US2432256A - Fungicides - Google Patents

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US2432256A
US2432256A US2432256DA US2432256A US 2432256 A US2432256 A US 2432256A US 2432256D A US2432256D A US 2432256DA US 2432256 A US2432256 A US 2432256A
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nitrogen
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sulfenamide
thiocarbamo
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/86—Benzo [b] furans; Hydrogenated benzo [b] furans with an oxygen atom directly attached in position 7
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/907—Resistant against plant or animal attack

Definitions

  • This invention relates to new and useful immovements, in fungicides.
  • the invention further relates to methods of treating plants, and to methods of protecting organic material subject to attack by fungi, as the immunizing or seed, and the mildewproofing of fabrics and other material.
  • thiocarbamosulfenamides in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen-and the nitrogen of the Application August in. 1945 Serial No. 613,950 r a sulienamide group has attached to it a hydrogen atom and an acyl group, are effective fungicides.
  • the structure or the compounds may be represented by the general formula where R and R each represent an acylic, alicyclic, heterocyclic, aromatic or aralkyl group or where R and R in combination represent allrylene (e. g. pentamethylene) or an alkylene containing a hetero O, N or 8 atom in the chain (e. g.
  • the compounds may be made by reacting the selected thiocarbamo sulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group. is a primary-amino nitrogen with the appropriate ketenc to give the desired acyl substituent on the sulfenamide; nitrogen.
  • the preparation 01 the thiocarbamosulfenamides in which the nitro: gen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group is described in the application of Philip T. Paul, Serial N0. 600,209, filed June 18; i
  • thiocarbamosulfensulfenamide (U. 8. Patent No. 2,318,482) in 200 cc. dry ether, ketene (from 500 cc. acetone) is introduced over a 6 hour period. The temperature of reaction is held at 20 C. and additional ether is added to keep the volume constant. At the end of the reaction the ether is evaporated and the residual oil crystallizes on, standing. Recrystailized from a benzene-ligroin mixture. Melting point 67 0. Yield 19.6 g. The ketene was prepared by the pyrolysis of acetone in accordance with the usual procedure.
  • N,N-diphenyl N- acetyl thio'carbamo sulfenamide M. P. 167 0.: and from N-methyl N-phenyl thiocarbamo sulfenamide (M. P. 86-87 C.), N-methyl N-phenyl N'-acetyl thiocarbamo sulfenamide M. P, 127- 128 C. is prepared.
  • the compounds of the present invention may be used as seed protectants and to protect plants. which term includes plant parts, and soil. from microorganisms harmful to seeds and plants. They may also be applied to prevent or retard fungus growth and the formation of, for example, mildew on organic material such as cellulosic material, rope, wood, fur, hair, feathers, cotton, wool, and leather. They may be applied as a dust. undiluted or mixed with a powdered solid carrier, such as clay or talc, or as a liquid or spray in a liquid carrier, as in solution in a suitable solvent, or suspended in a suitable nonsolvent, for example, water.
  • the composition contains a dispersing agent for the chemicals.
  • the compounds of the present invention are preferably applied to the seeds as by tumbling with the straight chemical, or with the chemical admixed with a powdered solid carrier.
  • foliage treatment the compounds of the present invention are preferably applied to the plant parts as by spraying with an aqueous suspension of the chemical containing a dispersing agent. Similar aqueous suspensions are preferred for the mildewproofing of textiles, such as cotton fabrics.
  • the chemicals may be applied'as to foliage by the aerosol method. Solutions for the aerosol treatment may be prepared by dissolving the chemical directly in the highly volatile liquid carrier or first dissolving the chemical in a less volatile solvent and then admixing such solution with the highly'volatile liquid aerosol carrier.
  • the compounds may be used admixed with carriers that are active of themselves, for example, other fungicides, or
  • a fungicidal composition comprising as an active ingredient a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of bacterlcides, insecticides, insectifuges, fertilizers,
  • Barley seeds known to be infected with the destructive root rotting fungus Helminthosporium sativum, were tumbled with 1% by weight of the chemical of the invention under evaluation.
