CN102876068A - Preparation method of phthaloyl azo dye - Google Patents
Preparation method of phthaloyl azo dye Download PDFInfo
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- CN102876068A CN102876068A CN2012104056473A CN201210405647A CN102876068A CN 102876068 A CN102876068 A CN 102876068A CN 2012104056473 A CN2012104056473 A CN 2012104056473A CN 201210405647 A CN201210405647 A CN 201210405647A CN 102876068 A CN102876068 A CN 102876068A
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Abstract
The invention discloses a preparation method of phthaloyl azo dye, which comprises the following steps of: mixing N-alkyl-4-nitrol-phthalimide with nitrobenzene compounds according to equal molar ratio, adding the mixture into alkali-containing solvent, feeding hydrogen into the solvent under the existence of catalyst, and conducting reaction for 4-24h at room temperature being approximately 98DEG C under low pressure or normal pressure to directly prepare the phthaloyl azo dye. Compared with the existing disclosed technique, the method provided by the invention has the advantages that the synthesis process flow is short and the defects of classic synthesis method of diazotization-coupling are avoided; the safety is high and only low-pressure or normal-pressure catalytic hydrogenation for coupling is needed; the energy consumption is low and the reaction is conducted at room temperature being approximately 98DEG C; the separation and the purification are simple to conduct and the intermediates are not needed to be purified or separated by using a great quantity of solvent; the quantity of the discharged sewage is less and the secondary environmental pollution is avoided.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of preparation method of phthalimide-based azoic dyestuff, relate in particular to the method that is prepared azoic dyestuff by two kinds of unsymmetrical structure nitro-compounds.
Background technology
Azoic dyestuff is a class important compound of chemical industry, and the phthalimide-based azoic dyestuff is the dispersed dye of a class excellent property, and the preparation method of phthalimide-based azoic dyestuff announces already.As patent of invention CN1069670C, CN1289607C, CN1326945C, CN1249171C, CN100379825C are disclosed, all be to adopt first N-alkyl-4-nitro-phthalic imidine is reduced into N-alkyl-4-amino-phthalic imidine, then through diazotization, make with the coupling of coupling component again.The disadvantage for preparing azoic dyestuff with diazo coupling reaction is that a large amount of nitrite of needs forms diazonium salt, can produce a large amount of inorganic salt and waste water, and these all cause very large impact to environment.
Summary of the invention
The applicant is in the patent of invention of CN101914036A at publication number, has described the oil of mirbane with the same structure, by the effect of catalyzer and hydrogenation, can form a kind of azobenzene derivatives of symmetrical structure.Further further investigation on this technical foundation, the applicant finds that the phthalimide-based azoic dyestuff can directly directly make the phthalimide-based azoic dyestuff by N-alkyl-4-nitro-phthalic imidine and benzene nitro-derivative.
In view of this, the object of the present invention is to provide a kind of method that is prepared the phthalimide-based azoic dyestuff by two kinds of unsymmetrical structure nitro-compounds.
For achieving the above object, the invention provides following technical scheme:
A kind of preparation method of phthalimide-based azoic dyestuff, formula (II) compound and formula (III) compound equimolar ratio example are mixed, join in the solvent that contains alkali, in the presence of catalyzer, pass into hydrogen, in room temperature～98 ℃, low pressure (0.1～0.2MPa) or normal pressure under reacted 4～24 hours, directly make formula (I) compound of azo structure.
Wherein, in formula (I), formula (II) and the formula (III), n=1,2 or 3; X is-H ,-CH
3,-C
2H
5,-Cl ,-Br; Y is-H ,-Cl ,-Br; R
1For-H ,-CH
3,-NHCOCH
3,-NHCOC
2H
5R
2For-H ,-CH
3R
3With R
4Identical, for-C
2H
4OCH
3,-C
2H
4OC
2H
5,-C
2H
4OCOCH
3,-C
2H
4OCOC
2H
5
Described catalyzer is the mixture of the one or both in Pt nano material, the Pd nano material.
The diameter of described catalyzer is 2nm～3nm.
Preferably, described catalyst levels accounts for the 0.01wt%～1wt% of formula (II) compound.
Described alkali is potassium hydroxide, sodium hydroxide, (CH
3)
3COONa, (CH
3)
3The mixture of one or two or more kinds among the COOK.
Described solvent is a kind of in m-xylene, o-Xylol, toluene, water, the 2-propyl alcohol.
By the phthalimide-based azoic dyestuff of aforesaid method preparation, to compare with existing public technology, technical progress of the present invention is: the synthesis technique flow process is short, has avoided the defective of the classical synthetic method of diazotization-coupling; Safe, only need low pressure or normal pressure catalytic hydrogenation coupling; Energy consumption is low, only needs room temperature～98 ℃ lower reaction; Separating-purifying is simple, does not need to purify or isolation of intermediate products with a large amount of solvents; The sewage of discharging is low, does not produce the secondary pollution to environment.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the invention, the accompanying drawing of required use was done to introduce simply during the below will describe embodiment, apparently, accompanying drawing relevant of the present invention in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the used common response device structure of the embodiment of the invention and reaction principle schematic diagram;
The scanning electron microscope (SEM) photograph of the Pt nano-wire catalyst that Fig. 2 embodiment of the invention is used.
