Note: Descriptions are shown in the official language in which they were submitted.
, CA 02828168 2013-08-23
PF0000071685/MKr
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1
As originally filed
Process for preparing di-, tri- and polyamines by homogeneously catalyzed
alcohol
amination
The present invention relates to a process for preparing primary di-, tri- and
polyamines
by homogeneously catalyzed alcohol amination of di-, tri- and polyols and of
alkanolamines having at least one primary hydroxyl group by means of ammonia
with
elimination of water in the presence of a complex catalyst which comprises at
least one
element selected from groups 8, 9 and 10 of the Periodic Table and also at
least one
donor ligand.
Primary amines are compounds which have at least one primary amino group (-
NH2).
Primary diamines have two primary amino groups. Primary triamines have three
primary amino groups. Primary polyamines have more than three primary amino
groups.
Primary amines are valuable products having many different uses, for example
solvents, stabilizers, for the synthesis of chelating agents, as starting
materials for the
production of synthetic resins, inhibitors, surface-active substances,
intermediates in
the production of fuel additives (US 3,275,554 A, DE 2125039 A and DE 36 11
230 A),
surfactants, drugs and crop protection agents, hardeners for epoxy resins,
catalysts for
polyurethanes, intermediates for the preparation of quaternary ammonium
compounds,
plasticizers, corrosion inhibitors, synthetic resins, ion exchangers, textile
assistants,
dyes, vulcanization accelerators and/or emulsifiers.
Primary di- and triamines are at present prepared by heterogeneously catalyzed
alcohol amination of primary diols and triols by means of ammonia.
WO 2008/006752 Al describes a process for preparing amines by reacting primary
or
secondary alcohols with ammonia in the presence of a heterogeneous catalyst
comprising zirconium dioxide and nickel. WO 03/051508 Al relates to a process
for
aminating alcohols using specific heterogeneous Cu/Ni/Zr/Sn catalysts.
Heterogeneous
catalysts comprising nickel oxide, copper oxide, zirconium oxide and
molybdenum
oxide for the amination of alcohols by means of ammonia and hydrogen are known
from EP 0 696 572 Al. In the abovementioned documents, the reactions are
carried
out at temperatures in the range from 150 to 210 C and ammonia pressures in
the
range from 30 to 200 bar. However, the undesired monoamination products and
cyclic
amines such as piperazines, pyrrolidines and morpholines are formed as main
products in the heterogeneously catalyzed processes described in the above
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documents. The desired primary diamines are obtained only in extremely low
yields, if
at all, in the above-described processes. The abovementioned documents
describe, in
particular, the reaction of diethylene glycol with ammonia.
0
NH3
o/
NH
0
0
Here, monoaminodiethylene glycol and morpholine are obtained as main products.
The
desired doubly aminated diaminodiethylene glycol is obtained only in extremely
low
yields, if at all, in the amination reactions of the abovementioned documents.
The highest yield of diaminodiethylene glycol of 5% is obtained according to
WO 03/051508 Al, with 22% of morpholine and 36% of monoaminodiethylene glycol
being formed as by-products.
In the amination of diethanolamine by means of ammonia, piperazine is obtained
as
main product. Here too, the monoamination product and the desired linear
diamination
product diethylenetriamine are obtained only in traces.
N NH2
NH3
HN NH
-H20
In the reaction of. polyetherols, undesired secondary reactions to form the
dimeric
secondary amine or polymeric coupling products are observed to a substantial
extent in
the above-described processes for heterogeneously catalyzed amination. These
by-
products are difficult to separate from the desired primary diamination
product.
H2N NH2
NH3
-H20
- n
H2N NH2
A further problem observed in the heterogeneously catalyzed amination of
polyetherols, in particular polyethylene glycol and polypropylene glycol
derivatives, is
the decomposition of these ethers under the above-described reaction
conditions,
since, in particular, the high temperatures and a supporting hydrogen pressure
are
necessary. Under these reaction conditions, gaseous decomposition products
which
make specific safety precautions necessary are formed.
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The homogeneously catalyzed amination of monoalcohols by means of primary and
secondary amines has been known since the 1970s, with ruthenium or iridium
catalysts
usually being described. The homogeneously catalyzed amination proceeds at
significantly lower temperatures of from 100 to 150 C compared to
heterogeneously
catalyzed reactions. The reaction of monoalcohols with primary and secondary
amines
is described, for example, in the following publications: US 3,708,539; Y.
Watanabe,
Y. Tsuji, Y. Ohsugi, Tetrahedron Lett. 1981, 22, 2667-2670; S. Bahn, S. Imm,
K. Mevius, L. Neubert, A. Tillack, J. M. J. Williams, M. Beller, Chem. Eur. J.
2010, DOI:
10.1002/chem.200903144; A. Tillack, D. Hollmann, D. Michalik, M. Beller,
Tetrahedron
Lett. 2006, 47, 8881-8885; D. Hollmann, S. Bahn, A. Tillack, M. Beller, Angew.
Chem.
mt. Ed. 2007, 46, 8291-8294; A. Tillack, D. Hollmann, K. Mevius, D. Michalik,
S. Bahn,
M. Beller, Eur. J. Org. Chem. 2008, 4745-4750; M. H. S. A. Hamid, C. L. Allen,
G. W. Lamb, A. C. Maxwell, H. C. Maytum, A. J. A. Watson, J. M. J. Williams,
J. Am.
Chem. Soc. 2009, 131, 1766-1774; 0. Saidi, A. J. Blacker, M. M. Farah,
S. P. Marsden, J. M. J. Williams, Chem. Commun. 2010, 46, 1541-1543; A.
Tillack,
D. Hollmann, D. Michalik, M. Beller, Tet. Lett. 2006, 47, 8881-8885; A. Del
Zlotto,
W. Baratta, M. Sandri, G. Verardo, P. Rigo, Eur. J. Org. Chem. 2004, 524-529;
A. Fujita, Z. Li, N. Ozeki, R. Yamaguchi, Tetrahedron Lett. 2003, 44, 2687-
2690;
Y. Watanabe, Y. Morisaki, T. Kondo, T. Mitsudo J. Org. Chem. 1996, 61, 4214-
4218,
B. Blank, M. Madalska, R. Kempe, Adv. Synth. Catal. 2008, 350, 749-750, A.
Martinez-
Asencio, D. J. Ramon, M. Yus, Tetrahedron Lett. 2010, 51, 325-327. The
greatest
disadvantage of the above-described systems is that only the amination of
monoalcohols by means of primary and secondary amines is possible using these
processes. The reaction of alcohols with ammonia, which represents the
economically
most attractive amination reaction, is not described in these studies.
The amination of diols by means of secondary amines using homogeneous iridium
and
ruthenium catalysts to form amino alcohols and linear diamines having tertiary
amino
groups has been described, for example, in EP 239 934; J. A. Marsella, J. Org.
Chem.
1987, 52, 467-468; US 4,855,425; K.-T. Huh, Bull. Kor. Chem. Soc. 1990, 11, 45-
49; N.
Andrushko, V. Andrushko, P. Roose, K. Moonen, A. BOrner, ChemCatChem, 2010, 2,
640-643 and S. Bahn, A. Tillack, S. Imm, K. Mevius, D. Michalik, D. Hollmann,
L.
Neubert, M. Beller, ChemSusChem 2009, 2, 551-557. In these studies, the
amination is
carried out at 100-180 C.
J. A. Marsella, J. Organomet. Chem. 1991, 407, 97-105 and B. Blank, S.
Michlik, R.
Kempe, Adv. Synth. Catal. 2009, 351, 2903-2911; G. Jenner, G. Bitsi, J. Mol.
Cat,
1988, 45, 165-168; Y. Z. Youn, D. Y. Lee, B. W. Woo, J. G. Shim, S. A. Chae,
S. C.
Shim, J. Mol. Cat, 1993, 79, 39-45; K. I. Fujita, R. Yamaguchi, Synlett, 2005,
4,
560-571; K.I. Fujii, R. Yamaguchi, Org. Lett. 2004, 20, 3525-3528; K. I.
Fujita, K.
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Yamamoto, R. Yamaguchi, Org. Lett. 2002, 16, 2691-2694; A. Nova, D. Balcells,
N. D.
Schley, G. E. Dobereiner, R. H. Crabtree, 0. Eisenstein, Organometallics DOI:
10.1021/om101015u; and M. H. S. A. Hamid, C. L. Allen, G. W. Lamb, A. C.
Maxwell,
H. C. Maytum, A. J. A. Watson, J. M. J. Williams, J. Am. Chem. Soc. 2009, 131,
1766-1774 and 0. Saidi, A. J. Blacker, G. W. Lamb, S. P. Marsden, J. E.
Taylor, J. M.
J. Williams, Org. Proc. Res. Dev. 2010, 14, 1046-1049 describe the amination
of diols
and of alkanolamines by means of primary amines using homogeneously dissolved
ruthenium- and iridium-based transition metal catalysts. However, the cyclic
compounds and not the desired linear diamines are formed here. The
economically
attractive amination of diols by means of ammonia to form primary amines is
not
possible using these systems.
S. Imm, S. Bahn, L. Neubert, H. Neumann, M. Beller, Angew. Chem. 2010, 122,
8303-
8306 and D. Pingen, C. Muller, D. Vogt, Angew. Chem. 2010, 122, 8307-8310
describe
the amination of secondary alcohols such as cyclohexanol with ammonia which is
homogeneously catalyzed by ruthenium catalysts. EP 0 320 269 A2 discloses the
palladium-catalyzed amination of primary allyl monoalcohols by means of
ammonia to
form primary allylamines. WO 2010/018570 and C. Gunanathan, D. Milstein,
Angew.
Chem. Int. Ed. 2008, 47, 8661-8664 describe the amination of primary
monoalcohols
by means of ammonia to form primary monoamines with the help of ruthenium-
phosphane complexes. The amination of primary di-, tri- and polyols is not
described in
these studies.
