CN103087023A - Method for preparing helico-(isobenzofuran-1(3H),9'-[9H]xanthene)-2'-carboxylic acid-6'-(diethylamino)-3-oxo-ethyl ester - Google Patents
Method for preparing helico-(isobenzofuran-1(3H),9'-[9H]xanthene)-2'-carboxylic acid-6'-(diethylamino)-3-oxo-ethyl ester Download PDFInfo
- Publication number
- CN103087023A CN103087023A CN2013100584696A CN201310058469A CN103087023A CN 103087023 A CN103087023 A CN 103087023A CN 2013100584696 A CN2013100584696 A CN 2013100584696A CN 201310058469 A CN201310058469 A CN 201310058469A CN 103087023 A CN103087023 A CN 103087023A
- Authority
- CN
- China
- Prior art keywords
- hour
- add
- warmed
- appropriate
- filter cake
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing helico-(isobenzofuran-1(3H),9'-[9H]xanthene)-2'-carboxylic acid-6'-(diethylamino)-3-oxo-ethyl ester. The method comprises the following steps of: in the presence of concentrated sulfuric acid, performing condensation reaction on 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid (KA1) and p-hydroxybenzoic acid; directly curing the condensate into lye and methylbenzene; separating water after curing; adding a catalyst for reaction to obtain a pressure-sensitive orange crude product; and performing desolution, methanol refining and drying to obtain a finished product. According to the method, the raw materials of the 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid and the p-hydroxybenzoic acid are adopted, and a reaction promoter tetrabutylammonium bromide is added, so that the product yield can be greatly improved and reaches more than 85 percent. The method is reasonable in process design, convenient to operate, strong in industrial controllability and good in product quality.
Description
Technical field
The present invention relates to a kind of preparation method who the present invention relates to pressure sensitive dye, especially relate to the preparation method of a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester.
Background technology
In prior art, the pressure-sensitive orange orange spiral of pressure sensitive dye (isobenzofuran-1 (3H), 9 '-[9H] xanthene) complicated process of preparation of-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, the industrial operation poor controllability, quality product is not high, and yield is lower, and only row reaches 70% left and right.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, the preparation method of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester that a kind of technological design rationally, effectively improves final product quality and yield is provided.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is the preparation method of 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) adding mass concentration in the reaction vessel is 96%-103.5% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature is controlled at 25-30 ℃, and stirs at 25-30 ℃ and dissolved fully to KA1 in 20-40 minute; Evenly add P-hydroxybenzoic acid, temperature is controlled at 40-45 ℃ again; The KA1 that adds and the weight ratio of P-hydroxybenzoic acid are 60:30-40; Then be warmed up to 65-75 ℃ in 3-5 hour, and be incubated 1.5-2.5 hour; Then be warmed up to 80-90 ℃ in 1.5-2.5 hour, and be incubated 1.5-2.5 hour; Obtain condenses;
(2) add appropriate water in reaction vessel, and be heated to 70-75 ℃, drip condenses, temperature is raised to 80-100 ℃, with appropriate vitriol oil washing reaction container and addition funnel, then splashes into together in another reaction vessel, cools to 55-65 ℃, filters; Wash filter cake with water, drain, obtain intermediate;
(3) adding appropriate water and mass concentration in the reaction vessel is the sodium hydroxide solution of 30-35%, add the intermediate filter cake, the sodium hydroxide solution stirring and adjusting pH to 7.5-9.0 that adds 30-35%, adding mass concentration after stirring is the 15-25% sodium carbonate solution, the catalyzer Tetrabutyl amonium bromide, add toluene, stirred 0.5-1.5 hour at 20-30 ℃, be warmed up to 35-45 ℃, stirred 2-4 hour, be warmed up to 45-55 ℃, stirred 0.5-1.5 hour, be warmed up to 75-85 ℃, stirred 7-9 hour, branch vibration layer, with appropriate water washing organic layer 1-3 time, the water that adds appropriate 75-85 ℃, 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 appropriate methyl alcohol in container, stir under room temperature, filter, methanol rinse is filtered, and obtains filter cake, and oven dry gets product.
In preparation method's of the present invention step (1), the KA1 that adds 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 the condition that the vitriol oil exists; 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid (being also 4-diethylin ketone acid) KA1 and P-hydroxybenzoic acid generation condensation reaction; this condenses directly is cured in buck and toluene; solidify and finish after minute water; add again catalyzer; 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 adds the reaction promotor Tetrabutyl amonium bromide, can improve widely product yield, and product yield is reached more than 85%.Compared with prior art, the inventive method technological design is reasonable, and is 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 consist of its Copyright law.
Embodiment 1, the preparation method of a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, and its step is as follows:
(1) adding mass concentration in the reaction vessel is 96% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature is controlled at 25 ℃, and stirs at 25 ℃ and dissolved fully to KA1 in 20 minutes; Evenly add P-hydroxybenzoic acid, temperature is controlled at 40 ℃ again; The KA1 that adds and the weight ratio of P-hydroxybenzoic acid are 60:30; Then be warmed up to 65 ℃ in 3 hours, and be incubated 1.5 hours; Then be warmed up to 80 ℃ in 1.5 hours, and be incubated 1.5 hours; Obtain condenses;
(2) add appropriate water in reaction vessel, and be heated to 70 ℃, drip condenses, temperature is raised to 80 ℃, with appropriate vitriol oil washing reaction container and addition funnel, then splashes into together in another reaction vessel, cools to 55 ℃, filters; Wash filter cake with water, drain, obtain intermediate;
(3) adding appropriate water and mass concentration in the reaction vessel is 30% sodium hydroxide solution, add the intermediate filter cake, add 30% sodium hydroxide solution stirring and adjusting pH to 7.5, adding mass concentration after stirring is 15% sodium carbonate solution, the catalyzer Tetrabutyl amonium bromide, add toluene, stirred 0.5-1.5 hour at 20 ℃, be warmed up to 35 ℃, stirred 2 hours, be warmed up to 45 ℃, stirred 0.5 hour, be warmed up to 75 ℃, stirred 7 hours, branch vibration layer, with appropriate water washing organic layer 1 time, add the appropriate water of 75 ℃, 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 appropriate methyl alcohol in container, stir under room temperature, filter, methanol rinse is filtered, and obtains filter cake, and oven dry gets product.
Embodiment 2, the preparation method of a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, and its step is as follows:
(1) adding mass concentration in the reaction vessel is 103.5% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature is controlled at 30 ℃, and stirs at 30 ℃ and dissolved fully to KA1 in 40 minutes; Evenly add P-hydroxybenzoic acid, temperature is controlled at 45 ℃ again; The KA1 that adds and the weight ratio of P-hydroxybenzoic acid are 60:40; Then be warmed up to 75 ℃ in 5 hours, and be incubated 2.5 hours; Then be warmed up to 80-90 ℃ in 2.5 hours, and be incubated 2.5 hours; Obtain condenses;
(2) add appropriate water in reaction vessel, and be heated to 75 ℃, drip condenses, temperature is raised to 100 ℃, with appropriate vitriol oil washing reaction container and addition funnel, then splashes into together in another reaction vessel, cools to 65 ℃, filters; Wash filter cake with water, drain, obtain intermediate;
(3) adding appropriate water and mass concentration in the reaction vessel is 35% sodium hydroxide solution, add the intermediate filter cake, add 35% sodium hydroxide solution stirring and adjusting pH to 9.0, adding mass concentration after stirring is 25% sodium carbonate solution, the catalyzer Tetrabutyl amonium bromide, add toluene, stirred 1.5 hours at 30 ℃, be warmed up to 45 ℃, stirred 4 hours, be warmed up to 55 ℃, stirred 1.5 hours, be warmed up to 85 ℃, stirred 9 hours, branch vibration layer, with appropriate water washing organic layer 3 times, add the appropriate water of 85 ℃, 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 appropriate methyl alcohol in container, stir under room temperature, filter, methanol rinse is filtered, and obtains filter cake, and oven dry gets product.
Embodiment 3, the preparation method of a kind of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, and its step is as follows:
(1) adding mass concentration in the reaction vessel is 98% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature is controlled at 28 ℃, and stirs at 28 ℃ and dissolved fully to KA1 in 30 minutes; Evenly add P-hydroxybenzoic acid, temperature is controlled at 42 ℃ again; The KA1 that adds and the weight ratio of P-hydroxybenzoic acid are 60:25; Then be warmed up to 70 ℃ in 4 hours, and be incubated 2 hours; Then be warmed up to 85 ℃ in 2 hours, and be incubated 2 hours; Obtain condenses;
(2) add appropriate water in reaction vessel, and be heated to 72 ℃, drip condenses, temperature is raised to 90 ℃, with appropriate vitriol oil washing reaction container and addition funnel, then splashes into together in another reaction vessel, cools to 60 ℃, filters; Wash filter cake with water, drain, obtain intermediate;
(3) adding appropriate water and mass concentration in the reaction vessel is 32% sodium hydroxide solution, add the intermediate filter cake, add 32% sodium hydroxide solution stirring and adjusting pH to 8.0, adding mass concentration after stirring is 20% sodium carbonate solution, the catalyzer Tetrabutyl amonium bromide, add toluene, stirred 2 hours at 25 ℃, be warmed up to 40 ℃, stirred 3 hours, be warmed up to 50 ℃, stirred 1 hour, be warmed up to 80 ℃, stirred 8 hours, branch vibration layer, with appropriate water washing organic layer 2 times, add the appropriate water of 80 ℃, 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 appropriate methyl alcohol in container, stir under room temperature, filter, methanol rinse is filtered, and obtains filter cake, and oven dry gets product.
Embodiment 4, the preparation experiment of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester:
In the 250ml flask, add 188 98% sulfuric acid, with 2-3 hour, evenly add KA1 60g, temperature is controlled at 25-30 ℃, and stirs 30 minutes at 25-30 ℃, guarantees that KA1 dissolves fully.With 1 hour, evenly add P-hydroxybenzoic acid 35g, temperature is controlled at 40-45 ℃.
Slowly be warmed up to 70 ℃ with 4 hours, and 70 ℃ of insulations 2 hours.Slowly be warmed up to 85 ℃ with 2 hours, and 85 ℃ of insulations 2 hours.Obtain condenses.
In the 500ml flask, add entry 234g, and be heated to 70-75 ℃, drip condenses CRM, allowable temperature is raised to 80-100 ℃, and is controlled in this temperature range, after dripping, with 20g vitriol oil washing 250ml flask and addition funnel, splash into together in the 500ml flask.Cool to 60 ℃, and filter.95g*2 cold water washing filter cake is drained, and obtains intermediate.
in the 1000ml flask, add entry 117g, 49.5g 32% sodium hydroxide solution, add top intermediate filter cake, stirring and adjusting PH, add 32% sodium hydroxide solution of 10g left and right, control PH=8.5, stirred 1 hour, add 195g 17% sodium carbonate solution, 0.8g catalyzer, add 135g toluene, stirred 1 hour at 20-30 ℃, be warmed up to 40 ℃, stirred 3 hours, be warmed up to 50 ℃, stirred 1 hour, be warmed up to 80 ℃, stirred 8 hours, branch vibration layer, 95g*2 water washing organic layer, add 95g80 ℃ of hot water, underpressure distillation toluene, filter, the 40g washing, filtration obtains filter cake.
Add filter cake and 115g methyl alcohol in the 500ml flask, stir 1 hour in room temperature, filter, the 55g methanol rinse is filtered, and obtains filter cake 90g oven dry 83.5g, yield 85%.
Claims (3)
1. the preparation method of a spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester, is characterized in that, its step is as follows:
(1) adding mass concentration in the reaction vessel is 96%-103.5% sulfuric acid, more evenly adds 2-(4-diethylamino-2-hydroxy benzoyl) phenylformic acid KA1, and temperature is controlled at 25-30 ℃, and stirs at 25-30 ℃ and dissolved fully to KA1 in 20-40 minute; Evenly add P-hydroxybenzoic acid, temperature is controlled at 40-45 ℃ again; The KA1 that adds and the weight ratio of P-hydroxybenzoic acid are 60:30-40; Then be warmed up to 65-75 ℃ in 3-5 hour, and be incubated 1.5-2.5 hour; Then be warmed up to 80-90 ℃ in 1.5-2.5 hour, and be incubated 1.5-2.5 hour; Obtain condenses;
(2) add appropriate water in reaction vessel, and be heated to 70-75 ℃, drip condenses, temperature is raised to 80-100 ℃, with appropriate vitriol oil washing reaction container and addition funnel, then splashes into together in another reaction vessel, cools to 55-65 ℃, filters; Wash filter cake with water, drain, obtain intermediate;
(3) adding appropriate water and mass concentration in the reaction vessel is the sodium hydroxide solution of 30-35%, add the intermediate filter cake, the sodium hydroxide solution stirring and adjusting pH to 7.5-9.0 that adds 30-35%, adding mass concentration after stirring is the 15-25% sodium carbonate solution, the catalyzer Tetrabutyl amonium bromide, add toluene, stirred 0.5-1.5 hour at 20-30 ℃, be warmed up to 35-45 ℃, stirred 2-4 hour, be warmed up to 45-55 ℃, stirred 0.5-1.5 hour, be warmed up to 75-85 ℃, stirred 7-9 hour, branch vibration layer, with appropriate water washing organic layer 1-3 time, the water that adds appropriate 75-85 ℃, 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 appropriate methyl alcohol in container, stir under room temperature, filter, methanol rinse is filtered, and obtains filter cake, and oven dry gets product.
