WO2020093459A1 - 一种敌草快阴离子盐的绿色制备方法 - Google Patents

一种敌草快阴离子盐的绿色制备方法 Download PDF

Info

Publication number
WO2020093459A1
WO2020093459A1 PCT/CN2018/116907 CN2018116907W WO2020093459A1 WO 2020093459 A1 WO2020093459 A1 WO 2020093459A1 CN 2018116907 W CN2018116907 W CN 2018116907W WO 2020093459 A1 WO2020093459 A1 WO 2020093459A1
Authority
WO
WIPO (PCT)
Prior art keywords
diquat
dibromide
mother liquor
reaction
dichloride
Prior art date
Application number
PCT/CN2018/116907
Other languages
English (en)
French (fr)
Inventor
薛谊
岳瑞宽
陈洪龙
袁意
王文魁
罗超然
刘小攀
周钰明
王明亮
孙伯旺
鲍杰华
Original Assignee
南京红太阳生物化学有限责任公司
东南大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南京红太阳生物化学有限责任公司, 东南大学 filed Critical 南京红太阳生物化学有限责任公司
Publication of WO2020093459A1 publication Critical patent/WO2020093459A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems

Definitions

  • the invention belongs to the field of chemistry and relates to a green preparation method of diquat anion salt, in particular to a preparation method of diquat dichloride or diquat bisulfate.
  • Diquat is an excellent contact desiccant and herbicide with systemic properties.
  • the traditional diquat is dibromide (CAS number: 85-00-7).
  • Diquat dibromide was first developed and industrialized by the British ICI (Imperial Chemical Industries) (predecessor of Syngenta). Its main preparation method is composed of 2,2'-bipyridine and 1,2-dibromoethane ring Combined reaction (US2823987), also pointed out that the anion change of diquat does not destroy its herbicidal activity.
  • Patent GB815348 mentions that the change of diquat anion does not destroy its herbicidal activity.
  • Related literature also mentions that the active ingredients of herbicides such as paraquat and diquat are cationic parts, and the related anions have no effect on their herbicidal activity (The dipyridylium herbicides, paraquat and diquat, P99).
  • the anion has no effect on its activity, C1 -, Br -, I -, CH 3 SO 4 2-, SO 4 2- influence of these ions on an equimolar amount of substrate are equal (J.Sci. Food Agric., 11, June, 1960, 309-315).
  • Bromine is a precious resource.
  • the traditional bromine extraction method is to enrich and extract bromine by a series of technological means such as brine or seawater concentration and oxidation, and then use it to manufacture important chemical products.
  • diquat dibromide will bring bromine into the environment during use, causing unnecessary waste.
  • chloride ion or sulfate (hydrogen) ion is suitable for the counter ion of diquat cation.
  • Patent US2823987 (example 4) mentioned that diquat dibromide salt solution and silver chloride were fully stirred and reacted to filter out silver bromide to obtain diquat dichloride salt solution.
  • Chloroethanol method uses 2,2'-bipyridine and 1-chloro-2-ethanol to prepare a dichloride salt and by-product ethylene glycol by co-heating to 130 ⁇ 170 °C.
  • the patent US3308124 provides a new method for preparing dichlorpyrene dichloride. Specifically, an equimolar amount of ethylene and chlorine are continuously fed by 2,2-bipyridine, a catalyst (such as NaCl, glass wool, silica gel, etc.) In the mixed solution composed of solvents (such as nitrobenzene, etc.), the dichloride salt of diquat is prepared by reaction at 80-160 ° C. The patent does not give the conversion of raw materials and product yield. At the same time, it was pointed out that dichloroethane and 2,2’-bipyridine could not produce dichlorpyridine under these conditions.
  • a catalyst such as NaCl, glass wool, silica gel, etc.
  • Ethylene glycol method US3651060 uses 2,2'-bipyridine, ethylene glycol and an acid to prepare dipyridonium salts with different anions.
  • the acid may be an inorganic acid (hydrochloric acid, hydrobromic acid, hydroiodic acid), an oxyacid (sulfuric acid, phosphoric acid, boric acid), and the ethylene glycol may be an ethylene glycol ester (such as ethylene carbonate).
  • the patent US3803147 mentions the preparation method of diquat dichloride (example 11).
  • the alkyl-bispyridinium dibromide ethylene-bis-pyridinium bromide
  • sodium amalgam in the solvent.
  • 1'-ethylene-1,1'-dihydro-2,2'-bipyridine dibromide (1,1'-ethylene-1,1'-dihydro-2,2'-bipyridyl) in dilute hydrochloric acid Dichloride is produced by oxidation under air atmosphere.
  • diquat dihydrogen sulfate mentioned in the patent US3651060 consists of 2,2'-bipyridine and ethylene glycol reacting fully under the action of sulfuric acid at 185 ⁇ 195 °C to obtain diquat disulfate Hydrogen salt, conversion rate 51%.
  • Bromine can be dissociated from the adduct by heating, and then bromine can be distilled out, but in the process, the hypobromous acid (HBrO) generated by the reaction of bromine and water can oxidize the bipyridinium salt, As a result, more diquat cations will be lost, which is unacceptable in industrial production.
  • hypobromous acid HBA
  • pyridine hydrobromide can continue to react with bromine to form tribromide.
  • This tribromide can be used as a brominating agent. It shows good performance in the reaction of double bond addition and substitution with phenol Reaction characteristics, such as common pyridine tribromide PHBP (formula III), DMAP ⁇ HBr 3 (formula IV), 1,2-Dipyridiniumditribromide-ethane (DPTBE, formula V), 1,10- (ethane-1, 2-diyl) phenanthrolinedinium bistribromide (EPDBT, formula VI), pentylpyridinium tribromide (formula VII), 1,1 '-(Ethane-1,2-diyl) dipiperidinium Bis (tribromide) (EDPBT, formula VIII) in their participation In the reaction, good results were obtained in terms of selectivity and yield. However, the bromination reaction of diquat dibromide adduct has not been reported.
  • diquat dibromide adduct (formula I) or diquat dichloride
  • the adduct (Formula II) has good bromination ability, and exhibits good reaction characteristics in addition reaction to double bonds and substitution reaction to phenols.
  • the inventors reacted the above adduct with ethylene to prepare 1,2-dibromoethane, which can continue to react with 2,2'-bipyridine to prepare diquat dibromide salt.
  • Diquat dibromide is used as raw material to prepare dichloride dichloride and 1,2-dibromoethane again, so as to realize the recycling of bromine and greatly reduce the process cost.
  • the inventor found that the dichlordichloride adduct reacts with ethylene to generate a large amount of 1-chloro-2-bromoethane. In order to avoid the formation of 1-chloro-2-bromoethane, the adduct cannot Contains dichlordichloride adduct.
  • the inventors provided a suitable preparation method of diquat dichloride or diquat bisulfate through process improvement, using diquat dibromide as raw material, and selecting hydrogen peroxide as the oxide, in hydrochloric acid or In the presence of sulfuric acid, by controlling the reaction temperature and the amount of raw materials, the bromide ion of diquat dibromide (approximately 70% of the total raw materials) is converted into bromine, which preferentially reacts with unreacted diquat dibromide Precipitate in the form of an adduct to obtain a solid containing only diquat dibromide adduct, without the presence of chloride ions, thus avoiding the production of 1-chloro-2-bromoethane when the adduct reacts with ethylene , Only 1,2-dibromoethane is obtained. 1,2-Dibromoethane is an important chemical intermediate, which can be applied to the diquat dibromide process, which truly realizes the recycling
  • a green preparation method of diquat fast anion salt comprising: in the presence of hydrochloric acid or sulfuric acid, the oxidation reaction of diquat dibromide mother liquor and oxidant to obtain diquat fast dichloride or diquat fast sulfate
  • the reaction solution is filtered, and the filtrate is adjusted to pH and concentrated to obtain diquat dichloride mother liquor or diquat disulfate mother liquor; the filter cake is diquat dibromide adduct, after drying, and Organic solvents are mixed, and ethylene is reacted until the system pressure no longer changes.
  • the reaction solution is filtered to obtain a filtrate containing 1,2-dibromoethane and diquat dibromide solid.
  • the diquat dibromide is washed, Dried and formulated into diquat dibromide mother liquor.
  • the reaction of the preparation method of the present invention is as follows:
  • the green preparation method of diquat fast anion salt according to the present invention specifically includes: the diquat fast dibromide mother liquor is mixed with hydrochloric acid or sulfuric acid, and then undergoes an oxidation reaction with an oxidant; after the reaction is completed, the temperature is lowered and filtered to adjust the pH value of the filtrate To 3-7, concentrate to obtain diquat dichloride or diquat bisulfate mother liquor; filter cake (diquat dibromide adduct) is washed with water, dried, and mixed with organic solvent (diquat dibromide) Salt adduct is slightly soluble in organic solvent), the reaction is filtered until the pressure no longer changes, the reaction solution is filtered, and the resulting filter cake is diquat dibromide, which is washed and dried to prepare diquat
  • the bromide mother liquor is used as the raw material, and is oxidized with hydrogen peroxide, hydrochloric acid or sulfuric acid to prepare diquat dibromide adduct
  • the cationic content in the diquat dibromide mother liquor is 20-30%.
  • the cationic content of the diquat dichloride or diquat bisulfate mother liquor is 20-30%.
  • the oxidant is hydrogen peroxide, preferably hydrogen peroxide with a mass fraction of 30-50%.
  • the mass fraction of the hydrochloric acid is 20% to 36%, preferably 30 to 36%; the mass fraction of the sulfuric acid is 30 to 98%, preferably 50 to 70%.
  • the molar ratio of diquat dibromide to oxidant is 1: 1 to 1.5.
  • the molar ratio of diquat dibromide to hydrochloric acid or sulfuric acid is 1: 1.4 to 2.0.
  • the temperature of the oxidation reaction is from 10 to 100 ° C, preferably from 10 to 60 ° C.
  • the filter cake obtained after filtering the reaction liquid obtained by the oxidation reaction is washed with water until the filter cake does not contain chloride ions, and the washing liquid is incorporated into the filtrate.
  • ammonium bicarbonate, sodium bicarbonate, sodium carbonate, ammonia, etc. to adjust the pH of the filtrate to 3-7.
  • Hydrogen peroxide decomposition enzyme or hydrogen peroxide decomposition catalyst is added to the filtrate to fully decompose and remove residual hydrogen peroxide to prevent bottle expansion after packaging.
  • the organic solvent is one or more of acetonitrile, DMF, DMSO, dichloromethane and the like.
  • the organic solvent used for washing diquat dibromide solids is the same as the organic solvent used for the reaction.
  • Ethylene is fed until the reaction pressure is 0.2-2.0 MPa, preferably 0.4-1.0 MPa.
  • the filtrate containing 1,2-dibromoethane is separated by distillation to obtain 1,2-dibromoethane and an organic solvent; 1,2-dibromoethane is applied and reacted with bipyridine Preparation of diquat dibromide salt; 1,2-dibromoethane content in the separated and recovered organic solvent ⁇ 20%.
  • the method of the invention is simple, suitable for industrial production, and the cation loss rate is less than 0.5%; bromine is converted into 1,2-dibromoethane through adducts, the recovery rate of bromine is more than 96%, and the purified 1,2-bis is recovered
  • the reaction of bromoethane with bipyridine continues to prepare diquat dibromide salt, thereby achieving the recycling of bromine and avoiding the waste of bromine.
  • the amount of waste water generated by the method of the present invention is extremely small, and the process is basically green.
  • FIG. 1 is a schematic diagram of the process for preparing diquat dichloride in Example 1.
  • FIG. 1 is a schematic diagram of the process for preparing diquat dichloride in Example 1.
  • the washing solution was combined with the filtrate (4321.3g), the content of 1,2-dibromoethane was 23.33%, which further proved that only diquat dibromide adduct was obtained; the acetonitrile containing 1,2-dibromoethane was sent Entering the rectification tower for rectification and separation to obtain 1,2-dibromoethane and acetonitrile.
  • the calculated cation loss rate is 0.38%, and the bromine recovery rate is 97.04%.
  • the calculated cation loss rate is 0.29% and the bromine recovery rate is 96.2%.
  • the calculated cation loss rate is 0.37%, and the bromine recovery rate is 96.5%.
  • the calculated cation loss rate is 0.18% and the bromine recovery rate is 97.2%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明属于化学领域，公开了一种敌草快阴离子盐的绿色制备方法，包括：在盐酸或硫酸存在的条件下，敌草快二溴盐母液与氧化剂反应得到含有敌草快二氯盐或敌草快硫酸氢盐的反应液，反应液过滤，滤液经调pH、浓缩处理得到敌草快二氯盐母液或敌草快硫酸氢盐母液；滤饼与有机溶剂混合，通入乙烯反应至体系压力不再变化为止，反应液过滤，得到含有1,2-二溴乙烷的滤液和敌草快二溴盐固体，敌草快二溴盐经洗涤、干燥，配制成敌草快二溴盐母液；滤液经回收得到1,2-二溴乙烷，与联吡啶反应制敌草快二溴盐。本发明方法简单，适合于工业化生产，阳离子损失率低于0.5％；溴回收率在96％以上，从而实现了溴素的循环利用，避免了溴素的浪费。

Description

一种敌草快阴离子盐的绿色制备方法 技术领域
本发明属于化学领域，涉及一种敌草快阴离子盐的绿色制备方法，具体涉及一种敌草快二氯盐或敌草快硫酸氢盐的制备方法。
背景技术
敌草快(diquat)是一种优良的接触性干燥剂及具有内吸性质的除草剂，传统敌草快是二溴盐(CAS号:85-00-7)。敌草快二溴盐最早由英国ICI(Imperial Chemical Industries)(先正达的前身)开发并工业化，其主要制备方法是由2,2’-二联吡啶与1,2-二溴乙烷环合反应(US2823987)，同时指出敌草快的阴离子改变并不破坏其除草活性。
Figure PCTCN2018116907-appb-000001
专利GB815348提到敌草快阴离子的改变不破坏其除草活性(herbicidal activity)。相关文献也提到如百草枯、敌草快等除草剂的活性成分是阳离子部分，相关阴离子对其除草活性没有影响(The dipyridylium herbicides,paraquat and diquat,P99)。在这些化合物中，阴离子对其活性没有影响，C1 -,Br -,I -,CH 3SO 4 2-,SO 4 2-这些离子对等摩尔量底物的影响是相等的(J.Sci.Food Agric.,11,June,1960,309-315)。
溴是珍贵的资源，传统的溴素提取方法是卤水或海水经过浓缩、氧化等一系列的工艺手段将溴元素富集并提取出来，然后用于制造重要的化工产品。敌草快二溴盐作为除草剂或干燥剂，在使用过程中将又将溴元素带入到环境中去，造成了无谓的浪费。
氯离子或者硫酸(氢)根离子作为相对廉价的资源，用于敌草快阳离子的反荷离子是合适的。
现有技术中尚没有关于敌草快二氯盐(1,1'-乙撑-2,2'-联吡啶二氯盐)合适的工业化制备方法，现有敌草快二氯盐的制备方法都为探索性的，从ICI公司的专利文献上可以看出有以下几种尝试：
1、离子交换法。专利US 2823987(example 4)中提到，敌草快二溴盐溶液与氯化银充分搅拌反应，过滤出溴化银，得敌草快二氯盐溶液。
Figure PCTCN2018116907-appb-000002
也有文献(Brit.J.industr.Med.,1966,23,133)报道可以用离子交换树脂，通过离子交换 得敌草快二氯盐。
2、氯乙醇法。GB1087052以2,2’-联吡啶、1-氯-2-乙醇共热至130～170℃制备敌草快二氯盐和副产物乙二醇。
Figure PCTCN2018116907-appb-000003
3、专利US3308124提供了一种新的敌草快二氯盐的制备方法，具体为等摩尔量的乙烯、氯气连续通入由2,2-联吡啶、催化剂(如NaCl、玻璃丝、硅胶等)、溶剂(如硝基苯等)组成的混合溶液中，于80～160℃条件下反应制得敌草快二氯盐，专利中未给出原料转化和产品收率情况。同时指出二氯乙烷和2,2’-联吡啶在此条件下无法制备出敌草快二氯盐。
Figure PCTCN2018116907-appb-000004
4、乙二醇法。US3651060以2,2’-联吡啶、乙二醇和酸共热制备不同阴离子的敌草快鎓盐。酸可以是无机酸(盐酸、氢溴酸、氢碘酸)、含氧酸(硫酸、磷酸、硼酸)，乙二醇可以是乙二醇酯(如碳酸乙二酯)。
Figure PCTCN2018116907-appb-000005
5、专利US3803147提及敌草快二氯盐(example 11)的制备方法，烷基双吡啶二溴盐(ethylene-bis-pyridinium bromide)在溶剂中用钠汞齐进行偶联，生成的1,1’-亚乙基-1,1’-二氢-2,2’-联吡啶二溴盐(1,1'-ethylene-1,1'-dihydro-2,2'-bipyridyl)在稀盐酸和空气氛围下氧化制得敌草快二氯盐。
Figure PCTCN2018116907-appb-000006
6、专利US3651060提到的敌草快硫酸氢盐的制备方法，由2,2’-联吡啶与乙二醇在硫酸的作用下，于185～195℃下充分反应，得敌草快二硫酸氢盐，转化率51％。
Figure PCTCN2018116907-appb-000007
从以上各个制备方法来看，ICI公司在开发敌草快时，敌草快二溴盐的制备相对较为容易，但敌草快二氯盐或敌草快硫酸氢盐的制备方法，无论从工艺条件的复杂性、收率、产品纯度及稳定性等各方面来讲，都没有找到更好的工艺路线，上述专利提到的敌草快二氯盐或者敌草快硫酸氢盐的制备方法不适用于工业化生产。
申请人在CN201610605417中采用氯气进行离子置换制备敌草快二氯盐，然后将溴素在高温条件下蒸馏出来，该方法存在一定的困难和局限性。申请人通过进一步研究发现：敌草快二溴盐溶液通入氯气时，能生成不溶于水的棕色固体，通过分析判断，该棕色固体是无定型非晶体固体，是敌草快二溴盐加合物(式Ⅰ)与敌草快二氯盐加合物(式Ⅱ)的混合物，难以得到纯净的敌草快二溴盐加合物。该混合物不溶于水，会从反应体系中析出，不能得到敌草快二氯盐单体化合物。通过加热的方式可以将溴素从加合物中解离出来，进而将溴蒸馏出来，但在该过程中，溴与水反应生成的次溴酸(HBrO)能将联吡啶鎓盐氧化掉，从而会损失较多的敌草快阳离子，这在工业生产中是不能接受的。
