CN105001028A - Synthesis method for asymmetric conjugate diyne compound - Google Patents
Synthesis method for asymmetric conjugate diyne compound Download PDFInfo
- Publication number
- CN105001028A CN105001028A CN201510262112.9A CN201510262112A CN105001028A CN 105001028 A CN105001028 A CN 105001028A CN 201510262112 A CN201510262112 A CN 201510262112A CN 105001028 A CN105001028 A CN 105001028A
- Authority
- CN
- China
- Prior art keywords
- synthetic method
- diyne
- reaction
- asymmetric
- asymmetric conjugation
- 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
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a synthesis method for asymmetric conjugate diyne compound. According to the synthesis method, two kinds of different terminal alkynes are used as raw material, copper is used as catalyst, and the asymmetric conjugate diyne compound is synthesized; the copper which is cheap and easy to get is used as the catalyst, reaction is conducted in the air, precious metal and additive are not needed, prefunctionalization on the alkynes is not needed, special reaction conditions such as microwave radiation are not needed, and the production cost is lowered; the reaction condition is mild, the operation is simple, the applicability of substrate is wide, both the selectivity and productivity of product are high, and good industrial application prospect is achieved.
Description
[technical field]
The present invention relates to organic synthesis field, be specifically related to a kind of synthetic method of asymmetric conjugation diyne compounds.
[background technology]
Asymmetric 1,3-conjugation two acetylene compound has rigid structure unit and unique characteristic electron, this kind of compound structure is common in natural product and antibacterials, simultaneously it or functional molecule material synthesize in important functional group, in addition alkynes alkynes linked reaction is also widely used in many synthetic chemistry fields, such as: synthesize broad variety acetylide, build large ring system acetylide, the application etc. in natural product synthesis and supramolecule field.Therefore the synthetic method particularly important of asymmetric conjugation two acetylene compound, is one of difficult point of organic synthesis and pharmaceutical chemistry research, and the exploration about this kind of compou nd synthesis route is also constantly being goed deep into.
So far, the method both at home and abroad for realizing Terminal Acetylenes coupling is main or based on the inherit and development of traditional Glaser-Hay Terminal Acetylenes with molecular oxidation linked reaction and Cadiot-Chodkiewicz cross-coupling reaction.From environment and economy benefit, Lei A W etc., propose with NiCl for 2009
26H
2the catalyst system of O (5mol%), CuI (5mol%), TMEDA (20mol%), oxygen or air are as oxygenant, wherein a kind of Terminal Acetylenes excessive (5equiv), the Terminal Acetylenes that catalysis two kinds is different, obtain asymmetric conjugation diyne compounds, yield 63 ~ 93%.In order to avoid using excessive Terminal Acetylenes, Lei A W etc., have carried out dynamics research to Pd catalysis Cadiot-Chodkiewicz cross-coupling reaction in 2012, use Pd (OAc)
2, TBAB, CuI catalyst system, iPr
2nH makes solvent, obtains higher yield 52 ~ 99%, but still there is Terminal Acetylenes and need first halogenation, use the problems such as a large amount of amine.In order to develop a kind of method of directly being synthesized asymmetric conjugation diyne compounds by Terminal Acetylenes, Shi X D etc., propose the linked reaction of Au catalysis Terminal Acetylenes, catalyst system is dppm (AuBr)
2(2.5mol%), Phen (10mol%), PhI (OAc)
2(2equiv), acetonitrile and Isosorbide-5-Nitrae dioxane make mixed solvent, yield 57 ~ 93%.Still exist in these methods and use excessive reaction substrate, the organic solvent that noble metal, use toxicity are larger and the shortcoming such as strong oxidizer, substrate narrow application range.In addition, although copper catalysis Glaser linked reaction has been found that nearly 150 years, it is only only applicable to same molecule linked reaction.It is applied to the research of synthesizing asymmetric conjugation diyne compounds and not yet makes a breakthrough.Therefore, the method developing easy synthesis asymmetric conjugation diyne compounds is extremely important.[reference: Glaser C.Ber.Dtsch.Chem.Ges.1869,2,422-424; Glaser, C.Ann.Chem.Pharm.1870,154,137-171; Tang J Y, Jiang H F, Deng G H, Zhou L.Chin.J.Org.Chem.2005,25,1503-1507; Annabelle L K, Shun S, Tykwinski R R.Angew.Chem.Int.Ed.2006,45,1034-1057; Yin W Y, He C, Chen M, Zhang H, Lei A W.Org.Lett.2009,11,709-712; Weng Y, Cheng B, He C, Lei A W.Angew.Chem.Int.Ed.2012,51,9547-9551; Peng H H, Xi Y M, Ronaghi N, Dong B L, Akhmedov N G, Shi X D.J.Am.Chem.Soc.2014,136,13174-13177.]
