N,N,N′‐Trialkyl‐1,8‐diaminonaphthalenes: Convenient Method of Preparation from Protonated Proton Sponges and the First X‐Ray Information.

Abstract

Amines Q 0810 N,N,N'-Trialkyl-1,8-diaminonaphthalenes: Convenient Method of Preparation from Protonated Proton Sponges and the First X-Ray Information. -The title compounds are obtained by partial dealkylation of the corresponding tetraalkyl derivatives under conditions A). In the presence of alkyl iodides, exchange of lower order alkyls by higher ones is observed. Substrates (XI) fail to give demethylated products. -(OZERYANSKII*, V. A.; POZHARSKII, A. F.; KOROLEVA, M. G.; SHEVCHUK, D. A.; KAZHEVA, O. N.; CHEKHLOV, A. N.; SHILOV, G. V.; DYACHENKO, O. A.; Tetrahedron 61 (2005) 17, 4221-4232; Dep. Org. Chem., Rostov State Univ., Rostov-on-Don 344090, Russia; Eng.) -Klein 34-128

Computational design of Brønsted neutral organic superbases—[3]iminoradialenes and quinonimines are important synthetic targets

“…47 Alder's seminal idea has resulted in a large number of related organic superbases utilizing amino nitrogen as a proton attractor and amino groups as chelating functionalities. [48][49][50][51][52][53][54][55][56][57][58][59] A useful extension of the DMAN pattern was materialized recently by syntheses of TMGN [1,8-bis(tetramethylguanidino)naphthalene] 60,61 and HMPN [1,8-bis(hexamethyltriaminophosphazenyl)naphthalene]. 62 This type of superbase has better kinetics and exhibits some other advantageous features compared to phosphazenes.…”

One‐scale basicities of diaminobenzenes and diaminonaphthalenes: from aniline to proton sponge

“…Finally, very good correlation was found between the dioxane and DMSO scales for proton sponges (Fig. ), indicating that the basicity of proton sponges are mostly governed by intrinsic properties of their monoprotonated cations (sterical inhibition to deprotonation of the incapsulated proton enhanced by the + M ‐effect of the ortho ‐substituents in case of 38 and 39 ) [5a,18] …”

“…Correlation of the basicities of proton sponges in aqueous dioxane and DMSO (see Table for chemical structures; for p K a in DMSO, see ref [1a] …”

“…Common anilines and naphthylamines were purified by standard methods or, in case of commercial sources, were used as received. Compounds 4 , 5 , 8 , 7 , 10 , 12 , 19 , 32 , 17 , 13 , 18 , 35 , 21 , 24 , 27 , 33 , 34 , 38 , and 39 , [5a] were prepared in accord with the previously published procedures. Bis(dimethylamino)naphthalenes 22 , 26 , and 30 were synthesized from the corresponding diamines following method .…”

“…The reason for this state of affairs are substantial differences in solubility of naphthylamines, naphthylammonium ions, and protonated dialkylaminonaphthalenes, sharply differing by polarity and hydrophobicity [1c,e] . Equally important is the availability of amines and polyamines of naphthalene series, many of which have become known recently because of the work carried out by our group [1c,e,5] …”