Cyclic anhydride, reaction with alcohol

LiAlH4 usually reduces open-chain anhydrides to give 2 moles of alcohol, With cyclic anhydrides the reaction with LiAIH4 can be controlled to give either diols or lactones572 (see 9-41). NaBH4 in THF, with dropwise addition of methanol, reduces open-chain anhydrides to one mole of primary alcohol and one mole of carboxylic acid.573 OS VI, 482. 

The scope of this reaction is similar to that of 10-21. Though anhydrides are somewhat less reactive than acyl halides, they are often used to prepare carboxylic esters. Acids, Lewis acids, and bases are often used as catalysts—most often, pyridine. Catalysis by pyridine is of the nucleophilic type (see 10-9). 4-(A,A-Dimethylamino)pyridine is a better catalyst than pyridine and can be used in cases where pyridine fails. " Nonbasic catalysts are cobalt(II) chloride " and TaCls—Si02. " Formic anhydride is not a stable compound but esters of formic acid can be prepared by treating alcohols " or phenols " with acetic-formic anhydride. Cyclic anhydrides give monoesterified dicarboxylic acids, for example,... 

The favored formation of a nucleoside 3 -(alkyl phosphate) was observed on treating the diphenyl phosphate anhydride of uridine 2, 3 -cyclic phosphate with benzyl alcohol.273 In a somewhat related reaction, on treatment with dicyclohexylcarbodiimide in aqueous pyridine, adenosine 2 (3 )-phosphate gave, initially, the 2, 3 -cyclic phosphate, which, on further reaction with the diimide, gave a mixture of the N-phosphonourea nucleoside 44 and its 2 -isomer, in unequal amounts.269 This type of reaction does not seem to occur with... 

Acetals are readily formed with alcohols and cyclic acetals with 1,2 and 1,3-diols (19). Furfural reacts with poly(vinyl alcohol) under acid catalysis to effect acetalization of the hydroxyl groups (20,21). Reaction with acetic anhydride under appropriate conditions gives the acylal, furfurylidene diacetate [613-75-2] (22,23). 

The reaction of cyclic anhydrides with amines can be different from that with alcohols, because in the case of amines, the amido acid formed during the first step (Eq. 2.9) can close a cycle to give an imide group (Eq. 2.10) ... 

Blaser and Spencer used aroyl halides in place of aryl halides, with aroyl chlorides being of specific interest as ubiquitous, relatively cheap compounds ( Blaser reaction ) [24], This latter reaction is normally conducted in aromatic solvents phosphines are not used here as catalyst ligands since they fully inhibit the reaction. In the same way, benzoic acid anhydrides can be used as the aryl source in combination with PdCl2 and catalytic amounts of NaBr [79]. In this reaction, one of the arenes is used in the coupling reaction by elimination of CO, whereas the other benzoate serves as the base. The benzoic acid thus formed can easily be recycled into the anhydride. The use of aryl and vinyl triflates according to Cacchi [25] and Stille [26] extends the scope of the Heck coupling to carbonyl compounds phenol derivatives act via triflate functionalization as synthetic equivalents of the aryl halides. The arylation of cyclic alkenes [27], electron-rich vinyl ethers [28], and allylic alcohols [29] is accessible through Heck reactions. Allylic alcohols yield C-C-saturated carbonyl compounds (aldehydes) for mechanistic reasons (y9-H elimination), as exemplified in eq. (6). 

The early work on this compound was confused by Pschorr s failure to recognize its phenolic nature. He noted the alkali-soluble nature of the methiodide and the production of a mono-acetyl derivative, but concluded, on account of the apparent insolubility of the parent base in alkali, that fission of the cyclic ether fink occurred during the reactions of the base with acetic anhydride and methyl iodide [7]. That /3-ethylthiocodide is indeed a phenol was demonstrated by Morris and Small [3] it gives coloured solutions with alcoholic ferric chloride and readily couples with diazonium salts in alkaline solution to give red dyes moreover it is soluble in alkali, though not readily so, being a very weakly acidic phenol. 

Phosgene is reported to combine with a wide range of oxygenated materials, including alcohols, ethers, ketones, carboxylic acids, anhydrides, lactones, esters, carbonic acid derivatives, etc. Only the reactions of COCIF with alcohols, phenols and cyclic ethers have been reported, resulting usually in the generation of fluoroformates. Such materials can often be usefully converted into the corresponding fluoro compound by means of decarboxylation in the presence of BF3, EtjO, pyridine, or other materials. 

The Diels-Alder reaction was utilized to construct bicyclo [2.2 1]heptane or bicyclo[2 2 l]heptene structures The reaction of isopropylidenecyclopentadiene with maleic anhydride produced the endo and exo configurational isomers of 8-isopropylidenebicyclo[2.2.1] hept-2-ene-5,6-dicarboxylic anhydride Similar reactions were applied to unsubstituted and l-(methoxycarbonyl)cyclopentadienes to give the corresponding anhydrides The anhydrides were reduced to alcohols, which were then allowed to react with thionyl chloride or tosyl chloride to give cyclic sulfites or tosylates Reaction of the tosylates with lithium chloride gave chlorinated compounds Hydration of the double bonds of the chlorinated compounds was accomplished by hydroboration-oxidation Diol 31 thus obtained was converted to 5,6-bis(chloromethyl)-7-isopropylidene-bicyclo[2 2 1] heptan-2-one [33] by chromium trioxide oxidation of the secondary hydroxyl group followed by dehydration at the C-7 substituent. 

Polymer plasticization can be achieved either through internal or external incorporation of the plasticizer into the polymer. Internal plasticization involves copolymerization of the monomers of the desired polymer and that of the plasticizer so that the plasticizer is an integral part of the polymer chain. In this case, the plasticizer is usually a polymer with a low Tg. The most widely used internal plasticizer monomers are vinyl acetate and vinylidene chloride. External plasticizers are those incorporated into the resin as an external additive. Typical low-molecular-weight external plasticizers for PVC are esters formed from the reaction of acids or acid anhydrides with alcohols. The acids include ortho- and iso-or terephthalic, benzoic, and trimellitic acids, which are cyclic or adipic, azeleic, sebacic, and phosphoric acids, which are linear. The alcohol may be monohydric such as 2-ethylhexanol, butanol, or isononyl alcohol or polyhydric such as ethylene or propylene glycol. The structures of some plasticizers of PVC are shown in Table 9.1. 

Chiral y-amino-acids (e.g. 180) have been prepared from the corresponding optically active /8-amino-acids by the addition of one carbon atom using the Arndt-Eistert reaction.w-Amino-acids are available from cyclic anhydrides by treatment with stannyl azide (to give an w-isocyanatocarboxylic acid) followed by addition of an alcohol. In contrast to simple enamines, oxidation of N-acyl-a-aminocrotonates with thallium nitrate leads to the corresponding a/8-dimethoxy derivatives. 

It has been also reported sicne 1958 [52] that itaconic anhydride (lAn), which is an another cyclic derivative of lA, polymerizes as well as other lA derivatives, but its reactivity is less than those of RII and RPhll. Poly(IAn) may be derived into some poly(IA) derivatives by reaction with amines and alcohols [63,64]. The polymerization reactivities of several itaconamides (lAm) and itaconamates (lAE) were also investigated [48]. It was found that iV, -dialkyl substituted lAm homopolymerize in the presence of a radical initiator, but iV,iV,iVj -tetraalkyl-substituted one did not give a polymer, because the latter consists of an a,7V, trisubsti-tuted acrylamide structure resemble to, y disubstituted methacrylamides. Similar results were obtained for polymerization of mono- and, V disub-stituted lAE. 

Likewise the acid or base catalyzed reaction of an alcohol and an acid anhydride is a regular method of esterification [4]. For many acids the most convenient experimental procedure is to form a mixed anhydride in situ by reaction with trifluoroacetic anhydride [23, 24] or the reagents listed above (method A). Cyclic anhydrides of dibasic acids yield monoesters with alcohols and this reaction is utilized in the preparation of glutamine (11) from glutamic acid (10) and in a similar synthesis of asparagine [35, 36]. 

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