CN102603651A - Novel synthesis process of high-purity pesticide intermediate - Google Patents
Novel synthesis process of high-purity pesticide intermediate Download PDFInfo
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- CN102603651A CN102603651A CN2012100517786A CN201210051778A CN102603651A CN 102603651 A CN102603651 A CN 102603651A CN 2012100517786 A CN2012100517786 A CN 2012100517786A CN 201210051778 A CN201210051778 A CN 201210051778A CN 102603651 A CN102603651 A CN 102603651A
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- Prior art keywords
- purity
- mixed solvent
- filtrating
- compound method
- dichloro pyrimidine
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title abstract 2
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- 239000000575 pesticide Substances 0.000 title description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- XJPZKYIHCLDXST-UHFFFAOYSA-N 4,6-dichloropyrimidine Chemical compound ClC1=CC(Cl)=NC=N1 XJPZKYIHCLDXST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 1
- 230000003311 flocculating effect Effects 0.000 claims 1
- NSWAMPCUPHPTTC-UHFFFAOYSA-N chlorimuron-ethyl Chemical group CCOC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(Cl)=CC(OC)=N1 NSWAMPCUPHPTTC-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- UNCQVRBWJWWJBF-UHFFFAOYSA-N 2-chloropyrimidine Chemical compound ClC1=NC=CC=N1 UNCQVRBWJWWJBF-UHFFFAOYSA-N 0.000 abstract 2
- JPZOAVGMSDSWSW-UHFFFAOYSA-N 4,6-dichloropyrimidin-2-amine Chemical compound NC1=NC(Cl)=CC(Cl)=N1 JPZOAVGMSDSWSW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002860 competitive effect Effects 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 239000012452 mother liquor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- VFEYBTFCBZMBAU-UHFFFAOYSA-N 4-chloro-6-methoxypyrimidin-2-amine Chemical compound COC1=CC(Cl)=NC(N)=N1 VFEYBTFCBZMBAU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000000442 meristematic effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a novel synthesis process of a chlorimuron-ethyl intermediate, i.e., high-purity 2-amino-4-chlorin-6-methoxypyrimidine (chloropyrimidine for short). The process comprises the following steps of: adding 2-amino-4,6-dichloropyrimidine (dichloropyrimidine for short) into a mixed solvent; raising the temperature and dropwise adding sodium methoxide; after reacting, adding a decolorizing agent; filtering, cooling, crystalizing and washing to obtain a high-purity target; and after a mixed mother solution is used for sufficient batches, performing distillation treatment. Due to the adoption of the process, the yield and total yield level of a high-purity product are increased, and the production difficulty is lowered greatly; and a high-end chlorimuron-ethyl product synthesized by using the high-purity chloropyrimidine intermediate produced with the process has strong competitive strength in domestic and international markets.
Description
Technical field:
The present invention relates to a kind of production technique of chlorimuronethyl midbody, be specifically related to the new preparation process of high-purity 2-amino-4-chloro-6-methoxy pyrimidine.
Background technology:
Chlorimuronethyl is before a kind of selectivity bud, post-emergence herbicide, can be absorbed by roots of plants, stem, leaf, in plant materials, conducts up and down, at eugonic meristematic cell performance herbicide effect, is mainly used in the soybean field and prevents and kill off broadleaf weeds.
The at present domestic technology that generally adopts is 2-amino-4, and the 6-dichloro pyrimidine reacts with sodium methylate in methanol system, with the methyl alcohol distillation, adds water crystallization then after reaction finishes, and obtaining content is 95～97% khaki color powder particles, i.e. a chloropyrimide bullion.Make solvent with toluene or ethylene dichloride then, decrease temperature crystalline obtains high single chloropyrimide behind the activated carbon decolorizing.
This method subject matter be because of chloropyrimide solubleness in this toluene or ethylene dichloride limited; Need high amounts of solvents; And the yield of high single chloropyrimide is merely about 80%; Also have about 13% low levels product to demote to use or make 2-amino-4, the 6-dimethoxypyridin, total recovery is about 93%.Method provided by the invention is then used methyl alcohol-sherwood oil system instead and is replaced traditional methanol system; Significantly improve the yield to 90% of high purity product; Obtain about 3～4% low levels one chloropyrimide after applying mechanically the mother liquor distillation; Because of significantly having reduced the high-temperature solvent still-process,, reach 94～95% so total recovery exceeds 1～2% than traditional technology.
