2-naphtylamine-6-sulfonyl aniline and preparation method and purposes
Affiliated technical field
The present invention relates to a kind of new naphthylamines sulfonanilide compounds and preparation method and purposes, specifically is exactly the compound that a kind of name is called the 2-naphtylamine-6-sulfonyl aniline, the preparation method and its usage of this compound.
Background technology
Through the retrieval of Hubei Province's Scientific And Technical Intelligence Center, there is no this compound of report both at home and abroad, there is not synthetic method yet.The amino common methods of protection is to make acetylation reagent with aceticanhydride under alkaline condition, and productive rate generally is about 85%, and the waste water of brownish black, contaminate environment are arranged.
The innovation and creation content
The object of the present invention is to provide a kind of name to be called the compound of 2-naphtylamine-6-sulfonyl aniline, the preparation method of this compound and purposes, this compound can be used as dyestuff intermediate, and its simple synthetic method is pollution-free, productive rate height, good product quality.
Concrete technical scheme is as follows:
A kind of name is called the compound of 2-naphtylamine-6-sulfonyl aniline, and its structural formula is:
The fusing point 218-220 of this compound ℃, can be used as dyestuff intermediate.
A kind of method of the 2-of preparation naphtylamine-6-sulfonyl aniline: it is with acetyl Broenner'sacid and chlorsulfonic acid, sulfur oxychloride effect, through ice analyse, wash and the sulfonyl chloride compound of acetyl Broenner'sacid, behind aniline reaction, obtain product through hydrolysis, neutralization again.The reaction formula for preparing this compound is:
According to technical scheme of the present invention, when synthetic by the acetyl Broenner'sacid: chlorsulfonic acid: the ratio of sulfur oxychloride=1: 2.8-3.1: 0.8-1.0 (weight ratio) is fed in raw material, stir down 2h at 45-50 ℃, ice is analysed, is washed then, with the gained intermediate in pH=11~12 time with the aniline effect, then at pH=14,95-98 ℃ of following hydrolysis 2h, be cooled to 50 ℃, be neutralized to neutrality with hydrochloric acid, product is separated out in cooling, filter, wash and promptly get qualified product twice.
According to technical scheme of the present invention, described acetyl Broenner'sacid is under alkaline condition, and Broenner'sacid and aceticanhydride stir 1.5h at 85-90 ℃, directly dries and gets.
In this step of acetylization reaction; the consumption of strict control water; after reaction is finished; negative pressure drying; thereby improved productive rate, avoided waste water, chlorosulphonation is crucial; feed ratio is pressed the acetyl Broenner'sacid: chlorsulfonic acid: sulfur oxychloride=1: 2.8-3.1: 0.8-1.0 (weight ratio) can reach the present invention's purpose.
Adopt technical scheme of the present invention, do not have brownish black waste water in this step of acetylization reaction, avoided environmental pollution, productive rate is near 100%, and can satisfy the specification of quality of subsequent reactions, greatly reduces production cost, improved economic benefit; In chlorosulfonation, strict control acetyl Broenner'sacid: chlorsulfonic acid: the ratio of sulfur oxychloride, its quality product reaches export requirement.
The fusing point 218-220 of compound of the present invention ℃, product is analyzed through HPLC, and content is greater than 98%, and total recovery 94% has good application prospects and prospect of export.
Embodiment
Embodiment 1
Add 100mL water, NaOH7g, Broenner'sacid 30g, aceticanhydride 16g in there-necked flask, 85-90 ℃ is stirred 1.5h down, and drying under reduced pressure gets the acetyl Broenner'sacid.
Add chlorsulfonic acid 31g, exsiccant acetyl Broenner'sacid 10.5g, sulfur oxychloride 9g in another there-necked flask, 45-50 ℃ is stirred 2h down, and pour into then ice in the frozen water that 120g ice adds 130g water and analyse, filtration, product washs to pH=4-5 with frozen water.
Wet the said products is packed in the there-necked flask, add entry 70mL, transfer pH=12, add the new aniline that steams of 7g with 50%NaOH, 20-25 ℃ is reacted 2h down, constantly adds alkali and keeps pH=12, adds 50%NaOH 14g then, 95-98 ℃ of hydrolysis 2h cools to 50 ℃, transfers pH=7 with 36% hydrochloric acid.Product is separated out in cooling, filters, and washes twice and gets qualified product, and overall yield 94% is analyzed content>98% through PHLC.
Embodiment 2
In the 250ml there-necked flask, add entry 35ml, sodium hydroxide 2.2g adds Broenner'sacid 10g after the stirring and dissolving, aceticanhydride 5.5g is warmed up to 70 ℃ of dissolvings, and 80~90 ℃ of stirring reactions 1 hour incline to vaporizer, dry to constant weight under the infrared lamp, get acetyl Broenner'sacid 12.70g, productive rate 98.6%.
In the 100ml there-necked flask, add chlorsulfonic acid 28g (be reflected in the Fume Hoods and carry out), stir and add exsiccant acetyl Broenner'sacid 10g down, 0.5 add chlorination sulfoxide 8g after hour again, 45 ℃ ± 2 times stirring reactions 1.5 hours, then under agitation in impouring 120g ice and the 120g water, separate out the bright yellow product, negative pressure filtration, frozen water are washed till pH=5~6.
Above-mentioned wet product is placed the 250ml there-necked flask, add entry 60ml, stir into pasty state, the solution that drips NaOH30% drips the new aniline 6.5g that steams to pH=11~12 o'clock, at room temperature stirs after adding 1.5 hours, the pH value can constantly descend, and should replenish NaOH in good time, to keep pH=11~12, add 30%NaOH20g then, 93~100 ℃ of stirring reactions 2 hours cool to 40 ℃, HCl with 18% transfers pH6~7, and product, filtration under diminished pressure are separated out in cooling, washing twice, total recovery about 94%.High pressure liquid chromatographic analysis: content 98%.