Cellulose amide derivatives

The methyl ester of oxycellulose, produced by alkaline permanganate oxidation of cuprammonium cellulose followed by treatment with diazomethane, has been reacted with protein by the azide method [34]. Acidic oxyce]]uloses are aiso able to react with alcohols and amines, including proteins, to form esters or amide derivatives. 

Cellulose Reaction with Formaldehyde and Its Amide Derivatives... 

Figure 1 shows the repeating glucose units of cellulose with the carbons labeled, including those with the reactive 2, 3, and 6 hydroxyls. Ihe most important reactions of cotton cellulose commercially are esterification and etherification, with the products of etherification ranking first. It is generally agreed today among textile scientists that durable press cellulosic textiles ow their smooth-drying and resilient properties to the reactivity of formaldehyde and its amide derivatives with cellulose to produce crosslinks between adjacent cellulose chains (Figure 2). Hovever, the theory that crosslinking was responsible for increased resiliency developed only after the treatmaits were in wide use.

Amide derivatives, cellulose, reaction with formaldehyde and its, 52... 

So, it seemed interesting to study the influence of substitutes in sulphuryl amides concerning light stabilizing effect intensity. For this purpose we modified cellulose diacetate (CDA) with the help of sulphuryl amide derivatives of carbazole and indan. 

Van Overbeke, A. Baeyens, W. Van den Bossche, W. Dewaele, C. Enantiomeric separation of amide derivatives of some 2-arylpropionic acids by HPLC on a cellulose-based chiral stationary phase. J.Pharm.Biomed.Anai, 1994, 12, 911-916 [chiral derivatization also, flurbiprofen, ketoprofen, tia-profenic acid]... 

Rhone-Poulenc indicates that cellulose acetate with a degree of substitution of about 2 is biodegradable, in agreement with its earlier reference [176]. Cellulose has been discussed as a renewable resource [177], A recent publication [178] on chitosan reacted with citric acid indicates that the ampholytic product is biodegradable. Chitosan acetate liquid crystals [179], hydrophobic amide derivatives [180], and crossUnked chitosan [181] are also claimed to be biodegradable. 

Benzofuran derivatives such as 2-cyanobenzofuran-5-sulfonic acid esters and amides have found wide application as color developers in photographic processes (44USP2350127). The substituted benzofurans (507), (508) and (509) are used as brightening agents in textiles, wool, paper, cellulose and nylon (53MI31201). 

Like cellulose, the primary biological function of chitin is for structural support. And like cellulose, it is quite insoluble. Strong acids hydrolyze the amide to give the protonated amine, which is soluble at low pH. Given its abundance in nature, there has always been interest in finding commercial application for chitin or its derivatives. So far these efforts have achieved only limited success. 

Figure 14 shows the plots of the ratio Mw/Mn of the CA fractions prepared by the SSF method 39 42), as a function of their Mw. Mw and Mn values were determined by light scattering and membrane osmometry, respectively. Except for a few fractions of CA(2.46) and CA(2.92), Mw/Mn values of CA fractions lie between 1.2 and 1.5, independently of their Mw values. Most of the fractions of cellulose derivatives reported in the literature were prepared by the SPF method 44) their Mw/Mn values range roughly from 1.2 to 3.7 (most of them 1.5-2.0) and moreover depend markedly on Mw. This indicates clearly that the SSF method is superior to SPF for cellulose derivatives, as it is also the case for synthetic polymers such as polystyrene 38). A computer simulation for a quasi-temary system carried out by K amide and Matsuda also showed the inconditional superiority of the SSF method 34 - 36 ... 

The possibility of crosslinking natural macromoleculcs, such as cellulose and proteic materials, via the Mannich reaction has also been inve.stigatcd. Cellulose derivatives, however, are mostly subjected to the analogous amidomcthylation reaction, " usually employing bis-methylol amides (urea, oxalyl, adipoyl derivativas, etc.) capable of reacting with the cellulose hydroxy groups. 

Amino polystyrene pyrazolone linker resin 58 provided various amide products 59 with a high conversion rate and good purity under mild conditions the resin linker was stable under the reaction conditions, resistant to hydrolysis, and reused repeatedly without loss of activity <03TL8063>. The preparation of pyrazoline derivatives 61 was accomplished with traceless solid-phase sulfone linker 60 with phenylhydrazine <030L1067>. Aniline cellulose-bound enaminones 62 reacted with phenylhydrazine under microwave irradiation to produce pyrazolocarboxylic acid derivatives 63 in high yields <03JCO465>. 

Apart from the reaction with halogen derivatives, use was also made, for the synthesis of silicon-containing cellulose esters, of the reaction of alcoholysis, with cellulose, of tetraalkoxysilanes or alkyl(aryl)trialkoxy-silanes and the amides of siliconic acids (64) ... 

Alcoholysis of the amides of alkylenephosphorous acids with cellulose led to the synthesis of hitherto unknown phosphorus-containing derivatives of cellulose (70), cellulose alkylenephosphites ... 

Accordingly, the spectrum of applicability of these CSPs can be derived. It appears that cellulose- and amylose-carbamate CSPs are excellent for the enantioseparation of SAs with hydrogen donor and/or acceptor sites (amides, carbamates, sulphonamides, hydroxy groups) as well as aromatic moieties, advantageously in combination with bulky groups close to the interaction sites. Due to the broad range of applicability a more detailed list of resolvable SAs would extend this report. However, further information is available from the application guide [172], from review articles [47,99,1(X), and from recently published enantioseparations (Table 9.4). 

The enantiomeric purity of 2-arylpropionic acids used as pharmaceuticals was determined after derivatizing to the corresponding amides with various PAA and HAA. End analysis was by HPLC-UVD, with simultaneous measurement at 230 and 254 nm, using a cellulose-based stationary phase. The best derivative for routine determinations was chosen in each case after establishing the chromatographic parameters of the enantiomeric pair of derivatives197. 

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