CA1049531A - Nonylamines - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

New nonadienylamines, nonatrienylamines and nonylamines are described, as well as a new process for their manufacture by reacting a 1,3-diolefine with a Schiff's base in the presence of certain nickel catalysts. The new compounds are suitable for combating micro-organisms, for example in the protection of materials.

Description

C~31 The present invention relates to new nonylamines, and a new process for their manufacture. The new compounds ~-~ are useful for combating micro-organisms, especially for . the protection of materials.
It has been found ~hat compounds of formula Ia and/or Ib '.` /R2 I R
; 1 3 ~CH - C - ~C - CH - C = C - C = CH ~Ia) r R4 15 15 14 14 15 15 . and/or '.,:', .,; /R2 . Rl~ = N - f, i............................ ¦ R3 ` fH f = f fH fH fH f = ICH ~Ib ) : lO wherein .~ Rl represen~s alkyl containing l to 8 carbon atoms .~ , ~. and which may be substltuted with alkoxy containing l to 4 ;'-;~ carbon atoms; cycloalkyl containing 5 to 8 carbon atoms, or aralkyl containing 7 to ll carbon atoms, Rl' represents alkylidene containing l to 8 carbon atoms and which may be substituted with alkoxy containing . l to 4 carbon atoms; cycloalkylidene containing 5 to 8 " ~;
k carbon atoms, or aralkylidene containing 7 to ll carbon atoms, ,', ':

,';:' ' ' .'.

, ! , : -- 2 .'~, ,: : .

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

9 5 ~
R2 represents hydrogen or-alkyl containing 1 to 8 carbon atoms, R3 represents hydrogen, alkyl con~aining 1 to ~ carbon atoms, phenyl whicll may be substituted wi~h halogen; furyl, thienyl, pyridyl-3 or pyridyl-4, and R4 and R5 independently of one another repres~nt hydrogen . or methyl, . can be prepared by reacting a 1,3-diolefine of formul.a II
. .
,5 i5 : R4 - CH = C - C = CH - R~ (II) :
in which R~ and R5 have the meaning given under formulae . Ia and Ib, at a temperature from -50C to +100C, in the presence of a catalyst whlch is obtained by reducing a nickel compound which is free from carbon monoxide, with or without ~he addition of an electron donor, and, . preferably, in the presence of a basic accelerator of . .
the reaction, with a compound of formula III

R - N = C ~ (III) . 1 ~ R3 , ~l ` wherein Rl, R2 and R3 nave the meanings given under :`~ formulae Ia and Ib.
, If desired, the resu~tant compo~mds of formula Ia or Ib ~" may be hydrogenated to give compounds of formula Ic ~, .

: ' ~
: 3 ., .

,,, ~
.~

.. . : . . . -:. . . . . . . . . .
;`' ~ : . : :, ' ,~ . :: ' . .
~ - . . . , , , ''...... ... ... , . ''' ;

: . : . ~ : . .
. .. .

~4~53~

Rl - NH - Cl \

C}l - CH - IH - fH CIH jH fH - fH2 (IC) 1~ R2, R3, R4 and R5 have the meanings given under formula Ia and Ib, respectively.
It ls known from the literature that the catalytic reaction of 1,3-diolefines with azines gives cyclic com-pounds, namely 1,2- diazacyclododecatrienes-1,5,9, under analogous reaction conditions. Furthermore, it is known to use certain Schiff~s bases, such as 1-~2'-pyridylmethylene-amino)-2-~n,N-dimethylamino~-ethane, as a ligand in nickel 1~ complex catalysts for the co-oli~omerisation of butadiene and ethylene. In this co-oligomerisation, trans l,4,9-~! decatriene is formed as the main product, with smaller pro-portions of 1,3,9-decatriene and 2,4,9-decatriene and/or cyclododecatriene.
In view of this state of the art, it is surprising, .
on the one hand, that the Schiff's bases of the formula III
. .
; can be made to react catalytically in the process according to the lnvention. On the other hand, it was not ~o be expected that the co-oligomerisation o a 1,3-diolefine with a a compound of the ormula III would give open-chain products exclusively, and, in fact, the co-oligomerisation products o 2 mols o 1,3-dioleine of the formula II and 1 mol of Schiff's base of the formula III are formed with a high . . :~
.:. :: -' ':
.",.;
, . ., , . . . . : .. :
,. . ~ , : ~ . : . . . .. .

:
9153~L ~
degree of selectivity, even if the 1,3-diolefine of the formula II is employed in excess. In addition, it is possible, by adding reaction accelerators, to achieve a i high velocity in the homogeneous nickel-(0)-ligand catalysis according to the invention.
If phenyl groups R3 are substituted by halogen, this may be, e.g., fluorine, chlorine or bromine.
Alkyl groups Rl, R2 and R3 and alkylidene groups ;i Rl' can be straight-chain or branched groups. If alkyl groups Rl or alkylidene groups Rl' are substituted with alkoxy containing 1 to 4 carbon atoms, such alkoxy groups ; are preferably not in the ~-position to the N atom to :, :
which the groups Rl and Rl' are linked. The following examples of such alkyl groups may be mentioned: the methyl, ethyl, 2-ethoxyethyl, n-propyl, isopropyl, 2-methyl-; propyl, 2,2-dimethylpropyl, n-butyl, sec-butyl, tert-- butyl, 2-methylbutyl, 3-methylbutyl, 3,3-dimethylbutyl, 3-methoxybutyl, n-pentyl, 4-methylpentyl, n-hexyl, .~ ~
3-ethylhexyl, n-heptyl and n-octyl groups, as well as the corresponding alkylidene groups.
i Examples of cycloalkyl groups Rl and cyclo-alkylidene groups Rl' containing 5 to 8 carbon atoms are cyclopentyl, cyclohexyl, and cyclooctyl, and the `~ corresponding cycloalkylidene groups.
.;, ~ .
If Rl represents an aralkyl group, and Rl' is an aralkylidene group, these may be the ben~yl, ' ? ~ i ';;'`,.`.`.
,';
'':.

, . , i`, ` ' .
/s, .~ , , ,, ~ .
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~-phenylethyl, benzylidelle ur ~-pherlyletllyli~ene groups.
PreEerred compounds are t:llose of formula Ia and Ib wherein Rl represents ~lkyl containing 1 ~o 8 carbon atoms, cycloalkyl containing 5 to ~3 carbon atoms, benzyl or ~-phenylethyl, Rl' represents alkylidene containing 1 Tto 8 carbon atoms, cycloalkylidene containing 5 to 8 carbon atoms, benzylidene or ~-phenylethylidene, R2 represents hydrogen or aL~yl conkaining 1 to 8 carbo atoms, R3 represents hydrogen, alkyl containing 1 to carbon atoms, phenyl which may be substitu~ed with halogen; Euryl, thienyl, pyridyl-~ or pyridiyl 4, the R49 each represent hydrogen and the R5s independently o one another represent hydrogen or methyl, or the R4s each represent metllyl and the R5s each represent hydrogen.
In accordance with a further preference, R
represents alkyl containing 1 to 8 carbon atoms, cyclo-héxyl or benzyl, Rl' represents alkylidene containing 1 to 8 carbon atoms, cyclollexylidene or benzylidene, R2 represents hydrogen or alkyl containing 1 to 8 carbon atoms, R3 represents hydrogen, alkyl contai.ning 1 to 8 carbon atoms, phenyl, chlorophenyl, furyl, thienyl, pyridyl-3 or pyridyl-4, and T he R4s and R5s each represent hydrogen.
Compo~mds which are very particularly preEerred are those oE fonnula Ia and Ib wherein Rl represents ~ :"
' alkyl containing 1 to 4 carbon atoms, Rl' represents .

'' ~ , .

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

1045~$3~L
alkylidene contairling l to 4 carbon atoms, R2 repre-sents hydro~en or methyl, R3 represents me~11yl or phenyl, and the R4s and R5s each represent hydro~en.
The following rnay be menLioned as speclf;c compounds which can be prepared by the process accor-ding to the invention~ n-propyl)-nonatrien-(3,6,8)-yl-n-butylamine, (l-ethyl)-nonatrien-(3,6,8)-yl-n-decylamine, (l-n-butyl)-nonatrien-(3,6,8)-yl-~-methoxy-ethylamine, (l-isopropyl)-nonatrien-(3,6,8)-yl-~-methylpropylamine, (l,l-dimethyl)-nonatrien-(3,6,8)-yl cyclohexylamine, (l-methyl-l-ethyl)-nonatrien-(3,6,8)-yl-tert-butylamine, N-nonatrien-(3,6,8)-yl-ben~ylamine, (l-phenyl)-nonatrien-(3,6,8)-yl-n-octylamine, (l-phenyl)-nonatrien-(3,6,8)-yl-~-methylpropylamine, (l-phenyl)-nonatri~l1-(3 ~,8)-yl-ter~.-butylamine, [l-(4-chloro-phenyl)1-nona~rien-(3,~,8)-yl-isopropylamine, 1l-(3,4- ..
,~, .
i~. dichlorophenyl)l-nonatrien-(~,6,8)-yl-beE1zylamine, .~ ll pyridyl(3)- or -pyridyl-(4)1-nonatrien-(3,6,8)-yl-.' ethylamine, ll-thienyl-(2)1-nonatrien-(3,6,8)-yl-ter~-- butylamine, ll-thienyl-(3)l-nonatrierl-(3~6~8)-yl-n-octylamin2, [l-furyl-(2)]-nonatrien-(3,6,8)-yl-n-propyl.-~, amine.
: .
Compounds of the formula Ib ;~ N-Butylidene-(l-n-propyl)-nonadien-(3,8)-yl-amine, N-methylidene-(l-methyl)-nonadien-(3,8)-yl-amine, N-ethylidene-(l-n-octyl)-nonad;en-(3,~) -yl-amine, ~` N-propylidene-~l-ethyl)-nonadien-(3,~)-yl-amine, .;~ .
` - 7 -. . , ....

.. . . . . . . .

.. . .
. `., `:

: ` :
: ~ :
. . . . .

1153~L
N-butylidene-(l-methyl-l-n-propyl)-nonadien-~3,8)-yl-amine, N-isopropylidene-(l,l-diethyl)-nonadien-(3,8)-yl-amine, N-tert-butylidene-N-nonadien-(3,8)-yl-amine, N-benzylidene-(1-~4-methylbenzyl)l-nonadien-(3,8)-yl-; amine, N-benzylidene-~ -methylpropyl)-nonadien-(3,8)-yl-amine, N-phenethylidene-(l-ethyl)-nonadien-(3,8)-yl-amine.
The 1,3-diolefines of the formula II and the Schiff's bases of the formula III, which are used as starting pro-ducts, are known or can be prepared in a manner which is in itself known.

2-Methyl-butadiene-1,3, 2,3,-dimethyl-butadiene-1,3 and hexadiene-2,~, but especially butadiene-1,3, are preferably used as the 1,3-diolefines of the formula II.
The catalysts which can be used in the process according to the invention are in themselves known. It is preferable to use those which are obtained, under reducing ` conditions, by the action of an electron-donor on compounds ~; of nickel which are free from carbon monoxide, particularly by the reduction of compounds of nickel which are free from : ,..:
. carbon monoxide using halogen-free organo-metallic compounds, ~ such as metal alkyls or metal aryls, in the presence of an ; electron-donor.
Examples of suitable compounds of nickel which are ` free from carbon monoxide, are nickel acetylacetonate, nickel dimethylglyoxime, nickel formate and dicyclopenta-dienyl-nickel; nickel acetylacetonate is preferred.
.. :'~', .
. ' ~ .
. . .

`::

, ' . : i' - , 9~3~
~ xamples of possible metal alkyls or metal aryls are n-butyl-lithium, methyl-lithium, tri-n-butyl-gallium and diethyl-zinc, but above all trialkyl-aluminium and dialkyl-alkoxy-aluminium, such as 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.
Lewis bases, such as cyclic ethers, alkylphosphines ; or arylphosphines, alkyl phosphites or aryl phosphites and the corresponding compounds of arsenic and antimony, for example dioxane, ~etrahydrofurane, tetrahydropyrane, tri-ethylphosphine, tricyclohexylphosphine, triphenylphosphine, triethylarsine, triphenylarsine, triphenyl-antimony, tri-phenyl phosphite, tris-o-cresyl phosphite, tris-o-methoxy-phenyl phosphite, o-biphenylyl-diphenyl phosphite and tris-o-biphenylyl phosphite, are employed as the electron-donors ~ligands). Triphenylphosphine is preferably used.
;I The nickel compound and the electron-donor are appropriately used in a mutual molar ratio of 1:1 to about 1:33 whilst the reducing agent is employed in about a 2-fold to 10-fold excess, relative to the nickel compound.
The catalyst is customarily prepared in situ by reducing the carbon monoxide-free nickel compound, option-ally in the presence of the elec~ron-donor, in an inert solvent which already contains the starting diolefine of . . .
; the formula II. The reduction can be carried out here by adding one of the abovementioned reducing agents or by :
,'' ;' : _ g .
, ' '.

53~
electrolytic means. On the other hand, it is also possible ; to use a previously isolated nickel C-complex, such as the ethylene-bis-~triphenylphosphine)-nickel O-complex, the bis-cyclooctadiene-(1,5)-nickel O-complex or the trans-cyclo- -dodecatriene-(1,5,9)-nickel O-complex, for the reaction of `~ the 1,3-diolefine of the formula II with the compound of the formula III. Such nickel O-complex catalysts can be pre-pared in a known manner, also by the reduction of a carbon monoxide-free compound of nickel in the presence of a suit-~; 10 able olefine and, optionally, a Lewis base.
Examples of basic reaction accelerators which can be employed are monoalkylhydrazines, such as methylhydrazine ;
and n-butylhydrazine, secondary,alipha~ic or cyclic amines, ~ -such as N,N-dimethylamine, N,N-diethylamine, N-methyl-N-n-propylamine, pyrrolidine, imidazolidine, pyrazolidine, piperidine, piperazine and morpholine, or pyridine and pyridine bases. Morpholine is the preferred reaction accelerator. In general, the reaction accelerators are used in a quantity of about 10 to 40 per cent by weight, relative to the compound of the formula III.
The reaction according to the invention to give com-, pounds of the formula Ia or Ib is advantageously carried out in the presence of an inert organic solvent. Possible inert . ~
; organic solvents are especially aliphatic or aromatic hydro-carbons, which are optionally halogenated, or aliphatic and cycloaliphatic ethers, such as n-hexane, n-heptane, benzene, , toluene, chlorobenzene, diethyl ether and dioxane. The ~ reaction is very particularly preferentially carried out :.:.
~., '. .
,' .
:

: -10-' .

