CN103923086A - Preparation method of 5-alkoxy-1,2,4-triazole[4,5-c]pyrimidine-3(2H)-thioketone - Google Patents
Preparation method of 5-alkoxy-1,2,4-triazole[4,5-c]pyrimidine-3(2H)-thioketone Download PDFInfo
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- CN103923086A CN103923086A CN201410127608.0A CN201410127608A CN103923086A CN 103923086 A CN103923086 A CN 103923086A CN 201410127608 A CN201410127608 A CN 201410127608A CN 103923086 A CN103923086 A CN 103923086A
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- pyrimidine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
Abstract
The invention relates to a preparation method of 5-alkoxy-1,2,4-triazole[4,5-c]pyrimidine-3(2H)-thioketone. The method comprises the following steps: dissolving 2-alkoxy-4-hydrazino-5(or 6)-halogenated pyrimidine into an organic solvent under protection of N2, adding a catalyst and carbon disulfide to be mixed, stirring for 0.5-3h, and raising the temperature to backflow; cooling after backflow reaction, acidizing and adjusting pH; carrying out suction filtration, recrystallizing solid in a recrystallization solvent, separating the solid, and carrying out vacuum drying. By utilizing the preparation method, the temperature is directly raised to backflow, an oxidizing agent of hydrogen peroxide is not used, the temperature of dropwise added hydrogen peroxide does not need to be controlled, and therefore, elemental sulfur can not be generated, the elemental sulfur does not need to be filtered to remove, the steps are simple, and the reaction is easy to control. The adopted catalyst has good catalytic performance, the reaction yield is greatly improved, the reaction condition is moderate, and special equipment is not needed.
Description
Technical field
The present invention relates to a kind of 5-alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, belongs to technical field of organic synthesis.
Background technology
5-alkoxyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones is the important intermediate of preparing triazolo pyrimidine class sulfonamides herbicide, and triazolopyrimidine sulfonamides compound contains triazole and the important active structure unit of pyrimidine two classes simultaneously, show good biological activity, at agricultural chemicals, be particularly used widely in weedicide field.
Triazolopyrimidine sulfonamides herbicide is after sulfonylurea and imidazolinone herbicide, the novel ultra-high efficiency weedicide of a class of being invented by The Dow Agrosciences, LLC., it is active suitable with sulfonylurea herbicide chaste tree, and action target is also acetolactate synthestase (ALS).If cloransulammethyl, two chlorine sulphur draft and florasulam are all triazolopyrimidine sulfonamides herbicides, their general formula as shown in the formula (II):
In formula (II), R
1, R
2respectively do for oneself H, F, Cl or-OCH
3,-OCH
2cH
3or-CO
2cH
3; R
3for H ,-CH
3or-CH
2cH
3; R
4, R
5h, F, Cl or Br respectively do for oneself.
Therefore, 5-alkoxyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones is the important as precursors of synthetic this compounds, it prepares significant.
At present, 5-alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones only has a kind of method of Tao Shi benefit agriculture: use hydrogen peroxide oxidation to close the method for ring.By 2-methoxyl group-4-diazanyl-5-FU, methyl alcohol, triethylamine, dithiocarbonic anhydride at N
2protection is lower to be mixed, stirring at room temperature.Then ice bath is cooled to 15 DEG C, uses syringe pump to drip 30% hydrogen peroxide, and time for adding exceedes 1h, maintains temperature of reaction 15 DEG C of left and right.After hydrogen peroxide dropwises, insulated and stirred 1h.The elemental sulfur that suction filtration generates except dereaction, filtrate is cooled to 0 DEG C, and hcl acidifying, separates out solid.
This preparation 5-alkoxyl group-1,2,4-triazole [4,5-c] method of pyrimidine-3 (2H)-thioketones is by oxidants hydrogen peroxide, and in the process of Cheng Huan the rate of addition to hydrogen peroxide, all stricter to temperature controlled requirement, and many technique of removing together elemental sulfur, these operations have not only increased the cost of reaction, and can increase extra drain on manpower and material resources in sulphur removal process, cause unnecessary trouble to industrialized production.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of simple to operate, mild condition, safe and reliable 5-alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones.
Technical scheme of the present invention is as follows:
A kind of 5-alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, comprises that step is as follows:
(1) at N
2under protection, by 2-alkoxyl group-4-diazanyl-5(or 6)-halogenated pyrimidine is dissolved in organic solvent, adds catalyzer and dithiocarbonic anhydride, and mix and blend 0.5～3h, is warming up to backflow, back flow reaction 1～5h; Described 2-alkoxyl group-4-diazanyl-5(or 6) mol ratio of-halogenated pyrimidine, catalyzer and dithiocarbonic anhydride is (0.8～1): (1～3): (1～5), described catalyzer is organic bases or mineral alkali;
(2) after back flow reaction, be cooled to-3～0 DEG C, acidifying is also adjusted pH to 1～5, occurs white precipitate;
(3) suction filtration carries out solid recrystallization in recrystallization solvent, separate solid, and vacuum-drying, obtains 5-alkoxyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones.
5-alkoxyl group-1 that the present invention makes, 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones structural formula as shown in the formula (I):
In formula (I), R is-CH
3or-CH
2cH
3; X and Y are respectively H, F, Cl or Br, and X and Y can identical also can be different, but X and Y can not be H simultaneously.This compounds prepared by the present invention has triazolo pyrimidine ring, can be used for synthetic triazolo pyrimidine SULPHURYL CHLORIDE, triazolopyrimidine sulfonamides compound, also can be used as raw material for medicine and pesticide field.
Raw materials used 2-alkoxyl group-4-diazanyl-5(or 6 in step of the present invention (1))-halogenated pyrimidine is conventional commercial product, also can prepare by prior art.Can be with reference to patent documentation WO9512597 preparation, white needle-like crystals, purity be greater than 99%, 2-alkoxyl group-4-diazanyl-5(or 6) general formula of-halogenated pyrimidine as shown in the formula (III):
In formula (III), X, Y are consistent with the group of representative in formula (I) with R.
According to the present invention, preferably, the 2-alkoxyl group-4-diazanyl-5(or 6 described in step (1))-halogenated pyrimidine is 2-oxyethyl group-4 diazanyl-6-5-FU, 2-methoxyl group-4-diazanyl-5-chloropyrimide, 2-oxyethyl group-4-diazanyl-5-FU, 2-methoxyl group-4-diazanyl-5-FU or 2-oxyethyl group-4-diazanyl-6-chloropyrimide.
5-alkoxyl group-1 that the present invention prepares, 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones is preferably the fluoro-5-of 7-oxyethyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, 8-chloro-5-methoxyl-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, the fluoro-5-of 8-oxyethyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, the fluoro-5-of 8-methoxyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones or the chloro-5-of 7-oxyethyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones.
According to the present invention, preferred, the organic solvent described in step (1) is methylene dichloride, methyl alcohol, ethanol, Virahol or the trimethyl carbinol, further particular methanol; Described 2-alkoxyl group-4-diazanyl-5(or 6) mol ratio of-halogenated pyrimidine, catalyzer and dithiocarbonic anhydride is 1:(1～2): (1～3); Described organic bases is pyridine, diethylamine, triethylamine or methylamine, and described mineral alkali is sodium hydroxide, sodium phosphate, sodium carbonate or ammoniacal liquor; The preferred organic bases of catalyzer, further preferred triethylamine;
2-alkoxyl group-4-diazanyl-5(or 6) quality of-halogenated pyrimidine is 0.08～0.50g/ml with the ratio of the volume of organic solvent.
According to the present invention, preferred, in step (1), reflux temperature is preferably 50～70 DEG C, more preferably 55～65 DEG C; Reflux time is preferably 2～4h.
