- An improved synthesis of 4-aminobutanenitrile from 4-azidobutanenitrile and comments on room temperature stability
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4-Aminobutanenitrile (1) is an important synthetic intermediate for neurological disorder therapeutics including Parkinson’s and Alzheimer’s diseases, and is an industrial precursor to pyrroline and pyrrolidine. Synthesis of 1 by Co(II) catalyzed reduction of 4-azidobutanenitrile (2) with NaBH4, or by a one-pot Staudinger reduction of 2 in THF, was low yielding. 1H-NMR analysis of the Staudinger reduction revealed the formation of iminophosphorane intermediate (3) after 22 h at rt, and that increasing the reaction temperature from rt to 40 °C promoted hydrolysis of 3 to 1. A modified Staudinger reduction of 2 involving pyridine as solvent, addition of water 3 h after triphenylphosphine, and a temperature increase to 40 °C, gave rise to 1 in 69% yield. 1 is unstable at rt, thus the hydrochloride salt of 1 (1?HCl) was prepared by bubbling HCl(g) through a solution of 1 in chloroform. 1?HCl is stable at rt and is hence the preferred form for storage.
- Capon, Patrick K.,Avery, Thomas D.,Purdey, Malcolm S.,Abell, Andrew D.
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p. 428 - 436
(2020/12/25)
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- Preparation method N-substituted piperidine -3- ketone (by machine translation)
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The invention provides N -substituted piperi- 3 3-ketone preparation method, which uses acrylonitrile (II) and nitromethane as raw materials to obtain 4 -substituted-N-alkoxycarbonylmethyl- 4 4-aminobutyronitrile (III), to obtain 4 - substituent - N N-alkoxycarbonylmethyl( (IV),substituted-piperi- 3 3-one N - by addition reaction and decarboxylation to yield (V),substituted-piperidin-3-one according. to the present invention by two-time substituent reaction, reaction, and decarboxylation to obtain, a compound obtained from, N -substituted-piperidin-3-one of, the invention. (I). The method is simple, process and, times of reaction and decarboxylation. (by machine translation)
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Paragraph 0077-0080
(2020/03/25)
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- PYRIMIDINE COMPOUNDS CONTAINING ACIDIC GROUPS
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The present disclosure relates to a class of pyrimidine derivatives having immunomodulating properties that act via TLR7 which are useful in the treatment of viral infections and cancers.
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Paragraph 1178; 1180
(2018/06/15)
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- Photostimulated reduction of nitriles by SmI2
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Despite their high electron-withdrawing strength, nitriles are not good electron acceptors and therefore are hard to reduce. In this work, using photostimulation in the visible region, we examined the reactivity of aliphatic and aromatic, mono- and dicyano compounds in reaction with SmI2. A proton donor that complexes efficiently with SmI2 must be used. Maximum yield was obtained at ca.0.2 M MeOH. Aromatic nitriles were more reactive than aliphatic nitriles, which exhibited negligible yields. Phenylacetonitrile presents an intermediate reactivity. The mechanism of the reaction involves coordination of the SmI2 to the lone pair of the nitrile nitrogen followed by an inner sphere electron transfer. Surprisingly, m-dicyanobenzene was less reactive than the monocyano derivative benzonitrile. This was traced to the lower ability of the dicyano compound to coordinate to the SmI2 due to, as was shown by quantum mechanical calculations, its lone pair having an energy significantly lower than that of benzonitrile. It is noteworthy that at the SmI2 initial concentration used (0.04M), light penetrates only the 0.4 mm outer layer of the reaction mixture. Therefore the photostimulation effect observed was due to irradiation of only 4% of the total reaction volume, implying that under optimal conditions the effect should be 25 times larger.
- Rao, Chintada Nageswara,Hoz, Shmaryahu
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experimental part
p. 4029 - 4034
(2012/06/29)
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- Direct stereospecific amination of alkyl and aryl pinacol boronates
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The direct amination of alkyl and aryl pinacol boronates is accomplished with lithiated methoxyamine. This reaction directly provides aliphatic and aromatic amines, stereospecifically, and without preactivation of the boronate substrate.
- Mlynarski, Scott N.,Karns, Alexander S.,Morken, James P.
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supporting information
p. 16449 - 16451,3
(2020/09/15)
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- ANTIFUNGAL AGENTS
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Compounds and compositions useful as antifungals are provided, as are methods of use and preparation of such compounds and compositions containing such compounds. In some embodiments, the compounds are bifunctional, comprising two active moieties connected by a linking moiety. The compounds of the invention are useful for treating infections by microorganisms.
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Page/Page column 30
(2012/04/23)
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- Rigidified Compounds for Modulating Heparanase Activity
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Disclosed are novel rigidified compounds having a rhodanine-like residue and at least one aryl or heteroaryl residue linked to the rhodanine-like residue, whereby a core structure of these compounds, as defined in the specification, is characterized as having one or zero free-to-rotate bonds. Also disclosed are pharmaceutical compositions containing these rigidified compounds and uses thereof for modulating the activity of heparanase and hence in the treatment of heparanase-associated diseases and disorders, and uses thereof for modulating the activity of heparin-binding proteins and hence in the treatment of heparin-binding proteins-associated diseases and disorders as well as in the treatment of medical conditions that are at least partially treatable by rhodanine or a rhodanine analog.
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Page/Page column 55-56
(2010/11/30)
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- VIGABATRIN BIOISOTERES AND RELATED METHODS OF USE
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Compounds bioisoteric to vigabatrin and related methods of use.
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Page/Page column 8; 15
(2010/11/26)
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- New substrates and inhibitors of γ-aminobutyric acid aminotransferase containing bioisosteres of the carboxylic acid group: Design, synthesis, and biological activity
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A series of potential substrates of γ-aminobutyric acid aminotransferase (GABA-AT) with lipophilic bioisosteres of the carboxylic acid group (2-7) were synthesized and tested. Most of the synthesized compounds showed substrate activities with GABA-AT; 1H-tetrazole-5-propanamine (6) was the best of those tested. The potential time-dependent inhibitor of GABA-AT, 1H-tetrazole-5-(α-vinyl-propanamine) (8), was designed based on the structures of 6 and the antiepilepsy drug vigabatrin (4-aminohex-5-enoic acid, 1). The synthesized compound 8 showed time-dependent inhibition of GABA-AT, but its potency is lower than that of vigabatrin. Methylation of the tetrazole group in 8 resulted in loss of time-dependent activity, suggesting that the tetrazole ring, the carboxylate bioisostere, exists in its deprotonated form in the enzyme active site.
- Yuan, Hai,Silverman, Richard B.
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p. 1331 - 1338
(2007/10/03)
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- One-pot sequence for the decarboxylation of α-amino acids
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Treatment of an α-amino acid with N-bromosuccinimide in water at pH 5 or in an alcoholic-aqueous ammonium chloride mixture, followed by addition of nickel(II) chloride and sodium borohydride, effected an overall decarboxylation via an intermediate nitrile to afford the corresponding amine in good yield.
- Laval, Gilles,Golding, Bernard T.
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p. 542 - 546
(2007/10/03)
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- Nickel and nickel-magnesia catalysts active in the hydrogenation of 1,4-butanedinitrile
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Several NiO-MgO systems were synthesized to be studied as nickel catalysts for the hydrogenation of 1,4-butanedinitrile in the gas phase and compared with a bulk NiO of controlled morphology. All samples were characterized by XRD, BET, TPR, TPD, SEM, and H2 chemisorption techniques. The Ni-MgO systems had higher activities than the Ni bulk catalyst. The most active catalyst at all reaction temperatures was type R4CB which had homogeneous particles of about 1000 A, the highest metal surface area, and the highest coverage with weakly bound hydrogen. The presence of basic magnesia suppresses the condensation reactions and consequently favors the elimination of amines, and prevents catalyst deactivation. The selectivity toward the different products not only depends on the catalytic properties but can also be modified by controlling the hydrogen/dinitrile ratio. The highest selectivity to 4-aminobutanenitrile was achieved by catalyst R4CB, with 85% at 100% conversion and working at a space velocity of 13,000 h-1 and 343 K. This selectivity could be increased by lowering the hydrogen/butanedinitrile ratio.
- Serra, Marc,Salagre, Pilar,Cesteros, Yolanda,Medina, Francisco,Sueiras, Jesus E.
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p. 210 - 219
(2007/10/03)
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- Cobalt(II) chloride-catalyzed chemoselective sodium borohydride reduction of azides in water
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Reduction of azides to amines and amides was carried out with NaBH4/CoCl2·6H2O in sole water at 25 °C under catalytic heterogeneous conditions. A broad spectrum of azides was reduced in a short time, chemoselectively in high yield and purity.
- Fringuelli, Francesco,Pizzo, Ferdinando,Vaccaro, Luigi
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p. 646 - 650
(2007/10/03)
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- N-(arylsulphonyl)amino acid derivatives having bradykinin receptor affinity
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PCT No. PCT/FR97/00026 Sec. 371 Date Jul. 2, 1998 Sec. 102(e) Date Jul. 2, 1998 PCT Filed Jan. 7, 1997 PCT Pub. No. WO97/25315 PCT Pub. Date Jul. 17, 1997The invention relates to compounds of formula in which R1 to R9, R16 and R17 are defined in claim 1. These compounds are pharmacologically active.
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- Strategies towards functionalised electronically conducting organic copolymers: Part 2. Copolymerisation
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Here we discuss the application of X-ray photoelectron spectroscopy and absorbance-reflectance FT-IR spectroscopy to establish and quantify reactivity relationships between a range of thiophene and pyrrole monomers. In particular we investigate the application of these techniques to the characterisation of conducting polymer materials grown potentiostatically from solutions containing a binary mixture of monomers. Our data have shown that XPS is especially effective in determining polymer composition and the linear correlation between this and solution composition has enabled prescriptive synthesis of copolymer materials from the different combinations of monomers described here. This technique is much more convenient and more reliable than elemental analysis. In contrast we show that FT-IR studies, whilst providing a useful qualitative guide to the functional group content of the material, do not facilitate detailed quantitative analysis because of large intrinsic errors.
- Ryder,Schweiger,Glidle,Cooper
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p. 1785 - 1793
(2007/10/03)
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- COMPARATIVE KINETIC AND MECHANISTIC STUDIES OF Cu(II) AND Hg(II) CATALYZED OXIDATION OF ORNITHINE MONOHYDROCHLORIDE BY ALKALINE CHLORAMINE-T
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In a comparative kinetic study of Cu(II) and Hg(II) catalyzed chloroamine-T ornithine monohydrochloride redox reaction, a first order dependence each on chloramine-T and ornithine monohydrochloride and inverse first order dependence on alkali have been observed.Cu(II) and Hg(II) ions catalyze the reactions significantly and the rate of disappearance of chloramine-T showed a first order dependence on both and .In the presence of Cu(II) the oxidation takes place both by uncatalyzed and catalyzed paths, but in presence of Hg(II) the uncatalyzed oxidation path is completely abolished.
- Sengar, Satish K. S.,Yadav, B. S.
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p. 513 - 520
(2007/10/02)
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