CN102286211B - Method for preparing acid orange-12 - Google Patents
Method for preparing acid orange-12 Download PDFInfo
- Publication number
- CN102286211B CN102286211B CN 201110225287 CN201110225287A CN102286211B CN 102286211 B CN102286211 B CN 102286211B CN 201110225287 CN201110225287 CN 201110225287 CN 201110225287 A CN201110225287 A CN 201110225287A CN 102286211 B CN102286211 B CN 102286211B
- Authority
- CN
- China
- Prior art keywords
- naphthol
- sodium
- solution
- acid orange
- indicator
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Coloring Foods And Improving Nutritive Qualities (AREA)
Abstract
The invention relates to a method for preparing acid orange-12, which comprises: performing beta-naphthol and concentrated sulfuric acid to obtain beta-naphthol-6-sodium sulfonate; performing diazotization of phenylamine and sodium nitrite to obtain benzene diazonium chloride; and performing coupling reaction of beta-naphthol-6-sodium sulfonate and benzene diazonium chloride to obtain the finished acid orange-12. The acid orange-12 provided by the invention can be well used in a direct implant-bone contact (DBC) process as a coloring agent, and can make protein and lysine measurement work easy, accurate and quick; and being water soluble, thermostable and insusceptible to ions of metals such as lead, calcium, manganese, copper and aluminum, the acid orange-12 can be used for coloring all food such as cakes, candies, wines, ice cream, beverage, cans, preserved fruits and the like and also can be used for coloring medicines. The acid orange-12 is high-performance coloring agent.
Description
Technical field
The invention belongs to field of fine chemical, especially a kind of preparation method of von Muller's indicator-12.
Technical background
Along with the development of nutrition science, the content of measuring protein in cereal, food and feeds, Methionin needs a kind of accurate, simple and easy, quick, low consumed analytical procedure to reach the parent material that filters out as soon as possible high protein, high-lysine.Von Muller's indicator-12 are 6-hydroxyl-5-(phenylazo-)-2-naphthene sulfonic acid, as the application of staining agent in staining method (being called for short the DBC method), make not only that in the analysis of crop protein and soil, the mensuration work of Nitrogen element and Methionin becomes simple and easy, accurate, quick, and successfully be applied to the analysis of the crop protein such as wheat class, corn, Chinese sorghum, millet, soybean and paddy, thereby this compound has been caused enough attention.
Along with the stdn of the DBC method of measuring protein, Methionin with apply, demand to staining agent von Muller's indicator-12 increases day by day, not only to develop the high-content reagent that does not contain foreign pigment, and a reasonable process that can manufacture will be provided, to satisfy domestic market demand.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, the preparation method of a kind of von Muller's indicator-12 is provided, present method has the advantages that preparation cycle is short, cost is low, purity is high.
The present invention realizes that the technical scheme of purpose is as follows:
Advantage of the present invention and positively effect are as follows:
1, the preparation method's of this von Muller's indicator-12 technique is simple, easy handling, and owing to adopting the vitriol oil to carry out Direct Sulfonation, therefore the reaction times with traditional sulfonation reaction foreshortened to 0.5-1 hour by 6 hours, greatly reduced cost.
2, von Muller's indicator provided by the invention-12 are well used in the DBC method as staining agent, make the mensuration work of protein and Methionin become simple and easy, accurate, quick, because it is soluble in water, to thermally-stabilised, be not subjected to the cation recognitions such as lead, calcium, manganese, copper, aluminium, can be used for the dyeing of all food, as cake, candy, drinks, ice-creams, beverage, can, preserved fruit etc., also can be used for the dyeing of medicine, is the efficient staining agent of a kind of performance.
Embodiment:
Below in conjunction with embodiment, the present invention is further described, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1:
The preparation method of a kind of von Muller's indicator-12, proportioning raw materials:
Concrete operation step is as follows:
(1) sulfonation: agitator is being housed, thermometer, add the 1305ml vitriol oil in the reaction flask of condenser, be heated to 90 ℃ in water-bath, under agitation add the 900g 2-Naphthol in batches, temperature of reaction is no more than 90 ℃, be warmed up to 100 ℃ after adding, stirred 1 hour, be cooled to 25 ℃, transfer PH=7.8 with 10N sodium hydroxide, consume the 3920ml sodium hydroxide solution, the white precipitate that filtration is separated out is crude product, carrying out recrystallization with 6000ml distilled water, to obtain the white plates crystallization be 2-Naphthol-6-sodium sulfonate, be placed in loft drier dry, temperature can not be over 110 ℃, after dry, weight is about 443g.
(2) diazotization: 51ml aniline and the solution of 40ml water are mixed generating anilinechloride in the reaction flask that agitator, thermometer, dropping funnel are housed with the 129ml concentrated hydrochloric acid, bathe with cryosel and be cooled to 0 ℃; Separately the 36g Sodium Nitrite is dissolved in 87ml water bathing with cryosel and is cooled to below 0 ℃, this solution slowly is added drop-wise in anilinechloride, temperature is no more than 5 ℃.With starch potassium iodide trial-production check terminal point, test paper becomes blueness and namely stops dripping sodium nitrite solution when dripping off soon, and the benzene diazonium chloride diazo benzene chloride that generate this moment is jonquilleous clear solution, then continues to stir 0.5 hour, and is stand-by in 0--5 ℃ of preservation.
(3) coupling: the 2-Naphthol that in the reaction flask that agitator, thermometer, dropping funnel are housed, sulfonation is generated-6-sodium sulfonate 120g is dissolved in the 6000ml aqueous solution of the 180g sodium carbonate for preparing in advance, PH=10.5, be down to 0 ℃, slowly drip benzene diazonium chloride diazo benzene chloride, temperature maintains 0--3 ℃, and in reaction, PH remains on 8-9.Drip off and transfer PH=4.5 with hydrochloric acid afterwards, continue to stir 1 hour, filter and obtain mauve crude product dyestuff 150g, obtain approximately 120g of finished product von Muller's indicator-12 with the 60 ℃ of dryings in vacuum drying oven of sterling after the 2250ml ethyl alcohol recrystallization.
Embodiment 2:
The preparation method of a kind of von Muller's indicator-12, proportioning raw materials:
Concrete operation step is as follows:
(1) sulfonation: add the 1308ml vitriol oil in the reaction flask that agitator, thermometer, condenser are housed, be heated to 88 ℃ in water-bath, under agitation add 900g 2-Naphthol, temperature of reaction to be no more than 90 ℃ in batches, be warmed up to 100 ℃ after adding, stirred 0.5 hour.Be cooled to 23 ℃, transfer PH=8.2 with 10N sodium hydroxide, consume the 3980ml sodium hydroxide solution, the white precipitate that filtration is separated out is crude product, carrying out recrystallization with 6000ml distilled water, to obtain the white plates crystallization be 2-Naphthol-6-sodium sulfonate, be placed in loft drier dry, temperature can not surpass 110 ℃, and dry rear weight is about 447g.
(2) diazotization: 51ml aniline and the solution of 40ml water are mixed generating anilinechloride in the reaction flask that agitator, thermometer, dropping funnel are housed with the 129ml concentrated hydrochloric acid, bathe with cryosel and be cooled to 0 ℃; Separately the 37g Sodium Nitrite is dissolved in 87ml water bathing with cryosel and is cooled to below 0 ℃, this solution slowly is added drop-wise in anilinechloride, temperature is no more than 5 ℃.With starch potassium iodide trial-production check terminal point, test paper becomes blueness and namely stops dripping sodium nitrite solution when dripping off soon, and the benzene diazonium chloride diazo benzene chloride that generate this moment is jonquilleous clear solution, then continues to stir 0.5 hour, and is stand-by in 0--5 ℃ of preservation.
(3) coupling: the 2-Naphthol that in the reaction flask that agitator, thermometer, dropping funnel are housed, sulfonation is generated-6-sodium sulfonate 120g is dissolved in the 6000ml aqueous solution of the 180g sodium carbonate for preparing in advance, PH=11, be down to 0 ℃, slowly drip benzene diazonium chloride diazo benzene chloride, temperature maintains 0--3 ℃, and in reaction, PH remains on 8-9.Drip off and transfer PH=4 with hydrochloric acid afterwards, continue to stir 1 hour, filter and obtain mauve crude product dyestuff 148g, obtain approximately 118g of finished product von Muller's indicator-12 with the 60 ℃ of dryings in vacuum drying oven of sterling after the 2220ml ethyl alcohol recrystallization.
Embodiment 3:
The preparation method of a kind of von Muller's indicator-12, proportioning raw materials:
Concrete operation step is as follows:
(1) sulfonation: add the 1310ml vitriol oil in the reaction flask that agitator, thermometer, condenser are housed, be heated to 85 ℃ in water-bath, under agitation add 900g 2-Naphthol, temperature of reaction to be no more than 90 ℃ in batches, be warmed up to 100 ℃ after adding, stirred 1 hour.Be cooled to 25 ℃, transfer PH=8.5 with 10N sodium hydroxide, consume the 4150ml sodium hydroxide solution, the white precipitate that filtration is separated out is crude product, carrying out recrystallization with 6000ml distilled water, to obtain the white plates crystallization be 2-Naphthol-6-sodium sulfonate, be placed in loft drier dry, temperature can not surpass 110 ℃, and dry rear weight is about 450g.
(2) diazotization: 51ml aniline and the solution of 40ml water are mixed generating anilinechloride in the reaction flask that agitator, thermometer, dropping funnel are housed with the 129ml concentrated hydrochloric acid, bathe with cryosel and be cooled to 0 ℃; Separately the 36g Sodium Nitrite is dissolved in 87ml water bathing with cryosel and is cooled to below 0 ℃, this solution slowly is added drop-wise in anilinechloride, temperature is no more than 5 ℃.With starch potassium iodide trial-production check terminal point, test paper becomes blueness and namely stops dripping sodium nitrite solution when dripping off soon, and the benzene diazonium chloride diazo benzene chloride that generate this moment is jonquilleous clear solution, then continues to stir 0.5 hour, and is stand-by in 0--5 ℃ of preservation.
(3) coupling: the 2-Naphthol that in the reaction flask that agitator, thermometer, dropping funnel are housed, sulfonation is generated-6-sodium sulfonate 120g is dissolved in the 6000ml aqueous solution of the 180g sodium carbonate for preparing in advance, PH=10.5, be down to 0 ℃, slowly drip benzene diazonium chloride diazo benzene chloride, temperature maintains 2--5 ℃, and in reaction, PH remains on 8-9.Drip off and transfer PH=4.5 with hydrochloric acid afterwards, continue to stir 1 hour, filter and obtain mauve crude product dyestuff 150g, obtain approximately 125g of finished product von Muller's indicator-12 with the 60 ℃ of dryings in vacuum drying oven of sterling after the 2325ml ethyl alcohol recrystallization.
The simultaneous test data.
| Denmark's sample | This institute sample | |
| Purity | 86％ | 94.06％ |
| PH value during molecular balance | 1.66 | 1.84 |
Claims (2)
1. the preparation method of von Muller's indicator-12, it is characterized in that: step is as follows:
⑴ sulfonation: add the vitriol oil in reaction flask, be heated to 80-90 ℃ in water-bath, under agitation add 2-Naphthol, temperature of reaction to be no more than 90 ℃ in batches, be warmed up to 100 ℃ after adding, stirred 0.5-1 hour, and be cooled to 20--25 ℃, transfer pH=7.5-8.5, the white precipitate that filtration is separated out, it is 2-Naphthol-6-sodium sulfonate that recrystallization obtains the white plates crystallization, drying, and temperature can not be over 110 ℃;
⑵ diazotization: aniline-water solution is mixed generating anilinechloride in reaction flask with concentrated hydrochloric acid, bathe and be cooled to 0 ℃; Separately sodium nitrite in aqueous solution is cooled to below 0 ℃, sodium nitrite solution is added drop-wise in anilinechloride, temperature is no more than 5 ℃, check terminal point with starch potassium iodide paper when dripping off soon, test paper becomes blueness and namely stops dripping sodium nitrite solution, the benzene diazonium chloride diazo benzene chloride that generate this moment is jonquilleous clear solution, then continues to stir 0.5 hour, and is stand-by in 0-5 ℃ of preservation;
⑶ coupling: in reaction flask, 2-Naphthol-6-sodium sulfonate is dissolved in sodium carbonate solution, pH=10-11, be down to 0 ℃, slowly drip benzene diazonium chloride diazo benzene chloride, temperature maintains 0-5 ℃, in reaction, pH remains on 8-9, drip off rear accent pH=4-5, continue to stir 0.5-1.5 hour, filter and obtain mauve crude product dyestuff, with after ethyl alcohol recrystallization in vacuum drying oven 60 ℃ of dryings obtain finished product von Muller's indicator-12, the consumption of described each component is as follows:
2-Naphthol 900 g
Vitriol oil 1300-1310 ml
10N sodium hydroxide 3900--4200 ml
Aniline 51 ml
Sodium Nitrite 36-38 g
Concentrated hydrochloric acid 129--130 ml
Sodium carbonate 180-200 g
Ethanol 2100-2400 ml
What described adjusting pH=7.5-8.5 used is 10N sodium hydroxide.
2. the preparation method of von Muller's indicator according to claim 1-12, it is characterized in that: described reaction flask is equipped with agitator, thermometer and condenser.
3, the preparation method of von Muller's indicator according to claim 1-12 is characterized in that: described concentrated hydrochloric acid consumption is 129--130 ml.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110225287 CN102286211B (en) | 2011-08-08 | 2011-08-08 | Method for preparing acid orange-12 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110225287 CN102286211B (en) | 2011-08-08 | 2011-08-08 | Method for preparing acid orange-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102286211A CN102286211A (en) | 2011-12-21 |
| CN102286211B true CN102286211B (en) | 2013-06-19 |
Family
ID=45332977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110225287 Expired - Fee Related CN102286211B (en) | 2011-08-08 | 2011-08-08 | Method for preparing acid orange-12 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102286211B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3640733A (en) * | 1969-12-10 | 1972-02-08 | Allied Chem | Edible substrates colored with monoazo dyestuffs |
| US3994963A (en) * | 1975-02-28 | 1976-11-30 | American Cyanamid Company | Schaeffer salt purification |
| US6387170B1 (en) * | 2000-08-28 | 2002-05-14 | Dominion Colour Corporation | Heat stable orange laked monoazo pigment |
| CN1507475A (en) * | 2001-05-09 | 2004-06-23 | 科莱恩有限公司 | Laked monoazo pigments based on naphtholsulfonic acids |
| CN1836014A (en) * | 2003-08-11 | 2006-09-20 | 佳能株式会社 | Ink, recording method, recording unit, ink cartridge, and recording device |
| CN101333339A (en) * | 2007-06-26 | 2008-12-31 | 上海染料研究所有限公司 | Preparation method for enhancing yield of edible sunset yellow |
-
2011
- 2011-08-08 CN CN 201110225287 patent/CN102286211B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3640733A (en) * | 1969-12-10 | 1972-02-08 | Allied Chem | Edible substrates colored with monoazo dyestuffs |
| US3994963A (en) * | 1975-02-28 | 1976-11-30 | American Cyanamid Company | Schaeffer salt purification |
| US6387170B1 (en) * | 2000-08-28 | 2002-05-14 | Dominion Colour Corporation | Heat stable orange laked monoazo pigment |
| CN1507475A (en) * | 2001-05-09 | 2004-06-23 | 科莱恩有限公司 | Laked monoazo pigments based on naphtholsulfonic acids |
| CN1836014A (en) * | 2003-08-11 | 2006-09-20 | 佳能株式会社 | Ink, recording method, recording unit, ink cartridge, and recording device |
| CN101333339A (en) * | 2007-06-26 | 2008-12-31 | 上海染料研究所有限公司 | Preparation method for enhancing yield of edible sunset yellow |
Non-Patent Citations (2)
| Title |
|---|
| 周春隆.酸性染料用中间体及杂环、金属络合酸性染料进展.《染料工业》.1993,第30卷(第6期),1-13. |
| 酸性染料用中间体及杂环、金属络合酸性染料进展;周春隆;《染料工业》;19931231;第30卷(第6期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102286211A (en) | 2011-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sompong et al. | Physicochemical and antioxidative properties of red and black rice varieties from Thailand, China and Sri Lanka | |
| CN105166862B (en) | The preparation method of high stability cellulose base natural edible anthocyania pigment compound | |
| Asaduzzaman et al. | Recovery of functional materials with thermally stable antioxidative properties in squid muscle hydrolyzates by subcritical water | |
| CN104120160A (en) | Preparation method for chlorella anti-oxidative peptide | |
| CN101869261B (en) | Method for manufacturing water-soluble lutein ester | |
| CN101156661A (en) | A debitterizing method of proteolysis matter | |
| CN105153099A (en) | Method for extracting procyanidins (OPC) from pitaya peels | |
| CN104530053A (en) | Preparation method of medicinal crystal form tofacitinib citrate | |
| CN103554976A (en) | Red reactive dye and preparation method thereof | |
| CN102286211B (en) | Method for preparing acid orange-12 | |
| CN102002110A (en) | Preparation method of polysaccharides from sea cucumber | |
| CN102617374B (en) | Method for preparing betaine hydrochloride | |
| CN101735032A (en) | Method for preparing sodium diacetate | |
| CN106748845B (en) | A kind of preparation method of L-carnitine salt micro mist | |
| CN108783452A (en) | A kind of preparation method of aloe extract | |
| JP2009201383A (en) | Functional food | |
| CN103145645A (en) | Preparation technology of mercapto-5-methyl-1,3,4-thiadiazole | |
| CN102150901B (en) | Method for reusing residual starch water from gluten manufacture | |
| CN101878851B (en) | Method for preparing peanut protein and soybean protein composite gel | |
| CN101838229B (en) | Method for separating and purifying all-trans xanthophyl powder | |
| CN103627764A (en) | Method for preparing antioxidant peptide by stepwise enzymolysis of corn germ meal | |
| CN108308492A (en) | A kind of preparation method of highly dissoluble plant polyphenol kind solid beverage | |
| CN101248892B (en) | Sea-tangle sesame paste | |
| CN103446185A (en) | Method for preparing soluble pearl calcium by use of pearl shells | |
| CN100429235C (en) | Process for preparing water soluble soybean polysaccharide with bean pulp and bean dreg as raw materials |
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 | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 300240 Tianjin Admiralty street Dongli District Xu Zhuangzi Patentee after: TIANJIN CHEMICAL REAGENT RESEARCH INSTITUTE CO., LTD. Address before: 300240 Tianjin Admiralty street Dongli District Xu Zhuangzi Patentee before: Tianjin chemical research institute |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130619 Termination date: 20160808 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |