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WO1996004229A1 - Preparation de composes organiques - Google Patents

Preparation de composes organiques Download PDF

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Publication number
WO1996004229A1
WO1996004229A1 PCT/GB1995/001764 GB9501764W WO9604229A1 WO 1996004229 A1 WO1996004229 A1 WO 1996004229A1 GB 9501764 W GB9501764 W GB 9501764W WO 9604229 A1 WO9604229 A1 WO 9604229A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic compound
fluorine
oxidation
aryl
solvent
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.)
Ceased
Application number
PCT/GB1995/001764
Other languages
English (en)
Inventor
Richard Dickinson Chambers
Graham Sandford
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
F2 Chemicals Ltd
Original Assignee
BNFL Fluorochemicals Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BNFL Fluorochemicals Ltd filed Critical BNFL Fluorochemicals Ltd
Publication of WO1996004229A1 publication Critical patent/WO1996004229A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation

Definitions

  • the present invention relates to the preparation of organic compounds.
  • it relates to the synthesis of compounds containing one or more carbonyl groups by oxidation of alcohols, diols and polyols.
  • Oxidants derived from chromium, manganese, ruthenium, silver, aluminium and cerium have all been the subject of intense study. However, the toxicity and, therefore, disposal problems associated with using such materials makes these methods environmentally less acceptable.
  • Non-metallic oxidants in general use include DMSO (dimethyl sulfoxide) with various oxidants, but the formation of significant quantities of by-products in such oxidations again causes disposal problems.
  • Halogens and related halogen containing compounds have also been studied as potentially useful oxidation systems. Yields of oxidations using these reagents are generally low and both chlorine and bromine may be used only if the structural features of the product do not allow chlorination or bromination at the ⁇ -position to the carbonyl.
  • 1,2-diols to 1,2-hydroxycarbonyl compounds are a special case and is not easily achieved by reaction of the free diols as, generally, oxidation of 1,2-diols results in carbon-carbon bond cleavage.
  • the formation of 1,2-hydroxycarbonyl compounds from 1,2-diols requires the use of oxidants such as silver carbonate, dimethyl sulfoxide-phosphorous pentoxide, dimethyl sulfoxide-chlorine, dimethyl sulfide-N-chlorosuccinimide or dimethyl sulfide-chlorine to effect such transformations.
  • Oxidation of 1,2-diols to 1,2-diones may be achieved with DMSO-oxalyl chloride.
  • a method for the oxidation of one or more hydroxyl groups in an organic compound to one or more carbonyl groups which comprises reacting the organic compound with elemental fluorine.
  • the said organic compound may be an aliphatic or aromatic alcohol, diol or polyol.
  • the organic compound is contained in a liquid through which fluorine is passed as a gas.
  • the rate of delivery of fluorine gas may vary between wide limits depending upon the scale of the reaction and may be adjusted to control the rate of the oxidation reaction.
  • the said liquid may comprise the appropriate organic compound to be oxidised together with a substantially inert solvent, eg a neutral substance such as water optionally together with an inert neutral organic solvent such as acetonitrile.
  • a substantially inert solvent eg a neutral substance such as water optionally together with an inert neutral organic solvent such as acetonitrile.
  • the liquid may optionally include also a solvent for fluorine, eg a fluorinated or perfluorinated organic compound such as a fluoro- or perfluoro-alkane.
  • the method according to the present invention may be carried out in a vessel in which the solution is present or alternatively a flowing stream of the solution may be contacted with a gaseous flow of fluorine in countercurrent fashion.
  • the method according to the present invention may be carried out at a temperature in the range -60°C to +90°C although a temperature of from -20°C to +50°C is preferred. Ambient temperatures eg 15°C to 25°C may conveniently be employed.
  • the ratio of fluorine to the organic compound to be oxidised may be varied within wide limits although it is preferred that the molar ratio is in the range 0.5 to 2.0:1, especially 1.1 to 1.25:1 (fluorine: organic compound) .
  • Fluorine is preferably passes slowly through a solution of the alcohol, diol or polyol in a solvent containing water at room temperature, thus oxidising the alcohol, diol or polyol in a reaction that can be easily controlled simply by adjusting the flow rate of the introduction of fluorine gas into the reaction vessel.
  • the desired product can be selected by adjustment of the amount of fluorine taking part in the reaction.
  • the rate may for example be less than lOml/min eg less than 5ml/min, for small scale apparatus and at higher rates for larger scale apparatus.
  • the ability to control the level of oxidation in the method according to the present invention allows for example 1,2-diols to be converted to either 1,2-hydroxycarbonyl compounds when one equivalent of fluorine is used in the oxidation, or to 1,2-diones when two equivalents of fluorine are passed through the reaction medium. Such control of the level of oxidation is not possible if the oxidant is the preformed HOF.MeCN reagent as employed in the prior art.
  • the present invention also allows, for example, the selective oxidation of any number of hydroxyl groups in either a cyclic or acyclic polyalcohol to the corresponding polycarbonyl derivative. .
  • R, R lf R 2 , R3 , R4, R5 and R 6 are each independently selected from hydrogen or the following groups which may be optionally substituted or contain optional hetero atoms: alkyl, alkoxy, cycloalky] , aryl, acyl, acyloxy nitro, cyano halogen.
  • R, R lf R 2 , R3 , R4, R5 and R 6 are each independently selected from hydrogen or the following groups which may be optionally substituted or contain optional hetero atoms: alkyl, alkoxy, cycloalky] , aryl, acyl, acyloxy nitro, cyano halogen.
  • any of the groups is or contains an alkyl group the group is preferably C- -n alkyl.
  • n is an integer in the range 1 to 8 inclusive.
  • the fluorinated product in the process according to "the present invention may be isolated by purging the reaction mixture with inert gas to remove any residual fluorine gas followed by neutralisation with sodium bicarbonate solution and extraction into a suitable solvent followed by purification by distillation or column chromatography.
  • the present process according to the present invention provides an inexpensive and convenient synthetic route for the oxidation of alcohols to the corresponding carbonyl derivatives.
  • trans-cyclohexane-l,2-diol (2.0g, 17mmol) and fluorine (17mmol) gave a crude yellow oil of 2-hydroxy- cyclohexanone; GC/MS (87% conversion; 100% yield) .
  • Reaction with 2, 4-dinitrophenylhydrazine gave the 2,4- dinitrophenylhydrazone of 2-hydroxy-cyclohexanone as an orange solid (3.7g, 85% yield based on 87% conversion); .p. 153°C (lit. 150°C) ; (Found: C, 49.4; H, 4.6; N, 18.9.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Procédé d'oxydation d'un ou de plusieurs groupe(s) hydroxyle(s) dans un composé organique afin d'obtenir un ou plusieurs groupe(s) carbonyle(s), ce procédé consistant à faire réagir le composé organique avec du fluor élémentaire. Ce composé organique peut être un alcool, un diol ou un polyol aliphatique ou aromatique et il est contenu dans un liquide à travers lequel on fait passer le fluor sous forme gazeuse.
PCT/GB1995/001764 1994-07-29 1995-07-26 Preparation de composes organiques Ceased WO1996004229A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9415312A GB9415312D0 (en) 1994-07-29 1994-07-29 The preparation of organic compounds
GB9415312.9 1994-07-29

Publications (1)

Publication Number Publication Date
WO1996004229A1 true WO1996004229A1 (fr) 1996-02-15

Family

ID=10759071

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1995/001764 Ceased WO1996004229A1 (fr) 1994-07-29 1995-07-26 Preparation de composes organiques

Country Status (3)

Country Link
GB (1) GB9415312D0 (fr)
WO (1) WO1996004229A1 (fr)
ZA (1) ZA956322B (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6242653B1 (en) 1998-08-21 2001-06-05 Basf Aktiengesellschaft Process for the preparation of α-diketones from ketols or ketals from ketols
JP2008308419A (ja) * 2007-06-13 2008-12-25 Ube Ind Ltd テトラヒドロピラン−４−オンの製法
RU2838317C1 (ru) * 2024-09-16 2025-04-14 Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук (ИОС УрО РАН) Способ получения циклогексанона

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3038941A (en) * 1959-03-23 1962-06-12 Du Pont Process for preparing polyfluoroaldehydes
US3165554A (en) * 1962-07-25 1965-01-12 Dow Chemical Co Oxidation of cyclic and aliphatic alcohols

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3038941A (en) * 1959-03-23 1962-06-12 Du Pont Process for preparing polyfluoroaldehydes
US3165554A (en) * 1962-07-25 1965-01-12 Dow Chemical Co Oxidation of cyclic and aliphatic alcohols

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6242653B1 (en) 1998-08-21 2001-06-05 Basf Aktiengesellschaft Process for the preparation of α-diketones from ketols or ketals from ketols
US6316676B1 (en) 1998-08-21 2001-11-13 Basf Aktiengesellschaft Process for the preparation of α-diketones from ketols or ketals from ketols
JP2008308419A (ja) * 2007-06-13 2008-12-25 Ube Ind Ltd テトラヒドロピラン−４−オンの製法
RU2838317C1 (ru) * 2024-09-16 2025-04-14 Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук (ИОС УрО РАН) Способ получения циклогексанона

Also Published As

Publication number Publication date
GB9415312D0 (en) 1994-09-21
ZA956322B (en) 1996-03-14

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