CN104829540A - Bromo-chloro dimethyl hydantoin synthesis method - Google Patents
Bromo-chloro dimethyl hydantoin synthesis method Download PDFInfo
- Publication number
- CN104829540A CN104829540A CN201510281613.1A CN201510281613A CN104829540A CN 104829540 A CN104829540 A CN 104829540A CN 201510281613 A CN201510281613 A CN 201510281613A CN 104829540 A CN104829540 A CN 104829540A
- Authority
- CN
- China
- Prior art keywords
- sodium
- reaction
- dimethyl hydantoin
- dimethyl hydantion
- sodium hypochlorite
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/80—Two oxygen atoms, e.g. hydantoin with hetero atoms or acyl radicals directly attached to ring nitrogen atoms
- C07D233/82—Halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a bromo-chloro dimethyl hydantoin synthesis method. The bromo-chloro dimethyl hydantoin synthesis method is characterized in that sodium sulfamate, sodium glycinate, urea or a mixture of the sodium sulfamate, the sodium glycinate and the urea is added into a dimethyl hydantoin solution to serve as sodium hypochlorite stabilizer, and the stabilizer can form an oxidation gland with oxidizing agent hypochloric acid to serve as a medium for oxidation and halogenation of dimethyl hydantoin for halogenation of the dimethyl hydantoin. The bromo-chloro dimethyl hydantoin synthesis method has the advantages that the stabilizer is capable of preventing decomposition of the sodium hypochlorite and preventing the sodium hypochlorite from deep oxidation and being decomposed into the dimethyl hydantoin, so that synthesis yield is increased and production cost is reduced; volatile and highly-corrosive chemical materials are unused, a reaction process is easy control, a production process is safe and environment friendly, and the method can be suitable for industrial production requirements.
Description
Technical field
The present invention relates to a kind of synthetic method of bromochlorodimethyl hydanton, particularly in dimethyl hydantion solution, add sodium hypochlorite stabilizer, stablizer can form oxidation ligand with oxidant hypochlorous acid, and the medium as dimethyl hydantion oxidative halogenation improves reaction conditions, belongs to field of fine chemical.
Background technology
Bromochlorodimethyl hydanton is a kind of disinfecting sterilized water treatment agent, be widely used in industrial water conditioning system, indoor and outdoor swimming (bath) pond, the disinfecting of sanitation system and cultivation water environment, various bacteria and virus can be killed, the aquaculture creature disease that Prevention and Curation is caused by bacterium and virus.Because its effective content of halogen is high, good stability, smell are little, release slowly, the not feature such as skin irritation and mucous membrane, there is the trend replacing chlorine and chlorinated isocyanurates class biocide, at present, market demand increases to rapidly tens thousand of ton, and the improvement of synthetic method is also in widespread attention.
The preparation method of bromochlorodimethyl hydanton has the indirect halogen process of hypohalite, bromide and the direct halogen process of the indirect halogen process of chlorine, halogen and alkali three kinds.The indirect halogen process of hypohalite adopts hypohalite to be the indirect halogenation 5 of halogenating agent, 5-dimethyl hydantion, this method production technique and equipment fairly simple, do not use hazardous chemical raw material, shortcoming is that hypohalite oxidation capacity is crossed by force and raw material easily decomposes, affect reaction yield and raw material consumption, be difficult to industrial applications.Bromide and the indirect halogen process of chlorine adopt and first with chlorine, the bromide anion in bromide are oxidized to bromine, to 5,5-dimethyl hydantion carries out bromination, and then carry out chlorination, although this method does not directly use volatile bromine raw material, the consumption of chlorine is larger, in addition, the use of raw material chlorine, storage and movement requirement are high, are not suitable for batch production on a small scale.Halogen and the direct halogen process of alkali add dimethyl hydantion in reaction mother liquor, first add bromine bromination, then pass into chlorinated with chlorine, be separated bromine hydantoin halides precipitation after reacting completely, washing precipitation, dry finished product, mother liquor can be recycled, and this method is the most frequently used production method of bromine hydantoin halides, and shortcoming is bromine, chlorine is volatile and severe corrosive Chemicals, require high to production unit and technological operation, safety and environmental protection outstanding problem.
Summary of the invention
The object of the invention is the deficiency of the safety and environmental protection outstanding problem overcoming existing bromochlorodimethyl hydanton synthetic method, provide a kind of production technique easy, do not use hazardous chemical raw material, the bromochlorodimethyl hydanton synthetic method of safety and environmental protection.
