[ C O N T R I B U T I O N FROM T H E
LABORATORY O F APPLIEDO R G A X I C
CHEMISTRY,
RESEARCH COUNCIL OF ISRAEL]
Studies in Selective Toxicity. 11. Substituted Phenyl Benzoates and Benzenesulfonates
Received February 17, 1956 Twenty-six phcnyl benzoates and txnzencsulfonatcs, mono-, di- or tri-substituted by methyl, chlorine, and/or bromine, have been synthrsizcd and tested for toxicity against larvae of ticks and both eggs and larvae of houseflies. N o significant toxicity has been observed.
usual methods from the appropriate benzoyl or benzenesulfonyl chlorides and phenol^.^ None of the compounds showed significant toxicity when tested by contact of ticks (second stage larvae of Ornithodorus tholoxani) with residual deposits of the compounds at l g. per sq. m. on glass surfaces; or by pre-emergence treatment of the larval rearing medium of houseflies (Musca domestics vicina Rlacy.) with the compounds a t 200 p.p.m.
Substituted phenyl benzoates and benzenesulfonates have been tested as miticides. 1-4 Fifteen new compounds belonging to thcse classes have been prepared. They have been tested together with eleven previouslv reported compounds against ticks and the larvae of house flies. The new compounds are substituted by methyl, chlorine, or bromine in one, two, or three positioris of A : A.
R1
oX-OD R4
Rz R3 EXPERIMENTSL‘
(S= CO or SO?; Ri, It,, R3, R, = 13, CH3, C1, or Br)
Preparation of compounds. Equivalent amounts of the benzoyl or benzenesulfonyl chloride and the phenol were
The new compounds have been prepared by the
Yield,
% I I1 I11 IV V VI VI1 VI11 IX
. Y SI XI1 SI11
XIV SV
x CH3 H H C1
MI’.,“C. (corr. 1.
Empirical Formula
Analysis Carbon Hydrogen Citlc’d Found Calc’d Found
= CO
H H €I C1 H H €1 I€
H Br H CI Br H Br €1 CI . C1 Br C1 x = hO2 €1 H RI. I3 CI1, H CI CH, €I H H Br €I c1 Br Br €1 Br CI H Br
11 C1
H CH, H Br CI
8
68 68 57 58 43 50 51 39
16 16 75 45 85 11 78 97
68 20 68 02 57 92 58 48 43.65 50 43 51 66 39 99
4 4 3 3 2 2 2 1
116 9-117 3 79 6- 80 6 46 6- 47 103 1-103 6 83.2 116.9-117.4 126.5-127
-16 55 55 47 41 30 37
02 22 22 72
46 54 55 47 41 30 37
2 3 3 3 2
78 85 40 98 45 72 85 85
91 6- 92 98 - 98 118 -118 101 5 114 8-115 102 8-103 I45 5 164 6-164
7-1 45 68 71 58 63 76
1 5 4
4 8
(1) Cross and Snyder, J . Econ. Entonzol., 41, 936 (1948). (2) Kenaga, J . Econ. Entomol., 42, 999 (1949). (3) Kenaga and Hummer, J. Econ. Entomol., 42, 996 (1949). ( 4 ) Kirb? and Itcad, J . Sci. Food A y r . , 5,323 (1954).
46
60 63
02 86 31 47 80 50 53
50 50 81 02 27 59 34 81
4 64 4 83 4 21 2 90 2 52 2 62 2 54 2.04
83 92 92 39 32 1 49 1 85
2 91 3 49 4 00 3.71 2 33 1.49 1 90
(5) Cf. Wagner and Zook, Synthetic Organic Chemistry, New York, S. Y . ,J. Wiley and Sons, Inc., 1953, Methods 286 and 552. (6) All melting points are corrected.
ti71
672
XEEMAN, MODIAIYO, AXD SHOR
heated together on a water-bath until evolution of hydrogen chloride ceased. After cooling, the solidified mass was triturated with an excess of 1 N aqueous sodium hydroxide for 10 minutes. The product was filtered off, washed with water until neutral, dried, and recrystallized from 95% ethanol. In addition to the new compounds listed in Table I the following compounds previously reported in the literature have been prepared and tested: p-cresyl benzoate, m.p. i2"; p-cresyl p-toluate, m.p. 90.2-91.8"; p-chlorophenyl pchlorobenzoate, m.p. 96'; 2,4-dichlorophenyl benzoate, m.p. 94.2-95.2"; phenyl p-toluenesulfonate, m.p. 95.8-97.5'; p-cresyl p-toluenesulfonate, m.p. 67.4-68.1 '; p-bromophenyl p-bromophenyl pp-toluenesulfonate, m.p. 92.3-95'; bromobenzenesulfonate, m.p. 121.6' ; p-chlorophenyl pbromobenzenesulfonate, m.p. 108.8-110' ; 2,4-dichlorophen-
VOL.
21
yl p-toluenesulfonate, m.p. 120.6-121 O ; and 2,4-dibromophenyl p-toluenesulfonate, m.p. 120.6-122.2'.
Aclznowledgmmt. Thanks are due to Professor E. D. Bergmann for his advice; and to Professor G. G. Mer and Dr. R. Cwilich of the Malaria Research Station of the Hebrew University, Rosh Pina; and to K. R. S. ilsher and R. Cordova of the Research Laboratories, Medical Corps, Israel Defence Forces, for biological tests. P. 0. Box 5192 JERUSALEM, ISRAEL
