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VfNI »ADC TECHNICAL REPORT 54- 148

o „_

CHEMICAL INVESTIGATIONS OF FLUORINE COMPOUNDS AS FUNGICIDES

C. C. FINGER h. it. K£fc»

DIVISION OF FLUORINE CHEMISTRY ILLINOIS STATE GEOLOGICAL SURVEY

AUGUST 1954

WRIGHT AIR DEVELOPMENT CENTER

WADC TECHNICAL REPORT 54- 148

CHEMICAL INVESTIGATIONS OF FLUORINE COMPOUNDS AS FUNGOiDES

G. C. Finger P. H. Reed

Divia'.on of Fluorine Chemistry Illinois Slate Geological Survey

Atgust 19$*

Materials Laboratory Contract No. AF 33(038)-26990

RDO No. 611- 15

Rriplit Air Development Center Air Research and Development Command

United States Air Force bright- Patterson Air Force Base, Ohio

Carpenter Lltho & Prtg. Co., Sprlngflel», 0. 200-8 Koveaber 1951*

FOREvJORD

This report was prepared by the Illinois State Geological Survey, under USAF Contract No. AF 33(038)-26990. The contract was initiated under Research and Development Order No. 611-15, "Preservative Chemicals", and was administered under the direction of the Materials Laboratory, Directorate of Research, Wright Air Development Center, with Dr. Alton E. Prince acting as project engineer.

KADC HI 54-148

•

JVC OX XIAO J.

Fifteen aromatic x'lvorine compounds were prepared for

fungieidal scr«»er!.1.aig tests since 1 September 1952, The syntheses

and properties of these compounds and intermediates are described

in detail except in cases of known or borrowed derivatives. Ten

of the test samples are new to the scientific literature. Classes

represented are fluorinated benzole acids, phenols, anisoles,

toluenes, biphenola, Mphenyl sulfide, and benzyl derivatives.

A search was wade for colorless and thermally stable

fungicides in the biphenyl and biphenyl sulfide classes. Three

solid fluorinated hydroxybiphenyls, also called biphenols, were

synthesized with 2,2'-dihydroxy-5,5-difluorobiphenyi showing the

most promise, When a sulfur linkage was introduced into the latter

to give a biphenyl sulfide, fungicldal potency was increased so

that 24-95 parts per million prevented growth of four test fungi.

Cotton thread impregnated with the sulfur compound

showed no discoloration or loss in tensile strength, and when

treated with 1000 ppm solution was completely protected. Likewise,

2-fluoro-6-nitrophenol, a potent fungicide, and the difluorobiphenols

did not appear to change the tensile strength of the thread.

WADC TR 54-148 iii

Ape mp • pep ^„„+Ml

Twelve compounds were prepared on a fairly large laboratory scale for the

Materials Laboratory for evaluation studies. A total of 1900 g. of material

packaged as lGO-200-g. samples were delivered for this purposa.

PUBLICATION REVIEW

This report has been reviewed and is approved.

FOR THE COLUNDER:

^l>"

U. R. ..IIITiXIHE Technical Director Materials Laboratory Directorate of Research

YJADC TR 54-148 i~

TABLE OP CONTENTS

Page

INTRODUCTION 1

SECTION I FLUORINE COMPOUNDS STUDIED

A. Benzole Acids 2

B. Phenols and Nitrophenols 3

C. Nitroanlsoles 5

D. Nitrotoluenes 6

E. Biphenols 6

P. Biphenyl Sulflde 8

G. Benzyl Derivatives 9

SECTION II KXPERIIffiNTAL PROCEDURES 10

SECTION III SUla-ARY 21

BIBLIOGRAPHY 24

APPKhDIX I SUi.ii.AHY OF PHYSICAL AND FUNGICIDAL PROPERTIES 26

APPENDIX II COMPOUNDS DELIVERED TO MATERIALS LABORATORY 32

COMPOUND INDEX 33

WADC TR 54-148

INTRODUCTION

The synthesis of some fluorinated qulnones by Finger

at »1-/ in 1949 at the Illinois State Geological Survey led to

the discovery of their fungicidal properties by Tehon=/ of the

Illinois State Natural History Survey. Air Force materiel pro-

tection scientists, desiring to include organic fluorides in

their search, for new fungicides, initiated a fungicidal screen-

ing program with Dr. L. R. Tenon in March 1950, and a chemical

research program with the Geological Survey in July 1951.

Thirty-five cempounds wer*» covered in the first chemi-

cal report-', of which the nitrophonol and dinitro types showed

the most promise. The most sensational discovery was l-fluoro-3-

bromo-4,6-dinitrobenzene which inhibits the growth of A. nigar

at 0.8 parts per million.

This final chemical research report covers the period

from 1 September 1952 to the end of the contract, 30 April 1954.

Fifteen compounds were synthesized for the screening program,

and some large-scale laboratory preparations were studied.

Complete information on the fungicidal investigation

program is found in the Tehon repr^ts^ and any fungicidal data

appearing in the chemical studies come from this source.

WADC TR 54-148

SECTION I

FLUORINE COMPOUNDS STUDIED*

A. Benzole Acids

Two fluorinated benzole acids were prepared, namely the

2,4-difluoro and 2,4,5-trifluoro compounds. They were conveniently

obtained by oxidation of the appropriate fl'.ioroacetophenones.

F o, fiOOH

rV F

2,4-Difluoro- benzoic Acid, M.p. 183-184°

III

C0CH8

0' C00H

F II

2,4,5-Trifluoro- benzoic Acid M.p. 97-98°

These acids are white solids, slightly water soluble,

soluble in alkali, acetone, alcohol, insoluble in petroleum ether,

and sublime upon heating.

