CN1552692A - Preparation of 1-Cl-4,8-dinitronaphthalene and 4-cl-1,8-dinitronaphthalene - Google Patents
Preparation of 1-Cl-4,8-dinitronaphthalene and 4-cl-1,8-dinitronaphthalene Download PDFInfo
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- CN1552692A CN1552692A CNA2003101159661A CN200310115966A CN1552692A CN 1552692 A CN1552692 A CN 1552692A CN A2003101159661 A CNA2003101159661 A CN A2003101159661A CN 200310115966 A CN200310115966 A CN 200310115966A CN 1552692 A CN1552692 A CN 1552692A
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- dinitronaphthalene
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Abstract
A process for preparing 1-Cl-4,8-dinitronaphthalene and 4-Cl-1,8-dinitronaphthalene includes such steps as dinitrifying the chloronaphthalene in organic solvent at 30-80 deg.c to obtain the mixture of target products, cooling, filtering to obtain said mixture. The organic layer in filtrate can be used cyclically.
Description
Technical field
The present invention relates in organic solvent, chloronaphthalene carry out dinitrobenzeneization, preparation 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene mixture with one step of nitration mixture.
Technical background
Synthetic in the past 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene has multiple.As with 4,5-dinitrobenzene-naphthalidine or 4,8-dinitrobenzene-naphthalidine is separately converted to 4-chloro-1,8-dinitronaphthalene or 1-chloro-4,8-dinitronaphthalene (J.Chem.Soc.1945,543 by Sang De mayer (Sandmeyer) reaction; J.Chem.Soc.1936,1338); Chloronaphthalene is handled step preparation 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, method (Rec.Trav.Chim.1962,81,209 of 8-dinitronaphthalene mixture with concentrated nitric acid or nitration mixture; Bull.Soc.Chim.France 1952,1022).The first method expensive raw material price, the operation loaded down with trivial details again; A kind of method in back is easily lumpd under nitration condition because of without solvent, and reaction is incomplete, and impurity is many, the problem that yield is low.
Summary of the invention
The purpose of this invention is to provide and a kind ofly in organic solvent, make 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene mixture by one step of chloronaphthalene and nitration mixture; Solve the problem that chloronaphthalene and nitration mixture lump easily simultaneously under the nitration reaction condition; Reduce 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the foreign matter content in the 8-dinitronaphthalene; Organic solvent that uses in present method and sulfuric acid circulation re-use.
For achieving the above object, with chloronaphthalene and organic solvent wiring solution-forming, reacted cooling among the present invention with nitration mixture in 30-80 ℃ at 6-12 hour, filter out 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture, organic layer in the filtrate and acid layer recycle, when the 1-chloro-4 that leaches, 8-dinitronaphthalene and 4-chloro-1, other impurity surpass when specifying index in the 8-dinitronaphthalene mixture, and organic solvent is steamed from organic layer and reuses.
Spendable organic solvent is inert C under nitration condition among the present invention
1-C
2The chloro thing, as methylene dichloride, trichloromethane, ethylene dichloride, and the mixture of any ratio of these solvents; The weight ratio of organic solvent and chloronaphthalene is 0.1-10: 1, be preferably 0.4-6: 1; Wherein the weight percent of each component of nitration mixture is respectively: sulfuric acid 60-86%; Nitric acid 8-34%; Water 6-25%; The mol ratio of nitric acid and chloronaphthalene is 2-3 in the nitration mixture: 1, be preferably 2.1-2.4: 1; Temperature of reaction 30-80 of the present invention ℃, be preferably 30-50 ℃.
Chloronaphthalene and a certain proportion of organic solvent are added in the reactor, temperature is brought up to 30-80 ℃, drip required nitration mixture, drip and finish, continue reaction 3-10 hour in 30-80 ℃, cooling filters out 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture, again organic layer in the filtrate and acid layer are separated with separating funnel, acid is used for the preparation of next nitration reaction nitration mixture behind the layer analysis, and organic layer is directly used in the next nitration reaction, organic solvent circulation 3-4 time after distillation remove wherein be used further to down criticize behind the impurity nitrated.
Also nitration mixture that can be required and organic solvent are added in the reactor, and temperature is brought up to 30-80 ℃, drip chloronaphthalene, drip and finish, continue to react 5-10 hour, tell the acid layer after stopping to stir in 30-80 ℃, be used for the preparation of next nitration reaction nitration mixture behind the acid layer analysis content, add water and be cooled to below 20 ℃ filtration, washing to organic layer, dry, obtain 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture.With separating funnel organic layer in the filtrate and water layer are separated, it is batch nitrated that organic layer is used further to down after impurity is removed wherein in distillation.
The present invention has easy and simple to handle, the characteristics that waste liquid is few, and the while can also make the 1-chloro-4 of higher degree, 8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene.
