WO2001060775A1 - Process for preparing alkoxy or arylmethoxy aroxyethanes - Google Patents
Process for preparing alkoxy or arylmethoxy aroxyethanes Download PDFInfo
- Publication number
- WO2001060775A1 WO2001060775A1 PCT/US2001/003328 US0103328W WO0160775A1 WO 2001060775 A1 WO2001060775 A1 WO 2001060775A1 US 0103328 W US0103328 W US 0103328W WO 0160775 A1 WO0160775 A1 WO 0160775A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- halide
- alkyl
- catalyst
- group
- chloride
- Prior art date
Links
- 0 CCC1(C2)C(*)(CC3(*)CC4)CCC(C)(C5)C2(C)[C@@]13C45OCCOC Chemical compound CCC1(C2)C(*)(CC3(*)CC4)CCC(C)(C5)C2(C)[C@@]13C45OCCOC 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
Definitions
- This invention relates to alkoxy or arylmethoxy ethanes.
- This invention particularly concerns a process for preparation of such compounds. More particularly, the invention teaches a novel process for preparation of 2-alkoxy (or 2- arylmethoxy)-1-aroxyethanes, a class of compounds useful in a variety of diverse applications such as improved sensitizers or modifiers for thermal sensitive papers and as dispersants, emollients, and texture enhancing agents in cosmetics and lotions.
- the substituted phenoxyethanol was reacted with p-xylylene chloride and aqueous sodium hydroxide using trioctylmethylammonium chloride as catalyst in chlorobenzene.
- the success of this tandem two step process depends on the complete conversation of the substituted phenol to the corresponding substituted phenoxyethanol in the first step; otherwise, a mixture of inseparable products are formed, resulting in low yield of the desired product.
- the present invention is a novel process for manufacturing 2-alkoxy (or 2- arylmethoxy) ⁇ 1-aroxyethanes using a one-pot, two-step procedure.
- the novel process comprises reacting substituted or unsubstituted phenol (or naphthol) with ethylene carbonate n the presence of a first catalyst, with or without solvent, and reacting the product formed in the first step with alkyl or aralkyl halide (sulfate or sulfonate) and metal hydroxide in the presence of a second catalyst with or without solvent.
- This invention teaches a process for preparing 2-alkoxy(or 2-arylmethoxy)-1- aroxyethanes. Particularly, this invention teaches a novel process for preparing 2- alkoxy (or 2-arylmethoxy)-1-aroxy-ethanes represented by the formula (I):
- P is selected from phenyl and naphthyl moieties.
- Formula (IIA) depicts when P in the structure of Formula 1 is replaced by phenyl
- Formula MB depicts when P in the structure of Formula I is replaced by naphthyl.
- the substituents Ri, R 2 and R 3 are independently hydrogen, alkyl, alkoxy, aryl, aralkyl, aralkoxy, halogen, alkoxyalkoxy and aralkoxyalkoxy; and R 4 , is independently alkoxyethyl, alkoxyethoxy and aralkoxyethoxy.
- the alkyl moieties in alkyl, alkoxy, aralkyl, aralkoxy, alkoxyalkyl, alkoxyalkoxy and aralkoxyalkoxy groups contain one through eight carbon atoms.
- This invention teaches an improved process for manufacturing 2-alkoxy (or 2- arylmethoxy)-1-aroxyethanes (VIII) using a one-pot, two-step procedure from readily available materials.
- the process of the invention is diagrammed as follows:
- R 5 is either a substituted or unsubstituted phenyl or naphthyl group.
- the substituents on the phenyl or naphthyl groups include alkyl (C f Cs), alkoxy (C C 8 ), aroxy, aralkoxy (d- C 8 alkyl) and halogen.
- alkyl (C f Cs) alkoxy (C C 8 )
- aroxy aralkoxy (d- C 8 alkyl)
- halogen halogen
- the process comprises reacting substituted or unsubstituted phenols (or naphthols) (III) with ethylene carbonate (IV) using catalyst 1 without a solvent and reacting the product formed (V) in the first step with alkyl or aralkyl halide (sulfate or sulfonate) (VI) and metal hydroxide in the presence of catalyst 2 with or without a solvent.
