Isopropenyl Acetate acetates

Isopropenyl acetate Acetic acid, isopropenyl ester (8) Acetic acid, (1-methylethenyl) ester (9) (-)... 

Isopropenyl acetate gives spinnable fibres on copolymerization with vinyl chloride. 

Isopropenyl acetate [108-22-5] which forms upon reaction of acetone [67-64-1] with anhydride, rearranges to acetylacetone [123-54-6] in the presence of BF3 (19) ... 

Ketones with labile hydrogen atoms undergo enol acetylation on reaction with ketene. Strong acid catalysis is required. If acetone is used, isoptopenyl acetate [108-22-5] (10) is formed (82—85). Isopropenyl acetate is the starting material for the production of 2,4-pentanedione (acetylacetone) [123-54-6] (11). 

The industrial precursor to 2,4-pentanedione is isopropenyl acetate, produced from acetone and ketene (307,308). The diketone is formed by the high temperature isomerization of isopropenyl acetate over a metal catalyst (309—311). 

Hydration and Dehydration. Succinic anhydride reacts slowly with cold water and rapidly with hot water to give the acid. For this reason it must be carefully stored in anhydrous conditions. Succinic acid can be dehydrated to the anhydride by heating at 200°C, optionally in the presence of a solvent (31). Dehydration can also be performed with clay catalysis in the presence of isopropenyl acetate under microwave irradiation (32) or with his (trichi oromethyl) carbonate at room temperature (33). 

Acetylsucrose [63648-81-7] has been prepared in 40% yield by direct acetylation of sucrose using acetic anhydride in pyridine at 40° C (36). The 6-ester has subsequently been obtained in greater than 90% yield, by way of 4,6-cycHc orthoacetate. Other selective methods for the 6-acylated derivatives include the use of alkyl tin reagents such as dibutyl tin oxide (37) and of dibutyl stannolane derivatives (38). Selective acetylation of sucrose by an enzymic process has also been described. Treatment of sucrose with isopropenyl acetate in pyridine in the presence of Lipase P Amano gave, after chromatography, 6-0-acetylsucrose (33%) and 4/6-di-O-acetylsucrose (8%). The latter compound has been obtained in 47% yield by the prolonged treatment (39). 

Enol esters are another useful family of acylating agents. The acetate of the enol form of acetone, isopropenyl acetate, is the most commonly used member of this group of... 

A -Dien-3-ol esters e.g., acetates) have greater utility as reaction intermediates than as protecting groups. They are prepared from A" -3-ketones by reaction with the acetic anhydride"" or by exchange with isopropenyl acetate. 

Enol esterification with acetyl chloride-acetic anhydride gives the A -trien-3-acetate, but reaction with isopropenyl acetate or with hot acetic anhydride-pyridine gives A " -trien-3-acetates. " Since A"" -3-ketones react with Girard reagents, these linear dienones can be separated from A ""-3-ketones. ... 

Unsubstituted 20-ketones readily form enol acetates. Reaction with isopropenyl acetate yields the kinetic A -isomer (86, R = CH3CO) which is equilibrated to the A -enol acetate (85, R = CH3CO) on exposure to acetic anhydride-/7-toluenesulfonic acid. Treatment of the 20-ketone according to the latter conditions gives the A -enol acetate directly. 

A -20-Dien-20-ol acetates are prepared by acid-catalyzed reaction with isopropenyl acetate.A -20-Semicarbazones can be prepared in the usual manner. ... 

The dimethyl acetal (94) is readily prepared from the 22-aldehyde (93) by direct reaction with methanol in the presence of hydrogen chloride. Ena-mines (95) are formed without a catalyst even with the poorly reactive piperidine and morpholine.Enol acetates (96) are prepared by refluxing with acetic anhydride-sodium acetate or by exchange with isopropenyl acetate in pyridine.Reaction with acetic anhydride catalyzed by boron trifluoride-etherate or perchloric acid gives the aldehyde diacetate. 

A series of benzimidazole and benzimidazolone derivatives from the Janssen laboratories has provided an unusually large number of biologically active compounds, particularly in the area of the central nervous system. Reaction of imidazolone itself with isopropenyl acetate leads to the singly protected imidazolone derivative 51. Alkylation of this with 3-chloro-l-bromopropane affords the functionalized derivative Use of this... 

Cyclic 1,3-diacetoxy-l,3-dienes can be generated in situ from cyclic 1,3-diketones under the influence of isopropenyl acetate. The dienes then undergo Diels-Alder reactions with maleic anhydride giving as products 1-acetoxybicycloalkane dicarboxylic anhydride derivatives (10). The procedure is also successful with cyclic 1,2- and 1,4-diketones as well as cyclic a,j3-unsaturated ketones. The products, after hydrolysis to... 

In a 500-ml round-bottom flask is placed a mixture of 25 g (0.178 mole) of dimedone, 21.8 g (0,22 mole, 25 % excess) of pulverized maleic anhydride, 0.1 g of /7-toluenesulfuric acid, and 150 ml of isopropenyl acetate. The mixture is refluxed for 72 hours, then cooled, and the acetone is removed at room temperature on a rotary evaporator. The resulting solution is cooled to —20° in a Dry Ice bath, whereupon the product crystallizes. It is collected by filtration to yield the crude product in about 80% yield. Recrystallization from hexane-ethyl acetate and decolorization by Norit gives colorless crystals, mp 164-166°. 

The reaction of 20 g (0.177 mole) of 1,3-cyclohexanedione (Chapter 5, Section II) with 21.8 g (0.22 mole) of maleic anhydride and 0.1 g of/j-toluenesulfonic acid in 150 ml of isopropenyl acetate is conducted as described above to give about 70% of the recrystallized product, mp 156-159°. 

Sulfolene (2,5-dihydrothiophene-l,1-dioxide) EK, MCB Isopropenyl acetate MCB Dimedon EK, MCB... 

In 1992, Oda et al. reported a one-pot synthesis of optically active cyanohydrin acetates from aldehydes, which were converted to the corresponding racemic cyanohydrins through transhydrocyanation with acetone cyanohydrin, catalyzed by a a strongly basic anion-exchange resin [46]. The racemic cyanohydrins were acetylated by a lipase from P. cepacia (Amano) with isopropenyl acetate as the acyl donor. The reversible nature of the base-catalyzed transhydrocyanation enabled continuous racemization of the unreacted cyanohydrins, thereby effecting a total conversion (Figure 4.21). 

Hence, enol esters such as isopropenyl acetate are good acylating agents for alcohols. Isopropenyl acetate can also be used to convert other ketones to the corresponding enol acetates in an exchange reaction ... 

CiHgO 67-65-0) see Fenofibratc Imiquimod Isoflurophate Nimodipine isopropenyl acetate... 

Isocyano-2-methylpropane, 55, 96 Isophorone,57,113 Isopropenyl acetate,. 57, 113 Isopropyl alcohol, 5t8, 78, 157... 

Isopropenyl acetate and allyl chloride behave similarly. In the polymerization of the latter monomer degradative chain transfer occurs more readily by removal of the chlorine atom to yield the unsubstituted allyl radical CH2—CH—CH2, which manages to add monomer occasionally. This is indicated by the formation of about three polymer molecules, having an average degree of polymerization of six units, for each molecule of benzoyl peroxide decomposing. 

Butadiene p-Methoxystyrene Vinyl acetate Vinyl chloride Diethyl maleate Isopropenyl acetate Vinyl chloride... 

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