US3468905A - N-(1-halo-1-nitroalkylthio)dicarboximides - Google Patents

N-(1-halo-1-nitroalkylthio)dicarboximides Download PDF

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Publication number
US3468905A
US3468905A US485619A US3468905DA US3468905A US 3468905 A US3468905 A US 3468905A US 485619 A US485619 A US 485619A US 3468905D A US3468905D A US 3468905DA US 3468905 A US3468905 A US 3468905A
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chloro
compounds
halo
nitropropylthio
nitroethylthio
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US485619A
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Gustave K Kohn
Joseph G E Fenyes
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Chevron USA Inc
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Chevron Research and Technology Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • 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
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/80—Two oxygen atoms, e.g. hydantoin with hetero atoms or acyl radicals directly attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/96—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having three double bonds between ring members or between ring members and non-ring members

Definitions

  • Typical dicarboximides are N-(l-chloro-l-nitroethylthio) phthalimide, N-(l-halo-lnitropropylthio) 5,5 dimethyl hydantoin, N,N-di-(lchloro-l-nitropropylthio) uracil and 1,1-bis-(chloro-1-nitropropylthio) parabanic acid. These carboximides are fungicidal.
  • A- is one of the following groups:
  • R is hydrogen or lower alkyl of from 1 to 6 carbons
  • R is hydrogen or lower alkyl, i.e., from 1 to 6 carbons
  • B is a l-halo-l-nitroalkyl group in which the halogen is of atomic number 17 to 35 and the alkyl is of from 2 to 6 carbons, i.e., ethyl through hcxyl.
  • X is halogen of atomic number 17 to 35
  • R is alkyl of from 1 to 5 carbons
  • the LZ-cyclohexylene ring has from 0 to 3 sites of olefinic unsaturation, i.e., 1,2- phenylene, 1,2-dihydropheny1ene, 1,2-tetrahydrophenylene and 1,2-hexahydrophenylene.
  • the ring may be considered as phthalimide and derivatives thereof.
  • the ring could be phthalimide, dihydrophthalimide, tetrahydrophthalimide and hexahydrophthalimide.
  • the ring may be unsubstituted or singly substituted with a chloro, bromo, nitro or alkyl group such as methyl, ethyl, butyl, amyl, etc.
  • the dihydro derivatives that is, dihydrophthalimide
  • dihydrophthalimide may be 1,3-, 1,4-, 2,4-, 3,5-, etc.
  • the tetrahydro derivative may be 1-, 2-, 3-, or 4.
  • Preferred compounds are phthalimide and A -tetrahydrophthalimide.
  • hydantoin compounds of this invention may be more rigorously represented by the formula wherein X is halogen of atomic number 17 to 35, i.e., chlorine or bromine, R is alkyl of from 1 to 5 carbons and R is hydrogen or lower alkyl. Included among the lower alkyl groups are, methyl, ethyl, propyl, butyl, amyl and hexyl. Preferred compounds are the 3-(1-halo-1-nitroalkyl) hydantoins.
  • Illustrative examples of some of the hydantoin compounds included in this invention are: 3-(1-chloro-1-nitroethylthio) hydantoin, 3-(l-bromo-l-nitrobutylthio) hydantoin, 3-(l-chloro-l-nitrohexylthio) hydantoin, 3-(1- chloro l-nitropropylthio)-5,5-dimethylhydantoin, 3-(1- bromo-l-nitroamylthio -5-methylhydantoin, 3-(l-ch1oro- 1 nitroethylthio)-5-ethylhydantoin, 3-(1-chloro-1-nitrobutylthio) 5 butylhydantoin, 3-(1-bromo-lnitroethylthio)5,5-dipropylhydantoin, etc.
  • the pyrimidine compounds of this invention may be further defined by the structure R (E-C N02 I HO N-S-G-R N-G N02 I I] l 0 wherein X is halogen of atomic number 17 to 35, R is alkyl' of from 1 to 6 carbons and R is hydrogen or methyl.
  • R is alkyl' of from 1 to 6 carbons
  • R is hydrogen or methyl.
  • di-( l-halo-l-nitroalkylthio) substituted parabanic acids of this invention are 1,3-bis-(1-chloro-1- nitroethylthio) parahanic acid, 1,3-bis-(1-bromo-l-nitrobutylthio) parabanic acid, l,3-bis-(l-chloro-l-nitrohexylthio) parabanic acid, etc.
  • the preparation of the unique N-(l-halo-l-nitroalkyl) dicar-boximides of this invention may be carried out by reacting an alkali metal salt of the corresponding imide with a l-halo-l-nitroalkylsulfenyl halide.
  • the imide may be contained in a suitable inert medium, such as an aromatic solvent, e.g., benzene, toluene, etc., an alcohol, e.g., methanol, ethanol, etc. or water.
  • the imide may be used directly in the form of its alkali metal salt or the salt may be formed in situ.
  • the solution or suspension of the alkali metal salt of the imide is vigorously stirred, preferably at low temperature while the sulfenyl halide is added.
  • the sulfenyl halide may be contained in a suitable inert solvent, such as petroleum ether or mixed hexanes, if desired. After a sufiicient reaction period the product is isolated by fitlration or by stripping off the solvent. The product then may, if desired, be recrystallized from a suitable solvent, such as methanol or an aromatic solvent.
  • the l-halo-l-nitroalkylsulfenyl halides used in the preparation of the compounds of this invention may he synthesized by reacting an alkali or alkaline earth metal salt of a primary nitroalkane with sulfur monochloride in the presence of an anhydrous, nonhydroxylic inert medium, such as ether, to form a bis-(l-nitroalkyl) disulfide and cleaving the disulfide with halogen, i.e., chlorine or bromine.
  • halogen i.e., chlorine or bromine
  • EXAMPLE H A 5.0 gm.-portion of the sodium "salt of cis-A -tetrahydrophthalimide was charged to a vessel. To this mixture was added 5.45 gm. l-chloro-l-nitropropylsulfenyl chloride in ether. The contents were stirred overnight and then filtered. The solids were washed with water and hexane and then dried. The product, N-(l-chloro-l-nitropropylthio)-cis-A -tetrahydrophthalimide, was observed as a. solid which melted at 104-405 (3. Its anlysis was: percent Cl: theory-11.64, foundl1.68; percent S: theory 10.52, foundl0.30.
  • EXAMPLE III A 3.0 gm.-portion of the monopotassium salt of hydantoin in ether was charged to a vessel. To this suspension 3.75 gm. l-chloro-l-nitropropylsulfenyl chloride were added. The contents were stirred for 1 hour and allowed to stand for 3 days. The mixture was filtered and the solids were slurried with water. The Water slurry was filtered and the solids were dried leaving 3.2 gms. 3-(1-chloro-l-nitropropylthio) hydantoin. It was observed as a white solid which melted at l57l 60 C. with decomposition. Its analysis was: percent Cl: theory-14.0, found 14.33; percent S: theory-12.65, foundl2.20.
  • EXAMPLE VI A 5 .0 gm.-portion of the dipotassium salt of parabanic acid dissolved in ether was charged to a vessel. To this mixture was added 10.0 gm. l-chloro-l-nitropropylsulfenyl chloride. The contents were stirred for 1 hour and allowed to stand for 3 days. The solids were filtered off and the ether was stripped from the filtrate. The stripped filtrate was further distilled to 60 C. at 1.0 mm. Hg to give 4 gms. 1,3-di-(1-chloro-l-nitropropylthio) parabanic acid. This product was observed to be a viscous orange oil.
  • a number of the invention compounds were evaluated for fungicidal elfectiveness by means of the mycelial drop test. This test is designed to measure the fungitoxic activity of fungicidal chemicals in terms of their degree of inhibition upon mycelial growth. Each compound to be tested was dissolved in acetone in dilutions as indicated in Table II. Paper discs previously inoculated by impregnation with equal amounts of particular fungus mycelium placed on potato dextrose agar medium were treated by applying a precise and equal volume of each of these fungicidal solutions to their center.
  • Each compound to be tested was dissolved in acetone to a concentration of 10 ppm. These solution were then pipetted into the wells of depression slides and allowed to dry. The wells were filled with a spore suspension of the specified test organism and incubated in a moist chamber overnight. A group of 100 spores was examined and the number of spores germinated and not germinated Was effected by the fungitoxic chemical. The results appear in Table IV.
  • N,N-di-(1-ch1orol-nitropropylthi0) uracil were tested for fungicidal activity in vivo.
  • the chemicals were tested for the control of bean rust.
  • thre replicate pinto bean plants growing in a standard University of California soil mix, in the 3-triplicate state and approximately 5 inches tall were sprayed at 15 psi. with an acetone solution of each of the compounds to be tested at a concentration of 500 ppm.
  • These suspension made uniform by means of an inert wetting agent and suitable filler.
  • the plants were dried at ambient greenhouse temperatures and then inoculated with a spray of approximately 30,000 urediospores per mil.
  • the solid carriers may be in the form of a dust, or used in conjunction with a suitable wetting agent to form a wettable powder.
  • the fungi-toxic compounds of the invention may also be formulated with other solvent, dispersing agents, or emulsifying agents. Further, these compounds may not only be applied alone or in mixtures with other compounds of the disclosed class, but may also be used in combination with other active toxicants in the formulation of fungicidal compositions.
  • the compounds may be applied to any environmental area which is a host to fungus or susceptible to fungus attack.
  • the fungicidal compositions may be sprayed or otherwise applied directly to a plant or other host, may be applied to the plant seed, sprayed upon the soil or other plant environment, or used in similar ways so as to effect the control of fungus and fungus diseases.
  • N-(1-ha1o-1-nitroa1ky1thio)phthalimide whereinthe if 5 alkyl group is of 2 to 6 carbon atoms. 0 A/ ⁇ N-SB r References Cited 0 UNITED STATES PATENTS (i V 10 3,036,088 5/1962 Harris 260326 NICHOLAS s.
  • RIZZO Primary Eitaminer wherein A is a 1,2-cyclohexy1ene ring having 0 to 3 sites of olefinic unsaturation substituted with 0 to 1 chloro, NARCAVAGE AsslstamExammer bromo, nitro or lower alkyl and B is a l-halo-l-nitroalkyl Us CL group in which the halogen is of atomic number 17 to 35 15 and the alkyl is of from 2 to 6 'carbon atoms.” 260-260, 309-5; 424 251"263

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)
US485619A 1965-09-07 1965-09-07 N-(1-halo-1-nitroalkylthio)dicarboximides Expired - Lifetime US3468905A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US48561365A 1965-09-07 1965-09-07
US48561965A 1965-09-07 1965-09-07
US81758868A 1968-12-06 1968-12-06

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US485619A Expired - Lifetime US3468905A (en) 1965-09-07 1965-09-07 N-(1-halo-1-nitroalkylthio)dicarboximides
US485613A Expired - Lifetime US3429931A (en) 1965-09-07 1965-09-07 1-halo-1-nitro disulfides
US817588*A Expired - Lifetime US3511838A (en) 1965-09-07 1968-12-06 1,5-di-(1-halo-1-nitroalkylthio)-2,6-dioxy pyrimidines

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US817588*A Expired - Lifetime US3511838A (en) 1965-09-07 1968-12-06 1,5-di-(1-halo-1-nitroalkylthio)-2,6-dioxy pyrimidines

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CH (2) CH493493A (enrdf_load_html_response)
DE (1) DE1568329A1 (enrdf_load_html_response)
GB (2) GB1102674A (enrdf_load_html_response)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3818031A (en) * 1971-03-26 1974-06-18 Ciba Geigy Corp Imidazolidinetrionecarboxylic acid derivatives
US4281139A (en) * 1978-10-02 1981-07-28 Monsanto Company Alkylthioimidazolidinetriones

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322506A (en) * 1989-07-31 1994-06-21 C. R. Bard, Inc. Irrigation system with high flow bypass for use with endoscopic procedure

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3036088A (en) * 1959-10-08 1962-05-22 Du Pont N-(fluoroalkylthio)-imides

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* Cited by examiner, † Cited by third party
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US2527293A (en) * 1950-10-24 Thomas f

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3036088A (en) * 1959-10-08 1962-05-22 Du Pont N-(fluoroalkylthio)-imides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3818031A (en) * 1971-03-26 1974-06-18 Ciba Geigy Corp Imidazolidinetrionecarboxylic acid derivatives
US4281139A (en) * 1978-10-02 1981-07-28 Monsanto Company Alkylthioimidazolidinetriones

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GB1102674A (en) 1968-02-07
US3511838A (en) 1970-05-12
DE1568329A1 (de) 1970-02-12
NL6612600A (enrdf_load_html_response) 1967-03-08
CH478118A (de) 1969-09-15
GB1094250A (en) 1967-12-06
US3429931A (en) 1969-02-25

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