The synthesis of substituted phenethylamines

855

SUBSTITUTED PHENETHYLAMINES

July 1968

C6H5CH2CHCH,0H

CeHjCH2CHCH20H

I

I p-YC6H4CH,NH

RCHO

C,HjCH,CHCH,OH

I

N=CHR VI11

NHZ

VI

1

(COOEt),

C,H;CH,CHCH,OH

CGH5CHZCHCHLOH

I

I

p - YC6HICONH

HNCNHR

U

X

Z

I

Ix

Socl,

VI1

xv

XI11

I

CeH5SNa

C~HSCH~CHCH~SCEH:,

I

C,H,CONH XIV

I

NaI04

C6HjCHz$!HCHZSOC,Hj C&COh XVI V-VII, X, X I I I : a, Y = C1; b, Y

benzylic secondary amines (VIa and b) preferentially undergo the intramolecular ring closure rather than the intermolecular reaction demonstrated by the primary amine (IV). Sumerous products, IXa-e, were prepared by the reaction of isocyanates and isothiocyanates with 2-amino-3-phenyl-1-propanol (IV). I n all cases, the expected ureas and thioureas were formed in preference t o the carbamates and thiocarbamates. Where ethyl chloroformate wus used, the expected carbamate, a-(hydroxymethy1)phenethylcarbamic acid ethyl ester (XI), was isolated. The reaction of thionyl chloride with 2-benzaniido-3phenyl-1-propanol (Xh) nnd 2-(p-chlorobenzamido)-3phenyl-1-propanol (Xa) converted the hydroxy groups to chloro groups, resulting in the compounds, 2-benz:~mido-l-chloro-3-phenylpropane (XIIIb), the optically

=

H

active ( R ) form of which has been reported,j and 2 - ( p chlorobe1~zamido)-l-chloro-3-phenylpropa1ie (XIIIa). The dl form had a melting point which differed from the ( 5 ) K. Koga, H. RIatsuo, and 14, 243 (1966).

S.S'amada, C h e m . Pharm. Bull. ( T o k y o ) ,