CN106831414A - The method of the adjacent alkenyl phenol derivatives of synthesis - Google Patents

The method of the adjacent alkenyl phenol derivatives of synthesis Download PDF

Info

Publication number
CN106831414A
CN106831414A CN201710055027.4A CN201710055027A CN106831414A CN 106831414 A CN106831414 A CN 106831414A CN 201710055027 A CN201710055027 A CN 201710055027A CN 106831414 A CN106831414 A CN 106831414A
Authority
CN
China
Prior art keywords
compound
formula
phenol derivatives
solvent
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710055027.4A
Other languages
Chinese (zh)
Inventor
周林
王亮
谢浩浩
张玉敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jianghan University
Original Assignee
Jianghan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jianghan University filed Critical Jianghan University
Priority to CN201710055027.4A priority Critical patent/CN106831414A/en
Publication of CN106831414A publication Critical patent/CN106831414A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof

Abstract

The invention discloses a kind of method for synthesizing adjacent alkenyl phenol derivatives, the synthetic method by Liv Ullmann C O coupling reactions, Olefination reaction, slough pyridine groups reaction and obtain adjacent alkenyl phenol derivatives.The method of the adjacent alkenyl phenol derivatives of synthesis of the present invention is by selecting different R1Group, obtains different phenol derivatives, you can obtain different types of adjacent alkenyl phenol derivatives.By cheap and easily-available phenol derivative raw material, the range of choice of raw material is expanded, and save cost.The product that the method for the present invention is obtained has abundant functional group, and reactable is strong.Work as R2When group selects specific group, o-hydroxy cinnamic acid derivative can also be obtained by further hydrolysis.Meanwhile, reactions steps of the present invention are simple, and reaction condition is gentle, it is to avoid use hazardous agents, easily operation, with very strong practicality.

Description

The method of the adjacent alkenyl phenol derivatives of synthesis
Technical field
The present invention relates to organic synthesis field, more particularly to a kind of method for synthesizing adjacent alkenyl phenol derivatives.
Background technology
Phenol derivatives is that a class has the compound of special hydroxyl, and is that many has the natural of important biomolecule activity The core texture of product and drug molecule.For example, all structures with phenol such as picric acid, salicylic acid, phenolphthalein.Phenol derivatives As a kind of Organic Chemicals, the chemical products such as novolak resin, bisphenol-A, lactams and intermediate are can be used to.In system The fields such as standby synthetic fibers, plastics, synthetic rubber, agricultural chemicals, spices, dyestuff play an important role.Importantly, absolutely mostly Number phenolic compound has special odor and certain toxicity, can be used for producing bactericide and preservative；Can in terms of medical treatment For surgical instruments and the excreta treatment of sterilizing.
Using the activity of phenolic hydroxyl group, can be reacted in hydroxyl institute by halo, oxidation, alkylation, acylation, carboxylated etc. Phenyl ring introduce a variety of substitution bases, to obtain various structures, the phenol derivatives that functional group is abundant.But synthesis The method of the special phenol derivatives with ortho position alkenyl group is fewer on phenyl ring.General utilization replaces water in the prior art Poplar aldehyde and phosphorus ylide carry out witting reactions, and alkenyl structures are introduced to the phenolic hydroxyl group ortho position of phenol derivatives.But, the party Method need to use substituted salicylic aldehydes as raw material, it is necessary to first to introducing substituted radical on salicylide, and reaction is complicated and to a certain degree On limit the diversity of product structure；And the dangerous reagent n-butyllithium of tool is used in course of reaction.At present, do not have One safe and simple method obtains the phenol compound that there is adjacent alkenyl to replace structure.
The content of the invention
In order to solve problem of the prior art, goal of the invention of the invention is to provide a kind of adjacent alkenyl phenol derivatives of synthesis Method, the method is safe and simple, and the compound structure that can synthesize enriches.
The technical scheme is as follows：
A kind of method for synthesizing adjacent alkenyl phenol derivatives, its step includes：
S1. the compound by structure as shown in formula (1) and compound of the structure as shown in formula (2) are in rhodium catalyst Under, mix with copper acetate, silver hexafluoroantimonate, 70~90 DEG C are heated in the second solvent carries out Olefination reaction, obtains structure Compound as shown in formula (3)：
S2. the compound by structure as shown in formula (3) sloughs pyridine groups and obtains adjacent alkenyl benzene of the structure as shown in formula (4) Amphyl：
Wherein, R1Alkyl, halogenated methyl, the alkoxy of C1-C4 selected from C1-C4, dimethylamino, lignocaine, C1-C4 Alkoxy carbonyl group, cyano group, halogen.
R2Alkoxy carbonyl group, diformamide base selected from C1-C4, benzenesulfonyl.
Preferably, R1Selected from methyl, methoxyl group, dimethylamino, trifluoromethyl, methoxycarbonyl group, cyano group, fluorine, chlorine, bromine, more Preferred R1It is trifluoromethyl, methoxycarbonyl group, dimethylamino, cyano group, fluorine.
The present invention controls the ortho position of position phenolic hydroxyl group on phenyl ring of oxyalkylene alkylation reaction using pyridine as homing device Carry out, therefore first pass through compound of the Liv Ullmann C-O coupling reactions composite structure as shown in formula (1).
The specific steps of compound of the above-mentioned composite structure as shown in formula (1), those skilled in the art may be referred to document (Yao,Jinzhong,Feng,Ruokun,Wu,Zaihong,Liu,Zhanxiang,Zhang,Yuhong, Adv.Syn.Catal., 2013,355,1517-1522.), it is also possible to select change of the other modes composite structure as shown in formula (1) Compound.Preferably, compound of the structure as shown in formula (1) is that compound by 2- bromopyridines, structure as shown in formula (5) carries out crow Germania C-O coupling reactions are obtained；
It is furthermore preferred that the Liv Ullmann C-O coupling reactions are under CuI, potassium phosphate, the catalytic action of pyridine carboxylic acid, In first solvent, 80~100 DEG C are reacted what is obtained.
First solvent is preferably DMSO (dimethyl sulfoxide (DMSO)).Compound as shown in formula (5) of 2- bromopyridines, structure, CuI, potassium phosphate, the mol ratio of pyridine carboxylic acid are 5:(5.5~10):(0.5~2):(7.5~12.5):(0.5~2.5), it is more excellent Elect 5 as:6:0.5:10:1.Reaction at 90 DEG C, with TLC (thin-layer chromatography chromatography) monitor reaction to completely after, reaction terminates A point liquid extraction is carried out with water and EA (ethyl acetate) afterwards, then organic phase washing (preferably using saturated common salt water washing), drying is (excellent Dried from anhydrous magnesium sulfate) after, carry out purifying the compound for obtaining structure as shown in formula (1) with silica gel column chromatography, purify Condition can be determined by experiment by those skilled in the art, and currently preferred mobile phase volume is than V (petroleum ether)：V (acetic acid Ethyl ester)=8:1.
