Preparation method of diamine compound containing thiazole ring

An amine compound, thiazole ring-containing technology, applied in the field of polymer synthesis, can solve the problems affecting the overall yield of the process route, long reaction time, complicated reaction device, etc., avoiding column chromatography and multiple recrystallization purification steps, Simplify the difficulty and technical requirements of process operation, simplify the effect of reaction process and device

Active Publication Date: 2014-05-14
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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Problems solved by technology

In the method, the bromine reagent used in the first step is liquid bromine. Because the liquid bromine needs to be washed with concentrated sulfuric acid to remove water and dry, there is a problem that the risk of pretreatment is complicated and difficult to enlarge; and the liquid bromine corrodes the reactor seriously, which will greatly Increase the equipment investment required for the amplification of the technical route; another important defect of this reaction is that there are many by-products, and the product needs to be recrystallized or further purified by column chromatography, which greatly affects the total yield of the entire process route
In the second step, using absolute ethanol as the reaction solvent can improve the purity of the product to a certain extent, but compared with absolute ethanol, absolute absolute ethanol requires further application of metal sodium or magnesium for dehydration treatment, and is very easy to absorb water, so higher cost
The third step is to use expensive Pd / C and highly toxic hydrazine hydrate as reducing agents, which not only has high cost, but also seriously affects environmental safety.
Compared with the foregoing disclosure, the method increases the first step is p-hydroxyacetophenone and K 2 CO 3 The potassium phenate was obtained after 24 hours of water separation by a water separator, and the prepared potassium phenate reacted with 4-chloronitrobenzene in a nucleophilic substitution reaction. Waste of power; greatly affects the manufacture and industrial application of related functional materials

Method used

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  • Preparation method of diamine compound containing thiazole ring
  • Preparation method of diamine compound containing thiazole ring
  • Preparation method of diamine compound containing thiazole ring

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] ①Put 45.00 g (C 8 h 8 o 2 , 136.15g / mol, 0.33 mol) p-Hydroxyacetophenone, 50.25 g (K 2 CO 3 , 138.21g / mol, 0.36 mol) anhydrous potassium carbonate, 54.67 g (C 6 h 4 ClNO 2 , 157.55g / mol, 0.35 mol) p-chloronitrobenzene and 150 mL DMAc, under continuous stirring, the reaction temperature was raised to 130-135°C to reflux the reaction mixture. After about 12 hours of reaction time, TLC followed the reaction process. After the reaction was completed, the reaction mixture was poured into 500 mL ice-water mixture (mass ratio 1:1), and a brownish-yellow precipitate precipitated out. Filter, wash the filter cake with water and ethanol successively, and put it into a vacuum drying oven at 40° C. to dry overnight. The crude product was recrystallized from ethanol to obtain 68.02 g of light yellow 4-(4'-nitrophenoxy)-acetophenone crystals. Yield: 80%. Melting point: 81~82℃;

[0022] ② Add 257.24 g (C 14 h 11 NO 4 , 257.24 g / mol, 1mol) 4-(4'-nitrophenoxy)-acetophenone ...

Embodiment 2

[0026] ①Put 40.85 g (C 8 h 8 o 2 , 136.15g / mol, 0.30 mol) p-Hydroxyacetophenone, 37.32 g (K 2 CO 3 , 138.21g / mol, 0.27mol) anhydrous potassium carbonate, 47.27 g (C 6 h 4 ClNO 2 , 157.55g / mol, 0.30 mol) p-chloronitrobenzene and 180 mL DMAc, under continuous stirring, the reaction temperature was raised to 135-140°C to reflux the reaction mixture. After about 10 hours of reaction time, TLC followed the reaction progress. After the reaction was completed, the reaction mixture was poured into 500 mL ice-water mixture (mass ratio 1:1), and a brownish-yellow precipitate precipitated out. Filter, wash the filter cake with water and ethanol successively, and put it into a vacuum drying oven at 40° C. to dry overnight. The crude product was recrystallized from ethanol to obtain 60.19 g of pale yellow 4-(4'-nitrophenoxy)-acetophenone crystals. Yield: 78%. Melting point: 81-82°C;

[0027] ②Add 514.48 g (C 14 h 11 NO 4 , 257.24 g / mol, 2mol) 4-(4'-nitrophenoxy)-acetophenone ...

Embodiment 3

[0031] ①Put 27.23 g (C 8 h 8 o 2 , 136.15g / mol, 0.20mol) p-Hydroxyacetophenone, 24.88 g (K 2 CO 3 , 138.21g / mol, 0.18 mol) anhydrous potassium carbonate, 31.51 g (C 6 h 4 ClNO 2 , 157.55g / mol, 0.20 mol) p-chloronitrobenzene and 70 mL DMAc under continuous stirring, the reaction temperature was raised to 140°C to reflux the reaction mixture. After about 12 hours of reaction time, TLC followed the reaction progress. After the reaction was completed, the reaction mixture was poured into 300 mL of ice-water mixture (mass ratio 1:1), and a brownish-yellow precipitate precipitated out. Filter, wash the filter cake with water and ethanol successively, and put it into a vacuum drying oven for 40 o C dried overnight. The crude product was recrystallized from ethanol to obtain 39.10 g of light yellow 4-(4'-nitrophenoxy)-acetophenone crystals. Yield: 76%. Melting point: 81-82 ℃;

[0032] ② Add 257.24 g (C 14 h 11 NO 4 , 257.24 g / mol, 1mol) 4-(4'-nitrophenoxy)-acetophenone a...

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Abstract

The invention discloses a method of preparing a diamine compound containing a thiazole ring. The method comprises the following steps: by taking 4-hydroxyl acetophenone and parachloronitrobenzene as initial raw materials, carrying out a reaction under the catalytic effect of K2CO3 to generate a nucleophilically substituted product; then, by taking trichloromethane as a solvent, carrying out a bromination reaction with 1,3-dibromo-5,5-dimethyl hydantoin under the effect of methyl benzenesulfonic acid to generate alpha-bromide; then, carrying out a reaction on the alpha-bromide and thiourea to obtain a mononitro product containing the thiazole ring; finally, by taking SnCl2 as a reducing agent, reducing the mononitryl product containing the thiazole ring to obtain the diamine compound containing the thiazole ring. The preparation method disclosed by the invention is mild in synthetic condition, low in cost and high in yield. Meanwhile, multifarious column chromatography and re-crystallized purifying steps for many times in the prior art are avoided, and the yield and purity of synthetic products are greatly improved, so that the diamine compound containing the thiazole ring is widely applied to preparing polyimide.

Description

technical field [0001] The invention relates to a preparation method of a diamine compound containing a thiazole ring, belonging to the technical field of polymer synthesis. Background technique [0002] In the molecular structure of diamine compounds containing thiazole rings, there are flexible ether oxygen bonds, non-coplanar groups and relatively rigid thiazole heterocycles. Among them, ether oxygen bonds can increase the flexibility of the molecular chain and improve the solubility of the corresponding polymer. ; The non-coplanar group has positive significance on the mechanical properties of the corresponding polymer; and the heteroatom of the thiazole heterocycle can provide a lone pair of electrons to coordinate with the metal substrate to increase the bonding performance of the corresponding polymer. Therefore, the compound is used to prepare polyimides containing thiazole heterocycles in the main chain, which have good bonding properties, mechanical properties and ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D277/40
CPCC07D277/40
Inventor 赵鑫刘刚耿庆芬
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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