18295-59-5Relevant academic research and scientific papers
Metastable Decompositions of Cyclopentanol Ions and +. Ions with the Oxygen on the First Carbon
Hudson, Charles E.,McAdoo, David J.
, p. 1 - 6 (1984)
Ionized cyclopentanol and +. ions with the oxygen on the first carbon lose methyl, ethylene, ethyl ethane and water in their metastable decompositions.We show by collisionally activated decompositions of the products that the losses of ethyl form CH3CH2CO+, the losses of ethylene form CH3C.HCH=O+H, and the losses of methyl probably yield CH3C(=O+H)CH=CH2.Deuterium labeling indicates that ethyl loss from ionized cyclopentanol occurs following α-cleavage of the ring, isomerization to the enol isomer of ionized n-pentanal and subsequent isomerization to the 3-pentanone ion.
Preparation method and application of Grignard reagent
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Paragraph 0062; 0063, (2020/12/29)
The invention relates to a preparation method and application of a Grignard reagent, the Grignard reagent is obtained by treating a halide with a structural formula as a raw material with magnesium inan organic solvent, X is a halogen atom and is selected from Cl, Br and I, R2 is an alkyl or aryl group containing 2-9 carbon atoms. The Grignard reagent is mainly applied to a synthetic process of dimopidol and hydrochloride thereof, and is used for introducing an alkyl side chain. The whole synthetic process of dimopidol and hydrochloride thereof is safe and efficient, each step of reaction operation is simple and safe, and the reaction yield is high so that industrial production can be realized.
Function of the alkyl side chains of Δlac-acetogenins in the inhibitory effect on mitochondrial complex I (NADH-ubiquinone oxidoreductase)
Ichimaru, Naoya,Abe, Masato,Murai, Masatoshi,Senoh, Mai,Nishioka, Takaaki,Miyoshi, Hideto
, p. 3555 - 3558 (2007/10/03)
We synthesized a series of Δlac-acetogenins in which the two alkyl side chains were systematically modified, and examined their inhibitory effect on bovine heart mitochondrial complex I (NADH-ubiquinone oxidoreductase). The results revealed that the physicochemical properties of the side chains, such as the balance of hydrophobicity and the width (or bulkiness) of the chains, are important structural factors for a potent inhibitory effect of amphiphilic Δlac-acetogenins. This is probably because such properties decide the precise location of the hydrophilic bis-THF ring moiety in the enzyme embedded in the inner mitochondrial membrane.
Rhodium(I) fluorothiolate complexes as hydroformylation catalyst precursors. Crystal structure of two polymorphs of trans-[Rh(SC6F5) (CO) (PPh3) 2]
Fierro,Martinez-Ripoll,Merchan,Rodriguez,Terreros,Torrens,Vivar-Cerrato
, p. 243 - 255 (2007/10/03)
The perfluorothiolate dinuclear compounds [Rh( μ,-SC6F5)(COD)]2 1 and [Rh( μ-SC6F5)(CO)2]2 2 react with PPh3 to give monomeric and dimeric complexes, the particular product depending upon the PR3/Rh ratio and reaction conditions. Reaction of 2 with 2 moles of PPh3 renders cis-7 and trans-[Rh( μ-SC6F5)((CO)(PPh3)]2 8, while with 4 moles of PPh3 trans[Rh(SC6F5)(CO)(PPh3)2]10a is obtained. This latter product can otherwise be prepared by Cl metathesis from trans-[RhCl(CO(PPh3)2] in toluene. This same reaction in dichloromethane however yields the cis isomer 10b. When a larger excess of PPh3 is used, a mixture of compounds 11a and 11b is formed. An X-ray crystal structure study shows trans[Rh(SC6F5)(CO)(PPh3)2] to exit as two polymorphs. 11a crystallises in the space group P21/n of the monoclinic system with a = 12.489(1), b= 15.430(5), c= 19.719(1) A, α = γ = 90, β = 92.84(1)°, and 11b is triclinic, space group P1 with a =9.764(2), b= 12.197(6), c= 17.880 A, α = 100.18(5), β = 101.92(2), γ = 113.61(2)°. Both PPh3 ligands are mutually trans and the difference in v(CO) stretching frequencies, 1989 and 1939 cm-1, can be explained in terms of o-phenyl H. . . CO interactions in the latter. The [Rh( μ-SC6F5)(COD)]2 1 and [Rh( μ-SC6F5)(CO)2]2 2/nPPh3 systems have been studied as catalyst precursors for the hydroformylation of 1-heptene in toluene at 30 bar and 343 K. Selectivity towards the linear aldehyde is enhanced when dimeric complexes are used.
Antiarthritic and suppressor cell inducing activity of azaspiranes: Structure-function relationships of a novel class of immunomodulatory agents
Badger,Schwartz,Picker,Dorman,Bradley,Cheeseman,DiMartino,Hanna,Mirabelli
, p. 2963 - 2970 (2007/10/02)
Spirogermanium (1;8,8-diethyl-N,N-dimethyl-2-aza-8-germaspiro[4.5]decane-2-propanamin e dihydrochloride) is a potent cytotoxic agent in vitro which has demonstrated limited activity in experimental animal tumor models. Subsequently, it has been reported that spirogermanium has antiarthritic and suppressor cell-inducing activity. We have synthesized a series of substituted 8-hetero-2-azaspiro[4.5]decane and 9-hetero-3-azaspiro[5.5]undecane analogues of spirogermanium to identify the heteroatom requirements for in vivo antiarthritic and suppressor cell-inducing activity. This structure-activity relationship study has identified that appropriately substituted silicon and carbon analogues of spirogermanium retain both antiarthritic and immunosuppressive activity, with the 8,8-dipropyl (carbon) analogue being among the most active. Following the identification of N,N-dimethyl-8,8-dipropyl-2-azaspiro[4,5]decane-2-propanamine dihydrochloride (9) as more active analogue than spirogermanium, a series of 8,8-dipropyl analogues with various amine substituents were synthesized. A number of these analogues had activity similar to that of 9. A correlation between activity in the adjuvant arthritic rat and the ability to induce suppressor cells (r = 0.894, p0.001) suggests an association between the two pharmacologic effects. While the precise biochemical mechanism(s) for the pharmacological activity is unclear, these data suggest that compounds within this series, e.g., N,N-dimethyl-8,8-dipropyl-2-azaspiro[4.5]decane-2-propanamine dihydrochloride, may provide effective therapy in diseases of autoimmune origin and/or the prevention of rejection in tissue transplantation.
REACTION OF α,β-UNSATURATED ALDEHYDES WITH HYDROGEN PEROXIDE CATALYSED BY BENZENESELENINIC ACIDS AND THEIR PRECURSORS
Syper, Ludwik
, p. 2853 - 2872 (2007/10/02)
Oxidation of α,β-unsaturated aldehydes with hydrogen perixide catalysed by benzeneselenic acids and their precursors has been investigated.Bis 2-nitrophenyl diselenide has proved to be the most effective catalyst.The major products resulting from the oxidation are vinyl formates (a) which on hydrolysis give saturated aldehydes or ketones (g) having the carbon chain shortened by one carbon atom, compared with the starting aldehydes.The minor products are formyloxyoxiranes (b), α-hydroxycarbonyl (e) and α-formyloxycarbonyl (f) compounds with the carbon chain shortened by one carbon atom.Carbonyl compounds d, formally derived from an oxidative fission of the carbon-carbon double bond, have been also isolated.Diformyloxy (4c) and formyloxyacetoxy phenylmethane (5c) have been isolated when cinnamaldehyde (4) or 1-phenyl-2-formyloxypropane (5a) were oxidized, respectively.Possible mechanisms of formation of these products are discussed.Similar products resulted when α,β-unsaturated aldehydes were oxidized with organic peroxy acids.
