Process for preparing cis-alkoxy-substituted spirocyclic phenylacetylamino acid esters and cis-alkoxy-substituted spirocyclic 1H-pyrrolidine-2,4-dione derivatives

Patent metadata

Field	Value
Publication number	US-9840459-B2
Application number	US-201615161978-A
Country	US
Kind code	B2
Filing date	May 23, 2016
Priority date	Mar 28, 2012
Publication date	Dec 12, 2017
Grant date	Dec 12, 2017

Abstract

The present invention relates to a novel process for preparing cis-alkoxy-substituted spirocyclic phenylacetylamino acid esters and cis-alkoxy-substituted spirocyclic 1H-pyrrolidine-2,4-dione derivatives, and also to novel intermediates and starting materials which are produced and/or used in the process according to the invention.

First claim

The invention claimed is:

1. A compound of formula (IIb)

in which
X represents alkyl, halogen, alkoxy, haloalkyl or haloalkoxy,
Y represents hydrogen, alkyl, alkoxy, halogen, haloalkyl or haloalkoxy, where only one of the radicals X or Y may represent haloalkyl or haloalkoxy,
A represents C1-C6-alkyl,
R′ represents alkyl,
R″ represents alkyl,
M represents an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminium or an ion equivalent of a transition metal or furthermore
represents an ammonium ion where optionally one, two, three or all four hydrogen atoms may be replaced by identical or different radicals from the groups C 1 -C 5 -alkyl, C 1 -C 5 -isoalkyl or C 3 -C 7 -cycloalkyl, each of which may be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulphur atoms, or furthermore
represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU), or furthermore
represents a heterocyclic ammonium cation, for example in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-di-methylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methyl sulphate, or furthermore
represents a sulphonium ion, or furthermore
represents a magnesium halide cation,

n represents the number 1 or 2.

2. A compound of formula (IV)

in which
X represents alkyl, halogen, alkoxy, haloalkyl or haloalkoxy,
Y represents hydrogen, alkyl, alkoxy, halogen, haloalkyl or haloalkoxy, where only one of the radicals X or Y may represent haloalkyl or haloalkoxy,
A represents C1-C6-alkyl,
R′ represents alkyl.

3. A process for preparing compounds of the formula (X)

in which
X represents alkyl, halogen, alkoxy, haloalkyl or haloalkoxy,
Y represents hydrogen, alkyl, alkoxy, halogen, haloalkyl or haloalkoxy, where only one of the radicals X or Y may represent haloalkyl or haloalkoxy,
A represents C 1 -C 6 -alkyl,
R′ represents alkyl,
R″ represents alkyl,
M represents an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminium or an ion equivalent of a transition metal or furthermore represents an ammonium ion where optionally one, two, three or all four hydrogen atoms may be replaced by identical or different radicals from the groups C 1 -C 5 -alkyl, C 1 -C 5 -isoalkyl or C 3 -C 7 -cycloalkyl, each of which may be mono- or poly substituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulphur atoms, or furthermore
represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, for example morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU), or furthermore
represents a heterocyclic ammonium cation, for example in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-di-methylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methyl sulphate, or furthermore
represents a sulphonium ion, or furthermore
represents a magnesium halide cation,

n represents the number 1 or 2,
wherein, in a one-pot reaction,
a compound of formula (IIa)

is converted in the presence of a base
into a compound of formula (IIb)

and reacted with a compound of formula (III)

in which Hal represents halogen,
in the presence of a strong base
ZLR″  (XI)

where
Z represents an alkali metal ion,
L represents oxygen or sulfur,
R″ has the meanings given above.

4. The process according to claim 3 , where the base and strong base used is sodium methoxide.

5. A compound of formula (I″)

in which
X represents alkyl, halogen, alkoxy, haloalkyl or haloalkoxy,
Y represents hydrogen, alkyl, alkoxy, halogen, haloalkyl or haloalkoxy, where only one of the radicals X or Y may represent haloalkyl or haloalkoxy,
Z represents an alkali metal ion,
A represents C 1 -C 6 -alkyl,
R″ represents alkyl.

Assignees

• Bayer Ip Gmbh
• Bayer Cropscience Ag

Inventors

• Farida Taraneh
• Maiwald Berndt
• Littmann Martin
• Etzel Winfried
• Warsitz Rafael
• Henck Nicolas
• Esser Michael

Classifications

• C07C233/52

  with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring · CPC title

• C07C2601/14

  The ring being saturated · CPC title

• C07C231/12 Primary

  by reactions not involving the formation of carboxamide groups · CPC title

• C07D209/54

  Spiro-condensed · CPC title

• C07C233/51 Primary

  having the carbon atom of the carboxamide group bound to an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings · CPC title