CA1078832A - 1-aza-1,5,9-cyclododecatrienes - Google Patents

Abstract

1-Aza-1,5,9-cyclododecatrienes Abstract of the Disclosure Compounds of the formula

Description

~~' 1 0~ ~ ~ 3 ~

The present invention relates to novel l-aza-1,5,9-cyclododecatrienes and a process ~or their prepara-tion.
It is known from German Offenlegungsschrift

2,330,087 that 1,2-diaza 1,5,9-cyclododecatrienes can be prepared by reac-ting 1,3-diolefins with azines in the presence o~ a catalyst which is obtained by reducing a -- carbonyl-~ree nickel compound in the presence of a chelating olefin and in the presence of an electron donor.
It has now been found that novel unsaturated heterocyclic compounds, i e. l-aza~1,5,9-cyclododeca-trienes of the formula I

~ 6 ( I ) '~ ~

~ 5 . 6 in which Rl and R3 independently of one another are hydro-gen or alkyl having 1-8 C atoms and R2 and R4 independ-ently of one another are alkyl having 1-8 C atoms, or Rl and R2 and/or R3 and R4 together with the bonding C atom form a cycloaliphatic ring having 4-8 C atoms, and R5 and R6 independently of one another ~re hydrogen or alkyl having 1-4 carbon atoms, can be prepared by reacting an . `j ' - ~ .

- - - . - i . . . . ~ .... . . . ., ....... ,.~ ,. . .

: - - . - : ........................... . . :
.

aza-butadiene of the formula II
. .

C - CH - N = C ~ (TI) ~ ~2 ~4 in which Rl to R4 are as defined under formula I~ in the presence of a catalyst which is obtained by reducing a carbonyl-free nickel compound in the presence of a chelating ole~in ~nd if appropriate in the presence o~ an electron donor, at a temperature between about -40C and +150C with a compound of the formula III
~ .
CH2=C - C z CH2 ~III) , in which R5 and R6 are as de~ined under formula I.
Alkyl groups Rl to R4 can be straight-chain or branched. Alkyl groups R5 and R6 are preferably straight-chain and have 1 or 2 C atoms. Alkyl groups Rl to R3 preferably have 1-5 C atoms and alkyl groups R4 preferably have 1-7 C atoms, Examples o~ alkyl groups Rl to R6 are: the methyl, ethyl, n-propyl, isopropyl, n- 9 sec.- and tert.-butyl, n-pentyl 9 2- or 3-pentyl, n-hexyl,

3-heptyl and n-octyl groups.
I~ Rl and R2 and/or R3 and R4 together with the bonding C atom form a cycloaliphatic ring, this is in particular an unsubstituted cycloalkyl ring having 5-8 C
atoms. Preferably, the said substituents, together with the bonding C atom, form`a cyclopentyl or cyclohexyl group.
Preferred compounds of the formula I are those in which R5 and R6 are each hydrogen, Rl and R3 independently of one another are hydrogen or alkyl having 1-5 C atoms, R2 is alkyl having 1-5 C atoms and RL~ is alkyl having 1-7 ~C-~toms, or in which R3, R5 and R6 are each hydrogen, Rl o~

and R2 together with the bonding C atom are cyclopentyl or cyclohexyl and R4 is alkyl having 1-7 C atoms.
Particularly preferred compounds are those of the formula I in which R3, R5 and R6 are each hydrogen, Rl and R2 independently of one another are alkyl having 1-4 C atoms, especially methyl, ethyl, n-propyl or n-butyl, or together with the bonding C atom are cyclohexyl, and R4 is alkyl having 1-7 C atoms, especially ethyl, iso-propyl, tert.-butyl, 2- or 3-pentyl or 3-hep-tyl.
The aza-butadienes of the formula II are known in some cases and can be prepared, for example, as follows:
By reacting ketones of the formula ~`CO with allylamine to give aza-butadienes of the formula II, in which Rl is hydrogen and R2 is methyl and R3 and R4 are as defined. With this process, in the main compounds of the formula IV
CH2 = CH - CH2 - N = C / 3 (IV) are formed initially and these can be isomerised in the presence of suitable catalysts, such a~ K20/A1203 cata-lysts9 at elevated temperatures,to give aza-butadienes of the formula II in which Rl to R4 are as defined above.
By reacting aldehydes of the formula l~`CH-CHO 3 R2~/
in which Rl' and R2' are alkyl groups having 1-8 C atoms or together with the bonding C atom are a cycloaliphatic ring having 4-8 C atoms, with ammonia to give compounds of the formula V
...... . ... .. .
~C e CH - N - C~ - CH
R2 ~2 . . . ~ . .
~ and, if desired, further reacting the compounds of the .

' .: - . .

.: : ,~ - : . - . . . ~ .

,:

1~7883Z
. _ ~ . . .

~ 4 --formula V with suitable aldehydes or ketones.
By isomerising compounds of the formula ~Ia or VIb R "
. ~
~H = N - CH2 - CH = ~H2 (VIa) or .. ' ' ' ~1 ~ R2"'-CH - C - C~I2 - N - CH - R4' (VIb) .. . ..
in which Rl" and R2" independently of one another are alkyl having 1-8 C atoms or together with the bonding C
atom are a cycloaliphatic ring having 4-8 C atoms, Rl''' is hydrogen or alkyl ha~Ting 1-8 C atoms, R?"' is hydrogen or alkyl having 1-7 C atoms and R~' is tertiary alkyl having 4-8 C atoms, at temperatures between about 0 and 80C and pre~erably about 10-50C, in the presence of an inert organic solvent, for example anhydrous benzene or toluene, and in the presence of an alkali metal alcohol-ate or alkaline earth metal alcoholate, such as sodium tert.-butylate or potassium tert.-butylate.
When compounds of the formula VIa are used,aza-butadienes of the formula II are formed in which Rl and R2 independently of one another are alkyl having 1-8 C
atoms or together with the bonding C atom are a cyclo-aliphatic ring having 4-8 C atoms, R3 is hydrogen and R4 is ethyl. When compounds o~ the Pormula VIb are used, on the other hand, aza-butadiènes of the formula II are obtained in which Xl is hydrogen or alkyl having 1-8 C
atoms, R2 is alkyl having 1-8 C atoms, R3 is hydrogen and R4 is tertiary alkyl having 4-8 C atoms.
The compounds of the formula VIa or VIb can, in turn, be prepared in a manner known per se by reacting . . . . . . ~ . ........... .. . . :- : :

.: . . - .. - , . : , . , , . ... : . 1 ~' . .

aldehydes 1 ~ CH-CHO with allylamine or by reacting an 2'~/ R~
amine of the formula R2"'-CH=C-CH2NH2 with an aldehyde of the formula R4'-CHO.
The starting compounds of the formula III are known or c~n be prepared in a manner kno~ per se.
Compounds preferably used are 2,3-dimethyl-1,3-butadiene and isoprene, but especially 1,3-butadiene.
The catalysts which can be used in the process according to the invention are known per se. Examples of suitable carbonyl-free nickel compounds are chelates or salts o~ inorganic and organic acids, such as nickel halides, for example nickel chloride, nickel iodide and nickel boride, nickel cyanide, nickel acetylacetonateg nickel benzoylacetonate, nickel carbonate, nickel formate, nickel acetate, nickel stearate, nickel oxalate, nickel benzoate, nickel sulphate and nickel dimethylglyoxime.
The nature of the anion in the carbonyl-free nickel com-pounds is not important. For reasons of accessibility and because of the good solubility in aprotic solvents, however, nickel stearate and nickel acetylacetonate are preferred.
Chelating ole~ins for the preparation of the catalysts which can be used according to the invention are? for example, ethylene and cyclic olefins with iso-lated double bonds, such as c,c-1,5-cyclooctadiene and t,t,c- or t,t,t-1,5,9-cyclododecatriene, but in particular conjugated dienes and tetraen~es, such as the starting com-pounds of the formula III and 2c,4t- or 2t,4t-hexadiene, 1,3-cyclooctadiene and cyclooctatetraene.
The electron donors (ligands) employed are Lewis bases, such as alkyl- or aryl-phosphines, alkyl phosphites or aryl phosphites and also the corresponding compounds of arsenic and antimony, for example triethylphosphine, tri-n-butylphosphine~ triphenylphosphine) triethylarsine, triphenyl-, .

:: . . - . . .
:
, . .

~)78~3~

arsine, triphenyl-antimony,triphenyl phosphite, tri-n-butyl phos-phite, tris-o-cresyl phosphite, tris-o-methoxyphenyl phos-phite, o-biphenyl-diphenyl phosphite and tris-o-biphenyl phosphite Alkyl- or aryl-phosphines and alkyl phos-phites or aryl phosphites are preferably used. Tri-phenylphosphine and ~riphenyl phosphite are particularly preferred.
- The preparation of the catalyst is usually carried out in situ by reducing ~he carbon~l-free nickel compound, i~ desired in the presence of the electron donor, in an inert organic solvent which already contains the starting material of the formula III. The reduction can be carried out by adding a reducing agent, such as halogen-~ree metal-organic compounds, especially halogen-free metal-alkyls or metal-aryls, or by an electrolytic rou-te, ; The preferred method is the reduction of the carbonyl-~ree nickel compound in situ with halogen-free metal-alkyls or metal-aryls in the presence of a compound o~
the formula III and in the presence of an electron donor, especially the preferred electron donors mentioned above.
On the other hand, it is also possible to us~ a previously isolated nickel-(O) complex, such as the ethylene-bis-(triphenylphosphine)-nickel-(O) complex, the bis-cyclo-octa-1,5-diene-nickel-(0) complex or the trans-cyclodo-deca-1,5,9-triene-nickel-(O) complex, for the reaction of the aza-butadiene of the formula II with the compounds of the formula III, Nickel-(O) complex catalysts of this type can be prepared in a kno~n manner, again by reduc-tion of a carbonyl-free nickel compound in the presence of a suitable chelating olefin o~ the abovementioned type and if desired in the presence of an electron donor (ligand), for example an alkyl- or aryl-phosphine.
Halogen-free metal-alkyls or metal-aryls are, for example, phenyl or alkyl compounds of lithium, gallium, magnesium or zinc~having up to 8 C atoms in the :...... : . . ................... . . .

