HU190819B - Herbicide compositions containing cyclohexane-1,3-dione derivatives and process for producing the active agents - Google Patents

Abstract

In the formula (I), the active ingredients of the herbicides of the present invention are: R * is hydrogen, C 2-6 alkanoyl, or benzoyl, optionally substituted with one or two nitro groups, or an alkali metal cation or a transition metal cation; - R 2 is C 1-5 alkyl, C 2-6 alkenyl, C 3-6 alkynyl, C 1-5 haloalkyl, C 2-6 haloalkenyl, or benzene ring optionally substituted with one or two halogen atoms substituted benzyl; - R 3 is C 1-6 alkyl and - n is 2, 3, 4 or 5 -

Description

This invention relates to herbicides containing cyclohexane-1,3-dione derivatives and to a process for the chemical preparation of the active ingredient.

It is known in the literature that certain formulations containing cyclohexane-1,3-dione derivatives can be used to control phylloxera. so e.g. the cyclohexane-1,3-dione derivative known as alloxydim sodium [methyl-3 (1-allyloxyimino)] in the "Pesticide Manual" (edited by Worthing CR; The British Crop Protection Council, 6th edition, 1979). butyl) -4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-ene carboxylate] and in weed control agents. The above compound is disclosed in U.S. Patent No. 464,655. U.S. Pat. No. 1,461,170 and U.S. Pat. No. 3,950,420.

More recently, at the 1980 British Crop Protection Conference (Weeds, Proceedings, Vol. 1, Research Reports 29, page 46, British Crop Protection Council, 1980), a new code named "NP 55" was added. cyclohexane-1,3-dione-type herbicide [active ingredient: 2- (N-ethoxy-butyrimidoyl) -5- (2-ethyl-thiopropyl) -3-hydroxy-2-cyclohexen-one] . This compound is disclosed in AU-A1-35 134/78. s. Australian patent application and conforming foreign patents.

Alloxydim sodium and NP 55, as already mentioned, are selective inhibitors of the growth of weeds (monocotyledonous plants) in broad-leaved (dicotyledonous) plants. The 1978 “Theoretical and Applied Chemistry IV. In Proceedings of the International Union of Pure and Applied Chemistry - Fourth International Congress of Pesticide Chemistry - Part 2, pp. 235-243. In a paper on the chemical structure and herbicidal activity of alloxydim sodium in 1979, Twataki and Hirono stated the selective herbicidal activity of certain 5-phenyl-substituted-cyclohexane-1,3-dione derivatives in wheat and oat crops:

"In introducing C-5 substituted phenyl groups (Table 6), selectivity was observed in wheat and oat (e.g. Avena fatua and Avena sativa). Only selective activity was observed for p-substituted phenyl derivatives, while selectivity was not observed for doubly or tri-substituted phenyl derivatives. The degree of activity or selectivity was even different for p-substituted phenyl derivatives. The best results were obtained for the p-methyl derivative, while the hydroxy or methoxy derivative gave moderately good results. "

It has been found that compositions containing cyclohexane-1,3-dione derivatives substituted in the 5-position with more than one methyl group have particularly valuable and favorable selective herbicidal activity in cereals.

The herbicides according to the invention contain as active ingredient compounds of the formula I.

In the formula (I):

R ¹ is hydrogen, C 2 -C 6 alkanoyl, or benzoyl optionally substituted by one or two nitro groups, or an alkali metal or transition metal cation;

- R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, C 2 -C 6 haloalkenyl, or optionally substituted with one or two halogen atoms in the benzene ring benzyl;

- R ³ is C 1 -C 6 alkyl and *

- n is 2, 3, 4 or 5.

If the active ingredients of formula (I) ^R1 represents acyl, the acyl group is not critical κ is the effect in terms of importance. Without limiting the scope of the patent to theoretical considerations, it is noted that the acyl group at the R ¹ position is known to be cleaved by hydrolysis in the plant to produce a compound of formula (I) wherein R ¹ is hydrogen. The acyl group may be a C 2 -C 6 alkanoyl group or a benzoyl group optionally substituted on the benzene ring with one to three halogens, nitro, methyl and / or methoxy groups.

When R ^{1 in the} active compounds of formula (I) represents an inorganic or organic cation, the meaning of the cation is not critical to the effect. Without limiting the scope of the patent to theoretical considerations, it is to be noted that the cation at the R ¹ site is cleaved in the plant to form a compound of formula (I) wherein R ¹ is hydrogen. R ¹ as an inorganic cation may represent an alkali metal cation or a transition metal cation or ammonium ion. R ^{1 is} an organic cation (R ⁴ ) ₄ N ⁺ cation - R ⁴ is C 1-6 alkyl; R ^{4 is the} same or different (C 1 -C 6) alkyl.

Note that R ¹ is hydrogen the compounds of formula (I) may be present in form of one of three tautomeric forms. The three tautomeric forms are shown in Esema [(IIa), (IIb) and (IIc)].

More preferred values of R ¹ are the hydrogen, benzoyl, sodium and potassium cations.

R ^{2 is} preferably ethyl, n-propyl, η-butyl, allyl, propargyl, 2-fluoroethyl, 2-chloroallyl, benzyl, halobenzyl, methylbenzyl or nitrobenzyl represents csoport.

R ² particularly preferably represents methyl, ethyl, n-propyl or allyl.

Preferably R ³ is ethyl or n-propyl.

n is preferably 3, 4 or 5.

Particularly advantageous groups of active compounds of formula I are those in which the benzene ring is substituted with at least the 2-, 4- and 6-positions of the methyl groups.

Compounds of formula I are preferred al-2I

190 Compounds of general formula XXIV form a group of S192

- in the formula

R ¹ is hydrogen, C 2 -C 6 alkanoyl, or benzoyl optionally substituted with one or two nitro groups, or an alkali metal or transition metal cation;

- R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, C 2 -C 6 haloalkenyl, or optionally substituted with four or two halogen atoms in the benzene ring benzyl;

- R ³ is C 1-6 alkyl and

- n is 0, 1 or 2.

Another preferred subgroup of compounds of formula I are compounds of formula XXI

- in the formula

- R * is hydrogen, C 2 -C 6 alkanoyl, or sodium or potassium;

- R ² is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl, C 1 -C 4 haloalkyl or C 2 -C 4 haloalkenyl, and

- R ³ is C 1-4 alkyl.

Another preferred subgroup of compounds of formula I are compounds of formula XXII

- in the formula

R ¹ is hydrogen, C 2 -C 6 alkanoyl, or sodium or potassium;

- ^R2 is C1-4 alkyl, C2-4 ⁵ alkenyl, C3-4 alkynyl, C1-4 haloalkyl or C2-4 haloalkenyl group and

- R ³ is C 1-4 alkyl.

¹⁰ by further preferred sub-group of compounds of formula (I) are the compounds of formula (XXIII)

- in the formula

R ¹ is hydrogen, C 2 -C 6 alkanoyl, or sodium or potassium;

¹⁵ - ^R2 is C1-4 alkyl, C2-4 alkenyl, C3-4 alkynyl, C1-4 haloalkyl or C2-4 haloalkenyl group and

- R ³ is C 1-4 alkyl.

²⁰ (S) compounds are highly preferred sub-group of compounds of formula (XXV)

- in the formula

- R ² is ethyl, allyl, propargyl or 3-chloro-2-allyl group and

- R ³ is methyl, ethyl or propyl.

Preferred representatives of the compounds of formula I are listed in Table I (physical constants of the compounds are described below).

Table I

Serial number of compound (CH ₃ ) " R ¹ R ² R ³ 1 2,3- (CH ₃ ) ₂ H c ₂ h _s C ₂ H ₅ 2 2,4- (CH ₃ ) ₂ H c ₂ h ₅ c ₂ h ₅ 3 2.5- (CH ₃ ) ₂ H c ₂ h ₅ C ₂ H _s 4 2.6- (CH ₃ ) ₂ H c ₂ h ₅ C ₂ H ₅ 5 3,4- (CH ₃ ) ₂ H c ₂ h ₅ c ₂ h ₅ 6 3,5- (CH ₃ ) ₂ H c ₂ h ₅ C ₂ H _s 7 2,4,6- (CH ₃ ) ₃ H C ₂ H ₅ c ₂ h ₅ 8 2,4,5- (CH ₃ ) ₃ H c ₂ h ₅ c ₂ h ₅ 9 2,3,5,6- (CH ₃ ) ₄ H C ₂ H ₅ c ₂ h ₅ 10 2,3,4,6- (CH ₃ ) ₄ H c ₂ h ₅ C ₂ H _s 11 3,4- (CH ₃ ) ₂ COC ₆ Hj C ₂ H _s c ₂ h ₅ 12 3,4- (CH ₃ ) ₂ COCH ₃ C ₂ H _s c ₂ h ₅ 13 2.5- (CH ₃ ) ₃ COC _e Hj C ₂ H _s C ₂ H _s 14 2,3- (CH ₃ ) ₂ COC ₆ H ₃ c ₂ h ₅ c ₂ h ₅ 15 2,4,6— (CH ₃ ) ₃ coc ₆ h ₃ C ₂ H ₅ C ₂ H _s 16 2,4,6— (CH ₃ ) ₃ H ch ₂ ch = ch ₂ n-C ₃ H ₇ 17 2,4,6— (CH ₃ ) ₃ H ch ₂ ch = ch ₂ c ₂ h ₅ 18 2,4,6— (CH ₃ ) ₃ H C ₂ H _s n C ₃ H ₇ 19 2,4,6— (CH ₃ ) ₃ H C ₂ H _s ch ₃ 20 2,4,6— (CH ₃ ) ₃ H n-C ₃ H ₇ c ₂ h ₅ 21 2,4,6— (CH ₃ ) ₃ H n-C ₄ H ₉ C ₂ H _s 22 2,4,6— (CH ₃ ) ₃ H the c ₂ h ₅ 23 2,4,6— (CH ₃ ) ₃ H b C ₂ H _s 24 2,4,6— (CH ₃ ) ₃ H ch ₂ = ch C ₂ H ₅ 25 2,4,6— (CH ₃ ) ₃ H ch ₂ ch ₂ f c ₂ h ₅ 26 2,4,6— (CH ₃ ) ₃ H CH ₂ C (C 1) = CH ₂ c ₂ h ₅ 27 2,4,6— (CH ₃ ) ₃ H ch ₂ c ₆ h ₅ C ₂ H _s 28 2,4,6— (CH ₃ ) ₃ H c c ₂ h ₅ 29 2,4,6— (CH ₃ ) ₃ H d c ₂ h ₅

190,819

Table I (continued)

Serial number of compound (CH ₃ ) " R ¹ R ² R ³ 30 2,4,6— (CH ₃ ) ₃ H e c ₂ h, 31 2,4,6— (CH ₃ ) ₃ H f c ₂ h, 32 2,4,6— (CH ₃ ) ₃ H g c ₂ h, 33 2,4,6— (CH ₃ ) ₃ H h c ₂ h, 34 2,4,6— (CH ₃ ) ₃ H i c ₂ h, 35 2,4,6— (CH ₃ ) j H n-C ₄ H ₉ n — C ₃ H. 36 2,4,6— (CH ₃ ) ₃ H the n — C ₃ H. 37 2,4,6— (CH ₃ ) ₃ H b n — C ₃ H. 38 2,4,6— (CH ₃ ) ₃ H ch ₂ c = ch n — C ₃ H. 39 2,4,6— (CH ₃ ) ₃ H ch ₂ ch ₂ f n — C ₃ H. 40 2,4,6— (CH ₃ ) ₃ H CH ₂ C (C 1) = CH ₂ n — C ₃ H. 41 2,4,6— (CH ₃ ) ₃ H c n — C ₃ H. 42 2,4,6— (CH ₃ ) ₃ H d n-C ₃ H- 43 2,4,6— (CH ₃ ) ₃ Na ⁺ c ₂ H, c ₂ h, 44 2,4,6— (CH ₃ ) ₃ j c ₂ h, c ₂ h, 45 2,4,6— (CH ₃ ) ₃ k c ₂ h, c ₂ h, 46 2,4,6— (CH ₃ ) ₃ 1 c ₂ h, c ₂ h, 47 2,4,6— (CH ₃ ) ₃ Na ⁺ ch ₂ ch = ch ₂ c ₂ h ₅ 48 2,4,6— (CH ₃ ) ₃ COC ₆ H, ch ₂ ch = ch ₂ c ₂ h, 49 2,4,6— (CH ₃ ) ₃ coc ₆ h, ch ₂ c = ch c ₂ h, 50 2,4,6— (CH ₃ ) ₃ coc „h ₅ c ₂ h, n-C ₃ H- 51 2,4,6— (CH ₃ ) ₃ coc ₆ h, ch ₂ ch = ch ₂ n-CJH. 52 2,3,4- (CH ₃ ) ₃ Η c ₂ h, c ₂ h, 53 2,3,5- (CH ₃ ) ₃ H c ₂ h, c ₂ h, 54 3,4,5- (CH ₃ ) H ₃ H c ₂ h, c ₂ h, 55 2,3,4,6- (CH ₃ ) ₄ H CJH, n-C ₃ H- 56 2,3,4,6- (CH ₃ ) ₄ H ch ₂ ch = ch ₂ c ₂ h, 57 2,3,4,6- (CH ₃ ) ₄ H ch ₂ ch = ch ₂ n-CJH. 58 2,3,4,6- (CH ₃ ) ₄ coc ₆ h, c ₂ h, c ₂ h, 59 2,3,4,5- (CH ₃ ) ₄ Na ⁺ CJH, c ₂ h, 60 2,3,4,5,6- (CH ₃ ) _s H c ₂ h, c ₂ h, 61 2,3,4,5,6- (CH ₃ ) ₅ H ch ₂ ch = ch ₂ c ₂ h, 62 2,3,4,5,6- (CH ₃ ) _s H c ₂ h, nC ₃ H. 63 2,3,4,5,6- (CH ₃ ) j H ch ₂ ch = ch ₂ n-CJH. 64 2,3,4,5- (CH ₃ ) ₄ H c ₂ h, c ₂ h, 65 3,4- (CH ₃ ) ₂ H n-C ₃ H ₇ c ₂ h ₅ 66 3,4- (CH ₃ ) ₂ H ch ₂ ch = ch ₂ c ₂ h ₅ 67 3,4- (CH ₃ ) ₂ H c ₂ h, n — C ₃ H. 68 3,4- (CH ₃ ) ₂ H n-C ₃ H ₇ nC ₃ H. 69 3,4- (CH ₃ ) ₂ H ch ₂ ch = ch ₂ n-CJH. 70 2,3,4,5,6- (CHJ, H C ₂ H, CH ₃ 71 2,3,6- (CH ₃ ) ₃ H c ₂ h, c ₂ h ₅ 72 2,3,4,5,6- (CH ₃ ), Na ⁺ c ₂ h, n-CJH. 73 2,3,4,5,6- (CH ₃ ), coc ₆ h. c ₂ h, n-CJH. 74 2,3,4,6- (CH 3) ₄ H ch ₂ ch ₂ f n-CJH. 75 2,3,4,5,6- (CH); H ch ₂ ch ₂ f n-CJH. 76 2,3,4,5,6- (CH); H ch ₂ ch ₂ f c ₂ h, 77 2,3,4,5,6- (CH ₃ ), H CH? n-CJH. 78 2,3,4,5,6- (CH ₃ ), Na ⁺ c ₂ h, c ₂ h, 79 2,3,4,5,6- (CH ₃ ), H n-C ₃ H ₇ CJH-n. 80 2,3,4,5,6- (CH ₃ ), H CH? c ₂ h, 81 2,3,4,5,6- (CH ₃ ), COC _for H, c ₂ h ₅ c ₂ h, 82 2,3,4,5,6- (CH ₃ ), H CH ₂ C (C 1) = CH ₂ n-CJH 83 2,3,4,5,6- (CH ₃ ), H the c ₂ h, 84 2,3,4,5,6- (CH,), l / 2Cu ²⁺ C ₂ H, n-CJH. 85 2,3,4,5,6- (CH ₃ ), 1/2 Ni ²⁺ C ₂ H, n-CJH 86 2,3,4,5,6- (CH ₃ ), H ch ₂ sch ₃ c ₂ h, 87 2.5- (CH ₃ ) ₂ H c ₂ h, c ₆ h, 88 2,4,6- (CH ₃ ) ₃ ⁺ N (n-C ₄ H ₉ ) ₄ c ₂ h, c ₂ h, 89 2,4,6- (CH ₃ ) ₃ m c ₂ h, c ₂ h, 90 2,4,6- (CH ₃ ) j n c ₂ h, c ₂ h,

190,819

Table I (continued)

Serial number of compound (CH ₃ ) " R ¹ R ² R ³ 91 2,4,6- (CH ₃ ) ₃ She C ₂ H ₅ c ₂ h ₅ 92 2,4,6- (CH ₃ ) ₃ P c ₂ h ₅ c ₂ h ₅ 93 2,4,6— (CH ₃ ) ₃ CH ₃ CO c ₂ h ₅ c ₂ h ₅ 94 2,4,6— (CH ₃ ) ₃ q c ₂ h ₅ c ₂ h ₅ 95 2,4,6- (CH ₃ ) ₃ r c ₂ h _s c ₂ h ₅

Footnotes to Table I

a) - trans. - CH ₂ CH = CHCH ₃

b) - trans. - CH ₂ CH ₂ CH = CH ₂ (c) - trans. - 4-Cl-CH ₂ C ₆ H ₄

d) - trans. - 4 — Br — CH ₂ C ₆ H ₄

e) - trans. - 4 — F — CH ₂ C ₆ H ₄

f) - trans. - 4-CH ₃ -CH ₂ C ₆ H ₄

g) - trans. - 4-NO ₂ -CH ₂ C ₆ H ₄

h) - trans. - 3-Cl-CH ₂ C ₆ H ₄

i) - trans. - 2,4-Cl ₂ -CH ₂ C ₆ H ₃

j) - trans. - 4-NO ₂ -COC _e H ₄

k) - trans. - 3-NO ₂ -COC ₆ H ₄

l) - trans. - 3,5- (NO ₂ ) ₂ -COC ₆ H ₃

m) - trans. - 4-CH ₃ -COC ₆ H ₄

n) - trans. - 2,4,6- (CH ₃ ) ₃ -COC ₆ H ₂

o) - trans. - 4-CH ₃ 0 -C 0 C ₆ H ₄

p) - trans. - 4-Cl-COC ₆ H ₄

q) - trans. - COC (CH ₃ ) ₃

r) - trans. - CH ₂ COOCH ₂ CH ₃

The present invention also provides a process for the preparation of compounds of formula (I)

- in the formula

- R 1 is hydrogen, C 2 -C 6 alkanoyl or optionally substituted with one to three halogen, nitro, methyl and / or methoxy substituents, an alkali metal cation, a transition metal cation or an ammonium ion of formula (R ⁴ ) ₄ N ⁺ , wherein R ^{4 is C 4} alkyl;

"R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, C 2 -C 6 haloalkenyl, or optionally one or two halo in the benzene ring. a benzyl group having a methyl and / or nitro substituent;

- R ³ is C 1-6 alkyl and

n is 2, 3, 4 or 5 such that

a), the benzaldehyde derivative of the formula V is reacted with acetone, the resulting ketone derivative of the formula VI is reacted with the malonic acid ester derivative of the formula VII, resulting in 5- (substituted phenyl) cyclohexane-1 Reacting the 3-dione derivative with an acid anhydride (XIV) or an acid halide (XV) to give the 2-acyl-5- (substituted phenyl) cyclohexane-1,3-dione derivative (XVII) with an alkoxyamine derivative of the Formula (II) and reacting the compound (II) thus obtained, which is a narrower group of the compounds (I), with the compound (XX), or

5- formula a) ₂ (IX), (substituted phenyl) is reacted with cyclohexane-l, 3-dione derivative (XIV) with an acid anhydride or (XV) with an acid halide represented by the formula to yield (XIII) offers two acyl _five general formula -5- (substituted phenyl) -cyclohexane-1,3-dione is reacted with an alkoxyamine derivative (XVII) and the resulting compound (XX) is a narrower compound of formula (I). iq. or by reacting a) ₃ (XIII), 2-acyl-5- (substituted phenyl) cyclohexane-l, 3-dione derivative (XVII) alkoxyamine derivative of formula of formula and the resulting compounds of general formula (I) ₅ formulas formula ⁰ subclass from the group of (II), (XX) with a compound of formula; obsession

a) _{4 is} reacted with a compound of formula (XX) _iQ, which is a narrower compound of formula (I)

- in the above formulas, R ¹ , R ² , R ³ and n are as defined above; R is C 1-6 alkyl; Hal is an atom and L is a leaving group, preferably halogen.

The preparation procedures are illustrated in Reaction Schemes A, B, C and D. The process consists of three or four steps.

Reaction A demonstrates the preparation of 5 (substituted phenyl) cyclohexane-1,3-dions of formula IX. The reaction is preferably carried out in two steps. The benzaldehyde derivative (V) is condensed with acetone, and the resulting ketone (VI) is condensed with the malonic acid ester (VII), with or without isolation of intermediate VIII (IX). 5- (substituted phenyl) cyclohexane-1,3-dione.

Alternatively, the thienaldehyde derivative (V) can be condensed with the malonic acid ester derivative (VII) and then the benzylidene malonate derivative (X) condensed with the acetic acetic acid derivative (XI). Isolation of the intermediate of formula (IX) with or without isolation affords the 5- (unsaturated phenyl) -cyclohexane-1,3-dione of formula (IX).

Alternatively, the cinnamic acid ester derivative (XXI) can be condensed with the acetic acetic acid derivative (XI) and, after isolation of the intermediate (VIII), the 5-substituted (IX) phenyl) cyclohexane-1,3-dione derivative.

In Scheme B, 2-acyl-5-51 compounds of formula IX

Acylation of 190 819 (substituted phenyl) -cyclohexane-1,3-dions is noted. The reaction may be carried out by reacting 5- (substituted phenyl) cyclohexane-1,3-dione of formula IX with one of the following acylating agents:

IV: A mixture of the acid anhydride of formula (XIV) with the corresponding acid salt or alkoxide of the acid, wherein M is an alkali metal and R is a C 1-6 alkyl group;

V. a mixture of an acid anhydride of formula XIV and the corresponding acid;

VI. An acid halide of formula XV;

VII. A mixture of an acid halide of formula (XV) and the corresponding acid;

VIII. an alkali metal or alkaline earth metal hydride, followed by an acid anhydride of formula XIV or an acid halide of formula XV.

The above reaction can be repeated as follows.

IX. Reacting 5- (substituted phenyl) cyclohexane-1,3-dione (IX) with an acid halide (XV) in the presence of pyridine to give the O-acyl intermediate (XVI); then

X. reacting the intermediate of formula XVI with a Lewis acid catalyst;

XI. reacting the intermediate of formula XVI with an acid corresponding to the acid halide of formula XV; obsession

XII. Intermediate (XVI) is reacted with imidazole.

In the formulas of Scheme B, "fish" means halogen.

Scheme C illustrates the preparation of compounds of formula I wherein R ¹ is hydrogen, i.e. compounds of formula II. The reaction is repeated as follows *

XIII. The compound (XIII) is converted to the compound (II) by the alkoxyamine derivative (XVII).

XIV. The compound (XIII) is reacted with hydroxylamine and the resulting oxime intermediate (XVIII) is converted to the compound (II) with an alkylating agent (XIX).

In Scheme C, L is a suitable leaving group, e.g. chloride, bromide, iodide, sulfate, nitrate, methyl sulfate, ethyl sulfate, tetrafluoroborate, hexafluorophosphate, hexafluorodimonate, methanesulfonate, fluorosulfonate, fluoromethane, sulfonate or trifluoromethanesulfonate.

R 'compounds of formula (I) wherein the acyl group from a compound of formula (I), R ¹ is hydrogen

i.e., the compounds of formula II are prepared by acylation. The reaction is illustrated in Scheme D.

R represents ^one inorganic or organic compound containing the cation of formula (I) can be prepared by reacting the corresponding compound of formula (I), ^R1 is a hydrogen atom - i.e., (II) a compound of formula

reacting with an inorganic or organic base or salt. so e.g. the compounds of formula I wherein R ¹ is an alkali metal ion may be prepared by reaction of the corresponding compound of formula II with an alkali metal hydroxide or alcoholate. Compounds of formula where ^R1 is a transitional metal ion or an organic cation (I) may be prepared from the corresponding compound (II) and the transition metal salt or organic base of the formula reacting similarly.

R Compounds of general formula (I) containing a transition metal ion or an organic cation and the corresponding alkali metal ion containing R ¹ of formula (I) and a compound of formula megfele- prepared as * ¹ Shoot transition metal salt or organic salt by reaction.

According to the process of the present invention

a) The benzaldehyde derivative of formula V is reacted with acetone and the resulting ketone derivative of formula VI is reacted with a malonic acid ester derivative of formula VII wherein R is C 1-6 alkyl - 5- (substituted) of formula IX converting phenyl) -cyclohexane-1,3 dione; or _; The benzaldehyde derivative (V) is reacted with the malonic acid ester derivative (VII) and the resulting benzylidene malonate derivative (X) is reacted with an acetic acetic acid ester (XI) wherein R is a C 1-6 alkyl group - ( Converting the 5- (substituted phenyl) cyclohexane-1,3-dione derivative of formula IX; or a cinnamic acid ester derivative of the Formula XXI wherein R is a C 1-6 alkyl group with an ester of an acetic acid of the Formula XI wherein R is a C 1-6 alkyl group of the 5- (substituted phenyl) Formula IX. ) -cyclohexane-1,3-dione;

b) the resulting 5- (substituted phenyl) -cyclohexane-1,3-dione derivative of the Formula IX is reacted with an acid anhydride of the Formula XIV or an acid halide of the Formula XV with the 2-acyl-5- compound of the Formula XIII; acylating to the (substituted phenyl) cyclohexane-1,3 dione;

c) converting a 2-acyl-5- (substituted phenyl) -cyclohexane-1,3-dione derivative of formula (XIII) with an alkoxyamine derivative (XVII) to a compound of formula (II); or reacting the 2-acyl-5- (substituted phenyl) cyclohexane-1,3-dione derivative of formula (XIII) with hydroxylamine, and the resulting oxime intermediate (XVIII) with a compound of formula (XIX): wherein L is a suitable leaving group - is converted to a compound of formula II; and then, if desired, rf) converting a compound of Formula II into a compound of Formula I with a compound of Formula XX, wherein L is a suitable leaving group, or an inorganic or organic base or salt.

Certain intermediates of formulas (VI), (VIII), (IX), (X), (XII), (XXI), (XIII), (XVI), and (XVIII) are novel compounds.

The herbicides containing the compounds of the formula I have a herbicidal action against monocotyledonous weeds and wild grasses, and in particular on cultivated plants.

They are selective against hard-to-control wild grasses breeding among 190 819 plants. The herbicidal agents of the present invention are particularly useful for controlling wild grasses (e.g., wild oats or grasses) growing on monocotyledonous crops (e.g., wheat, barley or other cereals).

The herbicides according to the present invention can be used to control monocotyledonous weeds (especially wild grasses, such as wheat or barley) grown in crop crops, such that the crop or crop is cultivated. A herbicidal composition comprising a compound of formula (I) is administered to the plant in an amount that will severely damage or destroy the weed, but will not significantly damage the crop.

Certain cyclohexane-1,3-dione derivatives, as mentioned above, have general herbicidal activity against weeds, but do not show useful selectivity in cereals (Australian Patent Application No. 464,655, Australian Patent Application No. 35,314/78, and numerous appropriate patent or patent application). It is also known from Iwataki and Hirono (Advaces in Pesticides Science - Part 2, pp. 235-243, Pergamon Press 1979) that certain selective herbicides can be obtained by introducing a phenyl group substituted at the 5-position of the cyclohexane-1,3-dione into cereals. a. However, according to the authors, "Selectivity was observed only for derivatives substituted at the p-position of the benzene ring, and no selectivity was observed for double or triple substituted benzene derivatives." In view of the above, it is completely unexpected and surprising to find that herbicidal compositions containing cyclohexane-1,3-dione derivatives containing two to five methyl ring-substituted phenyl rings are sensitive to monocotyledonous weeds (e.g. wheat or barley). wild oats or meadow grass) have a selective herbicidal action. It is particularly surprising that herbicides containing cyclohexane-1,3-dione derivatives having at least 2-, 4- and 6-positions of the benzene ring in the 5-position of the benzene ring are already very low against monocotyledonous weeds (e.g. they have a strong effect, but at the same time very sensitive monocot crops (especially wheat) are not damaged.

The herbicidal agents of the present invention may be applied to the plants (post-emergent application) or to the soil (pre-emergent application) before emergence of the plants. In general, post-emergent application has proven to be advantageous.

The present invention also provides a herbicidal composition comprising an effective amount of one or more compounds of formula I and inert carriers. The herbicidal compositions of the present invention have a plant growth inhibitory, plant-damaging or herbicidal activity.

The herbicidal compositions of the present invention may be solid, liquid or paste-like. The active ingredient may be formulated as ready-to-use diluted formulations or as concentrates to be diluted prior to use. Accordingly, the active ingredient content of the herbicidal compositions of the present invention will vary depending on the type of formulation, so that a ready-to-use agent (e.g., powder mix or aqueous emulsion) or concentrate (e.g., emulsifiable concentrate to be diluted or wettable powder) is prepared. The herbicidal compositions of the present invention contain from 0.002% to 95% by weight of the active ingredient. For example, solid compositions may be used. They may be in the form of powder mixtures, granules, granules and contain, in addition to the active ingredient, a solid carrier. Powder blends are prepared by mixing or milling the active ingredient with a solid carrier to form a finely divided mixture. The granules and granules are prepared by bonding the active ingredient to a solid carrier (e.g., pre-formed particulate solid carrier being coated or impregnated with the active ingredient or by agglomeration techniques).

As a solid support, e.g. the following may be used: minerals, e.g. kaolin, bentonite, kieselguhr, fuller earth, attapulgite, diatomaceous earth, talc, chalk, dolomite, limestone, lime, calcium carbonate, powdered magnesium oxide, magnesium sulfate, gypsum, calcium sulfate, pyrophyllite, silica, silicates and silica; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate and urea; natural substances of plant origin, e.g. cereal and seed meal, wood flour, walnut flour and powdered cellulose; and synthetic polymeric materials, e.g. ground and powdered plastics and resins, etc.

The solid compositions may also be in the form of dispersible and wettable powders, granules and granules; these compositions also contain, in addition to the active ingredient and the solid carrier, one or more surfactants which act as wetting, emulsifying and / or dispersing agents to facilitate dispersion of the active ingredient in the liquid.

The surfactants that can be used are of the cationic, anionic and nonionic types. Among the cationic surfactants, e.g. quaternary ammonium salts (such as long-chain alkyl ammonium salts such as acetyltrimethylammonium bromide) are mentioned. As anionic surfactant, e.g. soaps; alkali metal, alkaline earth metal ammonium salts of fatty acids; alkali metal, alkaline earth metal and ammonium salts of lignin sulfonic acid; alkali metal, alkaline earth metal and ammonium salts of arylsulphonic acids (including salts of naphthalenesulphonic acids such as di- and triisopropylnaphthalenesulphonic acids and butylnaphthalenesulphonic acids; salts of the condensation products of naphthalene derivatives with phenol and formaldehyde; alkali metal alkali metal monoesters of sulfuric acid or long-chain monoesters of sulfuric acid or alkyl sulfates such as lauryl sulfate; and ammonium salts thereof, and monoesters of sulfuric acid with fatty alcohol glycol ethers, etc.). As a nonionic surfactant eti7

Condensation products of -7 lene oxide with fatty alcohols (e.g. oleyl alcohol or cetyl alcohol); condensation products of ethylene oxide with phenols and alkyl phenols (e.g., isooctylphenol, octylphenol or nonylphenyl, etc.); condensation products of ethylene oxide with castor oil; partial esters derived from long-chain fatty acids and hexite anhydrides (e.g., sorbitol monolaurate; condensation products of the above partial esters with ethylene oxide); ethylene oxide / propylene oxide block copolymers; lauryl alcohol polyglycol ether acetals and lecithin derivatives may be used.

Liquid formulations are solutions or dispersions of the active ingredient in a liquid carrier optionally containing one or more surfactants as wetting, emulsifying and / or dispersing agents. As a liquid carrier, e.g. the following liquids may be used: water; mineral oil fractions (eg kerosene, white spirit, kerosene, coal tar oils and aromatic petroleum fractions); aliphatic, cycloaliphatic and aromatic hydrocarbons (e.g., paraffin, cyclohexane, toluene, xylenes, tetrahydronaphthalene and alkylated naphthalenes); alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol and propylene glycol); ketones (e.g. cyclohexanone and isophorone); highly polar organic solvents (e.g. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and sulfolane, etc.).

Suitable liquid formulations are aqueous suspensions, dispersions or emulsions of the active ingredient in surfactant; these formulations may be applied to the plants by spraying, spraying or irrigation. The above aqueous formulations are generally prepared by diluting the concentrated formulations with water. Concentrated compositions are preferably emulsifiable concentrates, pastes, oily dispersions, aqueous suspensions or wettable powders. Concentrates are required to be stored for extended periods of time and, after storage, dilute with water to provide homogeneous aqueous preparations for a sufficient period of time to be used in conventional spraying equipment. The concentrates will generally contain from 20 to 95% by weight, preferably from 20 to 60% by weight.

Emulsions or emulsifiable concentrates may be prepared by dissolving the active ingredient in an organic solvent containing one or more surfactants. Pasty formulations may be prepared by admixing the finely divided active ingredient with a finely divided solid carrier, one or more surfactants and optionally an oil. Oily dispersions are prepared by grinding the active ingredient, hydrocarbon oil and one or more surfactants. Aqueous suspension concentrates may be prepared by milling the active ingredient in a ball mill in the presence of water, preferably at least one suspending agent. Preferred suspending agents are hydrophilic colloids [e.g. poly (N-vinylpyrrolidone), sodium8

190,819 a

carboxymethylcellulose and vegetable gums, e.g. acacia, tragacanth]; hydrated colloidal mineral silicates (e.g. montmorrilonite, beidellite, nontronite, hectorite, saponite, sagonite and bentonite); other cellulose derivatives; or polyvinyl alcohol. Wettable powder concentrates may be prepared by mixing the active ingredient, one or more surfactants, one or more solid carriers, and optionally one or more suspending agents, and milling the resulting mixture to produce a powder of the desired particle size.

Aqueous suspensions, dispersions or emulsions of the concentrated compositions may be prepared by diluting the surfactant, optionally with water and / or oil.

It is noted that the compounds of formula (I) wherein R ¹ is hydrogen are acidic and may also be used in the form of salts with organic or inorganic bases as active ingredients in the herbicides according to the invention.

The compounds of formula (I) wherein R ¹ is hydrogen may also be used in the form of their salts with inorganic or organic bases. However, the salt may be prepared by in situ reaction of the appropriate compound of formula (I) wherein R 'is hydrogen with the appropriate organic or inorganic base.

The method of application of the herbicides according to the present invention depends to a large extent on the type of formulation and the devices and equipment available. The solid compositions may be applied by spraying, dusting or any other conventional means to the plant or area to be protected. Liquid formulations may be applied by spraying, spraying, irrigation or any other suitable conventional method.

The amount of herbicide applied to the vegetation to be protected depends on several factors - e.g. the activity of the active ingredient; the weeds to be killed; the type of preparation; and whether the active ingredient is taken up by the plant through the foliage or the root. As a general rule, the herbicides according to the invention may be applied in an amount of 0.005 to 20 kg of active ingredient per hectare, preferably 0.01 to 5.0 kg / ha.

One or more additional biologically active compounds may be added to the herbicides of the present invention. The herbicides of the present invention, as mentioned above, are generally more effective against monocotyledonous plants or grasses than against dicotyledonous plants or broadleaf weeds. Thus, in some applications, herbicides containing only the compound of formula (I) as active ingredient do not completely protect the crop. Accordingly, one or more other herbicides may optionally be added to the herbicides of the present invention.

The additional herbicidal agent optionally added, i.e. an agent having a structure other than formula I, has an additive effect.

Other herbicidal components have been found to be herbicidal active agents against broadleaf weeds. In addition, contact herbicides are advantageously used as auxiliary herbicidal agent.

The herbicidal compositions of the present invention may be formulated with the following additional herbicidal active ingredients:

Benzo-2,1,3-thiadiazin-4-one-2,2-dioxide derivatives, e.g. 3-Isopropyl-benzo-2,1,3-thiadiazin-4-one 2,2-dioxide (common name: bentazone).

B) Hormonal herbicides, in particular phenoxyalkane carboxylic acid derivatives, e.g. 4-chloro-2-methylphenoxy-acetic acid (common name MCPA), 2- (2,4-dichlorophenoxy) -propionic acid (common name dichlorprop), 2,4,5-trichlorophenoxy-acetic acid (common name:

2,4,5-T), 4- (4-chloro-2-methylphenoxy) -butyric acid (common name: MCPB), 2,4-dichlorophenoxy-acetic acid (common name: 2,4-D) , 4- (2,4-dichlorophenoxy) -butyric acid (common name: 2,4-DB), 2- (4-chloro-2-methylphenoxy) -propionic acid (common name: mecoprop) and their derivatives (e.g. salts, esters, amides, etc.).

C) 3- [4- (4-halophenoxy) phenyl] -1,1-dialkylurea derivatives, e.g. 3- [4- (4-chlorophenoxy) phenyl] -1,1-dimethylurea (common name: chloroxuron).

D) Dinitrophenols and their derivatives (e.g., acetates), e.g. 2-methyl-4,6-dinitrophenol (common name: DNOC), 2-tert-butyl-4,6-dinitrophenol (common name: dinoterb), 2-secondary butyl-4,6-dinitrophenol (free name) : dinoseb) and its ester (dinosebacetate).

E) Dinitroaniline herbicides, e.g. N ', N'-diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylene diamine (common name: dinitramine), 2,6-dinitro-N, N-dipro-pis-4-trifluoromethylaniline (common name: trifluoralin), and 4-methylsulfonyl-2,6-dinitro-N, N-dipropylaniline (common name: nitralin).

E) Phenyl urea type herbicides, e.g. N '(3,4-dichlorophenyl) -N, N-dimethylurea (common name: diuron) and N, N-dimethyl-N' - [3- (trifluoromethyl) phenyl] urea (common name: fluometuron).

G) Phenylcarbamoyloxyphenylcarbamates, e.g. 3 - [(methoxycarbonyl) amino] phenyl (3-methylphenyl) carbamate (common name phenmedipham) and 3 - [(ethoxycarbonyl) amino] phenyl phenyl carbamate (common name desmedipham).

H) 2-phenylpyridazin-3-one derivatives, e.g. 5 amino-4-chloro-2-phenylpyridazin-3-one (common name: pyrazone).

I) Uracil-type herbicides, e.g. 3-cyclohexyl-6,7-trimethyleneuracil (common name: lenacil), 5-bromo-3-secondary butyl-6-methyluracil (common name: bromacil) and 3-tert-butyl-5-chloro-6-methyluracil ( free name: terbacil).

J) Triazine-type herbicides, such as 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine (common name atrazine), 2-chloro-4,6-di- (ethyl- amino) -1,3,5-triazine (common name: simazine) and 2-azido-4-isopropylamino-6-methylthio-1,3,5-triazine (common name aziproptryne).

K) 1-alkoxy-2-alkyl-3-phenylurea derivatives, e.g. 3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea (common name: linuron), 3- (4-chlorophenyl) -1methoxy-1-methylurea (common name: monolinuror), and 3- (4-Bromo-4-chloro-phenyl) -1-methoxy-1-medical-bamide (common name: chlorobromuron).

L) Thiol-carbamate type herbicides, e.g. Spropil dipropyl thiocarbamate (common name: verola ⁵ te)

Al) 1,2,4-triazin-5-one herbicides, e.g. 4 amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one (common name: methamitron) and 4-amino-6-tert-butyl-4,5-dihydro-3 methylthio-l, 3,4-triazin-5-one ⁽¹⁰ common name metribuzin).

N) Benzoic acid type herbicides, e.g. 2,3,6-trichlorobenzoic acid (common name: 2,3,6-TBA), 3,6-dichloro-2-methoxybenzoic acid (common name: dicamba) and 3-amino-2,5- dichlorobenzoic acid (common name:

¹⁵ cUoramben).

O) Aniline-type herbicides, e.g. N-butoxymethyl-chloro-2 ', 6'-diethyl acetanilide (common name butachlor), the corresponding N-methoxy compound (common name alachlor), the corresponding N-isopropyl compound (common name ²⁰ propachlor) and 3 ', 4'-dichloropropionanilide (common name: propanil).

P) Dihalobenzonitrile herbicides, e.g.

2,6-dichlorobenzonitrile (common name: dichlobenyl), 3,5-dibromo-4-hydroxybenzonitrile (common name:

bromoxynil) and 3,5-diiodo-4-hydroxybenzonitrile (common name: ioxynil).

Q) Halogenalkonecarboxylic acid herbicides, e.g. 2,2-dichloropropionic acid (common name: dalapon), t'chloroacetic acid (common name: TCA) and their salts.

³⁰ R) Diphenyl ether herbicides, e.g. 4-nitrophenyl-2-nitro-4-trifluoromethylphenyl ether (common name: fluorodiphen), methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (common name: biphenox), 2-nitro- 5- (2-Chloro-4-trifluoromethyl-phenoxy) -benzoic acid and 2-chloro-4-trifluoromethyl-phenyl-3-ethoxy-4-nitrophenyl ether.

5) N- (heteroarylaminocarbonyl) benzenesulfonamides, e.g. 2-Chloro-N - [(4-methoxy-6-methyl-1,3,5-triazin-2-yl) -aminocarbonyl] -benzenesulfonamide (Common name DPX 4189) and

T) Various herbicides, e.g. N, N-dimethyldiphenylacetamide (common name: diphenamid), N- (naphthyl) phthalamic acid (common name naptalam) and 3 amino-1,2,4-triazole.

U) In addition to the compound of formula I, the herbicides according to the invention are, for example, an additional herbicide. may contain one of the following contact herbicides: containing 1,1'-dimethyl-4,4'-bipyridylium ion (common name: paraquat) or 1,1 '-ethylene-2,2'-bipyridylium ion (common name diquat) herbi50 cidek.

V) Organic arsenic compound type herbicides, e.g. monosodium methane arsenate (common name: MSMA) and

IF / Amino acid type herbicides, e.g. N- (phospho-55-methyl) -glycine (common name: glyphosate), salts and esters.

The invention is further illustrated by the following examples, without limiting it.

The amounts given in the examples are by weight and by weight unless otherwise stated.

-9190819

Example 1

Preparation of 2-fl- (ethoxyimino) propyl) -3-hydroxy-5-mesitylcyclohex-2-en-1-one (7) (i) 29.5 ml of a 1% aqueous sodium hydroxide solution. dropwise over a minute, a suspension of 10.0 g (68 mmol) of mesityl aldehyde in 50 mL of acetone and 50 mL of water. The reaction mixture was stirred at 65 ° C for 1.5 hours and then extracted with dichloromethane (200 mL). The organic extract was washed several times with water, dried over anhydrous sodium sulfate and the solvent was distilled off under reduced pressure in a rotary evaporator. 1.5 g (90%) of 1- (2,4,6-trimethylphenyl) butl-en-3-one are obtained in the form of a viscous oil which solidifies on standing. The white solid melts at 64 ° C.

Proton resonance spectrum: (CDCl ₃ ; δ ppm):

2.25 (12H, m); 6.30 (1H, d); 6.88 (2 H, s); 7.64 (1H,

d).

(ii) 10.1 g (60 mmol) of diethyl malonate are added to a solution of 1.4 g (60 mmol) of sodium metal in 50 ml of anhydrous ethanol and the mixture is refluxed. A mixture of 11.4 g (61 mmol) of 1- (2,4,6-trimethylphenyl) butylene-3-one and 50 ml of anhydrous ethanol is then added over 2 minutes, and the reaction mixture is refluxed for 2 hours. boil. A solution of sodium hydroxide (7.3 g, 180 mmol) in water (100 mL) was added and the mixture was refluxed for a further 4.5 hours. The solution was poured into water (200 mL) and the aqueous mixture was extracted twice with ethyl acetate (100 mL). The aqueous phase is acidified with concentrated hydrochloric acid and gently heated until the evolution of carbon dioxide stops. The aqueous mixture was extracted with ethyl acetate, dried over anhydrous sodium sulfate and the solvent was removed in a rotary evaporator in vacuo. Yield: 10.9 g (77.4%) of 3-hydroxy-5-mesityl-cyclohex-2-en-1-one as a pale yellow solid, m.p. 165 ° C. Proton Resonance Spectrum: (D ₆ -dimethylsulfoxide; δ, ppm): 2.0-4.1 (14H, m);

5.2 (1H, s); 6.8 (2 H, s); 11.2 (1H, broad s).

(iii) 15.0 ml of propionic anhydride are added to 0.47 g (9 mmol) of freshly prepared sodium methylate. After completion of the reaction, 5.0 g (22 mmol) of 3-hydroxy-5-mesitylcyclohex-2-en-1-one are added and the reaction mixture is refluxed for 2 hours at 160 ° C. Excess propionic anhydride is removed in vacuo using a rotary evaporator. To the residue was added 50 ml of 30% aqueous sodium hydroxide solution and the mixture was heated under reflux for 1 hour with vigorous stirring. The mixture was cooled, acidified with concentrated hydrochloric acid and extracted with dichloromethane. The organic extracts were dried over anhydrous sodium sulfate and the solvent removed in vacuo on a rotary evaporator. The residual brown oil was chromatographed on silica gel eluting with dichloromethane. 3.17 g (50.2%) of 3-hydroxy-5-mesityl-2-propionylcyclohex-2-en-1-one are obtained in the form of a pale yellow oil. Proton Resonance Spectrum: (CDCl ₃ ; δ, ppm): 1.60 (3H, t, J = 8Hz); 2.24 (3H, s); 2.37 (6H, s); 2.64-5.26 (7H, m); 6.84 (2 H, m); 18.26 (1H, s).

(iv) To a solution of 3-hydroxy-5-mesityl-210 propionylcyclohex-2-en-1-one (1.2 g, 4.2 mmol) in anhydrous ethanol (200 mL), first 0.45 g of ethoxyamine hydrochloride, and 18.4 ml of a 1% sodium hydroxide solution are added. After stirring at room temperature for 4 hours, the ethanol was removed on a rotary evaporator under vacuum. The residue is treated with dichloromethane and the organic phase is washed twice with dilute aqueous hydrochloric acid and twice with water. The organic layer was dried over anhydrous sodium sulfate and the solvent removed in vacuo. There was obtained 1.25 g (93%) of 2- [1- (ethoxyimino) propyl] -3-hydroxy-5-mesityl-cyclohex-2-en-1-one as a pale yellow oil.

The product is identified by proton magnetic resonance and C-13 nuclear magnetic resonance spectra, and spectroscopic data are shown in FIG. (Example 21).

Example 2

1, 2, 3, 4, 5, 6, 8, 9, and 10. Compound II (Table I) is prepared in a manner analogous to that described in Example 1 (i) to (iv) starting from the corresponding benzaldehyde derivatives. Each product is identified by its proton resonance and / or C-13 nuclear magnetic resonance spectra and the spectroscopic results are shown in FIG. (Example 21).

Example 3

Preparation of 3- (benzoyloxy) -2- [N- (ethoxyimino) propyl] -5-mesitylcyclohex-2-en-1-one (15)

a) To a solution of 0.42 g (1.28 mmol) of 2- [1- (ethoxyimino) propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one in 50 ml of acetone was added 6 ml of 1% aqueous sodium hydroxide solution was added. The mixture was stirred at room temperature for 5 minutes and then benzoyl chloride (0.2 g) was added dropwise. The reaction mixture was stirred for an additional 15 minutes and then the solvent was removed in vacuo using a rotary evaporator. The residue was purified by chromatography on silica gel eluting with dichloromethane. 0.38 g (68.6%) of the title compound are obtained as a pale yellow oil.

b) To a solution of 0.89 g of 2- [1- (ethoxyimino) propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one and 9.5 ml of tetrahydrofuran, 0.12 g of sodium hydroxide and A solution of 7 ml of water is added dropwise. Then 0.42 g of benzoyl chloride was added dropwise with stirring and the reaction mixture was stirred for 30 minutes at room temperature. The solvent was removed in vacuo and the residue taken up in dichloromethane and water. The dichloromethane solution was separated, washed twice with water, dried and the solvent removed in vacuo. The residual oil was triturated with petroleum ether (b.p. 50-60 ° C). The resulting solid was recrystallized from isopropanol. 0.79 g of the title compound is obtained as a solid, m.p. 94-95.5'C.

c) 2.4 g of 2- [1- (ethoxyimino) propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one, 25 ml of anhydrous methyl 10

To a mixture of 190 819 2 ethyl ketone and 1.65 g of anhydrous potassium carbonate, 1.12 g of benzoyl chloride are added dropwise with stirring. The reaction mixture was stirred at reflux for 30 minutes and then filtered. The residue on the filter was washed with diethyl ether, the filtrates were combined with the washings and the solvent removed in vacuo. The residue was taken up in ethyl acetate, the solution was washed twice with water, dried and the solvent was distilled off in vacuo. The residual dark brown oil was purified by preparative thin layer chromatography (silica gel, eluent: 75:25 hexane: diethyl ether). 1.9 g of the title compound are obtained.

