α,ω-functionalized C19 monomers

Article abstract of DOI:10.1002/cssc.201100187

High-oleic sunflower oil, a renewable resource, is efficiently incorporated into a sustainable and green chemical process: the synthesis of α,ω-functionalized C19 monomers. These monomers, derived from dimethyl 1,19-nonadecanedioate as a novel platform chemical, may find use as feedstock materials for the polymer industry.

Full text of DOI:10.1002/cssc.201100187

DOI: 10.1002/cssc.201100187
a,w-Functionalized C19 Monomers
Guido Walther,[a] Jens Deutsch,[a] Andreas Martin,[a] Franz-Erich Baumann,[b] Dirk Fridag,[c] Robert Franke,[c] and
Angela Kçckritz*[a]
With the increasing efforts to substitute fossil resources by re-
newable ones, there is a strong demand for the establishment
of both new basic chemicals and innovative synthesis meth-
ods. Meeting the high degree of purity needed for monomers
that are used for polymer synthesis is challenging. Intelligent
processing methods are necessary because available feed-
stocks often are mixtures of different components. Linear mol-
ecules are favored for the synthesis of high-grade polymers
such as polyamides or polyesters, but applications of mono-
mers with chain lengths beyond 13 carbons are scarce. Mono-
enic fatty acid derivatives might comprise a well-suited raw
material base because of their preformed linear structure. The
isomerization of the internal double bond to the end of the
chain, which is thermodynamically unfavorable, and further se-
lective reaction at this position to a,w-functionalized mono-
mers seems to be the bottle neck. Only a few successful ideas
have been developed so far. Behr and co-workers obtained
only 36% of the linear product in the hydroformylation of
methyl oleate.[1] A more convincing concept was presented by
Cole-Hamilton and co-workers.[2] The authors reported a highly
selective isomerizing methoxycarbonylation of methyl oleate
to dimethyl 1,19 nonadecanedioate. In the presence of
CH3SO3H and a sterically strongly hindered Pd bisphosphine
catalyst the double bond was shifted initially to the terminal
position in the chain. This reaction step was followed by the
addition of CO and the insertion of a methoxy group, which
proceeded exclusively at the C18 carbon for sterical reasons.
Mecking et al.[3] used this methoxycarbonylation recently for
the synthesis of new polyester types.
Scheme 1. Reaction scheme of a novel synthesis concept to obtain a,w-
functionalized C19 monomers via 1,19-diester 2 from high-oleic sunflower
oil (1; besides oleic acid radicals, 1 does also contain other fatty acid radicals
to a minor degree).
During the last years, intensive studies on the methoxycar-
bonylation of lower olefins and of unsaturated carboxylic acids
and esters have been published in the literature.[2,3,5] According
to our investigations, the formerly used catalytic system Pd/
bis(di-tert-butylphosphinomethyl)-benzene/CH3SO3H[2] is sur-
prisingly capable of a three-stage reaction in one batch. Conse-
quently, 1 was converted directly into 2 via a parallel and/or
subsequent sequence of transesterification/isomerization, and
methoxycarbonylation.[4] The highly selective reaction towards
2 was neither affected by the formation of glycerol nor by
minor components in the technical grade oil 1, such as free
fatty acids (approx. 0.1%) or unsaponifiables (approx. 1.5% lec-
ithin, sterols). Moreover, an up-scaling of the reaction over sev-
eral orders of magnitude was possible without any significant
loss in yield and selectivity.
In this contribution, a more global approach is presented, in-
volving i) catalytic reactions of high selectivity; and ii) the use
of a high-oleic sunflower oil (HOSO) as a vegetable oil (1), in-
stead of fatty esters, in a simplified one-pot procedure
(Scheme 1).[4] Such processing may be advantageous for tech-
nical applications. Thus, the 1,19-diester 2 is utilized as a plat-
form chemical for 1,19-building blocks, leading to novel poly-
mers.
The reaction conditions were optimized on microliter scale
(0.3 mL 1) with variation of the catalyst concentration, the
volumetric ratio of MeOH to 1, and the partial pressure of CO.
The one-pot reaction proceeded well over wide ranges of
these parameters (Table 1). The highest yield of 2 (97%) was
achieved in run 3a. In presence of half the amount of catalyst,
the product yield and selectivity did not significantly decrease
(cf. run 1b and run 3e). The catalyst revealed a limited stability
under reaction conditions. With proceeding reaction, Pd0 was
precipitated in a significant amount. The observed decomposi-
tion of the Pd bisphosphine complex probably resulted from
the protonation of phosphine functions by methanesulfonic
acid, followed by reduction of PdII by MeOH. The methoxycar-
[a] G. Walther, Dr. J. Deutsch, Dr. A. Martin, Dr. A. Kçckritz
Leibniz Institute for Catalysis at the University of Rostock
Albert-Einstein-Str. 29A, 18059 Rostock (Germany)
Fax: (+49)381 1281 289
E-mail: angela.koeckritz@catalysis.de
[b] Dr. F.-E. Baumann
Evonik Degussa GmbH, High Performance Polymers
45764 Marl (Germany)
[c] D. Fridag, Dr. R. Franke
Evonik Oxeno GmbH
45772 Marl (Germany)
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cssc.201100187.
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ChemSusChem 2011, 4, 1052 – 1054

ꢀ10 bar, catalyst concentration 0.5 mol%).[6] Up to now, only
the reduction of 2 to 3 with LiAlH4 has been reported in the lit-
erature.[3,9]
Table 1. Summary of the optimization of reaction parameters for the syn-
thesis of 2 from 1.[a]
Run
cPd
VMeOH/V (1)
pCO
Yield (2)
Selectivity to (2)
Linear aliphatic a,w-diamines are desirable building blocks
for polymers, such as polyamides. Recently, the first direct ami-
nation of primary[10a] and secondary[10b,c] alcohols with ammo-
nia to primary amines using ruthenium phosphine complexes
as catalysts was reported by the groups of Milstein, Beller, and
Vogt. In the present study, the diamine 5 was synthesized for
the first time by direct amination of 3 with ammonia in pres-
ence of carbonylchlorohydrido-(4,5-di-iso-propylphosphino-
methylacridino)ruthenium(II).[10a] Surprisingly, in the solvent 2-
methyl-2-butanol, the reaction proceeded as fast and selective
as reported for the amination of monoalcohols. Secondary
amines and oligomers were only formed to a minor extent.
The target compound 5 was obtained with 68% yield (not op-
timized) at rather mild conditions (1408C) with a catalyst con-
centration of only 0.25 mol% and an excess of ammonia with
respect to the diol.[6]
[mol%]
ratio
[bar]
[%]
[%]
1a
1b
1c
1d
1e
1f
2a
2b
2c
2d
2e
2f
3a
3b
3c
3d
3e
3f
4.8
2.4
1.2
4.8
2.4
1.2
4.8
2.4
1.2
4.8
2.4
1.2
4.8
2.4
1.2
4.8
2.4
1.2
4:1
4:1
4:1
3:1
3:1
3:1
4:1
4:1
4:1
3:1
3:1
3:1
4:1
4:1
4:1
3:1
3:1
3:1
10
10
10
10
10
10
20
20
20
20
20
20
30
30
30
30
30
30
94
95
57
92
85
66
82
84
72
94
66
66
97
85
63
90
91
64
94
95
68
94
87
72
94
93
81
94
92
70
97
89
73
94
93
71
The comprehensive approach presented here allows an effi-
cient and complete incorporation of vegetable oils, such as 1,
into a sustainable and green chemical process. The central role
of 2 as a platform chemical to provide a,w-functionalized C19
hydrocarbons is demonstrated. The diol 4 and the new dia-
[a] Reaction conditions: 0,3 mL 1, nPd/nLigand 1:5, 9.6 mol% CH3SO3H, 808C,
32 h.
bonylation of 40 mL 1 (cf. Experimental Section) gave 86% 2 mine 5 are available under mild catalytic conditions using
(isolated yield) with> 99% purity (corroborated by different chemically efficient procedures. Compounds 2, 4, and 5 might
analytical methods, cf.[6]). For comparison, the corresponding become valuable building blocks for the production of new
two-stage process (transesterification of 1 with MeOH, isolation types of polymers.
of methyl oleate and final isomerization/methoxycarbonylation
towards 2) was carried out under the same reaction condi-
tions. In the first reaction step methyl oleate was obtained
Experimental Section
with 98% yield. The overall yield of 2 after the methoxycarbo-
General procedure for the direct synthesis of 2 from 1: 0.96 mmol
nylation was 68%. The one-pot reaction of HOSO to 2 could (0.216 g) Pd(OAc)2, 4.80 mmol (1.89 g) 1,2-bis[(di-tert-butylphosphi-
no)methyl]benzene, 120 mL MeOH, 41 mmol (36.4 g) 1[11] and
be scaled up to a 12 L batch without any relevant decrease of
19 mmol (1.85 g) CH3SO3H were added consecutively to a stainless
steel autoclave. The reactor was pressurized with CO to 30 bar and
yield and selectivity.
Due to this satisfying availability, the diester 2 is revealed as
held at 808C for 32 h under vigorous stirring. In a three-step se-
