CN117126044B - Microwave-assisted synthesis method of methyl ketone compound - Google Patents
Microwave-assisted synthesis method of methyl ketone compound Download PDFInfo
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- -1 methyl ketone compound Chemical class 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000007144 microwave assisted synthesis reaction Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000003480 eluent Substances 0.000 claims description 9
- 238000010828 elution Methods 0.000 claims description 7
- 150000003462 sulfoxides Chemical class 0.000 claims 2
- 230000035484 reaction time Effects 0.000 abstract description 7
- 125000005002 aryl methyl group Chemical group 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000000605 extraction Methods 0.000 description 14
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 10
- 150000002924 oxiranes Chemical class 0.000 description 10
- 230000008707 rearrangement Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000269 nucleophilic effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000006462 rearrangement reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007093 Meinwald rearrangement reaction Methods 0.000 description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012973 diazabicyclooctane Substances 0.000 description 3
- IBWLXNDOMYKTAD-UHFFFAOYSA-N 2-(4-chlorophenyl)oxirane Chemical compound C1=CC(Cl)=CC=C1C1OC1 IBWLXNDOMYKTAD-UHFFFAOYSA-N 0.000 description 2
- QAWJAMQTRGCJMH-UHFFFAOYSA-N 2-(4-methylphenyl)oxirane Chemical compound C1=CC(C)=CC=C1C1OC1 QAWJAMQTRGCJMH-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000005192 alkyl ethylene group Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 2
- TZIAZLUAMDLDJF-UHFFFAOYSA-N 1-(2-bromophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=CC=C1Br TZIAZLUAMDLDJF-UHFFFAOYSA-N 0.000 description 1
- LWGNDIMNCPMZOF-UHFFFAOYSA-N 1-(2-chlorophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=CC=C1Cl LWGNDIMNCPMZOF-UHFFFAOYSA-N 0.000 description 1
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- IZPMETSEQUXCSH-UHFFFAOYSA-N 2-[(2-chlorophenyl)methyl]oxirane Chemical compound ClC1=CC=CC=C1CC1OC1 IZPMETSEQUXCSH-UHFFFAOYSA-N 0.000 description 1
- CCHJOAVOTFFIMP-UHFFFAOYSA-N 2-phenyloxetane Chemical compound O1CCC1C1=CC=CC=C1 CCHJOAVOTFFIMP-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000006942 Corey-Chaykovsky ring formation reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JYLCNTVVJABSEX-UHFFFAOYSA-N N#C[Co](C#N)(C#N)(C#N)C#N Chemical compound N#C[Co](C#N)(C#N)(C#N)C#N JYLCNTVVJABSEX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
Classifications
-
- 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
- C07C45/58—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 three-membered rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a microwave-assisted synthesis method of methyl ketone compounds, which comprises the following steps: adding a catalyst NaH and an organic solvent into a microwave reaction tube, dissolving the catalyst NaH in the organic solvent, then adding a catalyst trimethyl sulfoxide iodide and a monosubstituted ethylene oxide compound, reacting for 30 minutes under the condition of microwave heating, extracting after the reaction is finished, eluting and separating by using a chromatographic column, and separating to obtain the colorless oily compound. The microwave-assisted synthesis method of the methyl ketone compound is free from the use of a catalyst with a complex structure, simple and convenient to operate, short in reaction time and wide in substrate application range, and can be suitable for synthesizing alkyl methyl ketone, alkenyl methyl ketone and aryl methyl ketone.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a microwave-assisted synthesis method of methyl ketone compounds.
Background
The Meinwald rearrangement reaction is a common rearrangement reaction mode of oxiranes. Depending on the structural features of the reactants and the electronic and steric effects of the epoxy alpha-substituents, terminal epoxy typically will produce aldehydes under acid catalysis. Unlike acid-catalyzed Meinwald rearrangement, there are also a small number of reports of terminal epoxide rearrangements to the corresponding methyl ketone, and a few transition metal catalysts containing Fe, ru, co, rh or Pd can catalyze the rearrangement of monosubstituted epoxides to methyl ketones in some cases.
For example, umlagerung aliphatischer terminaler Epoxide zu Methylketonen durch Eisenalkyl-Reagenzien statt durch Co in the prior art 2 (CO) 8 The use of lithium tetramethyl iron Me is reported by oder Edelsetallkatalystatoren 4 FeLi 2 As a catalyst, the rearrangement of the monosubstituted alkyl oxirane into the corresponding methyl ketone can be realized, and meanwhile, the production of various alcohols is accompanied in the reaction process. Isomerization of Epoxides to Ketones by Pentacyanocobalt Complex. Chem. Reported that mono-substituted ethylene oxide is found in HCo (CN) 5 3- The rearrangement to methyl ketone under the action of the catalyst is an example, but this reaction also occurs in competition reaction of epoxy ring opening to form secondary alcohol, and the reaction of forming alcohol is the main reaction, and the selectivity of the reaction is poor.
