Alkylation of polyamines

A process for alkylating a polyamine by contacting, in a liquid media, a polyamine, an olefinic compound, carbon monoxide, and a hydrogen source in the presence of a catalytic amount of a rhodium atom containing compound selected from metallic rhodium, rhodium salts, rhodium oxides, rhodium carbonyls and ligands thereof at a temperature of from about 50.degree. C. to 250.degree. C. and at a pressure of from about 30 to about 300 atmospheres.

BACKGROUND OF INVENTION 
The present invention relates to the process of forming alkylated 
polyamines and, more particularly, to the process of forming fatty 
polyamines. The subject alkylated polyamines are presently formed by 
complex synthetic methods such as are described in U.S. Pat. Nos. 
3,898,188; 3,899,534; and 4,096,105. The single step catalytic process of 
the present invention permits the formation of the desired material in an 
economic manner. 
Catalytic aminomethylation of olefins with secondary monoamines, carbon 
monoxide and hydrogen is well known and was initially taught by Dr. Walter 
Reppe in Experiention, Vol. 5, p. 93 (1949); German Pat. No. 839,800 
(1952) and Liebigs Ann. Chem., Vol. 582, p. 148 (1953). The value of the 
process was, however, of limited value due to the required use of large 
quantities of toxic iron or nickel carbonyls as the catalyst, the rapid 
rate of consumption of the catalyst, the slow rate of reaction, and the 
poor yields obtained. Moreover, the reaction was taught to be restricted 
to monoolefins and to low molecular weight monoamines. 
Aminomethylation of other monoolefins has been carried out in the presence 
of other metal carbonyls, but the reactions have been found to be 
non-selective and produce, at best, only moderate yields of amines. For 
example, U.S. Pat. Nos. 2,422,631 and 3,234,283 disclose that lower 
olefins, carbon monoxide, hydrogen, and a secondary monoamine will form, 
in low yields, tertiary amines in the presence of cobalt hydrocarbonyl or 
dicobalt octocarbonyl as well as certain other cobalt compounds. 
More recently, U.S. Pat. Nos. 3,513,200 and 4,096,150 have disclosed the 
utilization of Group VIII metal compounds as suitable compounds to 
catalyze the reaction between monoamines and monomeric olefins with 
hydrogen and carbon monoxide to form low molecular weight tertiary amines. 
The above reactions are generally plagued by the formation of significant 
amounts of byproducts and by the required use of hydrogen which is both 
unsafe and expensive. The reactions are, therefore, not deemed suitable 
for the formation of specific compounds. 
Alkylated polyamines and products derived therefrom are highly desired 
compounds known to be useful as surfactants, flocculating agents, 
softeners and as a desired component of some coating compositions. 
Conventional methods of forming such alkylated polyamines have been 
difficult and costly. It is highly desired to find an economical process 
for forming alkylated polyamines and especially for the formation of fatty 
amines. 
SUMMARY OF THE INVENTION 
The present process is directed to a one-step, economical method of forming 
alkylated polyamines and, more particularly, fatty polyamines by 
contacting, in a liquid media, a polyamine, an olefinic compound, carbon 
monoxide, and water in the presence of a catalytic amount of a rhodium 
compound selected from metallic rhodium, rhodium salts, oxides, carbonyls, 
phosphines or ligands. The reaction is carried out in an inert solvent at 
temperatures of from 50.degree. to 250.degree. C. and at a pressure of 
from about 30 to about 300 atmospheres. 
DETAILED DESCRIPTION 
The subject invention is directed to a new and novel one-step, catalytic 
method of alkylating a polyamine by contacting, in an inert solvent, a 
compound having a multiplicity of primary and/or secondary amine groups, a 
monoolefin, water and carbon monoxide in the presence of certain rhodium 
compounds as the catalyst, as more completely described herein below. 
Organic compounds having at least two amino nitrogens therein which form 
either a primary or a secondary amino group are suitable in the subject 
process. These compounds are referred to in the instant disclosure as 
"polyamines" or "polyamine" and can be represented by the general formula 
EQU R.sup.1 NH(R.sup.3 NH).sub.x R.sup.2 
wherein R.sup.1 and R.sup.2 each separately represent a hydrogen atom or a 
hydrocarbyl such as an alkyl, aryl, alkaryl or aralkyl which, preferably, 
has from one to twelve carbon atoms or R.sup.1 and R.sup.2 together 
represent an alkylene group, R.sup.3 is an alkylene group and x is a whole 
integer of 1 or greater. Generally, when R.sup.1 or R.sup.2 is a 
hydrocarbyl it is preferred that each have from one to twelve carbon atoms 
such as methyl, ethyl, t-butyl, cyclopentyl, phenyl, tolyl and the like. 
