CN102399193A - Method for preparing 4,6-diamino-2-(cyclopropylamino)-5-pyrimidinecarbonitrile - Google Patents
Method for preparing 4,6-diamino-2-(cyclopropylamino)-5-pyrimidinecarbonitrile Download PDFInfo
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- CN102399193A CN102399193A CN2011104204733A CN201110420473A CN102399193A CN 102399193 A CN102399193 A CN 102399193A CN 2011104204733 A CN2011104204733 A CN 2011104204733A CN 201110420473 A CN201110420473 A CN 201110420473A CN 102399193 A CN102399193 A CN 102399193A
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Abstract
The invention discloses a method for preparing 4,6-diamino-2-(cyclopropylamino)-5-pyrimidinecarbonitrile, and belongs to the technical field of fine chemical synthesis. The method comprises the following steps of: reacting raw materials, namely N,N-dimethyl-S,S-dimethyl dithiocarbonate, organic alkali metal salt and malononitrile to obtain 1-methylmercapto-1-cyanamide-2,2-dicyano ethylene alkali metal salt, and reacting the compound with hydrochloric acid to obtain 2-chloro-4-amino-5-cyano-6-methylthiopyrimidine; refluxing the 2-chloro-4-amino-5-cyano-6-methylthiopyrimidine and cyclopropylamine in an ethanol solution to obtain 4-amino-2-(cyclopropylamino)-5-cyano-6-methylthiopyrimidine; oxidizing in a dichloromethane solvent by taking acetic acid and urea peroxide as a catalyst system to obtain 4-amino-2-(cyclopropylamino)-5-cyano-6-(methylsulfonyl)pyrimidine; and finally performing substitution by using ammonia water by taking acetonitrile as a solvent to obtain the final product. The method is a synthesis route which is suitable for industrial production and has high economy and operability.
Description
Technical field
The invention belongs to technical field of fine chemical synthesis, is a kind of preparation 4, the novel method of 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine and compound thereof.
Background technology
4,6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine has another name called the Dicyclanil or the third worm pyridine, and code name CGA183893, English chemical name are 4,6-Diamino-2-(cyclo-propyla-min-
O)-and 5-pyrimidinecarbonitrile, the novel cyanic acid that disclosed the 8th international chemistry of pesticide meeting in 1994 for Switzerland Ciba-Geigy company (at present for Novartis Co.,Ltd) is had a liking for and is suck insecticides.
People's such as Kritinsson USP 4783468 provides the preparation method of this compound; People's such as Kritinsson patent discloses can pass through 2-chloro-4,6-diamino--5-cyanopyrimidine and cyclopropylamine prepared in reaction in appropriate organic solvent.And the disclosed preparation method in the Chinese patent of delivering in 1994 94192888 of Switzerland Ciba-Geigy company: (N-cyanimino) methylcarbonate; Propane dinitrile reacts in the methanol solution of sodium methylate, prepares 1-alkoxyl group-1-cyanogen amino-2,2-dicyano ethene an alkali metal salt; In pressure reaction still, be reaction solvent further with ethanol; Feed ammonia gas react and obtain 1-amino-1-cyanogen amino-2,2-dicyano ethene an alkali metal salt is handled 1-amino-1-cyanogen amino-2 with the hydrochloric acid soln of secondary alcohol or water; 2-dicyano ethene an alkali metal salt; Generate 2-chloro-4,6-diamino--5-cyanopyrimidine is handled with the ethanolic soln of cyclopropylamine at last and is obtained title product.
Zhang Mei is published in " world's agricultural chemicals "---and in synthetic and application one literary composition of the new pesticides third worm pyridine method for preparing this compound is provided also: 2-cyanic acid-3-cyanogen amino-3-methylthio group vinyl cyanide obtains 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine with the salt s.t.; Handle through the ethanolic soln of cyclopropylamine again and obtain compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-first mercaptopyrimidine, in pressure reaction still, handle this compound and finally obtain title product with ammonia.
Though aforesaid method can satisfy Laboratory Request, its reaction conditions requires harsh, and its ammonolysis reaction will feed under the ammonia condition and accomplish at 90 pounds/square inch.The extraction that relates in the operation; Certain operations such as concentrating has caused its aftertreatment to become loaded down with trivial details; These factors make it high to the suitability for industrialized production equipment requirements in industrial production; Technological operation requires also too complicated, and the equipment input causes production cost to rise with the artificial increase that drops into, and there are very big deficiency in security and economy.These unfavorable factors have all restricted the suitability for industrialized production and the practical application of this compound widely.
Summary of the invention
The present invention is for overcoming above-mentioned prior art; Have now found that a kind of method of new this compound of preparation, reaction formula is following:
4, the preparation method of 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine, carry out according to following step:
(1) N, N-dimethyl--S, the alkaline alcohol solvent of S-dithiocarbonic acid dimethyl ester and propane dinitrile react down at 0 ~ 40 ℃ and obtain compound 1-methylthio group-1-cyanogen amino-2,2-dicyano ethene an alkali metal salt;
(2) the compound 1-methylthio group that step (1) is obtained-1-cyanogen amino-2; 2-dicyano ethene an alkali metal salt dissolves in 30 ℃ of water, is to handle through persalt under 20-40 ℃ to obtain compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine in temperature of reaction again;
(3) the compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine that step (2) is obtained is dissolved in the organic solvent, adds Na
2CO
3Carry out temperature rising reflux with cyclopropylamine, its reflux temperature is 78-79 ℃, obtains compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-first mercaptopyrimidine;
(4) compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid of obtaining of step (3)-6-first mercaptopyrimidine is through carbamide peroxide; The acetic acid catalysis system; Catalyzed oxidation in organic solvent obtains compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine;
(5) compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine of obtaining of step (4), carries out ammonification with the ammoniacal liquor doubly of molar equivalent 8-12 and finally obtains title product as solvent with acetonitrile.
Wherein step (3) compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine and cyclopropylamine optimum molar ratio are 1:1.1-1.5, and the mol ratio of yellow soda ash and compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine is 1:1.
Wherein the mol ratio of step (4) compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine and carbamide peroxide is 1:3-6; Wherein answering temperature is 38-40 ℃; Wherein organic solvent is that common solvent can both make reaction well carry out in the industrial production such as methyl alcohol, ethanol, acetone, acetonitrile, methylene dichloride, but methylene dichloride most preferably.
Wherein step (5) ammoniacal liquor be solvent be again reactant.This reaction optimal reaction temperature is 0-55 ℃.The recyclable utilization of its solvent.
This compound method very remarkable advantages of having compared with other compound methods:
(1) this compound method is a kind of comparative maturity, can be applicable to the method for a large amount of industrial synthesising target compounds.
(2) this method has been avoided reaction needed stress reaction device in the past; Ammonia is separated the step direct ammonification is changed into via the initial oxidation way of ammonification again; Adopted comparatively gentle reaction conditions, reduced in production energy consumption and the industrial production, reduced to produce and dropped into the requirement of production unit.
(3) this method has been used routine be easy to get low-cost methyl alcohol, ethanol, water, methylene dichloride, acetonitrile equal solvent; And simplified the industrial production aftertreatment; Optimized operational path, reduced the pressure that the three wastes bring to environment, strong compression production cost and aftertreatment input.
(4) this synthetic route is owing to the selection of its solvent and conversion unit, and its industrial safety performance is greatly improved.
(5) title product that obtains of this synthetic route, superior its content HPLC >=99.9%
The method of comprehensive above-mentioned this synthesising target compound is at present a kind ofly can be applicable to industrial production, the synthetic route that economy and operability are all very superior.
Embodiment 1
In the 500 mL four-hole boiling flasks that mechanical stirring, TM, moisture eliminator are housed, feed N
2Air is fallen in displacement.Drop into 200 g absolute ethyl alcohols (moisture requirement≤0.5%); Be cooled to 10 ℃ with ice-water bath; Drop into 18.8 g sodium ethylates (S,S-Dimethyl cyanoimidodithiocarbonate: sodium ethylate=1mol:1.1mol) then; Temperature control drops into 18.2 g propane dinitrile (S,S-Dimethyl cyanoimidodithiocarbonate: propane dinitrile=1mol:1.1mol) and S,S-Dimethyl cyanoimidodithiocarbonate 36.7 g in 10-20 ℃ of TR.Reaction is 12-15 hour under the 10-20 ℃ of temperature.Vacuum filtration, drying treatment obtain compound (II) 1-methylthio group-1-cyanogen amino-2,2-dicyano ethene sodium salt.This compound is the white solid powder, its content: HPLC >=98%.
Embodiment 2
In the 500 mL four-hole boiling flasks that mechanical stirring, TM, moisture eliminator are housed, feed N
2Air is fallen in displacement.Drop into 200 g absolute ethyl alcohols (moisture requirement≤0.5%); Be cooled to 10 ℃ with ice-water bath; Drop into 25.6 g sodium ethylates (S,S-Dimethyl cyanoimidodithiocarbonate: sodium ethylate=1mol:1.5mol) then; Temperature control drops into 24.9 g propane dinitrile (S,S-Dimethyl cyanoimidodithiocarbonate: propane dinitrile=1mol:1.5mol) and S,S-Dimethyl cyanoimidodithiocarbonate 36.7 g in 10-20 ℃ of TR.Reaction is 12-15 hour under the 10-20 ℃ of temperature.Vacuum filtration, drying treatment obtain compound (II) 1-methylthio group-1-cyanogen amino-2,2-dicyano ethene sodium salt.This compound is the white solid powder, its content: HPLC >=98%.
Embodiment 3
The compound 1-methylthio group that obtains-1-cyanogen amino-2; 2-dicyano ethene sodium salt; Input is equipped with TM, prolong, in the funnel that feeds intake, churned mechanically 1000 mL four-hole boiling flasks, drop into 100 g pure water, drips 263 g refined salt acid (S,S-Dimethyl cyanoimidodithiocarbonate: HCl=1mol:8mol).Reaction is 12 hours under 30-40 ℃ of temperature condition, and vacuum filtration with the washing of 100 g pure water, is used 100 g 2%Na again
2CO
3Solution washing, drying treatment product obtain 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine 37.5 g of off-white color, two step total recoverys 74.6%, content: HPLC>=95%, m.p.:267-268 ℃.
Embodiment 4
The compound 1-methylthio group that obtains-1-cyanogen amino-2; 2-dicyano ethene sodium salt; Input is equipped with TM, prolong, in the funnel that feeds intake, churned mechanically 1000 mL four-hole boiling flasks, drop into 100 g pure water, drips 460g refined salt acid (S,S-Dimethyl cyanoimidodithiocarbonate: HCl=1mol:12mol).Reaction is 12 hours under 30-40 ℃ of temperature condition, and vacuum filtration with the washing of 100 g pure water, is used 100 g 2%Na again
2CO
3Solution washing, drying treatment product obtain 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine 39.5 g of off-white color, two step total recoverys 78.6%, content: HPLC>=95%, m.p.:267-268 ℃.
Embodiment 5
In 500 mL four-hole boiling flasks, drop into 250 g ethanol successively, compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine 38.5 g, cyclopropylamine 12 g (2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine: cyclopropylamine=1mol:1.1mol), and solid Na
2CO
320.4g (2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine: Na
2CO
3=1mol:1mol), reaction system is warming up to backflow, reacted 5 hours; Decompression steams solvent; Be cooled to room temperature, in flask, add 200 g pure water, make temperature reduce to 10 ℃; Also with the washing of 100 g pure water, drying treatment obtains 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine 37.4 g to vacuum filtration.This compound is white or off-white color pressed powder, yield: 87.9%.m.p.：222-224℃。Content: HPLC >=98%
Embodiment 6
In 500 mL four-hole boiling flasks; Drop into 250 g ethanol successively; Compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine 38.5 g, cyclopropylamine 16.5 g (2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine: cyclopropylamine=1mol:1.5mol), and solid Na
2CO
320.4g (2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine: Na
2CO
3=1mol:1mol), reaction system is warming up to backflow, reacted 5 hours; Decompression steams solvent; Be cooled to room temperature, in flask, add 200 g pure water, make temperature reduce to 10 ℃; Also with the washing of 100 g pure water, drying treatment obtains 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine 37.7 g to vacuum filtration.This compound is white or off-white color pressed powder, yield: 88.6%.m.p.：222-224℃。Content: HPLC >=98%
Embodiment 7
At 500 mL TM, prolong are housed, in the funnel that feeds intake, churned mechanically four-hole boiling flask; Drop into dichloromethane solvent 220 g about temperature control to 20 ℃; 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine 37 g that the last step obtains drop into acetate 20 g, and carbamide peroxide 47.2 g (4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine: carbamide peroxide=1mol:3mol); Be warming up to 35 ℃ and stop heating; Naturally be warming up to back flow reaction 1-2 hour, heating keeps backflow 1-2 hour then, steams solvent.In flask, add the 200g pure water, be cooled to 10 ℃, the washing of suction filtration 100 g pure water.Drying treatment obtains 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine, and this compound is a white powder.
Embodiment 8
At 500 mL TM, prolong are housed, in the funnel that feeds intake, churned mechanically four-hole boiling flask; Drop into dichloromethane solvent 220 g about temperature control to 20 ℃; 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine 37 g that the last step obtains drop into acetate 20 g, and carbamide peroxide 94.5 g (4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine: carbamide peroxide=1mol:6mol); Be warming up to 35 ℃ and stop heating; Naturally be warming up to back flow reaction 1-2 hour, heating keeps backflow 1-2 hour then, steams solvent.In flask, add the 200g pure water, be cooled to 10 ℃, the washing of suction filtration 100 g pure water.Drying treatment obtains 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine, and this compound is a white powder.
Embodiment 9
4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine (case 7 obtains) drops into that 500 mL are equipped with TM, prolong, in the funnel that feeds intake, churned mechanically four-hole boiling flask; Drop into acetonitrile 120 g, drop into ammoniacal liquor 203 g (content>=23%) (4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine: NH
3H
2O=1mol:8mol) material melts clearly, and reaction is 5 hours under 45 ℃ of insulations.Steam solvent, be chilled to the room temperature suction filtration, washing obtains 4, and 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine bullion, bullion use the DMF recrystallization finally to obtain 20.4 g elaboration.Five step total recoverys are: 42%.Content: HPLC >=99.9%.m.p.：249-251℃。
Embodiment 10
4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine (case 8 obtains) drops into that 500 mL are equipped with TM, prolong, in the funnel that feeds intake, churned mechanically four-hole boiling flask; Drop into acetonitrile 120 g, drop into ammoniacal liquor 306g (content>=23%) (4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine: NH
3H
2O=1mol:12mol) material melts clearly, and reaction is 5 hours under 45 ℃ of insulations.Steam solvent, be chilled to the room temperature suction filtration, washing obtains 4, and 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine bullion, bullion use the DMF recrystallization finally to obtain 22 g elaboration.Five step total recoverys are: 48.4%.Content: HPLC >=99.9%.m.p.：249-251℃。
Claims (5)
1.4 the preparation method of 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine is characterized in that carrying out according to following step:
(1) N, N-dimethyl--S, the alkaline alcohol solvent of S-dithiocarbonic acid dimethyl ester and propane dinitrile react down at 0 ~ 40 ℃ and obtain compound 1-methylthio group-1-cyanogen amino-2,2-dicyano ethene an alkali metal salt;
(2) the compound 1-methylthio group that step (1) is obtained-1-cyanogen amino-2; 2-dicyano ethene an alkali metal salt dissolves in 30 ℃ of water, is to handle through persalt under 20-40 ℃ to obtain compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine in temperature of reaction again;
(3) the compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine that step (2) is obtained is dissolved in the organic solvent, adds Na
2CO
3Carry out temperature rising reflux with cyclopropylamine, its reflux temperature is 78-79 ℃, obtains compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-first mercaptopyrimidine;
(4) compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid of obtaining of step (3)-6-first mercaptopyrimidine is through carbamide peroxide; The acetic acid catalysis system; Catalyzed oxidation in organic solvent obtains compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine;
(5) compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine of obtaining of step (4), carries out ammonification with the ammoniacal liquor doubly of molar equivalent 8-12 and finally obtains title product as solvent with acetonitrile.
2. according to claim 14; The preparation method of 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine; It is characterized in that wherein step (3) compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine and cyclopropylamine mol ratio are 1:1.1-1.5, the mol ratio of yellow soda ash and compound 2-chloro-4-amino-5-cyano-6-first mercaptopyrimidine is 1:1.
3. according to claim 14; The preparation method of 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine is characterized in that wherein the mol ratio of step (4) compound 4-amino-2-(cyclopropyl amino)-5-cyanic acid-6-methanesulfonyl pyrimidine and carbamide peroxide is 1:3-6; Wherein answering temperature is 38-40 ℃; Wherein organic solvent is methyl alcohol, ethanol, acetone, acetonitrile or methylene dichloride.
4. according to claim 14, the preparation method of 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine, the temperature of reaction that it is characterized in that this reaction is 0-55 ℃.
5. according to claim 34, the preparation method of 6-diamino--2-cyclopropyl amino-5-itrile group pyrimidine is characterized in that
Wherein organic solvent is a methylene dichloride.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103168A (en) * | 1986-04-30 | 1987-12-16 | 希巴-盖格公司 | The pyrimidines that replaces |
| CN1128024A (en) * | 1993-07-26 | 1996-07-31 | 希巴-盖吉股份公司 | Process for the preparation of substituted 4,6-diamino-5-cyanopyrimidines |
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2011
- 2011-12-15 CN CN2011104204733A patent/CN102399193A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103168A (en) * | 1986-04-30 | 1987-12-16 | 希巴-盖格公司 | The pyrimidines that replaces |
| CN1128024A (en) * | 1993-07-26 | 1996-07-31 | 希巴-盖吉股份公司 | Process for the preparation of substituted 4,6-diamino-5-cyanopyrimidines |
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Application publication date: 20120404 |