Reactions of Trimethylsilyl Cyanide and <i>N</i>-(Trimethylsilyl) diphenylmethyleneamine with Nitrones and Thermal Decompositions of Their Adducts

Tsuge, Otohiko; Urano, Satoshi; Iwasaki, T.

doi:10.1246/bcsj.53.485

Cited by 13 publications

(6 citation statements)

References 9 publications

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“…Condensation of p- and m -anisaldehydes with p- and m -methoxyphenylacetonitriles in the presence of NaCN gave only the meso/erythro diastereomers of the succinonitriles 30a − c . Stereochemical assignments were based on analogy to meso - 30a , a known compound . Demethylation with BF 3 ·SMe 2 gave the desired bisphenolic succinonitriles ( 31a − c ).…”

Section: Resultsmentioning

confidence: 99%

“…A solution of NaCN (556 mg, 11.3 mmol, 3 equiv) in water (2.0 mL) was added slowly to a solution of p -anisaldehyde (509 mg, 3.74 mmol, 1 equiv) and (4-methoxyphenyl)acetonitrile (557 mg, 3.78 mmol, 1 equiv) in MeOH (3.0 mL), and the mixture was refluxed for 16 h. After cooling to room temperature, the precipitate was filtered and washed with water and 75% MeOH (aqueous) to give a pale beige solid. Recrystallization from hot acetic acid gave meso - 30a as white needles (448 mg, 1.53 mmol, 42%): mp 234−235.5 °C (lit …”

Section: Methodsmentioning

confidence: 99%

“…Recrystallization from hot acetic acid gave meso-30a as white needles (448 mg, 1.53 mmol, 42%): mp 234-235.5 °C (lit. 28 mp 239-241 °C); 1 H NMR (500 MHz, CD2Cl2) δ 7.13 (AA′ of AA′XX′, JAX ) 8.8, JAA′ ) 2.6, 4H), 6.90 (XX′ of AA′XX′, JAX ) 8.8, JXX′ ) 2.6, 4H), 4.22 (s, 2H), 3.81 (s, 6H); MS (EI) m/z 292 (M + , 100), 265 (M -HCN, 88). Anal.…”

Section: 3-bis(4-hydroxyphenyl)-2-methylpropionitrile (27)mentioning

confidence: 99%

“…Recrystallization from benzene gave dl-30a as white crystals (dr > 20:1): mp 191.5-193 °C (lit. 28 (39). According to a procedure previously described, 33 octacarbonyldiobalt (125 mg, 0.366 mmol, 1 equiv) was added to a stirred solution of propargyl alcohol 38 (99.5 mg, 0.352 mmol, 1 equiv) in methylene chloride (2 mL) at room temperature.…”

Section: 3-bis(4-hydroxyphenyl)-2-methylpropionitrile (27)mentioning

confidence: 99%

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Estrogen Receptor-β Potency-Selective Ligands: Structure−Activity Relationship Studies of Diarylpropionitriles and Their Acetylene and Polar Analogues

et al. 2001

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Through an effort to develop novel ligands that have subtype selectivity for the estrogen receptors alpha (ERalpha) and beta (ERbeta), we have found that 2,3-bis(4-hydroxyphenyl)propionitrile (DPN) acts as an agonist on both ER subtypes, but has a 70-fold higher relative binding affinity and 170-fold higher relative potency in transcription assays with ERbeta than with ERalpha. To investigate the ERbeta affinity- and potency-selective character of this DPN further, we prepared a series of DPN analogues in which both the ligand core and the aromatic rings were modified by the repositioning of phenolic hydroxy groups and by the addition of alkyl substituents and nitrile groups. We also prepared other series of DPN analogues in which the nitrile functionality was replaced with acetylene groups or polar functions, to mimic the linear geometry or polarity of the nitrile, respectively. To varying degrees, all of the analogues show preferential binding affinity for ERbeta (i.e., they are ERbeta affinity-selective), and many, but not all of them, are also more potent in activating transcription through ERbeta than through ERalpha (i.e., they are ERbeta potency-selective). meso-2,3-Bis(4-hydroxyphenyl)succinonitrile and dl-2,3-bis(4-hydroxyphenyl)succinonitrile are among the highest ERbeta affinity-selective ligands, and they have an ERbeta potency selectivity that is equivalent to that of DPN. The acetylene analogues have higher binding affinities but somewhat lower selectivities than their nitrile counterparts. The polar analogues have lower affinities, and only the fluorinated polar analogues have substantial affinity selectivities. This study suggests that, in this series of ligands, the nitrile functionality is critical to ERbeta selectivity because it provides the optimal combination of linear geometry and polarity. Furthermore, the addition of a second nitrile group beta to the nitrile in DPN or the addition of a methyl substitutent at an ortho position on the beta-aromatic ring increases the affinity and selectivity of these compounds for ERbeta. These ERbeta-selective compounds may prove to be valuable tools in understanding the differences in structure and biological function of ERalpha and ERbeta.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: 3-bis(4-hydroxyphenyl)-2-methylpropionitrile (27)mentioning

confidence: 99%

Section: 3-bis(4-hydroxyphenyl)-2-methylpropionitrile (27)mentioning

confidence: 99%

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Estrogen Receptor-β Potency-Selective Ligands: Structure−Activity Relationship Studies of Diarylpropionitriles and Their Acetylene and Polar Analogues

et al. 2001

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“…0.004 mol dm Ϫ3 ) in hexane, recorded 20 min after mixing (Table 1, expt. 8) ‡ NC-PBN ؒ was prepared in an unambiguous way, namely by treatment of PBN by trimethylsilyl cyanide 12 to give NC-PBN(SiMe 3 ), followed by hydrolysis of the latter and oxidation of the hydroxylamine NC-PBN(H) by air. amine derivative formed.…”

mentioning

confidence: 99%