Ketone-imides

An attempt to explain the colours of all carbon compounds by the existence of such rings possesses great interest, but it cannot be denied that the necessary conditions are absent in numerous dyestuffs, for example, thioketones, ketone-imides, and hydrazides arc such bodies, i. e. tetramethyldiamidothiobenzophenone and auramine,... 

Treatment of a thirteen-membered lactam with 1-naphthylmagnesium bromide forms both a cyclic enamine and the amino ketone. Imides of dicarboxylic acids produce with organometallic reagents cyclic enamino compounds such as 108 (n = 1,2) . ... 

C.-Y. Wang, G. Li, J.-M. Jiang, Synthesis and properties of fluorinated poly(ether ketone imide)s based on a new unsymmetri-cal and concoplanar diamine 3,5-dimethyl-4-(4-amino-2-trifluoromethylphenoxy)-4 -aminobenzophenone. Polymer 50 (7) (2009) 1709-1716. 

Dimethylamino-phenyl]-[4-p-tolaidino-naphthyl-(l )].keton-imid 14,121. 

Considerable attention has been devoted to the preparation of fluorine-containing polymers because of their unique properties and high temperature performance (I). Recently we reported the preparation and characterization of novel fluorine-containing polyimides and polyethers which exhibit low moisture absorption and low dielectric constants (2, 3). Fluorinated polyimides absorb 1 wt% water and have dielectric constants of about 2.8 (all dielectric constants reported in this paper were measured at 10 kHz) vtdiereas their non-fluorinated analogs absorb as much as 3 wt% water and have dielectric constants of about 3.2. Fluorinated polyarylethers, which are free of polar groups such as ketones, imides and sulfones, absorb as little as 0.1 wt% water and have dielectric constants less than 2.8. 

Nucleophilic displacement of an activated dihalo or dinitro compound with an activated bisphenoxide salt at high temperatures has been the most explored method of poly (aryl ether) synthesis [62], These synthetic strategies were further extended for the preparation of hb poly(aryl ether)s in one-step polymerization from AB2 monomers containing a phenolic group and two aryl fluorides, which were activated toward nucleophilic displacement by a sulfone, ketone, imide, or heterocycle [63-65]. Miller et al. [63], Hawker and Chu [65], and Shu and Leu [66] reported the synthesis of hb poly(aryl ether ket(Mie)s (hb-PAEKs) via the AB method. The structures of AB2 monomers reported by Hawker and Chu [65] are shown in Scheme 4 (1-5 and 1-6). The structiu es of AB2 monomers reported by Shu and Leu [66] are shown in 1-7, Scheme 4. 

Scheme 11 Structure of AB2 monomer with ketone-imide moiety [131]...

Baek JB, Qin H, Mather PT, Tan LS (2002) A new hyptabranched poly(arylene-ether-ketone — imide) synthesis, chain-end functionalization, and blending with a bis(maleimide). Macnnnolecules 35 4951-4959... 

Wang DH, Back JB, Tan LS (2(X)5) Phthalonitrile-terminated hyperbranched poly(arylene-ether-ketone-imide) synthesis and its blending with 4,4 -bis(3,4-dicyanophenoxy)biphenyl, phthalonitrile-terminated hyperbranched poly(arylene-ether-ketone-imide) synthesis and its blending with 4,4 -Bis(3,4-dicyanophenoxy)biphenyl. Polym Prepr 46 727-728... 

Yu Z, Possum E, Wang DH, Tan LS (2(X)8) Alternative approach to an AB2 monomer for hyperbranched poly(arylene ether ketone imide)s. Syn Commun 38 419-427... 

Almost insoluble in cold water. Higher alcohols (including benzyl alcohol), higher phenols (e.g., naphthols), metaformaldehyde, paraldehyde, aromatic aldehydes, higher ketones (including acetophenone), aromatic acids, most esters, ethers, oxamide and domatic amides, sulphonamides, aromatic imides, aromatic nitriles, aromatic acid anhydrides, aromatic acid chlorides, sulphonyl chlorides, starch, aromatic amines, anilides, tyrosine, cystine, nitrocompounds, uric acid, halogeno-hydrocarbons, hydrocarbons. 

The above is an example of the Guareschi reaction. It is applicable to most dialkyl ketones and to alicyclic ketones (e.g., cyclohexanone, cyc/opentanone, etc.). The condensation product (I) is probably formed by a simple Knoe-venagel reaction of the ketone and ethyl cyanoacetate to yield ethyl a-cyano-pp dimethylacrylate (CH3)2C=C(CN)COOCjHj, followed by a Michael ad tion of a second molecule of ethyl cyanoacetate finally, the carbethoxyl groups are converted to the cyclic imide structure by the action of ammonia. 

The imides, primaiy and secondary nitro compounds, oximes and sulphon amides of Solubility Group III are weakly acidic nitrogen compounds they cannot be titrated satisfactorily with a standard alkaU nor do they exhibit the reactions characteristic of phenols. The neutral nitrogen compounds of Solubility Group VII include tertiary nitro compounds amides (simple and substituted) derivatives of aldehydes and ketones (hydrazones, semlcarb-azones, ete.) nitriles nitroso, azo, hydrazo and other Intermediate reduction products of aromatic nitro compounds. All the above nitrogen compounds, and also the sulphonamides of Solubility Group VII, respond, with few exceptions, to the same classification reactions (reduction and hydrolysis) and hence will be considered together. 

Synthesis and Properties. A number of monomers have been used to prepare PQs and PPQs, including aromatic bis((9-diamines) and tetramines, aromatic bis(a-dicarbonyl) monomers (bisglyoxals), bis(phenyl-a-diketones) and a-ketones, bis(phenyl-a-diketones) containing amide, imide, and ester groups between the a-diketones. Significant problems encountered are that the tetraamines are carcinogenic, difficult to purify, and have poor stabihty, and the bisglyoxals require an arduous synthesis. 

A large variety of newer poly(ether imide)s has been described. Included among these are perfluorinated polymers (96), poly(ester ether imide)s (97), poly(ether imide)s derived from A/,Ar-diamino-l,4,5,8-naphthalenetetracarboxyHcbisimide (98), and poly(arylene ether imide ketone)s (99). In addition, many other heterocyHc groups have been introduced into polyether systems, eg, poly(pyrazole ether)s (100) and poly(aryl ether phenylquinoxaLine)s (101) poly(aryl ether oxazole)s with trifluoromethyl groups (102) and polyethers with other heterolinkages, eg, poly(arylether azine)s (103). 

Polyimides have been synthesized by Diels-Alder cycloaddition of bismaleimides and substituted biscydopentadienones (81,82). The iatermediate tricychc ketone stmcture spontaneously expeU carbon monoxide to form dihydrophthalimide rings, which are readily oxidized to imides ia the presence of nitrobenzene. 

Appllca.tlons. MCA is used for the resolution of many classes of chiral dmgs. Polar compounds such as amines, amides, imides, esters, and ketones can be resolved (34). A phenyl or a cycloalkyl group near the chiral center seems to improve chiral selectivity. Nonpolar racemates have also been resolved, but charged or dissociating compounds are not retained on MCA. Mobile phases used with MCA columns include ethanol and methanol. 

Other substitution reactions have been described with ketones, epoxides, anhydrides, acyl haUdes, amides, and imidates, among others (4). 

Cyanopyridazines add ammonia, primary and secondary amines and hydroxylamine to give amidines or amidoximes. Substituted amides, thioamides and carboximidates can be also prepared. With hydrazine, 3-pyridazinylcarbohydrazide imide is formed and addition of methylmagnesium iodide with subsequent hydrolysis of the imine affords the corresponding pyridazinyl methyl ketone. 

The thiation procedure described here is an example of a general synthetic method for the conversion of carbonyl to thiocarbonyl groups. Similar transformations have been carried out with ketones, carboxamides,esters,thioesters, 1 actones, " thiol actones, - imides, enaminones, and protected peptides. ... 

The ethyl cyanoacetate and methyl ethyl ketone were Eastman Kodak Company white label grade chemicals and were used without further purification. Commercial absolute ethanol was found to give a slightly better yield of the ammonium salt of the imide. 

Guareschi imides are useful synthetic intermediates. They are formed from a ketone reacting with two equivalents of the cyanoacetic esters and ammonia. This transformation is illustrated in the formation of 4,4-dimethylcyclopentenone 30.The synthesis was initiated with the Guareschi reaction of 3-pentanone 27 with 28 to generate imide 29. This product was hydrolyzed to the diacid and esterified. Cyclization of the diester via acyloin condensation followed by hydrolysis and dehydration afforded the desired target 30. 

It was anticipated that two of the three stereochemical relationships required for intermediate 12 could be created through reaction of the boron enolate derived from imide 21 with a-(benzyloxy)ace-taldehyde 24. After conversion of the syn aldol adduct into enone 23, a substrate-stereocontrolled 1,2-reduction of the C-5 ketone car-... 

In a similar way. ft-keto imide 19 undergoes stereodivergenl aldol reactions. Thus, conversion of 19 into the tin enolate, and subsequent addition of aldehydes, give predominantly the diastereomers 20. On the other hand, hydroxy ketones 21 are the main products when the chlorotitanium enolate of 19 is reacted with aldehydes53. ... 

Bourgeois et al. reported a new approach227 wherein poly(arylene ether sulfone) and poly(arylene ether ketone) were functionalized with anhydride and amine chain ends, respectively, to afford imide-linked copolymers. 

Hedrick et al. reported imide aryl ether ketone segmented block copolymers.228 The block copolymers were prepared via a two-step process. Both a bisphenol-A-based amorphous block and a semicrystalline block were prepared from a soluble and amorphous ketimine precursor. The blocks of poly(arylene ether ether ketone) oligomers with Mn range of 6000-12,000 g/mol were coreacted with 4,4,-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in NMP in the presence of A - me thy 1 morphi 1 i nc. Clear films with high moduli by solution casting and followed by curing were obtained. Multiphase morphologies were observed in both cases. 

Imide aryl ether ketone segmented block copolymers, 360 Imide chemistry, 292-295 Imide cyclization, 301 Imide exchange, polyimide syntheses by, 268... 

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