阅读说明：本技术 一种合成4-乙烯基异噁唑衍生物的方法 (Method for synthesizing 4-vinyl isoxazole derivative ) 是由 李建晓 林梓东 何丹 林智聪 江焕峰 于 2021-07-23 设计创作，主要内容包括：本发明属于医药和有机化工的技术领域,公开了一种合成4-乙烯基异噁唑衍生物的方法。所述方法：空气氛围下,在溶剂中将O-甲基炔酮肟醚与乙烯基苯醚类化合物在氧化剂、铵盐和钯催化剂的作用下进行反应,后续处理,获得4-乙烯基异恶唑衍衍生物。所述4-乙烯基异恶唑衍生物的结构为式I。本发明成功合成4-乙烯基异恶唑衍生物,本发明的方法原料易得,反应条件温和,底物普适性大,官能团兼容性好,为具有潜在生物和药理活性的异噁唑衍生物的高效合成提供重要的技术支持。(The invention belongs to the technical field of medicines and organic chemical industry, and discloses a method for synthesizing a 4-vinyl isoxazole derivative. The method comprises the following steps: in the air atmosphere, O-methyl alkynone oxime ether and vinyl phenyl ether compounds react in a solvent under the action of an oxidant, ammonium salt and a palladium catalyst, and the 4-vinyl isoxazole derivative is obtained after subsequent treatment. The structure of the 4-vinyl isoxazole derivative is shown in a formula I. The method successfully synthesizes the 4-vinyl isoxazole derivative, has the advantages of easily obtained raw materials, mild reaction conditions, large substrate universality and good functional group compatibility, and provides important technical support for the high-efficiency synthesis of the isoxazole derivative with potential biological and pharmacological activities.)

1. a method for synthesizing 4-vinyl isoxazole derivatives is characterized by comprising the following steps: the method comprises the following steps:

in the air atmosphere, reacting O-methyl alkynone oxime ether with a vinyl phenyl ether compound in a solvent under the action of a palladium catalyst, an ammonium salt and an oxidant, and performing subsequent treatment to obtain a 4-vinyl isoxazole derivative;

the structure of the O-methyl oxime ether is

Wherein R is¹Is substituted phenyl, unsubstituted phenyl, substituted alkyl or unsubstituted alkyl;

R²is substituted phenyl, unsubstituted phenyl, heteroaryl, substituted alkyl, unsubstituted alkyl;

R¹and R²Wherein, the substituted phenyl is that hydrogen on the benzene ring is substituted by alkyl, halogen, alkoxy and trifluoromethyl;

R¹and R²Wherein each of said substituted alkyl groups is a hydrogen on the alkyl group substituted with a halogen; r¹And R²Wherein each of the alkyl groups is an alkyl group having 2 to 6 carbon atoms;

the vinyl phenyl ether compound has the structure of

The R is³Is H, 4-methyl, 2-methyl, 4-ethyl, 4-tert-butyl, 4-chloro, 4-bromo, 4-fluoro, 4-methoxy;

the solvent is an organic solvent or an ionic liquid.

2. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 1, characterized in that:

the R is¹Specifically phenyl, p-methoxyphenyl, p-ethoxyphenyl, p-trifluoromethylphenyl and p-fluoroPhenyl, p-bromophenyl, p-chlorophenyl, o-bromophenyl, m-chlorophenyl, m-bromophenyl, p-methylphenyl, p-ethylphenyl, p-tert-butylphenyl, tert-butyl, n-butyl, cyclopentyl, cyclohexyl, 4-chlorobutyl, styryl, p-trifluoromethylthiophenyl;

the R is²Is phenyl, thienyl, furyl, p-ethoxyphenyl, p-trifluoromethylphenyl, p-fluorophenyl, p-bromophenyl, p-chlorophenyl, o-bromophenyl, m-chlorophenyl, m-bromophenyl, p-methylphenyl, p-ethylphenyl, p-tert-butylphenyl, tert-butyl, methyl, ethyl, propyl, isopropyl, cyclopentyl, cyclohexyl, n-butyl, 4-chlorobutyl, styryl, p-trifluoromethylthiophenyl;

the ionic liquid is imidazole type ionic liquid and comprises more than one of 1-propylamino-3-methylimidazole chlorine salt, 1-propylamino-3-methylimidazole tetrafluoroborate, 1-propylamino-3-methylimidazole hexafluorophosphate and 1-propylamino-3-methylimidazole bromine salt;

the organic solvent is more than one of N, N-dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, toluene, 1, 4-dioxane, acetonitrile, tetrahydrofuran, m-xylene, ethylene glycol monomethyl ether, polyethylene glycol and tetrahydropyrrole.

3. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 2, characterized in that: the organic solvent is more than one of N, N-dimethylformamide, ethylene glycol dimethyl ether, toluene, 1, 4-dioxane, tetrahydrofuran, m-xylene, ethylene glycol monomethyl ether and tetrahydropyrrole.

4. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 1, characterized in that:

the oxidant is more than one of 1, 2-naphthoquinone, 1, 4-naphthoquinone, anthraquinone, benzoquinone, tetrachloro-p-benzoquinone, dichlorodicyano benzoquinone, oxygen, silver oxide, copper chloride, copper bromide, ketone iodide, iodobenzene acetate, hydrogen peroxide, hypohalite and iodine;

the catalyst is a palladium catalyst and comprises more than one of palladium chloride, dichlorobis (triphenylphosphine) palladium, palladium trifluoroacetate, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, bis (allyl) palladium dichloride, palladium acetate, palladium bromide, palladium iodide and palladium dibenzylideneacetone.

5. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 4, characterized in that:

the oxidant is 1, 2-naphthoquinone;

the catalyst is palladium acetate.

6. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 1, characterized in that: the ammonium salt is a substance containing ammonium ions and comprises more than one of ammonium chloride, ammonium bromide, ammonium iodide, ammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetraethylammonium chloride and tetraethylammonium bromide.

7. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 6, characterized in that:

the ammonium salt is tetrabutylammonium bromide.

8. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 1, characterized in that: the reaction conditions are as follows: the reaction temperature is 60-120 ℃; the reaction time is 4-16 h;

the molar ratio of the O-methyl alkynone oxime ether to the vinyl phenyl ether compound is 1: 1-3;

the molar ratio of the catalyst to the O-methyl alkynyl ketone oxime ether is 0.001-0.2: 1;

the molar ratio of the oxidant to the O-methyl alkynyl ketone oxime ether is (0.5-2) to 1; the molar ratio of the ammonium salt to the O-methyl alkynyl ketone oxime ether is (2-3) to 1;

the subsequent treatment refers to cooling, extracting, concentrating and purifying by thin layer chromatography of the product after the reaction is finished.

9. The method for synthesizing 4-vinyl isoxazole derivatives according to claim 8, characterized in that:

the reaction temperature is 75-90 ℃;

the eluent of the thin layer chromatography is a mixed solvent of petroleum ether and ethyl acetate; the volume ratio of the petroleum ether to the ethyl acetate is (4-500) to 1.

10. A 4-vinyl isoxazole derivative synthesized by the method according to any one of claims 1 to 9, characterized in that:

the structure is as follows

Wherein R is¹Is substituted phenyl, unsubstituted phenyl, substituted alkyl or unsubstituted alkyl;

R²is substituted phenyl, unsubstituted phenyl, heteroaryl, substituted alkyl, unsubstituted alkyl;

R¹and R²Wherein, the substituted phenyl is that hydrogen on the benzene ring is substituted by alkyl, halogen, alkoxy and trifluoromethyl;

R¹and R²Wherein each of said substituted alkyl groups is a hydrogen on the alkyl group substituted with a halogen; r¹And R²Wherein the alkyl groups are each an alkyl group having 2 to 6 carbon atoms.

Technical Field

The invention relates to the technical field of medicine and organic chemical synthesis, in particular to a method for synthesizing a 4-vinyl isoxazole derivative.

Background

The isoxazole compound is a heterocyclic compound with high application value, is an important core skeleton of a plurality of natural products and drug molecules, and has obvious functions of resisting inflammation, resisting cancer and the like. The multi-substituted isoxazoles exhibit more potent biological and pharmacological activity. Some molecules containing isoxazole rings have antagonistic effects on sphingosine-1-phosphate and are expected to be therapeutic drugs for rheumatoid arthritis (s.h.waterson, j.guo, s.h.spergel, c.m.langevine, r.v.moquin, d.r.shen, m.yarde, m.e.cvijic, d.banas, r.liu, s.j.suchard, k.gilooly, t.taylor, s.rex-rara, d.j.shuster, k.w.mcirore, g.cornelius, c.d' ariezo, a.marino, p.balimane, b.warack, l.salter-Cid, m.nnnon, j.c.barrrish, p.h.carenter, w.m.pijiemn, j.31, m.r, k.j.m.m.m.m.m.m.m.m.m.r.m.m.r.m.m.h.r.r.r.r.r.r.r.r.r.r.j.j.j.j.j.j.j.j.j.j.m.m.j.m.j.m.j.j.m.j.j.j.m.j.j.m.j.j.m.j.j.m.m.j.m.m.j.j.j.j.j.j.j.j.m.m.j.j.j.m.j.j.j.j.j.j.j.j.j.j.m.j.j.j.m.m.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.m.j.j.j.j.j.j.j.j.j.j.j.j.m.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.m.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.m.j.j.j.m.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j.j; research shows that the lichenin and derivatives thereof have anticancer effect (A.Pyrczak-Felczykowska, R.Narlawar, A.Pawlik, B.Guzow-Krzeminska, D.Artymiuk, A.Hac, K.Rys, L.M.Rendina, T.A.Reekie, A.Herman-Antosiewicz, and M.Kassiou, J.Nat.prod., 2019, 82, 1768); the isoxazole-containing alkaloids inhibit cholinesterase and are therefore useful in the treatment of Psychotria psychosis (L.C.Klein-J nior, S.Cretton, Y.V.Heyden, A.L.Gasper, S.Nejad-Ebrahimi, P.Christen, and A.T.Henriques, J.Nat.prod., 2020, 83, 852).

In recent years, palladium-catalyzed cyclization of ketoxime ethers has been the method of preparing isoxazoles containing a terminal olefin. For example, Wuwanqing et al reported in 2019 that palladium-catalyzed reaction between an oxime ether of an alkynone and an allyl halide allows for the efficient synthesis of isoxazoles containing terminal olefins. However, this method has limitations, only the use of relatively active allyl halides, and no access to 4-vinylisoxazole and its derivatives (c.li, j.li, f.zhou, c.li, and w.wu, j.org.chem., 2019, 84, 11958); chen et al prepared a 4-vinylisoxazole using β -heteroatom elimination, however, they were harsh in reaction conditions, complex in procedure, and low in yield (z.she, d.niu, l.chen, m.a.gunawan, x.shanja, w.h.hersh, and y.chen, j.org.chem., 2012, 77, 3627).

There has been no report of synthesizing 4-vinyl isoxazole derivatives using vinyl phenyl ether as a reaction raw material. Therefore, the development of a synthetic method which is simple to operate and easy to obtain raw materials and uses vinyl phenyl ether and derivatives thereof as substrates to construct 4-vinyl isoxazole derivatives with diversified structures is still a challenging research subject.

Disclosure of Invention

In order to overcome the disadvantages and shortcomings of the prior art, the present invention aims to provide a method for synthesizing a 4-vinyl isoxazole derivative. The invention takes substituted vinyl phenyl ether as one of substrates, and O-methyl alkynone oxime ether is reacted with the substituted vinyl phenyl ether to obtain the 4-vinyl isoxazole with diversified structures. The method has the advantages of easily available raw materials, mild reaction conditions and wide substrate range, and provides important technical support for the efficient synthesis of isoxazole derivatives with potential biological and pharmacological activities.

The purpose of the invention is realized by the following technical scheme:

a method for synthesizing a 4-vinylisoxazole derivative comprising the steps of:

in the air atmosphere, O-methyl alkynone oxime ether and vinyl phenyl ether compounds react in a solvent under the action of a palladium catalyst, ammonium salt and an oxidant, and the 4-vinyl isoxazole derivative is obtained after subsequent treatment.

The O-methyl alkynone oxime ether has the structure

Wherein R is¹Is substituted phenyl, unsubstituted phenyl, substituted alkyl or unsubstituted alkyl;

R²substituted phenyl, unsubstituted phenyl, heteroaryl, substituted alkyl, unsubstituted alkyl.

R¹And R²Wherein, the substituted phenyl is that hydrogen on the benzene ring is substituted by alkyl, halogen, alkoxy and trifluoromethyl;

R¹and R²Wherein each of said substituted alkyl groups is a hydrogen on the alkyl group substituted with a halogen;

R¹and R²Wherein each of the alkyl groups is 2 to 6Alkyl of carbon atoms.

The R is¹Specifically, the phenyl group is a phenyl group, a p-methoxyphenyl group, a p-ethoxyphenyl group, a p-trifluoromethylphenyl group, a p-fluorophenyl group, a p-bromophenyl group, a p-chlorophenyl group, an o-bromophenyl group, an m-chlorophenyl group, an m-bromophenyl group, a p-methylphenyl group, a p-ethylphenyl group, a p-tert-butylphenyl group, a tert-butyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, a 4-chlorobutyl group, a styryl group, a p-trifluoromethylthiophenyl group or the like.

The R is²Is phenyl, thienyl, furyl, p-ethoxyphenyl, p-trifluoromethylphenyl, p-fluorophenyl, p-bromophenyl, p-chlorophenyl, o-bromophenyl, m-chlorophenyl, m-bromophenyl, p-methylphenyl, p-ethylphenyl, p-tert-butylphenyl, tert-butyl, methyl, ethyl, propyl, isopropyl, cyclopentyl, cyclohexyl, n-butyl, 4-chlorobutyl, styryl, p-trifluoromethylthiophenyl, etc.

The vinyl phenyl ether compound has the structure of

The R is³H, 4-methyl, 2-methyl, 4-ethyl, 4-tert-butyl, 4-chloro, 4-bromo, 4-fluoro, 4-methoxy, and the like.

The oxidant is 1, 2-naphthoquinone, 1, 4-naphthoquinone, anthraquinone, benzoquinone, tetrachloro-p-benzoquinone, dichlorodicyano benzoquinone, oxygen, silver oxide, copper chloride, copper bromide, ketone iodide, iodobenzene acetate, hydrogen peroxide, hypohalite, iodine, etc. The oxidizing agent is preferably 1, 2-naphthoquinone.

The catalyst is a palladium catalyst such as palladium chloride, dichlorobis (triphenylphosphine) palladium, palladium trifluoroacetate, dichlorobis (acetonitrile) palladium, dichlorobis (benzonitrile) palladium, bis (allyl) palladium dichloride (i.e., allyl palladium chloride dimer), palladium acetate, palladium bromide, palladium iodide, palladium dibenzylideneacetone, and the like. The palladium catalyst is preferably palladium acetate.

The ammonium salt is a substance containing an ammonium ion such as ammonium chloride, ammonium bromide, ammonium iodide, ammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetraethylammonium bromide, and the like. The ammonium salt is preferably tetrabutylammonium bromide.

The reaction conditions are as follows: the reaction temperature is 60-120 ℃, and preferably 75-90 ℃; the reaction time is 4-16 h.

The reaction is carried out in an air atmosphere.

The solvent is an organic solvent or an ionic liquid, and is preferably an organic solvent.

The ionic liquid is imidazole type ionic liquid and comprises more than one of 1-propylamino-3-methylimidazole chlorine salt, 1-propylamino-3-methylimidazole tetrafluoroborate, 1-propylamino-3-methylimidazole hexafluorophosphate and 1-propylamino-3-methylimidazole bromine salt.

The organic solvent is N, N-dimethylformamide, dimethyl sulfoxide, ethylene glycol dimethyl ether, toluene, 1, 4-dioxane, acetonitrile, tetrahydrofuran, m-xylene, ethylene glycol monomethyl ether, polyethylene glycol and tetrahydropyrrole. The organic solvent is preferably ethylene glycol dimethyl ether.

The molar ratio of the O-methyl alkynone oxime ether to the substituted vinyl phenyl ether is 1: 1-3.

The molar ratio of the catalyst to the O-methyl alkynyl ketone oxime ether is 0.001-0.2: 1.

The molar ratio of the oxidant to the O-methyl alkynyl ketone oxime ether is (0.5-2) to 1; the molar ratio of the ammonium salt to the O-methyl alkynyl ketone oxime ether is (2-3) to 1.

The subsequent treatment refers to cooling, extracting, concentrating and purifying by thin layer chromatography of the product after the reaction is finished.

The eluent of the thin layer chromatography is a mixed solvent of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is (4-500) to 1.

The structure of the 4-alkenyl isoxazole is as follows:

the reaction equation of the synthesis method of the method is as follows:

the principle of the invention is that in the air atmosphere, palladium is used as a catalyst, O-methyl alkynone oxime ether and substituted vinyl phenyl ether are used as raw materials, and the 4-vinyl isoxazole derivative is synthesized through cyclization/tandem reaction catalyzed by bivalent palladium. All raw materials in the method are cheap and easy to obtain, the method is simple, the operation is safe, the reaction condition is mild, and therefore, the method has potential application value.

Compared with the prior art, the invention has the following advantages and effects:

the method successfully synthesizes the 4-vinyl isoxazole derivative, has the advantages of easily available raw materials, mild reaction conditions, wide substrate range and good functional group compatibility, and provides important technical support for the high-efficiency synthesis of the isoxazole derivative with potential biological and pharmacological activities.

Drawings

FIG. 1 is a hydrogen spectrum of the product obtained in example 17;

FIG. 2 is a carbon spectrum of the product obtained in example 17;

FIG. 3 is a hydrogen spectrum of the product obtained in example 18;

FIG. 4 is a carbon spectrum of the product obtained in example 18;

FIG. 5 is a hydrogen spectrum of the product obtained in example 19;

FIG. 6 is a carbon spectrum of the product obtained in example 19;

FIG. 7 is a hydrogen spectrum of the product obtained in example 20;

FIG. 8 is a carbon spectrum of the product obtained in example 20;

FIG. 9 is a hydrogen spectrum of the product obtained in example 21;

FIG. 10 is the carbon spectrum of the product obtained in example 21;

FIG. 11 is a hydrogen spectrum of the product obtained in example 22;

FIG. 12 is a carbon spectrum of the product obtained in example 22;

FIG. 13 is a hydrogen spectrum of the product obtained in example 23;

FIG. 14 is a carbon spectrum diagram of the product obtained in example 23;

FIG. 15 is a hydrogen spectrum of the product obtained in example 24;

FIG. 16 is a carbon spectrum of the product obtained in example 24.

Detailed Description

The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.

Example 1

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 16 percent.

Example 2

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 4-naphthoquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, the crude product is separated and purified by thin layer chromatography to obtain a target product, and the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 20 percent.

Example 3

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of anthraquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, and the crude products are separated and purified by thin layer chromatography to obtain target products, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 21 percent.

Example 4

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 32 percent.

Example 5

In the air atmosphere, 10 percent (10 percent of the molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of 1-propylamino-3-methylimidazolium chloride ionic liquid and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, the crude products are separated and purified by thin layer chromatography to obtain target products, and the thin layer chromatography developing solution is petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, the yield was 30%.

Example 6

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of tetrahydrofuran and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 25 percent.

Example 7

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of dimethyl sulfoxide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 12 percent.

Example 8

In the air atmosphere, 10 percent (10 percent of the molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of polyethylene glycol 400 and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 0 percent.

Example 9

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium bromide, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of acetonitrile and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, and the crude products are separated and purified by thin layer chromatography to obtain target products, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 0 percent.

Example 10

In a 10mL graduated tube, 10% (10% of the molar amount of 1, 3-diphenylprop-2-yne-1-one-O-methyloxime ether) of bis (triphenylphosphine) palladium dichloride, 0.2mmol of 1, 3-diphenylprop-2-yne-1-one-O-methyloxime ether, 0.3mmol of vinylphenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide, 0.4mmol of tetrabutylammonium bromide were added under air atmosphere, stirring at 80 deg.C for 8 hr, stopping heating and stirring, cooling to room temperature, extracting, distilling under reduced pressure to obtain crude product, separating and purifying by thin layer chromatography to obtain the target product, wherein the thin layer chromatography developing solution is petroleum ether/ethyl acetate mixed solvent with volume ratio of 100: 1, and the yield is 18%.

Example 11

Adding 10 percent (10 percent of the molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium dichloride, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide into a 10mL graduated tube in air atmosphere, stirring for 8 hours at 80 ℃, stopping heating and stirring, cooling to room temperature, extracting, distilling under reduced pressure to obtain a crude product, separating and purifying by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, the yield was 20%.

Example 12

In a 10mL graduated tube, 10% (10% of the molar amount of 1, 3-diphenylprop-2-yne-1-one-O-methyloxime ether) of bis (acetonitrile) palladium dichloride, 0.2mmol of 1, 3-diphenylprop-2-yne-1-one-O-methyloxime ether, 0.3mmol of vinylphenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide, 0.4mmol of tetrabutylammonium bromide were added under air atmosphere, stirring at 80 deg.C for 8 hr, stopping heating and stirring, cooling to room temperature, extracting, distilling under reduced pressure to obtain crude product, separating and purifying by thin layer chromatography to obtain target product, wherein the thin layer chromatography developing solution is petroleum ether/ethyl acetate mixed solvent with volume ratio of 100: 1, and the yield is 40%.

Example 13

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether) of palladium acetate, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 45 percent.

Example 14

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether) of palladium acetate, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 10 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 45 percent.

Example 15

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether) of palladium acetate, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 90 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 45 percent.

Example 16

In an air atmosphere, 10 percent (10 percent of molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether) of palladium acetate, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyloxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of N, N-dimethylformamide and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 85 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 42 percent.

Example 17

In the air atmosphere, 10 percent (10 percent of the molar amount of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether) of palladium acetate, 0.2mmol of 1, 3-diphenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, and the crude products are separated and purified by thin layer chromatography to obtain target products, and the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 60 percent.

The structural characterization data of the product obtained in example 17 are as follows (nuclear magnetic spectrum as shown in fig. 1 (hydrogen-spectrum) and fig. 2 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ7.89-7.78(m，2H)，7.74-7.65(m，2H)，7.57-7.42(m，6H)，6.67(dd，J＝17.8，11.5Hz，1H)，5.42-5.31(m，2H).

¹³C NMR(100MHz，CDCl₃)δ165.9，162.3，130.0，129.5，129.4，128.9，128.9，128.6，128.1，127.6，124.7，120.4，112.7.

IR(KBr)：2996，2924，2853，1742，1632，1384，1246，1048，921，849，757，691，471cm^-1.

MS(EI，70eV)：m/z(％)＝246[M⁺]，218，191，165，128，105，77，51.

HRMS-ESI(m/z)：calcd for C₁₇H₁₄NO(M+H)⁺：248.1070，found：248.1067.

the structure of the resulting product was deduced from the above data as follows:

example 18

In an air atmosphere, 10 percent (10 percent of molar amount of 1- (4-methylphenyl) -3-phenyl-prop-2-alkyne-1-ketone-O-methyl oxime ether) palladium acetate, 0.2mmol of 1- (4-methylphenyl) -3-phenyl-prop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, the crude products are separated and purified by thin layer chromatography to obtain target products, the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, the yield was 65%.

The structural characterization data of the product obtained in example 18 are as follows (nuclear magnetic spectrum as shown in fig. 3 (hydrogen-spectrum) and fig. 4 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ7.89-7.79(m，2H)，7.64-7.57(m，4H)，7.56-7.44(m，3H)，7.31(d，J＝7.9Hz，2H)，6.74-6.61(m，1H)，5.38(dq，J＝14.1，1.5Hz，2H)，2.45(s，3H).

¹³C NMR(100MHz，CDCl₃)δ165.8，162.2，139.5，130.0，129.3，128.8，128.7，128.2，127.6，126.5，124.8，120.3，112.7，21.4.

IR(KBr)：3025，2924，2857，1751，1632，1425，1292，1173，1014，918，816，749，678，500em^-1.

MS(EI，70eV)：m/z(％)＝260[M⁺]，232，207，142，105，91，77，65.

HRMS-ESI(m/z)：calcd for C₁₈H₁₆NO(M+H)⁺：262.1226，found：262.1225.

the structure of the resulting product was deduced from the above data as follows:

example 19

In an air atmosphere, 10 percent (10 percent of molar amount of 1- (4-trifluoromethylphenyl) -3-phenyl-prop-2-alkyne-1-ketone-O-methyloxime ether) palladium acetate, 0.2mmol of 1- (4-trifluoromethylphenyl) -3-phenyl-prop-2-alkyne-1-ketone-O-methyloxime ether, 0.3mmol of 4-methylphenylvinylether, 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, the crude products are separated and purified by thin layer chromatography to obtain target products, and the thin layer chromatography developing solution is petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, the yield was 60%.

The structural characterization data of the product obtained in example 19 are as follows (nuclear magnetic spectrum as shown in fig. 5 (hydrogen-spectrum) and fig. 6 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ7.83(td，J＝5.7，2.8Hz，4H)，7.77(d，J＝8.2Hz，2H)，7.58-7.47(m，3H)，6.67(dd，J＝17.9，11.4Hz，1H)，5.43(dd，J＝11.4，1.2Hz，1H)，5.34(dd，J＝17.9，1.2Hz，1H).

³C NMR(100MHz，CDCl₃)δ166.4，161.1，133.1(q，J＝1Hz)，131.6(q，J＝33Hz)，130.3，129.3，128.9，127.8，127.6，125.6(q，J＝4Hz)，124.4，123.9(q，J＝270.0Hz)，121.1，112.6.

IR(KBr)：2926，1751，1629，1424，1325，1134，1065，841，669，478em^-1.

MS(EI，70eV)：m/z(％)＝315[M⁺]，287，246，144，115，105，77，51

HRMS-ESI(m/z)：calcd for C₁₈H₁₃NOF₃(M+H)⁺：316.0944，found：316.0941.

the structure of the resulting product was deduced from the above data as follows:

example 20

In an air atmosphere, 10 percent (10 percent of molar amount of 5-phenyl-2, 2-dimethylpent-4-alkyne-3-ketone-O-methyloxime ether) of palladium acetate, 0.2mmol of 5-phenyl-2, 2-dimethylpent-4-alkyne-3-ketone-O-methyloxime ether, 0.3mmol of vinylphenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, stirring at 80 deg.C for 8 hr, stopping heating and stirring, cooling to room temperature, extracting, distilling under reduced pressure to obtain crude product, separating and purifying by thin layer chromatography to obtain the target product, wherein the thin layer chromatography developing solution is petroleum ether/ethyl acetate mixed solvent with volume ratio of 100: 1, and the yield is 68%.

The structural characterization data of the product obtained in example 20 are as follows (nuclear magnetic spectrum as shown in fig. 7 (hydrogen-spectrum) and fig. 8 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ7.88-7.66(m，2H)，7.53-7.37(m，3H)，6.68(dd，J＝17.7，11.1Hz，1H)，5.66-5.23(m，2H)，1.44(s，9H).

¹³C NMR(100MHz，CDCl₃)δ169.6，165.4，129.5，128.6，128.5，127.5，126.8，122.1，112.9，33.3，28.9。

IR(KBr)：2924，2852，1633，1511，1367，1278，1044，922，833，731，689.

MS(EI，70eV)：m/z(％)＝227[M⁺]，212，170，144，115，105，77，57；

HRMS-ESI(m/z)：calcd for C₁₅H₁₈NO(M+H)⁺：228.1383，found：228.1380.

the structure of the resulting product was deduced from the above data as follows:

example 21

In an air atmosphere, 10 percent (10 percent of molar amount of 3- (4-chlorphenyl) -1-phenylprop-2-alkyne-1-ketone-O-methyl oxime ether) palladium acetate, 0.2mmol of 3- (4-chlorphenyl) -1-phenylprop-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of 4-chlorphenyl vinyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, the crude products are separated and purified by thin layer chromatography to obtain target products, the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, the yield was 71%.

The structural characterization data of the product obtained in example 21 are as follows (nuclear magnetic spectrum as shown in fig. 9 (hydrogen-spectrum) and fig. 10 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ7.84-7.73(m，2H)，7.68(m，J＝5.8，4.1，2.4Hz，2H)，7.54-7.46(m，5H)，6.63(dd，J＝17.8，11.4Hz，1H)，5.46-5.30(m，2H).

¹³C NMR(100MHz，CDCl₃)δ164.7，162.4，136.1，129.6，129.2，129.2，128.8，128.8，128.7，126.6，124.5，121.0，113.0.

IR(KBr)：2925，2855，1898，1749，1624，1409，1288，1170，1092，100，930，832，756，691，507cm^-1.

MS(EI，70eV)：m/z(％)＝281[M⁺]，267，252，207，191，139，111，96，73，51.

HRMS-ESI(m/z)：calcd for C₁₇H₁₃NOCl(M+H)⁺：282.0680，found：282.0678.

the structure of the resulting product was deduced from the above data as follows:

example 22

In an air atmosphere, 10% (10% of molar amount of 1-phenyl-3- (3-thienyl) prop-2-yne-1-one-O-methyloxime ether) of palladium acetate, 0.2mmol of 1-phenyl-3- (3-thienyl) prop-2-yne-1-one-O-methyloxime ether and 0.3mmol of 4-bromophenyl vinyl ether (R in the structure of the vinylphenyl ether compound) are added into a 10mL graduated tube³4-bromine), 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide, stirring at 80 ℃ for 8 hours, stopping heating and stirring, cooling to room temperature, extracting, distilling under reduced pressure to obtain a crude product, and separating and purifying by thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 73%.

The structural characterization data of the product obtained in example 22 are as follows (nuclear magnetic spectrum as shown in fig. 11 (hydrogen-spectrum) and fig. 12 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ7.95-7.85(m，1H)，7.74-7.66(m，2H)，7.59(dd，J＝5.1，1.3Hz，1H)，7.55-7.41(m，4H)，6.68(dd，J＝17.8，11.5Hz，1H)，5.48-5.42(m，1H)，5.42(dd，J＝12.0，1.5Hz，1H).

¹³C NMR(100MHz，CDCl₃)δ162.3，162.1，129.6，129.4，128.9，128.8，128.6，126.6，126.0，125.4，124.8，120.8，112.1.

IR(KBr)：2921，2852，1744，1636，1442，1373，1245，1049，921，855，781，685，477cm^-1.

MS(EI，70eV)：m/z(％)＝253[M⁺]，224，220，171，150，122，111，83，63，51.

HRMS-ESI(m/z)：calcd for C₁₅H₁₂NOS(M+H)⁺：254.0634，found：254.0630.

the structure of the resulting product was deduced from the above data as follows:

example 23

In an air atmosphere, 10 percent (10 percent of molar amount of 1-phenylhex-2-alkyne-1-ketone-O-methyl oxime ether) palladium acetate, 0.2mmol of 1-phenylhex-2-alkyne-1-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, crude products are obtained by extraction and reduced pressure distillation, and the crude products are separated and purified by thin layer chromatography to obtain target products, and the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 75 percent.

The structural characterization data of the product obtained in example 23 are as follows (nuclear magnetic spectrum as shown in fig. 13 (hydrogen-spectrum) and fig. 14 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ7.75-7.61(m，2H)，7.49-7.45(m，3H)，6.58-6.39(m，1H)，5.52-5.21(m，2H)，2.86(t，J＝7.5Hz，2H)，1.90-1.80(m，2H)，1.06(d，J＝7.4Hz，3H).

¹³C NMR(100MHz，CDCl₃)δ170.1，161.3，129.5，128.6，128.6，126.8，125.2，117.8，112.6，28.2，21.0，13.9.

IR(KBr)：2927，2858，1764，1641，1455，1264，1057，914，740cm^-1.

MS(EI，70eV)：m/z(％)＝212[M⁺]，198，170，143，128，115，104，77，55.

HRMS-ESI(m/z)：calcd for C₁₄H₁₆NO(M+H)⁺：214.1226，found：214.1223.

the structure of the resulting product was deduced from the above data as follows:

example 24

In an air atmosphere, 10 percent (10 percent of molar amount of 2, 2-dimethyl nonane-4-alkyne-3-ketone-O-methyl oxime ether) palladium acetate, 0.2mmol of 2, 2-dimethyl nonane-4-alkyne-3-ketone-O-methyl oxime ether, 0.3mmol of vinyl phenyl ether, 0.2mmol of 1, 2-naphthoquinone, 1mL of ethylene glycol dimethyl ether and 0.4mmol of tetrabutylammonium bromide are added into a 10mL graduated tube, after stirring for 8 hours at 80 ℃, heating and stirring are stopped, the mixture is cooled to room temperature, extraction and reduced pressure distillation are carried out to obtain a crude product, and the crude product is separated and purified through thin layer chromatography to obtain a target product, wherein the thin layer chromatography developing solution is a petroleum ether/ethyl acetate mixed solvent with the volume ratio of 100: 1, and the yield is 56 percent.

The structural characterization data of the product obtained in example 24 are as follows (nuclear magnetic spectrum as shown in fig. 15 (hydrogen-spectrum) and fig. 16 (carbon-spectrum)):

¹H NMR(400MHz，CDCl₃)δ6.56(dd，J＝17.5，11.1Hz，1H)，5.39(dd，J＝11.1，1.7Hz，1H)，5.28(dd，J＝17.5，1.7Hz，1H)，2.80-2.72(m，2H)，1.76-1.64(m，2H)，1.45-1.39(m，2H)，1.37(s，9H)，0.95(t，J＝7.3Hz，3H).

¹³C NMR(100MHz，CDCl₃)δ169.7，126.8，118.5，77.3，77.0，76.7，32.9，29.7，28.8，25.7，22.4，13.7.

IR(KBr)：2927，2860，1760，1634，1457，1378，1243，1054，917，851，739，645，543，453cm^-1.

MS(EI，70eV)：m/z(％)＝207[M⁺]，165，150，122，109，68，57.

HRMS-ESI(m/z)：calcd for C₁₃H₂₂NO(M+H)⁺：208.1696，found：208.1693.

the structure of the resulting product was deduced from the above data as follows: