CA1110255A - Method for the preparation of 2,5-dialkyl-4-hydroxy-2, 3-dihydrofuran-3-ones - Google Patents
Method for the preparation of 2,5-dialkyl-4-hydroxy-2, 3-dihydrofuran-3-onesInfo
- Publication number
- CA1110255A CA1110255A CA312,375A CA312375A CA1110255A CA 1110255 A CA1110255 A CA 1110255A CA 312375 A CA312375 A CA 312375A CA 1110255 A CA1110255 A CA 1110255A
- Authority
- CA
- Canada
- Prior art keywords
- dihydrofuran
- hydroxy
- preparation
- dialkyl
- ones
- 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
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
- Furan Compounds (AREA)
- Seasonings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
METHOD FOR THE PREPARATION OF 2,5-DIALKYL-4-HYDROXY-2,3-DIHYDROFURAN-3-ONES.
ABSTRACT OF THE DISCLOSURE :
A method is disclosed for preparing certain 2,5-dialkyl-4-hydroxy-2,3-dihydrofuran-3-ones, said method comprising the step of cyclizing the corresponding diol-diones with a cation exchange resin in an aqueous or an aqueous-alcoholic medium and at the reflux temperature of the reaction mixture. The method is cheap, convenient anc dependable.
ABSTRACT OF THE DISCLOSURE :
A method is disclosed for preparing certain 2,5-dialkyl-4-hydroxy-2,3-dihydrofuran-3-ones, said method comprising the step of cyclizing the corresponding diol-diones with a cation exchange resin in an aqueous or an aqueous-alcoholic medium and at the reflux temperature of the reaction mixture. The method is cheap, convenient anc dependable.
Description
ZSS
. .
This invention relates to a novel method for the preparation of 2,5-dialkyl-4-hydroxy-2,3-dihydrofuran-3-ones having the formula:
HO O
~ (I) R Rl wherein the two R groups are methyl radicals or wherein one of the R is a methyl radical and the other is an ethyl radical starting from compounds of the formula:
-CH3 fH-CO-CO-lH-R
OH H , (II) in which R is a methyl or an ethyl radical, by cyclization in aqueous solutions in the presence of ion exchange resins which are insoluble in the reaction medium. The product of ~formula (I) possess appreciable organoleptic properties so that they are considerably interesting for the alimentary, pharmaeeutieal and perfume industries.
The product of formula (II) can be obtained with eeonomically acceptable methods (see for example L. Re and G. Ohloff, USP 3 576 014 of Firmenich & Cie.; L. Re and V.
Caciagli, Ger. Offen. 2 426 051 of Snamprogetti S.p.A.) Previously, the best method for obtaining the compounds of formula (I) was based on the cyclization of the preeursors of formula (II) by mineral or organie aeids,or aeidie buffers soluble in the reaction medium.
The method aceording to the present invention affords the following advantages over the prior method:
1) The eyelization agents, whieh must be used in a great amount with respeet to the diol-dione with both methods, can be recovered by mere filtration and reused.
. .
This invention relates to a novel method for the preparation of 2,5-dialkyl-4-hydroxy-2,3-dihydrofuran-3-ones having the formula:
HO O
~ (I) R Rl wherein the two R groups are methyl radicals or wherein one of the R is a methyl radical and the other is an ethyl radical starting from compounds of the formula:
-CH3 fH-CO-CO-lH-R
OH H , (II) in which R is a methyl or an ethyl radical, by cyclization in aqueous solutions in the presence of ion exchange resins which are insoluble in the reaction medium. The product of ~formula (I) possess appreciable organoleptic properties so that they are considerably interesting for the alimentary, pharmaeeutieal and perfume industries.
The product of formula (II) can be obtained with eeonomically acceptable methods (see for example L. Re and G. Ohloff, USP 3 576 014 of Firmenich & Cie.; L. Re and V.
Caciagli, Ger. Offen. 2 426 051 of Snamprogetti S.p.A.) Previously, the best method for obtaining the compounds of formula (I) was based on the cyclization of the preeursors of formula (II) by mineral or organie aeids,or aeidie buffers soluble in the reaction medium.
The method aceording to the present invention affords the following advantages over the prior method:
1) The eyelization agents, whieh must be used in a great amount with respeet to the diol-dione with both methods, can be recovered by mere filtration and reused.
2) The isolation of the furan derivative from the reaction mixture is operatively simpler since it does not ZSi5 require the continuous removal of the product from the aqueous phase with ethyl ether and can be effected by mere evaporation, after filtration from the resin, of the aqueous filtrate, followed by extraction of the product from the residue with an appropriate solvent (preferably carbon tetrachloride) and by evaporation of said solvent.
3) The furan derivatives isolated from the reaction mixture do not require any further purification ~purity: 95~) whereas for the preparation according to the previous method of the derivative (I) in which the two R are methyl radicals, a purification by sublimation must be made after the isolation of the reaction raw product.
