EP0000640B1 - Tetrahydro-s-triazine thiones, process for their preparation and acaricidal compositions containing them. - Google Patents

Tetrahydro-s-triazine thiones, process for their preparation and acaricidal compositions containing them. Download PDF

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Publication number
EP0000640B1
EP0000640B1 EP78300162A EP78300162A EP0000640B1 EP 0000640 B1 EP0000640 B1 EP 0000640B1 EP 78300162 A EP78300162 A EP 78300162A EP 78300162 A EP78300162 A EP 78300162A EP 0000640 B1 EP0000640 B1 EP 0000640B1
Authority
EP
European Patent Office
Prior art keywords
lower alkyl
formula
methyl
tetrahydro
group
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
Application number
EP78300162A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0000640A1 (en
Inventor
Michael Raymond Graves Leeming
Subramaniyan Narayanaswami
Alexander Ballingall Penrose
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.)
Pfizer Ltd Great Britain
Pfizer Corp SRL
Original Assignee
Pfizer Ltd Great Britain
Pfizer Corp SRL
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 Pfizer Ltd Great Britain, Pfizer Corp SRL filed Critical Pfizer Ltd Great Britain
Publication of EP0000640A1 publication Critical patent/EP0000640A1/en
Application granted granted Critical
Publication of EP0000640B1 publication Critical patent/EP0000640B1/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/08—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • 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
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • A01N47/20—N-Aryl derivatives thereof

Definitions

  • This invention relates to a series of tetrahydro-s-triazine thiones having useful pesticidal properties.
  • the compounds are effective in destroying one or more stages in the life cycle of ticks which tend to infest the skins of animals such as sheep and cattle, and are therefore especially useful as ectoparasiticidal agents for treating such animals. They also have insecticidal properties, particularly against plant insects such as pea aphids.
  • ticks All stages in the life cycle of the ticks tend to damage the skins of afflicted animals and thereby spoil the state of the skins, with the consequence, for example, that cattle hides and sheep skins intended for the manufacture of leather and sheep skin, respectively, are reduced in quality. Furthermore, the ticks may facilitate the transmission of disease to the afflicted animal, and the general state of health and the quality of flesh of the animal may be detrimentally affected.
  • the present invention therefore provides novel tetrahydro-s-triazin-2[1H]-thiones of the general formula: wherein R is an alkyl, cycloalkyl, adamantyl, lower alkenyl or lower alkynyl group or a substituted- lower alkyl group wherein the substituent is a hydroxy, alkoxy, lower alkanoyloxy, carbamoyloxy, N-lower alkyl-carbamoyloxy, N-cycloalkyl-carbamoyloxy, N-arylcarbamoyloxy, thiocarbamoyloxy, N-lower alkyl-thiocarbamoyloxy, N-cycloalkyl-thiocarbamoyloxy, N-aryl-thiocarbamoyloxy, aryl-sulphonyloxy, mono or di-lower alkylamino or an aryl group;
  • R 1 is a lower alkyl or hydroxy-methyl group
  • X is a hydrogen atom or a lower alkyl group
  • lower applied to a substituent group means that it contains up to six carbon atoms: groups containing three or more carbon atoms may be straight or branched chain.
  • R is an alkyl group, it may contain up to twelve carbon atoms.
  • Halogen means fluorine, chlorine, bromine or iodine.
  • Aryl means a phenyl group which may optionally be substituted with one or more halogen atoms or lower alkyl, lower alkoxy, trifluoromethyl, cyano or hydroxy groups.
  • One preferred group of compounds according to the invention comprises compounds of the formula (I) wherein X is a lower alkyl group, particularly a methyl group at the 4-position. Also preferred are compounds of the formula (I) wherein R I is a lower alkyl group, particularly a methyl group and R is a lower alkyl group, particularly a methyl, isopropyl ort-butyl group, or a cyclohexyl or hydroxyethyl group.
  • Particularly preferred individual compounds of the invention include: 1-(2,4-dimethylphenyl)-3,5-dimethyl-tetrahydro-s-triazin-2 [1H]-thione; 1-(2,4-dimethylphenyl)-3-methyl-5-isopropyl-tetrahydro-s-triazine-2 [1 H]-thione and 1-(2,4-dimethylphenyl) -3-methyl-5-t-butyl-tetrahydro-s-triazine-2[1 H]-thione.
  • R I is alkyl
  • R is alkyl, cycloalkyl, alkenyl, alkynyl or hydroxyalkyl
  • X is hydrogen or halogen
  • Y is hydrogen, halogen or alkyl
  • n is 1 or 2; are disclosed in United States Patent Nos. 3505057 and 3505323 as herbicidal compounds, but there is no disclosure therein of compounds of the formula (1) above in which there is a methyl group at the 2-position of the phenyl group, nor is there any disclosure therein that compounds of the formula (IA) have acaricidal or insecticidal properties.
  • R I is lower alkyl
  • R II substituted thiourea of the formula (II) and an amine RNH 2 in the presence of formaldehyde according to the following equation: where R and X are as previously defined and R 2 is lower alkyl.
  • the reaction is generally performed in the presence of an aqueous organic solvent, e.g. aqueous dioxan, aqueous propanol or aqueous ethylene glycol and may conveniently be carried out by adding the amine to excess aqueous formaldehyde solution and then adding the thiourea, preferably as a solution in an organic solvent e.g. dioxan.
  • the reaction may be performed at a temperature between room temperature and the reflux temperature of the solvent and may take from several hours to several days to complete depending on the nature of the reactants and the temperature employed. We have found that the reaction is preferably performed at a temperature of 45-50°C to avoid the decomposition and formation of bi-products which sometimes occurs at higher temperatures, and generally takes two or three days to go substantially to completion at this temperature.
  • the reaction can with advantage be performed at a higher temperature e.g. by heating on a steam bath, and in this case the reaction is generally complete within 1% to 3 hours.
  • the product crystallises on cooling the solution otherwise the product is conveniently isolated by evaporation of the solvent or alternatively by adding a large excess of water to precipitate the product which is collected by filtration or by extraction into an organic solvent, e.g. diethyl ether, and removal of the solvent.
  • the crude product may be further purified, if desired, by conventional techniques, e.g. by recrystallisation or by chromatography.
  • the acid-addition salts of the compounds of the formula (I) may be made in a conventional manner, e.g. by mixing a solution of the free base in a suitable solvent, e.g. diethyl ether, with a solution of the appropriate acid, e.g. hydrochloric acid, in a suitable solvent, e.g. diethyl ether, and recovering the salt as a precipitate.
  • a suitable solvent e.g. diethyl ether
  • the appropriate acid e.g. hydrochloric acid
  • the starting thioureas of formula (II) are known compounds or they may be readily prepared by conventional reactions. For example the preparation of the compound of formula (II) wherein R 2 and X are each a methyl group is described in J. Chem. Soc., (1929) 945. Other compounds of formula (II) may be prepared in a similar manner by reaction of an appropriately ring substituted aniline derivative with an alkyl isothiocyanate. If desired, the starting thiourea need not be isolated but the crude reaction mixture may be treated directly with formaldehyde and the amine of formula RNH 2 to give the final product of formula (I) in a single step.
  • the amines of formula RNH 2 are all readily available compounds.
  • the compounds of the formula (I) have acaricidal activity, particularly against all stages in the life cycle, including gravid female ticks, of the cattle ticks Boophilus microplus, Haemaphysalis longicornus, Rhipicephalus appendiculatus and Boophilus decoloratus.
  • the eggs are returned to the incubator for a further 3 weeks after which time the percentage of eggs hatching is estimated.
  • the percentage effect is calculated as the overall reduction in the anticipated reproduction of the ticks using the weight of eggs laid and the percentage of eggs hatching.
  • the test may be repeated using smaller amounts of the acaricidal compound.
  • the open end is then crimped to form a sealed packet.
  • the treated paper containing the larvae is returned to the Kilner jar and kept for a further 48 hours in the incubator. 20-50 larvae are placed similarly in an untreated paper envelope to act as controls. At the end of the 48 hour test period the mortality is noted and recorded as a percentage after correction for any mortality among the untreated control ticks.
  • the test may be repeated using smaller amounts of the acaricidal compound.
  • ED 50 results can be obtained from dose response measurements using any of the afore-described tests.
  • Activity against Haemaphysalis longicornus nymphs may be measured in a similar manner to the above larvae test.
  • the invention also provides an acaricidal composition
  • a diluent or carrier may be a solid or a liquid, optionally together with an antioxidant, dispersing agent, emulsifying agent or wetting agent.
  • the compositions of the invention include not only compositions in a suitable form for application but concentrated primary compositions which may be supplied to the user and which require dilution with a suitable quantity of water or other diluent prior to application.
  • Typical compositions of the invention include, for example, dusting powders, dispersible powders, solutions, dispersions, emulsions and emulsifiable concentrates.
  • a dust may be made by mixing the appropriate amount of the finely divided active compound with a solid pulverulent diluent or carrier such as talc, clay, calcite, pyrophyllite, diatomaceous earth, walnut shell flour, silica gel, hydrated alumina, or calcium silicate.
  • a solid pulverulent diluent or carrier such as talc, clay, calcite, pyrophyllite, diatomaceous earth, walnut shell flour, silica gel, hydrated alumina, or calcium silicate.
  • the diluent or carrier is mixed with a solution of the active compound in a volatile organic solvent such as toluene, the solvent being subsequently removed by evaporation.
  • the active compound will be present in the dust in an amount of from 0.25 to about 4% by weight.
  • Dispersible powders of special value for spray applications may be made by adding a suitable dispersing agent to the active compound, or to a dust containing the active compound, so that a stable aqueous dispersion of the active compound is formed on mixing the powder with water.
  • the dispersible powders preferably contain from about 25 to 75% by weight of the active compound.
  • Emulsifiable concentrates comprise a solution of the active compound in a substantially water- immiscible non-toxic organic solvent containing an emulsifying agent.
  • suitable solvents include, for example, toluene, xylene, petroleum oil, and alkylated naphthalenes.
  • the concentrate will contain 5-75 gms. of the active compound per 100 ml. of solution.
  • the concentrates may be diluted with water prior to use to give a typical concentration of the active compound in the aqueous medium of from e.g. about 0.01 to about 0.1% w/v (g/100 ml), or approximately 100 to 1000 p.p.m.
  • the volatile solvents, e.g. toluene and xylene evaporate after spraying to leave a deposit of the active ingredient.
  • the made up spray ordip will generally be an emulsion.
  • compositions of the invention may be applied to ground, such as that around dairies, in order to combat e.g. cattle ticks, thereon. However, it is preferred to treat animals by spraying them or passing them through animal dips.
  • animals particularly cattle
  • acarids particularly cattle ticks
  • animals can be protected from acarids, particularly cattle ticks, by treating the animal externally with an acaricidal amount of a compound of the formula (I) or acaricidal composition as defined above.
  • compositions of the invention may also contain a pesticide, fungicide, additional acaricide, or the like.
  • Formaldehyde (4.86 g, 37% solution, 30 mmole) was added to a solution of 2,4-dimethyl-phenyl thiourea (4.5 g, 24 mmole) in dimethylformamide (40 ml) and the solution was stirred for 15 minutes at room temperature.
  • Methylamine (3.72 g 30 mmole) was added dropwise with stirring and the mixture was heated under reflux at 100°C for 4 hours. The solution was cooled and the solvent removed under vacuum to yield an oil.
  • Acetyl chloride (0.168 g, 1.5 mmole) was added dropwise with stirring to a cooled solution of 1-(2,4-dimethylphenyl)-5-(2-hydroxyethyl)-3-methyl-tetrahydro-s-triazin-2[lH]-thione (0.60 g, 1 mmole) in dry toluene (45 ml) containing triethylamine (0.3 g, 3 mmole). After 10 minutes the solution was allowed to warm to room temperature and stirring was continued for a further 3 hours. The solution was filtered and the solvent removed under vacuum.
  • Example 22 The method of Example 22 was followed using pivaloyl chloride to give 1-(2,4-dimethylphenyl)-3-methyl-5-(2-pivaloyloxy ethyl)-tetrahydro-s-triazin-2[1 H]-thione as an oil.
  • Phenylisocyanate (0.62 g,5.2 mmole) was added to a stirred solution of 1-(2,4-dimethylphenyl)-5-(2-hydroxyethyl )-3-methyl-tetrahydro-s-triazin-2[1H]-thione (1.0 g, 3.5 mmoles) and triethylamine (0.31 g, 5.2 mmole) in dry toluene (40 ml). The mixture was stirred at room temperature for 2 hours and the solvent was then removed under vacuum and the residual gum triturated with petroleum ether (b.p.
  • Example 24 The method of Example 24 was followed using methylisocyanate to give 1-(2,4-dimethylphenyl)-3-methyl-5-(2-N-methyl-carbamoyloxyethyl)-tetrahydro-s-triazin-2[1 H]-thione, m.p.110-113°C.
  • Example 26 The method of Example 26 was followed using methylisothiocyanate to give 1-(2,4-dimethyl- phenyl) -3-methyl-5-(2-N-methyl-thiocarbamoy- loxyethyl)-tetrahydro-s-triazin-2[1 H]-thione, m.p. 82-90°C.
  • Example 26 The method of Example 26 was followed using phenyl isothiocyanate to give 1-(2,4-dimethylphenyl)-3-methyl-5-(2-N-phenyl-thiocarba- moloxyethyl)-tetrahydro-s-triazin-2(1 H]-thione, m.p. 64-70 °C.
  • Aqueous formaldehyde (3.6 g, 4 mmole) was added to a suspension of N-2,4-dimethylphenyl-N'-methyl-thiourea (1.94 g, 2 mmole) in ethylene glycol (500 ml) followed by slow addition of a solution of N,N-dimethyl-ethylenediamine (1.76 g, 2 mmole) in a little ethylene glycol.
  • the mixture was heated for 1 hour at 80-90 °C and then cooled and poured into water.
  • the product was extracted into ether, the ether layer separated, washed with water, dried and evaporated.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP78300162A 1977-07-22 1978-07-19 Tetrahydro-s-triazine thiones, process for their preparation and acaricidal compositions containing them. Expired EP0000640B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB3099877 1977-07-22
GB3099877 1977-07-22

Publications (2)

Publication Number Publication Date
EP0000640A1 EP0000640A1 (en) 1979-02-07
EP0000640B1 true EP0000640B1 (en) 1981-06-03

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EP78300162A Expired EP0000640B1 (en) 1977-07-22 1978-07-19 Tetrahydro-s-triazine thiones, process for their preparation and acaricidal compositions containing them.

Country Status (26)

Country Link
US (1) US4193994A (cs)
EP (1) EP0000640B1 (cs)
JP (1) JPS5826912B2 (cs)
AR (1) AR220140A1 (cs)
AT (1) AT360033B (cs)
AU (1) AU509780B2 (cs)
BR (1) BR7804727A (cs)
CA (1) CA1110622A (cs)
CS (1) CS212231B2 (cs)
DE (1) DE2860744D1 (cs)
DK (1) DK236878A (cs)
EG (1) EG13455A (cs)
ES (2) ES471872A1 (cs)
FI (1) FI66179C (cs)
IE (1) IE47161B1 (cs)
IL (1) IL55182A (cs)
IN (1) IN148647B (cs)
IT (1) IT1097334B (cs)
MX (1) MX5559E (cs)
NZ (1) NZ187927A (cs)
PH (1) PH15775A (cs)
PT (1) PT68326A (cs)
SU (1) SU753359A3 (cs)
YU (1) YU160978A (cs)
ZA (1) ZA784164B (cs)
ZM (1) ZM6178A1 (cs)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1251294A (en) * 1983-04-22 1989-03-14 Mobay Chemical Corporation Polyether polyurethane prepolymers and cast elastomers made therefrom
JPS6046350A (ja) * 1983-08-25 1985-03-13 Otsuka Chem Co Ltd 合金鋳鉄及びその製造方法
US6160114A (en) * 1996-11-14 2000-12-12 American Home Products Corporation Substituted tetrahydro-1,3,5-triazin-2[1H]-thiones as anti-atherosclerotic agents
CA2271728A1 (en) * 1996-11-14 1998-05-22 American Home Products Corporation Substituted tetrahydro-1,3,5-triazin-2[1h]-thiones as anti-atherosclerotic agents

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505057A (en) * 1962-03-22 1970-04-07 Du Pont Method for the control of plants
US3505323A (en) * 1963-12-06 1970-04-07 Du Pont Tetrahydro-s-triazin-2-(1h)-ones and thiones

Also Published As

Publication number Publication date
FI66179B (fi) 1984-05-31
IN148647B (cs) 1981-04-25
JPS5424884A (en) 1979-02-24
ZA784164B (en) 1979-07-25
FI66179C (fi) 1984-09-10
AU509780B2 (en) 1980-05-22
IL55182A (en) 1983-05-15
ATA522978A (de) 1980-05-15
IL55182A0 (en) 1978-09-29
ES479261A1 (es) 1979-12-16
EG13455A (en) 1981-12-31
EP0000640A1 (en) 1979-02-07
NZ187927A (en) 1981-03-16
PH15775A (en) 1983-03-24
DE2860744D1 (en) 1981-09-10
CS212231B2 (en) 1982-03-26
YU160978A (en) 1982-08-31
AR220140A1 (es) 1980-10-15
PT68326A (en) 1978-08-01
IE781452L (en) 1979-01-22
JPS5826912B2 (ja) 1983-06-06
US4193994A (en) 1980-03-18
AT360033B (de) 1980-12-10
BR7804727A (pt) 1979-04-17
FI782192A7 (fi) 1979-01-23
ES471872A1 (es) 1979-10-01
CA1110622A (en) 1981-10-13
IE47161B1 (en) 1984-01-11
IT7826001A0 (it) 1978-07-21
SU753359A3 (ru) 1980-07-30
IT1097334B (it) 1985-08-31
ZM6178A1 (en) 1980-03-21
DK236878A (da) 1979-01-23
MX5559E (es) 1983-10-10
AU3825378A (en) 1980-01-24

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