Rhodium-catalyzed tandem isomerization/hydroformylation of the bio-sourced 10-undecenenitrile: Selective and productive catalysts for production of polyamide-12 precursor

Article abstract of DOI:10.1002/adsc.201300492

The hydroformylation of 10-undecenenitrile (1) - a substrate readily prepared from renewable castor oil - in the presence of rhodium-phosphane catalysts systems is reported. The corresponding linear aldehyde (2) can be prepared in high yields and regioselectivities with a (dicarbonyl)rhodium acetoacetonate-biphephos [Rh(acac)(CO)₂-biphephos] catalyst. The hydroformylation process is accompanied by isomerization of 1 into internal isomers of undecenenitrile (1-int); yet, it is shown that the Rh-biphephos catalyst effectively isomerizes back 1-int into 1, eventually allowing high conversions of 1/1-int into 2. Recycling of the catalyst by vacuum distillation under a controlled atmosphere was demonstrated over 4-5 runs, leading to high productivities up to 230,000 mol (2)×mol (Rh)^-1 and 5,750 mol (2)×mol (biphephos)^-1. Attempted recycling of the catalyst using a thermomorphic multicomponent solvent (TMS) phase-separation procedure proved ineffective because the final product 2 and the Rh-biphephos catalyst were always found in the same polar phase. Auto-oxidation of the linear aldehyde 2 into the fatty 10-cyano-2-methyldecanoic acid (5) proceeds readily upon exposure to air at room temperature, opening a new effective entry toward polyamide-12. Copyright

Full text of DOI:10.1002/adsc.201300492

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DOI: 10.1002/adsc.201300492
Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of
the Bio-Sourced 10-Undecenenitrile: Selective and Productive
Catalysts for Production of Polyamide-12 Precursor
Jꢀrꢀmy Ternel,a Jean-Luc Couturier,b Jean-Luc Dubois,c
and Jean-FranÅois Carpentiera,*
a
Organometallics, Materials and Catalysis; UMR 6226 Institut des Sciences Chimiques de Rennes, CNRS-University of
Rennes 1, F-35042 Rennes, France
Fax : (+33)-(0)223-236-939; phone: (+33)-(0)223-235-950; e-mail: jean-francois.carpentier@univ-rennes1.fr
ARKEMA, CRRA, BP 63, Rue Henri Moissan, F-69493 Pierre Bꢀnite, France
ARKEMA, 420 Rue d’Estienne d’Orves, F-92705 Colombes, France
b
c
Received: June 5, 2013; Revised: September 3, 2013; Published online: November 11, 2013
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300492.
Abstract: The hydroformylation of 10-undeceneni- ductivities up to 230,000 mol(2)·mol(Rh)À1 and
trile (1) – a substrate readily prepared from renewa- 5,750 mol(2)·mol(biphephos)À1. Attempted recycling
ble castor oil – in the presence of rhodium-phos- of the catalyst using a thermomorphic multicompo-
phane catalysts systems is reported. The correspond- nent solvent (TMS) phase-separation procedure
ing linear aldehyde (2) can be prepared in high proved ineffective because the final product 2 and
yields and regioselectivities with a (dicarbonyl)rhodi- the Rh-biphephos catalyst were always found in the
um acetoacetonate-biphephos [RhACTHNUTRGENUG(N acac)(CO)2-bi- same polar phase. Auto-oxidation of the linear alde-
phephos] catalyst. The hydroformylation process is hyde 2 into the fatty 10-cyano-2-methyldecanoic acid
accompanied by isomerization of 1 into internal iso- (5) proceeds readily upon exposure to air at room
mers of undecenenitrile (1-int); yet, it is shown that temperature, opening a new effective entry toward
the Rh-biphephos catalyst effectively isomerizes polyamide-12.
back 1-int into 1, eventually allowing high conver-
sions of 1/1-int into 2. Recycling of the catalyst by Keywords: hydroformylation; isomerization; nylon-
vacuum distillation under a controlled atmosphere 12; recycling; rhodium; tandem catalysis; 10-undece-
was demonstrated over 4–5 runs, leading to high pro- nenitrile
Introduction
carboxylic derivatives, which are direct precursors of
PA-12.[7] Hydroformylation of olefins based on homo-
The use of renewable compounds derived from the geneous transition metal catalysts is a major industrial
biomass has recently become a focus of interest for process that produces versatile intermediates for phar-
researchers in the context of depletion of fossil re- maceuticals and fine chemistry.[8,9] However, to the
sources.[1] Among them, fats and oils present a strong best of our knowledge, there is no report in the open
potential for a variety of applications.[2,3] In particular, literature on the hydroformylation of unsaturated
10-undecenoic acid derivatives constitute valuable fatty nitriles.[10]
feedstocks readily available from castor oil;[4] their
.
Efficient and selective catalytic systems exist for
transformation by ruthenium-catalyzed cross-metathe- the hydroformylation of C3–C5 olefins but that of
sis has recently opened up efficient routes towards longer chain alkenes remains more challenging. In
a series of synthetic intermediates which can be used fact, during the hydroformylation of fatty olefins, in-
for the production of industrially important technical ternal alkene isomers are formed in significant
polyamides (PAs) like PA-11 (Rislanꢁ) and PA-12.[5] amounts, which eventually plague both conversions
10-Undecenenitrile is a valuable, although yet and selectivities for the desired linear (terminal) alde-
largely unexplored,[5b] compound that can be readily hydes. The use of tandem hydroformylation/isomeri-
prepared upon ammoniation of 10-undecenoic acid.[6] zation catalyst systems is one key to overcome this
Its carbonylation can provide access to C12 a,w-amino problem and even makes possible the use of cheaper
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Scheme 1. Hydroformylation products arising from 10-undecenenitrile and internal isomers, and subsequent oxidation prod-
uct as precursor of nylon-12
mixtures of terminal and internal long-chain alkenes 1 leads to two aldehydes: the desired linear (l, 2) and
as feedstock. Thus, in the last decade, efforts have the branched (b, 3) ones (Scheme 1). These two prod-
been spent on the design of new ligands and related ucts, which accounted usually for >99% of the alde-
catalysts in order to reach high regioselectivity for hyde products formed, were readily isolated from
linear aldehydes in the hydroformylation of internal crude reaction mixtures by vacuum distillation and
1
olefins such as, for example, pentenenitriles.[10c–j] This characterized by H and 13C NMR spectroscopy (see
is in particular the case with biphosphite ligands relat- the Experimental Section and Supporting informa-
ed to biphephos developed at UCC[11] and DuPont- tion). The conversion and the b/l ratio were thus
1
DSM,[12] xantphos and derived ligands reported by easily determined by H NMR analysis of crude and
Van Leuween,[13] acetyl-phosphite and phosphonite li- purified reaction mixtures. Along with these two very
gands developed by Bçrner,[14] substituted naphos- major products, small amounts of hydrogenation
type ligands designed by Beller,[15] and recently tetra- product (4) and, sometimes, minor amounts of hydro-
phosphorous ligands developed by Zhang.[16] Exam- formylation products arising from internal olefins (1-
ples of regioselective isomerization–hydroformylation int) were detected (vide infra).
