Production of urethane compounds

A process for producing a urethane compound which comprises reacting at least one compound selected from the group consisting of a primary amine, a secondary amine and a urea compound with carbon monoxide and an organic hydroxyl compound in the presence of a catalyst system comprising: PA0 (a) at least one member selected from the group consisting of platinum group metals and compounds containing at least one platinum group element; and PA0 (b) at least one halogen-containing compound selected from the group consisting of alkali or alkaline earth metal halides, onium halides, compounds capable of forming onium halides in the reaction, oxo acids of halogen atoms and their salts, complex compounds containing halogen ions, organic halides and halogen molecules, in the presence of molecular oxygen and/or an organic nitro compound as an oxidizing agent at a temperature of from about 80.degree. C. to about 300.degree. C. under a pressure of from about 1 Kg/cm.sup.2 to about 500 Kg/cm.sup.2.

DESCRIPTION 
1. Technical Field 
This invention relates to the production of urethane compounds. More 
particularly, it relates to processes for producing urethane compounds by 
oxidative carbonylation which comprise reacting at least one compound 
selected from the group consisting of a primary amine, a secondary amine 
and a urea compound with carbon monoxide and an organic hydroxyl compound 
in the presence of an oxidizing agent and a specified catalyst system. 
2. Background Art 
Urethane compounds are important compounds useful for carbamate type 
agricultural medicines, and for conversion to isocyanate compounds by 
thermal decomposition. Such compounds have heretofore been available 
principally by reactions involving dangerous phosgene. Thus, it is desired 
to produce urethane compounds as the starting materials for the production 
of isocyanate compounds without using phosgene, and to do so at low cost. 
Heretofore, there have been proposed mainly two methods for the production 
of urethane compounds using carbon monoxide. More specifically, one method 
comprises reductively urethanating a nitro compound in the presence of an 
alcohol. For example, in the case of nitrobenzene, the reaction may be 
represented by the following equation: 
##STR1## 
wherein R represents an organic group. 
In this reaction, however, 3 mols of carbon monoxide are required per mol 
of nitrobenzene and two mols of the carbon monoxide are converted to 
carbon dioxide of no value. Thus, a disadvantage of the process is that 
only 1/3 of carbon monoxide is effectively employed. Moreover, in order 
continuously to carry out this reaction, carbon dioxide must be separated 
from a gaseous mixture of carbon monoxide and carbon dioxide. This 
compounds the difficulties of commercial practice of the method. 
The other method comprises oxidatively urethanating by reacting a primary 
amino compound or a N,N'-disubstituted urea with carbon monoxide and an 
alcohol in the presence of oxygen or an oxidizing agent such as an organic 
nitro compound. This method has advantages compared to the above described 
method since carbon monoxide is effectively utilized. However, it is 
required that a chloride of an element which is a Lewis acid and yet 
capable of performing redox reaction, such as cupric chloride, ferric 
chloride, iron oxychloride, vanadium chloride and vanadium oxychloride, be 
dissolved in the reaction system as a promoter (see U.S. Pat. No. 
4,297,501; European Pat. No. 36,895; and U.S. Pat. No. 4,304,922). 
Solutions of these chlorides are highly corrosive to metallic materials of 
reaction vessels, pipelines and valves. As a result, expensive metallic 
materials must be used. Further, when an aromatic urethane compound is 
produced, complicated and expensive procedures are required for the 
separation and recovery of these chlorides which are dissolved in the high 
boiling aromatic products such as aromatic urethanes or diarylureas. In 
addition, these promoters cannot be completely regenerated even by 
reoxidation in the reaction system since the hydrogen chloride formed in 
the redox reaction is converted to a hydrochloride of unreacted amine. As 
a result, there is partially reduced catalyst in the catalyst recovered. 
Therefore these promoters must be freshly prepared for each reaction. 
Thus, there has been an urgent need to develop a new process which will 
avoid the above described problems, and extensive studies have been 
conducted to achieve this result. 
DISCLOSURE OF THE INVENTION 
The present invention in one embodiment provides processes for producing 
urethane compounds which comprise reacting at least one compound selected 
from the group consisting of a primary amine, a secondary amine and a urea 
compound with carbon monoxide and an organic hydroxyl compound in the 
presence of a catalyst system comprising: 
(a) at least one member selected from the group consisting of platinum 
group metals and compounds containing at least one platinum group element; 
and 
(b) at least one halogen-containing compound selected from the group 
consisting of alkali or alkaline earth metal halides, onium halides, 
compounds capable of forming onium halides in the reaction, oxo acids of 
halogen atoms and their salts, complex compounds containing halogen ions, 
organic halides and halogen molecules, 
in the presence of molecular oxygen and/or an organic nitro compound as an 
oxidizing agent at a temperature of from about 80.degree. C. to about 
300.degree. C. at a pressure of from about 1 Kg/cm.sup.2 to about 500 
Kg/cm.sup.2. 
The present invention in another embodiment provides processes for 
producing urethane compounds which comprise reacting at least one compound 
selected from the group consisting of a primary amine, a secondary amine 
and a urea compound with carbon monoxide and an organic hydroxyl compound 
in the presence of a catalyst system comprising (c) a basic substance as 
an additional promoter in addition to the above described components (a) 
and (b) in the presence of molecular oxygen or an organic nitro compound 
at a temperature of from about 80.degree. C. to about 300.degree. C. at a 
pressure of from about 1 Kg/cm.sup.2 to about 500 Kg/cm.sup.2. 
Using the catalyst systems of this invention, urethane compounds can be 
obtained from primary or secondary amines and urea compounds with a high 
selectivity and a high yield. 
In the catalyst system of this invention, the halogen atom in the 
halogen-containing compound plays an important role as a promoter. The 
preferred halogen atoms are bromine and iodine, and iodine is more 
preferred. 
Such a fact is entirely unexpected from the prior art documents as 
described above (U.S. Pat. No. 4,297,501; European Pat. No. 36,895 and 
U.S. Pat. No. 4,304,922). 
More specifically, in the prior art references a catalyst comprising, as 
the main catalyst, a platinum group compound and, as a promoter, a 
chloride of an element capable of performing redox reaction in the 
reaction system is employed. As the representative example there is 
described a combination of palladium chloride and ferric chloride or a 
trivalent iron such as iron oxychloride. In such a system, the principal 
product of urethane compound may be considered to be produced according to 
the so called Wacker reaction type catalyst cycle wherein divalent 
palladium participates in the reaction and is reduced as the reaction 
progresses to zero valence palladium which is then re-oxidized with 
trivalent iron to form divalent palladium simultaneously with reduction of 
trivalent iron to divalent iron, which divalent iron is oxidized again 
with an oxidizing agent to be returned to trivalent iron. 
Thus, in the method of the prior art references it is apparent that the 
chloride of an element which will undergo redox action in the reaction 
system is essential as the re-oxidizing agent for the main catalyst. As 
the element having such a function, there are mentioned those susceptible 
of redox reaction selected from the elements of Group IIIa to Va and Group 
Ib to VIIIb in the Periodic Table, more specifically, such as copper, 
zinc, mercury, thallium, tin, titanium, arsenic, antimony, bismuth, 
vanadium, chromium, molybdenum, tungsten, manganese, iron, cobalt and 
nickel. Of these elements, only copper, vanadium, manganese, molybdenum, 
tungsten, antimony and iron are employed for the urethanation of an 
aromatic primary amine or an aromatic urea compound. There is no example 
for the urethanation of an aliphatic or alicyclic primary or secondary 
amine or an urea compound. 
In contrast, the method of this invention employs specifically selected 
halogen-containing compounds and, if necessary or if desired, a basic 
substance as an additional promoter. It is completely unnecessary to 
employ a metal element such as described above which will undergo redox 
action in the reaction system. It is rather preferred not to utilize such 
heavy metals for more smoothly advancing the reaction. Furthermore, in the 
previously known processes a chlorine ion is essential as an activator of 
the metal element having redox action, while in the reaction of the 
present invention, chlorine is not essential. In fact, bromine and iodine 
are preferred and iodine is especially preferred since bromine and iodine 
appear to give higher yields, and iodine gives the highest. For these 
reasons, the reactions of this invention are clearly different from the 
reaction disclosed in the prior art. 
It may be possible that the halogen-containing compound according to this 
invention contain the above described elements as one constituting 
component. 
The mechanism by which the halogen-containing compound which can be 
employed in this invention participates in the reaction is not clear. 
However, in combination with platinum group metals or compounds containing 
platinum group elements, they clearly play important roles as the catalyst 
components for the oxidative urethanation of primary and secondary amines 
and urea compounds. This is apparent from the fact that when only the 
halogen-containing compound is used or such a compound in combination with 
a basic substance as an additional promoter, the urethanation reaction 
does not take place. Also, if only the platinum group metal or a compound 
containing the platinum group element is employed, the urethanation hardly 
proceeds under the reaction conditions of this invention, or if there is a 
reaction, only a small amount of urethane compound is produced. 
Particularly, when only a metallic platinum group metal is used, harly any 
urethane compound is obtained. For example, with the use of palladium 
black alone which is a metallic palladium with zero valency, there is 
practically no reaction although palladium is one of the more effective 
catalyst components when employed in accordance with the reaction of this 
invention. However, together with a halogen-containing compound such as 
cesium iodide or tetramethylammonium iodide or with a combination of the 
halogen-containing compound and a basic substance such as a combination of 
iodine and trimethylamine, or a combination of iodoform and rubidium 
hydroxide, it is possible to obtain close to a quantitative yield of 
urethane compound. There is a particular advantage of the processes of 
this invention compared to the known processes in which a platinum group 
metal or compound is employed together with a Lewis acid such as ferric 
chloride. In the prior art process, the platinum or platinum group 
compound is eluted out with the acid into the reaction mixture. Recovery 
is a cumbersome and expensive procedure. In contrast, according to the 
method of this invention, substantially no platinum group metal is eluted 
out into the reaction mixture and thus, the expensive platinum group 
catalyst components can easily be separated and recovered, for example, by 
filtration. The importance of this advantage in commercial practice will 
be readily apparent to those skilled in the art. 
The use of a basic substance as an additional promoter markedly improves 
the yield and the selectivity of urethane compounds in accordance with the 
process of this invention. 
Any of a large selection of platinum group metals or compounds containing a 
platinum group element can be used in the process of the present 
invention. These include, for example, palladium, rhodium, platinum, 
ruthenium, iridium and osmium, metal blacks thereof and compounds 
containing these elements. These catalysts may be supported on any of a 
number of known carriers such as active carbon, graphite, silica, alumina, 
silica-alumina, silica-titania, titania, zirconia, barium sulfate, calcium 
carbonate, asbestos, bentonite, diatomaceous earth, polymers, ion-exchange 
resins, zeolite, molecular sieve, magnesium silicate and magnesia. 
Metallic catalysts may be prepared by supporting compounds containing these 
metal ions on a carrier and reducing them with hydrogen or formaldehyde. 
Alloys and intermetallic compounds containing these metals may also be 
employed. These may include those between these platinum group metals or 
those containing other elements such as selenium, tellurium, sulfur, 
antimony, bismuth, copper, silver, gold, zinc, tin, vanadium, iron, 
cobalt, nickel, mercury, lead, thallium, chromium, molybdenum and 
tungsten. 
Exemplary compounds containing platinum group elements which may be 
employed include inorganic acid salts such as the halides, sulfates, 
nitrates, phosphates and borates; organic acid salts such as the acetates, 
oxalates and formates; cyanides; hydroxides; oxides, sulfides; metal acid 
salts containing an anion such as a nitro group, a cyano group, a halogen 
atom and an oxalate ion; metal complexes with salts or complexes 
containing ammonia, an amine, a phosphine and a carbon monoxide ligand; 
and organometallic compounds having an organic ligand or an organic group. 
Of these catalyst components, those containing palladium or rhodium or both 
are particularly preferred. Suitable examples of such components include 
Pd black; carrier-supported palladium catalysts such as Pd-C, Pd-Al.sub.2 
O.sub.3, Pd-SiO.sub.2, Pd-TiO.sub.2, Pd-ZrO.sub.2, Pd-BaSO.sub.4, 
Pd-CaCO.sub.3, Pd-asbestos, Pd-zeolite and Pd-molecular sieve; alloys and 
intermetallic compounds such as Pd-Pb, Pd-Se, Pd-Te, Pd-Hg, Pd-Tl, Pd-P, 
Pd-Cu, Pd-Ag, Pd-Fe, Pd-Co, Pd-Ni and Pd-Rh and these alloys and 
intermetallic compounds supported on the carrier as described above; 
inorganic acid salts such as PdCl.sub.2, PdBr.sub.2, PdI.sub.2, 
Pd(NO.sub.3).sub.2 and PdSO.sub.4 ; organic acid salts such as 
Pd(OCOCH.sub.3).sub.2 and palladium oxalate; Pd(CN).sub.2 ; PdO; PdS; 
palladium acid salts represented by M.sub.2 (PdX.sub.4) and M.sub.2 
(PdX.sub.6) wherein M represents an alkali metal, an ammonium ion, a nitro 
group or a cyano group and X represents a halogen atom; amine complexes 
represented by [Pd(NH.sub.3).sub.4 ]X.sub.2 and [Pd(en).sub.2 ]X.sub.2 
where X is the same as defined above and en represents ethylenediamine; 
complex compounds or organometallic compounds such as PdCl.sub.2 
-(PhCN).sub.2, PdCl.sub.2 (PR.sub.3).sub.2, Pd(CO)(PR.sub.3).sub.3, 
Pd(PPh.sub.3).sub.4, PdCl(R)-(PPh.sub.3).sub.2, Pd(C.sub.2 
H.sub.4)(PPh.sub.3).sub.2 and Pd(C.sub.3 H.sub.5).sub.2 where R represents 
an organic group and Ph represents a phenyl group; complex compounds 
having a coordinated chelate ligand such as Pd(acac).sub.2 where acac 
represents an acetylacetonato group; rhodium black; carrier-supported 
rhodium catalysts similar to those of Pd; rhodium alloys and intermetallic 
compounds which may be supported on a carrier similar to those of Pd; 
inorganic acid salts such as RhCl.sub.3 and its hydrates, RhBr.sub.3 and 
its hydrates, RhI.sub.3, its hydrates and Rh.sub.2 (SO.sub.4).sub.3 and 
its hydrates; Rh.sub.2 (OCOCH.sub.3).sub.4, Rh.sub.2 O.sub.3, RhO.sub.2, 
M.sub.3 (RhX.sub.6) and hydrates thereof wherein M and X are the same as 
defined above; amine complexes of rhodium such as [Rh(NH.sub.3).sub.5 
]X.sub.3 and [Rh(en).sub.3 ]X.sub.3 ; rhodium carbonyl clusters such as 
Rh.sub.4 -(CO).sub.12 and Rh.sub.6 (CO).sub.16 ; complex compounds or 
organometallic compounds such as [RhCl(CO).sub.2 ].sub.2, RhCl.sub.3 
(PR.sub.3).sub.3, RhCl(PPh.sub.3 ).sub.3, RhX(CO)L.sub.2 where X is the 
same as defined above, L is a ligand comprising an organic phosphorous 
compound and an organic arsenic compound and Ph is a phenyl group; and 
RhH(CO)(PPh.sub.3).sub.3 where Ph is a phenyl group. In this invention 
there may be employed either one kind of these platinum group metals or 
compounds containing platinum group elements or a mixture of two or more 
kinds thereof. 
The amount of the platinum group element or compound containing a platinum 
group element which may be employed in this invention is not particularly 
limited. The amount of the platinum group element per se or in its 
compound is typically about 0.0001 to about 50% by mol per mol of the 
primary amine, secondary amine and/or urea compound employed. 
The halogen-containing compounds which can be used in this invention 
include alkali metal halides, alkaline earth metal halides, onium halides, 
compounds capable of forming onium halides in the reaction, oxo acids of 
halogen atoms and their salts, complex compounds containing halogen ions, 
organic halides and halogen molecules. 
Exemplary alkali metal halides and alkaline earth metal halides include 
single salts such as sodium fluoride, cesium fluoride, barium fluoride, 
lithium chloride, sodium chloride, potassium chloride, rubidium chloride, 
cesium chloride, magnesium chloride, calcium chloride, strontium chloride, 
barium chloride, lithium bromide, sodium bromide, rubidium bromide, cesium 
bromide, magnesium bromide, strontium bromide, barium bromide, lithium 
iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, 
magnesium iodide, calcium iodide, strontium iodide, and barium iodide; 
double salts such as sodium magnesium chloride, potassium magnesium 
chloride, potassium calcium chloride and potassium magnesium bromide; and 
polyhalides such as potassium bromofluoride, potassium iodochloride, 
rubidium iodochloride, cesium iodochloride, cesium iodochlorobromide, 
rubidium iodochlorobromide, potassium iodobromide, cesium iodobromide and 
rubidium iodobromide. 
The onium halide means a compound containing an element having a lone pair 
of electrons in which a proton or another cation type reagent is bonded to 
the lone pair of electrons to increase one covalent bond valency of the 
element having the lone pair of electrons to become a cation, and having a 
halogen anion electrovalently bound as the counter ion. 
Exemplary onium halides include ammonium compounds of the formula (R.sup.1 
R.sup.2 R.sup.3 R.sup.4 N.sup..sym.)X.sup..crclbar., phosphonium compounds 
having the formula (R.sup.1 R.sup.2 R.sup.3 R.sup.4 
P.sup..sym.)X.sup..crclbar., arsoium compounds having the formula (R.sup.1 
R.sup.2 R.sup.3 R.sup.4 As.sup..sym.)X.sup..crclbar., stibonium compounds 
having the formula (R.sup.1 R.sup.2 R.sup.3 R.sup.4 
Sb.sup..sym.)X.sup..crclbar., oxonium compounds having the formula 
(R.sup.1 R.sup.2 R.sup.3 O.sup..sym.)X.sup..crclbar., sulfonium compounds 
having the formula (R.sup.1 R.sup.2 R.sup.3 S.sup..sym.)X.sup..crclbar., 
oxysulfonium compounds having the formula [R.sup.1 R.sup.2 R.sup.3 
S.sup..sym. (O)]X.sup..crclbar., selenonium compounds having the formula 
(R.sup.1 R.sup.2 R.sup.3 Se.sup..sym.)X.sup..crclbar., telluronium 
compounds having the formula (R.sup.1 R.sup.2 R.sup.3 
Te.sup..sym.)X.sup..crclbar., stannonium compounds (R.sup.1 R.sup.2 
R.sup.3 Sn.sup..sym.)X.sup..crclbar. and iodonium compounds having the 
formula (R.sup.1 R.sup.2 I.sup..sym.)X.sup..crclbar.. In these formulae, 
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each independently represents a 
hydrogen atom or a group selected from the group consisting of aliphatic 
groups, aromatic groups, alicyclic groups, arylaliphatic groups and 
heterocyclic groups which may sometimes be a constituent of a ring 
containing an element having a lone pair of electrons; and X represents a 
halogen atom selected from the group consisting of F, Cl, Br and I. 
Compounds having two or more of such onium groups in the molecule and 
further polymers containing such onium groups in the main chain or a side 
chain thereof may also be employed. 
Such onium halides where a halogen is an anion can readily be obtained by 
the reaction of a hydrogen halide or an organic halide with the 
counterpart amine, nitrogen-containing compound, phosphine compound, 
arsine compound, stibine compound, oxy compound, sulfide compound, 
sulfoxide compound, selenide compound or telluride compound. These onium 
halides may be formed either outside the reaction system or in the 
reaction system. Furthermore, the onium halides prepared according to 
other methods may also be available and they may be formed in the reaction 
system according to other methods. 
Of these onium halides, ammonium halides, phosphonium halides, arsonium 
halides and sulfonium halides are preferred, and ammonium halides and 
phosphonium halides are the most preferred. An ammonium halide can be 
readily obtained by the reaction of a corresponding nitrogen-containing 
compound with a hydrogen halide or the reaction of a nitrogen-containing 
compound with an alkyl halide or an aryl halide. Such nitrogen-containing 
compounds include, for example, ammonia, amines such as primary amines, 
secondary amines and tertiary amines, hydroxylamines, hydrazines, 
hydrazones, amino acids, oximes, imidoesters, amides and various 
nitrogen-containing heterocyclic compounds. 
Exemplary hydrogen halide salts of nitrogen-containing compounds which can 
be employed include the salts of ammonia such as ammonium chloride, 
ammonium bromide and ammonium iodide; the salts of aromatic amines such as 
diphenylamine and triphenylamine; the salts of aliphatic amines such as 
methylamine, ethylamine, n-hexylamine, n-octylamine, dimethylamine, 
trimethylamine, diethylamine, triethylamine, di-n-butylamine, 
tri-n-propylamine, methylethylamine, dimethylethylamine, 
di-n-butylmethylamine, tri-n-butylamine, ethylenediamine and 
hexamethylenediamine; the salts of alicyclic amines such as 
cyclopropylamine, cyclohexylamine and N-methylcyclohexylamine; the salts 
of arylaliphatic amines such as benzylamine, N-methylbenzylamine, 
N,N-diethylbenzylamine and dibenzylamine; the salts of nitrogen-containing 
heterocyclic compounds such as piperidine, piperazine, morpholine, 
pyridine, quinoline, hexamethyltetramine, oxazole, thiazole, imidazole, 
triazole, benzotriazole and diazabicycloundecene; and the salts of amides 
such as dimethylacetamide and N-methylpyrrolidone. 
Exemplary quaternary ammonium halides which can be employed include 
aliphatic quaternary ammonium halides such as tetramethylammonium halides, 
tetraethylammonium halides, tetra-n-butylammonium halides, 
trimethylethylammonium halides, diethyldibutylammonium halides; alcyclic 
quaternary ammonium halides such as N,N,N-trimethylcyclohexylammonium 
halides; arylaliphatic quaternary ammonium halides such as 
tetrabenzylammonium halides and trimethylbenzylammonium halides; aromatic 
quaternary ammonium halides such as N,N,N-trimethylphenylammonium halides 
and N,N,N-triethylphenylammonium halides; and heterocyclic quaternary 
ammonium halides such as N-methylpyridinium halides, N-ethylquinolinium 
halides, N,N-dimethylpiperidinium halides and N,N'-dimethylimidazolinium 
halides. 
Exemplary polymers containing an ammonium halide group in the main chain or 
the side chain which can also be used include polymers having main 
constituent units of the following formulae: 
##STR2## 
In the above described formulae, R.sup.1, R.sup.2, R.sup.3 and X are the 
same as defined above, and R.sup.5 represents a divalent organic group. 
Exemplary phosphonium halides which can be used include symmetric 
tetraalkylphosphonium halides such as tetramethylphosphonium halides, 
tetraethylphosphonium halides and tetra-n-butylphosphonium halides; 
asymmetric tetraalkylphosphonium halides such as ethyltrimethylphosphonium 
halides and diethyldimethylphosphonium halides; symmetric 
tetraarylphosphonium halides such as tetraphenylphosphonium halides and 
tetra(p-tolyl)phosphonium halides; asymmetric tetraarylphosphonium halides 
such as (.alpha.-naphthyl)triphenylphosphonium halides; alkyl/aryl mixed 
phosphonium halides such as methyltriphenylphosphonium halides and 
phenyltrimethylphosphonium halides; and tetraaralkylphosphonium halides 
such as tetrabenzylphosphonium halides. 
Exemplary arsonium halides which can be used include symmetric 
tetraalkylarsonium halides such as tetramethylarsonium halides and 
tetraethylarsonium halides; asymmetric tetraalkylarsonium halides such as 
methyltriethylarsonium halides and diethyldimethylarsonium halides; 
symmetric tetraarylarsonium halides such as tetraphenylarsonium halides; 
and alkyl/aryl mixed arsonium halides such as methyltriphenylarsonium 
halides, ethyltriphenylarsonium halides and phenyltrimethylarsonium 
halides. 
Exemplary sulfonium halides which can be employed include symmetric or 
asymmetric alkylsulfonium halides such as trimethylsulfonium halides, 
triethylsulfonium halides and methyldiethylsulfonium halides; 
arylsulfonium halides such as triphenylsulfonium halides; alkyl/aryl mixed 
sulfonium halides such as dimethylphenylsulfonium halides and 
methyldiphenylsulfonium halides; and cyclic sulfonium halides such as 
bicyclo-(2,2,1)-heptane-1-sulfonium halides and thiopyrylium halides. 
Polymers having a phosphonium halide group or a sulfonium halide group in 
the main chain or the side chain which can also be employed include 
polymers having main constituent units of the following formulae: 
##STR3## 
wherein R.sup.1, R.sup.2, R.sup.3, X are the same as defined above. 
The oxo acids of halogen atoms and their salts mean oxygen acids of halogen 
atoms with an oxidation number of +1, +3, +5 or +7 and their salts. 
Exemplary oxo acids of halogen atoms and their salts which can be employed 
include hypochlorous acid, chlorous acid, chloric acid, perchloric acid, 
hypobromous acid, bromic acid, perbromic acid, hypoiodous acid, iodous 
acid, iodic acid, orthoperiodic acid, methaperiodic acid and their salts. 
The cations of the salts which can be employed may be any cations such as 
an ammonium ion and various metallic ions, and preferred cations are 
alkali metal ions and alkaline earth metal ions. 
Exemplary salts of the oxo acid of halogen atoms which can be employed 
include the hypochlorites such as sodium hypochlorite, potassium 
hypochlorite, calcium hypochlorite and barium hypochlorite; the chlorites 
such as sodium chlorite; the chlorates such as lithium chlorate, sodium 
chlorate, potassium chlorate, rubidium chlorate, cesium chlorate, 
magnesium chlorate and barium chlorate; the perchlorates such as aluminum 
perchlorate, calcium perchlorate, barium perchlorate, zinc perchlorate, 
cadmium perchlorate, mercury perchlorate, cerium perchlorate, lead 
perchlorate and ammonium perchlorate; the hypobromites such as sodium 
hypobromite and potassium hypobromite; the bromites such as sodium 
bromite; the bromates such as lithium bromate, sodium bromate, potassium 
bromate, rubidium bromate, cesium bromate, magnesium bromate, calcium 
bromate, strontium bromate, barium bromate, silver bromate, zinc bromate, 
cadmium bromate, mercury bromate, aluminum bromate, lanthanum bromate, 
samarium bromate, lead bromate and ammonium bromate; the perbromates such 
as potassium perbromate; the hypoiodites such as sodium hypoiodite, 
potassium hypoiodite, rubidium hypoiodite, cesium hypoiodite, calcium 
hypoiodite and barium hypoiodite; the iodates such as lithium iodate, 
sodium iodate, potassium iodate, potassium hydrogen iodate, rubidium 
iodate, cesium iodate, magnesium iodate, calcium iodate, strontium iodate, 
barium iodate, silver iodate, gold iodate, zinc iodate, cadmium iodate, 
mercury iodate, aluminum iodate, indium iodate, lanthanum iodate, cerium 
iodate, proseodium iodate, neodium iodate, gadrinium iodate, lead iodates 
and ammonium iodate; the periodates such as lithium periodate, sodium 
metaperiodate, dihydrogentrisodium orthoperiodate, trihydrogendisodium 
orthoperiodate, potassium metaperiodate, trihydrogendipotassium 
orthoperiodate, hydrogentripotassium dimesoperiodate, rubidium periodate, 
cesium periodate, barium periodate, silver metaperiodate, silver 
mesoperiodate, silver orthoperiodate, trihydrogensilver orthoperiodate, 
zinc periodate, cadmium periodate, lead periodate and ammonium periodate. 
The complex compounds containing halogen ions may be either cationic or 
anionic halogen-containing complex compounds. 
Exemplary complex compounds containing halogen ions include halogenic acid 
polyhalide salts such as ammonium dichlorobromate and tetramethylammonium 
tetrabromoiodate; metal acid halide salts such as potassium 
hexaiodotellurate, tetramethylammonium tetraiodomercurate, potassium 
tetraiodobismuthate, sodium tetrabromocuprate, cesium tetrabromoferrate, 
barium hexaiodostannate, potassium tetraiodoplumbate and potassium 
hexabromotellurate; complexes having ligands such as tetrabromo 
(diethylsuccinate)tin, octates(N,N-dimethylformamide)lanthanumtriiodide, 
hexakis(urea) chromiumtribromide, hexaamminechromiumtribromide, 
iodopentamminechromiumtribromide, tris(pyridine)molybdenumtriiodide, 
hexaamminecobalttribromide and bis(2,2'-bipyridine)copperdiiodide. 
The organic halide which can be employed in this invention is represented 
by the formula: 
EQU R.sup.6 (X).sub.m 
wherein 
R.sup.6 is an organic group having a valency of m; 
X is a halogen atom and m is an integer of 1 or more. 
When m is 2 or more, X may be two or more kinds of different halogen atoms. 
The halogen atom X may also be bonded to a hetero atom other than carbon 
such as nitrogen, phosphorus, oxygen, sulfur or selenium. 
Exemplary organic halides which can be employed in this invention include 
aliphatic mono- and poly-halides such as methyl halides, ethyl halides, 
propyl halides(respective isomers), butyl halides(respective isomers), 
hexyl halides(respective isomers), octyl halides(respective isomers), 
perfluoroheptyl halides(respective isomers), vinyl halides, allyl halides, 
methylene halides, haloforms, tetrahalogenomethanes, alkylidene halides, 
ethane dihalides(respective isomers), ethane trihalides(respective 
isomers), ethane tetrahalides, butane dihalides(respective isomers), 
hexane dihalides(respective isomers), dihaloethylenes(respective isomers); 
and aromatic mono- and polyhalides such as halogenobenzenes, 
dihalogenobenzenes (respective isomers), trihalogenobenzenes(respective 
isomers), tetrahalogenobenzenes(respective isomers), hexahalogenobenzenes, 
halogenonaphthalenes, dihalogenonaphthalenes(respective isomers), 
halogenotoluenes(respective isomers), halogenoethylbenzenes(respective 
isomers), phenyliododichloride, iodosobenzene and iodoxybenzene; alicyclic 
halides such as cyclohexane halides and cyclobutane halides; arylaliphatic 
halides such as benzyl halides and phenethyl halides; heterocyclic halides 
such as furan halides, tetrahydrofuran halides, thiophene halides, 
imidazole halides and piperidine halides; acid halides such as acetyl 
halides and benzoyl halides; and N-halides such as N-halogenosuccinimides, 
N-halogenoalkylamines, N-halogenoacetamides and N-halogenobenzamides. 
Further, these organic groups may have various substituents such as a 
nitro group, a lower alkyl group, a cyano group, an alkoxy group, an 
aryloxy group, an aromatic group, a sulfoxide group, a sulfone group, a 
carbonyl group, an ester group and an amido group, and may also have an 
unsaturated group. 
Exemplary halogen molecules which can be employed in this invention include 
chlorine molecule, bromine molecule and iodine molecule and halogeno 
intermolecules which consist of different halogen atoms such as 
chlorobromide, chloroiodide and bromoiodide. 
The above described halogen-containing compounds may be used as a single 
species or two or more species as a mixture. 
Of the halogen-containing compounds which can be used in this invention, 
those containing a bromine or iodine atom as the halogen atom are 
preferred, and those containing an iodine atom are more preferred. 
The amount of the halogen-containing compound which can be employed is not 
particularly limited, and the amount of the halogen atom in the 
halogen-containing compound is typically about 0.001 to 10000 mols per 
platinum group metal atom of the platinum group metal or the compound 
containing at least one platinum group element employed as the main 
catalyst. 
In the present invention a basic substance may be used as an additional 
promoter. However, when the halogen-containing compound is an alkali or 
alkaline earth metal halide, an onium halide, an oxo acid of a halogen 
atom or its salt, it is not always necessary to employ the basic substance 
as the additional promoter. On the other hand, when the halogen-containing 
compound is a complex compound containing a halogen ion, an organic halide 
or a halogen molecule, use of the basic substance increases the yield and 
the selectivity of a urethane compound produced and is accordingly 
preferred. 
The basic substance which can be used, if desired or necessary, in this 
invention may be either inorganic or organic. Suitable examples of such 
basic substances include alkali metals such as lithium, sodium and 
potassium; alkaline earth metals such as magnesium, calcium and barium; 
alkali metal oxides such as sodium oxide, sodium peroxide, sodium 
hyperoxide, potassium oxide, potassium peroxide, dipotassium trioxide, 
potassium hyperoxide, rubidium oxide, rubidium peroxide, dirubidium 
trioxide, rubidium hyperoxide, rubidium ozonide, cesium oxide, cesium 
peroxide, dicesium trioxide, cesium hyperoxide and cesium ozonide; 
alkaline earth metal oxides such as beryllium oxide, magnesium oxide, 
calcium oxide, calcium peroxide, strontium oxide, strontium peroxide, 
barium oxide and barium peroxide; hydroxides of alkali metals or alkaline 
earth metals such as lithium hydroxide, sodium hydroxide, potassium 
hydroxide, rubidium hydroxide, cesium hydroxide, beryllium hydroxide, 
magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium 
hydroxide; salts of a strong base and a weak acid such as sodium 
carbonate, sodium hydrogen carbonate, potassium carbonate, potassium 
hydrogen carbonate, barium carbonate, sodium silicate, magnesium silicate, 
potassium aluminate, calcium aluminate, sodium borate and barium borate; 
carbides such as calcium carbide and cesium carbide; hydroxides and oxides 
of aluminum group metals such as aluminum hydroxide, gallium hydroxide, 
indium hydroxide, thallium hydroxide and thallium oxide; oxides and 
hydroxides of rare earth metals such as lanthanum oxide, cerium oxide and 
cerium hydroxide; hydrides such as lithium hydride, sodium hydride, sodium 
borohydride, calcium hydride and lithium aluminum hydride; sulfides and 
hydrogen sulfides of alkali metals or alkaline earth metals such as sodium 
fulfide, sodium hydrogensulfide, potassium sulfide and calcium sulfide; 
quaternary ammonium hydroxides such as tetraethylammonium hydroxide and 
tetra-n-propylammonium hydroxide; quaternary phosphonium hydroxides such 
as methyltriphenylphosphonium hydroxide and tetramethylphosphonium 
hydroxide; tertiary sulfonium hydroxides such as triethylsulfonium 
hydroxide and triphenylsulfonium hydroxide; salts of a strong base and a 
weak organic acid such as sodium acetate, potassium benzoate, rubidium 
oxalate and barium propionate; alcoholates of alkali metals or alkaline 
earth metals such as sodium methylate, sodium ethylate and potassium 
ethylate; phenolates of alkali metals or alkaline earth metals such as 
sodium phenolate, potassium phenolate and magnesium phenolate; amides of 
alkali or alkaline earth metals such as lithium amide, sodium amide, 
calcium amide and lithium dimethylamide; tertiary amines and cyclic 
nitrogen-containing compounds having no N--H group such as trimethylamine, 
triethylamine, tri-n-butylamine, triphenylamine, diethylmethylamine, 
N,N-diethylaniline, N-methylpiperidine, N,N,-diethylpiperazine, 
N-methylmorpholine, triethylenediamine, hexamethylenetetramine, 
N,N,N',N'-tetramethylethylenediamine, dicyclohexylethylamine, 
1,2,2,6,6-pentamethylpiperidine, pyridine, quinoline, phenanthroline, 
indole, N-methylimidazole, 1,8-diazabicyclo-(5,4,0)-undecene-7(DBU) and 
1,5-diazabicyclo-(4,3,0)-nonene-5(DBN), etc.; crown compounds such as 
crown ethers, azacrown ethers, thiacrown ethers and azacrown; and 
complexes of these crown compounds with alkali metals or alkaline earth 
metals. Further, two or more groups exhibiting basicity may be present in 
the molecule also form part of a polymer such as anion exchange resins 
having a quaternary ammonium hydroxide group. Further, these basic 
substances or the groups having basicity may also be supported on or 
chemically bonded to a solid substance. These basic substances may be used 
either alone or as a mixture of two or more species. 
The amount of the basic substance which can be employed is not particularly 
limited and is typically about 0.01 to about 1000 mols per halogen atom in 
the halogen-containing compound. 
The amine with a replaceable hydrogen attached to the nitrogen which can be 
used as the starting material in this invention is a compound having at 
least one amino group represented by the following formulae in one 
molecule: 
EQU --NH.sub.2 or &gt;NH 
wherein the one line or the two lines bonded to a nitrogen atom indicate 
bonds between the nitrogen atom and other atoms or groups, such as a 
hydrogen atom, a halogen atom, an alkali metal, a hydroxyl group, an amino 
group, an aliphatic group, an alicyclic group, an aromatic group, an 
arylaliphatic group and a heterocyclic group. 
In the secondary amines, the nitrogen atom may itself be an element forming 
a ring as in pyrrole, piperidine, piperazine and morpholine. 
Exemplary primary amines which can be used include ammonia; aliphatic 
primary monoamines such as methylamine, ethylamine, propylamine(respective 
isomers), butylamine(respective isomers), pentylamine(respective isomers), 
hexylamine(respective isomers) and dodecylamine (respective isomers); 
aliphatic primary diamines such as ethylenediamine, 
diaminopropane(respective isomers), diaminobutane(respective isomers), 
diaminopentane(respective isomers); diaminohexane(respective isomers) and 
diaminodecane(respective isomers); aliphatic primary triamines such as 
1,2,3-triaminopropane, triaminohexane(respective isomers), 
triaminononane(respective isomers) and triaminododecane(respective 
isomers); alicyclic primary mono- and poly-amines such as 
cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, 
diaminocyclobutane, diaminocyclohexane(respective isomers) and 
triaminocyclohexane(respective isomers); arylaliphatic primary mono- and 
poly-amines such as benzylamine, di(aminomethyl)benzene(respective 
isomers), aminomethylpyridine (respective isomers), 
di(aminomethyl)pyridine (respective isomers), 
aminomethylnaphthalene(respective isomers) and 
di(aminomethyl)naphthalene(respective isomers); and heterocyclic primary 
amines such as aminofuran(respective isomers), 
aminotetrahydrofuran(respective isomers), aminothiophen(respective 
isomers), aminopyrrole(respective isomers), aminopyrrolidine(respective 
isomers); aromatic primary amines such as aniline, 
diaminobenzene(respective isomers), triaminobenzene(respective isomers), 
tetraaminobenzene(respective isomers), aminotoluene(respective isomers), 
diaminotoluene(respective isomers), aminopyridine(respective isomers), 
diaminopyridine(respective isomers), triaminopyridine(respective isomers), 
aminonaphthalene(respective isomers), diaminonaphthalene(respective 
isomers), triaminonaphthalene(respective isomers), 
tetraaminonaphthalene(respective isomers) and respective isomers of 
monoamines, diamines, triamines and tetraamines of diphenyl compounds 
represented by the formula: 
##STR4## 
wherein A represents a chemical bond or a divalent group selected from the 
group consisting of --O--, --S--, --SO.sub.2 --, --CO-- --CONH--, --COO--, 
--C(R.sup.7)(R.sup.8)-- and --N(R.sup.7)-- wherein R.sup.7 and R.sup.8 
each is a hydrogen atom, an aliphatic group or an alicyclic group. 
In these aromatic primary amines, at least one hydrogen atom in the 
aromatic ring may be substituted with a substituent such as a halogen 
atom, a nitro group, a cyano group, an alkyl group, an alicyclic group, an 
aromatic group, an aralkyl group, an alkoxy group, a sulfoxide group, a 
sulfone group, a carbonyl group, an ester group and an amido group. 
Of these aromatic amines, aniline, 2,4- and 2,6-diaminotoluene, 
chloroaniline(respective isomers), dichloroaniline(respective isomers), 
4,4'- and 2,4'-diaminodiphenylmethane and 1,5-diaminonaphthalene are 
preferred. 
Exemplary secondary amines which can be used in this invention include 
aliphatic secondary amines such as dimethylamine, diethylamine, 
dipropylamine(respective isomers), dibutylamine(respective isomers), 
dipentylamine (respective isomers), dihexylamine(respective isomers), 
ethylmethylamine, ethylpropylamine(respective isomers), 
butylmethylamine(respective isomers) and ethylhexylamine (respective 
isomers); alicyclic secondary amines such as dicyclopropylamine, 
dicyclohexylamine and methylcyclohexylamine; aromatic secondary amines 
such as N-methylaniline, N-ethylaniline, N-methyltoluidine(respective 
isomers), diphenylamine, N,N'-diphenylmethanediamine, 
N,N'-dimethylphenylenediamine(respective isomers), 
N-methylnaphthylamine(respective isomers) and dinaphthylamine(respective 
isomers); arylaliphatic secondary amines such as dibenzylamine, 
ethylbenzylamine and diphenethylamine; heterocyclic secondary amines such 
as difuranylamine and dithiophenylamine; and cyclic secondary amines such 
as pyrrolidine, pyrrole, 3-pyrrolidone, indole, carbazole, piperidine, 
piperazine, .beta.-piperidone, .gamma.-piperidone, imidazole, pyrazole, 
triazole, benzoimidazole, morpholine and 1,3-oxazine. 
In these primary amines and secondary amines, one or more hydrogens of the 
organic group bonded to the nitrogen may be substituted by a substituent 
such as a lower aliphatic group, an amino group, a carboxyl group, an 
ester group, an alkoxy group, a cyano group, a halogen atom, a nitro 
group, a urethane group, a sulfoxide group, a sulfone group, a carbonyl 
group, an amide, an aromatic group and arylaliphatic group. Further, these 
primary amines and secondary amines may also have an unsaturated bond. 
In this invention it is also possible to use compounds having an amino 
group and a hydroxyl group in the molecule such as ethanolamine, 
propanolamine and o-aminobenzyl alcohol. In such a case, cyclic urethanes 
can be produced. 
In order to produce urethane compounds to be employed as starting materials 
for the preparation of isocyanate compounds, it is preferred that the 
primary amines are used. 
The urea compound which can be employed as the starting material in this 
invention is a compound having at least one urea bond represented by the 
following formula in one molecule: 
##STR5## 
wherein the two lines bonded to a nitrogen atom indicate bonds between the 
nitrogen atom and other atoms or groups such as a hydrogen atom, a halogen 
atom, an aliphatic group, an alicyclic group, an aromatic group, an 
arylaliphatic group and a heterocyclic group, and the nitrogen atom or the 
urea bond by itself may be an element forming a ring. 
Suitable examples of such urea compounds which can be employed in this 
invention include non-substituted urea, i.e., urea and mono-, di-, tri- or 
tetra-substituted ureas. 
Exemplary mono-substituted ureas include aliphatic mono-substituted ureas 
such as methylurea, ethylurea, propylurea(respective isomers), 
butylurea(respective isomers) and hexylurea(respective isomers); alicyclic 
mono-substituted ureas such as cyclopropylurea, cyclobutylurea and 
cyclohexylurea; arylaliphatic mono-substituted ureas such as benzylurea 
and .beta.-phenethylurea; heterocyclic mono-substituted ureas such as 
furanylurea and thiophenylurea; aromatic mono-substituted ureas such as 
phenylurea, tolylureas and naphthylureas. 
Exemplary di-substituted ureas include aliphatic N,N-di-substituted ureas 
such as N,N-dimethylurea, N,N-diethylurea, N,N-di-n-propylurea, 
N,N-di-n-butylurea, N,N-di-n-hexylurea, N-ethyl-N-methylurea and 
N-ethyl-N-n-butylurea; alicyclic N,N-di-substituted ureas such as 
N,N-dicyclopropylurea, N,N-dicyclobutylurea, N,N-dicyclohexylurea, 
N-cyclopropyl-N-methylurea and N-cyclohexyl-N-ethylurea; arylaliphatic 
N,N-di-substituted ureas such as N,N-dibenzylurea and 
N-benzyl-N-methylurea; heterocyclic N,N-di-substituted ureas such as 
N,N-difuranylurea, N,N-dithiophenylurea and N-furanyl-N-methylurea; 
aromatic N,N-di-substituted ureas such as N,N-diphenylurea, 
N,N-p-tolylurea, N,N-o-tolylurea, N,N-m-tolylurea, 
N,N-di-.alpha.-naphthylurea, N,N-di-.beta.-naphthylurea, 
N-phenyl-N-methylurea, N-phenyl-N-p-tolylurea, 
N-.beta.-naphthyl-N-benzylurea and N-phenyl-N-cyclohexylurea; aliphatic 
N,N'-di-substituted ureas such as N,N'-dimethylurea, N,N'-diethylurea, 
N,N'-di-n-propylurea, N,N'-di-n-butylurea, N,N'-di-n-hexylurea, 
N-ethyl-N'-methylurea, N-ethyl-N'-n-butylurea and N-n-hexyl-N'-methylurea; 
alicyclic N,N'-di-substituted ureas such as N,N'-dicyclopropylurea, 
N,N'-dicyclobutylurea, N,N'-dicyclohexylurea, N-cyclopropyl-N'-methylurea 
and N-cyclohexyl-N'-ethylurea; arylaliphatic N,N'-di-substituted ureas 
such as N,N'-dibenzylurea and N-benzyl-N'-methylurea; heterocyclic 
N,N'-di-substituted ureas such as N,N'-difuranylurea and 
N,N'-dithiophenylurea; aromatic N,N'-di-substituted ureas such as 
N,N'-diphenylurea, N,N'-di-p-tolylurea, N,N'-di-o-tolylurea, 
N,N'-di-m-tolylurea, N,N'-di-.alpha.-naphthylurea, 
N,N'-di-.beta.-naphthylurea, N-phenyl-N'-p-tolylurea, 
N-phenyl-N'-.alpha.-naphthylurea, N-phenyl-N'-ethylurea, 
N-.alpha.-naphthyl-N'-benzylurea and N-phenyl-N'-cyclohexylurea; and ureas 
of cyclic nitrogen-containing compounds such as piperidylurea and 
pyrrolidinylurea. 
Exemplary tri-substituted ureas include aliphatic tri-substituted ureas 
such as trimethylurea, triethylurea, tri-n-propylurea, tri-n-butylurea, 
tri-n-hexylurea, N,N-dimethyl-N,-ethylurea, N,N-diethyl-N'-n-butylurea and 
N-methyl-N-ethyl-N'-n-butylurea; alicyclic tri-substituted ureas such as 
tricyclopropylurea, tricyclohexylurea, N,N'-dicyclohexyl-N'-methylurea, 
N-cyclohexyl-N'-methylurea, N-cyclohexyl-N-ethyl-N'-n-butylurea and 
N,N-diethyl-N'-cyclobutylurea; heterocyclic tri-substituted ureas such as 
trifuranylurea, trithiophenylurea and N,N'-difuranyl-N-methylurea; 
aromatic tri-substituted ureas such as triphenylurea, tri-p-tolylurea, 
tri-o-tolylurea, tri-m-tolylurea, tri-.alpha.-naphthylurea, 
tri-.beta.-naphthylurea, N,N-diphenyl-N'-methylurea, 
N,N'-diphenyl-N'-methylurea, N, N'-diphenyl-N-cyclohexylurea, 
N,N-dimethyl-N'-phenylurea, N-phenyl-N-ethyl-N'-benzylurea; and ureas of 
N-substituted cyclic nitrogen-containing compounds such as 
N-ethylpiperidylurea and N-methylpyrrodinylurea. 
Exemplary tetra-substituted ureas include aliphatic tetra-substituted ureas 
such as tetramethylurea, tetraethylurea, tetra-n-propylurea, 
tetra-n-hexylurea, diethyldimethylurea and ethyltrimethylurea; alicyclic 
tetra-substituted ureas such as tetracyclopropylurea, tetracyclohexylurea, 
dicyclohexyldiethylurea and cyclobutyltrimethylurea; arylaliphatic 
tetra-substituted ureas such as tetrabenzylurea, tribenzylmethylurea, 
dibenzyldiethylurea and benzyltrimethylurea; heterocyclic tetrasubstituted 
ureas such as tetrafuranylurea, tetrathiophenylurea and 
furanyltrimethylurea; aromatic tetrasubstituted ureas such as 
tetraphenylurea, tetra-p-tolylurea, tetra-m-tolylurea, tetra-o-tolylurea, 
tetra-.alpha.-naphthylurea, tetra-.beta.-naphthylurea, 
methyltriphenylurea, diethyldiphenylurea, dicyclohexyldiphenylurea, 
.alpha.-naphthyltriethylurea and .beta.-naphthyltriethylurea; cyclic ureas 
in which a urea bond is the member constituting a ring such as 
2-imidazolone, 2-imidazolidone, biotin, hydantoin, N, N'-hexamethylurea, 
parabanic acid and benzimidazole; compounds having at least two urea bonds 
in the molecule such as N,N'-dimethylcarbamoylhexamethylenediamine and 
N,N'-diphenylcarbamoylhexamethylenediamine; and polymeric ureas having 
units of the following formula in the molecule: 
##STR6## 
In these substituted urea compounds at least one hydrogen in the 
substituent may be substituted with a lower aliphatic group, an amino 
group, a carboxyl group, an ester group, an alkoxy group, a cyano group, a 
halogen atom, a nitro group, a urethane group, a sulfoxide group, a 
sulfone group, a carbonyl group, an amido group, an aromatic group or 
arylaliphatic group. 
In preparing urethane compounds useful as the starting material for 
isocyanate compounds it is preferred that N,N'-di-substituted ureas are 
employed. In order to readily obtain N-monoaromatic urethane compounds, 
N,N'-diarylureas are preferably employed. 
As is apparent from the above, any of a wide variety of urea compounds may 
be utilized in this invention. In carrying out the urethanation of a 
primary or secondary amine, the counterpart urea compound may sometimes be 
present as an intermediate in the reaction system but this urea compound 
is finally urethanated. 
According to this invention, the primary amine, the secondary amine and the 
urea compound may be singly or in various mixtures. 
The organic hydroxyl compounds which can be used in this invention are 
aliphatic and aromatic compounds such as monohydric or polyhydric alcohols 
or monohydric or polyhydric phenols. Such alcohols include C.sub.1-20 
straight or branched monohydric or polyhydric alkanols or alkenols and 
C.sub.3-20 monohydric or polyhydric cycloalkanols or cycloalkenols and 
C.sub.7-20 monohydric or polyhydric aralkylalcohols. Further, these 
alcohols may also have a substituent such as a halogen atom, a cyano 
group, an alkoxy group, a sulfoxide group, a sulfone group, a carbonyl 
group, an ester group and an amide group. 
Exemplary alcohols include aliphatic alcohols such as methanol, ethanol, 
propanol(respective isomers), butanol(respective isomers), 
pentanol(respective isomers), hexanol(respective isomers), 
heptanol(respective isomers), octanol(respective isomers), nonyl 
alcohol(respective isomers), decyl alcohol(respective isomers), undecyl 
alcohol(respective isomers), lauryl alcohol(respective isomers), tridecyl 
alcohol(respective isomers), tetradecyl alcohol(respective isomers) and 
pentadecyl alcohol(respective isomers); cycloalkanols such as cyclohexanol 
and cycloheptanol; alkylene glycol monoethers such as ethylene glycol 
monomethylether, ethylene glycol monoethylether, diethylene glycol 
monomethylether, diethylene glycol monoethylether, triethylene glycol 
monomethylether, triethylene glycol monoethylether, propylene glycol 
monomethylether and propylene glycol monoethylether; polyhydric alcohols 
such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene 
glycol, glycerine, hexanetriol and trimethylolpropane; and aralkyl 
alcohols such as benzyl alcohol. 
Exemplary phenols include phenol, various alkylphenols, various 
alkoxyphenols, various halogenated phenols, dihydroxybenzene, 
4,4'-dihydroxy-diphenylmethane, bisphenol-A and hydroxynaphthalene. 
Of the above described organic hydroxyl compounds, C.sub.1-10 aliphatic 
monoalcohols, C.sub.3-10 alicyclic or C.sub.7-15 aralkyl monoalcohols are 
preferred. 
In the case of the urethanation of a primary or secondary amine, the amount 
of the alcohol or phenol employed is typically at least one mol per amino 
group of the primary or secondary amine. In the case of the urethanation 
of a urea compound, the amount of the alcohol or phenol employed is at 
least two mols per urea group of the urea compound. In both cases it is 
preferred that the alcohol or phenol is employed as a reaction medium. In 
such a case the amount of the alcohol or phenol is typically about 3 to 
100 mols per amino group of the primary or secondary amine or per urea 
group of the urea compound. 
The carbon monoxide which can be employed as one starting material in this 
invention may be pure carbon monoxide or may contain other gases such as 
nitrogen, argon, helium, carbon dioxide, a hydrocarbon or a halogenated 
hydrocarbon. A small amount, i.e., less than about 10% by mol of hydrogen 
based on carbon monoxide does not affect adversely the urethanation using 
the catalyst system of this invention, and accordingly in this invention 
carbon monoxide containing such a small amount of hydrogen may be 
advantageously employed from the industrial viewpoint. 
The amount of carbon monoxide which can be employed is typically at least 
one mol, preferably about 2 to about 100 mols per amino group of the 
primary or secondary amine or per urea group of the urea compound. 
The oxidizing agent which can be used in this invention may be molecular 
oxygen or an organic nitro compound or a mixture thereof. Molecular oxygen 
is preferred. The molecular oxygen means pure oxygen or a gas containing 
oxygen such as air. The molecular oxygen may also be diluted by the 
addition of other gases not interfering with the reaction to air or pure 
oxygen including inert gases such as nitrogen, argon, helium and carbon 
dioxide. In some cases the molecular oxygen may also contain a gas such as 
hydrogen, carbon monoxide, a hydrocarbon and a halogenated hydrocarbon. 
The organic nitro compound which can be used in this invention may be 
either an alicyclic, aliphatic or aromatic nitro compound. Exemplary 
alicyclic nitro compounds include nitrocyclobutane, nitrocyclopentane, 
nitrocyclohexane, dinitrocyclohexane(respective isomers) and 
bis-(nitrocyclohexyl) methane. Exemplary aliphatic nitro compounds include 
nitromethane, nitroethane, nitropropane (respective isomers), 
nitrobutane(respective isomers), nitropentane(respective isomers), 
nitrohexane(respective isomers), nitrodecane(respective isomers), 
1,2-dinitroethane, dinitropropane(respective isomers), dinitrobutane 
(respective isomers), dinitropentane(respective isomers), 
dinitrohexane(respective isomers), dinitrodecane(respective isomers), 
phenylnitromethane, bis-(nitromethyl) cyclohexane and 
bis-(nitromethyl)benzene. Exemplary aromatic nitro compounds include 
nitrobenzene, dinitrobenzene(respective isomers), nitrotoluene(respective 
isomers), dinitrotoluene(respective isomers), nitropyridine(respective 
isomers), dinitropyridine(respective isomers), nitronaphthalene(respective 
isomers), dinitronaphthalene(respective isomers), and respective isomers 
of mononitro compounds and di-nitro compounds of the diphenyl compounds 
represented by the formula 
##STR7## 
wherein A is the same as defined above. 
In these nitro compounds, at least one hydrogen may be substituted by a 
substituent such as a halogen atom, an amino group, a cyano group, an 
alkyl group, an aliphatic group, an aromatic group, an aralkyl group, an 
alkoxy group, a sulfoxide group, a sulfone group, a carbonyl group, an 
ester group, an amido group. 
When molecular oxygen is used as the oxidizing agent in the present 
invention, the urethanation of, for example, a primary amine proceeds 
according to the general reaction equation as follows: 
EQU R.sup.9 (NH.sub.2).sub.n +1/2n.O.sub.2 +n.CO+n.R.sup.10 OH.fwdarw.R.sup.9 
(NHCOOR.sup.10).sub.n +n.H.sub.2 O 
wherein R.sup.9 and R.sup.10 each represents an organic group and n 
represents the number of amino groups in one molecule of an amino 
compound. 
In the case of a secondary amine the urethanation proceeds substantially in 
the same way as described above. 
The urethanation of a urea compound proceeds according to the general 
reaction equation as follows: 
##STR8## 
wherein R.sup.11, R.sup.12, R.sup.13 and R.sup.14 each represents a 
hydrogen atom, an aliphatic group, an alicyclic group, an arylaliphatic 
group, a heterocyclic group or an aromatic group and R.sup.10 represents 
an organic group. 
The molecular oxygen may be less or more than its equivalent amount, but a 
mixture of oxygen and carbon monoxide or a mixture of oxygen and an 
organic hydroxyl compound should be used in the range outside the 
explosion limit. 
When an organic nitro compound is used as the oxidizing agent, the organic 
nitro compound also participates in the reaction to form a urethane 
compound. Accordingly, when the structure of the organic group in the 
organic nitro compound is different from that in the primary or secondary 
amine or the substituent in the urea compound, different kinds of urethane 
compounds are obtained corresponding to the respective structures. When 
both have the same structure, the same urethane compound is obtained. In 
this case, the urethanation of, for example, a primary amine proceeds 
according to the following reaction equation: 
EQU 2R.sup.9 (NH.sub.2).sub.n +R.sup.15 (NO.sub.2).sub.n +3n.CO+3n.R.sup.10 
OH.fwdarw.2R.sup.9 (NHCOOR.sup.10).sub.n +R.sup.15 (NHCOOR.sup.10).sub.n 
+2n.H.sub.2 O 
wherein R.sup.9, R.sup.10, and n are the same as defined above, and 
R.sup.15 represents a residue of an organic nitro compound other than the 
nitro group and for simplicity the number of nitro groups in the organic 
nitro compound is assumed to be the same as that of amino groups in the 
primary amine. 
In the case of the urethanation of a urea compound with, for example, an 
organic mononitro compound, the reaction proceeds as follows: 
##STR9## 
wherein R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are the same 
as defined above, and R.sup.16 represents an organic residue of an organic 
nitro compound. 
When only an organic nitro compound is used as the oxidizing agent, the 
amount of the primary amine, secondary amine or urea compound to the 
organic nitro compound may preferably be one mol of the nitro group per 2 
mols of the amino group or the urea group. It is possible to practice the 
invention at a ratio apart from the stoichiometric ratio but it is 
advantageous to adopt an equivalent ratio of the amino group or urea group 
to the nitro group of 1.1:1 to 4:1, preferably 1.5:1 to 2.5:1. 
When molecular oxygen or other oxidizing agents are employed at the same 
time, the organic nitro compound may be used in an amount less than the 
stoichiometric amount. 
In the process of this invention, it is preferred to use an excess of an 
organic hydroxyl compound as the reaction medium. If necessary, other 
solvents which do not affect the reaction adversely may also be used. 
Exemplary solvents which can be employed include aromatic hydrocarbons 
such as benzene, toluene, xylene and mesitylene; nitriles such as 
acetonitrile and benzonitrile; sulfones such as sulforane, methylsulforane 
and dimethylsulforane; ethers such as tetrahydrofuran, 1,4-dioxane and 
1,2-dimethoxyethane; ketones such as acetone, methyl ethyl ketone; esters 
such as ethyl acetate and ethyl benzoate; and amides such as 
N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and 
hexamethylphosphoramide. 
Further, it is also possible to use, as a solvent, a halogenated aromatic 
hydrocarbon which is one kind of the organic halide to be used as the 
promoter in this invention such as chlorobenzene, dichlorobenzene, 
trichlorobenzene, fluorobenzene, chlorotoluene, chloronaphthalene and 
bromonaphthalene; a halogenated aliphatic hydrocarbon or a halogenated 
alicyclic hydrocarbon such as chlorohexane, chlorocyclohexane, 
trichlorotrifluoroethene, methylene chloride and carbon tetrachloride. 
The reaction according to this invention can hardly be affected adversely 
by the presence of a small amount of water. However, the presence of water 
might cause some side reactions such as the hydrolysis of urethane 
compounds and the water gas reaction of carbon monoxide and accordingly, 
it is possible to employ additives having a dehydrating action. Suitable 
examples of such additives include zeolites, orthoesters, ketals, acetals, 
enolethers and trialkyl orthoborates. 
In the process of this invention, the reaction is carried out at a 
temperature of from about 80.degree. C. to about 300.degree. C., 
preferably from 120.degree. to 220.degree. C. The reaction pressure is 
typically in the range of from about 1 Kg/cm.sup.2 to about 500 
Kg/cm.sup.2, preferably from about 20 Kg/cm.sup.2 to about 300 
Kg/cm.sup.2. The reaction time which may vary depending on the reaction 
system employed and other reaction conditions chosen is typically about 
one minute to about 10 hours. 
The reaction of this invention can be carried out either batch-wise or 
continuously by removing continuously the reaction mixture from the 
reaction system while continuously feeding the reactants into the reaction 
system.

A further understanding of the present invention, and the advantages 
thereof, can be had by reference to the following examples. 
The conversion of a primary or secondary amine, a urea compound, an organic 
nitro compound or molecular oxygen, the yield of a urethane compound, the 
selectivity of an urethane compound and the selectivity of molecular 
oxygen to the urethanation reaction were determined in the examples 
according to the following formulae: 
##EQU1## 
wherein A is a primary or secondary amine, a urea compound, an organic 
nitro compound or molecular oxygen. 
##EQU2## 
in case of a syn-urea compound employed as the starting material. 
##EQU3## 
The autoclave employed in the following examples were internally lined with 
titanium or made of Hastelloy-C..RTM. 
EXAMPLE 1 
In a 140 ml stirring type autoclave were charged 40 mmols of aniline, 40 ml 
of ethanol, 0.5 mg-atom of palladium black and 5 mmols of cesium iodide. 
After the air inside the autoclave had been replaced with carbon monoxide, 
carbon monoxide was pressurized into the autoclave to 80 Kg/cm.sup.2 and 
then oxygen was pressurized into the autoclave to 6 Kg/cm.sup.2, resulting 
in a total pressure of 86 Kg/cm.sup.2. The reaction was carried out at 
160.degree. C. for one hour with stirring, and subsequently the reaction 
mixture obtained was subjected to filtration. As the result of analysis of 
the filtrate, the conversion of aniline was 87% and the yield of ethyl 
N-phenylcarbamate was 85% with a selectivity of 98%. In the filtrate 
palladium was not detected. 
EXAMPLE 2 
The procedure of Example 1 was repeated except that 5 mmols of 
tetramethylammonium iodide were employed instead of the cesium iodide. The 
filtrate obtained was a yellowish solution. As a result, the conversion of 
aniline was 81% and the yield of ethyl N-phenylcarbamate was 80% with a 
selectivity of 99%. In the filtrate palladium was not detected. When 
ethanol was distilled from this solution under reduced pressure and then 
tetramethylammonium iodide was removed by washing with water, 5.3 g of 
yellow crystals were precipitated. The crude crystals thus obtained were 
ethyl N-phenylcarbamate of 99% purity and recrystallized once from ethanol 
to give white crystals of ethyl N-phenylcarbamate of 100% purity. 
EXAMPLE 3 
An anion exchange resin (Amberlyst.RTM. A-26, OH-form) having units of the 
formula: 
##STR10## 
was treated with hydroiodic acid to exchange the hydroxyl groups with 
iodine anions and then dried at 100.degree. C. under reduced pressure. One 
gram of the iodine-containing anion exchange resin, 40 mmols of aniline, 
40 ml of ethanol and 0.5 mg-atom of palladium black were charged into a 
140 ml stirring type autoclave. After the air inside the autoclave was 
replaced with carbon monoxide, carbon monoxide was pressurized into the 
autoclave to 80 Kg/cm.sup.2, and subsequently oxygen was pressurized into 
the autoclave to 6 Kg/cm.sup.2, resulting in a total pressure of 86 
Kg/cm.sup.2. The reaction was carried out with stirring at 150.degree. C. 
for one hour, and then the reaction mixture was subjected to filtration. 
As the result of analysis of the filtrate, the conversion of aniline was 
83% and the yield of ethyl N-phenylcarbamate was 81% with a selectivity of 
98%. 
When the above described procedure was repeated by using the palladium 
black and the anion exchange resin separated by filtration as such, the 
result obtained was as good as the above, i.e., the conversion of aniline 
was 82% and the yield of ethyl N-phenylcarbamate was 80% with a 
selectivity of 98%. 
The reaction solution obtained in either case was yellowish and when the 
reaction solution was distilled under reduced pressure, yellow crystals 
were precipitated. The crude crystals thus obtained were ethyl 
N-phenylcarbamate of 99% purity and recrystallized once from ethanol to 
give white crystals of a high purity. 
EXAMPLE 4 
The procedure of Example 1 was repeated except that 1 mmol of potassium 
metaperiodate was employed instead of the cesium iodide. As a result, the 
conversion of aniline was 89% and the yield of ethyl N-phenylcarbamate was 
85% with a selectivity of 96%. 
EXAMPLE 5 
The procedure of Example 1 was repeated except that 0.25 mmol of potassium 
tetraiodobismuthate was employed instead of the cesium iodide. As a 
result, the conversion of aniline was 81% and the yield of ethyl 
N-phenylcarbamate was 70% with a selectivity of 86%. 
EXAMPLE 6 
The procedure of Example 1 was repeated except that 0.3 mmol of iodoform 
and 1 mmol of rubidium hydroxide were employed instead of the cesium 
iodide. As a result, the conversion of aniline was 85% and the yield of 
ethyl N-phenylcarbamate was 82% with a selectivity of 97%. In the filtrate 
obtained no palladium was detected. The selectivity of the oxygen reacted 
to the urethanation was 93%. 
When the above described procedure was repeated except that the rubidium 
was not employed, the conversion of aniline ws 45% and the yield of ethyl 
N-phenylcarbamate was 41% with a selectivity of 91%, and the selectivity 
of the oxygen to the urethanation was 70%. 
The reaction solution obtained in either case was transparent and 
yellowish. 
It is clear from this example that a urethane compound can be obtained at a 
high selectivity using only an organic halide and palladium, and the yield 
and the selectivity can be remarkably increased by additional use of a 
basic substance. 
EXAMPLE 7 
The procedure of Example 1 was repeated except that 1 mmol of iodine and 1 
mmol of triethylamine were employed instead of the cesium iodide. As a 
result, the conversion of aniline was 90% and the yield of ethyl 
N-phenylcarbamate was 86% with a selectivity of 96%. In the filtrate no 
palladium was detected. 
When the above described procedure was repeated except that the 
triethylamine was not employed, the conversion of aniline was 42% and the 
yield of ethyl N-phenylcarbamate was 28% with a selectivity of 67%. 
COMATIVE EXAMPLE 1 
The procedure of Example 1 was repeated except that the cesium iodide was 
not employed. As a result, the conversion of aniline was 8% and the yield 
of ethyl N-phenylcarbamate was only 1.9%. 
COMATIVE EXAMPLE 2 
The procedure of Example 1 was repeated except that 1 mmol of triethylamine 
was employed instead of the cesium iodide. As a result, the conversion of 
aniline was 3% and the yield of ethyl N-phenylcarbamate was only 1% 
EXAMPLES 8 TO 119 
The procedure of Example 1 was repeated except that 0.5 mg-atom of a 
platinum group metal or a compound containing the platinum group element 
based on the metal element set forth in Table 1 was employed in the 
presence or absence of a basic substance set forth in Table 1 instead of 
the cesium iodide. 
The results are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
am-Ex- 
Containing Ator CompoundPt Group Metal 
Halogen-containing 
Basic 
##STR11## 
##STR12## 
ple 
Least One Pt 
Compound Substance Conversion 
Yield Selectivity 
No. 
Group Element*.sup.1 
(mmol) (mmol) (%) (%) (%) 
__________________________________________________________________________ 
8 Pd Black LiCl 5 -- 55 34 62 
9 " " 3 RbOH1 76 53 70 
10 " MgCl.sub.2 5 -- 71 50 70 
11 " KBr 5 -- 76 56 74 
12 " " 3 RbOH1 82 66 80 
13 " CsBr 5 -- 77 62 81 
14 " BaBr.sub.2 5 -- 50 39 78 
15 " LiI 5 -- 70 56 80 
16 " NaI 5 -- 69 62 90 
17 " KI 5 -- 79 72 91 
18 " RbI 5 -- 81 78 96 
19 " MgI.sub.2 5 -- 65 50 77 
20 " SrI.sub.2.3H.sub.2 O 
5 -- 45 32 71 
21 " BaI.sub.2.2H.sub.2 O 
5 -- 47 38 81 
22 " " 0.5 
KOH1 80 74 93 
23 5% Pd/C CsI 5 -- 83 75 90 
24 5% (PdTe)/C*.sup.2 
CsI 5 -- 88 81 92 
25 Lindlar Catalyst*.sup.3 
" 5 -- 80 70 88 
26 5% Pd/Al.sub.2 O.sub.3 
" 5 -- 85 79 93 
27 5% Rh/C " 5 -- 75 66 88 
28 RhI.sub.3 " 5 -- 80 66 83 
29 Ru Black " 5 -- 52 44 85 
30 IrCl.sub.3 
" 5 -- 53 34 65 
31 Pd Black NH.sub.4 Cl 5 -- 70 51 73 
32 " 
##STR13## 5 -- 73 53 73 
33 " NH.sub.4 Br 5 -- 77 63 82 
34 " 
##STR14## 5 -- 70 55 79 
35 " NH.sub.4 I 5 -- 85 79 93 
36 " (C.sub.2 H.sub.5).sub.3 N.HI 
5 -- 80 76 95 
37 " HI 5 
##STR15## 88 82 93 
38 " 
##STR16## 5 -- 85 82 97 
39 " [(CH.sub.3).sub.4 N].sup..sym. I.sup..crclbar. 
1 (C.sub.2 H.sub.5).sub.3 N1 
87 85 98 
40 5% Pd/C [(CH.sub.3).sub.4 N].sup..sym. I.sup..crclbar. 
5 -- 85 83 98 
41 5% (PdTe)/C*.sup.2 
" 5 -- 83 80 96 
42 5% Pd/Al.sub.2 O.sub.3 
" 5 -- 88 86 98 
43 Lindlar Catalyst*.sup.3 
" 5 -- 75 69 92 
44 5% Ph/C " 5 -- 77 69 90 
45 RhI.sub.3 " 5 -- 79 67 85 
46 5% Pt/C [(CH.sub.3).sub.4 N].sup..sym. I.sup..crclbar. 
5 -- 53 40 75 
47 Pd Black [(C.sub.6 H.sub.5).sub.4 P].sup..sym. Br.sup..crclbar. 
5 -- 75 66 88 
48 " [(C.sub.6 H.sub.5).sub.3 PCH.sub.3 ].sup..sym. I.sup..crclbar 
. (C.sub.2 H.sub.5).sub.3 N1 
85 82 96 
49 " [(CH.sub.3).sub.3 S].sup..sym. I.sup..crclbar. 
5 -- 40 28 70 
50 " " 2 (n-C.sub.4 H.sub.9).sub.3 N1 
75 66 88 
51 " [(C.sub.6 H.sub.5).sub.3 AsCH.sub.3 ].sup..sym. I.sup..crclba 
r. 5 -- 78 72 92 
52 " " 2 NaHCO.sub.31 
84 79 94 
53 5% Rh/C [(C.sub.6 H.sub.5)PCH.sub.3 ].sup..sym. I.sup..crclbar. 
5 -- 73 59 81 
54 RhI.sub.3 " 5 -- 75 60 80 
55 Ru Black " 5 -- 55 45 82 
56 Pd Black KH(IO.sub.3).sub.2 
1 -- 52 48 93 
57 " " 1 K.sub.2 CO.sub.31 
80 75 94 
58 " KBrO.sub.3 1 -- 50 42 84 
59 " " 1 DBU*.sup.51 
70 63 90 
60 " HIO.sub.3 1 -- 60 54 90 
61 " " 0.8 
CsOH1 82 75 92 
62 " KIO.sub.4 1 (C.sub.2 H.sub.5).sub.3 N1 
90 87 97 
63 " CsIO.sub.4 1 -- 90 86 96 
64 5% Pd/C KIO.sub.4 1 -- 88 83 94 
65 5% Rh/C " 1 -- 78 69 89 
66 Ru Black " 1 -- 60 50 83 
67 5% Pt/C " 1 -- 58 45 78 
68 Pd Black [(CH.sub.3).sub.4 N][I.sub.5 ] 
0.2 
-- 48 35 73 
69 " " 0.2 
RbOH1 78 72 92 
70 " K[PbI.sub.3 ].2H.sub.2 O 
0.4 
-- 60 53 88 
71 " " 0.3 
RbOH1 80 72 90 
72 Pd Black K.sub.2 [TeBr.sub.6 ] 
0.2 
-- 78 66 85 
73 " " 0.2 
Na.sub.2 B.sub.4 O.sub.7.10H.sub.2 O1 
85 80 90 
74 " K[BiI.sub.4 ].H.sub.2 O 
0.3 
(n-C.sub.3 H.sub.7).sub.4 NOH1 
87 82 94 
75 " K.sub.2 [HgI.sub.4 ].2H.sub.2 O 
0.3 
-- 66 59 90 
76 5% Rh/C K.sub.2 [TeBr.sub.6 ] 
0.4 
-- 70 57 81 
77 RhI.sub.3 K[BiI.sub.4 ].H.sub.2 O 
0.3 
-- 73 60 82 
78 Pd Black 
##STR17## 1 -- 32 24 75 
79 " 
##STR18## 1 -- 38 32 84 
80 " CH.sub.3 I 1 -- 40 36 90 
81 " " 0.8 
(C.sub.2 H.sub.5).sub.3 N1 
88 84 95 
82 " CI.sub.4 0.25 
-- 50 47 94 
83 " " 0.2 
C.sub.2 H.sub.5 ONa1 
88 83 94 
84 " CF.sub.3 (CF).sub.6 I 
1 -- 50 45 90 
85 Pd Black 
##STR19## 1 -- 48 42 88 
86 5% Rh/C CHI.sub.3 0.3 
-- 42 38 90 
87 " " 0.3 
RbOH1 78 70 90 
88 RhI.sub.3 CHI.sub.3 0.3 
-- 51 45 89 
89 " " 0.3 
RbOH1 78 70 90 
90 Ru Black " 0.3 
-- 40 30 75 
91 " " 0.3 
RbOH1 73 62 85 
92 IrCl.sub.3 
" 0.3 
-- 35 25 71 
93 " " 0.3 
RbOH1 58 46 80 
94 5% Pt/C " 0.3 
RbOH1 70 57 82 
95 Pd Black Br.sub.2 1 -- 38 21 55 
96 " " 1 RbOH1 68 60 88 
97 " I.sub.2 1 NaOH1 92 87 95 
98 " " 1 CsOH1 90 86 96 
99 " " 1 Ba(OH).sub.2.8H.sub. 2 O1 
75 69 92 
100 
" " 1 CaO1 70 62 89 
101 
" " 1 BaO1 76 71 93 
102 
" " 1 
##STR20## 92 89 97 
103 
" " 1 (n-C.sub.3 H.sub.7).sub.4 NOH*.sup.61 
75 72 96 
104 
Pd Black I.sub.2 1 DBU*.sup.51 
92 87 95 
105 
" " 1 CH.sub.3 COOK1 
52 44 84 
106 
" " 1 (CH.sub.3).sub.2 NLi1 
90 86 96 
107 
" " 1 NaHCO.sub.31 
85 80 94 
108 
" " 1 K.sub.2 CO.sub.31 
86 79 92 
109 
" " 1 Al(OH).sub.31 
53 47 89 
110 
" " 1 La.sub.2 O.sub.31 
55 47 85 
111 
5% Pd/C " 1 RbOH1 88 84 95 
112 
" " 1 (C.sub.2 H.sub.5).sub.3 N1 
89 85 95 
113 
5% (PdTe)/C*.sup.2 
" 1 RbOH1 86 80 93 
114 
" " 1 (C.sub.2 H.sub.5).sub.3 N1 
85 80 94 
115 
5% Rh/C " 1 (C.sub.2 H.sub.5).sub.3 N1 
82 75 92 
116 
RhI.sub.3 " 1 RbOH1 73 66 90 
117 
Ru Black " 1 RbOH1 58 49 84 
118 
IrCl.sub.3 
" 1 (C.sub.2 H.sub.5).sub.3 N1 
48 33 69 
119 
5% Pt/C " 1 (C.sub.2 H.sub.5).sub.3 N1 
62 48 78 
__________________________________________________________________________ 
*.sup.1 %: weight % 
*.sup.2 Lindlar catalyst: 5% by weight (PdPb)/CaCO.sub.3 where the atomic 
ratio of Pd to Pb is 1:2. 
*.sup.3 (PdTe)/C was prepared by supporting palladium chloride and 
tellurium dioxide at a mol ratio of 10 to 3 on active carbon and then 
reducing the resultant with hydrogen at 350.degree. C. 
##STR21## 
*.sup.5 DBU: 1,8diazabicyclo-[5,4,0]-undecene-7 
*.sup.6 (n-C.sub.3 H.sub.7).sub.4 NOH: 10% by weight aqueous solution of 
tetran-propyl-ammonium hydroxide 
EXAMPLE 120 
In a 140 ml stirring type autoclave were charged 40 mmols of 
cyclohexylamine, 40 ml of ethanol, 0.5 mg-atom of palladium black and 2 
mmols of cesium iodide. After the air inside the autoclave had been 
replaced with carbon monoxide, carbon monoxide was pressurized into the 
autoclave to 80 Kg/cm.sup.2 and then oxygen was pressurized into the 
autoclave to 6 Kg/cm.sup.2, resulting in a total pressure of 86 
Kg/cm.sup.2. The reaction was carried out at 160.degree. C. for one hour 
with stirring, and subsequently the reaction mixture obtained was 
subjected to filtration. As the result of analysis of the filtrate, the 
conversion of cyclohexylamine was 85% and the yield of ethyl 
N-cyclohexylcarbamate was 81% with a selectivity of 95%. 
EXAMPLE 121 
The procedure of Example 120 was repeated except that 2 mmols of 
tetramethylammonium iodide were employed instead of the cesium iodide. As 
a result, a yellowish filtrate was obtained, and the conversion of 
cyclohexylamine was 82% and the yield of ethyl N-cyclohexylcarbamate was 
80% with a selectivity of 98%. When ethanol was distilled from the 
filtrate and then tetramethylammonium iodide was removed by washing with 
water, yellowish crystals were precipitated. The crude crystals thus 
obtained were ethyl N-cyclohexylcarbamate of 98% purity and recrystallized 
once from ethanol to give white crystals of ethyl N-cyclohexylcarbamate of 
100% purity. 
EXAMPLE 122 
The procedure of Example 3 was repeated except that 40 mmols of 
cyclohexylamine were employed instead of the aniline. As a result, the 
conversion of cryclohexylamine was 85% and the yield of ethyl 
N-cyclohexylcarbamate was 82% with a selectivity of 97%. Further, the 
reaction was repeated in the same manner as in Example 3 and the result 
obtained was as good as the above, i.e., the conversion of cyclohexylamine 
was 83% and the yield of ethyl N-cyclohexylcarbamate was 81% with a 
selectivity of 98%. 
EXAMPLE 123 
The procedure of Example 120 was repeated except that 1 mmol of ethyl 
iodide, and 1 mmol of N,N,N',N'-tetramethylethylenediamine were employed 
instead of the cesium iodide and that 40 ml of methanol were employed 
instead of the ethanol. As a result, the conversion of cyclohexylamine was 
88% and the yield of methyl N-cyclohexylcarbamate was 83% with a 
selectivity of 94%. 
EXAMPLE 124 
The procedure of Example 120 was repeated except that 1 mmol of potassium 
metaperiodate was employed instead of the cesium iodide and that 50 ml of 
methanol were employed instead of the ethanol. As a result, the conversion 
of cyclohexylamine was 85% and the yield of methyl N-cyclohexylcarbamate 
was 78% with a selectivity of 92%. 
COMATIVE EXAMPLE 3 
The procedure of Example 120 was repeated except that the cesium iodide was 
not employed. As a result, the conversion of cyclohexylamine was 10% and 
the yield of ethyl N-cyclohexylcarbamate was only 3%. 
EXAMPLE 125 
The procedure of Example 120 was repeated except that 40 mmols of 
di-n-butylamine were employed instead of the cyclohexylamine and that 2 
mmols of methyltriphenylphosphonium iodide were employed instead of the 
cesium iodide. As a result, the conversion of di-n-butylamine was 85% and 
the yield of ethyl N,N-n-butylcarbamate was 78% with a selectivity of 92%. 
EXAMPLE 126 
The procedure of Example 120 was repeated except that 30 mmols of 
di-n-butylamine were employed instead of the cyclohexylamine and that 1 
mmol of iodine and 1 mmol of cesium hydroxide were employed instead of the 
cesium iodide. As a result, the conversion of di-n-butylamine was 70% and 
the yield of methyl N,N-di-n-butylcarbamate was 56% with a selectivity of 
80%. 
EXAMPLE 127 
The procedure of Example 120 was repeated except that 15 mmols of 
1,6-hexamethylenediamine were employed instead of the cyclohexylamine and 
that 2 mmols of tetramethylammonium iodide were employed instead of the 
cesium iodide. As a result, the conversion of 1,6-hexamethylenediamine was 
94% and the yield of diethyl 1,6-hexamethylenedicarbamate was 87% with a 
selectivity of 93%. 
EXAMPLE 128 
The procedure of Example 120 was repeated except that 40 mmols of 
benzylamine were employed instead of the cyclohexylamine, that 1 mg-atom 
of palladium black was employed instead of 0.5 mg-atom of palladium black 
and that 1 mmol of tetramethylammonium iodide and 1 mmol of triethylamine 
were employed instead of the cesium iodide. As a result, the conversion of 
benzylamine was 90% and the yield of ethyl N-benzylcarbamate was 85% with 
a selectivity of 94%. The selectivity of molecular oxygen to the 
urethanation was 92%. When the above described procedure was repeated 
except that the trethylamine was not employed, the selectivity of oxygen 
to the urethanation was 80%. 
EXAMPLE 129 
In a 200 ml stirring type autoclave were charged 50 mmols of benzylamine, 
50 ml of ethanol, 1 g of 5% by weight rhodium supported on active carbon 
and 3 mmols of cesium iodide. After the air inside the autoclave had been 
replaced with carbon monoxide, carbon monoxide was pressurized into the 
autoclave to 80 Kg/cm.sup.2 and oxygen was pressurized into the autoclave 
to 6 Kg/cm.sup.2, resulting in a total pressure of 86 Kg/cm.sup.2. The 
reaction was carried out at 160.degree. C. for one hour with stirring and 
the reaction mixture obtained was subjected to filtration. As the result 
of analysis of the filtrate obtained, the conversion of benzylamine was 
77% and the yield of ethyl N-benzylcarbamate was 69% with a selectivity of 
90%. 
EXAMPLE 130 
In 500 ml stirring type autoclave were charged 100 mmols of aniline, 150 ml 
of ethanol, 1 mg-atom of palladium black and 2 mmols of tetraethylammonium 
iodide. After the air inside the autoclave had been replaced with carbon 
monoxide, the autoclave was heated to 160.degree. C. and a mixed gas of 70 
Kg/cm.sup.2 of carbon monoxide and 30 Kg/cm.sup.2 of air was continuously 
fed into the solution mixture in the autoclave at a rate of 0.5 Nl/min. 
After one hour the reaction was stopped and the reaction solution was 
subjected to analysis. As a result, the conversion of aniline was 99% and 
the yield of ethyl N-phenylcarbamate was 97% with a selectivity of 98%. 
EXAMPLE 131 
In a 300 ml stirring type autoclave were charged 30 mmols of 
2,4-diaminotoluene, 50 ml of methanol, 1 g of 10% by weight palladium 
supported on active carbon and 8 mmols of rubidium iodide. After the air 
inside the autoclave had been replaced with carbon monoxide, carbon 
monoxide was pressurized into the autoclave to 120 Kg/cm.sup.2 and oxygen 
was pressurized into the autoclave to 8 Kg/cm.sup.2, resulting in a total 
pressure of 128 Kg/cm.sup.2. The reaction was carried out at 160.degree. 
C. for one hour with stirring and the reaction mixture obtained was 
subjected to filtration. As the result of analysis of the filtrate 
obtained, the conversion of 2,4-diaminotoluene was 80% and the yield of 
dimethyl tolylene-2,4-dicarbamate was 68% and the yield of the 
aminomonourethane which was a mixture of methyl 
3-amino-4-methylcarbanilate and methyl 2-methyl-5-aminocarbanilate was 8%. 
The total selectivity to the urethanation was 95%. 
EXAMPLE 1 
In a 300 ml stirring type autoclave were charged 30 mmols of 
2,4-diaminotoluene, 50 ml of ethanol, 1 mg-atom of palladium black, 2 
mmols of iodoform and 2 mmols of potassium hydroxide. After the air inside 
the autoclave had been replaced with carbon monoxide, carbon monoxide was 
pressurized into the autoclave to 100 Kg/cm.sup.2 and then oxygen was 
pressurized into the autoclave to 7 Kg/cm.sup.2, resulting in a total 
pressure of 107 Kg/cm.sup.2. The reaction was carried out at 160.degree. 
C. for one hour with stirring, and subsequently the reaction mixture 
obtained was subjected to filtration. As the result of analysis of the 
filtrate, the conversion of 2,4-diaminotoluene was 88% and the yield of 
diethyl tolylene-2,4-dicarbamate was 74% and the yield of the 
aminomonourethane which was a mixture of ethyl 3-amino-4-methylcarbanilate 
and ethyl 2-methyl-4-aminocarbanilate was 11%. The total selectivity to 
the urethanation was 95%. 
EXAMPLE 133 
In a 200 ml stirring type autoclave were charged 30 mmols of aniline, 15 
mmols of nitrobenzene, 50 ml of methanol, 0.5 mmol of palladium chloride 
and 5 mmols of tetrabutylammonium iodide. After the air inside the 
autoclave had been replaced with carbon monoxide, carbon monoxide was 
pressurized into the autoclave to 140 Kg/cm.sup.2, and the reaction was 
carried out at 180.degree. C. for 3 hours with stirring. As the result of 
analysis of the reaction solution obtained, the conversions of aniline and 
nitrobenzene were 20% and 26%, respectively, and 7 mmols of methyl 
N-phenylcarbamate were obtained. 
EXAMPLE 134 
In a 200 ml stirring type autoclave were charged 30 mmols of aniline, 15 
mmols of nitrobenzene, 50 ml of methanol, 0.5 mmol of palladium chloride 
and 5 mmols of potassium metaperiodate. After the air inside the autoclave 
had been replaced with carbon monoxide, carbon monoxide was pressurized 
into the autoclave to 120 Kg/cm.sup.2, and the reaction was carried out at 
180.degree. C. for 6 hours with stirring. As the result of analysis of the 
reaction solution obtained, the conversions of aniline and nitrobenzene 
were 28% and 34%, respectively, and 8 mmols of methyl N-phenylcarbamate 
were obtained. 
EXAMPLE 135 
In a 200 ml stirring type autoclave were charged 30 mmols of aniline, 15 
mmols of nitrobenzene, 50 ml of ethanol, 3 mmols of palladium chloride, 3 
mmols of tetraiodomethane and 3 mmols of rubidium hydroxide. After the air 
inside the autoclave had been replaced with carbon monoxide, carbon 
monoxide was pressurized into the autoclave to 120 Kg/cm.sup.2, and the 
reaction was carried out at 180.degree. C. for 5 hours with stirring. As 
the result of analysis of the reaction solution, the conversions of 
aniline and nitrobenzene were 21% and 29%, respectively, and 8 mmols of 
ethyl N-phenylcarbamate were obtained. 
EXAMPLE 136 
In a 140 ml stirring type autoclave were charged 20 mmols of 
N,N'-diphenylurea, 40 ml of ethanol, 0.5 mg-atom of palladium black and 5 
mmols of cesium iodide. After the air inside the autoclave had been 
replaced with carbon monoxide, carbon monoxide was pressurized into the 
autoclave to 80 Kg/cm.sup.2 and then oxygen was pressurized into the 
autoclave to 6 Kg/cm.sup.2, resulting in a total pressure of 86 
Kg/cm.sup.2. The reaction was carried out at 160.degree. C. for one hour 
with stirring, and subsequently the reaction mixture obtained was 
subjected to filtration. As the result of analysis of the filtrate, the 
conversion of N,N'-diphenylurea was 100% and the yield of ethyl 
N-phenylcarbamate was 98% with a selectivity of 98%. 
EXAMPLE 137 
The procedure of Example 136 was repeated except that 5 mmols of 
tetramethylammonium iodide were employed instead of the cesium iodide. The 
filtrate obtained was a yellowish solution. As a result, the conversion of 
N,N'-diphenylurea was 100% and the yield of ethyl N-phenylcarbamate was 
99% with a selectivity of 99%. 
When ethanol was distilled from this solution under reduced pressure and 
then tetramethylammonium iodide was removed by washing with water, yellow 
crystals were precipitated. The crude crystals thus obtained were ethyl 
N-phenylcarbamate of 99% purity and recrystallized once from ethanol to 
give white crystals of ethyl N-phenylcarbamate of 100% purity. 
EXAMPLE 138 
The procedure of Example 136 repeated except that 5 mmols of 
methyltriphenylphosphonium iodide were employed instead of the cesium 
iodide. As a result, the conversion of N,N'-diphenylurea was 98% and the 
yield of ethyl N-phenylcarbamate was 96% with a selectivity of 98%. 
EXAMPLE 139 
In a N-methylpyrolidone solution containing 10% by weight of 
m-phenylenediamine was added an equimolar amount of 
2,4-pyridinedicarboxylic acid chloride, and the reaction was carried out 
at a temperature of from 40.degree. C. to 60.degree. C. for 3 hours. The 
reaction solution thus obtained was added dropwise to a large amount of 
water with stirring, and the precipitate formed was washed with an aqueous 
sodium hydroxide solution and with water and then dried to give a pyridine 
ring-containing aromatic polyamide having units of the formula: 
##STR22## 
This polymer was treated with methyl iodide to give an iodine-containing 
polymer having quaternary pyridium iodide groups. 
One gram of the iodine-containing polymer thus obtained, 25 mmols of 
N,N'-diphenylurea, 50 ml of methanol and 0.5 mg-atom of palladium black 
were charged into a 200 ml stirring type autoclave. After the air inside 
the autoclave was replaced with carbon monoxide, carbon monoxide was 
pressurized into the autoclave to 80 Kg/cm.sup.2, and subsequently oxygen 
was pressurized into the autoclave to 6 Kg/cm.sup.2, resulting in a total 
pressure of 86 Kg/cm.sup.2. The reaction was carried out with stirring at 
160.degree. C. for one hour, and then the reaction mixture was subjected 
to filtration. As the result of analysis of the filtrate, the conversion 
of N,N'-diphenylurea was 98% and the yield of ethyl N-phenylcarbamate 96% 
with a selectivity of 98%. 
When the above described procedure was repeated by using the palladium 
black and the iodine-containing polymer separated by filtration as such, 
the result obtained was as good as the above, i.e., the conversion of 
N,N'-diphenylurea was 99% and the yield of ethyl N-phenylcarbamate was 97% 
with a selectivity of 98%. 
EXAMPLE 140 
The procedure of Example 136 was repeated except that 1 mmol of potassium 
metaperiodate was employed instead of the cesium iodide. As a result, the 
conversion of N,N'-diphenylurea was 96% and the yield of ethyl 
N-phenylcarbamate was 94% with a selectivity of 98%. 
EXAMPLE 141 
The procedure of Example 136 was repeated except that 0.25 mmol of 
potassium tetraiodobismuthate was employed instead of the cesium iodide. 
As a result, the conversion of N,N'-diphenylurea was 92% and the yield of 
ethyl N-phenylcarbamate was 87% with a selectivity of 95%. 
EXAMPLE 142 
The procedure of Example 136 was repeated except that 0.3 mmol of iodoform 
and 1 mmol of triethylamine were employed instead of the cesium iodide. As 
a result, the conversion of N,N'-diphenylurea was 95% and the yield of 
ethyl N-phenylcarbamate was 92% with a selectivity of 97%. In the filtrate 
obtained no palladium was detected. The selectivity of molecular oxygen to 
the urethanation was 94%. 
When the above described procedure was repeated except that the 
triethylamine was not employed, the conversion of N,N'-diphenylurea was 
85% and the yield of ethyl N-phenylcarbamate was 80% with a selectivity of 
94%, and the selectivity of molecular oxygen to the urethanation was 75%. 
The reaction solution obtained in either case was transparent and 
yellowish. 
EXAMPLE 143 
The procedure of Example 136 was repeated except that 1 mmol of iodine and 
1 mmol of triethylamine were employed instead of the cesium iodide. As a 
result, the conversion of N,N'-diphenylurea was 98% and the yield of ethyl 
N-phenylcarbamate was 96% with a selectivity of 98%. In the filtrate no 
palladium was detected. 
When the above described procedure was repeated except that the 
triethylamine was not employed, the conversion of N,N'-diphenylurea was 
48% and the yield of ethyl N-phenylcarbamate was 31% with a selectivity of 
65%. 
COMATIVE EXAMPLE 4 
The procedure of Example 136 was repeated except that the cesium iodide was 
not employed. As a result, the conversion of N,N'-diphenylurea was 10% and 
the yield of ethyl N-phenylcarbamate was only 3%. 
COMATIVE EXAMPLE 5 
The procedure of Example 136 was repeated except that 1 mmol of 
triethylamine was employed instead of the cesium iodide. As a result, the 
conversion of N,N'-diphenylurea was 5% and the yield of ethyl 
N-phenylcarbamate was less than about 1%. 
EXAMPLES 144 TO 175 
The procedure of Example 136 was repeated except that 0.5 mg-atom of a 
platinum group metal or a compound containing the platinum group element 
based on the metal element set forth in Table 2 was employed in the 
presence or absence of, as an additional promoter, a basic substance set 
forth in Table 2 instead of the cesium iodide 
The results are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Compound ContainingorPt Group Metal 
Halogen-containing 
Basic 
##STR23## 
##STR24## 
Example 
At Least One 
Compound Substance 
Conversion Yield 
Selectivity 
No. Pt Group Element*.sup.1 
(mmol) (mmol) (%) (%) (%) 
__________________________________________________________________________ 
144 Pd Black LiCl 5 -- 80 70 88 
145 " KBr 5 -- 88 79 90 
146 " RbI 5 -- 98 93 95 
147 " BaI.sub.2.2H.sub.2 O 
5 -- 75 69 92 
148 RhI.sub.3 CsI 5 -- 93 88 95 
149 Ru Black " 5 -- 80 72 90 
150 5% Pt/C " 5 -- 85 76 89 
151 Pd Black NH.sub.4 Br 
5 -- 90 83 92 
152 " [(C.sub.2 H.sub.5).sub.4 N].sup..sym. I.sup..crclbar. 
5 -- 98 94 96 
153 5% Pd/C [(CH.sub.3).sub.4 N].sup..sym. I.sup..crclbar. 
5 -- 100 98 98 
154 RhI.sub.3 " 5 -- 90 84 93 
155 Pd Black [(CH.sub.3).sub.4 P].sup..sym. I.sup..crclbar. 
5 -- 100 96 96 
156 " [(CH.sub.3)S].sup..sym. I.sup..crclbar. 
1 (n-C.sub.4 H.sub.9).sub.3 N1 
60 48 80 
157 5% Rh/C [(C.sub.6 H.sub.5).sub.3 PCH.sub.3 ].sup..sym. I.sup..crc 
lbar. 5 -- 93 88 95 
158 5% (PdTe)/C*.sup.2 
[(C.sub.6 H.sub.5).sub.3 PCH.sub.3 ].sup..sym. I.sup..crc 
lbar. -- 97 94 97 
159 Ru Black " -- 90 82 91 
160 Pd Black KBrO.sub.3 1 -- 62 56 90 
161 " RbIO.sub.4 1 -- 95 92 97 
162 " HIO.sub.3 1 CsOH1 80 74 92 
163 5% Rh/C KIO.sub.4 1 -- 82 75 92 
164 Ru Black " 1 -- 70 61 87 
165 Pd Black K.sub.2 [TeBr.sub.6 ] 
0.2 
-- 90 85 94 
166 " [(CH.sub.3).sub.4 N][I.sub.5 ] 
0.2 
-- 67 59 88 
167 " " 0.2 
RbOH1 76 68 90 
168 RhI.sub.3 K[BiI.sub.4 ].H.sub.2 O 
0.25 
-- 88 79 90 
169 5% Pt/C " 0.25 
-- 85 75 88 
170 Pd Black CH.sub.3 I 0.8 
(C.sub.2 H.sub.5).sub.3 N1 
92 85 92 
171 " CHI.sub.3 0.3 
RbOH1 94 89 95 
172 5% Rh/C CHI.sub.3 0.3 
(C.sub.2 H.sub.5).sub.3 N1 
90 83 92 
173 Pd Black I.sub.2 1 NaHCO.sub.31 
93 91 98 
174 " " 1 RbOH1 96 94 98 
175 5% Rh/C " 1 (C.sub.2 H.sub.5).sub.3 N1 
88 84 95 
__________________________________________________________________________ 
*.sup.1 %: weight % 
*.sup.2 (PdTe)/C was prepared by supporting palladium chloride and 
tellurium dioxide at a mol ratio of 10 to 3 on active carbon and then 
reducing the resultant with hydrogen at 350.degree. C. 
EXAMPLE 176 
In a 140 ml stirring type autoclave were charged 20 mmols of 
N,N'-dicyclohexylurea, 40 ml of ethanol, 0.5 mg-atom of palladium black 
and 2 mmols of cesium iodide. After the air inside the autoclave had been 
replaced with carbon monoxide, carbon monoxide was pressurized into the 
autoclave to 80 Kg/cm.sup.2 and then oxygen was pressurized into the 
autoclave to 6 Kg/cm.sup.2, resulting in a total pressure of 86 
Kg/cm.sup.2. The reaction was carried out at 160.degree. C. for one hour 
with stirring, and subsequently the reaction mixture obtained was 
subjected to filtration. As the result of analysis of the filtrate, the 
conversion of N,N'-dicyclohexylurea was 95% and the yield of ethyl 
N-cyclohexyl carbamate was 93% with a selectivity of 98%. 
COMATIVE EXAMPLE 6 
The procedure of Example 176 was repeated except that the cesium iodide was 
not employed. As a result, the conversion of N,N'-dicyclohexylurea was 8% 
and the yield of ethyl N-cyclohexyl carbamate was only 2%. 
EXAMPLE 177 
The proedure of Example 176 was repeated except that 20 mmols of urea were 
employed instead of the N,N'-dicyclohexylurea. As a result, the conversion 
of urea was 85% and the yield of ethyl carbamate was 80% with a 
selectivity of 94%. 
EXAMPLE 178 
The procedure of Example 176 was repeated except that 2 mmols of 
tetramethylammonium iodide were employed instead of the cesium iodide. As 
a result, a yellowish filtrate was obtained, and the conversion of 
N,N'-dicyclohexylurea was 96% and the yield of ethyl N-cyclohexyl 
carbamate was 94% with a selectivity of 98%. 
EXAMPLE 179 
The procedure of Example 178 was repeated except that 20 mmols of 
N,N'-di-n-butylurea were employed instead of the N,N'-dicyclohexylurea. As 
a result, the conversion of N,N'-di-n-butylurea was 94% and the yield of 
ethyl N-n-butylcarbamate was 88% with a selectivity of 94%. 
EXAMPLE 180 
The procedure of Example 3 was repeated except that 20 mmols of 
N,N'-dicyclohexylurea were employed instead of the aniline. As a result, 
the conversion of N, N'-dicyclohexylurea was 94% and the yield of ethyl 
N-cyclohexylcarbamate was 90% with a selectivity of 96%. Further, the 
reaction was repeated in the same manner as in Example 3 and the result 
obtained was as good as the above, i.e., the conversion of 
N,N'-dicyclohexylurea was 93% and the yield of ethyl N-cyclohexylcarbamate 
was 89% with a selectivity of 96%. 
EXAMPLE 181 
In a 140 ml stirring type autoclave were charged 20 mmols of 
N,N'-dibenzylurea, 40 ml of ethanol, 1 mg-atom of palladium black and 1 
mmol of potassium metaperiodate. After the air inside the autoclave had 
been replaced with carbon monoxide, carbon monoxide was pressurized into 
the autoclave to 70 Kg/cm.sup.2 and then air was pressurized into the 
autoclave to 30 Kg/cm.sup.2, resulting in a total pressure of 100 
Kg/cm.sup.2. The reaction was carried out at 160.degree. C. for one hour 
with stirring, and subsequently the reaction mixture obtained was 
subjected to filtration. As the result of analysis of the filtrate, the 
conversion of N,N'-benzylurea was 95% and the yield of ethyl 
N-benzylcarbamate was 90% with a selectivity of 95%. 
EXAMPLE 182 
The procedure of Example 181 was repeated except that 1 mmol of 
tetraiodomethane and 1 mmol of 1,5-diazabicyclo-[4,3,0]-nonene-5(DBN) were 
employed instead of the potassium metaperiodate. As a result, the 
conversion of N,N'-dibenzylurea was 95% and the yield of ethyl 
N-benzylcarbamate was 91% with a selectivity of 96%. 
EXAMPLE 183 
The procedure of Example 181 was repeated except that 1 mmol of 
tetraiodomethane was employed instead of the potassium metaperiodate. As a 
result, the conversion of N,N'-benzylurea was 80% and the yield of ethyl 
N-benzylcarbamate was 72% with a selectivity of 90%. 
EXAMPLE 184 
The procedure of Example 176 was repeated except that 20 mmols of 
N,N'-di-n-butylurea were employed instead of the N,N'-dicyclohexylurea and 
that 1 mmol of iodine and 1 mmol of potassium hydrogen carbonate were 
employed instead of the cesium iodide. As a result, the conversion of 
N,N'-di-n-butylurea was 73% and the yield of ethyl N-n-butylcarbamate was 
66% with a selectivity of 90%. 
EXAMPLE 185 
In a 200 ml stirring type autoclave were charged 30 mmols of 
N,N'-diphenylurea, 15 mmols of nitrobenzene, 50 ml of methanol, 0.5 mmol 
of palladium chloride and 5 mmols of tetrabutylammonium iodide. After the 
air inside the autoclave had been replaced with carbon monoxide, carbon 
monoxide was pressurized into the autoclave to 140 Kg/cm.sup.2, and the 
reaction was carried out at 180.degree. C. for 5 hours with stirring. As 
the result of analysis of the reaction solution obtained, the conversions 
of N,N'-diphenylurea and nitrobenzene were 26% and 33%, respectively, and 
15 mmols of methyl N-phenylcarbamate were obtained. 
EXAMPLE 186 
In a 200 ml stirring type autoclave were charged 30 mmols of 
N,N'-diphenylurea, 15 mmols of nitrobenzene, 50 ml of methanol, 0.5 mmol 
of palladium chloride and 5 mmols of cesium iodide. After the air inside 
the autoclave had been replaced with carbon monoxide, carbon monooxide was 
pressurized into the autoclave to 120 Kg/cm.sup.2, and the reaction was 
carried out at 180.degree. C. for 4 hours with stirring. As the result of 
analysis of the reaction solution obtained, the conversions of 
N,N'-diphenylurea and nitrobenzene were 25% and 30%, respectively, and 14 
mmols of methyl N-phenylcarbamate were obtained. 
EXAMPLE 187 
In a 200 ml stirring type autoclave were charged 30 mmols of 
N,N'-diphenylurea, 15 mmols of nitrobenzene, 50 ml of methanol, 1 mmol of 
potassium tetrabromopalladate, 2 mmols of iodine and 2 mmols of 
triethylamine. After the air inside the autoclave had been replaced with 
carbon monoxide, carbon monoxide was pressurized into the autoclave to 120 
Kg/cm.sup.2, and the reaction was carried out at 180.degree. C. for 6 
hours with stirring. As the result of analysis of the reaction solution, 
the conversions of N,N'-diphenylurea and nitrobenzene were 30% and 38%, 
respectively, and 15 mmols of methyl N-phenylcarbamate were obtained. 
EXAMPLE 188 
In a 200 ml stirring type autoclave were charged 15 mmols of 
p-phenylenediamine, 80 ml of ethanol, 0.5 mg-atom of palladium black and 
1.2 mmols of sodium iodide. After the air inside the autoclave had been 
replaced with carbon monoxide, carbon monoxide was pressurized into the 
autoclave to 100 Kg/cm.sup.2 and then air was pressurized into the 
autoclave to 30 Kg/cm.sup.2, resulting in a total pressure of 130 
Kg/cm.sup.2. The reaction was carried out at a temperature of from 
160.degree. C. to 170.degree. C. for two hours with stirring. As the 
result of analysis of the reaction solution obtained, the conversion of 
p-phenylenediamine was 95% and the yield of diethyl p-phenylenedicarbamate 
was 88% with a selectivity of 93%. 
EXAMPLE 189 
The procedure of Example 189 was repeated except that 30 mmols of 
diphenylamine were employed instead of the p-phenylenediamine. As a 
result, the conversion of diphenylamine was 83% and the yield of ethyl 
N,N'-diphenylcarbamate was 70% with a selectivity of 84%. 
EXAMPLE 190 
In a 140 ml stirring type autoclave were charged 8 mmols of 
1,8-diamino-4-aminomethyloctane, 50 ml of trifluoroethanol, 0.5 mg-atom of 
palladium black and 2 mmols of cesium iodide. After the air inside the 
autoclave had been replaced with carbon monoxide, carbon monoxide was 
pressurized into the autoclave to 80 Kg/cm.sup.2 and then oxygen was 
pressurized into the autoclave to 6 Kg/cm.sup.2, resulting in a total 
pressure of 86 Kg/cm.sup.2. The reaction was carried out at 200.degree. C. 
for one hour with stirring. As the result of analysis of the reaction 
solution obtained, the yield of a triurethane having the following 
formula: 
##STR25## 
was 94% with a selectivity of 95%. 
EXAMPLE 191 
The procedure of Example 136 was repeated except that 20 mmols of 
N-phenyl-N'-p-tolylurea were employed instead of the N,N'-diphenylurea and 
that 1 mmol of potassium iodide was employed instead of the cesium iodide. 
As a result, the conversion of N-phenyl-N'-p-tolylurea was 98% and the 
yield of ethyl N-phenylcarbamate and ethyl N-p-tolylcarbamate was 96%, 
respectively with a selectivity of 98%, respectively. 
EXAMPLE 192 
In a 200 ml stirring type autoclave were charged 50 mmols of aniline, 60 ml 
of cyclohexanol, 1 mg-atom of palladium black and 2 mmols of potassium 
iodide. After the air inside the autoclave had been replaced with carbon 
monoxide, carbon monoxide and hydrogen were pressurized into the autoclave 
to 120 Kg/cm.sup.2 and 1.5 Kg/cm.sup.2, respectively and then air was 
pressurized into the autoclave to 40 Kg/cm.sup.2. The reaction was carried 
out at a temperature of from 150.degree. C. to 170.degree. C. for one hour 
with stirring, and subsequently the reaction mixture obtained was 
subjected to filtration. As the result of analysis of the filtrate, the 
conversion of aniline was 98% and the yield of cyclohexyl 
N-phenylcarbamate was 95% with a selectivity of 97%. 
When the above described procedure was repeated except that the hydrogen 
was not employed, the conversion of aniline was 99% and the yield of 
cyclohexyl N-phenylcarbamate was 96% with a selectivity of 97%. 
This Example shows that a small amount of hydrogen present does not affect 
the urethanation reaction according to this invention. 
EXAMPLE 193 
In a 200 ml stirring type autoclave were charged 50 mmols of aniline, 50 
mmols of nitrobenzene, 60 mmols of methanol, 2 mmols of palladium chloride 
and 5 mmols of sodium iodide. After the air inside the autoclave had been 
replaced with carbon monoxide, carbon monoxide and hydrogen were 
pressurized into the autoclave to 130 Kg/cm.sup.2, and 12 Kg/cm.sup.2, 
respectively, resulting in a total pressure of 142 Kg/cm.sup.2. The 
reaction was carried out at 200.degree. C. for 3 hours with stirring. As 
the result of analysis of the reaction solution obtained, 68 mmols of 
methyl N-phenylcarbamate were formed, and 17 mmols of aniline and 10 mmols 
of nitrobenzene were unreacted. The selectivity of methyl 
N-phenylcarbamate from aniline and nitrobenzene was 93%. 
The foregoing examples illustrate, without limitation, the catalyst and 
process of the present invention. It is understood that changes and 
variations can be made in the examples without departing from the spirit 
and scope of the invention as defined in the following claims.