. ~
.: ' :

9S3~
under anhydrous conditions, above all in anhydrous toluene.
llowever, it is also possible to use an excess of the sta~ing diolefine of the formula II as a solvent, both as early as in the preparation of the catalyst and during the subsequent reaction with the compound of the formula III.
If the reaction is carried out in the presence of an organic solvent, it is possible - without significantly impairing the yields of compound of the formula Ia or Ib - to work both with stoichiometric quantities of the 1,3-diolefine of the formula II and the compound of the formula III, and with a slight excess of the 1,3-diolefine.
The process according to the invention can be carried out at normal pressure or at.excess pressure, for example an excess pressure of ~p to about 10 bars; it is preerable to work at an initial pressure of about 1 to 1.5 bars.
Although the reaction can be carried out at tempera-tures between -50C and ~100C, a temperature range from 20C
to 95C is preferred. At temperatures below approx. 70C, especially at temperatures between approx. 20 and 40C, nona- -:: .
` 20 trien-~3,6,8)-ylamines of the formula Ia and/or nonadien-~3,8)-ylamines of the formula Ib, but especially nonatrien-(3,6,8)-ylamines, are generally formed, depending on the reac-tion components. The temperature range from 20C to 40~C is .~ therefore preferred for the preparation of compounds of the formula Ia. At temperatures above approx. 70C, on the other hand, nonadien-~3,8)-ylamines of the formula Ib are formed virtually exclusively, in good to very good yields, even with-'`'. `:

, ~ ` -11-. !

", ' 953~L
out adding a reaction accelerator. Reaction temperatures be-tween 80 and 95C are therefore particularly prcferred for the preparation of compounds of the formula Ib.
; In general, it is advisable to carry out the reaction under a protective gas, such as nitrogen or argon. After the completion of the reaction, the catalyst is suitably deactivated for example by adding triphenyl phosphite to the reaction mixture. ~ -The compounds of the formula Ia or Ib which are produced in the reaction can, if desired, be converted into the corres-ponding saturated compounds of the formula Ic, in a manner which is in itself known, by hydrogenation, for example by cata-lytic means, for example using Raney nickel catalysts, palladium-charcoal catalysts ~5% Pd) or platinum dioxide. The hydrogen-ation is appropriately carried out in the presence of a suit-able inert organic solvent, such as methanol, ethanol, cyclo-hexane or dioxane, or mixtures of such solvents. Compounds of .
the formula Ia can, additionally, be hydrogenated with the addit-tion of anhydrous acetic acid. An increase in the rate of ;~ 20 hydrogenation can be achieved by this means.
The nonatrienes and nonadienes of the formula Ia or Ib, prepared in accordance with the invention, can be isolated and purified in a customary manner, for example by means of repeated distillation. -The new nonatrienes and nonadienes, as wsll as the saturated compounds of formula Ic, are colourless to slightly . ~ - .
. ~

.
.

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. .

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yellowish liquids.
~, In the following examples, the reactions were carried out under a proteckive gas Cnitrogen or argon).
~^ Example 1 ' .`~ f H2-CH2-CH3 , CH3-CH2-CH2-CH2-NH-C~
` CH CH CH CH CH CH CH CH
; 2.3 g ~8.94 mmols) of ni~kel acetylacetonate and 2.25 g ~8.56 mmols) of triphenylphosphine are reduced, at 0 to 20C, in 82 g o absolute toluene in which 35.5 g (0.651 mol) of 1,3-butadiene are dissolved, using 2.65 g ~20.35 mmols) of ethoxy-` lO diethyl-aluminium. After stirring the ~eaction mixture for one hour at 20C, a clear, orange-red catalyst solution is ormed. 30.95 g C0.243 mol) of N-butylidene-n-butylamine ~boiling point 145/760 mm Hg~ are then added all at once, at . :`,'i , q 0c, to the catalyst solution. The reaction mixture is now warmed to 40C and kept at this temperature for 20 hours ~ini-tial pressure approx. 1.2 bars). The reaction solution is then cooled to 0C, 10.5 g ~33.9 mmols) of triphenyl phosphite are added in order to deactivate the catalyst, and the mixture is distilled. In the course thereof, a 1st fraction is 2Q obtained, at a bath temperature of up to 50C/0.2 mm Hg, which contains ~according to gas chromatography) 14.1 g ~0.261 mol) ,~,......................................................................
.

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. .
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~ .

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that is to say 39.7% by weight, of unconverted 1,3-butadiene as well as 7.36 g ~58 mmols) a 23.8% by weight of N-butylidene-n-butylamine and 80 g of toluene. Subsequent refining distillation gives 22.~ g ~95.2 mmols) of ~l-n-propyl)-nona-trien-~3,6,8)-yl-n-butylamine; yicld: 51.2% of theory, rela-tive to N-butylidene-n-butylamine reacted ~conversion 76.1%);
boiling point 79C/0.2 mm Hg; nD = 1.4727.
~nalysis for C16H29N:
Calculated C 81.7% H 12.35% N 5.95%
Found C 81.1% H 12.35% N 6.2%.
Mass spectrum: molecule peak 235, fragment masses 234, 206, 192, 128, 112 and 72;
H -NMR spectrum:~~Cppm~: 3.4-5.1tm), 7.0-7.65~m), 7 9~m), 8.65Cm), 9.10 ~t) in the ratio 7:5:2:8:7;
IR spectrum ~liquid): ~C=C-C=C) - 1650, 1600 cm 1;
Hl -CH-CH2) - 900, 1000 cm 1; ~ ~-C=C-) - 967 cm 1; 6 ~CH3) -H -1315 cm~l.
Example 2 CH3-CH2-CH2-CH~N- ~

. CH2-cH=cH-cH2-cH2-cH2-cH=cH
` 2Q If the procedure is as indicated in Example 1, but the reaction conditions are altered in such a way that the catalysis takes place for 20 hours at 40C and for a further 48 hours at 25C, N-butylidene-~l-n-propyl)-nonadien-~3,8)-ylamine is :' ~ -14-:. :

~, ~04953~L
obtained as the predominant reaction product in a yield of 14%
of theory ~conversion 100%), boiling point 12C/0.2 mm Hg;
nD4 = 1.4560 Analysis for C16H29N:
Calculated C 81.7% H 12.35% N 5.95%
Found C 81.54% H 12.65% N 5.86%
Mass spectrum: molecule peak 235; fragment masses 236, 234, 220, 206, 192, 180, 166, 138, 126;
Hl-NMR spectrum: '~ Lppml: 2.57~t), 4.30~m), 4.72~m), 5.12~m), 7.21~quin), 7.50~m), 7.93~m), 8.61~m), 9.10~t) in the ratio 1:1:2:2:1:2:6:8:6;

, IR spectrum ~liquid): ~C=N)-1670 cm 1;
` H

v~C=C)-1645 cm 1; 6~-CH=CH2)-910,990 cm 1; ~C=C)-965 cm 1;
, ~CH3)-1375 cm 1. H
Example 3 " ~ /CH2-CH2-C113 ; ~;
,`": ~ CH3_CH2-CH2-CH2-NH-CH
~ ~ \
- CH2-cH2-cH2-cH2-cH2-cH2-cH2-cH3 The compounds prepared in accordance with Examples 1 ~nd 2, ~1-n-propyl~-nonatrien-~3,6,8)-yl-n-butylamine and N-butylidene-tl-n-propyl)-nonadien-~3-8)-ylamine, which are iso-2Q meric in respect of the position of the double bonds, are hydro-genated at normal pressure and room temperature ~25C) in metha-nol as solvent, using a Raney nickel catalyst, and with the absorption of 3 mols o hydrogen, in each case, to give (l-n-propyl)-nonyl-n-butylamine; boiling point 78C/0.2 mm Hg;
nD = 1.4405.
'` ' ~ -15-., .
--`' .

.

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Analysis for C16H35N:

; Calculated C 79.7% H 14.5% N 5.8%

Found C 79.6% H 14.4% N 5.9%

Mass spectrum: molecule peak 241, fragment masses 240, 226, 212, 198, 142 and 128;

Hl-NMR spectrum: ~ [ppm~: 7.41~m), 8.37~s), 8.70~s), 9.08~t) in the ratio 3:1:22:9.

Example 4 .. .

~ / CH
,~ CH3-cH2-cH2-cH=N- ~ 3 CH CH CH CH CH CH CH CH

; 10 The procedure is as described in Example 1, but using ; 31.6 g ~0.249 mol) of N-isobutylidene-n-butylamine instead of 3G.95 g ~0.243 mol) of N-butylidene-n-butylamine and 28.6 g (0.529 mol) of 1,3-butadiene. 34.4 g ~o.1465 mol) of N-butylidene~ isopropyl)-nonadien-~3,8)-ylamine are obtained by : means of refining distillationl as described in Example l;
yield 62% of theory, relative to N-isobutylidene-n-butylamine reacted ~conversion 95%); boiling point 68-70C/0.1 mm Hg, nD4=
1.4564. , Analysis for C16H29N:
Calculated C 81.6% H 12.3% N 6.0%
..
:~: Found C 81.8% H 12.4% N 6.0%

Mass spectrum: molecule peak 235, fragment masses 234, :.. ..
220, 206, 192, 178, 166, 126 and 67;
' ,` ':

,:, ''~ ' . . .
` -16-. . .
," -.. " . - , , ~
''. . ~ . '~ ' ' .

3i Hl-NMR spectrum~ ppm~: 2.54~t), 4.20(m), 4.68~m), 5.02 and 5.04~m), 7.44(m), 7.78 and 7.99~m), 8.50(m), 9.0 and 9.1~m) in the ratio 1:1:2:2:1:8:5:9, IR spectrum ~liquid): v~C=N) - 1670 cm 1; v~C=C) -H

1640 cm ; ~ ~-CH=CH2) - 910,990 cm 1; ~l=C) - 965 cm 1;

; ~ 3 and C~cH ) - 1380, 1376, 1365 cm E~ample 5 If, instead of using 2.25 g ~8.56 mmols) of triphenyl-phosphine, no addition at all of this phosphine ligand is made in Example 4, with the procedure being otherwise identical, N-butylidene-~L-isopropyl)-nonadien-~3,8)-ylamine is obtained in a yield of 55.1% of theory, relative to N-isobutylidene-n-~ butylamine reacted ~conversion 97.4~).
- Example 6 ,'' ~
, CH3 CH

; CH3-CH2-CH2-CH2-NH-CH C 3 2)7-CH3 N-Butylidene-~l-isopropyl)-nonadien-~3,8)-ylamine, pre-pared according to Examples 4 and 5, is hydrogenated in metha-nol as solvent at normal pressure and room temperature ~25C) using a Raney nickel catalyst, and with the absorption of 3 mols 2Q of hydrogen, to give ~l-isopropyl)-nonyl-n-butylamine; boiling point 75C/0.2 mm Hg; nD = 1.4396.
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. ~ .
~;
~ -17-.~ .
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Analysis for C]6~I35M:
Calcula-ted C 79.7,0 ~I 14.65' N 5.7%
Found C 79.5~' H 14.7% N 5.9%
Mass spectrum: molecu].e peak 241, fragment masses 240, 226, 212, 198, 142 c~nd 128;
Hl-NMR spectrum: ~- [ppm]: 7;52(t), 7 ~7(q), 8.29(m), 8,75(s), 9;17(d) and (t) in the ra-tio 2:1:1:19-12.
~' ~,'l~Z, ' ' " . .. .
.. ..
- CH~CH2-CH3 CH-NH-CH
: / \ ' ' .CH3 CH2~CH=CH-CH2-CH-CH-CH=CH2 .
The procedure is as described in Exc~mple 1, but USiJlg 10.8 g (0.109 mol) of N-propylidene-isopropylamine instead of ~0.95 g (0.243 mol) of N-butylidene n-butyl~nine7and 14.95 g (0. 77 mol) of 193-butadieneO Refining distillation9 as des cribed in Example 1~ gives 12.5 g (60.4 rnmols~ of (l-ethy].)-nonatrien-(3,6,8)-yl-isopropylamine; yield: 55.ll9b o~.theory~
relativè to N-propylidene-isopropylamine reac-ted (con~ersion 100%); boiling poin~ 55Gc/o . 2 ~rn Hg; n23 _ 1~4721.
An~lysis for C14H25N:
Calculated C 81.1% I-I 12.1% N 6.8%
Found C 80.8% H 12.49' N 6.8%.
Mass spectrwn: molecule peak X07~ fra~ment masses 19~, ,; ~ , .
; 178,and 100; :. :
H -~MR spectrum: T [ppm]: 3.4-4;6(m~, 4.66(m), 5 04~m~
~ 7;22(m), 7,55(quin)~ 7r98(m)7 8;65(quin), 9.00(d) ~d 9.15(t) in ...

~Yr~
; ~ r~
,~
, .... . , , . - I .
~ . . .,. -~ ~ , , . .
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0 ~'~ S3 the ratio 3:2:2:3:1:2:3:6:3;
, IR spectrum (liquid): v(C=C~C--C)-1~50, lG00 cm 1;

~( CH=CH2)-900, 1000 cm 1; ~(C=C)-970 cml , ~(C'I-f )-13'70, : H \CH3 1365 cm~l. .
... .
- Exam~le 8 I~ the procedure is as indicated in Example 7, but `~ withou-t the addition ol triphenylphosphine as a ligand, (1--ethyl)-nonatrien-(3,6 9 8)-yl-isopropylamine is isola-ted in a yield of 18~6 of theory (converslon 50.4,~).
, :

/ CH-NH-CH3 (CH2)7-cH3 (l-Ethyl)-nonatrien-(3,6,~)-yl-isopropylamine, prepared in acccrdance with Examples 7 and. 89 on hydrogenation using 1.. . Raney nickel in ethanol, and with thè absorption of 3 mols of ; hydrogen, gives ~l-ethyl)-nonyl-isopropylamine; boiling point 63.5C/0.2 mm Hg; nD4 ~ 1.4320.
~ Analysis for C14H31N:
; Calculated C 78.8% H 14~55~ N 6.55%
~ound C 78.935' H 14.64,~ N 6.54~' Mass spectrum: molecule peak 213, ~ragment masses 214, 212, 198, 184, 142 and 100;
Hl-NMR spectrum: T [ppm~: 7~22(sep), 7;61(quin), .
, , . . . , ~ .
. : . .. .. .

--` lO9L9531 8~75(s), 9~00((l), 9 17(m) in t~e ratio 1~ :6:7.
.J~xample 10 j C~
: /
- CH3-CH2-CH2-CH-N_C By-product ¦ CH3 , CH2-CH=CI~-C1'12 C~12-C~2-CT~2-CH2 .'': , .

.: C~
.. . / 3 Cll3-CH2-CII2-CI12 NH ~ Main product ¦ CH3 - CH2-CH=CH-CH2-CH=CH-CH=CH2 .
. The procedure is as described in Example 1, but using 16.85 g (0.149 mol) of N-isopropylidene-n-bu-tylamine instead of ~0~95 g (0 243 mol) of N-butylidene-n-~utylamine, 20.75 g (0.384 mol) of 1,3-butadiene ancl without ~riph~nylphosphine as a ligand. After the subsequent distilla-tion, 17.3 g (7~.3 :~
mmols) are obtained of a mixture of 39.6q6 of N-butylidene(l,l-dimethyl)-nonadien-(3,8)-ylamine and 60.456 of (l,l-dimethyl)-nonatrien-(3,6,8)-yl-n-butylamine. The yield of co-oligomer-isation products is 50.7% of theory, relative to N-isopropyl- :
idene-n-~utylamine reacted (~onversion 100%); boiling point 60-64C/0.2 mm Hg; n24 = 1.4729.
Analysis for C15H27N: :
Calculated. C 81.4% H 12.15% N .6.33 Found C 79.7% ~l 12.2% N 6.1 ., .
~, . .

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

. .

4~ S 3 ~
Mass spec~rum: mol~cule peak 221, fIagtnent rna;ser 222, 220, 20G, 17~, 152 and 114 (main produc-t);
Hl-NMR spectrum: (main product) 1~ppm~: 3.3-~l 4(m), , ~ .
4 52(m), 4,92 and 5 01(m); 7.15(q), 7.49(t) 7 7 92(m), 8.6~(m), ~ 8O98(s) and 9009(t) in the ratio 3:2:2:2:2:2:5:~;
'~ IR spestrum (liquid): (main product) v(C=C-C=C) -1650, 1610 cm 1; ~(-C~-I=C]~2)-905~ 1005 cm~l;
H ~ H3 o( ~C~) - 970 cm 1; o(`~C )-1360, 1377 cm 1 : b \ CH3 `' ~e~
:'. .
. .
-~ - CH
?~ / 3 CH3-c~2-c~2-c~I=N-c I C~3 C~l2-cH=cH-c~l2-c~l2-cH2-cH=c~l2 ;~ The procedure is as described in Example 10, bu-t using 2.25 g (8.56 n~nols) of triphenylphosphine as a ligan~. This gives, as the exciusive product, the by-product formed in Example 10, namely N~butylidene-tl,l-dimethyl~-nonadi~n-(3,8)-~lamine; yield 27.1% of -theory, r~lative -to N-isopropylidene-n-butylamine reacted (conversion 100%); boiling point GO-62C/
O.2 mm Hgs nD~ = 1.4624.
Analysis for C15H27N
;; Calculated C 81.4% H 12.155~o N 6~330/o ~ound C ~0.0% H 12.1% N 6. 20~.
Mass spectrum: molecule peak 221, fragment mas~es 222, ~ 22~, 206, 17~, 152, 112 and 95;
... .
r 2 1 , 1 ~, . . . .

953~
. : Hl-Nr~ spectrum: ~ ~ppm~: 2.5(-t), 4~ .7(ul), 4~95 . and 5 19(m), 7.5-8 1(m), 8,2-8 7(m), 8~87(s) and 9.1(t) in the ; ~ ratio 1 3:2:8:4:9;
IR spectrum (liquld): v(C=N) - 1675 cm 1; v(C. C) -1650 cm~l; ~ ( -C=CH2 ) - 910 ~ 990 cm~l;

~(-C=f- 3 972 CID l;~(~C ) - 1365, 1330 cm 1.

..:
C~l (~H3--C}~2--C'~2--CH2--NHi-l 1 . . . CH;5 ( V}~2 ) .7 C~3 .

The compounds prepared in accordance with Examples 10andlL~, namely ~ dime-thyl)-nonatrien-(3~6~8)-yl-n-butylamine and N-butylidene (l~l-dimethyl)-nonaidien-(3,8)-ylamine~ on hydro~en-ation in me thanol using a Raney nickel catalys-t, and WitiL the absorption of 3 mols of hydrogen in each case, give (l,].-dime-thyl )-nonyl-n-butylamine; boiling point 67C/O.1 mm l~g;
nD4 ~ ~ . 4~82 .
Analysi s f or C15H3~5N:
Calcula-ted C 79. 3,~ H 14. 550,6 N 6~155~
~ound C 79 . 2150' H 14 . 77% N 6 . 035~ .
~ ~!
;` Mass spectrum: molecule peak 2279 ~ragmen-t masses 226, 212 " :L84, 156 1 142 and 114i; -Hl-NMR spectrurn: I ~ppm]: 7. 57(t), 8,75(s), 8.96 and 9;00 in e~h ca~ ~), 9.15(t) in the rat.io 2:19:6:6.
., .

- 2~ -"~

. .

~~ ~iL04Lg~31 r-~
_,~mp~e 13 .~ CH3./C~I~
G-N -CH-CH
CH3C~13 : ~ 'H2-C~-CH-CH2-CM2-~H2--C~-C~ 2 ., The procedure is as described in Example 19 bu-t using 28.-3 g (0.2505 mol) of N-isobutylidene-isopropyl~nine instead of 30.95 g (0.243 mol) of N-butyli.den~-n-butylamine. A refin-ing distilla-tion gives 14.0 g (63.2 mmols) of N-isopropylid-ene~ isopropyl)-nonadien-(3,8)-ylamine; yield 50.2~6 of theory, relative to N-isobutylidene-isopropylamine reacted (con~ersion 50.l~%); boiling point 56C/0.2 mm l1~; n2~ _ ~ S86.
Analysis for C15Hz7N:
Calcula~ed C 81.455 H 12.2% N 6.34,t Found C 81.23% H 12.48~ N 6.29 Mass spectrum: molecule peak 221, fragment masses, 222, 220, zo6, 178~ 152, 136, 122 and 112;
Hl-NMR spectrum: ~ [ppm] 4.30(m), 4,76(m~, 5,14(m), 7~01(m), 7~7-8,1(m), 8.06(s), 8,30(s), 8.60(m)l 9.14 and 9,21~dd) in the ratio 1:2:2:1:6:3:3:3:6;
IR spectrum (liquid: v(C=N) - 1650 cm 1; v(C=C) -1640 cm 1; ~(-CH=CHz) - 910, 990 cm 1;

: ~(C=f) 970 cm 1; ~ ~ C ) - 1670, 1685 cm 1.
.. H C~13 -. .
~ 3 . ~ .

-~495i~

Example 14 .. f The procedure is as described in Example 13, but with-out the addition of triphenylphosphine. N-Isopropylidene-~l-isopropyl)-nonadien-~3,8)-ylamine is obtained in a yield of 19.3% of theory, relative to N-isobutylidene-isopropylamine reacted ~con~ersion 32.7%).
~xample 15 CH

3 \ CH -~
CH-NH-CH-CH ~

~( :H2)7~cH3 N-Isopropylidene-~l-isopropyl)-nonadien-~3,8)-ylamine prepared in accordance with Examples 13 and 14, on hydrogenation using Raney nickel in methanol, and with the absorption of - 3 mols of hydrogen, gives ~l-isopropyl)-nonyl-isopropylamine;
boiling point 57.5C/0.1 mm Hg; nD4 = 1.4384.
;` Analysis for C15H33N:
Calculated C 79.3% H 14.55% N 6.17%
Found C 78.62% H 14.79% N 6.49%
Mass spectrum: molecule peak 227, fragment masses 228, 226, 212, 184, 168, 142, 114, 98, 72 and 56;
Hl-NMR spectrum: 1~ ~ppm~: 7.58~-n), 8.75Cs), 9.02(d), ,~ 20 9.14 and 9.17~dd~ in the ratio 2:16:15 Example 16 ` CH3jC-NH-CH2-CH2-CH=CH-CH2-CH=CH-CH=CH2 f.
.''.

:, .

.
, _ i lO~L9531 . The procedure is as ~escribed in Example 1, ~ut using 18.65 g (0.2195 mol) of N-metllylid~ne-tert.butylamlrle ins~ead of 30095 g (0.2~3 mol) o~ N-~utylidene-n-butyl~nine. A reLin-ing distillation gives 5.43 ~ (2~.2 mmols) of N-nonatrien-(~96,8)-yl-tert,butylamine; yi~ld 19.65~ of tI~eory, relative to N-methylidene~tert.butylamiIle reacted (conversion 65.9Q');
boiling point 52C/0~2 mm ~Ig; n23 = 1.47400 Analysis ~or ClzH23N:
Calculated C 80.4S' H 1107% N 7.9~' Four.d C 7802% H 12~090 N 7.9%
Mass spectrum: molecule peak 193~ fra~ment masses 194, 178; 154, 121~ 114, 105, 86, 57, 41 and 30;
Hl-N~ spectrum: r [ppm3: 3;4-4;6(m), 4.~3tm), 4,99 ~d 5;04(m), 7024(m)" 7447(t)9 7,91(m)~ 8.68(s), 13,94(s) . in the ratio 3:2:2:2:2:2:1:9;
IR ~pectrum (liquid): ~ (C=C-C=C)-1650 9 lG05 cm 1;
(C=C~ =CH2)-900, 1005 cm 1; ~ )-972 cm ~;
CH
CH3)-1360, 1385 cm Example 17 .

CH3-N~I-CH ~ ~ ~ -" . I
,~ CH2-CH=C~I-CH2-CH-CH-'C~-CH2 The procedure ollowed is as in Example 1, but using .
33.0 g 50.277 mol~ of N-benzyliden~-met~lylamine instead of ` . 30.95 g (0.243 mol) of N-butylidene-n-butylamine,and 2g.8 g (0.551 mol) of 193-butadieIle. A refining distillation gives : - 25 -.

-~ F
- - . , ..

~ L9531 1805g ~105 mlllols) of (l-~}lenyl)-nonatri~ t3t6~8)-yl-met : amine; yi~ld 35 0 3S~o 0~ th~ory, relati~e to N-benzylidene-methylamine reacted (con~ersion ~2.50,~); boiling point 76-78C/OoOOl mm llg; n~3-5 = 1 5376 ~ Analysis for C16H21N:
: Calculated C 84.5% H 9 3% N 6020,b Found C 83 ~ 7' H 9.k~ N 6.1%
Mass spectrum: molecule peak 2279 fragment masses 212 9 120 ~ 103 and 91;
Hl-NMR spectrum: 1~ [ppm~: 2.~2(s), 3064 and 4.3~(m),

4.66(m)D 4.87 and 5001(m)~ 6.59(t), 7 28(m), 7 69(m)9 7.80(s), 8.02ts) in the ratio 5:3:2:2:1:2:2~
.- IR spectrum (liquid): ~ (N-H) - 3300 cm 1; ~ (C=C-C=C) 45, 160~ cm 1; ~ (-CH=C112) - 902, 1005 cm 1, ~ t-~-Ç~
970 cm 1; ~ (-CH3) - 1355 cm 1. H
~7 Exam~le 18 - If triphenylphosplline is not used in Example 17, ~n :
otherwise identical procedure ~ives (l-phenyl)-nonatrien-,6,8)-yl-methylamine in a ~leld of 13.4So of theory, relatl~e to N-benzylidene-methylamine r~ac-ted ~conversion . 75~o).
Example 19 .~`' . , , CH3-NH-CH~>

` ~C~2 )7--CH~s ;
,; ,. . .
... . .
The (l-phenyl)-n~natrien-(3,6,8)-yl-methyl~mine, pre-.~ par~d in accordance wi~h Examplrs 17 and 1~, is ~Iydroeenated ;~ "' ' ' .
., '''~ .

~. ' in methanol at normal pressure and room temperature (25°C), using a Raney nickel catalyst, and with the absorption of 3 mols of hyrogen, to give (1-phenyl)-nonyl-methylamine;
boiling point 98°C/0.1 mm Hg; n?3 = 1.5164.
Analysis for C16H27N:
Calculated C 82.36% H 11.66% N 6.0%
Found C 82.22% H 11.98% N 5.99%
Mass spectrum: molecule peak 233, fragment masses 232, 160, 156. 134, 120, 91 and 42;
H1-NMR spectrum: ? [ppm]: 2.75(s), 6.57(t), 7.75(s), 8.37(s), 8.75(s), 9.13(t) in the ratio 5:1:3:1:14:3.
Example 20 The procedure is as descrived in Example 1, but using 33.3 g (0.25 mol) of N-benzylidene-ethylamine instead of 30.95 g (0.243 mol) of N-butylidene-n-burylamine, and 26.15 g (0.483 mol) of 1,3-butadiene. After distillation, 9.5 g (39.4 mmols) are obtained of (1-phenyl)=nonatrien-(3,6,8)-yl-ehtylamine; yield 20.5% of theory, relative to N-benzulidene-ethylamine reacted (conversion 76,7%); boiling point 86-89°C/0.1 mm Hg; n?3 = 1.5337.
Analysis for C17H23N:
Calculated C 84.5% H 9.6% N 5.85%
Found C 82.8% H 9.7% N 5.6%
Mass spectrum: molecule peak 241, fragment masses ~ 9531 242~ 240, 226, 134l 106 ~l~ 91;
MR spectrum: r ~ppm]: 2,72(s); 3.6-5.2(m~, 6035(t39 7025(m), 7055(m)9 7.95(m); 8.40(s), 8.97(t) in t~e ratio 5:7:1:2:2:2:1:3;
IR spectrum (liquid): v (~-H) - 3300 cm 1;
(C=C-C-C) - 1645, 1600 cm 1; ~ (-CH=Cl~2) - 907, 1000 cm 1;
6 (~ 972 cm 1; ~ (~CH3).- 1380 cm ~3~ ' ' .
If triphenylphosphine is not used in ~xample 207 at otherwise identical procedure gives (l-phenyl)-nonatrien-: . .
~396,8)-yl-ethylamine in a yield of 30.3% of theory, relative to ~-benzylidene-ethylamine reacted (conversion 62.50/')o-The procedure is as described in Example 20, but - ~ using 73.8 g t0.565 mol) instead o:E 33 g ~0,25 mol) of N-benzylidene-ethylamine, and 57.3~:g (1.06 mols) of 1,3-, . . .
~ . butadiene. 28 R g (0,331 mol? of morpholine are added to . the reaction mixture, which is warmed to 40C and kept at ~his temperature for 2 hours. :~After deactivating the .
n~ckel catalyst by means of triphenyl phosphi-te, 85.7 g 356 mol) of (1-phenyl)-nonatrien-(3,6,8)-yl-ethylamine ar~ obtained by distilla-tion; yield 7~6 of theory, rela'ive , .
. .
~ . to N-benzylidene-ethylamine reacted (conversion 8506 Example 2~
~' ' ; ' ' - ' ~3-C~2-~-T~

,, ' ~
: ~r~ -28 - ;
.. ~
~. --.................. .. . . ..... ... . . _ . .. . .. ... . . .. .... .. ..
.,,` . . ......... ..................
.". ' - . 1 0 ~ 5 3~ .
. The (l-p~lenyl)-norlatrien-(3,6,8)-~1-ethyl~line, prepared in accordance with Examplcs 20, 21 and 22, is hydrogenated in methanol at no~nal pressure and room te~-. perature ~25C)~ using a R~ney nickel catalyst and ~ith -t}le absorption of 3 mols of hydrogen, to give (l-~henyl)-nonyl-et~ylamine; boiling point 90-93C/O.Ol mm ~Ig; n25 = 1.4865.
Analysis ~or C~7H29N: .
Calc~lated C 82.5% H 11.75% N 5.67%
Found C 82.695~o H 11.85Sb N 5.70%
Mass spectrum: molecule peak 247~ fraGment mas~es 246~ 218, 170 9 134, 104 and 91; ~ :
Hl-MMR spectrum: ~ [ppm]: 2.83(s)~ 6.53(t), 7.61 :~ (q~, 8.~9(m), 8.81(s), 9oOO(t) and 9.17(t) in ~he ratio

5:~:2:2:13:3:3.
Example 24 ' CH3-CH2-C~2 NH ~

; . ~H2-CH=C~-CH2-CH=CE~-C~I=CH2 - The procedure is as dcscribed in Example 1, but ~ :
using 34.2 g (0.2325 mol) o~ N-benzylidcne-n-propylamine ~ .instead of 30.95 g (0.243 mol) of N-butylidene-n-butylamine, and 26.7 g (0.494 mol) of 1,3-butadiene. ~fter distilla-tion9 17.5 g (68.6 mmols) of (1-phenyl)-nonatrien-(3,5,8)-: yl~n-propylamine are obtained; yi~ld 37.85' of theory, relative to N-benzylidene-n-propyl~nine reacte~ (conversion 77.~; boiling point 101-104C/O.OOl ~n H~; n23 _ 1~5282~
~nalysis for C18~Iz5N: :
Calculated C 8~o6%H 9~9~ N 505~' : , .
7~ 2~ -, ~g531 Found C ~305~'c ~1 9.97' - N 5,l~
Mass spectrum: molecule peak 255, fra~nent masses 254 9 22G 9 213 9 198 9 186, 148, 106 ~nd 91;
Hl-~lR spectr~n: r rpprn]: 2J78(S) 9 306-5.2(m),

6~40t~); 7030(m), 7.55(m), 7.95(1n)~ 8.50(m)9 9.0~(t) in the ratio.5:7:1:2:2:2:3:3;
IR spectrum (liqui~ (\N~ 3300 cm 1;
V (C-C-C=C) - 16509 1600 cm~~ C~=CI-12) - 905,998 cm~l; ~
}1 - -C-) - 972 cm 1; ~ (-CH~) - 1380 cm lo .
iExampl~ 25 If triphenylphosphine ié not used in ~xample 24, an - otherwise ideIltical procedure gives (l-phenyl3-nonatrien-~96,8~-yl-n-propylamine in a yield of 33.0% o theory, i .~ rela~ive to ~-~enzyli~ene-n-propylamine reacted (conversion 6~
. . . - :
Exc~m~lc 26 :
The procedure is as described in Example 22, but using 74.7 g t0.5425 mol) of N-benzylidene~n-propylamine instead of 737~ g (0.5G5 molj o~ N-benzylidene-ethylamin~, and 60~2 g (1.115 mols) of 1,3-butadiene. Thc subsequ~nt distillation ~ives 97.5 g of (1-phenyl)-nonatrien-(3,6,~)-yl-n-propylamine; yield 84.5% o~ theory, relative to M-b8n~ylid~ne-propyl ~ ine reacted (conversion ~3~5 ,~ ~ eH3-CH2~CH2-' (C~ ) -C~
: . , , .~; ~ ` 3 ~ . .. ,.. ~,; . , .......... , , ~. .

:

~L04953 The (l-phenyl)-nonatIien-(3,6,8)-yl-n-~)ropyl~nine, prepared in accordance with EXamP1eS 24, 25 and 26, is hydroeena~ed in meth~ol at ~lormal pressure an~ room t~m-perature (25C)9 using a Raney nickel catalyst and ~ritll ~he absorp~ion Or ~ mols of hydrogen, to ~iYe (l-pIIcnyl)-rlollyl-n-propylamine; boiling point 106-10~~/0.001 mm Hg;
nD4 = 1.4846.
Analysls for C~ iN: ; -. Calculated C 8~o8~ H 11~7,6 : N 5.36%
Found C 8206% H 1107,6 N 5.~S~
: Mass spectrum: molecule peak 2619 fra~ment masses 260, 232 and 148;
~ Hl-MMR spectrum: [ppm]: 2.75(s)~ 6.41(t), 7.59(t), : 8~36(m)~ 8078(s), 9.14(t) in the ratio 5:1:2:2:14:7. - ~:-~ ' ~ -, CH
: ~3-(cH2) ¦ CH~
` ~ CH2-C~I=C~I-C!~2-C~I=Ci~-c~=c~2 ;:
. The procedure is as described ill Example 1, but us~ng 35.5 g (0.21 mol) of N-isopropylidene-n-octylamine . ins~ead of 30.95 g (0.243 mol) of N-butylidene-n-butyl- :
aminep and 35.2 g (0~652 mol) of 1,3-butadiene. Distilla-~ tion 6i~es 21~6 g (78 mmols) of (151-dimethyl~-nonatrien-`. (3,6,8)-yl-n-octylamine; yi~ld 44.~' of theory, relative ;~ to N-isopropylidcne-n-octylamine reac~cd (convcrsion ~2.9 boiling point 103-105C/0.001 mm ~16; n23 = 1.4797.
Analysis for C19II35N~

1 _ .

~953~

Calculated C 82.3% H 12.65% N 5.05%
Found C 81.9% H 12.45% N 4.94%
Mass spectrum: molecule peak 277, fragment masses 278J 276, 262, 225, 217, 170 and 58;
H -NMR spectrum: 1~ Cppm~: 3.3-5.1~m), 7.18~m),

7.51~t), 7.94~m), 8.60~m), 8.99~s) and 9.10(t) in the ratio 7:2:2:2:13:9;
IR spectrum ~liquid): V ~C=C-C=C) - 1645, 1600 cm 1;
~-CH=CH2) - 900, 1000 cm 1; ~-C=C~-) - 970 cm 1;

CH

8~C~ ) - 1375, 1360 cm~l.

Example 28a Hydrogenation, as speci~ied in Example 27, of the ~l,l-dimethyl)-nona~rien-~3,6,8)-yl-octylamine obtained in accordance with Example 28 gives ~l,l-dimethyl)-nonyl-n-octylamine; boiling point 107-108C/0.01 mm Hg; n20 =
1.4444.
Analysis for ClgH41N:
Calculated C 80.50% H 14.5% N 4.95%
Found C 80.2% H 14.3% N 4.8%
Example 29 ', CH3-CH2-NH-CH{~
:"
., C~2-CH=CH-CH2-cH=cH-cH'cH2 :, The procedure is as described in Example 1, but ~sing 42.1 g ~0.251 mol) of N-4-chloroben~ylidene-ethylamine i;, ~, .

':;

', :
: ' ' '` ~04953~
~nstead of 30.95 g (0.243 mol) Or N-butylidene~ utyl2mi.nD, and 34.6 g (0.641 mol) of l,~-~utadiene. Di5tillation ~j.ves 1105 g (41~9 mmols) of tl-(4-chlorophenyl~]-nonatricn - (3,6,8)-; yl-ethylamine; yield 2Z.5~' of theory, relative t~ rJ-4-chloro-benzylidene-ethylamine reacte~ (conversion 74.1~); boili.llg point 99-102C/0.001 l~n ~g; n~5 = 1.5335O
Analysis for C17~z2NCl:
Calculated C 74.1' H 7.99~o N 5.07,b Cl 12.9~
Found C 73.6% H 8.1% N 4.~5' Cl 12.~3~
: Mass spectrum: molecule pe~c 275, fra~ment masses 168; 140;
Hl-Nnm spectrum: ~ ~ppm~: 2.80(s), 3.3-5.1(m), 6.46(t), 7024(m), 7.54(q~ 9 7070(m), 8~37(s), 8~95(t) in the ratio 4:7:1:2:2:2~
IR spectrum (liquid(: ~ (~N-H) - 3300 cm 1;
: V (C=C-C=C) - 1645, 1600 cm 1; ~ (-C~I=CH2) - 905, 1000 ~m 1;
) - 970 cm 1; ~ (C~I3) - 1375 cm 1.
, - I~ tri~llenylphosphine is not~used in Example 29, an ~;
otherwise idcntical procedure gives ~1-(4-chlorophenyl~
nonatrien-(~,6,8)-yl-ethylamine in a yièld of 10.330 of theory9 relative to N-4-chlorobenzylidene-ethylamine reacted ; t~on~ersion 50.16)~ ~
' ~ ~ . , .

C~3 MH-C~I ~ Cl .~ . I ~ .. .
CH;~-CH=CH-C~2-CH=C~-C~-CH2 , ~ ~ ~
~ 33 :' ` , ~. . .1 . ~
.

~4953~L .
The procedure is as descri~e~ x~nple 22, but using 7209 g (00476 mol) of N-4-c}llorobenzylidellc-methyl-amineg 69.7 g (1.295 mol) of 1,3-~utadicne and 4~,6 g (0.558 mol) of morplloline (reaction time: 2 hours at 40~C).
The subsequent distillation gives 3~.6 g (0.148 rnol) of [1-(4-chlorophenyl)]-nonatrien-(~,6,8)-yl-metl~yl~nine; yield 32.5% o~ theory 9 relative to N-~chlorobenzylidene methyl-amine reacted (conversion 81.5~); boiling point 93-96C/
0.001 mm Hg; n24 = 1054730 Analysi5 for C16~20NCl:
~alculated C 7~.5% H 7.655~ N 5.36% Cl 13,55,b Found C 7~003% H 7.80,b N 5.40~0 Cl 12.82Q~o Mass s~ectrum: molecule peak 261; frag~lel~t masses 260, 240, 154; . .
Hl-N~ spectrum: r [~pmJ: 2.~3~s), 3 3-4.65(m), 4.68(m), 4.99.and 5.10(m), 6060~t); 7.25(ln), 707~(m) and 7.80(s)9 8.53ts) in the ra~tio 4:3:2:2:1:2:5:1;
IR ~pectrum (liquid~ N-H) - 3330 cm 1;
(C=C-C=C) - 1640, 1600 cm 1; ~ (-CH=CI12) - 900, 1005 cm 1;
970 cm~
' ~
., - ~. .

