CA2019174A1 - Dibromopropanol derivatives, process for their preparation, and their use - Google Patents
Dibromopropanol derivatives, process for their preparation, and their useInfo
- Publication number
- CA2019174A1 CA2019174A1 CA002019174A CA2019174A CA2019174A1 CA 2019174 A1 CA2019174 A1 CA 2019174A1 CA 002019174 A CA002019174 A CA 002019174A CA 2019174 A CA2019174 A CA 2019174A CA 2019174 A1 CA2019174 A1 CA 2019174A1
- Authority
- CA
- Canada
- Prior art keywords
- dibromopropanol
- derivatives
- species
- formula
- alkyl
- 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.)
- Abandoned
Links
Classifications
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/48—Nitro-carboxylic acids; Derivatives thereof
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
- C07C255/12—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/36—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
Dibromopropanol derivatives, process for their prepara-tion, and their use A b s t r a c t The invention relates to new dibromopropanol derivatives of the formula
Description
The invention relates to new 2-cyano-2,3-dibromo-propanol derivatives, to a process for their preparation, and to their use as microbicides for the protection of materials.
The fact that brominated propanol derivatives, namely 2-bromo-2-nitro-3-hydroxy-propanol, are used as the preservative for functional liquids, is already known tsee Seifen-~le-Fette-Wachse 114 (1988) p. 319-323).
However, the action of this microbicide against moulds is not satisfactory; it is therefore recommended to apply this compound only in combination with highly fungicidal-ly active compounds, such as isothiazolinones, for preserving functional liquids (see Seifen-~le-Fette-Wachse loc.cit. p. 321-322). A further disadvantage of 2-bromo-2-nitro-3-hydroxy-propanol when used as a preserva-tive is, moreover, that it is hydrolyzed at pH values of >7.5 with the elimination of formaldehyde and nitrite, that is to say ecologically hazardous compounds.
Surprisingly, it has now been found that certain new dibromopropanol derivatives have a considerably im-proved microbicidal activity and, furthermore, do not form toxic compounds when they are hydrolyzed. Further-more, it has been found that some of these new dibromo-propanol derivatives have an action against Fusarium species, for example Fusarium nivale, which has hitherto not been achieved by known funyicides, and some have a good action against mildew.
The invention therefore relates to dibromopro-panol derivatives of the formula !
Le A 26 863 - 2 -~" 2 ~
Br R-C~-C-CH2-Br (I), l l OH CN
in which R represents an optionally substituted alkyl, cyclo-alkyl, axyl or heteroaryl radical.
Examples of R which may be mentioned are:
as optionally substituted alkyl radicals: C1-Cl~-alkyl radicals, such as the methyl, ethyl, n-propyl, i-propyl, n-butyl, tert.-butyl, n-hexyl, i-octyl and the n-dodecyl radical; C1-C4-alkyl radicals which are substituted by halogen ato~s, such as fluorine, chlorine or bromine, C1-C4-alkoxy, such as methoxy or ethoxy; C1-C4-alkylmercapto, such as methylmercapto, trifluoromethylmercapto and dichlorofluoromethylmercapto radicals, such as the 2-methoxyethyl, 2-ethoxyethylj 2-chloroethyl, 2-trifluoro-methylmercaptoethyl and 2,3-dibromopropyl radical;
as optionally substituted cycloalkyl radicals, the cyclohexyl radical and the cyclohexyl radicals which are substituted by halogen, in particular chlorine atoms, and/or C1-C4-alkyl groups, such as the 4-methylcyCloheXyl, 2,6-dimethylcyclohexyl and 4-tert.-butylcyclohexyl xadical;
as optionally substituted aryl radicals, in particular the phenyl radical and phenyl radicals which are sub-: stituted by halogen, nitro or cyano, such as the 2~
Ichlorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-::
Le A 26 863 - 3 -2 ~
:;
nitrophenyl and the 2,6-dichlorophenyl radical;
as optionally substituted heteroaryl radicals, the 2-, 3-or 4-pyridyl radical and pyridyl radicals which are substituted by halogen and/or C1-C4-alkyl groups, such as the 6-chloro-2-pyridyl radical.
R preferably represents a C1-C~-alkyl radical, or a phenyl radical which is substituted by chlorine or bromine, particularly~preferably a C3-C6-alkyl radical.
: The following compounds may be mentioned as ~ 10 representatives of the dibromopropanol derivatives of the :~ formula (I) according to the invention: 1,2-dibromo-2-: cyano-3-hydroxy-butane, : 1,2-dibromo-2-cyano-3-hydroxy-pentane, 1,2-dibromo-2-cyano-3-hydroxy-hexane, 1,2-dibromo-2-cyano-3-hydroxy-4-methyl-pentane, 1,2-dibromo-, 2-cyano-3-hydroxy-4,4-dimethyl-pentane, 1,2-dibromo-2-cyano-3-hydroxy-nonane, 1,2-dibromo-2-cyano-3-hydroxy-3-~: phenyl-propane, : 1,2-dibromo-2-cyano-3-hydroxy-3-(4-:~: bromophenyl)-propane, 1,2-dibromo-2-cyano-3-hydroxy-3-(2-chlorophenyl)-propane, 1,2-dibromo-2-cyano-3-hydroxy-3-(4-chlorophenyll-propane,:1,2-dibromo-2-cyano-3-hydroxy- ::
The fact that brominated propanol derivatives, namely 2-bromo-2-nitro-3-hydroxy-propanol, are used as the preservative for functional liquids, is already known tsee Seifen-~le-Fette-Wachse 114 (1988) p. 319-323).
However, the action of this microbicide against moulds is not satisfactory; it is therefore recommended to apply this compound only in combination with highly fungicidal-ly active compounds, such as isothiazolinones, for preserving functional liquids (see Seifen-~le-Fette-Wachse loc.cit. p. 321-322). A further disadvantage of 2-bromo-2-nitro-3-hydroxy-propanol when used as a preserva-tive is, moreover, that it is hydrolyzed at pH values of >7.5 with the elimination of formaldehyde and nitrite, that is to say ecologically hazardous compounds.
Surprisingly, it has now been found that certain new dibromopropanol derivatives have a considerably im-proved microbicidal activity and, furthermore, do not form toxic compounds when they are hydrolyzed. Further-more, it has been found that some of these new dibromo-propanol derivatives have an action against Fusarium species, for example Fusarium nivale, which has hitherto not been achieved by known funyicides, and some have a good action against mildew.
The invention therefore relates to dibromopro-panol derivatives of the formula !
Le A 26 863 - 2 -~" 2 ~
Br R-C~-C-CH2-Br (I), l l OH CN
in which R represents an optionally substituted alkyl, cyclo-alkyl, axyl or heteroaryl radical.
Examples of R which may be mentioned are:
as optionally substituted alkyl radicals: C1-Cl~-alkyl radicals, such as the methyl, ethyl, n-propyl, i-propyl, n-butyl, tert.-butyl, n-hexyl, i-octyl and the n-dodecyl radical; C1-C4-alkyl radicals which are substituted by halogen ato~s, such as fluorine, chlorine or bromine, C1-C4-alkoxy, such as methoxy or ethoxy; C1-C4-alkylmercapto, such as methylmercapto, trifluoromethylmercapto and dichlorofluoromethylmercapto radicals, such as the 2-methoxyethyl, 2-ethoxyethylj 2-chloroethyl, 2-trifluoro-methylmercaptoethyl and 2,3-dibromopropyl radical;
as optionally substituted cycloalkyl radicals, the cyclohexyl radical and the cyclohexyl radicals which are substituted by halogen, in particular chlorine atoms, and/or C1-C4-alkyl groups, such as the 4-methylcyCloheXyl, 2,6-dimethylcyclohexyl and 4-tert.-butylcyclohexyl xadical;
as optionally substituted aryl radicals, in particular the phenyl radical and phenyl radicals which are sub-: stituted by halogen, nitro or cyano, such as the 2~
Ichlorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-::
Le A 26 863 - 3 -2 ~
:;
nitrophenyl and the 2,6-dichlorophenyl radical;
as optionally substituted heteroaryl radicals, the 2-, 3-or 4-pyridyl radical and pyridyl radicals which are substituted by halogen and/or C1-C4-alkyl groups, such as the 6-chloro-2-pyridyl radical.
R preferably represents a C1-C~-alkyl radical, or a phenyl radical which is substituted by chlorine or bromine, particularly~preferably a C3-C6-alkyl radical.
: The following compounds may be mentioned as ~ 10 representatives of the dibromopropanol derivatives of the :~ formula (I) according to the invention: 1,2-dibromo-2-: cyano-3-hydroxy-butane, : 1,2-dibromo-2-cyano-3-hydroxy-pentane, 1,2-dibromo-2-cyano-3-hydroxy-hexane, 1,2-dibromo-2-cyano-3-hydroxy-4-methyl-pentane, 1,2-dibromo-, 2-cyano-3-hydroxy-4,4-dimethyl-pentane, 1,2-dibromo-2-cyano-3-hydroxy-nonane, 1,2-dibromo-2-cyano-3-hydroxy-3-~: phenyl-propane, : 1,2-dibromo-2-cyano-3-hydroxy-3-(4-:~: bromophenyl)-propane, 1,2-dibromo-2-cyano-3-hydroxy-3-(2-chlorophenyl)-propane, 1,2-dibromo-2-cyano-3-hydroxy-3-(4-chlorophenyll-propane,:1,2-dibromo-2-cyano-3-hydroxy- ::
3-(4-nitrophenyl)-propane, 1,2-dibromo-2-cyano-3-hydroxy-: : 3-~2,6-dichlorophenyl)-propane, 1,2-dibromo-2-cyano-3-hydroxy-3-cyclohexylpropane.
~; ` : The dibromopropanol derivatives of the formula (I) according to the invention are obtained by brominat-ing acryl compounds of the formula ~ ~ , : ~, ~- , ~ :
~:
Le A 26 863 - 4 ----` 2 ~ 7 ~
HO~fH-f=CH2 tII), R CN
in which R has the meaning indicated in the case of formula The acryl compounds of the formula (II) are known and are described, for example, in DE-OS ~German Publi-shed Specification) 2,155,113.
The invention also relates to this process for the preparation of the dibromopropanol deri~atives of the formula (I); the process is characterized in that the acryl derivatives of the formula (II) are brominated, if appropriate in the presence of an organic solvent which ;~ is inert under the reaction conditions.
Examples of organic solvents which are inert : under the reaction conditions and which may be mentioned are aliphatic chlorohydrocarbons, such as methylene chloride, ethylene chloride, chloroform and carbon tetrachloride, aromatic chlorohydrocarbons, such as chlorobenzene and ortho-dichlorobenzene, or glacial acetic acid.
The bromination is carried out at temperatures of ~rom 0 to 80C, preferably at temperatures of from 20 to 600C.
.
Le A 26 863 - 5 - .
'~ 7 ~
, ~', . , :
. "
In the bromination, the amount of bromine used i5 such that 1 to`l.2 mols of bromine are employed per mol of acryl compound of~the formula (II) to be halogenated.
The bromine i5 added and the bromination mixture -S i5 worked up in a manner known from pr~parative chemis-try.
The dibromopropanols of the formula (I) according to the invention are distinguished by powerful microbici-dal action and a good fungicidal activity, in particular against Fusarium species and mildew. They are consider-ably superior to the known brominated propanol deriva-tives, both with regard to their fungicidal action and with regard to their~broad range of effectiveness. The in-:: vention therefore also relates to the use of the dibromopro-panol derivatives of the formula (I) according to the invention as microbicides for the protection of indus~rial ma~erials a~d as fungicides in~plant protection.
; ~ Industrial materials according to the invention are non-live materials which have been manufactured for use in industry. For example, industrial materials which are to be protected by active compounds according to the ;invention from microbial change or destruction can be glues, sizes, paper and boardj textiles, leather, wood, :~:
paint and plastic articles, cooling lubricants and other ~ materials which can be colonized or decomposed by micro-organisms. Parts of production plants, for example cooling-water circuits, which may be impaired by micro-organisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may Ibe mentioned within the scope of the present invention ~:
:~:
Le A 26 863 - 6 -2 ~ 7 ~
are preferably glues, sizes, papers and boards, leather, wood, paints, cooling lubricants and heat-transfer liquids.
Microorganisms, capable of a degradation or a change of the industrial materials, which may be men-tioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), phytopathogenic fungi and also against slime organ1sms and algae.
Microorganisms of the following genera may be -mentioned as examples:
Alternaria, such as Alternaria tenuis, ~-Aspergillus, such as Aspergillus niger, Botrytis, such as Botrytis cinera, Chaetomium, such as Chaetomium globosum Coniophora, such as Coniophora puteana, ~ Lentinus, such as Lentinus tigrinus, ; ~ 20 Penicillium, such as Penicillium glaucum, Piricularia, such as Piricularia oryzae, -Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, -Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus. --Fungicides are employed in plant protection for Icombatin;g plasmodiophoromycetes, oomycetes, ~ .
