Selective synthesis of substituted amines

Selective mono- or di-amination of alkanediols is controllably obtained by catalytic reaction with secondary amines at moderate temperature and autogenous pressure, by selection of the catalyst employed. Ruthenium complexes compounded or admixed with selected organic phosphines, such as triphenylphosphine, favor high yields of alkanolamines, while ruthenium complexes in the absence of organic phosphines favor production of alkylenediamines. Iridium complexes with or without organic phosphines in admixture or chemical combination, also promote production of alkylenediamines.

TECHNICAL FIELD OF THE INVENTION 
The present invention relates to catalytic reactions of alkanediols with 
secondary amines and is particularly concerned with the controlled 
selective production of reaction products therefrom predominating 
respectively in (1) alkanolamines or (2) alkylenediamines. 
BACKGROUND OF THE INVENTION 
It is known to produce certain N-substituted alkanediamines and various 
alkanolamines from dichloroalkanes and alkylene oxides, respectively. 
These starting materials are expensive and/or extremely toxic. The toxic 
nature of some of the alkylene oxides is a special problem for small-scale 
users, since the unit costs of installing safe-guards and monitoring 
systems increase with decreasing production scale. 
Previous prior art attempts at aminating alkanediols have been limited to 
high temperature reactions utilizing heterogeneous catalysts. The high 
temperatures required in the prior art methods led to high operating 
pressures and low selectivities. 
A limited number of prior art disclosures describe the use of homogeneous 
catalysts, e.g. RhH(PPh.sub.3).sub.4, for the reaction of monoalcohols 
with amines. (See, for example, Grigg, et al, J. C. S. Chem. Comm., pp 
611-612 [1981]). 
European Patent Publication No. 034,480 describes in general the 
preparation of N-alkylamine or N,N-dialkylamine by reacting a primary or 
secondary amine with a primary or secondary alcohol in the presence of 
certain noble mtal catalysts, such as the metal, salt or complex of the 
noble metal. The preferred example of catalyst is a rhodium 
hydride-triphenylphosphine complex. Although the disclosure is concerned 
largely with reactions involving monofunctional alcohols, there is also 
disclosed the reaction of a primary amine with a diol for the formation of 
heterocyclic ring compounds containing the amine N atom. For this purpose, 
the diol used should contain at least four atoms in the chain so that 
cyclization can occur. The publication contains no disclosure of reaction 
of a diol with secondary amine, wherein cyclization is not possible. 
An article by Murahashi, et al. in Tetrahedron Letters (vol. 23, No. 2, pp. 
229-232, [1982]) describes the synthesis of secondary amines by reaction 
of alcohols with amines in the presence of RuH.sub.2 (PPh.sub.3).sub.4 
catalyst. By the reaction of butane diol or higher alkane diols with 
n-hexylamine, N-heterocyclic compounds are formed. 
U.S. Pat. No. 3,708,539 discloses the condensation of amines with alcohols 
in the presence of ruthenium or certain other noble metal catalysts 
introduced as halides. The process is preferably conducted in the presence 
of a biphilic ligand of the structure ER.sub.3, wherein E may be 
phosphorus or arsenic. Particular examples are directed to (1) reaction of 
butanol with dibutylamine obtaining tributylamine; (2) using hexanol as 
reactant in the same manner resulted in the formation of 
dibutylhexylamine. 
U.S. Pat. No. 4,487,967 discloses a process for selectively preparing 
severely sterically hindered secondary aminoether alcohols by reacting a 
primary amino compound with a polyalkenyl ether glycol in the presence of 
a hydrogenation catalyst at elevated temperatures and pressures. 
Reaction of diols with ammonia or alkylamines to produce diaminoalkanes is 
disclosed in U.S. Pat. No. 3,270,059. The reaction is carried out in the 
presence of hydrogen at 150.degree.-300.degree. C. and at a pressure of at 
least 10 atmospheres, over a solid catalyst which contains at least one 
metal from the group consisting of cobalt and nickel. When secondary 
amines are employed as reactants, tertiary diamines are obtained. Reaction 
of ethylene glycol with diethylamine under the conditions of the patent 
yields chiefly tetraethylethylene diamine and a lesser amount of 
diethylethanolamine. 
