CN107032939A - The synthetic method of α, β unsaturation nitroolefin derivative - Google Patents
The synthetic method of α, β unsaturation nitroolefin derivative Download PDFInfo
- Publication number
- CN107032939A CN107032939A CN201710345432.XA CN201710345432A CN107032939A CN 107032939 A CN107032939 A CN 107032939A CN 201710345432 A CN201710345432 A CN 201710345432A CN 107032939 A CN107032939 A CN 107032939A
- Authority
- CN
- China
- Prior art keywords
- unsaturation
- reaction
- synthetic method
- nitroolefin
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/02—Formation or introduction of functional groups containing nitrogen of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of α, the synthetic method of β unsaturation nitroolefin derivatives, vinyl compound one pot reaction in the system of iron containing tetaraary porphyrin (III), ammonium halide salt and TBHP, generates α, β unsaturation nitroolefin derivatives；It the method achieve under mild reaction conditions, the high yield synthesis α with high E stereoselectivities, β unsaturation nitroolefin.
Description
Technical field
The present invention relates to a kind of α, the synthetic method of β-unsaturation nitroolefin derivative, more particularly to a kind of alkenes chemical combination
Thing one pot reaction, high yield high selection in the system of iron containing tetaraary porphyrin (III), ammonium halide salt and TBHP
Property synthesizing trans-alpha, the method for β-unsaturation nitroolefin derivative 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
There is the α of high E stereoselectivities, the side of β-unsaturation nitroolefin in providing a kind of synthesis of high yield under mild reaction conditions
Method.
In order to realize above-mentioned technical purpose, the invention provides a kind of α, the synthesis side of β-unsaturation nitroolefin derivative
Method, this method is in iron containing tetaraary porphyrin (III), ammonium halide salt and TBHP by the structure vinyl compound of formula 1
System in one pot reaction, production 2 structure α, β-unsaturation nitroolefin derivative；
Wherein,
R、R1And R2It is independently selected from hydrogen, aryl, aliphatic group, heterocyclic radical or the aliphatic group containing substituent, and R, R1With
R2It is asynchronously aryl or hydrogen；Or, R and R2For cycloaliphatic ring alkyl or the cycloaliphatic ring alkyl containing aromatic ring.The aryl is preferred
For phenyl, substituted-phenyl or naphthyl；The aliphatic group is preferably C1~C12Alkyl；The heterocyclic radical be preferably pyridine radicals or
Thienyl；The aliphatic group containing substituent is preferably the C containing substituent1~C12Alkyl, substituent is common
Non- alkane substituent, such as halogen, hydroxyl, amino nitro；The cycloaliphatic ring alkyl is preferably C6~C8Cycloaliphatic ring alkyl；Institute
State the cycloaliphatic ring alkyl preferably C containing aromatic ring12~C14Cycloaliphatic ring alkyl containing phenyl ring.
More preferably substituted-phenyl has the structure of formula 3：
Wherein,
R3And R4It is independently selected from hydrogen, alkyl, alkoxy, haloalkyl, halogen, acetoxyl group or alkenyl, and R3And R4It is different
When be hydrogen.
Further preferred substituted-phenyl is p-methylphenyl, p-methoxyphenyl, to isobutyl phenenyl, to chloromethylbenzene
Base, p-fluorophenyl, p-bromophenyl, rubigan, to acetoxyl group, an aminomethyl phenyl, m-bromophenyl, Chloro-O-Phenyl, bromophenyl
Base, 2,5- 3,5-dimethylphenyls or 2- ethenylphenyls.
Most preferred vinyl compound is： The α of corresponding generation, β-unsaturation nitroolefin derivative
For：
The substituent that the vinyl compound of the present invention is carried out on nitration reaction, alkene can be saturation or undersaturated fat
Fat alkyl, can also be aryl, heterocyclic radical etc., but the efficiency that the alkene with different substituents is nitrified is presented substantially
Rule change.By taking the alkene containing a substitution as an example, the nitrification efficiency of aryl ethylene, heterocyclic vinyl and alkyl vinyl is successively
Reduction.And during aryl ethylene progress nitration reaction, the substituent on phenyl ring is not it is obvious that as having on the influence of nitration reaction efficiency
There is the phenyl ring (- CH of electron donating group3、-OCH3、-tBu、-CH2Cl) and the phenyl ring with electron withdraw group (- F ,-Cl ,-Br and
CH3COO-) nitration reaction can be smoothed out, and can obtain close nitrification efficiency.Alkene containing two substituents, such as 1,
1- diphenylethlenes, cyclenes and methyl styrene etc. can also obtain considerable nitrification efficiency, but many experiments show triphen
Ethene will not be nitrified.
