CN104086476A - Preparation method for N-methyl-4-nitrophthalimide - Google Patents
Preparation method for N-methyl-4-nitrophthalimide Download PDFInfo
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- CN104086476A CN104086476A CN201410225001.6A CN201410225001A CN104086476A CN 104086476 A CN104086476 A CN 104086476A CN 201410225001 A CN201410225001 A CN 201410225001A CN 104086476 A CN104086476 A CN 104086476A
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- methyl
- phthalic imidine
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- nitration
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- JBCHWGTZAAZJKG-UHFFFAOYSA-N 2-methyl-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(C)C(=O)C2=C1 JBCHWGTZAAZJKG-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006396 nitration reaction Methods 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 18
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 38
- 238000000605 extraction Methods 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 15
- 229960001701 chloroform Drugs 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 9
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical compound O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000047 product Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000002274 desiccant Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010413 mother solution Substances 0.000 abstract 2
- ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 2-methylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C)C(=O)C2=C1 ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- -1 sylvite imide Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a preparation method for N-methyl-4-nitrophthalimide. The preparation method comprises: firstly cooling fuming concentrated nitric acid to 5-8 DEG C, dropwise adding concentrated sulfuric acid and preparing the mixed acid at 10-15 DEG C; mixing N-methylphthalimide with concentrated sulfuric acid at 0 DEG C with stirring, then dropwise adding the mixed acid, and reacting for 3-4 h; using an extracting agent to extract a nitrated compound obtained in the reaction; layering, separating an upper-layer organic phase and a lower-layer sulfuric acid mother solution; recovering the upper-layer organic phase to obtain N-methyl-4-nitrophthalimide, performing centrifugation filtering and drying to obtain a finished product; and removing water in the lower-layer sulfuric acid mother solution through a drying agent, concentrating and applying to mixing of the mixed acid in the subsequent batch of the nitration reaction. According to the preparation method, by selecting proper low-temperature processing, acid adding sequence, molar ratio of reaction raw materials and the extracting agent, the yield and the purity are improved. The preparation method helps to reduce generation of by-products, improve the operation environment and reduce production cost.
Description
Technical field
The present invention relates to the synthetic method of medicine intermediate, refer to particularly a kind of preparation method of N-methyl-4-nitro phthalic imidine.
Background technology
N-methyl-4-nitro phthalic imidine (NMP) is the important intermediate of all kinds of monomer dianhydrides of synthesis of polyimides.
According to domestic and foreign literature, report, the synthetic method of N-methyl-4-nitro phthalic imidine mainly contains two kinds: a kind of is alkylated reaction preparation with potassium phthalimide and methyl iodide, or with sylvite imide and the methyl tosylate generation alkylated reaction of phthalic imidine; Another kind method is the ring-opening reaction based on phthalic anhydride and methylamine, then by the ring-closure reaction of phthalic imidine, finally N-methyl-phthalic imidine is obtained through nitration reaction.
Wherein, through nitration reaction, to obtain N-methyl-4-nitro phthalic imidine be more crucial step to N-methyl-phthalic imidine.In existing method, be to take diacetyl oxide as catalyzer, first N-methyl-phthalic imidine mixed with the vitriol oil, then reaction solution is cooled to 20 ℃ adds the concentrated nitric acid of being fuming, be then warming up to 55～60 ℃ of reactions 6 hours, finally extraction obtains.This method is because adopting frozen water to make vitriol oil cooling, can separate out N-methyl-3-nitro phthalic imidine and heat release causes yield lower, is 80% left and right.And, can produce in operation the problem of a large amount of nitrogen peroxide tobacco and a large amount of dilute sulphuric acid waste water, operating environment is poor, and eyes skin is had to intense stimulus, and acid solution treatment capacity is large, needs could discharge after neutralization, and production cost is high.
Summary of the invention
Object of the present invention will overcome the existing deficiency of prior art exactly, and a kind of preparation method of the methyl-4-of N-cheaply nitro phthalic imidine is provided.
For achieving the above object, the preparation method of N-methyl-4-nitro phthalic imidine that the present invention is designed, comprises and specifically comprises the following steps the nitration reaction of N-methyl-phthalic imidine:
1) concentrated nitric acid of being first fuming is cooled to 5～8 ℃, according to the vitriol oil, is 0.5～1.3:1～1.4 with the mol ratio of the concentrated nitric acid of being fuming, and slowly drips the vitriol oil, controls temperature at 10～15 ℃, is mixed with nitration mixture, standby;
2) ice bath is controlled temperature at 0 ℃, by N-methyl-phthalic imidine and the vitriol oil, according to mol ratio, be that 1:1.8～3.8 are uniformly mixed, according to the mol ratio of N-methyl-phthalic imidine and nitration mixture, be 1:1.5～2.7 again, the nitration mixture preparing to mixed solution and dripping, drip after 0.5 hour, react 3～4 hours;
3) after having reacted, the itrated compound generating with extraction agent extractive reaction, described extraction agent is ethyl acetate, tetracol phenixin or trichloromethane, the weight of described extraction agent is 1～1.2 times of N-methyl-phthalic imidine weight;
4) layering after extraction, separated upper organic phase and lower floor's sulfate liquor;
5) reclaim after upper organic phase, obtain N-methyl-4-nitro phthalic imidine, centrifuging, is dried to obtain finished product;
6) lower floor's sulfate liquor is removed and is anhydrated by siccative, and after concentrated, cover is used for preparing nitration mixture for next batch nitration reaction.
Preferably, step 1) in, the described vitriol oil is 0.5～0.9:1.1～1.4 with the mol ratio of the concentrated nitric acid of being fuming.
Preferably, step 2) in, the mol ratio of described N-methyl-phthalic imidine and the end acid vitriol oil, nitration mixture is 1:1.8～2.2:1.6～2.3.
By research, find step 3) in, use methylene dichloride as extraction agent, not only separation time is long, and can affect the purity of product.Therefore, preferably, described extraction agent is ethyl acetate, tetracol phenixin or trichloromethane.Best, described extraction agent is the mixing solutions of ethyl acetate and trichloromethane, and the volume ratio of described ethyl acetate and trichloromethane is 2:1, and the weight of described extraction agent is 1.2 times of N-methyl-phthalic imidine weight.
Further, step 6 of the present invention) in, when cover is used for preparing nitration mixture for next batch nitration reaction after described sulfate liquor is concentrated, add the location agent of nitration reaction adjacency pair position, the add-on of described nitration reaction adjacency pair position location agent is 1.5～3% of N-methyl-phthalic imidine weight.By research, find, use and to find by research, use diacetyl oxide as the location agent of nitration reaction adjacency pair position, reaction times length (need more than 4 hours) not only, and also it is lower to react the yield of N-methyl-4-nitro phthalic imidine of gained.Therefore, preferably, the location agent of described nitration reaction adjacency pair position is formic anhydride or propionic anhydride.Described siccative is discolour silica gel, calcium sulfate, aluminum oxide or Calcium Chloride Powder Anhydrous.
Beneficial effect of the present invention is: by selecting suitable subzero treatment, acid adding order, the mol ratio of reaction raw materials and the selection of extraction agent, improve yield and the purity of N-methyl-4-nitro phthalic imidine, yield reaches more than 93%, and purity is more than 98%.The present invention not only can reduce the generation of by product N-methyl-3-nitro phthalic imidine, and, can not produce volatility stimulator in operation, improved operating environment.Sulfuric acid spent acid cover after desiccant dryness is concentrated, for next batch nitration reaction nitration mixture, reduces sulfuric acid consumption, conservation expense, and spent acid has also reduced simultaneously, has saved again three wastes processing costs, has reduced production cost.
Embodiment
In order to explain better the present invention, below in conjunction with specific embodiment, the present invention is described in further detail, but they do not form restriction to the present invention.
Embodiment 1
The preparation method of N-methyl-4-nitro phthalic imidine, is obtained through nitration reaction by N-methyl-phthalic imidine, specifically comprises the following steps:
1) concentrated nitric acid of being first fuming is cooled to 5 ℃, according to the vitriol oil, is 0.5:1.1 with the mol ratio of the concentrated nitric acid of being fuming, and slowly drips the vitriol oil, controls temperature at 10 ℃, is mixed with nitration mixture, standby;
2) ice bath is controlled temperature at 0 ℃, by N-methyl-phthalic imidine and the vitriol oil, according to mol ratio, be that 1:1.8 is uniformly mixed, according to the mol ratio of N-methyl-phthalic imidine and nitration mixture, be 1:1.6 again, the nitration mixture preparing to mixed solution and dripping, drip after 0.5 hour, react 3 hours;
3) after having reacted, use the itrated compound of the mixing solutions extractive reaction generation of ethyl acetate and trichloromethane, the volume ratio of ethyl acetate and trichloromethane is 2:1, and the weight of extraction agent is 1.2 times of N-methyl-phthalic imidine weight;
4) layering after extraction, separated upper organic phase and lower floor's sulfate liquor;
5) after recovery upper organic phase, obtain N-methyl-4-nitro phthalic imidine, centrifuging, the dry finished product that to obtain;
6) lower floor's sulfate liquor is removed and is anhydrated by siccative calcium sulfate, and after concentrated, cover is used for preparing nitration mixture for next batch nitration reaction, and while preparing nitration mixture, adding formic anhydride, the add-on of formic anhydride is 1.5% of N-methyl-phthalic imidine weight.
After testing, the yield of gained N-methyl-4-nitro phthalic imidine is 96.3%, and purity is 99.1%.
Embodiment 2
The preparation method of N-methyl-4-nitro phthalic imidine, is obtained through nitration reaction by N-methyl-phthalic imidine, specifically comprises the following steps:
1) concentrated nitric acid of being first fuming is cooled to 8 ℃, according to the vitriol oil, is 0.9:1.4 with the mol ratio of the concentrated nitric acid of being fuming, and slowly drips the vitriol oil, controls temperature at 15 ℃, is mixed with nitration mixture, standby;
2) ice bath is controlled temperature at 0 ℃, by N-methyl-phthalic imidine and the end acid vitriol oil, according to mol ratio, be that 1:2.2 is uniformly mixed, according to the mol ratio of N-methyl-phthalic imidine and nitration mixture, be 1:2.3 again, the nitration mixture preparing to mixed solution and dripping, drip after 0.5 hour, react 3 hours;
3) after having reacted, use the itrated compound of the mixing solutions extractive reaction generation of ethyl acetate and trichloromethane, the volume ratio of ethyl acetate and trichloromethane is 2:1, and extraction agent weight is 1.1 times of N-methyl-phthalic imidine weight;
4) layering after extraction, separated upper organic phase and lower floor's sulfate liquor;
5) after recovery upper organic phase, obtain N-methyl-4-nitro phthalic imidine, centrifuging, the dry finished product that to obtain;
6) lower floor's sulfate liquor is removed and is anhydrated by siccative aluminum oxide, and after concentrated, cover is used for preparing nitration mixture for next batch nitration reaction, and while preparing nitration mixture, adding propionic anhydride, the add-on of propionic anhydride is 2.1% of N-methyl-phthalic imidine weight.
After testing, the yield of gained N-methyl-4-nitro phthalic imidine is 95.8%, and purity is 99.2%.
Embodiment 3
The preparation method of N-methyl-4-nitro phthalic imidine, is obtained through nitration reaction by N-methyl-phthalic imidine, specifically comprises the following steps:
1) concentrated nitric acid of being first fuming is cooled to 6 ℃, according to the vitriol oil, is 0.8:1.3 with the mol ratio of the concentrated nitric acid of being fuming, and slowly drips the vitriol oil, controls temperature at 12 ℃, is mixed with nitration mixture, standby;
2) ice bath is controlled temperature at 0 ℃, by N-methyl-phthalic imidine and the end acid vitriol oil, according to mol ratio, be that 1:2 is uniformly mixed, according to the mol ratio of N-methyl-phthalic imidine and nitration mixture, be 1:2.1 again, the nitration mixture preparing to mixed solution and dripping, drip after 0.5 hour, react 3 hours;
3) after having reacted, use the itrated compound of the mixing solutions extractive reaction generation of ethyl acetate and trichloromethane, the volume ratio of ethyl acetate and trichloromethane is 2:1, and the weight of extraction agent is 1.1 times of N-methyl-phthalic imidine weight;
4) layering after extraction, separated upper organic phase and lower floor's sulfate liquor;
5) after recovery upper organic phase, obtain N-methyl-4-nitro phthalic imidine, centrifuging, the dry finished product that to obtain;
6) lower floor's sulfate liquor is removed and is anhydrated by siccative Calcium Chloride Powder Anhydrous, and after concentrated, cover is used for preparing nitration mixture for next batch nitration reaction, and while preparing nitration mixture, adding propionic anhydride, the add-on of propionic anhydride is 1.8% of N-methyl-phthalic imidine weight.
After testing, the yield of gained N-methyl-4-nitro phthalic imidine is 96.6%, and purity is 99.3%.
