CN115745836A - Method for inducing reaction of alkyl neopentyl benzene and capture reagent by photocatalyst - Google Patents

Abstract

The application relates to the technical field of synthetic chemistry, in particular to a method for inducing alkyl neopentyl benzene to react with a capture reagent by a photocatalyst, which comprises the following steps: adding alkyl neopentyl benzene shown in the formula I and a capture reagent into nitroalkane solution containing an acridine salt photocatalyst, and carrying out catalytic reaction under the irradiation of blue light to obtain one of the following products;

Description

Method for inducing reaction of alkyl neopentyl benzene and capture reagent by photocatalyst

Technical Field

The application belongs to the technical field of synthetic chemistry, and particularly relates to a method for inducing alkyl neopentyl benzene to react with a capture reagent by using a photocatalyst.

Background

In recent years, photo-redox catalysis (photoredox catalysis) has rapidly progressed, drastically changing modern radical chemistry. At the heart of these developments, alkyl radicals play an essential role in the development of novel synthetic methods under photo/electrochemical catalysis.

Alkyl radical precursors typically undergo a single electron transfer with the aid of a photoredox catalyst to produce transient alkyl radicals that can participate in various bond formation processes in a chemically and stereoselective manner. Alkyl radical precursors have been developed that have a built-in redox group that can narrow the energy gap between the excited states of the substrate and the photosensitizer. Despite these advances, no reports have been made of the production of alkyl radicals in a precisely controlled manner from environmentally benign chemical feedstocks.

Disclosure of Invention

The application aims to provide a method for inducing an alkyl neopentyl benzene to react with a capture reagent by using a photocatalyst, and aims to solve the technical problem of how to use alkyl neopentyl benzenes (three-stage) to expand alkyl radicals and carbonium ion chemistry.

In order to achieve the purpose of the application, the technical scheme adopted by the application is as follows:

the application provides a method for inducing alkyl neopentyl benzene to react with a capture reagent by a photocatalyst, which comprises the following steps:

adding alkyl neopentyl benzene shown in the formula I and a capture reagent into nitroalkane solution containing an acridine salt photocatalyst, and carrying out catalytic reaction under the irradiation of blue light to obtain a product shown in the formula II, the formula III or the formula IV;

wherein the capture reagent is selected from the group consisting of benylallydinitrile, benzenesulfonamide, and 1, 1-bis (phenylsulfonyl) ethylene;

R ₁ 、R ₂ 、R ₃ and R ₄ Are each independently selected from C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Heteroalkyl group, C ₃ -C ₂₀ Cycloalkyl radical, C ₃ -C ₂₀ Heterocycloalkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Heteroalkenyl, C ₃ -C ₂₀ Cycloalkenyl radical, C ₃ -C ₂₀ Heterocycloalkenyl, C ₂ -C ₂₀ Alkynyl, C ₂ -C ₂₀ Heteroalkynyl, C ₃ -C ₂₀ Cycloalkynyl group, C ₃ -C ₂₀ Heterocycloalkynyl, C ₁ -C ₂₀ Alkoxy radical, C ₆ -C ₂₀ Aryl radical, C ₄ -C ₂₀ Heteroaryl group, C ₆ -C ₂₀ Aryloxy group, C ₄ -C ₂₀ Heteroaryloxy radical, C ₆ -C ₂₀ Aryl radical (C) ₁ -C ₂₀ ) Alkyl radical, C ₄ -C20 heteroaryl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkenyl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkynyl (C) ₁ -C ₂₀ ) Alkyl, cyano (C) ₁ -C ₂₀ ) Alkyl radical, C ₁ -C ₂₀ Alkyloxycarbonyl (C) ₁ -C ₂₀ ) Alkyl, silicon based C ₃ -C ₂₀ Any one of alkyl, halogen, trifluoromethoxy, sulfonamide and hydrogen atom, or R ₂ 、R ₃ And R ₄ At least two of which are linked to form a cyclic hydrocarbon; and R is ₂ 、R ₃ 、R ₄ Not a hydrogen atom.

The method for inducing the alkyl neopentyl benzene to react with the capture reagent by the photocatalyst realizes a method for generating alkyl radicals and carbocation ions by the unactivated alkyl neopentyl benzene (tertiary) substrate shown in the formula I, the substrate shown in the formula I is easily oxidized by the acridine salt photocatalyst under the irradiation of blue light and is directly cracked to deliver the alkyl radicals and the carbocation ions which can be accepted by various nucleophilic reagents, so that the alkyl neopentyl benzene substrate is transferred by a single electron to induce the carbon-carbon bond cracking of the alkyl neopentyl benzene substrate, the alkyl neopentyl benzene substrate reacts with the capture reagent, and the capture reagent can capture the radicals and the carbocation ions, so that the finally generated alkyl radicals and the carbocation ions can be captured by the capture reagent benzyl allyl dinitrile or benzenesulfonamide or 1, 1-bis (phenylsulfonyl) ethylene; the method has safe and controllable reaction process, simplifies the operation in the production process, obviously reduces the production cost for preparing the capture product shown in the formula II, the formula III or the formula IV, and greatly expands the designability and application prospect of the compound.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The compounds and derivatives thereof referred to in the examples of the present invention are named according to the IUPAC (International Union of pure and applied chemistry) or CAS (chemical abstracts service, columbus, ohio) naming system. Thus, the groups of compounds specifically mentioned in the examples of the present invention are illustrated and described as follows:

with respect to "hydrocarbon group", the minimum and maximum values of the carbon atom content in a hydrocarbon group are indicated by a prefix, e.g., the prefix (C) _a -C _b ) Alkyl represents any alkyl group containing from "a" to "b" carbon atoms. Thus, for example, (C) ₁ -C ₆ ) Alkyl refers to alkyl groups containing one to six carbon atoms.

"alkoxy" refers to a straight or branched, monovalent, saturated aliphatic chain bonded to an oxygen atom and includes, but is not limited to, groups such as methoxy, ethoxy, propoxy, butoxy, isobutoxy, t-butoxy, and the like. (C) _a -C _b ) Alkoxy means any straight or branched, monovalent, saturated aliphatic chain of an alkyl group containing from "a" to "b" carbon atoms bonded to an oxygen atom.

"alkyl" refers to a straight or branched, monovalent, saturated aliphatic chain including, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, and the like.

"heteroalkyl" means a straight or branched, monovalent, saturated aliphatic chain attached to at least one heteroatom, such as, but not limited to, methylaminoethyl or other similar groups.

"alkenyl" refers to straight or branched chain hydrocarbons with one or more double bonds, including but not limited to, groups such as ethenyl, propenyl, and the like.

"Heteroalkenyl" means a straight or branched chain hydrocarbon with one or more double bonds attached to at least one heteroatom, including but not limited to, for example, vinylaminoethyl or other similar groups.

