CN113549001B - Preparation method of N-alkyl-4-nitrophthalimide - Google Patents
Preparation method of N-alkyl-4-nitrophthalimide Download PDFInfo
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- CN113549001B CN113549001B CN202110869120.5A CN202110869120A CN113549001B CN 113549001 B CN113549001 B CN 113549001B CN 202110869120 A CN202110869120 A CN 202110869120A CN 113549001 B CN113549001 B CN 113549001B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 26
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 2-methylisoindole-1,3-dione Chemical group C1=CC=C2C(=O)N(C)C(=O)C2=C1 ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 7
- 239000010935 stainless steel Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 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 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 19
- -1 alkyl aldehyde Chemical class 0.000 abstract description 10
- 238000006396 nitration reaction Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 150000001412 amines Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000003973 alkyl amines Chemical class 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001546 nitrifying effect Effects 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical class COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical class COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- DLKDEVCJRCPTLN-UHFFFAOYSA-N 2-butylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCCC)C(=O)C2=C1 DLKDEVCJRCPTLN-UHFFFAOYSA-N 0.000 description 2
- JZDSOQSUCWVBMV-UHFFFAOYSA-N 2-ethylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CC)C(=O)C2=C1 JZDSOQSUCWVBMV-UHFFFAOYSA-N 0.000 description 2
- RLARUBPTQYKZKA-UHFFFAOYSA-N 2-propylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCC)C(=O)C2=C1 RLARUBPTQYKZKA-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940072395 n-butylphthalimide Drugs 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LSVBBJVITBGNFC-UHFFFAOYSA-N 2-butyl-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(CCCC)C(=O)C2=C1 LSVBBJVITBGNFC-UHFFFAOYSA-N 0.000 description 1
- FFBUYJAHSNPQDH-UHFFFAOYSA-N 2-ethyl-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(CC)C(=O)C2=C1 FFBUYJAHSNPQDH-UHFFFAOYSA-N 0.000 description 1
- HUDPLKWXRLNSPC-UHFFFAOYSA-N 4-aminophthalhydrazide Chemical compound O=C1NNC(=O)C=2C1=CC(N)=CC=2 HUDPLKWXRLNSPC-UHFFFAOYSA-N 0.000 description 1
- KMEBUNSLFRQSEM-UHFFFAOYSA-N 5-amino-2-methylisoindole-1,3-dione Chemical compound C1=C(N)C=C2C(=O)N(C)C(=O)C2=C1 KMEBUNSLFRQSEM-UHFFFAOYSA-N 0.000 description 1
- DIMVLSWEUOUYFE-UHFFFAOYSA-N 5-nitro-2-propylisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(CCC)C(=O)C2=C1 DIMVLSWEUOUYFE-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical group O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
The invention discloses a preparation method of N-alkyl-4-nitrophthalimide, which comprises the following steps: step 1) mixing phthalic anhydride, alkyl aldehyde and inorganic amine, reacting under the action of hydrogen, cooling, crystallizing and drying to obtain N-alkyl phthalimide; step 2) performing nitration reaction on the N-alkyl phthalimide obtained in the step 1), purifying and drying a product to obtain the N-alkyl-4-nitrophthalimide; wherein, the alkyl aldehyde in the step 1) is preferably C1-4 alkyl aldehyde. The preparation method has the advantages of wide sources of raw materials, low cost, simple process, easy mass production and the like. The synthesis is performed by a one-step method, the reaction efficiency is high, the device is simple and easy to operate, and the environment is protected.
Description
Technical Field
The invention relates to the field of organic chemistry, in particular to a preparation method of N-alkyl-4-nitrophthalimide.
Background
N-alkyl-4-nitrophthalimide is an important chemical intermediate and is widely applied to the fields of medicines, photoelectric materials, pesticides, dyes and the like. For example, N-alkyl-4-nitrophthalimide is reduced to obtain N-alkyl-4-aminophthalimide, and then the N-alkyl-4-aminophthalimide is subjected to azide to prepare the disperse dye. N-methyl-4-aminophthalimide is a typical electron donor-acceptor type material which can be used as a fluorescent probe and other marking materials, and is an important intermediate for synthesizing pesticides such as isoluminol, antibacterial agents, antitumor agents and the like. In the field of new materials, monomers such as N-methyl-4-nitrophthalimide self-condense to form polyimides under the action of catalysts. The current synthesis methods of N-alkyl-4-nitrophthalimide mainly comprise three methods:
(1) The method has the defects of complex preparation process, more byproducts, high price of 4-nitroaniline, difficult purification and the like, and the conversion rate is low when the 4-nitroaniline reacts with the alkylamine, so that the method is not suitable for industrial production.
(2) Phthalic anhydride is used as a raw material to be acylated into phthalimide, then the phthalimide reacts with an alkylating reagent to obtain N-alkyl phthalimide, and then the N-alkyl-4-nitrophthalimide is obtained by nitration. In the method, the alkylating reagent is usually halogenated alkane, dimethyl sulfate or dimethyl carbonate and the like, wherein the dimethyl sulfate has high toxicity, the halogenated alkane and the dimethyl carbonate have high price, and the phthalimide is firstly converted into corresponding potassium or sodium salt, so that the method has more steps and serious environmental pollution, and is not suitable for industrial production.
(3) The phthalic anhydride is used as a raw material to react with alkylamine to obtain N-alkyl phthalimide, and then the N-alkyl-4-nitro phthalimide is obtained through nitration. The method has cheap raw materials and easy reaction, but the gas phase reaction with the alkylamine requires high pressure and the alkylamine corrodes equipment, so that the cost is increased. The reaction with aqueous alkylamine solution requires the addition of solvents such as toluene and xylene as water scavengers, resulting in low product yields.
Aiming at the problems in the prior art, a new method for preparing the N-alkyl-4-nitrophthalimide, which has the advantages of simple synthesis method and high reaction efficiency, is urgently needed.
Disclosure of Invention
The invention provides a novel preparation method of N-alkyl-4-nitrophthalimide, which aims at the defects of complex synthesis method, high cost and low yield of N-alkyl-4-nitrophthalimide in the prior art.
The technical scheme provided by the invention is as follows:
a method for preparing N-alkyl-4-nitrophthalimide, comprising the following steps:
step 1) mixing phthalic anhydride, alkyl aldehyde and inorganic amine, reacting under the action of hydrogen, cooling, crystallizing and drying to obtain N-alkyl phthalimide;
and 2) performing nitration reaction on the N-alkyl phthalimide obtained in the step 1), purifying and drying a product to obtain the N-alkyl-4-nitrophthalimide.
The reaction equation of the preparation method provided by the invention is as follows:
the technical scheme provided by the invention adopts low-cost and easily-obtained phthalic anhydride as a raw material, and N-alkyl phthalimide is obtained by imidizing in one step in an aqueous solution reaction system. Compared with the method (1), the phthalic anhydride raw material is cheap and easy to obtain and has high conversion rate; compared with the method (2), the method does not use alkylating reagents such as dimethyl sulfate with high toxicity, halogenated alkane, dimethyl carbonate and the like, and the one-step synthesis equipment is simple and easy to operate; compared with the method (3), the method omits the defects of low product yield and alkylamine corrosion equipment caused by water removal solvents such as toluene, xylene and the like.
Preferably, in certain embodiments of the present invention, the alkyl aldehyde in step 1) above is preferably a C1-4 alkyl aldehyde.
Preferably, in certain embodiments of the present invention, the temperature of the reaction described in step 1) above is between 90 and 200 ℃.
More preferably, the temperature of the above reaction is 150 to 200 ℃.
Preferably, in certain embodiments of the present invention, the alkyl aldehyde described in step 1) above is formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde or butyraldehyde; the inorganic amine in the step 1) is one or more selected from ammonia water, urea or melamine.
Preferably, in certain embodiments of the present invention, the molar ratio of phthalic anhydride, aldehyde, amine described in step 1) above is 1:0.1 to 5:0.1 to 3, the mole ratio of the hydrogen to the phthalic anhydride in the step 1) is 1 to 20:1.
preferably, in some embodiments of the present invention, the time of the reaction described in the above step 1) is 0.5 to 2 hours, and the time of the nitration reaction described in the above step 2) is 0.5 to 5 hours.
Preferably, in some embodiments of the present invention, the reaction described in step 1) above is preceded by a step of introducing an inert gas to displace air in the reactor. The inert gas may be any one selected from nitrogen, carbon dioxide, and a rare gas, or a combination thereof.
Preferably, in certain embodiments of the present invention, the temperature of the nitration reaction described in step 2) above is from 0 to 70 ℃.
Preferably, in some embodiments of the present invention, the nitrifying agent used in the nitrifying reaction in the step 2) is one or more selected from fuming nitric acid, a mixture of concentrated sulfuric acid and fuming nitric acid, or a mixture of concentrated sulfuric acid and nitrate having a concentration of 95% or more.
Preferably, in certain embodiments of the present invention, the mass ratio of the N-alkylphthalimide described in step 2) above to nitrate ions in the nitrifying agent is 1:9-15.
In the present invention, the tail gas produced by the reaction can be recovered by condensation.
Preferably, in one embodiment of the present invention, the preparation method specifically includes:
step 1) adding phthalic anhydride, alkyl aldehyde and inorganic amine into a reactor according to a certain molar ratio, introducing nitrogen to replace air in the reactor, then introducing a certain amount of hydrogen, heating to a certain temperature to react for a certain time, cooling for crystallization, filtering, washing and drying to obtain the N-alkylphthalimide.
Step 2) slowly adding the obtained N-alkylphthalimide into a reaction kettle containing a certain amount of a pre-prepared nitrifying agent, controlling the proper temperature and preserving the temperature for a period of time, extracting, centrifuging, filtering, washing and drying to obtain the N-alkyl-4-nitrophthalimide.
The beneficial effects of the invention are as follows:
the preparation method has the advantages of wide sources of raw materials, low cost, simple process, easy mass production and the like. The synthesis is performed by a one-step method, the reaction efficiency is high, the device is simple and easy to operate, and the environment is protected.
Detailed Description
The invention discloses a preparation method of N-alkyl-4-nitrophthalimide, and a person skilled in the art can properly improve process parameters by referring to the content of the invention. It is to be particularly pointed out that all similar substitutes and modifications apparent to those skilled in the art are deemed to be included in the invention and that the relevant person can make modifications and appropriate alterations and combinations of what is described herein to make and use the technology without departing from the spirit and scope of the invention.
In the present invention, unless otherwise indicated, scientific and technical terms used herein have the meanings commonly understood by one of ordinary skill in the art. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components. The terms "such as," "for example," and the like are intended to refer to exemplary embodiments and are not intended to limit the scope of the present disclosure.
The following is a description of some of the terms appearing in the present invention.
The term "phthalic anhydride" refers to phthalic anhydride of formula C 8 H 4 O 3 Is a cyclic anhydride formed by intramolecular dehydration of phthalic acid. Phthalic anhydride is a white solid, is an important raw material in chemical industry, and is particularly used for manufacturing plasticizers.
The term "nitration" refers to the introduction of a nitro group (-NO) into an organic compound molecule 2 ) Is a process of (2). The reaction mechanism of the nitration of the aromatic compound is as follows: the-OH group of nitric acid is protonated, then a molecule of water is removed by a dehydrating agent to form a nitroxyl positive ion intermediate, and finally electrophilic aromatic substitution reaction is carried out with benzene ring, and a molecule of hydrogen is removed.
In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail with reference to specific embodiments.
Example 1:
296g of phthalic anhydride, 280ml of 37% industrial formaldehyde aqueous solution and 150ml of ammonia water are added into a 1L stainless steel magnetic stirring autoclave, after the air in the autoclave is replaced by nitrogen, 4mol of hydrogen is introduced, stirring is started, the temperature is raised to 100 ℃, the reaction is carried out for 1h, the temperature is reduced to 30 ℃, after the gas in the autoclave is replaced by nitrogen, the reaction solution is poured out, filtered, washed and dried, and a sample is obtained. The sample tested was N-methylphthalimide. The yield is 90% and the purity is 99% calculated by phthalic anhydride.
Slowly adding 1mol of the prepared N-methylphthalimide into a reaction kettle containing concentrated sulfuric acid and concentrated nitric acid in a molar ratio of 3:1, controlling the temperature below 10 ℃, heating to 50 ℃ in a water bath after the addition is finished, preserving the heat for 1h, extracting, filtering, washing and drying to obtain a sample. The sample obtained by detection is N-methyl-4 nitro-phthalimide, the yield is 97%, and the purity is 99%.
Example 2:
148g of phthalic anhydride, 220ml of industrial acetaldehyde aqueous solution with the mass fraction of 40% and 126ml of ammonia water are added into a 1L stainless steel magnetic stirring autoclave, 5mol of hydrogen is introduced after the air in the autoclave is replaced by nitrogen, the reaction is carried out for 1.5h when the temperature is raised to 120 ℃ by starting stirring, the temperature is reduced to 30 ℃, the gas in the autoclave is replaced by nitrogen, and then the reaction solution is poured out, filtered, washed and dried to obtain a sample. The sample tested was N-ethylphthalimide. Calculated by phthalic anhydride, the yield is 85% and the purity is 99%.
Slowly adding 0.4mol of the prepared N-ethylphthalimide into a 12mol fuming nitric acid reaction kettle, controlling the temperature below 10 ℃, heating to 50 ℃ in a water bath after the addition is completed, preserving the heat for 2 hours, extracting, centrifugally filtering, washing and drying to obtain a sample. The sample obtained by detection is N-ethyl-4 nitro-phthalimide, the yield is 95%, and the purity is 98%.
Example 3:
296g of phthalic anhydride, 460ml of industrial propionaldehyde and 144g of urea are added into a 1L stainless steel magnetic stirring autoclave, 16mol of hydrogen is introduced after the air in the autoclave is replaced by nitrogen, stirring is started, the temperature is raised to 130 ℃, the reaction is carried out for 2 hours, the temperature is reduced to 30 ℃, after the gas in the autoclave is replaced by nitrogen, the reaction solution is poured out, filtered, washed and dried, and a sample is obtained. The sample tested was N-propylphthalimide. The yield was 82% and the purity was 98% based on phthalic anhydride.
Slowly adding 1mol of the prepared N-propylphthalimide into a mixed solution reaction kettle containing concentrated sulfuric acid and potassium nitrate, controlling the temperature below 10 ℃, heating to 55 ℃ in a water bath after the addition is completed, preserving the heat for 4 hours, extracting, centrifugally filtering, washing and drying to obtain a sample. The sample obtained by detection is N-propyl-4 nitro-phthalimide, the yield is 90 percent, and the purity is 99 percent.
Example 4:
296g of phthalic anhydride, 276ml of industrial butyraldehyde and 151g of melamine are added into a 1L stainless steel magnetic stirring autoclave, 15mol of hydrogen is introduced after the air in the autoclave is replaced by nitrogen, stirring is started, the temperature is raised to 150 ℃, the temperature is kept for 2 hours, the temperature is lowered to 30 ℃, after the gas in the autoclave is replaced by nitrogen, the reaction solution is poured out, filtered, washed and dried, and a sample is obtained. The sample tested was N-butylphthalimide. The yield was 82% and the purity was 98% based on phthalic anhydride.
Slowly adding 1mol of the prepared N-butyl phthalimide into a mixed solution reaction kettle containing concentrated sulfuric acid and sodium nitrate, controlling the temperature below 10 ℃, heating to 60 ℃ in a water bath after the addition is completed, preserving the heat for 4 hours, extracting, centrifugally filtering, washing and drying to obtain a sample. The sample obtained by detection is N-butyl-4 nitro-phthalimide, the yield is 85%, and the purity is 99%.
Example 5:
296.22g of phthalic anhydride, 17.66ml of 37% industrial formaldehyde aqueous solution and 6.006g of urea are added into a 1L stainless steel magnetic stirring autoclave, after the air in the autoclave is replaced by nitrogen, 1mol of hydrogen is introduced, stirring is started, the temperature is raised to 90 ℃, the reaction is carried out for 0.5h, the temperature is reduced to 30 ℃, after the gas in the autoclave is replaced by nitrogen, the reaction solution is poured out, filtered, washed and dried, and a sample is obtained. The sample tested was N-methylphthalimide. The yield is 80% and the purity is 99% based on phthalic anhydride.
Slowly adding 1mol of the prepared N-methylphthalimide into a reaction kettle containing concentrated sulfuric acid and concentrated nitric acid in a molar ratio of 3:1, controlling the temperature below 10 ℃, heating to 0 ℃ in a water bath after the addition is finished, preserving the temperature for 0.5h, extracting, filtering, washing and drying to obtain a sample. The sample obtained by detection is N-methyl-4 nitro-phthalimide, the yield is 90 percent, and the purity is 99 percent.
Example 6:
148.11g of phthalic anhydride, 405ml of 37% industrial formaldehyde aqueous solution and 126g of melamine are added into a 1L stainless steel magnetic stirring autoclave, after the air in the autoclave is replaced by nitrogen, 20mol of hydrogen is introduced, stirring is started, the temperature is raised to 200 ℃, the reaction is carried out for 2 hours, the temperature is reduced to 30 ℃, after the gas in the autoclave is replaced by nitrogen, the reaction solution is poured out, filtered, washed and dried, and a sample is obtained. The sample tested was N-methylphthalimide. The yield is 95% and the purity is 99% based on phthalic anhydride.
Slowly adding 1mol of the prepared N-methylphthalimide into a 15mol fuming nitric acid reaction kettle, controlling the temperature below 10 ℃, after the addition, heating to 70 ℃ in a water bath, preserving the heat for 5 hours, extracting, filtering, washing and drying to obtain a sample. The sample obtained by detection is N-methyl-4 nitro-phthalimide, the yield is 97%, and the purity is 99%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. A preparation method of N-methyl-4-nitrophthalimide is characterized in that 148.11g of phthalic anhydride, 405ml of 37% industrial formaldehyde aqueous solution and 126g of melamine are added into a 1L stainless steel magnetic stirring autoclave, after the air in the autoclave is replaced by nitrogen, 20mol of hydrogen is introduced, stirring is started, when the temperature is raised to 200 ℃, the reaction is carried out for 2 hours, the temperature is reduced to 30 ℃, after the gas in the autoclave is replaced by nitrogen, the reaction solution is poured out, filtered, washed and dried, and a sample is obtained; the detected sample is N-methyl phthalimide; calculated by phthalic anhydride, the yield is 95 percent and the purity is 99 percent;
slowly adding 1mol of the prepared N-methylphthalimide into a 15mol fuming nitric acid reaction kettle, controlling the temperature below 10 ℃, after the addition, heating to 70 ℃ in a water bath, preserving the temperature for 5 hours, extracting, filtering, washing and drying to obtain a sample; the sample obtained by detection is N-methyl-4-nitro-phthalimide, the yield is 97%, and the purity is 99%.
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