Allylamine, reaction with

Formation of Amines. Mono-, di-, and triaEyl amines are prepared by reaction with ammonia. The ratio of reagents determines product distribution with sufficient time and excess of aEyl chloride, tetraaEylammonium chloride [13107-10-3] and triallylamine [102-70-5] predominate. Mixed amines are prepared in similar fashion by using a substituted amine in place of ammonia they may also be prepared with allylamine [107-11-9] and a suitable organic chloride. 

Z)-3-(Tributylstannyl)allylamine participates in a palladium-catalyzed cross-coupling reaction with 2-bromobenzaldehyde (73, R = H) to give 3//-2-benzazepine (75, R = H). A similar reaction with the corresponding acetophenone 73 (R = Me) produces 1 -methyl-3//-2-benzazepine (75 R = Me), whereas with ethyl 2-bromobenzoate (73, R = OMe), 3//-2-benzazepin-(12/7)-one (74) is formed.237... 

O-Allyl imidate esters undergo [3,3]-sigmatropic rearrangements to /V-allyl amides. Trichloromethyl imidates can be made easily from allylic alcohols by reaction with trichloroacetonitrile. The rearrangement then provides trichloroacetamides of IV-allylamines.260... 

Based on earlier experiences ring opening of the pyridine moiety in methyl 4-tetrazolo[l,5- ]pyridine carboxylate 70 on reaction with allylamine was predicted by Okawa et al. <1997T16061> (Scheme 19). Instead of the expected major structural change, however, a routine aminolysis was found to yield the allylamide 71. 

In contrast to the polyacrylamide homopolymers typical of CE,Fujimoto et al. incorporated charged functionalities into the neutral polyacrylamide chains to accelerate the migration of neutral compounds through a capillary column [90]. Despite this improvement, nearly 100 min were required to effect the separation of acetone and acetophenone, making this approach impractical even with the use of high voltage. Alternatively, Tanaka et al. [86] alkylated commercial poly-allylamine with alkyl bromides, followed by a Michael reaction with... 

Phosphorylated allenes 195 (R1 = H or Me) are a source of secondary ( )-allylamines. The allenes are treated with an amine R2NH2 (R2 = t-Bu or 4-MeCgH4 and the products, which exist as equilibrium mixtures of enamines 196 and imines 197, are olefinated by successive reaction with methyllithium and an aldehyde R3CHO (R = i-Bu, 4-MeCgH4, PhCH2CH2 etc). Reduction with sodium borohydride finally yields the... 

Examples of synthetic applications of these three principal reaction types can be illustrated by the TiCLt-catalyzed interaction of the allylamine 613 with 2-phenylpropanal 614 in refluxing toluene (equation 265)358 as well as by the ZnCl2 promoted rearrangement of N-allylated benzoyl substituted heterocyclic keteneaminals 615 (equation 266)359. 

Mn(acac)3 reacts with ethylenediamine (L2) or other primary amines (L) to yield [Mn"(acac)2L2], which can also be prepared by the reaction of the amine or diamine with [Mn(acac)2(H20)2]. Allylamine reacts with [Mn(acac)2-(H20)2] in ether to give a second complex, [Mn(acac)2(H2NCH2==CH2)]2 which is dimeric both in the solid and vapour phases. This is the First example of a dinuclear manganese(ii) acetylacetonate complex. Thermodynamic data have been reported for the manganese(ii)-acetylacetone system in propan-1-ol-water. ... 

Further functionalization at OH-2 was also explored [187]. From monosacchari-dic (ot-gluco, 129) and disaccharidic (a-malto, 143) CMGLs, several types of bisfunctionalized systems were synthesized by reaction with allylamine or propar-gylamine. For example, compound 155 was prepared and used in a synthesis of the nucleotide sugar analog 156 (Scheme 38). In the context of studies on the... 

The RRM precursor was synthesised in a multistep procedure from alcohol 33. The first allyl amino side chain was introduced by a Mitsunobu reaction with Ns protected allylamine with inversion of configuration. Attempts to introduce the second N-protected allylamine via an 7 -allyl Pd(0)-substitution failed. Changing the order of the substitution was also unsuccessful (Scheme 11). 

The polymer, [-CH2CH(CH2NHC6H4N02-p)-]n, PPNA, was synthesized by aromatic nucleophilic substitution reaction of poly(allylamine hydrochloride) with p-fluoronitrobenzene. PPNA so prepared has mol. wt. 

Reaction of dichlorothiophosphoryl units with allylamines gave corresponding phosphodendrimers with terminal allyl functions while reaction with propargyl-amine afforded molecules with terminal alkyne groups. Peripheral tri- and tetra-functionality could thus be attained [108]. 

An enantioselective version of this allylamine synthesis employs the chiral (S,S)-dimethylzirconium derivative 3, prepared from (S,S)-[l,2-ethylenebis(tetrahydro-l-indenyl]zirconium dichloride.3 Displacement of one methyl group by triflic acid followed by reaction with a lithium anilide results in a zirconaaziridine (a) with loss of methane. Reaction of a with a symmetrical alkyne provides a metallapyrroline (b), which is hydrolyzed to an (S)-allylamine (4) in 90-99% ee. The method tolerates variation in the lithium anilide. Terminal alkynes do not react with a, but 1-trimeth-... 

Only few examples of preparative isomerizations of cyclic allylamine to cyclic enamine have been reported. Thus, 1-methyl-1,2-dihydro-1-benzazocine (70) was converted into enamine 71 by reaction with t-BuOK-DMSO at room temperature262, 1-methyl-1,2-dihydroquinoline (72) was isomerized under the same conditions to enamine 73 and the indoloquinolizines 74 were isomerized with t-BuOK-DMSO at 100 °C to enamines... 

The high rate constant for reaction with OH and the low rate constant for reaction with eaq made the allylamine a good candidate for studying the two possible mechan-... 

The most frequently performed reaction with organometals concerns the well-known addition to the carbonyl group of ketobases. This reaction (Fig. 114) exhibits many affinities with reduction, as it affords an aminoalcohol (296), in this case tertiary, and involves analogous stereochemical features when chiral ketobases are employed. Again, the aminoalcohols produced can be further converted, by dehydration, into allylamines (R R C=CH—CHi—N<), which are useful in pharmaceutical chemistry. - ... 

Due to the relative rapidity of the reactions and to the protonation of the free amine by the excess scavenger during the deprotection of allyl carbamates, the risk of formation of allylamine seems very limited and has not been reported. In the reactions with dimedone, a possible complication is the formation of substantial amounts of hydrolytically stable oxo-enamine by condensation with the liberated amine. For this reason, the use of N,N-di-methylbarbituric acid is probably a safer solution. 

Various methods for the synthesis of allylamines have been reported.Reaction of allylic bromide (11) with amines gave Sn2 and Sn2 substitution products in the ratio Sn2 Sn2 ranging from ca. 1 20 for the reaction with piperidine to 9 1 for the reaction with diisopropylamine (Scheme 8). The product distribution changes with a slight change in the electron-withdrawing capacity of the arenesulfonyl group, as well as the structure of the amines. 

The membranes used in the present study contained 50.0 wt% PVA (60 mol % cross-linked by formaldehyde), 20.7wt% AIBA-K, 18.3wt% KOH, and 11.0wt% poly(allylamine), unless otherwise stated. Figure 9.3 presents a schematic of the C02 transport mechanism in the membranes. The membranes synthesized contained both AIBA-K and KHCO3-K2CO3 (converted from KOH) as the mobile carriers, and poly(allylamine) as the fixed carrier for C02 transport. AIB A is a sterically hindered amine, and its reaction with C02 is depicted in Equation 9.12.49 Poly(allylamine) is a nonhindered amine, and its reaction is shown in Equation 9.13. The reaction mechanism of the C02 with KHC03-K2C03 is presumably similar to that of hindered amine-promoted potassium carbonate described in Equation 9.14 50... 

Hydroxycodeinone was first represented as an a-hydroxy-ketone, but such a formulation was rejected by Gulland and Robinson [9] on account of the stability of the base towards alkaline silver and cupric solutions, and, moreover, the base does not behave as an allylamine in its reaction with cyanogen bromide [4, 13-16]. A /3-hydroxy-ketone structure was never seriously considered and is in any case at variance with the observed difficulty of dehydrating 14-hydroxycodeinone and its derivatives, but a y-hydroxy-ketone formulation is compatible with all the experimental facts. 14 Hydroxycodeinone does not show the properties of a methylene-ketone, but its dihydro-compound does, facts best explained by postulating the presence of the system —GO—0—C—C—OH in the former [9]. 

Interesting chemical reactivity of RuHCl(CO)(PPh3)3 has recently been reported [145]. Treatment of RuHCl(CO)(PPh3)3 with iVA -dimethylallylamine resulted in formation of a 7i-allylruthenium complex via C—N cleavage, while reaction with allylamine gives a azaruthenacycle complex (Scheme 10.17). 

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