PROCESS FOR PREPARING ALKANOLAMINES BY HOMOGENEOUSLY CATALYZED ALCOHOL AMINATION

PROCEDE DE PREPARATION D'ALCANOLAMINES PAR AMINATION D'ALCOOLS SOUS CATALYSE HOMOGENE

English Abstract

The invention relates to a method for producing alkanol amines which comprise a primary amino group (-NH2) and a hydroxyl group (-OH), by alcohol amination of diols comprising two hydroxyl groups (-OH), using ammonia, and elimination of water. The reaction is homogeneously catalyzed in the presence of at least one complex catalyst which contains at least one element selected from groups 8, 9 and 10 of the periodic table and at least one donor ligand.

French Abstract

L'invention concerne un procédé de préparation d'alcanolamines qui possèdent un groupement amino primaire (-NH2) et un groupement hydroxyle (-OH), par amination de diols, présentant deux groupements hydroxyle (-OH), avec de l'ammoniac, par déshydratation, la réaction étant conduite sous catalyse homogène en présence d'au moins un complexe catalyseur qui contient au moins un élément choisi dans les groupes 8, 9 et 10 du tableau périodique, ainsi qu'au moins un ligand donneur.

Claims

49
"Claims as enclosed to IPRP"
1. A process for preparing alkanolamines which have a primary amino group (-
NH2)
and a hydroxyl group (-OH) by alcohol amination of diols having two hydroxyl
groups (-OH) 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
of the Periodic Table and also at least one phosphorus donor ligand.
2. The process according to claim 1, wherein the complex catalyst is a
catalyst of
the formula (I):
<IMG>
where
L1 and L2 are each, independently of one another, PR a R b , NR a R b ,
sulfide,
SH, S(=O)R, C5-C10-heteroaryl comprising at least one heteroatom
selected from among N, O and S, AsR a R b , SbR a R b and N-
heterocyclic carbenes of the formula (II) or (III):
<IMG>
L3 is a monodentate two-electron donor selected from the group
consisting of CO, PR a R b R c, NO+, ASR a R b R c, SbR a R b R c, SR a R b ,
RCN, RNC, N2, PF3, CS, pyridine, thiophene, tetrahydrothiophene
and N-heterocyclic carbenes of the formula (II) or (III);

50
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, R a, R b, R c, R3, R4 and R5 are each, independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-
cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom
selected from among N, O and S, C5-C10-aryl or C5-C10-heteroaryl
comprising at least one heteroatom selected from among N, O and
S,
where the substituents are selected from the group consisting of:
F, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
Y is a monoanionic ligand selected from the group consisting of H, F,
CI, 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;
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, CI, Br, I, OH, NH2, NO2, -NC(O)R,
C(O)NR2, -OC(O)R, -C(O)OR, 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-heterocyclyl
comprising at least one heteroatom selected from among N, O and
S, C5-C10-aryl and C5-C10-heteroaryl comprising at least one
heteroatom selected from among N, O and S,
where the substitutents are selected from the group consisting of:
F, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
and
M is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium,
iridium or platinum.

51
3. The process according to claim 1 or 2, wherein R1 and R2 are both
hydrogen and
the complex catalyst is a catalyst of the formula (IV):
<IMG>
and X1, L1, L2, L3 and Y are as defined in claim 2.
4. The process according to claim 1 or 2, wherein R1 and R2 together with
the
carbon atoms to which they are bound form a phenyl ring which together with
the
quinolinyl units of the formula (I) forms an acridinyl unit and the complex
catalyst
is a catalyst of the formula (V):
<IMG>
and X1, L1, L2, L3 and Y are as defined in claim 2.
5. The process according to claim 1 or 2, wherein the complex catalyst is
selected
from the group of catalysts of the formulae (VI), (VII), (VIII), (IX), (X),
(XI), (XII)
and (XIII):

52
<IMG>
and X1, R a, R b and Y are as defined in claim 2.

53
6. The process according to claim 1 or 2, wherein the complex catalyst is a
catalyst
of the formula (XlVa):
<IMG>
7. The process according to claim 1 or 2, wherein the complex catalyst is a
catalyst
of the formula (XIVb):
<IMG>
8. The process according to claim 1, wherein the complex catalyst is a
catalyst of
the formula (XV):
<IMG>
where

54
L1 and L2 are each, independently of one another, PR a R b, NR a R b,
sulfide,
SH, S(=O)R, C5-C10-heteroaryl comprising at least one heteroatom
selected from among N, O and S, AsR a R b, SbR a R b or
N-heterocyclic carbenes of the formula (II) or (III):
<IMG>
L3 is a monodentate two-electron donor selected from the group
consisting of CO, PR a R b R c, NO+, ASR a R b R c, SbR a R b R c, SR a R b,
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, R a, R b, R c, R3, R4 and R5 are each, independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C3-C10-
cycloalkyl, C3-C10-heterocyclyl comprising at least one heteroatom
selected from among N, O and S, C5-C10-aryl or C5-C10-heteroaryl
comprising at least one heteroatom selected from among N, O and
S,
where the substituents are selected from the group consisting of:
F, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
Y is a monoanionic ligand selected from the group consisting of H, F,
CI, Br, I, OCOR, OCOCF3, OSO2R, OSO2CF3, CN, 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,

55
where the radicals X1 are selected independently from the group
consisting of hydrogen, F, CI, Br, I, OH, NH2, NO2, -NC(O)R,
C(O)NR2, -OC(O)R, -C(O)OR, 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-
heterocyclyl
comprising at least one heteroatom selected from among N, O and
S, C5-C10-aryl and C5-C10-heteroaryl comprising at least one
heteroatom selected from among N, O and S,
where the substituents are selected from the group consisting of:
F, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
and
M is iron,
cobalt, nickel, ruthenium, rhodium, palladium, osmium,
iridium or platinum.
9. The process
according to either claim 1 or 8, wherein the complex catalyst is a
catalyst of the formula (XVI):
<IMG>
10. The process according to any of claims 1 to 5, wherein Y in the complex
catalyst
is selected from among F, CI and Br.
11. The process according to any of claims 2 to 10, wherein L3 in the complex
catalyst is CO.
12. The process
according to claim 1, wherein the alcohol amination is carried out in
the presence of at least one complex catalyst comprising at least one element

56
selected from groups 8, 9 and 10 of the Periodic Table and also at least one
phosphorus donor ligand of the general formula (XXI),
<IMG>
where
n is 0 or 1,
R21, R22, R23, R24, R25, R26 are each,
independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-
alkyldiphenylphosphine (-C1-C4-alkyl-P(phenyl)2), C3-C10-cycloalkyl, C3-C10-
heterocyclyl comprising at least one heteroatom selected from among N, O
and S, C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom
selected from among N, O and S,
where the substituents are selected from the group consisting of: F, CI, Br,
OH, CN, NH2 and C1-C10-alkyl;
A is
i) a bridging
group selected from the group consisting of unsubstituted
or at least monosubstituted N, O, P, C1-C6-alkane, C3-C10-cycloalkane,
C3-C10-heterocycloalkane comprising at least one heteroatom selected from
among N, O and S, C5-C14-aromatic and C5-C6-heteroaromatic comprising
at least one heteroatom selected from among N, O and S,
where the substituents are selected from the group consisting of:
C1-C4-alkyl, phenyl, F, CI, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl;

57
or
ii) a bridging group of the formula (XXII) or (XXIII):
<IMG>
m, q are each, independently of one another, 0, 1, 2, 3 or 4,
R28, R29 are selected independently from the group consisting of C1-C10-
alkyl, F, CI, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl;
X11, X12 are each, independently of one another, NH, O or S,
X13 is a bond, NH, NR33, O, S or CR31R32;
R30 is unsubstituted or at least monosubstituted C1-C10-alkyl,
C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising at least one
heteroatom selected from among N, O and S, C5-C14-aryl or
C5-C10-heteroaryl comprising at least one heteroatom selected
from among N, O and S,
where the substituents are selected from the group consisting
of: F, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
R31, R32 are each, independently of one another, unsubstituted or at
least monosubstituted C1-C10-alkyl, C1-C10-alkoxy, C3-C10-
cycloalkyl, C3-C10-cycloalkoxy, C3-C10-heterocyclyl comprising
at least one heteroatom selected from among N, O and S, C5-
C14-aryl, C5-C14-aryloxy or C5-C10-heteroaryl comprising at least
one heteroatom selected from among N, O and S,

58
where the substituents are selected from the group consisting
of: F, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
Y1, Y2, Y3 are each, independently of one another, a bond, unsubstituted or at
least monosubstituted methylene, ethylene, trimethylene,
tetramethylene, pentamethylene or hexamethylene,
where the substituents are selected from the group consisting of: F,
CI, Br, OH, OR27, CN, NH2, NHR27, N(R27)2 and C1-C10-alkyl,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl.
13. The process according to any of claims 1 to 11, wherein the diol has two
functional groups of the formula (-CH2-OH).
14. The process according to any of claims 1 to 13, wherein the
preparation of the
alcoholamines is carried out at a temperature of from 110 to 160°C and
a
pressure of from 1 to 15 MPa.
15. 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 phosphorus
donor
ligand for the homogeneously catalyzed preparation of alkanolamines which have
a primary amino group (-NH2) and a hydroxyl group (-OH) by alcohol amination
of
diols having two hydroxyl groups (-OH) by means of ammonia.

Description

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1
Process for preparing alkanolamines by homogeneously catalyzed alcohol
amination
The present invention relates to a process for preparing alkanolamines by
homogeneously catalyzed alcohol amination of diols 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
phosphorus donor ligand.
Alkanolamines are compounds which have a primary amino group (-NH2) and a
hydroxyl group (-OH).
Alkanolamines 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, drugs, inhibitors, corrosion inhibitors, polyurethanes,
as hardeners
for epoxy resins, as surface-active substances and for gas scrubbing.
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.
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
by means of primary amines using homogeneously dissolved ruthenium- and
iridium-
based transition metal catalysts. However, the cyclic compounds and not the
desired
alkanolamines are formed here. The economically attractive amination of diols
by
means of ammonia to form alkanolamines has not been described for these
systems.
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EP 0 234 401 Al describes the reaction of ethylene glycol with ammonia in the
presence of a ruthenium carbonyl compound. In the process described in
EP 0 234 401 Al, the monoamination product (monoethanolamine) is formed among
other things. In addition, large amounts of the secondary and tertiary amines
(diethanolamine and triethanolamine) and cyclic products (N-
(hydroxyethyl)piperazine
and N,N'-bis(hydroxyethyl)piperazine) are formed as by-products.
All the above-described processes for the reaction of diols have the
disadvantage that
undesired secondary, tertiary and cyclic amines are formed to a major extent
in
addition to the desired alkanolamines.
It is an object of the present invention to provide a process for preparing
alkanolamines
by alcohol amination of diols by means of ammonia with elimination of water.
The object is achieved by a process for preparing alkanolamines which have a
primary
amino group (-NH2) and a hydroxyl group (-OH) by alcohol amination of diols
having
two hydroxyl groups (-OH) 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 phosphorus donor ligand.
It has surprisingly been found that alkanolamines can be obtained by the
homogeneously catalyzed amination of diols 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 phosphorus donor ligand. The process of the invention
has the
advantage that it gives alkanolamines 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
avoided.
Starting materials
In the process of the invention, starting materials having two hydroxyl groups
are used.
Suitable starting materials are virtually all diols which meet the
abovementioned
prerequisites. The diols 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, l).
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Suitable starting materials which can be used in the process of the invention
are, for
example, diols which have a functional group of the formula (-CH2-0H) and a
further
hydroxyl group (-OH).
In addition, diols having two functional groups of the formula (-CH2-0H) are
suitable.
As starting materials, it is possible to use all known diols. Preference is
given to diols
which have at least one functional group of the formula (-CH2-0H). Greater
preference
is given to diols which have two functional groups 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,
diethanolamine, 1,4-bis(2-hydroxyethyl)piperazine,
diisopropanolamine,
N-butyldiethanolamine, N-methyldiethanolamine, 1,10-decanediol, 1,12-
dodecanediol,
2,5-(dimethanol)-furan and C36-diol (mixture of isomers of alcohols having the
empirical formula C361-17402).
Another name for 2,5-(dimethanol)-furan is 2,5-bis(hydroxymethyp-furan.
Further suitable starting materials are diols of the general formulae (X(XI),
(XXXII) and
(XXXII!):
HOHO OH
OH
n1OH _n3
n2
(XXXI) (XXXII) (xxxiii)
where
n1 is 2-30;
n2 is 1-30 and
n3 is 1-30.
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Preference is given to diols having two functional groups of the formula (-CH2-
0H).
Particularly preferred diols 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-13-
propanediol, 2,2-dimethy1-1,3-propanediol (neopentyl glycol), diethylene
glycol,
triethylene glycol, polyethylene glycols, polypropylene glycols such as
1,2-polypropylene glycol and 1,3-polypropylene glycol, polytetrahydrofuran,
2,5-
(dimethanol)-furan and diethanolamine.
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):
\R1
N%R2
1/H
L3
(I)
where
L1 andL2 are each, independently of one another, phosphine (PRaRb), 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):
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R3 R4 R3 R4
DC.
N7N
= =
(ii) (iii)
L3 is a monodentate two-electron donor selected from the group
consisting of carbon monoxide (CO), PRaRbRc, NO+, AsRaRbRc,
5 SbRaRbRc, SRaRb, nitrite (RCN), isonitrile (RNC), nitrogen
(N2),
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 C1-010-alkyl, Craw-
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, ON, NH2 and C1-C10-alkyl;
is a monoan ionic ligand selected from the group consisting of H, F,
Cl, Br, I, OCOR, OCOCF3, OSO2R, OSO2CF3, ON, OH, OR and
N(R)2 or an uncharged molecule 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
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can be obtained from the catalyst of the formula I by reaction with
NaBH4 and unsubstituted or at least monosubstituted C1-C10-
alkoxy, 01-010-alkyl,
C3-C10-cycloalkyl, C3-C10-heterocycly1
comprising at least one heteroatom selected from among N, 0 and
S, 05-010-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 01-010-alkyl;
and
M
is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium,
iridium or platinum.
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 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, PRaRbRc, 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, 1=e, R3, R4 and R5 are each, independently of one another,
unsubstituted
01-010-alkyl, C3-010-cycloalkyl, C3-C10-heterocycly1 comprising at least
one heteroatom selected from among N, 0 and S, C5-C10-aryl or 05-010-
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
7
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
hydrogen, F, CI, 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
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
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
1 /I
LI------%-fil-L2
L3 I
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
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
,
8
together with the quinolinyl unit of the formula (I) forms an acridinyl unit
and the
complex catalyst is a catalyst of the formula (V):
\
N
1/H
C--------/T---------L2
L3 Y
(v)
and X1, Ll, . 2,
L 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:
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-
23
-
9
xl x'
\ ',..,....
0 / 0
N
N
" 1 /H 1 /H
Ra
Ra__,____-------/-M---------p/
Ra p________-----7y------õ_p/Ra
OC I \OC I \
Rb/ Y
Rb Rb/ Y
Rb
(VI) (VII)
)(
40
\ -,..,, xl
1 /H
0 \=k.''-,,..,,
/ 0
N
N..'
a
Ra R
_¨/-y----,p / I /H
N_____.-------7T---------._
p ., R3
Rb Y
Rb
Rb Y
Rb
(VIII) (IX)
xl x'
\
0 / 0
N
1 /H
Ra 1 /H
Ra----?"-------/ Ra ----7------N
/ Ra
/
Rb OC I \ / OC I
\
Y
Rb Rb Y
Rb
(X) (XI)
x' x1
0
\
N ON \ '''
1 /H I /H
RaN_,_--/-y---------__,_N /Ra Ra-.......NN /
/
Rb OC I \ / OC I
\
Y
Rb Rb Y Rb
(Xii) (XIII)
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
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
5 Ra and Rb are each, independently of one another,
unsubstituted or at least
monosubstituted 01-C10-alkyl, C3-010-cycloalkyl, 03-010-heterocycly1
comprising
at least one heteroatom selected from among N, 0 and S, 05-C10-aryl or 05-010-
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-C10-alkyl;
= is a monoanionic ligand selected from the group consisting of H, F, CI,
Br,
OCOR, 0000F3, OSO2R, OSO2CF3, ON, OH, OR, N(R)2;
= is unsubstituted or at least monosubstituted 01-010-alkyl, 03-C10-
cycloalkyl,
03-010-heterocycly1 comprising at least one heteroatom selected from among N,
0 and S, 05-010-aryl, C5-010-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,
ON, NH2 and 01-010-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, -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 C1-010-alkoxy, 01-C10-
alkyl,
03-010-cycloalkyl, C3-010-heterocycly1 cornprising at least one heteroatom
selected from among N, 0 and S, 05-010-aryl and C5-C10-heteroaryl comprising
at least one heteroatom selected from among N, 0 and S;
and
= is ruthenium or iridium.
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
11
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 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,
cyclohexyl, cyclopentyl, phenyl or mesityl;
is a monoanionic ligand selected from the group consisting of H, F, Cl, Br,
OCOCH3, 0000F3, OSO2CF3, ON and OH;
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, Cl, Br, 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 01-C10-alkoxy, Ci-C10-alkyl, 03-C10-cycloalkyl, C3-C10-
heterocyclyl
comprising at least one heteroatom selected from among N, 0 and S, 05-010-
aryl and C5-010-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;
= is a monoanionic ligand selected from the group consisting of H, F, Cl,
Br, I,
000CH3, OCOCF3, OSO2CF3, ON and OH;
X1 is hydrogen;
and
= is ruthenium or iridium.
In a particularly preferred embodiment, L3 is carbon monoxide (CO).
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
12
In a particularly preferred embodiment, the process of the invention is
carried out in the
presence of a complex catalyst of the formula (XlVa):
110
1/H
OC/
CI
(xlVa)
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):
1101
H
POC/ I
ci
(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
=
X1Ri
\
H H
R 2
L1Ru
=
L2
L3 I
(XV)
EK11-1973PC

