CN103087023B - The preparation method of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester - Google Patents
The preparation method of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester Download PDFInfo
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- CN103087023B CN103087023B CN201310058469.6A CN201310058469A CN103087023B CN 103087023 B CN103087023 B CN 103087023B CN 201310058469 A CN201310058469 A CN 201310058469A CN 103087023 B CN103087023 B CN 103087023B
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Abstract
The preparation method of the present invention is a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester.The method is under vitriol oil existent condition; 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid (KA1) and P-hydroxybenzoic acid generation condensation reaction; this condenses is directly cured in buck and toluene; solidification terminates after point water; add catalyzer again; be obtained by reacting the pressure-sensitive orange of product (Orange) crude product, then obtain finished product through precipitation, refining methanol, oven dry.The inventive method is by adopting raw material 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid and P-hydroxybenzoic acid; and add reaction promotor Tetrabutyl amonium bromide; product yield can be improved widely, make product yield reach more than 85%.The inventive method technological design is reasonable, easy to operate, and industrial controllability is strong, and good product quality.
Description
Technical field
The present invention relates to a kind of preparation method that the present invention relates to pressure sensitive dye, the preparation method of '-carboxylic acid-6 '-(the diethylin)-3-oxo-ethyl ester that especially relates to a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2.
Background technology
In prior art, the pressure-sensitive orange orange spiral (isobenzofuran-1 (3H) of pressure sensitive dye, 9 '-[9H] xanthene) complicated process of preparation of-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, industrial operation poor controllability, quality product is not high, and yield is lower, only row reaches about 70%.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, there is provided a kind of technological design rationally, the preparation method of '-carboxylic acid-6 '-(the diethylin)-3-oxo-ethyl ester that effectively improves the spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 of final product quality and yield.
Technical problem to be solved by this invention is realized by following technical scheme.The preparation method of the present invention is a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, it is characterized in that, its step is as follows:
(1) in reaction vessel, adding mass concentration is 96%-103.5% sulfuric acid, evenly add 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1 again, temperature controls at 25-30 DEG C, and within 20-40 minute, dissolves completely to KA1 25-30 DEG C of stirring; Evenly add P-hydroxybenzoic acid again, temperature controls at 40-45 DEG C; The KA1 added and the weight ratio of P-hydroxybenzoic acid are 60:30-40; Then in 3-5 hour, be warmed up to 65-75 DEG C, and be incubated 1.5-2.5 hour; Then in 1.5-2.5 hour, be warmed up to 80-90 DEG C, and be incubated 1.5-2.5 hour; Obtain condenses;
(2) in reaction vessel, add appropriate water, and be heated to 70-75 DEG C, drip condenses, temperature is raised to 80-100 DEG C, by appropriate vitriol oil washing reaction container and addition funnel, then instills together in another reaction vessel, cools to 55-65 DEG C, filters; Wash filter cake with water, drain, obtain intermediate;
(3) in reaction vessel, appropriate water is added and mass concentration is the sodium hydroxide solution of 30-35%, add intermediate filter cake, add the sodium hydroxide solution stirring and adjusting pH to 7.5-9.0 of 30-35%, adding mass concentration after stirring is 15-25% sodium carbonate solution, catalyzer Tetrabutyl amonium bromide, add toluene, 0.5-1.5 hour is stirred at 20-30 DEG C, be warmed up to 35-45 DEG C, stir 2-4 hour, be warmed up to 45-55 DEG C, stir 0.5-1.5 hour, be warmed up to 75-85 DEG C, stir 7-9 hour, branch vibration layer, with appropriate water washing organic layer 1-3 time, add the water of appropriate 75-85 DEG C, underpressure distillation toluene, filter, appropriate washing, filtration obtains filter cake, the weight ratio of sodium carbonate solution, Tetrabutyl amonium bromide and toluene is 190-200:0.7-0.9:130-140,
(4) add filter cake and proper amount of methanol in a reservoir, stirred at ambient temperature, filter, methanol rinse is filtered, and obtains filter cake, dries, gets product.
In the step (1) of preparation method of the present invention, the KA1 added and the weight ratio of P-hydroxybenzoic acid are preferably 60:35.In step (3), the weight ratio of sodium carbonate solution, Tetrabutyl amonium bromide and toluene is preferably 195:0.8:135.
The inventive method is under vitriol oil existent condition; 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid (being also 4-diethylin ketone acid) KA1 and P-hydroxybenzoic acid generation condensation reaction; this condenses is directly cured in buck and toluene; solidification terminates after point water; add catalyzer again; obtain the pressure-sensitive orange of product (Orange) crude product, then obtain finished product through precipitation, refining methanol, oven dry.Its concrete technology route is as follows:
The present invention passes through the proportioning of preferred feedstock 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid and P-hydroxybenzoic acid; and add reaction promotor Tetrabutyl amonium bromide; product yield can be improved widely, make product yield reach more than 85%.Compared with prior art, the inventive method technological design is reasonable, easy to operate, and industrial controllability is strong, and good product quality.
Embodiment
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
The preparation method of embodiment 1, a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, its step is as follows:
(1) in reaction vessel, adding mass concentration is 96% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature controls at 25 DEG C, and within 20 minutes, dissolves completely to KA1 25 DEG C of stirrings; Evenly add P-hydroxybenzoic acid again, temperature controls at 40 DEG C; The KA1 added and the weight ratio of P-hydroxybenzoic acid are 60:30; Then in 3 hours, be warmed up to 65 DEG C, and be incubated 1.5 hours; Then in 1.5 hours, be warmed up to 80 DEG C, and be incubated 1.5 hours; Obtain condenses;
(2) in reaction vessel, add appropriate water, and be heated to 70 DEG C, drip condenses, temperature is raised to 80 DEG C, by appropriate vitriol oil washing reaction container and addition funnel, then instills together in another reaction vessel, cools to 55 DEG C, filters; Wash filter cake with water, drain, obtain intermediate;
(3) in reaction vessel, appropriate water is added and mass concentration is the sodium hydroxide solution of 30%, add intermediate filter cake, add the sodium hydroxide solution stirring and adjusting pH to 7.5 of 30%, adding mass concentration after stirring is 15% sodium carbonate solution, catalyzer Tetrabutyl amonium bromide, add toluene, 0.5-1.5 hour is stirred at 20 DEG C, be warmed up to 35 DEG C, stir 2 hours, be warmed up to 45 DEG C, stir 0.5 hour, be warmed up to 75 DEG C, stir 7 hours, branch vibration layer, with appropriate water washing organic layer 1 time, add the appropriate water of 75 DEG C, underpressure distillation toluene, filter, appropriate washing, filtration obtains filter cake, the weight ratio of sodium carbonate solution, Tetrabutyl amonium bromide and toluene is 190:0.7:130,
(4) add filter cake and proper amount of methanol in a reservoir, stirred at ambient temperature, filter, methanol rinse is filtered, and obtains filter cake, dries, gets product.
The preparation method of embodiment 2, a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, its step is as follows:
(1) in reaction vessel, adding mass concentration is 103.5% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature controls at 30 DEG C, and within 40 minutes, dissolves completely to KA1 30 DEG C of stirrings; Evenly add P-hydroxybenzoic acid again, temperature controls at 45 DEG C; The KA1 added and the weight ratio of P-hydroxybenzoic acid are 60:40; Then in 5 hours, be warmed up to 75 DEG C, and be incubated 2.5 hours; Then in 2.5 hours, be warmed up to 80-90 DEG C, and be incubated 2.5 hours; Obtain condenses;
(2) in reaction vessel, add appropriate water, and be heated to 75 DEG C, drip condenses, temperature is raised to 100 DEG C, by appropriate vitriol oil washing reaction container and addition funnel, then instills together in another reaction vessel, cools to 65 DEG C, filters; Wash filter cake with water, drain, obtain intermediate;
(3) in reaction vessel, appropriate water is added and mass concentration is the sodium hydroxide solution of 35%, add intermediate filter cake, add the sodium hydroxide solution stirring and adjusting pH to 9.0 of 35%, adding mass concentration after stirring is 25% sodium carbonate solution, catalyzer Tetrabutyl amonium bromide, add toluene, stir 1.5 hours at 30 DEG C, be warmed up to 45 DEG C, stir 4 hours, be warmed up to 55 DEG C, stir 1.5 hours, be warmed up to 85 DEG C, stir 9 hours, branch vibration layer, with appropriate water washing organic layer 3 times, add the appropriate water of 85 DEG C, underpressure distillation toluene, filter, appropriate washing, filtration obtains filter cake, the weight ratio of sodium carbonate solution, Tetrabutyl amonium bromide and toluene is 200:0.9:140,
(4) add filter cake and proper amount of methanol in a reservoir, stirred at ambient temperature, filter, methanol rinse is filtered, and obtains filter cake, dries, gets product.
The preparation method of embodiment 3, a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, its step is as follows:
(1) in reaction vessel, adding mass concentration is 98% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature controls at 28 DEG C, and within 30 minutes, dissolves completely to KA1 28 DEG C of stirrings; Evenly add P-hydroxybenzoic acid again, temperature controls at 42 DEG C; The KA1 added and the weight ratio of P-hydroxybenzoic acid are 60:25; Then in 4 hours, be warmed up to 70 DEG C, and be incubated 2 hours; Then in 2 hours, be warmed up to 85 DEG C, and be incubated 2 hours; Obtain condenses;
(2) in reaction vessel, add appropriate water, and be heated to 72 DEG C, drip condenses, temperature is raised to 90 DEG C, by appropriate vitriol oil washing reaction container and addition funnel, then instills together in another reaction vessel, cools to 60 DEG C, filters; Wash filter cake with water, drain, obtain intermediate;
(3) in reaction vessel, appropriate water is added and mass concentration is the sodium hydroxide solution of 32%, add intermediate filter cake, add the sodium hydroxide solution stirring and adjusting pH to 8.0 of 32%, adding mass concentration after stirring is 20% sodium carbonate solution, catalyzer Tetrabutyl amonium bromide, add toluene, stir 2 hours at 25 DEG C, be warmed up to 40 DEG C, stir 3 hours, be warmed up to 50 DEG C, stir 1 hour, be warmed up to 80 DEG C, stir 8 hours, branch vibration layer, with appropriate water washing organic layer 2 times, add the appropriate water of 80 DEG C, underpressure distillation toluene, filter, appropriate washing, filtration obtains filter cake, the weight ratio of sodium carbonate solution, Tetrabutyl amonium bromide and toluene is 195:0.8:135,
(4) add filter cake and proper amount of methanol in a reservoir, stirred at ambient temperature, filter, methanol rinse is filtered, and obtains filter cake, dries, gets product.
The preparation experiment of embodiment 4, spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester:
To in 250ml flask, add 188 98% sulfuric acid, with 2-3 hour, evenly add KA1 60g, temperature controls at 25-30 DEG C, and stirs 30 minutes at 25-30 DEG C, guarantees that KA1 dissolves completely.With 1 hour, evenly add P-hydroxybenzoic acid 35g, temperature controls at 40-45 DEG C.
70 DEG C are slowly warmed up to 4 hours, and 70 DEG C of insulations 2 hours.85 DEG C are slowly warmed up to 2 hours, and 85 DEG C of insulations 2 hours.Obtain condenses.
To in 500ml flask, add water 234g, and be heated to 70-75 DEG C, drip condenses CRM, allowable temperature is raised to 80-100 DEG C, and controls in this temperature range, after dripping, by 20g vitriol oil washing 250ml flask and addition funnel, instill together in 500ml flask.Cool to 60 DEG C, and filter.95g*2 cold water washing filter cake, drains, obtains intermediate.
To in 1000ml flask, add water 117g, 49.5g 32% sodium hydroxide solution, add intermediate filter cake above, stirring and adjusting PH, add 32% sodium hydroxide solution of about 10g, control PH=8.5, stir 1 hour, add 195g 17% sodium carbonate solution, 0.8g catalyzer, add 135g toluene, stir 1 hour at 20-30 DEG C, be warmed up to 40 DEG C, stir 3 hours, be warmed up to 50 DEG C, stir 1 hour, be warmed up to 80 DEG C, stir 8 hours, branch vibration layer, 95g*2 water washing organic layer, add 95g80 DEG C of hot water, underpressure distillation toluene, filter, 40g washes, filtration obtains filter cake.
Add filter cake and 115g methyl alcohol in 500ml flask, stir 1 hour in room temperature, filter, 55g methanol rinse is filtered, and obtains filter cake 90g and dries 83.5g, yield 85%.
Claims (1)
1. the preparation method of a spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, it is characterized in that, its step is as follows:
(1) in reaction vessel, adding mass concentration is 98% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature controls at 28 DEG C, and within 30 minutes, dissolves completely to KA1 28 DEG C of stirrings; Evenly add P-hydroxybenzoic acid again, temperature controls at 42 DEG C; The KA1 added and the weight ratio of P-hydroxybenzoic acid are 60:25; Then in 4 hours, be warmed up to 70 DEG C, and be incubated 2 hours; Then in 2 hours, be warmed up to 85 DEG C, and be incubated 2 hours; Obtain condenses;
(2) in reaction vessel, add appropriate water, and be heated to 72 DEG C, drip condenses, temperature is raised to 90 DEG C, by appropriate vitriol oil washing reaction container and addition funnel, then instills together in another reaction vessel, cools to 60 DEG C, filters; Wash filter cake with water, drain, obtain intermediate;
(3) product ethyl sulfate esterification step (2) obtained: add appropriate water and mass concentration is the sodium hydroxide solution of 32% in reaction vessel, add intermediate filter cake, add the sodium hydroxide solution stirring and adjusting pH to 8.0 of 32%, adding mass concentration after stirring is 20% sodium carbonate solution, catalyzer Tetrabutyl amonium bromide, add toluene, stir 2 hours at 25 DEG C, be warmed up to 40 DEG C, stir 3 hours, be warmed up to 50 DEG C, stir 1 hour, be warmed up to 80 DEG C, stir 8 hours, branch vibration layer, with appropriate water washing organic layer 2 times, add the appropriate water of 80 DEG C, underpressure distillation toluene, filter, appropriate washing, filtration obtains filter cake, the weight ratio of sodium carbonate solution, Tetrabutyl amonium bromide and toluene is 195:0.8:135,
(4) add filter cake and proper amount of methanol in a reservoir, stirred at ambient temperature, filter, methanol rinse is filtered, and obtains filter cake, dries, gets product.
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| US5395948A (en) * | 1992-03-17 | 1995-03-07 | Ciba-Geigy Corporation | Fluoran color formers |
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| EP0727411A2 (en) * | 1995-02-14 | 1996-08-21 | Ciba-Geigy Ag | Process for the preparation of diphenylamines |
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