According to the present invention, preferred, in step (2), acidifying acid used is to be sulfuric acid or the acetic acid of hydrochloric acid, 5～20wt%, further preferred hydrochloric acid; Preferably regulate pH to 2～4.
According to the present invention, preferred, the recrystallization solvent described in step (3) is one or more the mixture in sherwood oil, hexanaphthene, methyl alcohol, ethanol, methylene dichloride, further preferred alcohol.
Reaction principle of the present invention is:
R is-CH
3or-CH
2cH
3; X and Y are respectively H, F, Cl or Br, and X and Y can identical also can be different, but X and Y can not be H simultaneously.
Beneficial effect:
1, the inventive method is directly warming up to back flow reaction, does not use oxidant hydrogen peroxide, need not control the temperature that drips hydrogen peroxide, therefore also can not generate elemental sulfur, need not remove by filter elemental sulfur, and step is simple, and reaction is easy to control.
2, the catalyzer that the inventive method adopts has good catalytic performance, has greatly improved reaction yield, and reaction conditions is also gentleer, without specific installation.
3, simple to operate, the mild condition, safe and reliable of the inventive method, and productive rate is higher, is applicable to industrialized production.
Brief description of the drawings
Fig. 1, Fig. 2 are respectively the fluoro-5-of 8-methoxyl group-1 that the embodiment of the present invention 1 makes, 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones
1h NMR and
13c NMR spectrogram.
Embodiment
Below by example, the invention will be further described, but do not limit the scope of the invention.
Raw materials used 2-alkoxyl group-4-diazanyl-5(or 6 in embodiment)-halogenated pyrimidine prepares by patent documentation WO9512597, white needle-like crystals, purity is greater than 99%.Other raw materials markets are buied.
In embodiment
1the test condition of H NMR: instrument title: nuclear magnetic resonance spectrometer, specifications and models: AVANCE II400, production firm: Bruker, uses solvent: dimethyl sulfoxide (DMSO) (DMSO-d6).
The fluoro-5-of embodiment 1:8-methoxyl group-1, the preparation of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones
At N
2under protection, by 2-methoxyl group-4-diazanyl-5-FU (79.1g, 0.5mol), methyl alcohol (500ml), triethylamine (55.7g, 0.55mol), dithiocarbonic anhydride (38.1g, 0.5mol) is in 25 DEG C of mix and blends, and solution slowly becomes oyster white non-homogeneous mixture.After stirring at room temperature 0.5h, be warming up to 58 DEG C of back flow reaction 2h.Stop heating, naturally cool to room temperature, then ice bath is cooled to 0 DEG C.Add dilute hydrochloric acid (510g, the 0.7mol) acidifying of 5wt%, adjust pH to 2, separate out the fluoro-5-of off-white color solid 8-methoxyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones.Suction filtration, by the solid obtaining recrystallization in ethanol, obtain the fluoro-5-of white solid 8-methoxyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones (95.1g, 0.475mol), productive rate is 94.9%, 166 DEG C of fusing points (decomposition).
NMR(d
6-DMSO):δ：
1H：4.01(s,3H),7.65(d,1H),14.54(brs,1H)；
13C：56.11,125.6,141.9,144.4,147.3,161.2。
The fluoro-5-of embodiment 2:7-oxyethyl group-1, the preparation of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones
At N
2under protection, by 2-oxyethyl group-4-diazanyl-6-5-FU (86.7g, 0.5mol), ethanol (500g), triethylamine (102g, 1.0mol), dithiocarbonic anhydride (68.5g, 0.9mol) is warming up to 72 DEG C of back flow reaction 3h after 25 DEG C of mix and blend 1h.Stop heating, naturally cool to room temperature, then ice bath is cooled to 0 DEG C.Add acetic acid,diluted (1200g, the 1.0mol) acidifying of 5wt%, adjust pH to 1, separate out the fluoro-5-of off-white color solid 7-oxyethyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones.Suction filtration, by the solid obtaining recrystallization in ethanol, obtain white solid 98.5g, productive rate 92%, 170 DEG C of fusing points.
