Acrolein derivatives

Of these producers, Atochem, Degussa, and Daicel are reported to be in the merchant acrolein business. Union Carbide suppHes only the acrolein derivative markets. Rhc ne-Poulenc also produces acrolein, primarily as a nonisolated intermediate to make methionine. A number of other small scale plants are located worldwide which also produce acrolein as an intermediate to make methionine. 

Many other acrolein derivatives produced via Diels-Alder reactions are classified as flavors and fragrances. Among those of commercial interest are lyral, (1) [31906-04-4] (91,92) andmyrac aldehyde, C 3H2oO, (2) [80450-04-0] (92,93). 

The crude dibromohydrin distils without any decomposition at 10-15 pressure if the temperature of the oil bath is not raised over 190°. Above this temperature formation of acrolein derivatives begins, which, even if present in very small amounts, makes the dibromohydrin lachrymatory. 

Villsmeier reaction on the dimethylacetal of methoxyacetaldehyde (141) with phosgene and dimethyIformamide affords the acrolein derivative, 142. Condensation of this with guanidine gives the pyrimidine, 143. (The enamine can be viewed as a latent aldehyde-the dimethylamino group is probably lost in the course of an addition elimination reaction with one of the guanidine groups.) This pyrimidine serves as starting material for sulfameter (111). ... 

Thermal ene reactions of 3-(alk-2-enyl)benzylamino-2-(methoxycarbonyl) acrolein derivatives have been reported to give the substituted 4,5-dihydro-lff-azepines 3 (R = H, Me, Ph, 2-furyl, CC Et) in good yield <00T1299>. 

The modification of the CpFe(L)2+ fragment in 39 with chiral phosphorus donor ligands based on chiral 1,2-dioles was investigated by Kxindig and coworkers and tested in the reaction of acrolein derivatives (Scheme 9.28) [72-74],... 

However, in the presence of Lewis acids such as AlBr3, without the presence of the CpFe(CO)2+ Lewis acid the [3 + 2[-cycloaddition process was more effective, giving the product in 45% yield. The application of a chiral cationic CpFe(diphosphine) complex as the catalyst (Scheme 9.37) for the asymmetric [3 + 2]-cycloaddition of nitrones to acrolein derivatives was described by Kiindig and coworkers [95],... 

The moderate Lewis acidity of ruthenium complexes was used to promote catalytic Diels-Alder reaction of dienes and acrolein derivatives [21-23]. The enantioselective Diels-Alder reaction of methacrolein with dienes was catalyzed with cationic ruthenium complexes containing an arene or cyclo-pentadienyl (Cp) ligand and a chiral ligand such as phosphinooxazoline, pyridyl-oxazoline, monoxidized 2,2 -bis(diphenylphosphino)-1, T-binaphthyl (BINPO)or l,2-bis[bis(pentafluorophenyl)phosphanyloxy]-l,2-diphenylethane (BIPHOP-F). The reaction gave the cycloadduct in high yields with excellent... 

Purified yeast Pol is able to perform limited nucleotide insertions opposite several DNA lesions such as TT (6-4) photoproduct, AAF-dG adduct, and (+) or ( )-trans-anti-BPDE-N2-dG adduct. Furthermore, Pol also catalyzes extension synthesis from opposite many types of lesions with varying efficiencies, including an AP site, cis-syn TT dimer, (64) photoproduct, AAF-dG adduct, (+) or (-)-trans-an//-BPDE-/V2-dG adduct, and an acrolein-derived dG adduct. Therefore, it has been proposed that Pol functions both as an insertion polymerase and an extension polymerase. It appears that the extension activity of Pol is versatile. Thus, it is believed that Pol is a major extension polymerase during translesion synthesis in eukaryotes. 

Diels-Alder reactions of cyclopentadiene and methacrolein with crotonaldehyde are also catalyzed by complexes formed in situ between NbCls or TaCls and bidentate ligands (2 equiv.) such as L-tartrate esters, or a-amino acids (e.g. tryptophan, alanine). Yields with the Ta catalysts are often somewhat better (14-78 %) than with the Nb catalysts. Good exo. endo ratios are obtained but enantioselectivities are still low (7-40 % ee) [185]. Methylrhenium trioxide is an efficient catalyst in these reactions and its best performance is in aqueous solution. Acrolein derivatives and methyl vinyl ketones react with a variety of dienes to give single diastereoisomers in very high yield with as little as 1 % catalyst loading [186]. Examples are shown in Sch. 49. The reaction is sluggish with disubstituted dienophiles and dienes. 

Pheny]-3 dimethy]aminoacrolein is a useful synthon as it reacts with 2 amino> azoles or 2-aminoazines with loss of the t-amino group. Hydrogenation converts it into indole-3-carboxaldehyde in low (15%) yield. Another synthetically useful acrolein derivative is the ( anoacetal (54.6), which cyclizes amino-iV-heterocycles on heating in methanol-hydrochloric acid. 

R. S. (2008) Mutagenic potential of DNA-peptide crosslinks mediated by acrolein-derived DNA adducts. Mutat. Res., 637, 161-172. 

Scheme 9.3 DNA interstrand cross-link formation mediated by the acrolein-derived y-OH-PdC adduct.

Zhang, S., Villalta, P., Wang, M., and Hecht, S. (2007) Detection and quantitation of acrolein-derived l.N -propanode-oxyguanosine adducts in human lung by liquid chromatography-electrospray ionization-tandem mass spectrometry. Chem. Res. Toxicol., 20, 565-571. 

Kanuri, M., Minko, I., Nechev, L., Harris, T., Harris, C., and Uoyd, R. (2002) Error prone translesion synthesis past y-hydroxypropano deoxyguanosine, the primary acrolein-derived adduct in... 

A., Tamura, P., Jacob, J., Voehler, M., Harris, T.M., Lloyd, R.S., Rizzo, C.J., and Stone, M.P. (2005) Spectroscopic characterization of interstrand carbinolamine cross-links formed in the 5 -CpG-3 sequence by the acrolein-derived y-OH-1, N2-propano-2 -deoxyguanosine DNA adduct. J. Am. Chem. Soc., 127,17686-17696. 

Nair, D.T., Johnson, R.E., Prakash, L., Prakash, S., and Aggarwal, A.K. (2008) Protein-template-directed synthesis across an acrolein-derived DNA adduct by yeast Revl DNA polymerase. Structure, 16, 239-245. 

Cases in which the attacking nucleophile is present in the silene molecule itself have also been reported. The ring closure of the silicon analogues of an acrolein derivative and thioacrolein to silaoxetenes232 and silathietenes233, which immediately undergo a 2 + 2 cleavage to yield an acetylene and a silanone or silanethione, has been proposed to account for the results of flash vacuum pyrolysis of silylated ketenes and thioketenes (equation 110). 

Yang, I.-Y, Miller, H., Wang, Z., Frank, E. G., Ohmori, H., Hanaoka, F., and Moriya, M. (2003). Mammalian translesion DNA synthesis across an acrolein-derived deoxy-guanosine adduct J. Biol. Chem. 278, 13989-13994. 

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