Selective catalysts for spinetoram production

Patent metadata

Field	Value
Publication number	US-10507461-B2
Application number	US-201715444793-A
Country	US
Kind code	B2
Filing date	Feb 28, 2017
Priority date	Mar 4, 2016
Publication date	Dec 17, 2019
Grant date	Dec 17, 2019

Abstract

This invention is based on the discovery that homogeneous catalysts, [Rh(C2H4)2Cl]2 and/or [Rh(COD)2][BF4], can be used to produce spinetoram in higher yields at lower catalyst loadings as compared to previous methodologies. In addition, one or more phosphorus ligand donors can also be added to further increase yields/efficiency. The methods and/or systems provided herein enable cost-effective ways to produce spinetoram in large quantity with relatively simple procedures.

First claim

I claim:

1. A process for producing spinetoram comprising:
selectively hydrogenating a mixture of 3′-O-ethyl spinosyn J and 3′-O-ethyl spinosyn L, in the presence of
(a) a homogeneous catalyst selected from the group consisting of [Rh(C 2 H 4 ) 2 Cl] 2 , [Rh(COD) 2 ][BF 4 ], [Rh(COD) 2 ][OTs], and combinations thereof, at a temperature between 15° C. and 100° C. with a hydrogen gas pressure between 5 psig and 200 psig, wherein the COD is 1,5-cyclooctadiene and the OTs is p-toluenesulfonate; and
(b) a phosphorus ligand donor selected from the group consisting of tris(3,5-dimethylphenyl)phosphine,

and combinations thereof.

2. The process of claim 1 , wherein the phosphorus ligand donor comprises tris(3,5-dimethylphenyl)phosphine.

3. The process of claim 1 , wherein the phosphorus ligand donor is selected from the group consisting of

4. The process of claim 1 , wherein the temperature is about 30° C., 45° C., or 65° C.

5. The process of claim 1 , wherein the hydrogen gas pressure is about 60 psig or 150 psig.

6. The process of claim 1 , wherein the yield of spinetoram is about or greater than 90% by 1 H nuclear magnetic resonance (NMR) spectroscopic analysis or high-performance liquid chromatography (HPLC) analysis.

7. The process of claim 1 , wherein the catalyst loading is between 0.01 mol % and 2 mol %.

8. The process of claim 1 , wherein the homogeneous catalyst is [Rh(C 2 H 4 ) 2 Cl] 2 .

9. A selective hydrogenation system for producing spinetoram comprising
(a) a mixture of 3′-O-ethyl spinosyn J and 3′-O-ethyl spinosyn L;
(b a homogeneous catalyst selected from the group consisting of [Rh(C 2 H 4 ) 2 Cl] 2 , [Rh(COD) 2 ][BF 4 ], [Rh(COD) 2 ][OTs], and combinations thereof, wherein the COD is 1,5 -cyclooctadiene and the OTs is p-toluenesulfonate: and
(c) a phosphorus ligand donor selected from the group consisting of tris(3,5-dimethylphenyl) phosphine,

and combinations thereof.

10. The system of claim 9 , wherein the phosphorus ligand donor comprises tris(3,5-dimethylphenyl)phosphine.

11. The system of claim 9 , wherein the phosphorus ligand donor is selected from the group consisting of

12. A process for producing spinetoram comprising providing the system of claim 9 to hydrogenate the mixture of 3-O-enthyl spinosyn J and 3′-O-ethyl spinosyn L at a temperature between 15° C. and 100° C. with a hydrogen gas pressure between 5 psig and 200 psig.

13. The process of claim 12 , wherein the yield of spinetoram is about or greater than 90% by 1 H nuclear magnetic resonance (NMR) spectroscopic analysis or high-performance liquid chromatography (HPLC) analysis.

14. The process of claim 12 , wherein the catalyst loading is between 0.01 mol % and 2 mol %.

Assignees

• Dow Agrosciences Llc

Inventors

• Foskey Takiya J

Classifications

• B01J31/2433

  comprising aliphatic or saturated rings · CPC title

• A01N43/22

  rings with more than six members · CPC title

• B01J31/22 Primary

  Organic complexes · CPC title

• C07H1/00

  Processes for the preparation of sugar derivatives · CPC title

• C07H17/08

  Hetero rings containing eight or more ring members, e.g. erythromycins · CPC title