Processes and catalyst compositions for hydrocyanation of monoolefins

Processes for hydrocyanation of nonconjugated acyclic aliphatic monoolefins, monoolefins conjugated to an ester group, or monoolefins conjugated to a nitrile group which utilize a catalyst precursor composition comprising a bidentate phosphite ligand and zero-valent nickel preferably in the presence of a Lewis acid prompter. Catalyst precursor compositions are also disclosed.

FIELD OF THE INVENTION 
This invention relates to processes and catalyst compositions useful in the 
hydrocyanation of monoolefins. In particular, the invention relates to the 
hydrocyanation of monoolefins using zero-valent nickel and a bidentate 
phosphite ligand in the presence of a Lewis acid promoter. 
BACKGROUND OF THE INVENTION 
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 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. Pat. Nos. 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-pentenenitrile 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. Pat. No. 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. 
U.S. Pat. No. 3,496,218 discloses a nickel hydrocyanation catalyst promoted 
with various boron-containing compounds, including triphenylboron and 
alkali metal borohydrides. U.S. Pat. No. 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. Pat. No. 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 invention 
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.; Pringle, P. G.; and Shaw, G.; J. 
Chem. Soc.; Chem. Commun., 803, 1991, Union Carbide, WO 93,03839. 
Also, some of the ligands of the present invention have been disclosed with 
rhodium in catalyst complexes useful for the hydroformylation of 
functionalized olefins; see, Cuny, G. D., Buchwald, S. L., J. Am. Chem. 
Soc. 1993, 115, 2066. 
The present invention provides for novel processes and catalyst precursor 
compositions which are more rapid, selective, efficient and stable than 
current processes and catalyst complexes employed 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 of the invention which hereinafter follows. 
SUMMARY OF THE INVENTION 
The present invention provides a process for hydrocyanation comprising 
reacting a nonconjugated acyclic aliphatic monoolefin, a monoolefin 
conjugated to an ester group, e.g., methyl pent-2-eneoate, or a monoolefin 
conjugated to a nitrile group, e.g., 3-pentenenitrile; with a source of 
HCN in the presence of a catalyst precursor composition comprising 
zero-valent nickel and a bidentate phosphite ligand of Formula I, 
##STR1## 
wherein each R.sup.1 is independently a tertiary substituted hydrocarbon 
of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to 
C.sub.12 alkyl; 
each R.sup.5 is independently a tertiary substituted hydrocarbon of up to 
12 carbon atoms; 
and wherein said reaction is carried out to produce a terminal 
organonitrile. Preferably, the reaction is carried out in the presence of 
a Lewis acid promoter. 
The present invention further provides a process for hydrocyanation 
comprising reacting a nonconjugated acyclic aliphatic monoolefin, a 
monoolefin conjugated to an ester group, e.g., methyl pent-2-eneoate, or a 
monoolefin conjugated to a nitrile group, e.g., 3-pentene-nitrile; with a 
source of HCN in the presence of a catalyst precursor composition 
comprising zero-valent nickel and a bidentate phosphite ligand of Formulas 
II, III, IV, or V, as set forth below, and wherein said reaction is 
carried out to produce a terminal organonitrile. Preferably, the reaction 
is carried out in the presence of a Lewis acid promoter. 
##STR2## 
wherein each R.sup.6 and R.sup.7 is independently a tertiary substituted 
hydrocarbon of up to 12 carbon atoms; and 
each R.sup.8 is independently H or a branched or straight chain alkyl of up 
to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 
alkyl. 
##STR3## 
wherein each R.sup.9 is independently H or a branched or straight chain 
alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to 
C.sub.12 alkyl; and 
each R.sup.10 is independently a tertiary substituted hydrocarbon of up to 
12 carbon atoms. 
##STR4## 
wherein each R.sup.14 is independently a tertiary substituted hydrocarbon 
of up to 12 carbon atoms or Si(R.sup.11).sub.3 where R.sup.11 is 
independently a branched or straight chain alkyl of up to 12 carbon atoms 
or phenyl. 
##STR5## 
wherein R.sup.12 is H or a branched or straight chain alkyl of up to 12 
carbon atoms; and 
each R.sup.13 is independently a branched or straight chain alkyl of up to 
12 carbon atoms. 
The monoolefins of the above-identified processes are described by Formulas 
VI or VIII, and the corresponding terminal organonitrile compounds 
produced are described by Formulas VII or IX, respectively. 
##STR6## 
wherein R.sup.2 is H, CN, CO.sub.2 R.sup.3, or perfluoroalkyl; 
y is 0 to 12; 
x is 0 to 12; and 
R.sup.3 is alkyl; or 
##STR7## 
wherein R.sup.2 is H, CN, CO.sub.2 R.sup.3, or perfluoroalkyl; 
x is 0 to 12; and 
R.sup.3 is alkyl. 