Principle of the present invention and main process add sodium hypochlorite stabilizer in dimethyl hydantion solution, when adding oxidizing agent sodium hypochlorite in reaction process, stablizer can be formed with hypochlorous acid and be oxidized ligand, it is as the medium of dimethyl hydantion oxidative halogenation, Sodium Bromide in reaction solution is oxidized to bromine by original position, the bromine that reaction produces carries out bromination reaction with dimethyl hydantion again and generates monobromo dimethyl hydantion, Sodium Bromide in reaction solution is utilized completely, sodium-chlor in reaction solution is oxidized to chlorine by oxidation ligand further, the chlorine that reaction produces carries out chlorination reaction with monobromo dimethyl hydantion again and generates bromochlorodimethyl hydanton.The oxidation ligand that stablizer and hypochlorous acid are formed improves the stability of clorox and reduces its oxidation activity, both can prevent the decomposition of clorox, can prevent again its deep oxidation from decomposing dimethyl hydantion raw material.
The sodium hypochlorite stabilizer adopted in the present invention is thionamic acid sodium, Sodium Glycinate, urea or its mixture, and its molar ratio is: clorox: stablizer=1:0.1-0.2.Due to stablizer soluble in water in, be very easy to and bromochlorodimethyl hydanton product separation, thus easily realize repeatedly recycling of stablizer.
The technical scheme that the inventive method is taked and synthesis step are:
(1) in reactor, dimethyl hydantion, Sodium Bromide, sodium hypochlorite stabilizer and deionized water is added, under agitation with cryosel bath, reaction solution is cooled to 5-25 DEG C, slowly add chlorine bleach liquor, when reaction solution is by colourless yellowing, when gradually becoming again white, bromination reaction completes;
(2) in bromination reaction liquid, slowly chlorine bleach liquor is added further, add the alkali that dilute hydrochloric acid neutralization reaction produces simultaneously, bromochlorodimethyl hydanton pale yellow precipitate is had to be formed gradually, control chlorination reaction temperature 5-25 DEG C, when precipitation no longer increases and has gas to release, chlorination reaction completes, and controls molar ratio to be: dimethyl hydantion: Sodium Bromide: stablizer: hydrochloric acid: clorox: deionized water=1:0.95-1.05:0.05-0.5:2-2.5:2-2.5:10-50;
(3) sedimentation and filtration that generate in reaction solution is separated, by washed with de-ionized water precipitation, dry high purity bromochlorodimethyl hydanton product;
(4) supplement in the mother liquor after product separation and add dimethyl hydantion and Sodium Bromide, in mother liquor, stablizer recycles, and enters next batch synthesis.
The raw material dimethyl hydantion adopted in technical solution of the present invention is industrial goods, purity 99.0%.
The raw material chlorine bleach liquor adopted in technical solution of the present invention is the clorox industrial goods of available chlorine content 5%-10%.
The sodium hypochlorite stabilizer adopted in technical solution of the present invention is thionamic acid sodium, Sodium Glycinate and urea industry product.
The raw material Sodium Bromide adopted in technical solution of the present invention is solid industrial product, also can be the industry byproduct reclaimed, such as, the sodium bromide solution byproduct that industrial by-product hydrogen bromide Alkali absorption obtains, adopts sodium bromide solution byproduct greatly can reduce raw materials cost.
Advantage of the present invention is: (1) have employed sodium hypochlorite stabilizer, prevents the oxygenolysis of dimethyl hydantion, and synthesis yield improves, and reduces clorox consumption simultaneously, thus reduces production cost; (2) the inventive method does not use volatile and industrial chemicals that is severe corrosive, and reaction process easily controls, production process safety and environmental protection, can be applicable to industrialization production requirements.
Embodiment
The object of the invention is to realize in the following ways, describe in detail below in conjunction with embodiment.
Embodiment 1
The industrial dimethyl hydantion 129.4g(1.0mol that content is 99% is added) in 2000ml four-hole bottle, Sodium Bromide 103g(1.0mol), thionamic acid sodium 11.9g(0.1mol), deionized water 360g, under agitation cools to 5 DEG C with cryosel bath, starts the chlorine bleach liquor 391g(1.1mol dripping available chlorine content 10%), within about 50 minutes, add, control setting-up point 5-10 DEG C, when gradually becoming again white after reaction solution yellowing, bromination reaction completes.Slowly add the chlorine bleach liquor 355g(1.0mol of available chlorine content 10% further), add simultaneously concentration expressed in percentage by weight be 15% hydrochloric acid be about 487g(2.0mol), with in and halogenating reaction produce alkali, bromochlorodimethyl hydanton pale yellow precipitate is had to be formed gradually, control chlorination reaction temperature 5-25 DEG C, when precipitation no longer increases and has gas to release, chlorination reaction completes.By the precipitation vacuum filtration in reaction residual liquor, with 200g washed with de-ionized water precipitation secondary, obtain bromochlorodimethyl hydanton product 237.8g 50-60 DEG C of vacuum-drying, purity 98.0%, total yield of products 96.5%.