Embodiment
Embodiment 1:
Have in the four-hole bottle of dropping funnel, thermometer, reflux condensing tube and strong agitator in 1000ml, add 195.1g (1.08mol) 90% α-chloronaphthalene and 390g ethylene dichloride, be warmed up to 35-38 ℃, drip the nitration mixture that is made into by 473.1g 98% sulfuric acid, 171.5g 97% nitric acid and 81.4g water in 3 hours, drip and finish, be warmed up to 48-50 ℃, continue reaction 8 hours.Be cooled to below 20 ℃, filter, washing, drying obtains light yellow 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture 156.5g.The HPLC analysis revealed that has UV-detector, 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the total content of 8-dinitronaphthalene mixture is 93%.With separating funnel organic layer and acid layer are separated, it is nitrated that organic layer is used for next time, is used to prepare nitrated nitration mixture next time behind the sour layer analysis content.
Embodiment 2:
Have in the four-hole bottle of dropping funnel, thermometer, reflux condensing tube and strong agitator in 1000ml, the organic layer that adds 195.1g (1.08mol) 90% α-chloronaphthalene and embodiment 1, be warmed up to 35-38 ℃, drip the nitration mixture that recovery acid solution 406g, 98% sulfuric acid 159g and 97% nitric acid 162g by embodiment 1 are made in 3 hours, drip and finish, be warmed up to 48-50 ℃, continue reaction 8 hours.Be cooled to below 20 ℃, filter, washing, drying obtains yellow 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture 287g.The HPLC analysis revealed that has UV-detector, 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the total content of 8-dinitronaphthalene are 79.8%.With separating funnel organic layer and acid layer are separated, it is nitrated that organic layer is used for next time, is used to prepare nitrated nitration mixture next time behind the sour layer analysis content.
Embodiment 3:
Have in the four-hole bottle of dropping funnel, thermometer, reflux condensing tube and strong agitator in 1000ml, nitration mixture and 80g ethylene dichloride that adding is made into by 473.1g 98% sulfuric acid, 171.5g 97% nitric acid and 81.4g water, be warmed up to 35-38 ℃, drip 195.1g (1.08mol) 90% α-chloronaphthalene in 3 hours, drip and finish, be warmed up to 48-50 ℃, continue reaction 8 hours.Stop to stir, tell the acid layer, be used for the preparation of next nitration reaction nitration mixture behind the sour layer analysis content.Add water and stir to organic layer and be cooled to below 20 ℃, filter, washing, drying obtains yellow 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture 289.5g.The HPLC analysis revealed that has UV-detector, 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the total content of 8-dinitronaphthalene are 78.6%.With separating funnel organic layer in the filtrate and water layer are separated, it is batch nitrated that organic layer is used further to down after impurity is removed wherein in distillation.
Claims (9)
1, a kind of preparation 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene, it is characterized in that chloronaphthalene and organic solvent wiring solution-forming, reacted with nitration mixture in 30-80 ℃, cooling at 6-12 hour, filter out 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture.
2, a kind of preparation 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene, it is characterized in that nitration mixture and organic solvent are added in the reactor, temperature is brought up to 30-80 ℃, drips chloronaphthalene, drip and finish, continue reaction 5-10 hour, cooling in 30-80 ℃, filter, washing, drying obtains 1-chloro-4,8-dinitronaphthalene and 4-chloro-1,8-dinitronaphthalene mixture.
3, according to claim 1 or 2 described preparation 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene is characterized in that temperature of reaction is 30-50 ℃.
4, according to claim 1 or 2 described preparation 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method of 8-dinitronaphthalene is characterized in that the organic solvent of described use is inert C1-C2 chloro thing under nitration condition, and the mixture of any ratio of these solvents; The weight ratio of organic solvent and chloronaphthalene is 0.1-10: 1.
5, preparation 1-chloro-4 according to claim 4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene is characterized in that described chloro thing is methylene dichloride, trichloromethane or ethylene dichloride.
6, preparation 1-chloro-4 according to claim 4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene, the weight ratio that it is characterized in that described organic solvent and chloronaphthalene is 0.4-6: 1.
7, preparation 1-chloro-4 according to claim 4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene is characterized in that the weight percent of described each component of nitration mixture is respectively: sulfuric acid 60-86%; Nitric acid 8-34%; Water 6-25%;
8, preparation 1-chloro-4 according to claim 7,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene is characterized in that the mol ratio of nitric acid and chloronaphthalene is 2-3 in the described nitration mixture: 1.
9, according to claim 7 or 8 described preparation 1-chloro-4,8-dinitronaphthalene and 4-chloro-1, the method for 8-dinitronaphthalene, the mol ratio that it is characterized in that nitric acid and chloronaphthalene in the described nitration mixture is 2.1-2.4 the most: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2003101159661A CN1552692A (en) | 2003-12-18 | 2003-12-18 | Preparation of 1-Cl-4,8-dinitronaphthalene and 4-cl-1,8-dinitronaphthalene |
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| CNA2003101159661A CN1552692A (en) | 2003-12-18 | 2003-12-18 | Preparation of 1-Cl-4,8-dinitronaphthalene and 4-cl-1,8-dinitronaphthalene |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475487B (en) * | 2008-12-30 | 2012-07-18 | 江苏吉华化工有限公司 | Recycling use method of nitration acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475487B (en) * | 2008-12-30 | 2012-07-18 | 江苏吉华化工有限公司 | Recycling use method of nitration acid |
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