CN112079698A - Process for preparing 1-chloro-1- (chloroacetyl) cyclopropane - Google Patents
Process for preparing 1-chloro-1- (chloroacetyl) cyclopropane Download PDFInfo
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- VHHGLRZRRBYTNE-UHFFFAOYSA-N 2-chloro-1-(1-chlorocyclopropyl)ethanone Chemical compound ClCC(=O)C1(Cl)CC1 VHHGLRZRRBYTNE-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 238000000034 method Methods 0.000 claims abstract description 33
- QRYFKVUKGKNACG-UHFFFAOYSA-N 1,3,5-trichloropentan-2-one Chemical compound ClCCC(Cl)C(=O)CCl QRYFKVUKGKNACG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XVRIEWDDMODMGA-UHFFFAOYSA-N 5-chloropentan-2-one Chemical compound CC(=O)CCCCl XVRIEWDDMODMGA-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012320 chlorinating reagent Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 210000003298 dental enamel Anatomy 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims description 2
- 229920006362 Teflon® Polymers 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 238000006561 solvent free reaction Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 24
- 239000006227 byproduct Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 5
- 230000003321 amplification Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- MNHVNIJQQRJYDH-UHFFFAOYSA-N 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1=CNC(=S)N1CC(C1(Cl)CC1)(O)CC1=CC=CC=C1Cl MNHVNIJQQRJYDH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005825 Prothioconazole Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000010606 normalization Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QBQZCJBWAMFUIC-UHFFFAOYSA-N 1,1,1-trichloropentan-2-one Chemical compound CCCC(=O)C(Cl)(Cl)Cl QBQZCJBWAMFUIC-UHFFFAOYSA-N 0.000 description 1
- KADOHHPNWMXGNG-UHFFFAOYSA-N 1-(1-chlorocyclopropyl)ethanone Chemical compound CC(=O)C1(Cl)CC1 KADOHHPNWMXGNG-UHFFFAOYSA-N 0.000 description 1
- OMQHDIHZSDEIFH-UHFFFAOYSA-N 3-Acetyldihydro-2(3H)-furanone Chemical compound CC(=O)C1CCOC1=O OMQHDIHZSDEIFH-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present disclosure provides a process for preparing 1-chloro-1- (chloroacetyl) cyclopropane using a microchannel reactor, the process comprising: B) reacting 1,3, 5-trichloro-2-pentanone with an alkali liquor in a solvent at-5 to 10 ℃ and a pressure of 1.0 to 10.0bar in a microchannel reactor for 5 to 30 minutes to obtain 1-chloro-1- (chloroacetyl) cyclopropane. The method disclosed by the invention has the advantages of good selectivity, high conversion rate and high product purity, and eliminates multi-substituted byproducts from the reaction source; the method has no high-temperature high-pressure reaction and is convenient to operate; moreover, the amplification effect of the reaction is small, and the industrial production is convenient.
Description
Technical Field
The present invention relates to the field of fine organic synthesis. In particular to a method for preparing 1-chloro-1- (chloracetyl) cyclopropane by using 1,3, 5-trichloro-2-pentanone as a raw material and a microchannel reactor.
Background
1-chloro-1- (chloroacetyl) cyclopropane is a key intermediate for preparing novel pesticide prothioconazole. The currently common industrial preparation method is to obtain a 1-chloro-1- (chloroacetyl) cyclopropane product by steps of multi-step chlorination, hydrolysis and the like of acetyl-gamma-butyrolactone, and the product is shown as a formula (1). For example, chinese patent nos. CN104292089A and CN105384617A disclose corresponding reactions, i.e., 1-chloro-1-acetylcyclopropane is prepared and then chlorinated to obtain 1-chloro-1- (chloroacetyl) cyclopropane.
The process needs two chlorination reactions, also relates to cyclization reaction under alkaline condition and the like, has long steps and low yield, is difficult to separate polychlorinated byproducts in the product, and has complex required equipment and high requirement on the equipment. Therefore, a simple and efficient method for preparing 1-chloro-1- (chloroacetyl) cyclopropane with industrial application prospect is still needed.
Disclosure of Invention
The inventor of the present disclosure found through repeated experiments that 1-chloro-1- (chloroacetyl) cyclopropane can be prepared from trichloropentanone by using a microchannel reactor. The method has high yield, high selectivity and no polychlorinated byproducts, and the disclosure is completed on the basis.
The purpose of the present disclosure is to provide a method for preparing 1-chloro-1- (chloroacetyl) cyclopropane with high conversion rate and high selectivity.
According to one aspect of the present disclosure, there is provided a method for preparing 1-chloro-1- (chloroacetyl) cyclopropane, the method comprising:
B) reacting 1,3, 5-trichloro-2-pentanone with an alkali liquor in a solvent at-5 to 10 ℃ and 1.0 to 10.0bar pressure in a microchannel reactor for 5 to 30 minutes to obtain 1-chloro-1- (chloroacetyl) cyclopropane,
wherein the solvent is selected from one or more of dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, methyltetrahydrofuran, diethyl ether and DMF; the alkali liquor is one or more alkali aqueous solutions selected from NaOH, potassium hydroxide, sodium carbonate and potassium carbonate; the mass ratio of the 1,3, 5-trichloro-2-pentanone to the solvent is 1:1 to 1: 5; the molar ratio of the 1,3, 5-trichloro-2-pentanone to the alkali liquor is 1:1 to 1: 1.5.
Advantageous effects
Compared with the prior art, the method disclosed by the invention has the advantages of good selectivity, high conversion rate and high product purity, and eliminates multi-substituted byproducts from the reaction source; the method has no high-temperature high-pressure reaction and is convenient to operate; moreover, the amplification effect of the reaction is small, and the industrial production is convenient.
Drawings
FIG. 1 is a diagram of a microchannel reactor apparatus;
FIG. 2 is a LC diagram of the reaction solution of the first embodiment;
FIG. 3 is an LC diagram of the reaction solution of comparative example one.
Detailed Description
To make the features and effects of the present invention comprehensible to those having ordinary knowledge in the art, general description and definitions are made with respect to terms and phrases mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In this document, the terms "comprising," "including," "having," "containing," or any other similar term, are intended to be open-ended franslational phrase (open-ended franslational phrase) and are intended to cover non-exclusive inclusions. For example, a composition or article comprising a plurality of elements is not limited to only those elements recited herein, but may include other elements not expressly listed but generally inherent to such composition or article. In addition, unless expressly stated to the contrary, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or". For example, the condition "a or B" is satisfied in any of the following cases: a is true (or present) and B is false (or not present), a is false (or not present) and B is true (or present), both a and B are true (or present). Furthermore, in this document, the terms "comprising," including, "" having, "" containing, "and" containing "are to be construed as specifically disclosed and to cover both closed and semi-closed conjunctions, such as" consisting of … "and" consisting essentially of ….
All features or conditions defined herein as numerical ranges or percentage ranges are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to have covered and specifically disclosed all possible subranges and individual numerical values within the ranges, particularly integer numerical values. For example, a description of a range of "1 to 8" should be considered to have specifically disclosed all subranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, and so on, particularly subranges bounded by all integer values, and should be considered to have specifically disclosed individual values such as 1,2, 3, 4, 5, 6, 7, 8, and so on, within the range. Unless otherwise indicated, the foregoing explanatory methods apply to all matters contained in the entire disclosure, whether broad or not.
If an amount or other value or parameter is expressed as a range, preferred range, or a list of upper and lower limits, it is to be understood that all ranges subsumed therein for any pair of that range's upper or preferred value and that range's lower or preferred value, whether or not such ranges are separately disclosed, are specifically disclosed herein. Further, when a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
In this context, numerical values should be understood to have the precision of the number of significant digits of the value, provided that the object of the invention is achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.
In this document, where Markush group (Markush group) or Option language is used to describe features or examples of the invention, those skilled in the art will recognize that a sub-group of all elements or any individual element within a Markush group or list of options may also be used to describe the invention. For example, if X is described as "selected from the group consisting of1、X2And X3The group "also indicates that X has been fully described as X1Is claimed with X1And/or X2Claim (5). Furthermore, where Markush group or option terms are used to describe features or examples of the invention, those skilled in the art will recognize that any combination of sub-groups of all elements or individual elements within the Markush group or option list can also be used to describe the invention. Accordingly, for example, if X is described as "selected from the group consisting of1、X2And X3Group consisting of "and Y is described as" selected from Y1、Y2And Y3The group "formed indicates that X has been fully described as X1Or X2Or X3And Y is Y1Or Y2Or Y3Claim (5).
The following detailed description is merely exemplary in nature and is not intended to limit the invention or the application thereof. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or the summary of the invention or the following detailed description or examples.
According to one embodiment of the present disclosure, there is provided a method for preparing 1-chloro-1- (chloroacetyl) cyclopropane, the method comprising:
B) reacting 1,3, 5-trichloro-2-pentanone with an alkali liquor in a solvent at-5 to 10 ℃ and a pressure of 1.0 to 10.0bar in a microchannel reactor for 5 to 30 minutes to obtain 1-chloro-1- (chloroacetyl) cyclopropane,
wherein the solvent is selected from one or more of dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, methyltetrahydrofuran, diethyl ether and DMF; the alkali solution is selected from NaOH, KOH, Na2CO3And K2CO3An aqueous solution of one or more bases of (a); the mass ratio of the 1,3, 5-trichloro-2-pentanone to the solvent is 1:1 to 1:5, preferably 1: 2; the molar ratio of the 1,3, 5-trichloro-2-pentanone to the alkali liquor is 1:1 to 1:1.5, preferably 1:1 to 1: 1.2.
According to the method, the 1-chloro-1- (chloroacetyl) cyclopropane can be prepared with high selectivity, high conversion rate and high product purity, and polysubstituted byproducts are eliminated from the reaction source; no high-temperature high-pressure reaction and convenient operation.
According to an embodiment of the present disclosure, the method further comprises, before step B):
A) reacting 5-chloro-2-pentanone with sulfuryl chloride or chlorine gas in a microchannel reactor at-5 to 25 ℃ and a pressure of 1.0 to 10.0bar for 5 to 30 minutes to give 1,3, 5-trichloro-2-pentanone.
According to the above production method, 1-chloro-1- (chloroacetyl) cyclopropane can be produced by a two-step reaction starting from 5-chloro-2-pentanone, and the two-step reaction formula is as follows.
The alpha-position CH of the carbonyl compound can generate substitution reaction under the action of a chlorination reagent to obtain an alpha-chloro product, a byproduct is a polychlorinated product, excessive chlorination reagent and high temperature are easy to generate polychlorinated reaction, and the reaction is exothermic reaction, so that the dosage of the chlorination reagent needs to be strictly controlled and heat generated by the reaction needs to be removed in time.
Two possible products of 1,3, 5-trichloro-2-pentanone cyclization under alkaline conditions are 1-chloro-1- (chloroacetyl) cyclopropane and 2, 5-dichlorocyclopentanone (formula 3), and it was found that the production of 2, 5-dichlorocyclopentanone as a byproduct increases with higher amounts of base and higher temperatures. Both 1-chloro-1-chloroacetyl cyclopropane and 2, 5-dichlorocyclopentanone are easy to further perform substitution reaction under the action of excessive alkali to obtain a series of complex products, and further become tar oil, so that the product yield is reduced. The control conditions of the reaction in this step mainly include: 1) the reaction is an exothermic reaction, and the reaction heat is removed in time; 2) strictly controlling the dosage of alkali; 3) the product should be quickly separated from the alkaline environment after being generated, or the dosage of the alkali should be adjusted, so that the alkali is completely consumed while the product is generated.
By using a microchannel reactor, the method of the present disclosure has the following features:
1) the heat transfer is rapid. The two reactions of the method disclosed by the invention are violent exothermic reactions, and the common kettle type reactor can not meet the requirement of instantly removing a large amount of heat, so that the local temperature rise in the reaction process is overhigh, a series of byproducts are generated, and the reaction yield is reduced. The heat transfer can be enhanced by adopting the microchannel reactor, so that the problem is solved;
2) and the mass transfer is enhanced. The reaction of the 1,3, 5-trichloro-2-pentanone solution and the liquid alkali is a liquid-liquid two-phase mixed reaction, and compared with a kettle type reactor, the mass transfer efficiency of the microchannel reactor can be improved;
3) the dosage of alkali is strictly controlled. In the kettle type reaction, even if the manner of dropwise adding alkali liquor is adopted, the product can still react with the alkali due to continuous accumulation in the reaction system, and is decomposed and deteriorated, the microchannel reactor is adopted, the proportion of the reaction liquid and the alkali liquor at the feeding point is strictly controlled, and the reaction liquid and the alkali liquor are separated from the reaction system after the reaction is finished, so that the product is prevented from being further converted into other byproducts.
As shown in fig. 1, according to one embodiment of the present disclosure, wherein the microchannel reactor comprises:
the device comprises a material tank 1, a feeding pump 1 and a preheating/cooling module 1 which are connected in sequence, and a material tank 2, a feeding pump 2 and a preheating/cooling module 2 which are connected in sequence, a mixer connected to the preheating/cooling module 1 and the preheating/cooling module 2, a microchannel reaction chamber connected to the mixer, a discharge chute connected to the microchannel reaction chamber, and a storage tank connected to the discharge chute.
Through such a microchannel reactor, it is possible to strictly control the reactant ratio, the feed temperature, and separately introduce the reactants, thereby effectively promoting the reaction.
Although not specifically limited, those skilled in the art will appreciate that the microchannel reactor may also contain known components such as valves, sensors, lines connecting the various components, etc., if desired.
According to one embodiment of the present disclosure, the material tanks 1 and 2 are composed of containers made of teflon or lined with enamel; the pipelines adopt silica gel or silicon carbide materials; the mixer is silica gel, and carbon fiber, quartz fiber or macroporous silica gel is filled in the mixer; the preheating/ cooling modules 1 and 2 are respectively used for controlling the temperature of the material or the mixture entering the mixer to be-20 to 120 ℃; the storage tank is composed of a container with polytetrafluoroethylene or enamel lining; the feed pumps 1 and 2 are liquid feed pumps or gas feed pumps, wherein the flow rate of the liquid feed pump is 0.006 to 600mL/min, the flow rate of the gas feed pump is 5 to 900mL/min, and the direction of the pump head is adjustable; the pipe diameter of the microchannel reaction chamber is 0.02-10 mm, and the interior of the reaction chamber is laminar flow or turbulent flow.
By using the microchannel reactor of the above-mentioned specific material, structure, or parameter, the reaction can be carried out more smoothly.
According to one embodiment of the present disclosure, wherein the microchannel reactor may optionally comprise a tail gas absorber.
According to one embodiment of the present disclosure, the step a) and the step B) use different microchannel reactors.
Thus, the different microchannel reactors can be used for operating an acidic medium (chlorinating agent) and an alkaline medium (lye), respectively.
According to one embodiment of the present disclosure, wherein, in step a), the reaction temperature of the reaction is controlled to be 0 to 5 ℃.
At this temperature, the heat generated by the chlorination reaction can be removed smoothly, thereby allowing the reaction to proceed as desired.
According to one embodiment of the present disclosure, wherein, in step a), the ratio of 5-chloro-2-pentanone to chlorinating agent is 1:2 to 1:5, preferably 1: 2.2 to 1: 2.5, the reaction process is liquid-liquid reaction or liquid-gas reaction.
By controlling the amount of chlorinating agent, the reaction can be carried out as desired.
According to one embodiment of the present disclosure, wherein, in step a), the reaction of 5-chloro-2-pentanone with the chlorinating agent is a solvent-free reaction.
In the case of no solvent, the 1,3, 5-trichloro-2-pentanone prepared in step A) can be directly used in the next reaction without isolation.
According to one embodiment of the present disclosure, wherein in step a), the off-gas absorber contents are selected from one or more of aqueous solutions of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium hydroxide and ammonia.
According to one embodiment of the present disclosure, wherein, in the step B), the reaction temperature of the reaction is controlled to be 0 to 5 ℃, and the reaction process is a liquid-liquid reaction.
The reaction at the above-mentioned specific temperature allows the heat generated by the cyclization reaction to be smoothly removed, thereby allowing the reaction to proceed as desired.
According to one embodiment of the present disclosure, wherein, in step B), the ratio of 1,3, 5-trichloro-2-pentanone to lye is 1:1 to 1: 1.2.
by controlling the dosage of the alkali liquor, the reaction can be carried out as expected, and the generation of the byproduct 2, 5-dichlorocyclopentanone is reduced.
According to one embodiment of the present disclosure, wherein, in step B), the 1,3, 5-trichloro-2-pentanone uses a solvent selected from one or more of dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, diethyl ether and DMF, preferably dichloromethane, preferably in a ratio of 1,3, 5-trichloro-2-pentanone: dichloromethane is prepared according to the mass ratio of 1: 2.
by using the above specific solvents, and specific amounts, the reaction can be carried out as desired, increasing the yield, selectivity and purity of the product.
According to the embodiment of the disclosure, the advantages of high mixing efficiency, high heat transfer efficiency and small amplification effect of the microchannel reactor are utilized, so that the 5-chloro-2-pentanone can perform selective double alpha-site chlorination reaction to obtain 1,3, 5-trichloro-2-pentanone, and further, the target product 1-chloro-1-chloroacetyl cyclopropane is obtained by reaction with alkali liquor in the microchannel reactor, and side reaction generation and product decomposition are stopped.
In order to further illustrate the invention, several specific examples are given below, it being apparent that the scope of the invention is not limited to these examples.
EXAMPLE 1,3, 5-trichloro-2-pentanone preparation
Using the apparatus shown in fig. 1 (including the tail gas absorber), the flow rate of 5-chloro-2-pentanone in the feed pump 1 was controlled to 0.5mL/min and passed through the preheating/cooling module 1 to reach a feed inlet temperature of 0 ℃; controlling the flow rate of sulfonyl chloride in the feed pump 2 to be 0.5mL/min, and enabling the sulfonyl chloride to pass through the preheating/cooling module 2 to reach the temperature of a feed inlet to be 0 ℃; the two materials enter a microchannel reaction chamber through a mixer, the residence time in the microchannel reaction chamber is 20min, the temperature of the mixer and the temperature of the microchannel reaction chamber are controlled in the whole process, and the material outlet temperature of the microchannel reaction chamber is ensured not to be higher than 5.0 ℃, so that 1,3, 5-trichloro-2-pentanone and sulfur dioxide are obtained. The generated waste gas sulfur dioxide is directly led into a tail gas absorption tank containing sodium hydroxide aqueous solution.
The crude product was washed with water and used directly in the next reaction. The conversion rate is more than 99%, the product GC analysis shows that the purity is 99% by an area normalization method, and the quantitative analysis is 98%.
EXAMPLE preparation of bis 1-chloro-1- (chloroacetyl) cyclopropane
1,3, 5-trichloro-2-pentanone prepared in example 1 was dissolved in 2 times the mass of dichloromethane using an additional apparatus as described in fig. 1 (not including a tail gas absorption apparatus) to give a starting liquid having a density of 1.26 g/mL; controlling the flow rate of a 1,3, 5-trichloro-2-pentanone/dichloromethane solution in the feeding pump 1 to be 1mL/min, and reaching the temperature of a feeding hole to be 0 ℃ through the preheating/cooling module 1; controlling the flow rate of liquid caustic soda (30% by mass of sodium hydroxide aqueous solution with the density of 1.34g/mL) in the feed pump 2 to be 0.30mL/min, and enabling the liquid caustic soda to pass through the preheating/cooling module 2 to reach the temperature of a feed inlet to be 0 ℃; the molar ratio of the two materials is 1: 1.2; and (2) the mixture enters a microchannel reaction chamber through a mixer, the residence time in the microchannel reaction chamber is 10min, the temperature of the mixer and the microchannel reaction chamber is controlled in the whole process, and the material outlet temperature of the microchannel reaction chamber is ensured to be not higher than 10 ℃ so as to obtain the 1-chloro-1- (chloroacetyl) cyclopropane.
After the crude product is subjected to liquid separation, the purity of the crude product is 97 percent through LC analysis (see figure 2) and an area normalization method, the conversion rate of raw materials is more than 99 percent, and the crude product can be directly used for preparing prothioconazole through the next reaction. Or distilling to obtain refined product 1-chloro-1- (chloroacetyl) cyclopropane with purity of more than 99%.
EXAMPLE III
1-chloro-1- (chloroacetyl) cyclopropane was prepared in the same manner as in examples one and two, except that 1,3, 5-trichloro-2-pentanone obtained in example one was used as it is in example two without being washed with water, and the aqueous base in example two was replaced with an aqueous KOH solution.
Purity > 97% and conversion > 99% by LC analysis, which is similar to figure 2.
Comparative example-preparation of 1-chloro-1- (chloroacetyl) cyclopropane by a kettle reaction
A500 mL three-necked flask was equipped with a constant pressure dropping funnel, a reflux condenser and a thermometer. A solution of 1,3, 5-trichloro-2-pentanone (94.8g, 0.5mol) prepared in example 1 and 2 times the mass of dichloromethane was placed in a flask, and 160g of a 15% aqueous sodium hydroxide solution (24 g, 0.6mol) was placed in a constant pressure dropping funnel; slowly dropwise adding sodium hydroxide; the reaction quickly releases heat, dichloromethane begins to boil and flows back, the dropwise addition is finished in about 3 hours, and the dropwise addition rate is controlled to prevent material spraying. Cooled to room temperature and analyzed by taking the material.
By LC analysis (see FIG. 3), only a small amount of the product 1-chloro-1- (chloroacetyl) cyclopropane was produced, the main product being 2, 5-dichlorocyclopentanone.
As can be seen from the above examples and comparative examples, the 1-chloro-1- (chloroacetyl) cyclopropane prepared according to the method of the present disclosure has good selectivity, high conversion rate, high product purity, and elimination of polysubstituted byproducts from the reaction source. The method can obtain the 1-chloro-1- (chloracetyl) cyclopropane through two-step reaction, and the product of the first-step reaction can also be directly used for subsequent reaction without purification, thereby greatly reducing the generation of reaction waste liquid. On the other hand, in the case of performing the reaction using a flask, since the reaction heat cannot be controlled, even if the base is added dropwise to a dichloromethane solution of 1,3, 5-trichloro-2-pentanone, the desired 1-chloro-1- (chloroacetyl) cyclopropane cannot be obtained but only 2, 5-dichlorocyclopentanone is obtained.
Claims (10)
1. A process for preparing 1-chloro-1- (chloroacetyl) cyclopropane, comprising:
B) reacting 1,3, 5-trichloro-2-pentanone with an alkali liquor in a solvent at-5 to 10 ℃ and 1.0 to 10.0bar pressure in a microchannel reactor for 5 to 30 minutes to obtain 1-chloro-1- (chloroacetyl) cyclopropane,
wherein the solvent is selected from one or more of dichloromethane, 1, 2-dichloroethane, tetrahydrofuran, methyltetrahydrofuran, diethyl ether and DMF; the alkali liquor is one or more aqueous solutions of alkali selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; the mass ratio of the 1,3, 5-trichloro-2-pentanone to the solvent is 1:1 to 1: 5; the molar ratio of the 1,3, 5-trichloro-2-pentanone to the alkali liquor is 1:1 to 1: 1.5.
2. The method according to claim 1, wherein the method further comprises, before step B):
A) reacting 5-chloro-2-pentanone with sulfuryl chloride or chlorine gas in a microchannel reactor at-5 to 25 ℃ under a pressure of 1.0 to 10.0bar for 5 to 30 minutes to obtain 1,3, 5-trichloro-2-pentanone,
3. the method of claim 1 or 2, wherein the microchannel reactor comprises:
the device comprises a material tank 1, a feeding pump 1 and a preheating/cooling module 1 which are connected in sequence, and a material tank 2, a feeding pump 2 and a preheating/cooling module 2 which are connected in sequence, a mixer connected to the preheating/cooling module 1 and the preheating/cooling module 2, a microchannel reaction chamber connected to the mixer, a discharge chute connected to the microchannel reaction chamber, and a storage tank connected to the discharge chute.
4. The method according to claim 1 or 2, wherein the material tanks 1 and 2 are composed of containers made of teflon or lined with enamel; the pipelines adopt silica gel or silicon carbide materials; the mixer is silica gel, and carbon fiber, quartz fiber or macroporous silica gel is filled in the mixer; the preheating/cooling modules 1 and 2 are respectively used for controlling the temperature of the material or the mixture entering the mixer to be-20 to 120 ℃; the storage tank is composed of a container with polytetrafluoroethylene or enamel lining; the feed pumps 1 and 2 are liquid feed pumps or gas feed pumps, wherein the flow rate of the liquid feed pump is 0.006 to 600mL/min, the flow rate of the gas feed pump is 5 to 900mL/min, and the direction of the pump head is adjustable; the pipe diameter of the microchannel reaction chamber is 0.02-10 mm, and the interior of the reaction chamber is laminar flow or turbulent flow.
5. The method of claim 2 wherein said steps a) and B) use different microchannel reactors.
6. The process according to claim 2, wherein in step a) the temperature of the reaction is controlled to be 0 to 5 ℃.
7. The process according to claim 2, wherein in step a) the ratio of 5-chloro-2-pentanone to chlorinating agent is 1:2 to 1:5, preferably 1: 2.2 to 1: 2.5, the reaction process is liquid-liquid reaction or liquid-gas reaction.
8. The process according to claim 2, wherein in step a) the reaction of 5-chloro-2-pentanone with the chlorinating reagent is a solvent-free reaction.
9. The method according to claim 1, wherein, in the step B), the temperature of the reaction is controlled to be 0 to 5 ℃, and the reaction process is a liquid-liquid reaction.
10. The process according to claim 1, wherein in step B) the ratio of 1,3, 5-trichloro-2-pentanone to liquid base is 1:1 to 1: 1.2.
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| CN113402381A (en) * | 2021-05-18 | 2021-09-17 | 常州新东化工发展有限公司 | Preparation method of chloroacetyl chloride |
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