CN109593030A - A kind of α, the preparation method of alpha-single chloro acetophenone compounds - Google Patents
A kind of α, the preparation method of alpha-single chloro acetophenone compounds Download PDFInfo
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- CN109593030A CN109593030A CN201811381378.5A CN201811381378A CN109593030A CN 109593030 A CN109593030 A CN 109593030A CN 201811381378 A CN201811381378 A CN 201811381378A CN 109593030 A CN109593030 A CN 109593030A
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- acetophenone compounds
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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
- 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
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Abstract
The invention discloses a kind of α, the preparation method of alpha-single chloro acetophenone compounds, its preparation process is as follows: i.e. using acetophenone compounds and chlorine as raw material, α is realized in micro passage reaction, the preparation of alpha-single chloro acetophenone compounds, the reaction can be carried out in the case where having solvent or condition of no solvent.The application is reacted using the dichloro- that micro passage reaction carries out acetophenone compounds Alpha-Methyl, and the chlorination reaction being related to is made to have the advantages of Atom economy is high, and reaction speed is fast, Environmental Safety, continuous production.
Description
Technical field
The invention belongs to technical field of organic synthesis, are related to microchannel chlorination reaction, in particular to a kind of α, alpha-single chloro
The microchannel chlorination synthetic technology of acetophenone compounds.
Background technique
α, alpha-single chloro acetophenone compounds are a kind of important organic synthesis intermediates, can be used as building block.
α, the synthesis of alpha-single chloro object under certain condition, pass through different chlorinations mainly using carbonyls as raw material
Agent chlorination is prepared.If foreign literature (Angew Chem Int Ed.2004,43 (41): 5507-5510.) are reported, N- is used
Chlorosuccinimide (NCS) is chlorinating agent, has reaction selectivity height, the high advantage of yield, but NCS is on the high side, contains
Chlorine dose is lower；Foreign literature (Green Chem, 2009,11 (2): 275-278) report makees chlorinating agent using two chlordantoins, one
Good chloro effect is also achieved under conditions of fixed." α, alpha-single chloro carbonyls are repeatable in water and acid for domestic literature
Utilizing the rapid synthesis in system " (the chemistry world such as Chen Zizhan, 2013,11 (13): 685-688) report is using trichlorine isocyanide
Uric acid is chlorinating agent, under Catalyzed by p-Toluenesulfonic Acid effect, prepares document α, alpha-single chloro carbonyls.But these methods are general
All over the problem is that the chlorine atom accounting in chlorinating agent is lower, cause Atom economy poor, the requirement with Green Chemistry is also
A certain distance.Above-mentioned method reported in the literature is that chlorination is carried out in traditional reaction kettle simultaneously, since chlorination is anti-
It answers general heat release violent, easily there are problems that hot-spot using traditional reaction kettle, cause reaction selectivity poor, yield is undesirable；
And the problem that the operating time is too long.
Summary of the invention
It is high that the purpose of the present invention is to provide a kind of Atom economies, and reaction speed is fast, Environmental Safety, continuous production α,
The method of alpha-single chloro acetophenone compounds.The present invention, which is used, has good quickly mixing to acetophenone compounds and chlorine
The micro passage reaction of effect and good heat transfer effect is reaction unit, makes acetophenone compounds and chlorine in quick, height
Under conditions of effect mixing, the chlorination of highly selective α hydrogen atoms of completion.
The present invention prepares α, and the method for alpha-single chloro acetophenone compounds passes through microchannel that is, using chlorine as chlorinating agent
Reactor prepares α, alpha-single chloro acetophenone compounds, comprising the following steps:
(1) solution and gas configuration: weigh acetophenone compounds be dissolved in methanol, ethyl alcohol, methylene chloride, dichloroethanes or
In ethyl acetate, it is made into the acetophenone compounds solution of mass fraction 50~100%, for use；Adjust the stream of chlorine and nitrogen
Amount mixes the two, and quality of chlorine gas score is 50~100%, for use；
(2) microchannel plate is answered: acetophenone compounds solution is pumped into micro passage reaction by feed pump continuous uniform,
Rate is 1~100ml/min, and the molar ratio of raw material acetophenone compounds and chlorine is 1:2~6, reaction temperature control -30~
100 DEG C, pressure is 1~5atm, and retention time is to collect product under 0.1~5min；
(3) post-process: reaction solution purges remaining chlorine with nitrogen, and precipitation isolates and purifies to obtain α, alpha-single chloro acetophenones
Compound.
The acetophenone compounds be acetophenone, melilotal, o-methyl-benzene ethyl ketone, methyl acetophenone or
Parachloroacetophenone.
The micro passage reaction is silicon carbide material.
The mass fraction of the acetophenone compounds solution is 75~100%.
Mass fraction of the chlorine in gaseous mixture is 75~100%.
The molar ratio of the raw material acetophenone compounds and chlorine is 1:2~3.
The reaction temperature is 20-80 DEG C.
The pressure is 1-2atm.
The reaction time is 0.1-3min.
The utility model has the advantages that it is provided by the invention using chlorine as chlorinating agent, α, alpha-single chloro benzene are prepared by micro passage reaction
The method of second ketone compounds.Compared with other chlorinating agents reported in background technique, have Atom economy high, at low cost
Advantage；And due to the good heat transfer effect of micro passage reaction, so that chlorination process becomes safely controllable；Compared to tank reactor
Reaction time also substantially shortens；The present invention is continuous process simultaneously, compares intermittently operated, it is easier to realize that industrialization is extensive
Production.
Detailed description of the invention
Fig. 1 is that microchannel plate answers process schematic.In figure: 1, stock bottle, 2, feed pump, 3, micro passage reaction, 4, control
Warm device, 5, counterbalance valve, 6, product receiving bottle, 7, vent gas treatment bottle.
Specific embodiment
Further illustrate the present invention with reference to embodiments, the purpose is to be better understood on contents of the present invention institute body
Existing substantive distinguishing features of the invention, therefore the cited case is not construed as limiting the scope of the invention.
Embodiment 1
The temperature of temperature regulating device is adjusted to 40 DEG C, system pressure 1-2atm, under solvent-free conditions, adjusts benzene feedstock
Ethyl ketone flow is 5mol/h, and material is squeezed into reaction system with metering pump and reacted, according to anti-by chlorine flowrate 11mol/h
It should require, set the residence time as 30s.Sampling carries out liquid phase analysis, reaction selectivity 99.5%, yield 99.0%.
Embodiment 2
The temperature of temperature regulating device is adjusted to 40 DEG C, system pressure 1-2atm, under the conditions of methanol as solvent, acetophenone
Methanol solution mass fraction be 80%, adjustment raw material acetophenone flow is 5mol/h, and chlorine flowrate 11mol/h uses metering pump
Material is squeezed into reaction system and is reacted, is required according to reaction, sets the residence time as 30 seconds.Sampling carries out liquid phase point
Analysis, reaction selectivity 99.3%, yield 99.1%.
Embodiment 3
The temperature of temperature regulating device is adjusted to 40 DEG C, system pressure 1-2atm, under solvent-free conditions, adjusts benzene feedstock
Ethyl ketone flow is 5mol/h, and quality of chlorine gas score is 80%, chlorine flowrate 11mol/h, and material is squeezed into reactant with metering pump
It is reacted in system, is required according to reaction, set the residence time as 30 seconds.Sampling carries out liquid phase analysis, reaction selectivity
99.4%, yield 99.0%.Embodiment 4
The temperature of temperature regulating device is adjusted to 60 DEG C, system pressure 1-2atm, under solvent-free conditions, adjusts raw material pair
Methyl acetophenone flow is 5mol/h, and material is squeezed into reaction system with metering pump and reacted by chlorine flowrate 11mol/h,
It is required according to reaction, sets the residence time as 30 seconds.Sampling carries out liquid phase analysis, reaction selectivity 98.1%, yield 97.6%.
Embodiment 5
The temperature of temperature regulating device is adjusted to 70 DEG C, system pressure 1-2atm, under solvent-free conditions, adjusts raw material pair
Chloro-acetophenone flow is 5mol/h, and material is squeezed into reaction system with metering pump and reacted by chlorine flowrate 11mol/h, root
It is required according to reaction, sets the residence time as 30 seconds.Sampling carries out liquid phase analysis, reaction selectivity 95.6%, yield 95.1%.
Embodiment 6
The temperature of temperature regulating device is adjusted to 60 DEG C, system pressure 1-2atm, under solvent-free conditions, adjusts benzene feedstock
Ethyl ketone flow is 5mol/h, and material is squeezed into reaction system with metering pump and reacted, according to anti-by chlorine flowrate 15mol/h
It should require, set the residence time as 30 seconds.Sampling carries out liquid phase analysis, reaction selectivity 97.5%, yield 98.2%.
Embodiment 7
The temperature of temperature regulating device is adjusted to 70 DEG C, system pressure 1-2atm, under solvent-free conditions, adjusts benzene feedstock
Ethyl ketone flow is 5mol/h, and material is squeezed into reaction system with metering pump and reacted, according to anti-by chlorine flowrate 11mol/h
It should require, set the residence time as 30 seconds.Sampling carries out liquid phase analysis, reaction selectivity 95.1%, yield 98.7%.
Embodiment 8
The temperature of temperature regulating device is adjusted to 70 DEG C, system pressure 1-2atm, under solvent-free conditions, adjusts benzene feedstock
Ethyl ketone flow is 5mol/h, and material is squeezed into reaction system with metering pump and reacted, according to anti-by chlorine flowrate 11mol/h
It should require, set the residence time as 30 seconds.Sampling carries out liquid phase analysis, reaction selectivity 99.1%, yield 98.0%.
Claims (9)
1. a kind of α, the preparation method of alpha-single chloro acetophenone compounds is answered that is, using chlorine as chlorinating agent by microchannel plate
Device prepares α, alpha-single chloro acetophenone compounds, comprising the following steps:
(1) solution and gas configuration: acetophenone compounds are weighed and are dissolved in methanol, ethyl alcohol, methylene chloride, dichloroethanes or acetic acid
In ethyl ester, it is made into the acetophenone compounds solution of mass fraction 50~100%, for use；The flow for adjusting chlorine and nitrogen, makes
The two mixing, quality of chlorine gas score are 50~100%, for use；
(2) microchannel plate is answered: acetophenone compounds solution is pumped into micro passage reaction, rate by feed pump continuous uniform
For 1~100ml/min, the molar ratio of raw material acetophenone compounds and chlorine is 1:2~6, reaction temperature control -30~100
DEG C, pressure is 1~5atm, and retention time is to collect product under 0.1~5min；
(3) post-process: reaction solution purges remaining chlorine with nitrogen, and precipitation isolates and purifies to obtain α, alpha-single chloro acetophenones chemical combination
Object.
2. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
Acetophenone compounds be acetophenone, melilotal, o-methyl-benzene ethyl ketone, methyl acetophenone or parachloroacetophenone.
3. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
Micro passage reaction be silicon carbide material.
4. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
The mass fraction of acetophenone compounds solution is 75~100%.
5. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
Mass fraction of the chlorine in gaseous mixture is 75~100%.
6. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
The molar ratio of raw material acetophenone compounds and chlorine is 1:2~3.
7. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
Reaction temperature is 20-80 DEG C.
8. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
Pressure is 1-2atm.
9. a kind of α according to claim 1, the preparation method of alpha-single chloro acetophenone compounds, which is characterized in that described
Reaction time is 0.1-3min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358387A (en) * | 2020-11-26 | 2021-02-12 | 福州大学 | Method for continuously producing monochloroacetone by micro-droplet reactor |
| CN114920636A (en) * | 2022-05-24 | 2022-08-19 | 东南大学 | Synthetic method of alpha chloro arylethanone compound |
| CN115724727A (en) * | 2022-11-24 | 2023-03-03 | 河北工业职业技术学院 | Method for preparing cyazofamid intermediate 2,2-dichloro-4' -methylacetophenone |
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| WO2000075094A2 (en) * | 1999-06-03 | 2000-12-14 | Ishihara Sangyo Kaisha, Ltd. | Method for producing a halogenated acetophenone |
| CN101016249A (en) * | 2007-02-28 | 2007-08-15 | 北京科技大学 | Method of synthesizing beta-adrenaline excitant lecdopamine |
| CN101230000A (en) * | 2007-01-25 | 2008-07-30 | 江苏中慧药物研究有限公司 | Method for preparing 2-chlorin-2-aryl acetate compounds |
| CN105384617A (en) * | 2015-12-11 | 2016-03-09 | 大连世慕化学有限公司 | Method using micro reactor to prepare 1-chloro-1'-chloroacetyl cyclopropane |
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2018
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| US3869513A (en) * | 1972-06-12 | 1975-03-04 | Buckman Labor Inc | Dinitro-dialklyamino-acetophenones |
| WO2000075094A2 (en) * | 1999-06-03 | 2000-12-14 | Ishihara Sangyo Kaisha, Ltd. | Method for producing a halogenated acetophenone |
| CN101230000A (en) * | 2007-01-25 | 2008-07-30 | 江苏中慧药物研究有限公司 | Method for preparing 2-chlorin-2-aryl acetate compounds |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358387A (en) * | 2020-11-26 | 2021-02-12 | 福州大学 | Method for continuously producing monochloroacetone by micro-droplet reactor |
| CN112358387B (en) * | 2020-11-26 | 2021-11-30 | 福州大学 | Method for continuously producing monochloroacetone by micro-droplet reactor |
| CN114920636A (en) * | 2022-05-24 | 2022-08-19 | 东南大学 | Synthetic method of alpha chloro arylethanone compound |
| CN114920636B (en) * | 2022-05-24 | 2023-12-22 | 东南大学 | Synthesis method of alpha chloro-aryl-ethanone compound |
| CN115724727A (en) * | 2022-11-24 | 2023-03-03 | 河北工业职业技术学院 | Method for preparing cyazofamid intermediate 2,2-dichloro-4' -methylacetophenone |
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