Methyl, alcohol crotonic acids

Methyl crotonate. Purify commercial crotonic acid by distiUing 100 g. from a 100 ml. Claisen flask attached to an air condenser use an air bath (Fig. II, 5, 3). The pure acid passes over at 180-182° and crystallises out on cooling, m.p. 72-73° the recovery is about 90 per cent. Place 75 g. of absolute methyl alcohol, 5 g. (2 -7 ml.) of concentrated sulphuric acid and 50 g. of pure crotonic acid in a 500 ml. round-bottomed flask and heat under reflux for 12 hours. Add water, separate the precipitated ester and dissolve it in ether wash with dilute sodium carbonate solution until effervescence ceases, dry with anhydrous magnesium sulphate, and remove the ether on a water bath. Distil and collect the methyl crotoiiato at 118-120° the yield is 40 g. 

In addition to the above-mentioned monomers, various acrylic and methacrylic esters, methacrylonitrile, itaconic acid, crotonic acid, methyl vinyl ketone, allyl alcohol, allyl amine etc., have been studied by Fischer... 

While alcohol oxidations have been the most common metal promoted reactions involving molecular oxygen, a number of other metal catalyzed oxidations of potential synthetic interest have been reported. Supported palladium catalysts are comparable to many soluble palladium catalysts in promoting the selective oxidations of alkenes and aromatics. 2-Butene was oxidized primarily to crotonic acid over Pd/C in water but methyl vinyl ketone and crotonaldehyde were also formed in significant amounts. When this oxidation was run in acetic acid the allyl acetates were the major products, particularly when a Pd/Al203 catalyst... 

However, the addition occurs contrary to the Markovnikov rule under irradiation by ultraviolet light or in the presence of peroxides 1 for instance, allyl-amine hydrochloride or a derivative thereof in alcoholic solution is thiolated by an excess of hydrogen sulfide under UV-irradiation, exclusively (yields up to 57%), to give 3-aminoalkanethiols.2 Addition of hydrogen sulfide is of use in the laboratory only when the reaction can be carried out in the liquid phase and is then preferably effected under the influence of a basic catalyst Dahl-bom,3 for instance, obtained 3-mefcapto-butyric acid from crotonic acid hydrogen sulfide in the presence of diethylamine in a closed vessel at 70° and 4-mercapto-4-methyl-2-pentanone is obtained in 80% yield from mesityl oxide and hydrogen sulfide with triethylamine as catalyst.4... 

Tallow Tallow alcohol Tosylamide/formaldehyde resin VA/crotonates copolymer Vinyl acetate/butyl acrylate copolymer Vinyl acetate/crotonic acid copolymer Vinylidene chloride/acrylonitrile copolymer Vinylidene chloride/methyl acrylate copolymer Vinylidene chloride/vinyl chloride copolymer Zinc laurate paper/paperboard, dry food-contact Acrylamides copolymer Acrylates copolymer Alkenyl succinic anhydride Ammonium maleic anhydride/diisobutylene copolymer Ammonium nitrate... 

Quatemized copolymers of vinyl pyrrolidone and dimethylaminoethylthacrylate, which is cationic, have been developed for the hair care and skin care industries because of their optimal substantivity, minimum buildup, and ability to form nontacky and continuous films. Other important comonomers include vinyl alcohol, styrene, maleic anhydride, acrylamide, acrylonitrile, crotonic acid, and methyl methacrylate. 

Hair sprays are applied to dry hair after styling has been finished. They are intended to give styling a hold and to prevent change of style by wind and humidity. Like setting lotions hair sprays contain polymers, such as copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinyl acetate and crotonic acid neutralized with alkanolamines, e. g., 2-amino-2-methyl-l,3-propandiol, small amounts of plasticizers, ->cetyl alcohol, silicones, disolved in ethanol or isopropanol without or with only a small amount of water, because more than 10-20% of water destroy the hair style. The polymer solution is filled up with propellants, such as propane and butane, in an aerosol can. In the hair care market, hair sprays rank second in sales only to shampoos. 

Methyl n-amyl carbinol. 247, 254 Methyl n-amyl ketone, 482 Methylaniline (mono), pure, from commercial methylaniline, 562, 570 P-Methylanthraquinone, 728, 740 Methyl benzoate, 780, 781 p-Methyl benzyl alcohol, 811,812 Methyl benzyl ketone, 727, 735 Methyl y-bromocrotonate, 926, 927 2-Methyl-2-butene, 239 Methyl n-butyl carbinol, 247,255 Methyl n-butyl ether, 314 Methyl n-butyl ketone, 475, 481 4-Methylcarbostyril, 855 p-Methylcinnamic acid, 719 4-Methylcoumarin, 853, 854 Methyl crotonate, 926, 927 Methylethylacetic acid, 354, 358 Methylethylethynyl carbinol, 468 Methyl ethyl ketone, 335, 336 purification of, 172 Methyl n-hexyl ether, 314 Methyl n-hexyl ketone, 335, 336 Methyl n-hexyl ketoxime, 348 Methyl hydrogen adipate, 938 Methyl hydrogen sebacate, 938,939 4-Methyl-7-hydroxycoumarin, 834 Methyl iodide, 287 Methyl isopropyl carbinol, 247,255 Methyl 4-keto-octanoate, 936... 

A new strategy for the synthesis of heterocyclic a-amino acids utilizing the Hantzsch dihydropyridine synthesis was developed in the laboratory of A. Dondoni." ° The enantiopure oxazolidinyl keto ester was condensed with benzaldehyde and fert-butyl amino crotonate in the presence of molecular sieves in 2-methyl-2-propanol to give a 85% yield of diastereomeric 1,4-dihydropyridines. The acetonide protecting group was removed and the resulting amino alcohol was oxidized to the target 2-pyridyl a-alanine derivative. 

The reaction is carried out in aqueous tetrahydrofuran, if acrylic acid is the desired product, or in aqueous alcohol if the ester is required. Nickel is introduced as bromide or iodide and is converted into carbonyl complexes under the reaction conditions, typically 200°C/100atm. One catalytic cycle which has been postulated for this process is shown in Fig. 12.18. Selectivity in the formation of acrylic acid from acetylene is better than 90%. Even from propyne, where anti-Markovnikov addition of [Ni]—H competes with the desired pathway, selectiv-ities of over 80% to methyl methacrylate H2C=C(Me)C02Me are achieved. The major by-product is methyl crotonate, MeCH=CHC02Me. 

Ethyl 2-methyl-4-pentenoate (in various solvents), 350 Ethyl 3-aminobenzoate, 526 Ethyl crotonate, 620 Ethyl cyanoacetate, 529 Ethyl iodide, 132 Ethyl methacrylate, 361 Ethyl propionate, 523 Ethylbenzene, 287 Ethyhnalonic acid, 159 A-Ethylnicotinamide, 345 Eurfuryl alcohol, 295... 

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