~ :
~: :
Le A 26 863 - 7 -2 ~ 7 ~
., `..
chytridiomycetesj zygomycetes, ascomycetes, basidiomy-cetes, deuteromycetes.
The following may be mentioned as examples of - .
pathogens causing fungal diseases which come under the abovementioned generic terms:
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
: :PIasmopara species, such as, for example, Plasmopara viticola; ;
Peronospora species,: such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
:
: Sphaerotheca species, such as, for example, Sphaerotheca~fuliginea;
Podosphaera specie~, such as, for example, Podosphaera leucotricha;
~ Venturia species, such as, for example, Venturia :~ inaequalis;
:~: Pyrenophora speciesj such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn:
Helminthosporium);
Cochliobolus species, such as, for example, : Cochliobolus sativus (conidia form: Drechslera, syn:
Helminthosporium);
Uromyces species, such as, for example, Uromyces appen-Idiculatus;
, Le A 26 863 - 8 -2 ~ 7 ~
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; .
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, - ~:
- Leptosphaeria nodorum; ~-Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae and ~
PseudocercosporeIla species, such as, for example, : Pseudocercosporella herpotrichoides.
Some of the active compounds according to the ;:
;~: invention have proved particularly useful for combating Fusarium species, such as, for example, Fusarium nivale, ~ in particular in cereals. Furthermore, some of the active :: compounds according to the invention have good fungicidal actions against powdery mildew, for example on grape vines (Uncinula), apples and cereals, such as barley and ~ wheat.
: The good toleration by plants of the active compounds in the concentration required for combating plant diseases permits treatment of aerial parts of the Le A 26 863 - 9 -~ 2 ~
plants, of vegetative propagation stock and seedsi, and of the soil.
Depending on the field of application, the active compounds according to the invention can be converted into the customary formulations, such as solutionsi, emulsions, suspensions, powders, pastes and granules.
These can~be prepared in a manner known per se, for example by mixing the active compounds with an extender which consists of liquid solvent and/or solid carriers, optionally with the use of surface-active agents, such as emulsifiers and/or dispersing agents, in the case of water being used as the extender, it being ~ possible for organic solvents such as alcohols to be used .~ as auxiliary substances.
:: 15 Liquid solvents for the active compounds can be, for~example, water:, alcohols, such as lower aliphatic alcohols, preferably ethanol or isopropanol, or benzyl-~:~: alcohol, ketones, such as acetone or methyl ethyl ketone, ;~ liquid hydrocarbons, such as mineral oil fractions, and halogenated hydrocarbons, such as 1,2-dichloroethane.
Microbicidal agents contain the active compounds ~; in general in an amount of l to 95%, preferably lO to 5%.
The application concentrations of the active compounds according to the invention depend on the species and the occurrence of the microorganisms to be combated, and also on the composition of the material to ~: : be protected. ~he optimum amount to be employed can be determined by test series. In general, the application ¢oncentrations are within the range of 0.001 to 5 ~i by Le A 26 863 - 10 -7 ~
.; ~, ~ ., weight, preferably of 0.05 to 1.0 ~ by weight, based on the weight of the material to be protected.
The active compounds according to the invention can also be used in mixtures with other known active compounds. The following active compounds may be men-tioned as examples: benzyl alcohol mono(poly)hemiformal and other formaldehyde-eliminating compounds, isothiazol-inone derivatives, benzoisothiazolinone, p-hydroxybenzoic esters, benzimidazolyl-methylcarbamates, tetramethyl-thiuram disulphide, zinc salts of dialkyl dithiocarbamates, 2,4,5,6-tetrachloroisophthalonitrile, thiazolylbenzimidazole, mercaptobenzothiazole, organic tin compounds, methylene bisthiocyanatej 2-thiocyanato-methylthio-benzothiazole, phenol derivatives, such as 2-phenylphenol, (2,`2'-dihydroxy-5,5'-dichloro)diphenyl-methane and ~3-methyl-4-chloro-phenol, N-trihalogeno-methylthio compounds, such as folpet, fluorfolpet and dichlorfluamid, and azole fungicides, such as triadime-~ ~ fon, triadimenol and bitertanol.
;~ 20 Example 1 63.8 g (0.5 mol) of 2-(1-hydroxybutyl~-acrylonit-riIe are dissolved in 200 ml of chloroform, and 79.9 g (0.5 mol) of bromine are added dropwise to the stirred solution at 60C in the course of 1.5 hours. ~hen the addition is complete, the reaction solution is stirred for 3 hours at 60C. The solution is subsequently cooled to room temperature and then washed three times with 20 ml portions of a 10~ strength sodium bisulphite solution.
After the solution has been dried over sodium sulphate, it is evaporated on a rotary evaporator.
Le A 26 863 - 11 -: :
.
. ~`
This gives 133.7 g (93.8% of theory) of an oil which, according to analysis by gas chromatography, contains 84.1% of 1,2-dibromo-2-cyano-3-hydroxyhexane.
The compound is characterized by its mass spectrum: M~
285.
Example 2 31.7 g (O.2 mol) of 2-(~-hydroxybenzyl)-acryloni-trile are dissolved in 150 ml of chloroform, and 32 g (0.2 mol) of bromine, dissolved in 50 ml of chloroform, : 10 are added dropwise to the stirred solution at 60C in the course of 1 hour. When the addition is complete, the reaction mixture is stirred for 3 1~2 hours at 60C. It : is subsequently cooled to room temperature and stirred with 20 ml of sodium bisulphite solution, the aqueous phase is separated off, and the organic phase is dried over sodium sulphate. The solvent is removed, and the : crude product which is then obtained is purified by column chromatography ~eluant: toluene/ethyl acetate 9:1;
silica gel).
This gives 31.7 g (= 49~7% of theory) of 1,2-dibromo-2-cyano-3-hydroxy-3-phenyl-propane in form of a yellow oil.
: The compound is characterized by its IR spectrum (3470 cm~l -OH; 2255 cm1 -CN).
The physical characteristic data of the dibromopropanols of the formula (I) which are obtained in an analogous manner and in which R has the meaning likewise given in the table, are compiled in the table which follows.
Le A 26 863 - 12 -a:
` ~
~' I, E ' , z z o Z L
~rl I I t8 ~1 E Ei E E-~ E
S-l ^ ~ u u ~ E E
.C ~ ^~ ~`3 ~ o o o o CO o o o ~_1 ~ N ~ ~ , ~ ~ ~ 10 O
T
_, _l '' 1~ r 1 T 1 J b r ~ ,a~
a I ~ ~ o e A 26 863 - 13 -2 ~ 7 4 ,1 I Z
h l l u E a~ u u N ~ ~ ~r N
_I
U
.,1 ~ C
1:4 L ~: E
b , , ,, a X
E~ EL1 Le A 26863 - 14 -Z ~ 7 ~
Use ExamPles ExamPle 14 In order to determine the~activity against fungi, ,,' ,-,, , the minimum inhibitory~concentrations ~MICs) of dibromo- ', '"
5 ~ propanols according;~to~the invention were determined: ' ',', Active~compounds ~according to the invention are ~ ,~
added at concentrations;from O.~ mg/l to 5000 mg/l to an agar which is~prepared~from ~brewer's wort and peptone. ; ,',, When the agar~has~solidified, it is contaminated with ,, 10 ~ pure cultures~of~the~test~'~organisms~1isted in the table. ,- ,~
The cultures are,~stored~for;~2~weeks~at 28C and 60 to 70~ ",'-,;-,', relative~atmo'spheric~humidity,~and;the MIC is determined. ',",,, MIC~is~the~lowest~concentration~ of~active compound'at ,~,,~,' which no growfth ~whatsoever by the microbe species used f~,','~i,~ 15~ takes p1ace;~it~is~lndicated'in Table 2 below. ,',,,-,, " ~ ~, : :
Le A 26 863 - 15 -:, :
o ~ o c~ o o o o o o o u ~ o u~ ~ oo l~ o u~ o _I f~U~ g O O ~ O O ~0 g 3 ~l ~
: x c~u~ o o o o o o o o o - -oL l'~ 5 o g NO Oo o o l ~
OOOOOIJ~OOO
tJ) ~ t~ O ~ O N ~ IJ~ -- O
: ~ .rl ~ ~ o o Ln O ~ ~ o ~ O O U~ O ~ U~ ~r~ ~ o I
U~ ~ _ ~1 o ~ O ~ ~ gO ~ O
5~ ~; ~ ~ ~
0 ~ O 0 O U~ O O ~ U~
1~ ~ o O o ~ o _I
O u ~ ~., g ~ O ~ ~ u~ ~ N - O
' ~ ~ ~ ' _I 1:1 0 _ ~
~ C~ E 'C h _~._ 0.\ ~ , L rl u11~ c.~ o u~ ~::
U U~ ~ C E-- L ~ cL :>
~ ~ E L J ~ 3 L N
h L-- ~E O -- ~ ~ O
tr) O L L O J O _ U a~ u .4 ~ _, 3 L m ~J C C U L
0 ~ _ ~ ~ ~ E~
E~E~ *
Le A 26 863 7 ~
., , ,, , ExamPle 15 Action against bacteria Active compounds according to the invention in concentrations of l to 5000 ppm are added to an agar , containing broth as the nutrient medium. The nutrient medium is now infected with the specific test organisms listed in Table II, and the infected medium i5 kept for 2 weeks at 28C and 60 to 70~ relative atmospheric , humidity. The MIC is the lowest concentration of active compound at which no growth whatsoever of the microbe species used takes place. The MIC values can be found in -Table 3.
Table 3 MIC values indicated in mg/l of the active lS compounds indicated below acting on bacteria.
MIC in mq/l of the active compounds Test organisms Compound of Example No.
Escherichia coli 200 1000 200 150 750 500 S~aphylococcus 2001000 200 500 500 100 aureus ~;
: .
. , Example 16 tAction against slime organisms) ; The compounds to be tested, dissolved in a small amount of acetone, are applied in Allen's nutrient ' 1~ ' Le A 26 863 - 17 -2 ~ 7 ~
. , solution (Arch. Mikrobiol. 17, 34 to 53 (1952)), which contains 0.2 g of ammonium chloride, 4.0 g of sodium nitrate, 1.0 g of dipotassium hydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesium sulphate, 0.02 g of iron chloride and 1% of caprolactam per 4 litres of sterile water, at concentrations of in each case 0.1 to 100 mg/l. At the beginning of the test, the individual nutrient solutions are infected with slime organisms (about 106 microorganism /ml) which have been isolated from spinning water circuits used in the production of nylon. After being cultured for 3 weeks at room tempera-ture, nutrient solutions containing the minimum inhibi-tory concentration (MIC) or higher concentrations of the iodopropargyl ether to be tested are still completely clear; the copious multiplication of the microbes and slime formation and the associated turbidity, which are observed after 3 to 4 days in nutrient solutions not containing active compound, do not take place.
~able 4 MIC value [mg/l] of the dibromopropanols accord-ing to the invention when acting on slime organisms.
Dibromopropanol of Example MIC [mg/l]
1 5 - ~10 2 s - <10 4 ~5 - (10 :
~'~
Le A 26 863 - 18 -~j 2 ~ 7 ~
. .
, ExamPle 17 ~Action against algae) A mixed culture of green algae, blue-green algae, brown algae and diatoms (Stichococcus bacillaris Naegeli, Euglena gracilis Klebs, Chlorella pyrenoidosa Chick, Phormidium foveolarum Gomont, Oscillatoria geminata Meneghini and Phaeodactylum tricornutum Bohlin) is added to Allen's nutrient solution tArch. Mikrobiol. 17, 34 to 53 (1952)) which contains 0.2 g of ammonium chloride, 4.0 g of sodium~nitrate, 1.0 g of dipotassium hydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesium sulphate and 0.02 g of iron chloride per 4 litres of sterile water, with air being bubbled through. After 2 weeks, the nutrient solution has a deep green-blue colour caused by proliPic growth of algae. The destruction of the algae as a result of adding active compounds accord-ing to the invention can be seen from the decolouration of the nutrient solution. -Table 5 Algae-destroying concentrations [mg/l] of the dibromopropanols according to the invention ` Compound ofDestroying concentration [mg/l]
Example No.
1 50 - ~100 2 )50 - <100 4 so - <IO0 Le A 26 863 - 19 -~""~ ""~,,, `,,~,-;,",, "";", ~'," ' .,.~,, ' , ' :~' ' :~ ;~ ~ :' i': ':, , .~, .
~ 3 7 ~
.
Comparison:
2-bromo-2-nitro-3-hydroxy-propanol >100 ExamPle 18 Fusarium nivale test (rye)tseed treatment The active compounds are applied in form of seed treatment powders. The latter are prepared by mixing (extending~ the specific active compound with ground minerals to give a finely-pulverulent mixture which guarantees uniform distribution on the seed surface.
For seed dressing, the infected seeds together with the treatment powder are shaken for 3 minutes in a sealed glass bottle.
Two batches of 100 rye grains are sown in standard soil at a depth of 1 cm, and the crop is cul-~; 15 tured in a greenhouse at a temperature of about 10C and a relative atmospheric humidity of about 95%, in seed boxes which receive a daily exposure to light of 15 hours.
About 3 weeks after sowing, the plants are evaluated for symptoms of snow mould.
In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the ~; compounds of the following Preparation Examples:
:
Le A 26 863 - 20 - -~ 7 ~
,, Table Fusarium nivale test (rye)/seed treatment Active compound Dosage rate Degree of of active effective-compound in ness in %
mg/kg of seed of the un- :
treated con-trol Br 500 89 Hl 3C6-fH-f -CH2Br OH CN
(Example 6) Br H5C2--CH-f-CH2Br 500 91 OH CN
(Example 4) according to the prior art: (US Patent Specification 4,446,076) Br H3C-C-CH2E~r 500 66 CN
Le A 26 863 - 21 -20~ 7~
~: !
Example 19 Erysiphe test (barley)/protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether ; To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. when the spray coating has dried on, the plants~are dusted with~the spores of Erysiphe graminis f.sp. hordei. ~ -- -The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80% to promote the development of -;~
mildew pustules.
Evaluation is carried oùt 7 days after the ~ - -inoculation.
In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of the following Preparation Examples~
~; ":'` .' ' :
, Le A 26 863 - 22 -'~' Table Brysiphe test (barley)/protective Acti~e compound Concentration Degree of of active com- effective-pound in the ness in %
spray liquor in of the un-% by weight treated control Br 0, 00025 75 Br~3fH-C-CH2Br OH CN
~Example 8) according to prior art:
(US Patent Specification 4,446,076) Cl ar ~ I o,00025 o Cl ~ C -CH2Br CN
Le A 26 863 - 23 -.,~ . ' ~ ! , ~ . ' . . . ..
~` ~J~ 7 ~
.
Example 20 Erysiphe test (wheat)/protective Solvent: lO0 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, l part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. When the spray coating has dried on, the plants are dusted with the spores of Erysiphe graminis f.sp. tritici.
The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80% to promote the development of miIdew pustules.
Evaluation is carried out 7 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of the following Preparation Examples:
: -, ':
ke A 26 863 - 24 ---~ 2 ~ 7 ~
Table Erysiphe test (wheat)/protective Active compound Concentration Degree of of active com- effective-pound in the ness in %
spray liquor in of the un-% by weight treated control Br Br ~ CH-~-CH2Br 0,0025 75 OH CN
(Example 8) according to the prior art:
(US Patent Specification 4,446,076) C1 Br Cl ~ ~ C -CH2Br 0,0025 16 C~l ,: , Le A 26 863 - 25 -
~; ` : The dibromopropanol derivatives of the formula (I) according to the invention are obtained by brominat-ing acryl compounds of the formula ~ ~ , : ~, ~- , ~ :
~:
Le A 26 863 - 4 ----` 2 ~ 7 ~
HO~fH-f=CH2 tII), R CN
in which R has the meaning indicated in the case of formula The acryl compounds of the formula (II) are known and are described, for example, in DE-OS ~German Publi-shed Specification) 2,155,113.
The invention also relates to this process for the preparation of the dibromopropanol deri~atives of the formula (I); the process is characterized in that the acryl derivatives of the formula (II) are brominated, if appropriate in the presence of an organic solvent which ;~ is inert under the reaction conditions.
Examples of organic solvents which are inert : under the reaction conditions and which may be mentioned are aliphatic chlorohydrocarbons, such as methylene chloride, ethylene chloride, chloroform and carbon tetrachloride, aromatic chlorohydrocarbons, such as chlorobenzene and ortho-dichlorobenzene, or glacial acetic acid.
The bromination is carried out at temperatures of ~rom 0 to 80C, preferably at temperatures of from 20 to 600C.
.
Le A 26 863 - 5 - .
'~ 7 ~
, ~', . , :
. "
In the bromination, the amount of bromine used i5 such that 1 to`l.2 mols of bromine are employed per mol of acryl compound of~the formula (II) to be halogenated.
The bromine i5 added and the bromination mixture -S i5 worked up in a manner known from pr~parative chemis-try.
The dibromopropanols of the formula (I) according to the invention are distinguished by powerful microbici-dal action and a good fungicidal activity, in particular against Fusarium species and mildew. They are consider-ably superior to the known brominated propanol deriva-tives, both with regard to their fungicidal action and with regard to their~broad range of effectiveness. The in-:: vention therefore also relates to the use of the dibromopro-panol derivatives of the formula (I) according to the invention as microbicides for the protection of indus~rial ma~erials a~d as fungicides in~plant protection.
; ~ Industrial materials according to the invention are non-live materials which have been manufactured for use in industry. For example, industrial materials which are to be protected by active compounds according to the ;invention from microbial change or destruction can be glues, sizes, paper and boardj textiles, leather, wood, :~:
paint and plastic articles, cooling lubricants and other ~ materials which can be colonized or decomposed by micro-organisms. Parts of production plants, for example cooling-water circuits, which may be impaired by micro-organisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may Ibe mentioned within the scope of the present invention ~:
:~:
Le A 26 863 - 6 -2 ~ 7 ~
are preferably glues, sizes, papers and boards, leather, wood, paints, cooling lubricants and heat-transfer liquids.
Microorganisms, capable of a degradation or a change of the industrial materials, which may be men-tioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), phytopathogenic fungi and also against slime organ1sms and algae.
Microorganisms of the following genera may be -mentioned as examples:
Alternaria, such as Alternaria tenuis, ~-Aspergillus, such as Aspergillus niger, Botrytis, such as Botrytis cinera, Chaetomium, such as Chaetomium globosum Coniophora, such as Coniophora puteana, ~ Lentinus, such as Lentinus tigrinus, ; ~ 20 Penicillium, such as Penicillium glaucum, Piricularia, such as Piricularia oryzae, -Polyporus, such as Polyporus versicolor, Aureobasidium, such as Aureobasidium pullulans, -Sclerophoma, such as Sclerophoma pityophila, Trichoderma, such as Trichoderma viride, Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa, Staphylococcus, such as Staphylococcus aureus. --Fungicides are employed in plant protection for Icombatin;g plasmodiophoromycetes, oomycetes, ~ .
~ :
~: :
Le A 26 863 - 7 -2 ~ 7 ~
., `..
chytridiomycetesj zygomycetes, ascomycetes, basidiomy-cetes, deuteromycetes.
The following may be mentioned as examples of - .
pathogens causing fungal diseases which come under the abovementioned generic terms:
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
: :PIasmopara species, such as, for example, Plasmopara viticola; ;
Peronospora species,: such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
:
: Sphaerotheca species, such as, for example, Sphaerotheca~fuliginea;
Podosphaera specie~, such as, for example, Podosphaera leucotricha;
~ Venturia species, such as, for example, Venturia :~ inaequalis;
:~: Pyrenophora speciesj such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn:
Helminthosporium);
Cochliobolus species, such as, for example, : Cochliobolus sativus (conidia form: Drechslera, syn:
Helminthosporium);
Uromyces species, such as, for example, Uromyces appen-Idiculatus;
, Le A 26 863 - 8 -2 ~ 7 ~
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; .
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, - ~:
- Leptosphaeria nodorum; ~-Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae and ~
PseudocercosporeIla species, such as, for example, : Pseudocercosporella herpotrichoides.
Some of the active compounds according to the ;:
;~: invention have proved particularly useful for combating Fusarium species, such as, for example, Fusarium nivale, ~ in particular in cereals. Furthermore, some of the active :: compounds according to the invention have good fungicidal actions against powdery mildew, for example on grape vines (Uncinula), apples and cereals, such as barley and ~ wheat.
: The good toleration by plants of the active compounds in the concentration required for combating plant diseases permits treatment of aerial parts of the Le A 26 863 - 9 -~ 2 ~
plants, of vegetative propagation stock and seedsi, and of the soil.
Depending on the field of application, the active compounds according to the invention can be converted into the customary formulations, such as solutionsi, emulsions, suspensions, powders, pastes and granules.
These can~be prepared in a manner known per se, for example by mixing the active compounds with an extender which consists of liquid solvent and/or solid carriers, optionally with the use of surface-active agents, such as emulsifiers and/or dispersing agents, in the case of water being used as the extender, it being ~ possible for organic solvents such as alcohols to be used .~ as auxiliary substances.
:: 15 Liquid solvents for the active compounds can be, for~example, water:, alcohols, such as lower aliphatic alcohols, preferably ethanol or isopropanol, or benzyl-~:~: alcohol, ketones, such as acetone or methyl ethyl ketone, ;~ liquid hydrocarbons, such as mineral oil fractions, and halogenated hydrocarbons, such as 1,2-dichloroethane.
Microbicidal agents contain the active compounds ~; in general in an amount of l to 95%, preferably lO to 5%.
The application concentrations of the active compounds according to the invention depend on the species and the occurrence of the microorganisms to be combated, and also on the composition of the material to ~: : be protected. ~he optimum amount to be employed can be determined by test series. In general, the application ¢oncentrations are within the range of 0.001 to 5 ~i by Le A 26 863 - 10 -7 ~
.; ~, ~ ., weight, preferably of 0.05 to 1.0 ~ by weight, based on the weight of the material to be protected.
The active compounds according to the invention can also be used in mixtures with other known active compounds. The following active compounds may be men-tioned as examples: benzyl alcohol mono(poly)hemiformal and other formaldehyde-eliminating compounds, isothiazol-inone derivatives, benzoisothiazolinone, p-hydroxybenzoic esters, benzimidazolyl-methylcarbamates, tetramethyl-thiuram disulphide, zinc salts of dialkyl dithiocarbamates, 2,4,5,6-tetrachloroisophthalonitrile, thiazolylbenzimidazole, mercaptobenzothiazole, organic tin compounds, methylene bisthiocyanatej 2-thiocyanato-methylthio-benzothiazole, phenol derivatives, such as 2-phenylphenol, (2,`2'-dihydroxy-5,5'-dichloro)diphenyl-methane and ~3-methyl-4-chloro-phenol, N-trihalogeno-methylthio compounds, such as folpet, fluorfolpet and dichlorfluamid, and azole fungicides, such as triadime-~ ~ fon, triadimenol and bitertanol.
;~ 20 Example 1 63.8 g (0.5 mol) of 2-(1-hydroxybutyl~-acrylonit-riIe are dissolved in 200 ml of chloroform, and 79.9 g (0.5 mol) of bromine are added dropwise to the stirred solution at 60C in the course of 1.5 hours. ~hen the addition is complete, the reaction solution is stirred for 3 hours at 60C. The solution is subsequently cooled to room temperature and then washed three times with 20 ml portions of a 10~ strength sodium bisulphite solution.
After the solution has been dried over sodium sulphate, it is evaporated on a rotary evaporator.
Le A 26 863 - 11 -: :
.
. ~`
This gives 133.7 g (93.8% of theory) of an oil which, according to analysis by gas chromatography, contains 84.1% of 1,2-dibromo-2-cyano-3-hydroxyhexane.
The compound is characterized by its mass spectrum: M~
285.
Example 2 31.7 g (O.2 mol) of 2-(~-hydroxybenzyl)-acryloni-trile are dissolved in 150 ml of chloroform, and 32 g (0.2 mol) of bromine, dissolved in 50 ml of chloroform, : 10 are added dropwise to the stirred solution at 60C in the course of 1 hour. When the addition is complete, the reaction mixture is stirred for 3 1~2 hours at 60C. It : is subsequently cooled to room temperature and stirred with 20 ml of sodium bisulphite solution, the aqueous phase is separated off, and the organic phase is dried over sodium sulphate. The solvent is removed, and the : crude product which is then obtained is purified by column chromatography ~eluant: toluene/ethyl acetate 9:1;
silica gel).
This gives 31.7 g (= 49~7% of theory) of 1,2-dibromo-2-cyano-3-hydroxy-3-phenyl-propane in form of a yellow oil.
: The compound is characterized by its IR spectrum (3470 cm~l -OH; 2255 cm1 -CN).
The physical characteristic data of the dibromopropanols of the formula (I) which are obtained in an analogous manner and in which R has the meaning likewise given in the table, are compiled in the table which follows.
Le A 26 863 - 12 -a:
` ~
~' I, E ' , z z o Z L
~rl I I t8 ~1 E Ei E E-~ E
S-l ^ ~ u u ~ E E
.C ~ ^~ ~`3 ~ o o o o CO o o o ~_1 ~ N ~ ~ , ~ ~ ~ 10 O
T
_, _l '' 1~ r 1 T 1 J b r ~ ,a~
a I ~ ~ o e A 26 863 - 13 -2 ~ 7 4 ,1 I Z
h l l u E a~ u u N ~ ~ ~r N
_I
U
.,1 ~ C
1:4 L ~: E
b , , ,, a X
E~ EL1 Le A 26863 - 14 -Z ~ 7 ~
Use ExamPles ExamPle 14 In order to determine the~activity against fungi, ,,' ,-,, , the minimum inhibitory~concentrations ~MICs) of dibromo- ', '"
5 ~ propanols according;~to~the invention were determined: ' ',', Active~compounds ~according to the invention are ~ ,~
added at concentrations;from O.~ mg/l to 5000 mg/l to an agar which is~prepared~from ~brewer's wort and peptone. ; ,',, When the agar~has~solidified, it is contaminated with ,, 10 ~ pure cultures~of~the~test~'~organisms~1isted in the table. ,- ,~
The cultures are,~stored~for;~2~weeks~at 28C and 60 to 70~ ",'-,;-,', relative~atmo'spheric~humidity,~and;the MIC is determined. ',",,, MIC~is~the~lowest~concentration~ of~active compound'at ,~,,~,' which no growfth ~whatsoever by the microbe species used f~,','~i,~ 15~ takes p1ace;~it~is~lndicated'in Table 2 below. ,',,,-,, " ~ ~, : :
Le A 26 863 - 15 -:, :
o ~ o c~ o o o o o o o u ~ o u~ ~ oo l~ o u~ o _I f~U~ g O O ~ O O ~0 g 3 ~l ~
: x c~u~ o o o o o o o o o - -oL l'~ 5 o g NO Oo o o l ~
OOOOOIJ~OOO
tJ) ~ t~ O ~ O N ~ IJ~ -- O
: ~ .rl ~ ~ o o Ln O ~ ~ o ~ O O U~ O ~ U~ ~r~ ~ o I
U~ ~ _ ~1 o ~ O ~ ~ gO ~ O
5~ ~; ~ ~ ~
0 ~ O 0 O U~ O O ~ U~
1~ ~ o O o ~ o _I
O u ~ ~., g ~ O ~ ~ u~ ~ N - O
' ~ ~ ~ ' _I 1:1 0 _ ~
~ C~ E 'C h _~._ 0.\ ~ , L rl u11~ c.~ o u~ ~::
U U~ ~ C E-- L ~ cL :>
~ ~ E L J ~ 3 L N
h L-- ~E O -- ~ ~ O
tr) O L L O J O _ U a~ u .4 ~ _, 3 L m ~J C C U L
0 ~ _ ~ ~ ~ E~
E~E~ *
Le A 26 863 7 ~
., , ,, , ExamPle 15 Action against bacteria Active compounds according to the invention in concentrations of l to 5000 ppm are added to an agar , containing broth as the nutrient medium. The nutrient medium is now infected with the specific test organisms listed in Table II, and the infected medium i5 kept for 2 weeks at 28C and 60 to 70~ relative atmospheric , humidity. The MIC is the lowest concentration of active compound at which no growth whatsoever of the microbe species used takes place. The MIC values can be found in -Table 3.
Table 3 MIC values indicated in mg/l of the active lS compounds indicated below acting on bacteria.
MIC in mq/l of the active compounds Test organisms Compound of Example No.
Escherichia coli 200 1000 200 150 750 500 S~aphylococcus 2001000 200 500 500 100 aureus ~;
: .
. , Example 16 tAction against slime organisms) ; The compounds to be tested, dissolved in a small amount of acetone, are applied in Allen's nutrient ' 1~ ' Le A 26 863 - 17 -2 ~ 7 ~
. , solution (Arch. Mikrobiol. 17, 34 to 53 (1952)), which contains 0.2 g of ammonium chloride, 4.0 g of sodium nitrate, 1.0 g of dipotassium hydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesium sulphate, 0.02 g of iron chloride and 1% of caprolactam per 4 litres of sterile water, at concentrations of in each case 0.1 to 100 mg/l. At the beginning of the test, the individual nutrient solutions are infected with slime organisms (about 106 microorganism /ml) which have been isolated from spinning water circuits used in the production of nylon. After being cultured for 3 weeks at room tempera-ture, nutrient solutions containing the minimum inhibi-tory concentration (MIC) or higher concentrations of the iodopropargyl ether to be tested are still completely clear; the copious multiplication of the microbes and slime formation and the associated turbidity, which are observed after 3 to 4 days in nutrient solutions not containing active compound, do not take place.
~able 4 MIC value [mg/l] of the dibromopropanols accord-ing to the invention when acting on slime organisms.
Dibromopropanol of Example MIC [mg/l]
1 5 - ~10 2 s - <10 4 ~5 - (10 :
~'~
Le A 26 863 - 18 -~j 2 ~ 7 ~
. .
, ExamPle 17 ~Action against algae) A mixed culture of green algae, blue-green algae, brown algae and diatoms (Stichococcus bacillaris Naegeli, Euglena gracilis Klebs, Chlorella pyrenoidosa Chick, Phormidium foveolarum Gomont, Oscillatoria geminata Meneghini and Phaeodactylum tricornutum Bohlin) is added to Allen's nutrient solution tArch. Mikrobiol. 17, 34 to 53 (1952)) which contains 0.2 g of ammonium chloride, 4.0 g of sodium~nitrate, 1.0 g of dipotassium hydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesium sulphate and 0.02 g of iron chloride per 4 litres of sterile water, with air being bubbled through. After 2 weeks, the nutrient solution has a deep green-blue colour caused by proliPic growth of algae. The destruction of the algae as a result of adding active compounds accord-ing to the invention can be seen from the decolouration of the nutrient solution. -Table 5 Algae-destroying concentrations [mg/l] of the dibromopropanols according to the invention ` Compound ofDestroying concentration [mg/l]
Example No.
1 50 - ~100 2 )50 - <100 4 so - <IO0 Le A 26 863 - 19 -~""~ ""~,,, `,,~,-;,",, "";", ~'," ' .,.~,, ' , ' :~' ' :~ ;~ ~ :' i': ':, , .~, .
~ 3 7 ~
.
Comparison:
2-bromo-2-nitro-3-hydroxy-propanol >100 ExamPle 18 Fusarium nivale test (rye)tseed treatment The active compounds are applied in form of seed treatment powders. The latter are prepared by mixing (extending~ the specific active compound with ground minerals to give a finely-pulverulent mixture which guarantees uniform distribution on the seed surface.
For seed dressing, the infected seeds together with the treatment powder are shaken for 3 minutes in a sealed glass bottle.
Two batches of 100 rye grains are sown in standard soil at a depth of 1 cm, and the crop is cul-~; 15 tured in a greenhouse at a temperature of about 10C and a relative atmospheric humidity of about 95%, in seed boxes which receive a daily exposure to light of 15 hours.
About 3 weeks after sowing, the plants are evaluated for symptoms of snow mould.
In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the ~; compounds of the following Preparation Examples:
:
Le A 26 863 - 20 - -~ 7 ~
,, Table Fusarium nivale test (rye)/seed treatment Active compound Dosage rate Degree of of active effective-compound in ness in %
mg/kg of seed of the un- :
treated con-trol Br 500 89 Hl 3C6-fH-f -CH2Br OH CN
(Example 6) Br H5C2--CH-f-CH2Br 500 91 OH CN
(Example 4) according to the prior art: (US Patent Specification 4,446,076) Br H3C-C-CH2E~r 500 66 CN
Le A 26 863 - 21 -20~ 7~
~: !
Example 19 Erysiphe test (barley)/protective Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether ; To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. when the spray coating has dried on, the plants~are dusted with~the spores of Erysiphe graminis f.sp. hordei. ~ -- -The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80% to promote the development of -;~
mildew pustules.
Evaluation is carried oùt 7 days after the ~ - -inoculation.
In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of the following Preparation Examples~
~; ":'` .' ' :
, Le A 26 863 - 22 -'~' Table Brysiphe test (barley)/protective Acti~e compound Concentration Degree of of active com- effective-pound in the ness in %
spray liquor in of the un-% by weight treated control Br 0, 00025 75 Br~3fH-C-CH2Br OH CN
~Example 8) according to prior art:
(US Patent Specification 4,446,076) Cl ar ~ I o,00025 o Cl ~ C -CH2Br CN
Le A 26 863 - 23 -.,~ . ' ~ ! , ~ . ' . . . ..
~` ~J~ 7 ~
.
Example 20 Erysiphe test (wheat)/protective Solvent: lO0 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, l part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound until dew-moist. When the spray coating has dried on, the plants are dusted with the spores of Erysiphe graminis f.sp. tritici.
The plants are placed in a greenhouse at a temperature of about 20C and a relative atmospheric humidity of about 80% to promote the development of miIdew pustules.
Evaluation is carried out 7 days after the inoculation.
In this test, a clearly superior activity com-pared with the prior art is shown, for example, by the compounds of the following Preparation Examples:
: -, ':
ke A 26 863 - 24 ---~ 2 ~ 7 ~
Table Erysiphe test (wheat)/protective Active compound Concentration Degree of of active com- effective-pound in the ness in %
spray liquor in of the un-% by weight treated control Br Br ~ CH-~-CH2Br 0,0025 75 OH CN
(Example 8) according to the prior art:
(US Patent Specification 4,446,076) C1 Br Cl ~ ~ C -CH2Br 0,0025 16 C~l ,: , Le A 26 863 - 25 -
Claims (6)
1. Dibromopropanol derivatives of the formula (I), in which R represents an optionally substituted alkyl, cyclo-alkyl, aryl or heteroaryl radical.
2. Dibromopropanol derivatives according to Claim 1, characterized in that R represents a C1-C6-alkyl radical.
3. Dibromopropanol derivatives according to Claim 1, characterized in that R represents a C3-C6-alkyl radical.
4. Process for the preparation of dibromopropanol derivatives of the formula (I), in which R represents an optionally substituted alky, cyclo-alkyl, aryl or heteroaryl radical, characterized in that acryl compounds of the formula (II), in which R has the meaning indicated in the case of formula (I) are brominated in a manner known per se, if appropriate in the presence of an organic solvent which is inert under the reaction conditions.
5. Use of the dibromopropanol derivatives according to Claims 1, 2 or 3 as microbicides in the protection of materials.
6. Use of the dibromopropanol derivatives according to Claims 1, 2 or 3 as fungicides in plant protection.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3920027.2 | 1989-06-20 | ||
| DE3920027A DE3920027A1 (en) | 1989-06-20 | 1989-06-20 | DIBROMPROPANOL DERIVATIVES, METHOD OF PREPARING THEM AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2019174A1 true CA2019174A1 (en) | 1990-12-20 |
Family
ID=6383076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002019174A Abandoned CA2019174A1 (en) | 1989-06-20 | 1990-06-18 | Dibromopropanol derivatives, process for their preparation, and their use |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0403884A3 (en) |
| JP (1) | JPH0331246A (en) |
| CA (1) | CA2019174A1 (en) |
| DD (1) | DD297958A5 (en) |
| DE (1) | DE3920027A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4206528A1 (en) * | 1992-03-02 | 1993-09-09 | Bayer Ag | CYANALKEN DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A MICROBICIDE FOR MATERIAL PROTECTION |
| US6959649B2 (en) | 2000-12-27 | 2005-11-01 | Daicel Chemical Industries, Ltd. | Inflator |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1009578B (en) * | 1973-01-22 | 1976-12-20 | Shell Bv | MICROBIOCIDES |
| US4442122A (en) * | 1981-12-22 | 1984-04-10 | Merck & Co., Inc. | 1,2-Dibromo-2-cyanoalkane antimicrobial compounds |
| US4446076A (en) * | 1981-12-22 | 1984-05-01 | Merck & Co., Inc. | Method of preparing 1,2-dibromo-2-cyano-(substituted)-alkane antimicrobial compounds |
-
1989
- 1989-06-20 DE DE3920027A patent/DE3920027A1/en not_active Withdrawn
-
1990
- 1990-06-07 EP EP19900110763 patent/EP0403884A3/en not_active Withdrawn
- 1990-06-18 CA CA002019174A patent/CA2019174A1/en not_active Abandoned
- 1990-06-18 JP JP2157785A patent/JPH0331246A/en active Pending
- 1990-06-18 DD DD90341779A patent/DD297958A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0331246A (en) | 1991-02-12 |
| EP0403884A2 (en) | 1990-12-27 |
| DE3920027A1 (en) | 1991-01-31 |
| DD297958A5 (en) | 1992-01-30 |
| EP0403884A3 (en) | 1992-04-08 |
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| Date | Code | Title | Description |
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| FZDE | Dead |