For the deficiency of aforesaid method, application copper cheap and easy to get to be catalyzer and air be oxygenant, simple to operate, the synthesis new way of asymmetric conjugation diyne compounds applied widely, has huge application prospect.
[summary of the invention]
The object of the invention is to develop and a kind ofly use copper cheap and easy to get for catalyzer, the terminal alkyne cross-coupling reaction that catalysis two kinds is different, highly selective and high productivity synthesize the method for asymmetric conjugation diyne compounds.
Goal of the invention of the present invention is achieved by the following technical solution:
A kind of structural formula is
the synthetic method of asymmetric conjugation diyne compounds, comprise following steps:
The mixed solvent getting two kinds of different terminal alkyne compound, copper catalyst, TMEDA, trichloromethane and organic solvent compositions is placed in reaction vessel, mixing; Under agitation at 30 ~ 70 DEG C, react 4 ~ 16h, be cooled to room temperature after reaction terminates, with saturated ammonium chloride solution washing, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, and thick product, through pillar layer separation, obtains target product.
In described structural formula I, R
1aryl, fatty group; R
2aryl, fatty group.
In above-mentioned synthetic method, described α-benzoinoxime is selected from least one in copper powder, cuprous chloride, cuprous bromide, cupric chloride, Red copper oxide.
In above-mentioned synthetic method, described TMEDA, makes part.
In above-mentioned synthetic method, described terminal alkyne compound is selected from phenylacetylene, 3-methylbutynol-3,1-acetylene naphthalene, 4-ethynyl toluene, 4-fluorobenzene acetylene, 4-acetylenylbenzene methyl ether, 4-ethynyl cyanophenyl, 4-acetylenylaniline, 3-thiophene acetylene, cyclohexyl-acetylene, trimethylammonium ethynyl silicon, phenylformic acid alkynes propyl ester, benzyl proyl ether.
In above-mentioned synthetic method, in described reaction process, organic solvent used is selected from least one in methylene dichloride, N,N-dimethylacetamide (DMAc), Isosorbide-5-Nitrae-dioxane, 1,2-ethylene dichloride, tetrahydrofuran (THF), DMF.
In above-mentioned synthetic method, be at least trichloromethane in described mixed solvent.
In above-mentioned synthetic method, in described mixed solvent, the volume ratio of trichloromethane and organic solvent is [1:1] ~ [4:1].
In above-mentioned synthetic method, mol ratio in described reaction system between catalyzer, TMEDA, the first terminal alkyne compounds, the second terminal alkyne compounds is [0.01 ~ 0.5]: [0.1 ~ 1]: 1:[1.0 ~ 2.0], temperature of reaction is 30 ~ 70 DEG C, and the reaction times is 4 ~ 16h.
In above-mentioned synthetic method, the organic solvent in described extraction step is at least one in ethyl acetate, trichloromethane or methylene dichloride.
Experimentally result, provided by the present invention a kind of be the method that the different terminal alkyne cross-coupling reaction of catalyst two kinds synthesizes asymmetric conjugation diyne compounds by copper.The method has catalyzer and cheaper starting materials, gained target product is easily separated, productive rate is higher, reaction conditions is gentle, the safe and reliable feature such as easy to operate.Solve the problem that copper catalysis Ge Laze linked reaction can not be applied to cross-coupling reaction between alkynes first, avoiding the asymmetric conjugation diyne compounds of synthesis needs the pre-functionalization of alkynes, with high costs, complicated operation, is unfavorable for the problems such as suitability for industrialized production.
[Brief Description Of Drawings]
Fig. 1 is the reaction formula synthesizing asymmetric conjugation diyne compounds.
[embodiment]
Be described further synthetic method of the present invention below in conjunction with synthesis example of the present invention, it should be noted that, embodiment does not form the restriction to application claims protection domain.
As shown in Figure 1, the synthesis step of asymmetric conjugation diyne compounds provided by the invention is: the mixed solvent (volume ratio is [1:1] ~ [4:1]) that copper catalyst (mol ratio 1%-50% is based on the first terminal alkyne compounds), TMEDA (mol ratio 10%-100% is based on the first terminal alkyne compounds), the second terminal alkyne compounds (mol ratio 100%-200% is based on the first terminal alkyne compounds), trichloromethane and organic solvent form is placed in reaction vessel, mixing; Under agitation react 4 ~ 16 hours at 30 ~ 70 DEG C, be cooled to room temperature after reaction terminates, wash with saturated ammonium chloride solution, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, thick product, through pillar layer separation, obtains asymmetric conjugation diyne compounds.
Synthesis example 1
The synthesis of oneself-3,5-diine-2-alcohol of 2-methyl-6-phenyl
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 3-methylbutynol-3,0.28mmol phenylacetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 81%.
1H NMR(400MHz,CDCl
3,TMS):δ7.48-7.46(m,2H),7.35-7.30(m,3H),2.45(s,1H),1.58(s,6H).
Synthesis example 2
The synthesis of oneself-3,5-diine-2-alcohol of 2-methyl-6-(naphthalene-1-base)
Add the mixed solvent (volume ratio is [3:1]) of 0.02mmol copper powder, 0.04mmol TMEDA, 0.2mmol 3-methylbutynol-3,0.28mmol 1-acetylene naphthalene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 72%.
1H NMR(400MHz,CDCl
3,TMS):δ8.32(d,J＝8.3Hz,1H),7.85(d,J＝8.2Hz,2H),7.74(dd,J＝7.2,0.7Hz,1H),7.60-7.50(m,2H),7.43-7.39(m,1H),2.23(s,1H),1.63(s,6H).
Synthesis example 3
The synthesis of oneself-3,5-diine-2-alcohol of 2-methyl-6-(p-methylphenyl)
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.02mmol TMEDA, 0.2mmol 3-methylbutynol-3,0.28mmol 4-ethynyl toluene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 72%.
1H NMR(400MHz,CDCl
3,TMS):δ7.38(d,J＝8.1Hz,2H),7.12(d,J＝8.1Hz,2H),2.34(s,3H),2.28(s,1H),1.57(s,6H).
Synthesis example 4
The synthesis of oneself-3,5-diine-2-alcohol of 6-(4-fluorophenyl)-2-methyl
Add the mixed solvent (volume ratio is [1:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 3-methylbutynol-3,0.28mmol 4-fluorobenzene acetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 84%.
1H NMR(400MHz,CDCl
3,TMS):δ7.47(dd,J＝3.6,5.4Hz,2H),7.02(t,J＝6.6Hz,2H),2.33(s,1H),1.59(s,6H).
Synthesis example 5
The synthesis of oneself-3,5-diine-2-alcohol of 6-(4-aminophenyl)-2-methyl
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 3-methylbutynol-3,0.28mmol 4-acetylenylaniline, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 75%.
1H NMR(400MHz,CDCl
3,TMS):δ7.28(d,J＝8.5Hz,2H),6.58(d,J＝8.5Hz,2H),3.92(s,2H),2.40(s,1H),1.56(s,6H).
Synthesis example 6
The synthesis of oneself-3,5-diine-2-alcohol of 2-methyl-6-(thiene-3-yl-)
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 3-methylbutynol-3,0.26mmol 3-thiophene acetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 80%.
1H NMR(400MHz,CDCl
3,TMS):δ7.55(d,J＝2.0Hz,1H),7.26(t,J＝2.8Hz,1H),7.12(d,J＝3.6Hz,1H),2.17(s,1H),1.57(s,6H).
Synthesis example 7
The synthesis of 5-phenyl penta-2,4-diine-1-yl benzoic acid ester
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol phenylformic acid alkynes propyl ester, 0.28mmol phenylacetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 92%.
1H NMR(400MHz,CDCl
3,TMS):δ8.10-8.06(m,2H),7.59(t,J＝7.4Hz,1H),7.51-7.43(m,4H),7.40-7.29(m,3H),5.07(s,2H).
Synthesis example 8
The synthesis of trimethylammonium (phenyl fourth-1,3-diine-1-base) silane
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol trimethylammonium ethynyl silicon, 0.24mmol phenylacetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 62%.
1H NMR(400MHz,CDCl
3,TMS):δ7.49-7.47(m,2H),7.36-7.28(m,3H),0.23(s,9H).
Synthesis example 9
The synthesis of (cyclohexyl fourth-1,3-diine-1-base) benzene
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol cuprous chloride, 0.04mmol TMEDA, 0.2mmol cyclohexyl-acetylene, 0.28mmol phenylacetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 10h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 62%.
1H NMR(400MHz,CDCl
3,TMS):δ7.48-7.45(m,2H),7.34-7.27(m,3H),2.61-2.49(m,1H),1.89-1.78(m,2H),1.77-1.68(m,2H),1.52-1.46(m,2H),1.39-1.30(m,2H),1.28-1.25(m,2H).
Synthesis example 10
The synthesis of 4-(phenyl fourth-1,3-diine-1-base) cyanophenyl
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 4-ethynyl cyanophenyl, 0.28mmol phenylacetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 14h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 68%.
1H NMR(400MHz,CDCl
3,TMS):δ7.61(q,J＝8.4Hz,4H),7.54(d,J＝6.8Hz,2H),7.42-7.33(m,3H).
Synthesis example 11
The synthesis of 1-methoxyl group-4-(phenyl fourth-1,3-diine-1-base) benzene
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 4-acetylenylbenzene methyl ether, 0.28mmol phenylacetylene, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 10h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 72%.
1H NMR(400MHz,CDCl
3,TMS):δ7.52-7.45(m,4H),7.33-7.31(m,3H),6.84(d,J＝7.5Hz,2H),3.82(s, 3H).
Synthesis example 12
The synthesis of 7-(benzyloxy)-2-methyl diine-2 in heptan-3,5-alcohol
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 3-methylbutynol-3,0.28mmol benzyl proyl ether, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 8h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 75%.
1H NMR(400MHz,CDCl
3,TMS):δ7.35-7.31(m,5H),4.60(s,2H),4.24(s,2H),2.19(s,2H),1.54(s,6H).
Synthesis example 13
The synthesis of 4-((4-p-methoxy-phenyl) fourth-1,3 diine-1-base) aniline
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol 4-acetylenylbenzene methyl ether, 0.28mmol 4-acetylenylaniline, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 12h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 87%.
1H NMR(400MHz,CDCl
3,TMS):δ7.45(d,J＝8.6Hz,2H),7.32(d,J＝8.3Hz,2H),6.84(d,J＝8.6Hz,2H),6.59(d,J＝8.3Hz,2H),3.88(s,2H),3.81(s,3H).
Synthesis example 14
The synthesis of 4-(phenyl fourth-1,3-diine-1-base) aniline
Add the mixed solvent (volume ratio is [3:1]) of 0.01mmol copper powder, 0.04mmol TMEDA, 0.2mmol phenylacetylene, 0.28mmol 4-acetylenylaniline, 0.4mL chloroform and Isosorbide-5-Nitrae-dioxane composition in the reactor.Be heated to 50 DEG C, Keep agitation 10h, stopped reaction, is cooled to room temperature, adds saturated ammonium chloride solution washing, and with dichloromethane extraction, dry, underpressure distillation is except desolventizing, and namely thick product obtains target product through pillar layer separation, productive rate 84%.
1H NMR(400MHz,CDCl
3,TMS):δ7.51(d, J＝7.6 Hz,2H),7.41-7.28(m,5H),6.60(d,J＝8.3 Hz,2H),3.89(s,2H).
Claims (9)
1. a synthetic method for asymmetric conjugation diyne compounds, comprises following step:
The mixed solvent getting two kinds of different terminal alkyne compounds, copper catalyst, Tetramethyl Ethylene Diamine (TMEDA), trichloromethane and organic solvent composition is placed in reaction vessel, mixing; Under agitation at 30 ~ 70 DEG C, react 4 ~ 16h, be cooled to room temperature after reaction terminates, wash with saturated ammonium chloride solution, then use organic solvent extraction, dry, underpressure distillation is concentrated except desolventizing, thick product, through pillar layer separation, obtains asymmetric conjugation diyne compounds.There is following structural formula:
In described general formula I,
R
1aryl, fatty group;
R
2aryl, fatty group.
2. the synthetic method of asymmetric conjugation diyne compounds according to claim 1, it is characterized in that, described α-benzoinoxime is selected from least one in copper powder, cuprous chloride, cuprous bromide, cupric chloride, Red copper oxide.
3. the synthetic method of asymmetric conjugation diyne compounds according to claim 1, is characterized in that must having TMEDA, make part.
4. the synthetic method of asymmetric conjugation diyne compounds according to claim 1, it is characterized in that, described terminal alkyne compound is selected from phenylacetylene, 3-methylbutynol-3,1-acetylene naphthalene, 4-ethynyl toluene, 4-fluorobenzene acetylene, 4-acetylenylbenzene methyl ether, 4-ethynyl cyanophenyl, 4-acetylenylaniline, 3-thiophene acetylene, cyclohexyl-acetylene, trimethylammonium ethynyl silicon, phenylformic acid alkynes propyl ester, benzyl proyl ether.
5. the synthetic method of asymmetric conjugation diyne compound according to claim 1, it is characterized in that, in described reaction process, organic solvent used is selected from methylene dichloride, N, N-N,N-DIMETHYLACETAMIDE (DMAc), 1,4-dioxane, 1, at least one in 2-ethylene dichloride, tetrahydrofuran (THF), DMF.
6. the synthetic method of asymmetric conjugation diyne compounds according to claim 1, it is characterized in that, be at least trichloromethane in described mixed solvent.
7. the synthetic method of asymmetric conjugation diyne compounds according to claim 1, is characterized in that, in described mixed solvent, the volume ratio of trichloromethane and organic solvent is [1:1] ~ [4:1].
8. the synthetic method of asymmetric conjugation diyne compounds according to claim 1, it is characterized in that, mol ratio in described reaction system between copper catalyst, TMEDA, the first terminal alkyne compounds, the second terminal alkyne compounds is [0.01 ~ 0.5]: [0.1 ~ 1]: 1:[1.0 ~ 2.0], temperature of reaction is 30 ~ 70 DEG C, and the reaction times is 4 ~ 16h.
