INDUSTRIAL AND ENGINEERING CHEMISTRY
July, 1946
of inorganic salts in general. As statcd in the preceding paper ( 6 ) , this moderately I o n solubility facilitates control of the leaching rate from a paint in n.1iic.h it is compounded. T h e leaching rate of toxic from a paint, jvhich determines the antifouling effectiveness, dc.priicls upon ninny factors in addition to the solubility of the toxic. The pmportion of toxic in tlir paint formulation, and the composition of the matrix, both influence the leaching rate profoundly, as Tablr- T', VI, and VI1 of a n earlier article (8) indicated. Thcsc variablw will be discuwxl in the succeeding papers of this series (6, 7 ) .
70 1
0 ) T e r i y , J. D., and Ketrliuni, B. 11.. Ihid,, 38, t o be puhli-hed. 1 7 ) Ketchurn, B. H., F e r ! > , J . D., and Bulns, A . E , , Jr., ILid., 38,
t o he published. B. 11.. Ferry, J. D . , Redfield, A. C . , and Burns, A . E., Jr., Ibid., 37, 4%-90 (IO-tSr. 9 ) Latimer. W.M., "Osidstioii States of the Elements", S e w T o r k , S ) Iietchum,
Prentice-Hall, 193s. P., and Ctiirnside, R . C . , J . SOC.Chem. Ind., 53, 33T (1934). Spxtnn H "Corrosion and Protection of Metals". 1906. ..~~ , -4 .. .~ Sherrill, h l . S.', Z. p h y s i k . Chem., 47, 103 (1904). T a r r , J. G., and Wonson, -4.II., U. S.Patent 40,515 (1SG3). Wall, A , , Brit. Patent 2198 (1857). K i n k l e r , IT.,J . Assoc. 0,ficial Agr. Clrem., 22, 341 (1939).
10) Eooksby, I I . 118
,1 . i 1.3) 14) , 15)
~
~
~
LITERATURE CITED
Bengougli, G . D., and M a y , I < . , J . Inst. Jletals. 32, S 1 (1924). Coulson, E . J., J . A8soc. O f i c i a l Agr. Chem., 19, 219-35 (1936': 2 0 , 175-38 (1937).
Dannatt, J., Brit. Patent 2645 (1SC.l). D o r r , €1. C . , C . S.Patent :131,3R3 (1885). F e r r y , J. D . , and C a r r i t t , L). E , , I S D . ESG. ~ H F . M , , 38, 612-17 (1946).
COITRIBUTION KO.345 of the Woods Hole Oceanographic Institution. Thin aork was done under a contract between t h e Institution and t h e Bureau of Ships, K a v y D e p a r t m e n t , which h a s approved its puhlication. The interest of Captain H. A. Ingram, U.S.S., in initiating t h e s t u d y is grateful!). acknouledged. T h e opinions presented here are those of the author? and do n o t necessarily reflect t h e official opinion of the N a v y Department o r t h e naval service a t Inrge.
