AU501112B2 - Miticidal phenoxyalkylamders - Google Patents

Description

OMOW~Afl*OF AUSTR.AUA PATRINTS IhU4

Conivention Application for a patent

STAUFF'ER CNEMICAL, COMPANY

11. 12'.'

of WeStPox-t, Connecticut 06880, United States of Amierica

15369/76 hereby' *pPlY' -for the grant a Patent for an invention entitled

"PRENOXY ALI(YLAMIDES5 AND THEIR. USE AS MITICIDES"

p p 3.

4. a. 3 APPLICATION ACCUED 4ND ADN 4

03 0 *4 AU.,OWItD 3 p whioh is described in the accomnpa:,'Lr';g rothplete specification. .4 *3 33 P Thsaplcto i o~'ninApplication and is based on the e.g 4 applicationS numbered. 591 727 and 591. 730 3 34 for a patent ot similar protection made in United States. of Alezica

.3 0~

K:USTRA IAA' 3..

6 on 30th JUNE, 1975 AND 30TH JUNE, 1975 *q 0 3 *3 MY kT93&T 04 Oraddress for service is:

C2are, SPRUJSON FERGUSON PATENT ATTORNEYS ESSO HOUSE, 127 KENT STREET SYDNEY. NEW SOUTH WALES. AUSTRALIA.

Dated this.NINETP]ENTH day of FEBRUARY STAUFFER CHEMICAL COMPANY

To: Registered Patent Attorney Th rui kw V pu

CO94MONWALTH OF AUS LIA A ACT DECLARATK N IN SU1PfPORTOF A CONVENT16N APPLICATION-FOR A FXTENT OR PATENT OF AMMITON In support of the Convention Application, made for a.,

for an invention entitled 11PHENOXY ALKYLAMIDES AND THEIR USE AS MITICIDES"

156976 Full imme and ad- L H~obart Ogden Thomas, Senior Vice President dtxes of fleciarant. Of STAUFFER C14EMICAL 4 COMPANY, Westport,. Connecticut 06880, United States of America,

do snlomnly and sincerely declare as follows:-

p*ater4.-eadditj.-n (or, in the case of an application by a body corporate) 1. 1 amt muthorised by STAUFFER CHEMICAL COMPANY,

the applicant for th patent to make this declaration. oIn, Ats be helf.

1113rt couiltryA nd 2. The basic application sas defined by Section 141 of the Acttwere*made in ofUnited States of America on the ,day of June, 19 75 15-y and on, the diy of June, 1975 both 'by Dori R. Baker and Francis H, Walker

fOremiof~p1iela

(or whe~re a pe'rson other than the inventor is the appicant) 3, DNRBR BAKER,. of 15 Muth Drive, Orinda, California 94563, Un-i-ted States of America, and FRANCIS HARRY WALKER, of 302 Montford Avenue, Xill Valley, California 94941, United States of America, .0

areis-thf actual inventorsof the invention and, the facts Upon which the applicant is/vf entitled to make the application are as follows, The said applicant is the assignee of the actual inventors.

were 4. 'The. baisic applicationsreferred to in paragraph 2 of this' Declaration "s the first applicationsmade in a Convention country in respect o f the inv ertioithe subject 0 0 of the application. 0

000 00 D~eclared at 'San Francisco- this -L ft 4 day of June 19 7( 'V Californiat STAUFFER CH~EMICAL COMPANY

ik: C,

(11) AU-B 15,t69/76

(12).PATENT SPECIFICATION AB RI DGEMENT (19) AU

(21) 15369/76 501P112 (22) 28, 6.76 (23) 28.6.76 (24) 30.6.75 (31) 591727 (32) 30.6.75 US 591730 30.6.75 us (43) 5.1.78 (44) 14.6.79 (51)2 C07C 103/34 A01N 9/24 C07C 121/453 C07C 59/25. (54) MITICIDAL PHENOXYALKYLAMIDES. (71) STAUFFER CHEMICAL COMPANY. (72) BAKER, WALKER, F.H. (74) SF 7 CLAIM 1. A compound having the formula Cl 0 CH3

Cl. -j I n' z~f R1 R2R3

wherein Rlis etemehloehy;3R2and R3are independently either hydrogen or methyl; and when R3 is hydrogen, n is either 1 or 2; and when R3 is methyl, n is 21. CLAIM 7. A compound having the formula

0 CH 3 -CH-C-NH-C X R CH3

whH-r-in Ris either methyl or ethyl; X is either chlorine or trifluoromethyl; and where X is chlorine, m is 3 with the proviso that the 2- and 4-positions are not Doth Occupied on the ?henyl ring; End where X is trifluoromethyl, m is 1.

21.4

PAET CT'1952469 I CF Ou

COMPLEFTE.. SPECOIFICATION (ORIGINAL) FOR OFFICE USE.

Class Int. Class Applicationi Number Lodged

Complete Specificaition Lodged. Acc~epted Published Priority: 153 6976

RtdArt OF O

STAUFFER CH=MCAL COMP~ANY

Ares ~of Applcant

#09 1 netp Westport# Connecticut 06880, United States of America

9\es o evc

DlON ROBR BAKER and PRANCIS HARRY WALKER

Spruson Ferguson, Patent Attorneys, Esso House, 127 Kent Street, Sydney, New South Wales, 2000 Australia.

Xlete Specificotion for the invention entitled

toPHENOXY ALRtYIAMIDES AND THEIR USE AS~ MITICIDES"

Ving statement is a full description of this invention, including the best method of performing

AUSTRALIA ,j

Background of the Invention

Various substite d amides, particularly N-substituted amides and substituted phenoxy amides, are known to be useful as

insecticides, miticides, and herbicides. Typical insecticidal properties of such compounds are taught in U.S. Patent 2,426,885 and its two continuations-in-part, U.S. 2,484,295 and U.S. 2,484,296. Herbicidal properties of such compounds are taught

in U.S. Patents 3,272,844, 3,439,018 and 3,564,607, and Belgian O' Patent 739,714.

l Brief Description of the Invention

This invention relates to a class of substituted phenoxy

alkyl amides and to their use as miticides when used in a mitici- a

dally effective amount. More specifically, this invention relates to phenoxy alkylamides having the formula

0 CH II 3

SR R R SU" C1 n

wherein R is either methyl or ethyl; R 2 and R 3 are independently

either hydrogen or methyl; and when R is hydrogen, n is either 1 or 2; and when R is methyl, n is 2; and to phenoxy alkylamides having the formula

0 CH t 3 N (II) X R CH 3 m

wherein R is either methyl or ethyl, and X is either chlorine or

trifluoromethyl, and where X is chlorine, m is 3 with proviso that

-2- 47 ON

ki ]f B the and 4-positions are not both occupied on the same phenyl ring; ,and v~here X is trifluoromethyl, m iL4 1.

The cliorine atoms whose positions on the phenyl ring are undesignated in formula will herein~after be referred to as "floating chlorine atoms." In the examples cited hereinbelov and in the claims which follow this specification, the f 10 tin S C', chlorine atoms will be assigned positions on. the phenyl ring. Jzz These positions will be identified in accordance with the -following numbering system:

4R4@ 4 ~1 w~4 4.

4. 4 4 .4 4 S CO)R R R *4 44 54 4 5 6 K 4 S

S 4 5 4 .44. S IQ By "imiticzidally effective amount" is meant the amount 445544 S of the herein disclosed miticidal compounds which when applied to the habitat of mites in any conventional manner will kill or sub- 95 .55. S. 4 stantially injure a significant portion of the population thereon. 0@ S 54*

S 4* 4 Detailed Description of the Invention The compounds of the formule are prepared by the 15 3 and n1 are as defi ned following general method, wherein RI, R 2 .9R. a 4 0 OS

S* S above: 4.

Reaction No. 1 Cl Cl 0 NaOH (a q.) 11 Br-CH-C-0fl ~1 R Cl R n

To a mixture of a molar amount of the phenol, snd at slight' molar excess of 'the acid is added, a slight mo1ar exce'ss of t

MM%aqueous NaOH. The produce acid is then washed with .tal solvents and recovered from the organic p~hase,

Reaction No. 2

0

-CH-C-OL I HC-N('CH 3 COC 2 R

east

a a 9 0 .CH-8-Cl HC 1 I]- a9 a R

A slight molar excess of phosgene is introduced into a molar amnount of the acid in a suitable solvent, t6 which a small amount of dimethyl formamide has been added. The excess phosgene and HI~ are then removed and the solvent is evaporated to leave the acid chloride.

