New methodology for the synthesis of benzoazacrown ethers by transformation of the macrocycle of benzocrown ethers

Gromov, S. P.; Dmitrieva, S. N.; Ведерников, А. И.; Churakova, M. V.

doi:10.1023/b:rucb.0000046237.00924.80

Russian Chemical Bulletin

2004

DOI: 10.1023/b:rucb.0000046237.00924.80

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New methodology for the synthesis of benzoazacrown ethers by transformation of the macrocycle of benzocrown ethers

S. P. Gromov

S. N. Dmitrieva

А. И. Ведерников

et al.

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Cited by 7 publications

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“…This is characteristic of barium perchlor ate complexes with benzoaza 15 crown 5 13. The anions Cl(1)O4 and Cl(4)O 4 are disordered over two posi tions with populations of 0.72 : 0.38 and 0.57 : 0.43, re spectively. That is why the coordination numbers of Ba(1) and Ba(2) vary from 10 to 12 and their coordination poly hedra are irregular.…”

mentioning

confidence: 94%

“…Cl(3)O4 , and Cl(4)O 4 form co ordination bonds simultaneously to both independent met al cations. This is characteristic of barium perchlor ate complexes with benzoaza 15 crown 5 13.…”

mentioning

confidence: 98%

“…Despite their simple structures, 1 aza 2,3 benzocrown ethers are poorly studied because most of their functional derivatives are scarcely accessible. 3 Earlier, 4 we have obtained formyl and nitro derivatives of N methylbenzoazacrown com pounds by stepwise transformation of the macrocycles of benzocrown ethers. This new strategy of the synthesis of functionalized azacrown ethers seems to be a promising * Dedicated to Academician I. L. Eremenko on his 60th birthday.…”

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confidence: 99%

“…alternative to the currently existing routes to 1 aza 2,3 benzocrown ethers. 4 In the present work, we obtained N alkylnitroben zoazacrown ethers 1b-d and compared the structural and complexing characteristics of azacrown ethers 1a-d and the model compounds nitrobenzo (2) and N (4 nitro phenyl)aza 15 crown 5 (3) using X ray diffraction, 1 H NMR spectroscopy, and DFT calculations. The sta bility constants of complexes of these crown ethers with alkali metal, alkaline earth metal, and ammonium ions were determined using 1 H NMR titration.…”

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confidence: 99%

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Nitro derivatives of N-alkylbenzoaza-15-crown-5: synthesis, structures, and complexation with metal and ammonium cations

et al. 2010

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A number of N alkylnitrobenzoaza 15 crown 5 with the macrocycle N atom conjugated with the benzene ring were obtained. The structural and complexing properties of these com pounds were compared with those of model nitrobenzo and N (4 nitrophenyl)aza 15 crown 5 using X ray diffraction, 1 H NMR spectroscopy, and DFT calculations. The macrocy clic N atom of benzoazacrown ethers are characterized by a considerable contribution of the sp 3 hybridized state and a pronounced pyramidal geometry; the crownlike conforma tion of the macrocycle is preorganized for cation binding, which facilitates complexation. The stability constants of the complexes of crown ethers with the NH 4 + , EtNH 3 + , Na + , K + , Ca 2+ , and Ba 2+ ions were determined by 1 H NMR titration in MeCN d 3 . The most sta ble complexes were obtained with alkaline earth metal cations, which is due to the higher charge density at these cations. The characteristics of the complexing ability of N alkyl nitrobenzoaza 15 crown 5 toward alkaline earth metal cations are comparable with analo gous characteristics of nitrobenzo 15 crown 5 and are much better than those of N (4 nitrophenyl)aza 15 crown 5.

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mentioning

confidence: 94%

“…Cl(3)O4 , and Cl(4)O 4 form co ordination bonds simultaneously to both independent met al cations. This is characteristic of barium perchlor ate complexes with benzoaza 15 crown 5 13.…”

mentioning

confidence: 98%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Nitro derivatives of N-alkylbenzoaza-15-crown-5: synthesis, structures, and complexation with metal and ammonium cations

et al. 2010

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“…5 N Phenyl sub stituted nitrogen containing heterocycles, in which the N atoms are conjugated with chromophoric groups, are of particular interest as photosensitive and photocontrolled molecular devices. 6 The present study is a continuation of investigations on cyclothiomethylation of amines with CH 2 O and H 2 S. [7][8][9] Another aim was to develop efficient methods for the synthesis of aryl substituted thiadiazoles. The latter com pounds are of practical interest.…”

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confidence: 99%

Cyclothiomethylation of aryl hydrazines with formaldehyde and hydrogen sulfide

et al. 2006

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Cyclothiomethylation of phenyl hydrazine with CH 2 O and H 2 S in a ratio of 1 : 3 : 2 in an acidic medium (HCl) afforded previously unknown 3 phenyl 1,3,4 thiadiazolidine (35% yield) and N phenyl(perhydro 1,3,5 dithiazin 5 yl)amine (35% yield). The analogous reaction in an alkaline medium (BuONa) produced N phenyl(perhydro 1,3 thiazetidin 3 yl)amine (22% yield). The reaction of 1,2 diphenyl hydrazine with CH 2 O and H 2 S in an alkaline medium gave 1,2,4,5 tetraphenylhexahydro 1,2,4,5 tetrazine and previously unknown 3,4 diphenyl 1,3,4 thiadiazolidine and 5,6 diphenyltetrahydro 1,3,5,6 dithiadiazepine in 39 and 22% yields, respectively. Cyclothiomethylation of benzyl hydrazine afforded previously unknown bis[(6 benzyl 4,2,6 thiadiazolidin 2 yl)methyl] sulfide (60% yield) and N ben zyl(perhydro 1,3,5 dithiazin 5 yl)amine (19% yield). The reaction of tosyl hydrazine produced 3 [(p tolyl)sulfonyl] 1,3,4 thiadiazolidine, N (perhydro 1,3,5 dithiazin 5 yl) p tolylsulfonamide, and 3,7 bis(p tolylsulfonylamino) 1,5 dithia 3,7 diazacyclooctane in 21, 38, and 41% yields, respectively.Earlier, 1 we have performed cyclothiomethylation of hydrazine with formaldehyde and hydrogen sulfide and prepared annelated 1,3,4 thiadiazolidines and 1,3,5 thia diazines. According to the available data, 2-4 1,3,4 thia diazole derivatives have found wide use as antibacterial and antiviral agents and as inhibitors of oxidation of cya nine dyes and metal complexing agents. 5 N Phenyl sub stituted nitrogen containing heterocycles, in which the N atoms are conjugated with chromophoric groups, are of particular interest as photosensitive and photocontrolled molecular devices. 6 The present study is a continuation of investigations on cyclothiomethylation of amines with CH 2 O and H 2 S. 7-9 Another aim was to develop efficient methods for the synthesis of aryl substituted thiadiazoles. The latter com pounds are of practical interest. We examined thio methylation of phenyl, 1,2 diphenyl, benzyl, and tosyl hydrazines with the H 2 S-CH 2 O system under neutral, acidic, and alkaline conditions. Results and DiscussionRecently, 10 we have found that the thiomethyla tion pathway of hydrazine with CH 2 O and H 2 S strongly depends on the starting component ratio, the heterocyclization temperature, and pH of the reaction mixture.In the present study, we examined cyclothio methylation of phenyl hydrazine hydrochloride (1•HCl) with CH 2 O and H 2 S in a ratio of 1 : 3 : 2 at pH 0.45-0.50 (method A). It was found that the reaction performed at 0 °C selectively produces 3 phenyl 1,3,4 thiadiazol idine (2), whereas N phenyl(perhydro 1,3,5 dithiazin 5 yl)amine (3) and 6 phenylperhydro[1,3,4]thiadiazi no [5,4 d] [1,3,5]dithiazine (4) are generated along with compound 2 at higher temperature (20-70 °C) (Scheme 1). At 70 °C, the amount of minor product 4 derived under these conditions from compound 3 is at most 8%.

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