Homoallylic coupling in 1,4-dihydronaphthalenes. 3. Crystal structure of 1,4-dihydronaphthoic acid

Abstract

mL, 103 mmol) was added at 0 °C to a stirred solution of the sulfone 4 (17.7 g, 50 mmol) in dry THF (100 mL) under argon. After 30 min, HMPTA (5 mL) and -butyrolactone (4.3 g, 50 mmol) were added at -78 °C. The reaction mixture was stirred for 3 h and then allowed to reach room temperature and quenched with aqueous NH4C1. The organic phase was extracted with ethyl acetate, washed with brine, dried over Na2S04, and evaporated in vacuo. The crude residue was chromatographed on a silica gel column, eluting with hexane-ethyl acetate (70:30), to separate the unreacted sulfone 4 (3.56 g, 20%) and then the sulfone 5 (12.1 g, 28.3 mmol, 55%): IR (neat) 3400 (m), 1720 (s), 1310 (s), 1070 (s), 1030 cm'* 1

Conformation of 1-phenyl-1,4-dihydronaphthalene

“…II the conformational resemblance of 1 and 2 is evident. In comparison with 5Jcis (pa-pa) of 5 (8.5 Hz) and 5«/cia (pe-pe) of 4 (1.8 Hz), 5s/cis values of both 1 and 2 have an intermediate value.…”

“…Very recently an X-ray analysis of 1,4-dihydronaphthoic acid (2) has been reported. 4 The cyclohexadiene part of this molecule was found to adopt a boat structure with the folding angle a = 169.2°and the carboxylic group occupying a pseudoaxial position. This structure corresponds to the "flattened boat" structure proposed by Marshall5 and the "somewhat puckered but not truly boat-shaped" structure proposed by Rabideau6 for this compound.…”

“…Received January 4,1984 The molecular geometry of 1,4-dihydronaphthalenes has been the subject of several investigations employing NMR spectroscopy1 and force-field calculations. 2'5 In most studies based on the interpretation of NMR spectra some ambiguity remains due to the uncertainty of the correlation between the homoallylic coupling constants (Vi^tram) and 5e/ii4(cis) and the folding angle a as defined in formula A.…”

Chemistry of naturally occurring polyamines. 9. Synthesis of spermidine and spermine photoaffinity labeling reagents

“…The oily residue was taken up in water, washed with CH2C12 (10 mL), and lyophilized. Chromatography of the crude product (Si02, 2:2:1 CH2Cl2-CH3OH-NH4OH) gave the desired 2 (0.11 g, 75%) as an oil: NMR (CD3OD) 5 Attempted purification of 2 using CH2Cl2-CH3OH-NH4OH in 6:3:1 proportion instead of 2:2:1 proportion resulted in extensive decomposition during concentration of the chromatography fractions.…”