CN113861103B - Method for synthesizing pyridine, bipyridine and terpyridine ligand - Google Patents

Method for synthesizing pyridine, bipyridine and terpyridine ligand Download PDF

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CN113861103B
CN113861103B CN202111173307.8A CN202111173307A CN113861103B CN 113861103 B CN113861103 B CN 113861103B CN 202111173307 A CN202111173307 A CN 202111173307A CN 113861103 B CN113861103 B CN 113861103B
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CN113861103A (en
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舒伟
任玉峰
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Southern University of Science and Technology
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D213/08—Preparation by ring-closure
    • C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
    • C07D213/12—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from unsaturated compounds
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/052—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being six-membered
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
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    • C07J—STEROIDS
    • C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract

A method for synthesizing pyridine, bipyridine and terpyridine ligands adopts a photosensitizer and cobalt oxime compound as a catalyst, and has the beneficial effects of safety, mildness, high efficiency and economy. Meanwhile, the cobalt oxime compound catalyst is insensitive to water and oxygen, has low reaction requirements, and can greatly reduce the operation difficulty.

Description

Method for synthesizing pyridine, bipyridine and terpyridine ligand
Technical Field
The invention belongs to the field of medicine synthesis, and relates to a method for synthesizing pyridine, bipyridine and terpyridine ligands.
Background
Pyridine is a very common heterocyclic compound that is found in many natural products, such as nicotine, nucleic acids, and the like. In addition, the pyridine skeleton and its derivatives have a wide range of pharmaceutical properties and pharmacological activities, and thus the pyridine skeleton is an important component of many clinical medicines and has been used in the treatment of various diseases such as cancer, antibacterial, antioxidant, antiviral, heart failure and various kinds of arthritis. In addition, pyridine backbones and derivatives thereof have sigma electron donating ability and pi electron accepting ability, and thus form stable metal chelates with various metal (iron, cobalt, nickel, copper, ruthenium, etc.) ions as monodentate, bidentate and polydentate ligands, and are widely used in the fields of catalytic materials, chemical analysis, luminescent materials, biological cell molecule modification, probes, etc.
Based on the chemical and biological activities of pyridines, scientists have developed a variety of methods for synthesizing pyridine backbones. However, the currently reported methods for synthesizing pyridine compounds often have problems such as insufficient universality, harsh reaction conditions, difficult raw material acquisition, more byproducts and the like.
Patent application CN106632019a discloses a preparation method of polysubstituted pyridine, but the method needs dimethyl sulfoxide as a solvent and an oxidant, and the reaction is carried out at 85-95 ℃ with a certain risk.
Therefore, there is a need to develop a green, efficient and mild process for preparing pyridines.
Disclosure of Invention
In order to solve the problems, the invention provides a synthesis method of pyridine compounds and application of a photosensitizer and cobalt oxime compound in preparation of pyridine compounds.
In a first aspect, the present invention provides a method for synthesizing a pyridine compound.
A method of synthesizing a compound of formula II comprising:
under the conditions of catalyst and illumination and acid and/or alkali, under the protection of inert gas, the compound shown in the formula I reacts with an ammonium source in a solvent, and is subjected to post-treatment to obtain the compound shown in the formula II; wherein,
The catalyst comprises a photosensitizer and a cobalt oxime complex;
R 1 including those selected from the group consisting of C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C9-C20 polycyclic aryl, substituted or unsubstituted C6-C20 heteroaryl, substituted or unsubstituted C3-C10 heterocyclyl, substituted or unsubstituted C3-C10 cycloalkyl, and substituted or unsubstituted C3-C10 cycloalkenyl;
R 2 including a member selected from the group consisting of C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and substituted or unsubstituted C3-C10 heterocyclyl;
R 3 comprising a member selected from the group consisting of a hydrogen atom, a C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 heteroaryl group, and a substituted or unsubstituted C3-C10 heterocyclic group;
R 4 including those selected from the group consisting of a hydrogen atom, a C1-C10 alkyl group, an ester group, a substituted or unsubstituted C6-C20 aryl group, a carbonyl group, and a cyano group; or alternatively
R 1 、R 4 Together with the atoms to which they are attached form a substituted or unsubstituted C3-C10 carbocyclic ring, a substituted or unsubstituted C3-C10 heterocyclic ring, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C9-C20 polycyclic aryl group.
In some embodiments, the synthetic method adds both an acid and a base.
The inert gas comprises nitrogen, argon, helium, neon, argon, krypton or xenon; preferably nitrogen.
The photosensitizer comprises at least one selected from the following structures:
the cobalt oxime complex comprises at least one selected from the following structures:
the ammonium source includes at least one selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium chloride, ammonium fluoroborate, ammonium fluoride, ammonium formate, and ammonium acetate. Preferably, the ammonium source is ammonium acetate.
The acid comprises an acid selected from the group consisting of trifluoroacetic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, scandium triflate, and yttrium triflate. Preferably, the acid is scandium triflate.
The base includes at least one selected from sodium acetate and triethylenediamine. Preferably, the base is triethylenediamine.
The solvent includes at least one selected from acetonitrile, dichloromethane, toluene, dioxane, dichloroethane and tetrahydrofuran, preferably acetonitrile.
The feeding mole ratio of the compound shown in the formula I to the ammonium source is 1:1-1:10. In some embodiments, the preferred feed molar ratio of the compound of formula I to the ammonium source is 1:2.
The molar ratio of the acid to the compound shown in the formula I is 5:100-50:100. In some embodiments, the preferred feed molar ratio of the acid to the compound of formula I is from 10:100 to 30:100. In some embodiments, the preferred molar ratio of acid to compound of formula I is 20:100.
The feeding mole ratio of the compound shown in the formula I to the alkali is 1:0.5-1:3. In some embodiments, the preferred feed molar ratio of the compound of formula I to the base is from 1:1 to 1:2. In some embodiments, the preferred feed molar ratio of the compound of formula I to the base is 1:1.5.
The charging mole ratio of the photosensitizer to the compound shown in the formula I is 0.5:100-10:100. In some embodiments, the preferred charge molar ratio of photosensitizer to compound of formula I is 1:100 to 5:100. In some embodiments, the preferred charge molar ratio of photosensitizer to compound of formula I is from 2:100 to 4:100. In some embodiments, the preferred charge molar ratio of photosensitizer to compound of formula I is 2:100.
The feeding mole ratio of the cobalt oxime compound to the compound shown in the formula I is 0.5:100-10:100. In some embodiments, the cobalt oxime complex is preferably dosed in a molar ratio to the compound of formula I of from 1:100 to 8:100. In some embodiments, the cobalt oxime complex is preferably dosed in a molar ratio to the compound of formula I of from 2:100 to 6:100. In some embodiments, the cobalt oxime complex is preferably dosed in a molar ratio to the compound of formula I of 3:100 to 5:100. In some embodiments, the preferred feed molar ratio of the cobalt oxime complex to the compound of formula I is 4:100.
The volume ratio of the substance of the compound shown in the formula I to the solvent is 0.01 mmol/1 mL-0.2 mmol/1 mL. In some embodiments, the preferred volume ratio of the amount of the compound of formula I to the solvent is from 0.05 mmol:1 mL to 0.15 mmol:1 mL. In some embodiments, the preferred volume ratio of the amount of the compound of formula I to the solvent is 0.1 mmol/1 mL.
The wavelength of the illumination is 420nm-475nm. In some embodiments, the illumination has a wavelength of 450nm to 460nm.
The reaction time is 12-36 h.
The temperature of the reaction is 10-40 ℃.
The post-processing includes: diluting with water and ethyl acetate, extracting the water phase with ethyl acetate twice, mixing the extracted organic phases, washing with saturated sodium chloride, drying with anhydrous magnesium sulfate, and separating.
The substitution includes substitution with alkyl, alkoxy, carboxyalkyl, alkanoyl, keto, alkylamino, halogen or nitro. In some embodiments, the substitution includes substitution with a methyl, ethyl, propyl, tert-butyl, methoxy, carboxymethyl, acetyl, keto, methylamino, chlorine atom, or nitro group.
