- Profiling of thiol-containing compounds by stable isotope labeling double precursor ion scan mass spectrometry
-
Here we developed a novel strategy of isotope labeling in combination with high-performance liquid chromatography-double precursor ion scan mass spectrometry (IL-LC-DPIS-MS) analysis for nontargeted profiling of thiol-containing compounds. In this strategy, we synthesized a pair of isotope labeling reagents (?-bromoacetonylquinolinium bromide, BQB; ?-bromoacetonylquinolinium-d7 bromide, BQB-d7) that contain a reactive group, an isotopically labeled moiety, and an ionizable group to selectively label thiol-containing compounds. The BQB and BQB-d7 labeled compounds can generate two characteristic product ions m/z 218 and 225, which contain an isotope tag and therefore were used for double precursor ion scans in mass spectrometry analysis. The peak pairs with characteristic mass differences can be readily extracted from the two precursor ion scan (PIS) spectra and assigned as potential thiol-containing candidates, which facilitates the identification of analytes. BQB and BQB-d7 labeled thiol-containing compounds can be clearly distinguished by generating two individual ion chromatograms. Thus, thiol-containing compounds from two samples labeled with different isotope reagents are ionized at the same time but recorded separately by mass spectrometry, offering good identification and accurate quantification by eliminating the MS response fluctuation and mutual interference from the two labeled samples. Using the IL-LC-DPIS-MS strategy, we profiled the thiol-containing compounds in beer and human urine, and 21 and 103 thiol candidates were discovered in beer and human urine, respectively. In addition, 9 and 17 thiol candidates in beer and human urine were successfully identified by further comparison with thiol standards or tandem mass spectrometry analysis. Taken together, the IL-LC-DPIS-MS method is demonstrated to be a promising strategy in the profiling of compounds with identical groups in metabolomics study.
- Liu, Ping,Huang, Yun-Qing,Cai, Wen-Jing,Yuan, Bi-Feng,Feng, Yu-Qi
-
-
Read Online
- Synthesis of α,β-unsaturated epoxy ketones utilizing a bifunctional sulfonium/phosphonium ylide
-
Herein, a new protocol for rapid synthesis of α,β-unsaturated epoxy ketones utilizing a bifunctional sulfonium/phosphonium ylide is described. This approach comprises two sequential chemoselective reactions between sulfonium and phosphonium ylides and two distinct aldehydes, which allows for the rapid construction of a variety of unsymmetric α,β-unsaturated epoxy ketones. This methodology allows the rapid construction of the core reactive functionality of a family of lipid peroxidation products, the epoxyketooctadecenoic acids, but can be further broadly utilized as a useful synthon for the synthesis of natural products, particularly those derived from oxidized fatty acids. Accordingly, a protocol utilizing this approach to synthesize the epoxyketooctadecenoic acid family of molecules is described.
- Eskandari, Roozbeh,Hess, Jeremy P.,Tochtrop, Gregory P.
-
supporting information
p. 7136 - 7139
(2021/07/28)
-
- Expeditious Syntheses to Pharmochemicals 1,3-Dihydroxyacetone, 1,3-Dichloro-, 1,3-Dibromo- And 1,3-Diiodoacetone from Glycerol 1,3-Dichlorohydrin Using Homogenous and Heterogenous Medium
-
New efficient and reproductive routes to production of 1,3-dihydroxyacetone (1), 1,3-dichloroacetone (6), 1,3-dibromoacetone (7) and 1,3-diiodoacetone (8) from glycerol 1,3-dichlorohydrin (3) were developed. The synthesis of 1 was processed in three steps from glycerol 2 (1,3-selective chlorination of 2 to 3, oxidation of 3 to 6 and subsequent di-hydroxylation) in 51% overall yield. On the other hand, 7 and 8 were produced from 3, via a trans-bromination and trans-iodination, respectively, followed by oxidation and hydroxylation steps, in 38-52% overall yield. It was used homogeneous media with different reagents (HCl/AcOH, pyridinium chlorochromate (PCC), PCC-HIO4) and heterogeneous media with reagents supported on polymer resins such as Amberlyst A26-HCrO4– form, PV-PCC (polyvinyl-pyridinium chlorochromate) and Amberlyst A26-OH– form or reagents supported on alumina such as KI/Al2O3, KBr/Al2O3, in solvent free conditions.
- Pereira, Vera Lúcia P.,da Silva, Fernanda Priscila N. R.,da Silva, Sara R. B.,dos Santos, Priscila F.
