N,N'-disubstituted piperazines

The present invention relates to novel N,N-disubstituted piperazines, processes for their preparation, their use as fungicides, fungicides which contain the novel active ingredients, and methods for controlling harmful fungi with these active ingredients.
N,N-Alkyl- or aryl-disubstituted piperazine derivatives have been disclosed as pharmacologically active agents and as feed additives (GB 850 662, U.S. Pat. No. 2 943 090, BE-588 826 U.S. Pat. No. 2 927 924, DE-28 09 209, BE 853 899, BE 840 326, DE-22 63 211, DE-20 50 684, BE 756 127, U.S. Pat. No. 4 523 014).
DE 30 28 483 discloses N,N'-dialkylpiperazines of the formula V ##STR2## where R.sup.1 is C.sub.1 -C.sub.12 -alkyl, cycloalkyl or hydroxyalkyl and R.sup.2 is alkyl-substituted or cycloalkyl-substituted C.sub.6 -C.sub.20 -aryl, as compounds which prevent bleaching of diazotypes.
DE-2 727 482 discloses the dialkylpiperazine derivative VI as a compound having a fungicidal action. ##STR3##
It is an object of the present invention to provide novel compounds of this type having improved properties as fungicides.
We have found that this object is achieved and that N,N'-disubstituted piperazines of the formula I ##STR4## where the group is unsaturated (.dbd.) or saturated (--) and A is --, --CH.dbd., --CH.sub.2 -- or --CH.sub.2 --CH.sub.2 --, R.sup.1 is branched or straight-chain C.sub.2 -C.sub.20 -alkyl, C.sub.3 -C.sub.20 -alkenyl, C.sub.3 -C.sub.20 -alkynyl, C.sub.4 -C.sub.12 -cycloalkyl, C.sub.4 -C.sub.12 -cycloalkenyl, C.sub.4 -C.sub.20 -alkylcycloalkyl, C.sub.4 -C.sub.20 -cycloalkenylalkyl, C.sub.4 -C.sub.20 -alkylcycloalkenyl, C.sub.9 -C.sub.11 -bicycloalkyl, C.sub.10 -C.sub.15 -bicycloalkylalkyl or C.sub.10 -C.sub.15 -alkylbicycloalkyl, and these radicals may be unsubstituted or monosubstituted to trisubstituted by hydroxyl, 1-3 halogen atoms, such as chlorine, bromine or fluorine, C.sub.1 -C.sub.5 -alkoxy or C.sub.3 -C.sub.9 -trialkylsilyl, R.sup.1 may furthermore be 5-membered to 7-membered heterocycloalkyl having 1 or 2 heteroatoms from the group consisting of oxygen and/or sulfur, 5-membered to 7-membered heterocycloalkylmethyl having 1 or 2 heteroatoms from the group consisting of oxygen and/or sulfur, or 5-membered to 7-membered heterocycloalkylmethyl which is monosubstituted to trisubstituted by C.sub.1 -C.sub.8 -alkyl and has 1 or 2 heteroatoms from the group consisting of oxygen and/or sulfur, and R.sup.2 is branched C.sub.3 -C.sub.10 -alkyl, branched C.sub.3 -C.sub.8 -alkoxy, C.sub.3 -C.sub.7 -cycloalkyl, trimethylsilyl or C.sub.3 -C.sub.8 -alkylthio, and their salts which are physiologically tolerated by plants are excellent fungicides and well tolerated by plants.
Salts of the piperazines are salts with any inorganic or organic acids, for example with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, dodecylbenzenesulfonic acid, formic acid, acetic acid, propionic acid, palmitic acid, perfluoroheptanoic acid, oxalic acid, malonic acid, benzoic acid, malic acid or dodecylsulfonic acid.
The novel [sic] N,N'-disubstituted piperazines of the formula I and their salts which are physiologically tolerated by plants contain chiral centers. They are generally obtained as racemates or may be obtained as diastereomeric mixtures.
In the case of some of the novel compounds, pure diastereomeric compounds can be isolated, for example, by distillation or column chromatography or on the basis of solubility differences. Pure enantiomeric compounds can be obtained, for example, by resolution of racemates with a chiral auxiliary reagent by a known method, for example via diastereomeric salts. Both the diastereomers of the novel N,N'-disubstituted piperazines of the formula I or their salts which are physiologically tolerated by plants and their stereoisomeric mixtures obtained in the synthesis are suitable for use as fungicides. The present invention relates to all these compounds.
Preferred compounds I are those in which A has the abovementioned meanings, so that the group ##STR5## has, for example, the following meanings: ##STR6## and R.sup.1 is C.sub.2 -C.sub.20 -alkyl, in particular C.sub.3 -C.sub.19 -alkyl, for example propyl, isopropyl, butyl, isobutyl, but-2-yl, tert-butyl, pentyl, pent-2-yl, pent-3-yl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, hex-2-yl, hex-3-yl, 2,3,3-trimethylbut-2-yl, 4-methylpent-2-yl, 4-methylpentyl, 3,3-dimethylbutyl, heptyl, hept-2-yl, hept-3-yl, hept-4-yl, diisopropylmethyl, 1,4-dimethylpentyl, 4,4-dimethylpentyl, octyl, 2-methylhept-3-yl, 5-methylhept-3-yl, oct-2-yl, oct-3-yl, oct-4-yl, 5,5-dimethylhexyl, 2,4,4-trimethylpentyl, 6-methylhept-2-yl, nonyl, non-2-yl, non-3-yl, non-4-yl, non-5-yl, 2,5,5-trimethylhexyl, 2,6-dimethylhept-4-yl, 3,5,5-trimethylhexyl, decyl, dec-2-yl, dec-3-yl, dec-4-yl, 2,3,5,5-tetramethylhexyl, undecyl, dodecyl, tridecyl, 1,5,9-trimethyldecyl or tetradecyl, C.sub.2 -C.sub.20 -hydroxyalkyl, in particular C.sub.2 -C.sub.8 -hydroxyalkyl, for example hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, 1-hydroxybut-2-yl or 2-hydroxybut-3-yl, C.sub.2 -C.sub.20 -haloalkyl having 1-3 halogen atoms, such as chlorine, bromine or fluorine, in particular C.sub.2 -C.sub.10 -haloalkyl having 1-3 halogen atoms, such as chlorine, bromine or fluorine, for example 3-chloropropyl, 6-chlorohexyl, trifluoroethyl, trichloroethyl, 5-chloropent-2-yl, 3-chlorobut-2-yl or 3,3-dichloroprop-2-yl, C.sub.1 -C.sub.5 -alkoxy-C.sub.2 -C.sub.20 -alkyl, in particular C.sub.2 -C.sub.4 -alkoxy-C.sub.2 -C.sub.10 -alkyl, for example methoxyethyl, ethoxy-ethyl, tert-butoxyethyl, 3-tert-butoxypropyl, 4-tert-butoxybutyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, ethoxyhexyl or 3-methoxyprop-2-yl, C.sub.3 -C.sub.9 -trialkylsilyl-C.sub.2 -C.sub.20 -alkyl, in particular C.sub.3 -C.sub.6 -trialkylsilyl-C.sub.2 -C.sub.10 -alkyl, for example trimethylsilylethyl, trimethylsilylpropyl, trimethylsilylbutyl, trimethylsilylpentyl or 6-trimethylsilylhexyl, C.sub.3 -C.sub.20 -alkenyl, in particular C.sub.3 -C.sub.14 -alkenyl, for example allyl, methallyl, dimethylallyl, hexenyl or 1,5,9-trimethyldecadienyl, C.sub.3 -C.sub.20 -alkynyl, in particular C.sub.3 -C.sub.14 -alkynyl, for example propargyl or 4,4-dimethylbut-2-yn-1-yl, C.sub.4 -C.sub.12 -cycloalkyl, for example cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclododecyl, C.sub. 4 -C.sub.12 -hydroxycycloalkyl, for example 4-hydroxycyclohexyl, C.sub.1 -C.sub.5 -alkoxy-C.sub.4 -C.sub.12 -cycloalkyl, such as 4-methoxycyclohexyl or 4-tert-butoxycyclohexyl, C.sub.3 -C.sub.9 -trialkylsilyl-C.sub.4 -C.sub.12 -cycloalkyl, for example 4-trimethylsilylcyclohexyl, C.sub.4 -C.sub.12 -cycloalkenyl, for example cyclopentenyl, cyclohexenyl or cycloheptenyl, C.sub.4 -C.sub.20 -alkylcyclohexyl, for example 3,3-dimethylcyclopentyl, 3,3,5-trimethylcyclopentyl, 4-methylcyclohexyl, 3-methylcyclohexyl, 3,3-dimethylcyclohexyl, 3-ethylcyclohexyl, 3,3,5-trimethylcyclohexyl, 4-isopropylcyclohexyl, 3-ethyl-5-methylcyclohexyl, 4-tert-butylcyclohexyl, 4-(2-methylbut-2-yl)-cyclohexyl or 4-(2,4,4-trimethylpent-2-yl)-cyclohexyl, C.sub.4 -C.sub.20 -alkylhydroxycycloalkyl, for example 4-hydroxy-3,6-dimethylcyclohexyl, 4-hydroxy-3,3-dimethylcyclohexyl or 4-hydroxy-3,3,5-trimethylcyclohexyl, C.sub.4 -C.sub.20 -cycloalkylalkyl, for example cyclohexylmethyl, cyclohexylethyl or cyclohexylpropyl, C.sub.4 -C.sub.20 -alkylcycloalkenyl, for example 4-isopropylcyclohexenyl or 4-tert-butylcyclohexenyl, C.sub.9 -.sub.11 -bicyclo-alkyl, for example bicyclo[4.3.0]nonyl or decalyl, C.sub.9 -C.sub.11 -hydroxybicycloalkyl, for example 6-hydroxy-2-decalyl or 7-hydroxy-2-decalyl, C.sub.10 -C.sub.15 -alkylbicycloalkyl, for example 9-methyl-2-decalyl, 5,9-dimethyl-2-decalyl or 5,5,9-trimethyl-2-decalyl, C.sub.10 -C.sub.15 -alkylhydroxybicycloalkyl, for example 6-hydroxy-9-methyl-2-decalyl, 6-hydroxy-5,9-dimethyl-2-decalyl or 6-hydroxy-5,5,9-trimethyl-2-decalyl, C.sub.8 -C.sub.10 -alkoxycycloalkyl, for example 1,4-dioxaspiro[4,5]decan-8-yl, 5-membered to 7-membered heterocycloalkyl having 1 or 2 heteroatoms from the group consisting of oxygen and sulfur, for example tetrahydropyranyl, tetrahydrothiopyranyl or dioxanyl, 5-membered to 7-membered heterocycloalkylmethyl having 1 or 2 heteroatoms from the group consisting of oxygen and sulfur, for example tetrahydropyranylmethyl or dioxanylmethyl, or C.sub.1 -C.sub.8 -alkyl-substituted 5-membered to 7-membered heterocycloalkylmethyl having 1 or 2 heteroatoms from the group consisting of oxygen and sulfur, for example 3,5-diethyldioxan-2-ylmethyl, 3,6-diethyldioxan-2-ylmethyl or 3,5-dimethyldioxan-2-ylmethyl, and R.sup.2 is branched C.sub.3 -C.sub.10 -alkyl or branched C.sub.3 -C.sub.8 -alkoxy, for example isopropyl, sec-butyl, isobutyl, tert-butyl, 2-methylbut-2-yl, 2,4,4-trimethylpent-2-yl, i-propyl, sec-butoxy or tert-butoxy, C.sub.3 -C.sub.7 -cycloalkyl, such as cyclopentyl, cyclohexyl or cycloheptyl, or C.sub.3 -C.sub.8 -alkylthio, for example tert-butylthio, sec-butylthio, isobutylthio or n-butylthio.
The compounds of the formula I can be prepared, for example, by N-alkylation of an N-alkylpiperizine of the structure II ##STR7##
(a) Reaction of a compound II with a compound R.sup.1 -X under basic conditions
Examples of radicals X are chlorine, bromine, iodine, methanesulfonyl, benzenesulfonyl, p-toluenesulfonyl and the radicals corresponding to the abovementioned anions X.
The reaction is carried out, for example, at 40.degree.-200.degree. C., in the presence or absence of an inert solvent. Preferred bases are inorganic bases, for example potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium hydride, potassium carbonate or sodium carbonate. Organic bases, such as triethylamine, dicyclohexylamine and diisopropylamine, are also suitable. The reaction can also be carried out using an excess of the piperazine derivative II.
(b) Reaction of a carbonyl compound III ##STR8## where the radicals R.sup.3 to R.sup.5 are defined so that the radical IV ##STR9## in its entirety corresponds to the radical R.sup.1, with a piperazine derivative II with simultaneous or subsequent reduction or hydrogenation.
(b.sub.1) In the direct method for the preparation of a compound I, a mixture of II and III is reacted with sodium cyanoborohydride or sodium borohydride in the presence of a solvent, for example methanol, ethanol, propanol or isopropanol, which may contain up to 25% by volume of water, and in the presence or absence of a metal salt, for example zinc(II) chloride, at 0.degree.-100.degree. C., preferably 20.degree.-80.degree. C., or with hydrogen in the presence of a solvent, for example methanol, ethanol, tetrahydrofuran or toluene, and of a hydrogenation catalyst, for example Raney nickel, platinum(IV) oxide, Ru.sub.2 O.sub.3 or palladium on carbon, in an autoclave at 100.degree.-150.degree. C. until the pressure remains constant.
(b.sub.2) In the two-stage reaction, an enamine is prepared from the compounds II and III under dehydrating conditions, and the said enamine is then reduced using a noble metal catalyst, such as Raney nickel, Raney cobalt, PtO.sub.2 or Ru.sub.2 O.sub.3, preferably palladium on carbon, and hydrogen.
The N-monosubstituted piperazines II used as starting compounds can be prepared by reactions which synthesize the piperazine ring (cf. for example PRATT, Y.T.: The Pyrazines and Piperazines, in: R. C. ELDERFIELD (Editor): Heterocyclic Compounds, Vol. 6, New York-London, 1957) or by derivatization of pyrazine derivatives. Possible syntheses are shown in scheme 1.
(a) For example, a substituted amine VII can be reacted with diethanolamine with acid catalysis (HCl, HBr or H.sub.2 SO.sub.4) at 200.degree.-250.degree. C. or with N,N-bischloroethylamine in an organic solvent, for example diethyleneglycol dimethyl ether, ethanol, acetone, acetone/water or dimethylformamide, in the presence of an auxiliary base, such as potassium carbonate or sodium carbonate, at 60.degree.-250.degree. C. to give II.
Where the compound VII is an aniline, the N-cyclohexylpiperazine derivative II' can be obtained from the resulting N-phenylpiperazine derivative II by catalytic hydrogenation.
(b) The cycloaliphatically N-substituted piperazines II' can also be obtained via reductive amination of N-formylpiperazine VIII with a correspondingly substituted cycloalkanone IX and a suitable reducing agent, for example sodium cyanoborohydride/zinc chloride, in methanol at 20.degree.-60.degree. C. and subsequent alkaline hydrolysis of the N-formyl-N'-cycloalkylpiperazine derivative X.

The Examples below illustrate the preparation of the novel compounds.
PREPARATION EXAMPLES
Method 1
Preparation of the starting compound N-(4-tert-butylphenyl)-piperazine
149 g (1 mole) of 4-tert-butylaniline, 178.5 g (1 mole) of bis-(2-chloroethylamine) hydrochloride and 138 g (1 mole) of potassium carbonate in 600 ml of diethylene glycol dimethyl ether are refluxed for 90 hours. The mixture is rendered strongly alkaline with 1 l of water and concentrated sodium hydroxide solution and stirred for 2 hours. The organic phase is extracted with 3.times.250 ml of methyl tert-butyl ether and the combined organic phases are washed with 2.times.250 ml of water, dried over sodium sulfate and evaporated down under reduced pressure. The residue is fractionated under reduced pressure to give 155 g (71% of theory) of a product of boiling point 114.degree.-117.degree. C./0.01 mbar and melting point 48.degree.-52.degree. C.
Method 2
Preparation of the starting compound N-(4-Tert-butylcyclohexyl)-piperazine
90 g (0.41 mole) of N-(4-tert-butylphenyl)-piperazine in 1.6 l of dioxane are hydrogenated over 5 g of ruthenium(IV) oxide at 130.degree. C. and under 150 bar for 74 hours. Working up in the usual manner gives a white solid.
EXAMPLE 1
N-(3,3-dimethylcyclohexyl)-N'-(4-tert-butylcyclohexyl)-piperazine (Compound No. 162)
5.0 g (22.3 millimoles) of N-(4-tert-butylcyclohexyl)-piperazine, 5.4 g (44.6 millimoles) of 3,3-dimethylcyclohexanone, 1.7 g (12.3 millimoles) of zinc(II) chloride and 1.6 g (24.5 millimoles) of sodium cyanoborohydride are stirred for 48 hours at 20.degree. C. The mixture is evaporated down under reduced pressure, the residue is hydrolyzed with 1N sodium hydroxide solution and the mixture is extracted with methyl tert-butyl ether. Working up the organic extract in the usual manner gives 3.7 g (50% of theory) of a product in the form of white crystals (mp. 90.degree.-92.degree. C.; for IR data, see Table 1b).
EXAMPLE 2
N-(4-Tert-butylphenyl-N'-(3,3-dimethylbutyl)-piperazine (Compound No. 17)
5 g (22.9 millimoles) of N-(4-tert-butylphenyl)-piperazine, 8.3 g (68.7 millimoles) of neohexyl chloride, 3.2 g (22.9 millimoles) of potassium carbonate and 3.8 g (22.9 millimoles) of potassium iodide are stirred for 16 hours at 140.degree. C. The mixture is taken up in dichloromethane and dilute sodium hydroxide solution. The organic phase is washed, dried over sodium sulfate and evaporated down under reduced pressure, and the residue is chromatographed over silica gel using 1:1 methyl tert-butyl ether/hexane to give 1.5 g (22% of theory) of a colourless oil (for IR data, see Table 1a).
The novel compounds listed in Tables 1a/b can be prepared similarly to Examples 1 and 2.
TABLE 1a__________________________________________________________________________ ##STR11##Comp. B.p. (.degree.C./mbar) IR absorption (cm.sup.-1)no. R.sup.1 R.sup.2 M.p. (.degree.C.) [Film]__________________________________________________________________________ 1 n-propyl tert.-butyl 2 isopropyl tert.-butyl 3 n-butyl tert.-butyl 41-45 2957, 2925, 2871, 2823, 1517, 1239, 1227, 819 4 isobutyl tert.-butyl 35-36 2954, 2926, 2869, 2816, 1518, 1454, 1232, 821 3 sec.-butyl tert.-butyl 4 tert.-butyl tert.-butyl 5 n-pentyl tert.-butyl 6 3-methyl-butyl tert.-butyl 145/0,2 2955, 2870, 2817, 1518, 1466, 1456, 1363, 1230 7 2,2-dimethyl-propyl tert.-butyl 8 pent-2-yl tert.-butyl 9 pent-3-yl tert.-butyl 10 1,2-dimethyl-propyl tert.-butyl 11 n-hexyl tert.-butyl 12 hex-2-yl tert.-butyl 13 Hex-3-yl tert.-butyl 14 1,2,2-trimethyl-propyl tert.-butyl 15 1,3-dimethylbutyl tert.-butyl 16 4-methyl-pentyl tert.-butyl 17 3,3-dimethyl-butyl tert.-butyl oil 2953, 2866, 2818, 1611, 1519, 1456, 1364, 1236, 1131, 820 18 n-heptyl tert.-butyl 19 hept-2-yl tert.-butyl 20 hept-3-yl tert.-butyl 21 hept-4-yl tert.-butyl 22 diisopropyl-methyl tert.-butyl 23 1,4-dimethyl-pentyl tert.-butyl 24 4,4-dimethyl-pentyl tert.-butyl 65 2955, 2903, 2867, 1517, 1468, 1365, 1236, 824 25 3,3-dimethyl-2-hydroxybutyl tert.-butyl 137-138 2964, 2949, 2833, 1520, 1365, 1333, 1232, 819 26 n-octyl tert.-butyl 27 2-methyl-hept-3-yl tert.-butyl 28 5-methyl-hept-3-yl tert.-butyl 29 oct-2-yl tert.-butyl 30 oct-3-yl tert.-butyl 31 oct-4-yl tert.-butyl 32 5,5-dimethyl-hexyl tert.-butyl 33 2,4,4-trimethyl-pentyl tert.-butyl oil 2958, 2899, 2866, 2828, 2810, 1516, 1374, 1237 34 6-methyl-hept-2-yl tert.-butyl 35 n-nonyl tert.-butyl 36 non-2-yl tert.-butyl 37 non-3-yl tert.-butyl 38 non-4-yl tert.-butyl 39 non-5-yl tert.-butyl 40 2,5,5-trimethyl-hexyl tert.-butyl 41 2,6-dimethyl-hept-4-yl tert.-butyl 42 3,5,5-trimethyl-hexyl tert.-butyl oil 2955, 2905, 2868, 2817, 1519, 1465, 1457, 1364, 1231 43 n-decyl tert.-butyl 44 dec-2-yl tert.-butyl 45 dec-3-yl tert.-butyl 46 dec-4-yl tert.-butyl 47 2,3,5,5-Tetramethylhexyl tert.-butyl 48 n-undecyl tert.-butyl 49 n-dodecyl tert.-butyl 50 n-tridecyl tert.-butyl 51 1,5,9-trimethyl-decyl tert.-butyl 52 n-tetradecyl tert.-butyl 53 2-hydroxyethyl tert.-butyl 54 3-hydroxypropyl tert.-butyl 55 4-hydroxy-butyl tert.-butyl 56 1-hydroxy-but-2-yl tert.-butyl 57 2-hydroxy-but-3-yl tert.-butyl 58 3-chloropropyl tert.-butyl 59 6-chlorohexyl tert.-butyl 60 3-chloro-2-butenyl tert.-butyl 61 2957, 2869, 2811, 1517, 1453, 1364, 1231, 1148, 1004, 824 61 trichloroethyl tert.-butyl 62 5-chloro-pent-1-yl tert.-butyl 63 3-chloro-but-2-yl tert.-butyl 64 3,3-dichloro-prop-2-yl tert.-butyl 65 2-methoxyethyl tert.-butyl 66 2-ethoxyethyl tert.-butyl 67 2-tert.-butoxyethyl tert.-butyl 68 3-tert.-butoxy-propyl tert.-butyl 69 6-methoxyhexyl tert.-butyl 70 3-methoxy-prop-2-yl tert.-butyl 71 trimethylsilylethyl tert.-butyl 72 3-trimethylsilyl-propyl tert.-butyl 73 6-trimethylsilyl-hexyl tert.-butyl 74 allyl tert.-butyl 75 3-methyl-but-2-en-yl tert.-butyl 76 1,5,9-trimethyl-deca-4,8- dienyl tert.-butyl 77 propargyl tert.-butyl 78 4,4-dimethyl-but-in-1-yl tert.-butyl 79 cyclopentyl tert.-butyl 80 3-methyl-cyclopentyl tert.-butyl 81 3,3-dimethyl-cyclopentyl tert.-butyl 82 3,3,5-trimethyl-cyclopentyl tert.-butyl 83 cyclohexyl oil 2967, 2948, 2924, 2853, 2828, 1518, 1231 813 84 3-methyl-cyclohexyl 85 3,3-dimethyl-cyclohexyl tert.-butyl 175/0,2 2951, 2931, 2862, 2811, 1519, 1450, 1235 820 86 3-ethyl-cyclohexyl tert.-butyl 87 3-ethyl-5-methyl-cyclohexyl tert.-butyl 80-82 2960, 2923, 2864, 1520, 1461, 1449, 1236 1228 88 4-methyl-cyclohexyl tert.-butyl 89 cycloheptyl tert.-butyl 90 4-isopropyl-cyclohexyl tert.-butyl (isomer mixture) 91 3,3,5-trimethyl-cyclohexyl tert.-butyl oil 2949, 2905, 2865, 2820, 1518, 1452, 1232, 823 92 3,3,5,5-tetramethylcyclo- tert.-butyl 133 2952, 2922, 2900, 2822, 2813, 1519, 1234, 820 hexyl 93 4-hydroxy-cyclohexyl tert.-butyl 94 4-tert.-butoxy-cyclohexyl tert.-butyl 95 cyclohex-2-en-yl tert.-butyl 96 4-tert.-butyl-cyclohexyl tert.-butyl 128-30 2963, 2939, 2866, 2813, 1521, 1446, 1366, (isomer mixture) 1246, 1232 97 trans-4-tert.-butyl-cyclohexyl tert.-butyl 98 4(2-methyl-but-2-yl)cyclohexyl tert.-butyl (isomer mixture) 99 trans-4(2-methyl-but-2-yl)- tert.-butyl cyclohexyl100 4(2,4,4-trimethyl-pent-2-yl) tert.-butyl cyclohexyl (isomer mixture)101 trans-4(2,4,4-trimethyl-pent- tert.-butyl 2-yl)cyclohexyl102 4-hydroxy-3-methyl-cyclohexyl tert.-butyl103 4-hydroxy-3,6-dimethyl-cyclo- tert.-butyl hexyl104 4-hydroxy-3,3-dimethyl-cyclo- tert.-butyl hexyl105 4-hydroxy-3,3,5-trimethyl- tert.-butyl cyclohexyl106 cyclohexylmethyl tert.-butyl107 cyclohexylethyl tert.-butyl 75-77 2946, 2920, 2851, 2818, 1517, 1447, 1234, 830108 4-tert.-butyl-cyclohex-3-en-yl tert.-butyl109 4-tert.-butyl-cyclohex-2-en-yl tert.-butyl110 1-decalyl (cis/trans mixture) tert.-butyl111 2-decalyl (cis/trans mixture) tert.-butyl 80 2961, 2922, 2854, 2825, 1612, 1518, 1447, 1364 1234, 8177112 trans-2-decalyl (eq/ax.-sub- stituted) tert.-butyl113 eq.-trans-2-decalyl tert.-butyl114 6-hydroxy-2-decalyl tert.-butyl115 7-hydroxy-2-decalyl tert.-butyl116 2-decalymethyl tert.-butyl117 9-methyl-trans-2-decalyl tert.-butyl118 5,9-dimethyl-trans-2-decalyl tert.-butyl119 5,5,9-trimethyl-trans-2-decalyl tert.-butyl120 6-hydroxy-9-methyl-2-decalyl tert.-butyl121 6-hydroxy-5,9-dimethyl-2- tert.-butyl decalyl122 6-hydroxy-5,5,9-trimethyl-2- tert.-butyl decalyl123 tetrahydropyran-4-yl tert.-butyl124 tetrahydrothiopyran-4-yl tert.-butyl125 dioxan-2-yl-methyl tert.-butyl126 tetrahydropyran-2-yl-methyl tert.-butyl127 tetrahydropyran-3-yl-methyl tert.-butyl128 3,5-dimethyl-dioxan-2-yl-methyl tert.-butyl129 3,5-diethyl-dioxan-2-yl-methyl tert.-butyl130 3,6-diethyl-dioxan-2-yl-methyl tert.-butyl131 1,4-dioxa-spiro[4,5]decan-8-yl tert.-butyl oil 2958, 2882, 1519, 1250, 1234, 1148, 1129 ##STR12##132 4-trimethylsilyl-cyclohexyl tert.-butyl133 n-propyl 1,1-dimethyl-propyl134 isopropyl 1,1-dimethyl-propyl135 n-butyl 1,1-dimethyl-propyl136 isobutyl 1,1-dimethyl-propyl137 sec.-butyl 1,1-dimethyl-propyl138 tert.-butyl 1,1-dimethyl-propyl139 n-pentyl 1,1-dimethyl-propyl140 3-methyl-butyl 1,1-dimethyl-propyl141 2,2-dimethyl-propyl 1,1-dimethyl-propyl142 pent-2-yl 1,1-dimethyl-propyl143 pent-3-yl 1,1-dimethyl-propyl144 1,2-dimethyl-propyl 1,1-dimethyl-propyl145 n-hexyl 1,1-dimethyl-propyl146 hex-2-yl 1,1-dimethyl-propyl147 hex-3-yl 1,1-dimethyl-propyl148 1,2,2-trimethyl-propyl 1,1-dimethyl-propyl149 1,3-dimethylbutyl 1,1-dimethyl-propyl 2959, 2876, 2818, 1518, 1465, 1450, 1364 1231150 4-methyl-pentyl 1,1-dimethyl-propyl151 3,3-dimethyl-butyl 1,1-dimethyl-propyl resin152 n-heptyl 1,1-dimethyl-propyl153 hept-2-yl 1,1-dimethyl-propyl154 hept-3-yl 1,1-dimethyl-propyl155 hept-4-yl 1,1-dimethyl-propyl156 diisopropyl-methyl 1,1-dimethyl-propyl157 1,4-dimethyl-pentyl 1,1-dimethyl-propyl158 4,4-dimethyl-pentyl 1,1-dimethyl-propyl oil 2955, 2877, 2817, 1518, 2475, 1466, 1364, 1247, 1229159 3,3-dimethyl-2-hydroxy- 1,1-dimethyl-propyl butyl160 n-octyl 1,1-dimethyl-propyl161 2-methyl-hept-3-yl 1,1-dimethyl-propyl162 5-methyl-hept-3-yl 1,1-dimethyl-propyl163 oct-2-yl 1,1-dimethyl-propyl164 oct-3-yl 1,1-dimethyl-propyl165 oct-4-yl 1,1-dimethyl-propyl166 5,5-dimethyl-hexyl 1,1-dimethyl-propyl167 2,4,4-trimethyl-pentyl 1,1-dimethyl-propyl oil 2959, 2914, 2877, 2816, 1518, 1464, 1455, 1229168 6-methyl-hept-2-yl 1,1-dimethyl-propyl169 n-nonyl 1,1-dimethyl-propyl170 non-2-yl 1,1-dimethyl-propyl171 non-3-yl 1,1-dimethyl-propyl172 non-4-yl 1,1-dimethyl-propyl173 non-5-yl 1,1-dimethyl-propyl174 2,5,5-trimethyl-hexyl 1,1-dimethyl-propyl175 2,6-dimethyl-hept-4-yl 1,1-dimethyl-propyl176 3,5,5-trimethyl-hexyl 1,1-dimethyl-propyl177 n-decyl 1,1-dimethyl-propyl178 dec-2-yl 1,1-dimethyl-propyl179 dec-3-yl 1,1-dimethyl-propyl180 dec-4-yl 1,1-dimethyl-propyl181 2,3,5,5-tetramethylhexyl 1,1-dimethyl-propyl182 n-undecyl 1,1-dimethyl-propyl183 n-dodecyl 1,1-dimethyl-propyl184 n-tridecyl 1,1-dimethyl-propyl185 1,5,9-trimethyl-decyl 1,1-dimethyl-propyl186 n-tetradecyl 1,1-dimethyl-propyl187 2-hydroxyethyl 1,1-dimethyl-propyl188 3-hydroxyethyl 1,1-dimethyl-propyl189 4-hydroxy-butyl 1,1-dimethyl-propyl190 1-hydroxy-but-2-yl 1,1-dimethyl-propyl191 2-hydroxy-but-3-yl 1,1-dimethyl-propyl192 3-chloropropyl 1,1-dimethyl-propyl193 6-chlorohexyl 1,1-dimethyl-propyl194 3-chloro-2-butenyl 1,1-dimethyl-propyl195 trichloroethyl 1,1-dimethyl-propyl196 5-chloro-pent-2-yl 1,1-dimethyl-propyl197 3-chloro-but-2-yl 1,1-dimethyl-propyl198 3,3-dichloro-prop-2-yl 1,1-dimethyl-propyl199 2-methoxyethyl 1,1-dimethyl-propyl200 2-ethoxyethyl 1,1-dimethyl-propyl201 2-tert.-butoxyethyl 1,1-dimethyl-propyl202 3-tert.-butoxy-ethyl 1,1-dimethyl-propyl203 6-methoxyhexyl 1,1-dimethyl-propyl204 3-methoxy-prop-2-yl 1,1-dimethyl-propyl205 trimethylsilylethyl 1,1-dimethyl-propyl206 3-trimethylsilyl-propyl 1,1-dimethyl-propyl207 6-trimethylsilyl-hexyl 1,1-dimethyl-propyl208 allyl 1,1-dimethyl-propyl209 3-methyl-but-2-en-yl 1,1-dimethyl-propyl210 1,5,9-trimethyl-deca-4,8- 1,1-dimethyl-propyl dienyl211 propargyl 1,1-dimethyl-propyl212 4,4-dimethyl-but-in-1-yl 1,1-dimethyl-propyl213 cyclopentyl 1,1-dimethyl-propyl214 3-methyl-cyclopentyl 1,1-dimethyl-propyl215 3,3-dimethyl-cyclopentyl 1,1-dimethyl-propyl216 3,3,5-trimethyl-cyclopentyl 1,1-dimethyl-propyl217 cyclohexyl 1,1-dimethyl-propyl 48 2966, 2926, 2855, 2829, 1519, 1451, 1248, 1228, 813218 3-methyl-cyclohexyl 1,1-dimethyl-propyl219 3,3-dimethyl-cyclohexyl 1,1-dimethyl-propyl oil 2951, 2930, 2863, 2811, 1519, 1463, 1951, 1364, 1235, 819220 3,3,5-trimethyl-cyclohexyl 1,1-dimethyl-propyl221 3,3,5,5-tetramethyl-cyclo- 1,1-dimethyl-propyl hexyl222 3-ethyl-cyclohexyl 1,1-dimethyl-propyl223 3-ethyl-5-methyl-cyclohexyl 1,1-dimethyl-propyl224 4-methyl-cyclohexyl 1,1-dimethyl-propyl225 4-isopropyl-cyclohexyl 1,1-dimethyl-propyl226 cycloheptyl 1,1-dimethyl-propyl227 4-hydroxy-cyclohexyl 1,1-dimethyl-propyl228 4-tert.-butoxy-cyclohexyl 1,1-dimethyl-propyl229 4-trimetylsolyl-cyclohexyl 1,1-dimethyl-propyl (cis/trans mixture)230 cyclohex-2-en-yl 1,1-dimethyl-propyl231 4-tert.-butyl-cyclohexyl 1,1-dimethyl-propyl 115 2964, 2940, 2865, 2818, 1520, 1447, 1366, (isomer mixture) 1248, 1228, 813232 trans-4-tert.-butyl-cyclo- 1,1-dimethyl-propyl hexyl233 4(2-methyl-but-2-yl)cyclo- 1,1-dimethyl-propyl hexyl (isomer mixture)234 trans-4(2-methyl-but-2-yl)- 1,1-dimethyl-propyl cyclohexyl235 4(2,4,4-trimethyl-pent-2-yl)- 1,1-dimethyl-propyl cyclohexyl (isomer mixture)236 trans-4(2,4,4-trimethyl-pent- 1,1-dimethyl-propyl 2-yl)cyclohexyl237 4-hydroxy-3-methyl-cyclohexyl 1,1-dimethyl-propyl238 4-hydroxy-3,6-dimethyl-cyclo- 1,1-dimethyl-propyl hexyl239 4-hydroxy-3,3-dimethyl-cyclo- 1,1-dimethyl-propyl hexyl240 4-hydroxy-3,3,5-trimethyl- 1,1-dimethyl-propyl cyclohexyl241 cyclohexylmethyl 1,1-dimethyl-propyl242 cyclohexylethyl 1,1-dimethyl-propyl243 4-tert.-butyl-cyclohex-3-en-yl 1,1-dimethyl-propyl244 4-tert.-butyl-cyclohex-2-en-yl 1,1-dimethyl-propyl245 1-decalyl (cis/trans mixture) 1,1-dimethyl-propyl246 2-decalyl (cis/trans mixture) 1,1-dimethyl-propyl247 trans-2-decalyl 1,1-dimethyl-propyl (eq/ax.-substituted)248 eq.-trans-2-decalyl 1,1-dimethyl-propyl249 6-hydroxy-2-decalyl 1,1-dimethyl-propyl250 7-hydroxy-2-decalyl 1,1-dimethyl-propyl251 2-decalylmethyl 1,1-dimethyl-propyl252 9-methyl-trans-2-decalyl 1,1-dimethyl-propyl253 5,9-dimethyl-trans-2-decalyl 1,1-dimethyl-propyl254 5,5,9-trimethyl-trans-2-decalyl 1,1-dimethyl-propyl255 6-hydroxy-9-methyl-2-decalyl 1,1-dimethyl-propyl256 6-hydroxy-5,9-dimethyl-2- 1,1-dimethyl-propyl decalyl257 6-hydroxy-5,5,9-trimethyl-2- 1,1-dimethyl-propyl decalyl258 tetrahydropyran-4-yl 1,1-dimethyl-propyl259 tetrahydrothiopyran-4-yl 1,1-dimethyl-propyl260 dioxan-2-yl-methyl 1,1-dimethyl-propyl261 tetrahydropyran-2-yl-methyl 1,1-dimethyl-propyl262 tetrahydropyran-3-yl-methyl 1,1-dimethyl-propyl263 3,5-dimethyl-dioxan-2-yl-methyl 1,1-dimethyl-propyl264 3,5-diethyl-dioxan-2-yl-methyl 1,1-dimethyl-propyl265 3,6-diethyl-dioxan-2-yl-methyl 1,1-dimethyl-propyl266267 1,4-dioxa-spiro[4,5-decan]-8-yl 1,1-dimethyl-propyl268 n-propyl sec.-butyl269 isopropyl sec.-butyl270 n-butyl sec.-butyl271 isobutyl sec.-butyl272 sec.-butyl sec.-butyl273 tert.-butyl sec.-butyl274 n-pentyl sec.-butyl275 3-methyl-butyl sec.-butyl276 2,2-dimethyl-propyl sec.-butyl277 pent-2-yl sec.-butyl278 pent-3-yl sec.-butyl279 1,2-dimethyl-propyl sec.-butyl280 n-hexyl sec.-butyl281 hex-2-yl sec.-butyl282 hex-3-yl sec.-butyl283 1,2,2-trimethyl-propyl sec.-butyl284 1,3-dimethyl-butyl sec.-butyl285 4-methyl-pentyl sec.-butyl286 3,3-dimethyl-butyl sec.-butyl 50 2959, 2871, 2820, 1612, 1516, 1456, 1234, 822287 n-heptyl sec.-butyl288 hept-2-yl sec.-butyl289 hept-3-yl sec.-butyl290 hept-4-yl sec.-butyl291 diisopropyl-methyl sec.-butyl292 1,4-dimethyl-pentyl sec.-butyl293 4,4-dimethyl-pentyl sec.-butyl oil 2955, 2872, 2816, 1516, 1454, 1377, 1346, 1246, 1232, 823294 3,3-dimethyl-2-hydroxy-butyl sec.-butyl295 n-octyl sec.-butyl296 2-methyl-hept-3-yl sec.-butyl297 5-methyl-hept-3-yl sec.-butyl298 oct-2-yl sec.-butyl299 oct-3-yl sec.-butyl300 oct-4-yl sec.-butyl301 5,5-dimethyl-hexyl sec.-butyl302 2,4,4-trimethyl-pentyl sec.-butyl303 6-methyl-hept-2-yl sec.-butyl304 n-nonyl sec.-butyl305 non-2-yl sec.-butyl306 non-3-yl sec.-butyl307 non-4-yl sec.-butyl308 non-5-yl sec.-butyl309 2,5,5-trimethyl sec.-butyl310 2,6-dimethyl-hept-4-yl sec.-butyl311 3,5,5-trimethyl-hexyl sec.-butyl312 n-decyl sec.-butyl313 dec-2-yl sec.-butyl314 dec-3-yl sec.-butyl315 dec-4-yl sec.-butyl316 2,3,5,5-tetramethyl-hexyl sec.-butyl317 n-undecyl sec.-butyl318 n-dodecyl sec.-butyl319 n-tridecyl sec.-butyl320 1,5,9-trimethyl-decyl sec.-butyl321 n-tetradecyl sec.-butyl322 2-hydroxyethyl sec.-butyl323 3-hydroxypropyl sec.-butyl324 4-hydroxy-butyl sec.-butyl325 1-hydroxy-but-2-yl sec.-butyl326 2-hydroxy-but-3-yl sec.-butyl327 3-chloropropyl sec.-butyl328 6-chlorohexyl sec.-butyl329 5-chloro-pent-2-yl sec.-butyl330 3-chloro-but-2-yl sec.-butyl331 3,3-dichloro-prop-2-yl sec.-butyl332 2-methoxyethyl sec.-butyl333 2-ethoxyethyl sec.-butyl334 2-tert.-butoxyethyl sec.-butyl335 3-tert.-butoxy-ethyl sec.-butyl336 6-methoxyhexyl sec.-butyl337 3-methoxy-prop-2-yl sec.-butyl338 trimethylsilylethyl sec.-butyl339 3-trimethylsilyl-propyl sec.-butyl340 6-trimethylsilyl-hexyl sec.-butyl341 allyl sec.-butyl342 3-methyl-but-2-en-yl sec.-butyl343 1,5,9-trimethyl-deca-4,8-dienyl sec.-butyl344 propargyl sec.-butyl345 4,4-dimethyl-but-yn-1-yl sec.-butyl346 cyclopentyl sec.-butyl347 3-methyl-cyclopentyl sec.-butyl348 3,3-dimethyl-cyclopentyl sec.-butyl349 3,3,5-trimethyl-cyclopentyl sec.-butyl350 cyclohexyl sec.-butyl351 3-methyl-cyclohexyl sec.-butyl352 3,3-dimethyl-cyclohexyl sec.-butyl 55 2953, 2928, 2873, 2819, 1517, 1452, 1378, 1234356 3,3,5-trimethyl-cyclohexyl sec.-butyl354 3,3,5,5-tetramethyl-cyclohexyl sec.-butyl355 3-ethyl-cyclohexyl sec.-butyl356 3-ethyl-5-methyl-cyclohexyl sec.-butyl357 4-methyl-cyclohexyl sec.-butyl358 4-isopropyl-cyclohexyl sec.-butyl359 cycloheptyl sec.-butyl360 4-hydroxy-cyclohexyl sec.-butyl361 4-tert.-butoxy-cyclohexyl sec.-butyl362 4-trimethylsilyl-cyclohexyl sec.-butyl (cis/trans mixture)363 cyclohex-2-en-yl sec.-butyl364 4-tert.-butyl-cyclohexyl sec.-butyl (isomer mixture)365 trans-4-tert.-butyl-cyclohexyl sec.-butyl366 4(2-methyl-but-2-yl)cyclohexyl sec.-butyl (isomer mixture)367 trans-4(2-methyl-but-2-yl)- sec.-butyl cyclohexyl368 4(2,4,4-trimethyl-pent-2-yl)- sec.-butyl cyclohexyl (isomer mixture)369 trans-4(2,4,4-trimethyl-pent- sec.-butyl 2-yl)cyclohexyl370 4-hydroxy-3-methyl-cyclohexyl sec.-butyl371 4-hydroxy-3,6-dimethyl-cyclo- sec.-butyl hexyl372 4-hydroxy-3,3-dimethyl-cyclo- sec.-butyl hexyl373 4-hydroxy-3,3,5-trimethyl- sec.-butyl cyclohexyl374 cyclohexylmethyl sec.-butyl375 cyclohexylethyl sec.-butyl376 4-tert.-butyl-cyclohex-3-en-yl sec.-butyl377 4-tert.-butyl-cyclohex-2-en-yl sec.-butyl378 1-decalyl (cis/trans mixture) sec.-butyl379 2-decalyl (cis/trans mixture) sec.-butyl380 trans-2-decalyl (eq/ax.- sec.-butyl substituted)381 eq.-trans-2-decalyl sec.-butyl382 6-hydroxy-2-decalyl sec.-butyl383 7-hydroxy-2-decalyl sec.-butyl384 2-decalylmethyl sec.-butyl385 9-methyl-trans-2-decalyl sec.-butyl386 5,9-dimethyl-trans-2-decalyl sec.-butyl387 5,5,9-trimethyl-trans-2-decalyl sec.-butyl388 6-hydroxy-9-methyl-2-decalyl sec.-butyl389 6-hydroxy-5,9-dimethyl-2- sec.-butyl decalyl390 6-hydroxy-5,5,9-trimethyl-2- sec.-butyl decalyl391 tetrahydropyran-4-yl sec.-butyl392 tetrahydrothiopyran-4-yl sec.-butyl393 dioxan-2-yl-methyl sec.-butyl394 tetrahydropyran-2-yl-methyl sec.-butyl395 tetrahydropyran-3-yl-methyl sec.-butyl396 3,5-dimethyl-dioxan-2-yl-methyl sec.-butyl397 3,5-diethyl-dioxan-2-yl-methyl sec.-butyl398 3,6-diethyl-dioxan-2-yl-methyl sec.-butyl399 1,4-dioxa-spiro[4,5-decan]- sec.-butyl 8-yl400 n-propyl cyclohexyl401 isopropyl cyclohexyl402 n-butyl cyclohexyl403 isobutyl cyclohexyl404 sec.-butyl cyclohexyl405 tert.-butyl cyclohexyl406 n-pentyl cyclohexyl407 3-methyl-butyl cyclohexyl408 2,2-dimethyl-propyl cyclohexyl409 pent-2-yl cyclohexyl410 pent-3-yl cyclohexyl411 1,2-dimethyl-propyl cyclohexyl412 n-hexyl cyclohexyl413 hex-2-yl cyclohexyl414 hex-3-yl cyclohexyl415 1,2,2-trimethyl-propyl cyclohexyl416 1,3-dimethyl-butyl cyclohexyl417 4-methyl-pentyl cyclohexyl418 3,3-dimethyl-butyl cyclohexyl oil 2958, 2924, 2852, 2819, 1518, 1235, 1233, 829419 n-heptyl cyclohexyl420 hept-2-yl cyclohexyl421 hept-3-yl cyclohexyl422 hept-4-yl cyclohexyl423 diisopropyl-methyl cyclohexyl424 1,4-dimethyl-pentyl cyclohexyl425 4,4-dimethyl-pentyl cyclohexyl oil 2953, 2925, 1517, 1448, 1364, 1251, 1241, 814426 3,3-dimethyl-2-hydroxy-butyl cyclohexyl427 n-octyl cyclohexyl428 2-methyl-hept-3-yl cyclohexyl429 5-methyl-hept-3-yl cyclohexyl430 5,5-dimethyl-hexyl cyclohexyl431 2,4,4-trimethylpentyl cyclohexyl 56 2956, 2926, 2845, 1518, 1447, 1239, 1229, 814432 6-methyl-hept-2-yl cyclohexyl433 n-nonyl cyclohexyl434 2,5,5-trimethyl-hexyl cyclohexyl435 2,6-dimethyl-hept-4-yl cyclohexyl436 3,5,5-trimethyl-hexyl cyclohexyl437 n-decyl cyclohexyl438 2,3,5,5-tetramethyl-hexyl cyclohexyl439 n-undecyl cyclohexyl440 n-dodecyl cyclohexyl441 n-tridecyl cyclohexyl442 1,5,9-trimethyl-decyl cyclohexyl443 n-tetradecyl cyclohexyl444 2-hydroxyethyl cyclohexyl445 3-hydroxyethyl Cyclohesyl446 4-hydroxy-butyl cyclohexyl447 1-hydroxy-but-2-yl cyclohexyl448 2-hydroxy-but-3-yl cyclohexyl449 3-chloropropyl cyclohexyl450 6-chlorohexyl cyclohexyl451 5-chloropent-2-yl cyclohexyl452 3-chlorobut-2-yl cyclohexyl453 3,3-dichloro-prop-2-yl cyclohexyl454 2-methoxyethyl cyclohexyl455 2-ethoxyethyl cyclohexyl456 2-tert.-butoxyethyl cyclohexyl457 3-tert.-butoxy-ethyl cyclohexyl458 6-methoxyhexyl cyclohexyl459 3-methoxy-prop-2-yl cyclohexyl460 trimethylsilylethyl cyclohexyl461 3-trimethylsilyl-propyl cyclohexyl462 6-trimethylsilyl-hexyl cyclohexyl463 allyl cyclohexyl464 3-methyl-but-2-en-yl cyclohexyl465 1,5,9-trimethyl-deca-4,8-dienyl cyclohexyl466 propargyl cyclohexyl467 4,4-dimethyl-but-yn-1-yl cyclohexyl468 cyclopentyl cyclohexyl469 3-methyl-cyclopentyl cyclohexyl470 3,3-dimethyl-cyclopentyl cyclohexyl471 3,3,5-trimethyl-cyclopentyl cyclohexyl472 cyclohexyl cyclohexyl resin473 3-methyl-cyclohexyl cyclohexyl474 3,3-dimethyl-cyclohexyl oil 2926, 2847, 1611, 1516, 1448, 1240, 1226, 1134, 815475 3,3,5-trimethyl-cyclohexyl cyclohexyl476 3,3,5,5-trimethyl-cyclohexyl cyclohexyl477 3-ethyl-cyclohexyl cyclohexyl478 3-ethyl-5-methyl-cyclohexyl cyclohexyl479 4-methyl-cyclohexyl cyclohexyl480 4-isopropyl-cyclohexyl cyclohexyl481 cycloheptyl cyclohexyl482 4-hydroxy-cyclohexyl cyclohexyl483 4-tert.-butoxy-cyclohexyl cyclohexyl484 4-trimethylsilylcyclohexyl cyclohexyl (cis/trans mixture)485 cyclohex-2-en-yl cyclohexyl486 4-tert.-butyl-cyclohexyl cyclohexyl (isomer mixture)487 trans-4-tert.-butyl-cyclohexyl cyclohexyl488 4(2-methyl-but-2-yl)cyclohexyl cyclohexyl (isomer mixture)489 trans-4(2-methyl-but-2-yl)- cyclohexyl cyclohexyl490 4(2,4,4-trimethyl-pent-2-yl)- cyclohexyl cyclohexyl (isomer mixture)491 trans-4(2,4,4-trimethyl-pent- cyclohexyl 2-yl)cyclohexyl492 4-hydroxy-3-methyl-cyclohexyl cyclohexyl493 4-hydroxy-3,6-dimethyl-cyclo- cyclohexyl hexyl494 4-hydroxy-3,3-dimethyl-cyclo- cyclohexyl hexyl495 4-hydroxy-3,3,5-trimethyl- cyclohexyl cyclohexyl496 cyclohexylmethyl cyclohexyl497 cyclohexylethyl cyclohexyl498 4-tert.-butyl-cyclohex-3-en-yl cyclohexyl499 4-tert.-butyl-cyclohex-2-en-yl cyclohexyl500 1-decalyl (cis/trans mixture) cyclohexyl501 2-Decalyl (cis/trans mixture) cyclohexyl502 trans-2-Decalyl (eq/ax.-sub- cyclohexyl stituted)503 eq.-trans-2-decalyl cyclohexyl504 6-hydroxy-2-decalyl cyclohexyl505 7-hydroxy-2-decalyl cyclohexyl506 2-decalylmethyl cyclohexyl507 9-methyl-trans-2-decalyl cyclohexyl508 5,9-dimethyl-trans-2-decalyl cyclohexyl509 5,5,9-trimethyl-trans-2-decalyl cyclohexyl510 6-hydroxy-9-methyl-2-decalyl cyclohexyl511 6-hydroxy-5,9-dimethyl-2- cyclohexyl decalyl512 6-hydroxy-5,5,9-trimethyl-2- cyclohexyl decalyl513 tetrahydropyran-4-yl cyclohexyl514 tetrahydrothiopyran-4-yl cyclohexyl515 dioxan-2-yl-methyl cyclohexyl516 tetrahydropyran-2-yl-methyl cyclohexyl517 tetrahydropyran-2-yl-methyl cyclohexyl518 3,5-dimethyl-dioxan-2-yl-methyl cyclohexyl519 3,5-diethyl-dioxan-2-yl-methyl cyclohexyl520 3,6-diethyl-dioxan-2-yl-methyl cyclohexyl521 3,3-dimethyl-butyl tert.-butoxy522 4,4-dimethyl-pentyl tert.-butoxy523 2,4,4-trimethyl-pentyl tert.-butoxy524 3,3-dimethyl-cyclopentyl tert.-butoxy525 3,3,5-trimethylcyclopentyl tert.-butoxy526 3-methyl-cyclohexyl tert.-butoxy527 3,3-dimethyl-cyclohexyl tert.-butoxy528 3-ethyl-cyclohexyl tert.-butoxy529 4-hydroxy-butyl tert.-butoxy530 2-tert.-butoxy-ethyl tert.-butoxy531 3-tert.-butoxy-propyl tert.-butoxy532 4-hydroxy-cyclohexyl tert.-butoxy533 4-hydroxy-3-methyl-cyclohexyl tert.-butoxy534 4-hydroxy-3,3-dimethyl-cyclo- tert.-butoxy hexyl535 3-ethyl-4-hydroxy-cyclohexyl tert.-butoxy__________________________________________________________________________
TABLE 1b__________________________________________________________________________ Comp. ##STR13## B.p.(.degree.C./mbar) IR-Absorp.(cm.sup.-1)no. A R.sup.1 R.sup.2 M.p.(.degree.C.) (Film)__________________________________________________________________________536 -- 3,3-dimethyl-butyl tert.-butyl537 -- 4,4-dimethyl-pentyl tert.-butyl538 -- 3,3-dimethyl-cyclopentyl tert.-butyl539 -- 3,3,5-trimethyl-cyclopentyl tert.-butyl540 -- 3-methyl-cyclohexyl tert.-butyl541 -- 3,3-dimethylcyclohexyl tert.-butyl542 -- 3-ethyl-cyclohexyl tert.-butyl543a CH.sub.2 n-propyl tert.-butyl (cis-trans isomer mixt.)543b CH.sub.2 n-propyl tert.-butyl (trans isomer)544a CH.sub.2 isopropyl tert.-butyl (cis-trans isomer mixt.)544b CH.sub.2 isopropyl tert.-butyl (trans isomer)545a CH.sub.2 n-butyl tert.-butyl (cis-trans isomer mixt.)545b CH.sub.2 n-butyl tert.-butyl (trans isomer)546a CH.sub.2 isobutyl tert.-butyl (cis-trans isomer mixt.)546b CH.sub.2 isobutyl tert.-butyl (trans isomer)547a CH.sub.2 sec.-butyl tert.-butyl (cis-trans isomer mixt.)547b CH.sub.2 sec.-butyl tert.-butyl (trans isomer)548a CH.sub.2 tert.-butyl tert.-butyl (cis-trans isomer mixt.)548b CH.sub.2 tert.-butyl tert.-butyl (trans isomer)549a CH.sub.2 n-pentyl tert.-butyl (cis-trans isomer mixt.)549b CH.sub.2 n-pentyl tert.-butyl (trans isomer)550a CH.sub.2 3-methyl-butyl tert.-butyl (cis-trans isomer mixt.) oil 2952, 2869, 2806, 2767, 1469, 1451, 1366, 1162550b CH.sub.2 3-methyl-butyl tert.-butyl (trans isomer)551a CH.sub.2 2,2-dimethyl-propyl tert.-butyl (cis-trans isomer mixt.)551b CH.sub.2 2,2-dimethyl-propyl tert.-butyl (trans isomer)552a CH.sub.2 pent-2-yl tert.-butyl (cis-trans isomer mixt.)552b CH.sub.2 pent-2-yl tert.-butyl (trans isomer)553a CH.sub.2 1,2-dimethyl-propyl tert,-butyl (cis-trans isomer mixt.)553b CH.sub.2 1,2-dimethyl-propyl tert.-butyl (trans isomer)554a CH.sub.2 n-hexyl tert-butyl (cis-trans isomer mixt.)554b CH.sub.2 n-hexyl tert.-butyl (trans isomer)555a CH.sub.2 1,2,2-trimethyl-propyl tert.-butyl (cis-trans isomer mixt.)555b CH.sub.2 1,2,2-trimethyl-propyl tert.-butyl (trans isomer)556a CH.sub.2 1,3-dimethyl-butyl tert.-butyl (cis-trans isomer mixt.)556b CH.sub.2 1,3-dimethyl-butyl tert.-butyl (trans isomer)557a CH.sub.2 4-methyl-pentyl tert.-butyl (cis-trans isomer mixt.)557b CH.sub.2 4-methyl-pentyl tert.-butyl (trans isomer)558a CH.sub.2 3,3-dimethyl-butyl tert.-butyl (cis-trans isomer mixt.) oil 2953, 2867, 2805, 2765, 1471, 1445, 1364, 1152558b CH.sub.2 3,3-dimethyl-butyl tert.-butyl (trans isomer)559a CH.sub.2 n-heptyl tert.-butyl (cis-trans isomer mixt.)559a CH.sub.2 n-heptyl tert.-butyl (cis-trans isomer mixt.)559b CH.sub.2 n-heptylert.-butyl (trans isomer)560a CH.sub.2 hept-2-yl tert.-butyl (cis-trans isomer mixt.)560b CH.sub.2 hept-2-yl tert.-butyl (trans isomer)561a CH.sub.2 diisopropyl-methyl tert.-butyl (cis-trans isomer mixt.)561b CH.sub.2 diisopropyl-methyl tert.-butyl (trans isomer)562a CH.sub.2 1,4-dimethyl-pentyl tert.-butyl (cis-trans isomer mixt.)562b CH.sub.2 1,4-dimethyl-pentyl tert.-butyl (trans isomer)563a CH.sub.2 4,4-dimethyl-pentyl tert.-butyl (cis-trans isomer mixt.)563b CH.sub.2 4,4-dimethyl-pentyl tert.-butyl (trans isomer)564a CH.sub.2 3,3-dimethyl-2-hydroxybutyl tert.-butyl (cis-trans isomer mixt.)564b CH.sub.2 3,3-dimethyl-2-hydroxybutyl tert.-butyl (trans isomer)565a CH.sub.2 n-octyl tert.-butyl (cis-trans isomer mixt.)565b CH.sub.2 n-octyl tert.-butyl (trans isomer)566a CH.sub.2 2-methyl-hept-3-yl tert.-butyl (cis-trans isomer mixt.)566b CH.sub.2 2-methyl-hept-3-yl tert.-butyl (trans isomer)567a CH.sub.2 5-methyl-hept-3-yl tert.-butyl (cis-trans isomer mixt.)567b CH.sub.2 5-methyl-hept-3-yl tert.-butyl (trans isomer)568a CH.sub.2 5,5-dimethylhexyl tert.-butyl (cis-trans isomer mixt.)568b CH.sub.2 5,5-dimethylhexyl tert.-butyl (trans isomer)569a CH.sub.2 2,4,4,-trimethyl-pentyl tert.-butyl (cis-trans isomer mixt.) oil 2950, 2867, 2807, 2767, 1476, 1467, 1457, 1365569b CH.sub.2 2,4,4-trimethyl-pentyl tert.-butyl (trans isomer)570a CH.sub.2 6-methyl-hept-2-yl tert.-butyl (cis-trans isomer mixt.)570b CH.sub.2 6-methyl-hept-2-yl tert.-butyl (trans isomer)571a CH.sub.2 n-nonyl tert.-butyl (cis-trans isomer mixt.)571b CH.sub.2 n-nonyl tert.-butyl (trans isomer)572a CH.sub.2 2,5,5-trimethyl-hexyl tert.-butyl (cis-trans isomer mixt.)572b CH.sub.2 2,5,5-trimethyl-hexyl tert.-butyl (trans isomer)573a CH.sub.2 2,6-dimethyl-hept-4-yl tert.-butyl (cis-trans isomer mixt.)573b CH.sub.2 2,6-dimethyl-hept-4-yl tert.-butyl (trans isomer)574a CH.sub.2 3,5,5-trimethyl-hexyl tert.-butyl (cis-trans isomer mixt.)574b CH.sub.2 3,5,5-trimethyl-hexyl tert.-butyl (trans isomer)575a CH.sub.2 n-decyl tert.-butyl (cis-trans isomer mixt.)575b CH.sub.2 n-decyl tert.-butyl (trans isomer)576a CH.sub.2 2,3,5,5-tetramethyl-hexyl tert.-butyl (cis-trans isomer mixt.)576b CH.sub.2 2,3,5,5-tetramethyl-hexyl tert.-butyl (trans isomer)577a CH.sub.2 n-undecyl tert.-butyl (cis-trans isomer mixt.)577b CH.sub.2 n-undecyl tert.-butyl (trans isomer)578a CH.sub.2 n-dodecyl tert.-butyl (cis-trans isomer mixt.)578b CH.sub.2 n-dodecyl tert.-butyl (trans isomer)579a CH.sub.2 n-tridecyl tert.-butyl (cis-trans isomer mixt.)579b CH.sub.2 n-tridecyl tert.-butyl (trans isomer)580a CH.sub.2 1,5,9-trimethyl-decyl tert.-butyl (cis-trans isomer mixt.)580b CH.sub.2 1,5,9-trimethyl-decyl tert.-butyl (trans isomer)581a CH.sub.2 n-tetradecyl tert.-butyl (cis-trans isomer mixt.)581b CH.sub.2 n-tetradecyl tert.-butyl (trans isomer)582a CH.sub.2 2-hydroxyethyl tert.-butyl (cis-trans isomer mixt.)582b CH.sub.2 2-hydroxyethyl tert.-butyl (trans isomer)583a CH.sub.2 3-hydroxypropyl tert.-butyl (cis-trans isomer mixt.)583b CH.sub.2 3-hydroxypropyl tert.-butyl (trans isomer)584a CH.sub.2 4-hydroxy-butyl tert.-butyl (cis-trans isomer mixt.)584b CH.sub.2 4-hydroxy-butyl tert.-butyl (trans isomer)585a CH.sub.2 1-hydroxy-but-3-yl tert.-butyl (cis-trans isomer mixt.)585b CH.sub.2 1-hydroxy-but-3-yl tert.-butyl (trans isomer)586a CH.sub.2 2-hydroxy-but-3-yl tert.-butyl (cis-trans isomer mixt.)586b CH.sub.2 2-hydroxy-but-3-yl tert.-butyl (trans isomer)587a CH.sub.2 3-chloropropyl tert.-butyl (cis-trans isomer mixt.)587b CH.sub.2 3-chloropropyl tert.-butyl (trans isomer)588a CH.sub.2 6-chlorohexyl tert.-butyl (cis-trans isomer mixt.)588b CH.sub.2 6-chlorohexyl tert.-butyl (trans isomer)589a CH.sub.2 5-chloro-pent-2-yl tert.-butyl (cis-trans isomer mixt.)589b CH.sub.2 5-chloro-pent-2-yl tert.-butyl (trans isomer)590a CH.sub.2 3-chloro-but-2-yl tert.-butyl (cis-trans isomer mixt.)590b CH.sub.2 3-chloro-but-2-yl tert.-butyl (trans isomer)591a CH.sub.2 3,3-dichloro-prop-2-yl tert.-butyl (cis-trans isomer mixt.)591b CH.sub.2 3,3-dichloro-prop-2-yl tert.-butyl (trans isomer)592a CH.sub.2 2-methoxyethyl tert.-butyl (cis-trans isomer mixt.)592b CH.sub.2 2-methoxyethyl tert.-butyl (trans isomer)593a CH.sub.2 2-ethoxyethyl tert.-butyl (cis-trans isomer mixt.)593b CH.sub.2 2-ethoxyethyl tert.-butyl (trans isomer)594a CH.sub.2 2-tert.-butyoxyethyl tert.-butyl (cis-trans isomer mixt.)594b CH.sub.2 2-tert.-butyoxyethyl tert.-butyl (trans isomer)595a CH.sub.2 3-tert.-butyoxy-ethyl tert.-butyl (cis-trans isomer mixt.)595b CH.sub.2 3-tert.-butyoxy-ethyl tert.-butyl (trans isomer)596a CH.sub.2 6-methoxyhexyl tert.-butyl (cis-trans isomer mixt.)596b CH.sub.2 6-methoxyhexyl tert.-butyl (trans isomer)597a CH.sub.2 3-methoxy-prop-2-yl tert.-butyl (cis-trans isomer mixt.)597b CH.sub.2 3-methoxy-prop-2-yl tert.-butyl (trans isomer)598a CH.sub.2 trimethylsilylethyl tert.-butyl (cis-trans isomer mixt.)598b CH.sub.2 trimethylsilylethyl tert.-butyl (trans isomer)599a CH.sub.2 3-trimethylsilyl-propyl tert.-butyl (cis-trans isomer mixt.)599b CH.sub.2 3-trimethylsilyl-propyl tert.-butyl (trans isomer)600a CH.sub.2 6-trimethylsilyl-hexyl tert.-butyl (cis-trans isomer mixt.)600b CH.sub.2 6-trimethylsilyl-hexyl tert.-butyl (trans isomer)601a CH.sub.2 allyl tert.-butyl (cis-trans isomer mixt.)601b CH.sub.2 allyl tert.-butyl (trans isomer)602a CH.sub.2 3-methyl-but-2-en-yl tert.-butyl (cis-trans isomer mixt.)602b CH.sub.2 3-methyl-but-2-en-yl tert.-butyl (trans isomer)603a CH.sub.2 1,5,9-trimethyl-deca-4,8- tert.-butyl (cis-trans isomer mixt.)603b CH.sub.2 1,5,9-trimethyl-deca-4,8- tert.-butyl (trans isomer)604a CH.sub.2 propargyl tert.-butyl (cis-trans isomer mixt.)604b CH.sub.2 propargyl tert.-butyl (trans isomer)605a CH.sub.2 4,4-dimethyl-but-yn-1-yl tert.-butyl (cis-trans isomer mixt.)605b CH.sub.2 4,4-dimethyl-but-yn-1-yl tert.-butyl (trans isomer)606a CH.sub.2 cyclopentyl tert.-butyl (cis-trans isomer mixt.)606b CH.sub.2 cyclopentyl tert.-butyl (trans isomer)607a CH.sub.2 3-methyl-cyclopentyl tert.-butyl (cis-trans isomer mixt.)607b CH.sub.2 3-methyl-cyclopentyl tert.-butyl (trans isomer)608a CH.sub.2 3,3-dimethyl-cyclopentyl tert.-butyl (cis-trans isomer mixt.)608b CH.sub.2 3,3-dimethyl-cyclopentyl tert.-butyl (trans isomer)609a CH.sub.2 3,3,5-trimethyl-cyclopentyl tert.-butyl (cis-trans isomer mixt.)609b CH.sub.2 3,3,5-trimethyl-cyclopentyl tert.-butyl (trans isomer)610a CH.sub.2 cyclohexyl tert.-butyl (cis-trans isomer mixt.) 75-78 2967, 2940, 2854, 2804, 2758, 1484, 1363, 1280, 1145610b CH.sub.2 cyclohexyl tert.-butyl (trans isomer)611a CH.sub.2 3-methyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.)611b CH.sub.2 3-methyl-cyclohexyl tert.-butyl (trans isomer)612a CH.sub.2 3,3-dimethyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.) 90-92 2949, 2864, 2807, 1471, 1447, 1365, 1339, 1266, 1144612b CH.sub.2 3,3-dimethyl-cyclohexyl tert.-butyl (trans isomer)613a CH.sub.2 3,3,5-trimethyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.) oil 2945, 2864, 2836, 2804, 2764, 1467, 1452, 1365613b CH.sub.2 3,3,5-trimethyl-cyclohexyl tert.-butyl (trans isomer)614a CH.sub.2 3,3,5,5-tetramethyl-cyclo- tert.-butyl (cis-trans isomer mixt.) hexyl614b CH.sub.2 3,3,5,5-tetramethyl-cyclo- tert.-butyl (trans isomer) hexyl615a CH.sub.2 3-ethyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.)615b CH.sub.2 3-ethyl-cyclohexyl tert.-butyl (trans isomer)616a CH.sub.2 3-ethyl-5-methyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.)616b CH.sub.2 3-ethyl-5-methyl-cyclohexyl tert.-butyl (trans isomer)617a CH.sub.2 4-methyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.)617b CH.sub.2 4-methyl-cyclohexyl tert.-butyl (trans isomer)618a CH.sub.2 4-isopropyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.)618b CH.sub.2 4-isopropyl-cyclohexyl tert.-butyl (trans isomer)619a CH.sub.2 cycloheptyl tert.-butyl (cis-trans isomer mixt.)619b CH.sub.2 cycloheptyl tert.-butyl (trans isomer)620a CH.sub.2 4-hydroxy-cyclohexyl tert.-butyl (cis-trans isomer mixt.)620b CH.sub.2 4-hydroxy-cyclohexyl tert.-butyl (trans isomer)621a CH.sub.2 4-tert.-butoxy-cyclohexyl tert.-butyl (cis-trans isomer mixt.)621b CH.sub.2 4-tert.-butoxy-cyclohexyl tert.-butyl (trans isomer)622a CH.sub.2 4-trimethylsolyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.)622b CH.sub.2 4-trimethylsolyl-cyclohexyl tert.-butyl (trans isomer)623a CH.sub.2 cyclohex-2-en-yl tert.-butyl (cis-trans isomer mixt.)623b CH.sub.2 cyclohex-2-en-ylo tert.-butyl (trans isomer)624a CH.sub.2 4-tert.-butyl-cyclohexyl tert.-butyl (cis-trans isomer mixt.) 145-47 2965, 2940, 2862, 2800, 2761, 1454, 1145, 1366, 1278, 1146624b CH.sub.2 4-tert.-butyl-cyclohexyl tert.-butyl (trans isomer)625a CH.sub.2 trans-4-tert.-butyl-cyclo- tert.-butyl (cis-trans isomer mixt.) hexyl625b CH.sub.2 trans-4-tert.-butyl-cyclo- tert.-butyl (trans isomer) hexyl626a CH.sub.2 4(2-methyl-but-2-yl)cyclo- tert.-butyl (cis-trans isomer mixt.) hexyl626b CH.sub.2 4(2-methyl-but-2-yl)cyclo- tert.-butyl (trans isomer) hexyl627a CH.sub.2 trans-4(2-methyl-but-2-yl)- tert.-butyl (cis-trans isomer mixt.) cyclohexyl627b CH.sub.2 trans-4(2-methyl-but-2-yl)- tert.-butyl (trans isomer) cyclohexyl628a CH.sub.2 4(2,4,4-trimethyl-pent-2- tert.-butyl (cis-trans isomer mixt.) yl)-cyclohexyl628b CH.sub.2 4(2,4,4-trimethyl-pent-2- tert.-butyl (trans isomer) yl)-cyclohexyl629a CH.sub.2 trans-4(2,4,4-trimethyl- tert.-butyl (cis-trans isomer mixt.) pent-2-yl)cyclohexyl629b CH.sub.2 trans-4(2,4,4-trimethyl- tert.-butyl (trans isomer) pent-2-yl)cyclohexyl630a CH.sub.2 4-hydroxy-3-methyl-cyclo- tert.-butyl (cis-trans isomer mixt.) hexyl630b CH.sub.2 4-hydroxy-3-methyl-cyclo- tert.-butyl (trans isomer) hexyl631a CH.sub.2 4-hydroxy-3,6-dimethyl- tert.-butyl (cis-trans isomer mixt.) cyclohexyl631b CH.sub.2 4-hydroxy-3,6-dimethyl- tert.-butyl (trans isomer) cyclohexyl632a CH.sub.2 4-hydroxy-3,3-dimethyl- tert.-butyl (cis-trans isomer mixt.) cyclohexyl632b CH.sub.2 4-hydroxy-3,3-dimethyl- tert.-butyl (trans isomer) cyclohexyl633a CH.sub.2 4-hydroxy-3,3,5-trimethyl- tert.-butyl (cis-trans isomer mixt.) cyclohexyl633b CH.sub.2 4-hydroxy-3,3,5-trimethyl- tert.-butyl (trans isomer) cyclohexyl634a CH.sub.2 cyclohexylmethyl tert.-butyl (cis-trans isomer mixt.)634b CH.sub.2 cyclohexylmethyl tert.-butyl (trans isomer)635a CH.sub.2 cyclohexylethyl tert.-butyl (cis-trans isomer mixt.)635b CH.sub.2 cyclohexylethyl tert.-butyl (trans isomer)636a CH.sub.2 4-tert.-butyl-cyclohex-3- tert.-butyl (cis-trans isomer mixt.) en-yl636b CH.sub.2 4-tert.-butyl-cyclohex-3- tert.-butyl (trans isomer) en-yl637a CH.sub.2 4-tert.-butyl-cyclohex-2- tert.-butyl (cis-trans isomer mixt.) en-yl637b CH.sub.2 4-tert.-butyl-cyclohex-2- tert.-butyl (trans isomer) en-yl638a CH.sub.2 1-decalyl tert.-butyl (cis-trans isomer mixt.)638b CH.sub.2 1-decalyl tert.-butyl (trans isomer)639a CH.sub.2 2-decalyl tert.-butyl (cis-trans isomer mixt.) resin 2923, 2858, 1467, 1449, 1365, 1339, 1158639b CH.sub.2 2-decalyl tert.-butyl (trans isomer)640a CH.sub.2 trans-2-decalyl tert.-butyl (cis-trans isomer mixt.)640b CH.sub.2 trans-2-decalyl tert.-butyl (trans isomer)641a CH.sub.2 eq.-trans-2-decalyl tert.-butyl (cis-trans isomer mixt.)641b CH.sub.2 eq.-trans-2-decalyl tert.-butyl (trans isomer)642a CH.sub.2 6-hydroxy-2-decalyl tert.-butyl (cis-trans isomer mixt.)642b CH.sub.2 6-hydroxy-2-decalyl tert.-butyl (trans isomer)643a CH.sub.2 7-hydroxy-2-decalyl tert.-butyl (cis-trans isomer mixt.)643b CH.sub.2 7-hydroxy-2-decalyl tert.-butyl (trans isomer)644a CH.sub.2 2-decalylmethyl tert.-butyl (cis-trans isomer mixt.)644b CH.sub.2 2-decalylmethyl tert.-butyl (trans isomer)645a CH.sub.2 9-methyl-trans-2-decalyl tert.-butyl (cis-trans isomer mixt.)645b CH.sub.2 9-methyl-trans-2-decalyl tert.-butyl (trans isomer)646a CH.sub.2 5,9-dimethyl-trans-2- tert.-butyl (cis-trans isomer mixt.) decalyl646b CH.sub.2 5,9-dimethyl-trans-2- tert.-butyl (trans isomer) decalyl647a CH.sub.2 5,5,9-trimethyl-trans-2- tert.-butyl (cis-trans isomer mixt.) decalyl647b CH.sub.2 5,5,9-trimethyl-trans-2- tert.-butyl (trans isomer) decalyl648a CH.sub.2 6-hydroxy-9-methyl-2- tert.-butyl (cis-trans isomer mixt.) decalyl648b CH.sub.2 6-hydroxy-9-methyl-2- decalyl649a CH.sub.2 6-hydroxy-5,9-dimethyl-2- tert.-butyl (trans isomer) decalyl649b CH.sub.2 6-hydroxy-5,9-dimethyl-2- tert.-butyl (cis-trans isomer mixt.) decalyl650a CH.sub.2 6-hydroxy-5,5,9-trimethyl- tert.-butyl (trans isomer) 2-decalyl650b CH.sub.2 6-hydroxy-5,5,9-trimethyl- tert.-butyl (cis-trans isomer mixt.) 2-decalyl651a CH.sub.2 tetrahydropyran-4-yl tert.-butyl (cis-trans isomer mixt.)651b CH.sub.2 tetrahydropyran-4-yl tert.-butyl (trans isomer)652a CH.sub.2 tetrahydrothiopyran-4-yl tert.-butyl (cis-trans isomer mixt.)652b CH.sub.2 tetrahydrothiopyran-4-yl tert.-butyl (trans isomer)653a CH.sub.2 dioxan-2-yl-methyl tert.-butyl (cis-trans isomer mixt.)653b CH.sub.2 dioxan-2-yl-methyl tert.-butyl (trans isomer)654a CH.sub.2 tetrahydropyran-2-yl-methyl tert.-butyl (cis-trans isomer mixt.)654b CH.sub.2 tetrahydropyran-2-yl-methyl tert.-butyl (trans isomer)655a CH.sub.2 tetrahydropyran-3-yl-methyl tert.-butyl (cis-trans isomer mixt.)655b CH.sub.2 tetrahydropyran-3-yl-methyl tert.-butyl (trans isomer)656a CH.sub.2 3,5-dimethyl-dioxan-2-yl- tert.-butyl (cis-trans isomer mixt.) methyl656b CH.sub.2 3,5-dimethyl-dioxan-2-yl- tert.-butyl (trans isomer) methyl657a CH.sub.2 3,5-diethyl-dioxan-2-yl- tert.-butyl (cis-trans isomer mixt.) methyl657b CH.sub.2 3,5-diethyl-dioxan-2-yl- tert.-butyl (trans isomer) methyl658a CH.sub.2 3,6-diethyl-dioxan-2-yl- tert.-butyl (cis-trans isomer mixt.) methyl658b CH.sub.2 3,6-diethyl-dioxan-2-yl- tert.-butyl (trans isomer) methyl659a CH.sub.2 1,4-dioxa-spiro[4,5-decan]- tert-butyl (cis-trans isomer mixt.) 8-yl659b CH.sub.2 1,4-dioxa-spiro[4,5-decan]- tert.-butyl (trans isomer) 8-yl__________________________________________________________________________
In general terms, the novel compouds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following plant diseases:
Erysiphe graminis in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,
Podosphaera leucotricha in apples,
Uncinula necator in vines,
Puccinia species in cereals,
Rhizoctonia solani in cotton,
Ustilago species in cereals and sugar cane,
Venturia inaequalis (scab) in apples,
Helminthosporium species in cereals,
Septoria nodorum in wheat,
Botrytis cinerea (gray mold) in strawberries and grapes,
Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice,
Phytophthora infestans in potatoes and tomatoes,
Fusarium and Verticillium species in various plants,
Plasmopara viticola in grapes,
Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.
The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient. The application rates are from 0.02 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, e.g., on Paecilomyces variotii.
Some of the novel compounds have a very good action on human-pathogenic fungi, such as Trichophyton mentagrophytes and Candida albicans.
The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 17 is mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 85 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of compound no. 558a is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.
IV. 20 parts by weight of compound no. 612a is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210.degree. and 280.degree. C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 17 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-.alpha.-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.
VI. 3 parts by weight of compound no. 85 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 558a is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 40 parts by weight of compound no. 612a is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.
IX. 20 parts by weight of compound no. 17 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in a greater fungicidal action spectrum.
The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.
Examples of fungicides which may be combined with the novel compounds are:
sulfur,
dithiocarbamates and their derivatives, such as
ferric dimethyldithiocarbamate,
zinc dimethyldithiocarbamate,
zinc ethylenebisdithiocarbamate,
manganese ethylenebisdithiocarbamate,
manganese zinc ethylenediaminebisdithiocarbamate,
tetramethylthiuram disulfides,
ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,
ammonia complex of zinc N,N'-propylenebisdithiocarbamate,
zinc N,N'-propylenebisdithiocarbamate and
N,N'-polypropylenebis(thiocarbamyl) disulfide;
nitro derivatives, such as
dinitro(1-methylheptyl)-phenyl crotonate,
2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,
2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and
diisopropyl 5-nitroisophthalate;
heterocyclic substances, such as
2-heptadecylimidazol-2-yl acetate,
2,4-dichloro-6-(o-chloroanilino)-s-triazine,
0,0-diethyl phthalimidophosphonothioate,
5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,
2,3-dicyano-1,4-dithioanthraquinone,
2-thio-1,3-dithio[4,5-b]quinoxaline,
methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,
2-methoxycarbonylaminobenzimidazole,
2-(fur-2-yl)-benzimidazole,
2-(thiazol-4-yl)benzimidazole,
N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,
N-trichloromethylthiotetrahydrophthalimide,
N-trichloromethylthiophthalimide,
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
2-thiocyanatomethylthiobenzothiazole,
1,4-dichloro-2,5-dimethoxybenzene,
4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,
2-thiopyridine 1-oxide,
8-hydroxyquinoline and its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,
2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,
2-methylfuran-3-carboxanilide,
2,5-dimethylfuran-3-carboxanilide,
2,4,5-trimethylfuran-3-carboxanilide,
2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,
N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,
2-methylbenzanilide,
2-iodobenzanilide,
N-formyl-N-morpholine-2,2,2-trichloroethylacetal,
piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),
1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,
2,6-dimethyl-N-tridecylmorpholine and its salts,
2,6-dimethyl-N-cyclododecylmorpholine and its salts,
N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,
N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine,
1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole
1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,
N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one,
1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-ol,
1-(4-phenylphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,
.alpha.-(2-chlorophenyl)-.alpha.-(4-chlorophenyl)-5-pyrimidinemethanol,
5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,
bis-(p-chlorophenyl)-3-pyridinemethanol,
1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,
1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,
and various fungicides, such as
dodecylguanidine acetate,
3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, hexachlorobenzene,
DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate,
methyl DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)-alanate,
N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,
methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,
5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,
3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,
3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,
N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,
2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-acetamide,
1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,
2,4-difluoro-.alpha.-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,
N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine, and
1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.
USE EXAMPLES
For comparison purposes, N-methyl-N'-3-(p-tert-butylphenyl)-2-methylpropylpiperazine (A) disclosed in DE 2,727,482 was employed.
USE EXAMPLE 1
Action on cucumber mildew
Leaves of pot-grown cucumber seedlings of the "Chinesische Schlange" variety were sprayed at the two-leaf stage with a spore suspension of cucumber mildew. After about 20 hours, these plants were sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20.degree. to 22.degree. C. and a relative humidity of 70 to 80%. The extent of fungus spread was determined 21 days after inoculation.
The results show that active ingredients 17, 24, 25, 83, 87, 96, 107, 111, 217, 219, 231, 558a, 569a, 610a, 612a, 624a and 639a have, when applied as 0.025 wt % spray liquors, a better fungicidal action (98%) than prior art active ingredient A applied as a 0.1% spray liquor (80%).
USE EXAMPLE 2
Action on wheat brown rust
Leaves of pot-grown wheat seedlings of the "Fruhgold" variety were dusted with spores of brown rust (Puccinia recondita). The pots were then placed for 24 hours at 20.degree. to 22.degree. C. in a high-humidity (90-95%) chamber. During this period the spores germinated and the germ tubes penetrated the leaf tissue. The infected plants were then sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were set up in the greenhouse at 20.degree. to 22.degree. C. and a relative humidity of 65 to 70%. The extent of rust fungus spread on the leaves was assessed after 8 days.
The results show that active ingredients 3, 4, 17, 24, 42, 60, 83, 85, 91, 96, 107, 111, 131, 151, 158, 167, 217, 219, 231, 293, 352, 418, 431, 474, 550a, 558a, 569a, 610a, 612a, 619a, 624a and 639a have, when applied as 0.025 wt % spray liquors, a better fungicidal action (98%) than prior art active ingredient A (60%).
USE EXAMPLE 3
Action on Plasmopara viticola
Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 48 hours in a water vapor-saturated chamber at 24.degree. C. and then in a greenhouse for 5 days at from 20.degree. to 30.degree. C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 3, 60, 85, 107, 111, 151, 219, 474, 558a, 569a, 610a, 612a and 639a have, when applied as 0.05% spray liquors, a better fungicidal action (97%) than prior art active ingredient A (60%) applied as a 0.1% spray liquor.
USE EXAMPLE 4
Action on Botrytis cinerea in paprika
Paprika seedlings of the "Neusiedler Ideal Elite" variety were sprayed, after 4 to 5 leaves were well developed, to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. After the sprayed-on layer had dried, the plants were sprinkled with a conidial suspension of the fungus Botrytis cinerea, and placed at 22.degree. to 24.degree. C. in a chamber of high humidity. After 5 days, the disease had spread to such a great extent on the untreated plants that the necroses covered the major portion of the leaves.
The results show that active ingredients 85, 91, 111, 217, 231, 472, 474, 486 and 639a have, when applied as 0.05% spray liquors, a better fungicidal action (94%) than prior art active ingredient A (10%).

Number	Name	Date
2927924	Mills	Mar 1960
3941789	Renth et al.	Mar 1976
4523014	Loev et al.	Jun 1985

Number	Date	Country
227269	May 1963	ATX
1108226	Jun 1961	DEX
2727482	Jan 1979	DEX
998509	Nov 1961	GBX

N,N'-disubstituted piperazines

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US Referenced Citations (3)

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Non-Patent Literature Citations (5)

Entry
Renth et al., Chem. Abst. 77-34573u (1972).
Renth et al., Chem. Abst. 81-120691 S (1974).
Maffrand et al., Chem. Abst. 86-43741 k (1977).
Verpe et al., Chem. Abst. 88-62415 q (1978).
Nesvadba et al., Chem. Abst. 92-41990 z (1980).