CN106032370B - A kind of preparation method of ring-type (1,3)-dithiolan derivatives object - Google Patents
A kind of preparation method of ring-type (1,3)-dithiolan derivatives object Download PDFInfo
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- CN106032370B CN106032370B CN201510101559.8A CN201510101559A CN106032370B CN 106032370 B CN106032370 B CN 106032370B CN 201510101559 A CN201510101559 A CN 201510101559A CN 106032370 B CN106032370 B CN 106032370B
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- TVOYKFMCMIOKGR-UHFFFAOYSA-N N#CC(c(cc1)ccc1[N+]([O-])=O)=C1SCCS1 Chemical compound N#CC(c(cc1)ccc1[N+]([O-])=O)=C1SCCS1 TVOYKFMCMIOKGR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a kind of cyclic annular (1,3) preparation method of dithiolan derivatives object is raw material using trithiocarbonic acid vinyl acetate and active methylene compound, under the catalysis of imidazole acetate ionic liquid, it is synthetically prepared to obtain cyclic annular (1,3) dithiolan derivatives object.It is catalyst that ionic liquid is used in the method for the present invention, and reaction condition is mild, and operation is simple and safe, achieves high conversion ratio and yield, has prodigious application value in the synthesis of similar sulfur heterocyclic compound.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to the preparation side of cyclic annular (1,3)-dithiolan derivatives object
Method.
Background technology
Cyclic annular (1,3)-dithiolan derivatives object is a kind of very important sulfur heterocyclic compound, is had in multiple fields
Important application can be used as food additives in field of food, it can be used as major pharmaceutical component in pharmaceutical science, and
Material Field can be as critically important thermo-sensitive material.Therefore it is of great significance about its synthesis, in the past few decades
In cause extensive concern.In document report, the preparation of this kind of cyclic annular (1,3)-dithiolan derivatives object mainly have with
Lower 3 kinds of methods：
(1) active methylene compound and carbon disulfide are in sodium hydroxide, potassium hydroxide or sodium ethoxide this quasi-alkali
Salt is first generated under effect, is then added halogenated alkane the reaction was continued and generate corresponding cyclic annular (1,3)-dithiolan derivatives object
(K.A.Jensen, L.Henriksen.Acta Chem Sca, 1968,1107-1128), as shown in following equation (1)：
(2) under the collective effect of potassium fluoride and alundum (Al2O3), active methylene compound, carbon disulfide and dibromo second
Alkane be obtained by the reaction cyclic annular (1,3)-dithiolan derivatives object (V.Didier, B.A.Abdelkrim, Synthesis, 1991,
301-303), as shown in following equation (2)：
(3) under heavy metallic salt such as the collective effect of silver salt and mantoquita and organic base, trithiocarbonic acid vinyl acetate with it is active
Methylene compound carries out reaction and generates cyclic annular (1,3)-dithiolan derivatives object (S.Isao, K.Eisaku, Jpn.Kok Tok
Koh, 1995,07233096), as shown in following equation (3)：
Can be used in method made above it can be found that in these preparation methods carbon disulfide and Bromofume this
The dangerous control chemical substance of class severe toxicity, while solvent, heavy metallic salt and highly basic etc. can be largely used, these defects limit this
The study on the synthesis of class compound.
Invention content
The method of the present invention provides a kind of preparation method of cyclic annular (1,3)-dithiolan derivatives object.Due to the spy of ionic liquid
Different physics and chemical property can be used as catalyst or solvent to participate in a variety of green chemistry chemical technology productions, and the present invention is innovatively
It proposes and a kind of preparing cyclic annular (1,3)-dithiolan derivatives object using a small amount of imidazole acetate ionic liquid for catalyst
Method.
Preparation method of the present invention is raw material, imidazoles vinegar using trithiocarbonic acid vinyl acetate and active methylene compound
Hydrochlorate ionic liquid is catalyst, and under nitrogen protection, heating is obtained by the reaction cyclic annular (1,3)-dithiolane shown in formula (2) and spreads out
Biology.
Wherein, R1Including CN or COMe；R2Including COOEt, CN, COMe, COOMe or 4-NO2-Ph。
The reaction of preparation method of the present invention is as shown below：
Wherein, R1Including CN or COMe；R2Including COOEt, CN, COMe, COOMe, COOEt or 4-NO2-Ph。
Preferably, cyclic annular (1, the 3)-dithiolan derivatives object of the present invention include hereinafter,
a:R1=CN, R2=COOEt,
b:R1=CN, R2=CN,
c:R1=COMe, R2=COMe,
d:R1=CN, R2=COOMe,
e:R1=COMe, R2=COOEt and
f:R1=CN, R2=4-NO2-Ph。
In the present invention, the imidazole acetate ionic liquid catalyst be 1- butyl -3- methylimidazoles acetate from
Sub- liquid (BmimOAc) or 1- butyl -2,3- methylimidazole acetate ionic liquids (BmmimOAc).
In the present invention, the active methylene compound be ethyl cyanoacetate, methyl cyanoacetate, the third two eyeballs, acetylacetone,2,4-pentanedione,
Ethyl acetoacetate or para orientation nitration.
The amount ratio of the substance of the trithiocarbonic acid vinyl acetate and active methylene compound is 1: 1~1: 5.It is preferred that compare
Example is 1: 4.
In the present invention, the catalytic amount of the imidazole acetate ionic liquid is opposite trithiocarbonic acid vinyl acetate substance
Amount 1%~20%.Preferable amount is 10%.
In the present invention, reaction carries out under nitrogen protection.
In the present invention, reaction can have solvent or it is solvent-free under the conditions of carry out.It is preferred that not using solvent.Using solvent
When, it can select any in DMF, DMSO, toluene, paraxylene, dioxane or ethylene glycol monomethyl ether, be obtained in different solvents
Similar reaction result.
In the present invention, reaction temperature is 0~120 DEG C.Preferable reaction temperature is 110 DEG C.
In the present invention, the reaction time is 0.25~3h.Preferred reaction time is 1h.
In the present invention, the separation of product circular (1,3)-dithiolan derivatives object is implemented in a manner of column chromatography chromatogram.
The present invention also proposes ring-type (the 1,3)-dithiolan derivatives object being prepared as stated above.
It is raw material that trithiocarbonic acid vinyl acetate is used in the method for the present invention, is a kind of industrial products being easy to get safely, phase
For using carbon disulfide and the dangerous hypertoxic raw material tool of this one kind of Bromofume to have great advantage, not only make reaction safer, together
When also reaction process is made more to be simple and efficient.During the reaction, use the ionic liquid of catalytic amount as catalyst in the present invention,
It is the novel side reported for the first time for preparing the reaction of cyclic annular (1,3)-dithiolan derivatives object by active methylene compound
Method.Such as sodium hydroxide, potassium hydroxide, sodium ethoxide or heavy metallic salt such as silver salt and mantoquita are used during prior art preparation more
Reaction is directly participated in, with this comparison, the present invention is made catalyst using ionic liquid and reacted with using highly basic or heavy metallic salt participation
Mechanism is different, and the dosage of ionic liquid is less, and catalytic activity is high, achieves high conversion ratio and yield, simplifies reaction process
Pollution is decreased simultaneously, has important application value in the synthesis of similar sulfur heterocyclic compound.
Specific implementation mode
Following embodiment can be used to that present invention be described in more detail, but be not intended to limit the present invention.The guarantor of the present invention
Shield content is not limited to following embodiments.Without departing from the spirit and scope of the invention, those skilled in the art can think
To variation and advantage be all included in the present invention, and using appended claims as protection domain
In a specific embodiment, in the method for the present invention, the use of nitrogen is protective gas, imidazoles acetate is added
Ionic liquid is catalyst, and trithiocarbonic acid vinyl acetate and active methylene compound are reaction raw materials, and oil bath heating is to 110 DEG C
After react 1h, the use of mesitylene is internal standard, passes through GC analyses and calculate yield and conversion ratio.In the methods of the invention, product point
It is carried out from by carrying out column chromatography chromatogram separation to reaction mixture after reaction.
Embodiment 1：1- butyl -3- methylimidazoles acetate ionic liquids (BmimOAc) are catalyzed trithiocarbonic acid ethylene
Ester and ethyl cyanoacetate reaction prepare cyano-(1,3)-dithiolane -2- subunit ethyl acetate
40mg (0.2mmol) 1- butyl -3- first is added under nitrogen protection in the 50mL twoport flasks with magnetic agitation
Base imidazole acetate ionic liquid (BmimOAc), 0.27g (2mmol) trithiocarbonic acid vinyl acetates and 0.9g (8mmol) cyanogen second
Acetoacetic ester (1a), reacts 1h after being heated to 110 DEG C.Obtain product cyano-(1,3)-dithiolane -2- subunit ethyl acetate
(2a), gas chromatographic analysis (GC) conversion ratio 93%, gas chromatographic analysis (GC) yield 84%.Structure is determined through nuclear magnetic resonance.1H NMR(400MHz；CDCl3；TMS):δ=4.26~4.31 (m, 2H), 3.54~3.63 (m, 4H), 1.34 (t, J=8.0Hz,
3H).13C NMR(400MHz；CDCl3；TMS):δ=183.6,163.1,115.9,89.8,61.9,40.4,37.3,14.2.
Embodiment 2：1- butyl -2,3- methylimidazoles acetate ionic liquids (BmmimOAc) are catalyzed trithiocarbonic acid
Vinyl acetate and ethyl cyanoacetate reaction prepare cyano-(1,3)-dithiolane -2- subunit ethyl acetate
42mg (0.2mmol) 1- butyl -2,3- is added under nitrogen protection in the 50mL twoport flasks with magnetic agitation
Methylimidazole acetate ionic liquid (BmmimOAc), 0.27g (2mmol) trithiocarbonic acid vinyl acetates and 0.9g
(8mmol) ethyl cyanoacetate (1a), reacts 1h after being heated to 110 DEG C.Obtain product cyano-(1,3)-dithiolane -2- subunits
Ethyl acetate (2a), gas chromatographic analysis (GC) conversion ratio 93%, gas chromatographic analysis (GC) yield 62%.Structure is total through nuclear-magnetism
It shakes determination.1H NMR(400MHz；CDCl3；TMS):δ=4.26~4.31 (m, 2H), 3.54~3.63 (m, 4H), 1.34 (t, J
=8.0Hz, 3H)13C NMR(400MHz；CDCl3；TMS):δ=183.6,163.1,115.9,89.8,61.9,40.4,
37.3,14.2.
Embodiment 3：1- butyl -3- methylimidazoles acetate ionic liquids (BmimOAc) are catalyzed trithiocarbonic acid ethylene
Ester and methyl cyanoacetate reaction prepare cyano-(1,3)-dithiolane -2- subunit methyl acetates
40mg (0.2mmol) 1- butyl -3- first is added under nitrogen protection in the 50mL twoport flasks with magnetic agitation
Base imidazole acetate ionic liquid (BmimOAc), 0.27g (2mmol) trithiocarbonic acid vinyl acetates and 0.79g (8mmol) cyanogen
Methyl acetate (1b), reacts 1h after being heated to 110 DEG C.Obtain product cyano-(1,3)-dithiolane -2- subunit methyl acetates
(2b), gas chromatographic analysis (GC) conversion ratio 82%, gas chromatographic analysis (GC) yield 74%.Structure is determined through nuclear magnetic resonance.1H NMR(400MHz；CDCl3；TMS):δ=3.83 (s, 3H), 3.57~3.62 (m, 4H)13C NMR(400MHz；CDCl3；
TMS):δ=184.1,163.6,115.9,89.3,52.6,40.4,37.4.
Embodiment 4：1- butyl -3- methylimidazoles acetate ionic liquids (BmimOAc) are catalyzed trithiocarbonic acid ethylene
Ester and the reaction of the third two eyeballs prepare 2- (1,3- dithiolane -2- subunits)-malononitrile
40mg (0.2mmol) 1- butyl -3- first is added under nitrogen protection in the 50mL twoport flasks with magnetic agitation
Base imidazole acetate ionic liquid (BmimOAc), 0.27g (2mmol) trithiocarbonic acid vinyl acetates and 0.53g (8mmol) third
Two eyeballs (1c), react 1h after being heated to 110 DEG C.Obtain product 2- (1,3- dithiolane -2- subunits)-malononitrile (2c), gas phase
Chromatography (GC) conversion ratio 70%, gas chromatographic analysis (GC) yield 54%.Structure is determined through nuclear magnetic resonance.1H NMR
(400MHz；CDCl3；TMS):δ=3.79 (s, 4H)13C NMR(400MHz；CDCl3；TMS):δ=187.6,112.9,
68.9,40.8.
Embodiment 5：1- butyl -3- methylimidazoles acetate ionic liquids (BmimOAc) are catalyzed trithiocarbonic acid ethylene
Ester and ethyl acetoacetate reaction prepare 2- (1,3- dithiolane -2- subunits)-ethyl acetoacetate
40mg (0.2mmol) 1- butyl -3- first is added under nitrogen protection in the 50mL twoport flasks with magnetic agitation
Base imidazole acetate ionic liquid (BmimOAc), 0.27g (2mmol) trithiocarbonic acid vinyl acetates and 1.04g (8mmol) second
Ethyl acetoacetic acid ethyl ester (1d), reacts 1h after being heated to 110 DEG C.Obtain product 2- (1,3- dithiolane -2- subunits)-acetoacetate second
Ester (2d), gas chromatographic analysis (GC) conversion ratio 35%, gas chromatographic analysis (GC) yield 26%.Structure is true through nuclear magnetic resonance
It is fixed.1H NMR(400MHz；CDCl3；TMS):δ=4.31~4.36 (m, 2H), 3.33 (s, 4H), 2.43 (s, 3H), 1.37 (t, J
=8Hz, 3H)13C NMR(400MHz；CDCl3；TMS):δ=194.2,179.8,166.4,118.7,61.2,37.8,36.9,
30.22,14.27.
Embodiment 6：1- butyl -3- methylimidazoles acetate ionic liquids (BmimOAc) are catalyzed trithiocarbonic acid ethylene
Ester and acetylacetone,2,4-pentanedione reaction prepare 3- (1,3- dithiolane -2- subunits)-acetylacetone,2,4-pentanedione
40mg (0.2mmol) 1- butyl -3- first is added under nitrogen protection in the 50mL twoport flasks with magnetic agitation
Base imidazole acetate ionic liquid (BmimOAc), 0.27g (2mmol) trithiocarbonic acid vinyl acetates and 0.8g (8mmol) acetyl
Acetone (1e), reacts 1h after being heated to 110 DEG C.Obtain product 3- (1,3- dithiolane -2- subunits)-acetylacetone,2,4-pentanedione (2e), gas
Analysis of hplc (GC) conversion ratio 43%, gas chromatographic analysis (GC) yield 18%.Structure is determined through nuclear magnetic resonance.1H NMR
(400MHz；CDCl3；TMS):δ=3.34 (s, 4H), 2.44 (s, 6H)13C NMR(400MHz；CDCl3；TMS):δ=
194.7,173.9,128.1,36.1,29.2,28.7.
Embodiment 7：1- butyl -3- methylimidazoles acetate ionic liquids (BmimOAc) are catalyzed trithiocarbonic acid ethylene
Ester and para orientation nitration reaction prepare α -1,3- dithiolane -2- subunit -4- nitrobenzene ethane nitriles
40mg (0.2mmol) 1- butyl -3- first is added under nitrogen protection in the 50mL twoport flasks with magnetic agitation
Base imidazole acetate ionic liquid (BmimOAc), 0.27g (2mmol) trithiocarbonic acid vinyl acetates and 1.3g (8mmol) are to nitre
Base benzene acetonitrile (1f), 10ml DMF react 1h after being heated to 110 DEG C.Pillar layer separation obtains product α -1,3- dithiolane -2-
Subunit -4- nitrobenzene ethane nitriles (2f) 0.053g detaches yield 10%.Structure is determined through nuclear magnetic resonance.1H NMR(400MHz；
DMSO；TMS):δ=8.31 (d, J=8Hz, 2H), 7.76 (d, J=8Hz, 2H), 3.75~3.85 (m, 4H)13C NMR
(400MHz；DMSO；TMS):δ=169.4,145.8,140.5,127.9,124.2,118.1,93.9,41.1,38.1.
Claims (8)
1. a kind of preparation method of ring-type (1,3)-dithiolan derivatives object, which is characterized in that with trithiocarbonic acid vinyl acetate and
Active methylene compound is raw material, and imidazole acetate ionic liquid is catalyst, and under nitrogen protection, heating is obtained by the reaction
Cyclic annular (1,3)-dithiolan derivatives object；It reacts as shown below：
Wherein, R1Including CN or COMe；R2Including COOEt, CN, COMe, COOMe or 4-NO2-Ph。
2. method as claimed in claim 1, which is characterized in that the imidazole acetate ionic liquid is 1- butyl -3- methyl miaows
Azoles acetate ionic liquid or 1- butyl -2,3- methylimidazole acetate ionic liquids.
3. method as claimed in claim 1, which is characterized in that the active methylene compound is ethyl cyanoacetate, cyanoacetic acid first
Ester, malononitrile, acetylacetone,2,4-pentanedione, ethyl acetoacetate or para orientation nitration.
4. method as claimed in claim 1, which is characterized in that the object of the trithiocarbonic acid vinyl acetate and active methylene compound
The amount ratio of matter is 1: 1~1: 5.
5. method as claimed in claim 1, which is characterized in that the catalytic amount of the imidazole acetate ionic liquid is opposite three
The 1%~20% of the amount of ethylene ester substance.
6. method as claimed in claim 1, which is characterized in that reaction have solvent or it is solvent-free under the conditions of carry out.
7. method as claimed in claim 1, which is characterized in that reaction temperature is 0~120 DEG C, and the reaction time is 0.25~3h.
8. method as claimed in claim 1, which is characterized in that the separation of product circular (1,3)-dithiolan derivatives object is with column chromatography
The mode of chromatography is implemented.
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| JPH05310730A (en) * | 1992-04-07 | 1993-11-22 | Agency Of Ind Science & Technol | Production of 2-@(3754/24)disubstituted methylene)-1,3-dithiol compound |
| JP2005274693A (en) * | 2004-03-23 | 2005-10-06 | Konica Minolta Medical & Graphic Inc | Heat developable photographic sensitive material |
| CN1687058A (en) * | 2005-04-26 | 2005-10-26 | 东北师范大学 | Method for synthesizing organic sulfur compound under condition without solvent |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05310730A (en) * | 1992-04-07 | 1993-11-22 | Agency Of Ind Science & Technol | Production of 2-@(3754/24)disubstituted methylene)-1,3-dithiol compound |
| JP2005274693A (en) * | 2004-03-23 | 2005-10-06 | Konica Minolta Medical & Graphic Inc | Heat developable photographic sensitive material |
| CN1687058A (en) * | 2005-04-26 | 2005-10-26 | 东北师范大学 | Method for synthesizing organic sulfur compound under condition without solvent |
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| Heterocyclic substituted arenediazonium salts with a long wavelength range of sensitivity-Part I.Monomethines and azamethines;Fanghaenel, E.等;《Journal fuer Praktische Chemie (Leipzig)》;19881231;第330卷(第4期);第592页方案3 * |
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