Fungicidal Activity of Bisphenols as Mildew Preventives on Cotton Fabric P A L L B. 3I.ARSH
~ Y D 3LiRI-
L. BUTLER
M
:iXY new fungicidal compounds irere iiivc.>tigatcd as 111.o-
spective mildew preventives for fabrics during World \Tar 11. T h e present paper reports biological testa on an esperimental series of bi-phenols and related materials of coniniercial origin, samples of which \\'ore made available to the Department of Agriculture with the suggestion that they be tc-tcd for fungicidal activity on fabric.' The t e h t s \Yere carried out primarily during the spring of 1944. Certain nc\v information i i presented concerning fungicidal activity as related to chemical ,Ltructurc. within this group of compound., together with ob-crvations and comments on biological test method. for uce in the selection of new fungicides. The compounds studied were 1arg:ly included in four differelit seriw whose parent compound- KCSIY:
I
I1
I11
IV
TeRt rchultR ~ I i o \ ~ ethat d kubstitution of t\vo clilorinc: or two bromine atoms for hydrogens in the positions para t o the phenolic hydroxyls invariably incitnsetl fungicidal potency over t h a t obBerved with the unhaloycnate,d diphenols: holvcvcr, further symmetrical halogen subst itutioii resultcd in compounds which were quite generally, :arid iv certain case> diatinctly, leas potcnt than the dihalogen derivatives. Considering the results as a
Biological tests have heen made to determine the fungicidal potency as Inildew preteritiyes o n cotton fabric of a group of hisphenols and related cornpoiinds. Substitiition of two chlorine or two bromine atonis for hydropens in t h e positions para to tlie phenolic hydroxyls iniariiibly increased fungicidal poten(,>-o \ c r t h a t observed i t i t h the iinhaloge~iateddiphenols; further syni1;ietrical halogen substitution resulted i n conipoiinds which were penerally, and in certain cases clintinctly, less potent than the dihalogeii deriJatives. 2 , 2 ' - ; \ l e t l i ~ l e i i e l ~ i ~ ( l - n i t r o ~ , h e ~ i\o. al )s completely lacking in nira*uraI)lc funpic,idal potency a t any of the concentrations tested: the banien-as also t r u e of chlorine-substitu ted deriw t i\ e-;of 2 , 2 '-me tliylenetliphenol in which both phenolic hydro Is had Iwen tilocked b) formation of ether linkages. hree- and foiir-ring cornpounds containing p-cresol or p-chlorophenol units joined by -CHwere distinct1)- less eflecti\e thiin the corresponding bisphenols. No coinpound n as found to he more fungicidal per u n i t w-eight on t h e fabric t h a n 2,2'-methy1enebis(4-chlorophenol). >lethods for testing faliric ~riild e w preientives are cliscuswd.
INDUSTRIAL AND ENGINEERING CHEMISTRY
702
con,. pound
No.
18
19 20 12
OCHi OCHI OCHa OH
C1 CI
.~.....
.,..
CI Br Rr
C1 C1
Coni-
Car-
0.8;'
0.8';
1fi
OH
OH Br OCHr
Br Br NO?
Br Br
Soil suspension
post, rinKton,
O.O25',l 0.05';
100
100
100
100 100
100
100
100
100
100 100 100 14 100
100
100
100 100 100 0 100 88
100
100
100
3 100
lowing quaiititiw pcr liter: 1.90 jii'anis SH,SO, 0.0553 0.15"
100 4 3 1 0 0
48 100 100 98 100 42 100 100 OH 100 100 30 I n all cases concentration on t h e fabric is expressed as
14
a
."..._....I
Carhons Nunihered. 1 3 4 .i 6 1 3' 4' 5' 6
Vol. 38, No. 7
INDUSTRIAL AND ENGINEERING CHEMISTRY
July, 1946
T.4BLE
703
ACTIVITYO F TWO-, THREE-, AND FOUR-RING COMPOUNDS RELATED TO 2,2’-lIETHYLEXEDIPHEXOL,A s 11. FUNGICIDAL LfEASURED BY THE RATING O F TREATED FABRIC IN S O I L BVRIAL AND Chaetomium q ~ O b O S t L I t 2TESTS
Cornpound
Prr Cent Strength Loss after Exposure t o 5011burial (9 d.i>s) Chaelomtum olobosum CarringtonCompost (14 dass) 0 1% 0 2 % 0 4 % 0 1 % 0 2 % 0 4 % 0 1% 0 2 % 0 4 %
Forniula
NO.
0 €I
OH
99
96
67
100
98
90
5
0
0
99
39
6
100
90
22
8
3
0
100
io0
100
100
100
100
77
33
23
io0
100
100
100
100
100
77
79
87
99
97
92
100
100
1ou
0
5
5
68
100
100
100
100
100
100
100
100
100
69
loo
100
100
100
100
100
100
100
100
70
CI OH
1
11
CI
OH
OH
OH
id
CI OH
‘b CI OH
73
CI OH
A - c
c1
\ /
c1 OH
““2-cJ
v CI
CI
OH H - A
67
CHs
CH3
nun., and 48 3, 23.5, and 26.97, particles irl the lower diameter classes of 0.2-0.02, 0.02-0.002, and irit(.iilied ttBst fungus. T h e soil burial test is similar in principle t o t w t s d e w i i x d lireviously from this ( I 2 , 1 2 ) antl other (2) laboratoric+ Accordirig t o the results reported here, tlie severity of t h r te>t is more nearly approximated by the Aspergillus niger test t h n by tiic txvo ritlier culture-bottle procedures. The soil suspension test is a somt~\vlist simplified procedure pstterned after a test descrilwtl i ~ yFurry and Zametkin ( 9 ) . The choice of a suitable test for milderv resiztance of i:iGrics is complicated by t h e fact t h a t a wide variety of fuiigi n w involved in fabric deterioration in actual scrvice. Tliii sifiialion, coupled with the fact t h a t microorganisms differ n.itlc,ly i i i wnsitivity t o fungicidal agents, has argued strongly in favor of tmts involving a heterogeneous mixture of organismh c i i c l i as i - commonly found in soils. Contact with warm, 1noi-t soil i c undoubtedly one of the most scvere conditionq for biological fabric
July, 1946
INDUSTRIAL AND ENGINEERING CHEMISTRY
deterioration, and certain niilitary agcnciea have stressed the point that many of their fahric items must he able t o withstand this condition. ;\lthough quantitative differences do exist among soil burial re.ults determined on identical fabrics under different conclitions with various soil.5, experience in ninny laborafories indicates t h a t certain fabric trcntments are consistently poor in all or essentially all tests and t h a t other treatments are consiqtent ly much.better. Ttie soil suspension test repre~entsa n attempt to rctain the heterogeneous microflora of the soil b u t t o bring the environmental conditions under closer control than in the soil burial test. r\ltlioiigh a heterogeneous microflora is retained in actual practic(,, the writers cannot defend the thesis t h a t soil suspension are merely simplified soil burial te The population of oryani-nis which grow on the fabric in soil suspension tests is qualitatively and quantitatively different from the population found on the same fabric in soil burial teqts in the same soil. l’reviou.-ly reported tests of 2,2’-methyle1icbis(~-chlorophenol), niimber 11 (commercially called “compound G - A ” ) , in parallel v i t h p~ntacliloroplioiiol,salicylanilide, tetrabromo-o-cresol, and otticr phenols ( I ? ) hnd already eGtablirlicd that the former com. pound has flunyicidal activity of a high order. I t is apparent from tile data pre-entetl here that other clovly al-o have high fungicidal activity which, hon. not exceed that of compound 11.. T h e possible uses for tlicse compounds have not becn thoroughly erplored, and it might he found tliat for specific uses certain of them noulti have distinct advantages over conipound 11. Compound 57, for example, niigtit he superior to compound 11 as a s p m y or du-t t o prevent “late hlight” of potatoes or other plant dileai;eh, etc. .-Uttioiigli compound 11 has been used commercially as n fabric preservative on a n extensive scale in the 1a.t three year.sedata. ACKNOWLEDGMENT
T h e authors are indebted in particular t o W. S. Gump, of Givaudan-Dclawanna, Inc., who synthesized the compounds used in this etudy, and t o E. Iiunz, R. Horsey, and Thomas Wallace of the same concern for advice and interest during the course of the work. LITERATURE CITED
t c 3 - b
(1) Britton, E. C . , and Bryner, F.. U. S. Patent 1,969,963 (1934). (2) Dean, J. D., Strickland, W. B., and Berard, W. N., Am. Dyes h f R e p t r . , 34, 195-201 (1945). (3) Furry. h I . S.,and Zametkin, M., Ibid.,32, 395-8 (1943). (4) Greathouse, G. A., Klemme, D . E., and Barker, H. D., IND. E s o . CHEST.,. &SAL. ED.,14, 614-20 (1942). (5) Gump, W. S..U. S. Patent 2.250.480 (1941). if3 Ibid.. 2.353.724 *-, -~ , - , - - ~ , (1944). ~~
( 7 ) I b i d . , 2,354,012 t19a4j. (8) Klarmann, E . , and Gates, L., Ibid.. 1,967,825 (1934). (9) Klarmann, E., and Yon TVoxern, J., J . Am. Chem. Soc., 51, 60510 (1929). (10) Kunz, E. C., Luthy, hl., and G u m p , ‘A‘. S., U. S. Patent 2,353,736 (1944). (11) Marsh, P. B., Greathouse, G. .1., Bollenbacher, K., and Butler, AI. L., ISD.ESG.CHEM.,36, 176-81 (1944). (12) hfarsh, P. B., Greathouse, G. A., Butler, M. L., and Bollenbacher, K.. U.S. Dept. Agr., Tech. BuZL 892, 1-22 (1945). (13) Thoin, C.. Humfeld, H., and Holinan, H . P., Am. Duestuff X e p t r . , 23, 581-6 (1934). (14) T r a u b . E. F., Sewhall. C. A., and Fuller, J. R.. Surgery, Gynecol. O L s t ~ t . ,79, 205-16 (1944).
AUTOXIDATION OF FURFURAL A. P. DUSLOP, PAUL R . STOUT, A N D S.i3IUEL SFADESH The Quaker Oats Company, Chicago, I l l .
Color and acid formation in furfural at room temperature are shown to be due to autoxidation, the course of which is different from that of benzaldehyde. It occurs at a considerably lower rate and the reaction is interrupted at a much lolier lebel of acidity. A mixture of acids is formed from furfural, not merely acetic acid or solely furoic acid as had been speculated previously. The changes may be prevented by storing furfural in an oxygen-free atmosphere, or effectively inhibited by adding to furfural a small quantity of a variety of baric substances such as tertiary amines or alkali metal soaps or phenolic antioxidants. ’Water causes a partial inhibition of the autoxidation.
I
S SOR1\IhL storage, furfural slon-ly dwkens in color; n change accompanied by formntion of ncid. The magnitude of these changes with reference t o the amount of furfural is small even niter relntively long periods of time. Severtheless, it was considered desirable t o find some means of preventing or retarding the reactions responsible, mid to accomplish this it \v:is necessary t o have some knowledge of the cniise. Previous to this Ivork, it was known that the color bodies in on distillation, and aged furfural were left behind a s a resi~lut~ t h a t tlie yield of rccovered furfural ~ r i gtiner:llly s high. In addition, stabilizers such as hydroquinone and pyrocntectiol h:id been found to inhihit color formntion. There hnJ been considerable
speculation regarding the nature of the formed acid. For example, acetic acid -xas postulated, a view originating in plant data since acetic acid and also acetaldehyde are by-products of the furfural manufacturing process. Another hypothesis attributed t h e development of acidity t o t h e formation of furoio acid, a belief based largely on the kno-xn behavior of benznldehyde. This was not unreasonable, since i t is true t h a t furfural parallels benzaldehyde in a number of well known reactions. Some of these reactions are illustrated in Figure 1, nhere R denotes the fury1 or phenyl radical. Under the influence of sodium cyanide, furfural condenses with itself t o form furoin, the furan analog of benzoin. Both aldehydes undergo the Cannizznro reaction in the presence of strong alkalies to give the eorresponding alcohol and ncid in equimolecular proportions. With ammonia, complex nldimines are formed: hydrofuramide from furfural, and liydrobenzamitfe from benzaldehyde. Under a p propriate conditions both can be oxidized t o the carboxy derivatives or reduced t o furfuryl or benzyl alcohols, respectively. The usual aldehyde tlcrivativcs can be prep:u.ed from either, as illustrated in this case by tlie oximes. O X l G E N IN COLOR A S D ACID FORIIATION
Preliminary studies soon showed tlint, n.1ic.n technical furfural was stored with free access t o nir a t room temperature, it darkened i n color and devclopcd :icidity much more rnpidly than