Preferably, the rhodium catalyst is preferably [RhCp*Cl2]2.Second solvent is preferably DMF (N, N- dimethyl formyls Amine).Compound of the structure as shown in formula (1) is preferably 1 with the mol ratio of compound of the structure as shown in formula (2):(1.2~2), More preferably 1:1.5.The material on the basis of compound of the structure as shown in formula (1), the molar percentage of rhodium catalyst is 5mol%, the molar percentage of copper acetate is 20mol%, and the molar percentage of silver hexafluoroantimonate is 20mol%.Under this condition The Olefination reaction for carrying out, yield can reach more than 90%, and the oxyalkylene hydrocarbonylation group for introducing is in the neighbour of phenolic hydroxyl group Position, simultaneous reactions temperature is relatively low, and reaction is gentle, it is not easy to influence trifluoromethyl, methoxycarbonyl group, dimethylamino, the cyanogen on phenyl ring The sensitive groups such as base, fluorine.Reaction can be carried out under nitrogen protection, it is also possible to be carried out in atmosphere, and reaction condition is loose easily real It is existing.Reaction obtains compound of the structure as shown in formula (3) after terminating with silica gel column chromatography separating purification, and purification condition can be by this Art personnel be determined by experiment, and currently preferred mobile phase volume is than V (petroleum ether)：V (ethyl acetate)=(1~ 5):1。
Preferably, it is in the step S2, compound of the structure as shown in formula (3) is molten the 3rd with Methyl triflate In agent, after 1~3h of heating response at 100~120 DEG C, again by product in the 4th solvent after removing solvent, gold is added Belong to the alcoholic solution of sodium, continue that pyridine groups can be sloughed after 0.5~1h of heating response at 100~120 DEG C, obtain structure such as formula (4) the adjacent alkenyl phenol derivatives shown in.
The 3rd solvent in the step step S2 is preferably toluene, compound and fluoroform of the structure as shown in formula (3) The mol ratio of methylmesylate, preferably 1:(1~3), more preferably 1:2.It is excellent after 1~3h of heating response at 100~120 DEG C Elect as and 2h is reacted at 100 DEG C, then remove toluene and obtain solid, then by solid dissolving in the 4th solvent of such as ethanol, The ethanol solution of metallic sodium is slowly added dropwise, continues to be reacted 30 minutes at 100 DEG C.Compound of the structure as shown in formula (3) and gold The mol ratio for belonging to sodium is preferably 1:20.Reaction carries out a point liquid extraction with water and EA after terminating, then organic phase is dried (preferably with nothing Aqueous sodium persulfate is dried) after, carry out purifying the adjacent alkenyl phenol derivatives for obtaining structure as shown in formula (4) with silica gel column chromatography. Purification condition can be determined by experiment by those skilled in the art, and currently preferred mobile phase volume is than V (petroleum ether)：V (ethyl acetate)=(5~8):1.
A kind of method it is a further object to provide Olefination reaction is carried out on phenyl ring：By structure such as formula (1) Shown compound under rhodium catalyst, is mixed with compound of the structure as shown in formula (2) with copper acetate, silver hexafluoroantimonate Close, 70~90 DEG C are heated in the second solvent carries out oxyalkylene alkylation reaction, obtains compound of the structure as shown in formula (3)：
Wherein, R1Selected from the alkyl for C1-C4, the alkoxy of C1-C4, amino, the alkoxy carbonyl group of C1-C4, cyano group, halogen Element；
R2Alkoxy carbonyl group, diformamide base selected from C1-C4, benzenesulfonyl.
Shown in the reaction scheme such as formula (6) of the adjacent alkenyl phenol derivatives of present invention synthesis：
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
The method of the adjacent alkenyl phenol derivatives of synthesis of the present invention is by selecting different R1Group, obtains different benzene Amphyl, you can obtain different types of adjacent alkenyl phenol derivatives.By cheap and easily-available phenol derivative raw material, The range of choice of raw material is expanded, and saves cost.The product that the method for the present invention is obtained has abundant function Group, reactable is strong.Work as R2When group selects specific group, o-hydroxy cinnamic acid can also be obtained by further hydrolysis Derivative.Meanwhile, reactions steps of the present invention are simple, reaction condition is gentle, high income, it is to avoid use hazardous agents, easily behaviour Make, with very strong practicality.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with reaction scheme to of the invention real The mode of applying is described in further detail.
[RhCp*Cl2]2From Sa En chemical technologies (Shanghai) Co., Ltd., purity 98%；
AgSbF6From Sa En chemical technologies (Shanghai) Co., Ltd., purity 98%；
Cu(OAc)2From Shanghai Aladdin chemical reagent Co., Ltd, purity 99%；
Acrylate comes from Shanghai Aladdin chemical reagent Co., Ltd, purity 98%；
Other reagents are all from Chemical Reagent Co., Ltd., Sinopharm Group, analyze pure.
Embodiment 1
In the present embodiment：R1It is methyl；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-1 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is depressurized dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：92%.
1H NMR(400MHz,CDCl3) δ 8.20-8.15 (m, 1H), 7.85 (d, J=16.1Hz, 1H), 7.73-7.68 (m, 1H), 7.56 (d, J=8.0Hz, 1H), 7.04 (d, J=8.0Hz, 1H), 7.01-7.69 (m, 2H), 6.90 (s, 1H), 6.43 (d, J=16.1Hz, 1H), 4.20 (q, J=7.1Hz, 2H), 2.35 (s, 3H), 1.28 (t, J=7.1Hz, 3H)
Embodiment 2
In the present embodiment：R1It is methoxyl group；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-2 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, yellow liquid, yield：88%.
1H NMR(400MHz,CDCl3) δ 8.18 (dd, J=4.7,1.6Hz, 1H), 7.82 (d, J=16.1Hz, 1H), 7.72 (ddd, J=8.3,7.3,2.0Hz, 1H), 7.61 (d, J=8.8Hz, 1H), 7.03-6.97 (m, 2H), 6.79 (dd, J= 8.8,2.6Hz, 1H), 6.62 (d, J=2.5Hz, 1H), 6.36 (d, J=16.1Hz, 1H), 4.19 (d, J=7.1Hz, 2H), 3.79 (s, 3H), 1.28 (t, J=7.1Hz, 3H)
Embodiment 3
In the present embodiment：R1It is N, N- dimethyl；R2Ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-3 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, yellow solid, yield：85%.
Compound II-3 is after tested：
1H NMR(400MHz,CDCl3) δ 8.19 (d, J=5.0Hz, 1H), 7.76 (d, J=16.0Hz, 1H), 7.72- 7.65 (m, 1H), 7.55 (d, J=8.9Hz, 1H), 7.01-6.94 (m, 1H), 6.92 (d, J=8.3Hz, 1H), 6.56 (dd, J =8.9,2.4Hz, 1H), 6.33 (d, J=2.6Hz, 1H), 6.25 (d, J=16.0Hz, 1H), 4.17 (q, J=7.1Hz, 2H), 2.97 (s, 6H), 1.26 (t, J=7.1Hz, 3H)
13C NMR(100MHz,CDCl3)δ167.83,163.85,154.38,152.79,147.94,139.49, 139.26,129.12,118.42,115.15,114.05,111.28,109.43,104.94,59.98,40.11,14.37.
HRMS m/z:calcd for C18H21N2O3[M+H+]313.1547,found 313.1552.
Embodiment 4
In the present embodiment：R1It is chlorine；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-4 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, yellow solid, yield：79%.
1H NMR(400MHz,CDCl3) δ 8.18 (dd, J=4.7,1.6Hz, 1H), 7.83 (d, J=16.2Hz, 1H), 7.75 (ddd, J=8.3,7.3,2.0Hz, 1H), 7.59 (d, J=8.5Hz, 1H), 7.20 (dd, J=8.4,2.0Hz, 1H), 7.12 (d, J=2.1Hz, 1H), 7.08-7.00 (m, 2H), 6.45 (d, J=16.1Hz, 1H), 4.21 (d, J=7.1Hz, 2H), 1.29 (t, J=7.1Hz, 3H)
Embodiment 5
In the present embodiment：R1It is bromine；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-5 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, colourless liquid, yield：80%.
Compound II-5 is after tested：
1H NMR(400MHz,CDCl3) δ 8.18 (d, J=3.0Hz, 1H), 7.81 (d, J=16.2Hz, 1H), 7.77- 7.71 (m, 1H), 7.52 (d, J=8.4Hz, 1H), 7.35 (dd, J=5.8,4.4Hz, 1H), 7.29-7.25 (m, 1H), 7.08- (t, J=7.1Hz, the 3H) of 6.99 (m, 2H), 6.47 (d, J=16.1Hz, 1H), 4.21 (q, J=7.1Hz, 2H), 1.29
13C NMR(100MHz,CDCl3)δ166.74,162.85,153.29,147.82,139.90,137.89, 128.99,128.33,126.41,125.56,124.32,120.20,119.36,111.98,60.56,14.36,14.27.
HRMS m/z:calcd for C16H15BrNO3[M+H+]348.0230,found 348.0237.
Embodiment 6
In the present embodiment：R1It is trifluoromethyl；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-6 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, colourless liquid, yield：65%.
1H NMR(400MHz,CDCl3) δ 8.16 (d, J=3.8Hz, 1H), 7.87 (d, J=16.2Hz, 1H), 7.79- 7.73 (m, 2H), 7.46 (d, J=8.2Hz, 1H), 7.38 (s, 1H), 7.10-7.03 (m, 2H), 6.54 (d, J=16.2Hz, 1H), 4.23 (q, J=7.1Hz, 2H), 1.30 (t, J=7.1Hz, 3H)
Embodiment 7
In the present embodiment：R1It is ester group；R2Ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-7 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：75%.
Compound II-7 is after tested：
1H NMR(400MHz,CDCl3) δ 8.15 (d, J=3.5Hz, 1H), 7.90 (s, 1H), 7.88-7.85 (m, 1H), 7.78-7.71 (m, 3H), 7.03 (dd, J=5.1,4.5Hz, 2H), 6.55 (d, J=16.2Hz, 1H), 4.36 (q, J= 7.1Hz, 2H), 4.22 (q, J=7.1Hz, 2H), 1.36 (t, J=7.1Hz, 3H), 1.29 (t, J=7.1Hz, 3H)
13C NMR(100MHz,CDCl3)δ166.54,165.45,163.13,152.69,147.77,139.83, 137.87,132.93,131.67,127.90,125.93,123.62,121.84,119.13,111.88,61.33,60.65, 14.29,14.26.IRν:1712,1634,1567,1465,1366,1237,1193,987,818,769,698.
HRMS m/z:calcd for C19H20NO5[M+H+]342.1336,found 342.1344.
Embodiment 8
In the present embodiment：R1It is cyano group；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-8 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, colourless liquid, yield：70%.
Compound II-8 is after tested：
1H NMR(400MHz,CDCl3) δ 8.16 (dd, J=4.9,1.2Hz, 1H), 7.86 (d, J=16.2Hz, 1H), 7.79 (ddd, J=8.2,7.3,2.0Hz, 1H), 7.74 (d, J=8.1Hz, 1H), 7.48 (dd, J=8.1,1.2Hz, 1H), 7.43 (d, J=1.5Hz, 1H), 7.12-7.06 (m, 2H), 6.55 (d, J=16.2Hz, 1H), 4.24 (q, J=7.1Hz, 2H), 1.30 (t, J=7.1Hz, 3H)
13C NMR(100MHz,CDCl3)δ166.25,162.40,152.78,147.68,140.19,136.99, 132.02,128.71,128.12,126.01,122.91,119.80,117.87,113.98,112.23,60.87,14.23.
HRMS m/z:calcd for C17H15N2O3[M+H+]295.1077,found 295.1085.
Embodiment 9
In the present embodiment：R1It is methyl；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-9 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：92%.
1H NMR(400MHz,CDCl3) δ 8.10 (d, J=3.6Hz, 1H), 7.78 (d, J=16.1Hz, 1H), 7.71- 7.66 (m, 1H), 7.53 (d, J=7.2Hz, 1H), 7.30 (d, J=7.1Hz, 1H), 7.18 (t, J=7.6Hz, 1H), 6.95 (dd, J=7.6,4.1Hz, 2H), 6.42 (d, J=16.1Hz, 1H), 4.18 (q, J=7.1Hz, 2H), 2.10 (s, 3H), 1.26 (t, J=7.1Hz, 3H)
Embodiment 10
In the present embodiment：R1It is methoxyl group；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-10 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, yellow solid, yield：90%.
1H NMR(400MHz,CDCl3) δ 8.09 (d, J=3.2Hz, 1H), 7.84 (d, J=16.1Hz, 1H), 7.73- 7.63 (m, 1H), 7.28 (dd, J=8.0,1.3Hz, 1H), 7.21 (t, J=8.0Hz, 1H), 7.01 (dd, J=12.8, 4.8Hz, 2H), 6.95 (dd, J=6.9,5.3Hz, 1H), 6.46 (d, J=16.1Hz, 1H), 4.19 (q, J=7.1Hz, 2H), 3.71 (s, 3H), 1.27 (t, J=7.1Hz, 3H)
Embodiment 11
In the present embodiment：R1It is fluorine；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-11 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, yellow solid, yield：73%.
1H NMR(400MHz,CDCl3) δ 8.09 (dd, J=5.0,1.2Hz, 1H), 7.82 (d, J=16.2Hz, 1H), 7.73 (ddd, J=8.3,7.2,2.0Hz, 1H), 7.46 (d, J=6.4Hz, 1H), 7.25-7.16 (m, 2H), 7.12-7.05 (m, 1H), 7.01 (ddd, J=7.2,5.0,0.9Hz, 1H), 6.49 (d, J=16.1Hz, 1H), 4.21 (q, J=7.1Hz, 2H), 1.29 (t, J=7.1Hz, 3H)
Embodiment 12
In the present embodiment：R1It is chlorine；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-12 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：78%.
1H NMR(400MHz,CDCl3) δ 8.08 (d, J=4.1Hz, 1H), 7.81-7.69 (m, 2H), 7.59 (d, J= 7.3Hz, 1H), 7.48 (d, J=8.0Hz, 1H), 7.22 (t, J=7.9Hz, 1H), 7.06 (d, J=8.3Hz, 1H), 7.01- (t, J=7.1Hz, the 3H) of 6.96 (m, 1H), 6.45 (d, J=16.1Hz, 1H), 4.19 (q, J=7.1Hz, 2H), 1.27
Embodiment 13
In the present embodiment：R1It is methoxyl group；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-13 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：62%.
1H NMR(400MHz,CDCl3):δ 8.15 (d, J=4.0Hz, 1H), 7.80 (d, J=16.4Hz, 1H), 7.70- 7.65 (m, 1H), 7.14 (d, J=2.4Hz, 1H), 7.05 (d, J=9.2Hz, 1H), 6.97-6.93 (m, 3H), 6.44 (d, J= 16.0Hz, 1H), 4.21 (q, J=7.1Hz, 2H), 3.83 (s, 3H), 1.28 (t, J=7.1Hz, 3H)
Embodiment 14
In the present embodiment：R1It is dimethyl；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-14 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：87%.
Compound II-14 is after tested：
1H NMR(400MHz,CDCl3) δ 8.16 (dd, J=4.9,1.6Hz, 1H), 7.80 (d, J=16.1Hz, 1H), 7.69 (ddd, J=8.4,7.3,2.0Hz, 1H), 7.43 (s, 1H), 6.99-6.94 (m, 2H), 6.88 (s, 1H), 6.42 (d, J =16.1Hz, 1H), 4.19 (q, J=7.1Hz, 2H), 2.26 (d, J=5.0Hz, 6H), 1.27 (t, J=7.1Hz, 3H)
13C NMR(100MHz,CDCl3)δ167.18,163.81,150.75,147.80,140.79,139.52, 138.98,133.71,128.81,124.75,123.57,118.48,118.45,111.47,60.31,20.06,19.30, 14.29.
HRMS m/z:calcd for C18H20NO3[M+H+]298.1438,found 298.1445.
Embodiment 15
In the present embodiment：R1It is dimethyl；R2It is ethyoxyl.
Step：In 10mL reaction bulbs, addition compound I-15 (0.3mmol), ethyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：85%.
1H NMR(400MHz,CDCl3) δ 8.10 (d, J=3.8Hz, 1H), 7.74 (d, J=16.1Hz, 1H), 7.70- 7.65 (m, 1H), 7.32 (s, 1H), 7.11 (s, 1H), 6.97-6.91 (m, 2H), 6.40 (d, J=16.1Hz, 1H), 4.17 (q, J=7.1Hz, 2H), 2.34 (s, 3H), 2.06 (s, 3H), 1.26 (t, J=7.1Hz, 3H)
Embodiment 16
In the present embodiment：R1It is methyl；R2It is methoxyl group.
Step：In 10mL reaction bulbs, addition compound I-16 (0.3mmol), methyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, i.e., Obtain pure product, white solid, yield：85%.
Compound II-16 is after tested：
1H NMR(400MHz,CDCl3) δ 8.18 (ddd, J=5.0,2.0,0.7Hz, 1H), 7.85 (d, J=16.1Hz, 1H), 7.71 (ddd, J=8.3,7.2,2.0Hz, 1H), 7.56 (d, J=8.0Hz, 1H), 7.06-7.02 (m, 1H), 7.00 (ddd, J=7.2,5.0,0.9Hz, 1H), 6.97 (dt, J=8.3,0.8Hz, 1H), 6.92-6.88 (m, 1H), 6.44 (d, J= 16.1Hz,1H),3.74(s,3H),2.35(s,3H).
13C NMR(100MHz,CDCl3)δ167.56,163.51,152.86,147.86,142.22,139.63, 139.18,127.93,126.27,124.53,122.88,118.73,118.25,111.70,51.58,21.52.
HRMS m/z:calcd for C16H16NO3[M+H+]270.1125,found 270.1123.
Embodiment 17
In the present embodiment：R1It is methyl；R2It is tert-butoxy.
Step：In 10mL reaction bulbs, addition compound I-17 (0.3mmol), tert-butyl acrylate (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=3:1 mixed solvent, i.e., Obtain pure product, white solid, yield：84%.
Compound II-17 is after tested：
1H NMR(400MHz,CDCl3) δ 8.19-8.15 (m, 1H), 7.75 (d, J=16.1Hz, 1H), 7.70 (ddd, J= 8.3,7.2,2.0Hz, 1H), 7.56 (d, J=8.0Hz, 1H), 7.04-6.97 (m, 2H), 6.96 (d, J=8.3Hz, 1H), (s, the 9H) of 6.90 (s, 1H), 6.35 (d, J=16.1Hz, 1H), 2.35 (s, 3H), 1.47
Embodiment 18
In the present embodiment：R1It is methyl；R2It is N, N- dimethyl.
Step：In 10mL reaction bulbs, compound I-18 (0.3mmol), acrylamide (0.45mmol), [RhCp* are added Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is anti-at being placed in 80 DEG C Should, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：It is cooled to room temperature, pressurization concentration.Slightly Product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=1:1 mixed solvent, that is, obtain Pure product, white solid, yield：77%.
Compound II-18 is after tested：
1H NMR(400MHz,CDCl3) δ 8.15 (dd, J=5.0,1.5Hz, 1H), 7.73 (d, J=15.6Hz, 1H), 7.67 (ddd, J=8.3,7.2,2.0Hz, 1H), 7.54 (d, J=8.0Hz, 1H), 7.04 (d, J=7.9Hz, 1H), 6.97 (ddd, J=7.2,5.0,0.8Hz, 1H), 6.92 (s, 2H), 6.89 (d, J=7.4Hz, 1H), 3.06 (s, 3H), 3.00 (s, 3H),2.35(s,3H).
13C NMR(100MHz,CDCl3)δ166.92,163.58,152.33,147.75,141.23,139.60, 136.71,128.48,126.31,125.65,123.26,118.58,118.48,111.30,37.35,35.83,21.41.
HRMS m/z:calcd for C17H19N2O2[M+H+]283.1441,found 283.1439.
Embodiment 19
In the present embodiment：R1It is methyl；R2It is benzene sulfuryl.
Step：In 10mL reaction bulbs, addition compound I-19 (0.3mmol), phenyl vinyl sulfone (0.45mmol), [RhCp*Cl2]2(5mol%), AgSbF6(20mol%), Cu (OAc)2(20mol%) and DMF (1mL), mixture is placed in 80 Reacted at DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Carry out post processing purification：Room temperature is cooled to, is pressurizeed dense Contracting.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=1:1 mixed solvent, i.e., Obtain pure product, colourless liquid, yield：68%.
Compound II-19 is after tested：
1H NMR(400MHz,CDCl3) δ 8.13 (dd, J=4.9,1.9Hz, 1H), 7.81 (d, J=7.7Hz, 2H), 7.79 (d, J=6.3Hz, 1H), 7.72 (dd, J=1.8,0.9Hz, 1H), 7.58-7.54 (m, 1H), 7.46 (dd, J=15.7, 8.0Hz, 3H), 7.05-7.00 (m, 2H), 6.97 (d, J=8.3Hz, 1H), 6.90 (s, 1H), 6.87 (d, J=15.5Hz, 1H),2.34(s,3H).
13C NMR(100MHz,CDCl3)δ163.11,153.31,147.80,143.40,140.83,139.84, 137.46,133.14,129.20,128.94,127.69,127.56,126.26,122.79,122.51,119.07,111.91, 21.60.
HRMS m/z:calcd for C20H18NO3S[M+H+]352.1002,found 352.0997.
Embodiment 20
In the present embodiment：R1It is methyl, R2It is ethyoxyl.
Step：Under nitrogen protection, addition compound II-1 (1.0mmol) in 50mL reaction bulbs, toluene (25mL), MeOTf (Methyl triflate) (2.0mmol), mixture is placed in 100 DEG C and reacts 2 hours.After being cooled to room temperature, toluene is removed Obtain white solid.White solid is dissolved in ethanol (10mL), and is slowly added dropwise the ethanol solution of sodium (20mmol) thereto (20mL) reacts 30 minutes at 100 DEG C.Carry out post processing purification：Room temperature is cooled to, H is added2O (50mL), uses ethyl acetate Extraction (3 × 30mL), anhydrous sodium sulfate drying is used after merging organic phase.Crude product silica gel column chromatography separating purification, mobile phase It is V (petroleum ether)：V (ethyl acetate)=5:1 mixed solvent, obtains final product pure product III-1.
1H NMR(400MHz,CDCl3) δ 7.95 (d, J=16.4Hz, 1H), 7.36 (d, J=8.0Hz, 1H), 6.73 (d, J =6.8Hz, 1H), 6.65 (s, 1H), 6.57 (d, J=16.4Hz, 1H), 6.06 (s, 1H), 4.26 (q, J=7.2Hz, 2H), 2.31 (s, 3H), 1.35 (t, J=7.2Hz, 3H)
Embodiment 21
In the present embodiment：R1 is methyl, and R2 is ethyoxyl.
Step：Under nitrogen protection, addition compound II-9 (1.0mmol) in 50mL reaction bulbs, toluene (25mL), MeOTf (2.0mmol), mixture is placed in 100 DEG C and reacts 2 hours.After being cooled to room temperature, remove toluene and obtain white solid.Will White solid is dissolved in ethanol (10mL), and it is anti-at 100 DEG C to be slowly added dropwise the ethanol solution of sodium (20mmol) (20mL) thereto Answer 30 minutes.Carry out post processing purification：Room temperature is cooled to, H is added2O (50mL), is extracted with ethyl acetate (3 × 30mL), merges Anhydrous sodium sulfate drying is used after organic phase.Crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (acetic acid Ethyl ester)=8:1 mixed solvent, obtains final product pure product III-2.
1H NMR(400MHz,CDCl3):δ=8.16 (d, J=16.1Hz, 1H), 7.35 (dd, J=7.7,1.8Hz, 1H), 7.16-7.14 (m, 1H), 6.84 (t, J=7.7Hz, 1H), 6.54 (d, J=16.1Hz, 1H), 6.21 (s, 1H), 4.27 (q, J =7.1Hz, 2H), 2.30 (s, 3H), 1.34 (t, J=7.1Hz, 3H)
Embodiment 22
In the present embodiment：R1It is methyl.
Step：In 25mL reaction bulbs, 2- bromopyridines (5mmol), m-methyl phenol (6mmol), pyridine -2- formic acid are added (1mmol), K3PO4(10mmol), CuI (0.5mmol) and DMSO (10mL), mixture react at being placed in 90 DEG C, and TLC is (with thin Chromatography is analysed layer by layer) detection extremely reaction is completely.Carry out post processing purification：Room temperature is cooled to, H is added2O(30mL).Use acetic acid second Ester (40mL) is extracted 3 times, merges organic phase, is washed with saturated aqueous common salt (100mL).Dried with anhydrous magnesium sulfate, filtering, decompression Concentration, crude product silica gel column chromatography separating purification, mobile phase is V (petroleum ether)：V (ethyl acetate)=8:1 mixed solvent, Obtain the I-1 in embodiment 1.
It should be noted that：The synthetic method of the adjacent alkenyl phenol derivatives that above-described embodiment is provided, only with above-mentioned synthesis Adjacent alkenyl phenol derivatives be illustrated, in actual applications, can as needed select Material synthesis other adjacent Alkenyl phenol derivatives, its specific synthetic method is similar to specific embodiment of the invention, and those skilled in the art can basis General knowledge carries out the adjustment of reaction condition, repeats no more here.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.

Claims (8)

1. a kind of method for synthesizing adjacent alkenyl phenol derivatives, it is characterised in that：Its step includes：
S1. the compound by structure as shown in formula (1) and compound of the structure as shown in formula (2) be under rhodium catalyst, with Copper acetate, silver hexafluoroantimonate mixing, 70~90 DEG C are heated in the second solvent carries out Olefination reaction, obtains structure such as formula (3) compound shown in：
S2. the compound by structure as shown in formula (3) sloughs pyridine groups and obtains adjacent alkenyl phenol of the structure as shown in formula (4) and spreads out It is biological：
Wherein, R1Alkyl, halogenated methyl, the alkoxy of C1-C4 selected from C1-C4, dimethylamino, lignocaine, the alkane of C1-C4 Oxygen carbonyl, cyano group, halogen；
R2Alkoxy carbonyl group, diformamide base selected from C1-C4, benzenesulfonyl.
2. the method for synthesizing adjacent alkenyl phenol derivatives according to claim 1, it is characterised in that：The structure such as formula (1) Shown compound is that compound by 2- bromopyridines, structure as shown in formula (5) carries out Liv Ullmann C-O coupling reactions and obtains；
3. the method for synthesizing adjacent alkenyl phenol derivatives according to claim 2, it is characterised in that：The Liv Ullmann C-O idols Connection reaction is that under CuI, potassium phosphate, the catalytic action of pyridine carboxylic acid, in the first solvent, 80~100 DEG C are reacted what is obtained.
4. the method for synthesizing adjacent alkenyl phenol derivatives according to claim 1, it is characterised in that：The rhodium catalyst is [RhCp*Cl2]2。
5. the method for synthesizing adjacent alkenyl phenol derivatives according to claim 1, it is characterised in that：The rhodium catalyst rubs Your percentage is 5mol%, and the molar percentage of copper acetate is 20mol%, and the molar percentage of silver hexafluoroantimonate is 20mol%.
6. the method for synthesizing adjacent alkenyl phenol derivatives according to claim 1, it is characterised in that：In the step S2, will Compound of the structure as shown in formula (3) and Methyl triflate in the 3rd solvent, at 100~120 DEG C heating response 1~ After 3h, again by product in the 4th solvent after removing solvent, the alcoholic solution of metallic sodium is added, continued at 100~120 DEG C Pyridine groups can be sloughed after 0.5~1h of heating response, obtain adjacent alkenyl phenol derivatives of the structure as shown in formula (4).
7. any one in the method for the adjacent alkenyl phenol derivatives of synthesis according to claims 1 to 6, it is characterised in that：Institute The first solvent is stated for DMSO, second solvent is DMF, the 3rd solvent is toluene, and the 4th solvent is ethanol.
8. a kind of method that Olefination reaction is carried out on phenyl ring, it is characterised in that：By compound of the structure as shown in formula (1) and knot Compound of the structure as shown in formula (2) mixes under rhodium catalyst with copper acetate, silver hexafluoroantimonate, adds in the second solvent Hot to 70~90 DEG C carry out Olefination reaction, obtain compound of the structure as shown in formula (3)：
Wherein, R1Selected from the alkyl for C1-C4, the alkoxy of C1-C4, amino, the alkoxy carbonyl group of C1-C4, cyano group, halogen；
R2Alkoxy carbonyl group, diformamide base selected from C1-C4, benzenesulfonyl.
CN201710055027.4A 2017-01-24 2017-01-24 The method of the adjacent alkenyl phenol derivatives of synthesis Pending CN106831414A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710055027.4A CN106831414A (en) 2017-01-24 2017-01-24 The method of the adjacent alkenyl phenol derivatives of synthesis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710055027.4A CN106831414A (en) 2017-01-24 2017-01-24 The method of the adjacent alkenyl phenol derivatives of synthesis

Publications (1)

Publication Number Publication Date
CN106831414A true CN106831414A (en) 2017-06-13

Family

ID=59119685

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710055027.4A Pending CN106831414A (en) 2017-01-24 2017-01-24 The method of the adjacent alkenyl phenol derivatives of synthesis

Country Status (1)

Country Link
CN (1) CN106831414A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109627163A (en) * 2018-12-18 2019-04-16 浙江工业大学 The directly Olefination method in phenol compound ortho position and Olefination phenol compound
CN111270260A (en) * 2020-02-09 2020-06-12 浙江师范大学 Method for alkenylating ortho-position of aromatic amide compound

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
BECHTOLDT, ALEXANDER等: "Ruthenium Oxidase Catalysis for Site-Selective C-H Alkenylations with Ambient O2 as the Sole Oxidant", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 *
BORAH, ARUN JYOTI等: "RhIII-Catalyzed Olefination of 2-Aryloxy-pyridines Using 2-Pyridyloxyl as the Removable Directing Group", 《EUROPEAN JOURNAL OF ORGANIC CHEMISTRY》 *
FABRY, DAVID C.等: "Merging Visible Light Photoredox Catalysis with Metal Catalyzed C-H Activations: On the Role of Oxygen and Superoxide Ions as Oxidants", 《ACCOUNTS OF CHEMICAL RESEARCH》 *
LIU, BIN等: "Palladium-Catalyzed Oxidative Olefination of Phenols Bearing Removable Directing Groups under Molecular Oxygen", 《JOURNAL OF ORGANIC CHEMISTRY》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109627163A (en) * 2018-12-18 2019-04-16 浙江工业大学 The directly Olefination method in phenol compound ortho position and Olefination phenol compound
CN109627163B (en) * 2018-12-18 2021-03-09 浙江工业大学 Method for directly olefination of ortho-position of phenol compound and olefination of phenol compound
CN111270260A (en) * 2020-02-09 2020-06-12 浙江师范大学 Method for alkenylating ortho-position of aromatic amide compound
CN111270260B (en) * 2020-02-09 2021-05-25 浙江师范大学 Method for alkenylating ortho-position of aromatic amide compound

Similar Documents

Publication Publication Date Title
Murali et al. Decoding directing groups and their pivotal role in C− H activation
CN106928201B (en) The method for synthesizing 2- vinyl indole derivatives
CN109311813B (en) Palladium-catalyzed meta-C-H functionalized universal ligands
CN102603660B (en) Preparation method of 1H-1,2,3-triazole compound
Liu et al. Application of primary halogenated hydrocarbons for the synthesis of 3-aryl and 3-alkyl indolizines
Rudzki et al. Selective copper-or silver-catalyzed decarboxylative deuteration of aromatic carboxylic acids
Wang et al. A Catalyst‐Free Minisci‐Type Reaction: the C–H Alkylation of Quinoxalinones with Sodium Alkylsulfinates and Phenyliodine (III) Dicarboxylates
CN112375068B (en) Terminal alkenyl indole derivative and preparation method thereof
Yu et al. TBHP/CoCl2‐Mediated Intramolecular Oxidative Cyclization of N‐(2‐Formylphenyl) amides: An Approach to the Construction of 4H‐3, 1‐Benzoxazin‐4‐ones
Faggyas et al. Multibond forming tandem reactions of anilines via stable aryl diazonium salts: one-pot synthesis of 3, 4-dihydroquinolin-2-ones
CN106831414A (en) The method of the adjacent alkenyl phenol derivatives of synthesis
CN110204487A (en) A kind of synthetic method of quinoline
Gan et al. Convenient chlorination of some special aromatic compounds using N-chlorosuccinimide
CN109627163B (en) Method for directly olefination of ortho-position of phenol compound and olefination of phenol compound
Khan et al. Chroman‐4‐one‐Based Amino Bidentate Ligand: An Efficient Ligand for Suzuki‐Miyaura and Mizoroki‐Heck Coupling Reactions in Aqueous Medium
CN110452267A (en) The phosphorylated qualone derivative and preparation method and application that a kind of 3- replaces
CN103980280A (en) Method for synthesizing quinazolino indazole derivatives under acidic condition
Singh et al. Recent Developments in the Synthetic Strategies of 4‐Quinolones and Its Derivatives
Jiang et al. Pd (II)-catalyzed oxidative cyclization reaction for the preparation of 2-substituted 1, 2, 3, 4-tetrahydroquinolines with halide functionality
CN111592509B (en) Method for synthesizing aryl (3-sulfuryl benzofuran-2-yl) ketone compound by copper catalysis
CN107216326B (en) The synthetic method of (1,2,3- triazole) [1,5-f] phenanthridines -10- carboxylic acid ethyl ester compound
CN108864115A (en) The method of the non-aromatic purine nucleosides of [3+2] cycloaddition asymmetry dearomatization synthesis of chiral
CN107151226A (en) A kind of preparation method of polysubstituted isoindolinone
CN103288707B (en) A kind of preparation method of 3-benzene sulfydryl indole derivative
CN108690031B (en) Synthetic method of furo [3,4-c ] quinoline/furo [3,4-c ] coumarin compound

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Wang Liang

Inventor after: Zhou Lin

Inventor after: Xie Haohao

Inventor after: Zhang Yumin

Inventor before: Zhou Lin

Inventor before: Wang Liang

Inventor before: Xie Haohao

Inventor before: Zhang Yumin

WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170613