CN107098811B - (E)-beta-nitrostyrene synthetic method - Google Patents
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Abstract
The invention discloses a kind of synthetic methods of (E)-beta-nitrostyrene, styrene one pot reaction in the system of iron containing tetaraary porphyrin (III), ammonium halide salt and tert-butyl hydroperoxide generates (E)-beta-nitrostyrene；The method achieve under mild reaction conditions, high yield synthesis has the beta-nitrostyrene of high E stereoselectivity.
Description
Technical field
The present invention relates to a kind of synthetic method of (E)-beta-nitrostyrene, in particular to a kind of styrene is containing four aryl
One pot reaction in the system of PORPHYRIN IRON (III), ammonium halide salt and tert-butyl hydroperoxide, high yield high selectivity (E)-β-
The method of nitrostyrolene, belongs to organic synthesis field.
Background technique
α, β-unsaturation nitroolefin are a kind of biologically active compounds.For example, unsaturated nitrofatty acid
It is a new class of endogenous anti-inflammatory medium；Unsaturated nitro-oleic acid can prevent mouse renal ischaemia and reperfusion injury.α simultaneously, β-is no
Saturation nitroolefin is a kind of important drug and organic intermediate compound, it is easy to a variety of different compounds are converted to,
Important role is suffered from many fields.For example, beta-nitrostyrene be used to prepare several phenyl ethylamines and it is antifungal in
Mesosome (" chemical abstracts " (Chemical Abstracts), vol.118, no.38576k).α, β-unsaturation nitroolefin also by
The Michael receptor being widely used in some reactions, such as the asymmetric Michael Reaction of aldehyde, ketone and nitroolefin, indoles, pyrrole
Cough up the Friedel-Crafts alkylated reaction with the stereoselectivity of nitroolefin；Between nitroolefin and nitroparaffins not
Symmetrical Michael addition；Asymmetric biological reducing of nitroolefin etc..
Therefore, based on the importance of nitroolefin, the synthetic method of nitroolefin derivative is decades ago just by researcher
Pay close attention to.Early in decades ago just it has been reported that being used for the classics side of synthesizing nitryl alkene using nitro compound as nitro source
Case.It is under alkaline condition, aldehydes or ketones and nitroparaffins to be subjected to condensation reaction and obtain nitro such as the Henle reaction more early reported
Alkene derivatives (such as reaction 1), but that there are reaction conditions is relatively harsh for Henle reaction, reaction yield is relatively low, and generates
The problems such as a large amount of spent lye.The some improved Henle reactions of follow-up report, as nitromethane and aldehyde compound pass through
β-nitroalcohol can be obtained in Henry condensation, and β-nitroalcohol is dehydrated through DCC/CuCl or trifluoroacetic anhydride/triethylamine again, or can also
Through MsCl/Et3Or P2Dehydration obtains α, β-unsaturation nitroolefin.For another example BrCH2NO2It is made under the catalysis of sodium iodide with aldehyde
The bromo- 1- nitroparaffin -2- alcohol of 1- is obtained, α, β-unsaturation nitro compds is made through samarium diodide β-elimination again in the bromo- 1- nitroparaffin -2- alcohol of 1-
Hydrocarbon.Being handled in the benzole soln of reflux with sodium carbonate after for another example β-nitroalcohol is acylated can be obtained the pretty good α of yield, β-unsaturation nitre
Base alkene, but these reactions need multistep, and yield is also not very high.As Chinese patent (CN106083597A) discloses one kind altogether
The synthetic method of yoke nitroolefin under the conditions of existing for the diamines, utilizes the nitro of fatty aldehyde and nitroparaffins to carry out aldol contracting
Close reaction, the elimination reaction of the conjugated nitroalkene carried out in reaction process by addition acid (such as reaction 2)；This method passes through
Catalyst of the diamines as nitro aldol reaction reduces side reaction and generates, improve product yield, but the reaction step is more,
There are a large amount of acid waste liquids to generate, pollutes environment.Chinese patent (104710315 A of CN) discloses a kind of α, β-unsaturation nitro
The green synthesis method (such as reaction 3) of olefin(e) compound, using functionalized ion liquid and water as catalyst system, aromatic aldehyde
Microwave heating reaction is carried out with nitroparaffins, reaction condition can be made mild, improves reaction yield；But this method utilize from
Sub- liquid is at high cost, it is difficult to industrial applications.
In addition, some synthesis α, β-unsaturation nitroolefin new method are reported successively.It such as reports than being with Asia earlier
Alkene is nitrified the research work [(Hassner at α, β-unsaturation nitroolefin and system improvement nitration condition by nitrate and iodine
Et al., J.Org.Chem., 1969,34 (9), p.2628-2632.), (TeTr.Lett., 1985,26 (9), p.1193-
1196),(chemistry Letters,1986,p.1747-1748)].These reactions are due to using a large amount of iodine, excess iodine
It is fairly cumbersome in last handling process, and reduce the yield of product.The Zambon Group S.P.A of Italy is special China's application
Sharp (CN1438977A) discloses the mixed of inorganic nitrite using styrene derivative as raw material, in the presence of peroxide and iodine
Conjunction object is nitrating agent synthesizing nitryl distyryl compound；This method is due to having used oxidant to greatly reduce nitrification olefin hydrocarbon
The usage amount of middle iodine simplifies processing step, but these methods all use to improve the yield of product to a certain extent
Nitrite endangers environment and human body big as nitrating agent.Currently, being tried there are also some using nitrogen-containing oxide as nitrification
Agent directly carries out nitration reaction with vinyl compound under metallic nickel oxide catalyst, obtains nitroolefin derivative (as instead
It answers 4), this method uses gas liquid reaction mode, and reaction efficiency is low, and can generate toxic gas, and yield yield is not also high.
Reaction 1:
Reaction 2:
Reaction 3:
Reaction 4:
Summary of the invention
For synthesizing α in the prior art, defect existing for β-unsaturation nitroolefin method, the purpose of the present invention is
In providing one kind, high yield synthesizes the method with the beta-nitrostyrene of high E stereoselectivity under mild reaction conditions.
In order to achieve the above technical purposes, the present invention provides a kind of synthetic method of (E)-beta-nitrostyrene, the party
Method is one pot reaction, life in the system of iron containing tetaraary porphyrin (III), ammonium halide salt and tert-butyl hydroperoxide by styrene
At (E)-beta-nitrostyrene.
Preferred scheme, reaction condition are as follows: under the conditions of air or protective atmosphere, reaction temperature is 100 DEG C~130 DEG C,
Reaction time is 3~9h.Optimal reaction temperature is 115~125 DEG C, and the reaction time is 5~7h.
Preferred scheme, the molar ratio of styrene, ammonium halide salt and tert-butyl hydroperoxide are 1:(1~2): (4~8).
Further preferred scheme, the molar ratio of styrene, ammonium halide salt and tert-butyl hydroperoxide are 1:(1.5~2): (6~8).
Preferred scheme, the ammonium halide salt are at least one of ammonium iodide, ammonium bromide, ammonium chloride.More preferably scheme,
Ammonium halide salt is ammonium iodide.Ammonium halide salt is as nitro source, oxidation of the ammonium halide salt in peroxide tert-butyl hydroperoxide
Effect is lower to generate nitro free radical, provides nitro substituent for (E)-beta-nitrostyrene.Many experiments show using ammonium bromide
The nitration reaction to alkene may be implemented with ammonium chloride, but nitrification efficiency is not very high, and when use ammonium iodide, nitrification effect
Rate can achieve 80% or more.
Preferred scheme, the system include acetonitrile and/or alcohol solvent.The polarity of solvent also has the nitrification of alkene
Certain influence, such as in acetonitrile and ethyl alcohol, nitration reaction can be gone on smoothly, and use the conducts such as water, DMF, DEC, toluene
Reaction dissolvent, cannot get (E)-beta-nitrostyrene or yield is at a fairly low.Acetonitrile is that optimal reaction is molten in the method for the present invention
Agent, the relatively other reaction dissolvents of reaction effect will be higher by very much.
Preferred scheme, the tetaraary porphyrin iron (III) are tetraphenylporphyrin iron chloride (such as TPPFeCl) and/or double
(tetraphenylporphyrin) iron (III) ((TPPFe)2O).The nitration reaction of tetaraary porphyrin iron (III) alkenes has special urge
Change activity, and other trivalent iron salts, divalent iron salt do not have catalytic action, and other four metal aryls porphyrins to the reaction
It closes object and does not also have catalytic activity, such as four metal aryl porphyrin coppers, four metal aryl Cobalt Porphyrins.Tetaraary porphyrin iron
(III) it is also possible to the derivative of tetraphenylporphyrin iron chloride, substituent group can be contained on phenyl ring, the amino, nitro of such as routine,
Alkyl, alkoxy, halogen etc..
More preferably scheme, the dosage of the tetaraary porphyrin iron chloride are the 2~10% of styrene mole.More preferably
It is 3~5%.Catalyst amount increases, and nitration reaction effect is substantially reduced.
The present invention by styrene synthesizes (E)-beta-nitrostyrene, and the reaction mechanism is as follows, with NH4I、TBHP、TPPFeCl
Acetonitrile solution be reaction system, pass through styrene (R and R2It is hydrogen, R1For benzene) it is substrate synthesis (E)-beta-nitrostyrene,
Reaction mechanism is specifically described as concrete example: firstly, TBHP is decomposed under the conditions of certain temperature generates oxygen and hydroxyl
Equal free radicals, quaternary ammonium cation are oxidized to nitrogen dioxide free radical by oxygen radical, and nitrogen dioxide free radical is catalyzed in TPPFeCl
Radical Addition is carried out to styrene under medium transferance, obtains reactive intermediate A, intermediate A captures hydroxyl free
Base obtains intermediate B, and intermediate B carries out cis- elimination, obtains the beta-nitrostyrene of high E formula solid selection.In reaction process
TPPFeCl primarily serves transferred free radical effect, can form unstable intermediate, but finally still exists with TPPFeCl, rises
To catalytic action.Reaction mechanism equation is as follows:
The present invention verifies the mechanism of ethylene nitration reaction of the invention by following reaction, illustrates the reaction machine
The reasonability of reason.TEMPO or BHT radical scavenger (reaction 1) is added during the nitration reaction of styrene, discovery is almost
It cannot get reaction product, illustrate that the reaction is related to radical reaction mechanism.Next, using intermediate 2- nitro -1- hydroxyl
Ethylo benzene (B) is in NH4In I and TBHP and TPPFeCl mixed system or in the NH for being free of TPPFeCl4In I and TBHP mixed system
Reaction (reaction 2), can obtain target product, illustrate that catalyst is barely affected elimination reaction.Present invention design simultaneously
Step-reaction experiment, first step reaction is NH in the case where no substrate styrene4I and TBHP is in TPPFeCl catalyst
Under the conditions of (a) with do not have to TPPFeCl catalysts conditions under (b) mix 30 minutes, be then respectively adding TEMPO, can by GC-MS
To detect that two reactions have the generation of TEMPO- nitro free radical analog, illustrate that the effect of TPPFeCl catalyst is not
Free radical is catalyzed to generate (such as 3 (a) of reaction and (b))；Second step reaction is to contain TEMPO- what (3 (a) of reaction) reaction generated
Nitro free radical analog mixture is divided into two parts, and styrene substrate and TPPFeCl catalyst (d) are added in portion, another
Add styrene substrate, but TPPFeCl catalyst (c) is not added, heating stirring is reacted 6 hours, as a result joined catalyst
The beta-nitrostyrene 2a (4 (c) of reaction and (d)) that higher yields can be obtained in the reaction of FeTPPCl, illustrates that TPPFeCl is urged
Agent mainly plays the role of catalysis free radical and reacts with styrene.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
1) technical solution of the present invention is for the first time using iron containing tetaraary porphyrin (III), ammonium halide salt and tert-butyl hydroperoxide
Hydrogen reaction system carries out nitration reaction to styrene, realizes styrene one pot reaction and generates (E)-beta-nitrostyrene, relatively
The prior art enormously simplifies processing step, is conducive to industrialized production.
2) technical solution of the present invention uses direct nitro source of the inorganic halide ammonium salt as styrene for the first time, compared to existing
Nitrogen-containing oxide, nitrite and organic nitre class compound in technology, have many advantages, such as at low cost, safe and environment-friendly.
3) technical solution of the present invention is catalyzed examination using tetaraary porphyrin iron (III) as the nitration reaction of styrene for the first time
Agent can realize the nitration reaction of styrene in a mild condition, and obtain higher yield and highly-solid selectively.
4) technical solution of the present invention realizes the one pot process of (E)-beta-nitrostyrene, and target product is easy to point
From purification, processing step is simplified, is conducive to industrialized production.
Detailed description of the invention
[Fig. 1] is the nucleus magnetic hydrogen spectrum figure of the target product of embodiment 1；
[Fig. 2] is the nuclear-magnetism carbon spectrogram of the target product of embodiment 1.
Specific embodiment
Implement to be intended to further illustrate the content of present invention below, rather than limits the protection scope of the claims in the present invention.
All solvents, metalloporphyrin, oxidant, ammonium salt and the alkene used in following embodiment is purchased from commercial source
It buys.
All target compounds are characterized using GC-MS and NMR (1H and 13C) spectroscopic data.
NMR model Bruker AV400MHz, relative displacement is indicated using ppm, with the relative displacement of trimethyl silane
On the basis of ppm=0.
1H relative displacement ppm=7.26, the 13C relative displacement ppm=77.00 of chloroform is remained in deuterated solvent.
GC-MS model Shimadzu GC-MS (QP-2010), the detector used is fid detector.
All nitration reactions carry out in the seal pipe (25mL) with threaded end.
Unless otherwise indicated, molecular sieve water removal is all added in all liq reagent to save.
The yield of target product in following embodiment by stereoselectivity be E formula structure target product carry out based on
It calculates, the stereoselectivity of reaction is almost 100%.
Embodiment 1
By styrene (0.5mmol), NH4I (1.5 equivalents, 0.75mmol, 108mg), TBHP (70% H2O, 6.0 equivalents,
3.0mmol, 384mg), TPPFeCl (the 3~5% of styrene mole) and acetonitrile (2mL) are added in seal pipe.First plus
Enter acetonitrile, styrene, NH is then added4I and TPPFeCl, is eventually adding TBHP.It is small that reaction is vigorously stirred 6 at 120 DEG C
When, and monitored by TLC.After the reaction was completed, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).
Finally, filtrate is concentrated with rotary evaporator, use petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel (200-
300 meshes) carry out column chromatography purifying.
Yellow solid:82% (61mg)1H NMR(400MHz,CDCl3) δ 8.01 (d, J=13.7Hz, 1H),
7.63-7.53 (m, 3H), 7.47 (tdd, J=8.5,5.2,3.6Hz, 3H)13C NMR(101MHz,CDCl3)δ139.04,
137.06,132.11,130.01,129.35,129.10.GC-MS(m/z):149.+.
Comparative experiments group 1:
Comparative examples 1~12 are reacted by following reaction equation:
Concrete operation step are as follows: by styrene (0.5mmol), NH4I (1.5 equivalents, 0.75mmol, 108mg), TBHP
(70% H2O, 6.0 equivalents, 3.0mmol, 384mg), catalyst (the 0~15% of styrene mole) and acetonitrile (2mL) add
Enter into seal pipe.It is firstly added acetonitrile, styrene, NH is then added4I and catalyst, are eventually adding TBHP.Reaction is existed
It is vigorously stirred at 120 DEG C 6 hours, and is monitored by TLC.After the reaction was completed, mixture is cooled to room temperature, then filters and is used in combination
Ethyl acetate (EA) washing.Finally, filtrate is concentrated with rotary evaporator, use petroleum ether (PE)/ethyl acetate (EA) as elution
Agent carries out column chromatography purifying using silica gel (200-300 mesh).
The yield of 1 different catalysts of table and the corresponding target product of dosage
From table 1 it follows that under the conditions of standard reaction, tetraphenylporphyrin iron chloride and double iron tetraphenylporphyrin reactions
With preferable catalytic action, satisfied yield can be obtained, the yield of especially tetraphenylporphyrin iron chloride is up to 82%.And
Target product is all hardly obtained using other inorganic divalent iron salts or trivalent iron salt.In addition, tetraphenylporphyrin iron chloride is urged
The dosage of agent should not be excessively used, and catalyst excess, product yield is substantially reduced, and catalyst is not added, hence it is evident that cannot get mesh
Product is marked, oxidation product is only able to find.
Comparative experiments group 2:
Comparative examples 13~21 are reacted by following reaction equation:
Concrete operation step are as follows: by styrene (0.5mmol), NH4X (1.5 equivalents, 0.75mmol), TBHP (70%
H2O, 6.0 equivalents, 3.0mmol, 384mg), TPPFeCl (the 5% of styrene mole) and acetonitrile (2mL) are added to seal pipe
In.It is firstly added acetonitrile, styrene, NH is then added4I and catalyst, are eventually adding TBHP.It will react at 120 DEG C acutely
Stirring 6 hours, and monitored by TLC.After the reaction was completed, mixture is cooled to room temperature, then filters and uses ethyl acetate
(EA) it washs.Finally, filtrate is concentrated with rotary evaporator, use petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silicon
Glue (200-300 mesh) carries out column chromatography purifying.
The yield of the corresponding target product of the different quaternary ammonium salts of table 2
From Table 2, it can be seen that the nitration reaction of styrene may be implemented using halogen quaternary ammonium salt, in addition to this other
Quaternary ammonium salt and ammonium hydroxide etc. all can not be as the nitro source of styrene nitration reaction.Furthermore it can also be seen that iodate from table 2
Ammonium has better yield with respect to ammonium bromide and ammonium chloride, and ammonium iodide is most suitable as styrene nitrating agent.
Comparative experiments group 3:
Comparative examples 22~31 are reacted by following reaction equation:
Concrete operation step are as follows: by styrene (0.5mmol), NH4I (1.5 equivalents, 0.75mmol, 108mg), oxidant
(6.0 equivalents, 3.0mmol), TPPFeCl (the 5% of styrene mole) and acetonitrile (2mL) are added in seal pipe.First plus
Enter acetonitrile, styrene, NH is then added4I and catalyst, are eventually adding TBHP.Reaction is vigorously stirred 6 hours at 120 DEG C,
And it is monitored by TLC.After the reaction was completed, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).Most
Afterwards, filtrate is concentrated with rotary evaporator, uses petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel (200-300
Mesh) carry out column chromatography purifying.
The yield of the corresponding target product of the different oxidants of table 3
From table 3 it is observed that only TBHP can aoxidize ammonium iodide, the nitration of styrene is realized, and reaction is not bullied
Atmosphere influences, and can obtain preferable yield in air and under protective atmosphere.And other common oxidants such as hydrogen peroxide, mistake
The inorganic organic peroxide such as potassium sulfate and di-tert-butyl peroxide is difficult to realize the nitration reaction of styrene.
Comparative experiments group 4:
Comparative examples 32~41 are reacted by following reaction equation:
Concrete operation step are as follows: by styrene (0.5mmol), NH4I (1~2 equivalent), oxidant (4~7 equivalent),
TPPFeCl (the 5% of styrene mole) and acetonitrile (2mL) are added in seal pipe.It is firstly added acetonitrile, benzene second is then added
Alkene, NH4I and catalyst, are eventually adding TBHP.Reaction is vigorously stirred 6 hours at 120 DEG C, and is monitored by TLC.Reaction
After the completion, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).Finally, being concentrated with rotary evaporator
Filtrate, uses petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, carries out column chromatography purifying using silica gel (200-300 mesh).
4 difference NH of table4The yield of the corresponding target product of I and TBHP ratio
NH as can be seen from Table 44The reaction ratio with substrate styrene of I and TBHP has the yield of product larger
Influence, NH4The molar ratio of I and styrene will reach 1.5 or more, meanwhile, TBHP and NH4The ratio of I will reach 4 or more,
Optimal reaction effect can be reached, and reacted in other proportional regions, although target product can be obtained smoothly, yield by
To limitation.
Comparative experiments group 5:
Comparative examples 42~51 are reacted by following reaction equation:
Concrete operation step are as follows: by alkene (0.5mmol), NH4I (1.5 equivalents, 0.75mmol, 108mg), TBHP (70%
H2O, 6.0 equivalents, 3.0mmol, 384mg), TPPFeCl (3~5%) and solvent (0~2mL) are added in seal pipe.First
Acetonitrile is added, styrene, NH is then added4I and TPPFeCl, is eventually adding TBHP.It is small that reaction is vigorously stirred 6 at 120 DEG C
When, and monitored by TLC.After the reaction was completed, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).