, , , ' , ; ', ~ .;,: , : ' ~l~78~32 alkyl moieties, such as phenyl-lithium, methyl-lithium, n-butyl-lithium, tri-n-butyl-gallium, dimethyl-magnesium and diethyl-zinc, but in particular trialkyl-aluminium and dialkyl-alkoxy-aluminium compounds having up to 8 C atoms in the alkyl moieties and 1 or 2 C atoms i~ the alkoxy moieties, for example trimethyl-aluminium, triethyl-aluminium, tri-n-butyl-aluminium, tri-n-octyl-aluminium and ethoxydiethyl-aluminium. The use of ethoxydiethyl-aluminium as the reducing agent has proved particularly advantageous.
When the preparation is carried out in situ, the nickel compound and the electron donor are advantageously used in a mutual molar ratio of 1:1 to 1:3, whilst the reducing agent is employed in an approximately 2-fold to 10-fold e~cess, based on the nickel compound.
~- The reaction according -to the invention is advan-tageously carried out in the presence of an inert organic aprotic solvent. Such solven-ts are, in particular, aliphatic or aromatic hydrocarbons, which can be halogena-ted, or aliphatic and cyclic ethers, such as n-hexane, n-heptane, benzene, toluene, chlorobenzene, methylene chloride, diethyl ether and dioxan. Particularly preferentially, the reaction is carried out in an anhyd-rous medium1 in particular in anhydrous benzene or toluene. However) it is also possible, both during the preparation of the catalyst in situ and during the sub-sequent reaction with the aza-butadiene of the formula II, to use an excess of the starting diolefin of the formula III as the solvent.
If the reaction is carried out in the presence of an organic solvent, it is possible to use either stoi-chiometric amounts of the 1,3-diolefin of the formula III
and the compounds of the formula II or a slight excess of the 1,3-diolefin of the formula III, without the yield of the compound of the formula I being significantly ... . . . . .
, :, ' .~ ' ~ ' ', ~V~ 3;Z
. ... . .

impaired, The reaction according to the inven-tion can be carried out under normal pressure or under excess pres-sure, for example under an excess pressure of up to about 10 bars. The reaction is preferably carried out under an initial pressure of about 1 to 1.5 bars.
Although the reaction can be carried out at tem-peratures between -40C and ~150C, a temperature range of +40C to +110C is preferred.
In general, it is advisable to carry out the reaction under a blanketing gas, such as nitrogen or argon.
The compounds of the formula I obtained from the reaction can be isolated and purified in a conve-ntional manner, for example by means of repeated distillation.
The novel l-aza-1,5,9-cyclododecatrienes of the formula I
are obtained in the form of colourless to slightly yellow-ish liquids and can be used, for example, to prepare acti~e compounds for combating plant pests, in particular phythopathogenic fungi.
Active compounds of this type can be prepared, ~or example, by converting a compound of the formula IJ in an aqueous or aqueous-organic medium in the presence of an inorganic acid which is non-oxidising under the reac-tion conditions,to a compound of the formula VII
- . : .

H2N - C - CH2- C = C -(CH2)~-C - C - CH2-C - CH0 X
R4 ` R n . ~ ~ 2 ~ _ --~ (VII) and catalytically hydrogenating the compound of the for-mula VII to a compound of the formula VIII

... . . . - ............... " . . .. ~ . . . ..... .. . :

, . . . . . . . ... .. . .

~)'78~13~
-_ 9 _ R3 ,~ ,6 ,5 ~6 ~1 }l2N - C - CH~ - CH - CH -(~H2)~-CH - CH - CH2 - C - CH2 ~4 R2 (VIII) in which formulae VII and VITI Rl to R6 are as defined under formula I, X is the anion of an inorganic acid which is non-oxidising under the reaction conditions and n is an integer corresponding to the valency of X.
The hydrolysis to the compounds of -the formula VII
is advantageously carried out in ~n aqueous medium.
Platinum-on-charcoal or palladium-on-charcoal catalysts are advantageously used for the catalytic hydrogenation to the amino-alcohols of the formula VIII.
Using the said active compounds, fungi occurring on plants or parts of plants can be controlled or destroyed.
The compounds are suitable, for example, for combating phytopathogenic ~ungi of the categories Basidiomycetes, such as rust fungi (for example ~uccinia), Fungi imper-fecti (for example Cercospora) and Phycomycetes (for example Oomycetes, such as Plasmopara and Phytophthora).
Amino-alcohols of the formula VIII can also be employed as active compounds for regulating plant growth.
~ ~ . . .
~H(CH3~2 . ., CH
C~I ~ ~

Under a blanketing gas (argon), 2,57 g (0.01 mol) of nickel acetylacetonate and 1.66 g (0.01 mol) o~ tri-ethyl phosphite are dissolved in 120 g of absolute toluene, a~ter which the solution is saturated at 20-25C with 1,3-butadiene. 3.9 g (0.03 mol) of ethoxydiethyl-al~minlum : ,.~ . . . .

