WO2020155595A1 - 一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法 - Google Patents

一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法 Download PDF

Info

Publication number
WO2020155595A1
WO2020155595A1 PCT/CN2019/098940 CN2019098940W WO2020155595A1 WO 2020155595 A1 WO2020155595 A1 WO 2020155595A1 CN 2019098940 W CN2019098940 W CN 2019098940W WO 2020155595 A1 WO2020155595 A1 WO 2020155595A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
formula
group
carbon
alkyl
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.)
Ceased
Application number
PCT/CN2019/098940
Other languages
English (en)
French (fr)
Inventor
付华
朱先进
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Publication of WO2020155595A1 publication Critical patent/WO2020155595A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B33/00—Oxidation in general
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/02—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms
    • C07C317/04—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
    • C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/14—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with at least one hydroxy group on a condensed ring system containing two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/30—Compounds having groups
    • C07C43/307—Compounds having groups having acetal carbon atoms bound to carbon atoms of six-membered aromatic rings
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/54—Benzaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/546—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/78—Acetophenone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • C07C49/786—Benzophenone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/788—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with keto groups bound to a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C07C49/807—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen all halogen atoms bound to the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/86—Ketones containing a keto group bound to a six-membered aromatic ring containing —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/04—Monocyclic monocarboxylic acids
    • C07C63/06—Benzoic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/33—Polycyclic acids
    • C07C63/331—Polycyclic acids with all carboxyl groups bound to non-condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/33—Polycyclic acids
    • C07C63/337—Polycyclic acids with carboxyl groups bound to condensed ring systems
    • C07C63/34—Polycyclic acids with carboxyl groups bound to condensed ring systems containing two condensed rings
    • C07C63/36—Polycyclic acids with carboxyl groups bound to condensed ring systems containing two condensed rings containing one carboxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
    • C07C63/70—Monocarboxylic acids
    • 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
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/227—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5304—Acyclic saturated phosphine oxides or thioxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
    • 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
    • C07C2601/14—The ring being saturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the invention belongs to the fields of chemical technology, materials and biomedicine, and specifically relates to an aerobic oxidation system containing sulfinic acid, sulfonic acid or derivatives thereof and a photo-accelerated oxidation method thereof.
  • Oxidation reaction is the most basic and extremely important type of reaction in nature. Among them, the selective oxidation of organic compounds is an important part of modern synthetic chemistry and oxidation reaction.
  • the current oxidation reaction using molecular oxygen as the oxygen source usually requires the participation of metal catalysts, ligands or biological enzymes, and is carried out under high temperature or high pressure conditions, which limits the industrial production of this type of conversion. Therefore, the research of aerobic oxidation reaction method under normal temperature and pressure is particularly important in actual production.
  • the oxidation of organic compounds usually requires a large amount of strong oxidants such as: KMnO 4 , CrO 4 , CH 3 COOOH, Na 2 S 2 O 8 or KIO 4 and so on.
  • strong oxidants generally have many problems in terms of storage, operation, cost and environmental protection; on the other hand, due to the use of strong oxidants, the product cannot stay in a relatively active intermediate oxidation state, which limits the application of this type of method.
  • a large amount of water washing is usually required, and the wastewater contains a large amount of heavy metal ions, which will cause serious environmental pollution problems. Therefore, it is very necessary and urgent to develop a new environmentally friendly aerobic oxidation system and method.
  • the object of the present invention is to provide a compound or mixture containing sulfinic acid or its derivatives, sulfonic acid or its derivatives, and which can generate sulfinic acid or its derivatives by reaction, and/or by reaction
  • An aerobic oxidation system that can generate compounds or mixtures of sulfonic acids or their derivatives.
  • the present invention adopts sulfinic acid or its derivatives, sulfonic acid or its derivatives, compounds or mixtures of sulfinic acid or its derivatives can be generated by reaction, and/or sulfonic acid or its derivatives can be generated by reaction
  • the compound or mixture of as an auxiliary agent is combined with a molecular oxygen-containing component to obtain the aerobic oxidation system. Under light conditions, the molecular oxygen is activated due to the auxiliary action of the auxiliary agent.
  • CH carbon-hydrogen bonds
  • CC carbon-carbon single bonds
  • C ⁇ C carbon heterobonds
  • CO carbon-oxygen Bond
  • CN carbon-nitrogen bond
  • CS carbon-sulfur bond
  • C-Se carbon-selenium bond
  • C-Si carbon-silicon bond
  • CP carbon-phosphorus bond
  • C carbon-nitrogen double bond
  • Another object of the present invention is to provide a photo-accelerated oxidation method, which adopts the above-mentioned aerobic oxidation system to realize the oxidation process of the reaction raw materials to prepare the oxidation products of the raw materials.
  • the invention provides a new method for the green synthesis of oxidation products (oxygen compounds and related oxidation products) of a variety of reaction materials with high efficiency, low cost, high oxygen atom economy, and high substrate broad spectrum. It is simple and practical The operation makes the inventive method very attractive and practical.
  • An aerobic oxidation system which includes:
  • the molecular oxygen-containing component includes at least one of oxygen, an oxygen-containing gas, and a raw material of a reaction system that can generate oxygen molecules in situ.
  • the amount of component 1) is 0.001-10 times the number of active sites of the reaction raw materials to be oxidized in the aerobic oxidation reaction that the aerobic oxidation system participates in.
  • component 2) is at least one selected from the group consisting of oxygen, oxygen-containing gas, and raw materials of a reaction system that can generate oxygen molecules in situ.
  • component 2) can be directly introduced, such as oxygen, oxygen-containing gas (such as air, a mixture of oxygen and inert gas, etc.), or it can be generated in situ, for example, oxygen can be generated in situ by adding The raw materials of the molecular reaction system, specifically KMnO 4 , KClO 3 or H 2 O 2, etc.
  • One or more of 3) additives such as acids, bases, salts, and organic or transition metal catalysts can also be added to the system.
  • the system consists of the aforementioned component 1), the aforementioned component 2) and optionally the aforementioned component 3).
  • the present invention also provides a photo-accelerated aerobic oxidation method, which adopts the aerobic oxidation system described above to prepare the oxidation product of the reaction raw material under light conditions.
  • the present invention adopts sulfinic acid or its derivatives, sulfonic acid or its derivatives, compounds or mixtures which can generate sulfinic acid or its derivatives by reaction, and/or compounds or compounds which can generate sulfonic acid or its derivatives by reaction.
  • the mixture is used as an auxiliary agent.
  • a series of compounds can be aerobically oxidized at room temperature (most reactions) to obtain corresponding oxidation products, which reduces the production cost.
  • the auxiliary agent used in the method can obtain higher value-added sulfonic acid derivatives after the reaction is completed, no waste is generated in the reaction system, and it is more energy-saving and environmentally friendly; the present invention can greatly reduce energy It completely solves the environmental pollution caused by heavy metals and acid solvents, and the problem of metal residues in products. Compared with the traditional production process method, the present invention greatly reduces overall power consumption, equipment investment and overall operating cost.
  • Figure 1 Schematic diagram of the principle of sulfinic acid and its derivatives as auxiliary promoters to catalyze molecular oxygen activation and aerobic oxidation processes;
  • FIG. 2 Schematic diagram of the principle of sulfinyl chloride used as an auxiliary promoter to catalyze molecular oxygen activation and aerobic oxidation processes;
  • FIG. 3 Schematic diagram of the principle of sulfonic acid and its derivatives as auxiliary promoters catalyzing molecular oxygen activation and aerobic oxidation processes;
  • R 1 , M and Ar are defined below.
  • the present invention proposes for the first time a class of auxiliary agents that promote molecular oxygen activation under light conditions, namely at least one of the following substances 1a) to 1d):
  • a compound or mixture of sulfonic acid or its derivatives can be produced by the reaction.
  • R 1 is selected from unsubstituted or optionally substituted with one or more substituents R a of the following groups: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, heterocyclyl , aryl, heteroaryl, alkoxy, aryloxy; each R a independently selected from oxo, halogen, hydroxy, mercapto, nitro, alkyl, substituted with one or more alkoxy R a1 Group, alkoxy group, one or more R a1 substituted alkoxy, cycloalkyl, one or more R a1 substituted cycloalkyl, siloxy, heterocyclyl, one or more R a1 substituted Heterocyclyl, aryl, one or more Ra1 substituted aryl, heteroaryl, one or more Ra1 substituted heteroaryl, aryloxy, one or more Ra1 substituted aryloxy,
  • the R 1 is selected unsubstituted or optionally substituted with one or more substituents R a of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl group, each of R a to each other Independently selected from oxo, halogen, alkyl, optionally halogen-substituted alkoxy, nitro, hydroxy, haloalkyl, alkyl substituted with one or more aryl groups (optionally substituted with alkyl and/or hydroxy) Group, sulfonyl, etc.
  • R a of the following groups: alkyl, cycloalkyl, heterocyclyl, aryl or heteroaryl group, each of R a to each other Independently selected from oxo, halogen, alkyl, optionally halogen-substituted alkoxy, nitro, hydroxy, haloalkyl, alkyl substituted with one or more aryl groups (optionally substitute
  • the alkyl group in R 1 is selected from C 1 -C 12 alkyl; the cycloalkyl group in R 1 is selected from C 3 -C 6 cycloalkyl; the heterocyclic group in R 1 is selected from From morpholinyl, tetrahydrofuranyl, pyrrolinyl; the aryl group in R 1 is selected from phenyl; the heteroaryl group in R 1 is selected from pyridyl, imidazolyl, and quinoxalinyl; a R a independently of one another selected from halogen (e.g.
  • the sulfinic acid is selected from benzene sulfinic acid, methyl sulfinic acid, ethyl sulfinic acid, cyclopropyl sulfinic acid, p-toluene sulfinic acid and the like.
  • R 1 is defined as described above.
  • the sulfonic acid is selected from benzenesulfonic acid, methanesulfonic acid, ethylsulfonic acid, cyclopropylsulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, 1,2,2-trifluoro- 2-hydroxy-1-trifluoromethylethane sulfonic acid, o-cresol sulfonphthalein (also known as cresol red, CAS registration number is 1733-12-6) and so on.
  • the sulfinic acid derivative is selected from sulfinate, sulfinate, sulfinyl halide and the like.
  • the sulfinate salt may be a metal sulfinate salt, an ammonium sulfinate salt or a phosphonium sulfinate salt, for example, having the structural formula shown in the following formula 3:
  • R 1 is defined as described above; M is a metal atom, NH 4 + or PH 4 + ; n is the number of valence states of M (for example, an integer of 1-4).
  • the M may be an alkali metal, alkaline earth metal, main group metal, transition metal, NH 4 + or PH 4 +, etc., such as Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al, Zn, Sn, Pb, NH 4 + or PH 4 + etc.
  • the sulfinate is selected from sodium benzene sulfinate, sodium methane sulfinate, sodium ethyl sulfinate, sodium propyl sulfinate, sodium cyclopropyl sulfinate, trifluoromethyl Sodium sulfinate, sodium difluoromethanesulfinate, sodium fluoromethanesulfinate, sodium p-toluenesulfinate, sodium pyridine-3-sulfinate, potassium trifluoromethanesulfinate, p-toluenesulfinate Potassium sulfonate, zinc trifluoromethanesulfinate, lithium trifluoromethanesulfinate, ammonium trifluoromethanesulfinate, etc.
  • the sulfinate may have the structural formula shown in the following formula 4:
  • R 1 is defined as described above, R 2 is selected from the following groups that are unsubstituted or optionally substituted with one or more Ra ' : alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl , Cycloalkynyl, heterocyclyl, aryl, heteroaryl, etc.; each Ra' is independently selected from oxo, halogen, hydroxyl, mercapto, nitro, alkyl, one or more Ra1' substitutions Alkyl, alkoxy, one or more Ra1' substituted alkoxy, cycloalkyl, siloxy, heterocyclyl, one or more Ra1' substituted heterocyclyl, aryl, one Or more Ra1' substituted aryl, heteroaryl, one or more Ra1' substituted heteroaryl, aryloxy, one or more Ra1' substituted aryloxy, acyl, sulfinyl , Sulfonyl,
  • the R 2 is selected from the following groups that are unsubstituted or optionally substituted with one or more Ra ' : alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, etc.; each R a 'are each independently selected from halogen, hydroxy, mercapto, nitro, alkyl, or a plurality of R a1' substituted alkyl group, an alkoxy group, or a plurality of R a1 'substituted alkoxy, cycloalkoxy Group, siloxy group, heterocyclic group, one or more Ra1' substituted heterocyclic group, aryl, one or more Ra1' substituted aryl, heteroaryl, one or more Ra1' substitution The heteroaryl group, aryloxy group, one or more R a1' substituted aryloxy, acyl, sulfinyl, sulfonyl, phosphoryl, etc.; each R a1' is
  • m0 is selected from 0 or 1 or 2 or 3;
  • R b1 and R b2 are the same or different, and are independently selected from H, alkyl, or R b1 and R b2 form a ring to form a hydrocarbyl ring or an aromatic ring (such as Benzene ring, naphthalene ring, anthracene ring, etc.);
  • R b3 and R b4 are the same or different, and are independently selected from H, alkyl, and aryl optionally substituted by one or more halogens or hydroxy.
  • the sulfinate is selected from (1R, 2S, 5R)-(-)-menyl-(S)-p-toluenesulfinate, methyl trifluoromethanesulfinate, trifluoromethane Phenyl sulfinate, etc.
  • the sulfinyl halide may have the structural formula shown in the following formula 5:
  • R 1 is defined as described above, and X 1 is selected from the following groups: fluorine, chlorine, bromine, and iodine.
  • the sulfinyl halide is selected from benzene sulfinyl chloride, trifluoromethyl thionyl chloride, tert-butyl sulfinyl chloride, trifluoromethyl sulfinyl bromide and the like.
  • the compound or mixture that can generate sulfinic acid or its derivatives through the reaction may be, for example, sulfinate (as shown in formula 4) and acid (such as hydrochloric acid, sulfuric acid, carbonic acid, formic acid, acetic acid, malonic acid, etc.)
  • acid such as hydrochloric acid, sulfuric acid, carbonic acid, formic acid, acetic acid, malonic acid, etc.
  • alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium methoxide, sodium tert-butoxide, etc.
  • alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium methoxide, sodium tert-butoxide, etc.
  • alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium methoxide, sodium tert-butoxide, etc.
  • the reaction of the above mixture
  • R 1 , R 2 , M and n are as defined above.
  • the sulfonic acid derivative is selected from the group consisting of sulfonate, sulfonate ester or sulfonic anhydride, sulfonyl halide, inorganic salt of sulfonyl halide and the like.
  • the sulfonate may be a metal sulfonate, an ammonium sulfonate or a phosphonium sulfonate, for example, it has the structural formula shown in the following formula 3':
  • R 1 , M and n are as defined above.
  • the sulfonate is selected from sodium benzenesulfonate, sodium methanesulfonate, sodium ethylsulfonate, sodium propylsulfonate, sodium trifluoromethanesulfonate, sodium difluoromethanesulfonate, fluorine Sodium methanesulfonate, sodium cyclopropylsulfonate, potassium triflate, zinc triflate, sodium p-toluenesulfonate, sodium 2,4,5-trichlorobenzenesulfonate, p-toluene Potassium sulfonate, ammonium trifluoromethanesulfonate, sodium pyridine-3-sulfonate, lithium trifluoromethanesulfonate, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, trifluoromethanesulfonic acid Copper, ammonium trifluo
  • sulfonic acid ester or sulfonic acid anhydride may have the structural formula shown in the following formula 4':
  • R 1 and R 2 are as defined above.
  • the sulfonic acid ester or sulfonic acid anhydride is selected from 3-fluoropropyl-4-methylbenzenesulfonate, 2-(thiophen-2-yl)ethyl p-toluenesulfonate, benzene p-toluenesulfonate Ethyl ester, diethyl p-toluenesulfonyloxymethylphosphonate, 4-nitrophenol triflate, 2-(tert-butyldimethylsilyl)oxyethanol triflate , Methyl trifluoromethanesulfonate, 1,4-butane sultone, 1,1'-bi-2-naphthol bis (trifluoromethanesulfonate), ethyl p-toluenesulfonate, 2 , 2,2-Trifluoroethyl methanesulfonate, 2,2,2-Trifluoroethyl me
  • the sulfonyl halide may have the structural formula shown in the following formula 5':
  • R 1 and X 1 are as defined above.
  • R 1 when R 1 is a N-containing heterocyclic group or heteroaryl group, it can form an inorganic salt of a sulfonyl halide with an inorganic salt.
  • the sulfonyl halide or inorganic salt of the sulfonyl halide is selected from trifluoromethanesulfonyl chloride, dodecylbenzenesulfonyl chloride, 2-methylpropanesulfonyl chloride, pyridine-4-sulfonyl chloride, 4-pyridinesulfonyl chloride Acid chloride hydrochloride, 4-morpholinesulfonyl chloride, 4-pyridinesulfonyl chloride hydrochloride, imidazole-4-sulfonyl chloride, 2-chloro-4-nitrobenzenesulfonyl chloride, tetrahydropyran-4-sulfonyl chloride , Quinoxaline-5-sulfonyl chloride, pyrroline-1-sulfonyl chloride, p-ethoxybenzenesulfonyl chloride, 2-phenyl-ethanesulfonyl chlor
  • the compound or mixture that can generate sulfonic acid or its derivatives by reaction can be, for example, sulfonic acid ester or sulfonic anhydride (as shown in formula 4') and acid (such as hydrochloric acid, sulfuric acid, carbonic acid, formic acid, acetic acid, malonic acid) Etc.), mixtures of sulfonic acid esters or sulfonic anhydrides (as shown in formula 4) and alkalis (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium methoxide, sodium tert-butoxide, etc.), sulfonic acid Mixture of acid salt (as shown in formula 3) and alkali (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium ethoxide, sodium methoxide, sodium tert-butoxide, etc.), sulfonic anhydride and nucleophile (such as alcohol, Thiols, amines
  • R 1 , R 2 , M and n are defined as described above; “OS bond cleavage” is “OS bond cleavage”, “nucleophile” is “nucleophile”, “eg” is “for example”, “Pyridine” means “pyridine” and “etc.” means “etc.”
  • the molecular oxygen-containing component of the present invention includes at least one of oxygen, an oxygen-containing gas, and the raw material of a reaction system that can generate oxygen molecules in situ.
  • the oxygen-containing gas may be a mixture of air, oxygen, and inert gas, or the like.
  • the raw materials of the reaction system that can generate oxygen molecules in situ are specifically KMnO 4 , KClO 3 or H 2 O 2 and so on.
  • the reaction system that can generate oxygen molecules in situ includes but is not limited to one of the following reaction types:
  • heating is “heating” and "Cat.” is “catalyst”.
  • an aerobic oxidation system which includes: 1) at least one of the following substances 1a) to 1d): 1a) sulfinic acid or its derivatives, 1b) sulfonic acid Or its derivatives, 1c) a compound or mixture that can generate sulfinic acid or its derivative through reaction, 1d) a compound or mixture that can generate sulfonic acid or its derivative through reaction; and 2) a component containing molecular oxygen, It includes at least one of oxygen, an oxygen-containing gas, and a raw material of a reaction system that can generate oxygen molecules in situ.
  • component 1) In the system, the specific selection of component 1) is as described above.
  • the proportion of component 1) in the system can be limited in the following ways:
  • the content of component 1) is not particularly limited. Specifically, it is related to the number of active sites of the reaction raw materials to be oxidized in the aerobic oxidation reaction; for example, the amount of component 1) is related to the aerobic oxidation
  • the amount of the reaction material to be oxidized in the aerobic oxidation reaction that the system participates in is related to, for example, relative to 1 mmol reaction substrate (ie, the reaction material to be oxidized), it is about 0.001-10eq (for example, 0.1-10eq, and then For example, 2-8 eq, and for example 2.5-5 eq), and the oxidation degree of the reaction raw materials can be controlled by the ratio of component 1) and the wavelength of the light source.
  • component 2) can be directly introduced, such as oxygen, oxygen-containing gas (such as air, a mixture of oxygen and inert gas, etc.), or it can be generated in situ, for example, oxygen can be generated in situ by adding The raw materials of the molecular reaction system, specifically KMnO 4 , KClO 3 or H 2 O 2, etc.
  • the system can also add one or more of component 3), namely additives such as acids, bases, salts, and organic or transition metal catalysts, to adjust the Oxidation and reactivity of the oxidation system, and used to realize one-pot synthesis of complex compounds.
  • component 3 namely additives such as acids, bases, salts, and organic or transition metal catalysts
  • the acid additive is selected from organic or inorganic acid compounds, and its addition amount is not particularly limited, as long as it is suitable for the required amount of the reaction.
  • the addition amount is the aerobic oxidation system involved in the aerobic oxidation system. 0.1-3eq of the raw materials to be oxidized in the oxidation reaction.
  • the acid additives may be one or more of acidic compounds such as formic acid, acetic acid, propionic acid, phosphoric acid, phosphorous acid, carbonic acid, hydrochloric acid, nitric acid, and sulfuric acid.
  • the alkali-based additives are selected from organic or inorganic alkali-based compounds, and the addition amount is not particularly limited, as long as it is suitable for the required amount of the reaction.
  • the addition amount is the aerobic oxidizing system involved in the aerobic oxidation system. 0.1-3eq of the raw materials to be oxidized in the oxidation reaction.
  • the alkali additives may be methylamine, dimethylamine, ethylamine, diethylamine, triethylamine, butylamine, aniline, and sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate,
  • alkaline compounds such as sodium bicarbonate, potassium bicarbonate, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate.
  • the salt-based additives are selected from organic or inorganic salts, and the addition amount is not particularly limited, as long as it is suitable for the required amount of the reaction.
  • the addition amount is the aerobic oxidation reaction that the aerobic oxidation system participates in. 0.1-3eq of the reaction material to be oxidized.
  • the salt additive may be one or more of quaternary ammonium salt, quaternary phosphonium salt, amine hydrochloride, amine sulfate, and sodium sulfate, potassium sulfate, magnesium chloride and other salt compounds.
  • the organic or transition metal catalyst is selected from phosphoric acid catalyst, organic amine catalyst, organic quaternary ammonium salt catalyst, organic sulfur catalyst, and transition metal palladium, ruthenium, rhodium, iridium, copper, iron, cobalt, nickel, platinum catalysts, etc. .
  • the addition amount is not particularly limited, as long as it is suitable for the required amount of the reaction.
  • the addition amount is 0.001-3 eq of the reaction raw material to be oxidized in the aerobic oxidation reaction participated by the aerobic oxidation system.
  • the organic or transition metal catalyst may be proline, tetrabutylammonium bromide, tetrabutylammonium iodide, palladium acetate, dichlorobis(triphenylphosphine)palladium, ruthenium trichloride, Copper chloride, cuprous chloride, cuprous cyanide, ferric chloride, ferrous chloride, iron acetylacetonate, nickel chloride, nickel bromide, nickel acetylacetonate, etc.
  • the present invention proposes for the first time a photo-assisted aerobic oxidation method, which uses the above-mentioned aerobic oxidation system to prepare the oxidation product of the reaction raw material under light conditions; specifically, the method uses the above-mentioned The aerobic oxidation system realizes the oxidation process of the reaction raw material to prepare the oxidation product of the reaction raw material.
  • the added amount of component 1) in the aerobic oxidation system is about 0.001-10eq (for example, 0.1-10eq, and for example 2-8eq) relative to 1mmol of the reaction substrate (ie reaction material to be oxidized). , For example, 2.5 ⁇ 5eq).
  • the aerobic oxidation system will activate molecular oxygen due to the auxiliary effect of the auxiliary agent under light conditions.
  • CH carbon-hydrogen bonds
  • CC carbon-carbon Single bond
  • C ⁇ C carbon-carbon triple bond
  • CO carbon-oxygen bond
  • CN carbon-nitrogen bond
  • CS carbon-sulfur bond
  • C-Se carbon-selenium bond
  • CH carbon-hydrogen bond
  • CC carbon-carbon single bond
  • C ⁇ C carbon-carbon triple bond
  • carbon-hydrogen bond CO
  • carbon nitrogen bond CN
  • carbon sulfur bond CS
  • carbon selenium bond C-Se
  • C-Si carbon silicon bond
  • CP carbon phosphorus bond
  • R 3 is selected from the following groups which are unsubstituted or optionally substituted by one or more R b : aryl, heteroaryl, etc.;
  • R 4 is selected from H, unsubstituted or optionally substituted by one or more The following groups substituted by R b : alkyl, cycloalkyl, alkoxy, heterocyclic, aryl, heteroaryl, halogen, hydroxyl, mercapto, nitro, amino, hydrazino, acyl, sulfinyl, Sulfonyl, phosphoryl, carboxy, ester, amide, etc.; R 3 and R 4 groups may optionally form a ring (for example, a carbocyclic or heterocyclic ring); each R b is independently selected from unsubstituted Or the following groups optionally substituted with one or more R b1 : halogen, hydroxyl, mercapto, nitro, cyano, alkyl, alkoxy, etc
  • the R 4 group is selected from the group consisting of H, unsubstituted or optionally substituted with one or more R b : C 1 -C 12 alkyl (preferably C 1 -C 6 alkyl, and more preferably C 1 -C 4 alkyl, such as methyl, ethyl, propyl, butyl, etc.), C 3 -C 12 cycloalkyl (preferably C 3 -C 7 cycloalkyl, more preferably C 3 -C 6 cycloalkyl , Such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), heterocyclic groups (such as tetrahydropyrrolyl, hydropyridyl, cyclopropylamino, cyclohexylamino, tetrahydrofuranyl, tetrahydropyranyl, etc.) Etc.), heteroaryl (such as pyrrolyl,
  • the compound of the structure shown in formula 6 may be one of the compounds shown in the following formula 6a:
  • Ar is selected from unsubstituted or optionally substituted aryl or heteroaryl with at least one R b , and R b is defined as described above;
  • R' is the same or different, and is independently selected from H, halogen, Hydroxy, mercapto, nitro, alkyl, alkoxy, cycloalkyl, heterocyclic, aryl, heteroaryl, amino, hydrazine, acyl, sulfinyl, sulfonyl, phosphoryl, ester, etc.
  • Each R' can also be substituted by one or more R b1 , and multiple R's can also form a ring (for example, a carbocyclic or heterocyclic ring);
  • m1 is an integer of 0-5;
  • R b1 and R 4 are defined as above Narrated.
  • the compound of the structure shown in Formula 6 may be: toluene, 4-fluorotoluene, 2-fluorotoluene, 3-fluorotoluene, 4-chlorotoluene, 2-chlorotoluene, 3-chlorotoluene, 4-bromotoluene, 2-bromotoluene, 3-bromotoluene, 4-iodotoluene, 2-iodotoluene, 3-iodotoluene, 4-trifluoromethyltoluene, 2-trifluoromethyltoluene, 3-trifluoromethyltoluene, 4 -Cyanotoluene, 2-cyanotoluene, 3-cyanotoluene, 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylanisole, 3 -Methyl anisole, 2-methyl anisole, 1,4-xylene, 1,3
  • R '3 R 3 ;
  • R 5 are the same or different, are independently from each other selected from unsubstituted or optionally substituted with one or more of R b the following groups: alkyl, cycloalkyl, alkenyl, Cycloalkenyl, alkynyl, cycloalkynyl, heterocyclyl, aryl, heteroaryl, amino, hydrazino, ester, acyl, sulfinyl, sulfonyl, phosphoryl, etc.; two R 5 can optionally be Into a hydrocarbyl ring; each R b is independently selected from the following groups unsubstituted or optionally substituted with one or more R b1 : halogen, hydroxyl, mercapto, nitro, cyano, alkyl, alkoxy, Cycloalkyl, alkenyl, alkynyl, heterocyclyl, aryl, heteroaryl, amino, carboxyl, ester
  • R 5 are the same or different, and are independently selected from the following groups that are unsubstituted or optionally substituted with one or more R b : C 1 -C 12 alkyl (preferably C 1 -C 6 alkyl, but also Preferably C 1 -C 4 alkyl, such as methyl, ethyl, propyl, butyl, etc.), C 3 -C 12 cycloalkyl (preferably C 3 -C 7 cycloalkyl, more preferably C 3 -C 6 Cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), heterocyclic group (such as tetrahydropyrrolyl, hydropyridyl, cyclopropylamino, cyclohexylamino, tetrahydrofuran, tetrahydro Pyranyl, etc.), heteroaryl (such as pyrrolyl,
  • the compound of the structure represented by formula 7 may be one of the compounds represented by the following formula 7a:
  • the compound of the structure shown in formula 7 may be: cumene, 4-fluoroisopropylbenzene, 2-fluoroisopropylbenzene, 3-fluoroisopropylbenzene, 4-chloroisopropylbenzene, 2-Chloroisopropylbenzene, 3-chloroisopropylbenzene, 4-bromoisopropylbenzene, 2-bromoisopropylbenzene, 3-bromoisopropylbenzene, 4-iodoisopropylbenzene, 2- Iodoisopropylbenzene, 3-iodoisopropylbenzene, 4-trifluoromethylisopropylbenzene, 2-trifluoromethylisopropylbenzene, 3-trifluoromethylisopropylbenzene, 4-cyano Isopropylbenzene, 2-cyanoisopropylbenzene, 3-cyanoisopropylbenzene, 4-isopropyl
  • R" 3 is selected from H, unsubstituted or optionally substituted with one or more R b following groups: alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, Heterocyclyl, aryl, heteroaryl, etc.;
  • R 7 is selected from H, unsubstituted or optionally substituted with one or more R b from the following groups: alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, heterocyclyl, aryl, heteroaryl, carboxyl, ester, acyl, sulfinyl, sulfonyl, phosphoryl, etc.; R 8 and R 9 are the same or different and are independently selected from each other H.
  • each R b is independently selected from the following groups which are unsubstituted or optionally substituted by one or more R b1 Groups: halogen, hydroxyl, mercapto, nitro, cyano, alkyl, alkoxy, cycloalkyl, alkenyl, alkynyl, heterocyclic, aryl, heteroaryl, amino, carboxy, ester, hydrazine Group, acyl group, sulfinyl group, sulfonyl group, phosphoryl group, etc.; each R b is independently selected from the following groups which are unsubstituted or optionally substituted by one or more R b1 Groups: halogen, hydroxyl, mercapto, nitro, cyano, alkyl, alkoxy, cycloalkyl, alkenyl, alkynyl, heterocyclic, aryl, heteroaryl, amino, carboxy, ester, hydrazine Group, acyl group, s
  • R 7 group is selected from the group consisting of H, unsubstituted or optionally substituted with one or more R b : C 1 -C 12 alkyl (preferably C 1 -C 6 alkyl, and more preferably C 1 -C 4 alkyl, such as methyl, ethyl, propyl, butyl, etc.), C 3 -C 12 cycloalkyl (preferably C 3 -C 7 cycloalkyl, more preferably C 3 -C 6 ring Alkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), heterocyclic groups (such as tetrahydropyrrolyl, hydropyridyl, cyclopropylamino, cyclohexylamino, tetrahydrofuryl, tetrahydropyridine, etc.) Pyranyl, etc.), heteroaryl (such as pyrrolyl,
  • the compound of the structure shown in Formula 8 can be: styrene, 4-fluorostyrene, 3-fluorostyrene, 2-fluorostyrene, 4-chlorostyrene, 2-chlorostyrene, 3-chlorobenzene Ethylene, 4-bromostyrene, 2-bromostyrene, 3-bromostyrene, 4-iodostyrene, 2-iodostyrene, 3-iodostyrene, 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, 4-cyclohexylstyrene, 3-cyclohexylstyrene, 2-cyclohexylstyrene, 4-acetylstyrene, 3-acetylstyrene, 2-acetylstyrene, 4- Methoxystyrene, 3-methoxystyrene, 2-methoxystyrene, 1,4-divinyl
  • R" 3 and R 8 are as defined above.
  • the compound of the structure shown in formula 9 can be: phenylacetylene, 4-fluorophenylacetylene, 3-fluorophenylacetylene, 2-fluorophenylacetylene, 4-chlorophenylacetylene, 2-chlorophenylacetylene, 3-chlorobenzene Acetylene, 4-bromophenylacetylene, 2-bromophenylacetylene, 3-bromophenylacetylene, 4-iodophenylacetylene, 2-iodophenylacetylene, 3-iodophenylacetylene, 4-hydroxyphenylacetylene, 3-hydroxyphenylacetylene, 2-hydroxyphenylacetylene, 4-cyclohexylphenylacetylene, 3-cyclohexylphenylacetylene, 2-cyclohexylphenylacetylene, 4-acetylphenylacetylene, 3-acetylphenylacetylene, 2-acetylene
  • R "'3 R " 3
  • R' 4 R 4 , but not H.
  • the compound of the structure shown in formula 10 can be: dimethyl sulfide, methyl ethyl sulfide, ethyl butyl sulfide, dicyclohexyl sulfide, diphenyl sulfide, 2,2'-di Pyridyl sulfide, phenyl methyl sulfide, phenyl trifluoromethyl sulfide, phenyl ethyl sulfide, phenyl propyl sulfide, phenyl isopropyl sulfide, phenyl cyclopropyl sulfide , Phenyl n-butyl sulfide, phenyl cyclopentyl sulfide, phenyl cyclohexyl sulfide, phenyl pyridyl sulfide, phenyl benzyl sulfide,
  • the compound of the structure shown in Formula 11 may be: phenyl phosphine, diphenyl phosphine, phenyl methyl phosphine, phenyl ethyl phosphine, phenyl propyl phosphine, phenyl n-butyl phosphine, naphthyl phosphine , Naphthylmethylphosphine, naphthylethylphosphine, naphthylpropylphosphine, naphthylbutylphosphine, anthrylphosphine, anthrylmethylphosphine, anthrylethylphosphine, anthrylpropylphosphine, anthrylbutane Phosphine, triphenylphosphine, tributylphosphine, tris(1-naphthyl)phosphine, etc.
  • R 3 is defined as described above; R '8 are the same or different, each independently selected from H, unsubstituted or optionally substituted with one or more R b substituents of the following groups: alkyl, cycloalkyl , Alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, heterocyclyl, aryl, heteroaryl, amino, etc.
  • the compound of the structure shown in formula 12 can be: benzyl alcohol, benzyl mercaptan, benzyl methyl ether, benzyl ethyl ether, benzyl cyclohexyl ether, dibenzyl ether, benzylamine, N-methyl Benzylamine, N-ethylbenzylamine, N-cyclopropylbenzylamine, N,N-dimethylbenzylamine, N-benzylmorpholine, N-benzyltetrahydropyrrole, tribenzylamine, N-benzene Benzylamine, dibenzylamine, N,N-diphenylbenzylamine, benzylhydrazine or benzylhydrazine hydrochloride, benzyl methyl sulfide, benzyl ethyl sulfide, benzyl propyl sulfide , Benzyl cyclopropyl
  • R 4 is defined as described above;
  • R 10 is selected from H, unsubstituted or optionally substituted with one or more R b from the following groups: alkyl, cycloalkyl, alkenyl, cycloalkenyl, Alkynyl, cycloalkynyl, heterocyclyl, aryl, heteroaryl, amino, hydrazine, carboxyl, ester, acyl, sulfinyl, sulfonyl, phosphoryl, etc.; optionally R 4 and R 10 can be Ring formation; each R b is independently selected from the following groups unsubstituted or optionally substituted with one or more R b1 : halogen, hydroxyl, mercapto, nitro, cyano, alkyl, alkoxy, ring Alkyl, alkenyl, alkynyl, heterocyclyl, aryl, heteroaryl, amino, carboxyl, ester, hydrazino, acyl
  • R 10 is selected from the group consisting of H, unsubstituted or optionally substituted with one or more R b : C 1 -C 12 alkyl (preferably C 1 -C 6 alkyl, more preferably C 1 -C 4 alkyl groups, such as methyl, ethyl, propyl, butyl, etc.), C 3 -C 12 cycloalkyl (preferably C 3 -C 7 cycloalkyl, more preferably C 3 -C 6 cycloalkyl, such as Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), heterocyclic groups (such as tetrahydropyrrolyl, hydropyridyl, cyclopropylamino, cyclohexylamino, tetrahydrofuranyl, tetrahydropyranyl, etc.) , Heteroaryl (such as pyrrolyl, pyridyl
  • R 4 and R 10 can form a C 3 -C 12 cycloalkyl group (preferably a C 3 -C 7 cycloalkyl group, and a C 3 -C 6 cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl, etc.), or heterocyclic groups (such as tetrahydropyrrolyl, hydrogenated pyridyl, cyclopropylamino, cyclohexylamino, tetrahydrofuranyl, tetrahydropyranyl, etc.)
  • a C 3 -C 12 cycloalkyl group preferably a C 3 -C 7 cycloalkyl group, and a C 3 -C 6 cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl, etc.
  • heterocyclic groups such as t
  • the compound of the structure shown in formula 13 can be: 1-phenylethanol, 4'-fluorophenyl-1-ethanol, 2'-fluorophenyl-1-ethanol, 3'-fluorophenyl-1- Ethanol, 4'-chlorophenyl-1-ethanol, 2'-chlorophenyl-1-ethanol, 3'-chlorophenyl-1-ethanol, 4'-bromophenyl-1-ethanol, 2'-bromo Phenyl-1-ethanol, 3'-bromophenyl-1-ethanol, 4'-iodophenyl-1-ethanol, 2'-iodophenyl-1-ethanol, 3'-iodophenyl-1-ethanol , 4'-trifluoromethylphenyl-1-ethanol, 2'-trifluoromethylphenyl-1-ethanol, 3'-trifluoromethylphenyl-1-ethanol, 4'-cyanophenyl -1-ethanol, 2'-cyanophenyl-1-ethanol, 2'
  • the aryl or heteroaryl group may also be optionally substituted by at least one substituent R b , and R b is as defined above;
  • R 11 is selected from alkyl or aryl substituted alkyl;
  • m5 is an integer, such as 0,1,2 ,3,4,5 together;
  • X 3 is an anion, including halogen (fluorine, chlorine, bromine, iodine), carboxylate, sulfonate, etc.;
  • R", m4, R 11 , m5, and X 3 are as defined above;
  • R 4a is a hydrocarbyl ring, an aryl group (such as a phenyl group) or a heteroaryl group;
  • R"a and R" are the same or different, and each other is independently selected from the above R ';m4' and m4 same or different, is an integer of 0-4; the same as or different from R '11 and R 11, each independently selected from alkyl or aryl substituted alkyl;
  • m5 " m5 is the same or different, is an integer of 0,1,2,3,4,5 ......;
  • '3 are the same or different from X 3 and X, is an anion, include halogen (fluorine, chlorine, bromine, iodine), carboxylate, Sulfonate, etc.;
  • q is an integer of 0-4 (for example, 0,1,2).
  • R"" 3 R 3
  • X 3 is defined as above;
  • m5' is an integer, such as 0,1,2,3,4,5... (exemplarily, it can be an integer of 0-10),
  • the three R"" 3 connected to the P atom are the same or different.
  • the compound of the structure shown in Formula 15 may be:
  • Ar may be the following groups that are unsubstituted or optionally substituted with one or more R b : five-membered or more aromatic ring, heteroaromatic ring, etc.; each R b is independent of each other It is selected from halogen, hydroxyl, mercapto, nitro, alkyl, alkoxy, cycloalkyl, heterocyclic, aryl, heteroaryl, carboxy, ester, amino, hydrazine, acyl, sulfinyl, Sulfonyl, phosphoryl, etc.
  • R 12 has the definition of R 4 , m4 and R 4 are defined as above, and when m4 is greater than or equal to 2, two adjacent R 12 can form a ring to form an aryl or heteroaryl group.
  • the aryl or heteroaryl group can also be optionally substituted by at least one R b ; each R b is independently selected from halogen, hydroxyl, mercapto, nitro, alkyl, alkoxy, cycloalkyl, heterocyclic group , Aryl, heteroaryl, carboxyl, ester, amino, hydrazine, acyl, sulfinyl, sulfonyl, phosphoryl, etc.
  • the compound of the structure shown in Formula 16 may be Formula 16-1 or Formula 16-2:
  • repeating unit represented by formula 17 may be one or more of the following structures:
  • the polymer may be, for example, a styrene homopolymer or a copolymer thereof.
  • the comonomer in the styrene copolymer may be selected from one or more of acrylonitrile compounds, butadiene compounds, etc., for example,
  • the copolymer includes repeating units as shown below:
  • Poly(styrene-co-acrylonitrile” is “poly(styrene-acrylonitrile copolymer)
  • polystylene-polybutadiene-polystyrene is “polystyrene-polybutadiene-polystyrene”
  • Styrene -Butadiene copolymers is “styrene-butadiene copolymer”
  • Acrylonitrile butadiene Styrene copolymers (ABS Resins) is “acrylonitrile-butadiene-styrene copolymer (ABS resin)”.
  • R"' 4 is selected from the following groups that are unsubstituted or optionally substituted with one or more R b : alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, hetero
  • R b is as defined above.
  • the compound of the structure represented by formula 18 may be one of the compounds represented by the following formula 18a:
  • the compound of the structure shown in Formula 18 may be: benzaldehyde, 4-fluorobenzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-chlorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzene Formaldehyde, 4-bromobenzaldehyde, 2-bromobenzaldehyde, 3-bromobenzaldehyde, 4-iodobenzaldehyde, 2-iodobenzaldehyde, 3-iodobenzaldehyde, 4-trifluoromethylbenzaldehyde, 2-trifluoromethyl Fluoromethylbenzaldehyde, 3-trifluoromethylbenzaldehyde, 4-cyanobenzaldehyde, 2-cyanobenzaldehyde, 3-cyanobenzaldehyde, 4-acetylbenzaldehyde, 3-acetylbenzaldehyde
  • R 3 and R 4 are as defined above.
  • the compound of the structure shown in Formula 19 may be one of the compounds of the structure shown in the following Formula 19-1, wherein Ar and R 13 are as defined in R', and R'is defined as described above.
  • the compound of the structure shown in formula 19 may be: aniline, 4-fluoroaniline, 2-fluoroaniline, 3-fluoroaniline, 4-chloroaniline, 2-chloroaniline, 3-chloroaniline, 4-bromoaniline, 2-bromoaniline, 3-bromoaniline, 4-iodoaniline, 2-iodoaniline, 3-iodoaniline, 4-trifluoromethylaniline, 2-trifluoromethylaniline, 3-trifluoromethylaniline, 4 -Cyanoaniline, 2-cyanoaniline, 3-cyanoaniline, 4-methylaniline, 3-methylaniline, 2-methylaniline, 4-aminoanisole, 3-aminoanisole, 2 -Aminoaniline, 1,4-dimethylaniline, 1,3-dimethylaniline, 1,2-dimethylaniline, mesitidine, 4-nitroaniline, 2,6-di Bromoaniline, 2,5-dibromoaniline, 2,4-di
  • R 4 and R 10 are defined as described above.
  • R 4 and R 10 may form a carbocyclic or heterocyclic ring, and the carbocyclic ring may be substituted by one or more R b .
  • the R 4 is an unsubstituted or optionally substituted aryl or heteroaryl group with one or more R b
  • the R 10 is unsubstituted or optionally substituted by one or more R b Aryl, heteroaryl, alkyl, cycloalkyl, halogen, etc.
  • said R 4 is unsubstituted or optionally substituted by one or more R b alkyl or cycloalkyl
  • said R 10 is unsubstituted or optionally substituted by one or more R b Aryl, heteroaryl, alkyl, cycloalkyl, halogen, etc.
  • R 4 and R 10 form a carbocyclic ring (e.g., C 3-10 cycloalkyl), which may be optionally substituted with one or more R b .
  • the compound of the structure represented by formula 20 may be one of the compounds of the structure represented by the following formula 20-1, formula 20-2, formula 20-3, and formula 20-4:
  • the compound of the structure shown in formula 20 can be: 2-phenylpropionic acid, 4'-fluorophenyl-2-propionic acid, 2'-fluorophenyl-2-propionic acid, 3'-fluorophenyl -2-propionic acid, 4'-chlorophenyl-2-propionic acid, 2'-chlorophenyl-2-propionic acid, 3'-chlorophenyl-2-propionic acid, 4'-bromophenyl-2 -Propionic acid, 2'-bromophenyl-2-propionic acid, 3'-bromophenyl-2-propionic acid, 4'-iodophenyl-2-propionic acid, 2'-iodophenyl-2-propionic acid Acid, 3'-iodophenyl-2-propionic acid, 4'-trifluoromethylphenyl-2-propionic acid, 2'-trifluoromethylphenyl-2-propionic acid
  • CFL Compact Fluorescent Lamp, compact fluorescent lamp
  • LED 200-600nm
  • the above substances, in the presence of the aerobic oxidation system, can be obtained separately according to different reaction conditions (adjusting reaction light source wavelength, reaction solvent, additives, molecular oxygen pressure, molecular oxygen content, reaction temperature or reaction time, etc.)
  • reaction conditions adjusting reaction light source wavelength, reaction solvent, additives, molecular oxygen pressure, molecular oxygen content, reaction temperature or reaction time, etc.
  • the reactant R 3 -CH 3 and the auxiliary agent of the present invention are reacted under light to obtain the corresponding carboxylic acid compound R 3 COOH.
  • the reactant R 3 -CH 3 and auxiliary additives in the above E2 are dissolved in an organic solvent to obtain a reaction mixture, which is irradiated with light (wavelength of about 300-425 nm) from a 3W Blue LED (blue LED lamp)
  • a reaction mixture which is irradiated with light (wavelength of about 300-425 nm) from a 3W Blue LED (blue LED lamp)
  • react in air or oxygen atmosphere at room temperature for an appropriate time to obtain the target compound R 3 COOH.
  • CFL Compact Fluorescent Lamp , a compact fluorescent lamp
  • 3W blue LED (blue LED) light wavelength of about 300-455nm
  • CFL Compact Fluorescent Lamp , a compact fluorescent lamp
  • 3W blue LED (blue LED) light wavelength of about 450-455nm
  • the reaction time is about 5-12 hours. If the reaction time is prolonged or the wavelength of the light source is changed, the aldehyde compound obtained by the reaction will continue to be converted into the corresponding carboxylic acid compound.
  • the reaction time is about 5-12 hours. If the reaction time is prolonged or the wavelength of the light source is changed, the target compound obtained by the reaction produces a carbon-carbon bond cleavage product between two carbonyl groups, which makes the reaction system complicated.
  • the reactant P(R' 3 )(R" 4 )(R' 4 ) in E7 and the auxiliary agent are dissolved in an organic solvent to obtain a reaction mixture.
  • the reactant R 3 -CH 2 -X 2 -(R 8 ) y and auxiliary additives in E8 are dissolved in an organic solvent to obtain a reaction mixture.
  • CFL Compact Fluorescent Lamp, which is a compact Fluorescent lamp
  • 3W Blue LED (blue LED lamp) light wavelength is about 420-455nm
  • the reaction time is about 5-12 hours. If the reaction time is prolonged or the wavelength of the light source is changed, the aldehyde compound obtained by the reaction will continue to be converted into the corresponding carboxylic acid compound.
  • the reactant R 4 -CH(OH)-R 10 and auxiliary additives in E9 are dissolved in an organic solvent to obtain a reaction mixture.
  • the light (wavelength of the 3W Blue LED) is about 380 Under -455nm) irradiation
  • the reactant (see E10) and the auxiliary agent of the present invention are reacted under light to obtain the target compound (see E10).
  • the reactants in E10 (see E10) and auxiliary additives are dissolved in an organic solvent to obtain a reaction mixture, which is irradiated with 3W Blue LED light (wavelength approximately 380-455nm), React in air or oxygen atmosphere at room temperature for an appropriate time to obtain the target compound (see E10).
  • the reactant (see E11) and the auxiliary agent of the present invention are reacted under light to obtain the target compound (see E11), where m5 is an integer greater than 1, m5 -1 represents m5 minus 1 (if m5 is 0, the end group C in R"" 3 is converted to an aldehyde group).
  • the aldehyde compounds obtained from the reaction will continue to be converted into corresponding carboxylic acid compounds.
  • the reactant (see E12) and the auxiliary agent of the present invention are reacted under light to obtain the target compound (see E12).
  • Lamp light (wavelength is about 420-455nm) irradiated, reacted in air or oxygen atmosphere at room temperature for an appropriate time to obtain the target compound (see E12).
  • the eleventh substance contains the repeating unit shown in formula 17 and the polymer will react as shown in the following formula:
  • the reactant (see E13) and the auxiliary agent of the present invention are reacted under light to obtain the target compound (see E13).
  • the reactants in E13 (see E13) and auxiliary additives are dissolved in an organic solvent to obtain a reaction mixture, which is irradiated with 3W Blue LED light (wavelength about 380-455nm), React in air or oxygen atmosphere at room temperature for a suitable time to obtain the target compound (see E13).
  • the reaction time is about 5-12h. If the reaction time is prolonged or the wavelength of the light source is changed, the aldehyde compounds obtained by the reaction will continue to be converted into corresponding carboxylic acid compounds.
  • the reactant R 3 CHO and auxiliary additives in the above E15 are dissolved in an organic solvent to obtain a reaction mixture, which is irradiated with 3W Blue LED light (wavelength approximately 380-455nm),
  • the target compound R 4 COOH is obtained by reacting in air or oxygen atmosphere at room temperature for an appropriate time.
  • the reactant R 4 -CHO and the auxiliary agent of the present invention are reacted under light to obtain the acetal R 4 -CH(OR) 2 .
  • the reactants R 4 CHO, ROH and auxiliary agents in the above E15' are dissolved in an organic solvent to obtain a reaction mixture, and the light of 3W Blue LED (wavelength is about 380-455nm)
  • the target compound acetal R 4 -CH(OR) 2 is obtained by reacting in air or oxygen atmosphere at room temperature for an appropriate time.
  • the reactant (see E16) and the auxiliary agent of the present invention are reacted under light to obtain the target compound (see E16).
  • the reactants in E16 (see E16) and auxiliary additives are dissolved in an organic solvent to obtain a reaction mixture.
  • the reactant (see E17) and the auxiliary agent of the present invention are reacted under light to obtain the target compound (see E17).
  • Lamp light (wavelength is about 380-480nm) irradiated, reacted in air or oxygen atmosphere at room temperature for an appropriate time to obtain the target compound (see E17).
  • component 2) is at least one selected from the group consisting of oxygen, an oxygen-containing gas, and a raw material of a reaction system that can generate oxygen molecules in situ.
  • the wavelength of the reaction light source can be adjusted in the range of 200-600nm.
  • the reaction is preferably carried out in an organic solvent.
  • the organic solvent is selected from organic solvents that can dissolve the reaction raw materials, such as methanol, ethanol, acetonitrile, ethyl acetate, acetone, dichloromethane, chloroform, cyclohexane, tetrahydrofuran, N,N-dimethylformamide , Dimethyl sulfoxide, 1,2-dichloroethane, ethylene glycol dimethyl ether, 1,4-dioxane, chlorobenzene, etc.
  • the amount of the organic solvent added is not particularly limited, as long as it can dissolve the reaction raw materials and auxiliary additives.
  • the reaction is carried out in a reaction vessel (such as a reaction tube) equipped with a stirring device (such as a magnetic stir bar).
  • a reaction vessel such as a reaction tube
  • a stirring device such as a magnetic stir bar
  • the reaction mixture in the reaction vessel needs to be completely irradiated under light.
  • the pressure of component 2) is controlled in the range of 1-20 atm; the content of component 2) is controlled in the range of 1%-100%.
  • the reaction is carried out at -20-80°C.
  • the reaction time can be in the range of 0.1-100h.
  • the crude target compound is separated by column chromatography to obtain the target compound.
  • halogen used in the present invention refers to fluorine, chlorine, bromine and iodine.
  • Alkyl used alone or as a suffix or prefix in the present invention is intended to include straight lines having 1 to 20, preferably 1 to 6 carbon atoms (or if a specific number of carbon atoms is provided, that specific number). Chain or branched saturated aliphatic hydrocarbon group.
  • C 1-6 alkyl means a straight or branched alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms
  • C 2-4 alkyl means having 2, 3 or 4 A straight or branched chain alkyl group of three carbon atoms.
  • alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.
  • alkenyl used alone or as a suffix or prefix in the present invention is intended to include those having 2 to 20, preferably 2-6 carbon atoms (or if a specific number of carbon atoms is provided, that specific number) Alkenyl is a linear or branched aliphatic hydrocarbon group.
  • C 2-6 alkenyl means an alkenyl group having 2, 3, 4, 5, or 6 carbon atoms.
  • alkenyl groups include, but are not limited to, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, 3 -Methylbut-1-enyl, 1-pentenyl, 3-pentenyl and 4-hexenyl.
  • alkynyl used alone or as a suffix or prefix in the present invention is intended to include those having 2 to 20, preferably 2-6 carbon atoms (or if a specific number of carbon atoms is provided, that specific number) A branched or straight chain aliphatic hydrocarbon group of alkynyl or alkyne.
  • ethynyl, propynyl e.g., 1-propynyl, 2-propynyl
  • 3-butynyl pentynyl, hexynyl, and 1-methylpent-2-ynyl.
  • aryl used in the present invention refers to an aromatic ring structure composed of 5 to 20 carbon atoms.
  • aromatic ring structures containing 5, 6, 7 and 8 carbon atoms which can be monocyclic aromatic groups, such as phenyl; those containing 8, 9, 10, 11, 12, 13 or 14 carbon atoms
  • the ring structure can be polycyclic, such as naphthyl, anthryl, and phenanthryl.
  • aryl also includes polycyclic ring systems having two or more rings in which two or more carbons are shared by two adjacent rings (the rings are "fused rings"), in which at least One ring is aromatic and the other ring may be, for example, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, and/or heterocyclyl.
  • polycyclic rings include, but are not limited to, 2,3-dihydro-1,4-benzodioxane and 2,3-dihydro-1-benzofuran.
  • cycloalkyl as used in the present invention is intended to include saturated cyclic groups having the specified number of carbon atoms. These terms may include fused or bridged polycyclic ring systems. Cycloalkyl groups have 3 to 40 carbon atoms in their ring structure. In one embodiment, the cycloalkyl group has 3, 4, 5, or 6 carbon atoms in its ring structure.
  • C 3-6 cycloalkyl means a group such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.
  • cycloalkenyl as used in the present invention is intended to include cyclic groups containing at least one alkenyl group having the specified number of carbon atoms. These terms may include fused or bridged polycyclic ring systems.
  • the cycloalkenyl group has 3 to 40 carbon atoms in its ring structure. In one embodiment, the cycloalkenyl group has 3, 4, 5, or 6 carbon atoms in its ring structure.
  • C 3-6 cycloalkenyl means a group such as cyclopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl.
  • cycloalkynyl as used in the present invention is intended to include cyclic groups containing at least one alkynyl group having the specified number of carbon atoms. These terms may include fused or bridged polycyclic ring systems.
  • the cycloalkynyl group has 6 to 40 carbon atoms in its ring structure. In one embodiment, the cycloalkynyl group has 6 carbon atoms in its ring structure.
  • C 3-6 cycloalkynyl means a group such as cyclopropynyl, cyclobutynyl, cyclopentynyl, or cyclohexynyl.
  • heteroaryl group used in the present invention refers to a heteroaromatic heterocyclic ring having at least one ring heteroatom (for example, sulfur, oxygen, or nitrogen).
  • Heteroaryl groups include monocyclic ring systems and polycyclic ring systems (e.g., having 2, 3, or 4 fused rings).
  • heteroaryl groups include, but are not limited to, pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, quinolinyl, isoquinolinyl, thienyl, imidazolyl, thiazolyl, indole Base, pyrrolyl, oxazolyl, benzofuranyl, benzothienyl, benzothiazolyl, isoxazolyl, pyrazolyl, triazolyl, tetrazolyl, indazolyl, 1,2,4 -Thiadiazole, isothiazolyl, benzothienyl, purinyl, carbazolyl, benzimidazolyl, benzoxazolyl, azabenzoxazolyl, imidazothiazolyl, benzo[1 ,4]dioxolyl, benzo[1,3]dioxolyl, etc.
  • the heteroaryl group has 3 to 40 carbon atoms and in other embodiments 3 to 20 carbon atoms. In some embodiments, the heteroaryl group contains 3 to 14, 4 to 14, 3 to 7, or 5 to 6 ring-forming atoms. In some embodiments, the heteroaryl group has 1 to 4, 1 to 3, or 1 to 2 heteroatoms. In some embodiments, the heteroaryl group has 1 heteroatom.
  • heterocyclic group refers to a saturated, unsaturated or partially saturated monocyclic, bicyclic or tricyclic ring containing 3 to 20 atoms, wherein 1, 2, 3, 4 or 5 ring atoms are selected from Nitrogen, sulfur, oxygen, or phosphorus, unless otherwise specified, can be connected via carbon or nitrogen, where the -CH 2 -group is optionally replaced by -C(O)-; where unless otherwise specified, the ring nitrogen atom Or ring sulfur atoms are optionally oxidized to form N-oxides or S-oxides or ring nitrogen atoms are optionally quaternized; wherein -NH in the ring is optionally acetyl, formyl, methyl or methanesulfonate Acyl substitution; and the ring is optionally substituted with one or more halogens.
  • heterocyclic group when the total number of S atoms and O atoms in the heterocyclic group exceeds 1, these heteroatoms are not adjacent to each other.
  • the heterocyclic group is bicyclic or tricyclic, at least one ring may optionally be a heteroaromatic ring or an aromatic ring, provided that at least one ring is non-heteroaromatic. If the heterocyclic group is a monocyclic ring, it must not be aromatic.
  • heterocyclic groups include, but are not limited to, piperidinyl, N-acetylpiperidinyl, N-methylpiperidinyl, N-formylpiperazinyl, N-methanesulfonylpiperazinyl, homopiperazinyl , Piperazinyl, azetidinyl, oxetanyl, morpholinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, indolyl, tetrahydropyranyl, dihydro -2H-pyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetrahydrothiopyran-1-oxide, tetrahydrothiopyran-1,1-dioxide, 1H-pyridin-2-one and 2,5 -Dioxoimidazolyl.
  • alkyl in the term “alkoxy” used in the present invention is the same as above.
  • hydrazino used in the present invention refers to the -NHNHR c group, and R c has the same definition as above.
  • amino group used in the present invention refers to -NHR c group or -N(R c ) 2 group, and R c is defined as above.
  • amino refers to the -NH 2 group.
  • carboxy refers to the -COOH group.
  • the reactant toluene (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture.
  • the reaction mixture was placed in a magnetic field.
  • Light reaction to complete the reaction about 12h.
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography to obtain the target compound benzaldehyde or GC-MS quantitative (yield 23%).
  • Example 2 uses the same method as Example 1, except that the auxiliary agent is the only difference, which is listed in Table 1a.
  • Examples 2a-2q use the same method as Example 1 (each reaction time is about 8 hours or more, and can last up to 12 hours or longer), the difference is only the reactants and the light conditions (light source wavelength), the specific list In Table 1b.
  • the reactant N,N-dimethylbenzylamine (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) are dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture
  • the reaction mixture is placed in a reaction tube containing a magnetic stirrer, and the reaction tube is placed under the blue light (wavelength 420-455nm) of the 3W blue LED (the reaction mixture is placed under the blue light). In room temperature, air or oxygen (1atm) atmosphere, the light reaction is completed (about 12h).
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography or quantitatively analyzed by GC-MS to obtain the target compound benzaldehyde (yield 23%) and benzoic acid (product Rate 37%).
  • Examples 3b-3h use the same method as in Example 3 (the time of each reaction is about 8 hours or more, and can last up to 12 hours or longer). The only difference is the reactants and the light conditions (light source wavelength). In Table 2a.
  • the reactant anisole (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture.
  • the mixed solution is placed in a reaction tube containing a magnetic stirrer, and then the reaction tube is placed under violet light (wavelength 360-380nm) (the reaction mixture is placed under violet light), and light is placed at room temperature, air or oxygen The reaction is complete (about 12h).
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography to obtain the target compound phenylmethyl sulfoxide (yield 95%).
  • the reaction formula of the reaction is as follows:
  • Examples 4a-4g use the same method as Example 4 (each reaction time is about 8 hours or more, and it can last up to 12 hours or longer). The only difference is the reactants and the light conditions (light source wavelength). In Table 3a.
  • the reactant cumene (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (1.0eq.) were dissolved in an organic solvent anhydrous CH 3 CN (2mL) to obtain a reaction mixture.
  • the reaction mixture was placed Place the reaction tube in a reaction tube containing a magnetic stirrer, and place the reaction tube under blue light (the reaction mixture is placed under blue light), and illuminate the reaction tube in an oxygen atmosphere at room temperature until the reaction is complete.
  • the reaction mixture was concentrated under reduced pressure to obtain the crude target compound, and the crude target compound was separated by column chromatography to obtain the target compound acetophenone (yield 65%).
  • Example 5a uses the same method as Example 5, except that the reactants are different, which are specifically listed in Table 4a.
  • Example 5a The characterization results of Example 5a are listed in Table 4b.
  • the reactant 2-naphthaleneethylene (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture.
  • the mixed solution is placed in a reaction tube containing a magnetic stirrer, and then the reaction tube is placed under a 34W CFL (the reaction mixture is placed under blue light), and the reaction is illuminated in room temperature, air or oxygen atmosphere until the reaction is complete.
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography to obtain the target compound 2-naphthaldehyde (yield 25%).
  • Example 6a uses the same method as Example 6, except for the reactants, which are specifically listed in Table 5a.
  • the reactant 1,2-diphenylacetylene (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain the reaction mixture, Place the reaction mixture in a reaction tube containing a magnetic stirrer, and then place the reaction tube under the blue light (wavelength 420-425nm) of 3W blue LED (the reaction mixture is placed under the blue light) at room temperature, Light reaction in air or oxygen atmosphere until the reaction is complete (about 12h). After the reaction is completed, the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography to obtain the target compound bibenzoyl (yield 41%).
  • the reactant benzyl alcohol (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture, and the reaction was mixed
  • the liquid is placed in a reaction tube containing a magnetic stir bar, and then the reaction tube is placed under blue light (wavelength 400-405nm) of 3W blue LED (the reaction mixture is placed under blue light), at room temperature, air or oxygen atmosphere Medium light reaction to complete the reaction (about 12h).
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography to obtain the target compound benzophenone (yield 96%).
  • Example 8a uses the same method as Example 8, except for the reactants, which are specifically listed in Table 7a.
  • Example 8a The characterization results of Example 8a are listed in Table 7b.
  • the reactants N-methylquinoline salt iodide (0.2mmol), cesium carbonate (2.0eq) and auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in an organic solvent anhydrous CH 3 CN (2mL) to obtain the reaction mixture, place the reaction mixture in a reaction tube containing a magnetic stirrer, and then place the reaction tube under blue light (the reaction mixture is placed under blue light) at room temperature, air Or light reaction in oxygen atmosphere until the reaction is complete. After the reaction is completed, the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography to obtain the target compound N-methylquinolinone (yield 45%).
  • Examples 9a-9b use the same method as Example 9, except for the additives, which are listed in Table 8a.
  • the reactant benzyltriphenylphosphine quaternary phosphate salt (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.25eq., 0.5eq or 1.0eq) are dissolved in an organic solvent anhydrous CH 3 CN (2mL)
  • an organic solvent anhydrous CH 3 CN (2mL) To obtain the reaction mixture, place the reaction mixture in a reaction tube containing a magnetic stir bar, and then place the reaction tube under the blue light (wavelength 400-405nm) of a 3W blue LED (the reaction mixture is placed in blue light). Bottom), illuminate the reaction in room temperature, air or oxygen atmosphere until the reaction is complete (about 12h).
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography or quantitatively analyzed by GC-MS to obtain the target compound benzaldehyde (yield 58%).
  • the reactant 2-tetralone (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture.
  • the reaction mixture is placed in a reaction tube containing a magnetic stir bar, and then the reaction tube is placed under the blue light (wavelength 400-405nm) of 3W blue LED (the reaction mixture is placed under the blue light), at room temperature, air Or light reaction in oxygen atmosphere until the reaction is complete (about 12h).
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography or quantitatively analyzed by GC-MS to obtain the target compound 2-naphthol (yield 28%).
  • the reactant benzaldehyde (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.25eq, 0.5eq or 1.0eq) are dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture.
  • the reaction mixture is placed in a reaction tube containing a magnetic stirrer, and the reaction tube is placed under blue light (wavelength 400-405nm) of 3W blue LED (the reaction mixture is placed under blue light), at room temperature, air or The light reaction in oxygen atmosphere until the reaction is complete (about 12h).
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography or quantitatively analyzed by GC-MS to obtain the target compound benzoic acid (yield 100%).
  • Examples 12a-12g use the same method as Example 12, except for the reactants.
  • the specific reactions are as follows:
  • the reactant 4-phenylbenzaldehyde (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.25eq, 0.5eq or 1.0eq) were dissolved in the organic solvent absolute ethanol (2mL) to obtain the reaction mixture , Place the reaction mixture in a reaction tube containing a magnetic stirrer, and then place the reaction tube under the blue light (wavelength 400-405nm) of a 3W blue LED (the reaction mixture is placed under the blue light) at room temperature , The light reaction in air or oxygen atmosphere until the reaction is complete (about 12h).
  • the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography or quantitatively analyzed by GC-MS to obtain the target compound 4-phenylbiphenyl acetal (yield 100 %).
  • the reactant polystyrene (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent anhydrous CHCl 3 (2mL) to obtain a reaction mixture.
  • the reaction mixture Place the reaction tube in a reaction tube containing a magnetic stir bar, and then place the reaction tube under the blue light (wavelength of about 400-405nm) of the 3W blue LED (the reaction mixture is placed under the blue light), at room temperature, air or oxygen atmosphere Medium light reaction to complete the reaction (about 12h). After the reaction is completed, the reaction mixture is concentrated under reduced pressure to obtain a crude target compound, and the crude target compound is separated by column chromatography or GC-MS quantitative analysis to obtain the target compound type and content.
  • the reactant aniline (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture, and the reaction mixture was placed Place the reaction tube in a reaction tube containing a magnetic stirrer under blue light (wavelength 400-405nm) of 3W blue LED (the reaction mixture is placed under blue light), and illuminate in room temperature, air or oxygen atmosphere The reaction is complete (about 12h). After the reaction is completed, the reaction mixture is concentrated under reduced pressure to obtain the crude target compound, and the crude target compound is separated by column chromatography to obtain the target compound diphenylurea (yield 93%).
  • the reactant cyclohexanoic acid (0.2mmol) and the auxiliary agent sodium trifluoromethanesulfinate (0.5eq or 1.0eq) were dissolved in the organic solvent dry CH 3 CN (2mL) to obtain a reaction mixture, and the reaction was mixed
  • the liquid is placed in a reaction tube containing a magnetic stir bar, and then the reaction tube is placed under blue light (wavelength 400-405nm) of 3W blue LED (the reaction mixture is placed under blue light), at room temperature, air or oxygen atmosphere Medium light reaction to complete the reaction (about 12h). Distilled target compound cyclohexanone (96% yield).
  • Examples 15a-15b use the same method as Example 15, except for the reactants.
  • the specific reactions are as follows:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

公开了一种需氧氧化体系及其光促需氧氧化方法，该需氧氧化体系包括1)下述物质1a)～1d)的至少一种：1a)亚磺酸或其衍生物；1b)磺酸或其衍生物；1c)通过反应可以生成亚磺酸或其衍生物的化合物或混合物；1d)通过反应可以生成磺酸或其衍生物的化合物或混合物；和2)含分子氧的组分，包括氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。该需氧氧化体系用于氧化方法时，在光照条件下，无需添加光敏化试剂，室温下即可需氧氧化一系列化合物得到相应的氧化产物，降低了生产成本；另外，所述方法能够大幅度降低能耗，彻底解决由重金属和酸性溶剂带来的废弃物排放污染环境的问题，以及产品中金属残留的问题。

Description

一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法
本申请要求2019年2月1日向中国国家知识产权局提交的专利申请号为201910105393.5，发明名称为“一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法”的在先申请的优先权。该在先申请的全文通过引用的方式结合于本申请中。
技术领域
本发明属于化工技术、材料和生物医药领域，具体涉及一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法。
背景技术
氧化反应是自然界中最基础也是极其重要的一类反应，其中，有机化合物的选择性氧化是现代合成化学、也是氧化反应的重要组成部分。
在过去的几十年中，直接氧化有机化合物中的C-H和C-C键使其功能化已被证明是从简单、现成的原料合成复杂产品的最直接和有效的方法。由于分子氧具有含量丰富，原子经济性高以及环境友好的特点，故分子氧作为绿色、环保和可持续的温和氧化剂而备受关注。因此，发展以分子氧作为氧化剂的理想氧化方法在工业生产和学术研究中均具有极其重要的意义。更重要的是，使用分子氧作为氧原子来源提供了简单分子的氧化反应构建含氧化合物以及氧化产物的最理想的方法。但是，目前的以分子氧作为氧源的氧化反应通常需要金属催化剂、配体或生物酶的参与，在高温或高压条件下进行，使得该类转化在工业化生产中受到限制。因此，常温常压下的需氧氧化反应方法的研究在实际生产中显得尤为重要。
另外，对于有机化合物的氧化通常需要大量的强氧化剂如：KMnO 4，CrO 4，CH 3COOOH，Na 2S 2O 8或KIO 4等。一方面，强氧化剂一般在储存、操作、成本以及环保等方面存在诸多问题；另一方面，由于强氧化剂的使用，使得产物无法停留在相对活性的中间氧化态，限制了这类方法的应用。在反应后处理方面，通常需要大量的水洗，且这些废水中含有大量的重金属离子，会造成严重的环境污染问题。因此，开发新型环保的需氧氧化体系及方法就十分必要和紧迫。
发明内容
为解决上述问题，本发明的目的在于提供一种含亚磺酸或其衍生物，磺酸或其衍生物，通过反应可以生成亚磺酸或其衍生物的化合物或混合物，和/或通过反应可以生成磺酸或其衍生物的化合物或混合物的需氧氧化体系。具体的，本发明采用亚磺酸或其衍生物，磺酸或其衍生物，通过反应可以生成亚磺酸或其衍生物的化合物或混合物，和/或通过反应可以生成磺酸或其衍生物的化合物或混合物作为辅助助剂，与含分子氧的组分配合得到所述需氧氧化体系，该体系在光照条件下，因所述辅助助剂的辅助作用而使得分子氧被活化，该活化的分子氧可用于氧化一系列碳氢键(C-H)、碳碳单键(C-C)、碳碳双键(C＝C)、碳碳三键(C≡C)及碳杂键(包括碳氧键(C-O)、碳氮键(C-N)、碳硫键(C-S)、碳硒键(C-Se)、碳硅键(C-Si)、碳磷键(C-P)、碳氮双键(C＝N)等)等，从而合成多种氧化产物。
本发明的另一目的在于提供一种光促氧化方法，所述方法采用上述的需氧氧化体系实现反应原料的氧化过程以制备得到所述原料的氧化产物。该发明为多种反应原料的氧化产物(含氧化合 物及相关氧化产物)的绿色合成提供了高效率，低成本，高氧原子经济性，高底物广谱性的新方法，其简单实用的操作使得该发明方法非常有吸引力和实用性。
本发明提供如下技术方案：
一种需氧氧化体系，该体系包括：
1)下述物质1a)～1d)的至少一种：
1a)亚磺酸或其衍生物；
1b)磺酸或其衍生物；
1c)通过反应可以生成亚磺酸或其衍生物的化合物或混合物；
1d)通过反应可以生成磺酸或其衍生物的化合物或混合物；
和2)含分子氧的组分，包括氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
其中，组分1)的量为所述需氧氧化体系参与的需氧氧化反应中待氧化的反应原料的活性位点数的0.001-10倍量。
所述体系中，组分2)选自氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
所述体系中，组分2)可以是直接引入的，如氧气、含氧气的气体(如空气、氧气与惰性气体的混合物等)，也可以是原位生成的，如加入可以原位生成氧分子的反应体系的原料，具体如KMnO 4、KClO 3或H 2O 2等等。
所述体系中还可以加入3)酸类、碱类、盐类等添加剂以及有机或过渡金属类催化剂中的一种或多种。
所述体系由上述组分1)、上述组分2)和任选地上述组分3)组成。
本发明还提供一种光促需氧氧化方法，所述方法采用上述的需氧氧化体系在光照条件下制备反应原料的氧化产物。
本发明的有益效果
本发明采用亚磺酸或其衍生物、磺酸或其衍生物、通过反应可以生成亚磺酸或其衍生物的化合物或混合物、和/或通过反应可以生成磺酸或其衍生物的化合物或混合物作为辅助助剂，在光照条件下，无需添加光敏化试剂，室温下(绝大多数反应)即可需氧氧化一系列化合物得到相应的氧化产物，降低了生产成本。值得注意的是，在该方法中所采用的辅助助剂在反应结束后能够得到附加值更高的磺酸衍生物，反应体系中无废弃物产生，更加节能环保；本发明能够大幅度降低能耗，彻底解决由重金属和酸性溶剂带来的废弃物排放污染环境的问题，以及产品中金属残留的问题。本发明与传统的生产工艺方法相比，整体耗电量，设备投资以及整体运营成本大大降低。
附图说明
图1亚磺酸及其衍生物作为辅助助剂催化分子氧活化及需氧氧化过程的原理示意图；
图2亚磺酰氯作为辅助助剂催化分子氧活化及需氧氧化过程的原理示意图；
图3磺酸及其衍生物作为辅助助剂催化分子氧活化及需氧氧化过程的原理示意图；
其中，R 1、M和Ar的定义见下文。
具体实施方式
[亚磺酸或其衍生物、磺酸或其衍生物、通过反应可以生成亚磺酸或其衍生物的化合物或混合物、 和/或通过反应可以生成磺酸或其衍生物的化合物或混合物]
如前所述，本发明首次提出了一类光照条件下促进分子氧活化的辅助助剂，即下述物质1a)～1d)的至少一种：
1a)亚磺酸或其衍生物；
1b)磺酸或其衍生物；
1c)通过反应可以生成亚磺酸或其衍生物的化合物或混合物；
1d)通过反应可以生成磺酸或其衍生物的化合物或混合物。
所述亚磺酸的结构式如式1所示：
Figure PCTCN2019098940-appb-000001
式1中，R 1选自未取代或任选被一个或多个R a取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、烷氧基、芳氧基等；每一个R a彼此独立地选自氧代、卤素、羟基、巯基、硝基、烷基、一个或多个R a1取代的烷基、烷氧基、一个或多个R a1取代的烷氧基、环烷基、一个或多个R a1取代的环烷基、硅氧基、杂环基、一个或多个R a1取代的杂环基、芳基、一个或多个R a1取代的芳基、杂芳基、一个或多个R a1取代的杂芳基、芳氧基、一个或多个R a1取代的芳氧基、磺酰基、亚磺酰基、酰基、酯基等；每一个R a1彼此独立地选自氧代、卤素、羟基、巯基、硝基、烷基、烷氧基、环烷基、杂环基、芳基、杂芳基、芳氧基、磺酰基、亚磺酰基、酰基、酯基等，所述R a1任选被一个或多个卤素、烷基、羟基取代。
具体的，所述R 1选自未取代或任选被一个或多个R a取代的下列基团：烷基、环烷基、杂环基、芳基或杂芳基，每一个R a彼此独立地选自氧代、卤素、烷基、任选卤素取代的烷氧基、硝基、羟基、卤代烷基、一个或多个芳基(任选被烷基和/或羟基取代)取代的烷基、磺酰基等。例如，所述R 1中的烷基选自C 1-C 12烷基；所述R 1中的环烷基选自C 3-C 6环烷基；所述R 1中的杂环基选自吗啉基、四氢呋喃基、吡咯啉基；所述R 1中的芳基选自苯基；所述R 1中的杂芳基选自吡啶基、咪唑基、喹喔啉基；所述每一个R a彼此独立地选自卤素(如氟、氯等)、C 1-C 12烷基、C 1-C 12烷氧基、一个或多个卤素取代的C 1-C 12烷氧基、硝基、羟基、卤代烷基(如三氟甲基等)、苯基、苯基取代的C 1-C 12烷基(其中苯基任选被烷基和/或羟基取代)(如二(甲基羟基苯基)甲基等)、任选卤素取代的C 1-C 12烷基磺酰基(如甲磺酰基、三氟甲基磺酰基等)。
具体的，所述亚磺酸选自苯亚磺酸、甲基亚磺酸、乙基亚磺酸、环丙基亚磺酸、对甲苯亚磺酸等。
所述磺酸的结构式如式2所示：
Figure PCTCN2019098940-appb-000002
式2中，R 1的定义如上所述。
具体的，所述磺酸选自苯磺酸、甲基磺酸、乙基磺酸、环丙基磺酸、三氟甲基磺酸、对甲苯磺酸、1,2,2-三氟-2-羟基-1-三氟甲基乙烷磺酸、邻甲酚磺酞(又称甲酚红，CAS登记号为1733-12-6)等。
所述亚磺酸衍生物选自亚磺酸盐、亚磺酸酯、亚磺酰卤等。
其中，所述亚磺酸盐可以为亚磺酸金属盐、亚磺酸铵盐或亚磺酸鏻盐，例如具有下述式3所示结构式：
Figure PCTCN2019098940-appb-000003
式3中，R 1定义如上所述；M为金属原子、NH 4 +或PH 4 +；n为M的价态数目(例如为1-4的整数)。具体的，所述M可以是碱金属、碱土金属、主族金属、过渡金属、NH 4 +或PH 4 +等，例如为Li、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、Al、Zn、Sn、Pb、NH 4 +或PH 4 +等。
具体的，所述亚磺酸盐选自苯亚磺酸钠、甲基亚磺酸钠、乙基亚磺酸钠、丙基亚磺酸钠、环丙基亚磺酸钠、三氟甲基亚磺酸钠、二氟甲基亚磺酸钠、氟甲基亚磺酸钠、对甲苯亚磺酸钠、吡啶-3-亚磺酸钠、三氟甲基亚磺酸钾、对甲苯亚磺酸钾、三氟甲基亚磺酸锌、三氟甲基亚磺酸锂、三氟甲基亚磺酸铵等。
其中，所述亚磺酸酯可以具有下述式4所示结构式：
Figure PCTCN2019098940-appb-000004
式4中，R 1定义如上所述，R 2选自未取代或任选被一个或多个R a’取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基等；每一个R a’彼此独立地选自氧代、卤素、羟基、巯基、硝基、烷基、一个或多个R a1’取代的烷基、烷氧基、一个或多个R a1’取代的烷氧基、环烷基、硅氧基、杂环基、一个或多个R a1’取代的杂环基、芳基、一个或多个R a1’取代的芳基、杂芳基、一个或多个R a1’取代的杂芳基、芳氧基、一个或多个R a1’取代的芳氧基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R a1’彼此独立地选自氧代、卤素、羟基、巯基、硝基、烷基、烷氧基、环烷基、杂环基、芳基、杂芳基、芳氧基、酰基、亚磺酰基、磺酰基、磷酰基等；R 1和R 2还任选地可以成环。
具体的，所述R 2选自未取代或任选被一个或多个R a’取代的下列基团：烷基、环烷基、杂环基、芳基、杂芳基等；每一个R a’彼此独立地选自卤素、羟基、巯基、硝基、烷基、一个或多个R a1’取代的烷基、烷氧基、一个或多个R a1’取代的烷氧基、环烷基、硅氧基、杂环基、一个或多个R a1’取代的杂环基、芳基、一个或多个R a1’取代的芳基、杂芳基、一个或多个R a1’取代的杂芳基、芳氧基、一个或多个R a1’取代的芳氧基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R a1’彼此独立地选自卤素、羟基、巯基、硝基、烷基、烷氧基、环烷基、杂环基、芳基、杂芳基、芳氧基等；R 1和R 2还任选地可以成环。
式4中，若R 1和R 2成环，具有下述式4a所示结构式：
Figure PCTCN2019098940-appb-000005
式4a中，m0选自0或1或2或3；R b1和R b2相同或不同，彼此独立地选自H、烷基，或者R b1与R b2 成环形成烃基环或芳香环(如苯环、萘环、蒽环等)；R b3和R b4相同或不同，彼此独立地选自H、烷基、任选被一个或多个卤素或羟基取代的芳基。
具体的，所述亚磺酸酯选自(1R,2S,5R)-(-)-孟基-(S)-对甲苯亚磺酸酯、三氟甲基亚磺酸甲酯、三氟甲基亚磺酸苯酯等。
其中，所述亚磺酰卤可以具有下述式5所示结构式：
Figure PCTCN2019098940-appb-000006
式5中，R 1定义如上所述，X 1选自下列基团：氟、氯、溴、碘。
具体的，所述亚磺酰卤选自苯亚磺酰氯、三氟甲基亚硫酰氯、叔丁基亚磺酰氯、三氟甲基亚磺酰溴等。
所述通过反应可以生成亚磺酸或其衍生物的化合物或混合物例如可以是亚磺酸酯(如式4所示)与酸(如盐酸、硫酸、碳酸、甲酸、乙酸、丙二酸等)的混合物、亚磺酸酯(如式4所示)与碱(如氢氧化钠、氢氧化钾、氢氧化锂、乙醇钠、甲醇钠、叔丁醇钠等)的混合物、亚磺酸盐(如式3所示)与碱(如氢氧化钠、氢氧化钾、氢氧化锂、乙醇钠、甲醇钠、叔丁醇钠等)的混合物等等。上述混合物的反应包括但不限于下述反应式所示情况：
Figure PCTCN2019098940-appb-000007
上述反应式中，R 1、R 2、M和n的定义如上所述。
所述磺酸衍生物选自磺酸盐、磺酸酯或磺酸酐、磺酰卤、磺酰卤的无机盐等。
其中，所述磺酸盐可以为磺酸金属盐、磺酸铵盐或磺酸鏻盐，例如具有下述式3’所示结构式：
Figure PCTCN2019098940-appb-000008
式3’中，R 1、M和n的定义如上所述。
具体的，所述磺酸盐选自苯磺酸钠、甲基磺酸钠、乙基磺酸钠、丙基磺酸钠、三氟甲基磺酸钠、二氟甲基磺酸钠、氟甲基磺酸钠、环丙基磺酸钠、三氟甲基磺酸钾、三氟甲基磺酸锌、对甲苯磺酸钠、2,4,5-三氯苯磺酸钠、对甲苯磺酸钾、三氟甲烷磺酸铵、吡啶-3-磺酸钠、三氟甲基磺酸锂、十二烷基苯磺酸钠、十二烷基磺酸钠、三氟甲基磺酸铜、三氟甲基磺酸铵等。
其中，所述磺酸酯或磺酸酐可以具有下述式4’所示结构式：
Figure PCTCN2019098940-appb-000009
式4’中，R 1和R 2的定义如上所述。
式4’中，若R 1和R 2成环，具有下述式4a’所示结构式：
Figure PCTCN2019098940-appb-000010
式4a’中，m0、R b1、R b2、R b3和R b4的定义同式4a。
具体的，所述磺酸酯或磺酸酐选自3-氟丙基-4-甲基苯磺酸酯、2-(噻吩-2-基)乙基对甲苯磺酸酯、对甲苯磺酸苯乙酯、对甲苯磺酰氧甲基膦酸二乙酯、4-硝基苯酚三氟甲基磺酸酯、2-(叔丁基二甲基硅烷基)氧基乙醇三氟甲磺酸酯、三氟甲基磺酸甲酯、1,4-丁磺酸内酯、1,1'-联-2-萘酚二(三氟甲基磺酸酯)、对甲苯磺酸乙酯、2,2,2-三氟乙基甲基磺酸酯、2,2,2-三氟乙基对甲苯磺酸酯、四溴酚蓝、酚红、甲磺酸甲酯、1,3-丙烷磺内酯、甲基磺酸异丙酯、三氟甲基磺酸酐、甲基磺酸酐、4-甲苯磺酸酐、九氟丁基磺酸酐、三氟乙酰三氟甲磺酸酯、苯磺酸酐等。
其中，所述磺酰卤可以具有下述式5’所示结构式：
Figure PCTCN2019098940-appb-000011
式5’中，R 1和X 1的定义如上所述。
式5’中，R 1为含N的杂环基或杂芳基时，可以与无机盐形成磺酰卤的无机盐。
具体的，所述磺酰卤或磺酰卤的无机盐选自三氟甲烷磺酰氯、十二烷基苯磺酰氯、2-甲基丙烷磺酰氯、吡啶-4-磺酰氯、4-吡啶磺酰氯盐酸盐、4-吗啉磺酰氯、4-砒啶磺酰氯盐酸盐、咪唑-4-磺酰氯、2-氯-4-硝基苯磺酰氯、四氢吡喃-4-磺酰氯、喹喔啉-5-磺酰氯、吡咯啉-1-磺酰氯、对乙氧基苯磺酰氯、2-苯基-乙烷磺酰氯、甲基甲烷二磺酰氯、2-甲氧基苯磺酰氯、2-氯吡啶-3-磺酰氯、2-氟-1-丙烷磺酰氯、三氟甲基磺酰氟、苯磺酰溴、丙基磺酰氟、三氟甲烷磺酰氟、吡啶-2-磺酰氟、苯甲基磺酰氟、全氟己基磺酰氟、全氟丁基磺酰氟、2-(2-碘-四氟乙氧基)四氟乙基硫酰氟、三氟甲基磺酰溴、苯磺酰溴等。
所述通过反应可以生成磺酸或其衍生物的化合物或混合物例如可以是磺酸酯或磺酸酐(如式4’所示)与酸(如盐酸、硫酸、碳酸、甲酸、乙酸、丙二酸等)的混合物、磺酸酯或磺酸酐(如式4所示)与碱(如氢氧化钠、氢氧化钾、氢氧化锂、乙醇钠、甲醇钠、叔丁醇钠等)的混合物、磺酸盐(如式3所示)与碱(如氢氧化钠、氢氧化钾、氢氧化锂、乙醇钠、甲醇钠、叔丁醇钠等)的混合物、磺酸酐与亲核试剂(如醇、硫醇、胺、吡啶等)的混合物等等。上述混合物的反应包括但不限于下述反应式所列情况：
Figure PCTCN2019098940-appb-000012
上述反应式中，R 1、R 2、M和n的定义如上所述；“O-S bond cleavage”是“O-S键断裂”，“nucleophile”是“亲核试剂”，“eg”是“例如”，“pyridine”是“吡啶”，“etc.”是“等”。
[含分子氧的组分]
本发明所述含分子氧的组分，包括氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
所述含氧气的气体可以是空气、氧气和惰性气体的混合物等等。
所述可以原位生成氧分子的反应体系的原料，具体如KMnO 4、KClO 3或H 2O 2等等。所述可以原位生成氧分子的反应体系包括但不限于以下反应类型之一：
Figure PCTCN2019098940-appb-000013
其中，“heating”是“加热”，“Cat.”是“催化剂”。
[需氧氧化体系]
如前所述，本发明首次提出了一种需氧氧化体系，该体系包括：1)下述物质1a)～1d)的至少一种：1a)亚磺酸或其衍生物，1b)磺酸或其衍生物，1c)通过反应可以生成亚磺酸或其衍生物的化合物或混合物，1d)通过反应可以生成磺酸或其衍生物的化合物或混合物；和2)含分子氧的组分，包括氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
所述体系中，组分1)的具体选择如前所述。组分1)在体系中的比例可以通过下述方式加以限定：
一般而言，组分1)的含量没有特别限定，具体的，与其参与的需氧氧化反应中待氧化的反应原料的活性位点数相关；例如，组分1)的量与所述需氧氧化体系参与的需氧氧化反应中待氧化的反应原料的加入量有关，例如，相对于1mmol反应底物(即待氧化的反应原料)而言，约为0.001～10eq(例如为0.1～10eq，再例如2～8eq，再例如为2.5～5eq)，且反应原料的氧化程度可通过组分1)的比例以及光源波长控制。
所述体系中，组分2)可以是直接引入的，如氧气、含氧气的气体(如空气、氧气与惰性气体的混合物等)，也可以是原位生成的，如加入可以原位生成氧分子的反应体系的原料，具体如KMnO 4、KClO 3或H 2O 2等等。
在本发明的一种实施方式中，所述体系中还可以加入组分3)即酸类、碱类、盐类等添加剂以及有机或过渡金属类催化剂中的一种或多种，以调节该氧化体系的氧化性和反应性，并用于实现一锅法合成复杂化合物。
其中，所述酸类添加剂选自有机或无机酸类化合物，其加入量没有特别限定，适用于所述反应的需要量即可，例如，其加入量为所述需氧氧化体系参与的需氧氧化反应中待氧化的反应原料的0.1-3eq。具体的，所述酸类添加剂可以为甲酸、乙酸、丙酸、磷酸、亚磷酸、碳酸、盐酸、硝酸及硫酸等酸性化合物中的一种或多种。
其中，所述碱类添加剂选自有机或无机碱类化合物，其加入量没有特别限定，适用于所述反应的需要量即可，例如，其加入量为所述需氧氧化体系参与的需氧氧化反应中待氧化的反应原料的0.1-3eq。具体的，所述碱类添加剂可以为甲胺、二甲胺、乙胺、二乙胺、三乙胺、丁胺、苯胺以及氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸铯、碳酸氢钠、碳酸氢钾、磷酸钠、磷酸氢二 钠、磷酸二氢钠、磷酸钾、磷酸氢二钾、磷酸二氢钾等碱性化合物中的一种或多种。
其中，所述盐类添加剂选自有机或无机盐，其加入量没有特别限定，适用于所述反应的需要量即可，例如，其加入量为所述需氧氧化体系参与的需氧氧化反应中待氧化的反应原料的0.1-3eq。具体的，所述盐类添加剂可以为季铵盐、季鏻盐、胺盐酸盐、胺硫酸盐以及硫酸钠、硫酸钾、氯化镁等盐类化合物中的一种或多种。
其中，所述有机或过渡金属类催化剂选自磷酸催化剂、有机胺催化剂、有机季铵盐催化剂、有机硫催化剂以及过渡金属钯、钌、铑、铱、铜、铁、钴、镍、铂催化剂等。其加入量没有特别限定，适用于所述反应的需要量即可，例如，其加入量为所述需氧氧化体系参与的需氧氧化反应中待氧化的反应原料的0.001-3eq。具体的，所述有机或过渡金属类催化剂可以为脯氨酸、四丁基溴化铵、四丁基碘化铵、醋酸钯、二氯二(三苯基膦)钯、三氯化钌、氯化铜、氯化亚铜、氰化亚铜、氯化铁、氯化亚铁、乙酰丙酮铁、氯化镍、溴化镍、乙酰丙酮镍等。
[光促需氧氧化方法]
如前所述，本发明首次提出了一种光促需氧氧化方法，所述方法采用上述的需氧氧化体系在光照条件下制备反应原料的氧化产物；具体的，所述方法是采用上述的需氧氧化体系实现反应原料的氧化过程以制备得到所述反应原料的氧化产物。
一般而言，需氧氧化体系中组分1)的加入量相对于1mmol反应底物(即待氧化的反应原料)而言，约为0.001～10eq(例如为0.1～10eq，再例如2～8eq，再例如为2.5～5eq)。
[反应原料]
如前所述，所述需氧氧化体系在光照条件下，因所述辅助助剂的辅助作用而使得分子氧被活化，该活化分子氧可用于氧化一系列碳氢键(C-H)、碳碳单键(C-C)、碳碳双键键(C＝C)、碳碳三键(C≡C)及碳杂键(包括碳氧键(C-O)、碳氮键(C-N)、碳硫键(C-S)、碳硒键(C-Se)、碳硅键(C-Si)、碳磷键(C-P)、碳氮双键(C＝N)等)等，从而合成多种氧化产物。因此，作为反应原料而言，可以是含有碳氢键(C-H)、碳碳单键(C-C)、碳碳双键(C＝C)、碳碳三键(C≡C)及碳杂键(包括碳氧键(C-O)、碳氮键(C-N)、碳硫键(C-S)、碳硒键(C-Se)、碳硅键(C-Si)、碳磷键(C-P)、碳氮双键(C＝N)等)等的有机小分子、杂环盐类化合物、有机膦盐化合物或聚合物。具体的，所述含有碳氢键(C-H)、碳碳单键(C-C)、碳碳双键(C＝C)、碳碳三键(C≡C)及碳杂键(包括碳氧键(C-O)、碳氮键(C-N)、碳硫键(C-S)、碳硒键(C-Se)、碳硅键(C-Si)、碳磷键(C-P)、碳氮双键(C＝N)等)等的有机小分子、杂环盐类化合物、有机膦盐化合物或聚合物例如是下述物质的一种：
1)具有式6所示结构的化合物：
Figure PCTCN2019098940-appb-000014
式6中，R 3选自未取代或任选被一个或多个R b取代的下列基团：芳基、杂芳基等；R 4选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烷氧基、杂环基、芳基、杂芳基、卤素、羟基、巯基、硝基、氨基、肼基、酰基、亚磺酰基、磺酰基、磷酰基、羧基、酯基、酰胺基等；R 3和R 4基团任选地可以成环(例如可以成碳环或杂环)；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷 基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基、芳基。
具体的，R 4基团选自H、未取代或任选被一个或多个R b取代的下列基团：C 1-C 12烷基(优选C 1-C 6烷基，还优选C 1-C 4烷基，如甲基、乙基、丙基、丁基等)、C 3-C 12环烷基(优选C 3-C 7环烷基，还优选C 3-C 6环烷基，如环丙基、环丁基、环戊基、环己基等)、杂环基(如四氢吡咯基、氢化吡啶基、环丙胺基、环己胺基、四氢呋喃基、四氢吡喃基等)、杂芳基(如吡咯基、吡啶基、喹啉基、异喹啉基、吲哚基、咪唑基、呋喃基、吡喃基等)、卤素(如氟、氯、溴、碘等)、硝基、C 1-C 12烷氧基(如甲氧基)、芳基(苯基、萘基、蒽基、菲基等)、酯基、酰胺基等；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。
进一步的，式6所示结构的化合物可以是下述式6a所示化合物中的一种：
Figure PCTCN2019098940-appb-000015
式6a中，Ar选自未取代或任选地被至少一个R b取代的芳基或杂芳基，R b的定义如上所述；R’相同或不同，彼此独立地选自H、卤素、羟基、巯基、硝基、烷基、烷氧基、环烷基、杂环基、芳基、杂芳基、氨基、肼基、酰基、亚磺酰基、磺酰基、磷酰基、酯基等，每一个R’还可以被一个或多个R b1取代，多个R’还可以成环(例如成碳环或杂环)；m1为0-5的整数；R b1、R 4的定义如上所述。
具体的，式6所示结构的化合物可以是：甲苯、4-氟甲苯、2-氟甲苯、3-氟甲苯、4-氯甲苯、2-氯甲苯、3-氯甲苯、4-溴甲苯、2-溴甲苯、3-溴甲苯、4-碘甲苯、2-碘甲苯，3-碘甲苯、4-三氟甲基甲苯、2-三氟甲基甲苯，3-三氟甲基甲苯、4-氰基甲苯、2-氰基甲苯，3-氰基甲苯、4-甲基苯乙酮、3-甲基苯乙酮，2-甲基苯乙酮、4-甲基苯甲醚、3-甲基苯甲醚、2-甲基苯甲醚、1,4-二甲苯、1,3-二甲苯、1,2-二甲苯、均三甲基苯、均三甲基溴苯、4-对甲基硝基苯、2,6-二溴甲苯、2,5-二溴甲苯、2,4-二溴甲苯、2,3-二溴甲苯、3,4-二溴甲苯、3,5-二溴甲苯，2,3-二溴甲苯、3,4-二溴甲苯、2,6-二碘甲苯、3,5-二碘甲苯、2,3-二碘甲苯、3,4-二碘甲苯、2,3,4,5,6-五氟甲苯、4-叔丁基甲苯、3-叔丁基甲苯、4-甲基苯甲酸甲酯、4-甲基苯甲酸乙酯、3-甲基苯甲酸甲酯、3-甲基苯甲酸乙酯、2-甲基苯甲酸甲酯、2-甲基苯甲酸乙酯、4-甲基苯酚、3-甲基苯酚、2-甲基苯酚、4-甲基苯甲醇、3-甲基苯甲醇、2-甲基苯甲醇、4-甲基苯硫酚、3-甲基苯硫酚、2-甲基苯硫酚、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2,6-二甲基吡啶、2-甲基喹啉、3-甲基喹啉、4-甲基喹啉、5-甲基喹啉、6-甲基喹啉、7-甲基喹啉、8-甲基喹啉、3,4-二甲基喹啉、4,5-二甲基喹啉、5,6-二甲基喹啉、5,7-二甲基喹啉、5,8-二甲基喹啉、6,8-二甲基喹啉、乙基苯、4-氟乙基苯、2-氟乙基苯、3-氟乙基苯、4-氯乙基苯、2-氯乙基苯、3-氯乙基苯、4-溴乙基苯、2-溴乙基苯、3-溴乙基苯、4-碘乙基苯、2-碘乙基苯，3-碘乙基苯，4-乙基苯乙酮、3-乙基苯乙酮，2-乙基苯乙酮、4-乙基苯甲醚、3-乙基苯甲醚、2-乙基苯甲醚、1,4-二乙基苯、1,3-二乙基苯、1,2-二乙基苯、均三乙基苯、均三乙基溴苯、3,4-氯乙基苯，4-硝基乙基苯、2,6-二溴乙基苯、2,5-二溴乙基苯、2,4-二溴乙基苯、2,3-二溴乙基苯、3,4-二溴乙基苯、3,5-二溴乙基苯、2,6-二碘乙基苯、3,5-二碘乙基苯、2,3-二碘乙基苯、3,4-二碘乙基苯、2,3,4,5,6-五氟乙基苯、4-叔丁基乙基苯、3-叔丁基乙基苯、4-乙基苯甲酸甲酯、4- 乙基苯甲酸乙酯、3-乙基苯甲酸甲酯、3-乙基苯甲酸乙酯、2-乙基苯甲酸甲酯、2-乙基苯甲酸乙酯、4-乙基苯酚、3-乙基苯酚、2-乙基苯酚、4-乙基苯甲醇、3-乙基苯甲醇、2-乙基苯甲醇、4-乙基苯硫酚、3-乙基苯硫酚、2-乙基苯硫酚，2-乙基吡啶、3-乙基吡啶、4-乙基吡啶、2,6-二乙基吡啶、2-乙基喹啉、3-乙基喹啉、4-乙基喹啉、5-乙基喹啉、6-乙基喹啉、7-乙基喹啉、8-乙基喹啉、3,4-二乙基喹啉、4,5-二乙基喹啉、5,6-二乙基喹啉、5,7-二乙基喹啉、5,8-二乙基喹啉、6,8-二乙基喹啉、2-苄基吡啶、3-苄基吡啶、4-苄基吡啶、二苯甲烷、1,2-二苯基乙烷、1-苯基-2-溴乙烷、1-苯基丙烷、3-苯基-1-丙醇、3-苯基-1-丙胺、1-苯基丁烷、1-苯基戊烷、1-苯基己烷、1-甲基萘、2-甲基萘、1-甲基蒽、2-甲基蒽、1-甲基菲、2-甲基菲、1-乙基萘、2-乙基萘、1-萘基丙烷、1-萘基丁烷、1-萘基戊烷、1-萘基己烷、1-蒽基乙烷、1-蒽基丙烷、1-蒽基丁烷、1-蒽基戊烷、1-蒽基己烷、1-菲基乙烷、1-菲基丙烷、1-菲基丁烷、1-菲基戊烷、1-菲基己烷等。
2)具有式7所示结构的化合物：
Figure PCTCN2019098940-appb-000016
式7中，R’ 3＝R 3；R 5相同或不同，彼此独立地选自未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基、肼基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；两个R 5任选可以成烃基环；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。
具体的，R 5相同或不同，彼此独立地选自未取代或任选被一个或多个R b取代的下列基团：C 1-C 12烷基(优选C 1-C 6烷基，还优选C 1-C 4烷基，如甲基、乙基、丙基、丁基等)、C 3-C 12环烷基(优选C 3-C 7环烷基，还优选C 3-C 6环烷基，如环丙基、环丁基、环戊基、环己基等)、杂环基(如四氢吡咯基、氢化吡啶基、环丙胺基、环己胺基、四氢呋喃基、四氢吡喃基等)、杂芳基(如吡咯基、吡啶基、喹啉基、异喹啉基、吲哚基、咪唑基、呋喃基、吡喃基等)、卤素(如氟、氯、溴、碘等)、硝基、C 1-C 12烷氧基(如甲氧基)、芳基(苯基、萘基、蒽基、菲基等)、酯基、酰胺基等；或者两个R 5一起形成环烷基(优选C 3-C 7环烷基，还优选C 3-C 6环烷基，如环丙基、环丁基、环戊基、环己基等)，每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。
进一步的，式7所示结构的化合物可以是下述式7a所示化合物中的一种：
Figure PCTCN2019098940-appb-000017
式7a中，Ar、R’、R 5、m1的定义如上所述。
具体的，式7所示结构的化合物可以是：异丙基苯、4-氟异丙基苯、2-氟异丙基苯、3-氟异丙基苯、4-氯异丙基苯、2-氯异丙基苯、3-氯异丙基苯、4-溴异丙基苯、2-溴异丙基苯、3-溴异丙基苯、4-碘异丙基苯、2-碘异丙基苯，3-碘异丙基苯、4-三氟甲基异丙基苯、2-三氟甲基异丙基苯， 3-三氟甲基异丙基苯、4-氰基异丙基苯、2-氰基异丙基苯，3-氰基异丙基苯、4-异丙基苯乙酮、3-异丙基苯乙酮，2-异丙基苯乙酮、4-异丙基苯甲醚、3-异丙基苯甲醚、2-异丙基苯甲醚、1,4-二异丙基苯、1,3-二异丙基苯、1,2-二异丙基苯、均三异丙基苯、均三异丙基苯溴苯、4-异丙基硝基苯、2,6-二溴异丙基苯、2,5-二溴异丙基苯、2,4-二溴异丙基苯、2,3-二溴异丙基苯、3,4-二溴异丙基苯、3,5-二溴异丙基苯，2,3-二溴异丙基苯、3,4-二溴异丙基苯、2,6-二碘异丙基苯、3,5-二碘异丙基苯、2,3-二碘异丙基苯、3,4-二碘异丙基苯、2,3,4,5,6-五氟异丙基苯、4-叔丁基异丙苯、3-叔丁基异丙苯、4-异丙基苯甲酸甲酯、4-异丙基苯甲酸乙酯、3-异丙基苯甲酸甲酯、3-异丙基苯甲酸乙酯、2-异丙基苯甲酸甲酯、2-异丙基苯甲酸乙酯、4-异丙基苯酚、3-异丙基苯酚、2-异丙基苯酚、4-异丙基苯甲醇、3-异丙基苯甲醇、2-异丙基苯甲醇、4-异丙基苯硫酚、3-异丙基苯硫酚、2-异丙基苯硫酚、2-苯基丁烷、2-苯基戊烷、3-苯基戊烷、2-苯基己烷、3-苯基己烷、2-苯基庚烷、3-苯基庚烷、4-苯基庚烷、1,1-二苯基乙烷、三苯基甲烷、环丁基苯、环戊基苯、环己基苯、2-萘基丙烷、2-萘基丁烷、2-萘基戊烷、2-萘基己烷、2-萘基庚烷、2-蒽基丙烷、2-蒽基丁烷、2-蒽基戊烷、2-蒽基己烷、2-蒽基庚烷、2-菲基丙烷、2-菲基丁烷、2-菲基戊烷、2-菲基己烷、2-菲基庚烷、2-吡啶基丙烷、2-吡啶基丁烷、2-吡啶基戊烷，3-吡啶基戊烷，2-喹啉基丙烷、2-吡喹啉基丁烷、2-喹啉基戊烷、3-喹啉基戊烷、2-环己基喹啉、3-环己基喹啉、4-环己基喹啉、5-环己基喹啉、6-环己基喹啉、7-环己基喹啉、8-环己基喹啉、2-环戊基喹啉、3-环戊基喹啉、4-环戊基喹啉、5-环戊基喹啉、6-环戊基喹啉、7-环戊基喹啉、8-环戊基喹啉、1-环己基异喹啉、3-环己基异喹啉、4-环己基异喹啉、5-环己基异喹啉、6-环己基异喹啉、7-环己基异喹啉、8-环己基异喹啉、1-环戊基异喹啉、3-环戊基异喹啉、4-环戊基异喹啉、5-环戊基异喹啉、6-环戊基异喹啉、7-环戊基异喹啉、8-环戊基异喹啉等。
3)具有式8所示结构的化合物：
Figure PCTCN2019098940-appb-000018
式8中，R” 3选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基等；R 7选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、羧基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；R 8和R 9相同或不同，彼此独立地选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基、肼基、羧基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。
进一步的，所述R 7基团选自H、未取代或任选被一个或多个R b取代的下列基团：C 1-C 12烷基(优选C 1-C 6烷基，还优选C 1-C 4烷基，如甲基、乙基、丙基、丁基等)、C 3-C 12环烷基(优选C 3-C 7环烷基，还优选C 3-C 6环烷基，如环丙基、环丁基、环戊基、环己基等)、杂环基(如四氢吡咯基、氢化吡啶基、环丙胺基、环己胺基、四氢呋喃基、四氢吡喃基等)、杂芳基(如吡咯基、吡啶基、 喹啉基、异喹啉基、吲哚基、咪唑基、呋喃基、吡喃基、噻吩基等)、卤素(如氟、氯、溴、碘等)、硝基、C 1-C 12烷氧基(如甲氧基)、芳基(苯基、萘基、蒽基、菲基等)、酯基、酰胺基等；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基；所述R 8和R 9相同或不同，彼此独立地选自H、未取代或任选被一个或多个R b取代的下列基团：C 1-C 12烷基(优选C 1-C 6烷基，还优选C 1-C 4烷基，如甲基、乙基、丙基、丁基等)、C 3-C 12环烷基(优选C 3-C 7环烷基，还优选C 3-C 6环烷基，如环丙基、环丁基、环戊基、环己基等)、杂环基(如四氢吡咯基、氢化吡啶基、环丙胺基、环己胺基、四氢呋喃基、四氢吡喃基等)、杂芳基(如吡咯基、吡啶基、喹啉基、异喹啉基、吲哚基、咪唑基、呋喃基、吡喃基等)、卤素(如氟、氯、溴、碘等)、硝基、C 1-C 12烷氧基(如甲氧基)、芳基(苯基、萘基、蒽基、菲基等)、酯基、酰胺基等；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。
具体的，式8所示结构的化合物可以是：苯乙烯、4-氟苯乙烯、3-氟苯乙烯、2-氟苯乙烯、4-氯苯乙烯、2-氯苯乙烯、3-氯苯乙烯、4-溴苯乙烯、2-溴苯乙烯、3-溴苯乙烯、4-碘苯乙烯、2-碘苯乙烯，3-碘苯乙烯、4-羟基苯乙烯、3-羟基苯乙烯、2-羟基苯乙烯、4-环己基苯乙烯、3-环己基苯乙烯、2-环己基苯乙烯、4-乙酰基苯乙烯、3-乙酰基苯乙烯，2-乙酰基苯乙烯、4-甲氧基苯乙烯、3-甲氧基苯乙烯、2-甲氧基苯乙烯、1,4-二乙烯基苯、1,3-二乙烯基苯、1,2-二乙烯基苯、4-硝基苯乙烯、2,6-二溴苯乙烯、2,5-二溴苯乙烯、2,4-二溴苯乙烯、2,3-二溴苯乙烯、3,4-二溴苯乙烯、3,5-二溴苯乙烯，2,6-二碘苯乙烯、3,5-二碘苯乙烯、2,3-二碘苯乙烯、3,4-二碘苯乙烯、4-三氟甲基苯乙烯、3-三氟甲基苯乙烯、2-三氟甲基苯乙烯、4-氰基苯乙烯、3-氰基苯乙烯、2-氰基苯乙烯、1,1-二苯基乙烯、1,1-二吡啶基乙烯、1,2-二吡啶基乙烯、1,1-二喹啉基乙烯、1,2-二喹啉基乙烯、1,1-二噻吩基乙烯、1,2-二噻吩基乙烯、2-苯基丙烯、2-苯基丁烯、2-苯基戊烯、3-苯基戊烯、1,1,2,2-四苯基乙烯、1,1,2-三苯基乙烯、1,2-二苯基乙烯、1-乙烯基萘、2-乙烯基萘、1-苯基-2-萘基乙烯、1,2-二萘基乙烯、1-甲基-1-苯基戊烯、1,4-二苯基-1,3-丁二烯、1,2-二蒽基乙烯、1,2-二菲基乙烯等。
4)具有式9所示结构的化合物：
Figure PCTCN2019098940-appb-000019
式9中，R” 3和R 8的定义如上所述。
具体的，式9所示结构的化合物可以是：苯乙炔、4-氟苯乙炔、3-氟苯乙炔、2-氟苯乙炔、4-氯苯乙炔、2-氯苯乙炔、3-氯苯乙炔、4-溴苯乙炔、2-溴苯乙炔、3-溴苯乙炔、4-碘苯乙炔、2-碘苯乙炔，3-碘苯乙炔、4-羟基苯乙炔、3-羟基苯乙炔、2-羟基苯乙炔、4-环己基苯乙炔、3-环己基苯乙炔、2-环己基苯乙炔、4-乙酰基苯乙炔、3-乙酰基苯乙炔，2-乙酰基苯乙炔、4-甲氧基苯乙炔、3-甲氧基苯乙炔、2-甲氧基苯乙炔、1,4-二乙炔基苯、1,3-二乙炔基苯、1,2-二乙炔基苯、4-硝基苯乙炔、2,6-二溴苯乙炔、2,5-二溴苯乙炔、2,4-二溴苯乙炔、2,3-二溴苯乙炔、3,4-二溴苯乙炔、3,5-二溴苯乙炔，2,6-二碘苯乙炔、3,5-二碘苯乙炔、2,3-二碘苯乙炔、3,4-二碘苯乙炔、4-三氟甲基苯乙炔、3-三氟甲基苯乙炔、2-三氟甲基苯乙炔、4-氰基苯乙炔、3-氰基苯乙炔、2-氰基苯乙炔、1,2-二苯基乙炔、1,2-二吡啶基乙炔、1-苯基2-吡啶基乙炔、1-乙炔基喹啉、1,2-二噻吩基乙炔、1-苯 基丙炔、1-苯基丁炔、1-苯基戊炔、2-乙酰氧基苯乙炔、3-乙酰氧基苯乙炔、4-乙酰氧基苯乙炔、2-乙炔基萘、1-苯基-2-萘基乙炔、1,2-二萘基乙炔、1,4-二苯基-1,3-丁二炔、1,2-二蒽基乙炔、1,2-二菲基乙炔等。
5)具有式10或式11所示结构的化合物：
Figure PCTCN2019098940-appb-000020
式10中，R”’ 3＝R” 3，R’ 4＝R 4但不为H。
式11中，R”’ 3＝R” 3，R’ 4＝R 4，R” 4与R’ 4相同或不同，彼此独立地选自前面R 4定义的范围。
具体的，式10所示结构的化合物可以是：二甲硫醚、甲基乙基硫醚、乙基丁基硫醚、二环己基硫醚、二苯基硫醚、2,2’-二吡啶基硫醚、苯基甲基硫醚、苯基三氟甲基硫醚、苯基乙基硫醚、苯基丙基硫醚、苯基异丙基硫醚、苯基环丙基硫醚、苯基正丁基硫醚、苯基环戊基硫醚、苯基环己基硫醚、苯基吡啶基硫醚、苯基苄基硫醚、1-萘基甲基硫醚、2-萘基甲基硫醚、1-萘基乙基硫醚、2-萘基乙基硫醚、1-萘基三氟甲基硫醚、2-萘基三氟甲基硫醚、1-萘基丙基硫醚、1-萘基环己基硫醚、2-萘基环己基硫醚、1-蒽基三氟甲基硫醚、2-蒽基三氟甲基硫醚、1-蒽基环己基硫醚、2-蒽基环己基硫醚、1-菲基三氟甲基硫醚、2-菲基三氟甲基硫醚、1-菲基环己基硫醚、2-菲基环己基硫醚、4-氟苯甲硫醚、2-氟苯甲硫醚、3-氟苯甲硫醚、4-氯苯甲硫醚、2-氯苯甲硫醚、3-氯苯甲硫醚、4-溴苯甲硫醚、2-溴苯甲硫醚、3-溴苯甲硫醚、4-碘苯甲硫醚、2-碘苯甲硫醚、3-碘苯甲硫醚、4-三氟甲基苯甲硫醚、2-三氟甲基苯甲硫醚、3-三氟甲基苯甲硫醚、4-氰基苯甲硫醚、2-氰基苯甲硫醚、3-氰基苯甲硫醚、4-甲基苯甲硫醚、3-甲基苯甲硫醚、2-甲基苯甲硫醚、4-乙酰基苯甲硫醚、3-乙酰基苯甲硫醚、2-乙酰基苯甲硫醚、4-甲氧基苯甲硫醚、3-甲氧基苯甲硫醚、2-甲氧基苯甲硫醚、4-甲硫基苯甲硫醚、3-甲硫基苯甲硫醚、2-甲硫基苯甲硫醚、4-硝基苯甲硫醚、2,6-二溴苯甲硫醚、2,5-二溴苯甲硫醚、2,4-二溴苯甲硫醚、2,3-二溴苯甲硫醚、3,4-二溴苯甲硫醚、3,5-二溴苯甲硫醚，2,6-二碘苯甲硫醚、3,5-二碘苯甲硫醚、2,3-二碘苯甲硫醚、3,4-二碘苯甲硫醚、2,3,4,5,6-五氟苯甲硫醚、4-叔丁基苯甲硫醚、3-叔丁基苯甲硫醚、4-甲硫基苯甲酸甲酯、4-甲硫基苯甲酸乙酯、3-甲硫基苯甲酸甲酯、3-甲硫基苯甲酸乙酯、2-甲硫基苯甲酸甲酯、2-甲硫基苯甲酸乙酯、4-羟基苯甲硫醚、3-羟基苯甲硫醚、2-羟基苯甲硫醚、4-甲硫基苯甲醇、3-甲硫基苯甲醇、2-甲硫基苯甲醇、4-甲硫基苯硫酚、3-甲硫基苯硫酚、2-甲硫基苯硫酚、2-甲硫基吡啶、3-甲硫基吡啶、4-甲硫基吡啶、2,6-二甲硫基吡啶、2-甲硫基喹啉、3-甲硫基喹啉、4-甲硫基喹啉、5-甲硫基喹啉、6-甲硫基喹啉、7-甲硫基喹啉、8-甲硫基喹啉、3,4-二甲硫基喹啉、4,5-二甲硫基喹啉、5,6-二甲硫基喹啉、5,7-二甲硫基喹啉、5,8-二甲硫基喹啉、6,8-二甲硫基喹啉等。
具体的，式11所示结构的化合物可以是：苯基膦、二苯基膦、苯基甲基膦、苯基乙基膦、苯基丙基膦、苯基正丁基膦、萘基膦、萘基甲基膦、萘基乙基膦、萘基丙基膦、萘基丁基膦、蒽基膦、蒽基甲基膦、蒽基乙基膦、蒽基丙基膦、蒽基丁基膦、三苯基膦、三丁基膦、三(1-萘基)膦等。
6)具有式12所示结构的化合物或其盐酸盐：
Figure PCTCN2019098940-appb-000021
式12中，R 3的定义如上所述；R’ 8相同或不同，彼此独立地选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基等，R b的定义同前；X 2选自O、S、Se、Si、N、P等杂原子；y选自1、2或3，与X 2的价态相关，X 2为二价时，y＝1，X 2为三价时，y＝2，X 2为四价时，y＝3；当y＝2或3时，两个R’ 8可以成环。
具体的，式12所示结构的化合物可以是：苯甲醇、苄基硫醇、苄基甲基醚、苄基乙基醚、苄基环己基醚、二苄醚、苄胺、N-甲基苄胺、N-乙基苄胺、N-环丙基苄胺、N,N-二甲基苄胺、N-苄基吗啉、N-苄基四氢吡咯、三苄胺、N-苯基苄基胺、二苄胺、N,N-二苯基苄胺、苄基肼或苄基肼盐酸盐、苄基甲基硫醚、苄基乙基硫醚、苄基丙基硫醚、苄基环丙基硫醚、苄基丁基硫醚、二苄基硫醚、苄基苯基硫醚、苄基环己基硫醚、苄基甲基硒醚、苄基乙基硒醚、苄基丙基硒醚、苄基环丙基硒醚、苄基丁基硒醚、二苄基硒醚、苄基苯基硒醚、苄基环己基硒醚、苄基甲基硅醚、苄基乙基硅醚、苄基丙基硅醚、苄基环丙基硅醚、苄基丁基硅醚、二苄基硅醚、苄基苯基硅醚、苄基环己基硅醚等。
7)具有式13所示结构的化合物：
Figure PCTCN2019098940-appb-000022
式13中，R 4的定义如上所述；R 10选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基、肼基、羧基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；任选地R 4和R 10可以成环；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基、芳基。
进一步的，R 10选自H、未取代或任选被一个或多个R b取代的下列基团：C 1-C 12烷基(优选C 1-C 6烷基，还优选C 1-C 4烷基，如甲基、乙基、丙基、丁基等)、C 3-C 12环烷基(优选C 3-C 7环烷基，还优选C 3-C 6环烷基，如环丙基、环丁基、环戊基、环己基等)、杂环基(如四氢吡咯基、氢化吡啶基、环丙胺基、环己胺基、四氢呋喃基、四氢吡喃基等)、杂芳基(如吡咯基、吡啶基、喹啉基、异喹啉基、吲哚基、咪唑基、呋喃基、吡喃基、噻吩基等)、卤素(如氟、氯、溴、碘等)、硝基、C 1-C 12烷氧基(如甲氧基)、芳基(苯基、萘基、蒽基、菲基等)、酯基、酰胺基等；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。R 4和R 10可以形成C 3-C 12环烷基(优选C 3-C 7环烷基，还优选C 3-C 6环烷基，如环丙基、环丁基、环戊基、环己基等)、或杂环基(如四氢吡咯基、氢化吡啶基、环丙胺基、环己胺基、四氢呋喃基、四氢吡喃基等)
具体的，式13所示结构的化合物可以是：1-苯基乙醇、4’-氟苯基-1-乙醇、2’-氟苯基-1-乙醇、3’-氟苯基-1-乙醇、4’-氯苯基-1-乙醇、2’-氯苯基-1-乙醇、3’-氯苯基-1-乙醇、4’-溴苯基-1-乙醇、2’-溴苯基-1-乙醇、3’-溴苯基-1-乙醇、4’-碘苯基-1-乙醇、2’-碘苯基-1-乙醇，3’-碘苯基-1-乙醇、4’- 三氟甲基苯基-1-乙醇、2’-三氟甲基苯基-1-乙醇，3’-三氟甲基苯基-1-乙醇、4’-氰基苯基-1-乙醇、2’-氰基苯基-1-乙醇、3’-氰基苯基-1-乙醇、4’-乙酰基苯基-1-乙醇、3’-乙酰基苯基-1-乙醇、2’-乙酰基苯基-1-乙醇、4’-甲氧基苯基-1-乙醇、3’-甲氧基苯基-1-乙醇、2’-甲氧基苯基-1-乙醇、4’-硝基苯基-1-乙醇、3’-硝基苯基-1-乙醇、2’-硝基苯基-1-乙醇、2’,6’-二溴苯基-1-乙醇、2’,5’-二溴苯基-1-乙醇、2’,4’-二溴苯基-1-乙醇、2’,3’-二溴苯基-1-乙醇、3’,4’-二溴苯基-1-乙醇、2’,6’-二碘苯基-1-乙醇、2’,5’-二碘苯基-1-乙醇、2’,4’-二碘苯基-1-乙醇、2’,3’-二碘苯基-1-乙醇、3’,4’-二碘苯基-1-乙醇、2’,3’,4’,5’,6’-五氟苯基-1-乙醇、4’-羟基苯基-1-乙醇、3’-羟基苯基-1-乙醇、2’-羟基苯基-1-乙醇、4’-甲基苯基-1-乙醇、3’-甲基苯基-1-乙醇、2’-甲基苯基-1-乙醇、4’-巯基苯基-1-乙醇、3’-巯基苯基-1-乙醇、2’-巯基苯基-1-乙醇、2’-吡啶基-1-乙醇、3’-吡啶基-1-乙醇、4’-吡啶基-1-乙醇、2’-喹啉基-1-乙醇、3’-喹啉基-1-乙醇、4’-喹啉基-1-乙醇、5’-喹啉基-1-乙醇、6’-喹啉基-1-乙醇、7’-喹啉基-1-乙醇、8’-喹啉基-1-乙醇、1-苯基丙醇、1-苯基丁醇、1-苯基戊醇、二苯基甲醇、1,2-二苯基乙醇、1-萘基乙醇、1-萘基丙醇、1-萘基丁醇、1-萘基戊醇、1-蒽基乙醇、1-蒽基丙醇、1-蒽基丁醇、1-蒽基戊醇、1-菲基乙醇、1-菲基丙醇、1-菲基丁醇、1-菲基戊醇、异丙醇、2-丁醇、2,3-丁二醇，2-戊醇、2,3-戊二醇、3-戊醇、2-己醇、3-己醇、2-庚醇、4-庚醇、1-羟基-4-甲基环己烷、1-羟基-4-氯环己烷、环己醇、1,4-环己二醇、环戊醇等。
8)具有式14或式14’所示结构的化合物：
Figure PCTCN2019098940-appb-000023
式14中，R”＝R’，m4为0-4的整数；当m4大于等于2时，相邻的两个R”可以成环，例如形成烃基环、芳基或杂芳基，所述芳基或杂芳基还可以任选被至少一个取代基R b所取代，R b的定义同前；R 11选自烷基或芳基取代烷基；m5为整数，如0,1,2,3,4,5……；X 3为阴离子，包括卤素(氟、氯、溴、碘)、羧酸根、磺酸根等；
式14’中，R”、m4、R 11、m5、X 3的定义同上；R 4a为烃基环、芳基(例如苯基)或杂芳基；R”a与R”相同或不同，彼此独立地选自上述的R’；m4’与m4相同或不同，为0-4的整数；R’ 11与R 11相同或不同，彼此独立地选自烷基或芳基取代烷基；m5”与m5相同或不同，为整数0,1,2,3,4,5……；X’ 3与X 3相同或不同，为阴离子，包括卤素(氟、氯、溴、碘)、羧酸根、磺酸根等；q为0-4的整数(例如0,1,2)。
具体的，式14所示结构的化合物可以是(下述通式中的R＝R’)：
Figure PCTCN2019098940-appb-000024
9)具有式15所示结构的化合
Figure PCTCN2019098940-appb-000025
式15中，R”” 3＝R 3，X 3的定义同上；m5’为整数，例如0,1,2,3,4,5……(示例性的可以是0-10的整数)，且与P原子相连的三个R”” 3相同或不同。
具体的，R”” 3选自未取代或任选被一个或多个R”’取代的芳基，R”’＝R’。
具体的，式15所示结构的化合物可以是：
Figure PCTCN2019098940-appb-000026
其中，Ar的定义如上所述；优选地，Ar可以是未取代或任选被一个或多个R b取代的下列基团：五元以上芳环、杂芳环等；每一个R b彼此独立地选自卤素、羟基、巯基、硝基、烷基、烷氧基、环烷基、杂环基、芳基、杂芳基、羧基、酯基、氨基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等。
10)具有式16所示结构的化合物：
Figure PCTCN2019098940-appb-000027
式16中，R 12具有R 4的定义，m4，R 4的定义如上，并且，当m4大于等于2时，相邻的两个R 12 可以成环，形成芳基或杂芳基，所述芳基或杂芳基还可以任选被至少一个R b所取代；每一个R b彼此独立地选自卤素、羟基、巯基、硝基、烷基、烷氧基、环烷基、杂环基、芳基、杂芳基、羧基、酯基、氨基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等。
具体的，式16所示结构的化合物可以是式16-1或式16-2：
Figure PCTCN2019098940-appb-000028
式16-1和式16-2中，Ar、m5和R 12的定义如上所述。
11)包含式17所示重复单元的聚合物：
Figure PCTCN2019098940-appb-000029
式17中，R 3的定义如上所述；R 8相同或不同，定义如上所述。
具体的，式17所示重复单元可以是下述结构中的一种或多种：
Figure PCTCN2019098940-appb-000030
所述聚合物例如可以是苯乙烯均聚物或其共聚物，苯乙烯共聚物中的共聚单体可以选自丙烯腈类化合物、丁二烯类化合物等中的一种或多种，例如所述共聚物包括如下所示重复单元：
Figure PCTCN2019098940-appb-000031
其中，“Poly(styrene-co-acrylonitrile”是“聚(苯乙烯-丙烯腈共聚物)”，“polystylene-polybutadiene-polystyrene”是“聚苯乙烯-聚丁二烯-聚苯乙烯”，“Styrene-butadiene copolymers”是“苯乙烯-丁二烯共聚物”，“Acrylonitrile butadiene Styrene copolymers(ABS Resins)”是“丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)”。
12)具有式18所示结构的化合物：
Figure PCTCN2019098940-appb-000032
式18中，R”’ 4选自未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基等，R b的定义同前。
进一步的，式18所示结构的化合物可以是下述式18a所示化合物中的一种：
Figure PCTCN2019098940-appb-000033
式18a中，Ar、R’、m1的定义如上所述。
具体的，式18所示结构的化合物可以是：苯甲醛、4-氟苯甲醛、2-氟苯甲醛、3-氟苯甲醛、4-氯苯甲醛、2-氯苯甲醛、3-氯苯甲醛、4-溴苯甲醛、2-溴苯甲醛、3-溴苯甲醛、4-碘苯甲醛、2-碘苯甲醛，3-碘苯甲醛、4-三氟甲基苯甲醛、2-三氟甲基苯甲醛，3-三氟甲基苯甲醛、4-氰基苯甲醛、2-氰基苯甲醛，3-氰基苯甲醛、4-乙酰基苯甲醛、3-乙酰基苯甲醛，2-乙酰基苯甲醛、4-甲氧基苯甲醛、3-甲氧基苯甲醛、2-甲氧基苯甲醛、对苯二甲醛、间苯二甲醛、邻苯二甲醛、均苯三甲醛、2-溴均苯三甲醛、4-硝基苯甲醛、2-硝基苯甲醛，3-硝基苯甲醛，2,6-二溴苯甲醛、2,5-二溴苯甲醛、2,4-二溴苯甲醛、2,3-二溴苯甲醛、3,4-二溴苯甲醛、3,5-二溴苯甲醛，2,6-二碘苯甲醛、3,5-二碘苯甲醛、2,3-二碘苯甲醛、3,4-二碘苯甲醛、2,3,4,5,6-五氟苯甲醛、4-叔丁基苯甲醛、3-叔丁基苯甲醛、4-醛基苯甲酸甲酯、4-醛基苯甲酸乙酯、3-醛基苯甲酸甲酯、3-醛基苯甲酸乙酯、2-醛基苯甲酸甲酯、2-醛基苯甲酸乙酯、4-羟基苯甲醛、3-羟基苯甲醛、2-羟基苯甲醛、4-醛基苯甲醇、3-醛基苯甲醇、2-醛基苯甲醇、4-醛基苯硫酚、3-醛基苯硫酚、2-醛基苯硫酚、2-吡啶甲醛、3-甲基吡啶甲醛、4-甲基甲醛、2,6-醛基吡啶、2-喹啉甲醛、3-喹啉甲醛、4-喹啉甲醛、5-喹啉甲醛、6-喹啉甲醛、7-喹啉甲醛、8-喹啉甲醛、3,4-醛基喹啉、4,5-醛基喹啉、5,6-醛基喹啉、5,7-醛基喹啉、5,8-醛基喹啉、6,8-醛基喹啉、4-联苯甲醛、3-联苯甲醛、2-联苯甲醛、1-萘甲醛、2-萘甲醛、5-萘甲醛、6-萘甲醛、9-蒽甲醛、2-蒽甲醛、1-菲甲醛、2-菲甲醛等。
13)具有式19所示结构的化合物：
Figure PCTCN2019098940-appb-000034
式19中，R 3、R 4定义如上所述。
进一步的，式19所示结构的化合物可以是下述式19-1所示结构的化合物中的一种，其中，Ar、R 13如R’的定义，R’定义如上所述。
Figure PCTCN2019098940-appb-000035
具体的，式19所示结构的化合物可以是：苯胺、4-氟苯胺、2-氟苯胺、3-氟苯胺、4-氯苯胺、2-氯苯胺、3-氯苯胺、4-溴苯胺、2-溴苯胺、3-溴苯胺、4-碘苯胺、2-碘苯胺，3-碘苯胺、4-三氟甲基苯胺、2-三氟甲基苯胺，3-三氟甲基苯胺、4-氰基苯胺、2-氰基苯胺，3-氰基苯胺、4-甲基苯胺、3-甲基苯胺，2-甲基苯胺、4-氨基苯甲醚、3-氨基苯甲醚、2-氨基苯甲醚、1,4-二甲基苯胺、1,3-二甲基苯胺、1,2-二甲基苯胺、均三甲基苯胺、4-硝基苯胺、2,6-二溴苯胺、2,5-二溴苯胺、2,4-二溴苯胺、2,3-二溴苯胺、3,4-二溴苯胺、3,5-二溴苯胺，2,3-二溴苯胺、3,4-二溴苯胺、2,6-二碘苯胺、3,5-二碘苯胺、2,3-二碘苯胺、3,4-二碘苯胺、2,3,4,5,6-五氟苯胺、4-叔丁基苯胺、3-叔丁基苯胺、4-氨基苯甲酸甲酯、4-氨基苯甲酸乙酯、3-氨基苯甲酸甲酯、3-氨基苯甲酸乙酯、2-氨基苯 甲酸甲酯、2-氨基苯甲酸乙酯、4-氨基苯酚、3-氨基苯酚、2-氨基苯酚、4-氨基苯甲醇、3-氨基苯甲醇、2-氨基苯甲醇、4-氨基苯硫酚、3-氨基苯硫酚、2-氨基苯硫酚、2-氨基吡啶、3-氨基吡啶、4-氨基吡啶、2-氨基喹啉、3-氨基喹啉、4-氨基喹啉、5-氨基喹啉、6-氨基喹啉、7-氨基喹啉、8-氨基喹啉、3,4-二氨基喹啉、4,5-二氨基喹啉、5,6-二氨基喹啉、5,7-二氨基喹啉、5,8-二氨基喹啉、6,8-二氨基喹啉、N-甲基苯胺、N-乙基苯胺、N-甲基-4-氟苯胺、N-乙基-4-氟苯胺、N-甲基-2-氟苯胺、N-甲基-3-氟苯胺、N-甲基-4-氯苯胺、N-甲基-2-氯苯胺、N-甲基-3-氯苯胺、N-甲基-4-溴苯胺、N-甲基-2-溴苯胺、N-甲基-3-溴苯胺、N-甲基-4-碘苯胺、N-甲基-2-碘苯胺、N-甲基-3-碘苯胺、N-甲基-4-硝基苯胺、N-甲基-2-硝基苯胺、N-甲基-3-硝基苯胺、N-甲基-4-甲氧基苯胺、N-甲基-2-甲氧基苯胺、N-甲基-3-甲氧基苯胺、N-甲基-2,3-二甲氧基苯胺、N-甲基-2,4-二甲氧基苯胺、N-甲基-2,5-二甲氧基苯胺、N-甲基-2,6-二甲氧基苯胺、N-甲基-2,3-二氯苯胺、N-甲基-2,4-二氯苯胺、N-甲基-2,5-二氯苯胺、N-甲基-2,6-二氯苯胺、N-甲基-3,4-二氯苯胺，N-甲基-3,5-二氯苯胺，N-甲基-2,3-二溴苯胺、N-甲基-2,4-二溴苯胺、N-甲基-2,5-二溴苯胺、N-甲基-2,6-二溴苯胺、N-甲基-3,4-二溴苯胺，N-甲基-3,5-二溴苯胺，2,3,4,5,6-五氟苯胺等。
14)具有式20所示结构的化合物：
Figure PCTCN2019098940-appb-000036
式20中，R 4，R 10定义如上所述，任选地R 4和R 10可以形成碳环或杂环，所述碳环可以被一个或多个R b取代。
在一个实施方式中，所述R 4为未取代或任选被一个或多个R b取代的芳基或杂芳基，所述R 10为未取代或任选被一个或多个R b取代的芳基、杂芳基、烷基、环烷基、卤素等。
在一个实施方式中，所述R 4为未取代或任选被一个或多个R b取代的烷基或环烷基，所述R 10为未取代或任选被一个或多个R b取代的芳基、杂芳基、烷基、环烷基、卤素等。
在一个实施方式中，R 4和R 10形成碳环(例如C 3-10环烷基)，所述碳环可以任选被一个或多个R b取代。
进一步的，式20所示结构的化合物可以是下述式20-1、式20-2、式20-3、式20-4所示结构的化合物中的一种：
Figure PCTCN2019098940-appb-000037
式20-1、式20-2、式20-3和式20-4中，Ar、R’、m1、m3的定义如上所述。
具体的，式20所示结构的化合物可以是：2-苯基丙酸、4’-氟苯基-2-丙酸、2’-氟苯基-2-丙酸、3’-氟苯基-2-丙酸、4’-氯苯基-2-丙酸、2’-氯苯基-2-丙酸、3’-氯苯基-2-丙酸、4’-溴苯基-2-丙酸、2’-溴苯基-2-丙酸、3’-溴苯基-2-丙酸、4’-碘苯基-2-丙酸、2’-碘苯基-2-丙酸，3’-碘苯基-2-丙酸、4’-三氟甲基苯基-2-丙酸、2’-三氟甲基苯基-2-丙酸，3’-三氟甲基苯基-2-丙酸、4’-氰基苯基-2-丙酸、2’-氰基苯基-2-丙酸、3’-氰基苯基-2-丙酸、4’-乙酰基苯基-2-丙酸、3’-乙酰基苯基-2-丙酸、2’-乙酰基苯基-2-丙酸、4’-甲氧基苯基-2-丙酸、3’-甲氧基苯基-2-丙酸、2’-甲氧基苯基-2-丙酸、4’-硝基 苯基-2-丙酸、3’-硝基苯基-2-丙酸、2’-硝基苯基-2-丙酸、2’,6’-二溴苯基-2-丙酸、2’,5’-二溴苯基-2-丙酸、2’,4’-二溴苯基-2-丙酸、2’,3’-二溴苯基-2-丙酸、3’,4’-二溴苯基-2-丙酸、2’,6’-二碘苯基-2-丙酸、2’,5’-二碘苯基-2-丙酸、2’,4’-二碘苯基-2-丙酸、2’,3’-二碘苯基-2-丙酸、3’,4’-二碘苯基-2-丙酸、2’,3’,4’,5’,6’-五氟苯基-2-丙酸、4’-羟基苯基-2-丙酸、3’-羟基苯基-2-丙酸、2’-羟基苯基-2-丙酸、4’-甲基苯基-2-丙酸、3’-甲基苯基-2-丙酸、2’-甲基苯基-2-丙酸、4’-巯基苯基-2-丙酸、3’-巯基苯基-2-丙酸、2’-巯基苯基-2-丙酸、2’-吡啶基-2-丙酸、3’-吡啶基-2-丙酸、4’-吡啶基-2-丙酸、2’-喹啉基-2-丙酸、3’-喹啉基-2-丙酸、4’-喹啉基-2-丙酸、5’-喹啉基-2-丙酸、6’-喹啉基-2-丙酸、7-’-喹啉基-2-丙酸、8-’-喹啉基-2-丙酸、二苯基乙酸、2-苯基丁酸、2-苯基丁酸、2-苯基戊酸、2,3-二苯基丙酸、2-萘基-2-丙酸、1-萘基-2-丙酸、1-萘基-2-丁酸、α-苯基环戊基乙酸、1-萘基-2-戊酸、9-蒽基-2-丙酸、10-蒽基-2-丙酸、1-蒽基-2-丁酸、1-蒽基-2-戊酸、1-菲基-2-丙酸、1-菲基-2-丁酸、1-菲基-2-戊酸、异丁酸、2-甲基丁酸、2-甲基戊酸、环戊基甲酸、3-甲基戊酸、2-甲基己酸、3-甲基己酸、环己基甲酸、2-甲基庚酸、4-甲基庚酸、4-甲基环己基甲酸、环庚基甲酸、1,4-环己二酸等。
[反应过程]
如前所述，所述光促需氧氧化反应是在光照条件下进行，所述光照的光源具体可以是CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)、白炽灯、LED(200-600nm)等光源。
上述物质，在所述需氧氧化体系存在的条件下，根据不同的反应条件(调整反应光源波长、反应溶剂、添加剂、分子氧压力、分子氧含量、反应温度或反应时间等)，可以分别得到以下氧化产物：
第1)种具有式6所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000038
以E1为例，在分子氧存在下，将反应物R 3-CH 2-R 4和本发明所述辅助助剂在光照下进行反应，得到R 3-(C＝O)-R 4。具体的，将E1中的反应物R 3-CH 2-R 4和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为450-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R 3-(C＝O)-R 4。
以E2为例，在分子氧存在下，将反应物R 3-CH 3和本发明所述辅助助剂在光照下进行反应，得到相应羧酸化合物R 3COOH。具体的，将上述E2中的反应物R 3-CH 3和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Blue LED(蓝色LED灯)的光(波长约为300-425nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R 3COOH。其中，若控制反应时间或改变激光波长，可以先得到相应醛R 3(C＝O)H，然后通过延长反应时间或改变激光波长，最终得到相应羧酸化合物R 3COOH。
第2)种具有式7所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000039
以E3为例，在分子氧存在下，将反应物R’ 3-CH(R 5)-R 5和本发明所述辅助助剂在光照下进行反应，得到R’ 3C(＝O)-R 5。具体的，将E3中的反应物R’ 3-CH(R 5)-R 5和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为300-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R’ 3C(＝O)-R 5。
第3)种具有式8所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000040
以E4为例，在分子氧存在下，将反应物R’ 3-C(R 7)＝C(R 8)-R 9和本发明所述辅助助剂在光照下进行反应，得到R’ 3C(＝O)-H。具体的，将E4中的反应物R’ 3-C(R 7)＝C(R 8)-R 9和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为450-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R’ 3C(＝O)-H。
所述反应的时间约为5-12h，若延长反应时间或改变光源波长，反应所得的醛类化合物将继续转化为相应的羧酸类化合物。
第4)种具有式9所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000041
以E5为例，在分子氧存在下，将反应物R’ 3-C≡C-R 8和本发明所述辅助助剂在光照下进行反应，得到R’ 3C(＝O)-C(＝O)-R 8。具体的，将E5中的反应物R’ 3-C≡C-R 8和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为420-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R’ 3C(＝O)-C(＝O)-R 8。
所述反应的时间约为5-12h，若延长反应时间或改变光源波长，反应所得的目标化合物产生两个羰基之间碳碳键断裂产物，使得反应体系变得复杂。
第5)种具有式10或式11所述结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000042
以E6为例，在分子氧存在下，将反应物R’ 3-S-R’ 4和本发明所述辅助助剂在光照下进行反应，得到相应亚砜产物R’ 3S(＝O)-R’ 4。具体的，将E6中的反应物R’ 3-S-R’ 4和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Purple LED(紫光LED灯)的光(波长约为380nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R’ 3S(＝O)-R’ 4。
以E6’为例，在分子氧存在下，将反应物R’ 3-S-R’ 4和本发明所述辅助助剂在光照下进行反应，得到相应砜产物R’ 3S(＝O) 2-R’ 4。具体的，将E6’中的反应物R’ 3-S-R’ 4和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Purple LED(紫光LED灯)的光(波长约为360nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R’ 3S(＝O) 2-R’ 4。
以E7为例，在分子氧存在下，将反应物P(R’ 3)(R” 4)(R’ 4)和本发明所述辅助助剂在光照下进行反应，得到P(＝O)(R’ 3)(R” 4)(R’ 4)。具体的，将E7中的反应物P(R’ 3)(R” 4)(R’ 4)和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为380-480nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物P(＝O)(R’ 3)(R” 4)(R’ 4)。
第6)种具有式12所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000043
以E8为例，在分子氧存在下，将反应物R 3-CH 2-X 2-(R 8) y和本发明所述辅助助剂在光照下进行反应，得到R 3C(＝O)-H。具体的，将E8中的反应物R 3-CH 2-X 2-(R 8) y和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为420-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R 3C(＝O)-H。
所述反应的时间约为5-12h，若延长反应时间或改变光源波长，反应所得的醛类化合物将继续转化为相应的羧酸类化合物。
第7)种具有式13所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000044
以E9为例，在分子氧存在下，将反应物R 4-CH(OH)-R 10和本发明所述辅助助剂在光照下进行反应，得到R 4-C(＝O)-R 10。具体的，将E9中的反应物R 4-CH(OH)-R 10和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Blue LED(蓝色LED灯)的光(波长约为380-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R 4-C(＝O)-R 10。
第8)种具有式14所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000045
以E10为例，在分子氧存在下，将反应物(见E10)和本发明所述辅助助剂在光照下进行反应，得到目标化合物(见E10)。具体的，将E10中的反应物(见E10)和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Blue LED(蓝色LED灯)的光(波长约为380-455nm)照射下，于空气或 氧气氛围中在室温下反应适当的时间得到目标化合物(见E10)。
第9)种具有式15所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000046
以E11为例，在分子氧存在下，将反应物(见E11)和本发明所述辅助助剂在光照下进行反应，得到目标化合物(见E11)，其中，m5为1以上的整数，m5-1代表m5减去1(若m5为0，则是R”” 3中的端基C转化为醛基)。具体的，将E11中的反应物(见E11)和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为420-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物(见E11)。
若延长反应时间或改变光源波长，反应所得的醛类化合物将继续转化为相应的羧酸类化合物。
第10)种具有式16所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000047
以E12为例，在分子氧存在下，将反应物(见E12)和本发明所述辅助助剂在光照下进行反应，得到目标化合物(见E12)。具体的，将E12中的反应物(见E12)和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为420-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物(见E12)。
第11)种物质包含式17所示重复单元的聚合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000048
以E13为例，在分子氧存在下，将反应物(见E13)和本发明所述辅助助剂在光照下进行反应，得到目标化合物(见E13)。具体的，将E13中的反应物(见E13)和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Blue LED(蓝色LED灯)的光(波长约为380-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物(见E13)。
所述反应的时间约5-12h，若延长反应时间或改变光源波长，反应所得的醛类化合物将继续转化为相应的羧酸类化合物。
第12)种具有式18所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000049
以E15为例，在分子氧存在下，将反应物R 4-CHO和本发明所述辅助助剂在光照下进行反应， 得到R 4-(C＝O)-OH。具体的，将上述E15中的反应物R 3CHO和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Blue LED(蓝色LED灯)的光(波长约为380-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物R 4COOH。
以E15’为例，在分子氧存在下，将反应物R 4-CHO和本发明所述辅助助剂在光照下进行反应，得到缩醛R 4-CH(OR) 2。具体的，将上述E15’中的反应物R 4CHO、ROH和辅助助剂溶解于有机溶剂中得到反应混合液，在3W Blue LED(蓝色LED灯)的光(波长约为380-455nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物缩醛R 4-CH(OR) 2。
第13)种具有式19所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000050
以E16为例，在分子氧存在下，将反应物(见E16)和本发明所述辅助助剂在光照下进行反应，得到目标化合物(见E16)。具体的，将E16中的反应物(见E16)和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为380-480nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物(见E16)。
第14)种具有式20所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000051
以E17为例，在分子氧存在下，将反应物(见E17)和本发明所述辅助助剂在光照下进行反应，得到目标化合物(见E17)。具体的，将E17中的反应物(见E17)和辅助助剂溶解于有机溶剂中得到反应混合液，在34W CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)或3W Blue LED(蓝色LED灯)的光(波长约为380-480nm)照射下，于空气或氧气氛围中在室温下反应适当的时间得到目标化合物(见E17)。
[一些具体反应条件]
上述反应中，组分2)选自氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
如上所列，反应光源波长可以在200-600nm范围内调节。
所述反应优选在有机溶剂中进行。所述有机溶剂选自可以溶解反应原料的有机溶剂，例如甲醇、乙醇、乙腈、乙酸乙酯、丙酮、二氯甲烷、三氯甲烷、环己烷、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、1,2-二氯乙烷、乙二醇二甲醚、1,4-二氧六环、氯苯等。
所述有机溶剂的加入量没有特别限定，能溶解反应原料和辅助助剂即可。
所述反应在装有搅拌装置(如磁力搅拌子)的反应容器(如反应管)中进行。
反应过程中，需将反应容器中的反应混合液置于光下完全照射。
反应过程中，控制组分2)的压力在1-20atm范围；组分2)的含量控制在1％-100％范围。
所述反应在-20-80℃进行。
所述反应时间可以在0.1-100h范围。
待反应完成后，将产物减压浓缩得目标化合物粗品。
进一步的，将所述目标化合物粗品经柱色谱分离得目标化合物。
[术语和定义]
除非另有说明，本申请说明书和权利要求书中记载的基团和术语定义，包括其作为实例的定义、示例性的定义、优选的定义、表格中记载的定义、实施例中具体化合物的定义等，可以彼此之间任意组合和结合。这样的组合和结合后的基团定义及化合物结构，应当属于本申请保护的范围内。
本申请说明书和权利要求书记载的数值范围，当该数值范围被定义为“整数”时，应当理解为记载了该范围的两个端点以及该范围内的每一个整数。例如，“0～10的整数”应当理解为记载了0、1、2、3、4、5、6、7、8、9和10的每一个整数。当该数值范围被定义为“数”时，应当理解为记载了该范围的两个端点、该范围内的每一个整数以及该范围内的每一个小数。例如，“0～10的数”应当理解为不仅记载了0、1、2、3、4、5、6、7、8、9和10的每一个整数，还至少记载了其中每一个整数分别与0.1、0.2、0.3、0.4、0.5、0.6、0.7、0.8、0.9的和。
本发明使用的“卤素”指氟、氯、溴和碘。
本发明单独使用或用作后缀或前缀的“烷基”意在包括具有1至20个，优选1-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的直链或支链饱和脂族烃基。例如，“C 1-6烷基”表示具有1、2、3、4、5或6个碳原子的直链或支链烷基，“C 2-4烷基”表示具有2、3或4个碳原子的直链或支链烷基。烷基的实例包括但不限于甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、戊基和己基。
本发明单独使用或用作后缀或前缀的“烯基”意在包括具有2至20个，优选2-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的包含烯基的直链或支链脂族烃基。例如，“C 2-6烯基”表示具有2、3、4、5或6个碳原子的烯基。烯基的实例包括但不限于乙烯基、烯丙基、1-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、2-甲基丁-2-烯基、3-甲基丁-1-烯基、1-戊烯基、3-戊烯基和4-己烯基。
本发明单独使用或用作后缀或前缀的“炔基”意在包括具有2至20个，优选2-6个碳原子(或若提供了碳原子的具体数目，则指该具体数目)的包含炔基或炔烃的支链或直链脂族烃基。例如乙炔基、丙炔基(例如l-丙炔基、2-丙炔基)、3-丁炔基、戊炔基、己炔基和1-甲基戊-2-炔基。
本发明使用的术语“芳基”指由5至20个碳原子构成的芳族环结构。例如：包含5、6、7和8个碳原子的芳族环结构，可以是单环芳族基团，例如苯基；包含8、9、10、11、12、13或14个碳原子的环结构，可以是多环的，例如萘基、蒽基、菲基。术语“芳基”还包括具有两个或更多个环的多环环系，其中两个或更多个碳为两个相邻环所共有(所述环为“稠环”)，其中至少一个环是芳族的且其它环例如可以是环烷基、环烯基、环炔基、芳基和/或杂环基。多环的实例包括但不限于2,3-二氢-1,4-苯并二氧杂环己二烯和2,3-二氢-1-苯并呋喃。
本发明使用的术语“环烷基”意在包括具有指定数目碳原子的饱和环基。这些术语可包括稠合或桥接的多环系统。环烷基在其环结构中具有3至40个碳原子。在一个实施方案中，环烷基在其环结构中具有3、4、5或6个碳原子。例如，“C 3-6环烷基”表示例如环丙基、环丁基、环戊基或环己基的基团。
本发明使用的术语“环烯基”意在包括具有指定数目碳原子的含至少一个烯基的环基。这些 术语可包括稠合或桥接的多环系统。环烯基在其环结构中具有3至40个碳原子。在一个实施方案中，环烯基在其环结构中具有3、4、5或6个碳原子。例如，“C 3-6环烯基”表示例如环丙烯基、环丁烯基、环戊烯基或环己烯基的基团。
本发明使用的术语“环炔基”意在包括具有指定数目碳原子的含至少一个炔基的环基。这些术语可包括稠合或桥接的多环系统。环炔基在其环结构中具有6至40个碳原子。在一个实施方案中，环炔基在其环结构中具有6个碳原子。例如，“C 3-6环炔基”表示例如环丙炔基、环丁炔基、环戊炔基或环己炔基的基团。
本发明使用的“杂芳基”指具有至少一个环杂原子(例如硫、氧或氮)的杂芳族杂环。杂芳基包括单环系统和多环系统(例如具有2、3或4个稠环)。杂芳基的实例包括但不限于吡啶基、嘧啶基、吡嗪基、哒嗪基、三嗪基、呋喃基、喹啉基、异喹啉基、噻吩基、咪唑基、噻唑基、吲哚基、吡咯基、噁唑基、苯并呋喃基、苯并噻吩基、苯并噻唑基、异噁唑基、吡唑基、三唑基、四唑基、吲唑基、1,2,4-噻二唑基、异噻唑基、苯并噻吩基、嘌呤基、咔唑基、苯并咪唑基、苯并噁唑基、氮杂苯并噁唑基、咪唑并噻唑基、苯并[1,4]二氧杂环己烯基、苯并[1,3]二氧杂环戊烯基等。在一些实施方案中，杂芳基具有3至40个碳原子且在其它实施方案中具有3至20个碳原子。在一些实施方案中，杂芳基包含3至14个、4至14个、3至7个或5至6个成环原子。在一些实施方案中，杂芳基具有1至4个、1至3个或1至2个杂原子。在一些实施方案中，杂芳基具有1个杂原子。
本发明使用的术语“杂环基”指包含3至20个原子的饱和、不饱和或部分饱和的单环、二环或三环，其中1、2、3、4或5个环原子选自氮、硫、氧或磷，除非另有说明，其可通过碳或氮来连接，其中-CH 2-基团任选被-C(O)-代替；其中除非另有相反说明，环氮原子或环硫原子任选被氧化以形成N-氧化物或S-氧化物或环氮原子任选被季铵化；其中环中的-NH任选被乙酰基、甲酰基、甲基或甲磺酰基取代；及环任选被一个或多个卤素取代。应该理解的是，当杂环基中S原子和O原子的总数超过1时，这些杂原子不彼此相邻。若所述杂环基为二环或三环，则至少一个环可任选为杂芳族环或芳族环，条件是至少一个环是非杂芳族的。若所述杂环基为单环，则其一定不是芳族的。杂环基的实例包括但不限于哌啶基、N-乙酰基哌啶基、N-甲基哌啶基、N-甲酰基哌嗪基、N-甲磺酰基哌嗪基、高哌嗪基、哌嗪基、氮杂环丁烷基、氧杂环丁烷基、吗啉基、四氢异喹啉基、四氢喹啉基、二氢吲哚基、四氢吡喃基、二氢-2H-吡喃基、四氢呋喃基、四氢噻喃基、四氢噻喃-1-氧化物、四氢噻喃-1,1-二氧化物、1H-吡啶-2-酮和2,5-二氧代咪唑烷基。
本发明使用的术语“烷氧基”中的“烷基”的定义同前。
本发明使用的术语“芳氧基”中的“芳基”的定义同前。
本发明使用的术语“酰基”是指R c-C(＝O)-基团，其中，R c选自未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基等，R b的定义同前。
本发明使用的术语“亚磺酰基”是指R c-S(＝O)-基团，其中，R c的定义同前。
本发明使用的术语“磺酰基”是指R c-S(＝O) 2-基团，其中，R c的定义同前。
本发明使用的术语“磷酰基”是指R d-P(＝O)(R e)-基团，其中，R d和R e相同或不同，彼此独立地选自未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烷氧基、羟基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基等，R b的定义同前。
本发明使用的术语“肼基”是指-NHNHR c基团，R c的定义同前。
本发明使用的术语“胺基”指-NHR c基团或-N(R c) 2基团，R c的定义同前。
本发明使用的术语“氨基”指-NH 2基团。
本发明使用的术语“羧基”是指-COOH基团。
本发明使用的术语“酯基”是指R c-C(＝O)-O-基团或R c-O-C(＝O)-基团，其中，R c的定义同前。
本发明使用的术语“酰胺基”是指R c-C(＝O)-NH-基团，其中，R c的定义同前。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的保护范围。此外，应理解，在阅读了本发明所公开的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本发明所限定的保护范围之内。
实施例1
将反应物甲苯(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于34W CFL或蓝光(波长为400-455nm)下(其中的反应混合液置于反应光源下)，于室温、空气或氧气氛围(1atm)中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物苯甲醛或GC-MS定量(产率23％)。
表征结果为： 1H NMR(800MHz,CDCl 3)δ10.03(s,1H),7.89(d,J＝7.0Hz,2H),7.64(t,J＝8.5Hz,1H),7.54(t,J＝7.7Hz,2H)； 13C NMR(201MHz,CDCl 3)δ192.46,,136.41,134.49,129.77,129.02。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000052
实施例2
实施例2采用实施例1同样的方法，不同仅是辅助助剂，具体列于表1a中。
表1a实施例2的具体反应条件
Figure PCTCN2019098940-appb-000053
实施例2a-2q
实施例2a-2q采用实施例1同样的方法(各反应的时间大约在8小时以上即可，可以持续到12小时或更长)，不同仅是反应物和光照条件(光源波长)，具体列于表1b中。
表1b实施例2a-2q的具体反应条件(分子氧种类为O 2)
Figure PCTCN2019098940-appb-000054
实施例2a、2b、2d和2e的表征结果列于表1c中。
表1c实施例2a、2b、2d和2e的表征数据
Figure PCTCN2019098940-appb-000055
实施例2c的反应式如下：
Figure PCTCN2019098940-appb-000056
实施例2d的反应式如下：
Figure PCTCN2019098940-appb-000057
实施例2e的反应式如下：
Figure PCTCN2019098940-appb-000058
实施例3
将反应物N,N-二甲基苄胺(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长420-455nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气(1atm)氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离或GC-MS定量分析得目标化合物苯甲醛(产率23％)和苯甲酸(产率37％)。
苯甲醛表征结果为： 1H NMR(800MHz,CDCl 3)δ10.03(s,1H),7.89(d,J＝7.0Hz,2H),7.64(t,J＝8.5Hz,1H),7.54(t,J＝7.7Hz,2H)； 13C NMR(201MHz,CDCl 3)δ192.46,,136.41,134.49,129.77,129.02。
苯甲酸表征结果为： 1H NMR(800MHz,MeOD)δ8.03-8.02(m,2H),7.60-7.56(m,1H),7.50-7.42(m,2H)； 13C NMR(201MHz,MeOD)δ168.46,132.64,130.51,129.32,128.06.
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000059
实施例3b-3h
实施例3b-3h采用实施例3同样的方法(各反应的时间大约在8小时以上即可，可以持续到12小时或更长)，不同仅是反应物和光照条件(光源波长)，具体列于表2a中。
表2a实施例3a-3h的具体反应条件(分子氧种类为O 2)
Figure PCTCN2019098940-appb-000060
实施例3b的反应式如下所示：
Figure PCTCN2019098940-appb-000061
实施例3c的反应式如下：
Figure PCTCN2019098940-appb-000062
实施例3d的反应式如下：
Figure PCTCN2019098940-appb-000063
实施例3e的反应式如下：
Figure PCTCN2019098940-appb-000064
实施例3f的反应式如下：
Figure PCTCN2019098940-appb-000065
实施例3g的反应式如下：
Figure PCTCN2019098940-appb-000066
实施例3h的反应式如下：
Figure PCTCN2019098940-appb-000067
实施例4
将反应物苯甲硫醚(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于紫光(波长为360-380nm)下(其中的反应混合液置于紫光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物苯基甲基亚砜(产率95％)。所述反应的反应式如下：
Figure PCTCN2019098940-appb-000068
实施例4a-4g
实施例4a-4g采用实施例4同样的方法(各反应的时间大约在8小时以上即可，可以持续到12小时或更长)，不同仅是反应物和光照条件(光源波长)，具体列于表3a中。
表3a实施例4a-4g的具体反应条件(分子氧种类为O 2)
Figure PCTCN2019098940-appb-000069
实施例4a的反应式如下所示：
Figure PCTCN2019098940-appb-000070
实施例4b的反应式如下所示：
Figure PCTCN2019098940-appb-000071
实施例4c的反应式如下所示：
Figure PCTCN2019098940-appb-000072
实施例4d的反应式如下所示：
Figure PCTCN2019098940-appb-000073
实施例4e的反应式如下所示：
Figure PCTCN2019098940-appb-000074
实施例4f的反应式如下所示：
Figure PCTCN2019098940-appb-000075
实施例4g的反应式如下所示：
Figure PCTCN2019098940-appb-000076
实施例5
将反应物异丙苯(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(1.0eq.)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于蓝光下(其中的反应混合液置于蓝光下)，于室温下氧气氛围中光照反应至反应完全。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物苯乙酮(产率65％)。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000077
实施例5a
实施例5a采用实施例5同样的方法，仅反应物不同，具体列于表4a中。
表4a实施例5a的具体反应条件
Figure PCTCN2019098940-appb-000078
实施例5a的表征结果列于表4b中。
表4b实施例5a的表征数据
Figure PCTCN2019098940-appb-000079
实施例5a的反应式如下所示：
Figure PCTCN2019098940-appb-000080
实施例6
将反应物2-萘乙烯(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于34W CFL下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物2-萘甲醛(产率25％)。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000081
实施例6a
实施例6a采用实施例6同样的方法，不同仅是反应物，具体列于表5a中。
表5a实施例6a的具体反应条件
Figure PCTCN2019098940-appb-000082
实施例6a的反应式如下所示：
Figure PCTCN2019098940-appb-000083
实施例7
将反应物1,2-二苯乙炔(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有 机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长420-425nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物联苯甲酰(产率41％)。
联苯甲酰表征结果为： 1H NMR(400MHz,CDCl 3)δ:7.98(d,J＝7.2Hz,4H),7.66(t,J＝7.2Hz,2H),7.53-7.49(m,4H)； 13C NMR(100MHz,CDCl 3)δ:194.52,134.83,133.01,129.87,128.99.
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000084
实施例8
将反应物二苯甲醇(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物二苯甲酮(产率96％)。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000085
实施例8a
实施例8a采用实施例8同样的方法，不同仅是反应物，具体列于表7a中。
表7a实施例8a的具体反应条件
Figure PCTCN2019098940-appb-000086
实施例8a的表征结果列于表7b中。
表7b实施例8a的表征数据
Figure PCTCN2019098940-appb-000087
实施例8a的反应式如下：
Figure PCTCN2019098940-appb-000088
实施例9
将反应物N-甲基喹啉盐碘化物(0.2mmol)，碳酸铯(2.0eq)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于蓝光下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物N-甲基喹啉酮(产率45％)。
表征数据为： 1H NMR(800MHz,CDCl 3)δ7.64(d,J＝9.4Hz,1H),7.53-7.56(m,2H),7.34(d,J＝8.4Hz,1H),7.21(t,J＝7.4Hz,1H),6.69(d,J＝9.4Hz,1H),3.70(s,3H)； 13C NMR(200MHz,CDCl 3)δ162.34,140.04,138.96,130.63,128.76,122.10,121.75,120.68,114.14,29.41.
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000089
实施例9a-9b
实施例9a-9b采用实施例9同样的方法，不同仅是添加剂，具体列于表8a中。
表8a实施例9a-9b的具体反应条件
Figure PCTCN2019098940-appb-000090
实施例10
将反应物苄基三苯基膦季磷盐(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.25eq.,0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离或GC-MS定量分析得目标化合物苯甲醛(产率58％)。
具有式15所示结构的化合物会发生下式所示反应：
Figure PCTCN2019098940-appb-000091
具体的本实施例的化合物的反应的反应式如下：
Figure PCTCN2019098940-appb-000092
实施例11
将反应物2-四氢萘酮(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有 机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离或GC-MS定量分析得目标化合物2-萘酚(产率28％)。
表征数据为：经 1H NMR(800MHz,CDCl 3)δ7.76(dd,J＝12.0,8.5Hz,2H),7.68(d,J＝8.2Hz,1H),7.43(t,J＝7.5Hz,1H),7.33(dd,J＝11.0,3.9Hz,1H),7.15(d,J＝2.2Hz,1H),7.10(dd,J＝8.8,2.5Hz,1H),4.91(s,1H)； 13C NMR(201MHz,CDCl 3)δ153.30,134.58,129.89,128.97,127.78,126.56,126.37,123.66,117.72,109.50.
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000093
实施例12
将反应物苯甲醛(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.25eq，0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离或GC-MS定量分析得目标化合物苯甲酸(产率100％)。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000094
实施例12a-12g
实施例12a-12g采用实施例12同样的方法，不同仅是反应物，具体的反应如下：
Figure PCTCN2019098940-appb-000095
Figure PCTCN2019098940-appb-000096
实施例12h
将反应物4-苯基联苯甲醛(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.25eq，0.5eq或1.0eq)溶解于有机溶剂无水乙醇(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离或GC-MS定量分析得目标化合物4-苯基联苯甲缩醛(产率100％)。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000097
实施例13
将反应物聚苯乙烯(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CHCl 3(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长约400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离或GC-MS定量分析得目标化合物种类及含量。
表征数据为： 1H NMR(800MHz,CDCl 3)δ10.03(s,1H),7.89(d,J＝7.0Hz,2H),7.64(t,J＝8.5Hz,1H),7.54(t,J＝7.7Hz,2H)； 13C NMR(201MHz,CDCl 3)δ192.46,136.41,134.49,129.77,129.02.
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000098
实施例14
将反应物苯胺(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。待反应完成后，将该反应混合液经减压浓缩得目标化合物粗品，将该目标化合物粗品经柱色谱分离得目标化合物二苯基脲(产率93％)。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000099
实施例15
将反应物环己甲酸(0.2mmol)和辅助助剂三氟甲烷亚磺酸钠(0.5eq或1.0eq)溶解于有机溶剂无水CH 3CN(2mL)中得到反应混合液，将该反应混合液置于含有磁力搅拌子的反应管中，再将该反应管置于3W blue LED的蓝光(波长400-405nm)下(其中的反应混合液置于蓝光下)，于室温、空气或氧气氛围中光照反应至反应完全(约12h)。经蒸馏的目标化合物环己酮(产率96％)。
所述反应的反应式如下：
Figure PCTCN2019098940-appb-000100
实施例15a-15b
实施例15a-15b采用实施例15同样的方法，不同仅是反应物，具体的反应如下：
Figure PCTCN2019098940-appb-000101
以上，对本发明的实施方式进行了说明。但是，本发明不限定于上述实施方式。凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种需氧氧化体系，其特征在于，所述体系包括：
    1)下述物质1a)～1d)的至少一种：
    1a)亚磺酸或其衍生物；
    1b)磺酸或其衍生物；
    1c)通过反应可以生成亚磺酸或其衍生物的化合物或混合物；
    1d)通过反应可以生成磺酸或其衍生物的化合物或混合物；
    和2)含分子氧的组分，包括氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
  2. 根据权利要求1所述的需氧氧化体系，其中，组分1)的量为所述需要氧化体系参与的需氧氧化反应中待氧化的反应原料的活性位点数的0.001-10倍量。
    优选地，所述体系中，组分2)选自氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
    优选地，所述体系中，组分2)可以是直接引入的，如氧气、含氧气的气体(如空气、氧气与惰性气体的混合物等)，也可以是原位生成的，如加入可以原位生成氧分子的反应体系的原料，具体如KMnO 4、KClO 3或H 2O 2等等。
  3. 根据权利要求1或2所述的需氧氧化体系，其中，所述体系中还进一步加入组分3)即酸类添加剂、碱类添加剂、盐类添加剂以及有机或过渡金属类催化剂中的一种或多种。
    优选地，所述体系由上述组分1)、上述组分2)和任选地上述组分3)组成。
  4. 一种光促需氧氧化方法，其特征在于，所述方法采用权利要求1-3任一项所述的需氧氧化体系在光照条件下制备反应原料的氧化产物。
  5. 根据权利要求4所述的光促需氧氧化方法，其中，所述光照的光源是CFL(CFL＝Compact Fluorescent Lamp，为紧凑型荧光灯)、白炽灯或LED(200-600nm)。
    优选地，所述光源的波长在200-600nm范围内调节。
  6. 根据权利要求4或5所述的光促需氧氧化方法，其中，组分1)的加入量相对于1mmol反应底物(即待氧化的反应原料)而言，约为0.001～10eq(例如为0.1～10eq，再例如2～8eq，再例如为2.5～5eq)。
  7. 根据权利要求4-6任一项所述的光促需氧氧化方法，其中，所述反应原料是含有碳氢键(C-H)、碳碳单键(C-C)、碳碳双键(C＝C)、碳碳三键(C≡C)及碳杂键(包括碳氧键(C-O)、碳氮键(C-N)、碳硫键(C-S)、碳硒键(C-Se)、碳硅键(C-Si)、碳磷键(C-P)、碳氮双键(C＝N)等)等的有机小分子、杂环盐类化合物、有机膦盐化合物或聚合物。
  8. 根据权利要求7所述的光促需氧氧化方法，其中，所述含有碳氢键(C-H)、碳碳单键(C-C)、碳碳双键(C＝C)、碳碳三键(C≡C)及碳杂键(包括碳氧键(C-O)、碳氮键(C-N)、碳硫键(C-S)、碳硒键(C-Se)、碳硅键(C-Si)、碳磷键(C-P)、碳氮双键(C＝N)等)等的有机小分子、杂环盐类化合物、有机膦盐化合物或聚合物是下述物质1)～14)中的一种：
    1)具有式6所示结构的化合物：
    Figure PCTCN2019098940-appb-100001
    式6中，R 3选自未取代或任选被一个或多个R b取代的下列基团：芳基、杂芳基等；R 4选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烷氧基、杂环基、芳基、杂芳基、卤素、羟基、巯基、硝基、氨基、肼基、酰基、亚磺酰基、磺酰基、磷酰基、羧基、酯基、酰胺基等；R 3和R 4基团任选地可以成环(例如可以成碳环或杂环)；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基、芳基。
    2)具有式7所示结构的化合物：
    Figure PCTCN2019098940-appb-100002
    式7中，R’ 3＝R 3；R 5相同或不同，彼此独立地选自未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基、肼基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；两个R 5任选可以成烃基环；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。
    3)具有式8所示结构的化合物：
    Figure PCTCN2019098940-appb-100003
    式8中，R” 3选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基等；R 7选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、羧基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；R 8和R 9相同或不同，彼此独立地选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基、肼基、羧基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基。
    4)具有式9所示结构的化合物：
    Figure PCTCN2019098940-appb-100004
    式9中，R” 3和R 8的定义如上所述。
    5)具有式10或式11所示结构的化合物：
    Figure PCTCN2019098940-appb-100005
    式10中，R”’ 3＝R’ 3，R’ 4＝R 4但不为H。
    式11中，R”’ 3＝R’ 3，R’ 4＝R 4，R” 4与R’ 4相同或不同，彼此独立地选自前面R 4定义的范围。
    6)具有式12所示结构的化合物：
    Figure PCTCN2019098940-appb-100006
    式12中，R 3的定义如上所述；R’ 8相同或不同，彼此独立地选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基等，R b的定义同前；X 2选自O、S、Se、Si、N、P等杂原子；y选自1、2或3，与X 2的价态相关，X 2为二价时，y＝1，X 2为三价时，y＝2，X 2为四价时，y＝3；当y＝2或3时，两个R’ 8可以成环。
    7)具有式13所示结构的化合物：
    Figure PCTCN2019098940-appb-100007
    式13中，R 4的定义如上所述；R 10选自H、未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基、氨基、肼基、羧基、酯基、酰基、亚磺酰基、磺酰基、磷酰基等；任选地R 4和R 10可以成环；每一个R b彼此独立地选自未取代或任选被一个或多个R b1取代的下列基团：卤素、羟基、巯基、硝基、氰基、烷基、烷氧基、环烷基、烯基、炔基、杂环基、芳基、杂芳基、氨基、羧基、酯基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等；每一个R b1彼此独立地选自卤素、羟基、烷基、芳基。
    8)具有式14或式14’所示结构的化合物：
    Figure PCTCN2019098940-appb-100008
    式14中，R”＝R’，m4为0-4的整数；当m4大于等于2时，相邻的两个R”可以成环，例如形成烃基环、芳基或杂芳基，所述芳基或杂芳基还可以任选被至少一个取代基R b所取代，R b的定义同前；R 11选自烷基或芳基取代烷基；m5为整数，如0,1,2,3,4,5……；X 3为阴离子，包括卤素(氟、氯、溴、碘)、羧酸根、磺酸根等；
    式14’中，R”、m4、R 11、m5、X 3的定义同上；R 4a为烃基环、芳基(例如苯基)或杂芳基；R”a与R”相同或不同，彼此独立地选自上述的R’；m4’与m4相同或不同，为0-4的整数；R’ 11与R 11相同或不同，彼此独立地选自烷基或芳基取代烷基；m5”与m5相同或不同，为整数0,1,2,3,4,5……；X’ 3与X 3相同或不同，为阴离子，包括卤素(氟、氯、溴、碘)、羧酸根、磺酸根等；q为0-4的整数(例如0,1,2)。
    9)具有式15所示结构的化合物：
    Figure PCTCN2019098940-appb-100009
    式15中，R”” 3＝R 3，X 3的定义同上；m5’为整数，例如0,1,2,3,4,5……(示例性的可以是0-10的整数)，且与P原子相连的三个R”” 3相同或不同。
    10)具有式16所示结构的化合物：
    Figure PCTCN2019098940-appb-100010
    式16中，R 12具有R 4的定义，m4，R 4的定义如上，并且，当m4大于等于2时，相邻的两个R 12可以成环，形成芳基或杂芳基，所述芳基或杂芳基还可以任选被至少一个R b所取代；每一个R b彼此独立地选自卤素、羟基、巯基、硝基、烷基、烷氧基、环烷基、杂环基、芳基、杂芳基、羧基、酯基、氨基、肼基、酰基、亚磺酰基、磺酰基、磷酰基等。
    11)包含式17所示重复单元的聚合物：
    Figure PCTCN2019098940-appb-100011
    式17中，R 3的定义如上所述；R 8相同或不同，定义如上所述。
    12)具有式18所示结构的化合物：
    Figure PCTCN2019098940-appb-100012
    式18中，R”’ 4选自未取代或任选被一个或多个R b取代的下列基团：烷基、环烷基、烯基、环烯基、炔基、环炔基、杂环基、芳基、杂芳基等，R b的定义同前。
    13)具有式19所示结构的化合物：
    Figure PCTCN2019098940-appb-100013
    式19中，R 3、R 4定义如上所述。
    14)具有式20所示结构的化合物：
    Figure PCTCN2019098940-appb-100014
    式20中，R 4，R 10定义如上所述，任选地R 4和R 10可以形成碳环或杂环，所述碳环可以被一个或多个R b取代。
  9. 根据权利要求4-8任一项所述的光促需氧氧化方法，其中，所述反应中，组分2)选自氧气、含氧气的气体和可以原位生成氧分子的反应体系的原料中的至少一种。
    优选地，反应过程中，控制组分2)的压力在1-20atm范围；组分2)的含量控制在1％-100％范围。
    优选地，所述反应在有机溶剂中进行。优选的，所述有机溶剂选自可以溶解反应原料的有机溶剂，例如甲醇、乙醇、乙腈、乙酸乙酯、丙酮、二氯甲烷、三氯甲烷、环己烷、四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、1,2-二氯乙烷、乙二醇二甲醚、1,4-二氧六环、氯苯等。
  10. 根据权利要求4-9任一项所述的光促需氧氧化方法，其中，所述反应在装有搅拌装置(如磁力搅拌子)的反应容器(如反应管)中进行。
    优选地，反应过程中，需将反应容器中的反应混合液置于光下完全照射。
    优选地，所述反应在-20-80℃进行。优选地，所述反应时间在0.1-100h范围。
PCT/CN2019/098940 2019-02-01 2019-08-01 一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法 Ceased WO2020155595A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910105393 2019-02-01
CN201910105393.5 2019-02-01

Publications (1)

Publication Number Publication Date
WO2020155595A1 true WO2020155595A1 (zh) 2020-08-06

Family

ID=71840133

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/098940 Ceased WO2020155595A1 (zh) 2019-02-01 2019-08-01 一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法

Country Status (2)

Country Link
CN (1) CN111517902B (zh)
WO (1) WO2020155595A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116283683A (zh) * 2023-02-20 2023-06-23 衡阳师范学院 一种光诱导催化合成二芳基硫醚胺类化合物的方法
CN118005468A (zh) * 2024-01-31 2024-05-10 常州大学 氮碳材料催化醇类和腈类合成n-烷基化酰胺类化合物的方法
JP2024523216A (ja) * 2021-06-09 2024-06-28 フーダン ユニバーシティー 飽和炭素－水素結合含有化合物の光促進酸化方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112358425A (zh) * 2020-11-19 2021-02-12 湖南科技学院 一种可见光促进芳基烷基硫醚化合物氧化合成芳基烷基砜化合物的方法
CN112375021A (zh) * 2020-11-20 2021-02-19 湖南生物机电职业技术学院 一种光催化氧化二芳基硫醚合成二芳基砜化合物的方法
CN114956933A (zh) * 2021-02-25 2022-08-30 清华大学 含同位素氧原子的标记物及其制备方法和应用
CN112961047B (zh) * 2021-03-03 2023-07-25 贵州大学 一种光热催化选择性氧化聚苯乙烯合成苯甲酸的方法
CN113292599B (zh) * 2021-05-21 2022-04-19 广东工业大学 一种苄基氧化膦类化合物及其制备方法和应用
CN114609263B (zh) * 2021-11-30 2024-06-18 苏州正济药业有限公司 一种(r)-2,4-二碘-3-甲基-1-烯及其对映异构体的检测方法
CN117263801B (zh) * 2023-09-19 2026-04-14 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) 一种光催化lmct制备二氟甲基类化合物的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5692232A (en) * 1979-12-27 1981-07-25 Mitsui Petrochem Ind Ltd Preparation of phenolic compound
CN108993590A (zh) * 2018-07-09 2018-12-14 湖南师范大学 一种钼掺杂十聚钨酸季铵盐高效光催化剂的制备方法
CN108993591A (zh) * 2018-07-10 2018-12-14 湖南师范大学 一种碳量子点掺杂十聚钨酸季铵盐的制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102617455B (zh) * 2011-12-26 2014-06-04 浙江工业大学 一种吡哆醛或盐酸吡哆醛的制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5692232A (en) * 1979-12-27 1981-07-25 Mitsui Petrochem Ind Ltd Preparation of phenolic compound
CN108993590A (zh) * 2018-07-09 2018-12-14 湖南师范大学 一种钼掺杂十聚钨酸季铵盐高效光催化剂的制备方法
CN108993591A (zh) * 2018-07-10 2018-12-14 湖南师范大学 一种碳量子点掺杂十聚钨酸季铵盐的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HONG YI , CHANGLIANG BIAN , XIA HU , LINBIN NIU ,AIWEN LEI: "Visible Light Mediated Efficient Oxidative Benzylic sp3 C-H to Ketone Derivatives Obtained under Mild Conditions Using O2.", CHEMICAL COMMUNICATIONS, vol. 51, no. 74, 24 July 2015 (2015-07-24), pages 14046 - 14049, XP055724058, ISSN: 1359-7345, DOI: 10.1039/C5CC06015J *
ZHIGUANG ZHANG,YUAN GAO, YUAN LIU, JIANJUN LI, HEXIN XIE, HAO LI, WEI WANG: "Organocatalytic Aerobic Oxidation of Benzylic sp3 C-H Bonds of Ethers and Alkylarenes Promoted by a Recyclable TEMPO Catalyst.", ORGANIC LETTERS, vol. 17, 29 October 2015 (2015-10-29), XP055724055, ISSN: 1523-7060, DOI: 10.1021/acs.orglett.5b02877 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2024523216A (ja) * 2021-06-09 2024-06-28 フーダン ユニバーシティー 飽和炭素－水素結合含有化合物の光促進酸化方法
JP7681352B2 (ja) 2021-06-09 2025-05-22 フーダン ユニバーシティー 飽和炭素－水素結合含有化合物の光促進酸化方法
EP4353707A4 (en) * 2021-06-09 2025-09-03 Univ Fudan PROCESS FOR LIGHT-ACTIVATED OXIDATION OF A COMPOUND CONTAINING A SATURATED CARBON-HYDROGEN BOND
CN116283683A (zh) * 2023-02-20 2023-06-23 衡阳师范学院 一种光诱导催化合成二芳基硫醚胺类化合物的方法
CN118005468A (zh) * 2024-01-31 2024-05-10 常州大学 氮碳材料催化醇类和腈类合成n-烷基化酰胺类化合物的方法

Also Published As

Publication number Publication date
CN111517902A (zh) 2020-08-11
CN111517902B (zh) 2022-06-14

Similar Documents

Publication Publication Date Title
CN111517902A (zh) 一种含亚磺酸、磺酸或其衍生物的需氧氧化体系及其光促氧化方法
Borah et al. Decarboxylative functionalization of cinnamic acids
CN110028403B (zh) 一种合成丁二酸类化合物的方法
Lin et al. Chemo-, regio-, and stereoselective trifluoromethylation of styrenes via visible light-driven single-electron transfer (SET) and triplet–triplet energy transfer (TTET) processes
Lei et al. Transmetalation of palladium enolate and its application in palladium-catalyzed homocoupling of alkynes: A room-temperature, highly efficient route to make diynes
Jamwal et al. Nano Pd (0) supported on cellulose: A highly efficient and recyclable heterogeneous catalyst for the Suzuki coupling and aerobic oxidation of benzyl alcohols under liquid phase catalysis
Liu et al. Recent progress in organophotoredox reaction
Feng et al. Cu (II)-Promoted palladium-catalyzed C–H ortho-arylation of N, N-dimethylbenzylamines
CN103420748B (zh) 一种铜催化醇氧化制备醛和酮的绿色方法
Wang et al. A walk around the application of nanocatalysts for cross-dehydrogenative coupling of C–H bonds
CN107935812B (zh) 钌催化烷基芳酮与二苯乙炔反应制备多芳取代萘衍生物的方法
Liao et al. Palladium-catalyzed desulfitative oxidative coupling between arenesulfinic acid salts and allylic alcohols: a strategy for the selective construction of β-aryl ketones and aldehydes
CN101757950B (zh) 一种催化剂体系及其在有机合成中导入多氟苯基的应用
CN110423217B (zh) 一种共轭烯炔化合物的制备方法
CN113387876B (zh) 一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法及产物
CN115232231A (zh) 一种无机盐催化聚烯烃链碳氢键酰亚胺化制备含肟醚官能团聚烯烃的方法
CN104045585A (zh) 新型三氟甲基化试剂及其制备和应用
Behmagham et al. Advancements in double decarboxylative coupling reactions of carboxylic acids
CN110038556B (zh) 具有混合结晶相的oms-2型复合材料、其制法及应用
CN107778204A (zh) 一种非罗考昔中间体的制备方法
CN106905227A (zh) 联芳基化合物的制备方法
Xian et al. Carbofunctionalization of Alkenes with Sulfoxonium Ylides through Visible‐Light‐Induced Copper/Photoredox Dual Catalysis
Sun et al. Photocatalytic Reductive Azaarenylation of Cyclopropanes via Consecutive Photo‐induced Electron Transfer: A Facile Route to α‐Quaternary Azaarenes
Lu et al. The Heck reaction in aqueous micelles
CN105837388B (zh) 烷基和烯基修饰的双官能团化联苯类化合物的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19913895

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19913895

Country of ref document: EP

Kind code of ref document: A1