CN111606860A - Preparation method of 4, 6-dichloropyrimidine - Google Patents
Preparation method of 4, 6-dichloropyrimidine Download PDFInfo
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- CN111606860A CN111606860A CN202010543408.9A CN202010543408A CN111606860A CN 111606860 A CN111606860 A CN 111606860A CN 202010543408 A CN202010543408 A CN 202010543408A CN 111606860 A CN111606860 A CN 111606860A
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- dichloropyrimidine
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- dimethylaniline
- substitution
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- XJPZKYIHCLDXST-UHFFFAOYSA-N 4,6-dichloropyrimidine Chemical compound ClC1=CC(Cl)=NC=N1 XJPZKYIHCLDXST-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000006467 substitution reaction Methods 0.000 claims abstract description 23
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000003337 fertilizer Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 10
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- DUFGYCAXVIUXIP-UHFFFAOYSA-N 4,6-dihydroxypyrimidine Chemical compound OC1=CC(O)=NC=N1 DUFGYCAXVIUXIP-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 11
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 230000009615 deamination Effects 0.000 claims description 3
- 238000006481 deamination reaction Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000002351 wastewater Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract description 8
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000005730 Azoxystrobin Substances 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- WFDXOXNFNRHQEC-GHRIWEEISA-N azoxystrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1OC1=CC(OC=2C(=CC=CC=2)C#N)=NC=N1 WFDXOXNFNRHQEC-GHRIWEEISA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
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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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a preparation method of 4, 6-dichloropyrimidine, which comprises the steps of neutralizing acidic waste liquid generated after substitution reaction by ammonia water, standing and layering for two times to obtain ammonium dihydrogen phosphate and ammonium chloride, wherein the ammonium dihydrogen phosphate and the ammonium chloride can be used as raw materials of a compound fertilizer for recycling, so that the preparation waste water is remarkably reduced; meanwhile, after the N, N-dimethylaniline serving as the catalyst is deaminated, the N, N-dimethylaniline can keep higher activity and be applied to the preparation of 4, 6-dichloropyrimidine again, so that the utilization rate of raw materials is improved.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of 4, 6-dichloropyrimidine.
Background
4, 6-dichloropyrimidine is an important intermediate for synthesizing sulfonamides and bactericide azoxystrobin, and the mainstream preparation methods at present can be divided into a phosphorus oxychloride chlorination method and a solid phosgene chlorination method, wherein the phosphorus oxychloride chlorination method comprises the following steps: reacting 4, 6-dihydroxypyrimidine with phosphorus oxychloride under the catalysis of tertiary amine to obtain a reaction mixture containing 4, 6-dichloropyrimidine; the mixture is purified to obtain pure 4, 6-dichloropyrimidine. The process in the prior art can generate mixed acidic wastewater of hydrochloric acid and phosphate containing a catalyst, the wastewater is generally treated by neutralizing the wastewater with liquid alkali, dissociating the catalyst, separating the catalyst layer by layer, recycling the separated catalyst layer, and recycling the separated catalyst layer to use, so that the wastewater which contains a large amount of sodium chloride and sodium phosphate and is difficult to treat is left, the wastewater is evaporated to generate a large amount of mixed waste salt of sodium chloride and sodium phosphate which has no value, the mixed waste salt is difficult to directly recycle, and the prepared catalyst has low activity and poor recycling effect. Therefore, it is necessary to provide a novel method for preparing 4, 6-dihydroxypyrimidine to solve the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of 4, 6-dichloropyrimidine, which is used for solving the problems that in the prior art, a preparation process of 4, 6-dihydroxypyrimidine generates waste water which is difficult to recycle, and the reutilization effect of a prepared catalyst is poor.
In order to solve the technical problems, the invention provides a preparation method of 4, 6-dichloropyrimidine, which comprises the following steps: gradually dripping N, N-dimethylaniline into a mixed solution of 4, 6-dihydroxypyrimidine and phosphorus oxychloride, and carrying out substitution reaction to obtain a substitution mixture; gradually adding the substituted mixture into water for first standing and layering, and separating to obtain a first upper layer liquid and a first lower layer liquid; adding the first lower layer liquid into water, adjusting the pH value to 7, and sequentially standing, separating, distilling and crystallizing to obtain a 4, 6-dichloropyrimidine product; gradually adding ammonia water into the first upper layer liquid until the pH value is 9.0-9.5, standing for layering for the second time, and separating to obtain a second upper layer liquid and a second lower layer liquid; adding a deaminating agent into the second supernatant, uniformly mixing, and performing vacuum dehydration at 70-100 ℃ to obtain recyclable N, N-dimethylaniline; and decoloring the second subnatant by active carbon, and freezing and salting out to obtain the recyclable compound fertilizer raw material.
