CN100412054C - 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid and its salts and synthesis method thereof - Google Patents
3-acetamino-5-amino-4-hydroxy benzene sulfonic acid and its salts and synthesis method thereof Download PDFInfo
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- CN100412054C CN100412054C CNB2006100264804A CN200610026480A CN100412054C CN 100412054 C CN100412054 C CN 100412054C CN B2006100264804 A CNB2006100264804 A CN B2006100264804A CN 200610026480 A CN200610026480 A CN 200610026480A CN 100412054 C CN100412054 C CN 100412054C
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- sulfonic acid
- hydroxy
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- reductive agent
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- SFUJTLIHMWZDTL-UHFFFAOYSA-N 3-acetamido-5-amino-4-hydroxybenzenesulfonic acid Chemical compound CC(=O)NC1=CC(S(O)(=O)=O)=CC(N)=C1O SFUJTLIHMWZDTL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000003839 salts Chemical class 0.000 title claims description 14
- 238000001308 synthesis method Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- RHPXYZMDLOJTFF-UHFFFAOYSA-N 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC([N+]([O-])=O)=C1O RHPXYZMDLOJTFF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 44
- 230000002829 reductive effect Effects 0.000 claims description 44
- 239000003153 chemical reaction reagent Substances 0.000 claims description 21
- 230000021736 acetylation Effects 0.000 claims description 20
- 238000006640 acetylation reaction Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012346 acetyl chloride Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 38
- 238000010189 synthetic method Methods 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HNBIMSMQXHTGGA-UHFFFAOYSA-N 2-acetamido-5-amino-4-hydroxybenzenesulfonic acid Chemical compound C(C)(=O)NC1=C(C=C(C(=C1)O)N)S(=O)(=O)O HNBIMSMQXHTGGA-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- MSTBFSKFKYRGFP-UHFFFAOYSA-N [Na].CC(=O)NC1=CC(S(O)(=O)=O)=CC(N)=C1O Chemical compound [Na].CC(=O)NC1=CC(S(O)(=O)=O)=CC(N)=C1O MSTBFSKFKYRGFP-UHFFFAOYSA-N 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- -1 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid 6-acetylaminohydroxyphenylarsonic acid Chemical compound 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- IEUBLHQHYNBJED-UHFFFAOYSA-N 3,5-diamino-4-hydroxybenzenesulfonic acid Chemical compound NC1=CC(S(O)(=O)=O)=CC(N)=C1O IEUBLHQHYNBJED-UHFFFAOYSA-N 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ULUIMLJNTCECJU-UHFFFAOYSA-N 3-amino-4-hydroxybenzenesulfonate;hydron Chemical compound NC1=CC(S(O)(=O)=O)=CC=C1O ULUIMLJNTCECJU-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a method for preparing 3-acetamido-5-amino-4-hydroxy-benzenesulfonic acid, which comprises the procedures that 1, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid is atetylated; 2, products obtained in procedure 1 react with a reductant, and then products of the 3-acetamido-5-amino-4-hydroxy-benzenesulfonic acid are obtained. The preparation method can also comprise the procedures that 1, the 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid reacts with the reductant; 2, products obtained in procedure 1 are atetylated, and then products of the 3-acetamido-5-amino-4-hydroxy-benzenesulfonic acid are obtained. The reductant is selected from hydrogen gas and is one or multiple of NaxHmSyOz with reducibility, wherein the x is an integral number from 1 to 10, the m is an integral number from 0 to 10, the y is an integral number from 1 to 10, and the z is an integral number from 0 to 10. The present invention also discloses a method for preparing 3-acetamido-5-amidol-4-hydroxyl benzene sulfonic acid salt. The methods avoid environmental pollution because of the existing iron powder reduction methods and can obtain high reaction yield, high product quality and high productive efficiency.
Description
Technical field
The present invention relates to the synthetic method of 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid and salt thereof.
Background technology
The 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid 6-acetylaminohydroxyphenylarsonic acid 2-amino-phenol-4-sulfonic acid that is otherwise known as has following structural formula:
3-acetamino-5-amino-4-hydroxy benzene sulfonic acid and salt thereof are mainly as the important intermediate of synthetic dyestuff.Their derived product has obtained using very widely in daily production and life.
In the prior art, the synthetic method of 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid and salt thereof is roughly as follows:,, get with iron powder reducing after acetylize as raw material with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid and salt (being generally sodium salt) thereof again.The main drawback of this method is that the iron powder reducing method can cause sizable pollution to environment, and the reaction yield of this method is low, and quality product is not high, and production efficiency is low.
Summary of the invention
The object of the present invention is to provide the synthetic method of a kind of 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid and salt thereof, this method has been avoided iron powder reducing method pollution on the environment, and can obtain higher reaction yield, quality product and production efficiency.
In a first aspect of the present invention, a kind of method of the 3-of preparation acetamino-5-amino-4-hydroxy benzene sulfonic acid is provided, this method may further comprise the steps: (1) carries out acetylization reaction to 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid; (2) product that step (1) is obtained and reductive agent reaction obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid product thus, and described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10.
In a second aspect of the present invention, a kind of method of the 3-of preparation acetamino-5-amino-4-hydroxy benzene sulfonic acid salt is provided, this method may further comprise the steps: (1) carries out acetylization reaction to 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt; (2) product that step (1) is obtained and reductive agent reaction obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt product thus, and described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10.
In a third aspect of the present invention, a kind of method of the 3-of preparation acetamino-5-amino-4-hydroxy benzene sulfonic acid is provided, this method may further comprise the steps: (1) with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid and reductive agent reaction, described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10; (2) product that step (1) is obtained carries out acetylization reaction, obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid product thus.
In a fourth aspect of the present invention, a kind of method of the 3-of preparation acetamino-5-amino-4-hydroxy benzene sulfonic acid salt is provided, this method may further comprise the steps: (1) with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt and reductive agent reaction, described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10; (2) product that step (1) is obtained carries out acetylization reaction, obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt product thus.
The present invention also provides a kind of method of the 3-of preparation acetamino-5-amino-4-hydroxy benzene sulfonic acid salt, this method may further comprise the steps: make the 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid by above-mentioned first aspect or the described method of the third aspect, and then be carried out to reactant salt, make required 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt.
In aforesaid method, described reductive agent preferably is selected from hydrogen, Na
2S, Na
2SO
3, Na
2S
2O
5, Na
2S
2O
4, NaHSO
3, Na
2S
2, Na
2S
3, Na
2S
4, Na
2S
5, Na
2S
6, Na
2S
7, Na
2S
8, Na
2S
9, Na
2S
10Or Na
2Among the HS one or more.More preferably, described reductive agent is selected from NaHSO
3(sodium bisulfite).
In aforesaid method, preferably utilize diacetyl oxide or Acetyl Chloride 98Min. to carry out described acetylization reaction as acetylation reagent.
In aforesaid method, reduction reaction is preferably carried out in 20-150 ℃ of temperature range; Described acetylization reaction preferably carries out in-10-100 ℃ temperature range.Be more preferably described reduction reaction and in 60-120 ℃ of temperature range, carry out, especially preferably in 70-100 ℃ of temperature range, carry out.Be more preferably described acetylization reaction and in 0-80 ℃ of temperature range, carry out, especially preferably in 20-50 ℃ of temperature range, carry out.
In aforesaid method, the consumption of described reductive agent is preferably reductive agent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid or its salt is 15: 1～1: 1, is more preferably 5: 1～1.5: 1.The consumption of described acetylation reagent is preferably acetylation reagent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid or its salt is 5: 1～1: 1, is more preferably 2: 1～1: 1.
Embodiment
The invention provides the synthetic method of 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid.
A kind of synthetic method may further comprise the steps: (1) carries out acetylization reaction to 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid; (2) product that step (1) is obtained and reductive agent reaction obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid product thus, and described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10.
This synthetic method can be represented with following reacting flow chart:
Another kind of synthetic method may further comprise the steps: (1) with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid and reductive agent reaction, described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10; (2) product that step (1) is obtained carries out acetylization reaction, obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid product thus.
This synthetic method can be represented with following reacting flow chart:
The invention provides the synthetic method of 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt.
A kind of synthetic method comprises that the 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid that will make with as above one of two kinds of methods is carried out to reactant salt again, makes required 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt.
Described salt-forming reaction can be any reaction that can form required 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt, as long as this instead would not have a negative impact to the present invention.Employed reagent of salt-forming reaction and reaction conditions are that those skilled in the art can rule of thumb determine.
Can also synthesize 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt as raw material with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt.
A kind of method is may further comprise the steps: (1) carries out acetylization reaction to 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt; (2) product that step (1) is obtained and reductive agent reaction obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt product thus, and described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10.
Another kind method may further comprise the steps: (1) with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt and reductive agent reaction, described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10; (2) product that step (1) is obtained carries out acetylization reaction, obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt product thus.
In above-mentioned several synthetic methods, used reductive agent is selected from hydrogen, has the Na of reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10.More preferably be selected from hydrogen, Na
2S, Na
2SO
3, Na
2S
2O
5(Sodium Pyrosulfite), Na
2S
2O
4(vat powder), NaHSO
3(sodium bisulfite), Na
2S
2, Na
2S
3, Na
2S
4, Na
2S
5, Na
2S
6, Na
2S
7, Na
2S
8, Na
2S
9, Na
2S
10Or Na
2Among the HS one or more.The particularly preferred reductive agent of the present invention is selected from NaHSO
3(sodium bisulfite).
The consumption of described reductive agent is a reductive agent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid or its salt is preferably 15: 1～and 1: 1, more preferably 5: 1～1.5: 1.
Reduction reaction better is to carry out in 20-150 ℃ of temperature range, is more preferably in 60-120 ℃ of temperature range and carries out, and especially preferably carries out in 70-100 ℃ of temperature range.The pressure of reduction reaction is 1-15kg/cm more fortunately
2In, better at 1-5kg/cm
2In.
In above-mentioned synthetic method, acetylization reaction can carry out under suitable temperature and pressure condition with acetylation reagent.The present invention can adopt any material that ethanoyl can be provided as acetylation reagent, as long as it can not have a negative impact to the present invention.Particularly preferred acetylation reagent comprises diacetyl oxide or Acetyl Chloride 98Min..The temperature and pressure of acetylization reaction is that those skilled in the art can rule of thumb determine.The temperature of acetylization reaction better is in-10-100 ℃ scope, is more preferably in 0-80 ℃ scope, preferably in 20-50 ℃ scope.
The consumption of acetylation reagent is an acetylation reagent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid or its salt is preferably 5: 1～and 1: 1, more preferably 2: 1～1: 1.
Major advantage of the present invention is as follows:
(1) synthetic method of the present invention can be avoided prior art iron powder reducing method pollution on the environment effectively.
(2) synthetic method of the present invention can obtain higher reaction yield and production efficiency, has good quality product simultaneously, and for example the purity of product is very high.
(3) synthetic method of the present invention has been simplified the equipment of industrial product and production technique, consider from ecological and economic angle, and be quite favourable.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage.
The preparation of embodiment 1 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid
Adding concentration is 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid 200 grams (being equivalent to 0.85 mole) of 100% in the reaction vessel that 1000 ml waters are housed; in reaction vessel, drip 100 milliliters of diacetyl oxides (being equivalent to 1 mole) in 20-25 ℃; dropwised in lasting 2 hours; carry out acetylization reaction and to chromatogram (HPLC) analysis demonstration reaction solution, do not contain raw material 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid, obtain intermediate 3-acetylaminohydroxyphenylarsonic acid 4-hydroxyl-5-nitrobenzene-sulfonic acid.
In reaction vessel, add NaHSO
3(sodium bisulfite) 300 grams (being equivalent to 4.17 moles), to chromatogram (HPLC) analysis demonstration reaction solution, do not contain intermediate 3-acetylaminohydroxyphenylarsonic acid 4-hydroxyl-5-nitrobenzene-sulfonic acid in about 10 hours in 80-85 ℃ of reaction, through purifying, drying obtains product 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid 180.2 grams.The outward appearance of products obtained therefrom is the near-white powder, and chromatogram content is 98% (HPLC mensuration), and chemical content is 98% (diazonium titration measuring), and product yield is 84% (in raw material 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid).
