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Synthetic method for preparing 2-acyl 4-allcyl phenol

A technology for the synthesis of alkylphenols and synthesis methods, which is applied in the field of synthesis of 2-acyl-4-alkylphenols, an important precursor of metal extractants, can solve problems such as unstable process routes, complicated operations, and high product purity, and avoid Difficulty in product purification, overcoming complex operation, and high yield

Inactive Publication Date: 2006-08-23
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In order to overcome the problems of low total yield, harsh equipment requirements, severe reaction conditions, unstable process route, difficult product separation and purification and low product purity in the prior art
[0006] The advantages and innovations of the present invention are that ① avoiding the use of high temperature and relatively expensive reagents; ② overcoming the problems of complex operation, harsh reaction conditions, and difficulties in product separation and purification; ③ obtaining high yield and high selectivity under mild conditions. The target product; ④The purity of the product is higher than that obtained by other production methods. The purity of the 2-acyl-4-alkylphenol obtained by the method provided by the patent of the present invention can generally reach more than 90%, while the 2-acylphenol prepared by the traditional method The purity of -4-alkylphenol generally only has 80-85%; ⑤ most of the by-product chlorinated hydrocarbons produced by the reaction can be recovered, and catalysts, such as aqueous aluminum chloride solution, etc., can also be recycled well. The colorless aluminum chloride aqueous solution can be used to prepare polyaluminum chloride (referred to as PAC) without further decolorization and purification, and PAC is a new type of inorganic polymer coagulant, which has replaced Ferric chloride, aluminum sulfate, and alum are widely used ("Review of the production method of polyaluminum chloride", Henan Chemical Industry, 1994, 8)

Method used

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  • Synthetic method for preparing 2-acyl 4-allcyl phenol
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  • Synthetic method for preparing 2-acyl 4-allcyl phenol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Embodiment 1: the preparation of 4-hexylphenetole

[0030] 17.8 g of 4-hexylphenol, 16.6 g of anhydrous potassium carbonate, and 100 mL of DMF were sequentially added to a 250 mL three-necked flask. Subsequently, 25.1 g of ethyl iodide was slowly added dropwise into the reaction system, vigorously stirred, and the reaction temperature was controlled at room temperature during the dropwise addition. After the dropwise addition, raise the temperature of the system to 60-70°C, continue to stir for 3 hours, cool to room temperature, pour the reaction solution into 400mL of water, extract the aqueous phase with ethyl acetate, combine the organic phases, and dry with anhydrous magnesium sulfate , to obtain a light yellow liquid after filtration, evaporate the solvent, and carry out vacuum distillation to obtain 19.6 grams of product (b.p.85-90°C / 1mmHg), 1 H NMR (CDCl 3 , 300MHz) δ7.10-7.03 (m, 2H), 6.99-6.89 (m, 2H), 3.82 (q, J=1.1Hz, 2H), 2.11-0.76 (m, 16H) ...

Embodiment 2

[0031] Embodiment 2: Preparation of (4-nonylphenyl) benzyl ether

[0032] 26.2 g of 4-nonylphenol, 11.9 g of pyridine, and 100 mL of dichloroethane were sequentially added to a 250 mL three-necked flask. Subsequently, 16.4 g of benzyl chloride was slowly added dropwise to the reaction system, vigorously stirred, and the reaction temperature was controlled at room temperature during the dropwise addition. After the dropwise addition, the system was heated to reflux, continued to stir for 3 hours, cooled to room temperature, poured the reaction solution into 400 mL of water, extracted the aqueous phase with ethyl acetate, combined the organic phases, dried with anhydrous magnesium sulfate, and filtered Obtain light yellow liquid, distill off solvent, carry out vacuum distillation to obtain product 28.5 grams (b.p.150-153 ℃ / 1mmHg), 1 H NMR (CDCl 3 , 300MHz) δ7.43-6.87 (m, 9H), 4.45 (s, 2H), 2.03-0.61 (m, 19H) ppm; the yield was 92%.

Embodiment 3

[0033] Embodiment 3: Preparation of (4-nonylphenyl) allyl ether

[0034] Into a 250 mL three-necked flask, 22.0 g of 4-nonylphenol, 20.7 g of anhydrous potassium carbonate, and 100 mL of methanol were successively added. Then 15.7 g of allyl bromide was slowly added dropwise to the reaction system and stirred vigorously. The reaction temperature was controlled at room temperature during the dropwise addition. to room temperature, pour the reaction liquid into 600 mL of water, then use ethyl acetate to extract the aqueous phase, combine the organic phases, dry using anhydrous magnesium sulfate, obtain a light yellow liquid after filtration, evaporate the solvent, and carry out vacuum distillation to obtain 24.2 g of the product (b.p.115-118℃ / 1mmHg), 1 H NMR (CDCl 3 , 300MHz) δ7.20-7.14(m, 2H), 7.05-6.97(m, 2H), 5.64-5.52(m, 1H); 5.33-5.03(m, 2H), 4.35-4.25(d×t, 2H ), 2.06-0.57 (m, 19H) ppm; the yield was 93%.

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Abstract

The present invention relates to the synthesis process of different kinds of 2-acyl-4-alkyl phenol, which is the important intermediate of metal extractant 5-alkyl-2-hydroxyalkyl benzopheonone oxime. Through a two-step reaction under relatively mild condition, the present invention can obtain the target product in high yield and high selectivity, and the solvent, the reaction produced halohydrocarbon and the catalyst aqua may be reused without exhaust. The synthesis process has industrial production foreground obviously.

Description

technical field [0001] The invention belongs to the field of chemical materials and relates to a synthesis method for preparing 2-acyl-4-alkylphenol, an important precursor of a metal extractant. Background technique [0002] 2-acyl-4-alkylphenol (I) is an important intermediate of metal extractant 5-alkyl-2-hydroxyalkylphenone oxime (II), which can be obtained by reacting with hydroxylamine to obtain 5-alkyl-2 -Hydroxyalkylphenone oxime (II). This type of ketoxime is widely used in the field of metal extraction. For example: 2-acetyl-4-nonylphenol is an important precursor of extractants for copper, nickel and other metal purification (see: U.S. Pat. No. 5,300,689; U.S. Pat. No. 5,969,185; U.S. Pat. No. 5,488,161; WO.95 / 01957; J. Prakt. Chem. 1989, 331(4), 617-630). Its structural formula is as follows: [0003] [0004] In U.S.Pat.No.5,300,689 describes a method for preparing 2-acyl-4-alkylphenols with Fries rearrangement, the method has low yield, high reaction tem...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/00C07C49/825
Inventor 邓敏智严政军李超忠
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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