Monocyclic diamine

Shortly after their first report of all-oxygen bridged cryptands, Dietrich, Lehn and Sauvage reported incorporation of sulfur in the strands. The experimental methods used were essentially similar to those applied in the syntheses of the parent cryptands. As in previous cases, a diacyl chloride was condensed with a diamine under high dilution conditions. In this case, however, the diamine contained sulfur atoms rather than oxygen. The synthesis of compound 5 was accomplished in two stages as illustrated below in Eq. (8.3). The first cyclization step affords the macrocyclic amine in 55% yield. The macrobicyclic product (5) is formed in 25% yield from the monocyclic diamine and the acid chloride. 

Medium-ring saturated monocyclic diamines (12) have pKa values > 12 in aqueous solution (88CC1528), (12, n = m = 4) has the highest pK[ resulting from internal hydrogen bonding as suggested by NMR measurements and force-field calculations. 

The treatment of perhydropyrido[ 1,2-a]pyrimidine 268 (R = H) with diisobutylaluminum hydride overnight afforded monocyclic diamine 679 (82TL4181 93JA6580). 

Medium-ring monocyclic diamines (lOa-e) have pA H.i values 12 in aqueous solution, so they cannot be measured by potentiometric methods <88CC1528>. Studies in DMSO with the proton sponge, 2,7-dimethoxy-l,8-bis(dimethylamino)naphthalene, indicate that (lOe) has the highest pATn value in this series. This results from internal hydrogen bonding as indicated by NMR measurements and effective force-field calculations. 

Various heterocyclic structures, among them 3-substituted-hexahydro-277-pyrimido[l,2- ]pyrimidin-2-ones 190, have been prepared by solid-phase synthesis. The acetates 187 were reacted with diaminoalkanes, the resulting diamines 188 cyclized with BrCN to the monocyclic compounds 189, which were cleaved and cyclized with Et3N to give 190 (Scheme 30) <2005TL5289>. 

Acylation of a / -configurated axially chiral diamine 1 containing a primary amino group with equimolar amounts of monocyclic anhydrides 2 and 4 in toluene or dichloromethane at low temperatures gives the amides 3 or 5 with good diastereoselectivity 10°. Diastereomeric ratios were determined by HPLC analysis after conversion to the methyl esters with diazomethane absolute configurations are based on chemical correlation. 

Monocyclic l,4-diazepin-5-ones and fused l,5-benzodiazepin-2-ones, e.g. (169) and (170), can be readily prepared by the reactions of 1,2-diamines with / -ketoesters (67AHC(8)21, p. 57, 68CRV747, p. 776, 71JHC797). Similarly reactions with malonic acids and esters give l,4-diazepine-5,7-diones (171) (67AHC(8)2l, pp. 55,69,68CRV747, p. 78l>. 

Both monocyclic (609) and benzo fused systems (610) have been prepared by the reactions of 1,2-diamines with chlorosulfonyl isocyanate (CIO2SNCO) (75GEP2409355). 

The construction of the macrobicyclic system is shown in Scheme 5.1. The acyclic starting materials are the diacid chloride 2 and the diamine 3.4 An alternative synthesis of the intermediate monocycle is given in Chapter 2 (Protocol 5). 

One can note that for this step the ratio of reagents 3 2 is 2 1, the excess diamine, 3, playing the role of base which takes up the hydrogen chloride liberated by the coupling reaction. The separation of the monocyclic diamide 4 from the reaction mixture containing amide oligomers is easy as the latter... 

The bis(amido) monocyclic zirconium metallocene (11) was obtained by the reaction of equimolar amounts of the zirconocene dichloride Cp2ZrCl2 and the dilithiated diamine (Me3SiN-(CH2)2-NSiMe3)Li2 in THF (Scheme 5). (The latter... 

Syntheses from a single monocyclic component 8.40.9.3, Syntheses from a monocyclic amine and an acyclic component 8.40.9.4, Syntheses from a diamine and one or more acyclic components 8.40.9.5, Syntheses by ring transformation. 

The next tetramine we will discuss is the monocyclic 1,4,8,11-tetraazacyclotetradecane (37) with an accompanying gas-phase enthalpy of formation of 18.0 3.3 kJmol . Summing the most recent value for the enthalpy of formation of its carbocyclic analog, cyclotetradecane (278 kJmol ), and 4- 5 results in a predicted value of 22 kJmol Ignoring any consequence of intramolecular hydrogen bonding and vie- and other diamine effects, we find agreement is satisfactory. 

The intermolecular diamination of 1,3-dienes with acyclic ureas to provide monocyclic or bicydic urea derivatives has been achieved by Uoyd-Jones and Booker-Milburn through use of a palladium catalyst combined with either benzo-quinone or O2 as an oxidant [65]. For example, diene 81 was converted to urea 82 in 82% yield (Eq. (1.37)). These transformations are mechanistically distinct from the reactions described above, and appear to involve intermediate jr-allylpalladium complexes. 

Monocyclic polyazamacrocycles with propylene units separating the nitrogen atoms (115) and (116), and (117) having two successive ethylene diamine units separated by five atoms, are found (110) to have respective pK values in the desired range (Figure 2.44). 

Diazepine derivatives, because of their interesting chemistry and great potential as therapeutic agents, still attract a great deal of synthetic activity each year 1981 is no exception. A simple procedure has been developed for the preparation of monocyclic azepine derivatives. The imidate (224) and N-methylethyl-enediamine form the bridged diamidine salt (225, R = H) in ethanol, and this has been used for a variety of transformations. N,N -Dimethylethylene diamine, however, fails to react in this way and instead straight-forward seven-membered condensation products (226) are produced, which may be further elaborated to bicycHc derivatives (227). 

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