CN104710254A - Preparation method of symmetric 1,4-disubstituted-1,3-diacetylene - Google Patents
Preparation method of symmetric 1,4-disubstituted-1,3-diacetylene Download PDFInfo
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- CN104710254A CN104710254A CN201510033947.7A CN201510033947A CN104710254A CN 104710254 A CN104710254 A CN 104710254A CN 201510033947 A CN201510033947 A CN 201510033947A CN 104710254 A CN104710254 A CN 104710254A
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- acetylene
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Abstract
The invention discloses a preparation method of symmetric 1,4-disubstituted-1,3-diacetylene. Homocoupling of alkyne is carried out in a solvent in the presence of an alkali with silver as a catalyst to obtain the symmetric 1,4-disubstituted-1,3-diacetylene. The method has the advantages of simple operation, obtaining of corresponding diacetylene compounds at room temperature without air isolation or addition of a phosphine ligand or a precious metal, simple post-treatment, and very good practicality and economic values.
Description
Technical field
The invention belongs to the field of chemical synthesis, the alkynes relating to a kind of silver-colored catalysis prepares the preparation method of symmetry Isosorbide-5-Nitrae-two replacement-1,3-diacetylene.
Background technology
It is the special compound of a class formation that Isosorbide-5-Nitrae-two replaces-1,3-diacetylene.From space structure, it comprises the carbon atom of four sp hydridization, and four carbon atom linearly arranges, and one-piece construction presents certain rigidity; Can conjugated structure be formed between two three keys, therefore be also referred to as conjugation diine.Conjugation diine itself is present in many natural compoundss, and its structure is common in natural product, antifungal drug, can also as the precursor of some dyestuff; Usually be applied in organic synthesis as the omnipotent module building molecule, in building-up reactions, conjugation diine can be used as multi-functional Equivalent perhaps; The structure of its rigidity, conjugation all comprises it in many novel organic functional materials also becomes core functional group in the synthesis of nanometer organic molecule material.This kind of diine also shows bright dipping and to live the characteristic of desinsection to also have recently report to find, is that the ecological light of the potential high-efficiency low-toxicity of a class is lived the key structure of agricultural chemicals.
The method and mechanism etc. that have had many sections of international and domestic academic papers to discuss the coupling of terminal alkyne autoxidation to prepare diine, relating to multiple fields such as organometallic catalytic, oxidative coupling, Green Chemistry, study mechanism, coordination chemistry, is a typical research topic.But agents useful for same is as expensive in the phosphine composition of trimethyl silicane alkynes, palladium etc., toxicity is large, and reaction needs several auxiliary reagent mostly, and reaction cost is high, and complex operation aftertreatment complex environment pollutes large.
Along with the development of transition-metal catalysis research, stoichiometric silver often by as auxiliary agent to improve metal ion reactive behavior (as palladium, ruthenium, rhodium etc.), and silver compound itself is very limited as the application of catalyzer.Recently, organic chemists utilize the σ of silver complex-and π-lewis acidity character to have studied the reaction of silver-colored catalysis, have found various chemical conversion, cover cycloaddition, cycloisomerisation, allylation, aldol reaction etc., and the research of asymmetric synthesis aspect also develops to some extent.The chemical reaction of silver catalysis has reaction conditions gentleness, catalyzer low price (current silver-colored price Jin Wei $4.19/ gram, 1/300 of not enough gold) etc. feature, therefore, the catalytic reaction exploring new silver complex is of great practical significance.
Silver catalyst participates in the characteristics and advantages that reaction has himself.Silver has the electroactive and lewis acidic character of high parent concurrently, can form silver-pi complex with pi-conjugated system by coordination, activation electrophilic reagent.Such silver-colored catalytic process have simple to operate, without the need to the feature such as isolated water and air, speed of reaction be fast, be a kind of regulatable reaction.Along with deepening continuously of research, the application of chemical reaction in organic synthesis of silver-colored catalysis is further extensive.The reaction research of nearest 2 years of silver catalysis mainly concentrates on ring and builds reaction, halogenating reaction, C-H functionalization and decarboxylic reaction.But still there is not the research of silver-colored catalysis terminal alkyne autoxidation coupling at present.
