SUBSTITUTED PYRROLINE-2-ONES AND THEIR USE AS HERBICIDES

Abstract

The present invention relates to novel herbicidally active pyrrolin-2-ones of the general formula (I) or agrochemically acceptable salts thereof and to their use for controlling broad-leaved weeds and weed grasses in crops of useful plants.

Claims

1. Pyrrolin-2-one of formula (I) or an agrochemically acceptable salt thereof, ##STR00052## where X represents C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, bromine, chlorine or fluorine; Y represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, bromine, chlorine or fluorine; R.sup.1 represents C.sub.1-C.sub.6-alkyl; R.sup.2 represents hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00053## in which R.sup.3 represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.4-alkyl; R.sup.4 represents C.sub.1-C.sub.4-alkyl; R.sup.5 represents C.sub.1-C.sub.4-alkyl, an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, nitro or cyano; R.sup.6, R.sup.6′ independently of one another represent methoxy or ethoxy; R.sup.7, R.sup.8 each independently of one another represent methyl, ethyl, phenyl or together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered ring, where one ring carbon atom may optionally be replaced by an oxygen or sulfur atom, E 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, a magnesium halogen cation, or an ammonium ion in which optionally one, two, three or all four hydrogen atoms are replaced by identical or different radicals from the groups C.sub.1-C.sub.10-alkyl or C.sub.3-C.sub.7-cycloalkyl which independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms; or represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, optionally morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[1.1.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU); or represents a heteroaromatic ammonium cation, optionally in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate or furthermore also represents a trimethylsulfonium ion.

2. The Compound of formula (I) according to claim 1 or an agrochemically acceptable salt thereof, wherein the radicals have the following meanings: X represents C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, bromine, chlorine or fluorine; Y represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, bromine, chlorine or fluorine; R.sup.1 represents C.sub.1-C.sub.6-alkyl; R.sup.2 represents hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy-C.sub.2-C.sub.4-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.2-C.sub.6-alkenyl or C.sub.2-C.sub.6-alkynyl; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00054## in which R.sup.3 represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.4-alkyl; R.sup.4 represents C.sub.1-C.sub.4-alkyl; R.sup.5 represents C.sub.1-C.sub.4-alkyl, an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl or C.sub.1-C.sub.4-alkoxy; E 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, a magnesium halogen cation, or an ammonium ion in which optionally one, two, three or all four hydrogen atoms are replaced by identical or different radicals from the groups C.sub.1-C.sub.10-alkyl or C.sub.3-C.sub.7-cycloalkyl which independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms; or represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, optionally morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[1.1.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU); or represents a heteroaromatic ammonium cation, optionally in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate or furthermore also represents a trimethylsulfonium ion.

3. The compound of formula (I) according to claim 1 or an agrochemically acceptable salt thereof, wherein the radicals have the following meanings: X represents C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, bromine, chlorine or fluorine; Y represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, bromine, chlorine or fluorine; R.sup.1 represents C.sub.1-C.sub.6-alkyl; R.sup.2 represents hydrogen, C.sub.1-C.sub.4-alkyl, methoxyethyl or ethoxyethyl, C.sub.1-C.sub.2-haloalkyl, cyclopropyl, C.sub.2-C.sub.4-alkenyl or C.sub.2-C.sub.4-alkynyl; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00055## in which R.sup.3 represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.2-alkoxy-C.sub.1-C.sub.2-alkyl; R.sup.4 represents C.sub.1-C.sub.4-alkyl; E represents an alkali metal ion, an ion equivalent of an alkaline earth metal, an ion equivalent of aluminium, an ion equivalent of a transition metal, a magnesium halogen cation or an ammonium ion, in which optionally one, two, three or all four hydrogen atoms are replaced by identical or different radicals from the groups C.sub.1-C.sub.10-alkyl or C.sub.3-C.sub.7-cycloalkyl.

4. The compound of formula (I) according to claim 1 or an agrochemically acceptable salt thereof, wherein the radicals have the following meanings: X represents methyl, ethyl, trifluoromethyl, trifluoromethoxy, bromine, chlorine or fluorine; Y represents methyl, propynyl or trifluoromethyl; R.sup.1 represents methyl or ethyl; R.sup.2 represents hydrogen or methyl; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00056## in which R.sup.3 represents methyl, ethyl, isopropyl or t-butyl; R.sup.4 represents methyl or ethyl; E represents a sodium ion or a potassium ion.

5. A process for preparing the compound of formula (I) according to claim 1 comprising cyclizing a compound of formula (II) ##STR00057## in which R.sup.9 represents alkyl, optionally methyl or ethyl, optionally in the presence of a suitable solvent or diluent, with a suitable base with formal cleaving off of the group R.sup.9OH.

6. A Compound of formula (II) ##STR00058## where X represents C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, bromine, chlorine or fluorine; Y represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, bromine, chlorine or fluorine; R.sup.1 represents C.sub.1-C.sub.6-alkyl; R.sup.2 represents hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00059## in which R.sup.3 represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.4-alkyl; R.sup.4 represents C.sub.1-C.sub.4-alkyl; R.sup.5 represents C.sub.1-C.sub.4-alkyl, an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, nitro or cyano; R.sup.6, R.sup.6′ independently of one another represent methoxy or ethoxy; R.sup.7, R.sup.8 each independently of one another represent methyl, ethyl, phenyl or together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered ring, where one ring carbon atom may optionally be replaced by an oxygen or sulfur atom, E 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, a magnesium halogen cation, or an ammonium ion in which optionally one, two, three or all four hydrogen atoms are replaced by identical or different radicals from the groups C.sub.1-C.sub.10-alkyl or C.sub.3-C.sub.7-cycloalkyl which independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms; or represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, optionally morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[1.1.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU); or represents a heteroaromatic ammonium cation, optionally in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, guinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate or furthermore also represents a trimethylsulfonium ion.

7. A Compound of formula (IV) ##STR00060## Where X represents C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, bromine, chlorine or fluorine; Y represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, bromine, chlorine or fluorine; R.sup.1 represents C.sub.1-C.sub.6-alkyl; R.sup.2 represents hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00061## in which R.sup.3 represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.4-alkyl; R.sup.4 represents C.sub.1-C.sub.4-alkyl; R.sup.5 represents C.sub.1-C.sub.4-alkyl, an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, nitro or cyano; R.sup.6, R.sup.6′ independently of one another represent methoxy or ethoxy; R.sup.7, R.sup.8 each independently of one another represent methyl, ethyl, phenyl or together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered ring, where one ring carbon atom may optionally be replaced by an oxygen or sulfur atom, E 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, a magnesium halogen cation, or an ammonium ion in which optionally one, two, three or all four hydrogen atoms are replaced by identical or different radicals from the groups C.sub.1-C.sub.10-alkyl or C.sub.3-C.sub.7-cycloalkyl which independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms; or represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, optionally morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[1.1.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU); or represents a heteroaromatic ammonium cation, optionally in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate or furthermore also represents a trimethylsulfonium ion.

8. A Compound of formula (IVa) ##STR00062## Where X represents C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, bromine, chlorine or fluorine; Y represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, bromine, chlorine or fluorine; R.sup.1 represents C.sub.1-C.sub.6-alkyl; R.sup.2 represents hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00063## in which R.sup.3 represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.4-alkyl; R.sup.4 represents C.sub.1-C.sub.4-alkyl; R.sup.5 represents C.sub.1-C.sub.4-alkyl, an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, nitro or cyano; R.sup.6, R.sup.6′ independently of one another represent methoxy or ethoxy; R.sup.7, R.sup.8 each independently of one another represent methyl, ethyl, phenyl or together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered ring, where one ring carbon atom may optionally be replaced by an oxygen or sulfur atom, E 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, a magnesium halogen cation, or an ammonium ion in which optionally one, two, three or all four hydrogen atoms are replaced by identical or different radicals from the groups C.sub.1-C.sub.10-alkyl or C.sub.3-C.sub.7-cycloalkyl which independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms; or represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, optionally morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[1.1.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU); or represents a heteroaromatic ammonium cation, in each case optionally protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate or furthermore also represents a trimethylsulfonium ion.

9. Compound of the general formula (XIII) ##STR00064## Where X represents C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-haloalkoxy, bromine, chlorine or fluorine; Y represents C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy, bromine, chlorine or fluorine; R.sup.1 represents C.sub.1-C.sub.6-alkyl; R.sup.2 represents hydrogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.3-C.sub.6-cycloalkyl-C.sub.1-C.sub.4-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-alkoxy or C.sub.1-C.sub.6-haloalkoxy; G represents hydrogen, a leaving group L or a cation E, where L represents one of the radicals below, ##STR00065## in which R.sup.3 represents C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.3-alkoxy-C.sub.1-C.sub.4-alkyl; R.sup.4 represents C.sub.1-C.sub.4-alkyl; R.sup.5 represents C.sub.1-C.sub.4-alkyl, an unsubstituted phenyl or a phenyl which is mono- or polysubstituted by halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkoxy, nitro or cyano; R.sup.6, R.sup.6′ independently of one another represent methoxy or ethoxy; R.sup.7, R.sup.8 each independently of one another represent methyl, ethyl, phenyl or together with the nitrogen atom to which they are attached form a saturated 5-, 6- or 7-membered ring, where one ring carbon atom may optionally be replaced by an oxygen or sulfur atom, E 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, a magnesium halogen cation, or an ammonium ion in which optionally one, two, three or all four hydrogen atoms are replaced by identical or different radicals from the groups C.sub.1-C.sub.10-alkyl or C.sub.3-C.sub.7-cycloalkyl which independently of one another may each be mono- or polysubstituted by fluorine, chlorine, bromine, cyano, hydroxy or interrupted by one or more oxygen or sulfur atoms; or represents a cyclic secondary or tertiary aliphatic or heteroaliphatic ammonium ion, optionally morpholinium, thiomorpholinium, piperidinium, pyrrolidinium, or in each case protonated 1,4-diazabicyclo[1.1.2]octane (DABCO) or 1,5-diazabicyclo[4.3.0]undec-7-ene (DBU); or represents a heteroaromatic ammonium cation, optionally in each case protonated pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, 2,6-dimethylpyridine, 5-ethyl-2-methylpyridine, collidine, pyrrole, imidazole, quinoline, quinoxaline, 1,2-dimethylimidazole, 1,3-dimethylimidazolium methylsulfate or furthermore also represents a trimethylsulfonium ion.

10. A Compound of formula (XII) ##STR00066##

11. A Compound of formula (XI) ##STR00067##

12. Compound of formula (X) ##STR00068##

13. Compounds 13-6, 13-7, 13-9, 13-10, 13-12, 13-13, 13-14, 13-15, 13-16, 13-19, 13-30, 13-31, 13-34, 13-35, 13-36, 13-37, 13-38, 13-39, 13-40, 13-41, 13-42, 13-43, 13-44, 13-46, 13-47, 13-50, 13-51 and 13-55 of formula (V) and/or a salt thereof.

14. An agrochemical composition, comprising a) at least one compound of formula (I) or an agrochemically acceptable salt thereof as defined in claim 1, and b) one or more auxiliaries and/or additives customary in crop protection.

15. An agrochemical composition comprising a) at least one compound of the formula (I) or an agrochemically acceptable salt thereof as defined in claim 1, b) one or more active agrochemical compounds other than component a), and optionally c) one or more auxiliaries and additives customary in crop protection.

16. A method for controlling one or more unwanted plants or for regulating the growth of one or more plants, comprising applying an effective amount of at least one compound of formula (I) or an agrochemically acceptable salt thereof, as defined in claim 1, to the plants, the seed or an area on which the plants grow.

17. A product comprising one or more compounds of the formula (I) or an agrochemically acceptable salt thereof, as defined in claim 1, as herbicide or plant growth regulator.

18. The product according to claim 17, wherein the compounds of the formula (I) or an agrochemically acceptable salt thereof are used for controlling one or more harmful plants or for regulating growth in plant crops.

19. The product according to claim 18, wherein the crop plants are transgenic or nontransgenic crop plants.

Description

A. CHEMICAL EXAMPLES

Synthesis of 3-(4-chloro-2-methoxy-6-methylphenyl)-4-hydroxy-7,11,14-trioxa-1-azadispiro[4.2.5.SUP.8..2.SUP.5.]pentadec-3-en-2-one (Example No. 1-4)

[0417] ##STR00039##

Step 1: Synthesis of (3-nitro-1,5,9-trioxaspiro[5.5]undecan-3-yl)methanol

[0418] ##STR00040##

[0419] 89.5 g (0.59 mol) of 2-(hydroxymethyl)-2-nitropropane-1,3-diol and 57.0 g (0.57 mol) of tetrahydro-4H-pyran-4-one were dissolved in a mixture of 570 ml of dichloromethane and 110 ml of tetrahydrofuran. At room temperature, 75 ml (0.59 mmol) of boron trifluoride etherate were carefully added dropwise. The mixture was then stirred at room temperature for 30 min. For work-up, the content was poured on a mixture of saturated aqueous sodium bicarbonate solution and ice. The mixture was filtered and, after phase separation, the organic phase was dried and the filtrate was freed from the solvent. The residue gave, together with the precipitate from the reaction of the reaction mixture with aqueous sodium bicarbonate solution and ice, altogether 88.8 g of the desired product.

Step 2: Synthesis of (3-amino-1,5,9-trioxaspiro[5.5]undecan-3-yl)methanol

[0420] ##STR00041##

[0421] 86.8 g (0.37 mol) of (3-nitro-1,5,9-trioxaspiro[5.5]undecan-3-yl)methanol in 500 ml of ethanol were hydrogenated in an autoclave (10.0 g of Raney nickel, 40 bar hydrogen, 40° C. until there was no further change in pressure, then 1 h of stirring). The mixture was filtered and the filtrate was freed of the solvent. 85.0 g (purity 93.0% by weight) of the desired product were obtained as residue.

Step 3: Synthesis of tert-butyl [3-(hydroxymethyl)-1,5,9-trioxaspiro[5.5]undecan-3-yl]carbamate

[0422] ##STR00042##

[0423] A solution of 86.6 g (0.40 mol) of di-tert-butyl dicarbonate in 350 ml of dichloromethane was added dropwise to a solution of 85.0 g (purity 93.0% by weight; 0.39 mol) of (3-amino-1,5,9-trioxaspiro[5.5]undecan-3-yl)methanol in 350 ml of dichloromethane. The reaction mixture was stirred at room temperature for 16 h. For work-up, the content was washed with 200 ml of water. The organic phase was dried, and the filtrate was freed of the solvent. This gave 117 g of the desired product.

Step 4: Synthesis of tert-butyl (3-formyl-1,5,9-trioxaspiro[5.5]undecan-3-yl)carbamate

[0424] ##STR00043##

[0425] 53.9 g (0.42 mol) of oxalyl chloride were initially charged in 750 ml of dichloromethane. At solution of 66.3 g (0.85 mol) of dimethyl sulfoxide in 100 ml of dichloromethane was slowly added dropwise at a temperature of −70° C. The mixture was subsequently stirred at this temperature for 20 min. A solution of 117 g (0.39 mol) of tert-butyl [3-(hydroxymethyl)-1,5,9-trioxaspiro [5.5]undecan-3-yl]carbamate in 350 ml of dichloromethane was then added dropwise at −70° C. The reaction mixture was stirred at this temperature for 1 h. 172 g (1.70 mol) of triethylamine were then added at this temperature. The mixture was then stirred at room temperature for 16 h. For work-up, 500 ml of water were added, and the content was then stirred for 15 min. After phase separation, the aqueous solution was extracted three times with in each case 200 ml of dichloromethane. The combined organic phases were dried and the filtrate was freed of the solvent. 107.5 g of the desired product were isolated as residue.

Step 5: Synthesis of 3-[(tert-butoxycarbonyl)amino]-1,5,9-trioxaspiro[5.5]undecane-3-carboxylic acid

[0426] ##STR00044##

[0427] 42.5 g (0.27 mol) of potassium permanganate were dissolved in 1.5 l of water and, at a temperature of 0-5° C., slowly added dropwise to a solution of 54.0 g (0.18 mol) of tert-butyl (3-formyl-1,5,9-trioxaspiro[5.5]undecan-3-yl)carbamate in 1.5 l of acetone. The reaction mixture was slowly warmed to room temperature and then stirred at room temperature for 16 h. For work-up, 20 g of sodium thiosulfate were added, and the content was then stirred at room temperature for 30 min. After filtration, the mixture was freed of the acetone, and the aqueous solution was washed with dichloromethane. The aqueous phase was stirred with activated carbon, filtered and then adjusted to a pH of 2-3 using 3N hydrochloric acid. This gave 24.10 g of the desired product.

Step 6: Synthesis of methyl 3-[(tert-butoxycarbonyl)amino]-1,5,9-trioxaspiro[5.5]undecane-3-carboxylate (Example No. 12-1)

[0428] ##STR00045##

[0429] 7.80 g (24.6 mmol) of 3-[(tert-butoxycarbonyl)amino]-1,5,9-trioxaspiro [5.5]undecane-3-carboxylic acid and 4.13 g (49.2 mmol) of sodium bicarbonate were initially charged in 35 ml of N,N-dimethylformamide. 4.54 g (32.0 mmol) of iodomethane were then added. The reaction mixture was then stirred at room temperature for 16 h. After filtration, water was added to the filtrate. The precipitated solid was separated off, washed with a little water and dried. This gave 5.80 g of the desired product.

Step 7: Synthesis of methyl 3-amino-1,5,9-trioxaspiro[5.5]undecane-3-carboxylate (Example No. 11-1)

[0430] ##STR00046##

[0431] At 0° C., 49.0 g (0.332 mol) of sodium iodide were added to a solution of 326 g (3.02 mol) of trimethylsilyl chloride in 2.0 l of acetonitrile, and the mixture was then stirred for 30 minutes. 100 g (0.302 mol) of methyl 3-[(tert-butoxycarbonyl)amino]-1,5,9-trioxaspiro[5.5]undecane-3-carboxylate were then added at 0° C., and the content was subsequently stirred at ambient temperature for 16 h. For work-up, the reaction mixture was cooled to 0° C. and the solid was filtered off with suction. The solid was washed with petroleum ether (2×500 ml). The solid was dissolved in 2.0 l of dry dichloromethane, Amberlyst® A21 free base (140 g) was added, the mixture was stirred for 2 h and filtered and the filter residue was washed with dichloromethane (2×100 ml). The filtrate was freed of the solvent. This gave 58 g of the desired target compound.

Step 8: Synthesis of methyl 3-[2-(4-chloro-2-methoxy-6-methylphenyl)acetamido]-1,5,9-trioxaspiro[5.5]undecane-3-carboxylate (Example No. 9-4)

[0432] ##STR00047##

[0433] 957 mg (4.46 mmol) of (4-chloro-2-methoxy-6-methylphenyl)acetic acid were dissolved in 30 ml of dichloromethane. Two drops of N,N-dimethylformamide were added, followed by 669 mg (5.27 mmol) of oxalyl chloride. The mixture was stirred at room temperature for 20 min and then heated at reflux for 1 h. The content was then concentrated under reduced pressure and the residue was dissolved in 25 ml of dichloromethane (solution 1). In a separate reaction vessel, 1.88 g of methyl 3-amino-1,5,9-trioxaspiro[5.5]undecane-3-carboxylate, isolated as crude product in Step 7 and used here directly without further work-up, were dissolved in 30 ml of dichloromethane. 1.23 g (12.2 mmol) of triethylamine were then added, and the mixture was stirred at room temperature for 5 min. The above-described solution 1 was then added dropwise over 30 min to this mixture. The mixture was subsequently stirred at room temperature for 3 d. For work-up, the content was stirred with 10 ml of water and, after phase separation, the organic phase was dried. The filtrate was freed of the solvent, and the residue was purified by chromatography, which gave 680 mg of the desired product having a purity of 90% by weight.

