CN103524415A - One-step synthesis method for caprolactam from cyclohexanol, hydrogen peroxide and hydroxylamine - Google Patents

One-step synthesis method for caprolactam from cyclohexanol, hydrogen peroxide and hydroxylamine Download PDF

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CN103524415A
CN103524415A CN201310516252.5A CN201310516252A CN103524415A CN 103524415 A CN103524415 A CN 103524415A CN 201310516252 A CN201310516252 A CN 201310516252A CN 103524415 A CN103524415 A CN 103524415A
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hexalin
selectivity
hydrogen peroxide
hso
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王荷芳
贾立元
王延吉
王媛媛
刘红涛
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Hebei University of Technology
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
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    • C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement

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Abstract

The invention provides a one-step synthesis method for caprolactam from cyclohexanol, hydrogen peroxide and hydroxylamine. In the method, the raw materials cyclohexanol, hydrogen peroxide and hydroxylamine are added in the same reactor with quaternary ammonium salt-type acidic ionic liquid and Na2WO4.2H2O as catalysts, and a one-step synthesis reaction can be carried out in the same system. The three phases of cyclohexanol oxidation, cyclohexanone oximation and cyclohexanone-oxime rearrangement in the reaction are integrated in the same system. The method solves the problem of long technological process caused by stepwise synthesis in traditional technologies, achieves short process synthesis technology for caprolactam, has low energy consumption and is environmentally friendly.

Description

A kind of method by hexalin, hydrogen peroxide and azanol synthesizing caprolactam in one step
Technical field
The present invention relates to the synthetic of hexanolactam, specifically a kind of technique by hexalin, hydrogen peroxide and the direct synthesis of caprolactam of azanol.
Technical background
Hexanolactam (CPL) is one of a kind of important industrial chemicals, mainly for the production of Polyamide Engineering Plastic and tynex, also can be used for producing antiplatelet drug-Padil, produces laurocapram etc., and purposes is very extensive.In recent years, along with the development of synthesising fibre industry, people still can not meet people's demand to also the grow with each passing day caprolactam production amount of ，Dan China of the demand of hexanolactam.In addition,, because traditional technology exists that reaction and separation processes device is many, technical process is long, production efficiency is low, energy consumption is high and the problem such as waste discharge, therefore clean, the efficient and safe abbreviated system of exploitation surely belongs to Caprolactam Industry important development direction from now on.
The industrial process of hexanolactam mainly contains: toluene method, photo-nitrosation of cyclohexane process and pimelinketone-hydroxylamine assay, wherein pimelinketone-hydroxylamine assay is most widely used.And pimelinketone can be oxidized and be obtained by hexalin, its process flow formula is as follows:
Figure BDA0000403022560000011
This reaction comprises three segment process: first hexalin carries out oxidizing reaction generation pimelinketone under the effect of catalyzer; Then, pimelinketone and azanol carry out oximation reaction generation cyclohexanone-oxime; Last cyclohexanone-oxime is reset and is generated hexanolactam under effect of sulfuric acid.There is technical process length, reset and use oleum to produce the problems such as low value ammonium sulfate and equipment corrosion in this method.
Be entitled as in the document of " ionic liquid phase-transfer catalysis hexalin oxidation prepare pimelinketone " (Journal of Molecular Catalysis, 6(2007), Shao Lili etc.), with hydrogen peroxide as oxygenant, [C 16mim] HSO 4[C 14mim] HSO 4as phase-transfer catalyst, Na 2wO 42H 2o is that catalyst hexalin generates pimelinketone, and the yield of pimelinketone approaches 100%.Ren etc. are at document " Preparation of cyclic ketoximes using aqueous hydroxylamine in ionic liquids " (Tetrahedron Letters, 42(2001)), point out, adopting 1-butyl-3-methyl imidazolium tetrafluoroborate is catalyzer, catalysis of pimelinketone and azanol reaction synthesizing cyclohexane 1 ketoxime effectively, yield is 95%, but system does not detect the generation of hexanolactam.Meanwhile, Zhao Jiangkun etc. is at document " acidic ion liquid-ZnCl 2catalysis of pimelinketone oxime liquid phase Beckmann rearrangement reaction " point out in (high chemical engineering journal, 5(2011)), in Acetonitrile, [HSO 3-b-N (CH 3) 3] HSO 4with ZnCl 2the catalyst system catalysis of pimelinketone oxime liquid phase Beckmann rearrangement reaction forming, under optimal conditions, pimelinketone transformation efficiency reaches 100%, and hexanolactam yield is 94.9%.
Above-mentioned three pieces of documents have only been investigated ionic liquid-catalyzed hexalin synthesizing cyclohexanone, pimelinketone carry out that oximation reaction generates cyclohexanone-oxime and by cyclohexanone-oxime the single step building-up process through Beckmann rearrangement synthesis of caprolactam, do not relate to by the one-step synthesis technique of the direct synthesis of caprolactam of hexalin and about the integrated reaction of hexalin synthesis of caprolactam and there is not yet report.
The Chinese patent (publication number CN102000555A) that is entitled as " for catalyzer and the methods for making and using same of the direct synthesis of caprolactam of cyclohexanone oxamidinating " discloses a kind of catalyzer for the direct synthesis of caprolactam of cyclohexanone oxamidinating, this catalyzer is the pillared type catalyzer of titanium, by pimelinketone, hydrogen peroxide, ammoniacal liquor and catalyzer drop in reactor, Ammoximation reaction temperature 70 C, reaction times 8h, after having reacted, add ionic liquid at room temperature N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate catalysis of pimelinketone oxime Bekmann resets, reset temperature 50 C, rearrangement time 30min, pimelinketone transformation efficiency is 46.4%, the selectivity of hexanolactam is 80.8%.In this system, the transformation efficiency of pimelinketone is not high.
Summary of the invention
Technical problem to be solved by this invention is: for existing in caprolactam production process, technical process is long, rearrangement is used oleum to produce the problems such as low value ammonium sulfate and equipment corrosion, provide a kind of and take hexalin, hydrogen peroxide and azanol as the direct synthesis of caprolactam novel method of raw material, raw material hexalin, hydrogen peroxide and azanol are joined in same reactor, make it under same system, carry out one-step synthesis reaction.That is to say the oxidation of three phases hexalin, pimelinketone oximate and the rearrangement of cyclohexanone-oxime that in this reaction, experience are integrated in an individual system and are carried out, select to have ionic liquid and the Na of acidic catalyst and phase transfer function 2wO 42H 2o is catalyzer, has solved the long problem of the technical process that in traditional technology, stepwise synthesis brings, and has realized the short flow process synthesis technique of hexanolactam, less energy-consumption and environmental friendliness.
The present invention solves this technical problem technical scheme used:
A method by hexalin, hydrogen peroxide and azanol synthesizing caprolactam in one step, comprises the following steps:
(1) by hexalin, Na 2wO 42H 2o and ionic liquid are put into the reactor with condensation facility, after dripping hydrogen peroxide, react 30～600min at 80 ℃ of normal pressures; Material mole proportioning is hexalin: hydrogen peroxide: Na 2wO 42H 2o: ionic liquid=1:1.2:0.055:0.02～0.08;
(2) when step (1) arrived after the reaction times, hexalin: oxammonium sulfate=2:1 in molar ratio, directly oxammonium sulfate is joined in the reactor in step (1), after 70～100 ℃ of continuation reaction 60～180min of normal pressure, through methylene dichloride, extract and obtain product hexanolactam;
Described ionic liquid is quaternary ammonium salt acidic ion liquid, and the molar weight of described hydrogen peroxide is with H 2o 2meter.
Described quaternary ammonium salt acidic ion liquid is preferably N-Methyl pyrrolidone hydrosulfate ionic liquid, Trimethylamine 99 hydrosulfate ionic liquid, triethylamine hydrosulfate ionic liquid, N-Methylimidazole hydrosulfate ionic liquid, N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, N, N, N-trimethylammonium-N-sulphur butyl-tosilate ionic liquid, N, N, N-trimethylammonium-N-sulphur butyl-dihydrogen phosphate ionic liquid, 1-(butyl-4-sulfonic group)-3-Methylimidazole hydrosulfate ionic liquid or N, N, N-triethyl-N-sulphur butyl hydrosulfate ionic liquid.
The invention has the beneficial effects as follows:
(1) the present invention directly joins hexalin, azanol, hydrogen peroxide in a reaction vessel and carries out, and proposes the novel process by hexalin synthesizing caprolactam in one step, and simplification of flowsheet, saves production cost, and reduces energy consumption.
(2) the present invention is by ionic liquid and Na for the catalyzer of the direct synthesis of caprolactam of hexalin 2wO 42H 2the catalyst system that O forms, utilize ionic liquid flexibly chemical modifiability change its acid and hydrophilic, lipophilicity, thereby change its acid catalysis ability and phase-transfer catalysis ability, can effectively improve the selectivity of transformation efficiency and the hexanolactam of hexalin.Wherein adopt ionic liquid [HSO 3-bmim] HSO 4with Na 2wO 42H 2o forms catalyst system and is applied to the direct synthesis of caprolactam reaction of hexalin, and the transformation efficiency of hexalin can reach 100%, the high energy of the yield of hexanolactam reach 53.6% and catalyzer recycling 5 times after, catalytic performance is still stable.
(3) selecting hydrogen peroxide is that oxygenant carries out hexalin oxidation and the alternative vitriol oil of quaternary ammonium salt acidic ion liquid carries out cyclohexanone-oxime Beckmann rearrangement, reduced the generation of by product ammonium sulfate, environmentally friendly, and final product also has pimelinketone and cyclohexanone-oxime except hexanolactam, and they are all important industrial chemicals.
Embodiment
Embodiment 1
The preparation of hydrosulfate ionic liquid:
The first step, is placed in there-necked flask by N-Methyl pyrrolidone, by the mol ratio of N-Methyl pyrrolidone and the vitriol oil, is 1:1, drips the vitriol oil in ice-water bath, carries out mechanical stirring.
Second step, after dropwising, continues to stir 30min, then heats up 80 ℃, stirs 3h.
The 3rd step, ethyl acetate washing 3 times for the material that second step is obtained, rotary evaporation is removed unreacting substance, and vacuum-drying obtains N-Methyl pyrrolidone hydrosulfate ionic liquid ([Hnmp] HSO 4).
Embodiment 2
Trimethylamine 99 hydrosulfate ionic liquid ([(CH 3) 3n +] HSO 4 -) preparation method with embodiment 1, difference is to adopt raw material trimethylamine aqueous solution to substitute N-Methyl pyrrolidone.
Embodiment 3
Triethylamine hydrosulfate ionic liquid ([(CH 3cH 2) 3n +] HSO 4 -) preparation method with embodiment 1, difference is to adopt raw material triethylamine aqueous solution to substitute N-Methyl pyrrolidone.
Embodiment 4
N-Methylimidazole hydrosulfate ionic liquid ([Hmim] HSO 4) preparation method is with embodiment 1, difference is to adopt raw material N-Methylimidazole to substitute N-Methyl pyrrolidone.
Embodiment 5
Sulfonic functional ion liquid [HSO 3-b-N +(CH 3) 3] X(X=HSO 4 -, HCF 3sO 4 -, p-TSA -, H 2pO 4 -, [HSO wherein 3-b-N +(CH 3) 3] HSO 4 -with reference to Chinese patent, application number 200710151001.6) preparation:
The first step: be the there-necked flask that 1:1 is placed in 250ml by Trimethylamine 99 and Isosorbide-5-Nitrae-butane sultone mol ratio, stirring reaction is 12 hours under room temperature condition.
Second step, the reaction solution that the first step is obtained takes out to revolve to steam and dewaters, and obtains white zwitter-ion solid.
The 3rd step, dehydrated alcohol, toluene and anhydrous diethyl ether for material that second step is obtained wash successively, and then vacuum-drying at 80 ℃ obtains zwitter-ion salt N, N, N-trimethylammonium-N-sulphur butyl ammonium.
The 4th step, the zwitter-ion salt that the 3rd step is obtained is put into Erlenmeyer flask, adds the equimolar vitriol oil, and constant temperature stirs 4 hours at 80 ℃, obtains N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid ([HSO 3-b-N +(CH 3) 3] HSO 4 -).
Embodiment 6
N, N, N-trimethylammonium-N-sulphur butyl-trifluoromethyl sulfonic acid ionic liquid ([HSO 3-b-N +(CH 3) 3] HCF 3sO 4 -) preparation method with embodiment 5, difference is to adopt trifluoromethanesulfonic acid to substitute the vitriol oil in the 4th step.
Embodiment 7
N, N, N-trimethylammonium-N-sulphur butyl-tosilate ionic liquid ([HSO 3-b-N +(CH 3) 3] p-TSA -) preparation method the same, difference is to adopt tosic acid to substitute the vitriol oil in the 4th step.
Embodiment 8
N, N, N-trimethylammonium-N-sulphur butyl-dihydrogen phosphate ionic liquid ([HSO 3-b-N +(CH 3) 3] H 2pO 4 -) preparation method is the same, difference is to adopt phosphoric acid to substitute the vitriol oil in the 4th step.
Embodiment 9
Sulfonic functional hydrosulfate ionic liquid [Y] HSO 4 -(Y=[HSO 3-bmim], [HSO 3-b-N +(CH 2cH 3) 3]) preparation:
The first step, is placed in there-necked flask by equimolar N-Methylimidazole and Isosorbide-5-Nitrae-butane sultone, 60 ℃ of stirring 4-6h of water-bath, and reactant becomes white solid.
Second step, washing with alcohol 3-5 time for the solid that the first step is obtained, is dried 6h at 110 ℃, obtains 1-(4-sulfonic group)-butyl-3-Methylimidazole zwitter-ion salt.
The 3rd step, adds the equimolar vitriol oil in the zwitter-ion salt that second step is obtained, and under room temperature, reacts after 0.5h, continues to stir 4～5 hours under 80 ℃ of water-baths.
The 4th step, the product that the 3rd step is obtained washs respectively three times with ethyl acetate and ether, removes unreacted nonionic resistates, dry 6h, obtains 1-(butyl-4-sulfonic group at 110 ℃)-3-Methylimidazole hydrosulfate ionic liquid ([HSO 3-bmim] HSO 4).
Embodiment 10
N, N, N-triethyl-N-sulphur butyl hydrosulfate ionic liquid ([(CH 3cH 2) 3n +-b-SO 3h] HSO 4 -) preparation method is the same, difference is to adopt raw material triethylamine aqueous solution to substitute N-Methylimidazole and the first step reaction to finish rear solid respectively with toluene and ether washing 3-5 time.
Embodiment 11
In the 100ml there-necked flask of prolong, thermometer is housed, add hexalin 50mmol, [(CH 3) 3n +] HSO 4 -ionic liquid 2mmol, Na 2wO 42H 2o2.75mmol carries out magnetic agitation, and dropwise adding mass concentration at 80 ℃ is that 30% hydrogen peroxide 7.7ml is (containing H 2o 260mmol), time for adding is 20min, dropwises rear constant temperature 300min.Then, add the oxammonium sulfate of 25mmol, at 80 ℃, continue to stir 150min, reaction solution is cooled to room temperature, add excessive methylene dichloride to extract, get upper organic phase and pack in sample plasma bottle, by gas-chromatography, analyze.Reaction result is: the transformation efficiency 30.7% of hexalin, the yield of hexanolactam is 5.51%, selectivity 1.24%, the selectivity 9.59% of pimelinketone, the selectivity 72.4% of cyclohexanone-oxime.
Embodiment 12
Step is with embodiment 11, and difference is that ionic liquid is [(CH 3cH 2) 3n +] HSO 4 -.Reaction result is, the transformation efficiency 26.0% of hexalin, and the yield of hexanolactam is 4.16%, selectivity 16.0%, the selectivity 9.81% of pimelinketone, the selectivity 74.2% of cyclohexanone-oxime.
Embodiment 13
Step is with embodiment 11, and difference is that ionic liquid is [Hmim] HSO 4.Reaction result is, the transformation efficiency 97.1% of hexalin, and the yield of hexanolactam is 32.1%, selectivity 33.1%, the selectivity 13.6% of pimelinketone, the selectivity 53.4% of cyclohexanone-oxime, the selectivity 33.1% of hexanolactam.
Embodiment 14
Step is with embodiment 11, and difference is that ionic liquid is [Hnmp] HSO 4.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 36.4%, the selectivity 11.4% of pimelinketone, the selectivity 52.2% of cyclohexanone-oxime.
Embodiment 15
Step is with embodiment 11, and difference is that ionic liquid is [HSO 3-b-N +(CH 2cH 3) 3] HSO 4 -.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 40.3%, the selectivity 9.45% of pimelinketone, the selectivity of cyclohexanone-oxime is 48.1%.
Embodiment 16
Step is with embodiment 11, and difference is that ionic liquid is [HSO 3-b-N +(CH 3) 3] HSO 4 -.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 49.1%, the selectivity 10.3% of pimelinketone, the selectivity 36.6% of cyclohexanone-oxime.
Embodiment 17
Step is with embodiment 11, and difference is that ionic liquid is [HSO 3-bmim] HSO 4.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 53.6%, the selectivity 14.6% of pimelinketone, the selectivity 31.7% of cyclohexanone-oxime.
Embodiment 18
Step is with embodiment 11, and difference is that ionic liquid is [HSO 3-b-N +(CH 3)] CF 3sO 4 -.Reaction result is, the transformation efficiency 6.81% of hexalin, and the yield of hexanolactam is 0.87%, selectivity 12.8%, the selectivity 0.00% of pimelinketone, the selectivity 87.2% of cyclohexanone-oxime.
Embodiment 19
Step is with embodiment 11, and difference is that ionic liquid is [HSO 3-b-N +(CH 3) 3] H 2pO 4 -.Reaction result is, the transformation efficiency 20.1% of hexalin, and the yield of hexanolactam is 5.21%, selectivity 25.9%, the selectivity 23.6% of pimelinketone, the selectivity 50.5% of cyclohexanone-oxime.
Embodiment 20
Step is with embodiment 11, and difference is that ionic liquid is [HSO 3-b-N +(CH 3) 3] p-TSA -.Reaction result is, the transformation efficiency 22.9% of hexalin, and the yield of hexanolactam is 4.71%, selectivity 20.6%, the selectivity 9.84% of pimelinketone, the selectivity 69.6% of cyclohexanone-oxime.
Embodiment 21
Step is with embodiment 16, and difference is temperature 70 C.Reaction result is, the transformation efficiency 96.1% of hexalin, and the yield of hexanolactam is 15.2%, selectivity 15.8%, the selectivity 23.2% of pimelinketone, the selectivity 58.8% of cyclohexanone-oxime.
Embodiment 22
Step is with embodiment 16, and difference is 90 ℃ of temperature.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 26.0%, the selectivity 22.4% of pimelinketone, the selectivity 49.4% of cyclohexanone-oxime.
Embodiment 23
Step is with embodiment 16, and difference is 100 ℃ of temperature.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 21.6%, the selectivity 31.4% of pimelinketone, the selectivity 39.5% of cyclohexanone-oxime.
Embodiment 24
Step is with embodiment 16, and difference is time 60min.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 23.0%, the selectivity 23.1% of pimelinketone, the selectivity 50.2% of cyclohexanone-oxime.
Embodiment 25
Step is with embodiment 16, and difference is time 120min.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 44.3%, the selectivity 15.4% of pimelinketone, the selectivity 37.2% of cyclohexanone-oxime.
Embodiment 26
Step is with embodiment 16, and difference is time 180min.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 41.4%, the selectivity 19.1% of pimelinketone, the selectivity 39.5% of cyclohexanone-oxime.
Embodiment 27
Step is with embodiment 16, and difference is ionic liquid [HSO 3-b-N +(CH 3) 3] HSO 4 -consumption be 1.0mmol.Reaction result is, the transformation efficiency 40.5% of hexalin, and the yield of hexanolactam is 15.6%, selectivity is 6.32%, the selectivity 39.2% of pimelinketone, the selectivity 55.4% of cyclohexanone-oxime.
Embodiment 28
Step is with embodiment 16, and difference is ionic liquid [HSO 3-b-N +(CH 3) 3] HSO 4 -consumption be 3.0mmol.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 48.2%, the selectivity 8.4% of pimelinketone, the selectivity 35.3% of cyclohexanone-oxime.
Embodiment 29
Step is with embodiment 16, and difference is ionic liquid [HSO 3-b-N +(CH 3) 3] HSO 4 -consumption be 4.0mmol.Reaction result is, the transformation efficiency 100% of hexalin, and the yield of hexanolactam and selectivity are 47.6%, the selectivity 7.7% of pimelinketone, the selectivity 34.7% of cyclohexanone-oxime.
Embodiment 30
After embodiment 16 reactions finish, with Rotary Evaporators, distill out the moisture in water, by the ionic liquid obtaining and NaWO 42H 2o carries out vacuum-drying at 60 ℃, and continues to react according to embodiment 16, with this catalyst recirculation, uses 4 times.Reaction result is, it is 48.6% that catalyst recirculation is used the yield of hexanolactam for the first time, recycling the yield of hexanolactam is for the second time 48.2%, and recycling the yield of hexanolactam is for the third time 47.9%, and the yield that recycles the 4th hexanolactam is 47.6%.
Can find out, in this patent, the synthetic of hexanolactam is to carry out in a reactor, avoided equipment to repeat to arrange, and simplifies and facilitated operation.Adopt ionic liquid [HSO 3-bmim] HSO 4with Na 2wO 42H 2o forms catalyst system and is applied to the direct synthesis of caprolactam reaction of hexalin, and the transformation efficiency of hexalin can reach 100%, the high energy of the yield of hexanolactam reach 53.6% and catalyst recirculation use after 4 times, catalytic activity does not obviously decline.

Claims (2)

1. by a method for hexalin, hydrogen peroxide and azanol synthesizing caprolactam in one step, it is characterized by and comprise the following steps:
(1) by hexalin, Na 2wO 42H 2o and quaternary ammonium salt acidic ion liquid are put into the reactor with condensation facility, after dripping hydrogen peroxide, react 30 ~ 600min at 80 ℃ of normal pressures; Material mole proportioning is hexalin, hydrogen peroxide, Na 2wO 42H 2o, quaternary ammonium salt acidic ion liquid=1:1.2:0.055:0.02 ~ 0.08;
(2) when step (1) arrived after the reaction times, hexalin: oxammonium sulfate=2:1 in molar ratio, directly oxammonium sulfate is joined in the reactor in step (1), after 70 ~ 100 ℃ of continuation reaction 60 ~ 180min of normal pressure, through methylene dichloride, extract and obtain product hexanolactam.
2. as claimed in claim 1 by hexalin, the method of hydrogen peroxide and azanol synthesizing caprolactam in one step, it is characterized by described quaternary ammonium salt acidic ion liquid and be preferably N-Methyl pyrrolidone hydrosulfate ionic liquid, Trimethylamine 99 hydrosulfate ionic liquid, triethylamine hydrosulfate ionic liquid, N-Methylimidazole hydrosulfate ionic liquid, N, N, N-trimethylammonium-N-sulphur butyl-monoammonium sulfate ionic liquid, N, N, N-trimethylammonium-N-sulphur butyl-tosilate ionic liquid, N, N, N-trimethylammonium-N-sulphur butyl-dihydrogen phosphate ionic liquid, 1-(butyl-4-sulfonic group)-3-Methylimidazole hydrosulfate ionic liquid or N, N, N-triethyl-N-sulphur butyl hydrosulfate ionic liquid.
CN201310516252.5A 2013-10-28 2013-10-28 One-step synthesis method for caprolactam from cyclohexanol, hydrogen peroxide and hydroxylamine Pending CN103524415A (en)

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CN109438397A (en) * 2018-11-20 2019-03-08 江苏科本药业有限公司 A kind of synthetic method of the intermediate of Suo Feibuwei
CN114477112A (en) * 2022-02-10 2022-05-13 河北工业大学 Method for preparing hydroxylamine by catalyzing cyclohexanone oxime with crosslinked acidic polymeric ionic liquid

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086487A (en) * 2014-07-18 2014-10-08 河北工业大学 Method for directly synthesizing caprolactam from cyclohexanone serving as raw material
CN104086487B (en) * 2014-07-18 2016-07-06 河北工业大学 A kind of method being directly synthesized caprolactam for raw material with Ketohexamethylene
CN109438397A (en) * 2018-11-20 2019-03-08 江苏科本药业有限公司 A kind of synthetic method of the intermediate of Suo Feibuwei
CN109438397B (en) * 2018-11-20 2022-06-24 江苏科本药业有限公司 Synthetic method of sofosbuvir intermediate
CN114477112A (en) * 2022-02-10 2022-05-13 河北工业大学 Method for preparing hydroxylamine by catalyzing cyclohexanone oxime with crosslinked acidic polymeric ionic liquid

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Application publication date: 20140122