CN103319910A - Preparation method of indophenol derivative - Google Patents
Preparation method of indophenol derivative Download PDFInfo
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- CN103319910A CN103319910A CN2012100765269A CN201210076526A CN103319910A CN 103319910 A CN103319910 A CN 103319910A CN 2012100765269 A CN2012100765269 A CN 2012100765269A CN 201210076526 A CN201210076526 A CN 201210076526A CN 103319910 A CN103319910 A CN 103319910A
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Abstract
The invention relates to a preparation method of an indophenol derivative, which is prepared by adding sodium carbonate and sodium persulfate into acetylamino-carrying phenol and N, N-dialkyl-carrying alkylaniline hydrochloride to make them undergo an oxidation reaction. The method can alleviate environmental pollution, increase reaction yield, and effectively overcome the defects in an indophenol derivative traditional preparation process.
Description
Technical field
The present invention relates to a kind of staining agent indophenols derivative and preparation method thereof.
Background technology
Indophenols derivative among the present invention is a kind of staining agent, is widely used in the dyeing of clothes dyeing and hair.Only have one piece of patent US20080182212 to report the synthetic method of similar compound in the prior art, and the purposes of such material has been described.The synthetic method of common this indophenols derivative is as follows:
But aforesaid method has following shortcoming: 1. the first step uses acyl chlorides that raw material is carried out acetylize, and environmental pollution is very large; 2. the synthetic target product of second step uses ammonium persulphate and triethylamine, also is the very large material of environmental pollution; 3. yield is lower.
Summary of the invention
For addressing the above problem, the present invention proposes a kind of new method for preparing the indophenols derivative, its technical scheme is:
A kind of preparation method of indophenols derivative, it is characterized by by with the phenol of kharophen with N, the alkyl benzene amine hydrochloride generation oxidizing reaction of N-dialkyl group makes.Its concrete steps are will be with the phenol of kharophen and with N, and the alkyl benzene amine hydrochloride of N-dialkyl group is dissolved in the solvent, add first the yellow soda ash reaction, then add Sodium Persulfate and make the indophenols derivative.
Therein in scheme, be 2,4-, two chloro-3-methyl 6-acetoamidophenols with the phenol of kharophen, with N, the alkyl benzene amine hydrochloride of N-dialkyl group is 4-N, N-diethyl-2-aminotoluene hydrochloride, and its reaction formula is as follows:
In technique scheme, with the phenol of kharophen and with N, the mol ratio of the alkyl benzene amine hydrochloride of N-dialkyl group is 1: (1.02-1.1).
In particular, its step is that the alkyl benzene amine hydrochloride of N-dialkyl group is dissolved in the solvent with the phenol of kharophen and with N, adds yellow soda ash, is cooled to 0 ℃, adds Sodium Persulfate in batches again, obtains red solid, obtains the indophenols derivative behind the recrystallization.
Wherein, yellow soda ash be (5-6.8) with mol ratio with the phenol of kharophen: 1, and Sodium Persulfate and be (0.1-2.2) with the mol ratio of the phenol of kharophen: 1.
In a preferred version, be to be made by diacetyl oxide and amino-phenol hydrochloride solution generation acetylization reaction with the phenol of kharophen.
In such scheme, the mol ratio of amino-phenol hydrochloride and diacetyl oxide is 1: (1.1-1.15), the solvent of described amino-phenol hydrochloride solution is acetonitrile.
Wherein, described amino-phenol hydrochloride is 2,4-, two chloro-3-methyl-6-amino-phenol hydrochloride, and reaction formula is
In another program, contain sodium-acetate in the amino-phenol hydrochloride solution, the mol ratio of itself and amino-phenol hydrochloride is (1.1-1.2): 1.
Than prior art, the alkali that uses in the reaction system in the method is yellow soda ash rather than triethylamine, and what oxygenant was used is Sodium Persulfate rather than ammonium persulphate, has reduced pollution, handled easily.The very large raising of yield can reach more than 60% simultaneously.And using diacetyl oxide and without acyl chlorides, reduced environmental pollution in acetylization reaction, is sodium-acetate and alkali is used, and safety conveniently is easy to industrialization.
Description of drawings
Fig. 1 is indophenols derivative 2-acetylaminohydroxyphenylarsonic acid 6-chloro-4[(4-diethylamino) 2-aminomethyl phenyl-imino-]-5-methyl isophthalic acid-oxo-2, the 1HNMR spectrogram of 5-hexanaphthene diene.1HNMR(400MHZ，CDCl3)δ8.30(1H)，δ8.24(1H)，δ6.88-6.90(1H)，δ6.64(1H)，δ6.57-6.59(1H)，δ3.40-3.46(4H)，δ2.54(3H)，δ2.37(3H)，δ2.20(3H)，δ1.20-1.25(6H)。
Embodiment
Embodiment 1:
In the there-necked flask of 250ml, drop into 20g 1, acetonitrile 150ml, sodium-acetate 8g (1.1eq.), room temperature drips acetic anhydride 10.3 (1.1eq.), white is outstanding turbid, slowly drip diacetyl oxide, separate out a large amount of white solids behind the 20min, suction filtration, 50ml washes filter cake, get 21g white solid 2,4-two chloro-3-methyl 6-acetoamidophenols, productive rate is 99%.
It is carried out the nucleus magnetic resonance test.1HNMR(400MHZ，DMSO-d6)δ10.01(1H)，δ9.64-9.69(1H)，δ7.64(1H)，δ2.32-2.38(3H)，δ2.07-2.11(3H)。
In the there-necked flask of 2000ml, drop into 2,4-, two chloro-3-methyl 6-acetoamidophenol 99.3g again, compound 4 is 91.1g, (1.1eq.), and methyl alcohol 1000ml, water 500ml, white is outstanding turbid, stirs 20min, the red intensification adds yellow soda ash 306.5g (6.8eq.), stirs 20min, the grey settled solution has the grey settled solution under the bottle, is cooled to 0 ℃ of interior temperature, add Sodium Persulfate 222.2g (2.2eq.), solution becomes scarlet at once in batches, adds in 30 minutes.Filter to get the 132.3g red solid, get the solid 2-acetylaminohydroxyphenylarsonic acid 6-chloro-4[(4-diethylamino of 83.7g shiny red with re-crystallizing in ethyl acetate) 2-aminomethyl phenyl-imino-]-5-methyl isophthalic acid-oxo-2,5-hexanaphthene diene (the 1HNMR spectrogram is seen Fig. 1), productive rate is 62%.
Embodiment 2:
In the 500ml there-necked flask, drop into 50g 1, acetonitrile 400ml, sodium-acetate 21.5g (1.2eq.), room temperature drips acetic anhydride 25.7g (1.15eq.), filters, and the 80ml washing gets 49.4g white solid compound 3.Productive rate is 96%.Dropping into compound 3 in the there-necked flask of 2000ml is 50g, and compound 4 is 48.1g (1.05eq.), each 500ml of first alcohol and water, the white suspension liquid adds yellow soda ash 113.2g (5eq.), the scarlet suspension liquid, be chilled to 0 ℃ of interior temperature, add Sodium Persulfate 112g in batches, the solution becomes scarlet is until blueness at once, added in 20 minutes, reaction 3h filters, and gets the 68g red solid, re-crystallizing in ethyl acetate gets 48g shiny red solid, and productive rate is 60%.
Embodiment 3:
In the 500ml there-necked flask, drop into 27.2g 1, acetonitrile 200ml, sodium-acetate 11.7g (1.1eq.), room temperature drips acetic anhydride 13.4 (1.12eq.), suction filtration, the 60ml washing gets 26g white solid compound 3.Productive rate is 93%.Dropping into compound 3 in the there-necked flask of 500ml is 5g, and 4 is 4.7g (1.02eq.), each 100ml of first alcohol and water, the white suspension liquid adds yellow soda ash 13.6g (6eq.), the scarlet suspension liquid, be chilled to 0 ℃ of interior temperature, add Sodium Persulfate 11.2g in batches, the solution becomes scarlet is until blueness at once, added in 20 minutes, reaction 3h filters, and gets the 6.6g red solid, re-crystallizing in ethyl acetate gets 6.2g shiny red solid, and productive rate is 80%.
