July 1966 YEW COMPOUNDS ti33

TABLE Ia M p , Solvent of 7--- Calcd, %--- -Found. %-----

No. b c R Y 'Cd recrystn Formula C H N P S C H N P S

Diethyl Phosphoryl Esters of Quinolinols, Hydroxystilbazoles, 4,4'-Hydroxydihydrostilbazole, and 4-(3-Pyridylazo)phenol 0

I Picrate- R I Picrate- R

1 3 . . . H 2 3 . . _ C H I 3 5 . . . H 4 5 . . . CHI 5 6 . _ _ H

159 EtOH I l l e Hz0 157 MeOH 117 lIeOH-EtzO C ~ H Z I N ~ O I I P 45 81 4 04 10.69 5 .91 46 23 3 96 10 56 5.72 178 MeOH

6 6 . . . CH3 , . . 137 MeOH c ~ ~ I I ? ~ N ~ o , ~ P 45.81 4.04 10.69 5 .91 46.00 3 . 8 3 10.54 5.87 7 7 . . . H , . , 168 RIeOH 8 7 . . . CH3 . . . 92 I I e O H CzoHziNaOiiP 4 5 . 8 1 4.04 10 .69 5 . 9 1 46 .27 3 . 9 5 10.70 6 . 0 1 9 8 . . . H . . . 123 Hz0

10 8 . . . CHB . . . 107 Hz0 C ? ~ H Z I N I O ~ I P 45 .81 4.04 10.69 5 . 9 1 45.86 4 . 4 3 10 68 5 .96 11 5' . . . H . . , 141 RleOH 12 5' . , , CHI . . , 133 31eOH 13 51 . . . CHI , , , 1299 Me&O CilHz&07PS 53 .95 5.61 3 . 0 0 6 . 6 3 6 .86 53.79 5 . 3 7 2 . 9 7 6 .34 6 .47 14 4 2 H CH=CH 154 RleOH 15 4 2 CHI CH=CH 157 RleOH CdIzsNp01lP 50.01 4 . 3 7 9 .72 5 . 3 7 49.95 4.04 9 . 8 8 5 , 3 8 16 4 3 H CH=CH 163 hleOH 17 4 3 CH3 CH=CH 127 RIeOH CtrHzsNaOiiP 5 0 . 0 1 4.37 9 .72 5 .37 50.05 3 . 8 6 9 .66 5 .44 18 4 4 H CH=CH 141 MeOH 19 4 4 H CH=CH 1218 MezCO-EtzO 20 4 4 CHI CH=CH 152 RIeOH 21 4 4 CHI CH=CH 168 MezCO CzsH3oNO7PS 57.79 5 .82 2 .70 5 . 9 6 6.17 57 .75 5 .76 2.90 5 . 8 0 6.06 22 4 4 H CHzCHp 103 MeOH-H?O 23 4 4 CHI CHzCH2 77 MeOH-HsO CziHziNaOllP 49.83 4 .71 9 .69 5 .36 49.68 4 . 8 1 9 . 6 7 5 .25 24 3 4 H N=N 133 hleOH 25 3 4 H N=N 1158 MeOH-Et20 26 3 4 CHI N=N 10.1 EtOH C2zHz3NsOi1P 45.68 4.01 14.53 5 .36 45.85 4 .40 14.35 5 .31

Bisquaternary Compounds Containing the Bridge CH,OCH, between the Two Ring Nitrogen Atoms 2 i 6 . . . . . , . . . 193 hIerCO

44.95 3 .67 10.70 5 . 8 8 28 5f . . . . . . , . . 134 EtOH-l\lezCO CaaHaoNsOzaPz 45 .20 3.79 10.55 5 . 8 3 29 4 2 . , , CH=CH 1Qi 3IeOH CasHasNsOzaPz 49 41 4 . 1 5 9 .60 5 .31 50.20 4 . 6 8 9 . 7 8 4 .57 30 4 3 , , , CH=CH 129 MeOH CasH4sNaOz3Pz 49 .41 4 . 1 5 9 . 6 0 5 , 3 1 49.26 4 .21 9 . 6 3 4 . 9 2 31 4 4 , , . CH=CH 192 3IeOH C ~ S H ~ S N S O ~ ~ P Z 49.41 4 . 1 5 9 .60 5 . 3 1 49.64 4 .48 9.39 5.29 32 4 4 . . . CH?CH? 87 MeOH 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

Lleltlng f Isoquinolinol. 0 p-

the picrate met,hod. points were taken on a Uni-Melt, apparatus. Toluenesulfonate.

* This number refers to the quinoline or pyridine rings. This number refers to the benzene ring. e Previously reported;z softens a t 108-110", melts a t 135-137'.

added a few minutea later, and much of the solvent wab evapo- rated at 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 at 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 com- pounds 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., Nut ley , S e w Jersey

Received Apr i l 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 data on some of the compounds described will be pub- lished a t a later da t e ; see also G. W. Duncan, S. C. Lyster, and .J. 13. Wright, Proc. Sac. Ezptl . B id . M e d . , 120, 725 (1965).

prepared. In two case^^^^ 6,12-diphenyldibenzodiazocines were formed by heating the corresponding 2-aminobenzophenone hy- drochlorides. We have found that dibenzodiazocines can be prepared conveniently and in good yields from 2-aminobenzo- phenones when Lewis acids are used as condensing agents.

Experimental Section

Ultraviolet spectra were determined in isopropyl alcohol usiiig a Cary 14 spectropho- tometer.

General Procedure.4-The corresponding 2-amiliobenzophe- none 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. In each case the crystalline reaction product waq recrystallized from a mix- ture 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.

All melting poiiiti are corrected.

(2) A. Sondheimer, Chem. Ber., 29, 1272 (1896). (3) A. Giacalone, Gazr. Chim. I tal . , 65, 120 (1935); Chem. Abstr., 29,

(4) Variations of the condensing agents and solvents gave different yields One representative example for the preparation

54509 (1935).

of the respective product. of each compound is shown in Table I on the folloxxing page.

l!l,i 2 0 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<ac~h ketoiie JWS prepared 1 . 1 ~ the iiiterartiiiii ( I F 2-naphthoyl chloride with the appropriate orgaiioc.atliiiiuni rengeiit. Table I l i d 3 previously unreported 2-iinphthyl ketoires .

. . ~ ~ ~

(11 Tile l 'n ivers i ty of Tennessee Aledlca l Cnits. AIempliis, 'Term. I S ) 11. R. JIenze and L. S u n n , .I. Org. Chrin . . 12, ,540 ( I Q 4 i ) . 13) 11. I I . l f e r r i t t a n d T. .I. Putnani. C p i l i p s i r r . 31 ( l Y 4 5 ) .