"alkynyl" refers to a straight or branched chain hydrocarbon with one or more triple bonds, including but not limited to, for example, ethynyl, propynyl, and the like.

"Heteroalkynyl" means a straight or branched chain hydrocarbon with one or more triple bonds attached to at least one heteroatom, including but not limited to, groups such as ethynyl, propynyl, and the like.

"aryl" refers to a cyclic aromatic hydrocarbon including, but not limited to, groups such as phenyl, naphthyl, anthryl, phenanthryl, and the like.

"heteroaryl" refers to a monocyclic or polycyclic or fused ring aromatic hydrocarbon in which one or more carbon atoms have been replaced with a heteroatom such as nitrogen, oxygen, or sulfur. If the heteroaryl group contains more than one heteroatom, these heteroatoms may be the same or different. Heteroaryl groups include, but are not limited to, groups such as benzofuranyl, benzothienyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzopyranyl, furanyl, imidazolyl, indazolyl, indolinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxadiazolyl, oxazinyl, oxazolyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridine [3,4-b ] indolyl, pyridyl, pyrimidinyl, pyrrolyl, quinolizinyl, quinolyl, quinoxalinyl, thiadiazolyl, thiatriazolyl, thiazolyl, thienyl, triazinyl, triazolyl, xanthenyl, and the like.

"cycloalkyl" refers to a saturated monocyclic or polycyclic alkyl group, possibly fused to an aromatic hydrocarbon group. Cycloalkyl groups include, but are not limited to, groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, indanyl, tetrahydronaphthyl, and the like.

"Heterocycloalkyl" means a saturated monocyclic or polycyclic alkyl group, possibly fused to an aromatic hydrocarbon group, in which at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different. Heterocycloalkyl groups include, but are not limited to, groups such as azepanyl, azetidinyl, indolinyl, morpholinyl, pyrazinyl, piperidinyl, pyrrolidinyl, tetrahydrofuryl, tetrahydroquinolinyl, tetrahydroindazolyl, tetrahydroindolyl, tetrahydroisoquinolinyl, tetrahydropyranyl, tetrahydroquinoxalinyl, tetrahydrothiopyranyl, thiazolidinyl, thiomorpholinyl, thioxanthyl, and the like.

"cycloalkenyl" refers to an unsaturated, monocyclic or polycyclic alkenyl group with one or more double bonds, possibly fused to an aromatic hydrocarbon group, including, but not limited to, cyclic ethenyl, cyclopropenyl, or other similar groups.

"Heterocycloalkenyl" means an unsaturated, monocyclic or polycyclic alkenyl radical having one or more double bonds, possibly condensed with an aromatic hydrocarbon radical, in which at least one carbon atom is replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different.

"cycloalkynyl" refers to an unsaturated, monocyclic or polycyclic alkynyl group having one or more triple bonds, possibly fused to an aromatic hydrocarbon group, including, but not limited to, cycloalkynyl, cyclopropynyl, or the like.

"Heterocycloalkynyl" means an unsaturated, monocyclic or polycyclic alkynyl radical having one or more triple bonds, possibly condensed with an aromatic hydrocarbon radical, in which at least one carbon atom has been replaced by a heteroatom such as nitrogen, oxygen or sulfur. If the heterocycloalkyl group contains more than one heteroatom, these heteroatoms may be the same or different.

The embodiment of the application provides a method for inducing an alkyl neopentyl benzene to react with a capture reagent by a photocatalyst, which comprises the following steps:

adding alkyl neopentyl benzene shown in the formula I and a capture reagent into nitroalkane solution containing an acridine salt photocatalyst, and carrying out catalytic reaction under blue light irradiation to obtain a product shown in the formula II, the formula III or the formula IV;

wherein the capture reagent is selected from the group consisting of benylallydinitrile, benzenesulfonamide, and 1, 1-bis (phenylsulfonyl) ethylene;

R ₁ 、R ₂ 、R ₃ and R ₄ Are each independently selected from C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Heteroalkyl group, C ₃ -C ₂₀ Cycloalkyl radical, C ₃ -C ₂₀ Heterocycloalkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Heteroalkenyl, C ₃ -C ₂₀ Cycloalkenyl radical, C ₃ -C ₂₀ Heterocycloalkenyl, C ₂ -C ₂₀ Alkynyl, C ₂ -C ₂₀ Heteroalkynyl, C ₃ -C ₂₀ Cycloalkynyl, C ₃ -C ₂₀ Heterocycloalkynyl, C ₁ -C ₂₀ Alkoxy radical, C ₆ -C ₂₀ Aryl radical, C ₄ -C ₂₀ Heteroaryl group, C ₆ -C ₂₀ Aryloxy radical, C ₄ -C ₂₀ Heteroaryloxy radical, C ₆ -C ₂₀ Aryl radical (C) ₁ -C ₂₀ ) Alkyl radical, C ₄ -C20 heteroaryl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkenyl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkynyl (C) ₁ -C ₂₀ ) Alkyl, cyano (C) ₁ -C ₂₀ ) Alkyl radical, C ₁ -C ₂₀ Alkyloxycarbonyl (C) ₁ -C ₂₀ ) Alkyl, silicon based C ₃ -C ₂₀ Any one of alkyl, halogen, trifluoromethoxy, sulfonamide and hydrogen atom, or R ₂ 、R ₃ And R ₄ At least two of which are linked to form a cyclic hydrocarbon; and R is ₂ 、R ₃ 、R ₄ Not a hydrogen atom.

Due to the high oxidation potential of the pure alkyl backbone, the direct generation of alkyl radicals from simple non-activated pure alkyl precursors remains a first challenge in photo-redox catalysis. In the examples of the present application, a new method of alkyl radical extension and carbocation chemistry using alkyl neopentylene (tertiary) based substrates is provided, which directly achieves simple carbon-carbon bond cleavage of pure alkyl backbones by oxidation of the benzene ring. Specifically, the embodiment of the present application realizes a method for generating alkyl radicals and carbocations from non-activated alkyl neopentylbenzene (tertiary) shown in formula I, wherein the substrate shown in formula I is easily oxidized by acridine salt photocatalyst under blue light irradiation, and is directly cleaved to deliver alkyl radicals and carbocations acceptable by various nucleophilic reagents, so that the embodiment of the present application transfers alkyl neopentylbenzene by a single electron to induce carbon-carbon bond cleavage, and reacts with a capture reagent, wherein the capture reagent can capture both radicals and carbocations, and the generated alkyl radicals and carbocations can be captured by the capture reagent benzyl allyl dinitrile or benzenesulfonamide or 1, 1-bis (phenylsulfonyl) ethylene. The reaction process of the method is safe and controllable, the operation in the production process is simplified, the production cost for preparing the capture product shown in the formula II, the formula III or the formula IV is obviously reduced, and the designability and the application prospect of the compound are greatly expanded.

