IP Library Patent Application 11507099
Patent Application
App. No. 11/507,099

Useful indole compounds

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Patent No.
US None
App. No.
11/507,099
Abstract

Indoles having various activities, including indoles that are CRTH2 are described. The compounds are useful for treating asthma, neuropathic pain, allegic rhinitis and other disorders.

Claims (280)

1 . A compound having Formula I

wherein

R 1 is H or a halogen;

R 2 is OH, a halogen, -CH 3 , wherein any carbon can be optionally, independently substituted with one or more halogen; or -OCH 3 , wherein any carbon can be optionally, independently substituted with one or more halogen;

R 3 is a halogen or -CH 3 ;

R 8 is H or Cl;

R 6 is independently selected from F, Cl, Br, -CH 3 , CF 3 , -OCH 3 , OCF 2 H, -OCFH 2 , -OCF 3 -CN, -SCF 3 , -SCH 3 , CF 2 H, or -SCF 2 H;

m is 1 , 2 , or 3 .

R 9 is -CH 2 CH 3 or -CH 3 ;

n= 1 , 2 , or 3 ;

R 5 is -CH 3 or H, wherein when n= 2 or 3 , R 5 is independently -CH 3 or H; and A is -OH, -OCH 3 , OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , or -OCH 2 CH 2 CH 2 CH 3 ;

2 . The compound of claim 1 wherein

3 . The compound of claim 1 wherein:

-CH 2 CH 2 C(O)OH, -CH 2 C(O)OH,-CH 2 CH 2 C(O)OCH 3 ,-CH 2 C(O)OCH 3 , -CH 2 CH 2 C(O) OCH 2 CH 3 , CH 2 C(O)OCH 2 CH 3 , -CH 2 CH 2 C(O)OCH 2 CH 2 CH 3 ,or -CH 2 C(O)OCH 2 CH 2 CH 3 .

4 . The compound of claim 1 wherein

-CH(CH 2 )C(O)OH, -CH(CH 2 )C(O)OCH 3 , -CH(CH 2 )CH 2 C(O) OH, -CH(CH 2 ) CH 2 C(O)OCH 3 , -CH(CH 2 )C(O)OCH 2 CH 3 , or -CH(CH 2 )CH 2 C(O)OCH 2 CH 3 .

5 - 7 . (canceled)

8 . The compound of claim 7 wherein R 9 is -CH 3 .

9 . (canceled)

10 . The compound of any of claim 1 wherein R 2 is F, Cl, -OCH 3 or -CH 3 .

11 . The compound of claim 10 where R 2 is -OCH 3 or -CH 3 .

12 . The compound of claim 11 wherein R 2 is -OCH 3 .

13 . The compound of claim 11 wherein R 2 is -CH 3 .

14 . The compound of claim 1 wherein R 2 is -OCH 3 singly or independently multiply substituted with one or more halogen or -CH 3 singly or independently multiply substituted with one or more halogen.

15 . The compound of claim 1 wherein R 2 is -OH.

16 . The compound of claim 1 wherein R 3 is a halogen.

17 . The compound of claim 16 wherein R 3 is F, Cl, or Br.

18 . The compound claim 17 wherein R 3 is Cl.

19 . The compound claim 17 wherein R 3 is Br.

20 . The compound claim 17 wherein R 3 is F.

21 . The compound of any of claim 1 wherein R 8 is H.

22 . The compound of claim 1 wherein

m= 1 , 2 , or 3 and each R 6 is independently a halogen, -SCF 3 , -SCH 3 , -CF 3 , -OCF 3 or -OCH 3 .

23 . The compound of claim 1 wherein R 6 is -SCF 3 .

24 . The compound of claim 1 wherein R 6 is -SCH 3 .

25 . The compound of claim 1 wherein R 6 is -CF 3 .

26 . The compound of claim 1 wherein R 6 is -OCF 3 .

27 . The compound of claim 1 wherein R 6 is -OCH 3 .

28 . The compound of claim 1 wherein R 6 is a halogen.

29 . The compound of claim 28 wherein R 6 is Cl.

30 . The compound of claim 28 wherein R 6 is F.

31 . The compound of claim 1 wherein

32 . (canceled)

33 . The compound of claim 1 wherein

m is 2 or 3 and at least one R 6 is in the meta position.

