2,2-Bis(4-hydroxyphenyl)-alkyl onium salt and process for the preparation thereof

Abstract
The present invention provides novel 2,2-bis(4-hydroxyphenyl)-alkyl onium salts as illustrated by 2,2-bis(4-hydroxyphenyl)-tridecyl(1,2-dimethylimidazolium)bromide and a process for preparation thereof by hydroxyalkylating acetoacetate to the corresponding hyroxyalkylacetoacetate, dealkoxycarbonylating the hydroxyalkyl acetoacetate to ω-hydroxyalkan-2-one and contacting the ω-hydroxyalkan-2-one with phenol in the presence of an acidic catalyst to give 2,2-bis(4-hydroxyphenyl)alkanol, brominating the 2,2-bis(4-hydroxyphenyl)alkanol to 2,2-bis(4-hydroxyphenyl)alkyl bromide, quaternizing 1,2-dimethylimidazole with the 2,2-bis(4-hydroxyphenyl)alkyl bromide to 2,2-bis(4-hydroxyphenyl)alkyl(1,2-dimethylimidazolium)bromide. The products can be used as reactive modifiers for layered phyllosilicates that can be used in the preparation of polymer-nanocomposites, wherein the said polymers are prepared from 2,2-bis(4-hydroxyphenyl)propane as one of the reacting monomers.
Description
Claims
  • 1. Novel 2,2-bis(4-hydroxyphenyl) alkylonium salts of formula (1):
  • 2. A process for the preparation of 2,2-bis(4-hydroxyphenyl)alkyl onium salts of formula (1), the said process comprising the steps of: a. mono brominating alkyl dialcohol by reacting it with a brominating agent in an organic solvent, at a temperature in the range of 40-150° C. to obtain α,ω-bromoalkylalcohol of formula (2):
  • 3. A process according to claim 2 wherein the alkyl dialcohol used in step (a) is 1,10 decanediol.
  • 4. A process according to claim 2 wherein the the α,ω-bromoalkylalcohol obtained is 10-bromodecan-1-ol.
  • 5. A process according to claim 2 wherein the organic solvent used in step (a) is selected from the group consisting of toluene, benzene, cyclohexane, ethoxyethane and tetrahydrofuran.
  • 6. A process according to claim 2 wherein brominating agent used in step (a) is selected from the group consisting of aqueous HBr, HBr (phase transfer), HBr/H2SO4, HBr/LiBr, (C5H5N+H)F(HF)−X/NH4Br, ZnBr2/PPh3/EtO2CN═N CO2Et, PBr3, P/Br2, Ph3P/Br2, Ph2PCH2CH2PPh2/Br2, nBu3P/Br2, (PhO)3P/Br2, (PhO)3P/C6H5CH2Br, CBr4/PPh3, Ph3P/NBS, Ph2PCH2CH2PPh2/CBr4, Ph3P/BrCl2CCCl2Br, SOBr2, Me2S/NBS, BH3/Br2, (Me3Si)2/(C5H5NH)Br3, Me3SiCl/LiBr and Me3SiBr.
  • 7. A process according to claim 2 wherein the monoalkylation at active methylene carbon of acetoacetate in step (b) is carried out by generating an anion at that carbon using a base selected from the group consisting of sodium methoxide, sodium ethoxide, NaH and K2CO3.
  • 8. A process according to claim 2 wherein the organic solvent used in step (b) is alcohol selected from the group consisting of methanol, ethanol, isopropanol, isobutanol, tetrahydrofuran, diethyl ether and hydrocarbon selected from cyclohexane, hexane, pet ether and decalin.
  • 9. A process according to claim 2 wherein the accelerating agent used in step (b) is selected from tetra n-butylammonium iodide, sodium iodide and potassium iodide.
  • 10. A process according to claim 2 wherein the alkali metal salt used in step (c) is selected from the group consisting of NaCl, NaBr, KCl, KBr, NaI, KI, NaCN, LiCl, LiI and KOAc.
  • 11. A process according to claim 2 wherein the ammonium salt used in step (c) is (H3C)4NOAc.
  • 12. A process according to claim 2 wherein the non-aqueous solvent used in step (c) is selected from the group consisting of dimethylsulfoxide, dimethyl acetate, dimethylformamide and hexamethylphosphoric triamide.
  • 13. A process according to claim 2 wherein the acidic catalyst in step (d) is selected from the group consisting of ion exchange resins in the acid form, acidic clays, sulfonated zirconia and excess of anhydrous hydrogen chloride in combination with a mercaptan.
  • 14. A process according to claim 2 wherein the brominating agent used in step (e) is selected from the group consisting of aqueous HBr, HBr (phase transfer), HBr/H2SO4, HBr/LiBr, (C5H5N+H)F(HF)−X/NH4Br, ZnBr2/PPh3/EtO2CN═N CO2Et, PBr3, P/Br2, Ph3P/Br2, Ph2PCH2CH2PPh2/Br2, nBu3P/Br2, (PhO)3P/Br2, (PhO)3P/C6H5CH2Br, CBr4/PPh3, Ph3P/NBS, Ph2PCH2CH2PPh2/CBr4, Ph3P/BrCl2CCCl2Br, SOBr2, Me2S/NBS, BH3/Br2, (Me3Si)2/(C5H5NH)Br3, Me3SiCl/LiBr and Me3SiBr.
  • 15. A process according to claim 2 wherein the amount of brominating agent used in step (e) is in slight excess over the stoichiometric amount by 5 to 25%.
  • 16. A process according to claim 2 wherein the alkylation in step (f) is done by reacting the compounds selected from the group consisting of tertiary amines, phosphines, imidazoles and pyridines with the 2,2-bis-4-(hydroxyphenyl)alkyl bromide.
  • 17. A process according to claim 2 wherein the organic solvent used in step (f) is selected from the group consisting of methanol, ethanol, isopropanol, butanol, isobutanol, toluene, benzene and tetrachloroethane.
Priority Claims (1)
Number Date Country Kind
0400/DEL/2006 Feb 2006 IN national