CN108707081A - A kind of alkene 1,2- difunctionalities dough reaction method - Google Patents
A kind of alkene 1,2- difunctionalities dough reaction method Download PDFInfo
- Publication number
- CN108707081A CN108707081A CN201810742506.8A CN201810742506A CN108707081A CN 108707081 A CN108707081 A CN 108707081A CN 201810742506 A CN201810742506 A CN 201810742506A CN 108707081 A CN108707081 A CN 108707081A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- substituted
- alkyl
- reaction
- formula
- 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.)
- Granted
Links
- 0 O=C(C1CCCCCC1)O*C(CC(c1c2cccc1)=O)C2=O Chemical compound O=C(C1CCCCCC1)O*C(CC(c1c2cccc1)=O)C2=O 0.000 description 4
- HDNRAPAFJLXKBV-UHFFFAOYSA-N CCc(cc1)ccc1OC Chemical compound CCc(cc1)ccc1OC HDNRAPAFJLXKBV-UHFFFAOYSA-N 0.000 description 2
- SGSFMKFJIQMWFY-UHFFFAOYSA-N CC(ON(C(c1c2cccc1)O)C2=O)=O Chemical compound CC(ON(C(c1c2cccc1)O)C2=O)=O SGSFMKFJIQMWFY-UHFFFAOYSA-N 0.000 description 1
- MCUQFEFGVOZAPE-ZROIWOOFSA-N Cc1c(C)c(NC(CCC2CCCC2)C/C=C\C(CC=C)COC)ccc1 Chemical compound Cc1c(C)c(NC(CCC2CCCC2)C/C=C\C(CC=C)COC)ccc1 MCUQFEFGVOZAPE-ZROIWOOFSA-N 0.000 description 1
- PVOREPSCWZFZME-UHFFFAOYSA-N Cc1cccc(NC(CC2C=CCCCC2)c(cc2)ccc2OC)c1C Chemical compound Cc1cccc(NC(CC2C=CCCCC2)c(cc2)ccc2OC)c1C PVOREPSCWZFZME-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N Cc1ccccc1O Chemical compound Cc1ccccc1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- WYAGOMKRJQNFHA-UHFFFAOYSA-N O=C(C1(CC1)c1ccccc1)ON(C(c1ccccc11)=O)C1=O Chemical compound O=C(C1(CC1)c1ccccc1)ON(C(c1ccccc11)=O)C1=O WYAGOMKRJQNFHA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
- C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/36—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings condensed with one six-membered ring
-
- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
- C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring 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 atoms of the carbocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/44—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing eight carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of alkene 1,2- difunctionality dough reaction methods, this method is with ethylene compounds shown in Formulas I, N- substituted phthalimides class compound shown in Formula II, amine shown in formula III is raw material, in the presence of photochemical catalyst, reaction promoter and organic solvent, under illumination, inert atmosphere, reaction is stirred at room temperature, obtains target product shown in formula IV.The method reaction condition of the present invention is mild, can carry out at room temperature, photochemical catalyst Ru (bpy)3Cl2It can be recycled and reused by the method for filtering.The present invention method also have it is easy to operate, reaction substrate is applied widely, generate process costs it is low, it is environmental-friendly, the advantages of.
Description
Technical field
The application belongs to technical field of organic synthesis, and in particular to a kind of alkene 1,2- difunctionality dough reaction methods.
Background technology
Ethylene is that one of maximum chemical products of yield, ethylene industry are the core of petrochemical industry, ethylene in the world
Product accounts for 75% of petroleum chemicals or more, occupies an important position in national economy.The reaction that alkenes compounds are participated in
There is particularly important status in organic synthesis, and because its is relatively cheap and be easy to get, and can also carry out more
Functional group conversions, therefore develop and realize that the high effective way of olefin functionalities is very necessary.
There is apparent high efficiency since alkene difunctional is combined to various useful compounds, it can be more with one-step synthesis
Site reaction product, not only economy but also efficient, thus in recent years, which is one and receives chemist favor
Research direction.And the research of the catalyst system and catalyzing in being reacted for alkene difunctionality dough is also of interest one of chemist
A research hotspot.From the point of view of document report, catalyst system and catalyzing is concentrated mainly on the oxygen such as transition metal-catalyzed and some peroxide
The effect of agent；Although Pd is main metallic catalyst, some are also reported in recent years and uses other transition metals
The catalyst system and catalyzing of such as Rh, Fe.Meanwhile the development that asymmetric alkene is Bifunctionalized, the application of various new reaction substrates, no
With the proposition of response strategy and the explanation of a variety of different reaction mechanisms and verify also constantly development and it is perfect.Although
The bifunctional dough reaction of transition metal-catalyzed alkene is successful in terms of having, and is widely used in medicine
In object synthesis, but the reaction of the bifunctional dough of alkene is often confined to the synthesis of common function dough product, meanwhile, reaction
The problems such as condition is harsher also limits its popularization and application in the industrial production.Therefore, develop efficient alkene difunctionality
Dough reaction is highly important.It concentrates on studies for this purpose, inventor passes through, in the present invention, it is proposed that a kind of novel alkene
1,2- difunctionality dough reacts new method.
Invention content
The purpose of the present invention is to overcome the deficiency in the prior art, and it is suitable to provide one kind simple for process, mild condition, reaction substrate
With the wide alkene 1,2- difunctionality dough reaction methods of range.
Alkene 1 provided by the invention, 2- difunctionality dough reaction methods, includes the following steps：
Ethylene compounds shown in Formulas I are added into Schlenk tube sealing reaction devices, N- replaces adjacent benzene two shown in Formula II
Carboximide class compound, amine shown in formula III, photochemical catalyst, reaction promoter and organic solvent, under illumination, inert atmosphere,
Reaction is stirred at room temperature, the reaction was complete through TLC detections, then post-treated obtains target product shown in formula IV.
In above-mentioned Formulas I-formula IV, R1Selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C6-20Virtue
Base, substituted or unsubstituted C4-20Heteroaryl, substituted or unsubstituted C1-20Alkyl-O-CO-；
R2、R3It is independently from each other hydrogen, substituted or unsubstituted C1-20Alkyl；
R4Selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C3-C20Naphthenic base, substitution or do not take
The C in generation3-C20Heterocyclylalkyl；
R5、R6Selected from hydrogen, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C3-C20Naphthenic base, substitution
Or unsubstituted C6-20Aryl, substituted or unsubstituted C4-20Heteroaryl or R5、R6Be connected with each other and with the nitrogen that is connected
Atom is together to form with or without other heteroatomic substituted or unsubstituted C3-C20Cyclic group；Condition is R5、R6No
It is hydrogen simultaneously.
In the arbitrary portion of the present invention, the substituent group in this any described " substituted or unsubstituted " statement is selected from
C1-C6Alkyl, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C6-C20Aryl
Acetenyl, C3-C8Naphthenic base, C1-6Alkyl-O-CO-.To those skilled in the art, it is to be understood that herein
In the number of substituent group in this so-called " substituted or unsubstituted " statement can be one or more, such as substituted benzene
When base, can have there are one, two, three, four or five substituent groups, the upper limit of substituent group quantity depends on the group
It can substituted site.
As the further preferred of technical solution of the present invention, wherein R1Selected from substituted or unsubstituted C1-6Alkyl, substitution
Or unsubstituted C6-14Aryl, substituted or unsubstituted C4-12Heteroaryl, substituted or unsubstituted C1-6Alkyl-O-
CO-；
R2、R3It is independently from each other hydrogen, substituted or unsubstituted C1-6Alkyl；
R4Selected from substituted or unsubstituted C1-12Alkyl, substituted or unsubstituted C3-C12Naphthenic base, substitution or do not take
The C in generation3-C12Heterocyclylalkyl；
R5、R6Selected from hydrogen, substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C3-C8Naphthenic base, substitution or
Unsubstituted C6-14Aryl, substituted or unsubstituted C4-12Heteroaryl or R5、R6It is connected with each other and former with the nitrogen being connected
Son is together to form with or without other heteroatomic substituted or unsubstituted C3-C12Cyclic group；Condition is R5、R6It is different
When be hydrogen.
Wherein, it is described substitution or it is unsubstituted in substituent group be such as defined herein before.
In the present invention, for the C1-20Alkyl, C1-12Alkyl enumerate, such as can be methyl, ethyl, third
Base, butyl, isopropyl, isobutyl group, tertiary butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, undecyl etc..
In the present invention, as C1-6Alkoxy, C1-6Alkyl example, moieties therein can be chosen in particular from
Above-mentioned " C1-20Alkyl " C that is enumerated1-6Alkyl type.
In the present invention, as C6-20Aryl, C6-14Aryl example, can be selected from for example phenyl, naphthalene, anthryl,
Phenanthryl etc..
In the present invention, the C4-C20Heteroaryl, C4-12Heteroaryl in hetero atom can be selected from O, S, N, tool
The heteroaryl of body can be selected from such as thienyl, furyl, pyridyl group.
In the present invention, as C3-C20Naphthenic base, C3-C12Naphthenic base example, such as such as monocycle can be selected from
Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl etc.；Bicyclic such as two Huan [2.2.2]Octyl, two Huan [2,2,1]Heptane
Base, decahydronaphthalene naphthalene；It is polycyclic such as adamantyl.
In the present invention, as C3-C20Heterocyclylalkyl, C3-C12Heterocyclylalkyl example, such as tetrahydrochysene can be selected from
Furyl, tetrahydro-thienyl, nafoxidine base, morpholinyl, piperazinyl, piperidyl etc..
According to present invention group definition above-mentioned, wherein described in " or R5、R6Be connected with each other and with the nitrogen-atoms one that is connected
It rises to be formed with or without other heteroatomic substituted or unsubstituted C3-C20Cyclic group " and " or R5、R6It is connected with each other
And to be formed with or without other heteroatomic substituted or unsubstituted C together with connected nitrogen-atoms3-C12Cyclic group "
In, as C3-C20Cyclic group, C3-C12The example of cyclic group can be selected from such as indoline baseFour
Hydrogen quinolylBenzo morpholinylDeng.
Still more preferably as technical solution of the present invention, wherein R1Selected from substituted or unsubstituted phenyl, substitution or
Unsubstituted naphthalene, substituted or unsubstituted pyridyl group, substituted or unsubstituted thienyl；
R2Selected from hydrogen；R3Selected from hydrogen or C1-6Alkyl
R4Selected from C1-12Alkyl, substituted or unsubstituted C3-C12Naphthenic base, C3-C12Heterocyclylalkyl；
R5、R6Selected from hydrogen, substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted
Naphthalene or R5、R6It is connected with each other and together with connected nitrogen-atoms to form indoline baseTetrahydric quinoline groupBenzo morpholinylCondition is R5、R6It is asynchronously hydrogen.
Wherein, it is described substitution or it is unsubstituted in substituent group be such as defined herein before.
According to present invention method above-mentioned, the photochemical catalyst is selected from Ir (ppy)3、Ru(bpy)3Cl2、Ru(bpy)3Cl2·6H2O、[Ir(dtbbpy)(ppy)2](PF6)2In any one, most preferably Ru (bpy)3Cl2。
The reaction promoter is three (pentafluorophenyl group) boron (C6F5)3。
The organic solvent is dimethyl sulfoxide (DMSO) (DMSO), N,N-dimethylformamide (DMF), acetonitrile (MeCN), N-
Any one in methyl pyrrolidone (NMP), most preferably DMSO.The dosage of solvent does not limit particularly, so that each material
It is fully dispersed.
The light source of the illumination is provided by such as 9-36W energy-saving lamps or is provided by 1-5W blue led light sources.
According to present invention reaction above-mentioned, the inert atmosphere is to reacting inert atmosphere, and not mechanically
It is considered inert gas.To those skilled in the art, it is to be understood that the inert atmosphere for being usually used in organic reaction can
To be selected from argon gas atmosphere or nitrogen atmosphere.
According to present invention reaction above-mentioned, the reaction determines the reaction time by TLC or GC-MS monitoring, generally
For, completion can be reacted within 24 hours.
According to present invention reaction above-mentioned, wherein ethylene compounds shown in Formulas I, N- shown in Formula II replaces adjacent benzene two
Carboximide class compound, amine shown in formula III, photochemical catalyst, reaction promoter molar ratio be 1:(1~3):(1~
3):(0.1%~2%):(5%~20%).Preferably, ethylene compounds shown in Formulas I, the adjacent benzene of N- substitutions shown in Formula II
Dicarboximide class compound, amine shown in formula III, photochemical catalyst, reaction promoter molar ratio be 1:1.5:1.5:
1%:10%.
According to present invention reaction above-mentioned, wherein the post-processing operation is as follows：Mixed liquor after the completion of reaction is subtracted
Pressure concentration, obtains residue, then by residue through target product, wherein silicagel column shown in the isolated formula IV of silica gel column chromatography
The eluent of chromatography is the mixed liquor of n-hexane and ethyl acetate.
Beneficial effects of the present invention are as follows：
1. the present invention is reported for the first time with ethylene compounds shown in Formulas I, N- shown in Formula II replaces phthalyl
Imine compound, amine shown in formula III is raw material, in the presence of photochemical catalyst, reaction promoter and organic solvent, illumination,
Under inert atmosphere, reaction is stirred at room temperature, obtains the synthesis strategy of target product shown in formula IV, which has no existing skill
Art is reported.
2. present invention process has, reaction condition is mild, can carry out at room temperature, photochemical catalyst Ru (bpy)3Cl2It can be with
It is recycled and reused by the method for filtering.
3, method of the invention has easy to operate, and reaction substrate is applied widely, and it is low, environmental-friendly to generate process costs
The advantages of.
Specific implementation mode
Below in conjunction with specific embodiment, further detailed description is carried out to the present invention.
Embodiment 1-12 reaction condition optimizations are tested
With shown in Formulas I -1 to N- substituted phthalimides class compound shown in methoxy styrene, Formula II -1,
It is reaction raw materials with 2,3- dimethylanilines shown in formula III -1, has inquired into differential responses condition for optimization of synthesis knot
Wherein representative embodiment 1-12 is selected in the influence of fruit.As a result as shown in Table 1.
