Of 1,3-propanediamine

Reaction of 1,3-propanediamine and 3-cyano-4-methyl-6-methylthio-l-phenyl-2-0X0-],2-dihydropyridine-5-carboxylate 385 yielded 7-cyano-8-methyl-6-oxo-],2,3,4-tetrahydro-6/7-pyrido[],2-a]pyrimidine-9-carboxylate (386) (94JHC393). 

Reaction of 1,3-propanediamine and a mixture of a and isomers of 5-bromo-5-deoxy-D-xylofuranose in H2O for 10 min gave 1 R-(la,8p,9a9aa)-7,8,9-trihydroxyperhydropyrido[l, 2-u]pyrimidine (112, R = H) in 27% yield (99T6759). Reaction of 5-bromo-5-deoxy-D-xylofuranose and A -methyl-1,3-propanediamine in H2O at room temperature afforded a 5 1 mixture of 1-methyl 117 and 5-methyl 118 derivatives of 7,8,9-trihydroxyperhydropyr-ido[l, 2-u]pyrimidine 112 (R = H). When this reaction was carried out in the presence of 3 moles of NEts the product ratio of 117 to 118 was 1 2. The influence of NEt3 on the product ratio may be a consequence of it scavenging HBr and freeing the more basic and more nucleophilic methylamino group for participation in the displacement reaction. 

Reaction of 3-amino-2-cyano-4-[(phenylamino)(methylthio)methylene]-2-pentenedioate (408) with a large excess of 1,3-propanediamine afforded ethyl 6-imino-l, 2,3,4-tetrahydro-6//-pyrido[l, 2-n]pyrimidine-9-carboxylate (409) as depicted in Scheme 16 (95JHC477). 

There is some question as to whether amine exchange has occurred in the attempted preparation of bisacetylacetonetrimethylenediiminocopper(II). Bis-(4-iminopentane-2-ono) copper (II) would result from either a cleavage or an amine exchange reaction. One piece of evidence that can be brought to bear on the problem is the observation that, when methylamine is used instead of ammonia, the desired product is obtained. The cleavage reaction should occur more readily in the presence of methylamine, inasmuch as a greater concentration of hydroxide ion would be present. However, only 30% of the amount of 1,3-propanediamine expected for amine exchange was obtained. 

Coordination of 1,3-propanediamine (tn) results in a six-membered ring and chair (c), boat (b) or twist (t) ring conformations are possible. The twist conformation can adopt enantiomeric <5 and X orientations of the C—C axis with respect to the N—M—N plane (24). Simple tn complexes appear to prefer the chair conformation, and although twist conformations are known, no boat conformations have been detected. 

Trihydroxyperhydropyrido[l,2-(2]pyrimidines 112, 113, 115 were obtained by the cyclization of 2-substituted perhydropyrimidines 300-302, obtained in the reactions of 1,3-propanediamine and D-xylose, L-arabinore and D-ribose, respectively, with Ph3P and CC14 in the presence of NEt3 in DMF at ambient temperature in 22-40% yields (98JOC391, 98T5097). Perhydropyrido[ 12-a]pyrimidine 112 was also prepared in crude form, containing dehydrated impurity, by the cyclization of compound 303 with... 

Aqueous hydrobromic acid (32.6 g, 0.2 mole of 48% HBr) is added slowly from a dropping funnel to a solution of 1,3-propanediamine (15 g, 0.2 mole) in 600 mL of degassed methanol. 2,3-Butanedione (biacetyl, 17.2 g, 0.2 mole) is added under nitrogen from a dropping funnel over a 30-minute period in a well-ventilated hood and the mixture is stirred. The solution slowly changes color from yellow to orange-red. After addition of the 2,3-butanedione is completed, hydrated cobalt(II) acetate (24.9 g, 0.1 mole) is added, and the solution is stirred under nitrogen for 3 hours at room temperature. To the resultant deep-purple solution is added about 70 mL of 48% aqueous hydrobromic acid, and air... 

A(A -Bis(3-aminopiopyl)ethylenediamme is prepared by the method of E. K. Barefield. Six moles of 1,3-propanediamine is dissolved in 1.4 L of absolute ethanol and the solution is cooled to 5° in an ice bath. To this solution is added 0.75 mole of 1,2-di-bromoethane from a dropping funnel with vigorous stirring. After the addition is complete, the reaction is heated to reflux temperature for I A hours.. Potassium hydroxide, 150 g, is added and the mixture is refluxed for a further 1 hour. The reaction mixture is cooled to room temperature and filtered to remove the solids. The filtrate is evaporated to a sludge on a rotary evaporator and the semisolid is extracted several times with diethyl ether. The ether solution is evaporated until a viscous liquid remains. The liquid is distilled in vacuo (b.p. 138-148°/2 ton) and stored over potassium hydroxide pellets in a bottle protected from light. The yield is 64 g. 

Carboxamides containing alkylamine arms like (34), synthesized from dialkylmalonate and ethylene-diamine, act as chelating dianionic N4-donors,44,45 whereas the geometric isomer (35) was prepared from 1,3-diaminopropane and chloroacetyl chloride.46 The hexadentate bis(pyrazine)-carboxamides (36) and (37) can be obtained by the addition of 1,3-propanediamine to the appropriate carboxylic acid.47 Compound (36), in the dianionic form, can be used to obtain homo- and hetero-metal bridged complexes, whereas (37) has been shown to yield tetranuclear copper(II) complexes involving opened-up dianionic ligand molecules.47... 

Marckwald and von Droste-Huelshoff treated the bis(p-toluenesulfo-namide) of 1,3-propanediamine with alkali, followed by trimethylene bromide, and obtained diazocine 7 (R = R1 = Ts) (1898CB3264). Shortly thereafter, Howard and Marckwald reported obtaining the free base 7 (R = R1 = H) by reacting the bistosyl derivative of 7 with hydrochloric... 

During their work on the total synthesis of diazasteroids, Burckh lter and Abramson8 investigated, as a model, the synthesis of 2-(2-ethoxy-carbonylethyl)-3,4,5,6-tetrahydropyrimidine hydrochloride (16) via the condensation of 1,3-propanediamines (14) with ethyl 3-ethoxycarbonyl-propionimidate hydrochloride (13). When 16 was heated above its melting point, and the melt was allowed to sublime, 2,3,4,6,7,8-hexa-hydro-6-oxopyrrololl,2-a]pyrimidine hydrochloride (17) was isolated in excellent yield [Eq. (3). ... 

Condensation of 1,3-propanediol ditosylate with the disodium salt of the bis(toluenesulfonamide) of 1,3-propanediamine affords ditosylate (19 R = = 4-MeC H4S02) in ca. 50% yield <90IC264>. 

Pd-catalyzed reactions of amines provide convenient methods for the synthesis of tertiary amines, diamines, polyamines, and heterocyclic amines. Typically, the Pd-catalyzed reaction of A-methylbenzylamine with A-methylbutylamine gives A-butyl-A-methylben-zylamine (95%) along with methylamine (Scheme 2). The treatment of azetidine (3) with the palladium catalyst in the presence of 1,3-propanediamine (4) at 120 °C gives N-(3-aminopropyl)-l,3-propanediamine (5), which undergoes further Pd-catalyzed reaction with 3 to give the tetramine 6 (75%) (Scheme 3). 

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