- Skipped cyclic ene- and dienediynes. 1. Synthesis, spectroscopic properties, and reactions of a new hydrocarbon ring family
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The three skipped cyclic C12H12 dienediynes, 4,9-dimethylene-1,6-cyclodecadiyne (1), (Z,Z)-4,10-cyclododecadiene-1,7-diyne (2), and 10-methylene-(Z)-4-cycloundecene-1,7-diyne (3), have been synthesized by cyclization of dilithium salts of diterminal enediynes with the corresponding dihalogenides. This simple approach only worked (with approx. 5% yield) when no CuCl catalyst was used. Besides 1-3, 4,9-diisopropylidene-1,6-cyclodecadiyne (30), the cyclic enediynes (Z)-4-cycloundecene-1,7-diyne (19) and (Z)-4-cyclododecene-1,7-diyne (20), as well as 4-methylene-1,6-cyclodecadiyne (22), 4-methylene-1,6-cycloundecadiyne (23), and their isopropylidene congeners 25 and 28 have been synthesized. Partial hydrogenation of 1-3 gives the corresponding homoconjugated tetraenes 37-39. The reaction of 30 with dicarbonyl(η5-cyclopentadienyl)cobalt yields a superphane of two cyclobutadiene units, stabilized by two CpCo moieties (47). The two cyclobutadiene rings are connected by four 2-isopropylidenepropano bridges. An X-ray investigation of the superphane shows that all four bridges adopt a pinwheel-like conformation.
- Gleiter, Rolf,Merger, Roland,Nuber, Bernhard
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- PREPARATION OF AMINO ACIDS AND AMINO ACID DERIVATIVES
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The invention relates to a method for synthesizing amino acids or amino acid derivatives involving cross metathesis of functionalized olefins and a tandem amination-reduction process. Amino acids and amino acid derivatives present many interesting physical and chemical properties finding many uses in the automotive, fuel, electronic, and textile industries.
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Paragraph 0220
(2018/04/20)
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- PYRAZOLE DERIVATIVES AND USES THEREOF AS INHIBITORS OF DLK
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The present invention provides for compounds of formula 0 and various embodiments thereof, and compositions comprising compounds of formula 0 and various embodiments thereof. In compounds of formula 0, the groups R1A, R1B, R1C, R1D, R2, R3, R4, R5 and R6 have the meaning as described herein. The present invention also provides for methods of using compounds of formula 0 and compositions comprising compounds of formula 0 as DLK inhibitors and for treating neurodegeneration diseases and disorders.
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Page/Page column 119
(2015/07/07)
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- SUBSTITUTED PYRAZOLES AND USES THEREOF
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The present invention provides for compounds of formula 0 and various embodiments thereof, and compositions comprising compounds of formula 0 and various embodiments thereof. In compounds of formula 0, the groups R1A, R1B, R1C, R1D, R2, R3, R4, R5 and R6 have the meaning as described herein. The present invention also provides for methods of using compounds of formula 0 and compositions comprising compounds of formula 0 as DLK inhibitors and for treating neurodegeneration diseases and disorders.
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Paragraph 0392; 0393
(2015/07/02)
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- Practical synthetic process for enantiopure 1-benzyl-3-hydroxypyrrolidine
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The synthesis of (S)-1-benzyl-3-hydroxypyrrolidine (S)-5 comprised the asymmetric hydroboration of 1-benzyl-3-pyrroline 4, followed by oxidation and chiral purification via diastereomeric salt formation. The asymmetric borane reagent was generated 'in situ' from NaBH4, BF3-OEt2, and (+)-α-pinene 1 (85% ee) and reacted with 4, prepared from cis-1,4-butenediol 3, to give crude product (S)-5. The following chiral purification via diastereomeric salt formation proceeded to afford (S)-5 with >99% ee. The optimized process was successfully scaled up to an industrial scale to produce a 252 kg batch of (S)-5.
- Morimoto, Masao,Sakai, Kenichi
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p. 1464 - 1468
(2008/12/20)
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- Catalytic conversions of chloroolefines over iron oxide nanoparticles 3. Electronic and magnetic properties of γ-Fe2O3 nanoparticles immobilized on different silicas
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Catalytic properties of superparamagnetic γ-ferric oxide nanoclusters, which are uniform in terms of size and magnetic properties were studied. The catalysts were supported on the activated silica gel matrix (AGM) prepared from the KSK-2 silica gel of globular structure and on the activated silica matrix (ASM) prepared from layered natural vermiculite. The clusters are active in some reactions of chloroolefin conversions: isomerization of dichlorobutenes and alkylation of benzene with allyl chloride. Their activity in these reactions is many times higher that of usual supported catalysts based on α-ferric oxide. Analysis of the Moessbauer spectra of the 2.5 wt.% Fe/AGM and 2.5 wt.%Fe/ASM samples before and after the reaction at T = 3-300 K shows that during the reaction some FeIII ions arranged in ～2-3-nm γ-Fe2O3 nanoclusters magnetically ordered at 6 K are reduced to form a high-spin FeII complex in the paramagnetic state. According to the macroscopic magnetization data (SQUID) of the initial clusters, curves with hysteresis are observed at 2 K in the plots of forward and backward magnetization, while the 2.5 wt.%Fe/ASM catalyst after the reaction at T = 2 K demonstrates a linear field dependence of the magnetization passing through the coordinate origin. Analysis of the Moessbauer spectra and magnetic properties suggests that during the catalytic reaction the Fe III ions in the γ-Fe2O3 nanoclusters interact with chloroolefin with the allylic structure to be partially reduced to the FeII ions that are bound in a complex containing chloride ions and OII ion(s) of the silicate matrix as ligands. This is a reason, probably, for the high catalytic activity of γ-Fe2O3 nanoparticles.
- Rostovshchikova,Kiseleva,Smirnov,Maksimov,Suzdalev,Prusakov,Tsodikov,Ikorskii
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p. 1768 - 1774
(2008/02/05)
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- Thionyl chloride-benzotriazole in methylene chloride: A convenient solution for conversion of alcohols and carboxylic acids expeditiously into alkyl chlorides and acid chlorides by simple titration
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A solution of 1:1 equivalent of thionyl chloride and benzotriazole in dry methylene chloride efficiently transforms alcohols and carboxylic acids into the corresponding alkyl chlorides and acid chlorides respectively at room temperature, with excellent yields by simple titration.
- Chaudhari, Sachin S.,Akamanchi, Krishnacharya G.
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p. 1763 - 1765
(2007/10/03)
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- Gas-sensitive and catalytic properties of ensembles of interacting palladium nanoparticles
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The electrophysical and catalytic properties of poly(p-xylylene) materials containing palladium nanoparticles are studied. It is shown that an ensemble of interacting nanoparticles is formed, whose conductivity exhibits a high sensitivity to gas adsorption. This structure also shows unusual catalytic properties.
- Vorontsov,Gerasimov,Golubeva,Grigor'ev,Zav'yalov,Zav'yalova,Trakhtenberg
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p. 1742 - 1744
(2007/10/03)
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- Synthesis of 2-Substituted Buta-1,3-dienes from 1,4-Dichlorobut-2-yne via Organoboranes
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The reaction of 1,4-dichlorobut-2-yne 1 with a stoichiometric amount of di-sec-alkylborane 2, prepared by the hydroboration of a sterically hindered anternal alkene with BH3 in tetrahydrofuran (THF), gave (Z)-(1,4-dichlorobut-2-en-2-yl)di-sec-alkylborane 3 stereospecifically.Treatment of compound 3 with methyllithium resulted in migration of an alkyl group from the boron atom to the adjacent carbon atom with elimination of two chlorine atoms to provide 2-sec-alkylbuta-1,3-dienes 5a-d.Similar treatment of (Z)-(1,4-dichlorobut-2-en-2-yl)-tert-alkyl-primary-alkylborane, prepared by the successive reaction of BH3 in THF with a tetrasubstituted ethene, relatively hindered terminal alkene, and compound 1, provided highly pure 2-tert-alkylbuta-1,3-dienes 5e and 5f whose alkyl group was derived from the tetrasubstituted alkene.On the other hand, similar treatment of compound 3, derived from a terminal or sterically unhindered unternal alkene by a modified hydroboration procedure, provided the corresponding 2-primary- (or 2-sec-)alkylbuta-1,3-dienes 5g-m. 2-(Alk-1-ynyl)buta-1,3-dienes 6a-c were provided by the successive reaction of dibromoborane-dimethylsulfide with compound 1, alk-1-ynyldiethylaluminium and methyllithium, although the yields were less good.Successive treatment of (Z)-(1,4-dichlorobut-2-en-2-yl)bis-(1,2-dimethylpropyl)borane 3b with alkylthiomagnesium bromide and methyllithium afforded exclusively 2-alkylthiobuta-1,3-dienes 8a-f whose alkylzhio group migrated from the boron atom via the borate complex.
- Hoshi, Masayuki,Arase, Akira
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p. 2693 - 2700
(2007/10/02)
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- RELATIONSHIPS OF ISOMERIZATION OF THE ALLYLIC TYPE.
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The authors report the results of thermodynamic and kinetic studies of allylic rearrangements of dichlorobutenes. It is shown that the controlling step in allylic rearrangement of dichlorobutenes is monomolecular decomposition of the pi -allyl complex of 1,4-DC-2-B with the catalyst. Therefore all attempts at activation of catalysts of allylic rearrangement are aimed at change of the charge density on the metal (Cu), facilitating migration of chlorine. The effective activating influence of the surface of inorganic supports, such as aluminum oxide, on isomerization of dichlorobutenes in presence of copper naphthenate was demonstrated for the first time left bracket 10 right bracket . The optimal ratio of copper naphthenate to Al//2O//3, doubling the yield of 3,4-DC-1-B by isomerization of 1,4-DC-2-B, was found with the aid of design of experiments.
- Levanova,Yanshevskaya,Asatryan,Saakyan,Kostand'yan,Malkhasyan,Martirosyan
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p. 790 - 793
(2007/10/02)
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- Metal-assisted Reactions. Part 17. Ring-opening and Dimerization of Cyclic Ethers by Titanium Halides
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Reaction of TiCl4 or TiBr4 with a variety of cyclic ethers gives, predominantly, products resulting from simple ring-opening or from ring-opening with simultaneous condensation to dimeric species.The variations in yields of these two kinds of products might be correlated qualitatively with an initial formation of the complex TiX4*2E (X = Cl or Br; E = cyclic ether) in which the ethers were held in a cis or trans relationship.Although such a correlation might suggest that TiCl4 but not TiBr4 exerts a template effect on the condensation, stereochemical considerations of the reaction products indicate otherwise.TiCl3 and VCl3 do not give similar results and TiF4 gives no reaction.
- Delaney, Paul A.,Johnstone, Robert A. W.,Entwistle, Ian D.
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p. 1855 - 1860
(2007/10/02)
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