CN107098811A - (E) synthetic method of β nitrostyrolenes - Google Patents
(E) synthetic method of β nitrostyrolenes Download PDFInfo
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Abstract
The invention discloses a kind of synthetic method of (E) β nitrostyrolenes, styrene one pot reaction in the system of iron containing tetaraary porphyrin (III), ammonium halide salt and TBHP, generates (E) β nitrostyrolenes；It the method achieve under mild reaction conditions, β nitrostyrolene of the high yield synthesis with high E stereoselectivities.
Description
Technical field
The present invention relates to a kind of synthetic method of (E)-beta-nitrostyrene, more particularly to a kind of styrene is containing four aryl
One pot reaction in the system of PORPHYRIN IRON (III), ammonium halide salt and TBHP, high yield high selectivity (E)-β-
The method of nitrostyrolene, belongs to organic synthesis field.
Background technology
α, β-unsaturated nitroolefin are the compounds that a class has bioactivity.For example, undersaturated nitrofatty acid
It is the new endogenous anti-inflammatory medium of a class；Unsaturated nitro-oleic acid can prevent mouse renal ischaemia and reperfusion injury.While α, β-no
Saturation nitroolefin is the important medicine of a class and organic intermediate compound, it is easy to change into a variety of different compounds,
Important effect is suffered from many fields.For example, during beta-nitrostyrene is for preparing several phenyl ethylamines and being antifungal
Mesosome (《Chemical abstracts》(Chemical Abstracts),vol.118,no.38576k).α, β-unsaturated nitroolefin also by
The asymmetric Michael Reaction of the Michael acceptors, such as aldehyde, ketone and nitroolefin that are widely used in some reactions, indoles, pyrrole
Cough up the Friedel-Crafts alkylated reactions with the stereoselectivity of nitroolefin；Between nitroolefin and nitroparaffins not
Symmetrical Michael additions；Asymmetric biological reducing of nitroolefin etc..
Therefore, just by researcher before the importance based on nitroolefin, the synthetic method many decades of nitroolefin derivative
Pay close attention to.Early in before many decades just it has been reported that using nitro compound as nitro source be used for synthesizing nitryl alkene classics side
Case.It is in the basic conditions, aldehydes or ketones and nitroparaffins to be subjected to condensation reaction and obtain nitro such as the Henle reaction of relatively early report
Alkene derivatives (such as reaction 1), but to there is reaction condition relatively harsh for Henle reaction, reaction yield is relatively low, and produces
The problems such as substantial amounts of spent lye.Some improved Henle reactions of follow-up report, such as nitromethane passes through with aldehyde compound
Henry condensations can obtain β-nitroalcohol, and β-nitroalcohol is dehydrated through DCC/CuCl or TFAA/triethylamine again, or also may be used
With through MsCl/Et3Or P2Dehydration obtains α, β-unsaturation nitroolefin.And for example BrCH2NO2Made with aldehyde under the catalysis of sodium iodide
The bromo- 1- nitroparaffins -2- alcohol of 1- is obtained, α, β-unsaturation nitro compds is made through samarium diodide β-elimination again in the bromo- 1- nitroparaffins -2- alcohol of 1-
Hydrocarbon.Handled after and for example β-nitroalcohol is acylated in the benzole soln of backflow with sodium carbonate and can obtain yield pretty good α, β-unsaturation nitre
Base alkene, but these reactions need multistep, yield nor very high.As Chinese patent (CN106083597A) discloses a kind of common
The synthetic method of yoke nitroolefin, under conditions of diamines presence, aldol contracting is carried out using the nitro of fatty aldehyde and nitroparaffins
Close the elimination reaction of the conjugated nitroalkene carried out in reaction, course of reaction by adding acid (such as reaction 2)；This method passes through
Diamines is as the catalyst of nitro aldol reaction, and reduction side reaction generation improves product yield, but the reactions steps are more,
There are a large amount of acid waste liquids to produce, pollute environment.Chinese patent (A of CN 104710315) discloses a kind of α, β-unsaturation nitro
The green synthesis method (such as reaction 3) of olefin(e) compound, it is used as catalyst system and catalyzing, aromatic aldehyde by the use of functionalized ion liquid and water
Microwave heating response is carried out with nitroparaffins, reaction condition can be made gentle, reaction yield is improved；But this method utilize from
Sub- liquid cost is high, it is difficult to industrial applications.
In addition, some synthesis α, the new method of β-unsaturation nitroolefin is reported successively.Such as report than being with Asia earlier
Alkene is nitrified into α by nitrate and iodine, and β-unsaturation nitroolefin and one are to improve the research work [(Hassner of nitration condition
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 as a result of substantial amounts 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) is disclosed using styrene derivative as raw material, the inorganic nitrite and iodine in the presence of peroxide it is mixed
Compound is nitrating agent synthesizing nitryl distyryl compound；This method using oxidant due to greatly reducing nitrification olefin hydrocarbon
The usage amount of middle iodine, so as to improve the yield of product to a certain extent, simplifies processing step, but these methods are all used
Nitrite endangers big as nitrating agent to environment and human body.At present, some are tried by the use of nitrogen-containing oxide as nitrification
Agent, nitration reaction is directly carried out with vinyl compound under metallic nickel oxide catalyst, obtains nitroolefin derivative (as instead
Answer 4), this method uses gas liquid reaction mode, and reaction efficiency is low, and can produce toxic gas, and yield yield is not also high.
Reaction 1：
Reaction 2：
Reaction 3：
Reaction 4：
The content of the invention
For synthesizing α in the prior art, the defect that the method for β-unsaturation nitroolefin is present, the purpose of the present invention be
In a kind of method of beta-nitrostyrene of the synthesis of high yield under mild reaction conditions with high E stereoselectivities of offer.
In order to realize above-mentioned technical purpose, the invention provides a kind of synthetic method of (E)-beta-nitrostyrene, the party
Method be by styrene in the system of iron containing tetaraary porphyrin (III), ammonium halide salt and TBHP one pot reaction, it is raw
Into (E)-beta-nitrostyrene.
It is preferred that scheme, reaction condition is：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.
It is preferred that scheme, the mol ratio of styrene, ammonium halide salt and TBHP is 1:(1~2):(4~8).
Further preferred scheme, the mol ratio of styrene, ammonium halide salt and TBHP is 1:(1.5~2):(6~8).
It is preferred that scheme, the ammonium halide salt is 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 TBHP
The lower generation nitro free radical of effect, nitro substituent is provided for (E)-beta-nitrostyrene.Many experiments show, using ammonium bromide
The nitration reaction to alkene can be realized with ammonium chloride, but nitrification efficiency is not very high, and when using ammonium iodide, nitrification effect
Rate can reach more than 80%.
It is preferred that scheme, the system include acetonitrile and/or alcohol solvent.The polarity of solvent also has to the nitrification of alkene
Certain influence, such as in acetonitrile and ethanol, nitration reaction can be smoothed out, 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 in the inventive method is molten
Agent, the relatively other reaction dissolvents of reaction effect will be higher by a lot.
It is preferred that scheme, the tetaraary porphyrin iron (III) is 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 possess catalytic action, and other four metal aryls porphyrins to the reaction
Compound does not also possess catalytic activity, such as four metal aryl porphyrin coppers, four metal aryl Cobalt Porphyrins.Tetaraary porphyrin iron
(III) can also be tetraphenylporphyrin iron chloride derivative, substituent can be contained on its phenyl ring, such as conventional amino, nitro,
Alkyl, alkoxy, halogen etc..
More preferably scheme, the consumption of the tetaraary porphyrin iron chloride is the 2~10% of styrene mole.More preferably
For 3~5%.Catalyst amount increase, nitration reaction effect is substantially reduced.
The reaction mechanism that the present invention synthesizes (E)-beta-nitrostyrene by styrene 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：First, TBHP decomposes generation oxygen and hydroxyl under the conditions of certain temperature
Deng free radical, quaternary ammonium cation is 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, reactive intermediate A, intermediate A capture hydroxyl free is obtained
Base, obtains intermediate B, and intermediate B carries out the cis beta-nitrostyrene for eliminating, obtaining high E formulas solid selection.In course of reaction
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 is verified by following reaction to the mechanism of the ethene nitration reaction of the present invention, illustrates the reaction machine
The reasonability of reason.TEMPO or BHT radical scavengers (reaction 1) are added during the nitration reaction of styrene, are found almost
It cannot get reaction product, illustrate that the reaction is related to radical reaction mechanism.Next, using intermediate 2- nitro -1- hydroxyls
Ethylo benzene (B) is in NH4In I and TBHP and TPPFeCl mixed systems or in the NH without TPPFeCl4In I and TBHP mixed systems
Reaction (reaction 2), can obtain target product, illustrate that catalyst is barely affected to elimination reaction.Present invention design simultaneously
Step-reaction experiment, first step reaction is the NH in the case of no substrate styrene4I and TBHP is in TPPFeCl catalyst
Under the conditions of (a) mixed 30 minutes with without (b) under TPPFeCl catalysts conditions, be then respectively adding TEMPO, can by GC-MS
There is the generation of TEMPO- nitro free radicals analog to detect two reactions, the effect for illustrating TPPFeCl catalyst is not
It is catalyzed free radical generation (such as 3 (a) of reaction and (b))；Second step reaction is to contain TEMPO- in (3 (a) of reaction) reaction generation
Nitro free radical analog mixture is divided into two parts, and styrene substrate and TPPFeCl catalyst (d) are added in portion, another
Plus styrene substrate, but TPPFeCl catalyst (c) is not added with, heating stirring is reacted 6 hours, is as a result adding catalyst
The beta-nitrostyrene 2a (4 (c) of reaction and (d)) of higher yields can be obtained in FeTPPCl reaction, illustrates that TPPFeCl is urged
Agent, which is mainly, plays a part of catalysis free radical and styrene reaction.
Compared with the prior art, the advantageous effects that technical scheme is brought：
1) technical scheme is first 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 generation (E)-beta-nitrostyrene, relatively
Prior art, enormously simplify processing step, be conducive to industrialized production.
2) technical scheme is first using direct nitro source of the inorganic halide ammonium salt as styrene, compared to existing
Nitrogen-containing oxide, nitrite and organic nitre class compound in technology, have the advantages that cost is low, safe and environment-friendly.
3) technical scheme is catalyzed as the nitration reaction of styrene by the use of tetaraary porphyrin iron (III) tries first
Agent, the nitration reaction of styrene can be realized in a mild condition, and obtain higher yield and highly-solid selectively.
4) technical scheme 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.
Brief description of the drawings
【Fig. 1】For the nucleus magnetic hydrogen spectrum figure of the target product of embodiment 1；
【Fig. 2】For the nuclear-magnetism carbon spectrogram of the target product of embodiment 1.
Embodiment
Implement to be intended to further illustrate present invention below, rather than limit the protection domain of the claims in the present invention.
All solvents, metalloporphyrin, oxidant, ammonium salt and the alkene used in following examples is all from commercial source purchase
Buy.
All target compounds are characterized using GC-MS and NMR (1H and 13C) spectroscopic data.
NMR model Bruker AV400MHz, relative displacement is represented using ppm, with the relative displacement of trimethyl silane
On the basis of ppm=0.
1H relative displacements 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.
The progress in the seal pipe at end (25mL) is threaded of all nitration reactions.
Unless otherwise indicated, molecular sieve water removal preservation is all added in all liq reagent.
The yield of target product in following examples is based on the target product progress that stereoselectivity is E formula structures
Calculate, 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, then add styrene, NH4I and TPPFeCl, is eventually adding TBHP.Reaction is stirred vigorously 6 at 120 DEG C small
When, and monitored by TLC.After the completion of reaction, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).
Finally, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel (200-
300 mesh sieves) 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.+.
Contrast experiment's group 1：
Comparative examples 1~12 are reacted by following reaction equation：
Concrete operation step is：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.Acetonitrile is firstly added, styrene, NH is then added4I and catalyst, are eventually adding TBHP.Reaction is existed
It is stirred vigorously 6 hours, and is monitored by TLC at 120 DEG C.After the completion of reaction, mixture is cooled to room temperature, then filters and is used in combination
Ethyl acetate (EA) is washed.Finally, filtrate is concentrated with rotary evaporator, elution is used as with petroleum ether (PE)/ethyl acetate (EA)
Agent, column chromatography purifying is carried out using silica gel (200-300 mesh sieves).
The yield of the different catalysts of table 1 and the corresponding target product of consumption
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 particularly 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 consumption of agent should not be excessively used, and catalyst excess, product yield is substantially reduced, and be not added with catalyst, hence it is evident that cannot get mesh
Product is marked, oxidation product is only able to find.
Contrast experiment's group 2：
Comparative examples 13~21 are reacted by following reaction equation：
Concrete operation step is：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.Acetonitrile is firstly added, 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 completion of reaction, mixture is cooled to room temperature, then filters and uses ethyl acetate
(EA) wash.Finally, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silicon
Glue (200-300 mesh sieves) 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 can be realized using halogen quaternary ammonium salt, in addition other
Quaternary ammonium salt and ammoniacal liquor etc. all can not as styrene nitration reaction nitro source.In addition it can also be seen that iodate from table 2
Ammonium has more preferable yield with respect to ammonium bromide and ammonium chloride, and ammonium iodide is most suitable as styrene nitrating agent.
Contrast experiment's group 3：
Comparative examples 22~31 are reacted by following reaction equation：
Concrete operation step is：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, then add styrene, NH4I and catalyst, are eventually adding TBHP.Reaction is stirred vigorously 6 hours at 120 DEG C,
And monitored by TLC.After the completion of reaction, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).Most
Afterwards, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel (200-300
Mesh sieve) 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 is influenceed, and preferable yield can be obtained in atmosphere 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 the nitration reaction of styrene.
