Fused pyrrolocarbazoles

A method for preparing a D-ring-fused pyrrolocarbazole, the method comprising the steps of:

• a) obtaining an indole defined by Formula IV:
• ##STR19## wherein:
• R.sup.2 is selected from the group consisting of H, SO.sub.2 R.sup.9, CO.sub.2 R.sup.9, and alkyl of 1-4 carbons;
• R.sup.3a and R.sup.4a are each independently selected from the group consisting of H, F, Cl, Br, I, --OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, NR.sup.7 R.sup.8, --SR.sup.11, where R.sup.11 is selected from the group consisting of H, aklyl of 1-4 carbons, aryl of 6-10 carbons and heteroaryl;
• alkyl, aryl, heteroaryl, --(CH.sub.2).sub.n S, --(CH.sub.2).sub.n OR.sup.9, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• b) reacting said indole with a 2-indanone defined by the general formula:
• ##STR20## wherein:
• R.sup.5a and R.sup.6a are each independently selected from the group consisting of H, F, CI, Br, I, alkyl, aryl, heteroaryl, CN, NO.sub.2, OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, CO.sub.2 R.sup.9, SO.sub.2 R.sup.9, SR.sup.11, --(CH.sub.2).sub.n S(O).sub.y R.sup.9, wherein y is an integer selected from the group consisting of 1 and 2;
• --(CH.sub.2).sub.n SR.sup.11, NR.sup.7 R.sup.8, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8, and X is selected from the group consisting of an alkylene group of 1-3 carbons and --C(R.sup.10).sub.2 --;
• under conditions capable of forming a 2-(2-cycloalkenyl)indolo tertiary alcohol defined by Formula V:
• ##STR21## c) eliminating the hydroxyl group of the alcohol of said Formula V to form a 2-(2-cycloalkenyl)indole defined by Formula VI:
• ##STR22## d) reacting said Formula VI with an imide defined by the general formula:
• ##STR23## wherein:
• R.sup.1 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl, arylalkyl, heteroaryl, and heteroarylalkyl;
• COR.sup.9, where R.sup.9 is selected from the group consisting of alkyl of 1-4 carbons, and aryl, --OR.sup.10, where R.sup.10 is selected from the group consisting of H and alkyl of 1-4 carbons;
• --CONH.sub.2, --NR.sup.7 R.sup.8, --(CH.sub.2).sub.n NR.sup.7 R.sup.8, wherein n is an integer of 1-4;
• and --O(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• wherein either
• 1) R.sup.7 and R.sup.8 independently are selected from the group consisting of H and alkyl of 1-4 carbons;
• or
• 2) R.sup.7 and R.sup.8 are combined together to form a linking group of the general formula --(CH.sub.2).sub.2 --X.sup.1 --(CH.sub.2).sub.2 --, where X.sup.1 is selected from the group consisting of O, S and CH.sub.2 ;
• under conditions which form a tetrahydropyrrolocarbazole defined by Formula VII:
• ##STR24## and e) dehydrogenating the tetrahydrocarbazole ring of said Formula VII under conditions which form a fused pyrrolocarbazole defined by Formula VIII. ##STR25## wherein:
• R.sup.2, R.sup.3a and R.sup.4a are as defined in (a) above;
• R.sup.5a, R.sup.6a and X are as defined in (b) above;
• and R.sup.1 is defined as in (d) above.

A method for making regiospecific D-ring-fused pyrrolocarbazole lactam isomers, said method comprising the steps of:

• a) obtaining a fused pyrrolocarbazole defined by Formula VIII:
• ##STR26## wherein:
• R.sup.1 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl, arylalkyl, heteroaryl, and heteroarylalkyl;
• COR.sup.9, where R.sup.9 is selected from the group consisting of alkyl of 1-4 carbons, and aryl, --OR.sup.10, where R.sup.10 is selected from the group consisting of H and alkyl of 1-4 carbons;
• --CONH.sub.2, --NR.sup.7 R.sup.8, --(CH.sub.2).sub.n NR.sup.7 R.sup.8, wherein n is an integer of 1-4;
• and --O(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• wherein either
• 1) R.sup.7 and R.sup.8 independently are selected from the group consisting of H and alkyl of 1-4 carbons;
• or
• 2) R.sup.7 and R.sup.8 are combined together to form a linking group of the general formula --(CH.sub.2).sub.2 --X.sup.1 --(CH.sub.2).sub.2 --, where X.sup.1 is selected from the group consisting of O, S and CH.sub.2 ;
• R.sup.2 is selected from the group consisting of H, SO.sub.2 R.sup.9, CO.sub.2 R.sup.9, and alkyl of 1-4 carbons;
• R.sup.3a and R.sup.4a are each independently selected from the group consisting of H, F, Cl, Br, I, --OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, NR.sup.7 R.sup.8, --SR.sup.11, where R.sup.11 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl of6-10 carbons and heteroaryl;
• alkyl, aryl, heteroaryl, --(CH.sub.2).sub.n SR.sup.11, --(CH.sub.2).sub.n OR.sup.9, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• R.sup.5a and R.sup.6a are each independently selected from the group consisting of H, F, Cl, Br, I, alkyl, aryl, heteroaryl, CN, NO.sub.2, OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, CO.sub.2 R.sup.9, SO.sub.2 R.sup.9, SR.sup.11, --(CH.sub.2).sub.n S(O).sub.y R.sup.9, wherein y is an integer selected from the group consisting of 1 and 2;
• --(CH.sub.2).sub.n SR.sup.11, NR.sup.7 R.sup.8, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8, and X is selected from the group consisting of an alkylene group of 1-3 carbons and --C(R.sup.10).sub.2 --;
• b) reducing the imide group of said fused pyrrolocarbazole under conditions which form fused pyrrolocarbazole lactam isomers defined by Formula IX and Formula X:
• ##STR27## wherein:
• R.sup.1 is defined in (a) above;
• and
• R.sup.2, R.sup.3a, R.sup.4a R.sup.5a, R.sup.6a and X are as defined in (a)(2) above;
• and
• c) separating the isomer of Formula IX from the isomer of Formula X under conditions which produce substantially pure regiospecific D-ring-fused pyrrolocarbazole lactam isomers.

A method of making regiospecific D-ring fused pyrrolocarbazole lactam isomer, said method comprising the steps of:

• a) obtaining a compound defined by Formula XI:
• ##STR28## wherein:
• R.sup.2 is selected from the group consisting of H, SO.sub.2 R.sup.9, CO.sub.2 R.sup.9, and alkyl of 1-4 carbons;
• R.sup.3a and R.sup.4a are each independently selected from the group consisting of H, F, Cl, Br, I, --OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, NR.sup.7 R.sup.8, --SR.sup.11, where R.sup.11 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl of 6-10 carbons and heteroaryl;
• alkyl, aryl, heteroaryl, --(CH.sub.2).sub.n SR.sup.11, --(CH.sub.2).sub.n OR.sup.9, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• R.sup.5a and R.sup.6a are each independently selected from the group consisting of H, F, Cl, Br, I, alkyl, aryl, heteroaryl, CN, NO.sub.2, OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, CO.sub.2 R.sup.9, SO.sub.2 R.sup.9, SR.sup.11, --CH.sub.2).sub.n S(O).sub.y R.sup.9, wherein y is an integer selected from the group consisting of 1 and 2;
• --(CH.sub.2).sub.n SR.sup.11, NR.sup.7 R.sup.8, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8, and X is selected from the group consisting of S, O, CO, alkylene of 1-3 carbons, --C(R.sup.10).sub.2 --, --CH.sub.2 Z--, where Z is selected from the group consisting of C(R.sup.11)(OR.sup.11), O, S, C(.dbd.NOR.sup.11), and NR.sup.11 ;
• --ZCH.sub.2 --, and --CH.sub.2 ZCH.sub.2 --;
• b) reacting said Formula XI with a lower alkyl .beta.-cyanoacrylate under conditions which form regiospecific tetrahydrocarbazole cyano-ester isomers defined by Formula XII and Formula XV:
• ##STR29## wherein R is a lower alkyl group;
• c) separating the isomer of Formula XII from the isomer of Formula XV under conditions which produce substantially pure regiospecific tetrahydrocarbazole cyano-ester isomers;
• d) (1) dehydrogenating the tetrahydrocarbazole ring of the isomer of Formula XII sufficient to form a carbazole cyano-ester defined by Formula XIII:
• ##STR30## and (2) dehydrogenating the tetrahydrocarbazole ring of the isomer of Formula XV sufficient to form a carbazole cyano-ester defined by Formula XVI:
• ##STR31## and e) (1) reacting the carbazole cyano-ester of Formula XIII under reductive conditions which produce regiospecific fused pyrrolocarbazoles defined by Formula XIV:
• ##STR32## wherein:
• R.sup.1 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl, arylalkyl, heteroaryl, and heteroarylalkyl;
• COR.sup.9, where R.sup.9 is selected from the group consisting of alkyl of 1-4 carbons, and aryl, --OR.sup.10, where R.sup.10 is selected from the group consisting of H and alkyl of 1-4 carbons;
• --CONH.sub.2, --NR.sup.7 R.sup.8, --(CH.sub.2).sub.n NR.sup.7 R.sup.8, wherein n is an integer of 1-4;
• and --O(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• wherein either
• 1) R.sup.7 and R.sup.8 independently are selected from the group consisting of H and alkyl of 1-4 carbons;
• or
• 2) R.sup.7 and R.sup.8 are combined together to form a linking group of the general formula --(CH.sub.2).sub.2 --X.sup.1 --(CH.sub.2).sub.2 --, where X.sup.1 is selected from the group consisting of O, S and CH.sub.2 ;
• R.sup.2, R.sup.3a, R.sup.4a R.sup.5a, R.sup.6a and X are as defined in (a) above;
• and
• (2) reacting the carbazole cyano-ester of Formula XVI under reductive conditions which produce regiospecific fused pyrrolocarbazoles defined by Formula XVII:
• ##STR33## wherein:
• R.sup.1 is defined as in (e)(1) above;
• R.sup.2, R.sup.3a, R.sup.4a R.sup.5a, R.sup.6a and X are as defined in (a) above.

A method of making a D-ring-fused pyrrolocarbazole, said method comprising the steps of:

• a) obtaining an indole defined by Formula IV:
• ##STR34## wherein:
• R.sup.2 is selected from the group consisting of H, SO.sub.2 R.sup.9, CO.sub.2 R.sup.9, and alkyl of 1-4 carbons;
• R.sup.3a and R.sup.4a are each independently selected from the group consisting of H, F, Cl, Br, I, --OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, NR.sup.7 R.sup.8, --SR.sup.11, where R.sup.11 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl of 6-10 carbons and heteroaryl;
• alkyl, aryl, heteroaryl, --(CH.sub.2).sub.n SR.sup.11, --(CH.sub.2).sub.n OR.sup.9, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• b) reacting said indole with a 2-benzocycloalkanone defined by the general formula:
• ##STR35## wherein:
• R.sup.5a and R.sup.6a are each independently selected from the group consisting of H, F, Cl, Br, I, alkyl, aryl, heteroaryl, CN, NO.sub.2, OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, CO.sub.2 R.sup.9, SO.sub.2 R.sup.9, SR.sup.11, --(CH.sub.2).sub.n S(O).sub.y R.sup.9, where y is an integer selected from the group consisting of 1 and 2;
• --(CH.sub.2).sub.n SR.sup.11, NR.sup.7 R.sup.8, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8, and X is an alkylene 2-3 carbons;
• under conditions which form Formula V:
• ##STR36## c) eliminating the hydroxyl group to form the corresponding Formula VI;
• ##STR37## d) reacting said Formula VI with an imide defined by the general formula:
• ##STR38## wherein:
• R.sup.1 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl, arylalkyl, heteroaryl, and heteroarylalkyl;
• COR.sup.9, where R.sup.9 is selected from the group consisting of alkyl of 1-4 carbons, and aryl, --OR.sup.10, where R.sup.10 is selected from the group consisting of H and alkyl of 1-4 carbons;
• --CONH.sub.2, --NR.sup.7 R.sup.8, --(CH.sub.2).sub.n NR.sup.7 R.sup.8, wherein n is an integer of 1-4;
• and --O(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• wherein either
• 1) R.sup.7 and R.sup.8 independently are selected from the group consisting of H and alkyl of 1-4 carbons;
• or
• 2) R.sup.7 and R.sup.8 are combined together to form a linking group of the general formula --(CH.sub.2).sub.2 --X.sup.1 --(CH.sub.2).sub.2 --, where X.sup.1 is selected from the group consisting of O, S and CH.sub.2 ;
• under conditions which form a tetrahydroarylalkylpyrrolocarbazole defined by Formula XVIII:
• ##STR39## and e) (1) dehydrogenating the D-ring of said pyrrolocarbazole under conditions which produce a fused pyrrolocarbazole defined by Formula XIX:
• ##STR40## i) wherein A.sup.1 and A.sup.2 are selected from the group consisting of H, H;
• H, --OR.sup.11 ;
• H, --SR.sup.11 ;
• H, --N(R.sup.11).sub.2 ;
• and a group wherein A.sup.1 and A.sup.2 together form a moiety selected from the group consisting of .dbd.O;
• .dbd.S;
• and .dbd.NR.sup.11 ;
• and
• ii) B.sup.1 and B.sup.2 are selected from the group consisting of:
• H, H;
• H, --OR.sup.11 ;
• H, --SR.sup.11 ;
• H, --N(R.sup.11).sub.2 ;
• and a group wherein B.sup.1 and B.sup.2 are selected from the group consisting of .dbd.O, .dbd.S;
• and .dbd.NR.sup.11 with the proviso that at least one of the pairs A.sup.1, A.sup.2 or B.sup.1, B.sup.2 is .dbd.O;
• and
• iii) R.sup.1 is defined in (d) above;
• R.sup.2, R.sup.3a, R.sup.4a are as defined in (a) above;
• R.sup.5a, R.sup.6a and X are as defined in (b) above;
• and
• e) (2) dehydrogenating the E-ring of said pyrrolocarbazote under conditions which produce a fused pyrrolocarbazole defined by Formula XX:
• ##STR41## i) wherein A.sup.1 and A.sup.2 are selected from the group consisting of H, H;
• H, --OR.sup.11 ;
• H, --SR.sup.11 ;
• H, --N(R.sup.11).sub.2 ;
• and a group wherein A.sup.1 and A.sup.2 together form a moiety selected from the group consisting of .dbd.O;
• .dbd.S;
• and .dbd.NR.sup.11 ;
• and
• ii) B.sup.1 and B.sup.2 are selected from the group consisting of:
• H, H;
• H, --OR.sup.11 ;
• H, --SR.sup.1 ;
• H, --N(R.sup.11).sub.2 ;
• and a group wherein B.sup.1 and B.sup.2 are selected from the group consisting of .dbd.O, .dbd.S;
• and .dbd.NR.sup.11 with the proviso that at least one of the pairs A.sup.1, A.sup.2 or B.sup.1, B.sup.2 is .dbd.O;
• and
• iii) R.sup.1 is defined in (d) above;
• R.sup.2, R.sup.3a, R.sup.4a are as defined in (a) above;
• and R.sup.5a, R.sup.6a and X are as defined in (b) above.

A method of making a D-ring-fused pyrrolocarbazole, said method comprising the steps of:

• a) obtaining a lower alkyl stannylindole defined by Formula XXI:
• ##STR42## wherein:
• R.sup.2 is selected from the group consisting of --CO.sub.2 H, --SO.sub.2 R.sup.9, --CO.sub.2 R.sup.9 and alkyl;
• R.sup.3a and R.sup.4a are each independently selected from the group consisting of H, F, Cl, Br, I, --OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, NR.sup.7 R.sup.8, --SR.sup.11, where R.sup.11 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl of 6-10 carbons and heteroaryl;
• alkyl, aryl, heteroaryl, --(CH.sub.2).sub.n SR.sup.11, --(CH.sub.2).sub.n OR.sup.9, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• b) coupling said Formula XXI with a compound defined by the general formula:
• ##STR43## wherein:
• R.sup.5a and R.sup.6a are each independently selected from the group consisting of H, F, Cl, Br, I, alkyl, aryl, heteroaryl, CN, NO.sub.2, OR.sup.9, --O(CH.sub.2).sub.n NR.sup.7 R.sup.8, CO.sub.2 R.sup.9, SO.sub.2 R.sup.9, SR.sup.11, --(CH.sub.2).sub.n S(O).sub.y R.sup.9, where y is an integer selected from the group consisting of 1 and 2;
• --(CH.sub.2).sub.n SR.sup.11, NR.sup.7 R.sup.8, and --(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• X is selected from the group consisting of S, O, CO, alkylene of 1-3 carbons, --C(R.sup.10).sub.2 --, --CH.sub.2 Z--, where Z is selected from the group consisting of C(R.sup.11)(OR.sup.11), O, S, C(.dbd.NOR.sup.11), and NR.sup.11 ;
• --ZCH.sub.2, and CH.sub.2 ZCH.sub.2 --;
• and Y is Br, I, or --OSO.sub.2 CF.sub.3 ;
• under conditions which form an indole defined by Formula XXII:
• ##STR44## c) separately reacting said Formula XXII with either:
• i) an imide defined by the general formula:
• ##STR45## or ii) a lower alkyl .beta.-cyanoacrylate;
• each independently under conditions which form an indolo-imide defined by Formula XXIII:
• ##STR46## and d) cyclizing said Formula XXIII under conditions which form a fused pyrrolocarbazole defined by Formula XXIV:
• ##STR47## wherein:
• R.sup.1 is selected from the group consisting of H, alkyl of 1-4 carbons, aryl, arylalkyl, heteroaryl, and heteroarylalkyl;
• COR.sup.9, where R.sup.9 is selected from the group consisting of alkyl of 1-4 carbons, and aryl, --OR.sup.10, where R.sup.10 is selected from the group consisting of H and alkyl of 1-4 carbons;
• --CONH.sub.2, --NR.sup.7 R.sup.8, --(CH.sub.2).sub.n NR.sup.7 R.sup.8, wherein n is an integer selected from the group consisting of 1-4;
• and --O(CH.sub.2).sub.n NR.sup.7 R.sup.8 ;
• wherein either
• 1) R.sup.7 and R.sup.8 independently are selected from the group consisting of H and alkyl of 1-4 carbons;
• or
• 2) R.sup.7 and R.sup.8 are combined together to form a linking group of the general formula --(CH.sub.2).sub.2 --X.sup.1 --(CH.sub.2).sub.2 --, where X.sup.1 is selected from the group consisting of O, S and CH.sub.2 ;
• R.sup.2, R.sup.3a, R.sup.4a are as defined in (a) above;
• and R.sup.5a, R.sup.6a and X are as defined in (b) above.