Diesters, from dihalides

Polyamine chain extension, 48-56 by acrylamide 51, 52. 53 by aziridine 48,49 by l-bromo-3-chloropropane, 55 by (2-bromoethyl)phthalimide, 51 by 3-bromopropylphthalimide, 53 by chloroacetonitrilc, 51 by chloroacetyl chloride. 50 by lV-(2-chloroethyl)acetamide, 52 by derivatives of chloroacetic acid. 50 by dichloro(o)-bromoalkyl)boranes. 56 by IV-ethylchloroacetamide, 52 by 3-phthalimidopropyl tosylate, 54 by /V-tosyl-2-bromoethylamine, 49 by 2-(N-tosylamino)ethyl tosylate. 49 by Af-tosylaminoacetyl chloride, 50 Polyamino diols. 59 Polyaza-crown macrocycles. 349-367 alkyl-substituted. 364.365 from bis-sulfonamides, 358-361 from diacid dichlorides, 352-357 from diesters, 352-357 from dihalides, 362-366 from diols, 366 from ditosylates. 362-366 Polyaza-crown macrocycles (miscellaneous), table. 392... 

Cesium phenolates were introduced by Kellogg [16] for the synthesis of crown compounds, after crown ether diesters had been obtained in good yields from the cesium salts of aromatic carboxylic acids and oligoethylene glycol dihalides... 

Diacyloxy compounds are intermediates in the conversion of olefins and 1,2-dihalides to glycols (method 95). Although the diesters are seldom isolated, yields are good where their isolation has been attempted. The well-known reaction of an alkyl halide with a silver salt of an acid is used infrequently. It is sometimes valuable in making esters from acids which isomerize during direct esterification. Thus, the labile double bond of 3 niethyl-3-butenoic acid is unaffected by conversion to the methyl ester by this method. ... 

Carboxylic acids can be converted by ancxlic decarboxylation into radicals and/or carbocations. The reaction conditions are simple an undivided beaker-type cell as reaction vessel, controlled current supplied from an inexpensive d.c. power supply and meAanol as solvent are in most cases sufficient. A scale-up is fairly easy and the yields are in general good. By the radical pathway 1,/i-diesters, -diketones, -dienes and -dihalides, chiral intermediates for synthesis, pheromones and unusual fatty acids are accessible in just a few steps. The addition of the intermediate radicals to double bonds affords additive dimers, whereby four building units, two alkyl radicals from the carboxylates and two alkenes, can be coupled in one step. Five-membered hetero- or carbo-cyclic compounds can be prepared by intramolecular addition starting from unsaturated carboxylic acids. 

Base-Catalyzed cyclization of diesters provide another synthetic route. For example, a Dieckmann condensation is used to prepare the benza-zocinone 113.246 A large number of hexahydro-l-benzazocin-5-ones were made in a similar manner.247 Belleau248 obtained the 2-benzazocine 105 (R = CH2CH2OH) from the condensation of ethanolamine with the appropriate dihalide. 

The displacement of halogen from phosphonic dihalides with thiols in the presence of an appropriate base leads to 5,S-diesters rather than (9,5-isomers (equation 30 Z = 0)2-7374,375 gych a reaction has been employed in the determination of the enantiomer composition of chiral thiols. The NMR spectra for a series of phosphonodithioates 163 (Z = O, R = Me, Ph, PhCH2) and also for analogous trithiophosphonates 163 (Z = S, R = Me or Ph) in which the group R is derived from a chiral thiol, showed that the best separation of P NMR signals for the diastereoisomeric forms was achieved when R = Me. Displacement reactions which involve the loss of chlorine from R2P(Z)C1 (Z = or Se ). RP(0)(SR )CP and RP(S)(NHR )C1 by thiols in the presence of a tertiary amine base, and many more, are widely exemplified. 

This reaction was first reported by Perkin in 1883. It is the nucleophilic alkylation between malonic ester and Q, o)-alkyl dihalide to form cyclic aliphatic 1,1-diester or acid and is known as the Perkin reaction or Perkin synthesis. Although it was once referred to as the Perkin condensation, this name should not be used for this type of reaction. Using this protocol, Perkin successfully prepared cyclopropane-, cyclobutane-, cyclopentane-, cyclohexane-, and cycloheptane-1,1-dicarboxylie acids. However, this reaction is often complicated by the side reaction that forms Q, o, a ,a -tetracarboxylic ester from the Sn2 reaction between malonic ester and o, a -alkyl dihalide, this side reaction can be depressed if alcoholic sodium malonic ester is added slowly to the o, a -alkyl dihalide with vigorous stirring. It is interesting that the K2CO3 promoted a reaction between dimethyl 1,3-acetonedicarboxylate and tran5 -l,4-dibromobutene yields vinyldihydrofuran. ... 

Phosphinic acids may be produced by oxidation of primary phosphines or primary phosphine oxides, but the products are liable to be contaminated with phosphonic acids (6.26). Phosphinic acids may also be produced by hydrolysis of phosphonous dihalides (6.164), phosphonous diesters (6.224) or phosphonous diamides (7.189). Good yields are obtained from the halides by adding alcohol, then refluxing with water. 

Phosphonothious acids may exist in equilibrium with the two phosphinothioic acids. The diesters can be made by reacting alcohols or thiols with an appropriate chlorophosphonite, in the presence of a base to remove hydrogen chloride (9.467, 9.468). A cyclic phosphonothionic ester can be obtained from phosphonic dihalides (9.528). 

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