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US3004036A - Carboximide compounds - Google Patents

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US3004036A
US3004036A US705787A US70578757A US3004036A US 3004036 A US3004036 A US 3004036A US 705787 A US705787 A US 705787A US 70578757 A US70578757 A US 70578757A US 3004036 A US3004036 A US 3004036A
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hept
compounds
maleimide
bean
hexachlorobicyclo
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US705787A
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Fan Hsing Yun
Harry G Durham
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Shell USA Inc
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Shell Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C07D209/72—4,7-Endo-alkylene-iso-indoles
    • C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3

Definitions

  • fungicidal and fungistatic compositions have long been manifest. In spite of this fact, however, a vast number of the compounds employed as fungicides have generally been found lacking in one or more of the basic requirements of a satisfactory fungicide.
  • a fungicidal composition In order to be commercially useful, a fungicidal composition must be compatible with adjuvants and other active ingredients; it must be economical; it should be soluble in common solvents and stable; and most important, it must not be toxic to the plants to which it is applied or to animal life. A prohibitive degree of phytotoxicity under the conditions uti lized for fungus control and toxicity toward warm blooded animals are among the most common shortcomings of present fungicides.
  • Another object of the present invention is to provide new and novel fungicidal compounds which can be economically prepared, distributed and applied to plants.
  • Yet another object of the present invention is to pro vide economical and stable fungicidal compositions containing these compounds.
  • Still another object of the present invention is to provide a method of combating fungi by applying these compositions to plants.
  • the present invention is concerned with organic compounds wherein one terminal position is occupied by a polyhalogenopolycycloalkene and the other terminal position is occupied by dicarboximide or derivative thereof.
  • dicarboximide as employed throughout this specification refers to the group Of the polyhalogenopolycycloalkenes which occupy one terminal position of the compounds encompassed by the present invention, halogenated bicyclo(2.2.l)hept-5- ene rings as shown in the following structural formula are preferred:
  • This basic carbon skeleton consists of not more than five linearly fused five membered rings.
  • the halogenated cycloalkene portion of the molecule may be attached directly to the nitrogen atom of the dicarboximide portion of the molecule, or alternatively, the terminal portions of the molecule may be separated by an alkyl radical of from 1 to 10 carbon atoms, or an aryl radical such as benzyl, tolyl, phenyl, naphthalenyl, or anthracenyl group or an aralkyl group, the alkyl portion of which has 1 to 10 carbon atoms and the aryl portion of which is a benzyl, tolyl, phenyl, naphthalenyl or anthracenyl group.
  • X represents hydrogen or halogen (preferably chlorine) and X represents hydrogen, halogen (preferably chlorine) or an alkoxy (preferably meth oxy) group. At least one X should be a halogen.
  • R may be a straight chain, branched chain or cyclic alkylene group of from 1 to 10 carbon atoms, an arylene group such as a tolylene, phenylene, naphthylene or anthrylene or an aralkylene group made up of the alkylene as described above and arylene groups.
  • R is preferably a short chain alkylene group.
  • y is 0 to 10.
  • W represents a straight chain aliphatic group of 2 to 5 carbons (preferably 2) either saturated or having one or more double bonds. W may be partially or totally h'alo genated, preferably with chlorine. W may also represent an. aryl radical such as benzene, toluene, naphthalene and anthracene or their halogenated derivatives. Each of 2 carbon atoms of W are bonded respectively to each of the two carboxyl groups of the decarboximide. When W is an aryl ring, each of two adjacent carbon atoms of the aryl rings are bonded to acarboxyl group of the dicarboximide.
  • the compounds of the present invention may thus be considered as dicarboximides having substituted therein halogenated polycyclic structures such as a polyhalopolycycloalkenyl radical or a halogenated 1,4,5,8- dimethanonaphthyl radical.
  • halogenated polycyclic structures such as a polyhalopolycycloalkenyl radical or a halogenated 1,4,5,8- dimethanonaphthyl radical.
  • the maleamic acids themselves are obtained'by reacting the appropriate polyhalogenopolycycloalkene amine with maleic arihydride. Detailed preparation of these ma'leanu'c acids is to be found in co-peuding application SerialNunibcr 705,782. The preparation of the amines is described in copending application Serial Number 705,781.
  • the compounds of the present invention possess fungicidal activity to a Wide variety of plant pathogens.
  • foliage fungicide screen three varieties of bean plants and four foliage fungus diseases were employed.
  • the chemicals were To facilitate deposit, the primary leaves are oriented to a vertical position by pinning them to a small wire staff. Either the upper or lower epidermis of the leaf is exposed to the spray stream, depending on the surface to be inoculated.
  • Test chemicals are prepared as 1% w./v. stock solutions in a solvent
  • the stock is diluted for spraying using a diluent consisting of distilled water+solvent (1:1 or with distilled water plus two solvents (2:1:1).
  • Triton X-l55 at 0.005% W. is used as a wetting agent for each concentration of toxicant. All chemicals are initially tested at a single concentration of 1000 p.p.m. If acceptable disease control is shown, the chemicals are retested at 1000 ppm. and the next lowest dilution of 500 ppm. Chemicals continuing to show disease control are retested in this fashion until the minimum effective concentration is determined. Phytotoxicity assessments are expressed as the maximum Safe concentration.
  • Spray applications are made using a laboratory sprayer.
  • the bean plants are selected for use at a stage when the two primary'leaves are about three-quarters expanded.
  • Crops and diseases used were tomato or potato blight (Phytophzhora infestanzs), celery blight (Septoria apiigraveolentis), bean mildew (Erysiphe polygom'), bean rust (Uromyces appendiculatus), and cucumber anthracnose (Colletotrichum lagenarium).
  • Foliage-fungicide activity index (F-F.A.I.)
  • fungicidal compounds :of the present invention may 'be'applied consists of solutions of'the active ingredient in suitable inert liquid-orz'semisolid diluents, in which the active ingredients are present-in molecular ly dispersed form.
  • l he form in which the agents to be :employed :are applied tto the objects treateddepends on the :nature :oftheobjecfland thepurpose of the application.
  • Suitable inert solvents 'for the manufacture of liquid preparations should be inflammable, .as odorless as possible and without any toxic-efiecton humans and animals when properly used. 'Neithershould they :have a corrosive etiect on the components of the preparations or T'ABLE 2.
  • --FLIAGE FU'NGICIDE Tesr Foliage-fungicide activity index Activitylndex at 0.24% Cone. (Upper figure) and %control 300.06% (Lower Figure) Phytoboxicity at 0.24% (upper figure) and 0.06% cone. (lower figure) respectively Chemical Compound Com- Com- 'P.i.* Sri. -E;p. U.a.
  • S.a. Septoria apii-graveolentic (late blight of celery).
  • E.p. Erysiphe pol 1011i (bean powdery mildew).
  • U.a, Ur0m1/ces appendiculatus (bean rust).
  • 0.1. Calletotrichmn lagemriu'm (cucumber anthracnose).
  • the active compounds of the present invention may be eused alone or in combination with other fungicidal, viricidal, insecticidal, or acaricidal materials, the action on which "may be either internal or external, with plant nutritives, .plant hormones and the like.
  • Wetting agents, .and if necessary or desirable, stickers such as the heavy hydrocarbons oils with a minimum viscosity of Engler at 50 C. can be present.
  • any conventional wetting agent which will not react with the'toxicant for example alkyl sulfate salts, alkyl Sary'l sulfonate salts, su'lfosuccinate salts, .ethers of polyethylene glycols and alkylated phenols, and the like can be employed.
  • the toxic agents are employed in the form of emulsions or suspensions, for example, in water, solvents such .as oils, emulsifiers, emulsion stabilizers and the like may be added. Materials which suppress phytotoxic action may also be added if desired. For example, glucose is known to protect tomato plants against damage by certain substances having a phytotoxic effect when employed in concentrated form.
  • the 'irnides and maleimides of the present invention may be applied by means of spraying.
  • .Spraying .of the plants to be treated may be performed with aqueous emulsions solutions or suspensions of the active agents.
  • the spray .liquid is generally applied at a rate of from about 75 to 150 gallons per acre. If spraying is effected with smaller quantities ofliquid as in low volume spraying, high concentrations of the active agents should be employed. If desired, a minoramount of the order of about 0.01 to about 0.05% by weight, of a wetting agent may be added to aid :in forming a suspension of the salt in the aqueous medium. Any of the conventional wetting agents 'can be employed.
  • Particularly suitable wetting agents are the sodium salts of a mixture of secondary hep'tadecyl sulfates, sold commercially under the name of Teepol and polyethylene glycol ethers of alkyl phenols sold under the trade name of Triton X400 and Triton X-l55.
  • Preferable concentrate compositions comprising an active compound of the present invention and a .suitable .Wetting agent are prepared, :and the concentrate is then dispersed in water prior to :use.
  • suitable solvents are high boiling oils, e.g. oils of vegetable origin such as castor oil, etc, and lower-boiling solvents with a flash point of at least 30 C., such as carbon tetrachloride, ethylene dichloride, hydrated naphthalene, alkylated naphthalene, sorbent naphtha, etc. Mixtures of solvents may also be used.
  • the active compounds of the present invention may also be applied in the form'o'f dusts utilizing as the inert vehicle such materials as tricalcium phosphate, precipitated chalk, bentonite, kieselguhr, etc.
  • these compounds may also be employed in the form of aerosols.
  • the active ingredient is dissolved or dispersed in a solvent boiling below room temperature at atmospheric pressure.
