Reinvestigation of the metalation of phenylcyclopropane: does the phenylcyclopropyl anion undergo ring-opening? (original) (raw)
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Handbook of Inorganic Chemicals
Information contained in this work has been obtained by The McGraw-Hill Companies, Inc. ("McGraw-Hill") from sources believed to be reliable. However, neither McGraw-Hill nor its authors guarantee the accuracy or completeness of any information published herein and neither McGraw-Hill nor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information. This work is published with the understanding that McGraw-Hill and its authors are supplying information but are not attempting to render engineering or other professional services. If such services are required, the assistance of an appropriate professional should be sought.
Pyridine N -Oxide and 4-Nitrophenol (1:1 Complex)
Acta Crystallographica Section C Crystal Structure Communications, 1998
Refinement Refinement on F 2 R(F) = 0.034 wR(F 2) = 0.050 S = 0.950 4535 reflections 366 parameters H atoms constrained w = l/[o.2(Fo 2) + (0.0141P) 2] where P = (Fo 2 + 2F~2)/3 (z~/o.)max = --0.001 Apmax = 0.139 e ,rt -3 z~ffmin = -0.111 e ,~-3 Extinction correction: none Scattering factors from International Tables for Crystallography (Vol. C)
Chemistry of gem-Dihalocyclopropanes. III. 1 A New Synthesis of Indenes
The Journal of Organic Chemistry, 1966
A NEW SYNTHESIS OF INDENES 81 2,4dinitrophenylhydrazone, m.p. 120-122'. The residue was slurried with about 2% hydrochloric acid. The dark crude material was slurried in a solution of potassium bicarbonate and filtered. The solid was chromatographed over 175 g. of silica (0.05-0.2 mesh) using a mixture of 20% methanol, 20% acetone, and 60% Skellysolve B. The product (0.9 g.) decomposed upon attempted purification. IIb and Pyrrolidine.-A solution of 3.5 g. (0.017 mole) of IIb and 25 ml. of pyrrolidine was heated at 120' in a glass bomb for 14 hr. The solvent was blown into an acid solution of 2,4dinitrophenylhydrazine. No precipitate wm observed. The residue was twice chromatographed over 200 g. of silica (0.05-0.2 mesh) using a mixture of 10% methanol, 10% acetone, and 80% Skellysolve B. The product was refluxed with Nuchar 190-N in methanol and filtered. The filtrate was concentrated to dryness and the residue was extracted with Skellysolve B to yield 0.5 g. of unstable solid. The filtrate was concentrated t o a small volume and refrigerated to yield 1.2 g. of unchanged starting material. A.-A mixture of 1.5 g. (0.0079 mole) of IIa, 2.0 g. of sodium hydroxide, and 10 ml. of water was refluxed for 16 hr., and 75 ml. of boiling acetic acid was added. The mixture was filtered and the solution was taken to dryness. The residue was treated with 50 ml. of water and filtered. The solid (0.72 g.) was refluxed twice with Nuchar 190-N in ethanol and filtered. The filtrate was diluted with water, refrigerated 3 hr., and filtered to yield 300 mg. of a solid, m.p. 95-110". The solid was extracted with hot Skellysolve B, concentrated to a small volume, and refrigerated to yield 200 mg. (18%) of solid, m.p. 9496". When this was mixed with an authentic sample of 2,3dirnethylindoles (m.p. 104105") the melting point was 99-102'. The infrared and ultraviolet spectra were identical with the spectra of the authentic 2,3-dimethylindole. B.-A mixture of 1.0 g. (0.005 mole) of IIIa, 6.0 g. of sodium hydroxide, and 8.0 ml. of water was refluxed in a stainless steel flask for 20 hr. The sublimed solid (0.4 g., 55%) was collected from the receiver: m.p. 103-104.5". There was no depression on mixture with an authentic sample of 2,3-dmethylindole. l-Methyl-2,3-diphenyliudole (VIIId).-A mixture of 0.5 g. (0.0015 mole) of IId and 10 ml. of 50% sodium hydroxide was refluxed for 18 hr. The mixture was then refluxed 2.5 hr. with 2,3-Dimethylindole (WIa). (8) A. Arbusow and W. Tichwinsky, Ber., 48, 2301 (1910). 70 ml. of acetic acid. The mixture was cooled in an ice bath and filtered. After recrystabation from acetic acid, the solid weighed 300 mg. (71%), m.p. 137-138'. There was no depression on mixture with an authentic sample of l-methyl-2,3diphenylindole.9 The infrared and ultraviolet spectra were identical with the spectra of an authentic sample of l-methyl-2,3dphenylindole. 1,2,3,4-Tetrahydrocarbazole (VIXg).-A solution of 5.0 g. (0.023 mole) of IIg and 50 ml. of 50% sodium hydroxide was heated at 125" for 17 hr., 10 ml. of water was added, and the solution was heated at 145" for 4 hr. The cooled mixture was poured into 400 ml. of water and stirred, and 100 ml. of concentrated hydrochloric acid was added. The mixture was maintained at 90" approximately 1 hr., cooled, and filtered. The solid was dissolved in ethanol, refluxed with Nuchar 190-N, and filtered. The filtrate was diluted with water, cooled in an ice bath, and filtered. After three recrystallizations, the product weighed 0.9 g. (22%), m.p. 114-115'. There was no melting point depression on mixture with an authentic sample.' O 2,3-Cycloheptenindole (WIh).-A solution of 1.9 g. (0.083 mole) of IIh, 6.0 g. of sodium hydroxide, and 25 ml. of water was heated at 135" for 17 hr., cooled, and poured into 75 ml. of water. The mixture was stirred until a fine suspension resulted and filtered. The filtrate was treated with 20 ml. (0.2 mole) of concentrated hydrochloric acid. The mixture was held at 90' for 30 min., cooled, and filtered. The solid was dissolved in ethanol, refluxed with Nuchar 19O-N, and filtered. The filtrate was diluted to 80% with water and refrigerated to yield 0.8 g. of product (53%), m.p. 141-143'. This compound showed no melting point depression when mixed with an authentic sample.11
The Journal of Organic Chemistry, 1992
To a stirred and cooled (-100 OC) solution of 4 (40 mg, 0.32 mmol) in THF (4 mL) was added via cannula a cooled (-100 OC) LDA solution prepared from i-PrzNH (49 pL, 0.34 mmol) and BuLi (1.48 M in hexane, 0.22 mL, 0.33 mmol) in THF (1.5 mL). After 8 min, dry DMPU (77 pL, 0.64 "01) was introduced, and to the mixture was added a solution of 63 (63 mg, 0.107 "01) in THF (1.5 mL) over a 2-min period.
Easy Access to New Heterocyclic Systems: 1,4-Oxazine and Substituted 1,4-Oxazines
The Journal of Organic Chemistry, 2007
Contents-Experimental details and characterization data: pages S1-S18-1 H and 13 C NMR spectra for compounds 1-10: pages S19-S51 S2 Experimental details THF was distilled from sodium/benzophenone ketyl immediately prior use. Dichloromethane was distilled over CaH 2 and methanol from magnesium turnings. The reactions were monitored by thin-layer chromatography (TLC) analysis using silica gel (60 F 254) plates. Compounds were visualized by UV irradiation and/or spraying with a solution of potassium permanganate, followed by charring at 150 °C. Column chromatography was performed on silica gel 60 (230-400 mesh, 0.040-0.063 mm). Melting points (mp [°C]) were taken on samples in open capillary tubes and are uncorrected. The infrared spectra of compounds were recorded on an Infrared Fourier Transform spectrophotometer using NaCl plates or KBr pellets. 1 H and 13 C NMR spectra were recorded on a spectrometer at 250 MHz (13 C, 62.9 MHz). Chemical shifts are given in parts per million from tetramethylsilane (TMS) as internal standard. Ionspray or electronic impact methodology were used to record mass spectra. Nomenclature of the obtained compounds follows the rules of IUPAC and was checked with AutoNom. 1 Petroleum ether (P.E.) had a boiling point range 40-60 °C. 4-(tert-butoxycarbonyl)-morpholine-3,5-dione (2). A solution of 3,5dioxomorpholine 1 2 (0.510 g, 4.43 mmol), di-tert-butyl dicarbonate (1.451 g, 6.65 mmol) and DMAP (0.054 g, 0.04 mmol) in acetonitrile (13 mL) was stirred at room temperature, under argon, for 1 h. After concentration, the residue was diluted in EtOAc. The organic phase was washed with brine, dried over anhydrous MgSO 4 and concentrated. The residue was diluted in a minimun of AcOEt. The addition of petroleum ether results in the formation of a precipitate, which is filtered through a filter paper. After concentration of the filtrate, a flash chromatography (petroleum ether:EtOAc, 7:3) afforded 2
Formation and crystal structure of a novel azabishomotwistane
The Journal of Organic Chemistry, 1990
solved in 10 mL of a 1O:l DMSO/water solution in a 25-mL round-bottom flask equipped with a reflux condenser, and the solution is heated in an oil bath at 80 "C for 30 min. After cooling, the solution is diluted with water and extracted with diethyl ether. The organic layer is thoroughly washed with water to remove all traces of DMSO and dried. After careful concentration of a rotary evaporator, pure nitrocyclopropane is obtained.14 Cyclopropanes 10, 11,13, and 14 are nonvolatile and are easily separated by flash column chromatography (ether/hexane, 0 4 % ) .
Patnaik P. Handbook of inorganic chemicals (MGH, 2003)(T)(1125s)
Information contained in this work has been obtained by The McGraw-Hill Companies, Inc. ("McGraw-Hill") from sources believed to be reliable. However, neither McGraw-Hill nor its authors guarantee the accuracy or completeness of any information published herein and neither McGraw-Hill nor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information. This work is published with the understanding that McGraw-Hill and its authors are supplying information but are not attempting to render engineering or other professional services. If such services are required, the assistance of an appropriate professional should be sought.