1
FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
& The Patent Rules, 2003
COMPLETE SPECIFICATION
1. TITLE OF THE INVENTION:
METHOD FOR THE CONTROLLED HYDROFORMYLATION AND ISOMERIZATION
OF AN OMEGA-UNSATURATED FATTY NITRILE/ESTER/ACID
2. APPLICANTS:
Name: ARKEMA FRANCE
Nationality: France
Address: 420 rue d'Estienne d'Orves, F-92700 Colombes, France.
Name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE
Nationality: France
Address: 3, Rue Michel-Ange, F-75016 Paris, France.
Name: UNIVERSITE DE RENNES 1
Nationality: France
Address: 2 Rue du Thabor, F-35065 Rennes, France.
3. PREAMBLE TO THE DESCRIPTION:
The following specification particularly describes the invention and the manner in which
it is to be performed:
2
Field of the invention:
The present invention is directed towards a novel method for the synthesis of
fatty nitrile/ester/acid aldehydes and concerns such aldehydes that are linear meeting
formula: OHC-(CH2)r+2-R able to be used in industry, the polymer industry in particular
such as polyamides and polyesters, said method comprising a hydroformylation step of
a ω-unsaturated fatty nitrile/ester/acid.
By "ω-unsaturated fatty nitrile/ester/acid" is meant any compound of formula:
CH2=CH-(CH2)r-R, where R is CN or COOR1,
. R1 being H or an alkyl radical having 1 to 4 carbon atoms,
. r is an integer index such that 1 ≤ r ≤ 13, advantageously 2 ≤ r ≤ 13 and,
preferably, 4 ≤ r ≤ 13.
Prior art:
Current trends in environmental issues in the energy and chemistry sectors
have led to giving priority to the use of natural raw materials from renewable resources.
For example, the polyamide industry uses a whole range of monomers formed
from diamines and diacids, from lactams and from ω-aminoacids. These monomers are
generally manufactured via chemical synthesis using as raw materials C2 to 4 olefins,
cycloalkanes or benzene, hydrocarbons derived from fossil sources. Only a few
monomers are currently manufactured from bio-sourced raw materials such as castor
oil allowing the manufacture of polyamide-11 marketed under the trade nameRilsan®;
erucic oil allowing the manufacture of polyamide-13/13, or lesquerolic oil for the
manufacture of polyamide-13.
Amongst renewable raw materials, the derivatives of fatty acids and in particular
the nitriles and esters of fatty acids have a strong potential for a variety of applications.
The hydroformylationof olefins using catalysts of homogeneous transition metals is a
major industrial method which produces polyvalent intermediates for pharmaceutical
products and fine chemicals.
However, the hydroformylation of derivatives of unsaturated fatty acids, e.g. of
unsaturated fatty nitriles, remains uninvestigated. There exist efficient, selective
catalytic systems for the hydroformylation of C3 to C5 olefins but they prove to be
inefficient and even impossible for alkenes having a longer chain.
3
In addition, throughout the hydroformylationof fatty olefins a certain number of
co-products are formed including isomers of internal alkenes and branched aldehydes
which lead to a reduction in yields and selectivity for desired linear aldehydes.
Patent US7026473 describes the hydroxycarbonylation or
methoxycarbonylation of pentenenitrile to 5-cyanovaleric acid or its ester (6 carbon
atoms) in the presence of CO (carbon monoxide) and water or alcohol respectively.
Solely an example of methoxycarbonylation with methanol is given. Via reduction, the
5-cyanovaleric acid (ester) forms 6-aminocaproic acid (ester), which in turn gives
e-caprolactam by cyclisation (the monomer of Nylon-6). The method described inthis
document has several drawbacks. The methoxycarbonylation step is slow and costly in
terms of catalyst. Conversion is not complete and requires lengthy reaction times. In
addition, on account of rapid isomerization there is shifting of the double bond even if it
is terminal leading to the formation of numerous co-products such as those mentioned
above, in particular branched products which have to be separated from the linear
product it is sought to produce. The document of patent WO97/33854 describes a
method to manufacture a linear aldehyde by hydroformylationof an alkene such as
hexene, butadiene, methyl 3-pentenoate or 3-pentenenitrile. This document shows that
it is much more difficult to obtain a linear aldehyde (small proportion of linear products
obtained) from a nitrile (3-pentenenitrile) than from an ester. Additionally, in prior art
hydroformylationfrom a nitrile a high proportion (21%, 16.3%) of reduced product is
obtained (valeronitrile), i.e. not containing any aldehyde due to hydrogenation of the
double bond by the catalyst. The obtaining of linear products with these methodsis
detrimental to conversion. In addition, the methods described in these documents do
not concern the manufacture of bio-resourced products.
The document of patent US6307108 describes methods to manufacture an
ester aldehyde by hydroformylation of ω-unsaturated ester.
As indicated above, existing hydroformylation methods generally lead to the
production of isomers of the starting reactant via isomerization of the double bond.
When these isomers are recycled back to the reaction they could to a certain extent
give backthe starting reactant by isomerization, but they also lead to undesirable coproducts,
i.e. branched aldehydes by hydroformylationof the internal double bond. Also,
these isomers are much less reactive than the initial ω-unsaturated compounds. As a
result, if they are fully recycled back to the reaction they will gradually build up until
they represent the most part of the reaction medium. In the methods described in the
prior art hydroformylationis generally performed with very long reaction times of at least
20 hours to promote conversion of initial reactants and isomerization products.
4
Productivity is therefore low. In addition the hydroformylation reaction is generally
conduct ina solvent medium in particular for recovery and recycling of the catalyst
(metal and ligands).
It is therefore the objective of the present invention to find a novel
hydroformylationmethod that is easy to implement and uses renewable raw materials
inasmuch as is possible.
In particular the present invention sets out to increase the productivity of the
hydroformylationreaction to obtain linear aldehydes, these linear aldehydes being
defined as those that are not branched, to improve product quality, reaction selectivity,
to minimize the obtaining of co-products, and in particular co-products of branched
aldehyde type, using the least possible amount of catalyst and therefore to target the
improved general economics of the method.
It is one particular objective of the present invention to simplify the
hydroformylationmethod applied to a ω-unsaturated fatty nitrile/ester/acid substrateand
to reduce the number of steps and ingredients used whilst allowing recycling of the
catalyst back to the reaction.
The Applicant has now discovered a novel method for the hydroformylationof an
unsaturated fatty nitrile/ester/acid substrate under conditions allowing the avoiding of
the aforementioned disadvantages, in particular by controlling parallel isomerization of
said substrate which leads to the formation of co-products including branched
aldehydes, the method allowing both improved productivity and selectivity as well as
efficient recycling of the hydroformylation catalyst.
Detailed description of the invention:
In the present description it is specified that when reference is made to ranges
the expressions of type "ranging from…to…" or "containing/comprising from… to…"
include the limits of the range. Conversely, expressions of the type "of between
…and…" exclude the limits of the range.
Unless otherwise indicated, percentages are expressed as molar percentages.
Unless otherwise indicated, the parameters to which reference is made are
measured under atmospheric pressure.
It is also specified that in the present description a "linear aldehyde" is an
aldehyde in which carbon monoxide has been added to the terminal carbon of the
olefin during hydroformylation, as opposed to a "branched aldehyde" in which carbon
monoxide has been added onto an internal carbon of the olefin.
5
Similarly, a "terminal isomer" is an isomer in which the unsaturation (double
bond) is terminal, as opposed to an "internal isomer", also called "isomer with internal
unsaturation" and denoted [1-int] wherein the unsaturation is not terminal.
The subject of the present invention is therefore a method to prepare a fatty
nitrile/ester aldehyde comprising the following steps:
1) hydroformylationof a ω-unsaturated fatty nitrile/ester/acid substrateselected from
among the compounds of formula:
CH2=CH-(CH2)r-R, where R is CN or COOR1,
. R1 being H or an alkyl radical having 1 to 4 carbon atoms,
. r is an integer index such that 1 ≤ r ≤ 13, advantageously 2 ≤ r ≤ 13 and,
preferably 4 ≤ r ≤ 13,
wherein said substrate is reacted with carbon monoxide and dihydrogen under the
following conditions:
- CO partial pressure, denotedPiCO, of 40 bar or lower, preferably in the range
of 5 to 20 bar,H2partialpressure denotedPiH2, of 40 bar or lower, preferably in
the range of 5 to 20 bar, and the ratio PiCO/PiH2 between the respective
partial pressures of CO and H2 is in the range of 0.5:1 to 3:1,
- temperature in the range of 70 to 150°C, preferably 100 to 130°C, more
preferably 100 to 120°C,
- reaction time of 24 h or less,
- in the presence of a catalyst comprising at least one group VIII metal,
preferably at least one metal selected from among rhodium, cobalt, ruthenium,
iridium and the mixtures thereof, preferably selected from among rhodium,
iridium and the mixtures thereof; and at least one bidentate ormonodentate
ligand, preferably at least one chelating diphosphine,
- [substrate]/[metal] molar ratio in the range of 5 000 to 100 000,
- [ligand]/[metal] molar ratioin the range of 10:1 to 100:1,
so as to obtain after the reaction:
. ahydroformylation product comprising at least one fatty nitrile/ester/acid aldehyde
of formula: OHC-(CH2)r+2-R, and
. anisomerate comprising at least one fatty nitrile/ester/acid isomer with internal
saturation, at least 80% of the internal isomer(s) of the isomerate being formed
of the ω-1 unsaturated isomer of formula CH3-CH=CH-(CH2)r-1-R; followed by:
2) separation and recovery of the fatty nitrile/ester/acid aldehyde and of the isomerate.
