1,2-Diamines special

Macrocycles have been prepared by formation of macrocyclic imines as well as by using variations of the Williamson ether synthesis ". Typically, a diamine or dialdehyde is treated with its counterpart to yield the Schiff s base. The saturated macrocycle may then be obtained by simple reduction, using sodium borohydride, for example. The cyclization may be metal-ion templated. In the special case of the all-nitrogen macrd-cycle, 15, the condensation of diamine with glyoxal shown in Eq. (4.14), was unsuccess-ful ... 

This is not the only method of forming tetrazo-compounds. Each amino-group of a diamine may be diazotised and coupled. Benzidine and its homologues, which ha e been utilised in this way, have a special value for the cotton dyer, as the shades produced are not only ery biilliant, but, unlike the maiorily of... 

Dichloro-s-triazine and its 6-alkyl analogs are as easily hydrolyzed by water as trichloro-s-triazine and, on suspension in aqueous ammonia (25°, 16 hr), the first is diaminated in good yield. 2,4-Bistrichloromethyl-6-methyl- and -6-phenyl-s-triazines (321) require a special procedure for mono-alkoxylation (0-20°, 16 hr, alcoholic triethylamine) disubstitution occurs at reflux temperature (8 hr). Aqueous triethylamine (100°, 3 hr) causes complete hydroxy-lation of 2,4,6-tris-trichloromethyl-s-triazine which can be mono-substituted with ammonia, methylamine, or phenoxide ion at 20°. 

Tile chloro derivative 33a (not isolated) interacts with pyridine-2,3-diamine in dichloromethane at room temperature to yield 73 (85%) (93BSB357). A further example deals with the reaction between the salt 39 and benzene-1,2-diamine, which gives an imine 74 (80%) under special experimental conditions (93BSB357). In order for the reaction to work, the salt 39 must be isolated prior to its employment (Section IV,C,8). No traces of the diimines were detected for both cases. However, the experimental conditions were not optimized for this purpose since no more than three equivalents of the diamines were used (Scheme 23). 

Biocides Especially for controlling Clostridium and similar organisms found in water present in aviation kerosene and diesel tanks. Biocides include special grades of isothiazolines, polyquats, diamines, and sulfones. 

A special case is if the methylene units in the even-even PA are in the diamine as long as in the diacid (as in PA-4,6, -6,8, and -8,10) so that an ordering in both a parallel and an antiparallel fashion is possible (Figs. 3.4a, b) 1" Because of this feature, these polymers have the highest order. 

In 1976, Meluch and Campbell at General Motors obtained a patent10 for a steam hydrolysis depolymerization of PUR. High-pressure steam hydrolyzes flexible PUR foams rapidly at temperatures of 232-316°C to form diamines and polyols. The diamines are distilled and extracted from the steam and the polyols are obtained from the hydrolysis residue. In 1977, Bayer AG obtained a patent for a continuous PUR hydrolysis process using a specially designed extruder.11... 

The most commonly used polyamides are linear but special ones are semi-aromatic with an aromatic diacid and a linear diamine or a linear diacid and an aromatic diamine. 

For some important groups of polymers, special names and systems of nomenclature were developed. For instance, the nylons were named according to the number of carbons in the diamine and dicarboxylic acid reactants used in their synthesis. The nylon produced by the condensation of 1,6-hexamethylenediamine (6 carbons) and adipic acid (6 carbons) is called nylon-6,6. Even here, there is no set standard as to how nylon-6,6 is to be written with alternatives including nylon-66 and nylon-6,6. 

Special terminology based on trade names has been employed for some polymers. Although trade names should be avoided, one must be familiar with those that are firmly established and commonly used. An example of trade-name nomenclature is the use of the name nylon for the polyamides from unsubstituted, nonbranched aliphatic monomers. Two numbers are added onto the word nylon with the first number indicating the number of methylene groups in the diamine portion of the polyamide and the second number the number of carbon atoms in the diacyl portion. Thus poly(hexamethylene adipamide) and polyfhexamethylene sebacamide) are nylon 6,6 and nylon 6,10, respectively. Variants of these names are frequently employed. The literature contains such variations of nylon 6,6 as nylon 66, 66 nylon, nylon 6/6, 6,6 nylon, and 6-6 nylon. Polyamides from single monomers are denoted by a single number to denote the number of carbon atoms in the repeating unit. Poly(e-caprolactam) or poly(6-aminocaproic acid) is nylon 6. 

The Schotten-Baumann reaction between dicarboxylic acid dichlorides and diamines can be performed not only in organic solvents, but also, by means of a special experimental technique known as interfacial polycondensation (see Examples 4-5 and 4-11). Both variants have the advantage of short reaction times at low temperature with simple equipment. 

As in the preparation of polyesters, also in the preparation of polyamides, the reaction temperature can be considerably reduced by using derivatives of dicarbo-xylic acids instead of the free acids. Especially advantageous in this connection are the dicarboxylic acid chlorides which react with diamines at room temperature by the Schotten-Baumann reaction this polycondensation can be carried out in solution as well as by a special procedure known as interfacial polycondensation (see Examples 4-11 and 4-12). 

OB to CQj —4.4%, yel crysts, mp I99°(dec), impact sensitivity 28—30cm with 2kg wt. This compd was prepd in the USA after WWII (Ref 3). It is an expl with heat of combstn 1830cal/g at const vol with water liq and ballistic mortar value 149% TNT. The repts describing its prepn other props are listed in Ref 2a It is reported that an aq so In of ediylene-diamine (1 mol) nitroform (2 mols) yielded die yel dinitroform salt, mp 118° (Ref 2a, p 59) Refs 1) Beil, not found 2) CA, not found 2a) K. Klager M.B. Frankel, Aerojet Special Rept 494(1951), 14, 59 BIOS/Gr-2 HEC No 5475 3) Dr W.L. Gilliland, Purdue Univ,... 

In the synthesis of all concave acids and bases, a difunctionalized molecule A-A was cyclized with a difunctionalized bridge component B-B. Because telo- and polymerizations are the main side reactions [29] the isolated macrocycles need not be the expected [1 -I- 1] addition products, the (-A-AB-B-)i cycles, [n - - n] Telomers with the general structure (-A-AB-B-) are also possible. These molecules have identical elemental analyses and similar IR and NMR data. Therefore the mass spectral analyses of the macrocycles are very important because this is the only method which can tell [1 -t- 1] and [2 -t- 2] addition products apart. Due to the high molecular weight of the concave acids and bases, special MS techniques were necessary in some cases [30]. In the case of the macrocyclic diamine 7 [R = NEt2, X = CH2(CH20CH2)2CH2], a [2 -t- 2] addition product could be isolated and characterized besides the desired [1 + 1] product [12a]. 

Perusal of the property and chemical structure tables will demonstrate the astonishing range of diamines that are paired with the 6F dianhydride. The 6F group in the dianhydride imparts good solubility and nearly precludes significant molecular ordering. For these and other reasons, it is an ideal monomer to be paired with diamines burdened by specialized functional tasks. 

The hydrolysis of adenosine 3. 5 -cyclic monophosphate (cAMP) by the cobalt complexes (215) was considered here earlier,187 as was the Ce(IV)-catalysed hydrolysis of phospho monoesters in nucleotides.189 A review (ca 100 references) on current data on the mechanism of cleavage-transesterification of RNA has appeared.258 In this review special attention was focused on the two crucial steps in the hydrolysis of RNA, i.e. cleavage-transesterification and hydrolysis of the cyclic phosphodiester (Scheme 14). The catalysis of various amines for the hydrolysis of RNA has been looked at and ethylenediamine and propane-1,3-diamine are highly active under physiological conditions because they exist as the catalytically active monocation forms.259... 

Another class of substances of interest as bifunctional diazo components consists of special diamines that can be manufactured by the reaction of aromatic amines with benzaldehyde or cyclohexanone, e.g.,16 and 16a. 

Chemical Composition. In polyamide 6 (PA 6, polymerization product of e-caprolactam) and polyamide 66 (PA 66, adipic acid polymerized with hexamethylene-diamine) one chain end consists of an amino group, which can be present in the free state or in the acylated form. Amino groups are of special importance for dyeing because they form ammonium groups in an acidic dyebath by addition of protons. The lower dye uptake in comparison to wool is caused by the comparatively low number of amino groups. The depth of color achieved on PA 6 is somewhat less than that on PA 66. 

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