Summary of the invention:
Method provided by the invention is then used mixed system instead and is replaced traditional methyl alcohol unitary system; Adopt the primary crystallization method promptly to obtain high-purity 2-amino-4-chloro-6-methoxy pyrimidine product; Improve the yield and the total recovery of high purity product, it is low to have overcome the traditional method yield, pollutes big and the big shortcoming of production difficulty; A kind of new production technique is provided, has obtained the better economic effect.
The object of the invention can reach through following measure:
A kind of new synthetic process of high-content pesticide intermediate, with 2-amino-4, the 6-dichloro pyrimidine drops in the mixed solvent; Temperature rising reflux; Add sodium methylate then, insulation reaction finishes the back cooling and adds the discoloring agent reflux decolour, filters the back decrease temperature crystalline; Mother liquid recycle, bullion can high single chloropyrimide products after with water washing.Wherein said mixed solvent be methyl alcohol, toluene, ethylene dichloride, acetonitrile and sherwood oil intermediary two or more.
Used mixed solvent is preferably methyl alcohol-sherwood oil, and its volume ratio is 1: 0.5～3.
The amount of used mixed solvent is 3～10 times of dichloro pyrimidine quality.
Used discoloring agent is a white diatomite, and its quality is 2%～20% of a dichloro pyrimidine quality.
Used mixed solvent mother liquid recycle number of times is 1-10 time.
The present invention adopts mixed solvent to replace original single solvent, has strengthened the solubleness of a chloropyrimide, has reduced solvent load and loss, finishes the back in reaction in addition and directly uses the bleaching agent bleaching post crystallization, has improved the yield of high purity product greatly.
This compound method has been saved a large amount of solvent still-process, has not only improved the visual appearance of product, has improved yield; And reduced sewage quantity; The high single chloropyrimide of producing is used for synthesizing high-quality chlorimuronethyl, can satisfy the demand of domestic and international high-end market, produces good economical effectiveness.
The practical implementation case:
Example 1: in the 250ml four-hole boiling flask, add 16.8g dichloro pyrimidine (0.1mol), 100ml methyl alcohol and 80ml sherwood oil, stir and be warming up to 40～50 ℃, drip like 18.2g sodium methoxide solution (0.101mol) fast, reacted 2 hours; Cooling adds 2g zeyssatite continued and refluxed heat filtering, washing leaching cake 1 hour; Filtrating merging is cooled to 0～10 ℃ of crystallization, suction filtration, and filtrating is applied mechanically; Get white needle-like crystals 14.1g, content 99.7%, molar yield 88.1% after the filter cake washing.
Example 2: in the 250ml four-hole boiling flask, adding 16.8g dichloro pyrimidine (0.1mol), " example 1 ", reclaim the about 170ml of mother liquor, 5ml methyl alcohol and 5ml sherwood oil, stir and be warming up to 40～50 ℃, drip fast like 18.2g sodium methoxide solution (0.101mol); Reacted 2 hours, cooling adds 2g zeyssatite continued and refluxed heat filtering 1 hour; Washing leaching cake, filtrating merging is cooled to 0～10 ℃ of crystallization, suction filtration; Filtrating is applied mechanically; Get white needle-like crystals 14.62g, content 99.3%, molar yield 91.01% after the filter cake washing.
Example 3: in the 250ml four-hole boiling flask, adding 16.8g dichloro pyrimidine (0.1mol), " example 2 ", reclaim the about 170ml of mother liquor, 5ml methyl alcohol and 5ml sherwood oil, stir and be warming up to 40～50 ℃, drip fast like 18.2g sodium methoxide solution (0.101mol); Reacted 2 hours, cooling adds 2.5g zeyssatite continued and refluxed heat filtering 1 hour; Washing leaching cake, filtrating merging is cooled to 0～10 ℃ of crystallization, suction filtration; Filtrating is applied mechanically; Get white needle-like crystals 14.52g, content 99.4%, molar yield 90.49% after the filter cake washing.Mother liquor distillation back is added 100ml water, stir after 30 minutes about 50 ℃, be cooled to the normal temperature suction filtration, filter cake washing gets khaki color powder 7.44g (96.5%), and average total molar yield is 94.4%.
The invention is not restricted to these disclosed embodiments, with the scope that covers described in the Patent right requirement book, and the various modification of claim scope change with equivalence.
Claims (5)
1. the new synthetic process of a high single chloropyrimide is characterized in that: dichloro pyrimidine is dropped in the mixed solvent, be warming up to backflow, then to wherein dripping sodium methylate; Dropwise back insulation back flow reaction, after detection level was qualified, cooling added zeyssatite; Temperature rising reflux, press filtration while hot then, the filtrating decrease temperature crystalline filters, and promptly gets high single chloropyrimide product after the filter cake washing; Filtrating is applied mechanically the distillation of many backs and is handled, and solvent is applied mechanically, and steams excess and adds water crystallization, obtains bullion.Wherein said mixed solvent for for methyl alcohol, toluene, ethylene dichloride, acetonitrile and sherwood oil intermediary two or more.
2. compound method according to claim 1 is characterized in that used mixed solvent is methyl alcohol-sherwood oil, and its volume ratio is 1: 0.5～3.
3. according to the described compound method of claim 1, the amount that it is characterized in that mixed solvent is 3～15 times of dichloro pyrimidine quality.
4. according to the described compound method of claim 1, it is characterized in that used flocculating aids is a white diatomite, its quality is 2%～20% of a dichloro pyrimidine quality.
5. according to the described compound method of claim 1, it is characterized in that it is 1～10 time that filtrating is applied mechanically number of times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100517786A CN102603651A (en) | 2012-02-27 | 2012-02-27 | Novel synthesis process of high-purity pesticide intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100517786A CN102603651A (en) | 2012-02-27 | 2012-02-27 | Novel synthesis process of high-purity pesticide intermediate |
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| Publication Number | Publication Date |
|---|---|
| CN102603651A true CN102603651A (en) | 2012-07-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100517786A Pending CN102603651A (en) | 2012-02-27 | 2012-02-27 | Novel synthesis process of high-purity pesticide intermediate |
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| Country | Link |
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| CN (1) | CN102603651A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294572A (en) * | 2015-10-13 | 2016-02-03 | 安徽泓德化工技术有限公司 | Preparation method of mono-methoxyl pyrilamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323789A (en) * | 2000-05-11 | 2001-11-28 | 湖南化工研究院 | Sulfonyl urea compound containing alkylthio or propenyl oxy radical and with herbicidal activity and its prepn. |
| CN1337158A (en) * | 2000-08-15 | 2002-02-27 | 连云港市第二农药厂 | Sulfony urea compound and its application as biiocidal herbicide |
| US20060035913A1 (en) * | 2002-10-26 | 2006-02-16 | Sylvia Huber | Method for the production of 2-amino-4-chloro-6-alkoxypyrimidines |
-
2012
- 2012-02-27 CN CN2012100517786A patent/CN102603651A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323789A (en) * | 2000-05-11 | 2001-11-28 | 湖南化工研究院 | Sulfonyl urea compound containing alkylthio or propenyl oxy radical and with herbicidal activity and its prepn. |
| CN1337158A (en) * | 2000-08-15 | 2002-02-27 | 连云港市第二农药厂 | Sulfony urea compound and its application as biiocidal herbicide |
| US20060035913A1 (en) * | 2002-10-26 | 2006-02-16 | Sylvia Huber | Method for the production of 2-amino-4-chloro-6-alkoxypyrimidines |
Non-Patent Citations (1)
| Title |
|---|
| 朱路: "2-氨基-4-氯-6-甲氧基嘧啶的合成", 《郑州大学学报(自然科学版)》, vol. 32, no. 2, 30 June 2000 (2000-06-30), pages 87 - 88 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294572A (en) * | 2015-10-13 | 2016-02-03 | 安徽泓德化工技术有限公司 | Preparation method of mono-methoxyl pyrilamine |
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Application publication date: 20120725 |