Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 95/28228 PCTIUS95104301
TT~ TT,F'
BIDENTATE PHOSPHITE AND NICKEL CATALYST
COMPOSITIONS FOR HYDROCYANATION OF MONOOLEFINS
FT_ ~.T,D O TH . TNV .NTTfIN
The invention generally relates to processes and
" catalyst precursor compositions useful for the
hydrocyanation of monoolefins. In particular, the
invention relates to the hydrocyanation of monoolefins
using catalyst precursor compositions comprising zero-
valent nickel and unsymmetrical bidentate phosphite
ligands.
BA .K ,RO rND O H . r NTT(1N
Hydrocyanation catalyst systems, particularly
pertaining to the hydrocyanation of olefins, are known
in the art. For example, systems useful for the
hydrocyanation of butadiene to form pentenenitrile (PN)
and in the subsequent hydrocyanation of pentenenitrile
(PN) to form adiponitrile (ADN), are known in the
commercially important nylon synthesis field.
The hydrocyanation of olefins using transition
metal complexes with monodentate phosphite ligand is
documented in the prior art. See for example; U.S.
3,496,215, 3,631,191, 3,655,723 and 3,766,237, and
Tolman, C. A.; McKinney, R. J.; Seidel, W. C.; Druliner,
J. D.; and Stevens, W. R.; Advances in Catalysis, 33, 1,
1985.
The hydrocyanation of activated olefins such as
With conjugated olefins (e. g., butadiene and styrene)
and strained olefins (e. g., norbornene) proceeds without
the use of a Lewis acid promoter, while hydrocyanation
of unactivated olefins such as 1-octene and 3-pentene-
nitrile requires the use of a Lewis acid promoter.
Teachings regarding the use of a promoter in the
hydrocyanation reaction appear, for example, in U.S.
3,496,217. This patent discloses an improvement in
hydrocyanation using a promoter selected from a large
number of metal cation compounds with a variety of
anions as catalyst promoters.
1
SUBSTITUTE SHEET (RULE 26)
W 0 95128228 ,; PCTIUS95104301
U.S. 3,496,218 discloses a nickel hydrocyanation
catalyst promoted with various boron-containing
compounds, including triphenylboron and alkali metal
borohydrides. U.S. 4,774,353 discloses a process for
the preparation of dinitriles, including ADN, from
unsaturated nitriles, including PN, in the presence of a
zero-valent nickel catalyst and a triorganotin catalyst
promoter. U.S. 4,874,884 discloses a process for
producing ADN by the zero-valent nickel catalyzed
hydrocyanation of pentenenitriles in the presence of a
synergistic combination of promoters selected, in
accordance with the reaction kinetics of the ADN
synthesis.
Bidentate phosphite ligands similar to those used
in the present i:2vention for the hydrocyanation of
monoolefins have been shown to be useful ligands in the
hydrocyanation of activated olefins. See, for example:
Baker, M. J., and Pringle, P. G.; J. Chem. Soc., Chem.
Commun., 1292, 1991; Baker, M. J.; Harrison, K. N.;
Orpen, A. G.; Pr.ingle, P. G.; and Shaw, G.; J. Chem.
Soc.; Chem. Commun., 803, 1991, Union Carbide, WO
93,03839. Also, similar ligands have been disclosed
with rhodium in the hydroformylation of functionaliaed
olefins; Cuny et al., J. Am. Chem. Soc. 1993, 115, 2066.
The present invention provides novel processes and
catalyst precursor compositions which are rapid,
selective, efficient and stable in the hydrocyanation of
monoolefins. Other objects and advantages of the
present invention will become apparent to those skilled
in the art upon reference to the detailed description
which hereinafter follows.
$ 1MMAR O TH . TNVFTTTT_QN
The present invention provides a process for hydro-
cyanation, comprising reacting a nonconjugated acyclic
aliphatic monoolefin or a monoolefin conjugated to an
ester group; e.g." methyl pent-2-eneoate, with a source
of HCN in the presence of a catalyst precursor
2
SUBSTITUTE SHEET (RULE 26)
2186351
WO 95/28228 PCTIUS95/04301
composition comprising zero-valent nickel and a
bidentate phosphate ligand of Formula I,
2
Formats I
wherein
each R1 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms;
each R2 is independently, H, X wherein X is C1, F
or Br, a C1 to C12 alkyl, or OR3 wherein R3 is
C1 to Clp alkyl;
to produce a terminal organonitrile. Preferably, the
reaction is carried out in the presence of a Lewis acid
promoter.
The present invention also provides a process for
hydrocyanation comprising reacting a nonconjugated
acyclic aliphatic monoolefin or a monoolefin conjugated
to an ester group; e.g., methyl pent-2-eneoate, with a -
source of HCN in the presence of a catalyst precursor
composition comprising zero-valent nickel and a
bidentate phosphate ligand selected from the group
consisting of Formulas II-VI as set forth below:
3
SUBSTITUTE SHEET (RULE 26)
R'O 95/28228 PCTIUS95/04301
R~
7
Formula II
wherein
each R6 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms; and
S each R~ is independently B, X wherein X is C1, F
or Br, a C1 to C12 alkyl, or ORe wherein R8 is
C1 to C12 alkyl;
to
Formula III
a
SUBSTITUTE SHEET (RULE 26)
WO 95!28228 PCTIUS95104301
wherein
each R9 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms;
each R10 is independently H, X wherein X is C1, F
' or Br, a C1 to C1z alkyl, or ORB wherein R8 is
C1 to C12 alkyl; and
' each R11 is independently a branched or straight
chain alkyl of up to 12 carbon atoms;
R
13
FOrmuI8IV
wherein
each R12 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms;
each R13 is independently H, X wherein X is C1, F
or Br, a C1 to C12 alkyl, or ORe wherein R8 is
C1 to C12 alkyl; and
each R14 is independently a branched or straight
chain alkyl of up to 12 carbon atoms;
5
SUBSTITUTE SHEET (RULE 26)
WO 95128228 2 i B 6 3 51 PCTIUS95104301
R16
R R1s
Formula V
wherein
each R15 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms; and
each Rls is independently H, X wherein X is C1, F
or Br, a C1 to C12 alkyl, or OR8 wherein Re is
C1 to C12 alkyl;
and
6
SUBSTITUTE SHEET (RULE 26)
W O 95128228 PCT/US95104301
R
is
1
Formula VI
wherein
each R1~ is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms; and
each Rls is independently H, X wherein X is C1, F
or Br, a C1 to C12 alkyl, or ORS wherein Re is
C1 to C1z alkyl;
to produce a terminal organonitrile. Preferably, the
reaction is carried out in the presence of a Lewis acid
promoter.
The monoolefins of the above-identified processes
are described by Formulas VII or IX, and the
corresponding terminal organonitrile compounds produced
are described by Formulas VIII or X, respectively.
Catalyst
Composition
CH3-(CH2)y-CH=CH-(CH2)x R19 -----------7.-NC-(CH2)y+x+3-819
VII Promoter, HCN VIII
wherein
R19 is H, CN, COZRZO, or perfluoroalkyl;
y is 0 to 12;
7
SUBSTITUTE SHEET (RULE 26)
WO 95/28228 218 6 3 5 PCTIUS95I04301
x is 0 to 12 when Rl9 is H, COZR20 or
perfluoroalkyl;
x is 1 to 12 when R19 is CN; and
RZO is alkyl; or
Catalyst
Composition
CH2=CH-(CHZ)% R19 _______~____j NC-(CH2)z+2-R19
TX Promoter, HCN X
wherein
R19 is H, CN, COpR20, or perfluoroalkyl;
x is 0 to 12 when R19 is H, C02R20 or
perflL~oroalkyl;
x is 1 to 12 when R19 is CN; and
R20 is alkyl.
The present invention further provides a catalyst
precursor composition comprising zero-valentnickel and
an unsymmetrical bidentate phosphite ligand of
Formula I~
R~
2
R2
Formula I
wherein
each Rl is independently a secondary or tertiary
substituted hydrocarbon of 3 to 12 carbon
atoms; and
8
SUBSTITUTE SHEET (RULE 26j
WO 95128228 ~ ~ ~ ~ ~ ~ ~ PCTlUS95104301
each RZ is independently H, X wherein X is Cl, F
or Br, a C1 to C12 alkyl, or OR3 wherein R3 is
C1 to C12 alkyl.
The present invention further provides a catalyst
precursor composition comprising zero-valent nickel and
an unsymmetrical bidentate phosphate ligand selected
from the group consisting of Formulas II-VI as set forth
below:
R~
Formula lI
wherein
each R6 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms; and
each R~ is independently H, X wherein X is C1, F
or Br, a Cy to C12 alkyl, or OR8-wherein R$ is
C1 to C12 alkyl;
9
SUBSTITUTE SHEET (RULE 26)
WO 95/28228 2 ~ ~ ~ ~ ~ ~ PCTIUS95104301
R
to ,
Formula III
wherein
each R9 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms;
each Rlo is independently H, X wherein X is C1, F
or Br, a C1 to Clg alkyl, or OR8 wherein Re is
C1 to C~2 alkyl; and
each R11 is independently a branched or straight
chain alkyl of up to 12 carbon atoms;
R13 R13 R13
RI3
R12
R
R13
~O i ' 'RR13
R14 ~~P~ 13
1
R13 R13 ~ \ RI3
R12 R13
R13 ~ / R13 R13 ~ / R13
R13 R13
Formula IV
SUBSTITUTE SHEET (RUL~ 26)
WO 95/28228 ~ PCTlUS95/04301
wherein
each R12 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms;
each R13 is independently H, X wherein X is C1, F
' or Br, a C1 to C12 alkyl, or ORe wherein Re is
C1 to C12 alkyl; and
' each R14 is independently a branched or straight
chain alkyl of up to 12 carbon atoms;
Ris
Formula V
wherein
each R15 is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms; and
each R16 is independently H, X wherein X is C1, F
or Br, a C1 to C12 alkyl, or OR8 wherein R8 is
C1 to C12 alkyl;
and
11
SUBSTITUTE SHEET (RULE 26)
W O 95128228 PCT/US95104301
R
a
FOrmul& VI
wherein
each R1~ is independently a secondary or tertiary
substituted hydrocarbyl of 3 to 12 carbon
atoms; and
each R18 is independently H, X wherein X is C1, F
or Br, a C1 to Clg alkyl, or OR8 wherein R8 is
C1 to C12 alkyl.
Preferably, the catalyst precursor compositions of
Formulas I-VI further comprise a Lewis acid promoter.
DETAI ~ .D D .S .RT m ON O TH . PREFERRED EMBODIMENTS
The catalyst precursor compositions of the
invention are comprised of a bidentate phosphate ligand
and zero-valent nickel. The preferred ligand of the
invention is described below by Formula I, wherein each
R2 is independently H, or a C1 to C12 alkyl, or OR3
wherein R3 is a C1 to C12 alkyl. Alkyl includes straight
chain or branched groups. R3 can be primary, secondary
or tertiary; examples include methyl, ethyl, isopropyl
and t-butyl. Each R2 may be the same or different. In
the preferred ligand, all R2 groups are H, except for
the two R2 groups meta to the R1 groups. These R2 groups
are OR3 wherein R3 is methyl. R1 is a secondary or
12
SUBSTITUTE SHEET (RULE 26)
WO 95/28228 PCTIUS95104301
tertiary substituted hydrocarbyl group containing up to
12 single bond carbon atoms. In the preferred ligand,
both R1 groups are tertiary butyl.
Formula I
As used herein, the terms "secondary or tertiary
substituted" refer to the first carbon of the
hydrocarbyl which is attached to the ring. The term
"hydrocarbyl" generally refers to a straight chain,
branched or aryl carbon structure containing single,
double or triple bonds, and substituted accordingly with
hydrogen.
Applicants have referred to the catalyst
composition of the invention as a "precursor"
composition only to indicate that, in all likelihood,
during the hydrocyanation reaction the structure of the
active catalyst composition may in fact be complexed to
an olefin.
The preferred ligands of the invention (i.e.,
Formula I) may be prepared by a variety of methods known
in the art, for example see descriptions in WO 93,03839,
U.S. 4,769,498; U.S. 4,688,651, J. Amer. Chem. Soc.,
115, 2066, 1993. The reaction of 2,2'-biphenol with
phosphorus trichloride gives l,l'-biphenyl-2,2'-diyl
phosphorochloridite. The reaction of this chloroidite
13
SUBSTITUTf SHEET (RULE 26)
CA 02186351 2005-02-28
. with 2,2'-dihydraxy-~,3~-di--t~butyl-5,5~-dialkoxy-1,7.~-
7oiphenyl in the presence of triethylamine gives the'
preferred bidentate phosphite ligand wherein R1 is
t-butyl.
Other bidentate phosphate ligands of the invention
axe described above by Formulas zl-VI. While. these
ligands may not be as presently preferred as Formula ~l,
,they nevertheless are aansidered useful ligands of the.
present invention. These ligands may be prepared by a
variety of methods known in the art: for example, see
U.S. Patent 5,202,297,
According to U.S. Patent
5,202,297, phosphorus trichloride is reacted with a diol
to ~orm a monochlorophosphite which 3s reacted with a
25 dial to forma hydroxyl-substituted diorganophosphite.
This diorganophosphite intermediate is reacted with
another monochlorophosphite to give the unsymmetrical
bidentate phosphate ligands of Formulas Iz-VZ.
' The zero-valent nickel can be prepared ar generated
according to techniques well known in the art (U. S.
3,996,217: 3,631,191; 3,846,461; 3,847,959; and
3, 903,120 ). , zero-
valent nickel compounds that contain ,agenda which ca.~,
be displaced by the organophosphoxus ligand are a
2S preferred source of zero-v~alent nickel. Two such
preferred zero-valent nickel compounds are Ni(C0D)2 (COb
is l, 5-cyclooctadiene) and N~. (P (O-a-C6HqCH3?~p2 (G2Ha)
both of which are known ~n the art. Alternatively,
d~-valent nickel compounds may be combined with a
reducing agent, and are then able to serve as suitable
sources of zero-valent nickel.in the reaction, Suitable
divalent nickel. compounds include compounds of the
formula NiXZ where Y is halide, carboxylate, or
acetylacetonate. Suitable reducing agents include metal
borohydrides, metal aluminum hydrides, metal alkyls, zn,
Fe, Al, Na, or HZ. Elembntal nickel, preferably nickel
powder, when combined with a halogenated cataylst, as
14
W095/28
~ ~ ~ ~~ ~
~
228
pCTIUS95104301
described in U.S. 3,903,120, is also a suitable source
of zero-valent nickel.
The nonconjugated acyclic aliphatic monoolefin
substrates of the invention include unsaturated organic
compounds containing from 2 to approximately 30 carbon
' atoms having at least one nonconjugated aliphatic
carbon-carbon double bond. The 3-pentenenitrile and
4-pentenenitrile are especially preferred. As a
practical matter, when the nonconjugated acyclic
aliphatic monoolefins are used in accordance with this
invention, up to about 10~ by weight of the monoolefin
may be present in the form of a conjugated isomer, which
itself may be subject to hydrocyanation. For example,
when 3-pentenenitrile is used, as much as 10~ by weight
thereof may be 2-pentenenitrile. Suitable unsaturated
compounds include olefins and olefins substituted with
groups which do not attack the catalyst, such as cyano.
These unsaturated compounds include monoolefins
containing from 2 to 30 carbons such as ethylene,
propylene, butene-1, pentene-2, hexene-2, etc.,
nonconjugated diolefins such as allene, and substituted
compounds such as 3-pentenenitrile, 4-pentenenitrile
and
methyl pent-3-enoate. The monoolefins may also be
conjugated to an ester group such as methyl
pent-2-enoate.
Two formulas are presented below which together
describe these substrates of the invention; Formulas
VII
and IX. Substrates of Formula VII yield terminal
organonitriles of Formula VIII, while Formula IX
substrates will yield terminal organonitriles of
Formula X.
CH3-(CHZ)Y CH=CH-(CH2)X R19
VII
wherein
R19 is H, CN, C02R2~, or perfluoroalkyl;
y is 0 to 12;
SUBSTITUTE SHEET (RULE 26)
21~63~~
W0 95/28228 PCTIUS95104301
x is 0 to 12 when Rl9 is H, COZR20 or
perfluoroalkyl;
x is 1 to 12 when R19 is CN; and
R20 is alkyl;
produces the terminal organonitrile product compound of
Formula VIII
NC-(CHZ)y+x+3-R19 ,
VIII
wherein
R19, y and x are as defined above.
CH2=CH-(CHZ)xRl9
IX
wherein
R19 is H, CN, C02R20. or perfluoroalkyl;
x is 0 to 12 when R19 is H, C02R20 or
perfluoroalkyl;
x is 1 to 12 when R19 is CN; and
R20 is alkyl,
produces the terminal organonitrile product compound of
Formula X
NC-(CH2)x+2-R19
X
wherein
R19 and x are as defined above.
Perfluoroalkyl is defined as CzF2z+1 where z is 1 to
12.
Preferred substrates are nonconjugated linear
alkenes, nonconjugated linear alkenenitriles,
nonconjugated linear alkenoates, linear alk-2-enoates
and perfluoroalkyl ethylenes. Most preferred substrates
include 3- and 4-pentenenitrile, alkyl 2- and 3- and
4-penteneoates, and CZF2z+1CH=CH2 (where z is 1 to 12).
The preferred products are terminal alkanenitriles,
linear alkanedinitriles, linear alkane(nitrile)esters,
16
SUBSTITUTE SHEET (RULE 26)
X186351
WO 95/28228 PCT/U595I04301
and 3-(perfluoroalkyl)propionitrile. Most preferred
products are adiponitrile, alkyl 5-cyanovalerate, and
CzF2a+1CH2CHZCN (where z is 1 to 12).
The present hydrocyanation process may be carried
out by charging a reactor with all of the reactants, or
' preferably the reactor is charged with the catalyst
precursor or catalyst components, the unsaturated
organic compound, the promoter and the solvent to be
used and the hydrogen cyanide added slowly. HCN may be
delivered as a liquid or as a vapor to the reaction.
Another technique is to charge the reactor with the
catalyst, promoter, and the solvent to be used, and feed
both the unsaturated compound and the HCN slowly to the
reaction mixture. The molar ratio of unsaturated
compound to catalyst generally is varied from about 10:1
to 2000:1.
Preferably, the reaction medium is agitated, such
as by stirring or shaking. The cyanated product can be
recovered by conventional techniques such as by
distillation. The reaction may be run either batchwise
or in a continuous manner.
The hydrocyanation reaction can be carried ouL with
or without a solvent. The solvent should be liquid at
the reaction temperature and pressure and inert towards
the unsaturated compound and the catalyst. Generally,
such solvents are hydrocarbons such as benzene or
xylene, or nitriles such as acetonitrile or
benzonitrile. In some cases, the unsaturated compound
to be hydrocyanated may serve as the solvent.
The exact temperature which is preferred is
dependent to a certain extent on the particular catalyst
being used, the particular unsaturated compound being
used and the desired rate. Generally, temperatures of
from -25 to 200°C can be used, with from 0 to 150°C
being preferred.
Atmospheric pressure is satisfactory for carrying
out the present invention and hence pressure of from
about 0.05,to 10 atmospheres are preferred due to the
17
SUBSTITUTE SHEET (RULE 26)
CA 02186351 2005-02-28
obvious eCCrlomic considerations although pressures of
frpm 0.05 to 100 atmospheres can be used if desired.'-
HCN may be added to the reaction as vapor or
liquid, or in a system utilizing a cyanohydrin as
carrier. See,, for example, U.S. 3,655,723.
Typ~.cally, the pxocesaes of this invention are
carried out ii7 the presence pf one or more Lewis acid
promoters which affect both the activity and selectivity
of the catalyst system. However, it should be
understood that the presence of a Lewis acid promoter is
riot deemed critical. to the invention, although it is
preferred. The promoter may be an inorganic ox oxgano-
metallic.compound in which the cation i.s selected from
the group consisting of scandium, titanium, vanadium,
chromium, manganese, iron, cobalt, copper, zinc, boron,
aluminum, yttrium, zirconium, niob~.um, molybdenum,
~adrriium, rhenium and tin. Examples include ZnBr2, ZnI2,
ZnCl2, ZnSOq, CuCl2, CuCl, Cu (03SCF3) y, CoCl2, GoI2,
FeClz, FeI2, FeClg, FeCl.2 (TIiF) 2, TiClq (THk') 2, TiClq,
. TiCl~, GlTi (OiPr) 3, MriCl2, SCC13, A1C13, (GgHl7) AlCly,
(CgHl7)2A1C1, (i~CqHg)2A1C1, Ph2A1C1, PhAlClg, ReClg,
ZrClq, NbGlS, VC13, CrCl2, MoClS, YC13, CdClz, LaCl3,
Er(Q3SCF3)3r Yb(02CCF3)3. SmCl3, 8Ph3, TaClS. Suitable
promoters are further described in U.S. 3,996,217: U.S.
3,996,218,; U,S. 9,779,353, These iaelude metal salts
(such as ZnCl2, Coi2, and SnCl2), and organometallic
compounds (such as R~r1C12, R3Sn03SCF3, and R38, whez~e R
is an alkyl ox aryl group).. '
a0 U.S. 4,$?4,889 describes how synergistic
combinations o~ promoters may be chosen to increase the
catalytic activity of the catalyst system_ Preferred
promoters axe CdCl2, 8nC12, 8 (Cglis) 3, and (C6H5) 35nX,
where X = CF3503, CH3C6H5SOg, ar (CgHS)3BCN. The amount
of promoter to nickel present in the reaction may be in
the range of 1:16 to 50:1,
I8
WO 95128228 PCTIUS95104301
R) A T...S
The following non-limiting examples further embody
and enable the processes and catalyst compositions of '
the invention. Generally, HCN reactions were done using
the following procedure unless otherwise noted.
The mixtures were heated in a thermostatically
controlled oil bath. HCN was delivered to the flask as
' an HCN/NZ gas mixture by bubbling dry nitrogen gas
through liquid HCN at 0°C (maintained in an ice bath);
this provides a vapor stream which is about 35~ HCN
(vol/vol). The rate of nitrogen gas flow determines the
rate of HCN delivery. Sample analysis was carried out
by gas chromatographic (GC) analysis.
EXAMPLE 1
~nthesis of the Li and of Formula I where each
R2 is OCH3 and each R1 is t-butyl (Ligand "A")
Ligand "A"
A solution of 2,2'-biphenol (28.1 g, 0.151 mol) in
49 mL phosphorus trichloride was heated at reflux for
2 hours. The excess PC13 was removed by distillation.
The residue was purified by vacuum distillation
(140-143°C at 0.5 mm Hg) to give 30.70 g (81~ yield)
1,1'-biphenyl-2,2'-diyl phosphorochloridite (as a clear
viscous oil which solidified to a white solid upon
standing at room temperature in an inert atmosphere for
an extended period of time), 31p(1H}NMg (121.4 MHz,
19
SUBSTITUTE SHEET (RULE 26)
WO 95128228 PCTIU595104301
dg-toluene): 8 180.1 (s), 85~ H3P04 external reference.
To a solution containing 1.018 g (2.84 mmoles) of
2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-
biphenyl and 0.575 g (5.68 mmoles) of NEt3 in 15 ml of
tetrahydrofuran (THF) was added 1.412 g (5.68 mmoles) of
1,1'-biphenyl-2,2'-diyl phosphorochloridite in 5 ml of
THF. The mixture was stirred overnight at room
temperature. The mixture was filtered through celite,
washed with THF and solvent removed to give 2.2 g of
white solid. Sip{1H) nmr (121.4 MHz, C6Dg): 145.15 s
and 138.5 s. IFi nmr (300 MHz,C6D6): singlet at 3.15 and
1.3 along with aromatic resonances.
EXAMPLE 2
Hydrocyanation of 3-Pentenenitrile with Ligand
("A"/Ni(COD)p wherein COD=bis(1,5-cyclooctadiene))
nickel: ZnCl2 promoter
340 mg of Ligand A and 40 mg of Ni(COD)2 were
dissolved in 5 ml of THF. The solvent was removed by
rotary evaporation and 5 ml of 3PN and IO mg of ZnCl2
were added. The mixture was treated with HCN at a
nitrogen flow rate of 12 cc/min and heated at 50, 60,
70, 80°C for 15 minutes at each temperature. After
heating at 80°C,. GC analysis indicated 24.3
adiponitrile (ADN), 5.6~ 2-methyl-glutaronitrile (MGN),
and 0.7~ of 2-ethylsuccinonitrile (ESN).
S1JBSTITUTE SHEET (RULE 26)
WO 95!28228 PCTIUS95104301
EXAMPLE 3
Synthesis of the Li and of Formula I where each
R2 and each R1 is t-pentyl (Ligand "B")
..
To a solution containing 2.0 g (8.0 mmoles) of
1,1'-biphenyl-2,2'-diyl phosphorochloridite in 10 ml of
toluene was added dropwise a solution containing 1.86 g
(3.99 mmoles) of 2,2'-dihydroxy-3,3',5,5'-tetra-t-
pentyl-1,1'-biphenyl and 0.9 g (8.9 mmoles) of NEt3 in
ml of toluene. The mixture was stirred overnight at
10 room temperature and then refluxed under nitrogen for
one hour. The mixture was filtered through celite,
washed with toluene and solvent removed to give 3.8 g of
white solid. 31p(1H) ~. (121.4 MHz, C6D6): 145.06 s and
137.1 s. 1H nmr (300 MHz,C6Dg): 2.0 (m, 4H), 1.8 (m,
15 4H), 1.5 (s, 12H), 1.3(s, 12H), 0.8 (m, 12H) along with
aromatic resonances. The 1H nmr spectrum also indicated
some toluene.
EXAMPLE 4
Hydrocyanations of 3-Pentenenitrile with
Ligand "B"/Ni(COD)2: ZnCl2 promoter
Carried out in a manner similar to Example 2,
except 380 mg of Ligand B and 40 mg of Ni(COD)2 were
dissolved in 5 ml of THF. The solvent was removed by
21
SUBSTITUTE SHEET (RULE 26)
R'O 95/28228 ~ ~ ~ ~ ~ ~ ~ PCT/US95104301
rotary evaporation and 5 ml of 3PN and 20 mg of ZnCl2
were added. The mixture Was treated with HCN at a
nitrogen flow -rate of 12 cc/min and heated at 50, 60,
70, 80, and 100°C for 15 minutes at each temperature.
After heating at 100°C, GC analysis indicated 7.2~ ADN,
l.l~ MGN, and 0.16 of ESN.
EXAMPLE 5
Synthesis of the Ligand of Formula I where each
R2 and each R1 are t-butyl (Ligand "C")
Ligand "C"
To a solution containing 1.2 g (4.8 mmoles) of
1,1'-biphenyl-2,2'-diyl phosphorochloridite in 20 ml of
toluene was added dropwise a solution containing 1.0 g
(2.4 mmoles) of 2,2'-dihydroxy-3,3',5,5'-tetra-t-butyl-
1,1'-biphenyl and 1.2 g (11.8 mmoles) of NEt3 in 20 ml
of toluene. The mixture was refluxed under nitrogen for
about two hours. The mixture was filtered through
celite, washed with toluene and solvent removed to give
2.1 g of white solid. 31p (1H) n~. (121.4 MHz, CgDS):
145.2 d (J = 4Hz) and 137.77 d (J s 4Hz). 1H nmr(300
MHz,C6D6): 1.77 s, 1.58 s along with aromatic
resonances. The 1H nmr spectrum also indicated some
toluene.
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SUBSTITUTE SHEET (RULE 26)
WO 95/28228 218 6 3 51 pCTlUS951D4301
EXAMPLE 6
Hydrocyanations of 3-Pentenenitrile with
Ligand "C"/Ni(COD)2: ZnCl2 promoter
Carried out in a manner similar to Example 2,
except 365 mg of LigandC and 40 mg of Ni(COD)2 were
dissolved in 5 ml of THF. The solvent was removed by
rotary evaporation and 5 ml of 3PN and 20 mg of ZnCl2
' were added. The mixture was treated with HCN at a
nitrogen flow rate of 12 cc/min and heated at 50, 60,
70, 80, and 100°C for 15 minutes at each temperature.
After heating at 100°C, GC analysis indicated 36.4 ADN,
7.0~ MGN, and 1.0~ of ESN.
Although particular embodiments of the present
invention have been described in the foregoing
description, it will be understood by those skilled in
the art that the invention is capable of numerous
modifications, substitutions and rearrangements without
departing from the spirit or essential attributes of the
invention. Reference should be made to the appended
claims, rather than the foregoing specification, as
indicating the scope of the invention.
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SUBSTITUTE SHEET (RULE 26)