Further, the R.sup.3 alkylene group can contain any number of carbon atoms 
and, preferably has from one to twelve carbons such as methylene, 
ethylene, tetramethylene, hexamethylene, phenylene, biphenylene, 
tetramethyl phenylene and the like. When R.sup.1 and R.sup.2 are together 
an alkylene, R.sup.1, R.sup.2 and R.sup.3 should not be greater than six 
carbon atoms in combination. 
Examples of such polyamines include ethylenediamine, propylene diamine, 
hexamethylene diamine, diethylenetriamine, triethylene tetraamine, 
trimethylenetriamine, N,N.sup.1 -dimethyl ethylenediamine, N,N.sup.1 
-dibutyl ethylenediamine,N-methyl, N.sup.1 -ethyl ethylenediamine, 
N,N.sup.1 -diphenyl ethylenediamine, phenylene diamine, piperazine, 
polyethylenimine and the like. 
The subject process requires the use of polyamine compounds which compounds 
have been found uniquely different from monoamines used in the processes 
of the prior art. The subject process including the required use of the 
subject polyamines yields desired products in a simple manner and in high 
yields. 
The olefinic unsaturated compounds which are useful in the present 
invention are olefinic compounds having from 2 to about 20 carbons and can 
be represented by the general formula. 
EQU R.sup.4 CH.dbd.CR.sup.5 R.sup.6 
wherein each R.sup.4, R.sup.5 and R.sup.6 represents hydrogen or a C.sub.1 
to C.sub.18 hydrocarbyl including alkyl, aryl, alkaryl, aralkyl, 
cycloalkyl and substituted derivatives in which the substituted group is 
inert to the reaction and may be selected from carboyl, tertiary amino, 
hydroxy, alkoxy, thio and the like. Further R.sup.4 and R.sup.5 combined 
can represent a C.sub.2 -C.sub.6 alkylene group or a substituted alkylene 
group wherein the substituted groups are the same as described above or a 
C.sub.1 to C.sub.14 hydrocarbyl group. 
Examples of useful olefins are the hydrocarbon olefins such as ethylene, 
propylene, butene-1, butene-2, isobutylene, pentene-2, 2-methylbutene-1, 
hexene-1, 3-ethylhexene-1, octene-3, 2-propylhexene-1, decene-2, 
4,4'-dimethyl nonene-1, dodecene-1, 6-propyldecene-1, tetradecene-5, 
7-amyldecene-3, hexadecene-1, 4-ethyltridecene-2, octadecene-1, 
5,5-dipropyldodecene-3, eicosene-7, etc. Of these the aliphatic 
hydrocarbon olefins having from about 10 to 20 carbons are preferred and 
most preferred are the alpha olefins having terminally unsaturated carbons 
when desiring to form fatty polyamines by the process of the subject 
invention. 
Other olefins that can be used include vinyl cyclohexane allyl cyclohexane, 
styrene, p-methyl styrene, alpha methyl styrene, beta methyl styrene, 
p-vinyl cumene, beta vinyl naphthalene, 1,2-diphenyl ethylene, allyl 
benzene, 6-phenylhexene-1, 1,3-diphenylbutene-1, 3-benzoheptene-3, 
o-vinyl, p-xylene, crotonyl alcohol, allyl carbinol, beta-allylethyl 
alcohol, allylmethylpropylcarbinol, allylphenol, etc. 
Cycloalkenes and their substituted derivatives include cyclobutene, 
cyclopentene, cyclohexene, methylcyclohexene, amylcyclopentene, 
cycloheptene, cyclooctene, cyclodecene, etc. 
The particular polyamine and the particular olefinic compound to be used 
will depend on the resultant product desired. 
The equivalent ratio of olefinic bond to each primary or secondary amino 
nitrogen contained in the reaction zone should be from about 1.05 to 3 
with from 1.05 to 2 being preferred. It is sometimes suitable to have the 
olefinic bond containing compound present in large excess and act as 
liquid media or at least a part of the liquid media in which the process 
is carried out. 
