CN110015983A - 1,2- dicarbapentaborane class compound and its synthetic method - Google Patents

1,2- dicarbapentaborane class compound and its synthetic method Download PDF

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CN110015983A
CN110015983A CN201910231645.9A CN201910231645A CN110015983A CN 110015983 A CN110015983 A CN 110015983A CN 201910231645 A CN201910231645 A CN 201910231645A CN 110015983 A CN110015983 A CN 110015983A
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phenyl
replace
benzyl
reaction
alpha
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姜雪峰
王明
代志洪
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East China Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/30—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms, not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/32—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D209/22—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals with an aralkyl radical attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses one kind completely new 1 as shown in formula (1), the synthetic method of 2- dicarbonyl compound, using alpha-alcohol ketone, sulphur reagent and alkyl bromide as reaction raw materials, under the action of alkali and additive, reaction obtains a series of new 1,2- dicarbonyl compound in a solvent.The present invention avoids the drawbacks of tradition is using unstable acyl chlorides synthesis 1-2 dicarbonyl compound by the way that under no metal catalyzed conditions, using sulphur reagent as sulphur source, a step constructs to obtain 1,2- dicarbapentaborane class compound；Synthetic method of the invention is simple, and raw material is cheap and easy to get, and substrate universality is wide, and yield (45%-86%) is preferable.

Description

1,2- dicarbapentaborane class compound and its synthetic method
Technical field
The invention belongs to organic compound synthesis and applied technical fields, are related to 1,2- dicarbapentaborane class compound and its synthesis Methods and applications.
Background technique
1,2- dicarbapentaborane class compound is a kind of very important compound, especially in natural products, drug molecule It is widely used, therefore, develops efficient, environmental protection, the synthesis 1 of step economy, the method for 2- dicarbapentaborane class compound seems outstanding It is important.
The method of 1,2- dicarbapentaborane class compound mainly passes through alpha-carbonyl acyl chlorides and is transformed.However, alpha-carbonyl acyl chlorides Preparation method be not used only the irritating reagent of pollution, and there are the disadvantages in the majority such as unstable, side reaction is more for own. Therefore, develop a kind of chemical stabilization, and 1, the 2- dicarbapentaborane reagent with wide spectrum purposes is of great significance.
Summary of the invention
In order to overcome the drawbacks described above of the prior art, the present invention innovatively proposes one kind without transition metal-catalyzed item Under part, directly by alpha-alcohol ketone, sulphur reagent and alkyl bromide multicomponent method efficient green building 1,2- dicarbapentaborane class The method of compound.Synthetic method of the invention is simple, and raw material is cheap and easy to get, and substrate universality is wide, yield (45%-86%) compared with It is good.
The invention proposes the synthetic methods of one kind 1,2- dicarbapentaborane class compound, in a solvent, shown in formula (1) Using alpha-alcohol ketone, sulphur reagent and alkyl bromide as reaction raw materials, under the action of alkali, additive, reaction is obtained such as formula (1) institute 1, the 2- dicarbapentaborane class compound shown.Shown in the reaction process following reaction formula (A):
Wherein,
Ar is phenyl, the alkyl-substituted phenyl of C1-C5, the phenyl of C1-C5 alkoxy substitution, the phenyl of halogen substitution, first Phenyl, the mesyl that phenyl, the hydroxyl that phenyl, the carbomethoxy of phenyl, cyano substitution that sulfuryl replaces replace replace replace Phenyl, furyl, benzofuranyl, indyl.
R is benzyl, the alkyl-substituted benzyl of C1-C5, the benzyl that nitro replaces, the benzyl of ester group substitution, halogen substitution Benzyl, C1-C5 alkyl, allyl and its derivative, propargyl, Alpha-Methyl phenethyl.
Preferably,
Phenyl, the cyanogen of Ar is phenyl, methyl substituted phenyl, methoxy-substituted phenyl, bromine replace phenyl, chlorine substitution Phenyl, the furyl, benzo furan that phenyl, the mesyl that phenyl, the hydroxyl of phenyl, carbomethoxy substitution that base replaces replace replace It mutters base, indyl.
R is benzyl, 4- methylbenzyl, 4- nitrobenzyl, 4- carbomethoxy benzyl, 4- luorobenzyl, ethyl, normal-butyl, allyl Base and its derivative, propargyl, Alpha-Methyl phenethyl.
In the present invention, the solvent be selected from water, acetonitrile, dioxane, toluene, dimethyl sulfoxide, n,N-Dimethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, cyclopentyl methyl ether (CPME), ether, One of t-butyl methyl ether, ethyl acetate, benzene, benzonitrile, carbon tetrachloride, carbon disulfide, methylene chloride, chloroform etc. or It is a variety of；It preferably, is the mixed solvent of water and cyclopentyl methyl ether.
In the present invention, the sulphur reagent is reaction sulphur source, selected from sulphur powder, vulcanized sodium, potassium sulfide, NaHS, sulphur hydrogenation One of potassium, sodium thiosulfate, thiocarbamide etc. are a variety of；It preferably, is sulphur powder.
In the present invention, the alkali is selected from potassium carbonate, sodium carbonate, lithium carbonate, saleratus, sodium bicarbonate, lithium bicarbonate, phosphorus Sour potassium, potassium hydrogen phosphate, potassium hydroxide, sodium hydroxide, triethylamine, diisopropyl ethyl amine, sodium formate, potassium formate, sodium acetate, vinegar In sour potassium, lithium hydroxide, lithium acetate, 1,8- diazabicylo, 11 carbon -7- alkene (DBU), 4-dimethylaminopyridine (DMAP) etc. It is one or more；It preferably, is saleratus.
In the present invention, the alpha-alcohol ketone, sulphur reagent, alkali molar ratio be 1: (1-5): (1-5)；Preferably, it is 1: 4: 2。
In the present invention, the additive is selected from tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, the tetrabutyl Ammonium fluoride, 4 bromide, tetramethyl ammonium chloride, tetramethyl-ammonium iodide, Methanaminium, N,N,N-trimethyl-, fluoride, tetraethylammonium bromide, tetrem Ammonium chloride, tetraethyl ammonium iodide, tetraethyl ammonium fluoride, 4-propyl bromide, 4-propyl ammonium chloride, tetrapropyl ammonium iodide, four One of propyl ammonium fluoride, 18- crown- 6,15- crown- 5 etc. are a variety of；It preferably, is tetrabutylammonium bromide.
In the present invention, the molar ratio of the alpha-alcohol ketone and additive is (1-10): 1；It preferably, is 5: 1.
In the present invention, the reaction preferably carries out under nitrogen protection.
In the present invention, when using shown in formula (A) using alpha-alcohol ketone, sulphur reagent and alkyl bromide as reaction raw materials, alkali, Under the action of additive, shown in reaction mechanism such as formula (B), firstly, the elicitation procedure of free radical occurs, elemental sulfur is in reaction system Middle generation free radical anion (S3 ·-), and this free radical anion captures the hydrogen at alpha-alcohol ketone 1a carbonyl ortho position, occurs freely The transmitting of base generates intermediate compound I, remaining S in subsequent intermediate compound I and system3 ·-It is coupled, generates intermediate II, intermediate Sulphur sulfide linkage heterolytic fission then occurs for hydrogen migration of the II Jing Guo intramolecular, dissociates sulphur anion HSS, obtained intermediate III isomerization For intermediate compound IV, double carbonyl thioester compound 2a of target are finally obtained by additional cylite capture.
In a specific embodiment: shown in the reaction process following reaction formula (A ').
Wherein,
The benzene of Ar group is phenyl, the alkyl-substituted phenyl of Cl-C5, Cl-C5 alkoxy replace phenyl, halogen substitution Phenyl, the mesyl that phenyl, the hydroxyl that phenyl, the carbomethoxy of phenyl, cyano substitution that base, methylsulfonyl replace replace replace take Phenyl, furyl, benzofuranyl, the indyl in generation.
R is benzyl, the alkyl-substituted benzyl of Cl-C5, the benzyl that nitro replaces, the benzyl of ester group substitution, halogen substitution Benzyl, C1-C5 alkyl, allyl and its derivative, propargyl, Alpha-Methyl phenethyl.
Preferably,
Phenyl, the cyanogen of Ar is phenyl, methyl substituted phenyl, methoxy-substituted phenyl, bromine replace phenyl, chlorine substitution Phenyl, the furyl, benzo furan that phenyl, the mesyl that phenyl, the hydroxyl of phenyl, carbomethoxy substitution that base replaces replace replace It mutters base, indyl.
R is benzyl, 4- methylbenzyl, 4- nitrobenzyl, 4- carbomethoxy benzyl, 4- luorobenzyl, ethyl, normal-butyl, allyl Base and its derivative, propargyl, Alpha-Methyl phenethyl.
The invention also provides 1, the 2- dicarbapentaborane class compound as shown in formula (1),
Wherein,
The benzene of Ar group is phenyl, the alkyl-substituted phenyl of C1-C5, C1-C5 alkoxy replace phenyl, halogen substitution Phenyl, the furyl, benzene that phenyl, the hydroxyl that phenyl, the carbomethoxy of phenyl, cyano substitution that base, methylsulfonyl replace replace replace And furyl, indyl.
R is benzyl, the alkyl-substituted benzyl of C1-C5, the benzyl that nitro replaces, the benzyl of ester group substitution, halogen substitution Benzyl, C1-C5 alkyl, allyl and its derivative, propargyl, Alpha-Methyl phenethyl.
Preferably,
Phenyl, the cyanogen of Ar is phenyl, methyl substituted phenyl, methoxy-substituted phenyl, bromine replace phenyl, chlorine substitution Phenyl, the furyl, benzo furan that phenyl, the mesyl that phenyl, the hydroxyl of phenyl, carbomethoxy substitution that base replaces replace replace It mutters base, indyl.
R is benzyl, 4- methylbenzyl, 4- nitrobenzyl, 4- carbomethoxy benzyl, 4- luorobenzyl, ethyl, normal-butyl, allyl Base and its derivative, propargyl, Alpha-Methyl phenethyl.
The invention also provides 1, the 2- dicarbapentaborane class chemical combination as shown in formula (1) being prepared as above-mentioned synthetic method Object.
The beneficial effects of the present invention are: the present invention innovatively proposes one kind under the conditions of without transition metal-catalyzed, One step directly by alpha-alcohol ketone, sulphur reagent and alkyl bromide multicomponent method efficient green building 1,2- dicarbapentaborane class The method of compound.Synthetic method of the invention is simple, and raw material is cheap and easy to get, and substrate universality is wide, yield (45%-86%) compared with It is good.
Specific embodiment
In conjunction with following specific embodiments, the present invention is described in further detail, and of the invention protects content not limit to In following embodiment.Without departing from the spirit and scope of the invention, those skilled in the art it is conceivable that variation and excellent Point is all included in the present invention, and using appended claims as protection scope.Implement process of the invention, condition, Reagent, experimental method etc. are among the general principles and common general knowledge in the art, this hair in addition to what is specifically mentioned below It is bright that there are no special restrictions to content.Data given by following embodiment include concrete operations and reaction condition and product.Product is pure Degree is identified by nuclear-magnetism.
In Examples 1 to 25, reaction temperature is 90 DEG C.
Embodiment 1
The synthesis of compound 2a:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent C PME (4mL), reaction system are heated to 90 DEG C of reactions 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2a (90%).1H NMR (400MHz, CDCl3) δ 8.14 (d, J=8.2Hz, 2H), 7.65 (t, J=7.4Hz, 1H), 7.49 (t, J=7.8Hz, 2H), 7.40-7.27 (m, 5H), 4.28 (s, 2H)13C NMR (100MHz, CDCl3) δ 191.9,185.7,136.3,134.8,131.5,130.6, 128.9,128.7,128.6,127.5,33.1.HRMS (EI) Calcd for C15H12O2S 256.0558, Found 256.0555.
Embodiment 2
The synthesis of compound 2a ':
Under nitrogen protection, by alpha-hydroxyacetophenone (3.0mmol), S8(12.0mmol, 4.0equiv), KHCO3 (6.0mmol, 2.0equiv), TBAB (0.6mmol, 20mol%) are added in the reaction tube for being placed with magneton, and nitrogen three is changed in evacuation Add H after secondary2O (60mmol, 20equiv) and solvent C PME (20mL), reaction system are heated to 90 DEG C and react 10 hours, contact plate inspection After survey alpha-hydroxyacetophenone is totally converted completely, bromic ether (6.0mmol, 2equiv) is added into system, the reaction was continued 2 hours Afterwards, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (30mL*3) extraction, anhydrous sodium sulfate is dry, mistake Filter, concentration, column chromatography for separation obtain yellow oil 2a ' (81%).1H NMR (400MHz, CDCl3) δ 8.16-8.08 (m, 2H), 7.68-7.62 (m, 1H), 7.54-7.47 (m, 2H), 3.06 (q, J=7.4Hz, 2H), 1.37 (t, J=7.4Hz, 3H) .13C NMR (100MHz, CDCl3) δ 193.0,186.4,134.8,131.6,130.7,128.8,23.3,14.2.HRMS (EI) Calcd for C10H10O2S 194.0402, Found 194.0405.
Embodiment 3
The synthesis of compound 2b:
Under nitrogen protection, by Alpha-hydroxy 4- methyl acetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, to be put It is equipped in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20 equiv) and solvent C PME (4mL), reactant System is heated to 90 DEG C and reacts 10 hours, and after contact plate detection alpha-hydroxyacetophenone is totally converted completely, benzyl bromine is added into system (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2b (72%).1H NMR (400 MHz, CDCl3) (s, the 3H) of δ 8.06 (d, J=8.3Hz, 2H), 7.41-7.27 (m, 7H), 4.28 (s, 2H), 2.4413C NMR (100MHz, CDCl3) δ 192.2,185.4,146.2,136.4,130.8,129.5,129.0,128.9,128.6, 127.5,33.2,21.8.HRMS (EI) Calcd for C16H14O2S 270.0715, Found 270.0710.
Embodiment 4
The synthesis of compound 2c:
Under nitrogen protection, by Alpha-hydroxy 3- methyl acetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, to be put It is equipped in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (180mg, 4 mmol, 20equiv) and solvent C PME (4mL), Reaction system is heated to 90 DEG C and reacts 10 hours, after contact plate detection alpha-hydroxyacetophenone is totally converted completely, adds into system Benzyl bromine (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds second Acetoacetic ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2c (82%).1H NMR (400MHz, CDCl3) δ 7.94 (d, J=8.9Hz, 2H), 7.47 (d, J=7.6Hz, 1H), 7.42-7.27 (m, 6H), 4.29 (s, 2H), 2.42 (s, 3H)13C NMR (100MHz, CDCl3) δ 192.2,186.1,138.7,136.4, 135.7,131.5,131.0,128.9,128.7,128.6,128.0,127.5,33.2,21.2.HRMS (EI) Calcd for C16H14O2S 270.0715.Found 270.0717.
Embodiment 5
The synthesis of compound 2d:
Under nitrogen protection, by Alpha-hydroxy 2- methyl acetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, to be put It is equipped in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20 equiv) and solvent C PME (4mL), reactant System is heated to 90 DEG C and reacts 10 hours, and after contact plate detection alpha-hydroxyacetophenone is totally converted completely, benzyl bromine is added into system (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2d (63%).1H NMR (400 MHz, CDCl3) δ 7.76 (d, J=8.0Hz, 1H), 7.51-7.45 (m, 1H), 7.40-7.28 (m, 7H), 4.28 (s, 2H), 2.53 (s, 3H)13C NMR (100MHz, CDCl3) δ 192.5,188.8,141.0,136.4,133.4,132.1, 132.0,130.9,129.0,128.7,127.6,125.6,33.3,21.2.HRMS (EI) Calcd for C16H14O2S 270.0715 Found 270.0718.
Embodiment 6
The synthesis of compound 2e:
Under nitrogen protection, by Alpha-hydroxy 4- methoxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, to be put It is equipped in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20 equiv) and solvent C PME (4mL), reactant System is heated to 90 DEG C and reacts 10 hours, and after contact plate detection alpha-hydroxyacetophenone is totally converted completely, benzyl bromine is added into system (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2e (61%).1H NMR (400 MHz, CDCl3) δ 8.18 (d, J=8.9Hz, 2H), 7.41-7.26 (m, 5H), 6.97 (d, J=8.9Hz, 2H), 4.26 (s, 2H), 3.88 (s, 3H)13C NMR (100MHz, CDCl3) δ 192.5,184.0,165.0,136.5,133.3,128.9, 128.6,127.4,124.3,114.2,55.5,33.1.HRMS (EI) Calcd for C16H14O3S 286.0664, Found 286.0667.
Embodiment 7
The synthesis of compound 2f:
Under nitrogen protection, by Alpha-hydroxy 4- chloro-acetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0 equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, is placed with magneton In reaction tube, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C Reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2f (74%).1H NMR (400MHz, CDCl3) (s, the 2H) of δ 8.11-8.05 (m, 2H), 7.48-7.42 (m, 2H), 7.36-7.22 (m, 5H), 4.2413C NMR (100MHz, CDCl3) δ 191.7,184.4,141.7,136.3,132.1,130.0,129.2,128.9,128.7,127.6, 33.3.HRMS(EI)Calcd for C15H11O2SCl 290.0168, Found 290.0172.
Embodiment 8
The synthesis of compound 2g:
Under nitrogen protection, by Alpha-hydroxy 3- chloro-acetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0 equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, is placed with magneton In reaction tube, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C Reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2g (76%).1H NMR (400MHz, CDCl3) δ 8.10 (t, J=1.8Hz, 1H), 8.03-7.98 (m, 1H), 7.59 (ddd, J=8.0,2.1,1.0Hz, 1H), 7.41 (t, J=7.9Hz, 1H), 7.36-7.24 (m, 5H), 4.24 (s, 2H)13C NMR (100MHz, CDCl3) δ 191.5, 184.4,136.2,135.1,134.7,133.2,130.5,130.1,128.9,128.9,128.7,127.7,33.4.HRMS (EI)Calcd for C15H11O2SCl 290.0168, Found 290.0166.
Embodiment 9
The synthesis of compound 2h:
Under nitrogen protection, by Alpha-hydroxy 4- bromoacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0 equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, is placed with magneton In reaction tube, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C Reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow oil 2h (65%).1H NMR (400MHz, CDCl3) (s, the 2H) of δ 8.04-7.97 (m, 2H), 7.66-7.59 (m, 2H), 7.38-7.23 (m, 5H), 4.2413C NMR (100MHz, CDCl3) δ 191.7,184.6,136.2,132.2,132.2,130.7,130.3,128.9,128.7,127.6, 33.3.HRMS(EI)Calcd for C15H11O2SBr 333.9663, Found 333.9665.