  • the method of combatting fungi on living plants comprising applying a fungicidal toxic amount of N- (1,4,5,6,7,7 hexach1orobicyc1o(2.2.1)hept 5 en 2- ylmethyl)maleimide to said plants.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

United States Patent 3,004,036 CARBOXIMIDE COMPOUNDS Hsing Yun Fan and Harry G. Durham, Modesto, Cahfi,
assignors to Shell Oil Company, a corporation of Delaware N Drawing. Filed Dec. 30, 1957, Ser. No. 705,787 11 Claims. (Cl. 260-326) The present invention is concerned with hydrocarbons wherein one terminal position is occupied by a polyhalogenopolycycloalkene and the other terminal position is occupied by a dicarboximide or derivatives thereof. These compounds have been found to possess significant toxicity toward and inhibition of a wide variety of fungi.
The need for elficient and economical fungicidal and fungistatic compositions has long been manifest. In spite of this fact, however, a vast number of the compounds employed as fungicides have generally been found lacking in one or more of the basic requirements of a satisfactory fungicide. In order to be commercially useful, a fungicidal composition must be compatible with adjuvants and other active ingredients; it must be economical; it should be soluble in common solvents and stable; and most important, it must not be toxic to the plants to which it is applied or to animal life. A prohibitive degree of phytotoxicity under the conditions uti lized for fungus control and toxicity toward warm blooded animals are among the most common shortcomings of present fungicides.
It is, consequently, the principal object of the present invention to provide new and novel compounds which are effective as, fungicides yet do not manifest prohibitive toxicity toward .warm blooded animals such as man.
Another object of the present invention is to provide new and novel fungicidal compounds which can be economically prepared, distributed and applied to plants.
Yet another object of the present invention is to pro vide economical and stable fungicidal compositions containing these compounds.
Still another object of the present invention is to provide a method of combating fungi by applying these compositions to plants.
Other objects and advantages will be apparent from the following description read in conjunction with the appended claims.
Generally speaking, the present invention is concerned with organic compounds wherein one terminal position is occupied by a polyhalogenopolycycloalkene and the other terminal position is occupied by dicarboximide or derivative thereof. The term dicarboximide as employed throughout this specification refers to the group Of the polyhalogenopolycycloalkenes which occupy one terminal position of the compounds encompassed by the present invention, halogenated bicyclo(2.2.l)hept-5- ene rings as shown in the following structural formula are preferred:
Of equal interest in the dimethanonaphthalene ring structure shown in the following structural formula:
This basic carbon skeleton consists of not more than five linearly fused five membered rings.
The halogenated cycloalkene portion of the molecule may be attached directly to the nitrogen atom of the dicarboximide portion of the molecule, or alternatively, the terminal portions of the molecule may be separated by an alkyl radical of from 1 to 10 carbon atoms, or an aryl radical such as benzyl, tolyl, phenyl, naphthalenyl, or anthracenyl group or an aralkyl group, the alkyl portion of which has 1 to 10 carbon atoms and the aryl portion of which is a benzyl, tolyl, phenyl, naphthalenyl or anthracenyl group. I
In these formulae X represents hydrogen or halogen (preferably chlorine) and X represents hydrogen, halogen (preferably chlorine) or an alkoxy (preferably meth oxy) group. At least one X should be a halogen.
R may be a straight chain, branched chain or cyclic alkylene group of from 1 to 10 carbon atoms, an arylene group such as a tolylene, phenylene, naphthylene or anthrylene or an aralkylene group made up of the alkylene as described above and arylene groups. R is preferably a short chain alkylene group. y is 0 to 10.
W represents a straight chain aliphatic group of 2 to 5 carbons (preferably 2) either saturated or having one or more double bonds. W may be partially or totally h'alo genated, preferably with chlorine. W may also represent an. aryl radical such as benzene, toluene, naphthalene and anthracene or their halogenated derivatives. Each of 2 carbon atoms of W are bonded respectively to each of the two carboxyl groups of the decarboximide. When W is an aryl ring, each of two adjacent carbon atoms of the aryl rings are bonded to acarboxyl group of the dicarboximide. The compounds of the present invention may thus be considered as dicarboximides having substituted therein halogenated polycyclic structures such as a polyhalopolycycloalkenyl radical or a halogenated 1,4,5,8- dimethanonaphthyl radical. 1 Illustrative of the types of compounds envisioned by the present invention are: e
N (1,4,5,6,7,7hexachlorobicyclo(2.2.l )hept-5-en-2-yl)-,
maleimide. N (1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-S-en-Z-ylmethyl)maleirnide. 2 chloro-N-(1,4,5,5,7,7-hexachlorobicyclo(2.2.1)hept-5- en-2-ylmethyl)maleimide N (5,6,7,8,9,9 hexachloro-l,2,3,4,4a,5,8,8a-octahydro- 1,4,5 ,8-dimethano-naphthalen-2-ylrnethyl)maleimide 2,3 dichloro N-( 1,4,5 ,6,7,7-hexachlorobicyclo(2.2.1)-
hept-5-en-2-ylmethyl) succinimide N (1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2-ylmethyl phthalimide N (1,4,5,6,7,7-hexabromobicyclo(2.2.l)hept-5-en-2-yl)- maleimide 2,3 difluoro N-10-(1,4,5,6,7,7-hexafluorobicyclo(2.2.1)-
hept-S-en-Z-yldecyl)pimelimide 2,3 'dibromo N-( l,4,5;6-tetrabromo 7,7-dimethoxybicyclo (2.2.1 )hept S-en-Z-yImethyD succinirnide N 2 1,4,5 ,6-tetrabromo-7,7 -diphentoxybicyclo(2.2.l)-
hept-S -en-2-yl:) ethyl) succinimide N (1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept-5-en-2-yltolyl)maleimide 2 fluoro N -(1,4,5,6,7,7-hexabromobicyclo(2.2.1)hept- 5-en-2-ylbenzyl)maleimide N (5,6,7,8,9,9 hexabromo-l,2,3,4a;5,8,8a-octahydro- 1,4,5,8-dimethanonaphthalen-Lylphenyl)maleimide N 1,4,5 ,6,7 ,7 hexachlorobicyclo(2.2.l)hept-5-en-2-ylanthryDmaleimide N (1,4,5,6,7,7 hexachlorobicyclo(2.2.1)l1ept-5-en-2-ylnaphthyDmaleimide Generally speaking, the maleimides ofthe present invention may be prepared by reacting the corresponding maleamic acid with acetic anhydride and the phthalirnides of the present invention may be prepared by reacting the corresponding amine withphthalic anhydride. The maleamic acids themselves are obtained'by reacting the appropriate polyhalogenopolycycloalkene amine with maleic arihydride. Detailed preparation of these ma'leanu'c acids is to be found in co-peuding application SerialNunibcr 705,782. The preparation of the amines is described in copending application Serial Number 705,781.
Examples of specific preparations of compounds encompassed by the present invention follow:
:EXAMPLE 1 N- (5,6,7,8,9,9-hexachloro-J ,2,3 ,4,4 [1,5 ,8,8a-ctdhydr0- I ,4,5,8-dimethanonaphthalen-Z-ylmethyl maleimide A mixture of 54 .g. ofN-.(5;6,7,8,8 hexaehloro-l,2,3,4, 4a,5,8,8a 'octahydro-l,4,5,'8-dimethanonaphthale'n-2 ylrnethyl)maleamic acid, 90 ml. of :acetic anhydride and 3 g. of sodium acetate was heated'at 70 for 16 hours then 2 hours at 90. The solution was poured into 250 ml. of water and stirred until solid formed. The crude solid was recrystallized from benzene to give 15 g. of serni-pure product, M.P. 156-62. Thebenzene filtrate was taken to dryness and extracted with hexane. The hexane extract was "taken to dryness and the residue triturated with benzene. The benzene extract was taken to dryness and-the residue triturated'with methanol to give more solid, '13 g. MzP. ISO-8. Recrystallization of the-two combined-crops gave 21 g. 'M.P. 160-2', of pure product of 40% yield. Analysis: Calcd. for CnHmClsNOgYCl, 44.6. Found: C1,
EXAMPLE II N- (1 ,4,5,6,7,7-hexachl0r0bicycl0 (2.2.1 hep t-5-en-2- ylmethyl) phthalimide A solution of .37 g. of 1,4;5,6,7,7 hexachlorobicyclo- (2.2.1)hept-S ene-Z-methylarnine hydrochloride in 200 ml. of water was made :a'lkaline to .phenolphthalein with 20% NaOH solution and extracted with hexane. The hexanesolution of freeamine was then added to asolution of 15 g. of phthalic anhydridein 200 ml. of benzene. After 20 minutes reflux .a solid fell out. It was collected to give "45 "g. of N-'(l,4,5;6,7,7 hexacljlorobicyclo(2.2.1) hept-S-en-Z-ylrnethyl)phthalamic acid, M.P. 180 180151 in'92% yie'lcl. Analyses: 'CalcdJfor C gH ClgNO i Cl, 44.6; neut. equiv. 478. Found: Cl, 44I5;'neut.-equiv.'4S0.
The ph'thalamic -a'cid was "heated "for 20 -n1inutes at 180.5". It evolved water and gave a colorless =li'quid which solidified on cooling. The residue was recrystallized from hexane to give 25 g. (60%) of the pure phthalimide, M.P. 131-2", after one further recrystallization from methanol. Analysis: Calcd. for C H Cl NO Cl, 46.3. Found: CI, 46.0.
EXAMPLE HI N-(I,4,5,6,7,7-hexachlorobicyclo(2.2.1 )hept-S-en-Z- yl) maleimide A total of 30 g. of N-(1,4,S,6,7,7-hexachlorobicyclo- (2.2.1)hept-5-en-2-yl)maleamic acid was added to a well stirred solution of 40 ml. of acetic anhydride and 1.5 g. of sodium acetate at 905. The mixture was kept at -5 for 1.5 hours after the-end of "the addition then it was poured into'water. The'soli'd'whichformedwas collected and extracted with .hot hexane leaving 25 g. of crude product, I'M;P. 161-4". Recrystallization of this material from hexane gave 11 g. of pure product, MZP. 166.9. Analysis: Calcd. for C I-1 61 CI, 53.8. Found: Cl, 53.5. Repetition -.of :the aboveexperiment and further workup with themother rliquor from the-above experiment-gave 21 goo'fssolidrMrP. 164-:6 and 10 g. of solid, MP. 16'3.5. The'total-of 42g. of .N- 1,'4,'5,6,7,7, -:hexachlorobicyclo(2.21)hept 5 en-2-;yl) nraleimide :is a 75% overall yield.
EXAMPLE IV T o a'well stirred solution of 50 ml. of acetic-anhydride and 3g. of sodium acetateat 100 was slowly-added 58 g. of 2 chloro-N-(1,4,5,6,7,7-hexachlorohicyclo(212.l) hept-5-en 2-ylmethyl)maleamic acid. Th'eresulting'solutionwas kept at 100 for 30 minutes then poured into 400 ml. of water and allowed to stand "for 24 hours. The water insoluble gum formed was dissolved -in hot hexane but failed 'to crystallize upon cooling "the solution. The hexane was removed and aportion of the 'oil crystallized from cold pentane to give '1 g.-of -product, M.P. 76-8. The mother liquor was concentrated and distilledto give a colorless liquid, 13:1. -210' '(025 1.0 'mm.). Recrystallizaion or the distillate "from pentane gave 40 g. (75%) ofth'e desired product, 'MzP.
756. Analysis of material, MIP. '76-8". Calcd. 'for C HsCl gNo z Cl, 55.9. Found: C], 55:8.
EXAMPLE V N-(1;4,5,6,7,7=hexachl0rdbicyclo(2.2;19hept 5-en-2- ylmethyl)maleimide There was added 46 grams of N-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2-ylmethyl)maleamic acid to 60 grams of acetic anhydride and lggrams of anhydrous sodium acetate stirred at 80. The mixture was kept at 100 for one hour then poured into 300 ml.- of water .and allowed to stand overnight. A total of 48 grams of crude N-( 1,4,5 ,6,7,7-hexachlorobicyclo( 2.2. 1 hept-S-en- 2-ylmethyl)rnaleimide was collected. The crude'was dissolved in hothexane and the solution was-filtered. Cooling the filtrate gave 13 grams of solid, M.P. 107-109 which had M.P. of 108-l10 afterone more recrystallization from hexane. This in turn was raised to 112- 113.5 upon further recrystallization from methanol. Workup of the mother liquors gave 26 ,grams of solid. M.P. 112-113 from methanol. The :yield was 60. Further recrystallization of the 112111315 material from methanol ,gave analytical material, :M.P. 1 1-3-'1 14. Calcd. for C H CI -NO C, 35.2; H, 1. 7; "Cl, 52.0. Found: C, 35.2; H, 1.5; Cl, 52.1.
EXAMPLE VI 2,3-dichl0r0-N-(1,4,5,6,7,7Jzexadhl0robicyclo(2.2.1 hept-5-en-2-ylmethyl )succinimide Chlorine was passed into asolution "of 45 grams of N (1,4,5,6,7,7 hexachlorobicyclo(2.2.l)hept 5-en-yland chlorinated under UV. irradiation for 2.5 hours.
The solvent was removed and the residue triturated with hexane to give a solid M.P. 118-122. One recrystallization from heptane gave 45 grams of product (86%), M.P. l22126. Recrystallization from benzene gave 34.5 grams of solid M.P. 125-132 C., 6.5 grams of solid, M.P. 122429. Analyses of solid melting at 125-132. Calcd. for C H cl NO C, 29.9; H, 1.45; Cl, 59.0. Found: C, 30.4; H, 1.7; CI, 59.0.
The compounds of the present invention possess fungicidal activity to a Wide variety of plant pathogens. In the foliage fungicide screen, three varieties of bean plants and four foliage fungus diseases were employed. Employing these hosts and pathogens the chemicals were To facilitate deposit, the primary leaves are oriented to a vertical position by pinning them to a small wire staff. Either the upper or lower epidermis of the leaf is exposed to the spray stream, depending on the surface to be inoculated.
When the mist type spray and the diluent mixture is applied, a drying interval of 1-2 hours is sufiicient before inoculation with spore suspensions using a specially constructed atomizer. Inoculations with bean mildew are made by dusting conidia over treated plants in the greenhouse.
After 24 hours incubation at 19 C. and 100% humidity, the plants are removed to the controlled environment greenhouse for sympton development. Disease control and phytotoxicity assessments are made within 7 days.
The following table summarizes the results of screenmg:
TABLE 1.FOLIAGE Funorcmn SCREEN Disease Control Min. Effective Cone. Phytotoxieity Max. Safe (P-P- Oonc. (p.p.m.)
P.p. E.p. U.p. 0.1. L. P. BV
N (1,4, 5,6, 7, 7-Hexachlorobieyclo- (2.2.1)hept-5-en-2-yl-methyl)- maleimide 125 500 125 15 1, 000 500 1, 000 2-Ohloro-N-(1,4,5,6,7,7 -hexaehlorobicyclo (2.2.1) hept- 5 -en- 2 ylrnethyDmaleimide 125 250-500 63425 32 2, 000 500 1, 000 N- (5,6,7,8,9,9-LE[eXach1oro-1, 2,3,
4, 4a,5,8,8a octahydro -1, 4 -exo,
endo 5,8 dimethanonaphthalen-2-ylmethyl -maleimide 125 1, 000 500 32 1, 000 1, 000 1, 000 2, 3-Diehloro-N- (1,4,5,6,7, 7-hexaehlorobieyelo (2.2.1)hept 5 en 2-ylmethyl)succinin1ide 125 250 63 32-63 2, 000 1, 000 1, 000 N- (1, 4, 5, 6,7,7-Hexach10robicyclophthalimide 1,000 1,000 1,000 1,000 l,000 1,000 1,000 N- (1,4, 5,6,7, 7-I-Iexaehlorobieycloide 250 500-1, 000 63 32 500 500 500-1, 000
a P. .=phytophth0m phaseolz' (downy mildew of lime. bean); E.p.=Erysiphe polygom (bean powdery mildew); U.p. romyces phaseoli (bean rust); O.l.=Col.letotrieh um.
b L=Lima bean, P=Pint0 bean, BV=Blaek Valentine bean.
screened for general as well as specific control activity and for phytotoxicity. Diseases and hosts are shown below:
BEAN HOSTS PATHOGENS Phaseolus vulgarts var. Pinto Urognyoes phaseoh var. ta)- P. pulgam's var. Black Valenmoo (rust) Erysiphe polygon/i (powdery ildew) Ool l ctotr ichum lindemuthianmim (anthracnose) Phytophthom p h a. s e o H (downy mildew) These four bean pathogens are of economic importance and represent each of the four classes of fungi. P. phaseoli is closely allied with P. infestans, the important potato and tomato pathogen. Thus, with the above selection, chemicals can be routinely screened for general or specific disease control activity and for phytotoxicity on a moderately susceptible plant type.
The test is carried out according to the following procedure: Test chemicals are prepared as 1% w./v. stock solutions in a solvent The stock is diluted for spraying using a diluent consisting of distilled water+solvent (1:1 or with distilled water plus two solvents (2:1:1). Triton X-l55, at 0.005% W. is used as a wetting agent for each concentration of toxicant. All chemicals are initially tested at a single concentration of 1000 p.p.m. If acceptable disease control is shown, the chemicals are retested at 1000 ppm. and the next lowest dilution of 500 ppm. Chemicals continuing to show disease control are retested in this fashion until the minimum effective concentration is determined. Phytotoxicity assessments are expressed as the maximum Safe concentration.
Spray applications are made using a laboratory sprayer. The bean plants are selected for use at a stage when the two primary'leaves are about three-quarters expanded.
tine P. limensis var. Fordhook The effectiveness of the present compounds as fungicidm is further evidenced by the following tests:
To obtain expanded disease control data, chemicals were sprayed as emulsions, solutions, or suspensions using concentrations of 0.24% w., 0.12% w. and 0.06% w. These correspond respectively to 2, 1, and 0.5 pound of toxicant per gallons of spray. Plants were sprayed to their run-off stage, dried for 24 hours, and inoculated with test fungus spores. After inoculation, the plants were held for 24-48 hours in a humidified incubation chamber at 19 C. They were then removed to the greenhouse for disease and phytotoxicity development.
Crops and diseases used were tomato or potato blight (Phytophzhora infestanzs), celery blight (Septoria apiigraveolentis), bean mildew (Erysiphe polygom'), bean rust (Uromyces appendiculatus), and cucumber anthracnose (Colletotrichum lagenarium).
From four replicated plants per concentration, a percentage disease control figure was obtained, which was based upon the improvement shown over the untreated checks as follow:
disease rating of untreated check -disease rating of treatment or standard disease rating of untreated check The percent disease control for a treatment was next compared with the percent control for the standard fungicide (captan at 0.24% w. of formulated chemical). as follows:
Foliage-fungicide activity index (F-F.A.I.)
1 percent control for treatment percent control for standard Where the disease control for the test chemical and A further form in whieh the fungicidal compounds :of the present invention :may 'be'applied consists of solutions of'the active ingredient in suitable inert liquid-orz'semisolid diluents, in which the active ingredients are present-in molecular ly dispersed form. l he form in which the agents to be :employed :are applied tto the objects treateddepends on the :nature :oftheobjecfland thepurpose of the application.
Suitable inert solvents 'for the manufacture of liquid preparations should be inflammable, .as odorless as possible and without any toxic-efiecton humans and animals when properly used. 'Neithershould they :have a corrosive etiect on the components of the preparations or T'ABLE 2.--FLIAGE FU'NGICIDE Tesr Foliage-fungicide activity index Activitylndex at 0.24% Cone. (Upper figure) and %control 300.06% (Lower Figure) Phytoboxicity at 0.24% (upper figure) and 0.06% cone. (lower figure) respectively Chemical Compound Com- Com- 'P.i.* Sri. -E;p. U.a. C 1 bined T b C B On bined Index N- (1 ,4,5,6,7,7- Hexachlorobicyelo (2.2.1)hept-5-en 115 I06 100 129 133 115 200 75 2-yl-rnethyl)malein1ide 100 100 100 100 I 100' '100 100 0 2- Chloro N- (1,4,5,6,7,7- hexachlorobieyclo (2.2.1) .100 125 95 11-8 250 75 hept-5-en2-ylmothyDmalelmide "100 :89 89 -100 200 0 B P.i.=Ph1 t0phthora infesta'ns (late blight oftomato).
S.a. =Septoria apii-graveolentic (late blight of celery). E.p.= Erysiphe pol 1011i (bean powdery mildew). U.a,= Ur0m1/ces appendiculatus (bean rust). 0.1. Calletotrichmn lagemriu'm (cucumber anthracnose). b T=tomato, C=celery, B=bean, Cu=cneumber.
The active compounds of the present invention may be eused alone or in combination with other fungicidal, viricidal, insecticidal, or acaricidal materials, the action on which "may be either internal or external, with plant nutritives, .plant hormones and the like. Wetting agents, .and if necessary or desirable, stickers such as the heavy hydrocarbons oils with a minimum viscosity of Engler at 50 C. can be present. Any conventional wetting agent which will not react with the'toxicant for example alkyl sulfate salts, alkyl Sary'l sulfonate salts, su'lfosuccinate salts, .ethers of polyethylene glycols and alkylated phenols, and the like can be employed. If the toxic agents are employed in the form of emulsions or suspensions, for example, in water, solvents such .as oils, emulsifiers, emulsion stabilizers and the like may be added. Materials which suppress phytotoxic action may also be added if desired. For example, glucose is known to protect tomato plants against damage by certain substances having a phytotoxic effect when employed in concentrated form.
The 'irnides and maleimides of the present invention may be applied by means of spraying. .Spraying .of the plants to be treated may be performed with aqueous emulsions solutions or suspensions of the active agents. The spray .liquid is generally applied at a rate of from about 75 to 150 gallons per acre. If spraying is effected with smaller quantities ofliquid as in low volume spraying, high concentrations of the active agents should be employed. If desired, a minoramount of the order of about 0.01 to about 0.05% by weight, of a wetting agent may be added to aid :in forming a suspension of the salt in the aqueous medium. Any of the conventional wetting agents 'can be employed. Particularly suitable wetting agents are the sodium salts of a mixture of secondary hep'tadecyl sulfates, sold commercially under the name of Teepol and polyethylene glycol ethers of alkyl phenols sold under the trade name of Triton X400 and Triton X-l55. Preferable concentrate compositions comprising an active compound of the present invention and a .suitable .Wetting agent are prepared, :and the concentrate is then dispersed in water prior to :use.
*the material of the storage vessel.
Examples of suitable solvents are high boiling oils, e.g. oils of vegetable origin such as castor oil, etc, and lower-boiling solvents with a flash point of at least 30 C., such as carbon tetrachloride, ethylene dichloride, hydrated naphthalene, alkylated naphthalene, sorbent naphtha, etc. Mixtures of solvents may also be used.
The active compounds of the present invention may also be applied in the form'o'f dusts utilizing as the inert vehicle such materials as tricalcium phosphate, precipitated chalk, bentonite, kieselguhr, etc.
These compounds may also be employed in the form of aerosols. For this purpose, the active ingredient is dissolved or dispersed in a solvent boiling below room temperature at atmospheric pressure.
We claim as our invention:
1. A polyhalo compound of the formula wherein X is a member of the group consisting of hydrogen and halogen, and at least one X is halogen, X is a member of the group consisting of hydrogen, halogen and lower alkoxy, R is selected from the group consisting of alkylene, phenylalkylene, tolylalkylene, naphthalenylalkylene and anthracenylalkylene in which alkylene is in each case alkylene of 1 to 10 carbon atoms, and tolylene, phenylene, naphthylene and anthrylene, y is a whole number from 0 to l, and W is -a member selected from the group consisting of alkylene of 2 to 5 carbon atoms, alkyleneof 2 to 5 carbon atoms, halosubstituted alkylene of 2 to .5 carbon atoms, .halo-subsitutedalkenyleneof 2 to 5 carbon atoms and .1 ,Z phenyI- ene, :andn is a whole number from 0 to 1.
2. A compound of the formula wherein W is straight-chain, halo-substituted alkylene 10 of 2 to 5 carbon atoms.
3. A compound of the formula CHrN XI X! K O wherein X and X are each halogen.
5. A compound of the formula wherein X and X are each halogen.
6. N-( 1,4,5 ,6,7,7-hexachlorobicyc1o(2.2. 1 )hept-S -en2- yl-rnethyl)maleimide.
7. 2-chloro-n (1,4,5,6,7,7 hexachlorobicyc1o(2.2.1) hept-5-en-2-yLmethyl)maleimide.
8. N (5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8aoctahydro -1,4,5,7- dimethanonaphthalen -2- y1methyl)- maleimide.
9. 2,3 dichloro -N- (1,4,5,6,7,7 hexachlorobicyclo- (2.2.1 -hept-5-en-2-y1methyl) succinimide.
10. N-( 1,4,5,6,7,7-hexachlorobicyc1o(2.2. 1 )hept-S-en- Z-yl) -ma1eimide.
11. The method of combatting fungi on living plants comprising applying a fungicidal toxic amount of N- (1,4,5,6,7,7 hexach1orobicyc1o(2.2.1)hept 5 en 2- ylmethyl)maleimide to said plants.
References Cited in the file of this patent UNITED STATES PATENTS 2,015,045 Teichmann Sept. 17, 1935 2,593,840 Buc Apr. 22, 1952 2,638,431 Harry May 12, 1953 2,642,373 Dazzi June 16, 1953 2,698,850 Long Jan. 4, 1955 2,795,589 Bluestone June 11, 1957 2,813,877 Lambrech Nov. 19, 1957

Claims (2)

1. A POLYHALO COMPOUND OF THE FORMULA
4. A COMPOUND OF THE FORMULA
US705787A 1957-12-30 1957-12-30 Carboximide compounds Expired - Lifetime US3004036A (en)

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US3098002A (en) * 1961-02-01 1963-07-16 Us Rubber Co Method of controlling fungi and algae with nu-phenyl-itaconimides
US3098003A (en) * 1961-02-01 1963-07-16 Us Rubber Co Itaconimide fungicides and algaecides
US3138523A (en) * 1962-04-06 1964-06-23 Us Rubber Co Method of protecting against arachnids with nu-(3-nitrophenyl) itaconimide
US4174342A (en) * 1978-03-27 1979-11-13 Abbott Laboratories N-(Acenaphthenyl)maleimides

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US2015045A (en) * 1932-12-03 1935-09-17 Texas Co Insecticide and fungicide
US2593840A (en) * 1949-12-30 1952-04-22 Gen Aniline & Film Corp mu-phthalimidomethyl derivatives of aniline, nitrobenzene, and nuclear substitution products thereof
US2638431A (en) * 1950-11-30 1953-05-12 Union Carbide & Carbon Corp 2-norcamphanemethanol and 2-norcamphanemethoxyethanol applied to plants to inhibit fungous growths
US2642373A (en) * 1950-03-25 1953-06-16 Monsanto Chemicals 2-hydroxyethyl 2-phenylethyl sulfide as a fungicide
US2698850A (en) * 1952-02-12 1955-01-04 Parke Davis & Co N-substituted phthalimide compound and method for obtaining the same
US2795589A (en) * 1953-03-04 1957-06-11 Velsicol Chemical Corp Nu-substituted imides of hexachloro bicyclo [2.2.1] heptene dicarboxylic acids
US2813877A (en) * 1954-09-07 1957-11-19 Union Carbide Corp N-substituted bicyclo-(2.2.1)-5-heptene-2, 3-dicarboximides

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Publication number Priority date Publication date Assignee Title
US2015045A (en) * 1932-12-03 1935-09-17 Texas Co Insecticide and fungicide
US2593840A (en) * 1949-12-30 1952-04-22 Gen Aniline & Film Corp mu-phthalimidomethyl derivatives of aniline, nitrobenzene, and nuclear substitution products thereof
US2642373A (en) * 1950-03-25 1953-06-16 Monsanto Chemicals 2-hydroxyethyl 2-phenylethyl sulfide as a fungicide
US2638431A (en) * 1950-11-30 1953-05-12 Union Carbide & Carbon Corp 2-norcamphanemethanol and 2-norcamphanemethoxyethanol applied to plants to inhibit fungous growths
US2698850A (en) * 1952-02-12 1955-01-04 Parke Davis & Co N-substituted phthalimide compound and method for obtaining the same
US2795589A (en) * 1953-03-04 1957-06-11 Velsicol Chemical Corp Nu-substituted imides of hexachloro bicyclo [2.2.1] heptene dicarboxylic acids
US2813877A (en) * 1954-09-07 1957-11-19 Union Carbide Corp N-substituted bicyclo-(2.2.1)-5-heptene-2, 3-dicarboximides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3098002A (en) * 1961-02-01 1963-07-16 Us Rubber Co Method of controlling fungi and algae with nu-phenyl-itaconimides
US3098003A (en) * 1961-02-01 1963-07-16 Us Rubber Co Itaconimide fungicides and algaecides
US3138523A (en) * 1962-04-06 1964-06-23 Us Rubber Co Method of protecting against arachnids with nu-(3-nitrophenyl) itaconimide
US4174342A (en) * 1978-03-27 1979-11-13 Abbott Laboratories N-(Acenaphthenyl)maleimides

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