sequences of internal alkenes in biphasic media, with
Preliminary control experiments indicated that iso-
a water-soluble system based on sulfonated naphos merization of 1 to 1-int is not a thermal but rather
derivatives, have been reported as well.[17] Also, a catalytic process, which is promoted by rhodium-hy-
a series of xantphos-type ligands has been applied in dride species produced in situ (Table 1, entries 1–3).
rhodium-catalyzed hydroaminomethylation (including The extent of isomerization is quite significant at
a hydroformylation step) to produce synthetically im- 1208C but, at 1008C, this reaction remains competi-
portant linear amines from internal olefins in very tive with hydroformylation, as discussed later in more
1
high yields and with very high regioselectivities (up to detail. H and 13C NMR analyses (see the Supporting
96%).[18]
Information, Figure S6) revealed that the isomeriza-
Herein we report a detailed study of the isomeriza- tion products 1-int recovered at the end of hydrofor-
tion–hydroformylation of 10-undecenenitrile (1) and mylation batches are cis/trans 9-undecenenitrile and
internal isomers (1-int) to the corresponding linear al- also sometimes products in which the double bond
dehyde (2) (Scheme 1). The reaction has been per- has migrated on over at least two carbons from the
formed with homogeneous rhodium-diphosphane cat- terminal positions, i.e., trans/cis 8-undecenenitrile and
alysts; the conditions for achieving high productivities possibly other internal isomers in lower amounts. Ex-
and selectivities are described, including an effective pectedly, the longer the reaction time, the more such
recycling of the hydroformylation catalyst, and dem- internal isomers were present in the final mixture
onstration of the ready auto-oxidation of aldehyde 2 (vide infra).
into the fatty nitrile carboxylic acid 5.
Several combinations of RhACTHUGNTERNNU(G acac)(CO)2 with (di)-
phosphine/phosphite ligands were then screened in
the homogeneous hydroformylation of 1. Representa-
tive results are summarized in Table 1, entries 4–11.
Chemoselective conversion into mixtures of aldehydes
2 and 3 was observed at 1008C with most catalyst sys-
tems; the hydrogenation by-product 4 was always
Results and Discussion
Single-Batch Hydroformylation of 10-Undecenenitrile
The hydroformylation studies were performed on formed in minute amounts with these systems and, at
a 95:5 mixture of 10-undecenenitrile (1) and internal 0.2 mol% Rh loading, isomerization of 1 to 1-int was
isomers (1-int, essentially cis/trans 9-undecenenitrile insignificant, except with the Rh-P
ACHTUNGRTEN(NGNU OPh)3 system. The
in the initial reagent).[19] The hydroformylation of Rh-PPh3 and Rh-P
AHCTUNGTRENNUNG
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Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of the Bio-Sourced 10-Undecenenitrile
Table 1. Hydroformylation of 10-undecenenitrile promoted by various Rh-based systems.[a]
Entry
Ligand
Bite angle
[deg]
Temp.
[8C]
1
1-int
2+3
4
Conv. 1
HF
2/3
G
[%][b]
[%][b]
[%][b]
[%][b]
[%][c]
[%][d]
1[e]
2[f]
3
4
5
6
7
8
9
–
–
–
–
–
–
–
120
120
120
100
100
100
100
100
100
100
100
100
100
0
5
5
68
5
9
5
5
5
5
5
8
–
–
7
80
74
5
12
10
6
–
–
25
0
0
0
0
0
2
3
2
0
0
–
–
7
–
–
100
84
84
5
11
13
8
55:45
71:29
68:32
69:31
46:54
76:24
97:3
60:40
99:1
PPh3
P
dppm
dppe
dppb
xantphos
bisbi
15
15
90
83
85
87
85
78
100
95
100
100
100
75
70
70
(OPh)3
–
72
85
98
107
113
123
10
11
7
12
11
18
biphephos
[a]
Reaction conditions (unless otherwise stated): 1/1-int (95:5 mixture)=5.0 mmol, [1]0/[Rh]=5,000, [ligand]/[Rh]=20, tolu-
ene=10 mL, P=20 bar CO/H2 (1:1), t=2 h.
Distribution (mol%) of remaining 1, internal alkenes 1-int (residual or formed during the reaction), aldehydes 2 and 3,
and hydrogenation product 4, as determined by NMR and GLC analyses.
[b]
[c]
[d]
[e]
[f]
Conversion of 1=1À[1]/([1]+[1-int]À
ACHTUNGTERN[NUGN 1-int]0 +[2+3]+[4]).
Selectivity for hydroformylation products=([2+3])/
G
ACHTUGNTERN[NUGN 1-int]0) with [1-int]0 =5.
No rhodium precursor.
No CO/H2 pressure.
high activity, enabling conversions of up to 85% other hand, reducing the ligand-to-rhodium ratio
within 2 h at 0.2 mol% Rh loading (TOF=2,000 hÀ1 down to 5 equiv. induced slightly more isomerization
at max. conv.). However, the regioselectivity for the (entries 5–7). Also, at relatively high olefin-to-rhodi-
linear aldehyde was expectedly poor with these non- um ratio (i.e., ꢀ50,000), the extent of competitive iso-
chelating ligands. Among the different chelating li- merization and also hydrogenation became slightly
gands investigated (Scheme 2), the best regioselectivi- more important (entries 3–5, 8 and 9). Prolonged re-
ty was eventually observed with the Rh-xantphos and action times did not allow further conversion of the
Rh-biphephos systems which gave, respectively, 97% internal olefins which eventually accumulated in the
and 99% of the linear aldehyde, yet with a relatively reaction medium. Yet, this Rh-xantphos system al-
lower activity at 1008C (TOF=ca. 300–450 hÀ1) and lowed at 1208C a remarkable productivity [TON up
along with small amounts of the hydrogenation by- to 75,000 mol(2)·mol(Rh)À1], with a chemo- and re-
product 4.
gioselectivity of 81% and 97%, respectively (entry 9).
The Rh-biphephos catalyst system showed higher
With the aim to determine the maximal productivi-
ty of each promising catalyst, the influence of experi- activities and regioselectivies than the corresponding
mental conditions on the outcome of the reaction was xantphos systems over the temperature range 80–
studied in more detail with the Rh-xantphos system 1408C (Table 3). TOFs in the range 2,000–3,500 hÀ1
first; the results are summarized in Table 2. The activ- along with excellent regioselectivities up to 99% were
ity expectedly increased in the temperature range observed; however, in all cases, a significant amount
100–1208C, without significant detrimental impact on of internal alkenes built (up to 25%; entries 1–4). Ad-
the chemo-/regioselectivities (entries 1–3). On the ditional experiments were conducted by increasing
Scheme 2. Chelating bisphosphane ligands with large bite angles used in this study.
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Table 2. Hydroformylation of 10-undecenenitrile promoted by the Rh-xantphos system.[a]
Entry
[1]0/[Rh]
Xantphos
[equiv. vs. Rh]
Temp.
