CN108863739B - Method for constructing cyclohexene derivative from arylethanone, 2-arylpropylene and dimethyl sulfoxide - Google Patents
Method for constructing cyclohexene derivative from arylethanone, 2-arylpropylene and dimethyl sulfoxide Download PDFInfo
- Publication number
- CN108863739B CN108863739B CN201810615199.7A CN201810615199A CN108863739B CN 108863739 B CN108863739 B CN 108863739B CN 201810615199 A CN201810615199 A CN 201810615199A CN 108863739 B CN108863739 B CN 108863739B
- Authority
- CN
- China
- Prior art keywords
- reaction
- dimethyl sulfoxide
- cyclohexene
- substituent
- constructing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- C07C45/61—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
- C07C45/67—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 isomerisation; by change of size of the carbon skeleton
- C07C45/68—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 isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Abstract
The invention discloses a method for constructing a cyclohexene derivative by arylethanone, 2-arylpropylene and dimethyl sulfoxide, which comprises the steps of carrying out one-pot reaction on arylethanone and 2-arylpropylene in a dimethyl sulfoxide solution system containing potassium persulfate and/or sodium persulfate to obtain the cyclohexene derivative; the method is implemented by a one-pot method, has mild reaction conditions, does not need an additional catalyst, has good selectivity and high yield, and is beneficial to industrial production.
Description
Technical Field
The invention relates to a method for synthesizing cyclohexene derivatives, in particular to a method for jointly constructing cyclohexene by arylethanone, DMSO and 2-arylpropylene, and belongs to the field of organic synthesis.
Background
The cyclohexene derivatives are a series of cyclohexene derivatives derived from cyclohexene ring parent by introducing different substituent groups on cyclohexene, and the cyclohexene derivatives reported at present are mainly used for medicines and perfumes. For example, Chinese patent (CN106496100A) discloses a cyclohexene compound, the structural formula of which is as follows:
(wherein, R is selected from H, M ion, C1-C6 alkyl; R6、R7、R8Independently selected from: H. c1-C4 alkyl, etc.; r1Selected from: amino groups, etc.; r2Selected from: H. C1-C4 alkyl, etc.; m is selected from: 0, 1; r3、R4Independently selected from: H. C1-C4 alkyl, etc.; n is selected from: 1-4; x is selected from: CH (CH)2O, S, etc.; r5Selected from: H. C1-C4 alkyl, etc.; r9、R10Independently selected from: H. C1-C4 alkyl and the like) which are mainly used as drugs for inhibiting influenza viruses, such as wild type and drug-resistant influenza viruses, have good inhibitory activity. For example, a cyclohexene derivative as a perfume is disclosed in the patent (CN 103068785A) of the switzerland chewden company, ltd, in china, and has the following structural formula:
(wherein R is an isobutyl group at C-3 or C-4; R 'is a hydrogen at C-3 or C-4 and the bond between C-3 and C-4 together with the dotted line represents a double bond; or R' is-CH 2-and together with C-3 and C-4 represents a cyclopropane ring and the bond between C-3 and C-4 together with the dotted line represents a single bond; R1 and R2 independently represent a group selected from hydrogen etc.; R3 is selected from methyl etc.; and R4 is hydroxyl and R5 is hydrogen; or R1, R2 and R3 independently represent a group selected from hydrogen, methyl etc.; and R4 and R5 together with the carbon atom to which they are attached represent a carbonyl group), compounds of this type having appreciable floral and citrus (hesperidic) notes, can be used as perfume ingredients. Based on the importance of cyclohexene derivatives in the prior art, the method for synthesizing cyclohexene becomes a research hotspot.
The existing cyclohexene is mainly obtained by monocyclic aromatic selective hydrogenation, transition metal is required to be used as a hydrogenation catalyst in the selective hydrogenation process, and the hydrogenation reaction conditions are harsh and difficult to control. Although cyclohexene can be obtained by the method, the method is not suitable for synthesizing most cyclohexene derivatives, and the main reason is that a substituent is easily influenced by hydrogenation reaction, and particularly when the substituent contains an unsaturated group or an active group, the target product of the cyclohexene derivative is difficult to obtain by hydrogenation reduction. The synthesis method of cyclohexene derivatives reported in the prior art mainly utilizes a diels alder addition reaction. The Diels-Alder addition reaction is an ideal method for constructing six-membered rings, and can utilize the reaction of conjugated diene and substituted olefin (dienophile) to generate substituted cyclohexene, such as the classical reaction, the synthesis of 3, 4-dimethylcyclohexene or 3, 5-dimethylcyclohexene from 1, 3-pentadiene and propylene, and the synthesis of 1, 4-dimethylcyclohexene or 2, 4-dimethylcyclohexene from isoprene and propylene. The patent (CN 102725258A) applied by Amelis company in China in the United states discloses cyclohexene 1, 4-carboxylate, and proposes that the cyclohexene 1, 4-carboxylate is synthesized by diels Alder addition reaction of muconic acid or carboxylate derivatives thereof and acrylic acid or esters thereof and the like. The diels alder addition reaction is a reversible reaction, it is difficult to obtain a high yield, and the addition reaction has two additions, the selectivity is poor, it is difficult to obtain a pure single addition, and in addition, the diels alder addition reaction often uses lewis acid as a catalyst, and lewis acid also has a promoting effect on the polymerization of the alkene, thereby generating a side reaction.
Disclosure of Invention
Aiming at the defects of the existing cyclohexene construction method, the invention aims to provide a method for constructing a cyclohexene derivative by using aryl ethanone to provide alpha-carbon, DMSO to provide methyl and 2-aryl propylene to provide propenyl.
In order to realize the technical purpose, the invention also provides a method for constructing the cyclohexene derivative by the arylethanone, the 2-arylpropylene and the dimethyl sulfoxide, which comprises the steps of carrying out one-pot reaction on the arylethanone and the 2-arylpropylene in a dimethyl sulfoxide solution system containing potassium persulfate and/or sodium persulfate to obtain the cyclohexene derivative;
the cyclohexene derivative has a structure of formula 1:
the arylethanones have the structure of formula 2:
the 2-arylpropene has the structure of formula 3:
wherein the content of the first and second substances,
Ar1is selected from aryl;
Ar2selected from aryl or aromatic heterocyclic radical.
In the 2-arylpropenes of the present invention, Ar1More preferably phenyl, substituted phenyl or naphthyl. Ar (Ar)1When the substituent is selected from substituted phenyl, the number of the substituent contained in the substituted phenyl is 1-2, and the substituent is selected from at least one of halogen substituent and alkyl. Halogen substituents such as fluorine, chlorine, bromine, iodine, and the like. Alkyl is C1～C10Alkyl groups of (a); more preferably C1～C5The lower alkyl group of (2) such as methyl, ethyl, propyl, etc., may also be a branched alkyl group such as isopropyl, isobutyl, etc. The choice of 2-arylpropenes is limited to the choice of aryl substituents which provide a large conjugated system enabling the methyl group on the alkenyl group to be sufficiently reactive to participate in the cyclisation. The aryl substituent can not be replaced by other substituent groups at will, and the target product can not be obtained by replacing aryl with aromatic heterocycle, alkyl and the like. When Ar is1When substituted phenyl is selected, the substituent is preferably para to the alkenyl, and may be a weak electron-donating group such as alkyl or a weak electron-withdrawing group such as halogen. However, it is difficult to obtain an ideal yield from a strongly electron-withdrawing group such as an amino group and an alkoxy group, and a strongly electron-withdrawing group such as a nitro group.
In the arylethanones of the invention, Ar2More preferred is phenyl, substituted phenyl, naphthyl, furyl, pyridyl or thienyl. Ar (Ar)2When the substituent is selected from substituted phenyl, the number of the substituent contained in the substituted phenyl is 1-2, and the substituent is selected from alkoxy, alkylthio, alkyl, trifluoromethoxy, halogen substituent, cyano, ester group, nitro, and the like,At least one of hydroxyl groups. Preferred alkoxy is C1～C10Further preferably C1～C5Alkoxy group of (2). Preferred alkylthio is C1～C10Alkylthio group of (3), more preferably C1～C5Alkylthio groups of (2). Preferred alkyl is C1～C10Alkyl groups of (a); more preferably C1～C5The lower alkyl group of (2) such as methyl, ethyl, propyl, etc., may also be a branched alkyl group such as isopropyl, isobutyl, etc. Preferred halogen substituents are fluorine, chlorine, bromine, iodine, and the like. Preferred ester groups are methoxyacetyl groups.
In the technical scheme of the invention, the arylethanone has wide selection range and Ar of the arylethanone2Aryl or aromatic heterocyclic groups can be selected, and all the substituent groups contain conjugated groups, and form a large conjugated system with carbonyl, so that the activity of alpha-carbon is improved. Ar (Ar)2When the substituted phenyl is selected, the yield of various common substituent groups on the substituted phenyl is kept about 60 percent. The position of the substituent is not particularly limited, and may be ortho, meta or para to the carbonyl group.
In a preferred embodiment, the ratio of the total molar weight of the potassium persulfate and the sodium persulfate to the molar weight of the arylethanone is 0.5-1.5: 1. More preferably 0.8 to 1.2: 1.
In a preferred scheme, the molar ratio of the arylethanone to the 2-arylpropylene is 1: 1-1.5.
In the preferable scheme, the concentration of the arylethanone in a dimethyl sulfoxide solution system is 0.1-0.5 mol/L. Dimethyl sulfoxide serves mainly as a benign solvent on the one hand and as a reaction substrate on the other hand, two methyl groups are provided by two dimethyl sulfoxides as two carbon atoms in the cyclohexene ring.
In a preferred embodiment, the reaction conditions are as follows: and reacting for 18-30 h at the temperature of 100-160 ℃ in a protective atmosphere. More preferred conditions are: reacting for 20-28 h at 130-150 ℃ in a nitrogen atmosphere. The protective atmosphere is generally nitrogen or an inert atmosphere.
In the invention, acetophenone, dimethyl sulfoxide and 2-phenyl propylene are used together to construct a cyclohexene ring for para-reactionThe mechanism should be explained. After reviewing and referring to relevant documents, a series of mechanism research experiments were designed, as shown in the following reaction equations (1) to (6). In order to prove whether the reaction goes through the reaction course of a free radical, the reaction (1) is designed, 2.0 equivalent (relative to acetophenone) of 2, 6-di-tert-butyl-p-cresol (BHT) is added under standard reaction conditions, the reaction is carried out for 8 hours, and the generation of a target product of the cyclohexene derivative can still be successfully detected through GC-MS, which indicates that the reaction is not inhibited and does not go through the reaction course of a free radical. To verify the presence of the reaction intermediates in the reaction, acetophenone was reacted with dimethyl sulfoxide and 2-phenylpropylene under standard reaction conditions for 8 hours, and by detection in GC-MS, the presence of compound B and compound C was detected in addition to the target cyclohexene derivative. In order to prove whether the compounds B and C are intermediates in the cyclohexene construction process, the reaction (2) and the reaction (3) are designed, the compound B is used as a raw material to replace 2-phenylpropylene, the reaction is carried out under standard conditions, and the compound C is used as a raw material to replace acetophenone. To further clarify the source of compound B, reaction (4) was further designed to react 2-phenylpropylene with dimethylsulfoxide directly under standard conditions, and the presence of compound B was detected by GC-MS, while compound A was also obtained. To further clarify the source of compound C, reaction (5) was further designed to react 2-phenylpropylene with dimethylsulfoxide directly under standard conditions, and the presence of compound C was detected by GC-MS, while compound D was also obtained. To obtain a more accurate verification of whether dimethyl sulfoxide is involved in cyclohexene cyclization, reaction (6) was designed to replace conventional dimethyl sulfoxide with isotopically labeled deuterated dimethyl sulfoxide under standard conditions, successfully detecting the presence of deuterium in the cyclohexene product and at two carbon atoms, indicating that two methyl groups are provided by dimethyl sulfoxide. Standard reaction conditions: in N2Next, acetophenone (0.5mmol), α -methylstyrene (0.75mmol) and DMSO (2mL),reacting for 24 hours at 140 ℃.
Reaction formula (1):
reaction type (2)
Reaction formula (3):
reaction type (4)
Reaction formula (5):
reaction formula (6):
according to the experiment, the invention provides a reasonable mechanism for constructing cyclohexene by acetophenone, dimethyl sulfoxide and 2-phenyl propylene: the following reaction equation. First, adopt K2S2O8Activating DMSO to obtain DMSO converted into dimethyl sulfide positive ions, simultaneously 2-phenylpropylene releases hydrogen protons to be converted into 2-phenylpropylene negative ions, acetophenone also releases hydrogen protons to be converted into acetophenone negative ions, the 2-phenylpropylene negative ions and the acetophenone negative ions are easy to couple with the dimethyl sulfide positive ions to generate sulfur methyl ether compounds A and D, and the sulfur methyl ether compounds A and D are in K2S2O8Under the action of oxidation, removing the micromolecule methyl mercaptan compound through a demethylation reaction to obtain compounds B and C, and carrying out Diels Alder reaction on the compound B and the compound C to finally obtain a target product.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the 1-position aryl substituent and the 4-position acyl substituent on the cyclohexene ring are easy to modify groups, and provide an effective intermediate for the synthesis of a compound taking cyclohexene as a parent.
2) According to the invention, aryl ethanone provides alpha carbon, 2-aryl propylene provides propenyl, and dimethyl sulfoxide provides methyl to successfully construct the cyclohexene derivative for the first time, so that a brand-new synthesis idea is provided for the construction of a cyclohexene ring.
3) The cyclohexene derivative of the invention does not need to use a catalyst in the synthesis process, and compared with the existing Diels-Alder reaction, the use of a Lewis catalyst is avoided, and the possibility of side reaction of olefin polymerization is reduced.
4) In the synthesis process of the cyclohexene derivative, aryl ethyl ketone, 2-aryl propylene and dimethyl sulfoxide are used as basic raw materials, and are conventional chemical raw materials, so that the cyclohexene derivative is low in cost and beneficial to industrial production.
5) The cyclohexene derivative synthesis process adopts a one-pot reaction, has mild reaction conditions and simple operation, and meets the requirements of industrial production.
6) The cyclohexene derivative synthesis process has high utilization rate of raw materials and the product yield is about 60 percent.
7) The application range of the cyclohexene derivative in the synthesis process of the cyclohexene derivative is wider, the cyclohexene derivative with various substituent groups can be constructed, the position selectivity of the substituent groups is strong, and the 1, 4-disubstituted cyclohexene derivative is obtained.
Drawings
FIG. 1 is a single crystal structural diagram of a compound (2,3,4,5-tetrahydro- [1,1' -biphenyl ] -4,4-diyl) bis (phenylmethanone).
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
All reactions were performed in Schlenk tubes unless otherwise noted.
All reaction starting solvents were obtained from commercial sources and used without further purification.
The product is separated by silica gel chromatographic column and silica gel (granularity is 300-400 meshes).
1H NMR (400MHz), 13C NMR (100MHz) and 19F NMR (376MHz) measurements were performed using a Bruker ADVANCE III spectrometer with CDCl3As solvent, TMS as internal standard, chemical shifts in parts per million (ppm) and reference shifts of 0.0ppm tetramethylsilane. The following abbreviations (or combinations thereof) are used to explain the multiplicity: s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, br is broad. Coupling constant J is in Hertz (Hz). Chemical shifts are expressed in ppm, with the center line for the triplet state referenced to deuterated chloroform at 77.0ppm or the center line for the heptad state referenced to deuterated DMSO at 39.52 ppm.