In particular, when the capture reagent is benzal allyl dinitrile

In the process, alkyl neopentyl benzene shown in the formula I and the benzyl allyl dinitrile capture reagent are subjected to catalytic reaction under the conditions to obtain a product shown in the formula II.

When the capture reagent is a benzenesulfonamide

Then, the alkyl neopentyl benzene shown in the formula I and the benzene sulfonamide capture reagent are subjected to catalytic reaction under the conditions to obtain a product shown in the formula III; the benzene sulfonamide capture reagent can better capture tert-butyl carbenium ions.

When the capture reagent is 1, 1-bis (phenylsulfonyl) ethylene

Then, the alkyl neopentyl benzene shown in the formula I and the 1, 1-bis (phenylsulfonyl) ethylene capture reagent are subjected to catalytic reaction under the conditions to obtain a product shown in the formula IV.

The capture product shown in formula II or formula IV obtained by the method can provide raw materials or reaction intermediates for synthesis of drug intermediates and preparation of functional materials; and because the captured product has high functionality, the method can provide diversified choices for synthesis of drug intermediates, functional materials and applications. Can be widely used for the synthesis of drug intermediates and the preparation of chiral ligands and functional materials, can effectively reduce the economic cost of the preparation of the drug intermediates and the functional materials, and provides the environmental friendliness of the preparation. Therefore, the method can be widely applied to the fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicine research, such as the fields of synthesis of pharmaceutical intermediates and preparation of functional materials.

In some embodiments, R ₂ 、R ₃ And R ₄ Are each independently selected from C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Heteroalkyl group, C ₃ -C ₂₀ Cycloalkyl, C ₃ -C ₂₀ Heterocycloalkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Heteroalkenyl, C ₃ -C ₂₀ Cycloalkenyl radical, C ₃ -C ₂₀ Heterocycloalkenyl, C ₂ -C ₂₀ Alkynyl, C ₂ -C ₂₀ Heteroalkynyl, C ₃ -C ₂₀ Cycloalkynyl group, C ₃ -C ₂₀ Heterocycloalkynyl, C ₁ -C ₂₀ Alkoxy radical, C ₆ -C ₂₀ Aryl radical, C ₄ -C ₂₀ Heteroaryl group, C ₆ -C ₂₀ Aryloxy radical, C ₄ -C ₂₀ Heteroaryloxy radical, C ₆ -C ₂₀ Aryl radical (C) ₁ -C ₂₀ ) Alkyl radical, C ₄ -C20 heteroaryl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkenyl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkynyl (C) ₁ -C ₂₀ ) Alkyl, cyano (C) ₁ -C ₂₀ ) Alkyl radical, C ₁ -C ₂₀ Alkyloxycarbonyl (C) ₁ -C ₂₀ ) Alkyl, silyl C ₃ -C ₂₀ Any one of an alkyl group, a halogen group, a trifluoromethoxy group, a sulfonamide group, and a hydrogen atom; and R is ₂ 、R ₃ 、R ₄ Not a hydrogen atom.

When R is ₂ 、R ₃ And R ₄ Are identical or different C ₁ -C ₂₀ Alkyl, in some embodiments, C ₁ -C ₂₀ The alkyl group may be (C) ₁ -C ₁₀ ) Alkyl, (C) ₁ -C ₅ ) Alkyl, (C) ₁ -C ₄ ) Alkyl, (C) ₁ -C ₃ ) Alkyl, (C) ₁ -C ₂ ) Alkyl groups, and the like. In some embodiments, (C) ₁ -C ₂₀ ) The alkyl group may be specifically a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, etc.

When R is ₂ 、R ₃ And R ₄ Are the same or different (C) ₁ -C ₂₀ ) When it is heteroalkyl, in one embodiment, (C) ₁ -C ₂₀ ) The heteroalkyl group may be (C) ₁ -C ₁₀ ) Heteroalkyl group, (C) ₁ -C ₅ ) Heteroalkyl group, (C) ₁ -C ₄ ) Heteroalkyl group, (C) ₁ -C ₃ ) Heteroalkyl group, (C) ₁ -C ₂ ) Heteroalkyl groups and the like. In some embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₃ -C ₂₀ ) Cycloalkyl, in one embodiment, (C) ₃ -C ₂₀ ) The cycloalkyl group may be (C) ₃ -C ₁₀ ) Cycloalkyl group, (C) ₃ -C ₅ ) Cycloalkyl group, (C) ₃ -C ₄ ) Cycloalkyl groups, and the like. In one embodiment, (C) ₃ -C ₂₀ ) Cycloalkyl groups may be cyclopropyl, cyclobutyl, cyclopentyl, and the like.

When R is ₂ 、R ₃ And R ₄ Are the same or different (C) ₃ -C ₂₀ ) When it is a heterocycloalkyl group, in one embodiment, (C) ₃ -C ₂₀ ) The heterocycloalkyl group may be (C) ₃ -C ₁₀ ) Heterocycloalkyl group, (C) ₃ -C ₁₀ ) Heterocycloalkyl, (C) ₃ -C ₅ ) Heterocycloalkyl group, (C) ₃ -C ₄ ) Heterocycloalkyl, and the like. In one embodiment, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₂ -C ₂₀ ) Alkenyl, in one embodiment, (C) ₂ -C ₂₀ ) The alkenyl group may be (C) ₃ -C ₁₀ ) Alkenyl, (C) ₃ -C ₅ ) Alkenyl, (C) ₃ -C ₄ ) Alkenyl, (C) ₂ -C ₃ ) Alkenyl groups, and the like. In some embodiments, (C) ₂ -C ₂₀ ) The alkenyl group may be ethenyl, propenyl, butenyl, pentenyl, etc.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₂ -C ₂₀ ) (iii) heteroalkenyl, in one embodiment, (C) ₂ -C ₂₀ ) Heteroalkenyl can be (C) ₂ -C ₁₀ ) Heteroalkenyl, (C) ₃ -C ₁₀ ) Heteroalkenyl, (C) ₃ -C ₅ ) Heteroalkenyl, (C) ₃ -C ₄ ) Heteroalkenyl, (C) ₂ -C ₃ ) Heteroalkenyl and the like. In some embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₃ -C ₂₀ ) Cycloalkenyl, in one embodiment, (C) ₃ -C ₂₀ ) Cycloalkenyl can be (C) ₃ -C ₁₀ ) Cycloalkenyl, (C) ₃ -C ₅ ) Cycloalkenyl, (C) ₃ -C ₄ ) Cycloalkenyl groups, and the like. In some embodiments, (C) ₃ -C ₂₀ ) Cycloalkenyl can be cyclopropenyl, cyclobutenyl, cyclopentenyl and the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₃ -C ₂₀ ) When heterocycloalkenyl, in one embodiment, (C) ₃ -C ₂₀ ) The heterocycloalkenyl can be (C) ₃ -C ₁₀ ) Heterocycloalkenyl, (C) ₃ -C ₅ ) Heterocycloalkenyl, (C) ₃ -C ₄ ) Heterocycloalkenyl, and the like. In some embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₂ -C ₂₀ ) In the case of alkynylIn one embodiment, (C) ₂ -C ₂₀ ) Alkynyl may be (C) ₂ -C ₁₀ ) Alkynyl, (C) ₃ -C ₁₀ ) Alkynyl, (C) ₃ -C ₅ ) Alkynyl, (C) ₃ -C ₄ ) Alkynyl, (C) ₂ -C ₃ ) Alkynyl and the like. In some embodiments, (C) ₂ -C ₂₀ ) The alkynyl group may be an ethynyl group, propynyl group, butynyl group, pentynyl group or the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₂ -C ₂₀ ) When heteroalkynyl is present, (C) is, in one embodiment ₂ -C ₂₀ ) Heteroalkynyl can be (C) ₂ -C ₁₀ ) Heteroalkynyl, (C) ₃ -C ₁₀ ) Heteroalkynyl, (C) ₃ -C ₅ ) Heteroalkynyl, (C) ₃ -C ₄ ) Heteroalkynyl, (C) ₂ -C ₃ ) Heteroalkynyl groups and the like. In some embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.

