Partially O-Alkylated thiacalix[4]arenes: Synthesis, molecular and crystal structures, conformational behavior

DVOŘÁKOVÁ, Hana, Jan LANG, Jiří VLACH, Jan SÝKORA, Michal ČAJAN, Michal HIML, Michaela POJAROVÁ, Ivan STIBOR a Pavel LHOTÁK. Partially O-Alkylated thiacalix[4]arenes: Synthesis, molecular and crystal structures, conformational behavior. Journal of Organic Chemistry. Columbus, OH, USA: the American Chemical Society, roč. 72, č. 19, s. 7157-7166. ISSN 0022-3263. 2007.

Základní údaje

• Originální název: Partially O-Alkylated thiacalix[4]arenes: Synthesis, molecular and crystal structures, conformational behavior
• Název česky: Parciálně O-alkylované thiacalix[4]areny: Syntéza, molekulové a krystalové struktury, konformační chování
• Autoři: DVOŘÁKOVÁ, Hana (203 Česká republika, garant), Jan LANG (203 Česká republika), Jiří VLACH (203 Česká republika), Jan SÝKORA (203 Česká republika), Michal ČAJAN (203 Česká republika), Michal HIML (203 Česká republika), Michaela POJAROVÁ (203 Česká republika), Ivan STIBOR (203 Česká republika) a Pavel LHOTÁK (203 Česká republika).
• Vydání: Journal of Organic Chemistry, Columbus, OH, USA, the American Chemical Society, 2007, 0022-3263.

Další údaje

• Originální jazyk: angličtina
• Typ výsledku: Článek v odborném periodiku
• Obor: 10401 Organic chemistry
• Stát vydavatele: Spojené státy
• Utajení: není předmětem státního či obchodního tajemství
• Impakt faktor: Impact factor: 3.959
• Kód RIV: RIV/00216224:14310/07:00019544
• Organizační jednotka: Přírodovědecká fakulta
• UT WoS: 000249371200010
• Klíčová slova anglicky: ALTERNATE CONFORMATION; CONE INTERCONVERSION; INFINITE CHANNELS; SOLID-STATE; X-RAY; COMPLEXATION; THIACALIXARENES; CONFORMERS; H-1-NMR; NMR
• Štítky: ALTERNATE CONFORMATION, Complexation, CONE INTERCONVERSION, CONFORMERS, H-1-NMR, INFINITE CHANNELS, NMR, SOLID-STATE, THIACALIXARENES, x-ray
• Příznaky: Recenzováno

Anotace

NMR spectroscopy, X-ray diffraction analysis, and quantum chemical calculations were used for conformational behavior study of partially alkylated thiacalix[4]arenes bearing methyl (1), ethyl (2), or propyl (3) groups at the lower rim. The conformational properties are governed by two basic effects: (i) stabilization by intramolecular hydrogen bonds, and (ii) sterical requirements of the alkoxy groups at the lower rim. While the monosubstituted derivatives la and 3a adopt the cone conformation in solution, distally disubstituted compounds 1b, 1'b, 2b, 2'b, 3b, and 3'b exhibit several. interesting conformational features. They prefer pinched cone conformation in solution, and, except for 3'b, they form also 1,2-alternate conformation, which is flexible and undergoes rather fast transition between two identical structures. The crystal structures of the compounds 1b, 2b, 2'b, and 3b revealed yet quite rare 1,2-alternate conformation forming molecular channels held together by pi-pi interactions. Different channels-with hexagonal symmetry, 0.26 nm wide-are formed in the crystal structure of the pinched cone conformation of 3b. An uncommon hydrogen bonding pattern was found in dimethoxy and dipropoxy derivatives 1'b and 3'b that adopt distorted cone conformations in crystal. Trialkoxy-substituted compounds 1c and 3c adopt the partial cone conformation in solution. A higher mobility of methyl derivative 1c enables also existence of the cone conformer.

Anotace česky

NMR spectroscopy, X-ray diffraction analysis, and quantum chemical calculations were used for conformational behavior study of partially alkylated thiacalix[4]arenes bearing methyl (1), ethyl (2), or propyl (3) groups at the lower rim. The conformational properties are governed by two basic effects: (i) stabilization by intramolecular hydrogen bonds, and (ii) sterical requirements of the alkoxy groups at the lower rim. While the monosubstituted derivatives la and 3a adopt the cone conformation in solution, distally disubstituted compounds 1b, 1'b, 2b, 2'b, 3b, and 3'b exhibit several. interesting conformational features. They prefer pinched cone conformation in solution, and, except for 3'b, they form also 1,2-alternate conformation, which is flexible and undergoes rather fast transition between two identical structures. The crystal structures of the compounds 1b, 2b, 2'b, and 3b revealed yet quite rare 1,2-alternate conformation forming molecular channels held together by pi-pi interactions. Different channels-with hexagonal symmetry, 0.26 nm wide-are formed in the crystal structure of the pinched cone conformation of 3b. An uncommon hydrogen bonding pattern was found in dimethoxy and dipropoxy derivatives 1'b and 3'b that adopt distorted cone conformations in crystal. Trialkoxy-substituted compounds 1c and 3c adopt the partial cone conformation in solution. A higher mobility of methyl derivative 1c enables also existence of the cone conformer.

Návaznosti

• IAA400200503, projekt VaV: Název: Léčiva na bázi sacharidů a calixarenů - design, struktura, protinádorová a protivirová aktivita

Investor: Akademie věd ČR, Léčiva na bázi sacharidů a calixarenů – design, struktura, protinádorová a protivirová aktivita

• MSM0021622413, záměr: Název: Proteiny v metabolismu a při interakci organismů s prostředím

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Proteiny v metabolismu a při interakci organismů s prostředím