The GC-MS adopts a GC-MS QP2010 device for detection, the HRMS adopts an Electron Ionization (EI) method for measurement, the type of the mass analyzer is TOF, and the EI is detected by an Esquire 3000plus instrument.
1. Condition optimization experiment:
the cyclohexene ring is constructed by acetophenone, dimethyl sulfoxide and 2-phenyl propylene, and a plurality of influencing factors such as oxidant and dosage thereof, reaction temperature, reaction solvent and additive are discussed to search for optimal reaction conditions.
The specific reaction process is as follows: acetophenone (0.5mmol), alpha-methylstyrene (0.75mmol), oxidant, additive (0.5mmol) and DMSO (2mL) in N2And reacting for 24 hours under the atmosphere.
The reaction route is as follows:
table 1: yield of target product cyclohexene derivative under different reaction conditions
1) Selection of additives
As shown in Table 1, the use of the additive has a great influence on the reaction, and a large number of experiments show that, as shown in items 1-6 and 11 in Table 1, no benign additive which is beneficial to improving the reaction efficiency and increasing the yield, such as DABCO, DBU, K and the like, has been found in the reaction process of constructing a cyclohexene ring by acetophenone, dimethyl sulfoxide and 2-phenylpropylene2CO3、Cs2CO3、Et3When alkaline substances such as N or NaOAc and the like are used as additives, the reaction is obviously inhibited, and the target product cyclohexene derivative is basically not obtained.
3) Selection of oxidizing agent
The invention tries a plurality of common oxidants in the field, such as items 11 and 12-18 in table 1, and oxidants such as potassium (sodium) persulfate, organic peroxide, inorganic hydrogen peroxide and the like are found to have good reaction effect only when the potassium (sodium) persulfate is used as the oxidant, and when tert-butyl hydroperoxide (TBHP), DTBP or hydrogen peroxide (H) is used2O2) Since the target product is hardly obtained as the oxidizing agent, potassium (sodium) persulfate is selected as the most preferable oxidizing agent.
4) Selection of the quantity of oxidant
After determining potassium persulfate, sodium persulfate and the like as the optimal oxidants, the influence of different amounts of the oxidants on the reaction is explored. As in items 11, 19 and 20 of table 1. When the amount of the oxidant is 0.5-1 equivalent, the conversion rate of the raw materials and the yield of the product are increased with the increase of the amount of the oxidant. And when the amount of the oxidizing agent is more than 1 equivalent, the yield is remarkably decreased. Therefore, 1 equivalent of potassium persulfate or sodium persulfate is the optimum amount for the reaction.
5) Selection of reaction temperature
The reaction temperature is an important factor affecting the chemical reaction process, and in order to obtain the optimum reaction temperature, the yield of the reaction at different temperatures was investigated, as in items 7 to 11 in Table 1. The target product can not be obtained basically at the temperature of less than 100 ℃, the reaction yield is obviously improved when the temperature reaches more than 120 ℃, the reaction yield reaches the highest when the temperature is raised to 140 ℃, and the reaction side reaction is obvious when the temperature is higher than 140 ℃. Thus, 140 ℃ is the optimum temperature for the reaction.
6) Selection of reaction solvent
Since DMSO is used as a reaction substrate and a solvent in the process of synthesizing dihydropyran, the DMSO is not replaceable by other solvents. The solvent of the invention can adopt DMSO, and can also adopt a mixed solvent of DMSO and other solvents.
2. Selection range of reaction substrates:
after the optimal cyclohexene synthesis conditions are determined, the substrate range and applicability of the reaction are explored, and the experimental results are shown in tables 2 and 3. Table 2 shows the results of different arylethanones reacted with 2-phenylpropene and DMSD. As can be seen from Table 2, aryl ketones, aryl heterocyclic ketones, etc. can effectively synthesize corresponding cyclohexene ring structures with 2-phenylpropene and DMSD under standard reaction conditions, and the yield of the target product is about 60%. Moreover, a large number of experiments show that the substituent on the benzene ring of the acetophenone containing the substituent has no obvious influence on the reaction, and various substituted acetophenones can be successfully used for constructing the cyclohexene derivative with 2-phenylpropene and DMSD. Mainly aryl or aromatic heterocyclic radical can provide a large conjugated system, can activate alpha methyl and easily lose hydrogen protons. Cyclohexene could not be constructed with other nonconjugated groups such as alkyl etc. with 2-phenylpropene and DMSD.
(1) The reaction equation for different arylethanones with 2-phenylpropene and DMSD is as follows:
weighing potassium peroxodisulfate (K)2S2O8) (135mg,0.5mmol) was placed in a 25ml Schlenk reaction tube, and added theretoDimethylsulfoxide (DMSO, 2ml), arylethanone (0.5mmol), 2-phenylpropene (89mg, 0.75mmol), and nitrogen gas was purged. Stirring was carried out at 140 ℃ for 24 hours. After completion of the reaction, it was cooled to room temperature, water (4ml) was added, and extraction was performed with ethyl acetate (3 x 5ml) and anhydrous Na2SO4Drying, distilling off the solvent under reduced pressure, and separating by a silica gel column (200-300 meshes) to obtain the target product.
TABLE 2 results of different arylethanones reacted with 2-phenylpropene and DMSD
(2) The reaction equation for arylethanones with different 2-arylpropenes and DMSD is as follows:
weighing potassium peroxodisulfate (K)2S2O8) (135mg,0.5mmol) was placed in a 25ml Schlenk reaction tube, to which was added dimethylsulfoxide (DMSO, 2ml), acetophenone (60mg, 0.5mmol), 2-aryl-propene (99mg, 0.75mmol), and nitrogen gas was introduced. Stirring was carried out at 140 ℃ for 24 hours. After completion of the reaction, it was cooled to room temperature, water (4ml) was added, and extraction was performed with ethyl acetate (3 x 5ml) and anhydrous Na2SO4Drying, distilling off the solvent under reduced pressure, and separating by a silica gel column (200-300 meshes) to obtain the target product.
Table 3 shows the reaction results of different 2-aryl propenes with acetophenone and DMSD, and experimental results show that the substituent at the 2-position of propene must be a group having a large conjugated system, such as aryl, other aromatic heterocyclic rings, alkyl, etc., which cannot meet the requirements, and the aryl of the large conjugated system is favorable for improving the activity of α -methyl. The substituent on the aryl is also selected according to the requirement, and can not be a substituent group with stronger electron pushing or pulling capacity, such as nitro, alkoxy and the like, while the substituent group with stronger electron pushing or pulling capacity, such as halogen, alkyl and the like, can meet the requirement.
TABLE 3 results of acetophenone reaction with different 2-arylpropenes and DMSD
Structural characterization of some dihydropyran derivatives in tables 2-3:
phenyl(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
(dd,J＝34.5,14.1Hz,2H),2.18(d,J＝12.0Hz,1H),1.88(ddd,J＝21.3,12.2,8.9Hz,1H).
13C NMR(101MHz,CDCl3)δ203.32,141.75,136.29,133.03,128.74,128.37, 128.34,126.92,125.08,123.14,41.31,28.76,27.21,26.29.
(3,4-dimethoxyphenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
6.21(d,J＝4.2Hz,1H),3.98(s,3H),3.97(s,3H),3.64–3.53(m,1H),2.64–2.60 (m,2H),2.52(ddd,J＝42.4,12.1,3.8Hz,2H),2.22–2.14(m,1H),1.92(ddd,J＝ 16.9,10.5,5.9Hz,1H).
13C NMR(101MHz,CDCl3)δ201.93,153.26,149.23,141.74,136.23,129.43, 128.31,126.88,125.03,123.25,122.76,110.58,110.03,56.10,56.02,40.82,29.08, 27.24,26.54.
(4-methoxyphenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
7.41(d,J＝7.4Hz,2H),7.33(t,J＝7.6Hz,2H),7.23(d,J＝7.3Hz,1H),6.97(d,J＝ 8.8Hz,2H),6.19(d,J＝4.2Hz,1H),3.88(s,3H),3.56(ddd,J＝12.0,6.6,3.8Hz, 1H),2.63–2.57(m,2H),2.57–2.35(m,2H),2.21–2.11(m,1H),1.89(tt,J＝13.1, 8.6Hz,1H).
13C NMR(101MHz,CDCl3)δ201.85,163.44,141.78,136.23,130.61,129.26, 128.30,126.86,125.05,123.28,113.85,55.50,40.95,28.92,27.26,26.43.
(4-(methylthio)phenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
3.55(t,J＝10.7Hz,1H),2.59(s,2H),2.53(s,3H),2.43(d,J＝17.7Hz,2H),2.16(d, J＝12.5Hz,1H),1.87(dd,J＝20.2,11.5Hz,1H).
13C NMR(101MHz,CDCl3)δ202.30,145.77,141.74,136.27,132.52,128.79, 128.32,126.90,125.15,125.06,123.16,41.09,28.81,27.21,26.34,14.82.
(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(p-tolyl)methanone；
10.3Hz,1H),2.59(s,2H),2.57–2.44(m,2H),2.43(s,3H),2.17(d,J＝12.9Hz, 1H),1.93–1.83(m,1H).
13C NMR(101MHz,CDCl3)δ202.94,143.78,141.77,136.24,133.76,129.39, 128.47,128.29,126.86,125.05,123.22,41.16,28.81,27.22,26.33,21.64.
(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(m-tolyl)methanone；
2.43(s,3H),2.18(d,J＝12.3Hz,1H),1.89(dt,J＝29.7,10.5Hz,1H).
13C NMR(101MHz,CDCl3)δ203.58,141.78,138.54,136.34,133.78,128.88, 128.59,128.33,126.91,125.56,125.08,123.19,41.33,28.83,27.22,26.29,21.46.
(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(o-tolyl)methanone；
1H),2.56(d,J＝11.8Hz,2H),2.49(s,2H),2.45(s,3H),2.15(d,J＝14.4Hz,1H), 1.83(dt,J＝18.3,11.4Hz,1H).
13C NMR(101MHz,CDCl3)δ207.83,141.77,138.45,137.62,136.36,131.76, 130.81,128.32,127.61,126.91,125.65,125.07,123.03,44.40,28.18,27.13,25.61, 20.84.
