CN104974008A - Novel method for catalytically synthesizing 1,3-diyne compound with simple, highly efficient and reusable copper catalytic system - Google Patents

Novel method for catalytically synthesizing 1,3-diyne compound with simple, highly efficient and reusable copper catalytic system Download PDF

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CN104974008A
CN104974008A CN201510306425.XA CN201510306425A CN104974008A CN 104974008 A CN104974008 A CN 104974008A CN 201510306425 A CN201510306425 A CN 201510306425A CN 104974008 A CN104974008 A CN 104974008A
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reaction
acetylene
synthetic method
phenylacetylene
luviset clear
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CN104974008B (en
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邱仁华
王正军
许新华
王爱军
王鹏辉
吕晶晶
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Hunan University
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Hunan University
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Abstract

The invention provides a novel method for catalyzing a terminal alkyne self-coupling reaction to produce a 1,3-diyne compound with a simple, highly efficient, alkali-free and reusable copper catalytic system. According to the invention, a commonly used organic solvent and water are adopted as a reaction solvent; a cheap and easy-to-obtain terminal alkyne is adopted as a raw material; and under the catalysis of a catalytic system composed of copper nitrate and Luviset Clear, a reaction is effectively carried out under a certain temperature, and the 1,3-diyne compound is prepared highly efficiently. Therefore, a green approach is provided for the preparation of the compound. The method mainly has the advantages of simple experimental operation, mild reaction conditions, and no alkali participation. The reaction is suitable for various different terminal alkynes, such that a raw material source range is wide. Copper nitrate with a low price is adopted as a reaction catalyst. With the catalyst, no other byproduct is produced, and the reaction is fast and highly efficient.

