CN106220629A - A kind of preparation method of diquat dibromide two villaumite - Google Patents
A kind of preparation method of diquat dibromide two villaumite Download PDFInfo
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- CN106220629A CN106220629A CN201610605417.XA CN201610605417A CN106220629A CN 106220629 A CN106220629 A CN 106220629A CN 201610605417 A CN201610605417 A CN 201610605417A CN 106220629 A CN106220629 A CN 106220629A
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- diquat dibromide
- villaumite
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- 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
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Abstract
The invention discloses the preparation method of a kind of diquat dibromide two villaumite, with diquat dibromide dibromo salt aqueous solution as raw material, it is oxidizing bromide ion with chlorine, generate bromine and diquat dibromide two villaumite, wherein, bromine reclaims through distillation condensation, after remaining bromine and chlorine are by being passed through air, oxygen, water vapour or inert gas purge, obtains diquat dibromide two villaumite.The preparation of this diquat dibromide two villaumite, with diquat dibromide dibromo salt aqueous solution as raw material, obtained by cheap chlorine oxidation, the production cost that the method has is low, and reaction is simple, the advantage that product yield is high, it is suitable for industrialized production, the more important thing is and obtain displacing expensive bromine, bromine, as a kind of widely used industrial chemicals, can sell as product；The preparation of diquat dibromide two villaumite can also be cycled to used in, overcome the problem that existing herbicide diquat dibromide production cost is high, there is obvious economic benefit.
Description
Technical field
The invention belongs to chemical industry and pesticide field, be specifically related to the preparation method of a kind of diquat dibromide two villaumite.
Background technology
Diquat dibromide is the steriland herbicide of a kind of function admirable, and the stem and leaf simultaneously applying also for Rhizoma Solani tuber osi and Radix Pachyrhizi Erosi is urged
Withered, diquat dibromide described on ordinary meaning i.e. refers to diquat dibromide dibromo salt, and by 2,2 '-bipyridyl and Bromofume ring-closure reaction obtain
Arrive.Be only second to the third-largest steriland herbicide of glyphosate and diquat dibromide as the whole world, in recent years, diquat dibromide market demand increases
Add very fast.While it is true, due to the price height of high bromine content and bromine itself in diquat dibromide dibromo salt, cause diquat dibromide to produce
High cost, limits the extensive application of diquat dibromide to a certain extent.
Play herbicide effect in diquat dibromide dibromo salt is its cationic moiety, unrelated with anion bromine.Relative due to chlorine
Atom mass rate bromine is much lower, and low price, prepares and replaces diquat dibromide two villaumite of bromide ion can overcome enemy's grass with chloride ion
The fast too high problem of dibromo salt production cost.Currently, with respect to diquat dibromide two villaumite synthetic method report less, specifically include that
(1) patent US3308124 mention can by dichloroethanes and 2,2 '-bipyridyl reaction obtain.But, due to two chloroethenes
Alkane specific activity Bromofume is low many, if directly with 2,2 '-bipyridyl ring-closure reaction needs High Temperature High Pressure, the enemy obtained under the conditions of this
Fast two villaumites of grass are serious to equipment corrosion, and produce a large amount of tar, and product quality is poor, and the method does not has industrialized production so far
It is worth.
(2) patent US2823987 by adding the AgCl of fresh preparation to the aqueous solution of diquat dibromide dibromo salt, through halogen ion
Exchange reaction obtains diquat dibromide two villaumite；This kind of method employs expensive silver chloride, and cost is high, and the response time is long, no
Be suitable to industrialized production.
(3) patent US3803147 is raw material with 1,1 '-ethylidene-1,1 '-dihydro-2,2 '-bipyridyl dibromo salt, dilute
Diquat dibromide two villaumite is prepared under hydrochloric acid and air effect.The method raw material is not easy to obtain, and is difficult to reaction thoroughly, and product purity is low,
Be not suitable for industrialized production.
Summary of the invention
Present invention aims to the problems referred to above and provide a kind of new method preparing diquat dibromide two villaumite, the method is raw
Producing low cost, reaction is simple, and product yield is high, is suitable for industrialized production.
In order to solve the problems referred to above, the present invention adopts the following technical scheme that as follows: the preparation side of a kind of diquat dibromide two villaumite
Method, with diquat dibromide dibromo salt aqueous solution as raw material, is oxidizing bromide ion with chlorine, generates bromine and diquat dibromide dichloro
Salt, wherein, bromine reclaims through distillation condensation, and remaining bromine and chlorine are by being passed through air, oxygen, water vapour or noble gas
After purging, obtain diquat dibromide two villaumite.
Preferably, in described diquat dibromide dibromo salt aqueous solution, diquat dibromide dibromo salt is the bromine after distillation condensation is reclaimed
Element, carries out additive reaction with ethylene and obtains Bromofume, then the Bromofume and 2 that will generate, and 2 '-bipyridyl carries out cyclization
Obtain.The recovery of bromine is cycled to used in the preparation of diquat dibromide dibromo salt, be equivalent to achieve in a mild condition dichloroethanes and
2,2 '-bipyridyl highly effective reaction obtains diquat dibromide two villaumite, generates, for industrialization, the approach that diquat dibromide two villaumite provides feasible, from
For another angle, overcome the problem that existing herbicide diquat dibromide production cost is high.
Wherein, the concrete operations condition of the preparation that the recovery of bromine is cycled to used in diquat dibromide dibromo salt uses prior art.
Described bromine condensation Distillation recovery, can be carried out, it is possible to carry out after the completion of reaction in course of reaction.
Described diquat dibromide dibromo salt aqueous solution mass concentration is 1%～80%, preferably 20%～40%.
Described oxidant chlorine is 1～10:1 with the mol ratio of diquat dibromide dibromo salt, preferably 1～3:1.
Described reaction temperature is 20～120 DEG C, preferably 50～110 DEG C.
Described noble gas is nitrogen or argon.
Beneficial effects of the present invention:
The inventive method prepares diquat dibromide two villaumite, with diquat dibromide dibromo salt aqueous solution as raw material, by cheap chlorine
Oxidation obtains, and the production cost that the method has is low, and reaction is simple, the advantage that product yield is high, is suitable for industrialized production, heavier
Want is to obtain displacing expensive bromine, and bromine, can be straight as product as a kind of widely used industrial chemicals
Pick out and sell；Bromofume can also be obtained with ethylene reaction, be cycled to used in diquat dibromide dibromo salt, the preparation of diquat dibromide two villaumite,
Its essence is to achieve dichloroethanes and 2 in a mild condition, 2 '-bipyridyl highly effective reaction, overcomes existing herbicide enemy's grass
The problem that fast production cost is high, has obvious economic benefit.
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, this embodiment
It is only used for explaining the present invention, is not intended that limiting the scope of the present invention.
Embodiment 1
Equipped with in the 2000ml four-hole boiling flask of mechanical agitator, thermometer and distilling apparatus, add 640g
(1.86mol) diquat dibromide dibromo salt, adds water and is configured to the diquat dibromide dibromo salt aqueous solution that mass concentration is 40%, opens stirring,
Being warming up to 80 DEG C, regulation chlorine is passed through speed, and maintaining reaction temperature is 85 DEG C of reactions, and the bromine produced in course of reaction is by cold
Solidifying device trapping, tail gas adds alkali liquor absorption.When reaction temperature is down to 80 DEG C, reaction terminates, and stops logical chlorine, and blowing air purging is molten
Bromine remaining in liquid and chlorine, KI-starch paper detects, and electronic scale metering reaction amounts to and consumes chlorine 185g (2.6mol),
Obtaining product diquat dibromide two villaumite 470g (1.85mol), molar yield 99.5%, the thick bromine of trapping is through except water, phosphorus pentoxide
It is dried, final bromine 286g, bromine yield 96.0%.
Embodiment 2
Equipped with in the 2000ml four-hole boiling flask of mechanical agitator, thermometer and reflux, add 640g
(1.86mol) diquat dibromide dibromo salt, adds water and is configured to the diquat dibromide dibromo salt aqueous solution that mass concentration is 40%, opens stirring,
Being warming up to 45 DEG C, regulation chlorine is passed through speed, and maintaining reaction temperature is 50 DEG C.When reaction temperature is down to 45 DEG C, reaction terminates,
Intensification separated bromine.Distillation terminates, remaining bromine and chlorine in logical nitrogen purged solution, and KI-starch paper detects.Electricity
Son claims metering reaction total to consume chlorine 156.2g (2.2mol), obtains product diquat dibromide two villaumite 468.6g (1.84mol), mole
Yield 99.1%, the thick bromine of trapping through being dried except water, phosphorus pentoxide, final bromine 286.8g, bromine yield 96.3%.
Embodiment 3
Equipped with in the 2000ml four-hole boiling flask of mechanical agitator, thermometer and distilling apparatus, add 320g
(0.93mol) diquat dibromide dibromo salt, adds water and is configured to the diquat dibromide dibromo salt aqueous solution that mass concentration is 20%, opens stirring,
Being warming up to 80 DEG C, regulation chlorine is passed through speed, and maintaining reaction temperature is 83 DEG C of reactions, and the bromine produced in course of reaction is by cold
Solidifying device trapping, tail gas adds alkali liquor absorption.When reaction temperature is down to 80 DEG C, reaction terminates, and stops logical chlorine, and blowing air purging is molten
Bromine remaining in liquid and chlorine, KI-starch paper detects.Electronic scale metering reaction amounts to and consumes chlorine 79g (1.1mol),
Product diquat dibromide two villaumite 235.7g (0.928mol), molar yield 99.8%, the thick bromine of trapping is through except water, phosphorus pentoxide
It is dried, final bromine 143.4g, bromine yield 96.4%.
Embodiment 4
Equipped with in the 2000ml four-hole boiling flask of mechanical agitator, thermometer and reflux, add 320g
(0.93mol) diquat dibromide dibromo salt, adds water and is configured to the diquat dibromide dibromo salt aqueous solution that mass concentration is 20%, opens stirring,
Regulating chlorine under room temperature condition and be passed through speed, maintaining reaction temperature is 30 DEG C.When reaction temperature is down to room temperature, reaction terminates,
Intensification separated bromine.Distillation terminates, remaining bromine and chlorine in logical nitrogen purged solution, and KI-starch paper detects.Electricity
Son title metering reaction amounts to and consumes chlorine 130g (1.8mol), obtains product diquat dibromide two villaumite 234.3g (0.92mol), mole receipts
Rate 99.2%, the thick bromine of trapping through being dried except water, phosphorus pentoxide, final bromine 143.5g, bromine yield 96.4%.
Embodiment 5
Take the bromine 2500g of the method gained according to embodiment 1, be equipped with the 2000ml four-hole boiling flask of condensing unit
In, open stirring, be slowly introducing ethylene, controlling reaction temperature is 35 DEG C, when solution becomes colorless, stops logical ethylene, normal pressure
Distillation, obtains Bromofume (129-132 DEG C of fraction) 2790g.2790g is added in equipped with the 2000ml four-hole boiling flask of condensing unit
Bromofume and 350g 2,2 '-bipyridyl, stirring, temperature rising reflux reaction 30h.Cooling, sucking filtration, washing with acetone, methanol aqueous solution
Recrystallization obtains 750g diquat dibromide dibromo salt list hydrate (purity 99.5%).Take the diquat dibromide dibromo salt list hydrate of gained
677g (equivalent diquat dibromide dibromo salt 640g), carries out according to the process of embodiment 1, obtains product diquat dibromide two villaumite 472g, mole
Yield 99.6%, the thick bromine of trapping through being dried except water, phosphorus pentoxide, final bromine 286g, bromine yield 96.0%.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. the preparation method of diquat dibromide two villaumite, it is characterised in that with diquat dibromide dibromo salt aqueous solution as raw material, with chlorine
For oxidizing bromide ion, generating bromine and diquat dibromide two villaumite, wherein, bromine reclaims through distillation condensation, remaining bromine
With chlorine by being passed through air, oxygen, water vapour or inert gas purge after, obtain diquat dibromide two villaumite.
The preparation method of diquat dibromide two villaumite the most according to claim 1, it is characterised in that described diquat dibromide dibromo salt
In aqueous solution, diquat dibromide dibromo salt is the bromine after distillation condensation is reclaimed, and carries out additive reaction with ethylene and obtains Bromofume,
Again the Bromofume generated and 2,2 '-bipyridyl are carried out cyclization and obtain.
3. according to the preparation method of diquat dibromide two villaumite described in claim 1 or 2, it is characterised in that described bromine distillation
Condensation is reclaimed, and can carry out, it is possible to carry out after the completion of reaction in course of reaction.
The preparation method of diquat dibromide two villaumite the most according to claim 1, it is characterised in that described diquat dibromide dibromo salt
The mass concentration of aqueous solution is 1% ~ 80%.
The preparation method of diquat dibromide two villaumite the most according to claim 4, it is characterised in that described diquat dibromide dibromo salt
The mass concentration of aqueous solution is 20% ~ 40%.
The preparation method of diquat dibromide two villaumite the most according to claim 1, it is characterised in that described oxidant chlorine with
The mol ratio of diquat dibromide dibromo salt is 1 ~ 10:1.
The preparation method of diquat dibromide two villaumite the most according to claim 6, it is characterised in that described oxidant chlorine with
The mol ratio of diquat dibromide dibromo salt is 1 ~ 3:1.
The preparation method of diquat dibromide two villaumite the most according to claim 1, it is characterised in that reaction temperature is 20 ~ 120
℃。
The preparation method of diquat dibromide two villaumite the most according to claim 8, it is characterised in that reaction temperature is 50 ~ 110
℃。
The preparation method of diquat dibromide two villaumite the most according to claim 1, it is characterised in that described noble gas is
Nitrogen or argon.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573342A (en) * | 2017-08-30 | 2018-01-12 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of the villaumite of 1,1 ' ethylene, 2,2 ' bipyridyl two |
| CN108207946A (en) * | 2018-04-12 | 2018-06-29 | 南京科翼新材料有限公司 | A kind of special assistant suitable for diquat dibromide dichloro salt aqua |
| CN108353915A (en) * | 2018-02-26 | 2018-08-03 | 南京红太阳股份有限公司 | A kind of soluble concentrate of two villaumite containing diquat dibromide and preparation method thereof |
| CN108432745A (en) * | 2018-02-26 | 2018-08-24 | 南京红太阳股份有限公司 | A kind of two villaumite containing diquat dibromide can glue and preparation method thereof |
| CN109232569A (en) * | 2018-11-07 | 2019-01-18 | 南京红太阳生物化学有限责任公司 | A kind of environment-friendly preparation method thereof of diquat dibromide anion salt |
| CN114957254A (en) * | 2022-06-10 | 2022-08-30 | 南京红太阳生物化学有限责任公司 | Preparation method of diquat dichloride |
| CN115894492A (en) * | 2022-12-12 | 2023-04-04 | 安徽红太阳生物化学有限公司 | Preparation method of diquat dichloride |
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| GB2580814B (en) * | 2017-08-30 | 2022-03-23 | Nanjing Redsun Biochemistry Co Ltd | Method for preparing 1,1'-Ethylene-2,2'-Bipyridinium Dichloride |
| US10858337B2 (en) | 2017-08-30 | 2020-12-08 | Nanjing Redsun Biochemistry Co., Ltd. | Method for preparing 1,1′-ethylene-2,2′-bipyridinium dichloride |
| GB2580814A (en) * | 2017-08-30 | 2020-07-29 | Nanjing Redsun Biochemistry Co Ltd | Method for preparing 1,1'-Ethylene-2,2'-Bipyridyl Dichloride Salt |
| WO2019041462A1 (en) * | 2017-08-30 | 2019-03-07 | 南京红太阳生物化学有限责任公司 | Method for preparing 1,1'-ethylene-2,2'-bipyridyl dichloride salt |
| CN107573342A (en) * | 2017-08-30 | 2018-01-12 | 南京红太阳生物化学有限责任公司 | A kind of preparation method of the villaumite of 1,1 ' ethylene, 2,2 ' bipyridyl two |
| CN107573342B (en) * | 2017-08-30 | 2020-06-16 | 南京红太阳生物化学有限责任公司 | Preparation method of 1,1 '-ethylene-2, 2' -bipyridyl dichloride salt |
| CN108353915A (en) * | 2018-02-26 | 2018-08-03 | 南京红太阳股份有限公司 | A kind of soluble concentrate of two villaumite containing diquat dibromide and preparation method thereof |
| CN108432745A (en) * | 2018-02-26 | 2018-08-24 | 南京红太阳股份有限公司 | A kind of two villaumite containing diquat dibromide can glue and preparation method thereof |
| CN108207946B (en) * | 2018-04-12 | 2020-12-22 | 南京科翼新材料有限公司 | Special auxiliary agent suitable for diquat dichloride aqueous solution |
| CN108207946A (en) * | 2018-04-12 | 2018-06-29 | 南京科翼新材料有限公司 | A kind of special assistant suitable for diquat dibromide dichloro salt aqua |
| CN109232569A (en) * | 2018-11-07 | 2019-01-18 | 南京红太阳生物化学有限责任公司 | A kind of environment-friendly preparation method thereof of diquat dibromide anion salt |
| WO2020093459A1 (en) * | 2018-11-07 | 2020-05-14 | 南京红太阳生物化学有限责任公司 | Green preparation method for diquat anion salt |
| CN109232569B (en) * | 2018-11-07 | 2021-05-25 | 南京红太阳生物化学有限责任公司 | Green preparation method of diquat anion salt |
| CN114957254A (en) * | 2022-06-10 | 2022-08-30 | 南京红太阳生物化学有限责任公司 | Preparation method of diquat dichloride |
| CN115894492A (en) * | 2022-12-12 | 2023-04-04 | 安徽红太阳生物化学有限公司 | Preparation method of diquat dichloride |
| CN115894492B (en) * | 2022-12-12 | 2023-06-16 | 安徽红太阳生物化学有限公司 | Preparation method of diquat dichloride |
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