March 1970
33.5
XETV COMPOUNDS
TABLE I1
RI
C&N *rS02NHN==(JR2 Compd
n2
nl
.\r
IIa p-CH3OCsH4 IIb P-C~H~OCGHI IIc p-n-C3H70GH4 IId p-CHaOCsH, IIe p.-C2H;OCGHI IIf p-n-C:jHiOCGH, u - c See footnotes i n Table I .
Cs& CsH: C& Ale
H H H COOEt
Me AIe
COOEt COOEt
reported as antituberculou- and antibacterial' agents. Compounds Ia, I b , IC.and Id all gave 100% control of JIeEoicZoyne app at an application rate corresponding to 29.18 kg 'acres8 Compound I b gave 90% control of Pucciiiia sorqhi when applied sumultaneously to foliage a t 500 ppm and to ,io11 at 14.6 lig 'acre.8 Experimental Section
1-Arylsulfonyl-4-phenylthiosemicarbazides(I).-The appropriate 1-arylsiilfonylhydrazide 4 mmol) way dissolved in 95% EtOH (20 ml), followed hy addition of phenyl isocyanate (5.4 g, 4 "01). Refliixing for 30 niiri iollowed by cooling of the aolution gave a white, crybtalliue rolid t,hat was recrystallized from MeOH or EtOH. 2-Arylsulfonylhydrazone-3-phenyl-4-thiazolines(I1).-The appropriate I ( 5 mmol) wa- di-..olved in DXIF (25 ml), and 5 mmol of a-bromoacetophenone ( 1 g, or ethyl a-chloroacetoacet,ate (0.82 g ) was added. The +olutioti was heated 30 min on a steam bath, the dark red liqllid XI. rhilled, and 3 S NHaOH was added to bring it, to pH h. ;\ddition of H 2 0 (100 ml) gave t'he product as a greenijh powder which was wa.5hed several times with H20 and recrystallized i v i i i i i EtOH. 1
Acknowledgment.-We thank Dr. Juan Estevan of the University of Barcelolin for elemental analyses and also the Diamond Shamrock C'orp. for generous supplies of several reagents. ( 5 ) P. C. E k m a n , E. A . Konogka. T . Gisi, R. H. Alizzoni, and R . L. Meyer, A n n . H a . Tuherc. I'ulniowtru Dw.,1 7 , i o 3 (1958); Chem. Ahstr., 63, A494.I' (1959). (6) R . H. AIiazoni and P. C. Eirman, J . Amer. Chem. S o c . . 80, 34il (1958). ( 7 ) I. Ishii, AI. Katagiri, 31. >akaniime, and T . Misato. .\-ippon .Yogei K n y u h u Kaiahi, 40, 4 3 i (1966): C ' i ~ r m .A b r t r . . 66, 92iOw (1987). 18) Personal communication from X I r , S o r m a n SI. Pollack, Diamond Shamrock Corp.
A n Aminopyriniidine Steroid' I).~J-ID11. PLLTAK DepaTtm r ti! o j Chemistry, .Vorthern Illinois C7niwmr1!/,DeKalb, Illinois ASD
60115
Yield, Mp, o c a
c-/C
180-182 dec 172-173 dec 163-164 dec 181- 182 187-188 194-195 dec
75 77 88
b
i2 84
73
Formula
Inalysis
C2?H,&303Sp C, H: S , d C23HPlN303sP c'?H, X,$ CnrH,3x3O;& C, H, S , S C ~ O H ~ ~ X ~ O ~ S P3 , s CZIH23S30;& C, H , S C22H25S3OjS2 c', H j s,i
ported.3 This work describes the first amiiio a i i d o g of this type. Experimental Section4
17fi-Acetoxy-2,4-diaza-l-hydroxy-3-methglamino-l,3,5~ 10)estratriene.--A solution of 50 mg of methyl 17@-acetoxy-1,5.jeco-2,3,~-trisiiorestraii-5-oii-l-oate,3~5 100 nig of methylguanidine sulfate, and 150 mg of anhydrous S a O l r i i i 5 nil of anhydrous EtOH was reflnxed 96 hr. The -teroidy were recovered from the HzO-diluted mixture v i t h CHCla. theii (lissolved in 2 ml of glacial HOhc and reflnsed for 16 h i . The material wab again recovered with CHCla after H2C) dil~itioiiof the reaction. Chromatography of the reaultaiit niistiii'e of *tarting material and product on a . d c a t l c plate (Nc-c Et0.4~-CHCla) gave 16 mg of product. Recrystallizatioii f i , r i m ETO.%C' gare pure material, nip 290 dec; vmaX 3460, 5340, 1610, l e j i O , 1-513 em-'; , , ,A 234, 290 niM: 261 mp. Anal. (CliH?iS303)N. (3) D. h f . Piatak and E. Caspi, Steroids, 3, 631 , 1 8 6 4 ) : E. Caspi and D. .\I. Piatak, t'rperientia, 14, 465 ( 1 9 6 3 ) . ( 4 ) Melting points are corrected. V h e n analyses are indicated I ) ? the symbol for the element, analytical results obtained for those elements ivere vithin d ~ O . 4of ~the ~ theoretical values. UT spectra ivere taken in AIeOH or RIeOH with 2 S HCI added (0.1 ml,5 ml). ( 5 ) E, Caspi, P. K. Grover, D . 31. Piatak, and T.Shimizii. J . Chrm. Snc., 3052 (1965).
Antituberculous Schiff Bases J. 11. ~IERCH.IXT A N D I).
H. CHOTHI.~
Inatititfe of Science, Bombay-32, I n d i a Received Spptenzber 1 6 , 196%
Schiff's bases formed by the conden~atioiiof iwiiazide [I] with various benzaldehyde, are reported t o possess antituberculous activity. We have prepared additional Schiff's bases (beiizylideiiei.onicotiiioy1 hydrazonei) which were tested for antituberculous activity by the technique of Doub and Younim-.?
ELI.\HI-C.ispr2 Experimental Section
Worcester Foundation j o i . Experimental Biology, Sh,.ewsbu,y, .IJassrirhusefts O l 5 @ Receii'erl October 17, 1969
Thus far, only two steroids where ring A is a pyrimidine ring capable of tautonieric forms have been re(1) This work was supported I,? C h - O i 1 3 i a n d Niv Deans Fund.
Puhlic Health Service Grants A-5326 and
(2) Recipient of Career Program .\ward Ch-K3-16614 from t h e Sational Cancer Institute.
Preparation of Schiff's bases.-Iwiiiazide (1 g) wan di-wlved iii E t O H (30 ml) and to it was added aldehyde" 1 3 g ) i n 20 ml of EtOH. The mixture was refluxed on a steam bath. 111 .ome cases, the compound separated while hot, in i,thew 011 coding or on dilution with H20. Most of the compi~iuid~ were pale yellow and crystallized from EtOH. (1) 11. Negiver, "Organisch-Chemische. .Irzneimittel iind ihre Synonyms," Akademie Verlag, Berlin, 1959, pp 199-200, ( 2 ) L. Donb and G. P. Toumans, Amer. Reu. Tuberr.. 61, 4 O i 1950). ( 3 ) S. R. Agramal, Y. B. Desai, H. C. Raushik, 31. S. Iilian. and 7. R . Merchant, J . Indian Chem. Soc., 99, 769 (1962).
R
-..
\l!l
I
11
('HO I
. . .
