CN110194729A - One inter-species nitro-beta-hydroxyethyl sulfuryl preparation method - Google Patents
One inter-species nitro-beta-hydroxyethyl sulfuryl preparation method Download PDFInfo
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- CN110194729A CN110194729A CN201910508830.8A CN201910508830A CN110194729A CN 110194729 A CN110194729 A CN 110194729A CN 201910508830 A CN201910508830 A CN 201910508830A CN 110194729 A CN110194729 A CN 110194729A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
Abstract
The invention discloses an inter-species nitro-beta-hydroxyethyl sulfuryl preparation methods, belong to dye chemical industry intermediate manufacturing technology field, the following steps are included: (1) aqueous solution of hydrazine hydrate is added into reaction unit, m-nitrobenzene sulfonyl chloride slowly or is several times added；After m-nitrobenzene sulfonyl chloride adds, changes temperature to 40~70 DEG C, maintain pH5.0~7.0, keep the temperature 0.5~1.5 hour；(2) ethylene oxide is added dropwise in Xiang Shangshu reaction solution, controls 50~70 DEG C of temperature, and maintain pH7.0~7.6 with dilute sulfuric acid, filtering obtains a nitro-beta-hydroxyethyl sulfuryl.Side reaction of the invention is few, and yield reaches 98.5% or more, improves than traditional handicraft nearly by 20%；The m-nitro sulfinic acid sodium purity is high generated is reacted, product per ton can reduce 5 tons of high-salt wastewaters and about 70kg waste residue compared with traditional handicraft, and technique more cleans, is environmentally friendly；Simple process, required equipment is few, greatly reduces the investment of equipment.
Description
Technical field
The present invention relates to an inter-species nitro-beta-hydroxyethyl sulfuryl preparation methods, belong to dye chemical industry intermediate manufacturing technology
Field.
Background technique
Between nitro-beta-hydroxyethyl sulfuryl be to prepare amino-beta-hydroxyethyl sulfone intermediate, and amino-beta-hydroxyethyl sulfone
It is to prepare C.I. active blue 19 and amino-beta-hydroxyethyl sulfone sulfate important source material.Between amino-beta-hydroxyethyl sulfone sulfuric acid
Ester is mainly used for synthesizing KN type and M type reactive dye, and bright in colour, various superior performances are widely used, by attention.
Currently, the traditional preparation method of nitro-beta-hydroxyethyl sulfuryl is: with excessive sodium sulfite in water with a nitro
Benzene sulfonyl chloride carries out reduction reaction, is then filtered, and filtrate generates a large amount of high-salt wastewater generally as discharge of wastewater, filter
Cake m-nitro sulfinic acid sodium obtains a nitro-beta-hydroxyethyl sulfuryl by carrying out ethoxyl etherification with ethylene oxide after purification.
Reaction equation is as follows:
Main reaction:
Side reaction:
The shortcomings that above method, is: 1. synthesizing in m-nitro sulfinic acid sodium reaction process, m-nitrobenzene sulfonyl chloride has 8%
~10% hydrolysis generates m-nitrobenzene sodium sulfonate, yield about 79%；2. containing in the waste water that the separation of m-nitro sulfinic acid sodium generates
There are 34~36g/L m-nitro sulfinic acid sodium, 27~33g/L m-nitrobenzene sodium sulfonate, also containing a large amount of inorganic salt-mixtures, 179
~180g/L sodium sulphate, 82g/L sodium chloride, 105~108g/L sodium sulfite, COD about 62000mg/L；3. m-nitro Asia sulphur
Sour sodium subtractive process will remove the insoluble matter of reaction, and product per ton generates 70kg solid waste.
Chinese invention patent application CN103304452A discloses one kind and extracts in aromatic hydrocarbons sulfinic acid sodio-derivative waste water
The method of effective component is further processed useful composition in recycling waste water, then discharges through the disposal of three wastes, although having in cost certain
Advantage, but technique is relatively complicated, and resulting waste water is still difficult to carry out biochemical treatment.
Chinese invention patent application patent CN107098834A is reported using lewis acid as catalyst, with aromatic series
It closes the adduct (DABSO) that object is raw material and Isosorbide-5-Nitrae-diazabicylo [2.2.2] octane and sulfur dioxide and carries out Fu in a solvent
Gram acylation reaction, the method for generating corresponding aromatic sulfinic acids class compound.This method has the disadvantage in that 1. Louis used
This acid catalyst and DABSO raw material dosage are larger, and a large amount of inorganic salts, Isosorbide-5-Nitrae-diazabicylo are generated in last handling process
[2.2.2] octane is difficult to recycle, and increases environment protection treating difficulty.2. post-processing step is more, process is cumbersome, it is used extraction and
Recrystallization solvent recycling trouble, is unfavorable for industrialized production.
Therefore it provides nitro-beta-hydroxyethyl sulfuryl preparation method between a kind of side reaction is few, high income, three waste discharge are few
Just become technical field technical problem urgently to be solved.
Summary of the invention
It is few the purpose of the present invention is overcoming the deficiencies of the prior art and provide a kind of few side reaction, high income, three waste discharge
Between nitro-beta-hydroxyethyl sulfuryl preparation method.
Above-mentioned purpose of the invention reaches by the following technical programs:
One inter-species nitro-beta-hydroxyethyl sulfuryl preparation method, comprising the following steps:
(1) synthesis of m-nitro sulfinic acid sodium: the aqueous solution of hydrazine hydrate being added into reaction unit, nitre between being then added
Base benzene sulfonyl chloride, temperature control 10~50 DEG C, maintain pH5.0~7.0；After m-nitrobenzene sulfonyl chloride adds, change temperature to 40
~70 DEG C, 0.5~1.5 hour is kept the temperature, m-nitro sulfinic acid sodium reaction solution is obtained；
(2) it nitro-beta-hydroxyethyl sulfuryl synthesis between: is dripped into the m-nitro sulfinic acid sodium reaction solution that step (1) obtains
Add the ethylene oxide of reacting dose, control 50~70 DEG C of temperature, maintain pH7.0~7.6, react 18~22 hours, terminates；It is cooled to
20~30 DEG C, filtering obtains a nitro-beta-hydroxyethyl sulfuryl.
Reaction equation of the invention is as follows:
Preferably, addition m-nitrobenzene sulfonyl chloride described in step (1) described in the step (1) or slowly disposable
It is added；Or it is slowly added to several times.
Preferably, pH described in the step (1) is maintained with liquid alkaline.
Preferably, pH described in the step (2) is maintained with dilute sulfuric acid.
Preferably, the molar ratio of m-nitrobenzene sulfonyl chloride described in the step (1) and the hydrazine hydrate is 1:0.5~1:
1.0。
Preferably, the concentration of the aqueous solution of hydrazine hydrate described in the step (1) is 10wt%~40wt%.
Preferably, the concentration of liquid alkaline described in the step (1) is 5wt%~30wt%.
The present invention has the advantages that 1. synthesize m-nitro sulfinic acid sodium when, side reaction is few, yield reach 98.5% with
On, it is improved than traditional handicraft nearly by 20%.2. react the m-nitro sulfinic acid sodium purity is high of generation, can directly and ethylene oxide into
Row ethoxyl etherification, product per ton can reduce 5 tons of high-salt wastewaters and about 70kg waste residue compared with traditional handicraft, technique more clean,
Environmental protection.3. simple process, required equipment is few, greatly reduces the investment of equipment.
Below by the drawings and specific embodiments, the present invention will be further described, but is not meant to protect the present invention
Protect the limitation of range.Anyone skilled in the art are not departing within the spirit and scope of the present invention, relatively following embodiments
It carries out various variations and still belongs to the range that the present invention is protected with modification, therefore protection scope of the present invention is with claims institute circle
Subject to fixed.
Detailed description of the invention
Fig. 1 is the liquid chromatogram for the m-nitro sulfinic acid sodium that the embodiment of the present invention 1 synthesizes.
Fig. 2 is nitro-beta-hydroxyethyl sulfuryl liquid chromatogram between the embodiment of the present invention 1 synthesizes.
Fig. 3 is the liquid chromatogram for the m-nitro sulfinic acid sodium that comparative example 1 synthesizes.
Fig. 4 is nitro-beta-hydroxyethyl sulfuryl liquid chromatogram between comparative example 1 synthesizes.
Specific embodiment
Embodiment 1
One inter-species nitro-beta-hydroxyethyl sulfuryl preparation method, comprising the following steps:
(1) it synthesizes m-nitro sulfinic acid sodium: the hydrazine hydrate aqueous solution that content is 10wt% being added in 500ml flask
100g (is equivalent to 0.2mol), is slowly added to the m-nitrobenzene sulfonyl chloride 115g (being equivalent to 0.4mol) that content is 77wt%, control
Temperature 50 C processed maintains pH7.0 with the liquid alkaline of 30wt%；Change temperature to 70 DEG C, maintains pH constant, reaction was completed within 0.5 hour；
Measure reaction solution quality 321g, content 25.65%, purity 99.06%, yield 98.5%；As shown in Figure 1, being implementation of the present invention
The liquid chromatogram for the m-nitro sulfinic acid sodium that example 1 synthesizes；Wherein, the numerical value at each peak is as shown in table 1 below in Fig. 1.
Table 1
(2) epoxy nitro-beta-hydroxyethyl sulfuryl between synthesizing: is added dropwise to m-nitro sulfinic acid sodium reaction solution obtained by step (1)
Ethane 27.8g controls temperature 50 C, and maintains pH7.4 or so with dilute sulfuric acid, and reaction was completed within 22 hours, is cooled to 30 DEG C, mistake
Filter, obtains a nitro-beta-hydroxyethyl sulfuryl, quality 93g, content 92.47%, yield 94.5%, purity 96.97%, as shown in Fig. 2,
It is nitro-beta-hydroxyethyl sulfuryl liquid chromatogram between the embodiment of the present invention 1 synthesizes；Wherein, the numerical value at each peak is such as in Fig. 2
The following table 2.
Table 2
Embodiment 2
(1) synthesize m-nitro sulfinic acid sodium: it is 40wt% hydrazine hydrate aqueous solution that content is added in 500ml flask
27.5g (is equivalent to 0.22mol), and the m-nitrobenzene sulfonyl chloride 115g that content is 77wt% is added in three times and (is equivalent to
0.4mol), 10 DEG C of temperature are controlled, maintains pH7.6 with the liquid alkaline of 10wt%；Change temperature to 40 DEG C, maintains pH constant, 1.5 is small
When reaction was completed；Measure reaction solution quality 462g, content 17.90%, yield 98.9%, purity 99.22%；
(2) nitro-beta-hydroxyethyl sulfuryl between synthesizing: ethylene oxide is added dropwise in Xiang Shangshu m-nitro sulfinic acid sodium reaction solution
27.9g controls temperature 70 C, and maintains pH7.0-8.2 with dilute sulfuric acid, and reaction was completed within 18 hours, is cooled to 20 DEG C, and filtering obtains
Between nitro-beta-hydroxyethyl sulfuryl, quality 94g, content 92.13%, yield 94.8%, purity 96.91%.
Embodiment 3
(1) it synthesizes m-nitro sulfinic acid sodium: the hydrazine hydrate aqueous solution that content is 30wt% being added in 500ml flask
66.7g (is equivalent to 0.4mol), and the m-nitrobenzene sulfonyl chloride 115g (being equivalent to 0.4mol) that content is 77wt% is added in five times,
Temperature is controlled at 20 DEG C, maintains pH6.0 with the liquid alkaline of 20wt%；Change temperature to 50 DEG C, maintain pH constant, terminates within 1 hour anti-
It answers；Measure reaction solution quality 341g, content 24.32%, yield 99.2%, purity 99.19%；
(2) nitro-beta-hydroxyethyl sulfuryl between synthesizing: ethylene oxide 28g is added dropwise in Xiang Shangshu m-nitro sulfinic acid sodium reaction solution,
Temperature 60 C is controlled, and maintains pH7.0 with dilute sulfuric acid, reaction was completed within 20 hours, is cooled to 28 DEG C, and filtering obtains a nitro-β-hydroxyl
Ethyl sulfone, quality 95g, content 91.58%, yield 94.9%, purity 96.79%.
Embodiment 4
(1) synthesize m-nitro sulfinic acid sodium: it is 20wt% hydrazine hydrate aqueous solution 80g that content is added in 500ml flask
(being equivalent to 0.32mol), being slowly added to content is 77wt% m-nitrobenzene sulfonyl chloride 115g (being equivalent to 0.4mol), controls temperature
15 DEG C, with the liquid alkaline of 20wt%, maintain pH5.0；Change temperature to 40 DEG C, maintains pH constant, reaction was completed within 1.5 hours；It measures
Reaction solution quality 335g, content 24.73%, yield 99.1%, purity 99.09%；
(2) ethylene oxide nitro-beta-hydroxyethyl sulfuryl between synthesizing: is added in Xiang Shangshu m-nitro sulfinic acid sodium reaction solution
27.9g controls temperature 70 C, and maintains pH7.2 with dilute sulfuric acid, and reaction was completed within 18 hours, is cooled to 26 DEG C, and filtering obtains nitre
Base-beta-hydroxyethyl sulfuryl, quality 94g, content 92.55%, yield 95%, purity 96.82%.
Embodiment 5
(1) it synthesizes m-nitro sulfinic acid sodium: it is water-soluble that the hydrazine hydrate that content is 20wt% being added in 5000L glass-lined kettle
Liquid 960kg (is equivalent to 3.84kmol), is slowly added to the m-nitrobenzene sulfonyl chloride 1380kg that content is 77wt% and (is equivalent to
4.8kmol), 15 DEG C of temperature are controlled, with 20wt% liquid alkaline, maintains pH5.0；Change temperature to 40 DEG C, maintains pH constant, 2 hours
Reaction was completed；Measure reaction solution quality 4000kg, content 24.88%, yield 99.2%, purity 99.20%；
(2) it nitro-beta-hydroxyethyl sulfuryl between synthesizing: is collected in above-mentioned m-nitro sulfinic acid sodium reaction solution and wards off glass in 8000L
In glass kettle, ethylene oxide 335kg is added dropwise, controls temperature 70 C, and maintain pH7.2 with dilute sulfuric acid, reaction was completed within 20 hours, cooling
To 26 DEG C, filtering obtains a nitro-beta-hydroxyethyl sulfuryl, quality 1130kg, content 92.48%, yield 95%, purity 96.90%.
Comparative example 1
(1) it synthesizes m-nitro sulfinic acid sodium: water 120ml being added in 500ml flask, put into sodium sulfite 76g, slowly
The m-nitrobenzene sulfonyl chloride 115g (being equivalent to 0.4mol) that content is 77wt% is added, 27 DEG C of temperature are controlled, with the liquid of 30wt%
Alkali maintains pH7.8；Heat preservation 6 hours, reaction terminates, and liquid chromatogram measures its purity 91.00%, and filtering obtains m-nitro Asia sulphur
Sour sodium filter cake 80g, content 83%, yield 79.4%, filtrate 273ml, the sodium 36.0g/L of sulfinic acid containing m-nitro, m-nitro
Sodium sulfonate 27.7g/L, sodium sulphate 180g/L, sodium sulfite 105g/L, sodium chloride 81.3g/L, COD 62500mg/L；Such as Fig. 3
It is shown, it is the liquid chromatogram for the m-nitro sulfinic acid sodium that comparative example 1 synthesizes；Wherein, the numerical value at each peak is such as in Fig. 3
The following table 3.
Table 3
(2) nitro-beta-hydroxyethyl sulfuryl between synthesizing: being added water 190ml in 500ml flask, and it is sub- to put into above-mentioned m-nitro
Sodium sulfonate filter cake is warming up to 55 DEG C, and activated carbon 1g decoloration is added, and filtering removes insoluble matter, generates containing solid 40% filter residue 5g, filter
Ethylene oxide 22.5g is added in liquid, controls 65 DEG C of temperature, and maintain pH7.3 with dilute sulfuric acid, reaction was completed within 19 hours, is cooled to 25
DEG C, filtering obtains a nitro-beta-hydroxyethyl sulfuryl, quality 76g, content 91.71%, yield 95%, purity 96.89%；Such as figure
It is nitro-beta-hydroxyethyl sulfuryl liquid chromatogram between comparative example 1 synthesizes shown in 4；Wherein, in Fig. 4 each peak numerical value
Such as the following table 4.
Table 4
Comparative example 2
(1) it synthesizes m-nitro sulfinic acid sodium: water 120ml being added in 500ml flask, put into sodium sulfite 76g, slowly
Addition content is 77wt% m-nitrobenzene sulfonyl chloride (being equivalent to 0.4mol) 115g, controls 30 DEG C of temperature, is tieed up with 30wt% liquid alkaline
Hold pH7.5；Heat preservation 5 hours, filtering, obtains m-nitro sulfinic acid sodium filter cake 76g, content 86%, yield 78.2%, filtrate
275ml, the sodium of sulfinic acid containing m-nitro 34g.0/L, m-nitrobenzene sodium sulfonate 33.2g/L, sodium sulphate 179g/L, sodium sulfite
108g/L, sodium chloride 82g/L, COD 65800mg/L.
(2) nitro-beta-hydroxyethyl sulfuryl between synthesizing: being added water 180ml in 500ml flask, and it is sub- to put into above-mentioned m-nitro
Sodium sulfonate filter cake is warming up to 53 DEG C, and activated carbon 1g is added, and decolourizes, and filtering removes insoluble matter, generates containing solid 40% filter residue 5g, filter
Ethylene oxide 22g is added in liquid, controls temperature 60 C, and maintain pH7.4 with dilute sulfuric acid, and reaction was completed within 21 hours, is cooled to 27 DEG C,
Filtering, obtains a nitro-beta-hydroxyethyl sulfuryl, quality 74g, content 92.43%, yield 94.7%, purity 96.88%.
Comparative example 3
(1) it synthesizes m-nitro sulfinic acid sodium: water 1200L being added in 5000L stainless steel kettle, put into sodium sulfite
760kg, being slowly added to content is 77wt% m-nitrobenzene sulfonyl chloride 1150kg (being equivalent to 4kmol), controls 30 DEG C of temperature, is used
30wt% liquid alkaline maintains pH7.5；Heat preservation 5 hours, filtering, obtains m-nitro sulfinic acid sodium filter cake 755kg, content 87%, yield
78.6%, filtrate 2750L, the sodium of sulfinic acid containing m-nitro 34g.0/L, m-nitrobenzene sodium sulfonate 27.2g/L, sodium sulphate 179g/
L, sodium sulfite 107g/L, sodium chloride 82g/L, COD 61800mg/L.Filtrate by CN103304452A patented method at
Reason recycling sulfinic acid sodium 89kg, processed waste water sulfinic acid containing m-nitro 1.4g/L, m-nitrobenzene sulfonic acid 23g/L, sodium sulphate
161g/L, sulfurous acid 63g/L, sodium chloride 74g/L, COD 22500mg/L.
(2) nitro-beta-hydroxyethyl sulfuryl between synthesizing: in 3000L stainless steel kettle, being added water 1800L, put into above-mentioned filter cake,
52 DEG C are warming up to, activated carbon 10kg is added, is decolourized, filtering removes insoluble matter, generates containing solid 40% filter residue 50kg, filtrate is collected
Into 5000L glass-lined kettle, ethylene oxide 222kg is added dropwise, controls temperature 70 C, and maintain pH7.2 with dilute sulfuric acid, ties within 18 hours
Shu Fanying, is cooled to 26 DEG C, filtering, obtains a nitro-beta-hydroxyethyl sulfuryl, quality 750kg, content 91.87%, yield 94.9%,
Purity 96.76%.
Compared with the conventional method compared with secondary when method of the invention has a characteristic that 1. synthesis m-nitro sulfinic acid sodium
Reaction is few, and yield reaches 98.5% or more, improves than traditional handicraft nearly by 20%；2. the m-nitro sulfinic acid sodium for reacting generation is pure
Degree is high, and ethoxyl etherification can be directly carried out with ethylene oxide, and product per ton can reduce by 5 tons of high-salt wastewater peace treaties compared with traditional handicraft
70kg waste residue, technique more clean, are environmentally friendly；3. simple process, required equipment is few, greatly reduces the investment of equipment.
Claims (7)
1. an inter-species nitro-beta-hydroxyethyl sulfuryl preparation method, comprising the following steps:
(1) synthesis of m-nitro sulfinic acid sodium: the aqueous solution of hydrazine hydrate is added into reaction unit, m-nitro is then added
Sulfonic acid chloride, temperature control 10~50 DEG C, maintain pH5.0~7.0；After m-nitrobenzene sulfonyl chloride adds, change temperature to 40~70
DEG C, 0.5~1.5 hour is kept the temperature, m-nitro sulfinic acid sodium reaction solution is obtained；
(2) it nitro-beta-hydroxyethyl sulfuryl synthesis between: is added dropwise into the m-nitro sulfinic acid sodium reaction solution that step (1) obtains anti-
The ethylene oxide that should be measured controls 50~70 DEG C of temperature, maintains pH7.0~7.6, reacts 18~22 hours, terminates；It is cooled to 20~
30 DEG C, filtering obtains a nitro-beta-hydroxyethyl sulfuryl.
2. described in accordance with the claim 1 nitro-beta-hydroxyethyl sulfuryl preparation method, it is characterised in that: in the step (1)
Addition m-nitrobenzene sulfonyl chloride described in the step (1) is slowly added at one time；Or it is slowly added to several times.
3. nitro-beta-hydroxyethyl sulfuryl preparation method between according to claim 2, it is characterised in that: in the step (1)
The pH is maintained with liquid alkaline.
4. described in accordance with the claim 3 nitro-beta-hydroxyethyl sulfuryl preparation method, it is characterised in that: in the step (2)
The pH is maintained with dilute sulfuric acid.
5. nitro-beta-hydroxyethyl sulfuryl preparation method between according to claim 4, it is characterised in that: in the step (1)
The molar ratio of the m-nitrobenzene sulfonyl chloride and the hydrazine hydrate is 1:0.5~1:1.0.
6. nitro-beta-hydroxyethyl sulfuryl preparation method between according to claim 5, it is characterised in that: in the step (1)
The concentration of the hydrazine hydrate aqueous solution is 10wt%~40wt%.
7. nitro-beta-hydroxyethyl sulfuryl preparation method between according to claim 6, it is characterised in that: in the step (1)
The concentration of the liquid alkaline is 5wt%~30wt%.
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| CN110938021A (en) * | 2019-12-18 | 2020-03-31 | 荆门市丽康源纺织科技有限公司 | Preparation method of dye intermediate 3- (β -hydroxyethyl sulfonyl) aniline |
| CN111072527A (en) * | 2019-12-18 | 2020-04-28 | 荆门市丽康源纺织科技有限公司 | Preparation method of dye intermediate 3- (β -hydroxyethyl sulfonyl) -nitrobenzene |
| CN111170897A (en) * | 2019-12-18 | 2020-05-19 | 荆门市丽康源纺织科技有限公司 | Preparation method of meta-ester and meta-ester |
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