The above transition metal catalyzed reaction of mono-substituted oxiranes to methyl ketones all occur during rearrangement of alkyl substituted epoxides and are mostly occasional individual examples, often accompanied by other side reactions, with poor reaction selectivity and little systematic and intensive research.
In addition to the rearrangement reaction of the end group epoxy to methyl ketone catalyzed by the transition metal catalyst, there is a class of rearrangement reactions which are catalyzed by Lewis acid and nucleophilic metal complexes together to obtain methyl ketone. For example, the use of Lewis acids in combination with nucleophilic transition metal complexes to catalyze the rearrangement of alkyl epoxides to methyl ketones is reported in Selective Rearrangement OfTerminal Epoxides into Methylketones Catalysed by a Nucleophilic Rhodium-NHC-Picer Complex and Selective Rearrangement Of Terminal Epoxides into Methylketones Catalysed by a Nucleophilic Rhodium-NHC-Picer Complex, respectively. However, these reactions have drawbacks such as narrow substrate application, poor selectivity for 2-aryloxirane reactions, etc.
The improvement of the catalyst in Regio-and Chemoselective Rearrangement ofTerminal Epoxides into Methyl Alkyl and Aryl Ketone increases the selectivity of rearrangement of 2-aryl ethylene oxide to methyl ketone, but is still accompanied by the formation of aldehyde and cannot be specifically rearranged to methyl ketone like alkyl ethylene oxide, and meanwhile, the transition metal catalyst used in the reaction process has a complex structure, is not easy to prepare and has high price and uneconomical.
Previous studies by applicant: nucleophilic Organic Base DABCO-Mediated Chemospecific Meinwald Rearrangement of Terminal Epoxides into Methyl Ketones nucleophilic organic base catalyzed rearrangement reaction of monosubstituted epoxy compound to methyl ketone by using DABCO as catalyst is applicable to aryl substituted epoxy compound, and the catalyst used in the reaction has low price and high yield, and can be purchased directly. However, the method has high reaction temperature and long reaction time. The reaction temperature can be reduced by adding Lewis acid, but the yield is reduced.
In summary, in the prior art, the method for generating the methyl ketone compound by using DABCO (triethylene diamine) as a catalyst has high yield and simple and convenient operation, but the method is only suitable for synthesizing styryl methyl ketone and aryl methyl ketone, is not suitable for alkyl methyl ketone, and has long reaction time, high temperature and lower safety. The reaction catalyzed by the combined action of the Lewis acid and the nucleophilic transition metal complex can prepare alkyl methyl ketone from alkyl ethylene oxide, but has poor effect on aryl ethylene oxide, and the reaction catalyst has complex structure and high cost. When the reaction is rhodium catalysis, benzene is also needed to be used as a solvent, the environmental protection performance is low, and when the catalyst is cobalt metal complex, the reaction time is long. Therefore, the invention provides a novel synthesis method of methyl ketone compounds.
Disclosure of Invention
The invention aims to provide a microwave-assisted synthesis method of methyl ketone compounds, which does not need to use a catalyst with a complex structure, is simple and convenient to operate, has short reaction time and wide substrate application range, can be suitable for synthesizing alkyl methyl ketone, alkenyl methyl ketone and aryl methyl ketone, and solves the problems that the catalyst in the prior art has a complex structure and long reaction time, and the conversion from epoxy compounds to methyl ketone is mainly suitable for synthesizing one of alkyl methyl ketone or aryl methyl ketone.
In order to achieve the above purpose, the invention provides a microwave-assisted synthesis method of methyl ketone compounds, which comprises the following steps: adding a catalyst NaH and an organic solvent into a microwave reaction tube, dissolving the catalyst NaH in the organic solvent, then adding a catalyst trimethyl sulfoxide iodide and a monosubstituted ethylene oxide compound, reacting for 30 minutes under the condition of microwave heating, extracting after the reaction is finished, eluting and separating by using a chromatographic column, and separating to obtain a colorless oily compound;
the reaction equation is:
r is one of phenyl, styryl, chlorophenyl, p-methylphenyl and 2-bromophenyl benzyl.
Preferably, the mono-substituted oxiranes include one of styryl oxirane, phenyl oxirane, p-chlorophenyl oxirane, p-methylphenyl oxirane, 2-bromophenyl benzyl oxirane.
Preferably, the organic solvent is anhydrous dimethyl sulfoxide, and the dosage of the organic solvent is 1-5mL.
Preferably, the amount of organic solvent used is 3mL.
Preferably, the catalyst NaH is 60% NaH and is used in an amount of 1-3mmol.
Preferably, the amount of NaH catalyst is 2mmol.
Preferably, the amount of the catalyst trimethylsulfoxide iodide is 0.05-0.2mmol, and the amount of the mono-substituted ethylene oxide compound is 0.1-1mmol.
Preferably, the catalyst is trimethyl sulfoxide iodide in 0.1mmol and the monosubstituted oxirane compound in 0.5mmol.
Preferably, the eluent PE/EA= (50-100) eluted by the chromatographic column: 1.
preferably, the volume of the microwave reaction tube is 10mL and the temperature of the microwave heating is 110 ℃.
The invention has the beneficial effects that:
the invention uses NaH and trimethyl sulfoxide iodide as catalysts, the catalyst has simple structure, simple operation, short reaction time and wide application range of substrates, and can be suitable for synthesizing alkyl methyl ketone, alkenyl methyl ketone and aryl methyl ketone. The provided synthetic method has mild reaction conditions and is easy to control.
The technical scheme of the invention is further described in detail through examples.
Detailed Description
The present invention will be further described with reference to examples in which various chemicals and reagents are commercially available unless otherwise specified.
The monosubstituted oxiranes are prepared commercially or by the Corey-Chaykovsky reaction.
Example 1
Synthesis of styryl methyl ketone
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of styryl ethylene oxide were added, and the mixture was heated to 110℃by microwaves to react for 30 minutes. The reaction equation is as follows:
after the reaction, extraction was performed using dichloromethane and water, and after the extraction, elution and separation were performed using a chromatography column, wherein the eluent was PE/ea=100:1, 58mg of a colorless oily compound was obtained by separation, and the yield was 80%.
1 H NMR(400MHz,CDCl 3 )δ7.55–7.47(m,3H),7.42–7.35(m,3H),6.72(d,J＝16.3Hz,1H),2.38(s,3H). 13 C NMR(101MHz,CDCl 3 )δ198.4,143.5,134.3,130.5,128.9,128.2,127.0,27.5.
Example 2
Synthesis of acetophenone
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of phenylethylene oxide were added, and the mixture was heated to 110℃by microwaves to react for 30 minutes. The reaction equation is as follows:
after the reaction was completed, extraction was performed using dichloromethane and water, and after the extraction, elution was performed using a chromatography column, and eluent PE/ea=50:1, 42mg of a colorless oily compound was isolated in a yield of 70%.
1 H NMR(400MHz,CDCl 3 )δ8.00–7.91(m,2H),7.57(t,J＝7.7Hz,1H),7.47(dd,J＝7.67.6,Hz,2H),2.601(s,3H). 13 C NMR(101MHz,CDCl 3 )δ198.1,137.0,133.1,128.7,128.2,26.4.
Example 3
Synthesis of p-chloroacetophenone
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of p-chlorophenyl ethylene oxide were added, and the mixture was heated to 110℃by microwave heating, and reacted for 30 minutes. The reaction equation is as follows:
after the reaction was completed, extraction was performed using dichloromethane and water, and after extraction, elution was performed using a chromatography column, eluent PE/ea=50:1, 58mg of a colorless oily compound was isolated, and the yield was 75%.
1 H NMR(400MHz,CDCl 3 )δ7.88(d,J＝8.8Hz,2H),7.36(d,J＝8.4Hz,2H),2.59(s,3H). 13 C NMR(101MHz,CDCl 3 )δ196.7,139.5,135.4,129.8,128.8,26.5.
Example 4
Synthesis of p-methylacetophenone
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of p-methylphenyl ethylene oxide were added, and the mixture was heated to 110℃by microwaves to react for 30 minutes. The reaction equation is as follows:
after the reaction was completed, extraction was performed using dichloromethane and water, and after extraction, elution was performed using a chromatography column, eluent PE/ea=50:1, and 48mg of a colorless oily compound was isolated in 72% yield.
1 H NMR(400MHz,CDCl 3 )δ7.86(d,J＝8.1Hz,2H),7.26(d,J＝7.9Hz,2H),2.58(s,3H),2.41(s,3H). 13 C NMR(101MHz,CDCl 3 )δ197.8,143.9,134.7,129.2,128.4,26.5,21.6.
Example 5
Synthesis of 2-bromophenyl acetone
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of 2-bromobenzyl ethylene oxide were added, and the mixture was heated to 110℃by microwave heating, and reacted for 30 minutes. The reaction equation is as follows:
after the reaction was completed, extraction was performed using dichloromethane and water, and after extraction, elution was performed using a chromatography column, eluent PE/ea=50:1, and 64mg of a colorless oily compound was isolated in 60% yield.
1 H NMR(300MHz,Chloroform-d)δ7.78–7.46(m,1H),7.42–6.85(m,3H),3.86(s,2H),2.21(s,3H). 13 C NMR(75MHz,CDCl 3 )δ205.0,134.8,132.9,131.6,128.9,127.7,125.0,50.8,29.8.
Example 6
Synthesis of 2-chlorophenyl acetone
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of 2-chlorobenzyl ethylene oxide were added, and the mixture was heated to 110℃by microwave heating, and reacted for 30 minutes. The reaction equation is as follows:
after the reaction was completed, extraction was performed using dichloromethane and water, and after extraction, elution and separation were performed using a chromatography column, eluent PE/ea=50:1, 55mg of a colorless oily compound was obtained by separation, and the yield was 65%.
1 H NMR(300MHz,Chloroform-d)δ7.50–7.37(m,1H),7.27(q,J＝5.1,4.7Hz,3H),3.88(s,2H),2.24(s,3H). 13 C NMR(75MHz,CDCl 3 )δ205.0,134.4,132.9,131.6,129.6,128.7,127.0,48.4,29.7.
Comparative example 1
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of phenyl ethane oxide were added, and the mixture was heated to 40℃by microwave heating to react for 30 minutes. Unreacted.
Comparative example 2
In a 10mL microwave reaction tube, 2mmol of 60% NaH was added, dissolved in 3mL anhydrous DMSO, and then 0.1mmol of trimethylsulfoxide iodide and 0.5mmol of phenyl ethane oxide were added, and the mixture was heated to 110℃by microwaves to react for 10 minutes. After the reaction is completed, water is used for extraction, triethylamine alkalized silica gel is used for column separation after the extraction, eluent PE/EA=50:1 is used for separation, and phenyl methyl ketone can be obtained, and the yield is 20%.
Comparative example 3
In a 25mL flask, 1.6mmol of 60% NaH was added, dissolved in 10mL of anhydrous DMSO, and 1.6mmol of trimethylsulfoxide iodide was added to react at room temperature for 1 hour, and 1mmol of phenyloxirane was added to react at 70℃for 1 day, and the product was phenyloxetane in 40% yield.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention and not for limiting it, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that: the technical scheme of the invention can be modified or replaced by the same, and the modified technical scheme cannot deviate from the spirit and scope of the technical scheme of the invention.
Claims (6)
1. The microwave-assisted synthesis method of the methyl ketone compound is characterized by comprising the following steps of: adding a catalyst NaH and an organic solvent into a microwave reaction tube, dissolving the catalyst NaH in the organic solvent, then adding a catalyst trimethyl sulfoxide iodide and a monosubstituted ethylene oxide compound, reacting for 30 minutes under the condition of microwave heating, extracting after the reaction is finished, eluting and separating by using a chromatographic column, and separating to obtain a colorless oily compound;
wherein the monosubstituted epoxy ethane compound is one of styryl epoxy ethane, phenyl epoxy ethane, p-chlorophenyl epoxy ethane, p-methylphenyl epoxy ethane and 2-bromophenyl benzyl epoxy ethane;
the catalyst NaH is 60 percent NaH, and the dosage is 1-3mmol;
the dosage of the catalyst, namely the trimethyl iodized sulfoxide, is 0.05-0.2mmol, and the dosage of the monosubstituted ethylene oxide compound is 0.1-1mmol;
the volume of the microwave reaction tube was 10mL and the temperature of microwave heating was 110 ℃.
2. The method for synthesizing microwave-assisted methyl ketone compounds according to claim 1, wherein the method comprises the following steps: the organic solvent is anhydrous dimethyl sulfoxide, and the dosage of the organic solvent is 1-5mL.
3. The method for synthesizing microwave-assisted methyl ketone compounds according to claim 1, wherein the method comprises the following steps: the amount of organic solvent used was 3mL.
4. The method for synthesizing microwave-assisted methyl ketone compounds according to claim 1, wherein the method comprises the following steps: the amount of NaH catalyst used was 2mmol.
5. The method for synthesizing microwave-assisted methyl ketone compounds according to claim 1, wherein the method comprises the following steps: the dosage of the catalyst, namely the trimethyl iodized sulfoxide is 0.1mmol, and the dosage of the monosubstituted oxirane compound is 0.5mmol.
6. The method for synthesizing microwave-assisted methyl ketone compounds according to claim 1, wherein the method comprises the following steps: eluent PE/EA from column elution = 50-100:1.
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