CN108947765A - A kind of method of bis-diazotized reaction one-step synthesis o-dibromobenzene - Google Patents
A kind of method of bis-diazotized reaction one-step synthesis o-dibromobenzene Download PDFInfo
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- CN108947765A CN108947765A CN201810928213.9A CN201810928213A CN108947765A CN 108947765 A CN108947765 A CN 108947765A CN 201810928213 A CN201810928213 A CN 201810928213A CN 108947765 A CN108947765 A CN 108947765A
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- dibromobenzene
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- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/20—Diazonium compounds
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Abstract
The present invention provides a kind of methods of bis-diazotized reaction one-step synthesis o-dibromobenzene, comprising the following steps: step 1: acetic acid 300ml and o-phenylenediamine 10.8g are added in the dry four-hole boiling flask of 500ML；Step 2: being then stirred, and after o-phenylenediamine dissolution, solution is cooled to certain temperature；Step 3: and then nitrosylsulfuric acid 70g is added dropwise into the solution of step 2, diazo liquid preparation is completed；Step 4: hydrobromic acid 200ml and cuprous oxide 0.2g are added in 1L four-hole bottle；Step 5: mixture in step 4 is carried out to be heated to certain temperature；Step 6: the diazo liquid that step 3 is obtained is added in the solution of step 5；Step 7: and then 100ML water is added and obtains weak yellow liquid 12g using steam distillation.
Description
Technical field
The present invention relates to chemicals preparation technical fields, more particularly to a kind of bis-diazotized reaction one-step synthesis o-dibromobenzene
Method.
Background technique
O-dibromobenzene is that the important organic intermediate raw material of one kind is also a kind of important OLED intermediate.It synthesizes at present
Method mainly has benzene bromination method, o-bromoaniline diazotising method, bromobenzene concentrated acid sulfonation method etc..Benzene bromination method product is complicated, to bromine
It is main component with terbromide, the o-dibromobenzene for isolating high-purity is very difficult, raw material neighbour's bromine of o-bromoaniline heavy nitrogen
Aniline mainly passes through o-bromonitrobenzene iron powder reducing method and is made, and generates a large amount of solid slag, and diazo-reaction can also produce
Raw a large amount of acid waste water, comprehensive benefit are very poor.Requirement of the bromobenzene concentrated acid sulfonation method to equipment is very high, and the temperature of reaction is also very
Height is generally used for researching and developing small-scale synthesis.
Such as Chinese patent " 106905105 A of CN " discloses a kind of preparation method of o-dibromobenzene, it is characterised in that presses
Following steps carry out: S1: being added water in a kettle, and sodium nitrite is then added while agitating, obtains after dissolving completely
Sodium nitrite solution, barrelling are spare；S2: being added hydrobromic acid in a kettle, is added with stirring o-bromoaniline, and the two is completely dissolved
After open frozen cooling, be down to 10 DEG C hereinafter, ice block cooling then is added from manhole, in 0-5 DEG C of at a temperature of a dropping step S1
In prepared sodium nitrite solution, stirred after being added dropwise cooling 1 hour；S3: removal impurity is filtered, it is molten to obtain diazonium salt
Liquid；S4: being added hydrobromic acid in the reaction kettle equipped with steam distillation device, is added with stirring cuprous bromide, and dissolution obtains completely
Obtain mixed solution；S5: the mixed solution in step S4 is heated to boiling, the diazonium salt solution prepared in a dropping step S3,
O-dibromobenzene is steamed simultaneously, continues to heat after dripping, carries out steam distillation, until there is no oily liquids generations；S6: it receives
The product obtained in collection step S5, washs qualified products, neutralized and is dehydrated, carry out rectifying or water to substandard product
Distillation；S7: water is added in the raffinate after step S5 distillation, cuprous bromide is obtained after agitated cooling, centrifugation and drying, is recycled
It uses.Although raw material used are relatively easy to obtain the technical solution, and cuprous bromide used can recycle that cost is relatively low,
But its preparation process is complex, and production efficiency is low.
In another example patent " 104086360 A of CN " discloses a kind of production technology of o-dibromobenzene synthesis, feature exists
In, comprising the following steps: a, weigh the bromophenyl ammonia of 170-172kg and 50% sodium hydroxide of 400-410kg；B, by bromophenyl
In ammonia and 50% sodium hydroxide investment reaction kettle, agitating device is opened, and ice cube will constantly be added in reaction kettle until temperature
Degree is 0 DEG C；C, the sodium nitrite of 68-70kg and the water wiring solution-forming of 120-130kg are weighed；D, by the mixture in reaction kettle after
It is continuous to stir and the solution configured in step c is added, and ice cube is continuously added, until temperature is at 10 DEG C or less；E, work as reaction
When generating excessive nitrous acid in kettle, stop reaction arrives weight ammonium salt solution, weight ammonium salt solution is taken out spare；F, it weighs
The cuprous bromide of 78-80kg and the hydrobromic acid wiring solution-forming of 95-100kg50%；G, by the solution heating in step f until boiling
It rises, and heavy ammonium salt solution obtained in step e is added in the state of constantly boiling, finished in 25-35min addition；H, will
It is passed through vapor in mixture after reacting in step g to be distilled, until not thering is oil droplet to steam；I, it will be distilled in step h
Distillate afterwards isolates bottom oil layer, and the concentrated sulfuric acid is added and is washed, be then passed through again water washing to PH be 6, then again
The sodium hydroxide solution for being added 50% continues to wash, until solution PH is 7；J, the mixture after washing in step is used
The anhydrous calcium oxide of 2-4kg is dried, and is then distilled, the mixture collected at 223-225 DEG C, as neighbour two
Then bromobenzene is packed and stored.Although the technical solution prepares material and is easy to get, but its preparation process temperature difference is larger, using ice
Block cooling, temperature are difficult to control, and are not suitable for batch preparation production.
Such as Chinese patent " 103833512 B of CN " discloses diazotising one-step synthesis o-dibromobenzene under a kind of high temperature again
Method, which comprises the following steps: by 500g mass fraction be 48% hydrobromic acid, 10g cuprous oxide, 172g adjacent
Bromaniline investment has in the four-hole boiling flask of blender, condenser, thermometer, and stirring is warming up between 80-100 DEG C, in liquid level
The lower solution that 72g sodium nitrite is added dropwise and is dissolved in 100g water after dripping off, changes distilling apparatus band water and distills out product, separate oil reservoir, use
After 100mL mass fraction is washed once for 5% liquid alkaline, then with after 100mL washing once, oil reservoir is separated, steams product under decompression
194g, content 99.2%, yield 82%.Although the technical solution leading portion preparation process is simple, subsequent extracted process needs more
Secondary distillation and wash-off are unfavorable for batch and prepare production.
One-step synthesis method o-dibromobenzene, following problems may be encountered: when the diazo-reaction of diamino compounds, one first
Amino is by diazotising, and for another amino due to the influence of diazonium cation, alkalinity is very weak, cannot be stood by diazotising
Azo amino-compound -- the structure of benzotriazole is generated in the molecule, therefore being in normal water solution system cannot
Access target product.
Summary of the invention
To overcome, preparation extraction process existing in the prior art is complex, is not suitable for batch production and one-step synthesis method
The problem of target product cannot be accessed in normal water solution system when o-dibromobenzene, the present invention provides a kind of dual nitrogen
Change the method for reaction one-step synthesis o-dibromobenzene.
Above-mentioned purpose that the invention is realized by the following technical scheme: the bis-diazotized reaction one-step synthesis o-dibromobenzene of one kind
Method, comprising the following steps:
Step 1: acetic acid 300ml and o-phenylenediamine 10.8g are added in the dry four-hole boiling flask of 500ML；
Step 2: being then stirred, and after o-phenylenediamine dissolution, solution is cooled to certain temperature；
Step 3: and then nitrosylsulfuric acid 70g is added dropwise into the solution of step 2, diazo liquid preparation is completed；
Step 4: hydrobromic acid 200ml and cuprous oxide 0.2g are added in 1L four-hole bottle；
Step 5: mixture in step 4 is carried out to be heated to certain temperature；
Step 6: the diazo liquid that step 3 is obtained is added in the solution of step 5；
Step 7: and then 100ML water is added and obtains weak yellow liquid 12g using steam distillation.
On this basis, the step 2 cooling temperature is -5 DEG C.
On this basis, the concentration of nitrosylsulfuric acid is 40% in the step 3.
On this basis, the concentration of hydrobromic acid is 48% in the step 4.
On this basis, heating temperature is 80 DEG C in the step 4.
On this basis, the diazo liquid that obtains step 3 in the step 5 is added to be used in the solution of step 4
It is to be added dropwise to be added.
On this basis, the content of o-dibromobenzene is 99.2% in weak yellow liquid in affiliated step 6.
Compared with prior art, the beneficial effects of the present invention are: bis-diazotized reaction is generally used for p-phenylenediamine, isophthalic two
In the synthesis of amine, the present invention uses o-phenylenediamine one-step synthesis o-dibromobenzene, solves preparation existing in the prior art and extracts
Process is complex, is not suitable for obtain in normal water solution system when batch production and one-step synthesis method o-dibromobenzene
The problem of to target product, has constructive meaning for the preparation synthesis of o-dibromobenzene.
Specific embodiment
With reference to embodiments, the present invention will be described in further detail.It should be appreciated that specific reality described herein
Example is applied only to explain the present invention, is not intended to limit the present invention.
The present invention schematically illustrates a kind of method of bis-diazotized reaction one-step synthesis o-dibromobenzene.
Embodiment 1
Acetic acid 300ml and o-phenylenediamine 10.8g are added in the dry four-hole boiling flask of 500ML, are then stirred, to
After o-phenylenediamine dissolution, solution is cooled to -5 DEG C, the nitrosylsulfuric acid 70g that concentration is 40% is then added dropwise into solution, i.e.,
Complete the preparation of diazo liquid；Hydrobromic acid 200ml and cuprous oxide 0.2g that concentration is 48% are subsequently added to 1L four-hole bottle
In and carry out being heated to 80 DEG C, the diazo liquid being prepared is added drop-wise in 1L four-hole bottle, then be added 100ML water, utilize water
Steam distillation obtains weak yellow liquid 12g, and the content for the o-dibromobenzene being prepared is 99.2%.
The beneficial effects of the present invention are: bis-diazotized react is generally used for p-phenylenediamine, and in the synthesis of m-phenylene diamine (MPD), this hair
It is bright to use o-phenylenediamine one-step synthesis o-dibromobenzene, it is complex, no to solve preparation extraction process existing in the prior art
Asking for target product cannot be accessed in normal water solution system when suitable for mass production and one-step synthesis method o-dibromobenzene
Topic has constructive meaning for the preparation synthesis of o-dibromobenzene.
The preferred embodiment of the present invention has shown and described in above description, as previously described, it should be understood that the present invention is not office
Be limited to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification and
Environment, and can be changed within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
It is dynamic.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of the present invention, then it all should be appended by the present invention
In scope of protection of the claims.
Claims (7)
1. a kind of method of bis-diazotized reaction one-step synthesis o-dibromobenzene, which comprises the following steps:
Step 1: acetic acid 300ml and o-phenylenediamine 10.8g are added in the dry four-hole boiling flask of 500ML；
Step 2: being then stirred, and after o-phenylenediamine dissolution, solution is cooled to certain temperature；
Step 3: and then nitrosylsulfuric acid 70g is added dropwise into the solution of step 2, diazo liquid preparation is completed；
Step 4: hydrobromic acid 200ml and cuprous oxide 0.2g are added in 1L four-hole bottle；
Step 5: mixture in step 4 is carried out to be heated to certain temperature；
Step 6: the diazo liquid that step 3 is obtained is added in the solution of step 5；
Step 7: and then 100ML water is added and obtains weak yellow liquid 12g using steam distillation.
2. the method for the bis-diazotized reaction one-step synthesis o-dibromobenzene of one kind according to claim 1, it is characterised in that: institute
Stating step 2 cooling temperature is -5 DEG C.
3. the method for the bis-diazotized reaction one-step synthesis o-dibromobenzene of one kind according to claim 1, it is characterised in that: institute
The concentration for stating nitrosylsulfuric acid in step 3 is 40%.
4. the method for the bis-diazotized reaction one-step synthesis o-dibromobenzene of one kind according to claim 1, it is characterised in that: institute
The concentration for stating hydrobromic acid in step 4 is 48%.
5. the method for the bis-diazotized reaction one-step synthesis o-dibromobenzene of one kind according to claim 1, it is characterised in that: institute
Stating heating temperature in step 4 is 80 DEG C.
6. the method for the bis-diazotized reaction one-step synthesis o-dibromobenzene of one kind according to claim 1, it is characterised in that: institute
The diazo liquid for obtaining step 3 in step 5 is stated to be added in the solution of step 4 using dropwise addition addition.
7. the method for the bis-diazotized reaction one-step synthesis o-dibromobenzene of one kind according to claim 2, it is characterised in that: institute
The content for belonging to o-dibromobenzene in weak yellow liquid in step 6 is 99.2%.
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Citations (7)
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|---|---|---|---|---|
| JPS62283942A (en) * | 1986-05-31 | 1987-12-09 | Nippon Kayaku Co Ltd | Production of 4-bromo-2,5-dichlorophenol |
| CN103249780A (en) * | 2010-12-20 | 2013-08-14 | 亨斯迈先进材料（瑞士）有限公司 | Disperse azo dyes |
| CN103833512A (en) * | 2014-02-20 | 2014-06-04 | 常州市正锋光电新材料有限公司 | Method of synthesizing o-dibromobenzene by diazotization in one step at high temperature |
| CN106905105A (en) * | 2017-02-16 | 2017-06-30 | 盐城市龙升化工有限公司 | A kind of preparation method of o-dibromobenzene |
| CN107075268A (en) * | 2014-09-15 | 2017-08-18 | 德司达染料分销有限公司 | High humidity rapid dispersion dyestuff and its mixture |
| CN107722663A (en) * | 2017-10-10 | 2018-02-23 | 浙江万丰化工有限公司 | A kind of azo dyes compounds and its preparation method and application |
| CN108047759A (en) * | 2017-12-26 | 2018-05-18 | 沈阳化工研究院有限公司 | A kind of epoxy type reactive disperse dyes and its preparation method and application |
-
2018
- 2018-08-15 CN CN201810928213.9A patent/CN108947765A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62283942A (en) * | 1986-05-31 | 1987-12-09 | Nippon Kayaku Co Ltd | Production of 4-bromo-2,5-dichlorophenol |
| CN103249780A (en) * | 2010-12-20 | 2013-08-14 | 亨斯迈先进材料（瑞士）有限公司 | Disperse azo dyes |
| CN103833512A (en) * | 2014-02-20 | 2014-06-04 | 常州市正锋光电新材料有限公司 | Method of synthesizing o-dibromobenzene by diazotization in one step at high temperature |
| CN107075268A (en) * | 2014-09-15 | 2017-08-18 | 德司达染料分销有限公司 | High humidity rapid dispersion dyestuff and its mixture |
| CN106905105A (en) * | 2017-02-16 | 2017-06-30 | 盐城市龙升化工有限公司 | A kind of preparation method of o-dibromobenzene |
| CN107722663A (en) * | 2017-10-10 | 2018-02-23 | 浙江万丰化工有限公司 | A kind of azo dyes compounds and its preparation method and application |
| CN108047759A (en) * | 2017-12-26 | 2018-05-18 | 沈阳化工研究院有限公司 | A kind of epoxy type reactive disperse dyes and its preparation method and application |
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