R. Kawahara, K.I. Fujita, R. Yamaguchi, J. Am. Chem. Soc. DOI:
10.1021/ja107274w
describe the amination of primary monoalcohols and triols by means of ammonia
using
an iridium catalyst which has Cp* (1,2,3,4,5-pentamethylcyclopentadienyl) and
ammonia as ligands. However, the reaction of primary monoalcohols with ammonia
using the catalyst system described there gives exclusively the undesired
tertiary
amines. The reaction of glycerol with ammonia leads exclusively to the
undesired
bicyclic quinolizidine.
EP 0 234 401 Al describes the reaction of diethylene glycol with ammonia in
the
presence of a ruthenium carbonyl compound. In the process described in
EP 0 234 401 Al, merely the monoamination product (monoethanolamine), the
secondary and tertiary amines (diethanolamine and triethanolamine) and cyclic
products (N-(hydroxyethyl)piperazine and N,N'-bis(hydroxyethyl)piperazine) are
formed. The desired 1,2-diethanolamine is not obtained in this process.
All the above-described processes for the reaction of diols and triols have
the
disadvantage that, as main products, the undesired secondary, tertiary and
cyclic
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amines are formed. In some cases minor amounts of monoamination products such
as
alkanolamines are also formed. The desired primary diamines, triamines and
polyamines are not accessible by this route.
5 It is an object of the present invention to provide a process for
preparing primary di-, tri-
and polyamines by alcohol amination of di-, tri- and polyols and of
alkanolamines by
means of ammonia with elimination of water.
The object is achieved by a process for preparing primary amines which have at
least
one functional group of the formula (-CH2-NH2) and at least one further
primary amino
group by alcohol amination of starting materials having at least one
functional group of
the formula (-CH2-0H) and at least one further functional group (-X), where (-
X) is
selected from among hydroxyl groups and primary amino groups, by means of
ammonia with elimination of water, wherein the reaction is carried out
homogeneously
catalyzed in the presence of at least one complex catalyst comprising at least
one
element selected from groups 8, 9 and 10 of the Periodic Table and also at
least one
donor ligand, in particular a phosphorus donor ligand.
It has surprisingly been found that primary di-, tri- and oligoamines can be
obtained by
the homogeneously catalyzed amination of diols, triols and polyols and also
alkanolamines by means of ammonia with elimination of water using the complex
catalysts which are used in the process of the invention and comprise at least
one
element selected from groups 8, 9 and 10 of the Periodic Table and also at
least one
donor ligand, in particular a phosphorus donor ligand. The process of the
invention has
the advantage that it gives primary di-, tri- and polyamines in considerably
improved
yields compared to the processes described in the prior art. In addition, the
formation of
undesired by-products such as secondary and tertiary amines and also cyclic
amines is
largely suppressed.
Starting materials
In the process of the invention, starting materials having at least one
functional group
of the formula (-CH2-0H) and at least one further functional group (-X), where
(-X) is
selected from among hydroxy groups and primary amino groups, are used.
In a further embodiment, starting materials in which (-X) is selected from
among
functional groups of the formulae (¨CH2-0H) and (-CH2-NH2) are used in the
process of
the invention. The starting materials then have at least one functional unit
of the
formula (-CH2-0H) and at least one further functional unit selected from among
functional units of the formulae (¨CH2-0H) and (-CH2-NH2).
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Suitable starting materials are virtually all alcohols which meet the
abovementioned
prerequisites. The alcohols can be straight-chain, branched or cyclic. The
alcohols can
also bear substituents which are inert under the reaction conditions of the
alcohol
amination, for example alkoxy, alkenyloxy, alkylamino, dialkylamino and
halogens
(F, Cl, Br, I).
Suitable starting materials which can be used in the process of the invention
are, for
example, dials, triols, polyols and alkanolamines, which have at least one
functional
group of the formula (-CH2-0H) and at least one further functional group (-X)
where
(-X) is selected from hydroxyl groups and primary amino groups.
In addition, diols, triols, polyols and alkanolamines which have at least one
functional
unit of the formula (-CH2-0H) and at least one further functional unit
selected from
among functional units of the formula (-CH2-0H) and (-CH2-NH2) are suitable.
As starting materials, it is possible to use all known diols which have at
least one
functional group of the formula (-CH2-0H). Examples of diols which can be used
as
starting materials in the process of the invention are 1,2-ethanediol
(ethylene glycol),
1,2-propanediol (1,2-propylene glycol), 1,3-propanediol (1,3-propylene
glycol),
1,4-butanediol (1,4-butylene glycol), 1,2-butanediol (1,2-butylene glycol),
2,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethy1-1,3-propanediol
(neopentyl
glycol), 1,5-pentanediol, 1,2-pentanediol, 1,6-
hexanediol, 1,2-hexanediol,
1,7-heptanediol, 1,2-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-
nonanediol,
1,2-nonanediol, 2,4-dimethy1-2,5-hexanediol, the neopentyl glycol ester of
hydroxypivalic acid, diethylene glycol, triethylene glycol, 2-butene-1,4-diol,
2-butyne-
1,4-diol, polyethylene glycols, polypropylene glycols such as 1,2-
polypropylene glycol
and 1,3-polypropylene glycol, polytetrahydrofuran (polytetramethylene glycol),
diethanolamine, 1,4-bis(2-hydroxyethyl)piperazine,
diisopropanolamine, 2,5-
(dimethanol)-furan, 1,4-bis(hydroxymethyl)-cyclohexane, N-butyldiethanolamine,
N-
methyldiethanolamine, 1,10-decanediol, 1,12-dodecanediol and C36-diol (mixture
of
isomers of alcohols having the empirical formula C36E17402)-
Another name for 2,5-(dimethanol)-furan is 2,5-bis(hydroxymethyl)-furan.
Preference is given to diols having two functional groups of the formula (-CH2-
0H).
Particularly preferred diols are 2-ethanediol (ethylene glycol), 1,2-
propanediol
(1,2-propylene glycol), 1,3-propanediol (1,3-propylene glycol), 1,4-butanediol
(1,4-butylene glycol), 2-methyl-1,3-propanediol, 2,2-dimethy1-1,3-propanediol
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(neopentyl glycol), 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-
octanediol,
1,9-nonanediol, diethylene glycol, triethylene glycol, polyethylene glycols,
polypropylene glycols, polytetrahydrofuran, diethanolamine, 1,10-decanediol,
1,12-
dodecanediol, 2,5-(dimethanol)-furan and C36-diol (mixture of isomers of
alcohols
having the stoichiometric formula C36H7402).
As diols, greatest preference is given to ethylene glycol, diethanolamine,
polytetrahydrofuran, diethylene glycol, 2,5-(dimethanol)-furan and 1,4-
butanediol.
As starting materials, it is possible to use all known triols which have at
least one
functional group of the formula (¨CH2-0H). Examples of triols which can be
used in the
process of the invention are glycerol, trimethylolpropane and triethanolamine.
Preference is given to triols which have at least two functional groups of the
formula
(-CH2-0H).
Very particularly preferred triols are glycerol, trimethylolpropane and
triethanolamine.
It is possible to use all known polyols which have at least one functional
group of the
formula (-CH2-0H) as starting materials. Examples of polyols which can be used
as
starting materials in the process of the invention are 2,2-bis(hydroxymethyl)-
1,3-
propanediol (pentaerythritol), sugars and polymers such as glucose, mannose,
fructose, ribose, deoxyribose, galactose, fucose, rhamnose, sucrose, lactose,
cellobiose, maltose and amylose, cellulose, xanthan and polyvinyl alcohols.
Preference is given to polyols which have at least two functional groups of
the formula
(-CH2-0H).
All known alkanolamines which have at least one primary hydroxyl group (-CH2-
0H)
and at least one primary amino group (-NH2) can be used as starting materials.
Examples of alkanolamines which can be used as starting materials in the
process of
the invention are monoaminoethanol, 3-aminopropan-1-ol, 2-aminopropan-1-ol,
4-aminobutan-1-ol, 2-aminobutan-1-ol, 3-aminobutan-1-ol, 5-aminopentan-1-ol,
2-aminopentan-1-ol, 6-aminohexan-1-ol, 2-aminohexan-1-ol, 7-aminoheptan-1-ol,
2-aminoheptan-1-ol, 8-aminooctan-1-ol, 2-aminooctan-1-ol, N-(2-
aminoethyl)ethanol-
amine, monoaminodiethylene glycol (2-(2-aminoethoxy)ethanol), N-(2-
hydroxyethyl)-
1,3-propanediamine and 3-(2-hydroxyethyl)amino-1-propanol.
Preference is given to alkanolamines which have at least one primary hydroxyl
group
(-CH2-0H) and at least one primary amino group of the formula (-CH2-NH2).
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Very particularly preferred alkanolamines are
monoaminoethanol,
monoaminodiethylene glycol (2-(2-aminoethoxy)ethanol), 2-aminopropan-1-ol,
3-aminopropan-1-ol and 4-aminobutan-1-ol.
Complex catalyst
In the process of the invention, at least one complex catalyst comprising at
least one
element selected from groups 8, 9 and 10 of the Periodic Table (IUPAC
nomenclature)
and also at least one donor ligand is used. The elements of groups 8, 9 and 10
of the
Periodic Table comprise iron, cobalt, nickel, ruthenium, rhodium, palladium,
osmium,
iridium and platinum. Preference is given to complex catalysts which comprise
at least
one element selected from among ruthenium and iridium.