Contrast experiment's group 4：
Comparative examples 32~41 are reacted by following reaction equation：
Concrete operation step is：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.Acetonitrile is firstly added, benzene second is then added
Alkene, NH4I and catalyst, are eventually adding TBHP.Reaction is stirred vigorously 6 hours at 120 DEG C, and monitored by TLC.Reaction
After the completion of, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).Finally, concentrated with rotary evaporator
Filtrate, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, column chromatography purifying is carried out using silica gel (200-300 mesh sieves).
The difference of table 4 NH4The yield of the corresponding target product of I and TBHP ratios
NH as can be seen from Table 44The I and TBHP reaction ratio with substrate styrene, has larger to the yield of product
Influence, NH4The molar ratio of I and styrene will reach more than 1.5, meanwhile, TBHP and NH4I ratio will reach more than 4,
Can reach optimal reaction effect, and be reacted in other proportions, although can smoothly obtain target product, but yield by
To limitation.
Contrast experiment's group 5：
Comparative examples 42~51 are reacted by following reaction equation：
Concrete operation step is：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.Reaction is stirred vigorously 6 at 120 DEG C small
When, and monitored by TLC.After the completion of reaction, mixture is cooled to room temperature, then filters and is washed with ethyl acetate (EA).
Finally, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel (200-
300 mesh sieves) carry out column chromatography purifying.
The yield of the different solvents of table 5 and the corresponding target product of consumption
Contrast experiment's group 6：
Comparative examples 52~59 are reacted by following reaction equation：
Concrete operation step is：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.Acetonitrile is firstly added, 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 completion of reaction, mixture is cooled to room temperature, then filters and uses ethyl acetate
(EA) wash.Finally, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silicon
Glue (200-300 mesh sieves) carries out column chromatography purifying.
The yield of the different solvents of table 6 and the corresponding target product of consumption 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 providing N sources.
Claims (10)
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 TBHP, generates (E)-beta-nitrostyrene.
2. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that：Reaction condition is：
Under air or protective atmosphere, reaction temperature is 100 DEG C~130 DEG C, and the reaction time is 3~9h；Styrene, ammonium halide salt and tertiary fourth
The mol ratio of base hydrogen peroxide is 1:(1~2):(4~8).
3. the synthetic method of (E)-beta-nitrostyrene according to claim 2, it is characterised in that：Styrene, ammonium halide
The mol ratio of salt and TBHP is 1:(1.5~2):(6~8).
4. the synthetic method of (E)-beta-nitrostyrene according to claim 2, it is characterised in that：Reaction temperature is 115
DEG C~125 DEG C, the reaction time is 5~7h.
5. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that：The ammonium halide salt is
At least one of ammonium iodide, ammonium bromide, ammonium chloride.
6. the synthetic method of (E)-beta-nitrostyrene according to claim 5, it is characterised in that：The ammonium halide salt is
Ammonium iodide.
7. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that：The system includes second
Nitrile and/or alcohol solvent.
8. the synthetic method of (E)-beta-nitrostyrene according to claim 7, it is characterised in that：The system includes second
Nitrile.
9. the synthetic method of (E)-beta-nitrostyrene according to claim 1, it is characterised in that：The tetaraary porphyrin
Iron (III) is tetraphenylporphyrin iron chloride and/or double iron (III) porphyrins of four aryl.
10. the synthetic method of (E)-beta-nitrostyrene according to claim 9, it is characterised in that：The four aryl porphin
The consumption of quinoline iron (III) is the 2~10% of styrene mole.
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Cited By (2)
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| CN111217707A (en) * | 2020-03-17 | 2020-06-02 | 西北师范大学 | preparation method of β -trans-nitroolefin |
| CN112409187A (en) * | 2020-11-30 | 2021-02-26 | 山东华夏神舟新材料有限公司 | Synthesis method of 6-amino-1- (4-aminophenyl) -1,3,3-trimethylindane |
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| CN111217707A (en) * | 2020-03-17 | 2020-06-02 | 西北师范大学 | preparation method of β -trans-nitroolefin |
| CN111217707B (en) * | 2020-03-17 | 2022-09-16 | 西北师范大学 | Preparation method of beta-trans-nitroolefin |
| CN112409187A (en) * | 2020-11-30 | 2021-02-26 | 山东华夏神舟新材料有限公司 | Synthesis method of 6-amino-1- (4-aminophenyl) -1,3,3-trimethylindane |
| CN112409187B (en) * | 2020-11-30 | 2022-09-02 | 山东华夏神舟新材料有限公司 | Synthesis method of 6-amino-1- (4-aminophenyl) -1,3,3-trimethylindane |
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