THE PREPARATION OF CYCLIC KETONES BY CATALYTIC OXIDATION OF DELTACARENE (-3)

Abstract: Cyclic terpenes containing at least one unsubstituted methylene group adjacent to a double bond are converted into cyclic mono- and/or diketones by oxidation with oxygen in the presence of a transition metal catalyst.

Description: DESCRIPTION "THE PREPARATION OF CYCLIC KETONES BY CATALYTIC OXIDATION OF CYCLIC TERPENES" The present invention relates to the manufacture of mono and/or diketonic derivatives of mono or sesqui-terpenic olefines by catalytic oxidation. Of the many substrates which have been oxidised in the presence of transition metal complexes, one of the most extensively studied groups of organic compounds has been oleo in hydrocarbons. Surprisingly, no attempt has so far been made to invent similar methods for selective oxidation of terpenic olefines to oxygencontaining products. The present invention provides a method for selective oxidation of terpenic olefines to oxygencontaining products. The present invention also opens up the possibility of further functionalisation of the parent olefines. The oxidized products can in most cases be converted into valuable chemicals. Thus, 2,6,6trimethyl bicyclo (3,1,1) hept-2-en-4-one can be converted into thymol by a simple catalytic dehydrogenation. The method of the present invention consists in oxidizing with oxygen or an oxygen-containing gas such as air , mono or sesqui-terpenic olefines using, as catalyst, a co-ordination or organometallic complex of V, Cr, Mn, Fe, Rh, Co, Cu, Ir, Ni, Pd, Pt and Cu. The olefines must satisfy one important condition, namely one or both of the allylic positions should be unsubstituted. Obviously, for a diketonic derivative, both such positions must be unsubstituted whereas for a monoketonic derivative at least one allylic position should be unsubstituted. Accordingly, the invention provides a process for the preparation of cyclic, monb and/or diketones which comprises reacting a cyclic mono or sesquiterpenoid hydrocarbon containing at least one unsubstituted methylene group adjacent to a double bond with oxygen or an oxygen-containing gas in the presence of, as catalyst, a carboxylate salt or co-ordination or organometallic complex of a transition metal. The following diagram illustrates some of these conversions: EMI2.1 <tb> <SEP> ¸ <SEP> M·t <SEP> (1) <tb> <SEP> 0 <tb> <SEP> · <SEP> oana/or <tb> ss <SEP> Catalyst <SEP> ss <SEP> and/or <SEP> X <tb> <SEP> 0 <SEP> 0 <tb> <SEP> (2) <SEP> (3) <tb> · <SEP> ¸ > <SEP> (4) <tb> <SEP> Catalyst <tb> <SEP> and/or <tb> <SEP> O <tb> <SEP> (5) <tb> <SEP> 0S <tb> Although some conversions into a mixture of mono- and diketonic derivatives can be effected by complexes of all the metals listed above, for high conversions and selectivities, the preferred metals are Mn(II) or Mn(III), Co(II) or Co(III), Cu(I) or Cu(II) and Fe(II) or Fe(III). The reactions presumably proceed through the well-known Haber-Weiss mechanism of radical auto-oxidation. It is known that under the conditions used for similar oxidations of olefines the original ligand environment of the metal ion does not remain unchanged. The effectiveness of the catalyst partly depends on its solubility and, therefore, any soluble compound of the preferred metals should be able to initiate and propagate the radical auto-oxidation in varying degree. Apart from the carboxylates such as stearates, oleates, acelates and benzoates of Co(II or III), Mn(II or III) and Cu(I or II) which have been widely used for the other oleo in oxidation reactions, the catalysts can be any one or more of the compounds represented by the formulae A, B, C and D as depicted below: : M (L,) X (0) q where L2 = 2,2' bipyridyl or Formula A substituted 2,2' bipyridyl or substituted or unsubstituted 1,10 orthophenanthrcline; and a) M = Cu, m = 2, n = 2, X = 1, Br or C1 and p = 2, q = 0 or b) M = Cu, m = 1, n = 1, X = NO2, p = 2, q = 0 or c) M = Mo, m = 1, n = 1, X = Br, p = 2, q = 2 M(O)m(RlCO)CH(COR2)n Formula B where, a) M = V, m = 1, n = 2, R1 and R2 which may be the same or different, represent CH3, C2H5, n-C3H7, CF3, C6H5, C6H5CH2 or b) M = Mo, m = 2, n = 2, R1 and R2 as shown in (a) or c) M = Co, m = O, n = 2, R1 and R2 as shown in (a) or d) M = Co, m = O, n = 3, R1 and R2 as shown in (a) or e) M = Mn, m = O, n = 2 as shown in (a) or f) M F Cu, m = O, n = 2 as shown in (a) or g) M = Rh, m = O, n = 3 as shown in (a) M = Fe, m = O, n = 3 as shown in (a) MLnXp Formula C where, a) M = Rh, L = PPh3, n = 3, X = C1, p = 1 or b) M = Rh, L = PPh3, n = 3, X = C1, p = 2 EMI4.1 Formula D where , M = Co, x = 2 or 3, R1 and Rv which may be the same or different and represent CH3, C2H5, C3H7, CF3, Ph, PhCH2. The oxidation reaction can be effected at a temperature from OOC to about 2500C and preferably at ambient room temperature up to about 1000C. Both air or pure oxygen can be used as the oxidising agent. The pressures employed are in the range of atmospheric to 1000 psi (70 kg./cm2). Optimisation of temperature and pressure is required depending on the substrate involved, and the desired ratio of the mono- to diketonic derivatives. The residence time of the reaction can be followed by taking periodic gas-chromatographic samples of the product mixture. The products are first isolated by chromatographic techniques and structures established by the usual spectroscopic methods. These are then used for rapid gas-chromatographic analysis. The reaction time varies with the desired ratio of mono- to diketonic derivatives, the pressure employed, the temperatures used and the like considerations. In the practice of these processes undiluted terpenic olefines are preferably used but they can also be diluted with solvents. The solvents employable include by way of example carbon tetrachloride, benzene, n-octane, decalin and ethyl acetate. The following Examples are given by way of illustration of the invention. Example 1 a-Pinene (15 parts) was contacted with 2,2'bipyridyl cuprous iodide dimer (0.5 part) at 50 C under air at a pressure of 100 psi (7 kg./cm2) for 600 minutes. The reaction mixture was vigorously stirred. The products were analysed by gas liquid chromatography showing 40% conversion of a-pinene to the corresponding mono-ketone derivative (1) in the diagram. Example 2 #3-Carene (20 parts) was contacted with bis (pentane-2,4-dionato) cobalt (II) (0.2 part) under 50 psi (3.5 kg./cm2) of oxygen for 60 minutes. The reaction mixture was vigorously stirred. The products were analysed by gas liquid chromatography showing 75% conversion of A3-carene. The converted material consisted of the 5-ketocarene (60%), 2,5-diketo-carene (10%) and other products (5%). Example 3 A3-carene (20 parts) was contacted with cobalt (II) stearate (0.5 part) under 250 psi (17.5 kg./cm2) of oxygen at 800C for 24 hours. The reaction mixture was vigorously stirred. The products were analysed by gasliquid chromatography showing 95 conversion of #3-carene. The converted material consisted of the 5-ketocarene (30%), 2,5-diketo-carene (50J,) and other products (15%). Example 4 Bicyclogeracrene (25 parts) was contacted with manganese (II) acetate (1 part) at 1200C under an oxygen pressure of 400 psi (28 kg./cm2). The reaction mixture was vigorously stirred for 12 hours. The products were analysed by gas-liquid chromatography showing 60% conversion of which the diketone and the monoketone (5) and (4) in the diagram were 50% and 5%.

Claims: C L A I M S 1. A process for the preparation of cyclic mono and/or dike tones which comprises reacting a cyclic mono or sesquiterpenoid hydrocarbon containing at least one unsubstituted methylene group adjacent to a double bond with oxygen or an oxygen-containing gas in the presence of, as catalyst, a carboxylate salt or a co-ordination or organometallic complex of a transition metal. 2. A process as claimed in claim 1, in which the oxygen-containing gas is air. 3. A process as claimed in claim 1 or claim 2, wherein the reaction is conducted at from 0 C to about 250"C, preferably from about ambient room temperature to about 100"C. 4. A process as claimed in any one of claims 1 to 3, wherein the reaction is conducted at a pressure of from 1 atmosphere to 1000 psi (70kg/cm2), preferably 50-400 psi (3.5-28 kg/cm2). 5. A process as claimed in any one of claims 1 to 4, in which the reaction is conducted in the presence of an inert liquid diluent. 6. A process as claimed in any of claims 1 to 5, wherein the catalyst is a carboxylate salt, co-ordination or organo-metallic complex of vanadium, chromium, rhodium, ruthenium, iridium, nickel, palladium, or platinum, or, more especially, manganese, cobalt, copper or iron. 7. A process as claimed in any one of claims 1 to 5, wherein the catalyst has the formula Mm(L ) x (0) 2np q where L2 is 2,2'-bipyridyl or substituted 2,2'-bipyridyl or unsubstituted, l,10-orthophenanthroline, and either (a) N is Cu, m = 2, X is I, Br or C1, p = 2, q = O; or (b) M is Cu, m = 1, n = 1, X is NO2, p = 2 and q = O; or (c) N is Mo, m = 1, n = 1, X = Br, p = 2 and q = 2. 8. A process as claimed in any one of claims 1 to 5, wherein the catalyst has the formula M(O)m(R1Co) CH(COR2)n where R1 and R2 which may be the same or different represent methyl, ethyl, n-propyl, trifluoromethyl, phenyl or benzyl, and either (a) M is V, m = 1, n = 2, or (b) M is Mo, m = 2, n = 2; or (c) M is Co, m = O, n = 2; or (d) M is Co, m = 0, n = 3, or (e) M is Mn, m = O, n = 2; or (f) M is Cu, m = O, n = 2; or (g) M is Rh, m = O, n = 3; or (h) M is Fe, in = O, n = 3. 9 A process as claimed in any one of claims 1 to 5, wherein the catalyst has the formula MLnXp where M is Rh, L is triphenylphosphine, n = 3, X = C1 and p = 1 or 2. 10. A process as claimed in any of claims 1 to 5, wherein the catalyst has the formula EMI8.1 where x = 2 or 3 and R1 and R2 which may be the same or different represent methyl, ethyl, propyl, trifluoromethyl, phenyl or benzyl. 11. A process as claimed in any of claims 1 to 10, wherein a-pinene is converted to 2,6,6-trimethylbicyclo (3,1,1) hept-2-en-4-one, #3-carene is converted to 3,7,7trimethylbicyclo(4,1,0)hept-3-en-5-one and/or 3,7,7 trimethylbicyclo(4,1,0)hept-3-en-2,5-dione, or bicyclogeracrene is converted to 4a11,11-trimethylbicyclo (8,1,0)undec-4,8-dien-7-one and/or 4,11,11-trimethyl bicyclo(8,1,0)undec-4-8-dien-6,7-dione. CLAIMS 1. A process for the preparation of cyclic mono and/or diketones which comprises reacting #3-carene with oxygen or an oxygen-containing gas in the presence of, as catalyst, a carboxylate salt or a co-ordination or organometallic complex of a transition metal. 2. A process as claimed in claim 1, in which the oxygen-containing gas is air. 3. A process as claimed in claim 1 or claim 2, wherein the reaction is conducted at from 0 C to about 2506C, preferably from about ambient room temperature to about 100"C. 4. A process as claimed in any one of claims 1 to 3, wherein the reaction is conducted at a pressure of from 1 atmosphere to 1000 psi (70kg/cm2), 2 preferably 50-400 psi (3.5-28 kg/cm ). 5. A process as claimed in any one of claims 1 to 4, in which the reaction is conducted in the presence of an inert liquid diluent. 6. A process as claimed in any of claims 1 to 5, wherein the catalyst is a carboxylate salt, co-ordination or organo-metallic complex of vanadium, chromium, rhodium, ruthenium, iridium, nickel, palladium, or platinum, or, more especially, manganese, cobalt, copper or iron. 7. A process as claimed in any one of claims 1 to 5, wherein the catalyst has the formula M (L ) X (O) where L2 is 2,2'-bipyridyl or substituted 2,2'-bipyridyl or unsubstituted, l,l0-orthophenanthroline, and either (a) M is Cu, m = 2, X is I, Br or C1, p - 2, q = O; or (b) M is Cu, m = 1, n = 1, X is NO2, p = 2 and q = O; or (c) M is Mo, m = 1, n = 1, X = Br, p = 2 and q = 2. 8. A process as claimed in any one of claims 1 to 5, wherein the catalyst has the formula M(O)m(R1CO) CH(COR2)n where R1 and R2 which may be the same or different represent methyl, ethyl, n-propyl, trifluoromethyl, phenyl or benzyl, and either (a) M is V, m = 1, n = 2, or (b) M is Mo, m = 2, n = 2; or (c) M is Co, m = O, n = 2: or (d) M is Co, m = 0, n = 3, or (e) M is Mn, m = O, n = 2; or (f) M is Cu, m = O, n = 2; or (g) M is Rh, m = O, n = 3; or (h) N is Fe, m = O, n = 3. 9. A process as claimed in any one of claims 1 to 5, wherein the catalyst has the formula ML X where M is Rh, L is triphenylphosphine, n = 3, X = C1 and p = 1 or 2. 10. A process as claimed in any of claims 1 to 5, wherein the catalyst has the formula EMI11.1 where x = 2 or 3 and R1 and R2 which may be the same or different represent methyl. ethyl, propyl, trifluoromethyl, phenyl or benzyl. 11. A process as claimed in any of claims 1 to 1O, wherein A3-carene is converted to 3,7,7-trimethylbicyclo [4.1.Oj hept-3-en-5-one and/or 3,7,7-trimethyl bicyclo (4.1.0)hept-3-en-2,5-dione.

Inventors: BHADURI, SUMIT C/O ALCEMIE R.C.P.L., MAHANDRU, MADAN MOHAN C/O ALCHEMIE R.C.P.L.
Applicants: CHEMICALS AND FIBRES OF INDIA LIMITED, INDIAN EXPLOSIVES LIMITED, THE ALKALI AND CHEMICAL CORPORATION OF INDIA LIMITED
Application year: 1981
Main classification: C07C49
IPC codes: C07C49, C07C45