Crotonic acid chloride

Propylaminobutyric acid dimethyl amide is dissolved in benzene and while cooling, crotonic acid chloride is added and mixed. Then, reaction mixture is filtered and freed from benzene to give 2-(N-propyl-crotonylamido)butyric acid dimethyl amide, melting point 128°-130°C. 

Product isolation is very simple as only the solvent has to be removed after separation from the polymer. The polymer can be returned to the active chlorinating agent by reaction with carbonyl chloride. A variation of this procedure does not require polymer-bound phosphorus halide but uses Lewis acid-Lewis base complexes between anion-exchange resins, such as Amberlite IRA 93, and phosphorus pentachloride (equation 4). Again, isolation of the resultant acid chloride is simple and the exhausted polymer can be regenerated for further use by simply washing it with aqueous acidic and basic solutions. Yields range from 51 % for crotonic acid chloride to 86% for decanoic acid chloride. 

The acylation of 10-undecenoic acid [2a] with acrylic acid chloride, carried out under the same reaction conditions used for the acylation of [la] with crotonic acid chloride, gave the corresponding allyl vinyl ketone [11] as a mixture of the (E)- and (Z)-stereoisomers [ E)] [ Z)] = 3 1, Fig. 4). Because of their allyl vinyl keto functionality, [10] and [11] should be suitable substrates for the Nazarov reaction. 

SCHEME 5. Nazarov cyclization of acylation product [10] obtained from the reaction of oleic acid [la] and crotonic acid chloride... 

Mix together in a 250 ml. flask carrying a reflux condenser and a calcium chloride drying tube 25 g. (32 ml.) of freshly-distilled acetaldehyde with a solution of 59-5 g. of dry, powdered malonic acid (Section 111,157) in 67 g. (68-5 ml.) of dry pyridine to which 0-5 ml. of piperidine has been added. Leave in an ice chest or refrigerator for 24 hours. Warm the mixture on a steam bath until the evolution of carbon dioxide ceases. Cool in ice, add 60 ml. of 1 1 sulphuric acid (by volume) and leave in the ice bath for 3-4 hours. Collect the crude crotonic acid (ca. 27 g.) which has separated by suction filtration. Extract the mother liquor with three 25 ml. portions of ether, dry the ethereal extract, and evaporate the ether the residual crude acid weighs 6 g. Recrystallise from light petroleum, b.p. 60-80° the yield of erude crotonic acid, m.p. 72°, is 20 g. 

Crotonic acid, esterification with sec-butyl alcohol, 41, 60 Crystal Violet, from condensation of oxalyl chloride with dimethyl-aniline, 41, 2-4... 

When aqueous NaOH is given as a base, isomerization of the product butenoic acids can be extensive depending on the nature and concentration of base. In dilute aqueous solutions alcohols do not react to form the respective esters, however, the reactions are strongly accelerated due to the increased solubility of the substrates in the catalyst-containing aqueous-alcoholic phase. For example, with 23-33 % (v/v) ethanol in water the [PdCl2(TPPTS)2]-catalyzed hydroxycarbonylation of allyl chloride proceeded with TOF-s of 1850-2400 h and with a vinylacetic/crotonic acid ratio of 21 [16]. Addition of [CuCb] increased the overall conversion rate (by a factor of 2 at [Cu]/[Pd] = 8) but at the same time the side reactions... 

Ethyl-3-methylpyridine (also known as aldehyde-collidine ) has been prepared by heating aldehyde-ammonia aldehyde-ammonia and acetaldehyde or paraldehyde aldol-ammonia and ammonia paraldehyde and ammonia <> 11,12 acetamide,1 or acetamide and phosphorus pentoxide ethylene glycol and ammonium chloride ethylidene chloride or bromide and ammonia ethylidene chloride and acetamide, ethylamine, or n-amylamine crotonic acid and a calcium chloride-ammonia complex 1 and by passage of acetylene or acetaldehyde and ammonia over alumina and other catalysts. 

It is customary to prepare the ester by reaction of the phenol with an unsaturated acid chloride, generally in the absence of solvents. Again, crotonic and 3,3-dimethylacrylic acid... 

Chromium trioxide, 60, 21 Clemmensen reaction, 60, 111 Copper chloride (CuCl) [7758-89-6], 61, 122 Crotonic acid, ethyl ester, ( )-, 61, 85 18-Crown-6-potassium cyanide complex, 60,129 Crum Brown-Walker reaction, 60, 4 Cuprous chloride, 60, 42, 121 61, 122 CYANIC ACID, PHENYL ESTER [1122-85-6], 61, 35... 

Other functional groups may be present in the molecule containing the double bond. Methallyl alcohol, H2C = C(CHjX HjOH, is hydrated by a mixture of 25% sulfuric acid in the presence of isobutyraldehyde to give the cyclic acetal of isobutylene glycol with the aldehyde. Hydrolysis of the acetal by dilute mineral acid gives isobutylene glycol (94%). Hydration of the double bond by aqueous sulfuric acid has been used to make chloro-i-butyl alcohol from methallyl chloride and /S-hydroxybutyric acid from crotonic acid. ... 

Benzene Benzoic acid Betol -Lead -Bromine Lead chloride Lead iodide -a-Crotonic acid -Diphenylamine -p-Dibrom benzene Acetic acid -Potassium -Potassium nitrate Laurie acid -Myristic acid... 

Seven grams of crystallised crotonic acid in 50 c.c. of warm water are heated with 7 grams of mercuric oxide until complete solution takes place. The solution is then evaporated to about 25 c.c., cooled, and treated with 200 e.c. of absolute alcohol. The white precipitate is washed with alcohol and ether, and dried over calcium chloride. 

An analogous methodology can be seen in the proposal to use chloroformamidinium salts as dehydrating agents. A A A /V -Tetramethylchloroformamidinium chloride, used as the condensation agent, is easily available by the reaction of A A A A -tetramethylurea and oxalyl dichloiide. The reaction of carboxylic acids (equation 33) can be achieved at -30 C in the presence of tiiethylamine. Thus, for instance, 2-furoic acid, cinnamic acid and crotonic acid yield e anhydrides in 84%, 83% and 83%, respectively. 

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