CN110845291B - Method for catalytic reduction of alkyne into olefin by visible light induction - Google Patents
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Abstract
The invention discloses a method for catalytic reduction of alkyne into olefin by visible light induction, which avoids the generation of over-reduced alkane product, and the yield can reach 99 percent. The method comprises the steps of taking alkyne as a raw material, adding a photosensitizer and a cobalt catalyst, then adding a phosphine ligand or a bipyridine ligand, an electron sacrificial reagent, acetic acid and an organic solvent under the protection of inert gas, and irradiating for 7-14 hours at room temperature by using blue light. And after the reaction is finished, spin-drying the reaction solution, and separating by silica gel column chromatography to obtain an olefin product. Wherein the organic solvent is 1,4-dioxane or tetrahydrofuran; the alkyne is aliphatic alkyne or aromatic alkyne. The method realizes reduction of alkyne through a hydrogen transfer strategy, avoids use of dangerous hydrogen, has no generation of over-reduced products, has mild reaction conditions and high reaction yield, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalytic synthesis of fine chemical products, and particularly relates to a method for catalytic reduction of alkyne into olefin through visible light induction.
Background
The alkene structure is the most basic building block for many biologically active molecules. For example, resveratrol, a stilbene derivative, has shown good antitumor, cardiovascular disease resistance, antioxidant and nervous system protection and other biological activities and pharmacological actions. In addition, olefins are also a very important class of organic synthesis building blocks, which are capable of undergoing various organic transformations and are therefore widely used in organic synthesis reactions. The synthesis of olefins has thus been an important research content for organic synthesis methodologies.
Among the various olefin synthesis methods available, transition metals catalyze the direct reduction of alkynes as the most direct and efficient method. For example, the most commonly used Lindlar catalysts are efficient methods for synthesizing cis-olefins. However, this method has the following two problems: (1) the preparation method of the Lindlar catalyst determines the catalytic activity of the Lindlar catalyst, and the reduction reaction using the Lindlar catalyst cannot usually inhibit the generation of over-reduction products, so that the chemical selectivity of the reduction reaction is not high, and the separation and purification are difficult. (2) The reduction reaction requires the use of hydrogen as a hydrogen source, resulting in special requirements in terms of equipment and safety. Transition metals developed in recent years to catalyze hydrogen transfer reactions with NH3-BH3Formic acid, methanol, hydrosilane and the like are taken as hydrogen sources, and although the use of hydrogen is avoided, the defects that a catalyst needs to be synthesized in multiple steps, the reaction temperature is high and the like are encountered.
In recent years, visible light-induced catalysis has attracted great attention due to its green and sustainable characteristics, and has become an important means in the field of organic synthesis. The metal hydrogen species is a key intermediate for reducing alkyne into olefin, wherein the visible light-induced catalysis of the generation of the cobalt hydrogen species is widely reported in the photolysis of water, photocatalytic coupling and visible light-induced catalysis of hydrogen release coupling reaction. However, the use of the cobalt hydride intermediate generated by visible light-induced catalysis for reduction of alkynes has not been investigated.
In summary, the research on the reaction system for reducing alkyne into olefin by using non-hydrogen source is one of the important research contents of synthetic chemistry, wherein the development of efficient visible light-induced catalysis of alkyne reduction into olefin is a necessary requirement for sustainable development, and is a problem to be solved at present.
Disclosure of Invention
The invention aims to provide a method for catalytic reduction of alkyne into olefin by visible light induction, which takes green sustainable visible light as an energy source, is milder, high-efficiency and high in chemical selectivity and can avoid the generation of a reduction product.
The method for catalytic reduction of alkyne into alkene by visible light induction comprises the steps of dissolving a photosensitizer, a cobalt catalyst, a ligand, an electron sacrificial reagent, acetic acid and alkyne in an organic solvent in an inert atmosphere, and carrying out alkyne reduction reaction under blue light irradiation to generate a target alkene product; the structural general formula of the alkyne is (Ar) R1-≡-R2(Ar，H)，R1And R2Any one selected from the following groups: alkyl, benzene ring, biphenyl, alkylbenzene, alkoxybenzene, halogenated benzene, esterbenzene, cyanobenzene and thienyl; in addition, when R is1When it is alkyl or aryl, R2Can be H; the organic solvent is 1,4-dioxane or Tetrahydrofuran (THF); the photosensitizer is Ir [ dF (CF)3)ppy)](dtbbpy)PF6(ii) a The cobalt catalyst is CoBr2(ii) a The ligand is n-Bu3P or 4,4 '-di-tert-butyl-2, 2' -bipyridine (dtbbpy), preferably n-Bu3P; the electron-sacrificing reagent is diisopropylethylamine.
The dosage of the photosensitizer is 0.5 to 1 percent, preferably 1 percent of the molar dosage of alkyne; the dosage of the cobalt catalyst is 5 to 10 percent, preferably 5 percent of the molar dosage of the alkyne; the dosage of the ligand is 5 to 15 percent, preferably 10 percent of the molar dosage of the alkyne; the dosage of the electronic sacrificial reagent is 2-4 times, preferably 3 times of the molar dosage of alkyne; the amount of the acetic acid is 3-6 times, preferably 5 times of the molar amount of the alkyne.
The reaction is carried out in an inert atmosphere, the reaction time is 7-14 hours, the atmosphere of various inert gases is suitable, and the reduction reactor is a sealable glass or quartz reactor.
The method for catalytic reduction of alkyne into olefin by visible light induction has the following characteristics: (1) using green sustainable visible light as an energy source; (2) the reaction condition is mild, the catalyst is cheap and easy to obtain, the reaction operation is simple, and the method is suitable for large-scale production; (3) the reaction has no over-reduction product alkane; (4) the cheap diisopropylethylamine (i-PrNEt) and acetic acid (AcOH) are used as hydrogen sources, so that the special requirements on devices and safety when hydrogen is used as the hydrogen source are avoided. In conclusion, the method has the advantages of cheap and easily-obtained reagents, mild reaction conditions, simple process operation, high reaction chemical selectivity (no over-reduction product generation), high reaction yield and the like.
Drawings
FIG. 1 is a hydrogen spectrum of a cis-trans olefin mixture obtained in example 1;
FIG. 2 is a hydrogen spectrum of the cis-trans olefin mixture obtained in example 4;
FIG. 3 is a hydrogen spectrum of the cis-trans olefin mixture obtained in example 5;
FIG. 4 is a hydrogen spectrum of the cis-trans olefin mixture obtained in example 6;
FIG. 5 is a hydrogen spectrum of the cis-trans olefin mixture obtained in example 7;
FIG. 6 is a hydrogen spectrum of the olefin product obtained in example 8;
FIG. 7 is a carbon spectrum of the olefin product obtained in example 8;
FIG. 8 is a hydrogen spectrum of the olefin product obtained in example 9;
FIG. 9 is a carbon spectrum of the olefin product obtained in example 9.
Detailed Description
A catalytic system for reducing alkyne into olefin by hydrogen transfer reaction under visible light induction; in the system with Ir [ dF (CF)3)ppy)](dtbbpy)PF6As a photosensitizer, CoBr2/(n-Bu3P or dtbbpy) as hydrogen transfer catalyst, diisopropylethylamine (i-Pr)2NEt) as electron-sacrificing agent, with i-Pr2The NEt and the AcOH are jointly used as a hydrogen source to catalyze alkyne to be reduced into olefin with high efficiency and high chemoselectivity.
The method can be carried out according to the following method:
(1) by first introducing solid reagents, e.g. photosensitizers, into the glass tubeIr[dF(CF3)ppy)](dtbbpy)PF6，CoBr2Solid alkyne materials, solid ligands, and the like;
(2) introducing argon gas into the tube, and adding liquid reagent such as DIPEA, AcOH, n-Bu under argon gas3P, 1,4-dioxane or THF and the like as a solvent, and sealing;
(3) irradiating with 50W blue light for 7-14 h;
(4) and after the reaction is finished, removing the solvent by rotary evaporation, and carrying out column chromatography separation to obtain an olefin product.
The present invention is further illustrated by the following specific examples.
EXAMPLE 1 reduction of tolane
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), tolane (35.6mg,1.0equiv), into a 10mL glass tube with a cover, followed by replacing the air in the reaction tube with argon, and adding n-Bu with a microsyringe under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 14 h. After the reaction is stopped, the reaction liquid is dried by spinning, 35.8mg of olefin products I-1a and I-1b are obtained by column chromatography separation, and the total yield of the reaction is quantified (>99%) cis-trans olefin ratio in the product: and Z/E is 3.5:1.
I-1a is a colorless liquid,1H NMR(400MHz,CDCl3)δ7.25-7.17(m,10H),6.59(s,2H)；13C NMR(100MHz,CDCl3) δ 137.2(2C),130.2(2C),128.9(4C),128.2(4C),127.1 (2C); i-1b is a white solid,1HNMR(400MHz,CDCl3)δ7.56(d,J＝7.6Hz,4H),7.40(t,J＝7.6Hz,4H),7.30(t,J＝7.6Hz,2H),7.15(s,2H).13C NMR(100MHz,CDCl3)δ137.3(2C),128.7(2C),128.7(4C),127.6(2C),126.5(4C)。
EXAMPLE 2 reduction of tolane
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), tolane (35.6mg,1.0equiv), into a 10mL glass tube with a cover, followed by replacing the air in the reaction tube with argon, and adding n-Bu with a microsyringe under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL THF, seal the reaction tube, 50W blue light irradiation for 14 h. After the reaction is stopped, spin-drying the reaction liquid, and separating by column chromatography to obtain 35.5mg of olefin products I-1a and I-1b, wherein the total reaction yield is 98 percent, and the cis-trans olefin proportion in the products is as follows: the physical property data was the same as in example 1, except that Z/E was 3.5:1.
EXAMPLE 3 reduction of tolane
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), tolane (35.6mg,1.0equiv), dtbbpy (5.4mg,10 mol%) was charged into a 10mL glass tube with a cap, followed by replacement of the air in the reaction tube with argon, and addition of i-Pr by a microinjector under argon conditions2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 14 h. After the reaction is stopped, spin-drying the reaction liquid, and separating by column chromatography to obtain 35.6mg of olefin products I-1a and I-1b, wherein the total reaction yield is 99%, and the cis-trans olefin proportion in the products is as follows: the other physical property data were the same as in example 1.
EXAMPLE 4 reduction of 4-Methoxybenzeneyne
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), 4-methoxydiphenylacetylene (41.7mg,1.0equiv) was charged into a 10mL glass tube with a cover, followed by replacement of the air in the reaction tube with argon and addition of n-Bu with a microsyringe under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 14 h. After the reaction is stopped, the reaction liquid is dried by spinning, and 41.7mg of olefin products I-2a and I-2b are obtained by column chromatography separation, and the total yield of the reaction is quantified (>99%) cis-trans olefin ratio in the product: and Z/E is 3.0:1.
I-2a is a colorless liquid,1H NMR(400MHz,CDCl3)δ7.36–7.13(m,7H),6.75(d,J＝8.7Hz,2H),6.58–6.47(m,2H),3.78(s,3H)；13C NMR(100MHz,CDCl3) δ 158.6,137.6,130.1(2C),129.7,129.6,128.8(2C),128.7,128.2(2C),126.9,113.6(2C), 55.17; i-2b is white solid, and the white solid is white solid,1H NMR(400MHz,CDCl3)δ7.51–7.45(m,4H),7.35(t,J＝7.2Hz,2H),7.24(t,J＝7.6Hz,1H),7.07(d,J＝16.0Hz,1H),6.98(d,J＝16.4Hz,1H),6.91(d,J＝8.8Hz,2H),3.84(s,3H)；13C NMR(100MHz,CDCl3)δ159.3,137.7,130.2,128.6(2C),128.2,127.7(2C),127.2,126.6,126.2(2C),114.1(2C),55.3。
EXAMPLE 5 reduction of methyl 4-phenylacetylene benzoate
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), methyl 4-phenylacetylenebenzoate (47.3mg,1.0equiv) was charged into a 10mL glass tube with a cap, followed by replacement of the air in the reaction tube with argon and addition of n-Bu with a microinjector under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 14 h. After the reaction is stopped, the reaction liquid is dried by spinning, and 47.4mg of olefin products I-3a and I-3b are obtained by column chromatography separation, and the total yield of the reaction is quantified (>99%) cis-trans olefin ratio in the product: and Z/E is 1.7:1.
I-3a is a colorless liquid,1H NMR(400MHz,CDCl3)δ7.93(d,J＝8.0Hz,2H),7.34(d,J＝8.4Hz,2H),7.26(s,5H),6.75(d,J＝12.4Hz,1H),6.65(d,J＝12.4Hz,1H),3.93(s,3H)；13C NMR(100MHz,CDCl3) δ 166.9,142.1,136.6,132.2,129.5(2C),129.2,128.8(4C),128.6,128.3(2C),127.5, 52.0; i-3b is white solid, and the white solid is white solid,1H NMR(400MHz,CDCl3)δ8.03(d,J＝8.3Hz,2H),7.60–7.53(m,4H),7.38(t,J＝7.6Hz,2H),7.3(d,J＝7.2Hz,1H),7.20(d,J＝16.4Hz,1H),7.13(d,J＝16.4Hz,1H),3.93(s,3H)；13C NMR(100MHz,CDCl3)δ166.9,141.8,136.8,131.2,130.0(2C),128.9,128.8(2C),128.2,127.6,126.8(2C),126.3(2C),52.1。
example 6 reduction of 2-methyl-5-phenylethynyl thiophene
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), 2-methyl-5-phenylethynyl thiophene (39.7mg,1.0equiv) was added to a 10mL glass tube with a cover, followed by replacement of the air in the reaction tube with argon, and addition of n-Bu with a microinjector under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 14 h. After the reaction is stopped, spin-drying the reaction liquid, and separating by column chromatography to obtain 35.7mg of olefin products I-4a and I-4b, wherein the total reaction yield is 89%, and the cis-trans olefin proportion in the products is as follows: Z/E is 1.2:1,
i-4a is a colorless liquid,1H NMR(400MHz,CDCl3)δ7.38–7.29(m,5H),6.77(d,J＝3.6Hz,1H),6.61(d,J＝12.0Hz,1H),6.54–6.53(m,1H),6.47(d,J＝12.0Hz,1H),2.35(s,3H)；13C NMR(100MHz,CDCl3)δ140.2,137.7,137.5,128.8(2C),128.6,128.4(2C),127.4,127.3,124.6,123.7,15.3；HRMS-ESI:m/z:[M+H]+calculated for C13H13s, 201.0732; found 201.0735; i-4b is a colorless liquid,1H NMR(400MHz,CDCl3)δ7.44(d,J＝7.2Hz,2H),7.33(t,J＝7.6Hz,2H),7.22(t,J＝7.2Hz,1H),7.15(d,J＝16.0Hz,1H),6.85(d,J＝3.2Hz,1H),6.79(d,J＝16.0Hz,1H),6.65–6.64(m,1H),2.48(s,3H)；13C NMR(100MHz,CDCl3)δ140.8,139.3,137.2,128.6(2C),127.3,127.0,126.4,126.1(2C),125.7,122.2,15.6。
example 7 reduction of 3-phenyl-2-propyn-1-ol
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), 3-phenyl-2-propyn-1-ol (26.4mg,1.0equiv) was charged into a 10mL glass tube with a cover, followed by replacement of the air in the reaction tube with argon, and n-Bu was added with a microinjector under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 7 h. After the reaction is stopped, spin-drying the reaction liquid, and separating by column chromatography to obtain 26.0mg of olefin products I-5a and I-5b, wherein the total reaction yield is 97%, and the cis-trans olefin ratio in the products is as follows: Z/E is 2.6:1,
i-5a, colorless liquid,1H NMR(400MHz,CDCl3)δ7.35(t,J＝7.2Hz,2H),7.6(t,J＝7.6Hz,1H),7.21(d,J＝7.6Hz,2H),6.57(d,J＝11.6Hz,1H),5.91–5.84(m,1H),4.44(d,J＝6.0Hz,2H),1.62(br,1H)；13C NMR(100MHz,CDCl3) Delta 136.5,131.1,131.0,128.8(2C),128.2(2C),127.2,59.7.I-5 b-colorless liquid,1H NMR(400MHz,CDCl3)δ7.39(d,J＝7.2Hz,2H),7.32(t,J＝7.2Hz,2H),7.25–7.23(m,1H),6.62(d,J＝16.4Hz,1H),6.41–6.34(m,1H),4.33(s,2H),1.45(br,1H)；13C NMR(100MHz,CDCl3)δ131.2,128.6(2C),128.5(2C),127.7,126.5(2C),63.8。
example 8 reduction of ethisterone
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), ethisterone (62.5mg,1.0equiv) was added to a 10mL glass tube with a cap, followed by replacement of the air in the reaction tube with argon and addition of n-Bu with a microsyringe under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 14 h. After the reaction is stopped, the reaction liquid is dried by spinning, and the olefin product I-6 which accounts for 62.6mg is obtained by column chromatography separation, (the total reaction yield is quantified)>99％)，
I-6, white solid is added in the reaction kettle,1H NMR(400MHz,CDCl3)δ6.03(dd,J＝17.6,10.8Hz,1H),5.73(s,1H),5.17–5.10(m,2H),2.45–2.26(m,4H),2.04–-1.94(m,2H),1.90–1.84(m,2H),1.72–1.50(m,6H),1.47–1.35(m,2H),1.29–1.22(m,2H),1.20(s,3H),1.07–1.00(m,1H),0.96(s,3H),0.91–0.84(m,1H)；13C NMR(100MHz,CDCl3)δ199.5,171.2,142.8,123.8,112.2,83.9,53.6,49.4,46.1,38.6,36.2,35.9,35.6,33.9,32.8,31.9,31.6,23.5,20.6,17.4,14.0.HRMS-ESI:m/z:[M+H]+calculated for C21H31O2,315.2319；found 315.2320。
example 9 reduction of estradiol
Ir [ dF (CF) is weighed respectively3)ppy)](dtbbpy)PF6(2.2mg,1mol％),CoBr2(2.2mg,5 mol%), estradiol (59.3mg,1.0equiv) was added to a 10mL glass tube with a cover, followed by replacement of the air in the reaction tube with argon, and n-Bu was added with a micro-syringe under argon3P(4.0mg,10mol％),i-Pr2NEt (77.6mg,3.0equiv), AcOH (60mg,5.0equiv),2mL of 1,4-dioxane, sealed reaction tube, and irradiated with 50W blue light for 14 h. After the reaction is stopped, the reaction liquid is dried by spinning, 59.2mg of olefin product I-7 is obtained by column chromatography separation, and the total reaction yield is quantified (>99％)，
I-7, white solid is added,1H NMR(400MHz,DMSO)δ8.98(s,1H),7.02(d,J＝8.4Hz,1H),6.50–6.47(m,1H),6.42(s,1H),6.04(dd,J＝17.2,10.8Hz,1H),5.11–5.00(m,2H),4.50(s,1H),2.72–2.68(m,2H),2.19–2.18(m,1H),1.97(bs,1H),1.78–1.72(m,3H),1.62–1.60(m,1H),1.52–1.50(m,1H),1.39–1.19(m,6H),0.82(s,3H)；13C NMR(100MHz,DMSO)δ154.9,144.3,137.1,130.4,126.0,114.9,112.7,111.2,82.7,48.3,46.3,43.3,39.3,35.3,31.9,29.2,27.1,26.1,23.0,14.1。
Claims (7)
1. a method for catalytic reduction of alkyne into olefin by visible light induction is characterized in that: dissolving a photosensitizer, a cobalt catalyst, a ligand, an electronic sacrificial reagent, acetic acid and alkyne in an organic solvent in an inert atmosphere, and carrying out alkyne reduction reaction under the irradiation of blue light to generate an alkene product;
the structural general formula of the alkyne is
，R1And R2Any one selected from the following groups: alkyl, phenyl, biphenyl, alkylphenyl, alkoxyphenyl, halophenyl, esterylphenyl, cyanophenyl, thienyl;
the organic solvent is 1,4-dioxane or tetrahydrofuran;
the photosensitizer is
；
The cobalt catalyst is CoBr2；
The ligand isn-Bu3P or
；
The electron sacrificial reagent is diisopropylethylamine.
2. The method of claim 1, wherein the catalytic reduction of alkyne into alkene is induced by visible light, and the method comprises: the dosage of the photosensitizer is 0.5 to 1 percent of the molar dosage of alkyne.
3. The method of claim 1, wherein the catalytic reduction of alkyne into alkene is induced by visible light, and the method comprises: the dosage of the cobalt catalyst is 5 to 10 percent of the molar dosage of alkyne.
4. The method of claim 1, wherein the catalytic reduction of alkyne into alkene is induced by visible light, and the method comprises: the dosage of the ligand is 5 to 15 percent of the molar dosage of alkyne.
5. The method of claim 1, wherein the catalytic reduction of alkyne into alkene is induced by visible light, and the method comprises: the dosage of the electronic sacrificial reagent is 2-4 times of the molar dosage of alkyne.
6. The method of claim 1, wherein the catalytic reduction of alkyne into alkene is induced by visible light, and the method comprises: the amount of the acetic acid is 3-6 times of the molar amount of the alkyne.
7. The method of claim 1, wherein the catalytic reduction of alkyne into alkene is induced by visible light, and the method comprises: the reaction time is 7-14 hours.
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| cis-Selective Transfer Semihydrogenation of Alkynes by Merging;Wan-Fa Tian等;《Adv. Synth. Catal》;20200124;第362卷;第1032-1038页 * |
| Dual Cobalt and Photoredox Catalysis Enabled Redox-Neutral Annulation of 2-Propynolphenols;Yao Zhu等;《Adv. Synth. Catal》;20210521;第363卷(第13期);第3372-3377页 * |
| Visible-Light-Driven Alkyne Hydro-/Carbocarboxylation Using CO2 via Iridium/Cobalt Dual Catalysis for Divergent Heterocycle Synthesis;Jing Hou等;《J. Am. Chem. Soc.》;20180329;第140卷(第15期);第5257-5263页 * |
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