When R is ₂ 、R ₃ And R ₄ Are the same or different (C) ₃ -C ₂₀ ) Cycloalkynyl, in one embodiment, (C) ₃ -C ₂₀ ) The cycloalkynyl group can be (C) ₃ -C ₁₀ ) Cycloalkynyl group, (C) ₃ -C ₅ ) Cycloalkynyl, (C) ₃ -C ₄ ) Cycloalkynyl, and the like. In some embodiments, (C) ₂ -C ₂₀ ) The cycloalkynyl group may be cyclopropynyl, cyclobutynyl, cyclopentynyl, or the like.

When R is ₂ 、R ₃ And R ₄ Are the same or different (C) ₃ -C ₂₀ ) When heterocycloalkynyl, in one embodiment, (C) ₃ -C ₂₀ ) The heterocycloalkynyl can be (C) ₃ -C ₁₀ ) Heterocycloalkynyl, (C) ₃ -C ₅ ) Heterocycloalkynyl, (C) ₃ -C ₄ ) Heterocycloalkynyl, and the like. In some embodiments, the heteroatom may be a halogen, nitrogen atom, sulfur atom, or the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₁ -C ₂₀ ) Alkoxy, in one embodiment, (C) ₁ -C ₂₀ ) The alkoxy group may be (C) ₁ -C ₁₀ ) Alkoxy group, (C) ₁ -C ₈ ) Alkoxy group, (C) ₁ -C ₆ ) Alkoxy group, (C) ₁ -C ₄ ) Alkoxy group, (C) ₁ -C ₃ ) Alkoxy group, (C) ₁ -C ₂ ) An alkoxy group. In some embodiments, (C) ₁ -C ₂₀ ) Alkoxy groups can be, but are not limited to, methyloxy, ethyloxy, propyloxy, and the like.

When R is ₂ 、R ₃ And R ₄ When the aryl groups are the same or different, the aryl groups may be, but are not limited to, monocyclic aryl groups, polycyclic aryl groups, and fused ring aryl groups. In one embodiment, the aryl group is a monocyclic aryl group. In some embodiments, aryl is phenyl.

When R is ₂ 、R ₃ And R ₄ When the same or different substituted aryl groups are present, the substituted aryl groups may be, but are not limited to, phenyl groups substituted singly or multiply in the ortho, meta, or para positions. Substituents include, but are not limited to, alkyl, substituted alkyl, halogen, alkoxyamino, nitro, -NR ₅ R ₆ 、-NR ₅ -CO-NR ₆ 、-OCONR ₅ 、-PR ₅ R ₆ 、-SOR ₅ 、-SO ₂ -R ₅ 、-SiR ₅ R ₆ R ₇ 、-BR ₅ R ₆ Wherein R is ₅ 、R ₆ 、R ₇ Which may be the same or different is as R above ¹ 、R ² The radicals shown. Wherein, when the substituent is alkyl, the water absorbing additive is alkyl such as but not limited to methyl, ethyl, propyl, butyl, isobutyl; when the substituent is a substituted alkyl group, the water absorbing additive is a substituted alkyl group such as, but not limited to, trifluoromethyl, trichloromethyl, trifluoroethyl, trichloroethyl; when the substituent is halogen, the water absorbing additive halogen is, for example, but not limited to, fluorine, chlorine, bromine, iodine; when the substituent is an alkoxy group, the water absorbing additive alkoxy group is, for example, but not limited to, methyloxy, ethyloxy, propyloxy. In one embodiment, the substituted aryl group may also be cyano (C) ₁ -C ₁₀ ) Alkyl (C) ₃ -C ₈ ) Aryl, substituted (C) ₃ -C ₈ ) And (4) an aryl group.

When R is ₂ 、R ₃ And R ₄ When the same or different heteroaryl groups are present, in one embodiment, the heteroaryl group can be (C) ₃ -C ₈ ) Heteroaryl, furan, thiophene.

When R is ₂ 、R ₃ And R ₄ In the case of identical or different substituted heteroaryl, in one embodiment the substituted heteroaryl may be substituted (C) ₃ -C ₈ ) Heteroaryl, alkoxy substituted furan, (C) ₃ -C ₈ ) Heteroaryl substituted furans, aliphatic chain substituted thiophenes.

When R is ₂ 、R ₃ And R ₄ When the same or different aryloxy groups are present, in one embodiment, the aryloxy group can be a phenoxy group, naphthoxy group, anthracenoxy group, phenanthroxy group.

When R is ₂ 、R ₃ And R ₄ Are identical or different aryl radicals (C) ₁ -C ₂₀ ) Alkyl, in one embodiment, the aryl (C) ₁ -C ₂₀ ) The alkyl group may be aryl (C) ₁ -C ₁₀ ) Alkyl, phenyl (C) ₁ -C ₁₀ ) Alkyl, phenyl (C) ₁ -C ₅ ) Alkyl, phenyl (C) ₁ -C ₄ ) Alkyl, phenyl (C) ₁ -C ₃ ) Alkyl, phenyl (C) ₁ -C ₂ ) Alkyl groups, and the like. In some embodiments, aryl (C) ₁ -C ₂₀ ) The alkyl group may be phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, phenylisobutyl, phenylpentyl, phenylisopentyl, phenylneopentyl.

When R is ₂ 、R ₃ And R ₄ Are identical or different heteroaryl (C) ₁ -C ₂₀ ) Alkyl, in one embodiment, the heteroaryl (C) ₁ -C ₂₀ ) The alkyl group may be heteroaryl (C) ₁ -C ₁₀ ) Alkyl, heteroaryl (C) ₁ -C ₁₀ ) Alkyl, heteroaryl (C) ₁ -C ₅ ) Alkyl, heteroaryl (C) ₁ -C ₄ ) Alkyl, heteroaryl (C) ₁ -C ₃ ) Alkyl, heteroaryl (C) ₁ -C ₂ ) Alkyl groups, and the like. Wherein the heteroaryl group may be (C) ₃ -C ₈ ) Heteroaryl, furan, pyridine, and the like.

