Glycerol acrolein

Hazardous Decomp. Prods. CO, CO2, heated to decomp., emits acrid smoke and fumes NFPA Health 4, Flammability 3, Reactivity 1 Uses Intermediate for pharmaceuticals and other org. chemicals mfg. of glycerol, acrolein, herbicides, resins, plasticizers, allyl diglycol carbonate, allyl glycidyl ether, crosslinking agents solvent Regulatory SARA reportable Manuf./Distrib. ABCR UK http //www.abcr.de, Aldrich http //www.sigma-aidrich.com, Alfa Aesar http //www.aifa.com. Avocado Research... 

HC CH(0H) CH20H. optically active. D-glyceraldehyde is a colourless syrup. May be prepared by mild oxidation of glycerol or by hydrolysis of glyceraldehyde acetal (prepared by oxidation of acrolein acetol). DL-glyceraldehyde forms colourless dimers, m.p. IBS-S C. Converted to methylglyoxal by warm dilute sulphuric acid. The enantiomers... 

When a mixture of aniline, nitrobenzene, glycerol and concentrated sulphuric acid is heated, a vigorous reaction occurs with the formation of quinoline. It is probable that the sulphuric acid first dehydrates the glycerol giving acrolein or acraldehyde (A), which then condenses at its double bond with the amino group of the aniline to give acrolein-aniline (B), The latter in its enol... 

I. Acrolein test. Heat 0-5 ml. with about i g. of finely powdered KHSO4. Acrolein, CH2 CH CHO, produced by dehydration of the glycerol, is readily detected by its characteristic and irritating odour smell cautiously). 

The simplest a 3 unsaturated aldehyde acrolein is prepared by heating glycerol with an acid catalyst Suggest a mechanism for this reaction... 

Glycerol, the simplest trihydric alcohol, forms esters, ethers, haUdes, amines, aldehydes, and such unsaturated compounds as acrolein (qv). As an alcohol, glycerol also has the abiUty to form salts such as sodium glyceroxide (see also Alcohols, polyhydric). 

Since aHyl chloride could be converted to glycerol by several routes, the synthesis of glycerol from propylene [115-07-1] became possible. Propylene can also be oxidized in high yields to acrolein [107-02-8]. Several routes for conversion of acrolein to glycerol are shown in Figure 1. 

By substituting paraldehyde for glycerol, 2-methylquinoline [27601-00-9] may be synthesized. The Skraup synthesis is regarded as an example of the broader Doebner-von Miller synthesis. In the case of the Skraup synthesis, the glycerol undergoes an acid-catalyzed dehydration to provide a small concentration of acrolein that is the reactive species. If acrolein itself is used as a reactant, it would polymerize. Crotonaldehyde is the reactive intermediate in the Doebner-von Miller synthesis (28). 

Lactic acid bacteria are common contaminants of distillers fermentations. E. lactis may produce excessive amounts of volatile acids. Some species convert glycerol to fdpropionaldehyde which may break down to acrolein during distillation, producing an acrid odor. 

S K R A U P Quitxiline synthesis Quinoline synthesis from anilines and acrolein or glycerol... 

Before the final assembling of the apparatus, the flasks are charged as follows One kilo of freshly fused and finely powdered acid potassium sulfate, 200 g. of powdered potassium sulfate, and 300 g. of dry glycerol (Note 3) are thoroughly mixed in each of flasks B and D. In each of flasks I and M is placed about i g. of hydroquinone to act as a stabilizer for the acrolein (Moureu, Compt. rend., 170, 26 (1920)). 

Satisfactory methods for the preparation of acrolein have been described by Wohl and Mylo,i Witzemann, andMoureu. In the Wohl and Mylo method the vapors of glycerol are passed over magnesium sulfate maintained at 330-340.° Witzemann s method involves the use of magnesium sulfate at elevated temperatures with the consequent danger of breaking the generating flasks. Moureu s method involves apparatus not always available. 

Benzanthrone has been prepared by three general methods, the first of which is generally regarded as the best (i) by heating a reduction product of anthraquinone with sulfuric acid and glycerol,1 or with a derivative of glycerol, or with acrolein. The anthraquinone is usually reduced in sulfuric acid solution, just prior to the reaction, by means of aniline sulfate, iron, , or copper. It has also been prepared (2) by the action of aluminum or ferric chloride on phenyl-a-naphthyl ketone, and (3) from i-phenylnaphthalene-2-carboxylic acid. ... 

Quinoline.—The formation of c[uinoline by Skratip s reaction may be explained as follows - The sulphuric acid converts the glycerol into aciolein, which then combines w-ith the aniline to form acrolein-aniline. The latter on o.xidation with nitrobenzene yields quinoline. 

For the Skraup synthesis, glycerol 2 is used as starting material in the presence of concentrated sulfuric acid (see scheme above) it is dehydrated to acrolein 6. Although it is assumed that the reactive carbonyl component in the Skraup reaction actually is acrolein, attempts to use acrolein directly, instead of glycerol, proved to be unsuccessful." ... 

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. ... 

Other routes for obtaining glycerol are also based on propylene. It can be produced from allyl chloride or from acrolein and isopropanol (see following sections). 

Biomass is a renewable resource from which various useful chemicals and fuels can be produced. Glycerol, obtained as a co-product of the transesterification of vegetable oils to produce biodiesel, is a potential building block to be processed in biorefineries (1,2). Attention has been recently paid to the conversion of glycerol to chemicals, such as propanediols (3, 4), acrolein (5, 6), or glyceric acid (7, 8). 

Several methods and reaction pathways have been reported for the conversion of glycerol in the literature, such as etherification, esterification [1], and oxidation [2], Via ionic dehydration acetol [3] and acrolein can be produced. The radical steps result in aldehydes, allyl alcohol, etc. [4], If the dehydration is followed by a hydrogenation step, propanediols (1,2- or 1,3-) can be obtained [5-6]. 

Northern crayfish, Orconectes viritis 101 pg/L for 7 days Acrolein not detected in tissues glycerol and lactic acid were the major metabolites 25... 

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