The selective conversion of primary amines to yield (I) N,N-dimethylalkyl- 
or (II) N,N-dialkylmethyl-amines by reaction with methanol in the presence 
of RuCl.sub.2 (Ph.sub.3 P).sub.3 catalyst, is disclosed in an article by 
Arcelli, et al. in the Journal of Organometallic Chemistry (vol. 235, pp. 
93-96 [1982]). The selectivity towards the I or II type compound is 
controlled by choice of the amount of catalyst and the ratio of reactants. 
SUMMARY OF THE INVENTION 
In accordance with the present invention, tertiary alkanolamines and 
alkanediamines are selectively produced in high yield from alkanediols 
selected from the group consisting of ethylene glycol and 1,3 propanediol, 
by reaction with secondary amines in the presence of ruthenium or iridium 
complexes. Selectivity favoring production of alkanolamines (i.e., 
mono-amination) is achieved by the use of a complex of a ruthenium 
compound with selected phosphine ligands, such as triphenylphosphine or a 
mixture of the ruthenium compound with such ligands. Selectivity toward 
production of alkanediamines (di-amination) is achieved by the use of an 
iridium complex catalyst with or without a phosphine modifier, or of the 
ruthenium compound in the presence of select phosphine components or in 
the absence of such components. 
DETAILED DESCRIPTION 
In practice of the invention, a solution of a secondary amine and 
alkanediol, such as ethylene glycol or 1,3 propanediol, is stirred in the 
presence of the ruthenium or iridium catalyst for two to six hours. The 
temperature range is maintained between about 100.degree. to 125.degree. 
C., with lower temperatures giving lower reaction rates and higher 
temperatures tending to effect dehydrogenation and/or decarbonylation of 
the diol. 
The secondary amines can be represented by the formula: HNR.sub.2 in which 
--NR.sub.2 is 
##STR1## 
and in which "alk" and "alk'" are alkyl groups of up to 20 carbon atoms. 
The alkanediols can include up to 12 carbon atoms with a linear or branched 
carbon skeleton. Preferably the hydroxyl functionalities should be 
separated by not more than one carbon. Examples of most preferred diols 
include ethylene glycol, and 1,3 propanediol. 
The concentration of the secondary amine may be in the range of 0.5 to 10 
mols per liter of reaction medium, and preferably 1 to 5 mols/liter. The 
catalyst concentration may be generally in the range of 10.sup.-4 to 
10.sup.-1 moles per liter of reaction medium, and preferably 10.sup.-3 to 
10.sup.-2 moles/liter. 
Selectivity of the reaction can be altered to give mainly mono-amination 
(production of alkanolamines) or di-amination (production of 
alkylenediamines), by proper choice of catalyst. Proven catalysts that 
favor mono-amination are: RuCl.sub.2 (PPh.sub.3).sub.3, 
RuHCl(PPh.sub.3).sub.3 ; RuCl.sub.3.xH.sub.2 O admixed with about 3 
moles/mole of PPh.sub.3 ; [Ru(NH.sub.3).sub.6 ]Cl.sub.3 admixed with 3 
moles/mole of PPh.sub.3 ; K.sub.2 [(RuCl.sub.5).sub.2 O], Ru(NO)Cl.sub.3, 
K.sub.2 RuCl.sub.5, K.sub.2 RuCl.sub.6, and [Ru(NH.sub.3).sub.6 ]Cl.sub.2, 
each admixed with about 3 moles/mole of PPh.sub.3. Also found to favor 
mono-amination was K.sub.2 RuO.sub.4 admixed with about 5 moles/mole 
PPh.sub.3. For these ruthenium-based systems, the selectivity preference 
progresses smoothly from mono- to di-amination as the amount of PPh.sub.3 
is decreased. In addition to the above listed ruthenium complexes other 
catalysts which are expected to favor mono-amination include: K.sub.2 
RuCl.sub.6, K.sub.2 RuCl.sub.5, RuCl.sub.2 (DMSO).sub.4, "Ruthenium Red" 
(ammoniated ruthenium oxychloride), anhydrous RuCl.sub.3, etc., each in 
admixture or molecular association with triphenylphosphine. 
In general, based on observations, it can be stated that triarylphosphines 
substituted in the para position behave quite similarly to unsubstituted 
triphenylphosphine in admixture or in chemical combination with the listed 
ruthenium catalytic compounds. Those with ortho substituents show 
decreased rates of reaction with the selectivity tending toward 
diamination. The situation is more complex in the case of mixed 
aryl-alkylphosphines, including the potentially chelating diphosphines, 
bis(diphenylphosphino)methane (DPPM) and bis(diphenylphosphino)ethane 
(DPPE). Also included in this category are triphenylphosphite and 
tri-isopropylphosphine. However, in most cases, it was observed that 
mono-amination is favored over di-amination by the addition of organic 
phosphine ligand as compared to the catalytic reaction in the absence of 
phosphine. As indicated by the listed examples, the organic phosphine 
compound may be initially introduced into the reaction medium as a 
separate component or in a form chemically combined with the platinum 
group metal catalyst, e.g. ruthenium or iridium. The organic phosphine 
compound or complex preferably is one corresponding to the formula: 
EQU PR.sub.1 R.sub.2 R.sub.3 
wherein R.sub.1 and R.sub.2 are each hydrogen or an alkyl or aryl 
hydrocarbyl group and R.sub.3 is a hydrocarbyl group; each said 
hydrocarbyl group separately containing up to 12 carbon atoms. 
Di-amination is selectively favored by RuCl.sub.3.xH.sub.2 O 
(phosphine-free), and by IrCl.sub.3.xH.sub.2 O (phosphine-free) or in 
admixture with triphenylphosphine, as well as by phosphine-free ruthenium 
mixtures and complexes such as: K.sub.2 [(RuCl.sub.5).sub.2 O], 
Ru(NO)Cl.sub.3, K.sub.2 RuCl.sub.5, K.sub.2 RuCl.sub.6, RuCl.sub.2 
(DMSO).sub.4, and "Ruthenium Red", in the absence of mixed or chemically 
associated phosphines. 
The catalysts employed in practice of the invention, without being bound to 
any particular theory, apparently function as homogeneous catalysts, since 
they are at least partially dissolved in the reaction medium. As a result, 
such catalysts obtain more selective product distribution than that 
obtained using heterogeneous catalysts. Moreover, catalyst modifiers, such 
as the triphenylphosphine in the instant case, have a marked effect on the 
activity of homogeneous catalysts. Thus, by the practice of the present 
invention, the selective manufacture of desired alkanolamines or of the 
desired di-amines is made possible utilizing readily available and 
relatively low toxicity starting materials. Furthermore, the desired 
products are readily obtained under relatively mild operating conditions, 
preferably at autogenous pressure, and temperatures in the range of about 
100.degree. to 125.degree. C., without requiring addition of hydrogen to 
the system, although hydrogen may be employed, if desired. 
The exact composition and structure of the active catalyst species 
promoting the reaction is not clear, since the form in which the catalyst 
is introduced may function merely as a precursor to the active structure 
formed in the medium under reaction conditions. While carbonyl complexes 
have been observed in reaction mixtures, the use of isolated neutral 
carbonyl complexes of ruthenium as such catalyst precursors were found to 
lead to lower catalytic activity. 
Among other active catalysts favoring di-amination, good results are 
obtained with IrH(Cl).sub.2 (PPh.sub.3).sub.3. Iridium carbonyl complexes, 
like the ruthenium carbonyl complexes, show decreased overall activity. 
Surprisingly, however, IrH.sub.2 Cl(PPh).sub.3 showed relatively low 
overall activity, but favored di-amination. 
The process of the invention may be carried out in the presence of added 
solvents or diluents, among which are preferred; N-methylpyrrolidinone, 
N,N-dimethylacetamide, dimethylsulfoxide (DMSO), water, 
1,2-dimethoxyethane. 
While on the basis of prior art disclosures, it was expected that ruthenium 
and rhodium-based catalysts would show similar behavior in the promotion 
of amination reactions, it was unexpectedly found in preliminary 
experiments that this was not the case in reactions of diols, particularly 
ethylene glycol and 1,3 propanediol, with secondary amines. 
Several experimental runs were carried out in accordance with the present 
process. These runs are set out in the examples reported below. These 
examples are only meant to illustrate the present invention and are not 
meant to be limiting. 
All of the runs, unless stated otherwise, were carried out under nitrogen 
atmosphere. The GC analyses were performed using a copper column with 15% 
Carbowax 20M on Gaschrom Q as the stationary phase. All reaction vessels 
were charged in a glove box under an inert (N.sub.2) atmosphere. 
The reactions at 120.degree. C. were carried out in a 22 ml Parr stainless 
steel pressure vessel while the reactions at 100.degree. and 110.degree. 
C. with liquid sampling were carried out in a small flask equipped with a 
septum sealed side arm and fitted with a reflex condenser. Quantitation 
was by the internal standard method with 1-methyl-2-pyrrolidinone added as 
the reference. Liquid amines were added directly to the reaction vessel 
while gaseous amines were first dissolved in ethylene glycol or other diol 
to form a solution of known concentration, of which a known volume was 
charged to the reaction vessel.

EXAMPLE 1 
A series of experimental runs were carried out with various diols and 
different secondary amines at a reaction temperature of 
120.degree.-125.degree. C. for 2-2.5 hours. The amine concentration in 
each of the runs was about 1.8M and the catalyst concentration about 
2.times.10.sup.-2 M. The reactants and catalysts employed in these runs 
are set out in Table 1, wherein the reactants are designated by: 
EG=ethylene glycol, PRDIOL=propanediol, MOR=morpholine, DMA=dimethylamine, 
DEA=diethylamine, DIPA=di-isopropylamine. Total selectivity (selec) is 
defined as 
##EQU1## 
of mono-aminated product(s) and Yd=yield of diaminated product(s). 
The relative selectivities, mono- vs di-, is expressed as a selectivity 
coefficient (r) wherein: 
##EQU2## 
TABLE 1 
______________________________________ 
Con- 
ver- Total 
Run sion Selec 
No. Amine Diol Catalyst % % r 
______________________________________ 
1 MOR EG RuCl.sub.2 (PPh.sub.3).sub.3 
100 92 0.09 
2 DMA EG RuCl.sub.2 (PPh.sub.3).sub.3 
100 85 0.04 
3 DMA 1,2 RuCl.sub.2 (PPh.sub.3).sub.3 
67 95 0.06 
PRDIOL 
4 DMA 1,3 RuCl.sub.2 (PPh.sub.3).sub.3 
85 66 0.01 
PRDIOL 
5 DIPA EG RuCl.sub.2 (PPh.sub.3).sub.3 
20 100 0 
6 MOR EG RuCl.sub.3.xH.sub.2 O 
100 96 0.83 
7 DMA EG RuCl.sub.3.xH.sub.2 O 
ca 90 &gt;90 0.89 
8 DMA 1,2- RuCl.sub.3.xH.sub.2 O 
41 81 0.39 
PRDIOL 
9 DMA 1,3- RuCl.sub.3.xH.sub.2 O 
70 51 0.88 
PRDIOL 
10 MOR EG IrCl.sub.3 + 3PPh.sub.3 
79 90 0.89 
11 DMA EG IrCl.sub.3 + 3PPh.sub.3 
76 72 0.87 
12 DMA 1,2- IrCl.sub.3 + 3PPh.sub.3 
36 66 0.36 
PRDIOL 
13 DMA 1,3- IrCl.sub.3 + 3PPh.sub.3 
45 43 0.93 
PRDIOL 
14 DEA EG RuCl.sub.2 (PPh.sub.3).sub.3 
98 92 0.01 
15 DEA EG RuCl.sub.3.xH.sub.2 O 
42 98 0.85 
______________________________________ 
EXAMPLE 2 
Another series of runs was carried out under conditions of Example 1 to 
determine the effect of the triphenylphosphine to ruthenium ratio (P:Ru) 
on the reaction of ethylene glycol with morpholine, catalyzed by mixtures 
of RuCl.sub.3.xH.sub.2 O with PPh.sub.3. The results are reported in Table 
2. 
TABLE 2 
______________________________________ 
Total 
Conversion Selectivity 
Run P:Ru % r % 
______________________________________ 
14 0 60 .91 82 
15 0 100 .83 95 
16 0 100 .83 96 
17 0.5 53 .53 91 
18 1.0 79 .22 90 
19 3.0 95 .05 91 
______________________________________ 
As seen from the above-tabulated results, by the judicious use of 
triphenylphosphine as catalyst modifier with ruthenium complexes, 
selectivity of the reaction can be altered to obtain high conversion to 
(i) mono-aminated or (ii) di-aminated products, as represented by the 
equations: 
EQU HOCH.sub.2 CH.sub.2 OH+HNR.sub.2 .fwdarw.HOCH.sub.2 CH.sub.2 NR.sub.2 
+H.sub.2 O (i) 
EQU HOCH.sub.2 CH.sub.2 OH+2HNR.sub.2 .fwdarw.R.sub.2 NCH.sub.2 CH.sub.2 
NR.sub.2 +2H.sub.2 O (ii) 
in which --NR.sub.2 is the same as that defined under the Detailed 
Description. 
EXAMPLE 3 
Another series of runs was carried out in the amination of ethylene glycol 
with various secondary amines in the presence of RuCl.sub.2 
(PPh.sub.3).sub.3 as the added catalyst at 120.degree. C. These runs were 
made using 5 ml of glycol to 0.011-0.012 mol. amine and 1 mol% Ru (based 
on amine). The results are tabulated in Table 3. 
TABLE 3 
______________________________________ 
Amine pyrrolidine 
morpholine dimethylamine 
Time (hr) 6 2 3 
Conv. (%) 100 100 100 
Selectivity (%) 
R.sub.2 NCH.sub.2 CH.sub.2 OH 
79 83 81 
R.sub.2 NCH.sub.2 CH.sub.2 NR.sub.2 
(observed) 9 4 
______________________________________ 
It will be seen from Table 3 that high conversion is obtained with the 
ruthenium catalyst at moderate temperature, and unexpectedly high 
selectivity to substituted ethanolamines. 
Some increase in pressure was noted in the runs at 120.degree. C., but 
these increases amounted to only about 15 psig (at 25.degree. C.) in a 22 
ml Parr vessel. In contrast, higher temperature runs led to net pressure 
increases of 60-70 psig. Thus, the lower temperature apparently prevents 
hydrogen loss from the reaction system--an observation consistent with 
higher sensitivity to the simple amination products at the lower 
temperatures. 
EXAMPLE 4 
The effect of varying the starting Ru complex on product distributions is 
shown in Table 4. These runs were made using ethylene glycol with 
morpholine as the secondary amine; 5 ml of glycol were used per gram of 
morpholine (=0.0115 mol) and 1 mol% Ru (based on morpholine). 
TABLE 4 
______________________________________ 
RuCl.sub.2. 
RuHCL. RuCl.sub.3.xH.sub.2 O + 
RuCl.sub.3. 
Complex (PPh.sub.3).sub.3 
(PPh.sub.3).sub.3 
3PPh.sub.3 
xH.sub.2 O 
______________________________________ 
Time (hr) 6 5.5 2 2 
Temp (.degree.C.) 
100 100 120 120 
Conv (%) 89 94 95 100 
Selec (%): 
R.sub.2 NCH.sub.2 CH.sub.2 OH 
94 90 88 15 
R.sub.2 NCH.sub.2 CH.sub.2 NR.sub.2 
3 2 2 80 
______________________________________ 
EXAMPLE 5 
While in the previous examples the secondary amine employed was free of 
other functional groups, the invention is also applicable to functionally 
substituted secondary amines. 
The procedure described in Example 3 was employed using 
N,N,N'-trimethylethylenediamine as the secondary amine. The reaction 
product was analyzed by gas-liquid chromatography and was found that 
2-[[2-(dimethylamino)ethyl]methylamino]ethanol had been formed in 91% 
yield, in a 2.5 hour operation. 
EXAMPLE 6 
While the reactions in accordance with the invention do not require the 
presence of added hydrogen, it may be desired in some instances to carry 
out the process in the presence of hydrogen. 
The procedure described in Example 3 was employed in the amination of 
ethylene glycol with morpholine as the secondary amine. The reaction 
vessel was charged with hydrogen (at 25.degree. C.) to a pressure of 50 
psig (=4.55 Kg/cm.sup.2). After heating the contents of the reactor at 
125.degree. C. for 2.5 hours, the vessel was cooled and vented. Analysis 
by gas-liquid chromatography showed 60% conversion of the morpholine to 
N-2-(hydroxyethyl)morpholine (63% selectivity) and 
1,2-bis(morpholino)ethane (30% selectivity). From the foregoing run it 
will be seen that the presence of hydrogen leads to a retardation of the 
reaction rate as well as to alteration of reaction selectivity. Thus, the 
ratio in this instance was r=0.32, as compared to r=0.09 in Run No. 1 of 
Table 1. 
A number of runs were carried out to determine the effect of various 
phosphine additives on RuCl.sub.3.xH.sub.2 O catalyzed reactions of 
morpholine with ethylene glycol. The conditions employed were 
substantially the same as used in Example 1, unless otherwise indicated. 
The results are reported in Table 5. 
TABLE 5 
______________________________________ 
Total 
Temp Time Conv. Selec 
L L:Ru (.degree.C.) 
hrs. (%) (%) r 
______________________________________ 
P(p-C.sub.6 H.sub.4 F).sub.3 
3.0 120 2.5 100 95 &lt;0.01 
P(Ph)Me.sub.2 
3.0 125 2.5 100 88 0.08 
P(p-tol).sub.3 
2.9 128 2.25 100 93 0.17 
P(C.sub.6 F.sub.5).sub.3 
2.5 120 3 22 60 &gt;0.6 
P(OPh).sub.3 
3.2 125 2.5 13 48 0.69 
DPPM 1 120 2 70 91 0.73 
PPh.sub.2 Me 
3.0 125 2.5 45 88 0.73 
P(i-Pr).sub.3 
3.8 120 2.5 12 44 0.75 
DPPE 1 125 2 13 57 0.82 
PPh(C.sub.6 F.sub.5).sub.2 
3.6 117 3 100 84 0.84 
P(o-C.sub.6 H.sub.4 NMe.sub.2) 
2.7 120 2 37 90 0.94 
P(o-tol).sub.3 
2.9 130 2.5 48 85 0.95 
______________________________________ 
Me = methyl; Ph = phenyl; tol = tolyl; 
DPPM = bis (diphenylphosphino)methane 
DPPE = bis (diphenylphosphino)ethane. 
Other runs made under the reported conditions gave the results shown in 
Table 6. 
TABLE 6 
______________________________________ 
% 
% Total 
Catalyst Conv. r Selectivity 
______________________________________ 
[(MePh.sub.2 P).sub.3 Ru(.mu.-Cl).sub.3 Ru(MePh.sub.2 P).sub.3 ] 
100 0.63 97 
[(Me.sub.2 PhP).sub.3 Ru(.mu.-Cl).sub.3 Ru(Me.sub.2 PhP).sub.3 ] 
100 0.15 89 
______________________________________ 
EXAMPLE 7 
To determine the effect of added phosphine compound to iridium catalyst, a 
run was carried out using IrCl.sub.3.xH.sub.2 O in the absence of 
phosphine or other catalyst modifier, under conditions employed in Example 
1 above. In the reaction of morpholine with ethylene glycol at 20% 
conversion of the morpholine, hydroxylethylmorpholine was obtained at 10% 
selectivity and 1,2-bis(morpholino)ethane at 56% selectivity. The results 
obtained in the same reaction with 3 moles PPh.sub.3 added per mole of 
IrCl.sub.3 is reported in Table 1, Run No. 10. In the presence of 
PPh.sub.3, higher overall conversion is obtained with the iridium catalyst 
and considerably higher selectivity (90%) to di-amination. 
While in the illustrative operating examples (at temperatures ranging from 
100.degree.-125.degree. C.) employing phosphine as a catalyst modifier, 
the ratio of P:Ru is up to about 3:1, the invention is not limited 
thereto. Good results have been obtained at P:Ru ratios up to 5:1, and 
while, at this temperature range, no special benefits are known to be 
obtained thereby, higher P:Ru ratios as up to about 10:1 may be employed. 
EXAMPLE 8 (Comparative) 
A comparative run was carried out in accordance with the general procedures 
set out for examples 1-7 above using the catalyst system and mono-alcohol 
disclosed in the Arcelli article cited above. Morpholine was reacted with 
methanol in the presence of RuCl.sub.2 (PPh.sub.3).sub.3 as a catalyst. 
The reaction was carried out at a temperature of 120.degree. C. for about 
21/2 hours. 
The resulting product was a clear, very dark red solution. Subsequent GC 
analysis indicated that there was only about an 8.4% conversion of 
morpholine. 
The results of this run indicate that, at the temperature range of the 
present invention, amination of a mono-alcohol with a secondary amine 
using the present catalyst system, results in a very low product yield. 
EXAMPLE 9 (Comparative) 
A comparative run was carried out in accordance with the general procedures 
set out in the above examples. In this example diethylamine, a secondary 
amine which was specifically recited in U.S. Pat. No. 3,270,059, was 
reacted with methanol in the presence of RuCl.sub.2 (PPh.sub.3).sub.3 at a 
temperature of 120.degree. C. 
The reaction was allowed to proceed for about 21/2 hours, after which a 
clear, amber supernatant solution was collected and a GC analysis was 
performed. The results of the GC analysis indicated that there was a 25.3% 
conversion with only an 8.2% aminated product yield. 
Examples 8 and 9 above indicate that, within the temperature range of the 
present invention (100.degree.-125.degree. C.), the present catalyst 
system does not produce a high yield of amination products when using a 
secondary amine and a mono-alcohol. Conversely, it has been found that 
only amination reactions using diols and secondary amines with the present 
catalyst system produce significant yields of the desired products at a 
temperature range between 100.degree.-125.degree. C. 
EXAMPLE 10 (Comparative) 
A run was carried out reacting morpholine with ethylene glycol using the 
same catalyst and under the same conditions as Example 1 above, except the 
reaction temperature was maintained at about 180.degree. C. The reaction 
product was analyzed as described above, and an essentially 1:1 
distribution between mono- and di-aminated product was found. 
This data indicate that the high temperatures disclosed in Arcelli needed 
to promote good yields in the reaction of methanol with primary amines, 
does not result in the desired product selectivity for reactions of diols 
with secondary amines. 
EXAMPLE 11 (Comparative) 
Under the same conditions (120.degree.-125.degree. C.) reported in Example 
1 (above) a run was carried out using as catalyst RhCl.sub.3.3H.sub.2 O 
(43% Rh) admixed with 3 moles PPh.sub.3 per mole Rh, in the amination of 
ethylene glycol by reaction with morpholine. The overall conversion to 
aminated products was 27% with 23% selectivity in the production of 
hydroxyethylmorpholine and 42% selectivity in the production of 
bix(morpholino)ethane. 
This example indicates that rhodium complexes have some activity under 
these conditions, but are generally inferior to ruthenium. Additionally, 
the rhodium catalyst did not exhibit the product selectivity; mono- vs. 
di-amination, that was achieved with the ruthenium. 
Having thus described the present invention, what is now deemed appropriate 
for Letters Patent is set out in the following appended claims.