CN114618581A - Novel catalyst for synthesizing allyl isothiocyanate - Google Patents
Novel catalyst for synthesizing allyl isothiocyanate Download PDFInfo
- Publication number
- CN114618581A CN114618581A CN202011436497.3A CN202011436497A CN114618581A CN 114618581 A CN114618581 A CN 114618581A CN 202011436497 A CN202011436497 A CN 202011436497A CN 114618581 A CN114618581 A CN 114618581A
- Authority
- CN
- China
- Prior art keywords
- reaction
- allyl isothiocyanate
- catalyst
- novel catalyst
- allyl
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
- B01J31/0232—Halogen-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0228
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
- C07C331/22—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
Abstract
The invention integrates the advantages of the existing process for synthesizing allyl isothiocyanate and aims to provide a novel catalyst for synthesizing allyl isothiocyanate. The novel catalyst plays a good role in catalysis in the reaction of thiocyanate and allyl halide, regardless of the occurrence of liquid-solid heterogeneous reaction or heterogeneous reaction. The method has the advantages of simple operation, high yield of final products, less impurities, shortened reaction time, improved yield, reduced cost, low energy consumption and strong market competitiveness.
Description
Technical Field
The invention belongs to the technical field of biology and new medicines, and relates to a novel catalyst for synthesizing allyl isothiocyanate.
Background
The allyl isothiocyanate is colorless to light yellow transparent oily liquid, has strong pungent smell, and is easy to be discolored and decomposed when being exposed to light. Slightly soluble in water and soluble in alcohols, ethers and carbon disulphide. Allyl isothiocyanate is an effective component of mustard oil, has very important positions in China and even the world due to medical efficacy, anticancer effect, antiseptic and bacteriostatic effects and soil disinfection effect, and is widely applied to industries such as food, chemical engineering, medicine, pesticide and the like.
A process for synthesizing allyl isothiocyanate includes the liquid-solid heterogeneous reaction between thiocyanate and allyl halide, and ordinary-pressure distillation and purification to directly synthesize target product. Heterogeneous phases often occur with certain catalysts. Namely, the allyl halide and the thiocyanate are simultaneously dissolved, so that the reaction is smoothly carried out. Common inorganic catalysts are potassium iodide and sodium iodide. Phase transfer catalysts such as polyethers (chain polyethylene glycol, chain polyethylene glycol dialkyl ether), cyclic crown ethers (18 crown 6, 15 crown 5, cyclodextrin, etc.), tertiary amines (R4N X, pyridine, tributylamine, etc.), quaternary ammonium bases, quaternary phosphonium salts, and quaternary ammonium salts. Commonly used quaternary ammonium salt phase transfer catalysts are benzyltriethylammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, and the like. And compounded catalysts such as sodium lauryl sulfate and tributyl phosphate. When water is used as the solvent, the surfactant may also be used as a catalyst. The surfactant is divided into ionic surfactant (including cationic surfactant and anionic surfactant), nonionic surfactant, amphoteric surfactant, compound surfactant, other surfactants, etc. There are many surfactants suitable for this synthesis process, to mention a few. However, regardless of the catalyst used, recovery of the catalyst is difficult, and further, high boiling is generated, and post-treatment of waste water and the like is also difficult.
The other method is to adopt an organic solvent to carry out homogeneous reaction on thiocyanate and allyl halide, and finally collect the product by a reduced pressure distillation method. The organic solvent simultaneously dissolves the allyl halide and the thiocyanate, so that the reaction is smoothly carried out. Sodium thiocyanate has certain solubility in an organic solvent in the whole synthesis process, and the sodium thiocyanate is dissolved and reacts along with the synthesis until the reaction equilibrium is finished. The method has the advantages of easily obtained raw materials and simple process, but has long reaction time, low yield and difficult post-treatment.
The invention integrates the advantages of two processes, and the novel catalyst for synthesizing allyl isothiocyanate is a component containing allyl isothiocyanate. During the reaction, a certain amount of catalyst, which is both a catalyst and a solvent, is added. A certain amount of catalyst is added to dissolve allyl halide and thiocyanate at the same time, so that the reaction is smoothly carried out, and when water is used as a solvent, a liquid-solid heterogeneous reaction is carried out, wherein the liquid-solid heterogeneous reaction is a phase transfer catalyst and the solvent; in the absence of water, it is also a phase transfer catalyst and solvent, allowing homogeneous reaction of the thiocyanate with the allyl halide.
Disclosure of Invention
The invention aims to provide a novel catalyst for synthesizing allyl isothiocyanate, namely a component containing the allyl isothiocyanate. During the reaction of thiocyanate and allyl halide, certain amount of catalyst is added to dissolve allyl halide and thiocyanate simultaneously for smooth reaction.
The invention is realized by the following method:
adding a certain amount of catalyst, then adding sodium thiocyanate and allyl chloride, slowly heating, sealing and preserving heat for reaction at a certain temperature, and carrying out central control detection. After the reaction is finished, salt is filtered out, allyl isothiocyanate is collected through reduced pressure distillation, and the yield (calculated by chloropropene) of the product reaches more than 95%.
Detailed Description
The present invention is further illustrated, but not limited to, by the following specific examples, which are set forth in the following examples, and which operate according to the procedures set forth above.
