Transformation of sulfide linkages to carbon-carbon double bond. Syntheses of cis- and trans-15,16-dimethyldihydropyrene and trans-15,16-dihydropyrene

Mitchell, Reginald H.; Boekelheide, V.

doi:10.1021/ja00812a045

Cited by 227 publications

(116 citation statements)

References 5 publications

Supporting

Mentioning

113

Contrasting

Unclassified

Order By: Relevance

“…3(2) c (17) 10,7 (6) SJX-3a and 115.4" in syn-1. The t@o phenyl rings are (5) not directly above one another in either compound.…”

Section: 8(2) C(11)mentioning

confidence: 88%

“…Discussion When 1 was first described (1,2) no other dithia~netacyclophanes 3 having defined stereochemistry were known. Mitchell and Boekelheide (5,14) were Can. J. Chem.…”

Section: C(8) 3937i7jmentioning

confidence: 99%

“…6 6.6 for the internal aryl hydrogens (Hi) which did not change on cooling. This observed position for Hi was assumed to be an average chemical shift for all contributing conformers, though it was quite clear from these and subsequent papers (3)(4)(5)(6) that the anticonformer of 1 was generally thought to be preponderant. This was not unreasonable at that time, since it was known that from 'Hmr (7) and X-ray (8) data that [2,2]metacyclophane only existed in the anti-form 2, and also it was observed (5) that in the coupling reaction of 2,6-bis(bromomethy1)toluene with sodium sulphide, the anti-conformer of 3a was formed in seven times the amount of syn-3a.…”

Section: Introduslionmentioning

confidence: 99%

See 2 more Smart Citations

The crystal and molecular structure of syn-2,11-dithia[3,3]metacyclophane

Anker¹,

Bushnell²,

Mitchell³

1979

Can. J. Chem.

View full text Add to dashboard Cite

. Can. J. Chem. 57, 3080 (1979).The crystal structure of syn-2,l I-dithia[3,3]metacyclophane, C16H16S2, has been determined by single crystal X-ray diffraction and refined to an R-value of 0.049. The crystal is monoclinic with cell dimensions a = 1898.2(5), b = 795.7(3), c = 924.1(4) pm, p = 100.03"(4). The 'Hmr data have been re-examined and compared with those obtained for other cyclophanes, together with 13Cmr data and are consistent with the fact that in solution 2,ll-dithia[3,3]metacyclophane, 1, exists as the syn-conformer with no appreciable participation of the anriconformer. All related dithia[3,3]metacyciophanes which have internal aryl hydrogens (i.e., no internal substituents) likewise appear to be syn from 'Wmr data.

show abstract

“…3(2) c (17) 10,7 (6) SJX-3a and 115.4" in syn-1. The t@o phenyl rings are (5) not directly above one another in either compound.…”

Section: 8(2) C(11)mentioning

confidence: 88%

“…Discussion When 1 was first described (1,2) no other dithia~netacyclophanes 3 having defined stereochemistry were known. Mitchell and Boekelheide (5,14) were Can. J. Chem.…”

Section: C(8) 3937i7jmentioning

confidence: 99%

Section: Introduslionmentioning

confidence: 99%

See 1 more Smart Citation

The crystal and molecular structure of syn-2,11-dithia[3,3]metacyclophane

Anker¹,

Bushnell²,

Mitchell³

1979

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…In some cases, e.g., 7 and 8, both conformers are capable of independent existence and can be isolated (6). In the case of 6 only one state, probably a rapidly averaging mixture of conformers, is found in solut~on, while in the solid state 6 is found as the syn conformer (5 An ORTEP drawing of tetrasulphide 1.…”

Section: Etomentioning

confidence: 99%

The crystal and molecular structure of 2,3,12,13-tetrathia[4,4]metacyclophane

Beveridge¹,

Bushnell²,

Mitchell³

1983

Can. J. Chem.

View full text Add to dashboard Cite

Conformations in a variety of cyclophane structures are discussed, as determined by X-ray diffraction in crystals and by 1Hmr in solution. Established nomenclature is brought forward (syn/anti and synclinal/anticlinal) and used to deal with an intermediate case which has been examined by both techniques. The crystal and molecular structure of the title compound, C16H16S4, is determined and refined to R = 0.0497. The crystal is orthorhombic, space group Pbca, a = 16.593(2), b = 10.018(2), c = 19.407(3) Å at 25(2) °C, Z = 8, Dcalc = 1.386 g cm−3. The molecular conformation in the crystal is anticlinal with a dihedral angle between the benzene rings of 101°. The benzene rings are displaced laterally by 0.727 Å and the sequence of torsion angles is similar in the two bridging chains.

show abstract

“…In general, the conjugation length and the orientation of the chromophores may play a distinctive role in this respect. Moreover, incorporation of a double bond in the tethering aliphatic chain(s) such as cyclophenes and cyclophandienes may alter the geometry of the molecules which may lead to unusual photophysical properties [28][29][30]. In the previous sections, we have demonstrated the unique synthetic approaches and useful physical properties of alternating benzene-furan oligomers.…”

Section: Synthesis Of Furan-containing [N2]cyclophenesmentioning

confidence: 94%

Heterophenes revisited

Luh

Lin

Chou

2008

Pure and Applied Chemistry

View full text Add to dashboard Cite

By employing the furan annulation protocol, a new series of furan-containing teraryl [n.2]cyclophenes (n = 2-6 and 12) are prepared. These cyclophenes exhibit chargetransfer character in the absorption spectra and unusually large Stokes shifts in the emission spectra. They have neither particularly strong electron-donating moieties nor electron-withdrawing groups, but exhibit unusual second-order nonlinear optical (NLO) properties. The π-systems in teraryl system and in the bridging double bond are highly twisted. Interaction between these twisted π-systems may account for the significant enhancement in hyperpolarizability. Thiophene analog behaved similarly. The five-membered heteroaromatic rings may not only serve as electron donors, but also may accommodate the appropriate geometry to enable the interactions between the oligoaryl systems and the double bond leading to unusual photophysical and NLO properties.

show abstract

Transformation of sulfide linkages to carbon-carbon double bond. Syntheses of cis- and trans-15,16-dimethyldihydropyrene and trans-15,16-dihydropyrene

Cited by 227 publications

References 5 publications

The crystal and molecular structure of syn-2,11-dithia[3,3]metacyclophane

The crystal and molecular structure of syn-2,11-dithia[3,3]metacyclophane

The crystal and molecular structure of 2,3,12,13-tetrathia[4,4]metacyclophane

Heterophenes revisited

Contact Info

Product

Resources

About