:' ' . ~ -'' , .
. ~ ,................................ .

z -- ~-o -are then slowly added dropwise, whils-t passing in a gentle stream of 1,3-butadiene, and during the addition the original green colour changes to light red in the course of 5 minutes. The reaction mixture is heated to 60C
and, whilst passing in a vigorous stream of 1,3-butadiene, 122.5 g (0.98 mol) of N-isobutylidene-2-methyl-propenyl-amine ~prepared by reacting isobutyraldehyde with ammonia in accordance with J.Org.Chem.26,1822-25 (1961); boiling ~oint 139-141C/760 mm Hg] are added dropwise in the course of 45 minutes at a rate such that the butadiene passed in is just consumed. After the dropwise addi-tion is complete, the reaction mixture is stirred at 60C
for a further 1 hour, whilst continuously passing in 1,3-butadiene, and then cooled to 20-25C. To deac-tivate the catalyst9 0.32 g (0.01 mol) of sulphur is added to the reaction solution and the solution is dis~illed.
A first fraction, which in addition to 120 g of toluene also contains traces of triethyl phosphite and butadiene dimers (gas chromatogram), is obtained at a bath tempera-ture of up to 50C/l mm Hg. Subsequent fine distilla-tion yields 212.5 g (0.912 mol~ of 3,3-dimethyl-12-iso-propyl-l-aza-1,5,9-cyclododecatriene; yield 93% of theory, based on converted N-isobutylidene-2-methyl-propenylamine (conversion 100%); boiling point 54-55C/
0.01 mm Hg; n20 = 1.4832. ~
Analysis for C16H27N (molecular weight 233):
calculated C 82.34% H 11.66% N 6.00%
found C 82~430/o H 12.00% N 6.10%
Mass spectrum:molecular peak 233; fragment masses 218, 190, 176, 125, 82 and 55.
lH-NMR spectrum: ~ (ppm): 2.94(s), 4.6-5.15(m), 7~5(m), 7.7-8,4(m), 8.85(s), 8.98(s), 9.10 and 9.16(dd) in a ratio of 1:4:1:9-3:3:6 IR spectrum (liq~;id): ~r (fC=N-) 1,665 cm 1 , ~,. . . . . .. ~-,. ~ .. . ..
.. . . . . ~ . - : - . : . . .
. - : - , ..... , . : .. . . .~ . . ..

.. . . . .. .. .. .... . . .
- .. , - -1~)78832 (\C / 3 ) 1,380 and 1,360 cm 1 (-C=C-) 960 cm~l.
H
~ ' Under a blanketing gas (argon), 2,8 g (0.011 mol) of nickel acetylacetonate and 2.8 g (0.011 mol) of tri-phenylphosphine in 75.7 g of absolute toluene, in which 36.35 g (0.673 mol) of 1,3-butadiene have been dissolved, are reduced with 3 g (0.023 mol) of ethoxy-diethyl-aluminium at 0 to 20C. The reacticn mixture is stirred for 1 hour at 20C and then cooled to 0C~ At this temperature~48.1 g (0.385 mol) of N-isobutylidene-2-methyl-propenylamine [l-isopropyl-4,/-dimethyl-2-aza-1,3-butadiene] are added all at once to the abovementioned solution. The reaction mixture is now warm~d to 40C
and kept at this temperature for 2 hours ~7ith continuous - stirring, The reaction solution is then cooled to 0C, 17.2 g (55.5 mmols) of triphenyl phosphite are added in order to deactivate the catalyst and the mixture is dis-tilled. A first ~raction, which in addition to 75.6 g of toluene also contains 5.0 g (40 mmols) of N-isobutyl-idene-2-methyl-propenylamine (gas chromatogram), is obtained at a bath temperature of up to 50C/0.2 mm Hg.
Subsequent fine distillation yields 4.50 g (0.193 mol) of 3,3-dimethyl-12-isopropyl-1-aza-1,5,9-cyclododecatriene;
yield 55.9% of theory, based on converted l-isopropyl-

4,4-dimethyl-2-aza-1,3-butadiene (conversion 89.6%).
~ea~
Example 1 is repeated except that the reaction temperature is raised to 90C and 2.8 g (0.011 mol) of triphenylphosphine are used in place of 1.66 g (0.01 mol) o~ triethyl phosphite. 3,3-Dimethyl-12-isopropyl-1-a7.a-1,5,9-cyclododecatriene is obtained,after a reaction .

.

, . .

.

~L0~383Z

time of 25 minutes,in a yield of 74% of theory (conversion 100%).
Example 4 Example 2 is repeated except that 3.4 g ~0.011 mol) of triphenyl phosphite are used in place of 2.8 g (0,011 mol) of triphenylphosphine. 3,3~Dimethyl-12-isopropyl~l-aza 1,5,9-cyclododecatriene is obtained in a yield of 65.2% of theory (conversion 96%~.
Example ~
Example 2 is repeated except that 1.6 g (0~01 mol) of tri-isopropylphosphine are used in place of 2.8 g ~0.011 mol) o~ triphenylphosphine. 3,3-Dimethyl-12-isopropyl-l-aza-1,5,9-cyclododecatriene is obtained in a yield of 65.7% of theory (conversion 100%).
Example 6 .. . . .
~ ~(C~}I5)2 ~ ~ .
C~5~
' C2115 ~J

The procedure described in Example 4 is repeated except that 72,4 g (0.4 mol) of 1-(3-pentyl)-4,4-diethyl- t 2-aza-1,3-butadiene [prepared by reacting 2-ethylbutyr-aldehyde with ammonia in accordance with U.S. Patent Speci~ication 27319,948] and 48.4 g (0.895 mol) of 1,3-butadiene are used. After working up as described in Example 29 56.8 g (0.197 mol) of 3,3-diethyl-12-(3-pentyl)-l-aza-1,5,9-cyclododecatriene are obtained, corresponding to a yield of 51.2~ of theory,based on con-verted 1-(3-pentyl)-4,4-diethyl-2-aza-1,3-butadiene (conversion 96.4%); boiling point 90-92C/10 3 mm Hg;
nD = 1.4840. -Analysis for C20H35N (molecular weight 289):
calculated C 83.0% H 12.1% N 4.9%

., , - . . . .
, . ~ , ~ .. .
- - . . . . . . . . . . .. .

~0~88~
, ~ound C 83.2% H 12 0% N 4,7~0~
Mass spectrum: molecular peak 289; ragment masses 274, 260 and 218.
H-NMR spectrum: ~ (ppm): 2.92(s)~ 4.6-5.2(m), 7.5-8.75 (m) and 8.9-9.2(m) in a ratio of 1:4:18:12.
IR spectrum (liquid): ~ (/C=N-) 1,657 cm 1 (-CH3 ) 1,375 cm 1 H
(-C=C-) 962 cm 1 -.. . . ..
~2H5 ~3 ~ ~

~H3 1 1 -~ The procedure described in Example 2 is repeated except that 48.5 g (0.437 mol) o~ N-propylidene-(2-methylpropenylamine) [l-ethyl-4,4-dimethyl-2 aza-1,3-butadiene] and 61.0 g (1.13 mols) of 1,3-butadiene are used. Distillation yields 62.0 g (0.283 mol) of 3,3-dimethyl-12-ethyl-1-aza-1,5,9-cyclododecatriene; yield 64.9% of theory~based on converted N-propylidene-(2-methyl-propenylamine) (conversion 100%); boi-ing point 65-66C/0~005 mm Hg; n20 = 1.4864.
Analysis for C15H25N (molecular weight 219):
calculated C 82.2% H 11.4% N 6.4%
~ound C 81.9% H 11.3% N 6.5%.
Mass spectrum:molecular peak 219; fragment masses 204 and 190.
H-NMR spectrum: ~ (ppm): 2.90(s), 4.5-5.2(m), 7.4~m), 7.7-8.2(m), 8.5(m3, 8.88(s), 9.0(s) and 9.25(t) in a ratio of 1:4:1:8:2:3:3:3.
IR spectrum (liquid): ~f ( /C=N-) 1,672 cm 1 (~ C ~ CH3 ) 1,385 and 1,370 cm~
. .

~' ' ' ' ` ` :
' :` ~ ' :

~078~3~
~, .

14 _ (-C=C-) 960 cm~
H
The N-propylidene-(2-methyl-propenylamine) used in the above example was prepared as follows:
25 g (0.223 mol) of potassium ter-t.-butyla-te are suspended in o~e litre of anhydrous diethyl ether.
921 g (8.3 mols) of isobutylidene-allylamine are then added dropwise in the course of 1 hour, with continuous stirring, at such a rate that the temperature o~ the reaction mixture does no-t rise above 20C. After the dropwise addition is complete~ the mixture is stirred for a further 5 hours at 20-22C. The reaction is then discontinued and the solvent is distilled over at a bath temperature of 40C and under a pressure of 200-50 mm Hg.
The residue is distilled at a bath temperature of 70C/
0.1 mm Hg into a receiver cooled with C02/methanol.
Subsequent fine distillation yields 808 g (7.93 mols) of N-propylidene-(2-methyl-propenylamine), corresponding to a yield of 87.6% of theory; boiling point 122C;
nD = 1.471.
Example 8 Example 7 is repeated except that the reaction temperature is raised to 90-95C. 3,3-Dimethyl-12-ethyl-l-aza-1,5,9-cyclododecatriene is obtained in a yield o~ 86% of theory (conversion 100%).
~ .
.
The procedure described in Example 2 is repeated except that 110 g (1.13 mols) of N-isopropylidene-propenylamine [prepared by reacting acetone with allyl-amine, cf. B.A.Kazanskii et al , Zhurnal Organicheskoi Khimii, Volume 6, No, 11,2197-9 (1970)] and 108 g (2 mols) of 1,3-butadiene are used. Distillation yields 187.0 g ~O.91 mol) of 3,12,12-trimethyl-1-aza-1,5,9-cyclododeca-triene; yield 80.5% o~ theory~based on converted N-iso-propylidene-propenylamine (conversion 100%); boiling .

-5 point 55C/0 03 mm Hg; nD = 1.4895.
Analysis for C14H23N (molecular weight 205):
calculated C 81.89% H 11.2~/o N 6.82%
found C 81.56% H 11.34% N 6. 91~o.
Mass spectrum: molecular peak 205; fragment masses 190, 97 and 82.
lH-NMR spectrum: ~ (ppm): 3,08(d), 4,9(m), 7 4-8.2(m), 8.72(s), 8.82(s) and 8.91(d) in a ratio of 1:4:9:3:~:3.
IR spectrum (liquid): ~f (C=N) 1,675 cm 1 (CH3) 1,380 and 1,370 cm 1 o (C=C) 960 cm~l.
~
The procedure described in Example 2 is repeated except that 160 g (1.28 mols) of N-2,2 dimethyl-propyl-idene-(propenylamine) and 120 g (2.22 mols) of 1,3-buta-diene are used. After a reaction time of 6 hours at 42C, distillation yields 161 g (o.69 mol) of 3-methyl-12-tert.-butyl-1-aza-1,5,9-cyclododecatriene; yield 76.5% of theory based on converted N-2,2-dimethyl-propylidene-(propenylamine) (conversion 70.5%); boiling point 65C/0.05 mm Hg; n20 = 1.4866.-Analysis for C16H27N (~olecular weight 233):
calculated C 82~340/o H 11.66% N 6.00%
found C 82,13% H 11.65% N 6.17%.
Mass spectrumo molecular peak 233; fragment masses 218, 190, 117, 162, 125 and 82.
lH-NMR spectrum ~ (ppm): 3,08(d), 4 75-5 15(m), 7.4-8.2(m), 8.95(d) and 9 O9(s) in a ratio of 1:4:10:3:9.
IR spectrum (liquid): ~f ~C=N) 1,670 cm 1 (CH3) 1,390 and 1,362 cm 1 ` ~ (C=C) 960 cm 1 The N-2,2-dimethyl-propylidene-(propenylamine) used ln the above example was prepared analogously to the :

- ~7~32 N-propylidene-(2-me-thyl-propenylamine) according to Example 7 (CI. final paragraph of Example 7) except that 10 g of potassium tert.-butylate, 330 g (2.95 mols) of (2,2-dimethyl-propylidene)-allylamine and 450 ml of ben-zene were used. After a reaction time of 3.5 hours at 40C, 325 g (2.9 mols), corresponding to a yield of 98.5%
of theory, OI N-2,2-dimethyl-propylidene-(propenylamine) are obtained as a mixture of the cis/trans isomers in a weight ratio of 66:35; boiling point 110C; n20 = ].4487.
~ , ' .
, .
~H CH

. . .
., . .. .. :
The procedure described in Example 2 is repeated except that 109 g (0,72 mol) OI N-propyiidene-(cyclo-hexylidene-methylamine) and 123 g (2.28 mols) of 1,3-butadiene are used. Distillation yields 115 g (0.444 mol) of 3-spiro-cyclohexane-12-ethyl-1-aza-1,5,9-cyclodo-decatriene; yield 61.6% of theory, based on converted N-propylidene-(cyclohexylidene-methylamine) (conversion 100%); boiling point 103C/0.03 mm Hg; nD = 1.5101.
Analysis for C18H29N (molecular weight 259):
calculated C 83,33% H 11.27% N 5.40%
found C 83.4% H 1104% N 5.3%
Mass spectrum: molecular peak 259; Iragment masses 230, 216 9 176, 150 and 122.
IR spectrum (liquid): v (C=N) 1l670 cm 1 ~ (CH3) 1,375 cm 1 o (C=C) 960 cm~l.
H

.

~7~3 The N propylidene-(cyclohexylidene-methylamine) used in the above example was prepared analogou~ly to the N-propylidene-(2-methyl-propenylamine) according to Example 7 (cf. final paragraph of Example 7) except that 5 g of potassium tert.-butylate, 240 g (1.59 mols) of cyclohexyl-methylidene-allylamine and 250 ml of tetra-hydrofuran were used. After a reaction time of 1 hour at 30C, 199 g (1.32 mols) of N-propylidene-(cyclo-hexylidene-methylamine) are obtained, corresponding to a yield of 83% of theory; boiling point 51-53C/0.~ mm Hg;
nD = 1.5072 Example 12 The procedure described in Example 2 is repeated except that 467 g (2,8 mols) of N-propylidene-(2-ethyl-hexen-l-yl-amine), 324 g (6 mols) of 1,3-butadiene, 15.7 g ~61 mmols) of nickel acetylace-tonate, 7.45 g (60 mmols) of trimethyl phosphite, 23.4 g (180 mmols) of ethoxy-diethyl-aluminium and 300 ml of toluene are used.
After a reaction time of 4 hours at 40C, working up as described in Example 2 yields 624 g (2.27 mols) of 3,12-diethyl-3-n-butyl-1-aza-1,5,9-cyclododecatriene as a mixture of isomers; yield 81% of theory,based on the converted N-propylidene-(2-ethyl-hexen-1-yl-amine~
(conversion 100%); boiling point 98-100C/0.3 mm Hg;
n20 = 1.4905.
Analysis for ClgH33N (molecular weight 275):
calculated C 82.84% H 12.07% N 5.08%
found C 82.78% ~ 12.33% N 5.04%.
Mass spectrum:molecular peak 275; fragment masses 246, 218, 190, 166, 138, 67, 55 and 41.
IR spectrum (liquid): v (C=N) 1,670 cm~l (CH3) 1,378 cm 1 (C=C) 962 cm 1.

' ~ ' ' '. , ~ '' ' ' '' ' , '' ' 78~32 lH-NMR spectrum ~ (ppm): 2.88(s) and 2,93(s), 4.8-5.1(m), 7.3(m), 7,7-8.8(m) and 9~1(m) in a ratio of 1:4:1:18:9.
The N-propylidene-(2-ethylhexen-1-yl-amine) used in the above example was prepared in a manner analogous to that described in the final paragraph of Example 7 except that 10 g of potassium tert.-butylate, 800 g (4.79 mols) of (2-ethyl-hexylidene)-alIylamine and 600 ml of tetrahydrofuran were used~ After a reaction time of 2 hours at 35C, 682 g (4.08 mols) of N-propylidene-(2-ethyl hexen-l-yl-amine) are obtained, corresponding to a yield of 85.2% of theory (mixture of isomers in a weight ratio o~ 55:45); boiling point 53-56C/l mm :Ig;
n20 = 1.4698.
~ .
- 710 g-(3.93 mols) of N-2-methyl-pentylidene-(2-methyl-penten-l-yl-amine) [prepared by reacting 2-methyl-valeraldehyde with ammonia in accordance with U.S. Pa~ent Specification 2,319,848~ and 432 g (8.0 mols) of 1,3-butadiene are reacted by a procedure analogous to that described in Example 12~ After working up the reac-tion mixture, 995 g (3.45 mols) of 3-methyl-3-n-propyl-12-(2-pentyl)-1-aza-1,5,9-cyclododecatriene are obtained as a mixture of isomers (2 main isomers);
yield 87.7~/o of theory,based on the converted N-2-methyl-~entylidene-(2-methyl-penten-1-yl-amine) (conversion lO~o);
boiling point 103-105C/0.3 mm Hg; nD = 1.4886.
Analysis for C20H35N (molecular weight 289 51):
calculated C 82.97% H 12,19% N 4.84%
found C 83.25% H 12.44% N 5.01%.
Mass spectrum: molecular peak 289; fragment masses 260, 246, 218, 176, 139 and 110.
lH-NMR spectrum ~ (ppm): 2.94(s), 4.6-5.1(m), 7.4(m), 7.7-8.3(m), 8.65(m), 8.87(s) and 9.07(m) in a ratio o~
1:4:1:9:8:3:9.
IR spectrum (liquid): v (C=N) 1,670 cm 1 .

... . . .............................. . .. . .. . .

- ~ , .. . ~:
.

~0~8~3:~

! ~ (CH3) 1,380 and 1,375 cm 1 o (C=C~ 960 cm~l.
Example 14 The procedure described in Example 12 is repeated except that 760 g (3.21 mols) of N-2-ethyl-hexylidene-(2-ethyl-hexen-1-yl-amine) ~prepared by reacting 2-ethyl-caproaldehyde with ammonia in accordance with U.S. Paten~
Specification 2,~19,848] and 378 g (7 mols) of 1,3-buta-diene are used. After working up the reaction mixture, 930 g (2.69 mols) of 3-ethyl-3-n-butyl-12-(~-heptyl)-1-aza-1,5,9-cyclododecatriene are obtained in the form of a 7:3 mixture of isomers 9 corresponding to a yield of 84%
o~ theory,based on the converted N-2-ethyl-hexylidene-(2-ethyl-hexen-1-yl-amine) (conversion 100%); boiling point 106-109C/0 1 mm Hg; n20 = l.L~95.
Analysis for C24H43N (molecular weight 345.62):
calculated C 83.41% H 12.54% N 4.05%
found C 83 51% H 1?.78% N 4.29%.
Mass spectrum: molecular peak 345; fragment masses 316, 302, 289, 247, 246, 218, 190, 138 and 69.
H-NMR spectrum ~ (ppm): 2.91(s) and 2.97(s), 4.8-5.15 (m), 7.23(m), 7.7-8.3(m), 8.5-8.9(m) and 9.1(m) in a ratio of 1:4:1:8:17:120 IR spectrum (liquid): ~ tC=N) ` 1,670 cm ~
(CH3) 1,377 cm 1 (C=C) 964 cm 1 H
Example 15 ~ -i~2N - C~ - (CH2)8 ~ C ~H2H
2~5 CH3 199 g (0.91 mol) o~ the 3,3-dimethyl-12-ethyl-1-aza-1,5,9-cyclododecatriene prepared according to Example .

.
. -~

-~aO71 3~3~

7 are added dropwise in the course of 15 minutes to a solution of 150 g (1.53 mols) of sulphuric acid in one litre of water. Impurities are removed by a subse-quent 20 minute steam distillation. The a~ueous sul-phuric acid solution is then hydrogenated at normal pres-sure and 20-25C in the presence of a platinum-on-char-coal catalyst (5% by weight of platinum) with the absorp-tion of 3 mols of hydrogen, to give 2,2-dimethyl-11-ethyl-ll-aminoundecanol. After filtering off the cata-lyst, the aqueous solution is neutralised with concen-trated sodium hydroxide solution and the amino-alcohol which separates out is e~tracted by shaking with toluene and distilled 149 g (0.613 mol) o~ 2,2-dimethyl~
ethyl-ll-aminoundecanol are obtained, corresponding to a yield o~ 67~o,6 of theory; boiling point 118C/~.05 ~m Hg; n20 = 1.4656.
The above amino-alcoholwas-tested to determine its fungicidal action, in particular its action against Cercospora personata (= C arachidicola) on groundnut plants: -3-week old groundnut plants were sprayed with a spray liquor (0.02% by weight of active substance) pre-pared from a wettable powder of the active ingredient A~ter about 12 hours,the treated plants were dusted with a conidia suspension of the fungus. The infected plants were then incubated for about 24 hours at ~ 90y relative atmospheric humidity and then placed in a green-house at about 22C. The infestation with fungi was evaluated after 12 days. ~ -Compared with an untreated control, plants whichwere treated with the above active ingredient had a low infestation with fungi.
', ' ' '., :

: . , ,~ . .
1~' ' ' . -

Claims (8)

WHAT IS CLAIMED IS:

1. A compound of the formula I

(I) in which R1 and R3 independently of one another are hydro-gen or alkyl having 1-8 C atoms and R2 and R4 independ-ently of one another are alkyl having 1-8 C atoms, or R1 and R2 and/or R3 and R4 together with the bonding C atom form a cycloaliphatic ring having 4-8 C atoms, and R5 and R6 independently of one another are hydrogen or alkyl having 1-4 C atoms.

2. A compound of the formula I according to claim 1, in which R5 and R6 are each hydrogen, R1 and R3 independ-ently of one another are hydrogen or alkyl having 1-5 C
atoms, R2 is alkyl having 1-5 C atoms and R4 is alkyl having 1-7 C atoms, or in which R3, R5 and R6 are each hydrogen, R1 and R2 together with the bonding C atom are cyclopentyl or cyclohexyl and R4 is alkyl having 1-7 C
atoms.

3. A compound of the formula I according to claim 1, in which R3, R5 and R6 are each hydrogen, R1 and R2 independently of one another are alkyl having 1-4 C atoms or together with the bonding C atom are cyclohexyl, and R4 is alkyl having 1-7 C atoms.

4. A process for the preparation of a compound of the formula I according to claim 1, which comprises react-ing an aza-butadiene of the formula II

(II) in which R1 to R4 are as defined in claim 1, in the pre-sence of a catalyst which is obtained by reducing a carbonyl-free nickel compound in the presence of a chelating olefin and if appropriate in the presence of an electron donor, at a temperature between about -40°C and +150°C with a compound of the formula III
(III) in which R5 and R6 are as defined in claim 1.

5. A process according to claim 4, which comprises carrying out the reaction at a temperature between +40°C
and +110°C.

6. A process according to claim 4, which comprises using a catalyst which is obtained in situ by reducing-a carbonyl-free nickel compound with a halogen-free metal-alkyl or metal-aryl in the presence of a compound of the formula III and in the presence of an electron donor.

7. A process according to claim 4, which comprises using a catalyst which is obtained in situ by reducing a carbonyl-free nickel compound with a halogen-free metal-alkyl or metal-aryl in the presence of a compound of the formula III and in the presence of an alkyl- or aryl-phosphine or in the presence of an alkyl phosphite or aryl phosphite.

8. A process according to claim 4, which comprises using nickel stearate or nickel acetylacetonate as the carbonyl-free nickel compound.