20734-58-1Relevant articles and documents
Fractionation Factors for the Aqueous Hydroxide Ion and Solvent Isotope Effects on the Ionisation of 1,8-Bis(dimethylamino)naphthalene (Proton Sponge)
Chiang, Yvonne,Kresge, A. Jerry,O'Ferrall, Rory A. More
, p. 1832 - 1839 (1980)
Isotopic fractionation factors φa and φb for the hydroxy hydrogen and hydrogen bonded water hydrogens of the solvated hydroxide ion are important in controlling solvent isotop effects upon reactions involving the hydroxide ion, and were required for a vibrational analysis of the solvated ion.The product φaφb3=0.434 is accurately available from e.m.f. measurements corrected for free energies of ion transfer between H2O and D2O, but separation of φa and φb, which requires measurements in H2O-D2O mixtures is known to be subject to considerable uncertainty.Thus careful measurements with 1,8-bis(dimethylamino)naphthalene gave KD2O/KH2O=0.420 (+/-) 0.006 for the ratio of basic ionisation constants in H2O and D2O and φp=0.901 (+/-) 0.014 for the fractionation factor of the protonated base, but measurements in 1:1 H2O-D2O gave an ionisation constant too small to be consistent with any reasonable fractionation factor model for the hydroxide ion.Alternative methods of dissecting φa and φb, from measurements of isotope separation factors between hydroxide solution water vapour and autoprotolysis constants of H2O-D2O mixtures, are critically reviewed and optimum values are assessed.The results are shown to be sensitive to experimental error and to medium effects but not to departures from the Rule of the Geometric Mean.
Base-promoted transformation of 2-C(O)R-1,8-bis(dimethylamino)naphthalenes into benzo[g]indole derivatives
Kachalkina, Svetlana G.,Borodkin, Gennady S.,Pozharskii, Alexander F.,Antonov, Alexander S.,Borodkina, Inna G.,Maltsev, Yuri F.,Filatova, Ekaterina A.,Filarowski, Aleksander,Ozeryanskii, Valery A.
, p. 182 - 184 (2015)
1,8-Bis(dimethylamino)naphthalenes bearing 2-positioned trifluoroacetyl or ethoxycarbonyl group on treatment with 2-lithio-1,8-bis-dimethylamino)naphthalene undergo base-promoted transformation into benzo[g]indole derivatives in small to moderate yield, representing previously unknown mode of the pyrrole ring closure which proceeds via deprotonation of the NMe group.
Ring lithiation of 1,8-bis(dimethylamino)naphthalene: Another side of the 'proton sponge coin'
Antonov, Alexander S.,Pozharskii, Alexander F.,Ozeryanskii, Valery A.,Filarowski, Aleksander,Suponitsky, Kyrill Yu.,Tolstoy, Peter M.,Vovk, Mikhail A.
, p. 17756 - 17766 (2015/10/19)
It has been found that 1,8-bis(dimethylamino)naphthalene (DMAN), unlike N,N-dimethylaniline, undergoes ring metallation in the n-BuLi-TMEDA-Et2O system with a low selectivity and in poor total yields. The situation is significantly improved in the t-BuLi-TMEDA-n-hexane system when 3- and 4-lithium derivatives become the only reaction products obtained in good yields. The formation of 3-Li-DMAN is especially desired since no method of direct meta-functionalization of DMAN is known to date. The relative stability and structure of DMAN lithium derivatives have been examined with the help of X-ray and multinuclear NMR measurements as well as DFT calculations.
peri-naphthalenediamines: XXXIV. 1,4,5,8-Tetrakis(dimethylamino)naphthalene: Alternative approaches to synthesis
Sorokin,Ozeryanskii,Pozharskii
, p. 699 - 708 (2007/10/03)
New methods were proposed for synthesizing 1,4,5,8-tetrakis(dimethylamino)naphthalene with an overall yield of 4 to 12% to replace the known procedure ensuring an overall yield of 2%. Catalytic hydrogenation was shown to be inapplicable for preparation of polyaminonaphthalenes from nitro compounds having 3 or 4 nitro gruops in the α-positions. Nucleophilic amination of 1,5-dinitronaphthalene in the system NH2OH/NaOH/MeOH yields 1-amino-4-nitronaphthalene. The nitration of 1,5-bis(p-tolylsulfonylamino)-naphthalene leads to formation of 2,6-dinitro rather than 4,8-dinitro derivative, as it was believed formerly. This was confirmed by transformation of the latter into 1,2,5,6-tetrakis(dimethylamino)naphthalene. 3-Nitro, 2,6-dinitro, 2,6-diamino, and 2,4,6,8-tetranitro derivatives of 1,5-bis(dimethylamino)naphthalene, nitro and amino derivatives of 1,4,5-tris(dimethylamino)naphthalene, and 4,5-diamino-1,8-bis(methylamino)naphthalene were synthesized. By treatment with perchloric acid 1,4,5,8-tetrakis(dimethylamino)naphthalene was oxidized to 2,3-dihydroperimidinium salt.