a useful platform chemical for the synthesis of highly pure
quence of reprocessing, the reaction products were filtered from
C19-diacid 3, -diol 4, and -diamine 5. The diacid 3 was synthe-
the catalyst using a thermostated Bꢁchner funnel (558C). Then, the
sized by alkaline hydrolysis of 2 with 99% yield (>99% purity
precipitated crude 2 was filtered (À38C) to separate it from un-
after recrystallization).[6] Unfortunately, the direct formation of
reacted educts and washed with cold MeOH (58C) to separate it
3 from 1 in a one-pot reaction with addition of H2O to the re- from the byproduct glycerol. Finally 2 was recrystallized from
methanol.[6]
action mixture failed (reaction conditions: 0.3 mL 1, 0.6 mL
Synthesis of 3: Under vigorous stirring, a solution of 875 mmol
MeOH,
VMeOH/VH O =0.375–6, 2.4 mol% Pd(OAc)2, 12 mol%
2
(49.1 g) KOH in 62.5 mL H2O was added dropwise to a solution of
252 mmol (90 g) 2 in 125 mL EtOH. The resulting mixture was
heated to reflux for 4 h before half concentrated HCl was added to
adjust the pH to 1. The product was washed with H2O and recrys-
tallized twice from glacial acetic acid.[6]
ligand, 9.6 mol% CH3SO3H, 30 bar, 1108C, 32 h). No conversion
was observed. In contrast, traces of water in the used technical
MeOH (0.1%) did not affect the reaction of 1 to 2.
Besides metal hydrides as stoichiometrically used reagents
(e.g., LiAlH4),[3] hydrogen can be utilized in presence of cata-
Synthesis of 4: 0.81 mmol (0.366 g) carbonylhydrido[6-(di-tert-bu-
lysts for the conversion of esters into alcohols.[7] However, only tylphosphinomethylene)-2-(N,N-diethylaminomethyl)-1,6-dihydro-
pyridine]ruthenium(II), 81 mmol (28.91 g) of 2 and 80 mL dioxane
were added to a stainless steel autoclave. The reaction was per-
formed at a pressure of ꢀ 10 bar hydrogen and 1158C for 38 h
under vigorous stirring. After cooling, the product was isolated
and recrystallized from toluene.[6]
Synthesis of 5: 0.025 mmol (0.015 g) carbonylchlorohydrido-(4,5-di-
iso-propylphosphinomethylacridino)ruthenium(II), 10 mmol (3.00 g)
of 3 and 20 mL 2-methyl-2-butanol were transferred into a hastel-
few catalysts are suitable to convert non-activated esters
under mild conditions.[8] The complex carbonylhydrido[6-(di-
tert-butylphosphinomethylene)-2-(N,N-diethylaminomethyl)-
1,6-dihydropyridine]ruthenium(II) revealed an outstanding cat-
alytic activity and proved to be able to catalyze ester hydroge-
nolysis under mild temperature and pressure.[8c] We used this
novel catalyst successfully for the selective reduction of 2 to its
corresponding diol 3 in 98% yield (1158C, H2 pressure loy autoclave. The reactor was pressurized with argon to 15 bar. Af-
ChemSusChem 2011, 4, 1052 – 1054
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Acknowledgements
The authors thank financial support from the Federal Ministry of
Food, Agriculture and Consumer Protection (FKZ 22001308). Dr.
H. Hꢀger and Dr. F.-M. Petrat (High Performance Polymers, Evonik
Degussa GmbH) are acknowledged for helpful discussions.
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Keywords: amination · methoxycarbonylation · polymers ·
renewable resources · sustainable chemistry
ˇ
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Received: April 12, 2011
Published online on June 7, 2011
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