Diamines, condensation

Diphenylcyclopropenone, 47, 62 Dii henyldiacetylene, 45, 39 Diphenyl disulfide, oxidation to methyl benzenesulfinate, 46, 62 1,1-Diphenylethylene, reaction with N,or diphenylmtrone, 46,129 N,N -Diphi iiyli tiiyleni diamine, condensation with triethyl orthoformate, 47, 14... 

Benzene-1,2-diamine condenses with l-aryl-3,3-disulfanylprop-2-en-l-oncs 12279 to give 1H-1,5-benzodiazepine-2(3//)-thiones 13. Selected examples are given.280... 

Benzene-1,2-diamines condense with fi-oxo esters in refluxing xylene to give l//-l,5-benzodi-azepin-2(37/)-ones 19. Selected examples are given.268-271... 

Bcnzene-1,2-diamine condenses with l-(dimethylamino)-3-(methylsulfanyl)-3-phenyl-2-aza-prop-2-eneiminium iodide (1), obtained from A, A -dirnethyl-A -(phenylthioxomethyl)form-amidine and iodomethane, to give a mixture of the 1,3,5-benzotriazcpine 2 and 2-phenylbenz-imidazole.375... 

Diamines condense with alkoxycarbonyl isocyanates (R02C—N=C=0), dialkyl iminodicarboxylates [HN(C02Me)2] or urea to give triazepinediones (495). 

Benzene-1,2-diamines condense with oxalic acid or its esters to give quinoxaline-2,3-diones... 

The cation-active surface-active compounds, which are usually quaternary ammonium or pyridinium derivatives, form another important group of textile auxiliaries. An example is Sapamine CH, which is diethylethylene diamine condensed with oleyl chloride and converted to the corresponding hydrochloride ... 

Oligomer products of diamine condensation with carbonyl compounds, using excess of one of bifunctional compounds have been used lately. These products are used as stabilizers of thermooxidative destruction for different polymers, moreover oligomer stabilizers are more interesting because they are washed out from the polymer at photofading and sweated out, while in use least of all [294]. 

Some pyridodiazepin-4-ones exist as different valence bond tautomers, and may even isomerize to five-membered ring-containing products. Pyridine-3,4-diamine condensed with ethyl acetoacetate in toluene to give a mixture of tautomeric diazepin-4-ones, but in xylene, the product was an imidazopyridine which was also obtained by dry fusion of the diazepin-4-one [2327],... 

A3-Methylpyridine-2,3-diamine or the isomeric JV2-methylpyridine-2,3-diamine condenses with diethyl mesoxalate to yield the corresponding ethyl mcthyloxopyrido[2,3-i]pyrazinecarb-oxylate 22.23 A2-Alkylpyridine-2,3-diamines 23 react with ethyl pyruvate in refluxing ethanol to give the corresponding 4-(aminoalkyl)-2-methylpyrido[2,3-h]pyrazin-3(4//)-ones 24.24 A similar condensation is reported of various 5-substituted Af2-alkylpyridine-2,3-diamines with 3-phenyl-2-oxopropanoic acid.25... 

Although both 50 and 51 have a quinoxaline structure, they are formed by diamine condensation at different carbonyl groups of the starting 1,3-dicarbonyl compound, which depends on the size of the fluoroalkyl substituent. The nucleophilic reagent attacks the sterically less hindered carbon atom of the carbonyl group. 

Aminoalkylquinoxalines (17) have been derived from a-amino acids (10) as shown in Scheme 2, the amino group is protected by formation of a phthalimide derivative (11). The intermediate chloromethyl ketone (12) is converted via a pyridinium salt (13) to a nitrone (14) which on hydrolysis yields the a-dicarbonyl compound (15) required for diamine condensation. Finally the phthalimide residue is removed from the condensation product (16) by hydrazine treatment. ... 

Reaction of disecondary amines and carbonyl compounds affords cyclic aminals if the amino groups are in suitable positions relative to one another (1,2-, 1,3-, or 1,4-). For example, 1,3-diamines condense readily with aldehydes or ketones to give hexahydropyrimidine derivatives,966 967 and disecpndary ethylenediamine derivatives give imidazolidines.968... 

Metal deactivators, which form inactive chelates or insoluble reaction products with transition metals originally present in a form that promotes the decomposition of peroxides to free radicals. Examples are ethylenediaminetetraacetic acid, salicylaldehyde-diamine condensation products or metalalkyl dithiocarbamates such as of nickel or zinc. 

The nitroketone (465) was converted to the oxime acetate (466) which was treated with diborane to reduce the imine group followed by hydrogen to reduce the nitro group and give the diamine (467). The diamine condensed with triethyl orthoacetate to yield dazepinil (471) Scheme 5.110.) [628]. An improved route began with o-toluidine (468) which was iV-protected to allow the directed metallation of the methyl group. Treatment with the SchifPs base (469) followed by deprotection and exposure to triethyl orthoacetate gave dazepinil in improved yield [629]. This benzodiazepine has antidepressant properties. 

The diester-diamine condensation reaction to give cyclic diamides was first reported by Tabushi et al. <77TL1049> and has been applied with some variations. For example, chiral diamides (48) were obtained from chiral tetraamines (Equation (18)) <89joci584>. 

The first account on 1,2-dione/diamine condensation carried out mechanochemically was given by Zefirov, who investigated solid-phase synthesis of benzo[Mphenazme 3 by reaction of phenylenediamine 1 with 2,3-naphthoquinone 2 (Scheme 3.1) [1]. Synthesis was carried out in an SVM-0.4 vibrational ball mill (120mL chamber volume). Cascade reaction mechanism consists of the four reactions substitution, elimination, cyclization, and elimination. 

Further mechanochemical 1,2-dione/diamine condensation reactions were described by Kaupp and Naimi-Jamal in their subsequent article [4]. Substituted quinoxalines 9 were obtained by ball milling of equimolar amounts of o-phenylenediamines 7 and benzyls 8 (Scheme 3.3, Table 3.1). Milling beaker was heated at different temperatures through double walls with fittings for circulating... 

In a similar manner as used for 1,2-dione/diamine condensations, Kaupp carried out stoichiometric mechanochemical reactions of o-mercaptoanihne 86 with ninhydrin in the three reaction cascade (substitution, cyclization, and elimination), which gave the salt of 10a-hydroxyindeno[2,l-( ]benz[l,4]thiazin-l l(10a//)-one 89 (Schane4.23) [15], Washing of product with NaHC03 was the simple woricup in this efQcient sol-vent-free synthetic protocol. 

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