DD282005A5 - PROCESS FOR PREPARING CYCLIC 2-BENZOYL-1,3-DION COMPOUNDS - Google Patents

Abstract

The invention relates to processes for the preparation of cyclic compounds of formula I which are obtained by reacting compounds of general formula II with the appropriate benzoic acid or one of its reactive derivatives, compositions containing them and their use as herbicides. Formula I {cyclic diones; benzoyl; Method; manufacture; herbicides; Unkrautbekaempfung}

Description

For this 2 pages formulas

Field of application of the invention

The invention relates to processes for the preparation of 2-aminol derivatives of cyclic 1,3-diones, compositions containing them and their use as herbicides.

Characteristic of the known state of the art

There are currently no technical solutions on cm mentioned area bokannt.

Object of the invention

The aim of the invention is to provide new 2-benzoyl derivatives of cyclic 1,3-diones and their agriculturally acceptable salts and their use as herbicides.

Explanation of the essence of the invention

The object of the invention is to produce new 2-benzoyl derivatives of cyclic 1,3-diones and their agriculturally acceptable salts.

The present invention provides new 2-benzoyl derivatives of cyclic 1,3-diones of the general formula I shown below, in which

X represents a methylene group, an oxygen or sulfur atom or NR ⁴ group, Y represents a -C (R ⁶ ) (R °) methylene group or an oxygen atom,

R ^{1 is} a hydrogen atom or a straight or branched chain alkyl group m ^; t is 1 to 6 carbon atoms, which is optionally substituted by one or more halogen atoms, or a cycloalkyl group having 3 to 6 carbon atoms, R ^{2 represents} a hydrogen atom or a radical R ⁷ or

R 'and R ² together represent an alkylene group having 2 to 6 carbon atoms, ¹ i, R ^{3 represents} a halogen atom, an amino or carbamoyl group (which may be substituted by one or two straight or branched chain alkyl groups having 1 to 6 carbon atoms), a straight chain - or branched chain alkoxycarbonyl or Alkat.oyl- or alkanoylamino group having 2 to 7 carbon atoms or a radical R, RO, RS, RSO or RSO ₂ , wherein R is a straight or branched chain alkyl group having 1 to 6 carbon atoms, optionally substituted by one or more halogen atoms is substituted,

R ^{4 is} a hydrogen atom or a straight- or branched-chain alkyl or alkoxycarbonyl group having in each case 1 to 6 or 2 to 7 carbon atoms,

R ^{6 is} a hydrogen atom or a straight- or branched-chain alkyl or alkoxycarbonyl group having in each case 1 to 6 or 2 to 7 carbon atoms,

R ^{e is} a hydrogen atom or a straight or branched chain alkyl group having 1 to 6 carbon atoms, R ^{7 is} a straight or branched chain alkyl group having 1 to 6 carbon atoms represented by one or more halogen atoms or a straight or branched chain alkylthio group having 1 to 6 Carbon atoms odor may be substituted by an (R ⁸ ) _n- phenyl-S group or a cycloalkyl group having 3 to 6 carbon atoms, for. A cyclohexyl or a tetrahydrothiapyran-3-yl group, or an (R ⁸ ) _n -phenyl group in which R ^{8 is} a halogen atom, a hydroxy, carboxy-nitro or cyano group, an amino or carbamoyl group (the is a straight-chain or branched alkoxycarbonyl or alkanoyl or alkanoylamino group having 2 to 7 carbon atoms or a radical R, RO, RS, RSO or RSO ₂ , wherein R represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms optionally substituted by one or more halogen atoms, wherein m is zero or an integer of 1 to 5 and η is zero or an integer of 1 to 5, with with the proviso that when X represents the methylene group and Y represents a -C (R ⁵ ) (R ⁶ ) methyl group, R ¹ and R ² do not simultaneously represent a hydrogen atom or a straight or branched chain alkyl group of 1 to 6 carbon atoms len, as well as their agriculturally acceptable salts.

When m or η is an integer between 2 and 5, the substituents R ³ and R ^{6 may} each be the same or different.

It will be further apparent to those skilled in the art that the compounds of formula I can exist in tautoner form, which means that the Η atom in the benzoyl substituted position of the ring can be on any of the vicinally substituted oxygen atoms and that the can be pre-lied with lower or higher proportions and in dynamic equilibrium. The chiral C atoms at the other positions of the ring lead to stereoisomers. The substituent R ', R ² , R ³ , R ⁴ , R ⁵ , R ^e , R ⁷ and R ⁸ further contribute in some cases to the formation of optical and / or stereoisomorie. All of these isomeric forms are included in the invention.

The agriculturally acceptable salts of the compounds of general formula I include salts with agriculturally acceptable bases and acids. These are salts whose cations or anions are known in the art for the formation of salts for agricultural or horticultural use.

The salts should preferably be water-soluble. Suitable salts with bases include alkali metal (e.g., sodium and potassium), alkaline earth metal (e.g., calcium and magnesium), ammonium salts, and salts of amines (e.g., diethanolamine, triethanolamine, octylamine, morpholine, and dioctylmethylamine).

Suitable acid addition salts of the compounds of general formula I that can be formed when the compounds have an amino group include salts with inorganic acids, e.g. Hydrochlorides, sulfates, phosphates and nitrates and salts with organic acids, eg. As acetic acid.

Whenever reference is made in the present description to the compounds of the general formula I, it is also intended to include salts with agriculturally acceptable bases or acids of the compounds of the formula I.

Preferred compounds of formula I are those in which X is a -NR ⁴ group, Yeine-C (R ⁵ ) (R ⁶ ) -methylene group, R ^{2 is} an alkyl or optionally a substituted phenyl group having the meaning given above for R ⁷ represent and the other symbols have the meaning given above.

The following compound classes of the general formula I are of particular interest as herbicides:

Compounds in which Y represents a-C (R ⁵ ) (C ⁶ ) -methylene group;

Compounds in which R ^{2 is} an Η-atom or a straight- or branched-chain alkyl group having 1 to 6 C atoms, which may optionally be substituted by one or more halogen atoms, or a cycloalkyl group having 3 to 6 C atoms or represents an (R ⁸ ) "- phenyl group, or R 'and R ² together represent an alkylene group having 2 to 6 C atoms;

Compounds in which R ^{1 is} a straight-chain or branched alkyl group having 1 to 6 C atoms which may be substituted by one or more halogen atoms or a cycloalkyl group having from 3 to 6 C atoms and R ^{2 is} a (R ^s ) " Phenyl group;

Compounds in which X is a methylene group, an oxygen or a sulfur atom or an NR ⁴ 'group in which R ⁴ ' is a hydrogen atom or a straight-chain or branched alkyl group having from 1 to 6 C atoms, Y is one -C (R ⁵ ) (R ⁶ ) methylene group, Λ ^{1 is} a hydrogen atom or a straight or branched chain alkyl group having from 1 to 6 carbon atoms, optionally substituted by one or more halo or a cycloalkyl group having 3 to 6C R ^{2 is} a straight-chain or branched alkyl group having 1 to 6 C atoms, which may be substituted by one or more halogen atoms or a cycloalkyl group having 3 to 6 carbon atoms or R ¹ and R ² together form an alkylene group with 2 represent up to 6 C atoms;

Compounds in which X represents an -NH group, Y represents a -C (R ⁶ ) (R ^e ) -methylene group, R 'represents a hydrogen atom or a straight- or branched-chain alkyl group having 1 to 6 C atoms, R ^{2 represents} a hydrogen atom or a straight or branched chain alkyl group having 1 to 6 carbon atoms;

Compounds in which X represents a methylene group, Y represents a -C (R ⁵ ) (R ^e ) -methylene group (preferably not the MethylengrupDe -CH ₂ -)

R 'represents a hydrogen atom or a straight- or branched-chain alkyl group having 1 to 6 C atoms and R ^{2 represents} a group (R ⁸ ) _n -phenyl- and in which R ^{3 is} preferably a hydroxy, carboxy, nitro or cyano group , an amino or carbarnoyl group (which may be substituted by one or two straight or branched chain alkyl groups having 1 to 6 carbon atoms /, a straight-chain or branched alkyl or alkoxy group which may be substituted by one or more halogen atoms, e.g. B. is a trifluoromethyl or Trifluormethoxy- or an alkoxycarbonyl or AlkanoyI- or alkanoylamino group each having 1 to 6 or 2 to 7 carbon atoms, or a group RS, RSO or RSO ₂ , in the R is a straight-chain or branched alkyl group with 1 to 6 carbon atoms, which is optionally substituted by one or more halogen atoms and most preferably represents a nitro group;

-, compounds in which X represents an oxygen or sulfur atom, Y represents a-C (R ⁵ ) (R ⁶ ) methylene group, R 'is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms and R ² a group (R ³ ) _n -phenyl;

Compounds in which the (R ³ ) _m substitution replaces 2-chloro, 2-trifluoromethyl or preferably 2-nitro with 4-trifluoromethoxy, 4-trifluoromethylthio / sulphinyl / sulphonyl, or preferably 4-chloro, 4-trifluoromethyl or 4-methylsulphonyl, and preferably without substitution at the 6-position of the benzoyl group; 2-nitro and 4-chloro-2-nitro are particularly preferred.

The following compounds of the formula I are of particular interest as herbicides:

1. 3- (4-Chloro-2-nitrobenzoyl) -6,6-dimothylpiperidine-2,4-dione

2. 3- {2-Nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

3. 3- (4-Chloro-2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

4. 1-Methyl-3- (2-nitrobenzoyl) -6-phenyl-piperidine-2-dione

5. 6,6-Dimethyl-3- (2-nitrobenzoyl) piperidine-2,4-dione

6. 3- (4-Chloro-2-nitrobenzoyl) piperidine-2,4-dione

7. 3- (4-Chloro-2-nitrobenzoyl) -5-methylpiperidine-2,4-dione G. 3- {4-Chloro-2-nitrobenzoyl) -1-methylpiperidine-2,4-dione 9. 3- (4-chloro-2-nitrobenzoyl) -6-methylpiperidine-2,4-dione

10. 3- (4-Chloro-2-nitrobenzoyl) -6-methylpiperidine-2,4-dione

11. 3- (3,4-Dichlorobenzoyl) -6-phenyl-piperidine-2,4-dione

12. 3- (3-Bromobenzoyl) -6-phenylpent, ridin-2,4-dione

13. 3- {2,6-Dichlorobenzoyl) -6-phenyl-piperidine-2,4-dione

14. 3- (5-M8thyl-2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

15. 3- (4-trifluoromethylbenzoyl) -6-phenyl-piperidine-2,4-dione

16. 3- (4-fluorobenzoyl) -6-phenyl-piperidine-2,4-dione

17. 3- (2-Chlorobenzoyl) -6-phenyl-piperidine-2,4-dione

18. 3- (2-trifluoromethylbenzoyl) -6-phenyl-piperidine-2,4-dione

19. 3- (2-fluoro-2-carbonyl) -6-phenyl-piperidine-2,4-diol

20. 3- (2,4-Bistri (luoromethylbenzoyl) -6-phenyl-piperidine-2,4-dione

21. 3- (2-Bromobenzoyl) -6-phenylpiperidine-2,4-dione

22. 3- (2-iodobenzoyl) -6-phenyl-piperidine-2,4-dione

23. 3- (2-Methylbenzoyl) -6-phenyl-piperidine-2,4-dione

24. 3-Benzoyl-6-phenyl-piperidine-2,4-dione

25. 3- (2-Chloro-4-fluorobenzoyl) -6-phenyl-piperidine-2,4-dione

26. 3- (4-Bromo-2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

27. 3- (2-nitro-4-trifluoromethylbenzoyl) -6-phenyl-piperidine-2,4-dione

28. 3- (2-Methoxybenzoyl) -6-phenyl-piperidine-2,4-dione

29. 3- (4-Acetyl-2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

30. 3- (2-Methylthiobenzoyl) -6-phenyl-piperidine-2,4-dione

31. 3- (2-trifluoromethoxybenzoyl) -6-phenyl-piperidine-2,4-dione

32. 3- (2,3,4-Trichlorobenzoyl) -6-phenyl-piperidine-2,4-dione

33. 3- (2,4,5-Trichlorobenzoyl) -6-phenyl-piperidine-2,4-dione

34. 3- (4-Methoxy-2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

35. 3- (5-Chloro-2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

36. 3- (2-Ethoxybenzoyl) -6-phenylpiperidine-2,4-dione

37. 3- (3-Nitrobenzoyl) -6-phenyl-piperidine-2,4-dione

38. 3- (3-Chlorobenzoyl) -6-phenyl-piperidine-2,4-dione

39. 3- (3-trifluoromethoxybenzoyl) -6-phenyl-piperidine-2,4-dione

40. 3- (3-trifluoromethylbenzoyl) -6-phenyl-piperidine-2,4-dione

41. 3- (3-Methylbenzoyl) -6-phenyl-piperidine-2,4-dione

42. 3- (3-Methoxybenzoyl) -6-phenyl-piperidine-2,4-dione

43. 3- (4-tert-Butylbenzoyl) -6-phenyl-piperidine-2,4-dione

44. 3- (4-iodobenzoyl) -6-phenyl-piperidine-2,4-dione

45. 3- (4-Chloro-2-nitrobenzyl) -6- (3,4-difluorophenyl) -piperidine-2,4-dione

46. 3- (4-Chloro-2-nitrobenzoyl) -6- (4-methylphenyl) -piperidine-2,4-dione

47. 3- (4-Chloro-2-nitrobenzoyl) -6- (4-methoxyphenyl) -piperidine-2,4-dione

48. S-M-chloro-nitrobenzylD-e-fS-chlorophenyi-piperidine ^ adion

4 ?. 3- (4-chloro-2-nitrobenzoyl) -6- (4-methylthiophenyl) piperidine-2,4-dione

50. 3- (4-Chloro-2-nitrobenzoyl) -6- (4-methyl-sulphinyl-phenyl) -piperidine-2,4-dione

