# US 4,393,244 A · Method and the manufacture of cyclic mono and/or diketones from cyclic mono or sesqui terpenes by catalytic oxidation

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- Number: US 4,393,244 A
- Document ID: US4393244A
- Status: Granted
- Kind: A
- Application number: 06/296,280
- Filed: 1981-08-26
- Granted: 1983-07-12
- Earliest claimed: 1981-08-26
- Assignees: Indian Explosives Limited
- Inventors: Sumit Bhaduri; Madan M. Mahandru
- Web page: https://patentgrep.com/patent/US4393244A

## CPC

- B01J 31/2404: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring}
- B01J 31/1815: {with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine}
- B01J 31/183: {with more than one complexing nitrogen atom, e.g. phenanthroline}
- B01J 31/2243: {At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand}
- C07C 45/34: in unsaturated compounds
- C07C 49/623: having two rings
- B01J 2231/70: Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J 2531/16: Copper
- B01J 2531/56: Vanadium
- B01J 2531/64: Molybdenum
- B01J 2531/72: Manganese
- B01J 2531/822: Rhodium
- B01J 2531/842: Iron
- B01J 2531/845: Cobalt
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## 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.

## Claims

### Claim 1

A process for the preparation of cyclic mono 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 a catalyst selected from the group consisting of compounds of the formulas:
M.sub.m (L.sub.2)nX.sub.p (O).sub.q
where
L.sub.2 is 2,2'-bipyridyl or 1,10-orthophenanonthroline, and either
(a) M is Cu, m=2, X is I, Br or Cl, p=2, q=0; or
(b) M is Cu, m=1, n=1, X is NO.sub.2, p=2 and q=0; or
(c) M is Mo, m=1, n=1, X=Br, p=2 and q=2;
R"L.sub.3 Cl
where
L is triphenylphosphine; ##STR3## where M is Co, X=2 to 3 and R.sub.1 and R.sub.2 which may be the same or different represent methyl, ethyl, propyl, trifluoromethyl, phenyl or benzyl; and
M(O).sub.m [(R.sub.1 CO)CH(COR.sub.2)].sub.n
where
R.sub.1 and R.sub.2 which may be the same or different represent methyl, ethyl, n-propyl, trifluoromethyl, phenyl or benzyl, and
(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=o, n=2, 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, m=o, n=3.

### Claim 2 (depends on 1)

A process as claimed in claim 1, in which the oxygen containing gas is air.

### Claim 3 (depends on 1, 2)

A process as claimed in claim 1 or claim 2, wherein the reaction is conducted at from 0.degree. C. to about 250.degree. C.

### Claim 4 (depends on 3)

A process as claimed in claim 3, wherein the temperature is from about ambient room temperature to about 100.degree. C.

### Claim 5 (depends on 3)

A process as claimed in claim 3, wherein the reaction is conducted at a pressure of from 1 atmosphere to 1000 psi.

### Claim 6 (depends on 5)

A process as claimed in claim 5, wherein the pressure is from 50-400 psi.

### Claim 7 (depends on 4)

A process as claimed in claim 4, in which the reaction is conducted in the presence of an inert liquid diluent.

### Claim 8 (depends on 1)

A process as claimed in claim 1, wherein .alpha.-pinene is converted to 2,6,6-trimethylbicyclo(3,1,1)hept-2-en-4-one.

### Claim 9 (depends on 1)

A process as claimed in claim 1, wherein .DELTA..sup.3 -carene is converted to 3,7,7-trimethylbicyclo(4,1,0)hept-3-en-5-one and/or 3,7,7-trimethylbicyclo(4,1,0)hept-3-en-2,5-dione.

### Claim 10 (depends on 1)

A process as claimed in claim 1, wherein bicyclogeracrene is converted to 4,11,11-trimethylbicyclo(8,1,0)undec-4,8-dien-7-one and/or 4,11,11-trimethylbicyclo(8,1,0)undec-4-8-dien-6,7-dione.