The type testing operation of wherein embodiment 1 is as follows：
It is added shown in Formulas I -1 to methoxy styrene (0.2mmol), -1 institute of Formula II into Schlenk tube sealing reaction devices
The N- substituted phthalimide class compounds (0.3mmol) shown, 23 dimethyl aniline shown in formula III -1
(0.3mmol), photochemical catalyst Ir (ppy)3(1mol%) and DMSO (2mL) shines, under argon gas atmosphere in 5W blue LED lights, in room
After temperature is stirred to react 24 hours, through TLC detections, the reaction was complete, and the mixed liquor after the completion of reaction is concentrated under reduced pressure, residue is obtained,
Again by residue through target product shown in the isolated formula IV -1 of column plastic column chromatography, the wherein eluent of silica gel column chromatography separation
For the mixed liquor of n-hexane and ethyl acetate.Yield 21%.1H NMR(400MHz,CDCl3)δ:7.23 (d, J=9.2Hz, 2H),
6.846.82 (m, 3H), 6.50 (d, J=7.6Hz, 1H), 6.27 (d, J=8.0Hz, 1H), 4.38 (t, J=7.2Hz, 1H),
3.77(s,3H),2.27(s,3H),2.12(s,3H),1.81-1.57(m,7H),1.26-1.13(m,3H),1.00-0.93(m,
3H)；13C NMR(100MHz,CDCl3)δ:158.3,145.3,137.1,136.2,127.1,126.0,119.7,118.9,
113.9,109.1,55.2,54.8,47.5,34.7,33.9,33.0,26.5,26.2,26.1,20.7,12.6；LRMS(EI,
70eV) m/z (%):337(M+,7),240(52),121(100)；HRMS m/z(ESI)calcd for C23H32NO([M+H]+)
338.2478,found 338.24740.。
Table one：
Wherein, the concrete operations of embodiment 2-12 and parameter remove the variable listed by above-mentioned table one and differ it with embodiment 1
Outside, remaining operation and parameter are same as Example 1.
DMSO, which is optimum response solvent, to be shown for the selection result of reaction dissolvent it can be seen from embodiment 1-12, and
MeCN, NMP can also obtain certain target product yield as reaction dissolvent, but be not so good as DMSO (embodiment 1-3).For light
Screening of catalyst the result shows that, Ru (bpy)3Cl2It is best photochemical catalyst, wherein when photochemical catalyst replaces with Eosin Y
When, reaction can not carry out (embodiment 4-6) well.On this basis, inventor is in order to further increase target product
Yield explores influence (embodiment 7-11) of the various different auxiliary agents for optimization reaction result, the results showed that three (phenyl-pentafluorides
Base) boron as reaction promoter when for the present invention reaction have very significant facilitation.Increase temperature for reaction and
Speech has adverse effect (embodiment 12).In addition, inventor has also carried out no light and without photochemical catalyst to having a competition respectively
Test, the results showed that no illumination condition and/or without using photochemical catalyst in the case of, reaction of the invention is can not to carry out
's.
Optimum process condition of the present invention is the technique of embodiment 11 it can be seen from the representative embodiment 1-12 in table one
Condition.On the basis of obtaining optimum process condition, inventor further selects the Formulas I, Formula II and formula III of different substituents anti-
Raw material is answered, reaction is to prepare the target compound of various formula IVs under optimum process condition (embodiment 11).
Embodiment 13
Using the compound of Formula II -2 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -2, yield 73%.1H NMR(400MHz,CDCl3)δ:7.22 (d, J=7.6Hz, 2H), 6.83-6.81 (m, 3H),
6.48 (d, J=7.2Hz, 1H), 6.23 (d, J=7.9Hz, 1H), 4.47-4.40 (m, 1H), 3.75 (s, 3H), 2.26 (s,
3H),2.11(s,3H),1.72(s,2H),1.50-1.40(m,6H),1.36-1.29(m,4H),1.03(s,3H)；13C NMR
(100MHz,CDCl3)δ:158.1,144.9,138.4,136.2,126.9,126.0,119.5,118.7,113.9,108.9,
55.2,53.9,38.6,38.3,33.4,26.3,22.1,22.0,20.8,12.6；LRMS (EI, 70eV) m/z (%):351(M+,7),240(42),97(100)；HRMS m/z(ESI)calcd for C24H34NO([M+H]+)352.2635,found
352.2630.。
Embodiment 14
Using the compound of Formula II -3 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -3, yield 76%.1H NMR(400MHz,CDCl3)δ:7.20 (d, J=8.4Hz, 2H), 6.85-6.80 (m, 3H),
6.49 (d, J=7.2Hz, 1H), 6.22 (d, J=8.0Hz, 1H), 4.44 (d, J=7.2Hz, 1H), 3.84 (s, 1H), 3.75
(s,3H),2.27(s,3H),2.11(s,3H),1.98-1.90(m,3H),1.70-1.56(m,14H)；13C NMR(100MHz,
CDCl3)δ:158.1,144.9,138.4,136.1,126.9,126.0,119.5,118.7,113.9,109.0,55.5,
55.2,53.0,43.1,36.9,32.9,28.6,20.8,12.6；LRMS (EI, 70eV) m/z (%):389(M+,10),240
(100)；HRMS m/z(ESI)calcd for C27H36NO([M+H]+)390.2791,found 390.2798.。
Embodiment 15
Using the compound of Formula II -4 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -4, yield 47%.1H NMR(400MHz,CDCl3)δ:7.18 (d, J=8.0Hz, 2H), 6.84-6.80 (m, 3H),
6.50 (d, J=7.6Hz, 1H), 6.23 (d, J=8.0Hz, 1H), 4.45-4.36 (m, 1H), 3.75 (s, 3H), 3.62 (s,
3H),2.26(s,3H),2.10(s,3H),1.79-1.71(m,6H),1.66-1.61(m,2H),1.57-1.49(m,6H)；13C
NMR(100MHz,CDCl3)δ:178.3,158.2,144.6,137.8,136.2,126.9,126.0,119.5,118.9,
113.9,108.9,55.2,53.7,51.8,51.6,38.7,31.1,31.0,28.5,20.7,12.6；(EI,70eV)m/z
(%):421(M+,7),301(56),240(100),107(77)；HRMS m/z(ESI)calcd for C27H36NO3([M+H
]+)422.2690,found 422.2697.。
Embodiment 16
Using the compound of Formula II -5 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -5, yield 44%.1H NMR(400MHz,CDCl3)δ:7.24 (d, J=8.4Hz, 2H), 6.86-6.82 (m, 3H),
6.50 (d, J=7.6Hz, 1H), 6.28 (d, J=8.0Hz, 1H), 4.31 (t, J=6.4Hz, 1H), 3.76 (s, 3H), 2.26
(s,3H),2.11(s,3H),1.91-1.35(m,12H),1.26-1.14(m,3H)；13C NMR(100MHz,CDCl3)δ:
158.3,145.3,136.8,136.2,127.2,126.0,119.7,118.9,113.9,109.1,57.0,55.2,46.0,
37.2,32.9,25.1,25.0,20.7,12.6；(EI, 70eV) m/z (%):351(M+,7),240(100),121(7)；HRMS
m/z(ESI)calcd for C24H34NO([M+H]+)352.2635,found 352.2642.。
Embodiment 17
Using the compound of Formula II -6 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -6, yield 50%.1H NMR(400MHz,CDCl3)δ:7.24 (d, J=8.4Hz, 2H), 6.84-6.82 (m, 3H),
6.50 (d, J=7.6Hz, 1H), 6.28 (d, J=8.0Hz, 1H), 4.30 (t, J=6.4Hz, 1H), 3.76 (s, 3H), 2.26
(s,3H),2.11(s,3H),1.84-1.48(m,12H),1.26-1.14(m,3H)；13C NMR(100MHz,CDCl3)δ:
158.3,145.3,136.8,136.2,127.2,126.0,119.7,118.9,113.9,109.1,57.0,55.2,46.0,
37.2,32.9,25.1,25.0,20.7,12.6；LRMS (EI, 70eV) m/z (%):323(M+,5),240(37),121
(100)；HRMS m/z(ESI)calcd for C22H30NO([M+H]+)324.2322,found 324.2329.。
Embodiment 18
Using the compound of Formula II -6 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -6, yield 46%.1H NMR(400MHz,CDCl3)δ:7.31 (d, J=8.0Hz, 1H), 7.23 (d, J=6.4Hz,
1H),6.85-6.78(m,3H),6.50-6.45(m,1H),6.20-6.14(m,1H),4.65-4.58(m,0.55H),4.37-
4.34(m,0.48H),3.97-3.86(m,2H),3.79-3.76(m,4H),2.27(s,3H),2.14-2.10(m,3H),
2.00-1.78(m,5H),1.54-1.45(m,1H)；13C NMR(100MHz,CDCl3)δ:158.4,158.2,146.0,
145.3,137.0,136.1,136.1,135.5,127.4,127.1,125.9,125.7,120.7,119.7,118.9,
118.3,113.9,113.8,109.4,108.6,78.5,76.2,67.9,67.8,58.2,55.3,55.2,55.1,45.2,
43.0,38.4,36.2,32.3,31.6,25.5,25.2,20.7,12.6,12.6；(EI, 70eV) m/z (%):325(M+,8),
240(28),71(100)；HRMS m/z(ESI)calcd for C21H28NO2([M+H]+)326.2115,found
326.2119.。
Embodiment 19
Using the compound of Formula II -8 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -8, yield 53%.1H NMR(400MHz,CDCl3)δ:7.33-7.12 (m, 7H), 6.79 (d, J=8.0Hz, 2H),
6.72 (t, J=7.2Hz, 1H), 6.46 (d, J=6.8Hz, 1H), 6.00 (d, J=7.6Hz, 1H), 4.20-4.09 (m, 2H),
3.74(s,3H),2.24(s,3H),2.14-1.99(m,2H),1.91(s,3H),0.89-0.78(m,3H),0.59-0.56(m,
1H)；13C NMR(100MHz,CDCl3)δ:158.3,145.0,144.2,136.7,135.9,129.0,128.5,127.1,
126.4,125.7,119.9,118.9,113.8,109.3,56.7,55.2,50.1,24.0,20.7,14.3,12.3,11.4；
(EI, 70eV) m/z (%):371(M+,6),240(100),207(12)；HRMS m/z(ESI)calcd for C26H30NO([M+
H]+)372.2322,found 372.2329.。
Embodiment 20
Using the compound of Formula II -9 as reaction raw materials, remaining reaction raw material, operation and parameter obtain target with embodiment 11
Product IV -9, yield 51%.1H NMR(400MHz,CDCl3)δ:77.24 (d, J=8.0Hz, 2H), 6.84-6.82 (m, 3H),
6.50 (d, J=7.2Hz, 1H), 6.27 (d, J=8.0Hz, 1H), 4.34 (t, J=7.2Hz, 1H), 3.76 (s, 3H), 2.26
(s,3H),2.11(s,3H),1.76-1.61(m,2H),1.41-1.26(m,5H),0.90-0.80(m,6H)；13C NMR
(100MHz,CDCl3)δ:158.3,145.3,137.1,136.2,127.1,126.0,119.7,118.9,113.9,109.1,
55.5,55.2,43.5,37.3,25.6,25.2,20.7,12.6,10.9,10.4；LRMS (EI, 70eV) m/z (%):325(M+,7),240(37),121(100)；HRMS m/z(ESI)calcd for C22H32NO([M+H]+)326.2478,found
326.2488.。
Embodiment 21
Using the compound of Formula II -10 as reaction raw materials, remaining reaction raw material, operation and parameter obtain mesh with embodiment 11
Mark product IV -10, yield 50%.1H NMR(400MHz,CDCl3)δ:7.22 (d, J=8.8Hz, 2H), 6.86-6.81 (m,
3H), 6.49 (d, J=7.6Hz, 1H), 6.25 (d, J=8.0Hz, 1H), 4.41 (t, J=6.0Hz, 1H), 3.86 (s, 1H),
3.76 (s, 3H), 2.26 (s, 3H), 2.11 (s, 3H), 1.71 (d, J=6.0Hz, 2H), 1.01 (s, 9H)；13C NMR
(100MHz,CDCl3)δ:158.3,145.0,138.2,136.2,127.0,126.0,119.6,118.8,114.0,109.0,
55.3,54.9,54.2,31.1,30.3,20.8,12.6；LRMS (EI, 70eV) m/z (%):311(M+,12),240(36),
121(42),57(100)；HRMS m/z(ESI)calcd for C21H30NO([M+H]+)312.2322,found
312.2330.。
Embodiment 22
Using the compound of Formula II -11 as reaction raw materials, remaining reaction raw material, operation and parameter obtain mesh with embodiment 11
Mark product IV -11, yield 52%.1H NMR(400MHz,CDCl3)δ:7.24 (d, J=8.8Hz, 2H), 6.86-6.82 (m,
3H), 6.50 (d, J=7.2Hz, 1H), 6.26 (d, J=8.0Hz, 1H), 4.26 (t, J=6.8Hz, 1H), 3.88 (s, 1H),
2.27 (s, 3H), 2.12 (s, 3H), 1.82-1.77 (m, 2H), 1.35-1.25 (m, 10H), 0.87 (t, J=7.2Hz, 3H)；13C
NMR(100MHz,CDCl3)δ:158.4,145.3,136.7,136.3,127.3,126.0,119.8,119.0,113.9,
109.2,57.7,55.2,39.3,31.8,29.5,29.2,26.5,22.7,20.8,14.1,12.6；LRMS(EI,70eV)m/z
(%):339(M+,9),240(52),121(100)；HRMS m/z(ESI)calcd for C23H34NO([M+H]+)
340.2635,found 340.2641.。
Embodiment 23
Using the compound of Formula II -12 as reaction raw materials, remaining reaction raw material, operation and parameter obtain mesh with embodiment 11
Mark product IV -12, yield 44%.1H NMR(400MHz,CDCl3)δ:7.23 (d, J=8.0Hz, 2H), 6.83 (d, J=
7.6Hz, 3H), 6.50 (d, J=7.2Hz, 1H), 6.26 (d, J=7.6Hz, 1H), 4.26 (t, J=6.4Hz, 1H), 3.76 (s,
3H),2.26(s,3H),2.11(s,3H),1.90-1.70(m,2H),1.41-1.19(m,20H),0.91-0.86(m,3H)；13C
NMR(100MHz,CDCl3)δ:158.3,145.3,136.6,136.2,127.2,126.0,119.8,118.9,113.8,
109.1,57.7,55.2,39.3,31.9,29.6,29.6,29.6,29.5,29.5,29.3,26.4,22.7,20.7,14.1,
12.6；LRMS (EI, 70eV) m/z (%):409(M+,14),240(100)；HRMS m/z(ESI)calcd for C28H44NO
([M+H]+)410.3417,found 410.3423.。
Embodiment 24
Using the compound of Formula II -13 as reaction raw materials, remaining reaction raw material, operation and parameter obtain mesh with embodiment 11
Mark product IV -13, yield 50%.1H NMR(400MHz,CDCl3)δ:7.23 (d, J=8.0Hz, 2H), 6.86-6.82 (m,
3H), 6.50 (d, J=7.2Hz, 1H), 6.27 (d, J=8.0Hz, 1H), 4.26 (t, J=6.8Hz, 1H), 4.13-4.08 (m,
2H),3.76(s,3H),2.30-2.24(m,5H),2.11(s,3H),1.82-1.75(m,2H),1.62-1.59(m,2H),
