Method for preparing cyclopenta[c]chromium compound

Abstract

The present invention discloses a method for preparing a cyclopenta[c]chromene compound. A cationic rare earth compound [Ln(CH).sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN is used as a catalyst, and p-methyl thiophenol is used as an accelerator for a catalytic reaction of a chalcone compound so as to prepare a product; and Ln, contained in the catalyst, represents a positive trivalent rare earth metal ion and is selected from one of La, Nd, Sm, Gd and Yb. According to the method, the starting materials are easy to obtain, the reaction process is simple, the catalyst usage is low, the catalyst is universally applicable to various substituted 2-hydroxy chalcones, and the obtained cyclopenta[c]chromene compound has not been reported. The catalyst synthesis method is simple and easy to obtain, and the yield of the target product is high.

Claims

1. A method for preparing a cyclopenta[c]chromene compound, comprising the following steps: under anhydrous and anaerobic conditions, using a chalcone compound as a reactant, using a cationic rare earth compound as a catalyst, using p-methyl thiophenol as an accelerator, and reacting in an organic solvent to prepare the cyclopenta[c]chromene compound, wherein the cationic rare earth compound has the following chemical structure: ##STR00008## wherein, Ln represents a positive trivalent rare earth metal ion; the chalcone compound has the following chemical structure: ##STR00009## 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; the anhydrous and oxygen-free conditions are inert atmosphere conditions.

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

4. The method for preparing the 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 the cyclopenta[c]chromene compound according to claim 4, wherein the molar ratio of the catalyst:the chalcone compound:the accelerator is (0.02 to 0.05):1:(1.1 to 1.2).

6. The method for preparing a 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 the 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

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

(1) Under the protection of argon, 0.70 g (2.5 mmol) of YbCl.sub.3 and 1.00 g (7.5 mmol) of anhydrous AlCl.sub.3 were added into a dehydrated and deoxidized reaction flask in a molar ratio is 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. to obtain crystalline [Yb(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN, a yield of 46%.

(2) Other [Ln(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN catalysts could be prepared using the same method of Example 1, with different rare earth chlorides.

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-hydroxy-chalcone to prepare cyclopenta[c]chromene compound

(3) [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-hydroxy-chalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, stirred for 2 minutes. p-Methyl thiophenol (0.0745 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 a flash column chromatography on a silica gel column (Eluent: V.sub.ethyl acetate:V.sub.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%. When the accelerator was changed to 2% or 5%, the yield was 65% or 71%, respectively. When the solvent was changed to acetonitrile or toluene, the yield was 45% or 46%, respectively. When the solvent was changed to DMF, the reaction cannot proceed. When the reaction was changed to 100 ° C., the yield was 52%. When the catalyst was changed to “3% YbCl.sub.3 +9% AlCl.sub.3,” the yield was 25%. When the catalyst was changed 3% YbCl.sub.3, the yield was 20%. When the accelerator was changed to 1-mercaptodecane, the yield was 24%.

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

(5) ##STR00005##

(6) .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

[La(CH.SUB.3.CN)9].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN catalyzed reaction of 2-hydroxy-chalcone to prepare cyclopenta[c]chromene compound

(7) [La(CH.sub.3CN)9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0158 g, 0.015 mmol, 3 mol %), 2-hydroxy-chalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. p-Methyl thiophenol (0.0745 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.sub.ethyl acetate:V.sub.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%.

EXAMPLE 4

[Nd(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN catalyzed reaction of 2-hydroxy-chalcone to prepare cyclopenta[c]chromene compound

(8) [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-hydroxy-chalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. p-Methyl thiophenol (0.0745 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.sub.ethyl acetate:V.sub.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 5

[Sm(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN catalyzed reaction of 2-hydroxy-chalcone to prepare cyclopenta[c]chromene compound

(9) [Sm(CH.sub.3CN).sub.9].sup.3+[(AlCl.sub.4).sub.3].sup.3−.CH.sub.3CN (0.0160 g, 0.015 mmol, 3 mol %), 2-hydroxy-chalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. p-Methyl thiophenol (0.0745 g, 0.6 mmol) and chlorobenzene (1 mL) were added, and 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.sub.ethyl acetate:V.sub.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 6

[Gd(CH.SUB.3.CN).SUB.9.].SUP.3+.[(AlCl.SUB.4.).SUB.3.].SUP.3−..CH.SUB.3.CN catalyzed reaction of 2-hydroxy-chalcone to prepare cyclopenta[c]chromene compound

(10) [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-hydroxy-chalcone (0.1121 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. p-Methyl thiophenol (0.0745 g, 0.6 mmol) and chlorobenzene (1 mL) were added, and 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.sub.ethyl acetate:V.sub.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 60%.

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 3-(4-chloro-2-hydroxyphenyl)-1-phenyl-2-propen-1-one 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(0.0273 g, 0.025 mmol, 3 mol %), 3-(4-chloro-2-hydroxyphenyl)-1-phenyl-2-propen-1-one (0.1293 g, 0.5 mmol) and chloro-benzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for 2 minutes. p-Methyl thiophenol (0.0745 g, 0.6 mmol) and chlorobenzene (1 mL) were added, and 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.sub.ethyl acetate:V.sub.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%. When p-methyl thiophenol was changed to 2-naphthol (0.0961 g, 0.6 mmol), the yield was 55%.

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

(13) ##STR00006##

(14) .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 8

[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-ketone to prepare cyclopenta[c] chrom-ene compound

(15) [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-ketone (0.1272 g, 0.5 mmol) and chlorobenzene (1 mL) were added into a dehydrated and deoxidized reaction flask, and stirred for a few minutes. p-Methyl thiophenol (0.0745 g, 0.6 mmol) and chlorobenzene (1 mL) were added, and 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.sub.ethyl acetate:V.sub.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%. When p-methyl thiophenol was changed to 2-naphthol (0.0961 g, 0.6 mmol), the yield was 29%.

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

(17) ##STR00007##

(18) .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).