CN1237063C - Fluorescent brightening agent and synthesis method of its mixture - Google Patents
Fluorescent brightening agent and synthesis method of its mixture Download PDFInfo
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- CN1237063C CN1237063C CN 03110862 CN03110862A CN1237063C CN 1237063 C CN1237063 C CN 1237063C CN 03110862 CN03110862 CN 03110862 CN 03110862 A CN03110862 A CN 03110862A CN 1237063 C CN1237063 C CN 1237063C
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Abstract
The present invention relates to a fluorescent brightening agent and a synthesis method of a mixture. Stilbene-4, 4'-dual-imine ester hydrochloric salt and ortho-aminophenol or a derivative is used as raw materials; a closed loop is condensed in media of acid radical and monohydric alcohol for preparing the fluorescent brightening agent and a mixture of symmetrical and asymmetrical dibenzoxazine and distyrene. The proportion of the mixture can be adjusted by different material proportions. A product prepared by the method can be used for the fluorescent brightening treatment of synthetic or natural polymeric materials.
Description
Technical field
The present invention relates to the synthetic method of a kind of white dyes and composition thereof.
Background technology
The method of usually synthetic dibenzoxazine diphenyl ethene compounds is with 4,4 '-stilbenedicarboxylicacid acid is a raw material, become symmetrical compound with O-aminophenol derivatives through pyrocondensation after being translated into acyl chlorides, perhaps be condensed into asymmetric compound with the Ortho-Aminophenol of different substituents through secondary respectively.Its concrete preparation example has detailed introduction in U.S. Pat P 4282355.There is severe reaction conditions in this preparation method, and product purity is low, and synthesizing 4, produces obnoxious flavour in 4 '-stilbenedicarboxylicacid acid process, easily environment is worked the mischief.Introduced the method for benzoxazole benzyl muriate synthetic dibenzoxazine diphenyl ethylene derivatives under the effect of alkali among the U.S. Pat P 4508903, though overcome condition harshness in the above-mentioned technology, shortcoming that quantity of three wastes is big, only synthetic symmetrical compound.Chinese patent application CN 1315474A discloses the method for benzoxazole benzyl muriate synthetic symmetry and asymmetric dibenzoxazine toluylene mixture under the alkali effect and the fluorescent brightening that product is successfully used to synthetic or natural polymerization material has been handled; But still need use inflammable, explosive sodium hydride in the building-up process, production cost is higher simultaneously.
Summary of the invention
In order to satisfy industrial actual needs, simplify the operation condition, improve safety factors and further reduce material cost, the present invention proposes the method for a kind of brand-new synthetic symmetry and asymmetric dibenzoxazine toluylene white dyes and composition thereof.
The technology used in the present invention route is: the cyano group benzyl chloride in the presence of sodium hydroxide or potassium hydroxide, is condensed into 4,4 ' one dicyano toluylene; In alcohol, feed hydrogen chloride gas subsequently, obtain stilbazo, 4 '-diimine ester hydrochloride, structural formula is:
In the formula: X is methyl or ethyl.
With stilbazo, 4 '-diimine ester hydrochloride and single Ortho-Aminophenol or O-aminophenol derivatives act in the medium of organic acid and low unit alcohol, can obtain symmetric toluylene dibenzoxazine compound; Structural formula is:
In the formula: R is hydrogen, (C
1-C
4) alkyl or halogen.
With stilbazo, 4 '-diimine ester hydrochloride carries out above-mentioned reaction with different Ortho-Aminophenol and derivative thereof, can obtain symmetry and asymmetric dibenzoxazine toluylene mixture.
Different Ortho-Aminophenols and derivant structure formula thereof are respectively:
Symmetrical and asymmetric dibenzoxazine toluylene mixture has following general formula:
In the formula: R
1, R
2Difference is selected from hydrogen, (C respectively
1-C
4) alkyl, halogen.
Reaction obtains (c), (d) and (e) ternary mixture.Its ratio can be determined by adjusting raw material (a) and ingredient proportion (b) as required.
Concrete preparation method of the present invention is: to cyano group benzyl chloride dimerization reaction under alkaline condition, obtain 4,4 '-dicyano toluylene; Subsequently with 4,4 '-dicyano toluylene is dispersed in the alcohol, for example methyl alcohol or ethanol, feeds exsiccant hydrogenchloride and makes stilbazo, 4 '-diimine ester hydrochloride; Stilbazo, 4 '-diimine ester hydrochloride and Ortho-Aminophenol or derivatives thereof are dissolved or suspended in organic acid and the low first pure medium, and the condensation closed loop becomes the dibenzoxazine diphenyl ethylene derivatives.Organic acid preferable formic acid or acetate that the condensation ring-closure reaction is used; Suitable low unit alcohol is (C
1-C
4) alcohol, particular methanol or ethanol.When different symmetry of preparation and asymmetric dibenzoxazine toluylene mixture, Ortho-Aminophenol or derivatives thereof (a) and charge ratio (b) by weight can be at (a): 5-95%, (b): adjusting in the scope of 95-5%.Preferable charge ratio is, (a): and 30-70%, (b): 70-30%.(a) and weight percent sum (b) be 100%.Stilbazo, the mol ratio of 4 '-diimine ester hydrochloride and the reaction of Ortho-Aminophenol or derivatives thereof is 1: 2-2.5, preferred 1: 2.05-2.1.Range of reaction temperature is a room temperature-75 ℃, preferred 40-70 ℃; Reaction times is 2-10 hour, and preferred range is 4-8 hour.
After reaction is finished, after filtration, washing, refining and dry, obtain product.
According to synthetic method proposed by the invention, by adjusting raw material Ortho-Aminophenol or derivatives thereof (a) and ingredient proportion (b), in the product each components contents scope can be controlled in (c): 5-90%, (d): 5-90% with (e): 5-50%.The weight percent sum of three components is 100%.
When using two or more Ortho-Aminophenol or derivatives thereofs to react, have more kinds of symmetries and asymmetric dibenzoxazine diphenyl ethene compounds in the mixture that obtains.
The invention has the advantages that the rational unit process order that has designed synthetic dibenzoxazine diphenyl ethene compounds, as last reactions steps, the raw materials cost of preparation compound is reduced the unit process of high yield.
Another advantage of the present invention is not use inflammable, explosive compound in the reaction process, makes reaction process safety, is convenient to operation.
The present invention can be according to the application need of white dyes, by adjusting the ratio that adds the Ortho-Aminophenol or derivatives thereof, directly obtain the polycomponent symmetry or the asymmetric dibenzoxazine toluylene mixture of single or preset proportion, thereby obtain the white dyes of better whitening effect.
Institute of the present invention synthetic symmetry and asymmetric dibenzoxazine toluylene and composition thereof can be used for the fluorescent brightening of synthetic or natural polymerization material to be handled.
Two or more symmetry and asymmetric dibenzoxazine diphenyl ethene compounds of institute of the present invention synthetic is combined into mixture when being used for brightening of synthetic or natural polymerization material, and its whitening effect is better than using the single component compound.
Embodiment
Following example is in order to further specifying the present invention, but is not construed as limiting the invention.
Example 1
4,4 '-dicyano toluylene prepares according to the synthetic method among the US 4519953;
With 7.1g (0.031mol) 4,4 '-dicyano toluylene is dispersed in the 200ml methyl alcohol, feeds the exsiccant hydrogen chloride gas to saturated, at room temperature stirring reaction is 50 hours, filters vacuum-drying, obtain stilbazo, 4 '-diimine methyl ester hydrochloride 11.0g.
With 11.0g (0.03mol) stilbazo, 4 '-diimine methyl ester hydrochloride and 6.7g (0.061mol) 2-amino-phenol joins in the 60ml methyl alcohol, adds glacial acetic acid 40ml subsequently.Stir down about slow heat temperature raising to 70 ℃, keep 6 hours to reaction end.Cool to 40 ℃, vacuum suction filter, filter cake washing after drying.Obtain 4,4 '-two (benzoxazoles-2-yl) toluylene 11.4g.
Example 2
With 11.0g (0.03mol) stilbazo, 4 '-diimine methyl ester hydrochloride, 3.4g (0.031mol) 2-amino-phenol, 3.9g (0.031mol) 4-methyl-2-amino-phenol join in the 60ml methyl alcohol, add glacial acetic acid 40ml subsequently.Stir down about slow heat temperature raising to 70 ℃, keep 6 hours to reaction end.Cool to 40 ℃, vacuum suction filter, filter cake washing after drying.Obtain mixture 11.9g.
Per-cent with the liquid chromatogram measuring mixture is:
4-(benzoxazole-2-yl)-4 '-(5-Jia base benzoxazole-2-yl) toluylene 49.5%; 4,4 '-two (benzoxazoles-2-yl) toluylene 22.7%; 4,4 '-two (5-Jia base benzoxazole-2-yl) toluylene 27.8%.
Example 3
With 11.0g (0.03mol) stilbazo, 4 '-diimine methyl ester hydrochloride, 2.6g (0.024mol) 4-methyl-2-amino-phenol and 6.9g (0.042mol) the 4-tertiary butyl-2-amino-phenol join in the 60ml methyl alcohol, add glacial acetic acid 40ml subsequently.Stir down about slow heat temperature raising to 70 ℃, keep 6 hours to reaction end.Cool to 40 ℃ of vacuum suction filters, filter cake washing after drying.Obtain mixture 13.7g.
Per-cent with the liquid chromatogram measuring mixture consists of:
4-(5-first base benzoxazole-2-yl)-4 '-(5-tertiary butyl benzo oxazole-2-yl) toluylene 44.0%; 4,4 '-two (5-Jia base benzoxazole-2-yl)-toluylene 8.2%; 4,4 '-two (5-tertiary butyl benzo oxazole-2-yl)-toluylene 47.8%.
Example 4
With 11.0g (0.03mol) stilbazo, 4 '-diimine methyl ester hydrochloride, 9.0g (0.063mol) 4-chloro-2-amino-phenol join in the 60ml methyl alcohol, add glacial acetic acid 40ml subsequently.Stir down about slow heat temperature raising to 70 ℃, keep 6 hours to reaction end.Cool to 40 ℃ of vacuum suction filters, filter cake washing after drying.Obtain 4,4 '-two (5-Lv benzoxazole-2-yl) toluylene 12.9g.
Example 5
With 11.0g (0.03mol) stilbazo, 4 '-diimine methyl ester hydrochloride, 2.3g (0.02lmol) 2-amino-phenol, 2.6g (0.021mol) 4-methyl-2-amino-phenol and 3.5g (0.02lmol) the 4-tertiary butyl-2-amino-phenol join in the 60ml methyl alcohol, add glacial acetic acid 40ml subsequently.Stir down about slow heat temperature raising to 70 ℃, keep 6 hours to reaction end.Cool to 40 ℃ of vacuum suction filters, filter cake washing after drying.Obtain mixture 12.7g.
Per-cent with the liquid chromatogram measuring mixture consists of:
4-(benzoxazole-2-yl)-4 '-(5-Jia base benzoxazole-2-yl) toluylene 21.3%; 4-(benzoxazole-2-yl)-4 '-(5-tertiary butyl base benzoxazole-2-yl) toluylene 24.0%; 4-(5-first base benzoxazole-2-yl)-4 '-(5-tertiary butyl benzo oxazole-2-yl) toluylene 21.0%; 4,4 '-two (benzoxazoles-2-yl) toluylene 11.0%; 4,4 '-two (5-Jia base benzoxazole-2-yl)-toluylene 9.7%; 4,4 '-two (5-tertiary butyl benzo oxazole-2-yl)-toluylene 13.0%.
Claims (8)
1, the synthetic method of a kind of white dyes and composition thereof is characterized in that: with stilbazo, 4 '-diimine ester hydrochloride (I) and Ortho-Aminophenol or derivatives thereof (II) are raw material,
(I)
In organic acid and low first pure blending agent, react, obtain dibenzoxazine diphenyl ethene compounds (III),
(III)
In the formula: X is methyl or ethyl;
R
1, R
2Can be identical or different, be selected from hydrogen, (C respectively
1-C
4) alkyl or halogen.
2, synthetic method according to claim 1 is characterized in that: raw material stilbazo in the building-up reactions, 4 '-diimine ester hydrochloride (I) counts 1 with the add-on of Ortho-Aminophenol or derivatives thereof (II) by mole: 2-2.5.
3, synthetic method according to claim 2 is characterized in that: raw material stilbazo in the building-up reactions, 4 '-diimine ester hydrochloride (I) counts 1 with the add-on of Ortho-Aminophenol or derivatives thereof (II) by mole: 2.05-2.1.
4, according to claim 1,2 or 3 described synthetic methods, it is characterized in that: the R in Ortho-Aminophenol or derivatives thereof (II)
1With R
2Not simultaneously, raw material (a) is not respectively by weight with the feed ratio of raw material (b): 5-95% and 95-5%; The weight percent sum of two kinds of raw materials is 100%.
5, synthetic method according to claim 1 is characterized in that: range of reaction temperature is a room temperature-75 ℃; Reaction times: 2-10 hour.
6, synthetic method according to claim 1 or 5, it is characterized in that: range of reaction temperature is 40-70 ℃; Reaction times: 4-8 hour.
7, synthetic method according to claim 1 is characterized in that: described organic acid is selected from formic acid or acetate; Low first alcohol is selected from methyl alcohol or ethanol.
8, be used for the purposes that the fluorescent brightening of synthetic or natural polymerization material is handled according to method institute synthetic white dyes of claim 1 and composition thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03110862 CN1237063C (en) | 2003-01-14 | 2003-01-14 | Fluorescent brightening agent and synthesis method of its mixture |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03110862 CN1237063C (en) | 2003-01-14 | 2003-01-14 | Fluorescent brightening agent and synthesis method of its mixture |
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| Publication Number | Publication Date |
|---|---|
| CN1517348A CN1517348A (en) | 2004-08-04 |
| CN1237063C true CN1237063C (en) | 2006-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03110862 Expired - Fee Related CN1237063C (en) | 2003-01-14 | 2003-01-14 | Fluorescent brightening agent and synthesis method of its mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143854B (en) * | 2006-09-15 | 2011-01-05 | 沈阳化工研究院 | Synthesis method for dibenzoxazole compounds |
| CN102070551B (en) * | 2010-12-29 | 2012-06-20 | 河北星宇化工有限公司 | Method for preparing 2,2'-(1,2-Ethenediyldi-4,1-phenylene)bisbenzoxazole |
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2003
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