GB787406A - Process for the manufacture of trimethylene oxide compounds containing hydroxyl groups - Google Patents
Process for the manufacture of trimethylene oxide compounds containing hydroxyl groupsInfo
- Publication number
- GB787406A GB787406A GB1144855A GB1144855A GB787406A GB 787406 A GB787406 A GB 787406A GB 1144855 A GB1144855 A GB 1144855A GB 1144855 A GB1144855 A GB 1144855A GB 787406 A GB787406 A GB 787406A
- Authority
- GB
- United Kingdom
- Prior art keywords
- carbonate
- phosgene
- ethyl
- trimethylene oxide
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Trimethylene oxide methylols having the formula <FORM:0787406/IV (b)/1> where R represents a methyl, ethyl or hydroxymethyl group are produced by reacting a polyhydroxyl compound of the formula R-C(CH2OH)3, where R is as above-defined, with a carbonic acid derivative of the general formula O=C(X)2, wherein X is a halogen atom or an alkoxy, cycloalkoxy, aryloxy or tetrahydrofurfuryloxy radical or X-X is a divalent dioxy-substituted alkylene, cycloalkylene or arylene radical, the hydroxy compounds corresponding to said radicals having a boiling point of at most 160 DEG C. at 0.1 mm. Hg., followed by eliminating carbon dioxide from the resulting product. Suitable carbonic acid derivatives are phosgene, the methyl, ethyl, butyl, amyl, hexyl, heptyl 2-ethyl-hexyl, cyclopentyl, cyclohexyl, phenyl, cresyl or tetrahydrofurfuryl esters of chlorocarbonic acid, and the corresponding dimethyl, diethyl, and so on, diesters of carbonic acid, and the carbonates of ethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-cyclohexanediol and pyrocatechol. In the first stage of the conversion, the polyhydroxyl compound is reacted with phosgene at - 10 DEG C. to +100 DEG C., with a chlorocarbonic acid ester at - 10 DEG C. to +160 DEG C., or with a carbonic acid diester at temperatures between 90 DEG and 160 DEG C., with the removal of 2 mols. of HX to form a 5-hydroxymethyl-2-m-dioxanone. This step may be effected at normal or reduced pressure. When using phosgene it is preferred to dissolve the polyhydric alcohol in a solvent and to remove the liberated hydrogen chloride by blowing air through the mixture or by boiling out. When using chlorocarbonic esters, the addition of at least the stoichiometric amount of a tertiary amine, e.g. pyridine, N,N-dimethyl aniline or triethyl amine, is preferred. When using carbonic acid diesters, an inorganic basic compound, such as an alkali metal hydroxide, carbonate or alcoholate may be added. The splitting off of carbon dioxide is generally effected at temperatures of above 120 DEG C. and may also be expedited by adding the aforesaid basic compounds. The product is advantageously distilled off as it is formed, under reduced pressure if desired. The products are useful as solvents and as intermediates in the manufacture of plasticizers and plastics. In examples, 3-ethyl-3-methylol-trimethylene oxide is obtained from 1,1,1-trimethylol propane with (1) phosgene in dioxane; (3) gaseous phosgene; (4) diethyl carbonate and potassium carbonate; (5) di-n-butylcarbonate and sodium butanolate; (6) di-(2-ethylhexyl) carbonate and sodium; (7) dicyclohexyl carbonate and sodium cyclohexanolate; (8) diphenyl carbonate and sodium phenolate; (9) ethylene glycol carbonate; (11) pyrocatechol carbonate and sodium; (12) butanediol - 1,3 - carbonate (obtained by re-esterifying butane-1,3-diol with diethyl carbonate in the presence of potassium carbonate below 120 DEG C.,); (13) ethyl chlorocarbonate and N,N-dimethylaniline; or (15) phenyl chlorocarbonate and pyridine; 3-methyl - 3 - methylol - trimethylene oxide is obtained from 1,1,1-trimethylol-ethane with (2) phosgene in dioxane; or (14) methyl chlorocarbonate in pyridine; 3,3-dimethylol-trimethylene oxide is obtained from pentaerythritol with (10) diethyl carbonate and potassium carbonate; or (16) ethyl chlorocarbonate and pyridine, minor amounts of 2,6-dioxa-4-spiroheptane also being formed.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1144855A GB787406A (en) | 1955-04-20 | 1955-04-20 | Process for the manufacture of trimethylene oxide compounds containing hydroxyl groups |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1144855A GB787406A (en) | 1955-04-20 | 1955-04-20 | Process for the manufacture of trimethylene oxide compounds containing hydroxyl groups |
Publications (1)
Publication Number | Publication Date |
---|---|
GB787406A true GB787406A (en) | 1957-12-11 |
Family
ID=6699241
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1144855A Expired GB787406A (en) | 1955-04-20 | 1955-04-20 | Process for the manufacture of trimethylene oxide compounds containing hydroxyl groups |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB787406A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4501905A (en) * | 1981-01-30 | 1985-02-26 | Bayer Aktiengesellschaft | Cyclic carbonic acid derivatives |
WO2000035895A1 (en) * | 1998-12-16 | 2000-06-22 | Perstorp Ab | Process for production of an oxetane |
EP1038869A1 (en) * | 1999-03-19 | 2000-09-27 | Dainippon Ink And Chemicals, Inc. | Process for the production of 3-alkyl-3-hydroxymethyloxetanes |
JP2000327673A (en) * | 1999-03-12 | 2000-11-28 | Ube Ind Ltd | Preservation of oxetane compound |
US9108911B1 (en) | 2014-03-26 | 2015-08-18 | Oxea Bishop Llc | Process for the manufacture of di-TMP |
CN112608288A (en) * | 2020-12-21 | 2021-04-06 | 深圳市普利凯新材料股份有限公司 | Preparation method of 3-ethyl-3-oxetanemethanol |
-
1955
- 1955-04-20 GB GB1144855A patent/GB787406A/en not_active Expired
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4501905A (en) * | 1981-01-30 | 1985-02-26 | Bayer Aktiengesellschaft | Cyclic carbonic acid derivatives |
WO2000035895A1 (en) * | 1998-12-16 | 2000-06-22 | Perstorp Ab | Process for production of an oxetane |
US6515152B1 (en) | 1998-12-16 | 2003-02-04 | Perstorp Ab | Process for production of an oxetane |
JP2000327673A (en) * | 1999-03-12 | 2000-11-28 | Ube Ind Ltd | Preservation of oxetane compound |
EP1038869A1 (en) * | 1999-03-19 | 2000-09-27 | Dainippon Ink And Chemicals, Inc. | Process for the production of 3-alkyl-3-hydroxymethyloxetanes |
JP2000273093A (en) * | 1999-03-19 | 2000-10-03 | Dainippon Ink & Chem Inc | Production of 3-alkyl-3-hydroxymethyloxetane |
US9108911B1 (en) | 2014-03-26 | 2015-08-18 | Oxea Bishop Llc | Process for the manufacture of di-TMP |
CN112608288A (en) * | 2020-12-21 | 2021-04-06 | 深圳市普利凯新材料股份有限公司 | Preparation method of 3-ethyl-3-oxetanemethanol |
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