CH3-C~12-CH2-NH ~
!
,., .. I~-CH=CH-CH2-C~=CH-CH=CM2 , ; , The procedure is as described in ExamI)le 1, bu~
using ~7.7 ~ (0.255 mol) of N~ yri-lylid~ne-n-propylami~le ' ' .. 1-~

4953~ . :
instead of 30.95 g (0~243 mol) of N-bu~ylid~ne-n-~utyl~r~
and 27.6 g (0.511 mol) of 1,3-butadiencO Dis~illatioll ~ives 2302 g (90.5 ~ol~) 0~ Cl-pyridyl-(4)J-nonatrien - (3,6,~)-yl-n-propylamine~ Yield 38.2So of theory~ relativc to ~J_(l~_ pyridylidene)-n-propyl~nine reacted tconversion 93,');
boil~ng point 110-113C!OoOOl mm ~Ie; n22 = 1.5347.
Analysis for C17H24N2 Calculated C 79.6% H 9.37~6 N 10,95%
Found C 7809~ H 3~3~ ~ 109655~
Mass spectrum: molecule peak 256, fragment masses 255 9 2 419 227 and 149; --.
. H~ R spec~rum: r [ppm]: 1.4(m)9 2.7(m), 3.3-5.1~m)p 604(t~9 70~5-7,65(m), 7095(m), ~.5(m), 9.05(t) iIl the ratio 2:2:7:1:4:2:3:3;
spectrum (liquid): ~ (,N-H) - 3300 cm 1;
(C=C-C=C) - 1650, 1600 cm 1; ~ -C~I=CI~2) - 905, 995 cm 970 cm~~ C~l3) - 1380 cm~l, .;, - . . ...
~_~ - , , I~ triphenylp~Iosphine is not used in ~xample 32, ~l otherwise identical procedure gi~es tl-pyridyl~ ]-nona- -trien-(3,6,8)-yl-n-propylamine iIl a yield of 1600~ of theory, relative to ~ 4-pyridylidene-n-propylamine reacted ~con-~ersion 77.5~0')0 Example 34 . ;'' :-CH3-N~I-C~- ~ N

C1~2-C~=CH-CH2-CH=CH-CH'CH~

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

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

~ . 1049S31 : . The procedure is as ~escribed in Ex~nple 2Z, b~t using 79.1 g ~0~659 mol~ of N-4-pyridylidene-methylamine,, 6405 g (1.195 mols) of 1,3-butadiene and 49.25 ~ (0.556 mol) of morpholine (reaction time 2 hours at 40C)o Distilla-~ tfon gives 83.2 g (0.365 mol) of [l-pyridyl-(~ nonatrien-(396,8)-yl-methylamine; yield 65.97~ of theory, relative to N-4-pyridylidene-methylamine reacted (conversion 84.3,~
boiling point 108-111C/OoOOl mm I~g; n2 4 = 1.5440.
--Analysis for C19H20N2:
Calculated C 78.9% H 8.760,6 N 12.255 Found C 78.~5~ ~ 8O85~ N 11.9%
- Mass spec~rum: molecule peak 228, fragment masse~
. . 227, 121;
: * -N~IR spectrum: ~ ~ppm]: 1~54~d) 9 2o8~(d) ~ .
3-3-406(m),.4.5~(m), 5.00 and 5.12(m), 605~(t) 9 7.23(m) 9 , 7.78(m) ~Id 7.80(s), 8.55(s) i.n the ratio 2:20~:2:2:1:2:5:].;
.~. IR spectrum (liquid): ~ (,N-H) - 3300 cm 1;
v (C=C-C=C) - 1650, 1600 cm 1; S ~-CH-CHz) - 903,~1005 cm 1;
970 cm 1; ~ (-CH3) - 1358 cm 1.
., ~ . .
~., .
CH~-NH-CH- ~

CH2-CH = CH - C~I2-CH=CII-C~I=CH2 The procedure is as describcd in Ex~nple 1, but using 32.8 g (0.273 mol) of N-m-pyridylidene-methylamine instead of 30.95 g ~0.2~3 mol) of N-butylidene-n-butyl~Iinc, ~Id 32~0 E
t0.593 mol) of 1~3-butadieneO The sub~equent distill~tion r . ~ ~ 3 6 ._._ . ... .. . .. .. . . . ..... .... . . ..... . ...
.,., ,. . , . 11~

. '. ' ' .

:
` ~

1)49531 g~ves 18.5 ~ (~,1.0 ~nols) o~ m-pyridyl)-nolla~rien-(3~6,~)-yl-methylamine; yield 47~45~ of -t~leory9 relative to N-m~
pyr~dylidene-me-thylamine reacted ~con~ersion 6401');
boilin~ point 96-99C/0.001 mm Hg; n20 = 1.54560 Analysis for Cl5H20N2:
Calculated C 79.0S H 8.8~b N 1202%
~ound C 78O05~ H 809~ N 11-8,b Mass spectrum: molecule peak 2289 ~ragment masses 161g 121 and 94; ~ . .
~ -NMR spectrum: ~ [ppmJ: 1.57(s), 2.45(d), 2.88tm~9 ~.3-4.65(m) 9 4,70(m), 5.00(m), 6,54(t) 9 7.29(m), 7072(m~ and 7.80(s)9 8.40(s) in the ratio 2~ 3:2:2:1:2:5:1;
IR spectrum (liquid)~ N-H) - ~300 cm 1;
(C-C ~=C3 - 16509 1600 cm 1; ~ CH=C~I2) - 905, 1005 ~m 1;
, -C=C-) ~ 972 cm~lO : - O
H . . .
.
ExamrJle 36 ;.
The procedure is as described in Ex~nple 22, but usin~ ~ -- 29.8 g ~0.24~ mol) of N-m-pyridylidene-methyl~nine, 3~.7 g gO.716 ~ol) of 1,3-butadicne and 28.9 g (0.332 mol) of .-morpholine. Distillation gives 22.9 g (0.1005 mol) of (1-~-pyridyl)-nonatrien-(3,6,8)-yl-methylamine; yield 48.80~ of theory, relative to N-m-pyridylidene-methylamine reacted (conversion 8~.5,6). ~ :
; : ~
~ ~ -..
. .
12-CH~-C1~3 CH3--CH2-CH2-C~2~ c\ ~ ' C~12-CH-CH-CH2-C~=CH-C~-C~2 ~ ~ -: ,~ ~ ~ 37 ~

.,.......... . . ~

:,, `-~ . 104953~ -The procedure is as ~escribed in ~x~nple 22, but using 69.4 ~ (0.546 mol) of N-butylidene-n-butylamine inst~ad of 73.8 g (00565 rnol~ of N-benzylidene-et)lylaminet 73 3 g (1.36 mols) of 1,3-butadiene and 30.0 ~ (0.345 mol) of morpholineO Distillation gives 54.9 g (0.234 mol) o~ n-propyl~-nonatrien-(3,6,8)-yl-n-butylamine; yield ~s9.60' of ~ theory9 relative to N-butylidene-n-butyl~nine reacted (con-Yi~rsion 86~2t~;)o The pllysical data of the reaction product are quoted in Example 1~ .
~ . :
I~9 in EXamP1e 379 instead o~ Usillg 2025 g (~ 5~ l~nols~
;.
. of tripllenylphosphine, no ad~it.ion of tllis p~lor,phine li~and :: is made 9 an otherwise identical procedure gives (l-n-propyl)-nonatrien-(3,6,8)-yl-n-butylamine in a yield of 21.2Q' of ~A . . .
~ . theory, relative to N-butylidene-n-butylamine reactecl (con-~ . version 82,2o) ~ Ex~mple 39 ~; 2~75 g (10 n~ols) of bis-cyclooctadiene-1,5-nick~
: t) and 2.62 g (10 mmols) of tripllenylphosplline are dissolved at-10 to 0C in 200 ml Of absolute bell~ene containing 54 ~
: . .
(1 mol) of 1,3-butadiene. A clear, l~omog~neous, orange~red ~olution is formed. 50 g (0.394 mol) o~ N-butylid6ne-n-butylamine are then added and the reaction mixture i5 stirl~d ~t 40C lor 20 ho~lrs. After ~Jorlcin~ up the reaction T~roduct a~ directed in ~xample 1, (1-nr~ropyl)-nor~ ien-(3,6,8)-yl-n-butylamine is obtained in virtually tll~ sarne yield a~ ~h~t inflicated in Examplc 1~ :
.
, 3 8 - .

,.................... .... - ... . .. ...... ..... . .. . . . ", r :, .

1~9~31 ~ .
; CH -CH -CH
NH-CH
t~H2 CH=C~I-CH2-CII=CI~C~I=CH2 The procedure is as ~escribed in Example l, but using 108 g (0;77 mol) of N-bu-tylid~ne-cyclohcxyl~nine instead of 30.95 g (0.243 mol) of N-bltylidene-n-butyl~1~.n~, ~nd 8~o6 g (1.55 mols) of l,3-butadiene. The subsequent dis'tillation gives 66.0 g (0.253 mol) of (l-n-propyl)-notla~
trien-t3,6,~)~yl-cyclohexylamine; yield 51.1/o Of theory, relative to N-butyl.idene-cyclohexylamine reacted (conversion 70.2gO~; boiling point 90-95C/O.OOl n~ H~ 1~ - 1.4963.
Anal.ysis for C~8H31N. ~
Calculated C 82.7~ H 11.9% ~ N 5.45' :
: Found C 82.5~ E~ 12.2~o N 5.6S~
:, .
Mass spectrun1: molecule peak 261, fra~n~nt masses 26~ 218, 192, 178, 154 and 72;
Hl-N~ spectrum: L ~ppm]: 3.3 - 4.6(m), /~.63(m), 4.86 and 5.lO(m) 9 7.24tm), 7.53(m), 7.96(m) 9 8.27(m), i 8070(m), 8.88(s), 9.12(t) in t~c ratio 3:2:2:2:2:2:5:9:1:3;
IR spectrum (liquid): ~`(C=C-C=C) - 1650, 1600 cm l (-C~I=C~2) - 900, lOOO cm l; ~ (-C=C-) ~ 970 cm l; ~ t-Ctl3) ~ -- 137Q c~
Exampl~_4l .., 2 C~2 ~I-C~ _ c~2-c~2-c~l2-c~2-c~l2-cH2-cH2 CH3 .
: . ~
. , ~ . ' . . ; ' ~ . , . . . . .. . . . . . .
" . .. _ .. ,.. .......... . .... , ..... .. , ._ ~
~,~ , , .

, - ~4953~
. The (l-n-propyl)-nona~rien-(3,~,8)-yl-cyclol-lexy~.a~ e, prepared in accordance with Ex~nple 40, is hy~roEenate~ at normal pressure and room tempera-ture (25C) 9 usin~ a palla-dium-charcoal ca-talyst in a mixture of ~l~cial acetic aci~/
methanol (~olun~e ratio 1:3)9 and with the a~sorption of 3 mols of hydrogen, to give (l-n-propyl)-nonyl-cyclohexyl-amine; boilin~ point 104 - 106C/0~001 mm Hg; nD3 = 1.1~5~6O
Analysis ~or C18H37N:
; Calculated C 80.9Q6 H 1309% N 5.2~S
~ound C 810050' II 13.97~ N 500o6 ~ ass spectrum: molecule peak 267, fra~ment masses 266, 2529 224 and 154;
* -MMR spectrum: 1C tppm]: 7.56~m~, ~.26(m), 8.74(sj, 9L13(t) in the ratio 2 6 22 ~o : Example 42 ~ .
,' ' ' :~ . .
CH3-ci~2~N~

~" CH2-C~=CH-CH2-CH=CH-C~f-CH2 The procedure is as described in E~ample 19 but usin~
30.35.g (0.247 mol~ of N-furfurylidene-e-thyl~nine instcad of , 30095 g (0.243 mol~ of N-butylidene-n-butylamine, and 36.9 g . gOo684 mol) of 193-but~dienec The subsequen~ d.istillation gives 37.0 g (0.160 mol) of (1-furyl)-nonatrien-(~,6,~)-yl-ethyl~mine; yield 72.7~o6 Of thcory, relativc to N-furfuryli.dene-ethylamine reacted (conversion 90.5%); boilin~ poin~ 84-8~C/
~ Ool mm H~; n20 = 1~ 5122.
: Analysis for C15~21N0:

`i~,, ~ .
..... .. , .. - - - .. ,,! ~
, 1 ' .

.

l ~A
104L9~3~

Calculated C 77.88% H 9.15% N 6.05% 0 6.92%
Found C 77~9~/O H 9.4% N 5.75% 0 6.7~/o Mass spectrum: molecule peak 231~ fragment masses , 230, 216, 164, 124 and 96;
-, H -NMR spectrum:7C ~ppmJ: 2.78(s), 3.3-4.6(m), 4.67(m), 5.04 and 5.15(m), 6.37(t), 7.30(m), 7.57(m), 8.49(s),

9.00~t) in the ratio i~l:5:2:2:1:2:4:1:3;
IR spectrum (liquid):~f(~N-H) - 3300 cm ` ~r (C~C-C=C) - 1650, 1600 cm ; o~ (-CH=CH2) - 1005, 900 cm (-C=C-) - 970 cm ; ~ (-CH3) - 1375 cm Example 43 --CH3-CH2-NH'C~H~

(CH2)7 CH3 The L l-furyl-(2 )J -nonatrien-(3,6,8)-yl-ethylamine, prepared in accordance with Example 42~ is hydrogenated at normal pressure and room temperature (25C), uslng a palla-dium-charcoal catalyst in methanol/glacial acetic acid (~olume ratio 3:1), and with the absorption of 3 molesof hydrogen, to give ~l-furyl-(2)3-nonyl-ethylamin~; boiling point 141 - 142.5 C/9 mm Hg; nD = 1.4644.
Analysis for C15N27N0:
Calculated: C 75~90~. H 11.46% N 5.90%
Found: C 75.67% H 11.35% N 5.60%
, Mass spectrum: molecule peak 237; fragment masses 236, 208~ 193, 170~and 124;
H -NMR spectruml~ppm~: 2.74(d)3 3.79(dd)~ 3.96 (d), 6~40(t), 7.53(quartet) and 7.61(s)~ 8.30(m), 8.79(s), ~,.

, -41-.- :
"`
~ .

.

953~

8~97(t), 9.16(t) in the ratio 1~ 3:2:12:3-3 Example 44 CH3-NH-CH- ~
(CH2)7 CH3 The (l-m-pyridyl)-nonatrien-(3,6,8)-yl-methylamine, prepared in accordance with Examples 35 and 363 is hydrogen-ated at normal pressure and room temperature (25C)~ using a palladium-charcoal catalyst in glacial acetic acid-methanol (volume ratio 1:3), and with the absorption of 3 mols of hydrogen~ to give (l-m-pyridyl)-nonyl-methylamine; boiling point 98-99 C/0.001 mm Hg; nD = 1.4972.
Analysis ~r C15H26N2:
Calculated: C 76.9% H 11. 1% N 12.9%
Found: C 76.3% H 10.7% N 12.1%
Mass spectrum: molecule peak 234, fragment masses 233, 204, 156, 121 and 94;
H ~NMR spectrum:~G ~ppmJ 1.59~d3 and 1.62(d)~
2.45(m), 2.87(m), 6.59(m)~ 7.62(s), 7.80(s), 8.39(m) 8.81(s)~ 9.18(t) in the ratio 2:1:1:1:1:3:2:12:3.
Example 45 `, CH3 ~ CH3 ~ ,-CH
. . ~ CH2-NH-C~ ~ .
CH2-CH=CH-CH2-CH=CH-C~=CH2 The procedure is as described in Example 22, but using 65.6 g (0.408 mol) of N-isobutylidene benzylamine, 60 g (1~11 mols) of 1~3-butadiene and 14.6 g (0.168 mol) of .:
, ~42-:' :

, . :
. . . . . . .

:.: ~ .. : . : . .
: : . : :: . . : :

~9~3~
morpholine. The reaction is complete after 20 hoursO
Distillation gives 57.1 g (0.212 mol) of (l-isopropyl)-nonatrien~(3,6,8)-yl-benzylamine: yield 95.9% of theory, relative to N-isobutylidene-benzylamine reacted ~ conversion 54.3%); boiling point 99-101C~O.OOl~m~Hg3~ nD = 1~5274.
Analysis for C19H27N:
Calculated: C 84.7% H 10.1% N 5.2%
Found: C 83.79% H 10.13% N 5.29%
Mass spectrum: molecule peak 269, fragment masses 268, 254, 226 and 162;
H -NMR spectrum:~ ~ppm~: 2.82(s), 3.3-4.5(m)~ -4.65(m)~ 5.02(m) and 5.13(m)~ 6.35(s)~ 7.24(m), 7.74(quin)~
8.00(m) and 8.24(m)~ 8.78(s)~ 9.14(d) in the ratio 5:3:2:2:2:
2:1:3:1:6;
IR spectrum (liquid);ly~(G=C-G=C) - 1650~ 1600 cm (-CH=CH2~ - 900~ 1005 cm , ~ (-C=C-) - 970 cm o~ (-CH 3) - 1363~ 1380 cm~l.
; `~CH3 Example 46 ` If morpholine is not used in Example 45~ an other-s wise identical procedure gives (l-isopropyl)-nonatrien-(3~6~8)-yl-benzylamine in a yield of 53.3% of eheory~
relative to N-isobutylidene-benzylamine reacted (conversion 41.5%).
~., ~
, :
v CH3 ~ ' , CH2-NH-cH
(CH2)7 3 , , .

,r' _43_ 1 .

:
:
,: , `, ' ' ~ ' -~L04953 1 The (l-isopropyl)-nonatrien~(3,6,8)-yl-ben~ylamine, prepared in accordance with Examples 45 and 46, is hydrogena-ted at normal pressure and room temperature (25 C)~uusi~g;la Raney-nickel catalyst in methanol~ and with the absorption of 3 mols of hydrogen, to give (l-isopropyl)-nonyl-benzylamine;
boiling point 96-99C/0.001 mm Hg; n~3 = 1.4807.
A~alysis for C19H33N;
Calculated: C^82.9% H 12.0% N 501%
Found: ~~ C 8207% H 12.3% N 5.2%
Mass spectrum: molecule peak 275, fragment masses 274, 260, 232 and 162;
H -NMR spectrum:~ ~ppm~: 2.68(m), 6.23(s), 7.66(m), 8.23(m), 8.71(s~, 8.89~s), 9.10(t) and 9.11(d) in the ratio 5:2:1:3:12:1:9.
Example 48 CH3 C~ :, ¦ 3 .' I
CH -0-CH -CH -CE=N-CH
~3~ ;2 2 2 CH=CH_CH2-CH2-CH2-C~=CH2 The procedure is as described in Example l, but using 47.1 g (0.329 mol) of N-isobutylidene-(3-methoxy)-propylamine instead of 30.95 g (0.243 mol) of N-butylidene-n-butylamine, and 45.1 g (0.834 mol) of 1,3-butadiene.
Distillation gives 42.7 g (0.171 mol) of N-(3-methoxy)-propylidene-(l-isopropyl)-nonadien-(3,8)_ylamine; yield 57.4% of theory~ relative to N-isobutylidene-(3-methoxy) propylamine reacted (conversion 90.6%); boiling point 84 86 Ct0.001 mm Hg; nD = 1.4609. ;

. , .
~'.

~44~ ~
-- ~ - ~ . . , - . . . .
, , . ~ , , :
.. . .

i - ~

.
' 1~9531 : j~

Analysis lor C16~129NO: -Calr.ulated: C 76.4G7~ H 11.62' N 5.57' Found: C 7G~55% H 11.71q' N 5.6G56 ~ Mass spectrwn: molccule pealc: none; fra~en-t ; masses 219, 204, 1929 176, 126 and 110;
~ -M ~ spectrum: ~ rppm]: 2~53(t)g 4.38(m), 4.78(m), 5.11(m) and 5.15(m) 9 6'.~ t), 6.75(s), 7053(m)~ 7.~1(m), 8.05~m), 8.28(m), 8.59(quin), 9.16 and 9.19(dd) in the ratio 2-2:2:3:3:2:4:1:2:6; ~:
:;~ - IR spectr~n (liquid): ~ (C=N) - 1670 cm~l, .
~(C=C~ - 1640 cm ~ CH=C~l2) - 909; 990 cm~l, ~ (-C=C~
965 cm , ~ t-CH 3 ) - 1365, 1380 cm~10 ~H3 ~-.~ .

~ C113 ~ ~

~113~ C~2~ 2-C!l2-NH- ~
CH2-CH-C~-CH2-CH-CH-C~-C~2~

The procedure is as described in Exc~mple 22, bu-t ~ using 47.8 g (0,334 mol) of N~ obutylidene-(3-me-~11oxy)- ~ -~r' propylamine, 45.3 ~ (0.837 mol) of 1,3-b~-tadiene and 29.8 ~ ~
'?` l0.342 mol) of morpholine. Distillation ~i~es 3~.6 g ~-tO.154 mol) of (1-isopropyl)-nonatrien-t3,6,8)-yl-(3-methoxy)-propylamine; yield ~6.7~ of th~ory, relative to~
N-isobutylidene-(3-methoxy)-propylaminè reactcd ~conver~ion 9~0~; boilin~ point ~6-89C~0.001 mm ~; n20 = 1.ll905.
.. . .
Analysis for Cl~T29N0 ;~
Calculated: C 76.5q' H 11.6' N 505~00 6.40~ :
'- ' ', , ... . . .... ... . .....
l ~ E
.
- . . . . . . .
~ - :

~049531 Found: -o C 75.7% H 11.4% N 5.4% 0 6.9%

Mass spectrum: molecule peak 251, fragment masses 250, 236, 208 and 144;

H -NMR spectrum:~ Lppm~ 3.3~5.2(m)~ 6049(t), 6.75(s), 7.0-7.5(m), 7.7-8.5(m), 8.85(s), 9.08(d) in the ratio 7:2:3:3:7:1:6;

IR spectrum (liquid)s~f (c=C-G=C) - 1643~ 1600 cm (N-H) - 3320 cm 1, S (-C~=CH2) - 900~ 1000 cm ~ S (-C=C-) C~ 3 ) ~ 1365~ 1380 cm H
C~3 ~e~
Ca3-NH-CH~

2-C~=CH-CH2-C~CH-C~=CH r The procedure is as described in Example 22, but using 47.7 g (0.381 mol) of N-2-thenylidene-methylamine, 46.0 g (0.853 mol~ of 1,3-butadiene and 29~0 g (0.334 mol) of morpholine. Distillation gives 55q3 g (0~238 mol) of ~;
~l-thienyl~(2)J-nonatrien-(3~6~8)_yl_methylamine; yield 62.8% of theory, relative to N-2-thenylidene-methylamine reacted (conversion 99.3%); boiling point 84-86C/0.001 ~m Hg; nD = 1.5506~ -Analysis for C14H19NS:

Calculated: C 72.06% H 8.20% N 6.00% S 13.74%

Found: C 71.43% H 8.34% N 6.25% S 13.30% ;~

Mass spectrum: molecule peak 233, fragment masses ~` 126;

'" :.
~ . ' ' ~ -46-'''' , ' .

953~
H -NMR spectrum: ~ ~ppm~: 2.91(m), 3.21(m), 3.2-4.5(m)~ 4.64(m)~ 5.01(m) and 5.13(m)~ 6.28(t)~ 7.25(m)~
7.64(m)~ 7073(s)~ 8.56(s~ in the ratio 1:2:3:2:2:1:2:2:3:1;
IR spectrum (liquid~: 3N-H) - 3320 cm 1; ~ (C-C-C=C) - 1645~ 1600 cm ~ CH-CH2) - 900~ 1000 cm ~ S (-C=C) - -968 cm ~ ~o ~N-CH3) - 1360 cm 1.
Example 51 ~NH~CIH ~
( 2)7 3 The ~l-thienyl-(2)~-nonatrien-(3,6,8)-yl-methylamine, prepared in accordance with Example 50, is hydrogenated at normal pressure and room temperature9 using a palladium-charcoal catalyst in methanol/glacial acetic acid (volume ratio 3:1), and with the absorption of 3 mols o~ hydrogen~
to give ~l-thienyl-(2)3-nonyl-methylamine; boiling point 81-83 C/OoOOl mm Hg; nD = 1.4976.
Analysis fior C14H25NS:
Calculated: C 70.3% H 10.5% N 5.8% S 13.4%
Found: C 70~7% H 10.8% N 5.8% S 13~3%
Mass spectrum: m~lecule peak 239~ fragment masses 210, 166, 156, 129 and 1263 Hl-NMR spectrum:~ ~ppm3: 2.91 (dd)~ 3.18(m)~ ~ -6.34~t~ 7.74(si~ 8.95(m)~ 8.66(s)~ 8.80(s)~ 9~18(t) in the ratio 1:2:1:3:2:1:12:3.
, ':
~ ' '."

:.-, : , ~

-47- ~
' .' . ' , .

, :

53~L
Example 52 ~CH2C}12CH3 CH3-CH2-CH2CH2 NH-IH C1~3 CIH3 CH-~ C-CH-Ctl=C-C-CH2 The procedure is as described in Example 22, but using 50.7 g (0.4 mol) of N-butylidene-n~butylamine, 75.9 g (0.925 mol) of 2,3~dimethyl-1,3-butadiene and 24.3 g ~0.279 mol) of morpholine. me reaction time is 20 hours. Dis-tillation gives 10.8 g (0.0372 mol) of ~N~ propyl)-3,4J7~8-tetramethyl-nonatrien-(396,8)-yl~-butylamine; yield 18.4% of theory~ relative to N-butylidene-n-butylamine reacted (con-version 50.6%~; boiling point 97-104C/0.001 mm Hg; nD =
1.4837.
Analysis for CloH37N:
Calculated: C 82.5% H 12.7% N 408%
Found: C 81.1% H 12.7% N 4.9% `
H -NMR spectrum:~lppm1: 4~5-5~3(m)9 7.42(m), 7.7(m)~
8.09(m). 8.40(m~ 8.65~m)~ 8.95(s)~ 9.11(t) in the ratio 3:2:2:3:12:8:1:6 Mass spectrum; molecule peak 291, fragment masses -~
, 276, 248~ 220, 194~ 166 and 128;
IR spectrum:~(~N-H) - 3300 cm j~ =C-0=C) -1640~ 1600 cm 1~ C=CH2) - 888 cm 1~ S (-CH3) - 1380 cm 1, Example 53 j 2 2 3 CH3-CH2-CH2-CH2-NH-fH ICH3 1 3 ~` ':

-48- ~

.: . .
: ' ~ . .

95~1 The LN~ propyl~-3,4,7,8-tetramethyl-nonatrien-(3,6,8)-yl~-butylamine, prepared in accordance with Example 52, is hydrogenated at normal pressure and room temperature (25C)~ using a palladium-charcoal catalyst in glacial ~cetic acid/methanol (volume ratio 1:3), and with the absorption of 3 mols of hydrogen, to give ~N-(l-propyl)-3,4~7,8-tetramethyl~
nonyl~-butylamine; boiling point 105 - 108 C/0.001 mm Hg;
nD20 -1~4537.
Analysis for C2~H43N:
Calculated: C 80~9% H 14.5% N 4.7%
Found: C 80.6% H 14.7% N 4.5%
Mass spectrum~: molecule peak 297~, fragment masses 282~ 254, 224, 128 and 86;
H -NMR spectrum-.~ Lppm~ 7.45(m)~ 8.3-8.9(m)~
9.0-9.25(m) in the ratio 3:18:22.

Example 54Q
& 3 CH (CH ) -CH N C/

CH2-CH=CH-CH-CH -CH -CH-CH

4.4 g (17.0 mmols) of nickel acetylacetonate and 4.5 g (17.2 mmols) of triphenylphosphine~ in 164 g of absolute toluene in which 15.0 (0.278 mol) of 1~3-butadiene are dissolved, are reduced at 0 to 20C by means of 5.6 g (43 mmols) of ethoxydiethyl-aluminium. After stirring the reaction mixture for one hour at 20C~ a clear~ orangewred catalyst solution is formed. The catalyst solution is then heated to 85C while 1~3-butadiene is continuously introduced, .

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S~l and 90.2 g (0.534 mol) of N-isopropylidene-n-octylamine are added dropwise over the course of 30 minutes. In the course thereof the heating bath is removed and the rate of dropwlse addition is regulated in such a way that the reaction tempera-ture is 85-90C. The reaction solution is then cooled to 0 C~ 23 g t74.1 Mols) of triphenyl phosphite are added -lin order to deactivate the ca~alyst and the mixture is distilled.
A 1st fraction which contains 163 g of toluene and 18.1 g (0.107 mol) of unreacted N-isopropylidene-n-octylamine (gas chromatogram) 15 obtained here at a bath temperature of up to 50C and a vacuum of 0.2 mm Hg. A subsequent refining dis~
tillation gives 84O0 g (0~304 mol) of N-octylidene-(l~
dimethyl)-nonadien-(3,8)-yl~amine; yield 71.1% of theory, relative to N~isopropylidene-n-octylamine reactedd (con~ersion 80.0Z); boiling point 86-93C/0~01 mm Hg; nD = 1.4506.
Analysis for ClgH35N
Calculated: C 82.3% H 12.65% N 5~05%
Found: C 8108% H 12.4% N 5.0%
Mass spectrum: molecule peak 277~ fragment masses 276~ 262 and 168; ~ ;
H -NMR spectrum~ ~p~ 2.51 (t)~ 4.29(m~, 4.71(m), S.ll(m) and 5.15(m)~ 7~98(m)~ 8.74(s)~ 8.92(s~ 9.15(~) in ;
the ratio 1:1:2:2:8:12:6:3;
IR spectrum (liquid):~)(C=N) - 1670 cm 1~ (C~C) -1645 cm ~ o~ (~CH~CH2) - 908~ 990 cm 1~ g (~C=C-) - 968 rm 1 / 3 ) - 1365, 1385 cm O H

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Ex~ le 55 / 3 CH~CH3 CH3-O~CH2-CH2~CH=N-CH

CH2-CH=CH-CH2-CH2-CH2-CH=CH2 The procedure is as described in Example 54~ but using 240.0 g (1.68 mols) of N-isobutylidene-(3-methoxy)-propylamine instead of 9092 g (0.534 mol) of N~isopropylidene-n-octylamine. Distillation gives 214.1 g (0.855 mol) of LN-(3-methoxy)-propylidene~ isopropyl)-nonadien-(398)-yl-amine; yield 67.7% of theoryg relative to N-isobutylidene-C(3-methoxy)-propylamine~ reacted (conversion 77.6%);
boiling point 84 - 86C/0.001 m~ Hg, n2 = 1.4606.
Analysis for C16H29N0:
Calculated: C 76.50% H 11.55% N 5.60% 0 6.36% ;
Found: C 76~52% H 11.80% N 5~49% 0 6.25%
Mass spectrum: molecule peak: none; fragnent masses 252~ 236~ 2083 176~ 150~ 142~ 110 and 843 H -NMR spectrum~ ~pm~ 2.50(t)~ 4.25(m)~ 4.73(m)~
5008(m) and 5.11(m)~ 6.46(t)~ 6.71(s)~ 7.48(m)~ 7.75(m)~
8.03(quin)~ 8.26(m)~ 8.58(quin)~ 9.16(d~) and 9.20(d) in the ratio 1:1:2:2:2:3:3:2:4:1:2:6;
IR spectrum (liquid~9V ~ N~H~ - 3300 cm ~'y'(C=N) -1672 cm 1~ ~ (0=C) - 1645 cm 1~ ~ (-CH=CH2~ - 910~ 990 cm o~ (-O=C-) - 970 cm l~ C~ 3) - 1360~ 1385 cm o (C-O-C) - 1125 cm~l 3 ,~ '' ' ., ,;

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,~}13 C}} .. . .
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~CII=~
CU=CH~CH2C~2CH2-C-L~--CH2 The procedure is as described in ~xample 54, bu~
using 43100 g ~2.G8 mols) o~ N-isobutylidcne-kenzyl~nille ins~ead of 90.2 g (0.534 mol) of N-isopropyli~ene-n-octyl-amine. Distillation gi~es 344~8 g (1.285 mols) of N-benzy~idene-(l-isopropyl)-nonadien-(3,B~-yl-amine; yield 73007' of theory9 relative to N-iso~utylidene-benzylamine reacted (con~ersion 65.75~); boi~in~ point 104 - 106C/0.~01 ~m H~; n20 = 1.5194.
~nalysis for ClgH27N~
Calculated: C ~4085' H 10.0,6 N 5.2%
Found: C 84.325~o B 10.015~ N 5;1556 Mass spectr~m: molecule peak 2699 ~ragment masses .~26B, 25~9 226, 1~0~ 143 and 91; ~
NMR spectrum: z~ rppmj:~ 1.93(s), 2.33(m), 2.71(m), .:
4~19(m), 4.70(m), 5,15(m) and 5.18(m~ 7.20(qu), 7.69(m), :~ . 8.10(m), 8.65(m)~ 9~12(d) in the ratio 1:2:3:1:2:2:1:2:5:2 IR spectrum (liquid): ~ (C-N) - 1650 cm l,:~(C=C) -1642 cm ~ CII=C~I2)- 910, 990 cm 1 9 ~ (-C=C- ) - 967 cm 1, ~-C~ 3) - 1365, 1370, 1377 cm~
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Clt2 C~ C~-CH~.C}~2C~12-C~ 2 The procedure i-s as descril~d in Exampl~ 54, but using 360 g (2.71 mols) of N-l)enzylidene etllyla~nille instea-l o~ 90.2 g (0.53~ mol) of N isopropylide~ -octyl~mine.
D~stillation gives 115,7 g (004~ mol) of N-etllylidene-(l-pllenyl )-noIIa :lien- ( 3 9 ~)-yl-amine; yield 49 0 5~ o~ theory, relati~e to ~-benzylid~ne-ethylamine react~d (conversion 35.8~,~), boiling point 87-89C/0.01 mm Hg; n~ = 1,51~5.
Analysis for C17H23N:
Caloulated: C 840650~ H 9.55% N 5.~%
ound: C 84.1Z~, H 9.62Sh N 5.94n,6 , Mass spcctrum: molecule p~ak: none; fra~men-t masses l94, 1~49 106 and 79;
Hl-NMR specl;rum: ~ [ppm]: 2.32(qu) 9 2.72(m), ,.
4023(m), 4.65(m~, 5.05(m) an~ 5.08(m), 5.9~(t), 7.49(m), :` 8.64(qu~n) in the ratio 1:5:1:2:2:1:2:7:2;
.-: IR spectrwn (liquid): V (C=N~ - 1670 cm 1, ~(C=C) -~1645 cm 19 ~ (-CH=C~I2) -.908, 990 cm~l9. ~ (-C=C-~ - 967 cm~lg CH3) - 1355, 1375 cm`~
: The new compound~ o~ the ~ormula Ia and Ib exllibit an anti-micro~ial action and are, therefore, sui;table for combating harmEul micro-organisms, for example in materisl protection.
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The anti-microbial compouncls of t~e present inv~n .
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tion can be used on a very broad basis, particularly to protect organic substrates against attack by harmful and pathogenic micro-organisms. The anti-microbial agents mentioned are, therefore, suitable as preservatives and disinfectants for industrial products of all kinds.
~ mongst the industrial products which can be pre-served or disinfected with the aid of the compounds, acco-ding to the~invention, of the formulae Ia and Ib~ the following may be mentioned as examples: glues, binders, paints, for example paints for walls and ceilings, containing an albuminous paint binde~ textile auxiliaries~ textile finishing agents~
permanent sizes based on polyvinyl alcohol, animal mucilages and oils, laequers and paints, dyeing or printing pastes and similar preparations based on organic and inorganic dyestuffs or pigments, and also those which contain casein or other organic compounds as an admixture~ printing thickeners made from -starch or cellulose derivatives, plasticisers, substances which tend to rot, such as leather and wood, celluloses, viscose spinning compositions and paper.
The compounds according to the invention can be employed in the cellulose and paper industry, for example for preventing the known formation of slime, which f S caused by micro-organisms~ in the equipment used for making paper.

;:
` The action of the compounds according to the inven-tion can also be utilised in preservative and disinfectant finishes for plastics, for example ~olyamides and polyvinyl ~hloride. When using plasticisers i~ is advantageous to add the antimicrobial additive, dissolved or dispersed in the . , ~

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plasticiser, to the plastic. Plastics with anti-microbial properties can be used for all kinds of use articles in whlch an acti~ity against the most diverse germs, such as, for example, bacteria and fungi, is desired~
that is to say~ for example, for foot mats, bathroom cur-tains~ toilet seats, foot grids in swimming pools~ wall coverings and the.like. Floor and furniture maintenance materials with a disinfectant action are obtained by incor-porating the compounds into suitable compositions of wax and polish.
The use forms of the active substances according to the invention can correspond to the usual formulations.
Thus, the active substances can be used, for example, in the form of solutions~ dispersions or emulsions, aerosols (sprays) and the like. Since the active compounds of the formula Ia and Ib are~ for the most part, insoluble in water or are only sparingly soluble in water~ custo~ary organi~ sol~ents~
such as toluene, xylene, methylcellosolve, acetone or tetra-hydrofurane~ '~tto which dispersing agents~ for example em lsifiers~ such as sulphonated castor oil~ fatty alcohol sulphates and the li,e and/or other auxiliary materials can additionally be added~ are used or-~he preparation of solutions~ Depending on the applications9 customary wetting agents and dispersing agents can be added to dispersions of active compounds~
The content of acti~e compounds in the agents accor-ding to the invention is generally between about 0.01 and 5 per cent by weight~ preferably 0.1 to 3 per cent by weight~

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relative to the weigh-t of the agent.
The compounds according to the invention can be used with advantage as preservative and disinfectant finishes for fibres and textiles, it being possible to apply them to natural and ar~ificial fibres, where they display a per- ~ -manent action against harmful micro-organisms, for example fungi and bacteria. The addition of the compounds can here take place before, simultaneously wi-th or after a treatment of these textiles with other substances, for example dyeing or printing pastes, flameproofing agents, agents for im~.
parting a soft handle, other finishes and the like.
Textiles treated in this way also exhibit a protection against the occurrence of perspiration odour, such as is caused by~micro-organism.
The agents used for the finishing or pro-tection of textiles should contain the active substances according to the invention in a finely divided form. Particular use iS
therefore made of solutions, dispersions and emulsions of the active substances. Aqueous dispers~ons can, for exa~le, be obtained from pastes or concentrates and can be ubed in liquid form or as an aerosol.
The aqueous solutions or dispersions appropriately contain surface-active agents, for example anionic compounds, such as soaps and other-carboxylates (for exanple alkali metal salts of higher fatty acids), derivatives of sulphur-oxygen acids ( for example -the sodium salt of dodecylbenzenesulphonic acid, water-s~luble salts of , sulphuric acid monoesters of higher-molecular alcohols or of polyethylene glycol :

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1~495~1 e-thers of the lat-ter, such as, say, soluble salts of dodecyl alcohol sulphate or of dodecyl alcohol polyethylene glycol ether sulphate), deriva-tives of phosphorus-oxygen acids (for example phosphates), derivatives with acid (electrophilic) nitrogen in the hydrophilic group ( for example disulphinic salts), cationic surface-active agents, such as amines and their salts ( foreexample lauryldiethy-lenetriamine), onium compounds or amine oxides, or non-ionic surface-ac~ive agen-ts, such as polyhydroxy compounds, surface-active agents based on mono- or poly-saccharides, higher-molecular ethylene glycols or polyethylene glycol ethers (for example polyethylene glycol ethe~ of higher fatty alcohols or polyethylene glycol ethers of higher-molecular, alkylated phenols). In addition the liquor can also contain customary auxil~ary materials, such as water-soluble perborates, polyphosphates, carb9nates silicates, optical b~ighteners, plasticisers, salts with an acid reaction, such as ammonium or zinc silicofluoride, or certain organic acids, such as oxalic acid, and also fini-,shing agents, for example those based on synthetic resins or starch.
The textile materials can be impregnated with the active substances, for example by hot or col, aqueous dye-baths, bleaching baths, chrome baths or after-treatment baths, it being possible to use various textile finishing processes, such as, for example, the padding process or the exhaustion process.
Owing to their greater solubility in organic solvents, the active substances are also well suited for application from non-aqueous media.
The active substances according to the present inven-tion ' ~

- ~7 -~ 0~5~5i3~ :
can be used on their own or together with other known anti-microbial agents for protecting textiles.
Possible textiles which are finished or protected are both fibres of natural origin, such as bhose containing cellulose, for example cotton, or those containing polypep-tides, for example wool or silk, or fibre materials of synthetic origin, such as those based on polyamide, polya-crylonitrile or polyester, or mixtures of these fibres.
In most cases the textile materials are adequately protected against a-ttack by fungi and bacteria by means of a content of 0.01 to 5% by weight, preferably 0.1 to 3% by weight, of the active substance, relative to the weight of the textile materials.
By combining the compounds according to the invention with surface-active substances, particularly detergent sub-, . . .
; stances, washing and cleansing agents with an excellent antibacterial or anti-mycotic action are obtained. The washing and cleansing agents can be present ~n any desired form, for example in liquid, pasty, solid, flake or gran-ular form. In order to prepare such agents, the compounds according to the invention can be incorporated into anionic ~` cationic or non-ionic surface-active agents of the kind mentioned previously or into mixtures of surface-active agents of various kinds.
; Aqueous prepara*ions of such washing and cleansing agents, containing compounds according to the invention can, be used, for example, for the antimicrobial finishing of textile materials. They are also suitable as antimicrobial i cleansing ag~nts in the food and drink industry, for example ''` " . .

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in breweries, dairies, cheese fac-tories and slaughterhou-ses.
:~ For disinfectant and preservative purposes, the com-pounds of the formulae Ia to Ic can also be used in comb-ination with known antimicrobial agents. Theses include, . for example:
Halogens and halogen compounds containing active halogen for example sodium hypochlorite, calcium hypochlorite, ` chloride of lime, sodium p-toluenesulphochloroamide, p-toluenesulphodichloroamide, N-chlorosuccinimide, 1,3-dich-- loro-5,5dimethylhydantoin, triohloroisocyanuric acid, pot-assium dichloroisocyanurate, iodine, iodine trichloride ~: and complex compounds of iodine and iodine trichloride -. with surface-active agents such as polyvinyl pyrrolidone, ;.` alkylphenoxy-polyglycols, polyoxypropylene glycols, alky-laminoethanesulphonic~acids.:and~alkylaminoethanesulphonates, ; larylsulphonates and quaternary ammonium compounds.
;~
~oron compounds, for example boric acid and borax.
Organometallic compounds, for example bis-tributyl-tin oxide, triphenyl-tin hydroxide, tributyl-tin salicylate, . tributyltin chloride, phenyl-mercury borate and phenyl-mercury acetate. Alcohols, for example hexyl alcohol, trichloroisobutyl alcohol, 1,2-propylene glycol, triethy-lene glycol, benzyl alcohol, 4-chlorobenzyl alcohol, 2,4-and 3,4-dichlorobenzyl alcohol:, 2-phenylethyl alcohol, 2-(4-chlorophenyl)-ethyl alcohol, ethylene glycol mono-phenyl ether, methanol, linalool and 2-bromo-2-nitro-1,3 propanediol ..
.: Aldehydes, for example formaldehyde, paraformaldehyde, glutaraldehyde, benzaldehyde, 4-chlorobenzaldehyde, 2,4-and ~ - 59 -;, .
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1~14953~.
3,4-dichlorobenzaldehyde, cinnamaldehyde, salicylaldehyde, 3,5-dibromosalicylaldehyde, 4-hydroxybenzaldehyde, anisal-dehyde and vanillin.
Carboxylic acids and derivatives, for example trichloro-acetic acid, monobromoace-tic acid glycol ester, Na and ca propionate, caprylic acid, undecylenic acid, Zn undecyle-nate, sorbic acid, K and Ca~sorbate, lactic acid, malonic acid, aconitic acid, citric acid, benzoic acid, 4-chloro-benzoic acid, benzoic acid benzyl ester, salicyclic acid 4--chlorosalicylic acid n-butyl-amide, salicylani~ide t 3,4',5-tribromosalicylanilide, 3,~3',4',5-te-trachloro-salicylanillde, 4-hydroxybenzoic acid, 4-hydroxybenzoic acid ethyl ester, gallic acid, mandelic acid, phenylpro-pionic acid, phenoxyacetic acid, dehydracetic acid and vanillic acid propyl ester.
Phenols, for example phenol, mono-and poly-chlorophenols, cresols, 4-chloro-3-methylphenol, 4-chloro-3,5-dimethyl-phenol, thymol, 4-chlorothymol, 4-t-amylphenol, saligegnin, 4-n-hexylresorcinol, carvacrol, 2-phenylphenol, 2-benzyl-4-chlorophenol,2,2'-dihydroxy-5,5'-dichlorodiphenylme-thane, 2,2'-dihydroxy-3,3'5,5l,6,6'-hexachlorodiphenylmethane, 2,2'-dihydroxy~5,5'-dichlorodiphenyl sulphide, 2,2'-dihyd-roxy-3,3',5,5'-tetrachlorodiphenyl sulphide, 2-hydroxy-2', 4,4'-trichlorodiphenyl ether and dibromosal~cyl.
Quinones,for example 2,5-dimethylquinone, 2,3,5,6--tetrach-lorobenzoquinone and 1,4 or 2,3-dichloro-1,4-mapthoquin-one.
Carbonic acid derivatives, for example pyrocarbonic acid diethyl ester, tetramethylthiuram sulphide, 3,4,4'-tri-: ' .

.
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chloro-N,N'-diphenylurea, 3--tri~luoromethyl-4,4'-dichloro-N,N'-diphenylurea, N-3-trifluoromethylphenyl~N'-2-ethylhe_ xylurea, 1,6-bis-(4'chlorophenyl-diguanidino)-hexane, dodecylmethylguanidine acetate, ammonium thiocyanate and 4,4'-diamidino-a,w-diphenoxyhexane.
Amines, ~or example dodecylpropylenediamine, dodecyldietyl-enetriamine and diaminobenzene dihydroiodide.
Quaternary ammonium compounds, ~or example alkyl-dimethyl-benzylammonium chloride, alkyl-dimethyl-ethylbenzylammon-ium chloride, dodecyl-dimethyl-3,4-dichlorobenzylammonium chloride, dodecyl-di-(2-hydroxyethyl)-benzylammonium chlor-ide, dodecyl-di(2-hydroxyethyl)-benzylammonium pentachloro-phenolate, dodecyl-di-(2-hydroxyethyl)-benzylammonium 4-methylbenzoate, dodecyl-dimethyl-phenoxyethylammonium bromide, 4-diisobutyl-phenoxyeth~xyethyl-dimethylben~yl~
ammonium chloride,4-diisobutyl-cresoxyeth~xyethyl-dimethy-lbenzylammonium chloride, dimethyl-ddideclylammodni~m cetyl-trimethylammonium bromlde, do ecy -pyrl lnlum chloride, cetyl-pyridinium chloride, dodecyl-isoquinolin-ium chloride, decamethylene-bis-4-aminoquinaldinium dich-loride, a-(p-tolyl-)-dodecyl-trimethylammonium methosulph-ate and (dodecanoyl-N-methylaminoethyl)-(phenylcarbamoyl-methyl)-dimethylammonium chloride Quaternary phosphonium compounds, for example dodecyl-triphenylphosphonium bromide.
Amphoteric compounds, for example dodecyl-di-(aminoethy~;)-j , glycine.

/ Heterocyclic compounds, ~or example 2-mercaptopyridine-N-oxide, the Na and Zn salt o~ 2-mercaptopyridine-N-oxide, 2,2'-., , ~ - 61 -.:

.' ' '~' . ,.~ , ' ' ,: . ' 1[)45~53~
dithiopyridine~ -di-N-oxide, 8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, 5-chloro-7-iodo-8-hydroxyquino-line, 5,7-dichloro-8-hydroxyquinoline, 5,7-dichloro-8-hydroxyquinaldine, bis-2-methyl-4-aminoquinolylcarbamide -hydrochloride, 2-mercaptobenzthiazole, 2-(2'-hydroxy-3', 5'-dichlorophenyl)-5-chlorobenzimidazole, 2-aminoacridine hydrochloride, 5,6,-di-chlorobenzoxazolone, 1-dodecyl-2-iminoimidazoline hydrochloride and 6-chlorobenzisothiazo-lone. ~-Determination~!of the minimum inhibitory concentrations (~MIC) a~ainst bacteria and fungi:
1.5% strength stock solutions, inlme-thylcellosolve, of the compounds according to the invention,for example (l,l-dimethyl)-nonatrien-(3,6 J 8)-yl-n-octylamine and 1-(4~chlorophenyl)-nonatrien-(3,6,8,)-yl-methylamine are pre~ared and these are subsequently diluted in such a way that the incorporationc:in each case of 0.3 ml of the stock solutions and more dilute solutions made from them in 15 ml of warm nutrient agar gives a series of concen-tra-tions of 300, 100, 30, 10, 3, 1 and so on ppm of active substance in the agar, The mixtures are cast whils-t still warm into plates and, after solidification, are inoculated with the following -test organisms:
Gram-positive bacteria Staphylococcus aureus . .

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Streptococcus faecalis Streptococcus agalac-tiae Bacillus subtilis Gram-negat_ve bacteria Escherichia coli Salmonella pullorum Salmonella cholerae-suis Proteus vulgaris Fungi Trichophyton mentagrophytes Candida albicans Aspergillus elegans After an incubation period of 48 hours at 37 C (bac-teria) or 5 days at 28 C (fungi), a determination is made of the minimum limiting concentration (ppm) of the active, substnace ht which the growth of the test organisms is stopped.
For the above compounds values of MIC are determined which are distinctly below the initial concentration of 300 ppm, for the fungi and/or bacteria mentioned.
Determination of the microbiocidal action A. In order to establish whether the active substances have destroyed the test germs employed in the previous experiment (biocidal effect) or merely inhibited their growth (biostatic effect), circles of sterile filter pap~r with diameter of 20 mm are placed on the inoculation areas of the germs which show no growth and, after a con-tact time of 30 minutes, the germs are transferred by means of these .'; .
- 63 _ , ':

~04g53:~L
circles to sterile agar which has been bloclced in respect of the active substnaces by means of Tween 80. The con-tact time is once more 30 minutes. If no growth of the t.
transferred germs is observed on the secandary agar plate, the germs on the first plate have been destroyed by -thé
active substance, that i$ to say, in the concentrations concerned, the active substance exerts a biocidal effect on the germs tested.
The following additional test is carried out ~n order to confirm the determination given above;:
B Solutions of the following composition are prepared using the active substances mentioned: 5% of active sub-stance, 5% of Na N-coconut-B-aminopropionate, 20% of Permutit-treated water and 70% of ethylcellosolve (ethy-lene glycol monoethyl ether).
Aliquot parts of these solutions are converted by means of sterile, distilled water into emulsions having an active substance content of 1,000 ppm, 500 ppm, 250 ppm and 125 ppm.
9.9 ml samples of the emulsions are inoculated with 0.1 ml of germ suspentions (approx. 107 germs/ml.) Test organisms:
Staphylococcus aureus Streptococcus faecalis Bacillus subtilis Proteus vulgaris After a one minute durations of action, a loop of each of the inoculated emulsions is put into 10 ml of sterile ., ;!
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brain-heart infusion broth, and the latter is then incu-bated for 24 hours a-t 37 C and -then assesed for turbidity ~growth of germs). The loop is a measure which is m~de of platinum wire and has a defined diameter, and is standardised for microbiological purposes.
In the above experiments the compounds tested showed a biocidal action.
Treatment of Textiles The compounds according to Examples 28 and 31 are dis-solved in a suitable formulation (ethylcellosolve/dimethylformamdie). The three substrates listed below are put into the formulation baths and are then squeezed out between two aluminium fo~ls; the sub-strates are then dried in air. They are aqueezed out in such a way that 2,500 ppm of active substance are located on the fabric in case )a 250 ppm in case b) and 25ppm in case C~.
Substrates:
l. Cotton, renforcé, mercerised,bleached, weight 121 g/m 2. Polyamide, nylon staple fabric, set, bleached, weight 140 g/m .
3. Polyes~er, Dacron staple fabric, type 54, set, bleached weight 130 g/m2.
The substrates are then tested against the test organisms mentioned below by the agar diffusion tes-t (modified AATCC Test Method 90, 1970).

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_cteria Staphylococcus aureus ATCC 6538 Escherichia coli NCTC 8196 Proteus vulgaris ATCC 9484 Fungi Candida albicans ATCC 10259 Trichophyton mentagrophytes ATCC 9533 Aspergillus elegans M 3637.
The test plates consist O-r a two-layer agar, that is to say of a base layer of uninoculated nutrient agar and a convering layer of inoculated nutrient agar.
Bacteria: nutrient agar Fungi: mycophilic agar.
The filtered suspension of germs is poured onto a solidified base layer. After the inoculated layer has solidified, 20 mm diameter circles of the treated subst rates are laid upon it. The bacteria and Candida plates are incubated for 24 hours at 37C; the fungi plates are incubated for 3 to 4 days at 28 C. After the incubation is plates are evaluated in respect of the zone of ihhibition.
If there is no zone of inhibition, the growth under the test piece is checked using a magnifying glass.
The compounds tested in -this way exhibit, in combin-ation wi~h the substrates used, a good action aga~nst the fungi and/or bacteria mentioned.

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Claims (11)

WHAT WE CLAIM IS:
1 A compound of formula Ia or Ib (Ia) and/or (Ib) wherein R1 represents alkyl containing 1 to 8 carbon atoms and which may be substituted with alkoxy containing 1 to 4 carbon atoms; cycloalkyl containing 5 to 8 carbon atoms, or aralkyl containing 7 to 11 carbon atoms, R1' represents alkylidene containing 1 to 8 carbon atoms and which may be substituted with alkoxy containing

1 to 4 carbon atoms; cycloalkylidene containing 5 to 8 carbon atoms, or aralkylidene containing 7 to 11 carbon atoms, R2 represents hydrogen or alkyl containing 1 to 8 carbon atoms, R3 represents hydrogen, alkyl containing 1 to 8 carbon atoms, phenyl which may be substituted with halogen; furyl.

thienyl, pyridyl-3 or pyridyl-4, and R4 and R5 independently of one another represent hydrogen or methyl.

2. A compound of formula Ia or Ib according to claim 1 wherein R1 represents alkyl containing 1 to 8 carbon atoms, cycloalkyl containing 5 to 8 carbon atoms, benzyl or .beta.-phenylethyl, R1' represents alkylidene containing 1 to 8 carbon atoms, cycloalkylidene containing 5 to 8 carbon atoms, benzylidene or .beta.-phenylethylidene, R2 represents hydrogen or alkyl containing 1 to 8 carbon atoms, R3 represents hydrogen, alkyl containing 1 to 8 carbon atoms, phenyl which may be substituted with halogen; furyl, thienyl, pyridyl-3 or pyridyl-4, the R4s each represent hydrogen and the R5s inde-pendently of one another represent hydrogen or methyl, or the R4s each represent methyl and the R5s each represent hydrogen .

3. A compound of formula Ia or Ib according to claim 1 wherein R1 represents alkyl containing 1 to 8 carbon atoms, cyclohexyl or benzyl, R1' represents alkylidene containing 1 to 8 carbon atoms, cyclohexylidene or benzylidene, R2 represents hydrogen or alkyl containing 1 to 8 carbon atoms, R3 represents hydrogen, alkyl containing 1 to 8 carbon atoms, phenyl, chlorophenyl, furyl, thienyl, pyridyl-3 or pyridyl-4, and the R4s and R5s each represent hydrogen.

4. A compound of formula Ia or Ib according to claim 1 wherein R1 represents alkyl containing 1 to 4 carbon atoms, R1' represents alkylidene containing 1 to 4 carbon atoms, R2 represents hydrogen or methyl, R3 denotes methyl or phenyl, and the R4s and R5s each represent hydrogen.

5. A process for the manufacture of a compound of formula Ia and/or Ib (Ia) and/or (Ib) wherein R1 represents alkyl containing 1 to 8 carbon atoms and which may be substituted with alkoxy containing 1 to 4 carbon atoms; cycloalkyl containing 5 to 8 carbon atoms, or aralkyl containing 7 to 11 carbon atoms, R1' represents alkylidene containing 1 to 8 carbon atoms and which may be substituted with alkoxy containing 1 to 4 carbon atoms; cycloalkylidene containing 5 to 8 carbon atoms, or aralkylidene containing 7 to 11 carbon atoms, R2 represents hydrogen or alkyl containing 1 to 8 carbon atoms, R3 represents hydrogen, alkyl containing 1 to 8 carbon atoms, phenyl which may be substituted with halogen; furyl, thienyl, pyridyl-3 or pyridyl-4, and R4 and R5 independently of one another represent hydrogen or methyl, characterized in that a 1,3-diolefine of formula II
( II) in which R4 and R5 have the meaning given under formulae Ia and Ib, is reacted at a temperature from -50°C to +100°C, in the presence of a catalyst which is obtained by reducing a nickel compound which is free from carbon monoxide, with or without the addition of an electron donor, with a compound of formula III

(III) wherein R1, R2 and R3 have the meanings given under formulae Ia and Ib.

6. A process as claimed in claim 5, characterized in that the reaction is carried out in the presence of a basic reaction accelerator.

7. A process as claimed in claim 5, characterized in that a catalyst is used which is obtained under reducing conditions by the action of an electron donor on a nickel compound which is free from carbon monoxide.

8. A process as claimed in claim 5, characterized in that a catalyst is employed which is obtained by reducing a nickel compound which is free from carbon monoxide, using a halogen-free metal alkyl or metal aryl compound, in the presence of an electron donor.

9. A process as claimed in claim 5, characterized in that a catalyst is employed which is obtained by reducing nickel acetylacetonate, using ethoxydiethyl-aluminium in the presence of triphenylphosphine.

10. A process as claimed in claim 6, characterized in that morpholine is used as a basic reaction accelerator.

11. A process as claimed in claim 5, characterized in that the reaction is carried out at a temperature between 20°C and 95°C.