565441A
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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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Abstract
The invention discloses a synthesis method of 3,5-dichloro-2-pentanone. In the method, [alpha]-acetyl-[gamma]-butyrolactone is subjected to chlorination by sulfonyl chloride. The product is then subjected to ring opening, decarboxylation and chlorination in a hot hydrochloric acid solution to prepare a crude product. The crude product then is subjected to pressure reduced distillation to obtain high-purity 3,5-dichloro-2-pentanone. In the method, a phase transfer catalyst and a Lewis acid catalyst are employed at the same time, thereby avoiding generation of black tar, accelerating the reaction and increasing the yield of chlorination of primary alcohol. The method is simple in operations and treatment, is high in yield and is suitable for industrial production.
Description
Technical field
The invention belongs to fine chemistry industry synthesis field, and in particular to the synthetic method of one kind 3,5- Dichloro-2-pentanones.
Background technology
3,5- Dichloro-2-pentanones are a kind of important organic medicinal pesticide synthesis intermediate.Not only can be used to synthesize γ-ammonia
Base butanoic acid regulator (clomethiazole), the compound (2- chloroethyl -3- methyl -5,6- two for suppressing leukemia and anti-tumor activity
Hydrogen-Isosorbide-5-Nitrae-dithiins etc.), can also be used to synthetic organic pesticide (prothioconazoles etc.).At present, commonly use α '-chloro- α-
In acid condition one kettle way is obtained 3,5- Dichloro-2-pentanones to acetyl group-gamma-butyrolacton with hydrochloric acid, and in the document of report, this is anti-
Should generally there is black coke shape material to produce, and yield only has 58.8%；Also with solid phosgene to α '-chloro- α-second in document
Acyl group-gamma-butyrolacton chloro is obtained, although the method three wastes are reduced, yield is up to 81.5%, and solid phosgene
Belong to severe poisonous chemicals, storage aspect is severely limited, be the chemicals that highway transportation is prohibited.Therefore, to 3,5- bis-
It is significant that the synthetic method of chloro- 2 pentanone carries out Improvement.
The content of the invention
Present invention is generally directed to above weak point, proposition is a kind of in high yield, the conjunction of tractable 3,5- Dichloro-2-pentanones
Into method.Its course of reaction is：
The concrete technical scheme of the synthetic method of 3,5- Dichloro-2-pentanones of the present invention is as follows：
It is that, with α-acetyl group-gamma-butyrolacton as raw material, the step of open loop two is obtained 3,5- bis- in Jing sulfonic acid chloride nucleophilic chloros and hot hydrochloric acid
Chloro- 2 pentanone, comprises the following steps that：
(1) sulfonic acid chloride nucleophilic chlorination：Equipped with add in agitating device, the 2L glass reactors of thermometer α-acetyl group-
Gamma-butyrolacton, sulfonic acid chloride Deca is added, and controls rate of addition, and reaction temperature is controlled at 5-10 DEG C, is monitored using thin layer chromatography
The extent of reaction, after question response is complete, reactant liquor is poured into water and is quenched, and obtains purer α '-chloro- α-acetyl group-γ-Ding Nei
Ester.
(2) ring-opening reaction：Phase transfer catalyst is dissolved in into the α '-chloro- α-acetyl group-gamma-butyrolacton solution of step (1) acquisition
In, then it is slowly dropped at the appointed time in the hot hydrochloric acid dissolved with lewis acid catalyst, certain temperature is kept, opened
Ring, decarboxylation, chlorination, after reaction terminates, direct vacuum distillation reactant liquor obtains the azeotropic of 3,5- Dichloro-2-pentanones and water
Thing, point liquid, alkali cleaning organic faciess, obtains highly purified 3,5- Dichloro-2-pentanones.