The present invention also provides for a catalyst precursor composition 
comprising zero-valent nickel and a bidentate phosphite ligand of Formula 
I, 
##STR8## 
wherein each R.sup.1 is independently a tertiary substituted hydrocarbon 
of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to 
C.sub.12 alkyl; and 
each R.sup.5 is independently a tertiary substituted hydrocarbon of up to 
12 carbon atoms. 
The present invention further provides for catalyst precursor compositions 
comprising zero-valent nickel and a bidentate phosphite ligand of Formulas 
II, III, IV, or V, set forth below. 
##STR9## 
wherein each R.sup.6 and R.sup.7 is independently a tertiary substituted 
hydrocarbon of up to 12 carbon atoms; and 
each R.sup.8 is independently H or a branched or straight chain alkyl of up 
to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to C.sub.12 
alkyl. 
##STR10## 
wherein each R.sup.9 is independently H or a branched or straight chain 
alkyl of up to 12 carbon atoms, or OR.sup.4 wherein R.sup.4 is C.sub.1 to 
C.sub.12 alkyl; and 
each R.sup.10 is independently a tertiary substituted hydrocarbon of up to 
12 carbon atoms. 
##STR11## 
wherein each R.sup.14 is independently a tertiary substituted hydrocarbon 
of up to 12 carbon atoms or Si(R.sup.11).sub.3 where R.sup.11 is 
independently a branched or straight chain alkyl of up to 12 carbon atoms 
or phenyl. 
##STR12## 
wherein R.sup.12 is H or a branched or straight chain alkyl of up to 12 
carbon atoms; and 
each R.sup.13 is independently a branched or straight chain alkyl of up to 
12 carbon atoms. 
Preferably, the catalyst precursor compositions of Formulas I, II, III, IV 
and V further comprise a Lewis acid promoter. 
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The catalyst precursor compositions of the invention are comprised of a 
bidentate phosphite ligand and zero-valent nickel. The preferred ligand of 
the invention is described below by Formula I, wherein each R.sup.1 is 
independently a tertiary substituted hydrocarbon containing up to 12 
carbon atoms, or OR.sup.4 wherein R.sup.4 is a C.sub.1 to C.sub.12 alkyl. 
R.sup.4 can be primary, secondary or tertiary; examples include methyl, 
ethyl, isopropyl and t-butyl. Each R.sup.1 may be the same or different. 
In a more preferred ligand both R.sup.1 groups are OR.sup.4 wherein 
R.sup.4 is methyl. R.sup.5 is a tertiary substituted hydrocarbyl group 
containing up to 12 single bond carbon atoms. 
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. 
##STR13## 
These ligands may be prepared by a variety of methods known in the art, for 
example see descriptions in WO 93,03839, U.S. Pat. No. 4,769,498; U.S. 
Pat. No. 4,688,651, J. Amer. Chem. Soc., 115 , 2066, 1993. The reaction of 
2,2'-biphenol with phosphorus trichloride gives 1,1'-biphenyl-2,2'-diyl 
phosphorochloridite. The reaction of this chloridite with 
2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl in the 
presence of triethylamine gives the most preferred ligand wherein R.sup.1 
is methoxyl. 
Other bidentate phosphite ligands of the invention are described above by 
Formulas II, III, IV, and V. While these ligands are not as preferred as 
Formula I, they nevertheless are considered useful ligands of the present 
invention. These ligands may be prepared according to the non-limiting 
examples set forth below. 
The zero-valent nickel can be prepared or generated according to techniques 
known in the art (U.S. Pat. Nos. 3,496,217; 3,631,191; 3,846,461; 
3,847,959; and 3,903,120 which are incorporated herein by reference). 
Zero-valent nickel compounds that contain ligands which can be displaced 
by the organophosphorus ligand are a preferred source of zero-valent 
nickel. Two such preferred zero-valent nickel compounds are Ni(COD).sub.2 
(COD is 1,5-cyclooctadiene) and Ni(P(O-o-C.sub.6 H.sub.4 
CH.sub.3).sub.3).sub.2 (C.sub.2 H.sub.4), both of which are known in the 
art. Alternatively, divalent 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 NiY.sub.2 where Y is halide, carboxylate, 
or acetylacetonate. Suitable reducing agents include metal borohydrides, 
metal aluminum hydrides, metal alkyls, Zn, Fe, Al, Na, or H.sub.2. 
Elemental nickel, preferably nickel powder, when combined with a 
halogenated cataylst, as described in U.S. Pat. No. 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-pentenenitriles and 4-pentenenitriles are especially 
preferred. 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 
2-pentenenitriles, 3-pentenenitriles, 4-pentenenitriles and methyl 
pent-3-enoate. The monoolefins may also be conjugated to an ester group or 
a nitrile group such as methyl pent-2-enoate and 2-pentenenitrile, 
respectively. 
Two formulas are presented below which together describe these substrates 
of the invention; Formulas VI and VIII. Substrates of Formula VI yield 
terminal organonitriles of Formula VII, while Formula VIII substrates will 
yield terminal organonitriles of Formula IX. 
EQU CH.sub.3 --(CH.sub.2).sub.y --CH.dbd.CH--(CH.sub.2).sub.x R.sup.2VI 
wherein 
R.sup.2 is H, CN, CO.sub.2 R.sup.3, or perfluoroalkyl; 
y is 0 to 12; 
x is 0 to 12; and 
R.sup.3 is alkyl; 
produces the terminal organonitrile product compound of Formula VI 
EQU NC--(CH.sub.2).sub.y+x+3 --R.sup.2 VII 
wherein 
R.sup.2, y and x are as defined above. 
EQU CH.sub.2 .dbd.CH--(CH.sub.2).sub.x R.sup.2 VIII 
wherein 
R.sup.2 is H, CN, CO.sub.2 R.sup.3, or perfluoroalkyl; 
x is 0 to 12; and 
R.sup.3 is alkyl, 
produces the terminal organonitrile product compound of Formula IX 
EQU NC--(CH.sub.2).sub.x+2 --R.sup.2 IX 
wherein 
R.sup.2 and x are as defined above. 
Perfluoroalkyl is defined as C.sub.z (F.sub.2z+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 2-, 3- and 
4-pentenenitrile, alkyl 2- and 3- and 4-penteneoates, and C.sub.x 
F.sub.2x+1 CH.dbd.CH.sub.2 (where x is 1 to 12). 
The preferred products are terminal alkanenitriles, linear 
alkanedinitriles, linear alkane(nitrile)esters, and 
3-(perfluoroalkyl)propionitrile. Most preferred products are adiponitrile, 
alkyl 5-cyanovalerate, and C.sub.x F.sub.2x+1 CH.sub.2 CH.sub.2 CN (where 
x is 1 to 12). 
The present hydrocyanation processes may be carried out by charging a 
reactor with all of the reactants, or preferably the reactor is charged 
with the catalyst precursor composition or catalyst components, the 
unsaturated organic compound, the optionally present 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, optionally present 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 distillation. The reaction may be run either batchwise or in a 
continuous manner. 
The hydrocyanation reaction can be carried out 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 composition. 
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 composition being used, the particular 
unsaturated compound being used and the desired rate. Generally, 
temperatures of from about -25.degree. to about 200.degree. C. can be 
used, with from about 0.degree. to about 150.degree. C. being preferred. 
Atmospheric pressure is satisfactory for carrying out the present invention 
and hence pressures of from about 0.05 to about 10 atmospheres are 
preferred due to obvious economic considerations. However, pressures of 
from about 0.05 to about 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 the carrier. See, for example, U.S. Pat. No. 
3,655,723 the contents of which are incorporated herein by reference. 
The processes of this invention can be and preferably are carried out in 
the presence of one or more Lewis acid promoters which affect both the 
activity and selectivity of the catalyst system. The promoter may be an 
inorganic or organometallic compound in which the cation is selected from 
the group consisting of scandium, titanium, vanadium, chromium, manganese, 
iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, 
molybdenum, cadmium, rhenium and tin. Suitable promoters are further 
described in U.S. Pat. Nos. 3,496,217; 3,496,218; and 4,774,353, the 
contents of which are incorporated herein by reference. These include 
metal salts (such as ZnCl.sub.2, CoI.sub.2, and SnCl.sub.2) and 
organometallic compounds (such as RAlCl.sub.2, R.sub.3 SnO.sub.3 
SCF.sub.3, and R.sub.3 B, where R is an alkyl or aryl group). 
U.S. Pat. No. 4,874,884 describes how synergistic combinations of promoters 
may be chosen to increase the catalytic activity of the catalyst system. 
Preferred promoters are CdCl.sub.2, ZnCl.sub.2, B(C.sub.6 H.sub.5).sub.3, 
and (C.sub.6 H.sub.5).sub.3 SnX, where X=CF.sub.3 SO.sub.3, CH.sub.3 
C.sub.6 H.sub.5 SO.sub.3, or (C.sub.6 H.sub.5).sub.3 BCN. The amount of 
promoter to nickel to promoter present in the reaction may be in the range 
of from about 1:16 to about 50:1.

EXAMPLES 
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/N.sub.2 gas mixture by bubbling dry nitrogen gas 
through liquid HCN at 0.degree. 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 chromatographlc (GC) analysis. The ligand, unless 
otherwise noted, was 
{2,2'-bis1,1'-biphenyl-2,2'-diyl)phosphite!-3,3'-di-t-butyl-5,5'dimethoxy 
-1,1'-biphenyl} (Ligand "A"). 
EXAMPLE 1 
Preparation of the Ligand of Formula I (Ligand "A") 
Ligand "A" (corresponding to Formula I) may be prepared using a literature 
procedure, for example see descriptions in WO 93,03839, U.S. Pat. No. 
4,769,498; U.S. Pat. No. 4,688,651, J. Amer. Chem. Soc., 115, 2066, 1993. 
A solution of 2,2'-biphenol (28.1 g, 0.151 mol) in 49 mL phosphorus 
trichloride was heated at reflux for 2 hr. The excess PCl3 was removed by 
distillation. The residue was purified by vacuum distillation 
(140.degree.-143.degree. 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 (RT) in an 
inert atmosphere for an extended period of time). .sup.31 P{.sup.1 H}NMR 
(121.4 MHz, d.sub.8 -toluene): .delta. 180.1 (s), 85% H.sub.3 PO.sub.4 
external reference. 
Then to a solution of 1,1'-biphenyl-2,2'-diyl phosphorochloridite (1.40 g, 
5.6 mmol) in 0.6 mL toluene at -40.degree. C. was added, over a 15 min 
period, a solution of 
2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl (1.00 g, 2.80 
mmol) and triethylamine (1.79 mL, 22.4 mmol) in 12 mL toluene. The 
resulting mixture was allowed to warm slowly (overnight) to room 
temperature. After the addition of water (6.5 mL), the reaction mixture 
was filtered. The residue was washed several times with water and dried in 
vacuo overnight to give a white solid. The solid was recrystallized from 
acetonitrile to give a white powder (0.72 g, 33% yield). .sup.1 H NMR (300 
MHz, CDCl.sub.3): .delta. 1.46 (s, 18H); 3.39 (s, 6H); 6.90-7.32 (m, 20H); 
.sup.31 P{.sup.1 H}NMR (121.4 MHz, d.sub.8 -CDCl.sub.3): .delta. 147.0 
(s), 85% H.sub.3 PO.sub.4 external reference. 
EXAMPLE 2 
Hydrocyanation of 3-Pentenenitrile with ligand/Ni(COD).sub.2 (bis 
(1,5-cyclooctadiene)nickel): ZnCl.sub.2 Promoter 
350 mg of Ligand "A" (0.44 mmoles) and 20 mg of Ni(COD).sub.2 (0.073 
mmoles) were dissolved in 5 mL of tetrahydrofuran (THF). The solvent was 
removed by vacuum evaporation. 5 mL of 3PN and 10 mg (0.073 mmoles) of 
ZnCl.sub.2 were added. The mixture was treated with HCN at 30 cc/min of 
N.sub.2 at 50.degree. C. for 15 minutes, 60.degree. C. for 15 minutes, and 
70.degree. C. for 15 minutes. After this time; GC analysis indicated area 
% of 77.1% ADN and 20.7% 2-methyl-glutaronitrile (MGN). 
The above procedure was repeated using 85 mg (0.11 mmoles) of Ligand "A". 
After heating at 70.degree. C.; G.C. analysis indicated area % of 45.6% 
ADN and 13.1% of MGN. 
EXAMPLE 3 
Hydrocyanation of 3-Pentenenitrile with Ligand/Ni(COD).sub.2 : SnCl.sub.2 
Promoter 
Performed the procedure of Example 2, but 170 mg of Ligand "A" (0.22 
mmoles) and 14 mg of SnCl.sub.2 (0.074 mmoles) as promoter were used. GC 
analysis indicated area % of 16.0% ADN and 3.9% of MGN. 
EXAMPLE 4 
Hydrocyanations of 3-Pentenenitrile with Ligand/Ni(COD).sub.2 : BPh.sub.3 
Promoter 
In a manner similar to Example 2, except using 170 mg of Ligand "A" (0.22 
mmoles) and 15 mg (0.062 mmoles) of BPh.sub.3 as promoter, hydrocyanation 
was carried out at 5 cc/min N.sub.2 at 40.degree. C. After 3 hours, GC 
analysis indicated area % of 5.3% ADN and 0.39% of MGN. 
Similarly, the experiment was repeated as above with 340 mg (0.43 mmoles) 
of Ligand "A", 40 mg of Ni(COD).sub.2 (0.14 mmoles) and 15 mg (0.062 
mmoles) of BPh.sub.3. Hydrocyanation was carried out at 3 cc/min N.sub.2 
at 40.degree. C. After 2 hours, GC analysis indicated area % of 39.1 ADN 
and 2.1% of MGN. 
EXAMPLE 5 
Hydrocyanation of 3-Pentenenitrile Using Ligand/Ni(COD).sub.2 : Ph.sub.3 
SnOTf Promoter 
Performed the procedure of Example 2 using 170 mg (0.22 mmoles) of Ligand 
"A" and 20 mg (0.073 mmoles) of Ni(COD).sub.2 with 10 mg (0.02 mmoles) of 
Ph.sub.3 SnOTf. Hydrocyanation was carried out at 12 cc/min N.sub.2 at 
50.degree. C. for 5 hours. GC analysis indicated area % of 47.9% ADN and 
2.0% of MGN. 
EXAMPLE 6 
Preparation of (COD)NiL 
After removing the solvent from a THF solution of Ligand "A" with 
Ni(COD).sub.2, .sup.31 P NMR in C.sub.6 D.sub.6 consisted of two singlets 
at 178.9 and 146.6 ppm. The resonance at 146.6 ppm corresponded to free 
Ligand "A". The compound with resonance at 178.9 ppm was determined to be 
(COD)NiL. A THF solution containing 50 mg (0.18 mmoles) of Ni(COD).sub.2 
and 215 mg of ligand (0.27 mmoles) was stirred overnight. A white 
precipitate formed which was filtered to give 0.206 g of (COD)NiL. .sup.31 
P NMR in C.sub.6 D.sub.6 : 178.9 ppm. .sup.1 H NMR in C.sub.6 D.sub.6 : 
7.7 (d, 2H), 7.2 (m, 8H), 7.0 (m, 6H), 6.9 (d, 2H), 6.6 (d, 2H), 4.8 (m, 
2H), 4.2 (m, 2H), 2.9 (s, 6H), 2.0 (m)+1.7 (s)+1.4 (m) (total area, 26H). 
EXAMPLE 7 
Preparation of Nickel Catalyst from Ni(acac).sub.2 /AlEt.sub.3 and Ligand 
A mixture containing 0.219 g (0.85 mmoles) of Ni(acac).sub.2 
(acac=acetylacetonate) and 1.004 g (1.28 mmoles) of Ligand "A" in 12 mL of 
toluene was cooled to 0.degree. C. and 1.3 mL of AlEt.sub.3 (25% solution 
in toluene, 2.5 mmoles) was added. The mixture was warmed to room 
temperature and then heated to 65.degree. C. for 15 minutes. The mixture 
was stirred overnight, concentrated by vacuum evaporation and hexane added 
to yield 1.00 g of yellow solid. .sup.31 P NMR in C.sub.6 D.sub.6 : 
singlets at 169.8 and 162.8 ppm. .sup.31 P NMR indicates a 1:1 mixture of 
NiL.sub.2 and NiL(ethylene). 
EXAMPLE 8 
Preparation of Nickel Catalyst from Ni(acac).sub.2 /AlEt.sub.3 and Ligand 
The procedure of Example 7 was repeated using 2.193 g (8.54 mmoles) of 
Ni(acac).sub.2, 10.073 g (12.8 mmoles) of Ligand "A" and 12.3 mL (23.4 
mmoles) of AlEt.sub.3. Hexane addition to the concentrated reaction 
mixture yielded 5.866 g of gray solid. This material was not soluble in 
C.sub.6 D.sub.6. .sup.31 P NMR in THF-d.sub.8 consisted of a singlet at 
166.9 ppm. This material was designated sample "8A". The filtrate was 
concentrated again and hexane added to precipitate out 1.916 g of yellow 
solid. .sup.31 P NMR in C.sub.6 D.sub.6 : 169.7 ppm. This material was 
designated sample "8B". 
EXAMPLE 9 
Preparation of Nickel Catalyst from Ni(acac).sub.2 /AlEt.sub.3 and Ligand 
The procedure of Example 8 was repeated using 1.102 g (4.29 mmoles) 
Ni(acac).sub.2, 5.062 g (6.43 mmoles) of Ligand "A", and 6.5 mL (12.4 
mmoles) of AlEt.sub.3. The mixture was not heated to 65.degree. C. but 
stirred at room temperature overnight. After concentrating and adding 
hexane, 4.340 g of yellow solid was isolated. .sup.31 P NMR in C.sub.6 
D.sub.6 matched that of Example 7 but also showed a small peak at 159.4 
ppm. NMR indicated a 2:1 ratio of LNi(ethylene): L.sub.2 Ni. 
EXAMPLE 10 
Hydrocyanation of 3-Pentenenitrile Using Catalyst Prepared from Example 7 
To 0.175 g (0.12 mmoles of nickel) of sample from Example 7 and 0.190 g 
(0.24 mmoles) of Ligand "A" were added 5 mL of 3PN and 20 mg (0.04 mmoles) 
of Ph.sub.3 SnOTf. The mixture was treated with HCN at 12 cc/min of 
N.sub.2 at 50.degree. C. After heating at 50.degree. C. for 2.5 hr, the 
mixture was heated at 70.degree. C. for 0.5 hour. GC analysis using 
indicated area % of 85.7% ADN and 4.0% of MGN. 
EXAMPLE 11 
Hydrocyanation of 3-Pentenenitrile Using Catalyst Prepared from Example 8 
(8A) 
0.175 g (0.11 mmoles of nickel) of sample "8A", and 0.190 g (0.24 moles) of 
Ligand "A" were added to 5 mL of 3-pentenenitrile and 20 mg (0.04 moles) 
of Ph.sub.3 SnOTf. The mixture was treated with HCN at 12 cc/min N.sub.2 
at 50.degree. C. After 2.5 hour, GC analysis indicated area % of 64.5% of 
ADN and 2.3% of MGN. 
EXAMPLE 12 
Hydrocyanation of 3-Pentenenitrile Using Catalyst Prepared from Example 8 
(8B) 
175 mg (0.11 moles of nickel) of sample "8B" and 190 mg (0.24 mmoles) of 
Ligand "A" in 5 mL of 3PN was added to 20 mg (0.04 mmoles) of Ph.sub.3 
SnOTf. The mixture was treated with HCN at 12 cc/min N.sub.2 at 50.degree. 
C. After 3 hours, GC analysis indicated area % of 21.9% ADN and 2.5% MGN. 
EXAMPLE 13 
Hydrocyanation of 3-Pentenenitrile Using Catalyst Prepared from Example 9 
To 0.175 g (0.15 moles of nickel) of the product from Example 9 and 0.190 g 
(0.24 moles) of Ligand "A" were added 5 mL of 3-pentenenitrile and 20 mg 
(0.04 moles) of Ph.sub.3 SnOTf. 500 mg of HCN in 2 mL of toluene was added 
and the mixture heated to 50.degree. C. After 1 hour, GC analysis 
indicated mole % of 37.4% ADN and 2.2% MGN. Another 500 mg of HCN in 2 mL 
of toluene was added and the mixture stirred at 70.degree. C. overnight. 
GC analysis indicated mole % of 64.7% ADN and 3.7% MGN. 
EXAMPLE 14 
Hydrocyanation of 3-Pentenenitrile Without Promoter 
170 mg (0.22 moles) of Ligand "A" and 20 mg (0.073 moles) of Ni(COD).sub.2 
were dissolved in 5 mL of THF. The solvent was removed by vacuum 
evaporation. To the mixture was added 5 mL of 3-pentenenitrile. The 
mixture was hydrocyanated at 12 cc/min N.sub.2 at 50.degree. C. After two 
hours, GC analysis indicated area % of 1.5% ADN, 0.1% MGN and 0.02% of 
2-ethylsuccinonitrile (ESN). 
EXAMPLE 15 
Hydrocyanation of Methyl-3-Pentenoate with Ph.sub.3 SnOTf Promoter 
170 mg (0.10 mmoles) of LNi (ethylene) and NiL.sub.2 in a mole ratio of 
1:1.5 and 190 mg (0.24 moles) of Ligand "A" were added 5 mL of 
methyl-3-pentenoate. To this mixture was added 20 mg (0.04 mmoles) of 
Ph.sub.3 SnOTf. The mixture was hydrocyanated at 12 cc/min N.sub.2 at 
50.degree. C. for 2 hours and at 70.degree. C. for 2 hours. After this 
time, GC analysis indicated area % of 0.8% 3-cyanomethylvalerate; 3.5% of 
4-cyano-methylvalerate and 59.9% of 5-cyanomethylvalerate. 
EXAMPLE 16 
Hydrocyanation of 1-octene with Zinc Chloride Promoter 
To 5 mL of THF was added 340 mg (0.43 moles) of Ligand "A" and 40 mg (0.14 
mmoles) of Ni(COD).sub.2. The solvent was removed and 3 mL of toluene, 2 
mL of 1-octene and 10 mg (0.073 mmoles) of ZnCl.sub.2 were added. The 
mixture was hydrocyanated at 12 cc/min N.sub.2 at 60.degree. C. After 2 
hours, GC analysis indicated area % of 16% n-octylcyanide. 
EXAMPLE 17 
Hydrocyanation of Perfluorobutyulethylene 
To 5 mL of THF was added 340 mg (0.43 moles) of Ligand "A" and 40 mg (0.14 
mmoles) of Ni(COD).sub.2. The solvent was removed and 5 mL of toluene, 2 
mL of perfluorobutylethylene and 10 mg (0.073 mmoles) of ZnCl.sub.2 were 
added. The mixture was hydrocyanated at 12 cc/min N.sub.2 at 40.degree. C. 
After 0.5 hours, GC analysis indicated that all of the olefin has been 
converted to perfluorobutyl-CH.sub.2 CH.sub.2 --CN. 
COMATIVE EXAMPLE 18 
Hydrocyanation Using Bidentate Ligand "B" 
##STR14## 
75 mg (0.12 mmoles) of the above Ligand "B" and 20 mg (0.07 mmoles) of 
Ni(COD).sub.2 were dissolved in 5 mL of THF and the solvent was removed. 5 
mL of 3-pentenenitrile and 10 mg (0.073 mmoles) of ZnCl.sub.2 were added. 
The mixture was treated with HCN at 40.degree. C. at 30 cc/min N.sub.2. No 
conversion to adiponitrile was observed after 1.5 hours. The procedure was 
repeated but with 0.150 g (0.24 mmoles) of the above Ligand "B" and HCN at 
30 cc/min N.sub.2 at 50.degree. C. for 15 min., 60.degree. C. for 15 min 
and 70.degree. C. for 15 min. After this time, no adiponitrile was 
observed. 
COMATIVE EXAMPLE 19 
Hydrocyanation Using Ligand "C" 
##STR15## 
To 160 mg (0.21 mmoles) of the above Ligand "C" and 20 mg (0.07 mmoles) of 
Ni(COD).sub.2 was added 5 mL THF. The solvent was removed and 5 mL of 
3-pentenenitrile and 10 mg (0.073 mmoles) of ZnCl.sub.2 were added. 
Hydrocyanation was done at 30 cc/min N.sub.2 at 50.degree. C. for 15 min, 
60.degree. C. for 15 min and 70.degree. C. for 15 min. No adiponitrile 
product was generated. 
EXAMPLE 20 
Hydrocyanation of 2-Pentenenitrile 
A mixture of NiL.sub.2 (L=Ligand "A") (0.100 g; 0.06 mmol), Ph.sub.3 
Sn(O.sub.3 SCF.sub.3) (0.030 g; 0.06 mmol), cis-2-pentenenitrile (0.017 g; 
0.21 mmol) in benzene (1.30 mL) and acetonitrile (0.50 mL) was heated 
(71.degree. C.) with stirring under nitrogen atmosphere in a septum capped 
glass vial. HCN (50 uL of 2.55M HCN in benzene; 0.0034 g HCN; 0.13 mmol) 
was injected into the mixture and aliquots removed periodically and 
analyzed by GC. After 1 hr, the mixture contained 2-pentenenitrile (0.082 
mmol), adiponitrile (0.110 mmol), 2-methylglutaronitrile (0.006 mmol), 
2-ethylsuccinonitrile (0.002 mmol), and valeronitrile (0.007 mmol). 
EXAMPLE 21 
Hydrocyanation Using Ligand "D" 
##STR16## 
This ligand, D, was prepared similarly to Ligand "A" starting with the 
oxidation of 2,4-di-t-butylphenol to give the biphenol followed by the 
reaction with 1,1'biphenyl-2,2'-diyl phosphorocholoridite. n-BuLi was used 
as the base instead of NEt.sub.3. 369 mg of Ligand "D" and 40 mg of 
Ni(COD).sub.2 were dissolved in 5 mL of THF and the solvent removed. 5 mL 
of 3PN and 20 mg of ZnCl.sub.2 were added. The mixture was treated with 
HCN at 80.degree. C. at 12 cc/min N.sub.2. After 1.5 hr, 31.1% of ADN, 
7.9% of MGN and 0.8% of ESN were obtained as determined by GC analysis. 
EXAMPLE 22 
Hydrocyanation Using Ligand "E" 
##STR17## 
This ligand, E, was prepared similarly to Ligand "A" starting with the air 
oxidation of 2,4-di-t-pentylphenol to give the biphenol followed by 
treatment with 1,1'biphenyl-2,2'-diyl phosphorochloridite. n-BuLi was used 
as the base instead of NEt.sub.3. .sup.31 P NMR in C.sub.6 D.sub.6 : 145.1 
ppm. 380 mg of Ligand "E" and 40 mg of Ni(COD).sub.2 were dissolved in 5 
mL of THF and the solvent removed. 5 mL of 3PN and 20 mg of ZnCl.sub.2 
were added. The mixture was treated with HCN at 50.degree., 60.degree., 
70.degree., 80.degree., and 100.degree. C. for 15 minutes each at 12 
cc/min N.sub.2. After heating at 100.degree. C., 36.8% of ADN, 8.5% of MGN 
and 0.9% of ESN were obtained as determined by GC analysis. 
EXAMPLES 23 TO 57 
Use of Other Lewis Acid Promoters in the Hydrocyanation of 3-Pentenenitrile 
L=Ligand "A"! 
A mixture NiL.sub.2 (0.230 g; 0.14 mmol) and L (0.110 g; 0.14 mmol), 
3-pentenenitrile (5.0 mL; 52 mmol), and a Lewis acid promoter (0.14 mmol) 
(indicated in the Table) was heated at 70.degree. C. and treated with HCN 
via vapor transfer as described above (N.sub.2 flow=12 cc/min) for 2 
hours. The results in terms of percent conversion and percent selectivity 
are presented in the Table below. Conversion and selectivity are defined 
as follows: 
EQU Conversion=100.times.(ADN+MGN+ENS)/(initial 3PN) 
EQU Selectivity=100.times.ADN/(ADN+MGN+ESN) 
where ADN is adiponitrile, MGN is 2-methylglutaronitrile, ESN is 
2-ethylsuccinonitrile, and 3PN is 3-pentenenitrile. 