1.44-1.35 (m, 4H), 1.24 (t, J=7.2Hz, 3H)；13C NMR(100MHz,CDCl3)δ:173.7,158.4,145.2,
136.3,136.2,127.2,125.9,119.8,119.0,113.9,109.1,60.2,57.5,55.2,39.0,34.2,
29.0,26.1,24.8,20.7,14.2,12.6；LRMS (EI, 70eV) m/z (%):383(M+,9),240(85),121
(100)；HRMS m/z(ESI)calcd for C24H34NO3([M+H]+)384.2533,found 384.2539.。
Embodiment 25
Using Formula II -3, the compound of III-2 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-14, yield 57%.1H NMR(400MHz,CDCl3)δ:(7.22 d, J=7.2Hz, 2H), 7.07 (t, J=
7.2Hz, 2H), 6.83 (d, J=7.2Hz, 2H), 6.61 (t, J=7.2Hz, 1H), 6.47 (d, J=7.6Hz, 2H), 4.44-
4.37(m,1H),3.93(s,1H),3.75(s,3H),1.94(s,3H),1.71-1.52(m,14H)；13C NMR(100MHz,
CDCl3)δ:158.2,147.1,138.2,129.0,127.0,116.8,113.9,113.1,55.2,55.0,53.1,43.0,
36.9,32.9,28.6；(EI, 70eV) m/z (%):361(M+,7),269(9),212(73),135(100)；HRMS m/z
(ESI)calcd for C25H32NO([M+H]+)362.2478,found 362.2470.。
Embodiment 26
Using Formula II -3, the compound of III-3 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-15, yield 35%.1H NMR(400MHz,CDCl3)δ:7.23 (d, J=8.0Hz, 2H), 6.83 (d, J=
7.6Hz, 2H), 6.68 (d, J=8.0Hz, 2H), 6.43 (d, J=7.6Hz, 2H), 4.37-4.28 (m, 1H), 3.77 (s, 3H),
3.68(s,3H),1.99-1.90(m,3H),1.70-1.51(m,14H)；13C NMR(100MHz,CDCl3)δ:158.1,
151.6,141.6,138.5,127.1,114.7,114.2,113.9,55.7,55.2,55.0,54.0,43.0,36.9,33.0,
28.6；LRMS (EI, 70eV) m/z (%):391(M+,3),242(18),135(100)；HRMS m/z(ESI)calcd for
C26H34NO2([M+H]+)392.2584,found 392.2594.。
Embodiment 27
Using Formula II -3, the compound of III-4 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-16, yield 47%.1H NMR(400MHz,CDCl3)δ:7.20 (d, J=7.6Hz, 2H), 6.97 (t, J=
7.6Hz, 1H), 6.84 (d, J=7.6Hz, 2H), 6.57 (d, J=8.0Hz, 1H), 6.46 (s, 1H), 6.33 (d, J=8.4Hz,
1H), 4.37 (t, J=5.6Hz, 1H), 4.00 (s, 1H), 3.77 (s, 3H), 1.99-1.92 (m, 3H), 1.72-1.48 (m,
14H)；13C NMR(100MHz,CDCl3)δ:158.3,148.2,137.4,134.7,130.0,127.0,116.8,114.0,
112.8,111.3,55.2,54.9,53.1,43.0,36.9,33.0,28.6；LRMS (EI, 70eV) m/z (%):397(M++2,
1),395(M+,3),246(39),135(100)；HRMS m/z(ESI)calcd for C25H31ClNO([M+H]+)
396.2089,found 396.2085.。
Embodiment 28
Using Formula II -3, the compound of III-5 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-17, yield 48%.1H NMR(400MHz,CDCl3)δ:7.23-7.19 (m, 3H), 6.95 (t, J=
8.0Hz, 1H), 6.83 (d, J=7.6Hz, 2H), 6.53 (t, J=7.6Hz, 1H), 6.37 (d, J=8.4Hz, 1H), 4.65 (s,
1H),4.42-4.38(m,1H),3.76(s,3H),2.02-1.90(m,3H),1.71-1.52(m,14H)；13C NMR
(100MHz,CDCl3)δ:158.3,142.8,137.5,128.8,127.6,126.9,118.8,116.7,114.0,112.2,
55.2,53.0,43.0,36.9,32.9,28.6；LRMS (EI, 70eV) m/z (%):397(M++2,1),395(M+,3),246
(38),135(100)；HRMS m/z(ESI)calcd for C25H31ClNO([M+H]+)396.2089,found
396.2083.。
Embodiment 29
Using Formula II -3, the compound of III-6 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-18, yield 31%.1H NMR(400MHz,CDCl3)δ:7.63 (d, J=8.0Hz, 1H), 7.19 (d, J=
7.6Hz, 2H), 7.01 (t, J=7.6Hz, 1H), 6.83 (d, J=7.6Hz, 2H), 6.35 (t, J=7.2Hz, 1H), 6.27 (d,
J=8.0Hz, 1H), 4.56 (s, 1H), 4.45-4.43 (m, 1H), 3.77 (s, 3H), 2.00-1.92 (s, 3H), 1.71-1.53
(m,14H)；13C NMR(100MHz,CDCl3)δ:158.3,146.0,138.8,137.3,129.2,126.9,118.1,
114.0,111.7,85.2,55.3,55.2,53.3,43.1,36.9,32.9,28.6；LRMS (EI, 70eV) m/z (%):487
(M+,4),338(35),135(100)；HRMS m/z(ESI)calcd for C25H31INO([M+H]+)488.1445,found
488.1455.。
Embodiment 30
Using Formula II -3, the compound of III-7 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-19, yield 35%.1H NMR(400MHz,CDCl3)δ:7.36 (d, J=7.6Hz, 1H), 7.23-7.19
(m, 3H), 6.85 (d, J=7.6Hz, 2H), 6.60 (t, J=7.6Hz, 1H), 6.42 (d, J=8.4Hz, 1H), 4.85-4.84
(m,1H),4.48(s,1H),3.77(s,3H),2.00-1.93(s,3H),1.71-1.54(m,14H)；13C NMR(100MHz,
CDCl3)δ:158.5,149.1,136.5,134.1,132.5,126.8,118.0,116.3,114.1,111.8,95.6,
55.2,54.9,52.9,42.9,36.8,32.9,28.5；LRMS (EI, 70eV) m/z (%):386(M+,2),269(13),237
(57),135(100)；HRMS m/z(ESI)calcd for C26H31N2O([M+H]+)387.2431,found 387.2437.。
Embodiment 31
Using Formula II -3, the compound of III-8 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-20, yield 50%.1H NMR(400MHz,CDCl3)δ:7.53 (d, J=7.2Hz, 2H), 7.38-7.32
(m, 4H), 7.23 (d, J=8.4Hz, 2H), 7.02 (t, J=7.6Hz, 1H), 6.84 (d, J=7.6Hz, 2H), 6.57 (t, J=
7.2Hz, 1H), 6.32 (d, J=8.0Hz, 1H), 5.08 (s, 1H), 4.51-4.43 (m, 1H), 3.75 (s, 3H), 1.97-1.90
(m,3H),1.69-1.54(m,14H)；13C NMR(100MHz,CDCl3)δ:158.2,147.8,137.7,131.8,131.3,
129.8,128.4,128.1,126.9,123.4,116.0,114.0,110.7,107.3,94.9,86.4,55.3,55.2,
53.2,43.1,36.9,32.9,28.6；HRMS m/z(ESI)calcd for C33H36NO([M+H]+)462.2791,found
462.2795.。
Embodiment 31
Using Formula II -3, the compound of III-9 as reaction raw materials, remaining reaction raw material, operation and parameter are obtained with embodiment 11
To target product IV-21, yield 48%.1H NMR(400MHz,CDCl3)δ:7.86 (d, J=8.0Hz, 1H), 7.76 (d, J=
6.8Hz, 1H), 7.45-7.43 (m, 2H), 7.26 (d, J=7.6Hz, 2H), 7.20-7.12 (m, 2H), 6.81 (d, J=
7.6Hz, 2H), 6.33 (d, J=7.2Hz, 1H), 4.70 (s, 1H), 4.63-4.59 (m, 1H), 3.73 (m, 3H), 1.97-1.88
(s,3H),1.75-1.61(m,14H)；13C NMR(100MHz,CDCl3)δ:158.2,141.9,137.7,134.2,128.7,
126.9,126.7,125.5,124.6,123.1,119.6,116.6,114.0,105.5,55.4,55.2,53.2,43.1,
36.9,33.0,28.6；(EI, 70eV) m/z (%):411(M+,20),262(100),230(12)；HRMS m/z(ESI)
calcd for C29H34NO([M+H]+)412.2635,found 412.2632.。
Embodiment 33
Using Formula II -3, the compound of III-10 as reaction raw materials, remaining reaction raw material, operation and parameter with embodiment 11,
