CN105732704A - 一种辛硫磷原药的合成工艺 - Google Patents
一种辛硫磷原药的合成工艺 Download PDFInfo
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- CN105732704A CN105732704A CN201610265200.9A CN201610265200A CN105732704A CN 105732704 A CN105732704 A CN 105732704A CN 201610265200 A CN201610265200 A CN 201610265200A CN 105732704 A CN105732704 A CN 105732704A
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- phoxim
- wastewater
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- ATROHALUCMTWTB-OWBHPGMISA-N phoxim Chemical compound CCOP(=S)(OCC)O\N=C(\C#N)C1=CC=CC=C1 ATROHALUCMTWTB-OWBHPGMISA-N 0.000 title claims abstract description 20
- 229950001664 phoxim Drugs 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 239000003814 drug Substances 0.000 title claims abstract description 14
- 239000002994 raw material Substances 0.000 title abstract description 3
- 229940079593 drug Drugs 0.000 title abstract 2
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 239000000575 pesticide Substances 0.000 claims abstract description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 claims description 4
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 claims description 4
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 claims description 4
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 230000032050 esterification Effects 0.000 abstract description 7
- 238000005886 esterification reaction Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 239000010446 mirabilite Substances 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 239000002728 pyrethroid Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/17—Esters of thiophosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机合成技术领域，具体涉及一种辛硫磷原药的合成工艺。所述工艺包括以下步骤：在亚硝酸甲酯制备过程中，通过高位槽将计量好的菊酯类农药合成中解析HCl后产生的废硫酸滴入酯化釜进行反应，反应结束后，静置分层，将下层的废水放入结晶釜中，加碱液中和，经降温、结晶后，离心分离出芒硝，剩余废水打入亚硝酸钠溶解釜中套用。所述工艺使酯化工序不再产生废水并可解决废酸的处理难题，大大节省了废水处理成本并遏制了对环境的污染。
Description
技术领域
本发明属于有机合成技术领域，具体涉及一种辛硫磷原药的合成工艺。
背景技术
辛硫磷的国际通用名称为Phoxim、有肟硫磷等，是生产中常用的广谱性有机磷杀虫剂。利用辛硫磷的胃毒、触杀和在黑暗条件下残效长等特性，可防治天牛等蛀干性害虫，符合环保、经济、安全和高效的原则。辛硫磷原药的现有合成路线中酯化工序是由盐酸作为原料，从而产生大量含有无机盐(氯化钠)的酯化废水，无法回收套用，处理成本很高且污染环境。
发明内容
为解决现有技术中存在的上述问题，本发明提供一种辛硫磷原药的合成工艺。
一种辛硫磷原药的合成工艺，包括以下步骤：
在亚硝酸甲酯制备过程中，通过高位槽将计量好的菊酯类农药合成中解析HCl后产生的废硫酸滴入酯化釜进行反应，反应结束后，静置分层，将下层的废水放入结晶釜中，加碱液中和，经降温、结晶后，离心分离出芒硝，剩余废水打入亚硝酸钠溶解釜中套用。
优选地，控制反应温度为30-45℃。
优选地，加碱液中和后降温至2-6℃，此时会产生大量结晶。
本发明所述辛硫磷原药的合成工艺具有如下优异效果：
(1)直接利用菊酯类农药合成中解析HCl后产生的废硫酸，不仅可解决此部分废酸的处理难题，又可降低辛硫磷原药的原料成本。
(2)芒硝易结晶回收，可从酯化废水中分离出来，作为副产品出售，剩余废水可直接套用作为前一工序溶解亚硝酸钠的用水，从而使酯化工序不再产生废水，大大节省了废水处理成本并遏制了对环境的污染。
(3)所述工艺对辛硫磷原药的质量指标无任何影响。
具体实施方式
下面结合实施例对本发明做进一步解释：
一种辛硫磷原药的合成工艺，包括以下步骤：
在亚硝酸甲酯制备过程中，通过高位槽将计量好的菊酯类农药合成中解析HCl后产生的废硫酸滴入酯化釜进行反应，严格控制反应温度为40℃，反应结束后，静置分层，将下层的废水放入结晶釜中，加碱液中和，降温到4℃左右产生大量结晶，离心分离出芒硝，剩余废水打入亚硝酸钠溶解釜中套用。
每生产1吨产品可减少酯化废水4吨左右；辛硫磷原油含量达到92％的优等品质量，辛硫磷合成收率达到国内较高水平，以乙基氯化物计：收率>92.5％，以苯乙腈计：收率>85％。
本发明并不限于实例所述形式，本领域的普通技术人员根据本发明做出的进一步拓展均落入本发明的保护范围。
Claims (3)
1.一种辛硫磷原药的合成工艺，其特征在于，包括以下步骤：
在亚硝酸甲酯制备过程中，通过高位槽将计量好的菊酯类农药合成中解析HCl后产生的废硫酸滴入酯化釜进行反应，反应结束后，静置分层，将下层的废水放入结晶釜中，加碱液中和，经降温、结晶后，离心分离出芒硝，剩余废水打入亚硝酸钠溶解釜中套用。
2.根据权利要求1所述的一种辛硫磷原药的合成工艺，其特征在于，控制反应温度为30-45℃。
3.根据权利要求1所述的一种辛硫磷原药的合成工艺，其特征在于，加碱液中和后降温至2-6℃。
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| CN201610265200.9A CN105732704A (zh) | 2016-04-26 | 2016-04-26 | 一种辛硫磷原药的合成工艺 |
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| CN201610265200.9A CN105732704A (zh) | 2016-04-26 | 2016-04-26 | 一种辛硫磷原药的合成工艺 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3244586A (en) * | 1962-04-30 | 1966-04-05 | Dow Chemical Co | Omicron-pyridyl phosphates and phosphorothioates |
| US3591662A (en) * | 1965-06-26 | 1971-07-06 | Bayer Ag | Phosphorus containing alpha oximino acetic acid nitriles |
| CN1073445A (zh) * | 1992-12-14 | 1993-06-23 | 山东临沂农药厂 | 辛硫磷的一种生产方法 |
| CN1115319A (zh) * | 1994-07-19 | 1996-01-24 | 石家庄化工厂胜芳分厂 | 辛硫磷引发聚合法生产工艺 |
| CN101717409A (zh) * | 2009-11-10 | 2010-06-02 | 孙德群 | 甲乙基有机磷类化合物及其应用 |
| CN103242166A (zh) * | 2012-02-09 | 2013-08-14 | 中国科学院福建物质结构研究所 | 一种制备亚硝酸甲酯气体的方法 |
-
2016
- 2016-04-26 CN CN201610265200.9A patent/CN105732704A/zh active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3244586A (en) * | 1962-04-30 | 1966-04-05 | Dow Chemical Co | Omicron-pyridyl phosphates and phosphorothioates |
| US3591662A (en) * | 1965-06-26 | 1971-07-06 | Bayer Ag | Phosphorus containing alpha oximino acetic acid nitriles |
| CN1073445A (zh) * | 1992-12-14 | 1993-06-23 | 山东临沂农药厂 | 辛硫磷的一种生产方法 |
| CN1115319A (zh) * | 1994-07-19 | 1996-01-24 | 石家庄化工厂胜芳分厂 | 辛硫磷引发聚合法生产工艺 |
| CN101717409A (zh) * | 2009-11-10 | 2010-06-02 | 孙德群 | 甲乙基有机磷类化合物及其应用 |
| CN103242166A (zh) * | 2012-02-09 | 2013-08-14 | 中国科学院福建物质结构研究所 | 一种制备亚硝酸甲酯气体的方法 |
Non-Patent Citations (2)
| Title |
|---|
| 王天桃等: "杀螨菊酯合成工艺的研究", 《中华卫生杀虫药械》 * |
| 陈震等: "偏氯菊酸对甲氧基苄酯的合成研究", 《化学试剂》 * |
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