Ethane- 1,2-diamine, reaction with

An apparent particle size effect for the hydrodechlorination of 2-chlorophenol and 2,4-dichlorophenol was observed by Keane et al. [147], Investigating silica supported Ni catalysts (derived from either nickel nitrate or nickel ethane-diamine) with particles in the size range between 1.4 and 16.8 nm, enhanced rates for both reactions were observed with increased size over the full range (Figure 13). As electronic factors can be ruled out in this dimension, the observed behavior is traced back to some sort of ensemble effect, known from CFC transformations over Pd/Al203... 

Other preparative methods have been reported.2,3 ds-Dibromobis(l, 2-ethane-diamine)cobalt(III) bromide is obtained in reasonable yield by evaporating a neutral aqueous solution of the trans isomer to dryness. The reaction between ds-diazidob is( 1,2-ethanediamine)cobalt(III) perchlorate and hydrobromic acid proceeds rapidly and quantitatively at ambient temperature, largely with retention of the cis configuration to yield the dibromo bromide.4,s The diazido starting complex6 7 can be made within 1 hour in greater than 90% yield. 

Sterically more demanding copper(II) chelates based on trans-cyclohexane-1,2-diamine reveal similar condensation chemistry [165]. The yield of macrocyclic products, however, decreases compared to the reaction with ethane-1,2-diamine-containing chelates. The formation of copper(II) complexes of half-capped ligands is favoured compared to capped species for steric reasons. The presence of two asymmetric carbon atoms in the starting ligson allows synthesis of new chiral macrocycles. The most suitable for macrocyclisation has proved to be the R,R S,S bis(cyclohexane-l,2-diamine)copper(II). The three isomers of H2LI36 possible... 

Related complexes of other metals, such as [M]L7)] where M = Fe, Co and Pd, have been prepared by the same method [276]. Both the reactions of precursor [Pd]L6)] and final formation of [Pd]L7)] proc easily. Palladium] II) seems to favour the template process in the same way as nickel(II) and copper]II). In contrast to palladium] II), platinum] II) is oxidised during construction of H2L6, and the resulting product in this case is [Pt ]L6)Cl2] . All attempts to produce the macrocyclic complex of platinum] II) were unsuccessful because, after the reaction with en, [Pt]L6)Cl2] + decomposed. The template reaction probably fails to take place due to the octahedral coordination of the metal, as the postulated mechanism for the ring closure reaction involves ethane-1,2-diamine taking up axial positions [277]. 

An 5n2 mechanism is reported for the exchange of C-labeled ethane-1,2-diamine (en) with [Cr(en)3] ion in N-methyl formamide solution. Ligand exchange with [Cr(Et2NCS)3] proceeds in DMF solution with activation parameters A// = 15.9 kcal mol and A5 =-23.9 cal mor but in dioxane solution the reaction is very slow below 90°C. ... 

The much more stable MIL-lOO(Cr) lattice can also be impregnated with Pd(acac)2 via incipient wetness impregnation the loaded catalyst is active for the hydrogenation of styrene and the hydrogenation of acetylene and acetylene-ethene mixtures to ethane [58]. MIL-lOl(Cr) has been loaded with Pd using a complex multistep procedure involving an addition of ethylene diamine on the open Cr sites of the framework. The Pd-loaded MIL-lOl(Cr) is an active heterogeneous Heck catalyst for the reaction of acrylic acid with iodobenzene [73]. 

Type I Urea-Urethane Oligomers. To 30g (0.5 mole) ethylene diamine and lOg dimethoxy ethane in a three-neck flask equipped with an overhead stirrer was added over a one-hour period, 185g (0.5 mole) of butanol half-blocked dllsocyanate. After the addition, the reaction was stirred overnight at room temperature. 

The synthesis of quadridentate imine chelates usually requires the combination of two equivalents of the carbonyl compound and a diamine, as in the formation of complexes of ligands (6),17 18 (7)19 and (8).20,21 In similar fashion, thermodynamic template reactions allow the very effective synthesis of quinquedentate and sexadentate metal complexes of ligands such as (9),22 (10),23 (ll),24 (12)25 and (13).26 Condensation of 1,1,1-tris(aminomethyl)ethane with pyridine-2-carbaldehyde alone yields... 

Enantioselective dihydroxylation with OsO4.7 The (S,S)-diamine 6 [1,2-diphe-nyl-l,2-bis(2,4,6-trimethylbenzylamino)ethane] is prepared by reaction of (S,S)-1 with mesitylaldehyde followed by NaBH4 reduction. It markedly accelerates reac-... 

A general synthetic approach consists of the reaction of 1,2-diaminopyrazines or A,A -dimethyl-ethane-1,2-diamines with glyoxal. This method has already been described in CHEC-I. Additionally, some new approaches have been developed. Nucleophilic exchange of the chlorine atoms of 5,6-dichloropyrazine-2,3-dicarbonitrile (118) by 1,2-diamino compounds affords the pyrazino[2,3-6]py-razines (119) and (120) (Scheme 20) <88LA1197>. Variation of the amines and treatment with hydrazine hydrate forms several polyaza derivatives <88LA1197>. 

There are few examples for the preparation of imines from N-(l-haloalkyl)azinium halides and primary diamines. Among those reactions reported, A-(chlorophenylmethyl)pyridinium chloride (33k), which has not been isolated, reacts with ethane-1,2-diamine and propane-1,3-diamine to afford the corresponding diimines 72 (Scheme 22, 45-80%) (89JOC4808 92BSB233). 

Benzodithiolethione with diamines gives cyclic amidines (90) in which two sulfur atoms are lost.145 The reaction of (V,(V -dialkyl-l,2-diamino-ethanes with 1,2-benzodithiolethione gives products 91146 which are nitrogen analogs of those obtained from alkenes (see Section III,G). 

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