34 . The compound of claim 1 wherein

35 . The compound of claim 1 wherein

m is 1 and R 6 is in the ortho or para position.

36 . The compound of claim 1 wherein R 1 and R 8 are H.

37 . The compound of claim 1 wherein

is -CH 2 C(O)OH.

38 . (canceled)

39 . The compound of claim 1 having the formula;

40 . The compound of claim 39 wherein R 6 is: -CH 3 , -CF 3 , -OCH 3 , OCF 2 H, -OCFH 2 , -OCF 3 , -CN, -SCF 3 , -SCH 3 , -CF 2 H.

41 . The compound of claim 40 wherein R 6 is: -OCH 3 , -OCF 2 H, -OCFH 2 , or -OCF 3 , -CN, SCF 3 , SCH 3 , -CF 2 H, or -SCF 2 H.

42 . The compound of claim 41 wherein R 6 is: -OCH 3 , -OCF 2 H, -OCFH 2 , or -OCF 3 .

43 . The compound of claim 39 wherein R 2 is H, F, Cl, -CH 3 , optionally, independently substituted with one or more halogen, or -OCH 3 , optionally, independently substituted with one or more halogen.

44 - 94 . (canceled)

95 . A method for treating asthma comprising administering the compound of any of claim 1 .

96 . A method for treating neuropathic pain comprising administering the compound of claim 1 .

97 . A method for treating allergic rhinitis comprising administering the compound of claim 1 .

98 - 100 . (canceled)

101 . A compound having Formula I:

wherein

R 1 is: H or a halogen;

R 2 is: H, a halogen, C 1 to C 6 alkyl, or R 2B O- wherein

R 2B is selected from:

(a) H;

(b) C 1 to C 6 alkenyl that is optionally independently substituted with one or more halogen; -OH, -NH 2 , -C(O)OH;

(c)

wherein each R 2A is independently: H a C 1 to C 6 alkyl, a C 2 to C 6 alkenyl, a C 2 to C 6 alkynl, a C 6 to C 10 aryl, a C 3 to C 10 cycloalkyl, or a C 7 to C 20 arylalkyl optionally independently substituted with one or more halogen, -OH, -C(O)OH, or -NH 2 ;

R 3 is H, a halogen, -CH 3 , -CF 3 , -CF 2 H, -OCF 2 H, -OCF 3 , -SCF 2 H, -SCF 3 or -CN;

Z is selected from;

wherein the carbonyl carbon is bonded to the N of the indole,

(e) C 1 to C 4 alkyl

wherein the carbonyl carbon is bonded to the N of the indole and q is 1 , 2 , 3 , or 4 ,

wherein the carbonyl carbon is bonded to the N of the indole,

wherein the carbonyl carbon is bonded to the N of the indole,

wherein the carbonyl carbon is bonded to the N of the indole, or

(j) a bond

A is selected from:

(a) -X 1 R 4 ,

(b) -X 2 ,

(d) a C 1 to C 6 alkyl, independently substituted with one or more halogen

(e) -C(O)OX 5 wherein X 5 is a C 1 to C 6 alkyl or alkenyl, independently substituted with one or more halogen; and

(f) -C(O)NH 2 ;

wherein

X 1 is -O-, -S-, -N(H)-or-N(H)S(O 2 )-;

R 4 is H; -OH, a C 1 to C 10 alkoxy, a C 1 to C 10 alkyl; a C 2 to C 10 alkenyl; a C 2 to C 10 alkynyl; a C 3 to C 8 cycoalkyl; a C 1 to C 6 hydroxyalkyl; a hydroxyl substituted C 6 to C 8 aryl; a primary, secondary or tertiary C 1 to C 6 alkylamino; primary, secondary or tertiary C 6 to C 8 arylamino; C 2 to C 6 alkylcarboxylic acid; a C 1 to C 6 alkylester; a C 6 to C 10 aryl; a C 6 to C 10 arylcarboxylic acid; a C 6 to C 10 arylester; a C 6 to C 10 aryl substituted C 1 to C 6 alkyl; a 4 to 8 membered unsaturated or saturated heterocycle or a 4 to 8 membered heteroaryl wherein the heteroatoms are selected from O, S, S( 0 ) 2 , N, and S(O); an alkyl-substituted or aryl-substituted 4 to 8 membered or or saturated heterocycle or 4 to 8 membered heteroaryl wherein the heteroatoms are selected from O, S, S(O) 2 N, and S(O), wherein one or more H within R 4 can be replaced by a halogen, -OH, or -C(O)OH, or -NH 2 ;

X 2 is;

(a) a benzyl group;

(b) a 6- membered unsaturated heterocycle having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S;

(c) a 5- membered unsaturated heterocycle having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S;

(d) a 5, 5 or 6, 5 unsaturated or aromatic fused ring having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S;

(e) -C(O)OH,

(f) a C 1 -C 4 alkyl,

(g) a C 1 -C 4 alkoxyl, and

(h) a C 1 -C 4 thioalkoxy that;

wherein X 2 can be independently singly or multiply substituted at any substitutable position with OH, -CN, lower alkyl, lower alkoxy, halogen, and -CH 3 , -SCH 3 , -OCH 3 , -CH 2 CH 3 , -OCH 2 CH 3 , or -SCH 2 CH 3 , wherein one or more H can be replaced by a halogen.

Y is C or N;

Q os O or S;

X 3 and X 4 are independently selected from H, -C(O)H, -C(O)OH, a C 1 to C 6 alkyl a benzyl, a 6-membered unsaturated or aromatic heterocycle having 1, 2, or 3 heteroatoms independently selected from N, O, and S, and a 5-membered unsaturated or aromatic heterocycle having 1, 2, or 3 heteroatoms independently selected from N, O, and S;

provided that when Y is N, X 3 is absent; n is 1 , 2 , 3 , 4 , or 5 ;

each R 5 is independently: H, -OH, halogen, or an optionally substituted C 1 to C 4 alkyl wherein the substituents are independently selected from a halogen and -OH;

represents a C 3 to C 6 saturated carbocycle; a C 6 aryl, C 3 C 6 non-saturated, non-aromatic carbocycle; a 6-membered heteroaryl having 1, 2, 3, 4 or 5 heteroatoms independently selected from O, S, S(O) 2 , N, S(O) and N (R 7 ); a 3- to 7 -membered saturated or non-saturated heterocycle having 1 , 2 , 3 , 4 or 5 heteroatoms independently selected from O, S, S(O) 2 , N, S(O) and N(R 7 ); a 6, 5-fused heteroaromatic ring system having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S; a 6, 6-fused heteroaromatic ring system having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S; a napthyl group;

each R 6 is independently H, -OH, a halogen, a C 1 -C 6 alkyl, -CN, -OCH 3 , -SCH 3 , -OCH 2 CH 3 , -SCH 2 CH 3 , -CH 2 CH 3 , -C(O)OCH 3 , -C(O)OH, a C 3 -C 6 alkoxy, a C 3 to C 6 saturated carbocycle, a C 6 aryl, C 3 - C 6 non-saturated , non-aromatic carbocycle, a 6-membered heteroaryl having 1, 2, 3, 4 or 5 heteroatoms independently selected from O, S, S(O) 2 , N, S(O) and N(R 7 ), a 3- to 7-membered saturated or non-saturated heterocycle having 1, 2, 3, 4 or 5 heteroatoms independently selected from O, S S(O) 2 , N, S(O) and N(R 7 ) wherein one or more H within R 6 can be replaced by a halogen;

m=1, 2, 3, 4, or 5;

R 7 is: H, a halogen, -CH 3 , -CN, -OCH 3 , -SCH 3 , -SCH 2 CH 3 , -OCH 2 CH 3 , -CH 2 CH 3 , or or a C 3 -C 6 alkoxy wherein one or more H can be replaced by a halogen;

R 8 is H, a halogen or -CH 3 , wherein one or more H can be replaced by a halogen; and

R 9 is Cl or a C 1 to C 6 alkyl, wherein one or more H can be replaced by a halogen.

102 - 222 . (canceled)

223 . A compound having Formula III

wherein

R 11 is selected from H, CH 3 , F, Cl, Br, -OH, -CF 3 ,CF 2 H, -OCH 3 , -OCF 2 H, -OCF 3 , SCH 3 , -SCF 2 H, -SCF 3 , -CN, -NO 2 , -SO 2 CH 3 , -SOCH 3 , SO 2 NH 2 ;

R 12 is selected from H, F, Cl, Br, -CH 3 , -OCH 3 , -CF 3 , CF 2 H, -ICF 2 H, -OCF 3 , SCH 3 ,-SCF 2 H, -SCF 3 , -CN, -SOCH 3 , -SO 2 CH 3 , -SO 2 NH 2 ; and

(a) R 13 is -C(O)OH; R 14 is H; and R 15 is H;

(b) R 13 is H; R 14 is -C(O)OH; and R 15 is H;

(c) R 13 is H; R 14 is H; and R 15 is -C(O)OH;

(d) R 13 is H; R 14 is -C(O)OH; and R 15 is -C(O)OH;

(e) R 13 is -C(O)OH; R 14 is H; and R 15 is -C(O)OH; or

(d) R 13 is selected from: H, C 1 -C 6 alkyl, -C(O)OH, and -PO(OH) 2 : R 14 is selected from H, C 1 -C 6 alkyl, -C(O)OH, and -PO(OH) 2 ; and R 15 is selected from -CH 2 PO(OH) 2 , -CH 2 CH 2 PO(OH) 2 , H, CH 3 , -CH 2 CO 2 H, -CH 2 CH 2 CO 2 H.

224 . A compound having Formula II

wherein

R 1 is: H or a halogen;

R 2 is: H, a halogen, C 1 to C 6 alkyl, or R 2B O- wherein

R 2B is selected from:

(a) H;

(b) C 1 to C 6 alkyl or a C 2 to C 6 alkenyl that is optionally independently substituted with one or more halogen; -OH, -NH 2 , -C(O)OH;

(c)

wherein each R 2A is independently: H, a C 1 to C 6 alkyl, a C 2 to C 6 alkenyl, a C 2 to C 6 alkenyl, a C 2 to C 6 alkynyl, a C 6 to C 10 aryl, a C 3 to C 10 cycloalkyl, or a C 7 to C 20 arylalkyl optionally independently substituted with one or more halogen, -OH, -C(O)OH, or -NH 2 ;

R 3 is H, a halogen, -CH 3 , -CF 3 , CF 2 H, OCF 2 H, -OCF 3 , -SCF 2 H, -SCF 3 or -CN

Z is selected from

wherein the carbonyl carbon is bonded to the N of the indole,

(e) C 1 to C 4 alkyl

wherein the the carbonyl carbon is bonded to the N of the indole and q is 1, 2, 3, or 4,

wherein the carbonyl carbon is bonded to the N of the indole,

wherein the carbonyl carbon is bonded to the N of the indole,

wherein the carbonyl carbon is bonded to the N of the indole, or

a bond

A is selected from:

(a) -X 1 R 4 ,

(b) -X 2 ,

(d) a C 1 to C 6 alkyl or alkenyl, independently substituted with one or more halogen,

(e) -C(O)PX 5 wherein X 5 is a C 1 to C 6 alkyl or alkenyl, independently substituted with one or more halogen; and

(f) -C(O)NH 2 ;

wherein:

X 1 is -O-, -S-, -N(H)- or -N(H)S(O 2 )-;

R 4 is H; -OH, a C 1 to C 10 alkoxy, a C 1 to C 10 alkyl; a C 2 to C 10 alkenyl; a C 2 to C 10 alkynyl; a C 3 to C 8 cycloalkyl; a C 1 to C 6 hydroxyalkyl; a hydroxyl substituted C 6 to C 8 aryl; a primary, secondary or tertiary C 1 to C 6 alkylamino; primary secondary or tertiary C 6 to C 8 arylamino; C 2 to C 6 alkylcarboxylic acid; a C 1 to C 6 alkylester; a C 6 to C 10 aryl; a C 6 to C 10 arylcarboxylic acid; a C 6 to C 10 arylester; a C 6 to C 10 aryl substituted C 1 to C 6 alkyl; a 4 to 8 membered unsaturated or saturated heterocycle or a 4 to 8 membered heteroaryl wherein the heteroatoms are selected from O, S, S(O) 2 , N, and S(O); an alkyl-substituted or aryl substituted 4 to 8 membered or saturated heterocycle pr 4 to 8 membered heteroaryl wherein the heteroatoms are selected from O, S, S(O) 2 , N, and S(O), wherein one or more H within R 4 can be replaced by a halogen, -OH, or -C(O)OH, or -NH 2 ;

(a) a benzyl group

(b) a 6-membered unsaturated heterocycle having 1, 2, 3 or 4 heteroatoms independently selected from N, O, and S;

(c) a 5-membered unsaturated heterocycle having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S;

(d) a 5, 5 or 6, 5 unsaturated or aromatic fused ring having 1, 2, 3, or 4 heteroatoms independently selected from N, O, and S;

(e) -C(O)OH,

(f) a C 1 -C 4 alkyl, and

(g) a C 1 -C 4 alkoxyl, and

(h) a C 1 -C 4 thioalkoxy that;

wherein X 2 can be independently singly or multiply substituted at any substitutable position with OH, -CN, lower alkyl, lower alkoxy, halogen, and -CH 3 , -SCH 3 , -OCH 3 , -CH 2 CH 3 , -OCH 2 CH 3 , or -SCH 2 CH 3 , wherein one or more H can be replaced by a halogen.

Y is C or N;

Q is O or S;

X 3 and X 4 are independently selected from H, -C(O)H, -C(O)OH, a C 1 to 6 6 alkyl, a benzyl, a 6-membered unsaturated or aromatic heterocycle having 1, 2, or 3 heteroatoms independently selected from N, O, and S, and a 5-membered unsaturated or aromatic heterocycle having 1, 2, or 3 heteroatoms independently selected from N, O and S;

provided that when Y is N, X 3 is absent;

n is 1, 2, 3, 4 or 5

each R 5 is independently: H, -OH, halogen, or an optionally substituted C 1 to C 4 alkyl, wherein the substituents are independently selected from a halogen and -OH;

represents: a C 3 to C 6 saturated carbocycle; a C 6 aryl, C 3 to C 6 non-saturated, non-aromatic carbocycle; a 6- membered heteroaryl having 1, 2, 3, 4 or 5 heteroatoms independently selected from O, S, S(O) 2 , N, S(O) and N(R 7 ); a 3- to 7-membered saturated or non-saturated heterocycle having 1, 2, 3, 4 or 5 heteroatoms independently selected from O, S, S(O) 2 , N, S(O) and N(R 7 ); a 6, 5-fused heteroaromatic ring system having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S; a 6, 6-fused heteroaromatic ring system having 1, 2, 3 or 4 heteroatoms independently selected from N, O and S; a napthyl group;

each R 6 is independently; H, -OH, a halogen, a C 1 -C 6 alkyl, -CN, -OCH 3 , -SCH 3 , -OCH 2 CH 3 , -SCH 2 CH 3 , -CH 2 CH 3 , -SO 2 CH 3 , -C(O)OCH 3 , -C(O)OH, a C 3 -C 6 alkoxy, a C 3 to C 6 saturated carbocycle, a C 6 aryl, C 3 -C 6 non-saturated, non-aromatic carbocycle, a 6-membered heteroaryl having 1, 2, 3, 4 or 5 heteroatoms independently selected from O, S, S(O) 2 , N, S(O) and N(R 7 ), a 3- to 7-membered saturated or non-saturated heterocycle having 1, 2, 3, 4 or 5 heteroatoms independently selected from O, S, S(O) 2 , N, S(O) and N(R 7 ) wherein one or more H can be replaced by a halogen;

m=1, 2, 3, 4, or 5;

R 7 is: H, a halogen, -CH 3 , -CN, -OCH 3 , -SCH 3 , -SCH 2 CH 3 , -OCH 2 CH 3 , -CH 2 CH 3 or or a C 3 - C 6 alkoxy wherein one or more H can be replaced by a halogen;

R 8 is: H, a halogen or -CH 3 , wherein one or more H can be replaced by a halogen; and

R 9 is Cl or a C 1 to C 6 alkyl, wherein one or more H can be replaced by a halogen.

225 - 245 . (canceled)

246 . A compound having Formula I

wherein

R 1 is H or a halogen;

R 2 is H, -OH, a halogen, CH 3 , wherein any carbon can be optionally, independently substituted with one or more halogen; or -OCH 3 , wherein any carbon can be optionally, independently substituted with one or more halogen;

R 3 is H, a halogen or CH 3 ;

Z is

-CH(CH 2 )- or CH 2 ;

R 8 is H or Cl;

R 6 is F, Cl, Br, -CH 3 , -CF 3 , -OCH 3 , -OCF 2 H, -OCF 3 , -CN, -SCF 3 , -SCH 3 , -CF 2 H, or -SCF 2 H;

m is 0, 1 2 or 3.

R 9 is H, a halogen, -CH 2 CH 3 or -CH 3 ;

n=1, 2, or 3

R 5 is -CH 3 or H, wherein when n=2 or 3, R 5 is independently -CH 3 or H; and A is selected from -OH, -OCH 3 , -OCH 2 CH 3 , -OCH 2 CH 2 CH 3 , -OCH 2 CH 2 CH 2 CH 3 ;;

provided that when

is -CH 2 C(O)OCH 3 ,

Z is CH 2 , R 1 is H, R 2 is -OCH 3 , R 3 is Cl, and R 9 is not Br or H;

further provided that when

Z is CH 2 , R 1 is H, R 2 is H, R 3 is -CH 3 , R 8 is H, and R 9 is -CH 3 ,

is not -CH 2 C(O)OCH 3 or -CH 2 C(O)OH;

further provided that when

Z is CH 2 , R 1 is H, R 2 is H, R 3 Cl, and R 8 is H, and R 9 is -CH 3 ,

is not -CH 2 C(O)OCH 3 ; and

further provided that when

R 1 is H, R 2 is H,R 3 -CH 3 , R 8 is H, and R 9 is -CH 3 ,

is not -CH 2 C(O)OH; and

further provided that when

R 1 is -CH 3 , R 2 is -OCH 3 , R 3 -CH 3 , R 8 is H, and R 9 is -CH 3 ,

is not -CH 2 C(O)OH; and

further provided that when

Z is CH 2 , R 1 is H, R 2 is F, R 3 H, R 8 is H, and R 9 is -CH 3 ,

is not -CH 2 C(O)OH.

247 - 288 . (canceled)

289 . A compound having the formula:

wherein

R 16 is H or Cl;

R 17 is H, F, Cl, -CH 3 , -OH, -OCH 3 or -OCF 3 ;

R 18 is H, F, Cl, or CH 3 ;

Z is

or CH 2 ;

R 19 is H or Cl;

R 21 is H, F, Cl, Br, -CH 3 , -CF 3 , -OCH 3 , -OCF 2 H, -OCG 3 or -CN;

m is 0, 1 or 2 and

R 20 is H, Cl, or CH 3 ,

provided that when Z is CH 2, R 20 is CH 3 , and

R 16 , R 17 , R 18 and R 19 are not all H;

further provided that when Z is CH 2 , R 20 is CH 3 ,

and R 17 is -OCH 3 , R 16 , R 18 and R 19 are not all H;

further provided that when Z is CH 2 , R 20 is Cl,

and R 17 is -CH 3 , R 16 , R 18 and R 19 are not all H;

further provided that when Z is CH 2 , R 20 is Cl,

and R 16 , R 17 , R 18 and R 19 are not all H;

further provided that when Z is CH 2 , and

R 16 , R 17 , R 18 and R 19 are not all H.

290 - 305 . (canceled)

306 . A compound A having the formula

wherein

Z is

or CH 2 ;

R 22 is -CH 3 , Cl or H;

R 23 is -OCH 3 , -CH 3 , -NH 2 , -C(O)OH, - C(O)OCH 3 , -C(O)NH 2 , CF 3 ,

R 23A is H, halogen, C 1 -C 6 alkoxy, -NO 2 , -CH 3 , CF 3 , -OCF 2 H, -OCF 3 , -CH 3 , -SCF 3 ,

wherein any substitutable position within a ring can be singly or multiply, independently substituted by halogen, C 1 -C 6 alkoxy, -CN, -CF 3 or NO 2 ,

R 24 is H or Cl;

R 25 is H, F, Cl, -OCH 3 , -CH 3 , OH, -OCF 3 ;

R 26 is H, F, Cl, or -CH 3 ;

R 27 is H;

R 28 is H, halogen, C 1 -C 6 alkoxy, -NO 2 , -CH 3 , -OCF 2 H, -OCF 3 , -CN, -SCH 3 , or -SCF 3

307 . The compound of claim 306 wherein R 23 is -OCH 3 , -CH 3 , -NH 2 , -C(O)NH 2 , -CF 3 ,

308 - 314 . (canceled)

315 . A compound having the formula

wherein

Z is

or CH 2 ;

R 22 is -CH 3 , Cl or H;

R 23 is -OCH 3 , CH 3 , -NH 2 , -C(O)OH, -C(O)OCH 3 , C(O)NH 2 , -CF 3 ,

R 23A is H, halogen, C 1 -C 6 alkoxy, -NO 2 , -CH 3 , CF 3 , -OCF 2 H, -OCF 3 , -CH 3 , -SCF 3 ,

wherein any substitutable position within a ring can be singly or multiply, independently substituted by halogen, C 1 -C 6 alkoxy, -CN, -CF 3 or NO 2 .

R 24 is H or Cl;

R 25 is H, F, Cl, -OCH 3 , -CH 3 , OH, -OCF 3 ;

R 26 is H, F, Cl or -CH 3 ;

R 27 is H;

R 28 is H, halogen, C 1 -C 6 alkoxy, -NO 2 , -CH 3 , -OCF 2 H, -OCF 3 , -CN, -SCH 3 , or -SCF 3 .

316 - 322 . (canceled)

323 . A compound having the formula

wherein

R 30 is H;

R 31 is O, H, -C(O)OH, halogen, -CH 2 C(O)OH, a C 1 -C 4 alkyl or alkenyl that is optionally substituted with a phenyl group, -OCH 2 C(O)OH, -SCH 2 C(O)OH, -OH, -N(H)CH 2 C(O)OH, -B(OH) 2 , -SO 3 H, -PO 3 H 2 , -CH 2 OH,

R 32 is H, a C 1 -C 4 alkyl or alkenyl that is optionally substituted with a phenyl group, halogen, -OH, -OCH 3 , -NH 2 , -SH, and -SCH 3 ;

R 33 and R 36 are independently selected from: H, a C 1 -C 4 alkyl or alkenyl that is optionally substituted with a phenyl group, -(CH 2 ) n C(O)C 6 H 5 wherein n is 1, 2, 3, or 4; -O(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3, or 4, -S(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3 or 4, -NH(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3 or 4, -C(O)C 6 H 5 , -N(CH 3 )C(O)(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n OC 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n SC 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n S(O) m C 6 H 5 wherein m is 1 or 2, -(CH 2 ) n N(H)C 6 5 , -(CH 2 ) n N(CH 3 )C(O)C 6 H 5 , C 6 H 5 , halogen, -OH, -OCH 3 , -CH 2 OH; and

R 34 and R 35 are independently selected from H, C 1 -C 3 alkyl or alkenyl, halogen, -OH, -OCH 3 , -NH 2 ;-SH;

wherein any phenyl group can be optionally independently substituted with 1, 2, 3, of 4 substituents selected from -OCH 3 , OCF 2 H, -OCF 3 , a C 1 -C 4 alkyl, -CN, SCH 3 , -SCF 2 H, -SCF 3 , -CF 3 , and -CF 2 H, and wherein R 32 is O, represents a single bond and when R 32 is other than O, represents a double bond.

324 . A compound having the formula

wherein

R 37 is H, -C 1 -C 4 alkyl, -(CH 2 ) n OC 6 H 5 , -(CH 2 ) n N(H)C 6 H 5 , -(CH 2 ) n C 5 H 5 , wherein n is 1, 2, 3 or 4;

R 38 is O, H, -C(O)OH, halogen, -CH 2 C(O)OH, a C 1 -C 4 alkyl or alkenyl, -OCH 2 C(O)OH, -SCH 2 C(O)OH, -OH, -N(H)CH 2 C(O)OH, -B(OH) 2 , -SO 3 H, -PO 3 H 2 , -CH 2 OH,

R 39 is H, -C(O)OH, halogen, -CH 2 C(O)OH, a C 1 -C 4 alkyl or alkenyl, -OCH 2 C(O)OH, -SCH 2 C(O)OH, -OH, -OH, -N(H)CH 2 C(O)OH, -B(OH) 2 , -SO 3 H, -PO 3 H 2 , -CH 2 OH, -C(O)OCH 3 , -C(O)OCH 2 CH 3 ,

R 40 and R 43 are independently selected from: H, a C 1 -C 4 alkyl or alkenyl, -(CH 2 ) n C(O)C 6 H 5 wherein n is 1, 2, 3, or 4; -O(CH 2 ) n C 6 H 5 wherein n is 1 , 2 , 3 , or 4, -S(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3 or 4, -NH(CH 2 ) n C 6 H 5 wherein n is 1 , 2 , 3 or 4, -C(O)C 6 H 5 , -N(CH 3 )C(O)(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n OC 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n N(H)C 6 H 5 , -(CH 2 ) n N(CH 3 )C(O)C 6 H 5 , C 6 H 5 , halogen, -OH, -OCH 3 , -CH 2 OH; and

R 41 and R 42 are independently selected from: H, C 1 -C 4 alkyl or alkenyl, halogen, -OH, -OCH 3 , -NH 2 , -SH;

wherein any phenyl group can be optionally independently substituted with 1, 2, 3 of 4 substituents selected from -OCH 3 , -OCF 2 H, -OCF 3 , a C 1 -C 4 alkyl, -CN, -SCH 3 , SCF 2 H, -SCF 3 , -CF 3 , and CF 2 H,

wherein where R 38 is O, represents a single bond and when R 38 is other than O, represents a double bond.

325 . A compound having the formula

wherein

represents a single or a double bond

R 45 is H, -C(O)OH, a halogen, -CH 2 C(O)OH, a C 1 -C 4 alkyl or alkenyl optional substituted with a phenyl group, -OCH 2 C(O)OH, O,-OH

-NHCH 2 C(O)H, B(OH) 2 , -SO 3 H, -PO 3 2 , -CH 2 OH,

R 46 is H, a C 1 -C 3 , alkyl or alkenyl, a C 1 -C 4 alkyl or alkenyl optional substituted with a

R 47 , R 48 are independently selected from: H, a C 1 -C 4 alkyl or alkenyl optional substituted with a phenyl group, -O(CH 2 ) n C 6 H 5 wherein n is 1 , 2 , 3 , or 4, -S(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3 or 4, -NH(CH 2 ) n C 6 H 5 wherein n is 1 , 2 , 3 or 4, -C(O)C 6 H 5 , -N(CH 3 )C(O)(CH 2 ) n C 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n OC 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n SC 6 H 5 wherein n is 1, 2, 3 or 4, -(CH 2 ) n S(O) m C 6 H 5 wherein m is 1 or 2 and l is 1, 2, 3 or 4, -(CH 2 ) n N(H)C 6 H 5 , -(CH 2 ) n N(CH 3 )C(O)C 6 H 5 , a phenyl group, halogen, -OH, -OCH 3 , -CH 2 OH;

R 49 , R 50 and R 51 are independently selected from H, C 1 -C 3 alkyl or alkenyl, a halogen, OH, -OCH 3 , -NH 2 , -SH; wherein when R 45 is O, R 44 is H and

represents a single bond and when R 45 is other than O represents a double bond, and wherein wherein any phenyl group can be optionally independently substituted with 1, 2, 3 of 4 substituents selected from -OCH 3 , -OCF 2 H, -OCF 3 , a C 1 -C 4 alkyl, -CN, -SCH 3 , SCF 2 H, -SCF 3 , -CF 3 , and -CF 2 H.

326 . The compound of claim 1 wherein m is 2.

Assignments (2)
CHANGE OF NAME Recorded Apr 17, 2008
From: MICROBIA, INC.
To: IRONWOOD PHARMACEUTICALS, INC.
Reel/Frame 020828/0232 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 11, 2007
From: BARTOLINI, WILMIN; CALI, BRIAN M.; CHEN, BARBARA; CHIEN, YUEH-TYNG; CURRIE, MARK G.; MILNE, G. TODD; PEARSON, JAMES PHILIP; TALLEY, JOHN JEFFREY; YANG, JING JING; ZIMMERMAN, CRAIG; MONREAL, ALEX W.
To: MICROBIA, INC.
Reel/Frame 019146/0463 →