Note: Descriptions are shown in the official language in which they were submitted.
Z3LZ679
001 -1-
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.
010DESCRIPTION OF THE INVENTION
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'
018 X CH - W
019
020 CH C~
022 O O (I)
02S
027 X
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~
001 -2-
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:
011 R O
012 1 11
013 CHaNCHCR I ( 1 )
015 O R O
0 16 ~
017 3~ -~, 4 CE~ ~ E~2NcHcRl X X
018 X '~==J X
020 (II) (III) (IV)
023 R O
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
035 X
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.
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001 -3-
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
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001 -4-
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.
004 UTILITY
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.
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5-
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.
035 PLANT-GROWTH-REGULATING TEST
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~' ?~ '
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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.
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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
017 WATERGRASS 313 125 50 20
0l9 Compound 2 0 0 4 0
020 Standard 84 76 68 55
021 MUNG BEANS
022 Compound 2 0 0 0 0
023 Standard 86 a4 81 61
0 24 CUCUMBERS
025` Compound 2 59 39 51 5
026Standard 77 6 2 65 45
027
