CN101531598A - Tert-butyl benzidine and preparation method thereof - Google Patents
Tert-butyl benzidine and preparation method thereof Download PDFInfo
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- CN101531598A CN101531598A CN200910049450A CN200910049450A CN101531598A CN 101531598 A CN101531598 A CN 101531598A CN 200910049450 A CN200910049450 A CN 200910049450A CN 200910049450 A CN200910049450 A CN 200910049450A CN 101531598 A CN101531598 A CN 101531598A
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- tertiary butyl
- benzidine
- butyl
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- iodoaniline
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Abstract
The invention provides benzidine containing a tert-butyl structure (3,3'-di-tert-butyl-4,4'-benzidine) and a preparation method thereof. In the method, 2-tertbutylaniline and iodine are used as raw materials to react for 5 to 6 hours at normal temperature to obtain 2-tert-butyl-4-iodoaniline with water as solvent, in the presence of sodium bicarbonate; then, the 2-tert-butyl-4-iodoaniline performs a coupling reaction for 6 to 8 hours at 115 DEG C with N,N-dimethyl formamide/water as solvent and tetrabutyl ammonium bromide as a phase transfer catalyst, in catalysis of palladium acetate, and in the presence of sodium carbonate. After the reaction is completed, benzidine containing the tert-butyl structure can be obtained through extracting, drying, column chromatography and recrystallization. The aromatic diamine can be used as a raw material for synthesizing soluble polyimide, a chain extender or an epoxy curing agent of polyurethane, and has wide application prospect.
Description
Patent of the present invention relates to a kind of 4 of tertiary butyl replacement, 4 '-benzidine and preparation method thereof of containing.
Japanese Patent JP 2007246427, JP 2005126331, German patent DE 3511545, DE 3511544 has reported a series of benzidines that contain side group, and its structural formula is as follows:
Wherein R is a methyl, trifluoromethyl, sec.-propyl; R
1Be methoxyl group, n-butoxy etc.
US 2005215823, and US 6835854, the benzidine of report, and its structure is as follows:
These aromatic diamines can be used as the monomer of synthesis of polyimides, also are used as curing agent for epoxy resin, are used for preparing the rubber antiaging agent widely.
The present invention is from Molecular Structure Design and practical application angle, and synthetic a kind of aromatic diamines that contains tertiary butyl structure, its structural formula are shown in (1), and chemistry is called 3,3 '-di-t-butyl-4,4 '-benzidine.The benzidine that synthetic of the present invention contains tertiary butyl structure can be used as the raw material of synthesizing soluble polyimide, and the chainextender of polyurethane or epoxy curing agent are used for preparing the rubber antiaging agent, and purposes is widely arranged.
Preparation method of the present invention is to be raw material with 2-tertiary butyl aniline, and sodium bicarbonate exists down, water as solvent, normal temperature descends and Iod R 5-6 hour, obtains the 2-tertiary butyl-4-Iodoaniline, then the 2-tertiary butyl-4-Iodoaniline, under 5% palladium catalyst action, with N, dinethylformamide/water is as solvent, and Tetrabutyl amonium bromide is as phase-transfer catalyst, in the presence of yellow soda ash, linked reaction takes place, reaction times 6-8 hour, 115 ℃ of temperature.Reaction is used ethyl acetate extraction after finishing, the oil reservoir anhydrous sodium sulfate drying, and column chromatography, last dehydrated alcohol recrystallization can obtain containing the aromatic diamines needle-like crystal of tertiary butyl.Reaction process can be expressed as follows:
The concrete preparation method of the present invention can be divided into three phases.Fs: at room temperature, do reaction medium with the aqueous solution of sodium bicarbonate, 2-tertiary butyl aniline and Iod R quantitatively obtain the 2-tertiary butyl-4-Iodoaniline; Subordinate phase: with N, dinethylformamide/water is as solvent, positive Tetrabutyl amonium bromide is as phase-transfer catalyst, the 2-tertiary butyl-4-Iodoaniline is under 5% palladium catalyst action, linked reaction takes place under alkaline condition, obtain containing 4 of the tertiary butyl 115 ℃ of temperature of reaction, the thick product of 4 '-benzidine; Phase III: thick product with ethyl acetate extraction after, the oil phase anhydrous sodium sulfate drying, column chromatography is used the dehydrated alcohol recrystallization at last, can obtain containing 4 of the tertiary butyl, the pure product of 4 '-benzidine.
3,3 '-di-t-butyl-4,4 '-benzidine structure (1) characterizes with mass spectrum, infrared spectra, nuclear magnetic resonance spectrum hydrogen spectrum and carbon spectrum respectively and is confirmed.
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: with 2-tertiary butyl aniline (7.46g, 0.05mol), sodium bicarbonate (7.5g, 0.09mol), water 50mL adds in the reactor, magnetic agitation, add several times under the ice-water bath iodine (12.7g, 0.05mol), after adding iodine, remove ice-water bath, normal temperature reacted 6 hours down.Reaction solution adds water, dichloromethane extraction, the oil phase anhydrous sodium sulfate drying, column chromatography, get final product the purified 2-tertiary butyl-4-Iodoaniline, productive rate can reach 93.2%.
With the 2-tertiary butyl-4-Iodoaniline (0.55g, 2mmol), and palladium 22.45mg (0.1mmol, 5mol%), positive Tetrabutyl amonium bromide (0.325g, 1mmol), and anhydrous sodium carbonate (0.212g, 2mmol) adding is equipped with in the reactor of reflux condensing tube, add Virahol 1mL under the magnetic agitation, N, dinethylformamide 4.5mL, water 1.75mL.Nitrogen protection is heated to 115 ℃, reacted 8 hours, and at last with the reaction solution ethyl acetate extraction, washing then, the oil reservoir anhydrous sodium sulphate, last column chromatography promptly gets the purified aromatic diamines (1) that contains tert-butyl structure, and productive rate is 71.52%.
Embodiment 2: with 2-tertiary butyl aniline (5.2g, 35mmol), sodium-chlor (4.1g, 70mmol), sodium periodate (7.5g, 35mmol), acetic acid 108mL, water 12mL add in the reactor, magnetic agitation, (5.8g, 35mmol), normal temperature reacted 6 hours down to add potassiumiodide several times.Reaction solution adds water, dichloromethane extraction, the oil phase anhydrous sodium sulfate drying, column chromatography, get final product the purified 2-tertiary butyl-4-Iodoaniline, productive rate is 40%.
With the 2-tertiary butyl-4-Iodoaniline (0.55g, 2mmol), and palladium 22.45mg (0.1mmol, 5mol%), positive Tetrabutyl amonium bromide (0.325g, 1mmol), and Tripotassium phosphate (0.424g, 2mmol) adding is equipped with in the reactor of reflux condensing tube, add Virahol 1mL under the magnetic agitation, N, dinethylformamide 4.5mL, water 1.75mL.Nitrogen protection is heated to 115 ℃, reacted 8 hours, and at last with the reaction solution ethyl acetate extraction, washing then, the oil reservoir anhydrous sodium sulphate, last column chromatography promptly gets the purified aromatic diamines (1) that contains tert-butyl structure, and productive rate is 80%.
Embodiment 3: with the 2-tertiary butyl-4-Iodoaniline (0.55g, 2mmol), and palladium 22.45mg (0.1mmol, 5mol%), positive Tetrabutyl amonium bromide (0.325g, 1mmol), and Anhydrous potassium carbonate (0.276g, 2mmol) adding is equipped with in the reactor of reflux condensing tube, add Virahol 1mL under the magnetic agitation, N, dinethylformamide 4.5mL, water 1.75mL.Nitrogen protection is heated to 115 ℃, reacted 8 hours, and at last with the reaction solution ethyl acetate extraction, washing then, the oil reservoir anhydrous sodium sulphate, last column chromatography promptly gets the purified aromatic diamines (1) that contains tert-butyl structure, and productive rate is 40%.
Claims (2)
1. one kind contains 4 of the tertiary butyl, 4 '-benzidine, and its molecular structure characteristic is as shown below:
2. one kind contains 4 of the tertiary butyl, the preparation method of 4 '-benzidine, and its feature comprises following three phases:
Fs: at room temperature, do reaction medium with the aqueous solution of sodium bicarbonate, 2-tertiary butyl aniline and Iod R quantitatively obtain the 2-tertiary butyl-4-Iodoaniline;
Subordinate phase: with N, dinethylformamide/water is as solvent, Tetrabutyl amonium bromide is as phase-transfer catalyst, the 2-tertiary butyl-4-Iodoaniline is under 5% palladium catalyst action, linked reaction takes place under alkaline condition, obtain containing 4 of the tertiary butyl 115 ℃ of temperature of reaction, the thick product of 4 '-benzidine;
Phase III: thick product with ethyl acetate extraction after, the oil phase anhydrous sodium sulfate drying, column chromatography is used the dehydrated alcohol recrystallization at last, can obtain containing 4 of the tertiary butyl, the pure product of 4 '-benzidine.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863775A (en) * | 2010-05-25 | 2010-10-20 | 重庆大学 | Method for one-step synthesis of diphenylenediamine derivatives through oxidative coupling reaction of phenylamine derivatives |
| CN103910882A (en) * | 2013-12-27 | 2014-07-09 | 上海交通大学 | High-Tg soluble polyimide and preparation method thereof |
-
2009
- 2009-04-16 CN CN200910049450A patent/CN101531598A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863775A (en) * | 2010-05-25 | 2010-10-20 | 重庆大学 | Method for one-step synthesis of diphenylenediamine derivatives through oxidative coupling reaction of phenylamine derivatives |
| CN101863775B (en) * | 2010-05-25 | 2013-03-13 | 重庆大学 | Method for one-step synthesis of diphenylenediamine derivatives through oxidative coupling reaction of phenylamine derivatives |
| CN103910882A (en) * | 2013-12-27 | 2014-07-09 | 上海交通大学 | High-Tg soluble polyimide and preparation method thereof |
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Application publication date: 20090916 |