CA1212679A - 1-methylene carbonyl derivatives of 3-aryloxy-4- phenyl-azet-2-one - Google Patents

Abstract

ABSTRACT OF DISCLOSURE

1-Methylene carbonyl derivatives of 3-aryloxy-4-phenyl-azet-2-ones are effective plant-growth regulators.

Description

002l-~T~IYLENE CARBOLJYL GERIVATIVES OF
0033-~RYLOXY-4-PII~YL-AZET-2-ONE

005BACKGROU~D O~ THE INVENTION
006A process for condensing aldehydes with amines is 007disclosed in J. Organic Chemistry, vol. 41, pp. 3491-3 (1976).
008N-Acyl-3-aryl-3-azetidinol intermediates are disclosed in 009~.S. Patent No. 4,088,644.

011The plant-growth-regulating compound of my invention 012 may be represented by the following formula (I):
014,~ R o 0154 r ,1 016X ~ CH-C-R' 020 CH C~
022 O O (I) 029 wherein R is hydrogen or alkyl of 1 to 3 carbon atoms; R' is 030 hydrogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon 031 atoms, thioalkyl of 1 to 6 carbon atoms, or NR R wherein R
032 and R2 are independently hydrogen or alkyl of 1 to 12 carbon 033 atoms; and Xl, X2, X3 and X4 are independently hydrogen, 034 chloro, bromo, fluoro, iodo, alkyl of 1 to 4 carbon atoms or 035 alkoxy of 1 to 4 carbon atoms.
036 Representative R' groups are methyl, ethyl, i propyl, 037 n-propyl, n-butyl, sec-butyl, n-pentyl, isohexyl, methoxy, 038 ethoxy, n-propoxy, i-propoxy, methylthio, ethylthio, hexylthio, 039 amino, methylamino, dimethylamino, methylethylamino, decyl-040 amino, dodecylamino.

~21Z~i7~

002 Preferably R' is alkoxy of 1 to 6 carbon atoms. Most 003 preferably R' is ethoxy.
004 Representative Xl, X2, X3 and X4 groups are chloro, 005 bromo, fluoro, iodo, methyl, ethyl, i-propyl, n-butyl, methoxy, 006 i-propoxy, sec-butoxy.
007 Preferably X , X , X , X4 and R are hydrogen.
008 The compounds of my invention may be prepared 009 according to the following scheme:

013 CHaNCHCR I ( 1 ) 0 16 ~
017 3~ -~, 4 CE~ ~ E~2NcHcRl X X
018 X '~==J X
020 (II) (III) (IV) 024 O 4 ~
025 " X ~ ll CHCR' 026 O ~CCl 3 ~
027 ,~ C~l2 X \r--N
028 IV + ~ ~ /L~ (2) 030 X X o o 033 x2 037 Reaction (1) may be conducted in a suitable organic 038 diluent at ambient temperature and atmospheric pressure.
039 Preferably the hydrochloride salt of the amine (III) may be 040 used and the reaction may then be conducted in presence of a 041 base, such as trialkylamine, to scavenge the hydrogen chloride.
042 The reaction may be conducted in the presence of a dehydrating 043 agent, such as magnesium sulfate, to scavenge the water 044 by-product.

~%~7~

002 Reaction (2) may be conducte~ in a suitable oryanic 003 diluent at ambient temperature at~ atmospheric pressure. The 004 reaction is preferably conducted in the presence of a base, 005 such as trialkylamine, to scavenge evolved hydrogen chloride.
007 Example 1 -- Preparation of Benzaldehyde 008 _Carbethoxymethylimine 009 To ethyl glycinate hydrochloride (36 .4 9) suspended 010 in 500 ml methylene chloride were added magnesium sulfate t22 011 g) and triethylamine ~72 ml, 52.4 g). Benzaldehyde (27.6 g) 012 was added dropwise at 15-20C with stirring. The mixture was 013 stirred at room temperature for two hours, filtered and 014 stripped. To the residue was added 300 ml diethylether and 150 015 ml brine. After separation the organic layer was collected, 016 and the aqueous layer was extracted with 100 ml ether. The 017 organic phases were combined, dried (MgSO4), filtered and 018 stripped to yield the title product as a pale yellow oil.
020 Example 2 -- Preparation of 021 1-Carbethoxymethyl-3-phenoxy-4-phenyl-azet-2-one 022 To a solution of phenoxyacetyl chloride (10.8 g) in 023 30 ml benzene was added dropwise a solution of the imine 024 product (12 9) prepared in Example 1 in 50 ml benzene. The 025 reaction was exothermic. The mixture was stirred at room 026 temperature for 20 minutes, then 7.5 g triethylamine was added 027 dropwise. The mixture was re~luxed for 90 minutes and allowed 028 to stand overnight at room temperature.
029 The mixture was poured into 200 ml ice water and 150 030 ml methylene chloride and the layers were separated. The 031 organic layer was washed with water, dried (;IgS04), filtered 032 and stripped to yield a yellow oil. The oil was chromato-033 graphed on silica gel (eluted with 50:50 methylene 034 chloride:benzene) to yield the title product as a yellow oil.
035 The testing of this product is reported in Table I as Compound 036 1. Calc. C:70.1, H:5.9, N:4.3; Fd. C:68.4S, H:5.86, N:3.97.
037 Following procedure analo~ous to Examples 1 and 2, 038 the compound 1-carbethoxymethyl-3-2,4-dichlorophenoxy-4-phenyl-039 a~et-2-one was prepared. The results of testing are shown in ~;~lZ679 -002 Table II as Compound 2. Calc. C:57.9, H:~.3, ~:3.6; Fd.
003 C:57.88, ~I:4.55, N:3.48.

005 The compounds of the present invention are, in 006 general, herbicidal and plant-growth regulating in post-007 emergent applications. The compounds are particularly 008 effective as post-emergent plant-growth~regulators.
009 The compounds, when applied to the soil surrounding 010 ~rowing plants in such an amount that the compounds will not 011 kill beneficial plants, also show efficient plant growth 012 regulating or retarding effects and may be advantageously 013 employed, for example, to prevent or retard the growth of 014 lateral buds in plants and to promote the thinning out of 015 superfluous fruits in various fruit trees.
016 The compounds can be applied in any of a variety of 017 composltions. In general, the compounds can be extended with a 018 carrier material of the kind used and commonly referred to in 019 the art such as inert solids, water and organic liquids.
020 The co~pounds will be included in such compositions 021 in sufficient amount so that they can exert a growth-regulating 022 effect. ~sually from about 0.5 to 95% by weight of the com-0~3 pounds are included in such formulations.
024 Solid co,~positions can be made ~ith inert powders.
025 The compositions thus can be homogeneous powders that can be 026 used as such, diluted with inert solids to form dusts, or 027 suspended in a suitable liquid medium for spray application.
028 The powders usually comprise the active ingredient admixed with 029 minor amounts of conditioning agent. Natural clays, either 030 absorptive, such as attapulgite, or relatively non-absorptive, 031 such as china clays, diatomaceous earth, synthetic fine silica, 032 calcium silicate and other inert solid carriers of the kind 033 conventionally employed in powdered growth-regulating composi-034 tions can be used. The active in~redient usually makes up from 035 0.5-90% of these powder compositions. The solids ordinarily 036 should be very finely divided. For conversion of the powders 037 to dusts, talc, pyrophyllite, and the like, are customarily 038 used.

~Zl;~67~
-002 Liquid compositions including the active compounds 003 described above can be prepared by admixing the compound with a 004 suitable liquid diluent medium. Typical of the liquid media 005 commonly employed are methanol, benzene, toluene, and the like.
006 The active ingredient usually makes up from about 0.5 to 50% of 007 these liquid compositions. Some of these compositions are 008 designated to be used as such, and others to be extended with 009 large quantities of water.
010 Compositions in the form of wettable powders or 011 liquids can also include one or more surface-active agents, 012 such as wetting, dispersing or emulsifying agents. The surface-013 active agents cause the compositions of wettable powders or 014 liquids to disperse or emulsify easily in water to give aqueous 015 sprays.
016 The surface-active agents employed can be of the 017 anionic, cationic or nonionic type. They include, for example, 018 sodium long-chain carboxylates, alkyl aryl sulfonates, sodium 019 lauryl sulfate, polyethylene oxides, lignin sulfonates and 020 other surface-active agents.
021 The amo~nt of compound or composition administered 022 will vary with the particular plant part or plant growth medium 023 which is to be contacted, the general location of application 024 -- i.e., sheltered areas such as greenhouses, as compared to 025 exposed areas such as fields -- as well as the desired type of 026 control. For plant growth regulating or retarding activity, it 027 is essential to apply the compounds at a concentration not so 028 high as to kill the plants. Therefore, the application rates 029 for plant growth regulating or retarding activity will 030 generally vary from 0.1 to 5 kg/ha, and preferably from 0.1 to 031 3 kg/ha.
032 Plant-growth-regulating tests on representative 033 compounds of the invention were made using the following 034 methods.

036 Uniform size Idaho 1-11 pinto be;lns, 13-16 days old, 1 037 plant per 4" pot, were used with monofoliate leaves fully ~IL212~' ?~ ' -GCIi -6-002 developed and first trifoliates beginning ~o unfold. Suffi-003 cient plants for 4 replicates per treatment were selected. On 004 each plant all growth 5 mm above the monofoliate leaf node was 005 removed with forceps one to four hours beEore application.
006 As a stock solution 100 mg of test material was 007 dissolved in 10 ml of acetone. Aliquots of lS0 ml were pre-008 pared of 200, 80 and 32 ppm by bringing 3, 1.2 and 0.48 ml to 009 the 150 ml volume with 147, 14~.8 and 149.52 ml deionized water 010 respectively. This is equivalent to 75, 30 and 12 gamma/cm of 011 soil area for the three rates.
012 To each of 4 pots, each containing one Pinto bean 013 plant, 30 ml of test solution was applied to the soil surface 014 using the 30 ml syringe or other suitable metering device. The 015 plants were incubated in a greenhouse maintained at 70-80F.
016 The plants were kept off the bottom of the metal greenhouse 017 trays by using expanded metal supported an inch above the tray.
018 The plants were watered by overhead irrigation throughout the 019 course of the test.
020 Plants were evaluated 12 to 16 days after treatment.
021 The following signs of physiological activity were noted:
022 flowering, bud break at the cotyledonary node, side branching, 023 compactness of the plant (a measure of internodal length), 024 phytotoxicity/dessication/defoliation and relative green color 025 (a measure of leaf thickness). These qualities were compared 026 to plants treated by ti-e standard, tri-iodo benzoic acid 027 (TIBA), and to untreated check plants (denoted as "Check (-)"
028 in Table I). Untreated check plants denoted as (+) were those 029 on which the monofoliate leaf nodes were not removed. The 030 results are shown in Table I.

~2~
-~ a) cv m 5~ 1 a I I I I
~ O
O Z

C h O
( ~ ~ u~ d' Ln ~ Ln Ln )-I O

JJ~ ~n ~ c ~1 u~
c~ "' a ~ ~ n n C
P~ Q
P~ 11 11 11 C O Ln o ~ ,-~
a~
a:~ u~
~ v O ~ u~
J~ ~: a~
C v o co ~9 ~ Cl~ ~ n ~ C
,~ t~ ~
Cl ,:>
e o o U
C ~ aJ
o 4 .~, V
~ ~ ~
:5 ~ o ~ r~
~ ~n aJ
~;
m .
3 ,Y
O ~ ~
)J~ O
w æ o ~ Ln a , c~ Ln v ~~l ~
t~~ ~
a~ o p~ ~
l ~
H ~: ~ alLl~
.,1 1~ ~ ~
~ ~ ~ C 3 :1 E
trl ~ ~ ~ c~ :a ~ ,~ ~ ~ C~ O O Q ~ O
~: 3 E~ o m m ~: ~ s v ~ .c _~ ~ ~ ~ X V ,-( ~' O ~ r(5 3 n~ V
U) ~ .~ O O :~S
(IS ~ C O
) I O t~ O
C E~ o o o o o o ~1) 3 ~-I aJ 5-1 O t,) , .... ... E~ OO V ~1 ~ ~J C
r~ o ~ .n o ~ I I f~ ~ 3 U~ 1 V
o ~ ,c ~ ~C
V V C~ O
U C) 3 ~1 a) o ~--1 u, r~ ~ ~ V
C I + ~ C
o ~ ~ o ~ ~, o ~ v 8 a~
~ a: ~ ~
O H C ~

O OO O O O O ~I r-l ~ 1 r-l ~ ~1 ~ ~1 ~(~ ~`J ~ ~I t`l ~ t~l O O O O O O O O O o O O o O O O O O O O O O O

~2~Z67~9 001 -8~

002 ROOT INHIBITION OF SEEDLI~GS
003 Ten seeds each of watergrass, mung beans and 004 cucumbers were placed in each of several Northrup~King 005 Seed Pack growth pouches. To each pouch was added lS ml ~f an 006 aqueous solution at the test concentration of cornpound 2. 'rhe 007 pouches were suspended ln containers under 12S-lS0 footcandles 008 of light Eor six days at room temperature. Root length is 009 measured for each species and expressed as percent inhibition 010 compared to untreated check samples. Activity is compared with 011 the standard MH-30 tmaleic hydrazide).
012 The results are shown in Table II.
014 TABLE II - ROOT INHIBITION (~ Inhibition) 016 Concentration, ppm 0l9 Compound 2 0 0 4 0 020 Standard 84 76 68 55 022 Compound 2 0 0 0 0 023 Standard 86 a4 81 61 025` Compound 2 59 39 51 5 026Standard 77 6 2 65 45

Claims (8)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED AS DEFINED AS FOLLOWS:

1. A compound of the formula (I) wherein R is hydrogen or alkyl of 1 to 3 carbon atoms; R' is hydrogen, alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, thioalkyl of 1 to 6 carbon atoms, or NR1R2 wherein R1 and R2 are independently hydrogen or alkyl of 1 to 12 carbon atoms; and X1, X2, X3 and X4 are independently hydrogen, chloro, bromo, fluoro, iodo, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.

2. A compound according to Claim 1 wherein R' is alkoxy of 1 to 6 carbon atoms.

3. A compound according to Claim 2 wherein R is hydrogen.

4. A compound according to Claim 3 wherein X1, X2, X3 and X4 are independently hydrogen, chloro, bromo, fluoro or iodo.

5. The compound according to Claim 4 wherein X1, X2, X3 and X4 are hydrogen R' is ethoxy.

6. The compound according to Claim 4 wherein X1 and X2 are 2-chloro and 4-chloro, respectively, R' is ethoxy, and X3 and X4 are hydrogen.

7. A method for regulating the growth of vegetation comprising applying to said vegetation or its habitat a growth regulating effective amount of a compound of the formula defined in claim 1.

8. The method of claim 7, wherein in the compound of the formula defined in claim 1, R' is ethoxy and R, X1, X2, X3 and X4 are hydrogen.