CN101723892B - Preparation method of 2-alkyl thioisonicotinamide - Google Patents
Preparation method of 2-alkyl thioisonicotinamide Download PDFInfo
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- CN101723892B CN101723892B CN2008101948400A CN200810194840A CN101723892B CN 101723892 B CN101723892 B CN 101723892B CN 2008101948400 A CN2008101948400 A CN 2008101948400A CN 200810194840 A CN200810194840 A CN 200810194840A CN 101723892 B CN101723892 B CN 101723892B
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Abstract
The invention provides a preparation method of 2-alkyl thioisonicotinamide, comprising the following steps of: preparing thioisonicotinamide through the reaction between 4-cyanopyridine as raw material and ammonium sulfide under the catalysis of sulphur; preparing crude 2-alkyl thioisonicotinamide through the hydrocarbonylation reaction between the thioisonicotinamide and fatty acid under the catalysis of lead tetraacetate (LTA), and refining to obtain the fine product by adopting ethanol. By adopting the reaction route of first sulfuric ammonization and then hydrocarbonylation, the positioning effect of the hydrocarbonylation reaction is improved, the generation of isomerized products in the reaction is reduced, and the operation is simplified; by adopting lead tetraacetate to substitute high-price silver nitrate, not only the cost is reduced, but also the reaction conversion ratio is improved, the two-step yield reaches up to 64 percent, the product purity reaches up to more than 98.5 percent, and the scale production is easy to realize.
Description
Technical field
The present invention relates to a kind of method of the 2-of preparation alkyl thioisonicotinamide, belong to the fine chemical technology field.
Background technology
2-alkyl-Thioisonicotinamide (2-alkyl-thioisonicotinamide) can be used for treating white plaque, like ethionamide and Protionamide.At present, the compound method of 2-alkyl-Thioisonicotinamide has: be raw material with methylethylketone and diacetyl oxide 1., obtain title product through eight step building-up reactionss, total recovery is 3%; 2. be raw material with the 4-cyanopyridine, get through two-step reaction.The first step is an alkylation reaction, 4-cyanopyridine and lipid acid and ammonium persulphate reaction, and Silver Nitrate is a catalyzer; Alkyl-4-the cyanopyridine that generates has many isomers, and the 2-substitution product is not only arranged, and also has 2-; The two substitution products of 6-need to obtain 2-alkyl-4-cyanopyridine through extraction, rectifying; Second step was the sulphur aminating reaction, and 2-alkyl-4-cyanopyridine and ammonium sulfide react under the catalysis of X 2073 and sulphur and generate 2-alkyl-Thioisonicotinamide, and total recovery reaches as high as: 34.7%.
Can show from above-mentioned prior preparation method, be that its process step of method of raw material is long with methylethylketone and diacetyl oxide, and yield is low, does not possess practical value.With the 4-cyanopyridine is raw material, and process hydrocarbonylation and sulphur aminating reaction prepare the method for 2-alkyl thioisonicotinamide, and its drawback is: the alkylation reaction selectivity is low, can produce isomerized products, needs to purify through steps such as extraction, rectifying; The catalyzer Silver Nitrate costs an arm and a leg, and can not recycle; The whole steps complex operation, cost is high.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, a kind of new method for preparing the 2-alkyl thioisonicotinamide is provided, be intended to effectively improve product gas purity, and adapt to industrialization production more.
The object of the invention is realized through following technical scheme:
The preparation method of 2-alkyl thioisonicotinamide, characteristics are: with the 4-cyanopyridine is raw material, and it is joined in the ammonium sulfide solution that contains sulphur; Heated and stirred; The sulphur aminating reaction takes place, and wherein, the mol ratio of 4-cyanopyridine and ammonium sulfide, sulphur is 1: (2～4): (0.3～1); Reaction finishes back suction filtration, washing, obtains Thioisonicotinamide; Then; In water, add Thioisonicotinamide, the vitriol oil, ammonium persulfate solution, lead tetra-acetate and lipid acid generation alkylation reaction; Wherein, the mol ratio of Thioisonicotinamide and lipid acid is 1: (1～3), the weight ratio of Thioisonicotinamide and lead tetra-acetate, the vitriol oil, ammonium persulphate are 1: (0.03～0.04): (0.5～1): (1～2); Obtain 2-alkyl thioisonicotinamide bullion, with obtaining elaboration after the solvent recrystallization.
Further, the preparation method of above-mentioned 2-alkyl thioisonicotinamide, the temperature of said sulphur aminating reaction are 40～60 ℃, and the reaction times is 2～6 hours.
Further, the preparation method of above-mentioned 2-alkyl thioisonicotinamide, the temperature of said alkylation reaction are 40～70 ℃, and the reaction times is 1～4 hour.
Further, the preparation method of above-mentioned 2-alkyl thioisonicotinamide, the concentration of said ammonium sulfide solution are 20%.
Further, the preparation method of above-mentioned 2-alkyl thioisonicotinamide, described ammonium persulfate solution is formulated by ammonium persulphate and water, and the weight ratio of water and ammonium persulphate is 2:1.
Further, the preparation method of above-mentioned 2-alkyl thioisonicotinamide, in the described alkylation reaction, the consumption of aqueous solvent is 5～10 times of Thioisonicotinamide weight.
Again further, the preparation method of above-mentioned 2-alkyl thioisonicotinamide, alkylation reaction finishes the back and separates out bullion with the ammoniacal liquor neutralization.
Again further, the preparation method of above-mentioned 2-alkyl thioisonicotinamide, the solvent of said recrystallization is an ethanol.
Substantive distinguishing features and obvious improvement that technical scheme of the present invention is outstanding are mainly reflected in:
It is starting raw material that the present invention adopts the 4-cyanopyridine, reacts under the catalysis of sulphur with ammonium sulfide earlier, generates Thioisonicotinamide; Under the catalysis of LTA, with lipid acid the alkyl substitution on the 2-position takes place again.Elder generation's sulphur ammonification is the reaction scheme of hydrocarbonylation again, has improved the locating effect of alkylation reaction, has reduced the generation of the isomerized products in the reaction, has simplified operation; In addition, substitute expensive Silver Nitrate, both reduced cost, improved reaction conversion ratio again with lead tetra-acetate.It is thus clear that, obviously be different from the prior art first hydrocarbonylation again the step of sulphur ammonification be the method for catalyzer with the Silver Nitrate, the invention has the advantages that the yield of sulphur ammonification is higher; The 2-alkyl substitution is because the activity of steric effect and LTA and selectivity is high, need not to extract, step such as rectifying, and whole technological operation is very simple; Total recovery is up to 64%; Product purity is easy to realize the production of mass-producing up to more than 98.5%, for the space has been expanded in the technical progress of this area.
Description of drawings
Below in conjunction with accompanying drawing technical scheme of the present invention is described further:
Thioisonicotinamide synthetic reaction formula among Fig. 1: the embodiment 1;
2-ethylenebis dithiocarbamate Isonicotinamide synthetic reaction formula among Fig. 2: the embodiment 1;
2-propyl dithiocarbamate Isonicotinamide synthetic reaction formula among Fig. 3: the embodiment 2.
Embodiment
The preparation method of 2-alkyl thioisonicotinamide of the present invention is a raw material with the 4-cyanopyridine, and 4-cyanopyridine and ammonium sulfide react under the catalysis of sulphur, obtain Thioisonicotinamide; Alkylation reaction takes place in Thioisonicotinamide and lipid acid under the catalysis of lead tetra-acetate (LTA), obtain 2-alkyl thioisonicotinamide bullion, obtains elaboration after making with extra care with ethanol.Can effectively improve the selectivity of alkylation reaction, significantly improve product gas purity, and not need the step of rectifying, better adapt to commercial application.
Concrete technology is: at first, sulphur is joined in 20% ammonium sulfide solution, heated and stirred is to dissolving; Add the 4-cyanopyridine; React, wherein, the mol ratio of 4-cyanopyridine and ammonium sulfide, sulphur is 1: (2～4): (0.3～1); The temperature of reaction is 40～60 ℃, and the time is 2～6 hours; Reaction finishes the back suction filtration, filter cake is used hot wash, obtains Thioisonicotinamide; Then; In water, add Thioisonicotinamide, the vitriol oil, ammonium persulfate solution, lead tetra-acetate and lipid acid generation alkylation reaction; Wherein, the mol ratio of Thioisonicotinamide and lipid acid is 1: (1～3), the weight ratio of Thioisonicotinamide and lead tetra-acetate, the vitriol oil, ammonium persulphate are 1: (0.03～0.04): (0.5～1): (1～2); The temperature of reaction is 40～70 ℃, and the time is 1～4 hour; Reaction finishes the back and separates out bullion with the ammoniacal liquor neutralization, with obtaining 2-alkyl thioisonicotinamide elaboration behind the ethyl alcohol recrystallization.
Embodiment 1:
Synthesizing of Thioisonicotinamide: 20% ammonium sulfide solution 294g is put in the four-necked bottle, stir adding sulphur 4.2g down, heated and stirred adds 4-cyanopyridine 45g to dissolving fully, is warming up to 40 ℃, is incubated 4 hours; Reaction formula is as shown in Figure 1.
Reaction is cooled to 25 ℃ after finishing, suction filtration, and filter cake is washed till neutrality with 70 ℃ of zero(ppm) water, obtains Thioisonicotinamide, the dry 47.3g that gets.
Synthesizing of 2-ethylenebis dithiocarbamate Isonicotinamide: the 56.8g ammonium persulphate is dissolved in the 113.6g water processes ammonium persulfate solution, subsequent use.In 240g water, add Thioisonicotinamide 47.3g, vitriol oil 23.6g, lead tetra-acetate 1.42g, stir adding propionic acid 50.7 grams, ammonium persulfate solution down, 60 ℃ of reactions 2 hours; Reaction formula is as shown in Figure 2.
Reaction is cooled to 25 ℃ after finishing, and slowly adds ammoniacal liquor and is neutralized to pH6～7, separates out 2-ethylenebis dithiocarbamate Isonicotinamide solid, suction filtration, washing, the dry 39.2g that gets.Ethanol refining refined prod 34.2g, fusing point: 161.5 ℃, content: 99.4%.
Embodiment 2:
Synthesizing of Thioisonicotinamide: 20% ammonium sulfide solution 441.6g is put in the four-necked bottle, stir adding sulphur 6.9g down, heated and stirred adds 4-cyanopyridine 45g to dissolving fully, is warming up to 50 ℃, is incubated 5 hours; Reaction is cooled to 25 ℃ after finishing, suction filtration, and filter cake is washed till neutrality with 70 ℃ of zero(ppm) water, obtains Thioisonicotinamide, the dry 49.8g that gets.
Synthesizing of 2-propyl dithiocarbamate Isonicotinamide: the 74.7g ammonium persulphate is dissolved in the 149.4g water processes ammonium persulfate solution, subsequent use.In 350g water, add Thioisonicotinamide 49.8g, vitriol oil 29.9g, lead tetra-acetate 1.6g, stir adding butyric acid 63.5g, ammonium persulfate solution down, 70 ℃ of reactions 2 hours; Reaction formula is as shown in Figure 3.
Reaction is cooled to 25 ℃ after finishing, and slowly adds ammoniacal liquor and is neutralized to pH6～7, separates out 2-propyl dithiocarbamate Isonicotinamide solid, suction filtration, washing, the dry 44.4g that gets.Ethanol refining refined prod 38.4g, fusing point: 140.8 ℃, content: 98.9%.
Embodiment 3:
Synthesizing of Thioisonicotinamide: 20% ammonium sulfide solution 368g is put in the four-necked bottle, stir adding sulphur 9.7g down, heated and stirred adds 4-cyanopyridine 45g to dissolving fully, is warming up to 60 ℃, is incubated 2 hours; Reaction is cooled to 25 ℃ after finishing, suction filtration, and filter cake is washed till neutrality with 70 ℃ of zero(ppm) water, obtains Thioisonicotinamide, the dry 51.8g that gets.
Synthesizing of 2-ethylenebis dithiocarbamate Isonicotinamide: the 77.8g ammonium persulphate is dissolved in the 155.6g water processes ammonium persulfate solution, subsequent use.In 363g water, add Thioisonicotinamide 51.8g, vitriol oil 38.9g, lead tetra-acetate 1.8g, stir adding propionic acid 61.1 grams, ammonium persulfate solution down, 40 ℃ of reactions 4 hours.
Reaction is cooled to 25 ℃ after finishing, and slowly adds ammoniacal liquor and is neutralized to pH6～7, separates out 2-ethylenebis dithiocarbamate Isonicotinamide solid, suction filtration, washing, the dry 46g that gets.Ethanol refining refined prod 41.2g, fusing point: 161.3 ℃, content: 99.2%.
Embodiment 4:
Synthesizing of Thioisonicotinamide: 20% ammonium sulfide solution 515.2g is put in the four-necked bottle, stir adding sulphur 11.1g down, heated and stirred adds 4-cyanopyridine 45g to dissolving fully, is warming up to 40 ℃, is incubated 6 hours; Reaction is cooled to 25 ℃ after finishing, suction filtration, and filter cake is washed till neutrality with 70 ℃ of zero(ppm) water, obtains Thioisonicotinamide, the dry 51g that gets.
Synthesizing of 2-propyl dithiocarbamate Isonicotinamide: the 86.7g ammonium persulphate is dissolved in the 173.4g water processes ammonium persulfate solution, subsequent use.In 408g water, add Thioisonicotinamide 51g, vitriol oil 40.8g, lead tetra-acetate 1.9g, stir adding butyric acid 71.5g, ammonium persulfate solution down, 50 ℃ of reactions 1 hour.
Reaction is cooled to 25 ℃ after finishing, and slowly adds ammoniacal liquor and is neutralized to pH6～7, separates out 2-propyl dithiocarbamate Isonicotinamide solid, suction filtration, washing, the dry 47.4g that gets.Ethanol refining refined prod 41.6g, fusing point: 140.6 ℃, content: 98.7%.
Embodiment 5:
Synthesizing of Thioisonicotinamide: 20% ammonium sulfide solution 368g is put in the four-necked bottle, stir adding sulphur 9.7g down, heated and stirred adds 4-cyanopyridine 45g to dissolving fully, is warming up to 50 ℃, is incubated 4 hours; Reaction is cooled to 25 ℃ after finishing, suction filtration, and filter cake is washed till neutrality with 70 ℃ of zero(ppm) water, obtains Thioisonicotinamide, the dry 51.6g that gets.
Synthesizing of 2-ethylenebis dithiocarbamate Isonicotinamide: the 87.7g ammonium persulphate is dissolved in the 175.4g water processes ammonium persulfate solution, subsequent use.In 360g water, add Thioisonicotinamide 51.6g, vitriol oil 25.8g, lead tetra-acetate 1.96g, stir adding propionic acid 69.2 grams, ammonium persulfate solution down, 40 ℃ of reactions 4 hours.
Reaction is cooled to 25 ℃ after finishing, and slowly adds ammoniacal liquor and is neutralized to pH6～7, separates out 2-ethylenebis dithiocarbamate Isonicotinamide solid, suction filtration, washing, the dry 44.6g that gets.Ethanol refining refined prod 39.4g, fusing point: 161.5 ℃, content: 99.1%.
In sum, the present invention is a starting raw material with the 4-cyanopyridine, reacts under the catalysis of sulphur with ammonium sulfide earlier, generates Thioisonicotinamide; Under the catalysis of LTA, with lipid acid the alkyl substitution on the 2-position takes place again.Elder generation's sulphur ammonification is the reaction scheme of hydrocarbonylation again, has improved the locating effect of alkylation reaction, has reduced the generation of the isomerized products in the reaction, thereby has simplified operation; In addition, substitute expensive Silver Nitrate, both reduced cost, improved reaction conversion ratio again with lead tetra-acetate.It is thus clear that, obviously be different from the prior art first hydrocarbonylation again the step of sulphur ammonification be the method for catalyzer with the Silver Nitrate, the invention has the advantages that the yield of sulphur ammonification is higher; The 2-alkyl substitution is because the activity of steric effect and LTA and selectivity is high, need not to extract, step such as rectifying, and whole technological operation is very simple; Product yield is up to 64%; Purity is easy to realize the production of mass-producing up to more than 98.5%, and application prospect is boundless.
Below only be concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop within the rights protection scope of the present invention.
Claims (7)
1.2-the preparation method of alkyl thioisonicotinamide is characterized in that: with the 4-cyanopyridine is raw material, and it is joined in the ammonium sulfide solution that contains sulphur; Heated and stirred; The sulphur aminating reaction takes place, and wherein, the mol ratio of 4-cyanopyridine and ammonium sulfide, sulphur is 1: (2～4): (0.3～1); Reaction finishes back suction filtration, washing, obtains Thioisonicotinamide; Then; In water, add Thioisonicotinamide, the vitriol oil, ammonium persulfate solution, lead tetra-acetate and lipid acid generation alkylation reaction; Wherein, the mol ratio of Thioisonicotinamide and lipid acid is 1: (1～3), the weight ratio of Thioisonicotinamide and lead tetra-acetate, the vitriol oil, ammonium persulphate are 1: (0.03～0.04): (0.5～1): (1～2); Obtain 2-alkyl thioisonicotinamide bullion, obtain elaboration after as solvent recrystallization with ethanol.
2. the preparation method of 2-alkyl thioisonicotinamide according to claim 1 is characterized in that: the temperature of said sulphur aminating reaction is 40～60 ℃, and the reaction times is 2～6 hours.
3. the preparation method of 2-alkyl thioisonicotinamide according to claim 1 is characterized in that: the temperature of said alkylation reaction is 40～70 ℃, and the reaction times is 1～4 hour.
4. the preparation method of 2-alkyl thioisonicotinamide according to claim 1 is characterized in that: the concentration of said ammonium sulfide solution is 20%.
5. the preparation method of 2-alkyl thioisonicotinamide according to claim 1 is characterized in that: described ammonium persulfate solution is formulated by ammonium persulphate and water, and the weight ratio of water and ammonium persulphate is 2: 1.
6. the preparation method of 2-alkyl thioisonicotinamide according to claim 1 is characterized in that: in the described alkylation reaction, the consumption of aqueous solvent is 5～10 times of Thioisonicotinamide weight.
7. the preparation method of 2-alkyl thioisonicotinamide according to claim 1 is characterized in that: alkylation reaction finishes the back and separates out bullion with the ammoniacal liquor neutralization.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741997A (en) * | 2002-12-23 | 2006-03-01 | 科学与工业研究委员会 | Process for conversion of cyanopyridines tonicotinamides and catalyst therefor, process for preparing said catalyst |
| CN1807415A (en) * | 2005-01-21 | 2006-07-26 | 北京化工大学 | 4-aminopyridine preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741997A (en) * | 2002-12-23 | 2006-03-01 | 科学与工业研究委员会 | Process for conversion of cyanopyridines tonicotinamides and catalyst therefor, process for preparing said catalyst |
| CN1807415A (en) * | 2005-01-21 | 2006-07-26 | 北京化工大学 | 4-aminopyridine preparation method |
Non-Patent Citations (1)
| Title |
|---|
| Chaturvedi.S.C.,et al.."Ethionamide derivatives and their antibacterial activity".《Indian J Pharm Sci》.1984,第46卷(第1期),第10-12页. |
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