DE2603864A1 - CYCLOHEXADIENE DERIVATIVES - Google Patents

Description

Dr. F. Zumstein Sr. - Dr. E. Assmann - Dr. R. Koc.iigsberr er Dipl.-Phys. R. Holzbauer - Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun.

P ATENTANWA LT C? 6 0 3 8 6

("j

collect phone * 22534, A _{n m0NC} hEM 2.

"TELEX: i2OO79
TCLCGHAMME Z ¹ JMPAT

POSTSCHCCK ACCOUNT

MLINCHEN 91) 39 f! 09 BLZ7OO1OO80

BANK ACCOUNT BANKHAUS H AUFHAUSER

KTO. NR 397907. E3LZ 70030GOO

Case A / 25471
H / bs

MAY & BAKER LIMITED, Dagenham, Essex / Great Britain C ^ clohexadiene derivatives

The invention relates to cyclohexadiene derivatives containing them Compositions and their use in the control of insects and fungi, and methods for their preparation.

As a result of research it was surprisingly found that cyclohexadiene derivatives of the general formula I.

have valuable insecticidal and fungicidal properties. In the above formula I, R denotes a straight or branched-chain alkyl radical with 1 to 6 carbon atoms, preferably methyl, R denotes a chlorine atom, a hydroxy radical, a straight or branched chain alkyl radical with 1 to 6 carbon atoms, preferably methyl, a straight or branched one Alkoxy radical with 1 to 6 carbon atoms, preferably methoxy or an alkanoyloxy group -OCOR, in which R

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- 2 - lo

denotes a straight or branched chain alkyl radical having 1 "to 6 carbon atoms, and X ¹ and X ² , which can be identical or different, each represent a chlorine or bromine atom; when R ^{1 has} the meaning given above and R ^{2 is} a chlorine atom , a hydroxy radical, an alkoxy radical or an alkanoyl group as defined above, or X ¹ and X have the same meaning and each share a chlorine or bromine

1 ?

atom when R and R are each a straight or branched chain Represent an alkyl group having 1 to 6 carbon atoms.

The cyclohexadiene derivatives of the general formula I have valuable insecticidal and fungicidal activity, in particular (i) against Coleoptera (beetles or beetle-like insects and weevils, grain beetles and seed beetles) [for example Diabrotica spp., Anthenomus spp. and Sitophilus spp., for example Sitophilus oryzae (rice beetle)], Diptera (mosquitoes or mosquitoes and flies) [for example Anopheles spp., Aedes spp. and Culex spp. (Mosquitoes), Ceratitis spp. (Fruit fly or fruit fly), REgoletis spp. (Fruit fly maggots or larvae), Hylemyia spp., Musoa autumnal! S and Musca domestica (flies)], Lepidoptera (butterflies, sawfly or sawfly and moths or moths) [eg Heliothis spp. (Cotton bollworm and larva of Bamawolleulenfalters, larva of the tobacco budworm, eg Heliothis virescens), Spodoptera spp., Including Spodoptera littoralis (larva dor budworm) and southern armyworm ( 'southern armyworm ¹¹⁾ Kamostra configurata ( "bertha armyworm ¹¹⁾ Ostrlnia spp . (Getr © idebohrer), Trichoplusia ni (larva of the cabbage white butterfly), Pieris spp. (Larva of the large cabbage white butterfly), Laphygma spp. (H © © TOÜrm © r), Agrotis spp. (Owl caterpillars), Diprion pini (pine tosw Spruce sawfly), Spargothis spp. (Grape Eottö), Cjüla pomonella (fruit maggot or codling moth), Sortriz spp. (Tortrix fruit tree maggot) and Plutella spp., E.g. Plutella xylostella] and Hemiptera (singing chirp, e.g. Aeneolamia epp , eg Phorodon huaiuli and plant bugs, sB B ^ edsrcus spp.), and (ii) against Alternaria spp., eg Alternaria solani, Botrytis spp., eg Botrytis oinerea, HQlminthosporium spp., eg Helmlnthosporiura avariumenae, Fusarium Epp., eg Fusarium Epp., eg Fusarium Epp sambucinum, Mycosphaerella spp., e.g. Myoosphaerella pinodes, dusty Heitau species or fires,

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e.g. Erysiphe spp., e.g. Erysiphe graminis and Podosphaera e.g. Podosphaera leucotriche, Phycomycetes, e.g. Phytophthora spj)., e.g. Phytophthora infestans, fires, e.g. Uromyces epp., e.g. Uromyces appendiculatus and Puccinia spp., Tilletia carien, Ustilago spp., Rhizoctonia spp. and Sclerotinia spp ..

The compounds of general formula I can be used to control insect pests and fungi which are harmful to the growth of crops, stored products, household goods, wood or tree stocks, farm and domestic animals and humans, including insect species that are harmful to animals and Cause or transmit disease to humans.

The compounds of the general formula I are particularly valuable: in the protection of maize, tobacco, cotton, cabbage and rapeseed crops against Heliothis spp., Spodoptera spp., Mamostra configurata, laphygma spp. and Agrotis spp., in the protection of stored products, for example grain and household goods, including toppiches and other textiles, against attack by beetles or beetle-like insects, grain beetles and. Moths;

when protecting field crops, e.g. maize, cotton, rice or potatoes and vegetables, e.g. beans or cucumbers, against the Attack by larvae and alluvial growth stages of herbivorous beetle-like insects and weevils, seed beetles and grain beetles;

in the protection of cotton, sugar cane and fruit trees against the attack of sucking insects, e.g. aphids, song chirps or Cicadas, plant bugs and mammals or parasites; in protecting fruit and forest trees from attack

of leaf or saw wasps, moths or moths and flies;

when protecting field crops, for example beetroot, types of chard and cabbage or rapeseed crops against attack by flies;

in the protection of wood and wood products against attack by beetles or beetle-like insects;

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ο υ

■ in controlling fungi by the iiaaen respectively; ίοκ;. Οπ caused disease en .Fußfäule and, in particular _be i cereals, eg iieluiinthosporiun avenae-, Tillßtia caricr-, Ustilago spp, Rhizoctonia spp and Fusarium spp. infections

by using ^ _.... · .. ^ - ~ w ^ ■ - ,.>, -.-., ..-,.-.-,

in the control of pigeon-like Meltau species' resp. Fires

of cereals, apples, pears, cucumbers and ornamental plants, e.g.

Roses;

in the control of leaf burns on cereals (Puccinia spp. ;; in the control of early. Meltau or fire (Alternaria Bolani) and late meltaus or brands (Phytophthora infestans)

with tomatoes;

in the control of late meltau or burn (Phytophthora

infestans) in potatoes;

in the control of Phycomycetes or algae infestation of plant cultures, E.g. the cocoa and the oil palm and in the control of the gray mold (Botrytis spp.) and the Storage rot (Sclerotinia spp.) Of stone crops, e.g. plums, apricots and peaches, soft fruits, e.g. strawberries, Raspberries, black and red currants and grapes.

Suitable means for applying the compounds of the formula I.

include:

The application to cultivated plants as foliar sprays, pigeons, -granulates and foams, as soil and root treatment agents through liquid agents, dusts, granulates, mists and foams and as seed preparations by liquid slurries and Dusts; use on animals as sprays, as products for spraying, as products for dipping, as products for effervescent treatments, Self-treatment methods, e.g. dust bags, dust baths, back treatment products and salt licks for animals, Infusion applications, dusts and applications through mist formation; for stored products and household goods as sprays, dust and smoke-like or smoke-producing products, uses in the maintenance of general health and animal health in the form of sprays, dusts, smoke-like or smoke-generating Products, misting products and poisoned

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Bait, in places of pest infestation, eg "in houses, _dl animal dwellings, dung heaps and sewage. S

As will be apparent to those skilled in the art, the compounds _B

gene of the general formula I at least one center of chirality _Έ

possess, this center of chirality being on the carbon atom which contains the substituents R ¹ and R ² in the compounds

of the general formula I if neither X and X nor R _c

and R ^{2 are} identical. Further centers of chirality can be found at _T

R ¹ and R ² occur. The presence of a chirality leads to, _Λ

as is well known, to an isomerism. I understand

that if, as in the present case, on the use of compounds,

of the general formula I as insecticides and fungicides or I

on compositions containing these or on new compounds; fertilization of the general formula I is referred to, such Reference is intended to include all such isomers of general formula I and mixtures thereof.

Preferred compounds according to the invention for the control of insects are those cyclohexadiene derivatives of the general formula I in which X ¹ and X have the same meaning and each represent a chlorine or bromine atom, R ^{1 represents} a methyl, ethyl, propyl or isopropyl radical and R a chlorine atom, a hydroxyl group, a methyl group, a methoxy group, a butoxy group, an isobutoxy group, an acetoxy group or a hexanoyloxy group and in particular 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dienone, 4-acetoxy-2, 6- -dibromo-4-methylcyclohexa-2,5-dienone, 2,6-dibromo-4-ethyl-4-hydroxycyclohexa-2,5-dienone, 2,6-dichloro-4-hexanoyloxy-4-methylcyclohexa- 2,5-dienone, 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone, 2,6-dichloro-4-ethyl-4-hydroxycyclohexa-2,5-dienone, 2,6 -Dibromo-4-hydroxy-4-propyIcyclohexa-2,5-dienone, 2,4,6-trichloro-4-isopropylcyclohexa-2,5-dienone, 2,6-dibromo-4-methoxy- ~ 4-propylcyclohexa- 2,5-dienone, 4-butoxy-2,6-dichloro-4-methylcyclohexa-2,5-dienone, 2, G- Dichloro ^ -isobutoxy ^ -methylcyclohexa-2,5-dienone and 2,6-dibromo-4-ethyl-4-methoxycyclohexa-2,5-dienone. Such compounds are of particular interest in the control of larvae of Lepidopterus pests such as Heliothis

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iz

virescens (Ta "baksworm" or larva of the tobacco hawk), e.g. by treating the leaves of host plants with sprays, dusts or foams.

Preferred compounds according to the invention for the control of fungi are those cyclohexadiene derivatives of the general formula I ₁ in which X ¹ and X ^{2 have} the same meaning and

jQtjoilB denote a chlorine or bromine ", R represents a methyl or ethyl group and R ² a straight-chain or branched alkoxy radical with ^{4 to} 1" to 6 carbon atoms, preferably a methoxy radical or an alkanoyloxy group -OCOR ⁵ , where R- * has the meaning given above, preferably in acetoxy or propionyloxy group, and in particular 2,6-dibromo-4-metho ^ -4-methylcyclohexa-2,5-dienone, 2, e-dibromo ^ -methyl ^ -propionyloxycyclohexa -a, 5-dienone and 4-Acetoxy-2 _t 6-dibromo-4-ethylcyclohexa-2 _f 5-dienone.

12 1 The compounds of the general formula I in which X, X, R and R ² üio have the meaning given above are, with the exception of 2,6-dibromo-4-hydroxy-4-methyIcyclohoxa-2,5-dienone, 4 -Aoetoxy-2,6-dibromo-4-methylcyclohexa-2,5-dienone, 2,6-bibromo- -4,4-dlm © thylcyclohexa-2,5-dienone, 2,6-dichloro-4-hydroxy- 4 ~ -methylcyclohexa-2,5-dienone, 4-acetoxy-2,6-dichloro-4-methylcycloh © sa-2,5-dienone and 2,4,6-trichloro-4-tert.-butylcyclohexa- -2 , 5-dienone new compounds which have not been described in the literature so far.

Accordingly, the invention also includes, as new and valuable compounds, those cyclohexadiene derivatives of the general formula I in which X ¹ , X ² , R ¹ and R have the meanings given above, with the proviso that (i) when X and X have the same meanings and each represent a chlorine or bromine atom and R represents a hydroxy radical or an acetoxy group, R has a meaning other than that of a methyl radical or (ii) when X and X ^ each represent a bromine atom and R ^{2 represents} a methyl group, R ¹ has a different meaning than that of a methyl radical or (iii) when X _9, X ² and R ² each represent a chlorine atom, R ^{1 has} a different meaning than that of a tert-butyl radical.

609832/1007

When investigating the insecticidal and g Activity carried out on representative compounds of the formula, the following results were obtained:

L The following tea compounds were used:

A β 2 _f 6-dibromo-4,4-dim®thylcyclohexa-2,5-dienone B - ^ thllhexa ^^

D _{a 2} ] 6-I> icalor-4,4-aie © tliylcyclohexa-2 _f 5-dienone

E - ^ Btttyryloxy ^ .ö-di ^ roiii-A-methylcyclohexa-Z, 5-dienone

H = ^ Aoetoyt

I = 2,6-dichloro-4-isobutyryloxy-4-methylcyclohexa-2 _t 5-dienone

J = 2 ^> , 6-dichloro-4-methyl-4-propionyloxycyclohexa-2,5-dienone

K = 4-butyryloxy-2,6-diohlor-4-methylcyclohexa-2 _f 5-dienone L α 2,6-dibromo-4-ethyl-4-hydrocyclohexa-2,5-dienone

M _s 4lAcetoxy-2,6-dibromo-4-ethylcyclohexa-2,5-dienone H = 2,6-dichloro-4-hexanoyloxy-4-methylcyclohex © -2 _t 5-dienone

O β 2U- ^dichloro " ⁴ ~ ^methyl " ⁴ "^" ^{methyltUtanOylOXy} ^ ~ ^CyClOlieXa ~

-2,5-dienone
ρ _ 2,6-dichloro-4-methyl-4- (4-methylpentanoyloxy) -cyclohexa-

-2 _f 5-dienon

ο = ajö

R = 2 6-dibromo-4-methoxy-4-methylcyclohexa-2,5-dienone S s 2 6-dibromo-4-chloro-4-methylcyclohexa-2 _t 5-dienone T s 2 _f 6-dibromo-4- liydroxy-4-methylcycloliexa-2 _f 5-dienone U = 2 6-dichloro-4-ethyl-4-hydroxycyclohexa-2 _t 5-dienone γ = 2 6-dichloro-4-heptanoyloxy-4-niethylcyclohexa-2,5- dienone V = 2 6-dibromo-4-hydroxy-4-propylcyclohexa-2,5-dienone χ ss 2 4,6-trichloro-4-isopropylcyclohexa-2,5-dienone y = 2 e-dibromo ^ -methoxy ^ - propylcyclohexa ^^ - dienone Z = 2 4 G-Trichlor ^ -oethylcyclohe.Ta ^^ - dienone AA β 2-bromo-6-chloro-4-methoxy-4-methylcyclohexa-2,5-dienone BB = 4-butoxy- 2,6-dichloro-4-methyloyelohexa-2 _f 5-dienone CC s 2 6-dichloro-4-isobutoxy-4-methylcyclohexa-2,5-dienone DD = 2-bromo-6-chloro-4-hydroxy-4 -methylcyGlohexa-2,5-dienori

6C9832 / 1007

K - 2-bromo-6-chloro-4-ethox; y ~ 4 ~ :, f thy j.ey o P - 2, G-dibrom-4-eth7l-4-meUio>:;, 'ey ■ ;. , .r / i '

2bÜ3öB4

';, Γ-servant di o ::; jn

Teat 1

KUben blade disks (diameter 46 mm) were placed in 2 / o Agar in plastic Petri dishes (diameter 9 cm) and infected, each disc with 10 in the second stage Tiarves of Plutella xyloote.Lla, on cabbage plants had been bred to death.

The test compounds were dissolved in a small amount of pure acetone and then with 50% vol / vol aqueous acetone to give solutions of $ 0.2, $ 0.1 and $ 0.05 w / v " ¹ These solutions were then applied to the infected beet leaf disks using a calibrated Potterturn: to achieve an application equivalent to applying approximately 60 gallons of spray fluid per acre The experimental treatment consisted of four replicated discs, the infected control discs being treated with only 5% v / v aqueous acetone.

The Petri dishes were kept ventilated with aluminum caps with insect-proof seal and covered at about 25 ⁰ C.

After 48 hours and 16 days, the number of living and dead larvae was determined and the percentage mortality calculated and using Abbot's formula, correcting if necessary, with the controls compared. .

The results obtained are shown in Table I below specified.

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b O 3 8 6

T ε ο

Test-
cerbindun Y ^ Concentration
' the
j used
solution ^ -Mortality
the
Larvae
(after 48 hours) 90 48 95 «^ -Mortality
the
Larvae
(after 16 days) A. AA j ο, ι 75 i
0.05 j 35 65 100 B. BB:
; I.
I. 0.05 60 0.1, 70 o _f i: loo 98 N cc 0.2 85 0.05 0.1
* 98 U 0.1 48 ο, ι 65 ν 0.1 38 80 y i 0.05 8th 46 f 0.2- 88 100 0.1 55 95 y 0.1 65 95 0.05! 53 79 ο, ι 80 61 100 98 I.
loo! 100 100

Vi 13 IU R (ve

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Update of Table I:

test
verb in-:
manure ^ Concentration
the
used
solution ^ «Mortality
the
Larver.
(after. 48Si23d; %-Mortality
the
Larvae
(after 16 days) DD 0.1 85 98 EE 0.1 93 100 FF
————— 0.05 53
• 89

guest 2

Crushed wheat and whole grain or meal were each mixed with a solution of test compound A in acetone Achieve a final concentration of 1000 parts per million treated on a weight basis (ppm). The acetone was then made by stirring the crushed wheat or whole grain meal removed in a stream of air until the acetone odor was no longer perceptible. Parts of it were then crushed with further Yieizen or meal to give a concentration of 500 ppm of test compound A diluted.

One intake unit (approx. 8 ml) of treated wholemeal flour was used then placed in a glass tube (diameter 28 mm, length 70 mm) and then a unit of measurement of treated crushed Wheat that has the same concentration of the test compound A contained. Control tubes were made to hold the whole wheat flour and the crushed wheat in either were untreated or treated with Aoeton alone. Four tubes of each concentration of test compound were used.

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O ü ■ -;

,. _1pvieil8 'i0 adult Sitophii _Ua All tubes were Dewe - _be ventilated pre-

_oryz ao (none) "f ^ / Se _n , ann in _oiM . Ιη, α-closures plugged. Bie" ehalten. Me determination ^ · hatot at 26 ⁰ O and high efficiency of the living and dead accumulated caier 6 weeks later carried out.

_{,, 1n of the} following Table II The results obtained are in η

specified.

T a * ° ^{Ί Ί e 1} ^ -

Sum of adult beetles Dei v '<er repetitions

concentration

the
Test compound A

Number of dead

the beetle after 6 weeks

Beetle

after 6 weeks.

Beetle after 5 sayings

(Only with acetone

treated

Control)

(Untreated control)

* It should be noted that this number may be affected by the tendency of the living beetles to the dead beetles consume.

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/ ■ ν, -, J "

These results show eic; ~; .jUrtiges Ab "ο tu a ^ cl.e; .i ^ a \ at a concentration before 1000 t> dt» of the Tci3 ⁺ .verbindur.g A - an almost complete auto-killing of Eefalla at a concentration of 500 ppm the Tc Si connection A.

Γ-- ent? - **

Acetone solutions containing 0.2? Δ and 0.1? Δ w / v of Test-A decalked, were prepared as in Test 1 above,,,, and on tobacco leaf logs

qH; 'siQ &i' / j'unge - .. larvae ^: from Heliothis virescens from be ? ^ φ £ ^^ '^ abftkBbl & tterscta.eiben feed and' replaced these: -g |

k $ ~ i old :, Soli® lben ^: untreated tobacco leaves from the 2nd: * | WbLÜQT Befeaadlung. In total, with each treatment, 9 larvae grew, 3 larvae grew under the container

were di®. survivors _;; Larvae to a || ^ || ^.'Nabxung: Ov © rg ^ 1lhr1; ^ una, lower St to ^ |||| held. ''"Aa 7. '"Testday; became -ί ||||

li®''E3ostaHt »tebestination durchehgeflhrt and'aan let it äiegg :, äba? X © ^ ad © n .S3i © isplar® arer dolls. <£ s'. Were: auoh loss of profit |||| g ^? δ © ^! Shepherd wag umä the puppet recorded. ■ "■■> ^: Wjllflfi

..äMiq ^! '© stealtenen Exgobniese.:. are in the following table III-; | ig ;;

boULt · - '.' ■ '■,'. ■ '■. · · "Llll

^! Table III · '' · ^: ·. '^ fW-

P «concentration solution used

fUMortality (7th day)

0.2

80

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i \

Test 4 ^e

Spore suspensions of Alternaria solani (A.ε.), ε

Botrytis cinerea (B.c.) »Fusariuci sambucinum (P.e.) and Ϊ Mycosphaerella pinodes (M.p.) by scratching agar plates

of 1- "to 2-week old fungi cultures with sterile distilled E

tera water using a glass rod. The Kulxure.i ε

were then filtered through muslin and that contained spores- j de FiItrat used for vaccination.

Heltnithosporium avenae (H.A.) - mycelium was used as a vaccine by Ί

Macerate a 2 week old liquid culture with education

produced a fine suspension. ^

The test compound (0.025 g) was distilled with sterile π

Water ("with approx. 1.0 ml of a 0.1 ^ solution of a non-ö

ionizing surfactants [Texofor FX 170] in sterile, 2

distilled water) in a boiling tube using d a Teflon block. The suspension obtained was

with 50 ml of sterile, distilled water to achieve a C

Final concentration of the test compound from 500 ppm to 50 ml C.

filled up. From a portion of this suspension suspensions were ^.e

ions containing 100 ppm and 20 ppm of test compound, ⁿ

prepared by {serial dilution with sterile water, C

The test tubes containing 4.0 ml of melted potato extract- S

agar contained at about 50 ⁰ C, were with 0.5 ml of 500 pprc- Ϊ

Suspension of the test compound and 0.5 ml of the sterile * e

Fungi vaccine delivered by the syringe to achieve an ^e

Treated final concentration of the test compound of 50 ppm. The "t

Pipes that are 10 ppm. and contained 2 ppm of test compound, ^r

were similarly obtained from suspensions containing 100 ppm G

and contained 20 ppm of the test compound. Two ^A.

Tubes for the repeat were made with each Fungiopezies for ^t

inoculated at each concentration of the tea compound. Untreated control ^s role vaccinated ebcni'alln with each Funciqpezies.

C 0 9 ίί Ί '/ / 1 0 1 7

The molten medium in the tubes was then tilted and the agar allowed to settle. The tubes were then incubated (Helminthosporium avenae) at 25 ⁰ C in either 2 days (Alternaria solani, Dotrytis cinerea, Fusariuci sambucinum and Mycosphaerella pinodes) or 5 days.

The minimum effective concentration (MEC) was then determined the approximately 2/3 inhibition of fungi growth of each test compound against each fungus species.

test 5

Barley plants were grown in 3 inch diameter "whalehide" pots in Levongton stew compost. There were ten plants in each pot and these were sprayed with the test compound at a stage of growth where the first leaf was fully developed and the second leaf between 2.54 and 7.62 cm (between 1 " and 3") in height Amount was.

0.06 g of the test compound was ground in distilled water (containing 0.025% of a non-ionizing surfactant [Texofor FX 170]) using a Teflon block and mixed with distilled water to 100 ml to give a 0.06% w / v test compound containing suspension, from which suspensions were prepared by serial dilution with distilled water containing $ 0.02 and $ 0.006 w / v test compound. For each treatment, four pots were sprayed individually on a rotating turntable using a conical nozzle (at 20 cm vertical height from the turntable and 25 cm horizontal distance from the center of the turntable). Three revolutions of the turntable resulted in a deposit of 4.8 μΐ / cir. "On the plants without drainage. After the spraying, the plants were dried in the air, statistically advantageous and then immediately afterwards infected with spores of Erysiphe graminin (Gerctenmeltau) by shaking Plants inoculated over the bohr-r.dclton plants. ■ | ¹ on the -Moltau infection persisted for a time

6 0 9 B Ί 2 I 1 0 0 7

O j

develop in a space of 5-7 days, after which the number of

Deaf damage to the first leaves of all plants

"were determined for each treatment, with 10 or less ^

Damage per treatment as complete protection against ^e

the infection were scored. It became the percentage In ~

The hibition of the infection was calculated at each dose and the concentration of the test compound which gave a 90% inhibition ^e & ^{ε of} the infection (EDqq) was determined. ^0B-

Readers * .. t 'ere sporangia of a bi- H- 20-day al - ^ culture from isolation of Phytophthora infestans (later ¹ X) to a "held agar of half a pea,

used. Man

There were aqueous suspensions of $ 0.6, $ 0.3, $ 15 and ^ ^

0.06 $ w / vol test compounds contained by the test. ^

described method produced. _Paa:

. wur <

Leaves of tomato plants (of the kind Suttone «» es

of All «) on its ventral surface with the help of a" Po ^ r ^

Tower where 1 ml of a suspension of the test compound per BIa- ^

at 0.35 at (5 psi) pressure. One be ^

sprayed control leaves with a $ 0.025 aqueous Hb ^ _ige;

of only one non-ionizing surfactant (tester yes λ _(Te

After the Sprühablagerungen were dry, ν, the VEN ^ spectral surfaces of the leaves gestures by spraying with a Sun _(au pension of zoospores and sporangia of Phytophthora infeß ^ n ^ ₀ (about 250000 / ml) was inoculated to order the sporangia.. ^ burst to bring the suspension of fungi material before Aulbringen to the sheets 6 hours in a refrigerator at <been - rebracht ^ after the infection of each leaf was dorsal ^ with the surface downward in a separate Petri.. Kuns.stoll- ^ cup introduced (with a diameter of 9 cm), which was lined with a damp filter paper ^. These shells wur- ^. the ■ 5 * _pf then in an exposed. incubator of about 15 0 ^O ^ Days. 5 days after infection, the pool was

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est he"-

of each sheet covered with meltau damage was determined and the total percentage inhibition of the fungi infection was calculated for each dose in comparison with the infected controls which had only been treated with the non- ionizing surfactant (Teiofor SL190). The concentration of test compound that gave 90% inhibition of infection _{(EDg 0} ) was determined graphically by plotting the log of dose versus percent inhibition.

Test 7

Aqueous suspensions were prepared by the procedure described in Example 5 above, $ 0.06, $ 0.03, and $ 0.015 Teet compound contained.

Miniature beans (of the "Pinto" variety) were grown individually in "Whalehide" pots 10.2 cm (4 inches) in diameter a John Innes No. 1 compost and sprayed it with a Test compound at a stage of growth at which the first pair of first leaves were fully developed. Per treatment 4 plants were used for replication.

The bean leaves were on their dorsal surface as in t

Test 5 described sprayed with one rotation of the turntable. The control plants were only given a $ 0.025

" _N \ igen aqueous solution of the non-ionizing surfactant 1 (0",

(Texofor FX 170) sprayed.

One mixed spores of Uromyces appendiculatus (bean brandy) (kept on garden bean plants, on which it was in free form Spores) with talc substitutes in a ratio of 100 parts by weight of talc substitute to 1 part by weight of uredospores.

The leaves of the test plants were at their dorsal upper 3al

Immediately after the spray composition of the test compound was dried, areas inoculated with the above-described mixture of the Taürrersafcr.raittelo and other sporiculate matter. In the connection ά: \ ί:. < Ι:; .- ^ · - ;;; vurdiin the

Plants in a genättifion V: .v ^ 'T.h; lr? wl-hrer / l "M '-'turr'e · hey

_at 15 ⁰ C and kept one before being distributed in ^^^^ Ι-οΙι “orden, relative humidity of 60 - 80 / δ staxi

α λιρ covered with burn pustules

Ten days after vaccination was the m _tinhiM tion of leaf area and the percentage ^ ^ infected .ungiinfektion for * "* ™ **% ^ _ht ionizing controls only reckoned with.

It became the focus of the
one **-!*. ^ «-«

the logarithm of the dose versus the
graphically applied.

The in, en Tests *, ₅ , 6 and 7 even bear markets are shown in Table IV below.

609832/1007

- 18 -

a T) e 1 1 e V

Test - Test 4 * - B.c. Ha. F.s. of the test link - 10 2 2 M.p. In vitro activity: MaC
Compound (ppm) - > 10 10 10 > 10 c A. s. 10 10 10 10 E. 2 - 10-50 2-10 2-10 10 F. - 10-50 2-10 2-10 2-10 U - I. 10-50 10-50 2-10 L. - 2 <2 2 2-10 M. - 10 2 <2 2 A. - I. I. 10-50 10 D. - I. I. I. I. G I. I. I. I. I. I. 10-50 I. I. J I. 10-50 I.
f I. K 2-10

609832/1007

2603364

Table IV continued:

Test-
link ι "
In vi-t Test 4 Ha. IEC des
) Testing A.s. ; ro activity: I.
Compound (ppm 10-50 F.S. M.p. O - B.C. 10-50 I. I. P. I. 2-10 I. I. Q - I. - 10-50 10-50 V - I. Z - H - - 50 10-50 2-10 Z I. I. <2 I. . I. R. <2 I. 10 <2 <2 S. 10 <2 10 > io > 10 T 2 > 1O ² 10 10 B. ² 10 10 > 10 > 10

603832/1007

Table IV continued:

L D 'J

Test-
ver
am-
manure • η Test 5 Test 6 Test 7 ι C. A. Protective effect ge
compared to barley
'Meltau ED _gQ
(^ Concentration
the toast connection
manure) Protective effect
.compared to lateea
Msltau at To- I
maten ED q _Q
(fo concentration
the test connection
manure) Protective effect ge
compared to beans
brand EDqq
(^ Concentration
the test connection
manure) E. D. «0.06 ~ 0.06 P. G 0.02 0.06 U I. 0.016 I * - J I ** <0.6 K 1*. I * - H ^ 0.06 0.06-0.15 - 0.3 I. I ** 0.6 - I ** I * - I ** 0.06-0.15 - I ** 0.06-0.15 - I ** 0.06-0.15 I ** Ο, «",

6 Ό ^ι 3 L ⁵ i. / "ι CC 7

Table IV continued:

In d <the j

Test-
ver '
am
manure Test 5 I. Test 6 Test 7 O Protective effect ge
compared to barley
Meltau ED _go
[^ Concentration
dex test conn
manure) Protective effect ge
compared to late
Meltau at To
mat EDq ₀
(^ Concentration
the test connection
manure) Protective effect ge
compared to beans
brand ED _go
(56 concentration
the test connection
manure) P. I ** I * - Q 0.6 - V <0.6 - H - '<Ο. 6th - Z I ** 0.06-0.15 R. I ** «0.6 - Ü I ** 0.06-0.15 0.033 T I ** I * - B. I ** I * - -

The one ent!

Gem; before, and Ver meh for Ver

Fe a at dae ent

ZUE

609S32 / 1Q07

Ge <

In Table IV above, the various symbols have the following meanings:

> means that at the highest dose tested

an effect of less than $ 90 was obtained. <means that at the lowest dose tested

an effect greater than $ 90 was obtained. X means that in the only dose tested one

Effect of $ 90 or more was obtained. I means that the test compound was inactive at the highest concentration tested (50 ppm). I * means that the test compound was inactive at the highest rate applied ($ 0.6).

I ** means that the test compound was applied at the highest Rate ($ 0.06) was inactive.

- means that the test compound is not in this test was used.

non-ionizing surfactant "Texofor PX 170" is ) ®ia Honylphenoläthylenoxidkondensat, which contains 17 moles of ethylene oxide ©.

: According to a further feature of the invention are compositions i Intended for use to control insects i u & d Fungi are suitable and as an active ingredient at least one of the • Compounds of general formula I together with one or

& © h * ng with the compounds of formula I and acceptable '] Itir use in such compositions suitable diluents.

Compositions according to the invention suitable for use growing crops or for the growth of crop plants is suitable for certain places, contain at least one compound of the general formula I together with one or more solid diluents.

Suitable solid diluents include aluminum silicate, Kieselguhr, corn husks, tricalcium phosphate, powdered cork,

609832/1007

- 23 - Λ ^ or

I from λ

Absorbent charcoal, magnesium silicate, clays such as kaolin, bentonite are covered

or attapulgite and such solid compositions can emul *

if desired, one or more compatible network, DiBper- ^^ ^

contain greed, emulsifying or coloring agents that - if it aids

are solid - can still serve as a diluent. contains

simple ·

Such solid compositions, which are in the form of dusts, dark

Granules or wettable powders can be present in

generally by impregnating the solid diluent with Zrsa

Solutions of the compounds of the formula I in volatile solution form,

averaging, evaporation of the solvents and, if necessary, grinding ^ _{m B (of} the products to obtain powders and, if desired, granulation of the products to produce granulates .;

! ande The wetting, dispersing and emulsifying agents that are used in particular in ί

wettable powders may be ionic or.; ^ be non-ionic type, such as. Sulforicinoleate, quaternary _cn en ammonium derivatives or products based on condensates "bed

have been making d soluble overall _vervi or mixtures of these types of agents: ethylene oxide with nonyl- and octyl phenol, or carboxylic acid \ _geme esters of anhydrosorbitols that by etherification _of the free _(J ^ _U hydroxy groups by condensation with _Äthylenox?.

Wettable powders according to the invention can be used immediately before their

Use with water to achieve ready-to-use

Suspensions are treated,

^K of

korn ¹ Liquid compositions according to the invention for application _,.

For crops that are growing and for

org the growth of crops certain places can be in

Form of solutions, suspensions and emulsions of the compounds

of the formula I are present, which are preferably wetting, dispersing or

V S-Tt

Contain emulsifiers. These emulsions, suspensions and,

Solutions can be prepared using aqueous, _ß

organic or aqueous-organic diluents, such as e.g.

Acetophenone, isophorone, toluene, xylene and mineral, tie- _. or vegetable oils (and mixtures of threefold thinner.

medium), the wetting, dispersing or emulsifying agents of the ionic,

609832/1007

or non-ionic type or mixtures thereof, see B. such of the type described above. Desired case the emulsions containing the compounds of the formula I can be used in the form of self-emulsifying concentrates that the active ingredient in dissolved form in the emulsifying agents or in solvents containing emulsifying agents which are compatible with the active ingredient, whereby the simple addition of water to such concentrates is usable Compositions results.

Compositions which are suitable for the formation of aerosols containing the compounds of SOrsaol I are also ^{within the scope of} the invention.

^{; el} ^ * 'l Gswünschtenfallo the inventive compositions may' contain other adjuvants such as binders or Adhesiva.

^ ^he .! The above for the application in growing- »ares ■ ;. _cnen crops and on for the growth of crops

: Specific locations compositions described may in general} common alternative for topical use in animals, and i for ^one protective use of stored products and household goods as well as wood \.

^{? s} The inventive compositions may also contain adjuvants. The compositions mentioned can contain mixtures of auxiliaries and compounds of the formula I in the form of combined formulations or as tank mixes. ^g Examples of such excipients include insecticides such as organic Phosphorester such as parathion, ie 0,0-diethyl-O-4-nitrophenyl-pho8phorothionat, T-lalathion, ie S- [1, 2-di- (Λthoκy ^een carbonyl) - ethyl] -0,0-dimethyl-phonphorothiolothionate, ^or Varaidothion, ie CO-Dimethyl-Si ^ -Ci-methylcarhainoyläthyl-thio) -

-phonphorOthiolat, Dia?,. inon, ie 0,0-diethyl-0- [2 ~ isopropyl- '♦ 6-methyl-4-pyrimidinyl] -phosphorothlonat, Monocrotophos, ie "^ * 0,0-Dimethyl-cls- 1-methyl-2- (N-me-1: hylüarbaraoyl) -vinyl-phosphate ^,! ~ Dimethoat, ie ö, O-dimethyl-S- (N-ne!; H.yloar ^ aiaoyltnethyI) -lnungf -phoaphorothiolothionat, Vhcc, al ι η, dh? - (6 - Ch] .or-r-oxc-

'Ctrhe * ι -,, ι τ> l Λ 1 Γ '< A '' ■ i I. . · ■ · -Ήλ, ■ i-, »., 'V i .1. .1.1 -, · -_. .. ι

-Β " ¹¹ hnti7.ri7-. 'I ZOTin — 3 ~ * y 1) -HGtHy J - ν- ¹ ,' —Q ■ '■■' '<' ^ ¹ '· *")' H ^ i! >> · 'Ol ( -Λιλ. \: I iM,! Ij, OTKi.>.,

2603364 -25- C // '

Bromophosethyl, ie 0- (4-bromo-2-, 5-dichlorophenyl) -0,0-diethylphosphorothionate, carbamates, for example carbaryl, ie 1-haphthyl-W- methyl carbamate, formetanate, ie 3- (dioethylaminonethylenimi .; o) - -phenyl-li-iaethylcarbamate, pyrethrins (natural and synthetic), e.g. bioallethrin, chlorinated hydrocarbons, e.g. DDT, i.e. 1,1,1-trichloro-2,2-bis- (p-chlorophenyl) -ethane, and their mixtures with their o, p'-isomers, BHC, ie mixed. Isomers of 1,2,3,4,5,6-hexachlorocyclohexane, toxaphene, i.e. camphechlor (an isomeric mixture of chlorinated camphenes containing 67-69% chlorine), dichlorobenzene, methyl bromide, ethylene dibromide, acaricides, e.g. quinomethionate, i.e. 6- Methyl-2,3-quinoxalinediyl-cyclic S, S-dithiocarbonate, dicofol, ie 2,2,2-trichloro-1,1-bis (p-chloropbenyl) ethanol and tetradifon, ie 2,4,4 *, 5-tetrachlorodiphenyl sulfone, non-insecticidal compounds such as the synergistic methylsndioxyphenol derivatives, for example piperonyl butoxide, ie 5- [2- (2-butoxyethoxy) ethoxymethyl] -6-propyl-1,3-benzodio ^ ol, sesamex, ie 2 - (3,4-methylenedioxyphenoxy) -3,6,9-trioxaundecane, 0,0-dimethyl-O-phenyl-phosphorothioate, fungicidal compounds, e.g. copper sulfate, dinocap, ie a mixture of 2,6-dinitro -4- oitylphenyl crotonates and 2,4-dinitro-6-octylphenylcrotonates ("Octyl" means the isomeric radicals 1-methylheptyl, 1-ethylhezyl and 1-propylpentyl), chloroxylenol, i.e. 4-chloro-3,5 ~ xylenol, ₍ methylthiophanate, i.e. 1 , 2-bis- (3-methoxycarbonyl-2- thioureido) - ^ -benzene, dichlorophene, i.e. bis- (5-chloro-2-hydroxyphenyl) -methar and thiram, i.e. tetramethylthiuram disulfide, preparations of ₃

Bacillus thuringiensis (toxins and organisms) and insect viruses. ₍

Many such auxiliary connections are state of the art well known. The only requirement is that it is compatible with the compounds of formula I and with other components of the Composition should be compatible.