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 vinyl compound, ammonium halide salt and TBHP is 1:(1~2):(4~
8).Further preferred scheme, the mol ratio of vinyl compound, 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, is α, β-unsaturation nitroolefin derivative provides nitro substituent.Many experiments show, adopt
The nitration reaction to alkene can be realized with ammonium bromide and ammonium chloride, but nitrification efficiency is not very high, and use ammonium iodide
When, nitrification efficiency 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 α, and β-unsaturation nitroolefin derivative or yield are at a fairly low.Acetonitrile is optimal in the inventive method
Reaction dissolvent, 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 1~15% of vinyl compound mole.More
Preferably 3~5%.Catalyst amount is increased or decreased, and nitration reaction effect is substantially reduced.
The present invention synthesizes α by olefin(e) compound, and the reaction mechanism of β-unsaturation nitroolefin derivative is as follows, with NH4I、
TBHP, TPPFeCl acetonitrile solution are reaction system, are substrate synthesis type 2 structure α, β-unsaturation by the vinyl compound of formula 1
Nitroolefin derivative, reaction mechanism is specifically described as example：First, TBHP decomposes life under the conditions of certain temperature
Into the free radical such as oxygen and hydroxyl, quaternary ammonium cation is oxidized to nitrogen dioxide free radical by oxygen radical, and nitrogen dioxide free radical exists
Radical Addition is carried out to vinyl compound under TPPFeCl catalytic media transferances, reactive intermediate A is obtained, it is middle
Body A captures hydroxyl radical free radical, obtains intermediate B, and intermediate B carries out the cis α, β-insatiable hunger for eliminating, obtaining high E formulas solid selection
With nitroolefin derivative.TPPFeCl primarily serves transferred free radical effect in course of reaction, can form unstable centre
Body, but finally still exist with TPPFeCl, play catalytic action.Reaction mechanism equation is as follows：
The present invention is verified by following reaction to the mechanism of the vinyl compound nitration reaction of the present invention, illustrates this
The reasonability of reaction mechanism, is illustrated by taking styrene nitration reaction as an example.Added during the nitration reaction of styrene
TEMPO or BHT radical scavengers (reaction 1), discovery is hardly obtained reaction product, illustrates that the reaction is related to free radical anti-
Answer mechanism.Next, using intermediate 2- nitro -1- hydroxyethyls benzene (B) in NH4In I and TBHP and TPPFeCl mixed systems
Or in the NH without TPPFeCl4Reaction (reaction 2), can obtain target product, illustrate catalyst in I and TBHP mixed systems
Elimination reaction is barely affected.The present invention devises step-reaction experiment simultaneously, and first step reaction is that do not having substrate alkene
In the case of hydrocarbon, NH4I and TBHP (a) under TPPFeCl catalysts conditions is mixed with without (b) under TPPFeCl catalysts conditions
30 minutes, TEMPO is then respectively adding, can detect two reactions by GC-MS has TEMPO- nitros radical type seemingly
Thing is generated, and the effect for illustrating TPPFeCl catalyst is not catalysis free radical generation (such as 3 (a) of reaction and (b))；Second step is anti-
It should be being divided into two parts (3 (a) of reaction) reaction generation containing TEMPO- nitro free radical analog mixtures, be added in portion
Styrene substrate and TPPFeCl catalyst (d), another adds styrene, but is not added with catalyst (c), and heating stirring reaction 6 is small
When, nitrostyrolene 2a (4 (c) of reaction and (d)), explanation as a result can be obtained in the reaction for adding catalyst Fe TPPCl
TPPFeCl catalyst, which is mainly, plays a part of catalysis nitro 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 vinyl compound, realizes the generation of vinyl compound one pot reaction α, β-unsaturation nitro
Alkene, compared with the prior art, enormously simplify processing step, is conducive to industrialized production.
2) technical scheme is used as the direct nitro source of alkenes compounds, phase using inorganic halide ammonium salt first
Than nitrogen-containing oxide of the prior art, nitrite and organic nitre class compound, have the advantages that cost is low, safe and environment-friendly.
