CN104387328A - Method of preparing 2-chloropyrimidine - Google Patents
Method of preparing 2-chloropyrimidine Download PDFInfo
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- CN104387328A CN104387328A CN201410708312.8A CN201410708312A CN104387328A CN 104387328 A CN104387328 A CN 104387328A CN 201410708312 A CN201410708312 A CN 201410708312A CN 104387328 A CN104387328 A CN 104387328A
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- reaction
- trichloropyrimidine
- barbituric acid
- zinc powder
- water
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- BIIMQLIFYYVQOB-YICFLHHFSA-N CC(/N=C(\C=C(/N)\Cl)/Cl)Cl Chemical compound CC(/N=C(\C=C(/N)\Cl)/Cl)Cl BIIMQLIFYYVQOB-YICFLHHFSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/30—Halogen atoms or nitro radicals
Abstract
The invention discloses a method of preparing 2-chloropyrimidine. The method comprises the following steps: firstly carrying out reaction on malonic acid bis-ethylacetate and urea with sodium methoxide as a catalyst to obtain barbituric acid, then carrying out reaction on the barbituric acid and phosphorus oxychloride with N, N-dimethylaniline as a catalyst to obtain 2, 4, 6-trichloropyrimidine, and finally carrying out redox reaction on the 2, 4, 6-trichloropyrimidine and zinc powder in a solvent of methanol and water under the alkaline condition to obtain the 2-chloropyrimidine, wherein the molar ratio of the 2, 4, 6-trichloropyrimidine to the zinc powder is 1:(1-1.2). According to the method disclosed by the invention, by virtue of the 2, 4, 6-trichloropyrimidine and the zinc powder with the molar ratio to be 1:(1-1.2), only chlorine on 4 and 6 bits on a pyrimidine ring of the 2, 4, 6-trichloropyrimidine can be reduced, so that the side effect of generating dichloride or pyrimidine is reduced; and by virtue of the reaction route, the 2-chloropyrimidine with high purity and yield is obtained.
Description
Technical field
The present invention relates to technical field prepared by 2-chloropyrimide, particularly relate to a kind of method preparing 2-chloropyrimide.
Background technology
2-chloropyrimide has another name called 2-chloropyridine quinoline, and molecular formula is C
4h
3clN
2, its molecular weight is 114.53, No. CAS is 1722-12-9, and it is a kind of white or pale yellow powder, and fusing point is 63 ~ 66 DEG C, and boiling point is 75 ~ 76 DEG C, and flash-point is 98 DEG C.Prior art prepares the technological deficiency that yield is lower and product purity is lower of the method existence of 2-chloropyrimide.
Summary of the invention
In view of this, the invention provides a kind of method preparing 2-chloropyrimide, the purity of the product of this preparation method is higher, yield is higher.
Prepare a method for 2-chloropyrimide, comprise the following steps:
(1) propanedioic acid ethyl diacetate and urea are reacted under the condition being catalyzer with sodium methylate, obtain barbituric acid, as reaction formula I,
(2) by barbituric acid under the condition being catalyzer with DMA, with phosphorus oxychloride reaction, obtain 2,4,6-trichloropyrimidine, as reaction formula II,
(3) be 1:(1 ~ 1.2 by mol ratio) 2,4,6-trichloropyrimidines and zinc powder in the solvent of first alcohol and water, under alkaline condition, obtain 2-chloropyrimide by redox reaction, as reaction formula III,
In the method for above-mentioned preparation, described in step (1), the temperature of reaction is 65 ~ 75 DEG C.
Wherein, in reaction described in step (1), the present invention is unrestricted to the form of sodium methylate, such as, can select the methanol solution of sodium methylate, such as 15 ~ 30wt%.The feed way of reactant without particular determination, such as, can adopt urea to drip continuously in propanedioic acid ethyl diacetate.React and carry out under comparatively strong acidic condition, being preferably pH value is 1.5 ~ 3.Regulating the acid of pH without specific restriction, such as, can be the concentrated hydrochloric acid of 38wt% by mass percentage concentration.The mol ratio of propanedioic acid ethyl diacetate, urea and sodium methylate is preferably 1:1.05 ~ 1.15:1.15 ~ 1.25, is 1:1.1:1.2 better.This mol ratio than 1:1:1, can ensure the barbituric acid obtaining better yield higher than the theoretical molar of reacting like this.What deserves to be explained is, can according to the fusing point of the barbituric acid reported in prior art and solubleness, select the barbituric acid in the reaction product of reacting this step to purify, such as recrystallization etc., at this just not in the process repeating its concrete purification.