It is ascertained that by controlling the total % of internal olefins [1-int] obtained
after the hydroformylation step, and by optimizing the distribution of these internal
6
olefins, by regulating parameters of pressure, temperature, reaction time and use of
catalyst conforming to the hydroformylation method of the invention, the method of the
inventionis precisely able to:
- improve regioselectivity regarding linear aldehydes/branched aldehydes which
are respectively denoted 2 and3in the reaction scheme and in the tables of the
examples below: 95:5 or higher, preferably 97:3 or higher; more preferably
99:1 or higher, i.e. to reduce the obtaining of branched aldehydes3,
and to optimize one or more of the other following parameters:
- improve chemoselectivity for hydroformylation products, denoted2+3: 70% or
higher and preferably 80% or higher;
- preferably increase the conversion rate of ω-unsaturated fatty nitrile/ester/acid
reactant (denoted1in the reaction scheme and in the tables of examples
below) to end products, i.e. to hydroformylation products (2 and3, but
especially2)and isomerate(denoted1-int in the reaction scheme and tables of
examples below),up to a value of at least 90%, a value on and after which
there exists strong industrial advantage;
- minimize % hydrogenation product of the double bond, the hydrogenation
product being denoted 4 in the reaction scheme and tables of examples
below: preferably no more than 7 %, more preferably no more than 5 %;
- efficiently recycle the catalyst;
- increase TON > 100 000, TON(turnover number) being defined as the number
of moles of converted ω-unsaturated fatty nitrile/ester/acidper mole of catalyst.
Step 2) to separate and recover the fatty nitrile/ester/acid aldehyde and
isomerate stops shifting of the internal unsaturation of the isomers via isomerization
and allows enhanced re-use of the isomerate.
Rather than recycling the internal isomers [1-int] in the hydroformylation
reaction (hereafter "HF"), or lengthening the hydroformylation reaction time to allow the
catalyst to isomerize the internal isomers to terminal isomers, and then
hydroformylating to linear aldehyde, the method of the invention implements the
hydroformylation step with gains in productivity translating as a hydroformylation step
which takes place in the shortest time possible and sufficient to obtain complete or
near-complete conversion(preferably > 90%, even 100%). With the method of the
invention it is possible to avoid recycling, to haltisomerization of the isomers, to reduce
the obtaining of hydrogenation product and thereby improve selectivity for linear
aldehyde.
7
In fact the technical solution of the method of the invention is to operate with
high (even complete) conversion of initial reactant without however seeking to convert
the isomerization products of this initial reactant, high conversion meaning a
conversion rate of at least 90%.
Unexpectedly, it is the control over synthesis of the isomers, and in particular
the halting of their isomerization through recovery thereof after the hydroformylation
step, which allows slowing of the reaction to be avoided, the HF catalyst to be
efficiently recycled and the productivity and selectivity of the HF reaction to be
increased.
The initial omega-unsaturated reactant:
- is partly converted by hydroformylation to fatty nitrile/ester/acid aldehyde that is
essentially linear 2 (preferably containing no more than 5% of branched compounds3),
and
- partly converted to1-intisomers characterized by limited (controlled) shifting of the
double bond towards internal positions, the internal isomers comprising at least 80 %
ofω-1 isomers.
In one particularly advantageous variant of the invention, the ω-unsaturated
fatty nitrile/ester/acid substratemeets formula CH2=CH-(CH2)r-R, with R=COOR1, R1
being H or an alkyl radical having 1 to 4 carbon atoms.
In the present description, "ω-x" indicates the position of the first unsaturation
starting from the side opposite the nitrile, ester or acid R group.
By "isomerate" in the meaning of the invention is meant at least one isomer with
internal unsaturation (ω-x: ω-1, ω-2, ω-3…) of the ω-unsaturated fatty
nitrile/ester/acid,which has a terminal unsaturation, the said isomerate possibly also
containing the initial non-converted substrate, i.e. the ω-unsaturated fatty
nitrile/ester/acid. The internal isomers of the isomerate may be cis and/or trans.
By "unsaturated fatty nitrile/ester/acid”in the meaning of the present invention is
to be understood unsaturated fatty nitrile or ester or acid, i.e. unsaturated fatty nitrile or
unsaturated fatty ester or unsaturated fatty acid.
By "ω-unsaturated fatty nitrile/ester/acid substrate" is meant an "unsaturated
fatty nitrile/ester/acid" of which at least 90 % comprises a terminal "ω" unsaturation, the
said substrate possibly comprising no more than 10 % of ω-1 unsaturated fatty
nitrile/ester/acid, i.e. no more than 10 % of "unsaturated fatty nitrile/ester/acid" having
an internal ω-1 unsaturation. In the event that the“ω-unsaturated fatty nitrile/ester/acid
substrate" should comprise saturated compounds, the latter not reacting during the
8
hydroformylation reaction, these must be removed after his reaction as must be the
hydrogenation product of the double bond 4.
The starting unsaturated fatty nitrile used in the method of the invention is
generally obtained from unsaturated (or hydroxylated) fatty acid or ester compounds by
nitrilation (ammoniation) of at least one acid or ester function of these compounds
which may be derived from raw materials of fossil origin or from renewable sources.
The unsaturated fatty acid or ester compounds can be obtained for example
using the method described in the document of patent US4510331. This document
particularly describes the preparation of 7-octenoic acid by isomerization of
2,7-octadien-1-ol to 7-octen-1-al, followed by oxidization of the latter to acid.
2,7-octadien-1-ol is produced industrially by reaction ("telomerization") of butadiene
with water in the presence of palladium catalyst in accordance with the method
described in the documents of patents GB2074156A and DE3112213. This type of
method uses raw materials of fossil origin.
Alternatively, unsaturated fatty nitriles are produced from unsaturated fatty acids
or esters of renewable origin, derived from natural oils. Thesemethods recently
developed by Arkema are notably described in the documents of patents:
WO2010055273, FR11.55174, FR11.56526 and FR11.57542.
By unsaturated fatty nitrile in the meaning of the invention is preferably meant
those obtained at least in part from natural unsaturated fatty acids.
Said unsaturated fatty nitrile can be obtained in particular from an unsaturated
fatty acid (or ester) of natural origin of formula:
(R’-CH=CH-[(CH2)q-CH=CH]m-(CH2)n-COO-)p-G
wherein: R’ is H, an alkyl radical having 1 to 11 carbon atoms optionally
containing a hydroxyl function,
q equals 0 or 1,
mis an integer index in the range of 0 to 5 and preferably 0 to 2,
n is an integer index in the range of 2 to 13,
p is an integer index such that 1 ≤ p ≤ 3, and
G is H (a hydrogen), an alkyl radical having 1 to 11 carbon atoms or a
radical having 2 to 3 carbon atoms carrying 1 or 2 hydroxyl functions,
the double bond(s) C=C possibly being of cis or trans conformation,
said preparation comprising the ammoniation (action whereby ammonia is added to a
product) of the carbonyl function of the unsaturated fatty acid (or ester) of natural origin
to a nitrile function.
9
The reaction scheme of the synthesis of nitriles from acids via ammoniation (or
nitrilation, the two terms being used indifferently) well known to persons skilled in the
art can be summarized as follows:
R-COOH + NH3 → [R-COO-NH4
+] → [R-CONH2] + H2O → RCN + H2O
This scheme applies both to natural fatty acids (esters) and to ω-unsaturated
fatty acids. The method can be a batch method in liquid or gas phase or a
continuousmethod in gas phase. The reaction is conducted at high temperature, higher
than 250°C and in the presence of catalyst which is generally a metal oxide and most
frequently zinc oxide. The continuous removal of the water formed also carries off the
ammonia which has not reacted and allows rapid completion of the reaction.
Ammoniation in liquid phase is well adapted for long fatty chains (having at least
10 carbon atoms). However, when operating with shorter chain lengths,ammoniation in
gas phase may become more suitable. It is also known from GB 641,955 to conduct
ammoniation using urea or cyanuric acid as agent. Any other ammonia source may
also be used.
According to one particular embodiment, the unsaturated fatty nitrile used in the
invention is produced from natural long chain unsaturated fatty acids. By "natural long
chain fatty acid" is meant an acid derived from the vegetable or animal kingdom
including algae or othermicro-organisms, and hence renewable, having 6 to 24 carbon
atoms, preferably having at least 7 carbon atoms (if the final aminoacid has at least
8 C), more preferably at least 8 carbon atoms, further preferably at least 10 carbon
atoms and still further preferably at least 14 carbon atoms per molecule. These various
acids are derived from vegetable oils extracted from various plants such as sunflower,
rapeseed,camelina, castor, lesquerella, olive, soybean, palm, coriander, celery, dill,
carrot, fennel, Limnanthes Alba (meadowfoam). They are also derived from the animal
world, whether land or marine and in the latter case both in the form of fish and
mammals as well as algae. In general it is in the form of fats from ruminants, fish such
as cod or sea mammals such as whales or dolphins.
As unsaturated fatty acid more particularly suitable for implementing the
invention, mention can be made of the following: petroselenic acid (cis-6-octadecenoic
acid), its derivative 6-heptenoic acid obtained by ethenolysis (cross metathesis with
ethylene), α-linolenic acid (6-9-12-octadecatrienoic), these acids able to be obtained
from coriander for example; cis-8-eicosenoic acid, cis-5,8,11,14- eicosatrienoic acid
(arachidonic acid), ricinoleic acidwhich after dehydration gives conjugated
8,10-octadecadienoic acid; caproleic acid (cis-9-decenoic), palmitoleic acid
(cis-9-hexadecenoic), myristoleic acid (cis-9-tetradecenoic), oleic acid
10
(cis-9-octadecenoic), 9-decenoic acid obtained by ethenolysis of an oleic acid for
example, elaidic acid (trans-9-octadecenoic), ricinoleic acid (12-hydroxy-cis-9-
octadecenoic), gadoleic acid (cis-9-eicosenoic), linoleic acid (9-12-octadecadienoic),
rumenic acid (9-11-octadecadienoic), conjugated linoleic acid (9-11-octadecadienoic),
these acids able to be obtained from sunflower seed, rapeseed, castor, olive, soybean,
palm, flax, avocado, sea-buckthorn, coriander, celery, dill, carrot, fennel, Limnanthes
(meadowfoam); 10-12 conjugated linoleic acid (10-12-octadecadienoic),
10-undecylenic acid obtained by thermal cracking of the methyl ester of ricinoleic acid
for example; vaccenic acid (cis-11-octadecenoic), gondoic acid (cis-11-eicosenoic),
lesquerolic acid (14-hydroxy-cis-11-eicosenoic), cetoleic acid (cis-11-docosenoic) able
to be obtained fromLesquerella oil (lesquerolic), Camelina sativa oil (gondoic), oil from
a plant of the Sapindaceae family, from fish fat, oil from microalgae (cetoleic) by
dehydration of 12-hydroxystearic acid itself obtained by hydrogenation of ricinoleic acid
(vaccenic acid and itstransequivalent), of conjugatedlinioleic acid
(9-11-octadecadienoic), obtained for example by dehydration of ricinoleic acid;
12-octadecenoic acid(cis ortrans) obtained for example by dehydration of
12-hydroxystearic aid (abbreviated 12HSA) itself obtained by hydrogenation of
ricinoleic acid, 10-12 conjugated linoleic acid (10-12-octadecadienoic), 12-tridecenoic
acid obtainedby thermal cracking of the ester (methyl ester in particular) of lesquerolic
acid; erucic acid (cis-13-docosenoic) and brassidic (trans-13-docosenoic) which can be
obtained for example from erucic rapeseed, Lunaria or CrambeMaritima; 13-eicosenoic
acid (cis or trans) obtained by dehydration of 14-hydroxyeicosanoic acid itself obtained
by hydrogenation of lesquerolic acid, 14-eicosenoic acid (cis ortrans) obtained by
dehydration of 14-hydroxyeicosanoic acid (abbreviation 14HEA) itself obtained by
hydrogenation of lesquerolic acid (dehydration can be conducted on both sides ofOH),
nervonic acid (cis-15-tetracosoic) which can be obtained from Malaniaoleifera and
Lunaria(lunariaannuaalso known under the name of silver dollar, money plant,
honesty); or the mixtures thereof. It is also possible to omit the dehydration step of the
12HSA and 14HEA acids by conducting conversion to nitrile directly on these
saturated, hydroxylated fatty acids as described in the document of the patent filed
under number FR11.56526. One advantage of this solution is that the hydrogenation of
ricinoleic acid in a mixture with the other fatty acids of castor oil leads to a mixture that
onlycontains 12HSA acid, stearic acid and palmitic acid as majority species.