Figure PCTCN2018116907-appb-000008
发明人在专利申请CN201710760340中，在酚类化合物存在的条件下对上述加合物进行研究，在制备1,1'-乙撑-2,2'-联吡啶二氯盐的同时，以酚类化合物为溴素吸收剂制得溴化物，但该方法所得的副产物溴化物需通过外卖来解决它的出路问题，这就额外增加了成本及相关不确定性，再者酚类物具有较难闻的气味及毒性，不利于环境及工人的身心健康。
众所周知，吡啶的氢溴酸盐能继续与溴反应生成三溴化物，该三溴化物可以作为溴化剂，在双键的加成反应，与酚类的取代反应等反应中都表现出很好的反应特性，如常见的吡啶的三溴盐PHBP(式Ⅲ)、DMAP·HBr 3(式Ⅳ)、1,2-Dipyridiniumditribromide-ethane(DPTBE，式Ⅴ)、1,10-(ethane-1,2-diyl)phenanthrolinedinium bistribromide(EPDBT，式Ⅵ)、pentylpyridinium tribromide(式Ⅶ)、1,1’-(Ethane-1,2-diyl)dipiperidinium Bis(tribromide)(EDPBT， 式Ⅷ)在其参与的相关反应中，在选择性和产率等方面都能得到较好的结果。但敌草快二溴盐加合物的溴化反应还没有见到报道。
Figure PCTCN2018116907-appb-000009
因此，有必要寻求一种合适的方法，既能顺利的生产敌草快二氯盐或者敌草快硫酸氢盐，又能使溴通过合理的方式转化为其他更重要的化合物或者实现溴元素的循环利用。
发明内容
发明人针对上述已知敌草快二氯盐或敌草快硫酸氢盐的制备技术中存在的问题，通过实验发现敌草快二溴盐加合物(式Ⅰ)或者敌草快二氯盐加合物(式Ⅱ)具有良好的溴化能力，在对双键的加成反应及对酚类的取代反应中表现出良好的反应特性。通过优化，发明人将上述加合物与乙烯反应制备1,2-二溴乙烷，1,2-二溴乙烷可以继续和2,2’-联吡啶反应制备敌草快二溴盐，敌草快二溴盐作为原料再次制备敌草快二氯盐和1,2-二溴乙烷，从而实现溴元素的循环利用，大大降低工艺成本。但发明人发现敌草快二氯盐加合物与乙烯反应，会生成大量的1-氯-2-溴乙烷，为了避免1-氯-2-溴乙烷的生成，加合物中不能含有敌草快二氯盐加合物。据此，发明人通过工艺改进，提供一种合适的敌草快二氯盐或敌草快硫酸氢盐的制备方法，以敌草快二溴盐为原料，选择双氧水作为氧化物，在盐酸或者硫酸存在下，通过控制反应温度、原料用量，使得敌草快二溴盐(约占原料总量的70％)的溴离子转化成溴素，溴素优先与未反应的敌草快二溴盐结合成加合物的形式析出，得到只含有敌草快二溴盐加合物的固体，无氯离子的存在，从而避免了加合物与乙烯反应时产生1-氯-2-溴乙烷，只得到1,2-二溴乙烷，1,2-二溴乙烷作为重要的化工中间体，可套用于敌草快二溴盐工艺，真正实现了溴 元素的循环套用，避免溴元素浪费。
本发明目的可以通过以下技术方案实现：
一种敌草快阴离子盐的绿色制备方法，包括：在盐酸或硫酸存在的条件下，敌草快二溴盐母液与氧化剂进行氧化反应得到含有敌草快二氯盐或敌草快硫酸氢盐的反应液，反应液过滤，滤液经调pH、浓缩处理得到敌草快二氯盐母液或敌草快硫酸氢盐母液；滤饼为敌草快二溴盐加合物，经干燥后，与有机溶剂混合，通入乙烯反应直至体系压力不再变化为止，反应液过滤，得到含有1,2-二溴乙烷的滤液和敌草快二溴盐固体，敌草快二溴盐经洗涤、干燥，配制成敌草快二溴盐母液。
本发明制备方法的反应如下所示：
Figure PCTCN2018116907-appb-000010
本发明所述的敌草快阴离子盐的绿色制备方法，具体包括：敌草快二溴盐母液与盐酸或硫酸混合后，与氧化剂进行氧化反应，反应结束后降温、过滤，调节滤液的pH值至3-7，浓缩得到敌草快二氯盐或敌草快硫酸氢盐母液；滤饼(敌草快二溴盐加合物)用水洗涤、干燥，与有机溶剂混合(敌草快二溴盐加合物微溶于有机溶剂中)，通入乙烯反应至压力不再变化，反应液过滤，得到的滤饼即为敌草快二溴盐，经洗涤、干燥，配制成敌草快二溴盐母液作为原料，与双氧水、盐酸或硫酸进行氧化反应制备敌草快二溴盐加合物、敌草快二氯盐或敌草快硫酸氢盐；滤液经精馏，分离得到有机溶剂和1,2-二溴乙烷，1,2-二溴乙烷与2,2’-联吡啶反应制备敌草快二溴盐，回收的有机溶剂套用。
所述的敌草快二溴盐母液中阳离子含量为20～30％。所述的敌草快二氯盐或敌草快硫酸氢盐母液中阳离子含量为20～30％。
所述的氧化剂为双氧水，优选为质量分数30～50％的双氧水。
所述的盐酸的质量分数为20％～36％，优选为30～36％；所述的硫酸的质量分数为 30～98％，优选为50～70％。
所述的敌草快二溴盐与氧化剂的摩尔比为1:1～1.5。
所述的敌草快二溴盐与盐酸或硫酸的摩尔比为1:1.4～2.0。
所述的氧化反应的温度为10～100℃，优选为10～60℃，发明人发现当温度＞60℃时，加合物有少量分解，因此氧化反应的温度进一步优选为30～50℃。
氧化反应得到的反应液过滤后得到的滤饼，用水洗涤至滤饼中不含有氯离子，洗涤液并入滤液。
采用碳酸氢铵、碳酸氢钠、碳酸钠、氨水等调节滤液的pH值至3-7。滤液中加入双氧水分解酶或双氧水分解催化剂，充分分解去除残留的双氧水，防止包装后发生涨瓶现象。
所述的有机溶剂为乙腈、DMF、DMSO、二氯甲烷等中的一种或多种混合。洗涤敌草快二溴盐固体所用的有机溶剂与反应用的有机溶剂相同。
通入乙烯至反应压力为0.2-2.0MPa，优选为0.4-1.0MPa。
作为优选技术方案，所述的含有1,2-二溴乙烷的滤液经精馏分离得到1,2-二溴乙烷和有机溶剂；1,2-二溴乙烷套用，与联吡啶反应制备敌草快二溴盐；经分离回收的有机溶剂中1,2-二溴乙烷含量≤20％。
本发明的有益效果：
本发明方法简单，适合于工业化生产，阳离子损失率低于0.5％；溴通过加合物转化为1,2-二溴乙烷，溴回收率在96％以上，回收提纯的1,2-二溴乙烷与联吡啶反应，继续制备敌草快二溴盐，从而实现了溴素的循环利用，避免了溴素的浪费。同时，本发明方法所产生的废水量极少，基本实现了工艺的绿色化。
附图说明
图1为实施例1制备敌草快二氯盐的流程示意图。
具体实施方式
下面结合实施例对本发明的技术方案做进一步说明，但本发明的保护范围不限于此：
实施例1
如图1，将敌草快二溴盐母液7000.5g(阳离子20.63％)与1114.8g盐酸(质量分数36％)在反应釜中混合，滴加到双氧水(质量分数29.8％)1078.1g，控制滴加速度，维持体系温度在40-50℃，滴加完毕，在该温度下充分搅拌反应1h。反应液至过滤干燥釜过滤，滤饼为敌草快二溴盐加合物，用1000g水充分洗涤，洗涤液并入滤液，再用少许碳酸氢铵调节pH值至4，在脱溶釜中浓缩出部分水后配制成敌草快阳离子含量26.40％的敌草快二氯盐母 液3875.5g。
滤饼经洗涤、干燥后得加合物干品1565.1g，将干燥的加合物、乙腈1800.2g置于高压釜内，通乙烯气体至压力0.8MPa，反应过程中适时补充压力，反应至气体压力不再下降为止，结束反应，反应液在过滤釜中过滤，得到的滤饼用适量乙腈充分洗涤，干燥后，配制成阳离子含量为20.63％的敌草快二溴盐母液2014.5g，溴离子含量17.90％。洗涤液与滤液合并(4321.3g)，1,2-二溴乙烷含量为23.33％，进一步证明只得到了敌草快二溴盐加合物；将含有1,2-二溴乙烷的乙腈送入精馏塔进行精馏分离，得到1,2-二溴乙烷和乙腈。
计算阳离子损失率为0.38％，溴回收率为97.04％。
实施例2
将敌草快二溴盐母液7000.3g(阳离子20.63％)与2176.8g硫酸(质量分数50％)混合，滴加到双氧水(29.8％)1080.1g，控制滴加速度，维持体系温度在40-50℃，滴加完毕，在该温度下充分搅拌反应1h。反应液过滤，滤饼用1000g水充分洗涤，洗涤液并入滤液，再用适量碳酸氢铵调节pH值4，浓缩出部分水后配制成敌草快阳离子含量26.40％的敌草快硫酸盐母液3880.1g。
滤饼经洗涤、干燥后得加合物干品1566.2g，将干燥的加合物、乙腈1805.1g置于高压釜，通乙烯气体至压力0.8MPa，反应过程中适时补充压力，反应至气体压力不再下降为止，结束反应，反应液过滤，得到的固体用适量乙腈充分洗涤，干燥后，配制成阳离子含量为20.65％的敌草快二溴盐母液2013.8g，溴离子含量17.50％。洗涤液与滤液合并4320.1g，1,2-二溴乙烷含量23.28％，未检测到1-氯-2-溴乙烷。
计算阳离子损失率为0.29％，溴回收率为96.2％。
实施例3
将敌草快二溴盐母液3500.5g(阳离子20.63％)与570.2g盐酸(36％)混合，滴加到双氧水(29.8％)560.1g，控制滴加速度，维持体系温度在40-50℃，滴加完毕，在该温度下充分搅拌反应1h。反应液过滤，滤饼用500g水充分洗涤，洗涤液并入滤液，再用少许碳酸氢铵调pH值4，浓缩出部分水后配制成敌草快阳离子含量26.40％的敌草快二氯盐母液1937.8g。
滤饼经洗涤、干燥后得加合物干品782.8g，将干燥的加合物、乙腈901.2g置于高压釜，通乙烯气体至压力0.8MPa，反应过程中适时补充压力，反应至气体压力不再下降为止，结束反应，反应液过滤，固体用适量乙腈充分洗涤，干燥后，配制成阳离子含量为20.63％的敌草快二溴盐母液1007.6g，溴离子含量17.80％。洗涤液与滤液合并2160.6g，1,2-二溴乙烷 含量23.20％，未检测到1-氯-2-溴乙烷。
计算阳离子损失率为0.37％，溴回收率为96.5％。
实施例4
将敌草快二溴盐母液700.5g(阳离子20.63％)与115.8g盐酸(36％)混合，滴加到双氧水(29.8％)110.1g，控制滴加速度，维持体系温度在40-50℃，滴加完毕，在该温度下充分搅拌反应1h。反应液过滤，滤饼用100g水充分洗涤，洗涤液并入滤液，再用少许碳酸氢铵调pH值4，浓缩出部分水后配制成敌草快阳离子含量26.50％的敌草快二氯盐母液387.5g。
滤饼经洗涤、干燥后得加合物干品156.1g，将干燥的加合物、乙腈180.2g置于高压釜，通乙烯气体至压力0.8MPa，反应过程中适时补充压力，反应至气体压力不再下降为止，结束反应，过滤，固体用适量乙腈充分洗涤，干燥后，配制成阳离子含量为20.63％的敌草快二溴盐母液201.5g，溴离子含量17.90％。洗涤液与滤液合并432.3g，1,2-二溴乙烷含量23.40％，未检测到1-氯-2-溴乙烷。
计算阳离子损失率为0.18％，溴回收率为97.2％。

Claims (10)

  1. 一种敌草快阴离子盐的绿色制备方法，其特征在于包括：在盐酸或硫酸存在的条件下，敌草快二溴盐母液与氧化剂进行氧化反应得到含有敌草快二氯盐或敌草快硫酸氢盐的反应液，反应液过滤，滤液经调pH、浓缩处理得到敌草快二氯盐母液或敌草快硫酸氢盐母液；滤饼与有机溶剂混合，通入乙烯反应至体系压力不再变化为止，反应液过滤，得到含有1,2-二溴乙烷的滤液和敌草快二溴盐固体，敌草快二溴盐经洗涤、干燥，配制成敌草快二溴盐母液。
  2. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于所述的敌草快二溴盐母液中阳离子含量为20～30％；所述的敌草快二氯盐或敌草快硫酸氢盐母液中阳离子含量为20～30％。
  3. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于所述的氧化剂为质量分数30～50％的双氧水；所述的盐酸的质量分数为20％～36％；所述的硫酸的质量分数为30～98％。
  4. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于所述的敌草快二溴盐与盐酸或硫酸的摩尔比为1:1.4～2.0。
  5. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于所述的敌草快二溴盐与氧化剂的摩尔比为1:1～1.5。
  6. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于所述的氧化反应的温度为10～100℃，优选为10～60℃，进一步优选为30～50℃。
  7. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于采用碳酸氢铵、碳酸氢钠、碳酸钠或氨水调节滤液的pH值至3-7。
  8. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于通入乙烯至反应压力为0.2-2.0MPa，优选为0.4-1.0MPa。
  9. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于所述的有机溶剂为乙腈、DMF、DMSO、二氯甲烷中的一种或多种混合；洗涤敌草快二溴盐所用的有机溶剂与反应用的有机溶剂相同。
  10. 根据权利要求1所述的敌草快阴离子盐的绿色制备方法，其特征在于含有1,2-二溴乙烷的滤液经精馏分离得到1,2-二溴乙烷和有机溶剂；1,2-二溴乙烷套用，与联吡啶反应制备敌草快二溴盐。
PCT/CN2018/116907 2018-11-07 2018-11-22 一种敌草快阴离子盐的绿色制备方法 WO2020093459A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811318062.1A CN109232569B (zh) 2018-11-07 2018-11-07 一种敌草快阴离子盐的绿色制备方法
CN201811318062.1 2018-11-07

Publications (1)

Publication Number Publication Date
WO2020093459A1 true WO2020093459A1 (zh) 2020-05-14

Family

ID=65077145

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/116907 WO2020093459A1 (zh) 2018-11-07 2018-11-22 一种敌草快阴离子盐的绿色制备方法

Country Status (2)

Country Link
CN (1) CN109232569B (zh)
WO (1) WO2020093459A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113214258A (zh) * 2021-05-14 2021-08-06 安徽国星生物化学有限公司 一种敌草快二氯盐合成方法及装置
CN114957254A (zh) * 2022-06-10 2022-08-30 南京红太阳生物化学有限责任公司 一种敌草快二氯盐的制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308124A (en) * 1963-06-05 1967-03-07 Ici Ltd Process for preparing 1, 1'-alkylene-2, 2'-bipyridylium dihalides
US3342830A (en) * 1964-06-08 1967-09-19 Ici Ltd Method for producing 2, 2'-bipyridylium salts
US3651060A (en) * 1968-10-04 1972-03-21 Ici Ltd 1 1'-ethylene-2 2'-bipyridlium salts
US3803147A (en) * 1968-04-02 1974-04-09 Ici Ltd Manufacture of bipyridylium salts and related compounds
CN106220629A (zh) * 2016-07-28 2016-12-14 南京红太阳生物化学有限责任公司 一种敌草快二氯盐的制备方法
CN106279166A (zh) * 2016-08-17 2017-01-04 南京红太阳生物化学有限责任公司 一种敌草快不同阴离子盐的制备方法
CN107573342A (zh) * 2017-08-30 2018-01-12 南京红太阳生物化学有限责任公司 一种1,1′‑乙撑‑2,2′‑联吡啶二氯盐的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR82187E (fr) * 1961-08-25 1964-01-04 Ici Ltd Sels quaternaires nouveaux
GB1185559A (en) * 1968-08-05 1970-03-25 Pennsalt Chemicals Corp Herbicidal Compositions
US3674788A (en) * 1971-01-15 1972-07-04 Great Lakes Chemical Corp Dipyridylium quaternary dihalide halogen complexes

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3308124A (en) * 1963-06-05 1967-03-07 Ici Ltd Process for preparing 1, 1'-alkylene-2, 2'-bipyridylium dihalides
US3342830A (en) * 1964-06-08 1967-09-19 Ici Ltd Method for producing 2, 2'-bipyridylium salts
US3803147A (en) * 1968-04-02 1974-04-09 Ici Ltd Manufacture of bipyridylium salts and related compounds
US3651060A (en) * 1968-10-04 1972-03-21 Ici Ltd 1 1'-ethylene-2 2'-bipyridlium salts
CN106220629A (zh) * 2016-07-28 2016-12-14 南京红太阳生物化学有限责任公司 一种敌草快二氯盐的制备方法
CN106279166A (zh) * 2016-08-17 2017-01-04 南京红太阳生物化学有限责任公司 一种敌草快不同阴离子盐的制备方法
CN107573342A (zh) * 2017-08-30 2018-01-12 南京红太阳生物化学有限责任公司 一种1,1′‑乙撑‑2,2′‑联吡啶二氯盐的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KARSTEN SONNENBERG ET AL.: "Closing the Gap Stru- ctural Evidence for the Missing Hexabromide Dianion [Br6]2", CHEM. EUR. J ., vol. 24, 24 January 2018 (2018-01-24), pages 1072 - 1075, XP055704951 *

Also Published As

Publication number Publication date
CN109232569B (zh) 2021-05-25
CN109232569A (zh) 2019-01-18

Similar Documents

Publication Publication Date Title
CN107573342B (zh) 一种1,1’-乙撑-2,2’-联吡啶二氯盐的制备方法
WO2020093459A1 (zh) 一种敌草快阴离子盐的绿色制备方法
CN103664712B (zh) 一种制备氟磺酰亚胺锂的方法
CN112500411A (zh) 一种1,1′-乙撑-2,2′-联吡啶二氯盐的制备方法
JPH02199002A (ja) 臭化水素酸およびメタノールの回収方法
CN105985248B (zh) 一种合成氨基联芳香类化合物的方法
CN107501059B (zh) 一种绿色环保的4-(4’-烷基环己基)环己酮的合成方法
CN113120925B (zh) 一种从异佛尔酮裂解料中回收碘化物的方法
CN105198710B (zh) 一种间叔丁基苯酚的合成方法
CN113307289A (zh) 一种含溴代烷烃的危险废物资源化回收方法
CN103086959A (zh) 一种生产3，5，6-三氯吡啶醇钠的新工艺
CN111170846B (zh) 一种制备3,3-二甲基-2-氧-丁酸的方法
CN106187870A (zh) 一种4‑甲基吡啶定位硝化为3‑硝基‑4‑甲基吡啶的方法
CN115043714A (zh) 一种绿色环保合成苯偶酰的方法
CN111303172B (zh) 一种制备依托度酸甲酯的方法
CN113896619A (zh) 4,4`-二溴二苯醚的制备方法
CN109575019A (zh) 一种5-溴-7-氮杂吲哚的制备方法
CN110655442A (zh) 一种邻氯三氯甲苯新型氯化工艺
CN104627964B (zh) 利用卤水制取溴的方法
CN115819420B (zh) 一种敌草快阴离子盐的制备方法
CN114560873B (zh) 一种3-氯甲基-6-氯-噁唑[4,5-b]吡啶-2(3H)酮的制备方法
CN105884582A (zh) 一种2,5-二氯苯酚的合成工艺
CN102391129A (zh) 一种2,7-二硝基芴酮的制取方法
CN112079756B (zh) 二烯丙基双酚s醚的制备方法
JPH0215063A (ja) ２−メトキシ−６−メチルアミノピリジンの製造法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18939175

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18939175

Country of ref document: EP

Kind code of ref document: A1