INDUSTRIAL AND ENGINEERING CHEMISTRY
1030
TABLEITr.
PERFORRlANCE I N
Compound
Compound Name 9,lO-Phenanthrapuinone 2,2’-Dihydroxy-o,5’-dichlorodiphenylmethane Salicyl anilide Rhodanine 8-Hydroxyquinoline Sodium diethyldithiocarhamate Tetramethylthiuramdisulfide 2,4-Thiaaolidinedione 2-Mercaptobenzothiaz?le Cetyltrimethylammoniuni bromide Pentachlorophenol 2- (Pentachloroplienoxy) ethanol
NO.
120 log 186 191 211 212 216 224 232 242
256 268
MILDEW-RESISTANCE TESTSO F Rating, Chaetomaun
Culture
( 2 weeks)
globosum
Strength Loss, % Soil Burial 2 weeks ’ 4 weeks 0 1
0
0
5
0
0 100 0
66 0 100 89
100 69 100 100
0
0
43
100
0
0 29 2
0 100 88
100
9 1
69
0
13
100 0 43
2.4
0 0 0
Compounds 247, 255, and 284 have the same number of carbon atoms and similar structures. Likewise, compounds 364
R=
JH3 /CH3
CHz-CH3
R=C /
‘CH1--CHt
255
CHs
R=C
CHr-CHz R=C’
\CH2-CH3
‘CH*--CH? 247
/ \
284
CH3
R=C
AHz
/
FUNGICIDES
0
0
-
VARIOUS
\
FH*
CHg-CH2 CHr-CH2 364 226 ( R represents the rhodanine nucleus)
and 225 have similar arrangements of carbon atoms. Comparison of the data in Tables I and I1 shows that with the exception of compound 255, which is not so effective as its related compounds, there is a striking similarity in the biological activity between the “open” and the “closed” forms. The deleterious effect of increased length of carbon chain, regardless of whether part of the molecule is present in an alicyclic or aliphatic structure, is shown by compounds 285 (Table I ) and 331 (Table 11). From the results in Tables I1 and I11 it may be seen that the excellent protection afforded by 5-cyclohexylidenerhodanine or 5-(p-methylcyclohexylidene)rhodanine may be reduced or lost if the hydrogen in the 3-position of the rhodanine nucleus is replaced by alkyl or aryl groups. All of the 3,5-disubstituted rhodanines included in this report would be useless for protec-
58 100
0
Vol. 45, No. 5
tion in soil burial, and of this group the 3-phenyl derivatives are ineffective even in the pure culture tests. It seems evident that the size and shape of the molecule as well as the presence of toxic groups are important factors in determining the protective power of mildew-proofing agents. Further correlations between the variations in structure of this interesting group of compounds and biological activity will form the basis of subsequent reports. However, many factors other than biological activity determine whether a given agent can be applied commercially as a cellulose preservative. LITERATURE CITED
(1) Alvord, E. B. (to Grasselli Chemical Co.), U. S.Patent 1,962,109
(June 5, 1934).
(2) American Society for Testing iwaterials, “ASTM Standards,” Part 111-A, pp. 1098-1104, Philadelphia, Pa., 1946. (3) Block, S.S.,IA-D. ESG. CHEM.,41, 1783 (1949). (4) Brown, F. C., and Bradsher, C. K., Nature, 168, 171 (1931). (5) Brown, F. C., Bradsher, C. K., Bond, S.hl., and Potter, M., J . Am. Chem. SOC.,73, 2357 (1951). (6) Brown, F. C., Bradsher, C. X., McCallum, S. G., and Potter, M.. J . Oru. Chem.. 15. 174 (1960). (7) Danielli, J. I?., “Cell Physiology and Pharmacology,” New York, Elsevier Publishing Co., 1950.
(8) Dodds, E. C., Goldberg, L., Lawson, W.,and Robinson, R., Nature, 141, 247 (1938). (9) Ferguson, J., Proc. Rog. Soc. (London),127B, 387 (1939). (10) Finholt. R. W.. Weeks. PI..and Hathawas. C.. IXD.ENG. CHEM.,44, 101 (1952). (11) Fuller, A. T., Biochem. J . , 3 6 , 548 (1942). 67, 112 (1945). (12) Geiger, W.B., and Conn, J., J . Am. Chem. SOC., (13) Horsfall, J. G., “Fungicides and Their Action,” Waltham, Mass.,
Chronica Botanica Co., 1946. (14) Klopping, H. L., and Kerk, G. J. M. van der, Rec. trav. chim., 70, 917, 949 (1951). (15) Lilly, V. G., and Barnett, H. L., “Physiology of the Fungi,” pp. 245-65. New York. McGraw-Hill Book Co.. 1951. (16) Marsh, P. B., Tertile Research J., 17, 597 (1947). (17) bliller, C. R., and Elson, W. O., J . Bact., 57, 47 (1949). (18) Nencki, RI.,Ber., 17, 2277 (1884). (19) Siu, R. G. H., “Microbial Decomposition of Cellulose with Special Reference to Cotton Textiles,” New York, Reinhold Publishing Corp., 1951. (20) Suter, C. &I., Chem. Revs., 28, 269 (1941). R E C E I ~ Efor D review June 14,1952. ACCEPTED September 13, 1952 This work was supported b y a contract with t h e Medical Division, Chemical Corps, U. S. Army.
(Mildew-Preventing Activity of Rhodanine Derivatives)
SOME 5-ARYLIDENE DERIVATIVES FRANCES C. BROWN, CHARLES I
