CN114181123A - Green synthesis method of 6-ethylthio-3 hepten-2-one - Google Patents
Green synthesis method of 6-ethylthio-3 hepten-2-one Download PDFInfo
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- CN114181123A CN114181123A CN202111383572.9A CN202111383572A CN114181123A CN 114181123 A CN114181123 A CN 114181123A CN 202111383572 A CN202111383572 A CN 202111383572A CN 114181123 A CN114181123 A CN 114181123A
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Abstract
The invention discloses a green synthesis method of 6-ethylthio-3 hepten-2-one, which takes acetone and 3-ethylthio butyraldehyde as raw materials, and obtains the 6-ethylthio-3 hepten-2-one through one-step reaction in the presence of a catalyst; the catalyst is a combination of a nitrogen-containing base catalyst and an acid catalyst. The invention adopts the combination of nitrogenous alkali and nitrogenous acid as the catalyst, can realize higher yield at lower temperature, and has low reaction temperature and mild reaction conditions. The invention can obtain the target product by one-pot reaction, has simple operation and high product yield and purity, and is an ideal route with wide prospect.
Description
Technical Field
The invention relates to a synthetic method of a clethodim intermediate, in particular to a synthetic method of a clethodim intermediate, namely 6-ethylthio-3 hepten-2 one, which is environment-friendly and mild in reaction conditions, and belongs to the technical field of chemical synthesis.
Background
Clethodim is a novel dry land post-emergence herbicide, has excellent selectivity, is obtained by research and development of Japan Caoda company, and can prevent and kill annual and perennial gramineous weeds.
The 6-ethylthio-3-hepten-2-one is a key intermediate in the clethodim synthesis process, and the current main synthesis method comprises the following steps: the methyl acetoacetate reacts with liquid alkali to prepare sodium acetoacetate, and the sodium acetoacetate and thioether aldehyde generate 6-ethylthio-3-heptylene-2-ketone under the conditions of acetic acid, other catalysts and solvents. The reaction formula is as follows:
during the synthesis process, methanol and CO are generated2The waste gas also produces a large amount of sodium acetate waste water, the atom economy is poor, and the environmental pollution is also caused.
CN101318919 reports a synthesis method of 6-ethylthio-3-hepten-2-one, in which 3-ethylthio butyraldehyde and acetone are reacted in an alkali solution, the reaction is carried out in a boiling state, and the reaction temperature is high. When the base is sodium hydroxide, the yield is low, only 63%, and when the base is sodium carbonate, the yield is high, 93%. When the reaction is carried out at a relatively low temperature, for example, 15 ℃, 6-ethylthio-3-hepten-2-one is produced in a small amount, 6-ethylthio-4-hydroxy-2-heptanone as a main product. The reaction temperature is high, and the target product cannot be formed at low temperature. And more inorganic salt wastewater can be generated in the reaction process, so that the environmental protection pressure is increased.
Wangshiyi discloses a preparation method of 6-ethylthio-3-hepten-2-one in literature (Wangshiyi, pesticide and medical intermediate 6-ethylthio-3-hepten-2-one [ J ]. Anhui chemical industry, 2005(01): 21-22). in the method, acetone and 3-ethylthio butyraldehyde are mixed, then 1% sodium hydroxide solution is dropwise added as a catalyst, and 6-ethylthio-3-hepten-2-one is synthesized at 65 ℃ after dropwise addition, and the yield is 85.9%. And the effect of reaction temperature on yield was also investigated in this document, from the results, the yield was lower at lower reaction temperatures, e.g. only 12.8% at 25 ℃ and only 56.7% at 45 ℃.
As can be seen from the prior art, the existing method for synthesizing 6-ethylthio-3-hepten-2-one by using alkali as a catalyst needs to obtain a product with higher yield at higher reaction temperature, which increases the production cost. And the alkaline catalyst can not be recycled and is discharged as wastewater, so that the post-treatment cost is increased.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a green synthesis method of 6-ethylthio-3-hepten-2-one, which is simple to operate, mild in reaction conditions, free of generation of a large amount of byproducts and wastewater, green and environment-friendly, high in product yield and good in application prospect.
The specific technical scheme of the invention is as follows:
a green synthesis method of 6-ethylthio-3 hepten-2 one uses acetone and 3-ethylthio butyraldehyde as raw materials, and obtains the 6-ethylthio-3 hepten-2 one through one-step reaction in the presence of a catalyst; the catalyst is a combination of a nitrogen-containing base catalyst and an acid catalyst.
Further, the nitrogen-containing base catalyst is pyridine, piperidine, pyrrole or a compound shown as a formula G3, wherein in the formula G3, R is1、R2、R3Each independently is hydrogen or C1-C4Alkyl of (2), preferably, R1、R2、R3Not hydrogen at the same time;
further, the compound of G3 may be ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, propylamine, etc., and preferably monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, propylamine.
Further, the nitrogen-containing basic catalyst may be one of ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, di-n-propylamine, diisopropylamine, pyridine, piperidine, pyrrole, etc., and preferably, the nitrogen-containing basic catalyst is the above-mentioned nitrogen-containing organic basic catalyst.
Preferably, the nitrogen-containing base catalyst may be dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, pyridine or piperidine.
Further, the acid catalyst is an inorganic acid or an organic acid. The inorganic acid can be hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, etc., and the organic acid can be C1-C4 organic acid such as formic acid, acetic acid, propionic acid, butyric acid, etc., and can also be benzoic acid, p-toluenesulfonic acid, proline, etc.
Preferably, the acid catalyst is formic acid, acetic acid, propionic acid, benzoic acid, p-toluenesulfonic acid or proline.
Furthermore, the base catalyst used in the invention is used for promoting aldol condensation reaction to generate an intermediate non-dehydrated product, the acid is used for dehydrating to promote the reaction to be carried out in the forward direction, and the base catalyst and the acid are synergistically promoted to be beneficial to improving the reaction speed and the product yield.
Further, the amount of the nitrogen-containing basic catalyst is 0.01 to 30%, preferably 1 to 30%, more preferably 1 to 10% by mass of 3-ethylsulfanylbutanal.
Further, the amount of the acid catalyst is 0.01 to 30%, preferably 0.01 to 5% by mass of 3-ethylsulfanylbutanal.
Further, the molar ratio of 3-ethylsulfanylbutanal to acetone is 1:1 to 10, preferably 1:1 to 5, more preferably 1: 1.5-3.
Further, the reaction temperature is-20 to 50 ℃, preferably 0 to 50 ℃, more preferably 0 to 30 ℃, and most preferably 20 to 30 ℃. Sampling in the reaction process to determine the content of the raw materials, and finishing the reaction after the reaction of the raw materials is finished. The invention can realize better yield at the temperature lower than 50 ℃, and particularly can carry out reaction at room temperature or normal temperature, and the condition is milder.
Further, in the above synthesis method, the order of adding the reaction raw materials may be according to the following steps: fully mixing acetone, a nitrogen-containing alkali catalyst and an acid catalyst, then dropwise adding 3-ethylsulfanyl butyraldehyde into the mixture, and reacting after completing dropwise adding to obtain 6-ethylsulfanyl-3 hepten-2-one. Such a reaction sequence is more advantageous for the forward direction of the reaction.
Further, acetone, a nitrogen-containing alkali catalyst and an acid catalyst are mixed for 0.5-1h at the reaction temperature, then 3-ethylthio butyraldehyde is dropwise added into the mixture at the reaction temperature for 1-1.5h, and after dropwise addition is finished, the mixture is reacted for 3-3.5h at the reaction temperature to obtain 6-ethylthio-3 hepten-2-one.
Further, after the reaction is finished, adding an organic solvent into the reaction solution for extraction, and then standing for layering, wherein the lower layer is a catalyst layer, and the upper layer is an organic layer. The catalyst layer can be directly recycled, and the organic layer can remove the solvent to obtain the product.
The invention has the following beneficial effects:
1. the invention takes acetone and 3-ethylthio butyraldehyde as raw materials, and compared with methyl acetoacetate and 3-ethylthio butyraldehyde as raw materials, methanol and CO are avoided2Sodium acetate and wastewater, green and environment-friendly, and high atom economy.
2. The invention takes acetone and 3-ethylthio butyraldehyde as raw materials, adopts a combination of nitrogen-containing alkali and acid as a catalyst, can realize higher yield at lower temperature, and has low reaction temperature and mild reaction conditions.
3. The invention can obtain the target product by one-pot reaction, has simple operation and high product yield and purity, and is an ideal route with wide prospect.
Drawings
FIG. 1 is a mass spectrum of 6-ethylthio-3-hepten-2-one obtained by the present invention.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be exemplary only and are not intended to be limiting. In the following examples, each of the reagents used was commercially available unless otherwise specified. In the following examples, terms not described in detail are all the meanings reported in the prior art, and operations and methods not described in detail can refer to the operations in the prior art.
Unless otherwise specified, the following concentrations are mass percent concentrations.
EXAMPLE 1 screening of the catalyst
11.67g of acetone (content: 99.5%) was added to a four-necked flask, and 0.37g of a nitrogen-containing organic base catalyst and 0.38g of an acid catalyst were added thereto, followed by stirring at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask over 1 hour. After the dripping is finished, the reaction is kept at 30 ℃ for 3 hours, and sampling GC detection shows that the content of 3-ethylthio butyraldehyde is less than 1%. After the reaction, 20g of toluene was added for extraction, and the mixture was allowed to stand for layering, with the lower layer being a catalyst layer and the upper layer being an organic layer. And (3) carrying out negative pressure distillation on the organic layer, and obtaining the product 6-ethylthio-3 heptene-2 one after the solvent is removed to be qualified.
The quality and yield of the products obtained for the different catalyst cases are shown in table 1 below:
EXAMPLE 2 screening of the amount of catalyst used
11.67g of acetone (content: 99.5%) was added to the four-necked flask, and then diethylamine and acetic acid of different masses were added thereto, respectively, and the mixture was stirred at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask over 1 hour. After the dripping is finished, the reaction is kept at 30 ℃ for 3 hours, and sampling GC detection shows that the content of 3-ethylthio butyraldehyde is less than 1%. After the reaction, 20g of toluene was added for extraction, and the mixture was allowed to stand for layering, with the lower layer being a catalyst layer and the upper layer being an organic layer. And (3) carrying out negative pressure distillation on the organic layer, and obtaining the product 6-ethylthio-3 heptene-2 one after the solvent is removed to be qualified.
The reaction times in terms of product at different catalyst levels are shown in Table 2 below.
EXAMPLE 3 screening of the amount of raw Material
Acetone (content: 99.5%) with different masses was added to each of the four flasks, and then 0.37g of diethylamine and 0.38g of acetic acid were added thereto, followed by stirring at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask at 30 ℃ for 1 h. After the dripping is finished, the reaction is kept at the temperature of 30 ℃, samples are continuously taken in the reaction process, and the reaction is stopped when GC detection shows that the content of the 3-ethylsulfanylbutanal is less than 1%. After the reaction is finished, negative pressure distillation is started to remove low boiling point components and the catalyst, and the product 6-ethylthio-3 heptene-2-one is obtained.
The reaction times in the product cases at different amounts of acetone are shown in Table 3 below.
Example 4 screening of reaction temperature
To a four-necked flask, 11.67g of acetone (99.5% content) was added, and 0.37g of diethylamine and 0.38g of acetic acid were added, followed by stirring at constant temperature for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (95% content) was added dropwise to the four-necked flask at the same temperature over 1 hour. After the dripping is finished, the reaction is kept at the temperature, samples are continuously taken in the reaction process, and the reaction is stopped when GC detection shows that the content of the 3-ethylsulfanyl butyraldehyde is less than 1%. After the reaction is finished, negative pressure distillation is started to remove low boiling point components and the catalyst, and the product 6-ethylthio-3 heptene-2-one is obtained.
The reaction times at different temperatures are shown in Table 4 below in the case of the products.
Example 5
To a four-necked flask, 11.67g of acetone (99.5% content) was added, and then 4.1g of an aqueous ammonia solution (containing 0.37g of ammonia) and 0.38g of acetic acid were added, respectively, and the mixture was stirred at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask over 1 hour. After the dripping is finished, the reaction is kept at 30 ℃ for 3 hours, and sampling GC detection shows that the content of 3-ethylthio butyraldehyde is less than 1%. After the reaction, 20g of toluene was added for extraction, and the mixture was allowed to stand for layering, with the lower layer being a catalyst layer and the upper layer being an organic layer. And carrying out negative pressure distillation on the organic layer, and obtaining 16.51g of the product 6-ethylthio-3 heptene-2 one with the purity of 73.5 percent after the solvent is removed to be qualified.
Comparative example 1
To a four-necked flask was added 11.67g of acetone (content: 99.5%), and 3.5g of 15% sodium carbonate solution was added, followed by stirring at 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask at 30 ℃ for 1 h. After the dripping is finished, the reaction is carried out for 3 hours at the temperature of 30 ℃. After completion of the reaction, the reaction solution was extracted with dichloromethane, and the resulting organic phase was dried over anhydrous sodium sulfate overnight, followed by distillation under reduced pressure to remove the solvent, whereby 8.72g of 6-ethylsulfanyl-3-hepten-2-one was obtained in a purity of 50.8%.
Comparative example 2
To a four-necked flask, 11.67g of acetone (99.5% content) was added, and 0.37g of diethylamine was added and stirred at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask at 30 ℃ for 1 h. After the dripping is finished, the reaction is kept at 30 ℃ for 3 hours, and sampling GC detection shows that the content of 3-ethylthio butyraldehyde is less than 1%. After the reaction, the negative pressure distillation is started to remove the low boiling point components and the catalyst, and 16.76g of the product 6-ethylthio-3 heptene-2-one with the purity of 77.1 percent is obtained.
Comparative example 3
To a four-necked flask, 11.67g of acetone (99.5% content) was added, and 0.38g of acetic acid was added and stirred at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask at 30 ℃ for 1 h. After the dripping is finished, the reaction is carried out for 3 hours at the temperature of 30 ℃, and sampling GC detection shows that no product is produced.
Comparative example 4
11.67g of acetone (content: 99.5%) was added to a four-necked flask, and 0.37g of sodium hydroxide (content: 95%) and 0.38g of hydrochloric acid were added thereto, respectively, and the mixture was stirred at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask over 1 hour. After the dripping is finished, the reaction is carried out for 3 hours at the temperature of 30 ℃, and no product is generated by sampling and GC detection.
Comparative example 5
11.67g of acetone (content: 99.5%) was added to a four-necked flask, and 0.37g of 0.37g N-methyl-n-pentylamine and 0.38g of hydrochloric acid were added thereto, followed by stirring at a constant temperature of 30 ℃ for 1 hour. Then 13.92g of 3-ethylsulfanylbutanal (content: 95%) is added dropwise into a four-neck flask over 1 hour. After the dripping is finished, the reaction is kept at 30 ℃ for 3 hours, and sampling GC detection shows that the content of 3-ethylthio butyraldehyde is less than 1%. After the reaction, the negative pressure distillation is started to remove the low boiling point components and the catalyst, and 13.11g of the product 6-ethylthio-3 heptene-2-one with the purity of 65.5 percent is obtained.
Claims (8)
1. A green synthesis method of 6-ethylthio-3 hepten-2-one is characterized by comprising the following steps: acetone and 3-ethylthio butyraldehyde are used as raw materials, and react in the presence of a catalyst in the next step to obtain 6-ethylthio-3 hepten-2-one; the catalyst is a combination of a nitrogen-containing base catalyst and an acid catalyst.
2. The green color synthesis method according to claim 1, wherein: the nitrogen-containing base catalyst is pyridine, piperidine, pyrrole or a compound shown as a formula G3, wherein in the formula G3, R1, R2 and R3 are respectively and independently hydrogen or C1-C4 alkyl; the acid catalyst is inorganic acid or organic acid;
3. the green color synthesis method according to claim 1, wherein: the nitrogen-containing base catalyst is ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, di-n-propylamine, diisopropylamine, pyridine, piperidine or pyrrole, preferably dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, pyridine or piperidine; the acid catalyst is hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, p-toluenesulfonic acid or proline, preferably formic acid, acetic acid, propionic acid, benzoic acid, p-toluenesulfonic acid or proline.
4. A green synthesis method according to any one of claims 1 to 3, characterized in that: fully mixing acetone, a nitrogen-containing alkali catalyst and an acid catalyst, then dropwise adding 3-ethylsulfanyl butyraldehyde into the mixture, and reacting after completing dropwise adding to obtain 6-ethylsulfanyl-3 hepten-2-one.
5. The green color synthesis method according to claim 4, wherein: mixing acetone, a nitrogen-containing alkali catalyst and an acid catalyst at a reaction temperature for 0.5-1h, then dropwise adding 3-ethylsulfanylbutanal into the mixture at the reaction temperature for 1-1.5h, and reacting at the reaction temperature for 3-3.5h after dropwise adding to obtain 6-ethylsulfanyl-3 hepten-2-one.
6. A green synthesis method according to any one of claims 1 to 3, characterized in that: the dosage of the nitrogen-containing alkali catalyst is 0.01-30%, preferably 1-30%, more preferably 1-10% of the mass of the 3-ethylsulfanylbutanal; the amount of the acid catalyst is 0.01 to 30% by mass, preferably 0.01 to 5% by mass, based on the mass of 3-ethylsulfanylbutanal.
7. A green synthesis method according to any one of claims 1 to 3, characterized in that: the molar ratio of 3-ethylsulfanylbutanal to acetone is 1:1 to 10, preferably 1:1 to 5, more preferably 1: 1.5-3.
8. A green synthesis method according to any one of claims 1 to 3, characterized in that: the reaction temperature is-20 to 50 ℃, preferably 0 to 50 ℃, more preferably 0 to 30 ℃, and most preferably 20 to 30 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957060A (en) * | 2022-06-29 | 2022-08-30 | 宁夏一帆生物科技有限公司 | Synthetic method of 6-ethylthio-3-hepten-2-one |
| CN115286500A (en) * | 2022-08-31 | 2022-11-04 | 山东新和成氨基酸有限公司 | Preparation method and composition of acetoacetic acid, 6-ethylthio-3-heptylene-2-ketone and intermediate thereof |
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2021
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957060A (en) * | 2022-06-29 | 2022-08-30 | 宁夏一帆生物科技有限公司 | Synthetic method of 6-ethylthio-3-hepten-2-one |
| CN115286500A (en) * | 2022-08-31 | 2022-11-04 | 山东新和成氨基酸有限公司 | Preparation method and composition of acetoacetic acid, 6-ethylthio-3-heptylene-2-ketone and intermediate thereof |
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Application publication date: 20220315 |