CN107032939B - Synthetic method of alpha, beta-unsaturated nitroolefin derivative - Google Patents
Synthetic method of alpha, beta-unsaturated nitroolefin derivative Download PDFInfo
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Abstract
The invention discloses a synthesis method of an alpha, beta-unsaturated nitroolefin derivative, wherein an alkene compound is subjected to one-pot reaction in a system containing tetraarylporphyrin iron (III), halogenated ammonium salt and tert-butyl hydroperoxide to generate the alpha, beta-unsaturated nitroolefin derivative; the method realizes the synthesis of the alpha, beta-unsaturated nitroolefin with high E stereoselectivity in high yield under mild reaction conditions.
Description
Technical Field
The invention relates to a method for synthesizing an alpha, beta-unsaturated nitroolefin derivative, in particular to a method for synthesizing a trans-alpha, beta-unsaturated nitroolefin derivative with high yield and high selectivity by one-pot reaction of an alkene compound in a system containing tetraarylporphyrin iron (III), halogenated ammonium salt and tert-butyl hydroperoxide, belonging to the field of organic synthesis.
Background
Alpha, beta-unsaturated nitroolefins are a class of compounds with biological activity. For example, unsaturated nitro fatty acids are a new class of endogenous anti-inflammatory mediators; the unsaturated nitrooleic acid can prevent ischemia and reperfusion injury of the kidney of the rat. Meanwhile, the alpha, beta-unsaturated nitroolefin is an important drug and organic intermediate compound, can be easily converted into various different compounds, and plays an important role in many fields. For example, β -nitrostyrene is an intermediate used in the preparation of several phenethylamines and fungicides (Chemical Abstracts, vol.118, No.38576 k). Alpha, beta-unsaturated nitroolefins are also widely used as Michael acceptors in reactions such as asymmetric Michael reactions of aldehydes, ketones with nitroolefins, and stereoselective Friedel-Crafts alkylation reactions of indoles, pyrroles with nitroolefins; asymmetric Michael addition between nitroalkenes and nitroalkanes; asymmetric biological reduction of nitroolefins, and the like.
Accordingly, the classical scheme for synthesizing nitroolefins using nitro compounds as a nitro source has been reported since decades, the Henry reaction, as reported earlier, is a condensation reaction of aldehydes or ketones with nitroalkanes under alkaline conditions to obtain nitroolefin derivatives (e.g., reaction 1), but the Henry reaction has problems of relatively severe reaction conditions, relatively low reaction yield, and generation of a large amount of waste lye, and subsequently, some improved Henry reactions have been reported, such as the Henry condensation of nitromethane with aldehyde compounds to obtain β -nitroalcohol, the dehydration of β -nitroalcohol via DCC/CuCl or trifluoroacetic anhydride/triethylamine, or the dehydration via MsCl/Et3Or P2Dehydration to α -unsaturated nitroolefin, such as BrCH2NO2For example, Chinese patent (CN106083597A) discloses a method for synthesizing a conjugated nitroalkene by using an aliphatic aldehyde and a nitro group of nitroalkane to carry out aldol condensation reaction in the presence of a diamine, wherein the elimination reaction of the conjugated nitroalkene is carried out by adding an acid in the reaction process (for example, reaction 2), the method reduces the generation of side reactions by using the diamine as a catalyst for the nitroaldol condensation reaction, improves the yield of the product, but has many reaction steps, produces a large amount of acidic waste liquid, and pollutes the environment.Chinese patent (CN 104710315A) discloses a green method for synthesizing an unsaturated nitroalkene compound (for example, reaction 3), uses a green method for synthesizing an aromatic nitroalkene compound (for example, reaction 3), and uses a microwave system for heating reaction, and can improve the yield of the nitroalkene by using the aromatic aldehyde and the aromatic aldehyde, and the nitroalkene compound, and the aromatic aldehyde(ii) a However, the ionic liquid used in the method is high in cost and difficult to be applied industrially.
In addition, several new methods for synthesizing α, β -unsaturated nitroolefins are reported in succession. As reported earlier, the nitration of olefins to alpha, beta-unsaturated nitroolefins using nitrite and iodine and a research work to improve nitration conditions [ (Hassner 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 employ large amounts of iodine, which is a troublesome work-up procedure and reduces the yield of the product. The patent (CN1438977A) applied by Sabao group company of Italy in China discloses that a nitrostyrene compound is synthesized by using a styrene derivative as a raw material and a mixture of inorganic nitrite and iodine in the presence of peroxide as a nitration reagent; the method greatly reduces the using amount of iodine in the process of nitrifying olefin by using the oxidant, thereby improving the yield of the product to a certain extent and simplifying the process steps, but the methods all adopt nitrite as a nitrifying reagent and have great harm to the environment and human bodies. At present, some methods utilize nitrogen-containing oxides as nitration reagents, alkene compounds are directly subjected to nitration reaction under the catalysis of metal nickel oxides to obtain nitroolefin derivatives (such as reaction 4), and the method adopts a gas-liquid reaction mode, so that the reaction efficiency is low, toxic gas is generated, and the yield is not high.
Reaction 1:
reaction 2:
reaction 3:
reaction 4:
disclosure of Invention
Aiming at the defects of the method for synthesizing alpha, beta-unsaturated nitroolefin in the prior art, the invention aims to provide a method for synthesizing alpha, beta-unsaturated nitroolefin with high E stereoselectivity under mild reaction conditions with high yield.
In order to realize the technical purpose, the invention provides a method for synthesizing alpha, beta-unsaturated nitroolefin derivatives, which comprises the steps of carrying out one-pot reaction on an alkene compound with a structure shown in a formula 1 in a system containing tetraarylporphyrin iron (III), halogenated ammonium salt and tert-butyl hydroperoxide to generate the alpha, beta-unsaturated nitroolefin derivatives with the structure shown in the formula 2;
wherein the content of the first and second substances,
R、R1and R2Independently selected from hydrogen, aromatic hydrocarbon group, aliphatic hydrocarbon group, heterocyclic group or substituted aliphatic hydrocarbon group, and R, R1And R2Not simultaneously being aromatic hydrocarbon or hydrogen; or, R and R2Is aliphatic cyclic hydrocarbon group or aliphatic cyclic hydrocarbon group containing aromatic ring. The aromatic hydrocarbon group is preferably a phenyl group, a substituted phenyl group or a naphthyl group; the aliphatic hydrocarbon group is preferably C1～C12An alkyl group; the heterocyclic group is preferably pyridyl or thienyl; the aliphatic hydrocarbon group having a substituent is preferably C having a substituent1～C12The substituent is common non-alkane substituent, such as halogen, hydroxyl, amino nitro and the like; the aliphatic cyclic hydrocarbon group is preferably C6～C8An aliphatic cyclic hydrocarbon group; the aromatic ring-containing aliphatic cyclic hydrocarbon group is preferably C12～C14Aliphatic cycloalkyl containing a benzene ring.
More preferred substituted phenyl groups have the structure of formula 3:
wherein the content of the first and second substances,
R3and R4Independently selected from hydrogen, alkyl, alkoxy, haloalkyl, halogen, acetoxy or alkenyl, and R3And R4Not hydrogen at the same time.
Further preferred substituted phenyl groups are p-methylphenyl, p-methoxyphenyl, p-isobutylphenyl, p-chloromethylphenyl, p-fluorophenyl, p-bromophenyl, p-chlorophenyl, p-acetoxy, m-methylphenyl, m-bromophenyl, o-chlorophenyl, o-bromophenyl, 2, 5-dimethylphenyl or 2-vinylphenyl.
The most preferred olefinic compounds are:
the corresponding α -unsaturated nitroolefin derivative formed is:
the alkene compound of the invention is subjected to nitration reaction, the substituent on the alkene can be saturated or unsaturated aliphatic alkyl, aromatic alkyl, heterocyclic radical and the like, but the nitration efficiency of the alkene with different substituents shows obvious regular change. For example, when an olefin having one substituent is used, the nitration efficiency of an aryl ethylene, a heterocyclic ethylene and an alkyl ethylene decreases in this order. When aryl ethylene is subjected to nitration reaction, the influence of the substituent on the benzene ring on the nitration reaction efficiency is not obvious, such as the benzene ring (-CH) with an electron-donating group3、-OCH3、-tBu、-CH2Cl) and benzene rings (-F, -Cl, -Br and CH) having electron withdrawing groups3COO-) nitration reaction can be smoothly carried out, and similar nitration efficiency can be obtained. Alkenes containing two substituents, e.g. 1, 1-diphenylethylene, cycloalkenes and methylphenylethyleneAlkenes and the like can also give considerable nitration efficiency, but a large number of experiments have shown that triphenylethylene is not nitrated.
In a preferred embodiment, the reaction conditions are: under the condition of air or protective atmosphere, the reaction temperature is 100-130 ℃, and the reaction time is 3-9 h. The optimal reaction temperature is 115-125 ℃, and the reaction time is 5-7 h.
Preferably, the molar ratio of the alkene compound, the ammonium halide salt and the tert-butyl hydroperoxide is 1 (1-2) to 4-8. More preferably, the molar ratio of the alkene compound, the ammonium halide salt and the tert-butyl hydroperoxide is 1 (1.5-2) to 6-8.
In a preferred embodiment, the ammonium halide salt is at least one of ammonium iodide, ammonium bromide and ammonium chloride. In a more preferred embodiment, the ammonium halide salt is ammonium iodide. The ammonium halide is used as a nitro source, and generates a nitro radical under the oxidation action of peroxide tert-butyl hydroperoxide to provide a nitro substituent for the alpha, beta-unsaturated nitroolefin derivative. A large number of experiments show that the ammonium bromide and the ammonium chloride can be used for realizing the nitration reaction of the olefin, but the nitration efficiency is not very high, and when the ammonium iodide is used, the nitration efficiency can reach more than 80%.
Preferably, the system comprises an acetonitrile and/or ethanol solvent. The polarity of the solvent also has a certain influence on the nitration of olefins, for example, in acetonitrile and ethanol, the nitration reaction can be carried out smoothly, and the alpha, beta-unsaturated nitroolefin derivatives cannot be obtained or the yield is quite low by adopting water, DMF, DEC, toluene and the like as reaction solvents. Acetonitrile is the best reaction solvent in the method, and the reaction effect is much higher than that of other reaction solvents.
In a preferred embodiment, the iron (III) tetraarylporphyrin is iron tetraphenylporphyrin chloride (e.g., TPPFeCl) and/or iron (III) bis (tetraphenylporphyrin) ((TPPFe)2O). The nitration reaction of the tetraarylporphyrin iron (III) alkene has special catalytic activity, but other ferric salts and ferrous salts have no catalytic action on the reaction, and other tetraarylmetalloporphyrin compounds also have no catalytic activity, such as tetraarylmetalloporphyrin copper, tetraarylmetalloporphyrin cobalt and the like. FourthlyThe iron (III) arylporphyrin can also be a derivative of iron tetraphenylporphyrin chloride, and the benzene ring of the iron (III) arylporphyrin can contain substituent groups such as conventional amino, nitro, alkyl, alkoxy, halogen and the like.
In a more preferable embodiment, the usage amount of the tetraarylporphyrin iron chloride is 1 to 15% of the molar amount of the alkene compound. More preferably 3 to 5%. The dosage of the catalyst is increased or reduced, and the nitration reaction effect is obviously reduced.
The reaction mechanism for synthesizing α -unsaturated nitroolefin derivatives from olefin compounds according to the invention is as follows, with NH4I. TBHP and TPPFeCl acetonitrile solution are used as a reaction system, a alkene compound of a formula 1 is used as a substrate to synthesize α -unsaturated nitroolefin derivatives with a structure of a formula 2, and the reaction mechanism is specifically explained by taking the example as an example, firstly, TBHP is decomposed under a certain temperature condition to generate free radicals such as oxygen, hydroxyl and the like, quaternary ammonium cations are oxidized into nitrogen dioxide free radicals by the oxygen free radicals, the nitrogen dioxide free radicals carry out free radical addition reaction on the alkene compound under the transfer action of a TPPFeCl catalytic medium to obtain an active intermediate A, the intermediate A captures the hydroxyl free radicals to obtain an intermediate B, the intermediate B carries out cis-elimination to obtain the α -unsaturated nitroolefin derivatives with high E-type stereo selection, TPPFeCl mainly plays a role in transferring the free radicals in the reaction process, an unstable intermediate can be formed, but finally exists in TPPFeCl to play a catalytic role, and the reaction mechanism equation is as follows:
the present invention verifies the mechanism of the nitration reaction of an olefinic compound of the present invention by the following reaction, and explains the rationality of the reaction mechanism, taking the nitration reaction of styrene as an example. The addition of TEMPO or BHT radical scavengers during the nitration of styrene (reaction 1) was found to give virtually no reaction product, indicating that the reaction is involved in a radical reaction mechanism. Next, the intermediate 2-nitro-1-hydroxyethylbenzene (B) is used in NH4Mixed system of I and TBHP and TPPFeCl or NH without TPPFeCl4Reaction in mixed system of I and TBHP (trans)And 2) can obtain target products, which shows that the catalyst is hardly influenced to the elimination reaction. Meanwhile, the invention designs a step-by-step reaction experiment, wherein the first step of reaction is NH under the condition of no substrate olefin4Mixing I and TBHP in the condition of TPPFeCl catalyst (a) and in the condition of not using TPPFeCl catalyst (b) for 30 minutes, then adding TEMPO respectively, and detecting that TEMPO-nitro radical analogues are generated in the two reactions by GC-MS, which shows that the TPPFeCl catalyst does not catalyze the generation of free radicals (such as reactions 3(a) and (b)); the second reaction step is to divide the mixture containing TEMPO-nitro radical analog produced by the reaction (reaction 3(a)) into two parts, add the styrene substrate and TPPFeCl catalyst (d) into one part, add the styrene but not add the catalyst (c), heat and stir for 6 hours, as a result, the nitrostyrene 2a can be obtained in the reaction with the catalyst FeTPPCl added (reactions 4(c) and (d)), which shows that TPPFeCl catalyst mainly plays a role in catalyzing the reaction of nitro radical and styrene.