Embodiment 10
The synthesis of compound 2i:
Under nitrogen protection, by Alpha-hydroxy 4- cyano-acetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, to be put It is equipped in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20 equiv) and solvent DMF (4mL), reaction system It is heated to 90 DEG C to react 10 hours, after contact plate detection alpha-hydroxyacetophenone is totally converted completely, benzyl bromine is added into system (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2i (55%).1H NMR (400 MHz, CDCl3) δ 8.28-8.22 (m, 2H), 7.83-7.76 (m, 2H), 7.39-7.27 (m, 5H), 4.27 (s, 2H) .13C NMR (100MHz, CDCl3) δ 191.0,184.2,136.0,134.8,132.4,131.1,129.0,128.8,127.8, 117.8,117.6,33.4.HRMS (EI) Calcd for C16H11NO2S 281.0511, Found 281.0515.
Embodiment 11
The synthesis of compound 2j:
Under nitrogen protection, by Alpha-hydroxy furans ethyl ketone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, is placed with magneton In reaction tube, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C Reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow oil 2j (65%).1H NMR (400MHz, CDCl3) δ 7.80 (dd, J=3.7,0.6Hz, 1H), 7.75 (dd, J=1.6,0.6Hz, 1H), 7.32-7.18 (m, 5H), 6.58 (dd, J=3.7,1.7Hz, 1H), 4.15 (s, 2H)13C NMR (100MHz, CDCl3) δ 190.7,171.5,150.1, 147.7,136.3,128.9,128.7,127.6,126.1,113.3,33.2.HRMS (EI) Calcd for C13H10O3S 246.0351 Found 246.0350.
Embodiment 12
The synthesis of compound 2k:
Under nitrogen protection, by Alpha-hydroxy benzofuran ethyl ketone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, is placed with magneton In reaction tube, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C Reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2k (66%).1H NMR (400MHz, CDCl3) δ 8.16 (d, J=0.7Hz, 1H), 7.72 (d, J=7.9Hz, 1H), 7.56 (d, J=8.4Hz, 1H), 7.52- 7.46 (m, 1H), 7.34-7.20 (m, 6H), 4.20 (s, 2H)13C NMR (100MHz, CDCl3) δ 190.4,173.7, 156.7,147.5,136.2,130.1,129.0,128.7,127.6,127.0,124.4,124.2,122.1,112.6, 33.3.HRMS(EI)Calcd for C17H12O3S 296.0507, Found 296.0509.
Embodiment 13
The synthesis of compound 2l:
Under nitrogen protection, by Alpha-hydroxy N- benzylindole ethyl ketone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0 Equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to placement Have in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system adds Heat to 90 DEG C react 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, bromic ether is added into system (1.0mmol, 2equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds ethyl acetate (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2l (62%).1H NMR (400MHz, CDCl3) δ 8.56 (s, 1H), 8.46 (d, J=7.8Hz, 1H), 7.39-7.27 (m, 6H), 7.21-7.15 (m, 2H), 5.37 (s, 2H), 2.97 (d, J=7.4Hz, 2H), 1.34 (t, J=7.4Hz, 3H)13C NMR (100MHz, CDCl3) δ 194.6,178.2,139.9,136.8,135.2,129.1,128.3,127.7,127.0,124.3,123.6,122.9, 110.6,51.2,23.1,14.2.HRMS (EI) Calcd for C19H17NO2S 323.0980, Found 323.0983.
Embodiment 14
The synthesis of compound 2m:
Under nitrogen protection, by Alpha-hydroxy 4- methyl esters benzoylformaldoxime (0.5mmol), S8(64.2mg, 2.0mmol, 4.0 Equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to placement Have in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system adds Heat to 90 DEG C react 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2m (64%).1H NMR (400MHz, CDCl3) δ 8.21-8.17 (m, 2H), 8.16-8.12 (m, 2H), 7.39-7.27 (m, 5H), 4.28 (s, 2H), 3.96 (s, 3H)13C NMR (100MHz, CDCl3) δ 191.5,185.2,165.9,136.2,135.2,134.9,130.7, 129.8,129.0,128.8,127.7,52.6,33.4.HRMS (EI) Calcd for C17H14O4S 314.0613, Found 314.0614.
Embodiment 15
The synthesis of compound 2n:
Under nitrogen protection, by Alpha-hydroxy 4- mesyl acetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, to be put It is equipped in the reaction tube of magneton, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20 equiv) and solvent DMF (4mL), reaction system It is heated to 90 DEG C to react 10 hours, after contact plate detection alpha-hydroxyacetophenone is totally converted completely, benzyl bromine is added into system (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2n (75%).1H NMR (400 MHz, CDCl3) δ 8.30 (d, J=8.5Hz, 2H), 8.06 (d, J=8.5Hz, 2H), 7.39-7.24 (m, 5H), 4.27 (s, 2H), 3.07 (s, 3H)13C NMR (100MHz, CDCl3) δ 191.0,184.3,145.4,135.9,135.8,131.5, 128.9,128.7,127.7,127.7,44.1,33.4.HRMS (EI) Calcd for C16H14O4S2334.0334, Found 334.0336.
Embodiment 16
The synthesis of compound 2o:
Under nitrogen protection, by Alpha-hydroxy 4-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3(100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%), which is added to, is placed with magneton In reaction tube, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C Reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2o (45%).1H NMR (400MHz, CDCl3) δ 8.14-8.07 (m, 2H), 7.38-7.25 (m, 5H), 6.94-6.87 (m, 2H), 6.15 (s, 1H), 4.26 (s, 2H).13C NMR (100MHz, CDCl3) δ 192.7,184.3,161.9,136.5,133.8,129.0,128.7,127.6, 124.5,115.9,33.3.HRMS (EI) Calcd for C15H12O3S 272.0507, Found 272.0509.
Embodiment 17
The synthesis of compound 2p:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (180mg, 4mmol, 20equiv) and solvent C PME (4mL), reaction system is heated to 90 DEG C reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, n-butyl bromide is added into system (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow oil 2p (83%).1H NMR (400 MHz, CDCl3) δ 8.15-8.06 (m, 2H), 7.67-7.60 (m, 1H), 7.52-7.46 (m, 2H), 3.05 (t, J =7.4Hz, 2H), 1.70-1.63 (m, 2H), 1.51-1.40 (m, 2H), 0.95 (t, J=7.3Hz, 3H)13C NMR (100MHz, CDCl3) δ 193.0,186.4,134.7,131.6,130.7,128.8,31.1,28.5,22.0,13.5.HRMS (EI)Calcd for C12H14O2S 222.0715, Found 222.0713.
Embodiment 18
The synthesis of compound 2q:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent C PME (4mL), reaction system are heated to 90 DEG C of reactions 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add allyl bromide, bromoallylene (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow oil 2q (56%).1H NMR (400MHz, CDCl3) δ 8.15-8.06 (m, 2H), 7.68-7.59 (m, 1H), 7.48 (dd, J=11.0,4.7Hz, 2H), 5.86 (ddt, J =16.9,10.0,6.9Hz, 1H), 5.38-5.30 (m, 1H), 5.18 (dd, J=10.0,0.9Hz, 1H), 3.68 (dd, J= 7.0,0.9Hz, 2H)13C NMR (100MHz, CDCl3) δ 192.0,185.9,134.8,131.9,131.5,130.7, 128.7,118.8,31.6.HRMS (EI) Calcd for C11H10O2S 206.0402, Found 206.0399.
Embodiment 19
The synthesis of compound 2r:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C of reactions 10 Hour, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add dimethallyl bromide (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow oil 2r (66%).1H NMR(400 MHz, CDCl3) δ 8.15-8.09 (m, 2H), 7.67-7.62 (m, 1H), 7.53-7.46 (m, 2H), 5.33- 5.25 (m, 1H), 3.69 (d, J=7.9Hz, 2H), 1.74 (s, 6H)13C NMR (100MHz, CDCl3) δ 193.0,186.4,137.9,134.7, 131.7,130.7,128.8,117.6,27.2,25.6,17.9.HRMS (EI) Calcd for C13H14O2S 234.0715, Found 234.0719.
Embodiment 20
The synthesis of compound 2s:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C of reactions 10 Hour, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add propargyl bromide (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow oil 2s (71%).1H NMR (400MHz, CDCl3) δ 8.21-8.14 (m, 2H), 7.70-7.62 (m, 1H), 7.54-7.46 (m, 2H), 3.76 (d, J=2.7Hz, 2H), 2.23 (t, J=2.7Hz, 1H)13C NMR (100MHz, CDCl3) δ 190.9,184.7,135.1,131.4,130.9, 128.9,77.9,71.5,17.4.HRMS (EI) Calcd for C11H8O2S 204.0245, Found 204.0246.
Embodiment 21
The synthesis of compound 2t:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent DMF (4mL), reaction system are heated to 90 DEG C of reactions 10 Hour, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add methylphenethyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow oil 2t (68%).1H NMR(400 MHz, CDCl3) δ 8.12-8.05 (m, 2H), 7.65-7.59 (m, 1H), 7.50-7.43 (m, 2H), 7.43- 7.38 (m, 2H), 7.36-7.30 (m, 2H), 7.30-7.23 (m, 1H), 4.87 (q, J=7.2Hz, 1H), 1.76 (d, J=7.2Hz, 3H)13C NMR (100MHz, CDCl3) δ 191.8,186.1,141.8,134.7,131.7,130.7,128.7,128.6,127.6, 127.3,43.2,22.1.HRMS (EI) Calcd for C16H14O2S 270.0715, Found 270.0718.
Embodiment 22
The synthesis of compound 2u:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent C PME (4mL), reaction system are heated to 90 DEG C of reactions 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add 4- methyl benzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2u (84%).1H NMR (400MHz, CDCl3) δ 8.18-8.13 (m, 2H), 7.69-7.63 (m, 1H), 7.54-7.48 (m, 2H), 7.28 (d, J=8.0Hz, 2H), 7.15 (d, J=7.9Hz, 2H), 4.27 (s, 2H), 2.35 (s, 3H)13C NMR (100MHz, CDCl3) δ 192.1,185.9, 137.3,134.8,133.2,131.6,130.7,129.4,128.8,128.7,33.0,21.0.HRMS (EI) Calcd for C16H14O2S 270.0715, Found 270.0717.
Embodiment 23
The synthesis of compound 2v:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent C PME (4mL), reaction system are heated to 90 DEG C of reactions 10 Hour, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add 4- nitrobenzyl bromine (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2v (55%).1H NMR (400MHz, CDCl3) (s, the 2H) of δ 8.19-8.09 (m, 4H), 7.69-7.62 (m, 1H), 7.57-7.46 (m, 4H), 4.3013C NMR (100MHz, CDCl3) δ 191.2,185.0,147.2,144.3,135.1,131.3,130.7,129.8,128.8,123.8, 32.4.HRMS(ESI)Calcd for C15H11NNaO4S[M+Na]+324.0301 Found 324.0305.
Embodiment 24
The synthesis of compound 2w:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (180mg, 4mmol, 20equiv) and solvent C PME (4mL), reaction system is heated to 90 DEG C reaction 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add 4- carbomethoxy benzyl bromine (0.75mmol, 1.5equiv) drops to room temperature after the reaction was continued 2 hours, and water dilution is added into system, adds acetic acid second Ester (10mL*3) extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2w (77%).1H NMR (400MHz, CDCl3) δ 8.11 (d, J=7.8Hz, 2H), 7.98 (d, J=8.2Hz, 2H), 7.64 (t, J=7.4 Hz, 1H), 7.52-7.39 (m, 4H), 4.27 (s, 2H), 3.89 (s, 3H)13C NMR (100MHz, CDCl3) δ 191.6,185.4, 166.6,141.7,134.9,131.4,130.7,129.9,129.3,128.9,128.8,52.0,32.8.HRMS (EI) Calcd for C17H14O4S 314.0613, Found 314.0608.
Embodiment 25
The synthesis of compound 2x:
Under nitrogen protection, by alpha-hydroxyacetophenone (0.5mmol), S8(64.2mg, 2.0mmol, 4.0equiv), KHCO3 (100mg, 1.0mmol, 2.0equiv), TBAB (32.3mg, 0.1mmol, 20mol%) are added to the reaction tube for being placed with magneton In, evacuation changes nitrogen and adds H afterwards three times2O (4mmol, 20equiv) and solvent C PME (4mL), reaction system are heated to 90 DEG C of reactions 10 hours, contact plate detection alpha-hydroxyacetophenone be totally converted completely after, into system add 4- fluorobenzyl bromide (0.75mmol, 1.5equiv), after the reaction was continued 2 hours, room temperature is dropped to, water dilution is added into system, adds ethyl acetate (10mL*3) Extraction, anhydrous sodium sulfate dry, filter, and are concentrated, and column chromatography for separation obtains yellow solid 2x (67%).1H NMR (400MHz, CDCl3) δ 8.16as a yellow solid-8.11 (m, 2H), 7.68-7.62 (m, 1H), 7.53-7.46 (m, 2H), 7.37-7.31 (m, 2H), 7.04-6.97 (m, 2H), 4.24 (s, 2H)19F NMR (376MHz, CDCl3)δ-114.40.13C NMR (100MHz, CDCl3) δ 191.9,185.6,162.1 (d,1JC-F=246.5Hz), 134.9,132.3 (d,4JC-F= 3.3Hz), 131.5,130.7,130.6 (d,3JC-F=8.2Hz), 128.8,115.5 (d,2JC-F=21.6Hz), 32.4.HRMS (EI)Calcd for C15H11O2SF 274.0464, Found 274.0461.
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect Protect range.

Claims (10)

1. one kind 1, the synthetic method of 2- dicarbapentaborane class compound, which is characterized in that in a solvent, with alpha-alcohol ketone, sulphur reagent It is reaction raw materials with alkyl bromide, under the action of alkali, additive, reaction obtains 1, the 2- dicarbapentaborane class as shown in formula (1) Compound, shown in the reaction process following reaction formula (A):
Wherein, Ar is phenyl, the alkyl-substituted phenyl of C1-C5, the phenyl of C1-C5 alkoxy substitution, the phenyl of halogen substitution, first Phenyl, the mesyl that phenyl, the hydroxyl that phenyl, the carbomethoxy of phenyl, cyano substitution that sulfuryl replaces replace replace replace Phenyl, furyl, benzofuranyl, indyl；
The benzyl of R is benzyl, the benzyl of the alkyl-substituted benzyl of C1-C5, nitro substitution, ester group replace benzyl, halogen substitution, C1-C5 alkyl, allyl and its derivative, propargyl, Alpha-Methyl phenethyl.
2. synthetic method as described in claim 1, which is characterized in that Ar is phenyl, methyl substituted phenyl, methoxy substitution Phenyl, bromine replace phenyl, chlorine replace phenyl, cyano replace phenyl, carbomethoxy replace phenyl, hydroxyl replace benzene Phenyl, the furyl, benzofuranyl, indyl that base, mesyl replace；R be benzyl, 4- methylbenzyl, 4- nitrobenzyl, 4- carbomethoxy benzyl, 4- luorobenzyl, ethyl, normal-butyl, allyl and its derivative, propargyl, Alpha-Methyl phenethyl.
3. synthetic method as described in claim 1, which is characterized in that the temperature of the reaction is 50-120 DEG C；And/or institute The time for stating reaction is 6-15 hours.
4. synthetic method as described in claim 1, which is characterized in that the sulphur reagent is reaction sulphur source, selected from sulphur powder, vulcanization One of sodium, potassium sulfide, NaHS, potassium bisulfide, sodium thiosulfate, thiocarbamide are a variety of.
5. synthetic method as described in claim 1, which is characterized in that the alkali is selected from potassium carbonate, sodium carbonate, lithium carbonate, carbon Potassium hydrogen phthalate, sodium bicarbonate, lithium bicarbonate, potassium phosphate, potassium hydrogen phosphate, potassium hydroxide, sodium hydroxide, triethylamine, diisopropyl second Base amine, sodium formate, potassium formate, sodium acetate, potassium acetate, lithium hydroxide, lithium acetate, 1,8- diazabicylo, 11 carbon -7- alkene One of DBU, 4-dimethylaminopyridine DMAP or a variety of.
6. synthetic method as described in claim 1, which is characterized in that the additive is selected from tetrabutylammonium bromide, the tetrabutyl Ammonium chloride, tetrabutylammonium iodide, tetrabutyl ammonium fluoride, 4 bromide, tetramethyl ammonium chloride, tetramethyl-ammonium iodide, tetramethyl Base ammonium fluoride, tetraethylammonium bromide, etamon chloride, tetraethyl ammonium iodide, tetraethyl ammonium fluoride, 4-propyl bromide, four One of propyl ammonium chloride, tetrapropyl ammonium iodide, tetrapropyl ammonium fluoride, 18- crown- 6,15- crown- 5 are a variety of.
7. synthetic method as described in claim 1, which is characterized in that the alpha-alcohol ketone, sulphur reagent, alkali molar ratio be 1: (1-5):(1-5)；And/or the molar ratio of the alpha-alcohol ketone and the additive is (1-10): 1.
8. synthetic method as described in claim 1, which is characterized in that the solvent be selected from water, acetonitrile, dioxane, toluene, Dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, tetrahydrofuran, Isosorbide-5-Nitrae-dioxy six Ring, cyclopentyl methyl ether, ether, t-butyl methyl ether, ethyl acetate, benzene, benzonitrile, carbon tetrachloride, carbon disulfide, methylene chloride, One of chloroform is a variety of.
9.1,2- dicarbapentaborane class compounds, which is characterized in that shown in its structure such as formula (1),
Wherein, Ar is phenyl, the alkyl-substituted phenyl of C1-C5, the phenyl of C1-C5 alkoxy substitution, the phenyl of halogen substitution, first Phenyl, the mesyl that phenyl, the hydroxyl that phenyl, the carbomethoxy of phenyl, cyano substitution that sulfuryl replaces replace replace replace Phenyl, furyl, benzofuranyl, indyl；
The benzyl of R is benzyl, the benzyl of the alkyl-substituted benzyl of C1-C5, nitro substitution, ester group replace benzyl, halogen substitution, C1-C5 alkyl, allyl and its derivative, propargyl, Alpha-Methyl phenethyl.
10. 1,2- dicarbapentaborane class compound as claimed in claim 9, which is characterized in that Ar is phenyl, methyl substituted benzene The benzene that phenyl, the carbomethoxy that phenyl, the cyano of phenyl, chlorine substitution that base, methoxy-substituted phenyl, bromine replace replace replace Phenyl, the furyl, benzofuranyl, indyl of phenyl, mesyl substitution that base, hydroxyl replace；
R be benzyl, 4- methylbenzyl, 4- nitrobenzyl, 4- carbomethoxy benzyl, 4- luorobenzyl, ethyl, normal-butyl, allyl and Its derivative, propargyl, Alpha-Methyl phenethyl.
CN201910231645.9A 2019-03-26 2019-03-26 1,2- dicarbapentaborane class compound and its synthetic method Pending CN110015983A (en)

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Cited By (1)

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CN114437061A (en) * 2020-10-30 2022-05-06 陕西莱特光电材料股份有限公司 Preparation method of diketone compound and preparation method of imidazole derivative

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114437061A (en) * 2020-10-30 2022-05-06 陕西莱特光电材料股份有限公司 Preparation method of diketone compound and preparation method of imidazole derivative
CN114437061B (en) * 2020-10-30 2023-09-12 陕西莱特光电材料股份有限公司 Preparation method of diketone compound and preparation method of imidazole derivative

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Application publication date: 20190716