CA1090821A - 4-nitro-2-trifluoromethyldiphenylamines - Google Patents
4-nitro-2-trifluoromethyldiphenylaminesInfo
- Publication number
- CA1090821A CA1090821A CA258,795A CA258795A CA1090821A CA 1090821 A CA1090821 A CA 1090821A CA 258795 A CA258795 A CA 258795A CA 1090821 A CA1090821 A CA 1090821A
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- Canada
- Prior art keywords
- nitro
- methyl
- chloro
- bromo
- ethyl
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
Abstract of the Disclosure The present invention relates to novel tertiary diphenylamines having a small alkyl group on the amino nitrogen and 4-nitro-2-trifluoromethyl substitution on one phenyl ring, which are intermediates for the preparation of important rodenticidal compounds.
Description
~L~'3~2~L
The present invention relates to novel tertiary diphenylamines having a small alkyl group on the amino nitrogen and 4-nitro-2-trifluoromethyl substitution on one phenyl ring, which are intermediates for the preparation of important rodenticidal compounds.
This invention belongs to the rodenticidal and - organic chemical arts and provides new intermediates for the preparation of rodenticides.
Rodenticides have long been the subject of re-search. Rats and mice carry many diseases, and create havocwhen they share the habitations of mankind. They soil and contaminate buildings, and destroy buildings and their contents by their tunneling and nest building. The animals, when present in numbers, consume or contaminate great amounts of food.
Many kinds of rodenticides have been discovered and many are still in use. Probably the best all round existing rodentlcide is the organic chemical compound, warfarin. Rodents, however, are developing resistance to existing rodenticides. The metallic poisons, such as arsenic and thallium compounds, are used to a degree but are obviously quite dangerous to people and to useful animals.
Tertiary diphenylamines such as those of this invention have not previously been known. Secondary di-phenylamines, however, have previously been known to be fungicides and insecticides.
A group of secondary diphenylamines having 4-nitro-2-trifluoromethyl substitution on one phenyl ring and 4 or 5 halogen atoms on the other are known.
~o~
The present invention provides novel diphenyl-amine compounds of the formula 02N~ N---o/ ~ ~R
~ ~F
wherein R represents methyl or ethyl;
Rl represents hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, nitro or trifluoromethyl;
R2 and R5 independently represent hydrogen, fluoro, chloro, bromo, nitro, methyl or trifluoromethyl, provided that no more than one of R and R represents nitro;
R3 and R4 independently repre~ent hydrogen, methyl, fluoro, chloro, bromo or trifluoromethyl;
provided that ~a) no more than one of R , R2, R , R4 and R5 represents methyl, except that R3 and R4 may both represent methyl;
b) when Rl, R2, R3, R4 or R5 represents methyl or fluoro, two or three of Rl, R and R
represent hydrogen, chloro or bromo;
c) no more than one of R , R , R , R4 and R5 represents trifluoromethyl, except that R3 and R4 may both represent trifluoromethyl;
d) when R2 or R5 represents trifluoromethyl, represents hydrogen, chloro or bromo;
X-4726 _3_ lO9Q82~
e) when one and only one of R3 and R4 represents trifluoromethyl, two or three of Rl, R2 and R5 represent hydrogen, chloro or bromo;
f) two fluorine atoms are not adjacent to each other;
g) when R2 or R5 represents nitro, Rl represents hydrogen, chloro, bromo or nitro;
h) when R I R , R , R or R5 represents tri-fluoromethyl, none of Rl, R2, R3, R4 and R5 represents fluoro or methyl, and i) at least one of Rl R2 R3 R4 d R5 i h than hydrogen.
The present invention also provides a process for preparing the novel dlphenylamine compounds of the formula I
wherein the symbols have the meanings sta~ed above, which comprises reacting an aniline compound of the formula - R ~ T2 ~
H-N--5~ R 1 II
R5==~4 wherein Rl, R2, R3, R4 and R5 are as defined above, and R'' is hydrogen, methyl or ethyl, with a 2-halo-5-nitro-benzotrifluoride compound of the formula \~=__~/
wherein X is halogen; followed by alkylating the compound so obtained wherein R'' is hydrogen.
i ~ I
~...~ . . .
~O~DQ~Z~
All of the compouncls below will be named as diphenylamines for the sake of consistency and clarity, even though the rules of nomenclat:ure may call for some compounds to be named otherwise.
All percentages ancl parts described hereafter refer to percentages and parts by weight, and all tempera-tures are on the Celsius scale.
The following exemplary compounds are mentioned to assure 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.
The present invention relates to novel tertiary diphenylamines having a small alkyl group on the amino nitrogen and 4-nitro-2-trifluoromethyl substitution on one phenyl ring, which are intermediates for the preparation of important rodenticidal compounds.
This invention belongs to the rodenticidal and - organic chemical arts and provides new intermediates for the preparation of rodenticides.
Rodenticides have long been the subject of re-search. Rats and mice carry many diseases, and create havocwhen they share the habitations of mankind. They soil and contaminate buildings, and destroy buildings and their contents by their tunneling and nest building. The animals, when present in numbers, consume or contaminate great amounts of food.
Many kinds of rodenticides have been discovered and many are still in use. Probably the best all round existing rodentlcide is the organic chemical compound, warfarin. Rodents, however, are developing resistance to existing rodenticides. The metallic poisons, such as arsenic and thallium compounds, are used to a degree but are obviously quite dangerous to people and to useful animals.
Tertiary diphenylamines such as those of this invention have not previously been known. Secondary di-phenylamines, however, have previously been known to be fungicides and insecticides.
A group of secondary diphenylamines having 4-nitro-2-trifluoromethyl substitution on one phenyl ring and 4 or 5 halogen atoms on the other are known.
~o~
The present invention provides novel diphenyl-amine compounds of the formula 02N~ N---o/ ~ ~R
~ ~F
wherein R represents methyl or ethyl;
Rl represents hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, nitro or trifluoromethyl;
R2 and R5 independently represent hydrogen, fluoro, chloro, bromo, nitro, methyl or trifluoromethyl, provided that no more than one of R and R represents nitro;
R3 and R4 independently repre~ent hydrogen, methyl, fluoro, chloro, bromo or trifluoromethyl;
provided that ~a) no more than one of R , R2, R , R4 and R5 represents methyl, except that R3 and R4 may both represent methyl;
b) when Rl, R2, R3, R4 or R5 represents methyl or fluoro, two or three of Rl, R and R
represent hydrogen, chloro or bromo;
c) no more than one of R , R , R , R4 and R5 represents trifluoromethyl, except that R3 and R4 may both represent trifluoromethyl;
d) when R2 or R5 represents trifluoromethyl, represents hydrogen, chloro or bromo;
X-4726 _3_ lO9Q82~
e) when one and only one of R3 and R4 represents trifluoromethyl, two or three of Rl, R2 and R5 represent hydrogen, chloro or bromo;
f) two fluorine atoms are not adjacent to each other;
g) when R2 or R5 represents nitro, Rl represents hydrogen, chloro, bromo or nitro;
h) when R I R , R , R or R5 represents tri-fluoromethyl, none of Rl, R2, R3, R4 and R5 represents fluoro or methyl, and i) at least one of Rl R2 R3 R4 d R5 i h than hydrogen.
The present invention also provides a process for preparing the novel dlphenylamine compounds of the formula I
wherein the symbols have the meanings sta~ed above, which comprises reacting an aniline compound of the formula - R ~ T2 ~
H-N--5~ R 1 II
R5==~4 wherein Rl, R2, R3, R4 and R5 are as defined above, and R'' is hydrogen, methyl or ethyl, with a 2-halo-5-nitro-benzotrifluoride compound of the formula \~=__~/
wherein X is halogen; followed by alkylating the compound so obtained wherein R'' is hydrogen.
i ~ I
~...~ . . .