Embodiment 4
The preparation method of N-methyl-4-nitro phthalic imidine, is obtained through nitration reaction by N-methyl-phthalic imidine, specifically comprises the following steps:
1) concentrated nitric acid of being first fuming is cooled to 7 ℃, according to the vitriol oil, is 1.3:1.4 with the mol ratio of the concentrated nitric acid of being fuming, and slowly drips the vitriol oil, controls temperature at 13 ℃, is mixed with nitration mixture, standby;
2) ice bath is controlled temperature at 0 ℃, by N-methyl-phthalic imidine and the end acid vitriol oil, according to mol ratio, be that 1:3.8 is uniformly mixed, according to the mol ratio of N-methyl-phthalic imidine and nitration mixture, be 1:2.7 again, the nitration mixture preparing to mixed solution and dripping, drip after 0.5 hour, react 3 hours;
3) after having reacted, use the itrated compound of the mixing solutions extractive reaction generation of ethyl acetate and trichloromethane, the volume ratio of ethyl acetate and trichloromethane is 2:1, and the weight of extraction agent is 1.1 times of N-methyl-phthalic imidine weight;
4) layering after extraction, separated upper organic phase and lower floor's sulfate liquor;
5) after recovery upper organic phase, obtain N-methyl-4-nitro phthalic imidine, centrifuging, the dry finished product that to obtain;
6) lower floor's sulfate liquor is removed and is anhydrated by siccative discolour silica gel, and after concentrated, cover is used for preparing nitration mixture for next batch nitration reaction, and while preparing nitration mixture, adding formic anhydride, the add-on of formic anhydride is 2.8% of N-methyl-phthalic imidine weight.
After testing, the yield of gained N-methyl-4-nitro phthalic imidine is 94.2%, and purity is 98.8%.
Embodiment 5
The preparation method of N-methyl-4-nitro phthalic imidine, is obtained through nitration reaction by N-methyl-phthalic imidine, specifically comprises the following steps:
1) concentrated nitric acid of being first fuming is cooled to 5 ℃, according to the vitriol oil, is 1.2:1.3 with the mol ratio of the concentrated nitric acid of being fuming, and slowly drips the vitriol oil, controls temperature at 10 ℃, is mixed with nitration mixture, standby;
2) ice bath is controlled temperature at 0 ℃, by N-methyl-phthalic imidine and the end acid vitriol oil, according to mol ratio, be that 1:3.1 is uniformly mixed, according to the mol ratio of N-methyl-phthalic imidine and nitration mixture, be 1:2.25 again, the nitration mixture preparing to mixed solution and dripping, drip after 0.5 hour, react 4 hours;
3) after having reacted, use the itrated compound of the mixing solutions extractive reaction generation of ethyl acetate, the weight of ethyl acetate is 1.1 times of N-methyl-phthalic imidine weight;
4) layering after extraction, separated upper organic phase and lower floor's sulfate liquor;
5) after recovery upper organic phase, obtain N-methyl-4-nitro phthalic imidine, centrifuging, the dry finished product that to obtain;
6) lower floor's sulfate liquor is removed and is anhydrated by siccative discolour silica gel, and after concentrated, cover is used for preparing nitration mixture for next batch nitration reaction, and while preparing nitration mixture, adding formic anhydride, the add-on of formic anhydride is 2.5% of N-methyl-phthalic imidine weight.
After testing, the yield of gained N-methyl-4-nitro phthalic imidine is 90.7%, and purity is 95.6%.
Claims (7)
1. a preparation method for N-methyl-4-nitro phthalic imidine, comprises and it is characterized in that the nitration reaction of N-methyl-phthalic imidine, comprises the following steps:
1) concentrated nitric acid of being first fuming is cooled to 5～8 ℃, according to the vitriol oil, is 0.5～1.3:1～1.4 with the mol ratio of the concentrated nitric acid of being fuming, and slowly drips the vitriol oil, controls temperature at 10～15 ℃, is mixed with nitration mixture, standby;
2) ice bath is controlled temperature at 0 ℃, by N-methyl-phthalic imidine and the vitriol oil, according to mol ratio, be that 1:1.8～3.8 are uniformly mixed, according to the mol ratio of N-methyl-phthalic imidine and nitration mixture, be 1:1.5～2.7 again, the nitration mixture preparing to mixed solution and dripping, drip after 0.5 hour, react 3～4 hours;
3) after having reacted, the itrated compound generating with extraction agent extractive reaction, described extraction agent is ethyl acetate, tetracol phenixin or trichloromethane, the weight of described extraction agent is 1～1.2 times of N-methyl-phthalic imidine weight;
4) layering after extraction, separated upper organic phase and lower floor's sulfate liquor;
5) reclaim after upper organic phase, obtain N-methyl-4-nitro phthalic imidine, centrifuging, is dried to obtain finished product;
6) lower floor's sulfate liquor is removed and is anhydrated by siccative, and after concentrated, cover is used for preparing nitration mixture for next batch nitration reaction.
