Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acids and salts thereof
Patent
1996-02-14
1998-03-24
Griffin, Walter D.
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acids and salts thereof
502164, 502172, 502173, 502321, 502313, 562407, 562409, 562544, 554138, C07C 5116, B01J 2354
Patent
active
057314608
DESCRIPTION:
BRIEF SUMMARY
This invention concerns the oxidative cleavage of alkenes and more specifically the catalysed oxidative cleavage of alkenes by reaction with hydrogen peroxide.
Alkenes represent convenient starting materials in the synthesis of organic chemicals because they are often readily available in good purity and at relatively low cost. Much of their utility depends on the introduction of additional or alternative functional groups to the alkene, and this is often conveniently achieved by reaction at the carbon-carbon double bond(s).
One common way of introducing functionality is to employ an oxidative cleavage of the double bond to produce one or more hydroxyl and/or carbonyl groups. Several methods are available for achieving this, including the use of reagents such as potassium permanganate and osmium and ruthenium tetraoxide, often known as stoichiometric reagents, and ozonolysis.
There are a number of difficulties associated with the use of such stoichiometric reagents. First, the need to employ the reagents in substantially stoichiometric or greater amounts means that relatively large and costly quantities are used. Second, it is often not a straightforward process to regenerate the reagent on completion of the oxidative cleavage and therefore there is a need to dispose of relatively large quantities of the spent reagent. This loss of chemicals coupled with the high cost of disposal of waste chemicals, particularly metal compounds, due at least in part to increasing regulatory pressure, increases the cost of the process. Third, the reagents employed are often volatile and highly toxic, particularly ruthenium and osmium tetraoxides so that there are usually handling difficulties associated with the use of such reagents.
In view of the problems associated with the use of stoichiometric reagents, an alternative method, namely ozonolysis has been proposed. Unfortunately, the use of ozonolysis brings with it its own difficulties. The handling of a reactive gas such as ozone often requires the construction of specialised dedicated chemical plant, which is highly capital intensive. Additionally, the generation of ozone is very energy intensive, which adds to the cost of the process. The highly reactive nature of ozone also makes its use less favoured because of the need for strict reaction control to prevent dangerous reaction runaways.
It would therefore be desirable to identify a further alternative oxidation system for the oxidative cleavage of alkenes.
One oxidant that is sometimes desirable to employ in chemical oxidations is an aqueous solution of hydrogen peroxide, because it is relatively cheap, easy to handle and is environmentally acceptable in that its decomposition products are water and oxygen. In order to achieve effective oxidations with hydrogen peroxide, it has often been found necessary to employ a catalyst. The use of catalysts can be favoured over the use of stoichiometric reagents because the quantities of catalyst required are relatively low, and in many instances, it is relatively easy to recycle the catalyst, resulting in reduced process costs. In their paper in J. Chem. Soc. Chem. Commun. 1987 (16) pp1266-7, Barak and Sasson disclose the use of RuCl.sub.3 as catalyst for the oxidation of styrene to benzaldehyde or acetophenone with hydrogen peroxide. Although this oxidation system avoids many of the problems associated with the use of stoichiometric reagents and with ozonolysis, the system has been found to have activity towards only a relatively restricted range of alkenes. Amongst those alkenes which are not oxidatively cleaved by the system of Barak and Sasson are such commercially important examples as oct-1-ene and non-2-ene.
In a paper presented at the DMGK-Conference "Selective Oxidations in Petrochemistry", September 16-18, 1992 in Goslar, Germany, Warwel et al disclose a ruthenium catalyst system for the oxidative cleavage of alkenes with peracetic acid. They then discuss the application of this ruthenium catalyst system to the oxidative cleavage of alkenes by hydrogen peroxide. The
REFERENCES:
patent: 3547962 (1970-12-01), Starks et al.
patent: 4606863 (1986-08-01), Nakazawa et al.
"Advanced Inorganic Chemistry", Third Edition, 1990. Francis A. Carey. pp.128-130, 1990-no month.
"Organic Chemistry". Francis A. Carey. pp. 873-875, 1987-no month.
Johnstone Alexander
Middleton Paul John
Sanderson William Ronald
Service Miranda
Griffin Walter D.
Preisch Nadine
Solvay Interox Limited
LandOfFree
Oxidative cleavage of alkenes with a catalyst system containing does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Oxidative cleavage of alkenes with a catalyst system containing , we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Oxidative cleavage of alkenes with a catalyst system containing will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2290001