It is known that monofluorobenzoic and the chlorobenzoic

acids have mild astringent and antiseptic properties; thus it was

•Temperature reported in °C.

WADC TR 54-148

thought that polyflucrobenzol^ acids may exhibit similar proper-

ties. Complete growth inhibition of A. nlger and C. globosum

for the difluoro acid occurred at about 350 and 525 ppm, respec-

tively, whereas the trifluoro acid was 480 and 700 ppm. These

potencies are not outstanding, and It might also be concluded

that increased fluorine content is of very little significance.

B. Phsnols and Nitrophenols

Five phenols were studied, three of the 2-halo-4-fluore,

and two of the fluoronitro types.

The 2-halo-4-fluoro types were studied because 2,4-di- 5/

halophenols" are reported to have better phenol coefficients

than the monohalophenols, and dissimilar halogens increase fungi-

cidal potency in dih&lodinitrobenzenes—*—'. With the synthesis of

a key intermediate, 2-amino-4-fluoroanisole (V) , other research

made available 2-bramo-4-fluorophenol (IX) and 2-chloro-4-fluoro-

phenol (X) as new compounds, and 2,4-difluorophenol (XI). The

scheme of synthesis and pertinent physical data are given. The

bromo compound may be obtained more conveniently by bromination

of 4-fluorophenol in aqueoua solution with a near 80J& yield.

WAI'<J th b4~148

OCHj OCH,

V F

B.p,

OK

Br

42-43* 89° (1 ram.)

IX

F

4-

X =* Br (VI), Cl (VII), F (VIII)

OH

Gl

F 23° (F.p.) 88° (4 ram.) X

OH

V F

22.4° 52° (19 ram.) XI

Growth inhibition for A. niger in parts per million was

about 140 of Br-F, 400 of Cl-F, and 400 of F-F as compared to 600

for 4-fluorophenol. This shows some advantage in multiple and

dissimilar halogens.

The nitrophenols studied since the last report are

indicated in the scheme of preparation, and both are known

0«N

OH

XII

2-Fluoro-6-nitrophenol M.p. 91-92*

OH

F

OH

N08

XIII

3-Fluoro-4,6-dlnitrophenol M.p. 79-80°

WADC TR 54-148

compounds. They are yellow solids, quite insoluble in water but

soluble in alkali, and are readily soluble in the usual organic

solvents.

Growth Inhibition for A. nlger was 11.5 ppa for XII and

150 pjsa for XIII. thus reaffirming previous observations of potency

exaltation of nitro groups* On the other hand. 2-nItro-4-chioro-

phsnol at 10-50 ppmr Is also quite effective as a fungicide.

Cotton parachute webbing Impregnated with XII showed a

yellow eolor and no apparent change in tensile strength.-'

C. KltroaniBoles

Conversion of a phenol to an anisole or methyl ether

derivative causes a decided decrease in funglcidal potency. This 5/

was again clearly demonstrated with 2,4-dlfluoro-6-nitrophenol

when it was converted to the anisole (XV)• The phenol prevents

A* niger growth at 50 ppm. whereas the anisole permits some growth

at 600 ppm.

OH OCH

0«5rNF 0aK 2 ,4-DIf luoro-6-nitroanisole M.^. 55-55.5°

Preparation of the nitroaniscle was readily acccauplished

by the nitration of 2,4-difluoroanisole in a 44$ yield.

SIADC T* 54-148 5

' r

D> Nltrotolvtenas

Sinoe 3-fluoro-4,6-dinitrotoluene (XVIII)~*^^ shows

excellent funglcldal prop vtleSj It appeared worth-while to study

the potency of two isomerie precursors, 3-fluoro-4-nitrotolu6ne

(XVII) and 3-fluoro-6-n5trotoli\ens (XVI) • These compounds are

available from the nitration of S-fluorotoluene and it is interest-

ing to note that both ntononitro compounds will yield the same di-

nitrc derivative. They are yellow solids except the dinltro com-

pound la almost colorless.

+ | and |i and

V XVI

M.p. 27-28° 53° 78-79° Potency (ppm) 1000 400 5.9

The concentrations required to inhibit growth of A. nlger

are indicated below the formulae in parts per million as potency.

K. Biphenols

The biphenols or hydroxybiphenyls and their chlorinated 5/

derivatives are known to have bactericidal properties , and same

of these compounds are available under various trade names. Since

fluorinated biphenols had not been investigated as possible fungi-

cides, and since it was possible that they may bo colorless, heat-

stable compounds suitable for incorporation into plastics, some

preliminary studies were undertaken.

WADC TR 54-148 6

Thre* fluorinated biphenols were prepared - 2,2,-d'!-

hydroxy-5,5'-difluorobiphsnyl (XXI), 3,3 ,-difluoro-4,4»-dihy-

droxyb-iphenyl (XXIV) and 2,2l-dihydroxy-3,3',5,5'-tetrafluoro-

biphenyl (XXVII)• The scheme of synthesis involved an Ullm&nn-'

coupling reaction on the appropriate iodofluoroanisoles to the

bianisoles followed by an aluminum chloride ether cleavage to

the biphenols.

OCH-

r ii1

F XIX

0CH3

0' 1

XXII

OCH OCH.

P P

XXIII

V V XXI

M.p. 138-139°

M.p. 189° xx rv

0CH8 P

0CHa OCH

XXV XXVI

These compounds are odorless, white solids, fairly

high melting, slightly soluble in hot water and petroleum ether,

WADC TR 54-148 7

moderately soluble In ethanox, and soluble in alkali.