3) nitration reaction of the technical scheme first by the use of tetaraary porphyrin iron (III) as vinyl compound is urged
Change reagent, the nitration reaction of various alkenes compounds can be realized in a mild condition, and obtain higher yield and height
Stereoselectivity.
4) technical scheme realizes α, the one pot process of β-unsaturation nitroolefin derivative, and target and produced
Thing is easily isolated purification, simplifies processing step, 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；
【Fig. 3】For the nucleus magnetic hydrogen spectrum figure of the target product of embodiment 2；
【Fig. 4】For the nuclear-magnetism carbon spectrogram of the target product of embodiment 2；
【Fig. 5】For the nucleus magnetic hydrogen spectrum figure of the target product of embodiment 20；
【Fig. 6】For the nuclear-magnetism carbon spectrogram of the target product of embodiment 20；
【Fig. 7】For the nucleus magnetic hydrogen spectrum figure of the target product of embodiment 22；
【Fig. 8】For the nuclear-magnetism carbon spectrogram of the target product of embodiment 22；
【Fig. 9】For the nucleus magnetic hydrogen spectrum figure of the target product of embodiment 27；
【Figure 10】For the nuclear-magnetism carbon spectrogram of the target product of embodiment 27.
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 1~21
Embodiment 1~21 is 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 (the 3~5% of styrene mole) and acetonitrile (2mL) are added to close
In tube sealing.Acetonitrile is firstly added, alkene, NH is then added4I and TPPFeCl, is eventually adding TBHP.Will reaction play at 120 DEG C
Strong 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.
Embodiment 1
Alkene：Target product：(C8H7NO2)；
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.+.
Embodiment 2
Alkene：Target product：(C9H9NO2)。
Yellow solid:77% (63mg)1H NMR(400MHz,CDCl3) δ 7.96 (d, J=13.6Hz, 1H), 7.55
(d, J=13.6Hz, 1H), 7.43 (d, J=8.1Hz, 2H), 7.25 (d, J=8.2Hz, 2H), 2.40 (s, 3H)13C NMR
(101MHz,CDCl3)δ143.04,139.08,136.17,130.06,129.12,127.17,21.56.GC-MS(m/z):
163.
Embodiment 3
Alkene：Target product：(C9H9NO3)；
Yellow solid:73% (65mg)1H NMR(400MHz,CDCl3) δ 7.97 (d, J=13.6Hz, 1H), 7.51
(dd, J=11.2,5.8Hz, 3H), 6.96 (d, J=8.8Hz, 2H), 3.87 (s, 3H)13C NMR(101MHz,CDCl3)δ
162.93,139.00,135.03,131.14,122.54,114.98,55.51.GC-MS(m/z):179.
Embodiment 4
Alkene：Target product：(C12H15NO2)；
Yellow solid；isolated yield:58% (60mg)1H NMR(400MHz,CDCl3) δ 7.99 (d, J=
13.6Hz, 1H), 7.58 (d, J=13.6Hz, 1H), 7.48 (d, J=2.0Hz, 4H), 1.34 (s, 9H)13C NMR(101MHz,
CDCl3)δ156.08,138.98,136.32,129.03,127.17,126.35,35.05,30.94.GC-MS(m/z):203.
Embodiment 5
Alkene：Target product：(C9H8ClNO2)；
Yellow solid:70% (69mg)1H NMR(400MHz,CDCl3) δ 7.98 (d, J=13.7Hz, 1H), 7.56
(dd, J=16.0,10.9Hz, 3H), 7.47 (d, J=8.2Hz, 2H), 4.60 (s, 2H)13C NMR(101MHz,CDCl3)δ
(141.45,138.16,137.40,129.98,129.41 d, J=3.1Hz), 45.22.GC-MS (m/z):197.
Embodiment 6
Alkene：Target product：(C8H6FNO2)；
Yellow solid:65% (54mg)1H NMR(400MHz,CDCl3) δ 7.98 (d, J=13.7Hz, 1H), 7.55
(t, J=12.0Hz, 3H), 7.15 (t, J=8.0Hz, 2H)13C NMR(101MHz,CDCl3)δ164.92,137.81,
(d, J=8.9Hz), 136.83,131.26 126.29 (d, J=3.6Hz), 116.78 (d, J=22.2Hz) ..GC-MS (m/z):
167.
Embodiment 7
Alkene：Target product：(C8H6ClNO2)；
Yellow solid:56% (51mg)1H NMR(400MHz,CDCl3) δ 7.95 (d, J=13.7Hz, 1H), 7.56
(d, J=13.7Hz, 1H), 7.51-7.46 (m, 2H), 7.45-7.37 (m, 2H)13C NMR(101MHz,CDCl3)δ138.21,
137.63,137.33,130.22,129.66,128.45.GC-MS(m/z):183.
Embodiment 8
Alkene：Target product：(C8H6BrNO2)；
Yellow solid:58% (67mg)1H NMR(400MHz,CDCl3) δ 7.95 (d, J=13.7Hz, 1H), 7.58
(t, J=10.4Hz, 3H), 7.42 (d, J=8.5Hz, 2H)13C NMR(101MHz,CDCl3)δ137.75,137.47,
132.74,130.36,128.94,126.78.GC-MS(m/z):228。
Embodiment 9
Alkene：Target product：(C10H9NO4)；
Yellow solid:61% (63mg)1H NMR(400MHz,CDCl3) δ 7.98 (d, J=13.7Hz, 1H), 7.56
(dd, J=11.1,7.8Hz, 3H), 7.20 (d, J=8.6Hz, 2H), 2.32 (s, 3H)13C NMR(101MHz,CDCl3)δ
168.84,153.45,137.96,137.07,130.37 127.60,122.71,21.08.GC-MS(m/z):207。
Embodiment 10
Alkene：Target product：(C8H6ClNO2)；
Yellow solid:53% (49mg)1H NMR(400MHz,CDCl3) δ 8.40 (d, J=13.7Hz, 1H),
7.62-7.56 (m, 2H), 7.50 (dd, J=8.0,1.2Hz, 1H), 7.43 (td, J=7.8,1.6Hz, 1H), 7.34 (t, J=
8.1Hz,1H).13C NMR(101MHz,CDCl3)δ138.81,136.01,135.08,132.81,130.72,128.57,
128.49,127.45.GC-MS(m/z):183.
Embodiment 11
Alkene：Target product：(C8H6BrNO2)；
Yellow solid:47% (54mg)1H NMR(400MHz,CDCl3) δ 8.38 (d, J=13.6Hz, 1H), 7.68
(dd, J=7.8,1.3Hz, 1H), 7.57 (dd, J=7.6,1.7Hz, 1H), 7.53 (d, J=13.6Hz, 1H), 7.41-7.31
(m,2H).13C NMR(101MHz,CDCl3)δ138.79,137.54,133.96,132.90(,130.29,128.43,
128.05,126.29.GC-MS(m/z):228
Embodiment 12
Alkene：Target product：(C9H9NO2)；
Yellow solid:55% (45mg)1H NMR(400MHz,CDCl3) δ 7.97 (d, J=13.7Hz, 1H), 7.57
(d, J=13.7Hz, 1H), 7.40-7.28 (m, 4H), 2.40 (s, 3H)13C NMR(101MHz,CDCl3)δ139.20,
139.17,136.86,132.96,129.93,129.65,129.20,126.31,21.18.GC-MS(m/z):163.
Embodiment 13
Alkene：Target product：(C8H6BrNO2)；
Yellow solid:45% (51mg)1H NMR(400MHz,CDCl3) δ 7.90 (d, J=13.7Hz, 1H), 7.67
(t, J=1.7Hz, 1H), 7.60 (dd, J=8.0,2.7Hz, 1H), 7.55 (d, J=13.7Hz, 1H), 7.47 (d, J=
7.8Hz, 1H), 7.32 (t, J=7.9Hz, 1H)13C NMR(101MHz,CDCl3)δ137.94,137.22,134.73,
131.95,131.55,130.75,127.57,123.28.GC-MS(m/z):228
Embodiment 14
Alkene：Target product：(C10H11NO2)；
Yellow solid:74% (82mg)1H NMR(400MHz,CDCl3) δ 8.26 (d, J=13.6Hz, 1H), 7.50
(d, J=13.6Hz, 1H), 7.32 (s, 1H), 7.22-7.14 (m, 2H), 2.42 (s, 3H), 2.34 (s, 3H)13C NMR
(101MHz,CDCl3)δ137.22,136.77,136.21,136.17,132.79,131.17,128.57,127.69,20.72,
19.28.GC-MS(m/z):163.
