GB565573A - Manufacture of dioxane derivatives - Google Patents
Manufacture of dioxane derivativesInfo
- Publication number
- GB565573A GB565573A GB133/43A GB13343A GB565573A GB 565573 A GB565573 A GB 565573A GB 133/43 A GB133/43 A GB 133/43A GB 13343 A GB13343 A GB 13343A GB 565573 A GB565573 A GB 565573A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydroxymethyl
- methyl
- benzodioxane
- give
- derivative
- 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
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
- C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D319/20—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring with substituents attached to the hetero ring
Abstract
2-Hydroxymethyl arylene-dioxanes, substituted in the aromatic nucleus are manufactured by reacting epihalogen hydrin with p alkaline solutions of ortho dihydric phenols containing at least one of the following nuclear substituents or a condensed ring; alkyl, alkoxy, carboxy, carbalkoxy, aminoalkyl and alkylamino. The 2-hydroxy group may be replaced by halogen which can be exchanged for an amino or other group, or other, e.g. acylated, derivatives may be produced. In examples: (1) o-methyl catechol in potash is mixed with epichlorhydrin to form 2 - hydroxymethyl - 5 - methyl - benzodioxane. Reaction with thionyl chloride gives the 2-chlormethyl compound which is heated with morpholine under pressure to produce 2-morpholinylmethyl - 5 - methyl - benzodioxane. The starting product is made by reduction of o-vanillin to o-methyl guaiacol and dimethylation with HBr or HCl in presence of a tertiary base. Vanillin similarly yields 1-methyl-3,4-dihydroxy-benzene which can be used for preparing an isomeric methyl-hydroxymethylbenzodioxane; (2) 1 - propyl - 3,4 - dihydroxy - benzene, made by catalytic hydrogenation of isoeugenol and demethylation, similarly yields 2-hydroxymethyl-6-propyl-benzodioxane which is converted to the chlorine and then to the morpholine derivative; (3) o-vanillin with dilute hydrogen peroxide gives pyrogallol-1-methyl ether which yields, by reaction with epichlorhydrin, 2-hydroxymethyl - 5 - methoxy-benzodioxane which can be converted to the chlormethyl and thence to the morpholine derivative. Other alkoxy benzodioxanes are obtained from the corresponding pyrogallol derivatives, e.g. the 1-ethyl ether; (4) 2-chlormethyl - 5 - methoxy - benzodioxane obtained as in (3) is heated with diethylamine to give the 2-diethylamino-methyl derivative. Piperidine, tetrahydroquinoline or isoquinoline give the corresponding 2-aminomethyl derivatives; (5) the same intermediate is heated with n-butylamine to give the 2-butylaminomethyl derivative. Homologues of butylamine up to stearylamine react similarly; (6) the product of (5) in benzene is treated with calcined sodium carbonate and dimethyl sulphate to produce the tertiary base. Diethyl sulphate yields the corresponding ethylbutylamino compound; (7) 2,3-dihydroxy-naphthalene in caustic potash is treated with epichlorhydrin to give 2-hydroxymethyl-naphthodioxane which with thionyl chloride forms the 2-chlormethyl compound, yielding the 2-morpholinylmethyl derivative with morpholine. Other o-dihydroxynaphthalenes, dihydroxyanthracenes and their derivatives such as dihydroxyanthraquinones react similarly; (8) 2-hydroxymethyl-naphthodioxane is hydrogenated in the presence of Raney nickel to give the tetrahydronaphthodioxane derivative which is converted to the 2-chlormethyl and thence to the 2-morpholinylmethyl compound; (9) 2-morpholinyl-methyl-5-methoxy-benzodioxane produced as in (3) is refluxed with hydrobromic acid with demethylation to the 5-hydroxy compound. The same compound can be made from pyrogallol and epichlorhydrin and exchange of the hydroxyl in the 2-hydroxymethyl group for chlorine and then for morpholinyl; (10) morpholine is treated with formaldehyde solution to form hydroxymethyl-morpholine which reacts with catechol to give morpholinylmethyl-dihydroxybenzene. Epichlorhydrin with this yields 2-hydroxymethyl - ar - morpholinylmethyl - benzodioxane; (11) 2-morpholinylmethyl-5-hydroxybenzodioxane produced as in (9) is heated with acetic anhydride to give the 5-acetoxy derivative.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH565573X | 1942-01-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB565573A true GB565573A (en) | 1944-11-16 |
Family
ID=4520573
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB133/43A Expired GB565573A (en) | 1942-01-05 | 1943-01-04 | Manufacture of dioxane derivatives |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB565573A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2699438A (en) * | 1952-04-19 | 1955-01-11 | Rayonier Inc | Linear polyesters of carboxy-2-hydroxymethyl benzodioxane |
US2906757A (en) * | 1959-09-29 | Their preparation | ||
US3170933A (en) * | 1963-01-28 | 1965-02-23 | Boehringer Sohn Ingelheim | 2-(gamma-methoxypropyl-aminomethyl)-1, 4-benzodioxane |
US4837336A (en) * | 1985-10-23 | 1989-06-06 | Glaxo Group Limited | Process for preparing heterocyclic compounds |
US4840965A (en) * | 1987-07-07 | 1989-06-20 | Syntex (U.S.A.) Inc. | Naphthalene anti-psoriatic agents |
EP0928791A1 (en) * | 1997-05-12 | 1999-07-14 | Daiso Co., Ltd. | Process for producing 1,4-benzodioxane derivatives |
-
1943
- 1943-01-04 GB GB133/43A patent/GB565573A/en not_active Expired
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2906757A (en) * | 1959-09-29 | Their preparation | ||
US2699438A (en) * | 1952-04-19 | 1955-01-11 | Rayonier Inc | Linear polyesters of carboxy-2-hydroxymethyl benzodioxane |
US3170933A (en) * | 1963-01-28 | 1965-02-23 | Boehringer Sohn Ingelheim | 2-(gamma-methoxypropyl-aminomethyl)-1, 4-benzodioxane |
US4837336A (en) * | 1985-10-23 | 1989-06-06 | Glaxo Group Limited | Process for preparing heterocyclic compounds |
US4840965A (en) * | 1987-07-07 | 1989-06-20 | Syntex (U.S.A.) Inc. | Naphthalene anti-psoriatic agents |
EP0928791A1 (en) * | 1997-05-12 | 1999-07-14 | Daiso Co., Ltd. | Process for producing 1,4-benzodioxane derivatives |
EP0928791A4 (en) * | 1997-05-12 | 2002-03-20 | Daiso Co Ltd | Process for producing 1,4-benzodioxane derivatives |
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