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 ) ,