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5,12‐Diacylated‐5,6,11,12‐tetrahydrodibenzo[ b,f ][1,4]‐diazocines and related compounds
Author(s) -
Yale Harry L.,
Spitzmiller Ervin R.
Publication year - 1976
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570130305
Subject(s) - chemistry , saponification , potassium hydroxide , ethylene glycol , phenylene , alkylation , medicinal chemistry , yield (engineering) , hydroxide , derivative (finance) , ethylene , organic chemistry , polymer , materials science , economics , financial economics , metallurgy , catalysis
Both N,N′ ‐(o‐phenylene)diformamide (1) and N,N′ ‐(4‐chloro‐1,2‐phenylene)diformamide (30) reacted with α,α‐dibromo‐o‐xylene (2) in DMF at 95–100° to give 5,6,11,12‐tetrahydrodibenzo‐[ b,f ][1,4]diazocine‐5,12‐dicarboxaldehyde (3a) and the corresponding 2‐chloro derivative (3b). With potassium hydroxide in ethylene glycol at 110°, 3a and 3b were selectively saponified to the 5‐carboxaldehyde derivatives (4) and either 21a or 22a. Reacylation of the latter led to a series of 5,12‐unsymmetrically diacylated derivatives, 5–18. Additionally, 4 was subjected (a) to a basecatalyzed addition to acrylonitrile to give the 12‐cyanoethyl derivative (19) and (b) alkylation with α‐bromotoluene to give the 12‐benzyl compound (20). Saponification of both carboxaldehyde groups in 3a,b required potassium hydroxide in ethylene glycol at 135° and gave the N,N′ ‐unsubstituted heterocycles (23 and 24) ; these were subsequently reacted with several aldehydes to yield the 5,12‐methano derivatives (25–29) .