  • a fungicidal composition comprising an aqueous suspension of a thiocarbamosulfenamide in which the nitrogen of the thi'ocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
  • a fungicidal composition comprising an aqueous suspension of a -thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group, said aqueous suspension containing a dispersing agent.
  • a fungicidal composition comprising an aqueous suspension of N,N-dimethyl N'-acetyl thiocarbamo-sulfenamide.
  • a fungicidal composition comprising an aqueous suspension of N.N-dimethy1 N-acetyi thiocarbamo-sulfenamide containing a dispersing agent.
  • the method of protecting organic material subject to attack by microorganisms which comprises applying to said material a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
  • the method of controlling fungi on growing plants which comprises treating the foliage of the plants with a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and arra'cylgroup.
  • the method of controlling fungi on growing plants which comprises treating the foliage of the plants with N,N-dimethy1 N-acetyl thiocarbamosuifenamide.
  • the method of controlling fungi on growing plants which comprises spraying the foliage of the plants with a thiocarbamosulfcnamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it ahydrogen atom and an acyl group.
  • the method of controlling fungi on growing plants which comprises spraying the foliage of the plants with N,N-dimethyl N-acetyl thiocarbamosulfenamlde.
  • the method of protecting seeds, plants and soil subject to attack or infestation by fungi which comprises treating said material with 9. mmcarbamosulfenamide in which the nitrogen of the thiocarbamo group is a. tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
  • the method of immunizing seed which comprises treating said seed with a thiocarbamosulfenarnide in which the nitrogen of the thincarbamo group'ls a tertiary-amino nitrogen and the nitrogen-of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
  • the method of immunizing seed which comprises treating said seed with N,N-dimetlrvl N'- acetyl thiocarbamosulfenamide.
  • the method of controlling fungi on living organisms which comprises treating said .organ- 25 isms with a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
  • the method of controlling fungi on living which comprises treating said organisms with N,N-dimethyl N'-acetyl thiocarbamosulfenamide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Patented Dec; 9, 1947 runcrcmas I, Joseph B. Shaptason, Woodbridge, (Jo nn assignor I to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing.
19 Claims. 1
This invention relates to new and useful immovements, in fungicides. The invention further relates to methods of treating plants, and to methods of protecting organic material subject to attack by fungi, as the immunizing or seed, and the mildewproofing of fabrics and other material.
I have found that thiocarbamosulfenamides in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen-and the nitrogen of the Application August in. 1945 Serial No. 613,950 r a sulienamide group has attached to it a hydrogen atom and an acyl group, are effective fungicides. The structure or the compounds may be represented by the general formula where R and R each represent an acylic, alicyclic, heterocyclic, aromatic or aralkyl group or where R and R in combination represent allrylene (e. g. pentamethylene) or an alkylene containing a hetero O, N or 8 atom in the chain (e. g. oxydiethylene, iminodiethylene, or thiodiethylene), and where X represents an alkyl group, The compounds may be made by reacting the selected thiocarbamo sulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group. is a primary-amino nitrogen with the appropriate ketenc to give the desired acyl substituent on the sulfenamide; nitrogen.
The preferred acyl substituent on the suifenamide nitrogen is the acetyl group formed by reaction of the thiocarbamosulfenamide with the simple ketene CH2=C=O. The preparation 01 the thiocarbamosulfenamides in which the nitro: gen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group is described in the application of Philip T. Paul, Serial N0. 600,209, filed June 18; i
1945. There is considerable confusion in the technical literature as to the "nomenclature of compounds containing the --S-N linkage. The
nomenclature followed in this specification considers the parent compound which would have the formula nm-c-s-mn i! nm-c-s-on The compound would thus be thiocarbamosulfenamide. There are two amino nitrogens in this formula, one belonging to the thiocarbamo group and the other to the sulfenamide group -S -NI-Ia. To differentiate these nitrogens, the thiocarbamo nitrogen is labeled "N" and the sulfenamide nitrogen is labeled N' in the nomenclature of the compounds. Thus, the thiocarbamo (N) nitrogen is a tertiary amino nitrogen in the compounds of the present invention, and the sulfenamide (N') nitrogen is a secondary nitrogen to which is attached an acyl group.
Examples of the above chemicalsthat may be used as fungicides according to the present invention are:
thiocarbamosulfensulfenamide (U. 8. Patent No. 2,318,482) in 200 cc. dry ether, ketene (from 500 cc. acetone) is introduced over a 6 hour period. The temperature of reaction is held at 20 C. and additional ether is added to keep the volume constant. At the end of the reaction the ether is evaporated and the residual oil crystallizes on, standing. Recrystailized from a benzene-ligroin mixture. Melting point 67 0. Yield 19.6 g. The ketene was prepared by the pyrolysis of acetone in accordance with the usual procedure. The ketene CHa=C=O may also be prepared by the action 3 of zinc on bromoacetyl bromide or on chloracetyl chloride in known manner. This latter method is the one used in preparing the higherketenesas by the action of zinc on the appropriate a halo-" acyl halide.
Similarly, when N,N-dimethyl thiocarbamo sulfenamide is reacted with the ketene in the above procedure, there is obtained N,N-dimethyi N'-acetyl thiocarbamo sulfenamide, M. P. 135' 0.; using morpholyl thiocarbamo sulfenamide for reaction with the same ketene in the above procedures results in N-oxydiethylene N-acetyi thio= carbamo sulfenamide, M. P. 163-184" 0.; using N,N-diphenyl thiocarbamo sulfenamide (M. P. 149 0.), there is obtained N,N-diphenyl N- acetyl thio'carbamo sulfenamide, M. P. 167 0.: and from N-methyl N-phenyl thiocarbamo sulfenamide (M. P. 86-87 C.), N-methyl N-phenyl N'-acetyl thiocarbamo sulfenamide M. P, 127- 128 C. is prepared. 1
The compounds of the present invention may be used as seed protectants and to protect plants. which term includes plant parts, and soil. from microorganisms harmful to seeds and plants. They mayalso be applied to prevent or retard fungus growth and the formation of, for example, mildew on organic material such as cellulosic material, rope, wood, fur, hair, feathers, cotton, wool, and leather. They may be applied as a dust. undiluted or mixed with a powdered solid carrier, such as clay or talc, or as a liquid or spray in a liquid carrier, as in solution in a suitable solvent, or suspended in a suitable nonsolvent, for example, water. Preferably when applied in aqueous suspension, the composition contains a dispersing agent for the chemicals. In seed treatment, the compounds of the present invention are preferably applied to the seeds as by tumbling with the straight chemical, or with the chemical admixed with a powdered solid carrier. In foliage treatment, the compounds of the present invention are preferably applied to the plant parts as by spraying with an aqueous suspension of the chemical containing a dispersing agent. Similar aqueous suspensions are preferred for the mildewproofing of textiles, such as cotton fabrics. The chemicals may be applied'as to foliage by the aerosol method. Solutions for the aerosol treatment may be prepared by dissolving the chemical directly in the highly volatile liquid carrier or first dissolving the chemical in a less volatile solvent and then admixing such solution with the highly'volatile liquid aerosol carrier. The compounds may be used admixed with carriers that are active of themselves, for example, other fungicides, or
infection (0% control). fection of seeds treated with chemicals of the 4 of dark colored Helminthosporium sporulating on the surface of the seeds and in a narrow zone on the filter paper around the seeds. The seeds under test were scored as to percent control. In every run where the seeds were not treated with a chemical there was found one hundred percent The control of the ininvention are shown in the table below:
Having thus described my invention, what I icBlaim and desire to protect by Letters Patent 1. A fungicidal composition comprising as an active ingredient a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of bacterlcides, insecticides, insectifuges, fertilizers,
hormones, buffering or softening agents. The following illustrates the invention: Barley seeds, known to be infected with the destructive root rotting fungus Helminthosporium sativum, were tumbled with 1% by weight of the chemical of the invention under evaluation.
Twenty-five of the seeds thus treated with one of the chemicals. and twenty-five of the infected seeds not treated with any chemical, were placed on pads of filter paper in separate petri dishes the sulfenamide group has attached to it a hydrogen atom and an acyl group. and a carrier therefor selected from the group consisting of powdered solid carriers, and water containing a dispersing agent.
2. A fungicidal composition comprising an aqueous suspension of a thiocarbamosulfenamide in which the nitrogen of the thi'ocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
' 3. A fungicidal composition comprising an aqueous suspension of a -thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group, said aqueous suspension containing a dispersing agent.
4. A fungicidal composition comprising an aqueous suspension of N,N-dimethyl N'-acetyl thiocarbamo-sulfenamide.
5. A fungicidal composition comprising an aqueous suspension of N.N-dimethy1 N-acetyi thiocarbamo-sulfenamide containing a dispersing agent.
6. The method of protecting organic material subject to attack by microorganisms which comprises applying to said material a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
7. The method of controlling fungi on growing plants which comprises treating the foliage of the plants with a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and arra'cylgroup.
8. The method of controlling fungi on growing plants which comprises treating the foliage of the plants with N,N-dimethy1 N-acetyl thiocarbamosuifenamide.
9. The method of controlling fungi on growing plants which comprises spraying the foliage of the plants with a thiocarbamosulfcnamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it ahydrogen atom and an acyl group.
10. The method of controlling fungi on growing plants which comprises spraying the foliage of the plants with N,N-dimethyl N-acetyl thiocarbamosulfenamlde.
11. The method of protecting seeds, plants and soil subject to attack or infestation by fungi which comprises treating said material with 9. mmcarbamosulfenamide in which the nitrogen of the thiocarbamo group is a. tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
12. The method of immunizing seed which comprises treating said seed with a thiocarbamosulfenarnide in which the nitrogen of the thincarbamo group'ls a tertiary-amino nitrogen and the nitrogen-of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
13. The method of immunizing seed which comprises treating said seed with N,N-dimetlrvl N'- acetyl thiocarbamosulfenamide.
14. The method of controlling fungi on living organisms which comprises treating said .organ- 25 isms with a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide group has attached to it a hydrogen atom and an acyl group.
15. The method of controlling fungi on living which comprises treating said organisms with N,N-dimethyl N'-acetyl thiocarbamosulfenamide.
16. The method 'of destroying fungus which comprises subjecting said fungus to the action of a thiocarbamosulfenamide in which the nitrogen of the thiocarbamo group is a tertiary-amino nitrogen and the nitrogen of the sulfenamide REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,972,981 Tisdale et al. Sept. 11. 1934 2,325,720
Urbschat et a1. Aug. 3, 1943
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441032A (en) * 1945-06-18 1948-05-04 Us Rubber Co Acyl thiocarbamo sulfenamides as new chemicals
US2640834A (en) * 1947-04-18 1953-06-02 Us Rubber Co Dithiocarbamates and derivatives thereof
US3158537A (en) * 1959-08-28 1964-11-24 Phillips Petroleum Co Repelling birds
US4006251A (en) * 1973-07-09 1977-02-01 The B. F. Goodrich Company Bactericidal and fungicidal composition containing thiocarbanyl sulfenamides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1972961A (en) * 1931-05-26 1934-09-11 Du Pont Disinfectant
US2325720A (en) * 1939-03-16 1943-08-03 Winthrop Chem Co Inc Parasiticide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1972961A (en) * 1931-05-26 1934-09-11 Du Pont Disinfectant
US2325720A (en) * 1939-03-16 1943-08-03 Winthrop Chem Co Inc Parasiticide

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2441032A (en) * 1945-06-18 1948-05-04 Us Rubber Co Acyl thiocarbamo sulfenamides as new chemicals
US2640834A (en) * 1947-04-18 1953-06-02 Us Rubber Co Dithiocarbamates and derivatives thereof
US3158537A (en) * 1959-08-28 1964-11-24 Phillips Petroleum Co Repelling birds
US4006251A (en) * 1973-07-09 1977-02-01 The B. F. Goodrich Company Bactericidal and fungicidal composition containing thiocarbanyl sulfenamides

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