2. preparation method according to claim 1, is characterized in that, in step (1), the KA1 that adds and the weight ratio of P-hydroxybenzoic acid are 60:35.
3. preparation method according to claim 1, is characterized in that, in step (3), the weight ratio of sodium carbonate solution, Tetrabutyl amonium bromide and toluene is 195:0.8:135.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310058469.6A CN103087023B (en) | 2013-02-25 | 2013-02-25 | The preparation method of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310058469.6A CN103087023B (en) | 2013-02-25 | 2013-02-25 | The preparation method of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103087023A true CN103087023A (en) | 2013-05-08 |
| CN103087023B CN103087023B (en) | 2015-09-16 |
Family
ID=48200205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310058469.6A Active CN103087023B (en) | 2013-02-25 | 2013-02-25 | The preparation method of spiral (isobenzofuran-1 (3H), 9 '-[9H] xanthene)-2 '-carboxylic acid-6 '-(diethylin)-3-oxo-ethyl ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103087023B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395948A (en) * | 1992-03-17 | 1995-03-07 | Ciba-Geigy Corporation | Fluoran color formers |
| EP0672730A1 (en) * | 1994-03-16 | 1995-09-20 | Ciba-Geigy Ag | Solid pastilles of mixtures of colour-formers |
| US5679856A (en) * | 1995-02-14 | 1997-10-21 | Ciba-Geigy Corporation | Process for preparing diphenylamines |
-
2013
- 2013-02-25 CN CN201310058469.6A patent/CN103087023B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5395948A (en) * | 1992-03-17 | 1995-03-07 | Ciba-Geigy Corporation | Fluoran color formers |
| EP0672730A1 (en) * | 1994-03-16 | 1995-09-20 | Ciba-Geigy Ag | Solid pastilles of mixtures of colour-formers |
| US5679856A (en) * | 1995-02-14 | 1997-10-21 | Ciba-Geigy Corporation | Process for preparing diphenylamines |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103087023B (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105237371B (en) | Method for preparing vanillin through catalytic oxidation degradation of lignin | |
| CN101328319A (en) | Water-soluble bridged ring polymethine 3H-indole cyanine dyes ultrasonic synthetic method | |
| CN106675789A (en) | Method for preparing biodiesel with low sulfur content from gutter oil | |
| CN103242205B (en) | Tri-monomer preparation method capable of reducing waste water production | |
| CN103450131B (en) | The preparation method of a kind of dehydroacetic acid (DHA) and sodium salt thereof | |
| CN111747840A (en) | Preparation method of 1, 4-naphthalenedicarboxylic acid | |
| CN105601512B (en) | A kind of high efficiency preparation method of gaultherolin | |
| CN100413928C (en) | Preparation technique of solvent red 179 | |
| CN107778175A (en) | The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two | |
| CN102295837B (en) | Preparation method for disperse yellow dye | |
| CN103436046A (en) | Method for preparing environment-friendly novel disperse blue 2BLN | |
| CN103087023A (en) | Method for preparing helico-(isobenzofuran-1(3H),9'-[9H]xanthene)-2'-carboxylic acid-6'-(diethylamino)-3-oxo-ethyl ester | |
| CN102633640B (en) | Integrated production technique of acetyl tributyl citrate (ATBC) | |
| CN114634410B (en) | Preparation method of paciclovir intermediate | |
| CN111484753A (en) | Sun-proof easy-to-wash red azo disperse dye and preparation method thereof | |
| CN102942543B (en) | Preparation method for 3-(Alpha-methoxy)methylenebenzofuran-2(3h)-one | |
| CN101717401B (en) | Preparing method of phthalocyaninatoaluminium chloride | |
| CN108640834A (en) | The synthesis technology of esmolol intermediate 3- (4- hydroxy phenyls) methyl propionate | |
| CN101735051B (en) | Method for preparing diisooctyl itaconate | |
| CN105732824A (en) | Preparation method of acetyl silk fibroin modified cellulose acetate | |
| CN1371899A (en) | Process for preparing propyl gallate | |
| CN104860834A (en) | Preparation method of disperse fluorescent dye intermediate 4-(N,N-diethylamino)salicylaldehyde | |
| CN102964411B (en) | Synthesis method of androstane-4,6-diene-17 alpha-methyl-17 beta-alcohol-3-ketone | |
| CN103626823B (en) | Technology for refining dehydropregnenolone acetate | |
| CN109810012B (en) | Preparation method of anhydrous solvent blue 122 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |