WO2006117800B1

WO2006117800B1 - Novel 3, 4-propylenedioxythiophene derivatives with pendant functional groups

Info

Publication number: WO2006117800B1
Application number: PCT/IN2006/000063
Authority: WO
Inventors: Anil Kumar; Sarada Prasad Mishra
Original assignee: Indian Institute of Technology Bombay
Current assignee: Indian Institute of Technology Bombay
Priority date: 2005-03-21
Filing date: 2006-02-23
Publication date: 2007-04-05
Anticipated expiration: 2007-09-21
Also published as: WO2006117800A2; WO2006117800A3

Abstract

The present invention relates to the syntheses of 3,4-propylenedioxythiophenes of the formula (I) wherein R represents a n-valent linear or branched, optionally substituted, aliphatic C1-Cn radical and Y represents a pendant functional group. Further, methods for the preparation of the said compounds are disclosed.

Claims

AMENDED CLAIMS received by the International Bureau on 22 January 2007 (22.01.2007)

1. Compounds of the formula I:

Characterized in that Y = -CH2OX, -L and - CH2OH

When Y is -CH2OX then

R is a linear or branched or cyclic, optionally substituted, aliphatic C1-C25 chain or an optionally substituted aromatic C6-C25 compound.

X = a linear or branched or cyclic, optionally substituted, aliphatic C1 -C25 chain or an optionally substituted aromatic C6-C25 compound (except benzylic or benzylic derivatives when R is a methyl group); -R¹OR", -CH2CH=CH2, -R'CHO, -R¹COOR", -R¹CONR¹¹¹R", -R¹COO-M+, -R¹-

NR¹¹R¹", -R'-N+R"R¹"R""A-, -R¹CN, -RTO43-, -R'SO3-M+, -(RO)yR¹¹, -C(O)R", -C(O)NR¹"

R", -CH2CCH,

R' a linear or branched or cyclic, optionally substituted, aliphatic C1 -C25 chain or an optionally substituted aromatic C6-C25 compound.

R" is hydrogen or a linear or branched or cyclic, optionally substituted, aliphatic C1-C25 chain or an optionally substituted aromatic C6-C25 compound.

R¹" is hydrogen or a linear or branched or cyclic, optionally substituted, aliphatic C1-C25 chain or an optionally substituted aromatic C6-C25 compound. R"" is hydrogen or a linear or branched or cyclic, optionally substituted, aliphatic C1 -C25 chain or an optionally substituted aromatic C6-C25 compound.

M+ = H+, metal ions, A- = Anions, y = an integer between 1 -15.

When Y = L then L = -CH2CH=CH2, -CH2CCH.

R is L or is hydrogen or is a linear or branched or cyclic, optionally substituted, aliphatic C1-C25 chain or an optionally substituted aromatic C6-C25 compound

2. A process for the preparation of compounds of the formula I when Y is CH₂OX in steps comprising: Step A: Reacting diethyl malonate with ethyl haloformate in dry organic solvent in presence of a base to produce the 2-ethoxycarbonyl-malonic acid diethyl ester Step A: Reacting diethyl malonate with ethyl haloformate in dry organic solvent in presence of a base to produce the 2-ethoxycarbonyl-malonic acid diethyl ester

Step B: Reacting 2-ethoxycarbonyl-malonic acid diethyl ester, obtained in step A₁ with aliphatic halides or aliphatic tosylate in organic solvents in presence of a base to produce alkyl 2- ethoxycarbonyl-malonic acid diethyl ester

Step C: Reacting alkyl 2-ethoxycarbonyl-malonic acid diethyl ester, obtained in step B, with a reducing agent in organic solvent to produce alkyl triols of the formula Il

R. /—OH

HO OH

Ii Step D: Reacting the alkyl triols of formula II, obtained in step C, with 3,4-dialkoxythiophene in dry organic solvent in presence of an acid as the catalyst to produce (3-alkyl-3,4-dihydro-2H- thieno[3,4-b][1 ,4]dioxepin-3-yl)-methanol (compounds of molecular formula I with Y = CH₂OH) Step E: Reacting the 3-3-alkyl-3,4-dihydro-2H-thieno[3,4-b][1 ,4]dioxepin-3-yl)-methanol, obtained in step D, with alkyl halides or alkyl tosylates or alkane sultones in presence of a catalyst and base in dry organic solvents to produce compounds of molecular formula I with Y = CH₂OX.

3. A process for the preparation of compounds of the formula 1 with Y = L = R and L= - CH₂CHCH₂, or -CH₂CCH in steps comprising:

Step F: Reacting diethyl malonate with allyl or propargyl halide in organic solvents in presence of a base to produce 2,2-diallyl maionic acid diethyl ester or 2,2-dipropargyi malonic acid diethyl ester, respectively

Step G: Reacting 2,2-diallyl malonic acid diethyl ester or 2,2-dipropargyl malonic acid diethyl ester, obtained in step F, with a reducing agent in organic solvent to produce 2,2-diallyl-1 ,3- propanediol or 2,2-dipropargyl-1 ,3-propanediol, respectively Step H: Reacting the 2,2-diallyl-1 ,3-propanediol or 2,2-dipropargyl-1 ,3-propanediol, obtained in step G, with 3,4-dialkoxythiophene in dry organic solvent in presence of an, acid as the catalyst to produce 3,3-diallyl-3,4-dihydro-2H-thieno[3,4-b][1 ,4]dioxepine or 3,3-dipropargyl-3,4-dihydro-

2H-thieno[3,4-b][1 ,4]dioxepine, respectively.

4. A process for the preparation of compounds of the formula 1 with Y = L = -CH₂CHCH₂, or - CH₂CCH in steps comprising:

Step I: Reacting diethyl malonate with allyl or propargyl halide in organic solvents in presence of a base to produce 2-ailyl malonic acid diethyl ester or 2-propargyl malonic acid diethyl ester, respectively Step K: Reacting 2-alkyl 2-allyl-malonic acid diethyl ester or 2-alkyl-2-propargyl-malonic acid diethyl ester, obtained in step J, with a reducing agent to produce 2-alky l-2-ally I- 1 ,3-propanediol or 2-alkyl-2-propargyl-1 ,3-propanediol, respectively

Step L: Reacting the 2-alkyl-2-allyl-1 ,3-propanediol or 2-alkyl-2-propargyl-1 ,3-propanediol, obtained in step K, with 3,4-dialkoxythiophene in dry organic solvent in presence of an acid as the catalyst to produce 3-alkyl-3-allyl-3,4-dihydro-2H-thieno[3,4-b][1 ,4]dioxepine or 3-alkyl-3- propargyl-3,4-dihydro-2H-thieno[3,4-b][1 ,4]dioxepine, respectively (compounds of the formula 1 with Y = L= -CH₂CHCH₂, or -CH₂CCH).

5. Use of the catalyst for the functionalization of compounds of molecular formula 1 when Y = CH₂OH to get compounds of molecular formula 1 with Y = CH₂OX wherein the catalyst was selected from the list: DABCO, DMAP, DBU, pyridine, or any other tertiary amine.