Growth inhibition of A. nlger was obtained at 140, 200

and 230 ppm for XXI, XXIV, and XXVII, respectively. These bi-

phenols are more potent than the simple fluorophenola, XXI shows

the most promise and on the basis of the tetrafluoro (XXVII)

compound multiple fluorine substitution is of no advantage,

Impregnation of cotton thread by the difluorobiphenola 4/

did not appear to affect the tensile strength"-' .

F. Blphenyl Sulfide

Sulfur and a number of its compounds are among the

oldest industrial fungicides known. Within recent years a great

deal of attention is being directed to organic sulfur compounds-^/

such as dithiocarbamates, thiuram disulfides, mercaptobenzothia-

zoles and others. It is interesting to note that 2,2'-dihydroxy-

3,3l,5,5'-tetrachlorobiphenyl sulfide-', known in the trade as

Actamer (Monsanto) and Lorothiodol (Hilton Davis Chemical Co.),

are reported as having bactericidal and fungicidal properties.

In view of the firngicldal activity of the fluorinated

biphenols, it was speculated that a sulfur linkage between the

phenyl groups would give increased potency. For a test case,

2,2'-dihydroxy-5,5,-difluorobiphenyi sulfide (XXVIII) was syn-

thesized from 4-fluorophsnol and sulfur dichloride. The compound

is a white solid with s. mild cresol-like odor, soluble in the

WADC TR 54-148 8

OH HO 3Clj o-<^>

M.p. 119° XXVIII

usual organic solvents and alkali, insoluble in water, and fairly

soluble in high boiling petroleum ether.

Fungioidal potency-' was inoreased by the introduction

of the sulfur linkage as indicated in the concentrations required

to stop growth of four test fungi,

CH HO OH HO

Q> <^-<Z> C. globosum 24 ppm 3. yerrucarla 26.5 " A", terreus 72 " E. nlger 95 *

r ^ J * s—7 ^

37 110 80

I4G « M

Cotton thread impregnated with the sulfur compound showed

no discoloration or loss in tensile strength, and when treated with 4/

a 1000 ppm solution was completely protected against fungus damage" -

G> Benzyl Derivatives

A sample of 2,4,6-trifluorobenzyl ohloride (XXIX)

possessed only very mild fungistatic potency.

The introduction of a -CH80H group in the aromatic nuoleus

increases solubility, and in the form of ealic/1 alcohol (saligenln)

WADC TR 54-148 9

a mild antiseptic is obtained* It was speculated that perhaps a

fluorinated salicyl alcohol nay offer some possibilities as a

fungicide. This compound at 600 ppm showed only 25$ reduced growth

OH £Ha0H

M.p. 61-63°

OH CHaQ

^ > H°n v pv~ V Vv V xxx

2-Hydroxy~3,5-difluorobenzyl alcohol

of A. niger, but complete inhibition of C. globe sum. It is in-

teresting to note that the parent compound is a better fungicide

than the benzyl derivative.

SECTION II

EXPERIMENTAL PROCEDURES

2,4-Difluoroacetophenone (I).—The usual Friedel-Crafts

acylation procedure was modified in that an excess of the aryl

halide was used to serve both as a reactant and solvent.

To a well-stirred mixture of 114 g. of 1,3-difluoroben-

zene—and 80 g. anhydrous aluminum chloride, 48 cc. of acetic

anhydride was added slowly and the resulting mixture refluxed for

one hour. After pouring over ice, steam distillation removed the

acetophenone and the unreacted difluorobenzene. A yield of 32 g.

(41$) of crude difluoroacetophenone was obtained and a vacuum

distillation gave pure 2,4-difluoroacetophenone, f.p. ca. +9C,

b.p. 89°, n§° 1.4881.

WADC TR 54-148 10

*w«£. Ceu.ou. i'Or uBH6raui u, 61.o4; H, 0»,07J F, 24.34.

Found: C, 61.47; H, 3.76; P, 24,47.

2,4,5-Trifluoroacetophenone (II) .-~Thls compound was ob-

tained by the above procedure, except that 1,2,4-trifluorobenzene—'

was the aryl halide.

The yield of the acetophenone was 45#c A vacuum distil-

lation gave pure 2,4,5-triflucroacetophenone, f.p. ca. 7°, b.p. 20

99-101° (20mm.), n£ 1.4718.

Anal. Calcd. for C8HoF80: C, 55.16; H, 2.69; F, 52.74.

Found: C, 55.12; H, 2.94; F, 32.58.

2,4-Dlfluorobenzoic Acid (III).—A mixture of 4.3 g. of

2,4-difluoroacetophenone, 8 g. of potassium permanganate, 160 ml.

water, 3 ml. of 10jt sodium hydroxide solution was refluxed 5 hours.

More permanganate solution was added during the refluxing to complete

the oxidation. After removal of the manganese dioxide by filtration,

acidification of the filtrate gave the crude difluorobenzoie acid as

a white precipitate, yield 3.7 g. (85$). Recrystallization from

water followed by sublimation gave pure 2,4-dlfluorobenzoic acid,

m.p. 183-184°. It is interesting to note that a mixed melting

point (131-182°) with 4-fluorobenzoic acid (m.p. 182-184°) shows

no significant depression.

Anal. Calcd. for C7H4Fa08: C, 53.18; H, 2,55; F, 24.04.

Found: C, 53.32; H, 2.44; F, 24.01.

WADC TR 54-148 11

2t4s5-Trifluorobenzolc Acid (IV).—This acid was prepared

from 2,4,5~trifruorcacetophenone by the oxidation procedure previ-

ously described.

Recrystallization of the crude acid from carbon tetra=

chloride followed by sublimation gave purs 2,4,5-trifluorobenzoic

acid, m.p. 97-98°.

Anal. Calcd. for C7HsF808: C, 47.74; H, la72. Pound:

C, 47.77; H, 1.67.

2-Amlno-4-fluoroanlsole (V).—To a mixture of 123 g. of

iron filings and one liter of ammonium chloride solution (0,78 N)

12/ with stirring, 122.5 g. of liquified 2-nitro-4-fluoroanisoie—J

was added slowly. After completion of the reduction, the amine

was removed by steam distillation as a heavy oil. Crude yield was

92 g. Vacuum distillation gave pure 2-amino-4=fluoroanisole, f.p.

ca. 3s, b.p. 117° (20mm.).

Anal. Calcd. for C7H8FN0: C, 59.56; H, 5.71; N, 9.92.

Found: C, 59.55; H, 5.53; N, 9.84.

The acetyl derivative after recrystallization from ethanol

followed by sublimation was obtained as white plates, m.p. 101*102°.

Anal, Calcd* for C9Hj.°FN0s: Ns 7,65. Found: N§ 7,60 =

2-Bromo-4-fluoroanlsola (VI) .—A Sandmeyer-cuprous bromide

reaction on 2-emino~4-fluoroanisole (V) gave an 89# yield of steam-

distilled crude product. Vacuum distillation gave pure 2-bromo-4-

fluoroanisole, f.p. ca. -27°, b.p. 79° (5mm.), ng 1.5447.

KADC TR 54-148 12

Anal. Calcd. for C7HsBrF0: C, 41.00; H, 2.95; Br, 38.98;

F, 9.27. Found: C, 41.19; H, 2.83; Br, 39.29; F, 9.07.

g-Chloro-4-fluoroanlsole (VII).—This compound was obtained

from V by a Sandmeyer-cuproua chloride synthesis in an 83$ crude yield.

The pure compound is a heavy colorless oil, b.p. ca* -17°,

b.p. 67° (5mm.), ng0 1.5173.

Anal. Calcd. for CTH6C1F0: C, 52.35; H, 3.77; Cl, 22.08;

F, 11.33. Found: C, 52.55; H, 3.75; Cl, 21.87; F, 12.12.

2t4-Dlfluoroanisole (VIII) .^-Schiemann—' reported the

synthesis of this compound from 2-fluoro-4-aminoanisole.

For this study it was prepared from V by the Schiemann

14/ transformation—' in an overall yield of about 50$. Data on the

20 pure compound are f.p. -15.5°, b.p. 151°, np 1.4705.

2-Bramo-4-fluorophenol (IX) *—This compound was borrowed

initially from other research and had been obtained from VI by

ether eleavage=^/ reactions, A more convenient method is the

direct bromination of 4-fluorophenol.

To a well-stirred suspension of 112 g. of 4-fluorophenol

in 500 ml. of water at 20°, 150 g» of liquid bromine was added drop-

wise over a period of two hours. The heavy oil layer was treated

with dilute sodium carbonate solution to alkalinity, and steam

distilled. After separation and drying of the oily distillate,

WADC TR 54-148 13

vacuum distillation gave a main fraction, b.p. 90° (2.5 mm.), which

solidified on cooling to pale yellow needles, m.p. 40-42°, yield

151 g. or 79$. The melting point of an analytically pure sample is

42-43°.

15/ 2-Chloro-4-fluorophenol (X)— .--This is a new compound„

f.p. ca. 23°, b.p. 88" (4 mm.), and was leaned to this project.

3g4-Difluorophonol (XI) .—The procedure used by Schiemann—'

ror preparing this compound was -used. An aluminum chloride ether

cleavage of VIII gave an 84$ yield of the crude phenol. Data on

the pure compound are m.p. 22.4°, b.p. 52° (19 mm,) or 74° (50 mm.).

2-Fluoro-6-nltrophenol (XII) . --This compound was prepared

from 2-fluoroanisole—-* as described iryfehe literature by Niemann

et al—'. The pure material, which was obtained by recrystalliza-

tion from aqueous ethanol, formed yellow needles, m.p, 91-92°, yield

44$.

3-Fluoro-4t6-dinitrophenol (XIII).—Hodgson obtained

this ccapound by the nitration of 3-fluorophenol, and recrystal-

lization from aqueous ethane! gave a white solid, m.p. 79-80°.

2.4-Dlfluoro^6-nltroanlsole (XV).—This compound had

been prepared previously by the methylation of 2,4-difluoro-6-

nitrophenol^/ in another gtv.dy& , An improved method described

•ADC TR 54-148 14

i "i i-'5*w» :» Ui»5*up»u InVOXVXng uiio OlrsCSi xii vri uxwii or U ,4-diriUOrO-

anisole.

To a solution of 75 g. (0.5 mole) of 2,4-difluoroanisole—

in 80 ml. of acetic anhydride with stirring, a mixture of 47 g.

(0.75 mole) of 100% nitric and 42 ml. of aoetic acids was added

slowly in 50 minutes, and the reaction temperature controlled at

35-40°with a water bath. Stirring was continued for six hours at

38-45°. After pouring over ice, the crude nitro layer was made

alkaline with sodium carbonate solution, and steam distilled. The

dried, steam distilled product on vacuum fractionatlon gave 41 g.

or 44JS yield of pure 2,4-difluoro-6-nitroanisole, b.p. 66-67°

(5 mm.). A small amount of an unidentified by-product was obtained.

3-Fluoro«-(S or 4)-nltrotoiuene (XVI and XVII). —These 21/ compounds were obtained by Schiemann—' by the nitration of 3-

fluoretoluene with fuming nitric acid. The 6-nitro compound is

obtained in the largest amount. Melting points of XVI and XVII

are 27-28° and 53°, respectively.

3-Flurro-4>6-dinltrotoluene (XVIII) .—This compound was

reported-' previously and was obtained in a 95JS yield by a mixed 21/

acid nitration of 3-fluorotoluene— , m.p. 76-79°.

2-Iodo-4-fluoroanisole (XXIX).—This compound was pre-

pared from 2-amino-4-fluoroanlsole (V) In a 78# yield of orude

ttADC TR 54-148 15

steam distilled product by the usual oandmeyer reaction. Vacuum

distillation gave pure 2-iodo-4-fluoroanlsolef f.p. ca. -21°,

b.p. 92° (3 mm.), n§° 1.5924.

Anal. Calcd. for C7HeFT0: C, 33.56; H, 2.40; F, 7.54;

I, 50.36. Found: C, 33.41; H, 2.41; F, 7.68; I, 50.69.

2s2'-DimethoxT-5.5t-fluoroblphenyl (XX).--An Ullmann

coupling reaction-' was performed on the preceding anisole to give

the desired bianisole.

The general procedure for the Ullmann coupling reaction

was to heat by an oil bath equal weights of the iodofluoroanisole

and copper bronze in a large test tcbe equipped with an air con-

denser. Reaction temperatures and heating time varied with the

compound in question, and occasionally more copper was added during

the reaction period. Extraction of the reaction mass in a Soxhlet

with acetorie removed the crude biphenyl.

A 70$ crude yield was obtained from the coupling of 2-

iodo-4-fluoroanisole at 190-210° for 2 1/2 hours. Recrystalliza-

tion from ethauol gave mhite needles. m„p» 121-121.5°.

Anal. Calcd. for- Ci4HlaFs0a: C, 67.19; H, 4.84; F, 15.19.

Found: C, 67.25; H, 4.63; F, 14.97.

2.2!-Dihydroxy-5,5,-difluorobiphenyl (XXI).--This compound

was prepared by an aluminum chloride split—' of the corresponding

ether.

WADC TR 54-148 16

A mixture of 0.3 g. of 2,2,-dimethoxy-5.5'-diflucrc-

biphenyl, 30 g. of anhydrous aluminum chloride and 80 ml. of

benzene wae refluxed overnight. The reaction mixture was poured

over ice, steam was blown through the mixture to remove the ben-

zene, and after the residue had cooled, the crude product was

recovered by filtration. Dilute sodium hydroxide solution was

added to the crude material and the resulting mixture extracted

with ether. Acidification of the alkaline extract reprecipitated

the biphenol, yield 6.3 g. (76#). Recrystallization from ethylene

dichlorlde gave pure 2-2'-dihydroxy-5,5'-difraoi-obipheryl as hard,

white crystals, m.p. 138-139°.

Anal. Calcd. for CiaH8FsOa: C, 64.87; H, 3.63; P, 17.10.

Pound: C, 65.06; H, 3.35; F, 17.38.

2-Fluoro-4-lodoanlsole (XXII)•—An 83# crude yield of

this compound was obtained from 2-fluoro-4-aminoanisole=2/ by a

Sandmeyer reaction. Recrystallization from ethanol followed by

vacuum sublimation gave the pure compound, m.p. 33.5-54°.

Anal. Calcd. for C7H6FI0: C, 33.36; H, 2.40; F, 7.54;

I, 50.36. Found. C, 35.48; H, 2.30; F, 6.87, 7.40; I, 51.51, 51.01,

S^-Dlfluoro^^'-dimethoxybiphenyl (XXIII) .—By the

general procedure under XX, the preceding aniscle was coupled by

heating at 190-210° for about four hour3, and a 70# yield of crude

biphenyl was obtained. A recrystallization from a benzene-ethanol

mixture gave the pure biphenyl as white platelets, m.p. 153-154°.

1ADC TP. 64-148 17

Anal. Caicd. for Ci^HiaP^O,: C, 67.19; H, 4.84; F,

15.19. Found: C, 67.08; H, 4,63; F, 15.00.

gf3t-Dlfluoro-4.4'-dlhydroxyblphenyl (XXIV) .—By the

procedure indicated under XXI, 3,3l-difluoro-4,4'-dlaiethoxybi-

phenyl was split with aluminum chloride to the corresponding bi-

phenol in a 92*8 crude yield. The crude product was recrystal-

lized from an ethanol-ethylene dichloride mixture to the pure

biphenol, m.p. 180.5-189°,

Anal. Caicd. for CiaH8FflOa: C, 64.87; H, 3.63; F,

17.10. Founds C, 64.92; H, 3.62; F, 17.04.

2-Iodo-4>6-dlfluoroanlsole (XXV) .—An amine hydroeiilfate

3lurpy was prepared by the slow addition of 2-amino-4,6-difiuoro-

9/ anisole-' with stirring to 34 ml. of concentrated sulfuric acid in

150 ml. of water at 60°. Diazctization was effected at 0-5° by

adding a solution of 15.2 g. of sodium nitrite in 50 ml. of water,

and at the end sulfamic acid was added to destroy excess nitrous

acid. The diazonium solution was poured slowly into a stirred

solution of 40 g. of potassium iodide in 60 ml. of water, and the

temperature held at 5-10° during the evolution of nitrogen. Sodium

thiosulfate solution was added to remove the iodine, and the mixture

was steam distilled. The crude product, 49 g., wasvacuum distilled

and a yield of 43 g. or 80# of pure iodo compound was obtained as a

heavy oil, b.p. 60-61° (3 mm.), n§° 1.54933.

WADC TR 54-148 18

Anal. Calcd. for C7H8P8IO; C, 31.13; H, 1.67; F, 14.07;

I, 47.00. Found: C, 31.31; H, 1.81; F, 14.28; I, 46.72.

2,2;-Dimethoxy-3,3tt5,5t-tetraflucroblphsnyl (XXVI) . —A

mixture of 27 g« of 2-iodo-4,6-difluoroanisole and 35 g. of copper

bronze powder was heated at 210° (bath temperature) for three hours,

The reaction mass was pulverized, extracted with acetone, and the

acetone extract poured into water, whereupon an oil separated and

solidified on cooling. Yield of crude product, 12.7 g. or 89#.

Recrystallization from aqueous ethanol and a final sublimation

gave the pure biphenyl, m.p. 49.5-50°.

Anal. Calcd. for C"i«HioF40a: C, 58.75; H, 3.52; F, 26.55,

Found: C, 58.54; H, 3.38; F, 26.35.

2,2,-Dlhydroxy-3t3>lt515

l-tetrafluoroblphenyl (XXVII) .—A

mixture of 9 g. of the preceding biphenyl, 26.6 g. of anhydrous

aluminum chloride, and 100 ml. of dry benzene was refluxsd for five

and one-half hours. After pouring the reaction mixture over ice,

the benzene was removed by steam distillation, and after chilling

the crude 3olid product was removed by filtration. An ether ex-

traction of the aqueous layer completed the recovery. The crude

product was dissolved in 10# sodium hydroxide solution, alkali-

insoluble material was removed by ether extraction, and acidifica-

tion with dilute hydrochloric acid precipitated the crude biphenyl

as a white solid, yield 7 g. or 86#, Recrystallization from a

WADC TR 54-148 19

benzene-petroleum ether (low boiling) mixture gave the pure compound

as a wiiiuo powder, la.p. XY5®•

Anal, Calcd. for CiaHeF^O,: C, 55.82: H, 2.34; F, 29,44.

Found: C, 55.57j H, 2.20; F, 29*31.

2,2t-Dlhydroxy-5,5t-dlfluoroblphenyl Sulflde (XXVIII).—

This compound is new and was prepared by the Dunning —' procedure

for compounds of this type.

Sulfur diehloride was freshly prepared by passing chlorine

into sulfur monochloride at -15° until the theoretical amount of

chlorine had bssn absorbed.

To 124 g. of 4-fluorophenol—' dissolved in one liter of

anhydrous carbon disulfide, 102 g. of freshly prepared sulfur di-

ehloride was added in four hours with Qtirring at room temperature.

Hydrogen chloride gas was evolved. The mixture was heated at re-

fluxing temperature overnight. After pouring over ice, about 68 g.

of emvla product as an orange precipitate was obtained, and the

filtrate gave & dark residue after removal of the carbon disulfide

by steam. The residue upon pouring into ice gave 38 g. more of

product, thus resulting in a crude yield of 106 g. or 41#. Re-

crystallization from ethylene diehloride gave white needles, and

vacuum sublimation gave the pure compound, m.p. 119°,

Anal. Calcd. for Ci»HeFa08S: C, 56.68; H, 3*17; F, 14.95;

3, 12.61. Found: C, 56,82; H, 3,38; F, 15.10; S. 12.41.

WADC TR 54-148 20

2,4,6-Trlfluorobonzyl Chloride (XXIX) .—This compound

is naw and waa borrowed from another project^ .

It is a colorless liquid with a slight pungent odor,

n§° 1.47088, b.p. 157°.

2-Hydrox;y-3,5-dlfluorobenzyl Alcohol (XXX) .—A mixture 13/ of 20 g. of 2,4-difluorophenol , 40 ml. of 37$S aqueous formal-

dehyde and 10 ml. of 40# sodium hydroxide solution was refluxed

gently for two hours. The reaction mixture was diluted by pour-

ing into 200 ml. of water. With stirring in an ice bath, the

diluted mixture *?as acidified with concentrated hydrochlorle

acid, and the crude product precipitated as smudgy needles,

yield 20.8 g. or 91#. This procedure was adopted from the wo? s. 25/ 26 27/

of Lederer^^and Manasse—*—' . Recrystallization from m-fluoro-

benzotrifluoride followed by sublimation gave white crystals,

m.p. 61-63°.

Anal. Calcd. for CTHeFa09: C, 52.50; H, 3.78; P, 23.73.

Found: C, 52.74; H, 3.60; F, 23.50.

The structure of this compound has not been proved

definitely, but all evidence points to the ascribed formula.

SECTION III

SUMMARY

The synthesis and properties of 15 aromatic fluorine

compounds prepared for the fungicidsi screening program are

described. Eight are representatives of types not studied

WADC TR 54-148 21

previously - namely, fluorlnated benzole acids, blphenols, biphenyl

sulrides and benzyl derivatives. The remainder may be classified

as halogenated phenols, nitrophenols, nitroanisolas, and niti'o-

tolusnes. This brings to about 50 the number of compounds studied

in the search for new fungicides applicable to the prevention of

mildew or fungus rot damage.

Increased fluorine substitution in the benzole acids does

not bring about any unusual potencies. The benzyl chloride and

benzyl alcohol specimens showed up very poorly in the screening

tests.

An outstanding case of potency exaltation by a nitro

group was discovered with 2-fluoro-6-nitrophenol which arrests

the growth of A. nlger at 11.5 ppm. The parent, 2-fluorophenol,

has very poor fungistatic properties. This may be a unique

structural condition as a second nitro group or fluorine atom

decreases the potency. With the 2-(P,Cl,Br)-4-fluorophenols, a

bromine atom appears to be about three times as effective as

fluorino in the 2-position, and thus gives further support to

potency boosting by dissimilar halogens.

The potency of 3-fluoro-4,6-dinitrotoluene to A. niger

is 250 times the 6-nitro and 100 times the 4-nitro precursors,

thus showing the effect of the second nitro group.

Two difluorobiphenola and a tetrafxuorobiphenol arrested

the growth of A. nlger in the range of 140-230 ppm. The tetra-

fluoro compound showed the lowest potency. A sulfur linkage was

ttADC TR 54-148 22

'

introduced between the phenyl groups of one biphenoi, and the

growth Inhibition concentration range on four test fungi was

changed from 57-140 ppm to 24-95 ppm. The biphenola and the

biphenyl sulfides may offer soi^e possibilities as colorless,

heat-stable fungicides.

Impregnation of cotton parachute webbing thread by

2-flucra-6-nitrophenol, the difluorobiphenols, and the biphenyl

sulfide did not appear to change th6 tensile strength of the

thread.

WADC TR 54-148 23

BIBLIOGRAPHY

1. Finger, G. C, Finnerty, J. L. and Schneider, H. G. FluorInated Qulnones and Hydyoqulnongs. Abstracts of Papers, p. 17K, 116th Meeting, American Chemical Society, Atlantic City, N. J., September 1949.

2. Tehon, L. R. Fungi3tatlc_ Potenclas of Some Fluor inated p-Benzoquinones. SCIENCE 114. 668(1951).

3. Finger, G. C, Read, F. H. and Dunbar, J. E. Chemical Investigation of Fluorine Compounds as Fungicides. United States Air Foree Technical Report No* 52-214, Wright Air Development Center, Wright-Patterson Air Force Base, Ohio, November 1952.

4. Tehon, L. R. Funflistatlc Capacities of Aromatic Ccrapounds In Relation to Cloth-Rot ting Fungi. Pt. I Flucrinated Quinones and Phenols, March 1951. Pt. II Fluor inated Phenols, Nitrobenzer.es, and

Anilines, August 1952. Pt. Ill Pluorinated Anisoles, Benzyls, Benzole Acids,

Biphenyls, Phenols, and Toluenes, November 1952. Pt. IV Fluorinated Phenols, Benzyl Alcohol, and

Biphenyls, January 1954. United States Air Force Technical Report No. 6518, Wright Air Development Center, Wright-Patterson Air Force Base, Ohio.

5. Suter, C. M. Relationships Between Structures and Bactericidal Properties of Phenols, Chem. Rev. 28, 269-299(1941).

6. Fanta, P. E. The Ullmann Synthesis of Blaryls, Chem. Rev. 38, 139-196(1946).

7. Block, S. 3« Chemicals for Fungu3 Control. Chem. Week 70, #4, 21-31(1952), Jan. 26 issue.

8* Anon, Battle of the Bacteriostats, Chem. Week 72, #11* 52-54(1953), Mar. 14 issue.

9. Finger, G. C. and Dunbar, J. E. Unpublished results.

10. Schiemann, G. and Pillarsky, R. Uber aromatigche Fluorver- blndungen. V. Mltteil., Ber. 62, 3055-3043(1929).

WADC TR 54-148 24

11. Schiemann, G. Daa Borfluoridverfahrsn *w r,a-„a+o~n,mr aromati3.:th«ir Fluorverbindungen, 19 MltTeTT:—57 pFakt.

1 Chem. 140p 97-116(1934).

I 12. Swarts, P. Sur quelques derives arcmatlques fluor<Sa. j Eec. trav.~chlm. 55, 158(1915) . "

1*. acmemann, G. and Seyhan, M. Uber ar-anatlsche Fluorver- blndungen, XXIII, Mlttell. Ber 703. 2596(l§57) .

14. Adams, Roger. Organic Reactions, John Wiley & Sons, New York, N. Y., 1949, Vol. V, Ch. 4.

15. Finger, G. C, et al. Unpublished results.

16. Schiemann, G., et al. Uber Fluorphenol6, 20 Mltteil. J. prakt. Chem. 145, 18-28(1955).

17. Schiemann, Gc„ et al. Per refraktometrisohe Wert dea Fluors in organ is chen Verblndungen, Z. physlk. Chem". 156, 414(1951).

18. Niemann, C, Benson, A. A. and Mead, J, F. The Synthesis of SSS'-Difluoro-d? fluoro-dl-thyronine' of SSS'-Difluoro-dl-thyronlne and 5,5-plodo-5'^S'-di" "~ " i, J. Am. Chem. Soc. 65, 2206(1941).

19. Hodgson, K. H. and Nixon, J. The Nitration of m-Fluorophenol, J. Chem. Soc. 1928, 1879.

20. Swarts, F. Sur quelques derives aromatlques flucres, Bull. Classe So l7]j A cad,. Roy. Beig. 1915, 241-278.

21. Schiemann, G. Uber aromatischo Fluorverblndungen, III. Nltrlerung der Fluor-toiuole., Ber, 62, 1794(1929).

22. Oesterlein, M. Uber Fhenylather, Monats. 57, 57(1931).

23. English, J., Mead, J. F., and Niemann, C. The Synthesis of 5,5-Dlfluoro- and 5-»Fluoro-5-iodo-dl-tyro3lne, J. Am. Chem. Soc. 62, 350(1940). ~

24. Dunning, F., Dunning, B. and Drake, W. E. Preparation and Bacteriological Study of Some Symmetrical Organic Sulfldes, J. Am. Chem. Soc 55, 5466(1931).

25. Lederer, L. Bine neu» Synthese von Phenolalkoholen, J. prakt. Chem. 50, 223(1894).

26. Manasse, 0. Uber eine Synthese aromatischer Oxyalkohole, Ber. 27, 2409(1894).

2*7. Manasse, 0. Zur Synthese aromatischer Oxyalkohole, Ber. 55, 5844(1962).

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APPKNDIX II

COMPOUNDS DELIVERED TO MATERIALS LABORATORY

(Twelve ooxapounds - 1900 g.)

• l-riuoro~3-onethyl»4,6-dinitr ©benzene

• l-Fluoro-3-chloro-4,6-dinitrobe:azene

• i-Fluoro-3-bromo-4,6-dinitrobenzene

• 1,3-Difluoro-4,6-dinitrobenzone

• 2,4-Dlnltrofluorobenzene

• 4-Fluoro-2,6-dinitrophenol

- 2-Nitro-4-fluorophenol

• 2-Eromo-4-flucr'ophenol

• 2,2'-Dihydroxy-5,5'-difluorobiphenyl

n n w

- 3,3'-Difluoro-4,4'-dihydroxybiphenyl

•2,2*-Dihydroxy-3,3',5,5'-tetrafluorobiphenyl

- 2*2'-Dihydroxy-5-5'-difluorobiphenyl Sulfide

(9/30/53)#

(9/30/55)#

(9/30/53)§

(1/7/54)#

(1/7/54)#

{12/16/53)#

(2/15/54)#

(3/2/54)

(3/27/53)

(3/2/54)

(4/23/53)

(3/2/54)

(3/19/54)

(12/11/53)

•New compound. #Deacribed in Tech, Repts No. 52-214.

WADC TR St

I

CuMPCtT;,!; INDEX

ACETOPHENCNES 2,4-Difluorofi.cstcPhenone 10 2,4.5-Trifluoroacetophenone — ~ ^J,

EEN20IC ACIDS •2,4-Difluorobenzoio Acid 11 *2f4,5-Ti-ifluorobenzoic Aeld 12

ANISGLES 2-Ajnino-4»fluoroanisole 12 2-Iodo-4-fluoroanisole 15 2-Bromo-4-fluorofcf*isol<» • 12 2-Cfal©re-4-fluoro&ni80l9 13 2-Fluoro-4-iodoanlaole --• 17 2.4-Difluoroanisol© • 13 2,4-Difluoro-6-nitroanisola —— —— 14

PHENOLS *2-Bromo-4-fluoropttenol 13 *2-Chloro-4-fluorophenol — ,——...- _ 14

2,4-Difluoropheno3- ' 14

NITROPHENOLS 2-Fluoro-6-nitropJienol • — 14 3-Fluoro-4,6-nltrOPhenol - ----- — . i4

NITHOTOLUENES 3-Fluoro-4-nitrot0luene 15 3- » -6- f —— 15 3- w -4f6-dlnl*rotoluene 15

BIANIS0LE3 (Biphenyia) 2,2t-Dlm«Jthoxy-5,$,-difluorobiphenyl - 16 S^'-Dlfluoro^^'-dlmethoxyblphenyl 17 2,2»-Dimothoxy-3,2',5»5,-tetrafluox»obiphenyI — 19

BIPEENOLS (Biphenyla) »2,2'-Dihydroxy-5,^,-difluoroblphenyi. 16 *3,3'-Difluoro-4,4'-dihydroxyblphenyl • - 19 *2,2»-Dlhydroxy-3,^l5,6'-tetrafluoroblphenyl - 19

BIPHENYL SULFIDE «2,2,-Dihyiroxy-5,$,-dm.uorobiphenyl Sulfide — 20

BENZYL DERIVATIVES , ^, ,„ „-, »2,4,6-Trlfluorobetizyl Chloride - 21 #2-Hydroxy-3,5-dif3-Uorobenzyl Alcohol 21

#New compounds (10) tested as fungicides in this report

WADC TR 54-148 33

firmed Services Technical Information keiiev j

Because of oar limited supply, you are requested to return this copy WHEN IT 8AS S£RV£!i YOUR PURPOSE so that, it may be made available to other requesters. Your co( peiaiion will be appreciated.

NOTICE: WHEN GOVERNMENT OR OTHER DRAWINGS, SPECIFICATIONS OR CTHttK DAI A ARE USED FOR ANY PURPOSE OTHER THAN IN CONNECTION WITH A DEFINTT BUT KU /If i GOVERNMENT PROCUREMENT OPERATION, THE U. S. GOVERNMENT THEREBY INCURS NO RESPONSIBILITY, NOR ANY OBLIGATION WHATSOEVER; AND THE FACT THAT THE GOVERNMENT MAY HAVE FORMULATED, FURNISHED, OR IN ANY WAY SUPPLIED THE SAID DRAWINGS, SPECIFICATIONS, OR OTHER DATA IS NOT TO BE REGARDED BY IMPLICATION OR OTHERWISE AS IN ANY MANNER LICENSING THE HOLDER OH AKY OTK&i PEKSON OR CORPORATION, OR CONVEYING ANY RIGHTS OP PERMISSION TO HAJMl-FACTU! USE OR SELL ANY PATENTED INVENTION THAT MAY IN ANY WAY BE RELATED IHEKETl'

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