CN107936607A - A kind of preparation method of bromo fluoresceins cosmetic dyes - Google Patents
A kind of preparation method of bromo fluoresceins cosmetic dyes Download PDFInfo
- Publication number
- CN107936607A CN107936607A CN201711262831.6A CN201711262831A CN107936607A CN 107936607 A CN107936607 A CN 107936607A CN 201711262831 A CN201711262831 A CN 201711262831A CN 107936607 A CN107936607 A CN 107936607A
- Authority
- CN
- China
- Prior art keywords
- bromo
- fluoresceins
- preparation
- bromine
- cosmetic dyes
- 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.)
- Pending
Links
- 0 C*(c1c(C(C2CC2)(c2ccc(*)cc2*c2c3)c2ccc3O*)c(I)c(*)c(*)c1*)=* Chemical compound C*(c1c(C(C2CC2)(c2ccc(*)cc2*c2c3)c2ccc3O*)c(I)c(*)c(*)c1*)=* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention discloses a kind of preparation method of bromo fluoresceins cosmetic dyes, involved dyestuff is specially 4', 5' dibromofluoresceins (C.I.45370:1), 2', 4', 5', 7' eosin (C.I.45380:2) 4,7 dichlorofluorescein (C.I.45405 of, 2', 4', 5', 7' tetrabromo:1) 4,5,6,7 tetrachlorofluorescein (C.I.45410 of, 2', 4', 5', 7' tetrabromo:1).Comprise the following steps：(I) under low temperature, sodium hypobromite solution is prepared in liquid caustic soda and aqueous sodium hypochlorite solution in bromine；(II) fluorescein or corresponding chlorofluorescein are dissolved or are partially dissolved in the solvent containing acid, and sodium hypobromite solution is instilled under room temperature and carries out bromination；(III) after arriving bromination terminal, if any remaining hypobromous acid, appropriate reducing agent is added to eliminate；After removing solvent, gained crude product washs desalination through dilute hydrochloric acid, dries and obtains target product.
Description
Technical field
The present invention relates to a kind of preparation method of cosmetic dyes, is contaminated more particularly to a kind of bromo fluoresceins cosmetics
The preparation method of material.
Background technology
By 2015 editions《Cosmetics safety technical specification》Described, the kind of bromo fluoresceins cosmetic dyes has 4', 5'-
Dibromofluorescein, 2', 4', 5', 7'- eosins, 2', 4', 5', the bromo- 4,7- dichlorofluoresceins of 7'- tetra-, 2', 4', 5',
The bromo- 4,5,6,7- tetrachlorofluoresceins of 7'- tetra-.These four dyestuffs and its respective disodium salt dyestuff or and being permitted for of color lake
The coloring of cosmetic.
There is a common unit process in the synthesis technique of aforementioned four dyestuff, that is, bromination, bromination process also base
This is consistent.According to described in document, bromination process can be divided into two major classes, and one kind is electrolysis bromination method, and another kind of is chemical reagent bromination
Method.
The representative document of electrolysis bromination method has：Electrochemical preparation of Erythrosine
And Eosin (Bulletin of Electrochemistry, 1987,3 (1) .pp.29-31.), are related to and prepare tetrabromo fluorescence
Element, using sodium bromide as bromating agent, the molar ratio of sodium bromide and fluorescein is 6.5:1, product yield 72.5%；
Electrochemical synthesis of eosin from fluorescein(Journal of Applied
Electrochemistry, 23 (1993), 808-812), it is related to and prepares eosin, using potassium bromide as bromating agent, bromination
The molar ratio of potassium and fluorescein is 7:1, the product yield 94.2% under optimal conditions, dye content 94.5%；
Electrochemical halogenation of fluorescein in batch and flow reactors
(Bulletin of Electrochemistry,2000,16(8):341-344), it is related to and prepares eosin, sodium bromide,
Potassium bromide, bromine can be used as bromating agent, and the wherein molar ratio of sodium bromide or potassium bromide and fluorescein is 7:1, bromine and fluorescence
The molar ratio of element is up to 20:1 (is then 40 in terms of bromine atoms：1), product yield 94%.
The representative document of chemical reagent bromination method has：The preparation method of CN 102351832A spirit soluble eosins, design four
Bromine fluorescein, using bromine as bromating agent, directly instill in the ethanol solution of fluorescein and complete bromination, and wherein bromine and fluorescein rubs
You are than being 9:1 (is then 18 in terms of bromine atoms：1).
The preparation method of CN 102351833A water soluble eosins, using bromine as bromating agent, bromine is added dropwise to the 95% of fluorescein
Bromination is completed in ethanol solution, the wherein molar ratio of bromine and fluorescein is 4.6:1 (is then 9.2 in terms of bromine atoms：1).
The bromination of 3111528 fluoresceins of US, is related to dibromofluorescein, and substantially technique is made in bromine instillation liquid caustic soda solution
Standby sodium hypobromite solution, sodium hypobromite are instilled to the alkaline solution of fluorescein again, then phosphoric acid pours into and completes bromination to obtain dibromo glimmering
Light element, the wherein molar ratio of bromine and fluorescein are 2.55:1 (is then 5.1 in terms of bromine atoms：1), product purity 96-99%,
Yield is not referred to.
Foregoing all documents there are one it is common the defects of, from charge ratio, the utilization rate of bromine atoms is below
50% (yet having no recycling of the statement later stage to remaining bromo element), this design on source just do not meet the reason of Green Chemistry
Read, and bromine is a kind of consumable resource, high all the way with the bromine market price nearly ten years so that this shortcoming is more
It is prominent.
The object of the present invention is to provide the good bromo fluoresceins cosmetics of the high usage and economy of a kind of bromine atoms
The preparation method of dyestuff.The bromo fluoresceins cosmetic dyes content that is prepared with this method is high, purity is high, high income.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of bromo fluoresceins cosmetics dye of high bromine atoms utilization rate
The preparation method of material.
Bromo fluoresceins cosmetic dyes according to the present invention are：4', 5'- dibromofluorescein (C.I.45370:1)、
2', 4', 5', 7'- eosin (C.I.45380:2) the bromo- 4,7- dichlorofluoresceins of, 2', 4', 5', 7'- tetra-
(C.I.45405:1) the bromo- 4,5,6,7- tetrachlorofluoresceins (C.I.45410 of, 2', 4', 5', 7'- tetra-:1).Corresponding chemical constitution
Formula is as follows：
Reaction equation according to the present invention can be described as follows：
1st, the preparation of sodium hypobromite
Br2+2NaOH→NaBr+NaBrO+H2O
NaClO+NaBr→NaCl+NaBrO
2nd, bromination
Wherein：R1, R2, R3, R4=H or Cl；R5=H or Br；X=Cl or H2PO4-。
For example above-mentioned reaction equation description of reaction mechanism according to the present invention：Can be bromine under alkaline case using sodium hypochlorite
Change the principle that sodium is replaced as sodium hypobromite, the bromine molecule of 1mol is successfully changed into 2mol sodium hypobromites；Sodium hypobromite exists
Hypobromous acid is converted into the case of acidity, so as to complete the bromination to object.
A kind of preparation method of bromo fluoresceins cosmetic dyes disclosed by the invention, its step include：
(I) under low temperature, sodium hypobromite solution is prepared in liquid caustic soda and aqueous sodium hypochlorite solution in bromine；
(II) fluorescein or corresponding chlorofluorescein are dissolved or are partially dissolved in the solvent containing acid, and step is instilled under room temperature
Suddenly the sodium hypobromite solution that prepared by (I) carries out bromination；
(III) after arriving bromination terminal, if any remaining hypobromous acid, appropriate reducing agent is added to eliminate；After removing solvent, gained is thick
Product wash desalination through dilute hydrochloric acid, dry and obtain target product.
Wherein, in step (I), the low temperature is 0~15 DEG C.
In step (I), the molar ratio of the bromine and sodium hypochlorite is 1: 0.98~1.0.
In step (II), when preparing 4 ', 5 '-dibromofluorescein, the molar ratio of the bromine and fluorescein is 1~1.05:
1。
In step (II), when preparing four bromo fluoresceins dyestuffs, the bromine and fluorescein or chlorofluorescein are rubbed
You are than being 2.1~2.3:1.
In step (II), the acid is acetic acid or phosphoric acid.
In step (II), the molar ratio of phosphoric acid and bromine is 0.6~0.9:1.
In step (II), the solvent is acetic acid or 95% ethanol.
In step (II), the room temperature is 20~30 DEG C.
In step (III), the reducing agent is sodium hydrogensulfite or sodium sulfite.
The present invention has been provided in particular in a kind of preparation side of the bromo fluoresceins cosmetic dyes of high bromine atoms utilization rate
Method, and there is splendid economy.
The innovation of the preparation process of the present invention is：On the premise of bromination mechanism is seen clearly, price is dexterously utilized
The sodium hypochlorite low in cost and easily available arrived, is changed into sodium hypobromite by sodium bromide, so that by the utilization rate of bromine atoms in the design of source
Bring up to close to 100%, and ultimate guarantee product is in high yield.
Compared with conventional preparation method, its outstanding advantage is the present invention：
(1) high bromine atoms utilization rate, meets green chemical concept；
(2) transforming agent of the sodium hypochlorite that is not only cheap but also being readily available as bromide ion, the higher economic value of tool are used.
The preparation method of the bromo fluoresceins cosmetic dyes of the present invention is made with reference to specific embodiment further
Explanation.
Embodiment
The experimental method of actual conditions is not specified in the following example, usually according to normal condition, or according to manufacturer
Proposed condition.Ratio and percentage are based on weight, unless stated otherwise.
Embodiment 1 (preparation of 4', 5'- dibromofluorescein)
In 250mL four-hole boiling flasks, 30.5g liquor natrii hypochloritises (10%, 43mmol) are added, external ice-water bath, is opened
Stirring, adds about 18g water, 32% liquid caustic soda of 12.2g, temperature of charge to after 0~5 DEG C, be slowly dropped into 7.0g bromines (99%,
43mmol), controlling reaction temperature is below 15 DEG C.Measure content (effective bromine about 20%) is simultaneously spare.
100g95% ethanol is added in 500mL four-hole boiling flasks, opens and stirs, addition 14.3g fluoresceins (97.5%,
42mmol), 40~50 DEG C are warming up to, dissolving.13.6g phosphoric acid (85%, 118mmol) is added, is cooled to 20~25 DEG C, 1.5 is small
When it is interior slowly be added dropwise the above-mentioned sodium hypobromite solutions of 67g (84mmol), present invention temperature control is at 20~25 DEG C.Insulated and stirred again
1 it is small when.
Reaction solution is warming up to 60 DEG C, and vacuum steams about 80g ethanol.Distill and water 150mL is added in the liquid of bottom, there is orange thing to analyse
Go out, be cooled to room temperature, filter, obtain rough filter cake.
Filter cake shares about 200mL diluted hydrochloric acid aqueous solutions (1+500) elution three times.Filter cake obtains 20.1g oranges in 100 DEG C of drying
Yellow target product (HPLC purity 98.4%, content 98.2%), yield 96.0%.
Embodiment 2 (preparation of 2', 4', 5', 7'- eosin)
Added in 250mL four-hole boiling flasks, addition 61.0g liquor natrii hypochloritises (10%, 86mmol), external ice-water bath,
Stirring is opened, adds about 36g water, 32% liquid caustic soda of 24.3g, temperature of charge is slowly dropped into 13.9g bromines to after 0~5 DEG C
(99%, 86mmol), controlling reaction temperature is below 15 DEG C.Measure content (effective bromine about 20%) is simultaneously spare.
250g acetic acid is added in 500mL four-hole boiling flasks, opens and stirs, addition 13.6g fluoresceins (97.5%,
40mmol), 50~60 DEG C are warming up to, it is quick to stir (300~400rpm) 30min.25~30 DEG C are cooled to, 3~4 is interior slow when small
Slow that the above-mentioned sodium hypobromite solutions of 134.0g (20%, 168mmol) are added dropwise, present invention temperature control is at 25~30 DEG C.Keep the temperature again
Stir 2 it is small when, sampling carry out liquid phase detection bromination terminal.Add appropriate sodium hydrogensulfite and eliminate remaining hypobromous acid.It is cooled to 15
DEG C, filter, obtain rough filter cake.
The mashing in about 100mL diluted hydrochloric acid aqueous solutions (1+500) of rough filter cake is uniform, filters, and is so repeated 3 times desalination.
Filter cake obtains 25.0g lightpinks target product (HPLC purity 97.8%, content 97.8%, 37.7mmol), receives in 100 DEG C of drying
Rate 94.3%.
Embodiment 3 (preparation of 2', 4', 5', 7'- eosin)
With " 12.9g fluoresceins (97.5%, 38mmol) " replacement " 13.6g fluoresceins (97.5%, 40mmol) ", remaining is same
Embodiment 2, obtains 24.0g lightpinks target product (HPLC purity 97.6%, content 97.5%, 36mmol), yield 95%.
Embodiment 4 (preparation of the bromo- 4,7- dichlorofluoresceins of 2', 4', 5', 7'- tetra-)
With " 15.6g4,7- tetrachlorofluorescein (97.5%, 38mmol) " replacement " 13.6g fluoresceins (97.5%,
40mmol) ", remaining is with embodiment 2, obtain 26.3g lightpinks target product (HPLC purity 98.2%, content 97%,
35.6mmol), yield 93.7%.
Embodiment 5 (preparation of the bromo- 4,5,6,7- tetrachlorofluoresceins of 2', 4', 5', 7'- tetra-)
With " 4,5,6,7- tetrachlorofluorescein 18.4g (97%, 38mmol) " replacement " 13.6g fluoresceins (97.5%,
40mmol) ", remaining is with embodiment 2, obtain 28.8g lightpinks target product (HPLC purity 97.4%, content 97.2%,
35.6mmol), yield 93.8%.
Embodiment 6 (preparation of the bromo- 4,5,6,7- tetrachlorofluoresceins of 2', 4', 5', 7'- tetra-)
In addition to " reaction temperature is controlled at 20~25 DEG C ", remaining obtains 27.3g lightpink target products with embodiment 5
(HPLC purity 95.6%, content 97.5%, 33.9mmol), yield 89.2%.
Embodiment described above is only that the preferred embodiment of the present invention is described, not to the model of the present invention
Enclose and be defined, on the premise of design spirit of the present invention is not departed from, technical side of the those of ordinary skill in the art to the present invention
The various modifications and improvement that case is made, should all fall into the protection domain that claims of the present invention determines.
Claims (10)
1. a kind of preparation method of bromo fluoresceins cosmetic dyes, it is characterised in that comprise the following steps：
(I) under low temperature, sodium hypobromite solution is prepared in liquid caustic soda and aqueous sodium hypochlorite solution in bromine；
(II) fluorescein or corresponding chlorofluorescein are dissolved or are partially dissolved in the solvent containing acid, and hypobromous acid is instilled under room temperature
Sodium solution carries out bromination；
(III) after arriving bromination terminal, if any remaining hypobromous acid, appropriate reducing agent is added to eliminate；After removing solvent, gained crude product warp
Dilute hydrochloric acid washs desalination, dries and obtains target product.
2. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (I)
In, the low temperature is 0~15 DEG C.
3. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (I)
In, the molar ratio of the bromine and sodium hypochlorite is 1:0.98~1.0.
4. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (II)
In, 4' is prepared, during 5'- dibromofluoresceins, the molar ratio of bromine and fluorescein is 1.0~1.05:1.
5. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (II)
In, when preparing four bromo fluoresceins dyestuffs, bromine is 2.1~2.3 with the molar ratio of fluorescein or chlorofluorescein:1.
6. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (II)
In, the acid is acetic acid or phosphoric acid.
7. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (II)
In, the molar ratio of phosphoric acid and bromine is 0.6~0.9:1.
8. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (II)
In, the solvent is acetic acid or 95% ethanol.
9. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step (II)
In, the room temperature is 20~30 DEG C.
10. the preparation method of bromo fluoresceins cosmetic dyes according to claim 1, it is characterised in that：Step
(III) in, the reducing agent is sodium hydrogensulfite or sodium sulfite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711262831.6A CN107936607A (en) | 2017-12-04 | 2017-12-04 | A kind of preparation method of bromo fluoresceins cosmetic dyes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711262831.6A CN107936607A (en) | 2017-12-04 | 2017-12-04 | A kind of preparation method of bromo fluoresceins cosmetic dyes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107936607A true CN107936607A (en) | 2018-04-20 |
Family
ID=61944692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711262831.6A Pending CN107936607A (en) | 2017-12-04 | 2017-12-04 | A kind of preparation method of bromo fluoresceins cosmetic dyes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107936607A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678765A (en) * | 2018-12-25 | 2019-04-26 | 维思普新材料（苏州）有限公司 | A kind of continuous preparation method of photoinitiator |
| CN110498802A (en) * | 2019-07-03 | 2019-11-26 | 山西大学 | A kind of dibromofluorescein derivative and its synthetic method and application |
| CN116355437A (en) * | 2023-03-13 | 2023-06-30 | 湖南金桥新材料科技有限公司 | Preparation method for improving saturation of bromofluorescein lake |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3111528A (en) * | 1962-01-19 | 1963-11-19 | Sun Chemical Corp | Bromination of fluorescein |
| CN103396388A (en) * | 2013-07-05 | 2013-11-20 | 天津市化学试剂研究所 | Preparation method of tetrabromophenolphthalein indicator |
-
2017
- 2017-12-04 CN CN201711262831.6A patent/CN107936607A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3111528A (en) * | 1962-01-19 | 1963-11-19 | Sun Chemical Corp | Bromination of fluorescein |
| CN103396388A (en) * | 2013-07-05 | 2013-11-20 | 天津市化学试剂研究所 | Preparation method of tetrabromophenolphthalein indicator |
Non-Patent Citations (1)
| Title |
|---|
| 化工部科学技术研究总院: "《精细化工品种手册》", 31 October 1986 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678765A (en) * | 2018-12-25 | 2019-04-26 | 维思普新材料（苏州）有限公司 | A kind of continuous preparation method of photoinitiator |
| CN110498802A (en) * | 2019-07-03 | 2019-11-26 | 山西大学 | A kind of dibromofluorescein derivative and its synthetic method and application |
| CN110498802B (en) * | 2019-07-03 | 2021-02-02 | 山西大学 | Dibromofluorescein derivative and synthesis method and application thereof |
| CN116355437A (en) * | 2023-03-13 | 2023-06-30 | 湖南金桥新材料科技有限公司 | Preparation method for improving saturation of bromofluorescein lake |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107936607A (en) | A kind of preparation method of bromo fluoresceins cosmetic dyes | |
| JP6020701B2 (en) | Green pigment for color filter and color filter | |
| CN101565472B (en) | Ketoxime ester photoinitiator | |
| Qiu et al. | Facile synthesis of novel disperse azo dyes with aromatic hydroxyl group | |
| CA1046709A (en) | Liquid preparations of reactive dyestuffs | |
| JP4668801B2 (en) | Pigment dispersant and use thereof | |
| EP0884312B2 (en) | Triazinylaminostilbene compounds | |
| JP2012522086A (en) | Process for producing easily dispersible purple pigment | |
| CN101955689A (en) | Triarylmethane class and rhodamine class color compositions and the pigment dispersion that uses this color compositions | |
| CN109642970A (en) | Pigment composition for color filter and colour filter | |
| CN109863208A (en) | Green filter color compositions and its manufacturing method | |
| CN103524446B (en) | Preparation method of fluorescent whitening agent | |
| CN1387554A (en) | Process for preparation of solutions of anionic organic compounds | |
| CN104592786B (en) | A kind of new special deep reactive orange or weld and preparation method thereof | |
| CN104087022B (en) | A kind of silicon dioxide of hud typed cladding pigment and preparation method thereof | |
| EP4053220A1 (en) | Method for chlorinating indanthrone blue, violanthrone or isoviolanthrone | |
| US4077974A (en) | Process for the halogenation of copper phthalocyanine | |
| CN105348853B (en) | A kind of orange active dye compound and its preparation method and application | |
| CN108435227A (en) | A kind of preparation method of efficient stable catalysis material | |
| CN105524485A (en) | Active red dye preparation method | |
| CN101381525B (en) | Method for preparing vat yellow 2 anthraquinone thiazole dyes | |
| US2133340A (en) | Acylamino phthalocyanine | |
| CN108440994A (en) | A kind of preparation method of active dark blue dye | |
| CN109651844A (en) | A kind of reactive dye and preparation method thereof | |
| KR102527026B1 (en) | Manufacturing method of zinc halide phthalocyanine pigment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180420 |