Claims (10)
1. the preparation method of an indophenols derivative, it is characterized by by with the phenol of kharophen with N, the alkyl benzene amine hydrochloride generation oxidizing reaction of N-dialkyl group makes.
2. the preparation method of indophenols derivative as claimed in claim 1, it is characterized in that its concrete steps are will be with the phenol of kharophen and with N, the alkyl benzene amine hydrochloride of N-dialkyl group is dissolved in the solvent, adds first the yellow soda ash reaction, then adds Sodium Persulfate and makes the indophenols derivative.
3. the preparation method of indophenols derivative as claimed in claim 1 or 2, it is characterized in that, phenol with kharophen is 2,4-two chloro-3-methyl 6-acetoamidophenols, with N, the alkyl benzene amine hydrochloride of N-dialkyl group is 4-N, N-diethyl-2-aminotoluene hydrochloride, and its reaction formula is as follows:
4. such as the preparation method of one of claim 1-3 claim described indophenols derivative, it is characterized by with the phenol of kharophen and with N, the mol ratio of the alkyl benzene amine hydrochloride of N-dialkyl group is 1: (1.02-1.1).
5. such as the preparation method of one of claim 1-4 claim described indophenols derivative, it is characterized by with the phenol of kharophen and with N, the alkyl benzene amine hydrochloride of N-dialkyl group is dissolved in the solvent, add yellow soda ash, be cooled to 0 ℃, add again Sodium Persulfate in batches, obtain red solid, obtain the indophenols derivative behind the recrystallization.
6. the preparation method of indophenols derivative as claimed in claim 2 is characterized by yellow soda ash and is (5-6.8) with mol ratio with the phenol of kharophen: 1, and Sodium Persulfate is (0.1-2.2) with mol ratio with the phenol of kharophen: 1.
7. the preparation method of indophenols derivative as claimed in claim 1, it is characterized by described phenol with kharophen is to be made by diacetyl oxide and amino-phenol hydrochloride solution generation acetylization reaction.
8. the preparation method of indophenols derivative as claimed in claim 7, the mol ratio that it is characterized by amino-phenol hydrochloride and diacetyl oxide is 1: (1.1-1.15), the solvent of described amino-phenol hydrochloride solution is acetonitrile.
9. the preparation method of indophenols derivative as claimed in claim 7, it is characterized by described amino-phenol hydrochloride is 2,4-, two chloro-3-methyl-6-amino-phenol hydrochloride, reaction formula is
10. the preparation method of indophenols derivative as claimed in claim 7 is characterized by in the amino-phenol hydrochloride solution and contains sodium-acetate, and the mol ratio of itself and amino-phenol hydrochloride is (1.1-1.2): 1.
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| CN2012100765269A CN103319910A (en) | 2012-03-20 | 2012-03-20 | Preparation method of indophenol derivative |
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| CN2012100765269A CN103319910A (en) | 2012-03-20 | 2012-03-20 | Preparation method of indophenol derivative |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105908236A (en) * | 2016-05-10 | 2016-08-31 | 广东长盈精密技术有限公司 | Coloring agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02218789A (en) * | 1989-02-20 | 1990-08-31 | Mitsubishi Kasei Corp | Liquid crystal composition |
| US20080182212A1 (en) * | 2007-01-25 | 2008-07-31 | Diehl Donald R | Stabilized dyes for thermal dye transfer materials |
-
2012
- 2012-03-20 CN CN2012100765269A patent/CN103319910A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02218789A (en) * | 1989-02-20 | 1990-08-31 | Mitsubishi Kasei Corp | Liquid crystal composition |
| US20080182212A1 (en) * | 2007-01-25 | 2008-07-31 | Diehl Donald R | Stabilized dyes for thermal dye transfer materials |
Non-Patent Citations (1)
| Title |
|---|
| 杨胜璧 等: "《化学危险品安全实用手册》", 31 July 1987, 四川科学技术出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105908236A (en) * | 2016-05-10 | 2016-08-31 | 广东长盈精密技术有限公司 | Coloring agent and preparation method thereof |
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