(1)
(2)
(3)
(4)
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the technical scheme of the invention firstly adopts a reaction system containing the tetra-aryl porphyrin iron (III), the halogenated ammonium salt and the tert-butyl hydroperoxide to carry out nitration reaction on the alkene compound, thereby realizing the one-pot reaction of the alkene compound to generate the alpha, beta-unsaturated nitroolefin.
2) The technical scheme of the invention adopts inorganic halogenated ammonium salt as a direct nitro source of the olefin compound for the first time, and has the advantages of low cost, safety, environmental protection and the like compared with the prior art containing nitrogen oxide, nitrite and organic nitro compounds.
3) The technical scheme of the invention utilizes the iron (III) tetraarylporphyrin as the nitration reaction catalytic reagent of the alkene compound for the first time, can realize the nitration reaction of various alkene compounds under mild conditions, and obtains higher yield and high stereoselectivity.
4) The technical scheme of the invention realizes the one-pot synthesis of the alpha, beta-unsaturated nitroolefin derivative, and the target product is easy to separate and purify, thereby simplifying the process steps and being beneficial to industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the target product of example 1;
FIG. 2 is a nuclear magnetic carbon spectrum of the target product of example 1;
FIG. 3 is a nuclear magnetic hydrogen spectrum of the target product of example 2;
FIG. 4 is a nuclear magnetic carbon spectrum of the target product of example 2;
FIG. 5 is a nuclear magnetic hydrogen spectrum of the target product of example 20;
fig. 6 is a nuclear magnetic carbon spectrum of the target product of example 20;
FIG. 7 is a nuclear magnetic hydrogen spectrum of the target product of example 22;
FIG. 8 is a nuclear magnetic carbon spectrum of the target product of example 22;
FIG. 9 is a nuclear magnetic hydrogen spectrum of the target product of example 27;
FIG. 10 is a nuclear magnetic carbon spectrum of the target product of example 27.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
All solvents, metalloporphyrins, oxidizing agents, ammonium salts and olefins used in the following examples were purchased from commercial sources.
All target compounds were characterized using GC-MS and NMR (1H and 13C) spectral data.
NMR model Bruker AV400MHz, relative displacement in ppm based on trimethylsilane relative displacement ppm ═ 0.
The relative displacement ppm of 1H and 13C of residual chloroform in the deuterated solvent were 7.26 and 77.00, respectively.
The GC-MS model is Shimadzu GC-MS (QP-2010), and the detector used is a FID detector.
All nitration reactions were carried out in sealed tubes (25mL) with a threaded end.
Unless otherwise stated, all liquid reagents were kept with molecular sieves added to remove water.
The yields of the target products in the following examples were calculated on the basis of the target product having a stereoselectivity of the formula E, and the stereoselectivity of the reaction was almost 100%.
Examples 1 to 21
Examples 1 to 21 were all reacted according to the following reaction equation:
the specific operation steps are as follows: olefin (0.5mmol), NH4I (1.5 eq, 0.75mmol, 108mg), TBHP (70% H)2O, 6.0 equiv.3.0 mmol, 384mg), TPPFeCl (3-5% of styrene molar mass) and acetonitrile (2mL) were added to a sealed tube. Adding acetonitrile first, then the olefin, NH4I and TPPFeCl, and finally TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated using a rotary evaporator and purified by column chromatography using Petroleum Ether (PE)/Ethyl Acetate (EA) as eluent and silica gel (200-mesh and 300-mesh sieves).
Example 1
Olefin (b):
and (3) target products:
(C8H7NO2)；
yellow solid 82% (61mg).1H NMR(400MHz,CDCl3)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)139.04,137.06,132.11,130.01,129.35,129.10.GC-MS(m/z):149.+.
Example 2
Olefin (b):
and (3) target products:
(C9H9NO2)。
77% yellow solid (63mg).1H NMR(400MHz,CDCl3)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)143.04,139.08,136.17,130.06,129.12,127.17,21.56.GC-MS(m/z):163.
Example 3
Olefin (b):
and (3) target products:
(C9H9NO3)；
yellow solid 73% (65mg).1H NMR(400MHz,CDCl3)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)162.93,139.00,135.03,131.14,122.54,114.98,55.51.GC-MS(m/z):179.
Example 4
Olefin (b):
and (3) target products:
(C12H15NO2)；
yield of single yellow solid 58% (60mg).1H NMR(400MHz,CDCl3)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).13CNMR(101MHz,CDCl3)156.08,138.98,136.32,129.03,127.17,126.35,35.05,30.94.GC-MS(m/z):203.
Example 5
Olefin (b):
and (3) target products:
(C9H8ClNO2)；
yellow solid 70% (69mg).1H NMR(400MHz,CDCl3)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)141.45,138.16,137.40,129.98,129.41(d,J＝3.1Hz),45.22.GC-MS(m/z):197.
Example 6
Olefin (b):
and (3) target products:
(C8H6FNO2)；
yellow solid 65% (54mg).1H NMR(400MHz,CDCl3)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)164.92,137.81,136.83,131.26(d,J＝8.9Hz),126.29(d,J＝3.6Hz),116.78(d,J＝22.2Hz)..GC-MS(m/z):167.
Example 7
Olefin (b):
and (3) target products:
(C8H6ClNO2)；
yellow solid 56% (51mg).1H NMR(400MHz,CDCl3)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)138.21,137.63,137.33,130.22,129.66,128.45.GC-MS(m/z):183.
Example 8
Olefin (b):
and (3) target products:
(C8H6BrNO2)；
yellow solid 58% (67mg).1H NMR(400MHz,CDCl3)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)137.75,137.47,132.74,130.36,128.94,126.78.GC-MS(m/z):228。
Example 9
Olefin (b):
and (3) target products:
(C10H9NO4)；
yellow solid 61% (63mg).1H NMR(400MHz,CDCl3)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)168.84,153.45,137.96,137.07,130.37 127.60,122.71,21.08.GC-MS(m/z):207。
Example 10
Olefin (b):
and (3) target products:
(C8H6ClNO2)；
53% yellow solid (49mg).1H NMR(400MHz,CDCl3)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)138.81,136.01,135.08,132.81,130.72,128.57,128.49,127.45.GC-MS(m/z):183.
Example 11
Olefin (b):
and (3) target products:
(C8H6BrNO2)；
47% yellow solid (54mg).1H NMR(400MHz,CDCl3)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)138.79,137.54,133.96,132.90(,130.29,128.43,128.05,126.29.GC-MS(m/z):228
Example 12
Olefin (b):
and (3) target products:
(C9H9NO2)；
yellow solid 55％(45mg).1H NMR(400MHz,CDCl3)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)139.20,139.17,136.86,132.96,129.93,129.65,129.20,126.31,21.18.GC-MS(m/z):163.
Example 13
Olefin (b):
and (3) target products:
(C8H6BrNO2)；
45% yellow solid (51mg).1H NMR(400MHz,CDCl3)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)137.94,137.22,134.73,131.95,131.55,130.75,127.57,123.28.GC-MS(m/z):228
Example 14
Olefin (b):
and (3) target products:
(C10H11NO2)；
yellow solid: 74% (82mg).1H NMR(400MHz,CDCl3)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)137.22,136.77,136.21,136.17,132.79,131.17,128.57,127.69,20.72,19.28.GC-MS(m/z):163.
Example 15
Olefin (b):
and (3) target products:
(C10H7NO2)；
44% yellow solid (43mg).1H NMR(400MHz,CDCl3)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)139.14,137.05,134.83,133.06,132.22,129.28,128.77,128.33,127.88,127.46,127.21,123.24.GC-MS(m/z):199.
Example 16
Olefin (b):
and (3) target products:
(C10H9NO2)；
34% yellow solid (30mg).1H NMR(400MHz,CDCl3)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)139.14,137.05,134.83,133.06,132.22,129.28,128.77,128.33,127.88,127.46,127.21,123.24.GC-MS(m/z):175.
Example 17
Olefin (b):
and (3) target products:
(C7H6N2O2)；
28% brown-yellow solid (21mg).1H NMR(400MHz,CDCl3)8.66(s,1H),7.95(dd,J＝38.3,13.1Hz,2H),7.78(t,J＝7.6Hz,1H),7.58–7.29(m,2H).13C NMR(101MHz,CDCl3)150.59,149.31,140.63,137.13,137.10,126.27,125.67.GC-MS(m/z):150.
Example 18
Olefin (b):
and (3) target products:
(C7H6N2O2)；
light grey solid: 22% (17mg).1H NMR(400MHz,CDCl3)8.74(s,2H),7.92(d,J＝13.7Hz,1H),7.65(d,J＝13.1Hz,1H),7.40(s,2H).13C NMR(101MHz,CDCl3)150.99,140.32,137.38,136.06,122.31.GC-MS(m/z):150.
Example 19
Olefin (b):
and (3) target products:
(C6H5NO2S)；
37% yellow solid (29mg).1H NMR(400MHz,CDCl3)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)135.31,134.61,133.72,132.06,131.59,128.85.GC-MS(m/z):155.
Example 20
Olefin (b):
and (3) target products:
(C8H15NO2)；
orange liquid: 22% (17mg).1H NMR(400MHz,CDCl3)7.33–7.23(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)142.71,139.41,77.00,31.27,28.60,28.30,27.53,22.32,13.84.GC-MS(m/z):157.
Example 21
Olefin (b):
and (3) target products:
30% yellow liquid (84mg).1H NMR(400MHz,CDCl3)7.24–7.18(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)142.81,139.52,31.87,29.59,29.58,29.54,29.41,29.30,29.22,29.05,28.42,27.68,22.65,14.08.GC-MS(m/z):241.
Examples 22 to 28
Examples 22 to 28 were all reacted according to the following reaction equation:
the specific operation steps are as follows: olefin (0.5mmol), NH4I (1.5 eq, 0.75mmol, 108mg), TBHP (70% H)2O, 6.0 equiv, 3.0mmol, 384mg), TPPFeCl (3-5%) and acetonitrile (2mL) were added to a sealed tube. Adding acetonitrile first, then the olefin, NH4I and TPPFeCl, and finally TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated using a rotary evaporator and purified by column chromatography using Petroleum Ether (PE)/Ethyl Acetate (EA) as eluent and silica gel (200-mesh and 300-mesh sieves).
Example 22
Olefin (b):
and (3) target products:
(C9H9NO2)；
49% yellow solid (40mg).1H NMR(400MHz,CDCl3)7.48–7.43(m,5H),7.31(d,J＝1.3Hz,1H),2.65(d,J＝1.3Hz,3H).13C NMR(101MHz,CDCl3)149.96,138.27,136.31,130.34,129.01,126.81,18.57.GC-MS(m/z):163.
Example 23
Olefin (b):
and (3) target products:
(C14H11NO2)；
yellow solid 42% (47mg).1H NMR(400MHz,CDCl3)7.49–7.31(m,7H),7.30–7.22(m,2H),7.22–7.16(m,2H).13C NMR(101MHz,CDCl3)150.37,136.96,135.45,134.30,130.82,129.21,128.82,128.79,128.70,128.40.GC-MS(m/z):225.
Example 24
Olefin (b):
and (3) target products:
(C14H11NO2)；
yellow solid 38% (31mg).1H NMR(400MHz,CDCl3)8.27(s,1H),7.57–7.50(m,3H),7.41–7.32(m,3H),7.27(dd,J＝13.5,5.6Hz,2H),7.13(d,J＝7.6Hz,2H).13C NMR(101MHz,CDCl3)149.59,134.79,131.34,131.16,130.72,130.52,130.02,129.87,129.19,128.68.GC-MS(m/z):225.
Example 25
Olefin (b):
and (3) target products:
(C9H9NO2)；
yellow solid 38% (31mg).1H NMR(400MHz,CDCl3)8.08(s,1H),7.48–7.40(m,5H),2.45(d,J＝0.8Hz,3H).13C NMR(101MHz,CDCl3)147.64,133.44,132.31,129.88,129.84,128.81,13.92.GC-MS(m/z):163.
Example 26
Olefin (b):
and (3) target products:
(C10H9NO2)；
38% (34mg) of yellow liquid.1H NMR(400MHz,CDCl3)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)147.87,136.36,131.54,131.21,130.12,130.09,127.87,127.28,27.87,22.32.GC-MS(m/z):175.
Example 27
Olefin (b):
and (3) target products:
(C6H9NO2)；
orange liquid 35% (22mg).1H NMR(400MHz,CDCl3)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)149.64,134.25,24.71,23.83,21.71,20.59.GC-MS(m/z):127。
Example 28
Olefin (b):
and (3) target products:
(C8H11NO2)；
orange liquid: 22% (17mg).1H NMR(400MHz,CDCl3)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).13CNMR(101MHz,CDCl3)151.52,135.18,128.62,127.64,27.04,26.66,26.29,25.63.GC-MS(m/z):153。
Comparative experimental group 1:
comparative examples 1 to 12 were all reacted according to the following reaction equation:
the specific operation steps are as follows: styrene (0.5mmol), NH4I (1.5 eq, 0.75mmol, 108mg), TBHP (70% H)2O, 6.0 equivalent, 3.0mmol, 384mg, catalyst (0-15% of styrene molar mass) and acetonitrile (2mL) were added to a sealed tube. Adding acetonitrile first, then the olefin, NH4I and catalyst, and finally adding TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated using a rotary evaporator and purified by column chromatography using Petroleum Ether (PE)/Ethyl Acetate (EA) as eluent and silica gel (200-mesh and 300-mesh sieves).
TABLE 1 yield of target product for different catalysts and amounts
As can be seen from Table 1, the reaction of iron tetraphenylporphyrin chloride with bis-iron tetraphenylporphyrin under standard reaction conditions gave good catalytic performance and a satisfactory yield, especially up to 82% of iron tetraphenylporphyrin chloride. And the target product can hardly be obtained by using other inorganic ferrous salts or ferric salts. In addition, the usage amount of the tetraphenylporphyrin ferric chloride catalyst is not suitable for excessive use, the catalyst is excessive, the product yield is obviously reduced, the target product cannot be obviously obtained without adding the catalyst, and only an oxidation product can be found.
Comparative experiment group 2:
comparative examples 13 to 21 were all reacted according to the following reaction equation:
the specific operation steps are as follows: styrene (0.5mmol), NH4X (1.5 eq, 0.75mmol), TBHP (70% H)2O, 6.0 equiv.3.0 mmol, 384mg), TPPFeCl (5% of styrene molar mass) and acetonitrile (2mL) were added to a sealed tube. Adding acetonitrile first, then the olefin, NH4I and catalyst, and finally adding TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated using a rotary evaporator and purified by column chromatography using Petroleum Ether (PE)/Ethyl Acetate (EA) as eluent and silica gel (200-mesh and 300-mesh sieves).
TABLE 2 yield of target product for different quaternary ammonium salts
As can be seen from table 2, the nitrosation reaction of styrene was achieved by using the halogen quaternary ammonium salt, and other quaternary ammonium salts and ammonia water were not used as the nitroxide source for the nitration reaction of styrene. It can also be seen from table 2 that ammonium iodide is in better yield than ammonium bromide and ammonium chloride, and is most suitable as a styrene nitrating agent.
Comparative experiment group 3:
comparative examples 22 to 31 were all reacted according to the following reaction equation:
the specific operation steps are as follows: styrene (0.5mmol), NH4I (1.5 equiv., 0.75mmol, 108mg), oxidant (6.0 equiv., 3.0mmol), TPPFeCl (5% of styrene molar mass) and acetonitrile (2mL) were added to a sealed tube. Adding acetonitrile first, then the olefin, NH4I and catalyst, and finally adding TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated using a rotary evaporator and purified by column chromatography using Petroleum Ether (PE)/Ethyl Acetate (EA) as eluent and silica gel (200-mesh and 300-mesh sieves).
TABLE 3 yields of target products for different oxidants
As can be seen from Table 3, only TBHP can oxidize ammonium iodide to realize nitrosation of styrene, and the reaction is not affected by atmosphere, and better yield can be obtained in air and under protective atmosphere. And other common oxidants such as hydrogen peroxide, potassium persulfate, di-tert-butyl peroxide and other inorganic organic peroxides are difficult to realize the nitration reaction of the styrene.
Comparative experiment group 4:
comparative examples 32 to 41 were all reacted according to the following reaction equation:
the specific operation steps are as follows: styrene (0.5mmol), NH4I (1-2 equivalent), oxidant (4-7 equivalent), TPPFeCl (5% of styrene molar weight) and BNitrile (2mL) was added to the sealed tube. Adding acetonitrile first, then the olefin, NH4I and catalyst, and finally adding TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated using a rotary evaporator and purified by column chromatography using Petroleum Ether (PE)/Ethyl Acetate (EA) as eluent and silica gel (200-mesh and 300-mesh sieves).
TABLE 4 different NH4Yield of target product corresponding to ratio of I to TBHP
From Table 4, NH can be seen4The reaction ratio of I and TBHP with the substrate styrene has a large influence on the yield of the product, NH4The molar ratio of I to styrene is more than 1.5, and TBHP and NH are simultaneously added4The ratio of I is more than 4 to achieve the best reaction effect, while the reaction in other ratio range can successfully obtain the target product, but the yield is limited.
Comparative experiment group 5:
comparative examples 42 to 51 were all reacted according to the following reaction equation:
the specific operation steps are as follows: olefin (0.5mmol), NH4I (1.5 eq, 0.75mmol, 108mg), TBHP (70% H)2O, 6.0 equiv, 3.0mmol, 384mg), TPPFeCl (3-5%) and solvent (0-2 mL) were added to a sealed tube. Adding acetonitrile first, then the olefin, NH4I and TPPFeCl, and finally TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated by a rotary evaporator, and the column was performed using Petroleum Ether (PE)/Ethyl Acetate (EA) as an eluent and silica gel (200-mesh and 300-mesh sieves)And (5) performing chromatographic purification.
TABLE 5 yields of target product for different solvents and amounts
Comparative experiment group 6:
comparative examples 52 to 59 were all reacted according to the following reaction equation:
the specific operation steps are as follows: olefin (0.5mmol, 50.2mg), NH4I (1.5 eq, 0.75mmol, 108mg), TBHP (70% H)2O, 6.0 equiv, 3.0mmol, 384mg), TPPFeCl (3-5%) and solvent (2mL) were added to a sealed tube. Adding acetonitrile first, then the olefin, NH4I and TPPFeCl, and finally TBHP. The reaction was stirred vigorously at 120 ℃ for 6 hours and monitored by TLC. After completion of the reaction, the mixture was cooled to room temperature, then filtered and washed with Ethyl Acetate (EA). Finally, the filtrate was concentrated using a rotary evaporator and purified by column chromatography using Petroleum Ether (PE)/Ethyl Acetate (EA) as eluent and silica gel (200-mesh and 300-mesh sieves).
TABLE 6 yields of target products corresponding to different solvents and reaction atmospheres
As can be seen from table 6, the target compound was obtained only in the presence of the ammonium salt, and the ambient atmosphere or solvent did not participate in providing the N source.
Claims (5)
1. A synthetic method of alpha, beta-unsaturated nitroolefin derivatives is characterized in that: the alkene compound with the structure shown in the formula 1 is subjected to one-pot reaction in a system containing tetraarylporphyrin iron (III), halogenated ammonium salt and tert-butyl hydroperoxide to generate the alpha, beta-unsaturated nitroolefin derivative with the structure shown in the formula 2;
wherein the content of the first and second substances,
R、R1and R2Independently selected from hydrogen, aromatic hydrocarbon group, aliphatic hydrocarbon group, heterocyclic group or substituted aliphatic hydrocarbon group, and R, R1And R2Not simultaneously being aromatic hydrocarbon or hydrogen; or, R and R2Is aliphatic cyclic hydrocarbon or aliphatic cyclic hydrocarbon containing aromatic ring;
the aromatic hydrocarbon group is phenyl, substituted phenyl or naphthyl;
the aliphatic hydrocarbon group is C1～C12An alkyl group;
the heterocyclic group is pyridyl or thienyl;
the aliphatic hydrocarbyl containing substituent is C containing substituent1～C12Wherein the substituent is halogen, hydroxyl, amino or nitro;
the aliphatic cyclic hydrocarbon group is C6～C8An aliphatic cyclic hydrocarbon group;
the aliphatic cyclic hydrocarbon group containing aromatic ring is C12～C14Aliphatic cycloalkyl groups containing a benzene ring;
the substituted phenyl has the structure of formula 3:
wherein the content of the first and second substances,
R3and R4Independently selected from hydrogen, alkyl, alkoxy, haloalkyl, halogen, acetoxy or alkenyl, and R3And R4Not hydrogen at the same time;
the ammonium halide salt is at least one of ammonium iodide, ammonium bromide and ammonium chloride;
the system comprises an acetonitrile and/or ethanol solvent;
the tetra-aryl porphyrin iron (III) is tetraphenyl porphyrin iron chloride and/or tetra-aryl diiron (III) porphyrin;
the molar ratio of the alkene compound, the halogenated ammonium salt and the tert-butyl hydroperoxide is 1 (1.5-2) to 6-8.
2. The method of synthesizing α, β -unsaturated nitroolefin derivatives according to claim 1, characterized in that: the substituted phenyl is p-methylphenyl, p-methoxyphenyl, p-isobutylphenyl, p-chloromethylphenyl, p-fluorophenyl, p-bromophenyl, p-chlorophenyl, p-acetoxy, m-methylphenyl, m-bromophenyl, o-chlorophenyl, o-bromophenyl, 2, 5-dimethylphenyl or 2-vinylphenyl.
3. The method for synthesizing the α, β -unsaturated nitroolefin derivative according to any one of claims 1 to 2, characterized in that: the reaction conditions are as follows: and under the air or protective atmosphere, the reaction temperature is 100-130 ℃, and the reaction time is 3-9 h.
4. The method of synthesizing α, β -unsaturated nitroolefin derivatives according to claim 1, characterized in that: the ammonium halide salt is ammonium iodide.
5. The method of synthesizing α, β -unsaturated nitroolefin derivatives according to claim 1, characterized in that: the dosage of the iron (III) tetraarylporphyrin is 1-15% of the molar weight of the alkene compound.
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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 |
-
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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 |
|---|
| NITRATION OF SUBSTITUTED STYRENES WITH NITRYL IODIDE;Wing-Wah Sy等;《Tetrahedron Letters》;19851231;第26卷(第9期);第1193-1196页 * |
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