CN105566285A - Method for preparing 5-methylthienyl-2-thiol from levulinic acid - Google Patents
Method for preparing 5-methylthienyl-2-thiol from levulinic acid Download PDFInfo
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- CN105566285A CN105566285A CN201610169913.5A CN201610169913A CN105566285A CN 105566285 A CN105566285 A CN 105566285A CN 201610169913 A CN201610169913 A CN 201610169913A CN 105566285 A CN105566285 A CN 105566285A
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- levulinic acid
- mercaptan
- thiotolene
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- 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
- C07D333/26—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 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 ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing 5-methylthienyl-2-thiol from levulinic acid, relating to thiophene compounds. The method comprises the following steps: adding levulinic acid into a solvent, and adding a Lawesson reagent to react; washing the product with an alkali, neutralizing 4-methoxyphenylphosphonic acid to obtain a salt, and transferring the salt into a water phase, wherein the target product 5-methylthienyl-2-thiol is retained in an organic phase and separated from the 4-methoxyphenylphosphonic acid; and carrying out reduced pressure distillation on the organic phase to obtain the 5-methylthienyl-2-thiol. The raw material reacts with the Lawesson reagent, and the 5-methylthienyl-2-thiol can be prepared by a cascade thionation-cyclization-isomerization process in one reaction procedure, so the steps are simple. The sodium carbonate or sodium bicarbonate solution is used for washing, so that the Lawesson reagent residue 4-methoxyphenylphosphonic acid can be effectively removed on the premise of not influencing the target product 5-methylthienyl-2-thiol. The obtained product has abundant reaction sites, such as aromatic thiophene rings, mercapto groups and the like, and has high plasticity.
Description
Technical field
The present invention relates to thiophenes, especially relate to a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid.
Background technology
Levulinic acid be a kind of can by lignocellulose in water through platform chemicals prepared by acid catalyzed degradation.
Chinese patent CN1762231A discloses a kind of preparation method of natural paste-form meat taste essence, the thiophene-based flavoring substance be wherein applied to is 3-thienyl mercaptan, 2-methyl-3-mercapto-thiophene, 2-methyl-3-sulfydryl-2,3-dihydro-thiophene, 2-methyl-4-sulfydryl-2,3-dihydro-thiophene or 2-methyl-4-sulfydryl-4,5-dihydro-thiophene.
Chinese patent CN104256499A discloses a kind of preparation method of chicken oily essence, is wherein applied to 2-methyl-3-furanthiol, 2-methyltetrahydrofuran-3-mercaptan as sweetener.
Chinese patent CN101074226A discloses the preparation method of a kind of dorzolamide hydrochloride intermediate 3-(thiophene-2-mercaptan) butyric acid, and one of them important intermediate is the grignard reagent of thiophene-2-mercaptan.
Chinese patent CN104803969A discloses a kind of acrylic type containing sulfo-sulfonate group high refractive index monomers and preparation method thereof, and wherein thiophene-2-mercaptan is one of raw material.
Chinese patent CN102881830A discloses a kind of organic solar batteries and preparation method thereof, wherein introduces mercapto-thiophene group for needing in the unimolecular film material of hole transmission layer.
At present, the thiophene-based chemical of industrial preparation all derives from fossil resource as oil etc.But, so far there are no preparing the relevant report of thiophenes as 5-thiotolene-2-mercaptan with biomass-based levulinic acid.
Summary of the invention
The object of the present invention is to provide low cost, high-level efficiency, a kind of continuable method being prepared 5-thiotolene-2-mercaptan by levulinic acid.
The present invention includes following steps:
1) levulinic acid is added in solvent, then add lawesson reagent reaction;
2) by step 1) products therefrom alkali cleaning, be transferred in aqueous phase by 4-methoxyphenyl phosphonic acids with salify, target product 5-thiotolene-2-mercaptan is retained in organic phase, and is separated with 4-methoxyphenyl phosphonic acids, and namely organic phase obtains 5-thiotolene-2-mercaptan through underpressure distillation.
In step 1) in, the proportioning of described levulinic acid and solvent can be (0.006 ~ 0.12) g: 1mL, and wherein, levulinic acid is calculated in mass, and solvent is calculated by volume; Described solvent can be selected from least one in toluene, dimethylbenzene, ethylbenzene etc., preferred toluene; The add-on of described lawesson reagent can be 0.5 ~ 3 of levulinic acid and solvent total amount in molar ratio; Described reaction can be reacted under 1bar nitrogen atmosphere or air atmosphere, and the temperature of reaction can be 90 DEG C ~ solvent boiling point, and the time of reaction can be 15min ~ 6h; In reaction process, lawesson reagent is converted into 4-methoxyphenyl phosphonic acids;
In step 2) in, described alkali cleaning can adopt sodium carbonate or sodium hydrogen carbonate solution washing, described sodium carbonate or sodium hydrogen carbonate solution can adopt mass percentage concentration be 3% ~ 10% sodium carbonate or sodium hydrogen carbonate solution, the consumption of described sodium carbonate or sodium hydrogen carbonate solution can be step 1 by volume) 1 ~ 3 times of products therefrom; The condition of described underpressure distillation can be: vacuum tightness 22torr, and temperature is 85 DEG C; The purity of gained 5-thiotolene-2-mercaptan can reach more than 95%.
Below provide the principle of reaction involved in the present invention:
Levulinic acid reacts with lawesson reagent in a solvent, carbonyl on No. four positions is generated unstable intermediate 4-thiocarbonyl group valeric acid by sulfo-, this intermediate experiences enolization-cyclization process at once and generates one-level thio product 5-methyl-2-ketone-(2,3)-dihydro-thiophene, 5-methyl-2-ketone-(2,5)-dihydro-thiophene.Can enol isomerization be there is 5-thiotolene-2-mercaptan be generated in No. two position carbonyls of two kinds of one-level thio product further with lawesson reagent generation thio reaction.Meanwhile, lawesson reagent is converted into 4-methoxyphenyl phosphonic acids, because 5-thiotolene-2-mercaptan is insoluble in water and acidity is better than carbonic acid, therefore can use sodium carbonate or sodium hydrogen carbonate solution washing removing 4-methoxyphenyl phosphonic acids.
The present invention take levulinic acid as raw material, can prepare also separating-purifying obtain 5-thiotolene-2-mercaptan through series connection thio reaction.In the industries such as this compound and more medicine, spices, conductive polymers, valuable thiophene-based raw material and intermediate have similar structure and properties, have great application potential.
Disclosed by the invention a kind of with biomass-based levulinic acid for the method that 5-thiotolene-2-mercaptan prepared by raw material has the advantage of low cost, high-level efficiency and sustainability.The present invention for raw material with lignocellulose base levulinic acid, generates 5-thiotolene-2-mercaptan through series connection thio reaction, is shown below under lawesson reagent effect.This process reaction mild condition, product yield is high, and separation and purification is simple, and products therefrom has high application potential in fields such as medicine, essence.
The invention has the advantages that:
The first, the present invention adopts the levulinic acid that can be transformed by biomass-based lignocellulose as raw material, has sustainability.
The second, raw material and lawesson reagent react, and can experience series connection sulfo--Cheng Huan-isomerization process and obtain 5-thiotolene-2-mercaptan in primary first-order equation, step is simple.
3rd, use sodium carbonate or sodium hydrogen carbonate solution washing, while not affecting target product 5-thiotolene-2-mercaptan, effectively lawesson reagent residue 4-methoxyphenyl phosphonic acids can be removed.
4th, the 5-thiotolene-2-mercaptan of gained has abundant reaction site as aromaticity thiphene ring, sulfydryl etc., has highly plastic.
Accompanying drawing explanation
Fig. 1 is by levulinic acid GC-MS collection of illustrative plates through series connection thio reaction products therefrom under lawesson reagent exists.
Fig. 2 is the mass spectrum of 5-thiotolene-2-mercaptan.
Fig. 3 is 5-thiotolene-2-mercaptan
1h-NMR spectrogram (solvent is deuterochloroform).
Fig. 4 is 5-thiotolene-2-mercaptan
13c-NMR spectrogram (solvent is deuterochloroform).
Embodiment
Following examples will the invention will be further described by reference to the accompanying drawings.
Embodiment 1
In 15mL toluene, add 0.23g levulinic acid, and add the lawesson reagent of the amount of 2 times of raw materials, 100 DEG C, react 5h under 1bar nitrogen atmosphere, obtain yellowish transparent liquid.This liquid is the sodium carbonate solution washing of 10% through 2 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 62%.