The product is identified by its proton resonance spectrum and the spectroscopic data are shown in Table IV. (Example 21).

Example 4

A 11, 12, 13, 14, 44, 45, 46, 48, 49, 50, 51,

58, 73, 81, 89, 90, 91, 92, 93, 94 and 95; compound 5, 5, 1, 7, 7, 7, 17, 24, 18, 16,

10, 62, 60, 7, 7, 7, 7, 7, 7 and 7; of the title compound was prepared in an analogous manner to one of the procedures described in Example 3 using the appropriate acid chloride (bromoacetic acid ethyl ester 95). All products are identified by their proton resonance spectra and the spectroscopic data obtained are shown in Table IV. (Example 21).

Example 5

Preparation of 2-N- (allyloxyimino) butyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one (16) (i) 5.0 g (21.7 mmol) of 3-hydroxy To a mixture of -5-mesitylcyclohex-2-en-1-one and 50 ml of dichloromethane was stirred under a nitrogen atmosphere, first 2.3 g (21.7 mmol) of n-butyryl chloride, followed by 1.7 g (21.7 mmol) millimoles) of pyridine. The reaction mixture was stirred at room temperature for 2 hours and then poured into slightly acidic water. The organic layer was separated and extracted well with dichloromethane. The combined organic phases and extracts were washed with water, dried over anhydrous magnesium sulfate and the solvent was removed on a rotary evaporator in vacuo. The residue is dissolved in 50 ml of 1,2-dichloroethane, 5.7 g (22 mmol) of tin (IV) chloride are added and the mixture is refluxed for 8 hours. The reaction mixture was cooled and poured into water. The aqueous mixture was extracted several times with dichloromethane. The combined organic extracts were dried over anhydrous magnesium sulfate and concentrated in vacuo on a rotary evaporator. The residue was purified by chromatography on silica gel eluting with dichloromethane. 2.4 g of 2-butyryl-3-hydroxy-5-mesityl-cyclohex-2-en-1-one are obtained.

Proton Resonance Spectrum: (CDCl ₃ : δ, ppm): 1.01 (3H, t); 1.30-1.60 (2 H, m); 2.23 (3H, s); 2.37 (6H, s); 2.40-3.45 (7 H, m); 6.83 (2 H, s); 18.24 (1H,

s).

(ii) To a mixture of 1.78 g (5.9 mmol) of 2-butyryl-3-hydroxy-5-mesitylcyclohex-2-en-1-one in 95% ethanol, 0.72 g of allyloxyamine hydrochloride was first stirred. followed by 0.25 g of sodium hydroxide

A solution of 3 ml of water was added. The progress of the reaction was monitored by TLC on silica gel (eluent: dichloromethane). After the reaction was removed using a rotary evaporator ^10, the ethanol in vacuo and the residue extracted with dichloromethane. The organic extract was washed with 5% aqueous hydrochloric acid, water, dried over anhydrous magnesium sulfate, and the solvent was removed in vacuo using a rotary evaporator. Oil ¹⁵ 1.6 g of 2- [l- (allyloxyimino) butyl] -3-hydroxy-5-mesyl-yl-cyclohex-2-en-l-one.

The product is identified by its proton resonance spectrum and the spectroscopic data are shown in Table IV. This is summarized in Table (Example 21).

Example 6

Preparation of 2- [1- (ethoxyimino) butyl] -3-hydroxy-5-mesityl-25 cyclohex-2-en-1-one (18)

Prepared from 2-butyryl-3-hydroxy-5mezitil-cyclohex-2-en-l-one [see Example 5 part (i)] and ethoxyamine hydrochloride there is obtained, in the first example ₃₀ part (iv) Prepared in an analogous manner to that described. The product is identified by its proton resonance spectrum and the spectroscopic data are shown in Table IV. (Example 21).

Example 7

Preparation of 2- [1- (allyloxyimino) propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one (17)

The title compound is 3-hydroxy-5-mesityl-2-propionyl-cyclohex-2-en-1-one [1. Example 1 (i) to (iii)] and allyloxyamine hydrochloride were prepared in a manner analogous to that described in Example 5 (ii). The product is identified by its proton resonance spectrum and the spectroscopic data are shown in Table IV. (Example 21).

Example 8

Preparation of 2- [1- (propoxyimino) propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one (20) (i) 13.0 g (0.056 mol) of 3-hydroxy-5-mesityl -cyclohex-2-en-1-one, 26 ml of propionic anhydride and 26 ml of propionic acid are stirred at 110 ° C until a homogeneous mixture is obtained. Trifluoromethanesulfonic acid (0.5 mL) was then added and the reaction mixture was refluxed at 110-120 ° C for 1 hour under a nitrogen atmosphere. The mixture was poured into ice water with stirring, then neutralized with sodium bicarbonate and extracted with diethyl ether. Brown oil obtained by evaporation of the ether extract by chromatography on silica gel eluting with dichloromethane 11

-111

190,819 scarves are cleaned. Yield: 12.5 g (77%) of 3-hydroxy-5-mesityl-2-propionyl-cyclohex-2-en-1-one as an almost colorless solid, m.p. 86-88 ° C.

(ii) 2-N- (Propoxyimino) propyl] -3-hydroxy-5-methylcyclohex-2-en-1-one (20) 3-hydroxy-5-mesityl-2-propionylcyclohex-2 by reaction of -en-1-one with propoxyamine hydrochloride in a manner analogous to that described in Example 1 (iv). The product is identified by its proton resonance spectra and the spectroscopic data are shown in Table IV. (Example 21).

Example 9

A 19, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30,

31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42,

52, 53, 54, 56, 57, 60, 61, 62, 63, 64, 65, 66,

67, 68, 69, 74, 75, 77, 79, and 82; by acylation of the corresponding 5-aryl-cyclohexane-1,3-dione derivative (Example 19) with a mixture of the corresponding carboxylic anhydride and carboxylic acid followed by reaction of the resulting acyl derivative with the corresponding hydroxylamine hydrochloride in a manner analogous to that described in Example 8. we produce it. All products are identified by their proton resonance spectra and their physical constants (melting point for solids and proton chemical shift for liquids) and the results are shown in Table IV. (Example 21).

Example 10

Preparation of 2- [1- (Ethoxyimino) -propyl] -3-hydroxy-5- (pentamethyl-phenyl) -cyclohex-2-en-1-one (60) (i) 0.65 g (0.027 mol) sodium hydride was added with stirring to a solution of 6.4 g (0.024 mol) of 3-hydroxy-5- (pentamethylphenyl) cyclohex-2-en-1-one and 100 ml of dimethylformamide at 60 ° C. After 15 minutes, propionic anhydride (3.3 g, 0.027 mol) was added and the reaction mixture was heated at 110-120 ° C for 3 hours, poured into water (300 mL) and extracted with diethyl ether (2 x 100 mL). The ethereal extracts were dried over anhydrous sodium sulfate and the solvent removed in vacuo on a rotary evaporator. The residual brown oil was purified by chromatography on silica gel (eluent: carbon tetrachloride / chloroform = 1: 1). 4.4 g (56%) of 3-hydroxy-5- (pentamethylphenyl) -2-propionylcyclohex-2-en-1-one are obtained in the form of an almost colorless solid.

(ii) 3-hydroxy-5- (pentamethylphenyl) -2-propionylcyclohex-2-en-1-one and ethoxyamine hydrochloride in accordance with Example 1; Example IV (iv). The resulting 2- [1- (ethoxyimino) -propyl] -3-hydroxy-5- (pentamethyl-phenyl) -cyclohex-2-en-1-one is identified by its proton resonance spectrum and the spectroscopic data are shown in Table IV. (Example 21).

II. example

Nos. 71, 76, 80, 83 and 86 Compound 5 is prepared by reaction of the corresponding arylcyclohexane-1,3-dione derivative (see Example 19) with the corresponding carboxylic anhydride followed by reaction of the resulting product with the corresponding hydroxylamine hydrochloride derivative in a manner analogous to that described in Example 10. live. All products are identified by their proton resonance spectra and spectroscopic data are shown in Table IV. (Example 21).

Example 12

Preparation of 2- [1- (ethoxyimino) ethyl] -3-hydroxy-5- (pentamethylphenyl) cyclohex-2-en-1-one (70) (i) 3.0 g of 3-hydroxy-5- ( pentamethylphenyl) -cyclohex2-en-1-one (see Example 19), 10 ml of acetic anhydride and 10 ml of acetic acid are heated to reflux with stirring until homogeneous. 0.5 g of p-toluenesulfonic acid are then added and the mixture is refluxed for a further 2 hours. After cooling, the reaction mixture was poured into water and extracted with ether. The ether extract was washed several times with water, dried over anhydrous magnesium sulfate and evaporated to dryness. The residual brown oil was purified by column chromatography (silica gel, eluent: dichloromethane). 1.50 g of 3-hydroxy-5-pentamethylphenyl-2-acetylcyclohex-2-en-1-one are obtained in the form of a crystalline solid.

(ii) 3-Hydroxy-5- (pentamethylphenyl) -2-acetylcyclohex2-en-1-one and ethoxyamine hydrochloride were reacted in a manner analogous to that described in Example 1 (iv). The resulting 2- [1- (ethoxyimino) ethyl] 3-hydroxy-5- (pentamethylphenyl) cyclohex-2-en-1-one (70) is identified by its proton resonance spectra and the spectroscopic data . (Example 21).

Example 13

Preparation of 2- [1- (ethoxyimino) benzyl] -3-hydroxy-5- (2,5-dimethylphenyl) cyclohex-2-en-1-one (87) (i) 0.53 g (0.022 mol) of sodium hydride (4.22 g, 0.020 mol; see Example 19) with 3-hydroxy-5- (2,5-dimethylphenyl) cyclohex-2-en-1-one and 60 ml of dimethyl formamide solution was added dropwise at 60 ° C. After 30 minutes, 5.0 g (0.022 mol) of benzoic anhydride was added. The reaction mixture was heated at 110-120 ° C for 4 hours, then poured into water (300 ml), acidified to pH 3 with hydrochloric acid and extracted with diethyl ether (2 x 100 ml). The ether extracts were washed with water, dried over anhydrous sodium sulfate and evaporated in vacuo. The residual crude product (brown oil) was dissolved in diethyl ether (200 mL), filtered, washed with sat. Aq. (II) acetate (300 mL) and evaporated to dryness in vacuo. The crude solid is collected in succession with hot water, cold water,

Wash with -121 diethyl ether and hexane and air dry. 6.0 g of 2-benzoyl-5- (2,5-dimethylphenyl) -3-hydroxycyclohex-2-en-1-one copper salt are obtained in the form of a pale green solid. Mp: 182-185 C.

The resulting copper salt was suspended in water, acidified with 3N hydrochloric acid and extracted with diethyl ether. The ether extract was washed with water, dried over anhydrous sodium sulfate and concentrated in vacuo. 2-Benzoyl-5- (2,5-dimethylphenyl) -3-hydroxycyclohex-2-en-1-one (4.20 g, 65%) is obtained as a pale yellow oil. Proton Resonance Spectrum (CDCl ₃ : δ, ppm): 2.33 (6H, s); 2.45-2.90 (4 H, m); 3.30-3.70 (1H, m); 6.90-7.15 (3H, bs); 7.30-7.80 (3 H, m); 8.00-8.30 (2 H, m).

(ii) 3-Hydroxy-5- (2,5-dimethylphenyl) -2-benzoylcyclohex-2-en-1-one and ethoxyamine hydrochloride in a manner analogous to that described in Example 1 (iv). with. The resulting 2- [1- (ethoxyimino) benzyl] -3-hydroxy-5- (2,5-dimethylphenyl) -2-cyclohex-2-en-1-one (87) is identified by its proton resonance spectrum and its spectrum (87). see Table IV, Example 21).

Example 14

Preparation of sodium salt of 2- [1- (ethoxyimino) -propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one (43)

A solution of 0.45 g sodium hydroxide in 2 ml water was added to a solution of 3.86 g of 2- [1- (ethoxyimino) propyl] -3-hydroxy-5-mesitylcyclohex-2-en-1-one in 50 ml acetone We are added. The solvent was removed in a rotary evaporator in vacuo. 3.98 g (99%) of the title compound are obtained as a yellow solid, m.p. 196 DEG C. (dec.).

Example 75

Nos 47 and 59; Compound (see Table I) is prepared by reacting the corresponding 2- [1- (alkoxyimino) -propyl] -3-hydroxy-5- (substituted phenyl) cyclohex-2-en-1-one. In a manner analogous to that described in Example 1b, it is reacted with sodium hydroxide. The products were identified by their melting point (Table IV, Example 21).

Example 16

Preparation of 2- [1- (ethoxyimino) butyl] -3-hydroxy-5- (pentamethylphenyl) cyclohex-2-en-1-one copper salt (84)

A solution of 2- [1- (ethoxyimino) butyl] -3-hydroxy-5- (pentamethylphenyl) cyclohex-2-en-1-one (400 mg, 1.1 mmol) in diethyl ether (50 mL) was added. mixed with a saturated aqueous solution of res (II) acetate and shaken. The reaction mixture was evaporated to dryness in vacuo. The solid residue was successively washed with hot water, cold ⁵ with water and diethyl ether and dried. The title compound was obtained as a light green solid (390 mg, 88%), m.p. 210 ° C.

¹⁰ Example 17

Preparation of 2- (1- (ethoxyimino) butyl] -3-hydroxy-5- (pentamethylphenyl) cyclohex-2-en-1-one nickel salt (85)

The title compound was prepared in a manner analogous to that described in Example 16. The title compound was identified by its melting point (see Table IV, Example 21).

²⁰ Example 18

Preparation of 2- (1- (ethoxyimino) -propyl] -3-hydroxy-5- (2,4,6-trimethyl-phenyl) -cyclohex-2-en-1-one tetrabutylammonium salt (88)

To a solution of 329 mg (10 mmol) of 2- [1- (ethoxyimino) propyl] 3-hydroxy-5- (2,4,6-trimethylphenyl) -cyclohex-2-en-1-yl and 5 ml of methanol 2 , 0 ml of a 25% solution of tetra-n-butylammonium hydroxide in methanol

3Q is given. The reaction mixture was allowed to stand at room temperature for 3 hours and then concentrated in vacuo on a rotary evaporator. The residue was taken up in a mixture of 15 ml of dichloromethane and 15 ml of water. The layers were separated and the organic phase is washed with 2 * 10 ml of water, ₃₅ and dried over anhydrous sodium sulfate and concentrated in vacuo. 340 mg of 2- [1- (ethoxyimino) -propyl] -3-hydroxy-5- (2,4,6-trimethyl-phenyl) -cyclohex-2-en-1-one are obtained in the form of a light brown oil. The product is identified by its proton _resonance spectrum _4θ and the spectroscopic data are _{shown in FIG} . (Example 21).

Example 79 ⁴⁵ Compounds of formula IX used in the preparation of compounds of formula I are prepared starting from the corresponding benzaldehyde derivative in a manner analogous to that described in Example 1 (i) and (ii).

Most of the 5-arylcyclohexane-1,3-dione derivatives of formula (IX) are solids. These compounds are generally characterized by means of nuclear magnetic resonance spectra and the resulting proton nuclear magnetic resonance spectroscopic data ⁵ (pmr) II. are summarized in Table.

-13190819

II. spreadsheet

Compound of Formula IX: (CH ₃ ) _n Appearance Proton chemical shift in ppm (D ₆ -DMSO) 2,3- (CH ₃ ) ₂ yellow solid, m.p. 209 'C 2.0-2.8 (10 H, m); 3.4-3.7 (1H, m); 5.28 (1H, s); 7.00 (3 H, m); 11.2 (HH, wide s) 2,4- (CH ₃ ) ₂ yellow solid, m.p. 167'C 2.0-2.8 (10 H, m); 3.40 (1H, m); 5.25 (1H, s); 6.9-7.3 (3 H, m); 11.15 (HH, wide s) 2,5- (CH ₃ ) ₂ pale yellow solid, m.p. 180'C 2.0-3.8 (11 H, m); 5.30 (1 H, s); 6.8-7.3 (3 H, m); 11.5 (HH, wide s) 2,6- (CH ₃ ) ₂ orange solid 2.0-3.8 (11 H, m); 5.28 (1H, s); 6.96 (3 H, m); 11.2 (HH, wide s) 3,4- (CH ₃ ) ₂ pale yellow solid, m.p. 162'C 2.0-2.6 (11H, m); 5.25 (1H, s); 7.00 (3H, tn); 11.0 (HH, wide s) 3,5- (CH ₃ ) ₂ yellow solid, m.p. 170'C 2.0-3.3 (11 H, m); 5.25 (1H, s); 6.8-7.0 (3 H, m); 11.5 (HH, wide s) 2,3,4- (CH ₃ ) ₃ brown solid 2.0-2.7 (13 H, m); 3.0-3.8 (1H, m); 5.28 (1H, s); 6.96 (2 H, m); 11.2 (HH, wide s) 2,3,5- (CH ₃ ) ₃ yellow solid, m.p. 206'C 2.20 (6H, s); 2.30 (3H, s); 2.3-3.0 (4 H, m); 3.50 (1H, m); 5.25 (1H, s); 6.90 (1 H, s); 7.10 (1H, s); 11.0 (HH, wide s) 2,3,6- (CH ₃ ) ₃ solid material 1.9-3.1 (13H, m); 3.80 (1H, m); 5.28 (1H, s); 6.91 (2 H, m); 11.3 (HH, wide s) 2,4,5- (CH ₃ ) ₃ mp 112 ° C not recorded 2,4,6- (CH ₃ ) ₃ m.p. 165'C 2.0-4.1 (14 H, m); 5.20 (1H, s); 6.80 (2 H, s); 11.2 (HH, wide s) 3,4,5- (CH ₃ ) ₃ colorless solid, m.p. 206'C 2.06 (3H, s); 2.20 (6H, s); 2.30-2.85 (4 H, m); 3.08 (1H, m); 5.28 (2 H, s); 6.91 (2 H, s); 11.4 (HH, wide s) 2,3,4,5- (CH ₃ ) ₄ colorless solid, m.p. 223'C not recorded 2,3,4,6- (CH ₃ ) ₄ yellow solid, m.p. 184'C 2.0-2.4 (12H, m); 2.4-3.2 (4 H, m); 3.60 (1H, m); 5.25 (1H, s); 6.80 (1H, s); 11.2 (HH, wide s) 2,3,5,6- (CH ₃ ) ₄ pale yellow solid, m.p. 258'C 2.20 (12H, s); 2.4-3.2 (4 H, m); 3.60 (1H, m); 5.25 (1H, s); 6.80 (1H, s); 11.2 (HH, wide s) 2,3,4,5,6- (CH ₃ ) j colorless solid, m.p. 235'C 2.09 (3H, s); 2.11 (6H, s); 2.20-2.50 (4 H, m); 3.93 (1H, m); 5.15 (1 H, s); 11.0 (OH,

wide s)

Example 20

Used in preparing the compounds of formula (I), (XIII), 2-acyl-5-arilciklohexán-l, 3-dione derivatives of the formula the corresponding 5- ⁵⁰ arilciklohexán-l, 3-dione derivatives by acylation of

Example 1 (iii), Example 5 (i), Example 8 (i), Example 10 (i), Example 12 (i) and Example 13

Prepared in a manner analogous to that described in Example 1 (i).

Most of the 2-acyl-5-arylcyclohexane-1,3-dione derivatives of formula (XIII) are obtained in the form of an oil. These compounds are generally characterized by nuclear magnetic resonance (NMR) spectra and proton nuclear magnetic resonance spectroscopy data (pmr) is shown in Table III. are summarized in Table.

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III. spreadsheet

(XIII) (CHJ _n t R ³ Appearance Proton chemical shift in ppm (CDC1 ₃₎ 2,3- (CH ₃ ) ₂ c ₂ h ₅ pale yellow solid, m.p. 100 'C 1.20 (3 H, t); 2.25 (6H, 2xs); 2.3-4.0 (7 H, m); 7.00 (3 H, s); 18.20 (1H, s) 2,4- (CH ₃ ) ₂ c ₂ h ₅ orange oil 1.10 (3 H, t); 2.30 (6H, s); 2.4-3.0 (4H, m); 3.10 (2H, q); 3.40 (1H, m); 7.00 (3 H, s); 18.10 (1H, s) 2,5- (CH ₃ ) ₂ C ₂ H _s oil 1.20 (3 H, t); 2.25 (6H, s); 2.40-3.80 (7 H, m); 7.00 (3 H, m); 18.20 (1H, s); 2,5- (CH ₃ ) ₂ c ₆ h ₅ pale yellow oil 2.33 (6H, s); 2.45-2.90 (4 H, m); 3.30-3.70 (1H, m); 6.90-7.15 (3H, bs); 7.30-7.80 (3 H, m); 8.00-8.30 (2 H, m) 2,6- (CH ₃ ) ₂ c ₂ h ₅ yellow oil 1.20 (3 H, t); 2.40 (6H, s); 2.4-4.0 (7 H, m); 7.00 (3 H, s); 18.10 (1H, s) 3,4- (CH ₃ ) ₂ c ₂ h ₅ pale yellow solid, m.p. 100 ° C 1.16 (3 H, t); 2.24 (6H, s); 2.56-3.28 (7 H, m); 6.96 (3 H, m); 18.24 (1H, s) 3,4- (CH ₃ ) ₂ n-C ₃ H ₇ pale yellow solid, m.p. 76'C 1.00 (3 H, t); 1.65 (2 H, m); 2.25 (6H, s); 2.5-3.3 (7H, m); 6.98 (3 H, m); 18.25 (1H, s) 3,5- (CH ₃ ) ₂ c ₂ h ₅ yellow solid, m.p. 113'C 1.10 (3 H, t); 2.30 (6H, s); 2.5-3.4 (7 H, m); 6.8-7.0 (3 H, m); 18.20 (1H, s) 2,3,4- (CH ₃ ) ₃ c ₂ h ₅ brown oil 1.20 (3 H, t); 2.20 (9 H, m); 2.50-2.90 (4 H, m); 3.10 (2H, q); 3.60 (1H, m); 6.95 (2 H, m); 18.10 (1H, s) 2,3,5- (CH ₃ ) ₃ c ₂ h _s yellow solid, m.p. 107 'C 1.20 (3 H, t); 2.20 (3H, s); 2.25 (6H, s); 2.45-3.20 (6 H, m); 3.60 (1H, m); 6.80 (1H, s); 6.85 (1H, s); 18.20 (1H, s) 2,3,6- (CH ₃ ) ₃ c ₂ h ₅ orange oil 1.20 (3 H, t); 2.25 (3H, s); 2.31 (3H, s); 2.37 (3H, s); 2.5-3.4 (6 H, m); 3.82 (1H, m); 6.94 (2 H, m); 1.18 (1H, s) 2,4,5- (CH ₃ ) ₃ c ₂ h ₅ yellow solid, m.p. 1.20 (3 H, t); 2.30 (9H, s); 2.4-4.0 (7 H, m); 7.00 (2 H, s); 18.20 (1H, s) 2,4,6- (CH ₃ ) ₃ ch ₃ colorless solid 2.24 (3H, s); 2.36 (6H, s); 2.64 (3H, s); 2.65-4.00 (5 H, m); 6.84 (2 H, s); 18.17 (1H, s) 2,4,6- (CH ₃ ) ₃ C ₂ H _s m.p. 86-88 C 1.60 (3H, t, J = 8Hz); 2.24 (3H, s); 2.37 (6H, s); 2.64-5.26 (7H, m); 6.84 (2 H, m); 18.26 (1H, s) 2,4,6- (CH ₃ ) ₃ n-C ₃ H ₇ oil 1.01 (3H, t); 1.30-1.60 (2 H, m); 2.23 (3H, s); 2.37 (6H, s); 2.40-3.45 (7 H, m); 6.83 (2 H, s); 18.24 (1H, s) 3,4,5- (CH ₃ ) ₃ c ₂ h ₅ m.p. 93 ° C 1.14 (3 H, t); 2.14 (3H, s); 2.28 (6H, s); 2.3-3.4 (7 H, m); 6.79 (2 H, s); 18.12 (1H, s) 2,3,4,5- (CH ₃ ) ₄ c ₂ h ₅ pale yellow solid, m.p. 97'C 1.15 (3 H, t); 2.20 (12 H, m); 2.40-2.90 (4 H, m); 3.10 (2H, q); 3.55 (1H, m); 6.80 (1H, s); 18.10 (1H, s) 2,3,4,6- (CH ₃ ) ₄ c ₂ h ₅ brown oil 1.20 (3 H, t); 2.1-2.4 (12H, 4xS); 2.4-4.0 (7 H, m); 6.90 (1H, s); 18.00 (1H, s) 2,3,4,6- (CH ₃ ) ₄ n-C ₃ H ₇ brown oil 1.00 (3 H, t); 1.65 (2 H, m); 2.1-2.4 (12H, 4 χ s); 2.4-3.4 (6 H, m); 3.80 (1H, m); 6.80 (1H, s); 18.30 (1H, s) 2,3,5,6- (CH ₃ ) ₄ c ₂ h ₅ brown oil 1.20 (3 H, t); 2.30 (12H, s); 2.4-4.0 (7 H, m); 6.80 (1H, s); 18.00 (1H, s) 2,3,4,5,6- (CH ₃ ) ₅ ch ₃ m.p. 183 'C not recorded 2,3,4,5,6- (CH ₃ ) ₅ c ₂ h ₅ m.p. 84 'C not recorded 2,3,4,5,6- (CH ₃ ) j nC ₃ H ₇ brown oil 1.00 (3 H, t); 1.70 (2 H, m); 2.18 (9H, s); 2.25 (6H, s); 2.25-3.40 (6 H, m); 3.90 (1H, m); 18.10 (1H, s)

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Example 21

Most of the compounds of the present invention are obtained in the form of an oil. These compounds are generally characterized by nuclear magnetic resonance spectra. In Table IVa below, proton resonance spectroscopy data (pmr) and Table IVb. Table C-13 neses magmág the resonance spectroscopic data shown for ⁵ Juk.

Table IVa

Serial number of compound Appearance Proton chemical shift in ppm (CDC1 ₃₎ First m.p. 70 ° C 1.04-1.39 (6 H, m); 2.28 (3H, s); 2.32 (3H, s); 2.63-4.01 (9 H, m); 7.07 (3 H, m); 15.03 (HH, wide s) Second pale yellow oil 1.10-1.39 (6Η, m); 2.28 (3H, s); 2.31 (3H, s); 2.40-2.70 (4 H, m); 2.97 (2H, q, J = 8Hz); 3.52 (1H, m); 4.10 (2H, q, J = 8Hz); 7.00-7.15 (3 H, m); 15.0 (HH, wide s) Third pale yellow oil 1.11-1.40 (6H, m); 2.31 (6H, s); 2.64-3.02 (6 H, m); 3.53 (1H, m); 4.12 (2H, q, J = 8Hz); 7.00-7.23 (3 H, m); 15.03 (HH, wide s) 4th pale yellow oil 1.12-1.40 (6 H, m); 2.41 (6H, s); 2.62-3.14 (6 H, m); 3.85 (1 H, m); 4.12 (2H, q, J = 8Hz); 7.01 (3 H, s); 15.03 (HH, wide s) 5th pale yellow oil 1.10-1.37 (6 H, m); 2.22 (6H, s); 2.60-2.92 (7 H, m); 4.07 (2H, q, J = 8Hz); 6.97-7.04 (3 H, m); 14.70 (HH, wide s) 1.08-1.39 (6 H, m); 2.30 (6H, s); 2.65-3.00 (7 H, m); 4.10 (2H, q, J = 8Hz); 6.85 (3H, s); 15.0 (1H, s) 6th pale yellow oil 7th pale yellow oil 1.13-1.48 (6 H, m); 2.23 (3H, s); 2.37 (6H, s); 2.604.23 (9 H, m); 6.83 (2 H, s); 14.99 (H, s) 8th pale yellow oil 1.07-1.40 (6 H, m); 2.21 (6H, s); 2.27 (3H, s); 2.36-3.07 (6 H, m); 3.42 (1H, m); 4.10 (2H, q, J = 8Hz); 6.95-7.23 (2 H, m); 15.0 (HH, wide s) 9th pale yellow oil 1.07-1.41 (6 H, m); 2.23 (6H, s); 2.27 (6H, s); 2.41-3.16 (6 H, m); 4.00-4.12 (3 H, m); 6.91 (1H, s); 15.0 (HH, wide s) 1.07-1.41 (6 H, m); 2.16 (3H, s); 2.24 (3H, s); 2.32 (3H, s); 2.35 (3H, s); 2.40-3.35 (6 H, m); 3.41-4.07 (3 H, m); 6.86 (1H, s); 15.0 (HH, wide s) 10th pale yellow oil 11th pale yellow oil 0.92-1.74 (6 H, m); 2.22 (6H, s); 2.24-3.15 (7 H, m); 3.99 (1H, q, J = 8Hz); 7.04-8.10 (8H, m) 12th pale yellow oil 0.90-1.34 (6 H, m); 2.16 (3H, s); 2.22 (6H, s); 2.24-3.15 (7 H, m); 4.13 (2H, q, J = 8Hz); 7.00-7.25 (3 H, m) 13th pale yellow oil 1.10-1.39 (6 H, m); 2.31 (6H, s); 2.64-3.02 (6 H, m); 3.53 (1H, m '; 4.12 (2H, q, J = 8Hz); 7.00-7.23 (3H, m); 7.38-8.10 (5H, m) 14th pale yellow oil 1.04-1.79 (6 H, m); 2.28 (3H, s); 2.32 (3H, s); 2.63-4.01 (9 H, m); 7.07 (3 H, m); 7.38-8.08 (5 H, m) 15th pale yellow oil 1.13-1.48 (6 H, m); 2.24 (3H, s); 2.42 (6H, s); 2.42-3.90 (9H, ml; 6.85 (2H, s); 7.24-8.08 (5H, m) 16th pale yellow oil 1.05 (3H, t); 1.30-1.60 (2 H, m); 2.23 (3H, s); 2.37 (6H, s); 2.40-3.90 (7 H, m); 4.61 (2 H, m); 5.34 (2 H, m); 5.80 (1H, m); 6.80 (2 H, s); 14.70 (1H, s) 17th pale yellow oil 1.10 (3 H, t); 2.21 (3H, s); 2.37 (6H, s); 2.5-3.95 (8 H, m); 4.52 (2 H, m); 5.34 (2 H, m); 5.80 (1H, m); 6.80 (2 H, s); 14.7 (1H, s) 18th pale yellow oil 1.05 (3H, t); 1.32 (3 H, t); 1.66 (2 H, m); 2.23 (3H, s); 2.37 (6 H, m); 3.42 (1H, m); 4.10 (2H, q, J = 8Hz); 6.95-7.23 15.13 (1H, s) 19th pale yellow oil 1.32 (: H, t); 2.23 (3H, s); 2.37 (6H, s); 2.41 (3H, s); 2.4-4.0 (5 H, m); 4.12 (2H, q); 6.83 (2 H, s); 14.7 (1H, s) 20th solid, m.p. Mp: 114 ° C 0.99 (3H, t); 1.21 (3 H, t); 1.69 (2 H, m); 2.23 (3H, s); 2.37 (1H, s); 2.3-3.9 (7 H, m); 4.01 (2 H, t); 6.83 (2 H, s); 14.99 JH, s)

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Table IVa (continued)

Serial number of compound Appearance 21st m.p. 70-72 ° C 22nd m.p. 89-91 ° C 23rd m.p. 69-71'C 24th pale yellow oil 25th pale yellow oil 26th pale yellow oil 27th pale yellow oil 28th pale yellow oil 29th pale yellow oil 30th m.p. 68-70 ° C 31st pale yellow oil 32nd solid, m.p. <50 'C 33rd pale yellow oil 34th m.p. <50 ° C 35th m.p. 76 'C 36th m.p. 68-70 ° C 37th m.p. 70-71 ° C 38th pale yellow oil 39th pale yellow oil 40th m.p. 92-94 ° C

Proton chemical shift in ppm (CDC1 ₃₎

Δ, 95 (3H, t); 1.20 (3 H, t); 1.2-1.8 (4 H, m); 2.24 (3H, s); 2.37 (6H, s); 2.3-3.9 (5 H, m); 2.95 (2H, q); 4.06 (2 H, t); 6.84 (2 H, s); 15.05 (1H, s)

I, 19 (3H, t); 1.77 (3H, d, J = 6Hz); 2.24 (3H, s); 2.37 (6H, s); 2.3-3.9 (5 H, m); 2.95 (2H, q); 4.47 (2H, d,

J = Hz); 5.6-5.9 (2 H, m); 6.83 (2 H, s); 14.9 (1H, s)

1.19 (3 H, t); 2.24 (3H, s); 2.37 (6H, s); 2.3-3.9 (5 H, m); 2.94 (2H, q); 4.12 (2 H, t); 5.0-5.3 (2 H, m); 5.6-6.0 (1H, m); 6.84 (2 H, s); 14.8 (1H, broad s)

1.19 (3 H, t); 2.24 (3H, s); 2.37 (6H, s); 2.4-3.9 (8H, m); 4.64 (2H, d, J = 2.4HZ); 6.84 (2 H, s); 13.90 (1H, s)

1.20 (3H, t); 2.24 (3H, s); 2.37 (6H, s); 2.4-3.9 (5H, ml; 2.95 (2H, q); 4.10-4.20 (1H, m); 4.36-4.48 (2H, ml; 4.89- 4.98 (1H, m); 6.84 (2H, s); 14.06 (1H, broad s)

1.22 (3H, t); 2.24 (3H, s); 2.38 (6H, s); 2.4-3.9 (5 H, m); 2.99 (2H, q); 4.60 (2 H, s); 5.47 (2 H, s); 6.84 (2H, s): 14.5 (1H, broad s)

1.9 (3H, t); 2.23 (3H, s); 2.35 (6H, s); 2.4-3.9 (5H, ml; 2.90 (2H, q); 5.06 (2H, s); 6.82 (2H, m); 7.36 (5H, m); 3 (1H, s)

1.18 (3 H, t); 2.24 (3H, s); 2.36 (6H, s); 2.4-3.9 (7 H, m); 5.03 (2 H, s); 6.83 (2 H, s); 7.33 (4H, s); 14.16 (1H, s)

1.18 (3 H, t); 2.24 (3H, s); 2.36 (6H, s); 2.4-3.9 (7 H, m); 5.02 (2 H, s); 6.83 (2 H, s); 7.37 (4H, d6); 14.5 (1H, s)

1.18 (3 H, t); 2.24 (3H, s); 2.36 (6H, s); 2.3-3.9 (7 H, m); 5.03 (2 H, s); 6.83 (2 H, s); 7.0-7.4 (4 H, m); 14.29 (1H, s)

1.18 (3 H, t); 2.22 (3H, s); 2.34 (9H, s); 2.3-3.9 (7 H, m); 5.01 (2 H, s); 6.82 (2 H, s); 7.21 (4H, d6); 14.45 (1H, s)

1.21 (3H, t); 2.24 (3H, s); 2.35 (6H, s); 2.4-3.9 (7 H, m); 5.18 (2 H, s); 6.83 (2 H, s); 7.88 (4H, d6); 13.74 OH, s)

1.20 (3H, t); 2.22 (3H, s); 2.34 (6H, s); 2.4-3.9 (7H, rr); 5.02 (2 H, s); 6.81 (2 H, s); 7.2-7.34 (4 H, m); 14.03 (1H, s)

1.20 (3H, t); 2.23 (3H, s); 2.35 (6H, s); 2.4-3.9 (7 H, m); 5.15 (2 H, s); 6.83 (2 H, s); 7.19-7.40 (3 H, m); 14.0 OH, s)

0.9-1.2 (6H, m); 1.3-1.8 (6 H, m); 2.25 (3H, s); 2.38 (6H, s); 2.4-3.9 (7 H, m); 4.07 (2 H, t); 6.84 (2 H, s); 14 (H wide s)

1.00 (3 H, t); 1.5-1.8 (5 H, m); 2.24 (3H, s); 2.37 (6H, s); 2.4-3.9 (7 H, m); 4.46 (2H, d, J = 6Hz); 5.4-6.0 (2 H, m); 6.84 (2 H, s); 14 (1H, wide s)

1.00 (3 H, t); 1.3-1.6 (2 H, m); 2.22 (3H, s); 2.36 (6H, S); 2.4-3.9 (7 H, m); 4.10 (2H, t); 5.0-5.3 (2 H, m);

5.6-6.0 (1H, m); 6.82 (2 H, s); 14.6 (1H, s)

0.97 (3H, t); 1.6 (2 H, m); 2.24 (3H, s); 2.37 (6H, s);

2.4-3.7 (8 H, m); 4.65 (2H, d, J = 2.4 Hz); 6.84 (2 H, s); 14.1 (1H, s)

1.00 (3 H, t); 1.3-1.6 (2 H, m); 2.24 (3H, s); 2.38 (6H, s); 2.4-3.9 (7 H, m); 4.1-4.2 (1H, m); 4.36-4.51 (2H, ra); 4.89-4.98 (1H, m); 6.84 (2 H, s); 14 (1H, bs) 1.00 (3H, t); 1.3-1.6 (2 H, m); 2.24 (3H, s); 2.37 (6H, s); 2.4-3.9 (7 H, m); 4.59 (2 H, s); 5.48 (2 H, s); 6.84 (2 H, s); 14 (1H, wide s)

-17IVa. Table (continued)

Serial number of compound Appearance Proton chemical shift in ppm (CDC1 ₃₎ 41st pale yellow oil 0.99 (3H, t); 1.4-1.7 (2 H, m); 2.21 (3H, s); 2.34 (6H, s); 2.4-3.9 (7 H, m); 5.00 (2 H, s); 6.81 (2 H, s); 7.30 (4H, s); 14.23 (1H, s) 42nd pale yellow oil 0.99 (3H, t); 1.4-1.7 (2 H, m); 2.23 (3H, s); 2.35 (6H, s); 2.4-3.9 (7 H, m); 5.00 (2 H, s); 6.83 (2 H, s); 7.36 (4H, d6); 14 (1H, wide s) 43rd pale yellow solid 196 ° C (dec.) material, op .: not recorded 44th pale yellow solid 45-50 'C m.p. 0.90-1.20 (6H, m); 2.10 (3H, s); 2.30 (6H, s); 2.2-3.7 (6 H, m); 3.99 (3 H, m); 6.85 (2 H, s); 8.10 (4H, d6) 45th pale yellow solid <50 'C m.p. 1.0-1.2 (6H, m); 2.10 (3H, s); 2.30 (6H, s); 2.3-3.6 (6 H, m); 3.99 (3 H, m); 6.80 (2 H, s); 8.20 (4H, m) 46th pale yellow solid 83'C m.p. 1.0-1.3 (6H, m); 2.25 (3H, s); 2.45 (6H, s); 2.5-4.2 (9 H, m); 6.80 (2 H, s); 9.20 (3 H, m) 47th yellow solid (decomposition) mp: 200 'C not recorded 48th pale yellow oil 1.04 (3H, t); 2.24 (3H, s); 2.42 (6H, s); 2.4-3.7 (5 H, m); 4.46 (2H, d, J = 6Hz); 5.12 (2 H, m); 5.64 (1H, m); 6.85 (2 H, s); 7.2-8.1 (5 H, m) 49th pale yellow oil 1.04 (1H, t); 2.22 (3H, s); 2.40 (6H, s); 2.4-3.9 (7 H, m); 4.55 (2H, d, J = 2.4 Hz); 6.82 (2 H, s); 7.4-8.1 (5H, in) 50th pale orange oil 0.83-5.10 (6H, m); 1.53 (2 H, m); 2.23 (3H, s); 2.42 (6H, s); 2.4-3.7 (7 H, m); 4.00 (2H, q, J = 8Hz); 6.84 (2 H, s); 7.28-8.08 (5 H, m) 51st orange oil 0.92 (3H, t); 1.53 (2 H, m); 2.23 (3H, s); 2.42 (6H, s); 2.5-44 (7H, m); 4.46 (2 H, d); 4.96 (2H, d6); 5.77 (1H, m); 6.84 (2 H, s); 7.2-8.1 (5 H, m) 52nd light brown oil 1.10 (3 H, t); 1.25 (3 H, t); 2.20 (3H, s); 2.26 (6H, s); 2.4-3.7 (5 H, m); 2.96 (2H, q); 4.11 (2H, q); 6.99 (2 H, s); 14.98 (1H, broad s) 53rd yellow oil 1.10-1.40 (6H, 2x); 2.20 (3H, s); 2.26 (6H, s); 2.86-3.01 (6 H, m); 3.56 (1H, m); 4.11 (2H, q); 6.89 (2 H, s); 15.02 (1H, s) 54th pale yellow oil 1.17 (3 H, t); 1.34 (3 H, t); 2.15 (3H, s); 2.28 (6H, s); 2.5-3.4 (7 H, m); 4.04 (2H, q); 6.87 (2 H, s); 14.95 (1H, s) 0.92-1.40 (6 H, m); 1.62 (2 H, m); 2.16 (3H, s); 2.24 (3H, s); 2.32 (3H, s); 2.34 (3H, s); 2.6-3.0 (6H, m); 3.74-4.23 (3 H, m); 6.85 (1H, s); 15.1 (1H, s) 55th yellow oil 56th pale yellow oil 1.19 (3 H, t); 2.14 (3H, s); 2.24 (3H, s); 2.32 (3H, s); 2.34 (3H, s); 2.4-3.14 (6 H, m); 3.80 (1H, m); 4.53 (2H, d, J = 6Hz); 4.35 (2 H, m); 5.90 (1H, m); 6.83 (1H, s); 14.5 (1H, broad s) 57th yellow oil 0.97 (3H, t); 1.62 (2 H, m); 2.13 (3H, s); 2.22 (3H, s); 2.29 (3H, s); 2.32 (3H, s); 2.60-3.02 (6 H, m); 3.80 (1H, m); 4.581 (2H, d, J = 6Hz); 5.24 (2 H, m); 5.80 (1H, m); 6.83 (1H, s); 14.65 (1H, s) 58th pale yellow oil 0.99 (3H, t); 1.17 (3 H, t); 2.17 (3H, s); 2.25 (3H, s); 2.39 (3H, s); 2.49 (3H, s); 2.4-3.5 (6 H, m); 3.5-4.13 (3 H, m); 6.87 (1H, s); 7.25-7.56 (3 H, m); 8.03-8.09 (2 H, m) 59th yellow solid (decomposition) mp: 250 'C not recorded 60th pale yellow solid 121 'C m.p. 1.00-1.30 (6H, m); 2.10 (9 H, s); 2.15 (6H, s); 2.2-3.3 (6 H, m); 3.6-4.15 (3 H, m); 14.80 (1H, s) 61st pale yellow solid <50 'C material, op. 1.21 (3H, t); 2.14 (9 H, s); 2.32 (6H, s); 2.43-3.86 (6H, m) 4.00 (1 H, m); 4.50 (2H, d, J = 7Hz); 5.37 (2H, m); 5.89 (1H, m); 14.53 (1H, s) 62nd light brown solid 1I6'C m.p. 1.00-1.32 (6H, 2 x t); 1.62 (2 H, m); 2.22 (9H, s); 2.32 (6H, s); 2.4-3.1 (6 H, m); 3.99 - 1.23 (3 H, m); 15.06 (1H, s)

-181

190,819

Table IVa (continued)

Serial number of compound Appearance Proton chemical shift in ppm (CDC1 ₃₎ 63rd pale bama oil 1.00 (3 H, t); 1.63 (2 H, m); 2.21 (9H, s); 2.31 (6H, s); 2.49-3.00 (6 H, m); 4.00 (1H, m); 4.52 (2H, d, J = 7 Hz); 5.36 (2 H, m); 5.88 (1H, m); 14.60 (1H, s) 64th yellow oil 1.04-1.40 (6H, 2xt); 2.19-2.27 (12 H, m); 2.67 (4 H, m); 2.97 (2H, q); 3.59 (1H, m); 4.11 (2H, q); 6.87 (1H, s); 15.0 (1H, bs) 65th pale yellow oil 0.98 (3H, t); 1.18 (3 H, t); 1.68 (2 H, m); 2.24 (6H, s); 2.5-3.4 (7 H, m); 4.00 (2 H, t); 6.9-7.1 (3 H, m); 14 (IH, windy s) 66th pale yellow oil 1J7 (3H, t); 2.25 (6H, s); 2.5-3.4 (7 H, m); 4.54 (2H, d, J = 6.4 Hz); 5.35 (2 H, m); 5.90 (1H, m); 6.9-7.2 (3 H, m); 14.6 (1H, s) 67th pale yellow oil 0.98 (3H, t); 1.32 (3 H, t); 1.6 (2 H, m); 2.25 (6H, s); 2.5-3.4 (7 H, m); 4.10 (2H, q); 7.00-7.25 (3 H, m); 15.1 (1H, bs) 68th pale yellow oil 0.98 (6H, t); 1.63 (4 H, m); 2.24 (6H, s); 2.5-3.4 (7H, ml; 4.01 (2H, q); 6.95-7.25 (3H, m); 14 (1H, bs) 0.98 (3H, t); 1.63 (2H, m); 2.25 (6H, s); 2.5-3.4 (7H, m'v, 4.52 (2H, d, J = 6.4Hz); 5.25 -5.44 (2H, m); 5.79-6.21 (1H, m); 6.90-7.25 (3H, m); 14.6 (1H, s) 69th pale yellow oil 70th m.p. 183 ° C 1.32 (3 H, t); 2.13-3.45 (23 H, m); 4.13 (2H, q); 14.68 (1H, bs) 71st pale yellow oil 1.12-1.40 (6 H, m); 2.22 (3H, s); 2.30 (3H, s); 2.38 (3H, s); 2.63-2.99 (6H, m); 4.004.24 (3 H, m); 5.93 (2 H, m); 14.99 (1H, bs) 72nd m.p.> 250 ° C not recorded 73rd pale yellow oil 0.92 (3H, t); 1.10 (3 H, t); 1.48 (2 H, m); 2.23-3.76 (22 H, m); 4.00 (2H, q); 7.45-8.09 (5 H, m) 74th pale yellow oil 0.99 (3H, t); 1.60 (2 H, m); 2.10-4.90 (23 H, m); 6.85 (1H, s); 13.95 (1H, bs) 75th pale bama solid, m.p. 132 'C 0.99 (3H, t); 1.63 (2 H, m); 2.22-4.94 (26 H, m); 14.00 (1H, broad s) 76th oil 1.21 (3 H, t); 2.22-4.89 (26 H, m); 13.94 (1H, bs) 77th m.p. 96 ° C not recorded 78th m.p.> 250 ° C not recorded 79th oil 0.99 (6H, 2x); 1.69 (4 H, m); 2.22-3.38 (22 H, m); 4.02 (2 H, t); 15.15 (1H, bs) 80th oil 1.19 (3 H, t); 2.22-2.83 (22 H, m); 3.90 (3 H, s); 14.71 (1H, broad s) 81st oil 1.09 (6H, 2x); 2.23-3.74 (22 H, m); 4.02 (2H, q); 745-8.08 (5 H, m) 82nd oil 10 (3H, t); 1.66 (2 H, m); 2.23-4.06 (22 H, m); 4.60 (2 H, s); 5.48 (2 H, s); 14.0 (1H, bs) 83rd oil 1.20 (3H, t); 1.77 (3 H, d); 2.23-4.20 (22 H, m); 4.47 (2 H, d); 5.74 (2 H, m); 14.0 (1H, bs) 84th pale green solid, m.p. 210'C not recorded 85th m.p. 240 ° C not recorded 86th oil 1.22 (3H, t); 2.22-4.22 (25 H, m); 5.12 (2 H, s); 14.04 (1H, s) 87th light brown oil 1.22 (3H, t); 2.31 (3H, s); 2.35-3.70 (5 H, m); 3.95-4.45 (2 H, m); 6.90-7.15 (3H, bs); 7.30-7.80 () H, m); 8.00-8.30 (2 H, m) 88th pale bama oil 0.71-1.82 (34 H, m); 2.22 (3H s); 2.36 (6H, s); 1.99-2.70 (4 H, m); 2.76-4.27 (U H, m); 4.07 (2H, q); 6.78 (2H, s) 89th oil (, 8-1.4 (6H, m); 2.26 (3H, s); 2.45 (9H, s); 2.45-4.0 (9H, m); 6.92 (2H, s); 7.34 (2H, d); 8.0 (2H, d) 90th oil 6.7-1.4 (6H, m); 2.25 (12H, s); 2.37 (6H, s); 2.37-4.0 (9 H, m); 6.85 (4H, s)

-191

190,819

Table IVa (continued)

Serial number of compound Appearance Proton chemical shift in ppm (CDC1 ₃₎ 91st oil 0.8-1.3 (6 H, m); 2.24 (3H, s); 2.42 (6H, s); 2.42-4.0 (12H, m + s); 6.85 (2 H, s); 6.9 (2 H, d); 7.95 (2H, d) 92nd oil 0.8-1.3 (6 H, m); 2.24 (3H, s); 2.44 (6H, s); 2.45-4.2 (9 H, m); 6.86 (2 H, s); 7.96 (2 H, d); 7.44 (2H, d) 93rd oil 1.01 (3H, t); 1.27 (3 H, t); 2.16 (3H, s); 2.20 (3H, s); 2.38 (6H, s); 2.4 4.3 (9H, m); 6.84 (2H, s) 94th oil 0.99 (3H, t); 1.23 (12H, s + t); 2.24 (3H, s); 2.40 (6H, s); 2.45-4.3 (9 H, m); 6.85 (2H, s) 95th m.p. 138-142 ° C 0.9-1.4 (9 H, m); 2.24 (3H, s); 2.38 (6H, s); 2.4-4.2 (11 H, m); 4.62 (2 H, s); 6.90 (2 H, s).

IV b. spreadsheet

Compound I3 C chemical shifts δ in ppm Number (CDC1 ₃₎

1. 11.26 (IC); 14.14 (IC); 14.68 (IC); 20.97 (2C); 33.91 (IC); 39-45 (2C); 70.26 (IC); 107.10 (IC); 122.79 (IC);

125.85 (IC); 128.50 (IC); 134.03 (IC); 137.22 (IC); 140.20 (IC); 166.53 (IC); 184-195 (2C).

2. 11.22 (IC); 14.01 (IC); 19.07 (IC); 20.69 (IC); 20.86 (IC); 33.32 (IC); 39-45 (2C); 70.21 (IC); 107.05 (IC); 124.82 (IC); 126.99 (IC); 131.48 (IC); 135.22 (IC); 136.14 (IC); 137.39 (IC); 166.53 (IC); 184-195 (2C).

3. 11.32 (IC); 14.19 (IC); 18.85 (IC); 21.07 (IC); 21.18 (IC); 33.75 (IC); 39-45 (2C); 70.37 (IC); 107.21 (IC);

125.85 (IC); 127.47 (IC); 130.78 (IC); 132.35 (IC); 135.02 (IC); 140.31 (IC); 166.59 (IC); 184-195 (2C).

4. 11.27 (IC); 14.14 (IC); 21.13 (IC); 21.94 (2C); 33.75 (IC); 39-45 (2C); 7O, 37 (1C); 107.21 (IC); 126.77 (IC); 129.91 (2C); 136.36 (2C); 137.49 (IC); 166.75 (IC); 184-195 (2C).

5. 11.32 (IC); 14.25 (IC); 19.34 (IC); 19.88 (IC); 21.02 (IC); 37.38 (IC); 39-45 (2C); 70.26 (IC); 107.48 (IC); 123.90 (IC); 128.07 (IC); 130.02 (IC); 135.17 (IC); 136.84 (IC);

140.15 (IC); 166.34 (IC); 184-195 (2C).

6. 11.21 (IC); 14.09 (IC); 20.86 (2C); 21.29 (IC); 37.54 (IC); 39-45 (2C); 70.26 (IC); 107.27 (IC); 124.33 (2C); 128.56 (IC); 138.20 (2C); 142.42 (IC); 166.48 (IC); 184-195 (2C).

Example 22

This example illustrates the preparation of the compositions of the present invention in an exemplary, non-limiting manner.

(a) Emulsifiable concentrates

No. 7 compound "Teri" ²⁰ N13 undergoing 3% v / v "Kemmat" SC15B-one dissolved in toluene containing 7% v / v. The resulting emulsifiable concentrate is diluted with water to a suitable concentration before use by spraying to obtain an aqueous emulsion for application to the plants.

The word 'Teric' is a trade mark and the product 'Teric' is a product obtained by ethoxylation of 13 nonylphenols.

The word 'Kesni' is a trade mark and the word 'Kemmin' refers to SCI 5B calcium dodecylbenzene sulphonate.

b) Aqueous slurry part by weight compound and 1 part by weight of "Dyapol" PT surfactant were added to "Teric" N8 aqueous ol35 (94 parts by weight) and the mixture was ground in a ball mill. The resulting stable aqueous suspension is diluted with water to the desired concentration to give a sprayable aqueous suspension.

The word "Dyapol" is a trademark and "Dyapol" PT is an anionic suspending agent.

"Teric" refers to the product obtained by ethoxylation of N8 nonylphenol.

c) Emulsifiable concentrate by weight part no. Compound 5, 5 parts Te ⁵⁰ ric N13 and 5 parts Kemm SC15B are dissolved in 80 parts Solvesso 150. The resulting emulsifiable concentrate is diluted with water to the desired concentration to give a sprayable aqueous emulsion.

⁵⁵ The word 'Solvesso' is a trade mark and the word 'Solvesso' represents 150 high-boiling aromatic kerosene fractions.

d) Dispersible Powder Weight Part No. 7 3 parts by weight of "Matexil" DA / AC, 1 part by weight of "Aerosol" OT / B and 86 parts by weight of kaolin 298 and then milled to a particle size of less than 50 microns.

The word "Matexil" is a trademark and "Matexil" is a DA / AC

-201

190,819 denotes the disodium salt of a condensation product of naphthalenesulfonic acid and formaldehyde.

The word "Aerosol" is a trade mark and the term "Aerosol" refers to a composition containing sodium sulfosuccinic acid dioctyl ester OT / B.

e) High Part Concentrate Weight Part No. 7 compound, 0.5 parts by weight of silica aerogel and 0.5 parts by weight of synthetic amorphous silica were ground in a hammer mill. The resulting powder composition has a particle size of less than 200 microns.

f) Dusting composition part by weight No. 7 10 parts by weight of attapulgite and 80 parts by weight of pyrophyllite are thoroughly mixed and thoroughly ground in a hammer mill. The resulting powder formulation has a particle size of less than 200 microns.

Example 23

This example illustrates the preparation of the compositions of the present invention, but is not limited thereto.

a) Emulsifiable concentrates by weight part no. Compound II was dissolved in toluene containing 7% by volume of "Teric" N13 and 3% by volume of "Kemal" SC15B. The resulting emulsifiable concentrate is diluted with water prior to use to a suitable concentration by spraying to obtain an aqueous emulsion for application to the plants.

b) Aqueous solution by weight compound and 1 part by weight of "Dyapol" PT surfactant are added to 2% w / v aqueous solution of "Teric" N8 (94 parts by weight). The resulting mixture is shaken and the resulting aqueous solution is diluted with water to the desired concentration to give a ready-to-use spray.

(c) High active ingredient concentrate by weight 84 compound, 2.5 parts by weight of silica aerogel and 2.5 parts by weight of synthetic amorphous silica were ground in a hammer mill. The resulting powder composition has a particle size of less than 200 microns.

d) Emulsifiable concentrate by weight part no. 5 parts of Teric N13 and 5 parts of Kemmin SC15B are dissolved in 80 parts of Solvesso 150. The resulting emulsifiable concentrate is diluted with water to the desired concentration to give a sprayable aqueous emulsion.

In a manner analogous to that described in Example 22 (a), (b) or (c), emulsifiable concentrates and / or suspensions are prepared and diluted with water, optionally containing a surfactant and / or an oil. The resulting aqueous compositions of appropriate concentration are described in Figures 24 and 24

It is used as described in Example 25 to determine pre-emergent and post-emergent herbicidal activity.

24-27. For example, the compositions are applied at 1000 liters / hectare.

Example 24

The compound to be tested is described in Example 23 (a), No. 7. The compound is formulated as described for Compound. 47, 59, 72, 78 and 88. however, the compound of Formula 23 was formulated as in Example 23 (b). No. 85 compound formation a

Example 23 (c).

The pre-emergent herbicidal activity is determined as follows:

The seeds of the test plants are planted in soil in pots, in rows of 2 cm deep, and the two pots, after seeding, are sprayed with an appropriate amount of the test composition. Seeds planted in the same pots but not sprayed with the composition of the present invention serve as controls. All pots are placed in a greenhouse, sprayed from above to initiate germination, and watered from below to promote the desired optimal plant growth. The pots are removed from the greenhouse after three weeks and the effect of the treatment is visually evaluated.

The results are given in Table V using the following scale from 0 to 5:

= 0-10% damage;

= 11-30% damage;

= 31-60% damage;

= 61-80% damage;

= 81-99% damage;

= 100% mortality.

Notation means that no experiment was performed.

In Table V, the test plants are denoted by the following abbreviations:

Bu = wheat

Vz = wild oats

Pe = over

Ka = porridge

Bo = pea

Ip = Ipomea

Mu = mustard

Nf = sunflower

-211

190,819

Table V.

Investigation of pre-emergent herbicidal activity

Serial number of test compound employee quantity (Kg / ha) Bu vz Pe Plant to be examined ip Mu nf K Bo 9th 2.0 3 5 5 5 0 0 0 0 9th 0.5 0 5 5 5 0 0 0 0 10th 2.0 1 5 5 5 0 0 0 0 10th 0.5 0 5 5 5 0 0 0 0 16th 2.0 4 5 5 5 0 0 0 0 16th 0.5 0 5 5 5 0 0 0 0 18th 2.0 2 5 5 5 0 0 0 0 18th 0.5 0 5 5 4 0 0 0 0 19th 2.0 3 5 5 5 0 0 0 0 19th 0.5 0 3 5 5 0 0 0 0 24th 2.0 0 5 5 5 0 0 0 0 24th 0.5 0 0 5 5 0 0 0 0 25th 1.0 2 5 5 5 0 0 0 0 25th 0.25 1 1 5 5 0 0 0 0 26th 1.0 1 4 5 5 0 0 0 0 26th 0.25 0 0 5 5 0 0 0 0 38th 2.0 0 2 5 4 0 0 0 0 38th 0.5 0 3 5 4 0 0 0 0 47th 2.0 4 5 5 5 0 0 0 0 47th 0.5 0 0 5 4 0 0 0 0 50th 2.0 4 5 5 5 0 0 0 0 50th 0.5 0 4 5 4 0 0 0 0 52nd 1.0 0 1 5 5 0 0 0 0 52nd 0.25 0 0 4 0 0 0 0 0 54th 2.0 3 4 5 5 0 0 0 0 54th 0.5 0 0 5 5 0 0 0 0 56th 1.0 0 3 5 5 0 0 0 0 56th 0.25 0 2 5 5 0 0 0 0 59th 1.0 4 5 5 5 0 0 0 0 59th 0.25 2 5 5 5 0 0 0 0 61st 1.0 0 2 4 5 0 0 0 0 61st 0.25 0 0 5 4 0 0 0 0 67th 1.0 0 5 5 1 0 0 0 0 67th 0.25 0 0 5 0 0 0 0 0 70th 0.5 4 3 5 5 0 0 0 0 70th 0,125 0 1 5 5 0 0 0 0 71st 0.5 1 4 5 5 0 0 0 0 71st 0,125 0 1 5 5 0 0 0 0 73rd 0.5 0 1 5 5 0 0 0 0 74th 0.5 0 3 5 5 0 0 0 0 75th 0.5 0 3 5 5 0 0 0 0 76th 0.5 0 2 5 5 0 0 0 0 84th 1.0 0 5 5 5 0 0 0 0

Example 25

The compound to be tested is described in Example 23 (a), no. The compound is formulated as described for Compound. 47, 59, 72, 78 and 88. however, the compound is formulated as in Example 23 (b). No. 85 The compound of formula 60 is formed according to Example 60 c).

The post-emergent herbicidal activity is determined by the following method:

Seeds of test plants are planted in soil in pots, in rows of 2 cm. Mono-g5 and dicotyledonous plants are sown separately in two pots. The four pots are placed in a greenhouse, lightly watered from above to initiate germination, and watered from below to promote optimal plant growth. After the plants have a height of approx. It reaches 10 to 12.5 cm, monocotyledonous and dicotyledonous plants are removed. sprayed with a suitable amount of the composition of the invention. After spraying, the pots are returned to the greenhouse and kept there for 3 weeks. The extent of damage is then visually determined and the results obtained are compared with untreated controls.

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The results obtained are shown in Table VI. are summarized in the table below and evaluated using the following 0-5 scale:

= 0-10% damage;

= 11-30% damage;

= 31-60% damage;

= 61-80% damage;

= 81-99% damage;

= 100% mortality.

Notation means that no experiment was performed. VI. In Table 1, the plants to be examined are indicated by the following abbreviations:

Bu = wheat;

Vz = wild oats;

Pe = perje;

Ka = porridge;

Bo = peas;

Ip = Ipomea;

Mu = mustard;

Nf = sunflower.

VI. spreadsheet

Examination of post-emergent herbicidal activity

Serial number of test compound employee quantity (Kg / ha) Bu vz Plant to be examined Pe Ká Bo Ip Mu nf First 2.0 1 5 5 5 0 0 0 0 First 0.5 0 3 4 4 0 0 0 0 Second 2.0 1 4 5 5 0 0 0 0 Second 0.5 0 2 4 5 0 0 0 0 Third 2.0 0 3 5 5 0 0 0 0 5th 2.0 3 2 5 5 0 0 0 0 5th 0.5 0 4 4 4 0 0 0 0 6th 2.0 3 5 5 5 0 0 0 0 6th 0.5 0 4 5 5 0 0 0 0 7th 2.0 2 5 5 5 0 0 0 0 7th 0.5 2 5 5 5 0 0 0 0 7th 0.25 0 5 5 5 0 0 0 0 7th 0,125 0 5 5 4 0 0 0 0 8th 2.0 1 5 5 5 0 0 0 0 8th 0.5 0 3 5 5 0 0 0 0 11th 2.0 0 4 5 5 0 0 0 0 11th 0.5 0 3 3 4 0 0 0 0 15th 2.0 1 5 5 5 0 0 0 0 15th 0.5 1 5 5 '5 0 0 0 0 15th 0.25 0 4 5 5 0 0 0 0 15th 0,125 0 5 5 4 0 0 0 0 16th 2.0 4 5 5 5 0 0 0 0 16th 0.5 2 5 5 5 0 0 0 0 18th 2.0 5 5 5 5 0 0 0 0 18th 0.5 3 5 5 5 0 0 0 0 19th 2.0 4 5 5 5 0 0 0 0 19th 0.5 0 5 5 5 0 0 0 0 22nd 1.0 0 5 5 5 0 0 0 0 22nd 0.25 0 5 5 5 0 0 0 0 24th 2.0 3 5 5 5 0 0 0 0 24th 0.5 0 5 5 4 0 0 0 0 25th 1.0 2 5 5 5 0 0 0 0 25th 0.25 0 5 5 5 0 0 0 0 26th 1.0 0 5 5 5 0 0 0 0 26th 0.25 0 4 5 4 0 0 0 0 28th 1.0 0 5 5 5 0 0 0 0 28th 0.25 0 5 5 4 0 0 0 0 36th 1.0 2 5 5 5 0 0 0 0 36th 0.25 0 5 5 5 0 0 0 0 38th 2.0 3 5 5 5 0 0 0 0 38th 0.5 1 5 4 4 0 0 0 0 39th 1.0 2 5 5 5 0 0 0 0 39th 0.25 0 5 5 5 0 0 0 0 40th 1.0 3 5 5 5 0 0 0 0 40th 0.25 0 5 5 5 0 0 0 She 40th 0,125 0 4 5 5 0 0 0 0 41st 1.0 0 5 5 5 0 0 0 0

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VI. Table (continued)

Serial number of test compound employee quantity (Kg / ha) Bu vz Plant to be examined Pe Ká Bo Ip Mu nf 41st 0.25 0 4 5 5 0 0 0 0 46th 1.0 4 5 5 5 0 0 0 0 46th 0.25 0 5 5 5 0 0 0 0 47th 2.0 .. 3 5 5 5 0 0 0 0 47th 0.5 0 5 5 5 0 0 0 0 50th 2.0 4 5 5 5 0 0 0 0 50th 0.5 0 4 5 5 0 0 0 0 51st 2.0 4 5 5 5 0 0 0 0 51st 0.5 0 4 5 5 0 0 0 0 52nd 1.0 0 5 5 5 0 0 0 0 52nd 0.25 0 4 5 5 0 0 0 0 53rd 1.0 0 5 5 5 0 0 0 0 53rd 0.25 0 3 4 4 0 0 0 0 54th 2.0 2 5 5 5 0 0 0 0 54th 0.5 0 3 4 5 0 0 0 0 55th 0.25 5 5 5 5 0 0 0 0 55th 0,125 3 5 5 5 0 0 0 0 57th 0.25 1 5 5 5 0 0 0 0 57th 0,125 1 4 4 5 0 0 0 0 58th 1.0 4 5 5 5 0 0 0 0 58th 0.25 3 5 5 5 0 0 0 0 59th 1.0 5 5 5 5 0 0 0 0 59th 0.25 3 5 5 5 0 0 0 0 60th 2.0 5 5 5 5 0 0 0 0 60th 0.5 3 5 5 5 0 0 0 0 61st 1.0 3 5 5 5 0 0 0 0 61st 0.25 1 5 5 5 0 0 0 0 62nd 1.0 5 5 5 5 0 0 0 0 62nd 0.25 2 5 5 5 0 0 0 0 62nd 0,125 1 5 5 5 0 0 0 0 63rd 1.0 0 5 5 5 0 0 0 0 63rd 0.25 0 4 4 4 0 0 0 0 64th 2.0 0 5 5 5 0 0 0 0 64th 0.5 1 5 5 5 0 0 0 0 66th 2.0 2 5 5 5 0 0 0 0 66th 0.5 0 5 5 5 0 0 0 0 67th 1.0 0 5 5 5 0 0 0 0 67th 0.25 0 4 4 4 0 0 0 0 70th 0.5 4 5 5 5 0 0 0 0 70th 0,125 0 4 3 5 0 0 0 0 71st 0.5 0 5 5 5 0 0 0 0 71st 0,125 0 3 5 5 0 0 0 0 72nd 0.5 1 5 5 5 0 0 0 0 72nd 0,125 0 5 5 5 0 0 0 0 73rd 0.5 0 4 5 5 0 0 0 0 73rd 0,125 0 4 5 5 0 0 0 0 74 0.5 0 4/5 5 5 0 0 0 0 74th 0,125 0 4/5 5 5 0 0 0 0 75th 0.5 0 4 5 5 0 0 0 0 75th 0,125 0 3 4 5 0 0 0 0 76th 0.5 2 2 5 5 0 0 0 0 76th 0,125 0 0 5 5 0 0 0 0 84th 1.0 0 5 5 5 0 0 0 0 84th 0,125 0 2 1 0 0 0 . 0 0

Example 26

The compound to be tested is described in Example 23 (d) in Example 5 (d). compound as formulated. 65

160 ml of a methyl cyclohexanone solution containing 21.9 g / l of "Span" 80 and 78.2 g / l of "Tween" 20 are diluted to 500 ml with water. "Span" is a trademark of 80 surfactants containing sorbitol monolaurate. "Tween" is 20 sorbitol monolaurate in 20 moles of diet24

-241

Is a trademark of a surfactant containing 190 819 condensation products of lene oxide. An appropriate amount of the test compound is added to the emulsion obtained above.

Dilute 5 to 5 ml of the test compound to 40 ml with water. The test plants are sprayed on young specimens of test plants listed in Table II (post-emergence test). Damage to plants is evaluated after 14 days and is reported on a scale of 0-5 (where 0 = 0-20% damage and 5 = total death).

The preemergent herbicidal activity is determined as follows: seeds of the test plants are seeded in shallow fractures formed on soil surfaces in plastic trays. The soil surface is leveled, sprayed and a thin layer of fresh soil is spread over the sprayed soil. Herbicidal activity is determined after 21 days and is given using a scale of 0-5 for the post-emergence test. The results obtained are shown in Table VII. are summarized in Table.

Notation means that no experiment was performed.

The test plants are abbreviated as follows

Cu = sugar beet

Re = rapeseed

Gya = cotton

Word = soybean

Ku = corn

Tb = winter wheat

Ri = rice

Sn = Senecio vulgar

Ip = Ipomea purpurea

But = Amaranthus retroflexus

Pi = Polygonum aviculare

C'a = Chenopodium album

Ga = Galium in apparatus

Xa = Xanthium pensylvanicum Ab = Abutilon theophrasti Co = Cassia obtusifolia Av - Avena fatua Dg = Digitaria sanguinalis A1 = Alopecurus myosuroides St = Setaria viridis Ec = Echinochloa crus-galli Sh = Sorghum halepense Ag = Agropyron repens Cn =

VII. Table A, Part

Serial number of test compound Rate of application (kg / ha) Cu from Gya Word Plant to be examined ku tb Ri sn Ip Am Pi ca 7th post 1.9 0 0 0 5 3 4 0 0 0 0 7th post 0.5 0 0 0 5 0 4 0 1 0 0 5th post 2.0 - - - - 2 - - - _ - - 5th post 1.0 - - - 1 - - - - - 5th post 0.5 - - - - 0 - - - - - 5th post 0.25 - - - - 0 - - - - - 11th post 2.0 - - - - 1 - - - - - 11th post 1.0 - - - - 1 - - - - - 11th post 0.5 - - - - 0 - - - - 11th post 0.25 - - - - 0 - - - - -

VII. Table B, Part

Serial number of test compound Rate of application (kg / ha) Plant to be examined ga Xa ab Co Av dg A1 St ec Sh Branch cn 7th post 1.9 0 0 0 0 5 3 5 4 5 4 2 0 7th post 0.5 0 0 0 0 4 3 4 5 5 3 0 0 5th post 2.0 - - - - 5 - 4 5 - - - - 5th post 1.0 - - - - 4 - 4 4 - - - - 5th post 0.5 - - - - 4 - 4 3 - - - - 5th post 0.25 - - - - 4 - 4 3 - - - - 11th post 2.0 - - - - 5 - 4 4 - - - - 11th post 1.0 - - - - 4 - 4 4 - - - - 11th post 0.5 - - - - 4 - 4 4 - - - - 11th post 0.25 - - - - 4 - 4 3 - - - -

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Example 27

In this example, the selective herbicidal activity of the compositions of the present invention is demonstrated.

The compound to be tested is described in Example 23 (d) in Example 5 (d). The compound is formulated as described for Compound.

160 ml of a solution of methyl cyclohexanone (21.8 g / l "Span" 80) and 78.2 g / l of "Tween" 20 are diluted to 500 ml with water. Trademark surfactant product containing "Span" 80 ¹⁰ sorbitol monolaurate. "Tween" 20 is a trademark of a surfactant containing 20 moles of condensation product of sorbitol monolaurate with ethylene oxide. The appropriate amount of test compound taken up in 5 ml of the above emulsion ^{of 15} ban.

Dilute 5 to 5 ml portions of the test compound with water to 40 ml and dilute to VIII with water. Sprays are sprayed on young specimens of the test plants listed in Table I (post-emergence test) at 1000 liters per hectare. Damage to plants 21. days are scored using a 0-9 scale (where 0 = 0-10% damage and 9 = total death). The degree of herbicidal damage is given by comparison with untreated control plants and results are reported in Table VIII. are summarized in Table.

Notation indicates that no experiment has been performed.

VIII. The abbreviations for test plants in Table 1 are as follows:

bay = winter wheat T = spring barley Av = Avena fatua A1 = Alopecurus myosuroides St = Setaria viridis

VIII. table

Serial number of test compound Rate of application (kg / ha) oB Tá Plant to be examined Av A1 St 5th 0.10 0 0 9 8 6 5th 0.20 1 1 9 9 8 5th 0.40 0 I 9 9 9 7th 0.03 0 1 8 8 8 7th 0.04 0 C 9 9 8 7th 0.08 1 1 - - - 7th 0.16 0 1 - - - 10th 0.04 0 I 9 9 8 10th 0.08 1 2 - - - 10th 0.16 2 5 - - - 15th 0.08 0 1 9 6 7 15th 0.16 1 1 - - - 15th 0.32 1 3 - - - 18th 0.03 0 1 9 9 8 18th 0.04 0 1 9 8 8 18th 0.08 - - 9 9 9 18th 0.16 0 0 - - - 60th 0.04 - - 9 8 9 60th 0.06 0 6 9 8 9 60th 0.08 0 5 9 8 9 60th 0.16 0 8 - - - 60th 0.32 0 9 - - - 62nd 0.02 - - 9 7 9 62nd 0.04 - - 9 9 9 62nd 0.06 0 5 9 9 9 62nd 0.08 0 7 9 9 9 62nd 0.16 0 9 - - - 62nd 0.32 0 9 - - 72nd 0.04 - - 9 9 9 72nd 0.06 0 0 9 9 9 72nd 0.08 0 3 9 9 9 72nd 0.16 0 7 - - - 72nd 0.32 1 9 - - - 78th 0.04 - - 9 7 8 78th 0.06 0 0 9 8 9 78th 0.08 0 2 9 9 9 78th 0.16 0 7 - - - 78th 0.32 0 9 - -

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Claims (10)

Claims 1. Herbicide, wherein the active ingredient comprises cyclohexane-l, 3-dione derivative origin ^{of 5%} an amount of from 0.002% to 95, comprising: (I) wherein R ¹ is hydrogen, C 2 -C 6 pentanoyl, or benzoyl optionally substituted with one or two nitro groups, or an alkali metal or transition metal cation; - R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, C 2 -C 6 haloalkenyl, or optionally substituted on the benzene ring with one or two halogen atoms benzyl; - R ³ is C 1-6 alkyl and - n is 2, 3, 4 or 5 in an inert solid support material - preferably granules ₂₀ or powder mineral or a clay, preferably kaolin, silica, silica, attapulgite or pyrophyllite - and / or a liquid diluent - for example, aromatic hydrocarbons, particularly preferably anisole, toluene, xylene or chlorobenzene, and optionally a cationic, anionic or nonionic surfactant, preferably a condensation product of ethylene oxide with an alkyl phenol and / or an alkaline earth metal salt of arylsulfonic acid. (Priority: May 25, 1982) 2. An herbicide comprising from 0.002 to 95% by weight of an active ingredient of a cyclohexane-1,3-dione derivative having the formula (I) - ^R1 is hydrogen, C2-6 alkanoyl or optionally one or two nitro groups, or benzoyl optionally substituted ³⁵ alkali metal cation; R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, or benzyl optionally substituted on the benzene ring with ⁴⁰ or two halogen atoms; - R ³ is C 1-6 alkyl and - n is 2, 3, 4 or 5 inert solid carriers, preferably particulate ⁴⁵ or powdered minerals or clays, particularly talc, kaolin, silica, silica, attapulgite or pyrophyllite and / or liquid diluents, preferably water, or an aromatic hydrocarbon, particularly preferably anisole, toluene, ⁵⁰ xylene or chlorobenzene, and optionally a cationic, anionic or nonionic surfactant, preferably a condensation product of ethylene oxide with an alkyl phenol and / or an alkaline earth metal salt of arylsulfonic acid. (Priority: November 20, 1981) ⁵⁵ The herbicide according to claim 1, characterized in that it contains as active ingredient a compound of the formula (XXIV) which is a narrower group of compounds of the formula I R ¹ is hydrogen, C 2 -C 6 -alkanoyl, or benzoyl optionally substituted with one or two nitro groups, or an alkali metal or transition metal cation; - R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, C 2 -C 6 haloalkenyl, or one or two halogen atoms in the benzene ring optionally substituted benzyl; - R ³ is C 1-6 alkyl and - n is 0, l or 2. (Priority: May 1982) 25.) The herbicide according to claim I, characterized in that it contains as an active ingredient a compound of the formula (XXI) which is a narrower group of compounds of the formula I R ¹ is hydrogen, C 2 -C 6 alkanoyl, or sodium or potassium; - R ² is C 1 -C 4 alkyl, C 2 -C 4 alkenyl *, C 3 -C 4 alkynyl, C 1 -C 4 haloalkyl or C 2 -C 4 haloalkenyl, and - R ³ is C 1-4 alkyl. (Priority: May 25, 1982) The herbicide according to claim 1, characterized in that it contains as active ingredient a compound of the general formula (XXII) which is a narrower group of the compounds of the formula I - R ¹ is hydrogen, C 2 -C 6 alanyl or sodium or potassium; - R ² is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl, C 1 -C 4 haloalkyl or C 2 -C 4 haloalkenyl, and - R ³ is C 1-4 alkyl. (Priority: May 25, 1982) The herbicide according to claim 1, characterized in that it contains as active ingredient a compound of the general formula (XXIII) which is a narrow group of the compounds of the formula I R ¹ is hydrogen, C 2 -C 6 alkanoyl, or sodium or potassium; - R ² is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl, C 1 -C 4 haloalkyl or C 2 -C 4 haloalkenyl, and - R ³ is C 1-4 alkyl. (Priority: May 25, 1982) The herbicide according to claim 1, characterized in that it contains as active ingredient a compound of the formula (XXV) which is a narrower group of the compounds of the formula I - R ² is ethyl, allyl, propargyl or 3-chloroallyl, and - R ³ is methyl, ethyl or propyl. (Priority: May 25, 1982) A process for the preparation of a compound of formula (I) for use as an active ingredient in a herbicidal composition according to claim 1, wherein - R ¹ is hydrogen, C 2 -C 6 alkanoyl or optionally substituted with one to three halogen, nitro, methyl and / or methoxy substituents, an alkali metal cation, a transition metal cation or an ammonium ion of formula (R *) ₄ N ⁺ wherein R ^{4 is C} 1-6 alkyl; - R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, C 2 -C 6 haloalkenyl, or optionally substituted on the benzene ring; -271 190,819 or two benzyl groups bearing two halogen and / or nitro substituents; - R ³ is C 1-6 alkyl and n is 2, 3, 4 or 5, characterized in that the benzaldehyde derivative j (V) is reacted with acetone, the resulting ketone derivative (VI) is reacted with the malonic acid ester derivative (VII), the resultant (IX) reacting a 5- (substituted phenyl) cyclohexane-1,3-dione derivative of the formula (II) with an acid anhydride (XIV) or an acid halide (XV) to give the 2-acyl-5- (substituted phenyl) cyclohexane (XIII) reacting the -1,3-dione derivative with an alkoxyamine derivative of Formula XVII and reacting the compound of Formula II thus obtained, which is a narrower group of compounds of Formula I, with a compound of Formula XX; or reacting the 5- (substituted phenyl) cyclohexane-1,3-dione derivative of formula (IX) with an acid anhydride of formula (XIV) or an acid halide of formula (XV) to give the 2-acyl-5- (substituted phenyl) cyclohexane-1,3-dione is reacted with an alkoxyamine derivative (XVII) and the resulting compound (II) is a narrower compound of formula (I) (XX) with a compound of the formula; or α ₃ ) reacting a 2-acyl-5- (substituted phenyl) -cyclohexane-1,3-dione derivative of formula (XIII) with an alkoxyamine derivative of formula (XVII); reacting a compound of formula (II), which is a narrow class of compounds of formula (II), with a compound of formula (XX); or j) reacting a compound of formula (II) which is a narrower compound of formula (I) with a compound of formula (XX) - in the above formulas, R ¹ , R ² , R ³ and n are as defined in the scope of the present claim; R is C 1-6 alkyl; Hal is halogen and L is a leaving group, preferably halogen. (Priority: May 25, 1982) 9. A process for the preparation of a compound of formula I for use as an active ingredient in a herbicidal composition according to claim 2, wherein R ¹ is hydrogen, C 2 -C 6 alkanoyl, or benzoyl optionally substituted with one or two nitro groups, or an alkali metal cation; - R ² is C 1 -C 5 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 5 haloalkyl, or benzyl optionally substituted on the benzene ring by one or two halogen atoms; - R ³ is C 1-6 alkyl and - n is 2, 3, 4 or 5 - characterized in that the benzaldehyde derivative j (V) is reacted with acetone, the resulting ketone derivative (VI) is reacted with the malonic acid ester derivative (VII), reacting a 5- (substituted phenyl) cyclohexane-1,3-dione derivative of the formula (II) with an acid anhydride (XIV) or an acid halide (XV) to give the 2-acyl-5- (substituted phenyl) (XIII) - cyclohexane-1,3-dione is reacted with an alkoxyamine derivative (XVII) and the resulting compound (II), which is a narrower group of compounds of formula (I), is reacted with a compound of formula (XX) ; or j (IX) with a 5- (substituted phenyl) cyclohexane is reacted with l, 3-dione derivative (XIV) with an acid anhydride or (XV) with an acid halide represented by the formula to yield (XIII) offers two ^25-acyl general formula The 5- (substituted phenyl) -cyclohexane-1,3-dione is reacted with an alkoxyamine derivative (XVII) and the resulting compound (II) is a narrower compound of formula (I). ) With ³⁰ alpha compounds; or reacting the 2-acyl-5- (substituted phenyl) -cyclohexane-1,3-dione derivative of formula (XIII) with an alkoxyamine derivative of formula (XVII) and then reacting the resulting compound of formula (I) ³⁵ subclass képle'ű narrower group of compounds which is (II), (XX) with a compound of formula; or reacting ₄ J with a compound of formula (II), which is a narrower group of compounds of formula (I), with a compound of formula (XX) ⁴⁰ - in the above formulas, R ¹ , R ² , R ³ and n are as defined in the scope of the present claim; R is C 1-6 alkyl; Hal is halogen and L is a leaving group, preferably ⁴⁵ halogens. (Priority: November 20, 1981) A process for the preparation of a compound of general formula (XXV) as defined in claim ^8, wherein ⁵ θ - R ² is ethyl, allyl, propargyl or 3-chloroallyl. and - R ³ is methyl, ethyl or propyl group, characterized in that using the corresponding starting materials. (Priority: May 25, 1982)