DE2805227A1 - METHOD OF REGULATING THE GROWTH OF PLANTS - Google Patents

Description

PATENT ADVOCATE /. ■ - -.

DR.RICHARD KNEiSSL ^ψ OR Π Κ Oil

Widonirayerstr. 45 4.0 UO C, 4th I.

D-8000 MUNICH 22 Tel 089/295125

Folder 24 394 Dr.K / rm ICI Case No. PP 29331/29817

IMPERIAL CHEMICAL INDUSTRIES LIMITED London / Great Britain

Process for regulating the growth of plants

809833/0880

"ϊ ~ ' 280 ^ 227

description

The invention relates to the use of heterocyclic compounds, which are imidazole or 1,2,4-triazole compounds, as Plant wax borne regulation agents. The invention further relates to some of the heterocyclic compounds themselves. The invention has reference to NL-PA 7 609 439, the details of which as in the this application should apply included.

The invention relates to a method for regulating the growth of plants, which is carried out by applying a compound of the general formula It

Y-N CH-Z — R "

wherein R ^ is alkenyl, alkynyl or optionally substituted Aralkyl or aralkenyl, R2 for cycloalkyl, alkyl or haloalkyl Y is = N- or = CH- and Z is C = O or a derivative thereof, or an acid addition salt or a Metallkoaplex applies such a connection.

The compounds can contain chiral centers. Such connections will be in. generally obtained in the form of racemic mixtures. However, these and other mixtures can by in the Technique known per se processes separated into the individual isomers for example by chromatography.

The alkyl groups, which can be straight-chain or branched, preferably contain 1 to 5 carbon atoms. Examples are methyl, ethyl, propyl (n- or i-propyl) and butyl

809833/0880

S ' 2605227'

(η-, i- or t-butyl). Suitable alkenyl and alkynyl groups, which can also be straight-chain or branched-chain are those with up to 7, preferably up to 4, carbon atoms. Examples are allyl and propargyl.

The aralkyl groups suitably contain 7 to 12 carbon atoms with 1 to 3 carbon atoms in the alkyl portion. The aralkyl group (eg benzyl) can be substituted in its alkyl part (eg CH ₂ ) and / or aryl part (eg phenyl). Suitable substituents on the aryl part (e.g. phenyl) are halogen, C _1- ^ -alkyl [e.g. methyl, ethyl, propyl (n- or i-propyl) and butyl (η-, i- or t-butyl)], halogeno- ( Oj ^ -alkyl), phenyl, halogenophenyl (e.g. chlorophenyl), cycloalkyl, nitro, cyano, C ₁ λ-alkoxy (e.g. methoxy or ethoxy), (C ₁ ^ -alkylene) -dioxy (e.g. methylenedioxy), (C ₁ ^ -alkoxy) - (C _{1-Z (alkyl)} (such as 2-methoxy or ethoxyethyl), mercapto, (C ^^ - AlkylJ-thio (for example methyl- or ethyl-thio), (C ₁ _ ₄ alkyl ) -sulfonyl (for example methyl or ethylsulfonyl), (C ₁ _ »- haloalkyl) -sulfonyl (for example trifluoromethylsulfonyl), phenylsulfonyl, unsubstituted or mono- or di- (C ₁ _ ^ - alkyl) -substituted sulfamoyl or carbamoyl, carboxy , _(C1 ^ - alkoxy) carbonyl (for example, methoxy or ethoxy-carbonyl), or unsubstituted or mono- or di- (C ₁ _ ^ - alkyl) -substituted amino, (C ₁ _g alkanoyl) amino, N - (C ₁ _ »- alkyl) -substituted (C ₁ _g alkanoyl) -amino, formylamino, N- (C ₁ _ ^ - alkyl) -substituted formylamino, phenylethyl, phenoxy or benzyloxy. suitable alkanoyl is acetyl or propionyl. The aralkyl group can contain more than one ring substituent. Examples of polysubstituted groups are those which are substituted with up to the maximum possible number (in particular 1, 2 or 3) of , for example, halogen atoms (in particular chlorine atoms) and / or nitro, methyl or methoxy groups. Suitable substituents on the alkyl part of the aralkyl group (e.g. benzyl) are halogen, C ₁ __ ^ - alkyl (e.g. methyl), phenyl or benzyl, where the latter two groups can optionally be substituted as indicated above for aryl, cyano, (C _1- ^ - AlkOXy) carbonyl (eg methoxy or ethoxycarbonyl) or trihalogenomethyl (eg trifluoromethyl).

809333/0880

- JiT -

> 28US227

Examples of suitable aralkyl groups are benzyl itself, <x-methylbenzyl, a-methylchlorobenzyl (e.g. oc-methyl-p-chlorobenzyl), cc-IIethyldichlorobenzyl (e.g. <x-methyl-2,4-dichlorobenzyl), a-methylbromobenzyl (e.g. a-methyl-p-bromobenzyl), a-methylfluorobenzyl (e.g. a-methyl-p-fluorobenzyl), α-ethylchlorobenzyl (e.g. a-ethyl-p-chlorobenzyl), a-ethylfluorobenzyl (e.g. a-ethylp-fluorobenzyl), chlorobenzyl (e.g. o-, m- or p-chlorobenzyl), dichlorobenzyl (e.g. 2,4-, 5,4- or 2,6-dichlorobenzyl), trichlorobenzyl (e.g. 2,3,6- or 2,4,5-trichlorobenzyl ), Tetrachlorobenzyl, pentachlorobenzyl, bromobenzyl (e.g. o-, m- or p-bromobenzyl), dibromobenzyl (e.g. 2,4-dibroinobenzyl), fluorobenzyl (e.g. o-, m- or p-fluorobenzyl), difluorobenzyl (e.g. 2,4 -Difluorobenzyl), pentafluorobenzyl, iodobenzyl (e.g. o-iodobenzyl), aminobenzyl (e.g. p-aminobenzyl), methylbenzyl (e.g. o-, m- or p-methylbenzyl), dimethylbenzyl (e.g. 2,6-, 2,5- or 3 , 4-dimethylbenzyl), ethylbenzyl (e.g. p-ethylbenzyl), butylbenzyl (e.g. pt-butylbenzyl), C yanobenzyl (e.g. o- or p-cyanobenzyl), nitrobenzyl (e.g. o-, m- or p-nitrobenzyl), (trifluoromethyl) benzyl [e.g. o-, m- or p- (trifluoromethyl) benzyl], methoxybenzyl (e.g. o-, m- or p-methoxybenzyl), ethoxybenzyl (e.g. o-, m- or p-ethoxybenzyl), chloronitrobenzyl (e.g. 3-nitro-4-chlorobenzyl), fluoronitrobenzyl (e.g. 2-nitro-4-fluorobenzyl), chlorofluorobenzyl (e.g. 2-chloro-4-fluorobenzyl, Z- fluoro-4-chlorobenzyl or 2-chloro-6-fluorobenzyl), fluorobromobenzyl (e.g. 2-fluoro-4-bromobenzyl), methylenedioxychlorobenzyl (e.g. 2-chloro-4,5- methylenedioxybenzyl), methoxybromobenzyl (e.g. 2-methoxy-5-bromobenzyl or 3-bromo-5-niethoxybenzyl), methoxynitrobenzyl (e.g. 2-methoxy-5-nitrobenzyl), benzyloxybenzyl (e.g. p-benz3'-loxybenzyl), phenylbenzyl (e.g. p-benz3'-loxybenzyl), -Phenylbenzyl), phenylethyl (e.g. 2-phenylethyl), diphenylethyl or naphthylmethyl.

The cycloalkyl group suitably has 3 to 6 carbon atoms. Preferably it is cyclopropyl, cyclo pentyl or cyclohexyl.

809833/0880

Preferably the haloalkyl group contains 1 to 3 halogen atoms. Examples are 2-chloroethyl and trifluoromethyl or trichloromethyl.

The halogen can consist of fluorine, chlorine, bromine or iodine.

The aralkenyl group suitably contains 8 to 13 carbon atoms with up to 4 carbon atoms in the alkenyl part. the Aryl and alkenyl portions of such a group can be substituted as indicated above for the aralkyl group. A suitable aralkenyl group is 3-phenylallyl.

The C = O derivative is suitably a ketal, hydrazone, Semicarbazone, imine, or oxime.

A preferred class of compounds includes those wherein R .. for propenyl, phenylpropenyl, propynyl, benzyl, α-methylbenzyl, α-methylchlorobenzyl, α-methyl-dichlorobenzyl, α-methyl-fluorobenzyl, a-methylbromobenzyl, a-ethylchlorobenzyl, a-ethylfluorobenzyl, Chlorobenzyl, dichlorobenzyl, trichlorobenzyl, pentachlorobenzyl, Bromobenzyl, dibromobenzyl, fluorobenzyl, difluorobenzyl, Iodobenzyl, aminobenzyl, methylbenzyl, dimethylbenzyl, ethylbenzyl, butylbenzyl, cyanobenzyl, nitrobenzyl, trifluoromethylbenzyl, Methoxybenzyl, ethoxybenzyl, chloronitrobenzyl, Fluoronitrobenzyl, chlorofluorobenzyl, fluorobromobenzyl, methylenedioxychlorobenzyl, Methoxynitrobenzyl, phenylbenzyl, diphenylethyl or benzyloxybenzyl, Y stands for = N-, R £ for cyclohexyl, Is propyl or butyl and Z is C = O. In addition, the corresponding compounds are preferred in which Y is = CH- stands.

Particularly preferred are those compounds in which R ^ is allyl, 3-phenylallyl, propargyl, benzyl, α-methylbenzyl, α-methylp-chlorobenzyl, a-methyl-2,4-dichlorobenzyl, a-methyl-p-bromobenzyl, a-methyl-p-fluorobenzyl, a-ethyl-p-chlorobenzyl, a-ethyl-p-fluorobenzyl, o-, m- or p-chlorobenzyl, 2,4-, 3,4-

809833/0880

or 2,6-dichlorobenzyl, 2,4,5- or 2,3,6-trichlorobenzyl, pentachlorobenzyl, o-, m- or p-bromobenzyl, 2,4-dibromobenzyl, o-, m- or p-fluorobenzyl, 2,4-difluorobenzyl, o-iodobenzyl, p-aminobenzyl, o-, m- or p-methylbenzyl, 2,5- or 3,4-dimethylbenzyl, p-ethylbenzyl, pt-butylbenzyl, o- or p-cyanobenzyl, o-, m- or p-nitrobenzyl, o-, m- or p- (trifluoromethyl) -benzyl, ο- or p-methoxybenzyl, o-, m- or p-ethoxybenzyl, 3-nitro-4-chlorobenzyl, 2 -Nitro-4-fluorobenzyl, 2-chloro-4-fluorobenzyl, 2-fluoro-4-chlorobenzyl, 2-chloro-6-fluorobenzyl, 2-fluoro-4-bromobenzyl, 2-chloro-4,5-diethylenedioxybenzyl, 3 -Bromo-5-methoxybenzyl, 2-methoxy-5-nitrobenzyl, p-benzyloxybenzyl, p-phenylbenzyl or ß, ß-diphenylethyl, Y = N-, R ₂ = cyclohexyl, i-propyl, t-butyl or i-Butyl stands vmd Z stands for C =O. Furthermore, particularly preferred compounds are those in which R _{1 is} 3-phenylallyl, benzyl, α-methyl-pchlorobenzyl, o- or p-chlorobenzyl, 2,4- or 3,4-dichlorobenzyl, o- or p-fluorobenzyl, m- Trifluoromethylbenzyl, o- or p-bromobenzyl, p-cyahobenzyl or 2-chloro-4-fluorobenzyl, Y is = CH-, R _{2 is} t-butyl and Z is C = O.

Suitable salts are salts with inorganic or organic acids, such as salt, nitric, sulfur, toluenesulfone, Acetic or oxalic acid.

The metal complex is suitably one, the copper, Contains zinc, manganese or iron. It preferably has the general formula:

where Z, Y, R ₁ and R _{2 have} the definitions given above, M stands for a metal, A stands for an anion (e.g. a chloride,

809833/0880

Bromide, iodide, nitrate, sulfate or phosphate anion), η for 2 or 4 and Y is O or an integer from 1 to 12.

Specific examples of suitable triazole and imidazole compounds are given in Tables I and II, respectively.

809833/0880

CN 0 CN ' I. CN 0 CN O CN cn O CN CN O Γ0 O
Il CN O O pi co S3 S3 O 33 VO S3 S3 O O iu 11
U S3 vo in CN U Γ O VD U U 'S * U r- U U co CN • U ιΗ Ι in I. I. r-H I. I. I. CQ *? I. r-i φ I. S3 O o> S3 S3 S. I. 33 ft 00 ε 1 33 LO I. XJ O CN vo. VD VO VD VD O vo vo vo co CN OO CN U O CN α U O O CN I. O S3 O
Jl I. I. in O
| j VO I. O
M. r-i e O
Il (13 ' U U II
U O
I] It
U Ui U
α O
) | II
. U O O
11 ₃ 3 Il
O J ₃ I. 3 3 I. Il
U CQ CQ 3 CQ CQ 3 Ρί CQ You I. cn I. CQ I. I. CQ I. CQ -P I. • P -P I. 4Y I. CN -P CN ** " I. r- S3 I. CN U I. 33 OO U S3 CN I. vo 33 33 U O vo I. I ^s O i-l 33 4) I. U VO ί> -H U ¹ O I. I. ^; · "# U ·. I. co ft co

80983 3/088

ΆΙ-

N • Ρ Φ

O
in
co
I.
ro
co 84-86 ° 88-89 ° 130-132 ° 140-142 ° 115-117 ° 185-187 ° O
co
I.
co
co 76-77 ° O = D O = D O = D C = O C = O C = O O
Il
Ό O
i!
U 9
6th t-bu t-bu t-bu t-bu t-bu i-Pr t-bu i-Pr 3
m B '
C?
Il
U
B.
U I.
CN
B.
O
«V
B.
vo
U
fa
O I.
CM
U
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O
i
O I.
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B.
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ro
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α
1
ri
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VD
CN I.
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B.
vo
α
I.
ii
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Ό
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CM CM
B.
U
B.
VO
α
O
I. I.
CN
1 - t
U
ro
B.
VO
U
CM
O
I.
in
O
OO
U
CN 1
CM
MI
U
in
B.
VD
U I.
CN
1-*
O
* ~ vo
U
I.
U
a
I.
O O H
ri CM
ri cn
ri H in
H vo
H Γ-
ri co
rl

309833/0880

-Al-

N -PQ) ca • Ρ UO

O CN CN 0 CN O 0 O CN CN O O CN O CN CN K O O cn cn ro K O cn a O a O U - I. in U CN 03 CN CJ r » rH CJ 03 U rH co ro I. "-1 rH I. rH I. I. rH ! ro I ' K cn cn CJ I. vo I. Qj rH I. a CO a 8th vo rH ■ sr r- co rH VO F- p » VO r »· VD rH O CN CN CJ rH CJ CJ O I. O cj rH O rH I. ro O rH I. O I. H rH Il ir » O Il O CN U O Il rH CJ U U S. Il CJ Ii U Il CJ CJ CJ 3 - I. 3 VO α 3 U U CJ I. S-i -H 03 O CJ 3 approx U (U
f U a, (U
■ r3 I.
+) I. I.
• P 05 t
4Y CU
■ •H! (U
■ - St. I. I. I.
4Y ■ HI ■ HI • sr O LO I. ro CN CN CN I. a I. VD I. CN I. CN I j ^ - » S. ro CJ. ι ** Π 23 [Il CJ a VO K . CJ ο / CJ I. UT U * I. VO ft U CN rH CN CN CN

309833/0880

143-146 ° 102-103 ° 86-88 ° 137-139 ° 58-59 ° 86-88 ° 131-133 ° 111-113 ° O = D C = O C = O O = D C = O O
Ii
CJ O = D O
Il
CJ t-bu t-bu t-bu t-bu t-bu t-bu i-Pr t-bu I.
ro
E.
CJ
VO
CJ
I.
rH
CJ
I.
ft I.
CN
B.
CJ
ro
vo
U
I.
I.
rH
CJ
I.
CN I.
CN
B.
CJ
"3 ·
B.
vo
CJ
1
1-1
CJ
I.
O CN
B.
CJ
B.
VO
CJ
I.
U
CQ
ft CN
a
U
a
VO
U
I.
H CN
a
U
a '*'
VO
CJ
I.
J-I
a
I.
ε CN
a
CJ
ro
a
VO
U
I.
1-1
U
-H
TS
I.
CN I.
CN
B.
CJ
3 *
VO
CJ
in
VO
U
I.
i OO
CN C \
CN O
ro iH
ro CN
ro ro
ro ro in
ro O
CN
OO
O
co O = D O I.
CN
B.
U
«A
a
VO
U
U
ft CN

809833/0880

Continuation of table T

co co co> N O OO

36 oFC _c H.CH ₀ - i-Pr C = O 77-78 ° 37 C ₆ Cl ₅ CH ₂ - t-bu C = O 188-190 ° 38 2 r 4, 5- ^ iCl-CgH ₂ CH ₂ - t-bu C = O 132-134 ° 39 2,3,6-triCl-CgII ₂ CII ₂ ~ t-bu C = O 111-113 ° 40 2-F-4-Cl-CgH ₃ CH ₂ - t-bu C = O. 110-112 ° 41 2,4-diF-CgH ₃ CH ₂ t-bu C = O 64-66 ° 42 PF-CgH ₄ CH (CH ₃ ) - t-bu C = O 138-139 ° 43+ P-Cl-CgH ₄ CH (C ₂ H ₅ ) - t-bu C = O 92-94 ° 44 ⁺ PF-CgH ₄ CH (C ₂ H ₅ ) - t-bu C = O 87-89 °

to ■

Φ H H Φ

N • Ρ Φ

144-146 ° 126-128 ° 164-166 ° 83-85 ° 73-75 ° 99-101 ° 94-96 ° O
ri
ί
Cv
vo 94-96 ° C = O C = O C = O C = O C = O C = O O = D O = D C = O t-bu .3
CQ
I. t-bu t-bu t-bu t-bu t-bu t-bu t-bu I.
co
te
CJ
O
ΓΠ
VD
CJ
U
a
I.
Qi I.
CN
U
co
te
VO
CJ
I.
CN ι
CN
U
co
►Π
** VO
Ü
U
CQ
•H
Ό
I.
CN CN
te
CJ
VO
U
O
ro
CJ
I.
O CN
te
CJ
"• 3 ·
* - *
U
co
O CN
te
CJ
• «3 ¹
VO
CJ
co
m
U
I. 1
co
K
CJ
K
O
-T ⁰
vo
U
1
il
U
I.
CN CN
W.
O
ro
CC
VO
CJ
I.
GJ
S.
-H
Ό
I.
in
CN CN
te
CJ
VO
U
O
CN
U
tn
CJ
CU in .46 co ΟΛ O
in ri
in CN
in co
m

809833/0880

Al-

H H (D

O
· <*
O
J
ro
O O
H
Γ- »
I.
σ \
VO 124-125 ° 64-65 ° O
σι
I.
O
c \ ι 82-85 ° 121-123 ° 110-113 ° C = O C = O 0 = 0 C = O C = O O
I!
O C = O C = O C = O 3
CQ
I. t-bu t-bu t-bu t-bu CO
• Ρ ' t-bu t-bu t-bu CN
K
CJ
tn
K
VP
CJ
O
in
EC
O CN
S.
O
K
VO
O
U
CU CN
K
CJ
ro
a -
VO
CJ
O
C)
T
in
r
SI
P.
I.
co CN
HI
O
S.
vo
CJ
O
ω
S.
cu CN
a
CJ
■ ^ »
κ
VD
α
ο
-P
63
I.
α * CN
U
ScT
VO
O
O
-P
W.
I.
O CN
SJ
CJ
ro
SC
VO
ϋ
I.
I.
I.
CN
O
I.
CN CN
a
CJ
VO
α
CN
I.
& CN
CJ
SJ *
vo
CJ
I.
S.
CJ
I.
O 'S ¹
in tn
tn vo
in in CO
ιη ιη O
VO rH
VO CN
VO

809833/0880

Table I continued

CXJ Ca>

O OO OO O

63 p- (t-Bu) -CgH ₄ CH ₂ t-bu C = O 126-127 ° 64 0-1-CgH ₄ CH ₂ t-bu C = O 100.5 ° 65 P-Et-CgH ₄ CH ₂ t-bu C = O 79-81 ° 66 P-Cl-C ₆ H ₄ CH ₂ i-Bu C = O 101-103 ° 67 2, 4- (IiCl-CgH ₃ CH ₂ i-Bu C = O 57-58 ° 68 PFC ₆ H ₄ CH ₂ i-Bu C = O 117-119 ° 69 In-NO ₂ -CgH ₄ CH ₂ t-bu C = O 93-96 ° 70 2-01-6-FC ^ II-CH ₀
D Δ Δ t-bu C = O 105-107 ° 71 P-CF ₃ -C ₆ II ₄ CH ₂ t-bu C = O

N • Ρ Q)

114 ° 59-60 ° 70-71 ° O = D O = D C = O 3
CQ
I.
-μ t-bu t-bu CS
K
ϋ
■ *! ·
K
vo
O
fa
U
ι
O CS
52
ϋ
"β ¹
VO
U
I.
O
-P
W.
k I.
CS
B.
U
m
- »* 4
VD
U
k
-H
ro ro
r- «A
r- in
r- O
σ>
in
i
r-
m O
11.
O i-Bu CS
«
U
rc
UJ
U
fa
I.
-3 ¹
I.
■ Η
O
CS CS

- "84. -

809833/0880

pi CN • 1-4 0 CN O CN O CM O CN O CN O CN O CN O cn O CN • 05 OS O a VO 53 m K a CM B. CO a t-i a CO- a a O O vo rj CO O CN V O U Crt U r- O O O U i-H 1 in i ■ «3 * r "4 rH I. en I. i-t »■ - * cn (U t / a W. CN K I. I. a r- a σ> »A4 1 I. a «ÖO VO VO vo CO VO f- \ O VO V0 VO vo in VO OO cn CJ O U O O CN
rH O υ O U O O O
i-f τ « O CJ O I. Il Ii I. O I. O ι H I. Il O a O I. Il t-i U O Ii J2 Il U Ό cn Il VO I! r-i U O 3 J ₃ I. O CJ U ta J ₃ U 3 Cn O U O CJ • HS 3 I. approx ft 3 I. ι W. ■ H pa α J, 3 ■ A (D ft 1 I. CQ ft η O I. Ό ι .-H 03 1 r- -P! 1 I. +>! •PI S. I. U I. I. r- CO + J! -P! I. I. -PI VO ΟΛ O - ^ CN I. ft I. CO I. co cn CM I. I. I. i co rf co CO

809833/0880

Table II continued

OO CD O

85 2-01-4-FC ₆ H ₃ CH ₂ t-bu C = O 132-134 ° 86 CFC ₆ H ₄ CH ₂ - t-bu C = O Oil * 87 0-Cl-CgH ₄ CH ₂ - t-bu C = O 82-83 ° 88 P-Br-CgH ₄ CH ₂ - t-BU C = O 112-114 ° 89 ⁺ P-Cl-C ₆ H ₄ CH (CH ₃ ) - t-bu C = O 109-119 ° 90 C ^ H ₁ -CH = CHCH ₀
whether & t-BU C = O 69-72 °

* The indicated structures of these compounds were determined by NMR and Mass spectrograph confirmed.

These compounds exist in the form of a 50: 50 mixture of the diastereoisomers obtain.

The invention further relates, as new compounds, to those compounds of the general formula I in which JL is benzyl, which is optionally substituted in the ring by 1 to 3 halogens, and R _{2 is} i-butyl. Of the compounds indicated in Tables I and II, the compounds with the numbers 2gf to 75 and 86 to 90 are not specifically indicated in NL-PA 7 609 439. They also form part of the present invention. They are useful for controlling fungi on plants.

The compounds of general formula I can be prepared in this way be that one imidazole or 1,2,4-triazole or a salt of which with an α-halogenoketone of the general formula II:

X-CH-ZR ₅ ^R 1

reacted, where X is halogen, preferably bromine or chlorine, and R-j, Rp and Z have the meanings given above. That Process can be carried out by making the reactants heated together in the absence of a solvent or diluent. However, it is preferably a solvent present.

Suitable solvents are non-hydroxylic solvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, suIfolan and tetrahydrofuran. Hydroxylated solvents such as methanol and ethanol can be used in certain cases, if the presence of the hydroxyl group does not interfere with the reaction. The process can be carried out in the presence of a base such as sodium hydride, Sodium ethoxide, excess imidazole or triazole, or an alkali metal carbonate (e.g. potassium carbonate). The reaction temperature depends on the selection of reactants, solvents and base, but generally will The reaction mixture is heated to reflux. The procedure persists

809833/0880

23 280 & 227

generally in the fact that you are the reactants in one Solvent dissolves and then isolates the product by the reaction solvent is removed in vacuo. Not implemented Imidazole or triazole can be removed by extracting the product with a suitable solvent, which is then washed with water. A crystallization or other cleaning procedures can then be carried out if necessary.

The α-calogenoketones can be prepared by known methods will.

The compounds of general formula I or the salts thereof can also be prepared by adding a compound of the general formula II:

γ—

wherein Y. and R ^ have the meanings given above, alkenylated, alkynylated, aralkylated or aralkenylated. Further details about this reaction can be found in DE-OS 2 610 022, the details of which are intended to be included in the present application.

Working examples, which illustrate & ± _e above reactions, can be found in NL-PA 7,609,439.

The salts and metal complexes of the compounds of the general Formula I can be prepared from the latter in a known manner will. For example, the complexes can be prepared by reacting the uncomplexed compound with a metal salt reacted in a suitable solvent. '

8098 3 3/0880

The compounds in which Z is a derivative of C = O can from the carbonyl compound using any of the standard procedures given in the literature.

The plant growth regulating effect of the compounds is expressed, for example, in a stunting effect or in a Dwarf growth effect on the vegetative growth of monocotyledon or dicotyledon wood or grass plants. Such For example, stunting or dwarfism can be useful in cereals and soybeans, where there is a reduction in Stalk growth can reduce the risk of overload. Atrophy of wood species is useful in control of growth under overhead electrical lines, etc. Connections which can cause stunting or dwarfism also be useful in modifying the growth of sugar cane or its ripening scheme, thereby increasing the concentration the sugar in the cane is increased at harvest. Peanut stunting can make harvesting easier. An inhibition of growth of grasses can support the maintenance of the lawn. Examples of suitable grasses are Stenotaphrum secundatum (St. Augustine grass), Cynosurus cristatus, Lolium multiflorum and perenne, Agrostis tenuis, Cynodon dactylon (Bermuda grass), Dactylis glomerata, Festuca spp. (e.g. Festuca rubra) and Poa spp. (e.g. Poa pratense). Cause at least some of these connections stunted grasses without significant phytotoxic effects and without harmful effects on the appearance (especially the color) of the grass. This makes these compounds attractive for use in ornamental lawns and strips of grass. They can also have an effect on the appearance of flower heads, for example in Qrasers. Finally, the connections can also make weed species that are present in the grass wither away. Examples of such weeds are sedge (e.g. Cyperus spp.) and dicotyledon weeds. The growth of non-harvestable vegetation (such as weeds and Cover vegetation) can be inhibited, which makes it easier to care for the planting and the crops. In orchards,

809833/0880

especially orchards that are subject to soil erosion the presence of a grass cover will be important. However, overgrowth requires considerable maintenance. The invention Connections could be useful in this situation as they can be used to limit growth, but without kill the plants, which would lead to soil erosion. In some cases, one type of grass can wither more than one other grass species. This selectivity can be used, for example, to improve the quality of lawns, in that the growth of undesired species is preferably suppressed.

The plant growth regulating effect can turn itself into a Express increase in fruit yield.

Other possible plant growth regulating effects that can be achieved by the compounds caused are changing the leaf angle and promoting the sprouting of monocot plants. The former effect can be useful, for example, when changing the leaf orientation of, for example, potato plantings so that more light falls on the fruit and an increase in photosynthesis and tuber weight is achieved. By an increase in sprouting in monocot crops (such as rice) can reduce the number of flowering shoots per unit area can be increased, whereby the total grain yield of these crops is increased. In a lawn there can be an increase sprouting lead to a denser sward, which can be more stressed.

The treatment of plants with the compounds according to the invention can cause the leaves to develop a darker green color.

Furthermore, the compounds can prevent the blooming of sugar beets, whereby the sugar yield is increased. You can also reduce the height of sugar beet without affecting

809833/0880

the sugar yield suffers significantly, which leads to an increase in the planting density enables.

Finally, the compounds can also restrict the vegetative growth of cotton, resulting in a higher cotton yield leads.

When carrying out the method according to the invention, the
Amount of the used to regulate the growth of the plants
Compound on various factors, such as the compound selected and the type of plant whose growth is to be regulated. However, a rate of 0.1 to
15 kg / ha, preferably 0.1 to 5 kg / ha, is used. However can
with certain plants even the application of rates within
these areas result in undesirable phytotoxic effects. Routine trials may therefore be necessary to find the best rate of application of a particular compound for a particular purpose
determine..

The compounds can be used as such for plant growth regulating purposes, but they become more useful for
such application formulated in compositions. Such
Plant growth regulating compositions contain one
Compound of the general formula I or a salt or a complex thereof as defined above and a carrier or
Diluents.

The compounds, salts and complexes can be applied in a variety of ways, for example, they can be applied, in a formulated or unformulated manner, directly to the foliage of a plant
be applied. They can also be applied to bushes and trees, seeds or other media in which plants, bushes or trees are growing or to be planted. You can finally also by spraying, dusting or in the form
a cream or paste. Besides, they can
can be used as steam. The application can be on any

809833/0880

Part of the plants, bushes or trees, "for example on the Leaves, stems, twigs or roots, or on the soil surrounding the roots or on the seeds before planting.

The term "plant" includes seedlings, bushes and trees "

The compositions may be in the form of dusts or granules comprising the active ingredient and a solid diluent or carrier such as eg. Kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt earth, diatomaceous earth and china clay. For example, compositions for the seed dressing may contain an agent, such as a mineral oil, which helps the composition to adhere to the seed. Alternatively, the active ingredient for Saatbeizzweske may be accomplished using ^e * ^nes organic solvent (such as N-methylpyrrolidone or dimethylformamide) are formulated.

The compositions can also take the form of dispersible powders, granules or granules which are a wetting agent contain to the dispersion of the powder or grains, which can also contain fillers and dispersants, in liquids to facilitate.

The aqueous dispersions or emulsions can be prepared by having the active ingredient or ingredients in an organic solvent, which optionally contains one or more wetting agents, dispersants or emulsifiers, dissolves and then introduces the mixture into water, which also contains one or more wetting agents, dispersants or May contain emulsifiers. Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, Toluene, kerosene, methylnaphthalene, the xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and Glycol ethers (e.g. 2-ethoxyethanol and 2-butoxyethanol).

809833/0880

The compositions to be used as sprays can also have the form of aerosols, the formulation in Presence of a propellant, such as fluorotrichloromethane and dichlorodifluoromethane, kept under pressure in a container will.

The connections can be made in the dry state with a pyrotechnic Mixture are mixed to produce a composition suitable for the production of one containing the compounds Smoke in confined spaces is suitable.

Alternatively, the compounds can be encapsulated in microcapsules and used as such.

By adding suitable additives, such as additives for improvement the distribution, the adhesive force and the resistance to rain of the treated surfaces, the different Compositions can be better adapted for different applications.

The compounds can also be used in a mixture with fertilizers (e.g. nitrogen-, potassium- or phosphorus-containing fertilizers). Compositions containing only fertilizer granules which have the compound and which, for example, are coated therewith, are preferred. Such granules suitably contain up to 25 % by weight of the compound.

The compositions can also take the form of liquid preparations which are used as dipping agents or sprays and which are generally aqueous dispersions and emulsions are, which the active ingredient in the presence of one or more wetting agents, dispersants, emulsifiers or Contain suspending agents. These agents can be cationic, anionic or non-ionic in nature.

809833/0880

Suitable cationic agents are quaternary ammonium compounds, such as cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (such as sodium lauryl sulfate) and Salts of sulfonated aromatic compounds such as sodium dodecylbenzenesulfonate, Sodium, calcium or ammonium lignosulfonate, butylnaphthalene sulfonate and mixtures of sodium diisopropyl and triisopropyl naphthalene sulfonate.

Suitable non-ionic agents are condensation products of ethylene oxide with fatty alcohols, such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl or nonyl phenyl and octyl cresol. Other non-ionic agents are partial esters derived from long chain fatty acids and hexitol anhydrides, the Condensation products of the partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (such as polyvinylpyrrolidone and sodium carboxymethyl cellulose) and the vegetable gums (such as gum acacia and gum tragacanth).

The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient (s), which concentrate is to be diluted with water before use. These concentrates often have to withstand a long storage time and, after such storage, must be able to be diluted with water, whereby they should give aqueous preparations which remain homogeneous for a sufficient time so that they can be used with a conventional spray device. The concentrates can contain up to 95% by weight , suitably 10 to 85% by weight, for example 25 to 60% by weight, of the active ingredient (s). If they are diluted for the production of aqueous preparations, then such preparations can contain various amounts of the active ingredient (s).

8 0 9 8 3 3/0880

hold, depending on the intended purpose, but aqueous preparations, the 0.0005 or 0.01 to 10% by weight of the active ingredient (s) can be used well.

The compositions can also contain one or more other compounds that exhibit biological activity (such as other growth stimulating substances, for example gibberellins and other compounds with a fungicidal or insecticidal Activity). They can also contain one or more stabilizers such as epoxides (e.g. epichlorohydrin).

The invention is illustrated in more detail by the following example. example

This example illustrates the plant growth regulating properties of connections. The compounds were first made up in a 5000 ppm solution in distilled water, whereupon the solution then on the foliage of young seedlings of wheat, barley, maize, rice, lolium ryegrass, soy, cotton, peanut, Lettuce, tomato, kango bean and fire bean was applied. Two replica attempts were made. After 21 days, calculated from the treatment, the plants were affected by the plant growth regulating effects and investigated phytotoxic symptoms .

In Table III is the stunting effect of the compounds indicated on vegetative growth using the following classification:

0 = ^ 20% inhibition

1 = 21 to hQ% inhibition

2 = 41 to 60% inhibition

3 = 61 to 30% inhibition

809833/0880

2305-227 ■

If no numbers are given, then the compound was largely inactive as a warning agent.

Further coating flow regulation properties are given as follows: "";. - ...

G = the leaves have a darker green color A = apical effect
T = sprouting effect

The symbol "-" is used to indicate that the compound has not been tested on the relevant plant.

The asterisk (*) shows that the compound was used at a concentration of 4000 ppm.

809833/0880

C.
U O
PA
Φ O
fa .α
ι CN O H - pH O fN CN i-l i-i -i-C O . " U t t 1-t I I O • ■ O
CN OQ
& ° CN O O rH ^^ Cl ^ ¹ LO VO OO ^^ ^^ ^ ϊ P ^
80 983 3/0880 i I "β ¹ VO P ^
ii ri eH tomato O
CN rH iH r-1 r-4 (3
cm OOOOOO <-t OO IGA I I head
salad I. Earth
nut I. tree
wool I. . ^ra
O
CO Lolium
Ryegrass rice
J Corn · barley ι ·
Si *
hf) • ö
•H
U
^>

ORIGINAL INSPECTfcD

Table III continued

19th 1 IG - • - - IG OT 2G - 0 - 2GA 20th 0 - - mm 0 - <- OAG 21st 1 1 0 1 2G 2A IG 22nd 2G 1 0 IGA 1 2G 2 IAG 23 * IG 1 1st floor 0 1 1 0 1 2AG CP
Cf 24 *
co 1 IAG 1 0 1 1 IAG Ca) ^D IG 0 i 0 1st floor 0 2G 0 3 IAG Approx
\ 26 * 0 0 0 1 C?
co 27 *
00 IG 0 1st floor 0 OA 3GA ° 29 * IAG 1 A. 2G 3A 30 * 1 - «4 1 - 2Ά 31 * 2G 2G A ''. 2 A. 32 * - IGA ¹ floor 1 - 33 * 2G

Table III continued

Zl

OO 43 * 1 1 1 - IG 1 - A. 0 - 2Α Ik, ' 34 * ° 39 *
co ^OJ - 1 Γ W 35 * OO . 44 * _ 2 36 * ω 40
<Λ> 37 * "^ 41 *
ο 45 * _mmi 38 * ⁰⁰ 42 *
OO ^{4 / ί} O 46 * 47 * - - 2 2Τ - 3GAT IG _ IA 3Α - • 3GA IG 3GAT • 2 IG 3GA 1 - - _ IGA - GA - A. - 2G 1 1 - 2GA 1 - 1 1 IG 1

CO O

Γίί

"■ 4

Table III continued

2 ■ 1 G 1 2G 2T 48 * 49 * 50 * 51 * c ⁵² CO oo 53 CO co 54 P. 55 GO € 3. 56 57 58 59 60 77

2GAT
2GA
3GT

2GA
A.

IA
* IA

IA

2A

2A
1

1
A.

2GA

3GA

3GA
2GAT

OA

IG 3G

2A 2A

3GA

IA

2GA

IA

Φ HH Ο) & CO Eh

(N

ο α

(N

1111

U <ζ IdJ <Η cn cm cm

1-4 Η

<ί rf!

CM - <H

CM rH I Il I I

I I I

CM CM

HOO

CTl O ii ΙΛ W5 t ^ 00-CPi

r ^ oococacooococo

8uyd33 / 0880

Claims (1)

1. Method of regulating the growth of plants, thereby it indicates that you have to go to the Plant, on the seeds of the plant or on the habitat the plant or the seed a connection of the general Formula 1: where R _{1 is} alkenyl, alkynyl or optionally substituted aralkyl or aralkenyl, R _{2 is} cycloalkyl, alkyl or haloalkyl, Y is == Ν- or = CH- and Z is C = O or a derivative thereof, or an acid addition salt or applying a metal complex of such a compound. 2. The method according to claim 1, characterized in that in the compound of the general formula I Rg for C ₃ _g * cycloalkyl (e.g. cyclohexyl), C ₁ e-alkyl (e.g. i-propyl, t-butyl or i-butyl) or halogeno-iC] c-alkyl) stands. 3. The method according to claim 1 or 2, characterized geke η η ζ eich η et that in the compound of the general formula IR ₁ for alkenyl or alkynyl with up to 4 carbon atoms, optionally substituted aralkenyl with 7 to 12 carbon atoms in the aryl part and 2 to 3 carbon atoms in the alkenyl part or optionally substituted aralkyl with 7 to 12 carbon atoms in the aryl part and 1 to 3 carbon atoms in the alkyl part. 4. The method according to claim 3, characterized ge k e η η ζ. eich - η e t that in the compound of the general formula IR ₁ 809833/0880 oronal _INSP c _TE d 2605227 represents benzyl which is optionally substituted in the ring by halogen, C _1-4 alkyl, halogens "(C ₁ _ ₄ alkyl), phenyl, halophenyl, C ^ g-cycloalkyl, nitro, cyano, C ₁ ^ alkoxy , (C _1-4 -alkylene) -dioxy, (C _1-4 -AIkOXy) - (C _1-4 -BIlCyI), (C _1-4 -alkyl) -thio, (C _1-4 -AIlJyI) - sulfonyl, (C ₁ ^ -haloalkyl) -sulfonyl, phenylsulfonyl, unsubstituted or mono- or di- (C _1-4 -alkyl) -substituted sulfamoyl or carbamoyl, carboxy, (C _1-4 -alkoxy) -carbonyl, unsubstituted or mono- or di- (C _{1 4} alkyl) -substituted amino, (C ₁ _g alkanoyl) amino, N- (C _1-4 -alkyl) -substituted (C ₁ ^ alkanoyl) amino, formylamino, N- (C ₁ · alkyl) -substituted formylamino, phenylethyl, phenoxy or benzyloxy, the number of ring substituents being 1, 2 or 3, and / or optionally being substituted on the α-carbon atom by a phenyl or benzyl, which is optionally as indicated above for benzyl, or _{substituted by C 1-4} -alkyl, cyano, (C _1-4 -alkoxy) carbonyl or trihalomethyl is ituated. Process according to claim 3 or 4, characterized in that in the compound of the general formula IR ₁ for allyl, 3-phenylallyl, propargyl, benzyl, α-methylbenzyl, α-methyl-p-bromobenzyl, α-methyl-p-fluorobenzyl, α-ethyl-p-chlorobenzyl, α-ethyl-p-fluorobenzyl, o-, m- or p-chlorobenzyl, 2,4-, 3,4- or 2,6-dichlorobenzyl, 2,4,5- or 2,3,6-trichlorobenzyl, pentachlorobenzyl, o-, m- or p-bromobenzyl, 2,4-dibromobenzyl, o-, m- or p-fluorobenzyl, 2,4-difluorobenzyl, o-iodobenzyl, p-aminobenzyl , o-, m- or p-methylbenzyl, 2,5- or 3,4-dimethylbenzyl, p-ethylbenzyl, pt-butylbenzyl, o- or p-cyanobenzyl, o-, m- or p-nitrobenzyl, o-, ! m- or p- (trifluoromethyl) -benzyl, ο- or p-methoxybenzyl, o-, m- or p-ethoxybenzyl, 3-nitro-4-chlorobenzyl, 2-nitro-4-fluorobenzyl, 2-chloro-4- fluorobenzyl, 2-eluoro-4-chlorobenzyl, 2-chloro-6-fluorobenzyl, 2-fluoro-4-bromobenzyl, 2-chloro-4,5-methylenedioxybenzyl, 3-bromo-5-methoxybenzyl, 2-methoxy-5- nitrobenzyl, p-benzyloxybenzyl, p-phenylbenzyl or ß, ß-diphenylethyl, Y is = N-, R _{2 is} cyclohexyl, isopropyl, t-butyl or isobutyl and Z is C = O. 809833/0980 6. The method according to claim 3 or 4, characterized in that in the compound of the general formula IR ^ for 3-phenylallyl, benzyl, α-methyl-p-chlorobenzyl, ο- or p-chlorobenzyl, 2,4- or 3, 4-dichlorobenzyl, o- or p-fluorobenzyl, m-trifluoromethylbenzyl, o- or p-bromobenzyl, p-cyanobenzyl or 2-chloro-4-luorobenzyl, Y stands for = CH-, R _{2 stands} for t-butyl and Z is C = O. ( 7J Compounds of the general formula I, in which R, j stands for benzyl which is optionally substituted by 1 to 3 halogenates, R _{2 stands} for i-butyl, Y stands for = N ~ or = CH- and Z for C = O or a derivative thereof, as well as the acid addition salts and metal complexes thereof. 809 8 3 3/0880