ChemInform Abstract: PERINAPHTHYLENEDIAMINES. II. GENERAL METHOD FOR THE SYNTHESIS OF TETRA‐, TRI‐, AND DI‐N‐SUBSTITUTED 1,8‐NAPHTHYLENEDIAMINES

Naphthalene 'proton sponges'

“…The proton sponge salt formed is converted into the base by treatment with an aqueous alkali. 25,26 b. Syntheses based on 1,1,3-trialkyl-2,3-dihydroperimidinium salts Far from all of the naphthalene `proton sponges' can be obtained by alkylation of peri-diamines or by functionalisation of the unsubstituted compound 6. Therefore, the author of this review with his coworkers have developed an alternative and practically versatile procedure for the synthesis of 1,8-bis(dialkylamino)naphthalenes from 1,1,3-trialkyl-2,3-dihydroperimidinium salts.…”

“…Thus if the nitrogen atoms have different substituents (e.g., Me and Et), quaternisation affects only the nitrogen atom carrying the smallest group. 25 Analogously, but owing to electronic (rather than steric) factors, methylation of 1,3-dimethyl-6-nitro-2,3-dihydroperimidine 54c gives exclusively the salt 55c. 30 The latter manifests an abnormal behaviour upon alkaline treatment.…”

Heterocyclic superbases: retrospective and current trends

“…Alkalis, alcoholates, and sodium acetate are classical bases. In water and alcohols, they permit the ionization of acids with pK a below 14-15 but when dimethyl sulfoxide (DMSO) is used as the solvent, their ionizing capacity is enhanced 12-13-fold, permitting the ionization of such weak acids as acetylenes and arylamines (pK a [22][23][24][25][26][27] [6]. Such media, for example, KOH-DMSO, have been classified as superbasic.…”

“…One of the first attempts in this direction involved the replacement of the peri-NMe 2 groups by other dialkylamino groups such as Et 2 N [22] and Pr 2 N groups in compounds 12a,b [23], pyrrolidino 13, piperidino 14 [23], and bridging groups as in diamines 15a-e and 16 [24,25]. It was supposed that alkyl groups with a stronger +I effect than for the methyl substituent should lead to increased basicity.…”

peri-Naphthylenediamines: XXXIX. Synthesis and Structure of N,N′,N′-Trimethyl-N-nitrosonaphthalene-1,8-diamine Derivatives

“…A solution of 1 mmol of compound Va, Vb [21], or Vc [22] in 5 ml of 50% aqueous acetic acid was cooled to 0-5°C, and a solution of 0.069 g (1 mmol) of sodium nitrite in 0.5 ml of water was added dropwise at such a rate that the temperature of the mixture did not exceed 5°C. The mixture was stirred for 30 min at that temperature and neutralized with a concentrated ammonia solution to pH 7-8, and the resulting dispersion was treated with chloroform.…”