Dicarboxylic acid chlorides

The first, and still widely used, polymer-supported ester is formed from an amino acid and a chloromethylated copolymer of styrene-divinylbenzene. Originally it was cleaved by basic hydrolysis (2 N NaOH, FtOH, 25°, 1 h). Subsequently, it has been cleaved by hydrogenolysis (H2/Pd-C, DMF, 40°, 60 psi, 24 h, 71% yield), and by HF, which concurrently removes many amine protective groups. Monoesterification of a symmetrical dicarboxylic acid chloride can be effected by reaction with a hydroxymethyl copolymer of styrene-divinylbenzene to give an ester a mono salt of a diacid was converted into a dibenzyl polymer. ... 

The dicarboxylic acid chlorides from sebacic and azelaic acid react with 2 moles of enamine to give the tetraketone (117), which on base cleavage... 

Monoesterification of a symmetrical dicarboxylic acid chloride can be effected by reaction with a hydroxymethyl copolymer of styrene-divinylbenzene to give an ester a mono salt of a diacid was converted into a dibenzyl polymer." ... 

Some of the typical conditions of polycondensations used for aliphatic and aromatic monomers are not suitable for furan derivatives, e.g., the melt polycondensation of 2,5-furan dicarboxylic acid chloride with 2,5-b/s(hydroxymethyl) furan at about 80 °C only yields a black insoluble product5. The hydrochloric acid liberated in the reaction is clearly responsible for the charring of the furanic diol which like its simpler homologue furfuryl alcohol, resinifies rapidly in acidic media (see below). 

In principle, the attainment of chemical equilibrium can be accelerated by catalysts however, in contrast to polyester formation, catalysts are not absolutely essential in the above-mentioned polycondensations. The first two types of reactions are generally carried out in the melt solution polycondensations at higher temperature, e.g., in xylenol or 4-fert-butylphenol are of significance only in a few cases on account of the poor solubility of polyamides. On the other hand, polycondensation of diamines with dicarboxylic acid chlorides can be carried out either in solution at low temperature or as interfacial condensation (see Sect. 4.1.2.3). 

As in the preparation of polyesters, also in the preparation of polyamides, the reaction temperature can be considerably reduced by using derivatives of dicarbo-xylic acids instead of the free acids. Especially advantageous in this connection are the dicarboxylic acid chlorides which react with diamines at room temperature by the Schotten-Baumann reaction this polycondensation can be carried out in solution as well as by a special procedure known as interfacial polycondensation (see Examples 4-11 and 4-12). 

A typical member (la) of this group of chiral C2-symmetrical ligands is prepared by reaction of pyridine-2,6-dicarboxylic acid chloride with L-valinol (60% yield). 

Macrocyclic lactams.1 These lactams have generally been prepared by reaction of dicarboxylic acid chlorides and diamines under high dilution. Yields are generally mediocre because linear polyamides are also formed. Actually, free dicarboxylic acids, when activated by diphenylphosphoryl azide, can condense with diamines to... 

Preparation of l,4-Dibromo-2,5-Dicarboxylic Acid Chloride Benzene... 

New guanine receptors were prepared based on 7-acetylamino-2-chloro-4-methyl-1,8-naphthyridine 480 (1988CC765). Amino alcohol 481 was prepared by the reaction of compound 480 with an excess of sodium 2-hydroxyethoxide. Compound 481 reacts with dicarboxylic acid chlorides 482 under high dilution conditions to form naphthyridine macrocycles 483. 

The required novel bifunctional monomers are synthesized by reacting cyclic ureas with aliphatic or aromatic dicarboxylic acid chlorides in the presence of triethylamine as hydrogen chloride scavenger. This reaction is best conducted in an inert organic solvent using an excess of the cyclic urea to prevent polymer formation (Scheme I). 

Reductive acylation. Treatment of anthracene and a dicarboxylic acid chloride with magnesium in DMF leads to the dibenzo bridged diketone product. ... 

Ketocarboxylic acids from dicarboxylic acid chloride esters... 

Arylimines can be obtained by the addition of N-silylated amides to aryl-lithium compounds (Scheme 200) 44 the imines may be isolated or reduced in situ to amines, or hydrolysed to carbonyl compounds. a-Ketodicarboxylic acid chloride imine chlorides, which readily undergo cyclization to N-heterocycles, have been prepared by -addition of dicarboxylic acid chlorides to isocyanides (Scheme 201).444 Two new formimidoylamino-substituted carbapenems (4) have been prepared by a route involving a hetero Diels-Alder reaction (Scheme 4).14... 

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

However, in the reaction of acetylenedicarboxylic acid with thionyl chloride in the presence of DMF, the anhydride (XCIII), rather than the corresponding dicarboxylic acid chloride, was obtained... 

For this reason, a two-step reaction of dihydrazides with dicarboxylic acid chlorides to form poly(hydrazide)s in the first step is favored. A wide variety of aromatic moieties can be used. In the second step, the cyclization to PODA is achieved by cyclodehydration at 300°C in vacuo, or by the application of dehydrating solvents. Likewise, the intermediate poly(hydrazide) can be cast or spun, and the fabricated material can be converted into the PODA form. 

PAIs can be prepared by the condensation of a monoanhydride of a tricarboxylic acid and a primary diamine. Further PAI can be prepared by tbe reaction of dicarboxylic acid chlorides and diamines. Here, either the diamines or diacid halides already contain imide linkages, or mutatis mutandis, amide linkages. Classical PAI are usually obtained by reacting equimolar amounts of trimellitic acid hahde anhydride and a diamine. ... 

Kricheldorf, H.R., Langanke, D., Spickermann, J., and Schmidt, M., Macrocycles 10. Macrocyclic Poly (l,4-butanediol-ester)s by Polycondensation of 2-stanna-1,3-dioxepane with Dicarboxylic Acid Chlorides, MacromoZeci/Zes, 32,3559,1999. 

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