Diamines 1,2-substituted

The one-pot synthesis of thiazolo[3,4-a]benzimidazoles has been reported using a microwave-assisted condensation-cyclization (see Scheme 17) of a substituted 1,2-diamine, substituted benzaldehyde and mercaptoacetic acid [74]. Heating the mixture at reflux for 12 min using a single-mode microwave reactor for the most part gave the fused benzimidazoles in improved yield and dramatically shorter times, when compared to classical conditions of heating at reflux in benzene for 24-48 h (Scheme 29). 

Several pyridine containing ligands of this type have been reported by Toftlund [2]. A combination of two aliphatic and four imine nitrogen functions seems to provide a ligand field at the crossover point. A versatile class of ligands of this type is based on aliphatic diamines substituted with four alkylpyridine groups. The simplest compound of this type is tetrakis(2-pyri-dylmethyl)-l,2-ethanediamine (tpen) (18). 

Both carbonyl and carboxyl groups in the a-position can be condensed with a suitable diamine with the formation of a heterocyclic derivative (Scheme 4.21). The properties of such a heterocycle are mostly unsuitable for GC and they are further modified by silylation. Properties suitable for ECD detection can be introduced into the molecule by using a diamine substituted with halogens on the benzene ring [115]. 

Para-diamines substituted in one amido-group react like primary amines, and the monamine may also be secondary or teidiary. In many such cases the formation of an ammonium-chloride group... 

Studies of the reactivity of l,3-a 5a-oxy(tetraethyleneoxy) derivative (99) have been extended to reactions with alkylene diamines. Substitution takes place at the PCI centre as a consequence of the interaction between the incoming nucleophile and the crown ether ligand already present, yielding compounds (100), (101) and (102). Only for H2N(CH2)3NH2 was the formation of a spiro derivative (103) was observed. Treatment of (99) with an excess of nucleophilic reagents leads to substitution of all chlorine... 

Polymeric derivatives of cw-diaminodichloroplatinum have been prepared240,241,242 because of the wide use of the anticancer monomeric drug cis-platinum. Polymeric platinum systems may function as medicinal agents. These polymers were prepared using diamines, substituted hydrazines, ureas, and thioureas and K2PtCl4. Structure 104 is representative of... 

Pyrido[3,4-b]pyrazines substituted in the pyridine ring are available from the reactions of suitably substituted 3,4-diaminopyridines and the appropriate dicarbonyl compounds. No problems are encountered with diamines substituted with halogen or hydroxy groups. Similarly the pyridones 7 provide the oxo compounds 8 and 9. In contrast, 3,4-diamino-5-nitropyridine did not react with glyoxal, and only a low yield of 2,3-dimethyl-8-nitropyrido[3,4-b]pyrazine could be obtained using diacetyl. ... 

N-Butylethanolamine coco/oleyl/soya diamine substitute N-lsotridecyloxypropyl 1,3-diaminopropane cocoa butter substitute, confectionery 1 -Palmitoyl-2-oleoyl-3-stearin cocoa butter substitute, cosmetics Hydrogenated vegetable oil cocoa butter substitute, frostings... 

Uses Emulsifier corrosion inhibitor flotation collector coco, soya oroleyl diamine substitute... 

Formation of a Quinoxaline. Heat together for 5 minutes under reflux 0 2 g. of phenanthraquinone dissolved in i ml. of glacial acetic acid and 0-2 g. of O -phenylene diamine also dissolved in i ml, of glacial acetic acid. The yellow substituted quinoxaline (p. 305) separates rapidly. Cool, filter and recrystallise from benzene m.p. 225 . 

N,N -Diacetylethylenediamine-N,N -dithioacetamide (42) reacts with oj-bromoacetophenone and its p-substituted derivatives to give the expected N,N -diacetyl-N,N -bis(4-phenyl-2-thiazolylmethylethylene diamine) (43) (Scheme 21) with R = H, Me, Cl, Br, MeO, yields ranged from 65 to 80% (482). 

A series of fiber-reactive dyes have been made by the reaction of Sulforhodamine B with chlorosulfonic acid, an appropriately substituted diamine, and cyanutic chloride to yield dyes, eg, a Sulforhodamine B derivative (34), with good hghtfastness (42). 

Amidation. Heating of the diammonium salt or reaction of the dimethyl ester with concentrated ammonium hydroxide gives adipamide [628-94-4] mp 228°C, which is relatively insoluble in cold water. Substituted amides are readily formed when amines are used. The most industrially significant reaction of adipic acid is its reaction with diamines, specifically 1,6-hexanediamine. A water-soluble polymeric salt is formed initially upon mixing solutions of the two materials then hea ting with removal of water produces the polyamide, nylon-6,6. This reaction has been studied extensively, and the hterature contains hundreds of references to it and to polyamide product properties (31). 

A series of cross-linkable copoly(amide—imides) is known to be possible from aromatic diamines and substituted isophthaloyl chlorides containing unsaturated imide rings as a pendent function (13). 

Condensation ofDianhydrides with Diamines. The preparation of polyetherknides by the reaction of a diamine with a dianhydride has advantages over nitro-displacement polymerization sodium nitrite is not a by-product and thus does not have to be removed from the polymer, and a dipolar aprotic solvent is not required, which makes solvent-free melt polymerization a possibiUty. Aromatic dianhydride monomers (8) can be prepared from A/-substituted rutrophthalimides by a three-step sequence that utilizes the nitro-displacement reaction in the first step, followed by hydrolysis and then ring closure. For the 4-nitro compounds, the procedure is as follows. 

Curing Systems. The most commonly used vulcanizing agent for the polyethers not containing AGE, that is, ECH and ECH—EO, is 2-mercaptoimidazoline, also called ethylenethiourea [96-45-7]. Other commercially appHed curing agents include derivatives of 2,5-dimercapto-l,3,4-thiadiazole, trithiocyanuric acid and derivatives, bisphenols, diamines, and other substituted thioureas. 

The type of synthesis in which the two-atom fragment supplies C-5 + C-6 is uncommon but useful in preparing pyrimidine- and 5,6,7,8-tetrahydroquinazoline-2,4-diamines. Thus, dicyandiamide (S78) with benzyl methyl ketone (S77) yields 6-methyl-5-phenylpyrimidine-2,4-diamine (S79), or with acetophenone it yields 6-phenylpyrimidine-2,4-diamine (62JOC2708). Likewise, with cyclohexanone it yields the tetrahydroquinazolinediamine (SSO) and by using N- substituted dicyandiamides, 2- and/or 4-alkylamino groups may be introduced (65JOC1837). 

The use of guanidine for cyclization gives amino substituted derivatives (e.g. 212) (52CB1012), and in this case o-aminonitriles may be used to furnish diamines (e.g. 8UOC1394). An unusual reaction involving nitriles occurred during the preparation of nicotinonitrile from the amide and ammonium sulfamate, when a 60% yield of the dimeric by-product (213) was formed via the nitrile (69BSB289). Similar products have been obtained from... 

Another type of bifunctional catalysis has been noted with a,cn-diamines in which one of the amino groups is primary and the other tertiary. These substituted diamines are from several times to as much as 100 times more reactive toward imine formation than similar monofunctional amines. This is attributed to a catalytic intramolecular proton transfer. 

Some instances of incomplete debromination of 5,6-dibromo compounds may be due to the presence of 5j5,6a-isomer of wrong stereochemistry for anti-coplanar elimination. The higher temperature afforded by replacing acetone with refluxing cyclohexanone has proved advantageous in some cases. There is evidence that both the zinc and lithium aluminum hydride reductions of vicinal dihalides also proceed faster with diaxial isomers (ref. 266, cf. ref. 215, p. 136, ref. 265). The chromous reduction of vicinal dihalides appears to involve free radical intermediates produced by one electron transfer, and is not stereospecific but favors tra 5-elimination in the case of vic-di-bromides. Chromous ion complexed with ethylene diamine is more reactive than the uncomplexed ion in reduction of -substituted halides and epoxides to olefins. ... 

Polyfluorinated a-diketones react with 1,2-diainino compounds, such as ortlio-phenylenediamine, to give 2,3-substituted quinoxalmes [103] Furthermore, the carboxyl function of trifluoropyruvates offers an additional electrophilic center. Cyclic products are obtained with binucleophiles [13, 104] With aliphatic or aromatic 1,2-diamines, six-memhered heterocycles are formed Anilines and phenols undergo C-alkylation with trifluoropyruvates in the ortho position followed by ring closure to form y-lactams and y-lactones [11, 13, 52, 53, 54] (equation 23). 

Dehydrofluorination by primary and secondary aliphatic amines occurs at room temperature and is the basis of diamine cross linkmg, which occurs by dehydrofluonnation and subsequent nucleophihc substitution of the double bond The locus of dehydrofluonnation is a VDF unit flanked by two perfluoroolefin units This selectively base-sensitive methylene group also undergoes elimination as the first step in phase-transfer-catalyzed cross-hnking with quaternary ammo mum or phosphomum salts, bisphenols, and morganic oxides and hydroxides as HF acceptors [31, 32]... 

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°. 

Bis(substituted amino)-4,8-bisethylthio (or carboxymethylthio)-pyrimido[5,4-d]pyrimidines (464) are aminated first at the 4-position with primary or secondary amines at 180° (2 hr) and then at the 8-position (200°, 4 hr). The 4,8-bisthioxo derivative of 464 is 4,8-diaminated with ethanolamine (170°, 1 hr). 2,6-Dianilino-4,8-dioxo(or diethoxy or dibenzyloxy) derivatives of 464 react at the 4-and 8-positions with primary or secondary amines at 180°. The 2,4,6,8-tetrachloro derivative is claimed to goto the tetrakis(triethylammonio) compound. ... 

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