CA1039750A - PROCESS FOR THE PREPARATION OF .alpha.-DIOL-.gamma.-DIOXO COMPOUNDS - Google Patents
PROCESS FOR THE PREPARATION OF .alpha.-DIOL-.gamma.-DIOXO COMPOUNDSInfo
- Publication number
- CA1039750A CA1039750A CA229,051A CA229051A CA1039750A CA 1039750 A CA1039750 A CA 1039750A CA 229051 A CA229051 A CA 229051A CA 1039750 A CA1039750 A CA 1039750A
- Authority
- CA
- Canada
- Prior art keywords
- preparation
- diol
- process according
- osmium tetroxide
- represent
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
Abstract
ABSTRACT OF THE DISCLOSURE
The invention relates to a process for the preparation of-.alpha.-diol-?-dioxo compounds having the general formula:
in which R1 and R4 which may be identical or different, each represent a lower alkyl radical and R2 and R3 each represent a hydrogen atom, comprising reacting a compound having the general formula:
wherein R1, R2, R3, R4 have the above meanings with an oxidizing mixture consisting of osmium tetroxide and an alkaline or alkaline earth metal chlorate, in the presence of water. The ?-diol-?
dioxo compounds according to the present invention are useful synthesis intermediates, for instance in the preparation via cyclization of furane derivatives, some of which may be employed as flavorants and perfumes.
The invention relates to a process for the preparation of-.alpha.-diol-?-dioxo compounds having the general formula:
in which R1 and R4 which may be identical or different, each represent a lower alkyl radical and R2 and R3 each represent a hydrogen atom, comprising reacting a compound having the general formula:
wherein R1, R2, R3, R4 have the above meanings with an oxidizing mixture consisting of osmium tetroxide and an alkaline or alkaline earth metal chlorate, in the presence of water. The ?-diol-?
dioxo compounds according to the present invention are useful synthesis intermediates, for instance in the preparation via cyclization of furane derivatives, some of which may be employed as flavorants and perfumes.
Description
16~39750 - The present invention relates to a process for the preparation of -diol -dioxo compounds having the general formula:
R2 3 ~ -R -CO-C - ~-co~R4 OH OH
in which R and R which may be identical or different, each represent a lower alkyl radical and R and R3 each represent a hy-drogen atom, which process comprises reacting a compound having - the general formula R _ co_1 - 1 co- R4 in whcih Rl, R2, R3, R4 have the above meanings, with an oxidizing mixture of osmium tetroxide and an alkaline or alkaline-earth chlorate, in the presence of water:
The ~-diol-~-dioxo compounds according to the present invention are useful synthesis intermediates, for instance in the preparation via cyclization of furane derivatives, some of which may be employed as flavorants or perfumes / see G. B~chi, E. Demo-le and F. Thomas, I. Org. Chem. 38, 123 (1973) and L. Re, B. Maurer, G. Ohlaff, Helv. 56, 1882 (1973)7. Compared to the known methods of preparation of the aforesaid~-diol-~-dioxo compounds, the method according to the invention has the advantage of being not only cheaper but also simpler form an operative point of view.
Furthermore, in the preparation of furane derivatives through cyclization, the method according to the invention of synthesis of ~-diol-~-dioxo compounds is particularly interesting . : ~ , . ;. ~.
;;~ since it enables the cyclization, through kno~ operations (see already cited G. B~chi et al.), of the aqueous mixture obtained at the end of the reaction, after recovery of osmium tetroxide, ~-without isolating the intermediate compound. ~
' 16)39750 , ...
According to the invention, the oxidizing agent , comprises osmium tetroxide. This compound can be used in cataly-tic amounts preferably of at least 20 mg per g of substrate, -since it is continuously regenerated by the chlorate through an oxidative scission of the adduct between osmium tetroxide and ~ -substrate. Chlorate must, therefore, be also present in at least stoichiometric amounts.
In accordance with the invention, osmium tetroxide : .
may be recovered at the end of the reaction by dragging under a ., .
nitrogen stream, osmium tetroxide being caught in a trap contain-; 10 ing the starting product with which it forms a non-volatile adduct, or by selective extraction by means of a suitable solvent ` such as CC14, benzene, Et2O and subsequent solvent evaporation after having add the extract to the starting products, or also by another techniques well known to any man skilled in the art.
The oxidation reaction is carried out in an aqueous environment at a temperature ranging from 0 to 100C, preferabl~3 from t25 to ~50C and under pressure to maintain the system in the liquid phase. When use is made of water unsoluble solid ~ ~ substrate, use is preferably made of an inert usual solvent :~
either miscible with water fro dissolving, at least partially, the substrate (THF, alcohols) or immiscible with water for I dissolving, also only partially, both the substrate and osmium .~; , . .
tetroxide (CC14, Et2O, benzene).
The present invention will be better understood with reference to the following non-restrictive examples.
~ I EXAMPLE 1.
; ~ PreParation of treo-3,4-dihYdroxYhexane-2,5-dione from . ::
~` ~ trans-3-hexene-2,5-dione To 15 ml of water were added 0.79 g (6.45 mmoles) of potassium chlorate, 250.4 mg (O.lO mmole) of osmium tetroxide and 0.50 g (4.46 mmoles) of trans-3-hexPne-2,5-dione. The mixture
R2 3 ~ -R -CO-C - ~-co~R4 OH OH
in which R and R which may be identical or different, each represent a lower alkyl radical and R and R3 each represent a hy-drogen atom, which process comprises reacting a compound having - the general formula R _ co_1 - 1 co- R4 in whcih Rl, R2, R3, R4 have the above meanings, with an oxidizing mixture of osmium tetroxide and an alkaline or alkaline-earth chlorate, in the presence of water:
The ~-diol-~-dioxo compounds according to the present invention are useful synthesis intermediates, for instance in the preparation via cyclization of furane derivatives, some of which may be employed as flavorants or perfumes / see G. B~chi, E. Demo-le and F. Thomas, I. Org. Chem. 38, 123 (1973) and L. Re, B. Maurer, G. Ohlaff, Helv. 56, 1882 (1973)7. Compared to the known methods of preparation of the aforesaid~-diol-~-dioxo compounds, the method according to the invention has the advantage of being not only cheaper but also simpler form an operative point of view.
Furthermore, in the preparation of furane derivatives through cyclization, the method according to the invention of synthesis of ~-diol-~-dioxo compounds is particularly interesting . : ~ , . ;. ~.
;;~ since it enables the cyclization, through kno~ operations (see already cited G. B~chi et al.), of the aqueous mixture obtained at the end of the reaction, after recovery of osmium tetroxide, ~-without isolating the intermediate compound. ~
' 16)39750 , ...
According to the invention, the oxidizing agent , comprises osmium tetroxide. This compound can be used in cataly-tic amounts preferably of at least 20 mg per g of substrate, -since it is continuously regenerated by the chlorate through an oxidative scission of the adduct between osmium tetroxide and ~ -substrate. Chlorate must, therefore, be also present in at least stoichiometric amounts.
In accordance with the invention, osmium tetroxide : .
may be recovered at the end of the reaction by dragging under a ., .
nitrogen stream, osmium tetroxide being caught in a trap contain-; 10 ing the starting product with which it forms a non-volatile adduct, or by selective extraction by means of a suitable solvent ` such as CC14, benzene, Et2O and subsequent solvent evaporation after having add the extract to the starting products, or also by another techniques well known to any man skilled in the art.
The oxidation reaction is carried out in an aqueous environment at a temperature ranging from 0 to 100C, preferabl~3 from t25 to ~50C and under pressure to maintain the system in the liquid phase. When use is made of water unsoluble solid ~ ~ substrate, use is preferably made of an inert usual solvent :~
either miscible with water fro dissolving, at least partially, the substrate (THF, alcohols) or immiscible with water for I dissolving, also only partially, both the substrate and osmium .~; , . .
tetroxide (CC14, Et2O, benzene).
The present invention will be better understood with reference to the following non-restrictive examples.
~ I EXAMPLE 1.
; ~ PreParation of treo-3,4-dihYdroxYhexane-2,5-dione from . ::
~` ~ trans-3-hexene-2,5-dione To 15 ml of water were added 0.79 g (6.45 mmoles) of potassium chlorate, 250.4 mg (O.lO mmole) of osmium tetroxide and 0.50 g (4.46 mmoles) of trans-3-hexPne-2,5-dione. The mixture
- 2 -~3~750 was stirred over 17 hours at room temperature in a closed vessel.
The water-insoluble liquid phase was extracted with dimethylfu-rane. To recover osmium tetroxide, nitrogen was bubbled through the reaction vessel connected, at its outlet, to a trap provided with a porous septum immersed in diemthylfurane and cooled. The osmium tetroxide, dragged by nitrogen, was caught through ~ formation of an adduct with hexenedione, that is not volatile.
