Magnetic Properties of Microcrystalline Poly(Phenyl- Diacetylenes) Carrying Radical or Carbene Centers on the Side Chain
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MAGNETIC PROPERTIES OF MICROCRYSTALLINE "POLY(PHENYLDIACETYLENES)" CARRYING RADICAL OR CARBENE CENTERS ON THE SIDE CHAINS. NOBORU KOGA, KATSUYA INOUE, NORIKO SASAGAWA, AND HIIZU IWAMURA Department of Chemistry, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113, Japan ABSTRACT 1-Phenyl-l,3-butadiyne derivatives (3 and 4) carrying stable t-butylnitroxide and diazomethyl groups, respectively, have been prepared. Mixed crystals of 3 and the corresponding hydroxylamine 2 ( 3u I) were obtained and used in the structure analysis. The final R and Rw values were 0.081 and 0.102, respectively. ESR spectra were obtaine on a Bruker ESP 300 X-band (9.41 GHz) spectrometer attached with an Air Products Helitran LTR-3110 cryostat. The magnetization and magnetic susceptibility data were obtained on an Oxford Instruments magnetic susceptibility system with a 7 T superconducting magnet. Differential scanning calorimetry was carried out on a Rigaku DPS-8151 Ver. 2.10 Thermal Analysis System. Materials 1-(3-(N-tert-butyl)hydroxylamino-4-chlorophenyl}-l,3butadiyne (2). A mixture of 100 mg (0.26 mmol) of the protected hydroxylamine and 10 mg of pyridinium p-toluenesulfonate in 50 ml of ethanol was heated at 55 'C for 3 hr. The reaction mixture was cooled, poured into 200 ml of water, and extracted with ether. The organic layer was dried over magnesium sulfate and concentrated in vacuo. To the benzene solution (50 ml) of the residue was added 10 mg of sodium hydride. The mixture was heated under reflux for 1 hr, cooled, filtered and the filtrate was evaporated at room temperature to yield pale yellow solids. Recrystallization from ether-hexane (1:1) gave 55 mg (86 %) of colorless triclinic crystals: mp 140 °C; 1-H NMR (270 MHz, CDC13) 3 1.20 (9H, s), 2.50 (1H, s), 5.36 (1H, brs), 7.23 (2H, dd, J=8.2, 1.9 Hz), 7.29 (2H, d, J=8.2 Hz), 7.76 (1H, d, J=l.9 Hz). Anal. Found: C, 67.66; H, 5.86; N, 5.65; Cl, 14.18 %. Calcd for C1 4 H1 4 NCIO: C, 67.88; H, 5.70; N, 5.65; Cl, 14.31 %. 1-(3-(N-tert-butylnitroxyl)-4-chlorophenyl}-l,3-butadlyne (3). A 5 ml aqueous solution of 500 mg of Fremy's salt was added dropwise to a mixture of 2 g of potassium dihydrogenphos-
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phate, 0.1 g of potassium hydroxide, 100 mg (0.40 mmol) of 2 in water-THF (3:1). The reaction mixture was stirred at room temperature for 3 hr and then extracted with ether. The organic layer was washed with cold water, dried over magnesium sulfate, and concentrated under reduced pressure at room temperature to yield red oil. The crude product was crystallized from npentane-ether (10:1) to give 75 mg (76 %) of red crystals: mp 81 - 82 °C; ESR(X-band) g = 2.0066, a(N) = 13.78 G. Anal. Found: C, 68.31; H, 5.48; N, 5.71; Cl, 14.36 %. Calcd for C1 4 H1 3 NCI0: C, 68.16; H, 5.31; N, 5.68; Cl, 14.37 %. 1-(p-Formylphenyl)-l,3-butadiyne tosylhydrazone. Calcd for C1 8 H1 3 N20 2 S: C, 67.06; H, 4.38; N, 8.69; S, Found: C, 66.82; H, 4.46; N, 8.58; S, 9.85 %.
Anal. 9.93.
1-{p-(Diazomethyl)phenyl}-l,3-butadlyne (4). A mixture of 37.8 mg of sodium methoxide and 220 mg of the tosylhydraz
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