peri-Naphthylenediamines. 35. Unusual behavior of “proton sponge”-derived Mannich bases

Aminomethylation of 1,8-bis(dimethylamino)naphthalene (proton sponge) afforded a series of its 4-dialkylaminomethyl-substituted derivatives. An attempt to introduce the second peri-dialkylaminomethyl group unexpectedly led to the formation of salts with the 2,2-dialkyl-6,7-bis(dimethylamino)-2-azonia-2,3-dihydrophenalene cation. The structure of one of these salts was established by X-ray diffraction analysis. Treatment of 1,8-bis(dimethylamino)-4-piperidinomethylnaphthalene with iodomethane gave a spiro compound rather than the expected N-[4,5-bis(dimethylamino)-1-naphthylmethyl]-N-methylpiperidinium iodide. This spiro compound was generated through cyclodimerization of the 1-naphthylmethyl carbocations. These transformations provide evidence that proton sponge-derived Mannich bases quaternized at the dialkylaminomethyl group are unstable and undergo the spontaneous transformation into the resonance-stabilized 4,5-bis(dimethylamino)-1-naphthylmethyl carbocation. By contrast, 4-dialkylamino-1-dimethylaminomethylnaphthalenes gave methoiodides, which are stable under standard conditions. The latter compounds undergo the nucleophilic substitution of the NR₃ group typical of such salts.     

Synthesis and characterization of new air stable primary amido substituted diborane(4) derivatives

Three new diborane(4) derivatives, 1,2-bis(2,4,6-trimethylanilide)-1,2-bis(dimethyamido)diborane(4) (1), 1,2-bis(2,4,6-trimethylanilide)-1,2-bis(duryl)diborane(4) (2) and 1,2-bis(anilide)-1,2-bis(duryl)diborane(4) (3), have been synthesized and characterized by means of elemental analysis, IR, ¹H, ¹³C and ¹¹B NMR spectroscopy. Additionally, the structures of compounds 1 and 2 have been determined by the single crystal X-ray diffraction technique. The compounds 1 and 2 crystallize in the monoclinic P21/c space group. All of the compounds were found to be air stable.     

Preparation of 1,1-disubstituted silacyclopentadienes

Several new 1,1-disubstituted siloles containing substituents on the ring carbon atoms have been synthesized. The new siloles: 1,1-dihydrido-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (5), 1,1-dihydrido-2,5-dimethyl-3,4-diphenylsilole (6), 1,1-dimethoxy-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (7), 1,1-bis(4-methoxyphenyl)-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (8), 1,1-dipropoxy-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (9), and 1,1-dibromo-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (13) were prepared from reactions originating from the previously reported, 1,1-bis(diethylamino)-2,5-bis(trimethylsilyl)-3,4-diphenylsilole (1) or 1,1-bis(diethylamino)-2,5-dimethyl-3,4-diphenylsilole (2). In addition, three other new organosilane byproducts were observed and isolated during the current study, bis(4-methoxyphenyl)bis(phenylethynyl)silane (11), bis(4-methoxyphenyl)di(propoxy)silane (12) and 1-bromo-4-bromodi(methoxy)silyl-1,4-bis(trimethylsilyl)-3,4-diphenyl-1,3-butadiene (14). Compounds 13 and 14 were characterized by X-ray crystallography and 14 is the first 1,1-dibromosilole whose solid state structure has been determined.     

Functionally Substituted Isocyanurates with Heteroatoms (O,S) in the N-Alkyl Chain

Alkylation of disodium benzyl and disodium methyl isocyanurates with ,'-dichlorodiethyl and ,'-dibromodiethyl ethers was used to prepare 1-benzyl and 1-methyl 3,5-bis[2-(2-haloethoxy)ethyl] isocyanurates whose reaction with thiourea followed by hydrolysis gave the corresponding 1-alkyl 3,5-bis[2-(2-mercaptoethoxy)ethyl] isocyanurates. 1-Benzyl and 1-methyl 3,5-bis[2-(2-chloroethyl)ethyl] isocyanurates were reacted with NaSCH₂CH₂OH to obtain the corresponding 1-alkyl 3,5-bis[2-(2-hydroxyethylthio)ethyl] isocyanurates. Treatment of the latter two esters with thionyl chloride gave 1-benzyl and 1-methyl 3,5-bis-[2-(2-chloroethylthio)ethyl] isocyanurates, respectively.     

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.     

New crown ether with indoxyl groups

Conclusions The reaction of diaminodibenzo-18-crown-6 with monochloroacetic anhydride in dioxane at room temperature gives 4,5-bis(chloroacetylamino)dibenzo-18-crown-6. The same reaction carried out in ethanol at reflux gives 4,5-bis(glycine hydrochloride)dibenzo-18-crown-6, which is converted in the presence of water to 8,9;17,18-bis(indoxyl)-18-crown-6.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1160–1162, May, 1989.     

Synthesis and near infrared electrochromic properties of metallodithiolene complexes

Four metallodithiolene complexes[4,8-bis(octyloxy)-1,3,5,7-tetrathia]?di[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)](3),[4,8-bis(octyloxy)-1,3,5,7-tetrathia]di[1,3-bis(diphenylphosphino)propane?nickel(II)](4),[4,8-bis(octyloxy)-1,3,5,7-tetra-thia]?[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)]?[1,3-bis(diphenylphosphino)propane·nickel(II)](5)and di[4,8-bis(octyloxy)-1,3,5,7-tetrathia]?[1,1′-bis(diphenylphosphino)ferrocene?palladium(II)]?nickel(II)(6)were synthesized and the near-infrared(NIR)electrochromic properties were studied.The spectroelectrochemical spectra and the electrochromic parameters such as optical contrast,switching time,optical density change,electrochromic efficiency and optical attenuation of complexes 3–6 were investigated in detail.The symmetric binuclear complex 4 showed relatively high electrochromic efficiency of63.0 and 75.4 cm~2/C both in the two oxidation states.The complexes exhibited excellent electroactive/electrochromic stability characterized by chronoamperometry(4000 cyclic switches).     

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.     

Reaction of acylacetylenes and methyl propiolate with N,N′-bis(dithiocarboxy)piperazine

The reaction of N,N-bis(dithiocarboxy)piperazine with acetylenic ketones and methyl propiolate gave N,N-bis(acylvinyldithiocarbo)- and N,N -bis(methoxy-carbonylvinyldithiocarbo)piperazines. Heating the compounds obtained with perchloric acid leads to intramolecular cyclization with the formation of N,N -bis[2-acyl(methoxycarbonyl)methyl-1,3-dithietanium]piperazine perchlorates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2637–2640, November, 1990.     

Alkylation of oxypurines by α,ω-dihaloalkanes 1. Reaction of xanthine sodium salts and some N-methyl derivatives with α,ω-dihaloalkanes

A method was developed for obtaining previously unknown 1,3,7-tris(-haloalkyl)-, 1,7-bis(-chloroalkyl)-3-methyl-, and 1,3-bis(-chloropentyl)-7-methylxanthines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya No. 9, pp. 2102–2105, September, 1989.     

Synthesis and reactions of thiophene sulfides. Communication 40. An unusual reaction of 2,5-bis(methylthio)-3,4-bis(o-hydroxyphenyliminomethyl)thiophene

Conclusions In polar solvents (ethanol and chloroform), 2,5-bis(methylthio)-3,4-bis-(o-hydroxyphenyliminomethyl) thiophene undergoes intramolecular rearrangement to 2,5-bis(methylthio)-3-(2-benzoxazolyl)-4-(o-hydroxyphenylaminomethyl) thiophene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2750–2753, December, 1985.     

Synthesis of 1,4-diazabicyclo[2.2.2]octane

Double intramolecular cyclization of N,N-bis(2-chloroethyl)-N-N-bis(2-cyanoethyl)ethylenediamine leads to 1,4-bis(2-cyanoethyl)-1,4-diazoniabicyclo[2.2.2]octane dichloride, which undergoes decyanoethylation to 1,4-diazabicyclo[2.2.2]octane when it is heated. The structures of the compounds were confirmed by their IR and PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 548–550, April, 1978.     

Synthesis of 1-Methyl and 1-Benzyl 3,5-Bis(ω-Mercaptoalkyl) Isocyanurates

1-Methyl and 1-benzyl 3,5-bis(-haloalkyl) isocyanurates were reacted with thiourea to obtain 1-methyl and 1-benzyl 3,5-bis[-[amino(imino)methylmercapto]alkyl] isocyanurates, respectively. Hydrolysis of the latter gave the corresponding 3,5-bis(-mercaproalkyl) izocyanurates.     

Synthesis of pyrimidinophanes containing nitrogen atoms in polymethylene bridges

The reactions of 1,3-bis(-bromobutyl- or -pentyl)-6-methyluracil with 1,3-bis(-ethylaminobutyl- or -pentyl)-6-methyluracil afforded pyrimidinophanes containing N atoms in bridging polymethylene chains. Individual geometric isomers of pyrimidinophanes were isolated. The structure of one of these isomers was established by X-ray diffraction analysis. Quaternization of the bridging N atoms with o-nitrobenzyl bromide gave rise to water-soluble pyrimidinophanes.     

Chloromethylation of substituted di(2-thienyl)methanes and the reductive desulfuration of some diamines of the thiopene series

The action of chloromethyl ether on di(2-thienyl)methane, 1, 1-di-(2-thienyl)ethane, 2, 2-di(2-thienyl)propane, 2, 5-bis(dimethyl-2-thienylmethyl)thiophene, and 1, 1, 1-tri(2-thienyl)ethane has given, respectively: 5-chloromethyl -2 -thienylthiophene, 1, 1-bis(5-chloro-methyl-2-thienyl)ethane, 2, 2-bis(5-chloromethyl-2-thienyl)propane, 2, 5-bis(dimethyl-5-chloromethyl-2-thienylmethyl)thiophene, 1-(2-thienyl)-1, 1-bis(5-chloromethyl-2-thienyl)-ethane, and the corresponding amines: 5-diethylaminomethyl-2-thienylthiophene, 1,1-Bis(5-diethylaminomethyl-2-thienyl)ethane, 2, 2-bis(5-aminomethyl-2 -thienyl)propane, 2, 2-bis(5-methylaminomethyl-2-thienyl)propane, 2, 5-bis(dimethyl-5-dimethylaminomethyl-2-thienylmethyl)thiophene, and 2, 8, 8, 14, 20, 20-hexamethyl-2, 14-diaza-3, 2, 3, 2--cyclotetrathiene. The reductive desulfonation over Raney nickel of the diacetyl derivatives of 2, 2-bis(5-aminomethyl-2-thienyl)propane and 2, 2-bis(5-methylaminomethyl-2-thienyl)propane has given the diacetyl derivatives of aliphatic amines.     

Reaction of azulene with 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol in a mixed solvent of methanol and acetonitrile in the presence of hydrochloric acid: a facile one-pot synthesis and properties of new triarylethylenes possessing an azulen-1-yl group

Reaction of azulene (1) with 1,2-bis[4-(dimethylamino)phenyl]-1,2-ethanediol (2) in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 °C for 3 h gives 2-(azulen-1-yl)-1,1-bis[4-(dimethylamino)phenyl]ethylene (3) (8% yield), 1-(azulen-1-yl)-(E)-1,2-bis[4-(dimethylamino)phenyl]ethylene (4) (28% yield), and 1,3-bis{2,2-bis[4-(dimethylamino)phenyl]ethenyl}azulene (5) (9% yield). Besides the above products, this reaction affords 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino)phenyl]ethane (6) (15% yield), a meso form (1R,2S)-1,2-di(azulen-1-yl)-1,2-bis[4-(dimethylamino)phenyl]ethane (7) (6% yield), and the two enantiomeric forms (1R,2R)- and (1S,2S)-1,2-di(azulen-1-yl)-1,2-bis[4-(dimethylamino)phenyl]ethanes (8) (6% yield). Furthermore, addition reaction of 3 with 1 under the same reaction conditions as the above provides 6, in 46% yield, which upon oxidation with DDQ (=2,3-dichloro-5,6-dicyano-1,4-benzoquinone) in dichloromethane at 25 °C for 24 h yields 1,1-di(azulen-1-yl)-2,2-bis[4-(dimethylamino)phenyl]ethylene (9) in 48% yield. Interestingly, reaction of 1,1-bis[4-(dimethylamino)phenyl]-2-(3-guaiazulenyl)ethylene (11) with 1 in a mixed solvent of methanol and acetonitrile in the presence of 36% hydrochloric acid at 60 °C for 3 h gives guaiazulene (10) and 3, owing to the replacement of a guaiazulen-3-yl group by an azulen-1-yl group, in 91 and 46% yields together with 5 (19% yield) and 6 (13% yield). Similarly, reactions of 2-(3-guaiazulenyl)-1,1-bis(4-methoxyphenyl)ethylene (12) and 1,1-bis{4-[2-(dimethylamino)ethoxy]phenyl}-2-(3-guaiazulenyl)ethylene (13) with 1 under the same reaction conditions as the above provide 10, 2-(azulen-1-yl)-1,1-bis(4-methoxyphenyl)ethylene (16), and 1,3-bis[2,2-bis(4-methoxyphenyl)ethenyl]azulene (17) (93, 34, and 19% yields) from 12 and 10 and 2-(azulen-1-yl)-1,1-bis{4-[2-(dimethylamino)ethoxy]phenyl}ethylene (18) (97 and 58% yields) from 13.     

Reaction of 1,4-bis(trimethylsilyl)-2-butene with aromatic aldehydes catalyzed by TiCl4: an approach to (1-vinylallyl)benzene type derivatives

1,4-bis(Trimethylsilyl)-2-butene 1 can react with alkyl and aromatic aldehydes in the presence of titanium tetrachloride to give α-(trimethylsilyl)methyl homoallylic alcohols and (1-vinylallyl)benzene type compounds in poor to good yield according to the related position of each substituents present on the aromatic ring. In the last case, the reaction involves a type electrophilic substitution of 1,4-bis(trimethylsilyl)-2-butene by aromatic aldehydes activated by TiCl₄, followed by a 1,2-migration of a vinyl group.     

Evidence of the central tetrathiafulvalene bond opening by copper(II) salts. In situ generation of 2,3-bis(2′-cyanoethylchalcogeno)-7,8-benzo-1,4,6,9-tetrathia-10-ceto spiro[4,5]decane

The two-electrons oxidation of 4,5-benzo-6,7-bis(2′-cyanoethylthio) TTF (CETBz-TTF) and 4,5-benzo-6,7-bis(2′-cyanoethylseleno) TTF (CESBz-TTF) with Cu²⁺X₂ (X = Cl⁻, ) leads to the formation of 2,3-bis(2′-cyanoethylchalcogeno)-7,8-benzo-1,4,6,9-tetrathia-10-ceto spiro[4,5]decane after opening of the -C-S- bond of the central TTF core.     

Syntheses and conversion of polyhedral compounds. 26. Synthesis of new heteropolyhedral compounds by heterocyclization of certain 3,7-disubstituted derivatives of 3,7-diaza-and 1,3,7-triazabicyclo-[3.3.1]nonanes

The following heterocyclization reactions have been carried out: heterocyclization of 3,7-diacryloyl-3,7-diazabicyclo[3.3.1]nonane by benzylamine, heterocyclization of 3,7-diacryloyl-, 3,7-bis(-bromopropionyl)-, and 3,7-bis(-chloroethyl)-3,7-diazabicyclo[3.3.1]nonanes by hydrogen sulfide, and heterocyclization of 3,7-bis(bromoacetyl)- and 3,7-diacryloyl-1,3,7-triazabicyclo[3.3.1]nonanes by benzylamine and hydrogen sulfide. New compounds were obtained, based on previously unknown thiadiaza-, triaza-, and tetraazatricyclic systems.For Communication 25, see [1].A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1133–1136, August, 1998.     

Reactions of azulenes with 1,2-diaryl-1,2-ethanediols in methanol in the presence of hydrochloric acid: comparative studies on products, crystal structures, and spectroscopic and electrochemical properties

Although reaction of guaiazulene (1a) with 1,2-diphenyl-1,2-ethanediol (2a) in methanol in the presence of hydrochloric acid at 60 °C for 3 h under aerobic conditions gives no product, reaction of 1a with 1,2-bis(4-methoxyphenyl)-1,2-ethanediol (2b) under the same reaction conditions as 2a gives a new ethylene derivative, 2-(3-guaiazulenyl)-1,1-bis(4-methoxyphenyl)ethylene (3), in 97% yield. Similarly, reaction of methyl azulene-1-carboxylate (1b) with 2b under the same reaction conditions as 1a gives no product; however, reactions of 1-chloroazulene (1c) and the parent azulene (1d) with 2b under the same reaction conditions as 1a give 2-[3-(1-chloroazulenyl)]-1,1-bis(4-methoxyphenyl)ethylene (4) (81% yield) and 2-azulenyl-1,1-bis(4-methoxyphenyl)ethylene (5) (15% yield), respectively. Along with the above reactions, reactions of 1a with 1,2-bis(4-hydroxyphenyl)-1,2-ethanediol (2c) and 1-[4-(dimethylamino)phenyl]-2-phenyl-1,2-ethanediol (2d) under the same reaction conditions as 2b give 2-(3-guaiazulenyl)-1,1-bis(4-hydroxyphenyl)ethylene (6) (73% yield) and (Z)-2-[4-(dimethylamino)phenyl]-1-(3-guaiazulenyl)-1-phenylethylene (7) (17% yield), respectively. Comparative studies of the above reaction products and their yields, crystal structures, spectroscopic and electrochemical properties are reported and, further, a plausible reaction pathway for the formation of the products 3-7 is described.