Method for Producing Alkylnitrobenzenes and Alkylanilines, Unbranched in the 1'-Position, from Nitrotoluenes
The present invention relates to a process for preparing nitrobenzene derivatives and aniline derivatives, which are of significance as intermediates for fungicidally active alkylanilides.
1 . A nitrobenzene derivative of the formula (IV)
where
R 1 is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl; and
R 3 is —CH═CH-i-propyl, —CH 2 CH 2 -t-butyl, —CH 2 CH 2 -i-propyl or
or
R 1 is halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl; and
R 3 is —CH═CH-t-butyl,
2 . A nitrobenzene derivative as claimed in claim 1 , of the formula (V)
where
R 1 is halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl.
3 . A nitrobenzene derivative as claimed in claim 1 , of the formula (VI)
where
R 1 is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl.
4 . A nitrobenzene derivative as claimed in claim 1 , of the formula (VII)
where
R 1 is halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl.
5 . A nitrobenzene derivative as claimed in claim 1 , of the formula (VIII)
where
R 1 is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl.
6 . A nitrobenzene derivative as claimed in claim 1 , of the formula (IX)
where
R 1 is halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl.
7 . A nitrobenzene derivative as claimed in claim 1 , of the formula (XII)
where
is halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl.
8 . A process for preparing a nitrobenzene derivative of the formula (I)
where
R 1 is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′═H, F or O—C 1-4 -alkyl, and
R 2 is i-propyl, cyclopropyl, ethylenyl or t-butyl,
comprising coupling a 2-halonitrobenzene of the formula (II)
with an alkene of the formula (III)
R 2 —CH═CH 2 (III)
where
R 1 and R 2 are defined as above, and
X is a halogen atom,
in the presence of a noble metal catalyst.
9 . A process for preparing a compound of the formulae (X) or (XI)
where
R 1 is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and O—C 1-4 -alkyl,
R 5 is —CH 2 CH 2 -t-butyl, —CH 2 CH 2 -i-propyl, or —CH 2 —CH 2 -cyclopropyl, and
R 6 is —CH 2 CH 2 -t-butyl, —CH 2 CH 2 -i-propyl, —CH 2 —CH 2 -cyclopropyl, —CH═CH-t-butyl,
—CH═CH-i-propyl,
comprising hydrogenating a compound of the formula (I)
where
R 1 is defined as above, and
R 2 is i-propyl, cyclopropyl, ethylenyl or t-butyl.
10 . A process for preparing a compound of the formula (XII)
where
R 1 is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′═H, F or O—C 1-4 -alkyl, and
R 7 is —CH 2 CH 2 -t-butyl,
—CH 2 CH 2 -i-propyl,
comprising hydrogenating a compound of the formula (XI)
where
R 1 is defined as above, and
R 6 is —CH═CH-t-butyl,
—CH═CH-i-propyl,
11 . A process for preparing a compound of the formulae (VII), (VIII) or (IX)
where
is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl,
comprising cyclopropanating a compound of the formula (XII)
where
R 1 is defined as above.
12 . A process for preparing a nitrobenzene derivative of the formula (IX)
where
R 1 is hydrogen, halogen, or —CR′(CF 3 ) 2 where R′ is selected from the group consisting of H, F and —O—C 1-4 -alkyl,
comprising cyclopropanating a nitrobenzene derivative of the formulae (VII) or (VIII)
where
R 1 is defined as above.
13 . The process as claimed in claim 11 , further comprising Simmons-Smith reaction with dihalomethane, zinc and/or copper.
14 . The process as claimed in claim 12 , further comprising Simmons-Smith reaction with dihalomethane, zinc and/or copper.