Ultimate analysis (C
7h
7fN
4oS):
Theoretical value (%): C, 39.2; H, 3.29; N, 26.2
Measured value (%): C, 38.9; H, 3.31; N, 26.3.
The chloro-5-of embodiment 3:7-oxyethyl group-1, the preparation of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones
At N
2under protection, by 2-methoxyl group-4-diazanyl-6-chloropyrimide (95.6g, 0.5mol), methyl alcohol (500ml), triethylamine (60.7g, 0.6mol), dithiocarbonic anhydride (91.4g, 1.2mol) is in 25 DEG C of mix and blends, and solution slowly becomes oyster white non-homogeneous mixture.After stirring at room temperature 2h, be warming up to 57 DEG C of backflows, in this process, oyster white non-homogeneous mixture gradually becomes yellow homogeneous phase solution, backflow 4h.Stop heating, naturally cool to room temperature, then cryosel bath is cooled to-3 DEG C.Add acetic acid,diluted (600g, the 0.5mol) acidifying of 5wt%, adjust pH to 4, separate out yellow solid.Suction filtration, the mixed solution washing of 2 × 50ml cold methanol and water, obtains the chloro-5-of faint yellow solid 7-oxyethyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones (96.4g, 0.44mol), productive rate is 89%, fusing point is greater than 187 DEG C (decomposition).
Ultimate analysis (C
7h
7clN
4oS):
Theoretical value (%): C, 36.4; H, 3.06; N, 24.3
Measured value (%): C, 36.7; H, 3.01; N, 24.1
Embodiment 4:8-chloro-5-methoxyl-1, the preparation of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones
At N
2under protection, by 2-methoxyl group-4-diazanyl-5-chloropyrimide (95.6g, 0.5mol), methyl alcohol (500ml), triethylamine (60.7g, 0.6mol), dithiocarbonic anhydride (91.4g, 1.2mol) is in 25 DEG C of mix and blends, and solution slowly becomes oyster white non-homogeneous mixture.After stirring at room temperature 2h, be warming up to 57 DEG C of backflows, in this process, oyster white non-homogeneous mixture gradually becomes yellow homogeneous phase solution, backflow 4h.Stop heating, naturally cool to room temperature, then cryosel bath is cooled to-3 DEG C.Add dilute hydrochloric acid (365g, the 0.5mol) acidifying of 5wt%, adjust pH to 4, separate out faint yellow solid 8-chloro-5-methoxyl-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones.Suction filtration, obtains white solid (96.4g, 0.44mol), and productive rate is 89%, and fusing point is greater than 200 DEG C (decomposition).
NMR(d
6-DMSO):δ：
1H：4.04(s,3H),7.67(s,1H),14.25(brs,1H)；
13C：56.18,110.08,140.46,145.76,150.11,161.32。
Claims (10)
1. 5-alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, comprises that step is as follows:
(1) at N
2under protection, by 2-alkoxyl group-4-diazanyl-5(or 6)-halogenated pyrimidine is dissolved in organic solvent, adds catalyzer and dithiocarbonic anhydride, and mix and blend 0.5～3h, is warming up to backflow, back flow reaction 1～5h; Described 2-alkoxyl group-4-diazanyl-5(or 6) mol ratio of-halogenated pyrimidine, catalyzer and dithiocarbonic anhydride is (0.8～1): (1～3): (1～5), described catalyzer is organic bases or mineral alkali;
(2) after back flow reaction, be cooled to-3～0 DEG C, acidifying is also adjusted pH to 1～5, occurs white precipitate;
(3) suction filtration carries out solid recrystallization in recrystallization solvent, separate solid, and vacuum-drying, obtains 5-alkoxyl group-1,2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones.