[8C]
Time
[h]
1
1-int
2+3
4
Conv. 1
HF
2/3
[%][b]
[%][b]
[%][b]
[%][b]
[%][c]
[%][d]
1
2
3
4
5
6
7
8
9
5,000
5,000
5,000
10,000
20,000
20,000
20,000
50,000
100,000
20
20
20
20
20
10
5
100
110
120
120
120
120
120
120
120
24
24
12
12
18
24
24
24
48
24
1
1
6
8
6
8
8
8
10
13
16
67
86
89
86
78
76
81
72
71
3
5
4
4
4
5
4
5
6
75
99
99
98
89
88
95
89
93
94
91
95
92
92
88
90
84
81
97:3
97:3
97:3
97:3
97:3
98:2
97:3
97:3
97:3
2
10
11
5
10
7
20
20
[a]
Reaction conditions (unless otherwise stated): 1/1-int (95:5 mixture)=5.0 mmol, toluene=10 mL, P=20 bar CO/H2 (1:1).
Distribution (mol%) of remaining 1, internal alkenes 1-int (residual or formed during the reaction), aldehydes 2 and 3,
and hydrogenation product 4, as determined by NMR and GLC analyses.
Conversion of 1.
[b]
[c]
[d]
Selectivity for hydroformylation products (see Table 1).
Table 3. Tandem isomerization/hydroformylation of undecenenitriles 1/1-int promoted by the Rh-biphephos system.[a]
Entry
[1]0/[Rh]
Biphephos
[equiv vs. Rh]
Temp.
[8C]
Time
[h]
1
1-int
2+3
4
Conv. 1
HF
2/3
[%][b]
[%][b]
[%][b]
[%][b]
[%][c]
[%][d]
1
2
3
4
5
20,000
20,000
20,000
20,000
5,000
20
20
20
20
20
80
4
4
4
4
49
26
2
0
0
0
0
31
0
0
0
52
5
0
0
63
8
0
0
52
6
20
20
21
25
25
13
5
16
21
10
5
26
49
72
70
70
80
86
48
74
83
86
25
69
82
84
16
65
79
81
27
67
79
83
19
55
77
82
19
57
75[e]
5
5
5
5
5
7
9
5
5
7
9
5
6
9
10
5
5
8
11
5
6
8
9
5
7
8
9
48
73
98
57
71
77
74
74
84
91
75
78
87
90
58
77
86
88
50
75
83
85
63
75
83
87
51
69
81
86
49
68
82
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
99:1
98:2
92:8[e]
100
120
140
120
100
100
100
100
67
100
100
100
45
4
24
48
2
24
48
72
2
24
48
72
2
24
48
72
4
24
48
72
24
48
72
96
24
48
96
6
20,000
20,000
20,000
50,000
100,000
100,000
20
10
5
120
120
120
120
120
120
7
18
20
9
95
100
100
34
6
8
16
22
13
8
16
21
13
8
18
23
15
9
19
24
12
92
100
100
45
9
20
20
10
94
0
0
58
15
0
100
100
39
10
84
100
100
41
88
100
0
11
56
11
0
6
8
10
[a]
Reaction conditions (unless otherwise stated): 1/1-int (95:5 mixture)=5.0 mmol, toluene=10 mL, P=20 bar CO/H2 (1:1).
Distribution (mol%) of remaining 1, internal alkenes 1-int (residual or formed during the reaction), aldehydes 2 and 3,
and hydrogenation product 4, as determined by NMR and GLC analyses.
Conversion of 1.
Selectivity for hydroformylation products (see Table 1).
In addition, 3% of internal aldehydes were formed in this case; [2]/[3]/ACTHNUTRGENUGN[int-ald]=92:4:4.
[b]
[c]
[d]
[e]
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Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of the Bio-Sourced 10-Undecenenitrile
terestingly, it appeared possible to reduce the biphe-
phos-to-rhodium ratio from 20 down to 5 without
much impact on the selectivity and activity (entries 6–
8). On the other hand, attempts to combine low load-
ings of rhodium and biphephos tend to produce larger
amounts of internal aldehydes[20] (entry 11).
Of note, the Rh-biphephos system features similarly
good catalytic performances when applied to the hy-
droformylation of related fatty functional alkenes,
such as methyl 10-undecenoate, 10-undecenal, 1-
bromo-10-undecene, and also the simple undecene.
Representative results obtained with those substrates
under typical reaction conditions are summarized in
Table 7. Good chemoselectivity and excellent regiose-
lectivity for the linear aldehydes were observed in all
cases.
Scheme 3. Tandem isomerization/hydroformylation of unde-
cenenitriles 1/1-int.
The tandem isomerization–hydroformylation was
the reaction time to assess whether the Rh-biphephos further investigated separately using mixtures of
system can isomerize back internal alkenes 1-int 1 and 1-int enriched (70–95%) in the latter internal
(mainly cis/trans 9- and 8-undecenenitrile, see the isomers, typically recovered at the end of a batch hy-
Supporting Information Figure S6) into its terminal droformylation experiment. Consistent with the
isomer 1 and allow eventually full conversion of alk- above mentioned one-pot experiments, the Rh-xant-
ACHTUNGTRENNUNGenes into aldehydes (Scheme 3). The results of such phos system proved ineffective towards internal ole-
experiments are summarized in Table 3, entries 5–11. fins: after 72 h, only 28% of this mixture (that is, es-
Indeed, hydroformylation of 1 by this catalyst system sentially 1 initially present) was converted into alde-
proceeds stepwise (Figure 1): first, 1 is converted re- hydes, leaving the 69% of 1-int unreacted (entry 1,
gioselectively (i.e., ca. 99%) into the linear aldehyde Table 4); in addition, a noticeable decrease in selec-
~
*
2 ( ) along with significant amounts of 1-int ( ); in tivity due to the formation of internal aldehydes and
a second time period, the latter internal alkenes are hydrogenation product 4 was noted.[20] On the other
slowly isomerized and all 1 thus generated is hydro- hand, conversion of 1-int proceeded at a good rate
formylated into 2. The reaction time to convert with the Rh-biphephos system, but the selectivity was
almost quantitatively the 1/1-int mixture into alde- also much affected, especially at relatively low sub-
hydes increased significantly at a high substrate-to- strate-to-Rh ratio (Table 4, entries 2–5).
rhodium ratio because larger amounts of 1-int were
These results suggest that, rather treating internal
formed in the first stages and less catalyst was present isomers 1-int separately (e.g., in a dedicated reactor),
to isomerize them back to 1 (entries 1, 2, 4 and 5). In- it may be actually more favorable to convert them in
a one-pot procedure. Adequate conditions to reduce
the reaction time for maximal conversion of 1-int into
the corresponding aldehydes were therefore sought.
The results are summarized in Table 5. In all cases,
after complete conversion of 1 at 1208C, the tempera-
ture was increased up to 1508C. This increase of tem-
perature allowed a gain of activity for conversion of
internal alkenes into aldehydes. However, it led also
to the detrimental formation of internal aldehydes
(Scheme 3),[20] to a lesser extent than in the separate
operation though, and significant amounts of hydro-
genation product 4 formed at this relatively high tem-
perature.
