Macrocycles polymers

Fig. 15 (a) Formation of a polymer (53 or 55) on reaction of a pyridine-hydrazone-pyridine derived dialdehyde 50 with 1 equiv. of diamine (51 or 52), and its reversible conversion into a macrocycle (54 or 56) in the presence of the appropriate metal ions (b) stylized representation of the polymer/macrocycle reversible switch... 

A polymer/monomer (polymer/repeat-unit or polymer/macrocycle) switch may become of practical importance where a polymer decorated with certain groups has specific size-dependent properties that the monomeric units do not have. The modulation of the conversion between polymeric and monomeric (or macrocyclic) states would also result in the modulation of these properties. Moreover, such size switches, represented by polymerization/depolymerization processes that operate under the control of external events, are examples of environmentally-friendly recyclable polymers (reduction of waste treatment). As well, if the polymer has low solubility and the polymer/monomer switch can work in spite of this, then it becomes possible to reversibly generate a precipitating (solid) polymeric material from a liquid solution of monomer. 

Perhaps the most functional group-tolerant approach is that of heterodifunctional click cyclization. This has shown compatibility with both a wide range of polymerization techniques and monomer types, as well as a diversity of side-chain functionality. Nonetheless, the preparation of larger polymer macrocycles remains... 

Studies on macrocyclic polymers have been of fundamental interest to the polymer community for some time now. Since, unlike linear polymers, macrocyclic polymers lack chain-ends, a comparison of the two over a broad spectrum of properties is expected to lead to an enhanced understanding of polymer properties in general. 

First the protected oligopeptide is coupled with polymer-bound nitrophenol by DCC. N"-Deblocking leads then to simultaneous cycliiation and detachment of the product from the polymer (M. Fridkin, 1965). Recent work indicates that high dilution in liquid-phase cycli-zation is only necessary, if the cyclization reaction is sterically hindered. Working at low temperatures and moderate dilution with moderately activated acid derivatives is the method of choice for the formation of macrocyclic lactams (R.F. Nutt, 1980). 

The polymerization of ethyleneimine (16,354—357) is started by a catalyticaHy active reagent (H or a Lewis acid), which converts the ethyleneimine into a highly electrophilic initiator molecule. The initiator then reacts with nitrogen nucleophiles, such as the ethyleneimine monomer and the subsequendy formed oligomers, to produce a branched polymer, which contains primary, secondary, and tertiary nitrogen atoms in random ratios. Termination takes place by intramolecular macrocycle formation. 

Stmctural and chemical modification of urethane containing polymer matri-ces with macrocycles - calixarenes having reactive hydrazide groups have been carried out and stmcture, physico chemical and sensor properties of polyure-thanesemicarbazides (PUS) synthesised have been studied. The polymers obtained (on the base of polypropylene glycol MM 1000 and polysiloxane diol MM 860, hexamethylene diisocyanate and calixarene dihydrazide) are identified by IR-spectroscopy, size exclusion chromatography (SEC), DSC, WAXS and SAXS methods. 

The original cyclooligomerization noted above was conducted using alkyl aluminum, zinc and magnesium compounds ". Both open-chained and cyclic polymers were obtained in addition to dioxane. The principal macrocyclic component of the mixture was apparently 12-crown-4 (EO-4) which was said to be valuable as a high boiling neutral solvent... . " The reaction is shown below in Eq. (1.2). 

Reinhoudt, Gray, Smit and Veenstra prepared a number of monomer and dimer crowns based on a variety of substituted xylylene units. They first conducted the reaction of 1,2-dibromomethylbenzene and a polyethylene glycol with sodium hydride or potassium Z-butoxide in toluene solution. Mixtures of the 1 1 and 2 2 (monomer and dimer) products were isolated and some polymer was formed . The reaction was conducted at temperatures from 30—60° and appeared to be complete in a maximum of one hour. The authors noted that the highest yield of 1 1 cyclic product was obtained with disodium tetraethylene glycolate instead of dipotassium hexaethylene gly-colate (see also Chap. 2) . Chloromethylation of 1,3-benzodioxole followed by reaction with disodium tetraethylene glycolate afforded the macrocycle (29% yield) illustrated in Eq. (3.20). 

Finally, the 1,3-dione systems prepared by Cram and Alberts deserve special note . These compounds, referred to as hexahosts are similar to the polymer-bound material illustrated as Compound 29 in Chap. 6. The synthesis is based on a methylene-bridged bis-dithiane unit. One of these may be cyclized with a polyethylene glycol, or more than one unit may be incorporated to give multiple 1,3-dione binding sites in the macrocycle. The former case is illustrated in Eq. (3.46). 

In 1930, in one of many pioneering studies, Carothers showed that certain condensation polymers could be cyclic or macrocyclic rather than exclusively linear. In addition to this very important observation, he showed that thermolysis in vacuo of certain polymers could also yield macrocyclic materials. Quite a number of papers have been published on this subject since that time, especially dealing with the chemistry of phthalate " , isophthalate " ", and terephthalate esters Many of these structures are tabulated at the end of this... 

Polymer-supported synthesis of natural macrocyclic lactones and other 0-heterocycles 99AG(E)1903. 

This compound has been investigated by several groups,379- 384 but due to its practical insolubility it has not been fully characterized. Another approach to obtain phthalocyanine network polymers is with the use of crown ethers385 or other groups like di oxy -para-p h enyle n e3 8 6 as bridging units between the macrocycles. Some attempts to obtain metal phthalocyanine substructures arranged as ladder polymers have also been proposed (see below).344... 

Trost and coworkers137 have reported the polymer-supported palladium catalyzed cyclization of 1, l-bis(phenylsulfonyl)epoxyalkene 235 which gives cycloalkanes 236 and 237 in a 2 1 ratio (equation 143). This method has proven useful for the synthesis of macrocyclic compounds under neutral conditions without using high dilution technique. Temperature and concentrations are critical. The best results are achieved if a reaction mixture of 0.1-0.5 m is added to a preheated (at 65 °C) suspension of the catalyst. 

In connection with studies on the ring-opening polymerization of cyclic acetals, we have undertaken investigations on the polymerization of bicyclic acetals, bicyclic oxalactone, and bicyclic oxalactam, which yield polysaccharide analogs, macrocyclic oligoesters, and a hydrophilic polyamide, respectively, some of which can be expected to be useful as novel speciality polymers. The monomers employed in the studies were prepared via synthetic routes presented in Scheme 1, starting from 3,4-dihydro-2H-pyran-2-carbaldehyde (acrolein dimer) I. 

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