CN108440474A - A kind of synthetic method of dihydropyran derivatives - Google Patents

A kind of synthetic method of dihydropyran derivatives Download PDF

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CN108440474A
CN108440474A CN201810614445.7A CN201810614445A CN108440474A CN 108440474 A CN108440474 A CN 108440474A CN 201810614445 A CN201810614445 A CN 201810614445A CN 108440474 A CN108440474 A CN 108440474A
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phenyl
dihydropyran
synthetic method
dihydropyran derivatives
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CN108440474B (en
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郭灿城
李慧
郭欣
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YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD
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YUANJIANG HUALONG CATALYTIC TECHNOLOGY CO LTD
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/18—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member containing only hydrogen and carbon atoms in addition to the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/20—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hydrogen atoms and substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D309/22—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

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Abstract

The invention discloses a kind of synthetic method of dihydropyran derivatives, this method be by aldehyde compound and 2 aryl propylene in the dimethyl sulfoxide solution system containing persulfate by one pot reaction to get dihydropyran derivatives；This method provides carbonyl by aldehyde compound for the first time, 2 aryl propylene provide acrylic and dimethyl sulfoxide (DMSO) provides methyl and builds dihydropyran ring jointly, the synthetic method is realized by one kettle way, and reaction condition is mild, is not necessarily to extra catalyst, the good, high income of selectivity, is conducive to industrialized production.

Description

A kind of synthetic method of dihydropyran derivatives
Technical field
The present invention relates to a kind of synthetic methods of dihydropyran derivatives, and in particular to one kind is by one kettle way by aldehydes The method that object builds dihydropyran jointly with 2- aryl propylene and dimethyl sulfoxide (DMSO) is closed, organic intermediate synthesis field is belonged to.
Background technology
Dihydropyran derivatives are a kind of important hexa-atomic Oxygenic heterocyclic compounds, and there is unique biology and drug to live Property, if Zanamivir is a kind of drug of resisiting influenza virus, Benesudon can be used as antibiotic usage, be a kind of heavy again The organic intermediate wanted can pass through water if 2- ethyoxyl -3,4- dihydropyran is relatively inexpensive synthesis of glutaraldehyde intermediate Solution obtains glutaraldehyde.Therefore, dihydropyran derivatives cause the concern of numerous organic chemists and drug scholar, and in the past Decades are studied most one of heterocyclic compounds.
Currently, there are many synthesis about dihydropyran to report, such as common Terminal Acetylenes hydrogen alkoxylate Cyclization； Oxo-Diels-Alder reaction synthesis；Michael additions/cyclisation cascade reaction synthesis；Knoevenagel /oxo-Diels- Alder cascade reactions synthesize.And most valuable method is using Diels-Alder reactions come synthesizing dihydro pyrans, it is such as classical Reaction be using conjugated diene and aldehyde radical under Louis (Lewis) acid catalysis, pass through Diels-Alder reaction Dihydropyran is obtained, as United States Patent (USP) (publication number US5162551) discloses benzaldehyde with conjugated diene in AlCl3Urge Change lower synthesis 2- phenyl -5,6- dihydro -2H- pyrans.Chinese patent (CN101143860A) disclose conjugated diene with it is anhydrous Formaldehyde synthesizes 5,6- dihydro-pyrans and its derivative under Louis acid catalysis effect by Diels-Alder reaction, Since Diels-Alder reaction is required to use lewis acid as catalyst, and need to carry out at high temperature, and Louis Acid can also cause olefinic polymerization simultaneously, cause side reaction more, it is difficult to control.Chinese patent (CN101481369A) discloses one Kind, as catalyst, 4,6 substitutions 3, -4- dihydros-is efficiently synthesized by aldehyde radical substituted cyclopropane alkanes compound by N-heterocyclic carbine The method of pyran-2-one derivative, the aldehyde radical substituted cyclopropane alkanes compound that this method uses are that one kind is difficult to the raw material obtained, Cost is higher.
Invention content
For it is existing structure dihydropyran ring method existing for defect, the purpose of the invention is to provide one kind by Aldehyde compound provides carbonyl, 2- aryl propylene provides acrylic and dimethyl sulfoxide (DMSO) provides methyl, common to build dihydro pyrrole Mutter the method for ring, which is realized by one kettle way, and reaction condition it is mild, without extra catalyst, selectivity is good, receives Rate is high, is conducive to industrialized production.
In order to achieve the above technical purposes, the present invention provides a kind of synthetic method of dihydropyran derivatives, this method Be by aldehyde compound and 2- aryl propylene in the dimethyl sulfoxide solution system containing persulfate by one pot reaction to get two Hydrogen pyran derivate；
The aldehyde compound has 1 structure of formula：
The 2- aryl propylene has 2 structure of formula：
The dihydropyran derivatives have 3 structure of formula：
Wherein,
R1For aryl, aromatic heterocyclic, alkyl or hydrogen；
Ar is aryl.
