Acid anhydrides, bicyclic

Anhydro-acylation of l,2-dihydro-2-oxo-l-pyridylacetic acid with acid anhydrides yields bicyclic meso-ionic 4-acyl-l,3-oxazol-5-ones (67). Huisgen and his co-workers have reported extensive studies of the monocyclic meso-ionic l,3-oxazol-5-ones (66), which they have lightheartedly named munchnones. Cyclodehydration of N-benzoyl-A -methyl-C-phenylglycine using acetic anhydride at 55° gives the 3-methyl-2,4-diphenyl derivative (66, R = = Ph R = Me) as... 

Formula 366) gives a bicyclic enol ether (Formula 367) which is hydrolyzed to Formula 368 (161,162). The sequence of Formulas 366-368 represents a potentially general synthesis of bicyclic cyclobutanone derivatives. A clever synthesis of m-3-cyclobutene-l,2-dicarboxylic acid anhydride (Formula 369) has been accomplished by irradiation of muconic anhydride (Formula 370) in ether (163). 

Another type of elimination reaction favoured under plasma conditions is the decarboxylation. Carbocyclic acids easily lose carbon dioxide to form the parent hydrocarbons. In acid anhydrides decarboxylation is followed by a decar-bonylation. Cyclic or bicyclic anhydrides fragment forming unsaturated compounds, a reaction which has been studied with phthalie anhydride 24>. This anhydride decomposes to dehydrobenzene which, in the absence of other compounds, dimerizes, trimerizes or polymerizes. Orientation experiments indicated similar results for aliphatic acid anhydrides. 

Methylation with dimethyl sulfate in alkali gave the methyl derivatives 28 and 29. Although formaldehyde attacks at N-2, aldol condensation of 10 with benzaldehyde gave the 3a-hydroxybenzyl compound (30) which is dehydrated to the 2-acetyl-3-benzylidene compound (31) with acetic anhydride.27 With acid anhydrides the2-acyl derivatives are obtained however, with acid chlorides in pyridine or dimethylaniline the bicyclic ketone (32) is formed.31 Despite the occurrence of the bicyclic product (32) and the bicyclic intermediate (13) there is no evidence for the existence of a bicyclic tautomer of 10.37... 

The action of a Zn/Cu couple on 1,3-dibromo ketones and secondary amides yields 2-dialkylamino-1,3-dioxolanes (451 equation 208). Fluorosulfonic peracid anhydride adds to trifluoroacetonitrile to give an amide acetal (452 equation 209). In the addition of (Z)-2-butene-l,4-diol to trichloroacetoni-trile, catalyzed by sodium, the 1,3-dioxepin (453 equation 210) is produced. Bicyclic amide acetals (454 equation 211) are byproducts in the reaction of lactim ethers with diketene. TTie methyl esters of perfluorinated carboxylic acids react with diethanolamine to afford bicyclic amide acetals (455 equation 212). Heating of maleic anilides (456 equation 213) with acetic acid anhydride/sodium acetate gives heterocyclic compounds (457) containing an amide acetal structure. ... 

The photochemical isomerization of the muconic acid anhydride (304) to the bicyclic compound (305) has been reported to occur in high yield. 

Enantiomeric separations of bicyclic acid anhydride 69, lactones 70 and 71 and carboximides 72 and 73 by complexation with la-c in organic solvents were also successful (Table 3.3-3) [26]. These complexations can probably be carried out in a water suspension medium and hence be described as green processes. rac-Panto-lactone (74) was separated to produce (S)-(-)-74 of 99% ee in 30% yield by complexation with Ic [27]. Enantiomerically impure monoterpenes were purified by inclusion complexation with a chiral host compound. For example, (lS,5S)-(-)-verbe-none (75a) of 78% ee gave 99% ee enantiomer by complexation with la. By similar treatment of 75b of 91% ee with la as above, (lR,5R)-(-i-)-75b of 98% ee was obtained [28]. 

Diels, Otto Fhul Hermann, 258-259, 270 Diels-Alder reaction, 257-275 bicyclic adduct, 454 carbocyclic rings, 454- 55 as cycloaddition reaction, 259 4-cyclohexene-ds-l,2-dicarboxylic acid anhydride, 257-268 defined, 259... 

Quaternary amonium salts [796], tertiary amines or pyridines [797], bicyclic tertiary amines, cryptants [798] or amphoteric alkylamino sulfonates [799] are suitable as accelerators for this 3-component esterification. Liberation of the aldehyde 280 from its depot form, the bisulphite adduct, may taken place under the reaction conditions in a hydrocarbon [800] or better in ethyl acetate [801]. In order to minimize the occurrence of side products, keeping the aqueous phase more alkaUne for removal of the casually produced small amounts of pyrethroid acid anhydride 305 [802] is recommended. More expedient is the activation of such anhydrides by 4-dimethyl-... 

Pyridazines with an appropriate side chain attached to the sulfur atom at position 3 can be transformed into bicyclic systems. For example, pyridazinyl /3-ketoalkyl sulfides are cyclodehydrated in sulfuric acid to give thiazolopyridazinium salts, and 3-carboxymethyl-thiopyridazines are transformed by acetic anhydride in pyridine into 3-hydroxythiazolo[3,2-6]pyridazinium anhydro salts (Scheme 52). 

A useful oxidizing reagent is silver(III) tristrifluoroacetate which can be generated from silver peroxide (AgO) and a tnfluoroacetic acid-tnfluoroacetic anhydride mixture [5f] This reagent readily oxidizes alicyclic and bicyclic hydro... 

The classic method for controlling stereochemistry is to perform reactions on cyclic substrates. A rather lengthy but nonetheless efficient example in the prostaglandin field uses bicyclic structures for this purpose. Bisacetic acid derivative S is available in five steps from Diels-Alder reaction of trans-piperylene and maleic anhydride followed by side-chain homologation. Bromolactonization locks the molecule as bicyclic intermediate Esterification, reductive dehalogen-... 

The diacetylated ethane-1-hydrox-1,1-diphosphonic acid is prepared by dissolving the diphosphonic acid in acetic acid and adding acetic anhydride [114]. The sodium salt can be directly converted to the free acid form by passing it through an hydrogen cation exchanger. The bicyclic dimer is prepared by basic hydrolysis of diacetylated cyclic dimer, as shown in Eq. (70) ... 

The first successful attempt to prepare bicyclic indolizinedione derivatives 210 was achieved by the reaction of dimethylmaleic anhydride with pyrrolylmagnesium bromide followed by the cyclization of the intermediate acid. The corresponding unsubstituted desmethyl compound cannot be prepared this way [90JCS(P1) 1463]. 

An angiotensin-converting enzyme inhibitor 64 was prepared in several steps from L-pyroglutamic acid. The formation of the bicyclic system was achieved with methylene glutaric anhydride (89TL3621). 

The tricycle (71) has been synthesized in 97 % yield via the nitration of the corresponding urea (70) with dinitrogen pentoxide in nitric acid. The high performance bicyclic N,N -dinitrourea known as TNPDU (73) is synthesized from the reaction of propanediurea (72) with acetic anhydride-nitric acid. ... 

The nitrolysis of hexamine at low temperature has led to the synthesis of a number of cyclic nitramines. The reaction of hexamine dinitrate (241) with 88 % nitric acid at -40 °C, followed by quenching the reaction mixture onto crushed ice, leads to the precipitation of 3,5-dinitro-3,5-diazapiperidinium nitrate (242) (PCX) in good yield PCX is an explosive equal in power to RDX but is slightly more sensitive to impact. The reaction of PCX (242) with sodium acetate in acetic anhydride yields l-acetyl-3,5-dinitro-l,3,5-triazacyclohexane (82) (TAX), which on further treatment with dilute alkali in ethanol yields the bicycle (243). ... 

The reaction of hexamine dinitrate (241) with 98% nitric acid at —30°C, followed by quenching with aqueous sodium nitrate, yields the nitrosamine (244). When the same reaction is cautiously quenched with ethanol the ethoxyether (245) is obtained. Treatment of the ethoxyether (245) with cold absolute nitric acid yields the bicyclic ether (246). ° Treatment of any of the cyclic nitramines (242)-(246) with nitric acid and ammonium nitrate in acetic anhydride yields RDX. ° Hexamine dinitrate is often used in low temperature nitrolysis experiments in order to avoid the initial exotherm observed on addition of hexamine to nitric acid. 

Reduction of dehydro-c-ascorbic acid phenylhydrazone (40) with LiAlH4 resulted in hydrogenation of the hydrazone residue and cyclization to bicyclic compound 41, which was dehydrogenated with boiling acetic anhydride during acetylation to give diacetate 43, then partly hydrolyzed to monoacetate 42 (Scheme 7) (72JOC3523). 

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