Embodiment
A kind of preparation method of phthalimide-based azoic dyestuff, formula (II) compound and formula (III) compound equimolar ratio example are mixed, join in the solvent that contains alkali, in the presence of catalyzer, pass into hydrogen, in room temperature～98 ℃, low pressure (0.1～0.2MPa) or normal pressure under reacted 4～24 hours, directly make formula (I) compound of azo structure.
Wherein, in formula (I), formula (II) and the formula (III), n=1,2 or 3; X is-H ,-CH
3,-C
2H
5,-Cl ,-Br; Y is-H ,-Cl ,-Br; R
1For-H ,-CH
3,-NHCOCH
3,-NHCOC
2H
5R
2For-H ,-CH
3R
3With R
4Identical, for-C
2H
4OCH
3,-C
2H
4OC
2H
5,-C
2H
4OCOCH
3,-C
2H
4OCOC
2H
5
Described catalyzer is the mixture of the one or both in Pt nano material, the Pd nano material.
The diameter of described catalyzer is 2nm～3nm.
Preferably, described catalyst levels accounts for the 0.01wt%～1wt% of formula (II) compound.
Described alkali is potassium hydroxide, sodium hydroxide, (CH
3)
3COONa, (CH
3)
3The mixture of one or two or more kinds among the COOK.
Described solvent is a kind of in m-xylene, o-Xylol, toluene, water, the 2-propyl alcohol.
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is described in detail, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work belongs to the scope of protection of the invention.
Each used raw material of the present invention all can be buied by market.
Embodiment 1
Synthesizing of Pt nanowires: simultaneously thermolysis of reduction methyl ethyl diketone platinum pentacarbonyl iron obtains the Fe/Pt nano wire of diameter 2nm～3nm (referring to Angew.Chem.Int.Ed.46 (2007) in 160 ℃ oleyl amine, 6333-6335), then heated and stirred erodes the Fe of Pt nano wire coated outside under acidic conditions, namely get Pt nanowires, the gained nano wire is carried out electron-microscope scanning, result such as accompanying drawing 2, from accompanying drawing 2 as can be known, the diameter of Pt nanowires is 2nm～3nm.
Embodiment 2
In the reaction flask of 20g m-xylene, at first add 2.85g compound (IIA) and 3.09g compound (IIIA), then add respectively 0.4g sodium hydroxide and 1.4mg platinum Nano compound.This system is put into autoclave pressure, by cooling, vacuumize, put hydrogen, circulate 3～4 times, put into hydrogen, return to room temperature.This system is in 80 ℃ oil bath, and the maintenance hydrogen pressure is 0.2Mpa, obtains product (IA) behind the heating 15h, and productive rate is 78%.
Embodiment 3
In the reaction flask of 20g toluene, at first add 3.64g compound (IIB) and 3.69g compound (IIIB), then add respectively 0.4g sodium hydroxide and 1.8mg platinum Nano compound.This system is put into autoclave pressure, by cooling, vacuumize, put hydrogen, circulate 3～4 times, put into hydrogen, return to room temperature.This system is in 50 ℃ oil bath, and the maintenance hydrogen pressure is 0.15Mpa, obtains product (IB) behind the heating 20h, and productive rate is 80%.
Embodiment 4
In the reaction flask of 20g toluene, at first add 2.06g compound (IIC) and 1.94g compound (IIIC), then add respectively 0.2g sodium hydroxide, 0.1g (CH
3)
3COONa and 1.4mg platinum Nano compound.This system is put into autoclave pressure, by cooling, vacuumize, put hydrogen, circulate 3～4 times, put into hydrogen, return to room temperature.This system is in 90 ℃ oil bath, and the maintenance hydrogen pressure is 0.2Mpa, obtains product (IC) behind the heating 16h, and productive rate is 79%.
Performance test
Through purifying, the nuclear-magnetism result of product is with the product of embodiment 4 preparation:
1H?NMR(400M,d-DMSO):1.1(6H,t,Ar-N-C-CH
3),3.0(3H,s,imide?N-CH
3),3.5(4H,q,Ar-NCH
2-C),6.8(2H,d,Ar-H),7.8(2H,d,Ar-H),8.0(2H,d,Ar-H),8.3(1H,q,Ar-H)。
In sum, by the phthalimide-based azoic dyestuff of aforesaid method preparation, compare with existing public technology, technical progress of the present invention is: the synthesis technique flow process is short, has avoided the defective of the classical synthetic method of diazotization-coupling; Safe, only need low pressure or normal pressure catalytic hydrogenation coupling; Energy consumption is low, only needs room temperature～98 ℃ lower reaction; Separating-purifying is simple, does not need to purify or isolation of intermediate products with a large amount of solvents; The sewage of discharging is low, does not produce the secondary pollution to environment.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that do not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other specific form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in the scope.Any Reference numeral in the claim should be considered as limit related claim.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but be not that each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets only is for clarity sake, those skilled in the art should make specification sheets as a whole, and the technical scheme among each embodiment also can through appropriate combination, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (5)
1. the preparation method of a phthalimide-based azoic dyestuff is characterized in that:
Formula (II) compound and formula (III) compound equimolar ratio example are mixed, join in the solvent that contains alkali, in the presence of catalyzer, pass into hydrogen, in room temperature～98 ℃, low pressure (0.1～0.2MPa) or normal pressure under reacted 4～24 hours, directly make formula (I) compound of azo structure
Wherein, in formula (I), formula (II) and the formula (III), n=1,2 or 3; X is-H ,-CH
3,-C
2H
5,-Cl ,-Br; Y is-H ,-Cl ,-Br; R
1For-H ,-CH
3,-NHCOCH
3,-NHCOC
2H
5R
2For-H ,-CH
3R
3With R
4Identical, for-C
2H
4OCH
3,-C
2H
4OC
2H
5,-C
2H
4OCOCH
3,-C
2H
4OCOC
2H
5
Described catalyzer is the mixture of the one or both in Pt nano material, the Pd nano material.
2. preparation method according to claim 1, it is characterized in that: the diameter of described catalyzer is 2nm～3nm.
3. preparation method according to claim 1, it is characterized in that: described catalyst levels accounts for the 0.01wt%～1wt% of formula (II) compound.
4. preparation method according to claim 1, it is characterized in that: described alkali is potassium hydroxide, sodium hydroxide, (CH
3)
3COONa, (CH
3)
3The mixture of one or two or more kinds among the COOK.
5. preparation method according to claim 1 is characterized in that: described solvent is a kind of in m-xylene, o-Xylol, toluene, water, the 2-propyl alcohol.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210405647.3A CN102876068B (en) | 2012-10-22 | 2012-10-22 | A kind of preparation method of phthaloyl azo dye |
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|---|---|---|---|
| CN201210405647.3A CN102876068B (en) | 2012-10-22 | 2012-10-22 | A kind of preparation method of phthaloyl azo dye |
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|---|---|
| CN102876068A true CN102876068A (en) | 2013-01-16 |
| CN102876068B CN102876068B (en) | 2015-08-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566939A (en) * | 2016-01-28 | 2016-05-11 | 俞杏英 | Orange disperse dye monomeric compound and preparation method and application thereof |
| CN105647224A (en) * | 2016-01-28 | 2016-06-08 | 俞杏英 | Phthalimide-azo disperse dye monomeric compound and preparing method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105733291B (en) * | 2016-01-28 | 2018-03-30 | 俞杏英 | A kind of high shifting red colouration dispersion dyes monomer compound and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6555664B1 (en) * | 1998-12-31 | 2003-04-29 | Ciba Specialty Chemicals Corporation | Phthalimidyl azo pigments, method for producing same and utilisation thereof |
| US20040116681A1 (en) * | 2001-02-07 | 2004-06-17 | Antoine Clement | Phthalimidyl azo dyes, process for the preparation thereof and the use thereof |
| CN101914036A (en) * | 2010-07-06 | 2010-12-15 | 苏州大学 | Method for preparing azobenzene derivatives |
-
2012
- 2012-10-22 CN CN201210405647.3A patent/CN102876068B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6555664B1 (en) * | 1998-12-31 | 2003-04-29 | Ciba Specialty Chemicals Corporation | Phthalimidyl azo pigments, method for producing same and utilisation thereof |
| US20040116681A1 (en) * | 2001-02-07 | 2004-06-17 | Antoine Clement | Phthalimidyl azo dyes, process for the preparation thereof and the use thereof |
| CN101914036A (en) * | 2010-07-06 | 2010-12-15 | 苏州大学 | Method for preparing azobenzene derivatives |
Non-Patent Citations (2)
| Title |
|---|
| LEI HU 等: "《A Highly Active Nano-Palladium Catalyst for the Preparation of Aromatic Azos under Mild Conditions》", 《ORGANIC LETTERS》 * |
| LEI HU等: "《Highly Efficient Synthesis of Aromatic Azos Catalyzed by Unsupported Ultra-thin Pt Nanowires》", 《CHEM.COMMUN》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566939A (en) * | 2016-01-28 | 2016-05-11 | 俞杏英 | Orange disperse dye monomeric compound and preparation method and application thereof |
| CN105647224A (en) * | 2016-01-28 | 2016-06-08 | 俞杏英 | Phthalimide-azo disperse dye monomeric compound and preparing method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN102876068B (en) | 2015-08-12 |
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Address after: 312073 new second village, Ma On Zhen, Keqiao District, Shaoxing, Zhejiang Patentee after: Zhejiang Wanfeng Chemical Co., Ltd Address before: 312073, Zhejiang, Shaoxing Province, Shaoxing County, Ma on the town of new village Patentee before: ZHEJIANG WANFENG CHEMICAL Co.,Ltd. |