A lactones

CflHaOa. An unstable acid which spontaneously forms a -lactone, coumarin, when the free acid is generated from its salts. See coumaric acid. 

A lactone is named by replacing the oic acid ending of the parent carboxylic acid by olide and identifying its oxygenated carbon by number This system is illustrated m the lactones shown m the preceding equations Both 4 butanolide and 5 pentanolide are... 

Lactones whose rings are three or four membered (a lactones and p lactones) are very reactive making their isolation difficult Special methods are normally required for the laboratory synthesis of small ring lactones as well as those that contain rings larger than SIX membered... 

Reaction with Lactones. Hydroxycarboxyhc acid ester complexes of titanium are formed by reaction of a tetraalkyl titanate with a lactone, such as P-propiolactone, y-butyrolactone, or valerolactone (35). For example. 

Oxiranones (a-lactones) 81JA686, 80AG(E)276), e.g. (6), are highly reactive, readily polymerizing (Scheme 18), possibly via a zwitterion (18). Such a species (19) would also account for the rearranged products (20) and (21) from (22 Scheme 19). 

Oxiranones (a-lactones) (Section 5.05.3.2.1), e.g. (6), in accord with their putative facile opening to zwitterions (Scheme 18), usually react readily with nucleophiles by alkyl-oxygen cleavage (Scheme 41) (71JA557), rather than the acyl-oxygen cleavage common for esters. 

The p-phenylbenzoate ester was prepared to protect the hydroxyl group of a prostaglandin intermediate by reaction with the benzoyl chloride (Pyr, 25°, 1 h, 97% yield). It was a more ciystalline, more readily separated derivative than 15 other esters that were investigated. It can be cleaved with K2CO3 in MeOH in the presence of a lactone. ... 

The DTBMS ester was prepared (THF, DTBMSOTf, Et3N, rt) to protect an ester so that a lactone could be reduced to an aldehyde. The ester is cleaved with aq. HF/THF or Bu4N F in wet THF. A THP derivative can be deprotected (pyri-dinium p-toluenesulfonate, warm ethanol) in the presence of a DTBMS ester. ... 

Hydroxy-1-naphthaleneacetic acid [10441-45-9] M 202.2, pK )-4.2, pKej,(2) -8.3. Treated with activated charcoal and crystd from EtOH/water (1 9, v/v). Dried under vacuum, over silica gel, in the dark. Stored in the dark at -20° [Gafni, Modlin and Brand J Phys Chem 80 898 1976. Forms a lactone (m 107°) readily. 

Xanthotoxin (Methoxalen, 9-methoxyfuro[3,2-g][l]benzopyran-7-one) [298-81-7] M 216.2, m 146-148 , 148 , 148-149 . Purified by recrystn from CgH6-pet ether (b 60-80°) as silky needles, Et0H-Et20 as rhombic prisms or hot H2O as needles. It is soluble in aqueous alkali due to ring opening of a lactone but recyclises upon acidification. It has UV EtOH at 219, 249 and 300nm (log e... 

Ring opening of a lactone, e.g. of e-caprolactone with dihydroxy or trihydroxy initiators ... 

This represents hydrastine as a seeondary amine and a free acid, though the alkaloid reacts with alkyl iodides on the whole as a tertiary amine and forms salts with alkalis rather as a lactone than as a free acid. These and other considerations led Freund and Rosenberg to suggest the alternative formula (IV), based on Roser s formula for narcotine (p. 204). 

Bicuculline, C2oHi,06N. (Items 1, 9, 10, 13, 14, 18, 20, 23-26, 34, 35, 38 list, p. 169). This alkaloid exists in two forms, m.p. 177° and m.p. 196°, and has [a], ° + 130- 5° (CHCI3). The hydrochloride has m.p. 259° (dec.) and from the methiodide, W-methylbicuculline, plates, m.p. 246°, has been prepared. Bicuculline contains no methoxyl groups it behaves as a lactone and is convertible by alkalis into bicucine, which is possibly the corresponding hydroxy-aeid (see below). It simulates hydrastine in its reactions and differs from that base by CH, indicating that a methylene-dioxy group replaces two methoxyl groups, and this view is supported by comparison of the products of oxidative hydrolysis of the two alkaloids. Both yield hydrastinine (p. 163) as the basic product, but while hydrastine provides as the second product, opianic acid,... 

Erythroidine behaves as a lactone and when one of its salts with an alkali or alkaline earth metal is catalytically hydrogenated under pressure, a mixture of dihydro-j3-erythroidines, with two tetrahydro- compounds is produced, from which dihydro- -erythroidine can be isolated as the hydrobromide. The dihydro- base has m.p. 85-6° (dec.), + 102-5° and... 

When monocrotaline is hydrogenolysed the acid scission product is monocrotalic acid, CgHigOj, m.p. 181-2°, [a]p ° — 5-33° (HgO), which provides a methyl ester, m.p. 79-80°, [ ]d°° — 16-2° (EtOH), containing one active H atom and a p-bromophenacyl ester, m.p. 162-3°. It is a lactonic acid, which on boiling with sodium hydroxide solution loses carbon dioxide and produces a/3-dimethyllaevulic acid (monocrotic acid, II). 

Heteratisine, C22H33O5N, crystallises in prisms, has m.p. 262-7° (dec.), [a]f7° + 40° (MeOH), forms a hydrochloride, m.p. 265-270° (dec.), contains one methoxyl and one methylimino group, two active hydrogens and a lactone ring, opened by alkali and re-formed on acidification. In a later paper the same authors describe the isolation of benzoylheteratisine, C29H3,03N, m.p. 213-4°, [a]jf° + 73° (EtOH), which yields a hydrochloride, m.p. 218-221° (dec.), and is hydrolysed to benzoic acid and heteratisine the latter they suggest may not exist naturally in the plant but may be produced from benzoylheteratisine during extraction. 

Annotinine, C gHjjOjN, (1). M.p. 232° perchlorate, m.p. 267°. In a later paper (1947) Manske and Marion record the results of the action of alkali and of halogen acids on annotinine, and of the oxidation of the base and discuss the reaction products. They conclude that two of the oxygen atoms are present as a lactone group and that the third oxygen may form an ether bridge in a 5- or 6-membered ring. 

Stemonidine, CjoHajOgN. The base has m.p. 116 , [a]jf° — 7 65 , and yields a hydrochloride, m.p. 260 (dec.), and a methiodide, m.p. 248 . It is a tertiary base and of the five oxygen atoms two are in a lactone group and a third is present as methoxyl the functions of the other two are unknown. The alkaloid is unaffected by hydrogen chloride (25 per cent.) in alcohol or acetic acid. The permanganate oxidation products vary with the conditions of the experiment —... 

On distillation with zinc dust the alkaloid gives an easily hydrogenated pyrrole base, and on dehydrogenation by platinised asbestos at 260-290 it yields (1) an amorphous dehydro-base, which forms an oxime and a methiodide, C17H23O4N. Mel, decomp. 227-8 , and contains a lactone and a methoxyl group, (2) a neutral pyrrole derivative, and (3) an acid giving a dark green colour with ferric chloride (1939). 

Callow, Gulland and Virden obtained evidence of the presence of four replaceable hydrogen atoms and of a lactone group, thus accounting for six out of the ten oxygen atoms required by the formula. The remaining... 

The mechanism of this degradation has received considerable attention, and for some species the reaction is equivalent to a nonenzymatic Baeyer-Villager reaction, producing first the 17j8-acetate. This functionality can then be hydrolyzed and oxidized to the ketone and may undergo a second Baeyer-Villager reaction to produce a lactone ... 

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