2. the preparation method of N-methyl-4-nitro phthalic imidine according to claim 1, is characterized in that: step 1) in, the described vitriol oil is 0.5～0.9:1.1～1.4 with the mol ratio of the concentrated nitric acid of being fuming.
3. the preparation method of N-methyl-4-nitro phthalic imidine according to claim 1, is characterized in that: step 2) in, the mol ratio of described N-methyl-phthalic imidine and the end acid vitriol oil, nitration mixture is 1:1.8～2.2:1.6～2.3.
4. the preparation method of N-methyl-4-nitro phthalic imidine according to claim 1, it is characterized in that: step 3) in, described extraction agent is the mixing solutions of ethyl acetate and trichloromethane, the volume ratio of described ethyl acetate and trichloromethane is 2:1, and the weight of described extraction agent is 1.2 times of N-methyl-phthalic imidine weight.
5. the preparation method of N-methyl-4-nitro phthalic imidine according to claim 1, it is characterized in that: step 6) in, when after described sulfate liquor is concentrated, cover is used for preparing nitration mixture for next batch nitration reaction, add the location agent of nitration reaction adjacency pair position, the add-on of described nitration reaction adjacency pair position location agent is 1.5～3% of N-methyl-phthalic imidine weight.
6. the preparation method of N-methyl-4-nitro phthalic imidine according to claim 1, is characterized in that: the location agent of described nitration reaction adjacency pair position is formic anhydride or propionic anhydride.
7. the preparation method of N-methyl-4-nitro phthalic imidine according to claim 1, is characterized in that: step 6) in, described siccative is discolour silica gel, calcium sulfate, aluminum oxide or Calcium Chloride Powder Anhydrous.
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| CN201410225001.6A CN104086476B (en) | 2014-05-26 | 2014-05-26 | The preparation method of N-methyl-4-nitrophthalimide |
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| CN201410225001.6A CN104086476B (en) | 2014-05-26 | 2014-05-26 | The preparation method of N-methyl-4-nitrophthalimide |
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| Publication Number | Publication Date |
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| CN104086476A true CN104086476A (en) | 2014-10-08 |
| CN104086476B CN104086476B (en) | 2015-12-30 |
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| CN201410225001.6A Active CN104086476B (en) | 2014-05-26 | 2014-05-26 | The preparation method of N-methyl-4-nitrophthalimide |
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Cited By (4)
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| CN107903203A (en) * | 2017-10-19 | 2018-04-13 | 五邑大学 | A kind of synthetic method of 3,4 pairs of nitrophthalimides |
| CN109305933A (en) * | 2018-10-30 | 2019-02-05 | 浙江万丰化工有限公司 | A method of preparing N- alkyl -4- nitrophthalimide |
| CN113396146A (en) * | 2018-12-21 | 2021-09-14 | 高新特殊工程塑料全球技术有限公司 | For preparing 4-nitro-N- (C)1-8Process for alkyl) phthalimides |
| CN113549001A (en) * | 2021-07-21 | 2021-10-26 | 华阳新材料科技集团有限公司 | A kind of preparation method of N-alkyl-4-nitrophthalimide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903203A (en) * | 2017-10-19 | 2018-04-13 | 五邑大学 | A kind of synthetic method of 3,4 pairs of nitrophthalimides |
| CN107903203B (en) * | 2017-10-19 | 2020-06-19 | 五邑大学 | A kind of synthetic method of 3,4-bisnitrophthalimide |
| CN109305933A (en) * | 2018-10-30 | 2019-02-05 | 浙江万丰化工有限公司 | A method of preparing N- alkyl -4- nitrophthalimide |
| CN113396146A (en) * | 2018-12-21 | 2021-09-14 | 高新特殊工程塑料全球技术有限公司 | For preparing 4-nitro-N- (C)1-8Process for alkyl) phthalimides |
| CN113549001A (en) * | 2021-07-21 | 2021-10-26 | 华阳新材料科技集团有限公司 | A kind of preparation method of N-alkyl-4-nitrophthalimide |
| CN113549001B (en) * | 2021-07-21 | 2024-03-22 | 华阳新材料科技集团有限公司 | A kind of preparation method of N-alkyl-4-nitrophthalimide |
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