Example one
In a 500mL four-necked flask equipped with a thermometer, a buffer balloon and a stirring device, 200g of a catalyst (allyl isothiocyanate) was charged, 100g of sodium thiocyanate and 100mL of allyl chloride were charged, and the reaction was carried out under sealed conditions, heated in a water bath, heated to 35 ℃ and maintained for 2 hours. The temperature is slowly raised to 50 ℃ within 1 hour, and the temperature is kept for 4 hours. The temperature is raised to 90 ℃ and the temperature is kept for 2 hours. And (5) central control detection. After the reaction is finished, salt is filtered out, and allyl isothiocyanate fractions are collected through reduced pressure distillation.
Example two
In a 500mL four-necked flask equipped with a thermometer, a buffer balloon and a stirring device, 150g of a catalyst (allyl isothiocyanate mother liquor) was charged, 30mL of water was charged, 100g of sodium thiocyanate and 100mL of allyl chloride were charged, and the reaction was carried out while maintaining the temperature in a sealed state, heated in a water bath, heated to 35 ℃ and maintained for 2 hours. The temperature is slowly raised to 50 ℃ within 1 hour, and the temperature is kept for 4 hours. The temperature is raised to 90 ℃ and the temperature is kept for 2 hours. And (5) central control detection. After the reaction is finished, salt is filtered out, an organic phase is separated out, and allyl isothiocyanate fractions are collected through reduced pressure distillation.
EXAMPLE III
In a 500mL four-necked flask equipped with a thermometer, a buffer balloon and a stirring device, 5g of a catalyst (allyl isothiocyanate high boiling), 200mL of water, 100g of sodium thiocyanate and 100mL of allyl chloride were added, and the mixture was sealed and reacted under heat, heated in a water bath, heated to 35 ℃ and kept at heat for 2 hours. The temperature is slowly raised to 50 ℃ within 1 hour, and the temperature is kept for 4 hours. The temperature is raised to 90 ℃ and the temperature is kept for 2 hours. And (5) central control detection. After the reaction is finished, separating out an organic phase, and carrying out reduced pressure distillation to collect allyl isothiocyanate fractions.
Claims (1)
1. A novel catalyst for synthesizing allyl isothiocyanate is characterized in that the catalyst contains a substance containing an allyl isothiocyanate component, and the addition amount of the catalyst and the proportion of thiocyanate are 0.001: 1-1000: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011436497.3A CN114618581A (en) | 2020-12-11 | 2020-12-11 | Novel catalyst for synthesizing allyl isothiocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011436497.3A CN114618581A (en) | 2020-12-11 | 2020-12-11 | Novel catalyst for synthesizing allyl isothiocyanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114618581A true CN114618581A (en) | 2022-06-14 |
Family
ID=81895597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011436497.3A Pending CN114618581A (en) | 2020-12-11 | 2020-12-11 | Novel catalyst for synthesizing allyl isothiocyanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114618581A (en) |
-
2020
- 2020-12-11 CN CN202011436497.3A patent/CN114618581A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108341776B (en) | Process for synthesizing chloroquinate | |
| RU2746995C2 (en) | Method for producing sulfur tetrafluoride | |
| CN104341342B (en) | A kind of high yield, highly purified DAST source powder synthesis technique | |
| CN111205176B (en) | Synthetic method of 3, 5-dihalogen-2-pentanone | |
| CN106220523A (en) | The preparation method of S 2 amino-butanamide | |
| US2964535A (en) | Purification of nu-methyl pyrrolidone | |
| CN114618581A (en) | Novel catalyst for synthesizing allyl isothiocyanate | |
| KR101650528B1 (en) | Preparing method of glycidyl esters of alpha-branched aliphatic monocarboxylic acids | |
| You et al. | Nickel-catalyzed cross-electrophile C-Ge coupling of benzyl pivalates and chlorogermanes | |
| CN102010397A (en) | Method for preparing cyclic carbonic ester in presence of difunctional catalyst | |
| CN104193781B (en) | A kind of synthetic method of sulfur phosphide | |
| CN109354595B (en) | Method for recovering triphenylphosphine oxide from Wittig reaction rectification residual liquid | |
| CN113527064A (en) | Preparation method of phloroglucinol | |
| JP5896521B2 (en) | Method for producing 2,2-dimethylpropanethioamide | |
| CN110590550A (en) | Synthesis method of allyl isovalerate | |
| CN111995641B (en) | Production method of alkyl phosphine | |
| CN109734564B (en) | Method for synthesizing trifluoroethyl aromatic compound | |
| CN110305083B (en) | Process for preparing 5-chloromethyl furfural from fructose | |
| JPS5829927B2 (en) | Method for producing alkyl halide | |
| JP2011057652A (en) | Method for producing 4,4'-dihydroxydiphenyl ether | |
| CA1263410A (en) | Preparation of monoalkylene glycols in two stages | |
| JP2004182607A (en) | Method for producing 4-chloro-3-hydroxybutyronitrile | |
| JPS635037A (en) | Production of 2,3-dichloro-1-propene | |
| CN109607480A (en) | A kind of waste hydrochloric acid edulcoration purification process in Sucralose chlorination reaction | |
| CN104974009A (en) | Dichlor fluorbenzene synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication |