IE43715B1 - Nitrotrifluoromethyl substituted diphenylamines,their preparation and rodenticidal compositions - Google Patents
Nitrotrifluoromethyl substituted diphenylamines,their preparation and rodenticidal compositionsInfo
- Publication number
- IE43715B1 IE43715B1 IE1765/76A IE176576A IE43715B1 IE 43715 B1 IE43715 B1 IE 43715B1 IE 1765/76 A IE1765/76 A IE 1765/76A IE 176576 A IE176576 A IE 176576A IE 43715 B1 IE43715 B1 IE 43715B1
- Authority
- IE
- Ireland
- Prior art keywords
- methyl
- dinitro
- chloro
- bromo
- trifluoromethyldiphenylamine
- Prior art date
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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
- A01N33/18—Nitro compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Novel diphenylamines of the formula where the substituents are defined in claim 1, are prepared. These compounds are obtained by reacting an aniline which has the substituents R<1>-R<5> with a 2-halo-5-nitrobenzotrifluoride. The resulting compound is subsequently subjected to n-alkylation to introduce the substituent R. If necessary, halogen substituents are introduced by halogenation in the 2-, 4- and/or 6- position. The novel compounds are used as active substance in rodenticides.
Description
The present invention relates to novel diphenylamine compound having alkyl substituents on the amino nitrogen, to a process for the preparation thereof, and to compositions and methods relating thereto. One phenyl > ting bears dinitro-trifluoromethyl substitution, and the other is preferably substituted with halogen or pseudohalogen groups. The novel compounds are useful as rodenticides.
This invention belongs to the rodenticidal art and .0 provides new compounds, methods and compositions for reducing populations of rats or mice.
It has long been known that rats and mice must be controlled. Rats and mice are known carriers of many diseases of which bubonic plague is the best known.
L5 The pestiferous animals also, when sharing the habitations of mankind, soil and contaminate the areas in which they live, and destroy buildings and their contents by their tunnelling and nest-building. The animals also consume foodstuffs, and contaminate what they do not consume. A >0 colony of rats in a grain-storage building can consume or destroy substantial‘amounts of food.
Many kinds of rodenticides have been, and still are, in use. Metallic poisons, such as arsenic and thallium compounds, are still in use, but obviously pose serious hazards to people and useful animals. Organic chemical poisons, of which warfarin is the best known, are in extremely wide use and have served well. However, rodents are developing resistance to such poisons.
Rodenticides are usually presented to rats or mice in the form of mixtures with foodstuffs. The concentration
-2ΰ 371 of rodenticide in the mixture is adjusted so that the rodents consume an amount of the rodenticide which is either acutely or chronically lethal. It is advisable not to make the mixture so concentrated that the rodent dies immediately, or even soon after eating. Rodents, and especially rats, are intelligent enough to understand the causal relationship between feeding and death if the time interval is very short. Thus, the best practice is to adjust the concentration of the rodenticide so that the
].(j rodents will be poisoned over a number of feedings at the poison bait.
In special circumstances, rodenticides are sometimes mixed in drinking water, or prepared as tracking powders, which are deposited in runways used by the rodents.
After the animals have walked through the loose poison powder, they lick their feet clean and thus ingest the rodenticide.
Tertiary diphenylamines such as those of the present invention have not previously been known. Secondary
ZO diphenylamines, however, have been known in the prior art to be fungicides and insecticides. It will be noted that the prior art does not enable the reader to prepare the present compounds, as will be explained in further detail below. Rodenticidal diphenylamines have not previously been known.
2t> The present invention provides novel diphenylamine compounds of the formula
.5 wherein R represents methyl, ethyl or propyl;
R3 represents hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, nitro or trifluoromethyl;
R and R independently represent hydrogen, fluoro, chloro, bromo, nitro, methyl or trifluoromethyl, provided that no 2 5 more than one of R and R represents nitro;
R3 and R4 independently represent hydrogen, methyl, fluoro, chloro, bromo or trifluoromethyl; provided that
2 3 4 5
a) no more than one of R , R , R , R and R
4 represents methyl, except that R and R may both represent methyl;
b) when R3-, R3, R3, R^ or R^ represents methyl
or fluoro, two or three of R , R and R represent chloro or bromo;
c) no more than one of R3, R3, R3, R^ and R^ . 3 represents trifluoromethyl, except that R and R may both represent trifluoromethyl;
1
d) when R or R represents trifluoromethyl, R represents chloro or bromo;
4
e) when one and only one of R and R represents
2 trifluoromethyl, two or three of R , R and
R3 represent chloro or bromo;
2 3 4 5
f) no more than four of R , R , R , R and R represent hydrogen;
g) two fluorine atoms are not adjacent to each other;
1
h) when R or R represents nitro, R represents chloro, bromo or nitro;
>5
-443715
i) when one of R3, R2, R3, R4 or R5 represents 12 3 4 trifluoromethyl, none of R , R , R , R and 5
R represents fluoro or methyl.
The present invention also provides a process for preparing novel diphenylamine compounds of formula I, which comprises
a) reacting an aniline compound of the formula
R — ·;
J f \ / n-NHR
IX
6 wherein R is hydrogen, methyl, ethyl or propyl; and r\ R2 , R3 , R4 and R3 are as defined above; with a 2-halo-5-nitrobenzotrifluoride compound of the formula ο N.....·*, V~/ III wherein X is halo and R is hydrogen or nitro, provided that R36 and at least one of R2 and R3 are hydrogen when 17 .
lb R is nitro;
b) N-alkylating the compound obtained in step a) wherein i 6
R is hydrogen;
c) nitrating the compound obtained in step b) wherein
R is hydrogen; and
d) if desired halogenating the compound obtained in step c) which lacks the desired halogen substituents.
The invention further provides a method of reducing a population of rats or mice which comprises supplying to a locus frequented by the rats or mice a rodenticidally-effective amount of a rodenticidal composition comprising an inert carrier and as active ingredient a rodenticidally-effective concentration of a diphenylamine compound of formula I wherein the symbols have the meanings stated above.
The invention also provides rodenticidal compositions which comprise an inert carrier and as active ingredient an effective rodenticidal concentration of a diphenylamine compound of formula I wherein the symbols have the meanings stated above.
All of the compounds below will be named as diphenylamines for the sake of consistency and clarity, even though the rules of nomenclature may call for some compounds to be named otherwise.
All percentages and parts described hereafter refer to percentages and parts by weight, and all tempera3 tures are on the Celsius scale.
The following exemplary compounds are mentioned to ensure that the reader fully understands the compounds of formula I. It will be understood that the invention is by no means limited to the compounds named below.
2,6-dibromo-4-chloro-N-methyl-21,41-dinitro-6'trifluoromethyldiphenylamine
2-bromo-4-chloro-N-ethyl~2',4'-dinitro-6'-trifluoromethyldiphenylamine
2,4-dichloro-N-methyl-2',4'-dinitro-6'-trifluoro0 methyldiphenylamine
-6^3715
2.6- dibromo-4-cyano-N-methyl-2', 4'-dinitro-6'trifluoromethyldiphenylamine
2-chloro-2',41-dinitro-N-propy.l-4,6'-bis (trifluoromethyl)diphenylamine
N-ethyl-2,6-dibromo-4-iodo-2',4'-dinitro-6'trifluoromethyldiphenylamine
N-propyl-2,6-dichloro-2’,4,4*-trinitro-6'trifluoromethyldiphenylamine
2-bromo-6-chloro-2',4,4'-trinitro-N-propyl10 6'-trifluoromethyldiphenylamine
4-bromo-2-chloro-N-methyl-2',4'-dinitro-6'tr i fluoromethyldiphenylamine
2,4-dibromo-6-chloro-N-ethyl-2',4'-dinitro-6'trifluoromethyldiphenylamine
2-bromo-6-chloro-N-methyl-2', 4' -dinitro-4, 6' bis(trifluoromethyl)diphenylamine
2-chloro-N-methyl-2',4,4'-trinitro-6'-trifluoromethyldiphenylamine
2.6- dibromo-4-iodo-N-methyl-2',4'-dinitro-6'20 trifluoromethyldiphenylamine
N-methyl-2,4,6-trichloro-21,4'-dinitro-6'trifluoromethyldiphenylamine
2.6- dibromo-N-methyl-2',4,4'-trinitro-6'-trifluoromethyldiphenylamine
N-ethyl-2-bromo-2‘,4'-dinitro-4,6'-bis(trifluoromethyl) diphenylamine
2.6- dibromo-4-cyano-2',4'-dinitro-N-propyl-6'trifluoromethyldiphenylamine
2.4.6- trichloro-2',4'-dinitro-N-propyl-6'30 trifluoromethyldiphenylamine
-74 3 715
2.6- dibromo-4-chloro-N-ethyl-2', 4'-dinitro6'-trifluoromethyldiphenylamine
2.6- dichloro-N-ethy1-21,4'-dinitro-4,6’-bis(tri fluoromethyl)diphenylamine
2.6- dibromo-N-methyl-2', 4'-dinitro-4,6'-bis(tri fluoromethyl)diphenylamine
2-chloro-4-iodo-N-methyl-2',41-dinitro-6'trifluoromethyldiphenylamine
2.6- dichloro-4-cyano-N-ethyl-2',4'-dinitro-6'I trifluoromethyldi’phenyiamine
2,4-dibromo-2',41-dinitro-N-propyl-6 *-trifluoro methyldiphenylamine
4-bromo-2-chloro-N-ethyl-2',41-dinitro-6'trifluoromethyldiphenylamine
2-chloro-4-cyano-N-methyl-21,4'-dinitro-61trifluoromethyldiphenylamine
2-bromo-N-ethyl-2',4,4'-trinitro-6 *-trifluoromethyldiphenylamine
2-chloro-4-iodo-2',4'-dinitro-N-propyl-6'-tri) fluoromethyldiphenylamine
2.6- dichloro-N-ethyl-2',4,4'-trinitro-6'-trifluoromethyldiphenylamine
2-bromo-4,6-dichloro-N-ethyl-21,41-dinitro-6'trifluoromethyldiphenylamine i 2-bromo-6-ohloro-4-cyano-2',4'-dinitro-N-propyl
6'-trifluoromethyldiphenylamine
2.6- dichloro-N-ethyl-4-iodo-2',4 *-dinitro-61 trifluoromethyldiphenylamine
N-ethyl-2,6-dibromo-4-chloro-2',4'-dinitro-6'0 trifluoromethyldiphenylamine
-843715
2-chloro-4-cyano-2',4'-dinitro-N-propyl-6'-trifluoromethyldiphenylamine
2-bromo-4-chloro-N-methyl-2', 4'-dinitro-6'-trifluoromethyldiphenylamine
2-chloro-2',4,4'-trinitro-N-propyl-6'-trifluorome thy ldipheny lamine
2-bromo-N-ethyl-4-iodo-2',4'-dinitro-6'-trifluoromethy Idiphenylamine
2,4-dichloro-N-ethyl-2',4'-dinitro-6'-trifluoromethy ldipheny lamine
2,4,6-tribromo-N-ethyl~2',4'-dinitro-6'-trifluoromethy ldipheny lamine
N-propyl-2-bromo-4-cyano-2',4'-dinitro-6'-trifluoromethyldiphenylamine
2-chloro-N-methyl-2',4'-dinitro-4,61-bis{trifluoromethyl) diphenylamine
N-methyl-2-bromo-4-iodo-2’,41-dinitro-6'-trifluoromethyldiphenylamine
2-bromo-4,6-dichloro-N-methyl-2',4’-dinitro-6'trifluoromethyIdiphenylamine
2-bromo-6-chloro-4-cyano-N-methyl-21,4'-dinitro6'-trifluoromethyIdiphenylamine
4-cyano-N-methyl-2',4'-dinitro-61-trifluoromethy1diphenylamine
2-bromo-4-chloro-2',4'-dinitro-N-propyl-6'-trifluoromethyldiphenylamine
-9N-ethyl-21,4,41-trinitro-6'-trifluoromethyldiphenylamine
N-methyl-2-bromo-21,4,4’-trinitro-6'-trifluoro methyldiphenylamine
2,6-dichloro-4-iodo-2',41-dinitro-N-propyl6’-trifluoromethyldiphenylamine
2-bromo-6-ehloro-N-methyl-21,4,41-trinitro-6'trifluoromethyldiphenylamine
N-propyl-4-bromo-2-chloro-21,4'-dinitro-6'-tri 10 fluoromethyldiphenylamine
4-bromo-2,6-dichloro-21,4'-dinitro-N-propyl-6' trifluoromethyldiphenylamine
2,6-dibromo-2',4,4'-trinitro-N-propyl-6'-trifluoromethyldiphenylamine
2-bromo-6-chloro-4-iodo-N-methyl-2',4'-dinitro
6'-trifluoromethyldiphenylamine
4-bromo-2,6-dichloro-N-methyl-21,4'-dinitro-6' trifluoromethyldiphenylamine
2-bromo-6-chloro-N-ethyl-4-iodo-21,4'-dinitro20 61-trifluoromethyldiphenylamine
2-bromo-4-cyano-N-ethyl-2',4'-dinitro-6'-trifluoromethyldiphenylamine
2,4-dibromo-6-chloro-2’,4 *-dinitro-N-propyl-6' trifluoromethyldiphenylamine
-10•53715
2-bromo-4-chloro-6 ,N-dimethyl-2 ’, 4 ’ -dinitro-6 ’ trifluoromethyldiphenylamine
2,4-dichloro-3-methyl-21,4'-dinitro-N-propyl6'-trifluoromethyldiphenylamine
2,4-dibromo-2',4'-dinitro-N-propyl-6,61-bis(trifluoromethyl) diphenylamine
4-bromo-2-chloro-N-ethyl-2',4'-dinitro-6, 6 ’ bis{trifluoromethyl)diphenylamine
2.6- dichloro-4,N-dimethyl-2',41-dinitro-6'-tri10 fluoromethyldiphenylamine
2-bromo-4,6-dichloro-N-methy1-21,4'-dinitro3,6'-bis(trifluoromethyl)diphenylamine
2.4.6- trichloro-3,N-dimethyl-2’,4'-dinitro-6'trifluoromethyldiphenylamine
2,4-dibromo-N-ethyl-6-methyl~21,4'-dinitro-6'trifluoromethyldiphenylamine
4-bromo-2-chloro-2',4'-dinitro-N-propyl~3,6'bis(trifluoromethyl)diphenylamine
2.6- dibromo-2 *,41-dinitro-N-propyl-4,61-bis(tri20 fluoromethyl)diphenylamine
N-ethyl-2,4-dinitro-3',5',6-tris(trifluoromethyl)diphenylamine
2.4.6- tribromo-N-ethyl-3-methyl-2',4'-dinitro6'-trifluoromethyldiphenylamine
2,6-dibromo-4-chloro-N-ethyl-2',4'-dinitro-3,6’bis(trifluoromethyl)diphenylamine
4-bromo-2,6-diehloro-N-ethyl-3-methyl-2',4'dinitro-6'-trifluoromethyldiphenylamine
2.6- dibromo-N-ethyl-4-methyl-21,4'-dinitro-6'30 trifluoromethyldiphenylamine
-114S71S
2-bromo-4-chloro-2', 41-dinitro-N-propyl-6,6 *bis(trifluoromethyl)diphenylamine
2-bromo-6-chloro-3,N-dimethyl-2',4'-dinitro-6'trifluoromethyldiphenylamine
2-bromo-4,6-dichloro-3-methyl-2',4'-dinitro-Npropyl-6 '-trifluoromethyldiphenylamine
4-bromo-2-chloro-5,N-dimethyl-2’,4'-dinitro-6'trifluoromethyldiphenylamine
4-bromo-2,6-dichloro-N-methy1-2',4'-dinitro3,6'-bis(trifluoromethyl)diphenylamine
2-bromo-6-chloro-N-ethyl-2',4'-dinitro-4,6'bis(trifluoromethyl)diphenylamine
2.4- dichloro-N-methyl-2',4'-dinitro-3,6'-bis(trifluoromethyl) diphenylamine
2.4- dibromo-3-methyl-2',4'-dinitro-N-propyl-6'trifluoromethyldiphenylamine
4-bromo-2-chloro-6,N-dimethyl-2',4'-dinitro-6'trifluoromethyldiphenylamine
2.4- dibromo-N-ethyl-2',4'-dinitro-3,6'-bis(trifluoromethyl)diphenylamine
2.4.6- tribromo-2', 41-dinitro-N-propyl-3,6'-bis(trifluoromethyl)diphenylamine
2-bromo-4-chloro-N-ethyl-3-methyl-21,4'-dinitro6 *-trifluoromethyldiphenylamine
2.4.6- trichloro-N-ethyl-2',4'-dinitro-3,6'-bis(trifluoromethyl)diphenylamine
2.6- dibromo-4-chloro-3-methyl-2',4'-dinitro-Npropyl-6 ' -trifluoromethyldiphenylamine
2-bromo-4-chloro-N-methyl-2',4'-dinitro-3,6'bis (trifluoromethyl)diphenylamine
-122.6- dichloro-2',4’-dinitro-N-propyl-4,61-bis(trifluoromethyl) diphenylamine
2,4-dibromo-3,5-dimethyl-2',4'-dinitro-N-propyl6'-trifluoromethyldiphenylamine
2,6-dichloro-3,5-N-trimethyl-2',4'-dinitro61-trifluoromethyldiphenylamine
2-bromo-4-chloro-N-ethyl-3,5-dimethyl-2', 4' dinitro-6'-trifluoromethyldiphenylamine
4-bromo-2-chloro-3,5,N-trimethyl-21,4'-dinitro10 6'-trifluoromethyldiphenylamine
4-bromo-N-methyl-2',41-dinitro-3,5,6'-tris{trifluoromethyl ) diphenylamine
2.4.6- trichloro-2',4'-dinitro-N-propyl-3,5,6'tris(trifluoromethyl)diphenylamine j .j 2,4-dibromo-N-ethyl-2*,4'-dinitro-3,5,6'-tris(tri fluoromethyl)diphenylamine
2.6- dibromo-4-chloro-N-ethyl-2' , 4'-dinitro-3,5,6' tris(trifluoromethyl)diphenylamine
2.4.6- tribromo-3,5,N-trimethyl-2',4'-dinitro-6'20 trifluoromethyldiphenylamine
4-ch.Loro-N-ethyl-2',4'-dinitro-2,6'-bis(trifluoro methyl)diphenylamine
4-bromo-2',41-dinitro-N-propyl-2,6'-bis(trifluoro methyl)diphenylamine
2,6-dibromo-N-ethyl-3-methyl-2',4,4'-trinitro6'-trifluoromethyldiphenylamine
2-bromo-6-chloro-3,N-dimethyl-2',4,4'-trinitro6'-trifluoromethyldiphenylamine
2.6- diehloro-N-ethyl-3-methyl-2',4,4'-trinitro30 6’-trifluoromethyldiphenylamine
-13s J'l i ϋ
2.6- dibromo-4-cyano-3-methyl-21,4'-dinitroN-propyl-6 '-trifluoromethyldiphenylamine
2-bromo-6-chloro-4-cyano-N-ethyl-3-methyl-2',41 dinitro-6 *-trifluoromethyldiphenylamine
2,6-dichloro-4-cyano-3,N-dimethyl-2',4·-dinitro
61-trifluoromethyldiphenylamine
2-bromo-6-chloro-2',4'-dinitro-N-propyl-4,6'bis(trifluoromethyl)diphenylamine
2.6- dibromo-N-ethyl-2', 4'-dinitro-4,6'-bis(triLO fluoromethyl)diphenylamine
2.6- dibromo-N-methyl-2',4,4'-trinitro-3,6 *-bis(trifluoromethyl)diphenylamine
2-bromo-6-chloro-N-ethyl-2',4,4'-trinitro-3,6'bis(trifluoromethyl)diphenylamine
2,6-dibromo-4-cyano-N-ethyl-21,4'-dinitro-3,6'bis(trifluoromethyl)diphenylamine
2-bromo-6-chloro-2’,4,4’-trinitro-N-propyl-3,6' bis(trifluoromethyl)diphenylamine
2,3,5-trichloro-N-methyl-2*,4,4’,6-tetranitro0 6'-trifluoromethyldiphenylamine
4-bromo-N-ethyl-2,21,41-trinitro-6 *-trifluoromethyldiphenylamine
4-chloro-2,2',4'-trinitro-N-propyl-61-trifluoro methyldiphenylamine
2,4-dibromo-N-ethyl-2',4',6-trinitro-5,6'-bis(trifluoromethyl)diphenylamine
4-bromo-2-chloro-N-methyl-21,4',6-trinitro-61trifluoromethyldiphenylamine
-142.3.4.5.6- pentachloro-N-methyl-2',41-dinitro-6'trifluoromethyldiphenylamine
2.3.4.5.6- pentabromo-N-ethyl-2',4'-dinitro-6'trifluoromethyldiphenylamine
4-bromo-2,5,6-trichloro-3-fluoro-2',4'-dinitroN-propyl-6'-trifluoromethyldiphenylamine
2.3.5.6- tetrabromo-4-fluoro-N-methyl-2 ', 4'-dinitro-6 '-trifluoromethyldiphenylamine
4-bromo-2,3,5,6-tetrachloro-N-methyl-21,4'-di10 nitro-6’-trifluoromethyldiphenylamine
3.5- dibromo-2,4,6-trichloro-2', 4'-dinitro-Npropyl-6 ' -trifluoromethyldiphenylamine
2.3.5.6- tetrachloro-N-ethyl-4-iodo-2',41-dinitro6’-trifluoromethyldiphenylamine
2,4,6~tribromo-3,5-dichloro-N-methyl-2',4'-dinitro61-trifluoromethyldiphenylamine
2.3.4.6- tetrachloro-N-ethyl-5-fluoro-2',4'-dinitro6'-trifluoromethyldiphenylamine
3-bromo-2,4,5,6-tetraohloro-N-methyl-2',4'-di20 nitro-6'-trifluoromethyldiphenylamine
2.3.6- tribromo-5-fluoro-4-iodo-2',4'-dinitro-Npropyl-6' -trif luoromethyldiphenylamine
2.3.4.5- tetrachloro-6-fluoro-N-methyl-2',4'-dinitro-6 ' -trifluoromethyldiphenylamine
2,3,4,6-tetrachloro-N-ethyl-2',4'-dinitro-6'tr ifluoromethyldiphenylamine
2.3.5.6- tetrabromo-2',4’-dinitro-N-propyl-6'trifluoromethyldiphenylamine
154371S
2.6- dibromo-3,5-dichloro-N-ethyl-2’,4'-dinitro6'-trifluoromethyldiphenylamine
2.3.4- tribromo-S-fluoro-N-methyl-2' ,4'-dinitro61-trifluoromethyldiphenylamine
2,3,4-trichloro-N-ethyl-5-fluoro-2', 4'-dinitro6'-trifluoromethyldiphenylamine
2.6- dibromo-4-fluoro-N-methyl-2', 4'-dinitro-6'trifluoromethyldiphenylamine
2.4- dichloro-3-fluoro-2',4'-dinitro-N-propyl.0 6’-trifluoromethyldiphenylamine
2-bromo-4-chloro-6-fluoro-N-methyl-2',4'-dinitro6'-trifluoromethyldiphenylamine
2.6- dibromo-3-fluoro-4-iodo-2',4'-dinitro-Npropyl-6 '-trifluoromethyldiphenylamine lb 2,3,6-trichloro-4-fluoro-N-methyl-2',4'-dinitro6'-trifluoromethyldiphenylamine
2- chloro-N-methyl-2',4'-dinitro-6'-trifluoromethyldiphenylamine
3- bromo-N-methyl-2',4'-dinitro-6'-trifluoromethyl :0 diphenylamine
2.6- dichloro-4-fluoro-2',4'-dinitro-N-propyl6*-trifluoromethyldiphenylamine
2.4.6- trichloro-N-ethyl-3-fluoro-2',4'-dinitro61-trifluoromethyldiphenylamine
4-bromo-2,6-dichloro-3-fluoro-N-methyl-2',4'dinitro-6'-trifluoromethyldiphenylamine
2.4- dibromo-N-ethyl-6-fluoro-2',4'-dinitro-6'trifluoromethyldiphenylamine
-164 3 713
2,6-dichloro-4-cyano-3-fluoro-N-methyl-2', 4'-dinitro-6 ’-trifluoromethyldiphenylamine
4-bromo-N-ethyl-2',4'-dinitro-2,61-bis(trifluoromethyl) diphenylamine
2,6-dichloro-3-fluoro-N,4-dimethy1-2’,4'-dinitro6'-trifluoromethyldiphenylamine
2.4- dibromo-3-chloro-N-methyl-21,4’-dinitro6,6'-bis(trifluoromethyl)diphenylamine
2,4,4'-trinitro-N-propyl-6-trifluoromethyldi10 phenylamine
3.4- dichloro-N-methyl-2',4'-dinitro-6'-trifluoromethyldiphenylamine
2.6- dichloro-3-fluoro-N-methyl-2',4,4'-trinitro6'-trifluoromethyldiphenylamine
4-iodo-N-methyl-2',4'-dinitro-6'-trifluoromethyldiphenylamine
2.6- dichloro-N-ethyl-3-bromo-2',4'-dinitro-4,6'bi s (tr if 1 uoronio t by1)d i pheny1 amine
3.5- dibromo-N-methyl-2',4'-dinitro-6'-trifluoro20 methyldiphenylamine
2-bromo-4-chloro-6-fluoro-N,3-dimethy1-2',4'-dinitro-6 '-trifluoromethyldiphenylamine
2.6- dichloro-N-methyl-2',4'-dinitro-3,5,6'tris(trifluoromethyl)diphenylamine
-173715
N-methyl-2,4-dinitro-4',6-bis(trifluoromethyl)diphenylamine
4-chloro-N-methyl-2 ' , 4'-dinitro-61-trifluoromethy Idiphenylamine
4-bromo-2-ohloro-N-ethyl-6-methyl-2',4'-dinitro6’-trifluoromethyIdiphenylamine t
3,5-dibromo-2-chloro-N-methyl-2',41-dinitro-6'trifluoromethyldiphenylamine
2.4- dichloro-N-ethyl-3-methyl-2',4',6-trinitro) 6'-trifluoromethyIdiphenylamine
2.3.4- tribromo-5-fluoro-2·,4',6-trinitro-N-propyl 6’-trifluoromethyIdiphenylamine
2,2', 4,4'-tetranitro-N-propyl-61-trifluoromethyldiphenylamine
2,4,6-trichloro-3,5-difluoro-N-methyl-2',4’-dinitro-6 1-trifluoromethyldiphenylamine
2.4- dibromo-6-chloro-N-ethyl-3,5-difluoro-2',4'dinitro-6'-trifluoromethyIdiphenylamine
2.4- dibromo-3,5-dichloro-N-methyl-2',41-dinitro) 6,6'-bis(trifluoromethyl)diphenylamine
2.4- diohloro-N-ethyl-3,5-difluoro-21,4',6trinitro-6'-trifluoromethyldiphenylamine
4-bromo-2-chloro-3,5-difluoro-6-methy1-2',41 dinitro-N-propyl-6'-trifluoromethyldiphenylamine
2,6-dibromo-3,5-difluoro-N-methyl-2',4’-dinitro6'-trifluoromethyldiphenylamine
2.4- dichloro-N-ethyl-3,5-difluoro-2',4'-dinitro6'-trifluoromethyIdiphenylamine
-182.6- dichloro-3,5-difluoro-4-iodo-N-methy1-2',41dinitro-61-trifluoromethyldiphenylamine
2.6- dichloro-4-cyano-N-ethyl-3,5-difluoro-21,4’dinitro-61-trifluoromethyldiphenylamine
2,6-dibromo-3,5-difluoro-2’,4,4’-trinitro-Npropyl-6’-trifluoromethyldiphenylamine
2.4- dichloro-3,6-difluoro-N-methyl-2’,4'-dinitro61-trifluoromethyldiphenylamine
2-bromo-4-chloro-3,6-difluoro-2',4'-dinitro-N10 propyl-6'-trifluoromethyldiphenylamine
4-bromo-2-chloro-N-methyl-2',4'-dinitro-6,6'bis(trifluoromethyl)diphenylamine
4-bromo-21,41-dinitro-N-propyl-6'-trifluoromethyldiphenylamine
2,4-dibromo-N-ethyl-2', 4'-dinitro-6,6'-bis(trifluoromethyl) diphenylamine
3.4- dibromo-N-methy1-2',4'-dinitro-6'-trifluorome thyldiphenyiamme
The following are the preferred compounds of this invention.
2.4.6- trichloro-N-ethyl-2',4’-dinitro-6'-trifluoromethyldiphenylamine
2.4.6- trichloro-N-methyl-21,41-dinitro-6 *-trifluoromethyldiphenylamine
2,4-dibromo-N-methyl-2',4'-dinitro-6'-trifluoromethyldiphenylamine
-192,4-dibromo-6-chloro-N-methyl-21,4'-dinitro6'-trifluoromethyldiphenylamine
2.4.6- tribromo-N-methyl-21,4’-dinitro-6'-trifluoromethy ldiphenylamine
N-methyl-2,4-dinitro-3',51-6-tris(trifluoromethyl) diphenylamine
2.6- dibromo-4-chloro-N-methyl-2',4 *-dinitro6'-trifluoromethyldiphenylamine
4-bromo-2,6-dichloro-N-methyl-2',4'-dinitro-6'LO trifluoromethyldiphenylamine
Preferred compounds are those wherein R represents 12 5 methyl, and those wherein R , R and R are halo.
Another preferred group of compounds are those 2 5 wherein R and R independently represent hydrogen, chloro, .5 bromo or fluoro, R represents methyl, and R^ represents hydrogen, chloro or bromo.
The new compounds of formula I cannot be prepared by simple direct methods, and are therefore prepared by a multiple-step process. It would be expected that such ;o compounds could be synthesized by the direct reaction of a substituted N-alkyl aniline with 2-chloro-3,5-dinitrobenzotrifluoride. Alternatively, one might expect to be able to prepare the corresponding secondary diphenylamine, and alkylate the nitrogen with an alkyl iodine or a similar alkylating reagent. In fact, except for those compounds that have either the 2- or 6-position unsubstituted, neither process has been found to be operable. For the great majority of the compounds, one of the embodiments of the process outlined below must be used.
A.
OaN—·;
z~\ R ϊ
P .·—«5
-halo . Η—N—4 S—R®
CFs Xr>>
OaN—<
Z\ , /~\ )·—halo + H2N—/· \ Z *“k n1 Ο n
OaN—' z~\ ϊ Ϊ
-.-«-/ \ »« /f -N—.
/·—·\
-IQ Γ,θ fi
OaN—1 •—·ν P yi—K .( ).-4-.( ).-p® *~\F /·—\ CFs R10 R® product ς- nitration optional halogenation
-21In the above formula, R6, R7, R8, R9 and R^8, respectively, have the values of R2, R2, R2, R^ and R2, respectively, or any of them may represent hydrogen. The process may be carried out using a starting aniline which bears some or all of the desired R1 through R2 substituents of the product, or with an unsubstituted aniline, depending upon the substituents, of the desired product. The halogen and nitro substituents of the aniline ring may be added at the end of the process. Thus, only any cyano, methyl or trifluoromethyl substituents of the aniline ring need be in
I place before the two rings are coupled. The final nitration step of the process above not only provides the 2-nitro group of the benzotrifluoride ring of the new compounds, but can also provide a nitro group on the aniline ring, when j such a group is desired.
The term halo indicates that the benzotrifluoride ring may be substituted with any convenient halogen atom. Chlorine and fluorine atoms are preferred, and chlorine is usually most convenient.
-22B.
ο ν~·:
,·—halo » Η Ν—·;
/V \ ___ / /*—·\
R15 R1<
X ZR13 /--ί η
/ \ , °χ-< /—Ν—\ /'-R ζ·=\
NO
-4‘
R12 \ ζ
Λ--·.
„ Β__Ζ \4-/ W \ ___ / ζ· ·\
R16 R14 product \|ζ optional halogenation
The alkylation step of embodiment B above is sterically hindered by ortho substituents on the aniline ring. Accordingly, R11, R12, R13, R14 and R15, respec1 2 3 4 5 tively, have the values of R , R , R , R and R , respec12 15 tively, except that at least one of R and R represents hydrogen. It is preferable to use a starting aniline which has the cyano, nitro, methyl or trifluoromethyl substituents of the desired product, but lacks the halogen substituents,
1.0 and to add the halogen atoms in final halogenation reactions.
The individual steps of the above process are not extraordinary in organic chemistry, and are conducted as
-23a skilled organic chemist would expect. The coupling reactions which join the aniline and benzotrifluoride rings are most readily carried out at relatively low temperatures in the range of -20® to 10° in dimethylformamide in the presence of sodium hydride. Other media are likewise useful. The reactions may be carried out, for example, in alkanols such as ethanol, in which solvents the reaction temperature may be higher, in the range of 10° to 25°.
Other solvents, including ketones such as acetone and methyl ethyl ketone and ethers including diethyl ether and tetrahydrofuran, are satisfactory reaction solvents.
In general, a strong base is needed to serve as acid scavenger. Sodium hydride, as mentioned above, is generally the most useful base, but other bases including inorganic bases such as sodium hydroxide and sodium carbonate, and organic tertiary amines such as pyridine and triethylamine, as well as a simple excess of the aniline starting compound, may be used.
Nitration of the benzotrifluoride ring is readily accomplished with concentrated nitric acid in acetic acid solution at room temperature. The reaction is not an uncommon nitration, and may be accomplished with other common nitration reagents, such as a mixture of concentrated nitric and sulfuric acids at elevated temperatures. No solvent is used in the nitration reactions other than the acids themselves.
N-Alkylation of the diphenylamines is performed with reagents such as a dialkyl sulfate or an alkyl halide in the presence of a base. When a dialkyl sulfate is used,
-24the preferred reaction solvent is acetone. Other solvents, such as tetrahydrofuran, dioxane and diethyl ether, are also useful, as are alkanes such as hexane and octane. Dimethylformamide is the preferred solvent for alkylations with alkyl halides, although acetone is also excellent. Other solvents as described above may be used.
