2.2.2- Trichloro acetaldehyde

SYNS ACETALDEHYDE,TRICHLORO-(9CI) ANHYDROUS CHLORAL CHLOR. L, anhydrous, inhibited pOT) CLORALIO GRASEX RCRA WASTE NUMBER U034 TRICHLOROACETALDEHYDE... 

Beilstein Handbook Reference) Acetaldehyde, trichloro- Anhydrous chloral BRN 0506422 CCRIS 852 Chloral Chloral, anhydrous, inhibited Cloralio EINECS 200-911-5 Grasex HSDB 2557 RCRA waste number U034 Trichloro-aoetaldehyde Trichloroethanal UN2075. Used in chemical synthesis and as a source of the drug chloral hydrate [302-17-0]. mp = -90° bp = 65.6° d = 1.273 soluble in H2O and organic solvents. Bristol-Myers Squibb Pharm. R D SmithKIine Beecham Pharm. 

When chlorine is passed into boiling ethanol, both chlorination of the methyl group and oxidation of the primary alcohol group to an aldehyde occur, giving trichloro-acetaldehyde or chloral ... 

In addition to chloroform, many other compounds containing the trichloro-methyl group, CI3C-, show marked physiological action. Thus trichloro-acetaldehyde or chloral hydrate, Cl3C CH(OH) (p. 342), and trichloro-tertiary-butanol or chloretone, CUC CfCHaliOH, are both hypnotics. Similarly, tribromo-ethanol or avertin, BraC-CHjOH, has strong anaesthetic properties. 

Acetaldehyde reacts with phosphoms pentachloride to produce 1,1-dichloroethane [75-34-3] and with hypochlorite and hypoiodite to yield chloroform [67-66-3] and iodoform [75-47-8], respectively. Phosgene [75-44-5] is produced by the reaction of carbon tetrachloride with acetaldehyde in the presence of anhydrous aluminum chloride (75). Chloroform reacts with acetaldehyde in the presence of potassium hydroxide and sodium amide to form l,l,l-trichloro-2-propanol [7789-89-1] (76). 

Gilbert, K.M., Whitlow, A.B., and Pumford, N.R., Environmental contaminant and disinfection by-product trichloro acetaldehyde stimulates T cells in vitro, Int. Immunopharmacol., 4, 25, 2004. 

Chloral hydrate Chloral hydrate, 2,2,2-trichloro-l,l-ethandiol (4.3.1), is synthesized either by chlorination of ethanol or chlorination of acetaldehyde and the subsequent addition of water molecules to the resulting trichloroacetic aldehyde [31],... 

Problem 15.68 Give the steps in the preparation of DDT, (p-CIC H4)2CHCCl3, from choral (trichloro-acetaldehyde) and chlorobenzene in the presence of H SO. ... 

Regioselective acylations of polyhydroxylated compounds such as carbohydrates, glycerols, steroids, or alkaloids have been carried out with lipases, esterases, and proteases [13, 20]. One example is the Candida antartica lipase (immobilized on acrylic resin) catalyzed monoacylation of the signalling steroid ectysone (1) giving selectively the 2-C)-acetate 2 (eq. (1)). Using vinyl acetate for this transesterification the reaction was irreversibly pushed to the product side, since the liberated enol instantaneously isomerizes to acetaldehyde [21]. The sometimes unfavorable aldehyde is avoided when 1-ethoxyvinyl acetates [22], trichloro- or -fluoroethyl esters [23 a, b], oxime esters [23 c] or thioesters [23 d] are employed for the quasi-irreversible reaction courses. 

The synthesis of trifluoromethylalkene dipeptide isosteres was reported by Wipf and coworkers [7]. As shown in Scheme 10.28, the multistep synthesis of Ala-XF[C(CF3)=CH]-Xaa type isosteres was achieved from l,l,l-trichloro-2,2,2-trifluoroethane. The carboxylation of trifluorotrichloroethane via trifluorodichloroethylzinc intermediate, esterification with benzyl alcohol, and Reformatsky addition-elimination with acetaldehyde... 

Blossom S, Pumford NR, Gilbert KM (2004) Activation and attenuation of apoptosis of CD4 T cells following in vivo exposure to two common environmental toxicants, trichloro-acetaldehyde hydrate and trichloroacetic acid. J Autoimmun, 23 211-220. 

Products were identified as 2,2,2-trichloroethanol and 2,2,2-trichloro-acetaldehyde by GC-MS and GC, respectively. Trichloroethanol (6.7 mu M) was completely degraded in 72 hours. When toluene was added to reaction mixtures, there was a 50% increase in the mineralization of (sup 14 C) TCE. M. vaccae s ability to cometabolize 2,4,6-trinitrotoluene (TNT) was also investigated. Two novel metabolites, as well as known reduction products, have been identified during catabolism of TNT with propane as cosubstrate. When M. vaccae was incubated with propane and (sup 14 C) TNT, 50% of the labelled carbon was found in the lipid fraction of cells. Analysis of this fraction demonstrated metabolism of sup 14 C into known phosphatides and other polar lipids indicating that ring cleavage had occurred. TNT or reduced intermediates were not found in any portion of the lipid fractions. 

Chloral can also be prepared by chlorinating aqueous acetaldehyde in preformed chloral626 or acetaldehyde in 7N-hydrochloric acid.627 In the latter case reaction is stopped after absorption of 1 mole of Cl2 at 18-20° at 35-40° chlorination leads to dichlorination and at 80-90° eventually to trichloro-acetaldehyde. 

Simple derivatives of (a-hydroxyalkyl)phosphonic and analogous acids have been obtained directly by procedures analogous to those adopted for the parent compounds. Thus, O-acetates of (2,2,2-trichloro-l-hydroxyethyl)phosphonic acid esters have been prepared through the interaction of the appropriate halogenated acetaldehyde and phosphorous-acetic acid anhydrides An aromatic aldehyde and dialkyl phospho-roisocyanatidite in the presence of water or an alcohol yields analogous 0-carbamoyl derivatives of (a-hydroxybenzyl)phosphonic diesters, probably through cyclic intermedi-ates ". ... 

Propane, 1,2-epoxy, 3,3,3-trichloro-. See 1,2-Epoxy-3,3,3-trichloropropane Propane, 1,1 -(ethylidenebis (oxy)) bis-. See Acetaldehyde dipropyl acetal Propane, 2-isocyanato-2-methyl-. See t-Butyl isocyanate... 

For synthesis of the monomer, chloral (trichloro acetaldehyde), see reference (2). 

---