Embodiment 2
Dimethyl hydantion 129.4g(1.0mol is added) in embodiment 1 mother liquor, Sodium Bromide 103g(1.0mol), slowly add the chlorine bleach liquor 710g(2.0mol of available chlorine content 10% further), add simultaneously concentration expressed in percentage by weight be 15% hydrochloric acid be about 487g(2.0mol), control temperature of reaction 5-25 DEG C, when precipitation no longer increases and has gas to release, chlorination reaction completes.By the precipitation vacuum filtration in reaction residual liquor, with 200g washed with de-ionized water precipitation secondary, obtain bromochlorodimethyl hydanton product 240.3g 50-60 DEG C of vacuum-drying, purity 98.0%, total yield of products 97.5%.
Embodiment 3
The industrial dimethyl hydantion 129.4g(1.0mol that content is 99% is added) in 2000ml four-hole bottle, Sodium Bromide 103g(1.0mol), urea 6.0g(0.1mol), deionized water 360g, under agitation cools to 5 DEG C with cryosel bath, starts the chlorine bleach liquor 391g(1.1mol dripping available chlorine content 10%), within about 50 minutes, add, control setting-up point 5-10 DEG C, when gradually becoming again white after reaction solution yellowing, bromination reaction completes.Slowly add the chlorine bleach liquor 355g(1.0mol of available chlorine content 10% further), add simultaneously concentration expressed in percentage by weight be 15% hydrochloric acid be about 487g(2.0mol), bromochlorodimethyl hydanton pale yellow precipitate is had to be formed gradually, control chlorination reaction temperature 5-25 DEG C, when precipitation no longer increases and has gas to release, chlorination reaction completes.By the precipitation vacuum filtration in reaction residual liquor, with 200g washed with de-ionized water precipitation secondary, obtain bromochlorodimethyl hydanton product 236.5g 50-60 DEG C of vacuum-drying, purity 97.5%, total yield of products 95.5%.
Embodiment 4
Dimethyl hydantion 129.4g(1.0mol is added) in embodiment 3 mother liquor, Sodium Bromide 103g(1.0mol), slowly add the chlorine bleach liquor 710g(2.0mol of available chlorine content 10% further), add simultaneously concentration expressed in percentage by weight be 15% hydrochloric acid be about 487g(2.0mol), control temperature of reaction 5-25 DEG C, when precipitation no longer increases and has gas to release, chlorination reaction completes.By the precipitation vacuum filtration in reaction residual liquor, with 200g washed with de-ionized water precipitation secondary, obtain bromochlorodimethyl hydanton product 237.8g 50-60 DEG C of vacuum-drying, purity 98.0%, total yield of products 96.5%.
Claims (2)
1. the synthetic method of a bromochlorodimethyl hydanton, it is characterized in that adding sodium hypochlorite stabilizer in dimethyl hydantion solution, when adding oxidizing agent sodium hypochlorite in reaction process, stablizer can be formed with hypochlorous acid and be oxidized ligand, as the medium of dimethyl hydantion oxidative halogenation, comprise following synthesis step:
(1) in reactor, dimethyl hydantion, Sodium Bromide, sodium hypochlorite stabilizer and deionized water is added, under agitation with cryosel bath, reaction solution is cooled to 5-25 DEG C, slowly add chlorine bleach liquor, when reaction solution is by colourless yellowing, when gradually becoming again white, bromination reaction completes;
(2) in bromination reaction liquid, slowly chlorine bleach liquor is added further, add the alkali that hydrochloric acid neutralization reaction produces simultaneously, bromochlorodimethyl hydanton pale yellow precipitate is had to be formed gradually, control chlorination reaction temperature 5-25 DEG C, when precipitation no longer increases and has gas to release, chlorination reaction completes, and controls molar ratio to be: dimethyl hydantion: Sodium Bromide: stablizer: hydrochloric acid: clorox: deionized water=1:0.95-1.05:0.05-0.5:2-2.5:2-2.5:10-50;
(3) sedimentation and filtration that generate in reaction solution is separated, by washed with de-ionized water precipitation, dry high purity bromochlorodimethyl hydanton product;
(4) supplement in the mother liquor after product separation and add dimethyl hydantion and Sodium Bromide, in mother liquor, stablizer recycles, and enters next batch synthesis.
2. the synthetic method of a kind of bromochlorodimethyl hydanton as claimed in claim 1, it is characterized in that adopted sodium hypochlorite stabilizer is thionamic acid sodium, Sodium Glycinate, urea or its mixture, its molar ratio is: clorox: stablizer=1:0.1-0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510281613.1A CN104829540A (en) | 2015-05-28 | 2015-05-28 | Bromo-chloro dimethyl hydantoin synthesis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510281613.1A CN104829540A (en) | 2015-05-28 | 2015-05-28 | Bromo-chloro dimethyl hydantoin synthesis method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104829540A true CN104829540A (en) | 2015-08-12 |
Family
ID=53807783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510281613.1A Pending CN104829540A (en) | 2015-05-28 | 2015-05-28 | Bromo-chloro dimethyl hydantoin synthesis method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104829540A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388122A (en) * | 2002-06-19 | 2003-01-01 | 定州市荣鼎水环境生化技术有限公司 | Prepn of bromochlorodimethyl hydantoin as disinfectant |
| CN1714647A (en) * | 2004-07-02 | 2006-01-04 | 罗门哈斯公司 | Microbicidal composition |
| CN102781849A (en) * | 2010-03-05 | 2012-11-14 | 栗田工业株式会社 | Water treatment method and ultrapure water production method |
-
2015
- 2015-05-28 CN CN201510281613.1A patent/CN104829540A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388122A (en) * | 2002-06-19 | 2003-01-01 | 定州市荣鼎水环境生化技术有限公司 | Prepn of bromochlorodimethyl hydantoin as disinfectant |
| CN1714647A (en) * | 2004-07-02 | 2006-01-04 | 罗门哈斯公司 | Microbicidal composition |
| CN102781849A (en) * | 2010-03-05 | 2012-11-14 | 栗田工业株式会社 | Water treatment method and ultrapure water production method |
Non-Patent Citations (2)
| Title |
|---|
| 刘传仁 等: "溴氯海因的合成及工艺研究", 《山东化工》 * |
| 陆华: "1-溴-3-氯-5，5-二甲基-2，4-咪唑啉啶二酮的合成", 《化工时刊》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110040688B (en) | Preparation method of stable chlorine dioxide solution | |
| JP5918109B2 (en) | Method for producing hypobromite stabilized composition and hypobromite stabilized composition | |
| CN100361582C (en) | Bactericidal and algae-killing composition and its production, river system sterilizing method | |
| AU784846B2 (en) | Process for generating stabilized bromine compounds | |
| NO314798B1 (en) | Process for continuous production of chlorine dioxide | |
| CZ39694A3 (en) | Process for preparing chlorine dioxide | |
| CN101519189A (en) | Method and device for preparing basic magnesium hypochlorite by using waste chlorine | |
| AU2005285645B2 (en) | A process for the production of chlorine dioxide | |
| JP2015507089A (en) | In situ production of biocidal bromine species by electrolysis | |
| CN106395749A (en) | Method for preparing high-purity chlorine dioxide through solid-state heterogeneous catalysis | |
| CN115363025A (en) | Efficient stable sodium hypochlorite disinfectant and preparation method thereof | |
| JP2019202907A (en) | Method for producing weakly-acidic hypochlorous acid water | |
| CN111440051A (en) | Synthesis method of 4-chloro-3, 5-dimethylphenol | |
| CA2760300A1 (en) | Chlorine dioxide generation | |
| CN104829540A (en) | Bromo-chloro dimethyl hydantoin synthesis method | |
| CN1611492A (en) | Bromochloro glucolylurea steribizing and disinfecting algae cide preparing method | |
| EP3215459B1 (en) | Hypochlorous acid solutions, process for preparing them and their uses | |
| CN107793384B (en) | Method for preparing 2, 5-dimethoxy-2, 5-dihydrofuran | |
| CN109133010A (en) | A kind of production method for sodium hypochlorite of paddling | |
| GB2171398A (en) | Cupric oxychloride | |
| CN1480043A (en) | Compound bactericide for treating water and its preparing method | |
| KR970000300B1 (en) | Process for the preparation of stabilized chlorine dioxide | |
| CN105669505A (en) | Preparing method of beta,beta'-dithiobis(dihydrocinnamicacid) | |
| CN1388122A (en) | Prepn of bromochlorodimethyl hydantoin as disinfectant | |
| CN111548316A (en) | Production method for continuously synthesizing sodium dichloroisocyanurate containing dihydrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150812 |
|
| WD01 | Invention patent application deemed withdrawn after publication |