Preparation from acrolein

P-Picoline may serve as an important source of nicotinic acid [59-67-6] for dietary supplements. A variety of substituted pyridines may be prepared from acrolein (75—83). 

The main use of acrolein is to produce acrylic acid and its esters. Acrolein is also an intermediate in the synthesis of pharmaceuticals and herhicides. It may also he used to produce glycerol hy reaction with isopropanol (discussed later in this chapter). 2-Hexanedial, which could he a precursor for adipic acid and hexamethylene-diamine, may he prepared from acrolein Tail to tail dimenization of acrolein using ruthenium catalyst produces trans-2-hexanedial. The trimer, trans-6-hydroxy-5-formyl-2,7-octadienal is coproduced. Acrolein, may also he a precursor for 1,3-propanediol. Hydrolysis of acrolein produces 3-hydroxypropionalde-hyde which could he hydrogenated to 1,3-propanediol. ... 

Due to their physiological importance, considerable efforts are currently devoted towards the total synthesis of 2,3-methanoamino acids (ACCs). The parent compound ACC 71 has been readily prepared from acrolein, through the base-induced (K2CO3) cyclization of 2-amino-4-chlorobutyronitrile [96] or from one-pot Strecker reaction of cyclopropanone hemiacetal [97]. 

Ethanal, propanal, butanal, heptanal and 3-phenylpropanal were obtained commercially. 3-Trimethylsilylpropanal was prepared from acrolein and trimethylsilyl chloride in tetrahydrofuran at about — 50 °C (5). 

Acetalization. /7-Chloropropionaldchydc diethyl acetal can be prepared from acrolein in 88% yield by reaction of ethanol in the presence of hydrogen chloride dissolved in ether and with a 4 A molecular sieve as water scavenger.2 In the absence of a molecular sieve the yield drops to 65%. If elhanolic hydrogen chloride is used the yield is 34%.3... 

An efficient asymmetric total synthesis of L-fructose combines the Sharpless asymmetric dihydroxylation with an enzyme-catalyzed aldol reaction. L-Glyceraldehyde, prepared from acrolein, is condensed to DHAP in a buffered water suspension of lysed cells of KI2 Escherichia coli containing an excess of L-rhamnulose-1-phosphate (Rha) aldolase E. coli raised on L-rhamnose as sole carbon source). The L-fructose phosphate obtained is hydrolyzed to L-fructose with acid phosphatase. Similarly, the RAMA-catalyzed condensation of D-glyceraldehyde with DHAP,... 

There are several reports in the literature of the synthesis of a-unsaturated y-sultones via the dehydrohalogenation of saturated halogenated y-sultones19,59,67,68. This general mode of synthesis is illustrated in equation 51. The sodium 2-alkenesulphonate was prepared from acrolein by earlier workers67,68, but more recently Roberts and his coworkers reported a much simplified synthesis via the sulphonation of 1-alkenes10. There is also a report59 of the preparation of a-unsaturated -sultones, a,y-unsaturated S-sultones and di-unsaturated y-sultones from the / -unsaturated <5-sultone 21 (equation 52). 

Glycerose forms an osazone, which melts at 131°. Glyceric aldehyde, which shows the properties of the aldoses, may be prepared from acrolein as indicated here —... 

Vlnyl-l,3-dloxane has been reported to be prepared from acrolein, 1,3-propanedlol and NATION at a rate of 16 M per hour at 82% acrolein conversion (24). 

DL-Met is prepared on the industrial scale (more than 100,000 tons annually) by a Strecker synthesis, using P-methylmercaptopropionaldehyde prepared from acrolein and methylmercaptan. nt-Met is used to supplement poltry feed. Both d- and L-forms are effective, so that no prior separation of enantiomers is necessary. [F.Takusagawa et al. Crystal Structure of S-Adenosylmethionine Synthetase / BioL Chem. 271 (1996) 136-147]... 

Vinyl-substituted cyanoacrylates have been used from time to time, either as modifiers for alkyl cyanoacrylates or on their own as adhesives. These cyanopentadienoates (2) are less reactive toward anionic polymerization than are the cyanoacrylates. This feature allows their preparation from acrolein and a cyanoacetate ester using a Lewis acid catalyst such as zinc chloride. " The monomer can be isolated and purified without going through a depolymerization step. 

Considering only one example, an equimolar mixture of 22D and MA converts to a 100% yield of copolymer when heated in toluene for 2-3 h at 55-60°C, with 1.0 wt. % AIBN initiator. In the preparation, the solid polymer precipitates rapidly from the toluene after only a few minutes reaction time. Linear and cyclic acetals with vinyl unsaturation are easily prepared from acrolein and alcohols or glycols. Monomers such as acrolein diethylacetal... 

The bicyclic acetal, 6,8-DBO, possesses the structural skeleton of the 1,6-anhydrosugars and, because it is readily prepared from acrolein dimer, its cationic polymerization has been investigated. Mostly Lewis acids (BF3, PF5) were used as initiators, and at low temperature (-78 °C) polymers with Mn up to 10 could be obtained although dispersity was broad. ... 

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