Oxone-aceton mediated metal free preparation of syn-diols

Patent metadata

Field	Value
Publication number	US-10774060-B2
Application number	US-201414392212-A
Country	US
Kind code	B2
Filing date	Jun 25, 2014
Priority date	Jun 25, 2013
Publication date	Sep 15, 2020
Grant date	Sep 15, 2020

Abstract

The present invention disclose a simple and high yielding process of Oxone-acetone mediated metal free syn-dihydroxylation of benzo fused olefins of formula (II) to obtain library of dioxolo compounds of formula (I). The invention further disclose a simple and high yielding process of Oxone-acetone mediated metal free syn-dihydroxylation of stilbene and its derivatives of formula (III) thereof. Also disclosed herein is Wacker-type oxidation of benzo-fused olefins of formula (X). The invention further disclose compounds of formula (I) which can be useful for the treatment of HIV, cancer or malaria.

First claim

We claim:

1. A simple, one step, stereospecific, oxone-acetone mediated, metal free process for preparation of a compound of Formula (I),

wherein,
R2 and R3 together represent dioxolo

and R1, or R4, or R5 that do not form the dioxolo group are independently selected from the group consisting of hydrogen, alkoxy, unsubstituted or substituted phenyl, halogen, hydroxy, nitro, amino, carbonyl, —COOH, cyano, azo, unsubstituted or substituted benzyl group, C1 to C6 cyclo rings optionally having one or more heteroatoms selected from N, O or S, heteroaryl, unsubstituted linear or branched alkyl radical having 2 to 10 C atoms, substituted linear or branched alkyl radical having 2 to 10 C atoms, in which one or more CH2 groups optionally each independently of one another be replaced by —C=O, —N—, —O—, —S—, —CH═CH—, or —C≡C—, unsubstituted linear or branched alkenyl radical having 2 to 10 C atoms, substituted linear or branched alkenyl radical having 2 to 10 C atoms, unsubstituted linear or branched alkynyl radical having 2 to 10 C atoms, and substituted linear or branched alkynyl radical having 2 to 10 C atoms;
Y is —CHR6, or heteroatom; wherein R6 is selected from hydrogen, methyl, and phenyl;
R is hydrogen or alkoxy; and
n is 0 or 1; with the proviso when n=0, Formula I forms five membered ring or three carbon chain, or when n=1, Formula I forms six membered ring; said process comprising:
(i) mixing compound of Formula (II):

wherein,
R1′, or R3′, or R5′ are independently selected from the group consisting of hydrogen, alkoxy, unsubstituted or substituted phenyl, halogen, hydroxy, nitro, amino, carbonyl, —COOH, cyano, azo, unsubstituted or substituted benzyl group, C1 to C6 cyclo rings which optionally having one or more heteroatoms selected from N, O or S, heteroaryl, unsubstituted linear or branched alkyl radical having 2 to 10 C atoms, substituted linear or branched alkyl radical having 2 to 10 C atoms, in which one or more CH2 groups optionally each independently of one another be replaced by —C=O, —N—, —O—, —S—, —CH═CH—, or —C≡C—, unsubstituted linear or branched alkenyl radical having 2 to 10 C atoms, substituted linear or branched alkenyl radical having 2 to 10 C atoms; unsubstituted linear or branched alkynyl radical having 2 to 10 C atoms and substituted linear or branched alkynyl radical having 2 to 10 C atoms;
R2′ is hydrogen;
R4′ is none;
Y′ is —CHR6′, or heteroatom; wherein R6′ is selected from hydrogen, methyl, and phenyl;
R′ is hydrogen or alkoxy;
n′ is 0 or 1; with the proviso when n′=0, Formula II forms five membered ring or three carbon chain, or when n′=1, Formula II forms six membered ring; and
‘. . . ’ between CR1 ‘R2’ and CR3′ represents a single bond, and ‘. . . ’ between CR3′ and CR4R5′ represents a double bond;
with powdered Oxone (H 3 K 5 S 4 O 18 ) and sodium bicarbonate (NaHCO 3 ) in a ratio in a range of 2:3 in a mixture of acetone, ethyl acetate, and water to obtain a reaction mixture;
(ii) stirring the reaction mixture obtained in step (i) at room temperature in a range of 25 to 30° C. for a period in a range of 2-5 hours; and
(iii) evaporating excess acetone under reduced pressure after completion of reaction, portioning the remaining reaction mixture between water and ethyl acetate and followed by purification to obtain compound of Formula I.

2. The process as claimed in claim 1 , wherein the mixture of acetone, ethyl acetate, and water is in a ratio of 5:1:1.

3. The process as claimed in claim 1 , wherein the compound of Formula I has the structure of Formula (VI):

wherein R′ is selected from hydrogen, alkoxy, phenyl which is unsubstituted or substituted, halogen, hydroxy, nitro, amino, carbonyl, —COOH, cyano, azo, benzyl group which is unsubstituted or substituted; C1 to C6 cyclo rings which may have one or more heteroatoms selected from N, O or S; a heteroaryl; a linear or branched alkyl radical having 2 to 10 C atoms which is unsubstituted or substituted; in which one or more CH2 groups may each, independently of one another, be replaced by —C═O, —N—, —O—,—S—, or —CH═CH—; a linear or branched alkenyl radical having 2 to 10 C atoms which is unsubstituted or substituted; and a linear or branched alkynyl radical having 2 to 10 C atoms which is unsubstituted or substituted.

4. The process as claimed in claim 1 , wherein the compound of Formula I is selected from the group consisting of:
(i) 2,2-dimethyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2a);
(ii) 2,2-dimethyl-3a-propyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2b);
(iii) 3a-(3-chloropropyl)-2,2-dimethyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2c);
(iv) 8-(4-bromobutyl)-2,2-dimethyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2d);
(v) 8-benzyl-2,2-dimethyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2e);
(vi) 3a-benzyl-2,2-dimethyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2f);
(vii) 3a-isopropyl-2,2-dimethyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2g);
(viii) 3a-cyclohexyl-2,2-dimethyl-8,8a-dihydro-3aH-indeno[2,1-d][1,3]dioxole (2h);
(ix) 2,2-dimethyl-3a-phenyl-8,8a-dihydro-3aH-indeno[1,2-d][1,3]dioxole (2i);
(x) 7-(2,2-dimethyl-8,8a-dihydro-3aH-indeno[2,1-d][1,3]dioxol-3a-yl)heptan-2-one (2j);
(xi) 3a-(but-3-enyl)-2,2-dimethyl-8,8a-dihydro-3aH-indeno[2,1-d][1,3]dioxole (2m); and
(xii) 2,2-dimethyl-3a-(2-(oxiran-2-yl)ethyl)-3a,8a-dihydro-8H-indeno[1,2-d][1,3]dioxole (6).

5. A simple, one step, stereospecific, oxone-acetone mediated, metal free process for preparation of a compound of Formula (I),

wherein,
R2 is hydrogen and R1, R3 and R4 that do not form the dioxolo group are independently selected from the group consisting of hydrogen, alkoxy, unsubstituted or substituted phenyl, halogen, hydroxy, nitro, amino, carbonyl, —COOH, cyano, azo, unsubstituted or substituted benzyl group, C1 to C6 cyclo rings optionally having one or more heteroatoms selected from N, O or S, heteroaryl, unsubstituted linear or branched alkyl radical having 2 to 10 C atoms, substituted linear or branched alkyl radical having 2 to 10 C atoms, in which one or more CH2 groups optionally each independently of one another be replaced by —C═O, —N—, —O—, —S—, —CH═CH—, or —C≡C—, unsubstituted linear or branched alkenyl radical having 2 to 10 C atoms, substituted linear or branched alkenyl radical having 2 to 10 C atoms, unsubstituted linear or branched alkynyl radical having 2 to 10 C atoms, and substituted linear or branched alkynyl radical having 2 to 10 C atoms;
Y is —CHR6; wherein R6 is selected from hydrogen, methyl, and phenyl, and wherein R5 together with CH of CHR6 represent dioxolo

R is hydrogen or alkoxy; and
n is 1, Formula I forms six membered ring; said process comprising:
(i) mixing compound of Formula (II) c :

wherein,
R1′, or R3′, or R5′ are independently selected from the group consisting of hydrogen, alkoxy, unsubstituted or substituted phenyl, halogen, hydroxy, nitro, amino, carbonyl, —COOH, cyano, azo, unsubstituted or substitu

Assignees

• Council Scient Ind Res

Inventors

• Ramana Chepuri Venkata
• Phatake Ravindra Suresh

Classifications

• Y02A50/30

  Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change · CPC title

• C07C49/755

  a keto group being part of a condensed ring system with two or three rings, at least one ring being a six-membered aromatic ring · CPC title

• C07C49/784

  with all keto groups bound to a non-condensed ring · CPC title

• C07D317/12

  with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms · CPC title

• C07C49/697

  containing six-membered aromatic rings · CPC title