Dehydration following (or simultaneously with) conversion to nitrile leads to a very
clean nitrile containing more than 85 % of monounsaturated nitrile. The same applies to
14HEA, as described in the document of patent FR11.56526.
11
Amongst the aforementioned unsaturated fatty acids, preference is given to
those which are most abundantly available and in particular unsaturated fatty acids at
position δ-9 or δ-10 with numbering starting from the acid group. Preference is
effectively given to the use of fatty nitriles and acids having 10 to 24 carbon atoms, and
preferably those having 10 carbons or 11 carbons with an unsaturation at
omega,orω position, i.e. at the end of the chain in relation to the acid group. For
example preference is given to fatty acids with 18 carbons having an unsaturation at
position δ-9 or 10 in relation to the nitrile or acid group, i.e. at position ω-9 or 8
respectively which by ethenolysisor butenolysis or other cross metathesis with an olefin
will lead to ω-unsaturated acids, and to ricinoleic acid which via thermal cracking of its
methyl ester gives the methyl ester of undecylenic acid.
The above-mentioned fatty acids can be isolated using any technique well
known to persons skilled in the art: molecular distillation including short path distillation,
crystallization, liquid-liquid extraction, complexing with urea including extraction with
supercritical CO2 and/or any combination of these techniques.
According to one particular embodiment of the method of the invention, the
unsaturated fatty nitrile is obtained from a fatty acid ester, the latter advantageously
being possibly selected from among the esters of the aforementioned fatty acids, in
particular the methyl esters thereof. The paths to obtain a fatty nitrile from a fatty acid
ester are described for example in document WO2010089512.
According to another embodiment, the unsaturated fatty nitrile is obtained from
a hydroxy fatty acid such as 12HSA and 14HEA. More generally the hydroxy fatty acid
can advantageously be selected from among those described in the patent application
filed under number FR11.56526.
Alternatively, the unsaturated fatty nitrile is obtained from a triglyceride, the
latter advantageously being possibly selected from among: a vegetable oil comprising
a mixture of triglycerides of unsaturated fatty acids such has sunflower seed oil,
rapeseed oil, castor oil, lesquerella, camelina, olive, soybean, palm, Sapindaceae in
particular avocado, sea buckthorn, coriander, celery, dill, carrot, fennel, mango,
Limnanthes Alba (meadowfoam) and the mixtures thereof; micro-algae; animal fats.
According to another embodiment, the unsaturated fatty nitrile is obtained from
a vegetable wax e.g. jojoba.
The obtaining of said unsaturated fatty nitrile from an unsaturated fatty
acid/ester is notably described in patent application WO2010055273, in particular under
the paragraphsdescribing the "first stage" ofthe method subjectof this document: i.e.
12
page 5 lines 12 to 32, page 7 lines 17 to 26, page 8 lines 1 to 9, page 10 line
29 to page 11 line 19.
According to one particular embodiment of the method of the invention, a
ω-unsaturated nitrile of formula CH2=CH-(CH2)p-CN obtained by conversion of an
unsaturated fatty acid/ester in two successive steps (of indifferent order) is used:
ethenolysis (cross metathesis with ethylene) and ammoniation, such as described in
document WO2010055273. According to another variant of the method, hydroxylated
fatty acids are used as raw material such as ricinoleic acid andlesquerolic acid which
meet the general formula R1 -CH=CH-(CH2)p-COOH where R1 is
CH3-(CH2)5CHOH-CH2- and p is 7 and 9 respectively. The acid in its methyl ester form
is subjected to pyrolysis leading to a ω-unsaturated ester of formula
CH2=CH-(CH2)p+1-COOCH3 which is converted by ammoniation, directly or via the acid,
to a ω-unsaturated nitrile. According to a further embodiment, the unsaturated fatty
nitrile is produced as described in document FR11.55174 viaammoniation of a
compound of fatty acid, ester or glyceride type leading to the corresponding
unsaturated nitrile. According to one particular embodiment of the invention,
hydrogenation of unsaturated hydroxylated fatty acids is conducted as described in the
method of document FR11.56526, these fatty acids containing at least 18 carbon
atoms per molecule, leading to saturated hydroxylated fatty acids, followed by
dehydration thereof leading to mono-unsaturated fatty acids, with in addition either an
intermediate nitrilation step of the acid function of the mono-unsaturated fatty acid
leading to an unsaturated nitrile, or an intermediate nitrilation step of the acid function
of the saturated hydroxylated fatty acid derived from the hydrogenation step with
concomitant dehydration leading to an unsaturated fatty nitrile. Particular conditions for
obtaining unsaturated fatty nitriles are described in document FR11.57542, comprising
the nitrilation of a ω-unsaturated acid/ester of formula CH2=CH–(CH2)n-COOR wherein
n is 7 or 8 and R is either H or an alkyl radical having 1 to 4 carbon atoms, via action of
ammonia in a reactor under continuous operation in gas phase or mixed gas-liquid
phase in the presence of a solid catalyst.
1) HYDROFORMYLATION
Hydroformylation, also called oxomethod, is a synthesis path for the preparation
of aldehydes from alkenes, discovered in 1938 by Otto Roelen atRuhrchemie. The
basic reaction is the following:
13
This method is widely used industrially to produce aldehydes in the C3-C19
range. Butanalis the main product synthesized by this reaction with about 75 % of total
production using hydroformylation as synthesis pathway. The hydroformylation step in
the method of the invention uses well known methods and devices alreadyemployed in
conventional hydroformylationmethods. All the usual modes for the adding and mixing
of reagents and components of catalyst(s) and usual separation techniques for the
conventional hydroformylation reaction can therefore be applied for this step in the
method of the invention. The hydroformylation stepfollowed in the method of the
invention has the advantage that it can be used directly in numerous existing devices.
This would not be the case for methoxycarbonylation or hydroxycarbonylationfor
example.
According to the invention, the pressure conditions of the hydroformylation
reaction are the following:
- CO partial pressure is 40 bar or lower,
- H2partial pressure is 40 bar or lower, and
- the ratio PiCO/PiH2 between the respective CO and H2 partial pressures is
in the range of 0.5:1 to 3:1.
In a first variant of the invention, hydroformylation is conducted under CO
partialpressure in the range of 5 to 20 barand advantageously in the range of 10 to 20
bar.
In a second more particularly advantageous embodiment,hydroformylationis
conducted under CO partialpressure in the range of 5 to 40 bar and preferably in the
range of 10 to 40 bar.
Advantageously, hydroformylationis conducted under H2 partial pressure in the
range of 5 to 20 barand preferably in the range of 10 to 20 bar.
Advantageously, the PiCO/PiH2 ratio between the respective CO and H2partial
pressures is in the range of 1:1 to 3:1.
It is to be noted that the more thePiCO/PiH2ratio tends towards the value of 3:1,
the more the formation of the ω-1 unsaturated isomer having the formula CH3-CH=CH-
(CH2)r-1-R is promoted.
Preferably, hydroformylationis conducted at a temperature in the range of 100
to 130°C, preferably 100 to 120°C, preferably at a temperature of substantially 120 °C.
Advantageously, hydroformylationis performed for a time in the range of 1 to 12h,
preferably in the range of 2 to 6 h, preferably in the range of 3 to 5 h, preferably in the
order of 4 h.
14
Hydroformylationis preferably carried out until a conversion rate of
ω-unsaturated fatty nitrile/ester/acid reactant is obtained in the range of 90 to 100%,
preferably in the range of 95 to 100%, preferably in the range of 97 to 100%.
Hydroformylationis carried out in the presence of a catalyst, this catalyst
comprising at least one Group VIII metal and at least one ligand, this ligand possibly
being monodentate or bidentate.
Advantageously, the catalyst comprises at least one phosphine, phosphite or
chelating diphosphine selected from among: PPh3, P(OPh)3, Dppm, Dppe, Dppb,
Xantphos and/or BiPhePhos, preferably Xantphos and/orBiPhePhos,
preferablyBiPhePhos.
Ph2P PPh2 Ph2P PPh2
Dppm Dppe
Ph2P
PPh2
Dppb
P
Ph
Ph Ph
P
OPh
PhO OPh
PPh3 P(OPh)3
O
PPh2 PPh2
Xantphos
In one particularly advantageous version of the invention, the ligand of the
catalyst is a bidentate ligand, which may in particular be a chelating diphosphine. The
chelating diphosphinemay be selected in particular from among Dppm, Dppe, Dppb,
Xantphos and/orBiPhePhos. This chelatingdiphosphineis preferably selected from
among Xantphos and/orBiPhePhos, and is more preferably BiPhePhos.
Advantageously, the metal of the catalyst is provided in the form of a precursor
comprising said metal and at least one compound selected from among
15
acetylacetonates, carbonyl compounds, cyclooctadienes, chlorine, and the mixtures
thereof. Advantageously, the hydroformylation catalyst comprisesrhodium,preferably
provided by a precursor such as Rh(acac)(CO)2, ruthenium, preferably provided by a
precursor such as Ru3(CO)12, where acac is an acetylacetonate ligand and CO is a
carbonyl ligand, and/or iridium, preferably provided by a precursor such as Ir(COD)Cl
where COD is a 1,5-cyclooctadiene ligand and Cl is a chlorine ligand, preferably it
comprises iridium. Advantageously hydroformylation is catalyzed by a system selected
from among: Rh-Xantphos, Rh-BiPhePhos, Ir-Xantphos, Ir-BiPhePhos and the
mixtures thereof.
The rhodium and iridiumcatalysts are preferred, they substantially improve
conversion. Rhodium and iridium catalysts have better selectivity for aldehydes, cause
less hydrogenation as parallel reaction and offer linear product/branched product ratios
distinctly in favor of linear products.
Preferably, the hydroformylation catalyst comprises rhodium, preferably
provided by a precursor such as Rh(acac)(CO)2, ruthenium, preferably provided by a
precursor such as Ru3(CO)12, where acac is anacetylacetonate ligand and CO is a
carbony ligand, and/or iridium preferably provided by a precursor such as Ir(COD)Cl
where COD is a 1,5-cyclooctadiene ligand and Cl is a chlorine ligand, and preferably
comprises iridium. Hydroformylation is advantageously catalyzed by a system selected
from among: Rh-Xantphos, Rh-BiPhePhos, Ir-Xantphos, Ir-BiPhePhosand the mixtures
thereof.
Preferably the [substrate]/[metal] molar ratio is in the range of 5000 to 50 000.
This embodiment of the method of the invention is particularly advantageous in
that an essentially linear hydroformylation product is obtained whilst only using a very
small amount of metal, which evidently is of appreciable economic interest at industrial
level.
In one particularly advantageous embodiment, the preparation methodof the
invention further comprises a pre-treatment step of the substrate prior to the
hydroformylation step.
This pre-treatment step is intended to remove any oxidization products of the
fatty nitrile/ester/acid substrate such as hydroperoxidesand degradation products of
these hydroperoxides,which might attack the metal of the catalyst used during the
hydroformylation reaction, to the detriment of the reactivity of said catalyst.
Said pre-treatment can be performed for example by distillation of the substrate
followed by purification via adsorption thereof in particular using alumina.
16
Preferably the [ligand]/[metal] molar ratio is in the range of 20:1 to 100:1,
preferably 40:1 to 100:1.
Advantageously,hydroformylationis carried out using a sufficient amount of
solvent to solubilize at least part of the catalyst (in particular one of the precursors or
both precursors of the catalyst), preferably in an amount of less than 1%, preferably
less than 1/1000 relative to the ω-unsaturated fatty nitrile/ester/acid reactant.
Therefore, hydroformylation can be conducted in an organic medium, e.g. in
solution in toluene, but it is preferably "solvent-free", i.e. in an amount less than 1%,
preferably less than 1/1000 relative to the ω-unsaturated fatty nitrile/ester/acid reactant.
According to one particular embodiment of the method of the invention, the
hydroformylationstep comprises the recycling of the hydroformylation catalyst system,
optionally completed by a supply of new (or "fresh") catalystand/or new (or "fresh")
ligand at a subsequent hydroformylation cycle.
2) SEPARATION AND RECOVERY
During the method, after halting the hydroformylation reaction, the products are
evaporated from the reaction medium to recover on the one hand the isomerate and on
the other hand the hydroformylation products.
Preferably, in a first fraction are recovered the isomers of the initial reactant–
and the initial reactant which has not reacted - and in a second fraction the nitrile
(ester) aldehydes derived from the hydroformylation reaction.
Advantageously, evaporation of the reaction medium is not complete so that it is
possible to recycle the catalyst and ligands back to the reaction.
When the reaction leads to an isomerate yield (containing the isomers of the
initial reactant) of several percent, this mixture could be recycled back to the reaction
having regard to the high cost of these raw materials. However, it is found that the
mixture of isomers is much less reactive than the initial reactant which has a terminal
double bond. Extensive recycling of isomerate leads to a phenomenon of build-up. In
addition, these isomers continue to isomerize, the double bond continues to be shifted
which in the end leads to more branched hydroformylation products (aldehydes) and
diminishes the quality of the end product. The method of the invention, and in particular
step 2), overcomes all these problems and, on the contrary, targets enhanced recovery
of the obtainedisomerate which finds numerous applications.
The hydroformylationmethod of the invention consumes compounds having a
terminal double bond easily and rapidly. As a result, the method allows the separating
of the compounds with internal double bond from the compounds with terminal double
17
bond. Since these isomers usually have very close physicochemical properties, they
are not easy to separate. Yet under the operating conditions applied in the method of
the invention, the isomer with terminal double bond is converted to a linear aldehyde
which means that the problem of separating internal and terminal isomers practically no
longer exists. The separation of the internal isomers is thereby facilitated.
The isomerate or isomers thus isolated find applications in the field of flavorings
and perfumes. For example Givaudan claimed (EP1174117) the use of said mixture of
isomers in formulations. The method for producing isomerate according to the invention
is also much simpler than prior art methods, as shown for example in the
aforementioned Givaudan patent document in the prior art and synthesis examples 1).
The methyl esters obtained following the method of the invention an also be
used for these applications. Reference can be made to the Sigma-Aldrich catalogue
"Flavors and Fragrances, 2003-2004" but also to the website
www.thegoodscentscompany.com which give numerous properties of these different
isomers. The esters obtained can also be converted to acids, aldehydes and alcohols
which in turn also have applications such as flavorings and perfumes.
Advantageously the method of the invention further comprises a step:
- to separate and recover isomers from the isomerate, and/or
- to convert at least one isomer of the isomerate to isomer derivative(s), in particular by
conversion of one or more isomer function(s) to an acid, aldehyde, alcohol and/or
amine function and/or by reaction(s) of the internal double bond of the isomers, in
particular by hydrogenation, epoxidation and/or polymerization.
Advantageously, the method of the invention further comprises the valorization
of the isomerate or of at least one of its isomers or the derivatives thereof, the said
valorization being selected from among: use, in particular as flavoring or perfume, in a
perfume composition, in particular in functional perfume products, in a composition of a
cosmetic or pharmaceutical product, in the textile industry, in the metal transformation
industry, as monomer in the polymer industry, in particular as monomer of an odor-free
or perfumed preparation: use as lubricant, emulsifying agent, surfactant, foam reducing
agent, conditioning agent, levelling agent, antistatic agent, solubilizing agent for inks, in
particular printing inks, cooling fluid and/or anticorrosion agent, these products possibly
being perfumed or odor-free.
A further subject of the invention is an isomerate able to be obtained with the
method of the invention, characterized in that it comprises at least one fatty
nitrile/ester/acid isomer with internal unsaturation, of which at least 80 % of the internal
18
isomer(s) of the isomerate are formed of the ω-1 unsaturated isomer of formula
CH3-CH=CH-(CH2)r-1-R.
A further subject of the present invention is the use of an isomerate of the
invention, or of at least one of the isomers thereof, or of their derivatives obtained in
particular with the method of the invention, particularly used as flavoring or perfume, in
a perfumecomposition, particularly a functional perfume,in a cosmetic or
pharmaceutical composition, in the textile industry, in the metal transformation industry,
as monomer in the polymer industry, in particular as monomer of an odor-free or
perfumed preparation; a product used as lubricant, emulsifying agent, surfactant, foamreducing
agent, conditioning agent, levelling agent, antistatic agent, solubilizing agent
for inks and in particular printing inks, cooling fluid and/or anticorrosion agent, these
products possibly being odor-free or perfumed.
A further subject of the invention is a perfume composition comprising an
isomerate of the invention, at least one of its isomers and/or the derivatives thereof
obtained in particular using the method of the invention.
A further subject of the invention is a consumer product comprising a perfume
composition of the invention.
According to one particular embodiment, the method of the invention also
comprises:
2’) an oxidation step in the presence of dioxygen during which the
nitrile/ester/acidaldehyde obtained at step 1) is converted to fatty nitrile/ester/acid acid
of formula HOOC-(CH2)r+2-R, or
2’’) a reduction step, during which the nitrile/ester/acidaldehyde obtained at step 1)is
converted to fatty nitrile/ester/acidalcohol of formula HO-CH2-(CH2)r+2-R or to an amino
alcohol of formula HO-CH2-(CH2)r+3-NH2 if a nitrile.
2’) OXIDATION(OR AUTO-OXIDATION, OR AUTOXIDATION)
After the hydroformylation step, the nitrile/ester/acid aldehyde obtained has the
advantage of oxidizing very easily in contact with dioxygen. Advantageously, the
oxidation step is conducted by dispersing dioxygen or a gaseous mixture containing
dioxygen in the product resulting from hydroformylation. Preferably, the oxidation step
is implemented without the addition of any solvent and/or without the addition of
dioxygen-activating catalyst. Preferably, the oxidation step is implemented under
dioxygen partial pressure ranging from 0.2 bar to 50 bar, in particular 1 bar to 20 bar,
preferably 1 to 5 bar. Advantageously, the dioxygen is continuously injected into the
reaction medium, preferably in the form of a stream of air or oxygen, preferably injected
19
in excess relative to the stoichiometry of the oxidation reaction. Preferably the molar
ratio of dioxygen relative to the product derived from the hydroformylation step is in the
range of 3:2 to 100:2. Preferably, oxidation is conducted at a temperature in the range
of 0°C to 100°C, preferably 20°C to 100°C, more preferably 30°C to 90°C, further
preferably 40°C to 80°C, optionally with two consecutive increasing temperature holds.
Advantageously the method of the invention further comprises:
3’) a reduction step during which the nitrile acid obtained at step 2’) is converted to
anω-aminoacid of formula HOOC-(CH2)r+3-NH2 for a nitrile acid; or
3’’) a hydrolysis step during which the ester acid obtained at step 2’) is converted to a
diacid of formula HOOC-(CH2)r+2-COOH for an ester acid.
According to one particular embodiment, the method of the invention further
comprises a step to synthesize a polymer, polyamide in particular, by polymerization
using the ω-aminoacid or diacid obtained at step 3’); or a polyester by
polymerizationusing the ester alcohol obtained at step 2’’).
3’) REDUCTION OR HYDROGENATION OF THE NITRILE FUNCTION TO AN AMINE
The synthesis step of fattyω-aminoesters or ω-aminoacids from the fatty ester
nitriles or acid nitriles respectively entails conventional reduction or hydrogenation. The
reduction of the nitrile function to a primary amine is well known to persons skilled in
the art.Hydrogenation is performed for example in the presence of precious metals (Pt,
Pd, Rh, Ru…) at a temperature between 20 and 100 °C under pressure of 1 to 100 bar,
and preferably 1 to 50 bar. It can also be performed in the presence of catalysts
containing iron, nickel or cobalt which can withstand more severe conditions with
temperatures in the order of 150 °C and high pressures of several tens of bars. To
promote the formation of the primary amine, ammonia partial pressure is preferably
applied.Advantageously the reduction step of the fatty acid nitriles to ω-amino fatty acid
uses hydrogenation with any conventional catalyst, and preferably Raneynickel and
cobalt catalysts, in particular Raney nickel whether or not deposited on a substrate
such as silica.
SYNTHESIS OF POLYAMIDES
The polymers able to be produced from the fatty nitrile/ester/acid aldehydes of
the present invention are specialty products, e.g. technical polyamides with respect to
polyamides, i.e. high-performing even very high-performing polyamides produced from
precursors or monomers having at least 8 carbon atoms, preferably at least 10 carbon
atoms; as opposed to so-called "commodity" polyamides,such as "nylon-6", for
20
whichthe marketing quantities (volumes) are very much higher and the costs much
lower than for technical polyamides.
According to one particular embodiment, the method of the invention is a
method to synthesize aω-aminoacid compound of formula:
HOOC-(CH2)r+2-CH2NH2,
from a mono-unsaturated fatty nitrile compound of formula :
CH2=CH-(CH2)r-CN
comprising the following steps:
- hydroformylation of the unsaturated nitrile compound to obtaina nitrile aldehyde
compound of formula HOC-(CH2)r+2-CN, then
- oxidation of the nitrile aldehyde compound to obtain the corresponding nitrileacid
compound of formula HOOC-(CH2)r+2-CN, and
- reducing the nitrile-acid compound to ω-aminoacid of formula
HOOC-(CH2)r+2-CH2NH2.
According to one advantageous embodiment, the method of the invention also
comprises a step to synthesize a polyamide by polymerization using the ω-aminoacid
obtained at step 3).
Starting from castor oil for example,methanolysis is carried out to obtain methyl
ricinoleate of formula:
CH3-(CH2)5-CHOH-CH2-CH=CH-(CH2)7-COOCH3
after which thermal cracking is performed to obtain methyl undecylenate:
CH2=CH-(CH2)8-COOCH3
which can be hydrolyzed to undecylenic acid:
CH2=CH-(CH2)8-COOH
followed by a nitrilation step to obtain the undecenenitrile:
CH2=CH-(CH2)8-CN
Alternatively, the conversion of the methyl ester of undecylenic acid to a nitrile is
performed directly.
The undecenenitrilethus obtained is used in the method of the invention at the
following steps:
1) hydroformylation of the nitrile in the presence of CO and H2, to obtain a nitrile
aldehyde having 12 carbons:
HOC-(CH2)10-CN
2) autoxidation of the aldehyde to acid, to obtain:
HOOC-(CH2)10-CN
21
3) reduction of thenitrile, to obtain the C12 aminoacid:
HOOC-(CH2)10-CH2-NH2
which, via polymerization, allows the production of polyamide-12 from a renewable
source.
Starting from an oil high in oleic acid (cis-9-octadecenoic acid) of formula:
CH3-(CH2)7-CH=CH-(CH2)7-COOR,
R being a glyceric radical meeting formula-CH2-CHOX-CH2OY,X and Y each
independently being H, another fatty chain of the triglyceride (oil) or oleic
radicals,
it is possible to proceed as follows:
- ethenolysis (cross metathesis with ethylene or other alpha olefin), to obtain at least:
CH3-(CH2)7-CH=CH2 + CH2=CH-(CH2)7-COOR
- methanolysis and separation of the fatty acids to isolate the methyl decenoate:
CH2=CH-(CH2)7-COOCH3
- hydrolysis of the ester to acid CH2=CH-(CH2)7-COOH,
- nitrilation of the acid to 9-decenenitrile CH2=CH-(CH2)7-CN
Thereafter the 9-decenenitrile is subjected to the following steps according to
the method of the invention:
- hydroformylation of the9-decenenitrile to C11 nitrile aldehyde: HOC-(CH2)9-CN
- autoxidationto form the C11 nitrile acid: HOOC-(CH2)9-CN
- reduction to form11-aminoundecanoic acid HOOC-(CH2)9-CH2-NH2.
Via polymerization of 11-aminoundecanoic acid, polyamide-11 is produced.
Alternatively the oleic acid can be converted to oleic nitrile, followed by
ethenolysis (or other cross metathesis with an alpha-olefin) to obtain the nitrile
containing 10 carbon atoms.
Examples
Unless otherwise indicated,all percentages are percentages in number of
moles.
1. Materials
Rh(acac)(CO)2 (marketed by STREM) was used as precursorfor
thehydroformylation catalyst. The phosphines (marketed by STREM) were used such
as received or synthesized.
22
2. Substrate:10-undecenenitrile (or 1,10-undecenitrile)
3. Hydroformylation reaction
The isomerate(1-int) contains a mixture of isomers with internal unsaturation (ω-
x :ω-1, ω-2, ω-3…) of the substrate (1) with terminal unsaturation (ω-unsaturated):
For simplification solely the isomers of trans type are illustrated in the above
schemes. Evidently the isomers of cis type are also produced.
General procedure:
The hydroformylationreactions are carried out in a 100 mL stainless steel
autoclaves. Under typical conditions, a solution in toluene (0.5 to 5 mL) of metal
precursor (0.001 to 0.0001 mmol), phosphine (0.002 to 0.02 mmol) and substrate (5 to
25 mmol) is mixed in a Schlenktube underargoninert atmosphere to form a
homogeneous solution. After agitation at ambient temperature for 1 hour, this solution
is cannulated into the autoclave previously provided with an inert atmosphere. The
reactor is sealed, purged several times with a CO/H2mixture (1:1), pressurizedat 20 bar
of this CO/H2mixture at ambient temperature and heated to the desired temperature
using a hot water bath or oil bath. During the reaction, the pressure is held constant
and several samples are taken to monitor conversion. After a suitable reaction time, the
+
linear, (2 ) branched, (3)
7
CN
OHC
7
CN
CHO
CN 7
x
7-x
CN
(1)
(1-int)
CN 7
(4)
+
+
cat
H2/CO
Solvent
x
7-x
CN
CHO
x
7-x
CN
0 ≤ x ≤ 7 CHO
6
CN
H
H
6
CN
H
H 5
CN
H
H
23
autoclave is returned to ambient temperature and then atmospheric pressure. The
mixture is collected and analyzed by NMR.
Example 1: Hydroformylation of 10-undecenenitrile (Rh-biphephos with S/Rh = 20,000
and L/Rh = 20)
A solution of Rh(acac)(CO)2 intoluene (0.65 mg, 0.00025 mmol), Biphephos
(4 mg, 0.005 mmol) and undecenitrile (826 mg, 5.0 mmol) was prepared in a
Schlenktube underargon inert atmosphere to form a homogeneous solution left under
agitation at ambient temperature for 1 h. The Biphephos/rhodium molar ratio was 20:1
and substrate/rhodium molar ratio 20,000:1. The solution was cannulated into a 100 ml
autoclave previously provided with an inert atmosphere. The reactor was sealed,
purged several times with a CO/H2gas mixture (1:1), pressurized at 20 bar CO/H2 (1:1)
at ambient temperature and heated to120 °C. After 5 h, 100 % undecenitrile was
consumed. After 5 h, the medium was returned to ambient temperature and
atmospheric pressure. The mixture was collected and analyzed by NMR. Analysis
showed that the reaction was complete and that there remained a proportion of internal
olefin of 19 %, a proportion of hydrogenation product(4) of 5 %, and that 86 % of the
products formed corresponded to branched aldehydes (1%) and linear aldehydes
(99%).
For subsequent valorization of the formed sub-products,the internal alkenes
were separated from the mixture by Kugelrhor distillation (135 °C, 1 mbar). 13C NMR
analysis showed that 80 % of these internal alkenes were 9-undecenenitrile whereas
20 % represented 8-undecenitrile.
Example 2: Hydroformylation of 10-undecenenitrile (Rh-biphephos with S/Rh = 20,000
and L/Rh = 100, 5 h)
A solution ofRh(acac)(CO)2 intoluene (0.65 mg, 0.00025 mmol), Biphephos
(20 mg, 0.025 mmol) and undecenitrile (826 mg, 5.0 mmol) was prepared in a
Schlenktube under argon inert atmosphere to form a homogeneous solution which was
left under agitation at ambient temperature for 1 h. The Biphephos /rhodium molar ratio
was 100:1 and the molar ratio of substrate/rhodium 20,000:1. The solution was
cannulated into a 100 mL autoclave previously provided with an inert atmosphere. The
reactor was sealed, purged several times with CO/H2gas mixture (1:1), then
pressurized at 20 bar CO/H2 (1:1) at ambient temperature and heated to 120 °C. After
4 h, the medium was returned to ambient temperature and atmospheric pressure. The
mixture was collected and analyzed by NMR. Analysis showed that the reaction was
complete and that there remained a 21 % proportion of internal olefin, 5 % proportion of
24
hydrogenation product and that 84 % of the formed products corresponded to branched
aldehydes (1%) and linear aldehydes (99%).
The internal alkenes were also separated from the mixture byKugelrhor
distillation (135 °C, 1 mbar). 13C NMR analysis showed that 95% of these alkenes were
9-undecenitrile whereas 5 % represented 8-undecenitrile.