Wherein：In step (1), α-acetyl group-gamma-butyrolacton is 1 with the mol ratio of sulfonic acid chloride:(1-1.05), react
Temperature is 5-10 DEG C, and sulfonic acid chloride time for adding is 2-2.5h, and the response time is controlled in 0-0.5h after completion of dropwise addition, and reaction terminates
Afterwards, add water and reaction is quenched, organic faciess can directly participate in next step reaction；
In step (2), lewis acid catalyst can use aluminum trichloride (anhydrous), anhydrous ferric chloride and anhydrous zinc chloride, excellent
Select aluminum trichloride (anhydrous)；Phase transfer catalyst is tetrabutyl ammonium bromide, tetraethylammonium chloride, preferred tetraethylammonium chloride.
In the step, α '-chloro- α-acetyl group-gamma-butyrolacton, 36% hydrochloric acid, lewis acid catalyst and phase transfer catalyst
Mol ratio is 1：(3-4)：(0.05-0.1)：(0.01-0.03), reaction temperature is 95-105 DEG C, α '-chloro- α-acetyl group-γ-
Butyrolactone time for adding is 4-8h, and preferred 6h, the response time is 0.5-1.0h, in vacuum distillation purification 3,5- Dichloro-2-pentanones,
Vapo(u)rizing temperature is 120-140 DEG C, and vacuum is-(0.04-0.06) MPa.
Compared with the conventional method, advantages of the present invention mainly has：
1), with α-acetyl group-gamma-butyrolacton as raw material, directly washing is achieved with the present invention after sulfonic acid chloride chlorination
Highly purified α '-chloro- α-acetyl group-gamma-butyrolacton, easy to operate, high income.
2), ring-opening reaction of the present invention improves reaction efficiency simultaneously using phase transfer catalyst and lewis acid catalyst,
The generation of black tars, simplifies post-reaction treatment avoid reacting simultaneously in.
3), first two steps total recovery of the present invention is up to 94%, and content 99%, reaction is typical, it is easy to which industrial operation is produced.
Description of the drawings
Fig. 1 is the gas phase spectrogram of α '-chloro- α-acetyl group-gamma-butyrolacton prepared by embodiment 1.
Fig. 2 is the gas phase spectrogram of 3,5- Dichloro-2-pentanones prepared by embodiment 1.
Specific embodiment
The synthetic method of 3,5- Dichloro-2-pentanones of the present invention is will be described in detail in following examples.
Embodiment 1
(1) sulfonic acid chloride nucleophilic chlorination：In equipped with mechanical agitation, the 2L glass reactors of thermometer, α-second is added
Acyl group-gamma-butyrolacton 640g (5mol), when ice maker circulating condensing is cooled to 5 DEG C, Deca sulfonic acid chloride 708g (5.25mol), about
2.5h drip.Extent of reaction is monitored using thin layer chromatography, is kept for 5-10 DEG C continue to react 0.5h, raw material has reacted completely.
After reaction terminates, reactant liquor is poured in water, point liquid removes a layer organic facies, is washed, anhydrous magnesium sulfate is dried.Obtain light yellow clear
Liquid α '-chloro- α-acetyl group-gamma-butyrolacton 801.7g, GC are analyzed, content 99.5%, yield 99.1%.
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), aluminum trichloride (anhydrous) 10.6g (0.08mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 145.8g, content 99%, yield 95%.
Embodiment 2
(1) sulfonic acid chloride nucleophilic chlorination：In equipped with mechanical agitation, the 2L glass reactors of thermometer, α-second is added
Acyl group-gamma-butyrolacton 640g (5mol), when ice maker circulating condensing is cooled to 5 DEG C, Deca sulfonic acid chloride 674g (5mol), about 2.5h
Drip.Extent of reaction is monitored using thin layer chromatography, is kept for 5-10 DEG C continue to react 0.5h, raw material has reacted completely.Reaction
After end, reactant liquor is poured in water, point liquid removes a layer organic facies, is washed, anhydrous magnesium sulfate is dried.Obtain light yellow clear liquid
α '-chloro- α-acetyl group-gamma-butyrolacton 756.5g, GC are analyzed, content 96.9%, yield 95.8%.
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
197g (2mol), aluminum trichloride (anhydrous) 10.6g (0.08mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 114.8g, content 98.7%, yield 75%.
Embodiment 3
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
394g (4mol), aluminum trichloride (anhydrous) 10.6g (0.08mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 142g, content 98.5%, yield 93%.
Embodiment 4
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), aluminum trichloride (anhydrous) 10.6g (0.08mol), are warming up to 100 DEG C or so backflows, then by 3.2g (0.01mol)
Tetrabutyl ammonium bromide is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 139.1g, content 97.5%, yield 92%.
Embodiment 5
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), aluminum trichloride (anhydrous) 6.6g (0.05mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 142.7g, content 97.9%, yield 94%.
Embodiment 6
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), aluminum trichloride (anhydrous) 13.3g (0.1mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 142.4g, content 96.7%, yield 95%.
Embodiment 7
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), anhydrous ferric trichloride 13.0g (0.08mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 119.7g, content 96.5%, yield 80%.
Embodiment 8
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), anhydrous zinc chloride 11.0g (0.08mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol) four
Ethyl ammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, and (content 99.5%, 1mol) is molten
In liquid, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 6h, drips rear insulation reaction 0.5h, reaction knot
Shu Hou, is down to room temperature, and vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid, uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 109.0g, content 96.3%, yield 73%.
Embodiment 9
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), is warming up to 100 DEG C or so backflows, then 1.7g (0.01mol) tetraethylammonium chloride is dissolved in into step (1) and is obtained
In α '-chloro- α-acetyl group-gamma-butyrolacton (164g, content 99.5%, the 1mol) solution for obtaining, in being slowly dropped into hot hydrochloric acid, drop
Plus 6h, rear insulation reaction 0.5h is dripped, after reaction terminates, room temperature is down to, vacuum distillation brownish red reactant liquor obtains 3,5- bis-
Chloro- 2 pentanone and the azeotropic mixture of water, divide liquid, with w (NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is done
It is dry, obtain 3,5- Dichloro-2-pentanone pale yellow-green liquid 99.4g, content 94.3%, yield 68%.
Embodiment 10
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), is warming up to 100 DEG C or so backflows, α '-chloro- α-acetyl group-gamma-butyrolacton 164g that step (1) is obtained,
In (content 99.5%, 1mol) solution, in being slowly dropped into hot hydrochloric acid, Deca 6h drips rear insulation reaction 0.5h, on reactant liquor
There are black tars in layer, after reaction terminates, is down to room temperature, vacuum distillation brownish red reactant liquor, obtain 3,5- Dichloro-2-pentanones with
The azeotropic mixture of water, point liquid, with w (NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- bis-
Chloro- 2 pentanone pale yellow-green liquid 72.2g, content 93.1%, yield 50%.
Embodiment 11
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
395g (3mol), aluminum trichloride (anhydrous) 10.6g (0.08mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 8h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 144.5g, content 98.1%, yield 95%.
Embodiment 12
(2) ring-opening reaction：It is equipped with water knockout drum, the four-hole boiling flask of thermometer in 1000mL, adds 36-38% concentrated hydrochloric acid
295g (3mol), aluminum trichloride (anhydrous) 10.6g (0.08mol), are warming up to 100 DEG C or so backflows, then by 1.7g (0.01mol)
Tetraethylammonium chloride is dissolved in the α '-chloro- α-acetyl group-gamma-butyrolacton 164g of step (1) acquisition, (content 99.5%, 1mol)
In solution, it is slowly dropped in the hot hydrochloric acid dissolved with lewis acid catalyst, Deca 4h drips rear insulation reaction 0.5h, reacts
After end, room temperature is down to, vacuum distillation brownish red reactant liquor obtains the azeotropic mixture of 3,5- Dichloro-2-pentanones and water, point liquid uses w
(NaHCO3The aqueous solution of)=5%, water are washed successively, and anhydrous magnesium sulfate is dried, and obtains 3,5- Dichloro-2-pentanone oyster liquid
Body 132.1g, content 97.9%, yield 87%.
Claims (10)
1. one kind 3, the synthetic method of 5- Dichloro-2-pentanones, it is characterised in that：Be with α-acetyl group-gamma-butyrolacton as raw material,
The step of open loop two is obtained 3,5- Dichloro-2-pentanones in Jing sulfonic acid chloride nucleophilic chloros and hot hydrochloric acid, comprises the following steps that：
(1) sulfonic acid chloride nucleophilic chlorination：Equipped with add in agitating device, the 2L glass reactors of thermometer α-acetyl group-
Gamma-butyrolacton, sulfonic acid chloride Deca is added, and controls rate of addition, and reaction temperature is controlled at 5-10 DEG C, is monitored using thin layer chromatography
The extent of reaction, after question response is complete, reactant liquor is poured into water and is quenched, and obtains purer α '-chloro- α-acetyl group-γ-Ding Nei
Ester.
(2) ring-opening reaction：Phase transfer catalyst is dissolved in into the α '-chloro- α-acetyl group-gamma-butyrolacton solution of step (1) acquisition
In, then it is slowly dropped at the appointed time in the hot hydrochloric acid dissolved with lewis acid catalyst, certain temperature is kept, opened
Ring, decarboxylation, chlorination, after reaction terminates, direct vacuum distillation reactant liquor obtains the azeotropic of 3,5- Dichloro-2-pentanones and water
Thing, Jing point of liquid, alkali cleaning organic faciess, obtains highly purified 3,5- Dichloro-2-pentanones.
2. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that：Step (1) sulfonic acid chloride nucleophilic
In chlorination, α-acetyl group-gamma-butyrolacton is 1 with the mol ratio of sulfonic acid chloride:(1-1.05).
3. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that：Step (1) sulfonic acid chloride nucleophilic
In chlorination, controlling reaction temperature is at 5-10 DEG C.
4. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that：Step (1) sulfonic acid chloride nucleophilic
In chlorination, sulfonic acid chloride time for adding controls to continue after 2-2.5h, completion of dropwise addition response time control in 0-0.5h.
5. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that：Step (1) sulfonic acid chloride nucleophilic
In chlorination, after reaction terminates, add water and reaction is quenched, organic faciess can directly participate in next step reaction.
6. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that step (2) ring-opening reaction
In, the consumption of α '-chloro- α-acetyl group-gamma-butyrolacton, 36% hydrochloric acid, lewis acid catalyst and phase transfer catalyst, massage
You are than being 1：(3-4)：(0.05-0.1)：(0.01-0.03).
7. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that step (2) ring-opening reaction
In, lewis acid catalyst is aluminum trichloride (anhydrous), and phase transfer catalyst is tetraethylammonium chloride.
8. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that step (2) ring-opening reaction
In, reaction temperature is 95-105 DEG C.
9. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that step (2) ring-opening reaction
In, α '-chloro- α-acetyl group-gamma-butyrolacton time for adding is 4-8h, and preferred 6h, the response time is 0.5-1.0h.
10. the synthetic method of 3,5- Dichloro-2-pentanones according to claim 1, it is characterised in that step (2) vacuum distillation
During purification 3,5- Dichloro-2-pentanones, vapo(u)rizing temperature is 120-140 DEG C, and vacuum is-(0.04-0.06) MPa.
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Cited By (2)
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| CN110357769A (en) * | 2019-08-21 | 2019-10-22 | 山东海利尔化工有限公司 | A kind of continuous flow method preparing 3,5- Dichloro-2-pentanone |
| CN114685253A (en) * | 2020-12-30 | 2022-07-01 | 南通泰禾化工股份有限公司 | Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone |
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| CN110357769B (en) * | 2019-08-21 | 2022-08-16 | 山东海利尔化工有限公司 | Continuous flow method for preparing 3, 5-dichloro-2-pentanone |
| CN114685253A (en) * | 2020-12-30 | 2022-07-01 | 南通泰禾化工股份有限公司 | Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone |
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