Cyclopenta[c]chromium compound and preparation method therefor

Abstract

The present invention discloses a cyclopenta[c]chromene compound and a preparation method thereof. A chalcone compound as a reactant, A cationic rare earth metal compound Ln(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN as a catalyst, and 2-naphthalenethiol as an accelerator, react in an organic solvent to prepare the cyclopenta[c]-chromene compound. Ln represents a positive trivalent rare earth metal ion, which is selected from the group consisting of La, Nd, Sm, Gd, and Yb. The starting materials are easy obtained, the reaction process is simple, and the yield of the target product is high, up to 85%.

Claims

1. A method for preparing a cyclopenta[c]chromene compound, comprising the following steps: under anhydrous and anaerobic conditions, a chalcone compound as a reactant, a cationic rare earth metal compound as a catalyst, and 2-naphthalenethiol as an accelerator, react in an organic solvent to prepare the cyclopenta[c]chromene compound; wherein the cationic rare earth metal compound has the following structure: ##STR00021## wherein, Ln represents a trivalent rare earth metal ion; wherein the chalcone compound has the following chemical structure: ##STR00022## wherein, R.sup.1 is selected from the group consisting of hydrogen, 3-chloro, 4-chloro, 4-methoxy, 5-chloro, 5-bromo, 5-methyl, 5-methoxy, and 6-chloro; R.sup.2 is selected from the group consisting of hydrogen, 3′-chloro, 3′-bromo, 3′-methoxy, 4′-chloro, 4′-bromo, 4′-phenyl, and 4′-methoxy.

2. The method for preparing the cyclopenta[c]chromene compound according to claim 1, wherein the organic solvent is selected from the group consisting of chlorobenzene, acetonitrile, dichloroethane, and toluene; Ln is selected from the group consisting of La, Nd, Sm, Gd, and Yb; and the anhydrous and anaerobic conditions are an inert atmosphere condition.

3. The method for preparing the cyclopenta[c]chromene compound according to claim 2, wherein the organic solvent is chlorobenzene and Ln is ytterbium.

4. The method for preparing cyclopenta[c]chromene compound according to claim 1, wherein a molar ratio of the catalyst:the chalcone compound:the accelerator is (0.01 to 0.08):1:(0.6 to 1.3).

5. The method for preparing cyclopenta[c]chromene compound according to claim 4, wherein the molar ratio of the catalyst:the chalcone compound:the accelerator is (0.03 to 0.07):1:(1.1 to 1.2).

6. The method for preparing cyclopenta[c]chromene compound according to claim 1, wherein a reaction temperature is 80 to 140° C.; and a reaction time is 24 to 72 hours.

7. The method for preparing cyclopenta[c]chromene compound according to claim 6, wherein the reaction temperature is a reflux temperature of the organic solvent, and the reaction time is 36 hours.

Description

EMBODIMENTS OF THE INVENTION

(1) The following further describes the present invention with reference to the embodiments:

Example 1: Synthesis of Catalyst [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN

(2) Under the protection of argon, 0.70 g (2.5 mmol) of YbCl.sub.3 and 1.00 g (7.5 mmol) of anhydrous AlCl3 were added into a dehydrated and deoxidized reaction flask according in a molar ratio of 1:3. 25 mL of acetonitrile was added to dissolve reactants. Centrifugal treatment was carried out after stirring for 24 hours at room temperature, taking the supernatant, concentrating and leaving it in a refrigerator at 0° C. The obtained crystal is [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN, yield 46%.

(3) Other [Ln(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN catalysts can be prepared by the same method, using different rare earth metal chloride.

Example 2: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(4) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 24 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 46%.

(5) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(6) ##STR00005##

(7) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.70 (d, J=8.0 Hz, 1H), 7.60 (d, J=8.4 Hz, 1H), 7.47-7.44 (m, 3H), 7.37-7.28 (m, 3H), 7.24-7.20 (m, 1H), 7.16-7.13 (m, 2H), 7.11-7.04 (m, 3H), 7.02-6.96 (m, 5H), 5.42 (s, 1H).

Example 3: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(8) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0381 g, 0.035 mmol, 7 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 24 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 87%.

Example 4: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(9) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 85%. When the catalyst was changed to “3% YbCl.sub.3+9% AlCl.sub.3,” “3% YbCl.sub.3,” or “3% FeCl.sub.3,” the yield was 59%, 30%, or 27% respectively. When the accelerator was changed to 1-mercaptodecane, the yield was 24%.

Example 5: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(10) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 60 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 81%.

Example 6: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(11) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 72 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 76%.

Example 7: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(12) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and acetonitrile (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and acetonitrile (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 47%.

Example 8: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(13) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and dichloroethane (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and dichloroethane (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 46%.

Example 9: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(14) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and toluene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and toluene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 43%.

Example 10: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(15) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred at 100° C. for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 64%.

Example 11: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(16) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred at 120° C. for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 80%.

Example 12: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(17) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0481 g, 0.3 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 61%.

Example 13: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzes the Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(18) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0801 g, 0.5 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 63%.

Example 14: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(19) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 1 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0801 g, 0.5 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 50%.

Example 15: [La(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(20) [La(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0158 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 66%.

Example 16: [Nd(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(21) [Nd(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0159 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 58%.

Example 17: [Sm(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(22) [Sm(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0159 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 61%.

Example 18: [Gd(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 2-Hydroxychalcone to Prepare Cyclopenta[c]Chromene Compound

(23) [Gd(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0161 g, 0.015 mmol, 3 mol %), 2-hydroxychalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 64%.

Example 19: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(3-chloro-2-hydroxyphenyl)-1-phenyl-2-propene-1-one to Prepare Cyclo-Penta[c]Chromene Compound

(24) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0273 g, 0.025 mmol, 5 mol %), 3-(3-chloro-2-hydroxyphenyl)-1-phenyl-2-propene-1-one (0.1293 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 62%.

(25) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(26) ##STR00006##

(27) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.57 (dd, J=8.0, 1.2 Hz, 1H), 7.54-7.52 (m, 2H), 7.42-7.36 (m, 3H), 7.33-7.29 (m, 1H), 7.17-7.10 (m, 4H), 7.03-7.01 (m, 5H), 6.99-6.97 (m, 1H), 5.77 (s, 1H).

Example 20: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(3-chloro-2-hydroxyphenyl)-1-phenyl-2-propene-1-one to Prepare Cyclo-Penta[c]Chromene Compound

(28) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0273 g, 0.025 mmol, 3 mol %), 3-(4-chloro-2-hydroxyphenyl)-1-phenyl-2-propen-1-one (0.1293 g, 0.5 mmol) and acetonitrile (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and acetonitrile (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 73%.

(29) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(30) ##STR00007##

(31) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.62 (d, J=2.0 Hz, 1H), 7.57 (d, J=8.8 Hz, 1H), 7.44-7.42 (m, 2H), 7.35-7.30 (m, 2H), 7.21 (dd, J=8.8, 2.0 Hz, 1H), 7.17-7.13 (m, 2H), 7.11 (d, J=2.0 Hz, 1H), 7.05-6.96 (m, 7H), 5.44 (s, 1H).

Example 21: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(2-hydroxy-4-methoxyphenyl)-1-phenyl-2-propene-1-one to Prepare Cyclo-Penta[c]Chromene Compound

(32) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0381 g, 0.035 mmol, 3 mol %), 3-(2-hydroxy-4-methoxyphenyl)-1-phenyl-2-propene-1-one (0.1272 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and toluene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 69%.

(33) The theoretical molecular formula and min NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(34) ##STR00008##

(35) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.63 (d, J=9.2 Hz, 1H), 7.46-7.44 (m, 2H), 7.35-7.28 (m, 2H), 7.17-7.13 (m, 2H), 7.09 (d, J=2.8 Hz, 1H), 7.01-6.97 (m, 6H), 6.88 (dd, J=8.8, 2.8 Hz, 1H), 6.68 (d, J=2.4 Hz, 1H), 6.64 (dd, J=8.4, 2.8 Hz, 1H), 5.45 (s, 1H), 3.88 (s, 3H), 3.86 (s, 3H).

Example 22: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(5-chloro-2-hydroxyphenyl)-1-phenyl-2-propene-1-ketone to Prepare Cyclo-Penta[c]Chromene Compound

(36) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 3-(5-chloro-2-hydroxyphenyl)-1-phenyl-2-propene-1-ketone (0.1293 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 68%.

(37) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(38) ##STR00009##

(39) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.61 (d, J=2.4 Hz, 1H), 7.54-7.52 (m, 1H), 7.43-7.41 (m, 3H), 7.32-7.27 (m, 3H), 7.16-7.12 (m, 2H), 7.04-6.95 (m, 7H), 5.39 (s, 1H).

Example 23: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(5-bromo-2-hydroxyphenyl)-1-phenyl-2-propene-1-ketone to Prepare Cyclo-Penta[c]Chromene Compound

(40) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 3-(5-bromo-2-hydroxyphenyl)-1-phenyl-2-propene-1-ketone (0.1515 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 68%.

(41) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(42) ##STR00010##

(43) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.78 (d, J=2.0 Hz, 1H), 7.57-7.56 (m, 1H), 7.50-7.43 (m, 5H), 7.34-7.31 (m, 1H), 7.17-7.13 (m, 2H), 7.05-6.96 (m, 7H), 5.37 (s, 1H).

Example 24: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(2-hydroxy-5-methylphenyl)-1-phenyl-2-propene-1-ketone to Prepare Cyclo-Penta[c]Chromene Compound

(44) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 3-(2-hydroxy-5-methylphenyl)-1-phenyl-2-propene-1-ketone (0.1191 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 82%.

(45) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(46) ##STR00011##

(47) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.52-7.47 (m, 2H), 7.46-7.44 (m, 2H), 7.30-7.26 (m, 2H), 7.15-7.11 (m, 4H), 7.06 (s, 1H), 7.00-6.98 (m, 6H), 5.27 (s, 1H), 2.35 (s, 3H), 2.28 (s, 3H).

Example 25: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(2-hydroxy-5-methoxyphenyl)-1-phenyl-2-propene-1-one to Prepare Cyclo-Penta[c]Chromene Compound

(48) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 3-(2-hydroxy-5-methoxyphenyl)-1-phenyl-2-propene-1-one (0.1271 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 77%.

(49) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(50) ##STR00012##

(51) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.44 (d, J=9.2 Hz, 1H), 7.38-7.36 (m, 2H), 7.23-7.20 (m, 1H), 7.09-7.04 (m, 3H), 7.01 (s, 1H), 6.95-6.92 (m, 7H), 6.87-6.80 (m, 2H), 5.07 (s, 1H), 3.71 (s, 3H), 3.50 (s, 3H).

Example 26: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(2-chloro-6-hydroxyphenyl)-1-phenyl-2-propene-1-one to Prepare Cyclo-Penta[c]Chromene Compound

(52) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0273 g, 0.025 mmol, 5 mol %), 3-(2-chloro-6-hydroxyphenyl)-1-phenyl-2-propene-1-one (0.1293 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 65%.

(53) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(54) ##STR00013##

(55) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.53 (dd, J=8.0, 1.2 Hz, 1H), 7.43-7.41 (m, 2H), 7.36 (dd, J=7.6, 1.2 Hz, 1H), 7.30-7.24 (m, 3H), 7.16-7.11 (m, 4H), 7.06 (dd, J=8.0, 1.2 Hz, 1H), 7.01-7.00 (m, 4H), 6.89 (dd, J=8.0, 0.8 Hz, 1H), 5.33 (s, 1H).

Example 27: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 1-(3-chlorophenyl)-3-(2-hydroxyphenyl)-2-propene-1-one to Prepare Cyclo-Penta[c]Chromene Compound

(56) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0273 g, 0.025 mmol, 5 mol %), 1-(3-chlorophenyl)-3-(2-hydroxyphenyl)-2-propene-1-one (0.1293 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 55%.

(57) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(58) ##STR00014##

(59) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.70 (dd, J=8.4, 1.2 Hz, 1H), 7.61 (d, J=8.0 Hz, 1H), 7.46-7.45 (m, 1H), 7.43 (dd, J=7.6, 1.2 Hz, 1H), 7.40-7.33 (m, 4H), 7.24-7.23 (m, 1H), 7.16 (t, J=8.0 Hz, 1H), 7.11-7.08 (m, 2H), 7.06-7.04 (m, 2H), 7.00 (t, J=7.6 Hz, 1H), 6.95-6.92 (m, 2H), 5.33 (s, 1H).

Example 28: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed the Reaction of 1-(3-bromophenyl)-3-(2-hydroxyphenyl)-2-propen-1-one to Prepare Cyclopenta[c]Chromene Compound

(60) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0381 g, 0.035 mmol, 7 mol %), 1-(3-bromophenyl)-3-(2-hydroxyphenyl)-2-propen-1-one (0.1515 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 54%.

(61) The theoretical molecular formula and NMR spectrum of the product obtained are shown as below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(62) ##STR00015##

(63) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.69 (d, J=8.0 Hz, 1H), 7.61-7.59 (m, 2H), 7.50 (d, J=8.0 Hz, 1H), 7.43-7.41 (m, 2H), 7.38-7.34 (m, 2H), 7.26-7.24 (m, 1H), 7.21-7.19 (m, 1H), 7.13-7.06 (m, 5H), 7.01-6.93 (m, 2H), 5.35 (s, 1H).

Example 29: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(2-hydroxyphenyl)-1-(3-methoxyphenyl)-2-propen-1-one to Prepare Cyclopenta[c]Chromene Compound

(64) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 3-(2-hydroxyphenyl)-1-(3-methoxyphenyl)-2-propen-1-one (0.1271 g, 0.5 mmol) and chloro-benzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 75%.

(65) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(66) ##STR00016##

(67) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.70 (dd, J=8.0, 1.2 Hz, 1H), 7.58 (d, J=8.4 Hz, 1H), 7.44 (dd, J=7.6, 1.2 Hz, 1H), 7.36-7.30 (m, 2H), 7.22-7.18 (m, 2H), 7.11-6.97 (m, 5H), 6.89-6.87 (m, 2H), 6.74 (d, J=7.6 Hz, 1H), 6.61 (dd, J=8.0, 2.0 Hz, 1H), 6.47-6.46 (m, 1H), 5.49 (s, 1H), 3.48 (s, 3H), 3.47 (s, 3H).

Example 30: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 1-(4-chlorophenyl)-3-(2-hydroxyphenyl)-2-propene-1-ketone to Prepare Cyclopenta[c]Chromene Compound

(68) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 1-(4-chlorophenyl)-3-(2-hydroxyphenyl)-2-propene-1-ketone (0.1293 g, 0.5 mmol) and chloro-benzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 70%.

(69) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(70) ##STR00017##

(71) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.69 (dd, J=8.4, 1.6 Hz, 1H), 7.59 (dd, J=8.4, 1.2 Hz, 1H), 7.45-7.33 (m, 5H), 7.25 (t, J=3.6 Hz, 1H), 7.23-7.16 (m, 2H), 7.12-6.99 (m, 5H), 6.92 (d, J=8.4 Hz, 2H), 5.33 (s, 1H).

Example 31: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 1-(4-bromo-phenyl)-3-(2-hydroxyphenyl)-2-propene-1-ketone to Prepare Cyclopenta[c]Chromene Compound

(72) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 1-(4-bromophenyl)-3-(2-hydroxyphenyl)-2-propene-1-ketone (0.1515 g, 0.5 mmol) and chloro-benzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 80%.

(73) The theoretical molecular formula and main NMR test data of the products obtained are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(74) ##STR00018##

(75) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.68 (dd, J=8.0, 1.6 Hz, 1H), 7.57 (dd, J=8.4, 1.2 Hz, 1H), 7.41 (dd, J=7.6, 1.6 Hz, 1H), 7.37-7.28 (m, 6H), 7.24-7.20 (m, 1H), 7.16 (d, J=8.4 Hz, 2H), 7.09-7.03 (m, 3H), 6.82 (d, J=8.4 Hz, 2H), 5.34 (s, 1H).

Example 32: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzes the Reaction of 1-(4-[1,1′-biphenyl])-3-(2-hydroxybenzene)-2-propen-1-one to Prepare Cyclopenta[c]Chromene Compound

(76) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 1-(4-[1,1′-biphenyl])-3-(2-hydroxybenzene)-2-propen-1-one (0.1501 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 70%.

(77) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(78) ##STR00019##

(79) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.72 (dd, J=8.0, 1.6 Hz, 1H), 7.61 (dd, J=8.0, 1.2 Hz, 1H), 7.52-7.49 (m, 2H), 7.46 (dd, J=7.2, 1.6 Hz, 1H), 7.42-7.39 (m, 4H), 7.35-7.27 (m, 10H), 7.24-7.18 (m, 3H), 7.12-7.10 (m, 2H), 7.07-7.03 (m, 3H), 5.45 (s, 1H).

Example 33: [Yb(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN Catalyzed Reaction of 3-(2-hydroxyphenyl)-1-(4-methoxyphenyl)-2-propen-1-one to Prepare Cyclopenta[c]Chromene Compound

(80) [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0163 g, 0.015 mmol, 3 mol %), 3-(2-hydroxyphenyl)-1-(4-methoxyphenyl)-2-propen-1-one (0.1271 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. 2-Naphthalenethiol (0.0961 g, 0.6 mmol) and chlorobenzene (1 mL) were then added, stirred and refluxed for 36 hours after mixing. Water was added to quench the reaction, extracting three times with ethyl acetate (10 mL×3), drying the extract with anhydrous sodium sulfate, filtering, removing the solvent under reduced pressure, and finally running flash column chromatography on a silica gel column (Eluent: V ethyl acetate:V petroleum ether is 1:20 to 1:15) to obtain a red-brown solid. The solid was placed under an oil pump and continued to be dried for about one day. The yield was 74%.

(81) The theoretical molecular formula and NMR spectrum of the product obtained are shown below. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

(82) ##STR00020##

(83) .sup.1H NMR (400 MHz, CDCl.sub.3) δ 7.67 (dd, J=8.0, 1.6 Hz, 1H), 7.58-7.56 (m, 1H), 7.45-7.40 (m, 3H), 7.36-7.29 (m, 2H), 7.23-7.17 (m, 1H), 7.10-7.08 (m, 1H), 7.06-7.03 (m, 1H), 7.00 (s, 1H), 6.94 (d, J=8.4 Hz, 2H), 6.67 (d, J=8.8 Hz, 2H), 6.59 (d, J=8.8 Hz, 2H), 5.48 (s, 1H), 3.76 (s, 3H), 3.72 (s, 3H).