CN107903203A - A kind of synthetic method of 3,4 pairs of nitrophthalimides - Google Patents
A kind of synthetic method of 3,4 pairs of nitrophthalimides Download PDFInfo
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- CN107903203A CN107903203A CN201710979520.5A CN201710979520A CN107903203A CN 107903203 A CN107903203 A CN 107903203A CN 201710979520 A CN201710979520 A CN 201710979520A CN 107903203 A CN107903203 A CN 107903203A
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- nitrophthalimides
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- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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Abstract
The present invention provides a kind of synthetic method of 3,4 pairs of nitrophthalimides, comprises the following steps：Phthalimide and phosphorus pentoxide are added in the solvent concentrated sulfuric acid, nitrating agent is added dropwise under 0 DEG C of ice bath, temperature is controlled below 10 DEG C at the same time, room temperature is warming up to after being added dropwise to complete, when stirring reaction 2 10 is small, stops being added to the water obtained reaction solution after reacting and washed to obtain precipitate, the filter residue obtained after precipitate is filtered is washed with bubble, then 3,4 pairs of nitrophthalimides are obtained with ethyl alcohol recrystallization.Raw materials used and reagent of the invention is cheap and easy to get, and cost is relatively low, and reaction condition is gentle, and post-processing operation is simple, beneficial to the large-scale industrial production of product.
Description
Technical field
The present invention relates to the synthetic method of the double nitrophthalimides of 3,4- of one kind.
Background technology
Nitro substituted phthalimide is a kind of important pharmaceutical intermediate and dyestuff intermediate, mainly passes through adjacent benzene
Dicarboximide occurs nitration reaction and is synthesized.According to domestic and international report, the nitrification of phthalimide and its derivative
Method mainly has two kinds：One kind is to carry out nitration reaction by the use of the concentrated sulfuric acid and ammonium nitrate as nitrating agent, reaction yield less than
60%；One kind is that reaction yield is more than 80% by the use of the concentrated sulfuric acid and concentrated nitric acid as nitrating agent.Related phthalyl is sub- at present
The report of amine and its derivative nitration method has focused largely on single nitro substitution reaction of phthalimide and its derivative
Aspect, for phthalimide and its derivative dinitro substitution product synthetic method then substantially without reference to.
The content of the invention
The technical problem to be solved in the present invention is to provide the synthetic method of the double nitrophthalimides of 3,4- of one kind, institute
Cheap and easy to get with raw material and reagent, cost is relatively low, and reaction condition is gentle, and post-processing operation is simple, beneficial to the big rule of product
Mould industrialized production.
In order to solve the above technical problems, the technical scheme is that：
The synthetic method of the double nitrophthalimides of 3,4- of one kind, comprises the following steps：
Phthalimide and phosphorus pentoxide are added in the solvent concentrated sulfuric acid, nitrification examination is added dropwise under 0 DEG C of ice bath
Agent, while temperature is controlled below 10 DEG C, room temperature is warming up to after being added dropwise to complete, when stirring reaction 2-10 is small, stopping will after reacting
Obtained reaction solution, which is added to the water, to be washed to obtain precipitate, and the filter residue obtained after precipitate is filtered is washed with bubble, then
The double nitrophthalimides of 3,4- are obtained with ethyl alcohol recrystallization.
Preferably, the mass fraction of the solvent concentrated sulfuric acid of the present invention is 98%, and phthalimide and solvent are dense
The mass ratio of sulfuric acid is (2.7-13.7):1.
Preferably, the mass ratio of phthalimide of the present invention and the solvent concentrated sulfuric acid is 8.2:1.Nitrating agent drips
Exothermic reaction can be occurred by adding in reaction system, and heat release can cause difficult temperature control than more serious to solvent dosage very little, and solvent
Cost can be increased if dosage is too many, therefore considered, optimum solvent dosage is the matter of the concentrated sulfuric acid and phthalimide
Amount is than being 8.2:1.
Preferably, nitrating agent of the present invention is by the concentrated nitric acid of 65% mass fraction and the concentrated sulfuric acid of 98% mass fraction
Mix, and the molar ratio of concentrated nitric acid in nitrating agent, the concentrated sulfuric acid and phthalimide is (2-3.2):1:1.
Preferably, the molar ratio of the concentrated nitric acid in nitrating agent of the present invention, the concentrated sulfuric acid and phthalimide is
2.8:1:1。
Preferably, the molar ratio of phosphorus pentoxide and phthalimide of the present invention is (0-3):1.
Preferably, the molar ratio of phosphorus pentoxide and phthalimide of the present invention is 2.5:1.Phosphorus pentoxide
The water byproduct generated in reaction is can absorb as catalyst, promotes reaction to be carried out to positive reaction direction, so that it is anti-to improve nitrification
Product yield.The appropriate molar amount of phosphorus pentoxide is 2 times of phthalimide mole in theory, but due to solvent and ring
The influence of moisture in border, its optimum amount is more than theoretical amount, therefore comprehensive cost consideration, optimum amount are sub- for phthalyl
2.5 times of amine mole.
Preferably, the volume of water and the volume ratio of the solvent concentrated sulfuric acid are (1-2) during washing of the present invention:1.
Preferably, the rate of addition of nitrating agent of the present invention is 2 seconds/drop.
Preferably, when the time of stirring reaction of the present invention is 6 small.
Compared with prior art, the invention has the advantages that：
1) present invention is tried using phthalimide as starting material by nitrification of the mixed solution of the concentrated sulfuric acid and concentrated nitric acid
Agent, ice bath synthesizes the double nitrophthalimides of 3,4- under the catalytic action of phosphorus pentoxide, and reaction principle is：
The present invention have selected suitable material molar ratio, catalyst amount, solvent dosage and reaction time, obtained adjacent benzene
The di-nitrated product yield of dicarboximide is up to more than 65.5%, the yield one of phthalimide mononitrated product at present
As up to 80%, but since nitro is inertia group, have passivation to phenyl ring, being re-introduced into a nitro can reduce to phenyl ring
Yield, therefore the attainable yield of the present invention is more satisfactory yield.
2) raw materials used and reagent of the invention is cheap and easy to get, therefore cost is relatively low, and the condition reacted is gentleer,
Post-processing operation is fairly simple, is conducive to the large-scale industrial production of product.
Brief description of the drawings
Attached drawing described herein is used for providing a further understanding of the present invention, forms the part of the application, not
Inappropriate limitation of the present invention is formed, in the accompanying drawings：
Attached drawing 1 is the double nitrophthalimides of 3,4- described in embodiment 11H-NMR spectrum.
Attached drawing 2 is the FTIR spectrograms of the double nitrophthalimides of 3,4- described in embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.Wherein, the dense H in embodiment 1-62SO4Mass fraction is
98%, dense HNO3Mass fraction be 65%.
Embodiment 1
Phthalimide 29.4g, dense H are added in 500mL three-necked flasks2SO4100mL and phosphorus pentoxide
52.8g, ice-water bath are cooled to 0 DEG C, are slowly added dropwise with the speed of 2 seconds/drop into nitrating agent (dense HNO328mL and dense H2SO4
The mixed solution of 11mL), while temperature is controlled below 10 DEG C, room temperature is warming up to after being added dropwise to complete, stirring reaction 4h, stops anti-
Should after obtained reaction solution be added to the water to be poured slowly into 100-200mL water washed, separate out yellow solid, yellow consolidated
The filter residue that body obtains after filtering is washed with bubble, then obtains pale yellow crystals 3, the double nitro phthalyls of 4- with ethyl alcohol recrystallization
Imines 12.8g, yield 43.4%, fusing point are 242-243 DEG C.Structural analysis is carried out to product, product1H-NMR spectrum is such as
Shown in attached drawing 1, shown in the FTIR spectrograms as attached drawing 2 of product.
Embodiment 2
Phthalimide 29.4g, dense H are added in 500mL three-necked flasks2SO4100mL and phosphorus pentoxide
52.8g, ice-water bath are cooled to 0 DEG C, are slowly added dropwise with the speed of 2 seconds/drop into nitrating agent (dense HNO334mL and dense H2SO4
The mixed solution of 11mL), while temperature is controlled below 10 DEG C, room temperature is warming up to after being added dropwise to complete, stirring reaction 8h, stops anti-
Should after obtained reaction solution be added to the water to be poured slowly into 100-200mL water washed, separate out yellow solid, yellow consolidated
The filter residue that body obtains after filtering is washed with bubble, then obtains pale yellow crystals 3, the double nitro phthalyls of 4- with ethyl alcohol recrystallization
Imines 15.7g, yield 53.2%, fusing point are 242-243 DEG C.
Embodiment 3
Phthalimide 29.4g, dense H are added in 500mL three-necked flasks2SO4150mL and phosphorus pentoxide
66.0g, ice-water bath are cooled to 0 DEG C, are slowly added dropwise with the speed of 2 seconds/drop into nitrating agent (dense HNO334mL and dense H2SO4
The mixed solution of 11mL), while temperature is controlled below 10 DEG C, room temperature is warming up to after being added dropwise to complete, stirring reaction 10h, stops
Obtained reaction solution is added to the water to be poured slowly into 100-200mL water after reaction and is washed, yellow solid is separated out, by yellow
The filter residue that solid obtains after filtering is washed with bubble, then obtains pale yellow crystals 3, the double nitro O-phthalics of 4- with ethyl alcohol recrystallization
Acid imide 17.3g, yield 58.4%, fusing point are 242-243 DEG C.
Embodiment 4
Phthalimide 29.4g, dense H are added in 500mL three-necked flasks2SO4150mL and phosphorus pentoxide
66.0g, ice-water bath are cooled to 0 DEG C, are slowly added dropwise with the speed of 2 seconds/drop into nitrating agent (dense HNO339mL and dense H2SO4
The mixed solution of 11mL), while temperature is controlled below 10 DEG C, room temperature is warming up to after being added dropwise to complete, stirring reaction 6h, stops anti-
Should after obtained reaction solution be added to the water to be poured slowly into 100-200mL water washed, separate out yellow solid, yellow consolidated
The filter residue that body obtains after filtering is washed with bubble, then obtains pale yellow crystals 3, the double nitro phthalyls of 4- with ethyl alcohol recrystallization
Imines 19.4g, yield 65.5%, fusing point are 242-243 DEG C.
Embodiment 5
Phthalimide 29.4g, dense H are added in 500mL three-necked flasks2SO4200mL and phosphorus pentoxide
79.2g, ice-water bath are cooled to 0 DEG C, are slowly added dropwise with the speed of 2 seconds/drop into nitrating agent (dense HNO339mL and dense H2SO4
The mixed solution of 11mL), while temperature is controlled below 10 DEG C, room temperature is warming up to after being added dropwise to complete, stirring reaction 10h, stops
Obtained reaction solution is added to the water to be poured slowly into 100-200mL water after reaction and is washed, yellow solid is separated out, by yellow
The filter residue that solid obtains after filtering is washed with bubble, then obtains pale yellow crystals 3, the double nitro O-phthalics of 4- with ethyl alcohol recrystallization
Acid imide 18.3g, yield 62.0%, fusing point are 242-243 DEG C.
Embodiment 6
Phthalimide 29.4g, dense H are added in 500mL three-necked flasks2SO4200mL and phosphorus pentoxide
79.2g, ice-water bath are cooled to 0 DEG C, are slowly added dropwise with the speed of 2 seconds/drop into nitrating agent (dense HNO345mL and dense H2SO4
The mixed solution of 11mL), while temperature is controlled below 10 DEG C, room temperature is warming up to after being added dropwise to complete, stirring reaction 8h, stops anti-
Should after obtained reaction solution be added to the water to be poured slowly into 100-200mL water washed, separate out yellow solid, yellow consolidated
The filter residue that body obtains after filtering is washed with bubble, then obtains pale yellow crystals 3, the double nitro phthalyls of 4- with ethyl alcohol recrystallization
Imines 16.7g, yield 56.3%, fusing point are 242-243 DEG C.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. one kind 3, the synthetic method of the double nitrophthalimides of 4-, it is characterised in that：Comprise the following steps：
Phthalimide and phosphorus pentoxide are added in the solvent concentrated sulfuric acid, nitrating agent is added dropwise under 0 DEG C of ice bath, together
When control temperature to be warming up to room temperature after being added dropwise to complete less than 10 DEG C, when stirring reaction 2-10 is small, stop to obtain after reacting
Reaction solution, which is added to the water, to be washed to obtain precipitate, and the filter residue obtained after precipitate is filtered is washed with bubble, then uses ethanol
It is recrystallized to give the double nitrophthalimides of 3,4-.
A kind of 2. synthetic method of the double nitrophthalimides of 3,4- according to claim 1, it is characterised in that：Institute
The mass fraction for stating the solvent concentrated sulfuric acid is 98%, and the mass ratio of phthalimide and the solvent concentrated sulfuric acid is (2.7-
13.7):1。
A kind of 3. synthetic method of the double nitrophthalimides of 3,4- according to claim 2, it is characterised in that：Institute
The mass ratio for stating phthalimide and the solvent concentrated sulfuric acid is 8.2:1.
A kind of 4. synthetic method of the double nitrophthalimides of 3,4- according to claim 3, it is characterised in that：Institute
Nitrating agent is stated to be mixed by the concentrated nitric acid of 65% mass fraction and the concentrated sulfuric acid of 98% mass fraction, and in nitrating agent
The molar ratio of concentrated nitric acid, the concentrated sulfuric acid and phthalimide is (2-3.2):1:1.
A kind of 5. synthetic method of the double nitrophthalimides of 3,4- according to claim 4, it is characterised in that：Institute
The molar ratio for stating the concentrated nitric acid in nitrating agent, the concentrated sulfuric acid and phthalimide is 2.8:1:1.
A kind of 6. synthetic method of the double nitrophthalimides of 3,4- according to claim 5, it is characterised in that：Institute
The molar ratio for stating phosphorus pentoxide and phthalimide is (0-3):1.
A kind of 7. synthetic method of the double nitrophthalimides of 3,4- according to claim 6, it is characterised in that：Institute
The molar ratio for stating phosphorus pentoxide and phthalimide is 2.5:1.
A kind of 8. synthetic method of the double nitrophthalimides of 3,4- according to claim 7, it is characterised in that：Institute
The volume of water and the volume ratio of the solvent concentrated sulfuric acid are (1-2) when stating washing:1.
A kind of 9. synthetic method of the double nitrophthalimides of 3,4- according to claim 8, it is characterised in that：Institute
The rate of addition for stating nitrating agent is 2 seconds/drop.
A kind of 10. synthetic method of the double nitrophthalimides of 3,4- according to claim 9, it is characterised in that：
When the time of the stirring reaction is 6 small.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710979520.5A CN107903203B (en) | 2017-10-19 | 2017-10-19 | Synthetic method of 3, 4-dinitrophthalimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710979520.5A CN107903203B (en) | 2017-10-19 | 2017-10-19 | Synthetic method of 3, 4-dinitrophthalimide |
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| Publication Number | Publication Date |
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| CN107903203A true CN107903203A (en) | 2018-04-13 |
| CN107903203B CN107903203B (en) | 2020-06-19 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456115A (en) * | 2022-02-15 | 2022-05-10 | 辽宁科技大学 | Preparation method of 3,6-diamino-1,8-naphthalimide series compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086476A (en) * | 2014-05-26 | 2014-10-08 | 湖北新舟化工有限公司 | Preparation method for N-methyl-4-nitrophthalimide |
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- 2017-10-19 CN CN201710979520.5A patent/CN107903203B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086476A (en) * | 2014-05-26 | 2014-10-08 | 湖北新舟化工有限公司 | Preparation method for N-methyl-4-nitrophthalimide |
Non-Patent Citations (2)
| Title |
|---|
| 吕亮等: "4-氨基邻苯二甲酰亚胺合成的新工艺", 《南京工业大学学报自然科学版》 * |
| 夏森林等: "侧链含邻苯二甲酰亚胺的聚酰亚胺液晶垂直取向剂的制备与表征", 《高分子学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456115A (en) * | 2022-02-15 | 2022-05-10 | 辽宁科技大学 | Preparation method of 3,6-diamino-1,8-naphthalimide series compounds |
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