CN109265329A - The preparation method of 3,5- Dichloro-2-pentanone - Google Patents
The preparation method of 3,5- Dichloro-2-pentanone Download PDFInfo
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- CN109265329A CN109265329A CN201710579153.XA CN201710579153A CN109265329A CN 109265329 A CN109265329 A CN 109265329A CN 201710579153 A CN201710579153 A CN 201710579153A CN 109265329 A CN109265329 A CN 109265329A
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Abstract
The present invention relates to field of fine chemical; disclose one kind 3; the preparation method of 5- Dichloro-2-pentanone; it is characterized in that; the preparation method includes: in the system existing for no solvent; α-acetyl group-gamma-butyrolacton and sulfonic acid chloride contact are subjected to chlorination reaction, then mix the material that the chlorination reaction obtains with water, hydrochloric acid is added dropwise into obtained mixture and carries out ring-opening reaction.This method is by realizing organic solvent-free one pot reaction, simplifying technological operation, reduce the three wastes and production cost, avoid and polluted using metallic catalyst bring using cheap industrial chemical as raw material.
Description
Technical field
The present invention relates to field of fine chemical, and in particular to the preparation method of one kind 3,5- Dichloro-2-pentanone.
Background technique
3,5- Dichloro-2-pentanones are the important intermediates of medical pesticide synthesis, and what especially synthesis Beyer Co., Ltd developed kills
The important intermediate of microbial inoculum prothioconazoles.A report is opened using 2- methyl -2- hydroxyl tetrahydrofuran as raw material through hydrochloric acid within 1975
The intermediate is generated with sulfonic acid chloride chlorination after ring, but the process recovery ratio is relatively low, latter step yield is only 70%.Nineteen eighty-three has
It is anti-that document report carries out photochemistry addition using 3- butene-2 -one with methylene chloride as raw material under univalent copper ion catalytic condition
The intermediate should can be obtained, which has used metallic catalyst and photochemical reaction condition, and therefore, process industryization implements phase
To difficulty.Separately there is CN106278850A to report using ethyl acetoacetate as raw material, obtains the chloro- 2- penta of 3,5- bis- through three-step reaction
The method of ketone, but the process route step is relatively long.
Currently, reporting that most synthetic routes is using α-acetyl group-gamma-butyrolacton as raw material, then through chlorination reaction point
From obtaining the chloro- α '-acetyl group-gamma-butyrolacton of α-, then in the presence of lewis acid catalyst such as aluminium chloride or phase transfer catalyst
Ring-opening reaction is carried out with hydrochloric acid, or is reacted in the presence of glacial acetic acid with hydrochloric acid.These techniques are not only cumbersome, but also are dividing
Generated during α '-acetyl group-gamma-butyrolacton chloro- from α-a large amount of three wastes and have lost reaction in generate can be used for
The raw material hydrochloric acid of reaction, economy are poor in next step.Moreover, catalyst or the increase three wastes are used in next step reaction
Processing is difficult or increases environmental pollution.In CN104292089A, the preparation chloro- α '-acetyl group-gamma-butyrolacton of α-is described
When, a small amount of sulfonic acid chloride, hydrochloric acid and sulfur dioxide are removed in vacuum distillation, and crude product is directly used in the next step.Equally, the operation is opposite
It is relatively complicated and have lost can be used in next step react raw material hydrochloric acid, and next step reaction in additionally used solvent
Glacial acetic acid increases production cost.
Summary of the invention
The complex process for preparing 3,5- Dichloro-2-pentanone the purpose of the invention is to overcome the prior art to exist, not ring
The problem of guarantor, provides the preparation method of one kind 3,5- Dichloro-2-pentanone, and it is convenient, economic and environment-friendly which facilitates.
To achieve the goals above, the present invention provides the preparation method of one kind 3,5- Dichloro-2-pentanone, wherein the preparation
Method includes: that α-acetyl group-gamma-butyrolacton and sulfonic acid chloride contact are carried out chlorination reaction in the system existing for no solvent,
Then the material that the chlorination reaction obtains is mixed with water, hydrochloric acid is added dropwise into obtained mixture and carries out ring-opening reaction.
The present invention reacts preparation 3,5- Dichloro-2-pentanone, technique by raw material α-acetyl group-gamma-butyrolacton using one kettle way
Be simple and convenient to operate, yield it is higher, shorten process cycle, be more suitable industrialized production；Avoid existing processes separating alpha-
The a large amount of three wastes generated during chloro- α '-acetyl group-gamma-butyrolacton；It is fed intake, is avoided using road using hydrochloric acid mode is added dropwise
Lewis acid catalyst or phase transfer catalyst, more economical environmental protection.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides the preparation method of one kind 3,5- Dichloro-2-pentanone, wherein the preparation method includes: not molten
In system existing for agent, α-acetyl group-gamma-butyrolacton and sulfonic acid chloride contact are subjected to chlorination reaction, it is then that the chlorination is anti-
The material that should be obtained is mixed with water, and hydrochloric acid is added dropwise into obtained mixture and carries out ring-opening reaction.
According to the present invention, in order to improve the yield of 3,5- Dichloro-2-pentanone, production cost is reduced, under preferable case, in institute
It states in chlorination reaction, the molar ratio of the dosage of α-acetyl group-gamma-butyrolacton dosage and sulfonic acid chloride is 1:1-1.5, preferably 1:
1-1.05。
According to the present invention, the condition of the chlorination reaction preferably includes: reaction temperature is 0-60 DEG C, preferably 0-20 DEG C；
Reaction time is 0.4-4h, preferably 0.5-2h.Under the conditions of the preferred chlorination reaction, 3,5- Dichloro-2-pentanones can be obtained
Higher yield.
According to the present invention, α-acetyl group-gamma-butyrolacton and the mode of sulfonic acid chloride contact can be mixed for existing reaction raw materials
The mode of conjunction is implemented, it is preferable that the mode of α-acetyl group-gamma-butyrolacton and sulfonic acid chloride contact are as follows: to α-acetyl group-γ-Ding Nei
Sulfonic acid chloride is added dropwise in ester.
According to the present invention, be added dropwise into α-acetyl group-gamma-butyrolacton sulfonic acid chloride rate can according to conventional rate into
Row, it is preferable that the drop rate of sulfonic acid chloride is 2-6mol/h.
According to the present invention, organic solvent is not needed in the preparation method, is only added after chlorination reaction a certain amount of
Water, and be added after water and directly carry out next step operation without isolation.Under preferable case, the dosage and α-acetyl group-γ-Ding Nei of water
The weight ratio of the dosage of ester is 0.1-10:1, preferably 0.2-5, further preferably 0.3-0.8:1.
According to the present invention, in order to improve the yield of 3,5- Dichloro-2-pentanone, production cost is reduced, under preferable case, in institute
It states in ring-opening reaction, dosage of the hydrochloric acid in terms of HCl and α-acetyl group-gamma-butyrolacton dosage molar ratio are 1-5:1, preferably
For 1.5-2.5:1.
According to the present invention, the concentration of the hydrochloric acid solution is preferably 15-36 weight %.
According to the present invention, the condition of the ring-opening reaction preferably includes: reaction temperature is 50-120 DEG C, preferably 90-110
℃；Reaction time is 1-15h, preferably 2-6h.Under the conditions of the ring-opening reaction, 3,5- Dichloro-2-pentanones can obtain higher
Yield.
According to the present invention, the mode that hydrochloric acid is added dropwise into the mixture to avoid in the preparation method using road
Lewis acid catalyst or phase transfer catalyst, more economical environmental protection.Therefore, in the preparation process in accordance with the present invention, ring-opening reaction exists
Do not have to carry out in the presence of lewis acid catalyst and/or phase transfer catalyst.In order to further increase the chloro- 2- of 3,5- bis-
The yield of pentanone, under preferable case, drop rate of the hydrochloric acid in terms of HCl is 1-5mol/h, preferably 2-4mol/h.
According to the present invention, the preparation method it is also preferable to include: after the ring-opening reaction, by the chloro- 2- of 3,5- bis-
Pentanone is separated from reaction product.The isolated mode can may include: to produce to reaction for extraction, the process of the extraction
Extractant is added in object, the organic layer being obtained by extraction is evaporated under reduced pressure.The extractant can be used in be existing
The extractant of 3,5- Dichloro-2-pentanone is extracted, such as the extractant is 1,2- dichloroethanes.
The present invention will be described in detail by way of examples below.In following embodiment,
The yield of 3,5- Dichloro-2-pentanone is calculate by the following formula:
In formula, Y: yield, %；mIt is real: with the weight of obtained 3,5- Dichloro-2-pentanone multiplied by the calculated practical production of purity
Amount, g；mReason: with the theoretical yield for 3, the 5- Dichloro-2-pentanone that the amount that α-acetyl group-gamma-butyrolacton participates in reaction calculates, g.
The measuring method of sample purity: (1) it prepares inner mark solution: weighing 12.5g repefral and hold to 500ml
It in measuring bottle, is dissolved with acetonitrile, constant volume to scale, ultrasound is simultaneously cooled to room temperature, shakes up stand-by.(2) standard solution is prepared: accurate to claim
It takes 3,5- Dichloro-2-pentanone standard specimen 80mg (being accurate to 0.1mg) into 50ml volumetric flask, is dissolved with acetonitrile, with pipette to appearance
Inner mark solution 3ml, constant volume to scale are pipetted in measuring bottle, ultrasound is simultaneously cooled to room temperature, shakes up stand-by.(3) it prepares sample solution: claiming
80mg (being accurate to 0.1mg) 3,5- Dichloro-2-pentanone sample is taken into 50mL volumetric flask, acetonitrile to be added to dissolve, with pipette to appearance
Inner mark solution 3ml, constant volume to scale are pipetted in measuring bottle, ultrasound is simultaneously cooled to room temperature, shakes up stand-by.(4) purity testing: analyzer
Device is Agilent GC7890 gas chromatograph (1 μ L of sample volume), after instrument stabilizer, continuously into several needle standard solution, until adjacent
When the peak area relative deviation of two needles is less than 1%, inner mark solution, standard solution and sample solution are detected respectively, passes through following formula meter
Calculate the purity (%) of 3,5- Dichloro-2-pentanone:
Wherein: CspThe concentration of-sample solution, mg/ml；RspThe peak area and inner mark solution of the item to be measured of-sample solution
Peak area ratio；CsdThe concentration of the item to be measured of-standard solution, mg/ml；RsdThe peak area of the item to be measured of-standard solution
With the ratio of the peak area of inner mark solution；P-standard sample 3,5- Dichloro-2-pentanone purity (%).
α-acetyl group-gamma-butyrolacton is coupled Science and Technology Ltd. purchased from Beijing, and the trade mark is Batch No:20170512；Sulphur
Acyl chlorides is coupled Science and Technology Ltd. purchased from Beijing, and the trade mark is Batch No:20170812.
Embodiment 1
α-acetyl group-gamma-butyrolacton 261.5g (2mol) is added into 1000ml four-hole bottle, controls 15 DEG C of temperature, is added dropwise
Sulfonic acid chloride 281g (2.04mol), rate of addition 4.08mol/h, after continuing temperature control stirring 1h to raw material conversion completely after dripping off,
100g water is added.Then, 100 DEG C are warming up to, starts that 36 weight % hydrochloric acid 344.7g (HCl of 3.4mol) are added dropwise, in terms of HCl
Rate of addition is 3.4mol/h, continues temperature control stirring 3h after dripping off.After reaction, it is down to room temperature, then, is added 1 to system,
2- dichloroethanes 500g extracts liquid separation, and organic layer obtains 3,5- Dichloro-2-pentanone, purity 98% through vacuum distillation, and yield is
90%.
Embodiment 2
α-acetyl group-gamma-butyrolacton 261.5g (2mol) is added into 1000ml four-hole bottle, controls 20 DEG C of temperature, is added dropwise
Sulfonic acid chloride 289g (2.1mol), rate of addition 2.1mol/h, after continuing temperature control stirring 0.5h to raw material conversion completely after dripping off,
209g water is added.Then, 110 DEG C are warming up to, starts that 15 weight % hydrochloric acid 1217g (HCl of 5mol), the drop in terms of HCl is added dropwise
Acceleration is 2.5mol/h, continues temperature control stirring 6h after dripping off.After reaction, it is down to room temperature, then, is added 1,2- to system
Dichloroethanes 500g extracts liquid separation, and organic layer obtains 3,5- Dichloro-2-pentanone, purity 98% through vacuum distillation, and yield is
89%.
Embodiment 3
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, the dosage of sulfonic acid chloride is 303g
(2.2mol).The yield of 3,5- Dichloro-2-pentanone is 88%.
Embodiment 4
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 3, unlike, before sulfonic acid chloride is added dropwise, control temperature
Degree is 40 DEG C.The yield of 3,5- Dichloro-2-pentanone is 84%.
Embodiment 5
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 3, unlike, continue temperature control after dripping sulfonic acid chloride
Stir 3h.The yield of 3,5- Dichloro-2-pentanone is 87%.
Embodiment 6
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, the dosage of water is 500g.3,5- bis-
The yield of chloro- 2 pentanone is 81%.
Embodiment 7
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, the dosage of hydrochloric acid is 243.3g
(HCl of 2.4mol).The yield of 3,5- Dichloro-2-pentanone is 78%.
Embodiment 8
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, after water is added, it is warming up to 70 DEG C.3,
The yield of 5- Dichloro-2-pentanone is 75%.
Embodiment 9
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, temperature control continues to stir after dripping hydrochloric acid
Mix 10h.The yield of 3,5- Dichloro-2-pentanone is 84%.
Embodiment 10
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, drop rate of the hydrochloric acid in terms of HCl is
5mol/h.The yield of 3,5- Dichloro-2-pentanone is 83%.
Comparative example 1
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, the adding manner of hydrochloric acid is not to be added dropwise,
But it is directly mixed with the material after chlorination reaction.The yield of 3,5- Dichloro-2-pentanone is 55%.
Comparative example 2
3,5- Dichloro-2-pentanone is prepared according to the method for embodiment 1, unlike, water is used to the ice second of identical weight
Acid replaces.The yield of 3,5- Dichloro-2-pentanone is 70%.
Preparation method of the invention does not need molten in chlorination reaction it can be seen from above-described embodiment and comparative example result
Agent does not need organic solvent in ring-opening reaction, does not have intermediate product separation process, easy to operate, will not generate the three wastes, and
The high income of 3,5- Dichloro-2-pentanone.The sulphur it can be seen from embodiment 1 is compared with embodiment 3, embodiment 6 and embodiment 7
The yield of 3,5- Dichloro-2-pentanone can be improved in the dosage of acyl chlorides, water and hydrochloric acid in preferred scope of the invention；By embodiment
3 can be seen that available higher yield under the conditions of currently preferred chlorination reaction with the comparison of embodiment 4, embodiment 5
3,5- Dichloro-2-pentanone；The present invention is excellent it can be seen from embodiment 1 is compared with embodiment 8, embodiment 9 and embodiment 10
Select the condition of hydrochloric acid drop rate and ring-opening reaction in range that the yield of 3,5- Dichloro-2-pentanone can be improved；By implementing
Example 1 can be seen that compared with comparative example 1 can obtain high receipts by the way of hydrochloric acid is added dropwise under conditions of no catalyst
The 3,5- Dichloro-2-pentanone of rate；It can be seen from embodiment 1 is compared with comparative example 2 in the identical situation of feed ratio, this
Invention uses yield of the water as ring-opening reaction solvent when than using high income of the glacial acetic acid as ring-opening reaction solvent when, and
And water phase is more cheap for glacial acetic acid, to substantially reduce cost.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. one kind 3, the preparation method of 5- Dichloro-2-pentanone, which is characterized in that the preparation method includes: to exist in no solvent
System in, by α-acetyl group-gamma-butyrolacton and sulfonic acid chloride contact carry out chlorination reaction, then the chlorination reaction is obtained
Material mixed with water, into obtained mixture be added dropwise hydrochloric acid carry out ring-opening reaction.
2. preparation method according to claim 1, wherein in the chlorination reaction, α-acetyl group-gamma-butyrolacton
The molar ratio of dosage and the dosage of sulfonic acid chloride is 1:1-1.5, preferably 1:1-1.05.
3. preparation method according to claim 1 or 2, wherein the condition of the chlorination reaction includes: that reaction temperature is 0-
60 DEG C, preferably 0-20 DEG C；Reaction time is 0.4-4h, preferably 0.5-2h.
4. preparation method according to claim 1 or 2, wherein the side of α-acetyl group-gamma-butyrolacton and sulfonic acid chloride contact
Formula are as follows: sulfonic acid chloride is added dropwise into α-acetyl group-gamma-butyrolacton.
5. the preparation method according to claim 4, wherein the drop rate of sulfonic acid chloride is 2-6mol/h.
6. preparation method according to claim 1 or 2, wherein the dosage and α-acetyl group-gamma-butyrolacton dosage of water
Weight ratio be 0.1-10:1, preferably 0.3-0.8:1.
7. preparation method according to claim 1 or 2, wherein in the ring-opening reaction, dosage of the hydrochloric acid in terms of HCl
It is 1-5:1, preferably 1.5-2.5:1 with α-acetyl group-gamma-butyrolacton dosage molar ratio.
8. preparation method according to claim 1 or 2, wherein the condition of the ring-opening reaction includes: that reaction temperature is
50-120 DEG C, preferably 90-110 DEG C；Reaction time is 1-15h, preferably 2-6h.
9. preparation method according to claim 1 or 2, wherein the concentration of hydrochloric acid is 15-36 weight %；
Preferably, drop rate of the hydrochloric acid in terms of HCl is 1-5mol/h, preferably 2-4mol/h.
10. preparation method according to claim 1 or 2, wherein the preparation method further include: in the ring-opening reaction
After, 3,5- Dichloro-2-pentanone is separated from reaction product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| 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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