2176
INDUSTRIAL AND ENGINEERING CHEMISTRY EKTOMOLOGICAL B I E l H O D
of the oil sample was emulsified with 9 ml. of 5% gun1 acacia solution, and the emulsion was injected into ten roaches at a dosage of 5.8 cu. mm. per gram weight,. T h e resulting mortality in 40 hours was 80%. From standard curves previously determined, this mortality corresponds to a dosage of 30 nig. of D D T per kg. of roach weight, or 30 micrograms of D D T per gram of roach weight. This indicates that 5.8 cu. mm. of oil emulsion contains 30 micrograms of D D T or 5.17 micrograms per cu. mni. As the dilution in preparing the emulsion is 1 to 10, there xre then 5.17 X 10 (dilution factor) or 51.7 microgramsof D D T per cu. mm. of the oil sample, or 5.17% (a specific gravity of 1 was also wc:d in preparing the standard curves). The chemical analytical w l u c for this sample was 5.27y0 D D T (Table IV). 0 1 i v milliliter
DISCUSSION O F RESULTS
.\!though these tests were conducted at temperatures up to 700' F.?the normal operating tcmperature of this generator is theriiiostatically controlled in the range around 600' F. The results of the three tests indicated that the percentage of D D T decomposed at t h r w tcmptmtures varied from about 3 t o S%, whicli is considered not t u be excessive for this method of dispersal. It is quite low in comparison t o decompositions encountered viith dispersal devices such as candles, in which the tlrcomposition 11:~skieen found t o be 25% and higher. Tahlcs I11 and 11- intiicatc. that) even at the highe5t temperaturesohpervc'd,rioriec)f thtLDDT was coniplctel!-pyrolyzrd; at the low-cr teniperaturrn apparently only i)ii(' chlorine atom n-:is ~ p l i r off each decomposed D D T molrcule, arid a t the higher tcmpersturrs from tv-u t o t l i i w chlorine atonib n-rre split off each drc , ~ i n l ~ i ~DDT s ~ d riiolecule. klowevei., f!oni the inwc.tic.itia1 st mdpc,int, t lie eliminntioii of oiily one chlorine atom :is hy(1rochloric acid results in a conipountl nrhich is ineffcctivct :IF an insecticide. Some question might be raised as to the effects on vegetation of the hydrogen chloride released by the small amount of D D T decomposed when dispersed by the thermal aerosol method. -1cdculation, such as the following, shows that the amounts of hydrogen chloride rplea,vd arr so .ma!! ns to he considered negli-
Vol. 41, No. 10
gible for practical pur'poses: 46.7 grams of hydrogen chloride are released hy every pound of decomposed D D T . rissuming decomposition of S%, which is the maximum found at 600" F., there would be 3.7 grams or 0.008 pound of hydrogen chloride released for every pound of D D T dispersed a t 600 o F. If the do+ age is 0.25 pound of D D T per acre, the hydrogen chloride released v-odd be 0.9 gram or 0.002 pound prr acre, xliirli i < thought l o he an insignificant amount. ACKIVOWLEDGRI ENT
The check entomo1ogic;tl analyses were performed by Leigh E. Chadwick of the Entomology Section, Medical Division. Arm? Chemical Crnter. LITERATURE CITED
C'hem. J . , 3, 56 (.July 194s).
nd Wilson, I. R . , J . Econ. Entomol., 40,3U!j iI ! I $7 ' , (4) (hlliiis, D. L.. and Glasgow. R . D., I b i d . , 39,241 (1946). (5) Fleck, E. E,, and Haller, H. L., IND.EXG.CHEN.,37, 403 (1H45). (6) Fleck, E. E., and Haller, H . L., J . .4m. Chon. S O C . ,66, 2095 f 1944). ii)Gcer. H., and Scol-ille, H., J r . . S a t l . Research Council (\-. ,,sect Comm. R p p t . 132 (1945). gow, Ti. D., and Collins, D. L., J . Econ. Entomol., 39, 227
(1946). (9) Gunther, F. -4.. ISD. ENC.CEiEar., ~ A L ED., . 17, 149 (1945:. (10) Hiiffman, C . If-., Saeser, C. R., and Hartnett, J. G., TUMR 1241, U. P. Dept. Commerce, Office of Tech. Services. K e p t .
PB 19862 (19461. i l l ) L a t t a . 11.. . I . Ecopi. Eiifvrnol., 38,66s (1945). 112) LeClnir, J . E., ISD. E s c . CHEM.,hs.~.. ED.,18,i 6 3
(1946).
(13) Xorton, H . E . , TDLfR 1304, U. P. Ilept. Commerce, Office o f Tech. Sen-ices, R e p t . PB 53246 (1947). i 14) Scheciiter, M .S., arid Hnller, FT. L., J . -4m.Chem. SOC.,66,2129
(1944). (15) Bcholefield, P. G., Bowden, S. T.. aiid Jones, W.J., J . SOC.Cheni. I n d . , 65, 384 (1946).
(16) War Department, Washington, D. V., 'I31 3-381, Generator. Smoke, hlechanical, XI2 (1944). ~ < > : c L I \P I )
I l r < ~ r m h c r31, 1948
Fungicidal Activity of Bisphenols P 4 U L B. I\3ilRSH, IIIARY L. BI-'I'LER, ASD BERKICE S. CL4RK S . D e p a r t m e n t of .4gricirltz~re,Beltscille, M d .
1 n continudtion of experinleiits previous11 reported (IP), t h i r t j -nine additional bisphenols and closely related compounds have been tested for fungicidal actiFitj as mildew prebentives on cotton fabric, bringing the total number of compounds tested to sevent5-three. Somc of these compounds are much more effective per unit weight on fabric t h a n others as fungicides, and the trend toward high act i \ i t ? is correlated with certain features of chemical structure. The data do not appear to warrant the selection of any siiigle bisphenol from among the group tested as having unique high potency b u t suggest rather t h a t high potenry is related to a certain generic t1pe of structure within the group. For convenience in presenting the data, 2,2'-methj lenebis(4-chlorophenol) has been selected arbitrarily from among t h e more active compounds and used as a point of reference for comparison with other compounds i n both a c t i \ i t j and chemical structure. Bis-CHCHg-, phenolic bridges consisting of -CHl-, -CHC&--, -CH=CII-, and -Sh a t e been found comor -SOT patible with high activity, whereas -SO-
bridges are much less satisfactory. The presence ot' halogen atoms in all four positions ortho to t h e bisphenolich? droxjls is consistently accompanied by low activity. Bromine has been found less desirable from the standpoint of fungicidal potenc) than chlorine i n bisphenols of high total halogen content. Bisphenols with a chlorothymol t ? pe of structure, with unusually high molecular weights, a coniplete lack of halogen, or ether linkages blocking both phenolic hydroxyls have been found low in activitj -
PIWYIOUS report ( 1 2 ) described experiments which dealt with the fungicidal activity of the bisphenols in tests as mildew preventives on cotton fabric. The present paper gives results of a continuation ef this earlier work. The previous report pointed out certain relations between chemical structure and fungicidal activity within the bisphenols. iimong the thirty-four diff erent compounds tested, several highly active materials were' notcd in a certain generic structural group, typified for conveil-
TABLEI . MELTINGPOISTSO F BISPHEXOLSA S D RELATED COXPOIJKDS TESTED FOR FUNGICIDAL ACTIVITY~ compound NO.
1
3
! 7 8 9 11 1” 13 14 15
18 18
19 2 1)
25
?
“6 27 28 29 30
31 32 33 38 3i
38 89 40
42 43
Melting Point,
2177
INDUSTRIAL AND ENGINEERING CHEMISTRY
October 1949
C.
Compound So.