, PF0000071973/MKr CA 02828167 2013-08-23
13
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:
11,r, H
\ ,,,,.Ri \ l=
NaBH4
10 H 1 ....1-1
b-
N----._ =
B
LI -------/RIU ------------L2 LI -----/RIU--j----L2
L3 L3
5 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 (XVI):
H, H
'---,
40
1
iik , i
N¨...B.
1 Fr
X OC I
H
10 (XVI)
The borane derivative of the formula XVI can be obtained according to the
following
reaction equation:
H H
A
all N / 0 Na11114 (1 Equnalent)
1110 lilliel
I.... H 2h Room temperature N''..-
X /I
a
.------13
OC
/K
In a further embodiment, the process of the invention is carried out using at
least one
complex catalyst comprising at least one element selected from groups 8, 9 and
10 of
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PF0000071973/MKr CA 02828167 2013-08-23
14
the Periodic Table (IUPAC nomenclature) and also at least one phosphorus donor
ligand of the general formula (XXI),
R21
yl_ A¨ y2 p/ R23
R22I I R24
Y3
/
R25 R26
_________________________________________ in
(XX1)
where
n is 0 or 1;
R21, R22, R23, R24, R26, R26 are each,
independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-
alkyldiphenylphosphine (-C1-C4-alkyl-P(pheny1)2), C3-C10-cycloalkyl, C3-C10-
heterocyclyl comprising at least one heteroatom selected from among N, 0
and S, C5-C14-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, CI, Br,
OH, ON, NH2 and C1-010-alkyl;
A is
i) a bridging group
selected from the group consisting of unsubstituted
or at least monosubstituted N, 0, P, C1-C6-alkane, C3-C10-cycloalkane,
C3-C10-heterocycloalkane comprising at least one heteroatom selected from
among N, 0 and S, C5-C14-aromatic and C5-C6-heteroaromatic comprising
at least one heteroatom selected from among N, 0 and S,
where the substituents are selected from the group consisting of:
C1-C4-alkyl, phenyl, F, Cl, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among Cram-alkyl and C5-010-aryl;
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
or
ii) a bridging group of the formula (XXII) or (XXIII):
(R28)m
(R29) (R28)m
X13 (R29)q
,,,..\-- '''..=`,/,..
1 1 1 1
)(11 x12
5 (XXII) (XXIII)
m, q are each, independently of one another, 0, 1, 2, 3 or 4;
R28, R29 are selected independently from the group consisting of
C1-C10-
10 alkyl, F, CI, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among CI-Gm-alkyl and C5-C10-aryl;
X11, x12 are each, independently of one another, NH, 0 or S;
X13 is a bond, NH, NR30, 0, S or CR31R32;
R3 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-C14-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, CI, Br, OH, CN, NH2 and C1-C10-alkyl;
R31, R32 are each, independently of one another, unsubstituted or
at
least monosubstituted C1-C10-alkyl, C1-C10-alkoxy, C3-C10-
cycloalkyl, C3-C10-cycloalkoxy, C3-C10-heterocycly1 comprising at
least one heteroatom selected from among N, 0 and S, C5-C14-
aryl, C5-C14-aryloxy 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, CI, Br, OH, CN, NH2 and Cl-Curalkyl;
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
,
=
16
Y1, y2, Y3
are each, independently of one another, a bond, unsubstituted or at
least monosubstituted methylene, ethylene, trimethylene,
tetramethylene, pentamethylene or hexamethylene,
where the substituents are selected from the group consisting of: F,
Cl, Br, OH, OR27, CN, NH2, NHR27, N(R27)2 and C1-C10-alkyl,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl.
According to the invention, A is a bridging group. When A is selected from the
group
consisting of unsubstituted or at least monosubstituted C1-C6-alkane, C3-C10-
cycloalkane, C3-C10-heterocycloalkane, C5-C14-aromatic and C5-C6-
heteroaromatic and
bridging groups of the formula (II) or (III), two hydrogen atoms of the
bridging group are
replaced by bonds to the adjacent substituents Y1 and Y2 when n = 0. When n =
1,
three hydrogen atoms of the bridging group are replaced by three bonds to the
adjacent substituents Y1, Y2 and Y3.
When A is P (phosphorus), the phosphorus forms two bonds to the adjacent
substituents Y1 and Y2 and one bond to a substituent selected from the group
consisting of C1-C4-alkyl and phenyl when n = 0. When n = 1, the phosphorus
forms
three bonds to the adjacent substituents Y1, Y2 and Y3.
When A is N (nitrogen), the nitrogen forms two bonds to the adjacent
substituents Y1
and Y2 and one bond to a substituent selected from the group consisting of C1-
C4-alkyl
and phenyl when n = 0. When n = 1, the nitrogen forms three bonds to the
adjacent
substituents Y1, Y2 and Y3.
When A is 0 (oxygen), n = 0. The oxygen forms two bonds to the adjacent
substituents
Y1 and Y2.
Preference is given to complex catalysts which comprise at least one element
selected
from among ruthenium and iridium.
In a preferred embodiment, the process of the invention is carried out 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 phosphorus donor
ligand of the
general formula (XXI), where
n is 0 or 1;
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
17
R21, R22, R23, R24, R25, R26 are each,
independently of one another,
unsubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-
heterocycly1
comprising at least one heteroatom selected from among N, 0 and S,
C5-C14-aryl or C5-C10-heteroaryl comprising at least one heteroatom
selected from among N, 0 and S;
A is
i) a bridging group
selected from the group consisting of unsubstituted
C1-C6-alkane, C3-C10-cycloalkane, C3-C10-heterocycloalkane comprising at
least one heteroatom selected from among N, 0 and S, C5-C14-aromatic
and C5-C6-heteroaromatic comprising at least one heteroatom selected
from among N, 0 and S;
or
ii) a bridging group of the formula (XXII) or (XXIII):
(R28)m
x
,p26,q (R286 13 (R23)q
'
x12
(XXII) (XXIII)
m, q are each, independently of one another, 0, 1, 2, 3 or 4;
R28, R26 are selected independently from the group consisting of
C1-C10-
alkyl, F, Cl, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among Cr-Clip-alkyl and C5-C10-aryl;
X11,
x12 are each, independently of one another, NH, 0 or S;
X13 is a bond, NH, NR30, 0, S or CR31 R32;
R3 is unsubstituted C1-C10-alkyl, C3-C10-cycloalkyl, C3-C10-
heterocyclyl comprising at least one heteroatom selected from
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
18
among N, 0 and S, 05-014-aryl or 05-010-heteroaryl comprising
at least one heteroatom selected from among N, 0 and S;
R31, R32 are
each, independently of one another, unsubstituted 01-C10-
alkyl, C1-010-alkoxy, C3-010-cycloalkyl, 03-010-cycloalkoxy,
03-010-heterocycly1 comprising at least one heteroatom selected
from among N, 0 and S, 05-C14-aryl, 05-014-aryloxy or C5-C10-
heteroaryl comprising at least one heteroatom selected from
among N, 0 and S;
Y1, Y2, Y3 are each, independently of one another, a bond, unsubstituted
methylene, ethylene, trimethylene, tetramethylene, pentamethylene
or hexamethylene.
In a further preferred embodiment, the process of the invention is carried out
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 phosphorus
donor
ligand of the general formula (XXV),
R21
p-y1-A-y2-.-p/R23
R22 R24
(XXV)
where
R21, R22, R23, r<-24
are each, independently of one another, unsubstituted or at
least monosubstituted 01-010-alkyl, 01-04-alkyldiphenylphosphine (-01-C4-
alkyl-P(pheny1)2), C3-010-cycloalkyl, 03-C10-heterocycly1 comprising at least
one heteroatom selected from among N, 0 and S, 05-C14-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, ON, NH2 and C1-C10-alkyl;
A is
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PF0000071973/MKr CA 02828167 2013-08-23
19
i) a bridging group selected from the group consisting of unsubstituted
or at least monosubstituted N, 0, P, C1-C6-alkane, C3-C10-cycloalkane,
C3-C10-heterocycloalkane comprising at least one heteroatom selected from
among N, 0 and S, C6-C14-aromatic and C6-C6-heteroaromatic comprising
at least one heteroatom selected from among N, 0 and S,
where the substituents are selected from the group consisting of:
C1-C4-alkyl, phenyl, F, CI, Br, OH, OR27, NH2, NHR27 or N(R27)2.
where R27 is selected from among C1-C10-alkyl and C6-C10-aryl;
or
ii) a bridging group of the formula (XXII) or (XXIII):
(R28)m
(R29)q (R28), X13 (R29)q
x11 x12
(XXII) (XXIII)
m, q are each, independently of one another, 0, 1, 2, 3 or 4;
R28, R29 are selected independently from the group consisting of C1-C10-
alkyl, F, CI, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among C1-C10-alkyl and C6-C10-aryl;
x11, )(12 are each, independently of one another, NH, 0 or S,
X13 is a bond, NH, NR30, 0, S or CR311332;
R3 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, C6-C14-aryl or
C6-C10-heteroaryl comprising at least one heteroatom selected
from among N, 0 and S,
EK11-1973PC

. PF0000071973/MKr CA 02828167 2013-08-23
where the substituents are selected from the group consisting
of: F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
R31, R32
are each, independently of one another, unsubstituted or at
5 least
monosubstituted C1-C10-alkyl, CrCuralkoxy, 03-010-
cycloalkyl, C3-C10-cycloalkoxy, 03-C10-heterocycly1 comprising at
least one heteroatom selected from among N, 0 and S, 05-014-
aryl, C5-C14-aryloxy 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, ON, NH2 and C1-C10-alkyl;
y1, y2
are each, independently of one another, a bond, unsubstituted or at
least monosubstituted methylene, ethylene, trimethylene,
tetramethylene, pentamethylene or hexamethylene,
where the substituents are selected from the group consisting of: F,
Cl, Br, OH, OR27, ON, NH2, NHR27, N(R27)2 and CI-Cm-alkyl,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl.
In a further preferred embodiment, the process of the invention is carried out
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 phosphorus
donor
ligand of the general formula (XXVI),
R21
\p-y1_A_y2-p/R23
/ I \
R22 R24
V3
1
P
/ \
R25 R26
(XXVI)
where
R21, R22, R23, R24, R25, R26 are each,
independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-
alkyldiphenylphosphine, C3-C10-cycloalkyl, C3-C10-heterocyclyl comprising
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
21
at least one heteroatom selected from among N, 0 and S, C5-C14-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;
A is a bridging group selected from the group consisting of
unsubstituted or at
least monosubstituted N, P, C1-C6-alkane, C3-C10-cycloalkane,
heterocycloalkane comprising at least one heteroatom selected from
among N, 0 and S, C5-C14-aromatic and C5-C6-heteroaromatic comprising
at least one heteroatom selected from among N, 0 and S,
where the substituents are selected from the group consisting of:
C1-C4-alkyl, phenyl, F, Cl, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl;
Y1, y2, y3 are
each, independently of one another, a bond, unsubstituted or at
least monosubstituted methylene, ethylene, trimethylene, tetramethylene,
pentamethylene or hexamethylene,
where the substituents are selected from the group consisting of: F, Cl, Br,
OH, OR27, CN, NH2, NHR27, N(R27)2 and C1-C10-alkyl,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl.
In a further preferred embodiment, the process of the invention is carried out
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 phosphorus
donor
ligand of the general formula (XXV), where
R21, R22, R23, .-.24
are each, independently of one another, methyl, ethyl,
isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, or mesityl;
A is
i) a
bridging group selected from the group consisting of methane,
ethane, propane, butane, cyclohexane, benzene, naphthalene and
anthracene;
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
22
or
ii) a bridging group of the formula (XXVII) or (XXVIII):
x13
111101 xi, Oil 111111 x12 10
(XXVii) (XXViii)
X11, x12 are each, independently of one another, NH, 0 or S;
X13 is a bond, NH, 0, S or CR31R32;
R31, R32 are
each, independently of one another, unsubstituted C1-C10-
alkyl;
Y1, y2 are each,
independently of one another, a bond, methylene or
ethylene.
In a particularly preferred embodiment, the process of the invention is
carried out 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 phosphorus
donor
ligand of the general formula (XXIX) or (XXX),
(R28)m
(R29)q (R286 (R29)q
X13
x11 x12
R21 R22 R23 Rza
R21 R22 R23 Rza
(XXIX) (XXX)
where the abovementioned definitions and preferences apply to m, q, R21, R22,
R23, R24,
R28, R29, x19, x12 and x13.
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
23
In a further particularly preferred embodiment, the process of the invention
is carried
out in the presence of at least one complex catalyst comprising at least one
element
selected from the group consisting of ruthenium and iridium and also at least
one
phosphorus donor ligand selected from the group consisting of
1 ,2-bis(diphenylphosphino)ethane (dppe), 1 ,3-bis(diphenylphosphino)propane
(dppp),
1 ,4-bis(diphenylphosphino)butane (dppb), 2,3-
bis(dicyclohexylphosphino)ethane
(dcpe), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene
(xantphos), 1,1,1-
tris(diethylphosphinomethyl)ethane (rhodaphos), bis(2-
diphenylphosphinoethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)-
1 0 ethane (triphos).
In a further particularly preferred embodiment, the process of the invention
is carried
out in the presence of a complex catalyst comprising ruthenium and also at
least one
phosphorus donor ligand selected from the group consisting of 4,5-
bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-
diphenylphosphino-
ethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos).
In a further particularly preferred embodiment, the process of the invention
is carried
out in the presence of a complex catalyst comprising iridium and also at least
one
phosphorus donor ligand selected from the group consisting of
4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos), bis(2-
diphenylphosphino-
ethyl)phenylphosphine and 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos).
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-a4-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 C1-C10-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, C5-C10-alkylaryloxy, C5-C10-heteroaryloxy comprising at least one
heteroatom
selected from among N, 0, S, oxo, C3-C10-cycloalkyl, phenyl, C5-C10-heteroaryl
comprising at least one heteroatom selected from among N, 0, S, C5-C10-
heterocycly1
comprising at least one heteroatom selected from among N, 0, S, naphthyl,
amino,
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
24
01-C10-alkylamino, 05-C10-arylamino, C5-010-heteroarylamino comprising at
least one
heteroatom selected from among N, 0, S, C1-C10-dialkylamino, 010-012-
diarylamino,
010-C20-alkylarylamino, 01-010-acyl, C1-010-acyloxy, NO2, C1-010-carboxy,
carbamoyl,
carboxamide, cyano, sulfonyl, sulfonylamino, sulfinyl, sulfinylamino, thiol,
01-010-
alkylthiol, 05-010-arylthiol and C1-010-alkylsulfonyl.
The above definition of 01-010-alkyl applies analogously to 01-C30-alkyl and
to C1-C6-
alkane.
For the present purposes, the term 03-C10-cycloalkyl refers to saturated,
unsaturated
monocyclic and polycyclic groups. Examples of 03-010-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 01-010-alkyl group.
The abovementioned definition of 03-010-cycloalkyl applies analogously to 03-
C10-
cycloalkane.
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)012]2,
[Ru(benzene)C12], [Ru(00)2C12], [Ru(00)3012]2 [Ru(COD)(allyI)], [RuCI3*H20],
[Ru(acetylacetonate)3], [Ru(DMS0)4C12], [Ru(PPh3)3(C0)(H)CI],
[Ru(PPh3)3(00)Cl2],
[Ru(Plph3)3(C0)(H)2], [Ru(PPh3)3C12],
[Ru(cyclopentadienyl)(PPh3)2C1],
[Ru(cyclopentadienyl)(C0)201],
[Ru(cyclopentadienyl)(C0)2F1],
[Ru(cyclopentadienyl)(00)212. [Ru(pentamethylcyclopentadienyl)(C0)201],
[Ru(penta-
methylcylcopentadienyl)(00)21-1],
[Ru(pentamethylcyclopentadienyl)(CO)2]2,
[Ru(indenyl)(C0)2C1], [Ru(indenyl)(00)21-11,
[Ru(indenyl)(00)2b, ruthenocene,
[Ru(binap)012], [Ru(bipyridine)2012*2H20], [Ru(COD)C12]2, [Ru(pentamethylcyclo-
pentadienyl)(COD)01], [Ru3(C0)12],
[Ru(tetraphenylhydroxycyclopentadienyl)(C0)21-1],
[Ru(PMe3)4(H)2], [Ru(PEt3)4(H)2], [Ru(PnlJr3)4(H)2],
[Ru(PnBu3)4(H)2],
[Ru(PnOcty13)4(H)21, [IrCI3*H20], KIrC14, K31r016, [Ir(COD)C1]2,
[Ir(cyclooctene)2C1]2,
[Ir(ethene)2C1]2, [Ir(cyclopentadieny1)012]2,
[Ir(pentamethylcyclopentadienyl)C1212,
[Ir(cylopentadienyl)(CO)2], [Ir(Pentamethylcyclopentadienyl)(C0)21,
[Ir(PPh3)2(C0)(H)l,
[Ir(PPh3)2(C0)(C1)], [Ir(PPh3)3(CI)].
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
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
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.
5
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.
10 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
15 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 0.2 to
15 MPa absolute, particularly preferably at a total pressure in the range from
1 to
15 MPa absolute.
The average reaction time is generally from 15 minutes to 100 hours.
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
1-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 ammonia can be introduced in gaseous form, liquid form or as a
solution
in the solvent or starting material.
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.
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26
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 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-amylalcohol.
To carry out the reaction in the liquid phase, ammonia, the diol optionally
together with
one or more solvents, together with the complex catalyst are introduced into a
reactor.
The introduction of ammonia, diol, 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
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, a hydroxyl group, preferably a primary hydroxyl
group
(-CH2-0H), of the starting material is reacted with ammonia to form a primary
amino
group (-NH2), with in each case one mole of water of reaction being formed per
mole of
reacted hydroxyl group.
The reaction of 1,2-ethylene glycol leads, for example, to the corresponding
2-aminoethanol.
The reaction output formed in the reaction generally comprises the
corresponding
alkanolamines, 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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27
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 and dioxane. As a result of suitable
choice of the
phosphine ligands, the catalyst preferentially dissolves in the solvent phase.
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 solvent can also be miscible with the starting materials and the product
under the
reaction conditions and only form a second liquid phase comprising the major
part of
the catalyst after cooling. As solvents which display this property, mention
may be
EK11-1973PC