The preparation of embodiment 2 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid sodium
3-acetamino-5-amino-4-hydroxy benzene sulfonic acid that embodiment 1 is made and 30% sodium hydroxide react in 25～35 ℃ for about 88 milliliters, and through purifying, drying makes product 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid sodium 177.6 grams.The outward appearance of products obtained therefrom is the near-white powder, and chromatogram content (HPLC mensuration) is 98%, and chemical content (diazonium titration measuring) is 98%, and product yield is 76% (in raw material 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid).
The preparation of embodiment 3 3-acetamino-5-amino-4-hydroxy benzene sulfonic acids
Adding concentration is that 100% 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid 200 grams (being equivalent to 0.85 mole) and concentration are 60%Na in the reaction vessel that 1000 ml waters are housed
2S (sodium sulphite) 200 restrains (being equivalent to 1.54 moles), reacts in 80-85 ℃ not contain raw material 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid in about 10 hours to chromatogram (HPLC) analysis demonstration reaction solution, promptly obtains intermediate 3,5-diamino-4-hydroxy benzenesulfonic acid.
Then, in 20-25 ℃ of dropping 100 milliliters of diacetyl oxide (being equivalent to 1 mole), dropwised in lasting 2 hours, to chromatogram (HPLC) analytical reaction liquid, do not contain intermediate 3,5-diamino-4-hydroxy benzenesulfonic acid, through purifying, drying obtains product 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid 135 grams.The outward appearance of products obtained therefrom is the near-white powder, and chromatogram content (HPLC mensuration) is 98%, and chemical content (diazonium titration measuring) is 98%, and product yield is 63% (in raw material 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid).
The preparation of embodiment 4 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid sodium
3-acetamino-5-amino-4-hydroxy benzene sulfonic acid that embodiment 3 is made and 30% sodium hydroxide react in 25～35 ℃ for about 66 milliliters, through purifying, make product 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid sodium 135 grams.The outward appearance of products obtained therefrom is the near-white powder, and chromatogram content (HPLC mensuration) is 98%, and chemical content (diazonium titration measuring) is 98%, and product yield is 57.8% (in raw material 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid).
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (25)
1. method for preparing the 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid, this method may further comprise the steps:
(1) 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid is carried out acetylization reaction;
(2) product that step (1) is obtained and reductive agent reaction obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid product thus, and described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10.
2. the method for claim 1 is characterized in that described reductive agent is selected from hydrogen, Na
2S, Na
2SO
3, Na
2S
2O
5, Na
2S
2O
4, NaHSO
3, Na
2S
2, Na
2S
3, Na
2S
4, Na
2S
5, Na
2S
6, Na
2S
7, Na
2S
8, Na
2S
9, Na
2S
10Or Na
2Among the HS one or more.
3. the method for claim 1 is characterized in that utilizing diacetyl oxide or Acetyl Chloride 98Min. to carry out described acetylization reaction as acetylation reagent.
4. the method for claim 1 is characterized in that described reduction reaction carries out in 20-150 ℃ of temperature range; Described acetylization reaction carries out in-10-100 ℃ temperature range.
5. the method for claim 1, the consumption that it is characterized in that described reductive agent is a reductive agent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid is 15: 1～1: 1.
6. the method for claim 1, the consumption that it is characterized in that described acetylation reagent is an acetylation reagent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid is 5: 1～1: 1.
7. method for preparing 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt, this method may further comprise the steps:
(1) 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt is carried out acetylization reaction;
(2) product that step (1) is obtained and reductive agent reaction obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt product thus, and described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10.
8. method as claimed in claim 7 is characterized in that described reductive agent is selected from hydrogen, Na
2S, Na
2SO
3, Na
2S
2O
5, Na
2S
2O
4, NaHSO
3, Na
2S
2, Na
2S
3, Na
2S
4, Na
2S
5, Na
2S
6, Na
2S
7, Na
2S
8, Na
2S
9, Na
2S
10Or Na
2Among the HS one or more.
9. method as claimed in claim 7 is characterized in that utilizing diacetyl oxide or Acetyl Chloride 98Min. to carry out described acetylization reaction as acetylation reagent.
10. method as claimed in claim 7 is characterized in that described reduction reaction carries out in 20-150 ℃ of temperature range; Described acetylization reaction carries out in-10-100 ℃ temperature range.
11. method as claimed in claim 7, the consumption that it is characterized in that described reductive agent is a reductive agent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt is 15: 1～1: 1.
12. method as claimed in claim 7, the consumption that it is characterized in that described acetylation reagent is an acetylation reagent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt is 5: 1～1: 1.
13. a method for preparing the 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid, this method may further comprise the steps:
(1) with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid and reductive agent reaction, described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10;
(2) product that step (1) is obtained carries out acetylization reaction, obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid product thus.
14. method as claimed in claim 13 is characterized in that described reductive agent is selected from hydrogen, Na
2S, Na
2SO
3, Na
2S
2O
5, Na
2S
2O
4, NaHSO
3, Na
2S
2, Na
2S
3, Na
2S
4, Na
2S
5, Na
2S
6, Na
2S
7, Na
2S
8, Na
2S
9, Na
2S
10Or Na
2Among the HS one or more.
15. method as claimed in claim 13 is characterized in that utilizing diacetyl oxide or Acetyl Chloride 98Min. to carry out described acetylization reaction as acetylation reagent.
16. method as claimed in claim 13 is characterized in that described reduction reaction carries out in 20-150 ℃ of temperature range; Described acetylization reaction carries out in-10-100 ℃ temperature range.
17. method as claimed in claim 13, the consumption that it is characterized in that described reductive agent is a reductive agent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid is 15: 1～1: 1.
18. method as claimed in claim 13, the consumption that it is characterized in that described acetylation reagent is an acetylation reagent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid is 5: 1～1: 1.
19. a method for preparing 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt, this method may further comprise the steps:
(1) with 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt and reductive agent reaction, described reductive agent is the Na that is selected from hydrogen, has reductibility
xH
mS
yO
zIn one or more, x is the integer of 1-10 in the formula, m is the integer of 0-10, y is the integer of 1-10, z is the integer of 0-10;
(2) product that step (1) is obtained carries out acetylization reaction, obtains 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt product thus.
20. method as claimed in claim 19 is characterized in that described reductive agent is selected from hydrogen, Na
2S, Na
2SO
3, Na
2S
2O
5, Na
2S
2O
4, NaHSO
3, Na
2S
2, Na
2S
3, Na
2S
4, Na
2S
5, Na
2S
6, Na
2S
7, Na
2S
8, Na
2S
9, Na
2S
10Or Na
2Among the HS one or more.
21. method as claimed in claim 19 is characterized in that utilizing diacetyl oxide or Acetyl Chloride 98Min. to carry out described acetylization reaction as acetylation reagent.
22. method as claimed in claim 19 is characterized in that described reduction reaction carries out in 20-150 ℃ of temperature range; Described acetylization reaction carries out in-10-100 ℃ temperature range.
23. method as claimed in claim 19, the consumption that it is characterized in that described reductive agent is a reductive agent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt is 15: 1～1: 1.
24. method as claimed in claim 19, the consumption that it is characterized in that described acetylation reagent is an acetylation reagent: the mol ratio of 3-amino-4-hydroxy-5-nitrobenzene-sulfonic acid salt is 5: 1～1: 1.
25. method for preparing 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt, this method may further comprise the steps: make the 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid by claim 1 or 13 described methods, and then be carried out to reactant salt, make required 3-acetamino-5-amino-4-hydroxy benzene sulfonic acid salt.
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| CN1223593C (en) * | 2003-06-04 | 2005-10-19 | 鲁南制药集团股份有限公司 | Preparation of Leiliqusai |
| CN1733713A (en) * | 2005-08-08 | 2006-02-15 | 扬州大学 | 5-aminoanthraquinone-1-sulfonate sodium synthesis technology |
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| CN1223593C (en) * | 2003-06-04 | 2005-10-19 | 鲁南制药集团股份有限公司 | Preparation of Leiliqusai |
| CN1733713A (en) * | 2005-08-08 | 2006-02-15 | 扬州大学 | 5-aminoanthraquinone-1-sulfonate sodium synthesis technology |
Non-Patent Citations (2)
| Title |
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| 两步一釜法合成邻乙酰氨基苯酚. 张强，宋东明.辽宁化工，第5期. 1999 |
| 两步一釜法合成邻乙酰氨基苯酚. 张强，宋东明.辽宁化工，第5期. 1999 * |
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