The alkylation of the polyamine has been found to readily occur when the 
chosen polyamine and the chosen olefinic compound, as described above, are 
contacted with carbon monoxide and water in the presence of a catalyst 
described herein below. It has been unexpectedly found that water acts as 
an effective source of hydrogen in the subject process, does not have the 
detrimental safety problems normally associated with hydrogen gas and, in 
general, enhances the yield of alkylated product. Water can be used in 
combination with hydrogen gas as the hydrogen source although poorer 
yields and safety problems complicate the reaction. Water alone is, 
therefore, the preferred hydrogen source. 
The reaction is performed under liquid phase conditions. Any suitable 
organic liquid can be employed which is inert to the reaction conditions, 
the reactants, the catalyst and the products. Examples of suitable 
solvents that can be used in accordance with this invention include 
hydrocarbons such as the aromatics, aliphatics or alicyclic hydrocarbons, 
ethers, esters, etc. 
Examples of suitable hydrocarbons that can be employed as the solvent 
include aromatic hydrocarbons such as benzene, toluene, xylene, ethyl 
benzene, tetralin, etc.; aliphatic hydrocarbons such as butane, pentane, 
isopentane, hexane, isohexane, heptane, octane, isooctane, naphtha, 
gasoline, kerosene, mineral oil, etc.; alicyclic hydrocarbons, such as 
cyclopentane, cyclohexane, methylcyclopentane, decalin, indane, etc. 
Ethers can also be employed as the reaction solvent, such as diisopropyl 
ether, di-n-butyl ether, ethylene glycol diisobutyl ether, methyl o-tolyl 
ether, ethylene glycol dibutyl ether, diisoamyl ether, methyl p-tolyl 
ether, methyl m-tolyl ether, dichloroethyl ether, ethylene glycol 
diisoamyl ether, diethylene glycol diethyl ether, ethylbenzyl ether, 
diethylene glycol diethyl ether, diethylene glycol dimethyl ether, 
ethylene glycol diethyl ether, ethylene glycol diphenyl ether, triethylene 
glycol diethyl ether, diethylene glycol di-n-hexyl ether, tetraethylene 
glycol dimethyl ether, tetraethylene glycol dibutyl ether, etc. 
Various esters can also be employed as the solvent, such as ethyl formate, 
methyl acetate, ethyl acetate, n-propyl formate, isopropyl acetate, ethyl 
propionate, n-propyl acetate, sec-butyl acetate, isobutyl acetate, 
ethyl-n-butylate, n-butyl acetate, isoamyl acetate, n-amyl acetate, ethyl 
formate, ethylene glycol diacetate, glycol diformate, cyclohexyl acetate, 
furfuryl acetate, isoamyl n-butyrate, diethyl oxalate, isoamyl 
isovalerate, methyl lenzoate, diethyl malonate, valerolactone, ethyl 
benzoate, methyl salicylate, n-propyl benzoate, n-butyl oxalate, n-butyl 
benzoate, diisoamyl phthalate, dimethyl phthalate, diethyl phthalate, 
benzyl benzoate, n-butyl phthalate, etc. A preferred class of ester 
solvents include the lactones, e.g., butyrlactone valerolactone and their 
derivatives having lower (C.sub.1 -C.sub.5) alkyl substituents. 
Alcohols can be employed as the reaction solvent. Preferably the alcohol is 
a C.sub.1 to C.sub.8 alcohol and can be a primary alcohol, such as 
methanol, ethanol, n-propanol and the like; secondary alcohols, such as 
isopropanol, 1-methyl pentanol and the like; and tertiary alcohols, such 
as t-butyl and t-amyl alcohols. 
Tertiary amines can also be employed as the reaction solvent, the nitrogen 
atom, by definition, being substituted with three hydrocarbyl groups which 
are inert with respect to the reaction, such as, for example, alkyl, aryl, 
alkaryl, aralkyl groups and the like. Examples of suitable tertiary amines 
include trimethylamine, triethylamine, tripopylamine, triisobutylamine, 
trihexylamine, triheptylamine, triamylamine, dibenzyl ethylamine, dibutyl 
ethylamine, dimethyl pentylamine, diphenyl ethylamine, diphenyl 
methylamine, dimethyl aniline, pyridine, dimethyl pyridine, methoxy 
pyridine, methyl pyrrolidine, N-ethyl pyrrolidine, N-methyl piperidine and 
the like. The preferred solvents are the teritary amines and, especially, 
trimethylamine pyridine, N-alkyl, substituted pyrrolidine and its 
derivatives or piperidine. 
The particular solvent to be used will depend on its ability to remain in 
the liquid state at both ambient and at reaction conditions to facilitate 
the mixing of the components, its solvating ability with respect to at 
least some of the reactants, and its ease of handling, as can be readily 
determined by the artisan. 
The reaction is performed under relatively mild conditions including 
temperatures from about 80.degree. to about 250.degree. C.; preferably 
from about 100.degree. to about 200.degree. C. Sufficient pressure should 
be used to maintain the reaction medium in a liquid phase. The reaction is 
carried forth at super-atmospheric pressure such as from about 30 to about 
300 atmospheres and, preferably, from about 30 to 100 atmospheres. Since 
the reaction is exothermic, the temperature can be maintained by suitable 
cooling of all or a portion of the reaction zone contents. The pressure 
can be maintained by the pressure of the carbon monoxide and, when used, 
hydrogen supplied to the reaction zone. If desired, a suitable inert gas, 
such as nitrogen, can also be charged to the reaction zone to supplement 
the partial pressures of the reaction gases. 
The ratio of the reactants can be widely varied. The mole ratio of carbon 
monoxide to the hydrogen source should be at least about 3:1. Higher 
ratios, such as 5:1 or above, are preferred. The carbon monoxide can be 
used in excess to form sufficient pressure required in the reaction zone, 
as described above. The mole ratio of hydrogen source to amino group can 
be varied from about 1:10 to 10:1 with from about 1:3 to 3:1 being 
preferred. Finally, the ratio of olefinic bond compound to the combined 
primary and secondary nitrogen atoms of the polyamine reactant should be 
such that the molar ratio should be at least from 1 to 1 and preferably 
from at least 1 to 2. 
The catalyst required to cause the formation of the desired alkylated 
polyamines comprises rhodium compounds selected from elemental rhodium, 
rhodium salts, rhodium oxides, rhodium carbonyls, rhodium ligands as 
described herein below. The preferred catalysts are formed from rhodium 
compounds in which the rhodium atom is the plus one valence state. The 
exact chemical and physical composition of the entity which acts as the 
catalyst for the subject reaction is not known with certainty because of 
the possible restructuring and/or interaction of the rhodium compound used 
and the reactants contained in the reaction zone. Whether the rhodium 
compounds described herein directly act as the catalyst or as the 
precursor for the catalyst entity which causes the presently desired 
aminomethylation is immaterial. The subject rhodium compounds will be 
referred herein as the "catalyst" as they have unexpectedly been found to 
aid directly and/or indirectly in the formation of desired alkylated 
polyamines by the present one-step process and to give the desired product 
in high yields. 
The rhodium compounds which are useful in catalyzing the subject reaction 
must have some degree of solubility in the liquid media in which the 
subject aminomethylation is to take place. The choice of liquid media 
and/or catalyst to be used in a particular reaction so that the catalyst 
has some degree of solubility can be readily determined by those skilled 
in the art using conventional methods. 
The catalyst found useful in the subject process can be a rhodium salt of 
an inorganic acid such as, for example rhodium chloride, rhodium nitrate, 
rhodium sulfate, rhodium perchlorate and the like or of an organic acid 
such as rhodium acetate and the like. The rhodium salts are well known 
commercial products formed conventionally by the reaction of rhodium oxide 
with an acid. The salt can be used in its anhydrous state or as a hydrated 
salt. The hydrated salts being preferred. 
The catalyst of the subject process can be rhodium ligand. The ligand can 
be formed in coordination with rhodium in any one of its valence states; 
that is of zero or plus 1, 2 or 3. The ligand moiety is formed from 
chemical moieties which contain unshared electrons such as atoms selected 
from nitrogen, oxygen, phosphorus or sulfur or which contains 
unsaturation. The ligand can be in the form of a carbonyl; an olefin such 
as ethylene, butene and the like; diolefines such as norbornadiene, 
cyclooctadiene-1,5 and the like; aliphatic, aromatic, aryl or aliphatic 
phosphites, such as triethyl phosphite, tributyl phosphite, trimethyl 
phosphite, triphenyl phosphite, dimethyl phenyl phosphite, tritolyl 
phosphite, tribenzyl phosphite, ditolyl phenyl phosphite, and the like; 
aliphatic and cyclic ethers such as dimethyl and diethyl oxide, dioxane, 
dialkyl ether glycols, acetyl acetone and the like; primary, secondary, 
and tertiary amines which contain alkyl, aryl, alkaryl, aralkyl, 
cycloalkyl groups or mixtures thereof such as trimethyl amine, diethyl 
amine, toluidine and the like; heterocyclic basis such as pyridine, 
bypyridine and the like; ammonia; sulfides such as dialkyl, diaryl, 
alicyclic heterocyclic sulfides and the like; and mixtures of said ligand 
components with rhodium. When the ligand is formed from uncharged ligand 
components with charged rhodium, the compound is formed into a stable 
neutral state with an anion such as chloride perchlorate, nitrate, 
hexaflourophosphate and the like. 
The ligand may be added directly to the reaction medium and/or introduced 
into the medium as a complex of the ligand precursor with the rhodium 
salt, chelate, hydride or carbonyl. For example, the appropriate precursor 
of the desired ligand can be introduced into the reaction zone with a 
rhodium precursor such as, for example rhodium oxide, a rhodium carbonyl 
as dirhodium dichloro tetracarbonyl, and the like. 
The catalyst materials which are useful in the subject process can be 
generically described by the formula: 
EQU Rh.sub.r [A].sub.a [B].sub.b [C].sub.c 
wherein A represents an anion of an inorganic salt such as nitro, sulfo, 
halo, especially chloro, and the like; B represents a chemical moiety 
containing an entity having at least one pair of unshared electrons such 
as carbonyl, olefin, phosphite, ethers, amines, sulfides and mixtures 
thereof; C represents an anion capable of forming a neutral compound, such 
as trifluorophosphite, a, b and c each represent a whole integer including 
0 and r represents a whole integer of 1 or greater. 
The catalyst material can be added directly to the reaction medium either 
prior or subsequent to the introduction of the required reactants. The 
ligand catalyst described above can be added directly or as a complex of 
the ligand precursor such as a rhodium salt, hydride or carbonyl as, for 
example, dirhodium dichloro tetracarbonyl and the like. 
The rhodium compound useful in the present invention can be metallic 
rhodium. The metallic rhodium can be in any form such as a powder, ribbon, 
or coated on an inert support. The inert support can be any conventional 
catalytic support as are well known such as formed from alumina, carbon, 
or a metal oxide, as, for example, an alkali or alkaline earth metal oxide 
and the like. The coating of metallic rhodium can be done by vapor 
disposition or other conventional methods and should be present in from 
about 2 to 8 percent by weight of the inert support. Although metallic 
rhodium has, per se, substantially no solubility in the liquid media 
contemplated for use, it is believed that metallic rhodium reacts with one 
or more of the required components in the reaction zone to form a product 
which is sufficiently soluble to cause the desired aminomethylation to 
proceed. The metallic rhodium is, most probably, a precursor for the 
actual catalytic rhodium compound required of the subject process. 
The catalyst has been found to be effective to cause the desired alkylation 
of a polyamide compound as described above when used in a molar ratio of 
rhodium atom to olefin bond of from about 1.times.10.sup.-4 to 
2.5.times.10.sup.-3 with preferably from about 1.times.10.sup.-4 to 
1.times.10.sup.-3. The most preferred range from both effectiveness and 
economy is from 5.times.10.sup.-4 to 2.times.10.sup.-3. Although greater 
amounts of catalyst can be used, such has not been found required. 
The rhodium catalysts found useful in the subject invention may be used in 
combination with other metal complexes which are known to cause 
aminomethylation as for example iron or cobalt carbonyl complexes and the 
like although poorer results are normally achieved. The rhodium catalyst 
should, therefore, be the sole or major catalyst used in the subject 
reaction. 
The preferred rhodium catalysts are those which have rhodium in its plus 1 
valence state and has been complexed with a carbonyl or diolefin or both. 
Water is the preferred hydrogen source. 
The reaction is carried out in a vessel which is preferably adapted for gas 
injection, agitation and heating. The liquid media is first introduced 
followed by the olefinic containing compound, the polyamine and the 
rhodium catalyst. Water can be added along with the other components. When 
the reaction is carried out under elevated temperature and pressure, the 
vessel is closed and charged to a specific partial pressure with carbon 
monoxide. Any additional pressure required can be obtained with an inert 
gas, such as nitrogen. The reactor and its contents are maintained at the 
desired elevated temperature of from about 100.degree. C. to 200.degree. 
C. for a period of time from about 15 minutes to about 10 hours with from 
about 30 minutes to 5 hours being sufficient and preferred in most 
instances. The vessel is then cooled down, where appropriate, degassed and 
the alkylated polyamine is recovered and tertiary amino nitrogen is 
determined by standard analytical techniques. The primary product is 
tertiary amine. 
The subject process has been found useful in forming fatty amines, 
especially odd carbon atom containing fatty amines. The later material are 
normally extremely difficult to produce by known techniques. In forming 
fatty amines one uses a C.sub.12 to C.sub.20 monoolefin compound such as 
disclosed herein above. When odd carbon atom containing fatty amine is 
desired one can readily form the same by using an even number carbon atom 
containing monoolefin having from twelve to twenty carbon atoms as the 
olefin reactant.

The following examples are for illustrative purposes only and are not meant 
to be a limitation on the subject invention except as indicated in the 
appended claims. All parts and percentages are by weight except where 
otherwise indicated. 
EXAMPLE I 
10.8 g. of piperazine, 25.3 ml of cyclohexene, 9 ml of water and 25 ml of 
N-methyl piperidine were placed in a 150 ml stainless steel reactor. 370 
mg of commercially obtained rhodium norbornadiene tris 
(dimethylphenylphosphine) hexafluorophosphine, [Rh(NBD) (CH.sub.3).sub.2 
P(C.sub.6 H.sub.5).sub.3 ].sup.- PF.sub.6.sup.+ was then placed in the 
reactor. The reactor was sealed and pressurized at ambient temperature of 
25.degree. C. with carbon monoxide to 1000 psi. The reactor was placed in 
an oil shaker bath for 6 hours at 140.degree. C. and then cooled to 
ambient temperature. The contents were removed and washed with diethyl 
ether and water. The ether washings were collected, and evaporated to 
dryness. The solid product was recrystalized with methanol. The product 
(70% yield) was identified by H-NMR to be the desired tertiary diamine 
.sup.13 C=77.52% M=10.10% H=12.3%. 
EXAMPLE II 
The process of Example I above was repeated using 134 ml of cyclohexene, 50 
g of piperizine, 42 ml of water, 200 ml of N-methyl piperidine and 400 mg 
of the same rhodium catalysts prepared in accordance with the procedure of 
Schrock and Osborn, JACS, 93 2397 (1971). The reactants were placed in a 2 
l stainless steel reactor which was sealed and pressurized with 1000 psi 
of CO at ambient temperature. The reaction was carried out at 150.degree. 
C. for 8 hours. The recovered tertiary diamine product (yield 70%) was 
identified by H-NMR. 
EXAMPLE III 
Several runs were made using different rhodium catalysts. In each of the 
runs 1.06.times.10.sup.-2 mole of cyclohexene, 5.3.times.10.sup.-3 mole of 
piperazine, 1.06.times.10.sup.-2 water were placed in 30 ml stainless 
steel reactors with 2 ml of N-methyl piperidine and selected rhodium 
catalysts, as indicated below. Each of the catalysts were used in an 
amount such that the moles ratio of olefin to rhodium atom was 500. The 
reactors were sealed, pressurized with 1000 psi of carbon monoxide and 
placed in a shaking oil bath for 7 hours at 160.degree. C. and then cooled 
to room temperature. The contents were removed and the recovered product 
was analyzed by gas-liquid chromatography internal standard methods. Each 
run gave the following percent conversion to tertiary amine: 
Rh.sub.6 (CO).sub.16 --95%; 
RhCl.sub.3 (C.sub.5 H.sub.5 N).sub.3 --92%; 
Rh(CO).sub.2 (C.sub.5 H.sub.7 O.sub.2)--94%; 
[RhCl(C.sub.7 H.sub.8)].sub.2 --94% 
EXAMPLE IV 
The procedure of Example III was repeated except that ethanol was used as 
solvent in lieu of N-methyl piperidine with the catalyst of [RhCl(C.sub.7 
H.sub.8)].sub.2. The recovered product was analyzed by gas-liquid 
chromatography and determined to be tertiary amine in 94% yield. 
EXAMPLE V 
The procedure of Example III is repeated except that the reactant 
piperazine is substituted with an equivalent amount of commercially 
obtained phenylene diamine, N,N'-diphenylethylenediamine and hexamethylene 
diamine. The product obtained in each case is analyzed by standard 
technique and found to give conversions similar to that obtained in 
Example III. 
While the invention has been described in connection with certain preferred 
embodiments, it is not intended to limit the invention to the particular 
forms set forth, but, on the contrary, it is intended to cover such 
alternatives, modifications and equivalents as defined by the appended 
claims.