YEWCOMPOUNDS
July 1966
ti33
TABLEIa No.
b
R
c
Mp, 'Cd
Y
Solvent of recrystn
7---
Formula
C
H
Calcd, %--N P
S
-Found. C H
%----N
P
S
Diethyl Phosphoryl Esters of Quinolinols, Hydroxystilbazoles, 4,4'-Hydroxydihydrostilbazole, and 4-(3-Pyridylazo)phenol
0
I
R 1 2 3 4 5 6 7 8 9 10 11
12 13 14 15 16 17 18 19 20 21 22 23 24 25 26
3 3 5
5 6
6 7 7 8 8 5' 5' 51 4 4 4 4 4 4 4 4 4 4 3 3 3
... H . . _ C H I ... H . . . CHI .__H . . . CH3 ... H . . . CH3 ... H . . . CHB ... H . , , CHI . . . CHI 2 H 2 CHI 3 H 3 CH3 4 H 4 H 4 CHI 4 CHI 4 H 4 CHI 4 H 4
H
4
CHI
,
..
,
.,
... ... ...
..
,
.., , , ,
CH=CH CH=CH CH=CH CH=CH CH=CH CH=CH CH=CH CH=CH CHzCHp CHzCH2 N=N N=N N=N
159 Ille 157 117 178 137 168 92 123 107 141 133 1299 154 157 163 127 141 1218 152 168 103 77 133 1158 10.1
I
Picrate-
EtOH Hz0 MeOH lIeOH-EtzO MeOH MeOH RIeOH IIeOH Hz0 Hz0 RleOH 31eOH Me&O RleOH RleOH hleOH RIeOH MeOH MezCO-EtzO RIeOH MezCO MeOH-H?O MeOH-HsO hleOH MeOH-Et20 EtOH
R
Picrate-
C ~ H Z I N ~ O I I P45 81 4 04
10.69
5.91
46 23
3 96
10 56
5.72
c ~ ~ I I ? ~ N ~ o45.81 ,~P
10.69
5.91
46.00
3.83
10.54
5.87
CzoHziNaOiiP
4.04
4 5 . 8 1 4.04
10.69 5 . 9 1
46.27 3 . 9 5
10.70 6 . 0 1
4.04
10.69
5.91
45.86
4.43
10 68
5.96
CilHz&07PS
5 3 . 9 5 5.61
3.00
6.63
53.79
5.37
2.97
6.34
CdIzsNp01lP
50.01
4.37
9.72
5.37
49.95
4.04
9.88
5,38
CtrHzsNaOiiP
5 0 . 0 1 4.37
9.72
5.37
50.05 3 . 8 6
9.66
5.44
CzsH3oNO7PS
57.79
5.82
2.70
5.96
57.75 5.76
2.90
5.80
CziHziNaOllP
49.83
4.71
9.69
5.36
49.68
4.81
9 . 6 7 5.25
C2zHz3NsOi1P
45.68
4.01
14.53 5 . 3 6
45.85
4.40
C ? ~ H Z I N I O ~ I P4 5 . 8 1
6.86
6.17
14.35
5.31
10.70 9.78 9.63 9.39
5.88 4.57 4.92 5.29
6.47
6.06
Bisquaternary Compounds Containing the Bridge CH,OCH, between the Two Ring Nitrogen Atoms 2i 28 29 30 31 32
6
5f 4 4 4 4
... ...
..,
2
.,,
3 4 4
,
...
,,,
. ... ,
... ,
..
CH=CH CH=CH CH=CH CH?CH?
193 134 1Qi
129 192 87
hIerCO EtOH-l\lezCO 3IeOH MeOH 3IeOH MeOH
CaaHaoNsOzaPz 4 5 . 2 0 3.79 CasHasNsOzaPz 49 41 4 . 1 5 CasH4sNaOz3Pz 49.41 4.15 C ~ S H ~ S N S O ~49.41 ~ P Z 4.15
10.55 5 . 8 3 9.60 5.31 9.60 5,31 9.60 5.31
44.95 50.20 49.26 49.64
3.67 4.68 4.21 4.48
a The formula weight of all compounds except those containing CH=CH and X=N, which were not tested, was correct to l.Z%l,,by the picrate met,hod. * This number refers to the quinoline or pyridine rings. Lleltlng This number refers to the benzene ring. points were taken on a Uni-Melt, apparatus. e Previously reported;z softens a t 108-110", melts a t 135-137'. f Isoquinolinol. 0 pToluenesulfonate.
added a few minutea later, and much of the solvent wab evaporated a t room temperature. The crude picrate wab obtained by cooling and was recrystallized from methanol. Analysis for Picrate.-All the picrates except those containing the chromophores CH=CH and X=N were analyzed by measuring the optical density a t 415 m r of a solution a t about 2 X J f in lOy0 ethanol. The method was standardized with picric acid and a few drops of dilute alkali. All compounds were correct with i l . Z 7 0 which is about the accuracy of the method. The identity of the unquaternized esters in those compounds containing a chromophore rests upon the correct analyses of the qiiaternized derivatives.
6,12 -Diphenyldibenzo [ b,f ] [1,5 Idiazocines W. METLESICS, T. RESSICK,G. SILVERMAN, R. TAVARES, A K D L. H. STERKBACH Department o j Chernical Research, Research Division, Hoffmann-La Roche Inc., Nutley, S e w Jersey Received April 9, 1964 Revised Manuscript Received January 27, 1966 Since 2,8-dichloro-6,12-diphenyldibenzo[b,j ] [1,5]diazocine was shown to have hormonelike act,ivity,' a number of analogs were (1) Pharmacological d a t a on some of the compounds described will be published a t a later d a t e ; see also G. W.Duncan, S.C. Lyster, and .J. 13. Wright, Proc. S a c . Ezptl. B i d . M e d . , 120, 725 (1965).
prepared. In two case^^^^ 6,12-diphenyldibenzodiazocines were formed by heating the corresponding 2-aminobenzophenone hydrochlorides. We have found that dibenzodiazocines can be prepared conveniently and in good yields from 2-aminobenzophenones when Lewis acids are used as condensing agents. Experimental Section All melting poiiiti are corrected. Ultraviolet spectra were determined in isopropyl alcohol usiiig a Cary 14 spectrophotometer. General Procedure.4-The corresponding 2-amiliobenzophenone was dissolved in an inert solvent, the catalyst was added, and the solution was heated under reflux for the time indicated. After cooling, the solution was washed with aqueous sodium hydroxide, and the solvent was removed in uacuo. I n each case the crystalline reaction product waq recrystallized from a mixture of methylene chloride and alcohol to give pale yellow prisms. Acknowledgement.-We are indebted to Dr. V. Toome and Rlr. S. Traiman for the spectrophotometric determinations and to Dr. A1 Steyermark and his staff for the microanalyses.
(2) A. Sondheimer, Chem. Ber., 29, 1272 (1896). (3) A. Giacalone, Gazr. Chim. Ital., 65, 120 (1935); Chem. Abstr., 29, 54509 (1935). (4) Variations of the condensing agents and solvents gave different yields of the respective product. One representative example for t h e preparation of each compound is shown in Table I on the folloxxing page.
l!l,i
20
0
.>
t i !I
I .! :i
:;
!I
1:i :i .i!J
2 1 1 0 1 :i:i S i 4-1 2 3 8
The Preparation of 5-Substituted 5-(2-Naphthyl)hydantoins ab Potential Anticonvulsant Y
Experimental Section 2-Naphthyl Ketone Precursors.--l
