IE44291B1 - 3,4-diphenyl-1.2.5.6-tetrahydrobenzoic acid derivatives - Google Patents

3,4-diphenyl-1.2.5.6-tetrahydrobenzoic acid derivatives

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IE44291B1
IE44291B1 IE1795/76A IE179576A IE44291B1 IE 44291 B1 IE44291 B1 IE 44291B1 IE 1795/76 A IE1795/76 A IE 1795/76A IE 179576 A IE179576 A IE 179576A IE 44291 B1 IE44291 B1 IE 44291B1
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alkyl
radical
unsubstituted
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Ciba Geigy Ag
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Priority claimed from CH1066575A external-priority patent/CH617421A5/en
Priority claimed from CH1066675A external-priority patent/CH617423A5/en
Priority claimed from CH1066475A external-priority patent/CH617418A5/en
Application filed by Ciba Geigy Ag filed Critical Ciba Geigy Ag
Publication of IE44291L publication Critical patent/IE44291L/en
Publication of IE44291B1 publication Critical patent/IE44291B1/en

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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
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    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
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Abstract

Derivatives of 1,2-Diphenyl-cyclohex-1-ene-4-carbpxylic acid, their salts and their esters are effective plant growth-regulating agents. They may inter alia be used to control wild oats and to inhibit the growth of suckers in tobacco plants.

Description

The present invention relates to 3,4-diphenyl-l,2,5,6tetrahydrobenzoic aoid derivatives having plant growth regulating properties.
The present invention provides plant growth regulant 5 compositions which contain, as active ingredient, a compound of the formula I wherein each of 0, V, w, X, Y and z, which may be the same or 10 different,represents hydrogen, halogen, C^-C^ alkyl, C-^-C^ alkoxy, Cj_-C4 alkylthio, NOj, CF3, COOH, CN, OH, SO3H, NH2 or -NH(C1-C4 alkyl) or N(C^-C4 alkyl)j, and each of U and X in addition can represent an unsubstituted phenyl radical, and G represents a group of the formula -0R°, OR or -SR, and R° represents hydrogen or a cation Μ n © , wherein M represents an alkali or alkaline earth cation or a cation of iron, copper, zinc, menganese, nickel or represents an ammonium radical of formula - 2 44382 © Rl— N- R4 /\ R2 R3 (in which each of R^, Rg, Rg and R^, which may be the same or different, represents hydrogen, benzyl or a C^-Cg alkyl radical which is unsubstituted or substituted by -OH, “NHg or C^-C4 alkoxy) and n is 1, 2 or 3 and is the valency of M, and represents a C^-C^g alkyl radical which is unsubstituted or substituted by halogen, nitro, cyano, C^-Cg alkoxy, Cg-Cg alkoxyalkoxy, Cg-Cg alkenyloxy, C^-Οθ alkylthio, Cg-Cg alkanoyl, Cg-Cg acyloxy, Cg-Cg alkoxycarbonyl, carbamoyl, bis(C1-C4 alkyl)- amino, tris(C1-C4 alkyl)ammonium, Cg-Cg cycloalkyl, Cg-Cg cycloalkenyl or by a phenyl, phenoxy or 5- or 6membered heterocyclic ring containing 1 to 3 heteroatoms which phenyl or phenoxy group or heterocyclic ring is unsubstituted or substituted by halogen, C1-C4 alkyl or εχ-04 alkoxy,· a Cg-C13 alkenyl radical which is unsubstituted or mono- to tetra-substituted by halogen or mono-substituted by phenyl or methoxycarbonyl? a Cg-Cg alkynyl radical; a Cg-C12 cycloalkyl radical which is unsubstituted or substituted by halogen or C^-C4 alkyl; a Cg-Cg cycloalkenyl radical; a phenyl radical which is unsubstituted or 4429 J substituted by halogen, cj~C^ alkyl, C^-C^ alkoxy, σ,-Cj alkylthio, N02, CF.J, COOH, CN, OH, SO3H, NH2 or -NH(C^-C^ alkyl) or -NfC^-C^ alkyl)2? or a 5- or 6-membered heterocyclic ring containing 1 to 3 heteroatoms, together with a solid extender and, optionally, a surface active agent or together with a liquid diluent and a surface active agent.
The active substances of the formula ί are accordingly. 10 subdivided into the free carboxylic acids, the Salts, the esters, and the thiol esters thereof.
In the above definitions, halogen denotes fluorine, chlorine, bromine or iodine.
Depending on the number of carbon atoms indicated, the term alkyl” by itself, or as moiety of a substituent, can mean for example: methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, sec. butyl, tert, butyl, and the isomers of pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, penta- 4 44291 decyl, hexadecyl, heptadecyl and octadecyl.
Depending on the number of carbon atoms indicated, alkenyl radicals by themselves, or as moiety of a substituent, are for example·, allyl, crotyl, methallyl, and isomers of 5 butenyl, pentenyl, hexenyl, heptenyl, octenyl. However, those alkenyl radicals which contain two or three double bonds (alkadienyls, alkatrienyls) are also to be understood as falling under this definition, for example butadienyl, pentadienyl, hexadienyl, heptatrienyl etc, ' By a carbamoyl radical as substituent of an alkyl group is meant e.g. a radical -NH-CO-OR5 or the radical __R5 -O-CO-N 3 o wherein R^ represents a C^-C^ alkyl radical or a phenyl group and Rg represents hydrogen or a C^-C^ alkyl radical.
A tri (C^-C^ alkyl)ammonium radical is an amine of cationic character which is substituted by three alkyl groups which can be the same or different. Possible anions are customary acid radicals, such as fluorides, chlorides, - 5 442S1 bromides, iodides (these latter also in the form of Br^ ® , I3 θ)j an8 also cyanide, thiocyanide, phosphate, nitrite, nitrate, chlorate, perchlorate, borate, and radicals of sulphur-containing acids, such as sulphonate, sulphite, hydrogen sulphate, sulphate, which can also be substituted by lower alkyl groups;’for example CHgO-SOg® or CgHgO-SOg ® .
Cg-Cg Cycloalkenyl radicals are cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl. ! ]_q Examples of Cg-Cg and Cg-Cgg cycloalkyl radicals are: cyclopropyl, .cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl.
Gg-CgAlkynyl radicals contain a triple bond in the terminal position or in one of the other possible chain positions. Examples are: propargyl,butynyl, hexynyl,octynyl, Five- to six-membered heterocyclic rings can contain nitrogen, oxygen and/or sulphur atoms as heteroatoms. Optionally they have aromatic character, but they can also be completely or partially hydrogenated. As examples there maybe cited; pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, morpholine, thiomorpholine, 1,2,4-6 44201 and 1,3,5-triazine and the hexahydro derivatives thereof; thiadiazine, pyrane; furane, thiophene, pyrrole and the tetrahydro derivatives thereof; thiazole, oxazole, carbazole, imidazole, imidazoline, imidazolidine, thiadiazole, thiadiazoline, thiadiazolidine.
An acyloxy group containing 2 carbon atoms denotes the acetoxy group and an alkoxycarbonyl group containing 2 carbon atoms denotes methoxycarbonyl. Alkali metals and alkaline earth metals as ions of the free carboxylic acids are in particular lithium, sodium, magnesium, calcium, strontium, barium.
The compound l,2-diphenyl-cyclohex-l-ene-4-carboxylic rt acid, which may also be termed 3,4-diphenyl-Δύ -tetrahydrobenzoic acid, is known [Liebigs Ann. 570, 201 (1950)].
No mention is made in the literature of a plant-influencing activity. Such an activity only becomes clearly evident when salt formation occurs, for example with the formation of the trimethylbenzylammonium salt. This activity occurs particularly clearly in respect of the esters and thioesters.
The Invention also provides the new compounds of 44391 the formula I in accordance with the-above definition, with the proviso, that at least one of the substituents U, V, W, X, Y or Z has a meaning different from hydrogen if G represents the substituent -OH. The invention also provides a method of Influencing plant growth, which comprises applying to plants or the locus in which they are growing compounds of the formula I especially the new compounds as defined in this paragraph.
Formula I includes- compounds wherein G represents a group of the formula -0R° or a group of the formula OR. Preferably the invention provides compounds of the formula I, a process for preparation, a method using them and compositions which contain them as active ingredient, wherein G represents a group -OR, and R represents a C^-C? alkyl radical which.is unsubstituted or substituted by halogen, cyano, C^-C^ alkoxy, 0χ-04 alkylthio, C^-Cg alkoxycarbonyl, by a C^-Cg aliphatic carbamoyl group, by an amino, mono-(C^-cp alkylamino, di(C^-cpalkylamino or tri(0^-0^)alkylammonium group, by a Cg-Οθ cycloaliphatic radical or by a phenyl or phenoxy group which is unsubstituted or substituted by halogen, C^-C^ alkyl or C^-C^ alkoxy, or by a 5to 6-membered heterocyclic ring containing 1 or 2 heteroatoms? a Cg-C? alkenyl radical which is unsubstituted or mono- to tetra- substituted by chlorine or bromine? a propynyl or butynyl radical; a C3-Cg cycloalkyl radical which is unsubsCituted or substituted by chlorine, bromine or methyl; a phenyl radical which is unsubstituted or mono- to trisubstituted by halogen, C^-C^ alkyl, C^-C^ alkoxy, C.^ alkylthio, NO2, CFp COOH, CN,' OH, SOgH, NH2 or -NHCCj-C^·alkyl) or -NCC^-C^ alkyl)2; or a a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms; whilst U, V, W, X, Y and 2 are as defined hereinbefore.
This group of compounds shall be designated subgroup Ia.
Within this group la, a subgroup of compounds with interesting activity is that in which U, V, W, X, Y and Z represent hydrogen, halogen, C^-C^ alkyl, C^-C^ alkoxy, methylthio, ethylthio, N02, CFg, COOH, CN, OH, SOgH, NHg, methylamino, ethylamino, dimethylamino, diethylamino or methylethylamino, whilst R is as previously defined. This more narrowly defined group shall be designated subgroup lb 2q An important subgroup within group Ib comprises those compounds in which U, V, W, X, Y and 2 represent hydrogen. This more narrowly defined group shall be designated subgroup Ic. A subgroup of compounds with interesting 4 291 activity belonging to the thioester series within the scope of the formula I is that in which U, V, W, X, Y and Z represent hydrogen and R represents a Cj-C? alkenyl radical or represents a C^-Cy alkyl radical which is unsubstituted or substituted by a C^-C^ alkoxy group. This last mentioned group is designated subgroup Id.
Esters of l,2-diphenyl-cyclohex-l-cyclohex-l-ene-4carboxylic acid which are very great biological importance are the 2-bromoethyl, neopentyl-(=l-ethylpropyl), 2-trichloroethyl, iso-butyl, 2-fluoroethyl, 2-dimethylaminoethyl and methylthio ester, hut especially the methyl ester (compound 2,1). _ . ' The compounds of the formula I include those in which represents a group of formula -SR and unsubstituted or substituted by C^-Cg alkoxy, C2~Cg alkoxycarbonyl, Cg-Cg cycloalkyl or by a phenyl radical or a 5- or 6-membered heterocyclic ring containing 1 to 3 heteroatoms. which phenyl radical is unsubstituted or substituted by halogen, C^-C^ alkyl or C^-C^ alkoxy; a Cg-C^2 alkenyl radical a Cg“Cl2 cycloalkyl radical which is unsubstituted . or substituted by C^-C^ alkyl; a phenyl radical which is unsubstituted or substituted 44381 by halogen, C^-C^ alkyl, C|-C4 alkoxy, C^-C4 alkylthio, NO2 or CFg, or a 5- or 6-membered heterocyclic ring containing 1 to 3 heteroatoms.
The invention also provides a process for the preparation of the compounds of the formula I, which comprises reacting acrylonitrile, acrylic acid, or a derivative of acrylic acid of the formula II CH2=CH-CO-G (II) wherein G is as defined for the compounds of formula I, with a diene of the formula III in a Diels-Alder reaction which is followed, when acrylic acid is used, if desired by an esterification with the appropriate alcohol R-OH or a reactive derivative thereof, or by an esterification with a thiol R-SH or a reactive derivative thereof, to obtain corresponding esters, and when acrylonitrile is used, by conversion of the nitrile group of the product obtain into a group of formula CO-G e.g. by a saponification of the nitrile group to give the carboxyl group followed by optional esterification thereof. The diene of the formula III may be formed in situ by elimination of 2 moles of water from - 11 44391 a diol of the formula Ilia (Ilia) in a modified Diels-Alder reactiori (c.f. Proc. Chem. Soc. .1963, 217). The substituents U, V, W, X, Y and Z in the formulae III and Ilia are as defined for formula I.
The process of the invention is consequently a cyclisation reaction in the presence of a functional acid group, which in turn is either in the form of an.acid or ester group, or, if desired, can be converted into such a group after the cyclisation is complete. - 12 4 4 291 It will be readily understood that there are a number of ways of accomplishing this ester formation which is necessary before or after cyclisation.
The following possibilities are cited as examples: a) reaction of -COOH with the halide, preferably chloride 5 or bromide, R-halogen in the absence, but preferably in the presence, of a base; b) reaction of -COOH with the alcohol R-OH in the presence of acid catalysts (HCl, H2SO^, Lewis acids); . c) transesterification of -COOR' (OR* is any alcoholic or phenolic group) with an excess of the desired alcohol R-OH, preferably also in the presence of an acid catalyst d) reaction of a basic reactive acid derivative -COX with the alcohol R-OH or the thioalcohol R-SH or the alkali salt thereof, wherein X represents a halide or another readily removable radical, such as benzene sulphate, tosylate or mesylate.
Acid halides are customarily obtained by halogenating the carboxyl group with, for example, SOgClj, COC12, (COCl)2, PClgj PBr^ or SF^.
The conversion of a l,2-diphenyl-cyolohexene-4carboxylic acid (G=OH) into salts Is carried out in conventional manner with a corresponding base defined in for- 13 * 44281. -mula I.
The cyclisation process of this invention may be carried out at normal pressure or elevated pressure in the temperature range between 80° and 200°C, preferably between 120° and 150°C, in solvents which are suitable for DielsAlder reactions, such as hydrocarbons (benzene, toluene, xylenes) [cf. H. Wollweber Diels-Alder-Reaktionfin, Georg Thieme Verlag, Stuttgart, 1972], The process, however, can also be carried out in the absence of a solvent.
' When using compound Ilia, the addition of dehydrating agents (splitting off of 2 moles of water) is necessary to form compound III as intermediate. It is possible to use conventional agents, such as AlgOg) p-toluenesulphonic acid, KHSO^, acetic anhydride/sodium acetate etc., for the de15 hydration.
The starting products of the formulae III and Ilia are partly known compounds are they can be obtained by methods which are known per se. for example; Grignard” reaction of the corresponding benzil derivatives CHg-Mg-halogen—> Ilia halogen ¢= preferably Cl [Bull. Soc. chim France 43, 873 (1928)] - Dimerisation of the corresponding acetophenone derivative a) electrochemically, b) by irradiation (h« ν), c) in the presence of aluminium powder U,X CO - CH '3 > Ilia w,z' a) [J. Am. Chem. Soc. 75, 5127 (1953)] b) [Tetrahedron 25, 4501 (1969)] c) [J. Org. Chem. 37, 2367 (1972)] - To prepare the optionally unsymmetrica] compounds of the 10 formula III or Ilia, in which U, V and W can have a meaning which is different from that of X, Y and Z, it is advantageous to carry out a Grignard reaction in one or two reaction steps with diacetyl, in accordance with the scheme U CH, I 3 co V Mg - halogen [J. Org. Chem. 28, 2154 (1963)] Mg - halogen Ilia halogen « preferably Cl -44391 The following Examples illustrate the process of the present invention including the manufacture of the starting products. The parts are parts by weight. Further compounds of the formula I which were obtained by the described process are listed in the subsequent table.
' ' Example 1 a) (1st method) A mixture of 50 parts of 2,3-diphenyl-2j3-dihydroxybutane and 0.5 part of freshly dehydrated KHSO^ is distilled for 50 minutes at 11 Torr and 200°C bath temperature. The fraction which is collected within the boiling range of 150ο-180°0/11 Torr yields 43.8 parts of crude 2,3-diphenyl1,3-butadiene. The product is stirred dire'ct with 21,5 parts of acrylic acid and 2 parts of hydroquinone under a nitro15 gen atmosphere for 3 hours at 130° to 140°C.
The cooled reaction product is treated with diethyl ether and extracted with 1 normal NaOH. The aqueous phase is acidified with concentrated hydrochloric acid and extracted with diethyl ether. The organic phase is dried over NagSO^ 44391 and concentrated in vacuo to yield 21 parts of 3,4-diβ phenyl--tetrahydrobenzoic acid with a melting point of 136°-140°C. b) (2nd method) A mixture of 7.2 partsof 2,3-diphenyl-2,3-dihydroxybutane, 3.2 parts of acrylic acid, 0.1 part of p-toluenesulphonic acid and 0.3 part of hydroquinone is dissolved in 12 parts of acetone and the solution is kept for 25 minutes in a Carius tube. The solution is concentrated in vacuo and the oily residue is worked up as described in a) above to yield 2.2 parts of 3,4-diphenyl-A -tetrahydrobenzoic acid with a melting point of 136°-140°C [Compound 1.1], The following salts for example of this compound can be prepared: Compound Cation M 1.2 Na+ m.p. )>250oC 1.3 1/2 Cu^ . m.p. >250°C 1.4 1/3 Fe+ + + 20 1.5 1/2 Ni+ + 1.6 1/2 Zn+ + 1.7 1/2 Mg+ + - 17 44391.
Compound Cation 1.8 1/2 Ca+ + 1.9 ®n(ch3)4 1.10 ®NH2(CH2-CH2-OH)2 m.p. 80 - 87°C 1.11 ® NH(CH2-CH2-OH)3 m.p. 83 - 86°C 1.12 ©N(nC4H9)4 oil 1.13 ©βι3(^8η17) m.p. 98 - 99°C 1.14 (ch3)3n-ch2-c6h5 resinous The following compounds of the formula Ie can be obtained 10 in the same way and the corresponding salts thereof by reaction with a base: (Ie) 4 3 91 Com- pound U V W Physical constant 1.15 4 - Cl H H m.p. 170 - 180°C 1.16 3 - CHg H H m.p. 112 - 116°C 1.17 4 - CHg H H m.p. 146 - 148°C 1.18 3 - COOH H H 1.19 4 - Phenyl H H m.p, 150 - 155°C 1.20 2 - Cl 4-C1 H 1.21 3 - Cl 4-C1 H 1.224 - C2H5 H H 1.23 2 - Cl 3-C1 4-C1 1.24 4-nC4ll9 H H 1.25 4-nC4H90 H H 1.26 4-SOgH H H 1.27 4-CN H H 1.28 4-N(CHg)2 11 H 1.29 3-N02 H H 1.30 3-CHgO H . H' 1.31 3-CHgO 5-Cl^O H 1. 32 2-CHg 4-CHj H 1.33 4-Br H H m.p. 135 - 140°C 1.34 3-Br H H semicrystailine 1.35. 3-CFg H H 44391 Example 2 A mixture of 57 parts of 3,4-diphenyl-Δ -tetrahydrobenzoic acid and 5 parts of concentrated ^SO^ is kept for 18 hours in 500 parts by volume of methyl alcohol at reflux temperature.
The solution is concentrated in vacuo and the oily residue is covered with a layer of ether and neutralised with 2 normal NaOH. The separated organic phase is dried over · Na^SO^ and concentrated in vacuo to yield 57 parts of 3,410 diphenyl- Δ3 -tetrahydrobenzoic acid methyl ester.
Boiling point: 121° - 125°C/O.OO1 Torr.
C H calculated: 82.16 % 82.19 % found : 6.90 % 7.06 % Example 3 A mixture of 7.2 parts of 2,3-diphenyl-2,3-dihydroxyhutane, 3.8 parts of acrylic acid methyl ester, 0.1 part - 20 4429 1 of p-toluenesulphonic acid and 0.3 part of hydroquinone dissolved in 12 parts of acetic anhydride is kept in a Carius tube for 24 hours at 130° - 140’C. The reaction product is distilled to yield 2.3 parts of 3,4-diphenyl5 Δ3 -tetrahydrobenzoic acid methyl ester.
Boiling point: 121° - 125°C/0.001 Torr.
Example 4 a) Manufacture of a starting product 27.8 parts of 3,4-diphenyl- Δ3 -tetrahydrobenzoic acid are suspended in a mixture of 60 parts by volume of abs. chloroform and 0.8 part of dimethyl formamide. Then 15.5 parts of thionyl chloride are added dropwise at 0°C in the course of 5 minutes. The mixture is stirred at 0°C for 15 minutes at room temperature and stirred for 20 minutes at 40°C. The clear, yellow solution is concentrated in vacuo and dried in a high vacuum at 50°C to yield 29 g of 3,4-άΐρ1ιεηγ1-Δ3 -tetrahydrobenzoyl chloride.
Boiling point: 16O°C/O.OO5 Torr. - 21 4 4 2 91 b) A solution of 14.25 g (0.048 mole) of 3,4-diphenyl-Δ^ tetrahydrobenzoyl chloride in 80 ml of abs, ether is added dropwise at room temperature to a solution of 2.4 g (0.04 mole) of 1-propanol, 80 ml of abs. ether and 5 ml of pyridine. After 5 hours the reaction mixture is filtered through silica gel. The end product, 3;4-diphenyl-cyclohex-3-ene-l-carboxylic acid-n-propyl ester is eluted with petroleum ether/ether (2:1) and distilled in vacuo.
Yield: 7.2 g; b.p. (0.01 Torr) 150°C (in a bulb tube). ' n25= 1.5665.
The following compounds of the formula I are obtained in this manner or by one of the other methods indicated hereinabove: (If) 44391 Compound R Physical constant 2.1 ch3 b.p. 121-125°C/0.001 Torr 2.2 c2h5 n20 1.5802 2.3 n-O3H7 n25 1.5665 2.4 isoC-gH? b.p. 165-170°C/0.0l Torr 2.5 n-C4Hg nJ5 1.5617 2.6 sec. C4Hg n25 1.5560 2.7 tert.C4Hg nJ5 1.5430 2.8 3-C5Hh n20 1.5560 2.9 η-0δΗι? n20 1.5270 2.10nC12H25 n20 1.5179 2.11nC18H37 m.p. 45 - 47°C 2.12 2-bromoethy1 „20 nD 1.5708 2.13 6-chlorohexyl(n) „20 nD 1.5625 2.14 3-nitrobutane-2-yl n25 1.5585 2.15 2,2,2-trichloroethyl n^° 1..5800 2.16 2-cyanoethyl m.p. 77 - 80°C 2.17 2-methoxyethyl η2θ 1.5691 2.18 2-n-butoxyethyl n20 1.5575 2.19 3-ethoxypropyl n20 1.5600 2.20 2[2-butoxyethoxy]ethy1 n25 1.5485 2.21 2-allyloxyethyl n20 1.5652 44391 .
Compound R Physical constant 2.22 2-n-octylthioethyl n^° 1.5523 2.23 3-acetylpropyl n^5 1.5636 2.24 -CH,-CH„-O-C-CH=CH, 2 2 II 2 0 np° 1.5640 2.25 2-fluoroethyl m.p. 65 - 66°C 2.26 2-chloroethyl m.p. 69 - 70°C 2.27 2-iodoethyl nJ5 1.6072 2.28 3-chloropropyl(n) np5 1.5753 2.29 3-bromopropy1(n) Πρ5 1.5845 2.30nC5Hll nJ5 1.5557 2.31 isoC.HL 4 9 n25 1.5592 2.32 1-ethoxycarbonyl-ethyl n^° 1.5570 2.33 3-N,H-dimethylaminopr opy 1 nj° 1.5675 2.34 (CH,), N-CH,CH,ff) 01Θ m.p. 210 - 212°C 2.35 cyclohexylmethy1 20 Up 1.5590 2.36 eyelooctyIme thyl n^5 1.5582 2.37 cyclohexene-(3)-1-y 1methyl nJ5 1.5697 2.38 3-phenylpropyl n^° 1.5873 2.39 2-[4-methoxyphenyl] ethyl m.p. 65 - 67°C 44281 Compound R Physical constant 2.40 2-phenoxyethyl 20 nD 1.5850 2.41 O~ch2- n25nD 1.5610 2.42 ι—ι k0>-CH2- 20 nD 1.5730 5 2.43 QLch2- oil 2.44 Q-CH2CH2- „20 nD 1.5892 2.45 / VcH,CH„<_/ 2 2 2° nD 1.5671 2.46 2-propenyl „20 D 1.5762 2.47 4-pentenyl „20 nD 1.5652 10 2.48 3,7-dimethyl-octa- 2,6-dien-l-yl „20 D 1.5594 2.49 l-chloroprop-2-yl „25 nD 1.5671 2.50 l-bromoprop-2-yl „25 nD 1.5822 2.51 l,4-dibromobut-2-yl oil 2.52 2,3-dibromopropyl(n) 25 nD 1.5865 15 2.53 9-octadecenyl „20 nD 1.5290 Compound R Physical constant 2.54 2-propynyl 20 rip 1.5806 2.55 3-hexynyl n20 1.5682 2.56 3-chloro-buten-(2)-l-yl n25 1.5741 5 2.57 3-pheny1-propen-(2)-l-yl n20 1.6065 2.58 cyclopropyl oil 2.59 cyclohexyl n20 1.5639 2.60 cyclooctyl n25 1.5632 2.61 cyclododecanyl m,p. 95 - 100°C 10 2.62 benzyl 20 np 1.5935 2.63 4-chlorobenzyl n20 1.5962 2.64 4-methoxybenzyl u20 1.5910 2.65 4-methyIbenzyl n20 1.5930 2.66 phenyl n20 1.5881 10 2.67 3-bromophenyl 20 n^ 1.6105 2.68 3}4-dichlorophenyl n20 1.5982 2.69 4-chloro-2-methylphenyl m.p. 118°C 2.70 4-methylthiophenyl oil 2.71 4-t-butylpheny1 ft20 1.5782 15 2.72 3-nitrophenyl n25 1.5940 2,73 4-sulphophenyl oil 2.74 3-cyanophenyl n25 1.5910 - 26 44291 Compound R Physical constant 2.75 3-trifluoromethylphenyl n25 1.5598 2.76 3-N,N- dime thylaminophenyl n25 1.6000 2.77 N-methylpiperidin-4-yl oil 2.72 tetrahydrofuran-3-yl m.p. 102 - 105°C 2.79 3-methoxycarbonyl-2methyl-prop-2-en-1-yl b.p. 210-215°C/0.001 Torr 2.80 2-N,N-dimethylaminoethyl b.p. 165°C/0.01 Torr 2.81 2-nitroethyl oil 2.82 cyclopropylmethyl oil 2.83 1-cyclopropyl-eth-1-yl n25 1.5643 The following compounds of the formula lg are also obtained in the manner of one of the methods indicated above: Com- pound U V W R - Physical constant 2.84 4-Cl H H ch3 D 1.5881 2.85 2.86 4-Cl -3-CH3 H H H HC2H5 ' ch3 20 nD 1.5684 2.87 2.88 3- CH3 4- CH3 H H H H c2k5 ch3 20 nD 1.5763 2.89 4-CH3 H H allyl 2.90 3-COOH H H CH3 2.91 4-phenyl H H ch3 m.p. 163-168° 2.92 2.93 2-Cl 4-Br 4-Cl H H H isoC3H/ CI13 20 nD 1.6180 2.94 4-C2H5 H H ch3 . 2.95 2.96 2- Cl 3- Br 3-Cl 11 4-Cl II c2H5 CH3 20 d 1.6085 2.97 3-CF3 H H ' CI13 2,98 4-SO3H H H θ2^5 2.99 4-CN 11 II CH3 oil 2.100 4-N(CH,)? H 11 ch3 2.101 3-N02 H H ch3 2.102 3-CH3O H H ch3 2,103 3~CH3O 5-CH3O 11 ch3 oil Example 5 2.3 parts of 3,4-diphenyl-Δ? -tetrahydrobenzoyl chloride are dissolved in 20 parts by volume of abs. diethyl ether.
At -5°C to 0°C and under a nitrogen atmosphere, a mixture of 0.95 part of benzylmercaptan and 0.6 part of abs. pyridine, dissolved in 10 parts by volume of ether, are added dropwise in the course of 10 minutes. The mixture is stirred for 30 minutes at 0°C and for 30 minutes at -room temperature. The reaction product is filtered and the fillo ter residue is washed with ether. The combined filtrates are washed with cold water, dried and concentrated in vacuo.
Yield: 2.2 parts of S-benzyl-3,4-diphenyl-Δ -tetrahydro thio 90 benzoate: n^ : 1.6099.
The following compounds of the formula lh are obtained in 15 this manner or by one of the methods indicated above: CO SR - 29 4 4 2 θ Compound R Physical constant 3.1 CH, m.p. 73 - 75°C 3.2C2H5 3.3 n-C3H7 3.4 isoCgH-, 25 n 1.5911 3.5nC4H9 n^5 1.5862 3.6 sec.C4E9 3.7 iso.C4H9 3.8 n-G5HLi n^5 1.5670 3.9 n-CgHi7 3.10n-CI2H25 3.11 2-me thoxye thy 1 3.12 2-n-butoxyethyl 3.13 1-ethoxycarbonylmethyl 3.14 3-phenylpropyl n^5 1.6052 3.15 2-propenyl 3.16 cyclohexyl m.p. 75 - 77°C 3.17 benzyl n^5 1.6099 3.18 4-chlorobenzyl n^5 1.6160 3.19 4-rne thoxybenzy1 3.20 phenyl m.p. 107 - 108°C 3.21 4-fluorophenyl Compound R Physical constant 3.22 4-bromo-3-methylphenyl m.p. 86 - 87°C 3.23 4-nitrophenyl 3.24 4-methoxyphenyl The active substances of the present invention of the formula I, and the corresponding compositions which contain them, intervene in the physiological processes of plant development and can be used for various purposes in connection with the increase in yield, ease of harvesting and labour-saving in measures taken on cultivated plants. The various effects of these active substances depend substantially on the time of application (from the ripening stage of the plant) and on the concentrations employed. However, these effects are in turn different de15 pending on the species of plant.
Compound structures of 4-phenyl-cyclohex-(3 or 4)ene-l-carboxylates are disclosed within a substantial group of compounds in general form in German Offenlegungsschrift 1,900,658. Anti-fertility properties are ascribed to such compounds, which appear to make them suitable for rodent con- 31 4429* trol. No particulars ara given on effects on plants. That compounds of the formula I of the present invention ace on plants is therefore completely surprising.
The active substances of this invention of the 5 formula I, and the compositions which contain them, influence the vegetative plant growth and sprout formation, flowering and fruit development. In addition, the supporting tissues of the stems of treated plants are strengthened.
The formation of undesired suckers in various plant species, for example tobacco plants, is very greatly diminished, and also the vegetative growth of vines is inhibited. The compounds of the present invention also promote secretion; for example the economically important latex flow from Hevea brasiliensis is stimulated. As experiments have shown, the rooting of cuttings and the tuber formation of potatoes are advantageously influenced. In many cultivations of ornamental and cultivated plants it is possible to control the time of flowering and the number of blossoms which is for example in pineapple plantations highly desirable.
If all the plants blossom simultaneously, then harvesting can take place within a comparatively short space of time. A displacement of the sex differentiation in the blossoms of cucurbitacaea, melon and cucumber plants in - 32 44291 favour of the female blossoms occurs. Influence on the sex differentiation can be employed in practice potentially, for example as an aid to hybridisation in seed cultivation or to increasing the yield, By influencing the flower-formation, sex differentiation and the vegetative growth, the active substances used according to the invention can substantially increase the yield of plants (e.g. fruit, seeds, leaves). For example, the vegetative growth of soya bean and other leguminous plants Ιθ is reduced and the generative growth promoted, whereby a direct increase in the yield is achieved. Experiments showed that a thinning of blossoms and fruits on fruit trees occurs. Furthermore, the ripening and colouring of fruit is accelerated and improved for example in stone fruits, oranges, melons, tomatoes, bananas, blueberries, figs, coffee, pepper and pineapples. The same applies to the ripening of other useful parts of plants, for example tobacco leaves. The formation of separation tissue greatly eases the detachment of fruit.
Special mention is also to be made of the possibility of inhibiting the growth of suckers in tobacco plants with the active substances of the present invention, when the leading shoot has been cut off shortly before flowering in - 33 44291 order to bring about the desired increase in growth of the leaves.
