IE62165B1 - Fungicidal and herbicidal agents, and substituted 2-cyclohexen-1- yl-amine derivatives and their preparation - Google Patents

Fungicidal and herbicidal agents, and substituted 2-cyclohexen-1- yl-amine derivatives and their preparation

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Publication number
IE62165B1
IE62165B1 IE417089A IE417089A IE62165B1 IE 62165 B1 IE62165 B1 IE 62165B1 IE 417089 A IE417089 A IE 417089A IE 417089 A IE417089 A IE 417089A IE 62165 B1 IE62165 B1 IE 62165B1
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alkyl
carbon atoms
substituted
chain
unsubstituted
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IE417089A
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IE894170L (en
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Franz Kunisch
Peter Babczinski
Dieter Arlt
Hans-Joachim Santel
Robert R Schmidt
Wilhelm Brandes
Harry Strang
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Bayer Ag
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Publication of IE894170L publication Critical patent/IE894170L/en
Publication of IE62165B1 publication Critical patent/IE62165B1/en

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    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
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    • 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
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
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Abstract

There is described the use of 2-cyclohexen-1-ylamine derivatives of the formula (I) 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.

Description

The present invention relates to the uss of substituted 2-cyclohexen-l-yl~amine derivatives, saae of which are known, ia pesticides, in particular as fungicides and herbicides, and to new substituted 2~cydohexen-l>yl5 aaaine derivatives and several processes for their preparation .
It is already known that certain tetrahydrophthalimides, such as, for example, cis-N-[(trichloromethyl)thio]-4cyclohexene-1,2-dicarboiad.de, have fungicidal properties (cf., for example. Science, (Washington) 115, 84 (1952)> US 2,553,770).
However, the action of these compounds is not always entirely satisfactory in all fields of application, in particular when low application rates and application concentrations are used.
Furthermore, it is already known that 2-eyeloaIkeaylamine derivatives and their salts, such as, for example, N-2cyclohexen-l-yl-2,2-dimethyl-propxonamd.de, have fungicidal properties (cf., for example, EP-OS (European Published Specification) 0,123,005).
In addition, M-benzyl-2-cyclohexen- 1-yl-amine derivatives, such as, for example, Si-4-methylbenzyl-2-cyclohexenylamine, have been described as intermediates for the preparation of substituted benzylcycloalkenylurea. derivatives (cf. EP-OS (European Published Specification) 0,1X3,028).
Moreover, substituted 2-eyelohsxen-1-yl-amine derivatives, euch as, for example, 6-carbomethoxy-2-cyclohexea1-yl-amine, are known as additives for lubricating oils (cf. US Patent Specification 4,582,6135...
Substituted 2-eyelohexen-1-yl-amine derivatives, such as, for example, 5-carbomethoxy-2-cyclohexea-l-yl-(4,4'dimethoxybenzhydrylamine), are also described as intermediates for the synthesi© of the natural substance (±) -gabaculia (cf. u. Org. Chem. 44, 3451-3457, 1979).
In addition, the Diels-Alder reaction of various Nacylasaino-1, 3 -butadienes with methyl acrylate to give the corresponding Si-acyl amino-2-cyclohexene derivatives,, such as, for example, 6-carbosaethoicy-2-cyclohexen“l-yl ethyl carbamate, is quantitatively investigated (cf. J. Asa. Chem. Soc., 100, 3182-9, 1978).
Furthermore, the synthesis of a plurality of 2-cyclohexen- 1-yl-amine derivatives has been described (cf. c. Had. Che»., 29, I - 8, 1986,· J. Med. Chem., 24, 788-94, 1981, Gassss. Chi». Ital. 57, 295-7 (1927), J. Asa. Che». Soc., 103, 28X6-22, 1981? J. Am- Che». Soc., 100, 3182-9, 1978? J. Asa. Che». Soc., 100., 5179-35, 1978 and Tetrahedron Lett», 25,, 2183-6, 1984, J. Org. Che»., 46, 2833-5, 1981, J. Asa. Chem. Soc», 105, 5373-9, 19835, however, nothing is known about their activity in the field of plant protection.
It has now been found that the substituted 2-cyelohexen1-yl-aaine derivatives, some of which are known, of the formula (X) in which represents hydrogen, alkyl or halogen.
R2 represents formyl, hydroxyalkyl, cyano or nitro, or represents oae of the radicals -J3S&8 -saes£’, ,XH -NH-CH-COOM,-CH2-O-C-R9 -C-H13, -PC©11),, “?«.
II II, Λ 11.
X~ X· -S(Q)nRx* or -CH=CH-RX5, R3 and S'4 are identical or different and ia each case represent hydrogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloscy or alkinyloxy, or represent unsubstituted or substituted aryl, or represent unsubstituted or substituted aralkyl, or represent unsubstituted or substituted heteroaryl, or represent unsubatituted or substituted heterocyclylalkyl, alkoxyalkyloxy or halogen, or represent one of the radicals -&H-R5, -NReR7 or -S (0)3-Rx% or R3 and R3 together represent one of the radicals -C-M-C~, -C-O-C- o- -5J„-0~G“ II 1,. II II II ‘ m II Ki0 0 0 0 0 which are bridged via the 6- and 5-positions, IS or R3 and K4 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 unsubstituted or substituted aryl, R6 represents alkyl or unsubstituted or substituted aryl, R7 represents alkyl or unsubatituted or substituted aryl, R® represents hydrogen, alkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl, R9 represents! alkyl or alkoxy? R?° represents hydroxyl? hydroxyalkyloxy? halogexxoalkyloxy? alkoxy? alkoxyalkyloxy? unsubstituted or substituted cycloalkyloxy? unsubstituted or substituted aralkyloxy? unsubstituted or substituted aryloxy? unsubstituted or substituted aralkyl? alkylthio or unsubstituted or substituted arylthio? or represents a group -OH? -NHR5? -NReR’ or -O-Z-NR5R% Rw represents hydrogen or alkyl? R12 represents hydrogen or alkyl? Ri3 represents alkyl? SM represents alkyl? alkoxy or unsubstituted or substituted aryl? or represents the group -OH? RX3 represents formyl or cyano? or represents the group II R3'9 represents hydrogen? alkyl or unsubstituted or substituted aryl? M represents hydrogen or represents aa equivalent of a corresponding alkali Metal cation? alkaline earth metal cation or annaoniun cation? n represents a number 0? 1 or 2? X and Z’ are identical or different and represent oxygen or sulphur? m represents a number 1 ©r 2? A represents hydrogen or an amino-protecting group and Z represents a straight-chain or branched alkyl chain, and their acid addition salts and metal salt complexes show powerful biological properties.
The compounds of the formula (I) can be present as geometric isomers (2/S isomers) or mixtures of isomers of varying composition. The invention claims the use of the pure isomers as well as the mixtures of isomers.
Is addition, the compounds of the formula (I) contain 1 to 4 chiral centres and can therefore be present in various mixtures of enantiomers and diastereomers, which, if appropriate, can be separated in a customary manner. The invention likewise claims the use of the pure enantiomers and diastereomers as well ss that of the mixtures» For reasons of simplicity,, the following will always refer to the use of compounds of the formula (I) even though, there will be meant the pure compounds as well as the mixtures of varying proportions of isomeric, enantiomeric and diastereomeric compounds.
Surprisingly, the substituted 2-cyclohexea-l-yl-amine derivatives of the formula (I), some of which are known, and their acid addition salts and metal salt complexes show better fungicidal properties when applied at appropriate concentrations than cis-2?- [(trichloromethyl) -thio] 4 - eye lohexene-1,2 -dicarboimide, which is known from the prior art and an active compound of a similar constitution and of the same type of action. The substituted 2cyclohexen-l-yl-amine derivatives of the formula (X), some of which are known, additionally also show very good herbicidal properties when applied at appropriate concentrations .
Foraaula (X) provides a general definition of the substituted 2-cyclohexen-l-yl-amine derivatives to be used according to ‘the invention. - 6 Unless defined otherwise, the radicals ia the general formulae have the following meaningss Alkyl - straight-chain or branched alkyl having 1 to 8, preferably 1 to 6,. in particular 1 to 4, carbon atoms.
Examples which may preferably be mentioned are optionally (substituted methyl» ethyl» a,- .and i.-propyl» n-; I-, saad t-butyl.
Alkenyl and the alkenyl moiety of optionally substituted alkenyloxy - straight-chain or branched alkenyl having 2 to 8» preferably 2 to 6, in particular 2 to 4» carbon atoms. Examples which may preferably be mentioned are optionally substituted ethenyl» 1-propenyl, 2-propenyl and 3-butenyl.
Alkinyl and the alkinyl moiety of optionally substituted 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 be mentioned are optionally substituted ethinyl, 1-propinyl, 2-propinyl and 3-butinyl.
Alkoxy - unsubstituted or substituted, straight-chain or branched alkoxy having 1 to 8» preferably 1 to 6» ia particular 1 to 4, carbon atoms. Examples which may preferably be mentioned are optionally substituted methoxy, ethoxy, n.- and i.-propoxy and η-, I-, is- and t25 butoxy.
Aryl - preferably unsubstituted or substituted phenyl or naphtyl. Is particular phenyl.
Aralkyl and aralkoxy - unsubstituted aralkyl or aralfcoxy or aralkyl or aralkoxy which is substituted In the aryl moiety and/or alkyl moiety, preferably having 6.or 10» In particular 6» carbon atoms in the aryl moiety (preferably phenyl or naphthyl, In particular phenyl) and preferably having 1 to S, In particular 1 to 6» carbon atoms in the - 7 alkyl moiety, it being possible for th© alkyl moiety to be straight-chain or branched. Examples which may preferably be mentioned are optionally substituted benzyl and phenylethyl or benzyloxy and phenylethyloxy.
Unsubstituted or substituted heterocyclic radicals in the general formulae denote heteroparaffiiaic, heteroaromafcic and heteroolefiaic 5-S-membered rings, preferably having 1 to 3,, in particular 1 or 2, identical or different hetero atoms. Hetero atoms are oxygen, sulphur or nitrogen. Hxamples which may preferably be mentioned are pyrrolidinyl, piperidinyl, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-fcriazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,3,4- and 1,2,4-oxadiasolyl, azepi&yl, pyrrolyl, isopyrrolyl, pyridyl, pyridazxnyl, pyrimidinyl, pyraziayl 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 aad bromine, aad particularly preferably fluorine .and chlorine.
The optionally substituted radicals of the general formulae can carry one or more, preferably 1 to 3, in particular 1 or 2, identical or different substituents. Examples of substituents which may preferably be mentioned are: Alkyl preferably having 1 to 4, ia particular 1 or 2, carbon atoms, such as methyl, ethyl, a.- and i.-propyl and a - -, i. - and t. -butyl j alkoxy preferably having 1 to 4, in particular 1 or 2, carbca atoms, such as methoxy, ethoxy, n.- and i.-propyloxy and a.-, i--, sec.- and t.butyloxy; alkylthio preferably having 1 to 4, in particular 1 or 2, carbon atoms, such as methyl thio, ethyl thio, a.- and i.-propyl thio and a.-, 1.-, sec.- and t.-butylthio? halogenoalkyl, halogeaoalkoxy aad halogeaoalkylthio, preferably having l to 4, in particular 1 or - 8 2? carbon atone and preferably 1 to 9? in particular 1 to ? halogen atoms? the halogen atoms being identical or different, and preferably being fluorine? chlorine or bromine? in particular fluorine? such as trifluoromethyl? trifluoromethoxy? and trifluoromethylthio; hydroxyl; halogen? preferably fluorine? chlorine? bromine and iodine? in particular fluorine? chlorine and bromine; cyano? nitro; amino; dialkylamino? preferably having 1 to 4? in particular 1 or 2? carbon atoms per alkyl group? such as methyl-ethyl-amino? and methyl-».-butyl-amino; carboxyl.
Compounds of th© formula (X) which are preferably used are those in which S,1 represents hydrogen? straight-chain or branched IS alkyl having 1 to 6 carbon atoms? or fluorine? chlorine or bromine? Ra represents formyl? straight-chain or branched hydroxyalkyl having 1 to 8 carbon atoms in the alkyl moiety, cyano or nitro? or represents one of the radicals “NHR5, NR6R7, “NH-CH-COOM, -CH~>-0~C~R9.
I. II ' R8 O -C-R10, -FOCR11)?, ?XR , -SiO)nR^ or -C3»CH-R15? R3 and R* are identical or different .and ia each case 25 represent hydrogen? in each case straight-chain os branched alkyl os alkoxy having 1 to 8 carbon atoms? in each ease straight-chain or branched alkenyl? alkinyl? alkenyloxy or alfcinyloxy? in each case having 2 to 8 carbon atoms? or - S represent alkoxyalky loxy, in each case having X to 8 carbon atoms in the individual alkyl moieties, or represent aryl ox’ aralkyl, in each case having S to 10 carbon atoms in the aryl moiety and where appropriate 1 to 4 carbon atoms in the alkyl moiety, and in each case being uaeubstituted or aoaosubetitatsd to pentasubstItuted in the aryl moiety by identical or different substituents, suitable aryl substituents being: halogen, nitro, cyano, amino, 0,-0,5-alkyl, 0,-C^-alkoxy or C,-C4-alkyl thio, halogeno- -alkyl, halogen©- (CL-C^) -alkoxy, halogen©- iC,-Gj -alkylthio,, each having 1 to 9 identical or different halogen atoms, and di~(C,_C«) -alkylamino, furthermore represent a 5- or 6-membered heterocyclic ring which can contain 1 to 3 oxygen, sulphur and/or nitrogen atoms as other hetero atoms and which is unsubstituted or monosubstituted to pentasubstituted by identical or different substituents, or represents heterocyclylalkyl which is unsubstituted or monosubstituted to pentasubstituted by identical or different substituents and which comprises a 5or 6-membered ring which may contain 1 to 3 oxygen, sulphur and/or nitrogen atoms as other hetero atoms and 1 or 2 carbon atoms in the alkyl moiety, possible substituents in the heterocycle in each case being: halogen, nitro, cyano, amino, Cj-Qj-alkyl, C,-C*-alkoxy, C^-C^-alkyl thio, halogeno-(Ci-C4)-alkyl, halogen©- (Cj-QJ-alkoxy and halogeno- (C,-Cs) -alkylthio, each having 1 to 9 identical or different halogen atoms, and di-(CxC4) -alkylamino, furthermore represent fluorine, chlorine or bromine, or represent a radical -MH-R5, -2SR6R7 or -SiO?a-Rx% or r’ and R3 together represent one of the radicals -C· 11 ',.
Ris> 0 -, -C-O-C- or ~7)„-0-Cii a 2 “ it 0 0 bridged via the 6- and 5-positionsf or R3 and Et* together represent an alkyl chain which has 3 or 5 4 carbon atoms and which is linked via the 4- and Impositions, B5 represents hydrogen, straight-chain or branched alkyl having 1 to & carbon atom®, or aryl which has 6 to 10 carbon atoms and which is unsubstituted or monosubstituted to pentasubs ti tuted by identical or different substituent®, suitable aryl substituents being the aryl substituents mentioned for R3, R® represents straight-chain or branched alkyl having 1 to S carbon atoms, or represents aryl which has 6 tc 10 carbon atoms and which is unsubstituted or xnonosubstituted to pentasubstituted by identical or different substituents, suitable aryl substituents being those aryl substituents mentioned for R3, R7 represents straight-chain or branched alkyl having 1 to 6 carbon atoms, or represents aryl which has 6 to 10 carbon atoms and which is unsubstituted or monosubsfcituted to pentasubstituted by identical or different substituents, suitable aryl substituents being those aryl substituents mentioned under R3, 2:5 R® represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms, ox represents aryl or aralkyl, in each case having 6 to 10 carbon atoms in the aryl moiety and where appropriate 1 to 4 carbon atoms in the alkyl moiety, and in each ease being unsubstituted or monosubstituted to pentasubstituted ia th® aryl moiaty by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned for R3, B? represents in each case straight-chain or branched alkyl or alkoxy having 1 to 5 carbon atoms, B?° represents hydroxyl, straight-chain or branched hydroxyalkyloxy having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyloxy having 1 to 8 carbon atoms and 1 to 17 identical or different halogen atoms, cycloalfeyloxy having 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 alkylthio having 1 to 6 carbon atoms or straight-chain or branched alkoxyalkyloxy in each case having 1 to 6 carbon atoms in the alkoxy moiety and alkyl moiety, or aryloxy, arylthio, aralkyl or aralkyloxy, in each case having S to 10 carbon atoms in the aryl moiety and where appropriate 1 to 8 carbon atoms in the alkyl moiety, aad in each case being unsubstituted or monosubstituted to peatasutastituted in the aryl moiety by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned for R3, or represents a group ~NRHS, -NRSR7 or -O-Z-NRSR6, r” represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms, R12 represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms, a13 represents straight-chain or branched alkyl having 1 to 6 carbon atoms., Rx's represents in each case straight-chain or branched alkyl_or alkoxy having 1 to 6 carbon atoms, or aryl which has 6 to 10 carbon atoms and which is unsubstituted or moaosubstituted to pentasubstituted by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned for R3» or represents the group -OM, R15 represents formyl or cyan©, or represents the group -C-R10 SI Rie represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, or aryl which has to 10 carbon atoms and which is uasubstituted or monosubstituted to pentasubstituted by Identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above for K3» si represents a number 1 or 2 and M represents hydrogen, or represents aa equivalent of a corresponding alkali metal cation, alkaline earth metal cation or .ammonium cation, a represents a number 0» 1 or 2» 2,0 X and X1 are identical or different and represent oxygen or sulphur, A represent® hydrogen or an amino-protecting group and Z represents a straight-chain or branched alkyl chain having 1 to 8 carbon atoms.
Other preferred compounds to be used according to the invention are addition products of acids and those substituted 2-cyclohexen-l-yl-amxne derivatives of the formula (X> in which R1, Ra, Ra and Si* have the meanings which have already been mentioned in connection with the description of the substances to be used according to the invention as being preferred.
The acids which caa be added on preferably include hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, ia particular hydrochloric acid, furthermore phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, trifluoroacetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, oleic acid, stearic acid, benzoic acid which is optionally monosubstituted to polysubstituted by nitro or halogen, gluconic acid, ascorbic acid, malic acid, sulphamic acid, sulphonic acids, such as, for example, p-tolueaesulphonic acid, 1,5-naphthalenedisulphonic acid and methanesulphonic acid, and imides, such as, for example, phthaliaide, saccharin and thiosaccharin.
In addition, other compounds which are preferably to be used according to the invention are addition products of salts of metals of main group X, II and XX and of tin, and furthermore salts of metals of sub-groups X, XI, VII and VXXI of the Periodic Table of the Elements and those substituted 2 - eye lohexen-l-yl-amine derivatives of the formula (X) in which R~, Br, R3 and R* have the meanings which have already been mentioned in connection with the description of the substances of the formula (I) to be used according to the invention, as being preferred for these substituents® Xa this context, salts of copper, zinc, manganese, 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!. Xn this connection, particularly preferred acids of this type are the hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid? nitric acid and sulphuric acid.
Compounds of the formula (Σ) which are particularly preferably used are those in which a’ represents hydrogen? straight-chain or branched alkyl having 1 to 4 carbon atoms? or fluorine? chlorine or bromine? Ra represents formyl? straight-chain or branched hydroxyalkyl having 1 to 4 carbon atoms in the alkyl moiety? cyano or nitro? or represents one of the radicals -CH,-O-C-R9, ~ j, ? ~S(O)nR^ or -CH=CH-R1S, R3 and St* are identical or different and in each ease represent hydrogen, in each ease straight-chain or branched alkyl or alkoxy having 1 to S carbon atoms.? in each case straight-chain or branched alkenyl? alkinyl? alkenyloxy or alkiayloxy, in each ease having 2 to 6 carbon atoms? or represent alkoxyalkyloxy? ia each case having 1 to S carbon atoms in the 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 pentasubstituted is the phenyl rsoiety by identical or different substituents? suitable phenyl substituents beings fluorine? chlorine? bromine? nitro? cyano, amino? C,»C2- alkyl, C-C,-alkoxy or C,-C,~ alkyl thio? halogeno-3i-alkyl? halogen©- -alkoxy and halogeno- (C,-C2) -alkylthio, in each case having 1 to 5 identical or different fluorine and/or chlorine atoms, furthermore represent a heterocyclic fives- ©r sixmembered 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- oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1.2.4- , 1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, which group is unsubstituted or monosubstituted to hrisubstituted by identical or different substituents and where appropriate linked via a methylene group, suitable substituents on the heterocycle in each case beings fluorine, chlorine, bromine, nitro, cyano, amino, Ο,-Cg-alkyl, C^C3-al!mxy, Cx-C.-alkylthio, halogeno-(C^-C,)-alkyl, halogeno-(Cx-Ca)-alkoxy and. halogen- {G»~C2> -alkylthio, each having 1 to 5 identical or different fluorine and/or chlorine atoms, and di-(C»-G,) -alkylamino, furthermore represent fluorine, chlorine or bromine, or represents one of the radicals -NH-R5, -NR®R7 or -S or R2 and K? together represent one of the radicals -C-N-C-, -C~O-C- or -7.)_-O-C- » III. II II II II ' 0 0 0 0 bridged via the 6- and 5-positions, or R3 and R* together represents an alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4- and 3-positions, Rs represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which unsubstituted or monosubs titufced to peatasubstitutad by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned for R3, R® . represents straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubstxtuted or monosubstituted to pentasubs ti tut ed by identical or different substituents, suitable phenyl substituents being those phenyl substituents mentioned for R3, R7 represents straight-chain or branched alkyl having to 4 carbon atoms, or phenyl which is unsubstituted or monosubs titufced to peatasuhstitufced by identical or different substituents, suitable phenyl substituents being those phenyl substituents mentioned for R3, R® represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms, or represents phenyl or phenylalkyl, where appropriate having 1 or carbon atoms in the alkyl moiety, aad in each case being uasuhstitufced or moaosubstituted to pentasubstituted in the phenyl aoiefcy by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned for R3, R® represents in each case straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, R10 represents hydroxyl, straight-chain or branched hydroxyalkyloxy having 1 to 6 carbon atoms, straight-chain ox branched halogenoalkyloaey having to 6 carbon atoms and 1 to 13 identical or different halogen stems, cycloalkyloxy having 3 to 6 carbon atoms which is unsubstituted or stonosubstituted to -trisubstituted by identical or different substituents from the aeries consisting of fluorine,, chlorine and bromine, in each case straight-chain or branched alkoxy or alkylthio having 1 to 4 carbon atoms, or straight-chain or branched alkoxyalkyloxy, in each case having 1 to 4 carbon atoms in th© alkoxy moiety or alkyl moiety, or phenyl oxy, phenylthio, phenylalkyl or phenylalkyloxy, where appropriate in each case having 1 to 6 carbon atoms in the alkyl moiety, and la each case unsubstituted or moaosubstituted to peatasubstituted in th® phenyl moiety by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned for R3, or represents a group OM, -MHR®, -MReR’ or -O-Z-MRSR®, R11 represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms, R12 represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms, Ri3 represents straight-chain or branched alkyl having 1 to 4 carbon atoms, Η14 represents in each case straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, or pheayl 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, Rls represents formyl or cyano, or represents the group -c-r10 o R1® represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is IS unsubstituted or monosubstituted to pentasubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above for R3» S sa represents a number 1 or 2 .and BS represents hydrogen, or represents aa equivalent of a corresponding sodium cation, potassium cation or ammonium cation, n represent© a number 0» 1 or 2, X and X1 are identical or different and represent oxygen or sulphur, A represents hydrogen or .an aaaiao-protecfciag group and Z represents a straight-chain or branched alkyl chain having 1 to S carbon atoms.
The term amino-protecting group” Is generally known and relates to groups which are suitable for protecting (for blocking) aa amino group from chemical reactions, but which are readily detachable after the desired reaction has been carried out on other sites of the molecule.
Representative of such groups are. In particular, unsubstituted or substituted acyl, aryl - for example DISP (2,4-dinitrophenyl>» aralkoxymethyl = for example BOM (S(benzyloxy)methyl), or aralkyl groups (for example benzyl, 4-nitrobenzyl» triphenylmethyl) . Incidentally, 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» ia particular 1 - 8, carbon atoms are preferred. In connection with the present invention, the term acyl group” is taken to mean acyl groups la the broadest sense. It comprises acyl groups derived from aliphatic, araliphatlc, aromatic or heterocyclic carboxylic acids or sulphonic _ acids, and in particular alkoxycarbonyl, aryloxycarbonyl and especially aralkoxycarbonyl group®» Examples of acyl groups of this type are alkanoyl, such as acetyl, propionyl, butyryl? aralkanoyl such as phenyl5 acetyl? aroyl such as benzoyl or toluyl? aryloxyalkanoyl, such as POA (phenoxyacetyl) ? alkoxycarbonyl, such as methoxycarbonyl, ethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, SOC (tert.-butoxyearboayl), 2-iodoethoxycarbonyl? aralkyloxycarboayl, such as CBS (Bcarbo10 benzoxy8) and 4-methoxvbenzyloxycarbonyl. Pref erred amino-protecting groups are benzyl, acetyl, methoxycarbonyl, allyloxycarbonyl, trichloroethyloxvcarbonyl, (“) -menthyloxycarboayl, tert-butoxycarbonyl and benzyloxycarbonyl.
The application furthermore relates to new substituted 2cyclohexen-l-yl-amine derivatives of the formula (la) in which (la) R1* represents hydrogen, alkyl or halogen, R2' represents formyl, hydroxyalkyl, cyano or nitro, or represents one of the radical© -CHn-O-C-R7', -C-R®' or O 0 „ f»W „ frat - w ®' R9', R4', R3' and R6' are identical or different and in each 25 case represent hydrogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy and alkinyloxy, or represent unsubsti tuted ©r substituted aryl, or .represent unsubstituted or substituted aralkyl, or represent unsubstituted or substituted heteroaryl, or represent unsubstituted or substituted hsterocyclylalkyl. or represent alkoxy&lkyloxy, or represent halogen, where at least two ©f the radicals R3', R*', R3' or Re' represent hydrogen, R7’ represents alkyl or alkoxy, R8' represents hydroxyl, hydroxyalkyloxy, halogenoalkyloxy, alkoxy or alkoxyalkyloxy, unsubstituted or substituted cycloalkyloxy, unsubstituted or substituted aralkyloxy, uneubstituted or substituted aryloxy, unsubstituted or substituted aralkyl, alkylthio or uneubstituted or substituted arylthio, or represents a group , -NER10', -NRU'R12' or -0M, R’’ represents formyl or cyano, or represents the group -C-s?8’ II R10' represents hydrogen, alkyl or unsubstituted or substituted aryl, R11' and RX2' are identical or different and in each case represent alkyl or unsubstituted or substituted aryl, Z represents a straight-chain or branched alkyl chain aad represents hydrogen, or represents an equivalent of a corresponding alkali metal cation, alkaline earth metal cation or ammonium cation or R3' and P?' together represent one of tha radicals -C-N~ -C-, -C-O-C-iCK,U-Q-C’ R13* 0 or bridged via the 6- and 5-positions, where R13' represents hydrogen? alkyl or unsubstituted or substituted aryl and m represents a number 1 or 2? or R*' and St3’ together represent aa alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4,- and 3-positions? and their acid addition salts and metal salt complexes? with the exception of the compounds 2-amino-cyclohex-3eae-carboacylic acid and ethyl 2-amiao-cyclohex-3-enecarhaxylate.
Formula (la) provides a general definition of the substituted 2-cvclohexen-1-yl-amine derivatives which were hitherto unknown.
Preferred compounds of the formula (la) are those ia which R1' represents hydrogen? straight-chain or branched alkyl having 1 to 6 carbon atoms? or fluorine? chlorine or bromine? R3' represents formyl? straight-chain or branched hydroxvalkyl having 1 to 8 carbon atoms in the alkyl moiety? cyano or nitro? or represents one of the radicals -CHa-O-C-R7'? -C-R8' or -CH=CH-R9'? O R3'? R*'? Rs’ and R®' are identical or different and in each case represent hydrogen? ia each case straight-chain or branched alkyl or alkoxy having 1 to 3 carbon atoms, in ©ach case straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, in each case having 2 to 9 carbon atoms, or alkoxyalkyloxy, in each case, having 1 to 3 carbon atoms in the individual alkyl moieties, or represent aryl or aralkyl, ia each case having 6 to 10 carbon atoms in the aryl moiety and where appropriate I fc© 4 carbon atoms in the alkyl moiety, and ia each case being unsubstituted or monosubs tituted to pentasuhstituted in the aryl moiety by identical or different substituents, suitable aryl substituents beings halogen, nitro, cyano, amino, ex-C4-alkyl, Cx-CJ4-alkosEy, Cx-C4-alkyl thio, halogeno- (Cx-C4) -alkyl, halogeno- (CxC«) -alkoxy, halogeno- -alkylthio, each having to 9 identical or different halogen, atoms, and di(C,-C,3 -alkylamino, furthermore represent a heterocyclic 5- or S-membered 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- oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1.2.4- , 1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, which group is unsubs tituted or moaosubstituted to trisubstituted by identical or different substituents and where appropriate linked via a methylene group, suitable substituents on the heterocycle in each case beings halogen, nitro, cyano, amino, C,-G4-alkyl, alkoxy or Cx-C4-alkyl thio, halogeno--alkyl, halogeno- <€\-<2,45 -alkoxy or halogeno- CCj-QJ -alkylthio, each having 1 to 9 identical or different halogen atoms, and di-(CX~CJ-alkylamino, furthermore represent fluorine, chlorine or bromine, where at least two of the radicals R9’, &*’„ 3s' ©r R6' represent hydrogen, R7' represents in each case straight-chain or branched alkyl or alkoxy having 1 to 6 carbon atoms.
R8' represents hydroxyl, straight-chain ox* branched hydroxy&lkyloxy having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyloxy having 1 to 8 carbon stows and 1 to 17 identical or different halogen atoms, cycloalkyloxy having 3 to δ carbon atoms which Is unsubstituted or monosubstituted to polysubstituted by identical or different halogen substituents, in each case straight-chain or branched alkoxy or alkylthio having 1 to 6 carbon atoms, or straight-chain or branched alkoxyalkyloacy, in each case having 1 to 6 carbon atoms in the alkoxy moiety or alkyl moiety, or aryloxy, arylthio, aralkyl or aralkyloxy, in each case hatring 6 to 10 carbon atoms la the aryl moiety and where appropriate 1 to 8 carbon atoms in the alkyl moiety, and in each case being unsubstituted or monosubstituted to penfcasubstitufced In the aryl moiety by Identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, or represents a group -O-E-MR^'R12', -MHR10', -KRU'R12' or -OM, R9' represents formyl or cyano, or represents the group “OR8' il R10' represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, or aryl which has S to 10 carbon atoms and which Is unsubstituted or monosubstituted to pentasubstituted by Identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, R11' represents straight-chain or branched alkyl having X to S carbon atoms, or aryl which has 6 to 10 carbon atoms and which is unsubstituted or. moaosubstituted to pentasubs ti tuted by identical or difi £erent substituents, suitable aryl substituents being the aryl substituents mentioned above, R12' 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 saonosubstituted to pentasubstituted by identical or dif5 ferent substituents, suitable aryl substituents being the aryl substituents mentioned above, BS represents hydrogen, or 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 R2' and R1' together represent one of the radicals -C-H11 '-3· Ri3 -C~, -C-O-CII II II 0 0 or bridged via the 6- and 5-positions. where R13' 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 saonosubstituted to pentasubstituted by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, and sot represents a number 1 or 2» or S?' and Rs' together represent an alkyl chain which has 3 or 4 carbon atoms and which is United via the 4- and 3-positions.
Other preferred compounds according to the invention are addition products of acids and those substituted 2-cyclohexen-1-yl-amine derivatives of the formula (la) in which R1', R2’, R3', &*'„ R5' aad Rs' have th© abovementioned meanings.
The acids which can be added ©a preferably include hydrohalic acids, such as, for example, hydrochloric acid or hydrobromic acid, in particular hydrochloric acid, furthermore phosphoric acid, nitric acid, monofunctional and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, trifluoroacetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,, sorbic acid and lactic acid, oleic acid, stearic acid, benzoic acid which is optionally monosubstituted or polysubstituted by nitro or halogen, gluconic acid, ascorbic acid, malic acid, sulphamic acid, sulphonic acids, such ae, for example, p~ toluenesulphonic acid, 1,5-naphtha!enedisulphonic acid and, methanesulphonic acid, aad imides, such as, for example, phthalimide, saccharin aad thiosaccharin,.
Ia addition, other preferred compounds according to the invention are addition products of salts of metals of main groups I, IX and III aad of tin, and furthermore salts of metals of sub-groups X, II, VII aad VIII of the Periodic Table of the Elements and those substituted 2cyclohexen-1-yl-amine derivatives of the formula (la) in which R1', R2', a3', R*', Rs' and Re' have the .'abovementioned meanings.
In this context, salts of copper, zinc, manganese, magnesium, calcium, tin, iron, cobalt and of nickel are particularly preferred. Suitable aniops 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 the hydrohalic acids, such as, for example, hydrochloric acid and hydrobromic acid, and furthermore phosphoric acid, nitric acid aad sulphuric acid.
Particularly preferred compounds of the formula (la) are those ia which R1' represents hydrogen? straight-chain or branched alkyl having 1 to 4 carbon atoms? or fluorine? chlorine or bromine? R2' represents formyl? straight-chain or branched hydroxyalkyl having 1 to 4 carbon atoms in the alkyl moiety? cyano or nitro? or represents one of the radicals -CBg-O-C -C-R' C-R8' or -CH«CH-R9', O R3', R“J'? Rs' and R5' are identical or different and in each case represent hydrogen? in each case straight-chain or branched alkyl or alkoxy having 1 to 6 carbon atoms? in each case straight-chain or branched alkenyl? alkinyl? alkenyloxy or alkiayloxy, in each case having 2 to 6 carbon atoms, or alkoxyalkvloxy, ia each case having 1 fc© 6 carbon atoms in the individual alkyl moieties? or represent phenyl or phenylalkyl, where appropriate having 1 or 2 carbon atoms in the alkyl moiety? and is 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? Cl-Ca -alkyl? C,-C3- alkoxy? C,-C,- alkyl thio? halogeno(C^-C,)-alkyl, halogeno- 2> -alkoxy and halogen©(Cj-Cj) -alkylthio? in each case having 1 to 5 identical or different fluorine and/or chlorine atoms? and di- (Cx-Cj) -alkylamine? furthermore represent a heterocyclic five- or sixmembered group from the series comprising furyl? thienyl? pyrrolyl, pyrazolyl, iaidasc-lyl? .1,2,3- or 1,2,4-triazolyl? oxazolyl? isoxazolyl? 1,2,4- or l?3,4-oxadiasolyl? thiazolyl, isothiazolyl, 1?2,3-, 1,2,4-, 1,2,5- or 1? 3?4-thiadiazolyl? pyridyl? pyridazinyl, pyrimidinyl and pyrazinyl, 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 case beings fluorine, chlorine, bromine, nitro, cyano, amino, Cj-C3-alkyl, Cx-C,-aXkoxy or Cx-C3alkylthio, halogen©- (C,-C,) -alkyl, halogen©- (Cx-Ca) alkoxy and halogen©- -alkylthio, ia each case having 1 to 5 identical or different fluorine and/or chlorine atoms, and di-(Cx-Ca)-alkylamino. furthermore represent fluorine, chlorine or bromine, where at least two of the radicals R3', R*', R5' and Rs' represent hydrogen, R7' represents in each ease straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, R®' represents hydroxyl, straight-chain or branched hydroxyalkyloxy having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyloxy having 1 to S carbon atoms and 1 to 13 identical or different halogen atoms, cycloalkyloxy having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstituted by identical or different substituents from the series consisting of fluorine, chlorine and bromine, in each case straight-chain or branched alkoxy or alkylthio having 1 to 4 carbon atoms, or straight-chain or branched alkoxyalkyloxy, in each case having 1 to 4 carbon atoms in the alkoxy moiety or alkyl moiety, or pheayloxy, phenyl30 thio, phenylalkyl or phenylalkyloxy, where appropriate in each case having 1 to 6 carbon atoms in the alkyl moiety, and in each case unsubstituted or monosubstituted to trisubstituted ia the phenyl moiety by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, or represents a group -O~Z-NR1X'R12', -NHR10', -NR11'®12' or -OM, R9' represents formyl or cyano, or represents the group -C-R8’ II o R10' represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, ©r phenyl which is unsubstitufced or aoaosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, R11' represents straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubstituted ©r monosubstituted to trisubstituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, R13' 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, H represents hydrogen, or represents as 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 S carbon atoms, or R2' and R3' together represent ona of th© radicals -C-N· R13’ Ο C-O-CII II ο ο bridged via the 6- and or - -positions. it R13' represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, or phenyl which Is uasubstituted or monosubstituted to tri subs tituted by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, and ία represents a number 1 or 2, or R4' and Rs' together represent an alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4- and 3-positions.