Description

A kind of easy, efficient, reusable copper catalyst system catalyzes and synthesizes the novel method of 1,3-bis-acetylene compound
[technical field]
The invention belongs to catalysis organic synthesis field, relate in particular to a kind of synthetic method of 1,3-bis-acetylene compound.
[background technology]
1,3-dialkynes derivative is present in occurring in nature in a large number, and their existence makes compound possess more excellent biological activity, such as antibacterial, antitumor, anticancer, AntiHIV1 RT activity or insecticidal properties.1,3-dialkyne is own to be extracted through the plant successfully from occurring in nature, fungi, bacterium, insect and marine organisms.1,3-dialkynes derivative (particularly synthesis of macromolecular cpd) in organic synthesis also has a wide range of applications, and they are the very highly active structure precursor of a class and reaction support.1,3-diine structure is also structure fragment indispensable in some functional materialss, and these functional materialss comprise polymkeric substance, liquid crystal, medicine, molecular wire and nonlinear molecule material etc.From Glaser since the synthesis of report 1,3-diyne in 1869, a large amount of novel methods has been had to be in the news out, especially in the majority with copper catalyst kind, comprising CuI, CuCl, CuBr, Cu (OAc) 2, CuC1 2, Cu (OH) 2and other supported copper catalyst etc.General copper catalysis end alkynes is in the system of coupling, and alkali is indispensable, and conventional has Et 3n, pyridine, TMEDA, KOH, K 2cO 3, Na 2cO 3deng.But, add alkali in the reaction and can accelerate reactor corrosion, and may environmental pollution be caused.There is certain theoretical and practical significance in the reaction of therefore developing alkali-free participation.
Copper has had as the classical catalyzer of catalysis end alkynes self-coupling reaction the history reaching more than 100 year so far, and along with continually developing of copper catalyst kind, its catalytic activity is also in continuous improvement.Still have now and be much in the news from the work of coupling as catalysis end alkynes about copper.Copper catalyst due to the advantage such as its low price, suitability be wide, simple and easy to get, and is extensively favored always.Therefore, develop that a kind of simple, efficient, alkali-free participates in, callable copper catalyst system catalysis end alkynes self-coupling reaction and still there is certain feasibility.
[summary of the invention]
The object of the invention is to carry out the novel method that catalysis end alkynes self-coupling reaction prepares 1,3-bis-acetylene compound, to improve productive rate and the speed of reaction of target product by developing that a kind of easy, efficient, alkali-free participates in, reusable copper catalyst system.
To achieve the above object of the invention, the present invention proposes following technical scheme:
A kind of method of synthesis 1,3-bis-acetylene compound makes reaction solvent with conventional organic solvent and water, be raw material with terminal alkyne, make catalyzer with cupric nitrate, with Luviset Clear for part, after reaction terminates, be separated to obtain 1,3-bis-acetylene compound through reverse preparative chromatography.
In above-mentioned synthetic method, described solvent is the one in methyl-sulphoxide, toluene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), DMF, acetone, ethanol, water.
In above-mentioned synthetic method, described copper catalyst is the one in cupric nitrate, cupric chloride, cupric bromide, copper sulfate, neutralized verdigris, cuprous iodide, cuprous bromide, cupric oxide.
In above-mentioned synthetic method, mole addition of described catalyzer is the consumption of 1-10%, Luviset Clear is 50-150mg.
In above-mentioned synthetic method, the preferred phenylacetylene of described raw material terminal alkyne, to methylbenzene acetylene, between methylbenzene acetylene, o-methyl-benzene acetylene, to Methoxy-phenylacetylene, 3-amino-benzene acetylene, to tert.-butylbenzene acetylene, to fluorobenzene acetylene, to trifluoromethyl phenylacetylene, 3-ethynyl pyridine, 3-thiophene acetylene, 3-phenoxy group-1-propine etc.
In above-mentioned synthetic method, the condition of described catalyzed reaction is: at 25-100 DEG C, react 0.5-5 hour.
Synthetic method provided by the present invention is that the preparation of 1,3-bis-acetylene compound opens new low cost " green " approach, and its advantage is: raw material sources are extensive, the selectivity of target product and productive rate are all higher, reaction conditions is gentle, and operation is easy, and wide application range of substrates is general.
[accompanying drawing explanation]
1,3-bis-acetylene compound synthesis path figure provided by the invention shown in accompanying drawing.
[embodiment]
Provided by the present inventionly catalyze and synthesize 1, the synthesis path of 3-bis-acetylene compound method, refer to accompanying drawing: insert in reaction vessel by raw material terminal alkyne, catalyzer and part etc., under the environment of 25-100 DEG C, react 0.5-5 hour after adding solvent, after having reacted, obtain target product through pillar layer separation.
Below in conjunction with concrete example of preparing, the present invention will be further described:
preparation example 1
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.01mmol, 50mg Luviset Clear and 2mL toluene, react 4h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 97%.
preparation example 2
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.10mmol, 150mg Luviset Clear and 2mL toluene, react and carry out 4h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 31%.
preparation example 3
1mmol phenylacetylene, Cu (OAc) is added in 10mL reaction tubes 20.02mmol, 86mg Luviset Clear and 2mL Isosorbide-5-Nitrae-dioxane, reacts and carry out 4h at 25 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 48%.
preparation example 4
1mmol phenylacetylene, CuCl is added in 10mL reaction tubes 20.05mmol, 76mg Luviset Clear and 2mL THF, carries out 4h at 100 DEG C.Reaction carries out 4h at 700 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 39%.
preparation example 5
In 10mL reaction tubes, add 1mmol phenylacetylene, CuO 0.07mmol, 126mg Luviset Clear and 2mL DMF, at 60 DEG C, carry out 4h.Reaction carries out 4h at 50 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 87%.
preparation example 6
1mmol phenylacetylene, Cu is added in 10mL reaction tubes 2i 0.03mmol, 96mg Luviset Clear and 2mL acetone, react and carry out 4h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 23%.
preparation example 7
In 10mL reaction tubes, add 1mmol phenylacetylene, CuBr 0.06mmol, 90mg Luviset Clear and 2mL ethanol, react and carry out 5h at 80 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 66%.
preparation example 8
In 10mL reaction tubes, add 1mmol phenylacetylene, CuBr 0.06mmol, 90mg Luviset Clear and 2mL ethanol, react and carry out 5h at 80 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 66%.
preparation example 9
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.03mmol, 96mg Luviset Clear and 2mL DMSO, carries out 4h at 25 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is extremely low.
preparation example 10
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.03mmol, 110mg Luviset Clear and 2mL DMF, carries out 5h at 40 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 27%.
preparation example 11
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.08mmol, 100mg Luviset Clear and 2mL DMSO, carries out 4h at 60 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 83%.
preparation example 12
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.03mmol, 96mg Luviset Clear and 2mL DMSO, carries out 4h at 80 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 86%.
preparation example 13
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.03mmol, 96mg Luviset Clear and 2mL Isosorbide-5-Nitrae-dioxane, carries out 0.5h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is extremely low.
preparation example 14
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.03mmol, 96mg Luviset Clear and 2mL DMSO, carries out 1h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 34%.
preparation example 15
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.03mmol, 56mg Luviset Clear and 2mL DMSO, carries out 4h at 30 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 46%
preparation example 16
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.05mmol, 96mg Luviset Clear and 2mL DMSO, carries out 4h at 90 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 73%
preparation example 17
1mmol phenylacetylene, Cu (SO is added in 10mL reaction tubes 4) 20.30mmol, 96mg Luviset Clear and 2mL H 2o, reacts and carry out 0.5h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 64%.
preparation example 18
1mmol phenylacetylene, CuBr is added in 10mL reaction tubes 20.30mmol, 96mg Luviset Clear and 2mL H 2o, reacts and carry out 0.5h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 59%.
preparation example 19
1mmol phenylacetylene, Cu (NO is added in 10mL reaction tubes 3) 20.03mmol, 96mg LuvisetClear and 2mL DMSO, carries out 5h at 100 DEG C.After reaction terminates, filter, concentrated, obtain Isosorbide-5-Nitrae-phenylbenzene-1,3-diacetylene through pillar layer separation, productive rate is 97%
The above embodiment only lists several concrete implementation method of the present invention, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (6)

1. the present invention is that a kind of novel copper catalyst system catalyzes and synthesizes 1, the method of 3-diyne compounds, it is characterized in that, with the catalyst system that copper catalyst and water-soluble Luviset Clear cheap and easy to get form, make reaction solvent with conventional organic solvent, reaction is effectively carried out at a certain temperature, obtains 1 expeditiously, 3-diyne compounds, and catalytic reaction system can repeatedly use.Here is the structure of Luviset Clear:
。
2. synthetic method according to claim 1, is characterized in that, described solvent is the one in methyl-sulphoxide, toluene, Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), DMF, acetone, ethanol, water.
3. synthetic method according to claim 1, is characterized in that, described copper catalyst is the one in cupric nitrate, cupric chloride, cupric bromide, copper sulfate, neutralized verdigris, cuprous iodide, cuprous bromide, cupric oxide.
4. synthetic method according to claim 1, is characterized in that, the consumption of copper catalyst is having used as 50-150mg of 1-10%, Luviset Clear.
5. synthetic method according to claim 1, it is characterized in that, the preferred phenylacetylene of described raw material terminal alkyne, to methylbenzene acetylene, between methylbenzene acetylene, o-methyl-benzene acetylene, to Methoxy-phenylacetylene, 3-amino-benzene acetylene, to tert.-butylbenzene acetylene, to fluorobenzene acetylene, to trifluoromethyl phenylacetylene, 3-ethynyl pyridine, 3-thiophene acetylene, 3-phenoxy group-1-propine etc.
6. synthetic method according to claim 1, is characterized in that, the condition of described catalyzed reaction is: at 25-100 DEG C, react 0.5-5h.
CN201510306425.XA 2015-06-02 2015-06-02 A kind of method that easy, efficient, reusable copper catalyst system catalyzes and synthesizes 1,3-, bis- acetylene compound Active CN104974008B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107513003A (en) * 2017-08-16 2017-12-26 佛山煜新科技有限公司 A kind of preparation method of 1,4 2 substitution, 1,3 diacetylene
CN115073259A (en) * 2022-06-20 2022-09-20 常州大学 Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof
CN115536484A (en) * 2022-09-26 2022-12-30 常州大学 Green preparation method of 1,4-diphenyl diacetylene

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CN102146015A (en) * 2011-03-02 2011-08-10 同济大学 1,3 conjugated diyne compound and preparation method thereof

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RAJU SINGHA ET AL.: "Transition metal free synthesis of 2,4,6-trisubstitutedpyrimidines via Cope-type hydroamination of 1,4-diarylbuta-1,3-diynes", 《RSC ADV.》 *
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107513003A (en) * 2017-08-16 2017-12-26 佛山煜新科技有限公司 A kind of preparation method of 1,4 2 substitution, 1,3 diacetylene
CN115073259A (en) * 2022-06-20 2022-09-20 常州大学 Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof
CN115073259B (en) * 2022-06-20 2023-09-29 常州大学 Preparation method for synthesizing 1, 4-diphenyl-1, 3-diacetylene or derivatives thereof
CN115536484A (en) * 2022-09-26 2022-12-30 常州大学 Green preparation method of 1,4-diphenyl diacetylene
CN115536484B (en) * 2022-09-26 2024-04-30 常州大学 Green preparation method of 1, 4-diphenyl diacetylene

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