In the step of obtaining the substituted mixture after the substitution reaction, the mass ratio of 4, 6-dihydroxypyrimidine, phosphorus oxychloride and N, N-dimethylaniline is (7-8): (9-10): (7-8).
The method comprises the following specific steps of carrying out a substitution reaction to obtain a substitution mixture: stirring and mixing 4, 6-dihydroxypyrimidine and phosphorus oxychloride according to the proportion at 40 ℃, gradually dripping N, N-dimethylaniline, and controlling the temperature not to exceed 58 ℃; and (3) after the dropwise addition is finished, maintaining for 20min, slowly heating to 70-85 ℃, maintaining for 2-4 h, cooling to below 35 ℃, adding a tetrachloroethylene solvent, and stirring for 30min to obtain a substitution mixture.
Wherein the mass ratio of the addition amount of the tetrachloroethylene solvent to the N, N-dimethylaniline is (32-40): (7-8).
Preferably, in the step of carrying out the first standing and layering, the substitution mixture is added into water to carry out hydrolysis reaction, and the mass ratio of the substitution mixture to the water is (55-66): (40-50), and controlling the hydrolysis reaction temperature not to exceed 30 ℃.
The method for obtaining the 4, 6-dichloropyrimidine comprises the following specific steps: adding the first lower layer liquid into water, adding soda ash to adjust the pH value to 7, standing for 20-30 min, taking the lower layer material, heating to 40-45 ℃, carrying out reduced pressure distillation, and separating out a tetrachloroethylene solvent; distilling at 100-110 ℃ under negative pressure, and then sequentially cooling, crystallizing, centrifuging and drying by double cones at 5-10 ℃ to obtain the 4, 6-dichloropyrimidine product.
Preferably, the deamination agent is any one of potassium hydroxide, sodium carbonate and calcium hydroxide.
Preferably, the recyclable compound fertilizer raw material is a mixture of ammonium dihydrogen phosphate and ammonium chloride.
The invention has the beneficial effects that: compared with the prior art, the invention provides the preparation method of the 4, 6-dichloropyrimidine, acidic waste liquid generated after ammonia water neutralization substitution reaction is adopted, and ammonium dihydrogen phosphate and ammonium chloride are obtained after twice standing and layering, and can be used as raw materials of compound fertilizers for recycling, so that the preparation waste water is obviously reduced; meanwhile, after the N, N-dimethylaniline serving as the catalyst is deaminated, the N, N-dimethylaniline can keep higher activity and be applied to the preparation of 4, 6-dichloropyrimidine again, so that the utilization rate of raw materials is improved.
Drawings
FIG. 1 is a process flow diagram of one embodiment of a process for preparing 4, 6-dichloropyrimidine according to the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to FIG. 1, FIG. 1 is a process flow diagram of one embodiment of the method for preparing 4, 6-dichloropyrimidine according to the invention. The invention provides a preparation method of 4, 6-dichloropyrimidine, which comprises the following steps:
(1) gradually dripping N, N-dimethylaniline into the mixed solution of 4, 6-dihydroxypyrimidine and phosphorus oxychloride for substitution reaction to obtain a substitution mixture. In the step, 4, 6-dihydroxypyrimidine and phosphorus oxychloride are stirred and mixed according to the proportion at 40 ℃, N-dimethylaniline is gradually dripped, the temperature is controlled not to exceed 58 ℃, and the preferred mass ratio of the 4, 6-dihydroxypyrimidine, the phosphorus oxychloride and the N, N-dimethylaniline is (7-8): (9-10): (7-8); after the dropwise addition is finished, maintaining for 20min, slowly heating to 70-85 ℃, maintaining for 2-4 h, cooling to below 35 ℃, adding a tetrachloroethylene solvent, and stirring for 30min, wherein the mass ratio of the added tetrachloroethylene solvent to the N, N-dimethylaniline is (32-40): (7-8) to obtain a substituted mixture.
Specifically, under the catalytic action of N, N-dimethylaniline, 4, 6-dihydroxypyrimidine and phosphorus oxychloride have the chemical reaction formula:
the method can produce more wastewater containing phosphoric acid and hydrochloric acid while preparing 4, 6-dichloropyrimidine after the substitution reaction, needs to adopt alkaline solution for neutralization, and is convenient for recycling the subsequent catalyst N, N-dimethylaniline.
(2) And (3) gradually adding the substituted mixture into water for first standing and layering, and separating to obtain a first upper layer liquid and a first lower layer liquid. In the step, the substitution mixture is gradually added into water to perform hydrolysis reaction, and the mass ratio of the substitution mixture to the water is preferably (55-66): (40-50), controlling the hydrolysis reaction temperature not to exceed 30 ℃, standing for the first time for layering, and separating to obtain a first upper layer liquid and a first lower layer liquid, wherein the first upper layer liquid mainly comprises PO4 -、Cl-And N, N-dimethylaniline, and the first subbing liquid mainly comprises 4, 6-dichloropyrimidineAnd tetrachloroethylene, and the treatment of the acidic waste liquid is mainly performed with respect to the first supernatant liquid.
(3) And adding the first lower layer liquid into water, adjusting the pH value to 7, and sequentially standing, separating, distilling and crystallizing to obtain a 4, 6-dichloropyrimidine product. Adding the first lower layer liquid into water, adding soda ash to adjust the pH value to 7, standing for 20-30 min, taking the lower layer material, heating to 40-45 ℃, carrying out reduced pressure distillation, separating out a tetrachloroethylene solvent, and completing the separation of the tetrachloroethylene solvent and 4, 6-dichloropyrimidine; distilling at 100-110 ℃ under negative pressure, and then sequentially cooling, crystallizing, centrifuging and drying by double cones at 5-10 ℃ to obtain the 4, 6-dichloropyrimidine product.
(4) And gradually adding ammonia water into the first supernatant until the pH is 9.0-9.5, standing for the second time for layering, and separating to obtain a second supernatant and a second subnatant. In the step, ammonia water is gradually added into the first upper layer liquid and adjusted to be alkaline, so that the main components in the solution are ammonium dihydrogen phosphate, ammonium chloride and N, N-dimethylaniline, after standing and layering, the main component in the second upper layer liquid is the N, N-dimethylaniline, and the main component in the second lower layer liquid is the ammonium dihydrogen phosphate and the ammonium chloride.
(5) Adding a deaminating agent into the second supernatant, uniformly mixing, and performing vacuum dehydration at 70-100 ℃ to obtain the recyclable N, N-dimethylaniline. In the step, because the second supernatant fluid contains N, N-dimethylaniline and excessive ammonia water, in the actual production, under the condition that the ammonia water is excessive, if the N, N-dimethylaniline is directly dehydrated and recovered, the activity of the N, N-dimethylaniline catalyst can be obviously reduced, and the N, N-dimethylaniline is not beneficial to being used as the catalyst for reuse, so the second supernatant fluid is firstly subjected to deamination treatment and then subjected to vacuum dehydration, the mode effectively solves the problem of low activity after the recovery of the N, N-dimethylaniline, and the recovered N, N-dimethylaniline can recover the catalytic activity for reuse, thereby improving the catalytic efficiency in recycling. In this embodiment, any one of potassium hydroxide, sodium carbonate and calcium hydroxide is preferable as the deaminating agent, and in other embodiments, a deaminating agent having a similar function may be selected according to the actual situation, which is not limited herein.
(6) And decoloring the second subnatant by active carbon, and freezing and salting out to obtain the recyclable compound fertilizer raw material. In the step, the main components of the raw materials of the obtained compound fertilizer are ammonium dihydrogen phosphate and ammonium chloride, and the mixed salt of the ammonium dihydrogen phosphate and the ammonium chloride can be sold to compound fertilizer production enterprises as a commodity to produce the compound fertilizer, so that the compound fertilizer can be well recycled, the problem that the waste water contains a large amount of sodium chloride and sodium phosphate waste salt which are difficult to treat in the prior art is solved, and the problem that the waste water generated in the preparation process of the 4, 6-dichloropyrimidine is difficult to utilize is solved.
Compared with the prior art, the invention provides the preparation method of the 4, 6-dichloropyrimidine, acidic waste liquid generated after ammonia water neutralization substitution reaction is adopted, and ammonium dihydrogen phosphate and ammonium chloride are obtained after twice standing and layering, and can be used as raw materials of compound fertilizers for recycling, so that the preparation waste water is obviously reduced; meanwhile, after the N, N-dimethylaniline serving as the catalyst is deaminated, the N, N-dimethylaniline can keep higher activity and be applied to the preparation of 4, 6-dichloropyrimidine again, so that the utilization rate of raw materials is improved.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A preparation method of 4, 6-dichloropyrimidine is characterized by comprising the following steps:
gradually dripping N, N-dimethylaniline into a mixed solution of 4, 6-dihydroxypyrimidine and phosphorus oxychloride, and carrying out substitution reaction to obtain a substitution mixture;
gradually adding the substituted mixture into water for first standing and layering, and separating to obtain a first upper layer liquid and a first lower layer liquid;
adding the first lower layer liquid into water, adjusting the pH value to 7, and sequentially standing, separating, distilling and crystallizing to obtain a 4, 6-dichloropyrimidine product;
gradually adding ammonia water into the first upper layer liquid until the pH value is 9.0-9.5, standing for the second time for layering, and separating to obtain a second upper layer liquid and a second lower layer liquid;
adding a deamination agent into the second supernatant, uniformly mixing, and performing vacuum dehydration at 70-100 ℃ to obtain the recyclable N, N-dimethylaniline.
2. The method for preparing 4, 6-dichloropyrimidine according to claim 1, wherein in the step of carrying out the substitution reaction to obtain the substitution mixture, the mass ratio of the 4, 6-dihydroxypyrimidine to the phosphorus oxychloride to the N, N-xylidine is (7-8): (9-10): (7-8).
3. The process for preparing 4, 6-dichloropyrimidine as claimed in claim 2 wherein the step of subjecting the mixture to substitution comprises:
stirring and mixing the 4, 6-dihydroxypyrimidine and phosphorus oxychloride according to the proportion at 40 ℃, gradually dropwise adding the N, N-dimethylaniline, and controlling the temperature not to exceed 58 ℃;
and (3) after the dropwise addition is finished, maintaining for 20min, slowly heating to 70-85 ℃, maintaining for 2-4 h, cooling to below 35 ℃, adding a tetrachloroethylene solvent, and stirring for 30min to obtain the substituted mixture.
4. The method for preparing 4, 6-dichloropyrimidine according to claim 3, wherein the mass ratio of the amount of the tetrachloroethylene solvent to the amount of the N, N-xylidine (32-40): (7-8).
5. The method for preparing 4, 6-dichloropyrimidine according to claim 1, wherein in the step of carrying out the first standing and layering, the substitution mixture is added into water to carry out hydrolysis reaction, and the mass ratio of the substitution mixture to the water is (55-66): (40-50), and controlling the hydrolysis reaction temperature not to exceed 30 ℃.
6. The method for preparing 4, 6-dichloropyrimidine according to claim 1, wherein the step of obtaining the 4, 6-dichloropyrimidine product comprises:
adding the first lower layer liquid into water, adding soda ash to adjust the pH value to 7, standing for 20-30 min, taking the lower layer material, heating to 40-45 ℃, carrying out reduced pressure distillation, and separating out a tetrachloroethylene solvent;
distilling at 100-110 ℃ under negative pressure, and then sequentially cooling, crystallizing, centrifuging and drying by double cones at 5-10 ℃ to obtain the 4, 6-dichloropyrimidine product.
7. The method of claim 1, wherein the deaminating agent is any one of potassium hydroxide, sodium carbonate, and calcium hydroxide.
8. The method for preparing 4, 6-dichloropyrimidine according to claim 1, wherein the second subnatant is decolorized with activated carbon and then frozen and salted out to obtain a recyclable compound fertilizer raw material, wherein the recyclable compound fertilizer raw material is a mixture of ammonium dihydrogen phosphate and ammonium chloride.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248446A (en) * | 2021-05-18 | 2021-08-13 | 泰州百力化学股份有限公司 | 4, 6-dichloropyrimidine purification and phosphorus recycling treatment process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082031A (en) * | 1993-05-20 | 1994-02-16 | 郑州市孝义制药厂 | The preparation method of sulfamonomethoxine |
| CN102432092A (en) * | 2011-10-25 | 2012-05-02 | 太原理工大学 | Composite desulfurization and deamination agent and process for synchronously treating ammonia nitrogen and sulfide in waste liquid by using same |
| CN102675216A (en) * | 2012-03-20 | 2012-09-19 | 河北临港化工有限公司 | Novel purifying treatment process for 4,6-dichloropyrimidine |
| CN104609633A (en) * | 2015-02-16 | 2015-05-13 | 阮氏化工（常熟）有限公司 | Method and device for utilizing sewage containing ammonia and sodium |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1082031A (en) * | 1993-05-20 | 1994-02-16 | 郑州市孝义制药厂 | The preparation method of sulfamonomethoxine |
| CN102432092A (en) * | 2011-10-25 | 2012-05-02 | 太原理工大学 | Composite desulfurization and deamination agent and process for synchronously treating ammonia nitrogen and sulfide in waste liquid by using same |
| CN102675216A (en) * | 2012-03-20 | 2012-09-19 | 河北临港化工有限公司 | Novel purifying treatment process for 4,6-dichloropyrimidine |
| CN104609633A (en) * | 2015-02-16 | 2015-05-13 | 阮氏化工（常熟）有限公司 | Method and device for utilizing sewage containing ammonia and sodium |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248446A (en) * | 2021-05-18 | 2021-08-13 | 泰州百力化学股份有限公司 | 4, 6-dichloropyrimidine purification and phosphorus recycling treatment process |
| CN113248446B (en) * | 2021-05-18 | 2022-06-14 | 泰州百力化学股份有限公司 | 4, 6-dichloropyrimidine purification and phosphorus recycling treatment process |
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