Carboxylic equivalent

While the sultame and the oxazolidinone auxiliaries represent carboxylate equivalents, which have to be reduced (and sometimes re-oxidized) to the required aldehyde function at C7, the strength of Enders SAMP and RAMP auxiliaries is their direct use as aldehyde and ketone equivalents. However, Nicolaou et al. [13, 16] for the synthesis of the protected building blocks 17a-c had to give up the correct oxidation state in order to allow necessary later manipulations. Considering the necessity of reduction, the cheaper and recoverable Evans-oxazolidinones 18 appear to be the auxiliaries of choice, as demonstrated by Schinzer et al. [21, 22, 36]. A similar methylation is described in an early publication of De Brabander et al. [38] where sultame 21 was methylated and reduced to the a-methylaldehyde 20b in only two steps in good yield and enantiomeric excess. 

Triazolium salts are readily reduced by treatment with sodium borohydride to give the corresponding triazolines. However, these products are unstable to conditions of acid work-up and fragment to give aldehydes. This property has been exploited to homologate aldehydes using 3-methylthio-1,4-diphenyl-1,2,4-triazolium chloride (266) as a masked carboxylate equivalent, as illustrated in Scheme... 

The s)mthesis of e /iro-L-j -hydroxyglutamic acid (844) makes use of the furan heterocycle as a carboxyl equivalent (Scheme 122) [185]. After reduction of 793a to 839 and acetylation (840), the aminal acetate and furan are coupled in the presence of zinc bromide and a catalytic amount of trimethylchlorosilane to give a 67 33 mixture of 841 and 842. In the absence of silane the reaction requires 12 h at room temperature for completion, but with silane present the reaction time is reduced to2hat —15°C. 

Functionality. The number of carboxyl equivalents was determined from the potentlometrlc acid-base titration. The number molecular weight iii of the CTPnBA was determined by the Vapor Pressure Osmometer measurement. The product of the number of acid equivalents by the molecular weight divided by the weight of the titrated PnBA sample is the calculated average number of carboxyl groups per chain of the poly n-butyl acrylate. 

A formidable obstacle subsequently emerged during attempts to install the C-9 carboxyl equivalent required according to the retrosynthon Dill... 

Scheme 14). Thus, although a cyano group could be introduced in excellent yield by reaction of the glycosidic epoxide D7b with Et2AlCN [51], attempts to hydrolyze the nitrile in derivatives of the cyanohydrin so obtained, D8a, were unsuccessful. A number of alternative carboxyl equivalents [52] were tried before adopting a propargyl ether shown in intermediate D8b. 

An extension of the Beirat reaction for the preparation of the first members of the 2-phosphonylated quinoxaline 1,4-dioxide series has been described (Dahbi et al. 2010). Contrary to their carboxylated equivalents, preparation of these new compounds could not be achieved under basic conditions but required the use of powdered molecular sieves (Scheme 2.87). Good and reproducible yields were obtained only when the initial suspension in THF was transformed into a pasty film by the slow evaporation of ca. 90 % of the initial solvent volume. 

Although two isomeric esters are theoretically possible, the main product is the 2-ester (formulated above) traces of the isomeric l-ester are eliminated during purification. These derivatives possess a free carboxyl group their equivalent weights may therefore be determined by titration with standard alkali and thus serve as an additional check upon the identity of the compound. 

The conversion of carboxylic acid derivatives (halides, esters and lactones, tertiary amides and lactams, nitriles) into aldehydes can be achieved with bulky aluminum hydrides (e.g. DIBAL = diisobutylaluminum hydride, lithium trialkoxyalanates). Simple addition of three equivalents of an alcohol to LiAlH, in THF solution produces those deactivated and selective reagents, e.g. lithium triisopropoxyalanate, LiAlH(OPr )j (J. Malek, 1972). 

Pyrano[3,4-b]indol-3-ones are the most useful equivalents of the indol-2,3-quinodimethane synthon which are currently available for synthetic application. These compounds can be synthesized readily from indole-3-acetic acids and carboxylic anhydrides[5,6]. On heating with electrophilic alkenes or alkynes, adducts are formed which undergo decarboxylation to 1,2-dihydro-carbazoles or carbazoles, respectively. 

Electron delocalization in carboxylate ions is nicely illustrated with the aid of elec trostatic potential maps As Figure 19 4 shows the electrostatic potential is different for the two different oxygens of acetic acid but is the same for the two equivalent oxygens of acetate ion... 

It IS possible to use only one molar equivalent of amine m these reactions if some other base such as sodium hydroxide is present m the reaction mixture to react with the hydro gen chloride or carboxylic acid that is formed This is a useful procedure m those cases m which the amine is a valuable one or is available only m small quantities... 

Sulfur Tetrafluoride and Aromatic Carboxylic Acids. Ben2otrifluorides also are prepared from aromatic carboxyhc acids and their derivatives with sulfur tetrafluoride (SF (106,107). Hydrogen fluoride is frequently used as a catalyst. Two equivalents of sulfur tetrafluoride are required ... 

Ring closure resulting from attack of a heteroatom on a carboxyl group or its equivalent is merely a case of intramolecular esterification or amide formation. The y-butyrolactones or pyrrolidones obtained from such reactions are usually regarded as the province of aliphatic chemistry, so only a few examples are offered by way of illustration in Scheme 15. 

Tautomerism Hydroxyl Exist largely in the oxo form Carboxylic acid (two equivalent structures)... 

The phenyl group became a practical protective group for carboxylic acids when Sharpless published a mild, effective one-step method for its conversion to a carboxylic acid. It has recently been used in a synthesis of the amino acid statine, where it served as a masked or carboxylic acid equivalent. ... 

The anhydrides are usually used at ratios of 0.85 1.1 moles anhydride carboxyl group per epoxy equivalent. Lower ratios down to 0.5 1 may, however, be used with some systems. The organic bases are used in amounts of 0.5-3%. These are usually tertiary amines such as a-methylbenzyldimethylamine and n-butylamine. 

Triazole has been prepared by the oxidation of substituted 1,2,4-triazoles, by the treatment of urazole with phosphorus pentasulfide, by heating equimolar quantities of formyl-hydrazine and formamide, by removal of the amino function of 4-amino-l,2,4-triazole, by oxidation of l,2,4-triazole-3(5)-thiol with hydrogen peroxide, by decarboxylation of 1,2,4-triazole-3(5)-carboxylic acid, by heating hydrazine salts with form-amide,by rapidly distilling hydrazine hydrate mixed with two molar equivalents of formamide, i by heating N,N -diformyl-hydrazine with excess ammonia in an autoclave at 200° for 24 hours, and by the reaction of 1,3,5-triazine and hydrazine monohydrochloride. ... 

The isocyanurate reaction occurs when three equivalents of isocyanate react to form a six-membered ring, as shown in the fifth item of Fig. 1. Isocyanurate linkages are usually more stable than urethane linkages. Model compound studies show no degradation of the trimer of phenyl isocyanate below 270°C [10,11]. Catalysts are usually needed to form the isocyanurate bond. Alkali metals of carboxylic acids, such as potassium acetate, various quaternary ammonium salts, and even potassium or sodium hydroxide, are most commonly used as catalysts for the isocyanurate reaction. However, many others will work as well [12]. 

Weakly acidic cation-exchange resins have carboxylic groups (COOH) as the exchange sites. When operated on the hydrogen cycle, the weakly acidic resins are capable of removing only those cations equivalent to the amount of alkalinity present in the water, and most efficiently the hardness (calcium and magnesium) associated with alkalinity, according to these reactions ... 

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