Granted Patent B2

US 8,536,328 · App. 13/100,515 · Granted Sep 17, 2013

Abstract

Claims (24)

1. A method for preparing a compound of Formula I, comprising the step of reacting a compound of Formula IA:

with a compound of Formula II:

wherein X is —S— or —O—;

Each n, m and a is independently selected from 0, 1, 2 or 3;

X 1 is selected from absent, —S—, —O—, —S(O)—, —S(O) 2 —, —N(R 10 )—, —C(O)—, —C(OR 10 )(R 11 )—, —[C(R 10 )(R 11 )] v —, —C(R 10 )(R 11 )═C(R 10 )(R 11 )—; wherein v is 0, 1, 2, 3, 4, 5; wherein each R 10 and R 11 is independently absent, hydrogen, halogen, aliphatic, substituted aliphatic, aryl or substituted aryl; alternatively two R 10 and R 11 together with the atoms to which they are attached may form an additional optionally substituted, 3, 4, 5, 6 or 7 membered ring;

Each R 1 , R 2 and R 3 is independently absent, hydrogen, halogen, aliphatic, substituted aliphatic, aryl or substituted aryl; alternatively two or more R 1 , R 2 and R 3 together with the atoms to which they are attached may form one or two additional optionally substituted, 3, 4, 5, 6 or 7 membered ring;

Each R A , R B , R C , and R D is independently selected from hydrogen, halogen, —CN, NH 2 , NR 100 R 101 , SR 100 , OR 100 , aliphatic, substituted aliphatic, aryl and substituted aryl;

wherein R 100 and R 101 , are independently selected from hydrogen, halogen, aliphatic, substituted aliphatic, aryl or substituted aryl;

in the presence of an acid;

wherein said compound of Formula IA contains a primary, secondary or tertiary amine having a pKa of about 6 to about 45.

2. The method according to claim 1 , wherein R 1 is selected from H, —C(R J )(R K )—OR 20 , —C(R J )(R K )—OC(O)OR 20 , —C(R J )(R K )—OC(O)R 20 , —C(R J )(R K )—OC(O)NR 20 R 21 , —(C(R J )(R K ))—OPO 3 MY, —(C(R J )(R K ))—OP(O)(OR 20 )(OR 21 ), —[C(R J )(R K )O] z —R 20 , —[C(R J )(R K )O] z —C(O)OR 2 O, —[C(R J )(R K )O] z —C(O)R 20 , —[C(R J )(R K )O] z —C(O)NR 20 R 21 , —[C(R J )(R K )O] z —OPO 3 MY, —[C(R J )(R K )O] z —P(O) 2 (OR 20 )M and —[C(R J )(R K )O] z —P(O)(OR 20 )(OR 21 );

wherein each R J and R K is independently selected from hydrogen, halogen, aliphatic, substituted aliphatic, aryl or substituted aryl;

each R 20 and R 21 is independently selected from hydrogen, aliphatic, substituted aliphatic, aryl or substituted aryl;

Y and M are the same or different and each is a monovalent cation; or M and Y together is a divalent cation; and

z is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

3. A method according to claim 2 , wherein R 1 is selected from Tables 1-4:

TABLE 1

TABLE 2

TABLE 3

TABLE 4

4. The method according to claim 1 , wherein said compound of Formula II is selected from 3,4-dichloro-5,6-dicyano-1,4-benzoquinone, 3,4,5,6-tetrachloro-1,2-benzquinone, ortho-benzoquinone and para-benzoquinone.

5. The method according to claim 1 , wherein said acid is selected from trifluoroacetic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, chlorosulfonic acid, dichloroacetic acid, trichloroacetic acid, acetic acid, propionic acid, sulfuric acid, phosphoric acid, nitric acid, camphorsulfonic acid, hydrochloric acid, oxalic acid, formic acid, propanoic acid, butanoic acid, pentanoic acid, benzoic acid, pyruvic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, citric acid, ascorbic acid, tartaric acid, maleic acid, hydrobromic acid, and mixtures thereof.

6. The method according to claim 1 , wherein the reaction is conducted in a solvent selected from tetrahydrofuran, tert-butylmethylether, dimethoxy-ethane, dioxane, benzene, toluene, xylene, dimethylformamide, acetone, acetonitrile, chloroform, dichloromethane, 1,2-dichloroethane, ethyl acetate, n-propyl acetate, isopropyl acetate, methyl-t-butyl ether, methyl butyl ketone and combinations thereof.

7. The method according to claim 1 , wherein said pKa range of primary, secondary or tertiary amine is between about 6 to about 30.

Assignments (9)