When R is ₂ 、R ₃ And R ₄ Are identical or different (C) ₂ -C ₂₀ ) Alkenyl (C) ₁ -C ₂₀ ) When it is an alkyl group, in one embodiment, the group (C) ₂ -C ₂₀ ) Alkenyl (C) ₁ -C ₂₀ ) The alkyl group may be (C) ₂ -C ₁₀ ) Alkenyl (C) ₁ -C ₁₀ )、(C ₂ -C ₅ ) Alkenyl (C) ₁ -C ₃ ). In certain embodiments, the (C) ₂ -C ₂₀ ) Alkenyl (C) ₁ -C ₂₀ ) The alkyl group may be a 2-butenyl group, 2-pentenyl group, 3-hexenyl group, 3-heptenyl group, or the like.

When R is ₂ 、R ₃ 、R ₄ Are identical or different (C) ₂ -C ₂₀ ) Alkynyl (C) ₁ -C ₂₀ ) When it is an alkyl group, in one embodiment, the group (C) ₂ -C ₂₀ ) Alkynyl (C) ₁ -C ₂₀ ) The alkyl group may be (C) ₂ -C ₁₀ ) Alkynyl (C) ₁ -C ₁₀ ) Alkyl, (C) ₂ -C ₅ ) Alkynyl (C) ₁ -C ₃ ) An alkyl group. In certain embodiments, the (C) ₂ -C ₂₀ ) Alkynyl (C) ₁ -C ₂₀ ) The alkyl group may be 2-butynyl, 2-pentynyl, 3-hexynyl, 3-heptynyl, etc.

When R is ₂ 、R ₃ And R ₄ Identical or different cyano radicals (C) ₁ -C ₂₀ ) Alkyl, in one embodiment, the cyano (C) ₁ -C ₂₀ ) Alkyl may be cyano (C) ₁ -C ₁₀ ) Alkyl, cyano (C) ₁ -C ₅ ) Alkyl, cyano (C) ₁ -C ₄ ) Alkyl, cyano (C) ₁ -C ₃ ) Alkyl, cyano (C) ₁ -C ₂ ) Alkyl groups, and the like. In certain embodiments, cyano (C) ₁ -C ₂₀ ) The alkyl group may be cyanomethyl, cyanoethyl, cyanopropyl, cyanobutyl, cyanopentyl, or the like.

When R is ₂ 、R ₃ And R ₄ When the alkyl groups are the same or different alkyl oxycarbonylalkyl groups, in one embodiment, the alkyl oxycarbonylalkyl groups may be (C) ₁ -C ₁₀ ) Alkyloxycarbonyl (C) ₁ -C ₁₀ ) Alkyl, (C) ₁ -C ₅ ) Alkyloxycarbonyl (C) ₁ -C ₅ ) Alkyl, (C) ₁ -C ₄ ) Alkyloxycarbonyl (C) ₁ -C ₄ ) Alkyl, (C) ₁ -C ₃ ) Alkyloxycarbonyl (C) ₁ -C ₃ ) Alkyl, (C) ₁ -C ₂ ) Alkyloxycarbonyl (C) ₁ -C ₂ ) Alkyl groups, and the like. In some embodiments, the alkyloxycarbonylalkyl group can be an ethoxycarbonylethyl group, an ethoxycarbonylmethyl group, a methoxycarbonylethyl group, a methoxycarbonylmethyl group, a propoxycarbonylpropyl group, a propoxycarbonylethyl group, a propoxycarbonylmethyl group, or the like.

When R is ₂ 、R ₃ And R ₄ When at least two of them are linked to form a cyclic hydrocarbon, may be R ₃ And R ₄ Or R is ₂ And R ₄ Or R is ₂ And R ₃ The linkages form cyclic hydrocarbons, leaving one as a separate hydrocarbyl group. Or, R ₂ 、R ₃ And R ₄ Are co-joined to form a cyclic hydrocarbon.

In some embodiments, R ₂ 、R ₃ And R ₄ Are each independently selected from C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Heteroalkyl group, C ₃ -C ₁₀ Cycloalkyl radical, C ₃ -C ₁₀ Heterocycloalkyl radical, C ₂ -C ₁₀ Alkenyl radical, C ₂ -C ₁₀ Heteroalkenyl, C ₃ -C ₁₀ Cycloalkenyl radical, C ₃ -C ₁₀ Heterocycloalkenyl, C ₂ -C ₁₀ Alkynyl, C ₂ -C ₁₀ Heteroalkynyl, C ₃ -C ₁₀ Cycloalkynyl group, C ₃ -C ₁₀ Heterocycloalkynyl, C ₁ -C ₁₀ Alkoxy radical, C ₄ -C ₁₄ Aryl radical, C ₄ -C ₁₄ Heteroaryl group, C ₄ -C ₁₄ Aryloxy radical, C ₄ -C ₁₄ Heteroaryloxy radical, C ₄ -C ₁₄ Aryl radical (C) ₁ -C ₁₀ ) Alkyl radical, C ₄ -C ₁₄ Heteroaryl (C) ₁ -C ₁₀ ) Alkyl radical, C ₂ -C ₁₀ Alkenyl (C) ₁ -C ₁₀ ) Alkyl radical, C ₂ -C ₁₀ Alkynyl (C) ₁ -C ₁₀ ) Alkyl, cyano (C) ₁ -C ₁₀ ) Alkyl radical, C ₁ -C ₁₀ Alkyloxycarbonyl (C) ₁ -C ₁₀ ) Alkyl and silyl radicals C ₃ -C ₁₀ Any one of alkyl groups. Further, R ₁ Is hydrogen, R ₂ 、R ₃ And R ₄ Are each independently selected from C ₁ -C ₁₀ Alkyl and C ₃ -C ₁₀ Any one of cycloalkyl groups.

In one embodiment, the structure of the acridine salt-based catalyst is as follows:

wherein X is a tetrafluoroborate anion, a hexafluorophosphate anion or a perchlorate anion; r ₄ 、R ₅ And R ₆ Are each independently selected from C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Heteroalkyl group, C ₃ -C ₂₀ Cycloalkyl radical, C ₃ -C ₂₀ Heterocycloalkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Heteroalkenyl, C ₃ -C ₂₀ Cycloalkenyl radical, C ₃ -C ₂₀ Heterocycloalkenyl, C ₂ -C ₂₀ Alkynyl, C ₂ -C ₂₀ Heteroalkynyl, C ₃ -C ₂₀ Cycloalkynyl, C ₃ -C ₂₀ Heterocycloalkynyl, C ₁ -C ₂₀ Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C) ₁ -C ₂₀ ) Alkyl, heteroaryl (C) ₁ -C ₂₀ ) Alkyl, (C) ₂ -C ₂₀ ) Alkenyl (C) ₁ -C ₂₀ ) Alkyl, (C) ₂ -C ₂₀ ) Alkynyl (C) ₁ -C ₂₀ ) Alkyl and cyano (C) ₁ -C ₂₀ ) Any one of alkyl groups. The catalyst has better photo-oxidation-reduction catalysis effect. In a preferred embodiment of the present application, the photocatalyst is selected from the group consisting of Mes-Acr-PhBF ₄ 。

Furthermore, the molar ratio of the acridine salt catalyst, the alkyl neopentyl benzene shown in the formula I and the capture reagent is (0.1-20): (0.2-40): 1-100). In this case, it is advantageous to obtain the target product.

In one embodiment, the nitroalkanes in the nitroalkane solution are selected from at least one of nitromethane, nitroethane, and nitropropane. The alkyl neopentyl benzene and benzyl allyl dinitrile or benzene sulfonamide capture reagent shown in the formula I is added into a nitroalkane solution containing an acridine salt photocatalyst, and under the irradiation of blue light, the nitroalkane solvent can better promote the reaction to obtain a product obtained by adding alkyl radicals or carbonium ions and the capture reagent. Furthermore, additives, particularly water and oxidants, are added in the catalytic reaction. This is advantageous in that the desired product is obtained in high yield.

Furthermore, the mole ratio of the acridine salt catalyst, the oxidant and the water is (0.1-20): (0.1-20): 0.2-40. Wherein the oxidant is at least one selected from the group consisting of a high-valent iodine compound, a peroxy compound, a quinone compound, a persulfate, potassium permanganate, oxygen, and N-fluorobenzenesulfonylimide. For example, the oxidizing agent is selected from ammonium persulfate.

Further, the method for inducing the reaction of the alkyl neopentyl benzene and the capture reagent by the photocatalyst provided by the application is as follows:

the alkyl neopentyl benzene substrate as a reactant plays a role of an electrophilic reagent or a nucleophilic reagent, and can attack substrates such as electron-deficient olefin, electron-rich amine and the like, so that the two reactants generate addition reaction. Therefore, the atom utilization rate of reactants is effectively improved, and the limitation of a substrate can be widened, so that a target product precursor with high enantioselectivity and extremely wide range is efficiently and greenly prepared, and a product with potential application value is obtained through a simple reduction reaction. The synthesis method has structural diversity and can be widely used for synthesizing a drug intermediate and a heterocyclic compound and preparing functional materials.

In the chemical reaction formula, the acridine salt catalyst, the oxidant and the additive water have synergistic effect, so that the catalytic system has low toxicity, the atom utilization rate and the reaction efficiency are improved, and byproducts are few; meanwhile, the reaction process is safe and controllable, and the operation in the preparation production process is simplified. The acridine salt photocatalyst can provide a better single-electron oxidation effect, so that the carbon-carbon bond breaking efficiency is improved in the catalytic reaction process.

In order to make the catalytic system exert more effective catalytic action, in one embodiment, the molar ratio of the acridine salt catalyst, the oxidant and the water is (0.1-20): (0.2-40). Under the condition, the reaction has high catalytic efficiency under the synergistic action of the photocatalyst acridine salt, the oxidant and water, and is favorable for improving the yield of reaction products. Preferably, the molar ratio of the acridine salt catalyst to the oxidant to the water is (0.2-20): 2.5 (1-10), in which case the highest yield of the target product is advantageously obtained.

The novel method for inducing the carbon-carbon bond to break to generate the alkyl radical provided by the embodiment of the application has the following advantages: the fragmentation method and the captured product have high functional group, and can be widely used in the research fields of organic synthetic chemistry, biochemistry, asymmetric catalysis, pesticides and medicine, such as the synthesis of pharmaceutical intermediates and the preparation of functional materials. In the embodiment of the application, by the above method, any one of the following structural formulas is obtained:

the following description will be given with reference to specific examples.

Example 1

A2- (2, 2-dimethyl-1-phenylpropyl) malononitrile compound and a preparation method thereof. The structural formula of the 2- (2, 2-dimethyl-1-phenylpropyl) malononitrile compound is shown as the following formula 1:

the preparation method comprises the following steps: the photocatalyst Mes-Acr-PhBF is added ₄ (0.01mmol, 4.6 mg), the capture reagent benzylidenemalononitrile (0.2mmol, 30.8 mg) and the oxidant ammonium persulfate (0.5mmol, 114mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Nitromethane and water (1 mL and 0.1 mL) were added followed by the alkyl neopentylbenzene (three stage)

(0.6 mmol). The reaction vessel was degassed, backfilled with argon and placed under a 450nm Kessil lamp for irradiation (40W). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 73% yield.

Correlation characterization analysis, the result of which is ¹ H NMR(400MHz,Chloroform-d)δ7.42(s,5H),4.25(d,J＝5.7Hz,1H),3.04(d,J＝5.6Hz,1H),1.13(s,9H). ¹³ C NMR (101MHz, chloroform-d) delta 136.26,129.32,128.74,128.63,113.20,113.11,56.79,34.96,28.49,25.06, this further confirms the molecular structure of the product as in molecular structure 1 above.

Example 2

A (3, 3-dimethylbutane-1, 1-methylsulfonyl) benzene compound and a preparation method thereof. The structural formula of the (3, 3-dimethylbutane-1, 1-methylsulfonyl) benzene compound is shown as formula 2:

the preparation method comprises the following steps: the photocatalyst Mes-Acr-PhBF is added ₄ (0.01mmol, 4.6 mg), capture reagent 1, 1-bis (phenylsulfonyl) ethylene (0.2 mmol), and oxidant ammonium persulfate (0.5 mmol, 114mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Nitromethane and water (1 mL and 0.1 mL) were added followed by alkyl neopentylbenzene (three stages)

(0.6 mmol). The reaction vessel was degassed, backfilled with argon and then placed450nm under Kessil lamp (40W). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 69% yield.

Correlation characterization analysis, the result is ¹ H NMR(400MHz,Chloroform-d)δ8.03–7.92(m,4H),7.74–7.68(m,2H),7.63–7.56(m,4H),4.44(t,J＝4.0Hz,1H),2.22(d,J＝4.1Hz,2H),0.91(s,9H). ¹³ C NMR (101MHz, chloroform-d) delta 138.20,134.51,129.95,129.06,81.76,36.62,31.22,29.23 this result further confirms the molecular structure of the product as in molecular structure 2 above.

Example 3

A 2- (2, 2-dimethyl-1-phenylbutyl) malononitrile compound and a preparation method thereof. The structural formula of the 2- (2, 2-dimethyl-1-phenylbutyl) malononitrile compound is shown as a formula 3:

the preparation method comprises the following steps: the photocatalyst Mes-Acr-PhBF is added ₄ (0.01mmol, 4.6 mg), the capture reagent benzylidenemalononitrile (0.2mmol, 30.8 mg) and the oxidant ammonium persulfate (0.5mmol, 114mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Nitromethane and water (1 mL and 0.1 mL) were added followed by the alkyl neopentylbenzene (three stage)

(0.6 mmol). The reaction vessel was degassed, backfilled with argon and placed under a 450nm Kessil lamp for irradiation (40W). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 70% yield.

Correlation characterization analysis, the result of which is ¹ H NMR(400MHz,Chloroform-d)δ7.42(qd,J＝5.0,4.5,3.1Hz,5H),4.23(d,J＝5.4Hz,1H),3.10(d,J＝5.4Hz,1H),1.42(qd,J＝7.4,1.9Hz,2H),1.15(s,3H),1.02(s,3H),0.92(t,J＝7.5Hz,3H). ¹³ C NMR(101MHz,Chloroform-d)δ136.00,129.58,128.73,128.62,113.32,113.12,55.09,37.48,33.42,24.85,24.76,24.54,8.19. This result further confirms the molecular structure of the product as in molecular structure 3 above.

Example 4

A2- ((1-ethylcyclohexyl) (phenyl) methyl) malononitrile compound and a preparation method thereof. The structural formula of the 2- ((1-ethylcyclohexyl) (phenyl) methyl) malononitrile compound is shown as the following formula 4:

the preparation method comprises the following steps: the photocatalyst Mes-Acr-PhBF is added ₄ (0.01mmol, 4.6 mg), the capture reagent benzylidenemalononitrile (0.2mmol, 30.8 mg) and the oxidant ammonium persulfate (0.5mmol, 114mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Nitromethane and water (1 mL and 0.1 mL) were added followed by the alkyl neopentylbenzene (three stage)

(0.6 mmol). The reaction vessel was degassed, backfilled with argon and placed under a 450nm Kessil lamp for irradiation (40W). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 63% yield.

Correlation characterization analysis, the result of which is ¹ H NMR(400MHz,Chloroform-d)δ7.43(ddt,J＝7.2,5.5,3.1Hz,5H),4.22(d,J＝5.1Hz,1H),3.23(d,J＝5.1Hz,1H),1.78–1.58(m,5H),1.55–1.42(m,5H),1.28(d,J＝1.8Hz,2H),0.88(t,J＝7.5Hz,3H). ¹³ CNMR (101MHz, chloroform-d) delta 135.56,130.01,128.65,128.55,113.60,113.26,52.38,39.69,31.65,31.58,29.72,25.44,24.29,21.29,21.25,7.15.

Example 5

A2- ((1-methylcyclohexyl) (phenyl) methyl) malononitrile compound and a preparation method thereof. The structural formula of the 2- ((1-methylcyclohexyl) (phenyl) methyl) malononitrile compound is shown as the following formula 5:

the preparation method comprises the following steps: the photocatalyst Mes-Acr-PhBF is added ₄ (0.01mmol, 4.6 mg), the capture reagent benzylidenemalononitrile (0.2mmol, 30.8 mg) and the oxidant ammonium persulfate (0.5mmol, 114mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Nitromethane and water (1 mL and 0.1 mL) were added followed by the alkyl neopentylbenzene (three stage)

(0.6 mmol). The reaction vessel was degassed, backfilled with argon and placed under a 450nm Kessil lamp for irradiation (40W). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 65% yield.

Correlation characterization analysis, the result is ¹ H NMR(400MHz,Chloroform-d)δ7.42(m,5H),4.28(d,J＝5.3Hz,1H),3.10(d,J＝5.4Hz,1H),1.68–1.36(m,7H),1.35–1.21(m,3H),1.19(s,3H). ¹³ C NMR(101MHz,Chloroform-d)δ135.74,129.75,128.64,128.54,113.50,113.28,56.76,37.33,36.79,36.55,25.66,24.27,21.79,21.45,20.32.HRMS(ESI-TOF)calculated for C ₁₇ H ₂₀ N ₂ (M-H ⁺ ) 251.1554, found 254.1555 the results further confirm the molecular structure of the product as in molecular structure 5 above.

Example 6

The preparation method of the compound shown in the formula 6 comprises the following steps: the photocatalyst Mes-Acr-PhBF is added ₄ (0.01mmol, 4.6 mg), the capture reagent benzylidenemalononitrile (0.2mmol, 30.8 mg) and the oxidant ammonium persulfate (0.5mmol, 114mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Nitromethane and water (1 mL and 0.1 mL) were added followed by alkyl neopentylbenzene (three stages)

(0.6 mmol). The reaction vessel was degassed, backfilled with argon and placed under a 450nm Kessil lamp for irradiation (40W). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 80% yield.

Correlation characterization analysis, the result is ¹ H NMR(500MHz,Chloroform-d)δ7.39(m,J＝7.5Hz,5H),4.26(d,J＝5.4Hz,1H),2.82(d,J＝5.3Hz,1H),2.04(q,J＝3.2Hz,3H),1.77–1.65(m,9H),1.61(m,3H). ¹³ C NMR(126MHz,Chloroform-d)δ135.34,129.70,128.63,128.57,113.48,113.33,58.09,40.44,36.58,36.39,28.43,23.79.HRMS(ESI-TOF)calculated for C ₂₀ H ₂₂ N ₂ (M-H ⁺ ) 289.1710, found.

Example 7

A 2- (1, 2-diphenyl hexyl) malononitrile compound and a preparation method thereof. The structural formula of the 2- (1, 2-diphenylhexyl) malononitrile compound is shown as the following molecular structural formula 7:

the preparation method comprises the following steps: the photocatalyst Mes-Acr-PhBF is added ₄ (0.01mmol, 4.6 mg), the capture reagent benzenesulfonamide (1.0 mmol) and the oxidant ammonium persulfate (0.5mmol, 114mg) were weighed into an oven-dried 8mL vial equipped with a magnetic star-bar. Anhydrous nitromethane (1 mL) was added followed by alkyl pivalols (three stage)

(0.2 mmol). The reaction vessel was degassed, backfilled with argon and placed under a 450nm Kessil lamp for irradiation (40W). The progress of the reaction was monitored by TLC. After completion, the reaction mixture was concentrated and purified by flash column chromatography on silica gel to obtain the desired product in 37% yield.

Correlation characterizationAnalysis, which results in a mixture of enantiomers: ¹ H NMR(400MHz,Chloroform-d)δ7.97–7.88(m,2H),7.60–7.46(m,3H),4.89(d,J＝24.8Hz,1H),1.24(d,J＝1.0Hz,9H). ¹³ C NMR(101MHz,Chloroform-d)δ143.43,132.11,128.86,126.92,54.67,30.13.HRMS(ESI-TOF)calculated for C ₁₀ H ₁₅ NO ₂ S(M+H ⁺ ) 214.0896, found 214.0897, the results further confirm the molecular structure of the product as in molecular structure 7 above.

The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. A method for inducing the reaction of alkyl neopentyl benzene and a capture reagent by a photocatalyst is characterized by comprising the following steps:

adding alkyl neopentyl benzene shown in the formula I and a capture reagent into nitroalkane solution containing an acridine salt photocatalyst, and carrying out catalytic reaction under blue light irradiation to obtain a product shown in the formula II, the formula III or the formula IV;

wherein the capture reagent is selected from the group consisting of benalylenitril, benzenesulfonamide or 1, 1-bis (phenylsulfonyl) ethylene;

R ₁ 、R ₂ 、R ₃ and R ₄ Are each independently selected from C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Heteroalkyl group, C ₃ -C ₂₀ Cycloalkyl radical, C ₃ -C ₂₀ Heterocycloalkyl radical, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Heteroalkenyl, C ₃ -C ₂₀ Cycloalkenyl radical, C ₃ -C ₂₀ Heterocycloalkenyl, C ₂ -C ₂₀ Alkynyl, C ₂ -C ₂₀ Heteroalkynyl, C ₃ -C ₂₀ Cycloalkynyl group, C ₃ -C ₂₀ Heterocyclic alkynyl group,C ₁ -C ₂₀ Alkoxy radical, C ₆ -C ₂₀ Aryl radical, C ₄ -C ₂₀ Heteroaryl, C ₆ -C ₂₀ Aryloxy group, C ₄ -C ₂₀ Heteroaryloxy radical, C ₆ -C ₂₀ Aryl radical (C) ₁ -C ₂₀ ) Alkyl radical, C ₄ -C20 heteroaryl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkenyl (C) ₁ -C ₂₀ ) Alkyl radical, C ₂ -C ₂₀ Alkynyl (C) ₁ -C ₂₀ ) Alkyl, cyano (C) ₁ -C ₂₀ ) Alkyl radical, C ₁ -C ₂₀ Alkyloxycarbonyl (C) ₁ -C ₂₀ ) Alkyl, silicon based C ₃ -C ₂₀ Any one of an alkyl group, a halogen group, a trifluoromethoxy group, a sulfonamide group and a hydrogen atom, or R ₂ 、R ₃ And R ₄ At least two of which are linked to form a cyclic hydrocarbon; and R is ₂ 、R ₃ 、R ₄ Not a hydrogen atom.

2. The method of claim 1, wherein R is ₂ 、R ₃ And R ₄ Are each independently selected from C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Heteroalkyl group, C ₃ -C ₁₀ Cycloalkyl radical, C ₃ -C ₁₀ Heterocycloalkyl, C ₂ -C ₁₀ Alkenyl radical, C ₂ -C ₁₀ Heteroalkenyl radical, C ₃ -C ₁₀ Cycloalkenyl radical, C ₃ -C ₁₀ Heterocycloalkenyl, C ₂ -C ₁₀ Alkynyl, C ₂ -C ₁₀ Heteroalkynyl, C ₃ -C ₁₀ Cycloalkynyl group, C ₃ -C ₁₀ Heterocycloalkynyl, C ₁ -C ₁₀ Alkoxy radical, C ₄ -C ₁₄ Aryl radical, C ₄ -C ₁₄ Heteroaryl group, C ₄ -C ₁₄ Aryloxy group, C ₄ -C ₁₄ Heteroaryloxy radical, C ₄ -C ₁₄ Aryl radical (C) ₁ -C ₁₀ ) Alkyl radical, C ₄ -C ₁₄ Heteroaryl (C) ₁ -C ₁₀ ) Alkyl radical, C ₂ -C ₁₀ Alkenyl (C) ₁ -C ₁₀ ) Alkyl radical, C ₂ -C ₁₀ Alkynyl (C) ₁ -C ₁₀ ) Alkyl, cyano (C) ₁ -C ₁₀ ) Alkyl radical, C ₁ -C ₁₀ Alkyloxycarbonyl (C) ₁ -C ₁₀ ) Alkyl and silyl groups C ₃ -C ₁₀ Any one of alkyl groups.

3. The method of claim 2, wherein R is ₁ Is hydrogen, R ₂ 、R ₃ And R ₄ Are each independently selected from C ₁ -C ₁₀ Alkyl and C ₃ -C ₁₀ Any one of cycloalkyl groups.

4. The method of claim 1, wherein the molar ratio of the acridinium salt catalyst, the alkyl pivalol of formula I, and the capture reagent is (0.1-20): (0.2-40): (1-100).

5. The process of claim 1 wherein the nitroalkanes of the solution of nitroalkanes are selected from at least one of nitromethane, nitroethane, and nitropropane.

6. The method of claim 1, wherein the acridine salt catalyst has the structure:

wherein X is a tetrafluoroborate anion, a hexafluorophosphate anion or a perchlorate anion; r ₄ 、R ₅ And R ₆ Are each independently selected from C ₁ -C ₂₀ Alkyl radical, C ₁ -C ₂₀ Heteroalkyl group, C ₃ -C ₂₀ Cycloalkyl radical, C ₃ -C ₂₀ Heterocycloalkyl, C ₂ -C ₂₀ Alkenyl radical, C ₂ -C ₂₀ Heteroalkenyl radical, C ₃ -C ₂₀ Cycloalkenyl radical, C ₃ -C ₂₀ Heterocycloalkenyl, C ₂ -C ₂₀ Alkynyl, C ₂ -C ₂₀ Heteroalkynyl, C ₃ -C ₂₀ Cycloalkynyl group, C ₃ -C ₂₀ Heterocycloalkynyl, C ₁ -C ₂₀ Alkoxy, aryl, substituted aryl, heteroaryl, substituted heteroaryl, aryloxy, heteroaryloxy, aryl (C) ₁ -C ₂₀ ) Alkyl, heteroaryl (C) ₁ -C ₂₀ ) Alkyl, (C) ₂ -C ₂₀ ) Alkenyl (C) ₁ -C ₂₀ ) Alkyl, (C) ₂ -C ₂₀ ) Alkynyl (C) ₁ -C ₂₀ ) Alkyl and cyano (C) ₁ -C ₂₀ ) Any one of alkyl groups.

7. The method of any of claims 1-6, wherein at least one of water and an oxidant is also added to the catalytic reaction.

8. The method of claim 7 wherein the molar ratio of said acridine salt catalyst, said oxidant and said water is (0.1-20): (0.2-40).

9. The method of claim 7, wherein the oxidizing agent is at least one selected from the group consisting of a hypervalent iodine compound, a peroxy compound, a quinone compound, a persulfate, potassium permanganate, oxygen, and N-fluorobenzenesulfonylimide.

10. The method of claim 9, wherein the oxidizing agent is selected from ammonium persulfate.