peri-Naphthylenediamines. 36. 5,6-Bis(dimethylamino)acenaphthylene in [4+2] cycloaddition reactions. Synthesis and characteristic features of protonation of “proton sponges” with the 8,9-diazafluoranthene structure

5,6-Bis(dimethylamino)acenaphthylene is readily involved in [4+2] cycloaddition reactions with symm-tetrazine derivatives to form new proton sponges with the diazafluoranthene skeleton. Under analogous condition, 1,8-bis(dimethylamino)-4-vinylnaphthalene gave 4-pyridazinyl derivatives. The relative reactivities of 5,6-bis(dimethylamino)acenaphthylene, 1,8-bis(dimethylamino)-4-vinylnaphthalene, 5-dimethylaminoacenaphthylene, and acenaphthylene in the reactions with 3,6-diphenyl-symm-tetrazine are in a ratio of 32 : 17 : 14 : 1. The site of protonation of 3,4-bis(dimethylamino)-7,10-diphenyl-8,9-diazafluoranthene is controlled by the basicity of the solvent. The reaction in acetonitrile afforded the cation stabilized by an intramolecular hydrogen bond, whereas the reaction in dimethyl sulfoxide gave rise to the resonance-stabilized cation. 6,7-Bis(dimethylamino)phenalen-1-one was protonated only at the carbonyl group.     

peri-naphthylenediamines

o-Nitro ando,o′-dinitro derivatives of 1,8-bis(dimethylamino)naphthalene and its acenaphthene analog were prepared for the first time by direct nitration with nitrogen dioxide or tetranitromethane. When 5,6-bis(dimethylamino)acenaphthene was treated with nitric acid in AcOH or MeCN or with nitronium tetrafluoroborate in MeCN, nitration was accompanied by partial demethylation of one of the NMe₂ groups. For Part 27, see Ref. 1. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1215–1220, July, 2000.     

peri-Naphthylenediamines. 32. Reactions of 4,5-bis(dimethylamino)-1-naphthyllithium and 4,5-bis(dimethylamino)-1-naphthylmagnesium bromide with electrophilic agents. New representatives of double naphthalene “proton sponges” with the structures of 1,1"-binaphthyl ketone and 1,1"-binaphthylmethanol

The 4-deuterio, 4-methyl, 4-iodo, 4-methylthio, 4-trimethylsilyl, and 4-ethoxycarbonyl derivatives of 1,8-bis(dimethylamino)naphthalene (proton sponge) and some related alcohols were prepared by the reactions of 4,5-bis(dimethylamino)-1-naphthyllithium or 4,5-bis(dimethylamino)-1-naphthylmagnesium bromide with the corresponding electrophilic reagents. New representatives of double proton sponges with the structures of 1,1"-binaphthyl ketone and 1,1"-binaphthylmethanol were synthesized. The pK _a values of selected compounds in DMSO were measured by competitive protonation.     

peri-Naphthylenediamines

Tertiary alcohols containing the 4,5-bis(dimethylamino)-1-naphthyl group were synthesized. The carbocations that formed from α-methyl-containing alcohols in an acidic medium underwent smooth El elimination to give the corresponding unsaturated derivatives of the “proton sponge” in good yields. At the same time, the carbocation generated from 4-(α-hydroxybenzhydryl)-1,8-bis(dimethylamino)naphthalene was converted into a benzo-[a]fluorene derivative as a result of a complex reaction which has been previously unknown in the chemistry of “proton sponges.” The structure of the latter derivative was established by X-ray diffraction analysis. For Part 26, see Ref. 1; this paper simultaneously presents Part 5 of the series “Resonance-stabilized α-naphthylmethyl carbocations and derived spiro compounds;” for Part 4, see Ref. 2. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1103–1108, June, 2000.     

peri-Naphthylenediamines

4,5,4′,5′-Tetrakis(dimethylamino)-1,1′-binaphthalene, unknown previously, was obtained in ∼20% yield by the oxidation of 1,8-bis(dimethylamino)naphthalene with Tl(OAc)₃ or Pb(OAc)₄ at low temperatures. Treatment of the reaction product with excess Li and then with O₂ gave, depending on the reaction temperature, perylene or 4,4′-bis(dimethylamino)-1,1′-binaphthalene in good yields, instead of expected 3,4,9,10-tetrakis(dimethyl-amino)perylene. For Part 23, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 93–98, January, 1998.     

peri-Naphthylenediamines

The reaction of 1,8-bis(dimethylamino)naphthalene (“proton sponge”) with trifluoroacetic anhydride afforded new derivatives of naphtho[1,8-c,d]pyran,viz., trans-) (4) andcis-1,3-dihydroxy-6,7-bis(dimethylamino)-1,3-bis(trifluoromethyl)-1H,3H-naphthol[1,8-c,d]pyran (5) and symmetrical 3,4,10,11-tetrakis(dimethylamino)-7,14-bis(trifluoromethyl)-7,14-epoxydinaphtho[1,8-a,b;1′, 8′-ef]cyclooctane (3), which belongs to a new type of double “proton sponges,” along with the expected 1,8-bis(dimethylamino)-4-trifluoroacetylnaphthalene. The structures of compounds3 and4 were established by spectral studies and X-ray diffraction analysis.     

Alumina-catalyzed cyclodimerization of 4-hydroxymethyl derivatives of 1,8-bis(dimethylamino)- and 1,8-dimethoxynaphthalenes to symmetrical spiro compounds

4-Hydroxymethyl derivatives of 1,8-bis(dimethylamino)- and 1,8-diiiiethoxynaphthalenes undergo cyclodirnerization on alumina to form symmetrical spir0, compounds of the head-to-tail type. The reaction is considered to be a two-step electrophilic substitution with the participation of naphthyhiiethyl carbocations.Translated fromIzvestiya Akademii Nauk, Seriya Khitnicheskaya, No. 4, pp, 1016–1018, April, 1996.     

peri-Naphthylenediamines

The action of concentrated HCl on 4,5-bis(diethylamino)-1-hydroxymethylnaphthalene resulted in its cyclodimerization of the “head-to-head” type to form a spiro-compound, but, unlike its 4,5-bis(dimethylamino)-analog, cyclodimerization products did not occur on Al₂O₃. The transformation of 4,5-bis(dimethylamino)-1-hydroxymethylnaphthalene on Al₂O₃, TiO₂, and SiO₂ afforded the previously unknown di[4,5-bis(dimethylamino)naphthyl-4]methane, a spiro-compound of the “head-to-tail” type. 4,5-Bis(diethylamino)-1-hydroxy-methylnaphthalene and 4,5-bis(diethylamino)naphthalene-1-carbaldehyde were synthesized. For Part 18, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 348–350, February, 1997.     

peri-Naphthylenediamines 18. 1,8-Bis(dimethylamino)-4-vinylnaphthalene

The 1-[1,8-bis(dimethylamino)-4-naphthyl[ethyl carbocation generated from the corresponding alcohol in benzene in the presence of Al₂O₃ undergoes elimination according to theE1 mechanism to give previously unknown 1,8-bis(dimethylami no)-4-vinyl naphthalene in a good yield. This compound was also synthesized from 1,8-bis(dimethylamino)-4-formylnaphthalene by the Wittig reaction. Polymerization of the vinylic derivative obtained was studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2297–2300, September, 1996.     

Heterocyclic analogs of pleiadiene. 67. Formylation of perimidones, 2,3-dihydroperimidines, and perimidines

Vilsmeier formylation of 1,3-dialkylperimidones, 1,3-dialkyl-2,3-dihydroperimidines, and 2-trifluoromethyl-perimidines is performed. The¹H NMR spectra of the resulting mono- and dialdehydes are discussed.For No. 66, see [1].Rostov State University, Rostov-on-Don 344006Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 365–374, March, 1999.