9. the synthetic method of asymmetric conjugation diyne compounds according to claim 1, it is characterized in that, the organic solvent in described extraction step is at least one in ethyl acetate, trichloromethane or methylene dichloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262112.9A CN105001028A (en) | 2015-05-21 | 2015-05-21 | Synthesis method for asymmetric conjugate diyne compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510262112.9A CN105001028A (en) | 2015-05-21 | 2015-05-21 | Synthesis method for asymmetric conjugate diyne compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105001028A true CN105001028A (en) | 2015-10-28 |
Family
ID=54373946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510262112.9A Pending CN105001028A (en) | 2015-05-21 | 2015-05-21 | Synthesis method for asymmetric conjugate diyne compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105001028A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419485A (en) * | 2015-12-23 | 2016-03-23 | 武汉威杜信息科技有限公司 | Anti-counterfeiting aqueous irreversible thermochromic printing ink and preparation method therefor |
| CN106631718A (en) * | 2016-12-12 | 2017-05-10 | 安徽师范大学 | Synthesis method of asymmetric conjugated diyne |
| CN109400496A (en) * | 2018-10-25 | 2019-03-01 | 宁波大学 | A kind of environment-friendly preparation method thereof of 1,3- diacetylene derivative |
| CN110078932A (en) * | 2019-04-23 | 2019-08-02 | 上海大学 | Chiral C3Supermolecule polymer and preparation method thereof |
| CN111068682A (en) * | 2019-12-27 | 2020-04-28 | 中国科学院青岛生物能源与过程研究所 | Biomass-based carbon material loaded monoatomic copper catalyst and preparation method and application thereof |
| CN113636904A (en) * | 2021-08-12 | 2021-11-12 | 浙江工业大学 | Green preparation method of conjugated diyne compound with participation of water-soluble vitamin E |
| CN114195610A (en) * | 2022-01-05 | 2022-03-18 | 海南大学 | Synthetic method of E-type internal olefin compound |
| CN114591198A (en) * | 2022-03-21 | 2022-06-07 | 江苏科技大学 | Preparation method of novel cyanoacetylene hydrocarbon compound |
| CN114957366A (en) * | 2021-12-17 | 2022-08-30 | 康龙化成(宁波)科技发展有限公司 | 1, 3-diyne lead compound and synthesis method thereof |
-
2015
- 2015-05-21 CN CN201510262112.9A patent/CN105001028A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| GUANGHUI ZHANG，ET AL.: "Direct Observation of Reduction of Cu(II) to Cu(I) by Terminal Alkynes", 《J.AM.CHEM.SOC.》 * |
| HSIN-YU HSIEH，ET AL.: "Discovery, Synthetic Methodology, and Biological Evaluation for Antiphotoaging Activity of Bicyclic[1,2,3]triazoles: In Vitro and in Vivo Studies", 《J.MED.CHEM.》 * |
| VALERIE T.TRIPP，ET AL.: "Development of Solid-Supported Glaser−Hay Couplings", 《ACS COMB.SCI.》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419485A (en) * | 2015-12-23 | 2016-03-23 | 武汉威杜信息科技有限公司 | Anti-counterfeiting aqueous irreversible thermochromic printing ink and preparation method therefor |
| CN105419485B (en) * | 2015-12-23 | 2018-07-13 | 武汉威杜信息科技有限公司 | False proof aqueous irreversible temperature sensitive ink of one kind and preparation method thereof |
| CN106631718A (en) * | 2016-12-12 | 2017-05-10 | 安徽师范大学 | Synthesis method of asymmetric conjugated diyne |
| CN109400496B (en) * | 2018-10-25 | 2021-04-06 | 宁波大学 | Preparation method of 1, 3-diacetylene derivative |
| CN109400496A (en) * | 2018-10-25 | 2019-03-01 | 宁波大学 | A kind of environment-friendly preparation method thereof of 1,3- diacetylene derivative |
| CN110078932A (en) * | 2019-04-23 | 2019-08-02 | 上海大学 | Chiral C3Supermolecule polymer and preparation method thereof |
| CN110078932B (en) * | 2019-04-23 | 2021-08-10 | 上海大学 | Chiral C3Supramolecular polymers and methods of making the same |
| CN111068682A (en) * | 2019-12-27 | 2020-04-28 | 中国科学院青岛生物能源与过程研究所 | Biomass-based carbon material loaded monoatomic copper catalyst and preparation method and application thereof |
| CN111068682B (en) * | 2019-12-27 | 2022-08-12 | 中国科学院青岛生物能源与过程研究所 | Biomass-based carbon material loaded monoatomic copper catalyst and preparation method and application thereof |
| CN113636904A (en) * | 2021-08-12 | 2021-11-12 | 浙江工业大学 | Green preparation method of conjugated diyne compound with participation of water-soluble vitamin E |
| CN114957366A (en) * | 2021-12-17 | 2022-08-30 | 康龙化成(宁波)科技发展有限公司 | 1, 3-diyne lead compound and synthesis method thereof |
| CN114957366B (en) * | 2021-12-17 | 2023-11-10 | 康龙化成(宁波)科技发展有限公司 | 1, 3-diacetylene lead compound and synthesis method thereof |
| CN114195610A (en) * | 2022-01-05 | 2022-03-18 | 海南大学 | Synthetic method of E-type internal olefin compound |
| CN114591198A (en) * | 2022-03-21 | 2022-06-07 | 江苏科技大学 | Preparation method of novel cyanoacetylene hydrocarbon compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105001028A (en) | Synthesis method for asymmetric conjugate diyne compound | |
| CN112961079B (en) | Method for dehydrating primary amide into nitriles by cobalt catalysis | |
| CN103224436A (en) | Preparation method of o-amino diaryl ketone compound | |
| CN105801575A (en) | Synthetic method of imidazo[1,2-a]pyridine | |
| CN111606849B (en) | Synthetic method of 2- (2-aminophenyl) quinoline compound | |
| CN107935925B (en) | Preparation method of polysubstituted phenanthridine compound | |
| CN105013535B (en) | A kind of catalyst and its synthetic method for preparing asymmetric conjugation diine hydrocarbon compound | |
| CN109400611B (en) | Synthesis method of 1-vinyl-4, 5-dihydropyrrole [1,2-a ] quinoxaline compound | |
| CN112920033A (en) | Preparation method of o-alkynyl phenylcyclobutanone and preparation method of naphthalenone | |
| CN113387886B (en) | 2-aminodibenzo [ c, e ] azepine compound and synthetic method thereof | |
| CN106966922B (en) | Synthesis method of functional substituted dicyanoethylene compound | |
| CN104817583A (en) | Carbon-bridged diacylamino rare earth amide and preparation thereof, and application of carbon-bridged diacylamino rare earth amide in catalysis of amidation of aldehyde and amine | |
| CN107814757A (en) | A kind of method for synthesizing polysubstituted pyrrole derivative | |
| CN110028448B (en) | Preparation method of 3-hydroxy-2,3-dihydroisoquinoline-1, 4-diketone compound | |
| Samzadeh-Kermani | Organocatalyst-Induced Multicomponent Reaction: An Efficient Procedure for the Activation of Amides | |
| CN109776546B (en) | Method for preparing indolopyrrolidone compound | |
| CN1386735A (en) | Process for condensating salicyladehyde with arylamine | |
| CN112010884A (en) | Synthesis method of phenyl (1-phenylethyl) silane | |
| CN106892866B (en) | 1, 2-disubstituted-4-quinolone and synthesis method thereof | |
| CN110746353A (en) | Aromatic compound and preparation method and application thereof | |
| CN109053556A (en) | Pyridyl group bridging-phenyl-amino pyridine compounds and their, complex and its synthesis and application | |
| CN112778352B (en) | Organosilicon compound and synthesis method thereof | |
| KR101578504B1 (en) | - Novel preparation method of quinoline -oxide derivative with amide group | |
| CN110981919B (en) | Method for synthesizing octatomic amidine cyclic palladium compound by one-pot method and application thereof | |
| CN109796372B (en) | Method for preparing polysubstituted alkenyl amidine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151028 |
|
| RJ01 | Rejection of invention patent application after publication |