With terephthaloyl chloride

Rather similar materials have been made available by Monsanto, made by reacting p-aminobenzhydrazide with terephthaloyl chloride (Figure 18.33). The fibre is marked as PABH-T X-500. 

Figure 3.1 HPLC traces of (a) cyclic PBT oligomers from the reaction of butane diol with terephthaloyl chloride (cyclic dimer at 3.6 min), and (b) linear oligomers from butane diol and dimethyl terephthalate...

The results of the various methods used to determine the molecular weight and degree of functionality of the diamine are shown in Table II. All of this evidence is consistent with the conclusion that the purified, isolated diamine possesses high difunctionality. When the diamine was chain extended with terephthaloyl chloride, a polymer product with a symmetrical molecular weight distribution was obtained (D.P. a 10). Inexact stoichiometry is most probably responsible for the limited extent of chain extension. 

As illustrated in Scheme 2,3,9-bis (4-hydroxy-3-methoxyphenyl)- 2,4,8,10-tetraoxa-spiro [5,5] undecane, designated bisphenol [IV], was synthesized from vanillin and pentaerythritol. Polyesters were obtained by the reaction of [IV] with terephthaloyll chloride or sebacoyl chloride (5). 

Some results of the modification of lignin sulfonate Ultra B002 by reaction with terephthaloyl chloride are summarized in Table VI. The total hydroxyl content of the lignosulfonates as well as their derivatives are presented in Table VII. The hydrolytic resistance of selected products is evaluated in Table VIII. The results presented in Tables VI-VIII stress several advantages of the derivatives with terephthaloyl chloride. The modified lignin sulfonates were insoluble, or only very slightly soluble, in organic solvents. They were, however, soluble in dimethyl sulfoxide. Ordered structures were identified by X-ray studies (16,17). 

The modification of lignin sulfonates with terephthaloyl chloride produces new polymeric materials containing ester groups. This modification can be used to utilize lignins also for improvement of chemical fiber properties. This is presently under investigation. 

Table VI. Effect of Modification with Terephthaloyl Chloride on the Properties of the Ultra B002 Product.

Table VII. Total Hydroxyl Content of Lignin Sulfonates and Their Derivatives with Terephthaloyl Chloride.

Table VIII. Hydrolytic Resistance of the Lignins Modified with Terephthaloyl Chloride...

In order to compare chiral recognition of the substrate p-chlorostyrene in the presence of chiral picket fences and basket handles carrying the same amino acids the porphyrins 167-169 were prepared in a straightforward manner from the known a,j8,a,j -tetra(o-aminophenyl)porphyrin 170, Fig. 28 [113]. Reaction with t-butoxycarbonyl-L-phenylalanine, removal of the protecting group and subsequent condensation with terephthaloyl chloride e.g. furnished the free base of 169. Iron was always introduced using Fe(CO)5/I2 and the... 

Multiblock polymers were prepared from PPO prepolymers with molecular weights 400, 1000, 2000, 3000, and weight fractions of PPO 25, 50, and 75%. PPO homopolymers were prepared by reacting PPO prepolymer with terephthaloyl chloride alone. A sample also was prepared containing 50% PDEGA of mol wt 2550. 

Diaryl phthalides, particularly phenolphthalein 281 and several phthalides derived from it, are widely used for the preparation of cardo polymers. The term is derived from the latin word for hinge or pivot, which is an apt name given that the aryl substituents are hinged on the C-3 carbon of the phthalide. In one application, compound 281 was used to prepare phthalamide 282 and both bisphenols were copolymerized with terephthaloyl chloride 283 to form polyesters. These formed strong flexible fdms with improved thermal stability and solubility <1997PSA3227>. 

The use of metal in Friedel-Crafts acylation has been patented for the production of diketones, significant in the field of material chemistry. Thus, l,4-bis(4-methoxybenzoyl)benzene 36 can be synthesized by double acylation of anisole with terephthaloyl chloride 35 in the presence of zinc or iron metal (Scheme 3.8). ... 

Thermoplastic polymers were also earlier reported to have been prepared by heating tricyclodecane dithiol with terephthaloyl chloride in a chlorinated solvent [16b]. Additional examples are cited for polythioesters based on bis-phenol A and random other polythioesters derived from bicyclic thiols. The starting diolefins for the dithols are prepared by the Diels-Alder synthesis using cyclopentadiene, acetylene, butadiene, etc. 

Cyclodextrin catenanes were synthesized for the first time by Stoddart s group in 1993 [66, 67] (Fig. 12.7). The molecular thread consisted conceptually of three parts, a hydrophobic aromatic core bearing on either side hydrophilic arms ending with amino groups that were dipped together by reaction with terephthaloyl chloride as in 13. 

Similar simple reactions can be carried out in solution. Terminal hydroxy groups can be esterified with trifluoroacetic anhydride or glutaric anhydride , although the reaction in the latter case is probably incomplete. Amino groups in the monolayer of cysteamine were reported to react with active esters, such as JV-hydroxysuccinimide (equation 8) . No characterization of the resultant monolayer was, however, given. Cysteamine mono-layers were also acylated with terephthaloyl chloride and an isocyanate derivative . ... 

The fiber may be spun from a solution of the polymer in dimethylformamide containing lithium chloride. In 1973, Du Pont commenced production of another aromatic polyamide fiber, a poly(p-phenylene terephthalamide) marketed as Kevlar. It is produced by the reaction of p-phenylenediamine with terephthaloyl chloride in a mixture of hexametylphosphoramide and N-methyl pyrrolidone (2 1) at -10 C. 

Fig.6. Proposed formula of a bis(benzophenoxazinyl) derivative obtained when reacting Nile Blue with terephthaloyl chloride.

Two examples may be given, by reacting the reduced form of Nile Blue with 1,5-dichloro-2,5-dinitrobenzene, one compound could be obtained with an E -value of —135 mV vs SCE (pH 7.0), and by reacting the iminoform of Brilliant Cresyl Blue with terephthaloyl chloride a compound could be obtained with an E -value of —55 mV vs SCE (pH 7.0). They were both found to be catalytically active for NADH-oxidation. No kinetic data are available yet, however. Purification and identification of both the commercially available phenoxazines (usually with a purity of 50-90 %) and of the reaction products are far from straightforward. 

The first papers on isohexide based semi-aromatic homo-polyesters were published by Thiem et al. in 1984 [10,11]. They prepared polyesters from all three isohexides by melt condensation with terephthaloyl chloride at elevated temperatures (Figure 9.3). Colourless, brittle oligomers were obtained with Mn 3000-8000. These materials exhibited very high TgS - that is. 

Later, Braun et al. reported the synthesis of a broad range of polyesters from isosor-bide/isomannide and acid dichlorides via melt condensation [12], The acid chlorides used include linear C4-C16 alkanoyl, ortho/iso/terephthaloyl, and 1,8- and 2,6-naphthalenoyl. Relatively high aliphatic polyesters were obtained, with up to 60 000 (GPC) for poly(isosorbide sebacate). Contrary to the aliphatic polyesters, the semi aromatic polyesters are highly viscous at high temperatures, hampering polycondensation. The TgS recorded for polyesters obtained by melt polymerization of isosorbide or isomannide with terephthaloyl chloride were 147 and 156 °C, respectively. 

The above condensation, carried out with terephthaloyl chloride, yields a polymer that melts at 450... 

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