Step 9: Synthesis of 3-(4-chloro-2-methoxy-6-methylphenyl)-4-hydroxy-7,11,14-trioxa-1-azadispiro[4.2.5.SUP.8..2.SUP.5.]pentadec-3-en-2-one (Example No. 1-4)

[0434] ##STR00048##

[0435] 640 mg (1.50 mmol) of methyl 3-[2-(4-chloro-2-methoxy-6-methylphenyl)acetamido]-1,5,9-trioxaspiro[5.5]undecane-3-carboxylate were dissolved in 6 ml of N,N-dimethylformamide. At room temperature, a solution of 336 mg (2.99 mmol) of potassium tert-butoxide in 3 ml of N,N-dimethylformamide was added in small portions over 10 min. The reaction mixture was then stirred at 60° C. for 2 h. For work-up, the mixture was freed of the solvent, and the residue was dissolved in 12 ml of water. 269 mg (4.49 mmol) of acetic acid were added to the solution. The mixture was stirred at room temperature for 15 min and then filtered. The residue was washed twice with in each case 2 ml of water and then dried. This gave 440 mg of the desired product.

Synthesis of sodium 3-(4-chloro-2-methoxy-6-methylphenyl)-2-oxo-7,11,14-trioxa-1-azadispiro[4.2.5.SUP.8..2.SUP.5.]pentadec-3-en-4-olate (Example No. 2-4)

[0436] ##STR00049##

[0437] 80 mg (0.20 mmol) of 3-(4-chloro-2-methoxy-6-methylphenyl)-4-hydroxy-7,11,14-trioxa-1-azadispiro[4.2.5.sup.8.2.sup.5]pentadec-3-en-2-one (Example No. 1-4) were dissolved in 10 ml of methanol. Subsequently, 40 mg (30% by weight; 0.22 mmol) of a solution of sodium methoxide in methanol were added. The mixture was stirred at room temperature for 30 min and then freed from the solvent. 80 mg of the desired product were obtained as residue.

Synthesis of 3-(4-chloro-2-methoxy-6-methylphenyl)-2-oxo-7,11,14-trioxa-1-azadispiro[4.2.5.SUP.8..2.SUP.5.]pentadec-3-en-4-yl propionate (Example No. 3-4)

[0438] ##STR00050##

[0439] 140 mg (0.35 mmol) of 3-(4-chloro-2-methoxy-6-methylphenyl)-4-hydroxy-7,11,14-trioxa-1-azadispiro[4.2.5.sup.8.2.sup.5]pentadec-3-en-2-one (Example No. 1-4) were dissolved in 30 ml of dichloromethane. 107 mg (1.06 mmol) of triethylamine were then added, and the reaction mixture was stirred at room temperature for 10 min. 36 mg (0.39 mmol) of propionyl chloride were then added. The content was stirred at room temperature for 20 h. For work-up, the mixture was stirred with 10 ml of water. After phase separation, the organic phase was dried and the filtrate was freed from the solvent. The residue was purified by chromatography, and 100 mg of the desired product were isolated.

Synthesis of 3-(4-chloro-2-methoxy-6-methylphenyl)-2-oxo-7,11,14-trioxa-1-azadispiro[4.2.5.SUP.8..2.SUP.5.]pentadec-3-en-4-yl ethyl carbonate (Example No. 4-4)

[0440] ##STR00051##

[0441] 140 mg (0.35 mmol) of 3-(4-chloro-2-methoxy-6-methylphenyl)-4-hydroxy-7,11,14-trioxa-1-azadispiro[4.2.5.sup.8.2.sup.5]pentadec-3-en-2-one (Example No. 1-4) were dissolved in 30 ml of dichloromethane. 107 mg (1.06 mmol) of triethylamine were then added, and the reaction mixture was stirred at room temperature for 10 min. 42 mg (0.39 mmol) of ethyl chloroformate were then added. The content was stirred at room temperature for 20 h. For work-up, the mixture was stirred with 10 ml of water. After phase separation, the organic phase was dried, and the filtrate was freed of the solvent. The residue was purified by chromatography, and 130 mg of the desired product were isolated.

[0442] NMR Data of Selected Examples

[0443] NMR Peak List Method

[0444] The 1H NMR data of selected examples are noted in the form of 1H NMR peak lists. For each signal peak, first the δ value in ppm and then the signal intensity in round brackets are listed. The δ value/signal intensity number pairs for different signal peaks are listed with separation from one another by semicolons.

[0445] The peak list for one example therefore takes the form of:

[0446] δ.sub.1 (intensity.sub.1); δ.sub.2 (intensity.sub.2); . . . ; δ.sub.i (intensity.sub.i); . . . ; δ.sub.n (intensity.sub.n)

[0447] The intensity of sharp signals correlates with the height of the signals in a printed example of an NMR spectrum in cm and shows the true ratios of the signal intensities. In the case of broad signals, several peaks or the middle of the signal and the relative intensity thereof may be shown in comparison to the most intense signal in the spectrum.

[0448] For calibration of the chemical shift of 1H NMR spectra we use tetramethylsilane and/or the chemical shift of the solvent, particularly in the case of spectra measured in DMSO. Therefore, the tetramethylsilane peak may but need not occur in NMR peak lists.

[0449] The lists of the 1H NMR peaks are similar to the conventional 1H NMR printouts and thus usually contain all peaks listed in a conventional NMR interpretation.

[0450] In addition, like conventional 1H NMR printouts, they may show solvent signals, signals of stereoisomers of the target compounds, which likewise form part of the subject matter of the invention, and/or peaks of impurities.

[0451] In the reporting of compound signals in the delta range of solvents and/or water, our lists of 1H NMR peaks show the usual solvent peaks, for example peaks of DMSO in DMSO-D.sub.6 and the peak of water, which usually have a high intensity on average.

[0452] The peaks of stereoisomers of the target compounds and/or peaks of impurities usually have a lower intensity on average than the peaks of the target compounds (for example with a purity of >90%).

[0453] Such stereoisomers and/or impurities may be typical of the particular preparation process. Their peaks can thus help in identifying reproduction of our preparation process with reference to “by-product fingerprints”.

[0454] An expert calculating the peaks of the target compounds by known methods (MestreC, ACD simulation, but also with empirically evaluated expected values) can, if required, isolate the peaks of the target compounds, optionally using additional intensity filters. This isolation would be similar to the relevant peak picking in conventional 1H NMR interpretation.

[0455] Further details of 1H NMR peak lists can be found in the Research Disclosure Database Number 564025.

[0456] Compounds 1-1 and 1-4 were measured in D.sub.2O. To this end, a drop of NaOD was added to obtain better solubility with the sodium salt thus formed and thus to obtain a better spectrum. Accordingly, the compounds characterized here are the correspnding sodium salts.

TABLE-US-00014 1-1: .sup.1H—NMR(400.6 MHz, D2O): δ = 6.6443 (2.2); 6.6428 (2.1); 6.6050 (2.1); 4.6964 (75.6); 4.2953 (3.0); 4.2658 (3.4); 3.6822 (1.3); 3.6673 (2.8); 3.6545 (1.4); 3.6435 (1.5); 3.6378 (2.1); 3.6263 (1.9); 3.6129 (1.2); 3.5684 (16.0); 3.5460 (1.2); 3.5397 (1.0); 3.5166 (1.0); 3.5102 (0.9); 2.1586 (9.3); 2.1357 (1.0); 2.1236 (1.4); 1.9137 (10.6); 1.7387 (1.1); 1.7251 (1.7); 1.7116 (1.1) 3-1: .sup.1H—NMR(400.0 MHz, CDCl3): δ = 7.2605 (16.6); 6.6817 (1.8); 6.6537 (3.0); 6.5218 (3.0); 5.2978 (1.8); 4.3338 (2.1); 4.3048 (2.4); 4.2497 (2.1); 4.2208 (2.4); 3.7872 (1.4); 3.7800 (2.8); 3.7649 (3.0); 3.7520 (3.2); 3.7299 (1.6); 3.7243 (1.4); 3.7072 (16.0); 3.6854 (2.0); 2.3644 (1.1); 2.3456 (3.5); 2.3267 (3.7); 2.3078 (1.4); 2.2894 (12.1); 2.1741 (12.9); 2.0655 (1.5); 2.0524 (2.2); 2.0416 (1.5); 1.8370 (1.6); 1.8235 (2.5); 1.8101 (1.6); 1.5727 (5.4); 1.0372 (3.8); 1.0184 (7.6); 0.9995 (3.6); −0.0002 (7.4) 4-1: .sup.1H—NMR(400.0 MHz, CDCl3): δ = 7.2606 (24.9); 6.6816 (0.9); 6.6671 (1.6); 6.6654 (1.8); 6.6637 (1.6); 6.5345 (1.6); 5.2975 (2.6); 4.3957 (1.6); 4.3669 (1.8); 4.3350 (1.7); 4.3064 (1.8); 4.0664 (0.6); 4.0542 (0.7); 4.0485 (2.0); 4.0364 (2.0); 4.0307 (2.1); 4.0186 (2.0); 4.0128 (0.7); 4.0008 (0.6); 3.7906 (0.9); 3.7842 (1.2); 3.7776 (1.3); 3.7620 (2.0); 3.7555 (1.6); 3.7499 (1.5); 3.7467 (1.6); 3.7402 (0.8); 3.7191 (16.0); 3.7121 (2.0); 3.6992 (1.7); 3.6855 (1.2); 2.2953 (8.2); 2.1878 (9.0); 2.0951 (0.7); 2.0819 (1.1); 2.0690 (0.7); 1.8413 (0.9); 1.8278 (1.3); 1.8141 (0.9); 1.5757 (2.7); 1.1529 (4.8); 1.1351 (10.4); 1.1172 (4.7); −0.0002 (11.0) 2-1: .sup.1H—NMR(400.6 MHz, D2O): δ = 6.6924 (3.0); 6.6574 (3.1); 4.6776 (35.9); 4.3537 (4.2); 4.3241 (4.6); 3.7240 (3.0); 3.7098 (2.7); 3.6954 (3.0); 3.6807 (1.8); 3.6673 (2.7); 3.6540 (1.8); 3.6180 (16.0); 3.5818 (1.3); 3.5760 (1.2); 3.2397 (5.0); 3.2384 (4.1); 2.2036 (12.1); 2.1695 (1.4); 2.1578 (1.9); 1.9603 (13.0); 1.7886 (1.5); 1.7751 (2.4); 1.7617 (1.5) 1-4: .sup.1H—NMR(400.6 MHz, D2O): δ = 6.8066 (1.6); 6.8052 (1.8); 6.8016 (2.3); 6.8001 (2.2); 6.7673 (2.2); 6.7624 (1.8); 4.7114 (128.9); 4.2716 (2.8); 4.2420 (3.2); 3.6637 (1.2); 3.6499 (2.6); 3.6434 (1.7); 3.6358 (1.4); 3.6203 (2.0); 3.6137 (1.8); 3.6073 (1.8); 3.5939 (1.2); 3.5646 (16.0); 3.5320 (1.1); 3.5255 (0.9); 3.5025 (1.0); 3.4961 (0.9); 2.1144 (0.8); 2.1004 (1.2); 2.0908 (0.8); 1.9218 (10.7); 1.7462 (1.7); 1.7208 (1.0); 1.7073 (1.5); 1.6936(1.0) 2-4: .sup.1H—NMR(400.6 MHz, D2O): δ = 6.8672 (1.6); 6.8657 (1.7); 6.8621 (2.1); 6.8607 (2.0); 6.8281 (2.1); 6.8231 (1.7); 4.6813 (58.2); 4.3387 (3.2); 4.3091 (3.7); 3.7268 (1.2); 3.7124 (2.6); 3.7059 (1.7); 3.6991 (1.4); 3.6830 (1.8); 3.6761 (1.9); 3.6719 (1.9); 3.6581 (1.2); 3.6273 (16.0); 3.5948 (1.1); 3.5883 (1.0); 3.5653 (1.0); 3.5589 (0.9); 3.2434 (11.1); 2.1797 (0.8); 2.1676 (1.1); 2.1557 (0.8); 1.9849 (10.6); 1.8049 (0.6); 1.7834 (1.0); 1.7698 (1.5); 1.7562 (1.0) 4-4: .sup.1H—NMR(400.0 MHz, CDCl3): δ = 7.2612 (22.7); 6.8626 (1.6); 6.8610 (1.7); 6.8578 (1.8); 6.8563 (1.7); 6.7372 (1.1); 6.7233 (1.9); 6.7187 (1.7); 5.2983 (4.9); 4.3915 (1.6); 4.3629 (1.8); 4.3291 (1.6); 4.3007 (1.7); 4.0972 (0.6); 4.0890 (0.8); 4.0793 (2.1); 4.0713 (2.2); 4.0615 (2.2); 4.0535 (2.1); 4.0437 (0.8); 4.0357 (0.7); 3.7818 (1.1); 3.7760 (2.4); 3.7633 (1.8); 3.7480 (3.4); 3.7424 (1.0); 3.7331 (16.0); 3.7195 (1.4); 3.7135 (2.1); 3.7003 (1.9); 3.6867 (1.3); 2.2121 (10.6); 2.0936 (0.8); 2.0806 (1.2); 2.0778 (1.2); 2.0680 (0.8); 1.8457 (1.0); 1.8322 (1.5); 1.8186 (1.0); 1.5770 (5.4); 1.1841 (5.0); 1.1663 (10.5); 1.1485 (4.8); −0.0002(12.0) 3-4: .sup.1H—NMR(400.0 MHz, CDCl3): δ = 7.2608 (29.2); 6.8514 (1.5); 6.8499 (1.6); 6.8467 (1.7); 6.8452 (1.6); 6.7120 (2.1); 6.7073 (1.8); 5.2984 (3.2); 4.3320 (1.7); 4.3031 (2.0); 4.2440 (1.8); 4.2151 (2.0); 3.7786 (2.3); 3.7723 (1.7); 3.7649 (1.7); 3.7503 (1.9); 3.7434 (1.4); 3.7292 (1.7); 3.7233 (16.0); 3.7136 (1.4); 3.7004 (2.8); 3.6943 (1.5); 3.6862 (1.3); 2.3810 (0.6); 2.3772 (0.7); 2.3620 (2.1); 2.3584 (2.2); 2.3430 (2.2); 2.3397 (2.2); 2.3241 (0.8); 2.3210 (0.7); 2.1993 (10.1); 2.0639 (0.8); 2.0511(1.2); 2.0435 (1.7); 2.0380 (0.8); 1.8417 (0.9); 1.8282 (1.4); 1.8147 (0.9); 1.5673 (4.5); 1.2585 (0.9); 1.0535 (4.4); 1.0347 (9.9); 1.0158 (4.2); −0.0002 (15.2) 8-1: .sup.1H—NMR(400.6 MHz, CDCl3): δ = 7.2639 (2.7); 6.6536 (1.9); 6.6522 (1.8); 6.5259 (1.9); 5.2968 (6.8); 4.4038 (1.7); 4.3735 (2.1); 4.3284 (1.8); 4.2983 (2.0); 4.0548 (0.6); 4.0468 (0.7); 4.0370 (1.9); 4.0292 (1.9); 4.0192 (2.0); 4.0115 (1.9); 4.0014 (0.8); 3.9937 (0.6); 3.9486 (1.0); 3.9448 (1.2); 3.9142 (1.5); 3.9116 (1.6); 3.8814 (1.1); 3.8775 (0.9); 3.7935 (1.3); 3.7874 (0.6); 3.7800 (1.8); 3.7721 (0.6); 3.7661 (1.4); 3.7330 (1.3); 3.7266 (0.7); 3.7194 (2.4); 3.7095 (16.0); 3.2964 (15.8); 2.2931 (9.1); 2.1644 (10.0); 2.0531 (0.7); 2.0466 (1.0); 2.0393 (1.1); 1.9069 (1.1); 1.8932 (1.5); 1.8796 (1.0); 1.1370 (4.4); 1.1193 (9.2); 1.1015 (4.2); −0.0002 (4.2) 2-2: .sup.1H—NMR(400.6 MHz, DMSO-d): δ = 6.7035 (1.8); 6.7019 (2.0); 6.6996 (2.2); 6.6981 (1.8); 6.6163 (2.1); 6.6128 (2.0); 4.1810 (1.7); 4.1715 (1.7); 4.1529 (1.9); 4.1435 (1.9); 3.6225 (1.1); 3.6096 (1.5); 3.5950 (1.1); 3.5649 (16.0); 3.5497 (1.7); 3.5361 (1.0); 3.3972 (0.9); 3.3912 (1.0); 3.3691 (0.8); 3.3631 (1.0); 3.3306 (1.0); 3.3246 (0.8); 3.3026 (1.0); 3.2966 (0.8); 3.1564 (6.0); 2.5230 (1.0); 2.5184 (1.2); 2.5097 (11.0); 2.5051 (23.7); 2.5005 (32.5); 2.4959 (21.7); 2.4914 (9.2); 2.0248 (10.0); 2.0065 (1.1); 1.9966 (1.2); 1.6534 (1.0); 1.6404 (1.4); 1.6267 (0.9); 0.0080 (0.8); −0.0002 (30.9); −0.0085 (0.8) 6-1: .sup.1H—NMR(400.6 MHz, DMSO-d): δ = 6.4634 (1.7); 6.4618 (1.8); 6.4309 (1.7); 4.2999 (1.5); 4.2776 (1.6); 4.2705 (1.8); 4.2482 (1.7); 3.6436 (1.0); 3.6311 (1.3); 3.6159 (1.0); 3.5798 (0.9); 3.5662 (1.6); 3.5524 (1.0); 3.5383 (16.0); 3.5128 (0.8); 3.5076 (1.0); 3.4851 (1.0); 3.4798 (0.8); 3.4558 (0.9); 3.4505 (0.8); 3.3229 (0.6); 3.2990 (1.6); 3.1559 (2.0); 3.0190 (15.2); 2.6691 (0.5); 2.5229 (1.5); 2.5183 (2.1); 2.5095 (28.6); 2.5049 (62.2); 2.5003 (87.1); 2.4957 (59.4); 2.4912 (25.9); 2.3274 (0.5); 2.2011 (7.9); 2.0377 (0.8); 1.9708 (9.2); 1.6588 (0.9); 1.6457 (1.3); 1.6317 (0.9); 0.0080 (1.9); −0.0002 (72.2); −0.0059 (0.6); −0.0067 (0.5); −0.0085 (2.0) 9-1: .sup.1H—NMR(400.0 MHz, CDCl3): δ = 7.2606 (15.6); 6.6570 (1.3); 6.5795 (1.3); 6.5595 (0.9); 5.2975 (1.2); 4.1123 (1.7); 4.1096 (1.1); 4.0852 (1.3); 4.0825 (2.0); 4.0794 (0.9); 3.8687 (2.1); 3.8657 (1.4); 3.8417 (1.3); 3.8386 (2.0); 3.8335 (13.4); 3.8186 (1.5); 3.7937 (1.2); 3.6972 (16.0); 3.6797 (1.2); 3.6657 (1.4); 3.6519 (1.3); 3.6299 (1.2); 3.6185 (6.1); 3.6027 (1.1); 2.3006 (15.5); 2.2909 (1.0); 2.2806 (0.7); 1.9789 (0.7); 1.9659 (1.0); 1.9527 (0.7); 1.5546 (0.8); 1.5411 (1.2); 1.5274 (0.8); −0.0002 (6.7) 9-4: .sup.1H—NMR(400.0 MHz, CDCl3): δ = 7.2623 (11.9); 6.8507 (1.1); 6.8469 (1.2); 6.7644 (1.3); 6.7597 (1.2); 6.4779 (0.8); 5.2983 (1.9); 4.1289 (1.7); 4.1260 (1.1); 4.1016 (1.3); 4.0988 (2.0); 4.0955 (1.0); 3.8786 (1.0); 3.8754 (2.1); 3.8723 (1.4); 3.8485 (14.0); 3.8158 (1.2); 3.8085 (0.7); 3.7051 (0.7); 3.6971 (16.0); 3.6855 (1.6); 3.6717 (1.2); 3.6370 (1.2); 3.6231 (1.6); 3.6146 (6.1); 3.6100 (1.5); 2.3239 (8.2); 2.0431 (0.5); 1.9963 (0.7); 1.9831 (1.0); 1.9701 (0.6); 1.5781 (0.9); 1.5645 (1.2); 1.5509 (0.8); −0.0002 (5.2) 13-50: .sup.1H—NMR(400.0 MHz, CDCl3): δ = 7.2598 (62.2); 7.0512 (2.4); 7.0478 (2.5); 6.7926 (2.4); 6.7896 (2.4); 4.0537 (1.2); 4.0363 (3.9); 4.0188 (3.9); 4.0014 (1.2); 3.8667 (9.1); 2.0366 (16.0); 1.4322 (0.9); 1.4070 (4.6); 1.3896 (9.7); 1.3722 (4.6); 1.2555 (1.2); 1.2435 (0.9); 0.0080 (2.5); −0.0002 (76.2); −0.0085 (2.4)

[0457] .sup.1H NMR spectra (no NMR peak list method):

[0458] Exemplary compound 1-2:

[0459] .sup.1H NMR (401 MHz, DMSO-d.sub.6) δ ppm 1.75 (br t, 2H), 2.00-2.09 (m, 9 H), 3.17 (d, 1H), 3.32 (s, 3H), 3.43-3.70 (m, 11 H), 4.02-4.15 (m, 1H), 4.30 (dd, 2H), 6.73-6.88 (m, 2H), 8.18 (s, 1H), 10.87 (br s, 1H)

[0460] Exemplary compound 5-1:

[0461] .sup.1H NMR (401 MHz, DMSO-d.sub.6) δ ppm 1.74 (br t, 2H), 1.98-2.02 (m, 3H), 2.05 (br t, 2H), 2.20-2.26 (m, 1H), 2.27 (s, 3H), 3.11-3.18 (m, 3H), 3.32 (s, 4H), 3.57-3.76 (m, 11 H), 4.39 (dd, 2H), 6.63 (s, 2H), 10.88 (s, 1H)

[0462] Exemplary compound 13-16:

[0463] .sup.1H-NMR (400.0 MHz, CDCl.sub.3, ppm): 11.8-9.8 (OH), 6.92 (s, 1H), 6.82 (s, 1H), 3.84 (s, 3H), 3.7 (s, 2H)

[0464] Exemplary compound 12-1:

[0465] .sup.1H-NMR (400.0 MHz, CDCl.sub.3, ppm): 5.55-5.35 (br m, 1H, NH), 4.22-4.18 (pseudo d, 2H), 4.00-3.85 (pseudo d, 2H), 3.75-3.66 (m, 7H), 2.03 (t, 2H), 1.81 (t, 2H), 1.47+1.44 (two singlets, 9H in total)

[0466] Exemplary compound 11-1:

[0467] .sup.1H-NMR (400.0 MHz, CDCl.sub.3, ppm): 4.26 (d, 2H), 3.80-3.62 (m, 9H), 2.01 (dt, 2H), 1.85 (dt, 2H)

[0468] Compound of the formula (VIII): (3-nitro-1,5,9-trioxaspiro[5.5]undecan-3-yl)methanol

[0469] .sup.1H-NMR (600 MHz, DMSO-d.sub.6, ppm): 5.47 (t, 1H); 4.39 (d, 2H); 4.10 (d, 2H); 3.72 (d, 2H); 3.54 (m, 4H); 1.95 (m, 2H), 1.60 (m, 2H)

[0470] Compound of the formula (IX): (3-amino-1,5,9-trioxaspiro[5.5]undecan-3-yl)methanol

[0471] .sup.1H-NMR (600 MHz, DMSO-d.sub.6, ppm): 3.60 (d, 2H); 3.54 (m, 4H); 3.45 (d, 2H); 3.44 (m, 1H); 3.37 (s, 2H); 1.87 (m, 2H; 1.67 (m, 2H); 1.06 (t, 2H)

[0472] Compounds of the formula (X): tert-butyl [3-(hydroxymethyl)-1,5,9-trioxaspiro[5.5]undecan-3-yl]carbamate

[0473] .sup.1H-NMR (400 MHz, DMSO-d.sub.6, ppm): 6.34 (bs, 1H); 4.74 (m, 1H); 4,02 (m, 2H); 3.70 (m, 2H); 3.59 (m, 2H); 3.55 (m, 4H); 1.90 (m, 2H); 1.66 (m; 2H); 1.46 ; 1.37 (s, 3H)

[0474] Compound of the formula (XI): tert-butyl (3-formyl-1,5,9-trioxaspiro[5.5]undecan-3-yl)carbamate

[0475] .sup.1H-NMR (400 MHz, CDCl.sub.3, ppm): 9.66 (s, 1H); 5.57 (s, 1H); 4.05 (m, 4H); 3.73 (t, 2H); 3.68 (t, 2H); 2.01 (m, 2H); 1.78 (m, 2H); 1.44 (s, 9H)

[0476] Compound of the formula (XII): 3-[(tert-butoxycarbonyl)amino]-1,5,9-trioxaspiro[5.5]undecane carboxylic acid

[0477] .sup.1H-NMR (400 MHz, DMSO-d.sub.6, ppm): 12.8 (s, 1H); 7.32 (bs, 1H); 4.10 (d, 2H); 3.86 (bd, 2H); 3.55 (tt; 4H), 1.83 (m, 2H); 1.69 (m, 2H); 1.38 (s, 9H)

B. FORMULATION EXAMPLES

[0478] a) A dusting product is obtained by mixing 10 parts by weight of a compound of the formula (I) and/or salts thereof and 90 parts by weight of talc as inert substance and comminuting the mixture in an impact mill.

[0479] b) A readily water-dispersible, wettable powder is obtained by mixing 25 parts by weight of a compound of the formula (I) and/or salts thereof, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as wetting agent and dispersant and grinding in a pinned-disc mill.

[0480] c) A readily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of the formula (I) and/or salts thereof with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range e.g. about 255° C. to more than 277° C.) and grinding to a fineness of below 5 microns in an attrition ball mill.

[0481] d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and/or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol as emulsifier.

[0482] e) Water-dispersible granules are obtained by mixing

[0483] 75 parts by weight of a compound of the formula (I) and/or salts thereof,

[0484] 10 parts by weight of calcium lignosulfonate,

[0485] 5 parts by weight of sodium laurylsulfate,

[0486] 3 parts by weight of polyvinyl alcohol and

[0487] 7 parts by weight of kaolin,

[0488] grinding the mixture in a pinned-disc mill, and granulating the powder in a fluidized bed by spray application of water as a granulating liquid.

[0489] f) Water-dispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill,

[0490] 25 parts by weight of a compound of the formula (I) and/or salts thereof,

[0491] 5 parts by weight of sodium 2,2′-dinaphthylmethane-6,6′-disulfonate,

[0492] 2 parts by weight of sodium oleoylmethyltaurate,

[0493] 1 part by weight of polyvinyl alcohol,

[0494] 17 parts by weight of calcium carbonate and

[0495] 50 parts by weight of water,

[0496] then grinding the mixture in a bead mill and atomizing and drying the resulting suspension in a spray tower by means of a one-phase nozzle.

C. BIOLOGICAL DATA

[0497] 1. Post-Emergence Herbicidal Effect and Crop Plant Compatibility

[0498] Seeds of monocotyledonous and dicotyledonous weed and crop plants are laid out in sandy loam soil in wood-fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated at the one-leaf stage. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then sprayed onto the green parts of the plants as aqueous suspension or emulsion at a water application rate equating to 600 to 800 l/ha with addition of 0.2% wetting agent. After the test plants have been left to stand in the greenhouse under optimal growth conditions for about 3 weeks, the action of the preparations is assessed visually in comparison to untreated controls (herbicidal action in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

[0499] Undesired Plants/Weeds:

TABLE-US-00015 ALOMY: Alopecurus myosuroides SETVI: Setaria viridis LOLRI: Lolium rigidum AVEFA: Avena fatua DIGSA Digitaria sanguinalis ECHCG: Echinochloa crus-galli HORMU: Hordeum murinum

TABLE-US-00016 TABLE 1a Post-emergence action at 20 g/ha against ALOMY in % Example Dosage number [g/ha] ALOMY 1-1 20 100 1-4 20 90 2-1 20 90 2-4 20 80 3-1 20 90 3-4 20 90 4-1 20 100 4-4 20 90 5-1 20 80

TABLE-US-00017 TABLE 1b Post-emergence action at 80 g/ha against ALOMY in % Example Dosage number [g/ha] ALOMY 1-1 80 100 1-4 80 100 2-1 80 100 2-4 80 100 3-1 80 100 3-4 80 100 4-1 80 100 4-4 80 100 5-1 80 90 6-1 80 90

TABLE-US-00018 TABLE 2a Post-emergence action at 80 g/ha against AVEFA in % Example Dosage number [g/ha] AVEFA 1-1 80 100 1-4 80 100 2-1 80 100 2-4 80 100 3-1 80 90 3-4 80 100 4-1 80 100 4-4 80 80

TABLE-US-00019 TABLE 3a Post-emergence action at 20 g/ha against DIGSA in % Example Dosage number [g/ha] DIGSA 1-1 20 100 1-4 20 80 2-1 20 90 2-4 20 90 3-1 20 90 3-4 20 100 4-1 20 90 4-4 20 90

TABLE-US-00020 TABLE 3b Post-emergence action at 80 g/ha against DIGSA in % Example Dosage number [g/ha] DIGSA 1-1 80 100 1-4 80 80 2-1 80 90 2-4 80 90 3-1 80 100 3-4 80 100 4-1 80 90 4-4 80 90

TABLE-US-00021 TABLE 4a Post-emergence action at 20 g/ha against ECHCG in % Example Dosage number [g/ha] ECHCG 8-1 20 80 5-1 20 100 6-1 20 90

TABLE-US-00022 TABLE 4b Post-emergence action at 80 g/ha against ECHCG in % Example Dosage number [g/ha] ECHCG 1-1 80 100 1-4 80 80 2-1 80 100 2-4 80 80 3-1 80 100 3-4 80 100 4-1 80 100 4-4 80 100 8-1 80 90 5-1 80 100 6-1 80 100

TABLE-US-00023 TABLE 5a Post-emergence action at 80 g/ha against LOLRI in % Example Dosage number [g/ha] LOLRI 1-1 80 100 1-4 80 100 2-1 80 100 2-4 80 90 3-1 80 100 3-4 80 100 4-1 80 100 4-4 80 90 8-1 80 90 5-1 80 90 6-1 80 90

TABLE-US-00024 TABLE 6a Post-emergence action at 20 g/ha against SETVI in % Example Dosage number [g/ha] SETVI 1-1 20 100 1-4 20 80 2-1 20 90 2-4 20 80 3-1 20 80 3-4 20 80 4-1 20 90 4-4 20 80 8-1 20 80 5-1 20 90 6-1 20 90

TABLE-US-00025 TABLE 6b Post-emergence action at 80 g/ha against SETVI in % Example Dosage number [g/ha] SETVI 1-1 80 100 1-4 80 90 2-1 80 90 2-4 80 80 3-1 80 90 3-4 80 90 4-1 80 100 4-4 80 90 8-1 80 100 5-1 80 90 6-1 80 90

TABLE-US-00026 TABLE 7a Post-emergence action at 80 g/ha against in % Example Dosage number [g/ha] HORMU 1-1 80 100 2-1 80 90 3-1 80 90 4-1 80 100

[0500] As shown by the results from Tables 1a/b, 2a, 3a/b, 4a/b, 5a, 6a/b, 7a, the compounds according to the invention have a good herbicidal post-emergence effectiveness against a broad spectrum of weed grasses and weeds. For example, the examples listed show, at an application rate of 80/20 g/ha, 80-100% activity against, inter alia, Alopecurus myosuroides, Avena fatua, Digitaria sanguinalis, Echinochloa crus-galli, Lolium rigidum and Setaria viridis. The compounds of the invention are therefore suitable for control of unwanted plant growth by the post-emergence method.

[0501] 2. Pre-Emergence Herbicidal Effect and Crop Plant Compatibility

[0502] Seeds of monocotyledonous and dicotyledonous weed plants and crop plants are laid out in sandy loam soil in wood-fibre pots and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), are then applied to the surface of the covering soil as aqueous suspension or emulsion at a water application rate equating to 600 to 800 L/ha with addition of 0.2% wetting agent.

[0503] After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the trial plants. The damage to the test plants is scored visually after a test period of 3 weeks by comparison with untreated controls (herbicidal activity in percent (%): 100% activity=the plants have died, 0% activity=like control plants).

TABLE-US-00027 TABLE 1a Pre-emergence action at 320 g/ha against ALOMY in % Example number Dosage [g/ha] ALOMY 8-1 320 100 5-1 320 90 6-1 320 100

TABLE-US-00028 TABLE 2a Pre-emergence action at 320 g/ha against AVEFA in % Example number Dosage [g/ha] AVEFA 8-1 320 100 5-1 320 100 6-1 320 90

TABLE-US-00029 TABLE 3a Pre-emergence action at 320 g/ha against ECHCG in % Example number Dosage [g/ha] ECHCG 8-1 320 100 5-1 320 100 6-1 320 100

TABLE-US-00030 TABLE 4a Pre-emergence action at 80 g/ha against LOLRI in % Example number Dosage [g/ha] LOLRI 8-1 80 100 5-1 80 100 6-1 80 100

TABLE-US-00031 TABLE 4b Pre-emergence action at 320 g/ha against LOLRI in % Example number Dosage [g/ha] LOLRI 8-1 320 100 5-1 320 100 6-1 320 100

[0504] As shown by the results from Tables 1a, 2a, 3a, 4a/b, the compounds according to the invention have a good herbicidal pre-emergence effectiveness against a broad spectrum of weed grasses and weeds. For example, the compounds, at an application rate of 80/320 g/ha, show 80-100% activity against, inter alia, Alopecurus myosuroides, Avena fatua, Echinochloa crus-galli and Lolium rigidum. The compounds of the invention are therefore suitable for control of unwanted plant growth by the pre-emergence method.