Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes

Thamina Akther, Md Monarul Islam, Shofiur Rahman, Paris E. Georghiou, Taisuke Matsumoto, Junji Tanaka, Pierre Thuéry, Carl Redshaw, Takehiko Yamato

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.

Original languageEnglish
Pages (from-to)3594-3600
Number of pages7
JournalChemistrySelect
Volume1
Issue number13
DOIs
Publication statusPublished - Jan 1 2016

Fingerprint

Hydroxyl Radical
Conformations
Hydrogen bonds
Friedel-Crafts reaction
Methenamine
X ray diffraction
Acylation
Boron
Structural analysis
Nuclear magnetic resonance spectroscopy
Carbon
Crystalline materials
Temperature

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Akther, T., Islam, M. M., Rahman, S., Georghiou, P. E., Matsumoto, T., Tanaka, J., ... Yamato, T. (2016). Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes. ChemistrySelect, 1(13), 3594-3600. https://doi.org/10.1002/slct.201600670

Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes. / Akther, Thamina; Islam, Md Monarul; Rahman, Shofiur; Georghiou, Paris E.; Matsumoto, Taisuke; Tanaka, Junji; Thuéry, Pierre; Redshaw, Carl; Yamato, Takehiko.

In: ChemistrySelect, Vol. 1, No. 13, 01.01.2016, p. 3594-3600.

Research output: Contribution to journalArticle

Akther, T, Islam, MM, Rahman, S, Georghiou, PE, Matsumoto, T, Tanaka, J, Thuéry, P, Redshaw, C & Yamato, T 2016, 'Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes', ChemistrySelect, vol. 1, no. 13, pp. 3594-3600. https://doi.org/10.1002/slct.201600670
Akther, Thamina ; Islam, Md Monarul ; Rahman, Shofiur ; Georghiou, Paris E. ; Matsumoto, Taisuke ; Tanaka, Junji ; Thuéry, Pierre ; Redshaw, Carl ; Yamato, Takehiko. / Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes. In: ChemistrySelect. 2016 ; Vol. 1, No. 13. pp. 3594-3600.
@article{f1cc1a75b2ed4f1784547704b925b867,
title = "Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes",
abstract = "A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.",
author = "Thamina Akther and Islam, {Md Monarul} and Shofiur Rahman and Georghiou, {Paris E.} and Taisuke Matsumoto and Junji Tanaka and Pierre Thu{\'e}ry and Carl Redshaw and Takehiko Yamato",
year = "2016",
month = "1",
day = "1",
doi = "10.1002/slct.201600670",
language = "English",
volume = "1",
pages = "3594--3600",
journal = "ChemistrySelect",
issn = "2365-6549",
publisher = "Wiley-Blackwell Publishing Ltd",
number = "13",

}

TY - JOUR

T1 - Synthesis, Structures and Conformational Studies of 1,2-Dimethyl[2.10]metacyclophan-1-enes

AU - Akther, Thamina

AU - Islam, Md Monarul

AU - Rahman, Shofiur

AU - Georghiou, Paris E.

AU - Matsumoto, Taisuke

AU - Tanaka, Junji

AU - Thuéry, Pierre

AU - Redshaw, Carl

AU - Yamato, Takehiko

PY - 2016/1/1

Y1 - 2016/1/1

N2 - A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.

AB - A series of 1,2-dimethyl[2.10]metacyclophan-1-enes (MCP-1-enes) containing different substituent groups has been synthesized to illustrate their conformational behavior. 4,22-dimethoxy-1,2-dimethyl[2.10]MCP-1-ene 3 was synthesized by a Grignard coupling reaction, Friedel-Crafts acylation reactions and McMurry coupling reaction from 1,10-dibromodecane. The formation of 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 was carried out by demethylation of compound 3 with boron tribromide at room temperature. The syn type conformation of 4 was characterized by X-ray diffraction and was found to form both intramolecular and intermolecular hydrogen bonds between the two hydroxyl groups. From this reaction an interesting compound [10]tetrahydrobenzofuranophane 5 was afforded on prolonging the reaction time. 5,21-diformyl-4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 6 has been prepared from 4,22-dihydroxy-1,2-dimethyl[2.10]MCP-1-ene 4 by using the Duff method in the presence of hexamethylenetetramine. Structural analysis by 1H NMR spectroscopy and X-ray diffraction confirmed that both the solution and the crystalline state of compound 6 adopts an anti-conformation which forms an intramolecular hydrogen bond between the formyl group and the hydroxyl group, which is an interesting finding for long carbon chain MCP compounds.

UR - http://www.scopus.com/inward/record.url?scp=85017174961&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85017174961&partnerID=8YFLogxK

U2 - 10.1002/slct.201600670

DO - 10.1002/slct.201600670

M3 - Article

AN - SCOPUS:85017174961

VL - 1

SP - 3594

EP - 3600

JO - ChemistrySelect

JF - ChemistrySelect

SN - 2365-6549

IS - 13

ER -