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28
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, which can be used in amounts
of from
0.01 to 100 molar equivalents based on the metal catalyst 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
alkanolamines
which have a primary amino group (-NH2) and a hydroxyl group (-OH) by alcohol
amination of diols having two hydroxyl groups (-OH) by means of ammonia.
EK11-1973PC

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29
In a preferred embodiment, the present invention provides for the use of a
homogeneously dissolved complex catalyst of the general formula (I):
NR2
I /H
L3 I
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 and N-
heterocyclic carbenes of the formula (II) or (III):
R3 R4
¨N R3 R4
N7N¨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, Rb7
1-t R3, R4, and R5 are each, independently of one another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C3-Cio-
cycloalkyl, 03-010-heterocycly1 comprising at least one heteroatom
selected from among N, 0 and S, C5-C10-aryl or 05-010-heteroaryl
comprising at least one heteroatom selected from among N, 0 and
S,
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PF0000071973/MKr CA 02828167 2013-08-23
,
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,
5 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;
X1 represents one, two, three, four, five, six
or seven substituents on
10 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,
15 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
20 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 alkanolamines which have a
primary
amino group (-NH2) and a hydroxyl group (-OH) by alcohol amination of diols
having
two hydroxy groups (-OH) 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).
In a further preferred embodiment, the present invention relates to the use of
a
homogeneously dissolved complex catalyst of the general formula (XV):
EK11-1973PC

. PF0000071973/MKr CA 02828167 2013-08-23
,
31
H., H
01\ R
HAL,,,,s:.........õ.õFi R2
N1- =
1
--- !
L1 L2
L3 I
H
(xv)
where
L1 and L2 are each, independently of one another,
PRaRb, NRaRb, sulfide,
5 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):
R3 R4 R3
( )¨(R4
¨N,N.....õN¨IRS
¨NN7N¨R5
= =
(ii) WO .
,
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;
20 R, Ra, Rb, --c,
K 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
25 S,
where the substituents are selected from the group consisting of:
F, Cl, Br, OH, CN, NH2 and C1-C10-alkyl;
EK11-1973PC

PF0000071973/MKr CA 02828167 2013-08-23
32
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 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, 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, ON, NH2 and C1-C10-alkyl;
and
is iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium,
iridium or platinum,
for the homogeneously catalyzed preparation of alkanolamines which have a
primary
amino group (-NH2) and a hydroxyl group (-OH) by alcohol amination of diols
having
two hydroxyl groups (-OH) 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 (XV).
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 phosphorus donor ligand of the general formula (XXI),
EK11-1973PC

. PF0000071973/MKr CA 02828167 2013-08-23
33
R21
\
ID- y1- A¨
R22
/
I \
R22 1 I R24
Y3
1
P
/ \
R25 R26
1 in
(XXI)
where
n is 0 or 1;
R21, R22, R23, R24, R25, R26 are each, independently of one
another,
unsubstituted or at least monosubstituted C1-C10-alkyl, C1-C4-
alkyldiphenylphosphine (-C1a4-alkyl-P(pheny1)2), C3-C10-cycloalkyl, C3-C10-
heterocyclyl comprising at least one heteroatom selected from among N, 0
and S, C5-C14-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, ON, NH2 and C1-C10ralkyl;
A is
i) a bridging group selected from the group consisting of unsubstituted
or at least monosubstituted N, 0, P, C1-C6-alkane, C3-C10-cycloalkane,
C3-C10-heterocycloalkane comprising at least one heteroatom selected from
among N, 0 and S, C5-014-aromatic and C5-06-heteroaromatic comprising
at least one heteroatom selected from among N, 0 and S,
where the substituents are selected from the group consisting of:
C1-04-alkyl, phenyl, F, Cl, Br, OH, OR27, NH2, NHR27 or N(R27)2,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl;
or
ii) a bridging group of the formula (XXII) and (XXIII):
EK11-1973PC

. PF0000071973/MKr CA 02828167 2013-08-23
,
34
(R28),õ (R29), (R286,>( .....
xi(R29),,,
>\-------- /,,,
1 1 1 1
-x11 )(12
(xxii) (xxiii)
m, q are each, independently of one another, 0, 1, 2, 3 or 4;
R28, R29 are selected independently from the group
consisting of C1-C10-
alkyl, F, Cl, Br, OH, OR27, NH2, NHR27 and N(R27)2,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl;
Xi', x12 are each, independently of one another, NH,
0 or S;
X13 is a bond, NH, NR30, 0, S or CR31R32;
R3 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-C14-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 Cl-Curalkyl;
R31, R32 are each, independently of one another, unsubstituted or at
least monosubstituted C1-C10-alkyl, C1-C10-alkoxy, C3-C10-
cycloalkyl, C3-C10-cycloalkoxy, C3-C10-heterocycly1 comprising at
least one heteroatom selected from among N, 0 and S, C5-C14-
aryl, C5-C14-aryloxy or Cs-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;
EK11-1973PC

. PF0000071973/MKr CA 02828167 2013-08-23
Y1, Y2, Y3 are each, independently of one another, a bond, unsubstituted or at
least monosubstituted methylene, ethylene, trimethylene,
tetramethylene, pentamethylene or hexamethylene,
5 where the substituents are selected from the group consisting
of: F,
Cl, Br, OH, OR27, CN, NH2, NHR27, N(R27)2 and C1-C10-alkyl,
where R27 is selected from among C1-C10-alkyl and C5-C10-aryl,
10 for the homogeneously catalyzed preparation of alkanolamines which have
a primary
amino group and a hydroxyl group by alcohol amination of diols having two
hydroxyl
groups (-OH) by means of ammonia.
The definitions and preferences described for the process of the invention
apply to the
15 use of the complex catalyst of the formula (XXI) for the homogeneously
catalyzed
preparation of alkanolamines which have a primary amino group (-NH2) and a
hydroxyl
group (-OH) by alcohol amination of diols having two hydroxyl groups (-OH) by
means
of ammonia.
20 The invention is illustrated by the following examples without being
restricted thereto.
Example
General method for the catalytic amination of alcohols by means of ammonia
according
25 to the invention
Ligand L, metal salt M or catalyst complex XlVb (for preparation, see below,
weighed
out under an inert atmosphere), solvent and the alcohol to be reacted were
placed
under an Ar atmosphere in a 160 ml Parr autoclave (stainless steel V4A) having
a
30 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
35 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). The results for the amination of 1,4-butanediol (tables la,
lb and 2),
diethylene glycol (tables 3a, 3b and 4), monoethylene glycol (table 5) and
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diethanolamine (table 6), 1,5-pentanediol, 1,9-nonanediol, 1,6-hexanediol and
1,10-
decanediol (table 7) and 2,5-(dimethanop-furan (table 8) are given below.
Synthesis of the catalyst complex XlVb
PCy2
,Br
fdl(¨ =
HFCY2\ [RuHCI(C0)(PPh3)3]
N Br N
Me0H Toluene
=;--)
PCy2 co ,
XIVb
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
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,
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,
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
[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 Ru-PNP Pincer 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 = 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,
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-P(CaH(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] =
60.89 (s, -CH2-P(CY)2).
[1] J. Chiron, J.P. Galy, Synlett, 2003, 15, 2349-2350.
[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,
13-21.
Ligand name CAS IUPAC
Triphos 22031-12-5 1,1,1-
tris(diphenylphosphinomethyl)ethane
Xantphos 161265-03-8 4,5-bis(diphenylphosphino)-9,9-
dimethylxanthene
Rhodaphos 22031-14-7 1,1,1-tris(diethylposphinomethyl)ethane
DPPEPP 23582-02-7 bis(2-
diphenylphosphinoethyl)phenylphosphine
Tetraphos 23582-03-8 tris[2-
(diphenylphosphino)ethyl]phosphine
dppb 7688-25-7 1,4-Bis(diethylphospino)butane
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Table 1a: Amination of 1,4-butanedioI using various catalyst systems
NH 3J
H0 ..õ........----....õ...---... + N H 2 N ...,.........-----..õ...õ--
---, + N
kJ ri --IN- N H 2 N H 2 H
a b
c
No. Solvent T Time NH3 Reaction Metal salt [M] Met.
[M] Ligand [L] Lig. [L] Conver Selectivity`
[ C] [h] [eq.] e) pressure (mol%)
(mol%)f) sion b a : b : c
[bar]
n
1 Toluene 155 12 6 49 [RuHCI(C0)(PPh3)3] 0.1 Triphos 0.1
74.7 59.1 0.7 6.7 0
N
2 Toluene 155 12 6 66e) [RuHCI(C0)(PPh3)3] 0.1 Triphos 0.1
61.8 78.0 0.6 5.4 co
I.)
co
3 Toluene 155 12 6 45 [RuHCI(C0)(PPh3)3] 0.1 Xantphos 0.1
35.0 81.8 0.0 6.4 H
6)
-,1
4 Toluene 155 12 6 47 [Ru(COD)methylallyI20.1 Tetraphos 0.1
6.0 8.5 0.0 1.6 I.)
0
, l
H
La
_
I
Toluene 155 12 6 ' 39 [RuHCI(C0)(PPh3)3] 0.2 Rhodaphos
0.2 39.8 17.5 0.0 4.6 0
co
1
6 Toluene 155 12 6 38 [RuHCI(C0)(PPh3)3] 0.2 DPPEPP 0.2
_ 66.6 68.1 0.1 11.0 I.)
u.)
a) 50 ml of solvent; Batch size: 25 mmol of 1,4-butanediol b) Evaluation by GC
(% by area); c) Product selectivity determined by GC; d) Injected cold:
5 bar H2, 8 bar NH3, e) Molar equivalents of NH3 per OH function on the
substrate; f) mol% based on number of OH functions on the substrate
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Table lb: Amination of 1,4-butanediol using various catalyst systems
No Solvent T Tim NH3 Reaction Metall salt [M] Met. [M] Ligand
[L] Lig. [L] Conver- Selectivity`
a) rci e[h] [Eq.]d) pressure (mol%)ef) (mol%)e)
sion b a : b : c
[bar]
1 THF 155 12 6 40 [RuHCI(C0)(PP 0.2 0.2
dppb
49.6 61.4 0.0 20.3
h3)3]
a) 50m1 of solvent; Batch size: 25 mmol of 1,4-butanediol; b) Evaluation by GC
(% by area); c) Product selectivity determined by GC; d) Molar 0
equivalents of NH3 per OH function on the substrate; e) mol% based on number
of OH functions on the substrate co
CO
0
0
CO
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Table 2: Amination of 1,4-butanediol using XlVb as catalyst system
NH, H0õ...õ,õ...........õ
+ +
J
HO---OH NH2 H2NN H2 N
N
H
a b
c
5
T Time NH3 Reaction
Selectivity
No. a) Solvent Further condition
Conversionb 0
pc] [h] [eq.]e) pressure [bar]
a b C
= 0
1 Toluene 155 12 6 42 54.6
72.2 8.8 17.7 "
op
.
I.)
2 Toluene 155 12 6 41 5.0
mol% of water 63.0 71.8 9.3 17.3 CO
H
0)
3 ' Toluene 155 12 6 55 5 bar
of H2 injected cold 25.0 81.0 4.8 13.6 -A
N
4 Toluene 155 12 9 47 61.1
74.2 8.9 15.7 0
H
5 p-Xylene 155 12 6 44 70.6
62.6 5.8 28.7 u.)
1
0
6 p-Xylene 155 12 6 40 - 42.0
78.8 3.5 16.5 0
,
I.)
7 p-Xylene 155 12 9 48 62.3
72.3 7.6 18.5 u.)
8 p-Xylene 155 12 18 78 48.1
75.9 2.6 17.4
9 Mesitylene* 155 12 6 39 - 58.3
70.5 6.7 20.3
a) Conditions unless indicated otherwise: 50 ml of solvent, batch size 25 mmol
of 1,4-butanediol, 0.1 mol% of catalyst complex XlVb (based
on number of OH functions on the substrate), b) Evaluation by GC (% by area),
c) Product selectivity determined by GC, e) Molar
equivalents of NH3 per OH function on the substrate
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Table 3a: Amination of diethylene glycol using various catalyst systems
NH3 /--\
HO (:),.,,NH2 + H2NN.7N0,N.,NH2 + 0 NH
a b c
No. Solvent') T Time NH3 Reaction Metal salt [M] Met. [M] Ligand
[L] Lig. [L] Conver- Selectivity C n
rC] [h] (eq.] ) pressure (mol%)f)
(mol%)f) sion b a : b : c 0
I.)
[bar]
0
I.)
0
1 Toluene 155 12 6 49 [RuHCI(C0)(PPh3)3] 0.1 Triphos
0.1 51.0 66.2 0.9 5.9 H
61
-A
2 Toluene 155 12 6 59 ) [RuHCI(C0)(PPh3)31 0.1 Triphos
0.1 16.2 87.3 0.1 2.3 I.)
0
CA
I
4 Toluene 155 12 6 44 [Ru(COD)methylally12] 0.1
Tetraphos 0.1 3.9 0.0 0.0 1.1 0
co
1
u.)
a) 50 ml of solvent; Batch size: 25 mmol of diethylene glycol; b) Evaluation
by GC (% by area); c) Product selectivity determined by GC; d) Injected
cold: 5 bar of H2, 8 bar of NH3; e) Molar equivalents of NH3 per OH function
on the substrate; f) mor/o based on the number of OH functions on the