In one embodiment, the process of the invention is carried out homogeneously
catalyzed in the presence of at least one complex catalyst of the general
formula (I):
\R
""H
L3 I
(I)
where
L1 andL2 are each,
independently of one another, phosphine (RRaRb), amine
(NRaRb), sulfide, SH, sulfoxide (S(=0)R), C5-C10-heteroaryl
comprising at least one heteroatom selected from among nitrogen
(N), oxygen (0) and sulfur (S), arsine (AsRaRb), stibane (SbRaRb)
and N-heterocyclic carbenes of the formula (II) or (III):
R3 R4 R3 R4
¨NN77N¨R5 ¨NN7N¨R5
= = = =
L3 is a
monodentate two-electron donor selected from the group
consisting of carbon monoxide (CO), PRaRbRc, NO, ASRaRbRc,
SbRaRbRc, SRaRb, nitrile (RCN), isonitrile (RNC), nitrogen (N2),
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,
9
phosphorus trifluoride (PF3), carbon monosulfide (CS), pyridine,
thiophene, tetrahydrothiophene and N-heterocyclic carbenes of the
formula (II) or (III);
R1 and R2 are both hydrogen or together with the carbon atoms to which they
are bound form a phenyl ring which together with the quinolinyl unit
of the formula I forms an acridinyl unit;
R, Ra, Rb, Rb, R3, R4 and R5 are each, independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-
cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom
selected from among N, 0 and S, C5-C10-aryl or C5-C10-heteroaryl
comprising at least one heteroatom selected from among N, 0 and
S,
where the substituents are selected from the group consisting of:
F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
Y is a monoanionic ligand selected from the
group consisting of H, F,
Cl, Br, I, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR and
N(R)2 or an uncharged molecule selected from the group
consisting of NH3, N(R)3 and R2NSO2R;
X' represents one, two, three, four, five, six or
seven substituents on
one or more atoms of the acridinyl unit or one, two, three, four or
five substituents on one or more atoms of the quinolinyl unit,
where the radicals X1 are selected independently from the group
consisting of hydrogen, F, Cl, Br, I, OH, NH2, NO2, -NC(0)R,
C(0)NR2, -0C(0)R, -C(0)0R, CN and borane derivatives which
can be obtained from the catalyst of the formula (I) by reaction with
NaBH4 and unsubstituted or at least monosubstituted C1-C10-
alkoxy, C1-C10-alkyl, C3-C10-cycloalkyl,
C3-C10-heterocycly1
comprising at least one heteroatom selected from among N, 0 and
S, C5-C10-aryl and C5-C10-heteroaryl comprising at least one
heteroatom selected from among N, 0 and S,
where the substitutents are selected from the group consisting of:
F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
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,
and
M is iron, cobalt, nickel, ruthenium, rhodium,
palladium, osmium,
iridium or platinum.
5
It should be pointed out here that the complex catalyst of the formula (I)
bears a
positive charge when Y is an uncharged molecule selected from the group
consisting of
NH3, NR3, R2NSO2R and M is selected from the group consisting of ruthenium,
nickel,
palladium, platinum and iron.
In a preferred embodiment, the process of the invention is carried out in the
presence
of at least one homogeneously dissolved complex catalyst of the formula (I),
where the
substituents have the following meanings:
L1 and L2, are each, independently of one another, PRaRb, NRaRb, sulfide,
SH,
S(=0)R, C5-C10-heteroaryl comprising at least one heteroatom selected
from among N, 0 and S;
L3 is a monodentate two-electron donor selected from
the group consisting
of CO, PRaRbRb, NO, RCN, RNC, N2, PF3, CS, pyridine, thiophene and
tetrahydrothiophene;
R1 and R2 are both hydrogen or together with the carbon atoms
to which they are
bound form a phenyl ring which together with the quinolinyl unit of the
formula (I) forms an acridinyl unit;
R, Ra, Rb, c, I-K¨ R3, R4 and R5 are each, independently of one another,
unsubstituted
Cy-Cm-alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least
one heteroatom selected from among N, 0 and S, C5-C10-aryl or C5-C10-
heteroaryl comprising at least one heteroatom selected from among N,
0 and S;
Y is a monoanionic ligand selected from the group
consisting of H, F, CI,
Br, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR and N(R)2;
X1 represents one, two, three, four, five, six or
seven substituents on one or
more atoms of the acridinyl unit or one, two, three, four or five
substituents on one or more atoms of the quinolinyl unit,
where X1 is selected independently from the group consisting of
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hydrogen, F, Cl, Br, I, OH, NH2, NO2, -NC(0)R, C(0)NR2, -OC(0)R,
-C(0)OR, ON and borane derivatives which can be obtained from the
catalyst of the formula (I) by reaction with NaBH4 and unsubstituted
01-010-alkoxy, 01-C10-alkyl, 03-010-cycloalkyl, 03-010-heterocycly1
comprising at least one heteroatom selected from among N, 0 and S,
05-010-aryl and 05-010-heteroaryl comprising at least one heteroatom
selected from among N, 0 and S;
and
M is ruthenium or iridium.
In a further preferred embodiment, the process of the invention is carried out
in the
presence of at least one homogeneously dissolved complex catalyst where R1 and
R2
are both hydrogen and the complex catalyst is a catalyst of the formula (IV):
xi,
10
(4"."--.'
1/H
L1-------/TL2
L3 Y
(iv)
and X1, Ll, L2, L3 and Y are as defined above.
In a further preferred embodiment, the process of the invention is carried out
in the
presence of at least one homogeneously dissolved complex catalyst where R1 and
R2
together with the carbon atoms to which they are bound form a phenyl ring
which
together with the quinolinyl unit of the formula (I) forms an acridinyl unit
and the
complex catalyst is a catalyst of the formula (V):
xi
\
101 ./ 11101
N
1/H
Ll-----%T----------L2
L3 1
y
(V)
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and X1, L1, L2, L3 and Y are as defined above.
Some complex catalysts (formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII)
and (XIII)) which
can be used in the process of the invention are shown by way of example below:
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xl x'
\
101
0 / 0
N'''''\,,.
N
1 /H Ra 1 /H
-.._
Ra a, R
.-......_ ---7-----/ Ra-
...__------7(1--------,p,/
/ OC I \ Rb/ OC I
Y \
Rb Y Rb Rb
(VI) (VII)
xl
\ xl
401
S / 0
N
N='-''\.,
I /H
Ra N___---7y-----,__p/ Ra I /H
/ OC I \ Ra......_ ¨/-y-----
., p,.../ Ra
Rb Y
Rb / OC I \
Rb Y Rb
(VIII) (IX)
xl xl
\
140
1.1 / 0
N
1 21
Ra I /H /
Rb OC \ Rb / OC \
Y Y
Rb Rb
(X) (XI)
xl xl
\
10 / 0
N N
I /H
Ra 1 /H ,., ,Ra
Ra...._._ ---7Nr-- / Ra.-
.... NTN /
/ OC \ / OC
\
Rb Y Rb Y
Rb Rb
(Xii) (XIII)
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In a further preferred embodiment, the process of the invention is carried out
in the
presence of at least one complex catalyst selected from the group of catalysts
of the
formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), where
Ra and Rb are each, independently of one another, unsubstituted or at least
nnonosubstituted C3-C10-
cycloalkyl, C3-C10-heterocycly1 comprising
at least one heteroatom selected from among N, 0 and S, C5-C10raryl or C5-C10-
heteroaryl comprising at least one heteroatom selected from among N, 0 and
S,
where the substituents are selected from the group consisting of: F, Cl, Br,
OH,
CN, NH2 and C1-C10-alkyl;
is a monoanionic ligand selected from the group consisting of H, F, Cl, Br,
OCOR, OCOCF3, OSO2R, OSO2CF3, ON, OH, OR, N(R)2;
is unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-cycloalkyl,
C3-C10-heterocycly1 comprising at least one heteroatom selected from among N,
0 and S, C5-C10-aryl, C5-C10-heteroaryl comprising at least one heteroatom
selected from among N, 0 and S,
where the substituents are selected from the group consisting of: F, CI, Br,
OH,
CN, NH2 and C1-C10-alkyl;
X1 represents one, two or three substituents on one or more atoms of the
acridinyl
unit or one or two substituents on one or more atoms of the quinolinyl unit,
where the radicals X1 are selected independently from the group consisting of
hydrogen, F, CI, Br, I, OH, NH2, NO2, -NC(0)R, C(0)NR2, -0C(0)R, -C(0)0R,
ON and borane derivatives which can be obtained from the catalyst of the
formula (I) by reaction with NaBH4 and unsubstituted C1-C10-alkoxy, C1-C10-
alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1 comprising at least one
heteroatom
selected from among N, 0 and S, C5-C10-aryl and C5-C10-heteroaryl comprising
at least one heteroatom selected from among N, 0 and S;
and
is ruthenium or iridium.
In a further preferred embodiment, the process of the invention is carried out
in the
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presence of at least one complex catalyst selected from the group consisting
of
catalysts of the formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and
(XIII), where
Ra and Rb are each, independently of one another, methyl, ethyl, isopropyl,
tert-butyl,
5 cyclohexyl, cyclopentyl, phenyl or mesityl;
is a monoanionic ligand selected from the group consisting of H, F, Cl, Br,
OCOCH3, OCOCF3, OSO2CF3, CN and OH;
10 X1 is a substituent on an atom of the acridinyl unit or a substituent
on an atom of
the quinolinyl unit,
where X1 is selected from the group consisting of hydrogen, F, CI, Br, OH,
NH2,
NO2, -NC(0)R, C(0)NR2, -0C(0)R, -C(0)0R, CN and borane derivatives which
15 can be obtained from the catalyst of the formula (I) by reaction with
NaBH4 and
unsubstituted C1-C10-alkoxy, C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-
heterocycly1
comprising at least one heteroatom selected from among N, 0 and S, C5-C10-
aryl and C5-C10-heteroaryl comprising at least one heteroatom selected from
among N, 0 and S;
is ruthenium or iridium.
In a further preferred embodiment, the process of the invention is carried out
in the
presence of at least one complex catalyst from the group consisting of the
catalysts of
the formulae (VI), (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), where
Ra and Rb are each, independently of one another, methyl, ethyl, isopropyl,
tert-butyl,
cyclohexyl, cyclopentyl, phenyl or mesityl;
Y is a monoanionic ligand selected from the group consisting of H, F, CI,
Br, I,
OCOCH3, OCOCF3, OSO2CF3, CN and OH;
X1 is hydrogen;
and
is ruthenium or iridium.
In a particularly preferred embodiment, L3 is carbon monoxide (CO).
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In a particularly preferred embodiment, the process of the invention is
carried out in the
presence of a complex catalyst of the formula (XlVa):
1101 /1110
N
1/H
00 I
CI
,,,,,/,
\ : K
(XlVa)
In a further particularly preferred embodiment, the process of the invention
is carried
out in the presence of a complex catalyst of the formula (XIVb):
1101 / 101101
N
1 /H
0.,p ----/Rr
o b oc
c,
(XIVb)
In a very particularly preferred embodiment, the process of the invention is
carried out
in the presence of a complex catalyst of the formula (XIVb).
In a further particularly preferred embodiment, the process of the invention
is carried
out in the presence of at least one homogeneously dissolved complex catalyst
of the=
formula (XV) in which R1, R2, R3, L1, L2 and L3 are as defined above.
H., H
10
\
HI
N--....Ei
I 4
LI-------/RIU----L2
L3
H
(xV)
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Complex catalysts of the formula (XV) can be obtained by reacting catalysts of
the
formula (I) with sodium borohydride (NaBH4). The reaction proceeds according
to the
general reaction equation:
xi xilt.HR,
1
0
\R \
NaBH4
D. 4101
N N----- =
/
L.1-------/RiuL2 LI------/R1uL2
0 L.3
Y H
In a further particularly preferred embodiment, the process of the invention
is carried
out in the presence of a complex catalyst of the formula (XVIa):
11101,1-1, s,,,,,
H
r._:_p
X OC I
H
(XVIa)
In a further particularly preferred embodiment, the process of the invention
is carried
out in the presence of a complex catalyst of the formula (XVI b):
0
N
o1/1
P OC/ I
ci
(XIVb) b
The borane derivative of the formula (XVIa) can be obtained according to the
following
reaction equation:
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H H
Na13114 (I Equivalent)
2h Room temperature
I H
I
CI
OC
The borane derivative of the formula (XVIb) can be obtained according to the
following
reaction equation:
H
NaBH4 (1 Equivalent), io H
11101 ISO
2h Room temperature
I 11
I ----P
= OC
o
For the purposes of the present invention, the term C1-C10-alkyl refers to
branched,
unbranched, saturated and unsaturated groups. Preference is given to alkyl
groups
having from 1 to 6 carbon atoms (C1-C6-alkyl). Greater preference is given to
alkyl
groups having from 1 to 4 carbon atoms (C1-C4-alkyl).
Examples of saturated alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-
butyl,
isobutyl, sec-butyl, tert-butyl, amyl and hexyl.
Examples of unsaturated alkyl groups (alkenyl, alkynyl) are vinyl, allyl,
butenyl, ethynyl
and propynyl.
The CI-Cm-alkyl group can be unsubstituted or substituted by one or more
substituents
selected from the group consisting of F, Cl, Br, hydroxy (OH), C1-C10-alkoxy,
C5-C10-
aryloxy, C6-C10-alkylaryloxy, C6-C10-heteroaryloxy comprising at least one
heteroatom
selected from among N, 0, S, oxo, C3-C10-cycloalkyl, phenyl, C6-C10-heteroaryl
comprising at least one heteroatom selected from among N, 0, S, C6-C10-
heterocycly1
comprising at least one heteroatom selected from among N, 0, S, naphthyl,
amino,
C1-C10-alkylamino, C6-C10-arylamino, C6-C10-heteroarylamino comprising at
least one
heteroatom selected from among N, 0, S, C1-C10-dialkylamino, C10-C12-
diarylamino,
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C10-C20-alkylarylamino, C1-C10-acyl, C1-C10-acyloxy, NO2, C1-C10-carboxy,
carbamoyl,
carboxamide, cyano, sulfonyl, sulfonylamino, sulfinyl, sulfinylamino, thiol,
Ci-Clo-
alkylthiol, C5-C10-arylthiol and C1-C10-alkylsulfonyl.
For the present purposes, the term C3-C10-cycloalkyl refers to saturated,
unsaturated
monocyclic and polycyclic groups. Examples of C3-C10-cycloalkyl are
cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. The cycloalkyl groups can
be
unsubstituted or substituted by one or more substituents as have been defined
above
for the C1-C10-alkyl group.
For the purposes of the present invention, C5-C10-aryl is an aromatic ring
system
having from 5 to 10 carbon atoms. The aromatic ring system can be monocyclic
or
bicyclic. Examples of aryl groups are phenyl, naphthyl such as 1-naphthyl and
2-naphthyl. The aryl group can be unsubstituted or substituted by one or more
substituents as defined above under C1-C10-alkyl.
For the purposes of the present invention, C5-C10-heteroaryl is a
heteroaromatic system
comprising at least one heteroatom selected from the group consisting of N, 0
and S.
The heteroaryl groups can be monocyclic or bicyclic. When the nitrogen is a
ring atom,
the present invention also comprises N-oxides of the nitrogen-comprising
heteroaryls.
Examples of heteroaryls are thienyl, benzothienyl, 1-naphthothienyl,
thianthrenyl, fury!,
benzofuryl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl,
pyridazinyl,
indolyl, isoindolyl, indazolyl, purinyl, isoquinolinyl, quinolinyl, acridinyl,
naphthyridinyl,
quinoxalinyl, quinazolinyl, cinnolinyl, piperidinyl, carbolinyl, thiazolyl,
oxazolyl,
isothiazolyl, isoxazolyl. The heteroaryl groups can be unsubstituted or
substituted by
one or more substituents defined above under C1-C10-alkyl.
For the purposes of the present invention, the term C3-C10-heterocycly1 refers
to five- to
ten-membered ring systems comprising at least one heteroatom from the group
consisting of N, 0 and S. The ring systems can be monocyclic or bicyclic.
Examples of
suitable heterocyclic ring systems are piperidinyl, pyrrolidinyl, pyrrolinyl,
pyrazolinyl,
pyrazolidinyl, morpholinyl, thiomorpholinyl, pyranyl, thiopyranyl,
piperazinyl, indolinyl,
dihydrofuranyl, tetrahydrofuranyl, dihydrothiophenyl,
tetrahydrothiophenyl,
dihydropyranyl and tetrahydropyranyl.
Alcohol amination
The homogeneous catalysts can be produced either directly in their active form
or only
under the reaction conditions from customary precursors with addition of the
appropriate ligands. Customary precursors are, for example, [Ru(p-
cymene)C12]2,
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[Ru(benzene)C12], [Ru(C0)2C12], [Ru(C0)3C12]2 [Ru(COD)(allyI)], [RuCI3*H20],
[Ru(acetylacetonate)3], [Ru(DMS0)4C12], [Ru(PPh3)3(C0)(H)CI],
[Ru(PPh3)3(CO)C12],
[Ru(PPh3)3(C0)(H)2], [Ru(PPh3)3C12],
[Ru(cyclopentadienyl)(PPh3)2C1],
[Ru(cyclopentadienyl)(C0)2C1],
[Ru(cyclopentadienyl)(C0)2F1],
5 [Ru(cyclopentadienyl)(C0)2]2, [Ru(pentamethylcyclopentadienyl)(C0)2C1],
[Ru(penta-
methylcylcopentadienyl)(C0)2F1],
[Ru(pentamethylcyclopentadienyl)(C0)2h,
[Ru(indenyl)(C0)2C1], [Ru(indenyl)(C0)2H],
[Ru(indenyl)(CO)2]2, ruthenocene,
[Ru(binap)Cl2], [Ru(bipyridine)2Cl2*2H20], [Ru(COD)C12]2, [Ru(pentamethylcyclo-
pentadienyl)(COD)C1], [Ru3(C0)12],
[Ru(tetraphenylhydroxycyclopentadienyl)(C0)21-1],
10 [Ru(PMe3)4(H)2], [Ru(PEt3)4(H)2], [Ru(PnPr3)4(H)2],
[Ru(PnBu3)4(H)2],
[Ru(PnOcty13)4(H)2], [IrCI3*H20], KIrCI4, K3IrC16, [Ir(COD)C1]2,
[Ir(cyclooctene)2C1]2,
[I r(ethene)2C1]2, [I r(cyclopentadienyl)C12]2, [I
r(pentamethylcyclopentadieny0C12]2,
[Ir(cylopentadienyl)(C0)2], [Ir(pentamethylcyclopentadienyl)(C0)21,
[Ir(PPh3)2(C0)(H)l,
[Ir(PPh3)2(C0)(C1)], [I r(PPh3)3(C1)].
For the purposes of the present invention, homogeneously catalyzed means that
the
catalytically active part of the complex catalyst is at least partly present
in solution in
the liquid reaction medium. In a preferred embodiment, at least 90% of the
complex
catalyst used in the process is present in solution in the liquid reaction
medium, more
preferably at least 95%, particularly preferably more than 99%; the complex
catalyst is
most preferably entirely present in solution in the liquid reaction medium
(100%), in
each case based on the total amount in the liquid reaction medium.
The amount of the metal component of the catalyst, preferably ruthenium or
iridium, is
generally from 0.1 to 5000 ppm by weight, in each case based on the total
liquid
reaction medium.
The reaction occurs in the liquid phase, generally at a temperature of from 20
to 250 C.
The process of the invention is preferably carried out at temperatures in the
range from
100 C to 200 C, particularly preferably in the range from 110 to 160 C.
The reaction can generally be carried out at a total pressure of from 0.1 to
20 MPa
absolute, which can be either the autogenous pressure of the solvent at the
reaction
temperature or the pressure of a gas such as nitrogen, argon or hydrogen. The
process
of the invention is preferably carried out at a total pressure in the range
from 0.5 to
10 MPa absolute, particularly preferably at a total pressure in the range from
1 to
6 MPa absolute.
The average reaction time is generally from 15 minutes to 100 hours.
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The aminating agent (ammonia) can be used in stoichiometric, substoichiometric
or
superstoichiometric amounts based on the hydroxyl groups to be aminated.
In a preferred embodiment, ammonia is used in a from 1- to 250-fold,
preferably a from
2-to 100-fold, in particular in a from 1.5- to 10-fold, molar excess per mole
of hydroxyl
groups to be reacted in the starting material. Higher excesses of ammonia are
also
possible.
The process of the invention can be carried out either in a solvent or without
solvent.
Suitable solvents are polar and nonpolar solvents which can be used in pure
form or in
mixtures. For example, it is possible to use only one nonpolar or one polar
solvent in
the process of the invention. It is also possible to use mixtures of two or
more polar
solvents or mixtures of two or more nonpolar solvents or mixtures of one or
more polar
solvents with one or more nonpolar solvents. The product can also be used as
solvent,
either in pure form or in mixtures with polar or nonpolar solvents.
Suitable nonpolar solvents are, for example, saturated and unsaturated
hydrocarbons
such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene and
mesitylene and linear and cyclic ethers such as THF, diethyl ether, 1,4-
dioxane, MTBE
(tert-butyl methyl ether), diglyme and 1,2-dimethoxyethane. Preference is
given to
using toluene, xylene or mesitylene.
Suitable polar solvents are, for example, water, dimethylformamide, formamide,
tert-
amylalcohol, tert-butanol and acetonitrile. Preference is given to using
water. The water
can either be added before the reaction, be formed as water of reaction during
the
reaction or be added after the reaction in addition to the water of reaction.
A further
preferred solvent is tert-amylacohol. Preferred is a mixture of tert-
amylalcohol and
water.
To carry out the reaction in the liquid phase, ammonia, the at least one
functional group
of the formula (-CH2-0H) and at least one further functional group of the
formula (-X)
having starting material, optionally together with one or more solvents,
together with
the complex catalyst are introduced into a reactor.
The introduction of ammonia, starting material, optionally solvent and complex
catalyst
can be carried out simultaneously or separately. The reaction can be carried
out
continuously, in the semibatch mode, in the batch mode, admixed in product as
solvent
or without admixing in a single pass.
It is in principle possible to use all reactors which are basically suitable
for gas/liquid
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reactions at the given temperature and the given pressure for the process of
the
invention. Suitable standard reactors for gas/liquid reaction systems and for
liquid/liquid
reaction systems are, for example, indicated in K.D. Henkel, "Reactor Types
and Their
Industrial Applications", in Ullmann's Encyclopedia of Industrial Chemistry,
2005, Wiley-
VCH Verlag GmbH & Co. KGaA, DOI: 10.1002/14356007.b04_087, chapter 3.3
"Reactors for gas-liquid reactions". Examples which may be mentioned are
stirred tank
reactors, tube reactors or bubble column reactors.
In the amination reaction, at least one primary hydroxyl group (-CH2-0H), of
the starting
material is reacted with ammonia to form a primary amino group (-CH2-NH2),
with in
each case one mole of water of reaction being formed per mole of reacted
hydroxyl
group.
Thus, the reaction of alkanolamines having only one primary hydroxyl group (-
CH2-0H)
forms the corresponding diamines. The reaction of monoaminoethanol thus leads
to
the corresponding 1,2-diaminoethane.
In the reaction of starting materials which have not only the functional group
of the
formula (-CH2-0H) but also a further hydroxyl group (diols), both hydroxyl
groups are
reacted with ammonia to form the corresponding primary diamines. The reaction
of
1,2-ethylene glycol thus leads to the corresponding 1,2-diaminoethane. The
reaction of
2,5-(dimethanol)-furan thus leads to 2,5-bis(aminomethyl)-furan.
In the reaction of starting materials which have not only the functional group
of the
formula (-CH2-0H) but also two further hydroxyl groups (triols), two or three
hydroxyl
groups are reacted with ammonia to form the corresponding primary diamines or
triamines. The formation of diamines or triamines can be controlled by the
amount of
ammonia used and by the reaction conditions. The reaction of glycerol thus
leads to
the corresponding 1,2-diaminopropanol or to 1,2,3-triaminopropane.
In the reaction of starting materials which have not only the functional group
of the
formula (-CH2-0H) but also more than three further hydroxyl groups (polyols),
two,
three or more hydroxyl groups are reacted with ammonia to form the
corresponding
primary diamines, triamines or polyamines. The formation of the corresponding
primary
diamines, triamines or polyamines can be controlled by the amount of ammonia
used
and by the reaction conditions.
The reaction output formed in the reaction generally comprises the
corresponding
amination products, the one or more solvents if used, the complex catalyst,
possibly
unreacted starting materials and ammonia and also the water of reaction
formed.
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Any excess ammonia present, any solvent present, the complex catalyst and the
water
of reaction are removed from the reaction output. The amination product
obtained can
be worked up further. The excess ammonia, the complex catalyst, any solvent or
solvents and any unreacted starting materials can be recirculated to the
amination
reaction.
If the amination reaction is carried out without solvent, the homogeneous
complex
catalyst is dissolved in the product after the reaction. This can remain in
the product or
be separated off therefrom by a suitable method. Possibilities for separating
off the
catalyst are, for example, scrubbing with a solvent which is not miscible with
the
product and in which the catalyst dissolves better than in the product as a
result of a
suitable choice of the ligands. The catalyst concentration in the product is
optionally
reduced by multistage extraction. As extractant, preference is given to using
a solvent
which is also suitable for the target reaction, e.g. toluene, benzene,
xylenes, alkanes
such as hexanes, heptanes and octanes and acyclic or cyclic ethers such as
diethyl
ether and tetrahydrofuran, which can after concentration by evaporation be
reused
together with the extracted catalyst for the reaction. It is also possible to
remove the
catalyst by means of a suitable absorbent. The catalyst can also be separated
off by
adding water to the product phase if the reaction is carried out in a solvent
which is
immiscible with water. If the catalyst in this case dissolves preferentially
in the solvent,
it can be separated off with the solvent from the aqueous product phase and
optionally
be reused. This can be brought about by selection of suitable ligands. The
resulting
aqueous diamines, triamines or polyamines can be used directly as technical-
grade
amine solutions. It is also possible to separate the amination product from
the catalyst
by distillation.
If the reaction is carried out in a solvent, the latter can be miscible with
the amination
product and be separated off by distillation after the reaction. It is also
possible to use
solvents which have a miscibility gap with the amination products or the
starting
materials. Suitable solvents for this purpose are, for example, toluene,
benzene,
xylenes, alkanes such as hexanes, heptanes and octanes and acyclic or cyclic
ethers
such as diethyl ether, tetrahydrofuran, tert-amylalcohol and dioxane. As a
result of
suitable choice of the phosphine ligands, the catalyst preferentially
dissolves in the
solvent phase, i.e. in the phase not comprising product. The phosphine ligands
can
also be selected so that the catalyst dissolves in the amination product. In
this case,
the amination product can be separated from the catalyst by distillation.
The product may also be used as solvent. The solvent can also be miscible with
the
starting materials and the product under the reaction conditions and only form
a second
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24
liquid phase comprising the major part of the catalyst after cooling. As
solvents which
display this property, mention may be made by way of example of toluene,
benzene,
xylenes, alkanes such as hexanes, heptanes and octanes. The catalyst can then
be
separated off together with the solvent and be reused. The product phase can
also be
admixed with water in this variant. The proportion of the catalyst comprised
in the
product can subsequently be separated off by means of suitable absorbents such
as
polyacrylic acid and salts thereof, sulfonated polystyrenes and salts thereof,
activated
carbons, montmorillonites, bentonites and zeolites or else be left in the
product.
The amination reaction can also be carried out in a two-phase system. In the
case of
the two-phase reaction, suitable nonpolar solvents are, in particular,
toluene, benzene,
xylenes, alkanes such as hexanes, heptanes and octanes in combination with
lipophilic
phosphine ligands on the transition metal catalyst, as a result of which the
transition
metal catalyst accumulates in the nonpolar phase. In this embodiment, in which
the
product and the water of reaction and any unreacted starting materials form a
second
phase enriched with these compounds the major part of the catalyst can be
separated
off from the product phase by simple phase separation and be reused.
If volatile by-products or unreacted starting materials or the water formed in
the
reaction or added after the reaction to aid the extraction are undesirable,
they can be
separated off from the product without problems by distillation.
It can also be advantageous for the water formed in the reaction to be removed
continuously from the reaction mixture. The water of reaction can be separated
off from
the reaction mixture directly by distillation or as azeotrope with addition of
a suitable
solvent (entrainer) and using a water separator or be removed by addition of
water-
withdrawing auxiliaries.
The addition of bases can have a positive effect on product formation.
Suitable bases
which may be mentioned here are alkali metal hydroxides, alkaline earth metal
hydroxides, alkaline metal alkoxides, alkaline earth metal alkoxides, alkali
metal
carbonates and alkaline earth metal carbonates, of 0.01 to 100 molar
equivalents,
based on the metal catalyst used, can be used.
The present invention further provides for the use of a complex catalyst
comprising at
least one element selected from groups 8, 9 and 10 of the Periodic Table and
also at
least one donor ligand for the homogeneously catalyzed preparation of primary
amines
which have at least one functional group of the formula (-CH2-NH2) and at
least one
further primary amino group by alcohol amination of starting materials having
at least
one functional group of the formula (-CH2-0H) and at least one further
functional group
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(-X), where (-X) is selected from among hydroxyl groups and primary amino
groups, by
means of ammonia.
In a preferred embodiment, the present invention provides for the use of a
5 homogeneously dissolved complex catalyst of the general formula (I):
V-,R1
2
I /H
(I)
where
I: and L2 are each, independently of one another, PRaRb,
NRaRb, sulfide,
SH, S(0)R, C5-C10-heteroaryl comprising at least one heteroatom
selected from among N, 0 and S, AsRaRb, SbRaRb and N-
heterocyclic carbenes of the formula (II) or (III):
-N
R3 Ni7,NR4 5 R3
-N -R5
-R N7N
= =
(II)
L3 is a monodentate two-electron donor selected from
the group
consisting of CO, PRaRbRc, NO, AsRaRbRc, SbRaRbRc, SRaRb,
RCN, RNC, N2, PF3, CS, pyridine, thiophene, tetrahydrothiophene
and N-heterocyclic carbenes of the formula ll or Ill;
R1 and R2 are both hydrogen or together with the carbon atoms
to which they
are bound form a phenyl ring which together with the quinolinyl unit
of the formula I forms an acridinyl unit;
R, Ra, Rb, Rc, R3, R4, and R5 are each, independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-
cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom
selected from among N, 0 and S, C5-C10-aryl or C5-C10-heteroaryl
comprising at least one heteroatom selected from among N, 0 and
EK10-1685PC
PF0000071685/MKr CA 02828168 2013-08-23
=
26
S,
where the substituents are selected from the group consisting of:
F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
is a monoanionic ligand selected from the group consisting of H, F,
Cl, Br, I, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, OH, OR and
N(R)2 or an uncharged molecule selected from the group
consisting of NH3, N(R)3 and R2NSO2R;
X' represents one, two, three, four, five, six or seven substituents on
one or more atoms of the acridinyl unit or one, two, three, four or
five substituents on one or more atoms of the quinolinyl unit,
where the radicals X' are selected independently from the group
consisting of hydrogen, F, Cl, Br, I, OH, NH2, NO2, -NC(0)R,
C(0)NR2, -0C(0)R, -C(0)0R, CN and borane derivatives which
can be obtained from the catalyst of the formula I by reaction with
NaBH4 and unsubstituted or at least monosubstituted C1-C10-
alkoxy, C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-heterocycly1
comprising at least one heteroatom selected from among N, 0 and
S, C5-C10-aryl and C5-C10-heteroaryl comprising at least one
heteroatom selected from among N, 0 and S,
where the substituents are selected from the group consisting of:
F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
and
M is iron,
cobalt, nickel, ruthenium, rhodium, palladium, osmium,
iridium or platinum,
for the homogeneously catalyzed preparation of primary amines which have at
least
one functional group of the formula (-CH2-NH2) and at least one further
primary amino
group by alcohol amination of starting materials having at least one
functional group of
the formula (-CH2-0H) and at least one further functional group (-X), where (-
X) is
selected from among hydroxyl groups and primary amino groups, by means of
ammonia, where the definitions and preferences described above for the process
of the
invention apply to the catalyst of the general formula (I).
EK10-1685PC
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27
In a further preferred embodiment, the present invention relates to the use of
a
homogeneously dissolved complex catalyst of the general formula (XV):
H
X1
00\ R
H ,H R
NI 2
L L2
L3 I
(xv)
where
L1 and L2 are each, independently of one another, PRaRb, NRaRb,
sulfide,
SH, S(=0)R, C5-C10-heteroaryl comprising at least one heteroatom
selected from among N, 0 and S, AsRaRb, SbRaRb or
N-heterocyclic carbenes of the formula (II) or (III):
(4 R3
¨(R
DJ.¨NNN¨R5
= =
(II) (III)
L3 is a monodentate two-electron donor selected from the group
consisting of CO, PRaRbRc, NO, ASRaRbRc, SbRaRbRc, SRaRb,
RCN, RNC, N2, PF3, CS, pyridine, thiophene, tetrahydrothiophene
and N-heterocyclic carbenes of the formula (II) or (III);
R1 and R2 are both hydrogen or together with the carbon atoms to
which they
are bound form a phenyl ring which together with the quinolinyl unit
of the formula (I) forms an acridinyl unit;
R, Ra, Rb, Rc, R3, R4 and R5 are each, independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-
cycloalkyl, C3-C10-heterocycly1 comprising at least one heteroatom
selected from among N, 0 and S, C5-C10-aryl or C5-C10-heteroaryl
comprising at least one heteroatom selected from among N, 0 and
S,
EK10-1685PC
= PF0000071685/MKr CA 02828168 2013-08-23
28
where the substituents are selected from the group consisting of:
F, Cl, Br, OH, ON, NH2 and 01-010-alkyl;
Y is a monoanionic ligand selected from the group consisting of H,
F,
Cl, Br, I, OCOR, 0000F3, OSO2R, OSO2CF3, ON, OH, OR and
N(R)2 or uncharged molecules selected from the group consisting
of NH3, N(R)3 and R2NSO2R;
X1 represents one, two, three, four, five, six or seven substituents
on
one or more atoms of the acridinyl unit or one, two, three, four or
five substituents on one or more atoms of the quinolinyl unit,
where the radicals X1 are selected independently from the group
consisting of hydrogen, F, Cl, Br, I, OH, NH2, NO2, -NC(0)R,
C(0)NR2, -0C(0)R, -C(0)0R, ON and borane derivatives which
can be obtained from the catalyst of the formula I by reaction with
NaBH4 and unsubstituted or at least monosubstituted 01-010-
alkoxy, C1-C10-alkyl,
03-C10-cycloalkyl, 03-C10-heterocycly1
comprising at least one heteroatom selected from among N, 0 and
S, O5-C-aryl and 05-C10-heteroaryl comprising at least one
heteroatom selected from among N, 0 and S,
where the substituents are selected from the group consisting of:
F, CI, Br, OH, ON, NH2 and 01-010-alkyl;
and
M is iron, cobalt, nickel, ruthenium, rhodium,
palladium, osmium,
iridium or platinum,
for the homogeneously catalyzed preparation of primary amines which have at
least
one functional group of the formula (-0H2-NH2) and at least one further
primary amino
group by alcohol amination of starting materials having at least one
functional group of
the formula (-CH2-0H) and at least one further functional group (-X), where (-
X) is
selected from among hydroxyl groups and primary amino groups, by means of
ammonia, where the definitions and preferences described above for the process
of the
invention apply to the catalyst of the general formula I.
The invention is illustrated by the following examples without being
restricted thereto.
EK10-1685PC
PF0000071685/MKr CA 02828168 2013-08-23
29
Examples
General method for the catalytic amination of alcohols by means of ammonia
according
to the invention
Catalyst complex XlVb (for preparation, see below, weighed out under an inert
atmosphere), solvent (such an amount that the total solvent volume is 50 ml)
and the
alcohol to be reacted were placed under an argon atmosphere in a 160 ml Parr
autoclave (stainless steel V4A) having a magnetically coupled inclined blade
stirrer
(stirring speed: 200-500 revolutions/minute). The indicated amount of ammonia
was
introduced at room temperature either in precondensed form or directly from
the
pressurized NH3 gas bottle. If hydrogen was used, this was effected by
iterative
differential pressure metering. The steel autoclave was electrically heated to
the
temperature indicated and heated for the time indicated while stirring (500
revolutions/minute) (internal temperature measurement). After cooling to room
temperature, venting the autoclave and outgassing the ammonia at atmospheric
pressure, the reaction mixture was analyzed by GC (30m RTX5 amine 0.32 mm
1.5 pm). Purification of the particular products can, for example, be carried
out by
distillation. The results for the amination of 1,4-butanediol (table 1a, 1 b),
diethylene
glycol (table 2) and monoethylene glycol (table 3), 2,5-furandimethanol (table
4),
alkyldiols (table 5), 1,4-bis(hydroxymethyl)-cyclohexane (table 6) and
aminoalcohols
(table 7) are given below.
Synthesis of the catalyst complex XlVb
PCy2
,Br
40/ 110
HPCy2 \ [RuHCI(C0)(PPh3)31
/ \ N Br PCy2 N \
Me0H Toluene
o CO \
XlVb
a) Synthesis of 4,5-bis(dicyclohexylphosphinomethyl)acridine
A solution of 4,5-bis(bromomethyl)acridine1
(5.2 g, 14.2 mmol) and
dicyclohexylphosphine (8.18 g, 36.8 mmol) in 65 ml of anhydrous, degassed
methanol
was heated at 50 C under an inert argon atmosphere for 66 hours. After cooling
to
room temperature, triethylamine (5.72 g, 56.7 mmol) was added and the mixture
was
EK10-1685PC
PF0000071685/MKr CA 02828168 2013-08-23
stirred for 1 hour. Evaporation of the solvent gave a whitish yellow solid in
a red oil.
Extraction by means of 3 x 40 ml of MTBE and concentration of the filtrate
gave a
reddish brown oil (1H NMR: mixture of product & HPCy2). Taking up in a little
warm
MTBE followed by addition of ice-cooled methanol resulted in precipitation of
a yellow,
5 microcrystalline solid. Oscillation and drying under reduced pressure
gave air sensitive
4,5-bis(dicyclohexylphosphinomethyl)acridine (2.74 g, 33%) as a yellow powder.
1H NMR (360.63 MHz, d8-toluene): 6 [ppm] = 8.07 (s, 1H, H9), 7.91 (d, J = 8.3
Hz, 2H,
Ar-H), 7.42 (d, J = 8.3 Hz, 2H, Ar-H), 7.21 (dd, J = 8.3 Hz, J = 7.2 Hz, 2H,
Ar-H), 3.89
(bs, 4H, -CH2-P), 1.96-1.85 (m, 8H, Cy-H), 1.77-1.54 (m, 20H, Cy-H), 1.26-1.07
(m,
10 16H, Cy-H). 31P{1H} NMR (145.98 MHz, d8-toluene): 6 [ppm] = 2.49 (s, -
CH2-P(Cy)2).
b) Synthesis of the catalyst complex XlVb
4,5-bis(dicyclohexylphosphinomethyl)acridine (1855 mg, 3.1
mmol) and
15 [RuHCI(C0)(PPh3)3]2 (2678 mg, 2.81 mmol) were heated at 70 C in 80 ml of
degassed
toluene for 2 hours. The resulting dark brown solution was evaporated to
dryness, the
residue was slurried in 3 x 20 ml of hexane and isolated by filtration. Drying
under
reduced pressure gave the catalyst complex XlVb (1603 mg, 75%) as an orange-
brown
powder. 1H NMR (360.63 MHz, d8-toluene): 6 [ppm] = 8.06 (s, 1H, H9), 7.43 (d,
J =
20 7.6 Hz, 2H, Ar-H), 7.33 (d, J = 6.5 Hz, 2H, Ar-H), 7.06-7.02 (m, 2H, Ar-
H), 5.02 (d, J =
11.9 Hz, 2H, -CHH-PCy2), 3.54 (d, J = 12.2 Hz, 2H, -CHH-PCy2), 2.87 (bs, 2H,
-P(C.H(CH2)5)2), 2.54 (bs, 2H, -P(CbH(CH2)5)2), 2.18 (bs, 2H, Cy-H), 1.88-1.85
(m, 8H,
Cy-H), 1.65 (bs, 6H, Cy-H), 1.42-1.35 (m, 14H, Cy-H), 1.17-0.82 (m, 12H, Cy-
H),
-16.29 (t, J = 19.1 Hz, 1H, Ru-H). 31P{1H} NMR (145.98 MHz, d8-toluene): 6
[ppm] =
25 60.89 (s, -CH2-P(CY)2).
[1] J. Chiron, J.P. Galy, Synlett, 2003, 15.
[2] Literature instructions: Inorganic Syntheses 1974, 15, 48. See also: T.
Joseph, S. S.
Deshpande, S. B. Halligudi, A. Vinu, S. Ernst, M. Hartmann, J. Mol. Cat. (A)
2003, 206,
30 13-21.
EK10-1685PC
BASF SE INV0071685/MKr
PF0000071685/MKr -
31
Table la: Reaction of 1,4-butanediol
L J L J
NH, Ho,.___,
NH, 4. H2N N H2 4.N N
H
a b c
Reaction
Selectivity
n
No') Solvent T 1 C] Time NH3 d pressure Further condition Conversion
[h] [eqr) a b c
0
[bar]
I.)
cc
I.)
1 Toluene 155 12 6 44 0.2 mol% of KOtBu 43.3 60.1 12.1
18.7 CO
H
Ol
2 Toluene 155 12 6 -41 1.0 mol% of KOtBu 37.0 61.9 11.4
18.7 0
I.)
3 Toluene 155 24 9 51 87.0 50.3 14.8
30.8 0
H
LO
I
4 Toluene 155 60 6 57 5 bar of H2 injected58.7 62.2 18.8
18.3 0
0
1
cold
I.)
u.)
p-Xylene 180 12 6 -51 - 100.0 0.6 51.0
43.6
6 p-Xylene 180 12 6 47 5.0 mol% of water
99.9 0.7 46.7 ' 48.6
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of 1,4-butanediol, 0.1 mol% of catalyst complex XlVb
(per alcohol group), b) evaluation by GC (% by area), c) product selectivity
determined by GC, d) molar equivalents of NH3 per OH
function on the substrate
EK10-1685PC
=
BASF SE INV0071685/MKr
PF0000071685/MKr
32
Table lb: Reaction of 1,4-butanediol
L ) L J
NH3 Ho +,...,,. H2N N H2 + N N
NH2H
a b c
Solvent T Time NH3 Reaction- Further
Conversion Selectivity CI
b)
No.a) (waterfree) rC] [h] [eq]d) pressure [bar]
conditions a) a b c
[oi]
I'M [Vo] rol
n
1 Toluol 155 12 6 46,1 0,2 mol% KOH (aq, 20%)
59.25 59.14 16.42 19.89 0
I.)
2 Toluol 155 15 6 42,0 -- 96.06
17.90 14.20 62.10 co
I.)
3 Toluol 155 24 6 40,2 -- 98.92
8.60 20.38 64.91 CO
H
al
4 Toluol 180 2 6 52,7 -- 91.52
36.35 25.76 35.39 co
I.)
Toluol 180 9 6 48,0 -- 100.00 0.12
19.90 73.67 0
H
6 Toluol 180 12 6 69,7 5 bar H2 94.19
30.09 37.23 31.62 u.)
1
0
7 Toluol 180 12 6 81,9 10 bar H2 89.85
36.24 35.41 27.66 co
1
8 Dioxane 180 12 6 44,3 -- 100.00
1.15 23.79 71.23 I.)
u.)
9 THE 180 12 6 46,9 -- 100.00
0.00 17.03 77.33
THE 180 12 9 62,3 -- 100.00
0.00 20.16 71.30
11 THE 180 12 6 71,7 5 bar H2 99.87
2.41 26.28 67.55
a) condition unless indicated otherwise: 50 ml solvent, batch size 25 mmol 1,4-
butanediol; b) evaluation by GC (% by area),
c) product selectivity determined by GC; d) molar equivalents NH3 per OH
function on the substrate; e) mol% based on the OH functions on the substrate
EK10-1685PC
BASF SE INV0071685/MKr
PF0000071685/MKr =
33
Table 2a: Reaction of diethylene glycol
NH3 /--\
HO .,.,-,.cs..---..,,OH ----3". HO ,.--..o ---..,,õ NH, + H2N o.-----
,,,,NH, + 0 NH
a b - c
Time NH3 Reaction Further
Conversion b) Selectivity
N0a) Solvent T [ C]
[h] [eq]d) pressure [bar] conditions a
b c n
1 Toluene 155 12 6 40
79.0 51.4 23.8 12.9 0
I.)
2 Toluene 155 12 6 43
82.4 55.3 20.1 10.9 0
I.)
0
3 Toluene 155 12 6 42 0.2 mol% of
KOtBu 69.8 41.8 31.9 14.3 H
Ol
CO
4 Toluene 155 12 6 43 1.0 mol% of
KOtBu 60.4 44.7 25.8 14.8 I.)
0
Toluene 155 60 6 58 5 bar of H2 66.5 57.1 31.0
9.9 H
LO
I
6 p-Xylene 155 12 6 38 1.0 mol% of
water 77.5 52.9 21.6 16.9 0
0
1
7 p-Xylene 155 12 6 41 5 mol% of water 84.0
49.0 21.1 12.8 I.)
u.)
8 p-Xylene 155 15 6 46
77.5 49.1 23.7 13.1
9 p-Xylene 155 24 6 44
96.3 17.0 48.6 19.9
p-Xylene 155 24 6 53 1.0 mol% of water
84.6 51.8 20.8 12.9
11 p-Xylene 180 12 6 50 100.0 0.4
46.1 27.9
12 p-Xylene 180 12 6 50 5 mol% of H20 100.0 0.4
48.2 27.4
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of diethylene glycol, 0.1 mol% of catalyst complex XlVb (per alcohol
group); b) evaluation by GC (% by area); c) product selectivity determined by
GC; d) molar equivalents of NH3 per OH function on the substrate; f)
batch size 35 mmol of diethylene glycol in 70 ml of solvent
EK10-1685PC
=
BASF SE INV0071685/MKr
PF0000071685/MKr
34
Table 2b: Reaction of diethylene glycol
NH3 /--\
HO ,...õ...---Ø.--,...,...õOH -10- HO ,,,------o.---..,, NH2 + H2N o -----
..,... NH2 +
0 NH
\____/
a b c
Solvent Catalyst T Time [h] NH3 Reaction Further
Conversion Selectivity `)
n
No.a) (waterfree) [ C] [eq]d) pressure (bar) conditions
e) b) a b c
[0,0]
rye] rya] rd .
"
.
i co
1 Toluol XlVb 155 12 2,0
12.3 83.52 37.60 13.93 25.58 N)
co
2 Toluol XlVb 155 12 6 40,9
0,2 mol% KOH (aq, 20%) 73.94 39.35 37.29 15.28 H
0)
CO
3 Toluol XlVb 155 24 6
43,6 97.31 18.10 36.58 21.66
I.)
4 Toluol XlVb 155 15 6 45,7
0.05 mol% XlVb 95.97 17.66 40.46 26.67 0
H
5 Toluol XlVb 155 12 6 65,5
5 bar H2 61.84 69.16 18.61 8.01 u.)
1
6 Toluol XlVb 155 12 6 36,0
25 g t-Butanol, 25 ml Toluol 86.90 44.98 26.76 15.52
0
co
1
7 Toluol XlVb 165 12 6
45,1 98.22 12.52 40.92 21.86 I.)
u.)
' 8 Toluol XlVb 170 12 6
45,7 99.81 4.39 43.66 26.02
9 Toluol XlVb 180 2 6 47,2
0,2 mol% XlVb 95.81 19.45 41.17 19.87
Toluol XlVb 180 9 6 45,5
100.00 0.75 39.21 29.46
11 Toluol XlVb 180 12 6
37,7 100.00 0.00 32.75 38.67
12 Toluol XlVb 180 12 6 69,7
5 bar H2 96.05 20.68 54.70 16.64
13 Toluol XlVb 180 12 6 75,6
10 bar H2 86.11 35.73 47.22 13.77
14 Dioxane XlVb 155 12 6 38,0
68.17 65.02 20.29 9.21
Dioxane XlVb 180 12 6 34,1 99.66
4.65 40.23 34.65
16 THE XlVb 155 12 6 41,0
70.97 54.46 19.41 11.95
17 THF XlVb 155 12 9 51,9
81.65 53.75 23.60 13.51
EK10-1685PC
BASF SE INV0071685/MKr
PF0000071685/MKr
18 THE XlVb 180 12 6 49,1
100.00 0.00 42.48 41.98
19 Toluol XlVa 155 12 6 40,7
68.02 69.62 9.60 9.52
20 Toluol XlVa 155 24 6 42,1
77.16 43.54 20.09 15.10
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of diethylene glycol, 0.1 mol% of catalyst complex XlVa or XlVb (per alcohol
group);
b) evaluation by GC (% by area); c) product selectivity determined by GC; d)
molar equivalents of NH3 per OH function on the substrate; e) mor/o based on
the OH function
on the substrate
(-)
0
co
co
co
0
0
CO
EK10-1685PC
BASF SE INV0071685/MKr
PF0000071685/MKr =
36
Table 3a: Reaction of MEG (monoethylene glycol)
HO
,OH NH3HO
OH NH, H2tr\ /NH2 + HOH
' ' 4.
a b c
Reaction Selectivity
T Time NH3 Further
Noal Solvent ,, pressure Conversion 1))
[ C] [h] [eqr) [bar] conditions a b
c n
0
I.)
1 Toluene 155 12 6 42 0.2 mol /0 of KOtBu ' 62.9
47.5 25.0 0.5 0
I.)
0
2 Toluene 155 12 6 41 1 mor/0 of KOtBu ' 75.9 39.9
26.8 0.3 H
Ol
CO
3 Toluene 155 12 6 44 . 19.3 48.3
21.8 0.6 I.)
0
4 Toluene 155 12 6 42 17 eq. of water 21.6 55.6
36.4 0.0 H
u.)
i
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of monoethylene glycol, 0.1 mol /0 of catalyst 0
co
complex XlVb (per alcohol group), b) evaluation by GC (% by area), c) product
selectivity determined by GC, d) molar equivalents i
iv
u.)
of NH3 per OH function on the substrate
'
EK10-1685PC
BASF SE INV0071685/MKr
PF0000071685/MKr -
37
Table 3b: Reaction of MEG (monoethylene glycol)
HO
NH3
HO
--õoH ...õNFI, + HzwNH, + HOH
a b c
Solvent catalyst T Time [h] NH3
Reaction Further Conversion Selectivity n
NO.a) (waterfree) [ C] [eq]d) pressure (bar) conditions e)
b) a b c 0
I.)
[y0]
rki [0/] [cm co
i,
CO
H
1 Toluol XlVb 155 12 6 39.8
0.2 mol% KOH (aq, 20%) 59.98 41.02 22.73 12.92 c7,
co
2 Toluol XlVb 180 12 6 46.8
- 94.72 11.00 19.72 44.48 I.)
0
3 Toluol XlVb 180 12 6 47.4
1 mol% KOtBu 100.00 0.66 21.17 49.04 H
u.)
4 Toluol XlVb 180 12 6 66.1
5 bar H2 85.23 15.49 26.30 45.17 1
0
5 p-Xylol XlVb 155 24 6 45.8
- 45.78 43.94 18.28 0.22 co
1
I.)
6 THE XlVb 155 12 6 41.7
2 mol% KOtBu 56.85 47.52 18.66 1.98 u.)
7 THE XlVb 180 12 6 47.2
- 88.49 10.02 22.50 46.63
8 Toluol XlVa 180 24 6 28.0
- 100.00 6.39 11.51 60.53
9 Toluol XlVa 155 12 6 40.8
1 mol% KOtBu 50.47 52.84 19.81 4.31
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of monoethylene glycol, 0.1 mol% of catalyst complex XlVa or XlVb (per alcohol
group);
b) evaluation by GC (% by area); c) product selectivity determined by GC; d)
molar equivalents of NH3 per OH function on the substrate; e) mol% based on
the OH
functions on the substrate
EK10-1685PC
BASF SE INV0071685/MKr
PF0000071685/MKr =
38
Tabelle 4: Reaction of 2,5-furandimethanol
HO OH NI-13 H 2N
\ 0/ OH H2N \ oi NH2
+
\ 0/
a b
0
Selectivity
Solvent Catalyst T
Time NH3 Reaction Conversion c) 0
N
CO
Pressure
I.)
No.a) (waterfree) rci [h] [eq]d) [bar] 12)
a b CO
H
0)
[ok]
ro] [IN CO
N
0
H
1 THF XlVb 140 21 6 35,2 100.00 0.40
96.36 u.)
1
2 THF XlVb 150 6 6 38,8 100.00 7.14
87.75 0
co
3 THF XlVb 150 12 6 40,4 100.00 0.27
84.44 '
I.)
4 THE XlVb 150 18 6 37,1 100.00 0.31
94.15 u.)
5 t-amylalcohol XlVb 140 9 6 31,4 99.59
9.55 84.97
6 t-amylalcohol XlVb 150 5 6 37,1 100.00
2.70 90.10
7 t-amylalcohol XlVb 150 18 6 37,9 100.00
0.00 95.60
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of 2,5-furandimethanol, 0.1 mol% of catalyst complex XlVb (per
alcohol group); b) evaluation by GC ( /0 by area); c) product selectivity
determined by GC; d) molar equivalents of NH3 per OH function on the
substrate
EK10-1685PC
BASF SE INV0071685/NIKr
PF0000071685/MKr -
39
Table 5: Reaction of alkyldiols
H
HO
NH3
(21F1 _____________________________________________________________ w H0NH2 +
H2NNH2 + 9
- n n - n n
a b C
n=1 bis 34
Solvent catalyst T Time NH3 Reaction Conversion
Selectivity n
No.a) Alcohol (waterfree) [ C] [h] [eq]d) pressure b)
a b c
0
. [bar] [Vo]
[0/0] [70] [%]1..)
.
0
1..)
CO
H
1 1,3-propanediol Toluol XlVb 135 12 6 41.1 99.73
8.95 35.79 0)
co
2 1,5-pentanediol Toluol XlVb 180 12 6 44.1 80.51
58.26 19.24 15.13 1..)
3 1,6-hexanediol Toluol XlVb 155 12 6 34.0
100.00 1.14 91.38 0.51 0
H
u..)
4e) 1,9-nonanediol THF XlVb 150 24 6 15.0 97.70
10.60 74.60 o1
1,10-decanediol Toluol XlVb 155 12 6 44.3 95.19
1.36 93.25 co
1
1..)
6 C36-diol THF XlVb 155 12 6 38.2 Amine
number (AZ) 0:197 u..)
AZ (primary amines): 196
AZ (secondary Amines) <1
AZ (tertiary amines): 1
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of alkyldiol, 0.1 mol% of catalyst complex XlVb (per alcohol group); b)
evaluation by GC ( /0 by
area); c) product selectivity determined by GC; d) molar equivalents of NH3
per OH function on the substrate; e) batch size: 50 mmol 1,9-nonanediol in a
100 ml autoclave;
f) definition of amine number (AZ), see Thieme ROmpp Chemielexikon
EK10-1685PC
,
'
BASF SE INV0071685/MKr
PF0000071685/MKr
Table 6: Reaction of 1,4-bis(aminomethyl)cyclohexane
OH NH2 NH2
NH3
+
HO HO H2N
a b
5
_______________________________________________________________________________
_____________
Solvent Catalyst T Time NH3 Reaction- Conversion
Selectivity c) n
No.a) Alcohol (waterfree) [*C] [h] [eq]d) pressure
b) a b 0
I.)
[bar] (%1 rid rol 0
I.)
_
CO
H
01
1 1,4-bis(hydroxymethyl)cyclohexane THE XlVb 155
12 6 45.5 100.00 0.63 94.35 co
I.)
0
H
CA
I
a) 50 ml solvent, 25 mmol 1,4-(bishydroxymethyl)cyclohexane, 0,1 mol% catalyst
complex XlVb (per alcohol group); 0
co
b) evaluation by GC (')/0 by area); c) product selectivity determined by GC;
d) molar equivalents NH3 per OH function on the substrate 1
I\)
u.)
EK10-1685PC
BASF SE INV0071685/MKr
PF0000071685/MKr =
41
Table 7: Reaction of am-alkanol amines
11
N
X OH NH3 X NH2 X
X
H2N
H 2N \ /
N
x,
H
N
a b
H
X = (CH2)1-3, C2H4OCH2
r)
0
iv
Solvent catalyst T Time
NH3 Reaction Conversion Selectivity c) op
I.)
No.a) Alcohol (waterfree) [ C] [h] [eq]d)
pressure b) a b CO
H
, [bar]
rid [ /0] roi c7,
op
I.)
0
1 3-aminopropane-1-ol Toluol XlVb 135 12 6 35.2
45.54 46.98 H
CA
I
2 e) 4-aminobutane-1-ol THF XlVb 180 12 6 24.8
77.21 9.48 85.24 0
0
3 2-(2-aminoethoxy)ethanol Toluol XlVb 155 15 6
41.7 41.01 50.29 24.58 1
I.)
4 monoaminoethanol Toluol XlVb 155 15 6 42.3
72.86 69.39 12.28 u.)
monoaminoethanol Toluol XlVb 180 12 6 71.5
95.92 66.17 19.25
a) conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of alkanol amine, 0.1 mol% of catalyst complex XlVb (per alcohol group);
b) evaluation by GC ( /0 by area); c) product selectivity determined by GC, d)
molar equivalents of NH3 per OH function on the substrate; e) batch size: 50
mmol in
300 ml-autoclave
5
EK10-1685PC