The heteroatom of the heterocyclic or heteroaromatic ring may be a nitrogen atom, an oxygen atom or a sulfur atom.
In some embodiments, the R 1 Including those selected from methyl, phenyl, 4-tolyl, 4-methoxyphenyl, 2-pyridyl, 6-methyl-2-pyridyl, 3, 5-dimethylphenyl, indanyl, 3, 4-dihydro-2H-chromene, thiopyranyl or the following c, d, e, f structures:
in some embodiments, the R 2 Including those selected from the group consisting of methyl, phenyl, 4-tolyl, 2-pyridyl, propyl, 6-methyl-2-pyridyl, 2-furyl, 5-methyl-2-thienyl, 3, 5-dimethylphenyl, 4-tert-butylphenyl and 4-nitrophenyl.
In some embodiments, the R 3 Comprising a group selected from the group consisting of a hydrogen atom, phenyl, methyl, 2-naphthyl, 4-chlorophenyl, N-methyl-2-pyrrolyl, 4-pyridyl, 3-thienyl, 2-thienyl, 4-methylphenyl, 4-tert-butylphenyl, 4-phenylphenyl and 2-furyl。
In some embodiments, the R 4 Including those selected from the group consisting of hydrogen atoms, phenyl groups, ester groups, methyl groups, 4-methoxyphenyl groups, carbonyl groups, and cyano groups.
In some embodiments, the R 1 、R 4 Together with the atoms to which they are attached, form a substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted cycloheptenyl, phenyl, 4-tolyl, 4-methoxyphenyl, substituted or unsubstituted pyridyl, 3, 5-dimethylphenyl, 1H-indenyl, 1, 2-dihydronaphthyl, 2H-chromene, thiopyranyl group.
In some embodiments, the R 1 、R 4 Together with the atoms to which they are attached, constitute the following structure:
wherein,represents a single bond, a carbon-oxygen double bond or a conjugated double bond; in the compounds of formula I, p1 and p3 are as followsWherein one represents a carbon-oxygen double bond, the other represents a single bond, p2 is marked +.>Represents a single bond; in the compounds of the formula II, p1, p2 and p3 are marked +.>Forming a conjugated double bond structure.
In some embodiments, the compound of formula II comprises a structure selected from the group consisting of:
in a second aspect, the invention provides an application of a photosensitizer and cobalt oxime complex in preparation of pyridine compounds.
Use of a photosensitizer and cobalt oxime complex for the preparation of a pyridine compound, said photosensitizer comprising at least one member selected from the structures of the photosensitizer of the first aspect; the cobalt oxime complex comprises at least one structure selected from the cobalt oxime complexes of the first aspect.
Advantageous effects
Compared with the prior art, the invention has the following technical effects:
(1) Based on the development concept of sustainable chemistry, the pyridine compound is prepared by adopting the photosensitizer and the cobalt oxime compound as the catalyst, and the method has the beneficial effects of safety, mildness, high efficiency and economy. Meanwhile, the cobalt oxime compound catalyst is insensitive to water and oxygen, has low reaction requirements, and can greatly reduce the operation difficulty.
Definition of terms
Unless otherwise indicated, the following terms and phrases as used herein are intended to have the following meanings:
in the present invention, the expressions "compound I" and "compound represented by formula I" mean the same compound.
"room temperature" in the present invention refers to an ambient temperature, which is from about 10 ℃ to about 40 ℃. In some embodiments, "room temperature" refers to a temperature from about 20 ℃ to about 30 ℃; in other embodiments, "room temperature" refers to a temperature from about 25 ℃ to about 30 ℃; in still other embodiments, "room temperature" refers to 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, and the like.
In the present invention, "trace" means a yield of less than 3%.
In the present invention, the dotted line "- -" in the chemical formula indicates a non-covalent bond such as hydrogen bond or van der Waals force.
"alkyl" is a hydrocarbon containing a normal, secondary, tertiary, or cyclic carbon atom. For example, the alkyl group may have 1 to 10 carbon atoms (i.e., C 1 -C 10 Alkyl), 1 to 8 carbon atoms (i.e., C 1 -C 8 Alkyl) or 1 to 6 carbon atoms (i.e., C 1 -C 6 Alkyl). Examples of suitable alkyl groups include, but are not limited to, methyl (Me, -CH 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (i-Pr, i-propyl, -CH 2 CH 2 CH 3 ) 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3 ) 1-pentyl (n-pentyl, -CH) 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-pentyl (-CH (CH) 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 And octyl (- (CH) 2 ) 7 CH 3 )。
"alkenyl" is a radical comprising a moiety having at least one unsaturation, i.e., carbon-carbon sp 2 A hydrocarbon of a normal carbon atom, a secondary carbon atom, a tertiary carbon atom or a cyclic carbon atom of the double bond. For example, alkenyl groups may have 2 to 10 carbon atoms (C 2 -C 10 Alkenyl), 2 to 12 carbon atoms (C 2 -C 12 Alkenyl) or 2 to 6 carbon atoms (C 2 -C 6 Alkenyl). Examples of suitable alkenyl groups include, but are not limited to, ethylene or vinyl (-ch=ch) 2 ) Allyl (-CH) 2 CH＝CH 2 ) Cyclopentenyl (-C) 5 H 7 ) And 5-hexenyl (-CH) 2 CH 2 CH 2 CH 2 CH＝CH 2 )。
"aryl" means an aromatic hydrocarbon radical derived by removing one hydrogen atom from a single carbon atom of the parent aromatic ring system. For example, an aryl group may have 6 to 20 carbon atoms, 6 to 14 carbon atoms, or 6 to 10 carbon atoms. Typical aryl groups include, but are not limited to, groups derived from benzene (e.g., phenyl), substituted benzene, naphthalene, anthracene, biphenyl, and the like.
The term "substituted" referring to alkyl, aryl, heterocyclyl, heteroaryl, carbocyclyl, and the like, e.g. "substituted C 1 -C 10 Alkyl "," substituted C 6 -C 20 Aryl "," substituted C 1 -C 20 Heterocyclic "and" substituted carbocyclyl "are intended to mean respectivelyRefers to C wherein one or more hydrogen atoms are each independently replaced by a non-hydrogen substituent 1 -C 10 Alkyl, C 6 -C 20 Aryl, arylalkyl, C 1 -C 20 Heterocycles, carbocyclyl. Unless otherwise indicated, when the term "substituted" is used in conjunction with a group having two or more moieties capable of substitution, such as arylalkyl, a substituent may be attached to the aryl moiety, the alkyl moiety, or both.
"heterocycle" or "heterocyclyl" as used herein includes, by way of example and not limitation, those heterocycles described in the following: paquette, leo A.: principles of Modern Heterocyclic Chemistry (w.a. benjamin, new York, 1968), in particular chapters 1, 3, 4, 6, 7 and 9: the Chemistry of Heterocyclic Compounds, A Series of Monographs (John Wiley & Sons, new York,1950 to now), in particular volumes 13, 14, 16, 19 and 28 and J.Am.chem.Soc. (1960) 82:5566. in a particular embodiment of the invention, "heterocycle" includes "carbocycle" as defined herein in which one or more (e.g., 1, 2, 3, or 4) carbon atoms have been replaced with a heteroatom (e.g., O, N or S). The term "heterocycle" or "heterocyclyl" includes saturated rings, partially unsaturated rings, and aromatic rings (i.e., heteroaromatic rings). Substituted heterocyclyl groups include, for example, heterocycles substituted with any substituent disclosed herein including carbonyl.
Examples of heterocycles include by way of example and not by way of limitation, pyridyl, dihydropyridinyl, tetrahydropyridinyl (piperidinyl), thiazolyl, tetrahydrothienyl, thioxotetrahydrothienyl, pyrimidinyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, tetrazolyl, benzofuryl, thianaphtyl, indolyl, indolenyl, quinolinyl, isoquinolinyl, benzimidazolyl, piperidinyl, 4-piperidonyl, pyrrolidinyl, 2-pyrrolidinonyl, pyrrolinyl, tetrahydrofuranyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, octahydroisoquinolinyl, azacinyl (azacyclooctanyl), triazinyl, 6H-1,2, 5-thiadiazinyl, 2H,6H-1,5,2-dithiazinyl, thienyl, thianthrenyl, pyranyl, isobenzofuranyl, chroenyl, xanthenyl, phenoflavinyl 2H-pyrrolyl, isothiazolyl, isoxazolyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, IH-indazolyl, purinyl, 4H-quinolizinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, 4 aH-carbazolyl, beta-carbolinyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl phenazinyl, phenothiazinyl, furazanyl, phenoxazinyl, isochroman, chromanyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, pyrazolinyl, piperazinyl, indolinyl, isoindolinyl, quinuclidinyl, morpholinyl, oxazolidinyl, benzotriazole, benzisoxazolyl, oxindolyl, benzoxazolinyl, indigoid and bis-tetrahydrofuranyl.
"heteroaryl" refers to an aromatic heterocyclic group having at least one heteroatom in the ring. Non-limiting examples of suitable heteroatoms that may be included on the aromatic ring include oxygen, sulfur, and nitrogen. Non-limiting examples of heteroaryl rings include all those aromatic rings listed in the definition of "heterocyclyl" including pyridyl, pyrrolyl, oxazolyl, indolyl, isoindolyl, purinyl, furanyl, thienyl, benzofuranyl, benzothienyl, carbazolyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, quinolinyl, isoquinolinyl, pyridazinyl, pyrimidinyl, pyrazolyl, and the like.
Whenever a compound described herein is substituted with more than one identical designated group (e.g., "R" or "R 1 ") it is understood that these groups may be the same or different, i.e., each group is independently selected.
In the invention, the Chinese names corresponding to the reagents are shown in the following table.
Short for short Chinese name
DCM Dichloromethane (dichloromethane)
THF Tetrahydrofuran (THF)
Dioxane Dioxaalkane
DCE Dichloroethane (dichloroethane)
Toulene Toluene (toluene)
MeCN Acetonitrile
DABCO Triethylene diamine
TFA Trifluoroacetic acid
sc(OTf) 3 Scandium triflate of trifluoromethyl
TsOH Para-toluene sulfonic acid
MsOH Methanesulfonic acid
Y(OTf) 3 Yttrium triflate
AcOH Acetic acid
Detailed Description
In order to better understand the technical solution of the present invention, some non-limiting examples are further disclosed below to further describe the present invention in detail.
The reagents used in the present invention are all commercially available or can be prepared by the methods described herein.
Example 1: screening of photosensitizers
Into a 10mL Schlenk tube were charged 25.2mg of compound a (0.1 mmol,1 eq) and 15.4mg of compound b (0.2 mmol,2 eq), 2.3ul of CH 3 COOH (0.02 mmol) and 16.8mg of triethylenediamine (0.15 mmol,1.5 eq), 0.002mmol of the corresponding photosensitizer and 0.004mmol of cobalt oxime complex Co (dmgH) were added as in Table 1 2 Cl (DMAP), vacuumizing and replacing 3 times by nitrogen, adding 1.0mL of anhydrous acetonitrile under the protection of nitrogen flow, irradiating for 24 hours by using a 30W blue LED lamp (with the wavelength of 420-475 nm) at the temperature of 25 ℃, extracting a reaction solution by using 5mL of water and 10mL of ethyl acetate after the reaction is finished, extracting an aqueous phase by using ethyl acetate (5 mL multiplied by 2), merging the extracted organic phases, washing the merged organic phases by using saturated saline solution, drying by using anhydrous magnesium sulfate, and separating and purifying by column chromatography (eluent is a petroleum ether and ethyl acetate system) to obtain a compound 2 (white solid); the yields of the obtained compound 2 are shown in table 1.
Table 1: screening results of photosensitizer
The obtained compound 2 is taken to detect the hydrogen spectrum and mass spectrum, and the result is that:
hydrogen spectrum: 1 H NMR(400MHz，Chloroform-d)δ8.20(dd，J＝7.3，1.9Hz，4H)，7.82(dd，J＝8.5，7.1Hz，1H)，7.71(d，J＝7.8Hz，2H)，7.53(dd，J＝8.4，6.6Hz，4H)，7.50-7.40(m，2H)； 13 C NMR(101MHz，Chloroform-d)δ156.87，139.55，137.53，129.03，128.74，127.05，118.68。
mass spectrometry: HR-MS (ESI) calcd for C 17 H 14 N + [M+H] + 232.1121 found 232.1119。
Example 2: screening of cobalt oxime complexes
The procedure was as described in example 1, except that the photosensitizer and cobalt oxime complex were replaced with the photosensitizer and cobalt oxime complex shown in Table 2, and the molar amounts of photosensitizer and cobalt oxime complex charged were the same as those of the photosensitizer and cobalt oxime complex, respectively, of example 1, and the other procedures were the same as those described in example 1; compound 2 was prepared and the yields of the resulting compound 2 are shown in table 2.
Table 2: screening results of cobalt oxime Complex
The obtained compound 2 was examined for its hydrogen spectrum and mass spectrum, and the results were the same as those shown in example 1.
Example 3: screening of ammonia sources
The procedure of example 1 was followed except that compound b, the photosensitizer and the cobalt oxime complex were replaced with the ammonia source, the photosensitizer and the cobalt oxime complex shown in Table 3, and the molar amounts of the ammonia source, the photosensitizer and the cobalt oxime complex to be fed were the same as those of compound b, the photosensitizer and the cobalt oxime complex of example 1, respectively, and the other procedures were the same as those described in example 1; compound 2 was prepared and the yields of the resulting compound 2 are shown in table 3.
Table 3: screening results of Ammonia Source
Example 4: screening of solvents
The procedure was as described in example 1, and the anhydrous acetonitrile, photosensitizer and cobalt oxime complex were replaced with the solvents, photosensitizers and cobalt oxime complexes shown in Table 4, the solvent addition volumes were the same as those of the anhydrous acetonitrile of example 1, the molar amounts of photosensitizer and cobalt oxime complex charged were the same as those of the photosensitizer and cobalt oxime complex of example 1, respectively, and the rest was the same as that of example 1; compound 2 was prepared and the yields of the resulting compound 2 are shown in table 4.
Table 4: results of screening for solvent
Example 5: screening of alkali
The procedure of example 1 was followed except that triethylenediamine, photosensitizer and cobalt oxime complex were replaced with the base, photosensitizer and cobalt oxime complex shown in Table 5, and the molar amounts of base, photosensitizer and cobalt oxime complex charged were the same as the base, photosensitizer and cobalt oxime complex of example 1, respectively, and the remainder was the same as the procedure of example 1; compound 2 was prepared and the yields of the resulting compound 2 are shown in table 5.
Table 5: results of alkali screening
Numbering device Photosensitizers Cobalt oxime complex Alkali Conversion of Compound a Yield rate
1 Ir(ppy) 2 (bpy)]PF 6 Co(dmgBF 2 ) 2 .2H 2 O K 2 CO 3 17％ Trace
2 Ir(ppy) 2 (bpy)]PF 6 Co(dmgBF 2 ) 2 .2H 2 O Cs 2 CO 3 5％ Trace
3 Ir(ppy) 2 (bpy)]PF 6 Co(dmgBF 2 ) 2 .2H 2 O NaOAc 48％ 28％
4 Ir(ppy) 2 (bpy)]PF 6 Co(dmgBF 2 ) 2 .2H 2 O KOAc 12％ Trace
5 [Ir(ppy) 2 (bpy)]PF 6 Co(dmgBF 2 ) 2 .2H 2 O Et 3 N 48％ Trace
6 [Ir(ppy) 2 (bpy)]PF 6 Co(dmgBF 2 ) 2 .2H 2 O DABCO 90％ 64％
Example 6: acid screening
The procedure of example 1 was followed except that scandium triflate, photosensitizer and cobalt oxime complex were replaced with the acid, photosensitizer and cobalt oxime complex shown in Table 6, and the molar amounts of acid, photosensitizer and cobalt oxime complex charged were the same as those of the acid, photosensitizer and cobalt oxime complex of example 1, respectively, and the other procedures were followed as described in example 1; compound 2 was prepared and the yields of the resulting compound 2 are shown in table 6.
Table 6: acid screening results
Example 7: condition control test
25.2mg of compound a (0.1 mmol,1 eq) and compound b (0.2 mmol,2 eq) were taken, the amounts of compound b fed being indicated in Table 7, and the acid and base described in Table 7 were added, respectively, in the molar amounts indicated in example 1; adding a photosensitizer and cobalt oxime compound according to Table 7, vacuumizing and replacing 3 times with nitrogen, adding 1.0mL of anhydrous acetonitrile under the protection of nitrogen flow, irradiating for 24 hours at 25 ℃ with a 30W blue LED lamp (with the wavelength of 420nm-475 nm) (no irradiation in group 3), extracting the reaction solution with 5mL of water and 10mL of ethyl acetate after the reaction is finished, extracting the water phase with ethyl acetate (5 mL multiplied by 2), merging the extracted organic phases, washing the merged organic phases with saturated saline, drying with anhydrous magnesium sulfate, and separating and purifying by column chromatography (the eluent is a petroleum ether/ethyl acetate system) to obtain a compound 2 (white solid); the yields of the obtained compound 2 are shown in table 8.
Table 7: condition control test of each variable condition
Table 8: results of the Condition control test
Numbering device Conversion of Compound a Yield rate
1 58％ trace
2 74％ 28％
3 33％ trace
4 63％ 22％
5 44％ 19％
6 100％ 42％
7 81％ 65％
8 59％ 43％
Example 8: preparation of Compound 1
12.8mg of compound 67 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 m)g，0.2mmol，2equiv.)，Co(dmgBF2)2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 63% by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 5.9mg of compound 1 (pale yellow oily liquid, yield 55%). The obtained compound 1 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the result is as follows:
1 H NMR(600MHz，Chloroform-d)δ7.45(t，J＝7.6Hz，1H)，6.94(d，J＝7.6Hz，2H)，2.51(s，6H)。
13 C NMR(151MHz，Chloreform-d)δ157.65，136.56，120.18，24.44。
HR-MS(ESI)calcd for C 7 H 10 N + [M+H] + 108.0808 found 108.0811。
example 9: preparation of Compound 3
19.0mg of compound 68 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). Then will have The organic phase was concentrated and added with dibromomethane as an internal nuclear magnetic standard after drying over anhydrous magnesium sulfate, and the reaction yield was 88% as determined by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 14.4mg of compound 3 (pale yellow oily liquid, yield 85%). The obtained compound 3 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.01-7.95(m，2H)，7.63(t，J＝7.7Hz，1H)，7.51(d，J＝7.8Hz，1H)，7.50-7.43(m，2H)，7.43-7.36(m，1H)，7.10(d，J＝7.6Hz，1H)，2.63(s，3H)。
13 C NMR(101MHz，Chloroform-d)δ158.39，157.02，139.82，136.89，128.71，128.69，127.02，121.61，117.65，24.78。
HR-MS(ESI)calcd for C 12 H 12 N + [M+H] + 170.0964 found 170.0963。
example 10: preparation of Compound 66
24.4mg of compound 69 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 94% as determined by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 19.8mg of compound 66 (pale yellow oily liquid, 89% yield). The obtained compound 66 was subjected to hydrogen spectrum Carbon spectrum and mass spectrum detection, the results are as follows:
1 H NMR(600MHz，Chloroform-d)δ7.44-7.40(m，2H)，7.39-7.35(m，1H)，7.29-7.26(m，2H)，6.84(s，1H)，2.97(t，J＝6.6Hz，2H)，2.58(t，J＝6.4Hz，2H)，2.51(s，3H)，1.95-1.86(m，2H)，1.71(qd，J＝9.0，7.6，4.5Hz，2H)。
13 C NMR(151MHz，Chloroform-d)δ156.81，154.68，150.02，139.63，128.50，128.24，127.63，126.74，121.57，33.01，27.09，24.01，23.09，23.06。
HR-MS(ESI)calcd for C 16 H 18 N + [M+H] + 224.1434 found 224.1441。
example 11: preparation of Compound 6
23.0mg of compound 70 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 85% by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification gave 16.3mg of compound 6 (pale yellow oily liquid, yield 78%). The obtained compound 6 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the result is as follows:
1 H NMR(400MHz，Chloroform-d)δ7.99-7.89(m，2H)，7.47-7.39(m，4H)，7.39-7.34(m，1H)，3.00(t，J＝6.4Hz，2H)，2.80(t，J＝6.3Hz，2H)，1.93(tdd，J＝8.4，5.3，2.6Hz，2H)，1.85(dtt，J＝9.4，6.1，2.8Hz，2H)。
13 C NMR(101MHz，Chloroform-d)δ157.27，154.71，139.95，137.45，130.75，128.64，128.36，126.85，117.95，32.86，28.58，23.23，22.82。
HR-MS(ESI)calcd for C 15 H 16 N + [M+H] + 210.1275 found 210.1277。
example 12: preparation of Compound 4
32.8mg of compound 71 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 81% by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 23.0mg of compound 4 (pale yellow oily liquid, yield 75%). The obtained compound 6 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the result is as follows:
1 H NMR(400MHz，Chloroform-d)δ8.27-8.17(m，4H)，7.90(s，2H)，7.81-7.71(m，2H)，7.58-7.50(m，6H)，7.50-7.42(m，3H。
13 C NMR(101MHz，Chloroform-d)δ157.54，150.23，139.62，139.10，129.14，129.07，129.00，128.73，127.22，127.16，117.16。
HR-MS(ESI)calcd for C 23 H 18 N + [M+H] + 308.1434 found 308.1431。
example 13: preparation of Compound 5
18.2mg of compound 72 (0.1 mmol,1 equiv.) are added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 93% as determined by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 14.0mg of compound 5 (pale yellow oily liquid, yield 87%). The obtained compound 5 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ6.77(s，1H)，2.87(t，J＝6.0Hz，2H)，2.59(t，J＝6.1Hz，2H)，2.44(s，3H)，2.16(s，3H)，1.83(tdd，J＝11.3，6.4，2.6Hz，4H)。
13 C NMR(151MHz，Chloroform-d)δ155.79，154.28，146.16，127.95，122.21，32.88，25.48，23.80，22.97，22.91，18.82。
HR-MS(ESI)calcd for C 11 H 16 N + [M+H] + 162.1277 found 162.1276。
Example 14: preparation of Compound 7
34.2mg of compound 73 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 m.times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 87% by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 27.3mg of compound 7 (white solid, 85% yield). The obtained compound 7 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ7.21-7.15(m，2H)，7.13(s，1H)，7.09(ddd，J＝9.1，4.3，2.0Hz，6H)，7.01-6.91(m，5H)，6.80-6.75(m，2H)，2.61(s，3H)。
13 C NMR(101MHz，Chloroform-d)δ157.90，156.92，150.01，141.01，139.68，137.93，131.61，131.52，129.91，129.31，127.86，127.63，127.61，127.25，127.20，126.40，123.26，24.47。
HR-MS(ESI)calcd for C 24 H 20 N + [M+H] + 322.1590 found 322.1586。
example 15: preparation of Compound 8
35.6mg of compound 74 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol, 2) equiv.)，Co(dmgBF2)2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 53% by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification gave 17.1mg of compound 8 (pale yellow oily liquid, yield 51%). The obtained compound 8 is taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the result is as follows:
1 H NMR(400MHz，Chloroform-d)δ8.49(dd，J＝7.8，1.7Hz，1H)，8.20-8.12(m，2H)，7.63(s，1H)，7.51(tdd，J＝10.0，6.3，3.3Hz，5H)，7.48-7.41(m，1H)，7.35(ddd，J＝13.0，7.7，1.7Hz，3H)，7.16(td，J＝7.5，1.1Hz，1H)，6.98(dd，J＝8.2，1.1Hz，1H)，5.27(s，2H)。