51. 3- (4-Chloro-2-nitrobenzoyl) -6- (4-methyl-sulphonyl-phenyl) -piperidine-2,4-dione

52. 3- (4-Chloro-2-nitrobenzoyl) -6- (2-bromophenyl) -piperidine-2,4-dione

53. 3- (4-Chloro-2-nitrobenzoyl) -6- (2-methoxyphenyl) -1-methylpiperidine-2,4-dione

54. 3- (4-Chloro-2-nitrobenzoyl) -6- (4-ethoxyphenyl) -1-methylpiperidine-2,4-dione

55. 3- (4-Chloro-2-nitrobenzoyl) -6- (4-methylthiophenyl) -1-methylpiperidine-2,4-dione

56. 3- (4-Chloro-2-nitrobenzoyl) -6-phenyl-1-methylpiperidine-2,4-dione

57. 3- (2,4-Dinitrobenzoyl! Piperidine-2,4-dioti

58. 3- (5-Chloro-2-nitrobenzoyl) piperidine-2,4-dione

59. 3- (2-Nitrobenzoyl) piperidine-2,4-dione

60. 3- (2-Chlorobenzoyl) piperidine-2,4-dione

61. 3- (3-trifluoromethylbenzoyl) piperidine-2,4-dione

62. 3- (2,4-dichlorobenzoyl) piperidine-2,4-dione

63. 3- (5-Methyl-2-nitrobenzoyl) piperidine-2,4-dione

64. 3- (2,4-Bistrifluoromethyl-benzenoyl) -piperidine-2,4-dione

65. 3- (2-trifluoromethylbenzoyl) piperidine-2,4-dione

66. 3-Benzoylpiperidine-2,4-dione

67. 3- (3,4-Dichlorobenzoyl) piperidine-2,4-dione

68. 3- (2,5-Dichlorobenzoyl) piperidine-2,4-dione

69. 3- {2-Ethoxybenzoyl) piperidine-2,4-dione

70. 3- (2,3,4-Trichlorobenzoyl) piperidine-2,4-dione

71. 3- (2,4,5-Trichlorobenzoyl) piperidine-2,4-dione

72. 3- (4-Bromo-2-nitrobenzoyl) piperidine-2,4-dione

73. 3- (4-cyano-2-nitrobenzoyl) piperidine-2,4-dione

74. 3- (2-nitro-4-trifluoromethylbenzoyl) piperidine-2,4-dione

75. 3- (4-Flupr-2-nitrobenzoyl) piperidine-2,4-dione

76. 3- (2-Methyl-3-nitrobenzoyl) piperidine-2,4-dione

77. 3- (2-Methyl-5-nitrobenzoyl) piperidine-2,4-dione

78. 3- (2-Bromobenzoyl) piperidine-2,4-dione

79. 3- (2-Methoxybenzoyl) piperidine-2,4-dione

80. 3- (3-Nitrobenzoyl) piperidine-2,4-dione

81. 3- (3-Bromobenzoyl) piperidine-2,4-dione

82. 3- (3-trifluoromethoxybenzoyl) piperidine-2,4-dione

83. 3- (3-Methoxybenzoyl) piperidine-2,4-dione

84. 3- (3-Chlorobenzoyl) piperidine-2,4-dione

85. 3- (3-Meihylbenzoyl) piperidine-2,4-dione

86. 3- (4-nitrobenzoyl) piperidine-2,4-dione,

87. 3- (4-trifluoromethylbenzoyl) piperidine-2,4-dione

88. 3- (4-Chlorobenzoyl) piperidine-2,4-dione

89. 3- (4-Cyanobenzoyl) piperidine-2,4-dione

90. 3- (4-bromobenzoyl) piperidine-2,4-dione

91. 3- (4-Methylbenzoyl) piperidine-2,4-dione

92. 3- (4-Methoxybenzoyl) piperidine-2,4-dione

93. 3- (4-Chloro-2-nitrobenzoyl) -5,6-dimethyl-piperidine-2,4-dione

94. 3- (4-Chloro-2-nitrobenzoyl) -6,6-pentamethylene-piperidine-2,4-dione

95. 3- (4-Chloro-2-nitrobenzoyl) -5,5-dimethyl-piperidine-2,4-dione

96. 3- (4-Chloro-2-nitrobenzoyl) -1,5,5-trimethyl-piperidine-2,4-dione

97. 3- (2,4-Bistrifluoromethylbenzoyl) -6,6-dimethyl-piperidine-2,4-dione

98. 3- (4-Fluoro-2-nitrobenzoyl) -6,6-dimethyl-piperidine-2,4-dione

99. 3- (2-nitro-4-trifluoromethylbenzoyl) -6,6-dimethylpiperidine-2,4-dione

100. 3- (2,3,4-trichlorobenzoyl) -6,6-dimethyl-piperidine-2,4-dione

101. 3- (2,4,5-Trichlorobenzoyl) -6,6-dimethyl-piperidine-2,4-dione

102. 3- (4-Bromo-2-nitrobenzoyl) -6,6-dimethyl-piperidine-2,4-dione

103. 3- (4-Methylsuiphonyl-2-nitrobenzoyl) -6,6-dimethylpiperidine-2,4-dione

104. 2- (4-Chloro-2-nitrobenzoyl) -5-phenylcyclohexane-1,3-dione

105. 4-Carbethoxy-2- (4-chloro-2-nitrobenzoyl) -5-phenylcyclohexane-1,3-dione

106. 3- (2-nitro-4-trifluoromethylbenzoyl) -6-methyl-tetrahydropyran-2,4-dione

107. 3- (4-Chloro-2-nitrobenzoyl) -6-phenyltetrahydropyran-2,4-dione

108. 2- (4-Chloro-2-nitrobenzoyl) -5- (2-ethylthiopropyl) -6-carbethoxycyclohexane-1,3-dione

109. 3- (2-nitro-4-trifluoromethylbenzoyl) -6-methyl-6-trifluoromethylpiperidine-2,4-dione

110. 3- (4-Methylsulfpho-2-nitrobenzyl) -piperidine-2,4-dione

111. 6,6-Dimethyl-3- (4-methoxy-2-nitrobenzoyl) -piperidine-2,4-dione

112. 3- (4-Fluoro-2-trifluoromethylbenzoyl) -6-phenyl-piperidine-2,4-dione

113. 3- (2-Chloro-4-trifluoromethylbenzoyl) -6-phenyl-piperidine-2,4-dione

114. 3- (4-Carbethoxy-2-nitrobenzoyl) -piperidine-2,4-dione

115. 3- (2-Chloro-4-trifluoromethylbenzoyl) -piperidine-2,4-dione

116. 3- (4-Fluoro-2-trifluoromethylbenzoyl) -piperidine-2,4-dione

117. 3- (2-nitro-4-trifluoromethylbenzoyl) -6-methylpiperidine-2,4-dione 11,8. 3 (2-nitro-4-trifluoromethylbenzoyl) -1,5,5-trimethylpiporidin-2,4-dione

119. 3- (4-Methoxy-2-nitrobenzoyl) piperidine-2,4-dione

120. 3- (4-Carbethoxy-2-nitrobenzoyl) -6,6-dimethylpiperidine-2,4-dione

121. 6, o-Dimethyl-3- (4-methyl-2-nitrobenzoyl) piperidine-2,4-dione

122. 3- (4-tert-butylbenzoyl) piperidine-2,4-dione

123. 3- (4,5-Dichloro-2-nitrob2nzoyl) piperidine-2,4-dione

124. 3- (4-Acetyl-2-nitrobenzoyl) piperidine-2,4-dione

125. 3- (4-Methyl-2-nitrobenzyl) piperidine-2,4-dione

126. 3- (2-Chloro-4-methylsulphonylbenzoyl) piperidine-2,4-dione

127. 3- (4-Chloro-5-methyl-2-nitrobenzoyl) piperidine-2,4-dione

128. 3- (2-Chloro-5-nitrobenzoyl) piperidine-2,4-dione

129. 3- (4-Bromo-2-methylbenzoyl) piperidine-2,4-dione

130. 3- (3-Bromo-4-methylbenzoyl) piperidine-2,4-dione

131. 3- (2-Methylthiobenzoyl) piperidine-2,4-dione

132. 3- (2-Methylbenzoyl) piperidine-2,4-dione

133. 3- (4-iodobenzoyl) piperidine-2,4-dione

134. 3- (3,5-Bistrifluoromethylbenzoyl) piperidine-2,4-dione

135. 3- (2-Chloro-4-methylsulphonylbenzoyl) -6,6-dimethylpipeiidine-2,4-dione 13S. 6,6-dimethyl-3- (4-fluoro-2-trifluoromethyl-benzoyl) -piperidine-2,4-dione

137. 3- (4,5-Dichloro-2-nitrobenzoyl) -6,6-dimethylpiperidine-2,4-dione

138. 3- (4-Chloro-5-methyl-2-nitrobenzoyl) -6,6-dimethylpiperidine-2,4-dione

139. 3- (4-Cyano-2-nitrobenzoyl) -6,6-dimethyl-piperidine-2,4-dione

140. 3- (Methylsulphonyl-2-nitrobenzoyl) -1,5,5-trimethylpiperidine-2,4-dione

141. 5-Methyl-3- (2-nitro-4-trifluoromethylbenzoyl) -piperidine-2,4-dione

142. 5 _/ 5-Dimethyl-3- (2-nitro-4-trifluoromethyl-benzoyl) -piperidine-2,4-ciione

143. 3- (2-Nitrc-4-trifluoromethylbenzoyl) -6,6-pentamethylene-piperidine-2,4-dione

144. 6-ethyl-6-methyl-3,2-nitro-4-trifluoromethyl-benzoyl) -piperidine-2,4-dione

145. 6,6-Diethyl-3- (2-nitro-4-trifluoromethylbenzoyl) -piperidine-2,4-dione

146. 3- (2-nitro-4-trifluoromethylbenzoyl) -1,6,6-trimethylpiperidine-2,4-dione

147. 3- (3,5-Bistrifluoromethylbenzoyl) -6,6-dimethylpiperidine-2,4-dione

Numbers 1 to 147 are assigned to the above compounds for identification and later reference. The compounds of general formula I which are of particular interest are numbered 104,105,106,107,109 and 1 -, 0,14, 20, 23-27, 34,45-48, 53-76,81-83,94-100,102,103,110,111,113 and 114-121.

According to a feature of the present invention, there is provided a method of controlling weed growth (ie, undesired vegetation) at a locus, comprising applying a herbicidally effective amount to that locus of at least one cyclic dione compound of general formula I. For this purpose, the cyclic dione compounds are usually used in the form of herbicidally active compositions (ie in association with suitable diluents or carriers and / or surfactants suitable for use in herbicidally active compositions), e.g. B. as described below. The compounds of general formula I exhibit herbicidal activity against dicotyledonous (i.e., broadleaf) and monocotyledonous (e.g., grassy) weeds when applied before and / or after appearance.

The term "pre-emergence application" means application to the soil in which the weed seeds or seedlings are present before they emerge from the soil.

The term "application after emergence" means application to the shoot or parts of the weeds that have emerged from the soil.The compounds of general formula I can be used, for example, for controlling broadleaf Unknuts, such as, for example, Aethusacynapium, Abutilontheophrastl, Amaranthus retroflexus, Amsinckia intermedia, Anagallis arvensis, Anthemis arvensls, Artriplox patula, Bldens pilosa, Brassica nigra, Capsella bursa pastorls, Chenopodium album, Chrysanthemum segetum, Clrsium arvense, Datura stramonium, Desmodium tortuosum, Emex australia, Euphorbia helloscopia, Fumaria officinalis, Galeopsis tetrahit, Galium aparlne, Ipomea purpurea, Lamium purpureum, Lapsana communis, Matricaria inodora, Monochorla vaglnalis, Paoaver rhoeas, Physalis Iqngifolia, plantation lanceolate, Polygonum spp., (Eg Polygonum lapathlefolium, Polygonum aviculare, Polygonum convolvulus and Polygonum persicarla ), Portulaca oleracea, Ra phanus raphanistrum, Rotala indica, Rumax obtusifolius, Saponaria vaccaria, Scandix pectenveneris, Senicio vulgaris, Sesbania flurida, Sida spinosa, Silane alba, Sinapis arvensl, Solanum nigrum, Sonchus arvensl, Spergula arvensis, Stellaria media, Thlaspl arvense, Trlbulus terrestria, Urtica urens, Veronica hederlfolia, Veronica persica, Viola arvensis and Xanthium strumarium and weeds grasses such as Alopecurus myosuroides, Apsra splca-venti, Agrostis stolonfera, Avena tatua, Avona ludoviciana, Brachiaria, spp., Bromus storilis, Bromus tectorum, Chenchrus spp., Cynodon dactylon, Digitaria sangulnalls, Echlnochlua crus-galli, Eleuslne indica, Setaria vidis, and Sorghum halepense, and reed grasses, such as Cyperus esculentus, Cyperus Iria, and Cyperus rotundus, and Eleocharis acicularii. The amount of compounds of general formula I to be applied will vary according to the nature of the weed, the compositions used, the time of use, the climatic and soil conditions and (when used against weeds in agricultural areas) according to the type of fruit The dosage will be such as to prevent weed growth without causing significant damage to the fruit Generally speaking, taking into account these circumstances, when using dosages from 0.01 kg to 20 kg of active ingredient per hectare, good results are obtained It is possible, for example, to use higher or lower dosages with respect to the need for special control in the specific case The compounds of the general formula I can be used for the selective control of weeds, for example for combating the species indicated above, by use before or after the Au strive in an aligned or unaligned form, e.g. For example, by directional or unoriented spraying of a weed-infested area used or intended to be grown, such as for wheat, barley, oats, corn and rice, soybeans, field and pea beans, peas, alfalfa, cotton, peanuts, flax Onions, carrots, cabbage, oilseed rape, sunflower, beetroot, meadows or cultivated grassland before or after sowing or sprouting fruit.

For selective weed control on weed-infested areas, the z. B. are used or to be used for the cultivation of the aforementioned fruits, dosages between 0.01 kg and 8.0 kg, preferably between 0.01 and 4.0 kg of active ingredient per hectare are particularly suitable.

The compounds of general formula I may also be used to control the growth of weeds, in particular of the aforementioned species, both before and after emergence in orchards and other tree plantations, for example larger and smaller forests, parks and plantations such as sugar cane, oil palm and rubber plantations are used. To this end, sifi can be applied in an aligned and unaligned manner (eg by directional or unoriented spraying) on top of weeds or on the ground by counting on the appearance of weeds; the application may take place before or after setting of the trees or planting in dosages between 0.25 and 10.0 kg, preferably between 0.5 and 8.0 kg of active ingredient per hectare.

The compounds of the general formula I can likewise be used for weed control, in particular of the abovementioned types, on surfaces without cultivation, on which nevertheless a weed control is desired. Examples of such non-cultivated areas are aerodrome installations, industrial plants, railway tracks, roadsides, riverbanks, irrigation and other hydraulic structures, crippled areas, as well as wasteland and uncultivated land, in particular when weed control is desired to reduce the risk of fire.

If a complete herbicidal action is intended, the active ingredient will usually be applied at dosages in excess of those used on fruit-growing areas. The exact dosage depends on the type of vegetation to be treated and the desired effect. Pre-treatment or post-emergence treatment, preferably pretreatment, in an aligned or unoriented manner (e.g., by directional or even unoriented spraying) at dosages between 1.0 and 20kg, preferably 5.0 and 10.0kg, of active ingredient per hectare is particularly suitable for this purpose.

When weed control is carried out by pre-outgrowing, the compounds of general formula I can be incorporated into the soil which is expected to infest. A further advantageous effect results from the fact that when using the Vorbindungen of the general formula I after the emergence, i. Application to the eponymous parts of the mature weeds above the ground, the compounds of general formula I usually come into contact with the ground and so can combat in advance in the soil, germinating weeds in advance. Where particularly long-lasting weed control is desired, the use of the compounds of general formula I may optionally be repeated.

According to a further feature of the present invention compositions are provided which are suitable for use as herbicides containing one or more of the cyclic dione compounds of general formula I in combination with preferably homogeneously dispersed in one or more compatible herbicidally acceptable diluents or carriers and / or surface-active agents (ie, diluents or carriers and / or surfactants which are considered suitable for use in herbicidal compositions in accordance with the prior art and which are compatible with the compounds of general formula I). The term "homogeneously dispersed" is used to include compositions in which the compounds of general formula I are dissolved in other components. The term "herbicidal compositions" is used broadly to not only cover compositions intended for are ready for use as Herb'.ide but also concentrates which must be diluted before use. Preferably, the compositions contain between 0.95 and 90% by weight of one or more compounds of general formula I.

The herbicidal compositions may contain both a diluent or a carrier and a surface active agent (e.g., a wetting agent, a dispersing or emulsifying agent). Suitable surfactants which may be present in the herbicidal compositions of this invention may be those of the ionic or nonionic type, e.g. B. Sulphoricinoleates, quaternary ammonium compounds, products based on condensates of ethylene oxide with alkyl and polyarylphenols, eg. As nonyl or octylphenols or carboxylic acid esters of anhydrosorbitols, which have been converted into a soluble form by etherification of the free hydroxyl groups by condensation with ethylene oxide, alkali metal and alkaline earth metal salts of sulfuric acid esters and sulfonic acids, such as. Sodium dinonyl and sodium dioctylsulfosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzenesulphonates.

The herbicidal compositions of the invention suitably contain up to 10%, e.g. Between 0.05% and 10% of a surfactant; however, if desired, they may also contain higher levels of surfactant, e.g. B. up to 15% for liquid emulsifiable suspension concentrates and up to 25% for liquid water-soluble concentrates.

Examples of suitable solid diluents or carriers are aluminum silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, adsorbed activated carbon (carbon black) and clays such as e.g. As kaolin and clays, such as. As kaolin and bentonite. The solid compositions (which may be in the form of dust, granules or wettable powders) are preferably prepared by grinding compounds of general formula I with solid diluents or carriers or by impregnating the solid diluents or carriers with solutions of the compounds of general formula I in volatile solvents , Evaporation of the solvents and optionally grinding of the products to obtain powders produced. Granules may be prepared by absorption of compounds of general formula I (dissolved in suitable solvents, which may optionally be volatile) onto the granular carrier and optionally evaporating the solvents, or by granulation of powdered compositions obtained as described above have been. Solid herbicidal compositions, particularly wettable powders and granules, may contain wetting or dispersing agents (e.g., of the type described above) which may also serve as a diluent or carrier in solid form.

Liquid compositions of the invention may be in the form of aqueous, organic or aqueous-organic solutions, suspensions or emulsions, which may also contain a surface-active agent. Suitable liquid diluents which can be added to the liquid compositions are water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral oils, animal and vegetable oils and light aromatic and naphthenic fractions of petroleum (and mixtures of these diluents). , Surface active agents which may be included in the liquid compositions may be ionic or nonionic (for example of the type described above) and, if present in liquid form, may serve as diluents or carriers. Powders, dispersible granules and liquid compositions in the form of concentrates may be mixed with water or other suitable diluents, e.g. Mineral oils and vegetable oils, especially in the case of liquid concentrates in which the diluent or carrier is an oil, to obtain ready-to-use compositions. Liquid compositions of the compound of the general formula I may optionally also be used as self-emulsifying concentrates containing the active ingredients dissolved in the emulsifiers or in solvents, the emulsifiers compatible with the active ingredients, so that the simple addition of water to such concentrates gives ready-to-use compositions.

Liquid concentrates in which the diluent or carrier is an oil can be used without further dilution by application of the electrostatic spray technique.

Herbicidal compositions according to the invention may also optionally contain conventional adjuvants, such as. As adhesives, protective colloids, thickeners, penetrating agents, stabilizers, sequestering agents, anti-caking agents, dyes and corrosion inhibitors

 These aids can also serve as carriers or diluents.

Preferred herbicidal compositions according to the present invention are aqueous suspension concentrates containing 10 to 70% of one or more compounds of general formula I containing 2 to 10% of a surface active agent, 0.1 to 5% w / v thickener and 15 to 87.9% by volume of water; wettable powders containing 10 to 90% w / w (w / w) of one or more compounds of general formula I, 2 to 10% w / w of a surface active agent and 8 to 88% w / w solid diluent or carrier; soluble powders containing 10 to 90% w / w (w / w) of one or more compounds of general formula 1.2 to 40% w / w sodium carbonate and 0 to 88% w / w solid diluent; liquid water-soluble concentrates containing 5 to 50%, e.g. B. 10 to 30% w / v of one or more compounds of the general formula 1.5 to 25% w / v of a surface active agent and 25 to 90%, especially 45 to 85Vol .-% water-miscible solvent, eg. Dimethylformamide, or a mixture of a water-miscible solvent and water; liquid-emulsifiable suspension concentrates containing 10 to 70% w / v of one or more compounds of the general formula 1.5 to 15% w / v of a surfactant, 0.1 to 5% w / v of a thickening agent and 10 to 84.9 vol .-% organic solvent; Granules containing 1 to 90%, for example 2 to 10% g / g of one or more compounds of the general formula 1,0,5 to 7%, z. 0.5 to 2% w / w of a surfactant and 3 to 98.5%, e.g. B. 88 to 97.5% g / g carrier granules, and emulsifiable concentrates containing 0.05 to 90% g / v and preferably 1 to 60% g / v of one or more compounds of the general formula 1,0,01 bis 10% w / v, preferably 1 to 10% w / v of a surfactant and 9.99 to 99.94%, and preferably 39 to 98.99% by volume of organic solvent. Herbicidal compositions according to the invention may further comprise compounds of general formula I in association with, and preferably homogeneously dispersed in, one or more pesticidal compounds, and optionally one or more diluents or carriers, surfactants and adjuvants already described above. Examples of other pesticidal active substances which may be included in or used in conjunction with the herbicidal compositions of the present invention, eg, to increase the range of weeds detected, are alachlor [2-chloro-2 ', 6'-diethyl-N - (methoxymethyl) acetanilide], asulam [methyl (4-aminobenzenesulphonyl) carbamate], alloxydium Na [sodium salt of 2- (1-allyl-oxyaminobutylidene) -5,5-dimethyl-4-methoxycarbonylcyclohexane-IS-dione), atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3 _y 5-triazine], barban [4-chlorobut-2-ynyl-N IS-chlorphenyDcarbamat], benzoylprop-ethyl [ethyl N-benzoyl-N - (3,4-dichlorophenyl-2-aminopropionate], bromoxynil [3,5-dibromo-4-hydroxybenzonitrile], butachloro [N- (butoxymethyl) -2-chloro-2 ', 6'-diethylacetanilide], butylate (S. -ethyl, N, N-diisobutyl (thiocarbamate)], carbetamide [DN-ethyl] -phenylcarbamoxyloxypropionamide, chlorfenprop-methyl [methyl 2-chloro-3- (4-chlorophenyl) propionate), chloropropham [isopropyl N- (3-chloro-phenyl) carbamate], C hlortoluron [N '- (3-chloro-4-methylphenyl) -N, N-dimothylurea], cyanazine [2-chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino-1, 3,5-triazine), cycloate [N'-cyclohexyl-N-ethyl-S-ethyl (thiocarbamate, 2,4-D- [2,4-dichlorophenoxyacetic acid], dalapon [2,2-dichloropropionic acid], 2,4 -DDB- [4- (2,4-dichlorophenoxy) butyric acid], Desmedipham [3- (ethoxycarbonylamino) phenyl N-phenyl-carbamate], dialkyl [S-2,3-dichloroallyl-N, N-di-isopropyl (thiocarbamate)], dicamba [3,6-dichloro-2-methoxybenzoic acid], dichloroprop [(±) -2- (2,4-dichlorophenoxylpropionic acid], difenzoquat [1,2-dimethyl-3,5-diphenyl-pyrazolium salts ], Dimefuron 4- [2-chloro-4- (3,3-dimethylureido) phenyl] -2-t-butyl-1,3,4-oxadiazolin-5-one, dinitramine [N ', N'-diethyl] 2,6-dinitro-4-tri-methyl-phenylenediamine), diuron [N '- (3,4-dichlorophenyl) -N, N-dimothylurea), EPTC [S-ethyl Ν, Ν-dipropyl-kthiocarbamate)], ethofumesate [2- Ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl methylsulphonate], flampropisopropyl [isopropyl (±) -2- (N-benzoyl-3-chloro-4- fluoroaniline) propionate), flampropmethyl [methyl (±) -2- (N-benzoyl-3-chloro-4-fluoro!! lin) -propionate, fluoromoturon [N'-3-trifluoromethyl-phenyl) -N, N- dimethylurea !, loxynil ^ -hydroxy-S-di-iodobenzonitrile, isoproturon [N '- (4-isopropylphenyl) -N, N-dimethylurea], linuron (N-β-di-chlorophenyl-N-methoxy-N-methylurea), MCPA [4-chloro-2-methylphenoxyacetic acid], MCPB [4- (4-chloro-2-methylphenoxy) butyric acid], mecoprop [(±) -2- (4-chloro-2-methylphenoxylpropionic acid), metamitron [4- Amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one], methabenzothiazuron [N- (benzothiazol-2-yl) -N, N'-dimethylurea], metribuzin [4- Amino-6-t-bulyl-3- (i.iethylthio) -1,2,4-triazine-5 (4H) -one], molinate [S-ethyl Ν, Ν-hexamethylene (thiocarbamate)], oxadiazone [3 - (2,4-dichloro-5-isopropoxyphene / 1) -5-t-butyl-1,3,4-oxadiazolin-2-one], paraquat [1,1'-dimethyl-4,4'-bipyridylium salts] , Pebulate [S-propyl N-butyl-N-ethyl (thiocarbamate)], phenmedipham [3- (methoxycarbonylamino) phenyl N- (3-methyl-phenyl) -carbamate], prometry (4.6 Bis-isopropylamino-2-methylthio-1,3,5-triazine, propachloro [2-chloro-N-isopropylacetanilide], propanilo [N- (3,4-dichlorophenyl) -propionamide 'F'ropham [isopropyl N-phenylcarbamate], Pyrazon [5-amino-4-chloro-2-phenylpyridazine-3- (2H) -one], Simazine [2-t: ior-4,5-bisethylamino '; o-1,3,5-triazine], TCA [Trichloroacetic acid], thiobencarb [S-OChlor-benzyU-NN-diethylthiolcarbamate], tri-allate [Sa.SS-trichloroallyl-N, N-diisopropyl (thiocarbamate)], and trifluoroalan [2,6-dinitro-N, N-dipropyl-4- trifluormethylanilinl; Insecticides, e.g. Carbaryl [naphth-1-yn-methylcarbamate]; synthetic pyrethroids, eg permethrin and cypermethrin and fungicides, e.g. For example, 2,6-dimethyl-4-tridecylmorpholine, methyl N- (1-butyl-carbamoyl-benzimidazol-2-yl) carbamate, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, isopropyl-i -carbamoyl-S-IS.o-dichlorophenyl dehydantin and 1- (4-chloro-phenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) -butan-2-one.

Other biologically active agents which can be added to or used with the herbicidal compositions of the present invention are plant growth regulators, e.g. As succinamic acid, (2-chloroethyl) trimethylammonium chloride and ^ -Chlorethan-phosphonic acid or fertilizers containing, for example, nitrogen, potassium and phosphorus and important for the growth of plants trace elements, eg. As iron, magnesium, zinc, manganese, cobalt and copper.

Pesticide-active substances and other biologically active substances which are in or with the inventive, z. B. the above-mentioned herbicidal compositions can be used and the acids are, optionally in the form of conventional derivatives, for. B. as alkali metal and amine salts and esters.

According to a further feature of the present invention there is provided a product comprising at least one of the cyclic dione compounds of general formula I or, preferably, a herbicidal composition as described above and preferably containing a herbicide concentrate which must be diluted prior to use at least one cyclic dione compound of the general formula I in a container for the aforementioned compound (s) of the general formula I or such a herbicidal composition and instructions attached to this container, indicating the manner in which it contains the aforementioned compound (s) of the general formula (I) or

Herbicidal compositions in the control of weeds. The containers are usually sole! .Β, which are commonly used for the storage of chemical substances, wekhe are solid at room temperature, and which are used for PflanzenvernUUingsmittol, especially in concentrate form, such as. As cans, optionally internally coated metal drums and Kunststoffmaterialicn, glass and plastic bottles or, if the container contents is a solid material -. As weed killers in granular form -, packs, z. B. of cardboard, plastic or metal, and bags. The containers are generally sized to contain such amounts of cyclic ionic compound or herbicidal compositions as to be sufficient to control the progeny growing on 4000m ^{2 of} land, but are at most dimensioned to assure normal ease of handling remains. The instructions for use are physically linked to the container, either printed directly on the container or on a label or tag attached to it.

The instructions for use usually indicate that the content of the yeast, if necessary after dilution, is used for weed control in dosages between 0.01 kg and 20.0 kg of active substance per hectare in the manner described above and for the purpose described above.

By means of herbicide activity tests carried out with representative compounds of formula I, the following results were obtained:

Test method Weed control experiment

a) General

Appropriate amounts of the test compounds 1-123 were dissolved in acetone to give solutions giving a dosage of 1000 g of test compound per hectare (g / ha) (excluding compounds 4 and 105, which were dosed at 2,000 g / ha) , The solutions were sprayed with a standard laboratory sprayer for hebicides using a flat fan flow at a speed of 2.9 km / h and applying an epiliquid quantity of 540 liters per hectare.

b) weed control: application before outgrowth

Weed seeds were sown on the surface of "John Innes No. 1 potting soil" (7 volumes of sterilized clay, 3 volume peat, 2 volumes of fine sand) in square 70mm wide and 75mm deep plastic pots.

Weed species approximate seed number μ, υ pot

1) brindle leaf weed Abutilontheophrasti 10 Sinapisarvensis 20 Chenopodium album 60 Ipomoeapurpurea 10

2) weed grasses

Avenafatua 15

Echinochloacrus galli 20

3) Rledgris cyperus sclera 3

The test compounds were applied to uncovered seeds as described under a) above, and after spraying, the seeds were covered with 25 ml of sharp sand. One pot of each weed species per treatment was not sprayed or just mi! Sprayed acetone. After the treatment, the pots were placed in a greenhouse and watered from above. 17-20 days after spraying, the weed-suppressing effect was observed by visual inspection. The results were found in percent growth reduction or killing of the grasses compared to the untreated control pots. The findings are presented below.

c) weed control: treatment after outgrowth

Weeds were planted and then replanted at the seedling stage in "John Innes No. 1 potting soil" in square 70mm wide and 75mm deep plastic pots, except for Avena fatua, which was sown directly into the test pot and not repotted, and the plants were then planted in the greenhouse At the time of spraying, the number of plants per pot and their stage of growth was as follows:

weed Number of plants growth · per pot stadium at spray 1) Broadleaf weed Abutilon theophrasti 3 1-2 leaves Sinapisarvensis 4 2 leaves Ci.o-nopodium album 4 2-4 leaves Ipomoeapurpurea 3 1-2 leaves 2) weed grasses Avenafatua 15 1-2 leaves Echinochloa crus-galli 4 2-3 leaves 3) Riedgräser Cyperusesculentus 4 3 leaves

The test compounds were applied to the plants as described under a) above. One pot per weed species and treatment was not sprayed or only with acetone as a counter-control. At the end of 24 hours after spraying, the pots were watered from above.

17-20 days after the spraying, the suppression of the growth of the weeds was confirmed by visual inspection. Dio results were expressed as percent growth reduction or killing of the weeds in preference to the plants in the control pots. The results obtained are listed below.

a) Broad-leaved weeds At = Abutilon thoophrasti Bk = Brassica kaber

Ca = Chenopodium album Ip = Ipomea purpurea

b) weed grasses

Af = Avenafatua

Ec = Echinochloacrus galli

c) Riedgräser

Ce = cyperia sculantus

Results

In the pretreatment trial, the following compounds gave 100% suppression of Chenopodium album and between 10 and 100% suppression of the other species:

1,3,4,6, 7,8,10, 20,34,56,59,62, 63, 64, 70, 72, 73, 74,75, 76,9 5,96, 97,98, 99,100,102,103,104,105,106,109,110,113,114 , 115,116,117,118,119,120 and 121.

Other compounds gave between 10 and 100% suppression of some, but not all, species.

In the follow-up trial, the following compounds gave 100% suppression of Chenopodium album and between 10 and 100% suppression of the other species:

1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 20, 23, 24, 25, 26, 27, 34, 45, 47, 48, 53, 54, 55, 56, 57.58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 81, 82, 93, 94, 95 96,97,98,99,100,102,103,104,106,109,110,111,113,114,115,116,117,118,119,120 and 121.

Other compounds gave between 10 and 100% suppression of some, but not all, species.

Ausführungsbeispielo

The following examples illustrate herbicidal compositions according to the invention.

example 1

It became a wettable powder:

3- (2-Nitrobenzoyl-6-phenyl-piperidine-2,4-dione 50% w / w

Ethylan BCP (a nonylphenol / ethylene oxide condensate containing 9 mol

Ethylene oxide per mole of phenol), 5% g / g

Aerosil (microfine particle size silica) 5% g / g

Celite PF (synthetic magnesium silicate carrier),

by absorption of the Ethylan BCP on the Aerosil, mixing with the other ingredients, and then grinding the mixture in a hammer mill.

Similar wettable powders can be prepared as described above, substituting other compounds of general formula I for the 3- (2-nitrobenzoyl) -6-phenylpiperidine-2,4-dione.

Example 2

An aqueous suspension concentrate was prepared from:

3- (2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione 50% w / v

Ethylene BCP 1% w / v

Sopropon T36 (the sodium salt of polycarboxylic acid) 0.2% w / v

Ethylene glycol 5% w / v

Rhodigel 23 (polysaccharide xanthan gum resin thickener) 0.15% w / v

distilled water to 100% by volume

intimately mixing the ingredients and then grinding in a ball mill for 24 hours.

Similar aqueous concentrates can be prepared as described above by replacing the 3- (2-nitrobenzoyl) -6-phenylpiperidine-2,4-dione with other compounds of general formula I.

Example 3

A soluble powder was prepared from:

3- (2-nitrobenzoyl) -6-phenyl-piperidine-2,4-dione 60% w / w

Sodium carbonate 40% g / g

by mixing the ingredients and grinding the thus obtained mixture in a hammer mill to obtain a soluble powder.

Similar soluble powders can be prepared as described above by replacing the 3- (2-nitrobenzoyl) -6-phenylpiperidine-2,4-dione with other compounds of general formula I.

The compounds of general formula I can be prepared by the use or transfer of conventional methods (i.e., methods heretofore used or described in the chemical literature), for example, by the methods described below.

According to a feature of the invention, the compounds of general formula I can be prepared by reacting a compound of general formula II with the appropriate benzoic acid or one of its reactive derivatives, e.g. Benzoyl cyanide, chloride or anhydride, or, for example, an aromatic N-benzoyl heterocycle, such as N-benzoyl imidazole.

The reaction of the compound of the general formula II with the benzoyl cyanide or the N-benzoylimidazole is generally carried out in the presence of zinc chloride or triethylamine in an inert organic solvent, such as. B.

Dichloromethane, carried out.

The reaction of the compound of general formula II with benzoic acid or benzoyl chloride is usually carried out in the presence of diethyl cyanophosphate and triethylamine in an in-organic solvent, such as dimethylformamide, or in the presence of 1,5-diazabicyclo [5.4.0] undecono- 5 in an inert organic solvent such as toluene at the reflux temperature of the reaction mixture.

According to a further feature of the present invention, the compounds of general formula I are prepared by the rearrangement of a compound of general formula III, optionally in situ using source of cyanide ions or in counterpart, of aluminum chloride or tines in position 4 substituted aminopyridine, for example 4-dimethylaminopyridine.

The cyanide ion source may be acetocyanohydrin, cyar hydrogen, trimethylsilyl cyanide or zinc cyanide in the presence of triethylamine in an inert organic solvent such as dichloromethane or acetonitrile.

The rearrangement using aluminum chloride may be carried out in an inert organic solvent such as 1,2-dichloroethane at room temperature.

The rearrangement using Verwen dun lι of substituted in position 4 aminopyridine can be carried out in an inert organic solvent such as toluene at the reflux temperature of the reaction mixture.

Compounds of the general formula III can be prepared by bonzoylation of a compound of the general formula II using a benzoyl halide. The compounds of general formula III and their preparation are features of the present invention.

Prior to the invention of general formula II, in which X is an -NR ⁴ group and Y is a -C (R ⁵ ) (R ⁶ ) -methylene group, by hydrolysis and decarboxylation of a compound of general formula IV or by the Reaction of a compound of general formula V can be represented with a diketene.

The new compounds of the general formula II and their illustration bildon features of the present invention. Novel compounds of general formula II, of particular interest are those in which:

(a) Y represents a-C (R ⁵ ) (R ^e ) methyl group, X represents a group NR ⁴ - as defined above and R 'and R ² are as defined above, with the proviso that R ¹ , R ^J and R ^{4 are} not simultaneously hydrogen atoms;

(b) X is a methylene group, R ^{2 is} a cycloalkyl group having 3 to 6 C atoms and R ^{1 is} as defined above;

(c) X represents an oxygen atom, R ^{2 represents} a straight-chain or branched alkyl group having 1 to 6 carbon atoms which may be substituted by one or more halogen atoms, or a cycloalkyl group having 3 to 6 carbon atoms and R 'has the meaning given above and R 'and R ² together represent an alkylene group having 2 to 6 C atoms;

(d) X represents a sulfur atom, R ^{2 represents} a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is substituted by one or more halogen atoms, R ^{1 has} the meaning indicated above, or R ¹ and R ² together form an alkylene group with 2 to 6 carbon atoms.

Compounds of the formula II as defined under a) can be prepared as described above.

Compounds of formula II as described under b), by treating the corresponding 4-alkoxycarbonyl-5-cycloalkylcyclohexan-1,3-dione with an aqueous solution of alkali metal hydroxide, for. Example, sodium hydroxide in the presence of an alcohol at a temperature of ^{0 0} C to the reflux temperature of the reaction mixture and subsequent acidification with, for example, aqueous hydrochloric acid are prepared.

Compounds of formula II as described under c), by treatment of the corresponding δ-hydroxy-ß-keto esters of the formula R'R ² C (OH) C (R ⁵ ) (R ^e ) C (= O) CHjCO 2 alkyl, in the various symbols have the meaning given above, with an aqueous solution of an alkali metal hydroxide, for. For example, sodium or potassium hydroxide at a temperature between ^{0 0} C and 50 ° C and subsequent acidification with, for example, aqueous hydrochloric acid are prepared.

Compounds of formula II as described under (d) can be prepared by treatment of the corresponding 4-oxo-Tetrahydroth 'ipyranthion with aqueous hydrogen peroxide in an inert organic solvent, for. For example, ethanol, in the presence of alkali metal hydroxide, for. As potassium hydroxide, at a temperature between -3O ⁰ C and 3O ⁰ C are prepared.

Other compounds of general formula II are known or can be prepared by the application or adaptation of known methods. The term "known method" as used in the specification means previously used or described in the literature.

Compounds of the general formula IV can be prepared by cyclization of a compound of the general formula VI in which R ^{9 represents} a straight-chain or branched alkyl group having 1 to 6 C atoms and R ' ^{0 represents} a straight-chain or branched alkyl group having 1 to 6 C atoms , ·

The reaction may be carried out in the presence of an alkali metal alkoxide in the corresponding alcohol, e.g. For example, sodium ethoxide in ethanol.

Compounds of general formula VI may be prepared by reacting a compound of general formula VII with an acid of general formula VIII or a reactive acid derivative, e.g. an acyl halide or by reacting the corresponding hydroxy compounds with an acyl nitrile.

Compounds of general formula VIII in which R ^{2 represents} a phenyl group and R ^{4 represents} an alkyl group can be prepared by hydrogenation of N-methyl-3-phenylisoxazolidin-3-one.

Compounds of general formula IV in which R ¹ and R ^{e represent} hydrogen atoms may also be prepared by catalytic hydrogenation of a compound of general formula IX using, for example, platinum oxide or palladium on carbon.

Compounds of general formula IX can be prepared similarly » ^- ie the compounds of general formula IV described above.

Salts with agriculturally acceptable bases of compounds of general formula I can be prepared from corresponding compounds of general formula I in a conventional manner, such as. B. by reacting stoichiometric amounts of the compounds of general formula I with the appropriate base z. An alkali metal hydroxide, carbonate or bicarbonate, an alkaline earth metal hydroxide or carbonate, ammonia or an amine (e.g., diethanolamine, triethanolamine, octylamine, morpholine or dioctylamine) in a suitable solvent.

Acid addition salts of compounds of general formula I which have an amino radical can be prepared from the corresponding compounds of general formula I by means of methods known per se, for. B. by reacting stoichiometric amounts of the compound of general formula I with the appropriate acid, for. As an inorganic acid, eg. As HCl, H ₂ SO ₄ , H ₃ PO ₄ or HNO ₃ or an organic acid, eg. Acetic acid, in a suitable solvent. If necessary, the salts can be purified by recrystallization from one, two or more suitable solvents.

Salts of the compounds of the general formula I are on the one hand as such already usable as herbicidally active compounds, but on the other hand can also be used in the purification of the corresponding compounds of general formula I, for. By exploiting the difference in solubility between the salts and the parent compounds in water and in organic solvents by methods known to those skilled in the art.

It will be understood by those skilled in the art that when practicing the method of the invention described above, it may be desirable to include chemical protecting groups in the reactants to prevent side reactions; For example, in the process for preparing the above-described derivatives, hydroxy substituents as described in the definition of R ³ groups in connection with general formula I above can be converted to benzyloxy groups prior to the reaction and the benzyl protecting groups subsequently removed. It is understood that the amino, carboxy and hydroxy groups present in certain reactants can be protected by any protecting group commonly used to protect amines, carboxylic acids or alcohols, the use of which does not adversely affect the rest of the molecule.

The amino group can be protected, for example, by groups such as tert-butoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, trichloroacetyl, trityl, benzyl, dibenzyl, benzyloxycarbonyl, p-nitrobenzyloxycarbonyl, p-methoxybenzyloxycarbonyl, chloroacetyl or trifluoroacetyl; the carboxy group can be protected by groups such as methoxymethyl , tertiary butyl, benzhydryl, p-nitrobenzyl or methoxybenzyl, and the hydroxy group may be protected by groups such as benzyl, trityl, tetrahydropyranyl or 2-methoxy-prop-2-yl.

The various protective groups could be removed simultaneously or successively.

1. The removal of the amine protecting group can be carried out, for example, as follows:

In the case of a tert-butoxycarbonyl, trityl or p-methoxybenzyloxycarbonyl group by treatment in acidic medium.

Preferably trifluoroacetic acid is used and the process is carried out at a temperature between 0 and 2O ⁰ C; also anhydrous or aqueous formic acid, para-toluenesulphonic acid or Methansulphonsäuro can be used in acetone or acetonitrile at a temperature between 2O ^{r 0} C and the reflux temperature of the reaction mixture. Under these conditions, the compound of general formula I may be trifluoroacetate, as a solvate with formic acid, methanesulfonate or para-toluenesulfonate and the amino group may therefrom by any method suitable for the recovery of amines from their salts, without Rest of the molecule to be released. Preferably, the process is carried out by bringing the compound into contact with an ion exchange resin or by allowing an organic base to act.

If the 2,2,2-trichloroethoxycarbonyl or p-nitrobenzyloxy group is used, this is done by reduction (in particular by reaction with zinc in acetic acid).

In the case of the chloroacetyl or trichloroacyl group, by the method disclosed in British Patent 1,454,589.

For benzyl, dibenzyl or benzyloxycarbonyl by catalytic hydrogenation.

In the case of a trifluoroacetyl group by treatment in a basic medium.

2. The removal of the protecting groups of the carboxy group is carried out as follows:

In the case of a tertiary butyl, p-methoxybenzyl or benzhydryl group by treatment in an acidic medium under the conditions described above for the removal of the trityl radical protecting group from the amino group. In the case of the benzhydryl radical, the process can be carried out in the presence of anisole.

In the case of a methoxymethyl group by treatment in a dilute acidic medium.

In the case of a p-nitrobenzyl group by reduction (in particular by treatment with zinc in acetic acid or by hydrogenolysis).

3. The removal of the protecting groups from the hydroxy groups is carried out as follows:

In the case of a benzyl, trityl or Tetrahydropyranylgruppa by acidolysis, for example with trifluoroacetic acid, aqueous or non-aqueous formic acid or para-toluenesulphonic acid.

In the case of the 2-methoxy-prop-2-yl group according to the method described in British Patent 2 021561.

It can be wünschenswe ¹ 1, the type of one or more substituents at an appropriate time during the synthesis of the compounds of the invention to change; Thus, for example, the compounds of general formula I in which R ^{3 represents} an amino group, alternatively from the corresponding compounds of general formula I in which R ^{3 represents} a nitro group, be prepared by application or adaptation for this conversion of known methods.

Compounds of the general formula I in which R ^{3 represents} an amino group can be converted into diazonium salts which are useful for syntheses as described in Morrison and Boyd "Organic Chemistry" (1959) and thus ultimately converted into, for example, an iodine atom.

The following examples and comparative examples illustrate the preparation of the compounds according to the invention.

Example 4 Compound I

A solution of 4-chloro-2-nitrobenzoyl chloride (4.4g) in dry dichloromethane (5ml) was added at 5-10 ° C with stirring to a solution of 6,6-dimethylpiperidine-2,4-dione (2.8g). and triethylamine (2.8ml) in dry dichloromethane (50ml) and the mixture was stirred at room temperature for 18 hours. Triethylamine (8.4 ml) and acetocyanohydrin (0.4 ml) were added successively to the solution and the mixture was stirred at room temperature for 4 hours. The resulting solution was washed successively with 2N hydrochloric acid (25ml) and water (3x 2RmI), dried over sodium sulfate and evaporated under reduced pressure to give a yellow solid which was recrystallized from acetonitrile. There was obtained 3- (4-chloro-2-nitrobenzoyl) -6,6-dimethylpiperidine-2,4-dione (4g), mp 162-162.5 ° C, as a yellow crystalline solid.

Example 5 Compounds 2 to 5

Acetone cyanohydrin (0.5 ml) was added by stirring a solution of 5,6-dihydro-4- (2-nitrobenzoyloxy) -6-phenylpyridine-2 (1H) -one (7.5 g) and triethylamine (6.7 g). in dry dichloromethane (100 ml) and the solution was stirred at room temperature for 18 hours. The solution was extracted successively with 2N hydrochloric acid (25ml) and water (3x25m) and with a 5% w / v aqueous sodium carbonate solution (4x50ml). The combined extracts were acidified with concentrated hydrochloric acid and the acidic solution extracted with dichloromethane (3x 75 ml). The combined extracts were washed with water (3 × 50 ml), dried over magnesium sulfate and evaporated under reduced pressure. A brown solid is obtained, which was recrystallised from a toluene-hexane mixture (7: 1.40 ml) to give 3- (2-nitrobenzoyl) -6-phenylpiperidine-2,4-dione (4.7 g). F. 146-150 ° C, as a salmon-colored crystalline solid.

The procedure is repeated in the same manner, but with replacement of 5,6-dihydro-4- (2-nitrobenzoyloxy) -6-phenylpyridin-2 (1 H) -one by 5,6-dihydro-4- (4-chloro-2 -nitrobenzoyloxy) -6-phenylpyridin-2 (1H) one to give 3- (4-chloro-2-nitrobenzoyl) -6-piperylpiperidine-2,4-dione, m.p.91-94 ° C, ( recrystallized from a mixture of tetracarbon of hexane [20.1; 42ml]) as a light brown crystalline solid.

The procedure is repeated in the same manner, but replacing 5,6-dihydro-4- (2-nitrobenzoyloxy) -6-phenylpyridin-2 (1 H) -one by 5,6-dihydro-4- (2-nitrobenzoyloxy) - 1-methyl-6-phenyl-pyridin-2- (1H) -one, to give 1-methyl-3- (2-nitrobenzoyl) -6-phenylpiperidin-2,4-dione, mp 144-146 ⁰ C, (recrystallized from a gum of toluene and hexane (4: 1, 101) as a buff crystalline solid.

The procedure is repeated in the same way, but replacing 5,6-dihydro-4- (2-nitrobenzoyloxy) -6-phenylpyridin-2 (1H) -one by 5,6-dihydro-6,6-dimethyl-4- (2-nitrobenzoyloxy) pyridine-2- (1 H) -one, to give 6,6-dimethyl-3 (2-nitrobenzoyl) piperidin-2,4-dione, mp 190-191 ⁰ C, (recrystallized from a mixture of toluene and hexane [1: 1; 25 ml]) as a cream crystalline solid.

Comparative Example 1

Triethylamine (3,4ml) in dry dichloromethane (100ml) at 0-5 ⁰ C under stirring to a solution of 2-nitrobenzoyl chloride (4.9 g) and 6-phenylpiperidine-2,4-dione (5g) and the mixture was stirred at room temperature for 3.5 hours. The solution was washed successively with 2N hydrochloric acid (25 ml), water (2x25 ml), 5% w / v aqueous sodium carbonate solution (25 ml) and water (3χ25 ml), dried over magnesium sulfate and evaporated under reduced pressure. A light yellow solid formed, which was recrystallized from a mixture of ethyl acetate and hexane (4: 1, 20 ml). This gave 5,6-dihydro-4- (2-nitrobenzoyl) -6-phenylpyridine-2 (1H) -one (4.8 g), mp 139-141 ⁰ C as a light yellow crystalline solid.

By proceeding in the same manner, but replacing 2-nitrobenzoyl chloride with 4-chloro-2-nitrobenzyl chloride, 5,6-dihydro-4- (4-chloro-2-nitrobenzoyloxy) -6-phenylpyridine-2 is obtained (1 H) -one, mp 116-118 ⁰ C (recrystallized from a carbon tetrachloride-hexane mixture (8: 1; 5ml]) as a light yellow crystalline solid.

The procedure is repeated in the same manner, but replacing 6-phenylpiperidine-2,4-dione by 1-methyl-6-phenyl-piperidine-2,4-dione, we obtain:

5.6-Dihydro-4- (2-nitrobenzoyloxy) -1-methyl-6-phenyl-pyridine-2'1H) -one as a dark brown resin.

If the procedure is repeated in the same way, but replacing 6-phenylpiperidine-2,4-dione by 6,6-dimethylpiperidine-2,4-dione, the following are obtained:

5,6-Dihydro-6,6-dimethyl-4- (2-nitrobenzoyloxy) pyridine-2 (1H) -one, m.p. 141-142.5 "C (recrystallized from a toluene-hexane mixture (5 : 1, 3OmI]) as a light brown crystalline solid.

Example 6

Compounds 6, 7, 9 and 10

A solution of 4-chloro-2-nitrobenzoyl chloride (5.8 g) in dry dichloromethane (10 ml) was added over 5 minutes while stirring a solution of piperidine-2,4-dione (3.0 g) and triethylamine (5.5 ml ) in dry dichloromethane (100 ml) and the mixture was stirred for 3 hours at room temperature. Then, acetone cyanohydrin (0.5 ml) was added and the mixture was stirred at room temperature for 18 hours. The solution was washed successively with 2N hydrochloric acid (50 ml) and water (2 x 100 ml), dried over sodium sulfite, and evaporated under reduced pressure to give a solid residue, which was recrystallized from ethyl acetate (70 ml) to give 3- (4- chloro-2-nitrobenzoyl) piperidine-2,4-dione (1.6g), mp 161-164 ⁰ C, was obtained as a light brown crystalline solid.

Piperidine-2,4-dione is a known compound (S.Toda et al., J. Antibiotics XXXIII, 173, [1980]).

The procedure is repeated in the same manner, but replacing piperidine-2,4-dione by 5-methylpiperidine-2,4-dione, to give 3- (4-chloro-2-nitrobenzoyl) -5-methylpiperidin-2, 4-dione, mp. 1 bo-158 ^° C (recrystallized from toluene) as a yellow crystalline solid.

By proceeding in a similar manner, but replacing piperidine-2,4-dione by 1-methylpiperidine-2,4-dione, there is obtained 3- (4-chloro-2-nitrobenzoyl) -1-methylpiperidine-2,4 -dione, mp 143-144 ⁰ C (recrystallized to a mixture of ethyl acetate and hexane) as radish brown crystalline solid.

If the procedure is repeated in the same manner but replacing piperidine-2,4-dione by 6-methyl-6-phenylpiperidine-2,4-dione, 3- (4-chloro-2-nitrobenzoyl) -6- methyl-6-phenylpiperidine-2,4-dione, mp 158-159 ⁰ C (recrystallized from a toluene-hexane mixture [1: 1]) as a cream crystalline solid.

By proceeding in the same manner but substituting 6-methylpiperidine-2,4-dione for piperidine-2,4-dione, 3- (4-chloro-2-nitrobenzoyl) -6-methylpiperidine-2 is obtained. 4-dione, m.p. 17O-172 ° C (recrystallized from an ethyl acetate-hexane mixture | 1: 1]) as a yellow crystalline solid.

Example 7

Compounds 11 to 18, 20 to 49, 52 to 65, 68 to 86, 88 to 103 and 110 to 147 If the procedure described in Example 6 is the same as described above, compounds of the general formula I which are described in the following are obtained Tables I and II are defined in more detail. In Table I, R ^{2 represents} an (R ⁸ ) "phenyl group.

Table I

.V

connection R ' R ³ R ⁴ n ⁶ R ⁶ R ⁸ Mp. "C No. 11 H 3,4-Cla H H H H 166-167 12 H 3-Br H H H H 126-127 13 H 2,6-Cl ₃ H H H  1 180.5 to 181.5 14 H 2-NO ₃ -O-CH ₃ H H H H 161-163 15 H 4-CF ₃ H H H H 197-199 16 H 4-F H H H H 172-173 17 H 2-CI H H H H 139-142 18 H 2-CF ₃ H H H H 149.5 to 151 20 H 2,4-bisCF ₃ H H H H 7 & -80 2i H 2-Br H H H H 143-145 22 H 2-1 H H H H 158-160 23 H 2-CH ₃ H H H H 151-152 24 H H H H H H 198-200 25 H 2-CI-4-F H H H H 130-131 26 H 2-NO ₃ -4-Br H H H H oil 27 H 2-NO ₃ -4-CF ₃ H H H H 130-131 28 H 2-OCH ₃ H H H H oil 29 H 2-NO ₃ -4 -CH ₃ CO H H H H 178-179 30 H 2-SCH ₃ H H H H oil '31 H 2-OCF ₃ H H H H 114-115 32 H 2,3,4-Cl ₃ H H H H 97-98 33 H 2,4,5-Cl ₃ H H H H oil 34 H 2-NO 2 -4-OCH ₃ H H H H 152-153 35 H 2-NO ₃ -O-CI H H H H 168-169 36 H 2-OC ₂ H ₅ H H H H 66 to 67.5 37 H 3-NO ₂ H H H H 140 to 141.5 38 H 3-CI H H H H 141.5 to 143 39 H 3-OCF ₃ H H H H 130-131 40 H 3-CF ₃ H H H H 138.5 to 140 41 H 3-CH ₃ H H H H 146.5 to 147.5 42 H 3-OCH ₃ H H H H 132-134 43 H 4-tert-C ₄ H ₉ H H H H 170.5 to 172.5 44 H 4-1 H H H H 212-214 45 H 2-NO ₂ -4-CI H H H 3,4-F ₃ 86-89 46 H 2-NO ₂ -4-CI H H H 4-CH ₃ 66-69 47 H 2-NO ₂ -4-CI H H H 4-OCH ₃ 73-74 48 H 2-NO ₂ -4-CI H H H 3-CI 130.5 to 132.5 49 H 2-NO ₂ -4-CI H H H 4-SCH ₃ 93-96 52 H 2-NO ₂ -4-CI H H H 2-Br 109-112

Table I (continued)

Table!!

connection R ¹ R ³ R ⁴ R ⁵ R ^e R ⁸ Mp. ° C No. 53 H 2-NO ₂ -4-CI CH ₃ H H 2-OCH ₃ 151-153 54 H 2-NO ₂ -4-CI CH ₃ H H 4-OC ₂ H ⁵ 119-121 55 H 2-NO ₂ -4-CI CH ₃ H H 4-SCH ₁ 75-77 56 H 2-NO ₂ -4-CI CH ₃ H H H 60-62 112 H 2-CF3-4-F H H H H 154-156 113. H 2-CI-4-CF ₃ H H H H 126-128

.V

connection R ¹ R ² R ³ R ⁴ R ⁵ R ⁸ Schmp.X No. 57 H H 2,4-diNO ₂ H H H 151-154 58 H H 2-NO2-5-CI H H H 165.5 to 167.5 59 H H 2-NO ₂ H H H 206-208 60 H H 2-CI H H H 209-210 61 H H 3-CF ₃ H H H 198-201 62 H H 2,4-Cl ₃ H H H 142-144 63 H H 2-NO ₂ -S-CH ₃ H H H 163-165 64 H H 2,4-bisCFa H H H 162-165 65 H H 2-CR3 H H H 189-191 68 H H 2,5-Cl ₂ H H H 164-166 69 H H 2-OC ₃ H ₅ H H H 101-104 70 H H 2,3,4-Cl ₃ H H H 172-176 71 H H 2,4,5-Cl ₃ H H H 139.5 to 140.5 72 H H 2-NO ₂ - ^ - Br H H H 168-171 73 H H 2-NO2-4-CN H H H > 250 ° C 74 H H 2-NO ₂ - ^ - CF ₃ H H H 154-156 75 H H 2-NO2-4-F H H H 170-172 76 H H 2-CH ₃ -S-NO ₃ H H H 161-163 77 H H 2-CH ₃ -S-NO ₂ H H H 198-200 78 H H 2-Br H H H 163-165 79 H H 2 -OCH ₃ H H H 149-153 80 H H 3-NO ₂ H H H 232-234 81 H H 3-Br H H H 202-204 82 H H 3-OCF ₃ H H H 151-152 83 H H 3-OCH ₃ H H H 139-142 84 H H 3-CI H H H 190-193 85 H H 3-CH ₃ H H H 157-160 86 H H 4-NO ₃ H H H 212-214 88 H H 4-CI H H H 182-184 89 H H 4-CN H H H 239-243 90 H H 4-Br H H H 179-182 91 H H 4-CH ₃ H H H 176-179 92 H H 4-OCH ₃ H H H 138-140 93 H CH ₃ 2-nor-4-CI H CHj H 146-148 94 - (CH ₁ J ₅ - 2-NO ^ CI H H H 150-152 95 H H 2-NO2-4-CI H CH ₃ CH ₃ 147-149 96 H H 2-NOH-CI CH ₃ CH ₃ CH ₃ 124-126 97 CH ₃ CH ₃ 2,4-bisCF ₃ H H H 175 to 175.5 98 CH ₃ CH ₃ 2-F-NÜ2-4 H H H 135-136 99 CH ₃ CH ₃ 2-NO ₂ - ^ - CF ₃ H H H 147-150

Table II (continued)

Compound No. R ¹ R ² R ³ R ⁴ R ⁵ R ^e Schmp.X 100 CH ₃ CH ₃ 2,3,4-Cl ₃ H H H 273-275 101 CH ₃ CH ₃ 2,4,5-Cl ₃ H H H 176-178 102 CH ₃ CH ₃ 2-NO2-4-Br H H H 144-147 103 CH ₃ CH ₃ 2-NO ₂ - ^ - SO ₂ CH ₃ H H H 168-170 110 H H 2-NO ₂ - ^ - SO ₂ CH ₃ H H H 157-158 111 CH ₃ CH ₃ 2-NO ₂ - ^ - OCH ₃ H H H 164-166 114 H H 2-NOr-4-CO ₂ Et H H H 135-137 115 " H H 2-CI-4-CF ₃ H H H 108-110 116 H H 2-CF3-4-F H H H 179-181 117 CH ₃ H 2-NOr-4-CF ₃ H H H 126-128 118 H H 2-NOr-4-CF ₃ CH ₃ CH ₃ CH ₃ 133-134 119 H H 2-NOr ^ -OCH ₃ H H H 173-175 120 CH ₃ CH ₃ 2-NO-1-CO ₂ Et H H H 184-185 121 CH ₃ CH ₃ 2-NO ₂ - ^ - CH ₃ H H H 165-167 122 H H 4-tert-C ₄ H ₉ H H H 159-161 123 H H 2-NO ₂ -4,3-CI ₂ H H H 146-148 124 H H 2-NOr-4-CH ₃ CO H H H 139-141 125 H H 2-NOr-4-CH ₃ H H H 168-170 126 H H 2-CI-4-SO ₂ CH ₃ H H H 187-188 127 H H 2-NO-C 1 -C-S-CH ₃ H H H 163-165 128 H H 2-CI-5-NO ₂ H H H 131-133 129 H H 2-CHa-4-Br H H H 156-158 130 H H 3-Br-4-CH ₃ H H H 168-170 131 H H 2-SCH ₃ H H H 116-118 132 H H 2-CH ₃ H H H 217-219 133 H H 4-1 H H H 144-146 134 H H 3,5- (CF ₃ J ₂ H H H 137-139 135 CH ₃ CH ₃ 2-CM-SO ₂ CH ₃ H H H 216 136 CH ₃ CH ₃ 2-CFa-4-F H H H 159-161 137 CH ₃ CH ₃ 2-NOr-4,5-CI ₂ H H H 179-180 138 CH ₃ CH ₃ 2-NO2-4-Cl-5-CH ₃ H H H 188-189 139 CH ₃ CH ₃ 2-nor-4-CN H H H 169 to 170.5 140 H H 2-NO ₂ - ^ 1-SO ₂ CH ₃ CH ₃ CH ₃ CH., 164-166 141 H H 2-NOr-4-CF ₃ H CH ₃ H 132-134 142 H H 2-NO ₂ 1-CFa H CH ₃ CH ₃ 145-146 143 - (CH ₂ I ₅ - 2-nor-4-CFa H H H 151-153 144 CH ₃ C ₂ H ₆ 2-NOr-4-CF ₃ H H H 163-164 145 C ₂ H ₅ C ₂ H ₆ 2-NOr-4-CF ₃ H H H 182-184 146 CH ₃ CH ₃ 2-NOr-4-CF ₃ CH ₃ H H 124-125 147 CH ₃ CH ₃ 3,5- (CF ₃ I ₂ H H H 166-167

Example 8

Links 104 and 105

A solution of 4-chloro-2-nitrobenzoyl chloride (4.4 g) in dry dichloromethane (5 ml) was stirred at a temperature of 5-10T with stirring a solution of 5-phylmecyclohexane-1,3-dione (3.7 g). and triethylamine (2.8 ml) in dry dichloromethane (50 ml), and the mixture was stirred at room temperature for 18 hours. To the solution was added triethylamine (8.4 ml) and acetone cyanohydrin (0.4 ml) successively, and the mixture was stirred at room temperature for 4 hours. The resulting solution was washed successively with 2N hydrochloric acid (25 ml) and water (3x25 ml), dried over sodium sulfate and evaporated under reduced pressure to give a brown solid, which was recrystallized from acetonitrile. There is obtained 2- (4-chloro-2-nitrobenzoyl) -5-phenylcyclohexone-1,3-dione (4.2 g), F.144-145 "C, as a light cream crystalline solid.

By proceeding in the same manner, but replacing 5-phenylcyclohexane-1,3-dione by 4-carbethoxy-5-phenylcyclohexane-1,3-dione, the following are obtained: 4-Carbethoxy-2- (4-chloro) 2-nitrobenzoyl) -5-phenyl-cyclohexane-1,3-dione, m.p. 57-59 ° C (purified by column chromatography) as a yellow crystalline solid.

Example 9

Compounds 106 and 107

2-Nitro-4-trifluoromethylbenzoyl chloride (4 g) was added at a temperature of 0-5 ⁰ C with stirring a solution of triethylamine (2.2 ml) and 6-methyltetrahydropyran-2,4-dione (2 g) in dry acetonitrile (25ml) and the mixture stirred at room temperature for 4 hours. The solution was added sequentially with triethylamine (6.4 ml) and acetone cyanohydrin (0.3 ml), and the mixture was stirred for additional 2 hours at room temperature. The mixture was diluted with dichloromethane (50ml) and washed sequentially with 2N hydrochloric acid (20ml) and water (3x 20ml). The

Dichloromethane solution was dried over sodium sulfate and evaporated under reduced pressure to give a brown resin, which was triturated with chloroform-hexane (1: 1, 20ml). There is obtained 3- (2-nitro-4-trifluoromethylbenzoyl) -6-methyltetrahydrc.pyran-2,4-dione (2.2g), m.p. 135-136.5 ° C, as a light cream crystalline solid. By proceeding in the same manner but using 6-phenyltetrahydropyran-2,4-dione instead of 6-methyltetrahydropyran-2,4-dione, 3 (2-nitro-4-trifluoromethylbenzoyl) -6-phenyltetrahydropyran is obtained -2,4-dione, mp 160-161 ⁰ C.

Example 10 Compound 108

A solution of 4-chloro-2-nitrobenzoyl chloride (1 g) in dry dichloromethane (5 ml) was stirred at a temperature of 0-10 ° C with stirring of a solution of triethylamine (0.62 ml) and 5- (2-ethylthiopropyl ) -6-carbethoxycyclohexane-1,3-dione (1.3g) in dry dichloromethane (20ml) and the mixture stirred at room temperature for 2 hours. The solution was added successively with triethylamine (1.9 g) and acetone cyanohydrin (0.1 ml), and the mixture was stirred at room temperature for a further 18 hours. The mixture was then washed successively with 2N hydrochloric acid (10 ml) and water (2 x 10 ml), dried over magnesium sulfate and evaporated under reduced pressure. 2- (4-Chloro-2-nitrobenzoyl) -5- (2-ethylthiopropyl) -6-carbethoxycyclohexane-1,3-dione (0.6g), m.p. 102-104 ° C, as an orange solid.

Example 11 Compound 109

A solution of 2-nitro-4-trifluoromethylbenzoyl chloride (2.6g) in dry acetonitrile (8ml) was stirred at room temperature with stirring to a solution of 6-methyl-6-trifluoromethylpiperidine-2,4-dione (2g) and dry triethylamine (1st , 4ml) in dry acetonitrile (25ml) and the mixture was stirred at room temperature for 18 hours. Dry triethylamine (4.5 ml) and aceto-cyanohydrin (0.5 ml) were added sequentially and the mixture was stirred for 8 hours at room temperature. The reaction mixture was washed successively with 2N hydrochloric acid (25 ml) and water (3x50 ml), dried over magnesium sulfate and evaporated under reduced pressure to give a yellow resin, which was then crystallized from a toluene-kexane mixture (15 ml: 10 ml).

There is obtained 3- (2-nitro-4-trifluoromethylbenzoyl) -6-methyl-trifluoromethylpiperidine-2,4-dione (3.2g), mp 164.5-165.5 ° C, as a yellow crystalline solid.

Example 12 Compound 66

Dry triethylamine (1.33g) was added at a temperature of 0-5 ° C with stirring to a suspension of piperidine-2,4-dione (1.13g), anhydrous zinc chloride (1.64g) and benzoyl cyanide (1.31g) g) in dry dichloromethane (50ml) and the mixture stirred at room temperature for 18 hours. The mixture was washed successively with 2N hydrochloric acid (2 × 30 ml) and water (3 × 30 ml), dried over magnesium sulfate and evaporated under reduced pressure to give a pale yellow solid which, after recrystallization from acetonitrile (0.5 ml) 3 Benzoyl-piperidine-2,4-dione (0.5g), mp 164-165 ° C as a cream solid.

Example 13 Compound 87

Dry triethylamine (3.24 g) was added at a temperature of 0-5 ⁰ C with stirring to a solution of diethyl phosphate (1.96 g), 4-trifluoromethylbenzoic acid (2,28g) and piperidine-2,4-dione (1, 13g) in dry dimethylformamide (50ml) and the mixture stirred for 5 hours at room temperature. The mixture was then diluted with dichloromethane (70ml) and the solution washed sequentially with 2N hydrochloric acid (70ml) and water (5x 30ml). The dichloromethane solution was dried over magnesium sulfate and evaporated under reduced pressure to give a brown solid, which was then recrystallized from toluene (11 ml). To give 3- (4-trifluoromethylbenzoyl) -piperidine-2,4-dione (0.44 g), mp 197-200 ⁰ C, as a pale green crystalline solid.

Example 14 Compound 67

A solution of 3,4-dichlorobenzoyl chloride (2.1 g) in dry acetonitrile (10 ml) was stirred at room temperature while stirring a solution of piperidine-2,4-dione (1.13 g) and dry triethylamine (1.31 g) dry acetonitrile (50ml) and the mixture was stirred at room temperature for 18 hours. Potassium cyanide (0.07 g), triethylamine (3.1 g) and tris (3,6-dioxaheptyl) amine (0.5 ml) were added successively, and the mixture was stirred at room temperature for 24 hours. The mixture was then evaporated under reduced pressure and the residue thus obtained was dissolved in dichloromethane (50 ml). The dichloromethane solution was washed successively with 2N hydrochloric acid (2 × 30 ml) and water (3 × 30 ml), dried over magnesium sulfate and evaporated under reduced pressure to give a brown solid, which was purified by column chromatography. To give 3- (3,4-dichlorobenzoyl) piperidine-2,4-dione (0.37 g), mp 171.5 to 174.5 ⁰ C, as a cream crystalline solid.

Example 15

Connection 19

A suspension of 5,6-dihydro-4- (2-fluoro-benzoyl-oxy) -6-phenylpyridine-2 (1H) -one (10.9g) in dichloroethane (10ml) was added at a temperature of -5 to + 5 ⁰ C while stirring a mixture of aluminum chloride (9.3g) and dichloroethane (50ml) was added, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was then a

Mixture of ice and concentrated hydrochloric acid (400g / 75ml) was added and the acidic mixture extracted with dichloroethane (3x 200ml). The combined extracts were then washed with water (2x200 ml), dried over magnesium sulphate and evaporated under reduced pressure to give a yellow oil, which was recrystallised from a methanol-water mixture (25 ml + 5 ml). 3- (2-Fluo-benzoyl) -6-phenyl-piperidine-2,4-dione (2.1 g), m.p. 116-116.5 ° C, as a pale yellow crystalline solid.

If, in the same manner as described above in Comparative Example 1, but replacing 2-nitrobenzoyl chloride by 2-fluorobenzoyl chloride, the following are obtained:

5,6-Dihydro-4- (2-fluorobenzoyloxy) -6-phenyl-pyridine-2 (1H) -one, m.p. 148-149 ° C (recrystallized from methanol) from colorless crystalline solid.

Example 16

Connections 50 and 51

A solution of m-chloroperbenzoic acid (1.48g) in dry dichloromethane (40ml) was added under stirring to a solution of 3- (4-chloro-2-nitrobenzoyl) -6- (4-methylthiophenyl) -piperidine-2,4-dione (1.5g) in dry dichloromethane (60ml) at a temperature of 5-10 ° C, and the mixture was then stirred at room temperature for 18 hours. The mixture was washed successively with 2N sodium methahydrogen sulfite solution (25 ml) and ¹ x water (2 x 50 ml), dried over magnesium sulfate and evaporated under reduced pressure to give a cream solid, which was recrystallized from a dioxane-hexane mixture (25 ml: 16 ml). There is obtained 3- (4-chloro-2-nitrobenzoyl) -6- (4-methylsulphonylphenyl) -piperidine-2,4-dione (0.58g), F.296-299 ° C, as a light yellow, crystalline solid.

By proceeding in the same manner but using half the amount of m-chloroperbenzoic acid, there are obtained 3- (4-chloro-2-nitrobeproyl) -6- (4-methylsulphinylphenyl) -piperidine-2,4-dione, F. 248-251 "C.

Example 17

A mixture of methyl 6,6-dimethylpiperidine-2,4-dione-3-carboxylate (26.3g), water (30ml) and concentrated hydrochloric acid (3 drops) in acetonitrile (300ml) was heated at reflux for 4 hours.

The cooled solution was evaporated under reduced pressure and the residue crystallized from water (50 ml) urnkristallisiert to form 6,6-dimethylpiperidine-2,4-dione (7.3 g), mp 183-184 ⁰ C as a cream crystalline solid.

The piperidinediones listed in Tables III and IV were prepared by the same procedure:

Table III

R ' R ⁴ R ⁵ R ^e R ⁸ Mp. ° C H H H H H 171-172 CH ₃ H H H H 185-187 H CH ₃ H H H 109-111 H H H H 3,4-F ₂ 116-120 H- H H H 4-CH ₃ 153-155 H H H H 4-OCH., 171-172 H H H H 3-CI 105-107 H H H H 4-SCH ₃ 169-173 H H H H 2-Br 93-95 H CH ₃ H H 2-OCH ₃ 168-170 H CH ₃ H H 4-OC ₂ H ₅ 130-133 H CH ₃ H H 4-SCH ₃ 99-102

Table IV

R ¹ R ² R ⁴ R ⁶ R ^e Mp. ° C H H CH ₃ H H oil H H CH ₃ CH ₃ CH ₃ 52-54 CH ₃ CH ₃ CH ₃ H H 101-102 CH ₃ CH ₃ H H H 182-183 H H H H H 100-101 H H H CH ₃ H 86-8S H CH ₃ H H H 120-123 H CH ₃ H CH ₃ H 115-118 - (CH ₂ ) S- H H H 153-155 H H H CH ₃ CH ₃ 125-127 CF ₃ CH ₃ H H H 153-154 CH ₃ C ₂ H ₆ H H H 136-137 C ₂ H ₆ C ₂ H ₆ H H H 129-130

Verglelchsbelsplol 2

A solution of methyl S-fethoxycarbonylacetamide-S-methyl butyrate (45g) and sodium metal (4.22g) in anhydrous methanol (450ml) was refluxed for 3 hours. The cooled mixture was evaporated under reduced pressure and the residue dissolved in water (200 ml). The aqueous solution was washed with ether (3x 100ml) (3x 100ml), acidified with 2N hydrochloric acid and the acidic mixture extracted with dichloromethane (3x 100ml).

The combined extracts were washed with water (2 x 100 ml), dried over magnesium sulfate and evaporated under reduced pressure. Obtained M3thyl-6,6-dimethylpiperidine-2,4-dione-3-carboxylate (26.3 g), mp 170-172 ⁰ C, as a cream crystalline solid.

The procedure is repeated in the same manner, but replacing methyl 3- (etoxycarbonylacetamide) -3-methyl-butyrate by ethyl 3-methoxycarbonylacetamide) -3-phenylbutyrate, to give methyl-e-methyl-e-phenylpiperidine ^ - dione S-carboxylate as a clear red oil.

By proceeding in the same manner but replacing methyl 3- (ethoxycarbonylacetamide) -3-methylbutyrate with methyl 3- (ethoxycarbonylacetamide) -N-methyl-3-phenylpropionate, methyl-i-methyl-e- phenylpiperidine ^ dione-S-carboxylate as a clear orange oil.

By proceeding in the same manner but substituting methyl-3- (etoxycarbonylacetamide) J-S-trifluoromethylbutyrate for methyl S-letoxycarbonylacetamide J-S-mei.i.lbutyrate, methyl 6-methyl-6-trifluoromethylpi is obtained [.eridin-2,4-dione-3-carboxylate, F. 150-152 ⁰ C, as a cream crystalline solid.

Comparative Example 3

A solution of Ethylmalonoylchlorid (31 g) in dry dichloromethane (50 ml) was added at a temperature of 0-5 ⁰ C to a well stirred mixture of methyl 3-aminoisovalerathydrochlorid (33.5 g) and dry triethylamine (58,5ml) in dry Dichloromethane (300ml) was added and the mixture stirred at room temperature for 18 hours. The mixture was washed successively with 2N hydrochloric acid (50 ml), water (50 ml), 2N sodium carbonate (25 ml) and water (3x50 ml), dried over magnesium sulfate and evaporated under reduced pressure. Methyl 3- (ethoxycarbonylacetamide) -3-methylbutyrate (45 g) is obtained as a clear orange oil.

By proceeding in the same manner, but substituting methyl-3-aminoisovalerate hydrochloride with methyl-3-rr) 9thylamino-3-phenylpropionate, we obtain:

Methyl 3- (ethoxycarbonylacetamide) -N-methyl-3-phenyl-propionate as a clear orange-colored oil.

By proceeding in the same manner, but substituting methyl-S-aminoisovalerate hydrochloride with methyl 3-amino-3-methyl-4,4,4-trifluorobutyrate, we obtain:

Methyl S-fethoxycarbonylacetamide J-S-trifluoromethyl butyrate as an orange clear oil.

Comparative Example 4

Concentrated sulfuric acid (80ml) was added at a temperature of 0-5 ⁰ C with stirring, a solution of methyl cyanoacetate (28ml) and ethyl-3-hydroxy-3-phenylbutyrate (65g) and the mixture stirred at room temperature for 18 hours. The mixture was added to crushed ice (250 g) and the resulting acidic mixture extracted with dichloromethane (3 × 100 ml). The combined extracts were washed with water (4 x 250 ml), dried over sodium sulfate and evaporated under reduced pressure. Ethyl S-t-methoxycarbonylacetamide J-S-phenylbutyrate (43.16 g) is obtained as a clear brown oil.

Comparative Example 5

Thionyl chloride (30ml) was added at a temperature of 0-5 ⁰ C with stirring, a solution of 3-methyl-amino-3-phenylpropionsäuro (39g) in wassorfreiem methanol and the mixture was stirred at room temperature for a period of 5 hours. The solution was evaporated under reduced pressure and the residue treated with 2N sodium carbonate (350 ml). The solution was then extracted with dichloromethane (2 x 100 ml). The combined extracts were washed with water, dried over magnesium sulphate and evaporated under reduced pressure. Riviethyl S -methylamino-S-phenylpropionate (36.9 g) is obtained as a clear orange oil.

By proceeding in the same manner, but substituting 3-amino-3-trifluoromethylbutyric acid for 3-methylamino-3-phenylpropionic acid, we obtain:

Methyl 3-amino-3-methyl-4,4,4-trifluorobutyrate as a clear colorless oil.

Comparative Example 6

A solution of N-methyl-3-phenylisooxazolidin-3-one (45g) in methanol (510ml) was added over 2.81kg / cm ² over 5% palladium on charcoal (0.5g) for 6h Hydrogenated for hours. The mixture was filtered and the filtrate was inoculated under reduced pressure. This gives S-methylamino-S-pher.ylpropionsäure (39g), mp 167-168 ⁰ C, as a bright orange kris'allinen solid

Comparative Example 7

A solution of trifluoromethylcrotonic acid (10g) and liquid ammonia (23ml) in ammonium hydroxide (27ml, density of solution [0.88]) was heated in a closed steel container at a temperature of 148-152 ° C for 16 hours. Obtained after evaporation of the cooled solution 3-amino-3-trifluoromethylbutyric acid (10.2g) as a viscous colorless oil.

Claims (23)

1. A process for preparing cyclic 2-benzoyl-1,3-dione compounds of the general formula (R ³ ) in which X represents a methylene group, an oxygen atom or a sulfur atom or an -NR ⁴ group, Y represents a -C (R ⁵ ) (R ⁶ ) methylene group or an oxygen atom, R ^{1 represents} a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms which may optionally be substituted by one or more halogen atoms, or eire cycloalkyl group 3-6 carbon atoms, R ^{2 represents} a hydrogen atom or an R ⁷ group or R ¹ and R ² together represent an alkylene group having 2 to 6 carbon atoms, R ^{3 represents} a halogen atom, a hydroxy, carboxy, nitro or cyano group, an amino or carbamoyl group (represented by one or two straight-chain or branched alkyl groups having 1 to 6 carbon atoms), a straight-chain or branched alkoxycarbonyl or alkanoyl or alkanoyl-arhino group having 2 to 7 carbon atoms or a group R, RO, RS, RSO or RSO ₂ , in which R is a straight-chain or branched alkyl group having 1 to 6 carbon atoms , which may optionally be substituted by one or more halogen atoms, R ^{4 represents} a hydrogen atom or a straight-chain or branched alkyl or alkoxycarbonyl group each having 1 to 6 or 2 to 7 carbon atoms, R ^{5 represents} a hydrogen atom or a straight-chain or branched alkyl or alkoxycarbonyl group having in each case 1 to 6 or 2 to 7 carbon atoms, R ^{6 represents} a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, R ^{7 represents} a straight-chain or branched alkyl group having 1 to 6 carbon atoms which may be substituted by one or more halogen atoms or a straight-chain or branched alkylthio group having 1 to 6 carbon atoms or by a group (R ⁸ ) _n- phenyl-S-, or represents a cycloalkyl group having 3 to 6 carbon atoms or the tetrahydrothiapyran-3-yl group, or a group (R ⁸ ) _n -phenyl-, in which R ^{8 represents} a halogen atom, a hydroxy, carboxy, nitro or cyano group, an amino or carbamoyl group (which may be substituted by one or two straight-chain or branched alkyl groups having 1 to 6 C atoms), a straight-chain or branched alkoxycarbonyl or alkanoxyl or alkanoylamino group having 2 to 7 carbon atoms or a group R, RO, RS, RSO or RSO ₂ , in which R represents a straight or branched alkyl group having 1 to 6 carbon atoms, which may optionally be substituted by one or more halogen atoms, where m is zero or an integer from 1 to 5, η is zero or an integer from 1 to 5, with the proviso that when X is a methyl group and Y is a -C (R ⁵ ) (R ⁶ ) methylene group represents, which R ¹ and R ² can not be simultaneously a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, or one of their agriculturally acceptable salts, characterized in that compounds of the formula II in which the various symbols have the given definition, react with the appropriate benzoic acid or one of its reactive derivatives, or with a benzoyl halide to give a compound of general formula III be benzoylated, in which the various symbols have the given definition, whereupon the compound III is rearranged using a source of cyanide ions or in the presence of aluminum chloride or a substituted in position 4 aminopyridines. 2. The method according to claim 1, characterized in that compounds are prepared in which R ^{1 represents} a hydrogen atom or a straight-chain or branched alkyl group η iit 1 to 6 carbon atoms, R ^{2 represents} a hydrogen atom or an R ⁷ group, R ^{3 has} the meaning given in claim 1, but does not stand for a carbamoyl group, R ⁷ denotes a straight-chain or branched alkyl group having 1 to 6 C atoms, which is represented by a straight-chain or branched alkylthio group having 1 to 6 C atoms or a group ( R ⁸ ) _n- phenyl-S- may be substituted, or a cyclohexyl group, the tetrahydrothiapyran-3-yl group or a group (R ⁸ ) _n -Phenyl-, in which R ^{8 has} the meaning given in claim 1, however, does not represent a carbamoyl group, and wherein other symbols have the meaning given in claim 1. 3. The method according to claim 1, characterized in that compounds are prepared in which Y represents a-C (R ⁵ ) (R ⁶ ) -Methylene group, X represents an NR ⁴ group, R ^{1 is} a hydrogen or latom represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, R ^{2 represents} a hydrogen atom or an R ⁷ group, R ^{3 has} the meaning given in claim 1, but not a carbamoyl group, R ^{7 is} a straight-chain or branched alkyl group having 1 to Represents 6 C atoms or a group (R ⁸ ) -phenyl, in which R ^{8 has} the meaning given in claim 1, but does not represent a carb'jmoyl group and the other symbols have the meaning given in claim 1. 4. The method according to claim 1 or 2, characterized in that compounds are prepared in which Y is a -C (R ⁵ ) (R ⁶ ) methylene group, wherein R ⁵ and R ^{6 have} the meaning given in claim 1. 5. The method according to any one of claims 1 to 4, characterized in that compounds are prepared in which X is an -NR ⁴ group, Y is a -C (R ⁵ ) (R ⁶ ) methylene group and R ^{2 is} an alkyl or is optionally substituted phenyl group having the meaning given in claim 1 for R ⁷ , and the other symbols have the meaning given in claim 1. 6. The method according to claim 1, characterized in that compounds are prepared in which R ^{2 is} a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, optionally substituted by one or more halogen atoms or a cycloalkyl group mil 3 to 6 C atoms, or for a group (R ⁸ ) _n- phenyl or R ¹ and R ² together represent an alkylene group having 2 to 6 carbon atoms. 7. The method according to claim 1, characterized in that compounds are prepared in which R ^{1 represents} a straight-chain or branched alkyl group having 1 to 6 carbon atoms, which is substituted by one or more halogeno or a cycloalkyl group having 3 to 6 C Atoms and R ^{2 is} a group (R ⁸ ) _n -phenyl-. 8. The method according to claim 1, characterized in that compounds are prepared in which X represents a methylene group, a Se uerstoff- or sulfur atom or an -NR ⁴ group in which R ^{4 is} a hydrogen atom or a straight-chain or branched alkyl group with 1 represents up to 6 C atoms, Y represents a -C (R ⁵ ) (R ⁶ ) -methylene group, Fv represents a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 C atoms, which if appropriate may be substituted by one or more halogen atoms, or a cycloalkyl group having 3 to 6 C atoms, R ^{2 represents} a straight-chain or branched alkyl group having from 1 to 6 carbon atoms which is substituted by one or more halogen atoms or a cycloalkyl group having 3 to 6 carbon atoms or R ¹ and R ² together represents an alkylene group having 2 to 6 carbon atoms represent. 9. The method according to claim 1, characterized in that compounds are prepared in which
X represents an -NH group, Y represents a -C (R ⁵ ) (R ⁶ ) -methylene group, R ^{1 represents} a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 C atoms, R ^{2 represents} a hydrogen atom or a geradketti & e or branched alkyl group having 1 to 6 carbon atoms. 10. The method according to claim 1, characterized in that compounds are prepared in which X creates a methylene group c, Y represents a -C (R ⁵ ) (R ⁶ ) group, R ^{1 is} a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 C atoms and R ^{2 is} a group (R ⁸ ) _n -phenyl-. 11. The method according to claim 10, characterized in that compounds are prepared in which R ^{3 is} a hydroxy, carboxy, nitro or cyano group, an amino or carbamoyl group (by one or two straight-chain or branched alkyl groups having 1 to 6 C atoms), a straight-chain or branched alkyl or alkoxy group which is substituted by one or more halogen atoms, an alkoxycarbonyl, alkanoyl or alkanoylamino group each having 1 to 6 and 2 to 7 carbon atoms or a group RS , RSO or RSO ₂ having 1 to 6 C atoms, which is optionally substituted by one or more halogen atoms. 12. The method according to claim 10 or 11, characterized in that compounds are prepared in which R ^{3 is} nitro. 13. The method according to claim 10,11 and 12, characterized in that compounds are prepared in which Y is not a methylene group -CH ₂ - represents. 14. The method according to claim 1, characterized in that compounds are prepared in which X represents an oxygen or sulfur atom, Y is a-C (R ⁵ ) (H ⁶ ) methylene group, R ^{1 is} a hydrogen atom or a straight-chain or branched alkyl group represents 1 to 6 carbon atoms and R ^{2 is} a group (R ⁸ ) _n -phenyl-. 15. The method according to any one of the preceding claims, characterized in that compounds are prepared in which the (R ⁸ ) _n substitution means that 2-chloro, , 2-trifluorometh, 'or 2-nitro is substituted by 4-trifluoromethoxy, 4-trifluoromethylthio, 4-trifluoromethylsulfinyl, 4-trifluoromethylsulfonyl, 4-chloro, 4-trifluoromethyl or 4-methylsulfonyl. 16. The method according to claim 15, characterized in that compounds are prepared in which the (R ⁸ ) "- substitution comprises a 2-nitro substitution. 17. The method according to claim 15 or 16, characterized in that compounds are prepared in which a substituent is absent in position 6 of the benzoyl group. 18. The method according to claim 1, characterized in that compounds are prepared in which a compound according to claim 1, which is described above as one of the compounds Nos. 1-10,14, 20, 23-27, 34, 45-48, 53rd -76, 81-83, 94-100, 102-107, 109-111 and 113-121. 19. The method according to claim 1, characterized in that the conversion of the thus obtained compound of formula I is carried out in another compound of formula I. 20. The method according to claims 1,19, characterized in that the conversion of the compound of formula I thus obtained follows an agriculturally acceptable salt. 21. A herbicidal composition comprising as active ingredient a cyclic 2-benzoyl-1,3-dione according to claim 1 or one of their agriculturally acceptable salts in association with an agriculturally acceptable diluent or carrier and / or surface active agent. A herbicidal composition according to claim 21 containing 0.05 to 90% by weight of active ingredient. 23. A method for controlling the growth of weeds at a locus by applying a cyclic 2-benzoyl-1,3-dione according to claim 1 or one of their agriculturally acceptable salts,