DDQ mediated one step dimerisation of beta-asarone or beta-asarone rich acorus calamus oil in the formation of novel neolignan

a technology of acorus calamus and beta-asarone, which is applied in the field of ddq mediated one step dimerisation of beta-asarone or beta-asarone rich acorus calamus oil in the formation of novel neolignan, can solve the problems of large reaction volume, difficult reproducibility, and maintain temperature, and achieve high purity of neolignan and side products

Inactive Publication Date: 2003-10-02
COUNCIL OF SCI & IND RES
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0006] Another object of the present invention is to utilize toxic .beta.-asarone rich calamus oil of tetraploid or hexaploid varieties (distributed extensively in Asian countries), thereby, enhancing the profitable use thereof.

Problems solved by technology

But this method is cumbersome and leads to a large reaction volumes, and is also difficult to reproduce.
However, above methods have a number of disadvantages including special handling of reagents, maintaining temperature below zero degree, expensive reagents and overall low yield, hence, none of the synthetic methods can be scaled up for industrial exploitation.

Method used

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  • DDQ mediated one step dimerisation of beta-asarone or beta-asarone rich acorus calamus oil in the formation of novel neolignan
  • DDQ mediated one step dimerisation of beta-asarone or beta-asarone rich acorus calamus oil in the formation of novel neolignan
  • DDQ mediated one step dimerisation of beta-asarone or beta-asarone rich acorus calamus oil in the formation of novel neolignan

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0043] Preparation 2,4,5-trimethoxyphenylpropane (dihydro asarone): The starting material 2,4,5-trimethoxyphenylpropane is prepared by hydrogenation of either .beta.-asarone (isolated from Acorus calamus oil) or commercially available calamus oil rich in asarones (i.e. .beta. and / or .alpha.,.gamma.-asarone) content.

[0044] (a) Hydrogenation of .beta.-asarone into 2,4,5-trimethoxyphenylprop-ane (dihydro asarone): .beta.-asarone was isolated by loading the crude calamus oil (17.00 g) on silica gel column and then eluted the column with hexane to remove unwanted non-polar compounds. Subsequent elution with hexane-ethylacetate mixture with increasing proportion of ethylacetate upto 10% gave 13.94 g (82%, w / w) of pure liquid; R.sub.f 0.63 (hexane:toluene: ethylacetate=1:1:0.1); .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta.6.84 (1H, s, H-6), 6.53 (1H, s, H-3), 6.50 (1H, dd, J=15.8 Hz and 1.5 Hz, H-1'), 5.78 (1H, dq, J=6.5 Hz and 15.8 Hz, H-2'), 3.88, 3.83 and 3.79 (s, 3H, each, 3-OCH.sub.3) an...

example ii

[0047] Preparation of 3-ethyl-2-methyl-3-(2",4",5"-trimethoxy)phenyl-1-(2'-,4',5'-trimethoxy)phenyl-1-propene: DDQ (6.13-7.97 g) was added over a period of 10-15 min to a ice cold and well stirred solution of 2,4,5-trimethoxyphenylpropane (5.67 g, 0.027 mol) in acetic acid (55 mL) and stirring was continued at room temperature for over night. The precipitated solid of DDQH.sub.2 was filtered and the filter cake washed twice with acetic acid. The combined acetic acid layer was evaporated and mixture was poured into water and extracted with dichloromethane (3.times.70 mL). The combined organic layer were washed with brine (3.times.15 mL), 10% sodium bicarbonate (2.times.10 mL), brine (3.times.15 mL) and dried over sodium sulphate. The residue obtained on evaporation of the solvents was chromatographed on silica gel using hexane-ethyl acetate mixture with increasing proportion of ethyl acetate upto 40% and the fractions having similar R.sub.f were mixed which after evaporation of solve...

example iii

[0052] Preparation of 3-ethyl-2-methyl-3-(2",4",5"-trimethoxy)phenyl-1-(2'-,4',5'-trimethoxy)phenylpropane: 0.20 mg of 5% Pd / C was added to a solution of 3-ethyl-2-methyl-3-(2",4",5"-trimethoxy)phenyl-1-(2',4',5'-tr-imethoxy)phenyl-1-propene (0.35 g, 0.84 mmole) in ethyl acetate (40 mL) and methanol (25 mL) and was shaken under atmosphere of hydrogen in paar reactor (5-20 psi) at room temperature till the disappearance of starting material. The catalyst was filtered and the solvent was removed under reduced pressure, which afforded a liquid. The liquid was purified on silica gel using above eluent system (hexane-ethyl acetate mixture) gave 3-ethyl-2-methyl-3-(2",4",5"-trimethoxy)phenyl-1-(2',4',5'-trimethoxy)phe-nylpropane (0.32 g) as a liquid in 91% yield; R.sub.f 0.47 (20% ethylacetate in hexane); .sup.1H NMR (CDCl.sub.3) .delta.6.77 (1H, s, H-3"), 6.68 (1H, d, H-6"), 6.54 (1H, d, H-6'), 6.51(1H, s, H-3'), 3.96 (6H,s, 2'-OCH.sub.3 and 2"-OCH.sub.3), 3.84 (6H, s, 4'-OCH.sub.3 and 4...

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Abstract

The present invention relates to a novel neolignan (NEOLASA-I) 3-ethyl-2-methyl-3-(2'',4'',5''-trimethoxy-phenyl-1-(2',4',5'-trimethoxy)phenyl-1-(2',4',5'-trimethoxy)phenyl-1-propene and a process for the preparation of high purity, higher yield neolignan, alpha-asarone, 2,4,5-trimethoxy-phenyl propionone from beta-asarone or beta-asarone rich Acorus calamus oil containing alpha and gamma-asarone by hydrogenating and dimerizing by treatment with DDQ in presence of an organic acid.

Description

[0001] The present invention relates to "DDQ mediated one step dimerisation of dihydro product of toxic .beta.-asarone rich Acorus calamus oil towards formation of novel neolignan: 3-ethyl-2-methyl-3-(2",-4",5"-trimethoxy)phenyl-1-(2',4',5'-trimethoxy)phenyl-1-propene" in which 2,4,5-trimethoxyphenylpropane (a dihydro product of asarone obtained via hydrogenation of .beta.-asarone rich Acorus calamus oil) of the formula (I), undergoes dimerisation in a single step towards formation of neolignan 3-ethyl-2-methyl-3-(2",4",5"-trimethoxy)phenyl-1-(2',4',5'-trim-ethoxy)phenyl-1 propene (named as NEOLASA-I) of the formula II along with biologically active .alpha.-asarone and 1-(2,4,5-trimethoxy)phenyl-1-prop-anone as side products, thereof. Further, neolignan (NEOLASA-I) is hydrogenated to obtain its corresponding dihydro product 3-ethyl-2-methyl-3-(2",4",5"-trimethoxy) phenyl-1-(2',4',5'-trimethoxy)ph-enylpropane (named as NEONLASA-II) so as to confirm the structure as well as to determi...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07C41/30C07C41/18C07C41/36C07C41/38C07C43/20C07C43/205C07C43/215
CPCC07C43/215C07C43/2055
Inventor SINHA, ARUN KUMARJOSHI, BHUPENDRA PRASADACHARYA, RUCHI
Owner COUNCIL OF SCI & IND RES
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