Chloroacetaldehyde, formation

Another difficulty in this reaction lies in the preparation of pure chloroacetaldehyde. The low yield observed is due to simultaneous formation of by-products (polyhalogenation). So vinylchloride was used as a starting material for this synthesis (449). A simpler method is to react chlorine with vinylchloride in aqueous solution and then to dehydrate the semihydrated chloroacetaldehyde by distillation through a column of calcium chloride heated to 70 to 90 C (451). 

The results initially obtained were due to the formation in both aqueous and alcoholic solution of resinous by-products. This formation results from the decomposition of the ammonium dithiocarbamate, or from the self-condensation of chloroacetaldehyde or the formation of intermediate products. 

The degradation of 1,2-dichloroethane by Pseudomonas sp. strain DCAl was initiated not by hydrolysis, but by monooxygenation with the direct formation of 1,2-dichloroethanol that spontaneously decomposed to chloroacetaldehyde (Hage and Hartmans 1999). 

Reaction of the purine 219 in a phosphate buffer with substituted chloroacetaldehydes 220 gave rise to formation of the fused linear 5 6 5 system 221 (Equation 58) <20040BC821>. 

EINECS 203-468-6, see Ethylenediamine EINECS 203-470-7, see Allyl alcohol EINECS 203-472-8, see Chloroacetaldehyde EINECS 203-481-7, see Methyl formate EINECS 203-523-4, see 2-Methylpentane EINECS 203-528-1, see 2-Pentanone EINECS 203-544-9, see 1-Nitropropane EINECS 203-545-4, see Vinyl acetate EINECS 203-548-0, see 2,4-Dimethylpentane EINECS 203-550-1, see 4-Methyl-2-pentanone EINECS 203-558-5, see Diisopropylamine EINECS 203-560-6, see Isopropyl ether EINECS 203-561-1, see Isopropyl acetate EINECS 203-564-8, see Acetic anhydride EINECS 203-571-6, see Maleic anhydride EINECS 203-576-3, see m-Xylene EINECS 203-598-3, see Bis(2-chloroisopropyl) ether EINECS 203-604-4, see 1,3,5-Trimethylbenzene EINECS 203-608-6, see 1,3,5-Trichlorobenzene EINECS 203-620-1, see Diisobutyl ketone EINECS 203-621-7, see sec-Hexyl acetate EINECS 203-623-8, see Bromobenzene EINECS 203-624-3, see Methylcyclohexane EINECS 203-625-9, see Toluene EINECS 203-628-5, see Chlorobenzene EINECS 203-630-6, see Cyclohexanol EINECS 203-632-7, see Phenol EINECS 203-686-1, see Propyl acetate EINECS 203-692-4, see Pentane EINECS 203-694-5, see 1-Pentene EINECS 203-695-0, see cis-2-Pentene EINECS 203-699-2, see Butylamine EINECS 203-713-7, see Methyl cellosolve EINECS 203-714-2, see Methylal EINECS 203-716-3, see Diethylamine EINECS 203-721-0, see Ethyl formate EINECS 203-726-8, see Tetrahydrofuran EINECS 203-729-4, see Thiophene EINECS 203-767-1, see 2-Heptanone EINECS 203-772-9, see Methyl cellosolve acetate EINECS 203-777-6, see Hexane EINECS 203-799-6, see 2-Chloroethyl vinyl ether EINECS 203-804-1, see 2-Ethoxyethanol EINECS 203-806-2, see Cyclohexane EINECS 203-807-8, see Cyclohexene EINECS 203-809-9, see Pyridine EINECS 203-815-1, see Morpholine EINECS 203-839-2, see 2-Ethoxyethyl acetate EINECS 203-870-1, see Bis(2-chloroethyl) ether EINECS 203-892-1, see Octane EINECS 203-893-7, see 1-Octene EINECS 203-905-0, see 2-Butoxyethanol EINECS 203-913-4, see Nonane EINECS 203-920-2, see Bis(2-chloroethoxy)methane EINECS 203-967-9, see Dodecane EINECS 204-066-3, see 2-Methylpropene EINECS 204-112-2, see Triphenyl phosphate EINECS 204-211-0, see Bis(2-ethylhexyl) phthalate EINECS 204-258-7, see l,3-Dichloro-5,5-dimethylhydantoin... 

Girard-T derivatives of chloroacetaldehyde, crotonaldehyde, and acrolein were not stable. Alternative methods were developed based upon the derivative formed by reaction of crotonaldehyde with hydroxylamine, and the formation of the hydrate of chloroacetaldehyde. 

FIGURE 5. The mehanism for the formation of etheno adducts by the reaction of chloroacetaldehyde and base components of nucleic acids. Structures of -adenosine and e-cytidine... 

Reaction of chloroacetaldehyde with adenine, adenosine as well as its nucleotides (see Section 7.1.1.3.7.) results in the formation of the so-called etheno compounds eAde, eA, eAMP, etc. These fused purine derivatives exhibit intensive fluorescence ethenoadenosine, for example, shows an emission maximum at 415 nm (excitation 310 nm) in aqueous solution (pH 7) with a quantum yield of 0.56 (life time 20 nsec).All adenine derivatives have similar fluorescence properties the nucleotide analogs show considerable substrate activities with different kinases. 

Other thermal rearrangements probably leading to sulfenes include (a) formation of chloroacetaldehyde from ethenesulfonyl chloride120 as in equation 28, (b) generation of formaldehyde and acetaldehyde from 3-thietanol 1,1-dioxide118 shown in equation 29, and (c) rearrangement121 of iV-phenylbenzothiazete 1,1-dioxide (39) to 41, probably via 40 (equation 30). 

Treatment of single-stranded nucleic acids with chloroacetaldehyde results in the formation of hydrated etheno derivatives of cytosine and adenine bases (112) and (113), which lose water slowly under physiological conditions to give the fluorescent bases 3,A -ethenocytosine (eC) and l,A -ethenoadenine (sA), respectively. DNA has been rendered fluorescent by this treatment, and the... 

The 4-hydroxylation pathway leads to the formation of phosphoramide mustard, which is the active byproduct, and acrolein. The alternate route is dechloroethylation, which is accompanied by formation of a neurotoxic and urotoxic metabolite, chloroacetaldehyde. Although qualitatively similar, the metaboKsm of ifosfamide differs from cyclophosphamide quantitatively. Whereas iV-dechloroethylation is a minor pathway for cyclophosphamide, it accounts for about 50% of the elimination of ifosfamide [237]. The metabolic products of R-ifosfamide are R-2-dechloroethyhfosfa-mide and S-3-dechloroethylifosfamide, whereas S-2-dechloroethyKfosfamide and R-3-dechloroethylifosfamide are the products of S-ifosfamide metabolism [238]. 

Next, total rat hver proteins were examined for the presence of linkages characteristic of ADP-ribosyl-cysteine. Trichloroacetic acid insoluble extracts of hver tissue were treated to remove non-covalently bound ADP-ribose and subsequently treated with mercuric ion and analyzed for ADP-ribose. Fig. 2 shows such an analysis along with control experiments. Panel A shows that analysis of an extract treated with mercuric ion exhibited a fluorescent peak that migrated at the expected elution position of etheno-ADP-ribose, the fluorescent derivative used for quantitative determination of ADP-ribose. Panel B shows the analysis in which mercuric ion was omitted from a parahel sample of hver extract. Panel C shows the result obtained when chloroacetaldehyde, which is required for the formation of the fluorescent derivative of ADP-ribose, was omitted. This control rules out the possibility of endogenously fluorescent compounds present in the ceh extract that were released by mercuric ion. Panel D shows that a small amoimt of authentic etheno-ADP-ribose added to extracts prepared as in... 

The equilibrium constants for the formation of hydrates of acetaldehyde and chloroacetaldehyde are 1 and 37, respectively. Explain whether you expect the equilibrium constant for formation of the hydrate of trichloroacetaldehyde to be greater or less than 37. 

Internal OH addition is the minor pathway (about 28% of the reaction), and leads to formation of formaldehyde and methylglyoxal. Products of the Cl-atom-initiated process have also been studied (Fantechi et al., 1998c Canosa-Mas et al 2001 Orlando et al., 2003). Chloroacetaldehyde (with formaldehyde co-product) is seen as a major product, by analogy to glycolaldehyde production in the OH system. 

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