Finally, the Rh-Biphephos system proved also com-
petent to perform in a highly concentrated medium or
even in bulk (i.e., solvent-free conditions) (Table 6
and Table 7). Very high selectivities in favor of linear
aldehydes were obtained, along with limited amounts
of internal alkenes and hydrogenation product (en-
tries 1–5).
Figure 1. Plots of 10-undecenenitrile (1, &) and internal al-
~
kenes (1-int, ) conversions and regioselectivity into linear
*
vs. branched aldehyde (2/3, ) as a function of time with
Rh-biphephos systems in tandem isomerization–hydrofor-
mylation experiments at 1208C (Table 3, entry 3).
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Table 4. Tandem isomerization/hydroformylation of 1-int-enriched mixtures.[a]
Entry
[1+1-int]0/[Rh]
Ligand
[equiv.]0
Time
[h]
1
1-int
2+3
int-ald
4
Conv.
[%][c]
HF
2/3
G
[%][b]
[%][b]
[%][b]
[%][b]
[%][b]
[%][d]
1
20,000
20,000
20,000
50,000
5,000
xantphos
10
biphephos
10
biphephos
20
biphephos
20
24
72
24
72
72
12
3
2
0
0
70
69
51
25
29
10
12
31
50
50
0
1
0
4
3
8
18
28
47
75
71
12
14
33
57
56
93:7
90:10
97:3
88:12
89:11
15
16
21
18
2
3
4[e]
5
72
0
38
39
4
19
62
45
85:15
biphephos
10
24
72
0
0
48
0
31
52
8
20
13
28
52
100
41
76
60:40
55:45
[a]
Reaction conditions (unless otherwise stated): 1/1-int (30:70 mixture)=5.0 mmol, toluene=10 mL, P=20 bar CO/H2
(1:1).
Distribution (mol%) of remaining 1 and internal alkenes 1-int, aldehydes 2 and 3, internal aldehydes (int-ald), and hy-
drogenation product 4, as determined by NMR and GLC analyses.
[b]
[c]
[d]
[e]
Conversion of 1/1-int=1À
Selectivity for hydroformylation products.
1/1-int (5:95 mixture)=15.0 mmol, toluene=1.0 mL, P=20 bar CO/H2 (1:1).
A
ACHTUNGTERN[NUGN 1-int]0 +[2+3]+[4])}.
Table 5. Tandem isomerization/hydroformylation of undecenenitriles 1/1-int promoted by the Rh-biphephos system at se-
quential temperatures.[a]
Entry [1]0/[Rh] Biphephos
Temp Time
1
1-int
2+3
int-ald
4
Conv. HF
2/b[e]
[equiv. vs. Rh] [8C]
[h]
[%][b] [%][b] [%][b] [%][b]
[%][b] [%][c]
[%][d]
1
2
3
4
5
20,000
20,000
20,000
50,000
100,000
20
5
120
150
150
120
150
150
120
150
150
120
150
150
120
150
150
12
2
0
0
8
1
0
1
0
0
7
0
0
8
1
0
21
10
4
24
12
5
22
9
4
23
14
4
25
16
9
72
83
84
63
77
80
71
78
79
65
70
74
60
67
67
0
0
0
0
1
2
0
4
5
0
0
2
0
0
2
5
7
12
5
9
13
6
9
12
5
16
20
7
98
77
87
88
72
83
86
76
86
88
74
74
80
69
71
73
99:1
99:1
99:1
99:1
97:3
96:4
99:1
92:8
90:10
99:1
97:3
95:5
99:1
98:2
96:4
+24
+48
16
+24
+48
24
+48
+72
24
+48
+72
48
100
100
92
99
100
99
100
100
93
100
100
92
2
20
20
+72
+96
16
22
99
100
[a]
[b]
Reaction conditions (unless otherwise stated): 1/1-int (95:5)=5.0 mmol, toluene=10 mL, P=20 bar CO/H2 (1:1).
Distribution (mol%) of remaining 1 and internal alkenes 1-int, aldehydes 2 and 3, internal aldehydes (int-ald), and hy-
drogenation product 4, as determined by NMR and GLC analyses.
Conversion of 1 (see Table 1).
Selectivity for hydroformylation products (2+3+int-ald).
Selectivity of linear to branched aldehydes (3+possible internal aldehydes)
[c]
[d]
[e]
Thus, overall, the single component Rh-biphephos combination with
a Rh-xantphos precursor, the
catalyst proved quite effective for this tandem isomer- amount of internal alkenes never decreased in the re-
ization-hydroformylation. Noteworthy, alternative action medium.
strategies to overcome the isomerization problem, re-
lying on the use of a dual catalytic system – Rh for
hydroformylation/Ru for isomerization – such as de- Recycling of the Hydroformylation Catalyst
scribed by Beller et al.[21] and by Nozaki et al.,[22]
proved ineffective in our case. Despite large loadings Even when achieving in single batch experiments pro-
(0.1–0.5 mol%) of such ruthenium co-catalysts, in ductivities exceeding 70,000 mol(2)·mol(Rh)À1 and
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Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of the Bio-Sourced 10-Undecenenitrile
Table 6. Tandem isomerization/hydroformylation of undecenenitriles 1/1-int promoted by the Rh-biphephos system at high
substrate concentration.[a]
Entry
[1]0/[Rh]
Biphephos
[equiv. vs. Rh]
[1]0
[M]
Time
[h]
1
1-int
2+3
4
Conv. 1
HF
2/3
[%][b]
[%][b]
[%][b]
[%][b]
[%][c]
[%][d]
1
2
3
20,000
20,000
20,000
10
10
20
5
48
48
4
24
48
4
24
48
48
0
0
1
0
0
9
0
0
0
2
2
89
88
75
84
87
65
83
85
86
9
10
4
6
7
5
8
9
5
100
100
99
100
100
91
100
100
100
94
93
80
88
92
76
87
89
86
98:2
97:3
99:1
98:2
98:2
99:1
99:1
99:1
99:1
bulk[e]
bulk[e]
20
10
6
21
9
4
50,000
20
20
bulk[e]
bulk[e]
6
8
5
100,000
[a]
Reaction conditions (unless otherwise stated): 1/1-int (95:5 mixture)=25 mmol, P=20 bar CO/H2 (1:1).
[b]
Distribution (mol%) of remaining 1, internal alkenes 1-int (residual or formed during the reaction), aldehydes 2 and 3,
and hydrogenation product 4, as determined by NMR and GLC analyses.
Conversion of 1.
Selectivity for hydroformylation products (see Table 1).
A minimal amount (0.5 mL) of toluene was used to introduce the catalyst precursors.
[c]
[d]
[e]
Table 7. Hydroformylation of fatty functional and simple alkenes promoted by the Rh-biphephos system.[a]
Entry
R
Subs
int
Aldeh
[%][b]
Hydrog
[%][b]
Conv. subs
[%][c]
Sel. aldeh
[%][d]
Aldeh l/b[d]
[%][b]
[%][b]
1
CN
0
0
15
32
12
16
11
10
14
10
79
82
71
51
75
5
7
4
3
3
100
100
84
66
87
83
86
89
81
90
99:1
99:1
99:1
99:1
99:1
2[e]
5
CO2Me
CHO
CH2Br
CH3
4
3
[a]
Reaction conditions (unless otherwise stated): substrate=5.0 mmol, [substrate]0/[Rh]=20,000. [biphephos]/[Rh]=20, tolu-
ene=10 mL, 1208C, 20 bar CO/H2 (1:1), 5 h reaction time (not necessarily optimized).
Distribution (mol%) of remaining substrate, internal alkenes (residual or formed during the reaction), aldehydes (linear
and branched) and hydrogenation product, as determined by NMR and GLC analyses.
Conversion of substrate.
[b]
[c]
[d]
[e]
Selectivity for hydroformylation products and linear-to-branched ratio.
[Methyl 10-undecenoate]0/[Rh]=10,000, 24 h reaction time (unoptimized).
10,000 mol(2)·mol(biphephos)À1
(Table 5
and (Figure 3, bottom spectrum).[23] Despite a rather high
Table 6), because of the high costs of rhodium and, to distillation temperature (1808C for 5–15 min), this
a lesser extent, of ligand, it is essential for industrial species remained remarkably stable. Yet, HRh(biphe-
perspectives to recycle the catalyst. For this purpose, phos)(CO)2 proved quite sensitive, and upon adventi-
we examined two strategies: vacuum distillation and tious contact with air, it degrades partially or totally
phase separation.
to an unknown phosphorus-containing species that
Vacuum distillation of the crude reaction mixture does not coordinate to Rh any longer (Figure 3,
can be readily achieved, allowing complete elimina- middle and top spectra). Thus, unsurprisingly, at-
tion of toluene solvent, and recovery of analytically tempted recycling experiments conducted without
pure aldehydes and of a residue that contains the cat- careful handling of the catalyst under inert conditions
alyst (Figure 2). A 31P NMR analysis of this residue led to poor results: just in the second run, the regiose-
showed it contains essentially HRh(biphephos)(CO)2 lectivity 2/3 dropped dramatically, and large amounts
Adv. Synth. Catal. 2013, 355, 3191 – 3204
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FULL PAPERS
vation at this stage. The overall productivity over
these 4 runs, including 3 recycling runs, reached yet
remarkable values [72,000 mol(2)·mol(Rh)À1 and
3,600 mol(2)·mol(biphephos)À1].
Other reaction conditions were investigated using
a higher initial [1/1-int]0/Rh ratio of 50,000, and no
temperature gradient but extended reaction times
(Table 9). Under such conditions, the catalyst could
be recycled over at least five runs, just by adding, like
previously, a novel charge of fresh ligand after each
runs (i.e., 20+4ꢃ5=40 equiv. overall). In this case,
the chemo- and regioselectivities just slightly de-
creased, and the productivity values increased up to
230,000 mol(2)·mol(Rh)À1 and 5,750 mol(2)·mol(bi-
phephos)À1).[24]
Figure 2. Kꢄgelrohr distillation of the crude hydroformyla-
tion reaction medium at 1808C/1 mmHg, showing the pale
colored residue that contains the catalyst (left) and the re-
covered colorless aldehydes 2/3 (right).
of internal olefins and hydrogenation product but also
Phase separation represents another approach for
of internal aldehydes were formed (Table 8, entry 1). the hydroformylation of a long-chain olefin and recy-
To prevent deteriorated performance, the catalyst was cling of the catalyst by the TMS (thermomorphic mul-
concentrated and recovered under an inert atmos- ticomponent solvent) phase separation procedure.[25]
phere and re-used by adding occasionally a novel The principle of TMS systems relies on the use of
charge of fresh biphephos in the recycling runs. Rep- mixtures of polar and non-polar solvents, which form
resentative results obtained using this procedure at higher temperature (that is the one used for per-
(Table 8, entries 2–6) evidenced that it allows main- forming hydroformylation) a homogeneous medium
taining a good chemo- and regioselectivity in favor of and a two phase system at lower temperature (e.g.,
the linear aldehyde over at least four runs. No accu- room temperature or 08C). Therefore, a simple sepa-
mulation of internal olefins was observed in the reac- ration of the catalyst typically contained in the polar
tion mixture, indicating that isomerization was also phase and the products contained in the non-polar
still effective over the different runs. Incomplete con- phase can be performed and the catalyst phase can be
version noted in the 4th cycle (during which no fresh easily recycled. Behr et al. reported recently the use
biphephos was added) indicates likely catalyst deacti- of this strategy on a regular long-chain alkene,
Figure 3. 31P{1H} NMR spectra (160 MHz, C6D6, 238C) of HRh(CO)2(biphephos) generated in situ under hydroformylation
conditions (bottom) and results of its partial (middle) and complete (top) degradation upon exposure to air.
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Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of the Bio-Sourced 10-Undecenenitrile
Table 8. Recycling of the Rh-biphephos system over 2–4 runs in the hydroformylation of 10-undecenenitrile at [undeceneni-
trile]0/[Rh]=20,000.[a]
Entry
Cycle
Biphephos[e]
extra [equiv.]
Temp
[8C]
Time
[h]
1
1-int
2+3
4
Conv. 1
HF
2/b
[f]
[%][b]
[%][b]
[%][b]
[%][b]
[%][c]
[%][d]
1[g]
2
I
II
I
–
0
–
120
120
120
130
120
130
120
130
120
130
72
24
24
48
24
48
24
48
24
48
0
2
10
0
57
0
62
0
69
10
4
88
26[i]
73
88
29
89
24
87
17
73
8
25
6
7
3
7
4
7
4
100
98
89
100
40
100
35
100
27
89
93
35
86
93
76
94
73
92
65
86
98:2
60:40[i]
99:1
99:1
99:1
98:2
98:2
98:2
99:1
97:3
40
11
5
11
4
10
6
10
8
3[h]
4[h]
5[h]
II
5
5
0
III
IV
9
[a]
Initial conditions: 1/1-int (95:5 mixture)=10 mmol, [1/1-int]0/[Rh]=20,000, [biphephos]0/[Rh]=10, toluene=5 mL, P=
20 bar CO/H2 (1:1).
Distribution (mol%) of remaining 1, internal alkenes 1-int (residual or formed during the reaction), aldehydes 2 and 3,
and hydrogenation product 4, as determined by NMR and GLC analyses.
Conversion of 1.
[b]
[c]
[d]
[e]
[f]
Selectivity for hydroformylation products (see Table 1).
Equiv, of extra biphephos added in IInd–IVth recycling runs.
Selectivity of linear to branched aldehydes (3+possible internal aldehydes).
The catalyst was recovered without precautions.
[g]
[h]
[i]
The catalyst was recovered under an inert atmosphere.
In addition, 7% of internal aldehydes were observed in this case.
Table 9. Recycling of the Rh-biphephos system over 5 runs in the hydroformylation of 10-undecenenitrile at [undeceneni-
trile]0/[Rh]=50,000.[a]
Entry
Cycle
Biphephos[e]
extra equiv.]
Temp
[8C]
Time
[h]
1
1-int
2+3
4
Conv. 1
HF
2/3
[%][b]
[%][b]
[%][b]
[%][b]
[%][c]
[%][d]
1
2
3
4
5
I
II
III
IV
V
–
5
5
5
5
120
120
120
120
120
72
72
72
72
72
0
0
0
0
0
6
5
5
6
7
88
89
88
86
85
6
6
7
8
8
100
100
100
100
100
93
94
93
91
90
99:1
99:1
99:1
99:1
98:2
[a]
Initial conditions: 1/1-int (95:5 mixture)=20 mmol, [1/1-int]0/[Rh]=50,000, [biphephos]0/[Rh]=20, toluene=15 mL, P=
20 bar CO/H2 (1:1).
Distribution (mol%) of remaining 1, internal alkenes 1-int (residual or formed during the reaction), aldehydes 2 and 3,
and hydrogenation product 4, as determined by NMR and GLC analyses.
Conversion of 1.
[b]
[c]
[d]
[e]
Selectivity for hydroformylation products (see Table 1).
Equiv. of extra biphephos added in IInd–Vth recycling runs.
namely 1-dodecene, with an Rh-biphephos system.[26] droformylation product 2 in representative TMS sys-
The catalyst (loaded at [dodecene]0/[Rh]=1,000 with tems, DMF/decane and propylene carbonate (PC)/
20 equiv. biphephos) was recycled over 30 runs with- decane, was performed (Table 10). The separation
out loss of selectivity, just by adding a novel charge temperature was set up at 08C based on Behrꢅs stud-
(6.6 equiv.) of fresh ligand after each run; an overall ies.[26] This study revealed that such TMS systems, al-
productivity of 30,000 mol(aldehyde)·mol(Rh)À1 and though highly effective in the hydroformylation of 1-
280 mol(aldehyde)·mol(biphephos)À1 was thus even- dodecene with Rh-biphephos, cannot be used in the
tually achieved.
case of 1/1-int. In fact, the Rh-biphephos catalyst and
The possibility to apply this procedure to the hy- the aldehydes formed (2) are dissolved in the same
droformylation of undecenenitrile with the Rh-biphe- polar phase, whatever the TMS parameters (nature of
phos system was examined. A preliminary study by the polar and apolar solvents, addition of a mediator,
1H NMR of the partition of substrate 1/1-int and hy- separation temperature). This is intrinsic to the
Adv. Synth. Catal. 2013, 355, 3191 – 3204
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Table 10. Partition of 1/1-int and 2 in various TMS systems.[a]
Polar solvent
(vol%)
Apolar solvent
(vol%)
Polar phase
Apolar phase
N
G
1 [%][b]
2 [%][b]
1 [%][b]
2 [%][b]
DMF (50)
DMF (30)
PC (50)
decane (50)
decane (70)
decane (50)
decane (70)
77
75
80
79
99
99
99
99
23
25
20
21
1
1
1
1
PC (30)
[a]
PC=propylene carbonate; 1/1-int (95:5)=2.5 mmol, 2=1.5 mmol, total solvent=6 mL, Separation temperature=08C.
Determined by NMR with an external standard.
[b]
nature of the reagent and products, the nitrile func- ing internal alkenes, which always form in significant
tionality making them definitively polar, in contrast amounts during the hydroformylation of 10-undecene-
to regular long chain olefins; as evidenced by the par- nitrile. Under adequate reaction conditions, nearly
tition data, the polarity is even more increased after full conversion of 10-undecenenitrile and internal iso-
hydroformylation reaction because of the telechelic mers into linear aldehyde 2, with small amounts of in-
bipolar nature of the nitrile-aldehydes.
ternal aldehydes and hydrogenation product, could be
Thus, although hydroformylation of 1/1-int could reached. Similarly good catalytic performances were
be achieved in three different TMS systems, with also obtained in the hydroformylation of related fatty
complete conversions (up to 99%) of the terminal functional alkenes, such as methyl 10-undecenoate,
olefin 1 and very good regioselectivities up to 99% 10-undecenal, 1-bromo-10-undecene, and also the
for the linear aldehyde (Supporting Information simple undecene. Recycling of the catalyst by vacuum
Table S2), the final product 2 and the Rh-biphephos distillation under a controlled atmosphere was dem-
catalyst were found in the same polar phase; it was onstrated over 4–5 runs, eventually affording very
therefore not possible to recycle the catalyst.
high productivities up to 230,000 mol(2)·mol(Rh)À1
and 5,750 mol(2)·mol(biphephos)À1. The hydroformy-
lation product 2 can be easily oxidized in the corre-
sponding fatty nitrile-carboxylic acid, opening a new
effective entry toward polyamide-12.
Oxidation of Hydroformylation Products
The auto-oxidation of aldehyde(s) 2(3) derived from
the hydroformylation of 10-undecenenitrile turned
out to be easy in toluene solution simply upon expo-
sure to air at room temperature (Scheme 1).[27] This
transformation was easily monitored by 1H and
13C NMR spectroscopy and found to proceed within
hours/days. The identity of the final products was con-
firmed by NMR and HR-MS (see the Experimental
Section and Supporting Information). While nitrile-al-
dehyde 2 obtained after distillation (99% pure) usual-
ly remains as a colorless liquid at room temperature,
the corresponding nitrile-carboxylic acid 5 derived
thereof is easily isolated as a colorless solid.
Experimental Section
All reactions involving Rh-phosphine catalysts were per-
formed under an inert atmosphere (argon) using standard
Schlenk techniques. Solvents (toluene, THF, etc.) were puri-
fied over alumina columns using
a MBraun system.
Rh(acac)(CO)2 was generously provided by Umicore Co.
AHCTUNGTRENNUNG
and used as received. Commercially available diphosphine
ligands (dmpe, dppe, dcpe, dfppe, dpp-benzene, xantphos,
biphephos, bisbi) were purchased from Strem Chemicals and
used as received. 10-Undecenenitrile (95%, contains 5% of
9- and other internal isomers), methyl 10-undecenoate and
undecenal were supplied by Arkema.
1H, 13C and 31P NMR spectra were recorded on Bruker
AC-300, AM-400 and AM-500 spectrometers. 1H and 13C
chemicals shifts were determined using residual signals of
the deuterated solvents and were calibrated vs. SiMe4. As-
signment of the signals was carried out using 1D (1H,
13C{1H}) and 2D (COSY, HMBC, HMQC) NMR experi-
ments. 31P NMR spectra were referenced externally to an
aqueous solution of H3PO4. High-resolution mass spectra
were recorded at the CRMPO, University of Rennes 1, on
a Zab Spec Tof apparatus. GLC-FID and GLC-MS analyses
were recorded on a Shimadzu GC-2014 and a Shimadzu
Conclusions
The tandem isomerization/hydroformylation of a mix-
ture of terminal and internal fatty unsaturated nitrile
compounds was performed efficiently by an
RhACHTUNGTRENNUNG(acac)(CO)2-biphephos catalyst system. The reac-
tion was performed at a very high substrate-to-rhodi-
um ratio (20,000–100,000) and allowed us to access
the desired linear aldehyde 2 with a high chemo- and
regioselectivity of up to 93% and 99%, respectively.
In contrast to an Rh-xantphos system, this Rh-biphe-
phos catalyst proved especially efficient for isomeriz- GC-2010/GC-MS2010S apparatus, respectively.
3200
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Rhodium-Catalyzed Tandem Isomerization/Hydroformylation of the Bio-Sourced 10-Undecenenitrile
10-Undecenenitrile (1)
Hydroformylation Products Derived from Methyl 10-
Undecenoate
1H NMR (CDCl3, 500 MHz, 238C): d=5.82 (m, 1H, CH=
CH2), 5.02 (m, 2H, CH=CH2), 2.39–2.35 (t, J=7.1 Hz, 2H,
CH2CN), 2.09–2.03 (td, 2H, J=6.9 and 1.2 Hz, CH2CH=
CH), 1.77–1.61 (m, 2H, CH2CH2CN), 1.55–1.23 (m, 10H,
CH2); 13C{1H} NMR (CDCl3, 125 MHz, 238C): d=139.0
(CH=CH2), 119.8 (CN), 114.2 (CH=CH2), 33.7, 29.1, 28.9,
28.8, 28.7, 28.6, 25.3, 17.1 (CH2).
These two products were recovered as an analytically pure
mixture after distillation (Tb =1808C at 0.75 mmHg).
1
Linear aldehyde: H NMR (CDCl3, 500 MHz, 238C): d=
9.87 (t, J=1.8 Hz, 1H, CHO), 3.61 (s, 3H, CH3O), 2.36 (td,
J=7.4 and 1.8 Hz, 2H, CH2CHO), 2.25 (t, J=7.5 Hz, 2H,
CH2COOMe), 1.46–1.55 (m, 4H, CH2CH2COOMe and
CH2CH2CHO), 1.16–1.38 (m, 12H, other
6
CH2);
13C{1H} NMR (CDCl3, 125 MHz, 238C): d=202.7 (CHO),
174.2 (COOMe), 51.3 (CH3O), 43.8 (CH2CHO), 34.1, 29.3,
29.2, 29.1, 29.0, 28.8, 24.8, 22.1 (other CH2).
Internal Isomers of Undecenenitrile (1-int)
Typical signals for these internal isomers were observed in
1H NMR (CDCl3, 500 MHz, 238C) at d=5.40–5.20 (m, 2H);
the CH3CH2 signal for cis/trans 8-undecenenitrile was ob-
Branched aldehyde: 1H NMR (CDCl3, 500 MHz, 238C):
d=9.66 (d, J=2.0 Hz, 1H, CHO), 3.61 (s, 3H, CH3O), 2.33–
2.38 (m, 1H, CHCHO), 2.25 (t, J=7.5 Hz, 2H,
CH2COOMe), 1.46–1.55 (m, 4H, CH2CH2COOMe and
CH2CH2CHO), 1.16–1.38 (m, 10H, CH2CH), 1.08 (d, J=
7.0 Hz, 3H, CH3); 13C{1H} NMR (CDCl3, 125 MHz, 238C): d
204.9 (CHO), 174.2 (COOMe), 51.3 (CH3O), 46.2
(CHCHO), 34.8, 29.8, 29.7, 29.6, 29.2, 28.7, 25.5, 23.1 (other
CH2), 14.0 (CH3).
1
served at d=0.92 (t, J=7.3 Hz, 3H); other H signals over-
lap with those of 1 (see the Supporting Information Fig-
ure S5). Alkene signals were also evidenced in 13C{1H} NMR
(CDCl3, 125 MHz, 238C) (see the Supporting Information
Figure S6): trans-9-undecene d=131.3 and 124.7; cis-9-unde-
cene d=130.5 and 123.8; trans-8-undecene d=132.2 and
128.8; cis-8-undecene d=131.8 and 128.8.
General Procedure for Hydroformylation Reactions
Hydroformylation Products Derived from 10-
Undecenal
In a typical experiment, a solution of RhACTHNUTRGENUG(N acac)(CO)2
(0.25 mg, 1.0 mmol), ligand (10 mmol) and 10-undecenitrile
(1, 826 mg, 5.0 mmol) in toluene (10 mL), pre-mixed in
a Schlenk flask, was transferred under argon into a 100-mL
stainless-steel autoclave, equipped with a magnetic stir bar.
The reactor was sealed, flushed several times with CO/H2
(1:1), charged with CO/H2 at the desired pressure at room
temperature, and then heated in an oil bath set at the de-
sired temperature under magnetic stirring. During the reac-
tion, aliquots were sampled at regular time intervals to mon-
itor the conversion and selectivities by NMR and GLC.
After the appropriate reaction time, the reactor was cooled
to room temperature and vented to atmospheric pressure.
The solution was analyzed by GLC and NMR (after evapo-
ration of toluene). The linear/branched (2/3) regioselectivity
was determined by 1H NMR spectroscopy, using the alde-
hyde resonances.
These two products were recovered as an analytically pure
mixture after distillation (Tb =1908C at 0.50 mmHg).
1
Linear aldehyde: H NMR (CDCl3, 500 MHz, 238C): d=
9.73 (t, J=1.8 Hz, 2H, CHO), 2.39 (td, J=7.4 and 1.8 Hz,
4H, CH2CHO), 1.54–1.65 (m, 4H, CH2CH2CHO), 1.18–1.35
(m, 12H, other 6 CH2); 13C{1H} NMR (CDCl3, 125 MHz,
238C): d=202.8 (2CHO), 43.8 (2CH2CHO), 29.3, 29.2, 29.0,
22.0 (other CH2).
Branched aldehyde: 1H NMR (CDCl3, 500 MHz, 238C):
d=9.58 (d, J=2.0 Hz, 2H, CHO), 2.43–2.48 (m, 1H,
CHCHO), 2.39 (td, J=7.4 and 1.8 Hz, 2H, CH2CHO), 1.54–
1.65 (m, 4H, CH2CH2CHO), 1.18–1.35 (m, 12H, other 6
CH2), 1.08 (d, J=7.0 Hz, 3H, CH3); 13C{1H} NMR (CDCl3,
125 MHz, 238C): d=205.0 (CHCHO), 202.8 (CH2CHO),
46.8 (CHCHO), 43.8 (CH2CHO), 29.9, 29.6, 29.6, 29.3, 29.3,
28.2, 26.6, 17.4 (CH2).
Hydroformylation Products (2) and (3) Derived from
10-Undecenenitrile (1)
Hydroformylation Products Derived from 1-Bromo-
10-undecene
These two products were recovered as an analytically pure
These two products were recovered as an analytically pure
mixture after distillation (Tb =1808C at 0.75 mmHg).
Linear aldehyde (2): H NMR (CDCl3, 400 MHz, 238C):
mixture after distillation (Tb =1808C at 0.75 mmHg).
