Azepine synthesis via a diels-alder reaction

A process for the preparation of a compound having the formula:

• ##STR162## or a tautomer thereof;
• wherein
• W is carbon, nitrogen, oxygen or sulfur;
• X is carbon or nitrogen;
• Y is carbon or nitrogen;
• and
• Z is carbon, nitrogen, oxygen or sulfur;
• the bond between X and Y is a single bond;
• R.sub.1 -R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• or R.sub.1 and R.sub.2 or R.sub.5 and R.sub.6 are an unshared electron pair where W and Z, respectively, are oxygen or sulfur;
• or R.sub.2 or R.sub.5 is hydrogen when W or Z respectively is nitrogen;
• or R.sub.3 or R.sub.4 is an unshared electron pair when X or Y respectively is nitrogen;
• with the proviso that X and Y are not other than carbon at the same time and that when one of W and Z is oxygen or nitrogen, then the other of W and Z is carbon;
• and
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a compound having the formula:
• ##STR163## which may exist as a mixture of cis and trans isomers;
• with a dienophile having the formula:
• ##STR164## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having the formula:
• ##STR165## (b) reduction of the quinone to the hydroquinone;
• (c) reduction of the 6,7-double bond;
• (d) oxidation to the quinone;
• and
• (e) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having Formula:

• ##STR166## or a tautomer thereof;
• wherein R.sub.1, R.sub.3, R.sub.4 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a compound having formula:
• ##STR167## wherein R.sub.1, R.sub.3, R.sub.4 and R.sub.6 are defined above;
• with a dienophile having the formula:
• ##STR168## wherein A and B are hydrogen;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having Formula:
• ##STR169## (b) oxidation to the naphthoquinone;
• and (c) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having Formula:

• ##STR170## or a tautomer thereof;
• wherein R.sub.1, R.sub.3, R.sub.4 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a compound having formula:
• ##STR171## wherein R.sub.1, R.sub.3, R.sub.4 and R.sub.6 are defined above;
• with a dienophile having the formula:
• ##STR172## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having Formula:
• ##STR173## (b) oxidation to the naphthoquinone;
• and (c) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having Formula:

• ##STR174## or a tautomer thereof;
• wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a compound having formula:
• ##STR175## wherein R.sub.2 and R.sub.5 together are an oxygen bridge, a sulfur bridge, or an amino bridge (N-R.sup.9, where R.sup.9 is alkyl, aralkyl or aryl);
• with a dienophile having the formula:
• ##STR176## wherein A and B are hydrogen;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having Formula:
• ##STR177## and (b) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having formula:

• ##STR178## or a tautomer thereof;
• wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a compound having formula:
• ##STR179## with a dienophile having the formula:
• ##STR180## wherein A and B are hydrogen;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having formula:
• ##STR181## (b) enolization to give a compound having formula:
• ##STR182## (c) hydrogenation to give a compound having formula:
• ##STR183## (d) oxidation to the quinone;
• and (e) treatment with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having formula:

• ##STR184## or a tautomer thereof;
• wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a compound having formula:
• ##STR185## with a dienophile having the formula:
• ##STR186## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having formula:
• ##STR187## (b) hydrogenation to give a compound having formula:
• ##STR188## (c) oxidation to the quinone;
• and (d) treatment with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having the Formula:

• ##STR189## wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and A is (CH.sub.2).sub.n, wherein n is 1 to 4;
• comprising
• (a) the Diels-Alder reaction of a compound having the Formula:
• ##STR190## with a dienophile having the Formula:
• ##STR191## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having the Formula:
• ##STR192## (b) hydrogenation of the quinone to the 5,6,7,8-tetrahydro-1,4-dihydroxynaphthalene;
• (c) oxidation to the quinone;
• and
• (d) treatment with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having the Formula:

• ##STR193## wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and A is (CH.sub.2).sub.n, wherein n is 1 to 4;
• comprising
• (a) the Diels-Alder reaction of a compound having the Formula:
• ##STR194## with a dienophile having the Formula:
• ##STR195## wherein A and B are hydrogen;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound having the Formula:
• ##STR196## (c) hydrogenation to the 5,6,7,8-tetrahydronaphtho-1,4-hydroquinone;
• (d) oxidation to the 5,6,7,8-tetrahydronaphtho-1,4-quinone;
• and
• (e) treatment with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having formulas:

• ##STR197## or a tautomer thereof;
• wherein R.sub.3 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialklylsilyoxy, phenyldialkylsilyoxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of the oxazole having the formula:
• ##STR198## wherein R.sub.1 is alkoxy and R.sub.3 and R.sub.6 are defined above, with the quinone having the formula ##STR199## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give a compound selected from the group consisting of the compounds having the formulas:
• ##STR200## (b) reductive ring opening and elimination of R.sub.1 --H to give a compound selected from the group consisting of the compounds having the formulas:
• ##STR201## (c) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having formulas:

• ##STR202## or a tautomer thereof;
• wherein R.sub.3 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of the oxazole having the formula:
• ##STR203## wherein R.sub.1 is alkoxy and R.sub.3 and R.sub.6 are defined above, with the quinone having the formula ##STR204## wherein A and B are hydrogen;
• and R.sub.7 is defined above;
• to give a compound selected from the group consisting of the compounds having the formulas:
• ##STR205## and (b) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having formulas:

• ##STR206## or a tautomer thereof;
• wherein R.sub.1 is hydrogen;
• R.sub.3 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels Alder reaction of the oxazole having the formula ##STR207## wherein R.sub.1, R.sub.3 and R.sub.6 are defined above;
• with the quinone having the formula ##STR208## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and R.sub.7 is defined above;
• to give a compound selected from the group consisting of the compounds having the Formulas:
• ##STR209## (b) reductive opening of the cyclic ether and elimination of water;
• and (c) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having the formulas:

• ##STR210## or a tautomer thereof;
• wherein R.sub.3 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a triazine having the formula:
• ##STR211## wherein R.sub.3 and R.sub.6 are defined above and R.sub.8 is hydrogen, alkyl or aryl;
• with the quinone having the formula ##STR212## wherein A and B are hydrogen;
• and R.sub.7 is is defined above;
• to give the compounds selected from the group consisting of those having the formulas:
• ##STR213## (b) oxidation to give the corresponding quinones which eliminate R.sub.8 --CN to give the corresponding diazanaphthoquinones, and
• (c) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having the formulas:

• ##STR214## or a tautomer thereof;
• wherein R.sub.3 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a triazine having the formula:
• ##STR215## wherein R.sub.3 and R.sub.6 are defined above and R.sub.8 is hydrogen, alkyl or aryl;
• with the quinone having the formula ##STR216## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and R.sub.7 is is defined above;
• to give the compounds selected from the group consisting of those having the formulas:
• ##STR217## (b) elimination of A--B and R.sub.8 --CN to give the corresponding diazanaphthoquinones, and
• (c) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having the formulas:

• ##STR218## or a tautomer thereof;
• wherein R.sub.3 and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• comprising
• (a) the Diels-Alder reaction of a triazine having the formula:
• ##STR219## wherein R.sub.3 and R.sub.6 are defined above and R.sub.8 is hydrogen, alkyl or aryl;
• with the quinone having the formula ##STR220## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• to give the compounds selected from the group consisting of the compounds having the formulas:
• ##STR221## or a tautomer thereof;
• and (b) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having the formulas:

• ##STR222## or a tautomer thereof;
• wherein R.sub.1, R.sub.3 and R.sub.4 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and Z is oxygen, sulfur or nitrogen which may be substituted by a trialkylsiloxy or phenyldialkylsiloxy group;
• comprising
• (a) the Diels-Alder reaction of the compound having the formula:
• ##STR223## wherein R.sub.1, R.sub.3, R.sub.4 and Z are defined above;
• with the quinone having the formula ##STR224## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and R.sub.7 is defined above;
• to give a compound selected from the group consisting of the compounds having the formulas:
• ##STR225## or a tautomer thereof;
• (b) reduction of the quinone to the hydroquinone;
• (c) hydrogenation to give a compound selected from the group consisting of the compounds having the formula:
• ##STR226## (d) oxidation to the quinone;
• and (e) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine selected from the group consisting of the compounds having the formulas:

• ##STR227## or a tautomer thereof;
• wherein R.sub.1, R.sub.3 and R.sub.4 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and Z is oxygen, sulfur or nitrogen which may be substituted by a trialkylsiloxy or phenyldialkylsiloxy group, comprising
• (a) the Diels-Alder reaction of the compound having the formula:
• ##STR228## wherein R.sub.1, R.sub.3, R.sub.4 and Z are defined above;
• with the quinone having the formula ##STR229## wherein A and B are hydrogen;
• and R.sub.7 is defined above;
• to give a compound selected from the group consisting of the compounds having the formulas:
• ##STR230## (b) enolization to give the corresponding hydroquinones;
• (c) hydrogenation to give a compound selected from the group consisting of the compounds having the formula:
• ##STR231## (d) oxidation to give the quinone selected from the group consisting of the compounds having the formulas:
• ##STR232## and (d) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having the formula:

• ##STR233## or a tautomer thereof;
• wherein R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and R.sub.9 and R.sub.10 are independently alkyl, comprising
• (a) the Diels-Alder reaction of a compound having the formula:
• ##STR234## wherein R.sub.9 and R.sub.10 are defined above;
• with a quinone having the formula ##STR235## wherein A and B are hydrogen;
• and R.sub.7 is defined above;
• to give a compound having the formula:
• ##STR236## (b) oxidation to the quinone, and (c) reaction with azide in acidic solution to give said azepine.

A process for the preparation of an azepine having the formula:

• ##STR237## or a tautomer thereof;
• wherein R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and R.sub.9 and R.sub.10 are independently alkyl;
• comprising
• (a) the Diels-Alder reaction of a compound having the formula:
• ##STR238## wherein R.sub.9 and R.sub.10 are defined above;
• with a quinone having the formula ##STR239## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and R.sub.7 is defined above;
• to give a compound having the formula:
• ##STR240## and (b) reaction with azide in acidic solution to give said azepine.

A process for preparing an azepine having the formula:

• ##STR241## wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• A is (CH.sub.2).sub.n, wherein n is 1 to 4;
• and X' and Y' are independently halogen;
• hydroxy and hydrogen;
• nitro and hydrogen;
• alkanoylamido and hydrogen;
• X' and Y' together form an oxirane ring;
• or X' and Y' are vicinal alkanoylamido alkanoyloxy groups;, comprising
• (a) the Diels-Alder reaction of the compound having Formula VII ##STR242## with the quinone having the formula ##STR243## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and R.sub.7 is defined above;
• to give the compound having formula ##STR244## (b) reduction of the quinone to the hydroquinone;
• (c) halogenation;
• hydroboration/doxidation;
• nitration;
• nitration, reduction of the nitro group to an amine followed by acylation of the amine;
• epxidation;
• or epoxidation, ring opening with an amino compound, and acylation;
• respectively, to give a compound having formula:
• ##STR245## (d) oxidation to the quinone;
• and (e) reaction with azide in acidic solution to give said azepine.

A method for preparing an azepine having the formula:

• ##STR246## wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and A is (CH.sub.2).sub.n, wherein n is 1 to 4;
• and X' and Y' are independently halogen;
• hydroxy and hydrogen;
• nitro and hydrogen;
• alkanoylamido and hydrogen;
• X' and Y' together form an oxirane ring;
• or X' and Y' are vicinal alkanoylamido alkanoyloxy groups;
• comprising
• (a) the Diels-Alder reaction of the compound having formula ##STR247## with the quinone having the formula ##STR248## wherein one of A and B is hydrogen and the other of A and B is alkoxy, chloro, bromo, iodo, tosyl or mesityl;
• and R.sub.7 is defined above;
• to give the compound having formula ##STR249## (b) reduction of the quinone to the hydroquinone;
• (c) halogenation;
• hydroboration/oxidation;
• nitration;
• nitration, reduction of the nitro group to an amine followed by acylation of the amine;
• epoxidation;
• or epoxidation, ring opening with an amino compound, and acylation;
• respectively, to give a compound having formula:
• ##STR250## (d) oxidation to the quinone;
• and (e) reaction with azide in acidic solution to give said azepine.

A method for preparing an azepine having the formula:

• ##STR251## wherein R.sub.1, R.sub.3, R.sub.4, and R.sub.6 are independently hydrogen, halo, haloalkyl, aryl, fused aryl, a heterocyclic group, a heteroaryl group, alkyl, alkenyl, alkynyl, arylalkyl, arylalkenyl, arylalkynyl, hydroxyalkyl, nitro, amino, cyano, acylamido, hydroxy, thiol, acyloxy, azido, alkoxy, carboxy, carbonylamido, alkylthiol, trialkylsilyloxy, phenyldialkylsilyloxy;
• R.sub.7 is alkyl, alkanoyl, trialkylsilyl, phenyldialkylsilyl or tetrahydropyranyl;
• and A is (CH.sub.2).sub.n, wherein n is 1 to 4;
• X' and Y' are independently halogen;
• hydroxy and hydrogen;
• nitro and hydrogen;
• alkanoylamido and hydrogen;
• X' and Y' together form an oxirane ring;
• or X' and Y' are vicinal alkanoylamido alkanoyloxy groups;
• and
• where one of A' and B' is hydrogen and the other of A' and B' is alkyl or aralkyl, comprising
• (a) the Diels-Alder reaction of the compound having Formula VII with a quinone having the Formula:
• ##STR252## where A', B' and R.sub.7 are defined above, to give a compound of the Formula:
• ##STR253## (b) halogenation;
• hydroboration/oxidation;
• nitration;
• nitration, reduction of the nitro group to an amine followed by acylation of the amine;
• epxidation;
• or epoxidation, ring opening with an amino compound, and acylation;
• respectively,
• to give a compound having formula:
• ##STR254## and (c) reaction with azide in acidic solution to give said azepine.