Amide Imides

Many oligomers with various functionalities have been prepared in our laboratory M). However, the amino terminated species has been studied most extensively due to its wide utility as a component of a large number of segmented copolymers (e.g. imides, amides, ureas, etc.). In order to prepare functional oligomers of this type, one must first prepare the disiloxane. One route to this was pointed out some years ago by Saam and Speier (28). They showed that it was possible to react allylamine with a protecting reagent such as hexa-... 

Chiral diazaphosphoramides 278 were obtained from imide-amide rearrangement of the corresponding oxazaphosphorimidate precursors 277 derived from optically active (R)-/V-l-bcnzylaminopropan-2-ol (276) (Scheme 66) [104],... 

The position of the equilibrium (equation 65) depends upon the nature of X, and the intramolecular hydrogen atom transfer can be monitored by H NMR magnetization transfer. This provides a model for the generalized imide-amide-amine interconversion by proton transfer. 

Amines (all types), imides Amide >NCOR Alkyl, Phenyl, - CH2NHCOAr, - CH2OCOR". 

Coordination carbonylation polycondensation has been extended from the synthesis of polyamides [scheme (15)] and polyarylates [scheme (16)] to reactions using other nucleophilic monomers that, with dihaloarenes and carbon monoxide, yield poly(imide-amide)s, poly(acylhydrazide)s, and poly(benzoxa-zole)s [165,170,171],... 

Phosphorsaure-alkyl(aryl)imid-amid-di ester... 

Figure 38 Synthesis of PAEKs incorporating various types of functional groups. Types of X groups incorporated imide, amide, sulfone, ester, azo, quinoxaline, aliphatic, fluoroaliphatic, fluoroaromatic. (From Ref. 164.)...

Asymmetric Alkylations. The use of nitrogen derivatives of carbonyl compounds (imines, imides, amides, sultams, oxazo-lines) is often the most efficient procedure for achieving a-alkylations. Chiral auxiliaries bearing heteroatoms in a 1,2-relationship appear to work best, as they have chelation sites for the metal cation. High levels of asymmetric induction can thus be achieved due to the system rigidity. Cyclic ketones have been alkylated via the lithiated enamine formed from L-f-leucine f-butyl ester (eq 1). High enantiomeric excesses and predictability of absolute configuration make this method attractive. 

The synthesis and equilibration reaction kinetics involved in the preparation of aminopropyl-terminated polysiloxanes has been studied most extensively because of the utility of the amino-terminated species as components of a large number of segmented copolymers such as imides, amides, and ureas. 

New synthetic pathways for the preparation of chiral cyclic oxaza- and diaza-phosphoramidates suitable for use in asymmetric chemistry were studied with respect to the imide-amide rearrangement of cyclic phosphorimidates (Scheme 23). New types of oligomeric organophosphorus compounds (112), formed by a novel ring opening polymerisation, have been identified. These compounds are stable intermediates in the imide-amide rearrangement. 

Crystalline AIN with low carbon incorporation (0.3%) can also be made from the imide-amide oligomer starting with H3Al-NMe3 as the aluminum source and an overpressure of NH3 In a similar manner, pyrolysis of a solid having the composition [Ga(NH)3/2] is useful in preparation of GaN having low carbon incorporation... 

Preparation of precursors imidates, amide hydrazones, and hydrazides 78... 

Once the appropriate imidates, amide hydrazones, or hydrazides are made successfully, the preparations of the target open-chain diazine (N-N) ligands is usually fairly straight-forward. 

Elements of Group V RPC12=NP(0)C12 compounds,390 and further aspects of imide-amide rearrangements, shown in equation (15), have been examined.391 New i.r. data... 

The infrared absorption spectrum of sulfacetamide sodium has been determined in KBr disc (4). The principal peaks appear at 825, 1090,1145,1264,1552,1600 cm 1. The infrared stretching frequencies of the amino group have been used to calculate the force constant, the band angle and the "S" character of the nitrogen orbitals of the N-H band (23,24). Infrared measurements of sulfonamides have been performed to study the imide-amide tautomerism (25) and to see if there is any change in the electronegativity of the SO2 group (26,27). Sulfacetamide in eye-drops and ointments has been identified by attenuated total reflectance (ATR) infrared spectra (28). 

But what is it about this system that makes us call it self-replicating How could we show that the system progresses through directed template catalysis rather than through simple chemical autocatalysis After all, (6) bristles with functional groups. The imide, amide, ribose and purine functionalities must all be considered as possible explanations for the autocatalysis observed. For example, imidazole is a well-known catalyst for acylation reactions, and the purine contains such a subunit. Could not this functionality be the cause The potentially catalytic functions of the product molecule had to be individually tested in the structural context of (6) and under the conditions where (6) acts as an autocatalyst. 

Rasmussen et al. [205] described the use of resin-bound triaryl bismuth diacetates as starting material for O, N and C arylations [206]. In their approach one of the non-polymer-bound aryl groups is transferred onto imides, amides, carbamates, imidazoles, ahphatic amines, anilines, and phenols to yield the corresponding N- and O-arylated compounds. In the case of p-naphthol the a-C-arylated naph-thol was obtained in 49-68% yield. The authors used 1.5 equiv. of P-naphthol, and... 

Dimethylol-5,5-dimethylhydantoin (DMDMH) and 3-methylol-2,2,5,5-tetramethylimidazolidinone (MTMIO) were mixed in different ratios in textile finishing systems for cellulose fabrics. The mixtures of 2,2,5,5-tetrame thylimidazolidinone (TMIO) and hydantoin rings on the grafted cellulose provided a combination of imide, amide and amine halamine stmctuies in different ratios after chlorination. These combinations improved both the power and stability of the biocidal properties of the treated cotton and polyester/cotton blend fabrics studied. Repeated laundering tests showed that even a small amount of added amine halamines could substantially reduce the loss of active chlorine and increase the power of the biocidal functions on the fabrics. The results were discussed. 12 refs. 

Groning, Hakkarainen [14-16,18] Polyamide 66 thermo-oxidation Cyclopentanones, pyridines, cyclic imides, amides, carhoxyhc acids, caprolactam PDMS-DVB... 

Kricheldorf has reported the synthesis of lyotropic poly(amide-imide)s and poly(benzoxazole-amide)s. These were prepared by the polycondensation of N,N-bis(trimethylsilyl)-p-phenylenediamine or N,AT -bis(trimethylsilyl)-3,3 -dim-ethylbenzidine with the diacyl chloride of trimellitimide of p-aminobenzoic acid, or the imide formed from p-amino benzoic acid and terephthalic acid. Lyotropic behaviour was observed in cone, sulphuric acid solution [38]. A series of thermotropic poly(imide-amide)s was prepared based on trimellitimides formed from trimellitic anhydride and an a, -bis(4-aminophenoxy) alkane with carbon chain lengths 9-12. Melting points were in the range 250-300 °C. They formed smectic A phases and tended to degrade around the isotropisation temperatures (around 350 °C). Pendant methyl groups or occupied meta- groups tended to prevent mesophase formation [39]. Novel LC poly(imide-amides) have also been synthesised from new diamine spacers derived from linear diaminoalkanes and 4-nitrophthalic anhydride. A smectic and nematic phase were observed when 4,4 -biphenyl dicarboxylic acid was used as co-monomer [40]. 

The structures and corresponding calculated MI values are given in Table 7 (nos. 1-5). Mesophases were observed for scores of MI=12 and 13 but not for the odd structures (MI range 9.5-11). In addition, a series of imide-amide oligomers were synthesised with molecular weights above 1000, in which the terminal groups were nadic anhydride. Mis ranged from 8.3 to 10.7 but no positive identification of mesophases were made in any of these (Table 7, nos. 6-9)... 

A series of lyotropic poly(imide-amide)s were synthesised [39], in which an ordered unit comprising trimellitimide condensed with p-aminobenzoic acid andp-phenylene diamine (PPD) was copolymerised in varying ratios (0,50 and 80%) with a terephthalic acid/PPD polyamide. The MI predicts all three polymers to be LC, but lyotropic behaviour was observed in only the first one (Table 13). This is particularly surprising because incorporating increasing quantities of the known lyotropic and more linear TPA/PPD units would be expected to produce definite lyotropic behaviour. Similarly, a copoly(amide-imi-de) of 3,3 -dimethyl benzidene and 4-amino benzoic trimellitimide was predicted by the MI to possess a mesophase but none was detected. These apparent failures may be due to the fact that the polymers which did show lyotropic behav-... 

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