IP Library Granted Patent US 8,119,667
Granted Patent B2
US 8,119,667 · App. 11/611,997 · Granted Feb 21, 2012

Carbonates of fenicol antibiotics

Assignee: Schering-Plough Animal Health Corporation
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Quick Facts
Patent No.
US 8,119,667
App. No.
11/611,997
Granted
Feb 21, 2012
Kind
B2
Abstract

Novel fenicol compounds having useful properties as antibiotic prodrugs, are provided, together with methods of making and using these new compounds.

Claims (51)

1. A fenicol carbonate of Formula I, or a solvate thereof,

wherein R 1 is selected from the group consisting of

R 2 is selected from a group consisting of dichloromethyl, difluoromethyl, chlorfluoromethyl, chloromethyl and methyl,

R 3 is selected from a group consisting of hydroxymethyl, fluoromethyl, difluoromethyl, trifluoromethyl and CH 2 O—C(O)O—R 5 ,

R 4 and R 5 are independently selected from the group consisting of substituted or unsubstituted C 1-10 straight, branched or cyclo alkyl, substituted or unsubstituted C 1-10 alkoxyalkyl, C 1-10 aryl, C 1-10 arylalkyl, substituted or unsubstituted C 1-10 straight, branched or cycloalkenyl.

2. The fenicol carbonate of claim 1 wherein R 4 and R 5 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl,n -decyl, n-dodecyl, n-octadecyl, 2-methyl-butyl, 1-ethyl-propyl, 3-methyl-prop-2-enyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2-propoxy-ethyl, 2-butoxy-ethyl, 1-methyl-2-methoxy-ethyl, cyclopropyl-methyl, cyclopentyl-methyl, cyclohexyl-methyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 3,7-dimethyloct-6-enyl, benzyl,2 -methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl, 2-methoxy-benzyl, 3-methoxy-benzyl,4-methoxy-benzyl, methyl-2-furyl, 2-(methoxy-ethoxy)-ethyl, 2-(ethoxy-ethoxy)-ethyl, 2-[2-(methoxy-ethoxy)-ethoxy]-ethyl, 2-[2-(ethoxy-ethoxy) -ethoxy]-ethyl, 2-(hydroxy-ethoxy)-ethyl, 2-[2-(hydroxy-ethoxy)-ethoxy]-ethyl,2-acetoxy-ethyl, 2-(acetoxy-ethoxy)-ethyl, 3-acetoxy-propyl, 2-carboxy-ethyl, 3-carboxy-propyl, 4-carboxy-butyl, 2-methoxycarbonyl-ethyl, 3-methoxycarbonyl-propyl, 4-methoxycarbonyl-butyl, 2-methoxycarbonyl-benzyl, 3-methoxycarbonyl -benzyl, 4-methoxycarbonyl-benzyl, 1-ethoxycarbonyl-ethyl, 1-methoxycarbonyl-ethyl, phenyl, 4-methyl-phenyl, 4-methoxy-phenyl, 4-carboxy-phenyl, 2-carboxy-phenyl, 4-methoxycarbonyl-phenyl, 2-methoxycarbonyl-phenyl and 4-acetylamino-phenyl.

3. The fenicol carbonate of claim 2 wherein R 4 and R 5 are independently substituted with a moiety selected from the group consisting of methyl, methoxy, carboxy, carboalkoxy and acyloxy.

4. The fenicol carbonate of claim 2 , wherein R 1 is selected from the group consisting of

R 2 is dichloromethyl or difluoromethyl, and R 3 is selected from the group consisting of hydroxymethyl, fluoromethyl and CH 2 O—C(O)O—R 5 .

5. The fenicol carbonate of claim 1 wherein R 1 is CH 3 SO 2 , R 2 is CHCl 2 and R 3 is CH 2 F.

6. The florfenicol carbonate of claim 5 , wherein R 4 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-octadecyl, 2-methyl-butyl, 1-ethyl-propyl, 3-methyl-prop-2-enyl, 2-methoxy-ethyl, 2-ethoxy-ethyl,2-propoxy-ethyl, 2-butoxy-ethyl, 1-methyl-2-methoxy-ethyl, cyclopropyl -methyl, cyclopentyl-methyl, cyclohexyl-methyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 3,7-dimethyloct-6-enyl, benzyl, 2-methyl-benzyl, 3-methyl-benzyl, 4-methyl-benzyl, 2-methoxy-benzyl, 3-methoxy-benzyl, 4-methoxy -benzyl, methyl-2-furyl, 2-(methoxy-ethoxy)-ethyl, 2-(ethoxy-ethoxy)-ethyl,2-[2-(methoxy-ethoxy)-ethoxy]-ethyl, 2-[2-(ethoxy-ethoxy)-ethoxy]-ethyl, 2-(hydroxy-ethoxy) -ethyl, 2-[2-(hydroxy-ethoxy)-ethoxy]-ethyl, 2-acetoxy-ethyl, 2-(acetoxy-ethoxy) -ethyl, 3-acetoxy-propyl, 2-carboxy-ethyl, 3-carboxy-propyl, 4-carboxy-butyl, 2-methoxycarbonyl-ethyl, 3-methoxycarbonyl-propyl, 4-methoxycarbonyl-butyl, 2-methoxycarbonyl-benzyl, 3-methoxycarbonyl-benzyl, 4-methoxycarbonyl-benzyl, 1-ethoxycarbonyl -ethyl, 1-methoxycarbonyl-ethyl, phenyl, 4-methyl-phenyl, 4-methoxy-phenyl, 4-carboxy-phenyl, 2-carboxy-phenyl, 4-methoxycarbonyl-phenyl, 2-methoxycarbonyl-phenyl and 4-acetylamino-phenyl.

7. The fenicol carbonate of claim 1 , wherein R 3 is CH 2 F.

8. The fenicol carbonate of claim 1 , wherein R 1 is CH 3 SO 2 R 2 is CHCl 2 , R 3 is OH and R 4 is ethyl.

9. The fenicol carbonate of claim 1 , wherein R 1 is CH 3 SO 2 , R 2 is CHCl 2 , R 3 is

and R 4 is ethyl.

10. The fenicol carbonate of claim 1 that is selected from the group consisting of

11. The fenicol carbonate of claim 1 that is selected from the group consisting of the following compounds

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl) propyl methyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl ethyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl propyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl isopropyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl isobutyl carbonate;

cyclopropylmethyl (1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl 3-methylbut-2-enyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl isopentyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl pentan-3-yl carbonate;

cyclohexyl (1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl 2-methoxyethyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl 2-ethoxyethyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl-2-butoxyethyl carbonate;

benzyl (1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl 4-methylbenzyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl 4-methoxybenzyl carbonate;

(S)-ethyl 2-(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propoxy)carbonyloxy)propanoate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl dodecyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl octadecyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl-(3R,S)-3,7-dimethyloct-6-enyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl 2-(2-methoxyethoxy)ethyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl octyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl 2-(2-(2-methoxyethoxy)ethoxy)ethyl carbonate;

(1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-fluoromethylsulfonyl)phenyl)propyl ethyl carbonate; and

bis((1R,2S)-2-(2,2-dichloroacetamido)-3-fluoro-1-(4-(methylsulfonyl)phenyl)propyl) ethane-1,2-diyl dicarbonate.

12. A fenicol carbonate compound of Formula II,

wherein R 1 is selected from the group consisting of

wherein a, c and e are integers that independently range in value from 0 through 4, b and d are integers that independently range in value from 0 through 2, provided that the sum of integers a, b, c, d and e range in value from 2 to 8,

R 51 and R 52 are independently selected from the group consisting of H, methyl, hydroxyl, methoxy, and acetoxy.

13. The compound of claim 12 wherein the sum of a, b, c, d and e ranges in value from 2 through 4.

14. The compound of claim 12 where R 1 is

15. The compound of claim 12 , having a structure selected from the group consisting of:

16. The compound of claim 1 , having the following structure

17. The compound of claim 15 , having the following structure

Assignments (8)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 29, 2019
From: MSD INTERNATIONAL HOLDINGS GMBH; INTERVET INC.; MERCK SHARP & DOHME (HOLDINGS) PTY LTD
To: INTERVET INC.
Reel/Frame 048176/0132 →
CHANGE OF NAME Recorded Jan 28, 2019
From: SCHERING-PLOUGH PTY. LIMITED
To: MERCK SHARP & DOHME (HOLDINGS) PTY LTD
Reel/Frame 048151/0525 →
CHANGE OF NAME Recorded Jan 25, 2019
From: SCHERING-PLOUGH ANIMAL HEALTH CORPORATION
To: INTERVET INC.
Reel/Frame 048144/0476 →
MERGER Recorded Jan 24, 2019
From: SCHERING-PLOUGH LTD.
To: MSD INTERNATIONAL HOLDINGS GMBH
Reel/Frame 048120/0380 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 25, 2007
From: ZHANG, JASON
To: SCHERING-PLOUGH ANIMAL HEALTH CORPORATION; SCHERING-PLOUGH LTD.; SCHERING-PLOUGH PTY. LIMITED
Reel/Frame 018803/0885 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 25, 2007
From: SHUSTER, DALE EDWARD
To: SCHERING-PLOUGH ANIMAL HEALTH CORPORATION; SCHERING-PLOUGH LTD.; SCHERING-PLOUGH PTY. LIMITED
Reel/Frame 018803/0783 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 25, 2007
From: GLINKA, TOMASZ W.
To: SCHERING-PLOUGH ANIMAL HEALTH CORPORATION; SCHERING-PLOUGH LTD.; SCHERING-PLOUGH PTY. LIMITED
Reel/Frame 018803/0796 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 25, 2007
From: CELLY, CHANDER SHEKHER; SIMMONS, ROBERT D.
To: SCHERING-PLOUGH ANIMAL HEALTH CORPORATION; SCHERING-PLOUGH LTD.; SCHERING-PLOUGH PTY. LIMITED
Reel/Frame 018803/0822 →
Continuity (3)
Provisional Application 60754967 · Dec 29, 2005
Provisional Application 60781487 · Mar 10, 2006
Related Publication 20070155799A1 · Jul 5, 2007