Process for preparing spirocyclic tetronic acid derivatives

Details Process for preparing spirocyclic tetronic acid derivatives Process for preparing spirocyclic tetronic acid derivatives

2001-03-12

2002-11-05

Rotman, Alan L. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acid esters

C560S193000, C560S194000, C549S296000, C549S297000, C549S298000

Reexamination Certificate

active

06476251

ABSTRACT:

The present invention relates to a novel process for preparing known spirocyclic tetronic acid derivatives.
The multi-step synthesis of spirocyclic tetronic acid derivatives is known (EP-A-528 156).
It has now been found that compounds of the formula (I)
in which
X represents alkyl, halogen, alkoxy or halogenoalkyl,
Y represents hydrogen, alkyl, halogen, alkoxy or halogenoalkyl,
Z represents alkyl, halogen or alkoxy,
n represents a number from 0 to 3, or the radicals X and Z together with the phenyl radical to which they are attached form the naphthalene radical of the formula
in which Y is as defined above,
A represents an in each case optionally substituted radical from the group consisting of alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl and alkylthioalkyl, represents in each case saturated or unsaturated and optionally substituted cycloalkyl or heterocyclyl or represents in each case optionally halogen-, alkyl-, halogenoalkyl-, alkoxy-, halogenoalkoxy-, cyano- or nitro-substituted aryl, arylalkyl or hetaryl,
B represents alkyl or alkoxyalkyl or
A and B together with the carbon atom to which they are attached represent a saturated or unsaturated, optionally substituted carbocycle or heterocycle,
R
1
represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxy, alkenyloxy, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally substituted cycloalkyl which may be interrupted by heteroatoms, represents optionally substituted phenyl or phenoxy, optionally substituted phenylalkyl or phenylalkyloxy, substituted hetaryl, substituted phenoxyalkyl or substituted hetaryloxyalkyl,
and the stereo- and enantiomerically pure forms of compounds of the formula (I) are obtained when compounds of the formula (II)
in which
X, Y, Z, n, A and B are each as defined above and
R
8
represents alkyl
are reacted with a base and compounds of the formula (III)
in which
R
1
is as defined above and
Hal represents halogen, in particular chlorine or bromine,
if appropriate in the presence of a diluent.
Using the process according to the invention, it is surprisingly possible to prepare the abovementioned compounds in a simpler manner in a one-pot process, without isolation of the intermediates, in higher purity and with better yields.
In the general formulae (I), (II) and (III), the substituents
X preferably represents C
1
-C
6
-alkyl, halogen, C
1
-C
6
-alkoxy or C
1
-C
3
-halogenoalkyl,
Y preferably represents hydrogen, C
1
-C
6
-alkyl, halogen, C
1
-C
6
-alkoxy or C
1
-C
3
-halogenoalkyl,
Z preferably represents C
1
-C
6
-alkyl, halogen or C
1
-C
6
-alkoxy,
n preferably represents a number from 0 to 3,
 or the radicals X and Z together with the phenyl radical to which they are attached form the naphthalene radical of the formula
in which Y is defined as above,
A preferably represents in each case optionally halogen-substituted C
1
-C
12
-alkyl, C
2
-C
8
-alkenyl, C
1
-C
10
-alkoxy-C
1
-C
8
-alkyl, represents optionally halogen-, C
1
-C
6
-alkyl- or C
1
-C
6
-alkoxy-substituted C
3
-C
8
-cycloalkyl, in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur or represents in each case optionally halogen-, C
1
-C
6
-alkyl-, C
1
-C
6
-halogenoalkyl-, C
1
-C
6
-alkoxy-, C
1
-C
6
-halogenoalkoxy-, cyano- or nitro-substituted phenyl or phenyl-C
1
-C
6
-alkyl,
B preferably represents C
1
-C
12
-alkyl or C
1
-C
8
-alkoxy-C
1
-C
6
-alkyl or
A, B and the carbon atom to which they are attached preferably represent C
5
-C
10
-cycloalkyl or C
5
-C
10
-cycloalkenyl in which optionally one methylene group is replaced by oxygen or sulphur and which are optionally substituted by C
1
-C
8
-alkyl, C
3
-C
10
-cycloalkyl, C
1
-C
8
-halogenoalkyl, C
1
-C
8
-alkoxy, C
1
-C
8
-alkylthio, halogen or phenyl or
A, B and the carbon to which they are attached preferably represent C
5
-C
8
-cycloalkyl or C
5
-C
8
-cycloalkenyl in which two carbon atoms are attached to one another by in each case optionally C
1
-C
6
-alkyl-, C
1
-C
6
-alkoxy- or halogen-substituted C
3
-C
6
-alkanediyl, C
3
-C
6
-alkenediyl or C
4
-C
6
-alkanedienediyl in which in each case optionally one methylene group is replaced by oxygen or sulphur,
R
8
preferably represents C
1
-C
6
-alkyl,
Hal preferably represents chlorine or bromine,
R
1
preferably represents in each case optionally halogen-substituted C
1
-C
20
-alkyl, C
1
-C
20
-alkoxy, C
2
-C
20
-alkenyl, C
3
-C
10
-alkenyloxy, C
1
-C
8
-alkoxy-C
1
-C
8
-alkyl, C
1
-C
8
-alkylthio-C
1
-C
8
-alkyl, optionally C
1
-C
6
-alkyl-, C
1
-C
6
-alkoxy-, fluorine- or chlorine-substituted cycloalkyl having 3 to 8 ring atoms which may be interrupted by oxygen and/or sulphur atoms,
 preferably represents in each case optionally halogen-, nitro-, C
1
-C
6
-alkyl-, C
1
-C
6
-alkoxy-, C
1
-C
6
-halogenoalkyl- or C
1
-C
6
-halogenoalkoxy-substituted phenyl or phenoxy;
 preferably represents in each case optionally halogen-, C
1
-C
6
-alkyl-, C
1
-C
6
-alkoxy-, C
1
-C
6
-halogenoalkyl-, C
1
-C
6
-halogenoalkoxy-substituted phenyl-C
1
-C
6
-alkyl or phenyl-C
1
-C
4
-alkyloxy,
 preferably represents optionally halogen- or C
1
-C
6
-alkyl-substituted hetaryl,
 preferably represents optionally halogen- or C
1
-C
6
-alkyl-substituted phenoxy-C
1
-C
6
-alkyl,
 preferably represents optionally halogen-, amino- or C
1
-C
6
-alkyl-substituted hetaryloxy-C
1
-C
6
-alkyl.
In the general formulae (I), (II) and (III), the substituents
X particularly preferably represents C
1
-C
4
-alkyl, fluorine, chlorine, bromine, C
1
-C
4
-alkoxy or C
1
-C
2
-halogenoalkyl,
Y particularly preferably represents hydrogen, C
1
-C
4
-alkyl, fluorine, chlorine, bromine, C
1
-C
4
-alkoxy or C
1
-C
2
-halogenoalkyl,
Z particularly preferably represents C
1
-C
4
-alkyl, fluorine, chlorine, bromine or C
1
-C
4
-alkoxy,
n particularly preferably represents a number from 0 to 2,
A, B and the carbon atom to which they are attached particularly preferably represent C
5
-C
8
-cycloalkyl in which in each case optionally one methylene group is replaced by oxygen or sulphur and which is optionally substituted by C
1
-C
6
-alkyl, C
1
-C
3
-halogenoalkyl, C
1
-C
6
-alkoxy, fluorine or chlorine, or
A, B and the carbon atom to which they are attached particularly preferably represent C
5
-C
6
-cycloalkyl in which two carbon atoms are attached to one another by in each case optionally C
1
-C
4
-alkyl-, C
1
-C
4
-alkoxy-, fluorine-, chlorine- or bromine-substituted C
3
-C
5
-alkanediyl, C
3
-C
5
-alkenediyl, in which in each case optionally one methylene group is replaced by oxygen or sulphur, or attached to one another by butadienediyl,
R
8
particularly preferably represents C
1
-C
4
-alkyl,
Hal particularly preferably represents chlorine or bromine,
R
1
particularly preferably represents in each case optionally fluorine- or chlorine-substituted C
1
-C
16
-alkyl, C
1
-C
16
-alkoxy, C
3
-C
6
-alkenyloxy, C
2
-C
16
-alkenyl, C
1
-C
6
-alkoxy-C
1
-C
4
-alkyl, C
1
-C
6
-alkylthio-C
1
-C
4
-alkyl, optionally methyl-, ethyl-, methoxy-, fluorine- or chlorine-substituted cycloalkyl having 3 to 7 ring atoms which may be interrupted by 1 or 2 oxygen and/or sulphur atoms,
 represents in each case optionally fluorine-, chlorine-, bromine-, nitro-, C
1
-C
4
-alkyl-, C
1
-C
4
-alkoxy-, C
1
-C
3
-halogenoalkyl- or C
1
-C
3
-halogenoalkoxy-substituted phenyl, phenoxy or benzyloxy,
 represents optionally halogen- or C
1
-C
6
-alkyl-substituted hetaryl.
In the general formulae (I), (II) and (III), the substituents
X very particularly preferably represents methyl, ethyl, propyl, i-propyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl,
Y very particularly preferably represents hydrogen, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy, ethoxy or trifluoromethyl,
Z very particularly preferably represents methyl, ethyl, i-propyl, butyl, i-butyl, tert-butyl, fluorine, chlorine, bromine, methoxy or ethoxy,
n very particularly preferably represents the number 0 to 1,
A, B and the carbon atom to which they are a

Affiliated with

Also associated with

Rating

Process for preparing spirocyclic tetronic acid derivatives does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for preparing spirocyclic tetronic acid derivatives, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for preparing spirocyclic tetronic acid derivatives will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2991620