Obtain target product IV-22, yield 52%.1H NMR(400MHz,CDCl3)δ:7.22 (t, J=7.2Hz, 2H), 7.15 (d, J
=8.0Hz, 2H), 6.80 (t, J=7.2Hz, 4H), 6.69 (t, J=7.2Hz, 1H), 5.10 (t, J=6.0Hz, 1H), 3.76
(s,3H),2.65(s,3H),1.90(s,3H),1.85-1.75(m,2H),1.67-1.49(m,12H)；13C NMR(100MHz,
CDCl3)δ:158.2,149.9,134.5,129.1,128.3,116.3,113.4,113.3,56.2,55.1,46.0,42.9,
37.0,32.6,32.1,28.7；(EI, 70eV) m/z (%):375(M+,7),226(100)；HRMS m/z(ESI)calcd
for C26H34NO([M+H]+)376.2635,found 376.2638.。
Embodiment 34
Using Formula II -3, the compound of III-11 as reaction raw materials, remaining reaction raw material, operation and parameter with embodiment 11,
Obtain target product IV-23, yield 61%.1H NMR(400MHz,CDCl3)δ:7.23 (d, J=8.0Hz, 2H), 7.05 (t, J
=7.6Hz, 1H), 6.97 (d, J=6.8Hz, 1H), 6.80 (d, J=7.6Hz, 2H), 6.61 (d, J=7.6Hz, 1H), 6.53
(t, J=7.2Hz, 1H), 4.82 (t, J=6.0Hz, 1H), 3.75 (s, 3H), 3.49-3.42 (m, 1H), 3.14-3.07 (m,
1H), 2.89-2.77 (m, 2H), 1.94-1.86 (m, 3H), 1.78 (d, J=6.4Hz, 2H), 1.67-1.48 (m, 12H)；13C
NMR(100MHz,CDCl3)δ:158.4,150.8,133.4,129.8,129.1,127.1,124.4,116.2,113.4,
106.4,55.1,53.2,46.3,44.7,43.0,37.0,32.6,28.7,27.9；(EI, 70eV) m/z (%):387(M+,
4),238(12),135(100)；HRMS m/z(ESI)calcd for C27H34NO([M+H]+)388.2635,found
388.2644.。
Embodiment 35
Using Formula II -3, the compound of III-12 as reaction raw materials, remaining reaction raw material, operation and parameter with embodiment 11,
Obtain target product IV-24, yield 63%.1H NMR(400MHz,CDCl3)δ:7.21 (d, J=8.0Hz, 2H), 7.05 (t, J
=7.6Hz, 1H), 6.92 (d, J=7.2Hz, 1H), 6.86 (d, J=8.4Hz, 1H), 6.80 (d, J=8.0Hz, 2H), 6.53
(t, J=7.2Hz, 1H), 5.13 (t, J=6.0Hz, 1H), 3.75 (s, 3H), 3.27-3.22 (m, 1H), 3.00-2.96 (m,
1H),2.70-2.60(m,2H),1.91-1.80(m,6H),1.68-1.52(m,13H)；13C NMR(100MHz,CDCl3)δ:
158.2,145.1,134.4,129.3,128.5,127.0,122.9,115.0,113.4,111.2,55.1,54.2,45.1,
43.0,37.0,32.8,28.7,21.9；LRMS (EI, 70eV) m/z (%):401(M+,9),252(100)；HRMS m/z
(ESI)calcd for C28H36NO([M+H]+)402.2791,found 402.2799.。
Embodiment 36
Using Formula II -3, the compound of III-13 as reaction raw materials, remaining reaction raw material, operation and parameter with embodiment 11,
Obtain target product IV-25, yield 59%.1H NMR(400MHz,CDCl3)δ:7.22 (d, J=7.2Hz, 2H), 7.04 (d, J
=8.0Hz, 1H), 6.89-6.70 (m, 4H), 6.59 (d, J=7.6Hz, 1H), 5.13 (t, J=6.0Hz, 1H), 4.11-4.08
(m,1H),3.84-3.76(m,1H),3.76(s,3H),3.26-3.24(m,1H),3.05-3.04(m,1H),1.95-1.89
(s, 3H), 1.78 (d, J=6.0Hz, 2H), 1.69-1.50 (m, 12H)；13C NMR(100MHz,CDCl3)δ:158.5,
144.1,134.7,133.2,128.8,121.5,116.7,116.6,113.4,112.6,64.2,55.1,54.2,44.1,
43.0,40.5,36.9,32.7,28.6；LRMS (EI, 70eV) m/z (%):403(M+,15),254(100)；HRMS m/z
(ESI)calcd for C27H34NO2([M+H]+)404.2584,found 404.2580.。
Embodiment 37
Using Formulas I -2, the compound of II-3, III-2 as reaction raw materials, remaining operation and parameter obtain mesh with embodiment 11
Mark product IV -26, yield 83%.1H NMR(400MHz,CDCl3)δ:7.20 (d, J=7.6Hz, 2H), 7.11-7.06 (m,
4H), 6.61 (t, J=7.2Hz, 1H), 6.47 (d, J=7.6Hz, 2H), 4.42 (t, J=5.2Hz, 1H), 3.97 (s, 1H),
2.30(s,3H),1.98-1.91(s,3H),1.71-1.53(m,14H)；13C NMR(100MHz,CDCl3)δ:147.1,
143.2,136.0,129.3,129.0,125.9,116.8,113.1,55.1,53.5,43.0,36.9,33.0,28.7,21.0；
LRMS (EI, 70eV) m/z (%):345(M+,3),196(100),135(30)；HRMS m/z(ESI)calcd for C25H32N
([M+H]+)346.2529,found 346.2519.。
Embodiment 38
Using Formulas I -3, the compound of II-3, III-2 as reaction raw materials, remaining operation and parameter obtain mesh with embodiment 11
Mark product IV -27, yield 71%.1H NMR(400MHz,CDCl3)δ:7.15-7.07(m,2H),6.97-6.92(m,2H),
6.69-6.61 (m, 1H), 6.48-6.40 (m, 2H), 5.88 (d, J=11.2Hz, 2H), 4.81-4.73 (m, 1H), 2.00-
1.92(m,3H),1.76-1.40(s,14H)；13C NMR(100MHz,CDCl3)δ:147.8,147.1,146.4,138.0,
129.2,117.2,112.9,112.6,112.0,107.3,101.5,53.3,52.9,43.2,36.9,33.3,28.7；LRMS
(EI, 70eV) m/z (%):455(M++2,3),453(M+,3),306(49),135(100)；HRMS m/z(ESI)calcd for
C25H29BrNO2([M+H]+)454.1376,found 454.1371.。
Embodiment 39
Using Formulas I -4, the compound of II-3, III-2 as reaction raw materials, remaining operation and parameter obtain mesh with embodiment 11
Mark product IV -28, yield 53%.1H NMR(400MHz,CDCl3)δ:7.11 (t, J=6.8Hz, 2H), 7.03-6.98 (m,
1H), 6.80-6.74 (s, 1H), 6.67 (t, J=7.6Hz, 1H), 6.51 (d, J=7.6Hz, 2H), 4.74-4.67 (m, 1H),
3.93(s,1H),2.27(s,3H),2.00-1.91(s,3H),1.71-1.57(m,14H)；13C NMR(100MHz,CDCl3)δ:
146.9,145.6,130.4,130.2,129.1,121.8,117.5,113.1,54.1,48.6,43.0,36.8,32.9,
28.6,13.9；LRMS (EI, 70eV) m/z (%):351(M+,4),202(31),135(100)；HRMS m/z(ESI)calcd
for C23H30NS([M+H]+)352.2093found 352.2099.。
Embodiment 40
Using Formulas I -5, the compound of II-3, III-2 as reaction raw materials, remaining operation and parameter obtain mesh with embodiment 11
Mark product IV -29, yield 33%.1H NMR(400MHz,CDCl3)δ:7.18 (d, J=7.6Hz, 2H), 7.07 (t, J=
7.2Hz, 2H), 6.83 (d, J=7.6Hz, 2H), 6.61 (t, J=7.2Hz, 1H), 6.42 (d, J=7.6Hz, 2H), 4.66 (s,
1H), 4.06 (s, 1H), 3.77 (s, 3H), 2.04-1.94 (m, 3H), 1.67-1.56 (m, 13H), 0.83 (d, J=7.2Hz,
3H)；13C NMR(100MHz,CDCl3)δ:158.0,147.0,136.8,129.0,127.5,116.6,113.6,113.1,
55.4,55.2,51.4,40.6,37.1,35.3,28.8,6.1；LRMS (EI, 70eV) m/z (%):375(M+,3),212
(100),135(10)；HRMS m/z(ESI)calcd for C26H34NO([M+H]+)376.2635,found 376.2646.。
Embodiment described above is merely a preferred embodiment of the present invention, and the simultaneously exhaustion of the feasible implementation of non-present invention.For
It is any apparent to made by it under the premise of without departing substantially from the principle of the invention and spirit for those skilled in the art
Change, should all be contemplated as falling with the present invention claims within.
Claims (10)
1. a kind of alkene 1,2- difunctionality dough reaction methods, which is characterized in that described method includes following steps：
Ethylene compounds shown in Formulas I are added into Schlenk tube sealing reaction devices, N- replaces phthalyl shown in Formula II
Imine compound, amine, photochemical catalyst, reaction promoter and organic solvent shown in formula III, under illumination, inert atmosphere, room temperature
It is stirred to react, through TLC detections, the reaction was complete, then post-treated obtains target product shown in formula IV；
Wherein, R1Selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C6-20Aryl, substitution or unsubstituted
C4-20Heteroaryl, substituted or unsubstituted C1-20Alkyl-O-CO-；
R2、R3It is independently from each other hydrogen, substituted or unsubstituted C1-20Alkyl；
R4Selected from substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C3-C20Naphthenic base, substituted or unsubstituted
C3-C20Heterocyclylalkyl；
R5、R6Selected from hydrogen, substituted or unsubstituted C1-20Alkyl, substituted or unsubstituted C3-C20Naphthenic base, substitution or not
Substituted C6-20Aryl, substituted or unsubstituted C4-20Heteroaryl or R5、R6Be connected with each other and with the nitrogen-atoms that is connected
Together to be formed with or without other heteroatomic substituted or unsubstituted C3-C20Cyclic group；Condition is R5、R6When different
For hydrogen；
In above-mentioned all group definitions, the substituent group in this described " substituted or unsubstituted " statement is selected from C1-C6Alkane
Base, C1-C6Alkoxy, C1-C6Acyl group, halogen ,-NO2、-CN、-OH、C6-C20Aryl, C6-C20Aryl ethane base,
C3-C8Naphthenic base, C1-6Alkyl-O-CO-；
And wherein, the photochemical catalyst is selected from Ir (ppy)3、Ru(bpy)3Cl2、Ru(bpy)3Cl2·6H2O、[Ir
(dtbbpy)(ppy)2](PF6)2In any one；
The reaction promoter is three (pentafluorophenyl group) boron (C6F5)3。
2. according to the method described in claim 1, it is characterized in that, R1Selected from substituted or unsubstituted C1-6Alkyl, substitution or
Unsubstituted C6-14Aryl, substituted or unsubstituted C4-12Heteroaryl, substituted or unsubstituted C1-6Alkyl-O-CO-；
R2、R3It is independently from each other hydrogen, substituted or unsubstituted C1-6Alkyl；
R4Selected from substituted or unsubstituted C1-12Alkyl, substituted or unsubstituted C3-C12Naphthenic base, substituted or unsubstituted
C3-C12Heterocyclylalkyl；
R5、R6Selected from hydrogen, substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted C3-C8Naphthenic base, substitution or do not take
The C in generation6-14Aryl, substituted or unsubstituted C4-12Heteroaryl or R5、R6Be connected with each other and with the nitrogen-atoms one that is connected
It rises to be formed with or without other heteroatomic substituted or unsubstituted C3-C12Cyclic group；Condition is R5、R6It is asynchronously
Hydrogen；
Wherein, described it is " substituted or unsubstituted " in substituent group it is as defined in claim 1.
3. according to the method described in claim 1-2 any one, which is characterized in that R1Selected from substituted or unsubstituted phenyl, take
Generation or unsubstituted naphthalene, substituted or unsubstituted pyridyl group, substituted or unsubstituted thienyl；
R2Selected from hydrogen；R3Selected from hydrogen or C1-6Alkyl；
R4Selected from C1-12Alkyl, substituted or unsubstituted C3-C12Naphthenic base, C3-C12Heterocyclylalkyl；
R5、R6Selected from hydrogen, substituted or unsubstituted C1-6Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene,
Or R5、R6It is connected with each other and together with connected nitrogen-atoms to form indoline baseTetrahydric quinoline groupBenzo morpholinylCondition is R5、R6It is asynchronously hydrogen；
Wherein, described it is " substituted or unsubstituted " in substituent group it is as defined in claim 1.
4. according to the method described in claim 1-3 any one, which is characterized in that the organic solvent is dimethyl sulfoxide (DMSO)
(DMSO), any one in N,N-dimethylformamide (DMF), acetonitrile (MeCN), N-Methyl pyrrolidone (NMP).
5. according to the method described in any of claim 1 to 4, which is characterized in that the light source of the illumination is saved by 9-36W
Energy lamp is provided or is provided by 1-5W blue led light sources.
6. according to the method described in claim 1-5 any one, which is characterized in that the photochemical catalyst is Ru (bpy)3Cl2, described organic solvent be selected from DMSO.
7. according to the method described in claim 1-6 any one, which is characterized in that the inert atmosphere is selected from argon gas atmosphere
Or nitrogen atmosphere.
8. according to the method described in claim 1-7 any one, which is characterized in that ethylene compounds shown in Formulas I, Formula II
Shown in N- substituted phthalimide class compounds, amine shown in formula III, photochemical catalyst, reaction promoter feed intake mole
Than being 1:(1~3):(1~3):(0.1%~2%):(5%~20%).
9. according to the method described in claim 8, it is characterized in that, ethylene compounds shown in Formulas I, N- takes shown in Formula II
For phthalimide derivatives, amine shown in formula III, photochemical catalyst, reaction promoter molar ratio be 1:1.5:
1.5:1%:10%.
10. according to the method described in claim 1-10 any one, which is characterized in that the post-processing operation is as follows：It will
Mixed liquor after the completion of reaction is concentrated under reduced pressure, and obtains residue, then by residue through shown in the isolated formula IV of silica gel column chromatography
Target product, wherein silica gel column chromatography separation eluent be n-hexane and ethyl acetate mixed liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810742506.8A CN108707081B (en) | 2018-07-09 | 2018-07-09 | Alkene 1, 2-bifunctional reaction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810742506.8A CN108707081B (en) | 2018-07-09 | 2018-07-09 | Alkene 1, 2-bifunctional reaction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108707081A true CN108707081A (en) | 2018-10-26 |
| CN108707081B CN108707081B (en) | 2020-12-15 |
Family
ID=63873988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810742506.8A Active CN108707081B (en) | 2018-07-09 | 2018-07-09 | Alkene 1, 2-bifunctional reaction method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108707081B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651209A (en) * | 2018-12-04 | 2019-04-19 | 湖南理工学院 | A kind of method that carbon-to-carbon σ-bond activation prepares (E) -1- phenyl -4- sulfonyl but-1-ene class compound |
| CN109912456A (en) * | 2019-04-24 | 2019-06-21 | 南昌航空大学 | A kind of preparation method of gamma-carboxylation alkyl nitrile compounds |
| CN110256211A (en) * | 2019-08-01 | 2019-09-20 | 南昌航空大学 | A kind of preparation method of 1,1- diarylalkane derivatives |
| CN111362795A (en) * | 2020-03-16 | 2020-07-03 | 中山大学 | Preparation method of substituted butyrate derivatives |
| CN112778068A (en) * | 2021-01-04 | 2021-05-11 | 南昌航空大学 | Copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction method |
| CN114456089A (en) * | 2022-03-29 | 2022-05-10 | 南昌航空大学 | Lewis acid promoted three-component reaction method of olefin, oxime ester and amine |
| CN114702429A (en) * | 2022-04-02 | 2022-07-05 | 南昌航空大学 | Method for constructing 3-alkyl indole compound by olefin dual-functionalization |
| CN116462561A (en) * | 2023-04-07 | 2023-07-21 | 深圳市鹏泰生物科技有限公司 | Alkylation method of visible light-promoted alkenyl cycloalkane compound |
-
2018
- 2018-07-09 CN CN201810742506.8A patent/CN108707081B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109651209A (en) * | 2018-12-04 | 2019-04-19 | 湖南理工学院 | A kind of method that carbon-to-carbon σ-bond activation prepares (E) -1- phenyl -4- sulfonyl but-1-ene class compound |
| CN109912456A (en) * | 2019-04-24 | 2019-06-21 | 南昌航空大学 | A kind of preparation method of gamma-carboxylation alkyl nitrile compounds |
| CN109912456B (en) * | 2019-04-24 | 2021-09-17 | 南昌航空大学 | Preparation method of gamma-carboxylation alkyl nitrile compound |
| CN110256211A (en) * | 2019-08-01 | 2019-09-20 | 南昌航空大学 | A kind of preparation method of 1,1- diarylalkane derivatives |
| CN110256211B (en) * | 2019-08-01 | 2022-02-25 | 南昌航空大学 | Preparation method of 1, 1-diaryl alkane derivative |
| CN111362795A (en) * | 2020-03-16 | 2020-07-03 | 中山大学 | Preparation method of substituted butyrate derivatives |
| CN112778068A (en) * | 2021-01-04 | 2021-05-11 | 南昌航空大学 | Copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction method |
| CN112778068B (en) * | 2021-01-04 | 2023-02-28 | 南昌航空大学 | Copper-catalyzed alkene 1, 2-alkoxy/polyhalogenated alkyl bifunctional reaction method |
| CN114456089A (en) * | 2022-03-29 | 2022-05-10 | 南昌航空大学 | Lewis acid promoted three-component reaction method of olefin, oxime ester and amine |
| CN114456089B (en) * | 2022-03-29 | 2023-05-23 | 南昌航空大学 | Lewis acid-promoted three-component reaction method of olefin and oxime ester with amine |
| CN114702429A (en) * | 2022-04-02 | 2022-07-05 | 南昌航空大学 | Method for constructing 3-alkyl indole compound by olefin dual-functionalization |
| CN116462561A (en) * | 2023-04-07 | 2023-07-21 | 深圳市鹏泰生物科技有限公司 | Alkylation method of visible light-promoted alkenyl cycloalkane compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108707081B (en) | 2020-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108707081A (en) | A kind of alkene 1,2- difunctionalities dough reaction method | |
| CN107857717A (en) | Aryl sulfoxid es, sulfide compound and its synthetic method and application | |
| CN108912036B (en) | Method for preparing allylindole compound by alkene 1, 4-bifunctional reaction | |
| CN112920145B (en) | Method for synthesizing 2, 5-furandicarboxylic acid by visible light catalysis | |
| CN104557602B (en) | Tricyclic diterpene derivative and preparation method thereof and the application in preparing antineoplastic thereof | |
| Schick et al. | Reaction of [60] fullerene with morpholine and piperidine: preferred 1, 4-additions and fullerene dimer formation | |
| Block et al. | 1, 3-Dithietane | |
| CN108863740B (en) | Preparation method of naphthalenone compound | |
| CN110305054A (en) | A kind of preparation method of disubstituted benzene vinyl derivatives | |
| CN112442002B (en) | Method for synthesizing 11-sulfenyl naphtho [2,3-b ] benzofuran compound | |
| CN109705001A (en) | The method that photocatalysis prepares 3- sulfonyl -1,2- dialin compound | |
| CN115785122A (en) | Indole derivative piperidine compound and synthetic method thereof | |
| CN114957037A (en) | Method for synthesizing beta-aminocarbonyl compound by photo-induced oxalyl oxime ester homolytic decarboxylation and activated olefin addition | |
| CN111362795B (en) | Preparation method of substituted butyrate derivatives | |
| CN110540516B (en) | Preparation method of 1-sulfonylmethyl-3, 4-dihydronaphthalene | |
| CN109867614A (en) | A kind of 4,4- dioxane sulphur-1- phenyl-3- butene-1 -one derivative and synthetic method | |
| CN108675935B (en) | Preparation method of 1, 1-diaryl alkane compound | |
| CN111056915A (en) | Synthesis method of 1, 2-dialkyl-1, 2-diaryl acetylene cyclobutane | |
| Trapani et al. | Use of phenacyl thiosalicylates for the preparation of 3-hydroxybenzo [b] thiophene derivatives | |
| CN113861086B (en) | Synthesis method of sulfur-containing gamma, gamma-diarylamine butyrylamide compound | |
| CN110963927A (en) | Allylation method of N-benzyl aniline compound | |
| CN113549020B (en) | Quinazoline derivatives, their preparation and use | |
| CN111792999B (en) | Dinaphthylamine compounds, and preparation method and application thereof | |
| CN110698490B (en) | Synthesis method of spiro-oxoindole-cyclopentenobutenoic acid lactone compound | |
| CN114920684B (en) | Selenium-containing benzamide compound and synthetic method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |