1-monosubstituted 1,3-diamines

Synthetically important chiral 1-monosubstituted 1,3-diamines (145) are synthesized in Mannich-t)fpe reactions of enecarbamates (140) with aromatic and aliphatic hemiaminal ethers (141) in the presence of phosphoric acid 95a. This process involves the highly reactive Mannich-t)fpe product (144), which is entrapped by a methanol molecule generated during the formation of the imine (143) derived from the hemiaminal ether (141) (Scheme 28.15) [72]. Similarly, diastereo- and enantio-enriched anti-l,2-disubstituted 1,3-diamines are prepared by the Mannich-type reaction of aldehydes, anilines, and enecarbamates in the presence of chiral phosphoric acid [73]. 

When p-ethylaminobenzoate and N,N-dimethyl-p-phenylene diamine sulfate were similarly treated with the dibromosulfone (I) for 2 h, the yield was only 32% and 15% respectively (Figure 1). A possible explanation is that the nucleophilicity of these monosubstituted anilines is weaker than that of aniline while a Na2C03 1,4-HBr elimination reaction could be competing with the substitution reaction, leading to the lower yield (18). 

The compounds described herein were prepared by three methods. The first route involves deprotonation/substitution at the N-H sites of 1, the second consists of a cleavage reaction of an Si-N derivative of 1 with PhBCI2, and the third route is a transamination reaction between a bis(dimethylamino)boryl derivative of 1 and an aliphatic diamine. In the first approach, compound 1 is deprotonated by treatment with one equivalent of n-BuLi. Quenching of the resulting anion with various electrophiles produces the monosubstituted products 2-4 (eq 3). 

Enantioselective osmylotion of alkenes. Osmium tetroxide forms a 1 1 wine-red complex with the chiral diamine l2 that effects efficient enantioselective dihy-droxylation of monosubstituted, oww-disubstituted, and trisubstituted alkenes (83-99% ee) at -110° in THF. The enantioface differentiation in all cases corresponds to that observed with t/mr-3-hexene and the complex with (-)-l. Essentially complete asymmetric induction is observed with frans-l-phenylpropene (99% ee). 

Lucet D. SabeUe, S. Kostelitz, O. Le Gall, T. Mioskowski, C. Enanti-oselective synthesis of a-amino acids and monosubstituted 1,2-diamines by... 

The nitro groups in TNB were replaced with alkoxy [7, 8] or perfluoroalkoxy [9-15] groupings using aromatic nucleophilic nitrodisplacement reaction [16-19] in accordance with Scheme 4.4. Monosubstituted dinitro compounds thus obtained were reduced to the corresponding diamines [7, 8, 11-15] in accordance with Scheme 4.5. The simplest of the target diamines, 3,5-diaminoanisole [7, 20, 21], was prepared in accordance with Scheme 4.6. 

The percentage of dicoordinated phosphorus compound present depends equally on the substituent R, on the solvent and on the temperature. It has been possible to prepare these oligomers from monosubstituted aliphatic or aromatic diamines, from amidrazones, from semicarbazides, from substituted thiosemicarbazides, from 2-aminophenol, from 2-aminothiophenol and even from the monoimines of orthophenylediamine (Table I). It seems that these oligomers are generally the thermodynamic products of the reaction, except perhaps for the amidrazones, and the 1-phenyl semicarbazide in which case they would be kinetic products (the thermodynamic products being the triazaphospholes). 

Lichtenhan et al. [23,24] prepared several monosubstituted POSS epoxides (XIX). The Cs-based chain epoxy (5-9 wt%) was used with 1,4-butanediol diglycidyl ether (EDGE) (XX), diglycidyl ether of Bisphenol A (DGEBA) (XXIII) and polyoxypropylene diamines (XXI) to prepare nano-reinforced epoxy network glasses (Scheme 6) [23]. 

In the case of primary aliphatic amines, the reaction products are dramatically affected by the solvent employed. For instance, in the presence of solvents apt to produce a specific solvation of amines (chloroform, and an amine chlorohydrate solution in methylene dichloride), the reaction with hexachloride precursors terminates to yield the trisubstituted product DD D" formed via route A. At the same time, the use of some other solvents (such as benzene, 1,4-dioxane, THF, methylene dichloride, DMF, and alcohols, or the corresponding amine media) led to the formation of the sole tetrasubstituted product (DD"D"). In addition, in the case of sterically unhindered primary amines an alternative isomer (D D D") is not isolated, which indicates reaction route A and a specific control of the tie reaction in the transition state by solvation interactions and intramolecular hydrogen bonds. In the case of the dichloride FeBd2(C12Gm)(BF)2 precursor, with both primary (cyclohexylamine) and secondary (diethylamine and piperazine) aliphatic amines, only a monosubstituted product of the Bd2D type is formed in chloroform, whereas in some other solvents, a diamine clathrochelate of the Bd2D" type is obtained with both sterically hindered and unhindered primary aliphatic amines. 

Depending on the reaction conditions, a-iminodicarboxylic acid derivatives or 2,6-di-piperazinediones [120] are formed from a-amino acids, oxocompounds and isocyanides. The isomeric 2,4-piperazinediones can thus also be formed by some of the U-4CR of vicinal diamines, isocyanides, oxocompounds and glyoxylic monoesters [121,122],The libraries of highly substituted 2-piperazones were produced by the chemists of Merck Inc. from N-monosubstituted ethylenediamines, carboxylic acids, isocyanides and chloroacetalde-hyde. 

Both 1 and 2 react with monosubstituted and tran -disubstituted alkenes to form complexes that give Bic-diamines on reductive cleavage (equation III). The reaction involves stereospecific cw-addition of the reagent. ... 

Reactions of diamines, diols, dihaloalkanes, and other polyfunctional reagents with polymer networks have been carried out for many purposes. If both groups of the reagent react with the polymer, a new cross-link is formed (Equation 2). If only one group reacts, the difunctional molecule is monosubstituted (Equation 3). Whether one or both groups react depends upon the DF of the polymer, shell dffusive or... 

Batog and co-workers used the Dimroth rearrangement to prepare a series of novel monosubstituted AT-(4-substituted-l//-l,2,3-triazol-5-yl)-1,2,5-oxadiazole-3,4-diamines (furazans). Substituted-5-amino-l, 2,3-triazole derivatives have previously been shown to display a variety of pharmacological activities, and the synthesis of furazans was undertaken in an effort to compare their reactivity and biological activity to known substituted-5-amino-1,2,3-triazole derivatives. 5-Amino-1,2,3-triazole derivatives 197, 199, 201 and 203 rearranged to form the mono-substituted diaminofurazans 198, 200, 202 and 204 upon continuous heating at 85-95 °C in DMF for 1 h, with yields of between 52 and 87%. 

Trivalent lanthanide inflates and Smta have been employed successfully as catalysts in the condensation of nitriles with primary amines and diamines into N,N -disubstituted and cyclic amidines, but monosubstituted... 

PreparaMon of Aldehydes and Ketones. Monosubstituted malonyl azides can be synthesized readily from the dihydrazides. Urethans of /em-diamines result when the azides are rearranged in alcohol these urethans are hydrolyzed rapidly by mineral adds to aldehydes. Diethyl benzylmalonate can be converted to phenylacetaldehyde in about 70% yield by this procedure. ... 

In situ generated [ CJisocyanic acid is probably the active agent when [ CJurea is used to ring-close free or monosubstituted 1,2- or 1,3-diamines or amino amides at... 

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