The preferred bases for use in the alkylation reactions are those which have a dehydrating effect, particularly sodium carbonate. However, other inorganic bases, such as the alkali metal carbonates, bicarbonates and hydroxides, can be used, as can the alkali metal hydrides.
The amount of base used depends upon the reaction temperature. The higher the reaction temperature in the alkylation step, the greater excess of base is needed. When the reaction temperature is approximately ambient, a small excess of base should be used, such as 2 moles of base per mole of diphenylamine. When very high reaction temperatures such as 100° are used, a large excass of base should be used, in the range of 10-fold.
It will be recognized that it is important to avoid contamination of the alkylation reaction mixture with water.
In general, alkylations with dialkyl sulfates are best performed at about 80°, although temperatures from approximately room temperature to the reflux temperature may be used. Conditions close to room temperature, such as from 20° to 35°, are preferred for alkyl halide alkylations, but elevated temperatures up even to as high as 150° may be used.
-25Halogenation of the aniline ring is comparatively simple. Chlorinations are usually best performed with elemental chlorine in acetic acid, or in methylene chloride or another halogenated hydrocarbon solvent. Brominations are also readily carried out with elemental bromine in an acid medium, but such other typical brominating agents as N-bromosuccinimide and dibromoisocyanuric acid are also quite effective.
Iodination is best carried out with iodine mono3 chloride as the reagent.
When a compound having no 4-substituent is to be made, it will often be necessary to block the 4-pOSition before halogenating. It is most convenient to use a sulfonic acid as the blocking group, because it is readily added and readily removed.
The starting substituted anilines and phenyl halides are readily obtained by methods which are commonly known in the chemical literature.
The trifluoromethyl-substituted anilines are best prepared, as chemists will recognize, by first obtaining a carboxylic acid-substituted aniline having the acid groups at the locations of the desired trifluoromethyl groups. The acid group is fluorinated with sulfur tetrafluoride.
It will be understood that the fluorinated aniline compounds are often prepared by first making a diazonitim fluoroborate salt at the position where the fluorine atom is desired. The salt is then decomposed with heat to leave a fluorine atom at the desired position. Alternatively, it has recently been found that fluorine atoms may be inserted
-26in phenyl rings with elemental fluorine at very low temperatures .
The following Examples, showing the preparation of typical compounds of formula I, are presented to assure that organic chemists can easily obtain any desired compound.
The products of the Examples were identified by nuclear magnetic resonance analysis, elemental microanalysis, thin-layer chromatography, and in some instances, by mass spectrophotometry and infrared analysis.
Example 1
2.4.6- trichloro-N-ethyl-21,4'-dinitro-6'-trifluoromethyldiphenylamine
A 3.5 g. portion of sodium hydride, obtained as an oil dispersion, was washed with petroleum ether and placed in a flask with 20 ml. of anhydrous dimethylformamide. The suspension was cooled to about -10° and the flask was blanketed with nitrogen. A solution of 8 g. of N-ethyl2.4.6- trichloroaniline in 20 ml. of anhydrous dimethylformamide was added over a 5-minute period, and the mixture was stirred for 1 hour, holding the temperature constant. A solution of 8.1 g. of 2-chloro-5-nitrobenzotrifluoride in 20 ml. of dimethylformamide was then added over a 5-minute period, and the complete mixture was stirred for 6 hours while the temperature was allowed to rise to ambient. The mixture was then poured over ice and brought to a total volume of about 1 liter with water. The resulting precipitate was separated by filtration, and washed with pentane to obtain 7.7 g. of 2,4,6-trichloro-N-ethyl-4'~ nitro-2'-trifluoromethyldiphenylamine.
-2743715
Two g. of the above intermediate were warmed with ml. of acetic acid until it dissolved. The solution was cooled to room temperature, and 5 ml. of concentrated nitric acid were added dropwise over a 10-minute period. The i reaction mixture was then stirred at room temperature.
After 2 days, the reaction mixture was quenched with a large amount of water, and the precipitate was separated by filtration and purified by column chromatography over silica gel with toluene as the eluent. Evaporation of the productl containing fractions produced 0.2 g. of pure 2,4,6-trichloro-N-ethyl-21,41-dinitro-61-trifluoromethyldiphenylamine, an oil, NMR peaks at 1.23, 4.01, 7.38, 8.55 and 8.76 ppm. Example 2
2,4,6-trichloro-N-methyl-21,41-dinitro-61-trifluoromethyl’ diphenylamine
Ten g. of 2,4,6-trichloro-N-methylaniline were reacted with 11 g. of 2-chloro-5-nitrobenzotrifluoride according to the process above, except that the temperature was room temperature and the reaction time was about 2
I hours. Five g. of 2,4,6-trichloro-N-methyl-4,-nitro-2'trifluoromethyldiphenylamine was recovered and nitrated according to the process of Example 1. The process yielded 2 g. of pure product, m.p. 125-126°C.
Theoretical Found c 37.80% 37.98% H 1.57 1.54 N 9.45 9.52 Cl 23.96 24.05
-284 3715
Example .3
2,4-dibromo-N-methy1-2 *,41-dinitro-6'-trifluoromethyldiphenylamine
A 27 g. portion of 2-chloro-3,5-dinitrobenzotrifluoride was added to 20 g. of aniline and 75 ml. of ethanol. After brief stirring at room temperature, the reaction mixture was seeded with a small sample of the desired intermediate product, and a precipitate formed immediately. The precipitate was separated by filtration and identified as 28.5 g. of 2,4-dinitro-6-trifluoromethyldiphenylamine .
The intermediate product was N-methylated in two different ways, both of which will be shown for the sake of clarity.
A. A 3.3 g. portion of the intermediate diphenylamine was taken up in 15 ml. of dimethylformamide, and 1.3 g. of sodium hydride was added. The mixture was stirred at room temperature, and 1.5 ml. of methyl iodide was added with the evolution of heat. After 1-1/2 hours, another 2 ml. of methyl iodide was added, and the mixture was warmed slightly. After 2 hours more, the reaction mixture was added to a large amount of cold water, and the aqueous layer was decanted. The remaining oil was taken up in diethyl ether and stirred with magnesium sulfate and charcoal.
After the solids were filtered away, the solution was evaporated to dryness to produce 2,4 g. of a dark red oil, which solidified upon cooling. The solid was heated with petroleum ether, cooled and filtered to produce 2.4 g. of N-methyl-2,4-dinitro-6-tri£luoromethyldiphenylamine, m.p. 84-86°.
-29B. Eleven g. of the intermediate diphenylamine were combined with 45 ml. of dioxane, 14 g. of sodium carbonate and 6 ml. of dimethyl sulfate and stirred at reflux temperature for 24 hours. Twelve ml. of additional dimethyl sulfate and 10 g. of sodium carbonate were then added, and the mixture was stirred at reflux temperature for 2 hours more. It was then poured into water and stirred for 4 hours. The aqueous layer was then decanted and the residue was taken up in methylene chloride and filtered. The solute ,0 was identified as approximately 10 g, of crude N-methyl-2,4dinitro-6-trifluoromethyldiphenylamine.
The methylene chloride solution obtained from paragraph B was brominated without further purification by the addition of excess elemental bromine. The solution was
L5 stirred and allowed to stand for 1 hour, and was washed with water and with sodium bisulfite solution. The organic solution was then filtered and evaporated to dryness, and the residue was recxystallized from ethanol to obtain 11 g. of 2,4-dibromo-N-methyl-2’,4 r-dinitro-6'-trifluoromethy1-
diphenylamine, m.p. ilo°. Theoretical Found C 33.70% 33.95% H 1.62 1.86 N 8.42 8.52 Example 4 2,4-dibromo-6-chloro-N-methyl-2' , 4'-dinitro·
methyldiphenylamine
A 2.5 g. portion of the product of Example 3 was dissolved in 10 ml. of methylene chloride, and the solution was saturated with elemental gaseous chlorine. After
-30437JS standing for 2 hours, the solution was evaporated to dryness under vacuum and the residue was recrystallized from ethanol
to produce 2.1 g, of product, m.p. 139-41 Theoretical Found 5 C 31.52% 31.78% H 1.32 1.35 N 7.38 8.10
Example 5
2,4,6-tribromo-N-methyl-21,41-dinitro-61-trifluoromethyl10 diphenylamine
A 2.5 g. portion of the product of Example 3 was dissolved in 25 ml. of diethyl ether and 1.5 ml. of concentrated sulfuric acid. The solution was stirred at room temperature while 0.7 g. of dibromoisocyanuric acid was added.
After 30 minutes of stirring, another 0.7 g. of dibromoisocyanuric acid and 1.5 ml. of sulfuric acid were added, and the addition was repeated again after another 15 minutes of stirring. Five minutes after the last addition, the reaction mixture was diluted with 50 ml. of diethyl ether and filtered. The organic layer was washed three times with 10 percent sodium carbonate solution, dried over magnesium sulfate and evaporated to dryness. The residue was recrystallized from ethanol to produce 2.4 g. of 2,4,6-tribromoN-methyl-2',4'-dinitro-6'-trifluoromethyldiphenylamine, m.p.
150-151°.
Theoretical Found
C 29.10% 29.02%
H 1.22 1.06
N 7.27 7.29
-313715
Example 6_
2,4,6-trichloro-21,41-dinitro-N-propyl-6'-trifluoromethyldiphenylamine
A 5 g. portion of the diphenylamine intermediate prepared in the first step of Example 3 was alkylated with propyl iodide in 80 ml. of dimethylformamide in the presence of 20 g. of sodium carbonate. The reaction mixture was stirred at 110° for 72 hours. The intermediate product was recovered by quenching the reaction mixture with water, extracting with methylene chloride, and evaporating the solvent under vacuum. The residue was taken up in acetic acid and the solution was saturated with chlorine and stirred at reflux for 4 hours. The product was purified by quenching the mixture in water, extracting with methylene chloride, washing the extract with sodium bicarbonate solution and then with water, and finally chromatographing on a silica gel column with pentane: toluene, 5:1. The yield
was 0.35 g. of 2,4, 6-trichloro-2'1,41-dinitro-N-propyl- 6'-trifluoromethyldiphenylamine. an oily liquid. Theoretical Found C 40.66% 40.66% H 2.35 2.22 N 8.89 8.71 Cl 22.50 22.45 The utility of this invention has been inves·
tigated by administering the compounds of Formula I to rodents in laboratory tests. The following reports of typical tests illustrate the outstanding rodenticidal efficacy of the compounds of Formula I.
-324 3 715
The first series of tests to be described were performed by mixing the compounds with an animal feed of cereal origin, and presenting the treated feeds to male albino rats of the Spraque-Dawley strain. The feed used 5 the following composition. Ingredient Percent Corn, Yellow, Ground 42.3 Oats, Ground 10.0 Wheat Middlings 10.0 10 Soybean Oil Meal, Solvent Extracted Dehulled, 50% 18.0 Skimmed Milk, Dried 5.0 Corn, Distillers Dried Solubles 2.5 Alfalfa Meal, Dehydrated, 17% 2.5 15 Whey, Whole Dried 1.0 Fish Meal with Solubles 4.0 Animal Fat, Beef Tallow 2.0 Dicalcium Phosphate, Feed Grade 0.5 Calcium Carbonate 1.0 20 Salt 0.3 Trace Mineral Premix 0.2 Vitamin Premix 0.6 Methionine Hydroxy Analog 0.1
Total 100.00
Compounds of formula I were mixed with portions of the above feed in concentrations described in the data tables below. Control rats in each experiment were fed on the same, untreated feed.
A treatment group of 4 or 5 rats was exposed to each lot of treated feed, and was allowed unlimited feed and water. The rats were individually weighed at death or
-334371S termination of each experiment, which ran for 10 days if the rats survived.
The tables below report the concentration of the compound in the feed, in parts per million parts of feed (ppm.), the number of days after starting the rats on treated feed when each rat died, and the weight change, positive or negative, of each rat during the 10-day experiment.
Compound of Example 1, 25 ppm. Rat No. Day of Death Weight Change 1 5 -64 g. 2 4 -38 g. 3 3 -35 g. 4 4 -53 g. 5 4 -44 g. Compound of Example 2, 15 ppm. Rat No. Day of Death Weight Change 1 5 -43 g. 2 4 -42 g. 3 3 -37 g. 4. 3 -28 g. 5 3 -37 g. Compound of Example 3, 100 ppm. Rat No. Day of Death Weight Change 1 6 -61 g. 2 7 -76 g. 3 5 -72 g. 4 5 -68 g. 5 5 -58 g.
-34The second series of tests to be described were performed in much the same way, except that the test animals were wild house mice (Mus musculus) and a different feed mixture was used. In ^hese tests, the weight change of the animals was not recorded.
Compound of Example 4, 50 ppm.
Animal No. Day of Death
3 '
3
3 5 2
Compound of Example 5, 50 ppm.
Animal No. Day of Death
3
2 ‘i :
The excellent rodenticidal results produced by the compounds are obvious on the face of the data. It will be observed that the compounds are effective at very low concentrations. Further, it is most significant that the compounds kill the rats with certainty, but not immediately. As has been explained, a good rodenticide allows time for many or all of the rats or mice of a colony to consume the poison bait before animals begin to die. It is clear that the compounds of formula I, when used in proper concentrations, work in the desired sure, but delayed, manner.
35In its most broad description, this invention provides a method of reducing a population of rats or mice which comprises supplying to a locus frequented by the rats or mice a rodenticidally-effective amount of a rodenticidal composition which comprises an effective rodenticidal concentration of a compound described above. The invention also provides the rodenticidal compositions which comprise inert carriers and effective rodenticidal concentrations of the compounds described above.
The details of the method, such as the times and places in which the rodenticidal compositions are supplied, and the carriers of the rodenticidal compositions, are common to the rodenticidal art. Some explanation of the various ways in which the method is carried out will be presented, however, for the convenience of the reader.
The method is effective in the control of rats and mice in general. For example, such pestiferous species as the following are controlled by the proper use of the present invention.
House mouse (Mus muscuius)
Norway rat (Rattus norvegicus)
Black rat (R. rattus rattus)
Roof rat (R. r. frugivorus)
White-footed mouse (Peromyscus leucopus)
Pack rat (Neotoma cinerea)
Meadow mouse (Microtus pennsylvanicus)
Those skilled in the rodenticidal art will understand that the present invention can also be used for the control of rodents other than rats and mice. Since rodents other than rats and mice are frequently beneficial, the
-364 3 71 β control of such other rodents is not contemplated as a regular part of the benefit of this invention. However, should the control of other rodents be desirable in particular circumstances, the invention can be used therefor.
This invention effectively controls rats and mice by both acute and chronic toxicity techniques. Proper adjustment of the concentration of the compound in the rodenticidal composition, as those of skill in the art will understand, allows the invention to reduce a population of rats or mice either by immediately poisoning the animals, or by chronically poisoning them over a number of feedings.
As has been explained, however, the delayed lethal effect of the compounds taught herein is an important factor in their rodenticidal usefulness. The maximum benefit of this invention is obtained by supplying to the locus of the rats or mice a rodenticidal composition which contains a concentration of the compound which is not acutely lethal in a single feeding, but which contributes to a lethal effect in the course of at least two feedings, and preferably a larger number of feedings. Accordingly it is also preferred to supply a sufficiently large amount of the rodenticidal composition to allow all the members of the population to feed on the composition two or more times.
A rat consumes about 5 to 50 grams of food per day; a mouse consumes about 1 to 5 grams per day, depending in each case on the animal's age, size, and state of health.
A pest control specialist can estimate the number of animals in a colony, and can supply to the locus of the animals appropriate quantities of treated feed, or other compositions, to provide an effective amount for each animal.
-37A preferred embodiment of the invention is, therefore, a method for reducing a population of rats or mice which comprises supplying to a locus frequented by the rats or mice a sufficient quantity for two or more feedings of a rodenticidal composition which comprises a sufficient concentration of a compound described above to be effectively rodenticidal upon two or more feedings. Another preferred embodiment of the invention is the rodenticidal composition just described.
Although the invention is described herein in terras of feedings”, the invention is also used by supplying rodenticidal compositions in the forms of tracking powders and drinking water compositions. It will be understood that such compositions are used in the same way as compositions based on foodstuffs, making appropriate adjustments to accommodate for the difference in the way the rodents ingest the compositions. The concentrations of the compounds in preferred drinking water or tracking powder compositions are effectively rodenticidal upon two or more waterings or cleanings, respectively. The term feeding is used herein to include watering and cleaning.
Rodenticidal compositions are based on inert carriers which include foodstuffs, drinking water and finely powdered solids. Compositions based on foodstuffs, which are the preferred inert carriers, may comprise any edible substance, since rats and mice are omnivorous. For example, such compositions may comprise cereals, meat byproducts or fats. Cereal foodstuffs which can be used in rodenticidal compositions include such substances as oatmeal, ground or cracked corn, soybean products, wheat and wheat byproducts and
-38waste rice. Any grain can be the basic of such compositions. Sweetening and flavor-enhancing agents can also be added to increase the attraction of the bait.
Fatty rodenticidal bait compositions are regularly made in inert ingredients such as peanut butter, other nut butters, milk solids, animal fats and vegetable oils. Rodenticidal compositions arc also sometimes based on animal products such as bone meal and on meat products including animal byproducts.
Tracking powders are composed of rodenticidal compounds dispersed in powdered so Lids. Virtually any powder can be used, including talc, chalk, ground clays, flour, nut shell flour, and powdered stone.
Rodenticidal compositions in drinking water comprise suspensions or dispersions oi the compounds. The compounds are quite water-insolubli, and it is therefore normally necessary to grind the compound to a fine particle size and suspend it. Suspending agents are commonly used in the pharmaceutical art, and are chosen from among the thickeners, such as carboxymethylcellulose, polyvinylpyrrolidone, gelatin and the alginates, and the surfactants, such as lecithin, alkylphenol polyethylene oxide adducts, alkyl sulfates, naphthalenesulfonates, alkylbenzenesulfonates and the polyoxyethylene sorbitan esters. It is sometimes also possible to use silicone antifoams, glycols, sorbitol and sugars as suspending agents.
The time when a rodenticidal composition of this invention is supplied to the locus of a colony of rats or mice is not critical. There are no seasons when a rodent
-39colony is particularly susceptible, or relatively immune, to the use of rodenticides. It is usually advantageous first to pre-bait the colony with an untreated composition. Preferably, sufficient of the treated composition should be supplied to last for the time during which the members of the colony feed at least twice.
The concentration of the compound in the composition depends on'the identity of the compound chosen, since they are of different potencies, upon the rapidity with which the population is desired to be reduced, and upon other factors as well. For example, if the population can be isolated, so that its only food or water source is a rodenticidal composition, the concentration obviously should be lower than if a variety of food sources are available.
In general, rodenticidal compositions should contain concentrations from 5 to about 2000 parts per million parts of the composition (ppm.). More preferably, concentrations from about 10 to about 500 ppm. should be used, although it will be understood that amounts both above and below the named range will be effective and even desirable in unusual circumstances.
It will be understood that additives and attractants can be usefully included in rodenticidal compositions of this invention. Such additives as, for example, odorants, sex hormones, and flavoring agents are regularly used in rodenticidal compositions, and can usefully be used in the compositions of this invention to assist in breaking down the suspicion of the rodents.
Claims (23)
1. CLAIMS:1. A diphenylamine of formula: wherein R represents methyl, ethyl or propyl; R 1 represents hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, nitro or trifluoromethyl; 2. 5 R and R independently represent hydrogen, fluoro, chloro, bromo, nitro, methyl or trifluoromethyl, provided that no 2 5 more than one of R and R represents nitro; R 3 and R^ independently represent hydrogen, methyl, fluoro, chloro, bromo or trifluoromethyl; provided that 1 2 3 4 5 a) no more than one of R , R , R , R and R 3. 4 represents methyl, except that R and R may both represent methyl; 1 2 3 4 5 b) when R , R , R , R or R represents methyl 12 5 or fluoro, two or three of R , R and R represent chloro or bromo; Ί Ο Ο X C c) no more than one of R , R , R , R and R represents trifluoromethyl, except that R and R may both represent trifluoromethyl; 2 5 1 d) when R or R represents trifluoromethyl, R represents chloro or bromo; 3 4 e) when one and only one of R and R represents 1 2 trifluoromethyl, two or three of R , R and R 5 represent chloro or bromo; -41371 η η ο A c f) no more than four of R , R , R , R and R represent hydrogen; g) two fluorine atoms are not adjacent to each other; 2 5 1 h) when R or R represents nitro, R represents chloro, bromo or nitro; i) when one of R 1 , R 2 , R 3 , R 4 and R 5 represents 12 3 4 trifluoromethyl, none of R , R , R , R and 5 R represents fluoro or methyl.
2. A compound of Claim 1 wherein R^ represents hydrogen, fluoro, chloro, bromo, iodo, cyano, nitro or trifluoromethyl. 2 5
3. A compound of Claim 1 or 2 wherein R and R independently represent hydrogen, fluoro, chloro, bromo, nitro or trifluoromethyl.
4. A compound of any of Claims 1 to 3 wherein R 4 and R independently represent hydrogen, fluoro, chloro, bromo or trifluoromethyl.
5. 2,4,6-Trichloro-N-ethyl-2’,4 1 -dinitro-6 1 -trifluoromethyldiphenylamine
6. 2,4,6-Trichloro-N-propyl-2 1 ,4'-dinitro-6’trifluoromethyldiphenylamine.
7. A compound of any of Claims 1 to 4 wherein R and R 5 independently represent hydrogen, chloro, bromo or' fluoro, R represents methyl, and R 3 represents hydrogen, chloro or bromo.
8. 2,4,6-Trichloro-N-methyl-2',4'-dinitro-6'-trifluoromethy ldiphenylamine -4243715
9. 2,4-Dibromo-N-methyl-2',4’-dinitro-6'-trifluoromethyldiphenylamine
10. 2,4-Dibromo-6-chloro-N-methyl-2',4'-dinitro-6'trifluoromethyldiphenylamine 5
11. 2,4,6-Tribromo-N-methyl-2 *,4'-dinitro-6'-trifluoromethyldiphenylamine.
12. A process for preparing a diphenylamine of formula I as claimed in Claim 1, which comprises a) reacting an aniline compound of the formula Lf LU R 1 -/ II wherein R is hydrogen, methyl, ethyl or propyl; and R 3 , R 3 , R 3 , R^ and R 3 are as defined above; with a 2-halo-5-nitrobenz.otrifluoride compound of the formula 0 N-i >-x III 15 wherein X is halo and R is hydrogen or nitro, provided that R 3 ^ and at least one of R 3 and R J are hydrogen 17 . when R is nitro; b) N-alkylating the compound obtained in step a) wherein X6 R is hydrogen; 20 c) nitrating the compound obtained in step b) wherein 17 R is hydrogen; and -43d) if desired halogenating the compound obtained in step c) which lacks the desired halogen substituents.
13. a rodenticidal composition which comprises an inert carrier and as active ingredient an effective rodenticidal concentration of a diphenylamine compound of any of Claims 1 to 11.
14. The composition of Claim 9 wherein the concentration of the active ingredient is from 5 to 2000 ppm.
15. The composition of Claim 14 wherein the concentration of the active ingredient is from 10 to 500 ppm.
16. The composition of any of Claims 13 to 15 wherein the inert carrier is a foodstuff.
17. A method of reducing a population of rats or mice which comprises supplying to a locus frequented by the rats or mice a rodentioidally-effeotive amount of the rodenticidal composition of any of Claims 13 to 16.
18. The method of Claim 17 wherein the concentration of the active ingredient is rodenticidally effective upon two or more feedings, and the amount of the composition is sufficient for two or more feedings. -4443715
19. A method of reducing a population of rats or mice as claimed in Claim 17 substantially as hereinbefoi'e described.
20. A rodenticidal composition as claimed in Claim 13 5 substantially as hereinbefore described.
21. A process according to Claim 12 for preparing a diphenylamine of formula I substantially as hereinbefore described with particular reference to any one of the Examples. 10
22. A diphenylamine of formula I as claimed in Claim 1, substantially as hereinbefore described with particular reference to any one of the Examples.
23. A diphenylamine of formula I whenever prepared by the process of Claim 12 or 21.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61711575A | 1975-09-26 | 1975-09-26 | |
| US70602276A | 1976-07-21 | 1976-07-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE43715L IE43715L (en) | 1977-03-26 |
| IE43715B1 true IE43715B1 (en) | 1981-05-06 |
Family
ID=27087951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE1765/76A IE43715B1 (en) | 1975-09-26 | 1976-08-10 | Nitrotrifluoromethyl substituted diphenylamines,their preparation and rodenticidal compositions |
Country Status (32)
| Country | Link |
|---|---|
| JP (1) | JPS5828863B2 (en) |
| AR (1) | AR225588A1 (en) |
| AT (2) | AT345266B (en) |
| AU (1) | AU508202B2 (en) |
| BE (1) | BE846419A (en) |
| BG (2) | BG28701A4 (en) |
| BR (1) | BR7606370A (en) |
| CA (1) | CA1090822A (en) |
| CH (1) | CH626322A5 (en) |
| CS (1) | CS189786B2 (en) |
| DD (2) | DD134431A5 (en) |
| DE (1) | DE2642148C2 (en) |
| DK (1) | DK154069C (en) |
| DZ (1) | DZ85A1 (en) |
| ES (1) | ES451857A1 (en) |
| FI (1) | FI62527C (en) |
| FR (1) | FR2325635A1 (en) |
| GB (1) | GB1560709A (en) |
| GR (1) | GR61721B (en) |
| HU (1) | HU177823B (en) |
| IE (1) | IE43715B1 (en) |
| IL (1) | IL50258A (en) |
| IT (1) | IT1078789B (en) |
| MX (1) | MX4391E (en) |
| NL (1) | NL185442C (en) |
| NO (1) | NO143025C (en) |
| PH (1) | PH12570A (en) |
| PL (2) | PL110942B1 (en) |
| PT (1) | PT65581B (en) |
| RO (3) | RO75109A (en) |
| SE (2) | SE435055B (en) |
| YU (1) | YU43438B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4215145A (en) | 1978-12-05 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Miticidal, fungicidal, and ovicidal sulfenamides |
| EP0026743B1 (en) * | 1979-09-28 | 1983-05-25 | Ciba-Geigy Ag | Polysubstituted diphenyl amines, their preparation and their use |
| US4323580A (en) | 1980-01-24 | 1982-04-06 | E. I. Du Pont De Nemours And Company | Miticidal, fungicidal and ovicidal diphenylsulfenamides |
| JPS56149406A (en) * | 1980-04-21 | 1981-11-19 | Mitsui Toatsu Chem Inc | Production of styrene polymer |
| US4298613A (en) | 1980-05-05 | 1981-11-03 | E. I. Du Pont De Nemours And Company | Agricultural heterocyclic sulfenamides |
| US4302451A (en) | 1980-05-05 | 1981-11-24 | E. I. Du Pont De Nemours And Company | Pesticidal phosphorus sulfenamides |
| US4341772A (en) * | 1980-05-05 | 1982-07-27 | E. I. Du Pont De Nemours And Company | Agricultural phosphorus-containing sulfenamides |
| JPS60206809A (en) * | 1984-03-29 | 1985-10-18 | Kanegafuchi Chem Ind Co Ltd | Production of copolymer |
| JPS61109460U (en) * | 1984-12-20 | 1986-07-11 | ||
| CA1287795C (en) * | 1985-12-06 | 1991-08-20 | David G. Hobbs | Composition for rodent control |
| JPS63188675U (en) * | 1987-05-25 | 1988-12-02 | ||
| JPH0372505A (en) * | 1989-05-24 | 1991-03-27 | Sanyo Chem Ind Ltd | Binder for electrophotographic toner |
| JPH0463459U (en) * | 1990-10-15 | 1992-05-29 | ||
| DE69600907D1 (en) * | 1995-07-18 | 1998-12-10 | Sumitomo Chemical Co | Process for controlling the rate of polymerization of a styrene resin |
| CN102199095B (en) | 2010-03-22 | 2014-04-09 | 中国中化股份有限公司 | Substituted diphenylamine compounds and preparation and application thereof |
| KR101599300B1 (en) | 2012-03-14 | 2016-03-03 | 시노켐 코포레이션 | Substitute diphenylamine compounds use thereof as antitumor agents |
-
1976
- 1976-08-10 IE IE1765/76A patent/IE43715B1/en not_active IP Right Cessation
- 1976-08-11 GR GR51457A patent/GR61721B/en unknown
- 1976-08-12 IL IL50258A patent/IL50258A/en unknown
- 1976-08-20 PH PH18820A patent/PH12570A/en unknown
- 1976-08-24 CA CA259,772A patent/CA1090822A/en not_active Expired
- 1976-08-30 MX MX764866U patent/MX4391E/en unknown
- 1976-08-31 AR AR264526A patent/AR225588A1/en active
- 1976-09-01 YU YU2143/76A patent/YU43438B/en unknown
- 1976-09-09 SE SE7609986A patent/SE435055B/en not_active IP Right Cessation
- 1976-09-10 PT PT65581A patent/PT65581B/en unknown
- 1976-09-16 CS CS766024A patent/CS189786B2/en unknown
- 1976-09-17 RO RO7696216A patent/RO75109A/en unknown
- 1976-09-17 RO RO7687562A patent/RO70677A/en unknown
- 1976-09-17 RO RO7696217A patent/RO75110A/en unknown
- 1976-09-20 DE DE2642148A patent/DE2642148C2/en not_active Expired
- 1976-09-22 GB GB39225/76A patent/GB1560709A/en not_active Expired
- 1976-09-22 BE BE1007640A patent/BE846419A/en not_active IP Right Cessation
- 1976-09-23 FI FI762718A patent/FI62527C/en not_active IP Right Cessation
- 1976-09-23 AT AT705576A patent/AT345266B/en not_active IP Right Cessation
- 1976-09-23 CH CH1208076A patent/CH626322A5/en not_active IP Right Cessation
- 1976-09-24 FR FR7628847A patent/FR2325635A1/en active Granted
- 1976-09-24 HU HU76EI700A patent/HU177823B/en unknown
- 1976-09-24 DD DD76201829A patent/DD134431A5/en unknown
- 1976-09-24 DD DD7600194974A patent/DD128782A5/en unknown
- 1976-09-24 IT IT27648/76A patent/IT1078789B/en active
- 1976-09-24 NL NLAANVRAGE7610602,A patent/NL185442C/en not_active IP Right Cessation
- 1976-09-24 ES ES451857A patent/ES451857A1/en not_active Expired
- 1976-09-24 BR BR7606370A patent/BR7606370A/en unknown
- 1976-09-24 NO NO763286A patent/NO143025C/en unknown
- 1976-09-24 BG BG7639026A patent/BG28701A4/en unknown
- 1976-09-24 DK DK431076A patent/DK154069C/en not_active IP Right Cessation
- 1976-09-24 BG BG7634277A patent/BG27538A3/en unknown
- 1976-09-25 PL PL1976209045A patent/PL110942B1/en unknown
- 1976-09-25 JP JP51115319A patent/JPS5828863B2/en not_active Expired
- 1976-09-25 PL PL1976192654A patent/PL107314B1/en unknown
- 1976-09-27 DZ DZ764292A patent/DZ85A1/en active
- 1976-09-27 AU AU18140/76A patent/AU508202B2/en not_active Expired
-
1977
- 1977-07-27 AT AT548577A patent/AT361245B/en not_active IP Right Cessation
-
1980
- 1980-09-24 SE SE8006682A patent/SE436392B/en unknown
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| IE43715B1 (en) | Nitrotrifluoromethyl substituted diphenylamines,their preparation and rodenticidal compositions | |
| US4783481A (en) | Rodenticides | |
| US4187318A (en) | Rodenticidal N-alkyldiphenylamines | |
| CA1087634A (en) | Diphenylamine compounds | |
| US4117167A (en) | Dinitroaniline derivatives | |
| JPS6368566A (en) | Arylpyridone compound, manufacture and insecticidal composition | |
| Li et al. | Design, synthesis, insecticidal, and acaricidal activities of novel pyrimidinamine derivatives containing a biphenyl ether | |
| US3950377A (en) | Diphenylamine derivatives | |
| KR800000730B1 (en) | Process for the preparation of n-alkyl diphenyl-amines | |
| KR840002065B1 (en) | Process for preparing phenyl propargyl amine derivatives | |
| KR800000732B1 (en) | Process for the preparation of n-alkyl diphenyl-amines | |
| US4517129A (en) | Process for the preparation of cyanotetrachlorobenzenes | |
| US4140778A (en) | N-pyridyl-N-phenylamines as rodenticides | |
| NO143023B (en) | DIFENYLAMINES FOR USE AS INTERMEDIATES IN THE PREPARATION OF RODENTICID EFFECTIVE COMPOUNDS | |
| KR800000731B1 (en) | Process for the preparation of n-alkyl diphenyl-amines | |
| US3052601A (en) | Phenolic lamprey larvicides | |
| US3865931A (en) | Pyridyl phenyl carbamate rodenticides | |
| SU702996A3 (en) | Phodenticide composition | |
| IE44018B1 (en) | Trinitro diphenylamines, their preparation and rodenticidal compositions | |
| DD244550A5 (en) | ALKANOYLANILIDEN | |
| NO143024B (en) | DIFENYLAMINES FOR USE AS INTERMEDIATES IN THE PREPARATION OF RODENTICID EFFECTIVE COMPOUNDS | |
| CA1100514A (en) | Imidazolidine derivatives useful as insecticides and acaricides | |
| RU2528419C2 (en) | 3,5-dinitro-2-(arylamino)-n-(4-nitroaryl)benzamides, having rodenticide activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Patent lapsed | ||
| HK2 | Errata: patent lapsed |