1-Methyl-2-phenyl-ethylamine

Wenn man bei der vorstehend beschriebenen Reaktion 2-Methyl-1-oxo-cyclohexan reduk-tiv z.B. mit (R)-1 -Phenyl-ethylamin aminiert, erhalt man (1 R,2S,aR)-2-Methyl-1 -(1 -phe-nyl-ethylamino)-cyclohexan (als Hydrochlorid 88%), das durch Hydrierung iiber Palla-dium/Kohle zu (17 ,2S)-1 - Amino-2-methyl-cyclohexan (als Hydrochlorid 78% 96% ee) und Ethylbenzol gespalten werden kann2. 

The procedure given above is an adaptation of the methylation method first used by Sommelet and Ferrand3 and developed more fully by Clarke, Gillespie, and Weisshaus.2 /3-Phenylethyldi-methylamine has been prepared from /9-phenylethylamine by alkylation with dimethyl sulfate 4 by the reaction of fi-phenyl-ethylamine and of N-methyl- S-phenylethylamine with formaldehyde 6 by catalytic reduction of phenylacetonitrile in the presence of dimethylamine 3 by the reaction of dimethylamine with /3-phenylethyl chloride 7 8 9 and with /3-phenylethyl bromide 9 and by the reaction of phenylacetaldehyde with dimethylamine.10... 

Very little new data have been obtained in this area since the publication of CHEC-II(1996). In a recent work, the optically active enantiomeric 1,3,4-thiazaphospholes 61 and 62 were synthesized by the reaction of 0-phenyl(chloro-methyl)isothiophosphonate with (R)-(+) and (. 

Waldmeier PC, Antonin KH, Feldtrauer JJ, Grunenwald C, Paul E, Lauber J, Bieck P. Urinary excretion of O-methylated catecholamines, tyramine and phenyl-ethylamine by volunteers treated with tranylcypromine and CGP 11305 A. Eur J Clin Pharmacol 1983 25 361-8. 

The most critical raw material for the production of Dilitiazem is p-anisic aldehyde. Approximately, 2.3-2.4 kg of /3-anisic aldehyde is required per kg of dilitiazem. Other important raw materials are D(+) alpha phenyl ethylamine (0.35kg/kg), 2-aminothiophenol (1.9kg/kg), methyl chloroacetate (1.9kg/kg), sodium methoxide (1.6kg/kg), chloroform (5.5kg/kg), methanol (9 kg kg), isopropyl alcohol (5kg/kg), etc. 

Tyrosine- and Phenylalanine-Derived Alkaloids Tyrosine and phenylalanine amino acids are bearing the phenyl-ethylamine moiety of many medicinally relevant alkaloids. Further hydroxylations on the aromatic carbocycle or on the aliphatic part can be observed. Methylations can occur on phenolic oxygens and on the amine, leading to catecholamines (adrenaline, noradrenaline, dopamine). Arylethylamines are also usual to react with endogenous aldehydes through Pictet-Spengler reactions [25], leading to important biosynthetic intermediates (Scheme 1.7) like ... 

MPPP methyl(phenyl)( -propyl)phosphine NEA 1 -(1 -naphthyl)ethylamine... 

D) 4 -[N-Ethyi-1 "-Methyl-2 -(4" -Methoxyphenyl)Ethylamino]Butyi-3,4-Dimethoxybenzoate Hydrochloride 10.3 g of 4 -iodobutyl-3,4-dimethoxybenzoate and 11.0 g of N-ethyl-p-methoxyphenylisopropylamine (obtained by catalytic reduction of an alcoholic solution of an excess quantity (60%) of p-methoxy-phenyl-acetone, to which was added a 33% (weight-for-weight) aqueous solution of ethylamine, with Pt as a catalyst), were boiled in 200 ml of methyl ethyl ketone for 20 hours, cooled and the iodine ion was determined the reaction was found to be complete. Then the methyl ethyl ketone was evaporated in vacuo and the residue was dissolved in 300 ml of water and 30 ml of ether the layers were separated and the water layer was extracted twice more with 20 ml portions of ether. 

Phenyl N-acetylcarbazate 1529 cyclizes on boiling with excess TCS 14/tri-ethylamine in toluene to give 5-methyl-l,3,4-oxadiazohne-2-one 1530 in 65-70% yield [41, 59, 60]. The same type of cyclization was subsequently described for re-... 

The amination of styrene, however, led to two products (1-phenyl-1-ethylamine and 2-phenyl-l-ethylamine) in a 1 3 ratio [113], indicating that the hydrozirconation was not completely regioselective [114,115]. Since it is well known that hydrozirconation of trisubsti-tuted alkenes places zirconium at the least hindered carbon of the chain by a process involving zirconium migration, this class of alkenes was not investigated [5,116], On the other hand, hydrozirconation/amination of 3-methyl-l,2-butadiene gave an allylic amine. Reaction of the latter could either occur at the terminal carbon or proceed with... 

The most successful modifier is cinchonidine and its enantiomer cinchonine, but some work in expanding the repertoire of substrate/modifier/catalyst combinations has been reported (S)-(-)-l-(l-naphthyl)ethylamine or (//)-1 -(I -naphth T)eth Tamine for Pt/alumina [108,231], derivatives of cinchona alkaloid such as 10,11-dihydrocinchonidine [36,71], 2-phenyl-9-deoxy-10, 11-dihydrocinchonidine [55], and O-methyl-cinchonidine for Pt/alumina [133], ephedrine for Pd/alumina [107], (-)-dihydroapovincaminic acid ethyl ester (-)-DHVIN for Pd/TiOz [122], (-)-dihydrovinpocetine for Pt/alumina [42], chiral amines such as 1 -(1 -naphtln I)-2-(I -pyrro 1 idiny 1) ethanol, l-(9-anthracenyl)-2-(l-pyrrolidinyl)ethanol, l-(9-triptycenyl)-2-(l-pyrrol idi nyl)cthanol, (Z )-2-(l-pyrrolidinyl)-l-(l-naphthyl)ethanol for Pt/alumina [37,116], D- and L-histidine and methyl esters of d- and L-tryptophan for Pt/alumina [35], morphine alkaloids [113],... 

Optica] resolution of these and related carboxylic acids were achieved using salt formation with alkaloids (strychnine, brucine, cinchonidine) 33,39,44 or with optically active amines [1-phenyl- or l-( 3-naphthyl)ethylamine]4o,44). The following rotations [a]D have been reported [8]paracyclophanecarboxylic acid (13) +18° (chloroform)441 [10]homologue (14) +80° (chloroform)39 and +67° (chloroform)40 its methyl-derivative (75) —28° (methanol)44 . Dioxa[10]paracyclophanecarboxylic acid (16) + 104° (ethanol)36 and bromo-dioxa[12]paracyclophanecarboxylic acid (79) —37° (acetone)33). 

Isocyanates methyl ethyl phenyl etc. Phosgene + amine methylamine ethylamine aniline etc. 

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