A kind of method of asymmetric catalytic synthesis (r)-4,7-dimethyl-1-tetralone

A technology of tetralone and dimethyl, which is applied in the field of new asymmetric catalytic synthesis of -4,7-dimethyl-1-tetralone, which can solve the problems of limiting biological activity research and synthetic application research

Inactive Publication Date: 2017-03-22
CHINA AGRI UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the content in related plants is very small, which limits further research on its biological activity and synthetic application.

Method used

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  • A kind of method of asymmetric catalytic synthesis (r)-4,7-dimethyl-1-tetralone
  • A kind of method of asymmetric catalytic synthesis (r)-4,7-dimethyl-1-tetralone
  • A kind of method of asymmetric catalytic synthesis (r)-4,7-dimethyl-1-tetralone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Synthesis of (S)-benzyl p-toluene propionate 2

[0024] Under the protection of argon, quickly weigh anhydrous CoI 2 (0.63g, 2mmol) in a 200mL Schlenk reaction flask, vacuum-dried for 30min. After cooling to room temperature, add (4S,4'S)-bis(4-benzyloxazolin-2-yl)-propane L1 (0.87g, 2.4mmol), inject anhydrous tetrahydrofuran (15mL) with a syringe, and stir at room temperature 1h. Then racemic benzyl 2-bromophenylpropionate (4.86 g, 20 mmol) was added, and after the addition was complete, the temperature of the mixture was lowered to -78°C. p-Tolylmagnesium bromide (30mL, 1.0M THF solution, 30mmol) was added slowly, and the stirring reaction was continued at -78°C for 8h. After the reaction was completed, saturated ammonium chloride aqueous solution (20 mL) was added to quench the reaction, and the organic layer was separated. The aqueous layer was extracted with ether (3 x 20 mL), and the organic layers were combined and washed with saturated aqueous sodium chlorid...

Embodiment 2

[0028] Synthesis of (S)-p-tolylpropanol 3

[0029] Under the protection of argon, inject anhydrous CH with a syringe 2 Cl 2 (25mL) was injected into a 100mL Schlenk reaction flask, and (S)-benzyl p-toluenepropionate 2 (3.81g, 15mmol) was slowly added. The temperature of the mixture was lowered to -78°C, and diisobutylaluminum hydride (DIBAL-H) ​​(22 mL, 1.5M solution in toluene, 33 mmol) was slowly added dropwise using a syringe pump. At this temperature, the reaction was stirred for 30 minutes, then the temperature was raised to 0° C., and the reaction was stirred for another 30 minutes. After the reaction, the temperature of the reaction solution was lowered to -78°C, and the reaction was quenched with methanol (1 mL). Then, an aqueous potassium sodium tartrate solution (66 mL, 0.5 M, 33 mmol) was added, the temperature of the mixture was raised to room temperature, and stirring was continued for 12 h. Separate the organic layer and the aqueous layer with CH 2 Cl 2 (3 ...

Embodiment 3

[0031] Synthesis of (S)-2-p-tolyl-1-bromopropane 4

[0032] Add (S)-p-tolylpropanol 3 (1.50g, 10mmol) and triphenylphosphine (3.15g, 12mmol) into a 100mL reaction flask, then add CH 2 Cl 2 (33mL), stir well. Add CBr slowly 4 (3.42g, 10.3mmol), the temperature of the reaction solution was raised to room temperature, and the stirring reaction was continued for 4h. Concentrate under reduced pressure to remove the solvent, add petroleum ether (40 mL) to the residue, filter with suction, wash the filter residue with petroleum ether, and combine the filtrates. with anhydrous Na 2 SO 4 After drying and concentration under reduced pressure, it was purified by silica gel column chromatography (petroleum ether) to obtain (S)-2-p-tolyl-1-bromopropane 4 (2.01g, yield 94%, optical purity 92%) in light yellow oily liquid . [α] D 20 =-22.7(c 1.3, CHCl 3 ). 1 H NMR (300MHz, CDCl 3 )δ7.15(d, J=8.3Hz, 2H), 7.11(d, J=8.3Hz, 2H), 3.58(dd, J=9.8,6.1Hz, 1H), 3.46(dd, J=9.8,8.0 Hz,1H),3...

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Abstract

The invention discloses a method for asymmetrically catalyzing and synthesizing (R)-4, 7-dimethyl-1-tetralone. According to the method, an asymmetrical Kumada cross coupling reaction is conducted on racemization 2-halogenated propionate ester catalyzed by bis oxazoline / cobalt and a methyl phenyl grignard reagent, and (S)-P-toluene propionate ester 2 is firstly generated; then, (S)-P-toluene propionate ester 2 is reduced to (S)-P-toluene propyl alcohol 3 through diisobutylaluminium hydride (DIBAL-H), and then (R)-4-p-methylphenyl-1-amylene 5 is obtained through bromine generation and coupling with and vinyl grignard reagent; next, a hydroboration-oxidation reaction and a Dess-Martin oxidizing reaction are sequentially conducted, and (R)-4-p-methylphenyl valeraldehyde 6 is obtained; finally, oxidation is conducted through silver oxide, an intramolecular Fourier acyl reaction is conducted, and (R)-4,7-dimethyl-1-tetralone is obtained in a ring-closure synthesis mode. The synthesis route is simple and concise, 8 reactions are conducted in all, the total yield is 27%, and the optical purity of a product is 90%.

Description

technical field [0001] The invention relates to the field of chemical synthesis of natural products, in particular to a novel method for asymmetrically catalytically synthesizing (R)-4,7-dimethyl-1-tetralone. Background technique [0002] 4,7-Dimethyl-1-tetralone (4,7-dimethyl-1-tetralone) is a common type of natural terpenoids, mainly found in salvia miltiorrhiza, lavender, cistus, cistus, etc. in the volatile oils of plants (Ali, A.; Tabanca, N.; Demirci, B.; Blythe, E.K.; Ali, Z.; Baser, K.H.C.; Khan, I.A., J. Agric. Food Chem. 2015, 63(2) , 447-456. Kaiser, R.; Lamparsky, D., Helv. Chim. Acta 1983, 66(6), 1843-1849. Weyerstahl, P.; Marschall, H.; Weirauch, M.; Thefeld, K. ; Surburg, H., Flavour Fragrance J.1998, 13(5), 295-318. Kivcak, B.; Akay, S.; Demirci, B.; Baser, K.H.C., Pharm.Biol. ), 360-366.). Studies by Imelouane et al. have shown that lavender essential oil containing 4,7-dimethyl-1-tetralone has anti-oxidative activity, and at the same time has anti-oxidat...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C49/67C07C45/46
CPCC07B2200/07C07C1/326C07C17/16C07C29/147C07C45/29C07C45/46C07C51/295C07C67/343C07C49/67C07C57/30C07C47/228C07C15/44C07C22/04C07C33/20C07C69/612
Inventor 钟江春边庆花武林周云李硕宁杨燕青王敏
Owner CHINA AGRI UNIV
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