IE894170L - Fungicidal and herbicidal agents, and substituted¹2-cyclohexen-1- yl-amine derivatives and their preparation - Google Patents

Fungicidal and herbicidal agents, and substituted¹2-cyclohexen-1- yl-amine derivatives and their preparation

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Publication number
IE894170L
IE894170L IE894170A IE417089A IE894170L IE 894170 L IE894170 L IE 894170L IE 894170 A IE894170 A IE 894170A IE 417089 A IE417089 A IE 417089A IE 894170 L IE894170 L IE 894170L
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Ireland
Prior art keywords
alkyl
carbon atoms
unsubstituted
straight
substituted
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IE894170A
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IE62165B1 (en
Inventor
Franz Kunisch
Peter Babczinski
Dieter Arlt
Hansjoachim Santel
Robert R Schmidt
Wilhelm Brandes
Harry Strang
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Thomond Mockler
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Publication of IE894170L publication Critical patent/IE894170L/en
Publication of IE62165B1 publication Critical patent/IE62165B1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
    • A01N33/10—Amines; Quaternary ammonium compounds containing oxygen or sulfur having at least one oxygen or sulfur atom directly attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
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    • C07C211/39—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of an unsaturated carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C225/20—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the carbon skeleton
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    • C07C229/48—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino or carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups and carboxyl groups bound to carbon atoms of the same non-condensed ring
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    • C07C229/50—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino or carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups and carboxyl groups bound to carbon atoms being part of the same condensed ring system
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    • C07C233/00—Carboxylic acid amides
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    • C07C233/45—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
    • C07C233/52—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring
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    • C07C233/63—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by carboxyl groups
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    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
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    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract

There is described the use of 2-cyclohexen-1-ylamine derivatives of the formula (I) <IMAGE> in which R<1> to R<4> and A have the meaning given in the description, in pesticides, in particular as fungicides and herbicides, and novel 2-cyclohexen-1-ylamine derivatives, and a plurality of processes for their preparation. [EP0376072A2]

Description

6 2 * !; 5 - 1 - The present invention relates to the use of substituted 2-eyelohexen-1-yl-amine derivatives , some of which are known, in pesticides, in particular as fungicides and herbicides, and to new substituted 2-cyclohexen-l-yl-5 amiss.© derivative.a and. several processes for their preparation .
It is already known that certain tetrahydrophthalixnides, such, as, for example, cis-N- [ (trichloromethyl) thio] -4-cyclohexene-l,2-dicarboimide, have fungicidal properties 10 (cf., far example, Science,, (Washington.) 115. 84 (1952) i US 2,553,770).
However, the action of these eosapounds is not always entirely satisfactory in all fields of application,, in particular when low application rates and application IS concentrations are used® Furthermore,, it is already known that 2-cycloalkenylamine derivatives and their salts, such, as? for example, N-2-cyclohexen -1 -yl - 2,2 - dimethyl ~propionemd.de, have fungi -cidal properties (cf -, for example, EP-OS (European 20 Published Specification) 0,128,006).
In addition, 3ar-benzyl~2-cycloheacen-l-yl-asaine derivatives, such as, for example, N-4-aethylbenzyl-2-cyclo-hexenylamine, have been described as intermediates for the preparation of .substituted benzylcycloalkenylurea 25 derivatives (cf. EP-OS (European Published Specification) 0,113,028).
Moreover, substituted 2-eye1ohexen-1-y1- amine derivatives, such as, for example, 6 - carbome thoxy - 2 - eye 1 ohexen -1-yl-amine, are known as additives for lubricating oils 30 (cf. US Patent Specification 4,582,613)- Substituted 2 - eye 1 ohexen- 1-yl-amine derivatives, such as, for example, S-carboiaethos^,-2-cycl©he3i£en-l-yl-(4,4" -dimethoscybenzhydrylamine), are also described as - 2 ~ intermediates for the synthesis of the natural substance ( + )-gabaculin (cf- J. Org. Chem. £4* 3451-3457, 1979).
In addition,, the Diels-Alder reaction of various N~ acylamino-1,3-butadienes with methyl acrvlate to give the 5 corresponding N-acylaanino-2 -cycloheacene derivatives, such as, for example, 6-carboa»ethoscy-2-eyclohexen»l-yl ethyl carbamate, is quantitatively investigated (cf. u„ Am. Chem. Soc», 100, 3182-9, 1979).
Furthermore, the synthesis of a plurality of 2-cycle>-10 hexen-l-vl-amine derivatives has been described (cf« J. Med- Chem., 2ji, 1 - 8, 1986; J. Med- Ch©sa., 24,, 788-94, 1931, Gaxz. Chin. Ital. 37, 295-7 £1927), J. Am. Cheat. Soc., 103, 2816-22, 1981; J. Am. Chem. Soc., 100, 3182-9, 1978; J. Am. Che®. Soc., 100,, 5179-85, 1978 and 15 Tetrahedron Lett., 25, 2183-6,? 1984, J. Org. Chem., 46., 2833-5, 1981, J. As. Chesi. Soc., 105, 5373-9, 19833 , however, nothing is kao««n about their activity in the field of plant protection.
It has now been found that the substituted 2 -eyclohaoceri-20 1-yl-amine derivatives, some of which ara known, of the formula (I) I • MH-A in which E1 represent® hydrogen, alkyl or halogen, 23 a2 represents formyl, hydroxyalicyl, cyan© or nite.ro, or rep-resents one of the radicals -3SER5, -5IESH7, ^,XR12 -NH-CH-C00H,-CH,-0-C-R9, -C-R10, -PCXR11)o, _ » L ^11 II II, l,H» B® 0 0 X" X- - 3 - * 5 10 15 20 P -S(0),,R14 or -CH^CH-E313, R3 and R4 are identical or differ cut and in each case represent hydrogen, alkyl, alkenyl, alkinyl* alkoxy, alkenyloxy or alkinyloxy, or represent unsubstituted or substituted aryl, or represent unsubstituted or substituted aralkyl, or represent unsubstituted or substituted heteroaryX, or represent unsubstituted or substituted heterocyclylalkyl, alkoxyalkyloxy or halogen, or represent one of the radicals -NH-R5, -NR®R7 or -S(0)3~R", or R2 and R3 together represent one of the radicals -C-H C~ , -C-O-C- o- -(CH?>_-0-C- HI,. I il II ' " I 0 0 0 0 0 which are bridged via the 6- and 5-positions, or E3 and R* together represent an alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4- and 3-positions, Rs represents hydrogen,, alkyl or unsubs t i tut ed or substituted aryl, Rs represents alkyl or unsubstituted or substituted aryl, R7 represents alkyl or unsubstituted or substituted aryl, R® represents hydrogen, alkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl, - 4 - R9 represents alkyl or alkoxy, R10 represents hydroxy!f hydroxyalkyloxy, halogenoalkvl -oxyg alkoxy, alkoxyalkyloxy, unsubstituted or substituted, cycloalkyloxy, unsubstituted or substituted 5 aralkyloxy, unsubstituted or substituted aryloxy, unsubstituted or substituted aralkyl, alkylthio or unsubstituted ©r substituted aryl thio, or represents a group -OH, -NHSs, -NR6R7 or -0-Z~NR5R\ Ru represents hydrogen or alkyl, 10 R12 represents hydrogen or alkyl, RiS represents alkyl, S14 represents alkyl, alkoxy or unsubstituted or substituted aryl, or represents the group -QM, E"3 represents formyl or cyano., or represents the group -r-=»l 0 V» la,\ II 0 15 R" represent® hydrogen, alkyl or ^substituted or substituted aryl, M represents hydrogen or represents an equivalent of a corresponding alkali metal cation, alkaline ear th metal cation or ammonium cation, 20 n represents a number Q, 1 or 2, X and Z1 are identical ©r different and represent oxygen or sulphur, ja. represents a auBsber 1 or 2, 3k represents hydrogen or asa amino-protecting group and - 5 - Z represents a straight-chain or branched alkyl chain„ and their acid addition salts and metal salt complexes show powerful biological properties.
The coaqpounds of the formula (I) cam be present as 5 geometric isomers (S/Z isomers) or mixtures of isomers of varying composition. The invention claims the uee of the pure isomers as well as the mixtures of isomers™ Is addition, the compounds of. the formula (I) contain 1 to 4 ehir&l centreLS and can therefore be present in 10 various mixtures o£ enantiomers and diastereomers, which, if appropriate,, caa be separated in a customary manner. The invention likewise claims the use of the pure enamtioisers and diastereomers as well as that of the mixtures. 15 For reasons of sisaplicity, the following will always refer to the use of compounds of the £ ansa, la (I) even though there will be meant the pure compounds as well as the mixtures of varying proportions of isomeric, enantiomeric and diastereomeric compounds. 20 Surprisingly, the substituted 2 -cyclohexen-l-yl-amine derivatives of the formula SI), some ©£ which are kno^n, and their acid addition salts and metal salt complexes show better fungicidal properties when applied at appropriate concentrations: than cis-N- [ (trichloromethyl) - thio] -25 4-cyclohexene-l, 2-dicarboimide, which is known from the prior art and asa active compound of a similar constitution and of the saas type of action. The substituted 2~ cyclohexen-1 -yl - amine derivatives of the formula CD * some of which are known, additionally also show very good 30 herbicidal properties when applied at appropriate concentrations .
Forsaula (ll1 provides a general definition of the substituted 2-eyelohexen-1-yl-amine derivatives to be used according to 'the invention. unless defined otherwise, the radicals in the general formulae have the following gleanings: Alkyl ~ s traight - chain or branched alkyl having 1 to 3, preferably 1 to 6, in particular 1 to 4, carbon atoms. 5 Examples which may preferably be mentioned are optionally substituted methyl, ethyl, a-- and i»-propyl,, n~; i-, s-and t-butyl.
Alkenyl and the alkenyl moiety of optionally substituted alkenyloxy - straight-chain or branched alkenyl having 2 10 to 8, preferably 2 to 6, in particular 2 to i carbon a.tome „ Examples which may preferably be mentioned are optionally substituted ethenyl, 1-propenyl, 2~propenyl and 3~buteayl.
Alkinyl and the alkinyl moiety of optionally substituted 15 alkinyloxy - straight-chain or branched alkinyl having 2 to 8# preferably 2 to 6, in particular 2 to 4, carbon atoms. Examples which may preferably fee mentioned are optionally substituted ethinyl, 1-propinyl, 2-propinyl and 3-butinyl. 20 Alkoxy - unsubstituted or substituted, straight-chain or branched alkoxy having 1 t© 8, preferably 1 to 6g in particular 1 to 4,, carbon atosis. Examples which may preferably be mentioned are optionally substituted methoxy, ethoxy, a.- and i.-propoxy and n~, i~, s- and t-25 butoxy- Aryl - preferably unsubstituted or substituted phenyl or naphtyl, in particular phenyl.
Aralkyl and aralkoxy - unsubstituted aralkyl or aralkoacy or aralkyl or aralkoxy which is substituted ±a the aryl 30 moiety and/or alkyl moiety, preferably having 6.or 10, in particular 6, carbon atoms is the aryl raoiety (preferably phenyl or naphthyl, in particular phenyl) and preferably having 1 t© S, in particular 1 to 6, carbon atoms in the - 7 - slkyl moiety, it being posaibla for the alkyl moiety to be straight-chain or branched. Examples which may preferably be mentioned are optionally substituted benzyl and phenyl e thy 1 or benzyloxy and phenyl e thy lossy. 5 Unsubstituted or substituted heterocyclic radicals in the general formulae denote heteroparaffialc, hoteroaromatic and heteroolefinic 5-6-mmshsrmd rings, preferably having 1 to 3, in particular 1 or 2, identical or different hetero atoms„ Hetero atoms are oxygen, sulphur or nitro-10 gen. Examples which may preferably be mentioned are pyrrolidinyl, piperidinyl, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, oxazolyl, isoxa-zolyl, thiazolyl, isothiazolyl, 1,3,4- and 1,2,4-oxadi-asolyl, azepiayl, pyrrolyl, isopyrrolyl, pyridyl 15 pyridazinyl, pyrimidinyl, pyrazinyl and 1,2,3-, 1,2,4-, 1,2,5- and 1,3,4-thiadiazolyl.
Halogen in the general formulae preferably denotes fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine, and particularly prefer-20 ably fluorine .and chlorine.
The optionally substituted radicals of the general formulae can carry ©a,@ or mors, preferably 1 to 3# in particular 1 or 2, identical or different substituents. Examples of substituents which may preferably be 25 mentioned are: Alkyl preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl,, a.- aad i»-propyl and a.-, i»- and t.-butyl; alkoxy preferably having 1 to 4, in particular 1 or 2, carbcn atoms, such as methoxy, 30 ethaxy, a. - and i. -propyloxy mid n. -, i- -, sec. - and t. -bu tyloxy; alkyl thi© preferably having 1 to 4, in particular 1 or 2, carbon atc®as„ such as methylthio, ethylthio, a. - and i. -propylthio and a. -, i. -, sec. - and t.-butylthio? halogenoalkyl, halogenoalkoxy and halogeno-35 alkylthio, preferably having 1 to 4, in particular 1 or - 8 - 2„ carbon, atoms and preferably 1 to 9, in particular 1 to 5, halogen atoms, the halogen atoms being identical or different,, and preferably being filtsorine,, chlorine or bromine, in particular fluorine, such as trifluoromethyl, 5 trifluoromathoxy, and tri fluorome thy 1 thio; hydroarjrl; halogen, preferably fluorine* chlorine,, bromine and, iodine, in particular fluorine, chlorine and bromine; cyan©? nitro; amino; dialkylamino, preferably having 1 to 4, in particular 1 or 2, carbon atoms per alkyl group, 10 such as methyl-ethyl-amino, and methyl-n.-butyl-amino; carboxyl.
Compounds of the formula (X) which are preferably used are those in which R1 represents hydrogen* straight-chain or branched IS alkyl having 1 to 6 carbon atoms, or fluorine, chlorine or bromine, R2 represents foraayl, straight-chain or branched hydroxy alkyl having 1 to 3 carbon atoms in the alkyl moiety, cyano or nitro,, or represents one of the 20 radicals -Win5, NR6R7, -NH-CH-COOM, -CH,-0-C-R9.
L II " H8 o ,XH12 -c-a10, -?(*r>j)2. -fr. . -s R3 and R4 together represent as alkyl chaia which has 3 or 5 4 carbon atoms aad which is linked via the 4- and 3- positions, E5 represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon Atoms,, or aryl which has 6 to 10 carbon atone and which is unsubstituted or 10 snonosubstituted to peeatasubstituted by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned for R3, R® represents straight-chain or branched alkyl having 1 to 6 carbon atoms, or represents aryl which has 6 15 to 10 carbon ato®s and which is unsubstituted or monosubstituted to pentasubstituted by identical or different substituents, suitable aryl substituents being those aryl substituents mentioned for Ra, R7 represents straight-chain or branched alkyl having 20 1 to 6 carbon atoms, or represents aryl which has 6 to 10 carbon atoms and which is unsubstituted or monosubstituted to pentasubstituted by identical or different substituents, suitable aryl substituents being those aryl substituents mentioned under R3,,, 25 E® represents hydrogen or straight-chain, or branched alkyl having 1 to 6 carbon a terns, or represents aryl or aralkyl, in each sase having 6 to 3L0 carbon atosas in the aryl moiety and where appropriate 1 to 4 carbon atoms in the alkyl naolety, and in each case 30 being unsubstituted or aaonosubstituted to - 11 - pentasubstituted ia the aryl moiety by identical or different substituents, suitable aryl substituents being the aryl sujostifcuem,ts mentioned far R3* represents in each case straight-chain or branched alkyl or alkoxy having 1 to 6 carbon Etom@f represents hydrozxyl, straight-chain or branched hydroxyalkyloxy having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyloxy having 1 to 8 carbon afcoias aad 1 to 17 identical or different halogen atoms,, cycloalkyloxv having 3 to 6 carbon atoms which is unsubstituted or monosubsti-tuted to polysubstituted by identical or different halogen substituents, in each ease straight-chain or branched alkoacy ©r alfcylthio having 1 to 8 carbon atoms or straight-chain or branched alkoxyalkyloxy ia each case having 1 to 6 carbon atoms in the alkoxy aoisty .and alkyl moiety,, or aryloxy, aryl-thio, aralkyl or aralkyloxy, in each case having S to 10 carbon atoms in the aryl moiety and where appropriate 1 to 8 earbon atoms in the alkyl moiety, aad in each aass being unsubstituted or mono-substitnted to pentasubstituted in the aryl moiety by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned for R3, or represents a group ~NER5, -NR®R7 or -0-Z-NRsR®, represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms, represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms, represents straight-chain or branched alkyl having 1 to The acids which can be added on preferably include hydrohalic acids? such as, for example, hydrochloric acid 5 and hydrobromic acid, ia particular hydrochloric acid, furthermore phosphoric acid, nitric acid,, monofunctional and bifunctional catrboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, trifluoroacetie acid, m&leic acid, succinic acid,, fumarie acid, tartaric 10 acid, citric acid,, salicylic acid,, sorbic acid, and lactic acid, oleic acid, stearic acid, benzoic acid which is optionally monosubstituted to polysubstituted by nitres or halogen,, gluconic acid, ascorbic acid, malic acid, sulphamic acid, sulphonic acids, such as, for example, 15 p-toluenesulphonie acid, 1,5-naphthaleoiedisulphonic acid and methanesulphonic acid, and imides, such as. Cor example, phthalimide, saccharin aad thiosaccharin.
In addition, other compounds which are preferably to be used according to tha invention are addition products of 20 salts of metals of main group X, II and II and of tin, and furthermore salts ofi netals of stab-groups I, II, VII and "if'III oi the Periodic Table of the Elements and those substituted 2-cvclohexen-1-yl-amine derivatives of the formula (2) in which a1, Ra, Rs and H1* have the meanings 25 which have already been mentioned ia connection with the description of the substances of the formula (I) to be used according to the invention, as being preferred for these substituents.
In this context, salts of copper, zinc, manganese, 30 magnesium, calcium, tin, iron, cobalt and of nickel are particularly preferred. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition, products. In this connection, particularly preferred acids of this type are 35 the hydrohalic acids, such as, for exasqale, hydrochloric acid and hydrobromic acid, aad furthermore phosphoric acid, nitric acid and sulphuric acid.
Compounds of the formula (I) which are particularly preferably used are those in which, Rx represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or fluorine, chlorine or bromine.
R2 represents formal straight-chain or branched hydroxyalkyl having 1 to 4 carbon atoms in the alkyl moiety, cyano or nitro, or represents one of the radicals "NHr5> NR6R7» -NH-CH-COOM, -CH,-0-C-*?9 | || " ' ea o vp X 2 ~C~R*0 _p/ V312 v „■** *' . . fj j|(AH ~tfV3 ' -S(0)nRl4 0 X1 x1" or -CK=CH-R1S, R3 and R4 are identical or different and in each case represent hydrogen, in each case straight-chain or branched alkyl or alkescy having 1 to € carbon atoms, in each case straight-chaia or branched alkenyl, alkinyl, alkeayloxy or alfciayloccy, in each ©as© having 2 to 6 carbon afcoiss^ or represent alkoscy-alkyloxy, in each case having 1 to S carbon afcos&s in tha individual alkyl moieties, or represent phenyl or phenylalkyl, where appropriate having 1 or 2 carbon atoms in the alkyl moiety,? and in each case being unsubstituted or monosubstituted to penta-subsfcituted ia the phenyl saoiety by identical or different substituents, suitable phenyl substituents being: fluorine* chlorine,,, brojtd,2a«-s * nitro,,. eyas.©* amino,, C,-Ca-alkyl, Cx-C3-alkoxy or C, -C,-alkylthio„ halogeno- (Cx-C3) -alkyl, halogeno- CC^-C,) -alkozcy and - 15 - halogeno- (C,~C2) -alkylthio, in each case having 1 to 5 identical or different fluorine and/or chlorine atoms, furthermore represent a heterocyclic five- or six-5 saamtoerad group from the series comprising fury!,, thienyl, pyrrolyl, pyrasolyl, imidazolyl, 1,2,3- ©r 1,2,4-triasolyl, oxazolyl, isoxazolyl, 1,2,4- or 1,3,4-oxadiazolyl, thiazolyl, isothiasolylif 1,2,3-, 1,2,4-, 1,2,5- or 1,3,4-thiadiazolyl, pvxidyl, 10 pyridazinyl, pyrimidinyl and pyrazinyl, which group is unsubstituted or monosubstituted to trisubssti-tuted by identical or different substituents aad, where appropriate linked via a methylene group, suitable substituents on the heterocycle is each 15 case beings fluorine, chlorine, bromine, nitro, cyano, amino, Cx-Ca-alkyl, C,-C3-alkoxy, Cj-Cj-alkyl-thio, halogeno- (C,-Ca) -alkyl, halogeno- {Cx-Ca) -alkoxy and halogen- JC,-C2) -alkylthio, each having 1 to S identical or different fluorine and/or chlorine 20 atoms, and di- (C^C,) -alkylamino, furthermore represent fluorine, chlorine or bromine, or represents one of the radicals -NH-R5, -NR®R7 or -S (0)a-H", or 25 R2 and R1 together represent one of the radicals 0 R16 bridged via the 6- and S-positions, or Rs and R* together represents an alkyl chain which has 3 30 or 4 carbon atoms and which is linked via the 4- and 3-positions, R5 represents ■ hydrogen, straight-chain or branched - IS - alkyl_ having 1 to 4 carbon atoms, or phenyl which unsubstituted or monosubstituted to pentasubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned for E3* represents straight-chaia or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubstituted or monosubstituted to p&ntasubstituted by identical ©r different substituents, suitable phenyl substituents being those phenyl substituents mentioned for a3, represents straight-chain or branched alkyl having 1 to 4 carbon atcais, or phenyl which is unsubstituted or raonosubstifcuted to pentasubstitutad by identical or different substituents, suitable phenyl substituents being those phenyl substituents mentioned for a3, represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon afconas, or represents phenyl or phenylalfcyl, where appropriate having 1 or 2 carbon atoms in the alkyl moiety, and in each ease being unsubstituted or aionosubstituted to pentasub-stituted in the phenyl saoiety by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned for a3, represents in each ease straight-chain ©r branched alkyl or alkoxy having 1 to 4 carbon a teens, represents hydroxy!, straight-chain or branched hydroxvalkyloxy having 1 to 6 carbon atoms, straight-chain ox branched halogenoalkyloxy having 1 to 6 carbon ato^s and 1 to 13 identical or different halogen afcacsas, cycloalkyloxy having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted by identical or different - 17 •• substituents from the series cons listing of fluorine, chlorine and bromine, in each case straight-chain or breached alkoxy or alkylthio having 1 to 4 carbon atoms, or straight-chain or branched alkoxyalkyloxy, ia each case having 1 to 4 carbon atoms ia the alkoxy moiety or alkyl moiety, off phenyl oxy, phenyl -thio ? pheaylalkyl or phenylalkyloxy, «here appropriate in each case having 1 to 6 carbon atoms ia the alkyl moiety# and in each case nmstabofcittited or monoeubstituted to pentasubstituted in the phenyl moiety by identical or different substituents, suitable phenyl substituents being the phenyl sub-stituents mentioned for R3,, or represents a group -OM, -NHX5, or -0-Z-«RsK6, represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atons? represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms, represents straight-chain or branched alkyl having 1 to 4 carbon atoms, represents ia each case straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, or phenyl which is unsubstituted or monosubstituted to pentasubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned for R3„ or represents the group -OM, represents formyl or cyano, or represents the group -C-H10 SI o represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is - 18 - unsubstituted or monoaubstituted to pentasubstituted by identical or different substituents, suitable phenyl substituents be.lag the phenyl substituents mentioned above for R3# S m represents a number 1 or 2 and M represents hydrogen, or represents aa equivalent of a corresponding sodium cation, potassium cation or ammonium cation, a represents a number 0, 1 or 2, 10 3E and X1 are identical or different and represent oxygen or sulphur, A represents hydrogen or .an asnino-protecting group and Z represents a straight-chain or branched alkyl chain having 1 to 6 carbon atoms.
IS The term "amino-protecting group" is generally known and relates to groups which are suitable for protecting (for blocking) an amino group from chemical reactions,, but which are readily detachable after the desired reaction has been carried out on other sites of the saolecule. 20 Representative of such groups are, ia particular, unsubstituted or substituted acyl, aryl - for ©xasaple DNP (2,4-dinitrophenyl>, aralkoxymethvl - for example BOM {H-(bsnzyloxy)methyl) , or aralkyl groups {for as-sample benzyl 2, 4-nitrob@nzvl, triphenylmethyl) . Incidentally, 25 since the amino-protecting groups are removed after the desired reaction (or sequence of reactions), their nature and size is not critical; however, those having 1 - 20, in particular 1 - 8, carbon atoms are preferred. In connection with the present invention, the tens "acyl 30 group" is taken to mean aeyi groups ia the broadest sense. It comprises acyl groups derived from aliphatic, ara,liphatic„ aroaatio or heterocyclic car&oxylic acids or - 19 - sulphonic _ acids,, and in particular alkoxycarbonyl, aryloxyc&rbonyl and especially ar a 1 koxyearboay1 groups™ Examples of acyl groups ©fi this type are alkanoyl , such as acetyl» propionyl, butyryl? aralkanoyl such as pb.es,yl -S acetyl; aroyl such, as benzoyl or toluylj; aryloxyalkanoyl, such as PDA (phenoxyacetyl); alkoxycarbonyl, suck as methoxycarbonyl, ethoxycarbonyl, 2,2,2-trichloroethoxy-carbonyl, BOC (tert.-butoxycarbonyl), 2-iodoethoxy-carbonyl; aralkyloxycarbonyl„ such as CBZ ("carbo-10 hmz%o?qfm) and 4 -saethoxybensyloxycarhonyl» Preferred ©sain©-protecting groups are benzyl^ acetylf m&thoxycarbonyl » allyloxycarbonvl, trichloroethyloxycarbonyl„ ( + ) -menthyloxyearbonyl, tert-butoxycarbonyl and benzyl-oxycarbonyl. 15 The application furthexsaore relates to new substituted 2-cyclohexen-1-yl-amine derivatives o£ the formula (la) m2 in which R1' represents: hydrogen,, alkyl or halogen, 20 R2' represents fozmyl, hydroxyalkvl , cyano or aitroe, or represents ©Jae of the radicals -CH,-0-C-E7% -C-R*' or II 81 O G -CE»CH~R'', R9', R"*', E3' and E6' are identical or different and in each 25 case represent hydrogen, alkyl,? alkenyl, alkinyl, alkoxy, alkenyloxy aad alkinyloxy, or represent unsubstituted or substituted arylj. or .represent unsubstituted or substituted aralkyl, or represent unsubstituted .or substituted heteroaryl, or repress-30 ent unsubstituted or substituted heterocyclylalkyl, - 20 - or represent alkoxyalkyloicv, or represent halogen. where at least two of the radicals H3', R"®', a3' or R6' represent hydrogen, a7' represents alkyl or alkoxy, 5 R8' represents hydroxyl, hydroxyalkyloxy, halogenoalkyl -oxy, alkoxy or alkoacyalkyloxy, unsubstituted or substituted cycloalkyloxy, unsubstituted or substituted aralkyloscy, unsubstituted or substituted aryloxy, unsubstituted or substituted aralkyl, 10 alkylthio or unsubstituted or substituted arylthio, or represents a group -O-Z-NR11^*2', -NER10', -NR"'R12' or -0M,, Es' represents £ormyl or cyana„ or represents the group -C-K®' II 0 15 a10' represents hydrogen, alkyl or unsubstituted or substituted aryl, R11' and R12' are identical or different and in each case represent alkyl or unsubstituted or substituted aryl, 20 Z represents a straight-chain or branched alkyl chain and M represents hydrogen,, or represents a» equivalent of a corresponding alkali metal cation, alkaline earth metal cation or ammonium cation 25 ©r Is' and Rs' together represent one of the radicals "S~? m"' ~S~0~!r -(CH»)™-0-C- II 1,,, II SS l\ or " " || o m*4 ooo o - 21 - bridged via the 6- and 5-positions, where R13' represents hydrogen, alkyl or unsubstituted or substituted aryl aad 5 m represents a nunriber 1 or 2, or R*' aad Rs' together represeat aa alkyl chaia which has 3 or 4 carbon atoms aad which is liaked via the 4- ai&d 3-positions, 10 and their acid addition salts and metal salt complexes, with fch© exception of the compounds 2 - amino - eye 1 ohex - 3 -ene-carboxylic acid auad ethyl 2-amino-cyclohex-3-ene-carboxylate.
Formula (la) provides a general definition of the substi-15 tuted 2 - cyclohexen-1 -yl - amine derivatives which were hitherto *mknown.
Preferred compounds of the formula (la) are those ia which R1' represents hydrogen, straight-chaia or branched 20 alkyl having 1 to 6 carbon atoms, or fluorine, chlorine or bromine, R3' represents formyl, straight-chain or branched hydroxyalkyl having 1 to 8 earboa atoms ia the alkyl saoiety, cyano or nitro, or represents one of the 25 radicals -CHj-O-C-R7', -C-R8' or -CH=CH-R9', I! R3',, R*', Rs' aad E®' are identical or different and ia e&eh case represeat hydrogen, ia each case straight-chaia - 22 - or branched .alkyl or alkoxy having 1 to 8 carbon atoms, ia each case straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, in each case having 2 to 3 carbon atoms,, or alkoxyalkyloxy, in each case having 1 to 3 carbon atoms in the individual alkyl moieties, or represent aryl or aralkyl, la each case having 6 to 10 carbon atoms is the aryl moiety and where appropriate 1 to 4 carbon atosss ia the alkyl moiety» and ia each case being unsubstituted or moaosubstituted to pentasuhstitiated ia the aryl moiety by identical or different substituents, suitable aryl substituents beings halo-gem, aitro, cyano, amino, Cj-C^-alkyl, Cx-C4-alko2cy, Ca-C«-alkyl thio, halogeno- (Cj-CJ -alkyl, halogeno- (Cj-C4) -alkoxy, halogeno- {€,-€4) -alkylthio, each having 1 to 9 identical or different halogen atoms,* and d±-(C,-0,s) -alkylamino, furthermore represent a heterocyclic 5- or 6-rnem-bered group from the series comprising furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3- or 1,2,4-triazolyl, oxazolyl, isoxazolyl, 1,2,4- or 1,3,4-oxadiazalyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyriaidiayl and pyrasisyl, %wb,ieh. group is unsubstituted or moaosubstituted to trisubstitu-ted by identical or different s^bsfcifciae*?,ts and where appropriate linked via a methylene •group, suitable substituents on the heterocycle in each case being: halogen, nitro, cyano, amiao, C,-C4-alkyl^ C,-C4-alkoxy or Ct - C4 - alkyl thio, halogeno-CCj-C^-alkyl, halogeno- CC,-C,4S -alkoxy or halogeno- -alkyl- thio, each having 1 to 9 Identical or different halogen atoms, and di- (Cx-C«) -alkylasaino, furthermore represent £luoriae, chloriae ©r brosa&ne, where at least two of the radicals R9', R1', Es' or R6' represent hydrogen, represents in each case straight-chain or branched alkyl or alkoxy having 1 to 6 carbon atoms, - 23 - R8' represents hydroxy1 t. straight-chain or branched hydr oseyal ky 1 oxy having i to 8 carbon atoms, straight-chain or branched haloganoalkylosry having I to 8 carbon atones and 1 to 17 identical or 5 different halogen atoms,, cycloalkvloxy hawing 3 to 6 carbon atoms which is unsubstituted or monosubstituted to polysubstituted by identical or different halogen substituents,, in each case straight-chain or branched alkoxy or alkylthi© 10 having 1 to 6 carbon atoms,, or straight-chain or branched alkoxyalkyloxy, ia each case having 1 to 6 carbon atoms in the alkoxy moiety or alkyl moiety,, or aryloxy, arylthio, aralkyl or aralkyloxv, in each case having 6 to 10 carbon atoms ia the aryl jaoiety 15 and where appropriate 1 to 8 carbon atoms ia the alkyl moiety,, and in sack ease being unsubstituted or monosubstituted to pentasubstituted in the aryl ssioiety by identical or different substituents, suitable aryl substituents being the aryl 20 substituents mentioned above, or represents a group -0-Z-WRxl'Rla', -NHR10', -NR^'S13' or -OM, R9' represents formyl or cyano, or represents the group -C-R8' II 0 R10' represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, or aryl which has 25 6 to 10 carbon atoms and which is unsubstituted or monosubstituted to pentasubstituted by identical or different substituents, suitable aryl substituents beiag the aryl substituents mentioned above, R11' represents straight-chain or branched alkyl having 30 JL &Q S carbon atoms, or aryl which has 6 to 10 carbon atoms and which is unsubstituted or. monosubstituted to pentasubstituted by identical or diff- " ferent substituents,, suitable aryl substituents being the aryl substituents SEenfcioaed above, a12' represents straight-chain or branched alkyl having 1 to 6 carbon atoms., or aryl which has 6 to 10 carbon atoms and which is unsubs ti tuted or monosub-stituted to pentasubstituted by identical or differ eat substituents, suitable aryl substituents being the aryl substituents mentioned above, H represents hydrogen,, ©r represents an equivalent of a corresponding alkali metal cation, alkaline earth metal cation or ammonium cation and Z represents a straight-chain or branched alkyl chain having 1 to 8 carbon atoms, or a2' and R1' together represent one of the radicals II I,,. II II | ~ " II 0 Bi3 O 0 O £ bridged via the 6- and 5-positions, where R13' represents hydrogen, straight-chaia or branched alkyl having 1 to 6 carhos, atoms or aryl which has 6 to 10 carbon atoms and which is unsubstituted or monosubstituted to pent&substituted by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, aad m represents a number 1 or 2, or R*' and H5' together represent an alkyl chain wS>ieh has 3 or 4 carbon atoms and which is linked via the 4- and 3-positions. - 25 - Other preferred compounds according to tha invention are addition products of acids and those substituted 2-cycio-hexen -1-yl - amino derivatives of tha formula. (Ia) in which R1', St2'? Rs'„ R4', Rs' aad R*' have the abovementioned 5 meanings.
The acids which can be added on preferably include hydrohalic acids, such as« for example,., hydrochloric acid or hydrobrosaic acid,, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid*, monofunctional 10 and birunctioaal carboxylic acids and hydroxycarboxy1ic acids,, such as, for example, acetic acid, trifluoroacetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid., citric acid, salicylic acid, sorbic aeid aad lactic acid,, oleic acid, stearic acid, benzoic acid which is 15 optionally monosubstituted or polysubstituted by sxitro or halogen, gluconic acid,, ascorbic acid, malic acid, sulphamic acid, sulphoxxic acids, such as, for example, p~ toluenesulphonic acid, 1,, 5-naphthalenedisulphonic acid and methanesulphonic acid, and imides, such as, for 20 example, phthaliad.de, saccharin and thiosaccharin.
In addition, other preferred compounds according to the invention are addition products of salts ©f metals of laain groups I, 1% and III and of tin,, and furthermore salts of metals o£ sub-groups I, II, VII and VIII of the 25 Periodic Table of the Elements aad those substituted 2-cyclohexen-1-yl-amine derivatives of the formula (la) is which R1' , Ra', R3', R4', R5' and R*' have the abovementioned meanings - In this context, salts of copper, ^ine? manganese, 30 magnesium, calcium, tin,, irone, cobalt aad of nickel are particularly preferred. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. In this connection, particularly preferred acids of this type are 35 the hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid, nitric acid aad sulphuric acid,, - 26 - Particularly preferred compounds of the formula (la) are those in which R1' represents hydrogen, straight-chaia or branched alkyl having 1 to 4 carbon atoms, or fluorine, S chlorine or brosaiae, R2' represents foraryl, straight-chain or branched hydroxvalkyl having 1 to 4 carbon atoms in the alkyl saoiety, cyano or nitre, or represents one ofi the radicals -CH2-0-C-a7% or -CE^CE-R9', 10 0 0 H3', H"®', Rb' and R'5' are identical or dififiereafc aad in each case represent hydrogen, in each case straight-chain or branched alkyl or alkoxy having 1 to 6 carbon atoms, ia each case straight-chain or branched 15 alkenyl, alkinyl, alkenyloxy or alkiayloxy, in each case having 2 to 6 oarbosi a tons, or alkoxyalkylajsy, in each case having 1 to S carbon atoms in the individual alkyl moieties, or represent phenyl or phenylalkyl, where appropriate ha^-iag 1 or 2 carbon 20 atoms in the alkyl moiety, and is each case being unsubstituted ©r moaosiabstitnted. to trisubstituted in the phenyl moiety by identical or different substituents, suitable phenyl substituents beingi fluorine, chlorine, bromine, nitro, cyaae,- aiaiso, 25 Ci-Cj-alkyl, C^-Cj-alkoxy, Cx - C2 - alkyl thio, halogen©- (Cj-Cj) -alkyl, halogeno- CCa-Ca) -aXkossy and halogeno-CCj_*-C2) -alkylthio, in each case having 1 to 5 identical or different fliaorine and/or chlorine atoms, and di- (Cj-Cj) -alkvlamino, 30 furthermore represent a heterocyclic five- or siac- saa^hered group frost the series comprising furyl, thienyl, pyrrolyl, pyrasolyl, imidazc-lyl, .1,2,3- or 1,2,4-triazolyl, oxazolyl, isewassolyl, 1,2,4- or 1,3,4-oxadiazolyl, fchiasolyl, isothiazolyl, 1,2,3-, 35 1,2,4-, 1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pyridasinyl,. pyrimidiavl aad pyrasiayl, which group is unsubstituted or monosubstituted to trisubstituted by ideatieal or different substituents .and where appropriate linked via a methylene, group,, suitable substituents oa the heterocycle ia each cas® beings fluorine,? ehlorine» bromine,, nitro, cvano, amino, C^-C,-alkyl, Ca-C,~alkosiy or C^-Cg-alkylthio, halogeno- (C4-CaJ -alkyl, halogeno- (Cx-Ca) -alkoxy and halogeno- {C,-C,| -alkylthio, ia each case having 1 to 5 identical or different fluorine aad/or chlorine atoms, and di~ (Cx-Ca) -alkylamino, furthermore represent fluorine,, chlorine or bromine, where at least two o£ the radicals R3', R4', R3' and H':' represeat hydrogen, represents ia each ease straight-chain or branched alkyl or alkorcy having 1 to 4 carbon atoms, represents hvdroxvl, straight-chain or branched hydroxyalkyloxy having 1 to 6 carbon atoms,, straight-chain, or branched halogeaoalkyloacy having 1 to S carbon atoms aad 1 to 13 identical ©r different halogen atoms, cycloalkyloxy having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents from tha series consisting of fluorine, chlorine aad bromine, in each case straight-chain or branched alkorcy or alkyl thio having 1 to 4 carbon, atoims*. or straight-chain or branched alkoxyalkyloxy, in each case having 1 to 4 carbon atoms in the alkoxy noiety or alkyl moiety, or phenyloxy, phenyl-thio, phenylalkyl or phenyialkyloxy, where appropriate in each case having 1 to 6 carbon atoms in the alkyl moiety,, aad is, each case unsubstituted or monosubstituted to trisubstituted ia the phenyl moiety by identical or different substituents, suitable phenyl substituents being the phenyl - 28 - substituents mentioned sbofi,, or represents a group -0~Z-NRlx Ria#, -NHR10', -NH"'R"' or -QM, represents fios^ayl or cyano, or represents the group -C-R8' fl 0 represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubstituted or monosubstituted to tri3ubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, represents straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubstituted or monosubstituted to trisubstitufced by identical or different substituents, suitable iDlb. X substituents being the phenyl substituents mentioned above, represents straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, represents hydrogen, or represents an equivalent of a corresponding alkali metal cation, alkaline earth metal cation or ammonium cation and represents a straight-chain or branched alkyl chain having 1 to 6 carbon atoms, and E3' together represent oaa ©f th© radicals - 29 - -C—N C-, -C-O-C- II I-,,. II II II or -b-0-C- o e13 ooo II o bridged via the 6- and 5-posit ions*, R13' represents hydrogen r straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl «?3aieh is unsubstituted or monosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above,, aad, m represents a number 1 or 2, or R4' and Hs' together represent aa alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4- and 3-positions.
Ia this connection, the same acid addition salts and metal salt cooqpleaces may be mentioned which have already been mentioned in the description of the preferred 2-cyc1ohexen-l-vl- amine derivatives, substituted according to the invention, of the formula (la).
The substituted 2-cyclohexen-l-yl-asiine derivatives ox the formula (la) are obtained when A) 2 - cvc 1 ohexen -1-yl - carboxy1 i c acid derivatives of the formula (II) R4' o-e14' in "shich - 30 - R1', Ra', R3', R*' , R5' and R6' have the abovementioned meaning and R1*' represents hydrogen, methyl or ethyl, are treated in a generally customary tmxin.Br with 5 chloroformic acid ester^ by the method of Curtius, if appropriate in the presence of a diluent, such as, for example, acetone., and in the presence of a. base, such as, for example, N,N-diisopropy 1 amine, at temperatures between -15#C and +10°C, and adding aa 10 azide, such as, for example, sodium azide, to this reaction mixture, if appropriate in the presence of a diluent, such, as, for example, water, at temperatures between -5°C and -s-25°C, and hydrolyzing the isocyanate, which occurs as an 15 intermediate, of the foramla (Ila) (Ila) in which R1', Br', R3', R4', R5' and R®' have the abovementioned meaning, 20 with water, if appropriate in the presence of an acid or a base, and, if desired, converting the resulting amines into acid addition salts and metal salt complexes [cf. J. Org. Chem. 26, (1961), 35113 .
In addition, the substituted 2-eyelohexen-l-vl-amine 25 derivatives of the formula (la) are obtained B) frocn the 2 -cyclohexen© derivatives of the formula (lib) (lib) in which R'\, Ha'£, E3',, R*3'„ Hs' aad R4' have the abovementioned meaning aad 5 A represents an amino-protecting group, in a Jraoi'sii manner by customary methods, for example by solvolysi®, such as hydrolysis or acidolysis, by reduction,, such as, for example, by hydrogen©lysis in the presence of a hydrogenation catalyst or by 10 means of a reduction system of metal and proton e's 1 ijsinating agent, where, depending on the nature of the protecting group,, various types of eliminating methods (also di££erent types) and selective elimination. methods can be used, if appropriate ia the 15 presence of a suitable solvent or diluent or a mixture thereof, where, if required with cooling, at roam temperature or with heating,, for example ia a temperature range of about -10°C to the boiling point of the reaction medium, preferably tros about 20 -ICC to about 150°C, the process is carried out, if required, ia a sealed vessel, under pressure, under an inert gas atmosphere and/or anhydrous conditions, and,, if desired, the resulting products are converted into acid addition salts or metal salt coie-25 plexes (c£. Protective Groups in Organic Synthesis, Th. W. Greene, Wiley Interscience, 1981).
The foraayl, acetyl or 2,2,2-trichloroacetyl group, -s-hich was mentioned before as, inter alia, amino-protecting group, caa be eliminated for example by hydrolysis., 30 The hydrolysis is carried out in a manner known per $e with the aid of water, it being advantageous to carry out the hydrolysis in the presence of .an acid or base -which - 32 - assists hydrolysis,, if appropriate in the presence of an inert solvent or diluent and/or with cooling or heating.
Escaiaples ©£ suitable acids are inorganic acids g, such as mineral acids, for axa»®>le sulphuric said*, phosphoric 5 acid or hydrohalic acids, organic carboxylic acids, such as lower alkanecarboxylic acids# for example glacial acetie acid, such as optionally unsaturated dicarboxylic acids, for example oxalic, malonic, maleic or £umaric acid., or staoh as hydroxycarboxy1ic acids * for example 10 tartaric acid or citric acid,, or sulphonic acids, such as Cx-C7-alkanesulphonic acid or optionally substituted benasenesulphonic acid, for exassple methanesulphonic aeid or p-toraaaesi3.lpb.onic acid.
Examples of suitable bases are the hydroxides, hydrides, 15 amides, alkanolates, carbonates, triphenylmethylides, di-Cj-C^-alkylamides, amino-C&-C7~alkylamides or e,~C7~alfcyl-silylamides of alkali metals, ©r naphthalene~amines, C4-C7-alkylamines, basic heterocyclic ccenpoTonds, ammonium hydroxides, and carbocyclic arises, Examples which aaay be 20 mentioned are lithium hydroxide,, sodium hydroxide, sodium hydride, sodium amide, sodium ethylate, potassium terfc-butvlate, potassium carbonate, lithium triphenyl-methvlide, lithium diisopropylamide, potassium 3-Camin©~ propyl) amide, potassium bis- (trimethylsilyl) -amide, 25 dimethyl -aminonaphthalene, diethylamiae or fcriethylamine, pyridine, benzyltrimethyl-amsaonium hydroxide, 1,5-diaza-bicyclo- [4.3.0]non-5-ena (DBN), and 1, 3-diaza-bicyclo-[5.4.03 undec-7-ene {D3U).
Acidolysis is successfully carried out, for example using 30 strong acids, it being advantageous to use trifluoro-acetie acid or perchloric acid, but also using other strong inorganic acids# such as hydrochloric acid or sulphuric acid# strong organic carboxylic acids, such as trichloroacetic acid^ or sulphonic acids, such as 35 benssenesulphonic acid or p- toluenesulphonic acid, An additional inert solvent may be present:. Preferably, - 33 - organic solvents, for escarp la carboxylic acids, such as acetic acid# ethers, such aa tetrahydrofuran or dioxane, amides, such, a® dimethylformamide (DMF), halogenated hydrocarbons, such as dichloramethane, furthermore also 5 alcohols, such as methanol# ethanel or isopropanol# aad water, are suitable as inert solvents.
Other tsui table solvents are mixtures of the above-mentioned solvents. Trifluoroacetic acid is preferably used ia excess without the addition of a further .solvents 10 perchloric aeid is preferably used ia the form. of a mixture of acetic acid and 70% strength perchloric aeid ia the ratio 9 : 1™ The reaction temperatures of these solvolyses are expediently between about 0 and about 50° C, the raactioa preferably being carried out between IS IS and 30°C (room temperature) .
A preferred way of eliminating the 30C group is for example using 40% strength trifluoroacetic acid ia methylene chloride or using about 3 to 5 N hydrochloric aeid ia dioxane at IS - 30°C, and a preferred way of 20 eliminating the PMOC group (9~fluorenylmethyloxycarbonyl} using an approximately 5« to 20% strength solution of dime thy lamina, diethylamine or piporidine in dimethyl-formamide at IS - 30°C., The DNP group {2,4-dinitrophenyl) can also successfully be eliminated, for example using an 25 approximately 3- to 10% strength solution of 2-mercap-toethanol ia dimethylformamide/water afc 15 - 30°C. Protecting groups which can ba removed by hydrogenolysis (for example BOM, CBZ or benzyl) can be eliminated, for example by treatment with hydrogen ia the presence ©£ a 30 catalyst (for example a noble-metal catalyst* such as palladium, expediently on a support# such as carbon) . Suitable solvents for this process are those mentioned above, in particular, for example, alcohols, such as methanol or ethanol, or amides, such as dime thy If ora-35 amide. Hydrogenolysis is usually carried out at temperatures of about 0 to 100"C and at a pressure of about 1 fco 200 bar, preferably at 20-30°C aad 1 to 10 bar. - 34 - Eydrogenolysis of the CBE group is easily carried out, for example, using 5- to 10% strength ?d~carbon in methanol at 20 - 30°C.
Sxamples which may be saentiojaed of asaino-protectijag 5 groups which are eliminated using a reducing system o£ saetal and proton-eliminating agent are (4-nitro)-benzyl-oxycarbonyl, 2-iodoethoxycarbonyl ©r 2,2,2-trichloro-ethoxycarbonyl or phenacyloxycarbonyl.
An example of the metal constituent of the metal reducing 10 (system is a non-noble metal, such as an alkali metal or alkaline earth metal, for example lithium, sodium, potassium, magnesium or calcium, ©r a transition saetal„ for example zinc, tin, iron or titanium, while possible proton- eliminating agents are, for exaasple, protonic 15 acids of the abovementioned type, such as hydrochloric acid or acetic acid, C,~C7~alcohols, such as ethanol, and/or amines, or ammonia. Examples of such systems are sodium/ammonia, sine/hydrochloric or acetic acid, or zinc/ethanol. 20 Furthermore, 4-nitrobenzvloxycarbonyl can be split, for example, using a dithionite, such as sodium dithionite, phenacyloxycarbonyl and 2 - halogeno - C2 - C7 - alkanoy 1 can be split, for example with the aid, of a nucleophilic reagent, such ae a thiolate, for example sodium thio-25 phenolate, or using thiourea and base and subsequent hydrolysis, and allyl or but-2-enyl can be split with the aid of a rhodium (III) halide, such as rhodium CXXX) chloride.
The compounds of the formula (X) which are known may be 30 prepared in analogy to the new compounds of the formula Ila) .
If, for exaaple, methyl 2-carboxy-5-methyl-cyclohex-3-ene - carboxylate and ethyl chloroforsaate are used as starting substances, U,Bf-diisopropylethylamin© is used as - 35 the base for step one, and eodiuia aside .and water are used for step two, the course of the reaction of preparation process (A) may be represented by the following equations 1. C1C00C2Hs/(C3H7-£)2NC2H5 2. M&Mg/iHgQ 3« A 4. hydrolysis 00-CH.
COOH OOH -> If, for example, tert-butyl 3-methyl-6-carbo:sy-2-cyclo-hexen-1 -yl - carbamate aad 1 il hydrochloric acid ara used as starting substances, the course of the reaction ©fi preparation, process (B) stoay be represented by the following equation: !CXx \/XC00H 811 ° ^ 2, N HC1 (TtS^C \^\C00H 1 MH2 % HC1 Formula (II) provides a general definition of the 2-cyclohexen-l-yl-carboxylic acid derivatives required as starting substances for carrying out preparation process IS (AS . In this formula '(11), R1', 32', H3', R4', Es' and R«' preferably? or in particular, represent those substituents which have been mentioned above ia the description of the new 2-cyclohexen-1-yl-amine derivatives of the formula (la) as being preferred, or particularly pre-20 ferred, for these radicals™ Sose of the 2-cyclohexen-l-yl-aarboxylic acid derivatives of the formula (II) are known and/or cas, be prepared by known processes in a sixsple, analogous manner (cf. Houben-Weyl, Hethoden der Qrganischan Chemie (Methods of - 36 - Organic Cheeaistrv] , 4th edition, ES.Muller, Ed. "vol... 5/Xe,, Georg Thi erne Verlag, Stuttgart, 1970 977; J« Cham. Soc. Parkin Trans. 1, 1557-62, 1981), for a*aspl© by cyclisising the known dienophilic compounds which have the formula 5 (III) ' > = CH-S®' (III) R2' in «b.ish R1' , H3' and E3' have the abovamentioned meaning,* aad which are known, with the corresponding diene-10 carboscylic acid derivatives of the formula (IV) ' »6" f "J (IV) 1 -CS-O CnCHCOOS14 ° jA u in which a4', Rs' and 31s' have the abovcaaentioned meaning and R1*' represents hydrog-10 ni trostyrene.
The compounds of the formula (III) are generally known compounds of organic chemistry.
Formula (117) provides a general definition of the di@ne~ carboxylic acid derivatives additionally required as 15 starting substances for the preparation of the 2-cyclohexen- 1-yl-carboxylic acid derivatives of the formula (II) . Ia this formula CIV), R4', Hs' and Es' represent those radicals which have already been stationed in connection with the description of the compounds of the 20 formula (la) according to the invention for these sub-stitueats.
The dienecarboxylic acid derivatives of the formula (IV) are known and/or caa be prepared ia a simple, analogous manner by processes known from the literature (cf. 'Seme 25 modem Methods of Organic Synthesis', W.Carruthers, Cambridge University Press,, 1986, p.125; Ace. Chess- Res-, 1979, 146).
Formula (lib) provides a general definition ©f the 2-cyclohexene derivatives required as starting substances 30 for carrying out preparation process |3^ .. In this formula (lib), a1', a2', E3', R4', Es',» R8' aad A preferably, or is particular, represent those substituents which have been mentioned above in the description of the new 2-cyclo-heacea-l~yl~amine derivatives of the formula {Xa) as being 35 preferred, or particularly preferred, for these radicals- - 38 - Some of the 2 -cyclohaxene derivatives of the formula (lib) ar® new and form a part. of the pre sent invention.
The. compounds which are listed below and which ara known, aad the enaatiomers and isomers thereof,, are excepted: 5 methyl 6-£orrayl-5-{ I Cphesyl^ethosyl -carbonyl] -amino}~3-cyclohexeae-l-carboxylate .aad me thy X 6~ C3-o;co~X-propenyX) -5-{ [ Cphenylsaethosy) -carbonyl] -amino}-3-cvcXo-hexeae-1 -carboxylate (cf - J. Med. Ghent., 29, 1 - 8, 1936; J. Med, Cheaa., 24. 788-94, 1981), methyl 3-cyclohexene-2-10 t (fcriehloroaeatyl) -amino) -1-carboxylate, 2,2,2-trichloro-M~ (6"£ormyl~2"Cyclohexea-l-yl)-acetamide, ethyl (6-£orxnyl~5~mathyl-2-cyclohexea-l-yl) -carbamate, methyl 2-[ (ethoxy-carbonyl) - amino] -6-methyl-3-eyclohexeae-l-carboxylate, methyl 2- [ (ethascycarboayl) -amino] ~5-methyl-15 3 - eyelohexeae -1 - carboxvlate, methyl 2-E (ethoxycarboayX) ~ amino] -3-cyclohexeae-1-carboxylate, ethyl 3-{2-Hethoxy-carbonyl) - amino] - S-methyl -3- eye lohexen-1 -yl }-2-propen-oate, pheavlmethyl (6-£ormyl-5-propyl-2-cyclohe35ea-l-yl) -carbamate, pheaylaethyl (6-formyl-5-methyl-2-cyclohexen-20 1-yl) -carbamate, methyl 2-[ (phenoxycarbonyl) "amino]-3-cyclohexene-1-carboxylate and ethyl 3-<6-methyl-2-{ [ (phenylmethoxy) - carbonyl jl -amino}-3-cyclohexen-l-yl>-2-propeaoate, pheayl 6-carbomethoxy-2-eye lohexen-1-yl-thiocarbamate, H- (6-carbcraethoxy-2 -cyelohexen-l~yl) -1-25 pyr r ol idine - carboxamide (cf. J. Am. Checw. Soe „,, 103, 2816-22, 1981? J. An. Ghem. See., 100* 3182-9, 1978; J. Am. Cheat. Soc., 100, 5179-35, 1973 aad Tetrahedron Lett. 25, 2183-S, 1984) , pheavlmethyl ( 6 -forsryl-5-peatyl- 2 -cyclohexen-l-yl)-carbamate (cf. J. Org. Ghem., 46, 2333-30 5, 1931} aad pheaylmethyl {6-formyl-5- [2- (methoxy-aethoxyj-ethyl]-2-cyclohexen-l-yl}-carbamate (cf. J. Aa. Ghem. Soc., IPS, 5373-9, 1983), methyl 2 - [ (p-toluene-sulphonyl) -amino] -3-oyclohexene-1 -carboxylate, t-butyl2-C (p~tol«enesulphonyl) -assis,©! -S-cyclahexeae-l-casrbostylafce, 35 bensyl 2 - [ Cp-toluenesulphonyl) -amiac] -3 -cyclohexene-1 -carboxylate and 2,4,6-trimethylphenyl 2-[(p-toluenesulphonyl) -amino] -3 -cyclohexene-l-carboasylate (cf. J- Org. Chexa.', 43. 1448-1455, (1973) . - 39 - The new 2-cyclohexexie derivatives of tha formula (lib) are obtained by cyclisiag di&nophilie coapounds of the forwula (III) <"1) „a^C-CH-K®' 5 in which Rv, R2" and E3' have the abovementioned meaning (B/a) with N - acyl - X - aiaino -1,3-butadi ene derivatives of the formula (IVa) QS' s5" *} (IVa) A-HH-CH RiS -0-CHsG C=CH-ST ia which 20 R4% Rs' aad R6' have the abovesaentioned meaning asd M%s' represents the acetyl radical or the ferinethy!-silyl radical. - 40 - initially in a first stage, if appropriate in the presence of a diluent, if appropriate in the presence of a catalyst, if appropriate in the presence of aa, iaerfc gas aad if appropriate wnder 5 pressure., and reacting the resulting 2 - eye lohexene derivatives of the formula (He) is, which 10 R1', Ra', a*', E4'„ Es* aad! R*1 ha^'e the ahovementiosieisi meaning and IS R1S* represents the acetyl radical or trimethylsilyl- radieal, ia a sacond step in a generally customary maaaere with 4,4' ~dimethoxybenzhydrylamine CDMBJ of the formula i'Vf) H3C -ch~nh2 (V]i [DHB) 20 if appropriate in the presence of a diluent, sueh as,, for exasqple, tetrahydrofuran, at temperatures firosa Q"C to the boiling point of the particular diluent used, and in the presence cf a catalyst, such as, for example, tetra&is Ctripheaylphosphirie) -palladium{0), of the £ omul a {VI), - 41 -[ (C3H3) ,P] 4Pd [cf. J. Org. Chem. 1979, 3451 (1978)], or (B/c) reacting the isocyanates which occur as intermediates in process (A), of the. formula (Ila) (Ila) is which ^ -C-0 R1', R2% RJ', R*', R5' aad R®' have the aboveinentioned meaning, with alcohols of the formula (VII) Rxs'-OE CV11) in which R1*' represeat© ia each case straight-chain or branched, optionally halogen-substituted alkyl, alkenyl, alkinyl or alkoxyalkyl having 1 to 12 carbon atoms (preferably 1 to 6 earhoso. atoms) or unsubstituted or substituted phenyl or benzyl, or (B/d) the substituted 2-cyclohexene derivatives of the formula (lib) are obtained when the 2-cyclohexene derivatives which can be obtained by process C3/a), CB/b) or (B/c), of the formula (XXd) 10 - 42 -■R4' in which [1 Lsko **''|S (lid) ?p2,s NH-fc R1', R3% R4', Es't, Es' aad A have the abovementioaed meaning, are reduced in a generally customary manner using a complex mats,! hydride, such as, for example, sodium borohydride, ia a suitable solvent, such as,, for example, alcohols,,, such as methanol, ethanol, butanol or isopropanol, arid ethers, such as, for example, diethyl ether or tetrahydrofuran, at temperatures front 0UC to 20BCg and the resulting 2~ cyclohexen- 1-yl - amine alcohols of the formula (lie) »s-& • R** tile) -OH KH-A in which 15 R1', R3', W, R5', R6' and A have the abovesaentioned meaning, are converted, for example into esters .aad ethers, by further reactions on the hydroxyl group. Furthermore, it is possible to obtain acyl derivatives or 20 carbamoyl derivatives of the compounds of the formula (lib) by reactions with, for example, acyl halides or carbamoyl chlorides, CB/a) 25 the substituted 2 -cyclo&easeae derivatives of the £ormila (lib) are obtained when the 2-cyclohexene derivatives which can be obtained by process - 43 - (B/a), (B/b) or (B/c), of the formula (lid) (lid) MH-A in which a1'* a3', a4', as'» R*' and A have the abovementioned meaning, are reacted with alkanephosphonic acid derivatives of the formula (VIII) SI7'oJ R*' O in which 10 R represents methyl or ethyl and R1#' represents the cyano group or represents tha alkoxycarbonyl group, if appropriate is the presence of a diluent, if appropriate in tha presence of a base and if appropriate in 15 the presence of an inert gas, Process (B/a) according to the invention for the preparation of the new 2 -cyclohexene derivatives of the formula (lib) is preferably carried out using diluents- Suitable diluents in this context are virtually all inert 20 organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as peataae, hexane, heptaae, eye 1 ohexane, petroleum ether,,, benzine, ligroin, benzene, toluene,, xylene, methylene chloride, ethylene chloride, chloroform, carbon - 44 - tetrachloride, chlorobenzena and o-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether,, tetrahydro-furan and dioxane, ketones, such as acetone, methyl ethyl 5 ketone, methyl isopropyl ketone aad methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitrile®, such as acetonitrile and propionitrile, amides, such as, for example, dimethylf ormamide, dimethyl-acetamide and N-mathylpyrrolidone, .aad dimethyl 10 sulphoxide, tetramethylene sulphone and hexame thylphos -phoric triaad.de.
Suitable inert gases in this context are nitrogen and virtually all noble gases, in particular argon- When carrying out process (B/a) for the preparation ot IS the 2-cyclohexeae derivatives of the forsrala (lib), the reaatios, temperatures caa be varied within a relatively wide range. In general, the process is carried out at temperatures between -70°C and +250°C, preferably between -50°C and +150°C. 20 For carrying out process (B/a} for the preparation of the 2-eyelohexene derivatives of the formula (lib), 1 to 30 moles, preferably 1 t© 3 moles, of the dienophilic compound of the formula (III), 0.01 bo 20,0 moles, preferably 0.1 to 5.0 moles, of catalyst .and if approp-25 riate 0.1 to 5% of a stabiliser which prevents free-radical polymerization, such as., for example, 4-tert-butylc&techol, ar© generally employed per mole of the M-acyl-1-amino-1,3-butadiene derivatives of the formula (IVa) . 30 The process according to the invention. for the preparation ©£ the 2-cycloheacene derivatives of the formula (lib) is generally carried oat tender increased pressure. Ia general, the process is carried out at a pressure of 1 to 200 bar, preferably at 5 to 20 bar. - 45 - Suitable catalysts Cor th® preparation of the new 2-cyclohexen-1-yl-carboxylic acid derivatives o£ th© formula (lib) according to process variant (B/a) are the catalysts %ribdch are customary for reactions of this type^ 5 Lewis acids, such a®, for example, titanium tetrachloride, tin tetrachloride, aluminium trichloride aad borosa trifluoride etherate, are preferably used* Under certain circumstances, hoover, it is also possible to carry out the process for the preparation of the new 10 2-cyclohexene derivatives of the formula (lib) without diluents and at a pressure of 1 to 200 bar.
In general,, the reactions are. carried out in a suitable diluent, and the reaction mixture is stirred for several hours at the specific tessperature required. Working up is 15 carried out in each, ease by customary methods. Is general, a procedure is followed in which the reaction mixture is either further concentrated under reduced pressure, or poured into water, and the product is isolated by extraction or filtration and purified by chroma-20 tography.
Formula (IVa) provides a general definition of the SJ-acyl-l~amino-l,3-butadiene derivatives additionally required as starting substances for the preparation of the 2 -cyclohescene derivatives of the formula (lib) 25 according to process variant (B/a) . In this formula (IVa) , R*'\, Hs' , Rs' and A represent those radicals which have already been mentioned in connection with the description of the compounds of the formula (Ia) according to the invention for these substituents. 30 The S? - acyl -1 - asaino-1,3 -butadiene derivatives of the formula (IVa) are known and/or eas be prepared in a simple, analogous manner by processes known from the literature [e£. J. Org- Cheia-, 43, 21S4 (19735 3 „ In this process, • suitable diluents for carrying out step - 46 - oae of process (B/fo) according to the invent ion are ■virtually all inert organic solvents. These preferably include aliphatic aa.ci aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclo-5 hexane , petroleum ether, benzine, ligroin, benzene, toluene# xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and ©-dichlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dim©thy1 ether aad diglycol di~ 10 methyl ether, tetrahydrofuraa aad dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone .and methyl isobutyl ketone, esters, such as methyl acetate aad ethyl acetate,, nitriles, sucli as, for example, acetonitrile and propionitrile, amides, such as, 15 for example, dinetbylforsaamidl@tS dimethylacetasaide aad N -me thylpyrrolidone, and dimethyl sulphoxide, tetra-me thylane sulphone aad hexamefchylphosphoric triamide - Suitable inert gases in this process are s,itroges, and virtually all noble gases, in particular argon- 20 When carrying out step one ©£ process fB/feJ according to the invention for the preparation ox the 2 -cyclohexeae derivatives of the formula CXXe), the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures 25 between -70#C and +250#C, preferably between -50°C aad +150°C.
For carrying out step one of process fB/b; according to the invention for the preparation of the 2 ~cyclohexene derivatives of the formula flic), 1 to 0.01 mole, 30 preferably 1 to 0.3 mole, of the substituted butadienes of the formula (XVbJ, 0.01 to 20.0 moles, preferably 0.1 to S»0 moles„ ox catalyst asd if appropriate 0-1 to 5% of a stabiliser which prevents free-radical polymerisation sueh as, for exaaple, 4 - tert-butylcateehol, are generally 35 employed per mole of the dienophilic ecaspounds of the formula (XXX). - 47 - Step one of the process according to the invention for the preparation of the 2-cyclohexene derivatives of the formula (lie) is generally carried out under increased, pressure. In general, the process is carried out at a 5 pressure of 1 to 200 bar, preferably at a pressure of 1 to 20 bar., Suitable catalysts for step one of process (B/b) according to the invention for the preparatioa of the new 2-cyclohexene derivatives ©fi the formula (He) are the 10 cacalysts customary for reactions or this fcypey Lewis acids, such as? for example, titanium tetrachloride, tin tetrachloride, aluminium trichloride and boron trifluoride etherate, are preferably used. under certain conditions, however, it is also possible to 15 carry out step one of process (B/b) according to the invention for the preparation ©£ the new 2-cyclohexene derivatives of the formula {lie} without diluents and at a pressure of 1 to 200 bar™ la general, the reactions are carried out ia a suitable 20 diluent, and the reaction mixture is stirred for several hours at the specific temperature required. Working-up is carried out in each ease by customary methods. In general, a procedure is followed in which the reaction mixture is either concentrated under reduced pressure or 25 poured into water, and the product is isolated by extraction or filtration and, purified by chromatography.
Formula ClVb) provides a general definition of the butadienes additionally required as starting substances for the preparation of the 2-eyelohexene derivatives of 30 the formula (lie).. In this formula (XVb), R5' and H*3' represent those radicals which have already been mentioned in connection with the description of the cosepounds of the formula CSa) according to the invention for these substituents. - 48 - Th© substituted butadienes of the formula (XVb) are known and/or can be prepared in a simple, analogous manner by processes known from the literature [cf - rj„ Org. Chem., 30* 2414 (1965)j. 5 4,4' -Dimethoaybenzhydrylaaaine (DM3) of the formula (V) and. tetrakis (triphonylphosphine) -palladium?0) of the foraxula (VI), which are additionally required as starting substances for step two of process (3/b) according to the invention, are generally kao^m, compounds of organic 10 chemistry [cf. J. Cham, Soc..,, 7385 (1965) 3 .
Formula (VIIJ provides a general definition o£ the alcohols required ass starting substances for carrying o*ct process (B/c) according to the invention, and they are generally known compounds of organic chemistry. 15 Process (3/e) according to the invention for the preparation of the new 2-cyclohexene derivatives of the formula CUb) is preferably carried out using diluents.
Suitable diluents in this process are virtually all inert organic solvents. These preferably include aliphatic and 20 aroisiatie,, optionally halogenated hydrocarbons, such as peeatane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, t©Xuenea, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride,. ehlorobenissene and o - dichlorobenz ene, 25 ethers, such as diethyl ether and dibutyl ether, glycol disaethyl ether and diglycol dimethyl ether, tetrahydro-reran and dioxane, ketones, s-ach as acetone, methyl ethyl ketone, methyl isopropyl ketone and snethyl isobutyl ketone, esters,, such as methyl acetate and ethyl acetate, 30 nitriles, such as acetonitrile asad propioaicrile, abides,, sash as« for example, diraefchylfosmaraide, dimethyl-aeiefcaaaid© and N -me thy lpyr r ol idono, aad dimethyl sul-pJaoacide, tetramethylene sulphone and hexasaethylphosphoric triamide. - 49 - Suitable inert gases in this context are nitrogen and virtually all nobis gases? in particular argon.
Mien carrying out process (B/e) for the preparation of the new 2-cyclohexene derivatives of the formula (lib) 5 the reaction temperatures can be varied within a relatively wide range, Is, general, the process is carried out at temperatures between -70 ®C and +150°C, preferably between -50 *0 and +100 °-C.
Process (B/e) for the preparation of the new 2~ 10 cyclohexene derivatives of the formula (lib) is generally carried out under atmospheric pressure- under certain circumstances,, however,,, the process can also be carried out under increased or reduced pressure.
For carrying out process (B/a) for the preparation of the 15 new 2-cyclohexene derivatives o£ the formula (lib), in general 1 to 5 s&oles, preferably 1 to 2 moles, of, the a1kanephosphonic acid derivatives of the formula (¥111) are generally employed per mole of the 2 - eye lohexen -1-y1-amine derivatives of the formula (XXdJ. 20 Bases which can be employed in process (B/e) according to the invention are all acid-binding agents which can customarily be employed for reactions of this type. Alkali saetal hydroxides, such as4. for example, sodium hydroxide and potassium hydroxide, alkaline earth metal 25 hydroxides,, such as, for example, calcium hydroxide, alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate and potassium carbonate,, sodium methylate, sodiusj ethylate, potassium methylated potassium ethylate, thalliusa methylate and thallium 30 ethylate, hydrides, such as, for example, sodium hydride, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, triaethylamine, diraethylaniline, dime thy IbenzylamdLne, pyridine, 1,5-diazabicyclo- [4.3.QJ -non-5-ene (D3N), 1, 8-diazabicyclo-35 [5.4.0]-undec-7-ene (D3U) and l,4-diazab±cyclo-[2.2.2] - - 50 - octane (DABGO), ar© preferably suitable™ la general, the reactions are carried out in a suitable diluent: in the presence of an acid acceptor# and the reaction mixture is stirred for several hours at the 5 specific temperature required- Working up in the process according to the invention is carried out in each case by customary methods.
Formula (¥111) provides a general definition of tha alkanaphosphonic aeicl derivatives required as starting 10 substances for carrying out process |B/e) for the preparation of the new 2 - cyclohexene derivatives of the formula CUb)„ and these alkanephosphonic aoid derivatives are known and/or can be prepared in a simple/ analogous snanner by processes known tram the literature. 15 The compounds of the formula (laJ, (II) and (XXa) to (lie]! can be obtained as fixtures of enantioaers or mixtures of diastereomers.
The invention comprises the pure isomers as well as the fixtures. These fixtures of diastereomars can be resolved 20 by customary methods, for exasaple by selective crystallization^ froa suitable solvents, or chromatography on silica gel or aluminium oxide, to give the components. Racemates caa be resolved by customary methods to give the individual enantiomers, for example 25 by salt formation with optically active acids, such as camphorsulphonic acid or dibensoyltartaric acid, and selective crystallisation, or by the formation of derivatives with suitable optically active reagents, separation of the diasterearneric derivatives and renewed splitting 30 or separation on optically active* eolussn material- Suitable acids for the preparation of acid addition salts of the compounds of the forssula CD are preferably those which have already been mentioned is connection with the description of the aeifi addition salts according to the - 51 - invention as being preferred acids.
The aeid addition salts of the compounds of the formula (X) can be obtained in a simple manner by customary salt formation methods , for example by dissolving a compound 5 of the general formula ^1) ia a suitable inert solvent and adding the aeid,, for example hydrochloric acid, and they can be isolated ia a known manner, for example by filtration,, and, if appropriate, purified by washing with. 2oi inert organic solvent. 10 Suitable salts o£ usetals for the preparation of metal salt complexes of the compounds o£ tha gaaaral formula (X) are preferably those which have been described further above.
The metal salt complexes of compounds of the general IS formula (X) can be obtained in a simple manner by customary processes, for example by dissolving the metal salt ia aa alcohol, for example eth&nol, and adding the solution to compounds of the general formula CD . Metal salt complexes caa be isolated in a kno«a manner, for 20 example by filtration* and,, if appropriate * they can be purified by recrystallization.
Tha active compounds according to the invention show a powerful biological action and can be employed in practice for combating undesired pests. For example, the 25 active compounds can ba employed for use as plant protection agents, in particular as fungicides.
Fungicidal agents ia plant protection are employed for combating Plasmodiophoranycetes, Oomycetes, Chytridio-mycetes* Zygomycetes, Ascoaaycetes, Basidiossycetes aad 30 Deuteromycetes.
Sosse causative organisms of fungal aad bacterial diseases which come under the generic names listed above may be mentioned as examples,, but not by way of limitation: - 52 - Xaathomon&s species, such as, for example, Xaathomoaas earapestris pv. orysae; Pseudomonas species, such as, for example, Pseudomonas syriagae pv. lachrymaas; S Krwiaia specias., such ass, for example, Erwinia amylovora; Pyfchium species, such as, for example, Pyfchium ultimuxa) Phyfcophfchora species# such as, for example, Phytophfchora iafestsuas? Pseudoperoaospora species, such as, for example, Pseud©-10 peroaospora humuli Off Pseudoperoaospora cufoeasisj Flasmopara species, such as, for example, Plasmopara viticola; Ptsroaospora species, such as,, for example, Peronospora piisi or P. brassicae; IS Srysiphe species, such ase, for example, Hrysiphe gramia~ i«7 Sphaerotheca species, such as, for example, Sphaerotheca fuligiaeaj Podosphaera species, such as, for example, Podosphaera 20 leucotricha; Veafcuria species, such as,, for example, Venturia iaae- qualie; Pyreaophora species, such as, for example, Pyreaophora teres or P. graxaiaea (conidia fas: Drechslera, svns 25 Helmiathosporiusa) i Cochliobolus species, such as, for example, Cochliobolus safcivus (coaidia forms Drechslera, sys: Selmiafcho-sporius&J ; Urcnyces species, such as, for example, Uromyces appen- 30 diculatus; Pusciaia species, such as, for enable,. Puccinia recon-difca; Tillafcia species, such as* for example, Tilletia caries; Usfcilagso species, such as, for example, Usfcilage auda or 35 ustilago aveaae; Pellicularia species, such as, for example, Pellicularia. sasakiii Pyricularia species, such as, for example, Pyricularia oryzaej - 53 ~ Fusarium species, such ao, for example, Fusariun cul- morumi Botrytis speciessuch as, Cor example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; 5 Leptosphaeria species, such as, for example, Leptosphaer- ia aodoriMj Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for sxam.ple, Iltsraaria 10 brassicae aad Pseudocercosporella species, such as, for example, PBeudocercosporella herpotrichoides» The good toleration, by plants, of the active compounds, at the concentrations required for combating plant 15 diseases, persaits treatment of above-ground parts of plants, of vegetative propagation stock aad seeds, and of the soil.
As plant protection agents, the active coxnqpotmd which can foe used according to the invention san be employed with 20 particularly good success protectively for cosafoafcing Phytophthora species on tomatoes and Venturia species in apples.
In addition, some of the active cosapounds which can be used according to the invention have a good action 25 against Pythiwa species, Altemaria species .and Cercospora species.
The active cosapounds according to the invention can be used as defoliants, desiccants, agents for destroying broad -leaved plants and, especially, as weed-killers. By 30 weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the asaowns used. - 54 - The active compounds according to tha invention can be used, for example, in connection with the following plants: Dicotyledon weeds e£ the eeaara; Sinapis, Lepidiuxa, 5 Galium, Stellaria, Matricaria, Jkntheiais,* Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa,, Rotala, Liaderaia, Lamium, Veronica, Abutilon, 2mex, 10 Da tiara,, Viola, Galeopsis, Papaver and Centaurea.
Dicotyledon cultures o£ tha generas Gossypium, Glycine, Beta? Daucus, Pbaseolus, Pisum, Solanum, Linaa, Xpomoea, Vicia, Nicotiana, kycopersicon, Arachis, 3rassica, Lactuca, Cucumis and Cucurbita. 15 Monocotyledon weeds of the qaaera; Schinochloa, Setaria, Panicum, Digitaria,, Phleum, Pea* Festuca, Sleusine, Brashiaria,, Lolium, 3romus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Konochoria, Fimbristylis, Sagittaria, Eleoeharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, 20 Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures o£ the genera = Oryssa^ Z&a, Triticum, Hordeum, Avena, Secale, Sorghum, Panieusa,* Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the 25 invention is in no way restricted to these genera,, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total combating of weeds, for example on industrial terrain .and rail tracks, and on paths and 30 squares with or without tree plantings - Squally, the eoaspounds can be employed for combating weeds in perennial cultures, for example afforestations, decorative tree - plantings, orchards, vineyards, citrus - 55 - groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations., oil pal® plantations,, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds in 5 annual culture©- The . active compounds according to the invention are highly suitable for selectively combating monocotyledon and dicotyledon weeds in monocotyledon crops,, in particular using the post-emergence method. 10 Depending on their particular physical and/or chemical properties,, the active compounds which, caa be used, according to the invention can ba converted to the customary formulations, such ae solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, IS very fins capsules in polymeric substances and ia coating compositions for seed,, aad furthermore ULV cold mist and warm mist formulations.
These formulations are produced ia a known manner, for example by mixing the active compounds with extenders, 210 that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-Sormiag agents. Ia the case of the use of water as an extender, organic solvents caa, for 25 example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the jaains aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzeaes, chloroethylenes or methylene chloride, 30 aliphatic hydrocarbons, such as cyclohexane or paraffins,, fas* example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers arid esters, ketones, such as acetone, methyl ethyl ketone, methyl Isohufcyl ketone or eye1ohexancne, strongly polar sol-3S vents, such as dimethylformamide and dimethyl sulphoxide, as well as water? by liquefied gaseous extenders or - 56 - carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen -and carbon dioxide; as 5 solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-disperse silica, alumina and silicates; as solid carriers 10 for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic aad organic meals, and granules of organic material such as sawdust, coconut shells,, maize 15 cobs and tobacco stalk®; as emulsifying and/or foam-forming agents there are suitable: for example, non-ionie and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, 20 alkyl sulphates, aryl sulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example ligninsulphite waste liquors and methylcellulose. &dhesiv«as such as carboxymethylcellulose and natural and 215 synthetic polymers in the forsa of powders, granules or latices, such as gum arabie, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids,, such as ceph,alin;s and lecithins, and synthetic phospholipids,, caa be used in the formulations. Other additives can be 30 mineral and vegetable oils.
Jfc is possible to use colorants such as inorganic pigments , for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuf fs, a 2:0 dyes tuffs and metal phthalocyanine dye-35 stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and ssin©„ - 57 - The formulations in general contain between 0., 1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For combating weeds,, the active compounds according to S the invention , as such or ia the Sons, of their £orxnulations, can also be used as mixtures with known herbicides, finished formulations or tank nixes being possible.
Possible components for the mixtures are known 10 herbicides, such as, for example, 1-amino-6-ethylthio-3-(2, 2 -dime thylpropy1)-1,3,5-triazine-2,4(IE,3H)-dione (AHETHYDIONE) or N- (2-benzothiazolyl) ~N,N' -dimethyl-urea (HSTA3ENZTHIAZURON) for combating weeds is cereals; 4-amino-3-methyl-6-phenyl-1,2»4-triazisa~5 (4H) -one (META-15 HITRON) for combating weeds ia sugar beet and 4-amino-6-<1,1-dimethyl ethyl) -3-methylthiO"l,2ir4-triazin-5 (4H) -one (M2TRIBUZIN) for combating weeds ia soya beans. Furthermore,, 2,4-dichlorophenoxyacetic acid £2,4-D); 4- (2,4-diehlorophenoxy) -butyric acid (2,4-DS) s 2,4-dichlorophen-20 oxypropionic acid (2,4-DP) p-3~isopropyl-2,l,3-benzothia-diazin-4-one 2,2-dioxide (BSNTCkZONE); methyl 5- (2,4-dichlorophenoxy) -2-nitrobenzoate (BI7SNOZ); N,N-dim@thyl-N' - (3-chloro-4-methylphenyl) -urea (CELORTOLURON) ; 2- [4-(2,4-dichlorophenoxy) -phenoxy] -propionic aeid,, its methyl 25 ester or its ethyl ester (DXCLOFO?) ; 4-amis,o-a-t-butyl-3» ethylthio-1,2,4-triazin-5(4E) -one (STHIOZIN)> 2-{4- 1(6-chloro-2-benzoxazolyl) -oxy] -phenoxy} -propanoic acid, its methyl ester or its ethyl ester (FBMOX&PRO?)i N,N-di-methyl-N' - (3 - tri£luor ome. thy Ipheny 1) -urea (FLUOMSTTJRON) ; 30 methyl 2- [4, 5-dihydro-4-methyl-4- (1-methylethyl) -5-oxo-lS-imidazol-2-yl] -4 (5) -methylbenzoate (IM&.ZAM3THA33NZ) j j4-ehloro-2-.iaetaylpheao;^y) -propionic acid (MCPP) ; N-(l-e thy lpropy 1) - 3,4 - dime thyl -2,6- dis&i t roasai 1 iae (P3NDXM5TS&.-LXN) i Q-CS-ehlor©-3-phesxyl»pyrida:ssin~4-yl) S-octyl 35 thiocarbonate (PYSIDATS); 4-ethylamino-2-1-butvlamino-6-me thyl thio - s -1 riass ine (TERBuTRYN) and 3,5,6- tr ichloro - 2 -pyricyloxyacetic acid (TRICIiOPYR) are also possible. 10 15 20 - 58 - Surprisingly, some mixtures also show a synergistic action.
Mixtures with, other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agent© which improve soil structure, are also possible.
The active compounds cam ba used as such, in the form of their formulation® or in tha us© fioraae prepared therefrom by further dilution,, such as ready-to-use solutions., suspensions, emulsions,, powders, pastes and granules. They are used ia the customary nnaxsiisr^ for example by watering,, spraying,, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants- They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range- It depends essentially on the nature of the desired effect. In general, the amounts used are between 0.01 and 10 kg of active compound per hectare of soil surface, preferably between 0.05 and 5 kg per ha- The preparation and use &£ the active compounds according to the invention can be seen from tha following examples - Preparation Bxaaaples s Example 1s 9H3 y^COOCHg KK2 3C HG1 (X-l) - 59 - (Process A) A solution of 5.4 g (0.05 mol) of ethyl chloroform&te ia 15 ml of acetone is added in the course of 30 minutes at -5®C to a solution of 10 g (0-05 Biol) of methyl 2-5 carboxy-5-methylcycloh&x~3-@n@~carboxylate and 8 g (0.062 mol) of N,N-diisopropyl~ethylamine in 30 mi of acetone. After the mixture had remained at 0°C for a further 30 minutes, an ice-cooled solution of 6.5 g (0.1 mol) of sodium azide in 15 ml of water is added dropwise. The 10 mixture is stirred at 0°C for 15 minutes and then worked up using water/toluene.
The organic phase, of which a residual volume of about 50 ml is obtained after drying and concentrating, is added dropwise to SO ml of boiling toluene,, and the course of 15 the reaction is monitored by IR spectroscopy. When the transition to the isocyanate is complete, the mixture is evaporated, the. residue is taken up in SO ml of tetra-hydrofuran and 50 ml of 1 N hydrochloric acid, and the mixture is stirred at 40°C for 10 hours. 20 After the mixture has been evaporated completely under reduced pressure, 2„8 g (30% of theory) of 4-methyl-6-c arbome t hoxy - 2 - eye 1ohexen-1-y1- amine hydrochloride are obtained.
*H-NHR data*' (DMSO, 200 MHz) ; 6 - 1.00 (3E) , 1.50-25 1.70(13), 1.85-2-00 and 2.15-2.35<2E), 2.85-3.00(IS), 3.63(3H), 3-80-3-85(2H), 5.70-5.90(2H) Tb.e aH~ltt£R spectra were recorded in dimethyl sulphoxide fDMSO) with tetramethylsilane (TMS) as the internal standard. The chemical shift is 30 indicated as 5 value in ppm.
~ SO - Bxamole 2 ; 'OOH (1-2) ^«2 3c HCl (Process 3) 2 g (7.3 wmaoI) of tert-butyl (3~methyl~6-carbo:Ky"2-5 eye lohexen-1-yl) -carbamate are introduced in 5 ml of 1 N hydrochloric acid. After tha mixture has bean kept at 50 °C for 4 hours it is evaporated to dryness, aad 1.3 g (87% of tha>ory) of 3-methyl-6-carbo2cy-2~cyclohexen-l-yl-amine hydrochloride are obtained as a white solid o£ 10 melting poiat 156-163°C.
Tha and products of the formula (15 which are listed in Table 1 below are obtained analogously to the methods described ia Sxasaples 1 and 2 and 15 following the instructions ia the descriptions of the processes according to the invention: R4 B?3 (I) Tabla 1 Ex. Ho, H1 R2 R3 R4 1-3 H COOH H 4-CH 1-4 H COOH H H 1-5 H CQOCH3 H H 1-6 H COOH 3,4-(CH2-CH2-CH 1-7 ' H C00CH3 H H 1-8 H COOH H 4— 1-9 H COQCH3 H 4—^ Physical consbants a,p.1 190-193 °C x HCl / uniform cla d^aataraoinar m.p.! 169-1728C x HCl / imifona cis dias taraomar 1H-NMR*) (CDC1,, 200 HHz): § = L.65-2.20(6H), 2 e 57- 2.60(1H)1 3.6G-3.70(2H), 3.71 (3H) , 5 -.18 (2H) aa.p.1 185-205°C x HCl 1H-HMRS) (CDClj, 200 KHz) 1 3 s 1.90-2.4(4B), 3,03-3.17 (IK), 3.78(3H), 4.2Q(1H), 6.00(2H), 8.25-9.65(3H) x HCl m.p.1 175 - 190°C x HCl {BMSO* 200 MHz) 1 6 = 2.75-2.05(111), 3.30-3.43 (1H), 3.65 and 3.68(3H)/ 5•75-6.00(2H), 7.10-7.40(5H) Table 1 - continuation Ex, Mo, R1 R2 E3 R4 I-10 H C00CH2CK20CH3 H 4-CH3 I = i1 H COOH H 4-C3H? I-12 CI COOH H . 4-CH3 1-13 H COOH H 4"c2% I-14 H COOH H 3-C2H5 I-IS CHg CD0CK3 H H I, ™ 1 fe H COOH H 3-CjjH^ 1-17 H CN H 4-CH3 A Physical constant® 1 H-mm*1 e dkso , 200 mhz 5 f H !■= I s OS C 311) } 3 a 301 3H J , 5.75-* 5,95(2H> » fltl0-8,50{3H) k HCl H m.p.} 1.00-IBS® C x HCl H m.p. r 200-214°C x HCl H s, p. ? 160-17 B° C x HC1 | * Cl H ia.p, ( 140-15OC to x HC 1 j H CDMSQ, 200 HHz): ■I 3 1 1 b and 1,29 ( isoasr, 3H), 3.650H), S,60-5,70 and 5 .05-6>Q0(2H), 8,20-0,50 (3H) / K HCl.
H m.p.t ISO1-IBS® C x HCl H HS-MHE (DMSOi 200 MHz 5 ? $■= 1.05{3H)j 1.80-2.10 and 2.20-2 >40(3H)1 3.4895{lH)j G165-5195(2H), 8.60-9.00(3H) / x HCl •TabIs 1 - Continuation Ex. No. R1 R2 R3 R4 J ~! fl H CM 11 4-C2 1-19 CI CN H 4-CH 1-20 H KOg S 4-CH 1-21 If - CH ° CH ~ C ■ 0 H 4-CH 1 0CaH5 1-22 H -CHsCH=CQOH H H 1-23 II -CH°CH=CbO H 4-CH t oc2i% 1-24 H ~CH2=0H H 4-CH A Physical constants H Ja«P.} 130-135°C x HCl H 1H-NMR (CDCI3s 200 MHz)t 6 ■ 1m15C3H11 1 *20-1140 and I.65-2.55(5K)i 3.60UH), 5 .60-5.85C2H) H a.p. | 215-221® C x HCl iH-KMR* 1 (CBC13 , 200 HHz ) ! H A» 1.02(3H)( 1.29<3H), 4 ,18C2H), 5.55-6.00C3H), 6»a3-7.10(lH) H ®.p.j 186-218° C x HCl H m.p.f 191-214® C x HCl H m.p.i 7 1-83° C x HCl Tab la 1 - Continuation sx.no, r1 r2 r3 r4 I = 28 ll 0 0 li If »§=■ CC-H-C)1 i o 4— 1-26 1-27 H H i! i! , S = {C - N - C) ■ JL 0 0 El 11 6,5-ce-M-ei1 4-CH3 H K ■UH^O-COCHo j£5 te3' H 4-CH-s 3 1-29 1-30 H -CG-M C CHg)2 H H . -C0-N(CH3)2 H H H Physical constants H. a.p.i S 1-S30 C x ■CPg.COOH H m.p.l 00-83® C x €PgC00H 1 m H m.p.l 78 = 81° G x CP3COOH 1 %-MMK®1 (CDCI31 200 MHz)! H & s 1 .08(314) 1 2,L0(3H)| 4.02-4.2fi(2H)j 5 ,?&-& -.00 (2H), 0.10°8.55(3H) x HCl H IRI 3S00-3350, 1655 cm"1 H IRI 1670 em"1 x CFgCGQH Tabla 1 - Continuation Ex. Ho. R1 H2 R3 R4 1-31 H -CO-N(CH3)2 H 4-CH3 1-32 H -CO-MH—p H 4-CH3 1-33 H -C0"0CH(GHt)9 H 4-CHn Ou 1-34 H -CO-CHg—C p H 4-CH3 I-3S F COOH H 4-CM3 I-3fc H -COQ-C^Hg-n H 4-CH3 1=37 H -C00C4H9°n H 4-OH3 i -3a H -COOC2H5 h 4-c.h3 Physical constants IRt i&FQ cm"1 x CPVCOOH 4)i»' ,p-.i 111-127® C 1H-HMR* 1 (CDC13 8 200 MHs)l Sb 1,05(3H)j 1.26(6H)J 5,0Q(1H), 5,53-5.80{2H) 1 H-HMR* * (CDC 13 , 200 HHE )! As ia05(3H), S.18(2H), 5«SO-S ,85(2H) |. 7 .25-7 .40C5H) 1 H-NMR*1 C CDC 13 , 200 HHa \ S 4* 1.80-2.6Q<3H>, 3 ,83-4,Q0C110 1 5 .65-5 .78 and 6,00-ft.13(2H) 1H-NMR*5 £DM80 s SCO KH*!t Ac 0 tfl9{3H), I ,03<3H), 2.84-2198{LK)i 4,00-4,20(2H), § .?0' = B ,90(2H) 1 8 .10-8 »40C 3H) IR! 35QQ-3410» 1735 cm"1 IRl 3500-3400, 1735 cm"1 Table 1 - Continuation Ibt.Ho, Rl R2 R3 R" I-39 H OH H 4-C2H5 1-40 H -CHgOH H 4-CH3 1-4 1 H ~€H2OH- H H I-48 H -COOH H 5-CH(CH3 1=43 H -COOH H 4-CH 3 1-44 H 6 |S«=CC»Q-CH2 = CH21- 4-CH3 1-45 H =C00C2Hb 5-CH3 H Physical constanba 1H=NMR*1 (CDClg, 200 MHz)I H lis 0 . 92C3H) , 1 . 27- I . 70C 5H} j 1 .90 = 2,1QC2H)» 2.7B-2.88 Cli-0, 3 .B3-3 »60( 1H) 1 5.65-S.80C2H) K6I Ri/i f«l. int.li 141 (7) , H 99 (32), 03 C100) CDMIOs. 2GiO HHz)! H &a i ,30-2, 10C5H1 5.63-5.82 aad S ,90-6 .08(2H), 0. ,00-8,40 (3H) H m.p. I 189-20S°C / x HCl H m.p. 1 130-138° C diaatoreoraar ratio-70130 / xHC 1 H 1H-NMR** CCDC13s. 200 MHz) S £ e 0 j. 80 ( 3H J j. 1^80-2.20 and 2,30-2.50 (4H), 2.90-3.05 ( iH> 1 4 • 20 = 4 .60 £ 21!) t 6*05-6 120 and 6 • 30" 6 s 4012H 3 * 7 s 30' (1HW x HCl H *H-NMR*' (DM601 200 MHz)t l-= 0.93(3H)f 1,21(3H), 2,S5-2.6S(IK), 4g10-4,25 C 2H), S.70-6i63(2H)t ■' ColD = <76.6 (c = 0,3 j h20) x HCl anantiomar of 1-3 h optical 20 rotation: [oc3D = -64,1 (c*0,3 , h->0) k HCl enaatioiaer of 1-3 is m.p.: i2g-i33i5c x HC 1 1 H 1H-NMR*5 SCDCI3, 200 MHz): 6 = 1f15(3H), I»25<6H), 2,71-2,85tlH), 5,00-5,18<1H), 1 5,87-6,08<2H), 8,30-8,70 (3H) / x HCl H MS {FAB) : 205 [H'f] k HCl H k ho0c-ch0-ch-co0h £» w j &b OH 1 h-nmr (dmso): £ = 1,00 (3h), 1 ,40 in, ih)j 2,20-2,60 (6h); 3,75 {ih)j 4,05 (1h); 5,60- 5 ^ 90 J 2H)» Table 1 = Continuation Ex. Ho. R1 R2 R3 R'1 1-52 H -COOH H 4-CH3 I-S3 H -COOH H 4-CH3 1-54 H -COOH K 4-CHg l-SS K -COOH H 4-CH3 1-56 H -COOH H 4-CH3 1-57 H -CH2"OH H 4-CH3 I-58 H -COOH H 4-CHq A Physical constants H x CH3-0-s°3H 1 H-NMR (DMSO): £ = 1,00 < 3H); 1,50 (m, IH); 2,25 {3H) ; 2,80 CiH)j 5,60-5,90 (2H) ; 7,10 (2H5 I ? ,50 (2H), H x CuS04 m.p.: 210- 219° C {dscomp.) H x HBr ! H-NMR (DHSO): & = 1,00 (3H), 1,50 (lH)i 2,SO (1H); 5 ,60-5j90 I2H)I 1i90 (br, 3H).
H x CH3C02H 1 H-NMR (DMSO) ; $ = 1 0,95 (3H)I 1,85 (3H); 5,60- g 5,.80 (2H). j H x HCl isomer of 1-3 1 H-NMR (CD30D) : 6 = 1,06 ( 3H) ; 1*83 (1H5| 2*00 ( IH); 2,38 {1H)j 2,81 <1H); 4,08 (1M); 5,60 {iH)1 6,00 (1H)9 H x HCl 1 H-NMR (DMSO)I & - 1,00 (31-ni 3,45 < 2H ) l 5.,70-5, 90 (2H5 j 8,06 (3H), H ^zwittex* iorfj|. ffl = p. : 208-21 1° C T&bls 1 - Continuation SX.NO. Rl RS R3 R4 1-59 H -C02CH3 1-60 H -C02CH3 1-61 K -CG2CH3 1-62 H ' -C02CH3 1-63 H -C02CH3 1-64 h -c02(ch2)2cich3 I-65 H -C02CH3 I -66 H -C02H H 4-CH3 h 4-CH 3.
H 4-CH3 H 4-CH3 H 4-CH3 H 4-CH3 H 4-ch3 H 4-CH3 Physical constants H K HH strongly hygroscopic 0 0 H k H02CCH2C(OH)- 90 (2HI I 5,70-5,90 (2H); 5,20 $3H), H x Cu(OAc)2 MS (FAB): 155 CM* -Cu(Ac)23 H x KO0CCH7CO0H MS (FAB.): 25 9 [H* I £t &e £* h x H02C-CH=CH-CH=CH-CH3 MS (FAB): 267 CM4] H x hc! m.p.: 203-206sC (doeomp.) Table 1 - Continuation Sx.Ho. r1 r2 r3 1-75 H _co2H H i-76 H -C02H 3-CH3 1-77 H -C02H 3-C6H5 1-78 H -C02"Na+ H 1-79 H -C02"NH44 H 1-80 H -C02CH3 3-C6H5 1-81 H -C02H H 1-02 H -C02H H 1-83 H -C02H 3-C6H5 1-84 h -C02H 3-CH(CH3)2 1-85 H -CM 3-CH(CH3)2 1-86 H "CM 3-C6H5 A Physical constant© H zwittor ion m.p, ; 98° C 4 -ch3 H X HCl m.p. ; 133-135° c 4 -CH-»CH 250° c {decomposition) 4 -ch3 h ® ■ P« ; )250° c (decomposition) 4 -ch2ch(ch3 h h 1 h-nmr C CDC 13)1 5 = 0,75-0,95 {9H)j 2,65-2,85 (ik); 3,75 (3h); 5,90 !1H)J 7,15-7,40 (5h), H H K h02cc02h a.p. : 147-150°C 0 II h H K JI hn Ti Of* V0 !m.p.: 106-112° C (decomposition) 4 -ch(ch3)2 H X HCl m.p. : 245-248° C 4 -ch2ch(ch3 }2 K . x HCl m.p. : 210-218° c 4 -CHzCH(CH3 J2 H x HCl m.p . : 1 64° c 4 -CH(CH3)2 H x HCL m.p. : 233-261° c TabJLe 3, - Continuation sx»nd. fl} I -87 1-88 H H -co2c2h5 -C02CH(CH3)2 h I! I -89 h "co2c6h5 H 1-90 H -co2c6h5 h 1-91 h ~ C Q ^ C I"1! ^ h 1-92 h -co2- H k HCl MS I 197 [H"f - HCl] H k HN MS: 231 CM4 - 183 3 0 0 H x HCl {snantiomaj?} m.p.: 210 - 21 3 , 5° C H x HCl (®nantiomar) m.p.! SOC - 210° C H x HCl MS i M of 207 by FAB spec tiroeicopy H x HCl (snanfciomair} MS (FAB): 191 [M 1-4 t H x HCl l®naakiem8i?) ms (fab): 191 [m1] Table 1 - Continuation Ex.No. r! r2 I -98 1-99 I - 100 I - 10 1 1-102 I - 103 1-104 1-105 1-106 B C02CH2-C6}l5 H C02CH2-2,4-Cl2C6H3 H C02CH2-C6H5 H C02CH2-2f1-C12C6H3 H C02CH2-2-C3C6H4 H C02CH2-3-ClC6H4 H C02CH2-4-ClC6H4 H C02CH2-4-N02C6H4 H C02CH2-2-C3Cf(H/j r4 a Physical constants H H 1 H-NMR (CDCl,)t 6 = 1,50 (2H); 2,60-2770 ( II!) 5 3,67 (IH)j 5,15 (2H); 5,75 (2H) J 7,32 (5H), H H x HCl MS? 23i [H* - 36] 4-CH3 H k HCl MS? 313 IM* - 36 3 4-CH3 H 1 H-NMR (CDClo)S 5 = 1,05 (3H)1 2,60 (2H3 I 2,,65-2,77 ( IH)I 5,26 {2H)I 5,56-5,80 C 2H)I 7,20-7j50 (4H) « 4-CH3 H 1 H-NMR (CDCl3): & = 1,06 C 3H)j 2,68-2,80 {IH); 3,77 (iH) j 5,IS C 2H)I 5,60-5,80 (2H)I 7,3 C4H), 4-CH3 H 1 H-NMR (CDCl3): 5 = 1,05 (3H)j 2,65-2,78 (IH); 5,15 ( 2H) I 5,60-5,80 ( 2H ) ; 7 ,.32 (4H) .
«•! US 4-CH3 H a ,p, : 118-124° C 4 - CH' H x HCl MS! 279 [H - 36] Tabla 1 - Continuation Bx.Mo.
R2 R'3 1-107 H C02CH2-3-ClCsH4 H 1-100 M C02CH2-4-ClC6H4 H 1-109 H C02CH2-4-N02C6H4 f! 1 - HO H C02CH2-2-ClC6H4 H I - 1 1 1 H C02CH2-3;C1C6H4 H 1-112 H C02CH2-4-ClC&H4 H 1-113 H C 0 5 C H o-4-N09CtHa ■ K 1-114 M C02CH2-2-CIC6H4 H 1-115 H C02CH2-3"C1C6H4 H 1-116 H C02CH2-4-ClC6!l(1 Ei A Physical constants 4-CH3 H 55 HCl MS' 279 [M* -36] 4-CH3 H x HCl m.p. : 167° C 4-CH3 » k HCl m.p. : 196-202° C H H 1 H-NMR {CDC 13) * & « 1,80- 2,15 14H)j 2,65-2,85 (3H); 5,29 (2H)j 5,78 (2H); 7 ,20-7,50 (4 H >• H • H 1H-NMR (CDCl3)' £ « 1,75- ■ 2,15 UK) , 2,56 (2H) ; 2,65-2,75 C1H)j 5,15 (2H)I 5,79 {2H)I 7,20-7,40 <4H) .
H Ji m.p.s 14 2° C H H 1 H-NMR (CDCl3); 6 = 1,75- 2,15 (6 H)| 5,28 £ 2H); 5,78 (2H > J 7*55 {2H); 8,20 (2K).
H H x HC! 1 H-NMR (DMSO): & = 1 ,95- 2,12 (4 H); 5,15-5,35 (2K); 5,65-6,05 (2H)J 7,30-7,60 (4H)J 8,25 C 3H).
H H x HCl 1 H-NMR CDHSO)S 6 - 1,95- 2,12 (4K>; 3,10 : 6 = 1,05 (3H); 2,68-2,80 2 H 1 H-NMR (CDCl-,): & - 0,90 (6H)I 2,60-2^70 {IH); 5,17 <2H); 5,60-5,05 (2H)j 7,35 (5H5 . 4-CH3 H x HCl 1 H-NMR CDHSO5: £ = 6,29 <-NH3 , 3H), 4-CH3 H x HCl 4H-NMg iDMSOJI £ = 8,35 <-NH3 , 3H), 1 9\ !l H x MCI H-NMg '{DMSO}; £ = 8,25 <-NH3 , 3H).
H H x HCl 1 H-NMg iDHSO3! 5 = 8t40 (-NH3 ,,3H).
H H k HCl MS: 291 CH'1 - 36 ] CH(CH3)2 H x HCl 1 H-HMR CDHSO): & = 0,85 H H H H (6H) < 2H) {5H) i,55-2«10 C 4HIJ 5,20 5,80-6,00 (2H)I 7,38 8,35 I3H). 1 H-NMR tCDCl3.ll & = 1,75- 2*15 C 6H)I 2,65-2,80 <1H>; 5,22 (2H)| 5,78 (2H); 7,20 7,50 C 3H), 1H-NKR (CDCl2): 6 = 1,75- 2,15 £ 6H)J 5,40 < 2H); 5,75 ( 2H ) ; 7 ,.20-7 ,40 ( 3H ) .
Male 1 - Continuation Ix.No< R* R2 1-134 H C02CH2-3,5-Cl2C6H3 1-135 H C02CH2-2,6-Cl2C6H3 H h R h h Physical eonstants H x HCl 1 H-NMg (DMSO): 6 = 8,43 £-NH3 , 3H).
H k HCl 1 H-NMg CDMSO): 6 = 8,25 (-NH3 , 3H), a) Th® *H-NMR spectra were recorded in deuteroehlorofonn (CDCl,) or dimethyl sulphoxide (DMSO) with tetromethylsilane (TMS} as the internal standard. Tha chemical shift is indicated as 6 value in ppm. - 78 - Preparation of the starting substances: 'OOCH3 (II) COOH & solution of 10 g (0-089 mol) of sorbie acidf, 24.1 sol (0 .,2"/ mol) of methyl acrylate, 0.1 g CO. 6 zmaol) of 4-tert. butylcatechol and 100 ml o£ diossane is reacted for 30 hours at a temperature of 110°C at 5 ha,r„ The dioxane is distilled off, and the polar by-products are separated off using the elueaat mixture petroleum ether/ethyl acetate (2 ; 1). 13.2 g (75% of theory) of methyl 2~ carboxy- 5 -me thylcyclohex- 3 - ene-carboxylate are obtained as a mixture of isomers. 1E-NMR",) (CDC13, 200 MHz) : & « 1.05 (d, 3E) ; 3.65 (s, 3H) , 5.40-5.90 (m, 2H) .
(Process B/a) A solution of 2 0.. 3 g (0.11 mol) of tert-butyl Jtraae-3-methyl-1,3-butadiene-1) -carbamate, 34 g (0.39 molj of methyl acrylate, 1 g (6 mmol) of 4 - tert-butylcatechol and 90 ml of dioxane is reacted for 20 hours at 110 "C and 6 bar. After the excess methyl acrylate has been distilled off, the mixture is separated s»s& silica gel using the eluent mixture petroleum ether/ethyl acetate (5 : l) . 24 g C80% of theory J ©f tare-butyl (3-methyl-£5- NH-C-OC(CHo), II 3 II 0 - 79 - carbomethoxy-2-eyelohexen-1-yl) -carbamate are obtained as a waxy solid.
'•H-NHR"1 (CDC1s„ 200 HHz) 1 5 » 1.42(9H), 1.68 (3H) , 1.70-2.00(413) , 2.70C1H), 3.68(3H), 4.50(IH), 4.80 (IH), 5 5.30-5.45(IE) •W-C-OC(CH3)3 0 5 g (10.6 saaool) of tart-butyl (3-methyl-6-carbomethoxy-2-cyclofcexen-l-yl) -carbamate are introduced into 40 sal of 1 N soditm hydroxide solution,? and the mixture is stirred 10 at 50eC until a clear solution has formed- The solution is extracted os.ee using diethyl ether, and a pH of 1 is than established at 0°C using concentrated hydrochloric acid. After the mixture has been extracted using diethyl ether and evaporated, 3.5 g (74% of theory) of tert-butyl 15 3 -methyl-6 ~carboxy~2-cyclohexen-l-yl-carbamate of melting point 132-136°C are obtained.
NH-C-OC (CH<3 ) -a \\ (IIb-3) 0 (Process 3/a) A solution of 18.8 g CO.13 mol) of ethyl trans-3-safer© - so acrylate in 100 ml of benzene is addad dropwise at room temperature to a solution of 20.1 g (0.11 mol) of tert-butyl-traas-1, 3"pentadiene-1 -carbamate aad 0.25 g (1.5 sraol) of 4-tert-butyleatechol in 50 ml ©f baassas, S aad the solution is stirred for 20 hours at room temperature. The solution is concentrated to half the -wol-iBue,, and crystals are allowed to rasas, at +4°C. 18.3 g (53% of theory) of ethyl 3- (N-tert-butylo;cycarbonylamino) -2-nitro-6-a»ethyl~4-cyclohexesi©-carbo3cylate of melting point 10 139-45°C are obtained.
H^C CI (Ilb-4J MH NO, I 2 0=C-0-c(CH3)3 MO- (Process 3/a) 10 g (55 mrnol) of tert-butyl (trans-1,3-pentadiene-1) -carbamate, 12.4 g (55 aonol) of trans-2- (2-chlor©-5-15 nitrophenyl) -nitroethene and 0.6 g (3-6 aanol) of 4-tert- butylcatechol ia 100 ml ©£ dioxane are reacted for 30 hours at 110°C and 4 bar. The reaction mixture is evaporated and recrvstallized twice £rom ethanol. 7 g (31% of theory) of fcert-hutyl 4-methyl-5 - C2-chloro-5-20 nitro-pheayl)-6-nitro-2-cyclohexen-l-yl-carbsumate of melting poiat 195-203°C are obtained. 0"C-0-C(CH3)3 *> 81 ■* (Process B/a) 5 10 {Process 3/c) A solution of 5-4 g {0-05 nol} of ethyl ehlorofornate ia 15 ml of acetone is added to a soltition of 10 g (0-05 IS mol) of methyl 2-carbo3ey-5-methylcyclohex-3-ene-carboxylate aad 8 g CO-062 ^olj of N,N-diisopropylethyl-aznine ia 30 ml ©f acetone at -5®C ia the course of 30 minutes. After the mixture has remained at 0°C for 30 saore minutes, aa ice-cooled solution o£ S»S g (0-1 mol) 20 of sodium aside ia IS ml of water is added dropwise. The mixture is stirred for 15 ainutas at 0°C aad then worked up using water/toluene.
The toluene phase, which is concentrated t© approximately 50 ml, is then added dropwise to a solution, boiling 25 ■ander reflux, of 3 g (0-04 mol) of tert-bucanol aad 25 sag (0.15 mmol} of tert-butylcatechol is 20 sal of tolueae-The course of the reaction is monitored by IE A solution of 1 g (5-5 mmol) of tert-butyl trans-1,3-pentadiene -1 - carbamate, 1-1 g (11 mmol) of malaic anhydride, 40 m,g (0-2 wmoX) of 4™tert-butylcatechol aad 3 ml of dioxane is heated at 100eC for 2 hours- The mixture is evaporated to dryness, aad 0-8 g (52% of theory) of tert-butyl (4-methyl-cyclohex-2-ene-5,S-dicarboxylic anhydride-1-yl) -carbamate of a melting point of 180-182°C is obtaiaed after recrystallization from benzene.
NH-C-O-C(CH3)o II 0 - 82 - spectroscopy.
The mixture is allowed to cool to room temperature aad concentrated. After separation by column chromatography on silica gel using the eluent petroleum ether/ethyl 5 acetate (6 : 1>, 4 g (30% of theory) of tert-butyl (4-m@ thy 1 - 6 - carbome thoxy- 2 - eye lohexen -1-yl) - carbamate o £ melting point 89-91°C are obtained- (Process B/d) 0 10 S g (21 mmol) of tert-butyl (4-methyl-6-forrayl-2-cyclo- hexen-l-yl5 -carbamate ar© dissolved ia 70 ml of tetra-hydro£uran, and, after 1.6 g (42 imtol} o£ ©odium boro-hydride have been' added, the mixture is stirred for IS minutes at 55°C. 17 ml of methanol are then slowly added IS dropwise at 55°C,„ and, when the addition is complete, stirring is continued for 3 hours at rocm temperature. forking-up is carried out zander aqueous conditions, the mixture is extracted using diethyl ether,, and, after drying o^er magnesium sulphate and evaporating, 4„8 g 20 (95% of theory) of 2- [ (tert-butyloxycarbonylamino) -5- methyl-3-cyclohexen-l-yl] -saethas&al is obtained as a white, waxy solid. xH-NMRm (CDC13, 200 MH^) s 5 - 1.00 (d, 3H) , 1.45Cs, 9Hj , 1.75-2.40 (m, 2H) , 3.28-3.52 and 3„S7~3»8Q {m, 2H5 , 25 4.00-4.30 and 4.45-4.75 (m, 2E) , 5.43-5.51 aad 5.63-5.78 Caa, 233) . - 83 - CH-3 ) 1 (lib-8) cx, (Process B/e) :h=ch-cooc2h5 HH-C-O-C (CHq) ~ II 3 3 0 24 g (CKI05 mol) of triethyl phosphoaoacetate are added dropwioe at Q°G to a suspension of 3.4 g (80% strength, in 5 oil - 0.1 mol) of sodium hydride, WSa®» the evolution of hydrogen, has ceased, a solution of 25 g CO. 105 mol) of tert-butyl (4-methyl- 6 -forsayl-2-cyclohexen-1 -yl) - carbamate ia 30 ml ofi tetrahydrofuran is added dropwise. After the reaction sdxiture has been stirred for 4 hours 10 at roosa temperature, it is added to 500 Jul of water, and the xaixture is extracted several fciiaeis using ethyl acetate. The combined organic phases are washed with water and saturated sodium chloride solution and dried aad concentrated. After purification by column chromato-15 graphy on silica gel using the elueat petroleum ether/ethyl acetate (5 : 1) „ 2S g (80% of theory) of ethyl trans- (2-N~tert-but©3cycarbonylasttiao-4-aaethyl-cyclohex- 2 - en) -1-yl) -acrylate. are obtaiaed. lH~NMR"' (CDCl,, 200 MSz) : 6 « 1.05{d, 3H) , 1.20-1.35 (tt, 20 3H) , 1-43 (is, 933) , 1.60-2.60 (n, 4H) , 4.15(q, 2H) , 4.25- 4.60(br.a, 2H) , 5.50~5.95{m, 33) , 6.36-7.10 (a, IS). "J) The lH-JttSR spectra were recorded in deuterochloro-form (CDC13) with tetramethylsilaae (TMS) as the internal standard. The chemical shift is indicated 25 as 5 -^alufe isa ppa.
The precursors of the formula (lib) (lib I1 nh-a which are listed in Table 2 below are obtained analogously to the methods described ia 5xsanpl@s (IIb-1) to (lib-8} and following the instructions in the descriptions of the iDrocasses aecordiae to the inventions = 85 - U o GO rt r-i © H sH ft u © c\ o\ ft a P9 ^ ^ noes JT"0«n 61 I 0 U» P9 2 <*■»» ►-»» ® « gs s w O M H CR ww ^w ui «*} H O W gei ■ * o " «*» w u w w> I <* fe* O •»*■»» ***** & M M - H a 0 w w SB HO *? II l> r c—^ t © Jr «o ca •* W K Ofcwrf (»%*) ImSM) l^F> kH 1 3 w (n«4 «»-J 4^M0 «■« w rs X X o u a ES3 ca oa tn V"!Sl s X X n n o u Wj«"> a X *a-& • % k J NS «vn ■ X X i 1 13 i o 9 : __ O-w-J (s-*-> no PS «*3 X X X X 3C o o a X o o o o a o o o a o o Q a o a o u LS s 1 3 1 9 n X tfiij S m S*S m ra l?§ m P, « ID a r» in !££» X s I»I IF**) X 1? o CJ o o a b «w w* *3 H -NO^ -COOCpHg H il o £ Ib*"2Q ^C^OC{CHg)^ H ~HGg \ ^ ^*^3 ./ \ t MQ» I lb- 29 -C-OCHg— p H -N02 -OUGCgHg CHg O r5' b6' Physical constants C?He H m.p.: 65-71®C .£0 tyf H H Sep.1 116-142 °C H H a;psi 121-122®C H H MSt 183 H* (12), 153, 127( 83, 57 (100) S 1 fl 9 ® " « sup.: 116-1219C H H m.p.i 95-96®C H H m.p.i 130-105°G m.p. : 88-91°C ■ K H Tabla 8 - Continuation R 1 s R2' -fr3 * R' ,4 * Ko.
I lb-30 -C-0-C3"h t 11 0 H -NOg -C00-C4H9-L CH3 CI llb-31 -C-0CtCH«»)'» H -NO* |j £ J & CH 3 CI IIb-32 -C-0C(CH3)3 H -MOg 0 C2f% NO1 p.
Zlh°33 -fill fig) 3 H -no2 -CI CHg, IIb-34 "C-0C(CH>s )■» H -HO- il 3 3 0 HO- NO* H Ub-35 -C-OC(CH3)3 H -m2 0 -NO2 CHg ' Physical constants If II H H H H H H H^-n H H H m.p,i 17 8-181°C m.p.s 180-183 °C m.p.: 168-174°C i.p3i 171=I7S°C ia.p. 98 = 107 ®C ib.p. i 205-206°C CD €& Table 2 - Continuation Ex. A R1 ' R2 Mo 3 R .3' r4' p5* r6• Physical constants IIb-36 -C-OC(CH3.)'3 H -HQ2 —<^ ^ 0 HOn CHo H H m.p.i 145-146°C 11b-J? -C-OC(CHg)g H ~NQg -COOCgHg -CHj> - (CHg)j»-CHj>~ H 0 MSi 356 M* (0.1), 57 {100} I lb-3Q -C-QCH-> I! i 2 . 0 CH«CH? H -H02 -COOC4H9-L H ZXb-39 "C-OCHo H II I 0 ch°ch9 H ■NOg -CQ0C4H?-t CHg H H M.T5-. i 123-124°C H m.p,s 120-126°C & Ub-40 -C-OOCCl"U)« H II 33 0 llb-41 -C-OCCC]"U)n H I! 33 !1 CI \ —'Cx )' 11- < 1! \ u o li CI > N- —cf 11 \ !! Q y-CI CH* OCH C CH-s) v —CI — OCH C CHg12 H H H m.p.i 186-1910C H m.p.s 204-2Q5#C Table 2 - Continuation Ex t A R1 ' R^s FS3' 0 II llb-42 -C-OC (CH3 H N02 -C00C2Hs — Ilb-SO =C-OC(CHg)g H H02 -C00-C4H9-t C; Hb-Si -C-OC(CH3)3 H NO2 -COO-C4H9-L H 0 m.p.i 197-199°C ffisp.! 165-168°C m.p.i 168-172*C xn ■ p. i I30-135eC m.p.s 18Q-185°C a,p.i 165-168°C EX.
M© • A R1 R llb-52 -C-QCtCHCH H i COOC?H £3 1^6 1 Physical conafc&afce aH-l®IR'' (CDC13, 200 MKz) H H 5 s 0.95-1.25(4 isomers, 3H), 1.42(s, SB}, 5,55-5.90 (m,2H), 9.60-9.05 (4 isomers, IH) H H IR {CHaCla) i 3300, 2950, 2710, 170*0 esi"1 H H IS (CH,Cla) i 3400, 2950, 2060, 1720 cm"1 H H MS i 201 [M* - iscbutane] {5) 103, 153, 127, 83, 57 H H m.p.i 106-136°C H H m.p.! 107-130CC H m.p. i 59-65°C to bl Table 2 - Continuation Ex, a rI r2 ' f}3' p}4' r5 ' ^6' Physical constants Ho. 1Ib-59 • C ■- OC (CH3) 3 li - CH2OH 0 K H H H (CDClj j. 200' » 6 = 1,45 CSH), 1.65-2.13 (410 , 3 , 30-3 3 ?S (211) , 4.08- 4,30 {IH}i 4^7Q-4.S8 (IH) , 5,45-5.93 1. it) — 60 —C—QC (CH«a ) •» H I! 3 3 -C II CI \ n—L S \ —CI H OC 1"[ C O f I ^ 5 ^ H H m.p.: 83°C III} — 61 — C—OC (CH^ ^ 1| HOrg |j U & 0 I lb-62 -C-OCCCHriii H COOH II 0 si noil -CHfCHn >•» H m.p. : 165-170°C H -CHCCHgJg H m.p.: 100-124°C lib-63 -C-OC(CHg)3 H C00CHg 0 I lb-64 -C-GCCeH^K H N0> || ti o m O ll 11 -CH(CH3)2 H m.p. I 85-93°C f NO- J»7 h H m.p.: 167-181°C Tab la 2 - Con fc lima fc ion Ex. A R1' r21 Ho, — ™0—OOHr^CaCJ 1 ^ H M0*5j j a a 0 IIb-66 -C-OC{CHq)n H -COOCoHr Til %J %* A U1 if I Ib-67 =C-OC(CH3)3 H -COOC4H9 ■ o XIb-68 -C-OC(CH3)3 H -C-N> || w1 tls & 3 o I lb-79 -C-OC(CH3)3 H -C02CH3 0 IIb-30 -C-OC(CH3)3 h -CO2CH3 IIb-01 -C-OC(CHt)o H -CO?H 0 11b-82 -C-OC(CH3)3 H -C02H 0 I lb-83 -C-OC(CH3)3 H -C02H R4 ' R5 ' ^6* Physical constants ^ch3 1 h-hmr c cdc i3 ji 6 = 0.90 ch H H <6H); 1,43 <9H); 3,68 CH3 C3H) ; 5,75 <2M .
CH3 CH3 H 1H-NMR (CDC13): 6 = 1,05 <3H5 I 1,40 (9H); \ ,60 (3H); 3 g 67 i3H)j 5,45 < IH) , x€K3 j ^ 1 H-HMR (CDCl3}5 £ = 0.73- \ / H 0.86 (8H)i 1,43 (9H) ; XH3 Vra"y 3,68 (3H); 5,82 (IH)j 7,15-7,30 (5H5 Hrjji CH H H m.p. s S 54- 158° C nch3 CH3 CH3 H m.p. : 14?-152° c -^CH3 / \ nch3 CH2CH —C ) H m.p. : 122-125® C Table 2 ~ Continuation Ex, A R1' r2- r3- p4' R5' R6•Physical constants Me a " I lb-84 -C-0C(CH3)3 H -H02 1] CH3 H H m.p.; 169-170° C 0 Hb-85 -C-0C(CHj)3 H -CN H CH2CH(CH3)2 CH(CH3)2 H m.p, : 117 - 121° C O lib-OS -C-OCtCHgJg H -CN H CHCCH^Jg C^Hg H m.p, : 84-105° C 0 I Ib-8 7 -C-0C2 C&H5 H m.p.: 151-171°C (Z) Q IIb-08 -C-OC(CH3J3 H -C02H H CH2CH(CH3)2 ch(ch3)2 H m.p.: 150-156°C 0 1 lb-89 -C-0C(CH3)3 H -C02H H j( fj H H MS J 307 [M4 ] 0 Yji- The iH-NMR spectra were recorded in dauterochlorofocm (CDC13) with tetramathylsilane CMS) as tha iafcsrnal standard., The chomieal ahi£t is indicated, as & value ia - 98 -CH- 0 I II h2c=c—ch=ch-nh-c-oc(ch3)3 (XVa-1) JR. solution of 54 g (0»5 mol) of ethyl chloro£ormate in 150 ml of acetone is added at -S°C ia the course of 30 minutes to a solution of 56 g (0.5 mol) of trans-4-5 zn£thyl~2,4-peatadienecarboxylic acid aad 80 g (0 „ 62 a»ol) of N,N-diisopropyl ethylamin® in 300 ml of acetone. After the mixture had remained at 0°C for 30 more minutes, an ice-cooled solution of 65 g CI mol) of sodium azide in 150 ml of water is added dropwise. The mixture is stirred 10 at 0°C for 15 minutes and then worked up using water/toluene. The toluene phase, which has baas, concentrated to about 300 ml, is then added dropwise fco a solution, boiling under reflux, of 29.6 g (0.4 aol) of tert-butanol and 250 mg (1.5 mmol) of tert-butylcatechol ia 200 ml of 15 toluene. The course of the reaction is monitored by IH spectroscopy. The mixture is allowed to cool to roost temperature and concentrated. After separation by column chromatography using the eluent petroleum ether/ethyl acetate (6 s 1) t 59 g (65% of theory) of tert-butyl 20 trans - 3 -methyl -1,3 -butadiene -1 - carbamate are obtained.
CHo I 1 (IV-2) h2c*c-ch*ch-cooh 4 1 2.5 g (0.1 mol) of lithium hydroxide are added at 0#C to 10 g (0.07 mol) of ethyl trans-4-methyl-2,4-pentadiene-carboxylate, dissolved in a solvent mixture of 75 ml of 25 methanol, 17 ml of tetrahydrofuran and 2.5 ml of water, and the mixture is stirred for 20 hours at room temperature. After the mixture has been diluted with 200 ml of water, it is extracted once using diethyl ether,? and a pE of 1 is established ia the aqueous phase at Q°C using 30 concentrated hydrochloric acid- The miKture is extracted using diethyl ether, the combined organic phases are washed several times with water and saturated sodium chloride solution, and, after drying aad concentrating, 6.1 g (76% of theory) of trans-4-methyl-2,4-pentadiene-35 carboxylic acid are obtained. - 99 - CHo | J (IV-1) h2c=c-ch=ch-cooc2hs 77 s (2.57 mol) of sodium hydride (80% strength ia oil) ar© added in portions at 0#C under a nitrogen atmosphere to a solution of 630 g (2.8 mol) of triethyl phosphono- acetate ia 500 ml of tetrahydrofuran. The cold bath is removed, and stirring is continued until the evolution of hydrogen has ceased (about 30 minutes) . A, solution of 200 g (2.8 mol) of methacrolein ia 2000 ml of te trahydrofuran is then added dropwise at 0°C, and stirring is continued for 1 hour at 0°C and for 2 hours at room, temperature. For working up, the batch is divided, water is added, and the mixture is extracted several times using ethyl acetate. After drying,, concentrating and distilling, 146 g (37% of theory) of ethyl trans-4-methyl-2,4-pentadieae-carboxylate of boiling point 76-90°C/20 bar are obtained.
Pas; Examples In the following TJs@ Examples, the compounds listed below are enployed as comparison substances s o cis-N- [ (trichloromethyl) thio] -4-cyclohexene-1,. 2-di-carboimide (disclosed in Science, (Washington) 115, 34 (1952); US Patent Specification 2f 553,770). - 100 - Bxaamole £ *wes,tnria test (apple) /protective Solvent: 4.7 parts by weight of acetone Etaulssifier: 0,3 parts by weight of alkylaryl poly- glycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is sodLxed with the stated amounts of solvent and oaoulsif ler, asd the concentrate is diluted with water to fch© desired concentration. 10 To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After t'he spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab causative organ! ssa CVenturia inaequalis) and 15 then remain in an incubation eabis. at 20°C and 100% relative atmospheric humidity - for 1 day.
The plants are then placed in a greenhouse at 20°C and a relative atmospheric humidity of shovLt 70%.
Evaluation is carried out 12 days after the inoculation - 20 In this test, for example the compound (1-3) according to the invention shows a better activity than comparison substance (A) . - 101 - Table A Venturia test (apple) / protective Degree of effectiveness ia % of th© untreated control at an active compound concentration ot Active compound S pom N-S-CC13 57 0 (known) (1~3) - 102 - Escam.'iolei 3 Phytophthora test (tomato) / protective Solvent: Smulsi£±er: 4.7 partis by weight of acetone 0.3 part by weight of alfcylaryl polyglycol ether To produce a suitable! preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and, emulsifier, and the concentrate is diluted with water to the desired concentration.
To test, for protective activity, young plants ara sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora inf Evaluation is carried out 3 days after the inoculation.
In this test, for example the substances (E-3) and (1-4! according to the invention show a very high degree cf effectiveness at an active compound concentration of 10 PPm- - 103 -Table B Phytophthora test (tomato)/protective/curative/systemic Degree of effectiveness in % of the untreated control at an active Active compound compound concentration of 10 ppm (1-3) 78 ( 1-4 ) - 104 - Example C Post-emergence test Solvents 5 parts by weight of acetone Emulsifier: 1 part by weight, of alkylaryl polyglycol ether To produce a suitable preparation ot active compound, 1 part by weight of active cozapound is mixed with the stated amount of solvent# the stated amount of exnulsifier ia addad aad the concentrate is diluted with water to the 10 desired concentration.
Test plants which have a height of 5 - 15 caa are sprayed with the preparation, of 'the active compound in such a way as to apply the particular amounts of active compound desired per "unit area. The concentration o£ the spray IS liquor is so chosen that the particular amounts of active compound desired are applied in 2^,000 1 of water/ha. After three weeks, the degree ©£ damage to the plants is rated in % damage ia comparison to the development ©fi the untreated control™ The figures denotes 20 0% b no action (like untreated control) 100% = total destruction In this test, for escawple. the compound (1-4) shown is Table C below shows a very good herbicidal actios,,,, ia particular in wheat- Table C Po@ t - emergence / greenhouse Active Application Ech ino- Amaran- Cheno- Xan- compound rats ia g/ha Hhaab ehtoa Pan t cure Abut Hon thus pod Sura Si da th i um a ■COOH H3N CI ■e ( I -4 ) 500 1 00 I 00 100 90 95 . 00 95 fl-iT o

Claims (1)

1. gate^t Claims - 106 - 1. Use of substituted 2 - eye lohexen -1-yl - amine deriva* ti%res ©fi the forsoula CD 10 r?4 S3 m NH-A ia which H* represents hydrogen, alkyl or halogen, R2 represents fonnyl, hydroxyalkyl, cyano or nitro, or represents one of the radical,s - *®as' -**w, -nh-ch-cooh, RS -CHj-0-C-R9, -C-RIO -?(XR"),, II II || 2' n\,13 ' 0 0 xs "l -S(0)aR" or -CE=CH-R", E3 and R* are identical or different and ia each case represent hydrogen, alkyl# alkeayl, alkinyl, alkoxy, alkenyloscy or alkinylojcy, or 15 represent unsubstituted or substituted aryl# ©r represent unsubstituted or substituted aralkyl, or represent unsubstituted or substituted hetero&ryl, or represent unsubstituted or substituted heterocyclylalkyl, alkoscyalkyloxy or 20 halogen, or reprsseat one of the radicals -NH-R5, -NRSR7 or -SC0)a-a", or Ra and Rs together represeat one of the radicals 107 -C-N- or '(CH?)--0-C- II 0 R1& II I. 0 0 0 0 10 15 20 which are bridged via the 6- and 5-positions, R3 aad R* together represent aa alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4~ aad 3-positions,, Bs represent© hydrogen,, alkyl ©ft' unsubstituted or substituted aryl, R® represents alkyl or unsubstituted or substituted aryl, R7 represents alkyl or unsubstituted or substituted aryl, H® represents hydrogen, alkyl, wasubsfcituted or substituted aryl or unsubstituted or substituted aralkyl, Rs represents alkyl or alkoxy, R10 represents hydrosyl, hydrosiyalkyloxy, halogen-oalkyloxy, alkorcy, alkosyalkylosy, unsubstituted ©r substituted eyeloalkyloxy, ^substituted or substituted aralkvloisy, unsubstifenced or substituted aryloxy, unsubstituted or snsb-stituted aralkyl, alkylthio or unsubstituted or substituted arylthio, or represents a group -OH, ~NERS, -NR6R7 or -0-Z-NRsR*, R11 represents hydrogen or alkyl, R12 represents hydrogen or alkyl, or - 108 -R"3 represents alkyl, R14 represents alkyl, alkoxy or unsubstituted or substituted aryl,, or represents tha group -OM, R~s represents forsryl or cyano, or represents the E1® represents hydrogen? alkyl or unsubstituted or substituted aryl, H represents hydrogen or represents an equivalent of a corresponding alkali metal cation,, alkaline earth saetal cation or asuatonium cation, n represents a number 0, 1 or 2, I aad X1 are identical ox different aad represent oxygen or sulphur, m represents a number 1 sr ^ A represents hydrogen or an amino-protecting groiqp and Z represents a straight-chain or branched alkyl chains asad their acid addition salts and metal salt complexes for combating pests,. Substituted 2-eyelohexen-1-yl-amine derivatives o£ the formula fT** group -C-R10 II 0 wh2 - 109 - in which R1' represents hydrogen, alkyl or halogen,, Ra' represents fiorarfl,, hydroxyalkyl, cyano or nitr©„ or represents one of the radi-5 cals -CEa~0-C-R7', -C-R®' or -CH*CH-R®', II II 0 o R3', R4', a5' and R8' are identical or different and in each case represent hydrogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy and alkinyloxy, or 10 represent unsubstituted or substituted aryl, or represent unsubstituted or substituted aralkyl, or represent unsubstituted or substituted heteroaryl, or represent unsubstituted or substituted heterocyclylalkyl, or represent 15 alkoxyalkyloxy, or represent halogen,, where at least two of the radicals R3', R4', Rs' or R6' represent hydrogen,, R7' represents alkyl or alkorcy, R"' represents hydroxy1, hvdroxyalkyloxy, halo-20 genoalkyloxv, alkoxy or alkoxyalkyloxy, unsub stituted or substituted cycloalkyloxy, unsubstituted or substituted aralkyloxy, unsubsti-tuted or substituted aryloxy, unsubstituted or substituted aralkyl, alkylthio or unsubsti-25 tuted ot substituted arylthio, or represents a group -O-Z-NR^'R13', -NER10', -NR^'R"' or -0M, R9' represents forsayl or cyano, or represents the group -C-R8' II 0 30 E10' represents hydrogen* alkyl or unsubstituted or - 110 -substituted aryl, R11' and a"' are ideatieal or different and in each case represeat alkyl or unsubstituted or substituted aryl^ Z represents a straight-chain or branched alkyl chaia and M represents hydrogen, or represents an equivalent of a corresponding alkali saetal cation, alkaline earth jaefcal cation or ammonium cation ©r a2' and a3' together represent one of the radicals -C-N C- p -C-O-C- _ / cm > „ „ II I . _. II II II or " 2 m li" 0 R13 0 0 0 " 0 bridged via the 6- and 5-positions, where RX3' represents hydrogen, alkyl or unsubstituted or substituted aryl and ie represents a number 1 or 2, or a4' and R5' together represent an alkyl ehaisi which has 3 or 4 carbon atoms and which is linked via the 4- and 3-positions, aad their aeid addition salts aad manal salt complexes, with the exception of the cosaoounds 2-aaino»cycloheae-3-ene-carbo3cyliG acid and ethyl 2-amino~ cyclohex-3-ene-carboxylate. Substituted 2-eyelohexen-1-yl-amine derivatives of the formula (la) according to CXaisi 2, ia which R1' represents hydrogen, straight-chaia or branched alkyl having 1 to 6 carboa atoms, or fluorine, ahlorla® or bromine, H3' repress safes formyl, straight-chaia or branched hydr oscy a 1 ky 1 having 1 to 8 carboa atoms ia the alkyl moiety., cyano or nitro, or represents one ©£ the radicals -CH.-O-C-St'', -C-H®' or !l « 0 0 ~CH=CHR9', a3', R*', Eb' asd H®' are identical or different and each case represeat hydrogen, in each case straight-chaia or branched alkyl or alkoxy having 1 to 8 carbon atoms, ins, each case straight-chaia ©r branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, ia each case haviag 2 to 8 carboa atoms, or alkoxyalkyloxy, ia each case having 1 to 8 carbon atoms ia the individual alkyl moieties, or represeat aryl or aralkyl, in each case having 5 to 10 carbon atojas is. the aryl moiety aad where appropriate 1 to 4 carbon atoms in the alkyl moiety, arid ia each case being unsubstituted or mono-substi tuted to pentasubstituted ia the aryl moiety by identical or different substituents, snitable aryl substituents being: halogen, nitro, cyano,, amino, Cj-Cj-alkyl, Cx-C«-alkoxy, Cj-C,-alkyl thio, halogeno- (Cj-C^ -alkyl, halogeno- CCs.-C.jj 5 -alkoxy, halogeno- (C,-C4) - alkyl-thio, each having 1 to 9 identical or different halogen atoms, and di- CCX-C4} ~alkyl-asaino, furthermore represeat a heterocyclic S- or 6-aiesshered group from the series comprising £uryl/ thieayl, pyrrolyl, pyraxolvl. - 1X2 - imidazolyl, 1,2,3- or 1,2,4-triaaolyl, oxazolyl, isoxazolyl, 1,2,4- or 1,3,4-oxadiazolyl, thiasolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5- or 1,3,4-thiadiassolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, which group is unsubstituted or monosubstituted to trisubstituted by ideatieal or different substituents aad where appropriate linked via a methylene group, suitable substituents on the heterocyele in each case being: halogen,, nitro,, cyaao, amis,©,, C,-^-alkyl,, C,-C4-alko:cy or C^-C*-alkyl thio, halogeno- (CU-C^) -alkyl halogeno- (C,-C^j -alkoxy,, halogen©- {CX-CJ -alkylthio, each having 1 to 9 identical or different halogen atoms, and di~ (C4-C4i -alkyl-ssiinc,? furthermore represent fluorine, chlorine or brouaine, where at least two ©f the radicals H3'# R4', Rs* or H®' represent hydrogen, represents in each case straight-chain or branched alkyl or alkoscy having 1 to 6 carbon atoms, represents hydroxyl, straight-chain or branched hydroxyalkyloxy having 1 to 8 carbon atoms, straight-chain or branched halogeno-alkyloxy having 1 to 3 carbon atoms and 1 to 17 identical or different halogen atoms,, cycioalkyloxy having 3 to 6 carbon atoms which is unsubstituted or monosubstituted t© polysubs ti tuted by identical or different halogen substituents, in each case straight-chain or branched alkossy ©r alkyl thio, aralkyl having t to 6 carbon atoms, or straight-chain, or branched alkoxyalkyloscy, ia each case having 1 t© 6 carbon atoms ia the alkoxy - 113 - moiety or alkyl moiety, ar aryloscy, aryl thio, aralkyl or ar&lkyloxy, ia each case having 6 to 10 carbon atoms in the aryl moiety and where appropriate 1 to S carboxj atoms ia the alkyl moiety, aad ia each case being unsuhsti-tuted or monosubstituted to pentasubstituted ia the aryl moiety by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, or represents a group -O-Z-NR^'R"', -NER10'» -NR1VR"' or -OH, represents formyl or cyano e> or represents the group -C-R8' II 0 represents hydrogen,, straight-chain or branched alkyl having 1 to 6 carbon atoms,, or aryl which has 6 to 10 carbon atoms and which is unsubstituted or monosubstituted to panta-subsstituted by identical or different substituents , suitable aryl substituents being the aryl substituents mentioned above, represents straight-chain or branched alkyl having 1 to -6 carbon atoms, or aryl which has 6 to 10 carbon atoms and which is unsubstituted or monosubsti tuted to pentasubsti tuted by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, represents straight-chain or branched alkyl having 1 to S carbon atoms, or aryl which has 5 to 10 carbon atoms and which is unsiuubsti-tuted or monosubstituted to pentasubsti tuted by identical or different substituents. - 114 - suitable aryl substituents being the aryl substituents mentioned above# represents hydrogen,, or represents .an equivalent of a corresponding alkali saetal cation, alkaline earth metal cation ©r aanaonium cation*. and % represents a straight-chain or branched alkyl chain having 1 to 8 carbon atoms or R2' and H3' together represeat one of the radicals "E"? n"a *S"°"S" -v- "(CH7)„-O-C-H l,3. I II II « 2 » II 0 R*J 000 0 bridged via the 6~ and 5-positions, *«fhere R13' represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or aryl which has 6 to 10 carbon atoias and which is unsubstituted or ssonosubstituted to pentasubsti tuted by identical or different substituents, suitable, aryl substituents being the aryl substituents mentioned above, and m represents a number 1 or 2, or a4' and a5' together represents an alkyl chain which has 3 or 4 carbon atoms. and which is linked via the 4- and 3-positions, and their acid addition salts aad metal salt complexes . - 115 - Substituted. 2 - eye lohexen - 1-yl - amine derivatives of the formula (la) according to Claim 2, in which E1' represents hydrogen,, straight-chain or branched alkyl having 1 to 4 carbon atoms, or fluorine, chlorine or bromine, R2' represents foroayl, straight-chaia or branched hydroxyalkyl having 1 to 4 cartoon atom® in the alkyl moiety, cyano or nitro, or represents! one of the radicals -CHa-0-C-R7', -C-R®' or I 11 O o -CH=CH~Rg g R3', R*'e R5' and W' are identical or different and in each case represent hydrogen, in each case straight-chaia or branched alkyl or alkoxy having 1 to 6 carbon atoms, in each case straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, ia each case having 2 to 6 carbon atoms, or alkoxyalkyloxy, in each case having 1 to 6 carbon atoms in the individual alkyl moieties, or represent phenyl or phenylalkyl, where appropriate having 1 or 2 carbon atoms in the alkyl jaoiety* and in each case being unsubstituted or monosubstituted to trisubstituted in the phenyl moiety by identical or different substituents, suitable phenyl substituents beings fluorine, chlorine, bromine, nitro, cyano, amino,, Cj-C2-alkyl, Cj-C,-alkoxy, C, - Ca-alkyl thio,, halogeno-C C% - C2 J - alkyl, halogeno - (Cx-CaJ - alkoxy and halogeno- CCj-Cj) -alkylthio, in each ease having 1 to 5 identical or different fluorine and/or chlorine atoms, and di~{Cx-C2| -alkylamino, furthermore represent a heterocyclic five- a>r six-mexabered group from the series comprising furyl, thienyl, pyrrolyl, pyraasolyl, - 1X6 - imidazolyl, 1,2,3- or 1,2,4-triazolyl, oxa-solyl, isoxasolyl, 1,2,4- or 1,3,4-oxadia-zolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pvridazinyl, pyrimidinyl and pyraseinyl, which group is unsubstituted or monosubstituted to trisubstituted by identical or different substituents and where appropriate linked via a methylene group, suitable substituents on the heterocycle ia each ease beings fluorine, chlorine, hroasdrMg,* aitro, cyano, axaino, Cx-Ca-alkyl, Cj-C,-alkoxy or Cx-C2-al3cylthio, halogeno- (Cj-Ca) -alkyl, halogeno- (Cx~Ca) -alkoxy and halogeno- {Cx~Ca) -alkylthio, is, each case having 1 to S identical or different fluorine and/or chlorine atemas, and di-(Ca-Ca) -alkyl-saino* furthermore represent fluorine, chlorine ar bromine,, where at least two of the radicals R1', R4', a5' and H5' represent hydrogen, represents in each, ease straight-chaia or branched alkyl or alkoxy having 1 to 4 carbon atoms, represents hydroxyl, straight-chain or branched hydroxyalfcyloxy having 1 to 6 carbon atoms, straight-chain or branched halogen©-alkyloxy having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, cycloalkyloxy having 3 to 6 carbon atoms which is unsubstituted or anoaosubsfcituted to fcris'iab-EZtituted by identical or different substituents fro® the series consisting of fluorine# chlorine and bromines, in each, ease straight-chain or branched alkoxy or alkylthio having 1 to 4 carbon atcsas, or straight-chain - 117 - or branched a I fcoscya 1 ky 1 osy c, is, each case having 1 to 4 carbon atoaie in the alkoxy moiety or alkyl saoiety£- or phenyloacy, phenyl-thio, phenylalkyl or phenylalkyloxy, where 5 appropriate in each ease having 1 to 6 carbon atoms in the alkyl moiety, anci in each case unsubstituted ox monosubstituted to triswbsti-tuted in the phenyl moiety by ideatieal or different substituents? suitable phenyl sub-10 stituents being the phenyl substituents mentioned above, or represents a group -0-Z~NXll'R12', -NHR10', -NRlva"' or -OH, Hs' represents forsayl or cyano, or represents the group -C-R® II 0 IS a10' represents hydrogen,, straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubstituted or sEonosubsti-tuted to trisubsti tuted by identical or different substituents, suitable phenyl 3ub-20 stituents being the phenyl substituents mentioned above, R11' represents straight-chaia or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsuhstitufced or monosubs ti tuted to trisubsti-25 tuted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, S3-2' represents straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is 30 unsubstituted or monosubstituted to trisubsti- tuted by identical or different substituents,. - 118 - suitable phenyl substituents being the phenyl substituents mentioned above,, M represents hydrogen, or represents an equivalent o£ a corresponding alkali saetal eatioa,, alkaline earth metal cation or ammonium eafcion aad Z represents a straight-chain or branched alkyl chaia having 1 to 6 carbon atoms, or R2' and R3' together represent one of the radicals — C"N C™„ -C-O-C- ~ / r*ij \ -m1"- II I,,. II II II or "="*'« ° S 0 R13 0 0 0 o bridged via the S- aad 5-positions, R13' represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms or phenyl which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents* suitable phenyl sub-stituents being tha phenyl substituents mentioned above, and au represents a number 1 or 2, or R*' and Rs' together represents an alkyl chain which has 3 or 4 carbon atoms aad which is linked via the 4- and 3-position®, aad their acid addition salts and metal salt complexes . The hydrochloride of the cis-diastereosaer of - 119 - 2-amino-cyclohex-3-en©-carboxylic &eid« The hydrochlorides of the enantiomers of 2-amino-cyclohex-3-ene-carboxylic acid of melting point 210 - 213»5°C aad 200 - 210°C» The 2 - amino- eyelohex- 3 - ene- carbo: (II) R I H2' ■ c-o 0-B14' in which 20 R1', Ra*, E3% R4', Es' and 3.*' have the above- mentioned meaning aad R14' represents hydrogen, methyl or ethyl, - 122 - are treated in a generally customary manner with chloroformic aeid e3ter, by the method of Curtius, if appropriate ia the presence of a diluent aad ia the presence of a base at temperatures between -15°C aad +19°C, and adding aa aside to this reaction mixture, if appropriate in the presence! of a diluent, at temperatures between ~5°C and 4-25°C, and hydrolyzing the isocyanate, which occurs as an intermediate, ot the formula (Ila) R4- (Ila) ia shieh N=C=0 R2', R3'* a*1', a5' and S*' have the abovementioned meaning, with %?afcer# if appropriate in tbe presence of aa acid or a base« aad,? if desired, converting the resulting amines into acid addition salts and saetal salt complexes, or the amino-protecting group is eliminated from the 2-cyclohexene derivatives of tha formula (lib) >4 • (lib) in which R1', R2', E3', R4', Es' aad R6' have the above-mentioned meaning and - 123 - A represents an amino-protecting group,, in a known manner by customary methods, if appropriate is the presence of a suitable solvent or diluent or a saiseture thereof, with eooliag,, at room temperature or with heating &nd{, if required,, in a sealed vessel, under pressure, in aa inert gas atmosphere and/or under anhydrous conditions, and, if desired,, converting the resulting products into acid addition salts or metal salt complexes. 2-Cyclohexene derivatives of the formula (lib) (lib) in which Rx\, H2'p H3'„ H4', Rs' and R6'' have the meaning indi* cated ia Claim 2 and A represents an amino-protecting group, with the exception of the compounds and the enan-tioMers and isomers thereof: methyl 6-£ormyl-5-{ [ (pixenylMe-carbonyl] -aminoJ-3-cyclohexene-l c&rboxylate and methyl 6- [3-oxo-l-propenyi)-5-{ [ (phenylmethoxy) -carbonyl) -amino}-3-cyclohexene-1 carboxylate, methyl 3-cyclohexene-2-[(triohlora-acetyl)-amino]-1-carboxylate, 2,2,2-trichloro-N-{6 £omyl-2-cyclohexen-l~yl) -acetaaiide, ethyl (6-formyl - 5 -methyl - 2 - eye lohexen-1 -yl} - earbassate , methyl 2- [ Cethoxy-carbonyl) -amino) -6~»ethyl-3-cyclohexene-1-carboxylate, methyl 2 - [(ethoxy-carbonyl) - amino J - 5 -me thyl - 3 - eye lohexene -1 - carboxy 1 ate, methyl 2-[Jethoxycarbonyl)-amino]-3- - 124 - cyclohexenes -1 - carboxylate, ethyl 3-{2~ [ (ethoscy-carbonyl) -amino] -6~mefchyl-3-cycl©heacen-l-yl}-2~ propanoate, pheny Imethy 1 <6-formyl-5-propyl-2~ cyclohexen-l-yl) -carbamate,? phenylsaethyl (6»formyl~ 5 5 -methyl - 2 - cyclohexen-1 -yl) - carbamate, methyl 2- [ Cphenoxycarboayl) -asniaoS -S-cycloheoceaae-l-car-boacylate aad ethyl 3-<(5-aaethyl~2-{ I Cphenylmethoxy} -carbonyl3 - aad.no} -3 -eye lohexen-1 -yl> - 2 -propenoat®, phenylaethy 1 (€-f ormyl-5-pentyl-2-cyelohexen-1 -ylJ -10 carbamate, phenyl S-carbomethoxy~2 -cyclohexen-1 -yl- thiocarbamate, N- {6-carbomethoxy ~2-eye lohexen-1-yl) -l-pyrrolidine-carbostamide, aaethyl, t-butyls benzyl and 2,4,6- triaethylphenyl 2-1 (p-tolueaesul-phonyl) -amino3 -3~cyclohe2cea-l-yl-carboxylatG and 15 phenvlaethy 1 {i-forayl^S- 12-C^ethox^ethoacy) - ethyl) -2-cyclohexen- 1-yl}-carbamate» 11. Pesticides* characterized ia that they contain at least one 2 - cyclohexen- 1-yl - amine derivative of the formula CD according to Claim % and using surface- 20 -active agents - 12. Method o£ samhatisg peses,? characterized ia that 2-cycloheacen-1 -yl -amine derivatives of the formula Clj according to Claim 1 are allowed to act on pests ana/or their environment - 25 13. Process for the preparation of pesticides, charac terised is that 2 - eye lohexen -1-yl - amine derivatives of the formula (I) according to Claim 1 are mixed with extenders and/or surface-active agnates. 14. Use according to claim 1f substantially as hereinbefore described. - 125 - 15. A substitued 2-cyclohexen-l-yl-amine derivative of the formula (Ia), given and defined in claim 2, or an acid addition salt or metal salt complex thereof, substantially as hereinbefore described and exemplified. 5 16. A process for the preparation of a substituted 2-cyclohexen-l-yl-amine derivative of the formula (Ia), given and defined in claim 2, or an acid addition salt or metal salt complex thereof, substantially as hereinbefore described and exemplified. 10 17. A substituted 2-cyclohexen-l-yl-amine derivative of the formula (Ia), given and defined in claim 2, or an acid addition salt or metal salt complex thereof, whenever prepared by a process claimed in a preceding claim. 15 18. A compound as claimed in claim 10, substantially as hereinbefore described. 19. A pesticide according to claim 11, substantially as hereinbefore described. 20. A method according to claim 12 of combating pests, 2 0 substantially as hereinbefore described. F. R. KELLY & CO. AGENTS FOR THE APPLICANTS.
IE417089A 1988-12-27 1989-12-21 Fungicidal and herbicidal agents, and substituted 2-cyclohexen-1- yl-amine derivatives and their preparation IE62165B1 (en)

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