- the reaction temperature may be selected from 50°C to 200°C depending on the phenol (or naphthol) used. Most of the phenols (or naphthols) react in the preferred temperature range from 140°C to 160°C.
- the catalyst 1 that is suitable for this reaction include metal halides, quarternary ammonium halides and quarternary phosphonium halides.
- Preferred catalysts include sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammoniumiodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, methyltrioctylammonium chloride (aliquat 336), tetraethylphosphonium chloride, tetraethylphosphonium bromide and tetraethylphosphonium iodide.
- the intermediate (V) was then mixed with alkyl or aralkyl halide (sulfate or sulfonate) (VI), metal hydroxide (VII) and catalyst 2, heated and stirred vigorously. Powdered metal hydroxide was used in the solvent free procedure. Aqueous solution (40-50%) of metal hydroxide was used with a solvent in the solvent procedure.
- Preferred metal hydroxides include sodium hydroxide and potassium hydroxide and the preferred solvents are aliphatic or aromatic hydrocarbons or chlorohydrocarbons.
- Catalyst 2 may be either quarternary ammonium salt or quarternary phosophonium salt.
- Preferred catalyst 2 are tetrabutylammonium hydrogen sulfate, tetrabutylammonium halide, tetraethylammonium halide, methyltrioctylammonium choride (also known as aliquat 336) and tetraethylphosphonium halide.
- the reaction temperature for the second step is dependent on the solvent used. The preferred temperature range is room temperature to 55°C for low boiling point solvents and 50-100°C for high boiling point solvents. For the solvent free procedure 90-100°C temperature range is preferred.
- step 2 (V) is converted to (VIII) using either a solvent-free or a solvent procedure.
- solvent-free procedure a solid liquid phase transfer catalysis reaction was selected because it gives complete conversion.
- Metal hydroxides should be finely powdered and the stirring should be vigorous to produce efficient conversion.
- solvent procedure an aqueous solution of the metal hydroxide and a suitable solvent was used as in traditional phase transfer catalysis reaction. Here again, vigorous stirring is recommended for optimum conversion.
- the solvent-free options and the one-pot process enable scale up for commercial production.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002368276A CA2368276C (en) | 2000-02-17 | 2001-02-01 | Process for preparing alkoxy or arylmethoxy aroxyethanes |
EP01903473A EP1183224B1 (en) | 2000-02-17 | 2001-02-01 | Process for preparing alkoxy or arylmethoxy aroxyethanes |
AT01903473T ATE272600T1 (en) | 2000-02-17 | 2001-02-01 | METHOD FOR PRODUCING ALKOXY-OR ARYLMETHOXY-AROXYETHANES |
JP2001559829A JP2003522810A (en) | 2000-02-17 | 2001-02-01 | Method for producing alkoxy or allylmethoxyethane |
AU31277/01A AU775089B2 (en) | 2000-02-17 | 2001-02-01 | Process for preparing alkoxy or arylmethoxy aroxyethanes |
DE60104614T DE60104614T2 (en) | 2000-02-17 | 2001-02-01 | PROCESS FOR THE PREPARATION OF ALKOXY OR ARYLMETHOXY AROXYETHANES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18327500P | 2000-02-17 | 2000-02-17 | |
US60/183,275 | 2000-02-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001060775A1 true WO2001060775A1 (en) | 2001-08-23 |
Family
ID=22672150
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/003328 WO2001060775A1 (en) | 2000-02-17 | 2001-02-01 | Process for preparing alkoxy or arylmethoxy aroxyethanes |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP1183224B1 (en) |
JP (1) | JP2003522810A (en) |
AT (1) | ATE272600T1 (en) |
AU (1) | AU775089B2 (en) |
CA (1) | CA2368276C (en) |
DE (1) | DE60104614T2 (en) |
ES (1) | ES2225475T3 (en) |
WO (1) | WO2001060775A1 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7846915B2 (en) | 2004-10-20 | 2010-12-07 | Resverlogix Corporation | Stilbenes and chalcones for the prevention and treatment of cardiovascular diseases |
WO2011089385A1 (en) | 2010-01-19 | 2011-07-28 | Cambrex Karlskoga Ab | New processes for producing benzophenone derivatives |
US8053440B2 (en) | 2007-02-01 | 2011-11-08 | Resverlogix Corporation | Compounds for the prevention and treatment of cardiovascular diseases |
US8114995B2 (en) | 2008-06-26 | 2012-02-14 | Resverlogix Corp. | Methods of preparing quinazolinone derivatives |
US8410109B2 (en) | 2005-07-29 | 2013-04-02 | Resverlogix Corp. | Pharmaceutical compositions for the prevention and treatment of complex diseases and their delivery by insertable medical devices |
US8952021B2 (en) | 2009-01-08 | 2015-02-10 | Resverlogix Corp. | Compounds for the prevention and treatment of cardiovascular disease |
US9073878B2 (en) | 2012-11-21 | 2015-07-07 | Zenith Epigenetics Corp. | Cyclic amines as bromodomain inhibitors |
US9238640B2 (en) | 2009-03-18 | 2016-01-19 | Resverlogix Corp. | Anti-inflammatory agents |
US9271978B2 (en) | 2012-12-21 | 2016-03-01 | Zenith Epigenetics Corp. | Heterocyclic compounds as bromodomain inhibitors |
US9321712B2 (en) | 2012-10-19 | 2016-04-26 | Fermion Oy | Process for the preparation of ospemifene |
US9610251B2 (en) | 2011-11-01 | 2017-04-04 | Resverlogix Corp. | Pharmaceutical compositions for substituted quinazolinones |
US9757368B2 (en) | 2009-04-22 | 2017-09-12 | Resverlogix Corp. | Anti-inflammatory agents |
US9765039B2 (en) | 2012-11-21 | 2017-09-19 | Zenith Epigenetics Ltd. | Biaryl derivatives as bromodomain inhibitors |
US10111885B2 (en) | 2015-03-13 | 2018-10-30 | Resverlogix Corp. | Compositions and therapeutic methods for the treatment of complement-associated diseases |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2987555A (en) * | 1961-06-06 | Hydroxyalkylated | ||
US4341905A (en) * | 1979-07-18 | 1982-07-27 | The Dow Chemical Company | Inorganic halide salt catalysts for hydroxyalkylation of phenols or thiophenols |
US5179068A (en) * | 1990-11-06 | 1993-01-12 | Mitsubishi Paper Mills Limited | Heat-sensitive recording material |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS504012A (en) * | 1972-12-16 | 1975-01-16 | ||
JPH01168489A (en) * | 1987-12-25 | 1989-07-03 | Honshu Paper Co Ltd | Thermal recording material |
-
2001
- 2001-02-01 WO PCT/US2001/003328 patent/WO2001060775A1/en active IP Right Grant
- 2001-02-01 CA CA002368276A patent/CA2368276C/en not_active Expired - Fee Related
- 2001-02-01 ES ES01903473T patent/ES2225475T3/en not_active Expired - Lifetime
- 2001-02-01 EP EP01903473A patent/EP1183224B1/en not_active Expired - Lifetime
- 2001-02-01 DE DE60104614T patent/DE60104614T2/en not_active Expired - Lifetime
- 2001-02-01 AU AU31277/01A patent/AU775089B2/en not_active Ceased
- 2001-02-01 JP JP2001559829A patent/JP2003522810A/en active Pending
- 2001-02-01 AT AT01903473T patent/ATE272600T1/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2987555A (en) * | 1961-06-06 | Hydroxyalkylated | ||
US4341905A (en) * | 1979-07-18 | 1982-07-27 | The Dow Chemical Company | Inorganic halide salt catalysts for hydroxyalkylation of phenols or thiophenols |
US5179068A (en) * | 1990-11-06 | 1993-01-12 | Mitsubishi Paper Mills Limited | Heat-sensitive recording material |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8093273B2 (en) | 2004-10-20 | 2012-01-10 | Resverlogix Corp. | Flavanoids and isoflavanoids for the prevention and treatment of cardiovascular diseases |
US8242130B2 (en) | 2004-10-20 | 2012-08-14 | Resverlogix Corp. | Flavanoids and isoflavanoids for the prevention and treatment of cardiovascular diseases |
US7846915B2 (en) | 2004-10-20 | 2010-12-07 | Resverlogix Corporation | Stilbenes and chalcones for the prevention and treatment of cardiovascular diseases |
US8410109B2 (en) | 2005-07-29 | 2013-04-02 | Resverlogix Corp. | Pharmaceutical compositions for the prevention and treatment of complex diseases and their delivery by insertable medical devices |
US9199990B2 (en) | 2007-02-01 | 2015-12-01 | Resverlogix Corp. | Compounds for the prevention and treatment of cardiovascular diseases |
US10532054B2 (en) | 2007-02-01 | 2020-01-14 | Resverlogix Corp. | Compounds for the prevention and treatment of cardiovascular diseases |
US8053440B2 (en) | 2007-02-01 | 2011-11-08 | Resverlogix Corporation | Compounds for the prevention and treatment of cardiovascular diseases |
US8889698B2 (en) | 2007-02-01 | 2014-11-18 | Resverlogix Corp. | Compounds for the prevention and treatment of cardiovascular diseases |
US8114995B2 (en) | 2008-06-26 | 2012-02-14 | Resverlogix Corp. | Methods of preparing quinazolinone derivatives |
US8952021B2 (en) | 2009-01-08 | 2015-02-10 | Resverlogix Corp. | Compounds for the prevention and treatment of cardiovascular disease |
US9238640B2 (en) | 2009-03-18 | 2016-01-19 | Resverlogix Corp. | Anti-inflammatory agents |
US10131640B2 (en) | 2009-03-18 | 2018-11-20 | Resverlogix Corp. | Anti-inflammatory agents |
US11407719B2 (en) | 2009-03-18 | 2022-08-09 | Resverlogix Corp. | Anti-inflammatory agents |
US10882828B2 (en) | 2009-03-18 | 2021-01-05 | Resverlogix Corp. | Anti-inflammatory agents |
US9757368B2 (en) | 2009-04-22 | 2017-09-12 | Resverlogix Corp. | Anti-inflammatory agents |
US9085519B2 (en) | 2010-01-19 | 2015-07-21 | Cambrex Karlskoga Ab | Processes for producing benzophenone derivatives |
WO2011089385A1 (en) | 2010-01-19 | 2011-07-28 | Cambrex Karlskoga Ab | New processes for producing benzophenone derivatives |
US9610251B2 (en) | 2011-11-01 | 2017-04-04 | Resverlogix Corp. | Pharmaceutical compositions for substituted quinazolinones |
US10016426B2 (en) | 2011-11-01 | 2018-07-10 | Resverlogix Corp. | Pharmaceutical compositions for substituted quinazolinones |
US9321712B2 (en) | 2012-10-19 | 2016-04-26 | Fermion Oy | Process for the preparation of ospemifene |
US9278940B2 (en) | 2012-11-21 | 2016-03-08 | Zenith Epigenetics Corp. | Cyclic amines as bromodomain inhibitors |
US9765039B2 (en) | 2012-11-21 | 2017-09-19 | Zenith Epigenetics Ltd. | Biaryl derivatives as bromodomain inhibitors |
US9073878B2 (en) | 2012-11-21 | 2015-07-07 | Zenith Epigenetics Corp. | Cyclic amines as bromodomain inhibitors |
US9271978B2 (en) | 2012-12-21 | 2016-03-01 | Zenith Epigenetics Corp. | Heterocyclic compounds as bromodomain inhibitors |
US10111885B2 (en) | 2015-03-13 | 2018-10-30 | Resverlogix Corp. | Compositions and therapeutic methods for the treatment of complement-associated diseases |
US10772894B2 (en) | 2015-03-13 | 2020-09-15 | Resverlogix Corp. | Compositions and therapeutic methods for the treatment of complement-associated diseases |
Also Published As
Publication number | Publication date |
---|---|
DE60104614T2 (en) | 2005-01-05 |
JP2003522810A (en) | 2003-07-29 |
AU3127701A (en) | 2001-08-27 |
ES2225475T3 (en) | 2005-03-16 |
CA2368276A1 (en) | 2001-08-23 |
AU775089B2 (en) | 2004-07-15 |
EP1183224B1 (en) | 2004-08-04 |
DE60104614D1 (en) | 2004-09-09 |
CA2368276C (en) | 2009-12-08 |
EP1183224A4 (en) | 2003-02-26 |
ATE272600T1 (en) | 2004-08-15 |
EP1183224A1 (en) | 2002-03-06 |
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