Parabanic acid aminals of the formula ##STR1## wherein R.sup.1 is ##STR2## wherein Z is selected from the group consisting of an aliphatic radical having 1-20 carbon atoms, an aromatic radical having 6-14 carbon atoms and an aliphatic-aromatic radical having 7-20 carbon atoms; PA1 R.sup.2 and R.sup.3 may be the same or different and each is selected from the group consisting of hydrogen, an aliphatic radical having 1-20 carbon atoms, an aromatic radical having 6-14 carbon atoms and an aliphatic-aromatic having 7-20 carbon atoms; R.sup.4 is hydrogen or ##STR3## with Z being as defined above; and R.sup.5 is the same as Z.

This invention relates to new parabanic acid aminals and to a process for 
the production thereof. 
These new compounds correspond to the following general formula: 
##STR4## 
wherein R.sup.1 represents an optionally substituted aliphatic, 
aliphatic-aromatic or aromatic carbamoyl radical; 
R.sup.2 and R.sup.3, which may be the same or different, each represents a 
hydrogen atom or an optionally substituted aliphatic, aliphatic-aromatic, 
aromatic radical; or together form a ring; 
R.sup.4 represents a hydrogen atom or an optionally substituted aliphatic, 
aliphatic-aromatic or aromatic carbamoyl radical; and 
R.sup.5 represents an optionally substituted aliphatic, aliphatic-aromatic 
or aromatic radical. 
An alternative method for numbering the compounds of this invention is 
##STR5## 
The optionally substituted aliphatic radicals preferably contain from 1 to 
20 carbon atoms, these radicals may contain up to 2 double bonds or 1 
triple bond. The optionally substituted cycloaliphatic radicals preferably 
contain from 5 to 12, more preferably 5 or 6 carbon atoms in the ring and 
are, of course, also regarded as aliphatic radicals in the context of the 
present invention. 
The optionally substituted aromatic radicals are preferably contain from 6 
to 14 carbon atoms, more preferably from 6 to 10 carbon atoms, more 
especially 6 carbon atoms in the ring system. In the case of the phenyl 
radical, it may optionally be attached to another aryl radical through an 
oxygen or sulphur atom. 
The aliphatic-aromatic radicals preferably contain from 7 to 20 carbon 
atoms. 
Carbamoyl radicals are radicals corresponding to the following structure: 
##STR6## 
wherein R.sup.7 has the meaning of R.sup.5 and represents an optionally 
substituted aliphatic radical, preferably having from 1 to 16 carbon 
atoms, an aliphatic-aromatic radical preferably having from 7 to 20 carbon 
atoms or an aromatic radical, preferably having from 6 to 14 carbon atoms, 
with the above meaning. 
Substituents on the above-mentioned aromatic and aliphatic radicals are, 
for example, C.sub.6 -C.sub.16 aryl (preferably phenyl), CN, NO.sub.2, 
alkyl mercapto and alkoxy groups preferably containing from 1 to 4 carbon 
atoms, carboxylic ester groups, preferably those with lower aliphatic 
alcohols, preferably containing from 1 to 8 and more especially from 1 to 
4 carbon atoms, and also the disubstituted amino group, preferably 
substituted by lower aliphatic radicals (preferably having from 1 to 4 
carbon atoms), halogen (preferably fluorine, chlorine, bromine), lower 
haloalkyl radicals (preferably having from 1 to 4 carbon atoms, the 
halogen preferably being fluorine and/or chlorine) and, in the case of the 
aromatic radicals, also lower alkyl groups, preferably containing from 1 
to 4 carbon atoms. 
The above-mentioned structure of the inventive compounds was confirmed by 
elemental analysis, mass spectra, .sup.1 H-NMR-spectra and .sup.13 
C-NMR-spectra. The IR-spectra show the carbonyl bands typical of parabanic 
acids at from 1710 to 1740 cm.sup.-1 (strong) and at from 1770 to 1800 
cm.sup.-1 (weak), in addition to urea carbonyl bands at from 1630 to 1700 
cm.sup.-1 (strong). 
The present invention also relates to a process for preparing the parabanic 
acid aminals according to the present invention wherein 2-imidazolines 
corresponding to the following general formula: 
##STR7## 
wherein R.sup.2 and R.sup.3 are as defined above; and 
R.sup.6 has the same meanings as R.sup.4 above, are reacted with organic 
monoisocyanates. 
The process according to the present invention for producing the new 
parabanic acid aminals is generally carried out as follows: 
The starting substances may be used in such quantities that from 0.5 to 10 
moles, preferably from 3 to 4 moles, of isocyanate groups are available 
per mole of 2-imidazoline. 
In general, it is best to carry out the reaction in a solvent or diluent, 
in which case the starting materials may either be dissolved or even 
simply suspended. It is, of course, also possible to carry out the 
reaction in the absence of a solvent or diluent. Solvents suitable for use 
in the process according to the present invention are compounds which are 
inert to NCO-groups, for example aromatic hydrocarbons, chlorinated 
aromatic hydrocarbons, benzonitrile, aliphatic hydrocarbons, esters and 
ketones. Particularly suitable solvents are toluene, xylene, mesitylene, 
chlorobenzene, dichlorobenzene, N-methyl pyrrolidone, dimethyl formamide, 
dimethyl acetamide, hexamethyl phosphoric acid triamide, tetramethyl urea, 
nitromethane and nitrobenzene. 
The reaction according to the present invention is carried out at 
temperatures of from -20.degree.to +250.degree. C. It is preferably 
carried out at temperatures of from 30.degree. to 200.degree. C., more 
especially at temperatures of from 80.degree. to 160.degree. C. 
It is generally best to carry out the reaction in the absence of moisture. 
It may be advantageous, especially in cases where readily volatile 
isocyanates are used, to carry out the reaction under pressure, for 
example at an excess pressure of from 0.5 to 10 atmospheres, preferably 
from 0.5 to 5 atmospheres. 
In order to accelerate the reaction and to suppress secondary reactions, it 
may be advantageous to add acidic or basic catalysts, especially the 
catalysts normally used in isocyanate chemistry, such as metal alcoholates 
and tertiary amines. 
The reaction according to the present invention is exemplified by the 
following reaction equation: 
##STR8## 
The following .DELTA..sup.2 -imidazolines are preferred for carrying out 
the process according to the present invention: 
2-imidazoline 
4-methyl-2-imidazoline 
4-ethyl-2-imidazoline 
4-cyclohexyl-2-imidazoline 
4-phenyl-2-imidazoline 
4-(p-chlorophenyl)-2-imidazoline 
4,5-dimethyl-2-imidazoline 
5-ethyl-4-methyl-2-imidazoline 
5-methyl-4-phenyl-2-imidazoline hexahydrobenzimidazole 
1-(methylcarbamoyl)-2-imidazoline 
1-(n-propylcarbamoyl)-2-imidazoline 
1-(cyclohexylcarbamoyl)-2-imidazoline 
1-(phenylcarbamoyl)-2-imidazoline 
1-(3,4-dichlorophenylcarbamoyl)-2-imidazoline 
1-(p-nitrophenylcarbamoyl)-2-imidazoline 
1-(methylcarbamoyl)-4-methyl-2-imidazoline 
1-(phenylcarbamoyl)-hexahydrobenzimidazole 
1-(p-tolylcarbamoyl)-5-(naphthyl)-1-2-imidazoline 
Organic isocyanates preferably used for carrying out the process according 
to the present invention are aliphatic monoisocyanates having from 2 to 21 
carbon atoms or aromatic monoisocyanates having from 7 to 15 carbon atoms. 
It is particularly preferred to use methyl, ethyl, allyl, n-propyl, 
n-butyl, iso-butyl, tert.-butyl, n-amyl, dodecyl, olely, stearyl, 
cyclohexyl, 1-chloro-2-ethyl, methoxy methyl, 1-cyano-3-propyl, phenyl, 
o-tolyl, p-tolyl, benzyl, m-tolyl, 4-chlorophenyl, 3,4-dichlorophenyl, 
2-nitrophenyl, 3-cyanophenyl, 4-methoxyphenyl and 1-naphthyl isocyanate. 
The compounds according to the present invention may be used as auxiliaries 
for textiles and rubber and also as pharmaceuticals and plant protection 
agents. For example the compounds of the present invention are active 
against Fusicladium or apple seedlings. They may be applied to the 
seedlings from solutions or suspensions at concentrations of from 0,001 to 
1 percent by weight.

EXAMPLE 1 
7.0 parts by weight, of 2-imidazoline and 50 parts by weight of cyclohexyl 
isocyanate are stirred for 25 hours at 110.degree. C. in 25 parts by 
weight, of toluene. On cooling, a deposit is precipitated and is filtered 
off under suction and washed with ether, giving 38.3 parts by weight, of 
the parabanic acid derivative 1,3-dicyclohexyl-6,9-bis-cyclohexyl 
carbamoyl-2,4-dioxo-1,3,6,9-tetraaza-spiro [4.4]-nonane, melting at 
188.degree.-190.degree. C. 
______________________________________ 
C H N 
______________________________________ 
C.sub.31 H.sub.50 N.sub.6 O.sub.4 
Calculated 65.23 8.83 14.72 
Observed 65.0 9.0 14.9 
______________________________________ 
EXAMPLE 2 
2.8 parts by weight, of 2-imidazoline and 9 parts, by weight, of methyl 
isocyanate are heated for 50 hours at 150.degree. C. in a sealed tube. On 
cooling, a resin-like product is formed and is rubbed with cyclohexane, 
giving 2.5 parts, by weight, of the parabanic acid derivative 
1,3-dimethyl-6,9-bis-methyl carbamoyl-2,4-dioxo-1,3,6,9-tetraaza-spiro 
[4.4]-nonane, melting at 272.degree. C. (decomposition). IR (KBr): 1776 
cm.sup.-1, 1721 cm.sup.-1, 1647 cm.sup.-1 (C.dbd.O) 
EXAMPLE 3 
3.5 parts by weight of 2-imidazoline and 16.6 parts by weight, of allyl 
isocyanate are stirred for 26 hours at 110.degree. C. in 10 parts by 
weight, of toluene. On cooling, a colourless deposit is precipitated and 
is filtered off under suction and washed with toluene, giving 3.8 parts by 
weight, of the parabanic acid derivative: 1,3-diallyl-6,9-bis-allyl 
carbamoyl-2,4-dioxo-1,3,6,9-tetraaza-spiro [4.4]-nonane, melting at 
171.degree. C. MS: Mole peak 402 
EXAMPLE 4 
47.6 parts by weight, of phenyl isocyanate are added dropwise over a period 
of 1 hour at 100.degree. C. to 7 parts by weight, of 2-imidazoline in 25 
parts by weight, of chlorobenzene, followed by stirring for 3 hours at 
130.degree. C. On cooling, a deposit is precipitated which is filtered off 
under suction and washed with chlorobenzene, giving 23 parts, by weight, 
of the parabanic acid derivative: 2,4-dioxo-1,3-diphenyl-6-phenyl 
carbamoyl-1,3,6,9-tetraaza-spiro [4.4]-nonane, melting at 248.degree. C. 
Molecular weight (osmometric): Found 431, calculated 427.5 
EXAMPLE 5 
9.45 parts by weight, of 1-phenyl carbamoyl-2-imidazoline and 11.9 parts by 
weight, of phenyl isocyanate are heated for 1 hour at 140.degree. C. in 20 
parts by weight, of xylene. On cooling, a deposit is precipitated which is 
filtered off under suction and washed with a little toluene, giving 16.7 
parts by weight, of the parabanic acid derivative: 
2,4-dioxo-1,3-diphenyl-6-phenyl carbamoyl-1,3,6,9-tetraazaspiro 
[4.4]-nonane, melting at 246.degree. C. 
EXAMPLE 6 
2.54 parts by weight, of 1-methyl carbamoyl-2-imidazoline and 7.98 parts by 
weight, of p-tolyl isocyanate are stirred for 63 hours at 110.degree. C. 
in 15 parts by weight, of toluene. On cooling, a colourless deposit is 
precipitated and is filtered off under suction and washed with toluene, 
giving 3.8 parts by weight, of the parabanic acid derivative: 
2,4-dioxo-6-methyl carbamoyl-1,3-di-(4-tolyl)-9-(4-tolyl 
carbamoyl)-1,3,6,9-tetraaza-spiro [4.4]nonane, melting at 254.degree. C. 
EXAMPLE 7 
1.68 parts by weight, of 4-methyl-2-imidazoline and 12.2 parts by weight, 
of p-chlorophenyl isocyanate are stirred for 73 hours at 110.degree. C. in 
10 parts by weight, of toluene. On cooling, a colourless deposit is 
precipitated which is filtered off under suction and washed with toluene, 
giving 12.7 parts by weight, of the parabanic acid derivative: 
2,4-dioxo-1,3-bis-(p-chlorophenyl)-6,9-bis-(p-chlorophenyl 
carbamoyl)-7-methyl-1,3,6,9-tetraaza-spiro [4.4]-nonane, melting at 
180.degree. C. IR (KBr): 1787 cm.sup.-1, 1725 cm.sup.-1, 1683 cm.sup.-1 
(C.dbd. O). 
EXAMPLE 8 
(a) 3.5 parts by weight of 2-imidazoline and 28.2 parts by weight, of 
3,4-dichlorophenyl-isocyanate are stirred for 2 hours at 110.degree. C. in 
50 parts by weight, of toluene. On cooling, a colourless deposit is 
precipitated and is filtered off under suction and washed with 
cyclohexane, giving 24.0 parts by weight, of the parabanic acid 
derivative: 1,3-bis-(3,4-dichlorophenyl)-6,9-bis-(3,4-dichlorophenyl 
carbamoyl)-2,4-dioxo-1,3,6,9-tetraaza-spiro [4.4]-nonane, melting at 
233.degree.-234.degree. C. 
______________________________________ 
C H Cl N 
______________________________________ 
C.sub.31 H.sub.18 Cl.sub.8 N.sub.6 O.sub.4 
Calculated 45.28 2.21 34.50 10.22 
(822.2) Observed 45.3 2.3 34.1 10.1 
______________________________________ 
(b) 0.1 parts by weight of the compound prepared according to (a) are 
dissolved in 4.7 parts by weight of acetone. This solution is suspended in 
95 parts by weight of water after the addition of 0.3 part by weight 
polyglycolalkylarylether. This suspension shows a very good effectivity 
against Fusicladium especially on apple seedlings. The Fusicladium-test is 
described in various U.S. patent specifications such as U.S. published 
patent application No. B 407,014 or in the U.S. Pat. No. 3,895,020 and in 
"Plant pathology" by George N. Agrios, Academic Press (New York). 
EXAMPLE 9 
0.7 parts by weight, of 2-imidazoline and 5.3 parts by weight, of p-tolyl 
isocyanate are stirred for 130 hours at 110.degree. C. in 10 parts by 
weight, of toluene. On cooling a colourless deposit is precipitated which 
is filtered off under suction and washed with toluene, giving 3.8 parts by 
weight, of the parabanic acid derivative: 
2,4-dioxo-1,3-di-p-tolyl-6,9-di-p-tolyl carbamoyl-1,3,6,9-tetraaza-spiro 
[4.4]-nonane, melting at 248.degree. C. 
EXAMPLE 10 
1.24 parts by weight, of hexahydrobenzimidazole and 7.52 parts by weight, 
of 3,4-dichlorophenyl isocyanate are stirred for 25 hours at 130.degree. 
C. in 10 parts by weight, of chlorobenzene. On cooling, a colourless 
deposit is precipitated and is filtered off under suction and washed with 
ether, giving 4.8 parts by weight, of the parabanic acid derivative: 
1,3-bis-(3,4-dichlorophenyl)-6,9-bis-(3,4-dichlorophenyl 
carbamoyl)-2,4-dioxo-1,3,6,9-tetraaza-7,8-tetramethylene-spiro 
[4.4]-nonane, melting at 246.degree. C.