Tris acetaldehyde

The reactions involved are similar in both cases, and closely parallel to those which give rise to chloroform. The sodium hypochlorite probably first oxidises the potassium iodide to potassium hypoiodite, which then oxidises the ethanol to acetaldehyde and then iodinates the latter to tri-iodo ... 

Gassman and co-workers developed a synthetic route from anilines to indoles and oxindoles which involves [2.3]-sigmatropic rearrangement of anilinosul-fonium ylides. These can be prepared from Ai-chloroanilines and ot-thiomcthyl-ketones or from an aniline and a chlorosulfonium salt[l]. The latter sequence is preferable for anilines with ER substituents. Rearrangement and cyclizalion occurs on treatment of the anilinosulfonium salts with EtjN. The initial cyclization product is a 3-(methylthio)indole and these can be desulfurized with Raney nickel. Use of 2-(methylthio)acetaldehyde generates 2,3-unsubstituled indoles after desulfurization[2]. Treatment of 3-methylthioindoles with tri-fiuoroacetic acid/thiosalieylie acid is a possible alternative to Raney nickel for desulfurization[3]. 

A reagent more reactive than tris(dimethylamino)arsine employed by Weingarten and White 39) was tetrakis(dimethylamino)titanium (145). With this compound it was possible to prepare N,N-dimethyl(l-isopropyl-2-methylpropcnyl)amine (147) from diisopropyl ketone. Weingarten and White 39) have suggested a possible mechanism for this reaction (see p. 88). If benzaldehyde 39,111), formaldehyde 111), or acetaldehyde 39) is used, the corresponding gem diamine or aminal (143) is formed. 

Historical. PE was first isolated by Tollens who was examining the effect of heat and reagents on formaldehyde. Apparently the crude formaldehyde he was working with contained a small % of acetaldehyde, which accounts for the PE formed. Although Tollens isolated it in 1882, it was not identified as PE until 1888 (Ref 2). Further details of the prepn and props of PE appeared in 1891 (Ref 3). The prepn is essentially a condensation betw 3 moles of formaldehyde and 1 of acetaldehyde to give an intermediate tris(hydroxymethyl)-acetaldehyde which is not isolated. An Intermolecular oxidn/redn then takes place betw this intermediate, and a 4th mole of formaldehyde, giving PE and formic ac (Ref 13, p 2). This type reaction is discussed under Cannizzaro Reaction in the Encycl (Vol 2, C25)... 

Pleopentaerythritol. A mixt of polypentaery-thritols consisting of di- and tri-pen taerythritols with some tetra- and other compds, which remain after the separation of PE from mother liquor in the prepn of PE by the condensation of formaldehyde and acetaldehyde in the presence of alkali... 

The ethyl radical directly attacks the heteroaromatic base, while the acetaldehyde acts as a source of acetyl radical. Photochemical oxy-alkylation has also been tried with ethers. The reaction has been successfully carried out with pyridines, quinolines, isoquinolines,cinno-lines, and quinoxalines. Particularly good yields were obtained with caffeine (16) (Scheme 14). ... 

This method accommodates aryl aldehydes with both electron-deficient and electron-rich aryl substitutents. Acetaldehyde is also a competent couphng partner, providing the corresponding amido ketone in 62% yield. Acyl substitution of the tosyl amide varies to include hydrogen, methyl, tert-butoxy, and phenyl producing the desired a-amido ketones in moderate to high yields. Expansion of this methodology to synthesize di- and tri-substituted imidazoles was reported by Murry and co-workers (Scheme 7) [54]. 

Figure 2. Illustration of the importance of the choice of reaction conditions on the determination of initial velocity. Shown are four conditions applied to examine the rate behavior of Escherichia coli NAD+-dependent coenzyme A-linked aldehyde dehydrogenase (Reaction NAD+ + CoA-SH + Acetaldehyde = NADH + Acetyl-S-CoA + H+). All assay mixtures contained enzyme, 0.5 mM NAD+, 8 /jlW CoA-SFI, 16 mM acetaldehyde, and 22.5 mM Tris buffer at pFI 8.1. (a) Time-course observed when enzyme was added to the standard assay (b) time-course observed when enzyme was added to standard assay augmented with 10 mM 2-mercaptoethanol (c) time-course observed when enzyme was first preincubated for 15 min with 8 /jlW CoA-SH, 16 mM acetaldehyde, 10 mM 2-mercaptoethanol, and 22.5 mM Tris buffer at pH 8.1, and the reaction was initiated by addition of NAD+ (d) time-course observed when enzyme was preincubated with lOmM 2-mercaptoethanol for 15 min andthen addedtostandard assay augmented with 10 mM 2-mercaptoethanol. The data are most compatible with the idea that the enzyme has an active-site thiol group that must be reduced to express full catalytic activity during assay.

This pyridoxal-phosphate-dependent enzyme [EC 2.1.2.1], which has a recommended EC name of glycine hydroxymethyltransferase, catalyzes the reversible reaction of 5,10-methylenetetrahydrofolate with glycine and water to produce tetrahydrofolate and L-serine. The enzyme will also catalyze the reaction of glycine with acetaldehyde to form L-threonine as well as with 4-tri-methylammoniobutanal to form 3-hydioxy-N, N, N -trimethyl-L-lysine. 

Optimization of the previously reported Mannich-type reaction of trimethyl (pent-2-en-3-yloxy)silane with the sulfone Is derived from phenyl acetaldehyde (Table 5, entry 11) led to the corresponding (3-amino ketone in a good yield with moderate diastereoselectivity (2 mol% Bi(0Tf)3-4H20, yield = 84%, 24v/24v syn/anti = 72 28) (Scheme 8). Reduction of the major diastereoisomer 24v with lithium tri-ferf-butoxyaluminohydride afforded 25 as the only one diastereoisomer. Further cyclization of the latter with NaH afforded 4-benzyl-6-ethyl-5-methyl-l,3-oxazinan-2-one 26. The relative configuration of the six-membered carbamate was established as cis-cis by NMR analysis. 

Students may have seen the acetaldehyde decomposition reaction system described as an example of the application of the pseudo steady state (PSS), which is usually covered in courses in chemical kinetics. We dealt with this assumption in Chapter 4 (along with the equilibrium step assumption) in the section on approximate methods for handling multiple reaction systems. In this approximation one tries to approximate a set of reactions by a simpler single reaction by invoking the pseudo steady state on suitable intermediate species. 

Just to check that you ve understood these ideas, what would happen if we tried to condense acetaldehyde as enolic component with benzophenone (PhsC o) ... 

Not only can the a-methylene carbanion be produced and stabilized, but it can also undergo base-catalyzed aldol-type reactions without decomposition of the chelate ring. The most-studied reactions involve carbanion additions to acetaldehyde to produce threonine and allothreonine. This can be achieved for bis(glycinato)copper(II),48,49 tris(glycinato)cobalt(III)50,51 or glycinato-bis(l,2-diaminoethane)cobalt(III),52 with the best yield being obtained in the last case, where the... 

The IUPAC rules for naming aldehydes append the suffix -al to the parent name. The aldehyde carbon is always the first carbon in the chain, so a locant is not necessary. The simplest aldehyde, methanal, is commonly known as formaldehyde, a highly toxic gas used to preserve biological specimens. Ethanal is the next aldehyde, although most organic chemists call it acetaldehyde. 2,2,2-Tri-chloroethanal, more commonly known as chloral, reacts with water to form the sedative chloral hydrate. Phenylmethanal, more commonly known as benzalde-hyde, is used as artificial cherry or almond flavoring. Nomenclature examples of aldehydes are shown in Figure 11.34. 

Chemically these are described as mono-, di-, and tri-substituted acetaldehydes. 

Synthesis of (-I-) calanolide A (Scheme 8-11) was achieved by enzyme catalyzed resolution of the aldol products ( )-53. Compound 7 with acetaldehyde by aldol reaction in the presence of LDA/TiCU stereoselectively produced a mixmre of ( )-53 and ( )-54 (94% yield), the ratio of which was 96 4. ( )-53 was then resolved by lipase AK-catalyzed acylation reaction in the presence of tert-butyl methyl ether and vinyl acetate at 40 °C to obtain 41% yield of (+)-55 and 54% yield of the acetate (—)-56. Mitsunobu cyclization of (+)-55 in the presence of tri-phenylphosphine and dielthyl azodicarboxylate afforded 63% yield of (-l-)-43 with 94% ee as determined by chiral HPLC. Luche reaction on (+)-43 with CeCla 7H2O and triphenyl phosphine oxide and NaBH4 in the presence of ethanol at 30 °C gave the crude product. It was purified by column chromatography on silica gel to give 78% yield of a mixture containing 90% of (+)-calanolide A and 10% (+)-calanohde B, which were further separated by HPLC. 

Boron Enolates. The oxazinones can be converted to their corresponding boron enolates by treatment with Di-n-butylboryl Tri-fluoromethanesulfonate and Triethylamine in CH2CI2. The boron enolates react with aldehydes at —78 °C to give p-(hydroxy)alkyl-substituted oxazinones. Condensation of the boron enolate with acetaldehyde followed by recrystallization of the major product and then deprotection affords allothreonine (eqs 8 and 9). This approach has been used in the asymmetric synthesis of di-aminopimelic acid and derivatives thereof. ... 

---