; The content of the trap could be used, after addition of water and potassium chlorate, for another preparation.
; The reaction mixtùrewas dry evaporated under a 15 mmHg -;~ 10 vacuum at room temperature. The residue was extracted several times with ethyl acetate and the extracts, joined together, were ; dried (anhydrous sodium sulphate) and dry evaporated under vacuum.
0.51 g of a raw product was obtained, which, after having been again crystallized from ligroin, gave 0.31 g (47.6~ yield) of pure treo-3,4-dihydroxyhexan-2,5-dione, having a melting point of 88-90C. The obtained infrared and NMR spectra agreed with the ~
known ones (G. B~chi et al.) ;
~ EXAMPLE 2.
;~ Preparation of eritro-3,4-dihydroxyhexane-2,5-dione ~, .
from cis-3-hexene-2,5-dione To 6 ml of water were added 0.25 g (2.05 mmoles) of i~
j potassium chlorate, 10.2 mg (0.04 mmole) of osmium tetroxide q~ and 0.20 g (1.78 mmoles) of cis 3-hexene-2,5-dione. The mixture was stirred at room temperature for 6 hours in a closed vessel.
i Osmium tetroxide was recovered by selective extraction ' with carbon tetrachloride, followed by the addition of hexenedione ~ ;
to the extract, so as to form a non-volatile adduct between the ~ olefin and osmium tetroxide, and by a solvent evaporation. The I evaporation ~esidue could then be used, after addition of water ~;
and potassium chlorate, for another preparation.
The reaction mixture was dry evaporated under vacuum ~ 3 ~
,, . . ... . . . . - ~ .
1~)39750 (15 m~g) at room temperature. The residue was extracted several times with ethyl acetate and the extracts, joined together, were dried (anhydrous sodium sulphate) and dry evaporatèd under vacuum. 0.20 g of a white crystalline products was obtained having a melting point of 48-51C. Via crystallization from chloroform-carbon tetrachloride (1:1), 0.13 g (50~ yield) of pure eritro-3,4-dihydroxyhexane-2,5-dione was obtained having a m.p. of 56-60 C, and IR and NMR spectra agreeing with the known ones (G. B~chi et al.).
, ' '.
. ~ . .
., .
.~ .. .
., . ,~, , .
`.
~1 .
, . .
~ , ~
.
i - 4 -~ -, ~ '
The water-insoluble liquid phase was extracted with dimethylfu-rane. To recover osmium tetroxide, nitrogen was bubbled through the reaction vessel connected, at its outlet, to a trap provided with a porous septum immersed in diemthylfurane and cooled. The osmium tetroxide, dragged by nitrogen, was caught through ~ formation of an adduct with hexenedione, that is not volatile.
; The content of the trap could be used, after addition of water and potassium chlorate, for another preparation.
; The reaction mixtùrewas dry evaporated under a 15 mmHg -;~ 10 vacuum at room temperature. The residue was extracted several times with ethyl acetate and the extracts, joined together, were ; dried (anhydrous sodium sulphate) and dry evaporated under vacuum.
0.51 g of a raw product was obtained, which, after having been again crystallized from ligroin, gave 0.31 g (47.6~ yield) of pure treo-3,4-dihydroxyhexan-2,5-dione, having a melting point of 88-90C. The obtained infrared and NMR spectra agreed with the ~
known ones (G. B~chi et al.) ;
~ EXAMPLE 2.
;~ Preparation of eritro-3,4-dihydroxyhexane-2,5-dione ~, .
from cis-3-hexene-2,5-dione To 6 ml of water were added 0.25 g (2.05 mmoles) of i~
j potassium chlorate, 10.2 mg (0.04 mmole) of osmium tetroxide q~ and 0.20 g (1.78 mmoles) of cis 3-hexene-2,5-dione. The mixture was stirred at room temperature for 6 hours in a closed vessel.
i Osmium tetroxide was recovered by selective extraction ' with carbon tetrachloride, followed by the addition of hexenedione ~ ;
to the extract, so as to form a non-volatile adduct between the ~ olefin and osmium tetroxide, and by a solvent evaporation. The I evaporation ~esidue could then be used, after addition of water ~;
and potassium chlorate, for another preparation.
The reaction mixture was dry evaporated under vacuum ~ 3 ~
,, . . ... . . . . - ~ .
1~)39750 (15 m~g) at room temperature. The residue was extracted several times with ethyl acetate and the extracts, joined together, were dried (anhydrous sodium sulphate) and dry evaporatèd under vacuum. 0.20 g of a white crystalline products was obtained having a melting point of 48-51C. Via crystallization from chloroform-carbon tetrachloride (1:1), 0.13 g (50~ yield) of pure eritro-3,4-dihydroxyhexane-2,5-dione was obtained having a m.p. of 56-60 C, and IR and NMR spectra agreeing with the known ones (G. B~chi et al.).
, ' '.
. ~ . .
., .
.~ .. .
., . ,~, , .
`.
~1 .
, . .
~ , ~
.
i - 4 -~ -, ~ '
Claims (6)
1. Process for the preparation of ?-diol-?-dioxo compounds having the general formula:
in which R1 and R4, which may be identical or different, each represent a lower alkyl, and R2 and R3 each represent a hydrogen atom, which process comprises reacting a compound having the general formula:
wherein R1, R2, R3, R4 have the above meanings, with an oxidizing mixture consisting of osmium tetroxide and an alkaline or alka-line-earth metal chlorate, in the presence of water.
in which R1 and R4, which may be identical or different, each represent a lower alkyl, and R2 and R3 each represent a hydrogen atom, which process comprises reacting a compound having the general formula:
wherein R1, R2, R3, R4 have the above meanings, with an oxidizing mixture consisting of osmium tetroxide and an alkaline or alka-line-earth metal chlorate, in the presence of water.
2. Process according to claim 1, characterized in that the reaction is carried out at temperatures of from 0 to 100°C.
3. Process according to claim 3, characterized in that the reaction is carried out at temperatures of from +25 to +50°C.
4. Process according to claim 1, characterized in that the reaction is carried out at a pressure under which the system is in the liquid phase.
5. Process according to claim 1, characterized in that the water is added with an inert solvent.
6. Process according to claim 1, further comprising recovering osmium tetroxide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2389874A IT1014990B (en) | 1974-06-12 | 1974-06-12 | PROCEDURE FOR THE PREPARATION OF ALPHA DIOL RANGE DIOSSO COMPOUNDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1039750A true CA1039750A (en) | 1978-10-03 |
Family
ID=11210734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA229,051A Expired CA1039750A (en) | 1974-06-12 | 1975-06-11 | PROCESS FOR THE PREPARATION OF .alpha.-DIOL-.gamma.-DIOXO COMPOUNDS |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5111703A (en) |
| BE (1) | BE830111A (en) |
| CA (1) | CA1039750A (en) |
| CH (1) | CH605523A5 (en) |
| FR (1) | FR2274593A1 (en) |
| GB (1) | GB1470734A (en) |
| IT (1) | IT1014990B (en) |
| LU (1) | LU72707A1 (en) |
| NL (1) | NL7507039A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56148944A (en) * | 1980-03-15 | 1981-11-18 | Shiyuuichi Higuchi | Weft yarn sending nozzle of loom |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3488394A (en) * | 1966-05-11 | 1970-01-06 | Fmc Corp | Oxidation of olefinic compounds to glycols |
-
1974
- 1974-06-12 IT IT2389874A patent/IT1014990B/en active
-
1975
- 1975-06-05 FR FR7517604A patent/FR2274593A1/en active Granted
- 1975-06-10 LU LU72707A patent/LU72707A1/xx unknown
- 1975-06-11 CA CA229,051A patent/CA1039750A/en not_active Expired
- 1975-06-11 BE BE157226A patent/BE830111A/en not_active IP Right Cessation
- 1975-06-11 CH CH755975A patent/CH605523A5/xx not_active IP Right Cessation
- 1975-06-12 JP JP7024375A patent/JPS5111703A/en active Pending
- 1975-06-12 GB GB2528075A patent/GB1470734A/en not_active Expired
- 1975-06-12 NL NL7507039A patent/NL7507039A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5111703A (en) | 1976-01-30 |
| DE2525827B2 (en) | 1977-01-20 |
| CH605523A5 (en) | 1978-09-29 |
| FR2274593A1 (en) | 1976-01-09 |
| DE2525827A1 (en) | 1975-12-18 |
| LU72707A1 (en) | 1975-10-08 |
| BE830111A (en) | 1975-10-01 |
| GB1470734A (en) | 1977-04-21 |
| IT1014990B (en) | 1977-04-30 |
| NL7507039A (en) | 1975-12-16 |
| FR2274593B1 (en) | 1977-07-08 |
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