Dicarboxylic acid chloride synthesis

Posner s reagent has also been used for synthesis of bis-f-butyl diketones by reaction with dicarboxylic acid chlorides (equation I). ... 

The polycondensation of a diol and the diester of a dicarboxylic acid (e.g., the dimethyl ester) can be carried out in the melt at a considerably lower temperature than for the corresponding reaction of the free acid. Under the influence of acidic or basic catalysts a transesterification occurs with the elimination of the readily volatile alcohol (see Example 4.3). Instead of diesters of carboxylic acids one can also use their dicarboxylic acid chlorides, for example, in the synthesis of high-melting aromatic polyesters from terephthaloyl dichloride and bisphenols. The commercially very important polycarbonates are obtained from bisphenols and phosgene, although the use of diphenyl carbonate as an alternative component is of increasing interest (see Example 4.4). Instead of free acids, cyclic carboxylic... 

Another laboratory method of synthesis of diisocyanates is the thermolysis of bisacylazides (4) (Curtius reaction). For example, dicarboxylic acid chlorides react... 

Hattori T, Kagawa K, Kakimoto M and Imai Y (1993) Novel 2-step synthesis of poly(benzo-thiazoles) via new precursor polyamides from 2,5-bis[(cyanoethyl)thio]-l,4-phenylenediamine and aromatic dicarboxylic-acid chlorides. Macromolecules 26 4089-4093. 

Synthesis of carboxylic acid esters from dicarboxylic acid chloride esters via ketocarboxylic acid esters s. 11, 900... 

The synthesis of block copolymers can be easily carried out if functional groups such as acid chloride ( COCl), amines ( -NH2), or alcohols (-"UH) are present at chain ends. This way, a polymer of one kind (say, polystyrene or polybutadiene) with dicarboxylic acid chloride (ClCO COCl) terminal groups can react with a hydroxy-terminated polymer (OH> OH) of the other kind (say, polybutadiene or polystyrene), resulting in an AB type block copolymer, as follows ... 

The benzoic acid derivative 457 is formed by the carbonylation of iodoben-zene in aqueous DMF (1 1) without using a phosphine ligand at room temperature and 1 atm[311]. As optimum conditions for the technical synthesis of the anthranilic acid derivative 458, it has been found that A-acetyl protection, which has a chelating effect, is important[312]. Phase-transfer catalysis is combined with the Pd-catalyzed carbonylation of halides[3l3]. Carbonylation of 1,1-dibromoalkenes in the presence of a phase-transfer catalyst gives the gem-inal dicarboxylic acid 459. Use of a polar solvent is important[314]. Interestingly, addition of trimethylsilyl chloride (2 equiv.) increased yield of the lactone 460 remarkabiy[3l5]. Formate esters as a CO source and NaOR are used for the carbonylation of aryl iodides under a nitrogen atmosphere without using CO[316]. Chlorobenzene coordinated by Cr(CO)j is carbonylated with ethyl formate[3l7]. 

Claisen ester condensation, 6, 279 Thiazolecarboxylic acid chlorides reactions, 6, 279-280 Thiazolecarboxylic acid hydrazides synthesis, 6, 280 Thiazolecarboxylic acids acidity, 6, 279 decarboxylation, 6, 279 reactions, S, 92 6, 274 Thiazole-2-carboxylic acids decarboxylation, S, 92 Thiazole-4-carboxylic acids stability, S, 92 Thiazole-5-carboxylic acids decarboxylation, S, 92 Thiazole-4,5-dicarboxylic acid, 2-amino-diethyl ester reduction, 6, 279 Thiazole-4,5-dicarboxylic acids diethyl ester saponification, 6, 279 Thiazolediones diazo coupling, 5, 59 Thiazoles, 6, 235-331 ab initio calculations, 6, 236 acidity, S, 49 acylation, 6, 256 alkylation, S, 58, 73 6, 253, 256 analytical uses, 6, 328 antifogging agents... 

Cefpimizole (51) appears to be less active in vitro than cefotaxime and cefoperazone and to have a somewhat narrower activity spectrum although some strains of Pseudomonas are susceptible. It is not orally active, but its performance in vivo appears superior to what would be expected from its in vitro data. Its synthesis begins by acylation of cephaloglycin (48) with the bis acid chloride of imidazole-4,5-dicarboxylic acid (49) to give amide 50. The acetyl moiety at C-3 of this intermediate is displaced with 4-pyridineethanesulfonic acid and sodium iodide to give cef-pimazole (51) [16]. 

The first synthesis of derivatives (77) of pentatetraene-carboxylic acid has been reported using a Wittig reaction of 1-H-allene-l,3-dicarboxylate monoester chlorides (76) in the presence of triethylamine.60 In one case an intermediate was obtained and was converted to (77) by further treatment with base. The reaction of carbon suboxide with phosphonium ylides has also... 

Synthesis. Functionalized monomers (and oligomers) of sebacic acid (SA-Me2) and 1,6 -bis(/ -carboxyphenoxy)hexane (CPH-Me2) were synthesized and subsequently photopolymerized as illustrated in Figure 1. First, the dicarboxylic acid was converted to an anhydride by heating at reflux in methacrylic anhydride for several hours. The dimethacrylated anhydride monomer was subsequently isolated and purified by dissolving in methylene chloride and precipitation with hexane. Infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis results indicated that both acid groups were converted to the anhydride, and the double bond of the methacrylate group was clearly evident. 

Chinese chemists have reported the synthesis of pentacyclo[4.3.0.0 , 0 ]nonane-2,4-bis(trinitroethyl ester) (88). This compound may find potential use as an energetic plastisizer in futuristic explosive and propellant formulations. The synthesis of (88) uses widely available hydroquinone (81) as a starting material. Thus, bromination of (81), followed by oxidation, Diels-Alder cycloaddition with cyclopentadiene, and photochemical [2 - - 2] cycloaddition, yields the dione (85) as a mixture of diastereoisomers, (85a) and (85b). Favorskii rearrangement of this mixture yields the dicarboxylic acid as a mixture of isomers, (86a) and (86b), which on further reaction with thionyl chloride, followed by treating the resulting acid chlorides with 2,2,2-trinitroethanol, gives the energetic plastisizer (88) as a mixture of isomers, (88a) and (88b). Improvements in the synthesis of nitroform, and hence 2,2,2-trinitroethanol, makes the future application of this product attractive. 

Fully aromatic polyamides are synthesized by interfacial polycondensation of diamines and dicarboxylic acid dichlorides or by solution condensation at low temperature. For the synthesis of poly(p-benzamide)s the low-temperature polycondensation of 4-aminobenzoyl chloride hydrochloride is applicable in a mixture of N-methylpyrrolidone and calcium chloride as solvent. The rate of the reaction and molecular weight are influenced by many factors, like the purity of monomers and solvents, the mode of monomer addition, temperature, stirring velocity, and chain terminators. Also, the type and amount of the neutralization agents which react with the hydrochloric acid from the condensation reaction, play an important role. Suitable are, e.g., calcium hydroxide or calcium oxide. 

Optically active namral and unnamral amino acids as well as various cyclic amino alcohols have been utilized in the synthesis of a wide variety of bis(oxazo-line) ligands. As previously mentioned, the first bis(oxazoline) ligands, py-box la-d, were synthesized by Nishiyama and co-workers in 1989. The common material for their syntheses was pyridine 2,6-dicarboxylic acid 19. Conversion of 19 to the acid chloride was achieved by treatment with thionyl chloride, as illustrated in Figure 9.4. This was followed by condensation with (5)-valinol in the presence of triethylamine. Conversion of the resulting bis(amidodiol) 20 to py-box-ip lb was achieved by sequential treatment of 20 with thionyl chloride at 50 °C followed by cyclization with aqueous sodium hydroxide in methanol to afford py-box-/p lb in 60% overall yield. The same synthetic scheme can be used to obtain the other... 

The synthesis of optically active polyamides, or nylons, is a growing area of interest. From 1980 to 1991 there have been many citations in Chemical Abstracts on this subject. For example, optically active polyamides have been prepared for the resolution of optical isomers. The polyamides are prepared from optically active amines or dicarboxylic acids. One polyamide was prepared from (-)-(ram-l,2-diaminocyclohexane and terephthaloyl chloride and was used to resolve 2,2 -dihydroxy-6,6 -dimethylbiphenyl [31]. These optically active polyamides can be used in chromatography applications to resolve other optically active compositions. 

An important reaction for synthesis of alkyl and dialkylethanoic acids (RX and R X are primary or secondary alkyl halides) dicarboxylic acids (RX = haloester) unsaturated acids (RX = an unsaturated halide, best for allylic halides) /3-keto acids (R = acyl chloride) (see Sections 18-8C and 18-8D). 

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