(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(4-(trifluoromethoxy)phenyl)methanone；
2.17(d,J＝12.7Hz,1H),1.95–1.82(m,1H).
19F NMR(376MHz,CDCl3)δ-57.56.
13C NMR(101MHz,CDCl3)δ201.71,152.58,141.62,136.35,134.49,130.37, 128.35,126.99,125.07,122.85,120.54,41.40,28.65,27.13,26.20.
(4-fluorophenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
2.39(m,2H),2.17(d,J＝12.4Hz,1H),1.88(dt,J＝12.2,9.0Hz,1H).
13C NMR(101MHz,CDCl3)δ201.67,141.65,136.31,130.96,128.32,126.94, 125.05,122.96,115.91,115.70,41.26,28.73,27.15,26.25.
(4-chlorophenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
3.1Hz,2H),2.48(dd,J＝33.7,14.1Hz,2H),2.16(d,J＝13.0Hz,1H),1.94–1.81(m,1H).
13C NMR(101MHz,CDCl3)δ202.07,141.64,139.45,136.34,134.56,129.79, 129.05,128.34,126.97,125.06,122.90,41.33,28.68,27.14,26.20.
4-(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-carbonyl)benzonitrile；
2H),2.49(dd,J＝30.1,14.0Hz,2H),2.18(d,J＝12.0Hz,1H),1.96–1.82(m,1H).
13C NMR(101MHz,CDCl3)δ201.89,141.48,139.35,136.43,132.64,128.76, 128.37,127.08,125.07,122.52,117.98,116.29,41.69,28.45,27.02,26.01.
methyl 4-(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-carbonyl)benzoate；
21.0,10.6Hz,1H).
13C NMR(101MHz,CDCl3)δ202.79,166.25,141.61,139.61,136.36,133.79, 129.95,128.28,126.97,125.06,122.81,52.48,41.70,28.56,27.11,26.11.
(4-nitrophenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
8.0,5.4,2.7Hz,1H),2.67–2.61(m,2H),2.60–2.44(m,2H),2.26–2.18(m,1H), 1.98–1.87(m,1H).
13C NMR(101MHz,CDCl3)δ201.69,150.28,141.45,140.87,136.46,129.33, 128.36,127.08,125.06,123.98,122.44,41.96,28.42,27.01,25.98.
(3-nitrophenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
(s,2H),2.51(dd,J＝27.3,13.9Hz,2H),2.19(d,J＝13.7Hz,1H),1.98–1.85(m, 1H).
13C NMR(101MHz,CDCl3)δ201.01,148.60,141.49,137.56,136.47,133.97, 130.06,128.38,127.33,127.08,125.09,123.20,122.48,41.61,28.52,27.01,26.05.
(2-nitrophenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
1H),3.02(d,J＝10.2Hz,1H),2.71–2.55(m,2H),2.54–2.40(m,2H),2.22(d,J＝ 13.0Hz,1H),1.95–1.81(m,1H).
13C NMR(101MHz,CDCl3)δ205.58,145.78,141.62,137.69,136.38,134.33, 130.48,128.31,128.02,126.97,125.09,124.58,122.60,46.62,28.17,27.13,25.57.
(2-hydroxyphenyl)(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
1H),6.91(t,J＝7.5Hz,1H),6.17(s,1H),3.69–3.55(m,1H),2.61(s,2H),2.58– 2.40(m,2H),2.17(d,J＝13.7Hz,1H),1.93(dd,J＝15.5,7.2Hz,1H).
13C NMR(101MHz,CDCl3)δ209.53,163.17,141.57,136.43,136.36,129.87, 128.37,127.03,125.08,122.77,118.94,118.88,118.45,40.94,28.91,27.13,26.47.
naphthalen-2-yl(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
7.6Hz,2H),7.35(t,J＝7.3Hz,2H),7.24(s,1H),6.22(s,1H),3.78(s,1H),2.65(s, 2H),2.56(dd,J＝27.1,14.2Hz,2H),2.25(d,J＝12.5Hz,1H),2.01–1.90(m,1H).
13C NMR(101MHz,CDCl3)δ203.33,141.77,136.34,135.63,133.64,132.69, 129.87,129.66,128.66,128.52,128.40,127.85,126.99,126.86,125.12,124.34, 123.21,41.39,29.01,27.26,26.43.
furan-2-yl(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
2.6Hz,1H),2.64(d,J＝3.0Hz,2H),2.61–2.42(m,2H),2.21(dd,J＝11.4,3.4Hz, 1H),2.00–1.87(m,1H).
13C NMR(101MHz,CDCl3)δ192.33,152.37,146.38,141.75,136.24,128.30, 126.89,125.06,122.94,117.31,112.24,42.04,28.18,27.17,25.91.
18.(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(thiophen-2-yl)methanone；
1H),2.61(d,J＝3.9Hz,2H),2.59–2.36(m,2H),2.21(d,J＝13.3Hz,1H),2.01–1.87(m,1H).