Finally, filtrate is concentrated with rotary evaporator, use petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel (200-
300 meshes) carry out column chromatography purifying.
The yield of 5 different solvents of table and the corresponding target product of dosage
Comparative experiments group 6:
Comparative examples 52~59 are reacted by following reaction equation:
Concrete operation step are as follows: by alkene (0.5mmol, 50.2mg), NH4I (1.5 equivalents, 0.75mmol, 108mg),
TBHP (70% H2O, 6.0 equivalents, 3.0mmol, 384mg), TPPFeCl (3~5%) and solvent (2mL) are added to seal pipe
In.It is firstly added acetonitrile, styrene, NH is then added4I and TPPFeCl, is eventually adding TBHP.It will react at 120 DEG C acutely
Stirring 6 hours, and monitored by TLC.After the reaction was completed, mixture is cooled to room temperature, then filters and uses ethyl acetate
(EA) it washs.Finally, filtrate is concentrated with rotary evaporator, use petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silicon
Glue (200-300 mesh) carries out column chromatography purifying.
The yield of 6 different solvents of table and the corresponding target product of dosage reaction atmosphere
As can be seen from Table 6, target compound, ambiance or solvent could be only obtained under ammonium salt existence condition
It is not involved in and the source N is provided.
Claims (6)
1. a kind of synthetic method of (E)-beta-nitrostyrene, it is characterised in that: styrene iron containing tetaraary porphyrin (III),
One pot reaction in the system of ammonium halide salt and tert-butyl hydroperoxide generates (E)-beta-nitrostyrene；
Reaction condition are as follows: under air or protective atmosphere, reaction temperature is 100 DEG C~130 DEG C, and the reaction time is 3~9h；Benzene second
The molar ratio of alkene, ammonium halide salt and tert-butyl hydroperoxide is 1:(1~2): (4~8)；
The ammonium halide salt is at least one of ammonium iodide, ammonium bromide, ammonium chloride；
The system is using acetonitrile and/or ethyl alcohol as solvent；
The tetaraary porphyrin iron (III) is tetraphenylporphyrin iron chloride and/or double iron (III) porphyrins of four aryl.
2. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that: styrene, ammonium halide
The molar ratio of salt and tert-butyl hydroperoxide is 1:(1.5~2): (6~8).
3. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that: reaction temperature 115
DEG C~125 DEG C, the reaction time is 5~7h.
4. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that: the ammonium halide salt is
Ammonium iodide.
5. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that: the system uses second
Nitrile is as solvent.
6. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that: the tetaraary porphyrin
The dosage of iron (III) is the 2~10% of styrene mole.
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|---|---|---|---|---|
| JPH08198818A (en) * | 1995-01-20 | 1996-08-06 | Mitsui Petrochem Ind Ltd | Production of nitroolefin |
| CN1438977A (en) * | 2000-06-28 | 2003-08-27 | 萨宝集团公司 | Process for the preparation of nitroalkenes |
| CN101765579A (en) * | 2007-07-31 | 2010-06-30 | 住友化学株式会社 | Method for producing beta-nitrostyrene compound |
| CN103497082A (en) * | 2013-09-24 | 2014-01-08 | 台州学院 | Method for preparing beta-nitrostyrolene and derivatives thereof |
| CN105152935A (en) * | 2015-09-06 | 2015-12-16 | 安徽理工大学 | Method for preparing beta-nitrostyrolene compound |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08198818A (en) * | 1995-01-20 | 1996-08-06 | Mitsui Petrochem Ind Ltd | Production of nitroolefin |
| CN1438977A (en) * | 2000-06-28 | 2003-08-27 | 萨宝集团公司 | Process for the preparation of nitroalkenes |
| CN101765579A (en) * | 2007-07-31 | 2010-06-30 | 住友化学株式会社 | Method for producing beta-nitrostyrene compound |
| CN103497082A (en) * | 2013-09-24 | 2014-01-08 | 台州学院 | Method for preparing beta-nitrostyrolene and derivatives thereof |
| CN105152935A (en) * | 2015-09-06 | 2015-12-16 | 安徽理工大学 | Method for preparing beta-nitrostyrolene compound |
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