Summary of the invention
The present invention is directed to above shortcoming, provide a kind of alkynes of silver-colored catalysis to prepare the method for symmetry Isosorbide-5-Nitrae-two replacement-1,3-diacetylene, to reach simple to operate, aftertreatment is simple, object with low cost.
For achieving the above object, the present invention takes following technical proposals to realize:
A kind of symmetric Isosorbide-5-Nitrae-two replaces the preparation method of-1,3-diacetylene, adopts silver catalyst, and in the presence of base, alkynes in a solvent autoimmunity syndrome obtains symmetrical Isosorbide-5-Nitrae-two replacement-1,3-diacetylene.
Further, alkynes is phenylacetylene, to methylbenzene acetylene, between methylbenzene acetylene, o-methyl-benzene acetylene, between dimethyl benzene acetylene, adjacent dimethyl benzene acetylene, to Methoxy-phenylacetylene, O-methoxy phenylacetylene, meta-methoxy phenylacetylene, p-ethyl-phenylacetylene, to propylbenzene acetylene, to acetylbenzene acetylene, to fluorobenzene acetylene, to chlorobenzene acetylene, to bromobenzene acetylene, to iodobenzene acetylene, p-nitrophenylacetylene, 1-naphthalene acetylene, 2-naphthalene acetylene, 2 pyridine acetylene, cyclohexenyl acetylene, n-butyl-acetylene, n-hexyl acetylene, n-heptylacetylene, n-octyl acetylene, one in positive decyl acetylene.
Further, described silver catalyst is Silver Nitrate, Silver monoacetate, trifluoroacetic acid silver, one or more in trifluoro-methane sulfonic acid silver, and preferably, silver catalyst is Silver Nitrate.
Further, described alkali is one or more in sodium carbonate, salt of wormwood, sodium-acetate, Potassium ethanoate, preferably sodium carbonate.
Preferably, the consumption of silver catalyst is 1% of alkynes amount of substance.
Preferably, the consumption of alkali is 0.5 of alkynes amount of substance.
Further, solvent is acetonitrile, methyl-sulphoxide, DMF, N,N-dimethylacetamide, one or more in 1-Methyl-2-Pyrrolidone, and preferably, solvent is acetonitrile.
Preferably, temperature of reaction is 50 DEG C.
Preferably, the reaction times is 2 hours.
Under optimum condition, the present invention adopts acetonitrile to be solvent, and under the catalysis of Silver Nitrate, without the need to any part, without the need to the protection of rare gas element, aliphatics and aromatic series alkynes can obtain various different symmetry Isosorbide-5-Nitrae-two and replace-1,3-diacetylene compound.The equation reacting basic is:
In a word, beneficial effect of the present invention is:
No matter aliphatic or aromatic alkynes can react smoothly alkynes provided by the invention is by autoimmunity syndrome under silver-colored catalysis, and the Isosorbide-5-Nitrae-two that obtains of high yield replaces-1,3-diacetylene compound, has very high practicality and selectivity;
This reaction, without any need for the protection of rare gas element, can well be carried out in atmosphere;
This reaction can be carried out under 50 degree of conditions, and the reaction times is short, and reaction yield is high, no coupling product, just can obtain product through simple aftertreatment;
In the method, do not need to add Phosphine ligands as additive, only need the Silver Nitrate cheap and easy to get of catalytic amount (1%) as catalyzer, with low cost.
Embodiment
Describe the present invention below in conjunction with specific embodiment.
Embodiment 1
By 1mmol to Methoxy-phenylacetylene, 0.01mmol Silver Nitrate and 0.5mmol sodium carbonate add in the round-bottomed flask filling 1ml acetonitrile, under 50 degrees Celsius stir 2 hours.React complete filtering solid, after being spin-dried for solvent, post is separated and obtains product, productive rate 94%.
1H NMR(400MHz，CDCl
3，TMS)δ7.46(d，J＝8.4Hz，4H)，6.85(d，J＝8.8Hz，4H)，3.81(s，6H).
13C NMR(100MHz，CDCl
3)：δ160.3，134.1，114.2，113.8，81.3，72.8，55.3.HRMS calcd for C
18H
10O
2：262.0994，found：262.0997.
Embodiment 2
By 1mmol to acetylbenzene acetylene, 0.01mmol Silver Nitrate and 0.5mmol sodium carbonate add in the round-bottomed flask filling 1ml acetonitrile, under 50 degrees Celsius stir 2 hours.React complete filtering solid, after being spin-dried for solvent, post is separated and obtains product, productive rate 90%.
1H NMR(CDCl
3，400MHz)δ7.94(d，J＝8.4Hz，4H)7.62(d，J＝8.4Hz，4H)，2.62(s，6H).
13C NMR(100MHz，CDCl
3)：δ196.7，137.1，132.7，128.3，126.0，81.9，76.6，26.6.HRMS calcd for C
20H
14O
2：286.0994.found：286.0993.
Embodiment 3
By the 1-naphthalene acetylene of 1mmol, 0.01mmol Silver Nitrate and 0.5mmol sodium carbonate add in the round-bottomed flask filling 1ml acetonitrile, stir 2 hours under 50 degrees Celsius.React complete filtering solid, after being spin-dried for solvent, post is separated and obtains product, productive rate 89%.
1H NMR(CDCl
3，400MHz)δ8.44(d，J＝8.0Hz，2H)，7.82-7.92(m，6H)，7.43-7.68(m，6H).
13C NMR(100MHz，CDCl
3)：δ133.9，133.0，132.1，129.6，128.3，127.2，126.6，126.1，125.1，119.5，81.0，78.8.HRMS calcd for C
24H
14：302.11096，found：302.1092.
Embodiment 4
By the 2-pyridine acetylene of 1mmol, 0.01mmol Silver Nitrate and 0.5mmol sodium carbonate add in the round-bottomed flask filling 1ml acetonitrile, stir 2 hours under 50 degrees Celsius.React complete filtering solid, after being spin-dried for solvent, post is separated and obtains product, productive rate 86%.
1H NMR(400MHz，CDCl
3，TMS)δ8.62(d，J＝4.8Hz，2H)，7.68-7.73(m，2H)，7.55(d，J＝7.6Hz，2H)，7.30-7.33(m，2H).
13C NMR(100MHz，CDCl
3)：δ150.4，141.7，136.1，128.5，123.7，80.8，73.4.HRMS calcd for C
14H
8N
2：204.0687，found：204.0689.
Embodiment 5
By the 2-pyridine acetylene of 1mmol, 0.01mmol Silver Nitrate and 0.5mmol sodium carbonate add in the round-bottomed flask filling 1ml acetonitrile, stir 2 hours under 50 degrees Celsius.React complete filtering solid, after being spin-dried for solvent, post is separated and obtains product, productive rate 92%.
1H NMR(400MHz，CDCl
3，TMS)δ6.24-6.25(m，2H)，2.10-2.12(m，8H)，1.57-1.65(m，8H).
13C NMR(100MHz，CDCl
3)：δ136.8，134.3，130.3，129.3，126.5，121.7，79.5，78.3.HRMS calcd for C
16H
18：210.1409，found：210.1412.
Embodiment 6
By the positive decyl acetylene of 1mmol, 0.01mmol Silver Nitrate and 0.5mmol sodium carbonate add in the round-bottomed flask filling 1ml acetonitrile, stir 2 hours under 50 degrees Celsius.React complete filtering solid, after being spin-dried for solvent, post is separated and obtains product, productive rate 85%.
1H NMR(CDCl
3，200MHz)δ0.88(t，J＝6.2Hz，6H)，1.26-1.55(m，32H)，2.24(t，J＝6.8Hz，4H).
13C NMR(100MHz，CDCl
3)：δ77.5，65.2，31.8，29.7，29.5，29.3，29.1，28.8，28.3，22.7，19.3，14.0.HRMS calcd for C
24H
42：330.3287，found：330.3283.
Although the present invention with preferred embodiment openly as above; but it is not for limiting the present invention; any those skilled in the art without departing from the spirit and scope of the present invention; the Method and Technology content of above-mentioned announcement can be utilized to make possible variation and amendment to technical solution of the present invention; therefore; every content not departing from technical solution of the present invention; according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all belong to the protection domain of technical solution of the present invention.
Claims (10)
1. the preparation method of symmetric Isosorbide-5-Nitrae-two replacement-1, a 3-diacetylene, is characterized in that, adopt silver catalyst, and in the presence of base, alkynes in a solvent autoimmunity syndrome obtains symmetrical Isosorbide-5-Nitrae-two replacement-1,3-diacetylene.
2. preparation method according to claim 1, it is characterized in that, alkynes is phenylacetylene, to methylbenzene acetylene, between methylbenzene acetylene, o-methyl-benzene acetylene, between dimethyl benzene acetylene, adjacent dimethyl benzene acetylene, to Methoxy-phenylacetylene, O-methoxy phenylacetylene, meta-methoxy phenylacetylene, p-ethyl-phenylacetylene, to propylbenzene acetylene, to acetylbenzene acetylene, to fluorobenzene acetylene, to chlorobenzene acetylene, to bromobenzene acetylene, to iodobenzene acetylene, p-nitrophenylacetylene, 1-naphthalene acetylene, 2-naphthalene acetylene, 2-pyridine acetylene, cyclohexenyl acetylene, n-butyl-acetylene, n-hexyl acetylene, n-heptylacetylene, n-octyl acetylene, one in positive decyl acetylene.
3. preparation method according to claim 1, is characterized in that, described silver catalyst is Silver Nitrate, Silver monoacetate, trifluoroacetic acid silver, one or more in trifluoro-methane sulfonic acid silver.
4. preparation method according to claim 3, is characterized in that, described silver catalyst is Silver Nitrate.
5. preparation method according to claim 1, is characterized in that, described alkali is one or more in sodium carbonate, salt of wormwood, sodium-acetate, Potassium ethanoate.
6. preparation method according to claim 1, is characterized in that, the consumption of silver catalyst is 1% of alkynes amount of substance.
7. preparation method according to claim 1, is characterized in that, the consumption of alkali is 0.5 of alkynes amount of substance.
8. preparation method according to claim 1, is characterized in that, solvent is acetonitrile, methyl-sulphoxide, DMF, N,N-dimethylacetamide, one or more in 1-Methyl-2-Pyrrolidone.
9. preparation method according to claim 1, is characterized in that, temperature of reaction is 50 DEG C.
10. preparation method according to claim 1, is characterized in that, the reaction times is 2 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016947A (en) * | 2015-07-15 | 2015-11-04 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN108440228A (en) * | 2018-04-27 | 2018-08-24 | 郑州大学 | The complex-catalyzed molecular oxygen oxidation synthesis in water 1 of water-soluble transition metal, the method for 3- diacetylene class compounds |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009029890A (en) * | 2007-07-26 | 2009-02-12 | Nagoya Institute Of Technology | Diacetylene compound having fluorine-containing phthalocyanine moieties |
| CN101948365A (en) * | 2010-09-09 | 2011-01-19 | 同济大学 | Preparation method of 1,4-diaryl-1,3-butadiyne |
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009029890A (en) * | 2007-07-26 | 2009-02-12 | Nagoya Institute Of Technology | Diacetylene compound having fluorine-containing phthalocyanine moieties |
| CN101948365A (en) * | 2010-09-09 | 2011-01-19 | 同济大学 | Preparation method of 1,4-diaryl-1,3-butadiyne |
| CN102146015A (en) * | 2011-03-02 | 2011-08-10 | 同济大学 | 1,3 conjugated diyne compound and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016947A (en) * | 2015-07-15 | 2015-11-04 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN105016947B (en) * | 2015-07-15 | 2017-01-18 | 河南师范大学 | Method for synthesizing 1,3-butadiyne compound by copper (II) carboxymethylcellulose catalysis of terminal alkyne compound |
| CN108440228A (en) * | 2018-04-27 | 2018-08-24 | 郑州大学 | The complex-catalyzed molecular oxygen oxidation synthesis in water 1 of water-soluble transition metal, the method for 3- diacetylene class compounds |
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