US3006954A - Urea and thiourea compounds - Google Patents

Urea and thiourea compounds Download PDF

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US3006954A
US3006954A US705786A US70578657A US3006954A US 3006954 A US3006954 A US 3006954A US 705786 A US705786 A US 705786A US 70578657 A US70578657 A US 70578657A US 3006954 A US3006954 A US 3006954A
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hept
thiourea
ylmethyl
hexachlorobicyclo
grams
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US705786A
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David E Ramey
Silverman Milton
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Shell USA Inc
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Shell Oil Co
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Priority to US1152A priority patent/US3006808A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/14—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/18—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of a saturated carbon skeleton containing rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C275/22—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
    • C07C335/08—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/90—Ring systems containing bridged rings containing more than four rings

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. 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;
  • the principal object of the present invention to provide new and novel compounds which are effective as fungicides yet do not manifest prohibitive phytotoxicity or 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 provide 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 polyhalogenocycloalkene such as hexachlorobicyclo(2.2.l)hept-S-ene and the other terminal position is occupied by a urea or thiourea radical.
  • a polyhalogenocycloalkene such as hexachlorobicyclo(2.2.l)hept-S-ene
  • the other terminal position is occupied by a urea or thiourea radical.
  • the cycloalkene portion of the molecule may be attached directly to the urea or thiourea radical or alternatively, the terminal positions of the molecule may be separated by alkyl, aryl, or aralkyl radicals.
  • halogenated bicyclo(2.2.1)hept-S-ene rings as shown in the following structural formula are preferred:
  • the basic skeleton consists of not more than five linearly fused five membered rings.
  • R represents a straight chain, branched chain or cyclic alkylene group of 1-10 carbon atoms, an arylene group such as phenylene, tolylene, naphthylene and anthrylene, or an aralkylene group wherein the alkylene portion contains 1-10 carbon atoms and the aryl portion is chosen from such groups as phenyl, benzyl, tolyl, naphthal'enyl, and anthracenyl.
  • Y is 0 to 10.
  • Z is oxygen or sulfur, preferably oxygen.
  • X represents hydrogen or a halogen (preferably chlorine) and X represents hydrogen, a halogen (preferably chlorine) or an alkoxy (preferably methoxy) group. At least one X is preferably a halogen.
  • R and R individually represent hydrogen, aliphatic groups of 1-10 carbon atoms, saturated and unsaturated, both substituted and unsubstituted, aromatic groups such as phenyl, benzyl, tolyl, naphthalenyl and anthracenyl or aralkyl groups wherein the alkyl portions contain 1-l0 carbon atoms and the aryl portions are chosen from such groups as phenyl, benzyl, tolyl, naphthalenyl and anthracenyl.
  • R and R" may also individually represent a polyhalogenocycloalkene of the type already described and illustrated.
  • cycloalkenes may be attached directly to a nitrogen atom as in 1,3-bis(l,2,3,4-tetrachloro-7- oxobicyclo(2.2.1)hept-5-en-2-yl)-2 thiourea tetramethyl diacetal or separated by an aliphatic group of 1-10 carbon atoms as in 1,3-bis(1,2,3,4-tetrachloro-7-oxobicyclo- (2.2.1 hept-S-en-Z-ylmethyl) -2-thiourea tetramethyl diacetal.
  • the compounds of the present invention may thus be considered as ureas and thioureas having substituted therein halogenated polycyclic structures such as polyhalopolycyclic alkenyl radical or a halogenated 1,4,5,8-dimethanonaphthyl radical.
  • isothiocyanates can be prepared as adduotion products as in the reaction of hexachlorocyclopentadiene with allyl isothiocyanate to form hexachlorobicycloheptenylmethyl isothiocyanate.
  • the ureas of the present invention may, if desired, be prepared by reacting the appropriate polyhalogenopolycycloalkene amine with an alkylcarbamoyl chloride. The preparation of the amines is described in co-pending application Serial Number 705,781, filed December 30, 1957.
  • EXAMPLE V.3 (1,4,5,6,7,7 HEXACHLOROBICY- CLO(2.2.1)HEPT-5-EN-2-YLMETHYL) 1,1 BIS- (Z-HYDROXYETHYL) -2-THIOUREA
  • a solution of 21 grams of diethanolamine in ml. of methanol was added to 74 grams of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2 ylmethyl isothiocyanate in 200 ml. of methanol. After standing at 30 for 24 hours the solvent was removed under vacuum leaving a viscous syrup which was soluble in benzene. After standing, the oil became a glassy solid, M.P. 75100.
  • the black oily solid was taken up in 150 ml. of dioxane, charcoaled, and filtered. Two volumes of methanol and one of water were added. The precipitate The solid was recrystallized from'lOO ml. of heptane to give 9.0 g. of product, M.P. 186188.5. A second crop of 3 g., M.P. 176-182 was obtained by concentrating the mother These two crops were combined and recrystallized from ethyl acetate to give 8.0 g. (38% yield) of product as needles, M.P. 188l90.
  • Erysiphe pol /gem (powdery mildew) Colletotrichum lindemuthz'anum (anthracnose) Phytophthora phaseoli (downy mildew.
  • 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 diluent consisting of distilled water plus two co-solvents.
  • Triton X-155 at 0.005% w. (2:1:1) -0.10% W. is used as a wetting agent for each concentrationof toxicant.
  • All chemicals are initially tested at a single concentration of 1000 p.p.m. If acceptable disease' control is shown, chemicals are retested at 1000 p.p.m. and the next lowest dilution of 500 p.p.m. Chemicals continuing to show disease control are retested in this fashion until the minimum elfective 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.
  • 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 th surface to be inoculated.
  • C.l. Collctotrichum Li'n'demuthianum (bean anthracnose).
  • Crops and diseases used were tomato or potato blight (Phytophthora infestans), celery blight (Septoria apiigraveolentis), bean mildew (Erysiphe polygoni), bean rust (Uromyces appendiculatus), and cucumber anthracnose (Collettotrichum GmbH').
  • Pereent control for treatment Percent control for standard 100 Where the disease control for the test chemical and standard was equivalent, the index value was unity, 100. Values above 100 indicated superiority. It will be understood however that compounds showing index values substantially below 100 may also be of considerable value.
  • Readings for plant injury were obtained on tomatoes, beans, celery and cucumber. Both chronic toxicity (yellowing, distortion, etc.) and acute toxicity (tissue death) were recorded. The scale used was from -400. 0 represented no visible poisoning and 400 was the most severe manifestation.
  • the active compounds of the present invention may be used alone or in combination with other fungicidal, viriciadal, 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 hydrocarbon oils with a minimum viscosity of 10 Engler at C. can be present.
  • any conventional wetting agent which will not react with the toxicant for example, alkyl sulfate salts, alkyl aryl sulfonate salts, sulfosuccinate salts, ethers from 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 ureas and thiourea compounds 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 to 150 gallons per acre. If spraying is effected with smaller quantities of liquid as in low volume spraying, high concentrations of the active agents should be employed. If desired, a minor amount of 5 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 heptadecyl sulfates, sold commercially under the name of Teepol and polyethylene glycol ethers of alkyl phenols sold under the trade name of Triton X-100 and Triton X155.
  • 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.
  • a further form in which the fungicidal compounds of the present invention may be applied consists of solutions of the active ingredient in suitable inert liquid or semisolid diluents, in which the active ingredient is present in molecularly dispersed form.
  • the form in which the agents to be employed are applied to the objects treated fungicide test Chemical compound 1-(1,4,5,6,7,7-hexach1orobicyclo (2.2.1) -hept-5-en-2-y1methyl) -2thiourea.
  • Suitable inert solvents for the manufacture of liquid preparations should not be readily inflammable, as odorless as possible and Without any toxic eifect on humans and animals when properly used. Neither should they have a corrosive efiect on the components of the preparations or the material of the storage vessel.
  • suitable solvents are high boiling oils, eg. 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 of dusts utilizing as the inert vehicle such materials as tricalcium phosphate, precipitated chalk, bentonite, kaolin, kieselgnhr, 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.
  • R is alkylene of from 1 to carbon atoms and R and R" are each alkenyl of from 1 to 10 carbon atoms.
  • R is alkylene of from 1 to 10 carbon atoms and R and R are each alkyl of from 1 to 10 carbon atoms.

Description

United States Patent Ofiice 3,005,954 Patented Oct. 31, 1961 The present invention is concerned with organic compounds wherein one terminal position is occupied by a polyhalogenopolycycloalken'yl radical and the other terminal position is occu-pied by a urea or thiourea radical. These compounds have been found to possess significant toxicity toward and inhibition of a wide variety of fungi.
The need for efficient 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 phy-to-toxicity under the conditions utilized for fungus control and toxicity toward warm blooded animals are among the most common shortcomingsof 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 phytotoxicity or 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 provide 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, features 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 polyhalogenocycloalkene such as hexachlorobicyclo(2.2.l)hept-S-ene and the other terminal position is occupied by a urea or thiourea radical.
The cycloalkene portion of the molecule may be attached directly to the urea or thiourea radical or alternatively, the terminal positions of the molecule may be separated by alkyl, aryl, or aralkyl radicals.
Of the polyhalogenopolycycloalkenes which occupy one terminal position of the compounds of the present invention, halogenated bicyclo(2.2.1)hept-S-ene rings as shown in the following structural formula are preferred:
Of equal interest is the dimethanonaphthalene ring structure shown in the following structural formula:
X n R x/\/\ (R) -NHON\ n l X The present invention also encompasses the polycyclic structures shown in the following general formula:
The basic skeleton consists of not more than five linearly fused five membered rings.
In these formulae R represents a straight chain, branched chain or cyclic alkylene group of 1-10 carbon atoms, an arylene group such as phenylene, tolylene, naphthylene and anthrylene, or an aralkylene group wherein the alkylene portion contains 1-10 carbon atoms and the aryl portion is chosen from such groups as phenyl, benzyl, tolyl, naphthal'enyl, and anthracenyl. Y is 0 to 10. Z is oxygen or sulfur, preferably oxygen.
X represents hydrogen or a halogen (preferably chlorine) and X represents hydrogen, a halogen (preferably chlorine) or an alkoxy (preferably methoxy) group. At least one X is preferably a halogen.
R and R individually represent hydrogen, aliphatic groups of 1-10 carbon atoms, saturated and unsaturated, both substituted and unsubstituted, aromatic groups such as phenyl, benzyl, tolyl, naphthalenyl and anthracenyl or aralkyl groups wherein the alkyl portions contain 1-l0 carbon atoms and the aryl portions are chosen from such groups as phenyl, benzyl, tolyl, naphthalenyl and anthracenyl. R and R" may also individually represent a polyhalogenocycloalkene of the type already described and illustrated. These cycloalkenes may be attached directly to a nitrogen atom as in 1,3-bis(l,2,3,4-tetrachloro-7- oxobicyclo(2.2.1)hept-5-en-2-yl)-2 thiourea tetramethyl diacetal or separated by an aliphatic group of 1-10 carbon atoms as in 1,3-bis(1,2,3,4-tetrachloro-7-oxobicyclo- (2.2.1 hept-S-en-Z-ylmethyl) -2-thiourea tetramethyl diacetal. The compounds of the present invention may thus be considered as ureas and thioureas having substituted therein halogenated polycyclic structures such as polyhalopolycyclic alkenyl radical or a halogenated 1,4,5,8-dimethanonaphthyl radical.
Examples of specific compounds encompassed by the present invention follow:
1 (1,4,5,6,7 -hexachlorobicyclo(2.2.1)hept 5 en 2- ylmethyl) -2-thiourea 3-(1,4,5,6,7,7-hex-achlorobicyclo(2.2.1)hept 5 en 2- yimethyl -1,1-dimethyl-2-thiourea 1-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept 5 en 2- ylmethyl) -3 -isopropyl-2-thiourea 1,1-diallyl-3-(1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept- 5 -en-2-ylmethyl) -2-thiourea 3-(l,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept 5 en 2- ylmethyl) -1 1 bis (Z-hydroxyethyl -2-thiourea 1,1-di-sec-b'utyl-3-(l,4,5,6,7,7 hexachlorobicyclo(2.2.1)-
kept-5 -en-2-ylmethyl) -2-thiourea 3-(1,4,5,6,7,7-hexachlorobicyclo(2.2.l)hept 5 en 2- ylmethyl) 1, l-dimethylurea 3-(bicyclo(2.2.1)hept-S-en-Z-ylmethyl) 1,1 dimethyl- 2-thiourea 1,3-bis(1,2,3,4-tetrachloro 7 oxobicyclo(2.2.1)hept-5- en-2-ylmethyl)-2-thiourea tetramethyl diacetal. (10-(1,4,5,6,7,7-hexabromo-bicyclo(2.2.1)hept 5 en 2- yl) decyl) urea l-(1,4,5,6,7,7 hexafluorobicyclo(2.2.l)hept 5 en 2- ylbenzyl) -3isopropyl-2-thiourea 1,1-dia1lyl-3 (1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept- 5 -en-2-yltolyl) -2-thiourea 3-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept 5 en 2- ylnaphthyl -1, 1-bis(2-hydroxyethyl)-2-thiourea 3-(1,4,5,'6,7,7-hexachlorobicyclo(2.2.l)hept 5 en 2- y1anthryl)-1,1-didecylurea 3'-(10-( (bicyclo(2.2.1)hept 5 en 2 yl)decyl)phenyl)- I, l-dimethyl-Z-thiourea 1-(l,4,5,6,7,7-hexachlorobicycl-o(2.2.1)hept 5 en 2- yl-2-thiourea 1-(5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8a octahydro- 1,4,5',8-dimethano-2-naphthalen-2-yl) -2-thiourea 1-(10-(5,6,7,8,9,9 hexabromo 1,2,3,4,4a,5,8,8a octahydro-1,4,5,8 dimethanonaphthalen 2 yl)decyl) 2- thiourea 3-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept 5 en 2- ylmethyl) 1 -b enzyl- 1-tolyl-2-thiourea 3-(3-( 1,4,5,6,7,7 -hexabromobicyclo(2.2.1)hept 5 en- 2-y1 propyl) -1-naphthyl-1-anthryl-2-thiourea 3 (bicyclo(2.2.1)hept-S-en-Z-ylmethyl) 1,1 di(decylphenyl) -2-thiourea 1-(5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8a octahydro- 1,4,5,8-dimethanonaphthalen-2-yl)-2-thiourea Generally speaking the thiourea of the present invention may be prepared by reacting the corresponding polyhalogenopolycycloalkene isothiocyanate with the appropriate amine. These isothiocyanates can be prepared as adduotion products as in the reaction of hexachlorocyclopentadiene with allyl isothiocyanate to form hexachlorobicycloheptenylmethyl isothiocyanate. The ureas of the present invention may, if desired, be prepared by reacting the appropriate polyhalogenopolycycloalkene amine with an alkylcarbamoyl chloride. The preparation of the amines is described in co-pending application Serial Number 705,781, filed December 30, 1957.
Examples of specific preparations of compounds encompassed by the present invention follow:
EXAMPLE I. l (1,4,5,6,7,7 HEXACHLOROBICY- CLO(2.2.l)I-IEPT 5 EN 2- YLMETHYL) 2- THIOUREA To a solution of 8 grams of anhydrous ammonia in 175 ml. of anhydrous ethanol was added 50 grams of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept 5 en 2 ylmethyl isothiocyanate. After standing at room temperature over night the solvent was stripped to give a viscous dark oil which could not be crystallized immediately. Upon standing for about 3 months partial crystallization occurred. The solid was dissolved in ethanol and reprecipitated by addition of ether. The tan flocculent material, 35 grams, was recrystallized several times from ether to give 28 grams of a pure white material, M.P. 75 with decomposition.
Analysis.Calcd. for C H CI N S: C1, 54.8; N, 7.2; S, 8.2. Found: Cl, 53.0; N, 6.9; S, 7.4.
EXAMPLE II.3 (1,4,5 ,6,7,7 HEXACHLOROBICY- CLO(2.2.1)HEPT 5 EN 2 YLMETHYL) -1,1-DI- METHYL-Z-THIOUREA A solution of 20* grams of dimethylamine in about 20 ml. of ethanol was added to a solution of 55.8 grams of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept 5 en 2 ylmethyl isothiocyanate in 150 m1. of ether at The mixture was stored in a refrigerator at 2 overnight. The resulting White solid was collected on a Biichner funnel and washed well with cold ether; 58 grams, M.P. 158 160". Upon recrystallization from 95% ethanol a first crop, 37 grams, melted at 160-161".
AnalySis.--Calcd. for C11HI2CI5N2SZ Cl, N, S, 7.7. Found: CI, 50.8; N, 6.1; S, 7.3.
EXAMPLE III. 1-(1,4,5,6,7,7-HEXACHLOROBICY- CLO(2.2.1)HEPT EN 2 YLMETHYL) -3-ISO PROPYL-Z-THIOUREA A solution of 0.2 mole (73.6 grams) of 1,4,5,6,7,7- hexachlorobieyclo(2.2.1 )hept-5-en-2-ylmethyl isothiocyamate in m1. of ethanol was reacted with 12 grams (0.2 mole) of isopropylamine at 40 for one half hour, then kept at room temperature overnight. The mixture was poured into water; the solid was collected, M.P. 145- 152. It was recrystallized from a mixture of benzene- 4 hexane to give 27 grams of pure product, M.P. 154- 15.6".
Analysis.Calcd. for C H Cl N S: CI, 49.5; N, 6.5. Found: Cl, 49.2, 49.4; N, 6.3.
EXAMPLE IV. 1,1 DIALLYL3-(1,4,5,6,7,7-HEXA- CHLOROBICYCLO(2.2.1)HEPT 5 EN 2 YL- METHYL) -2-THIOUREA To a solution of 75 grams of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-S-en-Z-ylmethyl isothiocyanate in 200 ml. of ether was added a solution of 20 g. of diallylamine in 100 ml. of ether over a period of 20 minutes. When no solid had formed after 3 days hexane was added and most of the ether was boiled off. On cooling grams of solid was obtained. 40 grams of this was recrystallized to give a first crop of 26 grams, M.P. 131.5-132.5.
Analysis.-Calcd. for C H Cl N S: Cl, 45.5; N, 6.0. Found: Cl, 45.4; N, 5.9.
EXAMPLE V.3 (1,4,5,6,7,7 HEXACHLOROBICY- CLO(2.2.1)HEPT-5-EN-2-YLMETHYL) 1,1 BIS- (Z-HYDROXYETHYL) -2-THIOUREA A solution of 21 grams of diethanolamine in ml. of methanol was added to 74 grams of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2 ylmethyl isothiocyanate in 200 ml. of methanol. After standing at 30 for 24 hours the solvent was removed under vacuum leaving a viscous syrup which was soluble in benzene. After standing, the oil became a glassy solid, M.P. 75100.
Analysis.Calcd. for C H N SO Cl Cl, Found: Cl, 44.9.
EXAMPLE VI.-1-DI SEC BUTYL 3 (1,4,5,6,7,7- HEXACHLOROBICYCLO(2.2.1)HEPT 5 EN 2- YLM ETHYL) -2-THIOUREA Thirteen grams of di-sec-butylamine was added to 37 grams of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2- ylmethyl isothiocyan-ate in 10 ml. of benzene. After the exothermic reaction subsided 200 ml. of hexane was added and the solution cooled to give 29 grams of product, M.P. 106 1082 and concentration of the mother liquor gave 7 grams more solid, M.P. 103106.
Analysis.Calcd. for C'1H24C16N2S: Cl, 42.4. Found: C1, 42.5, 42.6.
EXAMPLE VII.-3 (1,4,5,6,7,7-HEXACHLOROBICY- CLO(2.2.1)HEPT 5 EN 2 YLMETHYL-1,l-DI- METHYL UREA A solution of 33 grams of 1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-ene-2-methylamine, 10.8 grams ,of dime-thylcarbamoyl chloride, 8 grams of pyridine and 100 ml. of toluene was stirred at steam bath temperature for 16 hours. It was then poured on ice and the product was taken up in benzene. The benzene solution was washed with dilute HCl and then with water. After drying the benzene solution, the solvent was removed and the oily residue was recrystallized from ether to give 3 grams of product, M.P. -173. The combined crops were recrystallized from a chloroform-ether mixture to give 6.4 grams of pure product, M.P. -6".
Analysis. Calcd. for C H CI N O: Cl, Found: Cl, 53.1, 53.3.
EXAMPLE VIII.--3 (BICYCLO(2.2.1)HEPT-5-EN-2 YLMETHYL) -1,1-DIMETHY-2-THIOUREA Found:
refluxed with stirring for 16 hours.
was collected and washed with methanol.
liquors.
EXAMPLE lX.l,3-BIS(1,2,3,4 TETRACHLORO-7- OXOBICYCLO(2.2.1)HEPT -EN-2-YLMETHYL)- Z-THIOUREA TETRAMETHYL DIACETAL A mixture of 21 grams of 1,2,3,4-tetrachloro-7-oxobicyclo(2.2.1)hept-S-en-Z-ylmethyl isothiocyanate dimethyl acetal and 800 ml. of 2% sodium hydroxide solution was After cooling the crude solid was collected and recrystallized from benzene- .hexane mixture to give 15' grams of product, M.P.
Analysis.--Calcd. for C H Cl N O4S: C, 36.9; H, 3.5; Cl, 41.6; S, 4.7. Found: C, 36.6; H, 3.8; Cl, 41.7, 41.8; S, 5.1.
EXAMPLE X.1-(5,6,7,8,9,9-HEXACHLORO-1,2,3,4,
4a,5,8,8a-OCTAHYDRO 1,4,5,8 DIMETHANO- NAPHTHALEN-Z-YL) -2-TH1OUREA A two-phase system consisting of 92 g. (1.0 mole) of bicyclo(2.2.l)hepta-2,5-diene, 76 g. of ammonium thiocyanate, and 75 ml. of water in a 500ml. flask was stirred on the steam bath while 100 g. of concentrated hydrochloric acid was added dropwise over a period of one hour. After cooling, the mixture was diluted with ether and the ether phase was separated, washed with water, and dried over anhydrous sodium sulfate. Distillation, and redistillation gave 92 g. (61% yield) of water-white product, B.P. 63.5-65' (0.1 mm.); n D 1.5602, bicyclo- (2.2.1 )hept-5-en-2-yl isothiocyanate.
Analysis.Calcd. for C H NS: N, 9.28; S, 21.2; mol. Found: N, 9.16; S, 20.9; mol. wt. 156.
A mixture of 13 g. (0.05 mole) of hexachlorocyclopentadiene and 7.6 g. (0.05 mole) of bicyclo(2.2.1)hept- 5-en-2-yl isothiocyanate was heated at 160-170 for 17 hours.
The black oily solid was taken up in 150 ml. of dioxane, charcoaled, and filtered. Two volumes of methanol and one of water were added. The precipitate The solid was recrystallized from'lOO ml. of heptane to give 9.0 g. of product, M.P. 186188.5. A second crop of 3 g., M.P. 176-182 was obtained by concentrating the mother These two crops were combined and recrystallized from ethyl acetate to give 8.0 g. (38% yield) of product as needles, M.P. 188l90.
Analysis.-Calcd. for C H NSCl Cl, 50.2; S, 7.55. Found: Cl, 50.0; S, 7.45.
A mixture of 10 g. of the Diels-Alder adduct of hexachlorocyclopentadiene and bicyclo(2.2.1)hept-S-en-Z-yl isothiocyanate, 100 ml. of dioxane and 100 ml. of concentrated ammonium hydroxide was heated on the steam bath with stirring for two hours. Seventy ml. of concentrated ammonium hydroxide and 40 ml. of dioxane were added and heating and stirring were continued. After two hours, another 30 m1. of concentrated ammonium hydroxide was added. After one hour and 20 minutes, the mixture was allowed to cool to room temperature and stand over the weekend. The solid was collected and recrystallized first from methanol and then from benzene to give product as pure white powder, M.P. 209 with decomposition.
Analysis.Calcd. for C H Cl N S: C, 35.4; H, 2.72;
Bean hosts Phaseolus vulgaris var. Pinto. Uromgges phaseoli var. typiea rus P. vulgarz's var. Black Valentine.
P. limensis var. Fordlrood 242.
Erysiphe pol /gem (powdery mildew) Colletotrichum lindemuthz'anum (anthracnose) Phytophthora phaseoli (downy mildew.
These four bean pathogens are of economical 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 diluent consisting of distilled water plus two co-solvents. Triton X-155, at 0.005% w. (2:1:1) -0.10% W. is used as a wetting agent for each concentrationof toxicant. All chemicals are initially tested at a single concentration of 1000 p.p.m. If acceptable disease' control is shown, chemicals are retested at 1000 p.p.m. and the next lowest dilution of 500 p.p.m. Chemicals continuing to show disease control are retested in this fashion until the minimum elfective 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. 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 th surface to be inoculated.
With the mist type spray and the diluent mixture which is applied, a drying interval of 1-2 hours is sufficient 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 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 screening.
Table 1.Foliage fungicide screen Disease control (min. effective conc. Phytotoxicity, max. Sar'e" p.p.m.) (cone. p.p.m.) Chemical compound P 1. E.p. U.a. 0.2. L b P. B.V.
3-(1,4,5,6,7,7-hexacl'ilorobieyolo(2.2.1)-hept-5en-2ylmethyl)-l,l-dimethyl- 2-thiourea 250 1, 000-2, 000 500 500 2, 000 500 1, 0002, 000 1,1-diallyl-3-(l, exachlorobicyclo(2.2.1)hept-5-en-2-y11nethyl) 2- thiourea 1, 000 1. 000 1, 000 1, 000 1, 000 1, 000 1, 000 3-(1,4,5,6,7,7-l1exachlorobioyclo(2.2.1)hept-5-en-2-ylmethyl)-1,l-bis(2-hydroxyethyD-lthiourea l, 000 1, 000 1, 000 500-1, 000 1, 000 1, 000 1, 000 3- (1,4,5,6,7,7-hexachlorobieyclo (2 2 1)hept- 2-ylmethyl) -1,1-dirnethy1- urea 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000 1, 000
* P.p.=Ph,1/tophthom phaseoli (downy mildew of lima bean); E.p.=Erysiphe polygom' (bean powdery mildew); U.a.= Uromyces phaseoli (bean rust);
C.l.= Collctotrichum Li'n'demuthianum (bean anthracnose).
b L=Lima bean; P=Pinto bean; BV=Black Valentine bean.
The effectiveness. of the present compounds as fungicides is further evidenced by the following tests.
To obtain expanded disease control data, chemicals were sprayed mainly as emulsible concentrates using concentrations of 0.24% w., 0.12% w., and 0.06% W. These correspond respectively to 2, 1 and 0.5 lbs. toxicant per 100 gallons of spray. Plants were sprayed to the run-oif stage, dried for 24 hours, and inoculated with test fungus spores. After inoculation, the plants wene held :for 2448 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 (Phytophthora infestans), celery blight (Septoria apiigraveolentis), bean mildew (Erysiphe polygoni), bean rust (Uromyces appendiculatus), and cucumber anthracnose (Collettotrichum langenarium').
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 follows:
Disease rating of untreated checkdisease rating of treatment or standard Disease rating of untreated cheek Foliage-fungicide activity index (F-F.A.I.)
Pereent control for treatment Percent control for standard 100 Where the disease control for the test chemical and standard was equivalent, the index value was unity, 100. Values above 100 indicated superiority. It will be understood however that compounds showing index values substantially below 100 may also be of considerable value.
In most cases comparisons were made at the 0.24% w. (2 lbs/100 gal.) concentration.
Readings for plant injury were obtained on tomatoes, beans, celery and cucumber. Both chronic toxicity (yellowing, distortion, etc.) and acute toxicity (tissue death) were recorded. The scale used was from -400. 0 represented no visible poisoning and 400 was the most severe manifestation.
The following table summarizes the results of these tests:
Table 2-F0liage FOLIAGE-FUNGIGIDE ACTIVITY INDEX The active compounds of the present invention may be used alone or in combination with other fungicidal, viriciadal, 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 hydrocarbon oils with a minimum viscosity of 10 Engler at C. can be present. Any conventional wetting agent which will not react with the toxicant for example, alkyl sulfate salts, alkyl aryl sulfonate salts, sulfosuccinate salts, ethers from 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 ureas and thiourea compounds 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 to 150 gallons per acre. If spraying is effected with smaller quantities of liquid as in low volume spraying, high concentrations of the active agents should be employed. If desired, a minor amount of 5 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 heptadecyl sulfates, sold commercially under the name of Teepol and polyethylene glycol ethers of alkyl phenols sold under the trade name of Triton X-100 and Triton X155. 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.
A further form in which the fungicidal compounds of the present invention may be applied consists of solutions of the active ingredient in suitable inert liquid or semisolid diluents, in which the active ingredient is present in molecularly dispersed form. The form in which the agents to be employed are applied to the objects treated fungicide test Chemical compound 1-(1,4,5,6,7,7-hexach1orobicyclo (2.2.1) -hept-5-en-2-y1methyl) -2thiourea.
3-(1%5,6,7,7-hexachlorobicyclo(2.2.1)-hept-5-en-2ylmetl1yl)-1,l-dimethyl- 2-t iourea.
1-(1%5,6,7,7-hexachlorobicycl0(2.2.1)hept-5-en-2-ylmethyl)-3-is0pr0pyl- 2-t iourea.
1,1i1dia1lyl-3- (1,4, 5,6,7,7-hexachlorobicyclo (2.2.1)hept-5-en-2-ylmethyl) -2- t iourea.
3- (1,4, 5,6,7,7-hexachlorobicyclo (2.2.1)hept-5-en-2-ylmethyl) -1, l-bis (Z-hydroxyethyl)-2-thiourea.
1,1-di-sec-butyl-3-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2-ylmethyl)-2-thiourea.
3-(1,4,5,6,7,7-hexachlorobicyclo(2.2.1)hept-5-en-2-ylrnethyl)-l,1-d imethylurea.
3-[bicycl0(2.2.1)hept-5-en-2-yl-methyll-1,l-dimethyl-Z-thiourea 1,3-bis(1,2,3,4-tetrachloro-7-oxobicyclo (2.2.1)hept-5-en-2-ylmethyl) -2- thiourea tetramethyl diacetal.
Activity index at 0.24% cone. (upper Phytotoxicity at 0.24% (upper figure and percent control at 0.06% figure) and 0.06% cone. (lower (lower figure) figure) respectively Com- Com- P.i.= S.a E4). U.a. 0.2. bined T b O B On bined index P.p.=Phytophthora phaseoli (downy mildew of lima bean); E.p.=Erysiphe polygom' (bean powdery mildew); U.a.= Urpmyces phaseoli (bean rust) C.Z.= Oolletotrichum Lindemuthianum (bean anthracnose). b T=tomato; C=ce1ery; B=bean; Ou=cucumber.
depends on the nature of the object and the purpose of the application.
Suitable inert solvents for the manufacture of liquid preparations should not be readily inflammable, as odorless as possible and Without any toxic eifect on humans and animals when properly used. Neither should they have a corrosive efiect on the components of the preparations or the material of the storage vessel. Examples of suitable solvents are high boiling oils, eg. 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 of dusts utilizing as the inert vehicle such materials as tricalcium phosphate, precipitated chalk, bentonite, kaolin, kieselgnhr, 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. 1 (1,4,5,6,7,7 heXachlorobicyclo'(2.2.1)hept en2-ylmethyl) -2-thiourea.
2. 1 -(1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept -5- en-Z-ylmethyl) -3 -isopropyl-2-thiourea.
3. 1,1 diallyl 3 (1,4,5,6,7,7 hexachlorobicyclo (2.2.1 )hept-S-en-Z-ylmethyl) -2-thiourea.
4. 3 (1,4,5,6,7,7 hexachlorobicyclo(2.2.1)hept 5- en-ylmethyl) -,1-bis(2-hydroxyethyl) -2-thiourea.
5. 1,1 di sec butyl 3-(1,4,5,6,7,7 hexachlorobicyclo (2.2. 1 -hept-5-en-2-yl methyl) -2-thiourea.
.6. A compound of the formula wherein "R is alkylene of from 1 to carbon atoms and R and R" are each alkenyl of from 1 to 10 carbon atoms.
8. A compound of the formula wherein R is alkylene of from 1 to 10 carbon atoms and R and R are each alkyl of from 1 to 10 carbon atoms.
10 9. A compound of the formula S R 01 01 R N(iN 5 01- -01 wherein R is alkylene of from 1 to 10 carbon atoms and R and R" are each alkenyl of from 1 to 10 carbon atoms. 10 10. A compound of the formula selected from the group consisting of X fi X R1TT-C X X' X H R X Z R X 1TI(iN Ear H X X i X/\/\R N C N X- -X H- -H X X NGN l 4 X X wherein X is halogen, X is selected from the group consisting of hydrogen, halogen and lower alkoxy, R is alkylone of from 1 to 10 carbon atoms, Z is selected-from the group consisting of oxygen and sulfur, and R and R" are individually selected from the group consisting of hydrogen, alkyl of from 1 to 10 carbon atoms, alkenyl of from 1 to 10 carbon atoms and hydroxyethyl.
References Cited in the file of this patent UNITED STATES PATENTS 2,015,045 Teichmann Sept. 17, 1935 2,061,243 Lubs et a1. Nov. 7, 1936 2,106,552 Jenkins et al. Jan. 25, 1938 2,621,211 \Behnisch Dec. 9, 1952 2,635,115 Bernstein Apr. 14, 1953 2,638,431 Harry May 12, 1953 2,642,373 Dazzi June 16, 1953 2,662,096 Huebner Dec. 8, 1953 2,688,039 Huebner et a1 Aug. 31, 1954 2,768,970 Schmidt Oct. 30, 1956 OTHER REFERENCES Grob et a1.: Helv. Chim. Acta, Vol. 90, pp. -140 0 (1957).

Claims (2)

1. 1 - (1,4,5,6,7,7 - HEXACHLOROBICYCLO(2.2.1)HEPT - 5EN-2-YLMETHYL)-2-THIOUREA.
10. A COMPOUND OF THE FORMULA SELECTED FROM THE GROUP CONSISTING OF
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US3203878A (en) * 1961-02-02 1965-08-31 Dehydag Deutsche Hydriewerke G Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product
US3304167A (en) * 1960-12-15 1967-02-14 Hercules Inc Norbornyl and substituted norbornyl ureas and thioureas, weed control compositions and methods
US3534141A (en) * 1965-07-22 1970-10-13 Bayer Ag Bicyclic-substituted ureas and their insect- and mite-repellent compositions and methods of use
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US3203878A (en) * 1961-02-02 1965-08-31 Dehydag Deutsche Hydriewerke G Acid metal electroplating bath containing an organic sulfonic acid-thioureadithiocarbamic acid reaction product
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