In step (2), the temperature of described reaction is preferably 40 ~ 50 DEG C, more preferably 45 DEG C.The mol ratio of barbituric acid and phosphorus oxychloride is 1:5.1 ~ 5.5, is 1:5.3 better.When meeting the mol ratio of above-mentioned preferably temperature of reaction and barbituric acid and phosphorus oxychloride, 2,4,6-trichloropyrimidines of larger yield can be obtained.After completion of the reaction, the temperature of this step reaction product can bring up to 100 ~ 110 DEG C, and constantly stir.Then add such as ice cube wherein to lower the temperature, stratification, take off a layer solid and be thick product.Then carry out washing with alkali lye dry, 2,4,6-trichloropyrimidine product can be obtained.
In redox reaction described in step (3), under the prerequisite that zinc powder is enough or excessive, on the pyrimidine ring of 2,4,6-trichloropyrimidine 2,4, the chlorine on 6 all can be reduced.But due to 2, the reducing activity of 4,6 upper chlorine makes different, specifically, 4, the reducing activity of the chlorine on 6 is identical, be far longer than, and the chlorine on 2, thus 4, chlorine on 6 is preferably reduced, and only has after the chlorine on 4,6 is reduced, and 2 upper chlorine start to be reduced.Based on this, control 4 by the reaction mole number of zinc powder, 6 upper chlorine are reduced just, and namely the mole number of zinc powder is 2,4,6-trichloropyrimidine equivalent, then can ensure that 2 upper chlorine are not reduced.The present invention 2,4,6-trichloropyrimidine and zinc powder mol ratio are preferably 1:(1 ~ 1.2), this mol ratio is larger than 1:1, zinc powder can be made so slightly to exceed reductase 12, theoretical value needed for chlorine on the pyrimidine ring of 4,6-trichloropyrimidine on 4,6, substantially eliminate the consumption that zinc powder produces because of side reaction, fully ensure that 4, the chlorine on 6 is reduced, and improves the yield of 2-chloropyrimide.The temperature of reaction is preferably 76 ~ 84 DEG C, is 80 DEG C better.The time of reaction is preferably 6 ~ 8h, is 7h better.In order to reduce reaction product volatilization, the device of this reaction can be equipped with reflux.The volume ratio of methyl alcohol and water is 1:1.5 ~ 3, is 1:2.5 better.Material the present invention of alkaline condition can be provided not to be restricted, such as, can be caustic soda.Reaction product after completion of the reaction, can be cooled to 78 ~ 82 DEG C, hot wash filter cake by this step.Filtrate and part washing lotion merge, and add granular caustic soda, below 50, alkali analyses 1h.Separate jelly after adding ethyl acetate, regulate pH=7.5 ~ 8 with hydrochloric acid, then separate oily matter, reclaim ethyl acetate, separate out white crystal, fusing point is 123 ~ 124 DEG C, i.e. 2-chloropyrimide, finally by product 40 ~ 50 DEG C of oven dry.
First the present invention reacts under the condition being catalyzer with sodium methylate with propanedioic acid ethyl diacetate and urea, obtain barbituric acid, then be under the condition of catalyzer with DMA, with phosphorus oxychloride reaction, obtain 2,4,6-trichloropyrimidine, last mol ratio is 1:(1 ~ 1.2) 2,4,6-trichloropyrimidine and zinc powder obtain 2-chloropyrimide by redox reaction in the solvent of first alcohol and water, under alkaline condition.Mol ratio is 1:(1 ~ 1.2) 2,4,6-trichloropyrimidines and zinc powder can make that the pyrimidine ring of 2,4,6-trichloropyrimidine only has 4, the chlorine on 6 is reduced, and reduces and generates dichloride or with the generation of the side reaction of pyrimidine.By above-mentioned reaction scheme, obtain the 2-chloropyrimide that purity is higher, yield is higher.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
Below implement involved industrial chemicals to be mode commercially available or well-known to those skilled in the art and to obtain.As space is limited, below eliminate the concrete available sources of these industrial chemicals, should not be considered as the query to the present invention program's embodiment to this.
Embodiment 1
1.05mol urea is dropped in 1000mL four-hole bottle, the methanol solution (wherein methyl alcohol contains 1.15mol) of the sodium methylate of 25wt%, slowly 1mol diethyl malonate is dripped under reflux temperature, stirring and refluxing 2h, obtains a large amount of white powdery solids, and concentrating under reduced pressure obtains white sodium salt dry powder, add 38wt% dilute hydrochloric acid solution wherein, add water and regulate pH to 1.5, be heated to 65 DEG C, make reaction 4h.After completion of the reaction, be cooled to 0 DEG C of crystallize out, filter out crystal.Obtain white powder with methanol/water mixed solution recrystallization, be product barbituric acid.
In 1000mL four-hole bottle, drop into 5.1mol phosphorus oxychloride, DMA (60mL), is heated to 40 DEG C, in 30 ~ 60min, adds barbituric acid in batches, and temperature maintains 40 DEG C.After barbituric acid adds, slowly heat up, make temperature remain on 100 ~ 105 DEG C, stir 1.5 ~ 2h, obtain deep yellow transparent liquid, this liquid is poured into and fills in the beaker of frozen water, abundant stirring, remove supernatant liquid after leaving standstill, retain lower floor's light yellow solid, washing this light yellow solid to pH with the potassium hydroxide solution of massfraction 3% is 8 ~ 9, filtration, drying, obtain product 2,4,6-trichloropyrimidine.
Be that the methyl alcohol of 1:3 is added to water and adds in reactor and mix by volume ratio, in reactor, add caustic soda, and mol ratio be 2,4,6-trichloropyrimidines and the zinc powder of 1:1, at 76 DEG C of back flow reaction 8h.After completion of the reaction, distill, recycle-water and methyl alcohol.Cool 77 ~ 85 DEG C of filtrations, with hot wash filter cake.Filtrate and part washing lotion merge, and add granular caustic soda, below 50 DEG C, alkali analyses 1h.Separate jelly after adding ethyl acetate, regulate pH=7.5 ~ 8 with hydrochloric acid, then separate oily matter, reclaim ethyl acetate, separate out white crystal, fusing point is 123 ~ 124 DEG C, finally 40 ~ 50 DEG C of oven dry, namely obtains product 2-chloropyrimide.
Embodiment 2
1.15mol urea is dropped in 1000mL four-hole bottle, the methanol solution (wherein methyl alcohol contains 1.25mol) of the sodium methylate of 25wt%, slowly 1mol diethyl malonate is dripped under reflux temperature, stirring and refluxing 3h, obtains a large amount of white powdery solids, and concentrating under reduced pressure obtains white sodium salt dry powder, add 38wt% dilute hydrochloric acid solution wherein, add water and regulate pH to 3, be heated to 75 DEG C, make reaction 2h.After completion of the reaction, be cooled to 0 DEG C of crystallize out, filter out crystal.Obtain white powder with methanol/water mixed solution recrystallization, be product barbituric acid.
In 1000mL four-hole bottle, drop into 5.5mol phosphorus oxychloride, DMA (60mL), is heated to 40 DEG C, in 30 ~ 60min, adds barbituric acid in batches, and temperature maintains 50 DEG C.After barbituric acid adds, slowly heat up, make temperature remain on 100 ~ 105 DEG C, stir 1.5 ~ 2h, obtain deep yellow transparent liquid, this liquid is poured into and fills in the beaker of frozen water, abundant stirring, remove supernatant liquid after leaving standstill, retain lower floor's light yellow solid, washing this light yellow solid to pH with the potassium hydroxide solution of massfraction 3% is 8 ~ 9, filtration, drying, obtain product 2,4,6-trichloropyrimidine.
Be that the methyl alcohol of 1:1.5 is added to water and adds in reactor and mix by volume ratio, in reactor, add caustic soda, and mol ratio be 2,4,6-trichloropyrimidines and the zinc powder of 1:1.2, at 84 DEG C of back flow reaction 6h.React complete distillation, recycle-water and methyl alcohol.Be cooled to 77 ~ 85 DEG C of filtrations, with hot wash filter cake.Filtrate and part washing lotion merge, and add granular caustic soda, below 50 DEG C, alkali analyses 1h.Separate jelly after adding ethyl acetate, regulate pH=7.5 ~ 8 with hydrochloric acid, then separate oily matter, reclaim ethyl acetate, separate out white crystal, fusing point is 123 ~ 124 DEG C, finally 40 ~ 50 DEG C of oven dry, namely obtains product 2-chloropyrimide.
Embodiment 3
1.10mol urea is dropped in 1000mL four-hole bottle, the sodium methylate () of 25wt%, methanol solution (wherein methyl alcohol contains 1.20mol), slowly drips 1mol diethyl malonate under reflux temperature, stirring and refluxing 2h, obtain a large amount of white powdery solids, concentrating under reduced pressure obtains white sodium salt dry powder, adds 38wt% dilute hydrochloric acid solution wherein, adds water and regulates pH to 2.5, be heated to 65 ~ 75 DEG C, make reaction 3h.After completion of the reaction, be cooled to 0 DEG C of crystallize out, filter out crystal.Obtain white powder with methanol/water mixed solution recrystallization, be product barbituric acid.
In 1000mL four-hole bottle, drop into 5.3mol phosphorus oxychloride, DMA (60mL), is heated to 40 DEG C, in 30 ~ 60min, adds barbituric acid in batches, and temperature maintains 45 DEG C.After barbituric acid adds, slowly heat up, make temperature remain on 100 ~ 105 DEG C, stir 1.5 ~ 2h, obtain deep yellow transparent liquid, this liquid is poured into and fills in the beaker of frozen water, abundant stirring, remove supernatant liquid after leaving standstill, retain lower floor's light yellow solid, washing this light yellow solid to pH with the potassium hydroxide solution of massfraction 3% is 8 ~ 9, filtration, drying, obtain product 2,4,6-trichloropyrimidine.
Be that the methyl alcohol of 1:2.5 is added to water and adds in reactor and mix by volume ratio, in reactor, add caustic soda, and mol ratio be 2,4,6-trichloropyrimidines and the zinc powder of 1:1.1, distills, recycle-water and methyl alcohol after 80 DEG C of back flow reaction 7h.Be cooled to 77 ~ 85 DEG C of filtrations, with hot wash filter cake.Filtrate and part washing lotion merge, and add granular caustic soda, below 50 DEG C, alkali analyses 1h.Separate jelly after adding ethyl acetate, regulate pH=7.5 ~ 8 with hydrochloric acid, then separate oily matter, reclaim ethyl acetate, separate out white crystal, fusing point is 123 ~ 124 DEG C, finally 40 ~ 50 DEG C of oven dry, namely obtains product 2-chloropyrimide.
Embodiment 4
1.08mol urea is dropped in 1000mL four-hole bottle, the sodium methylate of 25wt%, methanol solution (wherein methyl alcohol contains 1.18mol), slowly drips 1mol diethyl malonate under reflux temperature, stirring and refluxing 2h, obtain a large amount of white powdery solids, concentrating under reduced pressure obtains white sodium salt dry powder, adds 38wt% dilute hydrochloric acid solution wherein, adds water and regulates pH to 2, be heated to 70 DEG C, make reaction 3h.After completion of the reaction, be cooled to 0 DEG C of crystallize out, filter out crystal.Obtain white powder with methanol/water mixed solution recrystallization, be product barbituric acid.
In 1000mL four-hole bottle, drop into 5.2mol phosphorus oxychloride, DMA (60mL), is heated to 40 DEG C, in 30 ~ 60min, adds barbituric acid in batches, and temperature maintains 45 DEG C.After barbituric acid adds, slowly heat up, make temperature remain on 100 ~ 105 DEG C, stir 1.5 ~ 2h, obtain deep yellow transparent liquid, this liquid is poured into and fills in the beaker of frozen water, abundant stirring, remove supernatant liquid after leaving standstill, retain lower floor's light yellow solid, washing this light yellow solid to pH with the potassium hydroxide solution of massfraction 3% is 8 ~ 9, filtration, drying, obtain product 2,4,6-trichloropyrimidine.
Be that the methyl alcohol of 1:2 is added to water and adds in reactor and mix by volume ratio, in reactor, add caustic soda, and mol ratio be 2,4,6-trichloropyrimidines and the zinc powder of 1:1.05, distill after 80 DEG C of backflow 7h, recycle-water and methyl alcohol.Be cooled to 77 ~ 85 DEG C of filtrations, with hot wash filter cake.Filtrate and part washing lotion merge, and add granular caustic soda, below 50 DEG C, alkali analyses 1h.Separate jelly after adding ethyl acetate, regulate pH=7.5 ~ 8 with hydrochloric acid, then separate oily matter, reclaim ethyl acetate, separate out white crystal, fusing point is 123 ~ 124 DEG C, finally 40 ~ 50 DEG C of oven dry, namely obtains product 2-chloropyrimide.
Embodiment 5
1.12mol urea is dropped in 1000mL four-hole bottle, the sodium methylate of 25wt%, methanol solution (wherein methyl alcohol contains 1.23mol), slowly drips 1mol diethyl malonate under reflux temperature, stirring and refluxing 2h, obtain a large amount of white powdery solids, concentrating under reduced pressure obtains white sodium salt dry powder, adds 38wt% dilute hydrochloric acid solution wherein, adds water and regulates pH to 2, be heated to 75 DEG C, make reaction 2h.After completion of the reaction, be cooled to 0 DEG C of crystallize out, filter out crystal.Obtain white powder with methanol/water mixed solution recrystallization, be product barbituric acid.
In 1000mL four-hole bottle, drop into 5.4mol phosphorus oxychloride, DMA (60mL), is heated to 40 DEG C, in 30 ~ 60min, adds barbituric acid in batches, and temperature maintains 45 DEG C.After barbituric acid adds, slowly heat up, make temperature remain on 100 ~ 105 DEG C, stir 1.5 ~ 2h, obtain deep yellow transparent liquid, this liquid is poured into and fills in the beaker of frozen water, abundant stirring, remove supernatant liquid after leaving standstill, retain lower floor's light yellow solid, washing this light yellow solid to pH with the potassium hydroxide solution of massfraction 3% is 8 ~ 9, filtration, drying, obtain product 2,4,6-trichloropyrimidine.
Be that the methyl alcohol of 1:2 is added to water and adds in reactor and mix by volume ratio, in reactor, add caustic soda, and mol ratio be 2,4,6-trichloropyrimidines and the zinc powder of 1:1.15, distill after 80 DEG C of backflow 8h, recycle-water and methyl alcohol.Be cooled to 77 ~ 85 DEG C of filtrations, with hot wash filter cake.Filtrate and part washing lotion merge, and add granular caustic soda, below 50 DEG C, alkali analyses 1h.Separate jelly after adding ethyl acetate, regulate pH=7.5 ~ 8 with hydrochloric acid, then separate oily matter, reclaim ethyl acetate, separate out white crystal, fusing point is 123 ~ 124 DEG C, finally 40 ~ 50 DEG C of oven dry, namely obtains product 2-chloropyrimide.
2-chloropyrimide embodiment 1 ~ 5 obtained carries out transformation efficiency and yield is tested, and what deserves to be explained is, these tests the means of testing be familiar with by those skilled in the art, concrete testing method does not repeat at this.Its test result is as following table:
Table 1
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. prepare a method for 2-chloropyrimide, it is characterized in that, comprise the following steps:
(1) propanedioic acid ethyl diacetate and urea are reacted under the condition being catalyzer with sodium methylate, obtain barbituric acid, as reaction formula I,
(2) by barbituric acid under the condition being catalyzer with DMA, with phosphorus oxychloride reaction, obtain 2,4,6-trichloropyrimidine, as reaction formula II,
(3) be 1:(1 ~ 1.2 by mol ratio) 2,4,6-trichloropyrimidines and zinc powder in the solvent of first alcohol and water, under alkaline condition, obtain 2-chloropyrimide by redox reaction, as reaction formula III,
2. method according to claim 1, is characterized in that, described in step (1), the temperature of reaction is 65 ~ 75 DEG C.
3. method according to claim 1, is characterized in that, described in step (1), the pH value of reaction is 1.5 ~ 3.
4. method according to claim 1, is characterized in that, described in step (1), the mol ratio of propanedioic acid ethyl diacetate, urea and sodium methylate is 1:1.05 ~ 1.15:1.15 ~ 1.25.
5. method according to claim 1, is characterized in that, described in step (2), the temperature of reaction is 40 ~ 50 DEG C.
6. method according to claim 1, is characterized in that, described in step (2), the mol ratio of barbituric acid and phosphorus oxychloride is 1:5.1 ~ 5.5.
7. method according to claim 1, is characterized in that, described in step (3), the temperature of redox reaction is 76 ~ 84 DEG C.
8. method according to claim 1, is characterized in that, the time of redox reaction described in step (3) is 6 ~ 8h.
9. method according to claim 1, is characterized in that, in step (3), the volume ratio of methyl alcohol and water is 1:1.5 ~ 3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108586360A (en) * | 2018-06-13 | 2018-09-28 | 峨眉山宏昇药业股份有限公司 | A kind of preparation method of the chloro- 3- methyluracils of 6- |
| RU2737721C2 (en) * | 2017-12-15 | 2020-12-02 | Алексей Георгиевич Александров | Method for preparing pharmaceutical substance based on piribedil |
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| CN1148043A (en) * | 1995-10-17 | 1997-04-23 | 化学工业部沈阳化工研究院 | 4-aryloxy (arylthio or arylamino) pyrimidine derivative with herbicide active, and method for prepn. of same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2737721C2 (en) * | 2017-12-15 | 2020-12-02 | Алексей Георгиевич Александров | Method for preparing pharmaceutical substance based on piribedil |
| CN108586360A (en) * | 2018-06-13 | 2018-09-28 | 峨眉山宏昇药业股份有限公司 | A kind of preparation method of the chloro- 3- methyluracils of 6- |
| CN108586360B (en) * | 2018-06-13 | 2021-07-30 | 峨眉山宏昇药业股份有限公司 | Preparation method of 6-chloro-3-methyl uracil |
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Application publication date: 20150304 |