The principal kind of plant regulation, however, resides in the special property of the compounds of the formula I to effect in specific weeds a growth inhibition so pronounced that it approximates to a herbicidal action and the compounds can be used in practice for this purpose. When applied to a large number of monocotyledonous and dicotyledonous weeds (Setaria, Alopecurus,- Sinapis, Galium 10 · etc.), the compounds effect a stunted growth. From the point of view of maintaining cultivated land, this effect provides a particularly advantageous weed control to the extent that, independently of the growth of useful plants, a uniform, low plant cover is retained, which counteracts soil erosion by wind or water. The marked selective activity of the compounds of the formula I, which either has no effect on the important major crops, such as sugar beet, wheat, barley, rye and others, or even - as in types of cereals - increases the breaking strength of the plant 2o through slight growth reduction, results in an economically very interesting method of protecting cultivations of plants from the spread of weeds. A particularly advantageous feature of the compounds of the formula I is the pronounced - 34 44391 herbicidal-like growth inhibition of wild oats (Avena fatua). which are among the most important grass-like weeds in crops of useful plants, above all in cereals. Experience has shown wild oats to be among the most dif5 ficult weeds to control. They are controlled only imperfectly by a few herbicides, but not at all by the majority of commercially available herbicides.
The invention therefore provides simultaneously a method of controlling weeds in crops of useful plants by ' applying compounds of the formula 1, which cause stunted growth,or compositions which contain them.
Such a method of inhibiting plant growth does not bring about any change in the sense of a mutation in the life cycle of the plant which is determined by genetic characteristics.
The maintenance of pure grass cultivations, such as those In public parks and gardens, in urban areas, industrial sites, or along main roads, railway embankments or the embankments of water bodies, has to be'considered in connection with the reduction in growth of grasses. In all such cases it is normally necessary to cut the turf or grass periodically. This operation is not only time-consuming, complicated and expensive in respect of labour and machinery, but involves the personnel concerned and road users in considerable hazard in the traffic sector.
For this reason there is therefore an urgent need in areas with extensive traffic networks on the one hand to maintain and care for the grassy covering necessary for strengthening road shoulders and embankments on traffic routes, and on the other hand to keep it at reasonable height by simple means during the entire vegetation period. This need is fulfilled in a very advantageous manner by applying the compounds of the formula I, The active substances of the formula I can be applied to the surface to be treated simultaneously or successively with further active substances. These active substances can be both fertilisers, trace element agents or other preparations which influence plant growth. However, they can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of these preparations, if appropriate together with additional carriers or further additives which assist· application.
; The compositions according to the invention may be solid or liquid and may contain substances conventionally used in the art of formulation, for example; natural and regenerated substances, solvents, dispersing agents, slotting - 36 44291 agents, stickers, thickeners, binders or fertilizers.
For application, the compounds of formula X can be in the following application forms.
Solid preparations: dusts, tracking agents, granulates (coated granulates, impregnated granulates and homogranulates); Liquid preprations: a) water-dispersible active substance concentrates: wettable powders, pastes or emulsions; 1° · b) solutions.
To these mixtures can also be added additives.which stabilise the active substance and/or non-ionic, anionic and cationic substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (stickers) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Examples of suitable stickers are: olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyi cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols 2o having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (Carbowaxes-Carbowax is a Registered Trade Mark), fatty alcohol poly37 ethylene glycol ether having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation product of urea and formaldehyde, and also latex products.
Water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are compositions which can he diluted with water to any desired concentration. They consist of active substance, extender,optionally additives which stabilise the lo. active substance, surface-active substances and anti-foam agents and, optionally, solvents.
The content of active substance in the above described compositions is generally between 0.1 and 95%, preferably between 1 and 80%. Application forms can be diluted to as low a content of active substance as 0.001%. As a rule the rates of application are from 0.1 to 10 kg of active substance per hectare, preferably from 0.25 to 5 kg per hectare.
The active substances of formula I can be formulated for example in the following way: Dusts: The following substances are used for the preparation of a) a 5% b) a 2% dust: - 38 44391 a) 5 parts of active substance 95 parts of talcum b) 2 parts of active substance part of highly dispersed silicic acid 97 parts of talcum The active ingredients are mixed and ground with the extenders.
Granulate: The following substances are.used to obtain a 5% granulate: parts of active substance 0.25 parts of epichlorohydrin 0.25 parts of cetyl polyglycol ether 3.50 parts of polyethylene glycol parts of kaolin (particle size 0.3 - 0.8 mm) The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, then the polyethylene glycol and cetyl polyglycol ether are added. The resultant solution is sprayed onto kaolin and the acetone is subsequently evaporated in vacuo.
Wettable Powder The following ingredients arc used to prepare a 25% wettable powder. - 39 44291 parts of active substance, 4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5'parts of sodium dibuty! naphthalenesulphonate 19.5 parts of silicic acid., 19.5 parts of Champagne chalk, 28.1 parts of kaolin; The active substances are intimately mixed in suit 10 able mixers with the additives, and the mixture is then milled in appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of desired concentration.
Emulsifiable concentrates: The following substances are used to produce a % emulsifiable concentrate: 250 parts of active substance 150 parts of a condensation product of 1 mole of tributylphenol and 10 moles of ethylene oxide as wetting agent. The preparation is bulked to a volume of 1000 ml with xylene.
By diluting such concentrates with water it is possible to obtain emulsions of desired concentration which are - 40 suitable for application to plants to inhibit their growth.
To illustrate the plant growth influencing properties of the compounds of the formula I, the herbicidal/growth··inhibiting activity was determined by means of the following tests. 44281 Test A Herbicidal post-emergence application Weeds in the 2- to 6-leaf stage (or up to the tillering stage with grasses) which have been sown in pots and kept in a greenhouse are sprayed with an aqtieous emulsion of active substance (obtained from a 25% emulsifiable concentrate) in rates of application of 0.5 to 4 kg of active substance per hectare. The plants are then kept at 20° to 24°C and 45 to 60% relative humidity. The test is evaluated 25 days after treatment. The evaluation is made using the following linear rating: = plants unaffected (controls) = plants withered Q - 2 = intermediate stages of activity Composition of the emulsifiable concentrate from which the spray broth was obtained: parts of active substance, 32.5 parts of methyl ethyl ketone, 32.5 parts of active substance and 10 parts of a - 41 mixture of nonylphenolpolyoxyethylene and calcium dodecylsulphonate.
The evaluation of the test shows that the compounds of the formula I, and in the present instance especially those of the groups Ic/Id, for example the methyl ester, ethyl ester and thiomethyl ester of 3,4-diphenyl-cyclohex-3-ene-l~ carboxylic acid, effected a pronounced reduction in growth of Amaranthus, Sinapis, Ipomoea, Galium, Rumex and Setaria, but chiefly of Avena fatua, whilst important plant crops, · such-as wheat, barley, maize, cultivated sorghum millet, rice, sugar beet and cotton were not injured. The vegetative, growth of soya plants was inhibited, but otherwise their further development was normal. ' Test B 15 Growth inhibition of grasses (postermegence method) Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic dishes filled with an earth/turf/sand mixture and watered normally; Each week the emergent grasses were cut back to a height of 4 cm above the soil and then sprayed with aqueous spray broths of the active substances of the formula I 40 days after sowing and 1 day after the last cutting. The amount 44391 of active substance corresponded to a rate of application of 5 kg per hectare. The growth of the grasses was evaluated 10 and 21 days after application using the following linear scale rating: 1 = pronounced inhibition (no further growth from the time of application) » no inhibition (growth as untreated control) The active substances of the formula I showed a marked growth inhibition (rating 1 to 4).
Test C Inhibition of the growth of undesired suckers in tobacco plants Tobacco of the variety Xanthi was reared in a greenhouse. The leading shoot was cut off shortly before flowering.
One day later, 3 plants at a time were sprayed from above with 10 ml of an aqueous preparation of a compound of the formula I. The selected active substance concentrations corresponded to rates of application of 10 kg, 6 kg and 3 kg per hectare. The inhibiting action on the suckers of the 6 uppermost leaf axils was determined 14 days after application.
The compounds of the formula I effected in this test a - 43 44291 pronounced inhibition of the sucker growth even when used in low rates of application, in particular the esters and thioesters of subgroup Ib, wherein R represents haloethyl, optionally substituted benzyl, but especially C.,-C7-alkyi or C^-Cg-alkenyl.

Claims (15)

CLAIMS:
1. A plant growth regulant composition which composition contains, as active ingredient, a compound of the formula I: wherein
2. A composition according to claim 1, which contains, as active ingredient, a compound of formula I wherein G represents a group of the formula -0R°. 3. To 7 and 10. 21. A method of influencing plant growth, which method comprises applying to plants or the locus in which they are growing a compound of formula I as defined in claim 8, 9 or 11. -51-44391 22, A method of inhibiting plant growth, which comprises applying to plants or the locus in which they are growing a compound, of formula I as defined in claim 8, 9 or 11. 23. A coinpound of formula I as defined in claim 1
3. A composition according to claim 1, which contains, as active ingredient, a compound of formula I wherein G represents a group of the formula -OR.
4. A composition according to claim 1, which contains, as active ingredient, a compound of formula I wherein G represents a group OR in which R represents a C^-C^ alkyl radical which is unsubstituted or substituted by halogen, cyano, C 1 ~C 4 alkoxy, 0^-0 4 alkylthio, C 2 -C 5 alkoxycarbonyl, by a C^-Cg aliphatic carbamoyl group, by an amino, mono-(C 1 -C 4 )alkylamino, di(C^-C^)alkylamino or 44391 tri(C^-C^)alkylammonium group, by a Cg-Cg cycloaliphatic radical, by a phenyl or phenoxy group which is unsubstituted or substituted by halogen, alkyl or C^-C^ alkoxy, or by a 5- or 6membered heterocyclic ring containing 1 or 2 heteroatoms; a Cg-Cy alkenyl radical which is unsubstituted or mono- or tetra-substituted by chlorine or bromine; a propynyl or butynyl radical; a Cg-Cg cycloalkyl radical which Is unsubstituted or substituted by chlorine, bromine or methyl; a phenyl radical which is unsubstituted or mono- to tri-substituted by halogen, C-^-C^ alkyl, C^-C 4 alkoxy, C x -C 4 alkylthio, NOg, CFg, COOH, CN, OH, SOgH, NHg, -NH(C.,-C 4 alkyl) or -Ν(Ο χ -α 4 alkyl) 2 ; or a 5- or 6-membered heterocyclic ring containing 1 or 2 heteroatoms. 5. With the proviso that at least one of the substituents U, V, W, X, Y and Z is other than, hydrogen when G is OH. 24. 25. 26. A A A compound of formula I as defined compound of formula I as defined in in in claim 2. claim 3. compound of formula I as defined claim 4. 10 27. A compound of formula I as defined in claim 5. 28. A compound of formula I as defined in claim 6. 29. A compound of formula I as defined in claim 7. 30. A compound of formula I as defined in claim 8. 31. A compound of formula I as defined in claim 9. 15 32. A compound of formula I as defined in claim 10. 33. A compound of formula I as defined in claim 11. 34. l,2-Diphenyl“cyclohex-l-ene-4-earboxylic acid methyl ester. 35. A process for preparing a compound of formula 20 I according to claim 23, which process comprises reacting acrylonitrile or a compound of formula II ch 2 =ch-co-g with a diene of the formula III (II) (HI) 44292 (wherein U, V, W, X, Y and Z are as defined in claim 1 with the proviso that at least one of the substituents U, V, W, X, Y and Z is other than hydrogen when G is OH) and, when acrylonitrile is used, subsequently converting the nitrile group of the product obtained into a group of formula CO-G as defined above. 36. A process according to claim 35 wherein the diene of the formula III is formed in situ by elimination of 2 moles of water from a diol of the formula Ilia. 37. A process for preparing a compound of formula I according to claim 23 substantially as described with reference to any one of the Examples. 38. A compound of formula I according to claim 23 prepared
5. A composition according to claim 4, which contains as active ingredient, a compound of formula I in which each of U, V, W, X, Y and Z, which may be the same or different, represents hydrogen, halogen, C 1 ~C 4 alkyl, C^-C 4 alkoxy, methylthio, ethylthio, NOg, CFg, COOH, CN, OH, SOgH, NHg, methylamino, ethylamino, dimethylamino, diethylamino or methylethylamino. - 48 44291 5 each of U, V, W, X, Y and Z, which may be the same or different, represents hydrogen, halogen, C^ C 4 alkyl, c 1 c 4 alkoxy, C 1 ~C 4 alkylthio, N0 2 , CF^, COOH, CN, OH, SO-jH, NH 2 , -NHCCj-Cj alkyl) or -N(C^-C 4 alkyl) 2 , and each of U and X in addi10 tion can represent an unsubstituted phenyl radical, and G represents a group of the formula -0R°, -OR or -SR, and R° represents hydrogen or a cation M n ®, wherein 15 M represents an alkali or alkaline earth cation, a cation of iron, copper, zinc, manganese or nickel, or an ammonium radical of formula (in which each of R^, R 2 , Rg and R 4 , which may be the same or different, represents hydrogen, benzyl or a C^-Cg alkyl radical which is unsubstituted or substituted by -OH, -NH 2 or C^-C^ alkoxy) and n is 1, 2 or 3 and is the valency of M; and R represents a C^-C^g alkyl radical which is unsubstituted or substituted by halogen, nitro, cyano, C^-Cg alkoxy, 0 2 _ 0θ alkoxyalkoxy, Cg-Cg alkenyloxy, C^-Cg alkylthio, C 2 ~Cg alkanoyl, C 2 -Cg acyloxy, C 2 -Cg alkoxycarbonyl, carbamoyl, bis (C^-C^ alkyl)amino, trisfC^-C^ alkyl)ammonium, Cg-Cg cycloaikyl, Cg-Cg cycloalkenyl or by a phenyl, phenoxy or 5or 6-membered heterocyclic ring containing 1 to 3 heteroatoms which phenyl or phenoxy group or heterocyclic ring is unsubstituted or substituted by halogen, C^-C^ alkyl or alkoxy; a Cg-C^g alkenyl radical which is unsubstituted or mono- to tetra-substituted by halogen or monosubstituted by phenyl or methoxycarbonyl; a Cg-Cg alkynyl radical; a C 3 “C l2 cycloaikyl radical which is unsubstituted or substituted by halogen or C-^-C^ alkyl; a Cg-Cg cycloalkenyl radical; a phenyl radical which is unsubstituted or substituted by halogen, C^-C 4 alkyl, C^-C 4 alkoxy, Ο χ -Ο 4 alkylthio, N0 2 , CFj, COOH, CN, OH, SO 3 H, NH 2 or -NH(C^-C 4 alkyl) or -N(C^-C 4 alkyl) 2 ; or a 5- or 6-membered heterocyclic ring containing 1 to 3 heteroatoms, together with a solid extender and, optionally, a surface active agent or together with a liquid diluent and a surface active agent.
6. A composition according to claim 5, which contains, as active ingredient, a compound of formula I in which all of U, V, W, X, Y and Z represents hydrogen atoms.
7. A composition according to claim 1, which contains, as active ingredient, a compound of formula I in which all of U, V, W, X, Y and Z represent hydrogen atoms and G represents a group -OR in which R represents a Cg-Cy alkenyl radical or a C^-Cy alkyl radical which is unsubstituted or substituted by a C^-C^ alkoxy group.
8. A composition according to claim 1, which contains, as active ingredient, a compound of formula I in which represents a group of formula -SR and represents a C^-C^ 2 alkyl radical which is unsubstituted or substituted by C^-Οθ alkoxy, C 2 “Cg alkoxycarbonyl, Cg-Cg cycloalkyl or by a phenyl radical or a 5- or 6-membered heterocyclic ring containing 1 to 3 heteroatoms which phenyl radical is unsubstituted or substituted by halogen, C l -C 4 alk y· 1 · or C i -C 4 alkoxy; a C 3 ~Cj. 2 alkenyl radical; a C 3 -C ]_2 cycloalkyl radical which is unsubstituted or substituted by Cj-C 4 alkyl; a phenyl radical which is unsubstituted or substituted by halogen, C^-C^j alkyl, C “C 4 alkoxy, C 1 ~C 4 alkylthio, N0 2 or CFg, or a 5- or 6-membered heterocyclic ring containing 1 to 3 heteroatoms. 49 4 4 2θ i
9. A composition according to claim 1, which contains, as active ingredient, a compound of formula I in which all of U, V, W, X, Y and Z represent hydrogen atoms and G represents a group -SR in which R represents a C 3 ~C 7 alkenyl radical or a C^-C^ alkyl radical which is unsubstituted or substituted by a C^-C^ alkoxy group.
10. A composition according to claim 1, which contains, as active ingredient, the 2-bromoethyl ester, neopentyl ester, 2,2,2-trichloroethyl ester, isobutyl ester, 2fluoroethyl ester, or 2-dimethylaminoethyl ester Of l,2-diphenyl-cyclohex-l-ene-4-carboxylic acid.
11. A composition according to claim 1, which contains, as active ingredient, the methylthio ester of 1,2-diphenylcyclohex-l-ene-4-carboxylic aoid.
12. A composition according to. claim 1, which contains, as active ingredient, l,2-diphenyl-cyclohex-l-ene-4carboxylic acid methyl ester.
13. A composition according to claim 1, which contains, as active, ingredient, a compound of formula I as defined in claim 1 with the proviso that at least one of the substituents U, V, W, X, Y and Z is other than hydrogen when G is OH.
14. A method of influencing plant growth, which method comprises applying to plants or the locus in which they are growing a compound of formula I as defined in claim 1 or 13. 50 4 4 2 91 15. A method of inhibiting plant growth, which comprises applying to plants or the locus in which they are growing a compound of formula I as defined in any one of claims 1 or 13. 16. A method of controlling Ayena fatua (wild oats), which comprises applying to the wild oats or the locus in which they are growing the compound as defined in claim 12. 17. A method of influencing plant growth, which method comprises applying to plants or the locus in which they are growing a compound of formula I as defined in claim 2 or 12. IS. A method of inhibiting plant growth, which comprises applying to plants or the locus in which they are growing a compound of formula I as defined in claim 2 or 12. 19. A method of influencing plant growth, which method comprises applying to plants or the locus in which they are growing a compound of formula I as defined in any one of claims 3 to 7 and 10. 20. A method of inhibiting plant growth, which comprises applying to plants or the locus in which they are growing a compound of formula I as defined in any one of claims
15. By the process claimed in claim 35, 36 or 37.
IE1795/76A 1975-08-15 1976-08-13 3,4-diphenyl-1.2.5.6-tetrahydrobenzoic acid derivatives IE44291B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH1066575A CH617421A5 (en) 1975-08-15 1975-08-15 Plant growth-regulating composition
CH1066675A CH617423A5 (en) 1975-08-15 1975-08-15 Plant growth regulator.
CH1066475A CH617418A5 (en) 1975-08-15 1975-08-15 Plant growth regulators.

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IE44291B1 true IE44291B1 (en) 1981-10-07

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AT (1) AT344752B (en)
AU (1) AU507074B2 (en)
BG (1) BG27357A3 (en)
BR (1) BR7605355A (en)
CA (1) CA1069913A (en)
CS (1) CS189595B2 (en)
DD (1) DD127675A5 (en)
DE (1) DE2636389A1 (en)
DK (1) DK367976A (en)
ES (1) ES450723A1 (en)
FR (1) FR2320700A1 (en)
GB (1) GB1539091A (en)
GR (1) GR60796B (en)
IE (1) IE44291B1 (en)
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DK367976A (en) 1977-02-16
NL7609063A (en) 1977-02-17
TR19118A (en) 1978-07-01
CS189595B2 (en) 1979-04-30
LU75586A1 (en) 1977-04-22
CA1069913A (en) 1980-01-15
IL50231A (en) 1981-02-27
BR7605355A (en) 1977-08-16
AU507074B2 (en) 1980-01-31
DE2636389A1 (en) 1977-02-24
AT344752B (en) 1978-08-10
DD127675A5 (en) 1977-10-05
FR2320700B1 (en) 1979-09-28
AU1683476A (en) 1978-02-16
ATA603676A (en) 1977-12-15
BG27357A3 (en) 1979-10-12
GR60796B (en) 1978-08-30
FR2320700A1 (en) 1977-03-11
ES450723A1 (en) 1977-12-01
JPS5223050A (en) 1977-02-21
IE44291L (en) 1977-02-15
GB1539091A (en) 1979-01-24
IL50231A0 (en) 1976-10-31

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