Linear aldehyde: H NMR (CDCl3, 500 MHz, 238C): d=
1
1
d=9.86 (t, J=1.8 Hz, 1H, CHO), 2.37–2.33 (td, J=7.3 and
1.8 Hz, 2H, CH2CHO), 2.39–2.33 (t, J=7.1 Hz, 2H,
CH2CN), 1.65–1.50 (m, 4H, CH2CH2CN and CH2CH2CHO),
1.55–1.15 (m, 12H, other 6 CH2); 13C{1H} NMR (CDCl3,
125 MHz, 238C): d=202.9 (CHO), 119.8 (CN), 43.8
(CH2CHO), 29.3, 29.2, 29.1, 29.0, 28.7, 28.6, 25.4, 22.1, 17.1.
Branched aldehyde (3): 1H NMR (CDCl3, 400 MHz,
238C): d=9.72 (d, J=2.0 Hz, 1H, CHO), 2.39–2.33 (t, J=
7.1 Hz, 2H, CH2CN), 2.18–2.14 (m, 1H, CHCHO), 1.65–
1.50 (m, 2H, CH2CH2CN), 1.55–1.15 (m, 12H, CH2CH),
1.15 (d, J=7.0 Hz, 3H, CH3); 13C{1H} NMR (CDCl3,
125 MHz, 238C): d=205.4 (CHO), 119.8 (CN), 46.8
(CHCHO), 29.3, 29.2, 29.1, 29.0, 28.7, 28.6, 25.4, 22.1, 17.1
(CH2).
9.78 (t, J=1.8 Hz, 1H, CHO), 3.42 (t, J=6.9 Hz, 2H,
CH2Br), 2.41–2.47 (td, J=7.4 and 1.8 Hz, 2H, CH2CHO),
1.42–1.50 (m, 4H, CH2CH2Br and CH2CH2CHO), 1.19–1.40
(m, 14H, other 7 CH2); 13C{1H} NMR (CDCl3, 125 MHz,
238C): d=202.6 (CHO), 43.6 (CH2CHO), 33.8 (CH2Br),
32.6, 29.6, 29.5, 29.4, 29.3, 28.9, 28.6, 28.2, 25.1 (other CH2).
1
Branched aldehyde : H NMR (CDCl3, 500 MHz, 238C):
d=9.62 (d, J=2.0 Hz, 1H, CHO), 3.42 (t, J=6.9 Hz, 2H,
CH2Br), 2.44–2.48 (m, 1H, CHCHO), 1.79–1.85 (m, 2H,
CH2CHCHO), 1.42–1.50 (m, 2H, CH2CH2Br), 1.19–1.40 (m,
12H, CH2CH), 1.11 (d, J=7.0 Hz, 3H, CH3); 13C{1H} NMR
(CDCl3, 125 MHz, 238C): d=204.1 (CHO), 46.1 (CHCHO),
33.8 (CH2Br), 31.3, 29.9, 29.8, 29.6, 28.7, 28.6, 28.0, 26.6
(other CH2), 15.1 (CH3).
Adv. Synth. Catal. 2013, 355, 3191 – 3204
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
3201

Jꢀrꢀmy Ternel et al.
FULL PAPERS
Angew. Chem. Int. Ed. 2011, 50, 10502; b) P. Gallezot,
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2008, 5, 631.
Typical Procedure for Vacuum Distillation of the
Hydroformylation Reaction Mixture and Recycling of
the Catalyst
The crude hydroformylation reaction mixture was trans-
ferred under an argon atmosphere into a 50-mL flask. After
removal of the solvent under reduced pressure at room tem-
perature, the mixture was distillated in a Kꢄgelrohr system
at 1808C at 1 mmHg pressure. Two different fractions were
thus obtained: the pure hydroformylation products were col-
lected in the first flask and the catalyst, in solution with re-
sidual aldehydes and undecenenitrile, was recovered in the
boiler. This residual phase was collected under an inert at-
mosphere and reused, with or without adding fresh ligand,
for a subsequent hydroformylation run.
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Typical Procedure for Oxidation of Aldehydes 2/3
The pure hydroformylation products previously distilled
(5.4 g, 30 mmol) were dissolved in diethyl ether (10 mL) and
the solution was stirred in air for 48 h. A white crystalline
solid progressively formed, which was collected by filtration;
concentration of the solution afforded additional crops of
analytically pure nitrile-carboxylic acids 4/5.
Oxidation Products (4) and (5) Derived from
Hydroformylation Products (2) and (3)
Products 4 and 5 were recovered as an analytically pure
mixture by filtration of the crude oxidation product.
11-Cyano-undecanoic acid (4): 1H NMR (CDCl3,
400 MHz, 238C): d=2.37–2.33 (m, 2H, CH2COOH), 2.39–
2.33 (t, J=7.1 Hz, 2H, CH2CN), 1.65–1.50 (m, 4H,
CH2CH2CN and CH2CH2COOH, 1.55–1.15 (m, 12H,
CH2CH); 13C{1H} NMR (CDCl3, 125 MHz, 238C): d=179.53
(COOH), 119.84 (CN), 33.91 (CH2COOH), 29.23, 29.19,
29.13, 28.98, 28.71, 28.63, 25.35, 24.63, 17.12 (CH2); mp 55–
608C.
10-Cyano-2-methyl-decanoic acid (5): 1H NMR (CDCl3,
400 MHz, 238C): d=2.39–2.33 (t, J=7.1 Hz, 2H, CH2CN),
2.05–1.95 (m, 1H, CHCHO), 1.65–1.50 (m, 2H, CH2-
CH2CN), 1.55–1.15 (m, 12H, CH2CH), 1.15 (d, J=7.0 Hz,
3H, CH3); 13C{1H} NMR (CDCl3, 125 MHz, 238C): d=
177.82 (COOH), 118.62 (CN), 43.89 (CHCOOH), 30.23,
29.82, 29.18, 28.70, 28.55, 26.19, 21.98, 18.71 (CH2), 12.41
(CH3); ESI-HR-MS: m/z=234.1469 [M+Na]+, calcd. for
C12H21NO2Na: 234.1470; m/z=256.1293 [MÀH+2Na]+,
calcd. for C12H20NO2Na2: 256.1289.
[6] J.-L. Dubois, J.-P. Gillet, (to Arkema), WO Patent
Acknowledgements
2008/145941A9, 2008.
[7] HydroxyACTHNUGRTNEUNG(alkoxy)carbonylation of 10-undecenenitrile
This work was supported by the European FP7 Eurobioref
project (No. 241718) and Arkema Co. We thank Umicore Co.
for a generous gift of RhACTHUNTRGNEU(GN acac)(CO)2.
offers a potentially more direct, alternative route to-
wards PA-12; note however that catalytic productivities
and selectivities achieved in Pd-catalyzed hydroxy-
AHCTUNGTRENNUNG
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Adv. Synth. Catal. 2013, 355, 3191 – 3204
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Jꢀrꢀmy Ternel et al.
FULL PAPERS
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above.
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