More detailedly, for thé preparation of the derivative of formula (I),the starting diol-dione of formula (II) is reacted in a mixture of water with a hydrophilic solvent (such as methano, ethanol, dioxan and others) or, preferably in pure water with a cation exchange resin (such as Amberlite IR 122,* IR 124*, IR 112,* IR 200* or IR 120,* preferably with the latter) at a temperature comprised between 50C and 150C
(preferably 100C) and in an inert atmosphere (such as nitrogen).
In the case of the diol-dione of formula (II) in which R is an et~yl radical, the cyclization gives a mixture of the two isomers 2-ethyl-5-methyl-2,3-dihydrofuran-3-one and 5-ethyl-2-methyl-2,3-dihydrofuran-3-one in a ratio of about 2:1, which can be used as such in the food, pharmaceutical and perfum industries.
The working details will be clearer, anyhow, from the scrutiny of the ensuing examples:
E X A M P L E
Preparation of 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran-3-one To 1.040 g of 2,5-dihydroxyhexane-3,4-dione (raw) dissolved in 20 mls water are added 4.75 g of Amberlite IR
* Trademark 3 .~
120* resin and the mixture is refluxed with stirring in an atmosphere of nitrogen during 4 hours.
The aqueous solution, upon filtration of the resin, is neutralized with 2N-NaOH and evaporated to dryness under vacuum at room temperature. The oily residue which is obtained is extracted three times with a 10 ml portion of carbon tetra-chloride each time. After removing the solvent in vacuum at room temperature there is obtained a residue of 0.327 g (yield 32% from hexindiol) of 2,5-dimethyl-4-hydroxy'-2,3-dihydrofuran-3-one, an oily substance which crystallizes spontaneously and has a gas-chromatographic purity of 95% (the gas-chromatographic analysis have been made with a Hewlett-Packard* instrument Model 7620-A equipped with thermoconductivity detector. Column 6-foot by 1/8 in. of 4~ SE 30 on silanized Chromosorb G*(60-80 mesh) 170C for 6 mins, then 170C to 230C (30C per min.) with 8 mls/min helium, using eicosane as the internal standard) m.p.
60C - 70C, IR, mass and NMR spectra in accordance with - literature (J.O. Rodin et al., J. Food Science, 30, 280 (1965)).
Preparation of 2-ethyl-5-methyl-4-hydroxy-2,3-dihydrofuran-3-one, and 5-ethyl-2-methyl-4-hydroxy-2,3-dihydrofuran-3-one.
To 1.139 g of 2,5-dihydroxyheptane-3,4-dione (raw) (prepared from 3-heptine-2,5-diol) dissolved in 20 mls water are added 4.75 g of Amberlite IR 120* resin and the mixture is refluxedin a nitrogen atmosphere for 6 hours. The aqueous solution, after having filtering off the resin, is neutralized with 2-N NaOH and evaporated to dryness under vacuum at room temperature. The oily residue which is obtained is extracted with three successive portion of 10 ml each of carbon tetra-chloride. After removing the solvent under vacuum at room temperature an oily residue is obtained, 0.325 g (yield 29% from heptine diol), composed by a mixture of 2-ethyl-5-methyl-4-* (trade mark)
More detailedly, for thé preparation of the derivative of formula (I),the starting diol-dione of formula (II) is reacted in a mixture of water with a hydrophilic solvent (such as methano, ethanol, dioxan and others) or, preferably in pure water with a cation exchange resin (such as Amberlite IR 122,* IR 124*, IR 112,* IR 200* or IR 120,* preferably with the latter) at a temperature comprised between 50C and 150C
(preferably 100C) and in an inert atmosphere (such as nitrogen).
In the case of the diol-dione of formula (II) in which R is an et~yl radical, the cyclization gives a mixture of the two isomers 2-ethyl-5-methyl-2,3-dihydrofuran-3-one and 5-ethyl-2-methyl-2,3-dihydrofuran-3-one in a ratio of about 2:1, which can be used as such in the food, pharmaceutical and perfum industries.
The working details will be clearer, anyhow, from the scrutiny of the ensuing examples:
E X A M P L E
Preparation of 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran-3-one To 1.040 g of 2,5-dihydroxyhexane-3,4-dione (raw) dissolved in 20 mls water are added 4.75 g of Amberlite IR
* Trademark 3 .~
120* resin and the mixture is refluxed with stirring in an atmosphere of nitrogen during 4 hours.
The aqueous solution, upon filtration of the resin, is neutralized with 2N-NaOH and evaporated to dryness under vacuum at room temperature. The oily residue which is obtained is extracted three times with a 10 ml portion of carbon tetra-chloride each time. After removing the solvent in vacuum at room temperature there is obtained a residue of 0.327 g (yield 32% from hexindiol) of 2,5-dimethyl-4-hydroxy'-2,3-dihydrofuran-3-one, an oily substance which crystallizes spontaneously and has a gas-chromatographic purity of 95% (the gas-chromatographic analysis have been made with a Hewlett-Packard* instrument Model 7620-A equipped with thermoconductivity detector. Column 6-foot by 1/8 in. of 4~ SE 30 on silanized Chromosorb G*(60-80 mesh) 170C for 6 mins, then 170C to 230C (30C per min.) with 8 mls/min helium, using eicosane as the internal standard) m.p.
60C - 70C, IR, mass and NMR spectra in accordance with - literature (J.O. Rodin et al., J. Food Science, 30, 280 (1965)).
Preparation of 2-ethyl-5-methyl-4-hydroxy-2,3-dihydrofuran-3-one, and 5-ethyl-2-methyl-4-hydroxy-2,3-dihydrofuran-3-one.
To 1.139 g of 2,5-dihydroxyheptane-3,4-dione (raw) (prepared from 3-heptine-2,5-diol) dissolved in 20 mls water are added 4.75 g of Amberlite IR 120* resin and the mixture is refluxedin a nitrogen atmosphere for 6 hours. The aqueous solution, after having filtering off the resin, is neutralized with 2-N NaOH and evaporated to dryness under vacuum at room temperature. The oily residue which is obtained is extracted with three successive portion of 10 ml each of carbon tetra-chloride. After removing the solvent under vacuum at room temperature an oily residue is obtained, 0.325 g (yield 29% from heptine diol), composed by a mixture of 2-ethyl-5-methyl-4-* (trade mark)
-4-1~ 2~5 hydroxy-2,3-dihydrofuran-3-one and 5-ethyl-2-methyl-4-hydroxy-2,3-dihydrofuran-3-one (2:1 approx.) of a gaschromatographical purity of 94% (gas chromatographic conditions as for 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran-3-one), b.p. 62C - 65C
(0.015 mmHg) with mass and NMR spectra in accordance with the data of the literature.
(0.015 mmHg) with mass and NMR spectra in accordance with the data of the literature.
Claims (3)
1. A method for the preparation of substituted dihydro-furans of the formula (I) wherein R and R1 are methyl radicals or in which either radical is a methyl radical whereas the other is an ethyl radical, by cyclization of compounds of formula (II) wherein R and R1 have the meanings explained above, characterized in that the cyclization reaction is carried out in the presence of a catalyst composed by cation exchange resins and insoluble in the reaction medium.
2. Method according to claim 1, characterized in that the reaction is carried out at a temperature comprised between 50°C
and 150°C in an inert atmosphere.
and 150°C in an inert atmosphere.
3. Method according to claim 1 or 2, characterized in that the reaction is carried out in an aqueous or an aqueous-alcoholic solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2880077A IT1087026B (en) | 1977-10-20 | 1977-10-20 | PROCEDURE FOR THE PREPARATION OF 2,5-DIALKYL-4-HYDROXY-2,3-DIIDROFURAN-3-ONI |
| IT28800A/77 | 1977-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1110255A true CA1110255A (en) | 1981-10-06 |
Family
ID=11224207
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA312,375A Expired CA1110255A (en) | 1977-10-20 | 1978-09-29 | Method for the preparation of 2,5-dialkyl-4-hydroxy-2, 3-dihydrofuran-3-ones |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5463068A (en) |
| BE (1) | BE871421A (en) |
| CA (1) | CA1110255A (en) |
| CH (1) | CH636611A5 (en) |
| DE (1) | DE2845843C3 (en) |
| FR (1) | FR2406636A1 (en) |
| GB (1) | GB2006205B (en) |
| IT (1) | IT1087026B (en) |
| LU (1) | LU80371A1 (en) |
| NL (1) | NL7810532A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2831676A1 (en) * | 1978-07-19 | 1980-02-07 | Basf Ag | NEW BIS-EPOXY-DIALKOXY ALKANES, THEIR PRODUCTION AND USE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1383492A (en) * | 1970-12-21 | 1974-02-12 | Unilever Ltd | Dicarbonyl compounds and preparation of dihydrofuranones therefrom |
-
1977
- 1977-10-20 IT IT2880077A patent/IT1087026B/en active
-
1978
- 1978-09-29 CA CA312,375A patent/CA1110255A/en not_active Expired
- 1978-10-11 GB GB7840115A patent/GB2006205B/en not_active Expired
- 1978-10-16 LU LU80371A patent/LU80371A1/en unknown
- 1978-10-17 FR FR7829553A patent/FR2406636A1/en active Granted
- 1978-10-18 JP JP12745678A patent/JPS5463068A/en active Pending
- 1978-10-19 CH CH1083578A patent/CH636611A5/en not_active IP Right Cessation
- 1978-10-20 DE DE19782845843 patent/DE2845843C3/en not_active Expired
- 1978-10-20 BE BE191250A patent/BE871421A/en not_active IP Right Cessation
- 1978-10-20 NL NL7810532A patent/NL7810532A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2406636B1 (en) | 1981-08-14 |
| JPS5463068A (en) | 1979-05-21 |
| NL7810532A (en) | 1979-04-24 |
| FR2406636A1 (en) | 1979-05-18 |
| LU80371A1 (en) | 1979-03-19 |
| GB2006205B (en) | 1982-03-31 |
| DE2845843C3 (en) | 1980-12-18 |
| BE871421A (en) | 1979-04-20 |
| DE2845843B2 (en) | 1980-04-30 |
| GB2006205A (en) | 1979-05-02 |
| CH636611A5 (en) | 1983-06-15 |
| DE2845843A1 (en) | 1979-04-26 |
| IT1087026B (en) | 1985-05-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |