JMC 1973, 16, 937-939.pdf

Chemical Communications, 2010

Journal of Organic Chemistry, 1989

t) ppm. (lE,3E)-l-Phenyl-4-(phenylthi0)-1,3,5-hexatriene (7k) was prepared on a 0.50-mmol scale from tram-cinnamaldehyde in 83% yield. The triene was found to be unstable and polymerized on standing at room temperature and was not fully characterized: Rf0.25 (1% ether/petroleum ether); 'H NMR (CDCl,, 300 MHz) 6 7. 18-7.46 (m, 11 H), 6.99 (dd, J = 16.5, 10.5 Hz, 1 H), 6.58-6.98 (m, 2 H), 7.75 (d, J = 16.5 Hz, 1 H), 5.33 (dt, J = 10.5, 1.5 Hz, 1 H) ppm; 13C NMR (CDCl,, 75 MHz) 6 136.87 (s), 136.48 (d), 135.50 (s), 135.16 (d), 132.72 (s), 130.53 (d), 129.70 (d), 128.90 (d), 128.65 (d), 128.09 (d), 126.67 (d), 126.34 (d), 123.30 (d), 118.99 (t) ppm.

Journal of the American Chemical Society, 1979

J Org Chem, 1985

Preparation of a+ Aspartyl-L-phenylalanine Methyl Ester Hydrochloride 9. L-Phenylalanine (7.4 g, 0.045 mol) was stirred in 90 mL of water. The pH of this solution was adjusted to 10.2 (0-2 'C) with 50% NaOH. Then a solution of pure NCA 7 (8.3 g, 0.048 mol) in 8 mL of THF was added in 15 min with vigorous stirring. The pH was maintained at 10.0-10.2 by the addition of 7 N NaOH solution. The reaction mixture was then stirred at 0-2 'C for 2 h (pH 10.0-10.2). One equivalent of 37% hydrochloric acid (9.7 g) was added at the end of the hold period. Liquid chromatography indicated an 80-82 % yield of aspartyl ester 8 based on L-phenylalanine. This clear solution was extracted twice with 50-mL portions of ethyl acetate. To the aqueous solution, 4.2 g of 37% HC1 (0.043 mol) was added. The solution was concentrated in vacuo to a total weight of 31.1 g. Another 8.4 g (0.085 mol) of 37% HC1 was added, and the reaction slurry was held at 40 'C for 6 h to convert 8 to a-L-aspartyl-Lphenylalanine hydrochloride 10. Solid (NaC1) was collected and washed with 2.6 g (0.026 mol) of 37% HCl and 7.5 g of methanol. Seed crystals were added to the combined filtrate and washings. The resulting solution was stirred at ambient temperature for 68 h. The thick slurry was cooled to 0-2 "C, and the solid was collected by filtration and washed with 7 mL of cold water. The dry weight of 9 was 9 g (55% yield' based on L-phenylalanine). This material was then neutralized with sodium hydroxide to give aspartame 1," [(YI2OD 30.3" (c 1.0, HOAc), authentic sample, [(YI2OD 30.1' (c 1.0, HOAc).

Inorganic Chemistry, 1997

The 1 H-NMR spectra of complexes involving the paramagnetic metal center [(NH 3 ) 5 Ru III ] coordinated at ring nitrogens have been examined with pyridine, purine, nucleoside, and nucleotide ligands along with 31 P-NMR of the nucleotide complexes and EPR of representative complexes. Variations in the spectra have been investigated as a function of the coordination site and pH. Pseudocontact and contact shifts have been calculated for various protons, and an attempt has been made to correlate sugar conformations in coordinated 5′GMP, 5′IMP, Guo, and Ino with paramagnetically induced shifts. The compound [(7MeGuaκ N9 )(NH 3 ) 5 Ru]Cl 3 ‚3H 2 O crystallizes in the orthorhombic space group Pna2 1 with cell parameters a ) 25.375(4) Å, b ) 11.803(4) Å, c ) 6.958 Å, Z ) 4, and R ) 0.042. The autoxidation of [L(NH 3 ) 5 Ru III ], where L ) Guo, dGuo, and 1MeGuo, to the corresponding 8-oxo complexes under atmospheric oxygen is first order in the complex and [OH -]. For L ) Guo, k ) 6.6 × 10 -5 M -1 s -1 , ∆H* ) 58 kJ/mol, and ∆S* ) -124 J/(mol K). (5) Schachner, E. R.; Gil, M. C.; Som, P.; Oster, Z. H.; Atkins, H. L.; Subramanian, G.; Badia, J.; Srivastava, S. C.; Richards, P.; Treves, S. J. Nucl. Med. 1981, 22, 352. (6) Schachner, E. R.; Gil, M. C.; Som, P.; Oster, Z. H.; Atkins, H. L.; Subramanian, G.; Badia, J.; Srivastava, S. C.; Richards, P.; Treves, S. Nucl. Med. Commun. 1983, 4, 94. (7) Gariepy, K. C.; Curtin, M. A.; Clarke, M. J. J. Am. Chem. Soc. 1989, 111, 4947-52. (8) Clarke, M. J.; Jansen, B.; Marx, K. A.; Kruger, R. Inorg. Chim. Acta 1986, 124, 13-28. (9) Rubin, J. R.; Sabat, M.; Sundarlingam, M. Nucl. Acid Res. 1983, 11, 6571. (10) LaChance-Galang, K. J.; Doan, P. E.; Clarke, M. J.; Rao, U.; Yamano, A.; Hoffman, B. J. Am. Chem. Soc. 1995, 117, 3529-3538. (11) Clarke, M.; Bailey, V. M.; Doan, P.; Hiller, C.; LaChance-Galang, K. J.; Daghlian, H.; Mandal, S.; Bastos, C.; Lang, D. Inorg. Chem. 1996, 35, 4896-4903. (12) Bastos, C. M.; OCain, T. D.; Gordon, K. A.; Sampo, T. M.; Clarke, M. J.; Daghlian, H. In

Journal of the American Chemical Society, 1992

the dry nitrogen atmosphere of a glovebox. Reactions involving NF,' salts were carried out in 3/4 in. 0.d. Teflon-FEP ampules closed by a stainless steel valve. The I9F and ' H NMR spectra were measured at 84.6 and 90 MHz, respectively, on a Varian Model EM390 spectrometer, with 4-mm Teflon-FEP tubes (Wilmad Glass Co.) as sample containers and CFCI, and TMS, respectively, as internal standards, with negative shifts being upfield from the standards. Raman spectra were recorded on either a Cary Model 83 or a Spex Model 1403 spectrophotometer by use of the 488-nm exciting line of an Ar ion or the 647.1-nm line of a Kr ion laser, respectively. Baked-out Pyrex melting point capillaries were used as sample holders. Infrared spectra were recorded on a Perkin-Elmer Model 283 spectrophotometer as AgCl disks that were pressed in a Wilks minipress inside the drybox. The NF,BF,-N(CH,),F-CH,CN System. NF4BF4 (0.54 mmol) and N(CH,)4F (0.60 mmol) were loaded inside the drybox into a '/, in. Teflon-FEP ampule. On the vacuum line, dry CH,CN (3 mL liquid) was added at-196 "C, and the mixture was warmed to-31 "C for 30 min. The ampule was cooled to-78 "C, and the volatile material (0.45 mmol) was expanded into the vacuum line and shown by fractional condensation at-210 "C and infrared spectroscopy to consist mainly of NF, (0.40 mmol). The mixture in the ampule was then warmed for 3 h to-31 "C and for 1 h to room temperature, and an additional amount of NF, (0.13 mmol) was evolved. The solid residue (90.9 mg, weight calculated for 0.54 mmol of N(CH,),BF, and 0.06 mmol of unreacted N(CH,),F = 92.9 mg) was shown by vibrational spectroscopy to consist mainly of N(CH3),BF4. When the reaction was repeated using a 5-fold excess of N(CH,),F at-31 OC, the NF, evolution was 95% complete after 30 min. The NF4BF4-N(CH3),F-CHF3 System. NF4BF4 (2.19 mmol) and N(CH,),F (2.24 mmol) were combined in a Teflon ampule, and CHF, (50.26 mmol) was added at-196 OC. The mixture was warmed to-78 OC for 3 h and then cooled again to-196 "C, and the noncondensable gases (0.45 mmol of F2) were measured. Subsequently, the ampule was warmed to the melting point of CHF, (-155 "C), and the volatile material was removed in a dynamic vacuum by fractional condensation through traps kept at-186 and-210 "C. The-210 "C trap contained NF, (2.16 mmol). The solid residue, after being pumped on at room temperature (360 mg), consisted mainly of N(CH,)4BF4 (weight calculated for 2.19 mmol of N(CH,),BF, and 0.05 mmol N(CH,),F = 357 mg). When the reaction was repeated at-142 "C, only 10% of the theoretical amount of NF, was evolved in 3 h.

Arkivoc, 2011

The versatile, hitherto unreported 2-cyano-3-(dimethylamino)-N-(4-phenylthiazol-2-yl)acrylamide 2 was synthesized and allowed to react with hydroxylamine, hydrazine and guanidine to afford regioselectively the isoxazole 4, pyrazole 6 and pyrimidine 8 derivatives, respectively. The reaction of 2 with thiourea and / or ethyl glycinate in a basic medium afforded the regioisomeric pyrimidinethione 9 and 3,5-dioxo-1,4-diazepine-6-carbonitrile 14. Compound 2 reacts also with 2-amino-4-phenylthiazole, 2-amino-4-methylpyridine, 2-aminotetrazole, 2-aminobenzothiazole and 2-aminobenzimidazole to give the corresponding bridgehead nitrogen heterocycles namely thiazolo[3,2-a]pyrimidine 18, tetrazolo[1,5-a]pyrimidine 19, pyrimido [2,1-b]benzothiazole 21, and pyrido[1,2-a]benzimidazole 23. The mechanistic aspects for the formation of the newly synthesized compounds is discussed.

The 1 H-NMR spectra of complexes involving the paramagnetic metal center [(NH 3 ) 5 Ru III ] coordinated at ring nitrogens have been examined with pyridine, purine, nucleoside, and nucleotide ligands along with 31 P-NMR of the nucleotide complexes and EPR of representative complexes. Variations in the spectra have been investigated as a function of the coordination site and pH. Pseudocontact and contact shifts have been calculated for various protons, and an attempt has been made to correlate sugar conformations in coordinated 5′GMP, 5′IMP, Guo, and Ino with paramagnetically induced shifts. The compound [(7MeGuaκ N9 )(NH 3 ) 5 Ru]Cl 3 ‚3H 2 O crystallizes in the orthorhombic space group Pna2 1 with cell parameters a ) 25.375(4) Å, b ) 11.803(4) Å, c ) 6.958 Å, Z ) 4, and R ) 0.042. The autoxidation of [L(NH 3 ) 5 Ru III ], where L ) Guo, dGuo, and 1MeGuo, to the corresponding 8-oxo complexes under atmospheric oxygen is first order in the complex and [OH -]. For L ) Guo, k ) 6.6 × 10 -5 M -1 s -1 , ∆H* ) 58 kJ/mol, and ∆S* ) -124 J/(mol K). (5) Schachner, E. R.; Gil, M. C.; Som, P.; Oster, Z. H.; Atkins, H. L.; Subramanian, G.; Badia, J.; Srivastava, S. C.; Richards, P.; Treves, S. J. Nucl. Med. 1981, 22, 352. (6) Schachner, E. R.; Gil, M. C.; Som, P.; Oster, Z. H.; Atkins, H. L.; Subramanian, G.; Badia, J.; Srivastava, S. C.; Richards, P.; Treves, S. Nucl. Med. Commun. 1983, 4, 94. (7) Gariepy, K. C.; Curtin, M. A.; Clarke, M. J. J. Am. Chem. Soc. 1989, 111, 4947-52. (8) Clarke, M. J.; Jansen, B.; Marx, K. A.; Kruger, R. Inorg. Chim. Acta 1986, 124, 13-28. (9) Rubin, J. R.; Sabat, M.; Sundarlingam, M. Nucl. Acid Res. 1983, 11, 6571. (10) LaChance-Galang, K. J.; Doan, P. E.; Clarke, M. J.; Rao, U.; Yamano, A.; Hoffman, B. J. Am. Chem. Soc. 1995, 117, 3529-3538. (11) Clarke, M.; Bailey, V. M.; Doan, P.; Hiller, C.; LaChance-Galang, K. J.; Daghlian, H.; Mandal, S.; Bastos, C.; Lang, D. Inorg. Chem. 1996, 35, 4896-4903. (12) Bastos, C. M.; OCain, T. D.; Gordon, K. A.; Sampo, T. M.; Clarke, M. J.; Daghlian, H. In

J Am Chem Soc, 1986

cis-9,10-Diethyl-9,1O-dihydroanthracene (cis-6) was prepared by reductive alkylation of anthra~ene.'~ trans -9,lO-Diethyl-9,10-dihydroanthracene (trans-6) was prepared by Li/NH, reduction of 9.1 0-diethylanthracene.'* 9,10-Ethano-9,10-dihydroanthracene (7) was prepared from dibenzobarrelene by Li/NH, reduction.20 Benzanthrene (8) was prepared from commercial benzanthrone by reduction with a fourfold excess of LiAIH4/AIC13.21 Ethylbenzanthrene (Sa) was prepared from 8 (0.55 g, 2.5 mmol) by proton abstraction with n-butyllithium (3.1 mmol) in THF at -78 OC followed by the addition of excess bromoethane. Ether extraction yielded Sa as a yellow oil which was microdistilled for analysis. NMR (CCI,) 6 0.5 (t, 3 H), 1.7 (quintet, 2), 4.1 (t. I), 7.5 (m, IO). Fieser, M. Reagents for Organic Synthesis; Wiley: cis-9-Ethyl-10-tert-butyl-9,lO-dihydroanthracene (9) was prepared by epimerization of 1,9-Ethano-9,10-dihydroanthracene (1 1) was prepared from ace-anthrene2, (230 mg, 1 mmol) and sodium (60 mg, 2.5 mmol) according to the general procedure for metal-ammonia reduction. After normal quenching with dilute ammonium chloride solution and ether extraction, the solid product was recrystallized from methanol/water to yield 1,9ethano-9,IO-dihydroanthracene as white crystals: mp 81-82 OC (60 mg, 0.3 mmol, 33%); NMR (CDCI,) 6 2.0 (m, 1 H), 2.9 and 3.1 (m, 3). 3.8 . (23) Aceanthrene was prepared starting from aceanthrenequinone according to the synthesis reported by Becker et al. (Becker, H. D.; Hansen, L.; Nadersson, K. J. Org. Chem. 1985, 50, 277) with one exception. 2-Aceanthrone was prepared with pyridine hydrochloride reagent as described by Plummer et al. (Plummer, B. F.; AI-Saigh, 2. Y.; Arfan, M. J . Org Chem. 1984, 49, 2069). Melting points of intermediate compounds were identical with those reported by Becker et al. The Complexation of Sodium Ion by the Cryptand 4,7,13-Trioxa-1 , 10-diazabicyclo[ 8.5.5leicosane (C2 l C5) in a Range of Solvents.

Canadian Journal of Chemistry, 1981