118.5-120.5 45 160-168 4i 107-110 49 137-138.5 51 180 db 52 162-164 53 99-128 178-179, checkc 177 5 -178 18%-174 d 57 171-173 58 205-209 d 59 1616-167 ijL 181.5-182.5 d 67 95-98 68 71-73 107-108 d 188 71 02.5-94 72 140.5-143.5 73 224 d !? 220.5-224.5 ,J d 269 78 150-153 slight d 79 210 d 80 217-220 81 245-246 83 223 d 86 189 d 87 144-145.5 155-160 101 106-109, check 1 0 6 . ~ - 1 0 7 . 5 102 60-61. c h e c k 6 1 3024
:; !;
RIelting Point,
C.
120-141, check 139.5-140 1,9-183 239-241 196-197 177.5-178 205.5-208 211-211.5 210-212 178-179 178.5-183 188.5-191 158-159 12.5-126 213-215d 176-179 130.5-131 117.5-118.5 190.5-194 130.5-133 232-235d 320-235d 160-162 90.5-91.5
128.5-129.5 171-172 157-159 188-18Qd 111-112 2°9.5-210.5, check w - 2 1 1 244-248, c h e r k 244-24.5.2 I?-125 2.71.5-252
‘3 All figures except those marked “check” a r e from drterniinatioiia n i t l i a Fisher-Johns Plectricaliy heated aluminum ataw?, melting point apiiaratiiq. .The temperature was generally kaised 2 O or Ies: per minnre in t h e last f p n degrees before melting. Supplies of compounds 17, 50, 63, 65, O G . 84, and 85 were inadvertently exhausted before melting points were taken. b Designation d after t h e temperature indicates t h a t decomposition ocrurred primarily after melting: d preceding the temperature indicates pronounced change in colur or appearance before melting. c The figures following t h e designation “ r h e r i ” x e r c obtained by h n qchutz precision thermometers in a mcchanirallj. stirred, srilfiiric acid. inelting point apparatus.
cedure; the first p:irt was identical with the Metarrhiziurn glutinosum culture bott,le test Dreviouslv listed under the heading - “culture bottle procedure B,” and the secoiid part consisted of a soil suspension inoculation on t,hesame fabric strips. U.S. Department of Agriculture isolate 1334.2, known fornicr1.v as Metarrhizium glutinosum, vias shown recently by White aILil Downing (29) to be a misnamed culture of .llyrothen’urn ter.rucari,i, and should be known henceforth under t h a t name. T h e sttitit’ isolate, S o . 1334.2, was used in the present as in the preview work. T h e incubation period for the W y r o t h e c i u t n test as 11 days, as was also the period for the subsequc.nt soil surpeii>ii)ti incubation. I t is thought that the data lirre presented, in corijuncrioti w i l i i previously published information (12, I S ) , niay prove useful :IC reference data for other workers iiiterested in applyiiig the san~i’ or similar methods to previously untested compounds. The experimental compounds R-ereapplied to fabric froin solvent solutioii as described previously (12); an %ounce duck, of 119pound original breaking strength, and called “Q duck” in this laboratory, was employed throughout. The compounds, includiiig those used in the earlier work (1.9))x e r e white or almost white. solids, with the exception of 43, 45, 47, and 100, which were bright yellow solids. I n general the compounds tested were believed t o have high or very high purity. Table I lists the melting points of the various samples. lleltirig point figures were located in Beilstein (f4,1 5 ) for compounds 3, 4, 5, 7 , 8, 33, 30, 37, 38,40,12,43. 45, 49, 51, 52, 53, 57, 58, 78, and 86, and in the patent literature for compounds 15 and 16 ( 7 ) , 51, 52, and .53 ( 6 ) , and 57, 59, and 61 ( I O ) . I n general the-r figurea were in reasonably good agreement n i t h those &on-n in Table I . Gallacio (3)reported 177 178” C. to be the true ni~ltirigpomt for purified cornpound 11. RELATION OF STRUCTURE TO ACTIVITY
ienee in presenting the d a t a by “compound 11,” 2,2’-methyIenebis(4-chlorophenol); compounds deviating in certain ways froni this general type of structure were found to be lower in activity. Lower activity was associated with lack of halogen, more halogen, replaceinent of the phenolic hydrogens t o form ethers, or increased molecular size. T h e information to be presented here includes d a t a from experiments on thirty-nine bisphenols not previously tested, as well as new data for comparative purposes on sevrral of the compounds included in t h e earlier work. TEST PROCEDURES AND COMPOUNDS
T h e test methods were, in general, similar to or ideiiticul with those described in greater detail in the earlier paper (12). ribsence of specific mention to the contrary here niay be considered to indicate conformity of the methods used in the experimciita t o be reported here with those recorded there. The Chaetomium globasurn test was carried o u t according t o the procedure previously described, consisting in brief of the planting of treated and untreated or control strips of fabric on mineral salts agar without sterilization, followed by inoculation with the fungus, incubation for 12 days a t approximately 30” C.: and determination of the residual strength of the fabric. Untreated control strips invxriably showed complete loss of tensile strength a t the end of the test period. T h e Aspergillus niger test was also carried out nccording t o the method described in the previous paper, the procedure consisting essentially of inoculating the test strips on a glucose-mineral salts agar directly Kith a suspension of spores of the fungus and rating them after %day incuhatiori on a scale ranging from 0 (no grovvth) t o 6 (heavy growth). The soil bnrial test was carried out in glass-covered 20-gallon aquaria as previously outlined, except that’ a Chester series sandy loam from Maryland was used in place of the Carrington series Sebraska soil. The Uyrothaciurn-soil suspension test was a .combination pro-
ISFLCENCE OF TYPEO F BRIDGE.Table I1 prese1lt:i re.\ults of experiments t o investigate the importance of the type of bridge in determining the fungicidal activity of :t bisphenol. The --CH=CH--, -CHCH,---, aiirl -CHC6Hbridges in compounds 73, 81, and 83, respectively, were found compatible n i t h high activity. Cnoxidized sulfur in the bridge was similarly conipatible with high activity (compound 57 j, whereas an --SOzor -SObridge reduced activity. Thus, compound 72, with an -SO2bridge, was much less active than compound 57 ivith a n -Sbridge, compound 84 n-ith an -SObridge was lcss active than compound 71 with an -Sbridge, and compound 3024 with an -SObridge was less active than compound 85with x n bridge. Bechhold and Ehrlich ( 2 ) found that the -SO1-- britlgts , . 111 ”tetrabromodihydrory-diphenyl sulfone,” (HOC,H2Urz)2S(Js, brought about greatly reduced bactericidal action in coinparisoil instead n i t h that of a similar compound containing a --CHzof an --SO*bridgr. Compound 100, obtained late in the 0 0 ,
li
I
course of this investigatiou, contailis a -C--Cbridge arid was teFted in parallel with several other compourds reported in Tahle \-I. I t is obviously less active t,han compound 12 (Table 0 0
iI I1
IV), ail indication that a -C-Chigh activity.
bridge is not conducive t o
Table 111presents P O S I T I O N AND D E G R O EF~& L O G E S A T I O N . data bearing on the importance of different positions, degrees, and types of halogen substitution in determining the fungicidal activity of a bisphenol. Attention is directed t o the data on the first six compounds which comprise a series of three paired inaterials. Compound 36 is lop- in activity in comparison with coinpound 13. I n compound 36 all four of the positions ortho t o the bisphenolic hydroxyls are occupied by halogen; in compound 13 only two of the four ortho positions are thus occupied. There are several indications from the data that, within the group of the bisphenols,
Vol. 41, Wo. 10
INDUSTRIAL AND ENGINEERING CHEMISTRY
2118
03
73 22
81
63 .?I5
10
4
0
0
0
:3
57
18
0
0
0
0
101)
100
100
100
6
6
6
6
81
28
4
100
100
6
6
6
4
100
100
1011
100
100
6
6
6
6
100
100
I00
77
20
3
0
lIH,
100
I8
63
98
!,
1MI
I (W
100
100
100
1IN)
100
100
100
I00
I00
5i
72
bS3 CI
100
CI
71
84
3024 a
HOCT)--SO--C>OH
100
Eight replicates in the Chaetomitrm test, three in mil burial twt, three in Aspergillus niger test.
the presence of halogen in all four of the positions ortho to the phenolic hydroxyls leads to very low fungicidal activity. Compounds 37 and 49, for example, also possess this type of halogen substitution and are lower in activity than two of their respective isomers with only two ortho halogens per molecule-namely, compounds 14 and 52. Compounds 32 and 33, likewise with four halogen atoms in the positions ortho to the phenolic hydroxyls, were found low in activity. Compound 32 was distinctly lower in activity than isomeric compound 16, the latter having only one halogen adjacent to each phenolic group. Comparison between the r t w d t ~obtained with unhdogenated compound I and those
with isomeric compound 3 suggests the p o ~ i b i i i t ythat the poeition of the bisphenolic bridge may be a factor influencing fungicidnl activity; compounds having bridges in positions ortho to phenolic hydroxyls are superior to those having bridges in the para or 4,4' positions. IClurmann, Shternov, nrid Gates (9) found the niembars of an homologous series of p-alkyl-o-chloroplienolsto be consistently and distinctly less gcrmicidal than their isomers in a series of 0alkyl-pchlorophenol~~.Suter (28) reproduced theso s u t h m ' data und added the remark: "It may be that an interaction of the hydroxyl and chloro groups is responsiblo for the deareased effeo-
0ctob.r 1949
INDUSTRIAL A N D ENQXNEERING CHEMISTHY
21'19
13
36 If10
tl
II
IOIJ
1 no
0
fi
0
100
40
3
2
1on
100
100
100
60
8
0
100
84
40
100
100
88
100
07
0
3
5
1
4
4
4
79
a7
73
lill
7
100
100
I00
100
100
R
0
76
3
9s
80
100
71
0
100
87
J
6
14
37 0
52 94
2
1
1
95
56
IS
100
84
13
100
100
4
n
o
0
15
IO
n
93
97
4
n
41
1
32
83
1s
2
11 15
0
0
13
Eleven replicates in C'hodomium teat, three io Hyrothwium-soil aimpension teat, three in aoil burial. throe in Aspcrgillur
n
aiger tcbt.
0
?
2
INDUSTRIAL AND ENGINEERING CHEMISTRY
2180 TABLE
11’.
Conipound NO.
Name
Vol. 41, No. 10
RELATIVE FUXGICIDAL EFFECTIVESESS O F BROIIINE-COXTAIXISG .4ND CHLORINE-CONTAINING BISPHESOLS __ 5 Strength Loss in ____ Soil Burial G r o v ( 1 1 OI Chaelomium T e s t Myrothecium teat -_ Soil suspension Com- Carrinz- - - - L ’ ~ ~..~. ~’~rJ 0.1%
0.27,
0.4%
0.025%
0.057, 0.147,
U.2%
0.0255
0.05%
0 I$
0
ton
:)WT
0
1 ‘ ;
11
.2”;
Compounds with T w o Halogen Atoms per llcilccrili. 11 12 50 51 57 5X
2,2‘-Methylenebis 2,2’-Methylenebis (4-chlorophenol)
0
(4-bromophenol) 2,2’-Dihydroxy-5,5’dichlorodipheny!, 2,2‘-Dihydroxy-5,3 dibromodiphenyl 2,2’-Thiobis (4-chlorophenol) P,P’-Thiobia (4-bromophenol)
-
0
[I
0
0
0
0
0
0
17 12
14
0
0
0
..
..
0
0
91
100
8 14
. .
0
0
17
38
0
I)
I1
0
2
48
43
>
..
..
50
59
n
I)
5
0
0 I>
3
79
0
0
I)
34
3
6
3
lor1
65
23
15
0
(1
6
0
3
IU
100
2
0
46
11
U
0
0
3
8
100
25
0
0
36
77
U
5
0
0
6
lj
Cornpounds with Four or More Halogen Atoms per Molecule 1 ,-I 1 !t
.52
33
2,2’-hIethylenebis (3,4,6-trichlorophenol) P,2’-.\Iethylenebis (3,4.6-tribromophenol) 2,2’-Dihydroxy-3,3’.5,,5’-tetrachlorodiphenyl 2,2’-I)ihydroxy-3,3’,5,5’-tetrabromodiphenyl
0
0
I)
40
0
0
0
100
10
6
0
63
88
6
29
4
,J
37
3
1
2
100
100
88
3
9s
100
?>
03
1
0
..
..
ion
100
0
19
33
43
1
95
66
2’2
87
26
100
100
100
2
x5
100
1
7
I)
tivcliii>a3 of tl,cw cur~ipoundsas roiiipsred with their isoniers.“ :t!~;iliig.- of’ high lialogc~ncontent in Tables 111 and I\. z i u * h u h R-hatever m:iy he t h e true causal factors, these finding3 do bear ciently Inrge t o hc rc,tained in significant form even on :I ~iiolsr a t least a supcrficial similarity to the results in Table I11 oil cornparison basis and oliviously do iioi represent a simple re,qull of paired compounds 13 arid 36, 14 and 37. 52 arid 49, and I5 and 32, the fact t h t 1)romine has a higher iitornic weight thnn chloiino. which c how I o w r activity for the conlpounils with more 1i:ilogrii R-GROI-PSL-BSTITUTIOSB. Although certain typr’. of l t - ~ r i i i i p in t h e pusitions ort!io t o the phenolic hydroxyls. .iilvtitulions niay be made upon the phcnolic riiigs i r i lit, coniCOMPARISOS O F B n o m s E ASD CHLORISE. Inforniatioii bearpouritl l i type of structure without greatly impairing iict i v i t r . ing on t h e problem of whether bromine is ~ i i ~ or r e less effectivc, other t y l i e s riinj- be highly detrimental. Tlvo related cnsvs in t h a n chlorine in inducing high fungicidal effectiveness in a bi.-nhich substitution caused marked loss in activity are illuzi I,:] t v t l phenol was included in d a t a presented in the earlier paper, but }I>- ihc, d:~t:ii i i Tahle V. Compounds 80 and 87, similar iii .t rucwas nor discussed from this viewpoint, since it did not. seem at the t iire t o ti:? closely related and highly active compounds 11 ii ud 57 time ti1 he sufficient t o warrant more than tentative conclusions. tiur n i ! l i isopropyl and methyl groups in the thymol type of conResiilts obtained more recently and presented in Table IIT. hovfigui,:it ion, were very low in activity. An interesting paralicl is c w r , may be usell iri combination n-ith the previous data t o d(,f o u r ~ c li n i l i i~ 1 : i t : i of I-pe of' bisphrnolic t)r.itlgc. Bridges cori..isting (I.
oi'
? ,I
- -CH?--. -S--ststoward hydrogen is offered as a possible explanation of differences between chromia and mol?hdma catalj sts w-hich have been reported in the literature.
T
HE oxides of chromium and molybdenum have been r t w g Iiized as excellent catalysts for the dehydrocj-clization of non-
arcni:ttic hytlrocvrbons since the reactions were first d e s c r i i d by X o l d a m k i I and Kamusher ( l a ) aiid by Grosse, Morrcll, 2nd Xhttox (6) yome tn-elve years ago. Since then considerable cffort has been applied t o studies of the catalysts and of the reactions occurring over them. During the same period the use of molyhdenum oxide supported on aluinin:t has been realized i n commercial processes for the catalytic reforming of naphtIi:+ ($, ?, 8. 14). Some of these developments have led to the i m p r r k ) r i t h a t considerable differences exist in the catalytic powers of molybdena and chromia, and t h a t the former is the preferable reforming catalyst. D a t a accumulated during several years’ study of clironiiaalumina catalysts led t o the conclusion t h a t , for the catalytic reforming of naphtha, chromia is fully as good as molybdena. T h e present authors’ results suggest, that the considerable differences between the twvo catalysts reported in the literature are a
result riot so much of fundamental differences iii ct~talytic:tctivity a s of differences in conditions of catalyst preparation an(1 operation, and particularly of difference in response to Iij-drogen pressure. Publication of results of naphtha ”hydroforming” with it molybdena-alumina catalyst ( 7 ) permits coniparisori with the which performance of chroniia-alumina under hydrogen pressur
