Processes for the conversion of myrcene to citral

Claim 2

A process for producing citral comprising contacting myrcene with palladium (II) chloride in the presence of an inert aqueous alkylamide solvent and a metal oxoanionic salt at a temperature of at least about 80° C.

Claim 3

A process according to claim 1 wherein said temperature is at least about 90° C.

Claim 4

A process according to claim 1 wherein the palladium (II) chloride is selected from the group consisting of PdCl 2 and PdCl 2 loosely coordinated with ligand donors.

Claim 5

A process according to claim 3 wherein the ligand donors are selected from the group consisting of acetonitrile, benzonitrile, 1,5-cyclooctadiene and dimethyl sulfoxide.

Claim 6

A process according to claim 4 wherein the palladium (II) chloride is dichlorobisacetonitrile palladium.

Claim 7

A process according to claim 1 wherein the inert aqueous amide solvent is selected from the group consisting of N-substituted aqueous pyrrolidones, N-substituted aqueous caprolactams and N,N-disubstituted aqueous alkylamides.

Claim 8

A process according to claim 6 wherein the solvent is a substituted aqueous pyrrolidone which is aqueous N-methylpyrrolidone.

Claim 9

A process according to claim 1 wherein the metal oxoanionic salt is selected from the group consisting of Li 2 B 4 O 7 , Li 2 B 10 O 16 , Li 2 SiO 3 , Li 3 PO 4 , Li 2 WO 4 , Li 2 CrO 4 , Li 2 MoO 4 , LiTiO 3 , LiCoO 2 , Li 2 CO 3 , Li 2 SO 4 , Li 2 SnO 3 , Na 2 B 4 O 7 , Na 2 B 10 O 16 , Na 2 SiO 3 , Na 2 SnO 3 , Na 3 VO 4 , Na 3 PO 4 , Na 2 WO 4 , Na 2 CrO 4 , Na 2 MoO 4 , NaTiO 3 , NaCoO 2 , Na 2 CO 3 , Na 2 SO 4 , Na 2 TeO 4 , K 3 VO 4 , K 2 B 4 O 7 , K 2 B 10 O 16 , K 2 SiO 3 , K 2 SnO 3 , K 3 PO 4 , K 2 WO 4 , K 2 CrO 4 , K 2 MoO 4 , KTiO.sub. 3, K 2 SnO 3 , K 2 TeO 4 , KCoO 2 , K 2 CO 3 , K 2 SO 4 , MgB 4 O 7 , MgB 10 O 16 , MgSiO 3 , Mg 3 (PO 4 ) 2 , MgWO 4 , MgCrO 4 , MgMoO 4 , Mg(TiO 3 ) 2 , Mg(CoO 2 ) 2 , MgCO 3 , MgSO 4 , CaB 4 O 7 , CaB 10 O 16 , CaSiO 3 , Ca 3 (PO 4 ) 2 , CaWO 4 , CaCrO 4 , Ca(TiO 3 ) 2 , Ca(CoO 2 ) 2 , CaCO 3 , CaSO 4 , Cu 2 B 4 O 7 , Cu 2 B 10 O 16 , Cu 2 SiO 3 , Cu 3 PO 4 , Cu 2 WO 4 , Cu 2 CrO 4 , Cu 2 MoO 4 , CuTiO 3 , CuCoO 2 , Cu 2 CO 3 , Cu 2 SO 4 , CuB 4 O 7 , CuB 10 O 16 , CuSiO 3 , Cu 3 (PO 4 ) 2 , CuWO 4 , CuCrO 4 , CuMoO 4 , Cu(TiO 3 ) 2 , Cu(CoO 2 ) 2 , CuCO 3 , CuSO 4 , Ag 2 B 4 O 7 , Ag 2 B 10 O 16 , Ag 2 SiO 3 , Ag 3 PO 4 , Ag 2 WO 4 , Ag 2 CrO 4 , AgTiO 3 , AgCoO 2 , Ag 2 CO 3 , Ag 2 SO 4 , Al 2 (B 4 O 7 ) 3 , Al 2 (B 10 O 16 ) 3 , Al 2 (SiO 3 ) 3 , AlPO 4 , Al 2 (WO 4 ) 3 , Al 2 (CrO 4 ) 3 , Al 2 (MoO 4 ) 3 , Al(TiO 3 ) 3 , Al(CoO 2 ) 3 , Al 2 (CO 3 ) 3 , Al 2 (SO 4 ) 3 , SnB 4 O 7 , SnB 10 O 16 , SnSiO 3 , Sn 3 (PO 4 ) 2 , SnWO 4 , SnCrO 4 , SnMoO 4 , Sn(TiO 3 ) 2 , Sn(CoO 2 ) 2 , SnCO 3 , SnSO 4 , Sn(B 4 O 7 ) 2 , Sn(B 10 O 16 ) 2 , Sn(SiO 3 ) 2 , Sn 3 (PO 4 ) 4 , Sn(WO 4 ) 2 , Sn(CrO 4 ) 2 , Sn(MoO 4 ) 2 , Sn(TiO 3 ) 4 , Sn(CoO 2 ) 4 , Sn(CO 3 ) 2 , Sn(SO 4 ) 2 , PdB 4 O 7 , PdB 10 O 16 , PdSiO 3 , Pd 3 (PO 4 ) 2 , PdWO 4 , PdCrO 4 , PdMoO 4 , Pd(TiO 3 ) 2 , Pd(CoO 2 ) 2 , PdCO 3 , PdSO 4 , Pd(B 4 O 7 ) 2 , and Pd(B 10 O 16 ) 2 .

Claim 10

A process according to claim 8 wherein the metal oxoanionic salt is selected from the group consisting of Li 2 B 4 O 7 , Li 2 B 10 O 16 , Li 2 SiO 3 , Li 2 MoO 4 , Li 2 SO 4 , Li 2 CO 3 , Li 2 TeO 4 , Li 3 PO 4 , Na 2 B 4 O 7 , Na 2 B 10 O 16 , Na 2 SiO 3 , Na 2 SnO 3 , Na 2 MoO 4 , Na 2 TeO 4 , Na 3 PO 4 , Na 3 VO 4 , K 2 TeO 4 ,K 2 B 4 O 7 , K 2 B 10 O 16 , K 2 CO 3 , K 2 SiO 3 , K 2 SnO 3 , K 2 MoO 4 , K 3 VO 4 , MgB 4 O 7 , MgB 10 O 16 , MgSiO 3 , MgMoO 4 , Cu 2 B 4 O 7 , Cu 2 B 10 O 16 , Cu 2 SiO 3 , Cu 2 MoO 4 , CuB 4 O 7 , CuB 10 O 16 , CuSiO 3 , CuMoO 4 , SnB 4 O 7 , SnB 10 O 16 , SnSiO 3 , SnMoO 4 , Sn(B 4 O 7 ) 2 , Sn(B 10 O 16 ) 2 , Sn(SiO 3 ) 2 and Sn(MoO 4 ) 2 .

Claim 11

A process according to claim 9 wherein the metal oxoanionic salt is selected from the group consisting of Li 2 MoO 4 , Na 2 MoO 4 , and K 2 MoO 4 .

Claim 12

A process according to claim 1 wherein the myrcene is in the form of a myrcene and limonene mixture.

Claim 13

A process according to claim 11 wherein the myrcene to limonene ratio is about 80 to about 20.

Claim 14

A process according to claim 1 further comprising contacting the myrcene with palladium (II) chloride in the presence of an oxidizing agent.

Claim 15

A process according to claim 13 wherein the oxidizing agent is a member selected from the group consisting of hydrogen peroxide, benzoquinone, a copper (II) salt, a cerium (IV) salt, an iron (III) salt and a silver (I) salt.

Claim 16

A process according to claim 14 wherein the oxidizing agent is a copper (II) salt or an iron (III) salt and said process is conducted in the presence of oxygen.

Claim 17

A process for producing citral comprising contacting a palladium-myrcene complex of the formula ##STR4## with a metal oxoanionic salt in the presence of an inert organic solvent.

Claim 18

A process for producing citral comprising contacting a palladium-myrcene complex of the formula ##STR4## with a metal oxoanionic salt in the presence of an inert organic solvent.

Claim 19

A process according to claim 16 wherein the process is carried out at a temperature of at least about 80° C.

Claim 20

A process according to claim 17 wherein the process is carried out at a temperature of at least about 90° C.

Claim 21

A process according to claim 16 wherein the metal oxoanionic salt is selected from the group consisting of Li 2 B 4 O 7 , Li 2 B 10 O 16 , Li 2 SiO 3 , Li 3 PO 3 , Li 2 WO 4 , Li 2 CrO 4 , Li 2 MoO 4 , LiTiO 3 , LiCoO 2 , Li 2 CO 3 , Li 2 SO 4 , Na 2 B 4 O 7 , Na 2 B 10 O 16 , Na 2 SiO 3 , Na 3 PO 4 , Na 2 WO 4 , Na 2 CrO 4 , Na 2 MoO 4 , NaTiO 3 , NaCoO 2 , Na 2 CO 3 , Na 2 SO 4 , K 2 B 4 O 7 , K 2 B 10 O 16 , K 2 SiO 3 , K 3 PO 4 , K 2 WO 4 , K 2 CrO 4 , K 2 MoO 4 , KTiO 3 , KCoO 2 , K 2 CO 3 , K 2 SO 4 , MgB 4 O 7 , MgB 10 O 16 , MgSiO 3 , Mg 3 (PO 4 ) 2 , MgWO 4 , MgCrO 4 , MgMoO 4 , Mg(TiO 3 ) 2 , Mg(CoO 2 ) 2 , MgCO 3 , MgSO 4 , CaB 4 O 7 , CaB 10 O 16 , CaSiO 3 , Ca 3 (PO 4 ) 2 , CaWO 4 , CaCrO 4 , Ca(TiO 3 ) 2 , Ca(CoO 2 ) 2 , CaCO 3 , CaSO 4 , Cu 2 B 4 O 7 , Cu 2 B 10 O 16 , Cu 2 SiO 3 , Cu 3 PO 4 , Cu 2 WO 4 , Cu 2 CrO 4 , Cu 2 MoO 4 , CuTiO 3 , CuCoO 2 , Cu 2 CO 3 , Cu 2 SO 4 , CuB 4 O 7 , CuB 10 O 16 , CuSiO 3 , Cu 3 (PO 4 ) 2 , CuWO 4 , CuCrO 4 , CuMoO 4 , Cu(TiO 3 ) 2 , Cu(CoO 2 ) 2 , CuCO 3 , CuSO 4 , Ag 2 B 4 O 7 , Ag 2 B 10 O 16 , Ag 2 SiO 3 , Ag 2 PO 4 , Ag 2 WO 4 , Ag 2 CrO 4 , AgTiO 3 , AgCoO 2 , Ag 2 CO 3 , Ag 2 SO 4 , Al 2 (B 4 O 7 ) 3 , Al 2 (B 10 O 16 ) 3 , Al 2 (SiO 3 ) 3 , AlPO 4 , Al 2 (WO 4 ) 3 , Al 2 (CrO 4 ) 3 , Al 2 (MoO 4 ) 3 , Al(TiO 3 ) 3 , Al(CoO 2 ) 3 , Al 2 (CO 3 ) 3 , Al 2 (SO 4 ) 3 , SnB 4 O 7 , SnB 10 O 16 , SnSiO 3 , Sn 3 (PO 4 ) 2 , SnWO 4 , SnCrO 4 , SnMoO 4 , Sn(TiO 3 ) 2 , Sn(CoO 2 ) 2 , SnCO 3 , SnSO 4 , Sn(B 4 O 7 ) 2 , Sn(B 10 O 16 ) 2 , Sn(SiO 3 ) 2 , Sn 3 (PO 4 ) 4 , Sn(WO 4 ) 2 , Sn(CrO 4 ) 2 , Sn(MoO 4 ) 2 , Sn(TiO 3 ) 4 , Sn(CoO 2 ) 4 , Sn(CO 3 ) 2 , Sn(SO 4 ) 2 , PdB 4 O 7 , PdB 10 O 16 , PdSiO 3 , Pd 3 (PO 4 ) 2 , PdWO 4 , PdCrO 4 , PdMoO 4 , Pd(TiO 3 ) 2 , Pd(CoO 2 ) 2 , PdCO 3 , PdSO 4 , and Pd(B 4 O 7 ) 2 .

Claim 22

A process according to claim 19 wherein the metal oxoanionic salt is selected from the group consisting of Li 2 B 4 O 7 , Li 2 B 10 O 16 , Li 2 SiO 3 , Li 2 MoO 4 , Na 2 B 4 O 7 , Na 2 B 10 O 16 , Na 2 SiO 3 , Na 2 MoO 4 , K 2 B 4 O 7 , K 2 B 10 O 16 , K 2 SiO 3 , K 2 MoO 4 , MgB 4 O 7 , MgB 10 O 16 , MgSiO 3 , MgMoO 4 , Cu 2 B 4 O 7 , Cu 2 B 10 O 16 , Cu 2 SiO 3 , Cu 2 MoO 4 , CuB 4 O 7 , CuB 10 O 16 , CuSiO 3 , CuMoO 4 , SnB 4 O 7 , SnB 10 O 16 , SnSiO 3 , SnMoO 4 , Sn(B 4 O 7 ) 2 , Sn(B 10 O 16 ) 2 , Sn(SiO 3 ) 2 and Sn(MoO 4 ) 2 .

Claim 23

A process according to claim 20 wherein the metal oxoanionic salt is selected from the group consisting Li 2 B 4 O 7 , Li 2 B 10 O 16 , K 2 B 4 O 7 and K 2 B 10 O 16 .

Claim 24

A process according to claim 16 wherein the inert aqueous organic solvent is selected from the group consisting of N-substituted aqueous pyrrolidones, N-substituted aqueous caprolactams, N,N-disubstituted aqueous acetamides, and substituted and unsubstituted toluene in water.

Claim 25

A process according to claim 22 wherein the solvent is an N-substituted aqueous pyrrolidone which is aqueous N-methylpyrrolidone.

Claim 26

A process according to claim 24 wherein the solvent is unsubstituted toluene in water.