Action Of Diazomethane Research Articles

Determination of Di-n-Butyl Phosphate in Organic Streams of FBTR Mixed Carbide Fuel Reprocessing Solution by Gas Chromatographic Technique

The present work describes the amount of Di-n- butyl phosphate (DBP) produced when PUREX solvent (30%tri-n-butyl phosphate (TBP) mixed with 70% hydrocarbon diluent) is exposed to intensive radiolytic and chemical at- tack during the separation of uranium and plutonium from fission products of FBTR mixed carbide fuel reprocessing solution. DBP is the major degradation product of Tri-n-butyl phosphate (TBP). Amount of DBP formed in the lean organic streams of different fuel burn-up FBTR carbide fuel reprocessing solutions were analyzed by Gas Chromatographic technique. The method is based on the preparation of diazo methane and conversion of non-volatile Di-n-butyl phosphate in to volatile and stable derivatives by the action of diazomethane and then determined by Gas Chromatography (GC). A calibration graph was made for DBP over a concentration in the range from 200 to 1800 ppm with correlation coefficient of 0.99587 and RSD 1.2%. The degraded 30% TBP-NPH solvent loaded with heavy metal ions like uranium was analyzed after repeated use and results are compared with standard ion chromatographic technique. A column comparison study to select of proper gas chromatographic column for the separation of DBP from other components in a single aliquot of injection is also examined.

Reactions of levoglucosenone and its derivatives with diazo compounds

The reaction of levoglucosenone with methyl diazoacetate gives first 1-pyrazoline, which then, depending on the reaction conditions, either undergoes denitrogenation to form a mixture of cyclopropane and unsaturated compounds, or isomerizes into 2-pyrazoline capable of easy cyclodimerizing in the presence of pyridine through the addition of the N—H fragments to the carbonyl groups. The product of levoglucosenone reduction, 6,8-dioxabicyclo [3.2.1]oct-2-en-4-ol, affords the corresponding cyclopropane upon the action of diazomethane in the presence of a Pd catalyst, whereas its reaction with methyl diazoacetate in the presence of Rh 2 (OAc) 4 leads to the insertion of methoxycarbonyl carbene into the OH bond. From the ester obtained, l-diazo-3-6,8-dioxabicyclo[3.2.1]oct-2-en-4-yloxypropan-2-one was synthesized in several steps, its denitrogenation under the action of copper compounds is accompanied by the intramolecular insertion of the carbene into the C(4)—H bond of the levoglucosenone fragment to yield the corresponding spirane.

Synthesis of two analogues of ubiquinones and their action on mitochondrial respiration

With the aim of obtaining ubiquinone analogues, a fraction of 5-n-alkyl(C19-C25)resoreinols isolated fromAzotobacter chroococcum 92 cells was converted by the action of diazomethane into mono-O-methyl derivatives, which were oxidized with m-chloroperbenzoic acid. The main oxidation products were characterized by spectrophotometric methods as 2-alkyl-6-methoxy-1,4-benzoquinones and 3-alkyl-5-methoxy-1,2-benzoquinomes. Both types of product accelerated the respiration of mitochondria on succinate in a similar way to natural CoQ10, but, in contrast to it, inhibited respiration on an NAD-dependent substrate.

Diisophorone and Related Compounds, Part 28 [1] Diisophorane-4-spiro-2′-(oxiranes)

The action of diazomethane on 3,4-dioxodiisophoranes yields 3-oxodiisophorane-4-spiro- 2′-(oxiranes). Their reactions, spectral properties and fragmentation patterns under electron impact, and those of compounds derived from them , conform to their proposed structures.

Synthesis of New Xanthene Derivatives with Expected Antischistosomal Activity

AbstractN‐(9H‐Xanthen‐9‐yl)succinimide (1) is prepared by the reaction of xanthene with N‐bromosuccinimide. Hydrolysis of 1 with 5% NaOH yields 3‐[(9H‐xanthen‐9‐yl)aminocarbonyl]propionic acid (3a). The corresponding methyl ester 3c is obtained from 3a by the action of diazomethane. The butanol derivative 4a can be obtained by reduction of 3a or 3c with LiAlH4. Treatment of 1 with LiAlH4 yields the pyrrolidine derivative 5. N‐(9H‐Xanthen‐9‐yl)phthalimide (2) undergoes similar reactions like its analogue 1.

Action of diazomethane on methyl (Z(or E))-2-(acylamino)cinnamates. A new route to methyl (Z)-2-(acylamino)-3-methylcinnamates

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAction of diazomethane on methyl (Z(or E))-2-(acylamino)cinnamates. A new route to methyl (Z)-2-(acylamino)-3-methylcinnamatesCarlos Cativiela, Maria D. Diaz de Villegas, Jose A. Mayoral, and Enrique MelendezCite this: J. Org. Chem. 1985, 50, 17, 3167–3169Publication Date (Print):August 1, 1985Publication History Published online1 May 2002Published inissue 1 August 1985https://doi.org/10.1021/jo00217a030RIGHTS & PERMISSIONSArticle Views188Altmetric-Citations15LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (386 KB) Get e-Alerts Get e-Alerts

Diisophorone and related compounds—IV : 2,7-Epoxydiisophoranes: synthesis and reactions of 3,4-diketo-2,7-epoxydiisophoran-1-OL

Selenium dioxide oxidises 2,7 - epoxydiisophoran - 1 - ol - 3 - one to the corresponding yellow 3,4-diketone. This is reduced to diisophor - 2(7) - en - 1 - ol - 3 - one (“diisophorone”) by Zn in acetic acid or on catalytic hydrogenation, or to 2,7 - epoxydiisophorane - 1,3,4 - triol by LAH or NaBH 4. Alkaline H 2O 2 cleaves ring A of the 3,4-diketone, providing a degradation of the diisophorane- to the bicyclo[3.3.1]nonane-system. The resulting 3 - (2' - carboxy - 2',2' - dimethyl)ethyl -2, 3 - epoxy -1 - hydroxy - 5,7,7 - trimethylbicyclo(3.3.1]nonane - 2- carboxylic acid is convertible into its dimethyl ester by the action of diazomethane.

1-Isopropyl-3-tert-butyl-1,2-diaza-1,3-butadiene in [4 + 2]-cycloaddition reactions

1-Isopropyl-3-tert-butyl-1,2-diaza-1,3-butadiene (I), which is formed as a result of the reaction of α-chloropinacoline with isopropyl hydrazine, exists in the form of a mixture of cisoid and transold conformations and is extremely active in the diene synthesis with maleic anhydride, maleimide, dimethyl fumarate, and methyl vinyl ketone. The conformations of the derivatives obtained, which contain a Δ2-tetrahydropyridazine ring, were established on the basis of the PMR spectra. 1-Isopropyl-3-tert-butyl-trans-5,6-dicarbomethoxy-Δ2-tetrahydropyrid-azine was obtained from dimethyl fumarate and I; this was confirmed by a comparison of data on it with the characteristics of the cis isomer, synthesized by the action of diazomethane on the anhydride of 1-isopropyl-3-tert-butyl-Δ2-tetrahydropyridazine-5,6-dicarboxylic acid.

Action de Me 2NHAlCl 3 sur les acylferrocènes : Préparation et propriétés de sels de ferrocénylimmonium

The action of Me 2NHAlCl 3 on acylferrocenes is a convenient route to ferrocenylimmonium ions FcC(R) N + Me 2. Derivatives with R = H(I), Ph(II), 2-(CH 3) 2 (III) have been prepared. We examined some properties of the salts: NMR, action of diazomethane and reduction with potassium borohydride. This reduction is illustrated by the synthesis of the endo amine (IV). ▪

Synthese du methyl‐2 p‐chlorophenyl‐4 pentane diol‐2,4(fenpentadiol) marque AU 14C

AbstractMethyl‐2 p‐chlorophenyl‐4 pentane diol 2,4 14C‐4 (Rd 292‐Fenpentadiol), a psychotropic drug, was prepared by means of the action of methyl magnesium iodure on p‐chlorophenyl‐3 hydroxy‐3 ethyl butyrate 14C‐3. The latter was obtained by means of the Reformatzri reaction between ethyl bromoacetate and p‐chloroacetophenon 14CO, which was obtained by the action of iodhydric acid on p‐chlorophenyl diazoacetophenon 14CO, resulting from the action of diazomethane on p‐chlorobenzoyl 14C chlorure. The necessary p‐chlorobenzoic carboxyl 14C acid was obtained through carbonatation of p‐chlorphenyl magnesium bromure, free from any isomere a or m. The total yield compared to 14CO3Ba was 31% Specific activity : 25, 3 mCi/mM.

Preparation of certain bromomethyl- and iodomethyl-substituted disilanes

A very convenient route to bromomethyl-substituted organodisilanes involving reaction of the corresponding (methoxymethyl)disilanes with triphenyldibromophoshporane is described. (Iodomethyl)disilanes were best prepared by treatment of the (bromomethyl)disilanes with sodium iodide in acetone, although they coulc be made by the action of phosphoric acid and potassium iodide on the (methoxymethyl)disilanes, with yields and purities being much lower. 1,2-Bis(chloromethyl)tetramethyldisilane was prepared pure, but in very low yield, by the action of diazomethane on sym -dimethyltetrachlorodisilane followed by methylation of the remaining siliconchlorine bonds.

Stereospecific chain-branching by c-alkylation at the ketonic and enolic positions of 1,6-anhydro-2,3- o-isopropylidene-β- D- lyxo-hexopyranos-4-ulose

Attempted base-catalyzed C-formylation at the enolic (C-3) position of 1,6-anhydro-2,3- O-isopropylidene-β- D- lyxo-hexopyranos-4-ulose ( 1) gives instead a dimer ( 8) of 1. The ketone 1 is, however, C-alkylated stereospecifically at C-3 by the action of paraformaldehyde in methanolic potassium carbonate; concomitant reduction at C-4 occurs, and 1,6-anhydro-3- C-(hydroxymethyl)-2,3- O-isopropylidene-β- D-talopyranose ( 3) is formed. The ketone 1 undergoes stereospecific attack at C-4 by Grignard reagents, and the 4- C-methyl ( 13), 4- C-vinyl ( 10), and 4-C-ethynyl ( 11) derivatives of 1,6-anhydro-2,3- O-isopropylidene-β- D-talopyranose were so prepared. Ozonolysis of 10 and 11 gives the corresponding 4- C-formyl ( 14) and 4- C-carboxy ( 16) derivatives, respectively. The spiro epoxide 12 formed by action of diazomethane on the ketone 1 has been characterized as the D- talo isomer by its conversion on reduction into the 4- C-methyl derivative 13.

Covalent hydration in the tetrazolo [1,5-c]quinazoline series (structure of the products of hydration of 5-methyl(phenyl)-9-bromotetrazolo[1,5-c]-quinazolines)

1(2)-Methyl-5-(2-acylamino-5-bromophenyl)tetrazoles (VIa,b), the structures of which were proved by alternative synthesis, were obtained by the action of diazomethane on the products of covalent hydration of 5-methyl(phenyl)-9-bromotetrazolo[1,5-c]quinazolines. A comparison of the IR and UV spectra of the hydration products and VIa and VIb confirms that the former have the 5-(2-acylamino-5-bromophenyl)tetrazole structure (IIa,b) in the crystalline state and in solution.

The addition of diazomethane to ?-ethynylpyridines

The action of diazomethane on β-ethynylpyridines substituted in the pyridine ring or analogous compounds with an alkyl group in place of the acetylenic hydrogen atom has given 3-(pyridin-3-yl)pyrazoles. When the acetylenic hydrogen atom is replaced by an electron-accepting carboxyl group, the polarization of the triple bond interferes with the reaction, which then leads to a mixture of 3- and 4-(pyridin-3-yl)pyrazoles with the simultaneous methylation of the nitrogen of the pyrazole ring.

Correction - The Action of Diazomethane on Ribonucleosides, Preparation of Ribonucleoside 2'- and 3'- Methyl Ethers

Correction - The Action of Diazomethane on Ribonucleosides, Preparation of Ribonucleoside 2'- and 3'- Methyl Ethers

Purine studies. VI. Formation, hydrolysis, and aminolysis of some purine sulphoxides and sulphones.

The action of diazomethane on 2-, 6-, or 8-methylthiopurine gives a separable mixture of the appropriate 9-methyl derivative and a by-product, respectively N(1 or 7),8-dimethyl-2-, 3-methyl-6-, or 3-methyl-8-methylthiopurine. Each 9-methylated methylthiopurine can be oxidised by m-chloroperbenzoic acid to the corresponding sulphoxide and sulphone. These undergo hydrolysis in N-sodium hydroxide at rates which vary little from sulphoxide to sulphone but which show a marked positional order: 8 > 6 2. 9-Methyl-6-methylsulphinylpurine reacts with ethanolic piperidine four times faster than the corresponding sulphone or chloro-analogue. The 1H n.m.r. spectrum of each methylthiopurine shows a significant downfield shift (ca. 0.5 p.p.m.) of the H-8 peak on changing solvent from deuteriochloroform to [2H6]dimethyl sulphoxide; peaks for H-2 and H-6 show much smaller shifts in either direction.

2-Deoxy sugars Part XIII. 1,3-dideoxy-d- erythro-hexulose

The known 3,4,5-tri- O-benzoyl-2-deoxy- d- erythro-pentose (prepared in three steps from 2-deoxy- d- erythro-pentose) was oxidized to 3,4,5-tri- O-benzoyl-2-deoxy- d- erythro-pentonic acid, which was converted into the corresponding acid chloride. Treatment of the acid chloride with ethereal diazomethane afforded the diazomethyl ketone, which underwent reduction to give crystalline 4,5,6-tri- O-benzoyl-1,3-dideoxy- d- erythro-hexulose, obtained alternatively, in 46% yield, by the action of diazomethane on 3,4,5-tri- O-benzoyl-2-deoxy- d- erythro-pentose. Mercaptalation of the benzoylated 1,3-dideoxy- d- erythro-hexulose with methanethiol yielded syrupy 4,5,6-tri- O-benzoyl-1,3-dideoxy- d- erythro-hexulose dimethyl dithioacetal which, on debenzoylation, gave 1,3-dideoxy- d- erythro-hexulose dimethyl dithioacetal (likewise a syrup), which was converted into crystalline 6- O-adamantoyl-1,3-dideoxy- d- erythro-hexulose dimethyl dithioacetal. Debenzoylation of 4,5,6-tri- O-benzoyl-1,3-dideoxy- d- erythro-hexulose afforded 1,3-dideoxy- d- erythro-hexulose as an impure syrup.

Étude de la configuration des cyano-1, diphényl-1,2 cyclopropanes substitués par résonance magnétique nucléaire

Configuration of a series of ten 1-cyano, 1, 2-diphenyl-cyclopropanes generated by the action of diazomethane upon the corresponding trans α-cyanostilbenes was established using N.M.R, spectra. Comparison between experimental and calculated data made possible the assignation to all compounds of a configuration in which the proton at carbon-2 lies in the trans position relating to the cyano group at the carbon-1. According to this result and owing to the configuration of the parents α-cyanostilbenes, the decomposition of the Δ-1 pyrazoline, which is an intermediate in the reaction considered, takes place stereospecifically.

Composés multispiranniques, dérivés de la di-isopropylidène-2,4 cyclobutanone

In the action of diazomethane on di-isopropyliden-cyclobutanone (DiPC), three products showing a multispirannic structure were isolated : the first one C12H18ON4, Fus. 118-20° C, which is to be considered as generated by two consecutive cyclo-additions, is the dispiro [bis (4,4-dimethyl, 1-pyrazolin, 3-yl) 2', 4'] cyclobutanone ; the second one, C13H20ON4, Fus. 101-3° C, generated from 2 by the further reaction of diazomethane getting the methylene radical fixed on the carbonyl group, may be called trispiro [bis (4,4-dimethyl, 1-pyrazolin, 3-yl) 2', 4' 2-oxirane, 1'] cyclobutane (5) and the last one, Ci3H2oON4, Fus. 149-51° C, which is an isomer of the former, resulting from the insertion of a methylene group in the cyclobutanone ring, is the dispiro [bis (4,4-dimethyl, 1-pyrazolin, 3-yl) 2', 4'] cyclopentanone (4). Rather unexpected was the decarbonylation, by U.V. photolysis, of 2, getting the unknown, CnHiSN4, Fus. 128-30° C, which was the dispiro [bis (4,4-dimethyl, 1-parazolin, 3-yl) 2', 4'] cyclopropane. Finally, it was also possible with the COREY reactant acting on D/PC to synthétisé a mixture of both cis, Fus. 72-3° C, and trans, Fus. 101-2° C, isomers of the dispiro [bis (2,2-dimethyl, 1-cyclopropyl) 2', 4'] cyclobutanone, CiiHisO, in quantitative yield. Spectroscopic data are given to assess the structure of the compounds described.

The constitution of isamic acid

The structure of isamic acid, prepared by the reaction of isatin with ammonia, has been established. It is that of the ylid XIIa or XIIc, different from the ylid XIIb first suggested by the present authors in an earlier communication. The difference lies in an unsuspected exchange of nitrogen functions.The nature of the oxidation products with hydrogen peroxide (VII), with nitric acid, and with potassium permanganate (XXVII) has been elucidated; these do not differ from those suggested earlier.In the Appendix the action of diazomethane on N-acetyl isatoic acid is described. Three molecules of reagent are consumed in esterification, homologation, and epoxide formation.