4-Thio coumarins

A compound of the formula X

• 247
• wherein R3 is as described for the compound of formula I,
• R6 is selected from halogen, halogenated methyl, methoxy, and ethoxy;
• R7 is selected from H, halogen, halogenated methyl, methoxy, and ethoxy;
• R8 is selected from H, halogen, halogenated methyl, methoxy, and ethoxy, and
• R9 is selected from H, halogen, halogenated methyl, methoxy, and ethoxy.

A process for the preparation of a compound of the formula I

• 255
• wherein a compound of the formula (IV)
• 256
• is reacted with a thiol of the formula R1SH, in the presence of a base, wherein R0 in combination with the oxygen atom to which it is attached, forms a leaving group, and wherein
• R1 is selected from
• an unsubstituted or substituted aromatic group, wherein the substituted aromatic group may be substituted with one or more of halogen, hydroxy, lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, thio-lower alkyl, C1-C8 acyl, lower alkyl ester, amide, and lower alkyl amide;
• a substituted or unsubstituted aralkyl group, wherein the substituted aralkyl group may be substituted with one or more of halogen, hydroxy, lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, thio-lower alkyl, C1-C8 acyl, lower alkyl ester, amide, and lower alkyl amide;
• an unsubstituted or substituted alkyl group, wherein the substituted alkyl group may be substituted with one or more halogen, hydroxy, and lower alkoxy;
• and
• an unsubstituted or substituted cycloalkyl group, wherein the substituted cycloalkyl group may be substituted with one or more halogen, hydroxy, and lower alkoxy;
• R3 is selected from halogen, hydroxy, amino, lower alkyl, lower alkoxy, lower alkenyl, and lower alkynyl, wherein the lower alkyl, lower alkoxy, lower alkenyl and lower alkynyl may be unsubstituted or may be substituted with one or more of halogen, hydroxy, and lower alkoxy;
• or R3 is a group of the formula
• Z-(CH2)a—Yb—(CH2)c-Qd-(CH2)e—
• wherein Y and Q are independently selected from an aromatic group, O, S, —CR═CR—, —C≡C—,
• 257
• each R is independently selected from H or lower alkyl,
• Z is selected from H, —CO2R, —OR, —SR, —NR2,
• 258
• a, c and e are independently selected from values from 0 to 10;
• b and d are independently selected from 0 and 1, provided that when a=0 then b=0, and when c=0 then d=0;
• or R3 may occupy two adjacent positions to form a fused aromatic ring,
• n is selected from values between 0 and 4;
• R5 is selected from hydrogen, lower alkyl, lower alkenyl, lower alkynyl, and lower aralkyl, each of which may be unsubstituted or substituted with one or more substituents selected from halogen, lower alkyl, and lower alkoxy, thio-lower alkyl, C1-C8 acyl, lower alkyl ester, amide, and lower alkyl amide;
• or R5 may be a group of the formula
• 259
• wherein
• R2 is selected from
• an unsubstituted or substituted aromatic group, wherein the substituted aromatic group may be substituted with one or more of halogen, hydroxy, lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, thio-lower alkyl, C1-C8 acyl, lower alkyl ester, amide, and lower alkyl amide;
• a substituted or unsubstituted aralkyl group, wherein the substituted aralkyl group may be substituted with one or more of halogen, hydroxy, lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, thio-lower alkyl, C1-C8 acyl, lower alkyl ester, amide, and lower alkyl amide;
• an unsubstituted or substituted alkyl group, wherein the substituted alkyl group may be substituted with one or more halogen, hydroxy, and lower alkoxy;
• and
• an unsubstituted or substituted cycloalkyl group, wherein the substituted cycloalkyl group may be substituted with one or more halogen, hydroxy, and lower alkoxy;
• R4 is selected from halogen, hydroxy, amino, lower alkyl, lower alkoxy, lower alkenyl, and lower alkynyl, wherein the lower alkyl, lower alkoxy, lower alkenyl and lower alkynyl may be unsubstituted or may be substituted with one or more of halogen, hydroxy, and lower alkoxy;
• or R4 is a group of the formula
• Z-(CH2)a-Yb-(CH2)c-Qd-(CH2)e—
• wherein Y and Q are independently selected from an aromatic group, O, S, —CR═CR—, —C≡C—,
• 260
• each R is independently selected from H or lower alkyl,
• Z is selected from H, —CO2R, —OR, —SR, —NR2,
• 261
• a, c and e are independently selected from values from 0 to 10;
• b and d are independently selected from 0 and 1, provided that when a=0 then b=0, and when c=0 then d=0;
• or R4 may occupy two adjacent positions to form a fused aromatic ring,
• and, m is selected from values between 0 and 4.