US3376335A - Carbamic acid esters - Google Patents

Carbamic acid esters Download PDF

Info

Publication number
US3376335A
US3376335A US423596A US42359665A US3376335A US 3376335 A US3376335 A US 3376335A US 423596 A US423596 A US 423596A US 42359665 A US42359665 A US 42359665A US 3376335 A US3376335 A US 3376335A
Authority
US
United States
Prior art keywords
acid esters
carbamic acid
carbon atoms
chloro
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US423596A
Other languages
English (en)
Inventor
Goliasch Karl
Pelster Heinrich
Muhlbauer Ernst
Heiss Rudolf
Scheinpflug Hans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Application granted granted Critical
Publication of US3376335A publication Critical patent/US3376335A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms

Definitions

  • the present invention relates to new ca-rbamic acid esters which have fungitoxic properties, and to a process for the production thereof.
  • One object of the present invention consists in disclosing new carbamic acid esters which have fungitoxic properties. Another object consists in providing several processes for the production of these new carbamic acid esters. It is also an object of the invention to provide new agents for combating phytopathogenic fungi. Further objects can be seen from the following description and the examples.
  • R stands for hydrogen, alkyl, alkenyl, alkox'y, dialkylamino, dialkenylamino, alkylmercapto, alkenylmercapto, halogen and/or nitro,
  • A stands for alkylene with 1 to carbon atoms
  • R stands for chlorine, alkoxy, alkylmercapto, cycloalkoxy or a 'heterocyclic radical
  • n stands for a number from 1 to 5
  • R preferably stands for hydrogen, alkyl, alkenyl, alkoxy, dialkylamino and alkylmercapto, each with 1 to 4 carbon atoms in the alkyl radicals, for dialkenylamino and alkenylmercapto, each with 2 to 4 carbon atoms in the alkenyl radicals, as well as for chlorine, bromine and nitro.
  • R preferably stands for chlorine, alkoxy with 1 to 10 carbon atoms, alkylmercapto with 1 to 4 carbon atoms, cycloalkoxy with 5 to 6' ring atoms and heterocyclic radicals with 5 to 6 ring atoms which preferably contain oxygen, nitrogen or sulphur.
  • phenols which can be used according to the invention, there may be mentioned: phenol, 4-. methyl-, 3-methyl-4-chloro-, 2-allyl-, 3-methoxy-, 2- ChlOI'Or, 3-chloro-, 4-chloro-, 2,4-dichloro 2,4-dichloro-, 6-nitro-, 2,4,6-tri'chloro-, pentachloro, 2-chlo1ro4-nitro-, 3-methyl-4-dimethylamino-, 2-diallylamino-, 4-methylmercapto 3amethyl-4-methylmercapto-, 3,5-dimethyl-4- methylmercapto-, 2-isopropyl-4-methylmercapto-, 3-lmethyl-4-allylmercapto-phenol.
  • isocyanates or amines to be used according to the invention are l-chloroethyl-2-, l-chlorobutoxypropyl-, 1-chloro-n-'hexyl-6-, methoxymethyl-, methoxypropyl-, ethoxypropyl-, sec. buto-xypropyl-, cyclohexoxypropyl-, -isopropyloxypropyl-, 2-ethylhexoXypropyl-, methylmercaptoethyl-, ethylmercaptopropyl-isocyanate or -amine.
  • the process (a) is expediently carried out in the presence of inert organic solvents within a temperature range between -50 and +150 C., and bases, preferably tertiary amines such as triethylamine and pyridine, are optionally added as catalysts.
  • the first step of process (b) is expediently carried out at pH values below 6 in aqueous or alcoholic solvents Within a temperature range between about 50 and +150 C.
  • the second step of this process is expediently performed in the presence of inert organic solvents within a temperature range of about 20 to C.
  • the first step of process (c) is expediently carried out at pH values between 6 and 9 in the presence of inert organic solvents, with the addition of an inorganic agent splitting off acid, such as a sodium hydroxide solution, at temperatures between and 100 C.
  • the second step of this process is expediently performed in the presence of inert organic solvents at temperatures between 50 and 150 C.
  • Suitable inert organic solvents are, for example, hydrocarbons, such as benzine and benzene; chlorinated hydrocarbons, such as methylene chloride and dichlorobenzene; ethers, such as diethyl ether and dioxan; ketones, such as acetone and cyclohexanone, as well as acetonitrile and dimethyl formamide.
  • hydrocarbons such as benzine and benzene
  • chlorinated hydrocarbons such as methylene chloride and dichlorobenzene
  • ethers such as diethyl ether and dioxan
  • ketones such as acetone and cyclohexanone, as well as acetonitrile and dimethyl formamide.
  • reaction components are used in about equimolar amounts, but the phosgene can also be employed in excess.
  • the reaction is carried out in the, usual manner. Working up is performed by known methods;
  • the compounds according to the invention have a strong fungitoxic effect and are distinguished by a broad spectrum of activity. Due to their low toxicity towards warm-blooded animals, they are suitable for combating undesirable fungus growth. Their good compatibility with higher plants enables them to be used as plant protective agents against fungus diseases.
  • the compounds according to the invention have proved especially satisfactory for controlling rice diseases. They have an excellent protective effect when combating Piricularia oryzae in rice.
  • the substances according to the invention also have an especially good activity against a number of other fungi, such as species of Mycosphaerella, Cercospora, Corticium, Alternaria, Septoria, and against Botrytis cinerea.
  • the compounds according to the invention also have a fungitoxic acivity against fungi which attack the plant from the soil and sometimes cause tracheomycoses, such as Phz'alophora cinerescens, Verticillium alboatrum, Fusarizzm oxysp.f.cubense, Fusarium oxysp.f.dianthi.
  • fungitoxic acivity against fungi which attack the plant from the soil and sometimes cause tracheomycoses, such as Phz'alophora cinerescens, Verticillium alboatrum, Fusarizzm oxysp.f.cubense, Fusarium oxysp.f.dianthi.
  • the compounds according to the invention as leaf fungicides, have mainly a protective effect, a mixture with curative agents is advantageous.
  • Organic mercury compounds such as phenyl-mercury acetate, and also antibiotics, such as Plasticidin S, are suitable for this purpose.
  • a substantial reduction of the mercury content can be achieved in the mixed preparation.
  • the disadvantages occurring when organic mercury compounds are used by themselves, such as the toxicity towards warm-blooded animals, can thus be reduced.
  • preparations of protective and of curative effect as in the mixture mentioned above, an increased effectiveness can be attained.
  • the compounds according to the invention can be transformed into the usual formulations, such as emulsifiable concentrates, spray powders, pastes, soluble powders, dusts and granulates. These are prepared in known manner, for example by extending the active ingredients with solvents and/ or carriers, if desired with the use of emulsifiers and/or dispersing agents (cf. Agricultural Chemicals, March 1960, pages 35-38).
  • Suitable auxiliaries for this purpose are mainly solvents, such as aromatics (e.g. xylene, benzene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g.
  • emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylenefatty acid esters, polyoxyethylene-fatty alcohol ethers, alkylsulphonates and arylsulphonates), and dispersing agents, such as lignin, sul.
  • the compounds according to the invention can be pres ent in the formulations in admixture with other known active ingredients.
  • the formulations generally contain between 0.1 and 95, preferably between 0.5 and 90, percent by weight of active compound.
  • the compounds to be used or their preparations are applied in usual manner, for example by spraying, dusting, sprinkling or atomizing.
  • the active ingredient can be used in concentrations between 0.2 and 0.005%, dependent upon the intended application. In special cases, however, it is possible to exceed or to remain below this range of concentration.
  • Solvent 1 part by weight of acetone Dispersing agent: 0.05 part by weight sodium oleate
  • Other additives 0.2 part by weight gelatin
  • Water 98.75 parts by weight H O
  • the amount of active compound required for the desired concentration of the active compound in the spray liquid is mixed with the stated amount of solvent, and the concentrate obtained is diluted with the stated amount of water containing the stated additives.
  • Example B Piricularia test/solid preparation of active compound Solvent: 10 parts by weight acetone Dust Base: 100 parts by weight 0.5% Mg. stearate 4.0% silicic acid 0.5% Mg. stearate Piricularz'a, oryzae and placed in a room at 2426 C.
  • n n 0003 A S M mm m u W g E Q Q n n n H e n O 0 353: 0 6 C m I 0 O h 33% 000 00 n F 0002 00 U 0001 v n 1 1 m a C P 4 C 0 C r. :1 2 3 0024 24. n u 004 n 04 u 0004 T m .h h e.mfl 0 d 1 52? u n n m h w m m n m W 3.858 0013 14 n n 004 04.
  • hosgene is re- (1) C1 moved in a vacuum. After the mixture is filtered off with 01 OG""NH(CH2)GCl 2,4 dichlorophenyl N-(6-chloro-n -hexyl) carbamatet 73 MP. 55-56 c.
  • D is alkylene of l-8 carbon atoms and R is a member selected from the group consisting of alkoxy of 1-10 carbon atoms, chloro, cycloalkoxy of 56 carbon atoms in the ring, alkyl mercapto of 1-4 carbon atoms and 12 2.
  • the compound of the formula D is allzylene of 18 carbon atoms; and R is alkoxy of 1-l0 carbon atoms. 3.
  • the compound of the formula 4 The carbamic acid ester of the formula 5.
  • the carbamic acid ester of the formula References Cited UNITED STATES PATENTS 7/1960 Jones et al. 167-30 X 4/1964 Surrey et al. 260-479 9/1965 Heiss et al. 260-479 FOREIGN PATENTS 5/1963 Belgium. 11/1962 Germany.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US423596A 1964-01-25 1965-01-05 Carbamic acid esters Expired - Lifetime US3376335A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF0041833 1964-01-25

Publications (1)

Publication Number Publication Date
US3376335A true US3376335A (en) 1968-04-02

Family

ID=7098832

Family Applications (1)

Application Number Title Priority Date Filing Date
US423596A Expired - Lifetime US3376335A (en) 1964-01-25 1965-01-05 Carbamic acid esters

Country Status (8)

Country Link
US (1) US3376335A (en))
BE (1) BE658752A (en))
CH (1) CH441861A (en))
ES (2) ES308529A1 (en))
FR (1) FR1452615A (en))
GB (1) GB1025049A (en))
IL (1) IL22692A (en))
NL (1) NL6500915A (en))

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865866A (en) * 1970-01-30 1975-02-11 Sumitomo Chemical Co Carbamic acid esters
US4812590A (en) * 1987-06-25 1989-03-14 Merck & Co., Inc. Carbamates of 4-hydroxyanisole as prodrugs for chemotherapy of melanoma

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE632152A (en)) *
US2945780A (en) * 1955-03-24 1960-07-19 Fmc Corp Synergistic insecticidal compositions
DE1139113B (de) * 1961-01-17 1962-11-08 Basf Ag Verfahren zur Herstellung von N-ª‰-Halogenalkylcarbaminsaeureestern
US3131213A (en) * 1957-05-21 1964-04-28 Sterling Drug Inc 2, 6-dimethyl and 2, 6-diethylphenyl n-(aminoalkyl) carbamates and acid addition salts thereof
US3206502A (en) * 1961-03-21 1965-09-14 Bayer Ag 2-sec.-butenyl phenyl n-methyl carbamate and 2-sec. butenyl-4-methyl phenyl n-methylcarbamate

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE632152A (en)) *
US2945780A (en) * 1955-03-24 1960-07-19 Fmc Corp Synergistic insecticidal compositions
US3131213A (en) * 1957-05-21 1964-04-28 Sterling Drug Inc 2, 6-dimethyl and 2, 6-diethylphenyl n-(aminoalkyl) carbamates and acid addition salts thereof
DE1139113B (de) * 1961-01-17 1962-11-08 Basf Ag Verfahren zur Herstellung von N-ª‰-Halogenalkylcarbaminsaeureestern
US3206502A (en) * 1961-03-21 1965-09-14 Bayer Ag 2-sec.-butenyl phenyl n-methyl carbamate and 2-sec. butenyl-4-methyl phenyl n-methylcarbamate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3865866A (en) * 1970-01-30 1975-02-11 Sumitomo Chemical Co Carbamic acid esters
US4812590A (en) * 1987-06-25 1989-03-14 Merck & Co., Inc. Carbamates of 4-hydroxyanisole as prodrugs for chemotherapy of melanoma

Also Published As

Publication number Publication date
FR1452615A (fr) 1966-04-15
ES308529A1 (es) 1965-05-01
CH441861A (de) 1967-08-15
NL6500915A (en)) 1965-07-26
IL22692A (en) 1968-07-25
ES310863A1 (es) 1965-12-16
GB1025049A (en) 1966-04-06
BE658752A (en)) 1965-07-26

Similar Documents

Publication Publication Date Title
DE2513730A1 (de) Halogenacetanilide als mikrobizide wirkstoffe
DE2350944C2 (de) N-(1'-Methoxycarbonyl-äthyl)-N-haloacetyl-2-6- dialkylaniline, Verfahren zu deren Herstellung und diese Verbindungen enthaltende fungizide Mittel
DE2513789C2 (de) N-(1'-Methoxycarbonyl-äthyl)-N-haloacyl-2,6-dialkylaniline, Verfahren zu deren Herstellung und diese Verbindungen enthaltende fungizide Mittel
DE2741437A1 (de) Anilinderivate, verfahren zu ihrer herstellung und schaedlingsbekaempfungsmittel
US3624091A (en) Oxime-o-carbonic acid esters
KR920004578B1 (ko) 살균성 아닐린 유도체의 조성물
EP0098953B1 (de) Substituierte Maleinsäureimide, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel
US3376335A (en) Carbamic acid esters
CS270566B2 (en) Fungicide and method of its active substance production
EP0075172B1 (de) N-Sulfenylierte Benzylsulfonamide, ein Verfahren und ihre Verwendung als Mikrobizide
DD248357A5 (de) Verfahren zur herstellung von 9,10-phenonthrendion-derivaten
DE69823191T2 (de) 1,2,3-thiadiazol-derivate, mittel zur kontrolle von pflanzenkrankheiten und methode zu seiner anwendung
CH627343A5 (en) Microbicide
DE2919825C2 (en))
EP0122553B1 (de) N-Sulfenylierte Phenethylsulfonamide
JPH0247993B2 (en))
US3629458A (en) Fungicidal methods and compositions comprising trichloroacetaldehyde aminals
JPS61286364A (ja) カルバミン酸ベンザルドキシム誘導体類
DD201969A5 (de) Fungizide mittel
CA1185989A (en) N-sulphenylated ureas, a process for their preparation, fungicidal agents containing them and their use
EP0291809B1 (de) 2-Anilino-chinoline, Verfahren zu ihrer Herstellung und diese enthaltende Fungizide
US3247217A (en) Certain benzimidazole derivatives
EP0003974B1 (de) Trifluormethylimino-thiazolidin-Derivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Fungizide
HU180674B (en) Fungicide composition and process for producing oxasolidine-2,4-dion derivatives as active agents
EP0011802A1 (de) Neue Phenoxy-phenoxypropionsäureamide, Verfahren zu ihrer Herstellung, sie enthaltende herbizide Mittel und ihre Verwendung zur Bekämpfung von Schadpflanzen