substrate
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Table 3b: Amination of diethylene glycol using various catalyst systems
NH
/ \
+
N H
\ __ /
a
No. Solvent a) T Tim NH3 Reaction Metal salt [M] Met. [M] Ligand N
Lig. [L] Conver- Selectivity
[ C] e [eq.]e) pressure (mol /0)0
(mol%)f sion b a : b : c
[h] [bar]
0
1 Toluol 180 12 6 654) [RuHCI(C0)(PPh3)3] 0.2 Triphos
0.2 97.6 26.4 13.4 54.0 co
co
2 Toluol 155 12 6 40 [RuHCI(C0)(PPh3)3] 0.2 DPPEPP 0.2
21.5 46.0 0.0 2.3
a) 50 ml of solvent; Batch size: 25 mmol of diethylene glycol; b) Evaluation
by GC (% by area); c) Product selectivity determined by GC; d) Injected
0
cold: 5 bar of H2, 8 bar of NH3; e) Molar equivalents of NH3 per OH function
on the substrate; f) mol% based on the number of OH functions on the
substrate
0
co
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Table 4: Amination of diethylene glycol using XlVb as catalyst system
NH3
rTh
HO7N .,C1H --31. H07-N, ,-N7NH2 + H2N07.7NH2 + 0 NH
0 0
a b
c
Conver- Selectivity
No.a) Solvent T pC] Time [h] NH3 [eq.]d) Reaction
Further conditions
pressure [bar]
a b c
sionb)
0
1 Toluene 135 12 6 38
40.4 85.8 2.5 6.7
0
2 Toluene 135 12 6 38 0.2 mol% of KOtBu
11.7 69.8 3.4 5.0 I.)
co
3 Toluene 135 12 ' 6 36 1 mol% of water
37.9 86.4 2.1 6.0 I.)
CO
H
4 Toluene 135 12 6 37
42.1 87.1 3.3 6.5 Ol
-,1
Toluene 135 12 9 42
33.8 81.4 1.5 5.5 "
0
H
6 Toluene 135 12 ' 18 57
36.5 78.4 2.9 9.4 u.)
1
0
7 Toluene 135 15 1.1 9
49.1 76.4 3.2 8.7 co
1
I.)
8 Toluene 135 24 6 37
60.9 75.8 9.3 8.3 u.)
9 Toluene 135 60 9 45 cat: 0.05 mol%
28.1 81.7 6.3 2.5
Toluene 155 12 6 40 5.0 mol% of water
74.8 57.2 18.5 11.1
11 Toluene 155 12 6 66 5 bar of H2
61.8 69.2 18.6 8.0
12 Toluene 155 12 9 63
5 bar of H2 + 1.0 mol% of water 55.5 72.7 16.0 6.8
13 Toluene 155 12 9 66 5 bar of H2
53.1 75.0 14.1 5.8
14 p-Xylene 155 12 6 48
74.4 65.8 11.5 9.5
p-Xylene 155 12 6 38 1.0 mol% of water
77.5 52.9 21.6 16.9
16 p-Xylene 155 24 6 53 1.0 mol% of water
84.6 51.8 20.8 12.9
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17 p-Xylene 180 12 " 6 50
100.0 0.4 46.1 27.9
18 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 (based on number
of OH functions on the substrate); b) Evaluation by GC (% by area); c) Product
selectivity determined by GC; d) Molar equivalents of NH3 per OH function
on the substrate
0
1.)
co
1.)
co
0
0
CO
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Table 5: Amination of monoethylene glycol using XlVb as catalyst system
i--\
5
HO NH3 ..-.......õOH õ..
HO.,,NH2 4. H2N NF12 + HN\_)1H
a b c
Reaction
Selectivity n
Time
No.a) Solvent T [ C] NH3 [eq.]d) pressure Further conditions
Conversion!)
0
[h]
a b c I.)
[bar]
co
I.)
co
1 Toluene 135 12 6 35 14.0
68.6 16.6 0.5 H
61
-A
2 Toluene 135 12 6 38 0.2 mol% of KOtBu
39.3 65.8 18.9 0.7 I.)
3 Toluene 135 12 9 44 11.0
71.9 17.5 0.7 0
H
CA
4 Toluene 135 12 12 48 10.6
68.2 17.5 2.5 1
0
co
5 Toluene 135 12 18 54 13.7
69.0 15.6 2.7 1
I.)
u.)
6 p-Xylene 155 3 6 38 18.2
56.9 19.5 1.0
a) Conditions unless indicated otherwise: 50 ml of solvent; Batch size: 25
mmol of monoethylene glycol, 0.1 mol% of catalyst complex XlVb (based on
number of OH functions on the substrate); b) Evaluation by GC (% by area); c)
Product selectivity determined by GC; d) Molar equivalents of NH3 per
OH function on the substrate
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Table 6: Amination of diethanolamine using XlVb as catalyst system
NH
H2NN H2
3 i.--\
HO,..N.--..,,...OH -0- HO .........1 isNH2 + H2N ,,,,,,\ N .."..,,,NH2 + HN
NH +
H H H \..._./ 2
a b c d
Reaction
Selectivities n
No.a) Solvent T Time NH3,, pressure Further conditions Conversion b
0
rC] [h] [eq.]-
a b c d I.)
co
[bar]
I.)
.
co
1 Toluene 135 12 9 43 22.7
51.9 0.4 0.0 31.2 H
(5)
-
--I
2 Toluene 155 12 6 44 - 49.0
41.4 1.8 0.0 30.2 I.)
0
3 Toluene 155 24 6 42 ' 69.0
32.6 2.1 0.0 30.6 H
u.)
..
4 Toluene 155 12 6 45 32.5
31.8 1.8 0.0 34.6 1
0
co
5 Toluene 155 12 9 54 57.5
47.4 2.5 4.1 34.3 1
I.)
..
u.)
6 Toluene 155 12 6 44 -1 mol% of KOtBu 25.7
34.8 3.3 0.0 25.3
7 Toluene 155 12 12 57 50.8
39.8 1.3 3.0 36.6
8 Toluene 155 12 6 44 1 mol% of water 51.7
40.5 1.4 3.4 33.8
9 Toluene 155 12 6 43 5 mol% of water 50.6
42.2 1.4 -4.6 30.8
Toluene 155 12 6 60 5 bar of H2 33.4 51.1
1.4 4.4 30.6
a) Conditions unless indicated otherwise: 50 ml of solvent; Batch size: 25
mmol of diethanolamine, 0.1 mol% of catalyst complex XlVb (based on
number of OH functions on the substrate); b) Evaluation by GC (% by area); c)
Product selectivity determined by GC; d) Molar equivalents of NH3
per OH function on the substrate
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Table 7: Amination of (1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,9-
Nonanediol) using various catalyst systems
HO,,
NH3
lir! -0- HO.,--(1.
n NH2 +
n n 2
a b
Time Reaction Solvent
n
No T NH3 Met. [M]
Lig. [L] Conver- Selectivity c
a) Substrate
[ C] [h] lee pressure (water- Metall salt [M]
(mol%)n Ligand [L]
(mol%) sion b)
a : b 0
IV
[bar] free)
co
I.)
co
1 1,6-Hexanediol 155 12 6 42 Toluol [RuHCI(C0)(PPh3)3] 0.10
Triphos 0.10 83.0 61.3 25.7 H
Ol
_
-V
2 1,6-Hexanediol 155 12 6 36 Toluol ' [RuHCI(C0)(PPh3)3] 0.10
Xantphos 0.10 33.4 84.9 4.6 I.)
0
3 1,6-Hexanediol 155 12 6 40 Toluol [RuHCI(C0)(PPh3)3] 0.10
DPPEPP -0.10 70.7 66.5 16.0 H
LO
I
4 1,6-Hexanediol 155 12 6 44 Toluol [RuHCI(C0)(PPh3)3] 0.10
Rhodaphos 0.10 35.1 53.0 2.0 0
CO
1,10 -
I
IV
5 155 24 6 39 Toluol [RuHCI(C0)(PPh3)3] 0.20
Triphos 0.20 85.7 43.0 44.4 u.)
Decanediol
_
7 1,5-Pentanediol 155 12 6 40 Toluol [RuHCI(C0)(PPh3)3] 0.10
Triphos 0.10 70.3 66.8 1.3
_
8 1,5-Pentanediol 155 12 6 45 Toluol [RuHCI(C0)(PPh3)3] 0.10
DPPEPP 0.10 50.9 64.6 7.1
9d) 1,9-Nonanediol 155 24 12 14 Mesitylene [RuHCI(C0)(PPh3)3] 0.20
Triphos 0.20 79.3 54.0 31.1
a) 50 ml of solvent; Batch size: 25 mmol of dial; b) Evaluation by GC (% by
area); c) Product selectivity determined by GC ( /0 by area); d) Batch size:
50
mmol of substrate; Batch size: 50 mmol of dial; e) Molar equivalents of NH3
per OH function on the substrate; f) mol% based on the number of OH
functions on the substrate
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Table 8: Amination of 2,5- dimethanolfuran
HOOH H2N
\ 0/ OH H2N \ (Di NH2
0
NH3 +
\ /
a b
0
0
Time konz. Reaction Solvent
Con- Selectivity K)
No TMet. [M] Ligand Lig. [L]
. c co
I.)
Substrate [h] [mo1/1] NH3 a, pressure (water-
Metall salt [M] version co
a) [ C] [eq.]¨
(mol%)e) [L] (mol%)e) b) H
[bar] free)
a : b 0,
-.3
1 2,5-dimethanolfuran 140 24 1 6 15 THF [RuHCI(C0)(PPh3)3]
0.20 Triphos 0.20 46.8 63.1 10.2 "
0
_
H
tert-
2 2,5-dimethanolfuran 140 3 0,5 6 32 XlVb
0.10 - - 84.6 49.2 43.6 i
0
butanol
co
i
iv
a) 40m1 of solvent; Batch size: 40 mmol of diol; b) Evaluation by GC (a)/0 by
area); c) Product selectivity determined by GC (% by area); d) Molar
equivalents of u.)
NH3 per OH function on the substrate; e) mol% based on the number of OH
functions on the substrate
EK11-1973PC