In this connection, the same acid addition salts and metal salt complexes may be mentioned which have already been mentioned in the description of the preferred 2cyclohexen-1-yl-amine derivatives, substituted according to the invention, of the formula (la).
The substituted 2-cyclohexen-l-yl-amine derivatives of the formula (la) are obtained when A) 2-cyclohexen-l-yl-carboxylic acid derivatives of the formula (II) (II) in which R1', R2', R3’,, R*' e R5' and R*' have the abovementioned meaning and R1*' represents hydrogen, methyl or ethyl, are treated in a generally customary manner 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, a?-di isopropyl amine, at temperatures between -15eC and +10*C, and adding an azide, such as, for example, sodium azide, to this reaction mixture, if appropriate In the presence os a diluent, such as, for example, water, at temperatures between -5®C and -*-25*C, and hydrolyzing the isocyanate, which occurs as an Intermediate, of the formula (Ila) la which Rv, R3', S3’, R4', R5' and R®' have the abovementioned meaning, 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. 2jS, (1961), 35113.
In addition, the substituted Z-cyclohexen-l-yl-amine derivatives of the formula (la) are obtained S) from the 2-cyclohexene derivatives of the formula (lib) (Uh) in which and S*' have the abovementioned meaning and A represents an amino-protecting group, ia a known manner by customary methods, for example by solvolysis, such as hydrolysis or acidolysis, hy reduction, such as, for example, by hydrogenolysis in the presence of a hydrogenation catalyst or by maaas of a reduction system of metal and protoneliminating agent, where, depending on the nature of the protecting group, various types os eliminating methods, (also different types) and selective elimination methods can. be used, if appropriate in the presence of a suitable solvent or diluent or a mixture thereof, where, if required with cooling, at room temperature or with heating, for example in a temperature range of about -10°C to the boiling point of the reaction medium, preferably from about -10®G 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 complexes (cf. Protective Groups in Organic Synthesis, Th. W. Green®, Kiley Interscience, 1981) .
The formyl, acetyl or 2,2,2-trichloroacetyl group, which was mentioned before as, inter alia, .amino-protecting group, can be eliminated for example by hydrolysis.
The hydrolysis is carried out ia a manner known per se with the aid of water, it being advantageous to carry out the hydrolysis in the presence of .an acid or bus® which assists hydrolysis, if appropriate in the presence of as inert solvent or diluent and/or with cooling or heating.
Examples of suitable acids are inorganic acids, such as mineral acids, for es;awple sulphuric acid, phosphoric acid or hydrohalic acids, organic carboxylic acids, such as lower alkanecarboxylic acids, for example glacial acetic acid, such as optionally unsaturated dicarboxylic acids, for example oxalic, malonic, maleic or fumaric acid, or such as hydroxycarboxylie acids, for example IQ tartaric acid or citric acid, or sulphonic acids, such as C1-C7-alkanesuIphoaic acid or optionally substituted benzenesulphonic acid, for example methanesulphonic acid or p-tolueaesulphonic acid.
Examples ©£ suitable bases are the hydroxides, hydrides, amides, alkanolates, carbonates, tripheny Imethyl ides, diCx-C7-alkylamides, amino-C,-G7-alkylamides or e,-C7-alkylsilylamides of alkali metals, ©r naphthalene-amines, C\C7-alkylamines, basic heterocyclic compounds, ammonium hydroxides, and carbocyclic amines, Examples which may be mentioned are lithium hydroxide, sodium hydroxide, sodium hydride, sodium amide, sodium, ethylate, potassium tertbutylate, potassium carbonate, lithium tripheuylmethvlide, lithium diisopropylamide, potassium 3-(aminopropyl) amide, potassium bis-(trimethylsilyl)-amide, dimethyl-aminonaphthalene, diethylamine or triethylamine, pyridine, benzyl trimethyl-ammonium hydroxide, 1,5-diazabicyclo-(4.3.0]non-5-eae (DBM), and 1,3-diaza-bicyclo[5.4.03undec-7-ene (DBU).
Acidolysis is successfully carried out, for example using strong acids, it being advantageous t© use trifluoroacetic 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, ©r sulphonic acids, such as benzeaesulphonic acid or p-toluenesulphoaic acid. An additional inert solvent may be present.. Preferably, organic solvents, for example carboxylic acids, such as acetic acid, ethers, such aa tetrahydrofuran or dioxane, amides, such as dimethylformamide (DMF), halogenated hydrocarbons, such as dichloromethane, furthermore also alcohols, such as methanol, ethanol or isopropanol, aad water, are suitable as inert solvents.
Other suitable solvents are mixtures of the abovementioned solvents. Trifluoroacetic acid is preferably used in excess without the addition of a further solvent, perchloric acid Is preferably used in the form of a mixture of acetic acid and 70% strength perchloric acid in the ratio 9:1. The reaction temperatures of these eolvolyses are expediently between about 0 and about 50°C, the reaction preferably being carried out between IS 15 and 30°C (room temperature) .
A preferred way of eliminating the BOC group Is for example using 40% strength trifluoroacetic acid la methylene chloride or using about 3 to 5 N hydrochloric acid in dioxane at 15 - 30°C, and a preferred way of eliminating the FMOC group (9-fluorenylmethyloxycarbonyl) using an approximately 5- to 20% strength solution ©f dimethylamine, diethylamine or piperidine In dimethylformamide at 15 - 30QC- The DNP group (2,4-dinitropheayl) cat also successfully be eliminated, for example using an approximately 3- to 10% strength solution of 2-mercaptoethanol In dimethylformamide/water at 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 in the presence of a 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 dimethylform35 amide. Hydrogenolysis Is usually carried out at tessera tures of about 0 to 100°C and at a pressure of about 1 to 200 bar, preferably at 20-30°C and 1 to 10 bar.
Hydrogenolysis of the CBZ group is easily carried out, for example» using 5- to 10% strength Rd-carbon ia methanol at 20 - 3Q°C.
Examples which may be mentioned of amiao-protecting 5 groups which are eliminated using a reducing system os metal and proton-eliminating agent are (4-nitro)-benzyloxycarbonyl, 2-iodoethoxycarbonyl or 2,2,2-trichloroethoxycarbonyl or phenacyloxycarbonyl.
An example of the metal constituent of the metal reducing system is a non «noble metal» such as an alkali metal or alkaline earth metal, for example lithium, sodlu».» potassium,, magnesium or calcium, or a transition metal, for example zinc, tin, iron or titanium, while possible proton-eliminating agents are, for example, protonic acids of the abovementioned type, such as hydrochloric acid or acetic acid, C.-C,-alcohols, such as ethanol, and/or amines, or ammonia. Examples of such systems are sodium/ammonia, zinc/hydrochloric or acetic acid, or zinc/ethanol.
Furthermore,, 4-nitrobeasyloxycarbonyl can be split, for example, using a dithionite, such as sodium dithionite, phenacyl oxycarbonyl and 2-halogeno-C3-C7- alkanoyl can be split, for example, with the aid of a nucleophilic reagent, such as a thiolate, for example sodium thio25 phenolate, or using thiourea and base and subsequent hydrolysis, and allyl or but-2-enyl can be split with the aid of a rhodiumilll) halide, such as rhodium(lll) chloride „ The compounds of the formula (I) which are known may be prepared in analogy to the new compounds of the formula (la) » If, for example, methyl 2-carboxy-5-methyl-cyclohex-3ene-carboxylate and ethyl chlorof ornate are used as starting substances, SJ»N-diisopropylethylamiae is used as the base for step one, and sodium aside .and water are used for step two, the course of the reaction of preparation process (A) may be represented hy the following equations ch3 oo-ch3 1. CICOOCgHgtCC3H7-a)?NC?Hg 2. MaH3/H2O 3. a 4. hydrolysis COOK If, for example, tert-butyl 3-methyl-6-carboxy-2-eyelohexea- 1-yl-carbamate and 1 i« hydrochloric aeid are used ae starting substances, the course of the reaction of preparation process (B) may be represented by the following equation: H. ' ΎΥ Xx^COOH BiH-C-0~CiCH3)3 a K HCl ’> Formula (II) provides a general definition of the 2cyclohexen- 1-yl -carboxylic acid derivatives required as starting substances for carrying out preparation process (A). Xn this formula -(II), R1’, R2', R3', R*’, R5' 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 pre20 ferred, for these radicals.
Some of the 2-cyclohexen-1-yl-carboxylic acid derivatives of the formula (XX) are known and/or can be prepared by known processes in a simple, analogous manner (cf. Houben-Weyl, Methoden der Organischen Chemie (Methods of Organic Chemistry] ? 4th edition, R.Muller, Bd. Vol. 5/lc, Georg Thieme Verlag? Stuttgart? 1970? 977; J. Chem. Soc.
Perkin Trans. 1? 1557-62? 1981), for «sesmple by cyclizing the known dienophilic compounds which have the formula (ΪΙΪ) (IW ?.2’ in which R1', R’’ and R3' have the abovementioned meaning, and which are known, with the corresponding dienecarboxylic acid derivatives of the formula (IV) R* -CHsC-CsCHCOOe?14 ° in which R4', Rs' and Re' have the abovementioned meaning and Rw' represents hydrogen, methyl or ethyl, if appropriate in the presence of a diluent, if appropriate in the presence of a catalyst? if appropriate in the presence of as inert gas and if appropriate under pressure, at tewerafcurss between ~50°C and 150eCFormula (III) provides a general definition of the dienophilic compounds required as starting substances for the preparation of the 2-cyclohexen-l-yl-carboxylic acid derivatives of the formula (ΪΪ) and of the 2-cyclohexene derivatives of the formula .(lib). la this formula (III), R3' .and R3' represent those radicals which have already been mentioned in connection with the description of the compounds of the formula (la) according to the invention for these substituents.
The following may be mentioned by way of example for c oxapounds of the formula (III), but without imposing any limitation: acrylic acid, acrylic acid esters, such as, for example, methyl acrylate and ethyl acrylate, acrylic acid amides, such as, for example, N,N~dimethylacrylamide, acrylonitrile and chloroacrylonitrile, maleic anhydride, maleic acid imides, such as, for example, Nphenylmaleimide, vinyl derivatives, such as, for example, vinylphoaphonic acid, dimethyl vinylphosphonate and ωnitrosfcyrene.
The compounds of the formula (III) are generally known compounds of organic chemistry.
Formula (TV) provides a general definition of the dienecarboxylic acid derivatives additionally required as starting substances for the preparation of the 2-cyclohexea- 1-yl -carboxylic acid derivatives of the formula (II). In this formula (IV), R*', R5' and R®' represent those radicals which have already been mentioned in connection with the description of the compounds of the formula (la) according to the invention for these substituents .
The dienecarboaeylic acid derivatives of the formula (IV) are known and/or can be prepared ia a simple, .analogous manner by processes known. from the literature (cf. 'Some modem Methods of Organic Synthesis', W.Caxruthers, Cambridge University Press, 198S, p.125,s Acc. Chem. Res., 1979, 146).
Formula (lib) provides a general definition of the 2 = cyclohexene derivatives required as starting substances for carrying out preparation process (3) . In this formula (lib), Rv, Ra', R’’, R*', S’*, ae* and A preferably, or is particular, represent those substituents which have bees, mentioned .above in the description of the new 2-cyclohexen-1-yl-amine derivatives of the formula (la) as being preferred, or particularly preferred, for these radicals.
Some of the 2-cyclohexene derivatives of the formula (lib) are new and fossa a part, of the present invention.
The compounds which are listed below and which are known, and the enantiomers and isomers thereof, are excepted: methyl 6-£oroyl-5-{ [ (pheaylmethoxy)-carbonyl]-amino}-3cyclohexene-I-carboxylate and methyl 6-(3-ozco-lpropeayl) -5-{ [ (phenyImethoxy) -carbonyl] -amino}-3-cyclohexene-1-carboxylate (cf- o. Med. Chem., 29, 1-8, 1935; J. Med. Chem., 24, 788-94, 1981), methyl 3-cyclohexene-210 [(trichloroacetyl) -amino] -1-carboxylate, 2,2,2-trichloroM- (S-formyl-2-cyclohfexen-l-yl) -acetamide, ethyl (6formyl-5-methyI-2-cyclohexen-l-vl)-carbamate, methyl 2((ethoscy-carbonvl) -amino] -6-methyl-3-cyclohexene-1carboxyl&te, methyl 2- [ (ethoxycarbonyl) -amino] -5-methylIS 3-cyclohexeae-l-carboxylate, methyl 2-E(ethoxycarbonyl)amino] -3-cyclohexene-1-carboxylate, ethyl 3-{2- [(ethoxycarbonyl) -aaino] - S -methyl - 3 -eyelohexen-1 - yl} - 2 -propenoate, phenylmethyl (6-£ormyl-5-propyl-2-cyclob.e2sea-l-yl5 carbamate, phenylmethyl (6 - formyl - 5 -methyl - 2 - cyclohexea20 1-yl) -carbamate, methyl 2-[(phenoxycarbonyl)-asaino]-3cyclohexene-l-carboxylate and ethyl 3-<6-aaethyl-2{ [ (pheaylmethoxy) -carbonyl] -amino}-3-cyclohexen-l-yl>-2propenoate, phenyl S-carbenethoxy-2-eyelohexea-X-yIthiocarbamate, Si- (S-carbomethoxy-S-cyclohexea-l-yl) -125 pyrrolidine-carboxamide (c£. J. Am. Cha». Soc., 103, 2816-22, 1981,- J. Am. Che®. See., 100, 3132-9, 1973; J. Asa. Chem. Soc., 100, 5179-85, 1978 and Tetrahedron Lett. 25, 2183-6, 1984) , phenylmethyl (6-£ormyl-5-peatyl-2cyclohexea-l-yl)-carbamate (cf. J. Org. Chem., 46, 283330 5, 1931) and phenylmethyl {6-forsayl-S-[2-(xaethoxymechoxy) -ethyl] -2-cyclohexen-l-yl}-carbamate (cf. J. Am. Chem. Soc., IOS, 5373-9, 1983), methyl 2-[(p-toluenesulphonyl)-amino] -3-cyclohexene-l-carboxylate, t-butyl2[ (p-tolueaesulphonyll -amino] -3-cyclohexene-l-carboxylafce, benzyl 2-[ (p-toluenesulphonyl)-amino]-3-cyclohexeae-lcarboxylate and 2,4,€-trimethylphenyl 2-[(ptoluenesulphonyl) -amino] -3-cyclohex σ. Org. Chem.', 43, 1448-1455, (1973).
The new 2-cyclohexene derivatives of the formula (lib) are obtained by cycllsiag dienophilic compounds of th® formula (III) (III) <2 β ^C-CH-S3* ia which Rv, R3' and R3’ have the abovementioned meaning (B/a) with M-acyl-l-amino-i,3-butadiene derivatives of the formula (IVa) (IVa) ia which Rs', R*' and A have the abovementioned meaning, if appropriate ia the presence ©fi a diluent, if appropriate ia the presence of a catalyst, I£ appropriate in the presence of an inert gas and ifi appropriate wader pressure, or (B/b) with substituted butadienes of the formula (IVb) RXS ' -g-CHsC-C»CH· (IVb) in which R·*’, Rs* aad R6' have the abovementioned meaning and B13’ represents the acetyl radical or the fcriaefchylsllyl radical. initially in a first stage, if appropriate in the presence of a diluent, if appropriate in the presence of a catalyst, if appropriate ia the presence of an inert gas and if appropriate under pressure. and reacting the resulting 2-cyclohexene derivatives of the formula (IXc) in which R1', R2', Rs', R4', R5' and R*' have the abovementioned meaning and R1S* represents the acetyl radical or trisaethylsilylradieal, In a second step ia a generally customary manner, with 4,4' -dimethoxybeashydrylamiae (DM8) of the formula (v) If appropriate in the presence of a diluent, such as, for example, tetrahydrofuran, at temperatures from 0®C to the belling point of the particular diluent used, and in the presence ©f a catalyst, such as, for example, tetrakis(triphenylphosphine)palladium/©), of the formula (VI), [ (C3H3) ,P] ,Pd (VI) [cf. J. Org. Chem. 1979» 3451 (1978)]» or (B/c) reacting the isocyanates which occur as intermediates in process (A)» of the formula (Ila) in which (Ila) R1'» R2'» RJ', R*'» R2*' and R*' have the abovementioned meaning, with alcohols of the formula (VIZ) R1®' - OH (VII) ia which R1S' represents in each case straight-chain or branched, optionally halogen-substituted alkyl, IS alkenyl, alkinyl or alkoxyalkyl having 1 to 12 carbon atoms (preferably 1 to S carbon atoms) or uasubstituted or substituted phenyl or benzyl» (3/d) the substituted 2-cyclohexene derivatives of the formula (lib) are obtained when the 2-cyclohexene derivatives which can be obtained by process (3/a), (3/b) or (B/c), of the formula (lid) (lid) >xe R1', R3', R’1', Rs', Re' aad A have the abovementioned meaning, ®3’ •CHO - 42 SS’%Z\^3’ (I Lcho in which I3H-K are reduced In a generally customary manner using a complex metal hydride, such as, for example, sodium borohydride, In a suitable solvent, such as, for example, alcohols, such as methanol, ethanol, butanol or Isopropanol, and ethers, such as, for example, diethyl ether or tetrahydrofuran, at temperatures from 0°C to 20°C, aad the resulting 2cyclohexen-l-yl-amine alcohols of the formula (He) (lie) in which -»X* n)' *}** $! g £% .g meaning, R3' „ Rei' and A have the abovementioned are converted, for example into esters .and ethers, by further reactions on the hydroxyl group. Furthermore, it is possible to obtain acyl derivatives or carbamoyl derivatives of the compounds of the formula (lib) by reactions with, for example, acyl halides or carbamoyl chlorides, or (3/e) the substituted 2-cyclohexene derivatives of the formula (lib) are obtained when the 2-cyclohexene derivatives which can be obtained by process (B/a) t, (B/b) or (B/c), of the formula (Ud) in which Rs ' RH~A (lid) 5 Ο1’ ϊ?3’ w4’ «Λ £ Λ ff M /* meaning, R5’, R5' aad A have the abovementioned are reacted with alkanephosphonic acid derivatives of the formula (VIII) s17'oj (νιΙΙ) ^Ρ~0Κ2~Β8' R*' 0 A in which S17’ represents methyl or ethyl and RX6' represents the cyano group or represents the alkoxycarbonyl group, if appropriate in the presence of a diluent? If appropriate in the presence of a base and if appropriate In 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 pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dlchlorobenzene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuraa and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as acetonitrile and propioaitrile, amides, such as, for example, disaethylxomaaiide, dimethylacetamide and N-saethy Ipyrrolidone, .and dimethyl sulphoxide, betramethyleae sulphone and heacamethylphosphoric trlaaoide.
Suitable inert gases In this context are nitrogen and virtually all noble gases, ia particular argon.
When carrying out process (3/a) for the preparation o£ 15 the 2-cyclohexene derivatives of the f omul a (Hb)» the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between -70 ®C and +250°C, preferably between -50eC and +150eC.
For carrying out process (3/a) for the preparation o£ the 2-cyclohexeae derivatives of the formula (IXb), 1 to 30 moles, preferably 1 to 3 moles, of the dlenophilic compound of the foxmula (XIX), 0.01 to 20.0 moles, preferably 0.1 to 5.0 moles, of catalyst .and If approp25 rlate 0.1 to 5% of a stabilizer which prevents freeradical polymerization, such as, for example, 4-tertbutylcatechol, are generally employed per mole of the iiacyl-1-aadjoo-1,3-butadiene derivatives of the formula (XVa) .
The process according to the invention for the preparation of the 2-cyclohexene derivatives of the formula (lib) is generally carried out under Increased pressure. In general, the process is carried out at a pressure of 1 to 200 bar, preferably at 5 to 20 bar.
Suitable catalysts for the preparation of the new 2cyclohexen-l-yl-carboxylic acid derivatives o£ th© formula (lib) according to process variant (B/a) are the catalysts which are customary for reactions or this type? Lewis acids, such a®, for example, titanium tetrachloride, tin tetrachloride, aluminium trichloride and boron trifluoride etherate, are preferably used.
Under certain circumstance©, however, it is also possible to carry out the process for the preparation of the new 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 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 further concentrated under reduced pressure, or poured into wafer, and the product is isolated by extraction or filtration and purified by chromatography .
Formula (IVa) provides a general definition of the ϊϊacyl-1-amino-1, 3-butadiene derivatives additionally required as starting substances for the preparation of the 2-cyclohexene derivatives of the formula (lib) according to process variant (3/a). In this formula (IVa), R*', Rs', St*' and A represent those radicals which have already been mentioned ia connection with the description of the compounds of the formula (Ia) according to the invention for these substituent©.
The Si-acyl-l-amino-l, 3 -butadiene derivatives of the formula (IVa) are knows and/or can be prepared in a simple, analogous manner by processes known from the literature [cf, J. Org. Chem., 43, 2154 (1978)], la this process,· suitable diluents for carrying out step - 4S oae of process (3/b) according to the invention are virtually all inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum, ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon, tetrachloride, chlorobenzene and odichlorobeazene, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as, for example, acetonitrile and propionitrile, amides, such as, for example, dimethyl foraaadde, dimefchylacetasaide and K-mefchylpyrrolidone, and dimethyl sulphoxide, tetramethylene sulphone and hexasaethylphosphorio ferlamide.
Suitable inert gases in this process are nitrogen, and virtually all noble gases, ia particular argon.
When carrying out step one of process (3/fei according to the invention for the preparation of the 2-cyclohexene derivatives of the formula (lie), the reaction temperatures can be varied within a relatively wide range. In general, the process is carried out at temperatures between -70*C and +250eC, preferably between -50°C and +150eC.
For carrying out step one of process (3/b) according to the invention for the preparation of the 2-cyclohexene derivatives of the formula (He), 1 to 0.01 mole, preferably 1 to 0.3 mole, of the substituted butadienes of the formula (XVb), 0.01 to 20.0 moles, preferably 0.1 to 5.0 moles, os catalyst and if appropriate 0.1 fc© 5% of a stabilizer which prevents free-radical polymerization such as, for example, 4-tert-bufcylcatechol, are generally employed per mole of the dienophilic ccmpouuds of the formula (III).
Step one of the process according to the invention for the preparation of the 2-cyclohexene derivatives of the formula (lie) ie generally carried out under increased pressure. In general, the process is carried out at a pressure of 1 to 200 har, preferably at a pressure of 1 to 20 bar.
Suitable catalysts for step one of process (B/fo) according to the invention, for the preparation of the new 2-cyclohexene derivatives of the formula (lie) are the catalysts customary for reactions of this type? Lewis acids, such as, for example, titanium tetrachloride, tin. tetrachloride, aluminium trichloride aad boron trifluoride etherate, are preferably used. under certain conditions, however, it is also possible to carry out step one of process (B/b) according to the invention for the preparation of the new 2-cyclohexene derivatives of th® formula (lie) 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 hourfs at the specific temperature required. Working-up is carried out ia each ease by customary methods. In general, a procedure Is followed in which the reaction mixture Is either concentrated under reduced pressure or poured into water, aad the product Is isolated by extraction or filtration and purified by chromatography.
Formula (IVb) provides a general definition of the butadienes additionally required as starting substances for the preparation of the 2-cyclohexene derivatives of th© formula (lie). In this formula (IVb), R'*', R5' and Rs' represent those radicals which have already been mentioned is connection with the description of the compounds of the formula (la) according to the invention for these substituents.
The substituted butadienes of the tor-aula (IVb) are known and/or caa be prepared in a simple, analogous manner by processes known from the literature (cf. J. Org. Chen», , 2414 (1965)). 4,4'-Dimethoxybenzhydrylamine (DM3) of the formula (V) aad. tetrakis (triphenylphosphine) -palladium(0) of the formula (VI) , which are additionally required as starting substances for step two of process (3/b) according to the invention, are generally known compounds of organic chemistry (cf. J. Chem. Soc., 7285 (1965)].
Formula (VII) provides a general definition of the alcohols required as starting substances for carrying out process (B/c) according to the invention, and they are generally known compounds of organic chemistry.
Process (3/e) 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 process are virtually all Inert organic solvents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenseae, ethers, such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl ketone, methyl Isopropyl ketone and methyl isobutyl ketone, esters, such as methyl acetate and ethyl acetate, nitriles, such as acetonitrile and propionitrile, amides, sash as, for example, dimethylformamide, dimethylacetamide and M-methylpyrrolidone, and dimethyl sulphoxide, tetramethyleae sulphone and hexamethylphosphoric triamide.
Suitable inert gases In this context are nitrogen and virtually all noble gases, in particular argon.
When carrying out process (B/e) for the preparation of the new 2-cyclohexene derivatives of the formula (lib), the reaction temperatures can be varied within s relatively wide range. In general, the process is carried out at temperatures between -70°C and +150°C, preferably between -50C 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 (Ξ/e) for the preparation of the 15 new 2-cyclohexene derivatives of the formula (lib), In general 1 to 5 moles, preferably 1 to 2 moles, of the alkanephosphonic acid derivatives of the formula (VIIX) are generally employed per mole of the 2-cyclohexen-l-ylamlae derivatives of the formula (XXd).
Bases which can bs 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 metal hydroxides, such as, for example, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as, for example, calcium hydroxide, alkali metal carbonates and alkali metal alcoholates, such as sodium carbonate and potassium carbonate, sodium methylate, sodium ethylate, potassium methylate, potassium ethylate, thallium methylate and thallium ethylate, hydrides, such as, for example, sodium hydride, furthermore aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dime thy Ibensy lamine, pyridine, 1,5diazabicyclo-[4.3.0]-aon-5-ene (DBM), 1,8-diazabicyclo35 £5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-£2.2.2]50 octane (DA3C0), are preferably suitable» la general, the reactions are carried out la a suitable diluent in the presence of aa acid acceptor, and the reaction mixture is stirred for several hours at the specific temperature required- Working up in the process according to the invention is carried out ia each case by customary methods.
Formula (vill) provides a general definition of the alkamephosphonic acid derivatives required as starting substances for carrying out process (B/e) for the preparation of the new 2-cyclohexene derivatives of the formula (lib), and these alkanephosphonic acid derivatives are known and/or can be prepared In a simple, analogous manner by processes known from the literature» The compounds of the formula (la), (11) and (Ila) to (Ile) can be obtained as mixtures of enantiomers or mixtures of diastereomers.
The invention comprises the pure isomers as well as the mixtures. These mixtures of diastereomers can be resolved by customary methods, for example by selective crystallization, from suitable solvents, or chromatography on silica gel or aluminium oxide, to give the components. Racemates can be resolved by customary methods to give the individual enantiomers, for example by salt formation with optically active acids, such as caarcmorsulphoaic acid or dibensoyltartaric acid, and selective crystallization, or by the formation of derivatives with suitable optically active reagents, separation of the diastereoaerie derivatives and renewed splitting or separation on optically active column material» Suitable acids for the preparation of acid addition salts of the compounds of the formula (I) are preferably those which have already been mentioned in connection with the description of the acid addition salts according to the invention as being preferred acids.
Th® acid addition salts o£ th© compounds of the formula (I) caa be obtained in a simple naoaer by customary salt formation methods, for example by dissolving a compound S of the general formula (I) in a suitable inert solvent and adding th© aoid, for example hydrochloric acid, and they caa be isolated in a known manner, for example by filtration, and, if appropriate, purified by washing with an inert organic solvent.
Suitable salts of metal© for the preparation of metal salt complexes of the compounds of the general formula (1) are preferably those which have been described further above.
The metal salt complexes of compounds of the general formula (I) can be obtained, in a simple manner by customary processes, for example by dissolving the metal salt in an alcohol, for example ethanol, and adding the solution to compounds of the general formula (I) . Metal salt complexes can be isolated in a known manner, for example by filtration, and, if appropriate, they can be purified by recrystallization.
The active compounds according to th© invention show a powerful biological action and can be> employed in practice for combating undesired pests. For example, the active compounds caa be employed for us© as plant protection agents, in particular as fungicides.
Fungicidal agents in plant protection are employed for combating Plasmodiophoronycetes, Oozaycetes, Chytridiomycetes. Zygomycetes, Ascomycetes, Basidiozaycetes and Deuteromycetes.
Some causative organisms of fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, hut not by way of limitation: Xanthamonas species, such as, for example, Xaathomonae cawpestris pv„ oryzae; Pseudomonas species, such as, for example, Pseudomonas eyringae pv. lachrymans; Srwiaia species, such as, for example, Erwinia amylovora; Pythium species, such as, for example, Pythium ultimum; Phytopkfchora species, such as, for example, Phytophthora iafestaas; Pseudpperonospora species, such as, for example, Pseudo** 10 peroaospora humuli or Pseudoperoaospora cubeasl®; Plasmopara species, such as, for example, Plasmopara viticola; Peroaospora species, such as, for example, Peronospoza pisi or P. brassicae; Eryaiphe species, such as, for example, Erysiphe graasiais? Sphaerotheca species, such as, for example, Sphaerotheca fuXigiuea; Podosphaera species, such as, for example, ©odosphaera 20 leucotricha; Venturia species, such as, for example, Venturia iaaequails; Pyrenophora species, such as, for example, Pyreaophora teres ©r P. graminea (conidia forms Drechslera, syns Eelminthosporium)? Cochliobolus species, such as, for example, Cochliobolus sativus (conidia forms Drechslera, sys: Helmxnthosporium) ; Uremycea species, such as, for example, Oromycea appen30 diculatus? Pucclnia species, such as, for example, Pucclnia recondifca, Tilletxa species, such as, for example, Tllletla caries; wsullage species, such as, for example, Usfcilago auda es UstIIago aveaae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyrlcularla species, such as, oryzae; for example, Pyriculazia S3 Fusarium species, such as, for example, Fusarium culaorv®: Botrytis species, such as, £or example, Botrytis einerea; Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such ae, for example, Cercospora canescene; lltemaria species,, such as, for example, Alteraaria brassicae and Pseudocercosporella species, such as, for example, Poeudocercosporella herpotrichoides.
The good toleration, by plants, of the active compounds, at the concentrations required for combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seeds, and of the soil.
As plant protection agents, the active compound which can be used according to the invention can be employed with particularly good success protectively for combating Phytophthora species on tomatoes and Venturia species in apples.
In addition, some of the active compounds which can be used according to the invention have a good action against Pythiua species, Altemaria species .and Cercospora species.
The active compounds according to the invention can be used as defoliants, desiccants, agents for destroying broad-leaved plants and, especially, as weed-killers. By 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 amount used. - 54 The active compounds according to the invention can be used, for example, ia connection with the following plants; Dicotyledon weeds of .the genera: Sinapis, bepidium, Galium, Stellaria, Matricaria, Jmthernis, Galinsoga, Cheaopodiuzn, Urfcica, Senecio, Amaraathus, Portulaca, Xaathiuat, Convolvulus, Xpomoea, Polygonum, Sesbaaia, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, ninderaia, Lamium, Veronica, Abutilon, Bmes, Datura, Viola, Galeopsis, Papaver .and Centaurea.
Dicotyledon cultures of the ceaara; Gossypium, Glycine, Beta, Daucus, Bhaseolus, Risusa, Solanum, Linum, Xpomoea, Vieia, Micotiana, Lycopersicon, Arachis, Brassica, Lacfuca, Cucumis and Cucurhita.
Monocotyledon weeds of the genera; Schinochloa, Sef aria, Banicum, Digitaria, Rhleum, Boa, Pestuca, Sleusine, Brachiaria, helium, Brossus, Avena, Cyperus, Sorghum, Agropyron, Cyaodoa, Monochoria, Fimhrisfylis, Sagittaria, Sleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to th© invention is in no way restricted to these genera, hut also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, fox the total combating of weeds, for example on industrial terrain .and rail tracks, and on paths and squares with or without tree plantings- Equally, the compounds can he employed for combating weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, and for the selective combating of weeds ia annual cultures.
Th© . active compounds according co the invention are highly suitable for selectively combating monocotyledon and dicotyledon weeds in monocotyledon crops, in particular using the post-emergence method.
Depending on their particular physical and/or chemical properties, the active compounds which can be used according to the invention can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine capsules in-polymeric substances and In coating compositions for seed, and furthermore ULV cold mist and warm mist formulations.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, 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-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable In the mains aromatics, such as xylene, toluene or alkylaaphthalexj.es, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar sol35 vents, such as dimethylformamide aad dimethyl sulphoxide, as well as water? by liquefied gaseous extenders or 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 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 highlydisperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed aad fractionated natural rocks such as calcite, marble, pumice, sepiolite aad dolomite, as well as synthetic granules of inorganic aad organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs .and tobacco stalks; as emulsifying and/or foamforming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, aryl sulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example Xlgninsulphite waste liquors and methylcellulose» Adhesives such as carbossymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arable, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalin/s and lecithins, and synthetic phospholipids, can be used In the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example Iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and saetal phthalocyanine dye35 stuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 per cent by weight of active eoa^ound, preferably between 0.5 and 90%.
For combating weeds, the active compounds according to 5 the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, such as, for example, 1-amino-6-ethylthio-3(2,2 - dime thy Ipropyl) -1,3» 5-triazin©-2,4(1Ξ,3Ξ) -dione (AMETHYDIONS) or N- (2-benzothiazolyl) -ΚΙ,Ν' -dimethyl-urea (HHTABENZTHIAZUROW) for combating weeds in cereals; 4amlno-3-methyl-6-phenyl-Ι» 2»4-triazin~5 (4Ξ) -one (META15 MITROKT) for combating weeds in sugar beet and 4-amino-6(1»1-dimethylethyl)-3-methylthio-l,2»4-triazia-5(4H)-one (MHTRIBuZIM) for combating weeds in soya beans. Furthermore» 2» 4-dichlorophesxoxyacetic acid (2» 4-D); 4-(2,4dichlorophenoxy)-butyric acid (2»4-D3) ? 2,4-dichlorophen20 oxypropionic acid (2,,4-DR) ? 3-isopropyl-2» 1,, 3-bensothiadiazin-4-one 2,2-dioxide (BSKTAZONE); methyl 5-(2,4dichlorophenoxy) -2-nitrobenzoate (ΞΙΡΞΝΟΧ); Βϊ,Ν-dimethylSF - (3-chloro-4-methylphenyl) -urea (CHLORTOLUROH); 2-[4(2,4-dichlorophenoxy) -phenoxy) -propionic acid, its methyl ester or Its ethyl ester (DICLOPOR),? 4-anino-6-t-butyl-3@thylthio-l,2»4-triazia-5 (4Ξ)-one (ΞΤΞΙΟΖΏί) ? 2-(4-((6chloro-2-benzoxazolyl)-oxy) phenoxy}-propanoic acid, its methyl ester or its ethyl ester (FRNOZARROR) ; N,S?-dimethyl-N - (3 -trifluorome thy lphenyl) -urea (FLUOMSTURCM) ? methyl 2-[4,5-dihydro-4-jaefchyl-4-(l-saethylethyl)-5-ox©1Ξ-imidazol-2-yl) -4 (5) -methylbenzoate (ΙΜΑΖΑΜΞΤΗΑΒΞ^ίΖ) $ (4-chloro-2-isethylphenoxy)-propionic acid (MCRR) $ 2ϊ-(1© thy Ipropyl )-3,4- dime thyl -2,6- dial t roani 1 ine (PSNDIMSISALIS?) ι O- (6-chloro-3-phenyl-pyridazin-4-yl) S-©ctyl thiocarbonate (RTRIDATS); 4-efchylamin©-2-t-bufcylasaino~6methylthio-s-triazine (ΤΒΚ3υΤΗ22ϊ) and 3» 5» S-trichloro-2pyridyloxyacetic acid (TRZCLORTR) ar® also possible.
Surprisingly, some mixtures also show a synergistic actios,.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or ia th® us® forms prepared therefrom by further dilution, such as ready-fco~u.se solutions, suspensions, emulsions, powders, pastes aad granules.
They ar® used ia the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of th® plants.
They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range- Xt depends essentially on the nature of the desired effect. Zn 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 aad use of the active compounds according to the Invention can be seen from, the following examples.
Preparation Exampless Example Is (X-l) hk2 x Hex (Process! A) A solution of 5.4 g (0.05 mol) of ethyl chlorofozxa&t® ia 15 ml of acetone is added ia the course of 30 minutes at -5°C to a solution of 10 g (0.05 mol) of methyl 2carboxy-5-methylcyclohex-'3-en@-carboxylate and 8 g (0.062 mol) of N,N-diieopropyl~ethylamine In 30 mi of acetone. After the mixture had remained at 0eC for a further 30 minutes, aa ice-cooled solution of 6.5 g (0.1 mol) of sodium azide ia 15 ml of water is added dropwise. The mixture is stirred at 0°C for 15 minutes and then worked up using wafcer/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 the reaction is monitored by IR spectroscopy. When the transition to the Isocyanate is ccm^>lete, the mixture is evaporated, the residue is taken up in 50 ml of tetrahydrofuran and 50 ml of 1 £? hydrochloric acid, and the mixture is stirred at 40eC for 10 hours.
After the mixture has been evaporated completely under reduced pressure, 2.8 g (30% of theory) of 4-methyl-6carbomethoxy-2-cyclohexen-l-yl-amine hydrochloride are obtained.
XH-BBSR data*1 (DMSO, 200 MSz) ,· & = 1.00(33), 1.501.70(lH), 1.85-2-00 and 2.15-2.35(2«), 2.85-3.00(1«), 3.68(322), 3.80-3.85(23), 5.70-5.90(2«) *’ The “H-WiR spectra were recorded in dimethyl sulphoxide (DMSO) with tetramethylsilane (TMS) as the internal standard. The chemical shift is indicated as «5 value in ppm.
Sxample 2 : OOH (1-2) (Process 3) g (7.® raaol) o£ tert-butyl <3-methyl-6-carboxy-25 eyelohexen-1-yl)-carbamate are introduced ia 5 al of 1 N hydrochloric acid. After the mixture has been kept at 50°C for 4 hours it is evaporated to dryness, and 1.3 g (87% of theory) of 3 -methyl- 6-carboxy-2“Cyclohexen- 1-yl amine hydrochloride are obtained as a white solid of melting point 156-163°C.
The end products of the formula (I) (I) which are listed in Table 1 below are obtained analogously to the methods described in Examples 1 and 2 and following the instructions ia the descriptions of th© processes according to the Invention: Sx. Ho. R1 R3 R4 A Physical constants _ Table 1 1-3 Ii I COOH H 4-CH3 H m.p.j 190-193°C x HCl / uniform cis dlastereontei I - 4 1“ ί COOH Η H H m.p.i 169-172eC x HCl / uniform cis diastereomer I - 5 i- 5 CQOCHg Η H H (CDClj, 200 MHz} ί δ = 1.65-2,20(6S), 2.572.68(IH), 3.60-3.70(2H), 3.71 (3H) , 5.70 (2H) 1-6 I 1 COOH 3,4 -< CH 2-CH2“CH2CH 2) H a.p.i 185-205eC x HCl 5 M I - 7 · I { cooch3 Η H H 'H-HMR*’ (CDClj, 200 MHz) ί a s 1.90-2.4(4H), 3.03-3.17 (IH), 3.78(3H), 4.20(IH), 6.00(211), 8.25-9.65(3H) x HCl ϊ-e i I-! COOHH Λ~dz H m.p.i 175 - 190®C x HCl 1-9 I H COOCHg H 4—·ζ ~^> H (DMSO, 200 MHz) i δ = 2.75-2.85(IH), 3.30-3.43 (IH) , 3.65 and 3.68(311), 5.75-6.00(2H), 7.10-7 ,40 (5H) Table 1 - continuation RA Physical constants Ex s No, RJ l'“W H COQCHgCHgOCHg H = 11 H I “12 Cl I - 13 H 1-14 H IIS CHg COOH H COOH It COOH H COOH H COOCHg H I “16 COOH I “17 CH 1 H-NMR*1' (DMSO j 200 MHz )ί 4-CHg H Is 1,05(311), 3,30(311), 5,75-5,95(211), 8,10-8,50(311) x HC 1 4 “ C 2 H y H m.p. } 100-185® C x HC). 4 -CHj H m.p, ί 200-21.4® C x HCl 4-¾¾ H m, p. I 16 0 - 17 8° C x HC). I 3-CzHs H m.p, ( 140-15 0®C x HCl et to 1 H H bl-NHR** (DMSO, 200 MHz): 1 a 1,16 and i,29 ( isom@rf 311),. 3,65(311), 5,60-5,70 and 5,85-6,00(211), 0,20-8.,50 (311) / x HCl. 3-C4H9 H m.p.i iflO-108®C x HC 1. 4 CH*» H1H-NMR ί DMS0, 200 ΜΗz5: ί·= 1.05(3)1), 1,80-2.10 and 2,20-2,4O(3H), 3,48(IH), 3,95(IH), 5,65-5,95(2H), 8,60-9,ΟΟί3H) $ x HCl Tabla 1 - Continuation R* A Physical constants Ex.No, I 1 ΟΙ - 19 1-20 I ”21 1=22 Ϊ-23 1-24 SV H CN H Cl. CN H NQgl II -CHbCH“C*O h r OCgHg H -CHsCH-COOH H H -CH°GH=C®0 1 OCgHg -CHg-OH R4 4-CgH 4-CH 3 - CH3 4-CH3 H — CHg 4-CH 3 H Et'P·: 130-135® C x HCl H 1H-N14R (CDClg, 200 MHz): « 1.15(3HJ, 1.20-1.40 and I,β5-2.55(5ΗΪ, 3,60(IH), 5,60-5.85(21() H si.p,. 215-221® C κ HCl (CBCl-j, 200 KHz )8 H A® 1.02OH), 1,29(3H), 4,18ί2H), S,55-6,00ί3H), 6,63-7,10(IH) H ni.p.j 166-218® C x HCl H Sl.p.i 191-214® C X HCl H ffl.p.i 71-83® C x HCl Tabla 1 - Continuation Sxβ Ho R2 R! A Physical constants I = 25 ii 0 Ii Ii 6»5 =(C-N-C) Λ O 0 Ii II .5 = {C - H “ C) «Ο H. ai.p.i 51-53° C x CRgCOOH 1-27 O 0 ii Ii 6,5-{C-M-C) ciuo-eoeiu tel 4-CHg It 4-CKg H ffi.p.S 80-83° C x CRgCOOH J H ai.p.l 75-81° C x CF3C00H 1 ί “29 1-30 K -CG-MSCMglg H H . =CO-NiCH3)2 H iCDClg, ZOOHHz): H £ s i,08i3H), 2,1O(3H5, 4.02=4.26(211), 5,76-6,00 (2H), 8.10=8.55(3H) x HCl H IR! 3500-3350, 1655 cm-1 H 1R{ 1670 em” & x CFgCOOH Table 1 - Continuation R! R* Physical constants Ex.Ho β 1-31 'τ' &ΐι I - ddi 1-33 1-34 “ 3 '5 -3fc 1=37 i -aa -CO-N(CH3)2 H H -CO-NR-4 J H H -CO-OCHieHrs'U H Su3 ¢1¾ H -CO-CH? £lS H COOH H -COO-C4Hg-n li H -COOC^H^-n H H -COOC2Hg H R4 4-CH3 4-CH3 4-CH-j - C H 3 — C H 3 4-CH, CuJ 4-CH3 4-0¾ IRf 1670 era'1 κ CPtjCOOH w E.p.i 111- 1276 C (CQClrp 200MHz)i 5« 1,O5(3H1, 1,26(610, 5,08( IH) j 5· ,53-5,50( 2ΗΪ iCI3Cl3i 200 MHz).· As 1»OS(3H), 5,18(210, 5,605,85(210, 7 ,25-7,40( 5ΗΪ ’ hl-KMR^ (CDCl3, 200 MHz H W A« 1,16(310 j 1,80-2,60(310. ’ 3,83-4,00(IH), 5,65-5,78 and 6,00-6,13(210 1H-HMR*5 (DMSO s 200 MHz 5; Ac 0,89(310, 1,03(310, 2.842,90( NO , 4,00-4,20(210 , § ,70 = 5,90(210 , 8,10-8,40(310 IRf 350Q-341O, 1735 cm1 IR{ 3500-3400, 1735 cm 1 Tabla 1 - Continuation Physical constants Ex.No, R1Ra R3 1-39 H CM H 4-C2Hs 1-40 « =ch2oh JI 4“CH3 1-41 H -ch2oh· H H 1-42 H -COOH H 5-CHiCHg) 1=43 H -COOH if 4-CHg 1-44 n 6 ,S = (C-O-C1U“ II 2 0 W 4-CH3 1-45 H -COOCgHg s-ch3 H bi-NMR** (CDClg, 200 MHz)I 0.92C3H), 1.27-1.70(5ΗΪ, 1,90 = 2,10(210, 2.78-2.00 (1ΗΪ, 3.S3=3.6O(1H), B.66S.80C2H) MSI ml a f^el. int.il 141 1 (DMSO, 200 MHz)I δ* 1,30-2,10(5«), 5,63-5.82 and 5,90-6,00(211), G, 00-8,40 <3H) m.p.J 109-206°C / x HCI ai.p.i i30-130® G dies tereomar ratio’* 30 / xHC 1 1H-NMR*} C CDC13 , 200 MHz Ϊ ·. ie 0,80 OH), 1.,00-2.20 and 2 i 30 = 2.B0 (4H>, 2.90-3.05 (IH), 4,20=4.60(2H), 8,056,20 and 6.30=6,40( 2H 5 , 7,30' (11U i x HCI ht-HMR*’ (DMSO, 200 MHz): 0,93(311), i,21(3H), 2,552.66(1H), 4,10-4.25(2«), S, 70 = 6,63(211), ' '0-8.30 (3HH x HCI Fl· H R Λ Physical eonstasts Table 1 = Centinuatioa Sx.He r 1 r2 ί - 48 -COOH 4-CH3 1-47 -COOH 4-CH3 ί -48 H -CONH— H 1-49 H -COOCH(CH3)2 H 4-CH3 4-CH-j 1-50 xOH H - IV li och3 0 4-CH3 optical go H rotation ί Colp = <76.6 (0=0.3, H20) x HCl enantiomer of 1-3 H optical 20 rotation; [a3q = -84.1 (0=0,3, H70) x HCl enantiomer of ϊ - 3 U m.p.; 12fi-133®C x HCl H 1H-NMR* 5 (COC Ϊ 3, 200 ΜΗ z): 6= 1,15(3H), i,25(6H), 2.712,85(1 Η) , 5,00-5,16(1)4), .87-6,08(2H), 8,30-8,70 (3ΗΪ / x HCl H MS (FAB): 205 [M'f ] x HCl ) cn '.S S 1-51 COOH 4-CH3 H x HO^C-ClU-CH-COoH £» J &B OH 1 H-NMR (DMSO): & = 1,00 (3H), 1,40 (nt, IH) j 2,20-2,60 (614); 3,75 (IH); 4,05 (IH); 5,605,90 (2H)» Tabla 1 = Continuation R3 R A Physical eons tan,ts lx. No, R* R‘ 1-52 H -COOH H 4-CH 31H-HMR (DMSO): 5 = 1,00 ( 3H ) ; 1,50 Cm, IH); 2,25 <3H); 2,SO (IH)J 5,60-5,90 (2H); 7,10 ί2H) j 7,50 ί 2H) , 1-53 I-54 •COOH •COOH 4-CH3 -CHg 1-55 -COOH H 4-CH1-56 -COOH H 4-CH3 Η x CuSO4 m.p.: 2ΐ0;-219° C idecomp.) Η κ HBr ! H-HMR (DMSO): & = 1,00 (OH), 1,50 (1H)J 2,SO (IH)J 5,605,90 (2H); 7,90 (br, OH). Η x CH3CO2H 1 H-HMR (DMSO)J A = 0,95 (3H)1 ),85 (OH)) 5,605,80 (2H), x HCl isomsr of 1-3 1 H-HMR (CD3OD): δ == 1,06 (OH); 1,83 (IH); 2,00 (IH); 2,38 (IH); 2,81 (IH); 4,08 UH); ,60 (1H); 6,00 (1H)» 1-57 -CH?-OH 4-CH3 1-50 H -COOH H 4-CH-» Η x HCl 1 H-HMR (DMSO); δ = 1,00 (OH); 3,45 <2H); 5,70-5,90 (2H); 8,06 ( OH ) . ^zwitter iorf| ffl.pe ; 208-21 I® C Tabla 1 - Continuation R3 R4 Physical constants Ss.Se. r 1 R2 1-59 -60 1-61 I -62 1-63 1-64 1-65 H -C02CH3 H co2ch3 H -CO2CH3 H 1-66 - CH. 4-CHg.
- CHH02CCH2C(OH) - (CO2H)CH2C02H hygroscopic HO2CCO2H m.p.: 152- 158°C -co2ch3 h -co2ch3 h H -CO2(CH2)20CH3 H -CO2CK3 H H -CO2H H 4-CH.
HOgS 4-CHg 4-CHo 4-CH. 4-CH3 Ci-UC02H n|® 1,4763 ng® 1.,4791 CHjffl.p.: i25-l2e°C I m.p.i 69» 5-90° C S 1 H-NMR (DMSO): $ = 1,00 ( 3H ) ; 1,50 (IH); 2,00 (IH); 2,30 (IH); 2,85 (IK); 3,90 (IH); 5,60-5,95 (2H); 7,61 <5H).
Table 1 = Continuation R* R ' A Physical constants Ex . No , R1 R* 1-67 H -co2h H 4-CH3 1-88 H -C02ίCHg 3 sCHg H 4-CH3 1 -69 H -CO2CH2CH(CH3)2 H 4 - C f 13 1-70 H -CO2CH2CH(CH3)2 H 4 - C H 3 1-71 H -CO'gH H 4-CHg 1 -72 H -co2h H 4-CHg 1-73 H -co2h H 4-CH3 1-74 H -co2h H CHiCHg) H x HO2CCO2H *H-NMR ίDMSO): 6 = 1,05 <3H), 1.45 (1K)J 2.05 UH), 2.31 UH); 2.85 (IK); 3 .SO UH); 5,60-5.80 (2H).
H 1H-NMR 3); δ = 0.901,08 (9H); 2,60-2.73 UK); 1 3.90 <2HH 5,60-5,80 (2H). m Θ H x HCl 1 -NMR (DMSO): δ = 0.85- 1 1.05 (9K); 2,90-3,00 UH); 3.90 (2ΗΪ1 5,70-5,90 (2H); 5j20 <3H).
H x Cu(OAc)2 MS (FAB ί1 155 CM* -CuUcigl H x HO?CCH->COoH MS (FAB·): 259 [M* 1 H x HO2C-CH=CH-CH=CH-CH3 MS (FAB); 267 CM*] H x HCl a.p.: 203-206®C (doeomp.) Table 1 - Continuation R ' A Physical constant® zwittar ion m.p,; 98° C ISX e HO , R1 R2 R3 ί -75 H -co2h H Ϊ -76 H -co2h 3-Of 3 Ϊ -77 H -co2h 3 - C £ H s 1-78 H ~ C 0 N a H i -79 H -co2-m-V * H I -SO H - C 0 2 C H 33 £ 6 H 5 1-81 H -co2h H 1-02 H -co2h H 1-83 H -co2h 3-C6H5 1 -84 H “ CO^K 3-CH(CH3): 1-85 H -CN 3-CH(CH3); 1-86 H -CN 3-C6H5 H 4-CH3 H x HCl m.p.; 133-135®C 4-CH2CH (CH3)2 H x NC1 a.p. : 14 0 - 14 5® C 4-CH3 H m.p. >250®C (decomposition) 4-CH3 11 Hl ,p « : )250°C (decomposition) 4-CH2CH(CH3)2 H1H-NMR (CDCijH 5 = 0,750,95 (9H); 2,65-2,35 (IH); 3,75 (3H); 5,90 (IH)ί 7,157,40 (5ΗΪ, H H x ho2cco2h a.ρ3 : 147-150® C (decomposition) 0 li H H x HN h >s«r O' ^0 Jffl.p.: 106-1 12° c (decomposition) 4 -CH(CH3)2 H x HCl m, ρ,: 245-248® 4 - C H 2 C H (C Η 3) 2 K x HCl HI s P a J 210-218® 4-CH2CH(CH3)2 H x HCl m.p a: 1 64® C 4-CH(CH3)2 H x HCL m.p. : 233-261° Table 3, - Continuation I§5£ 1 O e R1 R2 R' J -87 H ‘C02C2H5 H Ϊ -88 H -CO2C1I(CH3)2 I! I -89 H -CO2C&Hg H 1-90 H 'CO2C6H5 H 1-91 H “ C G ~>C H H Ϊ -92 H -CG2—/” S H 1-93 H -co2h H I-94 H -co2h H 1-95 H - C 0 2 H H 1 -96 H -co2ch3 K r -97 H — C O 2 C H *j H R4 H H 4-CH3 - C H j Physical constants HCl 2Π s JS1 e J 1 39 - 143° C HCi 231 a J3 s * 188-188,5® C m.P ε ’ H7° C 4-CH(CH3)2 4-CH3 H H x HCl 1 H-NMR (DMSO) A = 1,00 (3H); 1,40 UH); 2,30 (IH); 5,65-5,95 (2H); 7.,20 (5H).
H x HCl MS; 197 (M* - HCl] MS? 231 EM* 183 3 I H x HCl enantiomer) ffi.p. : 210- 21 3,5° C Η κ HCl (enantiomer) ai.p,: 208-210® C MS! M* of 207 by FAB spectroscopy (enantiomer3 MS i FAB ): 191 EM* 3 ί ©nan bioxaer) MS (FAB): 191 EM*] H x HCl H x HCl H x HCl TabΙο 1 - Continuation EaC 3 β R1 R2 R3 R4 A Physical constants 1 -98 Η co2ch2-c6h5 Π H H 1 H-NMR (CDCl,)i δ = 1,50 ( 2H) ; 2,60-2^70 (111)5 3,67 UH); 5,15 (2H5; 5,75 <2H); 7,32 (5K). ϊ -99 Η COgCHg“ S $4 CI gCHg H . 4-CH3 H 1 H-HMR (CDClg): δ « 1,05 (d, 3H); 2,75-2,85 (IH); 5,22 <2H); 5,78 <2H); 7,227,40 (3H). ί -100 Η co2ch2-c6h5 H H Η x HCl MS: 231 CM* - 36 3 I - 10 3 Η CO2CH2-2,4-C12C6H3 H 4-CH3 Η x HCl MS? 313 [M* - 363 1-102 1-ί C02CH2-2-ClC6H4 H 4-CH3 H 1 H-HMR (CDCl,): 5 = 1,05 (3H); 2,60 (2H); 2,65-2,77 UH) I 5,26 <2H); 5,56-5,80 (2H),‘ 7,20-7,50 (4H)« 1-103 Η C02CH2-3-ClC6H4 H 4-CH 3 H 1 H-NMR (CDClg): δ = 1,06 (3H)i 2,68-2,80 (IH); 3,77 (IH); 5,15 (2H); 5,60-5,80 (2H); 7,3 (4Hi, ΐ - 104 Η CO2CH2-4-CIC6H4 H 4 - C H g H 1 H-HMR (CDCl3)s δ = 1,05 (3H); 2,65-2,78 (IH); 5,15 (2H); 5,60-5,80 (2K); 7,.32 ( 4H ) . 1-105 Κ CO2CH2-4-HO2C6K4 H 4 -CH3 H m.p,: 118-124°C 1 - 1 0& Η CO2CH2-2-C3C,,H4 11 4-CHg Η κ HCl MS: 279 (M* - 36] Table 1 - Continuation Bx.Η©b 1-107 1- IQS 1-109 3-110 1-111 1-112 Ϊ-Π3 1-114 1-115 i - ] 16 R* R2 H CO2CH2-3-ClC6H4 H CO2CH2-4-ClC6H4 H CO2CH2-4-NO2C6H4 H C02CH2-2-C1C&H4 H CO2CH2-3;C1C6H4 H C02CH2-4-ClC&H4 H C0,CH7-4-H0,CaHa H C02CH2-2-CIC6H4 H CO2CH2-3-ClC6H4 H CO2CH2-4-ClC6II4 R4 A Physical constants 4 “ CHg Η x HCl MS; 279 [M* -36] 4 -CHg. Η x HCl m.p.: 167® C 4-CH3 Η x HCl m.p.: 196-202°C Ή H 1 H-NMR (CDCl3): 6 = 2,15 (4H); 2,65-2,85 5,29 (230) 5,78 (2H) 7,50 (4H), 1 e 80- ( 3H) ; ) 7,20- H H 1 H-NMR iCDCl3): I « 2,15 (410,.2,56 ( 2H ) 2,75 (lH)j 5,15 ί2H) (2H)) 7,20-7,40 (4H) I ,.75) 2,65i 5,79 β H H m.p.: 14 2cC H H ’H-NMR (CDClgi: 1 = 1,75- Π Firsts t LUL 1 2 » 0 “ i * » ’ 2,15 (650) 5,26 (2H); 5,78 (210) 7,55 (2H)i 8,20 <2H).
H H x HCl ’H-NMR (DMSO): 1 = 1,952,12 (450 ) 5,15-5,35 (210) 5,65-6,05 (2H)) 7,30-7,60 (4H)) 6,25 OH). H H x HCl 1 H-NMR (DMSO): 6 1,95- 2,12 (4H>) 3,10 (IH); 5,19 (2H); 7,39 UH) J 8,25 (3H) H H x HCi MS: 265 (M1 - 36] Table 1 Bx=No3 ί - ί ί 7 - ί 1 δ ϊ-ί 19 1-120 1-121 1-122 1-123 Continuation R1 r2 r3 H CO2CH2-4-NO2C6H4 Η H CO2CH2-3,5-(OCH3)2C6H3 Η H CO2CH2-2-MO2C6H4 Η Η CO2CH2-2,4-Cl2C6H3 Η Η C02CH2-3-N02C6H4 Η Η CO2CH2-3,5-{OCH3)2c6H3 Η Η CO2CH2-3-NO2C6K4 Η R*5 Λ Physical constants Η Η 1 H-NMR (DMSO): δ = 1,902,15 MH)J 5,33 (211)1 5,706,05 (2Η)Ι 7,70 ί2Κ5; 3,20 (2Η5ΐ 8,45 (3Η), 4-CH3 Η M-S-NKR (CDC13) ϊ δ = 1,03 (3Η5ί 3,79 (6Η)ί 5,10 (2K); 5,50-5,80 (2Η)1 6,40-6,55 (3ΙΪ) , 4-CH3 Η 1 H-NMR (CDCi3)i δ = 1,05 ί3Η); 5,56 (2Η)ί 5,60-5,05 (2Η)1 7,45-7,70 <3Η)J 8,10 ( IH) , 1H-NMR ίCDC13): δ - 2,652,73 (1Η), 2,70 (1Η3J 5,21 (2ΗΪ1 5,78 (2Η)ί 7,20-7,35 ( 3Η) . Μ3ί 276 CM'1'3 J «·.} ϋί ί Η Η 1H-NMR iC0Cl3): δ = 3,79 (6Η)ί 5<10 UH)) 5,,30 (2H); 6,4 0 - 6,, 6 0 ( 3 Η ί » 4-CH3 Η 1H-NMR (CDC13): δ = 1,05 ί3Η); 2,68-2,00 <1Η)ί 5,28 (2Η)1 5,55-5,80 (2H); 7,507,75 (2Η)1 8,15-8,30 < 2Η) ( Tabla 1 ° Continuation iSx. H©= R* R2 R3 R4 A Physical constants 1-124 HCO2CH2“C6i'i5 H 4-CHiCH3)2 H1 H-NMR (CDC13); δ = 0,90 (6HB 2,60-2^70 UH); 5, 17 (2ΗΪ; 5,60-5,05 ί2H)J 7,35 (5H3 . 1-125 H CO2CH2-3,5-{0CH3)2C&H3 H 4-CH3 Η x HCI *H-HKg (DMSO3: δ = 8,29 ί-ΝΗ3 , 3ΗΪ, 1-126 H CC2CH2-2-NO2C6H4 H 4-CH3 Η x HCI ‘H-NMg (DMSO)i δ = 8,35 <-NH3 , 3ΗΪ, Ϊ-127 H CO2CK22,4-C12C6H3 H li H x HCI 1 H-HMg (DMSO): δ = 8,25 <-NH3 , 3H>. 1-128 H CO2CH2-3-NO2C6H4 H H Η κ HCI 1 H-NMg (DMSO): δ = 8,40 ί-ΗΗ3 , 3H). 1-129 H CO2CH2-3,5-ίOCHgί2C6H3 H H Η x HCI MS! 291 [M1 - 36ϊ 1-1.31 H co2oh2c6h5 H 4-CH3)2 Η x HCI 1 H-NMR (DMSO)! δ = 0,85 (6H); 1,55-2,10' (4H)J 5,20 <2H)i 5,80-6,00 (2H)1 7,38 (5H)J 8,35 i3H), 1-132 H CO2CH2-3,5-Cl2C6H3 H H Hs H-NMR (CDC13H S = 1,752,15 (6H)1 2,65-2,80 (1H)J 5,22 (2H)j 5,70 (2H) 7,20- 7,50 <3H), 1-133 H CO2CH2-2,6-Cl2C6H3 H H 111 H-NMR (CDC13); δ = 1,752,15 (6H)) 5,40 (2H); 5,75 <211)1 7,20-7,40 (3H).
Table 1 - Continuation gx.No. R1 R2 R' A Physical constants I- 134 H CO2CH2-3i5-Cl2C6H3 1-135 H C 0 2CH 2 — 2 ,8-Cl2Cg(H3 Η Η H x HCl 1 H-NMg (DMSO)ί δ = 8,43 (-NH3 , 3H>. Η l-ϊ H x HCl 1 H-NMg (DMSO): δ = 8,25 ί-ΝΗ3 , 3H), s) The XH-NKR spectra were recorded in deuterochloroform (CDClj) or dimethyl sulphoxide (DMSO) with tetramethylsilane (TMS) as th© internal standard, The chemical shift is Indicated as δ value in ppm.
Preparation of the starting substances; A solution of 10 g (0.089 moi) of sorbic acid,, 24.1 sal (0.27 mol) ok methyl acrylate, 0.1 g (0.6 mmol) ot 4-tert butylcatecbol and 100 ml of dioxane is reacted for 30 hours at a temperature of 110®C at 5 bar. The dioxane Is distilled off, and the polar by-products are separated off using the eluent mixture petroleum ether/ethyl acetate (2 ; 1). 13.2 g (75¾ of theory) of methyl 210 carboxy-5-methylcyclohex-3-ene-carboxylate are obtained as a mixture of isomers.
(CDC13, 200 MSs) s δ = 1.05 (d, 3Ξ) ; 3.65 (s, 3Ξ) , 5.40-5.90 (m, 2H) .
{Process 3/a) A solution of 20.5 g (0.11 mol) of tert-butyl (trans-3methyl-1,3-butadiene-l) -carbamate / 34 g (0.39 mol) of methyl acrylate, 1 g (6 mmol) of 4-terf-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 on silica gel using the eluent mixture petroleum ether/ethyl acetate (5 : 1) . g (80% of theory) of tert-butyl (3-methyl-679 carbomethoxy-2-cyclohexen-l-yl) -carbamate are obtained ass a waxy solid.
^-NMK’’ (CDC1S, 200 MBs) ϊ δ = 1.42(9«), 1.68 (38), 1.70-2.00(48), 2.70(18), 3.68(38), 4.50(18), 4.80 (18), .30-5.45(18) γ ^cooh HH-C-OC(CHg)^ II 33 0 (IIb-2) g (IS.6 mmol) of tert-butyl (3-methyl-6-carbomethoxy-2cyclohexea-l-yl) -carbamate are introduced into 40 sal of 1 H sodiua hydroxide solution, and the mixture is stirred at 50®C until a clear solution has formed- The solution is extracted once using diethyl ether, and a pS ox 1 is then 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 3 -as thyl - 6 -carboxy- 2 -cyclohexen-1-yl - carbamate of melting point X32-13S°C are obtained.
(IIb-3) (Process B/a) A solution of 18»8 g (0.13 mol) of ethyl trans-3-sitr© acrylate ia 100 al of benzene is added dropwise at room temperature to a solution of 20.1 g (0.11 mol) of tertbutyl -tr,ans-1,3«pentadiene-X-carbamate aad 0,25 g (1.5 mmol) of 4-tert-butyleat©chol in 50 ml of benzene, and the solution, is stirred for 20 hours at room temperature. The solution is concentrated to half the volume, and crystals are allowed to form at +4°C. 18.3 g (53% of theory) of ethyl 3-(N-tert-butylo:cycarbonylamino) -2nitro-6-methyl-4-cyclohexene-carboxylate of malting point 139-45®C are obtained.
O=C-O“C(CH3i3 (Process 3/a) g (55 mmol) of tert-butyl (trans-1,, 3-peatadlene-l) carbamate, 12.4 g (55 mmol) of trans-2-(2-chloro-515 nitrophenyl)-aitroethene and 0.6 g (3.S mmol) of 4-tertbutyleatechol la 100 ml of dioxane are reacted for 30 hours at X10 °C and 4 bar. The reaction mixture is evaporated aad recrystallized twice from ethanol. g (31% of theory) of tert-butyl 4-methyl-5-(2-chloro-520 nitro-pheayl)-e-aitro-Z-cyclohexea-l-yl-carbamate of melting point 195-203°C are obtained.
(IIb-5) O«C-O-C3)3 (Process 3/a) A solution of 1 g (5.5 mmol) of tert-butyl trans-1,3pentadiene-1 -carbamate, 1.1 g (11 mmol) of maleic anhydride, 40 mg (0.2 amsol) of 4-tert-butyleatechol and 3 ml of dioxane is heated at 100 “C for 2 hours. The mixture is evaporated to dryness, and 0.8 g (52% of theory) of tert-butyl (4-methyl-cyclohex-2-ene-5,5dicarboxylic anhydride-1-yl)-carbamate of a melting point of 180-182°C is obtained after recrystallization from benzene. ch3 OOCH* (lxb-6) HH-C-O“C(CK~)~ II o (Process 3/c) A solution of 5.4 g (0.05 mol) of ethyl chloroformate in 15 ml of acetone is added to a solution of 10 g (0.05 mol) of methyl 2-carbo3ey-5*'methylcyclohex-3-enecarboxylate and 8 g (0.062 mol) of K,H-diisopropylethylamine in 30 ml of acetone at -5®C in the course of 30 minutes. After the mixture has remained at 0®C for 30 more minutes, an ice-cooled solution of 6.5 g (0.1 mol) of sodium azide In 15 ml of water is added dropwise. The mixture Is stirred for 15 minutes at 0°C and then worked up using water/toluene.
The toluene phase, which is concentrated to approximately 50 al, is then added dropwise t© a solution, boiling under reflux, of 3 gr (0.04 mol) of tert-butanol and 25 mg (0.15 mmol) of tert-butylcatecbol in 20 ml of toluene. The course of the reaction is monitored by IB spectroscopy.
The mixture is allowed to cool to room temperature and concentrated. After separation by column chromatography on silica gel using the eluent petroleum ether/ethyl acetate (6 : 1), 4 g (30% of theory) of tert-butyl (4me thyl - 6 - carhome thoxy- 2 - eye lohaxea -1-yl) - carbamate o f melting point 89-91°C are obtained- (Process B/d) 0 g (21 mmol) ©fi tert-butyl {4-methyl-6-formyl-2-cycloheacen-l-yl) -carbamate are dissolved in '70 ml of tetrahydrofuran, and, after 1.6 g (42 mmol) of ©odium borohydride have been added, the mixture is stirred for IS minutes at 55 ®C. 17 ml of methanol are then slowly added dropwise at 55eC, and, when the addition is complete, stirring is continued for 3 hours at room temperature. Working-up is carried out under aqueous conditions, the mixture is extracted using diethyl ether, and, after drying over magnesium sulphate and evaporating, 4.8 g (95% of theory) of 2-[(tsrt-bufcyloxycarbonylamiao)-5methyl-3-cyclohexen-l-yl]-methanol Is obtained as a white, waxy solid.
(CDC1S, 200 s δ = 1.00(d, 3H> , 1.45 Cs, 9Ξ) , 1.75-2.40 (m, 2S> , 3.28-3.52 and 3.67-3.SO fe., 2Ξ), 4.00-4.30 and 4.45-4.75 (m, 2Ξ), 5.43-5.51 and 5-63-5.78 fe, 2Ξ) .
(IIb-8) (Process B/e) g (0.105 mol) of triethyl phosphonoacetate are added dropwise at O’C to a suspension of 3.4 g (80% strength in oil ~ 0.1 mol) of sodium hydride. Whea the evolution of hydrogen has ceased, a solution of 25 g (0.105 mol) of tert-butyl (4-aaethyl6-forayl-2-cyclohex©n-l“yl)carbamate in 30 al of tetrahydrofuran is added dropwise. After the reaction mixture has been stirred for 4 hours at room temperature, it Is added to 500 ml of water, and the mixture 1© extracted several times using ethyl acetate. The combined organic phases are washed with water and saturated sodium chloride solution and dried and concentrated. After purification by column chromatography on silica gel using the. eluent petroleum ether/ethyl acetate (5 s 1), 26 g (80% of theory) of ethyl trans- (2-N-tert-butoxycarbonylaiaiao-4“aj©thyIcyclohex-2-ea) -1-yl) -acrylate. are obtained.
^-NMET’ (CDC1V 200 MHz) s & = 1.05(d, 3H) , 1.20-1.35(m, 3Ξ), 1.43(8, SB), 1.60-2.60(^ 4H) , 4-15(q, 2Ξ)» 4.254.60(br.a, 2B), 5.50-5.95(m, 3Ξ) » 6.86-7.10 (sa, IS).
The 3H-»® spectra were recorded in deuterochlorofoza (CDClg) with tetrasnethylsilane (TMS) as the internal standard. The chemical shift is Indicated as δ value In ppm.
The precursors of the formula (Uh) NH-A (IXb) which are listed ia Table 2 below gously to the methods described ia (lib-8) aad. following the instruct are obtained aaalo, Examples (IXb-X) to XOHl'S sLXi descri©Table „2, BXe A R1‘ r21r3· r4* He.
R5· 5 Physical constants IIb-9 -C-GC(CHq)g H Jl lib» 10 “C=0C(CH3U H II IIb-11 -C-OCCCH.Og H J J G lib-12 -G-OC(CHg)^ H II 3 3 o ITb-13 -G-QC(CH3)3 H -COOH -COOH -COOCHg -COOCHg -COOCHg Η H H CHg Η H H -CH2-iCHg) H m.p.: 110-118eC H m.p.i 194-195°C (CDC13, 200 MEz) Η Η δ = 1,42(911), 1.70-2.10(4H), 2,73-2,85(111), 3.68(311), 4,48-4.59(111), 4.85-4.95 (HI), 5.60-5.86(2H) -ch20 lib“I4 -C-OCiCHgJg H -COOH il J 3 G H -CHg-(CHg) -ch2 H *11-1»®*’ (CDClj, 200 MBz) = 1.44(9H), 1.58-1.78 (111) , · 2<08-2.20(IE) , 3.30-3.40(IE)» β 3.62C3H), 4.60-4.80(2H), 6.90 (2H), 7.12-7.35(5H) i )( (CDClj, 200 MHz) δ = 0,80-2.30 (20BE) , 2,602.71(111), 3.85(311), 4,50(2H), 5.43(111) m.p.s 160-168eC Tabla 2 - Continuation R4 ’ R58 Physical constants Ex. a Ho·. Ri* ·%, 9 R^ R llb=15 -C-QCiCHg^ 0 CHg -COOCHg H IIb-l6 -C-GCiCHo)^ ii J 0 H - εοϊ'Ήΐ*ί il J 1 Ls *“ 1T · C e 0 C ί C 1I *a) ra ό· II -COOCHg H Ilh =10 -C=OCiCH,)q II 3 3 0 Ii -CQOCHg 11 Uh=17 =6=00(01½)^ || IL? tl ϋ H -COOH H I lb“20 -G-OCCCH-»)^ II 0 H -COOH H llb=2i =C=OC(CH-,)«, 21 fc! U H -COOH H CHg c3h7 h CgHg H C-glf5 H H n-C4H9 H CgHij H lH-NMR*’ (CDCI,, 200 Mils) δ = 1.18{3H), 1.44(911), 3.S8(3H), 5.50-5.80(211) H m.p.i 148-150°C aH-NMHa’ (CDClj, 200 KHz) δ s 0.99(311), 1.20-1.48(311), 1.85-2.12(211), 3.67(311), 4.52(211), 5.71C2H) m.p 73-85®C m.p.: 149-1S7®C OS lK-HMR*’ (CDClj, 200' MBs) β a 0.83(311), 1.10-1.50 and 1.80-2.00(2011), 2.70-2.85 (IB), 4.40-4. SO and 5.005.20(111), 5.35(211) a.p.i 120-128°e (hygroscopic) Tabla 2 - Continuation ’ R&· Physical constants Ex. Ho. A Rl‘ ϊϊ2 ’ R3 ’ 1lb-22 • Τ'3 · ΠΡ ? Ptl ft ftuj Uw i Lti !*} # **3 j | tJ 0 H -COOCHg H H 1ib-23 _ί5_ flf5 / i^tl ft “ Lsw U L? 1, G e ! eft J *3 n J 3 0 H -COOH H c3ii7 1 lb-<24 β» f3 m f f^lul ft |j J J 0 H -CH H lib-25 -C-OCiCH^)«i II fl H -CH ii CHq llb-2& u °C*OC ΐ CH«a ) il 0 Cl -CH H Cl'Ig Hb-27 “C»OCtCH^)q II 3 3 0 H -HO* 8L9 -COQCgHg Ii I lb-20= C “ OC ΐ CH «a )«» li 3 3 0 H -H09 -Q HO CHg 2 IIb-29 -Ο-ΟΟΗ,-θΗ -»O2 - o COQC gHg ch3 H m.p.s 65-71®C H m.p.; XXS-X42®C H m.p.i X21-122®C H MS; 183 M*CX2), 153, X27, 83, 57(100} H m.p.; 11S-121®C « m.p.; 95-9S®C m.p m.p. s 130-185*6 88-91®C Continuation RJ i?3· FT ?5· ’ Physical constants Ex e A Ho b IIb-30 -C-O-Cli-s t o H “NOg -COO-C4H9-l CH3 rn.p.i 173-18I°C lib-31 »C-OC(CH3) m.p.: 103-183eC lib-32 -C-OC(CH3)3 li “ 3 3 ^C^OC C CH «□ 3 tl IIb-34 “C-OCieiUH II 3 3 IIb-35 -C-OCiCHgU II J 3Q.p.: 150-17-4aC ,, m.p. i 171-17S°C H ri ., ,, ai.p. 9S-107®C n^-n H m.p·: 203-20'SaC Η H ! © © I Table 2 - Continuation II b- 37 -C-OC ί CH-J) -, f· jj 3 3 I -NGg -COOCgHg -CH?-iCH,)^-CH5- Se se &e ii G MS; 358 M* (0,1), 57 (100) I3h-3fl -C-GCH·, H II I 2 . o ch»ch2 IIb-39 -G-OCH, H II I ώ CH=C1U IIb-40 -C-OCteiUH H 11 3 3 .: O 1I b-4 1 -C-OC ί CllH 33 MOg -COQC4H9-l H NO 3 -COOC4H?-L Clh H H ii H m.p,i 123-124°C H m.p.s 120-126’C H m.p,ί 185-lSleC m.p,; 204-2Q5eC H m MX Table 2 - Continuation Ex, 2s R3’ PP R1 Physical constants o il lib-42 -C-OCiCH^b, H || fe? fej o m.p. s 182-134 °C M llb-43 -C-DCiCH-,ϊ-, 1-1 f f few Ϊb 44 “OOC(GHg)g, H XIb-45 -C-OCiClU)q H II 3 3 ' o II -C* M— m.p.i 08-93*C Π 11 K fel? II o II HN- H m.p. 45-51eC __P o CH3 H ]{ m.p.s 132-135®C ι »© o f Table 2 = Continuation 6’ Physical coastante Ex. A No. Rl *R2' R4 ’ llb=4ii -C-GC(CHgi^ 0 Ii MOg -COG-C4H9-t -o IIb-47 -C-GCECHglg 0 H ng2 /-Cl CHg I'Ib-Ίδ -G-GCiCHgig 0 II NOg -G~\ \_t- CHg Hb-49 -C-QCiCHgig Q H ng2 -CQQCjgHg -o iib-so =c»oeiciuu II 3 0 ΪΙ NOg -cqg-c4h9-i CHg IIb-5 1 -C-OCiCH-,1, II 3 3 0 H HQ2 -coo-c4h9- l H m.p.; 197-199®C m.p.s lS5-168eC it II SQi 3 p.i 168-172*C I co H j p.s 130-135eC 18Q-1S5°C 1G5-1€0°C Tabla 2 gx, A R1 ' R2* R H© · 1 Physical constants llb-52 -c-ociciM'.! If J 1 o ii CHO aH-NMRs) (CDClj, 200 MHz) Η δ s 0.95-1.25(4 isomers, 3H) , 1.42 (s, SH), 5,55-0.90 (m,2H), 9.60-9.35 («1 isomers, IH) IIb-53 -C-OC(CH3)3 II CHO O Xlb-54 -C-OCiCH-sl'-i H II 3 J IIb-55 -C-OCiCHoJ-a F II 0' lXb-56 =C-0C(Ci'U)q H II 3 3 IIb-57 “C-OCiCHa), H || tl %£ IIb-58 -C-OCiCH3)3 If H IR (CHjClj) ί 3300, 2950, 2710, 1700 2E1 CHO H CHO H -CH«CH H I COOH -CH=CU H I COOH -CH»CH H CK3 H ch3 h CH3 η II H COOC2H5 H IS (CHaCla) i 3400, 2950, 2860, 1720 cm1 H MS s 201 [M* - isobutene] (5), , 183, 153, 127, 83, 57 vo H m.p,s 106-135°C H a, p. 107-130®C H m.p.§ 59-65°C Tabla 2 - Continuation R* ’ R 21r3 R r5 1r6 “ Physical constants Ex, Nc, llto-S? -C-OCCCHgig H -CHoOH Η H if J t'5* IIb—60 “C*OC(CHq ϊq 1I II 3 3 H J. lb* 61 ™C“OCCCHqiq 1/. N0*> |j di -U a® b » 6 2 “ C - OC ί CH q 1 q II COOH II J nb-63 “C“OC(eHg)g H COOCHq II a 3 □ IIb-64 “C-OC(CHg)g H NO? j| <7 <1 s£ o il NO g !! H H ·, H lllH-NMR*’ {CDCl3ί 200· 24Hz} δ = 1,45 (9H), 1.55-2.13 (4H), 3.30-3,75 (211) e 4.084,30 {IK}, 4.70-4.SB (IK), 5.45-5.93 C2H) 11 11 m.p,ί 83 ®C •CH ί CHqΪ q dl l<£ 11 m. p. s 16 5 -17 0 ° C -CHiCHgJg H m.p.! 100-124°C -CHCCHg)2 11 a.p.s 85-93®C H H m.p.s 167-181°C HO 2 Table 2 - Con fc inua fcion BX. M©. A R1 ’ 1r31 R4 ‘Rs Cl 11 b - 6 S l “C-OCl-UCCl-i 11 H WO2 C H rg H 0 Cl. 11 b - 6 6 “C* OC ί CH g Ϊ g H -COOC^Hr H SS w1 ch3 H Physical constants H m.p.: 99-100®C H a.p.i ?0-75eC □ IIb-67 = c ii 0 “OC ί CHg)g H -COOC4H9 H cilg H I11/=-68 »c ii ”OC( CHg ) g H -C-NiCIUU H «ί ώ H H I'i Q H it 0 11 b “ h 9'dCd OC (CHg 1 g It eJ '* H — C Ν ΐ CH »5) ο II il d ““ dig il £ 11 0 IIb-70 -t >0C(CH3)3 il -i\. H CHg H ! JJ OCHg 0 0 H Di.p,: S5”7l*C H m.p.ί 115-118®C , w }|k H m.p.i 121-124®C ' KS [m/Z, % rel.infc.]s 305 [K*3(G.9), 249 (21), 205 (10), 188(15), 83 (100), 57 (68) Tabla 2 - Continuatlen Kx, No a R2' R R6'Physical constants A lib-72 -C-OCHoCH?GCH^ || I ib-73 -C-OCf-UCi-UOCHq ΊΙ Go G$ Ll Ii G Hb-74 -C-CtU II IIb-75 -C-iCH?)sCHg IIb-76 -C-(CH2)16CH3 Ii IIb-77 -C-OCiCHoU II G H -C-GC If o H -CO2CH3 H -MO 2 — < H -CO2H H -C02H H -CGoH H -CO2CH2CH(CH35 CH3 Η H m.p.·. 72-7 8° C CH3 Η H ng® 1.4802 CH3 Η H m.p. ί 166-170°C CHg Η H m.p.: 202-220°C ’ “ tO tn CHg Η H m.p.: 144-146°C CH3 Η H m.p.: 1073 c CH3 Η H m.p, .· 6 3-64° c Tabla 2 - Continuation Ex. & * Ho. »3 R!R6 · Physical constants lib»78 -C-0C(CK3)o li 3 3 o lib-79 -C-OCiCHo)q II H -COgCHg H -CO2CH3 IIb-30 -C-OCiCH^iq II H -CQgCHg lib-81 -C-QCiCI-hH If J o IIb-82 -C-OC3)g il H -C02H H -CO2H «zch3 CH xch3 H H1H-NMR iCDCIg)s UHU 2,43 <9H) <3H); 5,75 <2H) & = 0.90 1 3,68 6 H CHg ch3 H1 H-NMR (CDC13)5 6 = 1.05 (3H); 1.40 <9K) 5 1.60 C3H); 3,67 (3H) 5 5.45 < 1H) , ^CHg /--; K1H-NMR (CDC13); δ = 0.73 H CH^Cii / H 0,86 i8H){ 1,43 ί 9H ί ; \;h3 \=. z 3.6S ί 3H Ϊ- j 5.82 ί 1 Η ); 7,15-7,30 (5H). H CH H H m.p. ; 154-158s CVCH3 H dig C H rj H m.p. : ί 47-152° C <1© Sh IIb-83 -C-OC(CHo)o Si o H -CO2H H CH2CH H m.p.: 122-i25°C 'CH- x, Tabla 2 = Continuation ISX. A No.
R1’ R2* r3· r4‘ r5‘ R&·Physical constant® IIb-84 -C-0CiCH3i3 H -HQ? tj) CH3 Η H m.p. ! 1 69- 170° C IIb-85 -C-OC(CHo)^ II 3 3 H -CN H CH2CH(CH3)2 CH3)2 H m.p.: 117-i21°C IIb-Q& -C-0C(CH3i3 H -CN H CH(Ci13)2 C6H5 Hm.p.: 84-105°C IIb-87 -C-OCCCi-UU II iib-sa -c-occch-,)·, II lib-89 -C-0C(CiU)3 II 3 3 H -CO2H H -CO2H H -CO2H H CK(CH352 C6Hs H E.p.: 151-17 1°C CZ) H CH2CH(CK3)2 CH(CH3)2 H m.p.: 150-156°C TA H MS: 307 [M‘3 s) Th© ’li-NMR spectra were recorded in deuterochloroform (CDClj) with tetramsthylsilane (TMS) as th© internal standard.. The chemical shift is indicated as δ value in ppm. io SS (XVa-1) 3¼ h2c CH II =C—CH=CH-NH~C-OC(CH A solution of 54 g (0.5 mol) of ethyl chloroformate ia 150 sol 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 methyl-2,4-pentadienecarboxylic acid and 80 g (0.62 mol) of N, M-di isopropyl ethylamine In 300 ml of acetone. After the mixture had remained at 0°C for 30 more minutes, aa ice-cooled solution of 65 g (1 mol) of sodium azide in 150 ml of water Is added dropwise. The mixture Is stirred at 0°C for 15 minutes and then worked up using water/toluene. The toluene phase, which has been concentrated to about 300 al, is then added dropwise to a solution, boiling under reflux, of 29.6 g (0.4 mol) of tert-butanol and 250 mg (1.5 raaol) of tert-butyleatechol in 200 ml of toluene. The course of the reaction Is monitored by IR spectroscopy. The mixture is allowed to cool to room temperature and concentrated. After separation by column chromatography using the eluent petroleum ether/ethyl acetate (6 s 1), 59 g (65% of theory) of tert-butyl trans-3-methyl-1,3-butadiene-1-carbamate are obtained.
I 31 ίϊν-2) h2c-c-ch-ch-cgqh 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-pentadienecarboxylate, dissolved In a solvent mixture of 75 ml of 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 pH of 1 is established la the aqueous phase at 0°C using concentrated hydrochloric acid. The mixture is extracted using diethyl ether, the combined organic phases are washed several times with water and saturated sodium chloride solution, and, after drying and concentrating, 6.1 g (76% of theory) of trans-4-methyl-2,4-pentadiea©carboscylic acid are obtained.
(IV-1) - 9S CrU I h2c=c-ch=ch-cooc2h5 g (2 „57 mol) of sodium hydride (80% strength in oil) are added in portions at 0“C under a nitrogen atmosphere to a solution of 630 g (2.8 mol) of triethyl phosphono5 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) ox saethacrolein in 2000 ml of tetrahydrofuran 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, aad the mixture is extracted several time® using ethyl acetate, lifter drying, concentrating and distilling, 146 g (37% of theory) of ethyl trans-4-methyl-2,4-pentadi>3ae15 carboxylate of boiling point 76-90°C/20 bar are obtained.
Use .Bxamoles In the following Use Examples, the compounds listed below eis-Βϊ-((trichloromethyl)thio]-4-cyclohexene-l,2-dicarboimide (disclosed in Science, (Washington) 115, 34 (1952) ?, HS Patent Specification 2,553,770)„ 100 Example A Venturia test (apple)/protective Solvents 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl poly5 glycol 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 ar© sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, the plants are Inoculated with an aqueous conidia suspension of th® appl® scab causative organism (Venturia inaecualis) and then remain la an incubation cabin at 20°C and 100% relative atmospheric humidityfor 1 day.
Th© plant© are then placed In a greenhouse at 20®C and a relative atmospheric humidify of about 70%.
Evaluation Is carried out 12 days after the inoculation20 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 in % of th© untreated control at an active compound concentration of Active compound 5 ppm (1-3) 102 Example 3 Phyfcophthora test (tomato) / protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 part by weight of alkylaryl 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, aad the concentrate is diluted with water to the desired concentration» To test for protective activity, young plants are 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 infestans.
The plants are then placed in an incubation cabin at about 20°C and a relative atmospheric humidity of 100%» Evaluation is carried out 3 days after the inoculation.
In this test, for example the substances (S-3) aad (1-45 according to the invention show a very high degree of effectiveness at an active compound concentration of 10 PP®· 103 Table Β Phytophthora test (tomato)/protective/curative/systemic Degree of effectiveness in % of the untreated control at aa active Active compound compound concentration of 10 ppm (1-4) 104 Example C Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active couapousd, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 ea 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 am. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied la 2,000 1 of water/ha. After three weeks, the degree of damage to the plants is rated in % damage In comparison to th® development of the untreated control. The figures denote: 0% - ao action (like untreated control) 100% = total destruction In this test, for example the compound ¢1-4) shown in Tabic C below shows a very good herbicidal action. In particular in wheat.

Claims (20)

1. Patent Claims
1. Use of substituted 2-eyclohexen-1-yl-amine derivatives o£ the formula (X) (1) NH-A iu which 3? represents hydrogen, alkyl or halogen, S 2 represents formyl, hydroxyalkyl, cyano or nitro, or represents one of the radicals ΝΞ3 5 , -NK e K 7 , NH-CH-COOM, “CHg-Q-C-Rs “C-ε? 10 , -PO® 11 ) II o II o 5x XR*2
2. » II Rl3 X 1 SiOkR 1 * or -CB=CSE-3‘\ K 3 and H* are identical or different and in each case represent hydrogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy or alkinyloxy, or represent uneubstituted or substituted aryl, or represent unsubstituted or substituted aralkyl, or represent unsubstituted or substituted hetero&ryl, or represent unsubstituted or substituted heterocyclylalkyl, alkoxyalkylosy or halogen, or represent one of the radicals -NH-R\ -N3 S 3 7 or -S(0i a -3 M , or St 2 and R s together represent one of the radicals 107 f'l. 6 II 0 ο ' Τ°ΐ ° Τ 0 0 JJ which are bridged via the 6- and 5-positions. or £t 3 and EC 1 together represent an alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4- aad 3-positions,, H s represent© hydrogen, alkyl or unsubstituted or substituted aryl, H 5 ’ represents alkyl or unsubstituted or substituted aryl, B 7 represent® alkyl or unsubstituted or substituted aryl, R® represents hydrogen, alkyl, unsubstituted or substituted aryl or unsubstituted or substituted aralkyl, R s represents alkyl or alkoxy, a” represents hydroxyl, hydroxyalkyloxy, halogenoalkyloxy, alkoxy, alkoxyalkyloxy, unsubstituted or substituted cycloalkyloxy, unsubstituted or substituted aralkyloxy, unsubstituted or substituted aryloxy, unsubstituted or substituted aralkyl, alkylthio or unsubstituted or substituted arylthio, or represents a group -OH, -ΪΪΞΒ 5 , -HB S R 7 or -O-S-SiR’B*, R 11 represents hydrogen or alkyl, R ia represents hydrogen or alkyl. 108 a X3 represents alkyl, a 14 represents alkyl, alkoxy or unsubstituted or substituted aryl, or represents the group -0M, B xs represents formyl or cyano# or represents the. group -C-R 10 II ο represents hydrogen, alkyl or unsubstituted or substituted aryl, M represents hydrogen or represents an equivalent of a corresponding alkali metal cation, alkaline earth metal cation or ammonium cation, a represents a number 0, 1 or 2, X and S l are identical or different and represent oxygen or sulphur, m represents a number 1 or 2, A represents hydrogen or an amino-protecting group and S represents, a straight-chain or branched alkyl chain, and their acid addition salts and metal salt complexes for combating pests. 2, Substituted 2-cyclohexea-1-yl-amine derivatives of th® formula (la) [laS - 109 in which in R 1 ' represents hydrogen, alkyl or halogen, a 3 ' represents forsayl, hydroxyalkyl, cyano or nitro, or represents one of the radicals -CH a -O-C-R 7 ', -C-R*' or -CS=GH-R 9 ', R 3 ', R*', R 5 ' and R®' are identical or different and each case represent hydrogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy and alkinyloxy, or 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 alkoxyalkyloxy, or represent halogen, where at least two of the radicals R 3 ', R 4 ', R’’ or R 6 ' represent hydrogen, R 7 ' represents alkyl or alkoxy, S 15 ' reproLseats hydroxyl, hydroxyalkyloxy, halogenoalkyloxy, alkoxy or alkoxyalkyloxy, unsubstituted or substituted cycloalkyloxy, unsubstituted or substituted aralkyloxy, unsubstituted or substituted aryloxy, unsubstituted or substituted aralkyl, alkylthio or unsubsfcituted or substituted arylthio, or represents a group -O-3S-HR U 'R 12 ', -HER 10 ', -HR U *R 12 ' or -OM, R 9 ' represents forsayl or cyano, or represents the group -C-R 8 ’ II R 10 ' represents hydrogen, alkyl or unsubstituted or 110 substituted aryl, R 11 ' and R 12 ' are identical or different and in each ease represent alkyl or unsuhstituted or substituted aryl, S represents a straight-chain or branched alkyl chain and M represents hydrogen, or represents an equivalent of a corresponding alkali metal cation, alkaline earth metal cation or ammonium cation or R 2 ' and R 3 ' together represent one of the radicals -C-N-C-, -C-O-CII II o o OH 13 ' 0 or ~(CH->) -0-Cbridged via the 6- and 5-positions, where R 13 ' represents hydrogen, alkyl or usasubstituted or substituted aryl and m represents a number 1 or 2, or R*' and R s ’ together represent 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 and zaeral salt complexes, with the exception of the compounds 2-amino-cyclohex-3-ene-carboxylic acid and ethyl 2-amino-cyclohex-3-ene-carboxylate. Ill
3. Substituted 2-cyclohexea-l-yl-amine derivatives of the formula (la) according to Claim 2, in which represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, or
4. 5 fluorine, chlorine or bromine, H 3 ' represents formyl, straight-chain or branched hydrosryalkyl having 1 to 8 carbon atoms in the alkyl moiety, cyano or nitro, or represents one of the radicals -CH,-O-C-R 7 ', -C-R®' or in R H 10 0 0 -CH=CHR 9 ', Η 3 ', R*', R s ' and R 6 ' are identical or different and In each case represent hydrogen, In each case straight-chain or branched alkyl or alkoxy 15 having 1 to S carbon atoms, in each case straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, In each case having 2 to 8 carbon atoms, or alkoxyalkyloxy, in each case having 1 to 8 carbon atoms ia the 20 individual alkyl moieties, or represent aryl or aralkyl. In each case having S fc© 10 carbon atoms is the aryl moiety and where appropriate 1 to 4 carbon atoms ia the alkyl moiety, and in each case being unsubstituted or mono25 substituted to pentasubstituted In the aryl moiety by identical or different substituents, suitable aryl substituents beings halogen, nitro, cyano, amino, Cj-C^-alkyl, Ct-C*-alkoxy, Cj-C,,-alkyl thio, halogen©- (Cj-C^J-alkyl, halo30 geno- (C x -C 4 ) -alkoxy, halogeno- {C.-Q*} -alkylthio, each having 1 to 9 identical or different halogen atoms, and dl-(C x -C 4 )-alkylfurthermore represent a heterocyclic 5- or 35 6-membered group from the series comprising furyl, thienyl, pyrrolyl, pyraxolyl, 112 isaidasolyl, 1,2,3- or 1,2,4-triazolyl, oxasolyl, isoxaaolyl, 1,2,4- or 1,3,4oxadiasolyl, thiasolyl, ieothiasolyl, 1,2,3-, 1,2,4-, 1,2,5- or 1,,3,4-thiadiasolyl, pyridyl, 5 pyridazlnyl, pyriaidlayl and pyrazisyl, which group Is ussuhstltuted or saoaosubsfcitufced ft© trisubstituted by identical or different substituents and where appropriate linked via a methylene group, suitable substituents oa the 10 heterocycle in each case beings halogen, nitro, cyano, amino, C-C^-alkyl, C x “C 4 -alkoxy or C,-C 4 -alkyl thio, halogeno- {C-CJ -alkyl halogen©- (C,-C^S -alkoxy, halogeno- (C x -C 4 ) alkylthio, each having 1 to 9 identical or 15 different halogen atoms, and di- (Cj-CJ -alkylfurthermore represent fluorine, chlorine or bromine, where at least two ©£ the radicals R 3 ', &*', K s ' 20 or S*' represent hydrogen, 8?’ represents in each case straight-chain or branched alkyl or alkoxy having 1 to 6 carbon atoms, R 8 ' represents hydroxyl, straight-chain or 25 branched hydroxyalkyloxy having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyloxy having 1 to 3 carbon atoms and 1 to 17 identical or different halogen atoms, cycloalfeyloxy having 3 to 6 carbon atoms which 30 is unsubsti tuted or monosub®ti tuted to polysubstituted by identical or different halogen substituents, ia each case straightchain or branched alkoxy or alkylthio, aralkyl having 1 fc© 6 carbon atoms, or straight-chain 35 or branched alkoxyalky lossy, in each cage having 1 to © carbon atoms la the alkoxy 1X3 moiety or alkyl moiety, or aryloxy, arylthio, aralkyl or aralkyloxy, ia each case having 6 to 10 carbon atoms in the aryl moiety aad where appropriate X to 8 carbon, atoms ia the 5 alkyl moiety, aad ia each case being unsuhstituted or monosubstituted to pentasubstituted ia the aryl moiety by identical or different substituents, suitable aryl substituent© being the aryl substituents mentioned above, or 10 represents a group -O-Z-NR xl 'S i3 ', -NHR 10 '» -NR lv R ia ' or -ΟΜ» R*' represents formyl or cyano, or represents the group -C-R 8 ' II R 10 ' represents hydrogen, straight-chain or 15 branched alkyl having 1 to 6 carbon atoms, or aryl which has 6 to 10 carbon atoms aad which is unsubstituted or monosubstituted to pantasubstituted by identical or different substituents, suitable aryl substituents being the 20 aryl substituents mentioned above, R 11 ' 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 monosubstituted to penta,substituted 25 by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, R 13 ' represents straight-chain or branched alkyl having 1 to S carbon atoms, or aryl which has 30 6 to 10 carbon atoms aad which is unsubstituted or moaosubstituted to pentasubstituted by identical or different substituents. 114 suitable aryl substituents being the aryl sub stituents mentioned above, BS represents hydrogen, or represents .an equivalent of a corresponding alkali metal cation, alkaline earth saefcal cation or ammonium cation, and Z represents a straight-chain or branched alkyl chain having 1 to 3 carbon atoms or R 2 ' and B 3 ' together represent ©ne of the radicals -C-ν c-. -c-o-r- - 2 ) m -0-C~ .13· -C-, -c-o-cII II II or 0 0 0 0 o bridged via the 6- and 5-positions, where R 13 ' 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 peafcasubstituted by identical or different substituents, suitable aryl substituents being the aryl substituents mentioned above, and m represents a number 1 or 2, or B?' and R s ' together represents an alkyl chain which has 3 or 4 carbon atoms. and which is linked via the 4- aad 3-positions, and their acid addition salts and metal salt complexes „ 115 Substituted 2-cyclohexen-1-yl-amine derivatives of the formula (la) according to Claim 2, in which R 1 ' represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or fluorine, chlorine or bromine, S, 2 ' represents formyl, straight-chain or branched hydroxyalkyl having 1 to 4 carbon atoms in the alkyl moiety, cyano or nitro, or represents one of the radicals -CSL-O-C-R 7 ', -C-R 8 ' or δ n ° o -Cj3=CH-R § , S 3 ’, BL*', R 5 ' and SL e ’ are identical or different and in each case represent hydrogen, in each case straight-chain or branched alkyl or alkoxy having 1 to 5 carbon atoms, in each ease straight-chain or branched alkenyl, alkinyl, alkenyloxy or alkinyloxy, in each case having 2 to 6 carbon atoms, or alkoxyalkyloxy, In each case having 1 co 6 carbon atoms in the 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 unsubss tituted or monosubs tituted to trisubstituted in the phenyl moiety by identical or different substituents, suitable phenyl substituents being: fluorine, chlorine, bromine, nitro, cyano, amino, C x -C 2 alkyl, C x -C 3 -alkoxy, C x -C 2 -alkyl thio, halogeno(C x -C a ) -alkyl, halogeno-(C x -C a )-alkoxy and halogeno- (C x -C 2 ) -alkylthio, in each case having 1 to 5 identical or different fluorine and/or chlorine atoms, and di-(C x -C a ) alkylamino, furthermore represent a heterocyclic five- or six-aeaabered group from the series comprising furyl, thienyl, pyrrolyl, pyrazolyl, 116 imidazolyl, 1,2,,3- ar 1,2,4-fcriazolyl, oxazolyl, isoxazolyl, 1,2,4- or 1,3,4-oxadiazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,2,4-, 1,2,5- or 1,3,4-thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, which group is uneubstituted or monosubstituted to trisubstituted by identical or different substituents and where appropriate linked via a methylene group, suitable substituents on the heterocycle in each case being: fluorine, chlorine, bromine, nitre, cyano, amino, C,=C S alkyl, G.-G,- alkoxy or Ci-C 2 -alkyl thio, halogeno- (C x -C a ) -alkyl, halogeno- (C x ~C a ) -alkoxy and halogen©- (C x -C a ) -alkylthio, in each case having 1 to 5 identical or different fluorine and/or chlorine atoms, and di-(C,-C 3 >-alkylamino, furthermore represent fluorine, chlorine or bromine, where at least two of the radicals R 3 ', R*', 3 s ' and 3 s ' represent hydrogen, 3 7 ' represents in each ease straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms, 3®' represents hydroxyl, straight-chain or branched hvdroxyalkyloxy having 1 to 6 carbon atoms, straight-chain or branched halogen©alkyloxy having 1 to S carbon atoms and 1 t© 13 Identical ©r different halogen atoms, cycloalkyloxy having 3 to 6 carbon atoms which is unsubstituted or monosubstituted to trisubstltuted by identical or different substituents from the series consisting of fluorine, chlorine and bromine, in each case straight-chain or branched alkoxy ©r alkylthio having 1 to 4 carbon atoms, or straight-chain 117' IS or branched alkoxy-alky loxy, in each case having 1 to 4 carbon atoms in the alkoxy moiety or alkyl moiety, or phenyloxy, phenylthio, phenylalkyl or phenylalkyloxy, where appropriate in each ease having 1 to 6 carbon atoms in the alkyl moiety, and in each case unsubstitutod or moaosubstituted to trisubsti» tuted in th® phenyl moiety by identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, or represents a group -Ο-Ζ-ϊίΗ 11 '^ 13 ', -NHR 10 ’, -HR 1V R 13 ’ or -OM, R s ’ represents formyl or cyano, or represents the group “C-R 8 ' II o R 10 ' represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, or phenyl which is unsubs tituted or mono substituted to trisubstituted by Identical or different substituents, suitable phenyl substituents being the phenyl substituents mentioned above, R 11 ' 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, R 13 ' 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. 118 5» suitable phenyl substituents being the phenyl substituents mentioned above, M represents hydrogen, or represents an equivalent of a corresponding alkali saetal cation, alkaline earth metal cation or amiaoniusa cation and S represents a straight-chain or branched alkyl chain having 1 to 6 carbon atoms, or R 3 ' and R 3 ' together represent ose ©fi the radicals - (CH 2> ir -0CII II or 8 “ II 0 0 S bridged via the S- and 5-positions. II o r 13 ‘ o R 13 ' represents hydrogen, straight-chain or branched alkyl having 1 to δ 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, and ax represents a number 1 or 2, or R*' and R*' together represents aa alkyl chain which has 3 or 4 carbon atoms and which is linked via the 4- and 3-positions. and their acid addition salts and metal ©alt co» plexes. The hydrochloride of the cis-diastereomer of 119 2-amino-cyclohex-3-en©-carboxylic acid.
5. 6. The hydrochlorides of the enantiomers of 2-aminocyclohex-3~ene-carboxylic acid of melting point 2X0 - 213.5 e C and 208 - 210®C. 5
6. 7. The 2-amino-eyclohex-3-ene-earb©xylic acid isomer of melting point 98 ®C»
7. 8. The hydrochloride o£ th® ethyl 2-amino-cyclohex-3eae-carboxylate-isomer of melting point 139 148°C.
8. 9. Process for the preparation of substituted 2-cyclohexea-l-yl-asaiae derivatives of the formula {la) (Ia) in which B 1 ' represents hydrogen, alkyl or halogen, R a ' represents formyl, hydroxyalkyl t cyan© or nitro, or represents one of the radicals -CSL-O-C-R 7 '» -C-R 8 ' or -CH=CH-R e ', ϋ ϋ R 3 ', R 4 ', 3 s ' and R s ' are identical or different and 20 in each case represent hydrogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy and alkiayloxy, or represent unsubstituted or substituted aryl, or represent unsubstituted or substituted aralkyl, or represent 25 unsubstituted ©r substituted heteroaryl» or represent unsubstituted or substituted heterocyclvlalkyl, or represent alkoxyalkyloxy, or 120 represent halogen, where at least two of the radicals R 3 ', R*', R 5 ' or R®' represent hydrogen, SL 7 ' represents alkyl or alkoxy, H®' represents hydroxyl, hydroxyalkyloxy, halogenoalkyloxy, alkoxy or alkoxyalkyloacy, unsubstituted or substituted cycloalkyloxy, unsubstituted or substituted aralkyloxy, «asubstituted or substituted aryloxy, unsubstituted or substituted aralkyl, alkylthio or wnsubstifcufced or substituted arylthio, or represents a group -Ο-Ζ-ΝΗ 11 '^ 13 ', -K3R 10 ', -NR XV R 12 ' or -OM, a*' represents formyl or cyano, or represents the group ~C-R 8 ’ II o R 10 ' represents hydrogen, alkyl or uasubstituted or substituted aryl, R X1 ' and R X2 ' are Identical or different and In each case represent alkyl or uasubstituted or substituted aryl, Z represents a straight-chain or branched alkyl chain and M represents hydrogen, or represents an equivalent of a corresponding alkali metal cation, alkaline earth metal cation or ammonium cation or R 2 ' and R 3 ' together represent ose o£ the radicals -C-N 11 '. 3 · 0 H i3 - 121 -C- , -c-o-co™ ooo bridged via the 6- and 5-positioas 2 ) ra -0-C0 where R i3 ' represents hydrogen, alkyl or unsubsfcifcuted or substituted aryl and ω represents a number 1 or 2, or R*' and R s ' together represent aa, alkyl chain which has 3 or 4 .carbon atoms sad which is linked via the 4- and 3-positions, and their acid addition salts and metal salt complexes, with the exception of the compounds 2-amino-cyclohex-3-ene-carhoxylic acid and ethyl 2- amino-cyclohex-3-ene-carboxylate, charac teri zed in that A) 2-cyclohexea-l-yl-carboxylic acid derivatives of the formula (II) Q-R 14 ' la which R 1 ', R 2 ', R 3 ', R*’, R 5 ' and R®’ have the abovementioned meaning and R 1 *' represents hydrogen, methyl or ethyl. 122 are treated ia a generally customary manner with chloroformic acid ester, by the method of Curtins, if appropriate in the presence of a diluent and in the presence of a base at temperatures between -15°C and «-10°C, and adding an aside to this reaction mixture, if appropriate in the presence of a diluent, at temperatures between ~5 W C and *25°C, and hydrolysing the isocyanate, which occurs as an intermediate, of the formula (Ila) in which (Ila) IS R 1 ', R 2 ', St 3 ', R'*’, R s ' and R*' have the abovementioned meaning, 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, or 0) the amino-protecting group is eliminated from the 2-cyclohexene derivatives of the formula (lib) (Sib) in which R° R“ R 3 R 4 ', above-mentioned meaning and R e ’ have the and 123 A represents sn ©mino-protectiag group. in & known manner by customary methods, if appropriate ia the presence of a suitable solvent or diluent or a mixture thereof, with 5 cooling,, at room temperature or with heating and, 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
9. 10 addition salts or metal salt complexes. 10. 2-Cyclohexene derivatives of the fonrula (IXb) (lib) In which IS R s '„ 3 2 ', 3 s ', 3£*', 3 s ' and R b ' have the meaning indicated In Claim 2 and A represents an amiao-protecting group, with the exception of the compounds and the enantiomers and Isomers thereofs methyl 6-formyl-5{ [ (pheny Ime thoxy) -carbonyl] -amino}-3-cyclohexene-120 carboxylate and methyl 6-(3-oxo-1-propenyl)-5{ [ (phenyImethoxv) -carbonyl] -amino}-3-cyclohexene-1carboxylate, methyl 3-cyclohexene-2-[(trichloroacetyl) -amino]-1-carboxylate, 2,2,2-trichloro-M-(6forrayl-2-cyclohexen-l-yl)-acetamide, ethyl (625 formyl-5-methyl-2-cyclohexea-1-yl) -carbamate, ae thyl 2 - [ (e thoxy- carbonyl) - amino] - 6 -methyl - 3 cyclohexene-1-carboxylate, methyl 2-[(ethoxycarbonyl) -amino] -5-methyl-3-cyclohexene-l-carboxylat®, methyl 2-[ (ethoacycarboayl)-amino]-3124 cyclohexene-1-carboxy late, ethyl 3-{2~ £ (ethoscycarbonyl) -amino] -S-methyl-S-eyeloheaoaa-l-ylJ-Spropenoate, phenylmethyl (S-formyl-S-propyl-lcyclohexeu-l-yl) -carbamate, phenylmethyl (6-formyl5 5-mefchyl-2-eyeIohexen-l~yl)-carbamate, methyl 2[ (phenoxycarboayl) -ands©3 -3-cyclohexene-1-carboacylate and ethyl 3~<©-sefchyl-2-{E(phenylme thoxy)carbonyl ] - amino} - 3 - eyclohexen-1 -yl > - 2 -propenoat©, phenylmethyl iS-formyl-S-peatyl-S-cyolohexen-l-yl) 10 carbamate, phenyl 5-carbomethoxy-2-cyclohexen-l-ylthiocarbanate, N- < 6 - oarbosaethoxy- 2 -cyclohexen-1 yl)-1-pyrrolidine-carboxandde, methyl, t-butyl, beasyl and 2,4, δ - t rime thy lphenyl 2 - |> (p- toluenesul phonyl) -amino] -3-cycloheiacen-l-yl-carboxylate and 15 phenylmethyl {S-formyl-5- E2-(methoxymethoasy) ethyl) -2-cyclofcexen-l-yl}-carbamate.
10. 11. Pesticides, characterised ia that they contain at least one 2 - eye lohexen-1-yl-amine derivative of the formula (I) according to Claim 1 and using surface20 -active agents
11. 12. Method of coxabating pests, characterised in that 2cyclohexen-1-yl-amine derivatives ©£ the formula (X) according to Claim 1 are allowed to act on pests and/or their environment.
12. 13. Process for the preparation of pesticides, characterised in that 2 - eye lohexen- 1-yl-amine derivatives of the formula (X) according to Claim 1 are mixed with extenders and/or surface-active agents.
13. 14. Use according to claim 1, substantially as hereinbefore described. 125
14. 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
15. 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
16. 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
17. 18. A compound as claimed in claim 10, substantially as hereinbefore described.
18. 19. A pesticide according to claim 11, substantially as hereinbefore described.
19.
20. A method according to claim 12 of combating pests, 20 substantially as hereinbefore described.
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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