Alcohol Allylamine

On treatment of phosphine with I-butene, cyclohexene, allyl alcohol, allylamine or allyl chloride, the corresponding primary, secondary and tertiary organophosphines are obtained in yields ranging from 2 to 67%. The reaction between phosphine and 1-butene is, among others, used for the industrial preparation of tributylphosphine. ... 

Pulsed Plasma Polymerization. Allyl alcohol, allylamine and acrylic acid were polymerized in pulsed plasma to retain a maximum in functionalities in the resulting plasma polymer. The retention of functional groups during the plasma process, introduced by functional-group carrying monomers and followed by deposition to polymer layers, was primarily measured by XPS including the chemical derivatization of these groups as described in Experimental. These layers were also checked for side-products by respective IR spectra. The results are summarized in Table 1. 

Keywords Allyl alcohol, Allylamine, Aza-allyl, Azomethine, BINAP, BIPHEMP, Citronellal, Cobalt, DIOP, Enol, Enamine, Imine, Isomerization, Kinetic resolution. Nitrogen-triggered, Rhodium, Ruthenium... 

TiCl4 immobilized on surface of PE modified by graft polymerization of vinylpyridine, acrylonitrile, methyl vinyl ketone, allyl alcohol, allylamine, allyl sulfide or acrylic acid, has been studied with IR spectroscopy and XPS I166J. Cluster aggregates of Ti(IV) fixed on the surface, were discovered. Their formation did not cause the reduction of Ti(IV). In binary catalytic systems of Ti(IV) on an organo-aluminum polymeric support, Ti(IV) was reduced to Ti(III), and Ti(II) appeared at 343 K. The high and stable activity of immobilized titanium compounds during ethylene polymerization was attributed to deceleration of Ti(IV) reduction processes. 

Acrolein Acrylonitrile Acrylyl chloride Allyl alcohol Allylamine... 

A comparison of Rh and Ru catalysts in the hydroformylation of linear butenes [110] or 3,3,3-trifluoropropene allowed the conclusion that the latter are less active [111]. Moreover, in the hydroformylation of propene, inferior regioselectiv-ity was observed [112]. Apparently, ruthenium catalysts can exhibit pronounced isomerization activity, which is supported by heteroatoms in the substrate (e.g., allyl alcohols, allylamines) [113]. 

Beller and coworkers [142] broadened these investigations to include several other terminal-functionalized and nonfunctionalized olefins as substrates (allyl alcohols, homoallyl alcohols, allylamines, homoallylamines, vinyl cyclohexane, 3-arylprop-l-enes). For example, in a basic medium, Fe3(CO)j2 converted 1-octene cleanly into 2-octene (Scheme 5.31). Moreover, Z-2-octene was converted into the corresponding -isomer. Temperatures of80-100 °C were required to achieve nearly quantitative yields. 

Other unsaturated substrate analogs that have been tried as enzyme inhibitors include allyl amine and allyl alcohol. Allylamine is a pseudo-irreversible inhibitor of flavin-linked monoamine oxidase i.e., in the presence of allylamine, the enzyme shows a time-dependent inactivation that cannot be reversed by dialysis. When radiolabeled allylamine is used, radioactivity is incorporated at the same rate as the enzyme is inhibited. However, inhibition is relieved and radioactivity is removed from the enzyme upon incubation with the substrate, benzylamine. 

The 4-hydroxy-1-alkene (homoallylic alcohol) 81 is oxidized to the hetni-acetal 82 of the aldehyde by the participation of the OH group when there is a substituent at C3. In the absence of the substituent, a ketone is obtained. The hemiacetal is converted into butyrolactone 83[117], When Pd nitro complex is used as a catalyst in /-BuOH under oxygen, acetals are obtained from homoallylic alcohols even in the absence of a substituent at C-3[l 18], /-Allylamine is oxidized to the acetal 84 of the aldehyde selectively by participation of the amino group[l 19],... 

Allylamines are difficult to cleave with Pd catalysts. Therefore, amines are protected as carbamates, but not as allylamines. Also, allyl ethers used for the protection of alcohols cannot be cleaved smoothly, hence alcohols are protected as carbonates. In other words, amines and alcohols are protected by an allyloxycarbonyl (AOC or Alloc) group. 

Pyrrohdinone (2-pyrrohdone, butyrolactam or 2-Pyrol) (27) was first reported in 1889 as a product of the dehydration of 4-aminobutanoic acid (49). The synthesis used for commercial manufacture, ie, condensation of butyrolactone with ammonia at high temperatures, was first described in 1936 (50). Other synthetic routes include carbon monoxide insertion into allylamine (51,52), hydrolytic hydrogenation of succinonitnle (53,54), and hydrogenation of ammoniacal solutions of maleic or succinic acids (55—57). Properties of 2-pyrrohdinone are Hsted in Table 2. 2-Pyrrohdinone is completely miscible with water, lower alcohols, lower ketones, ether, ethyl acetate, chloroform, and benzene. It is soluble to ca 1 wt % in aUphatic hydrocarbons. 

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... 

In an analogous fashion to the reductive deprotection of allyl alcohols and allyl esters, the deallylation of allylamines is also possible (Eq. 337).270... 

In parallel to the asymmetric catalytic isomerization of allylamines, [Rh(BINAP) (solvent)2]C104 is a very efficient catalyst for the isomerization of allylic alcohols.9,11 By employing 0.5mol% of the catalyst, good to excellent conversions were achieved even in the case of substrates that are more difficult to isomerize, such as allylic alcohols having two alkyl groups in the terminal position (R1 = R2 = Me) and 2-cyclohexen-l-ol (Scheme 19). 

Although the asymmetric isomerization of allylamines has been successfully accomplished by the use of a cationic rhodium(l)/BINAP complex, the corresponding reaction starting from allylic alcohols has had a limited success. In principle, the enantioselective isomerization of allylic alcohols to optically active aldehydes is more advantageous because of its high atom economy, which can eliminate the hydrolysis step of the corresponding enamines obtained by the isomerization of allylamines (Scheme 26). 

Metal-catalyzed C-H bond formation through isomerization, especially asymmetric variant of that, is highly useful in organic synthesis. The most successful example is no doubt the enantioselective isomerization of allylamines catalyzed by Rh(i)/TolBINAP complex, which was applied to the industrial synthesis of (—)-menthol. A highly enantioselective isomerization of allylic alcohols was also developed using Rh(l)/phosphaferrocene complex. Despite these successful examples, an enantioselective isomerization of unfunctionalized alkenes and metal-catalyzed isomerization of acetylenic triple bonds has not been extensively studied. Future developments of new catalysts and ligands for these reactions will enhance the synthetic utility of the metal-catalyzed isomerization reaction. 

Type I (fast homodimerization) Terminal olefins, allylsilanes" Terminal olefins, allylsilanes," 1° allylic alcohols, ethers, and esters, " allyl boronate esters, allyl halides, alkyl-substituted allenes Terminal olefms, allyl boronate esters, 1° allylic alcohols, ethers, and esters,styrenes (no large ortho substit.), " " allyl allylsilanes, allyl sulfides, allyl phosphonates, " allyl phosphine oxides, protected allylamines ... 

Type III (no homodimerization) Acrylonitrile," protected 3° allylamines" Vinyl trialkoxysilanes, vinyl siloxanes 1,1-Disubstituted olefins, " non-bulky trisubstituted olefms, vinyl phosphonates, " vinyl phosphine oxides,phenyl vinyl sulfone, acrylonitrile, 4° allylic carbons (all alkyl substituents), protected 3° allylic alcohols, 7,Aolefm of 2-subst. 1.3- butadienes, 7,Aolefin of electronically deactivated 1.3- butadienes ... 

Type IV (spectators to CM) 1,1-Disubstituted olefms " 1,1-Disubstituted olefms, disub. o ,/ -unsaturated carbonyls, 4° allylic carbon-containing olefins, perfluorinated alkane olefins, 3° allylamines (protected)" Vinyl nitro olefins, protected trisubstituted allyl alcohols, a,/ -olefin of 2-subst. 1.3- butadienes, a,/ -olefm of electronically deactivated 1.3- butadienes ... 

Some nucleophiles other than carbon nucleophiles are allylated. Amines are good nucleophiles. Diethylamine is allylated with allyl alcohol[7], Allylamines are formed by the reaction of allyl alcohol with ammonia by using dppb as a ligand. Di- and triallylamines are produced commercially from allyl alcohol and ammonia[l74]. 

Beak and co-workers have also produced the key alcohol intermediate 74 by the sparteine-mediated lithiation and conjugate addition of allylamines to nitroalkenes to give Z-enecarbamates in good yields with high enantio- and diastereoselectivty (Scheme 16). Thus treatment of the allylamine 87 with n-BuLi in the presence of (-)-sparteine followed by conjugate addition to nitroalkene 88 gave the desired enecarbamate 89 in... 

C3H5.HNC6H2(N02)2-C6H2(N02)2NH.C3H5 mw 444.36, N 18.91%, orn-red ndls (from phenol or salicylic acid methyl ester), mp 205° (dec) was prepd by heating at 100° in a sealed tube 3, 5, 31, 51-tetranitro-4, 4 -dimethaxy (or diethoxy) -diphenyl with allylamine in alcohol (Refs 1 3)... 

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