2. 5-according to claim 1 alkoxyl group-1,2,4-triazole [4,5-c] preparation method of pyrimidine-3 (2H)-thioketones, it is characterized in that the 2-alkoxyl group-4-diazanyl-5(or 6 described in step (1))-halogenated pyrimidine is 2-oxyethyl group-4 diazanyl-6-5-FU, 2-methoxyl group-4-diazanyl-5-chloropyrimide, 2-oxyethyl group-4-diazanyl-5-FU, 2-methoxyl group-4-diazanyl-5-FU or 2-oxyethyl group-4-diazanyl-6-chloropyrimide.
3. 5-according to claim 1 alkoxyl group-1, 2, 4-triazole [4, 5-c] preparation method of pyrimidine-3 (2H)-thioketones, it is characterized in that, described 5-alkoxyl group-1, 2, 4-triazole [4, 5-c] pyrimidine-3 (2H)-thioketones is the fluoro-5-of 7-oxyethyl group-1, 2, 4-triazole [4, 5-c] pyrimidine-3 (2H)-thioketones, 8-chloro-5-methoxyl-1, 2, 4-triazole [4, 5-c] pyrimidine-3 (2H)-thioketones, the fluoro-5-of 8-oxyethyl group-1, 2, 4-triazole [4, 5-c] pyrimidine-3 (2H)-thioketones, the fluoro-5-of 8-methoxyl group-1, 2, 4-triazole [4, 5-c] pyrimidine-3 (2H)-thioketones or the chloro-5-of 7-oxyethyl group-1, 2, 4-triazole [4, 5-c] pyrimidine-3 (2H)-thioketones.
4. 5-according to claim 1 alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, is characterized in that, the organic solvent described in step (1) is methylene dichloride, methyl alcohol, ethanol, Virahol or the trimethyl carbinol.
5. 5-according to claim 1 alkoxyl group-1,2,4-triazole [4,5-c] preparation method of pyrimidine-3 (2H)-thioketones, it is characterized in that the 2-alkoxyl group-4-diazanyl-5(or 6 described in step (1)) mol ratio of-halogenated pyrimidine, catalyzer and dithiocarbonic anhydride is 1:(1～2): (1～3); Described organic bases is pyridine, diethylamine, triethylamine or methylamine, and described mineral alkali is sodium hydroxide, sodium phosphate, sodium carbonate or ammoniacal liquor.
6. 5-according to claim 1 alkoxyl group-1,2,4-triazole [4,5-c] preparation method of pyrimidine-3 (2H)-thioketones, it is characterized in that the 2-alkoxyl group-4-diazanyl-5(or 6 described in step (1))-halogenated pyrimidine is 0.08～0.50g/ml with the ratio of the quality volume of organic solvent.
7. 5-according to claim 1 alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, is characterized in that, and the reflux temperature described in step (1) is 50～70 DEG C, and reflux time is 2～4h.
8. 5-according to claim 1 alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, is characterized in that, in step (2), acidifying acid used is to be sulfuric acid or the acetic acid of hydrochloric acid, 5～20wt%.
9. 5-according to claim 1 alkoxyl group-1, the preparation method of 2,4-triazole [4,5-c] pyrimidine-3 (2H)-thioketones, is characterized in that, regulates pH to 2～4 in step (2).
10. 5-according to claim 1 alkoxyl group-1,2,4-triazole [4,5-c] preparation method of pyrimidine-3 (2H)-thioketones, it is characterized in that, the recrystallization solvent described in step (3) is one or more the mixture in sherwood oil, hexanaphthene, methyl alcohol, ethanol, methylene dichloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111217817A (en) * | 2020-02-26 | 2020-06-02 | 山东潍坊润丰化工股份有限公司 | Preparation method of triazolopyrimidine herbicide |
| CN114437083A (en) * | 2022-02-11 | 2022-05-06 | 德州绿霸精细化工有限公司 | Synthetic method of thioketone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217817A (en) * | 2020-02-26 | 2020-06-02 | 山东潍坊润丰化工股份有限公司 | Preparation method of triazolopyrimidine herbicide |
| CN114437083A (en) * | 2022-02-11 | 2022-05-06 | 德州绿霸精细化工有限公司 | Synthetic method of thioketone |
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