The range of choice of aldehyde compound is wider in technical scheme of the present invention, R1The selection of substituent group is to dihydropyran Structure influence be not obvious, R1The yield of dihydropyran when various common substituent groups is selected to be held in 60% or so.R1It is excellent It is selected as phenyl, substituted-phenyl, naphthalene, thienyl, furyl, pyridyl group or C1~C10Alkyl.R1When selected from substituted-phenyl, take The substituent group number for including for phenyl is 1~3, substituent group be selected from halogenic substituent, alkyl, trifluoromethyl, nitro, cyano or At least one of alkoxy；The position of substituent group does not have particular/special requirement, can be ortho position, the meta or para position of aldehyde radical, but a large amount of Experiment shows that bromine substituent can obtain ideal dihydropyran derivatives yield in aldehyde radical meta or para position, but bromine takes Dai Ji there is no dihydropyran product at aldehyde radical ortho position, and other substituent groups in addition to bromine can be obtained at aldehyde radical ortho position Ideal yield, this is unexpected.R1When selected from alkyl, alkyl can be straight chained alkyl, or branched alkyl, alkyl Carbon atom number is preferably no more than C5Short-chain alkyl.
The range of choice of 2- aryl propylene is confined to selection aryl substituent, aryl substituent in technical scheme of the present invention Big conjugated system is provided, can make the methyl on alkenyl that there is enough activity to participate in cyclisation.Aryl substituent cannot be arbitrarily by it Its substituent group is replaced, such as heteroaromatic, alkyl replacement aryl cannot obtain target product.Ar can be phenyl, substituted benzene Base or naphthalene.When Ar selects substituted-phenyl, the substituent group number that substituted-phenyl includes is 1~2, and the position of substituent group is best It is the contraposition of alkenyl.Substituted-phenyl to substituent group also have selection require, substituent group can be weak electron donating group, such as alkyl, Can be weak drawing electron group, such as halogen.And strong electron donating group hales electron group, such as nitro such as amido, alkoxy, it is difficult To obtain ideal yield.
The molar ratio of preferred scheme, the persulfate and aldehyde compound is 0.5~2:1, more preferably for 0.8~ 1.2:1。
Preferred scheme, the persulfate are mainly the persulfate of alkali metal containing and/or the persulfuric acid of alkali metal containing Hydrogen salt, most preferred persulfate include at least one of potassium peroxydisulfate, sodium peroxydisulfate, potassium hydrogen persulfate, hydrogen persulfate sodium.
The molar ratio of preferred scheme, aldehyde compound and 2- aryl propylene is 1:1~1.5.
Preferred scheme, a concentration of 0.1~0.5mol/L of the aldehyde compound in dimethyl sulfoxide solution system.Dimethyl Sulfoxide acts on of both primarily serving, and on the one hand plays the role of good solvent, is on the other hand used as reaction substrate, provides one A methyl is as a carbon atom in dihydropyran ring.
The condition of preferred scheme, the reaction is：Under protective atmosphere, at a temperature of 120~160 DEG C, reaction 18~ 30h.More preferably condition is：In a nitrogen atmosphere, at a temperature of 130~150 DEG C, 22~26h is reacted.
The present invention with benzaldehyde and dimethyl sulfoxide and 2- phenylpropens build jointly dihydropyran ring come to reaction mechanism into Row explanation.By consulting and refer to pertinent literature, a series of mechanism study experiment is devised, following reaction equation (1)~ (4) shown in.In order to prove whether the reaction passes through the reaction mechanism mechanism of reaction of free radical, reaction (1) is devised, under the conditions of standard reaction The 2,6-di-tert-butyl p-cresol (BHT) of 2.0 equivalents (opposite benzaldehyde) is added, reacts 8h, it as a result still can be suitable by GC-MS Profit detects the generation of dihydropyran derivatives target product, illustrates that reaction is not suppressed, reacts no experience one certainly By the reaction mechanism mechanism of reaction of base.In order to prove that the reaction whether there is reaction intermediate, by benzaldehyde and dimethyl sulfoxide and 2- phenyl third Alkene reacts 8 hours under the conditions of standard reaction, by being detected in GC-MS, in addition to detecting target product dihydropyran derivatives, The presence of compound B is also detected that simultaneously.In order to prove whether compound B is intermediate in dihydropyran building process, if Reaction (2) has been counted, 2- phenylpropens has been replaced by raw material of compound B, reacts, surprisingly find at the standard conditions, pass through GC- MS successfully is detected dihydropyran derivatives.In order to further understand fully the source of compound B, reaction (3) is further devised, it will 2- phenylpropens are directly reacted at the standard conditions with dimethyl sulfoxide, by being found that depositing for compound B in GC-MS detections , while having also obtained compound A.In order to obtain whether more accurately verification dimethyl sulfoxide participates in dihydropyran cyclisation, design Reaction (4) is replaced conventional dimethyl sulfoxide (DMSO) using the deuterated dimethyl sulfoxide of isotope labelling and is at the standard conditions reacted, at The presence of deuterium is detected to work(in dihydropyran product.Standard reaction condition：In N2Under, by benzaldehyde (0.5mmol), α-first Base styrene (0.6mmol) and DMSO (2mL), 140 DEG C, reaction is for 24 hours.
It reacts (1)：
It reacts (2):
It reacts (3)：
It reacts (4)：
According to above-mentioned experiment, the present invention is proposed builds dihydro pyrrole jointly by benzaldehyde and dimethyl sulfoxide and 2- phenylpropens It mutters the reasonable mechanism of ring：Shown in following reaction equation.First, using K2S2O8DMSO is activated, obtains that DMSO is made to be converted to diformazan Base sulphur cation C, while 2- phenylpropens discharge Hydrogen Proton, are converted to 2- phenylpropen anion D, and C and D are easy to idol Connection generates sulphur first ether compound A, and sulphur first ether compound A is in K2S2O8Under oxidation, removed by demethylation small Molecule methyl mercaptan compound obtains compound B, and compound B occurs ODA with benzaldehyde and reacts, and finally obtains target product.
Compared with the prior art, the advantageous effects that technical scheme of the present invention is brought：
1) present invention successfully builds dihydropyran by aldehyde compound, 2- aryl propylene and dimethyl sulfoxide (DMSO) for the first time and derives Object provides a kind of completely new synthesis thinking for the structure of pyranoid ring.
2) without using catalyst, relatively existing this Ah of Deere in the building-up process of dihydropyran derivatives of the invention Er De reacts, and avoids the use of louis catalyst, reduces the possibility of olefinic polymerization side reaction.
3) aldehyde compound, 2- aryl propylene and dimethyl are used in dihydropyran derivatives building-up process of the invention Sulfoxide is all existing conventional industrial chemicals as base stock, of low cost, is conducive to industrialized production.
4) one pot reaction is used in dihydropyran derivatives building-up process of the invention, and reaction condition is mild, operation Simply, meet demand of industrial production.
5) raw material availability is high in dihydropyran derivatives building-up process of the invention, and product yield is 60% or so.
6) wider to the accommodation of substrate raw material in dihydropyran derivatives building-up process of the invention, it can build more The dihydropyran derivatives of kind substituent group, and substituting group position is selectively strong, obtains disubstituted 3, the 6- dihydropyran of 2,4- Derivative.
Description of the drawings
【Fig. 1】For the mono-crystalline structures figure of compound 2- (4- nitrobenzophenones) -4- phenyl -3,6- dihydro -2H- pyrans.
Specific implementation mode
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention It encloses.
Unless otherwise stated, all reactions carry out in Schlenk test tubes.
All reaction raw materials solvents are obtained from commercial source, and are used without further purification.
Product separation uses silica gel chromatographic column, silica gel (- 400 mesh of 300 mesh of granularity).
1H NMR (400MHz), 13C NMR (100MHz) and 19F NMR (376MHz) detections use Bruker ADVANCE III spectrometers, with CDCl3For solvent, using TMS as internal standard, chemical shift is in terms of parts per million (ppm), with tetramethylsilane 0.0ppm is with reference to displacement.Multiplicity is explained using following abbreviation (or combinations thereof)：S=is unimodal, and d=is bimodal, and t=is triple Peak, q=quartets, m=multiplets, br=broad peaks.The unit of coupling constant J is hertz (Hz).Chemical shift indicates with ppm, With reference to deuterochloroform the center line of 77.0ppm triplets or with reference to deuterated DMSO 39.52ppm septets center line.
GC-MS is detected using GC-MS QP2010 equipment, and HRMS is measured using electron ionization (EI) method, mass-synchrometer Type is TOF, and EI is detected using Esquire 3000plus instruments.
1. condition optimizing is tested:
For building dihydropyran ring jointly by benzaldehyde and dimethyl sulfoxide and 2- phenylpropens, to oxidant and its use Multiple influence factors such as amount, reaction temperature, reaction dissolvent and additive are inquired into, to seek best reaction condition.
Specific reaction process：By benzaldehyde (0.5mmol), α-methylstyrene (0.6mmol), oxidant, additive (0.5mmol) and DMSO (2mL), in N2Under atmosphere, reaction is for 24 hours.
Reaction route is as follows：
Table 1：The yield of target product dihydropyran derivatives under the conditions of differential responses
1) selection of additive
As seen from Table 1, the use of additive has a great impact to reaction, and many experiments show such as project 1 in table 1 ~6 and 11, in benzaldehyde and dimethyl sulfoxide and 2- phenylpropens build the reaction process of dihydropyran ring, it has not been found that having Conducive to the benign additive for improving reaction efficiency, increasing yield, such as DABCO, DBU, K2CO3、Cs2CO3Equal alkaline matters conduct Additive cannot get target product dihydropyran substantially in use, apparent inhibition reaction, and add Et3N or NaOAc are only obtained Obtain the lower target product dihydropyran of yield.
3) selection of oxidant
The present invention has attempted the several frequently seen oxidant in this field, such as project 11 and 15~21 in table 1, oxidant such as over cure There is preferable reaction to imitate when being found only at persulfate as oxidant for hydrochlorate, organic peroxide, inorganic hydrogen peroxide etc. Fruit, as use tert-butyl hydroperoxide (TBHP), DTBP or hydrogen peroxide (H2O2) when being used as oxidant almost without obtaining target Therefore product selects persulfate as optimal oxidant.But the ammonium persulfate in persulfate is not appropriate for as this The oxidant of inventive method, it may be possible to which ammonium ion causes adverse effect to reaction.
4) selection of oxidizer
After determining that potassium peroxydisulfate and sodium peroxydisulfate etc. are best oxidant, the oxidant of different amounts is explored to reaction It influences.Such as project 11~14 in table 1.When the dosage of oxidant is between 0.5~1 equivalent, with the increase of oxidant content, The conversion ratio of raw material and the yield of product also increase therewith.And when the dosage of oxidant is more than 1 equivalent, yield declines bright It is aobvious.Therefore, the persulfate of 1 equivalent is the optimum amount of reaction.
5) selection of reaction temperature
Reaction temperature is to influence a key factor of chemical reaction process, and optimal reaction temperature, has studied in order to obtain The yield of the reaction at different temperatures, such as project 7~11 in table 1.In less than 120 DEG C temperature, it substantially cannot get target production Object, when temperature reaches 120 DEG C or more, reaction yield significantly improves, and increases the temperature to 140 DEG C, reaction yield reaches highest, and high In 140 DEG C, reaction side reaction is apparent.Therefore, 140 DEG C of optimum temperatures for the reaction.
6) selection of reaction dissolvent
Since DMSO is to be used as reaction substrate and solvent simultaneously during synthesizing dihydro pyrans, being other solvents can not replace It changes.DMSO may be used in the solvent of the present invention, while can also use the mixed solvent of DMSO and other solvents.
2, the range of choice of reaction substrate：
After the optimal synthesis condition of dihydropyran is determined, the substrate spectrum and applicability of reaction are probed into, it is real Result is tested as shown in table 2 and table 3.Table 2 is different aldehyde compounds and 2- phenylpropens and the reaction result of DMSO.From table 1 In as can be seen that aryl aldehyde, heteroaromatic aldehyde, formaldehyde etc. can have with 2- phenylpropens and DMSO under the reaction condition of standard Effect ground synthesizes corresponding dihydropyran ring structure, and the yield of target product is 60% or so.Also, many experiments, which show to contain, to be taken The benzaldehyde of Dai Ji, influence of the substituent group to reaction are not obvious, various substituted benzaldehydes can smoothly with 2- phenylpropens And DMSO builds dihydropyran.Sole exception to be 2- bromobenzaldehydes as substrate and 2- phenylpropens and DMSO can not build two Hydrogen pyrans, it may be possible to which the influence of bromine atom, mechanism remain unknown.
Table 3 is different 2- aryl propylene and benzaldehyde and the reaction result of DMSO, the experimental results showed that, 2 take on propylene Must be the aryl for having big conjugated system for base, other heteroaromatics, alkyl etc. cannot be satisfied requirement, big conjugated system Aryl is conducive to improve the activity of Alpha-Methyl.And the substituent group on aryl selection be also by what is required, cannot be push away electronics or Draw the stronger substituent group of electronic capability, such as nitro, alkoxy, and if push away electronics or draw electronic capability compared with substituent group, Such as halogen, alkyl are satisfied by requirement.
(1) reaction equation of different aldehyde compounds and 2- phenylpropens and DMSO：
Reaction process:
Weigh potassium persulfate (K2S2O8) (135mg, 0.5mmol) be placed in the Shi Lunke reaction tubes of 25ml, then thereto Dimethyl sulfoxide (DMSO, 2mL), aldehyde compound (0.5mmol) is added, 2- phenylpropens (71mg, 0.6mmol) are filled with nitrogen. At 140 DEG C, stir 24 hours.It after the completion of reaction, is cooled to room temperature, adds water (4mL), ethyl acetate extracts (3*5mL), anhydrous Na2SO4Dry, after solvent is fallen in vacuum distillation, silicagel column (200-300 mesh) separation obtains target product.
The different aldehyde compound of table 2. and 2- phenylpropens and DMSO reaction results
The structural characterization of part dihydropyran derivatives in table 2：
2,4-diphenyl-3,6-dihydro-2H-pyran:
1H NMR(400MHz,CDCl3) δ 7.44 (s, 2H), 7.41 (s, 3H), 7.37 (s, 1H), 7.34 (d, J=4.1Hz, 3H), 7.27 (d, J=12.0Hz, 1H), 6.22 (s, 1H), 4.72-4.64 (m, 1H), 4.64-4.49 (m, 2H), 2.71 (q, J =17.1Hz, 2H)
13C NMR(101MHz,CDCl3)δ142.39,140.04,134.41,128.54,128.51,127.71, 127.42,126.00, 124.80,122.25,76.02,66.89,34.94。
2-mesityl-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.41 (d, J=7.4Hz, 2H), 7.32 (t, J=7.4Hz, 2H), 7.23 (dd, J =16.5,9.4Hz, 1H), 6.85 (s, 2H), 6.26 (s, 1H), 5.01 (d, J=10.9Hz, 1H), 4.49 (q, J= 17.1Hz,2H),2.98– 2.86(m,1H),2.46(s,1H),2.41(s,6H),2.25(s,3H).
13C NMR(101MHz,CDCl3)δ139.94,136.85,136.17,134.74,134.30,130.11, 128.54,127.42, 124.68,122.62,73.86,66.82,31.26,20.87,20.83。
4-phenyl-2-(p-tolyl)-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.41 (d, J=7.3Hz, 2H), 7.33 (d, J=6.8Hz, 4H), 7.28-7.24 (m, 1H), 7.20 (d, J=7.4Hz, 2H), 6.21 (s, 1H), 4.64 (d, J=9.7Hz, 1H), 4.60-4.48 (m, 2H), 2.76–2.62(m, 2H),2.36(s,3H).
13C NMR(101MHz,CDCl3)δ140.10,139.42,137.36,134.46,129.19,128.49, 127.38,125.97, 124.79,122.28,75.88,66.85,34.90,21.21。
4-phenyl-2-(m-tolyl)-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.42 (d, J=7.2Hz, 2H), 7.34 (t, J=7.3Hz, 3H), 7.28 (s, 2H), 7.23 (d, J=7.6Hz, 1H), 7.13 (d, J=7.3Hz, 1H), 6.21 (s, 1H), 4.64 (d, J=9.9Hz, 1H), 4.53 (d, J=21.7Hz, 2H), 2.68 (dd, J=23.0,12.9Hz, 2H), 2.38 (s, 3H)
13C NMR(101MHz,CDCl3)δ142.33,140.08,138.22,134.48,128.50,128.45, 128.42,127.40, 126.66,124.81,123.09,122.23,76.10,66.92,34.97,21.54。
4-phenyl-2-(o-tolyl)-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.54 (d, J=7.4Hz, 1H), 7.42 (d, J=7.2Hz, 2H), 7.34 (t, J =7.3Hz, 2H), 7.30-7.24 (m, 2H), 7.19 (t, J=9.3Hz, 2H), 6.23 (s, 1H), 4.85 (d, J=9.9Hz, 1H),4.63–4.48 (m,2H),2.75–2.60(m,2H),2.38(s,3H).
13C NMR(101MHz,CDCl3)δ140.40,140.08,134.72,134.62,130.36,128.52, 127.49,127.41, 126.44,125.62,124.77,122.25,72.96,66.93,33.56,19.26。
2-(4-methoxyphenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.41 (d, J=7.5Hz, 2H), 7.35 (dd, J=16.2,7.8Hz, 4H), 7.29-7.24 (m, 1H), 6.92 (d, J=7.6Hz, 2H), 6.20 (s, 1H), 4.62 (d, J=9.7Hz, 1H), 4.53 (s, 2H),3.81(s,3H), 2.76–2.59(m,2H).
13C NMR(101MHz,CDCl3)δ159.17,140.11,134.58,134.47,128.50,127.39, 127.37,124.81, 122.29,113.91,75.63,66.87,55.35,34.81。
2-(4-chlorophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.41 (d, J=7.5Hz, 2H), 7.39-7.32 (m, 6H), 7.29 (d, J= 6.7Hz, 1H), 6.21 (s, 1H), 4.66 (t, J=6.3Hz, 1H), 4.63-4.47 (m, 2H), 2.65 (s, 2H)
13C NMR(101MHz,CDCl3)δ140.94,139.90,134.20,133.31,128.64,128.53, 127.49,127.35, 124.79,122.20,75.23,66.80,34.89。
2-(3-chlorophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.45 (s, 1H), 7.39 (d, J=7.2Hz, 2H), 7.34 (d, J=6.9Hz, 2H), 7.31-7.26 (m, 4H), 6.19 (s, 1H), 4.63 (t, J=6.7Hz, 1H), 4.53 (q, J=17.3Hz, 2H), 2.65 (s,2H).
13C NMR(101MHz,CDCl3)δ144.49,139.87,134.43,134.15,129.79,128.54, 127.75,127.51, 126.19,124.80,124.05,122.16,75.24,66.82,34.86。
2-(2-chlorophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.65 (d, J=7.2Hz, 1H), 7.41 (d, J=7.0Hz, 2H), 7.37-7.32 (m, 4H), 7.24 (dd, J=10.0,5.8Hz, 2H), 6.22 (s, 1H), 5.04 (d, J=10.4Hz, 1H), 4.67-4.51 (m, 2H), 2.85 (d, J=16.5Hz, 1H), 2.55-2.46 (m, 1H)
13C NMR(101MHz,CDCl3)δ140.23,139.92,134.46,131.63,129.29,128.59, 128.51,127.46, 127.37,127.13,124.83,121.99,72.82,66.97,33.45。
2-(4-fluorophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.40 (d, J=6.3Hz, 4H), 7.33 (t, J=7.2Hz, 2H), 7.29-7.23 (m, 1H), 7.06 (t, J=8.1Hz, 2H), 6.20 (s, 1H), 4.69-4.60 (m, 1H), 4.59-4.46 (m, 2H), 2.71- 2.58(m,2H). 13CNMR(101MHz,CDCl3)δ163.50,161.06,139.96,138.25,134.29,128.52, 128.02-127.25 (m), 124.80,122.22,115.33 (d, J=21.3Hz), 75.33,66.86,34.97.
2-(2-fluorophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.51 (t, J=7.2Hz, 1H), 7.33 (d, J=7.1Hz, 2H), 7.26 (d, J =6.8Hz, 2H), 7.21-7.16 (m, 2H), 7.11 (t, J=7.3Hz, 1H), 6.97 (t, J=9.1Hz, 1H), 6.13 (s, 1H), (dd, J=28.1,13.3Hz, 2H) of 4.91 (d, J=10.0Hz, 1H), 4.55-4.35 (m, 2H), 2.62
13C NMR(101MHz,CDCl3) δ 160.79,158.35,139.94,134.43,128.99 (d, J=8.2Hz), (128.52,127.47,127.24 d, J=4.3Hz), 124.85,124.51 (d, J=3.4Hz), 122.03,115.24 (d, J =21.6Hz), 69.90 (d, J=2.5Hz), 66.91,33.96.
2-(4-bromophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.51 (d, J=7.6Hz, 2H), 7.41 (d, J=7.6Hz, 2H), 7.34 (dd, J =12.5,7.0Hz, 4H), 7.28 (d, J=7.0Hz, 1H), 6.21 (s, 1H), 4.64 (t, J=6.7Hz, 1H), 4.59- 4.44(m,2H),2.66 (s,2H).
13C NMR(101MHz,CDCl3)δ141.47,139.90,134.18,131.58,128.52,127.67, 127.49,124.78, 122.19,121.42,75.25,66.78,34.85。
2-(3-bromophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.63 (s, 1H), 7.46-7.40 (m, 3H), 7.36 (t, J=7.9Hz, 3H), 7.30-7.26 (m, 2H), 6.22 (s, 1H), 4.65 (t, J=6.7Hz, 1H), 4.56 (q, J=17.3Hz, 2H), 2.67 (d, J =1.8Hz, 2H)13CNMR(101MHz,CDCl3)δ144.75,139.86,134.15,130.68,130.07,129.09, 128.53,127.50, 124.79,124.51,122.66,122.15,75.18,66.82,34.88。
4-(4-phenyl-3,6-dihydro-2H-pyran-2-yl)benzonitrile：
1H NMR(400MHz,CDCl3) δ 7.68 (d, J=7.7Hz, 2H), 7.56 (d, J=7.7Hz, 2H), 7.40 (d, J =7.7Hz, 2H), 7.35 (t, J=7.2Hz, 2H), 7.29 (d, J=6.7Hz, 1H), 6.22 (s, 1H), 4.73 (d, J= 9.5Hz, 1H), 4.56 (q, J=17.3Hz, 2H), 2.65 (t, J=11.4Hz, 2H)
13C NMR(101MHz,CDCl3)δ147.77,139.69,133.95,132.36,128.56,127.62, 126.50,124.77, 122.14,118.89,111.35,75.06,66.75,34.82。
2-(4-nitrophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 8.25 (d, J=7.7Hz, 2H), 7.62 (d, J=7.8Hz, 2H), 7.40 (d, J =7.7Hz, 2H), 7.35 (t, J=7.3Hz, 2H), 7.29 (d, J=6.7Hz, 1H), 6.23 (s, 1H), 4.79 (d, J= 9.7Hz, 1H), 4.58 (q, J=17.3Hz, 2H), 2.77-2.56 (m, 2H)
13C NMR(101MHz,CDCl3)δ149.78,147.35,139.66,133.91,128.58,127.64, 126.56,124.78, 123.76,122.15,74.89,66.76,34.89。
2-(3-nitrophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 8.34 (s, 1H), 8.17 (d, J=8.2Hz, 1H), 7.79 (d, J=7.6Hz, 1H), 7.56 (t, J=8.0Hz, 1H), 7.41 (d, J=7.6Hz, 2H), 7.36 (t, J=7.3Hz, 2H), 7.29 (d, J= 6.7Hz, 1H), 6.23 (s, 1H), 4.78 (d, J=9.9Hz, 1H), 4.59 (q, J=17.4Hz, 2H), 2.77-2.62 (m, 2H).
13C NMR(101MHz,CDCl3)δ148.41,144.63,139.70,133.92,131.96,129.44, 128.57,127.62, 124.81,122.57,122.17,121.03,74.72,66.82,34.82。
2-(2-nitrophenyl)-4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.94 (d, J=8.2Hz, 1H), 7.89 (d, J=7.8Hz, 1H), 7.68 (t, J =7.6Hz, 1H), 7.46 (d, J=7.8Hz, 1H), 7.41 (d, J=7.5Hz, 2H), 7.34 (t, J=7.2Hz, 2H), 7.28 (d, J=6.7Hz, 1H), 6.20 (s, 1H), 5.22 (d, J=10.2Hz, 1H), 4.54 (q, J=17.5Hz, 2H), 2.97 (d, J=16.4Hz, 1H), 2.66-2.54 (m, 1H)
13C NMR(101MHz,CDCl3)δ147.83,139.83,137.86,134.46,133.63,128.50, 128.25,128.15, 127.52,124.92,124.19,121.85,71.75,66.98,34.35。
4-phenyl-2-(4-(trifluoromethyl)phenyl)-3,6-dihydro-2H-pyran：
4.65-4.50 (m, 2H), 2.69 (t, J=13.9Hz, 2H)
13C NMR(101MHz,CDCl3)δ146.43,139.82,134.10,128.55,127.55,126.16, 125.47,125.43, 124.78,122.20,75.26,66.79,34.94。
2-(naphthalen-1-yl)-4-phenyl-3,6-dihydro-2H-pyran：
Colourless oil,HRMS(APCI):286.1355
1H NMR(400MHz,CDCl3) δ 8.13 (d, J=7.6Hz, 1H), 7.89 (d, J=7.2Hz, 1H), 7.82 (d, J =8.0Hz, 1H), 7.72 (d, J=7.0Hz, 1H), 7.53-7.47 (m, 3H), 7.43 (d, J=7.4Hz, 2H), 7.34 (t, J =7.3Hz, 2H), 7.25 (d, J=8.8Hz, 1H), 6.29 (s, 1H), 5.46-5.33 (m, 1H), 4.65 (s, 2H), 2.97- 2.81(m,2H).
13C NMR(101MHz,CDCl3)δ140.01,137.96,134.62,133.86,130.55,128.95, 128.53,128.20, 127.45,126.09,125.63,125.55,124.81,123.48,123.35,122.24,73.46, 66.93,34.20.
4-phenyl-2-(thiophen-2-yl)-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.42 (d, J=7.1Hz, 2H), 7.35 (t, J=7.1Hz, 2H), 7.30 (s, 1H), 7.26 (d, J=3.5Hz, 1H), 7.08 (s, 1H), 7.01 (s, 1H), 6.18 (s, 1H), 4.97 (d, J=9.2Hz, 1H), 4.54 (s, 2H), 2.83 (dd, J=21.5,12.8Hz, 2H)
13C NMR(101MHz,CDCl3)δ145.34,139.95,133.92,128.54,127.51,126.62, 124.94,124.87, 124.08,122.22,71.82,66.55,34.66。
4-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.38 (d, J=7.7Hz, 2H), 7.32 (t, J=7.4Hz, 2H), 7.24 (s, 1H), 6.11 (s, 1H), 4.31 (s, 2H), 3.92 (t, J=5.3Hz, 2H), 2.51 (s, 2H)
13C NMR(101MHz,CDCl3)δ140.30,134.17,128.44,127.30,124.71,122.45,65.90, 64.50,27.23。
(2) reaction equation of different propene compounds and benzaldehyde and DMSO：
Reaction process：
Weigh potassium persulfate (K2S2O8) (135mg, 0.5mmol) be placed in the Shi Lunke reaction tubes of 25ml, then thereto Dimethyl sulfoxide (DMSO, 2ml), benzaldehyde (54mg, 0.5mmol) is added, propene compound (0.6mmol) is filled with nitrogen. At 140 DEG C, stir 24 hours.It after the completion of reaction, is cooled to room temperature, adds water (4ml), ethyl acetate extracts (3*5ml), anhydrous Na2SO4Dry, after solvent is fallen in vacuum distillation, silicagel column (200-300 mesh) separation obtains target product dihydropyrane compound.
The different propene compound of table 3. and benzaldehyde and the reaction result of DMSO
The structural characterization of part dihydropyran derivatives in table 3：
4-(4-methylphenyl)-2-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.46 (d, J=7.3Hz, 2H), 7.40 (t, J=7.3Hz, 2H), 7.33 (d, J =7.5 Hz, 3H), 7.17 (d, J=7.6Hz, 2H), 6.19 (s, 1H), 4.73-4.65 (m, 1H), 4.62-4.49 (m, 2H), 2.76– 2.63(m,2H),2.36(s,3H).
13C NMR(101MHz,CDCl3)δ142.49,137.22,137.16,134.22,129.18,128.51, 127.66,126.01, 124.66,121.36,76.04,66.88,34.97,21.12。
4-(naphthalen-2-yl)-2-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.86-7.78 (m, 4H), 7.66 (d, J=8.5Hz, 1H), 7.54-7.41 (m, 6H), 7.36 (d, J=6.7Hz, 1H), 6.41 (s, 1H), 4.75 (s, 1H), 4.69-4.57 (m, 2H), 2.92-2.73 (m, 2H).
13C NMR(101MHz,CDCl3)δ142.46,137.05,134.12,133.48,132.78,128.60, 128.18,128.06, 127.78,127.60,126.31,126.05,125.91,123.29,123.17,122.84,76.12, 67.01,35.00。
4-(4-chlorophenyl)-2-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.44 (d, J=7.4Hz, 2H), 7.39 (t, J=7.3Hz, 2H), 7.32 (q, J =7.9 Hz, 5H), 6.21 (s, 1H), 4.66 (d, J=9.5Hz, 1H), 4.63-4.46 (m, 2H), 2.74-2.58 (m, 2H)
13C NMR(101MHz,CDCl3)δ142.2,138.46,133.43,133.12,128.61,128.54,127.76, 126.06, 125.95,122.81,75.92,66.79,34.86。
4-(4-fluorophenyl)-2-phenyl-3,6-dihydro-2H-pyran：
1H NMR(400MHz,CDCl3) δ 7.44 (d, J=7.2Hz, 2H), 7.39 (t, J=7.3Hz, 2H), 7.32 (q, J =7.9 Hz, 5H), 6.21 (s, 1H), 4.66 (d, J=9.6Hz, 1H), 4.60-4.49 (m, 2H), 2.75-2.59 (m, 2H)
13C NMR(101MHz,CDCl3)δ142.21,138.46,133.43,133.12,128.61,128.55, 127.76,126.06, 125.95,122.81,75.92,66.79,34.86。

Claims (9)

1. a kind of synthetic method of dihydropyran derivatives, it is characterised in that：Aldehyde compound is with 2- aryl propylene containing over cure By one pot reaction to get dihydropyran derivatives in the dimethyl sulfoxide solution system of hydrochlorate；
The aldehyde compound has 1 structure of formula：
The 2- aryl propylene has 2 structure of formula：
The dihydropyran derivatives have 3 structure of formula：
Wherein,
R1For aryl, aromatic heterocyclic, alkyl or hydrogen；
Ar is aryl.
2. a kind of synthetic method of dihydropyran derivatives according to claim 1, it is characterised in that：
R1For phenyl, substituted-phenyl, naphthalene, thienyl, furyl, pyridyl group or C1~C10Alkyl；
Ar is phenyl, substituted-phenyl or naphthalene.
3. a kind of synthetic method of dihydropyran derivatives according to claim 2, it is characterised in that：
R1When selected from substituted-phenyl, the substituent group number that substituted-phenyl includes is 1~3, and the substituent group replaces selected from halogen At least one of base, alkyl, trifluoromethyl, nitro, cyano or alkoxy；
When Ar is selected from substituted-phenyl, the substituent group number that substituted-phenyl includes is 1~2, and substituent group is selected from halogenic substituent, alkane At least one of base.
4. a kind of synthetic method of dihydropyran derivatives according to claim 1, it is characterised in that：The persulfate Molar ratio with aldehyde compound is 0.5~2:1.
5. a kind of synthetic method of dihydropyran derivatives according to claim 4, it is characterised in that：The persulfate Including at least one of potassium peroxydisulfate, sodium peroxydisulfate, potassium hydrogen persulfate, hydrogen persulfate sodium.
6. a kind of synthetic method of dihydropyran derivatives according to claim 1, it is characterised in that：Aldehyde compound with The molar ratio of 2- aryl propylene is 1:1~1.5.
7. a kind of synthetic method of dihydropyran derivatives according to claim 1, it is characterised in that：Aldehyde compound exists A concentration of 0.1~0.5mol/L in dimethyl sulfoxide solution system.
8. according to a kind of synthetic method of dihydropyran derivatives of claim 1~7 any one of them, it is characterised in that：Institute The condition for stating reaction is：Under protective atmosphere, at a temperature of 120~160 DEG C, 18~30h is reacted.
9. a kind of synthetic method of dihydropyran derivatives according to claim 8, it is characterised in that：The item of the reaction Part is：In a nitrogen atmosphere, at a temperature of 130~150 DEG C, 22~26h is reacted.
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