(2-Naphthoxy)acetyl chloride,a simple fluorescent reagent

In continuing the search for fluorescent reagents for analytical derivatization in chromatography, we found a simple chemical, (2-naphthoxy)acetyl chloride, with potential fluorophore/chromophore characteristics for the highly sensitive detection of analytes with an amino function. The reagent has an auxochrome (a substituted alkoxy moiety) attached to the fluorophoric/chromophoric naphthalene system, resulting in favorable spectrophotometric properties. The reagent can be easily prepared from (2-naphthoxy)acetic acid and has been used in organic synthesis; it is initially introduced as a fluorescent reagent to derivatise amantadine and memantine (amino pharmaceuticals) as model analytes. The resulting naphthoxy derivatives of the drugs can be analyzed at sub-microM levels by HPLC with fluorimetric detection (excitation wavelength 227 nm, emission wavelength 348 nm). Application of the reagent to the fluorimetric derivatization of important biological amines for sensitive detection can be expected.     

Bis(pyridine)iodonium tetrafluoroborate (IPy2BF4): a versatile oxidizing reagent

The use of bis(pyridine)iodonium tetrafluoroborate (IPy(2)BF(4)) as an oxidizing agent towards different types of alcohols is reported. The observed reactivity involves different reaction pathways, as a function both of the structures of the starting materials and of the experimental conditions. Interestingly, the title iodine-containing compound is capable of a tuneable reaction with simple cycloalkanols, providing straight and selective access either to omega-iodocarbonyl compounds or to ketones, a previously unreported and chemoselective range of oxidation potential. Furthermore, appropriate conditions for the preparation of aldehydes and esters from primary alcohols by easily performed experimental procedures were also established. The beta-scission reactions of cycloalkanols and the alpha-oxidation processes of primary, secondary and benzylic alcohols are discussed.     

Polymer-supported triphenylphosphine ditriflate: a novel dehydrating reagent

A new type of polymeric dehydrating reagent, readily prepared by the treatment of polymer-supported triphenylphosphine oxide with triflic anhydride, was found to be effective in a variety of dehydration reactions such as ester and amide formation; the polymer-supported triphenylphosphine oxide was easily recovered and reused several times without the loss of activity.     

Triethylsilane-indium(III) chloride system as a radical reagent

[reaction: see text] A novel generation method of indium hydride (Cl2InH) was found by the transmetalation of InCl3 with Et3SiH. In the intramolecular cyclization of enynes, the previously reported system (NaBH4-InCl3) has a problem of side reactions with the coexistent borane. In contrast, the problem was solved by the presented system, which affords effective hydroindation of alkynes.     

Phenylsulfenyl chloride/N,N-diisopropylethylamine: A useful reagent for cyclic ether formation (sulfenyletherification)

A general method for the formation of cyclic ethers and lactones is described. The procedure employs phenylsulfenyl chloride and N,N-diisopropylethylamine to generate an episulfonium ion intermediate from which the cyclic products arise by internal nucleophilic displacement.     

Diethyl chlorophosphite: a versatile reagent

Diethyl chlorophosphite (DECP) was previously described as a reducing agent for nitro compounds to the corresponding amines (Fischer, B.; Sheihet, L. J. Org. Chem. 1998, 63, 393). Here, the utility of this reagent was extended to chemical conversions of other oxygenated functional groups. In this paper we report on the scope of the reaction of DECP with N-oxides, epoxides, sulfones, sulfoxides, hydroxylamines, ketoximes, and aldoximes. The chemoselectivity of DECP is described, and conditions for a stepwise multiple conversion of functional groups on the same molecule with this reagent are provided.     

Ferric chloride: a mild and versatile reagent for the formation of 1,6-anhydro glucopyranoses

A novel method for the preparation of 1,6-anhydro glucopyranoses (mono- and disaccharides) utilizing anhydrous FeCl₃ as Lewis acid is described. Treatment of methyl 6-O-benzyl and 6-O-p-methoxybenzyl-α/β d-glucopyranosides derivatives with FeCl₃ in CH₂Cl₂ at room temperature and 40°C afforded 1,6-anhydro glucopyranosides in moderate to good yields, through a debenzylation and intramolecular glycosidation in one step. A plausible reaction pathway is proposed.     

The Vilsmeier reagent: a useful and versatile reagent for the synthesis of 2-azetidinones

(Chloromethylene)dimethylammonium chloride (Vilsmeier reagent), prepared easily from N,N-dimethylformamide and oxalyl chloride or thionyl chloride, works as a versatile acid activator reagent for the direct [2+2] ketene-imine cycloaddition of substituted acetic acid and imines in one-pot synthesis under mild conditions. Monocyclic, spirocyclic and 3-electron-withdrawing group β-lactams were synthesized by this method and optimization of conditions were performed.     

Reaction of AgN3 with SOCl2: evidence for the formation of thionyl azide, SO(N3)2

Pure thionyl azide SO(N(3))(2), which is the only gaseous reaction product, has been generated in a vacuum by the heterogeneous reaction of SOCl(2) vapor with AgN(3) at room temperature at a SOCl(2) vapor pressure of 1 x 10(-3) Torr. Evidence for the formation of SO(N(3))(2) is given by on line photoelectron spectroscopy (PES) combined with outer valence Green's function (OVGF) calculations with the 6-311++G(2df) basis set. The good agreement between the PES experiment and the OVGF calculation shows that SO(N(3))(2) has C(1) symmetry. The first ionization energy of SO(N(3))(2) is 10.18 eV.     

Chromium (II) chloride : a new reagent for cross-aldol reactions

The proposed cross aldolization of α-bromoketones with aldehydes in presence of Chromium (II) chloride is an excellent stereospecific reaction. One exception to the stereospecific orientation is reported.     

O-(2,3,4,5,6-pentafluorophenyl)methylhydroxylamine hydrochloride: a versatile reagent for the determination of carbonyl-containing compounds.

A review on the use of O-(2,3,4,5,6-pentafluorophenyl)methylhydroxylamine hydrochloride (PFBHA) for the determination of carbonyl-containing compounds is presented. PFBHA has been used in the determination of such diverse compounds as thromboxane B2, prostaglandins, amygdalin and a variety of other aldehydes, ketones and acids. PFBHA has been used for the determination of these compounds found in water, blood, urine, air and even clothing. The review covers literature referenced in Chemical Abstracts from 1975, when PFBHA was first synthesized, through March 1992.     

High-performance liquid chromatographic assay of N(G)-monomethyl-L-arginine, N(G),N(G)-dimethyl-L-arginine, and N(G),N(G)'-dimethyl-L-arginine using 4-fluoro-7-nitro-2, 1,3-benzoxadiazole as a fluorescent reagent

N(G)-Monomethyl-L-arginine (L-NMMA), N(G),N(G)-dimethyl-L-arginine (ADMA), and N(G),N(G)'-dimethyl-L-arginine (SDMA) are emerging cardiovascular risk factors. A high-performance liquid chromatographic method with fluorescence detection for the simultaneous determination of L-NMMA, ADMA and SDMA is described. The assay employed 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F) as a fluorescent derivatization reagent. After solid phase extraction with cation-exchange column, the methylated arginines were converted to fluorescent derivatives with NBD-F, and the derivatives were separated within 32 min on a reversed-phase column. Nomega-Propyl-L-arginine was Used as an internal standard. Extrapolated detection limits were 12 nM (12 fmol per injection) for L-NMMA and 20 nM (20 fmol per injection) for ADMA and SDMA, respectively, with a signal-to-noise ratio of 3. The calibration curves for L-NMMA, ADMA and SDMA were linear within the range of 50-5000 fmol. The method was applied to the quantitative determination of L-NMMA, ADMA and SDMA in 200 microl of rat plasma. The concentrations of L-NMMA, ADMA and SDMA in rat plasma were 0.16 +/- 0.03, 0.80 +/- 0.25 and 0.40 +/- 0.21 microM, respectively (n = 5).     

A novel active ester synthesis reagent (N,N′-disuccinimidyl carbonate)

A convenient reagent for active ester synthesis --N,N′-disucinimidyl carbonate-- was prepared. This reagent was useful for the preparation of active esters and peptides in stead of dicyclohexylcarbodiimide.     

Bis(trimethylsilyl)peroxide as a versatile reagent for selective generation of oxyphosphoryl group

Bis(trimethylsilyl)peroxide, Me₃SiOOSiMe₃, (BSPO) oxidizes phosphines and phosphites to respective oxyphosphoryl derivatives with retention of the configuration at the phosphorus atom. It also converts thiophosphory] function to oxyphosphoryl function with inversion of the configuration at phosphorus. High yields and high stereoselectivities of these processes render them useful for the synthetic application.