Reaction No. 3

.0

00 S S 00 0 Ii3' (C2 H5 PN 09 90 ~a 12 13 R1 R R

F~CH 1'3

Ci1 R R R

YI

The acid chloride is added to a solution containing

Sbo t the acetylenic amine and the triethylamine at 10-15 0 C.

SAfter successive washings, the product is recovered from the

Sorganic phase.

The compounds of formula are prepared analogously.

The examples shown herein are illustrative of the method of preparation of the compounds of both formulas.

EXAMPLE I N-dimethylpropynyl-)( (2,3,5-trichlorophenoxy)butyramide. (Compound No. 3 in Table I below)

44.0 g (0.55 mole) of 50% aqueous sodium hydroxide was

added to a mixture of 42.5 g (0.22 mole) 2,3,5-trichlorophenol

V and 43.4 g (0.26 mole) 2-bromobutyric acid, with rapid stirring

S.at an initial temperature of 15°C. The temperature rose to over the course of the addition and was held between 15*C and 0 C with a cold water bth. At the completion of the sodium

hydroxide additior, the cold bath was removed and the mixture -was heated to 110 0 C for 15 minutes. Then 50 ml water, 53 ml

perchloroethylene, and 42 ml concentrated hydrochloric acid were

added to the reaction mixture and the mixture was heated to

then phase-separated. The organic layer was cooled and the Sproduct, -'-(2,3,5-trichlorophenoxy)butyric acid crystallized. The acid was separated by filtration to give 43.1 g (69.1% yield) of the acid, m.p. 65-700 C.

0.2 ml dimethyl formamide was added to a slurry of 50.3 g (0.18 mole) of X-(2,3,5-trichlorophenoxy)butyric acid in

1 11 1 1 1 1

I

4 1

toluene. 8011 1l The, slurry was then heated to 60% $.14 a 500 ml flask which was Uftted with a gaii-in~let tube, a stirrer, a thermometer, And, "a dry ice-isopropyl al Icohol, condenser. 22 g (0.23 moIe) of fhosgene was passed inio the mixture at a, moderate rate. The dry ice condenser was then removed and replaced with a ater-cooled condenser. Excess phosgene and HCl were removed by an argon, purge through the solution at 60*C. The solution was then cooled and. the solvent was removed in vacuum to leave 43.4 g (807. yield) of an oil, cK -2 Schloride,,

S (0.03 mole) of the acid chloride was added drop-

vise to .9 iixttlre of 2.9 g (0.035 mole) dime thylpropargylamine

00 and 'L.6 (0,035 mole) triethylamine in 100 ml of dichloromethane at 10-1500, Some cooling in an ice bath was necessary to maintain the temperature. After the addition of the acid chloride, the 0 .0 mixture as allowed to come to room temperature and the product vfs isolated by washing with, in succession, 100 ml portions of 2 0

viater, dilivte IICIO 5% Na 2 C0 3 solution, and water. The organic *09 phase was dried over magnesium sulfate and the solvent was removed in vacuum to leave 7.7 g (73.6% yield) of an oil, m.p. 118-120*C, which wa~s identitied by infrared spectroscopy as N-dimethylpropynyl- 0( -(2,3,5-trichlorophenoxy)butyramide.

EXAMP'LE 11 Iq-methVl-N-isobutyrnyl-C<X (Compound No. 4 in Table I below) -trichlorophenoxy)butyryl chloride was prepared in a manner identical to that described in Example 1. 7.0 g

(0,02 mole) of the WW.4 chloride was added diropuise to a mixture, of 2,.3j g (0.03. mole) of N4-metbyl-2-am-inQo-3'ibutyne and, 2.9 g (0'.03 mole) of triethylamine in 100 ml dichioromethane at 10-15"C. From this point a.procedure identical to that of Example I was folwdt ild71~(84.87. yield) of N-methyl-N-isobutynyl-o%-

(2,3,5-trichlorophenoxy)butyramide., m.p. 73-77 0 characterized W~ by infrared spectroscopy.,

EXAMPLE III SN-dimethylacetonitrilo-cl(-(3,4., -trichloropheno~y)butyraJnid. (Compound No. 8 in Ta'.N1e I below) 50.8 g (0.63 mole) of 50%i _-ueoos sodium hydroxide was

added to a mixture of 50 g (0.25 mole) of 3.4,5-trichlorophenol and 50 g (0.30 mole) of 2-bromobutyric acid, with rapid stirring at an initial temperature of 15*C. The temperature rose to 4500 over the course of the addition and was held between 1500 and 4500 with a cold bath. At the completion of the sodium hydroxide 04 addition,. the cold bath was removed and the mixture was heated to 11000 for 15 minutes. Then 62 ml water, 125 ml perchloro-

ethylene, and 50 ml concentrr,-td hydrochloric acid were added to the reaction mixture. The mixture was heated to 8500, then phase-separated. The organic layer was cooled and the product, -'-(3,4,5-trichlorophenoxy)butyric acid, crystallized. The acid

was separated by filtration and amounted to 54.2 g (76% yield),

0.2 ml dimethyl forinamide was added to a slurry of

54.2 g (0.19 mole) of c?-(3,4,5-tridchlorophenoxy)butyric acid in ml toluene. The slurry was then. heated to 6000 in a 500 ml

!Ask fitted with a gas-inlet tube, a stirrer, a thermiometer and, a dry ice-isopreopy. elc'hol condenser. 22 g mole)

of phosgene was p~issed into the mixture at a moderate rate. The dry ice condenser was then removed and replaced with a water- cooled condenser. Excess phosgene and HUl were removad, as the tT solution wag purged with argon at 60*C. The solution was then cooled, and the solvent was removed in vacuum to leave 54.9 g

(95.6% yield) of a liquid, nD 1.5506, which was c-345 4 trichlorophenoxy)butyryl chlorid~e.

g (0.03 mole) of the acid chloride was added drop- wise to a mixture of 2.5 g (0.03 mole) of c' -aminoisobutyronitrile

[made by the procesure of J.V. Dubsky and W.D. Wensink, Ber. 49,

1136 (1916)] and 3.1 g (0.03 mole) of triethylamine in 100 ml methylene chloride at 10-15%C. An ice bath was used to maintain

the temperature. Af ter the addition of the acid chloride, the mixture was allowed to come to room temperature and che product was isolated by washing with, in succession, 100 ml portions of water, dilute HCl, 5% Na2 CO3 solution and water. The organic

phase was dri~ed over magnesium sulfate and the solvent was removed in vacuum to give 5.6 g(48.7% yield) of the product, identified

by infrared spectroscopy as N-dimethylacetonitrilo- c2(.(3,4,5-

trichlorophenoxy)butyranide, m.p. 162-164*C.

EXAMPLE IV N-dimethylacetonitrilo- ,,-(2,3,5-trichlorophenoxy)butyramide. (Compound No. 9 in Table I below) 44.0 g (0.55 mole) of 50% aqueous rGodium hydroxide was added to a mixture of 42.5 g (0.22 mole) ofT 2,3,5-trichiorophenol and 43.4 g 26 mole) of 2-bromobutyric acid, with rapid stirring at an initial tempeiture of 1C.The,temperature rose to over the course of the addition during which time a, cold water bath. was applied. At the completion of the sodium hydroxide addition,, the cold bath, was removed and, the mixture. was; heated to

110*C for a 15 -minute, period. Then 50 ml of water, 53 mil of (0 perchioroethylene, and 42 ml of concentrated hydr;,chloric a cid IZz ,were added and the mixture vas heated to 85*C, ethen pha se-sepa rated. 'The organic layer was cooled and the product, aS-(2,3,5-

Lt~j 1.-I' trichlorophenoxy)butyric acid, crystallized. The acid was

isolated by filtration to give 43.1 g (69.1% yield) of trichlorophenoxy)butyric acid, m.p. 106-114*C. 400 p. 0 a Ow 4. 0*

00 9 0.2 ml of dimethyl formamide was added to a slurry of 0w 9@ 4 ~b a

a 50.3 g (0.18 mole) of -u-(2,3,5-trichlorophenoxy'butyric acid in a @4 4 4 Oau 0 4 80 MI. of itoluene. The slurry was derL heated to 60% in a 500 ml S a q..aao a a fla-sk fitted with a gas-inlet tube, a stirrer, a thermometer, and

-3 d'ry ice-isopropyl alcohol condenser. 22 g (0.23 anole) of phos-

gene wa passed into the mixture at a moderate rate. The dry ice *0 0

condensor was then removed and replaced with the water-cooled

*condenser. Excess phosgene and I-Id were removed by an argon purge 'S 4 4 go.. of the solution at 60'C. The solution was then cooled, and the

solvent was removed in vacuum to leave 43.4 g (80% yield) of an 0 S. 0 oil, vhich ,3,5-trichlorophenoxy)butyryl chloride. 0*

4 S @0

g (0.03 mole) of the acid chloride was added dropr-

wise to a mixtuire of 2.9 g (0.04 mole) of isobutyroni trile

and 3.7 g (0.04 mole) of triethylamine in 100 ml methylene chloride, maintained at a temperature of 10-15 0 C by an ice bath. After the

addition of the ac..d chloride, the mixture was allowed to come to room temp.. rature and the product was isolated by washing with, in succession, 100 ml portions'of water, dilute HC1, Na CO3 solution and water. The organic phase was dried over magnesium sulfate and the solvent was removed in va cuum to leave 7.8 g (74.4% yield) of N-dimethylacetonitrUlo-04-(2, cobutyramide, m.p. 137-140 C, characterized by, infrared, spectroscopy.

Other compounds, such as those included in the fallowing

,,table.,can be prepared in a manner analogous to that shown in the examples above, starting with t',e appropriate materials. The compounds in the table are representative of those emdoodied in the pret,.t invention. Compound numbers have been assigned to e q them for purposes of identification throughout the balance of

the specification.

09

1. 00

TABLE I

M.P. 00.. COX2OUND orn NUMBE R COMPOUND

1 Cl 1. 5374

0 CHE 2 Cl 78-830C 0;215 CH3 a 6S

a, a a. a ClCl3 a a

a. 0-CH-C-NTH-C-C_=Cl- 118- 1200C a p a a .a L;2 H 5 CE3 a. a~ *q a S 0

73-7700 Cl

0 CH. 4 a. fr II1 1 CI 0o-CE-C--N-C-C~- 'CH 88-980C 0;2115 CE3 a* a a *5 Cl I. a a. -a a 0 CE3 sa I II 121-1230C C-C,===CH -GE-C-N- 51k3 CE3 Cl

0 CH. CE-C -N-Cl-C==_CE 1.5486 W113 0113

III

TABLE I (conti£nued)

COMPOUND NIJM2BER ci COMPOUND MYELTING POINT

8 162-164 0C 0 i :GS 2 H5 CH3

cD I Cl Ln9 0- CH-C-NIl-C- C ?N 137-14OC V-4

ok 021 CH3

*i 4. 72-750*C 0 3. r *004

CF 3 4t 4,- 99 r

409 4*-d 4,

133-1360C 1 U"3 1, 0605

009i *s e Cl 0" 0 CH S. OS i SH3 00 0000i 0 3-C 3-NI-C-CN 136-1400C 1 C3 CH 3 00 0: 0 00

4. 0 00i i 49;

-12-

B i: i

7 LT

Miticidal activity of each of the above compounds on

the two-spotted mite [Tetranychus urticae (Koch)] was evaluated

as follows:

Pinto bean plants (Phaseolus approximately 10 cm tall, are transplanted into sandy loam soil in 3-inch clay pots and thoroughly infested with two-spotted mites of mixed ages and sexes. Twenty-four hours later the infepted plants are Sinverted and dipped for 2-3 seconds in 50-50 acetone-water solu-

tions of the test chemicals. Treated plants are held in the

greenhouse, and seven days later mortality is determined for

both the adult mites and the nymphs hatching from eggs which

were on the plants at the time of treatment. Test concentrations *o

.6.g range from about 0.0 8% down to that at which 50% mortality occurs. &t

The following is a table of the results of the above

test procedure, indicating the effective concentration at which

mortality was achieved.

TABLE II

Effective Concentrations on Two-Syttted Mite

[fTetranychus urticae (Koch)]

CPOUID NUHR PE Eggs 1 .03

2 .03

3 .001 .008

4 .005 .03

.08

6 .005 .008

7 .05

-13-

1

Table II (continued) COMPOUNDNUMBER PE EGGS 8 ,008 .01 9 .005 .03

11 .005 .03 12

PE Post-embryontic

Greater than

Neither the examples nor the tables hereinabove are intended to limit the invention in any manner.

The compounds of this invention are generally embodied

in a form suitable for convenient application. For example, the compounds can be embodied in miticidal compositions in the form of emulsions, suspensions, solutions, dusts, and aerosol sprays. U.

In addition to the active compounds, such compositions generally

contain the adjuvants which are normally found in miticide pre-

parations. One such composition can contain either a single

miticidally active compound or a combination of miticidally active compounds. The miticide compositions of this invention can contain

as adjuvants organic solvents such as sesame oil, xylene, or heavy petroleum; water; emulsifying agents; surface active agents; talc; pyrophyllite; diatomite; gypsum; clays; or propellants such as dichlorodifluoromethane; or a combination of these. If desired, however, the active compounds can be applied directly to feed- stuffs, seeds, or other such matter on which the pests feed. When applied In such a manner, it will, be advantageous to use a com- pound which is not volatile. Ln eanneel-tin wft ttL. aot"4tyl SPresently diselesed mitieiial nbmpeur.Ja, +t sheuld-bez fully unde' tt d that the compounds need not be active as-such. purposes of this in on will be fully served by a compound which is rendered active by an externil-a fluence such as light, or bl, some physiological action which the, c~oin S4.U tse Ingested Into th. bodyv of the_ peat.

The precise manner in which the miticidal compounds of it) this invention should be used in any particular instance will be readily apparent to a person skilled in the art. The concentration of the active miticide in a typical composition can vary within rather wide limits. Ordinarily, the miticide will comprise not more than about 15.07. by weight of the composition. The preferred range of concentration of the ruiticide is about 0.1 to about by weight.

4. go

Claims (1)

1. The claims defining the inventicn are as follows:

   1. A compound having the formula (C1

   0 CH3 -CH-C EEH -4 Cl n R n

   wherein R is either methyl or ethyl; R and R are independently

   either hydrogen or methyl; and when R 3 is hydrogen, n is either

   1 or 2; and when R S is methyl, n is 2.

   4 9

   S2. A compound according to Claim 1 in which R is

   S. ethyl, R is hydrogen, and R is methyl.

   3. A compound according to Claim 2 in which the two

   floating chlorine atoms occupy the 2- and 5-positions on the

   phenyl ring. O 4 *4

   4. A method of controlling mites comprising applying

   to the habitate thereof a miticidally effective amount of a com-

   pound having the formula Cl. 4O CH 3 U 1- J S, H R l R 2 k3 Cl n

   wherein R is either methyl or ethyl; R and R 3 are independently

   either hydrogen or methyl; and when R is hydrogen, n is either

   1 or 2; and when R is methyl, n is 2.

   I~

   _1 I_ I

   A method according to Claim 4 wherein R is ethyl, R 2 is hydrogen, and R3 is methyl.

   6. A method according to Claim 5 in which the two

   floating chlorine atoms occupy the 2- and -positions on the

   phenyl ring.

   7. A compound having the formula

   SH--NH-C -CEN X R CH 3 3 *M wherein Ris either methyl or ethyl; X is either chlorine or

   5. trifluoromethyl; and where X is chlorine, m is 3 with the proviso B

   that the 2- and 4-positions are not both occupied on the-eefme-

   S phenyl ring; and where X is trifluoromethyl, m is 1.

   8. A compound according to Claim 7 in which X is

   chlorine and R is ethyl. S S ***oo

   9. A compound according to Claim 8 in which the chlorine **o

   atoms occupy the and 5-positions on the phenyl ring.

   A compound according to Claim 8 in which the

   chlorine atoms occupy the and 5-positions on the phenvl

   ring.

   11. A method of controlling mites comprising applying

   to the habitat thereof a miticidally effective amount of a com-

   pound having the formula

   N ~VH 3 iI -0-HCNH -C m R36

   wherein R is either methyl or ethyl; X is either, chlorine or trifluoromethyl; and wherp X is chlorine, m is 3 with the proviso cothat the 2- and 4-positions are not both occupied, on the same Sphenyl ring; and where X is trifluoromethyl, m is 1.

   12. A method according to Claim 11 in which X is chlorine and R is ethyl. 9ee* S 59 5. *0 S S 13. A method according to Claim 12 in which the @000 0* 00 *0 S J -CIL& -1 J- LLLV. jLLCIL~ 0 9

   5 *9 0 ring. S.6 0 059 0 S 00 ~JSee 0 144 A method according to Claim 12 in which the chlorine atoms occupy the and 5-positions nn the 0O S phenyl ring. S.. *09 S DATED this FIRST day of JUNE, 1976 *5 S *ee. STAUFFER CHEMICAL

   a. 5 5, S~ Patent Attorneys for the Applicant *5 5* S SPRUSON FERGUSON