Acetone Dimethylhydrazone Research Articles

Synthesizing phosphorus hydrazones as a method to dispose unsymmetrical dimethylhydrazine

This paper deals with studying the possibility of obtaining a phosphorus-containing derivative of acetone N, N-dimethylhydrazone. It is shown that the phosphorylated derivative is not obtained by directly phosphorylating the acetone dimethylhydrazone, but via Abramov reaction from aminoacetone that is afforded in the interaction of diphenylphosphorous acid with the acetone N, N-dimethylhydrazone.

NDMA formation mechanisms from typical hydrazines and hydrazones during ozonation: A computational study.

N-nitrosodimethylamine (NDMA) as the most frequently detected disinfection by-product has aroused widespread concern due to its unusually high carcinogenicity, however, there is still limited understanding of its formation mechanisms. In this study, the formation mechanisms of NDMA from some typical hydrazines and hydrazones with high NDMA conversion yields (60%∼90%) during ozonation, i.e., unsymmetrical dimethylhydrazine (UDMH), 1-formyl-2,2-dimethylhydrazine (FDMH), formaldehyde dimethylhydrazone (FDH) and acetone dimethylhydrazone (ADMH), were investigated by using DFT method with the M05 functional. A new NDMA formation mechanism from hydrazines during ozonation was proposed, in which the initial step is hydrogen abstraction rather than previously reported oxygen addition. For hydrazones, the C atom of the -N = C moiety in hydrazones is preferred to be attacked by ozone to generate N,N-dimethylaminonitrene (DMAN), which is an important intermediate in NDMA formation during ozonation. Moreover, the reactivity order of the following H atoms in hydrogen/hydride ion abstraction (HA) by ozone is -NH2 > -N(CH3)2 > -CO-NH ∼ =C(CH3)2 > =CH-. Additionally, formation pathways of some experimentally detected compounds, i.e., HOOOH, HOOH and HCOH, in the ozonation of hydrazine were elucidated in this study. The results are expected to expand our understanding of NDMA formation mechanisms and ozone reaction characteristics.

Газохроматографическое определение 1,1-диметилгидразина в образцах воды методом твердофазной микроэкстракции с дериватизацией

1,1-Dimethylhydrazine (1,1-DMH) used as a rocket fuel component is highly reactive and unstable compound. It greatly complicates its accurate and express determination in environmental samples. Goal of this work was to develop a method for its express determination in water samples based on solid-phase microextraction with preliminary derivatization. Acetone was selected as reagent for derivatization because during its reaction with 1,1-DMH, volatile and hydrophobic acetone dimethylhydrazone (ADMH) was formed. It was established that fiber based on 100-micron polydimethylsiloxane provides the most efficient extraction of ADMH from water at extraction time 2 min. Optimal concentration of acetone was 30 mg/mL. The minimum time for reaction of 1,1-DMH with acetone is 10 minutes. Addition of acids and alkali reduced ADMH response that may be caused by degradation of 1,1-DMH and reduction of derivatization rate. Addition of salt allowed to increase the response of ADMH however made impossible the quantitative determination of 1,1-DMH. Dependence of ADMH response on the concentration of 1,1-DMH at optimized parameters is linear in the concentrations range of 0.1-100 mg/L and can be used for quantitative determination of 1,1-DMH in water. Detection limit of the developed method is 0.02 mg/L. Reproducibility index of the method in the whole range of concentrations did not exceed 7%, accuracy index - 15%. Developed method is simple, inexpensive, accurate, automated and can be recommended for implementation in laboratories conducting environmental monitoring in areas of rocket-carriers fall.

N-nitrosodimethylamine (NDMA) formation from the ozonation of model compounds

Nitrosamines are a class of toxic disinfection byproducts commonly associated with chloramination, of which several were included on the most recent U.S. EPA Contaminant Candidate List. Nitrosamine formation may be a significant barrier to ozonation in water reuse applications, particularly for direct or indirect potable reuse, since recent studies show direct formation during ozonation of natural water and treated wastewaters. Only a few studies have identified precursors which react with ozone to form N-nitrosodimethylamine (NDMA). In this study, several precursor compound solutions, prepared in ultrapure water and treated wastewater, were subjected to a 10 M excess of ozone. In parallel experiments, the precursor solutions in ultrapure water were exposed to gamma radiation to determine NDMA formation as a byproduct of reactions of precursor compounds with hydroxyl radicals. The results show six new NDMA precursor compounds that have not been previously reported in the literature, including compounds with hydrazone and carbamate moieties. Molar yields in deionized water were 61–78% for 3 precursors, 12–23% for 5 precursors and <4% for 2 precursors. Bromide concentration was important for three compounds (1,1-dimethylhydrazine, acetone dimethylhydrazone and dimethylsulfamide), but did not enhance NDMA formation for the other precursors. NDMA formation due to chloramination was minimal compared to formation due to ozonation, suggesting distinct groups of precursor compounds for these two oxidants. Hydroxyl radical reactions with the precursors will produce NDMA, but formation is much greater in the presence of molecular ozone. Also, hydroxyl radical scavenging during ozonation leads to increased NDMA formation. Molar conversion yields were higher for several precursors in wastewater as compared to deionized water, which could be due to catalyzed reactions with constituents found in wastewater or hydroxyl radical scavenging.

Synthesis of (R)-2,3-dihydro-2,5-dimethyl-2-isopropylfuran

The synthesis of (R)-2,3-dihydro-2,5-dimethyl-2-isopropylfuran (1), an insect pheromone, via a 1,3-oxathiane is reported. Key steps are the preparation of (S)-2,3-dimethylbutane-1,2-diol (7) from isobutyryloxathiane 5 and reaction of lithiated acetone dimethylhydrazone with tosylated diol 8. NMR spectra of the key tautomeric precursors, 2/2'/3, to 1 have been analyzed in detail, and the enantiomeric excess of these precursors was determined by a chiral shift 13 C NMR experiment

Synthesis of Spiroacetal Pheromones via Metalated Hydrazones

The synthesis of simple alkyl substituted spiroacetals by α,α′-alkylation of metalated acetone dimethylhydrazone with appropriate electrophiles and subsequent acid catalyzed cleavage and ring closure of the products is described.

Synthesis of exogonic acid and related compounds

Hydroxymercuration, cyclization, and reduction of appropriate hydroxy ketones or enones carrying a suitably located α,β-unsaturated ester function is an efficient route to exogonic acid (2-(carboxymethyl)-7-methyl-1,6-dioxaspiro[4.4]nonane), a resin constituent of the Brazilian tree Ipomoea operculata (Martin), and related [4.5] and [5.5] spiroketal systems. Procedures incorporating stereocontrol at C-2 and C-7 of exogonic acid are also reported and involve sequential alkylation with epoxypropane and 1,2-epoxy-4-(tetrahydropyranyloxy)butane of anions (or dianions) derived from methyl acetoacetate or acetone dimethylhydrazone.

Simple Synthesis of (Z)-12-Nonadecen-9-one, (Z)-13-Icosen-10-one, the Sex Pheromone of Peach Fruit Moth, and (Z)-5-Undecen-2-one, a Biologically Active Molecule from the Pedal Gland of the Bontebok

Abstract A simple and convenient synthesis of (Z)-12-nonadecen-9-one, (Z)-13-icosen-10-one, the sex pheromone of the peach fruit moth, and (Z)-5-undecen-2-one, the pheromone from the pedal gland of the bontebok, is described. These pheromones were readily synthesized using successive alkylation of acetone dimethylhydrazone in one-pot.

ChemInform Abstract: Acetone Dimethyl Hydrazone: Useful Synthon for the Synthesis of Pheromones with Keto and Spiroketal Functions.

AbstractThe key step in the syntheses of the pheromones (III) and (IX) is the regioselective bisalkylation of acetonedimethylhydrazone (I) either with the protected bromoalcohol (II) or with n‐nonyl bromide (VIII) and Z‐3‐nonenyl bromide (VII).

Acetone Dimethyl Hydrazone: Useful Synthon+for the Synthesis of Pheromones with Keto and Spiro Ketal Functions

Abstract The use of α-lithiated dimethyl hydrazones as an efficient enolate equivalent for the alkylation of ketones has been reported1,2,3. Due to the ragioselectivity exhibited by acetone dimethyl hydrazone (1) towards the formation of bis alkylated products, we have used the easily avaiLable (1) as a convenient synthon for achieving a short and simple synthesis of pheromones, 1,7-dioxaspiro (5,5) undecane4 (2) and Z-6-Heneicosen-11-one (2). The key step in both the syntheses is the regioselective bis alkylation of (1) using butyl lithium as a base, as shown in Scheme I.

ChemInform Abstract: THE FACILE SYNTHESIS OF UNSYMMETRICAL KETONES USING ACETONE DIMETHYLHYDRAZONE

AbstractDas nach Literaturverfahren erhaltene Acetonhydrazon (II) wird mit den Alkylhalogeniden (III) zu den Monoalkylderivaten (IV) umgesetzt, die in einem weiteren Alkylierungsschritt mit den Alkylhalogeniden (V), die zum Teil mit den Alkylhalogeniden (III) identisch sind, zu den asymm. Dialkylhydrazonen (VI) umgesetzt werden, aus denen dann die asymm. Ketone (VII) erhalten werden.

The Facile Synthesis of Unsymmetrical Ketones Using Acetone Dimethylhydrazone

Abstract Unsymmetrical ketones were prepared by successive alkylation of acetone dimethylhydrazone. Application of this reaction to the synthesis of dihydrojasmone is described.

Reaction of ethyl diazoacetate with acetone dimethylhydrazone and acetone ketazine

1. The reaction of ethyl diazoacetate with acetone ketazine in the presence of copper bronze at 100–110° leads to formation of 1-isopropylidene-2-carbethoxymethylhydrazine, ethyl glyoxalate isopropylidenehydrazine, and 3,5,5-trimethyl-1-carbethoxymethyl-Δ2-pyrazoline. The routes for formation of the indicated products have been considered. 2. The ease of isomerization of acetone ketazine into 3,5,5-trimethyl-Δ2-pyrazoline ander the conditions of reaction of ethyl diazoacetate with acetone ketazine has been established. 3. The formation of the appropriate aziridines has not been detected in reactions of carbethoxycarbene with compounds containing a C=N bond, but products of the formal insertion of this carbene at the N-H bond of amines formed under the reaction conditions have been isolated. 4. In the case of reaction of ethyl diazoacetate with 3,5,5-trimethyl-Δ2-pyrazoline, which contains both an N-H bond and also a C=N bond, an exclusive tendency of carbethoxycarbene toward insertion at the N-H bond has been shown.

Addition of acetone dimethylhydrazone to dimethyl acetylenedicarboxylate

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAddition of acetone dimethylhydrazone to dimethyl acetylenedicarboxylateStephen F. NelsenCite this: J. Org. Chem. 1969, 34, 8, 2248–2250Publication Date (Print):August 1, 1969Publication History Published online1 May 2002Published inissue 1 August 1969https://doi.org/10.1021/jo01260a003RIGHTS & PERMISSIONSArticle Views106Altmetric-Citations6LEARN 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 (409 KB) Get e-Alerts Get e-Alerts

Reaction of diazoacetic esters with acetone dimethylhydrazone

Reaction of diazoacetic esters with acetone dimethylhydrazone