CN107129432B - Synthesis method of ultraviolet absorbent 4,4' -dihexyl benzophenone - Google Patents
Synthesis method of ultraviolet absorbent 4,4' -dihexyl benzophenone Download PDFInfo
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- CN107129432B CN107129432B CN201710416860.7A CN201710416860A CN107129432B CN 107129432 B CN107129432 B CN 107129432B CN 201710416860 A CN201710416860 A CN 201710416860A CN 107129432 B CN107129432 B CN 107129432B
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention discloses a method for synthesizing an ultraviolet absorbent 4,4' -dihexyl benzophenone, which comprises the following steps: taking p-hydroxybenzoic acid as an initial raw material, and protecting hydroxyl groups by acetylation; under the catalysis of zinc chloride and phosphorus oxychloride, the intermediate p-hydroxybenzoic acid phenyl ester is synthesized by reacting with phenol Fredel-Crafts; preparing an intermediate 4, 4-dihydroxy benzophenone by deacetylation protective group and Fries rearrangement; finally salifying with potassium carbonate, and synthesizing with 1-bromohexane under catalysis of tetrabutylammonium bromide through a Williamson reaction to obtain a 4,4' -bis (hexyloxy) benzophenone product; the invention has the following advantages: the reaction condition is mild, the temperature is low at normal pressure, and the quality control is stable; the conversion rate of the raw materials is high, and the side reaction is effectively inhibited; less three wastes, light pollution and benefit to the environment and the labor protection of the producer.
Description
Technical Field
The invention relates to a synthesis method of an ultraviolet absorbent, in particular to a synthesis method of an ultraviolet absorbent 4,4' -dihexyl benzophenone.
Background
The ultraviolet absorbent (benzophenone derivative) is a polymer material functional assistant which is widely applied, can strongly absorb ultraviolet rays, and is also widely applied to the fields of daily chemical industry, medicines, pesticides, plastics, coatings and the like. Because the damage of the earth's ozone layer is more and more serious, the solar ultraviolet ray radiates the earth more and more intensely, so the ultraviolet ray absorbent is one of the necessary functional additives of various high molecular materials, skin protection articles and the like. In recent years, demand for high-quality ultraviolet absorbers has been increasing at home and abroad. The following developments have been made internationally: sulfonic acid-containing, amino-type, hetero-benzene azole, diazo-benzene, and benzotriazole ultraviolet absorbers. There are few reports on the synthesis of the title compound.
Disclosure of Invention
The invention aims to overcome the limitations, and provides a method for synthesizing the ultraviolet absorbent 4,4' -dihexyl benzophenone, which has the advantages of easily obtained raw and auxiliary materials, mild reaction conditions, safe and simple operation, high conversion rate, stable product quality, less three wastes and easy disposal.
The purpose of the invention is realized by the following technical scheme: a method for synthesizing an ultraviolet absorbent 4,4' -dihexyl benzophenone comprises the following steps:
step A: protecting hydroxyl by acetylation of p-hydroxybenzoic acid;
and B: under the catalysis of zinc chloride and phosphorus oxychloride, the intermediate p-hydroxybenzoic acid phenyl ester is synthesized by reacting with phenol Fredel-Crafts;
and C: preparing an intermediate 4, 4-dihydroxy benzophenone by deacetylation protecting group and Fries rearrangement;
step D: and finally salifying with potassium carbonate, and synthesizing with 1-bromohexane under the catalysis of tetrabutylammonium bromide through a Williamson reaction to obtain a 4,4' -bis (hexyloxy) benzophenone product.
Preferably, step a is specifically: adding 0.375mol of p-hydroxybenzoic acid into cyclohexane, dripping 0.44-0.46 mol of acetyl chloride at 30-35 ℃, reacting for 2 hours at 35-40 ℃ after finishing dripping, distilling at normal pressure to recover excessive acetyl chloride and solvent cyclohexane, adding ethanol for recrystallization to obtain 0.36mol of p-acetoxybenzoic acid, wherein the yield is 97%;
the step B specifically comprises the following steps: sequentially adding 0.36mol of p-acetoxybenzoic acid, 0.38-0.40 mol of phenol, 0.42-0.44 mol of phosphorus oxychloride and 0.72-0.75 mol of zinc chloride into dichlorobenzene, carrying out heat preservation reaction at 65-70 ℃ for 2 hours, cooling to 30 ℃, pouring into ice water in a trickle manner, standing, removing water, and washing to be neutral; dripping 90-120 ml of 28% ammonia water into the organic phase at 10-15 ℃, reacting at room temperature for 3h after dripping, standing, removing water, adding water again, carrying out azeotropic distillation at normal pressure to remove solvent dichlorobenzene, filtering, and recrystallizing a filter cake with ethanol to obtain 0.34mol of phenyl p-hydroxybenzoate with the yield of 94.4%;
the step C is specifically as follows: adding 0.34mol of phenyl p-hydroxybenzoate and 0.38-0.45 mol of aluminum trichloride into anhydrous carbon disulfide, stirring, heating, carrying out reflux reaction for 6 hours, cooling to 30 ℃, pouring into ice water in a trickle manner, standing, removing water, and washing to be neutral; distilling under normal pressure to remove solvent carbon disulfide, and recrystallizing with ethanol-water (1: 3) to obtain about 0.33mol white crystal 4, 4-dihydroxy benzophenone with yield of 97%;
the step D is specifically as follows: adding 0.33mol of 4, 4-dihydroxy benzophenone, 0.25-0.28 mol of potassium carbonate, 0.70-0.75 mol of 1-bromohexane and 0.014-0.019 mol of tetrabutylammonium bromide into acetone, stirring, heating and refluxing for 48 hours, changing the reaction material liquid from yellow green to white, distilling at normal pressure to remove solvent acetone, washing with water to remove salt, and recrystallizing with ethanol to obtain 0.31mol of white flaky crystal product 4, 4-dioxybenzophenone, wherein the yield is more than or equal to 92 percent, and the content is (HPLC method): not less than 99.5%; melting point is 104.5-105.0 ℃.
The reaction formula of each step is as follows:
in summary, the invention has the following advantages: the reaction condition is mild, the temperature is low at normal pressure, and the quality control is stable; the conversion rate of the raw materials is high, and the side reaction is effectively inhibited; less three wastes, light pollution and benefit to the environment and the labor protection of the producer.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
Example 1:
(1) adding 51.8g (0.375mol) of p-hydroxybenzoic acid into 100ml of cyclohexane, dripping 35.30g (0.45mol) of acetyl chloride at the temperature of 30-35 ℃, and carrying out heat preservation reaction for 2h at the temperature of 35-40 ℃ after dripping. Distilling under normal pressure to recover excessive acetyl chloride and cyclohexane solvent, adding ethanol for recrystallization to obtain 65.5g of p-acetoxybenzoic acid with a yield of 97%;
(2) sequentially adding 65.5g (0.36mol) of p-acetoxybenzoic acid, 35.8g (0.38mol) of phenol, 66(0.43mol) of phosphorus oxychloride and 98g (0.72mol) of zinc chloride into 180ml of dichlorobenzene, carrying out heat preservation reaction at 65-70 ℃ for 2h, cooling to 30 ℃, pouring trickle into 300ml of ice water, standing for dewatering, and washing to be neutral; dripping 90ml of 28% ammonia water into the organic phase at 10-15 ℃, reacting at room temperature for 3h after dripping, standing, removing water, adding water again, carrying out azeotropic distillation at normal pressure to remove solvent dichlorobenzene, filtering, and recrystallizing a filter cake with ethanol to obtain 85g (0.34mol) of phenyl p-hydroxybenzoate with the yield of 94.4%;
(3) adding 85g (0.34mol) of phenyl p-hydroxybenzoate and 53g (0.4mol) of aluminum trichloride into 200ml of anhydrous carbon disulfide, stirring, heating, refluxing for 6 hours, cooling to 30 ℃, pouring into 300ml of ice water in a trickle manner, standing, removing water, and washing to neutrality; distilling under normal pressure to remove solvent carbon disulfide, and recrystallizing with ethanol-water (1: 3) to obtain white crystal 4, 4-dihydroxy benzophenone 71g (0.33mol), with yield of 97%;
(4) to 250ml of acetone were charged 71g (0.33mol) of 4, 4-dihydroxybenzophenone, 35g (0.25mol) of potassium carbonate, 116g (0.7mol) of 1-bromohexane, and 4.5g (0.014mol) of tetrabutylammonium bromide, and the mixture was refluxed for 48 hours while being stirred at an elevated temperature to turn the reaction mixture from yellow-green to white. Distilling under normal pressure to remove solvent acetone, washing with water to remove salt, and recrystallizing with ethanol to obtain white flaky crystal product 4, 4-di-hexyloxy benzophenone. 118.4g (0.31mol), yield 92%; content (HPLC method): 99.5 percent; the melting point is 104.2-104.8 ℃.
Example 2:
(1) adding 51.8g (0.375mol) of p-hydroxybenzoic acid into 100ml of cyclohexane, dripping 36.10g (0.46mol) of acetyl chloride at the temperature of 30-35 ℃, and carrying out heat preservation reaction for 2h at the temperature of 35-40 ℃ after dripping. Distilling under normal pressure to recover excessive acetyl chloride and cyclohexane solvent, adding ethanol for recrystallization to obtain 65.4g of p-acetoxybenzoic acid with a yield of 97%;
(2) sequentially adding 65.4g (0.36mol) of p-acetoxybenzoic acid, 37.7g (0.4mol) of phenol, 67.5(0.44mol) of phosphorus oxychloride and 98g (0.72mol) of zinc chloride into 180ml of dichlorobenzene, carrying out heat preservation reaction at 65-70 ℃ for 2 hours, cooling to 30 ℃, pouring trickle into 300ml of ice water, standing for dewatering, and washing with water to be neutral; dripping 90ml of 28% ammonia water into the organic phase at 10-15 ℃, reacting at room temperature for 3h after dripping, standing, removing water, adding water again, carrying out azeotropic distillation at normal pressure to remove solvent dichlorobenzene, filtering, and recrystallizing a filter cake with ethanol to obtain 84.8g (0.34mol) of phenyl p-hydroxybenzoate with the yield of 94.3%;
(3) adding 84.8g (0.34mol) of phenyl p-hydroxybenzoate and 60g (0.45mol) of aluminum trichloride into 200ml of anhydrous carbon disulfide, stirring, heating, refluxing for 6 hours, cooling to 30 ℃, pouring into 300ml of ice water in a trickle manner, standing, removing water, and washing to neutrality; distilling under normal pressure to remove solvent carbon disulfide, and recrystallizing with ethanol-water (1: 3) to obtain white crystal 4, 4-dihydroxy benzophenone 71.2g (0.33mol), with yield of 97.1%;
(4) to 250ml of acetone were charged 71.2g (0.33mol) of 4, 4-dihydroxybenzophenone, 40g (0.28mol) of potassium carbonate, 116g (0.7mol) of 1-bromohexane and 5g (0.016mol) of tetrabutylammonium bromide, and the mixture was refluxed for 48 hours while being stirred at an elevated temperature, whereupon the reaction mixture turned from yellow-green to white. Distilling under normal pressure to remove solvent acetone, washing with water to remove salt, and recrystallizing with ethanol to obtain white flaky crystal product 4, 4-di-hexyloxy benzophenone. 118.3g (0.31mol), yield 92.1%; content (HPLC method) 99.6%; the melting point is 104.1-104.5 ℃.
Example 3:
(1) adding 51.8g (0.375mol) of p-hydroxybenzoic acid into 100ml of cyclohexane, dripping 34.50g (0.44mol) of acetyl chloride at the temperature of 30-35 ℃, and carrying out heat preservation reaction for 2h at the temperature of 35-40 ℃ after dripping. Distilling under normal pressure to recover excessive acetyl chloride and cyclohexane solvent, adding ethanol for recrystallization to obtain 65.5g of p-acetoxybenzoic acid with a yield of 97%;
(2) sequentially adding 65.5g (0.36mol) of p-acetoxybenzoic acid, 35.8g (0.39mol) of phenol, 66(0.43mol) of phosphorus oxychloride and 104g (0.73mol) of zinc chloride into 180ml of dichlorobenzene, carrying out heat preservation reaction at 65-70 ℃ for 2h, cooling to 30 ℃, pouring trickle into 300ml of ice water, standing for dewatering, and washing to be neutral; dropping 120ml of 28% ammonia water into the organic phase at 10-15 ℃, reacting at room temperature for 3h after dropping, standing, removing water, adding water again, carrying out azeotropic distillation at normal pressure to remove solvent dichlorobenzene, filtering, and recrystallizing a filter cake with ethanol to obtain 85g (0.34mol) of phenyl p-hydroxybenzoate with the yield of 94.4%;
(3) adding 85g (0.34mol) of phenyl p-hydroxybenzoate and 50g (0.38mol) of aluminum trichloride into 200ml of anhydrous carbon disulfide, stirring, heating, refluxing for 6 hours, cooling to 30 ℃, pouring into 300ml of ice water in a trickle manner, standing, removing water, and washing to neutrality; distilling under normal pressure to remove solvent carbon disulfide, and recrystallizing with ethanol-water (1: 3) to obtain white crystal 4, 4-dihydroxy benzophenone 71g (0.33mol), with yield of 97%;
(4) to 250ml of acetone were charged 71g (0.33mol) of 4, 4-dihydroxybenzophenone, 35g (0.25mol) of potassium carbonate, 124g (0.75mol) of 1-bromohexane and 6g (0.019mol) of tetrabutylammonium bromide, and the mixture was refluxed for 48 hours while being stirred at an elevated temperature, whereupon the reaction mixture turned from yellow-green to white. Distilling under normal pressure to remove solvent acetone, washing with water to remove salt, and recrystallizing with ethanol to obtain white flaky crystal product 4, 4-di-hexyloxy benzophenone. 118.5g (0.31mol), yield 92.1%; content (HPLC method): 99.5 percent; melting point is 104.5-105.0 ℃.
Example 4:
(1) adding 51.8g (0.375mol) of p-hydroxybenzoic acid into 100ml of cyclohexane, dripping 34.50g (0.45mol) of acetyl chloride at the temperature of 30-35 ℃, and carrying out heat preservation reaction for 2h at the temperature of 35-40 ℃ after dripping. Distilling under normal pressure to recover excessive acetyl chloride and cyclohexane solvent, adding ethanol for recrystallization to obtain 65.5g of p-acetoxybenzoic acid with a yield of 97%;
(2) sequentially adding 65.5g (0.36mol) of p-acetoxybenzoic acid, 35.8g (0.38mol) of phenol, 66(0.43mol) of phosphorus oxychloride and 104g (0.75mol) of zinc chloride into 180ml of dichlorobenzene, carrying out heat preservation reaction at 65-70 ℃ for 2h, cooling to 30 ℃, pouring trickle into 300ml of ice water, standing for dewatering, and washing to be neutral; dropping 120ml of 28% ammonia water into the organic phase at 10-15 ℃, reacting at room temperature for 3h after dropping, standing, removing water, adding water again, carrying out azeotropic distillation at normal pressure to remove solvent dichlorobenzene, filtering, and recrystallizing a filter cake with ethanol to obtain 85g (0.34mol) of phenyl p-hydroxybenzoate with the yield of 94.4%;
(3) adding 85g (0.34mol) of phenyl p-hydroxybenzoate and 50g (0.42mol) of aluminum trichloride into 200ml of anhydrous carbon disulfide, stirring, heating, refluxing for 6 hours, cooling to 30 ℃, pouring into 300ml of ice water in a trickle manner, standing, removing water, and washing to neutrality; distilling under normal pressure to remove solvent carbon disulfide, and recrystallizing with ethanol-water (1: 3) to obtain white crystal 4, 4-dihydroxy benzophenone 71g (0.33mol), with yield of 97%;
(4) to 250ml of acetone were charged 71g (0.33mol) of 4, 4-dihydroxybenzophenone, 35g (0.26mol) of potassium carbonate, 124g (0.72mol) of 1-bromohexane and 6g (0.016mol) of tetrabutylammonium bromide, and the mixture was stirred, heated and refluxed for 48 hours to turn the reaction mixture from yellow-green to white. Distilling under normal pressure to remove solvent acetone, washing with water to remove salt, and recrystallizing with ethanol to obtain white flaky crystal product 4, 4-di-hexyloxy benzophenone. 118.5g (0.31mol), yield 92.1%; content (HPLC method): 99.5 percent; melting point is 104.5-105.0 ℃.
Example 5:
(1) adding 51.8g (0.375mol) of p-hydroxybenzoic acid into 100ml of cyclohexane, dripping 34.50g (0.44mol) of acetyl chloride at the temperature of 30-35 ℃, and carrying out heat preservation reaction for 2h at the temperature of 35-40 ℃ after dripping. Distilling under normal pressure to recover excessive acetyl chloride and cyclohexane solvent, adding ethanol for recrystallization to obtain 65.5g of p-acetoxybenzoic acid with a yield of 97%;
(2) sequentially adding 65.5g (0.36mol) of p-acetoxybenzoic acid, 35.8g (0.39mol) of phenol, 66(0.43mol) of phosphorus oxychloride and 104g (0.74mol) of zinc chloride into 180ml of dichlorobenzene, carrying out heat preservation reaction at 65-70 ℃ for 2h, cooling to 30 ℃, pouring trickle into 300ml of ice water, standing for dewatering, and washing to be neutral; dropping 120ml of 28% ammonia water into the organic phase at 10-15 ℃, reacting at room temperature for 3h after dropping, standing, removing water, adding water again, carrying out azeotropic distillation at normal pressure to remove solvent dichlorobenzene, filtering, and recrystallizing a filter cake with ethanol to obtain 85g (0.34mol) of phenyl p-hydroxybenzoate with the yield of 94.4%;
(3) adding 85g (0.34mol) of phenyl p-hydroxybenzoate and 50g (0.38mol) of aluminum trichloride into 200ml of anhydrous carbon disulfide, stirring, heating, refluxing for 6 hours, cooling to 30 ℃, pouring into 300ml of ice water in a trickle manner, standing, removing water, and washing to neutrality; distilling under normal pressure to remove solvent carbon disulfide, and recrystallizing with ethanol-water (1: 3) to obtain white crystal 4, 4-dihydroxy benzophenone 71g (0.33mol), with yield of 97%;
(4) to 250ml of acetone were charged 71g (0.33mol) of 4, 4-dihydroxybenzophenone, 35g (0.27mol) of potassium carbonate, 124g (0.74mol) of 1-bromohexane and 6g (0.018mol) of tetrabutylammonium bromide, and the mixture was refluxed for 48 hours while being stirred at an elevated temperature, whereupon the reaction mixture turned from yellow-green to white. Distilling under normal pressure to remove solvent acetone, washing with water to remove salt, and recrystallizing with ethanol to obtain white flaky crystal product 4, 4-di-hexyloxy benzophenone. 118.5g (0.31mol), yield 92.1%; content (HPLC method): 99.5 percent; melting point is 104.5-105.0 ℃.
Claims (1)
1. A method for synthesizing an ultraviolet absorbent 4,4' -dihexyl benzophenone is characterized in that: the method comprises the following steps:
the step A specifically comprises the following steps: adding 0.375mol of p-hydroxybenzoic acid into cyclohexane, dripping 0.44-0.46 mol of acetyl chloride at 30-35 ℃, reacting for 2 hours at 35-40 ℃ after finishing dripping, distilling at normal pressure to recover excessive acetyl chloride and solvent cyclohexane, adding ethanol for recrystallization to obtain 0.36mol of p-acetoxybenzoic acid, wherein the yield is 97%;
the step B specifically comprises the following steps: sequentially adding 0.36mol of p-acetoxybenzoic acid, 0.38-0.40 mol of phenol, 0.43-0.44 mol of phosphorus oxychloride and 0.72-0.75 mol of zinc chloride into dichlorobenzene, carrying out heat preservation reaction at 65-70 ℃ for 2 hours, cooling to 30 ℃, pouring into ice water in a trickle manner, standing, removing water, and washing to be neutral; dripping 90-120 ml of 28% ammonia water into the organic phase at 10-15 ℃, reacting at room temperature for 3h after dripping, standing, removing water, adding water again, carrying out azeotropic distillation at normal pressure to remove solvent dichlorobenzene, filtering, and recrystallizing a filter cake with ethanol to obtain 0.34mol of phenyl p-hydroxybenzoate with the yield of 94.4%;
the step C is specifically as follows: adding 0.34mol of phenyl p-hydroxybenzoate and 0.38-0.45 mol of aluminum trichloride into anhydrous carbon disulfide, stirring, heating, carrying out reflux reaction for 6 hours, cooling to 30 ℃, pouring into ice water in a trickle manner, standing, removing water, and washing to be neutral; removing the solvent carbon disulfide by atmospheric distillation, and carrying out distillation by using ethanol-water 1: 3, recrystallizing to obtain 0.33mol of white crystal 4, 4-dihydroxy benzophenone with the yield of 97 percent;
the step D is specifically as follows: adding 0.33mol of 4, 4-dihydroxy benzophenone, 0.25-0.28 mol of potassium carbonate, 0.70-0.75 mol of 1-bromohexane and 0.014-0.019 mol of tetrabutylammonium bromide into acetone, stirring, heating and refluxing for 48 hours, changing the reaction feed liquid from yellow green to white, distilling at normal pressure to remove solvent acetone, washing with water to remove salt, recrystallizing with ethanol to obtain 0.31mol of white flaky crystal product 4, 4-di-hexyloxy benzophenone, wherein the yield is more than or equal to 92%, and the content is more than or equal to 99.5% by using an HPLC method; melting point is 104.5-105.0 ℃.
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| CN1696094A (en) * | 2005-04-28 | 2005-11-16 | 武汉大学 | Method for preparing 4,4'-dihydroxy benzophenone |
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