The compositions according to the invention generally contain γ

between 0.001 and 95 wt ^ cyclohexadiene derivatives of the research _ε

mel I and are used in such a dose that according to _e

the imagination of the farmer, veterinary or any _β

other expert according to the species of the respective pest γ lings and the nature of the crop to be treated, area, des

609832/1007

rc ^260386;

_the animal to be treated, the stored product or the household goods to be treated, the desired effect is achieved. Solid and liquid compositions for application in itself) "" in the growth of crops and located for the V / grow th of ^e)> crops certain surfaces, for topical application

goods in animals in timber and stored products and household ^a "and whose environments contain generally between 0.001 and 60, in particular between 0.01 and 10 wt .- ^ cyclo bexadienderivate of formula I.

Another feature of the invention is a method for the control of insects and fungi and for the protection of crops, animals, wood, stored products and household goods by administering at least one of the cyclohexadiene derivatives of the formula I in the manner described above.

Methods of Interest include: A method of protecting corn, tobacco, cotton and cabbage plants from caterpillars by the application of a compound isr formula I in a dose of between 10 and 2000 g / ha, preferably in the form of a composition, e.g. a spray, Si © contains between 0.001 and 2.0% by weight of the compound of the formula I.

A method for protecting field crops, e.g. maize, Bauntwoll®, rice or potatoes and vegetables, e.g. _{beans or GwEtQU 9} against herbivorous beetles or beetle-like beetles and weevils, grain beetles or seed beetles by using a gate binding of the formula I in a dose of between 100 and 5000 g / ha, preferably of a composition, for example in the form of a crack or dust, which contains between 0.01 and 2.0 Gßu .- # compound of the formula I and an ancestor for the protection of Cotton, sugar cane and fruit trees against the attack of sucking insects or Sohmarotzorn by using a compound of the formula I in a dose of 100 to 2000 g / ha, preferably from a Zucanmonoctzung, for example a spray, between 0.01 and 5.0 Qew .-? Compound of formula I contains.

6B9832 / 1Q07

260386;

According to a further feature of the present invention, articles of manufacture are provided which contain at least one of the cyclohexadiene derivatives of the formula I or, preferably, an insecticidal or fungicidal composition, as described above, and preferably an insecticidal or fungicidal concentrate, which before its use must be diluted and to- D: contains at least one of the cyclohexadiene derivatives of the formula I _; - / in a container for the above derivative or the derivatives of the general formula I or the insecticidal or fungi e: contain cidal composition and instructions for the s; The aforementioned container indicate the manner in which the said (s) o <compound (s) of the general formula I or insecticidal or Nj fungicidal composition contained in this are to be used for the control of insects or fungi. The proportions are generally of the type customary for the storage of chemical substances which are solid at ambient temperatures and of insecticidal and fungicidal compositions, especially in the form of concentrates, and are ι b, such as metal cans or -büchsen and drums, the j ζ may be internally lackieret and plastics materials, bottles of glass \ a and plastics materials and, when the material in \ P the container is a solid, for example a granular insecticidal \ ~ and fungicidal composition, they can boxes or,! ■ be boxes or cans, for example of cardboard, plastics materials and metal, or sacks ^H j. The containers generally white. j ο sufficient capacity to contain the amounts of cyclohexadiene j ° derivatives or insecticidal or fungicidal compositions j necessary for the treatment of at least 4050 m (1 acre) j ° ground, of at least one animal, at least one stored product; domestic product or Hausheitsgut, including at least one con- Teppichjzur \ E troll of diseases associated with these insects or fungi suffi- β heights, but they do not exceed the size that is common for conventional methods of treatment j. The instructions are preferably j directly connected to the container, for example by: being printed directly on it or on a label attached to it or a tag attached to it. The To->'instructions typically specify that the contents of the container after dilution if necessary to control insects

609832/10 0 7 ■

26Ü38G4

and Fungi is to be used in the manner and for the purposes described above.

The invention does not include compositions containing 2,6 ~ dibromo -. ^ - hydroxy ^ -methylcyclohexa ^^ - dienone or 2,6-dichloro-4-aydroxy-4-methylcyclohexa-2,5-dienone together with Yiasser or a common organic solvent, e.g. ethanol, acetic acid, Acetic anhydride, benzene, diethyl ether, petroleum ether

S or ligroin, alone or in the presence of sodium acetate, sodium hydrogen carbanate, sodium carbonate, sodium hydroxide, Contain potassium hydroxide, nitric acid, sulfuric acid, hydrogen chloride, hydrogen bromide or zinc chloride; the 4-acetoxy-2,6-dibromo-4-methylcyclohexa-2,5-dienone together with methanol,

ι dilute aqueous acetic acid solution or acetic anhydride

η contain alone or in the presence of sodium acetate or zinc dust; the 4-acetoxy-2,6-dichloro-4-methylcyclohexa-2,5-dienes together with ethanol or acetic acid or acetic anhydride alone or in the presence of sodium acetate or benzene or Contain petroleum ether; the 2,6-dibromo-4,4-dim8thylcyclohexa-

Q -2,5-dienone together with water or a customary organic Solvents, e.g. diethyl ether, petroleum ether, cyclohexane, hexane, carbon tetrachloride, pyridine or 2,4,6-collidine alone or in the presence of bromine, hydrogen chloride, sodium bisulfite or sodium hydrogen carbonate or contain the 2,4,6-trichloro -4-tert-butylcyclohexa-2,5-dienone together with chlorine, acetone or contain hexane.

The following examples explain the compositions according to the invention:

260386;

example 1 ^m>

A wettable powder is produced: ^{n #}

^ -Acetoxy ^ o-dibromo - ^ - methylcyclohexa ^^ - dienone 50 % w / w. h <

Ethylan CP (octylphenol-ethylene oxide condensate) 2.5 % weight / weight e:

and -J ¹

Celite PF (synthetic magnesium silicate) 47.5 % w / w a; by dissolving the Ethylan CP in a minimal volume of acetone

and the resulting solution to a stirred mixture of Cyclo Bj

Add hexadiene and Celite PF and put the product in an ^E:

Milled corrugated mixer. The wetted ^ -

bare powder can be suspended in water and placed in a 2.

Dose of 2 kg in 1000 1 spray fluid per hectare for control ^E '

of Heliothis virescens can be applied to maize. ^

Example 2 * ■ '■

An emulsifiable concentrate is prepared from: ^E

2,6-dibromo-4-hydroxy-4-nethylcyclohexa-2,5-dienone 10 % w ^{/ v o1} · ^R Duoterics MB1 / MB2 (mixture of anionic and ^a

non-ionic emulsifiers, the calcium ^w

alkylarylsulfonates contain) 10 % w / v ⁰ * · ^d

and S.

1: 1 v / v mixture of cyclohexanone and

Aromasol ¹¹ H "(an aromatic solvent that I

contains isomeric trimethylbenzenes) to achieve ^

from, '100 Vol.-96 '

by using the cyclohexadiene and duoterics MB1 / MB2 '

if necessary with heating in a proportion of the ^]

Mixture of cyclohexanone and Aromasol "h" dissolves and then the remaining part of the mixture of cyclohexanone and Aromasol "H" is added with stirring. That on this Emulsifiable concentrate obtained in this way can be diluted with water and ground in a dose of? kg of cyclohexadiene derivative in 500 1 spray fluid per hectare to control 'Ragoletis pomonella on apples.

6C9832 / 10Q7

- ⁷ JO-

260386;

3ew
} ew

A similar e _m u _lg ierbares concentrate

"earth. By reacting the _{2, 6-b} ro _m Dl _{-4-hydroxy-4-m} ethyl oyolo- TEL ₂ 5-dlenon by -Dlbro ^ ^ -methoxy ^ ethyl -cyclo hexa-2-5 dlenon replaced, diluted with water and this In

he; L _iS of * U. Cyclohex ^ lenderlvat in 500 X Spra ,, u per hectare for the control of Phytophora Infestans on potatoes] ew. applies.

Example 3 . _ΊΊ . _β11β .

A water soluble concentrate is made from.

; , -Acetoxy-ae-di.rom- ^ ethylcyclohexa- ^

2.5 dlenon

Ethylan TU (Nonylphenol Ethylene Oxide ^ ^ ^

Condensate) ^

sr: tis

Heat in a portion of the cyclohexanone, dissolve and then, while stirring, the remaining portion of the cyclohexanol i """tf. £ · «... rloellol» concentrate obtained on these catfish can be diluted with water and applied in a dose of 2 K ₈ ^ Ιοη. »- dlenderlvat in 2000 1 spray fluid per hectare to control Spodoptera llttoralis on cotton.

Example 4

Granulates are produced from:

2,6-di-bromo-4,4-dimethylcyclohexa-

5% Gew./G ^ew · 2,5-dienone

Waxoline Red OS [4-o-TolylaiO-o-tolul-

, 0.2 # w / w and

dln-2-naphthol]

15/30 attapulgite (sorptive silica clay) granules 9 ^, 8 ft ^ 'by the cyclohexadiene and Waxoline Red OS paint Men In _ß e acetone dissolves, then the acetone solution on granules sprUht or drip IMT. stirring and then allowing the acetone to evaporate with constant stirring. The granules obtained in this way can be used in a dose of 5 _kß active ingredient per hectare for the control of Ostrlnia nubilalis on maize.

609832/1007

Example 5

An oil suspension concentrate is prepared from: 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dlenone 40 % wt.

Ethylan TU (nonylphenol-ethylene oxide condensate) 10 Si wt.

Bentone 38 (magnesium montmorillonite derivative) 0.5 # wt. Aromasol "H" (isomeric trimethylbenzenes-containing aromatic solvent) to achieve of 100 Vol.-Ji by adding the cyclohexadiene and ethylan TU with stirring dissolves in a portion of the Aromasol "H". Bentone is added and the mixture is stirred until the Bentone 38 is complete is dissolved and the mixture has reached a constant viscosity and then gives the remaining part of the Add Aromasol "H". The oil suspension concentrate obtained can be used alone or after dilution with 50 1 kerosene in one dose of 2 kg of active ingredient per hectare by spraying in the air to control foam chirps, e.g. Aeneolamia spp. on sugar cane be applied.

Example 6

An aqueous suspension concentrate is prepared from:

2,6-dibromo-4,4-dimethylcyclohexa-

and

50

2.5

o, 1

Weight ^{A o1}
Weight ^{A o1}
Gev: .A ^o1

2,5-dienone Ethylan CP (octylphenol-ethylene oxide condensate) Methofos CM 125 (carboxymethyl cellulose thickener)

Deionized water to achieve 100 # by adding the cyclohexadiene and ethylan TU with stirring to suspended a portion of the deionized water. One adds Add Methofos CM 125 and stir the mixture until the Methofos CM 125 has completely dissolved and the mixture becomes one has reached constant viscosity and then adds the remaining part of the deionized water with stirring. That on Aqueous suspension concentrate obtained in this way can be used in

^and

Water 200 1 and Ai

Belsp

Man s

befin

the π

table *

: to egg

barely

; stel

¹ Scha

to the

Ins

At ■ Man 2,6-

2.5 ice a valley sil

i; Dei Erl

'5 l each

kt d (UI a

609832/1007

2503864

Suspended Water and In a Dot; Ir. from ', V * r. Active ingredient in 200 1 sprayfluld / na to control Heliothi, virencena and Anthonomus r ^ ndls can be used on cotton.

Example 7 . .

It provides a foam for use in in growth that are available crops such as Saumolle and Hol, prepared by mixing 1 i VolAol Perlankrol ESD-60 (sodium salt of a synthetic primary Alkoholäthcrsulfats - a schaumblldendes Hlotel) to a dilution of a wettable powder, a emulglerbaren concentrate or water-soluble concentrate, such as _e forth like estellt "example 1, 2 or J.zur obtain a foam admits of s for the control of Insektenschadlin _B, for example, is applied to control the egebenen in examples 3 and 6 to _e Insektenschädllngon .

Example 8

One produces a dust or a powder:

² ' ⁵ - ^dlenon 1 * oew / oew and

Elsenic oxide

a 2:! mixture based on the weight of superfine ^ Talc and light kaolin (synthetic magnesium and aluminum silicates) to achieve 100% by weight.

The dust obtained in this way or the powder obtained in this way can be used in Halssanen in a dose of 5 to 200 g, preferably 50 to 100 g of the composition, ie 25 kg of seeds to protect the species against (Agrotis spp.) will.

A similar dust or powder containing 30 % Gev, /; ew 2 e-dibromo ^ -i.ethoxy-t-methyl-cyclohexa-aS-ilenone.

'°. _pU . " _Nd " el wheat seeds in a dose of 2000 g can be produced una ati

, »R, ₀ nl ^ K Swen to protect the Snnwin ncfcn-

be applied.

6 0 ^f J 3 3? / ^ G 0 · '

2 ü ü "J 3 ti

The active ingredients in the formulations described in Examples 1, 4, 5 * 6 and 8 can be replaced by a similar mer. ~ E on another compound of the general formula I. The Förrr.u- described in Examples 2, 3 and 7; Formulations can be prepared by suitably adding an analogous amount of 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone, 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dienone , 2,6-dibromo-4-methoxy-4-methylcyclohexa- ^{2,5-dlenone and} 4-acetoxy-2,6-dibromo-4-methylcyclohexa-2,5-dienone are used.

i Cy (The cyclohexadiene derivatives of the general formula I can, |

be made by the following processes: j

1 2 'ΓΟ1

1.) For compounds of this formula in which X and X have the same } _y

Have meaning and each represent a chlorine or bromine atom. ο {the

and R is an alkyl radical, by reacting a |

J Brc cyclohexenone of the general formula J

ο I

1 2 'fwn

(where R has the meaning given above and R v ^where

a straight-chain or branched alkyl radical with 1 to 6 · ^sit

Carbon atoms means) with chlorine or bromine in a ■ ^{Z # B}

inert organic solvent, e.g. a chlorinated Tem

Hydrocarbon, e.g. chloroform, at a temperature of ^Beh

0 to 50 ⁰ C and treatment of the product after isolation]

with a liquid organic base, which acts as an acid-binding V>

Agent acts, preferably a collidine at elevated temperature, "j preferably at the boiling point of the mixture. The reaction can, given- J?

if In a solvent medium such as a hydrocarbon? |

substance (e.g. benzene) or dry acetone. ^; | ( ^where

The organic base in turn can be used as a solvent medium | ^a

to serve. , | ^ste

I an I ums'

• '^;-'i

609832/1007 ^

260386Λ

pie Reaction of the cyclohexenone with chlorine or bromine can take place in the presence of a catalyst, e.g. iodine, and with irradiation the reaction mixture can be carried out with artificial light. If these conditions are applied, the implementation preferably carried out at 0 ° C and the preferred solvent medium is carbon tetrachloride. The procedure is particularly applicable when chlorine is used.

In the absence of a catalyst, the reaction of cyclohexenone with chlorine or bromine is preferably carried out at 10 to 20 ° C. and the preferred solvent medium is chloroform. Bromine is preferred under these conditions. 2.) In the case of compounds of the general formula I in which X and X have the same meaning and each represent a chlorine or bromine atom and R ² denotes an alkyl radical, by reacting a cyclohexanone of the general formula

III

1 2 ¹

(wherein R and R have the meaning given above) with chlorine or bromine in an organic solvent, for example an alkanoic acid, preferably acetic acid, at a temperature of 10 to 50 ⁰ C, preferably 20 to 50 ° C and treatment; of the product of the general formula obtained

X ¹ '

IV

1 '1'

(where the symbols X have the same meaning and X

represents a chlorine or bromine atom and R and R have the meaning given above) with a liquid organic base that acts as an acid-binding agent, preferably a Kollldin, at elevated temperature, 2.Π. 100 to 105 ° C. The implementation can, if necessary, in a medium medium such as

609832/1007

hydrogen (e.g. benzene) or dry acetone. The organic base on your part can _al . Serve solvent medium.

This process is particularly suitable for manufacturing of any compounds of the formula I. wherein X and X?

Represent brora atoms. "" _4_ _a 2 "

5 ·) In the case of compounds of the general formula I in which R_ denotes an AlLy radical, by reacting an alcohol. H OH (where R ² 'has the meaning given above) and ChI ₀₁ . or bromine with a phenol of the general formula OH

Old * grain 10 ° C aiii

(wherein X ^1, X ² and R ¹ is as hereinbefore defined) at a temperature of 0 to 5O ⁰ C, preferably 10 to 20 ⁰ C, optionally in the presence of an inert organic solvent but preferably in the presence of an excess of alcohol which serves as a solvent for the reaction. Instead of chlorine or bromine, a halogenating agent such as N-bromosuccinimide, N-chlorosuccinimide, a dioxane-bromine complex; Pyridinium hydrobromide perbromide or pyrrolidone hydrotribromide can be used.

4.) For compounds of the general formula I in which R is a hydroxy radical, by treating a compound of the general formula V with fuming nitric acid (specific density ■] ( _R 5 ₍ 1.51)) in an inert organic solvent such as a chlorinated hydrocarbon , preferably methylene chloride, at a temperature of 0 to 50 ° C, preferably 5 j and 20 ⁰ C, j _ode i eg over a period of 1/2 hr., and then. _un t "heating the reaction mixture, preferably at the boiling point. , eg \ during a period of 3Λ up to 1 hour, in order to obtain a compound which falls under the general formula I and has the general formula: · \

G09832 / 100V

(woi si ts

Gegc a «

Lor

VI

OH

12 1

wherein X, X and R have the meanings given above.

Alternatively, a compound of the general formula V with ■ j tconz. Nitric acid (specific gravity 1.42) in glacial acetic acid at 0 to ί 10 ° C are treated and the intermediate product obtained

_χ 2 general formula

VII

12 1

(wherein X, X and R are as defined above) in an inert hydrocarbon solvent (preferably benzene), preferably at the boiling point of the solution, to achieve a compound of the general Formula VI are heated.

1-

.B. nd

In both of the above alternatives, a further reaction of a compound of the general formula VI with an alkanoic acid chloride R ^ COCl or an alkanoic acid anhydride (R ^ CO) g0, in which R ^ has the meaning given above, in the presence of a base such as a sodium alkanoate (e.g. sodium acetate) or an organic base such as triethylamine or preferably pyridine, to obtain a compound that falls under the general formula I and the general formula:

VIII

OCOR

609832/1007

" ⁵⁷ " ^% '260386;

1 ? 1 "*>
has, wherein X, X, R and R ^ have the _{meanings given above O} q », connect. The implementation can be given- B _a . if carried out in a solvent medium such as a hydrocarbon 8. (e.g. benzene) or dry acetone. The R ² organic base, in turn, can be used as a solvent medium pH <

to serve. i voi

6.) For those compounds of general formula I, \ All

Ο £

where R represents an alkanoyloxy group, by reaction \ bei

a compound of the general formula V with a lead J we;

■ χ · χ I

tetra-alkanoate Pb (OCOR ^) ^ in an alkanoic acid R-TOOH, where j spa

P? has the meaning given above or in a | Dej

inert organic solvents, e.g. benzene, to achieve I and

a compound of the general formula VIII. Ä Ub <

7.) In those compounds of formula I in which R ² % im

means a hydroxy radical by reacting a heavy metal < 10

salt, preferably a silver salt, e.g. silver nitrate, in each case

in an inert water-miscible organic solvent / I mec

preferably dioxane and water with a cyclohexadienone of the f Nat

general formula \ cat

P 'j practice

I the

_xv I Aue

J How

12 1 * ^cor

(wherein X, X and R are as defined above? _aui

own) at a temperature of 0 to 100 ⁰ C, preferably \

10 to 20 ⁰ C, optionally with the connection of a further i _and

Implementation of the product obtained of the general formula VI Ϊ " _a "

■ χ gerr

with an alkanoic acid chloride R ^ COCl or an alkanoic acid q>

anhydride (R ⁵ CO) ₂ O, in which R ^{5 has} the meaning given above; _χ ί has, in the presence of a base, for example a sodium alkanoate (for example sodium acetate) or an organic base, for example triethylamine or preferably pyrldine, to obtain a compound of the general formula I in which R ^ is an alkanoyloxy group. The implementation can optionally in one

609832/1007

Solvent medium such as a hydrocarbon (e.g. benzene) or dry acetone can be carried out. The organic ^ien "Base in turn may serve as a solvent medium.

' 8.) In those compounds of general formula I in which

p
R represents an alkoxy radical by anodic oxidation of one

12 1 phenol of the general formula V (in which X, X and R are the Have the meanings given above) in the presence of a

; Alcohol R OH (wherein R is as defined above; has) in a divided or undivided cell untör rejuvenation turn an inert anode with a high voltage SauerstoffUberj, _Z .B. Platinum, platinized titanium or carbon. Can be) The anolyte in the case of a divided cell or in the case of \ undivided cell, the electrolyte, optionally containing one j excess of the alcohol, but preferably a ι Inert polar solvent, for example acetonitrile, at least \ 10% v / v alcohol contains , should contain an inert salt of an inorganic acid which should be soluble in the reaction medium, preferably lithium perchlorate or sodium perchlorate. In an undivided cell, the: cathode should be an inert material with a low hydrogen overvoltage, e.g. platinum. In a divided cell, the nature of the cathode and catholyte is not essential except that they should be inert and have low resistances. The current density can

ρ
1 to 100 mA.cm or the conversion can be at a controlled potential, for example from 0.7 to 1.3 volts, with respect to a mercury / mercury chloride / potassium chloride / calcium perchlorate / 0.1 molar sodium perchlorate-in-acetonitrile electrode and at an initial concentration of the phenol of the general formula V of 0.01 to 1.0M.

9.) (1) For the compounds of the general formula I in which X ¹ , X ² and R ² each have a chlorine atom (
of a phenol of the general formula

1 ? P.
X, X and R each represent a chlorine atom by reaction

609832/10 0 7

rf

260386;

(in which R ^{1 has} the meaning given above) with chlorine in an excess of three equivalents in an inert organic solvent, for example a chlorinated hydrocarbon, for example methylene chloride, at a temperature of 0 to 50 ° C., preferably 0 to 10 C.

(ii) In the case of those compounds of the general formula I in which X and R each represent a chlorine atom, by reaction of a phenol of the general formula

OH

XI

^R.
(wherein X ¹ and R have the meaning given above) with chlorine, namely two equivalents, in an inert organic solvent, for example a chlorinated hydrocarbon, for example methylene chloride, at a temperature of 0 to 50 ⁰ C, preferably 0 to 10 ⁰ C. .

(iii) For those compounds of the general formula I in which R represents a chlorine atom, by reacting a phenol of the general formula V with chlorine, namely one equivalent, in an inert organic solvent, for example a chlorinated hydrocarbon, for example methylene chloride, at one temperature from 0 to 50 ⁰ C, preferably 0 to 10 ⁰ C.

Optionally, at the above three methods bine further reaction of the resulting compound of formula I (a) mLteinem heavy metal salt, preferably a silver salt, in an inert water-miscible organic solvent, preferably dioxane and water, at a temperature of 0 to 100 ⁰ C, preferably 10 to 20 C, and optionally a further reaction of the compound of the general formula VI obtained to obtain a compound of the general formula VIII described above, or (b) with an alcohol η OH (in which R

the V

rature

rather

Erzic

one

gel

mitt <

Opposition

for

beso

the

Vert or hex- & K, her <

Verl ode hex & K her

ι
[

S Vei

i VOI

ι before

I. (WC

I. sii

I. Fo:

• dei

? It

ί ²⁰

^: Ve ar ai

609832/1007

Sl

260386 ^

the meaning given above buckles) at a temperature from 10 to 16O C, 'preferably and generally more usual at the reflux temperature of the reaction mixture

2 Obtaining a compound of the general formula I in which R

represents an alkoxy radical, connect. The implementation can optionally carried out in the presence of an inert organic solvent, but it is preferably carried out in Presence of an excess of the alcohol acting as a solvent for the implementation is carried out. This procedure is; particularly suitable for the production of those compounds • of the general formula I, in which R is a methoxy radical.

; Compounds of the general formula II can by application or transfer of substituted cyclohex-2-enona for the production known methods, as described, for example, by F. Bordwell & K. Wellman in J. Org. Chem. 28, 25 ^ 9 (1963), getting produced.

: Compounds of the general formula III can by application or transfer of substituted cyclohexanones for the production known methods, such as those used by F. Bordwell

^; & K. Wellmann in J. Org. Chem. 28, 25 ^ 9 0962).

Compounds of the general formula V (in which R, X and X have the meanings given above) can be prepared by reacting zinc powder with a cyclphexadienone of the general formula I (in which X ¹ , X ² and R ^{1 have} the meanings given above and R is a chlorine atom represents) or the general

11?

Formula IX (in which R, X and X have the meanings given above possess) in an aqueous alkanoic acid, preferably acetic acid, at a temperature of 10 to 100 ° C., preferably 20 to 55 ° C.

Compounds of the general formula V (in which R the above

12 has the meaning given and X and X have the same meaning and each represent a chlorine or bromine atom)

609832/1007

by reacting a phenol of the aU ^ e r.en For, X (in which R ^{1 has} the meaning given above) mt - ,,. or or bromine, namely two equivalents, in an inert or,;, -. nlschen solvent, for example a ™ chlorinated hydrocarbon ^ rr, for example chloroform, at a temperature of 0 ⁰ C to the RucRfl.etemperatur the Reaktionemiechune and subsequent reaction of the corresponding CyclohexadienonPder formula I or IX, when ^ forms expectant described above with zinc powder for of compounds of the general formula V are produced.

Compounds of the general formula V (in which R ^{1 has} the meaning given above and X ¹ and X ^ have different meanings and one of these radicals is a chlorine atom and the other is a bromine atom) can be prepared by reacting a phenol of the general formula X (in which R has the meaning given above) with either -chlorine or bromine, namely one equivalent of an inert organic solvent, for example a chlorinated hydrocarbon, z.3. Chloroform, at a temperature of ⁰ C to the reflux temperature of the reaction mixture and subsequent reaction of the monohalogenated phenol intermediate of the general formula XI with the other halogen, namely one equivalent, in an inert organic solvent, for example a chlorinated hydrocarbon, for example chloroform, at a Temperature from 0 ⁰ C to the reflux temperature of the reaction mixture. If necessary, the reaction of the corresponding formed cyclohexadienone of the formula I or IX, as described above, with zinc powder to obtain compounds of the general formula V can follow.

12 1

Compounds of the general formula IX (in which X, X and R have the meaning given above) can by applying or transferring the above for the preparation of the compounds of the general formula I, in which R represents a chlorine atom, are prepared. One A special transfer is the replacement of the inert organic solvent used here with glacial acetic acid.

609832/1007

^{η of} the general formula χ can by applying

«Under" Λ ^{& δυΩί2 are produced by known} methods. tf "known under the expression methods," as he is verwandet herein _{slnd methods 2U} ^^ _§ ^ _ ^^

applies or has been described in the chemical literature.

Compounds of the general formula Xl can be prepared

TZrTn ^ ^{rCh UmSet2Ung Gines Phenol of} the general formula X (where R has _the meaning given above) with chlorine or bromine, namely one equivalent, In an inert organic solvent, ₂ . _B. a chlorinated hydrocarbon, for example chloroform, at a temperature from ⁰ ° C. to the reflux temperature of the reaction mixture.

The compounds of the formula IX in which X ¹ , X ² _and R ^{1 have} the meaning given above are, with the exception of ^^, ö-tribromo- ^ methylcyclohexa-g ^ -dienone and 2,4,6-tribromo- ^ • tert-butylcyclohexa-2, _5- dienone new compounds that have not been described in the literature so far. Accordingly, the invention also includes, as new and valuable compounds, those cyclohexadiene intermediates of the general formula IX, in which X, X and R have the meanings given above, with the proviso that (i) when X ¹ and X ^{2 have} the same meanings and each represent a bromine atom, R ^{1 has} a different meaning than that of a methyl or tert-butyl group.

As will be apparent to the person skilled in the art, the compounds encompassed by the general formula ix can have at least one center of chirality, this center of chirality being on the carbon atom which has an alkyl * group R and bromine as substituents in compounds of the formula IX when X ¹ and X are not identical. Another center of chirality can occur at R. The presence of a chirality is known to lead to isomers. It goes without saying that if the present case refers to the use of compounds of the general formula IX as intermediates or to new compounds of the

609832/1007

Reference is made to Formula IX, one such reference is also intended to include all isomers of the general formula IX and mixtures thereof.

For example, the compounds described above can be prepared by the following reference methods and procedures will.

Procedure 1

9.0 g of 4,4-dimethylcyclohexa-2-enone were dissolved in 100 ml of chloroform and the mixture was stirred while 12 ml of bromine, dissolved in 60 ml of chloroform, were added. The mixture was left to stand at room temperature for 16 hours, poured into excess water and neutralized with saturated aqueous sodium hydrogen carbonate solution. About 500 ml of diethyl ether was added, the aqueous layer was removed, and the organic layer was washed with water, dried over magnesium sulfate and evaporated to give an oil. 150 ml of 2,4,6-collidine were added to this oil and the mixture was refluxed for 2 hours and left to stand at room temperature for 16 hours. The mixture was then poured into water and extracted with riethyl ether. The ether extract was washed with 10 # hydrochloric acid until it was free of collidine and then dried with water over magnesium sulfate and evaporated. Crystallization of the residue from acetone-petroleum ether (bp. 60 to 8O ⁰ C) gave, after treatment with active charcoal 6.5 g of 2,6-dibromo-4,4-dimethyl-cyclohexa-2,5-dienone with a mp. Of 149 to 15O ⁰ C.

That used as the starting material in the above manufacture 4,4-Dimethylcyclohex-2-enone was prepared according to F. Bordwell ft K. Wellmann, J. Org. Chem. 28, 2549 (1963).

Procedure_ g

A solution of 5.8 g of 2,6,6-tribromo-4,4-dimethylcyclohex-2-enone was heated in 59.5 ml of 2,4,6-collidine for 1 hour. at 100 to 105 ° C. the mixture was filtered off and the filtrate

609832/1007

2 6 0 3 8 fi 4

poured into 7 ¹ 5 nil 2N-5 hydrochloric acid. 700 ml of ethyl alcohol were added, the ethereal layer was separated and two with 100 ml of 2N hydrochloric acid were dried over Marnesite, sulfate. η evaporated to give a brown solid. Crystallization from ether-hexane (2: 1) gave 2.9 g of 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dlenone with a melting point of 143 to 145.degree.

That used as the starting material in the above manufacture 2,6,6-Tribromo-4,4-dimethylcyclohex-2-enone was prepared as follows:

JO g of bromine in βθ ml of glacial acetic acid were added dropwise to a stirred solution of 5 * 87 g of 4,4-dimethylcyclohexanone in 90 ml of glacial acetic acid at 25.degree. After the addition was complete, the solution was stirred for 3 hours, poured into water and neutralized with saturated aqueous sodium hydrogen carbonate solution. The mixture was extracted with diethyl ether, the extract was dried over magnesium sulfate and evaporated to dryness. The residue in petroleum ether (bp. 60 bis'80 ⁰ C) was dried in the presence of decolorizing carbon. The mixture was filtered off and cooled. The crystalline solid thus formed was collected by filtration and, after crystallization from hexane, gave 6.18 g of 2,6,6-tribromo-4,4-dimethylcyclohex-2-enone with a melting point of 48 to 50 ^° C.

That used as the starting material in the above manufacture 4,4-Dimethylcyclohexanone was prepared according to F. Bordwell & K. Wellman, J. Org. Chem. 28, 2549 (1963).

Purchase procedure 1

To a stirred solution of 432 g of p-cresol in 43ΟΟ ml of chloroform at room temperature, 445 ml of bromine dropwise.

After the addition of v.-urde the mixture for a further 5 hours.

stirred and then removed about 3000 ml of solvent by evaporation. The remaining solution was saturated with aqueous Sodium hydrop-.encarbonnt and then washed with water, over Magnesium sulfate dried and evaporated. The residue was

609B32M007

crystallized from petroleum ether (b.p. 60 to 80 ° C.) and gave 1 \ / c

971 g of 2,6-dibromo-p-cresol with a melting point of 45 to 48 ° C. with Γ

Reference method 2 with \

170.4 g of chlorine were added to a stirred solution of 130 g of mineral

Bubble p-cresol into 1200 ml of chloroform. After the kris' *

Addition, the mixture was stirred at room temperature for 1/2 hour, 4-me '

with saturated aqueous sodium hydrogen carbonate solution and ergal

then washed with water, dried over sodium sulfate and _;

evaporated to dryness. The residue was obtained with .A Indei of 159.3 S 2,6-dichloro-p-cresol with a bp. From 120 to 130 ° C /; 2.6-

18 mm Hg distilled. . f geei

'serve

Process 3 ^ste *

17.6 ml of fuming nitric acid were added dropwise
(specific gravity 1.51) to a stirred solution of 106J4 g
2,6-dibromo-p-cresol, prepared as described in reference method 1, in 500 ml of methylene chloride, the temperature being the
The reaction mixture was kept at 10 ^° C. After completion ^of the addition, the mixture was 2.1 hrs. At room temperature overall ^fah stirred and then a 3/4 hour. Heated to reflux. ^dur The solvent was removed in vacuo and the ^NAC Festütoff obtained treated with toluene to obtain 89.9 g of 2,6-dibromo-4-hy- ^droxy-and 4-methyl-cyclohexa-2,5-dienone with a mp. of 129 ^{to Wa £}

131 ⁰ C were obtained. ^e

4-i By proceeding in an analogous manner, but using the

2,6-dibromo-p-cresol with an appropriate amount of ^{2,6-dichloro-n-n} k'resol, which had been prepared as in reference 2 method, replaced ^sp 2,6-dichloro-4-hydroxy-4 ^{-methylcyclohexa-2,5-dienone} 'produced with a mp. 118-120 ⁰ C.

Procedure 4

A solution of 5.0 g of 2,6-dibromo-4-hydroxy-4-methyl- 'cyclohexa "P, 5 ~ o * ienone, prepared as described in process J> , was heated,

and 5 g of sodium acetate in 20 ml of acetic anhydride during

609332 / 10D7

1 1/2 hours at 100 ° C. The solution was poured into water and extracted with dietary ether. The ether extract was with: water saturated aqueous sodium hydrogen carbonate and again Washed with "water, dried over magnesium sulfate and under Evaporated to give a yellow solid which by Crystallization from aqueous methanol 3.9 g of 4-acetoxy-2,6-dibromo-4-methylcyelohexa-2,5-dienone with a m.p. of 117 to 118 C.

revealed.

by proceeding in an analogous manner, but using the

2 e-Dibromo ^ -hydroxy- ^ methylcyclohexa - ^ - dienone by a suitable amount of 2,6-dichloro-4-hydroxy-4-methylcyclohexa> 2,5-dienone prepared as described in process 3, replaced 4-acetoxy-2,6-dichloro-4-methylcyclohexa-2,5-dienone

with a m.p. of 82 to 84 ° C.

Procedure 5

One added 17.7 * ß 3lei-tetra-acetate to a stirred solution from 5 32 g of 2,6-dibromo-p-cresol, prepared as in Reference Process 1, in 25 ml of glacial acetic acid. The reaction was monitored by thin layer chromatography and the mixture, after the starting material was no longer available, poured into water and extracted with dietary ether. The Xtherschlcht was with Washed with water, dried over sodium sulfate and evaporated to dryness. It could be shown by thin layer chromatography that the residue had the same Rf-Vert as U-Acetoxy ^ o-dibromo ^ -methylcyclohexa ^ S-dienone, the like described in Method 4. The infrared spectrum of the product agreed with that of 4-acetoxy-2,6-dibromo-4-methylcyclohexa-2,5-dienone Agree.

Procedure 6

Procedure 6

2.55 g of silver nitrate were added to a stirred solution of 2.12 g of 2 4 δ-Trlehlor ^ -tnethylcyclohexa ^ .S-ciienon in a 4 _; 1 mixture of'üioxan and water (500 ml). The mixture was stirred for 15 hours at room temperature, filtered and dietary ether added to the filtrate. The ether was washed with water, dried over sodium

603832/1007

dried sulfate and evaporated to dryness. The residue was treated with toluene to give 0.2 g of 2,6-dichloro-4-hydroxy-IM 4-methylcyclohexa-2,5-dienone with a melting point of 123 ° C. I <-

The starting material used in the above production I c applied 2,4,6-trichloro-4-methylcyclohexa-2,5-dienone as I v; described in Example 13 below.

Purchase procedure 3

3 × 52 g of bromine were added dropwise to a stirred solution of 5.32 g of 2,6-dibromo-p-cresol, prepared as described in Reference Method 1, in 50 ml of glacial acetic acid at room temperature. After the addition was complete, the mixture was stirred for a further 2 hours, ^{poured into 1 u of} water and the resulting precipitate was removed by filtration. The crystallization of the precipitate from diethyl ether-petroleum ether (3 p. 60 to 80 ° C.) gave 5.33 g of 2,4,6-tribromo-| ν 4-methylcyclohexa-2,5-dienn, mp. 84 to 88 ⁰ C.

Procedure 7

By proceeding analogously to the procedure described above in process 6, but using the 2,4,6-trichloro-4-methylcyclohexa-2,5-dienone by a suitable amount of 2,4,6-tribromo-I »-methylcyclohexa-2,5-dienone (prepared as described in reference process 3) was obtained after washing the ether extract with 2N aqueous sodium hydroxide and then with water, drying over sodium sulfate and evaporation of the ether 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone with a mp of 118 ° C. When mixed with that prepared in method 3 2,6-Dibromo-4-hydroxy-4-methyl-cyclohexa-2,5-dienone, no lowering of the melting point occurred and the infrared spectrum of the Product was identical to that of 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone.

The following reference examples and examples illustrate the preparation new compounds according to the invention.

609832/1007

260386 ',

Example Q

Was dissolved 10 g of ^4,4-J Dimcthylcyclohex-2-enone in 100 tnl of carbon tetrachloride and filmed added a crystal of iodine. The solution, which was kept at 0 ° C., was passed through for a period of '+8 3tdn. Chlorine gas and irradiated with two 100 watt lamps. The mixture was poured into water and neutralized with saturated aqueous sodium hydrogen carbonate, extracted with diethyl ether,

the ether extract washed with water, ü '' * "- '" "" • »read ·.

dried and evaporated. M: m added 150 ml

to the residue and heated the mixture

Reflux and then left for 16 hours at room temperature. The mixture was filtered, the precipitate was washed with diethyl ether and converted to ^A " " ¹⁰ ^ ⁰ Wi "DiKthA

S ^ .r. ^. U * .O «^ -, ichlo ₂ , ₅ '.dlenon with a pp. From 31 to 8? C.

22 _m l of bromine was added dropwise to a stirred solution, 06 »Λ 6-Mbrom-P-fcre.ol. produced as in Be.ue.ver of 106.4 s ^? ' ^b ' ethanol at room temperature.

_fanren , described 1 »■ ^ ^ ^ ^

and cooled down
Kristalli

yclohexa-

revealed.

By

V ^ to the catfish described in procedure 1, however, the acetic anhydride was replaced by an _E eelgne. E-lnr, where J ^{edo was} replaced, 2.6 S _{te H} en _E e Pro _{P =} r , NH ^ _{yloxycyclohc ;; a. 2, 5} -aienon with a

2,6-dibromo - ^ - methyl * ♦ pi J
_F p. from 110 to 112 C.

2 6 0 3 8 6

By proceeding in an analogous manner, but using the When acetic anhydride was replaced by a suitable amount of butyric anhydride, 2,6-dibromo-4-butyryloxy-4-methylcyclohexa-2,5-dienone was produced with a melting point of 89 to 90 ° C.

By proceeding in an analogous manner, but replacing the acetic anhydride with a suitable amount of isobutyric anhydride, 2,6-dibromo-4-isobutyryloxy-4-methylcyclohexa-2,5-dienone with a melting point of 87 ° C. was prepared.

example 12th

The mixture was heated a mixture of 5 g of 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone (prepared as described in Method 3) ^ 20 ml of pyridine and 10 ml of hexanoic anhydride for 2 hr. At 100 ⁰ C, then poured into water and extracted with diethyl ether. The ether layer was washed with dilute hydrochloric acid, aqueous sodium hydrogen carbonate and then with water, dried over magnesium sulfate and evaporated to dryness. The residual oil crystal !, catalyzed upon standing, and the addition of a small amount of petroleum ether (bp. 60 to 8o ° C) followed by crystallization gave a mixture of acetone-petroleum ether (bp. 60 to 8O ⁰ C) 3 * 1 g 2 , 6-Dibromo-4-hexanoyloxy-4-methylcyclohexa-2,5-dienone with a melting point of 53 ° C.

Reference example 1 By working analogously to the manner described in reference method 1

proceeded, however, the p-cresol by a suitable

Replaced amount of 4-ethylphenol was obtained after distillation of the Residual 2,6-dibromo-4-ethylphenol with a boiling point of

86 to 87 ° C / O, 04 mm Hg.

By proceeding in an analogous manner, but replacing the P-cresol with a suitable amount of 4-propylphenol, after distillation of the residue, 2,6-dibromo-4-propylphenol with a boiling point of 122 to 126 ° C./0 was obtained .06 mm Hg.

6098 3 2/1007

By proceeding in an analogous manner, but using the Replaced p-cresol with an appropriate amount of 4-isopropylphenol, after distillation of the residue, 2,6-dibromo-4-isopropylphenol was obtained with a bp of 115 to 116 ° C / O, 15 mm Hg.

By proceeding in a similar manner, but replacing the p-cresol replaced by a suitable amount of 4-sec-butylphenol / was obtained after distillation of the residue of 2,6-dibromo-4-sec-butylphenol with a bp. Of 128 to 130 ° C / 0.3 mm Hg.

By else was going on / in an analogous V, but substituting p-cresol by a suitable amount of 4-tert-butyl phenol, was obtained after treatment of the residue with a small quantity of cold chloroform, 2,6-dibromo-4-tert .-Butylphenol with a melting point of 71 to 72 ^° C.

By proceeding in an analogous manner, but replacing the p-cresol with a suitable amount of 4-hexylphenol, after distillation of the residue, 2,6-dibromo-I-4-hexylphenol was obtained with a boiling point of 160 ° C / O, O5 mm Hg.

By proceeding in an analogous manner, but with single use one equivalent of bromine used was obtained after distillation of the residue 2-bromo-4-methylphenol with a boiling point of 104 to 106 ° C / 17 mm Hg.

Reference example 2

21.3 g of chlorine were bubbled into a stirred solution of 22.5 g of 4-sec-butylphenol in 150 ml of chloroform and the temperature rose to the reflux temperature. After the addition was complete, the mixture was stirred for 2 hours at room temperature, washed with saturated aqueous sodium hydrogen carbonate solution and then with water, dried over sodium sulfate and evaporated to dryness. The residue was distilled to give 20.2 g of 2,6-dichloro-4-sec-butylphenol with a bp of 87 to 97 ° C./0.15 mm Hg.

609832/1007

By proceeding in an analogous manner, but using the Replacing 4-sec-butylphenol with an appropriate amount of 4-tert-butylphenol gave 2,6-dichloro-4-tert-butylphenol with a bp 94 ° C / 0.1 mm Hg, m.p. 42 to 45 ° C.

By proceeding in a similar manner but substituting the 4-sec-butylphenol by a suitable amount of 4-ethyl phenol, was obtained 2,6-dichloro-4-ethylphenol with a bp. 86-88 ⁰ C / 0, 6 mm Hg.

By proceeding in an analogous manner, but using the 4-sec-butylphenol with a suitable Kenge 2-bromo-4-methylphenol (prepared as described in Reference Example 1) and used one equivalent of chlorine was obtained

Bp. 76 ° C / E, 08 now Hg.

Example 13

Chlorine was bubbled into a stirred solution of 27 # 2 g of 4-isopropylphenol in 200 ml of methylene chloride while cooling with an ice bath until thin-layer chromatography in the reaction mixture showed no more 4-isopropylphenol. The mixture was washed with saturated aqueous sodium hydrogen carbonate solution and then with water, dried over sodium sulfate and evaporated to dryness. The residual oil was obtain 7.4 g of 2,4,6-trichloro-4-isopropylcyclohexa-2,5-dienone with a bp. Of 100 to 11O ⁰ C / 0.25 mm Hg distilled.

By proceeding in an analogous manner, but replacing the 4-isopropylphenol with a suitable amount of p-cresol and allowing chlorine to bubble into the reaction mixture for 3 hours, after treatment of the residue with petroleum ether (boiling point 60 to 80 ° C. ) of 2,4,6-trichloro-4-methylcyclohexa-2,5-dienone with a mp. 97-98 ⁰ C, after crystallization from acetone-petroleum ether _(bp. $ 0 to 80 ° C).

609832/1007

2 6 Ü 3 8 G

By proceeding in an analogous manner, but using the 4-isopropylphenol with an appropriate amount of 4-propylphenol replaced and added 3.5 equivalents of chlorine, were obtained 2,4,6-trichloro-4-propylcyclohexa-2,5-dienone with a 3dp. from 105 to 110 ° C / 0.07 mm Hg.

By proceeding in an analogous manner, but with the 4-isopropylphenol replaced by a suitable amount of 2-bromo-4-methylphenol, prepared as described in Reference Example 1; replaced and added two equivalents of chlorine, were obtained after treatment the residue with petroleum ether (bp. 60 to 8o ° C) 2-bromo-4,6-dichloro-4-methylcyclohexa-2,5-dienone with a Mp «from 103 to 106 ° C after crystallization from acetone-petroleum ether (Bp 60 to 80 ° C).

By else was going on / in an analogous V, being allowed, however, the bubbled 4-isopropylphenol by a suitable amount of 4-sec-butyl phenol and chlorine substituted for 2 hr. Through the reaction mixture, there was obtained 2,4,6-trichloro -4-sec-butylcyclohexa-2,5-dienone with a bp. of 121 ⁰ C / 0.3 mm Hg.

By proceeding in an analogous manner, but replacing the 4-isopropylphenol with a suitable amount of 4-butylphenol and adding three equivalents of chlorine, 4-butyl-2,4,6-trichlorocyclohexa-2,5-dlenone with a bp . from 108 to: 112 ° C / 0.1 mm Hg.

By proceeding in a similar manner but substituting the 4-isopropylphenol by a suitable amount of 4-tert-butyl phenol, was obtained after treatment of the solid residue with petroleum ether (bp. 60 to 8O ⁰ C) 2,4,6 -Trichlor-4-tert-butylcyclohexa-2,5-dienone with a melting point of 106 ° C.

By proceeding in an analogous manner, except that the 4-isopropylphenol was replaced by a suitable amount of P-bromo-o-chloro-4-methylphenol (manufactured as described in 3ozur, see game 2) replaced and an equivalent chlorine uufvib, orr.iolt after treatment the solid residue with Prtrolathor (b.p. 60 to 80 C)

h L * Γ i J. ' I ~ w'

2-bromo-4,6 ~ dichloro-4-methylcyclohexa-2,5-dienone with a mp. Of 103 to 1O5 ° C after crystallization from acetone-petroleum ether (bp. 60 to 80 ⁰ C).

By proceeding in an analogous manner, but replacing the 4-isopropylphenol with a suitable amount of 2,6-dibromo-p-cresol (prepared as described in reference process 1) and adding one equivalent of chlorine, 2,6-diol was obtained rom-4-chloro-4-methylcyclohexa - '?, 5-dienone with a melting point of 126 ⁰ C after crystallisation of the solid residue from acetone-petroleum ether. (b.p. 60 to 8O ⁰ C.).

By proceeding in an analogous manner, except that the 4-isopropylphenol was replaced by a suitable amount of 4-ethylphenol and 3.5 equivalents of chlorine were added, after treatment of the residue with petroleum ether (b.p. 60 to 80 ° C.) 2.4 was obtained , 6-trichloro-4-äthylcyclohexa-2,5-dienone with a mp. of 69 to 7O ⁰ C, after crystallization from acetone-petroleum ether (bp. 60 to 8O ⁰ C).

Reference example 3

50.33 g of powdered zinc were added in portions over 1/2 hour to a stirred suspension of 167.7 g of 2,4,6-trichloro-4-isopropylcyclohexa-2,5-dienone, prepared as described in Example 13, in 450 ml glacial acetic acid and 150 ml water. The temperature was allowed to ^{rise to 55 °} C. and this temperature was maintained. After the addition was complete, the mixture was stirred for 15 hours at room temperature, filtered off and the filtrate was evaporated to dryness in vacuo, giving a yellow oil which was then dissolved in diethyl ether. The ether was washed with water, saturated aqueous sodium hydrogen carbonate solution and then with water, dried over sodium sulfate and evaporated. The residue was distilled to give 84.3 β of 2,6-dichloro-4-isopropylphenol with a bp of 87 to 88 ° C./0.15 mm Hg.

609832/1007

81.5 ° C / O, 1 mm Hg.

^{S £ iS £ i £ l} - ^Lii nalo _K to the manner described in method 3 by proceeding analogously to the . _p . _creso l with a suitable

^glnS ; ΓΙηΤβ rrt- ^ ylphenol (manufactured as in

th amount of 2.6 « _{e <,} 2,6-dibromo-

rssc ^ - ^ ¹ - ^{with an Fp} · ^of - 91 ⁰ C ago.

* 2,5-dienone with a mp. Of ₉ 3-102 C forth.

2,5-dlenon with a mp. Of

proceeded in a normal manner, but this was done by adding an analogous _amount of 2,6-dibromo-

2,6-dibromo-p-uresol * ™ * «™ \ _n ^ ug example, described) 4- _P ro _P ylphenol (manufactured as _{ßropyicyciohexa} _

replaced, one put 2,6-Dlbrom y _{crystallization}

2,5-dienone with a m.p. of 111 ois
from cyclohexane.

in analoper Weise'vorßing, but replacing the by in an analogous amount _geelgnete

2.6-Dlbron-p-lcresol by ei B ^ ^ Reference example:

2,6-dichloro-U-propyIpheno (herg _lor _ _{4. Hydroxy} _ ₄ .

described) he ^ ^ - ^ _{ρ? <} _ "■ ^" _{Λ after} propyleyclohexa-2 ^ -dieno
Crystallization from cyclohexane.

6D9B32 / 1007

By proceeding in an analogous manner, but replacing the 2,6-dibromo-p-cresol with a suitable amount of 2-bromo-6-chloro-4-methylphenol (prepared as described in reference example 2), 2- bromo-6-chloro-4-hydroxy-4-methylcyclohexa-2,5-dienone with a mp. 125-126 ° C after recrystallization from acetone-petroleum ether (bp. 60 to 80 ⁰ C) ago.

Example 15

4.4 ml of fuming nitric acid (spec. Density 1.51) were added dropwise to a stirred solution of 29.39 g of 2,6-dibromo-4-isopropylphenol, prepared as described in Reference Example 1, in 125 ml of methylene chloride, the Temperature of the reaction mixture between 8 ⁰ C and 10 ⁰ C was kept. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The mixture was washed with saturated aqueous sodium hydrogen carbonate and then with water and then refluxed for 1 hour. The mixture was cooled to room temperature and washed with saturated aqueous sodium hydrogen carbonate and then with water, dried over magnesium sulfate and evaporated in vacuo. The solid obtained was treated with toluene and gave 9.42 g of 2,6-dibromo-4-hydroxy-4-isopropylcyclohexa-2,5-dienone with a melting point of 99 to 101 ° C. after recrystallization from toluene-petroleum ether (Bp 60 to 80 ° C.

By proceeding in an analogous manner, but replacing the 2,6-dibromo-4-isopropylphenol with a suitable amount of 2,6-dichlorom-isopropylphenol (prepared as described in the reference example), 2,6-dichloro- 4-hydroxy-4-isopropylcyclohexa-2,5-dienone with a mp. of II8 to 119 ⁰ C forth.

By proceeding in an analogous manner, but with the 2,6-dibromo-4-isopropylphenol with a suitable amount of 2,6-dichloro-4-tert-butylphenol (prepared as described in reference example 2) replaced 2,6-dichloro-4-hy- j

809832 / ^ 007

sr- · ¹ * * i

603864

124 ° C

one in

-n with a ? p. from

n. ^ ilr .. ',. «Obcl one however the o ^ lp.>-> · _ _{eUt wlc} ir. DCZU ₆ S-

^{ϊ? ι} '^οΐη;■':; ■. _uti

105 ° C.

By proceeding in an analogous manner, but using the 2,6-dibromo-4-iyopropylphenol with an appropriate amount of 2,6-Dlbromo-4-tert-butylphenol (prepared as described in Reference Example 1) was replaced after treatment with cyclohexane 2,6-dibromo-4-hydroxy-4-tert.-butylcyclohexa-2,5 dienone with a melting point of 127 to 128 ° C (decomposition) after crystallization from "ethyl acetate-petroleum ether (bp. 40 to 60 ° C)

here.

By proceeding in an analogous manner, except that the 2,6-dibromo-4-isopropylphenol was replaced by a suitable amount of 2,6-dichloro-4-sec-butylphenol (prepared as in Example 2 ^v »♦ - ■» ♦ ■ - * ». One put η

SSiSEiSl -! ^ - _ln procedure «· proceed as described

by analogously to er ₆ _ _Dlbrom.4 -hydroxy-4-methyl-Bing. where. to Jedoe. d _{note HenRe 2/6} . _Dlbron . oyelohe »-2.5-dienon by ^ _(produced as In

* -zml- ^ ^an * ^yCyCy ° ^h , "Izte. , one shared it-Acetoxy-2,6- _B eisplel, 4 - '^. / ^ ηοή with a pp. of

T from acetone-petroleum ether. (sap.

60 to 80 ⁰ C)

EO983271OO7

2603364

By proceeding in a similar manner, but replacing the 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone by an appropriate amount of 2,6-dichloro-4-Mthyl-4-hyclroxycyclohexa-2 _J Replaced 5-dienone (prepared as described in Example 14), 4-acetoxy-2,6-dlcnlor-4-ethylcyclohexa-2,5-dienone with a pp. Of 68 to 70 ⁰ C after crystallization from petroleum ether (boiling point 60 to 80 ^° C.) .

By proceeding in a similar manner, but replacing the 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone by an appropriate amount of 2, 6-dibromo-4-hydroxy-4-propylcyclohexa-2, 5-dienone (prepared as described in example 14) replaced, one set of 4-acetoxy-2 _i 6-dibromo-4-propylcyclohexa-2,5-dienone with a mp. 91-92 ⁰ C, after crystallization from petroleum ether (b.p. 60 to 80 ^° C.).

By proceeding in an analogous manner, except that the 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone is replaced by a suitable amount of 2,6-dibromo-4-hydroxy-4-is ^ propylcyclohexa- 2,5-dienone (prepared as described in example 15) replaced, one set of 4-acetoxy-2,6-dibromo-4-isopropylcyclohexa-2,5-dlencn of mp. 115-116 ⁰ C after crystallization from acetone - Petroleum ether (b.p. 60 to 80 ° C).

By proceeding in an analogous manner, except that the 2,6-dibromo-4-methylcyclohexa-2,5-dienone is replaced by a suitable amount of 2,6-dichloro-4-hydroxy-4-isopropylcyclohexa-2,5- dienone (prepared as described in example 15) replaced, one set of 4-acetoxy-2,6-dichloro-4-isopropylcyclohexa-2,5-dienone with a mp. 80-82 ⁰ C, after crystallization from petroleum ether (bp. 60 up to 80 ⁰ C).

Example 17

2.96 g of 2-methylbutanoyl chloride was added dropwise to one Stirred solution of 5 g of 2,6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone (prepared as described in process 3) in 20 ml

- 58 -

dry pyridine. After the exothermic reaction had subsided, the mixture was heated for 1/2 hour. stirred at room temperature, poured into diethyl ether and the ethereal solution washed with 2N aqueous sodium hydroxide and then with water, dried over magnesium sulfate and evaporated. The residue was treated with petroleum ether (b.p. 60 to 80 ° C.) and crystallized from acetone-petroleum ether (b.p. 60 to 80 ° C.), 2.5 g of 2,6-dibromo-4-methyl-4- (3 methylbutanoyloxy) cyclohexa-2,5- dienone with a melting point of 102 to 104 ° C.

By proceeding in an analogous manner, but replacing the 5-methylbutanoyl chloride with an appropriate amount of 2-ethylbutanoyl chloride , 2,6-dibromo-4- (2-ethylbutanoyloxy) -4-methylcyclohexa-2,5-dienone was obtained with a m.p. of 110 to 112 ⁰ G was obtained.

By proceeding in an analogous manner, but replacing the 2-methylbutanoyl chloride with a suitable amount of 2-methylbutanoyl chloride, 2,6-dibromo-4-methyl-4- (2-methylbutanoyloxy) -cyclohexa-2,5-dienone was prepared with a pp. from 96 to 98 ^° C.

By else was going on / in an analogous V, but replacing the 2 _J .6-dibromo-4-hydroxy-4-methylcyclohexa-2,5-dienone by an appropriate amount of 2,6-DichloΓ-4-ethyl-4-hydroxycyclohexa -2,5-dienone (prepared as described in Example 14) replaced, after distillation of the residue 2,6-dichloro-4-ethyl-4- (3-methylbutanoyloxy) -cyclohexa-2,5-dienone with a

Bp from 125 to IJO ⁰ C / 0.1 mm Hg. Example 18

A mixture of 5 g of 2,6-dichloro-4-hydroxy-4-methylcyclohexa-2,5-dienone (prepared as in process> described), 10 ml of pyridine and 10 ml of propionic anhydride during

609832Μ0Ό7

1 1/2 hrs. At 10O ⁰ C, then poured into water and extracted

\ with diethyl ether. The ethereal layer was saturated with ν

With aqueous sodium hydrogen carbonate and then with water

Wash ε, dried over sodium sulfate and dried to dryness

steams. The crystallization of the residue from aqueous | Methanol gave 3.1 g of 2,6-dichloro-4-methyl-4-propionyloxy- |

cyclohexa-2,5-dienone with a melting point of 127 to 129 ° C. |

ί By proceeding in an analogous manner, but using the

j) propionic anhydride with a suitable amount of butyric acid

replaced anhydride, 4-butyryloxy-2,6-dichloro-4-methyl-

i | cyclohexa-2,5-dienone with a melting point of 81 to 82 ^° C. is produced.

By proceeding in an analogous manner, but replacing the propionic anhydride with a suitable amount of hexanoic anhydride, 2,6-dichloro-4-hexanoyloxy-4-methylcyclohexa-2,5-dienone with a melting point of 41 to 42 was obtained after distillation ° C after crystallization from petroleum ether (bp 40 to 60 ° C) produced.

Example 19

3.5 g of isobutyryl chloride were added to a stirred solution of 5 g of 2,6-dichloro-4-hydroxy-4-methylcyclohexa-2,5-dienone (prepared as described in Method 3) in 35 ml of dry pyridine. After the addition was complete, the mixture was stirred for 1 hour at room temperature, poured into diethyl ether and the ethereal solution was washed with water, 2N aqueous sodium hydroxide and again with water, dried over magnesium sulfate and evaporated. The residue was crystallized from petroleum ether (bp. 60 to 80 ⁰ C) to give 4.2 g of 2,6-dichloro-4-isobutyryloxy-4-methylcyclohexa-2,5-dienone with a mp. 103-106 ° C crystallized.

By proceeding in ane? .. ogre catfish, whereby one however If isobutyryl chloride was replaced by a suitable amount of pentanoyl chloride, 2,6-dichloro-4-methyl-4-pentanoyloxycyclohexa-2,5-dienone with an eleventh melting point of 43 to 45 ° C. was prepared.

609832/1007

By, in an analogous way earlier,; / ,, wohr. ·] One Jf.'l '/ ^ h'] .- ir; Isobutyryl replaced by a ßeeigneto Kon ^ o ^ at -Methylbutanoylchlorid, was adjusted 2,6-dichloro-4-methyl-4- (3-methylbutanoyloxy) -cyclohexa-2,5-dlenon of mp. 87-89 ⁰ C here.

By proceeding in an analogous manner, but using the Isobutyryl chloride was replaced by a suitable amount of heptanoyichloride, it was produced after distillation 2,6-Dlchlor-4-heptanoyloxy-4-methylcyclohexa-2,5- <iienone with a bp of 120 to 125 ° C / 0.1 mm Hg.

By proceeding in an analogous manner, but with the isobutyryl chloride by a suitable amount of Replaced 2-ethylbutanoyl chloride, 2,6-dichloro-4- (2-ethylbutanoyloxy) -4-methylcyclohexa-2,5-dienone was produced with a pp. from 98 to 1O1 ° C.

By proceeding in an analogous manner, but with the isobutyryl chloride by a suitable amount of ty-methylpentanoyl chloride replaced, 2,6-dichloro-4-methyl-4- (4-methylpentanoyloxy) -cyclohexa-2,5-dienone was produced with a melting point of 58 to 60 ° C. after crystallization from aqueous methanol.

Example 20

A mixture of 5 # 92 g of 2,6-dibromo-U-ethyl-4-hydroxy-cyclohexa-2,5-dienone (prepared as described in the example), 10 ml of pyridine and 10.3 nil propionic anhydride was heated for 1 liter / 2 hrs. at 100 ⁰ C and then poured into water and extracted with diethyl ether. The ethereal layer was washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate and then with water, dried over magnesium sulfate and evaporated to dryness. The residue turned off

6Q9B32M007

¹

<5 acetone petroleum ether (b.p. 60 to 80 C) to achieve I I

* 4.85 g of 2,6-dibromo-4-ethyl-4-propionyloxycyclohexa-2,5-dienone

* Crystallized with a pp. 55 to 57 ° C.

'By proceeding in an analogous manner, but with that

ii ₍ propionic anhydride by a suitable amount of butter

j replaced acid anhydride, one put 2,6-dibromo-4-butyrylox}> -

1 4-ethylcyclohexa-2,5-dienone with a melting point of 58 to 61 ° C hsr.

; ■ By proceeding in an analogous manner, using Jodoch the

f ^s propionic anhydride by a suitable amount of

1 replaced isobutyric anhydride, 2,6-dibromo-

Ä 4-ethyl-4-isobutyryloxycyclohexa-2,5-dienone with a melting point.

jj from 80 to 85 ^° C.
tit

By proceeding in an analogous manner, but using the ! · 'Propionic anhydride with a suitable amount of

Hexanoic anhydride replaced, one set after distillation '2,6-Dibromo-4-ethyl-4-hexanoyloxycyclohexa-2,5-dienone with bp 150-155 ° C / 0.1 mm Hg.

Example 21

A mixture of 5 g of 2,6-dichloro-4-ethyl-4- '·' hydroxycyclohexa-2,5-dienone (prepared as described in the example), 10 ml of pyridine and 10 ml of propionic anhydride was heated for 1 1/2 hours to 100 C, then poured into water and extracted with diethyl ether. The ethereal layer was washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate and |,. then washed with water, dried over sodium sulfate and [evaporated to dryness. The remaining oil was obtained with 4.9 g of 2,6-dichloro-4-ethyl-4-propionyloxycyclohexa-2,5-dlei

distilled.

^; hexa-2,5-dienone with a bp from II5 to 120 ° C / 0.05 mm Hg

By proceeding in an analogous way, but with that Propionic urine hydride with a suitable amount of butyric acid

■ r. Γ 0 P? :. ι 1 C 0 7

Replaced anhydride, ^ -Butyryloxy ^ .e-dlchlor-i-ethylcSLa- _S .5-dlenon .It became a. 3d _P. manufactured from 120 to I ₂₅ VM ₅ mm.

"The proceeding in! Analogously catfish, but substituting the Propionsaureanhydrld by a suitable amount of isobutyric anhydride was so-dichloro-4-^ -athyl lsobutyryloxycyclo _h exa. ₂ . ₅ -dienon with a. Sdp from

1 * 0 to 146 ° C / O.O5 -Hi and « ^{lnem F} » ^{of 55 Me 39} ° ^.

By proceeding analogously, but replacing the proplonic anhydride with a suitable amount of hexyl anhydride, ₂ .6-Di.hloM-.th »l-4-h _e * anoylo * y _O yclohexa-2,5- dienon with a bp of 118 ° C / O.O5 mm Hg.

^ eÄie a mixture of 4.8 g ^ propylcyclohexa ^ .S-dlenon (prepared as in Example 14b.- \ , hLi Π 6 ml pyrldine and 13.6 ml propionic anhydride :: TXt 10Λ. SOB then in water and extracted

Tt diethyl ether. The ethereal layer was washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate and then with water, dried over sodium sulfate and evaporated to dryness. The residue was removed from petroleum ether (40 to 60 ° C.) to give 4.7 g of 2,6-di-bromo-4-propionyloxy -'.-propylcyclohexa ^ .S-dlenone with a melting point of

102 to 1OJ ⁰ O crystallized.

"The one he was going manner in analo _E, wherein one but replacing the rroplonsKureanhydrld by a suitable" close to Buttersaureanhydrld was -Dibro ^ ^ ^ -prooylcyclohexL2.5 -butyryloxy-dienone with a mp. _50-5 1 ° C manufactured.

609832/1007

. By proceeding in an analogous manner, but using the Replacing propionic anhydride with an appropriate amount of isobutyric anhydride became 2,6-dibromo-4-isobutyryloxy-4-propylcyclohexa-2,5-dienone obtained with a m.p. of 74 to 75 ° C.

By proceeding in an analogous manner, except that the 2,6-dibromo-4-hydroxy-4-propylcyclohexa-2,5-dienone was replaced by a suitable amount of 2,6-dibromo-4-hydroxy-4-isopropylcyclohexa-2 , 5-dienone (prepared as described in Example 15), 2,6-dibromo-4-isopropyl-4-propionyloxycyclohexa-2,5-dienone with a melting point of 49 to 50 ^° C. was obtained.

By proceeding in an analogous manner, except that the 2,6-dibromo-4-hydroxy-4-propylcyclohexa-2,5-dienone is replaced by a suitable amount of 2,6-dibromo-4-hydroxy-4-tert. butylcyclohexa-2,5-ciienon (prepared as described in example 15) replaced and the mixture during 11 hrs. at 70 ⁰ C heated, was added 2,6-dibromo-4-propionyloxy-4 ~ tert-butylcyclohexa-2,5 -dienon obtained with a mp. 109-110 ⁰ C.

By proceeding in an analogous manner, except that the 2,6-dibromo-4-hydroxy-4-propylcyclohexa-2,5-dienone is replaced by a suitable amount of 2,6-dichloro-4-hydroxy-4-tert. butylcyclo-. hexa-2,5-dienone (prepared as described in Example 15) replaced and the mixture ^{heated for 24 hours at 70 0} C, one obtained 2,6-dichloro-4-propionyloxy-4-tert-butylcyclohexa-2, 5-dienone with a melting point of 100 to 102 ^° C.

By proceeding in an analogous manner, except that the 2,6-dibromo-4-hydroxy-4-propylcyclohexa-2,5-dienone is replaced by a suitable amount of 2,6-dibromo-4-hydroxy-4-sec. butyleyclohexa-2,5-dienone (prepared as described in example 15) replaced and the mixture during 1 hr. at 100 ⁰ C heated, there was obtained 2,6-Dlbrom-4-propionyloxy-4-sec-butylcyclohexa-2, 5-dienone with a melting point of 66 to 68 ^° C.

609832/1007

l ^ Terhitzte g a mixture of 9.95 ^ G-dichloro-i-hydroxy-4-propylcyclohexa - ?, 5-dier.on (prepared as described in Example 14), 30 ml of pyridine and 0} _m l of acetic anhydride while 24 hrs. at 70 ⁰ C. the solution was evaporated to dryness in vacuo and the residue dissolved in diethyl ether. The ether was washed with water, with dilute hydrochloric acid, with saturated aqueous sodium carbonate and again with water, dried over sodium sulfate and evaporated to dryness. The residue was crystallized from petroleum ether to obtain 6.5 g of 4-Acetox _y (bp 60 to 80 C.) -. _2, 6 ~ dichloro-4- ropylcyolohexa.2.5 _P-dienone with a melting point of 0 to _{7 7} 1 ° C crystal!

Indom In one analo _E he was going manner, wherein _m replaced at However, the Essi ^ äureanhydrid by a suitable amount of Isobutterrtü '' nh "drld, _m received on after distillation of the

; received _m an, -Aceto ^ -. ^ - di ^ .- tert _bUty l _Oy clo _hexa . ₂ , ₅ .dlenon with a pp. From 107.5 to 108.5 C.

η proceeded in an analogous manner , but the TZZ or ^ drLv -.- prop ^ cclo.ea-a 5-aienon d.rch a 2,6-Dlcnio ι g.niehior-i-hydroxy-t-tert.- butyloyolof WW an 7, 6 you just _{got drunk)}

herge, e - _ _P

^ e proceeded, but the * ^ -Dlchlor -.- hydroxy -.- P ^ ylcyeXohexa - ^ - dienone by a

609832/1007

-65- 260336 *. I.

Replaced a suitable amount of 2,6-dibromo-4-hydroxy-4-sec-butylcyclohexa-2,5-dienone (prepared as described in Example 15) and ^{heated the mixture at 100 °} C. for 1 hour to give 4 Acetoxy-2 _> 6-dibromo-4-sec-butylcyclohexa-2,5-dienone with a melting point of 102 to 104 ° C. |

By proceeding in an analogous manner, but with the 2, e-dichloro ^ -hydroxy ^ -propylcyclohexa · ^, 5-dienone by a suitable amount of 2-bromo-6-chloro-4-hydroxy-4-methylcyclohexa-2 , 5-dienone (prepared as described in example 14) replaced and the mixture for 2 hrs. at 100 ⁰ C heated, to give 4-acetoxy-2-bromo-6-chloro-4-methylcyclohexa-2,5-dienone with mp. 85-88 ⁰ C, after crystallization from acetone-petroleum ether (bp. 60 ° -80 ° C).

Example 24

A mixture of 4.86 g of 2,6-dibromo-2-hydroxy-4-tert-butylcyclohexa-2,5-dienone (prepared as described in the example), 5 ml of butyric anhydride and 12 ml of pyridine was heated for 24 hours ? 0 ° C and then evaporated to dryness in vacuo. The residue was dissolved in diethyl ether and the ether was washed with water, dilute hydrochloric acid, saturated aqueous sodium carbonate and again with water, dried over sodium sulfate and evaporated to dryness. The residue was crystallized from petroleum ether (bp. 60 to 8O ⁰ C) to give 2.9 g of 2,6-dibromo-4-butyryloxy-4-tert-butylcyclohexa-2,5-dienone with a mp. Of 84 to 85 ⁰ C crystallizes.

By proceeding in an analogous manner, but using the 2,6-dibromo-4-hydroxy-4-tert-butylcyclohexa-2,5-dienone by a suitable amount of 2,6-dichloro-4-hydroxy-4-tert-butylcyclohexa-2,5-dienone (prepared as described in Example I5) was obtained after crystallization of the Residue 4-butyryloxy-2,6-dichloro-4-tert-butylcyclohexa-2,5-dienone with a bp from 1J50 to 155 ° c / 0.2 mn Hg.

By proceeding in an analogous manner, however, the 2,6-dibromo-4-hydroxy-4-tert.-butylcyclohexa-2,5-di ^ non by a suitable amount of 2,6-dibromo-4-hydroxy- 4-sec-butylcyclohexa-2,5-dienone (prepared as written bell in example 15) replaced and the mixture for 1 hr. auf.100 ⁰ C heated to yield, after distillation of the residue of 2,6-dibromo-4- butyryloxy-4-sec-butylcyclohexa-2,5-dienone with a bp 225 ° C / 0.1 mm Hg.

Example 25

A mixture of 8.62 g of 2,6-dibromo-4-hydroxy-4-isopropylcyclohexa-2: 5-dlenone (prepared as described in Example), 30 ml of isobutyric anhydride and 30 ml of pyridine was heated for 1 1/2 3 days . to 100 ⁰ C, poured into water and extracted with Di'äthyläther, The ethereal layer was washed with dilute hydrochloric acid, saturated aqueous sodium bicarbonate and äarin with water, dried over magnesium sulfate and evaporated to dryness ·. The residue was distilled and removed from petroleum ether (boiling point 40 to 60 ° C.) to give 7.18 g of 2,6-dibromo-4-isobutyryloxy-4-isopropylcyclohexa-2,5-dienone with a melting point of 42 to 44 ° C and a bp of 137 to 140 ° C / 0.3 mm Hg crystallized.

By proceeding in an analogous manner, but using the

2 _# 6-dibromo-4-hydroxy-4-isopropylcyclohexa-2,5-dienone by I.

an appropriate amount of 2,6-dichloro-4-hydroxy-4-isopropylcyclohexa-2,5-dienone (prepared as described in Example 15) replaced and the mixture was heated 24 hours. at 7O ⁰ C, was obtained after distillation of the Residue 2,6-dichloro-4-isobutyryloxy-4-isopropylcyclohexa-2,5-dienone with a bp of 138 to 140 ° C./0.1 mm Hg.

By proceeding in an analogous manner, but using the 2,6-dibromo-4-hydroxy-4-isopropylcyclohexa-2,5-dienone a suitable amount of 2,6-dibromo-4-hydroxy-4-tert.-butyl-

609832/1007

cyclohexa-2,5-dienone (prepared as described in Example 15) replaced and the mixture heated to 70 ° C. for 24 hours, 2,6-dibromo-4-isobutyryloxy-4-tert.-butylcyclohexa-2 was obtained, 5-dienone of the residue from petroleum ether having a melting point. of 79 C, after crystallization (bp. 40 to 60 ⁰ C).

By proceeding in an analogous manner, except that the 2,6-dibromo-4-hydroxy-4-isopropylcyclohexa-2,5-dienone is replaced by a suitable amount of 2,6-dichloro-4-hydroxy-4-tert. butylcyclohexa-2,5-dienone (prepared as described in example 15) replaced and the mixture heated '24 hrs. at 70 ⁰ C, there was obtained 2,6-Dicblor-4-isobutyryloxy-4-tert-butylcyclohexa-2, 5-dienone of mp. 58-61 ° C after crystallization of the residue from acetone-petroleum ether (bp. 60 to 8O ⁰ C).

By proceeding in an analogous manner, but using the 2,6-dibromo-4-hydroxy-4-isopropylcyclohexa-2,5-dienone a suitable amount of 2,6-dibromo-4-hydroxy-4-sec-butylcyclohexa-2, 5-dienone (prepared as described in Example 15) was obtained after distillation of the residue 2,6-dibromo-4-isobutyryloxy-4-sec-butylcyclohexa-2,5-dienone with a bp of 200 to 205 ° C / 0.1 mm Hg.

Example 26

A mixture of 2.55 g of 2,6-dichloro-4-hydroxy-4-tert-butylcycloh3xa-2,5-dienone (prepared as described in Example 15), 12 ml of pyridine and 8.4 g of 5- Methyl butanoic anhydride to 70 ⁰ O for 24 hours, then poured into water and extracted with diethyl ether. The ethereal layer was washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate and then with water, dried over magnesium sulfate and evaporated to dryness. The residue was filtered with petroleum ether (bp. 60 to 80 ⁰ C), and the filtrate was evaporated to dryness and distilled to give 1.55 g of 2,6-dichloro-4- (5-methylbutanoyloxy) -4-tert- butylcyclohexa-2,5-dienone with

609832/1007

P - 68 -

\: bp 126 to 151 ° c / 0.4 mm Hg were obtained.

Ϊ Example 27

|; A mixture of 14.7 g of 2,6-dibromo-4-iso- \\ propylphenol (prepared as described in Reference Example 1) and 17.8 g of N-bromosuccinimide in 200 ml of dry methanol was refluxed for 15 hours in water and extracted with diethyl ether. The ethereal layer was washed with 2N aqueous hydrochloric acid and then with water, dried over magnesium sulfate and evaporated to dryness. The residue was extracted from petroleum ether (60 to 80 ° C) to give

with a melting point of II5 to 117 ° C. crystallized.

By proceeding in an analogous manner, but using the 2,6-dibromo-4-isopropylphenol with a suitable amount of 2,6-dibromo-4-ethylphenol (prepared as in reference example 1 described), one obtained 2,6-dibromo-4-ethyl-4-methoxycyclohexa-2,5-dienoh with a m.p. of 7.5 to 75 C.

By proceeding in an analogous manner, but replacing the 2,6-dibromo-4-isopropylphenol with a suitable amount of 2,6-dibromo-4-propylphenol (prepared as described in Reference Example 1), the residue was obtained after distillation 2,6-dibromo-4-methoxy-4-propylcyclohexa-2,5-dienone, sap. 130 ° C / 0.1 _mm Hg.

By proceeding in an analogous manner, but with the 2,6-dibromo-4-ir, opropylphenol by a suitable amount of 2,6-dibromo-4-sec-butylphenol (prepared as described in reference example 1) was obtained after distillation dos residue P, 6-dibromo-4-methoxy-4-sec-butylcyclohexa - ?, 5-dienone with a 3dp. of 100 ° C / 0.15 mm Hg.

609832/1007

By proceeding in an analogous manner, but replacing the 2,6-dibromo-4-isopropylphenol with a suitable amount of 2,6-dibromo-4-tert-butylphenol (prepared as described in Reference Example 1), one obtained after Distillation of the residue 2 _r 6-dibromo-4-methoxy-4-tert-butylcyclohexa-2,5-dienone with a bp of 120 ° C / 0.1 mm Hg.

By proceeding in an analogous manner, but using the 2,6-Dibromo-4-isopropylphenol with an appropriate amount of 2,6-Dibromo-4-hexylphenol (prepared as in Reference Example 1 described), after distillation of the residue, 2,6-dibromo-4-hexyl-4-methoxycyclohexa-2,5-dienone was obtained with a bp of 120 to 124 ° C / 0.2 mm Hg.

By proceeding in an analogous manner, except that the 2,6-dibromo-4-isopropylphenol by a suitable amount of 2,6-dichloro-p-cresol (prepared as in reference example 2 described), one obtained 2,6-dichloro-4-methoxy-4-methylcyclohexa-2,5-dienone with a melting point of 162 to 103 ° C after crystallization from methanol.

By proceeding in an analogous manner, but replacing the 2,6-dibromo-4-isopropylphenol with a suitable amount of 2,6-dichloro-4-ethylphenol (prepared as described in Reference Example 2), 2,6- dichloro-4-ethyl-4-methoxycyclohexa-2,5-dienone with a mp. 82-83 ⁰ C.

By proceeding in an analogous manner, but replacing the 2,6-dibromo-4-isopropylphenol with an appropriate amount of 2,6-dichloro-4-isopropylphenol (prepared as described in Reference Example 3), 2,6- dichloro-4-isopropyl-4-methoxycyclohexa-2,5-d 'lenon of mp. 94-96 ⁰ C.

By proceeding in an analogous manner, but using the 2,6-dibromo-4-isopropylphenol with an appropriate amount of 2i6-dibromo-p-cresol (prepared as in reference procedure 1 described) and replaced the N-3romsuccinimide with a replaced an appropriate amount of N-chlorosuccinimide was obtained 2,6-dibromo-4-methoxy-4-methylcyclohexa-2,5-dienone with a Mp 159 ° C.

By proceeding in an analogous manner, except that the 2,6-dibromo-4-isopropylphenol by a suitable amount of 2,6-dibromo-p-cresol (prepared as in reference procedure 1 described) and replaced the N-bromosuccinimide with a suitable amount of pyrrolidone hydrotribromaldehyde 2,6-dibromo-4-methoxy-4-methy] cyclohexa-2,5-dienone with a melting point of 158 to 160 C.

By proceeding in an analogous manner, but replacing the 2,6-dibromo-4-isopropylphenol with a suitable amount of 2-bromo-6-chloro-4-methylphenol (prepared as described in Reference Example 2), 2- Bromo-6-chloro-4-methoxy-4-methylcyclohexa-2,5-dienone with a melting point of 154 to 158 ^° C

Example 28

A solution of 0.5 g of 2,4,6-trichloro-4-methylcyclohexa-2,5-dienone, prepared as in Example 13, in 15 ml of methanol was refluxed for 15 hours. The mixture was poured into water and the solid obtained was separated by filtration and placed in a desiccator to give 0.3 g of 2,6-dichloro-4-methoxy-4-methylcyclohexa-2,5-dienone, mp 157 Oi ₅ 160 ° C. When mixed with 2,6-dichloro-4-methoxy-4-methylcyclohexa-2,5-dienone, which was prepared as described in Example 27, no decrease in the melting point was obtained.

GO 9 0 3 2/1007

By proceeding in an analogous manner, but replacing the methanol with a suitable amount of ethanol, 2,6-dichloro-4-ethoxy-4-methylcyclohexa-2 was obtained after extraction from water with diethyl ether and subsequent drying over magnesium sulfate and evaporation , 5-dienone with a melting point of 63 ^° C.

By proceeding in an analogous manner, but replacing the S ^ O-trichloro - ^ - methylcyclohexa-S ^ -dienone with a suitable amount of S ^ O-trichloro - ^ - isopropylcyclohexa ^ pdienone (prepared as described in Example 13) to yield, after extraction from water with diethyl ether and subsequent washing of the ether with 2N wHflrlgem sodium hydroxide and then with water and drying over sodium sulfate and evaporation gave a residue which after treatment with petroleum ether (bp. 60 to 80 ⁰ C) 1.3 g 2,6-dichloro ^ -isopropyl-

4-methoxycyclohexa-2,5-dienone with a melting point of 93 to 9 ° C revealed.

By proceeding in a similar catfish, _wob el man However, the methanol is replaced by a flattened amount of isopropanol to yield, after extraction from water with DlSthyläther and by subsequent washing of the ether with SN-waßrlgem sodium hydroxide and then with water, drying over sodium sulfate and evaporation S ^ -Dlchlor- ^ isopropoxy-A-methylcyclohexa-as-dlenon with a p _p . _{W bls 5Q} o _{c and a} bp from 60 to 70 ° C / O, 08 mm Hg.

Methanol "/" T ^ ""'"^**'" ° ^{bel ma} "^ ° <= ^h ^ 1 methane by _{e s} eel" ete lot ah Butano! Replaced,

obtained wan after extraction _a “. u

unn *, „ κ u, ^{tralctlon from} V: water with diethyl ether

Na r umh _d ^anSC r ^ießendeS ^ ** ^ '^ *

! u at un ^r r7 ^{And then with WATER} ' ^TrOC ^ - «br Sodium

u fa and E ndampfen ^ Butoxy ^ .e.diohlor. ^ 2,5-dienone with a pp. _of ^ _Με ο _{β and β1η} ^ ξ

6 0 9032/1007

260336;

bin 9 ¹ J ⁰ CA) ₁ OO ~ '" ^λ '<'«' ■

Ind-, Γ n; an in analogue Kel.o vorr.l> -..-., With nan however the methanol d, rch a, · r. «- l, - ,.« te. · * ... - * Replaced in isobutanol, nan got after Kxt.-n.ct) on now Var-ser with oil ethyl ether and by _e n, chlleeu..üo. Washing, ether "with? N-wäßrl _B em Natrlumhyaroxyd and then with water, drying but sodium. sulfate and Kin ^ npOn ,, ö-lHchlor- ^ isobutoxy-K-methylcyclohexa-KS-dlenon with a melting point of ₅ ? to 57 C and a b.p. from -75 to ßoVo.OU mm Hr.

in*-. n.in In ana! o _K cr catfish »orßlnR. except for the fact that methanol oa.xh a _C eei designated V. _e ^ to sec-Eutanol replaced, he., eit one NAO extraction from War.ncr with "iKthylather and

T,,. "" ■,, ""., Mdes Wnr.chon of the ether, nit PN-waBiugen by an.chlR. nd ,, _Tl . _oclmen above Natrlura-

Matriumhydroxya and u.mn with «n. . ,

λ ihiinethylt-sec-butoxy-

en ^, D -. it..1x04

with a bp of 70V0.0 * «π K ₆ .

,. _1r , analogori-r way before (; ln _{G (} where however the

by putting in naUr, .r ^ ^^ ^^^^ ^

_{o T} , _ron .i »6-dichloro ^ -methylcyclohexa-2,5-ciienon

η 'h r'-tractlon from water with Mäthyllither and through an-

Nnoh ^LAtr for ^{U of} _{the ether mlt} SN-aqueous sodium hydroxide

_closing «W _; e dos ^ _{sodium sulphate urd Elr} . _steam

a fp. of 8? to 8 ', ⁰ C after crystallization from acetone-Petrolüthcr (bp. 60 to 80 ° C).

by In _ANALOG it manner before _K LNR to give However, since, TV, .thanol replaced by an iced amount of hexanol, erh "In What after extraction from, .., - n", t nlHtnylütner and washing Lchlleßenden do Ether with ".-" l.erir.em inner lum-

C 0 9 F- 3 2/1 0 0 7

260 3 8 b

hydroxyd then with water, drying over sodium sulfate and evaporation of an oil which was ^{distilled at 170 0} C to remove the Hexanolo, the residue after distillation with 2,6-dichloro-4-hexyloxy-4-methylcyclohexa-2,5-dienone a bp of 144 ^° C / 0.2 mm Hg.

Example 29

A solution of 2.51 g of 2,6-dibromo-p-cresol, prepared as described in reference method 1, in 50 ml Acetonitrile and 50 ml of methanol, which contained 42.16 g of sodium perchlorate monohydrate, in the anode chamber of a divided cell using a smooth platinum anode and separated from the cathode chamber by an ion exchange membrane, which was a smooth platinum cathode in a catholyte of sodium perchlorate monohydrate contained in acetonitrile and methanol, from. Each electrode area was 20 cm and a current of 500 mA was passed through _; until 186 % of the theoretical charge required to achieve a "two electron" reaction had been passed through. The anolyte was diluted with water and the organic solvent evaporated in vacuo. The precipitate was separated by filtration, washed with water and recrystallized from methanol to obtain 2,6-dibromo-4-methoxy-4-methylcyclohexa-2,5-dienone with a mp. 154-156 ⁰ C crystallized.

The infrared spectrum of the product was identical to that of 2,6-dibromo-4-methoxy-4-methylcyclohexa-2,5-dienone, which had been prepared as described in Example 10.

Claims (1)

Claims Method for the control of insects and fungi, characterized in that one insecticidal or fungicidal effective amount of at least one cyclohexadiene derivative of the following general formula at a site with insect or fungi infestation applies: wherein R ^{1 represents} a straight-chain or branched alkyl radical with 1 6 carbon atoms, R ^{2 represents} a chlorine atom, a hydroxy radical, a straight-chain or branched alkyl radical with 1-6 carbon atoms, a straight-chain or branched alkoxy radical with 1-6 carbon atoms or an alkanoyloxy group -OCOIr, wherein R ^ is a straight or branched chain 1 2 denotes an alkyl radical with 1-6 carbon atoms and X and X have the same or different meanings and each represent a chlorine or bromine atom when R is a straight-chain or branched alkyl radical with 1 - 6 carbon atoms ο
and R denotes a chlorine atom, a hydroxyl group, an alkoxy group or an alkanoyloxy group as defined above, or X * and X have the same meaning and each denotes a chlorine or bromine atom if R and R each represent a straight-chain or branched alkyl radical with 1-6 Represents carbon atoms. 609832/1007 2,6-dibromo-4,4-dimethylcyclohexa-2,5-dienone, 4-acetoxy-2,6-dibromo - ^ - methylcyclohexa ^^ - dienone, 2,6-dibromo-4-ethyl-4-hydroxycyclohexa- 2,5-dienone, 2,6-dichloro-4-hexanoyloxy-4-methylcyclohexa-2,5-dienone, 2.6
dienone, 2, δ-dichloro ^ -ethyl ^ -hydroxycyclohexa ^, 5-dienone, 2,6-dibromo-4-hydroxy-4-propylcyclohexa-2,5-dienone, 2,4,6-trichloro-4-isopropylcyclohexa -2,5-dienone, 2,6-dibromo-4-methoxy-4-propylcyclohexa-2,5-dienone, 4-3utoxy-2,6-dichloro-4-methylcyclohexa-2,5-dienone, 2.6 dichloro-4-isobutoxy-4-methylcyclohexa-2,5-dienone and 2, 6-dibromo-4-ethyl-4-methoxycyclohexa-2,5-dienone. 5 ·) Method according to one of claims 1-4, characterized characterized in that the insects are at least one of the following: Coleoptera, Diptera, Lepidoptera and Hemiptera. 2.) method for the control of insects cerruiS claim 1, j; ^k characterized in that the cyclohexadiene derivative of the in [; ^D. Claim 1 given formula does not represent a compound in which \ ^A R represents a chlorine atom. I. IP 2.) Method for the control of insects according to claim 1, | characterized in that the cyclohexadiene derivative used is a compound of the general formula according to ^: iß claim 1, wherein X ¹ and X ^{2 have} the same meaning and each represent a ^{chlorine or a bromine atom, R 1} a methyl, ethyl, propyl or isopropyl radical and R represents a chlorine atom, a hydroxy radical, a methyl radical, a methoxy radical, a butoxy radical, I an isobutoxy radical. an acetoxy group or a hexanoyloxy group means. 4.) A method for controlling insects according to claim 1, characterized in that the cyclohexadiene derivative used ^e is at least one of the following: ^υ ir 609832/1007 2603364 6.) Method according to one of claims 1 - 5, characterized in that that the insects are at least one of the following: Diabrotica spp., Anthonornus spp., Sitophilus spp., Anopheles spp., Aedes spp., Culex spp., Ceratitis spp., Ragoletjs spp., Hylemia spp., Heliothis spp., Spodoptera spp., Ostrinia spp., Pieris spp., Laphygma spp., Agrotis spp., Spargothis spp., Tortrix spp., .T. Plutella spp., Aeneolamia spp., And Dysdercus spp .. . [.. 7 ·) Method according to any one of claims 1-6, characterized by gell indicates that the insects are at least one of the following: ! '; Sitophilus oryzae, Musca autumnalis, Musca domestica, Heliothis J; virescens, Spodoptera littoralis, Spodoptera eridania, Mamestra configurata, Trichoplusia ni, Diprion pini, Cydia pomonella, Plutella xylostella and Phorodon humuli. ί ■, j 8.) Method for controlling fungi according to claim 1, Ji characterized in that the cyclohexadiene derivative used f represents a compound of the formula given in claim 1 j: and X and X have the same meaning and each is a Represent chlorine or bromine atom, R ^{1 represents} a methyl or ethyl radical and R represents a straight-chain or branched alkoxy radical having 1-6 carbon atoms or an alkanoyloxy group - (wherein R ^ has the meaning given in claim 1, represents. 9.) Method according to claim 8, characterized in that R ^{2 represents a} methoxy radical or an acetoxy or propionyloxy group. 10.) A method for the control of fungi according to claim 1, 8 or 9, characterized in that the cyclohexadienderlvate used is at least one of the following compounds: 4-methyl-A-propionyloxycyclohexa-2,5-dienone and ^ -acetoxy-2,6-dibromo-4-ethylcyclohexa-2,5-dienone. 609332/1007 - ^7T "260386 *. 11.) A method for controlling fungi according to claim 1, 8, 9 or 10, characterized in that the fungi at least one of the following are: Alternaria spp., Botrytis spp., Helmintho sporium spp., Fusarium spp., Mycosphaerella spp., dusty Meltau species, Phycomycetes, brandies, Tilletia caries, Ustilago spp. * Rhizoctonia spp. and Sclerotinia spp. 12.) The method according to claim 11, characterized. that the fungi are at least one of the following: Erisiphe spp., Podosphaera spp., Phytophthora spp., Uromyces spp. and Puccinia spp. 13.) The method according to claim 11, characterized in that the fungi are at least one of the following: Alterriaria solani, Botrytis cinerea, Helminthosporium avenae, Fusarium sambucinum, Mycosphaerella pinodes, Erysiphe graminis, Podosphaera leucotriche, Phytophthora infestans and Uromyces appendiculatus. . lh) The method according to any of claims 1-13, characterized in that the cyclohexadiene derivative is applied at the site of insect or Fungibefalls in the form of a composition which is suitable for use in the control of insects and fungi, and at least a cyclohexadiene derivative of the general formula given in claim 1, in which R, R, X and X have the meanings given in claim 1, together with one or more diluents which are compatible with the cyclohexadiene derivative and suitable for use in such compositions. 15 x) A method according to any one of claims 1-14, characterized in 'that the cyclohexadiene derivative to control the active stages of the insects and fungi, the crop located for in the growth, stored products, household goods wood or wood products, Farm - and are harmful to pets and humans. r <- ■ -) I ; 7/1 η Γ) " ^7Ö " 260386; Process _e emäß one of claims 1 A 1 * and 15 °. "T" W.-.- u-'i / ^ -1 ΡΠ-Ι & - - · marked that the . .r ^ »-. Mn 1 S. LiHJar \ , > ~ »-— - - ., Mamestra to control Hello «,«. * «^ - - <- figurata, Laphygma s _PP . and Agrotis s _PP . characterized in that the _control Cyc Method according to claim 17, characterized in that that the stored products are grain. ₁₉ ) Method according to claim 17, characterized in that the household goods are textiles. -α flnc-nruch 19, characterized in that 20.) method according to claims i? that the textiles are carpets. ₉₁ χ method according to one of claims 1 - 7, 1 »and I ₅ , 2i.) Method b _lohexadle n derivative on FeId- ^{gekennZeiChnet} '.. ^d ^ rr control of the larvae and ex- mustard-eating beetles or beetle-like , seed beetles or grain beetles is used. Food according to claim 21, characterized in that _{3 is} maize, cotton, rice or the potato. _{25} method E} e «ä3 claim Pl, characterized in that the vegetables are beans or cucumbers. , iiß one of Claims 1 - 7, Ik and I ₅ , that the cyclohexadiene derivative is used 6098 32 / V0Q7 I - 79 - < is used in cotton, sugar cane or fruit trees to control 1 sucking insects or parasites. | j. 25) The method according to claim 14, characterized in \ that the sucking insects or parasites aphids, singing | are chirping or cicadas, plant bugs and suckers or parasites. 26.) Method according to one of claims 1 - 7, 14 and 15, characterized in that the cyclohexadiene derivative in fruit and forest trees is used to control sawsaws, sawfly, moths, moths and flies. 27.) Method according to one of claims 1 - 7, 14 and 15, characterized in that the cyclohexadiene derivative is used in field crops to control flies. 28.) The method according to claim 27, characterized in that the field crop is a beet, chard or a cabbage crop is. 29.) Method according to one of claims 1 - 7, i4 and 15, characterized in that the cyclohexadiene derivative is used in wood or wood products for protection against attack of beetles or beetle-like insects. 20.) Method according to one of claims 1 and 8-15, characterized in that the cyclohexadiene derivative is used is used to control diseases caused by fungi on seeds and foot rot by applying it as a seed preparation. 51.) procedure according to; Claim JO, characterized in that that the cyclohexadiene derivative is used to control diseases caused by fungi on the seeds and foot rot in cereals is applied. 52.) Method according to claim J50 _or Jl, characterized 609832/1007 - P.O - η indicates that the Kungus is one or more of the "Ehrcrc d avcnac, Tlllctla caries, Us, HeUdnp Rhlzoctonia spp. and Fucarium spp different types of meltau in cereals, apples, pears trolls of bibuu «» b cucumbers and ornamental plants. _3M method cemSB claim 35, characterized _e e. ™ i = hnet that the ornamental plants are pants. ", ■ r> one of claims 1 and 8-12, »·> ..!" "- Let, there, the CC-- - 15, _proceed ^^^^. "^ ,. t _Z ur Ko, - ^αΓ - ^! ^ ϊίΓ ^ Χπ ⁰ ^ 'sputen "eltaus oei tomatoes at _e e" ends r r • α Mnpm of claims 1 and 8-15. 38.) ^AV t ^e t 7 _a: dal ^ olohexadicn derivative, for Kontrol.e aurcb Beicenm "lom">. ^ _{Kulturpflan2enanpflanz} un _B s Toggle from Phycomyceteniniei ^ x is turned. according to claim ^, characterized in that Hi 1_. "^." - r procedure for measure one of the claims! and 8 - II and ' ⁰ ^, = signified by this. that the cyclohexadiene derivative ¹⁵ "I vonoraueehlmnelart" and La _E brandon von Stein- Γ ^ Γ ^ Γ pay attention or we.ntrau.en at _C e _W cnde _{t W will} . 609832/1007 41.) The method according to claim 40, characterized in that that the stone fruits plums, apricots or peaches and the soft fruits strawberries, raspberries, black or red currants are. 42.) The method according to claim 15, characterized in that that 'the cyclohexadiene derivative in growing crops in the form of foliar sprays, dusts, granules or -foaming is applied. 4 ^.). Method according to claim 15, characterized in that that the cyclohexadiene derivative is used as a soil or root treatment j medium in the form of a liquid medium, dust, granules, a \ smoke-producing agent or foam is used. 44.) The method according to claim 15, characterized in that that the cyclohexadiene derivative is used in the form of a seed preparation by liquid slurries and dusts. ) Method according to claim 15, characterized in that that the cyclohexadiene derivative in farm or domestic animals in the form of a spray, a spray, an immersion agent, in Fo: m an effervescent agent applied by a self-treatment method, by infusion or as dust or mist will. 46.) The method according to claim 45, characterized in that that the self-treatment method involves dusting, dusting, rubbing the back, or using a lick of cattle salt includes. 47.) The method according to claim 15, characterized in that that the cyclohexadiene derivative is used in stored products or household goods in the form of a spray, dust or smoke will. 609832/1007 260386. ^ - ¹ ^ ·) method cemä: 3 claim 15, characterized · characterized in that the cyclohexadiene derivative to maintain public health or the health of animals in the form of sprays, sticks, mist-forming agents or poisoned bait in places of the infestation is applied. 49.) The method according to claim 15, characterized in that the point of infestation is a dwelling, an animal housing, a dung heap or water. 50.) The method according to claim 15, characterized in that the cyclohexadiene derivative is a compound according to claim 2, 3 or 4 and the cyclohexadiene derivative is used to control Lepidopterus pests. . I 51 ·) Method according to claim 50, characterized in that I that the Lepidopterus pest is Heliothis virescens. 52.) The method according to claim 50 or 51, characterized in that the cyclohexadiene derivative on leaves of host I plant in the form of sprays, dusts or foams applied l will. I 53.) Insecticidal and fungicidal compositions, thereby I characterized that they contain at least one cyclohexa- I diene derivative of the general formula given in claim 1, [wherein R ¹ , R ² , X ¹ and X ^{2 have} the meanings given in claim 1 I own, along with one or more of the aforementioned \ Cyclohexadiene derivative compatible and for use in j such compositions contain suitable diluents I. keep. ! f 5 ^.) Insecticidal compositions according to claim 55t dall characterized in that they contain at least one cycloid as active ingredient hexadiene derivative of the formula given in claim 1, wherein R, ■ 12 I X and X have the meaning given in claim 1 and R f 'is a hydroxy radical _# a straight-chain or branched alkyl!. remainder with 1-6 carbon atoms, 609832/1007 a geracl / .r-ttj.- unc gen or branched alkoxy radical with 1 - 6 carbon. *. * ™ _{Oläcr denotes} an Aikanoyloxyeruppe -OCOH ⁵ , where B an _eerf ,! - si ' λ χ. «LwiT-nct · with 1 - 6 carbon atoms. _n chain or branched alkyl radical with ι ι 60 represents included. · ■ · ' ke per ct 55.) Insecticidal compositions according to claim 53, characterized in that they contain at least one cyclohexadiene derivative of the general formula given in claim 1 as active ingredient, I ei wherein R ¹ , R ² , X ¹ and X ^{2 have} the meaning given in claim j> j Bt or contain a cyclohexadiene derivative according to claim 4. Hey 56.) Cyclohexadiene derivatives of the Bi general formula given in claim 1, wherein R ¹ , R ² , X ¹ and X ^{2 have} the meaning given in claim ^ yes, with the proviso that (i) when X (and X ² have the same meaning and each represent a chlorine or bromine atom and R ^{2 represents} a hydroxy radical or an acetoxy group, R ^{1 has} a meaning different from that of a methyl radical, or (ii) when R ¹ and X each represent a bromine atom and R ² a Means methyl radical, R has a different meaning than that of a methyl radical or (iii) when X ¹ , X ² and R ² each represent a chlorine atom, R has a different meaning than that of a tert-butyl group. 57.) Cyclohexadiene derivatives according to claim 56, characterized in that R ^{2 represents} a hydroxy radical, a straight-chain or branched alkyl radical with 1-6 carbon atoms, a straight-chain or branched alkoxy radical with 1-6 carbon atoms or an alkanoyl.oxy group -OCOR ⁵ , wherein R is a straight-chain or branched alkyl radical having 1-6 carbon atoms. 58.) Cyclohexadiene derivatives according to claim 56 or 57, characterized in that R represents a methyl radical. 59.) Cyclohexadiene derivatives according to claim 56, characterized 6098 ° 2/1007 in that X and possess ¹ and X ² have the same meaning in each case a bromine or chlorine atom, R represents a methyl radical and R ² designate the meaning given in Claim 1 \ sits. 60.) Cyclohexadiene derivatives according to claim 56, characterized in that X ¹ and X ^{2 have} the same meaning and each represent a chlorine or bromine atom, R ¹ denotes a methyl, ethyl, propyl or isopropyl radical and R a chlorine atom , denotes a hydroxy group, a methyl group, a methoxy group, a butoxy group, an isobutoxy group, an acetoxy group or a hexanoyloxy group with the proviso that (i) when X and χ ^{2 have} the same meaning and each represent a chlorine or bromine atom and R ² represents a hydroxy radical, R has a different meaning than that of a methyl radical or (ii) when X ¹ and X ² each represent a bromine atom and R represents a methyl radical, R ^{1 has} a different meaning than that of a methyl radical. 61.) Cyclohexadiene derivatives according to claim 56, characterized in that X ¹ and X ^{2 have} the same meaning and each represent a chlorine or bromine atom, R is a methyl or ethyl group and R ^{2 is} a straight-chain or branched alkoxy radical with 1 - 6 carbon atoms or an alkanoyloxy group -OCOR ⁵ , in which R ^{5 represents} a straight-chain or branched alkyl radical with 1-6 carbon atoms. 62.) Cyclohexadiene derivatives according to claim 6l, characterized in that R ² denotes a methoxy radical or an acetoxy or proponyloxy group. 65.) 2.6 6k.) 2, i 65.) Z.Ö-dichloro ^ - ethyl-'l-hydroxycyclohexa ^ .S-dienone. 66.) 2,6-Dibromo - ^ - hydroxy-n-propylcyclohexa-2,5-dienone. 6 0 9 3 3 2/1007 67.) 2,4, δ-Trichloro ^ isopropylcyclohexa ^, 5-dienone. | ■ \ 68.) 2,6-dibromo-4 ~ methoxy-4-propylcyclohexa-2,5-dienone. i 69.) 4-Butoxy-2,6-dichloro-4-methylcyclohexa-2,5-dienone. I. 70.) 2,6-dichloro-4-isobutoxy-4-methylcyclohexa-2,5-dienone. \ ν I 71.) 2,6-Dibromo-4-ethyl-4-methoxycyclohexa-2,5-dierion. ξ 72.) 2, ö -dibromo ^ -methoxy ^ -methylcyclohexa ^, 5-dienone. | 7Y. ) 2, o-dibromo ^ -methyl ^ -propionyloxycyclohexa ^; 5-dienon. 75.) 2,6-dichloro-4,4-dimethylcyclohexa-2,5-dicnone, 2,6-dibromo-4-butyryloxy-4-methylcyclohexa-2,5-dienone, 2,6-dibromo-'lisobutyryloxy- 4-methylcyclohexa-2,5-dienone, 2,6-dibromo-4-hexanoyloxy-4-methylcyclohexa-2,5-dienone, 2,4,6-trichloro-4-methylcyclohexa-2,5-dienone, 2, 4, ö-Trichlor - ^ - propylcyclohexa ^, 5-dienone, 2-bromo-4,6-dichloΓ-4-methylcyclohexa-2,5-dienone, 2,4,6-trichloro-4-sec.-butylcyclohexa- 2,5-dienone, 4-butyl-2,4,6-trichlorocyclohexa-2,5-dienone, 2, o-dibromo ^ -chloro ^ -methylcyclohexa ^, 5-dienone, 2,4,6-trichloro-4 ethylcyclohexa-2,5-dienone, 2,6-dichloro-4-hydroxy-4-propylcyclohexa-2,5-dienone, 2-bromo-6-chloro-4-hydroxy-4-methylcyclohexa-2,5-dienone , 2,6-dibromo-4-hydroxy-4-isopropylcycloVlexa-2,5-dienone, 2,6-dichloro-4-hydroxy-4-isopropylcyclohexa-2,5-dienone, 2,6-dichloro-4-hydroxy -4-tert-butylcyclohexa-2,5-dienone, 2,6-dibromo-4-hydroxy-4-sec-butylcyclohexa-2,5-dienone, 2,6-dibromo-4-hydroxy-4-tert .-Butylcyclohexa-2,5-dienone, 2,6-dichloro-4-hydroxy-4-sec.-butylcyclohexa-2,5-dienone, 4-acetoxy-2,6-dichloro -4-ethylcyclohexa-2,5-dienone, 4-acetoxy-2,6-dibromo-4-propylcyclohexa-2,5-dienone, 4-acetoxy-2,6-dibromo-4-isopropylcyclohxa-2,5-dienone , 4-acetoxy-2,6-dichloro - ^ - isopropylcyclohexa-2,5-dienone, 2,6-dibromo-4-methyl-4- (3-methylbutanoyloxy) cyclohexa-2,5-dienone, 2,6- Dibromo-4- (2-ethylbutanoyloxy) -4-methylcyclohexa-2,5-dienone, 2,6-dibromo-n-methyl- (2-methylbutanoyloxy) -4-methylcyclohexa-2,5-dionone-2-, 6-dichloro -4-ethyl-4- (5- _me thylbutanoyloxy) cyclohexa-2, 5-dienone, S / ö-dichloro-N-methyl-lupropionyloxycyclohexa ^, 5-d ionone, Ji-paityryloxy-S, 6-dichloro-4 -methylcyclohexa- ?, 5-dienone, oyloxyW, 2,6-Dlbro »- 5-dlenone, 2,6-di-bromo-4-butyryl xycycl hexa 2 c, _ethyl . _{4th isobutyryl} ; ; 4 _l oXo 5-dlonon _{ropionyloxyoyclohexa} . ₂ . ₅ ο n? _h ^ Ϊ Khyl -'.- isobutyryloxycyclohaxaa.S. 2.6- _2, 6-hl4athyl y
ty _xa _ - '. hex ^ ^ -de on
:: T; ; Γηοη! 2 eiichior - ^ - proplonyloxy-i.-tcrt.-butyl- cyolohexa.2,5-dionon, 2.. _{% loheJta} . oydonexa-2. ₅ -dl »n. - -toxy ^^.". ^^^, "^. ^ 5. ² ' ⁵ Tl eiy-2 e-dichloro-t-tert-butylcyclohexa-SS-dler.on. -2.5-dienone. . :; SU ^. o _h exl2, _5d ien ^, _rT sel.-butylcyclohexa-aS-dionone. 2.6-Dlbro _ra - -lsobutyry oxy-4,, »,„ v,? s-dlenone, 2,6-dichloro-t-isobutyryloxy-4 -butyl = yclo _h e _X a-2, ₅ -dlcnon, ae iclohexa ^^ - aienon. ₂ .6- _Dlb ro _m -4- _m et _h ox _ri - _S oo -bu yl- -2 5-dienone, ae-dibromo -'.- mcthoxy-t-tert.-butyloyclc- ^ thxycyclohexaS ^ , 2 5-dlenon. S.e 2 e-dichloro- ^ methoxyy ^ i'SSdlenon. 2.6 dichloro »N-Butyryloxy ^ .ö-dichloro-U-tert.-butylcyclohexa-a.S-dienone, 609832/1007 ir 4-.isopropyl-4-methoxycyclohexa-2,5-dienone, 2-bromo-6-chloro-4- methoxy-4-methylcyclohexa - 2 _f 5-dienone, 2,6-dichloro-H-ethoxy-4- 2 (methylcyclohexa-2,5-dienone, 2,6-dichloro-4-isopropoxy-4-methyl- cyclohexa-2,5-dienone, 2,6-dichloro-4-methyl-4-sec-butoxycyclohexag _; 2,5-dienone, 2-bromo-6-chloro-4-ethoxy-4-methylcyclohexa-2,5-di- ^cnone d. t and 2,6-dichloro-4-hexyloxy-4-ynethylcyclohexa-2,5-dienone. w 76.) Insecticidal and fungicidal compositions according to claim 52 »54 and 55», characterized in that they are 0.001 95 Contain wt .- # of the cyclohexadiene derivative. 77.) Insecticidal and fungicidal solid or liquid compositions according to claim 55, 54 or 55 for use at Cultivated plants in the process of growth and locations intended for the growth of cultivated plants, for topical application with animals, with wood, with stored products, with household goods and their surroundings, characterized in that they contain 0.001-60 wt .- # cyclohexadiene derivative. 78.) Insecticidal and fungicidal compositions according to An-Spruch 77, characterized in that it is 0.01-10 wt Cyclohexadiene derivative contain. 79 ·) Insecticidal and fungicidal compositions according to claim 53 »54, 55» 76, 77 or 78, characterized in that they contain at least one auxiliary compound or an auxiliary substance. 80.) Insecticidal and fungicidal compositions according to claim 79 »characterized in that the adjuvant is an insecticide, a ■ non-insecticidal synergistic methylenedioxyphenol derivative, is a fungicide, a Bacillus thuringiensis preparation, or an insect virus. 81.) The method according to claim 16, characterized in that the cyclohexadiene derivative in a dose between 10 and 609832/100? - Γ-8 - (L 2000 g per hectare is used. 82.) Method according to claim B1, characterized in that that the cyclohexadiene derivative applied as a composition which contains 0.001 to 2.0% by weight of cyclohexadiene derivative. ; 83.) The method according to claim 82, characterized in that that the composition is used in the form of a spray. 64.) The method according to claim 21, 22 or 23, characterized in that that the cyclohexadiene derivative is used in a dose of up to 5000 g per hectare. 85.) The method according to claim 84, characterized in that that the cyclohexadiene derivative is used as a composition containing 0.01 to 2.0 parts by weight of the cyclohexadiene derivative. 66.) The method according to claim 85, characterized in that that the composition is in the form of a dust or spray. 87.) The method according to claim 24 or 25, characterized in that that the cyclohexadiene derivative is used in a dose of 100 to 2000 β per hectare. 88.) The method according to claim 87, characterized in that that the cyclohexadiene derivative is used as a composition containing 0.01 to 5.0 wt .- ^ cyclohexadiene derivative. # 9.) Method according to claim 88, characterized in that that the composition is applied in the form of a spray. 609832/1007