Example 3: Hydroformylation of 10-undecenenitrile (Rh-biphephos with S/Rh = 50,000
and L/Rh = 20; solvent-free)
A solution ofRh(acac)(CO)2 (0.13 mg, 0.0005 mmol) in toluene (0.5 ml),
Biphephos (8 mg, 0.01 mmol) and undecenitrile(4,12 g, 25.0 mmol) was prepared in a
Schlenktube under argon inert atmosphere to form a homogeneous solution which was
left under agitation at ambient temperature for 1 h. The Biphephos /rhodium molar ratio
was 20:1 and substrate/rhodium molar ratio 50,000:1. The solution was cannulated into
a 100 mL autoclave previously provided with an inert atmosphere. The reactor was
sealed, purged several times with CO/H2gas mixture (1:1), thenpressurized at 20 bar
CO/H2 (1:1) at ambient temperature and heated to 120 °C. After 4 h, 100% of the
undecenitrilehad been consumed. The reaction was left to continue for 48 h for
maximum internal olefin consumption. The mixture was collected and analyzed by
NMR after 48 h. Analysis showed that the reaction was complete and that there
remained a 6% proportion of internal olefin, 7 % hydrogenation product and 87 % of the
formed products corresponded to branched aldehydes (1%) and linear aldehydes
(99%).
25
Example 4: Kinetics of the hydroformylationreaction, solvent-free and in solution
(Rh-biphephos with S/Rh = 20,000 and L/Rh = 20 ;)
Table 1[a]
Input [1]0/[Rh] biphephos [1]0 Time 1 1-intw w-1 w-2 2+3 4 Conv.1 HF
2/3
[eq vs. Rh] [M] [h] [%][b] [%][b] [%][b] [%][b] [%][b] [%][b] [%][c] [%][d]
1 20000 20 1 M 2 30 17 82 18 49 4 68 75 99/1
3 6 22 71 29 68 4 94 76 99/1
4 0 20 74 26 75 5 100 79 99/1
5 0 19 75 25 76 5 100 80 99/1
2[e] 20000 20 solvent-free[e] 2 25 15 84 16 56 4 74 80 99/1
3 4 21 78 22 69 6 96 76 99/1
4 0 20 80 20 74 6 100 78 99/1
5 0 19 81 19 75 6 100 79 99/1
[a] Reaction conditions unless otherwise specified: 1/1-int (95:5 mixture) = 5 mmol, toluene (5 ml),
P = 20 bar CO/H2 (1:1).
[b] Distribution (%mol)of remainder1, internal alkenes1-int (residual or formed during the reaction),
aldehydes 2 and 3, and hydrogenation product4, such as determined by NMR and GLC.
[c] Conversion of1.
[d] Selectivity for hydroformylation products (2+3).
[e] A minimum amount of toluene (0.5 mL) was used to add the catalyst precursors. It is considered
to be solvent-freehydroformylation.
Example 5: Hydroformylation of 1,10-undecenenitrile (Ir-biphephos with S/Ir= 20,000
and L/Ir= 20 ) (Input 2)
A solution of [Ir(COD)(Cl)]2 (0.83 mg, 0.00025 mmol) in toluene (5
mL),Biphephos (4 mg, 0.005 mmol) and undecenitrile (5.0 mmol) was prepared in a
Schlenktube under argon inert atmosphere to form a homogeneous solution then left
under agitation at ambient temperature for 1 h. The Biphephos /iridium molar ratio was
20:1 and substrate/iridium molar ratio 20,000:1. The solution was cannulated into a
100 mL autoclave previously provided with an inert atmosphere. The reactor was
sealed, purged several times with CO/H2gas mixture (1:1), thenpressurized at 20 bar
CO/H2 (1:1) at ambient temperature and heated to 120 °C. After 18 h, 100 % of the
undecenenitrilehad been consumed. The mixture was collected and analyzed by NMR
after 18 h. Analysis showed that the reaction was complete and that there remained a
22 % proportion of internal olefin (of which 85 % 9-undecenenitrile), 5 % hydrogenation
26
product while 73 % of the formed product corresponded to branched aldehydes (<1 %)
and linear aldehydes (>99%).
The protocol of Example 5 above was reproduced with another ligand
(Xantphos, Input 1) or another solvent (THF or NMP, Inputs 3 and 4 respectively).
All results are given in Table 2 below:
Table 2[a]
Input Ligand Solvent 1 1-int 9-undec 8-undec 2+3 4 Conv.1 HF
2/3
[%][b] [%][b] [%][b] [%][b] [%][b] [%][b] [%][c] [%][d]
1 Xantphos Toluene 82 7 95 5 9 2 14 69 98/2
2 Biphephos Toluene 0 22 84 16 73 5 100 77 >99/1
3 Biphephos THF 0 26 88 12 69 5 100 73 >99/1
4 Biphephos NMP 25 18 95 5 52 5 74 74 >99/1
[a] Reaction conditions unless otherwise specified: 1/1-int (95:5 mixture) = 5.0 mmol,
[1/1-int]0/[Ir] = 20,000, [ligand]/[Ir] = 20, P = 20 bar CO/H2 (1:1), 5 mL of solvent.
[b] Distribution (%mol) of remainder1, internal alkenes1-int (residual or formed during the reaction),
aldehydes 2 and 3, and hydrogenation product4, such as determined by NMR and GLC analysis.
[c] Conversion of1.
[d] Selectivity for hydroformylation products (2+3).
Example 6: Hydroformylation of methyl-10- undecenoate(Rh-biphephos with
S/Rh = 50,000 and L/Rh = 20; solvent-free)
A solution of Rh(acac)(CO)2 (0.13 mg, 0.0005 mmol) in toluene (0.5 ml),
Biphephos (8 mg, 0.01 mmol) and methyl-10-undecenoate (25.0 mmol) was prepared
in a Schlenktube under argon inert atmosphere to form a homogeneous solution then
left under agitation at ambient temperature for 1 h. The Biphephos /rhodium molar ratio
was 20:1 and substrate/rhodium molar ratio 50,000:1. The solution was cannulated into
a 100 mL autoclave previously provided with an inert atmosphere. The reactor was
sealed, purged several times with CO/H2gas mixture(1:1), then pressurized at 20 bar
CO/H2 (1:1) at ambient temperature and heated to 120 °C. After 5 h, 100 % of the
undecenoatehas been consumed. The reaction was left to continue for 48 hfor
maximum internal olefin consumption. The mixture was collected and analyzed by
NMR after 48 h. Analysis showed that the reaction was complete and that there
remained a 6 % proportion of internal olefin, 9 % hydrogenation product while 85 % of
the formed products corresponded to branched aldehydes (1%) and linear aldehydes
(99%).
27
Example 7: Oxidation of hydroformylation products
The aldehydes resulting fromhydroformylation of the previously distilled
undecenitrile(5.4 g, 30 mmol) were dissolved in ether (10 mL) and left under agitation
in air for 48 h. A white crystalline solid was gradually formed and collected by filtration;
it corresponded to the corresponding carboxylic acid.
Example 8: Hydrogenation of the nitrile acid
A solution of Ni/Raney (40 mg) in water/ethanol mixture (2 ml / 2 mL), ammonia
(3 mmol, 1M in methanol) and nitrile acid (360 mg, 2 mmol) was prepared in a
Schlenktube at ambient temperature. The solution was cannulated into a 100 mL
autoclave previously provided with an inert atmosphere. The reactor was sealed,
purged several times with H2 gas then pressured at 40 bar H2 at ambient temperature
and heated to 130 °C. After 12 h, 100 % of the nitrile acidhad been hydrogenated. The
reactor was depressurized at ambient temperature and 5 mL of acetic acid were
added. The catalyst was extracted by filtration and the filtrate evaporated. A white
precipitate was obtained after washing in ether (15 mL). NMR and IR analysis showed
that the zwitterionicproduct had been obtained.
Example 9: Comparison between the effect of 2 different ligands
Conditions: S/Rh = 20,000, 20 bar CO/H2 (1:1), 120 °C, 5 h, Toluene
(5ml),[1+1-int]0 = 5 mmol.
Table 3
Input Ligand
Ligand Conv. 1-
inttotal
% 9- % 8- Sel. (%)[b] Hydrogenated
product
[equiv]0 (%) undecen undecen 2 3 4
1 Xantphos 100 42 8 95 5 98 2 4
2 Biphephos 20 100 19 79 21 99 1 5
3 Biphephos 100 100 21 95 5 99 1 5
Observations:
A large excess of ligand (100 Eqfor Inputs 1 and 3 in Table 3) in relation to the
undecenenitrile substrate:
- does not lead to a global reduction in isomerization products (19% vs. 21% -
Input 2 vs Input3);
28
- on the other hand,it has a positive effect on the distribution of internal olefins by
increasing the content of ω-1 unsaturated isomers compared toω-2 unsaturated
ones.The isomerization reaction was slowed beyond the ω-1 position due to the
presence of ligand excess. If too much ligand, the latter ends up competing with
the reactants for access to the metal.
The following examples show that isomerization is limited with larger ligand
quantity.
Experiments were conducted to evaluate the importance of excess ligand in the
hydroformylation-isomerization reaction of 1, in particular on the distribution of internal
isomers 1-int.
The results are grouped together in Table 4.
WithRh(acac)CO2, [Ir(cod)Cl]2 andIr(cod)(acac) as catalysts, a notable positive
effect was observed on selectivity for 9-undecenitrile by increasing the
[biphephos]/[metal] ratio from 20 to 100 (see Table 4, Inputs 1-3, 4-6 and 7-8).
Table 4[a]
Input Catalyst biphephos 1 1-int 9-/8- 2+3
2/3
4 Conv.
1 HF
[equiv]0 [%][b] [%][b] undec [%][b] [%][b] [%][c] [%][d]
1[e] Rh(acac)(CO)2 20 1 17 79/21 77 99/1 5 99 82
2[e] Rh(acac)(CO)2 50 1 17 84/16 77 99/1 5 99 82
3[e] Rh(acac)(CO)2 100 1 19 90/10 76 99/1 4 99 81
4 [Ir(cod)Cl]2 20 0 22 86/14 73 99/1 5 100 77
5 [Ir(cod)Cl]2 50 0 23 93/7 71 99/1 6 100 75
6 [Ir(cod)Cl]2 100 18 16 100/0 60 99/1 6 81 78
7 Ir(cod)(acac) 20 3 21 92/8 64 99/1 12 97 70
8 Ir(cod)(acac) 100 36 13 95/5 43 99/1 8 62 73
[a] Reaction conditions unless otherwise specified: 1/1-int (95:5 mixture) = 5.0 mmol,
[1/1-int]0/[M] = 20,000, [ligand]/[Ir] = 20, P = 20 bar CO/H2 (1:1), 5 mL toluene, 120°C, reaction time :
5h (Rh) and 20h (Ir).
[b] Distribution (%mol) of remainder1, internal alkenes1-int, aldehydes2 and 3, and hydrogenation
product 4, such as determined by NMR and GLC analysis.
[c] Conversion of1.
[d] Selectivity for hydroformylation products (2+3)
29
Example 10: Study on the effect of the CO/H2ratio
Conditions: S/Rh = 20,000, L/Rh = 20, L: Biphephos, 120 °C, 5h, Toluene
(5ml),[1+1-int]0 = 5 mmol.
Table5
Input
Total
P CO H2 CO/H2 Conv. 1-int % 9- % <8- Sel. (%)[b] Hydrogenated
product
(bar) (bar) (bar) (%) alkene[c 4
] undecen undecen 2 3 ald.
Int.
1 20 10 10 1/1 100 19 79 21 99 1 - 5
2 20 5 15 1/3 100 18 74 26 99 1 - 7
3 20 15 5 3/1 100 28 77 23 97 3 - 25
Observations: The CO/H2ratio at 20 bar and after 5h:
- influences the distribution of internal olefins: the content of ω-1 unsaturated
isomersincreases compared to ω-2 unsaturated isomers content with the
CO/H2 ratio;
-more especially influences selectivity: the more the CO/H2ratio decreases, the
more selectivity increases (fewer hydrogenation products are formed).
Example 11: Comparison of different [ligand]/[metal] ratios:
Table6
Observations:
The more the ligand/metal ratio increases, themore the content of ω-1
unsaturated isomers increases compared to the content ofω-2 unsaturated isomers.
Input Substrate L/Rh
Time Conv.
(%)[c]
1-int
total
% 9-
undecen
% 8-
undecen
Sel. (%)[b] Hydrogenatedp
(h) n-2 iso-3 sub- roduct
pdt
1* Methyl 10-
undecenoate 20 5 100 12 63 37 99 1 - 8
1** Methyl 10-
undecenoate 100 5 100 12 82 18 99 1 - 8
2* 10-
undecenenitrile 20 5 100 16 79 21 99 1 - 5
2** 10-
undecenenitrile 100 5 100 20 95 5 99 1 - 6
30
Example 12: Effect of total CO/H2 pressure on hydroformylation-isomerization of 1/1-
intcatalyzed by Rh- andIr-biphephos:
The impact of pressure was investigated under optimized conditions for Ir- and
Rh-biphephoscatalysts. The results obtained are grouped together in Table 7 below.
Irrespective of the pressure applied (20 or 80 bar), the activity and selectivity for
aldehyde 2 are not affected (Table 7, Inputs 1-4 and 5-8).
However, the percentage of internal olefins asformed decreases with pressure
increase (Table 7, Inputs1-4 and 5-8).
For both types of catalyst, a higher pressure generates better selectivity to the
benefit of hydroformylation and better control over the distribution of internal isomers to
the benefit of 9-undecenenitrile (in ranges of 86-95 % with Rh and 90-97% withIr).
Table 7[a]
Input Catalyst H2/CO 1 1-int 9-/8- 2+3
2/3
4 Conv.
1 HF
[bar] [%][b] [%][b] undec [%][b] [%][b] [%][c] [%][d]
1 Rh(acac)(CO)2 10 0 37 86/14 58 99/1 5 100 60
2[e] Rh(acac)(CO)2 20 0 21 89/11 75 99/1 4 100 79
3 Rh(acac)(CO)2 40 0 18 93/7 78 99/1 4 100 82
4 Rh(acac)(CO)2 80 0 15 95/5 82 99/1 3 100 86
5 Ir(cod)(acac) 10 2 35 90/10 58 99/1 5 98 63
6 Ir(cod)(acac) 20 1 20 92/8 75 99/1 4 99 80
7 Ir(cod)(acac) 40 2 21 95/5 73 99/1 4 97 79
8 Ir(cod)(acac) 80 3 17 97/3 77 99/1 3 97 84
[a] Reaction conditions unless otherwise specified: 1/1-int (95:5 mixture) = 5.0 mmol,
[1/1-int]0/[Ir] = 20,000 and [1/1-int]0/[Rh] = 50,000, [ligand]0/[M] = 20, solvent(5 mL): toluene (Rh) or
acetonitrile (Ir), 120°C, reaction time: 5h (Rh) and 20h (Ir,), CO/H2pressure (1:1).
[b] Distribution (%mol) of remainder1, internal alkenes1-int, aldehydes 2 and 3, and hydrogenation
product 4, such as determined by NMR and GLC analysis.
[c] Conversion of1.
[d] Selectivity for hydroformylation products (2+3)
Example 13: Effect of CO/H2ratio at 40 baron hydroformylation-isomerization of 1/1-
intcatalyzed by Rh- andIr-biphephos:
31
According to the results of Table 8 below, it is observed that an increase in CO
partial pressure improves chemoselectivity and hence yields of aldehydes, and allows
reduced isomerization (less shifting of the double bond along the chain).
In addition, fewer hydrogenation products4are formed.This finding appears to
show that at higher total pressure, there is promoting of thehydroformylationreaction
over hydrogenation.
Concomitantly, better control over the distribution of internal isomers is
achieved.
These observations confirm those already made in Example 10, according to
Table 5.
Table 8[a]
Input Catalyst CO/H2 1 1-int 9-/8- 2+3
2/3
4 Conv.
1 HF
at 40 bar [%][b] [%][b] undec [%][b] [%][b] [%][c] [%][d]
1 Rh(acac)(CO)2 1/1 0 18 93/7 78 99/1 4 100 82
2 Rh(acac)(CO)2 1/3 0 20 85/15 71 96/4 9 100 74
3 Rh(acac)(CO)2 3/1 0 16 94/6 81 99/1 3 100 85
4 Ir(cod)(acac) 1/1 2 21 95/5 73 99/1 4 97 79
5 Ir(cod)(acac) 1/3 18 22 90/10 54 97/3 6 81 70
6 Ir(cod)(acac) 3/1 52 9 96/4 38 99/1 1 45 88
[a] Reaction conditions unless otherwise specified: 1/1-int (95:5 mixture) = 5.0 mmol,
[1/1-int]0/[M] = 20,000, [biphephos]0/[M] = 20, solvent (5 mL): toluene (Rh) or acetonitrile (Ir), CO/H2total
pressure of 40 bar, 120°C, reaction time: 5h (Rh) and 20h (Ir).
[b] Distribution (%mol) of remainder1, internal alkenes1-int, aldehydes 2 and 3, and hydrogenation
product 4, such as determined by NMR and GLC analysis.
[c] Conversion of1.
[d] Selectivity for hydroformylation products (2+3)
32
Example 14: Bulk, solvent-freehydroformylation and isomerization reaction:
Table 9[a]
Input Catalyst [1]0/[Rh] Time 1 1-int 9/8-
undec Trans/ 2+3
2/3
4 Conv.
1 HF
[M] [h] [%][b] [%][b] ratio Cis [%][b] [%][b] [%][c] [%][d]
1 Rh(acac)(CO)2 20000 5 1 20 84/16 65/35 75 99/1 4 99 80
2 Rh(acac)(CO)2 50000 5 9 21 89/11 62/38 65 99/1 5 91 76
3 Ir(cod)(acac) 20000 20 8 16 94/6 60/40 72 99/1 4 92 83
4[e] Ir(cod)(acac) 20000 20 18 14 95/5 58/42 63 99/1 4 81 83
[a] Reaction conditions unless otherwise specified: 1/1-int (95:5mixture) = 25.0 mmol,
[biphephos]0/[M] = 20, CO/H2pressure(1:1) = 40 bar, 120°C, minimum content (0.5 mL) oftoluene (Rh) or
acetonitrile (Ir)was used to add catalyst precursors.
[b] Distribution (%mol) of the remainder1, internal alkenes1-int, aldehydes 2 and 3, and hydrogenation
product4, such as determined by NMR and GLC analysis.
[c] Conversion of 1.
[d] Selectivity for hydroformylation products (2+3)
[e] P = 80 bar CO/H2 (1:1).
Example 15: Hydroformylationreaction of 1/1-int in the presence of Rh-biphephos:
Table 10[a]
Input Catalyst T H2/CO 1 1-int 9/8-
undec Trans/ 2+3
2/3
4 Conv.
1 HF
[° C] [bar] [%][b] [%][b] ratio Cis [%][b] [%][b] [%][c] [%][d]
1 Rh(acac)(CO)2 120 20 0 21 89/11 68/32 75 99/1 4 100 79
2[e] Rh(acac)(CO)2 80 20 0 17 90/10 65/35 78 99/1 5 100 82
3 Rh(acac)(CO)2 120 40 0 18 93/7 62/38 78 99/1 4 100 82
4 Rh(acac)(CO)2 120 80 0 15 95/5 58/42 82 99/1 3 100 86
[a] Reaction conditions unless otherwise specified: 1/1-int (95:5 mixture) = 5.0 mmol,
[substrate]0/[Rh] = 20,000, [biphephos]0/[M] = 20, toluene (5 mL), 5h, CO/H2pressure (1:1).
[b] Distribution (%mol) of remainder1, internal alkenes1-int, aldehydes 2 and 3, and hydrogenation
product 4, such as determined by NMR and GLC analysis.
[c] Conversion of1.
[d] Selectivity for hydroformylationproducts (2+3)
[e] Reaction time = 20h.
It is observed that total pressure forms one means to control isomerization, by
acting on shifting of the double bond, and the ratio between isomers with cis and
transinternal unsaturation.
33
Example 16: Effect of CO/H2 ratio on hydroformylation-isomerization of 1/1-intcatalyzed
by Rh- andIr-biphephos :
The catalystsIr- and Rh-biphephos also allow thehydroformylation and
isomerization of unsaturated fatty esters such as methyl-10-undecenoate
(R=COOCH3).
Results under the conditions used for conversion of the unsaturated nitrile are
grouped together in Table 11 below.
Good chemoselectivity and excellent regioselectivity for the formation of linear
aldehydes are obtained.
Table 11[a]
Input Catalyst Subs int 9-/8- ald
Selald
H2
Conv.
Subs HF
[%][b] [%][b] undec [%][b] [%][b] [%][c] [%][d]
3 Rh(acac)(CO)2 0 11 80/20 82 99/1 7 100 86
4 Ir(cod)(acac) 2 13 90/10 80 99/1 5 98 86
[a] Reaction conditions unless otherwise specified: substrate = 5,0 mmol, [substrate]0/[M] = 20,000,
[biphephos]0/[M] = 20, solvent (5 mL): toluene (Rh) or acetonitrile (Ir), 120°C, P=20 bar CO/H2 (1:1),
Reaction time: 5h (Rh) or 20h (Ir).
[b] Distribution (%mol) of substrate remainder, internal alkenes (residual or formed during the reaction),
aldehydes (linear or branched) and hydrogenation product such as determined by NMR and GLC
analysis.
[c] Conversion of substrate.
[d] Selectivity for hydroformylationproducts and linear/branched ratio.
34
We claim:
1- A method to prepare a fatty nitrile/ester/acid aldehyde comprising the
following steps:
1) hydroformylationof a ω-unsaturated fatty nitrile/ester/acid substrate selected from
among the compounds of formula CH2=CH-(CH2)r-R, where R is CN or COOR1, R1
being H or an alkyl radical having 1 to 4 carbon atoms, r is an integer index such that
1 ≤ r ≤ 13, advantageously 2 ≤ r ≤ 13 and preferably4 ≤ r ≤ 13, wherein said substrate
is reacted with carbon monoxide and dihydrogen under the following conditions:
- CO partial pressure of 40 bar or lower, H2partial pressure of 40 bar or lower,
and the PiCO/PiH2 ratio between the respective CO andH2 partial pressures is
in the range of 0.5:1 to 3:1,
- temperature in the range of 70 to 150°C,
- reaction time of 24 h or less,
- in the presence of a catalyst comprising at least one Group VIII metal and at
least one bidentate ormonodentate ligand,
- [substrate]/[metal] molar ratio in the range of 5 000 to 100 000
- [ligand]/[metal] molar ratio in the range of 10:1 to 100:1,
so as after the reaction to obtain:
- a hydroformylationproduct comprising at least one fatty nitrile/ester/acid
aldehyde of formula: OHC-(CH2)r+2-R, and
- an isomerate comprising at least one fatty nitrile/ester/acid isomer with internal
unsaturation of which at least 80% of the internal isomer(s) of the isomerate
are formed of the ω-1-unsaturated isomer of formula CH3-CH=CH-(CH2)r-1-R;
followed by:
2) separationand recovery of the fatty nitrile/ester/acid aldehyde and of the isomerate.
2- The method according to claim 1 wherein the ω-unsaturated fatty
nitrile/ester/acid substrate meets formula CH2=CH-(CH2)r-R, with R=COOR1, R1 being
H or an alkyl radical having 1 to 4 carbon atoms.
3- The method according to claim 1 or 2 wherein hydroformylationis conducted
under CO partialpressure in the range of 10 to40 bar, under H2 partialpressure in the
range of 5 to 20 bar, and/or with a PiCO/PiH2 ratio between the respective CO and
H2partial pressures in the range of 1:1 to 3:1.
35
4- The method according to any of the preceding claims wherein
hydroformylationis conducted at a temperature within the range of 100 to 130°C,
preferably 100 to 120°C, preferably at a temperature of substantially 120°C.
5- The method according to any of the preceding claims wherein
hydroformylationis conducted for a time in the range of 1 to 12 h, preferably in the
range of 2 to 6 h, preferably in the range of3 to5 h, preferably in the order of 4 h.
6- The method according to any of the preceding claims wherein the ligand of the
catalyst is a bidentate ligand, advantageously a chelating diphosphine selected from
among Dppm, Dppe, Dppb, Xantphos and/orBiPhePhos, preferably selected from
among Xantphos and/orBiPhePhos,and is further preferably BiPhePhos.
7- The method according to any of the preceding claims wherein the metal of the
catalyst is provided in the form of a precursor comprising said metal and at least one
compound selected from among acetylacetonates, carbonyl compounds,
cyclooctadienes, chlorine, and mixtures thereof.
8- The method according to claim 7 wherein the hydroformylation catalyst
comprises rhodium, preferably provided by a precursor such as Rh(acac)(CO)2,
ruthenium, preferably provided by a precursor such as Ru3(CO)12, where acac is an
acetylacetonate ligand and CO is a carbonyl ligand, and/or iridium, preferably provided
by a precursor such asIr(COD)Cl where COD is a 1,5-cyclooctadiene ligand and Cl is a
chlorine ligand, preferably it comprises iridium.
9- The method according to any of claims 6 to 8 wherein hydroformylationis
catalyzed by a system selected from among: Rh-Xantphos, Rh-BiPhePhos,
Ir-Xantphos, Ir-BiPhePhos and the mixtures thereof.
10- The method according to any of the preceding claims wherein the
[substrate]/[metal] molar ratio is in the range of 5000 to 50 000.
11- The method according to any of claims 7 to 10 wherein the [ligand]/[metal]
molar ratio is in the range of 20:1 to 100:1, preferably 40:1 to 100:1.
36
12- The method according to any of the preceding claims wherein
hydroformylationis performed using a sufficient amount of solvent to solubilize at least
part of the catalyst, preferably in an amount of less than 1%,preferably less than
1/1000 relative to the ω-unsaturated fatty nitrile/ester/acid reactant.
13- The method according to any of the preceding claims wherein the
hydroformylation step comprises recycling of the hydroformylation catalyst, optionally
completed by the providing of new catalyst and/or ligand at a subsequent
hydroformylation cycle.
14- The method according to any of the preceding claims further comprising,
prior to the hydroformylation step, a step to pre-treat the substrate, this pre-treatment
being performed for example by distillation of the substrate followed by purification via
adsorption of the substrate using alumina.
15- The method according to any of the preceding claims further comprising a
step:
- to separate and recover the isomers from the isomerate, and/or
- to convert at least one isomer of the isomerate to isomer derivative(s), in particular by
conversion of one or more isomer functions to an acid, aldehyde, alcohol and/or amine
function, and/or by reaction(s) of the internal double bond of isomer(s), in particular
hydrogenation, epoxidation and/or polymerization.
16- The method according to claim 1 further comprising:
2’) an oxidation step in the presence of dioxygen during which the nitrile/ester/acidaldehyde
obtained at step 1) is converted to fatty nitrile/ester/acidacid of formula
HOOC-(CH2)r+2-R, or
2’’) a reduction step during which the nitrile/ester/acid aldehyde obtained at step1)is
converted to fatty nitrile/ester/acidalcohol of formula HOC-(CH2)r+2-R, or to an amino
alcohol of formula HOC-(CH2)r+3-NH2 for nitrile.
17- The method according to claim 16 wherein the oxidation step is
implemented by dispersing dioxygen or a gaseous mixture containing dioxygen in the
product resulting from hydroformylation.
37
18- The method according to claim 16 or 17 wherein the oxidation step is
implemented without the addition of solvent and/or without the addition of dioxygenactivating
catalyst.
19- The method according to one of claims 16 to 18 wherein the oxidation step
is implemented under dioxygen partial pressure ranging from 0.2 bar to 50 bar, in
particular1 bar to 20 bar, preferably 1 to 5 bar.
20- The method according to one of claims 16 to 19 wherein the dioxygen is
continuously injected into the reaction medium, preferably in the form of a stream of air
or oxygen, preferably injected in excess relative to the stoichiometry of the oxidation
reaction.
21- The method according to one of claims 16 to 20 wherein the molar ratio of
dioxygen relative to the product derived from the hydroformylationstep is in the range of
3:2 to 100:2.
22- The method according to one of claims 16 to 21 wherein oxidation is
conducted at a temperature in the range of 0 °C to 100 °C, preferably 20 °C to 100 °C,
more preferably 30 °C to 90 °C, further preferably 40 °C to 80 °C, optionally with two
consecutive temperature holds at increasing temperature.
23- The method according to claim 16 also comprising:
3’) a reduction step during which the nitrileacid obtained at step 2’) is converted
toω-aminoacid of formula HOOC-(CH2)r+3-NH2 with regard to a nitrileacid; or
3’’) a hydrolysis step during which the ester acid obtained at step 2’) is converted to
diacid of formula HOOC-(CH2)r+2-COOH with regard to an ester acid.
38
24- The method according to any of the preceding claims further comprising a
polymer synthesis step, in particular a polyamide, by polymerization using the ω-
aminoacid or diacid obtained at 3’); or polyester, by polymerization using the ester
alcohol obtained at step2’’).
Dated this 29th day of November, 2015.
(CHETAN CHADHA)
PATENT AGENT
39
ABSTRACT
METHOD FOR THE CONTROLLED HYDROFORMYLATION AND ISOMERIZATION
OF AN OMEGA-UNSATURATED FATTY NITRILE/ESTER/ACID
The present invention concerns a method to synthesize a fatty nitrile/ester
aldehyde comprising the following steps:
1) hydroformylation of a ω-unsaturated fatty nitrile/ester/acid substrate under particular
conditions of partial pressure, temperature, reaction time, conversion rate of
theω-unsaturated fatty nitrile/ester/acid reactant, catalyst, [substrate]/[metal] molar
ratio and [ligand]/[metal] molar ratio so as after the reaction to obtain:
- a hydroformylationproduct comprising at least one fatty nitrile/ester/acid
aldehyde of formula: OHC-(CH2)r+2-R, and
- an isomerate comprising at least one fatty nitrile/ester/acid isomer with internal
unsaturation in which at least 80% of the internal isomer(s) of the isomerate are
formed of the ω-1 unsaturated isomer of formula CH3-CH=CH-(CH2)r-1-R;
followed by:
2) separation and recovery of the fatty nitrile/ester/acid aldehyde and of the isomerate.