~O~DQ~Z~
All of the compouncls below will be named as diphenylamines for the sake of consistency and clarity, even though the rules of nomenclat:ure may call for some compounds to be named otherwise.
All percentages ancl parts described hereafter refer to percentages and parts by weight, and all tempera-tures are on the Celsius scale.
The following exemplary compounds are mentioned to assure 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-4'-nitro-2' trifluoromethyldiphenylamine 2-bromo-N-ethyl-4'-nitro-2'-trifluoromethyldi-phenylamine 2,4-dichloro N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dibromo-4-cyano-N-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine N-ethyl-2,6-dibromo-4-iodo-4'-nitro-2'-trifluoro-methyldiphenylamine 2-bromo-6-chloro-N-methyl-4,4'-dinitro-2'-tri-fluoromethyldiphenylamine 4-bromo-2-chloro-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4 dibromo-6-chloro-N-ethyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-bromo-6-chloro-N-methyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine X-4726 _5_ ~q~901~Z~
N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenyl-amine 2,6-dibromo-4-iodo-N-methyl-4'-dinitro-2'-trifluoromethyldiphenylamine N-methyl-2,4,6-trichloro-4'-nitro 2'-trifluoro-methyldiphenylamine 2,6-dibromo-N-methyl-4,4'-dinitro-2'-trifluoro-methyldiphenylamine N-ethyl-2-bromo-4'-nitro-2',4-bis(trifluoromethyl)-diphenylamine 4-cyano-N-ethyl-4'-nitro-2'-trifluoromethyldi-phenylamine 4-chloro-N-ethyl-4'-nitrs-2'-tri1uoromethyl-diphenylamine 2,6-dichloro-N-ethyl-4'-nitro-2',4-bis(trifluoro-methyl)diphenylamine 2,6-dibromo-N-methyl-4'-nitro-2',4-bis(trifluoro-methyl)diphenylamine 2-chloro-4-iodo-N-methyl-4'-nitro-2 9 -trifluoro-methyldiphenylamine 2j6-dichloro-4-cyano-N-ethyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2,~-dibromo-N-ethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 4-bromo-2-chloro-N-ethyl-4'-nitro-2'-trifluoro-- methyldiphenylamine 2-chloro-4-cyano-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2-bromo-N-ethyl-4,4'-dinitro-2'-trifluoromethyl-diphenylamine 2-chloro-N-ethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6 dichloro-N-ethyl-4,4'-dinitro-2'-trifluoro-methyldiphenylamine 2-bromo-4,6-dichloro-N-ethyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2,6-dichloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoro-methyldiphenylamine N-ethyl-2,6-dibromo-4-chloro-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-chloro-4-cyano-N-methyl-4'-nitro-2'-trifluord-methyldiphenylamine 2-bromo-4-chloro-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2-chloro-N-ethyl-4,4'-dinitro-2'-trifluoromethyl-diphenylamine N-ethyl-4'-nitro-2',4-bis(trifluoromethyl)di-phenylamine 2-bromo-N-ethyl-4-iodo-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4-dichloro-N-ethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,4,6-tribromo-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamlne 2-bromo-4-cyano-N-ethyl-4'-nitro-2'~trifluoro-methyldiphenylamine 2,6-dichloro-N-ethyl-4'-nitro-2',4-bis(trifluoro-methyl)diphenylamine 08;~1 2-chloro-N-methyl-4'-nitro-2',4-bis~trifluoro-methyl)diphenylamine 2-bromo-4-iodo-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2-bromo-4,6-dichloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro-4-cyano-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2-bromo-4-chloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine N-ethyl-4,4'-dinitro-2'-trifluoromethyldiphenyl-amine N-methyl-2-bromo-4,4'-dinitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoro-methyldiphenylamine 2-bromo-6-chloro-N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 4-bromo-2-chloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,6-dibromo-N-ethyl-4,4'-dinitro-2'-trifluoro-methyldiphenylamine 2-bromo-6-chloro-4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine N-ethyl-2,6-dichloro-4-cyano-4'-nitro-2'-tri-fluoromethyldiphenylamine 4-bromo-2,6-dichloro-N-methyl-4'-nitro-2'-t.rifluoromethyldiphenylamine 2-bromo-6-chloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-cyano-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4-dibromo~6-chloro-N-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-bromo-4-chloro-6,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-N-ethyl-3-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine N-ethyl-4'-nitro-2,2'-bis(trifluoromethyl)diphenyl-amine 4-bromo-2-chloro-N-ethyl-4'-nitro-2',6-bis(tri-fluoromethyl)diphenylamine 4,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenyl-amine 2-bromo-N-methyl-4'-nitro-2',3-bis(trifluoro-methyl)diphenylamine
N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenyl-amine 2,6-dibromo-4-iodo-N-methyl-4'-dinitro-2'-trifluoromethyldiphenylamine N-methyl-2,4,6-trichloro-4'-nitro 2'-trifluoro-methyldiphenylamine 2,6-dibromo-N-methyl-4,4'-dinitro-2'-trifluoro-methyldiphenylamine N-ethyl-2-bromo-4'-nitro-2',4-bis(trifluoromethyl)-diphenylamine 4-cyano-N-ethyl-4'-nitro-2'-trifluoromethyldi-phenylamine 4-chloro-N-ethyl-4'-nitrs-2'-tri1uoromethyl-diphenylamine 2,6-dichloro-N-ethyl-4'-nitro-2',4-bis(trifluoro-methyl)diphenylamine 2,6-dibromo-N-methyl-4'-nitro-2',4-bis(trifluoro-methyl)diphenylamine 2-chloro-4-iodo-N-methyl-4'-nitro-2 9 -trifluoro-methyldiphenylamine 2j6-dichloro-4-cyano-N-ethyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2,~-dibromo-N-ethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 4-bromo-2-chloro-N-ethyl-4'-nitro-2'-trifluoro-- methyldiphenylamine 2-chloro-4-cyano-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2-bromo-N-ethyl-4,4'-dinitro-2'-trifluoromethyl-diphenylamine 2-chloro-N-ethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6 dichloro-N-ethyl-4,4'-dinitro-2'-trifluoro-methyldiphenylamine 2-bromo-4,6-dichloro-N-ethyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2,6-dichloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoro-methyldiphenylamine N-ethyl-2,6-dibromo-4-chloro-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-chloro-4-cyano-N-methyl-4'-nitro-2'-trifluord-methyldiphenylamine 2-bromo-4-chloro-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2-chloro-N-ethyl-4,4'-dinitro-2'-trifluoromethyl-diphenylamine N-ethyl-4'-nitro-2',4-bis(trifluoromethyl)di-phenylamine 2-bromo-N-ethyl-4-iodo-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4-dichloro-N-ethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,4,6-tribromo-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamlne 2-bromo-4-cyano-N-ethyl-4'-nitro-2'~trifluoro-methyldiphenylamine 2,6-dichloro-N-ethyl-4'-nitro-2',4-bis(trifluoro-methyl)diphenylamine 08;~1 2-chloro-N-methyl-4'-nitro-2',4-bis~trifluoro-methyl)diphenylamine 2-bromo-4-iodo-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2-bromo-4,6-dichloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro-4-cyano-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2-bromo-4-chloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine N-ethyl-4,4'-dinitro-2'-trifluoromethyldiphenyl-amine N-methyl-2-bromo-4,4'-dinitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoro-methyldiphenylamine 2-bromo-6-chloro-N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 4-bromo-2-chloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,6-dibromo-N-ethyl-4,4'-dinitro-2'-trifluoro-methyldiphenylamine 2-bromo-6-chloro-4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine N-ethyl-2,6-dichloro-4-cyano-4'-nitro-2'-tri-fluoromethyldiphenylamine 4-bromo-2,6-dichloro-N-methyl-4'-nitro-2'-t.rifluoromethyldiphenylamine 2-bromo-6-chloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-cyano-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4-dibromo~6-chloro-N-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-bromo-4-chloro-6,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-N-ethyl-3-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine N-ethyl-4'-nitro-2,2'-bis(trifluoromethyl)diphenyl-amine 4-bromo-2-chloro-N-ethyl-4'-nitro-2',6-bis(tri-fluoromethyl)diphenylamine 4,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenyl-amine 2-bromo-N-methyl-4'-nitro-2',3-bis(trifluoro-methyl)diphenylamine
3,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenyl-amine 2,4-dibromo-N-ethyl-6-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine N-ethyl-4'-nitro-2',3-bis(trifluoromethyl)di-phenylamine 2,6-dibromo-N-ethyl-4'-nitro-2',q-bis(trifluoro-methyl)diphenylamine N-ethyl-4-nitro-2,3',5'-trisltrifluoromethyl)-diphenylamine 2,4,6-tribromo-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethyldiphenylamine
4-bromo-2,6-dichloro-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethy.ldiphenylamine 2,6-dibromo-N-ethyl-4-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-bromo-6-chloro-3,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4,6-dichloro-3,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-chloro-N-ethyl-4'-nitro-2,2'-bis(trifluoro-methyl3diphenylamine 4-bromo-2-chloro-5,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-2,6-dichloro-N-methyl-4'-nitro-2',3-bis(trifluoromethyl)diphenylamine 2-bromo-6-chloro-N-ethyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine 2,4-dichloro-N-methyl-4'-nitro-2',3-bis(trifluoro-methyl)diphenylamine 2,4-dibromo-3,N-dimethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 4-bromo-2-chloro-6,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dibromo-N-ethyl-4'-nitro-2',3-bis~trifluoro--methyl)diphenylamine ~o~%~
2,4,6-tribromo-N-ethyl-4'-nitro-2',3-bis(tri-fluoromethyl)diphenylamine 2-bromo-4-chloro-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4,6-trichloro-N-ethyl-4'-nitro-2',3-bis(tri-f luoromethyl)diphenylamine 2,6-dibromo-4-chloro-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-chloro-N methyl-4'-nitro-2',3-bis(tri-10 f luoromethyl~diphenylamine' 2,6-dichloro-~-methyl-4'-nitro-2',4-bis(tri-fluoromethyl~diphenylamine N-ethyl-3,5-dimethyl-4'-nitro-2'-trifluoromethyl-diphenylamine ~ -2,6-dichloro-3,5,N-trimethyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-bromo-4-chloro-N-ethyl-3,5-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-2-chloro-3,5,N-trimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-N-methyl-4'-nitro-2',3,5-tris(trifluoro-methyl)diphenylamine 2,4,6-trichloro-N-ethyl-4'-nitro-2',3,5-tris-(trifluoromethyl)diphenylamine 2,4-dibromo-N-ethyl-4'-nitro-2',3,5-tris(tri-fluoromethyl)diphenylamine 2,6-dibromo-4-chloro-N-ethyl-4'-nitro-2',3,5-tris~trifluoromethyl)diphenylamine ~o~
2,4,6-tribromo-3,5,N-trimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-chloro-N-ethyl-4'--nitro-2,2'-bis(trifluoro-methyl~diphenylamine 2,6-dibromo-N-ethyl-3-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro--3,N~dimethyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2,6-dichloro-N-ethyl-3-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-4-cyano-3,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro-4-cya~o-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dichloro-4-cyano-3,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro-N-ethyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine 2,6-dibromo-N-ethyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine 2,6-dichloro-N-ethyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine 2,6-dibromo-N-methyl-4,4'-dinitro-2',3-bis-(trifluoromethyl)diphenylamine 2-bromo-6-chloro-N-ethyl-4,4'-dinitro-2',3-bis(trifluo:romethyl)diphenylamine 2,6-dibromo-4-cyano-N-ethyl-4'-nitro-2',3-bis(trlfluoromethyl)diphenylamine ~09~
2-bromo-6-chloro-N-ethyl-4r4~-dinitro-2~ t 3~
bist~rifluoromethyl)diphenylamine 2,3,5-trichloro-N-methyl-4,4',6-trinitro-2'- -trifluoromethyldiphenylamine 4-bromo-N-ethyl-2,4'-dinitro-2'-trifluoromethyl-diphenylamine 4-chloro-N-ethyl-2,4'-dinitro-2'-trifluoromethyl-diphenylamine 2,4-dibromo-N-ethyl-4',6-dini~ro-2',5-bi~(tri-fluoromethyl)diphenylamine 4-bromo-2-chloro-N-methyl-4',6-dinitro-2l-trifluoromethyldiphenylamine 2,3,4,5,6-pentachloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,3,4,5,6-pentabromo-N-ethyl-4'-nitro-2~-tri-fluoromethyldiphenylamine 4-bromo-2,5,6-tri~hloro-N-ethyl-3-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,3,5,6-tetrabromo-4-fluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-2,3,5,6-tetrachloro-N-methyl-4'-nitro-2'~trifluoromethyldiphenylamine 3,5-dibromo-2,4 r 6-trichloro-N-ethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,3,5,6-tetrachloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoromethyldiphenylamine 2,4,6-tribromo-3,5-dichloro~N-methyl-4'-nitro-2'-trifluoromethyldlphenylamine ~L~963 ~
2,3,4,6-tetrachloro-N-ethyl-5-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 3-bromo-2,4,5,6-tetrachloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylam:ine 2,3,6-tribromo-5-f:Luoro-N-methyl-4-iodo-4'-nitro-2'-trifluoromethyldiphenylamine 2-fluoro-N-methyl 4'-nitro-2'-trifluoromethyl-diphenylamine 2,3,4,6-tetrachloro-N-ethyl-4l-nitro-2'-tri-fluoromethyldiphenylamine 2,3,5,6-tetrabromo-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,6-dibromo-3,5-dichloro-N-ethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-fluoro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,3,4-trichloro-N-ethyl-5-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-4-fluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-N-ethyl-3-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-chloro-6-fluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-3-fluoro-4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-fluoro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine ~L~908;~L
2-chloro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 3-bromo-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-N-ethyl-4-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,4,6-trichloro-N-ethyl-3-fluoro-4'-nitxo-2'-trifluoromethyldiphenylamine 3-fluoro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,4-dibromo-N-ethyl-6-fluoro-4'-nitro-2'-tri-fluoromethyldiphenylamine 4-cyano-3-fluoro-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 4-bromo-N-ethyl-4'-nitro-2,2'-bis(trifluoromethyl)-diphenylamine 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-3-fluoro-40N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dibromo-3-chloro-N-methyl-4'-nitro-2',6-bis(trifluoromethyl)diphenylamine N-ethyl-4,4'-dinitro-2-trifluoromethyldiphenyl-amine 3,4-dichloro-N-met~yl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-3-fluoro-N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine ~o~
4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldi-phenylamine 4-bromo-N-methyl-4'-nitro-2',3,5-tris~triflucro-methyl)diphenylamine 2,6-dichloro-N-ethyl-3-bromo-4'--nitro-2',4-bis(trifluoromethyl)diphenylamine 3l5-dibromo-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2-fluoro-3,N-dimethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-N-methyl-4'-nitro-2',3,5-tris(tri-fluoromethyl)diphenylamine N-methyl-4-nitro-2,4'-bis(trifluoromethyl)di-phenylamine 4-chloro-N~methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 4-bromo-2-chloro-N-ethyl-6-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-chloro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,4-dichloro-N-ethyl-3-methyl-4',6-dinitro-2'-trifluoromethyldiphenylamine 2,3,4-tribromo-N-ethyl-5-fluoro-4',6-dinitro-2'-trifluoromethyldiphenyl.amine N-methyl-2,4,4'-trinitro-2'~trifluoromethyldi~
phenylamine 2,4,6-trichloro-3,5-difluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine - 109~3Zi 2,4-dibromo-6-chloro-N-ethyl-3,5-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dibromo-3,5-dichloro-N-methyl-4~-nitro-2',6-bis~trifluoromethyl)diphenylamine N-ethyl-3,5-difluoro-4',6-dinitro-2'-trifluoro-methyldiphenylamine 4~bromo-2-chloro-3,5-difluoro-6,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-3,5-difluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-N-ethyl-3,5-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-N-ethyl-4'-nitro-2'-~rifluoromethyl-diphenylamine 2,6-dichloro-3,5-difluoro-4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dichloro-4-cyano-N-ethyl-3,5-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-3~,5-difluoro-N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-3,6-difluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-chloro-N-ethyl-3,6-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-2 chloro-N-methyl-4'-nitro-2',6-bis-(trifluoromethyl)diphenylamine 2,4-dibromo-N-ethyl-6-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 10~ 3Z~
2,4-dibromo-N-ethyl-4'-nitro-2',6-bis(trifluoro-methyl)diphenylamine 3,4-dibromo-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine The following are the preferred compounds of this invention.
2,4,6-trichloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4,6-trichloro-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4-dibromo-N-methyl-4'-nitro-2'-~rifluoromethyl-diphenylamine N-methyl-4-nitro-2-trifluoromethyldiphenylamine N-ethyl-4-nitro-2-trifluoromethyldiphenylamine 2,4-dibromo-6-chloro N-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2,4,6-tribromo-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine N-methyl-4-nitro-2,3',5'-tris(trifluoromethyl)-diphenylamine 2,6-dibromo-4-chloro-N-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 4-bromo-2,6-dichloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine The compounds of formula I are prepared according to the process sketched below. It will be noted that the two phenyl rings, which will be reerred to as the ben o-trifluoride ring and the aniline ring, may be coupled either before or after the alkyl R group is attached to the amino nitrogen.
~9~
O~N ~ --halo + H -F~ ~ R
OnN- ~ ~ - halo ~ HzN- ~ R~
O~N- ~ --F~ R~
~F~ R~ R9 .o 2 0 ~--o~
\CF Rl o Ra ~1, / optional product \ halogenation X-~72~ -19-~9~8~,~
The term "halo" indicates that the benzotrifluoride ring may be substituted with any convenient halogen atom.
Chlorine and fluorine atoms are preferred, and chlorine i5 usually most convenient.
In the above formula, R6, R7, R8, R9 and R10, respectively, have the values of Rl, R , R3, R and R , respectively, of the desired product, 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 through R substituents of the product, or with an unsub-stituted aniline, depending upon the substituents of the desired product. The halogen substituents of the anilinP
ring may be added at the end of the process. Thus, only any cyano, nitro, methyl or trifluoromethyl substituents of the aniline ring of the deslred compound need be in place before the two rings are coupled.
All of the compounds described above are new compounds, including both the final products produced by the process above and the intermediates which have not gone through the optional halogenation.
The individual steps of the above processes are not extraordinary in organic chemistry, and are conducted as a 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 1(~9~Z:~
useful. The reactions may be carried out, for example, in alkanols such as ethanol, in ~hich 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 tetra-hydrofuran, 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 car-bonate, and organic tertiary amines such as pyridine and triethylamine, as well as a simple excess of the aniline starting compound, may be used.
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, the preferred reaction solvent is acetone. ~ther solvents, such as tetrahydrofuran, dioxane and diethyl ether, are also useful, as are alkanes such as hexane and octane. Dimethyl-formamide is the preferred solvent for alkylations withalkyl 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, par-ticularly sodium carbonate. However, other inorganic bases, such as the alkali metal carbonates, bicarbonates and hydroxides, can be used, as can the alkali metal hydrides.
X-4726 ~21-~C~9~8z~
The amount of base used depends upon the reaction ~emperature. 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 e~cess 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.
Halogenation of the aniline ring is comparatively simpleO Chlorinations are usually best performed with elemental chlorine in acetic acid, or in methyIene chloride or the like halogenated 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 ~uite effective.
Iodination is best carried out with iodine mono-chloride as the reagent.
~ ~o~
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 sul-fonic acid as the blocking group, because it is readily added and readily removed.
The starting substituted anilines and phenyl halides are readlly 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 deslred trifluoromethyls. The acid group is fluorinated with sulfur tetrafluoride.
It will be understood that the fluorinated aniline compounds are often prepared by first making a diazonium fluoroborate saIt 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 recentiy been found that fluorine atoms may be inserted in phenyl rings with elemental fluorine at very low tem-peratures.
~ he 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.
;` ~
- ~39~Z~
.
.
Example 1 2 ! 4 ! 6-tri_hloro-N-ethyl-4'-nitro-2'-trifluoromethyldiphenyl-amine 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-ethyl-2,4,6-trichloroaniline in 20 ml. of anhydrous dimethyl-formamide 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 pre-cipitate was separated by filtration, and washed with pentane to obtain 7.7 g. of 2,4,6-trichloro-N-ethyl-4'-nitro=2'-trifluoromethyldiphenylamine, NMR peaks at 1.36, 1.48, 1.60, 3.85, 4.00, 4.15 and 4.23 ppm.
Example 2 ~ 2,4,6-_richloro-N-methyl-4'-nitro-2'-trifluoromethyldi-ph nylamine Two g. of 2,4,6-trichloro-N-methylaniline was coupled with 2.2 g. of ?-chloro-5-nitrobenzotrifluoride as described in Example 1. The product was identified as 1 g.
of 2,4,6-trichloro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine, m.p. 128-129.
~ot~n~
Theoretical Found C 42.08% 42.37%
H 2.02 2.2~
N 7.01 7.03 -N-methyl-4-nitro-2-trifluoromethyldiphenylamine A 5.35 g. portion of N-methylaniline was reacted with 11.3 g. of 2-chloro-5-nitrobenzotrifluoride in the presence of sodium hydride as described in Example 1. The product was taken up in diethyl ether and decolorized with activated charcoal, and the ether was evaporated under vacuum to leave the product in the form of an orange-red oil. Trituration of the oil with hexane produced the product - in a purified form, m.p. 68-70. The yield was ~.2 g.
- TheoreticalFound C56.76~ 56.84%
H 3.74 3.93 N 9.46 9.49 Example 4 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine Following the general process of Example 1, 2~6 g.
of 4-cyano-N-methylaniline was coupled with 4.5 g. of 2-~ chloro-5-nitrobenzotrifluoride in the presence of sodium hydride at about 5. The product was recrystallized from ethanol to produce 4 g. of product, m.p. 11~-120.
TheoreticalFound C56.07~ 56.00 H 3.12 3.25 N 13.08 13044 .
~L~9~
Example _ 4,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine The general process of Example 1 was used to couple 10 g. of ~-toluidine with 21 g. of 2-chloro-5-nitro-benzotrifluoride. The reaction mixture was poured over crushed ice, and the volume was adjusted to 1.8 1. with water. It was found that an appreciable amount of tar had - formed, and the aqueous mixture was therefore extracted with diethyl ether. The organic solution was dried with sodium - 10 sulfate, filtered and evaporated to dryness under vacuum.
- The residue left after drying was purified by chromatography on a silica gel column with toluene,as -the eluent. The product-containing fractions were combined and evaporated to dryness to produc~ 4.1 g. of acceptably pure 4-methyl-4'-nitro-2'-trifluoromethyldiphenylamine.
One g. of the above intermediate was dissolved in 20 ml. of acetone and alkylated with 2 ml. of dimethyl sulfate in the presence of~sodium hydride at reflux tem-perature. The reaction mixture was diluted with water, and extracted with diethyl ether. The organic layer was dried with magnesium sulfate and evaporated under vacuum to produce an oil, which was chromatographed on a silica gel -~ column to produce 1 g. of pure 4,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine, a liquid.
Theoretical Found -C 58.07~ 58.20%
H 4.22 4~37 N 9.03 8.97 S. ~',.
,. . .
Example _ N-methyl-4-nitro-2,4'-bis(trifl _ ometh~l)diJ~ ylamine A 10 g. portion of 4 aminobenzotrifluoride was coupled with 14 g. of 2-chloro-5-nitrobenzotrifluoride according to the process of Example 1. The product was purified by chromatography over silica gel with toluene as the eluent to produce 2.9 g. of 4-nitro-2,4'-bis(trifluoro-methyl)diphenylamine.
The above intermediate was alkylated with 9.1 g.
of dimethyl sulfate in acetonè in the presence of sodium hydride. The product was purified as described in Example 5 to produce 3.4 g. of pure N-methyl 4-nitro-2,4'-bis(tri-fluoromethyl)diphenylamine, a liquld.
TheoreticalFound C49.46% 49.20 H 2077 2.93 N 7.69 7.99 Example 7 N-methyl~4-nitro-2,3'-bis(trifluoromethyl)diphenylamine A 16.1 g. portion of 3-aminobenzotrifluoride was alkylated with 14 g. of dimethyl sulfate in acetone in the presence of 16 g. of sodium carbonate. After 3 hours of stirring at reflux temperature, the reaction mixture was diluted with diethyl ether and filtered. Evaporation of the reaction mixture to dryness under vacvum left a viscous oil, which was ta]cen up in 40 ml. of dimethylformamide. Twelve g. of sodium hydride was added, and 10 ml. of 2-chloro-
2,4,6-tribromo-N-ethyl-4'-nitro-2',3-bis(tri-fluoromethyl)diphenylamine 2-bromo-4-chloro-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4,6-trichloro-N-ethyl-4'-nitro-2',3-bis(tri-f luoromethyl)diphenylamine 2,6-dibromo-4-chloro-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-chloro-N methyl-4'-nitro-2',3-bis(tri-10 f luoromethyl~diphenylamine' 2,6-dichloro-~-methyl-4'-nitro-2',4-bis(tri-fluoromethyl~diphenylamine N-ethyl-3,5-dimethyl-4'-nitro-2'-trifluoromethyl-diphenylamine ~ -2,6-dichloro-3,5,N-trimethyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2-bromo-4-chloro-N-ethyl-3,5-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-2-chloro-3,5,N-trimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-N-methyl-4'-nitro-2',3,5-tris(trifluoro-methyl)diphenylamine 2,4,6-trichloro-N-ethyl-4'-nitro-2',3,5-tris-(trifluoromethyl)diphenylamine 2,4-dibromo-N-ethyl-4'-nitro-2',3,5-tris(tri-fluoromethyl)diphenylamine 2,6-dibromo-4-chloro-N-ethyl-4'-nitro-2',3,5-tris~trifluoromethyl)diphenylamine ~o~
2,4,6-tribromo-3,5,N-trimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-chloro-N-ethyl-4'--nitro-2,2'-bis(trifluoro-methyl~diphenylamine 2,6-dibromo-N-ethyl-3-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro--3,N~dimethyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2,6-dichloro-N-ethyl-3-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-4-cyano-3,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro-4-cya~o-N-ethyl-3-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dichloro-4-cyano-3,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-6-chloro-N-ethyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine 2,6-dibromo-N-ethyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine 2,6-dichloro-N-ethyl-4'-nitro-2',4-bis(tri-fluoromethyl)diphenylamine 2,6-dibromo-N-methyl-4,4'-dinitro-2',3-bis-(trifluoromethyl)diphenylamine 2-bromo-6-chloro-N-ethyl-4,4'-dinitro-2',3-bis(trifluo:romethyl)diphenylamine 2,6-dibromo-4-cyano-N-ethyl-4'-nitro-2',3-bis(trlfluoromethyl)diphenylamine ~09~
2-bromo-6-chloro-N-ethyl-4r4~-dinitro-2~ t 3~
bist~rifluoromethyl)diphenylamine 2,3,5-trichloro-N-methyl-4,4',6-trinitro-2'- -trifluoromethyldiphenylamine 4-bromo-N-ethyl-2,4'-dinitro-2'-trifluoromethyl-diphenylamine 4-chloro-N-ethyl-2,4'-dinitro-2'-trifluoromethyl-diphenylamine 2,4-dibromo-N-ethyl-4',6-dini~ro-2',5-bi~(tri-fluoromethyl)diphenylamine 4-bromo-2-chloro-N-methyl-4',6-dinitro-2l-trifluoromethyldiphenylamine 2,3,4,5,6-pentachloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,3,4,5,6-pentabromo-N-ethyl-4'-nitro-2~-tri-fluoromethyldiphenylamine 4-bromo-2,5,6-tri~hloro-N-ethyl-3-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,3,5,6-tetrabromo-4-fluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-2,3,5,6-tetrachloro-N-methyl-4'-nitro-2'~trifluoromethyldiphenylamine 3,5-dibromo-2,4 r 6-trichloro-N-ethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,3,5,6-tetrachloro-N-ethyl-4-iodo-4'-nitro-2'-trifluoromethyldiphenylamine 2,4,6-tribromo-3,5-dichloro~N-methyl-4'-nitro-2'-trifluoromethyldlphenylamine ~L~963 ~
2,3,4,6-tetrachloro-N-ethyl-5-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 3-bromo-2,4,5,6-tetrachloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylam:ine 2,3,6-tribromo-5-f:Luoro-N-methyl-4-iodo-4'-nitro-2'-trifluoromethyldiphenylamine 2-fluoro-N-methyl 4'-nitro-2'-trifluoromethyl-diphenylamine 2,3,4,6-tetrachloro-N-ethyl-4l-nitro-2'-tri-fluoromethyldiphenylamine 2,3,5,6-tetrabromo-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,6-dibromo-3,5-dichloro-N-ethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-fluoro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,3,4-trichloro-N-ethyl-5-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-4-fluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-N-ethyl-3-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-chloro-6-fluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-3-fluoro-4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 4-fluoro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine ~L~908;~L
2-chloro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 3-bromo-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-N-ethyl-4-fluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,4,6-trichloro-N-ethyl-3-fluoro-4'-nitxo-2'-trifluoromethyldiphenylamine 3-fluoro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,4-dibromo-N-ethyl-6-fluoro-4'-nitro-2'-tri-fluoromethyldiphenylamine 4-cyano-3-fluoro-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 4-bromo-N-ethyl-4'-nitro-2,2'-bis(trifluoromethyl)-diphenylamine 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-3-fluoro-40N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dibromo-3-chloro-N-methyl-4'-nitro-2',6-bis(trifluoromethyl)diphenylamine N-ethyl-4,4'-dinitro-2-trifluoromethyldiphenyl-amine 3,4-dichloro-N-met~yl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-3-fluoro-N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine ~o~
4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldi-phenylamine 4-bromo-N-methyl-4'-nitro-2',3,5-tris~triflucro-methyl)diphenylamine 2,6-dichloro-N-ethyl-3-bromo-4'--nitro-2',4-bis(trifluoromethyl)diphenylamine 3l5-dibromo-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2-fluoro-3,N-dimethyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,6-dichloro-N-methyl-4'-nitro-2',3,5-tris(tri-fluoromethyl)diphenylamine N-methyl-4-nitro-2,4'-bis(trifluoromethyl)di-phenylamine 4-chloro-N~methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 4-bromo-2-chloro-N-ethyl-6-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-chloro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine 2,4-dichloro-N-ethyl-3-methyl-4',6-dinitro-2'-trifluoromethyldiphenylamine 2,3,4-tribromo-N-ethyl-5-fluoro-4',6-dinitro-2'-trifluoromethyldiphenyl.amine N-methyl-2,4,4'-trinitro-2'~trifluoromethyldi~
phenylamine 2,4,6-trichloro-3,5-difluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine - 109~3Zi 2,4-dibromo-6-chloro-N-ethyl-3,5-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dibromo-3,5-dichloro-N-methyl-4~-nitro-2',6-bis~trifluoromethyl)diphenylamine N-ethyl-3,5-difluoro-4',6-dinitro-2'-trifluoro-methyldiphenylamine 4~bromo-2-chloro-3,5-difluoro-6,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-3,5-difluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-N-ethyl-3,5-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-N-ethyl-4'-nitro-2'-~rifluoromethyl-diphenylamine 2,6-dichloro-3,5-difluoro-4-iodo-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dichloro-4-cyano-N-ethyl-3,5-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 2,6-dibromo-3~,5-difluoro-N-methyl-4,4'-dinitro-2'-trifluoromethyldiphenylamine 2,4-dichloro-3,6-difluoro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine 2-bromo-4-chloro-N-ethyl-3,6-difluoro-4'-nitro-2'-trifluoromethyldiphenylamine 4-bromo-2 chloro-N-methyl-4'-nitro-2',6-bis-(trifluoromethyl)diphenylamine 2,4-dibromo-N-ethyl-6-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 10~ 3Z~
2,4-dibromo-N-ethyl-4'-nitro-2',6-bis(trifluoro-methyl)diphenylamine 3,4-dibromo-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine The following are the preferred compounds of this invention.
2,4,6-trichloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4,6-trichloro-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine 2,4-dibromo-N-methyl-4'-nitro-2'-~rifluoromethyl-diphenylamine N-methyl-4-nitro-2-trifluoromethyldiphenylamine N-ethyl-4-nitro-2-trifluoromethyldiphenylamine 2,4-dibromo-6-chloro N-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 2,4,6-tribromo-N-methyl-4'-nitro-2'-trifluoro-methyldiphenylamine N-methyl-4-nitro-2,3',5'-tris(trifluoromethyl)-diphenylamine 2,6-dibromo-4-chloro-N-methyl-4'-nitro-2'-tri-fluoromethyldiphenylamine 4-bromo-2,6-dichloro-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine The compounds of formula I are prepared according to the process sketched below. It will be noted that the two phenyl rings, which will be reerred to as the ben o-trifluoride ring and the aniline ring, may be coupled either before or after the alkyl R group is attached to the amino nitrogen.
~9~
O~N ~ --halo + H -F~ ~ R
OnN- ~ ~ - halo ~ HzN- ~ R~
O~N- ~ --F~ R~
~F~ R~ R9 .o 2 0 ~--o~
\CF Rl o Ra ~1, / optional product \ halogenation X-~72~ -19-~9~8~,~
The term "halo" indicates that the benzotrifluoride ring may be substituted with any convenient halogen atom.
Chlorine and fluorine atoms are preferred, and chlorine i5 usually most convenient.
In the above formula, R6, R7, R8, R9 and R10, respectively, have the values of Rl, R , R3, R and R , respectively, of the desired product, 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 through R substituents of the product, or with an unsub-stituted aniline, depending upon the substituents of the desired product. The halogen substituents of the anilinP
ring may be added at the end of the process. Thus, only any cyano, nitro, methyl or trifluoromethyl substituents of the aniline ring of the deslred compound need be in place before the two rings are coupled.
All of the compounds described above are new compounds, including both the final products produced by the process above and the intermediates which have not gone through the optional halogenation.
The individual steps of the above processes are not extraordinary in organic chemistry, and are conducted as a 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 1(~9~Z:~
useful. The reactions may be carried out, for example, in alkanols such as ethanol, in ~hich 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 tetra-hydrofuran, 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 car-bonate, and organic tertiary amines such as pyridine and triethylamine, as well as a simple excess of the aniline starting compound, may be used.
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, the preferred reaction solvent is acetone. ~ther solvents, such as tetrahydrofuran, dioxane and diethyl ether, are also useful, as are alkanes such as hexane and octane. Dimethyl-formamide is the preferred solvent for alkylations withalkyl 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, par-ticularly sodium carbonate. However, other inorganic bases, such as the alkali metal carbonates, bicarbonates and hydroxides, can be used, as can the alkali metal hydrides.
X-4726 ~21-~C~9~8z~
The amount of base used depends upon the reaction ~emperature. 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 e~cess 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.
Halogenation of the aniline ring is comparatively simpleO Chlorinations are usually best performed with elemental chlorine in acetic acid, or in methyIene chloride or the like halogenated 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 ~uite effective.
Iodination is best carried out with iodine mono-chloride as the reagent.
~ ~o~
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 sul-fonic acid as the blocking group, because it is readily added and readily removed.
The starting substituted anilines and phenyl halides are readlly 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 deslred trifluoromethyls. The acid group is fluorinated with sulfur tetrafluoride.
It will be understood that the fluorinated aniline compounds are often prepared by first making a diazonium fluoroborate saIt 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 recentiy been found that fluorine atoms may be inserted in phenyl rings with elemental fluorine at very low tem-peratures.
~ he 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.
;` ~
- ~39~Z~
.
.
Example 1 2 ! 4 ! 6-tri_hloro-N-ethyl-4'-nitro-2'-trifluoromethyldiphenyl-amine 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-ethyl-2,4,6-trichloroaniline in 20 ml. of anhydrous dimethyl-formamide 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 pre-cipitate was separated by filtration, and washed with pentane to obtain 7.7 g. of 2,4,6-trichloro-N-ethyl-4'-nitro=2'-trifluoromethyldiphenylamine, NMR peaks at 1.36, 1.48, 1.60, 3.85, 4.00, 4.15 and 4.23 ppm.
Example 2 ~ 2,4,6-_richloro-N-methyl-4'-nitro-2'-trifluoromethyldi-ph nylamine Two g. of 2,4,6-trichloro-N-methylaniline was coupled with 2.2 g. of ?-chloro-5-nitrobenzotrifluoride as described in Example 1. The product was identified as 1 g.
of 2,4,6-trichloro-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine, m.p. 128-129.
~ot~n~
Theoretical Found C 42.08% 42.37%
H 2.02 2.2~
N 7.01 7.03 -N-methyl-4-nitro-2-trifluoromethyldiphenylamine A 5.35 g. portion of N-methylaniline was reacted with 11.3 g. of 2-chloro-5-nitrobenzotrifluoride in the presence of sodium hydride as described in Example 1. The product was taken up in diethyl ether and decolorized with activated charcoal, and the ether was evaporated under vacuum to leave the product in the form of an orange-red oil. Trituration of the oil with hexane produced the product - in a purified form, m.p. 68-70. The yield was ~.2 g.
- TheoreticalFound C56.76~ 56.84%
H 3.74 3.93 N 9.46 9.49 Example 4 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyldiphenylamine Following the general process of Example 1, 2~6 g.
of 4-cyano-N-methylaniline was coupled with 4.5 g. of 2-~ chloro-5-nitrobenzotrifluoride in the presence of sodium hydride at about 5. The product was recrystallized from ethanol to produce 4 g. of product, m.p. 11~-120.
TheoreticalFound C56.07~ 56.00 H 3.12 3.25 N 13.08 13044 .
~L~9~
Example _ 4,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine The general process of Example 1 was used to couple 10 g. of ~-toluidine with 21 g. of 2-chloro-5-nitro-benzotrifluoride. The reaction mixture was poured over crushed ice, and the volume was adjusted to 1.8 1. with water. It was found that an appreciable amount of tar had - formed, and the aqueous mixture was therefore extracted with diethyl ether. The organic solution was dried with sodium - 10 sulfate, filtered and evaporated to dryness under vacuum.
- The residue left after drying was purified by chromatography on a silica gel column with toluene,as -the eluent. The product-containing fractions were combined and evaporated to dryness to produc~ 4.1 g. of acceptably pure 4-methyl-4'-nitro-2'-trifluoromethyldiphenylamine.
One g. of the above intermediate was dissolved in 20 ml. of acetone and alkylated with 2 ml. of dimethyl sulfate in the presence of~sodium hydride at reflux tem-perature. The reaction mixture was diluted with water, and extracted with diethyl ether. The organic layer was dried with magnesium sulfate and evaporated under vacuum to produce an oil, which was chromatographed on a silica gel -~ column to produce 1 g. of pure 4,N-dimethyl-4'-nitro-2'-trifluoromethyldiphenylamine, a liquid.
Theoretical Found -C 58.07~ 58.20%
H 4.22 4~37 N 9.03 8.97 S. ~',.
,. . .
Example _ N-methyl-4-nitro-2,4'-bis(trifl _ ometh~l)diJ~ ylamine A 10 g. portion of 4 aminobenzotrifluoride was coupled with 14 g. of 2-chloro-5-nitrobenzotrifluoride according to the process of Example 1. The product was purified by chromatography over silica gel with toluene as the eluent to produce 2.9 g. of 4-nitro-2,4'-bis(trifluoro-methyl)diphenylamine.
The above intermediate was alkylated with 9.1 g.
of dimethyl sulfate in acetonè in the presence of sodium hydride. The product was purified as described in Example 5 to produce 3.4 g. of pure N-methyl 4-nitro-2,4'-bis(tri-fluoromethyl)diphenylamine, a liquld.
TheoreticalFound C49.46% 49.20 H 2077 2.93 N 7.69 7.99 Example 7 N-methyl~4-nitro-2,3'-bis(trifluoromethyl)diphenylamine A 16.1 g. portion of 3-aminobenzotrifluoride was alkylated with 14 g. of dimethyl sulfate in acetone in the presence of 16 g. of sodium carbonate. After 3 hours of stirring at reflux temperature, the reaction mixture was diluted with diethyl ether and filtered. Evaporation of the reaction mixture to dryness under vacvum left a viscous oil, which was ta]cen up in 40 ml. of dimethylformamide. Twelve g. of sodium hydride was added, and 10 ml. of 2-chloro-
5-nitrobenzotrifluoride was then added to the mixture.
~09~
After 1 hour of stirring at about 80, the solu-tion was slowly added to 300 ml. of water and the two-phase mixture was acidified with 50 ml. of concentrated hydro-chloric acid. The oily layer was then decanted, and was purified by chromatography`over silica gel with 1:1 benz-ene:hexane. The product-containing fractions were collected and evaporated to dryness to produce 1.3 g. of N-methyl-4-nitro-2,3'-bis(trifluoromethyl)diphenylamine, a liquid.
Theoretical Found C 49.46% 50.22 H 2.77 3.01 N 7.69 7.38 The intermediates of formula I are used in the preparation of an important series of rodenticides by nitration of the vacant position of the benzotrifluoride ring ortho to the amino nitrogen. The nitration step may also nitrate any vacant position on the aniline ring ortho or ~ to the amino nitrogen. Hence, rodenticides having one of those posltions unsubstituted should be made by another route, not by use of these intermediates. When a rodenticide having a 2- or 4-nitro substituent is desired, however, that substituent may be added in the final nitra-tion step.
The cyano, methyl and trifluoromethyl substituents of the rodenticides come from corresponding substituents of ~he starting anilines from which the intermediates of this invention are made. The nitro substituents also come from the starting compounds, except for those added in the final nitration step as described above.
~OgO8Z~
Depending upon the intermediate to be used and the desired rodenticide, additional halogenation steps may be needed before the final nitration. Such halogenations are performed as described earlier in this document.
Nitration of the benzotrifluoride ring has been 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.
~09~
After 1 hour of stirring at about 80, the solu-tion was slowly added to 300 ml. of water and the two-phase mixture was acidified with 50 ml. of concentrated hydro-chloric acid. The oily layer was then decanted, and was purified by chromatography`over silica gel with 1:1 benz-ene:hexane. The product-containing fractions were collected and evaporated to dryness to produce 1.3 g. of N-methyl-4-nitro-2,3'-bis(trifluoromethyl)diphenylamine, a liquid.
Theoretical Found C 49.46% 50.22 H 2.77 3.01 N 7.69 7.38 The intermediates of formula I are used in the preparation of an important series of rodenticides by nitration of the vacant position of the benzotrifluoride ring ortho to the amino nitrogen. The nitration step may also nitrate any vacant position on the aniline ring ortho or ~ to the amino nitrogen. Hence, rodenticides having one of those posltions unsubstituted should be made by another route, not by use of these intermediates. When a rodenticide having a 2- or 4-nitro substituent is desired, however, that substituent may be added in the final nitra-tion step.
The cyano, methyl and trifluoromethyl substituents of the rodenticides come from corresponding substituents of ~he starting anilines from which the intermediates of this invention are made. The nitro substituents also come from the starting compounds, except for those added in the final nitration step as described above.
~OgO8Z~
Depending upon the intermediate to be used and the desired rodenticide, additional halogenation steps may be needed before the final nitration. Such halogenations are performed as described earlier in this document.
Nitration of the benzotrifluoride ring has been 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.
Claims (8)
1. A diphenylamine compound of the formula wherein R represents methyl or ethyl;
R1 represents hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, nitro or trifluoromethyl;
R2 and R5 independently represent hydrogen, fluoro, chloro, bromo, nitro, methyl or trifluoromethyl, provided that no more than one of R2 and R5 represents nitro;
R3 and R4 independently represent hydrogen, methyl, fluoro, chloro, bromo or trifluoromethyl;
provided that a) no more than one of R1, R2, R3, R4 and R5 represents methyl, except that R3 and R4 may both represent methyl;
b) when R1, R2, R3, R4 or R5 represents methyl or fluoro, two or three of R1, R2 and R5 represent hydrogen, chloro or bromo;
c) no more than one of R1, R2, R3, R4 and R5 represents trifluoromethyl, except that R3 and R4 may both represent trifluoromethyl;
d) when R2 or R5 represents trifluoromethyl, R1 represents hydrogen, chloro or bromo;
e) when one and only one of R3 and R4 represents trifluoromethyl, two or three of R1, R2 and R5 represent hydrogen, chloro or bromo;
f) two fluorine atoms are not adjacent to each other;
g) when R2 or R5 represents nitro, R1 represents hydrogen, chloro, bromo or nitro;
h) when R1, R2, R3, R4 or R5 represents tri-fluoromethyl, none of R1, R2, R3, R4 and R5 represents fluoro or methyl, and i) at least one of R1, R , R3, R4 and R5 is other than hydrogen.
R1 represents hydrogen, fluoro, chloro, bromo, iodo, cyano, methyl, nitro or trifluoromethyl;
R2 and R5 independently represent hydrogen, fluoro, chloro, bromo, nitro, methyl or trifluoromethyl, provided that no more than one of R2 and R5 represents nitro;
R3 and R4 independently represent hydrogen, methyl, fluoro, chloro, bromo or trifluoromethyl;
provided that a) no more than one of R1, R2, R3, R4 and R5 represents methyl, except that R3 and R4 may both represent methyl;
b) when R1, R2, R3, R4 or R5 represents methyl or fluoro, two or three of R1, R2 and R5 represent hydrogen, chloro or bromo;
c) no more than one of R1, R2, R3, R4 and R5 represents trifluoromethyl, except that R3 and R4 may both represent trifluoromethyl;
d) when R2 or R5 represents trifluoromethyl, R1 represents hydrogen, chloro or bromo;
e) when one and only one of R3 and R4 represents trifluoromethyl, two or three of R1, R2 and R5 represent hydrogen, chloro or bromo;
f) two fluorine atoms are not adjacent to each other;
g) when R2 or R5 represents nitro, R1 represents hydrogen, chloro, bromo or nitro;
h) when R1, R2, R3, R4 or R5 represents tri-fluoromethyl, none of R1, R2, R3, R4 and R5 represents fluoro or methyl, and i) at least one of R1, R , R3, R4 and R5 is other than hydrogen.
2. A compound of Claim 1 wherein R1 represents hydrogen, fluoro, chloxo, bromo, iodo, cyano, nitro or trifluoromethyl.
3. A compound of Claim 2 wherein R2 and R5 independently represent hydrogen, fluoro, chloro, bromo, nitro or trifluoromethyl.
4. A compound of claim 3 wherein R3 and R4 independently represent hydrogen, fluoro, chloro, bromo or trifluoromethyl.
5. Any of the following compounds of Claim 4:
2,4,6-trichloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine N-methyl-4-nitro-2,4-bis(trifluoromethyl)di-phenylamine.
2,4,6-trichloro-N-ethyl-4'-nitro-2'-trifluoro-methyldiphenylamine 4-cyano-N-methyl-4'-nitro-2'-trifluoromethyl-diphenylamine N-methyl-4-nitro-2,4-bis(trifluoromethyl)di-phenylamine.
6. A compound of claim 3 wherein R2 and R5 independently represent hydrogen, chloro, bromo or fluoro and R represents methyl.
7. A compound of claim 6 wherein R1 represents hydrogen, chloro or bromo.
8. Any of the following compounds of Claim 7:
2,4,6-trichloro-N~methyl-4'-nitro-2'-trifluoro-methyldiphenylamine N-methyl-4-nitro-2-trifluoromethyldiphenylamine N-methyl-4-nitro-2,3'-bis(trifluoromethyl)di-phenylamine.
2,4,6-trichloro-N~methyl-4'-nitro-2'-trifluoro-methyldiphenylamine N-methyl-4-nitro-2-trifluoromethyldiphenylamine N-methyl-4-nitro-2,3'-bis(trifluoromethyl)di-phenylamine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70602476A | 1976-07-21 | 1976-07-21 | |
| US706,024 | 1976-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090821A true CA1090821A (en) | 1980-12-02 |
Family
ID=24835902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA258,795A Expired CA1090821A (en) | 1976-07-21 | 1976-08-10 | 4-nitro-2-trifluoromethyldiphenylamines |
Country Status (30)
| Country | Link |
|---|---|
| JP (1) | JPS601299B2 (en) |
| AT (1) | AT343623B (en) |
| BE (1) | BE846206A (en) |
| BG (1) | BG28844A3 (en) |
| CA (1) | CA1090821A (en) |
| CH (1) | CH599923A5 (en) |
| CS (1) | CS186249B2 (en) |
| DD (1) | DD127400A5 (en) |
| DE (1) | DE2640461A1 (en) |
| DK (1) | DK430976A (en) |
| ES (1) | ES451904A1 (en) |
| FI (1) | FI762498A (en) |
| FR (1) | FR2359117A1 (en) |
| GB (1) | GB1549411A (en) |
| GR (1) | GR61291B (en) |
| HU (1) | HU175077B (en) |
| IE (1) | IE43932B1 (en) |
| IL (1) | IL50256A (en) |
| IN (1) | IN142337B (en) |
| IT (1) | IT1065257B (en) |
| MX (1) | MX4393E (en) |
| NL (1) | NL7610496A (en) |
| NO (1) | NO143024C (en) |
| PL (1) | PL106778B1 (en) |
| PT (1) | PT65678B (en) |
| RO (1) | RO70077A (en) |
| SE (1) | SE435056B (en) |
| SU (1) | SU626688A3 (en) |
| YU (1) | YU214776A (en) |
| ZA (1) | ZA764841B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5774611A (en) * | 1980-10-28 | 1982-05-10 | Mitsubishi Precision Co Ltd | Attitude reference apparatus employing single axis platform |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2212825A (en) * | 1937-12-31 | 1940-08-27 | Du Pont | Nitro-trifluoromethyl-aryl amines and process for making them |
| BE577941A (en) * | 1958-04-22 |
-
1976
- 1976-08-09 IE IE1760/76A patent/IE43932B1/en unknown
- 1976-08-10 GB GB33174/76A patent/GB1549411A/en not_active Expired
- 1976-08-10 CA CA258,795A patent/CA1090821A/en not_active Expired
- 1976-08-11 GR GR51459A patent/GR61291B/en unknown
- 1976-08-11 ZA ZA00764841A patent/ZA764841B/en unknown
- 1976-08-12 IN IN1467/CAL/1976A patent/IN142337B/en unknown
- 1976-08-12 HU HU76EI691A patent/HU175077B/en unknown
- 1976-08-12 IL IL7650256A patent/IL50256A/en unknown
- 1976-08-25 IT IT26533/76A patent/IT1065257B/en active
- 1976-08-30 SE SE7609587A patent/SE435056B/en unknown
- 1976-08-30 MX MX764868U patent/MX4393E/en unknown
- 1976-08-31 FI FI762498A patent/FI762498A/fi not_active Application Discontinuation
- 1976-09-01 YU YU02147/76A patent/YU214776A/en unknown
- 1976-09-07 AT AT664076A patent/AT343623B/en not_active IP Right Cessation
- 1976-09-08 DE DE19762640461 patent/DE2640461A1/en not_active Withdrawn
- 1976-09-09 CH CH1148176A patent/CH599923A5/xx not_active IP Right Cessation
- 1976-09-10 DD DD194749A patent/DD127400A5/xx unknown
- 1976-09-15 BE BE1007627A patent/BE846206A/en not_active IP Right Cessation
- 1976-09-15 FR FR7627686A patent/FR2359117A1/en active Granted
- 1976-09-16 CS CS7600006026A patent/CS186249B2/en unknown
- 1976-09-17 RO RO7687563A patent/RO70077A/en unknown
- 1976-09-20 NO NO763217A patent/NO143024C/en unknown
- 1976-09-21 NL NL7610496A patent/NL7610496A/en active Search and Examination
- 1976-09-24 SU SU762403404A patent/SU626688A3/en active
- 1976-09-24 DK DK430976A patent/DK430976A/en not_active Application Discontinuation
- 1976-09-27 ES ES451904A patent/ES451904A1/en not_active Expired
- 1976-10-04 PT PT65678A patent/PT65678B/en unknown
- 1976-10-26 PL PL1976193263A patent/PL106778B1/en unknown
- 1976-10-28 BG BG7634547A patent/BG28844A3/en unknown
- 1976-11-18 JP JP51139414A patent/JPS601299B2/en not_active Expired
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| MKEX | Expiry |