13C NMR(101MHz,CDCl3)δ196.26,143.81,141.70,136.26,133.74,131.76, 128.34,128.19,126.94,125.07,122.97,43.09,28.94,27.20,26.59.
pyridin-2-yl(2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)methanone；
6.2Hz,1H),2.71–2.58(m,2H),2.51(d,J＝11.7Hz,2H),2.20(d,J＝11.7Hz,1H),1.85(dt,J＝ 11.2,5.9Hz,1H).
13C NMR(101MHz,CDCl3)δ204.55,152.97,148.98,142.09,136.99,136.30, 128.26,127.04,126.75,125.12,123.30,122.46,39.99,28.29,27.16,25.68.
(4'-methyl-2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(phenyl)methanone；
2H),2.34(s,3H),2.17(d,J＝11.2Hz,1H),1.93–1.83(m,1H).
13C NMR(101MHz,CDCl3)δ203.40J,138.89,136.57,136.34,136.09,132.98, 129.01,128.71,128.35,124.93,122.26,41.37,28.76,27.24,26.29,21.07
(4'-fluoro-2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(phenyl)methanone；
2.18(d,J＝13.6Hz,1H),1.94–1.82(m,1H).
13C NMR(101MHz,CDCl3)δ203.20,161.98(d,J＝245.7Hz),137.86,136.25, 135.35,133.05,128.74,128.35,126.57(d,J＝7.8Hz),123.03,115.07(d,J＝21.2 Hz),41.17,28.66,27.31,26.21.
(4'-chloro-2,3,4,5-tetrahydro-[1,1'-biphenyl]-4-yl)(phenyl)methanone；
Hz,2H),2.18(d,J＝12.8Hz,1H),1.94–1.81(m,1H).
13C NMR(101MHz,CDCl3)δ203.10,140.14,136.23,135.24,133.06,132.58, 128.75,128.40,128.34,126.33,123.73,41.11,28.66,27.08,26.17。
Claims (6)
1. a method for constructing a cyclohexene derivative by using arylethanone, 2-arylpropylene and dimethyl sulfoxide is characterized by comprising the following steps: performing one-pot reaction on arylethanone and 2-arylpropylene in a dimethyl sulfoxide solution system containing potassium persulfate and/or sodium persulfate to obtain a cyclohexene derivative;
the cyclohexene derivative has a structure of formula 1:
formula 1
The arylethanones have the structure of formula 2:
formula 2
The 2-arylpropene has the structure of formula 3:
formula 3
Wherein the content of the first and second substances,
Ar1selected from naphthyl or substituted phenyl; ar (Ar)1When the substituent is selected from substituted phenyl, the number of the substituent contained in the substituted phenyl is 1-2, and the substituent is selected from halogen substituent and C1~C10At least one of alkyl groups;
Ar2selected from phenyl, substituted phenyl, naphthyl, furyl, pyridyl or thienyl; ar (Ar)2When the substituent is selected from substituted phenyl, the number of the substituent contained in the substituted phenyl is 1-2, and the substituent is selected from C1~C10Alkoxy radical, C1~C10Alkylthio radical, C1~C10At least one of alkyl, trifluoromethoxy, halogen substituent, cyano, methoxyacetyl, nitro and hydroxyl;
the reaction conditions are as follows: and reacting for 18-30 h at the temperature of 100-160 ℃ in a protective atmosphere.
2. The method for constructing cyclohexene derivatives from arylethanones, 2-arylpropenes and dimethyl sulfoxide according to claim 1, wherein: ar (Ar)1When selected from substituted phenyl groups, the substituted phenyl groups contain para substituents.
3. The method for constructing cyclohexene derivatives from arylethanones, 2-arylpropenes and dimethyl sulfoxide according to claim 1, wherein: the ratio of the total molar weight of the potassium persulfate and the sodium persulfate to the molar weight of the arylethanone is 0.5-1.5: 1.
4. The method for constructing cyclohexene derivatives from arylethanones, 2-arylpropenes and dimethyl sulfoxide according to claim 1, wherein: the molar ratio of the arylethanone to the 2-arylpropene is 1: 1-1.5.
5. The method for constructing cyclohexene derivatives from arylethanones, 2-arylpropenes and dimethyl sulfoxide according to claim 1, wherein: the concentration of the arylethanone in the dimethyl sulfoxide solution system is 0.1-0.5 mol/L.
6. The method for constructing cyclohexene derivatives from arylethanones, 2-arylpropenes and dimethyl sulfoxide according to claim 1, wherein: the reaction conditions are as follows: reacting for 20-28 h at 130-150 ℃ in a nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810615199.7A CN108863739B (en) | 2018-06-14 | 2018-06-14 | Method for constructing cyclohexene derivative from arylethanone, 2-arylpropylene and dimethyl sulfoxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810615199.7A CN108863739B (en) | 2018-06-14 | 2018-06-14 | Method for constructing cyclohexene derivative from arylethanone, 2-arylpropylene and dimethyl sulfoxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108863739A CN108863739A (en) | 2018-11-23 |
| CN108863739B true CN108863739B (en) | 2021-01-12 |
Family
ID=64338995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810615199.7A Active CN108863739B (en) | 2018-06-14 | 2018-06-14 | Method for constructing cyclohexene derivative from arylethanone, 2-arylpropylene and dimethyl sulfoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108863739B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248478B (en) * | 2020-02-10 | 2022-06-28 | 河南工业大学 | Method for constructing pyridine derivative containing gamma-chiral center by cross-coupling of visible light asymmetric catalysis olefin |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759458A (en) * | 2016-08-22 | 2018-03-06 | 沅江华龙催化科技有限公司 | α, the method for β unsaturation aryl ketones compounds are synthesized by dimethyl sulfoxide (DMSO) and aryl methyl ketone |
-
2018
- 2018-06-14 CN CN201810615199.7A patent/CN108863739B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107759458A (en) * | 2016-08-22 | 2018-03-06 | 沅江华龙催化科技有限公司 | α, the method for β unsaturation aryl ketones compounds are synthesized by dimethyl sulfoxide (DMSO) and aryl methyl ketone |
Non-Patent Citations (5)
| Title |
|---|
| A New Five-Membered Ring Forming Process Based on Palladium(0)-Catalyzed Arylative Cyclization of Allenyl Enones;Tsukamoto, Hirokazu;《Organic Letters》;20080530;第10卷(第13期);2633-2636 * |
| Design of a Small-Molecule Catalyst Using Intramolecular Cation−π Interactions for Enantioselective Diels-Alder and Mukaiyama-Michael Reactions: L-DOPA-Derived Monopeptide•Cu(II) Complex;Ishihara, Kazuaki;《Organic Letters》;20060406;第8卷(第9期);1921-1924 * |
| Tandem Diels-Alder and Retro-Ene Reactions of 1-Sulfenyl- and 1-Sulfonyl-1,3-dienes as a Traceless Route to Cyclohexenes;Jin Choi;《J. Am. Chem. Soc》;20140625;第136卷;9918-9921 * |
| Transition metal-free C(sp3)–H bond coupling among three methyl groups;Yufeng Liu;《Chem. Commun.》;20171231;第53卷;5346-5349 * |
| Transition Metal-Free α‑Csp3‑H Methylenation of Ketones to Form C=C Bond Using Dimethyl Sulfoxide as Carbon Source;Yu-Feng Liu;《The Journal of Organic Chemistry》;20170626;第82卷;7159-7164 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108863739A (en) | 2018-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tiecco et al. | Efficient asymmetric selenomethoxylation and selenohydroxylation of alkenes with a new sulfur containing chiral diselenide | |
| Angnes et al. | Photoredox-catalyzed synthesis of alkylaryldiazenes: formal deformylative C–N bond formation with alkyl radicals | |
| Liu et al. | Synthesis of chroman-4-one and indanone derivatives via silver catalyzed radical ring opening/coupling/cyclization cascade | |
| Tang et al. | “One-pot” sequential preparation of isoquinoline-1, 3 (2H, 4H)-dione derivatives by reacting N-alkyl (aryl)-N-methacryloyl benzamides with benzyl alcohols and sodium benzenesulfinates | |
| CN106946817A (en) | A kind of methene cyclopropanes derivative and ether compound C (sp3) H keys reaction method | |
| CN103524320A (en) | Substituted benzophenone and preparation method thereof | |
| Shankar et al. | An efficient and improved synthesis of 1, 5-diketones: versatile conjugate addition of nucleophiles to α, β-unsaturated enones and alkynones | |
| CN108863739B (en) | Method for constructing cyclohexene derivative from arylethanone, 2-arylpropylene and dimethyl sulfoxide | |
| Miao et al. | Iodine-catalyzed coupling of β-hydroxyketones with aromatic amines to form β-aminoketones and Benzo [h] quinolones | |
| CN108358877B (en) | Furyl o-diketone derivative and preparation method thereof | |
| CN108610248B (en) | Cyclohexene derivative and synthesis method thereof | |
| CN108610249B (en) | Synthetic method of 1, 4-disubstituted cyclohexene derivative | |
| Pandia et al. | Manganese (I) catalyzed cross-coupling of secondary allylic alcohols and primary alcohols | |
| Yang et al. | Construction of C–O bond via cross-dehydrogenative coupling of sp [] C–H bond with phenols catalyzed by copper porphyrin | |
| Li et al. | PhI (OAc) 2-mediated additions of 2, 4-dinitrophenylsulfenamide with methylenecyclopropanes (MCPs) and a methylenecyclobutane (MCB) | |
| Galloway et al. | Progress towards metal-free radical alkylations of quinones under mild conditions | |
| Brinson et al. | Two new anthraquinone photoreactions | |
| JP2021037465A (en) | Aromatic ring redox photocatalyst having high reduction power | |
| CN108610317B (en) | Synthetic method of 3, 6-dihydropyran derivative | |
| JP5504898B2 (en) | Method for producing difluorocyclopropane compound | |
| CN109574818A (en) | A kind of polysubstituted indenone derivative and preparation method thereof | |
| CN108530410B (en) | Method for constructing dihydropyran ring by benzaldehyde, α -methyl styrene compound and dimethyl sulfoxide | |
| CN110452107B (en) | Preparation method of 2-acyl-3, 4-dihydronaphthalene derivative | |
| Yin et al. | Direct Conversion of Aromatic Ketones to Arenecarboxylic Esters via Carbon–Carbon Bond-Cleavage Reactions | |
| CN108675923B (en) | Method for constructing spiro compound by using cyclic ketone compound, 2-aryl propylene and dimethyl sulfoxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |