CA1082205A - Miticidal and aphicidal 2-higher alkyl-3-hydroxy-1,4- naphthaquinone carboxylic acid esters - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Miticidal and aphicidal compounds Or the following formula, processes for preparing them, compositions containing them, and methods of using them to protect plants and animals from damage caused by these pests:

where R1 = alkyl of 8-14 carbon atoms either branched, cyclic, or straight chain;
R2 = alkyl of 1-17 carbon atoms either branched or straight chain, alkenyl of 2-17 carbon atoms, cycloalkyl of 3-6 carbon atoms, alkoxy of 1-4 carbon atoms, -CH2OCH3. -CH2OCH2CH3-or -CH=CH-COOH;
X = hydrogen, fluorine, chlorine, bromine, methyl, or methoxy;
Y = hydrogen, fluorine, chlorine, bromine, methyl, or methoxy;
provided, when R1 is alkyl of 8-11 carbon atoms, at least one of X and Y is other than hydrogen; provided further, when R1 is 12-14 carbon atoms and both X and Y are hydrogen, then R2 is not alkyl or 1-6 carbons nor cycloalkyl of 3-6 carbons.

Description

TITLE

MITICIDAL AND ~PHICIDAL 2-HIGHER
~LKXL~3 HYDROX~ 1,4~NAPHTHOQUINONE
CAR~OXYLIC ~CID ESTERS
...... -- " :
B~CKGROUND
This invention relates to miticidal and aphicidal compounds which are 2-hi~her alkyl~3-hydroxy-1,4-naphtho-quinone carboxylic acid esters.
~ ,$. Patents 2,553,647 and 2,553,648 disclose bxoadl~ 2-alkyl~3-h~droxy~1,4~naphthoquinone carboxylic ac;ds and their corresponding ester derivatives. These compounds are described as having antagonistic action against organisms which cause malarial infections.
U.S. Patent 2,572,946 discloses the use of non-acylated compounds as miticides; it contains no teaching~
of acylat~d compounds~
Nakanishi et al. JACS 1952, 3910-3915 discloses the _-undecyl analog of 2-alkyl-3-acetoxy-1,4-naphtho-quinone. No use for the composition is disclosed.
UMMARY
According to this invention there is provided miticidal and aphicidal compounds of the followiny formula, processes for preparing them, compositions containing them, and methods of using them to protect plants and animals from damage caused by these pests.

X O O
[~0 C-R2 y O
where .; ~ ' ".
' ' , ' ' ' ' ' ' rlO8;Z;~:~5 Rl = alkyl of 8-14 carbon atoms either branched, cyclic, or strai.ght chain;
R2 = alkyl of 1-17 carbon atoms either branched or straight chain, al]cenyl of 2-17 carbon atoms, cycloalkyl of 3-6 carbon atoms, alkoxy o~ 1-4 carbon atoms, -CH20CH3, -CH20C~12CH3, or -CM=CH-COOH;
X = hydrogen, fluorine, chlori.ne, bromine, methyl, or methoxy;
Y = hydrogen, fluorine, chlorine, bromine, methyl, or methoxy;
. provided, when Rl i5 alkyl of 8-11 carbon atoms, at least one of X and Y is other than hydrogen; provided further, when Rl is 12-14 carbons and both X and Y are hydrogen, then R2 is not alkyl of 1-6 carbons nor cycloalkyi of 3-6 carbons.
Combination of the compounds of this invention with other miticides often provides better total mite c-ntrol than either material alone. Among such products ~ ' :. -' '~
'' `

221~5 which may be used adYantageousl~ with them are chloro-dimeform ("Galecron"), ~ormetanate ("Carzol"), propargite ("Omite"), tetradiFon ("Tedion"), and benomyl. Such mixtures are noyel.

DETAILED DESCRIPTION
These compounds are miticides and aphicides. That is to sayr when an effective amount of such compounds is brought into contact with mites or aphids, these pests are killed. The compounds are thus useful for protecting plants and animals from damage caused by mites or aphids.
The invention also includes miticidal and aphicidal compositions which contain at least one compound as active ingredient, and processes for preparing these compounds.
Preferred for their ease of synthesis are those compounds where R is straight chain alkyl of 8-14 carbon atOms- !
More preferred for their greater biological activity are those compounds where R is straight chain alkyl ~ of 12-14 carbon atoms; these compouncls also have a direct ; 20 lethal contact action against the eggs of mites. Mi-te eggs expose,d to sprays of these compounds are killed and hatching fails to occur. Rates slightly higher than those used to kill the motile mite forms are generally required for good ovicidal effect.

It is preferred that R is alkyl of 1-6 carbon atoms, more preferably straight chain of 1-6 carbon atoms, alkenyl of 2 or 3 carbon atoms, methoxy or ethoxy, most preferably ethyl or methyl. Specificallyr the following compounds are preferred for their highest miticidal and ,~ 30 aphicidal activity:

?, `

3-propio~yloxy-2-n-t~tradel~yl-1,4-naphthoqulnon~;

2-n-dodecyl-3-propionyloxy-1,4 naph~hoquinon~;
2-~-dodecyl-3-m~thoxycarbonylo~-1,4~n~phthoqul~one, 2-n-dodec~1-3-eth~ycarbonylo~y~1,4~naphtho~uinone.

3-aceto~y-5-chloro-2-dodecyl-1,4-naphthoquinone.
In a speci~ic ~bodlment o* the ~n~ta~t in~ention, th~ co~pound~ o~ the in~tan* ~n~nti~n are applied ln adm~xtur~ with a $up~rior oil, prePerably a minor a u~t o~
Su~erior oil, e~ 18~ than 5% by weight. Th~ resulti~g mitlcldal act~vity i8 grea~er ~han the additl~e re~ultæ.
Superior oil~ are dlscus~d in Chapman et al.

~ Jour~ Eco~.
Ent., 1962~ 55:737-43. The resultl~g mixture o~ eom~ound and Superior oil i~ nov~l.
~ynth~
CompoundQ can be prepared ~y the procedures de-3crib~d in the pr~viou ly ¢i~ed J Am Chem. Soc, art~cle and in U.S. Pat~nt No~O 2,553,647 sncl t648. me ~ tep ~n the ~y~he8i~ m~y be ac~ompll~h~d by treatin~ th~ corre-spo~din~ 2-~lkyl-3 hydroxy-1,~-n~ph~hoquinon~ (III) with the appro~rlate acid ¢hlor~de or anhydride ln the pr~sen~ o~ a~
lea~t ~n equ~valent o~ an amine such a~ pyridine or ~rlethyl-amlne, or by treatlng the ~alt o~ the 2~alkyl-3-hydroxy-1,

4;naphthog~no~e wnth the approprlate a~id chlor~de or anhydrlde in an in~r~ ~olvent.
Compo~nd~ can b~ prepared el~her (a) ~rom the approprtately-~ubstituted ~ph~hol by the method taught ~n publi~hed German O~enlegungschriPt ~2,520,739, (11/~751, or (b) from the appropriate 4~ph~n~1-3-o~obutanolc e~ter a~
taugh~ by Fl~er, et al~, U.S.P. 29553,647:

(C') ~ ~ ~

x ~ :
o , ~011 ~' x ( III) Y O

~:) ,C,R2 O
K
X O ,~ ~I2CCHC02C~2C~3 (b) ¢~ C~2ccH2co2cE~2 3 ~ W II~
Y .

The f~al ~tep in th~ 3yIlthe~i3 may be accompllshed by treat ing Ith~ corresporlding 2alky1-3-~ydroxy 1,4_naphth~quinone ., .
(III~ w~th the appropriate acid chloride ox ar~ydrid~ in the pre~enco o~ at least an equi~alen~ o~ an amlne ~u¢h a~ Eyrldin~
or tri~th~lamin~, or by treatlng the ~alt Or the ~lkgl-3-10 h~dro~-1,4-~e.phthoquinone with the appropri~ acid chloride or an ~ dride ~n a~ rt ~ol~tent.
Th~ ~ollow~ng ex~mpl~s ~ur~her ill~tra~ proce~se~
~:~ ror prepar~ng ~he~e compound~O
. ~

Preparation o~ 3-A~etox~-2-n-dodec~1-1,4-naphthoquino~
~: 4 -. , .
, ~ ~ .. ...

o o OC-C$3 n C12H25 of 20~ part~ o~ 2-n-dodecyl-3-h~drox5r-1, 4-napht~Loquinone, 0.81 part~ o~ triet~ylamlne, o.63 part~ oP
acet3~1 ¢hloride a~d 50 part~ o~ ~tfflleno chlorid~ wa~
~tirred at room temperature ~or 30 halurJ3o ~he re~ultiIle mixtur~ wa~ di~trlbu~ed be~ween met~;ylene ehloride and wat~r. The meth~rlene c~loride layer wa~ ~parat~d, dried oYer ~e~ium sul~ate, then ~iltered and e~raporated under ~educed pre~ . The re~due was cry~talllzed ~rom petrol-eum ~ther (b.~. 30-6Q~) to ~e 1.2 parts o~ 3~acetoxy~2-n dod~cgl-1,4-naphthoq ~ one, m,p~ 57-58C.

Pr~paration o~ 2-n Dodsc~1-3-propion~loxy-1,4~aph~ho~ui~ne ~____ ~--C1~5 A mixture o~ 4.0 parts o~ 2-n-d~decyl-3-hydro~y-1, 4'naph~hoguinone, 4.4 part~ o~ propionie anhgdrld23 ~nd 50 part~ o~ ~yridine wa~ ~tirred at roo~ temperature ~or 16 hour~. The re~ultlng mixture ~a~ ev~porated ~nder r~-duced pr~sur~ to rem~v~ ths p~ridine. ~he resi~u~ wa3 ¢~y-st~lllzed from methanol to ~lve 2.9 partB C~ 2-n-dodec~l-3-propionyloxy-1,4-naph~hoquinone, m~p. 42 -44 C o ; - 5 -:' . : . - - , . , ~:
:, ' ~

Exam~

Preparation Or the Sodlum Salt of 2-n-Dodecyl-3-hydroxy-1 4-na~ht,hoaulnone A dispersion Or 1.9 par~s o~ sodlum hydrlde ln 250 parts Or tetrahydroruran was added to a solution o~
26 parts Or 2-_-dodecyl-3-hydroxy-1,4-naphthoquinone in 450 parts o~ tetrahydrofuran at room temperature. The mixture was stirred at room temperature for 1 hour, then flltered to ~ive a burgundy solutlon of the sodium salt.

~ Example 4 Preparatlon of 2-n-DodecyI-3-methoxycarbonyloxy-1,4-naphtho~u:inone Sixty parts of the above-mentioned sodium salt solution was stirred with 0.59 parts of methyl chloro-~ormate in 10 parts o~ tetrahydrofuran at room temperature.
The mixture was stirred ror 1 hour,then allo~ed to stand overnight. The resulting suspension was filtered and the riltrate evaporated to dryness. The residue was crystallized rrom acetonitrile to give 2.0 parts of 2-n-dodecyl-3-methoxy-20 carbonyloxy-194-naphthoquinone, m.p. 70-72C.
By using the appropriate 2-alkyl-3-hydroxy-l~4 naphthoquinone and the appropriate acid chloride or anhydride~
the rollowing compounds shown in Table I could be similarly prepared by anyone skilled in the art, using the procedure outlined in Examples 1 throu~h 4.

~' ' .
, .

.
' . . - - . ~ .

.~..
;

2~5 ~rable 1 O

Me 1~ in g Rl . , R2 ~ ~: ) -n-C12H25 -OC}~3 70 72 -~-C12H25 OCH2C 3 42-47 CH
-n-C12~25 -0-CHCH2CH3 [IR~o 1753 cm ]
-n-cl2H25 -c~l2ocll3 69-71 -n-C12H25 -cl~2oc~T2c~l3 }~ -(C}T ) CH3 [IR >=o 1791 cm 1]
n--C12 25 2 7 -n-C12H25 -(C}~2 ) 12CH3 51-53 ; ' -n-C12H2~i -(CH2)16CH3 ` -n-C12H25 -cH-CH2 -n-C12~25 -CH=C}TCH343. 5-44 . 5 C1~3 -_-C1?lT25 -C=CH2 N2D5 1. 5202 : ~ 25 -n-C12H25 -C}l=CH-CO~HND 1. 5162 -n---C12~25 -CH=CH-CHsCH-CH3 68-74 -n-C12~25 _(cll2~7c~cllc~l2c~Tac~T(c~T;~)4cH3 . '' ' ` .
` :; ~ 7 ~

j . . . . .

~able 1 (co~in~
R Polr~t -CH2CH2~ C~I3 68-69 n C12H25 ~(CH2~5~3 ~2D5 1~5141 n C12H25 -(C~I2)6CH3 54-57 /--~7 '' -CH~ CH3 91-93 -n-C H25 ~(C~ -G~ (CH2)7C}~3 DMP~E 5 ~C~ O O
~- CH2cc~Icoc~I2c~I3 CC~3 ~' q~ material was prepared ~ccord~rlg to th~ proce-clure o~ ~. Viscontinî and X~,. M~rckl~ng, ~el,. gb~
~cta, ~, 2280 (1952). To 2.65 par~ o~ magnesium tuxning~
as ad~ed 15 part~ ~b~olut~ ethanol at room temperature and 0.5 parts o~ carbon tetraehloride. As 800n as the in~tial r~ction ~ub~de~ 100 parts o~ d~ ethe~ ~as a~ded. The 20 n~x~ure ~raæ ætirxed wi~hout coolin~ w~tll the reaction cea~ed, thon 19.6 parts of ethyl 3-oxobutanoate in 20 part~
of dry ether was added with ice cooli~g an~ good ætirring.
A~ter the resulting prec~pltate dis~olved, the ~olution was c~ol~d in an ice salt bath and 16 parts o~ 2 me~
phenglac~tyl chloride was ~lowl~ ~dded. ~h2 ml~cture wa~

.
.

:
.. . . . .
-~ . , ~ .

allow~d to stand overnight at room temperature and the~
eombined with iGe and ~ul~uric acid. me ether layer wa~
sel~arated, ws.~hed wi~h water, drled over sodium ~ at~
and ~tripped to glve et~rl 2-ace~1~-(2-meth;rl~3henyl)-3- -oxob~tanoate a~ a crude oil.
~ 6 C~3 0 n n I2CCEI2COC~2CH3 ~ollowing the method o~ Eunsdîecker ~, 10 75, 454(1942~7~ 26 parts o~ et~l 2-acetyl-4~(2-meth;rl- `
phenyl)-3-oxobu~anoate wa~ stirred ~or 10 hours at room :
ten~perature with 100 parts ethanol and 608 parts c~ sodium ~thoxide. The mi~ture wa8 diluted ~lth water and e~tracted ~lth ether. The sol~ent wa6 $hen evaporat~d to give ethyl 4-(2-meth~lph~nyl)-3-oxobutanoate.
~ ~ 7 : Preparation o~ Eth~l 2-~L2-M~Ihylpher~l)aeetyl~tetradecanoate ~ ' ' ~ H3 g o (C~)llC~ .
, .
Three part~ Or ethyl 4--(2-methylphenyl)-3-o~o-butanoate, 1 part o~ sodium ~thoxide, ~.6 part~ of l-brom~
dodeeane~ 0.5 part8 o~ pota8sium iodide and 50 part~ oP
ab~olute ethanol were re~lux~d together for 4 hour~ a~d :
then ~tirred 18 hour8 at room temperatur~. Th~ mlxture was .

.

evaporat~d to a ~mall volume, diluted with 100 part~ wat~r and extracted ~ith ether. The ether extract waæ wa~hed nlth ~turated ~odium bicarbonateJ ~aturated sod1um chloride ~olutlon and dried over magn~ium ~ul~ate. E~aporation o~ the eth~r ~ave 6 part~ o~ crude ethyl 2-((2-meth~lphe~yl)-ace~ tetrade~anoate as an oil ~hich wa~ not ~urther puri~ed.
EXAMEIE 8 :

C12~25 Four part~ o~ crude ethyl 2-((2-m~thylphenyl)~
ace~yl3tetradecanoate ob~ainèd in Example 7 was comb$ned ~ith 12 part~ o~ cold conc~ntra~d sul~uric ac~d and ~tlrred at roo~ ~e~peratur~ ~or 66 hour~. The m~xture wa~ poured ~to ice w~ter a~d mado slightly ba~l.c by the sddition Or

5 ~ a~ueous ~otlum hydroxide. EnOUg~L ethanol ~a~ added to di~olYe the organic matter and al~ wa~ the~ bubbled through the ~olution ~or 3 h~ur~9 ~he result~ng 801ut~n was ax-tracted ~ith 100 part~ petroleum ether (twice), acidir~ed with hydro~hlorl~ acid and re-extracted with diethylether.
The.et~er extraet wa~ waeh2d with ~aturated aodium chloride, dried over mag~e~ium sul~at~ and evaporated. ~he r~idu~ ~
was tak~n up ln aceton~rile and riltered. The ~iltrat~
~as evaporated to dryne~ and th~ residue triturated with pekroleum ether to give 0.2 g o~ 2 dodec~1-3-hydro~-5-m~th~l-1,4-napthoquinone, ~.p. 92-93C.

-- 10 _ ~ _9 O
~ n~C12H25 ,:~
OC~3 CH~, o n O
3.8 p~rts o~ 2 dodecyl-3hydro~y-5-methyl-1,4 naph~hoquinone, 8 parts Or aceti~ anhydride and 32 part~ ~
o~ pyridlne were ~tirred at ro~m tem~erature for 16 h~ur~. :
The re~ulting mlxtuxe wa~ evaporated under reduc~d pre~ur~
to remo~e th~ p~rid~ne. The r~sldue nas recry3talllz~d ~rom ~ethanol to give 2.5 parts o~ 3-a¢etoxy-2-dodecyL5;
~ethyl~ naphthoquinon~ ~.p~ 69-75C.

. .
Preparatlon or :L~(5-~hlor~ h~droxynaph~halen-2-yl)- :
1 dodecanone ' .:

OE O :
~, C (CH2~0C~3 Cl A mlxtur~ of 16.6 part~ Or 5~chloro-1-napthalenol [~r ~ nn ana Kircho~, ~ Ann., 247, 372 (1888)~
19~2 part~ o~ dodec~noic acid and 132 part8 0~ boron ~rl~l~orid~ ~ther complex (48% BF3) w~ 3~irr~d under ni~rogen on a steam bath ~or 6 hour~. Water (114 part33 wa~
added and ~ther dis~illed o~ b~ ~rther heating. The r0sulting m~xture ~a~ eooled in ~ce and a tan ~olid wa~

.

s f'iltered and recrystallized ~ro~ ~thanol to give 18 par~
Or yello~ 1-(5-chloro 1~ dro~ynaph~hal~n-2-yl)-l-dodec-anone, m.p. 86-87C.
EXA~ 11 .
~_: l ~ a ~n~
OH
~J n-Cl~25 A so~ution o~ 17.4 part~ o~ 1-(5-ch:Loro-l-hydro~naphthalen-2-yl)-1-dodecalloIl~ and 107 part~ o~ 37%
~2ydro~hlorlc aeid ln 2.5 part~ o~ ethanol was contacted with ~tirr~ng at re~ c during 26 hours, ~7ith 40 partB 0 zinc d~lst which ha~ been amalgsmated by treatment ~h 3 part~ o~ mercurlc ehloride ~nd 53 parts o~ 2.1% }~rdro-chlorlc acid ~ollowed by wa~hing with ethanol. T~e zinc amalgam ~a~ added in 3ma11 p~rtion~ t~rough~ut the reactl~n period. Upo~ coolir~, a ~olid separated. P,~ter dis~olu~ion o~ thi~ ~olid in eths,nol, zine amalgam was fflt~red, sIld eooling gav~ 0.5 part~ Or ~tarting material which wa~ ~iltered.
Concentration oP the ~iltrateJ purl~ication by recrystalllza~
tlon ~roDI ethanol, and column chromatograph;~r on ~ilica ~sel 20 UBi~ chlorobutane as elu~nt gave 12 partæ of 5-chloro~2-dodecyl~ aphthaletlol, m.p~ 68-70C.

Pr~paratior~ o~ 5-Chloro-2-dodecyl-1,4-napht~og,uinone O

Cl ., .,.,-.
.

A mixture o~ 5 0 4 part~ o~ 5-chloro-2-dodecyl 1-naphthalerlol, 18 parts o~ 96% ~ul~ic acid, 7105 parts o~
gl~cial acetic acid, and 29 part~ o~ water was s-tirred at 70C and 8.~5 parts o~ cold 30% h~drogen pero~ide wa~ ~
a.dded dropui~e over 8 hours4 Stirrirl~ at 70~C wa~ con- ::
tinued ~or anoth~r 17 hour~,. The m~xkure wa~ cooled and ::
an orange ~olid taken up in met~ ne chlorlde, and ~he extr~ct ~rash~d ~ith water, dried and stripped~ The re~
sulting tan solid wa~ pur:L~ied by columrl chromatography 10 ~rom l-chlorotutane on ~ ca gel to gi~e 2 parts o~
5-chloro-2-dodecyl-1,4-n~phthoquinone, m~p~ 57.5-58.5C.
~A~E 13 Pre~aration o~ 5-Chloro~2-dodecyl-3-hydro~-1,4-n~phtho~uinone o ~ n C12~25 A mixture o~ 1.7 part~ o~ 5-chloro-2-dod~cyl-1,4-naphtho~uinone, 25 part~ ethanol, 0.626 parts anhydrous ~odiu~ carbonate and 6u3 part~ w~ter w~ contacted with 1.13 p~rt~ o~ 30% hydrogen peroxide at 32~C and then re-~lux~d ~or 10 minutes. The resulting mlxture wa~ then cooied to 50C a~d ~ solution o~ 1.5~ part~ o~ pota~slum hydroxid~ in 49.5 parts o~ etha~ol ~a~ added to it. The resultiag deep red mlxture wa~ then h~ated to 50C o~er 2~ ~lnut~s and the temperature held there Por 45 mln~te~.
A~ter co~ling to 10C the mlx~ur2 waæ then contacted with 251 par~s o~ 2.72% hydrochloric ~c~d. me resulting yellow cr~stal~ were filtered, dried and puri~ied by column chromatogPaph~ on sllica gel U8:t~g l-chlorobutall~ as eluent.
Solvent remo~ral gave 1.,4 parts o~ 5-chloro-2 dodecyl-3 dro~y-l, 4-naphth~quinon~, m, p . 102 -104. 5 C .
EXA~PrE 14 Preparation o~ 3-Aceto~ 5~chloro-2-dodeeyl-1,4-naphtho~
auinone ~,, , _ . _ , ~'C12E25 ....
~OCC~3 Cl O
A solution o~ 0. 95 p~t;B 0~ 5-chloro-2 dodecyl-3 -h;ydr :3~;y-17 4-naph~hoquinon~ in 20 parts o~ yrdrous tetrahydro~uran lYa~ added ullder nitro~Sen to a mixtllre o~
o.o635 part~ o~ di~pe~sed ~odium hydrldle in 40 part~ o~
t~tra~rdrofuran with stlrring at room te~perature~, A~ter 45 mlnutes o~ stirring, a solution o~ 0.275 part~ Or acetyl chloride in 30 parts o~ t~trah~dro~uran wa3 added and the mixture stirr~d ~or 5 hour~. The tetrah~dro~uran W~8 st~ipp~d under reduced pr~sur~ and the residue ~aken up in methyl~n~ chloride and then wa~hed with water, 10%
~ydrochloric acid, ~our ~re t~me~ wit;h water, dr~ed o~er æodlum ~ a~e and ætrlpped. The result~ng yellow 601id wa~ puri~ied b~ column ~hromatography on silica gel UBing l-chlorobutane ~8 eluent. Sol~ent rem~val ga~e 0.9 part~
oP 3-acetoxy-5-chloro-2-dode~ 1,4-naphthoquinone, m.p~
57-59C.
~ y uslng the appropria~e 2-alkyl-3-hydroxy-1,4-naphthoquinone ~nd th~ ~ppropriat~ acid chloride or an-hydride, the ~ollowin~ compounds shown in Table 2 could be simllarl~ prepared by an~one skilled ln the art, using the procedure ou~lined in Example~ 5 throu~h 14~, Z~5 .~ ..
o ~ ~ ' O l ' , ~c~
.

~ I ~ , .

o C~ "

~1 o ~ x I ~) ~ c~ c~ c~ c~ o m c~ ~ o c~
X~ .

~ 5: C~
N ~ ~ ~ ~ ~ a-~ ~ C~ C~
N ¦ C,) C~ C~ C~ c~ C l o :1: Cl X :T t_) ~) C

:C ' , .

1 N ~ ~ ~ ~ N ~I

' .
.

~L~8ZZ05 .~' ~ I I , ~ t ' t t ~ ' t ' I t t t .~ . .

~ , ' ~-7 ' ~ ' ' .

1~

~ CN

O ~ r ~ ~ r ~ , m r r 1 ~J ~ N ~ ~L` ~ ~ ~ ' L ) I: r. r.
r r. ,~ r .r r ~ 3 ~ 1 ~ L~

Formulation and U5e . .
The~e compound~ are u~e~ul a~ mlticide~ and can be used to protect both pl~nt~ and an~mals ~rom damage cau~ed by th~e pe~t~. More sp~ci~ically, fruit~, fi~ld crop~, vegetable~, ornamentals, bird~ ~nd oth~r warm-blooded an~mal~ includ~ng man can al~o be protected.
Wh~n mites come into contaet with theee com-pounds, eltheP in khe ~orm o~ direct spr~y~ or by ~alkinæ over ~ur~ace~ which have be~n tre~ted, they rapldly become irritated and leave the area or ar~ killed i~ they ha~e been exposed to a suf~icie~tly high dosage. While moBt plants or ~nlmals are able to tolerate thz pre~ence Or ver~ ~mall numbers o~ mike~ without apparent adverse e~fect, ~he re~roductlve Gapaci~y o~ these pest~ ls enormou~, Genera}ly, mite population~ rapldl~ build up, easily out~
stripping parasite and predator capabili~ies ~or control.
Groweræ notin~ rapid mlte build~up muæt take immediate aetlon to prevent damage to economica3.1y ~mpor~ant crop~O
muæ, a method i~ needed ~or immediat~ly reduclng mite ~0 bulld-up a~d thereby preventing damag~ to important erop~.
The ~ompounds o~ thi~ i~vention alæ~ ha~e a dlrect lethal contact action a~ainst the ~gæ o~ mi~e~. Mite eg~ expo~ed to ~pray~ of th~æe compounds are kill~d and h*~chln~ falls to occur. Rates æligh~ly hi~her than tho~e used to kill ~he motlle mite ~orms are generall~ required ~or good o~icidal e~fect.
; Thes~ compou~ds are ~03t e~ectl~e ~or the control o~
mites. ~ry 8m311 quanitltes o~ these compou~ds are re-quired ~or miticidal acti~ity; additionally, the com-pounds are not rapldly wa~hed Prom le~ve~ ~y raln.

3Z'~1~5 They do not have an~ adverse effect on ladybird beetles, which are important mite predators, and the compounds rapidly degrade in the environment. The compounds are also effective against phosphorous-resistant strains of mites.
The quantity of compound needed for miticidal activity will vary depending on the specific situation.
Among the variables that must be considered in deciding on the quantity of chemical to be used are the specific compound itself, the specific mite to be controlled, - weather conditions, the type of crop, the stage of develop-ment of the crop, the volume of spray applied, population pressure, and the interval between appiications. For plant pxotection, solutions or suspensions containing as little as 5 ppm of active ingredient in a spray solution may prove effective under a given set of circumstances. For field usage, however, in high-volume applications, a~ueous spray preparations containing 40-~,000 ppm of active ingredient are generally useful. Preferred are suspensions containing 80-1,000 ppm, and most preferred are those containin~ 150-500 ppm. On an area basis, in general, .03 to 15 kilograms of active ingredient per hectare are acceptable, preferably .06 to 8 kilograms, and most preferably .1 to 4 kg. When applied in an orchard, spraying is continued until run-off is observed.
It may be desirable or useful to mix the com-pounds of this inventlon ~ith othcr agricultural ~esticides or adjuvants. Such mixtures oftcn incrcase the cffectivc-ncss of thc a~plication on mitcs and broadcn thc scopc oE
control to embracc othcr pests such as insccts, fung;, nematodes, or bacteriaO A ml~ture with a re~ined petroleum sprag oll or Superior oil ha~ been shown to pro~ide ~reater than additl~e result~ on mite~O Other pesticide~ with which the compound~ of thi~ invention may be mixed to achieve broader-spectrum aetivi~y inelude:
diazinon - OgO-di~th~l 0-(2-læopropyl-4-methyl-6-pyrimidyl)pho~phorothloate di~lfoton - O,O-d~ethyl S-2(eth~1thlo)ethyl-pho~phorodithloate 10 phorate - O,O-diethyl S-(ethylthio)m~thylphos-phorodithioate oxamyl - S~methyl l-(d~methylcarbamoyl)-N-~(meth~lcar~am~)o~y~thlo~ormimldate meth~m~l - S-methyl N~methylcarbamogloxy)th~o-acetimidate benomy butylcarbamoyl-2-benzlmidazole-carbamic acid, methyl ester captan - N trichlorom2~hylthiophthalimide maneb - ethylenebi~dithiocarbamic acid, manganese ~alt carboxin ~ 5,6-dih~dro-2-methyl-1,4-oxathiin-3-¢arboxanilide ~treptom~cin ~ 2,4-diguanidino-3,5,6-trihydro~ycy~lo-hexyl-5~deo~y-2-o-(2-deo~y-2-methylamino_x-gl~copyranosyl-3 ~ormglpentofuranoside azinphosmethyl - 0,0-dim~thyl-5-~4-o~o-1,2,3-b~nzo-tr~zin-3-(4H)ylmet~yl~pho~phorodi~
thioate.
0 m~ ~ompound~ are especially suited for the protection o~ ing plant~ such a~ ~ruit-bearin~ tree~, ~, .~ - , . .

.' ' .

~'~ .'~6~Z~ S

nut-bearing trees, ornamental trees, forest trees, vegetable crops, horticultural crops (including ornamentals, small fruit and berries) and grain and seed crops. ~pple trees, peach trees, cotiton, citrus trees~ beans and peanuts are particularly susceptible to mite damage and can ~e protected hy application of the compounds of this invention.
To assure control throughout the growing season (e.g., June through August in the Northern Hemisphere) multiple applications at desired intervals can be utilized.
Many species of mites are controlled by the compounds of this invention. The following is a list of representative susceptible mites along with the types o~
damage that they can cause: Panonychus ulmi (European red mite) and Tetranychus urticae (two-spotted mite) which ~re commonly called "orchard mites", and which attack a great many deciduous trees, such as apple, pear, cherry, plum and peach trees; Tetranychus atlanticus (Atlantic or strawberry -mite), T. cinnabarinu (carmine spider mite) and T. pacificus (Pacific mite); which attack cotton and numerous other crop plants; Paratetranchus citri (citrus red mite) and others which attack citrus; Phyllocoptruta oleivora which causes citrus rust; Bryobia praetiosa (clover mite) which attacks clover, alfalfa and oth~r crops; Ac~ria neocynodomis which attacks ~rasses and other plants; Tetranycllus medanieli which a~tacks deciduous ~ruit in nortl~western U.S.; and Oli~ony~hus pratensis which attacks sor~hum and other grasses.
Useful formulations of these compounds can be prepared in conventional ways. They include dusts, ~ranules, pell~s, solutions, suspensions, emulsions, wettable powder~, e~ulæi~lable concentrates and the like. Man~ o~
the~e m~y be applied directly. Sprayable ~ormulations can be extend~d in suitable media and u~ed at 6pray volume~ o~ :
~rom a Tew pints to several hundred gallon~ per acre. High ~trength compositions are prim3ri~y u~ed as lnter~ediates ~or ~urther ~orm~lat~on. The formulations, broadlg~ contai~
about 1~ to 99% by we~ght of ~cti~e in~redient(~) and at least on~ of a) abou~ 0.1~ t~ 20% æur~actant(e~ and b) about 5% to 99% ~olid or llquid diluent(s). M~re speci~ically~
they wlll cont~l~ the~e inæredients ln the ~ollowlng approxi-mate proportions:
Table 3 Acti~e Dilu- Surfac-~ ent(8) Wettable Powder~ 20-90 0-74 1-10 O:Ll Suspe~slone, Em~l~io~s, Solu~ion~
(incl~ding Emul~ifi-able Concentrate~) 5-50 40-95 0-15 Aq~eou~ SU~penslons 10-50 40-84 1-20 Du3t~ 1-25 70-99 0- 5 G.ra~ul~8 ~ Pellet~ 1-95 5-99 0-15 ~i~h-3treng~h Co~po~ltion~ 90-99 0-10 0- 2 -Lower or h~her level~ o~ active i~gredient can, o~ cour~e, be pre~ent depending on the in~ended u~e and the phy~ical properties o~ the compound~ Eigher ratios o~ 9Ur-~actan~ to acti~e inæred~ent are sometimes de~irable, and are achieved by incorporation into the formulation or by 30 tank mlxin~.

- ~1 Typical ~olid diluent~ are de~cribed in Watkln~
et alc ll~laadbook Or Insectlcide Du~t Dlluent~ and Carriers~, 2nLd Ed., ~orland BoOksg Galdwell, N., J. me m~re absorptiv~
dlluent~ are pre~erred for wettable powd~rs and the den~er one~ for du~ts . ~pical li~uid di luent~ and ~olvent~ are described in Mar~den, ~Sol~ent~ ~uide", 2nd Edn., Int~r-sc~ence, N~w York, 1950. Solublllt~r un~er 0.1~ $~ pre-~erred for ~ ension con~entrate~; 801ution concentrate~
are preferably ~k~le again~t pha~e ~eparation at 0C..
10 ~McCutcheon~ ~ Detergentæ and Ensulsifier Annual", Allured Publo Corp., Ridgewood3 N~w Jsr~, as well a~ Si~el~y and Wood, "Encyclopedia of ~ur~ace ActiYe ~gent~n, Chemical Publ. CO~J Inc., ~ew York, 1964~ t sur~actants and re~a~mend~d use~. ~11 formulati~ns ca~ contain minor amountæ
Or additlveQ to red~e ~oam, cakln~, corro~ion, mlcrobiolo-al growth, ~tc.
The m~thods o~ m~kl~g su¢h composition~ ar~ ~ell knownO Solution~ are pre~ared by ~impl~ mixing the ingre-dlents. Flne, solid co~po~itions anemade by blending and, usuall~, grind~ng as i~ a hammer mill or *luid e~er~y m$11.
Susp2nslon~ ~re prep~red ~y ~et-milling (~ee, l.e~, Llttler U.S. Patent 3,o60~o84?. Granule~ and pellet~ may b~ made by spr~ying th@ acti~e ~terial upon pre~orm~d gra~ular carrl~rs or by agglomeration te~hnigue~ See J. E. Brown~g, "A~glo~eration", ~ , De~ember 4, 1967, pp~
1~7 ~f. and Perry's 5~3~ r~b~nk, 4th Ed., M~Graw~ . Y., 1963, pp. 8-59 ~.
Por ~urther information r~garding the art o~
~ormulation, see, ~or example:
3o J.B. Buchanan, ~.S. Patent 3,5~6,834 ~pril 27, 1971, ColO 5, Line 3 through Col. 7, Line 70 and ~xs. 1-4, 17, 106, 123-140.

.. . . . . .
. . . ~ .

R. R. Sha~er, U~S. Patent 3,560,616 February 2, 1971, Col. 3, Line 48 through Col. 7, line 26 and E~ample~
3_9~ 18.
E. So~ers, ~Formulation~, Chapter 6 in Torge~on, 'IFungicides''~.~ol. I 7 Academlc Pre~s, ~. Y..19670 Still another llquid ~ormulation which i~ part~-cularl~ ~onvenient for smRll-~cale u~e is the "aerosol" ~or- :
mulation ~rh~ch 1~ pack~ge~ under presæure in a ~uitable container. The ~ctlv~ i~gredient may b~ present in a ~uspen-~ion, emul~ion or ~olution~ For slmplici~y in preparation and use, solution~ are preferred. The ~re~ure may b~
3upplied b~ low-boili~g liquids ~uch as propane or chloro-~luoro carbons or by relatively ~olu~le gase~ sueh as carbon dioxid~ or nitrou~ ~xideO The chloro-fluoro carbons are pre~erred for a combination o~ good ~ol~ent power and lack o~ ~lammabilit~.
Mitlcidal abili~ o~ the~e compound~ i8 20 illu~trated in the following examples: -~{
Test unit~ conæistlr~ o~ plant pots containin~3 two red kidney bean plaIlts in the 2-l~ar stage w~re infested with 2-~potted mites and ~pra~ved to run-o~f~ with æolution~
~u~pen~ion~ o~ ~h~ compounds o~ thlB ln rention. Solutionsf-su~pengionæ were made by di~æol~ing weighed quantit~es o.~ the active ln~3redient~ ln 10 ml o~ a~etone and then d~luting to volume with water containin~ ~ 014 at 1:3000. Mortalit3r was evaluated two da~ after ~pra~r~ng.

: - 23 -- . . , , ,, , :. ', .. ::

s Table 5 O O
~O-C-R2 R
O
R% M~rtalil;y at .002%
Rl 2Sprag Concentration~

n-C12H25 -( CH2~7~3 96 n C12H25 (C~z)l2cEI3 99 n-C12~25 -GH=CHCH3 100 ~-C12~25 -CX-C~ICH=C~IC8398 n-C12H25 -OC~I3 100 10n-C12~I25 -OC2~5 99 n-C12E25 -C~2-0-CH3 97 n-C12~25 -CH=C~ICO~H 100 n-C13~27 3 99 n ~12H25 {~
n-C12~25 -OCHCE2CH3 60 C~

- 24 _ .:

.. , ~. . . .. ~ ~ . . . .

.. .. , .. . ~ ,. ,.. . ~ ~ . . .. .

-~ 2~

Te~t units con~isting of plan~ po~ contalning two r~d kidney beans ln th~ 2-lea~ stage w~re infe~ted with 2-~potted mite~ and ~prayed to run-o~f w~th dispersion~
o~ 3-aceto~g-5~chloro 2-dodecyl 1,4-naphtho~ulnone at variou~
rate~. Di~per~ions were made ~y di~solving an appropriat~ly weighed quantity o~ the act~ve ingredient in 10 ml o~ acetone and then diluting wlth water containin TREM 014 at 1:3000~ . -Mortali~ was e~aluated 2 day8 a~t2r ~praying. A table 10 o~ re$ults isset forth belsw:
Con~entration of Mortali~y ~24 hour~) 100 ~ ' 2~5 88 EX~MPLE 17 Red kidney bean plant~ ~n the 2-lea~ stage were ~ in~e~ted ~ith mitee wh~ch were allowed to o~ipo~it. ~bout ! 24 hours later the ~ a~es w~re dlpped in tetraethyl pyro~
pho~phate solu~lon to kill the mites. A~ter drying, the : plant~ ~ere 8pr~ed wlth te~t d~per~ion~ Or 3~acetox~-~
chloro-2-dodec~ 4-naphthoquinone at various rate~.
Disper~ion~ were m~de b~ dlssolving an appropriately welghed quanti~y o~ the actlve lngFed~ent in 10 ml o~
acetone and then d~luting wlth water containlng ~REM 01 ; &t 1:30000 H~tch~ng activity was observed and results wer~
re~orded ~iYe days later.

.

::

2Ç~

Concent~ration o~
~~

loO

12., 5 79 Control (O) - 26 - :~

,"' : :'

Claims (26)

CLAIMS:

1. A compound of the formula:

where R1 = alkyl of 8-14 carbon atoms either branched, cyclic, or straight chain;
R2 = alkyl of 1-17 carbon atoms either branched or straight chain, alkenyl of 2-17 carbon atoms, cycloalkyl of 3-6 carbon atoms, alkoxy of 1-4 carbon atoms -CH2OCH3, -CH2OCH2CH3, or -CH=CH-COOH;
X = hydrogen fluorine, chlorine, bromins, methyl, or methoxy;
Y = hydrogen, fluorine, chlorine, bromine, methyl, or methoxy;
provided, when R1 alkyl of 8-11 carbon atoms, at least one of X and Y is other than hydrogen; provided further, when R1 is 12-14 carbons and both X and Y are hydrogen, then R2 is not alkyl of 1-6 carbons nor cycloalkyl of 3-6 carbons.

2. A mixture of a compound or Claim 1 and a Superior Oil.

3. A mixture of a compound of Claim 1 and a compounds selected from the group consisting of chlordimeform, formetantante propargite, tetradifon, and benomyl.

4. A compound of Claim 1 where at least one of X and Y is other the hydrogen.

5. The compound of Claim 4 where R1 is alkyl of 11-14 carbon atoms, either branched or straight chain.

6. The compound of Claim 4 where R2 is alkyl of 1-6 carbon atoms, alkenyl of 2 or 3 carbon atoms, methoxy or ethoxy.

7. The compound of Claim 4 where either X or Y
is hydrogen.

8. The compound of Claim 4 where R1 straight chain alkyl of 11-14 carbon atoms.

9. The compound of Claim 4 where R2 is methyl or ethyl.

10. The compound of Claim 4 where R1 is alkyl of 11-14 carbon atoms, either branched or straight chain; R2 is alkyl of 1-6 carbon atoms, alkenyl of 2-3 carbon atoms;
methoxy or ethoxy; and wither X or Y is hydrogen.

11. The compound of Claim 10 where R1 is straight chain alkyl of 11-14 carbon atoms.

12. The compound of Claim 10 where R2 is methyl or ethyl.

13. The compound of Claim 4 where R1 is straight chain alkyl of 11-14 carbon atoms; R2 is methyl or ethyl;
and Y is hydrogen.

14. The compound of Claim 13: 3-acetoxy-5-chloro-2-n-dodecyl-1,4-naphthoguinone.

15. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 1.

16. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 4.

17. A method for protecting plants from or aphids which comprises applying ring to the plant a miticidally or aphicidally effiective amount of a compound of Claim 5.

18. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 6.

19. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 7.

20. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 8.

21. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 9.

22. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 10.

23. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally r effective amount of a compound of Claim 11.

21. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 12.

25. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 13.

26. A method for protecting plants from mites or aphids which comprises applying to the plant a miticidally or aphicidally effective amount of a compound of Claim 14.