Embodiment 15
Alkene：Target product：(C10H7NO2)；
Yellow solid:44% (43mg)1H NMR(400MHz,CDCl3) δ 8.13 (d, J=13.6Hz, 1H), 7.98
(s, 1H), 7.87 (dd, J=8.2,6.0Hz, 3H), 7.68 (d, J=13.6Hz, 1H), 7.62-7.51 (m, 3H)13C NMR
(101MHz,CDCl3)δ139.14,137.05,134.83,133.06,132.22,129.28,128.77,128.33,
127.88,127.46,127.21,123.24.GC-MS(m/z):199.
Embodiment 16
Alkene：Target product：(C10H9NO2)；
Yellow solid:34% (30mg)1H NMR(400MHz,CDCl3) δ 8.13 (d, J=13.6Hz, 1H), 7.98
(s, 1H), 7.87 (dd, J=8.2,6.0Hz, 3H), 7.68 (d, J=13.6Hz, 1H), 7.62-7.51 (m, 3H)13C NMR
(101MHz,CDCl3)δ139.14,137.05,134.83,133.06,132.22,129.28,128.77,128.33,
127.88,127.46,127.21,123.24.GC-MS(m/z):175.
Embodiment 17
Alkene：Target product：(C7H6N2O2)；
Brownish yellow solid:28% (21mg)1H NMR(400MHz,CDCl3)δ8.66(s,1H),7.95
(dd, J=38.3,13.1Hz, 2H), 7.78 (t, J=7.6Hz, 1H), 7.58-7.29 (m, 2H)13CNMR(101MHz,
CDCl3)δ150.59,149.31,140.63,137.13,137.10,126.27,125.67.GC-MS(m/z):150.
Embodiment 18
Alkene：Target product：(C7H6N2O2)；
Yellowish gray solid:22% (17mg)1H NMR(400MHz,CDCl3)δ8.74(s,2H),7.92
(d, J=13.7Hz, 1H), 7.65 (d, J=13.1Hz, 1H), 7.40 (s, 2H)13C NMR(101MHz,CDCl3)δ150.99,
140.32,137.38,136.06,122.31.GC-MS(m/z):150.
Embodiment 19
Alkene：Target product：(C6H5NO2S)；
Yellow solid:37% (29mg)1H NMR(400MHz,CDCl3) δ 8.15 (d, J=13.4Hz, 1H), 7.56
(d, J=5.0Hz, 1H), 7.47 (t, J=8.9Hz, 2H), 7.15 (dd, J=5.1,3.7Hz, 1H)13C NMR(101MHz,
CDCl3)δ135.31,134.61,133.72,132.06,131.59,128.85.GC-MS(m/z):155.
Embodiment 20
Alkene：Target product：(C8H15NO2)；
Orange liquid:22% (17mg)1H NMR(400MHz,CDCl3)δ7.33–7.23(m,1H),6.99(d,J
=13.4Hz, 1H), 2.27 (d, J=7.2Hz, 2H), 1.34 (s, 2H), 1.30-1.28 (m, 2H), 1.16 (d, J=9.6Hz,
2H),0.90(s,4H).13C NMR(101MHz,CDCl3)δ142.71,139.41,77.00,31.27,28.60,28.30,
27.53,22.32,13.84.GC-MS(m/z):157.
Embodiment 21
Alkene：Target product：
Yellow liquid:30% (84mg)1H NMR(400MHz,CDCl3)δ7.24–7.18(m,1H),6.93(dt,
J=13.4,1.5Hz, 1H), 2.21 (ddd, J=14.9,7.4,1.5Hz, 2H), 1.21 (s, 18H), 0.83 (t, J=6.8Hz,
3H).13C NMR(101MHz,CDCl3)δ142.81,139.52,31.87,29.59,29.58,29.54,29.41,29.30,
29.22,29.05,28.42,27.68,22.65,14.08.GC-MS(m/z):241.
Embodiment 22~28
Embodiment 22~28 is 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 acetonitrile (2mL) are added in seal pipe.First plus
Enter acetonitrile, then add alkene, NH4I and TPPFeCl, is 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.
Embodiment 22
Alkene：Target product：(C9H9NO2)；
Yellow solid:49% (40mg)1H NMR(400MHz,CDCl3)δ7.48–7.43(m,5H),7.31(d,J
=1.3Hz, 1H), 2.65 (d, J=1.3Hz, 3H)13C NMR(101MHz,CDCl3)δ149.96,138.27,136.31,
130.34,129.01,126.81,18.57.GC-MS(m/z):163.
Embodiment 23
Alkene：Target product：(C14H11NO2)；
Yellow solid:42% (47mg)1H NMR(400MHz,CDCl3)δ7.49–7.31(m,7H),7.30–7.22
(m,2H),7.22–7.16(m,2H).13C NMR(101MHz,CDCl3)δ150.37,136.96,135.45,134.30,
130.82,129.21,128.82,128.79,128.70,128.40.GC-MS(m/z):225.
Embodiment 24
Alkene：Target product：(C14H11NO2)；
Yellow solid:38% (31mg)1H NMR(400MHz,CDCl3)δ8.27(s,1H),7.57–7.50(m,
3H), (d, J=7.6Hz, the 2H) of 7.41-7.32 (m, 3H), 7.27 (dd, J=13.5,5.6Hz, 2H), 7.1313C NMR
(101MHz,CDCl3)δ149.59,134.79,131.34,131.16,130.72,130.52,130.02,129.87,
129.19,128.68.GC-MS(m/z):225.
Embodiment 25
Alkene：Target product：(C9H9NO2)；
Yellow solid:38% (31mg)1H NMR(400MHz,CDCl3)δ8.08(s,1H),7.48–7.40(m,
5H), 2.45 (d, J=0.8Hz, 3H)13C NMR(101MHz,CDCl3)δ147.64,133.44,132.31,129.88,
129.84,128.81,13.92.GC-MS(m/z):163.
Embodiment 26
Alkene：Target product：(C10H9NO2)；
Yellow liquid:38% (34mg)1H NMR(400MHz,CDCl3) δ 7.81 (s, 1H), 7.32 (ddd, J=
11.0,8.3,3.9Hz, 2H), 7.27-7.17 (m, 2H), 3.03 (dd, J=12.7,5.0Hz, 2H), 2.94 (dd, J=12.7,
5.4Hz,2H).13C NMR(101MHz,CDCl3)δ147.87,136.36,131.54,131.21,130.12,130.09,
127.87,127.28,27.87,22.32.GC-MS(m/z):175.
Embodiment 27
Alkene：Target product：(C6H9NO2)；
Orange liquid:35% (22mg)1H NMR(400MHz,CDCl3) δ 7.30 (ddd, J=5.7,4.1,
1.5Hz, 1H), 2.59-2.51 (m, 2H), 2.35-2.28 (m, 2H), 1.79-1.72 (m, 2H), 1.61 (dtd, J=9.2,
6.0,2.9Hz,2H).13C NMR(101MHz,CDCl3)δ149.64,134.25,24.71,23.83,21.71,20.59.GC-
MS(m/z):127。
Embodiment 28
Alkene：Target product：(C8H11NO2)；
Orange liquid:22% (17mg)1H NMR(400MHz,CDCl3) δ 7.35 (t, J=5.7Hz, 1H), 5.57
(s, 2H), 3.03 (t, J=6.3Hz, 2H), 2.68-2.55 (m, 2H), 2.55-2.42 (m, 4H)13C NMR(101MHz,
CDCl3)δ151.52,135.18,128.62,127.64,27.04,26.66,26.29,25.63.GC-MS(m/z):153。
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, alkene, NH is then added4I and catalyst, are eventually adding TBHP.It will react 120
It is stirred vigorously 6 hours, and is monitored by TLC at DEG C.After the completion of reaction, mixture is cooled to room temperature, then filters and uses second
Acetoacetic ester (EA) is washed.Finally, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent,
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, alkene, NH is then added4I and catalyst, are eventually adding TBHP.Reaction is acutely stirred at 120 DEG C
Mix 6 hours, and monitored by TLC.After the completion of reaction, mixture is cooled to room temperature, then filtering and with ethyl acetate (EA)
Washing.Finally, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel
(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 alkene, 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).Finally,
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, alkene is then added
Hydrocarbon, 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, alkene, 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, alkene, NH is then added4I and TPPFeCl, is eventually adding TBHP.Reaction is acutely stirred at 120 DEG C
Mix 6 hours, and monitored by TLC.After the completion of reaction, mixture is cooled to room temperature, then filtering and with ethyl acetate (EA)
Washing.Finally, filtrate is concentrated with rotary evaporator, with petroleum ether (PE)/ethyl acetate (EA) as eluant, eluent, using silica gel
(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. the synthetic method of a kind of α, β-unsaturation nitroolefin derivative, it is characterised in that：The structure vinyl compound of formula 1 containing
One pot reaction in the system of tetaraary porphyrin iron (III), ammonium halide salt and TBHP, production 2 structure α, β-no
Saturation nitroolefin derivative；
Wherein,
R、R1And R2It is independently selected from hydrogen, aryl, aliphatic group, heterocyclic radical or the aliphatic group containing substituent, and R, R1And R2No
It is simultaneously aryl or hydrogen；Or, R and R2For cycloaliphatic ring alkyl or the cycloaliphatic ring alkyl containing aromatic ring.
2. the synthetic method of α according to claim 1, β-unsaturation nitroolefin derivative, it is characterised in that：The virtue
Alkyl is phenyl, substituted-phenyl or naphthyl；
The aliphatic group is C1~C12Alkyl；
The heterocyclic radical is pyridine radicals or thienyl；
The aliphatic group containing substituent is the C containing substituent1~C12Alkyl；
The cycloaliphatic ring alkyl is C6~C8Cycloaliphatic ring alkyl；
The cycloaliphatic ring alkyl containing aromatic ring is C12~C14Cycloaliphatic ring alkyl containing phenyl ring.
3. the synthetic method of α according to claim 2, β-unsaturation nitroolefin derivative, it is characterised in that：It is described to take
There is the structure of formula 3 for phenyl：
Wherein,
R3And R4It is independently selected from hydrogen, alkyl, alkoxy, haloalkyl, halogen, acetoxyl group or alkenyl, and R3And R4It is asynchronously
Hydrogen.
4. the synthetic method of α according to claim 3, β-unsaturation nitroolefin derivative, it is characterised in that：It is described to take
For phenyl be p-methylphenyl, p-methoxyphenyl, to isobutyl phenenyl, to chloromethyl phenyl, p-fluorophenyl, p-bromophenyl,
Rubigan, to acetoxyl group, an aminomethyl phenyl, m-bromophenyl, Chloro-O-Phenyl, o-bromophenyl, 2,5- 3,5-dimethylphenyls or 2-
Ethenylphenyl.
5. the synthetic method of the α according to any one of Claims 1 to 4, β-unsaturation nitroolefin derivative, its feature exists
In：Reaction condition is：Under air or protective atmosphere, reaction temperature is 100 DEG C~130 DEG C, and the reaction time is 3~9h；Alkenes
The mol ratio of compound, ammonium halide salt and TBHP is 1:(1~2):(4~8).
6. the synthetic method of α according to claim 5, β-unsaturation nitroolefin derivative, it is characterised in that：The halogen
Change ammonium salt is at least one of ammonium iodide, ammonium bromide, ammonium chloride.
7. the synthetic method of α according to claim 6, β-unsaturation nitroolefin derivative, it is characterised in that：The halogen
Change ammonium salt is ammonium iodide.
8. the synthetic method of α according to claim 1, β-unsaturation nitroolefin derivative, it is characterised in that：The body
System includes acetonitrile and/or alcohol solvent.
9. the synthetic method of α according to claim 1, β-unsaturation nitroolefin derivative, it is characterised in that：Described four
Aryl-porphyrin iron (III) is tetraphenylporphyrin iron chloride and/or double iron (III) porphyrins of four aryl.
10. the synthetic method of α according to claim 9, β-unsaturation nitroolefin derivative, it is characterised in that：It is described
The consumption of tetaraary porphyrin iron (III) is the 1~15% of vinyl compound mole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710345432.XA CN107032939B (en) | 2017-05-17 | 2017-05-17 | Synthetic method of alpha, beta-unsaturated nitroolefin derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710345432.XA CN107032939B (en) | 2017-05-17 | 2017-05-17 | Synthetic method of alpha, beta-unsaturated nitroolefin derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107032939A true CN107032939A (en) | 2017-08-11 |
| CN107032939B CN107032939B (en) | 2020-09-11 |
Family
ID=59537107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710345432.XA Active CN107032939B (en) | 2017-05-17 | 2017-05-17 | Synthetic method of alpha, beta-unsaturated nitroolefin derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107032939B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217707A (en) * | 2020-03-17 | 2020-06-02 | 西北师范大学 | preparation method of β -trans-nitroolefin |
| CN111704548A (en) * | 2020-05-20 | 2020-09-25 | 郑州师范学院 | Method for preparing nitroolefin from aryl ethane and nitrate |
Citations (6)
| 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 |
| CN104710315A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院大连化学物理研究所 | Alpha, beta-nonsaturated nitroolefin compound eco-friendly synthesis method |
| CN105152935A (en) * | 2015-09-06 | 2015-12-16 | 安徽理工大学 | Method for preparing beta-nitrostyrolene compound |
-
2017
- 2017-05-17 CN CN201710345432.XA patent/CN107032939B/en active Active
Patent Citations (6)
| 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 |
| CN104710315A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院大连化学物理研究所 | Alpha, beta-nonsaturated nitroolefin compound eco-friendly synthesis method |
| CN105152935A (en) * | 2015-09-06 | 2015-12-16 | 安徽理工大学 | Method for preparing beta-nitrostyrolene compound |
Non-Patent Citations (1)
| Title |
|---|
| WING-WAH SY等: "NITRATION OF SUBSTITUTED STYRENES WITH NITRYL IODIDE", 《TETRAHEDRON LETTERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111704548A (en) * | 2020-05-20 | 2020-09-25 | 郑州师范学院 | Method for preparing nitroolefin from aryl ethane and nitrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107032939B (en) | 2020-09-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Copper-catalyzed radical relay for asymmetric radical transformations | |
| Fingerhut et al. | Non-heme iron catalysts for epoxidation and aziridination reactions of challenging terminal alkenes: towards sustainability | |
| Goswami et al. | Metal‐Catalysed Azidation of Organic Molecules | |
| Yang et al. | Magnesium catalysis in asymmetric synthesis | |
| JP2007016036A (en) | Long-lived homogenous oxidation catalysts | |
| CN104193600B (en) | A kind of method preparing aldehydes or ketones for promoter air oxidation alcohol with aluminium oxide | |
| Song et al. | Photoinduced copper-catalyzed enantioselective coupling reactions | |
| CN107032939A (en) | The synthetic method of α, β unsaturation nitroolefin derivative | |
| Steinlandt et al. | Stereogenic-at-iron catalysts with a chiral tripodal pentadentate ligand | |
| CN107098811B (en) | (E)-beta-nitrostyrene synthetic method | |
| Chen et al. | Biologically inspired nonheme iron complex-catalyzed cis-dihydroxylation of alkenes modeling Rieske dioxygenases | |
| Kumari et al. | Efficient iron (III) porphyrins-catalyzed oxidation of guanidoximes to cyanamides in ionic liquids | |
| CN110003011A (en) | It is a kind of using nitrate as the preparation method of the nitroolefin derivative in nitro source | |
| Yamashita et al. | Catalytic Asymmetric Mannich‐Type Reactions Using a Novel Chiral Iron Complex | |
| CN106995373B (en) | Using ammonium iodide as nitro source one-pot synthesis α, β-unsaturation nitroolefin derivative method | |
| CN105646382A (en) | Preparation method of 1,3,5-trisubstituted 1,2,4-triazole compound | |
| Zhou et al. | Recent advances on radical-mediated cyanoalkylation/cyanation using AIBN and Analogues as the radical sources | |
| CN107417535B (en) | A kind of one-pot synthesis method of highly selective (E)-beta-nitrostyrene derivative | |
| JP2017530956A (en) | Asymmetric catalytic synthesis of nitropyrazole amide compounds | |
| Yu et al. | MnII complexes with tetradentate N4 ligands: Highly efficient catalysts for the epoxidation of olefins with H2O2 | |
| CN106995372B (en) | A method of (E)-beta-nitrostyrene derivative is catalyzed and synthesized based on tetaraary porphyrin iron | |
| Hayashi | Catalytic Asymmetric Diels‐Alder Reactions | |
| CN103977839A (en) | Ionic organic metal tungstate epoxidation catalyst and preparation method thereof | |
| Li et al. | A new metal− organic complex with coordination unsaturated Co (II) as high-efficiency heterogeneous catalyst for selective oxidation of alkylbenzenes | |
| Innocenti et al. | Dual Iminium-and Lewis Base Catalyzed Morita–Baylis–Hillman Reaction on Cyclopent-2-enone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |