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1.
Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co+2FeII) and ferricyanides (Co+2FeIII) in an ozone flow. The CN stretching bands occur at 2085 cm–1 for Co+2FeII and at 2160 cm–1 for Co+2FeIII. After the ozonization process of Co+2FeII, an intense band approximately at 2125 cm–1 is detected. This intermediate band must correspond to a mixed valence state of the type: FeII–CN–Co2+–NC–FeIII Mössbauer spectra recorded in situ during the ozonization of Co+2FeII show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co+2FeII after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable. 相似文献
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3.
The 1-ferrocenyl-2-methyl-1-propylamine (2a)is the most effective chiral template in asymmetrically induced peptide synthesis by stereoselective four component condensation (4CC). Two routes for the synthesis of this amine via its N,N-dimethyl derivative (12a) an described. One route involves the conversion of 12a into the corresponding azide 14a by treatment with methyl iodide/sodium azide in diglyme/water and subsequent reduction of the azide. The preferred other route consists of treating 12a with thioglycolic acid/formic acid to yield the carboxymethylmercapto derivative 9a and transformation of the latter into 2a with aqueous ammonia/ammonium chloride/mercuric chloride. Some related reactions are also discussed. 相似文献
4.
The primary amino group of 3-(2-aminoethyl)-3-(4-chlorophenyl)-2,3-dihydro-1H-isoindol-1-one ( 1 ) was acylated with acetyl chloride, benzoyl chloride and phenyl acetyl chloride to form the amides 2a -c, respectively. These were cyclized in phosphorus oxychloride to give the 1-substituted-4a-(4-chlorophenyl)-4,4a-dihydropyrimido [6,1-a]isoindol-9(3H)-ones 3a-c . Heating of 1 in formic acid lead to the formation of 4a-(4-chlorophenyl)-4,4a-dihydropyrimido[6,1-a]isoindol-9(3H) -one (3d) . Heating of 1 in the presence of phosgene lead to the formation of 4a-(4-chlorophenyl)-2,3,4,4a-tetrahydropyrimido[6,1-a]isoindole-1, 9-dione (4). 相似文献
5.
van den Brand JF Ent R Anthony PL Arnold RG Arrington J Beise EJ Belz JE Bosted PE Bulten H Chapman MS Coulter KP Dietrich FS Epstein M Filippone BW Gao H Gearhart RA Geesaman DF Hansen J Holt RJ Jackson HE Jones CE Keppel CE Kinney ER Kuhn S Lee K Lorenzon W Lung A Makins NC Margaziotis DJ McKeown RD Milner RG Mueller B Napolitano J Nelson J O'Neill TG Papavassiliou V Petratos GG Potterveld DH Rock SE Spengos M Szalata ZM Tao LH van Bibber K Wasson DA White JL Zeidman B 《Physical review D: Particles and fields》1995,52(9):4868-4871
6.
Makins NC Ent R Chapman MS Hansen J Lee K Milner RG Nelson J Arnold RG Bosted PE Keppel CE Lung A Rock SE Spengos M Szalata ZM Tao LH White JL Coulter KP Geesaman DF Holt RJ Jackson HE Papavassiliou V Potterveld DH Zeidman B Arrington J Beise EJ Belz E Filippone BW Gao H Lorenzon W Mueller B McKeown RD O'Neill TG Epstein M Margaziotis DJ Napolitano J Kinney E Anthony PL van Bibber K Dietrich FS Gearhart RA Patratos GG Kuhn SE van den Brand JF Bulten H Jones CE 《Physical review letters》1994,72(13):1986-1989
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8.
The purpose of this investigation was to elucidate the biological significance of the tripeptide sequence 11–13, -Lys-Pro-Val · NH2 contained in α-melanocyte-stimulating hormone. To this end the in vitro melanotropic activities of 21 synthetic peptides related to the hormone were determined and compared with one-another and with results reported in the literature. The tripeptide amide, H · Lys-Pro-Val · NH2, its Nα-acetylderivative, and -weakly, but distinctly-Nα-acetyl-L-lysine-amide were found to be hormonally active. The following conclusions were drawn: (1) α-melanophore-stimulating hormone possesses two message sequences (active sites), -Met-Glu-His-Phe-Arg-Trp-Gly-, and -Lys-Pro-Val · NH2 which are capable of independently triggering the hormone receptor responsible for melanin dispersion. (2) In correct covalent combination, the two message sequences act in a ‘cooperative’ manner to potentiate their activities on the receptors. (3) -Lys-Pro-Val- is an address sequence in adrenocorticotropic hormone and a message sequence in α-melanocyte-stimulating hormone. This implies that the two receptors (adrenal and melanocyte), albeit recognizing -Met-Glu-His-Phe-Arg-Trp-Gly- as stimulus, differ fundamentally in their response to -Lys-Pro-Val-. 相似文献
9.
Cong Zhang Christian Ludin Marcel K. Eberle Helen Stoeckli-Evans Reinhart Keese 《Helvetica chimica acta》1998,81(1):174-181
(S)-5,5,5,5′,5′,5′-Hexafluoroleucine ((S)- 13 ) of 81 % ee is prepared from hexafluoroacetone ( l ) and ethyl bromopyruvate (= ethyl 2-oxopropanoate) in 7 steps with an overall yield of 18% (Schemes 1 and 2). Key step in this sequence is the highly enantioselective reduction of the carbonyl group in α-keto ester 4 either by bakers' yeast (91 % ee) or by ‘catecholborane’ 6 utilizing an oxazaborolidine catalyst, yielding hydroxy ester (R)- 5 with 99% ee. The absolute configuration was determined by X-ray analysis of the HCl adduct (S,R)- 9b of (2S)-N-[(R)- l-phenylethyl]-5,5,5,5′,5′,5′-hexafluoroleucine ethyl ester. 相似文献
10.
Synthesis of [D -alanine1, 4′-azido-3′, 5′-ditritio-L -phenylalanine2, norvaline4]α-melanotropin as a ‘photoaffinity probe’ for hormone-receptor interactions. The synthesis of an α-MSH derivative containing 4′-azido-3′,5′-ditritio-L -phenylalanine is described: Ac · D -Ala-Pap(3H2)-Ser-Nva-Glu-His-Phe-Arg-Trp-Gly-Lys-Pro-Val · NH2. This hormone analogue is being used for specific photoaffinity labelling of receptor molecules. The synthesis was performed in a way to minimize the number of radioactive steps and to introduce the radio-active and the photoaffinity label exclusively into position 2. The dipeptide N(α)-acetyl-D -alanyl- (4′-amino-3′,5′-diiodo)-L -phenylalanine was tritriated and transformed into the azido compound, N(α)-acetyl-D -alanyl-(4′-azido-3′,5′-ditritio)-L -phenylalanine which was then condensed with H · Ser-Nva-Glu(OtBu)-His-Phe-Arg-Trp-Gly-Lys(BOC)-Pro-Val · NH2 to the tridecapeptide. The α-MSH analog displayed a specific activity of 11 Ci/mmol, and a biological activity of about 4 · 109 U/mmol (10% of α-MSH). 相似文献