13 C NMR(101MHz，Chloroform-d)δ156.47，156.20，148.78，147.34，139.16，137.58，131.22，129.12，128.80，128.74，128.63，128.48，126.96，125.38，123.83，122.33，122.17，119.99，116.78，65.96。
HR-MS(ESI)calcd for C 24 H 18 NO + [M+H] + 336.1383 found 336.1379。
example 16: preparation of Compound 9
35.4mg of compound 75 (0.1 mmol,1 equiv.) are added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and trifluormethylScandium sulfonate (9.8 mg,0.02 mmol), vacuum and displacement with nitrogen 3 times, 1.0mL of anhydrous acetonitrile under nitrogen flow protection. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 58% as determined by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 18.3mg of compound 9 (pale yellow solid, yield 55%). The obtained compound 9 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.59(dd，J＝7.8，1.4Hz，1H)，8.22-8.16(m，2H)，7.61(s，1H)，7.55-7.45(m，5H)，7.45-7.40(m，4H)，7.34(td，J＝7.4，1.5Hz，1H)，7.25-7.21(m，1H)，2.99-2.92(m，2H)，2.87(dd，J＝9.3，6.0Hz，2H)。
13 C NMR(101MHz，Chloroform-d)δ154.44，152.60，149.27，139.57，139.36，138.19，135.23，129.06，128.83，128.72，128.66，128.48，128.02，127.93，127.48，127.08，126.82，125.75，119.95，28.18，25.30。
HR-MS(ESI)calcd for C 25 H 20 N + [M+H] + 334.1590 found 334.1586。
Example 17: preparation of Compound 10
34.0mg of compound 76 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed in 30W blueAfter the completion of the reaction, the Schlenk tube was opened and the reaction mixture was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 65% by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 18.8mg of compound 10 (white solid, 59% yield). The obtained compound 10 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.27(d，J＝7.4Hz，1H)，8.23-8.13(m，2H)，7.69(s，1H)，7.69-7.65(m，2H)，7.60-7.39(m，9H)，4.03(s，2H)。
13 C NMR(101MHz，Chloroform-d)δ161.18，157.20，146.43，144.13，141.21，139.92，138.93，132.90，128.89，128.77，128.75，128.72，128.57，128.26，127.24，127.20，124.98，121.43，118.24，34.44。
HR-MS(ESI)calcd for C 24 H 18 N + [M+H] + 320.1434 found 320.1431。
example 18: preparation of Compound 11
40.4mg of compound 77 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfateAfter that, the organic phase was concentrated and dibromomethane was added as an internal nuclear magnetic standard, and the reaction yield was determined to be 51% by nuclear magnetic hydrogen spectrum. Column chromatography separation and purification gave 18.0mg of compound 11 (white solid, yield 47%). The obtained compound 11 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.23-8.13(m，2H)，7.78(s，1H)，7.49(dd，J＝8.3，6.5Hz，2H)，7.46-7.41(m，1H)，7.41-7.35(m，2H)，7.22(ddd，J＝10.5，5.0，2.0Hz，6H)，7.17-7.11(m，2H)，7.10-7.03(m，3H)，6.95-6.89(m，2H)。
13 C NMR(101MHz，Chloroform-d)δ156.92，154.55，149.66，139.88，138.80，138.00，136.81，131.87，130.40，129.17，128.30，127.99，127.67，126.90，126.68，126.48，126.36，126.32，126.05，125.56，119.36。
HR-MS(ESI)calcd for C 29 H 22 N + [M+H] + 384.1747 found 384.1742。
example 19: preparation of Compound 12
32.4mg of compound 78 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 92% as determined by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification to obtain 26.7m g compound 12 (white solid, 88% yield). The obtained compound 12 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.04-7.86(m，2H)，7.50(s，1H)，7.42-7.30(m，8H)，3.57(s，3H)，2.63(s，3H)。
13 C NMR(151MHz，Chloroform-d)δ168.53，156.49，154.79，147.88，137.79，137.72，128.36，127.77，127.64，127.57，126.76，126.19，125.48，117.51，51.19，22.18。
HR-MS(ESI)calcd for C 20 H 18 NO 2 + [M+H] + 304.1332 found 304.1329。
example 20: preparation of Compound 13
35.6mg of compound 79 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 63% by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 17.1mg of compound 13 (white solid, 51% yield). The obtained compound 13 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.11-8.06(m，2H)，7.60(d，J＝3.7Hz，2H)，7.57(d，J＝1.4Hz，1H)，7.52-7.35(m，8H)，7.30(d，J＝7.8Hz，2H)，2.44(s，3H)，2.27(s，3H)。
13 C NMR(101MHz，Chloroform-d)δ159.45，153.96，151.61，140.39，139.36，138.54，137.70，129.40，128.82，128.79，128.62，128.47，127.88，126.95，126.92，119.83，21.36，18.08。
HR-MS(ESI)calcd for C 25 H 22 N + [M+H] + 336.1747 found 336.1744。
example 21: preparation of Compound 14
37.8mg of Compound 80 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 77% as determined by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 25.3mg of compound 14 (white solid, 71% yield). The obtained compound 14 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.17-8.13(m，4H)，8.11(s，1H)，7.91(s，2H)，7.90(d，J＝8.4Hz，1H)，7.88-7.85(m，1H)，7.84-7.79(m，1H)，7.75(dd，J＝8.5，1.6Hz，1H)，7.49-7.42(m，6H)，7.40-7.35(m，2H)。
13 C NMR(151MHz，Chloroform-d)δ157.63，150.14，139.65，136.34，133.57，133.48，129.12，128.98，128.77，128.49，127.81，127.22，126.81，126.75，126.52，124.88，117.35。
HR-MS(ESI)calcd for C 27 H 20 N + [M+H] + 358.1590 found 358.1586。
example 22: preparation of Compound 15
42.2mg of Compound 81 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 44% as determined by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 16.4mg of compound 15 (white solid, 41% yield). The obtained compound 15 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.20-8.11(m，4H)，7.71(s，2H)，7.70-7.60(m，2H)，7.53-7.46(m，2H)，7.10-6.98(m，4H)，3.89(s，6H)。
13 C NMR(101MHz，Chloroform-d)δ160.60，157.12，148.78，137.77，135.03，132.11，129.28，128.46，128.40，115.41，114.08，55.41。
HR-MS(ESI)calcd for C 25 H 21 ClNO 2 + [M+H] + 402.1255 found 402.1252。
example 23: preparation of Compound 16
33.1mg of compound 82 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 64% by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 18.6mg of compound 16 (white solid, 60% yield). The obtained compound 16 was subjected to hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.25-8.10(m，4H)，7.72(s，2H)，7.52(dd，J＝8.2，6.5Hz，4H)，7.50-7.39(m，2H)，6.84(t，J＝2.3Hz，1H)，6.53(dd，J＝3.7，1.8Hz，1H)，6.29(dd，J＝3.7，2.7Hz，1H)，3.84(s，3H)。
13 C NMR(101MHz，Chloroform-d)δ157.20，142.16，139.57，132.38，129.08，128.75，127.11，125.90，117.67，110.70，108.59，35.65。
HR-MS(ESI)calcd for C 22 H 19 N 2 + [M+H] + 311.1543 found 311.1540。
Example 24: preparation of Compound 17
37.2mg of compound 83 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 78% by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification gave 25.6mg of compound 17 (white solid, 73% yield). The obtained compound 17 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.10-8.04(m，2H)，7.61(s，1H)，7.49(t，J＝7.5Hz，2H)，7.45-7.39(m，1H)，7.22(dd，J＝5.4，1.8Hz，3H)，7.13(dd，J＝6.6，2.9Hz，2H)，7.01(d，J＝8.4Hz，2H)，6.81(d，J＝8.5Hz，2H)，3.79(s，3H)，2.52(s，3H)。
13 C NMR(151MHz，Chloroform-d)δ157.41，156.32，154.31，148.76，138.85，138.40，132.38，130.35，129.48，128.25，127.73，127.69，126.87，126.20，125.96，118.33，112.52，54.12，23.32。
HR-MS(ESI)calcd for C 25 H 22 NO + [M+H] + 352.1696 found 352.1693。
