PROCESS FOR PREPARING AMINO-PHENYL-UREAS AND AMINO- CARBANYLATES

PROCEDE D'OBTENTION D'AMINO-PHENYL-UREES ET D'AMINO- CARBANYLATES

English Abstract

ABSTRACT OF THE DISCLOSURE :
Process for preparing aminophenyl-ureas
and amino-carbanylates by direct amination of phenylureas
and carbanylates respectively by means of N-chloro-
amines, in a redox type system, in an acid reaction
medium.

Claims

The embodiments of the invention in which an
exclusive property or privilege is claimed are defined
as follows:
1. Process for preparing aminophenyl-ureas and
amino-carbanylates by direct amination of phenylureas and
carbanylates respectively by means of N-chloro-amines, in
a redox type system, in an acid reaction medium.
2. Process according to claim 1, characterized
in that there are employed N-chloro-amines having general
formula:
<IMG>
wherein:
R3 may be an alkyl, cycloalkyl, aralkyl;
R4 may be hydrogen or an alkyl, cycloalkyl, aralkyl;
R3,R4 may also form with N a piperidine ring.
3. Process according to claim 1, characterized
in that the phenyl-ureas employed have the general formula:
<IMG>
wherein:
R, R1, either like or unlike each other, may be hydrogen
or an alkyl, cycloalkyl, aryl, aralkyl;
R2 may be hydrogen or an alkyl, cycloalkyl, aryl, aralkyl;
27

A is a benzene ring either or not containing substi-
tuents, with at least a free position.
4. Process according to claim 1, characterized
in that aminophenyl-ureas having the following general formula
are obtained:
<IMG>
wherein:
R, R1, R2, R3, R4 and A have the meanings defined in claims
2 and 3 hereinbefore.
5. Process according to claim 1, characterized in
that the carbanylates employed have the following general
formula:
<IMG>
wherein:
R1 may be an alkyl, cycloalkyl, aryl, aralkyl;
R2 may be hydrogen, or an alkyl, cycloalkyl, aryl, aralkyl;
A is a benzene nucleus having at least a free position
and where the substituents present on R1, R2 and A
are selected from amongst the halogen, nitrile, sul-
phonic groups and esters thereof, the carboxylic
28

group and esters thereof, the amino, hydroxyl, alkoxyl,
alkoxyl-substituted, alkyl, alkyl-substituted,
acylamino, ureic, cycloalkyloxy groups.
6. Process according to claim 1, characterized
in that the amino-carbanylates having the following general
formula are obtained:
<IMG>
wherein :
R1, R2, R3, R4 have the same meanings as defined in claims
2 and 5 hereinbefore.
7. Process according to claim 1, characterized in
that the reaction medium contains a strong acid selected
from the group consisting of sulphuric acid, trifluoroacetic
acid and mixtures thereof with acetic acid, and a salt
selected from the group consisting of ferrous, cuprous and
titanous salts.
8. Process according to claim 7, characterized in
that the acid reaction medium contains ferrous sulphate.
9. Process according to claim 7, characterized
in that the acid reaction medium contains concentrated H2S04
or mixtures thereof with solvents, in which H2S04 is employed
at a concentration by weight equal to at least 25%.
29

10. Process according to claim 1, characterized
in that N-chloro-amine is employed in molar ratios comprised
between 1:3 and 3:1 in respect of phenyl-urea.
11. Process according to claim 8, characterized
in that ferrous sulphate is employed in molar ratios
comprised between 1:1 and 1:100 in respect of N-chloro-amine.
12. Process according to claim 11, characterized
in that ferrous sulphate is employed in molar ratios
comprised between 1:1.2 and 1:50 in respect of N-chloro-amine.

Description

~L~9Z~L~5
This invention relates to a particularly sirnple and
selective process for preparing amino-phenyl-ureas and arnino-
carbanylates.
- Such products are of great interest in the field of
the fine chemi~als and chiefly in that of the dyes, as they are
basic intermediates for the dyes synthesis. In particular they
are useful as herbicides and as coupling compounds in the
preparation of the azo dyes, as is described, for example, in
Belgian patent.s Ns. 694,733, 702,400 and 694,633.
The process of the present invention is prac-ticed by
treating the phenyl-ureas or the carbanylates in suitable acid
solvents, such as sulphuric acid, trifluoroacetic acid or
mixtures thereof with acetic acid, with a suited N-halogen
amine, and with a redox system containing salts, such as, e.g.,
ferrous, titanous or cuprous salts, at more or less low
temperatures, for example around the room temperature.
; The phenyl-ureas and the carbanylates can be substituted
at the nitrogen, for example, by alkyls, aralkyls, cycloalkyls,
aryls, optionally suhstituted. Also, phenyl can be substituted,
for instance, by halogens, alkyls, a nitro-group, a cyano-group,
a hydroxyl, an alkoxyl, optionally substituted.
The method of synthetising aromatic N-alkyl-amines
; by amination of aromatic substrates with N-chloro-amines, in
the presence of a reducing salt in an acid reaction medïum,
has been described in US patent N. 3,483,255, where aromatic
compounds either not substituted or monosubstituted with
chlorine, bromine, iodine, -OCH3 are alkylaminated.
It was expectable that, by operating according to said
method, N-chloro-ureas and chlorination products of the side
chains in the substituted ureas should form.
For the carbanylates-too it was expectable that, by
operating according to said method, by-products should form,
- 1 - '"~

~z~s
such as, e.g. N-chloro-carbanylates, chlorination products
of the side chains in the substituted carbanylates, and
furthermore that the carbanylates could be hydrolised in
the reaction conditions.
It has now been surprisingly found that the
new synthesis method of the present invention does not
cause the formation of the above-said products, but rather
is accompanied by high yields and a high selectivity for
preparing substituted aminobenzenes, either using phenyl-ureas or
carbanylates, or using phenyl-substituted phenyl-ureas and carbanylates~
It is an object of the present invention to
provide a particularly simple industrial process for the
production of substituted amino benzenes, which permits to
obtain products whose synthesis according to conventional
methods is usually very difficult.
Other objects of the invention will be
apparent from the discussion which follows.
In general, the process of this invention
relates to a process for preparing aminophenyl-ureas and
amino~carbanylates by direct amination of phenylureas and
carbanylates respectively by means of N-chloro-amines, in
a redox type system, in an acid reaction medium.
The reaction occurs in a very broad temper-
ature range: from -60 to +100C; good results are achieved
for example, between 0C and ~0C.
The molar ratios between N-chloro-amine and
aromatic substrate (phenyl-ureas or carbanylates) vary as a
function of the synthe5~s: generally they may range from 1:3 to 3:1.
The catalyst may vary in respect oE N-chloro-amine
.. ,,j
~J'

~0~2~S
from 1:1 to 1:100 by mols, according to the case, preferably
from 1:1,2 to 1:50.
Also with regard to the acid mixture, it is possible
to employ the most different ratios in respect of the aromatic
substrate~
A high selectivity and good yields can be achieved,
in several cases, by using 300 to 1000 ml for each mole of such
aromatic substrate.
Using H2S04, the best results are attained at a concentration
by weight of H2S04 equal to at least 25%.
A way of conducting the process is the following.
Into a reactor equipped with stirrer, thermometer, tap funnel
and cooler, there are introduced :
- the acid mixture
- the phenyl-urea of the carbanylate
- the N-chloro-amine dissolved in an acid mixture
- the catalyst.
At the conclusion of the reaction, the reactor
contents are poured onto ice, under stirring, and the starting
product, if still present, is extracted from the acid solution
by means of a proper solvent, for example chloroform, CC14,
ethyl acetate, ethyl ether, toluene, chlorobenzene, dichloro-
benzene, nitrobenzene, cyclohexane, etc.
After alkalinization with a concentrated al]caline sol-
ution, for example caustic soda at 30%, the reaction product
is extracted.
Use is made of the solvent most ~uitcd ~o each case, Tho
selection is essentially bound to the coefficient of distribution
of the product between solvent and aqueous solution.
Some employable solvents are, for example: chloroform,
carbon tetrachloride, ethyl ether, toluene, cyclohexane, etc.
After distillation of the solvent, the finished
-- 3 --

9212S
products are obtained generally at a purity degree already
useful for the successive uses. In some cases it may be useful
to effect a crystallization from a proper solvent or a frac-
tionated precipitation such as hydrochlori~e, sulphate, phosphate,
etc.
As N-halogen-amine it is possible to use, for instance:
- N-chloro-methyl amine
- N-chloro-dimethyl-amine
- N-chloro-methyl-ethylamine
- N-chloro-methyl-benzyl-amine
- N-chloro-diethyl-amine
- N-chloro-chloro-morpholine
- N-chloro-piperidine and the like.
Employable phenyl-ureas are, for example :
; - N-phenyl-urea
- N-methyl-N-phenyl-urea
- N-phenyl-N'-methyl-urea
- N-phenyl-N',N'-dime-thyl-urea
- N-methyl-N-phenyl-N'-methyl-urea
- N-methyl-N-phenyl-N',N'-dimethyl-urea
- N-phenyl-N'-ethyl-urea
- N-ethyl-N-phenyl-urea
- N-phenyl-N', N'-diethyl-urea
- N-ethyl-N-phenyl-N'ethyl- urea
- N-ethyl-N-phenyl-N',N'-diethyl-urea
- N-phenyl-N'-phenyl-urea
- N-methyl-N-phenyl-N'-phenyl-urea
- N-methyl-N-phenyl-N'-methyl-N'-phenyl-urea
- N-ethyl-N-phenyl-N'-phenyl-urea
- N-ethyl-N-phenyl-N'-ethyl-N'-phenyl-urea
- N-phenyl-N'-ethyl-N'-phenyl-urea
- N-methyl-N-phenyl-N',N'-diethyl~urea
-- 4 --

9Z~ZS
- N-methyl-N-phenyl-N'-methyl-N'-ethyl-urea
- N-ethyl-N-phenyl-N'-methyl-N'-ethyl-urea
- N-ethyl-N-phenyl-N',N' dimethyl-urea
- N-ethyl-N-phenyl-N'-methyl-N'-ethyl-urea
- N-phenyl-N'-phenyl-N'-methyl-urea
- N-phenyl-N'-ethyl-N'-phenyl-urea
- N-methyl-N-phenyl-N'-methyl-N'-ethyl-urea
- N-methyl-N-phenyl-N'-methyl-N'phenyl-urea
- N-methyl-N-phenyl-N'-ethyl-N'-phenyl-urea
- N-ethyl-N-phenyl-N'-methyl-N'-ethyl urea
- N-ethyl-N-phenyl-N'-methyl-N'phenyl-urea
- N-ethyl-N-phenyl-N'-ethyl-N'phenyl-urea
- N-2-nitro-phenyl-urea
- N-2-chloro-phenyl-urea
- N-2-bromo-phenyl-urea
- N-2-iodo-phenyl-urea
- N-2-methyl-phenyl-urea
: - N-2-isopropyl-phenyl-urea
- N-2-chloro-phenyl-N-methyl-N'-ethyl-urea
- N-2-methyl-phenyl-N',N'-dimethyl-urea
- M-2-methyl-phenyl-N'-2-methyl-phenyl-urea
- N-2-cyano-phenyl-urea
- N-2-acetoamino-phenyl-urea
- N-2-methoxy-phenyl-urea
- N-2-methoxy-phenyl-N',N'-dimethyl-urea
- N-2-methoxy-phenyl-N'-ethyl-urea
- N-2-methoxy-phenyl-N',N'-diethyl-urea
- - N-methyl-N-2-ethoxy-phenyl-urea
- N-2-hydroxy-phenyl-urea
- N-3-chloro-phenyl-urea
- N-3-methyl-phenyl-urea
- N-methyl-N-3-chloro-phenyl-urea

~Z~2S
- N-ethyl-N-3-chloro-phenyl-urea
- N-methyl-N-3-chloro-phenyl-N'-dimethyl-urea
- N-3-chloro-phenyl-N',N'-diethyl-urea
- N-3-methyl-phenyl-N',N'-diethyl-urea
- N-3-ethoxy-phenyl-urea or N-3-methoxy-phenyl-urea
- N-3-hydroxy-phenyl-urea
- N-2-tert.-butyl-phenyl-urea
- N-3-nethoxy-phenyl-N',N'-diethyl-urea
- N-methyl-N-3-methoxy-pherlyl-urea
- N-4-chloro-phenyl-urea
- N-4-methyl-phenyl-urea
- N-4-hydroxy-phenyl-urea
- N-4-methoxy-phenyl-urea
- N-4-ethoxy-phenyl-urea
- N-4-acetamino-phenyl-urea
- N-4-ureido-phenyl-urea
- N-ethyl-N-4-chloro-phenyl-N',N'-diethyl-urea
- N-methyl-N-4-methoxy-phenyl-urea
- N-4-methoxy-phenyl-N',N'-dimethyl-urea
- N-4-methoxy-phenyl-N'-ethyl-urea
- N-4-methoxy-phenyl-N'-methyl-urea
- N-methyl-N-4-methoxy-phenyl-N',N'-dimethyl-urea
- N-methyl-N-4-methoxy-phenyl-N',N'-diethyl-urea
- N-4-ethoxy-phenyl-N'-ethyl-urea
- N-4-ethoxy-phenyl-N',N'-dimethyl-urea
- N-ethyl-N-4-ethoxy-phenyl-N',N'-diethyl-urea
- N-2.5-dimethoxy-phenyl-urea
- N-2.5-dimethyl-phenyl-urea
- N-4-methoxy-phenyl~N'/4'-methoxy-phenyl-urea
- N-4-ethoxy-phenyl-N'-4'-ethoxy-phenyl-urea
- N-phenyl-N'-3',5'-dinitro-phenyl-urea
- N-4-methyl-phenyl-N'-3'-5'-dinitro-phenyl-urea
-- 6 --

~39Z12S
- N-~-ethoxy-phenyl-N'-3'-5'-dinitro-phenyl-urea
- N-4-methoxy-phenyl-N'-3'-5'-dinitro-phenyl-urea
- N-phenyl-N'-3'-5'-dicyano-phenyl-urea
- N-4-methyl-phenyl-N'-3'-5'-dicyano-phenyl-urea
- N-4-methoxy phenyl-N'-3'-5'-dicyano-phenyl-urea
- N-4-ethoxy-phenyl-N'-3',5'-dicyano-phenyl-urea
- N-phenyl-N'-3'-nitro-5'-cyano-phenyl-urea
- N-phenyl-N'-chloroethyl-urea
- N-phenyl-N'-cyanoethyl-urea
- N-phenyl-N'-sulphopropyl-urea
- N-phenyl-N'-hydroxyphentyl-urea
- N-phenyl-N'-ethoxy-valeryl-ùrea
- N-phenyl-N'-aminobutyl-urea
- N-methyl-N-phenyl-N'-hydroxypropyl-urea
- N-ethyl-N-4-ethoxy-phenyl-N'-sulphopropyl-urea
- N-4-ethoxy-phenyl-N'-cyanoethyl-urea
- N-4-(2-hydroxy-ethoxy)-phenyl-N'-hydroxy-ethyl-urea
- ~-methyl-N-4-methyl-propionatoxy-phenyl-N'-
chloroethyl-urea
- N-4-~2-hydroxy-ethoxy)-phenyl-urea
- N-4-methyl-pripionatoxy-phenyl-urea
- N-4-cyanoethoxy-phenyl-urea
- N-4-cyclohexoxy-phenyl-urea
- N-4-methoxy-pripionyl-oxy-phenyl-urea
- N-4-(2-ethoxy-ethoxy)-phenyl-urea
- N-4-isopropoxy-phenyl-urea
N-4 t-butoxy-phenyl-urea
- N-methyl-N-4-cyclohexoxy-phenyl-urea
- N-methyl-N-4-(2-hydroxy-ethoxy)-phenyl-urea
- N-ethyl-N-4-methyl-propionatoxy-phenyl-urea
- N ethyl-N-phenyl-N'-cyclohexyl-urea
- N-phenyl-N'-cyclohexyl-urea

~19~2~25
- N-4-methoxy-phenyl-N'-cyclohexyl-urea
- N-methyl-N-4-ethoxy-phenyl-N'-cyclohexyl-urea
-~ N-ethyl-N-4-methoxy-phenyl-N'-cyclohexyl-urea
- N-4-cyclohexoxy-phenyl-N'-cyclohexyl-urea
- N-ethyl-N-4-(2-hydroxy-ethoxy)-phenyl-N'-
cyclohexyl-urea
- N-methyl-N-phenyl-N'-ethyl-urea.
Employable carbanylates may be the derivatives of methyl
or ethyl carbanylate, such as ~or example:
- N-methyl-methyl carbanylate
- 4-methoxy-methyl carbanylate
- N-methyl-~-methoxy-methyl carbanylate
- N-ethyl-methyl carbanylate
- N-ethyl-4-methoxy-methyl carbanylate
- 2-nitro-methyl carbanylate
- 2-chloro-methyl carbanylate
- 2-bromo-methyl carbanylate
- 2-iodine-methyl carbanylate
- 2-methyl-methyl carbanylate
- 2-ethyl-methyl carbanylate
- 2-isopropyl-methyl carbanylate
- 2-tert.butyl-methyl carbanylate
- N-methyl-2-chloro-methyl carbanylate
- N-ethyl-2-methyl-methyl carbanylate
- 2-cyano-methyl carbanylate
- 2-methoxy-methyl carbanylate
- 2-hydroxy-methyl carbanylate
- 2-ethoxy-methyl carbanylate
- N-ethyl-2-ethoxy-methyl carbanylate
N-methyl-2-acetylamino-methyl carbanylate
- 3-chloro-methyl carbanylate
- 3-methyl-methyl carbanylate

)9;~ S
- 3-methoxy-methyl carba:nylate
- 3-hydroxy-methyl carbanylate
- 3-ethoxy-methyl carbanylate
- N-methyl-3-methoxy-methyl carbanylate
- N-methyl-3-methyl-methyl carbanylate
- N-ethyl-3-ethoxy-methyl carbanylate
~ N-ethyl-3-methoxy-methyl carbanylate
- 4-chloro-methyl carbanylate
- 4-methoxy-methyl carbanylate
- 4-methyl-methyl carbanylate
- 4-ethoxy-methyl carbanylate
- 2.5-dimethoxy~methyl carbanylate
- 2.5-dimethyl-methyl carbanylate
- 4(beta-hydroxy~-ethoxy-methyl carbanylate
- 4-methoxypropionyl-oxy-methyl carbanylate
- 4-(beta-cyano~-ethoxy-methyl carbanylate
- 4-cyclohexyloxy-methyl carbanylate
- 4-(beta-ethoxy)-ethoxy-methyl carbanylate
- 4-isopropyl-oxy-methyl carbanylate
- 4-t-butyl-oxy-methyl carbanylate
- N-cyclohexyl-methyl carbanylate
- N-ethyl-4-ethoxy-methyl carbanylate
- N-cyclohexyl-4-methoxy-methyl carbanylate
- N-ethyl-4-cyclohexyl-oxy-methyl carbanylate
- N-methyl-4-(beta-cyano)-ethoxy-methyl carbanylate
- N-ethyl-4-(beta-hydroxy)~ethoxy-methyl carbanylate
- N-methyl-4-methoxy-pripionyl-oxy-methyl carbanylate
- N-ethyl-4-(beta-ethoxy)-ethoxy-me-thyl carbanylate.
For the compounds listed hereinbefore it is understood
that the methyl of the ester group can be substituted by an
ethyl.
Other employable carbanylates are for exam~le :
_ g _

~LQ~2~XS
- beta-chloro-ethyl earbanylate
- beta-cyano-ethyl carbanylate
- propyl earbanylate
- isopropyl carbanylate
- tert.-butyl earbanylate
- eyelohexyl carbanylate
- beta-hydroxy-ethyl earbanylate
- beta-ehloro-ethyl N-methyl-earbanylate
- eyelohexyl N-ethyl-earbanylate
- eyclohexyl N-eyelohexyl-carbanylate
- beta-eyano-ethyl N-methyl-carbanylate
- propyl 4-methoxy-carbanylate
- tert.-butyl 4-methoxy-carbanylate
- isopropyl N-methyl-4-methoxy-carbanylate
- N-cyelohexyl-4-cyclohexyl-oxy-eyelohexyl earbanylate
- N-ethyl-4-ethoxy beta eyano-ethyl earbanylate.
The proeess for aminating phenyl~ureas ean be represent-
ed as follows:
~ _ e - N ~ \ R
N - I - N
Rl N
wherein :
- R and Rl, like or unlike eaeh other, may be hydrogen or an
alkyl, eyeloalkyl, aryl, arylkyl, optionally substituted,
- R2 may be hydrogen or an alkyl, eye].oalkyl, aryl, aralkyl,
-- 10 --

2~L25
optionally substituted;
- R3 and R4, like or unlike each other, may be alkyl, cyclo-
alkyl, aralkyl, optionally substituted and furthermore one
of the two, either R3 or R4, may be hydrogen. R3 and R4 may
also be the residue of a cyclo, optionally substituted,
containing or not containing other hetero-atoms;
- A is a benzene ring either or not containing substituents,
with at least a free position.
The substituents of Rl, R2, R3, R4 and A may be, for
example, halogen, nitrile, sulphonic, carboxylic groups and
esters thereof, amino-hydroxyl, alkyl, alkyl-substituted,
alkoxyl, alkoxyl-substituted, acylamino, cycloalkyloxy, ureic
groups, etc.' in particular the substituents of the alkyl and
alkoxyl groups may be, for example, halogen, hydroxyl, carboxylic,
sulphoric groups and esters thereof, a nitrile, an alkoxyl.
When Rl, R2, R3 and R4 mean an alkyl or an alkoxyl,
their alkyl chains contain preferably 1 to 5 carbon atoms.
The process for aminating the carbanylates with N-
chloro-amines can be represented as follows:
O O R
\ / ~ ~> + Cl - N~ ~0 ,N~
wherein :
Rl, R2 may be, for example, an alkyl or cycloalkyl, an aryl,
an aralkyl, optionally substituted;
30 R2 may be also hydrogen,
R3, R4 may, for example, an alkyl or cycloalkyl, an aralkyl,
optionally substituted, and furthermore one of the two

Z~,Z~
may be also hydrogen,
R3, R4 may constitute the residue of a cyclo, optionally
substituted, either or not containing hetero-atoms;
A is a benzene nucleus, having at least a free position.
The substituents of Rl, R2, R3, R4 and A, may be, for
example, halogen, nitrile, sulphonic, carboxylic groups and
esters thereof, amino, hydroxyl, alkyl, alkyl-substituted,
alkoxyl, alkoxyl-substituted, acylamino, cycloalkyloxy, ureic
groups, etc.; furthermore the substituen-ts of the alkyls and
alkoxyls may be, for instance, halogen, hydroxyl, carboxylic,
sulphonic groups and esters thereof, nitrile, oxygen-alkyl.
When Rl, R2, R3, R~ mean an alkyl or an alkoxyl,
their alkyl chains contain preferably from 1 to 5 carbon atoms.
In accordance with the process of this invention when
a substituted benzene reactant is a phenyl urea type, such as:
N-phenyl-urea
; N-phenyl-N'-ethyl-urea
N-methyl-N-phenyl-N',N'-dimethyl-urea
N-methyl-N-phenyl-N'-ethyl-urea
a selective linking in para position in respect of nitrogen
in A is obtained.
If phenyl is substituted in para position, i.e. if
products of the following type are used:
N-4-methoxy-phenyl-urea
N-4-methoxy-phenyl-N'-ethyl-urea
N-4-ethoxy-phenyl-N'-ethyl-urea
N-4-hydroxy-phenyl-urea
N-4-cyclohexoxy-phenyl-N',N'-dimethyl-urea
N-methyl-N-4-chloro-phenyl-urea
N-4-ethoxy-phenyl-N',N'-dimethyl-urea
a selective linking in meta position in respect of N in A is
obtained.
- 12 -

~0~2~S
Conversely, if phenyl is substi-tuted in ortho position,
i.e. if products of the following -type are used:
N-2-methyl-phenyl-urea
N-2-methyl-phenyl-N',N'-dimethyl-urea
N-2-chloro-phenyl-N'-ethyl-urea
~-methyl-N-2-bromo-phenyl-urea, etc.
a selective linking in para position in respect o nitrogen in
A is obtained.
As to the carbanylates, when starting products such as:
methyl carbanylate
ethyl carbanylate
N-methyl-ethyl carbanylate
N-ethyl-methyl carbanylate
are used, a selective linking in para position in respect of
nitrogen in A is obtained.
If phenyl is substituted in para position, i.e. if
products of the following type are utilized:
4-methoxy-methyl carbanylate
~ 4-ethoxy-methyl carbanylate
4-methoxy-ethyl carbanylate
4-ethoxy-ethyl carbanylate
N-methyl-4-methoxy-methyl carbanylate,
a selective linking in meta position in respect of nitrogen
in A is obtained.
Conversely, if phenyl is substituted in ortho position,
i.e. if products such as the following ones are used:
2-methyl-methyl carbanylatc
2-chloro-ethyl carbanylate
2-methyl-ethyl carbanylate
a selective linking in para position in respect of nitrogen
in A is obtained.
The following examples are given merely to illustrate

1~1392~Z5
the present invention and are not intended to limit more
general aspects thereof.
In such examples, unless otherwise specified, the term "parts"
is to be understood as expressed in units by weight.
For the examples relating to phenyl-ureas, the yield is cal-
culated on the amount of N-chloro-amine used, while for the
examples concerning the carbanylates, the yield is calculated
on the amount of converted carbanylate.
A) Preparation of amino-phenyl-ureas
EXAMPLE 1
Into a reactor equipped with stirrer, cooler, thermo-
meter and dropping funnel, 60 parts of concentrated H2S04 were
charged and, keeping the temperature below 10C, 8.2 parts of N-
phenyl-N'-ethyl-urea were charged.
Successively, under stirring, there were added thereto 41.7
parts of a sulphuric solution of N-chloro-dimethyl-amine at
9.65%, corresponding to 4 parts at 100%.
7 parts of FeS04.7H20 were then charged batchwise.
It was allowed to react for 2 hours, whereupon the reactor
contents were poured onto 150 parts of minced iceO
After extraction with chloroform, the solven-t was distilled
and 2.4 parts of starting product were obtained.
Waters were alkalized with 30% NaOH and, after extraction
with chloroform, the solvent was distilled, thus obtaining
7.7 parts of N-para-dimethylamino-phenyl-N'-ethyl-urea at
a titre of 93.4%. Yield: ahout 69.5%. Melting point =
154-156.5C.
EXAMPLE 2
Into a reactor like that of example 1, there were
charged: 23.8 parts of a sulphuric solution of N-chloro-piper-
idine at 25.2% corresponding to about 6 parts at 100%,
60 parts of concentrated H2SO~
- 14 -

2~L2S
and, keeping the -temperature below 0C, ~.2 parts of N-phenyl-
N'-ethyl-urea were added thereto.
7 parts of FeSo~.7H20 were then charged batchwisev
It was reacted for 2 hours, whereupon the reactor contents
were poured onto 150 parts of minced ice.
After extraction with chloroform, the solvent was distilled
and 2.9 parts of starting product were obtained.
8.9 parts of N-para-piperidino-phenyl-N'-ethyl-urea at a titre
of 90.2% were obtained. Yield = 65%, melting point = 162.5-
164.5C.
EXAMPLE 3
Into a reactor like that of example 1, 150 parts
of concentrated H2S04 were charged.
ICeeping the temperature below 20C, 19.4 parts of N-4-methoxy-
phenyl-N'-ethyl-urea were charged.
Then, under stirring, 37.5 parts of a sulphuric solution of
N-chloro-dimethyl-amine at 21.2%, equal to about 8 parts at
100%, were added thereto.
14 parts of FeS04.7 H20 were successively added batchwise.
It was allowed to react for 2 hours, whereupon the reactor
contents were poured onto 300 parts of minced ice.
After extraction with chloroform, the solvent was distilled
and 1.7 parts of starting product were obtained.
After alkalinization with 30% NaOH, extraction with chloro-
form and distillation of the solvent, there were obtained:
22.3 parts of N-3-dimethylamino-4-methoxy-phenyl-N'-ethyl-
urea at a titre of 94%.
Yield : about 90%, melting point = 114.5 - 115.5C.
EXAMPLE 4
Into a reactor like that of example 1, 60 parts of
concentrated H2S03 were charged and, keeping the temperature
below 10C, 9 parts of N-4-ethoxy-phenyl-urea were added thereto.

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Under stirring, there were then char~ed : 40 parts of a sul-
phuric solution of N-chloro-dimethyl-amine a-t 9.94%, corres-
ponding to about 4 parts at 100C.
6 parts of FeC12 were then charged batchwise.
Following the modalities of exarnple 1, there were obtained :
9 parts of N-3-dimethyl-amino-4-ethoxy-phenyl-urea at 94.7%.
Yield : 76.4%, melting point = 134 - 137C.
EXAMPLE 5
Into a reactor like that of e~ample 1, 50 parts of
concentrated H2S03 were charged and, keeping the temperature
below -5C, 10.4 parts of N-4-ethoxy-phenyl-N',N'-dimethyl-urea
were added~ Successively, 4 parts of N-chloro-dimethyl-amine,
dissolved in 35 parts of concentrated H2S04, were charged under
stirring.
3.5 parts of FeS04.7 H20 were then charged batchwise.
By operating similarly to example 1, it was possible to ob-
tain 9.6 parts of N-3-dimethyl amino-4-ethoxy-phenyl N',N'-
dimethyl-urea at a titre of 94.4%.
Yield = 72%; melting point = 129 - 131.5C.
By operating analogously with example 3, the following products
were prepared :
Ex.No. Acid Catalyst Formula Chromato-
mixture graphic
analysis
OCH3 /CH2-CH2
, \CH Eluent N
6 96% H2S04 FeS04.7H20 ~ \CH CH / R.F~=0.5
Unitary
/ N \
H C=0
/N \
H C2H5
- 16 -

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OC2H5
/C2H5 R.F.= 0.1
796% H2S04 FeS04^7H2 ~ \C2H5 Unitary
,~N\
H C=0
NH2
OC2H5
I~CH2-CH ~ Eluent N.l
896% H2SO4 FeS04O7H20 j C 2 CH~ R F = 0.1
~N \
H C=0
NH2
C2H5 / CH3 R.F.= 0.1
996% H2SO4 FeS04~7~I2 ~ - ~ \ Unitary
H C=0
NH2
I /CH2-CH2\ Eluent N.l
10 6% 2S04 Fe 4 7 2 ~ ~ CH -CH " 2 Unitary
H~N~C o
/ N \
CH3 CH3
/ H
CH3 C-N
\ N/ 2 5 Eluent N.l
I R.F.= 0.65
2 44 2 ~ Unitary

9Zl;~5
CH CH3
N-C-N~ Eluent N. 1
¦ ~CH3 R.F.= 0.65
2 4 4 2 ~ Unitary
N _
CH3 CH3
H
H ~ C-N
~N o \ C H Eluent N.l
13 conc. H2S04 FeS04.7H20 ~ _ CH3 R F = 0.2
CH3 \CH3
H C-N Eluent N. 1
\N/ \C2H5 R F =0 2
14 conc- H2S04 e 4 2
,N \
CH3 CH3
C-N
N C2H5
I Eluent N. 2
15 conc. H2S0 = 80 FeS04.7H20 ~ CH3 R F - 0 1
Acetlc acld 20 I CH3
. OCH3
- 18 _

:~0~2~L25
H O H
11 /
N-C-N Eluent N. 1
C2H5 R.F.= 002
16 conc. H2S0~ TiC13 ~ Unitary
/ \ .,
CH3 CH3
All the products were diluted on silicic acid.
Eluent N. 1 : benzene = 79 parts, methanol = 14 parts,
acetic acid = 7 parts.
Eluent N.2: toluene = 50 parts, ethyl acetate = 50 parts.
The product of example N. 15 exhibited the same melting
point and the same spectra as the one obtained in example N. 3.
The product of example N. 16 exhibited the same melting point
and the same spectra as the one obtained in example N. 1.
B) Preparation of amino-carbanylates
EXAMPLE 1
Into a reactor equipped with stirrer, cooler, thermo-
meter and dropping funnel there were charged :
60 parts of concentrated H2S04
and, keeping the temperature below 0C, there were charged-
9.75 parts of 4-methoxy-ethyl carbanylate.
Under stirring, the following was then added :
19.1 parts of a sulphuric solution of N-chloro-dimethyl-
amine at 20.8%, corresponding to about 4 parts at 100%.
7 parts of FeS04.7H20 were then charged batchwise.
It was allowed to react for 2 hours, whereupon the reactor
contents were poured onto 150 parts of minced ice.
After extraction with chloroform, the solvent was distilled
and 3.68 parts of unreacted product were obtained.
Waters were alkalized with 30% NaOH and, after extraction with
chloroform, the solvent was distilled, thus obtaining
7.26 parts of 3-N,N-dimethyl-amino-4-methoxy ethyl carbanylate

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acid at a titre of 90.7%. Yield ~ 95%.
The product eluted on salicylic acid exhibited a R.F. of
0.5 with the eluent consisting of 50 parts of toluene, 50
parts of ethyl acetate, and a R.F. of 0.5 with the eluent
consisting of 79 parts of benzene, 14 parts of methanol,
7 parts of acetic acid.
By operating according to example 1, but varying the starting
materials, i.e. the type of carbanylate and of chloro-amine,
the following products were prepared:
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