Cinnamal chloride

The alcoholysis of cinnamal chloride was followed by measuring the optical density of the reaction mixture. (Andrews, JACS 69 3062, 1947). The... 

Fifty grams (0.38 mole) of freshly distilled cinnamaldehyde is added to 85 g. of phosphorus pentachloride with agitation and exclusion of moisture from the apparatus. The mixture is stirred and heated on a water bath for 2-3 hours. The excess phosphorus pentachloride and the phosphorus oxychloride are distilled off under vacuum, and the residue is subjected to further vacuum distillation. The product is collected at 121-122°/14 mm., and the solid obtained is recrystallized from petroleum ether (b.p. 40-60°). Cinnamal chloride is obtained in 82-85% yield, and the product melts at 58.5-59°. 

Cinnamic acid chloride Cinnamic chloride Cinnamoyl chloride EINECS 203-065-5 NSC 4683 p-Phenylactyloyl chloride 3-Phenyl-2-propenoyl chloride 2-Propenoyl chloride, 3-phenyl-. Reagent for determination of small amounts of water, chemical intermediate. Yellow crystals mp = 36° bp = 257°, bp2 = 101° d = 1.1617 very soluble in ligroin. ICI Spec. Janssen Chimica LatKaster Synthesis Co. Penta Mfg. Pfalz Bauer. 

Cinnamic acid, 3-phenyl propyl ester. See 3-Phenylpropyl cinnamate Cinnamic alcohol. SeeCinnamyl alcohol, Cinnamic aldehyde. See Cinnamal Cinnamic aldehyde ethylene glycol acetal. See Cinnamaldehyde ethylene glycol acetal Cinnamic chloride. See Cinnamoyl chloride Cinnamol. See Styrene Cinnamomum camphora. See Camphor Cinnamomum camphora oil. See Camphor (Cinnamomum camphora) oii Cinnamomum cassia. See Cinnamon (Cinnamomum cassia) extract Cinnamon (Cinnamomum cassia) Cinnamon (Cinnamomum cassia) oii... 

CAS 102-92-1 EINECS/ELINCS 203-065-5 Synonyms Cinnamic acid chloride Cinnamic chloride Cinnamoyl chloride, predominantly... 

Feruloyl Esterases. Psychrophilic feruloyl esterases are employed in industry for biomass degradation, biotransformation, and isolation of ferulic acid derivatives useful as antioxidant, antimicrobial, and photoprotectant properties. For instance, one studied feruloyl esterase from the psychrophilic bacterium, P. haloplanktis TAG 125, is a family 1 carbohydrate esterase and displays significant activity toward pNP-acetate, a- and yS-naphthyl acetate, and 4-methylumbelliferyl p-trimethylammonio cinnamate chloride (a model substrate for determining ferulolyl esterase activity) (23). 

Cinnamic acid can be readily esterified by the Fischer-Speier method without any risk of the addition of hydrogen chloride at the double bond. Proceed precisely as for the preparation of ethyl benzoate (p. 104), using 20 g. of cinnamic acid and 20 ml. of rectified spirit. When the crude product is poured into water, a sharp separation of the ester is not readily obtained, and hence the addition of about 10 ml. of carbon tetrachloride is particularly desirable. Finally distil off the carbon... 

Benzal chloride is hydrolyzed to benzaldehyde under both acid and alkaline conditions. Typical conditions include reaction with steam in the presence of ferric chloride or a zinc phosphate catalyst (22) and reaction at 100°C with water containing an organic amine (23). Cinnamic acid in low yield is formed by heating benzal chloride and potassium acetate with an amine as catalyst (24). 

Nearly all uses and appHcations of benzyl chloride are related to reactions of the active haUde substituent. More than two-thirds of benzyl chloride produced is used in the manufacture of benzyl butyl-phthalate, a plasticizer used extensively in vinyl flooring and other flexible poly(vinyl chloride) uses such as food packaging. Other significant uses are the manufacture of benzyl alcohol [100-51-6] and of benzyl chloride-derived quaternary ammonium compounds, each of which consumes more than 10% of the benzyl chloride produced. Smaller volume uses include the manufacture of benzyl cyanide [140-29-4], benzyl esters such as benzyl acetate [140-11-4], butyrate, cinnamate, and saUcylate, benzylamine [100-46-9], and benzyl dimethyl amine [103-83-8], and -benzylphenol [101-53-1]. In the dye industry benzyl chloride is used as an intermediate in the manufacture of triphenylmethane dyes (qv). First generation derivatives of benzyl chloride are processed further to pharmaceutical, perfume, and flavor products. 

Treatment of benzal chloride [98-87-3] with anhydrous sodium acetate at 180—200°C provides another economically attractive route to cinnamic... 

The chloride is readily available as a by-product of benzyl chloride [100-44-7] production (see Chlorocarbon and chlorohydrocarbons-BENZYL chloride, BENZAL CHLORIDE, AND benzotrichloride). The yield is comparable to the Perkin-based process, but the difficulty associated with removal of trace halogenated impurities makes the resultant cinnamic acid less desirable for many appHcations. 

As with poly(vinyl alcohol), poly(vinyl cinnamate) is prepared by chemical modification of another polymer rather than from monomer . One process is to treat poly(vinyl alcohol) with cinnamoyl chloride and pyridine but this is rather slow. Use of the Schotten Baumann reaction will, however, allow esterification to proceed at a reasonable rate. In one example poly(vinyl alcohol) of degree of polymerisation 1400 and degree of saponification of 95% was dissolved in water. To this was added a concentrated potassium hydroxide solution and then cinnamoyl chloride in methyl ethyl ketone. The product was, in effect a vinyl alcohol-vinyl cinnamate copolymer Figure 14.8)... 

Condensation of m-fluorobenzaldehyde with malonic acid leads to the trans cinnamic acid 96 acylation of the acid chloride with cyclopropylaminc leads to amide 97 (cinflumide), a muscle relaxant [24]. 

Ethylene oxide (2.5 ml, 0.05 mole) is condensed in a 50-ml round-bottom flask containing 5 ml of methylene chloride by introducing the gas via a tube into the ice-cooled flask. To the cooled flask are added triphenylphosphine (6.6 g, 0.025 mole), benzaldehyde (2.6 g, 0.025 mole), and ethyl bromoacetate (4.2 g, 0.025 mole). The flask is closed with a drying tube, brought to room temperature, and allowed to stand overnight. Fractional distillation of the solution then yields 2-bromoethanol, bp 55717 mm followed by the desired ethyl cinnamate, bp 142-144717 mm (27171 atm) in about 90% yield. The residue consists of triphenylphosphine oxide, mp 150°. 

Benzyl Ginnamate.—The cinnamic acid ester of benzyl alcohol is a natural constituent of storax, tolu, and Peru balsams. It is a crystalline Bubstance with a characteristic sweet balsamic odour. It may be prepared by heating sodium cinnamate, alcohol, and benzyl chloride together under a reflux condenser. It is a useful ester where a sweet balsamic odour is required to be introduced into a perfume, especially cf the heavy type. It forms white, glistening prisms, which melt at 39°, and.decompose when heated to 350°. The best commercial specimens have the following characters —... 

Pentaerythritol Tetrabenzoate, C33H2808, mw 552.55, OB to C02 -208.5% needles, mp 99—101° prepd by the action of Bz chloride on PE (Refs 1 2). A mixt of PETN with PE tetrabenzoate and a PE cinnamate (structure unspecified) has been patented as a progressive burning gun pro pint (Ref 3)... 

The arylation of alkenes by treatment with a diazonium chloride (or bromide) solution and cupric chloride (or bromide) is called the Meerwein arylation reaction, after its discoverer (Meerwein et al., 1939). Originally, it was discovered using a,P-unsaturated carbonyl compounds, namely coumarin (Scheme 10-43) and cinnamic derivatives (Schemes 10-44 and 10-45). As Scheme 10-45 shows, the Meerwein reac-... 

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