CN107673989B - The preparation method of one inter-species bromine azo aromatic compound - Google Patents
The preparation method of one inter-species bromine azo aromatic compound Download PDFInfo
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- CN107673989B CN107673989B CN201710969614.4A CN201710969614A CN107673989B CN 107673989 B CN107673989 B CN 107673989B CN 201710969614 A CN201710969614 A CN 201710969614A CN 107673989 B CN107673989 B CN 107673989B
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- azo
- bromine
- aromatic compound
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- bromide reagent
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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
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/06—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings
- C07C245/08—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings with the two nitrogen atoms of azo groups bound to carbon atoms of six-membered aromatic rings, e.g. azobenzene
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation method of one inter-species bromine azo aromatic compound is reacted with bromide reagent using azo aromatic compound and is made, the bromide reagent tetrabutyl tribromide amine, and reaction process is：Aromatic azo-compound, bromide reagent, catalyst, alkali and solvent are directly added into reaction unit, catalyst is bis- (the 4 isopropyl methyl phenyl) rutheniums of dichloro；Alkali is potassium carbonate；Bromide reagent is tetrabutyl tribromide amine；The solvent is toluene or benzene, and the mole dosage of tetrabutyl tribromide amine is 24 times of aromatic azo-compound molal quantity, and agitating and heating temperature is reacted 24 hours, separation product obtains a bromine azo aromatic compound to 110 DEG C.
Description
Technical field
The present invention relates to a kind of organic syntheses, the more particularly to preparation method of an inter-species bromine azo aromatic compound, belong to
Chemical field.
Background technology
Aromatic azo-compound with unique texture is widely used in dyestuff, luminescent material and diagnosis and treatment reagent etc. and much leads
Domain.The type, quantity of substituent group and the difference of position etc., all generate different physicochemical properties on azo aromatic skeleton.
It is always a research hotspot that development and exploration, which efficiently synthesize various structure azo aromatic compound new methods,.Up to now,
The a variety of effective ways for synthesizing different azo aromatic compounds, symmetrical azo aromatic compound synthetic method has been developed in people
It is relatively easy, it need to only be can be obtained by by the reduction of nitroaromatic and the oxidation of arylamine；Without symmetrical azo
The synthesis of aromatic compound needs to prepare using compounds such as nitroso compound or aryl diazonium salts, a kind of preparation process
Reaction equation it is as follows：
It is unstable under room temperature convenient for synthesis although such compound is simple and easy to get, it is easy to explode or decomposes in light.Cause
No matter this which kind of method, synthesis is all difficult to for bromine azo aromatic compound between asymmetry.
Invention content
It is an object of the invention to overcome above-mentioned present in the synthesis of bromine azo aromatic compound between current asymmetry ask
Topic, provides the preparation method of an inter-species bromine azo aromatic compound.
To achieve the purpose of the present invention, following technical solutions is used：The preparation of one inter-species bromine azo aromatic compound
Method, it is described between bromine azo aromatic compound have formula III structure, using the azo aromatic compound and bromination of structure shown in formula I
Bromine azo aromatic compound between III structure of formula is made in reagent reaction, and the bromide reagent is tetrabutyl tribromo shown in formula II
Change amine, reaction equation is as follows：
Wherein：R is hydrogen or methoxyl group or methyl, reaction process are：By aromatic azo-compound, bromide reagent, catalysis
Agent, alkali and solvent are directly added into reaction unit, and the catalyst is bis- (the 4- isopropyl methyls phenyl) rutheniums of dichloro；It is described
Alkali is potassium carbonate；The bromide reagent is tetrabutyl tribromide amine；The solvent is toluene or benzene, and tetrabutyl tribromide amine rubs
Your dosage is 2-4 times of aromatic azo-compound molal quantity, and agitating and heating temperature is reacted 24 hours, separation product obtains to 110 DEG C
To a bromine azo aromatic compound.
The positive advantageous effects of the present invention are：This synthetic route is simple, and raw material is easy to get, and synthesizes involved each
Raw material property is stablized, the hidden danger do not exploded or decomposed in light, and reaction condition is mild.
Specific implementation mode
In order to more fully explain the implementation of the present invention, the embodiment of the present invention is provided, these embodiments are only
Elaboration to the present invention, does not limit the scope of the invention.
Embodiment 1：
36mg (0.2mmol) azobenzene, 290mg are added in 20mL pressure resistance reaction tubes（0.6 mmol）Tetrabutyl tribromo
Change amine, bis- (the 4- isopropyl methyls phenyl) rutheniums of 6mg (0.01mmol) dichloro, 55mg（0.4mmol）Potassium carbonate, 1mL toluene, nitrogen
It is sealed under the conditions of gas, is heated to 110 DEG C of reactions, stirs 24 hours, after reaction, pillar layer separation obtains target product 3- bromine azos
Benzene 35mg, yield 67%.
Embodiment 2：
42mg (0.2mmol) 4,4 '-dimethyl azobenzene, 290mg are added in 20mL pressure resistance reaction tubes（0.6 mmol）
Tetrabutyl tribromide amine, bis- (the 4- isopropyl methyls phenyl) rutheniums of 6mg (0.01mmol) dichloro, 55mg（0.4mmol）Potassium carbonate,
1mL toluene seals under condition of nitrogen gas, is heated to 110 DEG C of reactions, stirs 24 hours, and after reaction, pillar layer separation obtains target production
Object 4,4 '-dimethyl 3- bromine azobenzene 38mg yields are 62%.
Embodiment 3：
42mg (0.2mmol) 4,4 '-dimethyl azobenzene, 290mg are added in 20mL pressure resistance reaction tubes（0.6 mmol）
Tetrabutyl tribromide amine, bis- (the 4- isopropyl methyls phenyl) rutheniums of 6mg (0.01mmol) dichloro, 55mg（0.4mmol）Potassium carbonate,
1mL toluene seals under condition of nitrogen gas, is heated to 110 DEG C of reactions, stirs 24 hours, and after reaction, pillar layer separation obtains target production
Object 4,4 '-dimethoxy 3- bromine azobenzene 46mg yields are 71%.
Following table one is the product of technical solution using the present invention synthesis and corresponding yield：
Claims (1)
1. the preparation method of an inter-species bromine azo aromatic compound, it is described between bromine azo aromatic compound there is the knot of formula III
Structure, it is characterised in that：Bromine azo between III structure of the formula of being made is reacted with bromide reagent using the azo aromatic compound of structure shown in formula I
Aromatic compound, the bromide reagent are tetrabutyl tribromide amine shown in formula II, and reaction equation is as follows：
Wherein：R is hydrogen or methyl, and reaction process is：By aromatic azo-compound, bromide reagent, catalyst, alkali and solvent
It is directly added into reaction unit, the catalyst is bis- (the 4- isopropyl methyls phenyl) rutheniums of dichloro；The alkali is potassium carbonate；Institute
It is tetrabutyl tribromide amine to state bromide reagent；The solvent is toluene or benzene, and the mole dosage of tetrabutyl tribromide amine is fragrance
2-4 times of azo-compound molal quantity, agitating and heating temperature are reacted 24 hours to 110 DEG C, and separation product obtains a bromine azo virtue
Aroma compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710969614.4A CN107673989B (en) | 2017-10-18 | 2017-10-18 | The preparation method of one inter-species bromine azo aromatic compound |
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| CN201710969614.4A CN107673989B (en) | 2017-10-18 | 2017-10-18 | The preparation method of one inter-species bromine azo aromatic compound |
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| Publication Number | Publication Date |
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| CN107673989A CN107673989A (en) | 2018-02-09 |
| CN107673989B true CN107673989B (en) | 2018-10-19 |
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