-
p. 1725 - 1731
(2020/10/09)
-
- 1,3-bis(R-group ferrocene)-2-propyl alcohol and synthesis method
-
The invention relates to a synthesis method of 1,3-bis(R-group ferrocene)-2-propyl alcohol (R is C2-C4 alkyl). The synthesis method comprises the following steps: dissolving ferrocene in a solvent; slowly adding a halogenated (or hydroxyl and olefin) compound with the carbon number of 2-4 and a catalyst for reaction; performing washing with water, evaporating the solvent and performing rectification to obtain R-group ferrocene; adding acetone and a solvent in another reactor; slowly adding bromine for reaction for a period of time, and then performing washing with water, evaporating the solvent and performing recrystallization to obtain 1,3-dibromoacetone; carrying out Friedel-Crafts alkylation reaction on the R-group ferrocene and the 1,3-dibromoacetone to obtain 1,3-bis(R-group ferrocene) acetone; adding reducing agents such as sodium borohydride in the 1,3-bis(R-group ferrocene) acetone to obtain the 1,3-bis(R-group ferrocene)-2-propyl alcohol as the product. The synthesized bisferrocene derivative is used in a solid propellant and a burning rate regulator, and cannot migrate easily when reacting with a curing agent.
- -
-
Paragraph 0027; 0028; 0029; 0036; 0037; 0038; 0045-0047
(2017/04/14)
-
- Cyclopenta[d]pyrimidines And Substituted Cyclopenta[d]pyrimidines As Antitubulin and Microtubule Targeting Agents, Monocyclic Pyrimidines As Tubulin Inhibitors, And Pyrrolopyrimidines As Targeted Antifolates And Tubulin and Multiple Receptor Tyrosine Kinase Inhibition And Antitumor Agents
-
The present invention provides a compound of Formula I, and salts thereof, and a pharmaceutical composition comprising a compound of Formula I: wherein R1 is selected from the group consisting of and R2 is an alkyl group having from one to ten carbon atoms, or wherein R2 is selected from the group consisting of R1 is an alkyl group having from one to ten carbon atoms; and R is H, or an alkyl group having from one to ten carbon atoms, and R3 is H, an alkyl group having from one to ten carbon atoms, or a halogen. Preferably the compound of Formula V includes wherein R3 is a halogen, and most preferably wherein the halogen is chlorine. Methods of treating a patient with cancer with these compounds are also provided.
- -
-
-
- PROCESS FOR PREPARIING 1,3-DIBROMOACETONE, 1-3-DICHLOROACETONE AND EPICHLOROHYDRIN
-
A process for preparing 1,3-dibromoacetone, 1-3-dichloroacetone and epichlorohydrin which comprises: (a) reacting acetone with 2 moles of bromine to make a mixture of brominated acetone derivatives and byproduct hydrogen bromide; (b) equilibrating the mixture of brominated acetone derivatives and hydrogen bromide to produce 1,3-dibromoacetone as the major product; (c) crystallizing the 1,3-dibromoacetone; and (d) isolating the 1,3-dibromoacetone. The process may further include the steps of (e) reacting the 1,3-dibromoacetone with a chloride source to produce 1,3-dichloroacetone; (f) hydrogenating the isolated 1,3-dichloroacetone to produce 1,3-dichlorohydrin; and (g) cyclizing the 1,3-dichlorohydrin with a base to produce epichlorohydrin.
- -
-
Page/Page column 12-13
(2008/06/13)
-
- Gamma-ketoacid dipeptide derivatives as inhibitors of caspase-3
-
This invention encompasses the novel compounds of Formula I, which are useful in the treatment of caspase-3 mediated diseases. The invention also encompasses certain pharmaceutical compositions comprising compounds of Formula I as well as methods for treatment of caspase-3 mediated diseases.
- -
-
-
- Clean, high-yield preparation of S,S and R,S amino acid isosteres
-
The present invention provides compounds and methods that can be used to convert the intermediate halomethyl ketones (HMKs), e.g., chloromethyl ketones, to the corresponding S,S- and R,S-diastereomers. More particularly, the present invention provides: (1) reduction methods; (2) inversion methods; and (3) methods involving the epoxidation of alkenes. Using the various methods of the present invention, the R,S-epoxide and the intermediary compounds can be prepared reliably, in high yields and in high purity.
- -
-
-
- Gamma-ketoacid dipeptides as inhibitors of caspase-3
-
This invention encompasses the novel compounds of Formula I, which are useful in the treatment of caspase-3 mediated diseases. The invention also encompasses certain pharmaceutical compositions comprising compounds of Formula I as well as methods for treatment of caspase-3 mediated diseases.
- -
-
-
- Pyrazinones, compositions containing such compounds and methods of use
-
Compounds represented by formula I: as well as pharmaceutically acceptable salts, esters, N-oxides and hydrates thereof are disclosed. Pharmaceutical compositions and methods of use are also included. The compounds are active against the caspase-3 enzyme, and thus are useful to treat fin caspase-3 mediated diseases and conditions.
- -
-
-
- Synthesis and reactions of (E)- and (Z)-1,3-dibromo-2-methoxypropene
-
(Z)-1,3-Dibromo-2-methoxypropene is prepared in 90% yield by dehydrohalogenation of 1,2,3-tribromo-2-methoxypropane with diisopropylaminein dichloromethane. The E-isomer can be obtained as the only product in almost quantitative yield by UV irradiation of
- Edvardsen, Kjetil Roe,Benneche, Tore,Tius, Marcus A.
-
p. 3085 - 3089
(2007/10/03)
-
- Process and intermediates for the preparation of oxazoline derivatives
-
PCT No. PCT/US97/20798 Sec. 371 Date May 13, 1999 Sec. 102(e) Date May 13, 1999 PCT Filed Nov. 13, 1997 PCT Pub. No. WO98/22448 PCT Pub. Date May 28, 1998Arthropodicidal oxazoline derivatives and processes and intermediates for the preparation thereof are disclosed. The intermediates are racemic or enantiomerically enriched compounds having formula (I), wherein R and n are disclosed in the specification.
- -
-
-
- SUBSTITUTED OXOBUTYRIC ACIDS AS MATRIX METALLOPROTEASE INHIBITORS
-
The present invention provides pharmaceutical compositions and methods for treating certain conditions associated with matrix metalloproteases comprising administering an amount of a compound or composition of the invention which is effective to inhibit the activity of at least one matrix metalloprotease, resulting in achievement of the desired effect. The compounds of the present invention are either of the generalized formula: STR1 wherein y is 0, 2, or, 3, r is 0-6, Z is (CH 2) 7 or (CH 2) e--C 6 H. sub.4--(CH 2) f, wherein e is 0-1 and f is 0-5, and R 15 is--H,--Cl,--OMe or STR2 wherein n is 0-4, R 17 is C 2 H 5, alkyl, benzyl, and R 16 is STR3 wherein t is 0-2, x is 0-4, and R 4 is one of the following: halide, alkyl of 1-6 carbons, OR, NR 2, NO 2 (R=H or alkyl of 1-6 carbons).
- -
-
-
- PEPTIDE, PEPTIDE ANALOG AND AMINO ACID ANALOG PROTEASE INHIBITORS
-
Methods of use of compounds and compounds for the treatment of disorders characterized by the cerebral deposition of amyloid are provided. Among the compounds are those of formulae (I), (II) and (III): STR1 in which R. sub.1 is preferably 2-methyl propene, 2-butene, norleucine; R 2, R 4, and R 8 are each independently methyl or ethyl; R 3 is preferably iso-butyl or phenyl; R 5 is preferably iso-butyl; R 6 is H or methyl; R 7--(Q) n is preferably benzyloxycarbonyl or acetyl; Q is preferably--C(O)--; R B is preferbly iso-butyl; R A =--(T) m--(D) m--R 1, is which T is preferably oxygen or carbon, and D is preferably a mono-unsaturated C 3-4 alkenyl being more preferred; and X is an alcohol, particularly a secondary alcohol.
- -
-
-
- SELECTIVE MONOBROMINATION OF KETONES BY BIS(DIMETHYLACETAMIDE)HYDROGEN TRIBROMIDE
-
A unified procedure for the α-monobromination of ketones by bis(dimethylacetamide)hydrogen tribromide in methanol is proposed.Methyl aryl ketones with donating and moderately accepting substituents in the ring readily enter into the reaction. 1-Bromo ketones are mostly formed during the bromination of methyl alkyl ketones.
- Rodygin, M. Yu.,Mikhailov, V. A.,Savelova, V. A.
-
p. 881 - 887
(2007/10/02)
-
- Oxybromination Catalysed by the Heteropolyanion Compound H5PMo10V2O40 in an Organic Medium: Selective para-Bromination of Phenol
-
Selective bromination of phenol and its derivatives and the bromination of ketones and alkenes have been achieved by oxybromination at ambient conditions catalysed by the mixed addenda heteropolyanion compound H5PMo10V2O40, which is dissolved in a nonpolar chlorohydrocarbon solvent by complexation with tetraglyme.
- Neumann, Ronny,Assael, Igal
-
p. 1285 - 1287
(2007/10/02)
-
- Reactions of 2,2'-(Azo-2-phenoxypropane) with Bromine: a Novel Route to o- and p-Bromophenol
-
o- and p-Bromophenol have been synthezied from the reactions of 2,2'-(azo-2-phenoxypropane) with different concentrations of bromine in 68 and 88percent yields, respectively.
- Kim, Kyongtae,Chang, Young-Chan
-
p. 1159 - 1160
(2007/10/02)
-
- Bromine-Hydrolysis Control in the Cerium Ion-Bromate Ion-Oxalic Acid-Acetone Belousov-Zhabotinskii Oscillator
-
Chemical oscillations in reacting systems containing BrO3(1-) have been interpreted as a switching phenomenon in which control of the overall reaction is passed back and forth between a set of radical reactions, whose major effect is the removal of Br(1-).Control switches to the radical reactions when is driven low enough.Oscillation occurs because Br(1-) is an indirect product of the radical reactions, causing control to be returned to the nonradical reactions.Bromide ion control of BrO3(1-)-driven oscillations has been challanged on the basis that in some systems the usual source of Br(1-) from the radical reactions is absent.It has been suggested that the oscillations are fact Br2 controlled.It is shown here that one of these puzzling oscillators can be simulated as Br(1-) controlled.By implication the others also can be.Bromine is an important intermediate in these systems as the controlling Br(1-) comes from Br2 hydrolysis and is in equilibrium with Br2 and HOBr.We call such an oscillator Br2-hydrolysis controlled.The simulation is based on 31 elementary reactions of which 9 are reversible.It was constructed on the basis of a large number of experiments on simpler, nonoscillatory reactions involving the same reactants and is much simpler than the mechanism of other BrO3(1-)-driven oscillators because of the relative simplicity in it of the reactions of oxalic acid and acetone.The rate constants thus determined were used without modification to obtain an essentially quantitative simulation of the oscillatory system.It is thus the most complete and quantitatively accurate simulation of a BrO3(1-)-driven oscillator with an organic substrate yet carried out.The complete mechanism can be reduced to a simple five-variable Oregonator-like model that contains no expendable stoichiometric factor and whose rate parameters all can be related directly to the concentration of a principal reactant.
- Field, Richard J.,Boyd, Patrick M.
-
p. 3707 - 3714
(2007/10/02)
-
- Chlorination of Aliphatic Ketones in Methanol
-
The chlorination of aliphatic ketones in methanol has been examined.The product distributions in methanol differ substantially from those obtained by chlorination in carbon tetrachloride.The reaction in methanol favors addition of chlorine to the least substituted carbon α to the carbonyl group.The effect is especially pronounced if an α carbon bearing two substituents is present.The distribution of products is determined by the relative stability of the enol ethers formed from the ketone under the reaction conditions.
- Gallucci, R. R.,Going, R.
-
p. 2532 - 2538
(2007/10/02)
-
- SILYL- AND GERMYL-CYCLOPROPANONES
-
1.The reactions of silylcyclopropanones with compounds containing a mobile hydrogen atom and also with alkoxy, dialkylamino, and dialkoxyphosphinooxy derivatives of Group IVB elements give adducts at the carbonyl group of the cyclopropanone, and, when heated, these undergo isomerization with opening of the three-membered ring exclusively at the C1-C2 bond and with the formation of β-heteroelement-substituted propionic derivatives. 2.Acetic acid and bis(trifluoroacetic) anhydride in reaction with (trimethylsilyl)cyclopropanone form relatively stable products of addition at the carbonyl group. 3.Bromine and iodotrimethylsilane react with silylcyclopropanones with breakage of the C2-C3 bond of the cyclopropanone ring and give the corresponding O- and C-isomeric derivatives of α-silylated ketones containing halogen atoms in the molecule. 4.The reactions of silyl- and germyl-cyclopropanones with diazomethane and with azido-silanes and -germanes can provide a method of synthesis of heteroelement-substituted (Si, Ge) cyclobutanones and β-lactams.
- Zaitseva, G. S.,Krylova, G. S.,Perelygina, O. P.,Baukov, Yu. I.,Lutsenko, I. F.
-
p. 1935 - 1947
(2007/10/02)
-