Embodiment 2
In 10mL dimethylbenzene, add 0.06g levulinic acid, and add the lawesson reagent of the amount of 1 times of raw material, 110 DEG C, react 1h under 1bar nitrogen atmosphere, obtain yellowish transparent liquid.This liquid is the sodium carbonate hydrogen solution washing of 5% through 1 times of volume, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 46%.
Embodiment 3
In 20mL toluene, add 0.6g levulinic acid, and add the lawesson reagent of the amount of 1.5 times of raw materials, 110 DEG C, react 4h under 1bar air atmosphere, obtain yellowish transparent liquid.This liquid is the sodium carbonate solution washing of 7.5% through 3 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 64%.
Embodiment 4
In 15mL toluene, ethylbenzene and dimethylbenzene mixed solution (volume ratio is 1: 1: 1), add 0.35g levulinic acid, and add the lawesson reagent of the amount of 3 times of raw materials, 110 DEG C, react 6h under 1bar nitrogen atmosphere, obtain yellowish transparent liquid.This liquid is the sodium carbonate solution washing of 4% through 1.5 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 51%.
Embodiment 5
In 10mL toluene, add 1.2g levulinic acid, and add the lawesson reagent of the amount of 1 times of raw material, 110 DEG C, react 4h under 1bar air atmosphere, obtain yellowish turbid solution.This liquid is the sodium hydrogen carbonate solution washing of 5% through 2 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 55%.
Embodiment 6
In 10mL toluene, add 0.12g levulinic acid, and add the lawesson reagent of the amount of 1.25 times of raw materials, 110 DEG C, react 15min under 1bar air atmosphere, obtain yellowish transparent liquid.This liquid is the sodium hydrogen carbonate solution washing of 5% through 3 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 48%.
Embodiment 7
In 20mL ethylbenzene, add 0.46g levulinic acid, and add the lawesson reagent of the amount of 1.5 times of raw materials, 110 DEG C, react 2h under 1bar air atmosphere, obtain yellowish transparent liquid.This liquid is the sodium hydrogen carbonate solution washing of 8% through 2.5 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 62%.
Embodiment 8
In 20mL ethylbenzene and dimethylbenzene mixed solution (volume ratio is 1: 1), add 2mmol levulinic acid, and add the lawesson reagent of the amount of 1.25 times of raw materials, 110 DEG C, react 1h under 1bar nitrogen atmosphere, obtain yellowish transparent liquid.This liquid is the sodium hydrogen carbonate solution washing of 10% through 2 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is respectively 73%.
Embodiment 9
In 20mL toluene and dimethylbenzene mixed solution (volume ratio is 3: 1), add 0.23g levulinic acid, and add the lawesson reagent of the amount of 2 times of raw materials, 95 DEG C, react 1.5h under 1bar nitrogen atmosphere, obtain yellowish transparent liquid.This liquid is the sodium carbonate solution washing of 5% through 3 times of volumes, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 77%.
Embodiment 10
In 15mL toluene and ethylbenzene mixed solution (volume ratio is 2: 1), add 0.12g levulinic acid, and add the lawesson reagent of the amount of 1 times of raw material, 90 DEG C, react 1h under 1bar nitrogen atmosphere, obtain yellowish transparent liquid.This liquid is the sodium carbonate solution washing of 3% through 1 times of volume, mass concentration, and be separated through underpressure distillation and obtain 5-thiotolene-2-mercaptan, productive rate is 17%.
By levulinic acid through the GC-MS collection of illustrative plates of series connection thio reaction products therefrom see the mass spectrum of Fig. 1,5-thiotolene-2-mercaptan see Fig. 2,5-thiotolene-2-mercaptan under lawesson reagent exists
1h-NMR spectrogram is see Fig. 3,5-thiotolene-2-mercaptan
13c-NMR spectrogram is see Fig. 4.
The present invention adopts the levulinic acid that can be transformed by lignocellulose under lawesson reagent exists, to prepare 5-thiotolene-2-mercaptan as raw material through series connection thio reaction.Particularly, add in less polar aprotic solvents using levulinic acid as raw material, with lawesson reagent reacting by heating under nitrogen or air atmosphere, after cooling, product liquid can obtain 5-thiotolene-2-mercaptan through alkali cleaning and underpressure distillation.This system is simply efficient, with low cost, provides one by the effective way of biomass-making for 5-thiotolene-2-mercaptan.
Claims (10)
1. prepared a method for 5-thiotolene-2-mercaptan by levulinic acid, it is characterized in that comprising the following steps:
1) levulinic acid is added in solvent, then add lawesson reagent reaction;
2) by step 1) products therefrom alkali cleaning, be transferred in aqueous phase by 4-methoxyphenyl phosphonic acids with salify, target product 5-thiotolene-2-mercaptan is retained in organic phase, and is separated with 4-methoxyphenyl phosphonic acids, and namely organic phase obtains 5-thiotolene-2-mercaptan through underpressure distillation.
2. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 1, it is characterized in that in step 1) in, the proportioning of described levulinic acid and solvent is (0.006 ~ 0.12) g: 1mL, wherein, levulinic acid is calculated in mass, and solvent is calculated by volume.
3. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 1, is characterized in that in step 1) in, described solvent is selected from least one in toluene, dimethylbenzene, ethylbenzene.
4. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 3, is characterized in that described solvent is selected from toluene.
5. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 1, is characterized in that in step 1) in, the add-on of described lawesson reagent is 0.5 ~ 3 of levulinic acid and solvent total amount in molar ratio.
6. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 1, it is characterized in that in step 1) in, described reaction is reacted under 1bar nitrogen atmosphere or air atmosphere, and the temperature of reaction is 90 DEG C ~ solvent boiling point, and the time of reaction is 15min ~ 6h.
7. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 1, is characterized in that in step 2) in, described alkali cleaning adopts sodium carbonate or sodium hydrogen carbonate solution washing.
8. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 7, it is characterized in that described sodium carbonate or sodium hydrogen carbonate solution adopt mass percentage concentration be 3% ~ 10% sodium carbonate or sodium hydrogen carbonate solution.
9. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 7, is characterized in that the consumption of described sodium carbonate or sodium hydrogen carbonate solution is step 1 by volume) 1 ~ 3 times of products therefrom.
10. a kind of method being prepared 5-thiotolene-2-mercaptan by levulinic acid as claimed in claim 1, is characterized in that in step 2) in, the condition of described underpressure distillation is: vacuum tightness 22torr, and temperature is 85 DEG C.
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| CN201610169913.5A CN105566285B (en) | 2016-03-23 | 2016-03-23 | A kind of method that the mercaptan of 5 methylthiophene 2 is prepared by levulic acid |
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| CN201610169913.5A CN105566285B (en) | 2016-03-23 | 2016-03-23 | A kind of method that the mercaptan of 5 methylthiophene 2 is prepared by levulic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112375065A (en) * | 2019-12-20 | 2021-02-19 | 湖北中烟工业有限责任公司 | Process for the preparation of 2-thiophenecarboxylate derivatives |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053287A2 (en) * | 2000-01-20 | 2001-07-26 | Siemens Aktiengesellschaft | Di(het)arylaminothiophene derivatives |
| CN104844542A (en) * | 2015-05-04 | 2015-08-19 | 厦门大学 | Method for preparing gamma-valerolactone by levulinic acid ester without solvents |
| KR20160024702A (en) * | 2014-08-26 | 2016-03-07 | 명지대학교 산학협력단 | Synthesis of furan, thiophene, and pyrroles from acetoacetic esters |
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- 2016-03-23 CN CN201610169913.5A patent/CN105566285B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001053287A2 (en) * | 2000-01-20 | 2001-07-26 | Siemens Aktiengesellschaft | Di(het)arylaminothiophene derivatives |
| KR20160024702A (en) * | 2014-08-26 | 2016-03-07 | 명지대학교 산학협력단 | Synthesis of furan, thiophene, and pyrroles from acetoacetic esters |
| CN104844542A (en) * | 2015-05-04 | 2015-08-19 | 厦门大学 | Method for preparing gamma-valerolactone by levulinic acid ester without solvents |
Non-Patent Citations (1)
| Title |
|---|
| JACQUES BRUNET ET AL.: "Sulfurization of γ-oxo esters; study of the resulting sulfur compounds", 《PHOSPHORUS AND SULFUR AND THE RELATED ELEMENTS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112375065A (en) * | 2019-12-20 | 2021-02-19 | 湖北中烟工业有限责任公司 | Process for the preparation of 2-thiophenecarboxylate derivatives |
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