Forskning ved Københavns Universitet - Københavns Universitet

Forside

Sulfur-Bridged pen-Naphthalenes: Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningfagfællebedømt

Standard

Sulfur-Bridged pen-Naphthalenes : Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene. / Guttenberger, Hans G.; Bestmann, Hans J.; Dickert, Franz L.; Jorgensen, Flemming S.; Snyder, James P.

I: Journal of the American Chemical Society, Bind 103, Nr. 1, 01.01.1981, s. 159-168.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningfagfællebedømt

Harvard

Guttenberger, HG, Bestmann, HJ, Dickert, FL, Jorgensen, FS & Snyder, JP 1981, 'Sulfur-Bridged pen-Naphthalenes: Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene', Journal of the American Chemical Society, bind 103, nr. 1, s. 159-168. https://doi.org/10.1021/ja00391a029

APA

Guttenberger, H. G., Bestmann, H. J., Dickert, F. L., Jorgensen, F. S., & Snyder, J. P. (1981). Sulfur-Bridged pen-Naphthalenes: Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene. Journal of the American Chemical Society, 103(1), 159-168. https://doi.org/10.1021/ja00391a029

Vancouver

Guttenberger HG, Bestmann HJ, Dickert FL, Jorgensen FS, Snyder JP. Sulfur-Bridged pen-Naphthalenes: Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene. Journal of the American Chemical Society. 1981 jan 1;103(1):159-168. https://doi.org/10.1021/ja00391a029

Author

Guttenberger, Hans G. ; Bestmann, Hans J. ; Dickert, Franz L. ; Jorgensen, Flemming S. ; Snyder, James P. / Sulfur-Bridged pen-Naphthalenes : Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene. I: Journal of the American Chemical Society. 1981 ; Bind 103, Nr. 1. s. 159-168.

Bibtex

@article{d80457f6732a4b13af5309bc1a90a75f,
title = "Sulfur-Bridged pen-Naphthalenes: Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene",
abstract = "The sulfur-bridged 1,8-peri-naphthalenes 3H,7H-naphtho[1,8-de]-1,2-dithiepin (8) and 4H,8H-naphtho[1,8-ef]-1,2,3-trithiocin (9) have been prepared. Their variable-temperature 1H NMR spectra reveal the presence of conformations undergoing rapid equilibration. For the disulfide (8) line-shape analysis yields a single interconversion with ∆H* = 9.3 kcal/mol and ∆S* = -1.2 cal/(mol K). Two processes are resolvable for the trisulfide (9), a relatively rapid one with ∆H* = 15.4 kcal/mol and ∆S* = -1.1 cal/(mol K) and a slower exchange with ∆G* = 17.9 kcal/mol. Interpretation of the DNMR data was assisted by molecular mechanics calculations and photoelectron spectroscopic measurements. It is concluded that the disulfide (8) exists as an unsymmetrical twist-boat conformer with an S-S dihedral angle of ca. 40°. On the NMR time scale, racemization occurs via a boat conformation (Cs symmetry) with a predicted barrier of ∆E = 7.5 kcal/mol. The calculations suggest, however, an accompanying but lower energy transformation (∆E = 5.4 kcal/mol) which interconverts superimposable enantiomers by way of a twist transition state of C2 symmetry. For the trisulfide (9) the force field calculations indicate the boat structure to be 0.6 kcal/mol more stable than the chair conformation. Boat-boat interchange is suggested to take place through an intermediate twist form (∆E = 13.6 kcal/mol) and is lower in energy than the corresponding boat-chair equilibration.",
author = "Guttenberger, {Hans G.} and Bestmann, {Hans J.} and Dickert, {Franz L.} and Jorgensen, {Flemming S.} and Snyder, {James P.}",
year = "1981",
month = "1",
day = "1",
doi = "10.1021/ja00391a029",
language = "English",
volume = "103",
pages = "159--168",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "ACS Publications",
number = "1",

}

RIS

TY - JOUR

T1 - Sulfur-Bridged pen-Naphthalenes

T2 - Synthesis, Conformational Analysis, and Photoelectron Spectroscopy of the Mono-, Di-, and Trisulfides of 1,8-Dimethylnaphthalene

AU - Guttenberger, Hans G.

AU - Bestmann, Hans J.

AU - Dickert, Franz L.

AU - Jorgensen, Flemming S.

AU - Snyder, James P.

PY - 1981/1/1

Y1 - 1981/1/1

N2 - The sulfur-bridged 1,8-peri-naphthalenes 3H,7H-naphtho[1,8-de]-1,2-dithiepin (8) and 4H,8H-naphtho[1,8-ef]-1,2,3-trithiocin (9) have been prepared. Their variable-temperature 1H NMR spectra reveal the presence of conformations undergoing rapid equilibration. For the disulfide (8) line-shape analysis yields a single interconversion with ∆H* = 9.3 kcal/mol and ∆S* = -1.2 cal/(mol K). Two processes are resolvable for the trisulfide (9), a relatively rapid one with ∆H* = 15.4 kcal/mol and ∆S* = -1.1 cal/(mol K) and a slower exchange with ∆G* = 17.9 kcal/mol. Interpretation of the DNMR data was assisted by molecular mechanics calculations and photoelectron spectroscopic measurements. It is concluded that the disulfide (8) exists as an unsymmetrical twist-boat conformer with an S-S dihedral angle of ca. 40°. On the NMR time scale, racemization occurs via a boat conformation (Cs symmetry) with a predicted barrier of ∆E = 7.5 kcal/mol. The calculations suggest, however, an accompanying but lower energy transformation (∆E = 5.4 kcal/mol) which interconverts superimposable enantiomers by way of a twist transition state of C2 symmetry. For the trisulfide (9) the force field calculations indicate the boat structure to be 0.6 kcal/mol more stable than the chair conformation. Boat-boat interchange is suggested to take place through an intermediate twist form (∆E = 13.6 kcal/mol) and is lower in energy than the corresponding boat-chair equilibration.

AB - The sulfur-bridged 1,8-peri-naphthalenes 3H,7H-naphtho[1,8-de]-1,2-dithiepin (8) and 4H,8H-naphtho[1,8-ef]-1,2,3-trithiocin (9) have been prepared. Their variable-temperature 1H NMR spectra reveal the presence of conformations undergoing rapid equilibration. For the disulfide (8) line-shape analysis yields a single interconversion with ∆H* = 9.3 kcal/mol and ∆S* = -1.2 cal/(mol K). Two processes are resolvable for the trisulfide (9), a relatively rapid one with ∆H* = 15.4 kcal/mol and ∆S* = -1.1 cal/(mol K) and a slower exchange with ∆G* = 17.9 kcal/mol. Interpretation of the DNMR data was assisted by molecular mechanics calculations and photoelectron spectroscopic measurements. It is concluded that the disulfide (8) exists as an unsymmetrical twist-boat conformer with an S-S dihedral angle of ca. 40°. On the NMR time scale, racemization occurs via a boat conformation (Cs symmetry) with a predicted barrier of ∆E = 7.5 kcal/mol. The calculations suggest, however, an accompanying but lower energy transformation (∆E = 5.4 kcal/mol) which interconverts superimposable enantiomers by way of a twist transition state of C2 symmetry. For the trisulfide (9) the force field calculations indicate the boat structure to be 0.6 kcal/mol more stable than the chair conformation. Boat-boat interchange is suggested to take place through an intermediate twist form (∆E = 13.6 kcal/mol) and is lower in energy than the corresponding boat-chair equilibration.

UR - http://www.scopus.com/inward/record.url?scp=0000518768&partnerID=8YFLogxK

U2 - 10.1021/ja00391a029

DO - 10.1021/ja00391a029

M3 - Journal article

AN - SCOPUS:0000518768

VL - 103

SP - 159

EP - 168

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 1

ER -

ID: 218715006