example 25: preparation of Compound 18
32.9mg of compound 84 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15) .4mg，0.2mmol，2equiv.)，Co(dmgBF2)2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 73% as determined by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 23.1mg of compound 18 (white solid, 75% yield). The obtained compound 18 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.86(s，2H)，8.20(dd，J＝7.9，4.0Hz，4H)，7.89(d，J＝4.0Hz，2H)，7.70(s，2H)，7.53(dt，J＝11.0，5.1Hz，4H)，7.47(q，J＝7.3，6.2Hz，2H)。
13 C NMR(151MHz，Chloroform-d)δ158.07，150.32，147.28，146.96，139.05，129.45，128.85，127.16，122.10，116.67。
HR-MS(ESI)calcd for C 22 H 17 N 2 + [M+H] + 309.1386 found 309.1383。
example 26: preparation of Compound 19
33.0mg of Compound 85 (0.1 mmol,1 equiv.) is introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube is placed in a 30W blue light lamp to irradiate for 24 hours, and the reaction is reversed After completion, the Schlenk tube was opened and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 73% as determined by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 21.6mg of compound 19 (white solid, 70% yield). The obtained compound 19 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.75(s，2H)，8.73(ddd，J＝4.8，1.8，0.9Hz，2H)，8.67(dt，J＝7.9，1.1Hz，2H)，7.94-7.82(m，4H)，7.51(dd，J＝8.3，6.5Hz，2H)，7.48-7.43(m，1H)，7.35(ddd，J＝7.5，4.8，1.2Hz，2H)。
13 C NMR(101MHz，Chloroform-d)δ156.23，155.89，150.38，149.12，138.48，136.95，129.05，128.95，127.37，123.87，121.42，118.98。
HR-MS(ESI)calcd for C 21 H 16 N 3 + [M+H] + 310.1339 found 310.1337。
example 27: preparation of Compound 20
33.4mg of compound 86 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate After drying, the organic phase was concentrated and dibromomethane was added as an internal nuclear magnetic standard, and the reaction yield was determined to be 78% by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification gave 23.5mg of compound 20 (white solid, 75% yield). The obtained compound 20 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.24-8.18(m，4H)，7.88(s，2H)，7.77(dd，J＝3.0，1.4Hz，1H)，7.58-7.54(m，2H)，7.53-7.49(m，4H)，7.49-7.43(m，2H)。
13 C NMR(101MHz，Chloroform-d)δ157.67，144.48，140.29，139.54，129.10，128.73，127.14，127.08，126.04，123.03，116.32。
HR-MS(ESI)calcd for C 21 H 16 NS + [M+H] + 314.0998 found 314.0996。
example 28: preparation of Compound 22
32.5mg of compound 87 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 87% by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 25.2mg of compound 22 (white solid, 83% yield). The obtained compound 22 was taken for hydrogen, carbon and mass spectrometry detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.67(ddd，J＝4.8，1.8，0.9Hz，1H)，8.49(dt，J＝7.9，1.1Hz，1H)，8.30(s，1H)，7.83(td，J＝7.7，1.8Hz，1H)，7.47-7.42(m，4H)，7.41-7.38(m，1H)，7.32(ddd，J＝7.5，4.7，1.2Hz，1H)，3.66(s，3H)，2.71(s，3H)。
13 C NMR(151MHz，Chloroform-d)δ169.61，155.90，155.49，155.42，149.21，149.09，138.71，137.02，128.58，128.57，127.93，127.90，124.07，121.66，119.04，52.26，23.16。
HR-MS(ESI)calcd for C 19 H 17 N 2 O 2 + [M+H] + 302.1285 found 305.1282。
Example 29: preparation of Compound 25
35.7mg of compound 88 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 69% by nuclear magnetic hydrogen spectroscopy. Purification by column chromatography gave 22.8mg of compound 25 (pale yellow oily liquid, yield 68%). The obtained compound 25 was subjected to hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.70-8.65(m，2H)，8.48(dd，J＝7.7，1.7Hz，1H)，8.36(s，1H)，7.87(td，J＝7.7，1.9Hz，1H)，7.52-7.44(m，3H)，7.41-7.38(m，2H)，7.38-7.32(m，2H)，7.17(td，J＝7.5，1.1Hz，1H)，6.99(dd，J＝8.1，1.1Hz，1H)，5.29(s，2H)。
13 C NMR(151MHz，Chloroform-d)δ156.48，156.04，154.88，149.03，148.48，147.65，137.41，136.99，131.26，128.68，128.59，125.21，123.86，123.83，123.73，122.33，121.38，120.67，116.87，66.08。
HR-MS(ESI)calcd for C 23 H 17 N 2 O + [M+H] + 337.1335 found 337.1331。
example 30: preparation of Compound 26
40.5mg of compound 89 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 42% as determined by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 14.2mg of compound 26 (white solid, 37% yield). The resulting compound 26 was taken for hydrogen, carbon and mass spectrometry detection as follows:
1 H NMR(600MHz，Chloroform-d)δ8.70(d，J＝4.8Hz，1H)，8.62(d，J＝8.0Hz，1H)，8.48(s，1H)，7.84(td，J＝7.7，1.8Hz，1H)，7.39(dd，J＝6.8，2.8Hz，2H)，7.33(dd，J＝7.4，4.9Hz，1H)，7.25-7.19(m，6H)，7.16(p，J＝3.6Hz，2H)，7.08(tt，J＝8.6，4.6Hz，3H)，6.97-6.92(m，2H)。
13 C NMR(151MHz，Chloroform-d)δ157.69，156.04，154.27，150.94，149.00，140.93，139.64，137.90，137.00，134.45，131.40，130.18，129.47，127.82，127.74，127.56，127.43，127.29，126.68，123.77，121.60，121.01。
HR-MS(ESI)calcd for C 28 H 21 N 2 + [M+H] + 385.1699 found 385.1696。
example 31: preparation of Compound 27
34.1mg of compound 90 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 75% as determined by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 22.7mg of compound 27 (white solid, 71% yield). The obtained compound 27 was subjected to hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.75-8.65(m，2H)，8.44(d，J＝1.7Hz，1H)，8.26(d，J＝7.5Hz，1H)，7.93-7.84(m，1H)，7.72(dd，J＝7.2，1.8Hz，2H)，7.56(d，J＝7.4Hz，1H)，7.55-7.50(m，2H)，7.50-7.40(m，3H)，7.32(dd，J＝7.1，4.7Hz，1H)，4.02(s，2H)。
13 C NMR(151MHz，Chloroform-d)δ160.85，156.68，155.67，149.07，146.59，144.15，141.06，138.75，136.95，134.59，128.76，128.54，128.40，127.24，125.04，123.56，121.41，121.27，118.64，34.63。
HR-MS(ESI)calcd for C 23 H 17 N 2 + [M+H] + 321.1386 found 321.1383。
Example 32: preparation of Compound 28
30.9mg of Compound 91 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 53% by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification gave 14.1mg of compound 28 (white solid, 49% yield). The resulting compound 28 was taken for hydrogen, carbon and mass spectrometry detection as follows:
1 H NMR(600MHz，Chloroform-d)δ8.68(d，J＝4.7Hz，1H)，8.48(d，J＝7.9Hz，1H)，8.29(d，J＝1.8Hz，1H)，7.84(td，J＝7.7，3.9Hz，1H)，7.45(d，J＝1.9Hz，5H)，7.38-7.31(m，1H)，2.63(s，3H)，2.02(s，3H)。
13 C NMR(151MHz，Chloroform-d)δ206.43，155.55，155.47，153.71，149.21，147.51，138.25，137.05，135.83，128.97，128.93，128.64，124.03，121.58，119.16，32.04，23.02。
HR-MS(ESI)calcd for C 19 H 17 N 2 O + [M+H] + 289.1335 found 289.1333。
example 33: preparation of Compound 30
25.4mg of compound 92 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 61% by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 13.5mg of compound 30 (white solid, 58% yield). The obtained compound 30 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.70(dd，J＝4.7，1.5Hz，2H)，8.62(dd，J＝7.9，1.2Hz，2H)，8.45(dd，J＝7.8，1.1Hz，2H)，7.96(td，J＝7.8，1.1Hz，1H)，7.86(tt，J＝7.7，1.4Hz，2H)，7.33(ddt，J＝7.4，4.9，1.3Hz，2H)。
13 C NMR(151MHz，Chloroform-d)δ156.22，155.32，149.12，137.95，136.93，123.79，121.22，121.05。
HR-MS(ESI)calcd for C 15 H 12 N 3 + [M+H] + 234.1026 found 234.1023。
example 34: preparation of Compound 33
35.6mg of compound 93 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 85% by nuclear magnetic hydrogen spectroscopy. Purification by column chromatography gave 27.1mg of compound 33 (pale yellow oily liquid, yield 81%). The obtained compound 33 was subjected to hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.73(dd，J＝4.9，1.7Hz，1H)，8.70(dt，J＝8.0，1.1Hz，1H)，8.59(ddd，J＝4.8，1.8，0.9Hz，1H)，8.32(s，1H)，7.78(td，J＝7.8，1.9Hz，1H)，7.53(dd，J＝7.6，1.7Hz，1H)，7.44-7.33(m，5H)，7.26-7.19(m，2H)，3.00-2.91(m，2H)，2.84(dd，J＝8.6，5.5Hz，2H)。
13 C NMR(101MHz，Chloroform-d)δ156.08，154.69，152.09，151.49，149.89，148.92，148.80，138.73，136.96，135.87，134.13，131.83，128.90，128.45，128.19，123.72，123.64，122.19，122.12，27.60，24.98。
HR-MS(ESI)calcd for C 23 H 18 N 3 + [M+H] + 336.1495 found 336.1487。
Example 35: preparation of Compound 35
38.6mg of compound 94 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 99% as determined by nuclear magnetic hydrogen spectrometry. Column chromatography separation and purification gave 35.0mg of compound 35 (white solid, 96% yield). The obtained compound 35 was taken for hydrogen, carbon and mass spectrometry detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.80-8.72(m，4H)，8.67(dq，J＝8.0，1.3Hz，2H)，7.88(ddt，J＝8.0，5.1，2.0Hz，4H)，7.56-7.49(m，2H)，7.36(ddt，J＝6.1，4.6，2.5Hz，2H)，1.38(s，9H)。
13 C NMR(101MHz，Chloroform-d)δ156.33，155.80，152.32，150.17，149.08，136.94，135.48，127.03，125.89，123.79，121.42，118.80，34.74，31.33。
HR-MS(ESI)calcd for C 25 H 24 N 3 + [M+H] + 366.1965 found 366.1956。
example 36: preparation of Compound 37
At 1033.1mg of Compound 95 (0.1 mmol,1 equiv.) are added to a ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 95% by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 28.2mg of compound 37 (white solid, 91% yield). The obtained compound 37 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.77(dd，J＝3.8，1.8Hz，4H)，8.73(d，J＝4.7Hz，2H)，8.67(d，J＝7.9Hz，2H)，7.94-7.86(m，2H)，7.82-7.77(m，2H)，7.41-7.35(m，2H)。
13 C NMR(151MHz，Chloroform-d)δ156.42，155.73，150.48，149.22，147.49，146.09，137.03，124.16，121.76，121.41，118.70。
HR-MS(ESI)calcd for C 20 H 15 N 4 + [M+H]+311.1291 found 311.1285。
example 37: preparation of Compound 39
32.0mg of compound 96 (0.1 mmol,1 equiv.) was added to a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), vacuum and nitrogen were applied3 times of displacement, under the protection of nitrogen flow, 1.0mL of anhydrous acetonitrile is added. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 78% by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification gave 23.0mg of compound 39 (white solid, yield 77%). The obtained compound 39 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(600MHz，Chloroform-d)δ8.74(d，J＝4.8Hz，2H)，8.72(d，J＝1.6Hz，2H)，8.65(d，J＝7.9Hz，2H)，7.92-7.83(m，2H)，7.59(d，J＝2.1Hz，1H)，7.36(td，J＝5.5，2.8Hz，2H)，7.16-7.09(m，1H)，6.57(q，J＝2.2Hz，1H)。
13 C NMR(151MHz，Chloroform-d)δ156.06，155.89，151.94，149.08，143.73，139.61，136.98，123.92，121.35，115.22，112.14，109.25。
HR-MS(ESI)calcd for C 19 H 14 N 3 O + [M+H]+300.1131 found 300.1125。
Example 38: preparation of Compound 43
34.4mg of compound 97 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution is layered, the water phase is usedEthyl acetate was extracted twice (5 ml×2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was 93% as determined by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 28.7mg of compound 43 (light oily liquid, 89% yield). The obtained compound 43 was subjected to hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.78-8.70(m，3H)，8.67(dd，J＝8.0，1.1Hz，1H)，8.45(d，J＝7.8Hz，1H)，7.95-7.83(m，3H)，7.75(t，J＝7.7Hz，1H)，7.52(dd，J＝8.3，6.5Hz，2H)，7.49-7.41(m，1H)，7.34(ddd，J＝7.5，4.8，1.2Hz，1H)，7.20(d，J＝7.6Hz，1H)，2.68(s，3H)。
13 C NMR(101MHz，Chloroform-d)δ157.91，156.34，156.24，155.81，155.65，150.30，149.08，138.73，137.06，136.90，128.94，128.93，127.38，123.79，123.39，121.43，119.10，118.83，118.41，24.68。
HR-MS(ESI)calcd for C 22 H 18 N 3 + [M+H] + 324.1495 found 324.1488。
example 39: preparation of Compound 54
41.5mg of compound 98 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase is then combined with saturated salineAfter washing and drying over anhydrous magnesium sulfate, the organic phase is concentrated and dibromomethane is added as an internal standard of nuclear magnetism, and the reaction yield is 97% through nuclear magnetism hydrogen spectrum determination. Purification by column chromatography gave 33.8mg of compound 54 (pale yellow oily liquid, 89% yield). The resulting compound 54 was taken for hydrogen, carbon and mass spectrometry detection as follows:
1 H NMR(400MHz，Chloroform-d)δ8.70(d，J＝4.8Hz，1H)，8.55-8.45(m，2H)，8.01(d，J＝1.6Hz，1H)，7.82(td，J＝7.7，1.8Hz，1H)，7.76-7.68(m，2H)，7.49(t，J＝7.4Hz，2H)，7.43(dd，J＝8.4，6.3Hz，1H)，7.31(dd，J＝7.5，4.8Hz，1H)，6.81(d，J＝12.6Hz，1H)，6.44(d，J＝12.7Hz，1H)，2.08-2.01(m，2H)，1.76(dt，J＝11.9，7.0Hz，2H)，1.64-1.57(m，2H)，1.54(s，3H)1.12(d，J＝4.1Hz，6H)。
13 C NMR(101MHz，Chloroform-d)δ156.93，156.47，155.96，149.04，148.90，138.76，136.87，135.64，133.24，131.83，129.19，129.01，128.85，126.88，123.63，121.47，120.40，116.67，39.37，34.99，32.33，28.46，21.22，19.35。
HR-MS(ESI)calcd for C 27 H 29 N 2 + [M+H] + 381.2325 found 381.2319。
example 40: preparation of Compound 60
36.3mg of compound 99 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed under a 30W blue light for 24 hours, and after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was diluted with 5mL of water and 10mL of ethyl acetate. After the reaction solution is layered, the water phase is used Ethyl acetate was extracted twice (5 ml×2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 95% by nuclear magnetic hydrogen spectrometry. Purification by column chromatography gave 30.0mg of compound 60 (pale yellow oily liquid, yield 88%). The obtained compound 60 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.55(dd，J＝4.9，1.7Hz，1H)，8.43(d，J＝8.1Hz，1H)，7.96(s，1H)，7.73(td，J＝7.8，1.8Hz，1H)，7.39-7.27(m，5H)，7.19(q，J＝4.6Hz，1H)，3.25(dtd，J＝9.9，6.9，3.5Hz，1H)，2.84(q，J＝5.0Hz，1H)，2.72(pd，J＝6.9，4.7Hz，1H)，2.02-1.87(m，2H)，1.83-1.71(m，1H)，1.47-1.36(m，1H)，1.05(dd，J＝7.1，2.8Hz，3H)，0.76(d，J＝6.9Hz，6H)。
13 C NMR(101MHz，Chloroform-d)δ159.37，151.76，150.69，148.90，140.55，136.90，136.14，128.69，128.24，128.05，127.49，123.30，121.23，119.96，45.76，32.04，29.33，28.42，21.78，21.63，19.21，18.62。
HR-MS(ESI)calcd for C 24 H 27 N 2 + [M+H] + 343.2169 found 343.2162。
example 41: preparation of Compound 65
53.9mg of Compound 100 (0.1 mmol,1 equiv.) are introduced into a 10ml Schlenk tube, [ Ir (ppy) 2 (bpy)]PF 6 (0.002 mmol), ammonium acetate (15.4 mg,0.2mmol,2 equiv.), co (dmgBF 2) 2.2H2O 6 (0.004 mmol), DABCO (16.8 mg,0.15mmol,1.5 equiv.) and scandium triflate (9.8 mg,0.02 mmol), were evacuated and replaced 3 times with nitrogen, and 1.0mL of anhydrous acetonitrile was added under the protection of nitrogen flow. The reaction tube was placed on a 30W blue light lamp for 24 hours, after the completion of the reaction, the Schlenk tube was opened, and the reaction solution was treated with 5mL of water and 10mL of ethyl acetateDiluting with ethyl acetate. After the reaction solution had been separated, the aqueous phase was extracted twice with ethyl acetate (5 mL. Times.2). The organic phase was then combined and washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated to give dibromomethane as an internal nuclear magnetic standard, and the reaction yield was determined to be 85% by nuclear magnetic hydrogen spectroscopy. Column chromatography separation and purification gave 42.5mg of compound 65 (white solid, 82% yield). The obtained compound 65 was taken for hydrogen spectrum, carbon spectrum and mass spectrum detection, and the results were as follows:
1 H NMR(400MHz，Chloroform-d)δ8.66(ddd，J＝4.8，1.9，0.9Hz，1H)，8.52(dt，J＝8.0，1.1Hz，1H)，8.29(s，1H)，7.82(td，J＝7.7，1.8Hz，1H)，7.62-7.56(m，2H)，7.50-7.44(m，2H)，7.44-7.39(m，1H)，7.31-7.26(m，1H)，5.41(dt，J＝3.5，1.8Hz，1H)，4.68-4.55(m，1H)，2.88-2.67(m，2H)，2.45-2.31(m，3H)，2.16-2.08(m，1H)，2.04(s，3H)，1.96-1.84(m，3H)，1.81-1.72(m，2H)，1.72-1.60(m，4H)，1.14(d，J＝2.7Hz，6H)，0.86(tdd，J＝9.9，4.4，2.1Hz，2H)。
13 C NMR(101MHz，Chlorofbrm-d)δ173.58，170.54，156.83，154.11，148.81，146.17，140.12，138.80，137.02，134.17，128.53，128.47，128.24，123.22，122.11，121.38，118.27，73.86，56.10，50.66，45.69，38.16，36.94，33.86，31.39，30.90，30.53，27.77，26.93，21.45，20.64，19.40，17.44。
HR-MS(ESI)calcd for C 35 H 39 N 2 O 2 + [M+H] + 519.3006 found 519.2997。
While the methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations and combinations of the methods and applications described herein can be made and applied within the spirit and scope of the invention. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included within the present invention.

Claims (8)

1. A method of synthesizing a compound of formula II comprising:
，
under the conditions of catalyst and illumination and acid or alkali addition, under the protection of inert gas, the compound shown in the formula I reacts with an ammonium source in a solvent, and is subjected to post-treatment to obtain the compound shown in the formula II; wherein,
the catalyst comprises a photosensitizer and a cobalt oxime complex;
R 1 selected from the group consisting of C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, substituted or unsubstituted C3-C10 heterocyclyl, substituted or unsubstituted C3-C10 cycloalkyl, and substituted or unsubstituted C3-C10 cycloalkenyl;
R 2 selected from the group consisting of C1-C10 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C6-C20 heteroaryl, and substituted or unsubstituted C3-C10 heterocyclyl;
R 3 Selected from the group consisting of a hydrogen atom, a C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C6-C20 heteroaryl group, and a substituted or unsubstituted C3-C10 heterocyclic group;
R 4 selected from the group consisting of a hydrogen atom, a C1-C10 alkyl group, an ester group, a substituted or unsubstituted C6-C20 aryl group, a carbonyl group, and a cyano group; or alternatively
R 1 、R 4 Together with the atoms to which they are attached form a substituted or unsubstituted C3-C10 carbocyclic ring, a substituted or unsubstituted C3-C10 heterocyclic ring, a substituted or unsubstituted C6-C20 heteroaryl group, a substituted or unsubstituted C6-C20 aryl group,
the ammonium source is at least one selected from ammonium bicarbonate, ammonium carbonate, ammonium carbamate, ammonium chloride, ammonium fluoroborate, ammonium fluoride, ammonium formate and ammonium acetate,
the alkali is at least one of sodium acetate and triethylene diamine;
the photosensitizer comprises at least one of the following structures:
，
the cobalt oxime complex comprises at least one of the following structures:
。
2. the method of claim 1, the acid comprising trifluoroacetic acid, acetic acid, p-toluenesulfonic acid, methanesulfonic acid, scandium triflate, and yttrium triflate; and/or the solvent comprises at least one of acetonitrile, dichloromethane, toluene, dioxane, dichloroethane and tetrahydrofuran.
3. The process according to claim 2, the acid being scandium triflate and/or the solvent being acetonitrile.
4. The method of claim 1, wherein the molar ratio of the compound of formula I to the ammonium source is 1:1 to 1:10; and/or the molar ratio of the acid to the compound shown in the formula I is 5:100-50:100; and/or the feeding mole ratio of the compound shown in the formula I to the alkali is 1:0.5-1:3; and/or the charging mole ratio of the photosensitizer to the compound shown in the formula I is 0.5:100-10:100; and/or the feeding mole ratio of the cobalt oxime compound to the compound shown in the formula I is 0.5:100-10:100; and/or the volume ratio of the amount of the substance of the compound shown in the formula I to the solvent is 0.01 mmol/1 mL-0.2 mmol/1 mL.
5. The method of claim 1, wherein the light has a wavelength of 420nm-475nm; and/or the reaction time is 12 h-36 h; and/or the temperature of the reaction is 10 ℃ to 40 ℃.
6. The method of claim 1, the post-processing comprising: diluting with water and ethyl acetate, extracting the water phase with ethyl acetate twice, mixing the extracted organic phases, washing with saturated sodium chloride, drying with anhydrous magnesium sulfate, and separating.
7. The method of claim 1, said R 1 Selected from methyl, phenyl, 4-tolyl, 4-methoxyphenyl, 2-pyridyl, 6-methyl-2-pyridyl, 3, 5-dimethylphenyl, indanyl, 3, 4-dihydro-2H-chromene, thiopyranyl or the following c, d, e, f structure:
；
the R is 2 Selected from the group consisting of methyl, phenyl, 4-tolyl, 2-pyridyl, propyl, 6-methyl-2-pyridyl, 2-furyl, 5-methyl-2-thienyl, 3, 5-dimethylphenyl, 4-tert-butylphenyl and 4-nitrophenyl;
the R is 3 Selected from the group consisting of a hydrogen atom, phenyl, methyl, 2-naphthyl, 4-chlorophenyl, N-methyl-2-pyrrolyl, 4-pyridyl, 3-thienyl, 2-thienyl, 4-methylphenyl, 4-t-butylphenyl, 4-phenylphenyl and 2-furyl;
the R is 4 Selected from the group consisting of a hydrogen atom, a phenyl group, an ester group, a methyl group, a 4-methoxyphenyl group, a carbonyl group, and a cyano group; or alternatively
R 1 、R 4 Together with the atoms to which they are attached, form a substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, substituted or unsubstituted cycloheptenyl, phenyl, 4-tolyl, 4-methoxyphenyl, substituted or unsubstituted pyridyl, 3, 5-dimethylphenyl, 1H-indenyl, 1, 2-dihydronaphthyl, 2H-chromene, thiopyranyl group.
8. Use of a photosensitizer and cobalt oxime complex for the preparation of a pyridine compound, said photosensitizer comprising at least one of the structures of the method of claim 1; the cobalt oxime complex comprising at least one of the structures in the method of claim 1.
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