TABLE 
______________________________________ 
Ex. Promoter Conversion % 
Selectivity % 
______________________________________ 
23 ZnBr.sub.2 26 83 
24 ZnI.sub.2 59 82 
25 ZnCl.sub.2 64 76 
26 ZnSO.sub.4 31 79 
27 CuCl.sub.2 7 89 
28 CuCl 13 80 
29 Cu(O.sub.3 SCF.sub.3).sub.2 
4 95 
30 CoCl.sub.2 28 74 
31 CoI.sub.2 28 79 
32 FeI.sub.2 25 79 
33 FeCl.sub.3 14 71 
34 FeCl.sub.2 (THF).sub.2 * 
52 75 
35 TiCl.sub.4 (THF).sub.2 * 
12 87 
36 TiCl.sub.4 25 80 
37 TiCl.sub.3 24 85 
38 MnCl.sub.2 41 79 
39 ScCl.sub.3 13 88 
40 AlCl.sub.3 15 85 
41 (C.sub.8 H.sub.17)AlCl.sub.2 
26 82 
42 (i-C.sub.4 H.sub.9).sub.2 AlCl 
3 83 
43 Ph.sub.2 AlCl 
13 81 
44 ReCl.sub.5 22 97 
45 ZrCl.sub.4 25 87 
46 NbCl.sub.5 2 85 
47 VCl.sub.3 7 85 
48 CrCl.sub.2 1 80 
49 MoCl.sub.5 3 78 
50 YCl.sub.3 48 88 
51 CdCl.sub.2 60 80 
52 LaCl.sub.3 31 87 
53 Er(O.sub.3 SCF.sub.3).sub.3 
34 90 
54 Yb(O.sub.2 CCF.sub.3).sub.3 
36 84 
55 SmCl.sub.3 40 83 
56 BPh.sub.3 40 95 
57 TaCl.sub.5 4 85 
______________________________________ 
*Tetrahydrofuran 
EXAMPLE 58 
Preparation of the Ligand of Formula II Where R.sup.6 and R.sup.7 are 
t-butyl and R.sup.8 is OCH.sub.3 (Ligand "F") 
##STR18## 
To 1.44 g of the dichlorodite derived from PCl.sub.3 and 
2-t-butyl-4-methoxyphenol in 20 mL of toluene was added 1.66 g of 
4-t-butylcalix4!arene and 1.3 g of triethyl amine in 20 mL of toluene. 
The mixture was stirred overnight and refluxed for one hour. The cooled 
mixture was filtered through celite, washed with toluene and solvent 
removed to give 2.04 g of the desired product as a white solid. .sup.31 P 
{1H} (121.4 MHz, C.sub.6 D.sub.6): 116.06 ppm. 
EXAMPLE 59 
Hydrocyanation Using Ligand "F" 
464 mg of Ligand "F" and 0.040 g of Ni(COD).sub.2 were dissolved in 5 mL of 
tetrahydrofuran. The solvent was removed and 20 mg of ZnCl.sub.2 and 5 mL 
of 3-pentenenitrile (3-PN) were added. The mixture was treated with HCN 
with a nitrogen flow rate of 12 cc/min. The oil bath was initially at 
50.degree. C. After 15 minutes, the temperature controller was set at 
60.degree. C. After 15 minute intervals, the temperature controller was 
set at 70.degree., 80.degree., and 100.degree. C. After 15 minutes at the 
last temperature setting, GC analysis indicated 19.0% adiponitrile (ADN), 
6.3% 2-methylglutaronitrile (MGN) and 3.8% 2-ethylsuccinonitrile (ESN). 
EXAMPLE 60 
Preparation of the Ligand of Formula II Where R.sup.6 and R.sup.7 are 
t-butyl and R.sup.8 is H (Ligand "G") 
##STR19## 
To 1.22 g of dichlorodite derived from PCl.sub.3 and 2-t-butylphenol in 20 
mL of toluene was added 1.66 g of 4-t-butylcalix4!arene and 1.3 g of 
triethylamine in 20 mL of toluene. The mixture was stirred overnight and 
refluxed for one hour. The cooled mixture was filtered through celite, 
washed with toluene and solvent removed to give 1.926 g of the desired 
product as a white solid. .sup.31 P {1H}(121.4 MHz, C.sub.6 D.sub.6): 
115.6 ppm. 
EXAMPLE 61 
Hydrocyanation Using Ligand "G" 
342 mg of Ligand "G" and 0.040 g of Ni(COD).sub.2 were dissolved in 5 mL of 
tetrahydrofuran. The solvent was removed and 20 mg of ZnCl.sub.2 and 5 mL 
of 3PN were added. The mixture was treated with HCN with a nitrogen flow 
rate of 12 cc/min. The oil bath was initially at 50.degree. C. After 15 
minutes, the temperature controller was set at 60.degree. C. After 15 
minute intervals, the temperature controller was set at 70.degree., 
80.degree., and 100.degree. C. After 15 minutes at the last temperature 
setting, GC analysis indicated 17.1% ADN, 6.4% MGN, and 5.9% ESN. 
EXAMPLE 62 
Preparation of the Ligand of Formula III Where R.sup.9 is OCH.sub.3 and 
R.sup.10 are t-butyl (Ligand "H") 
##STR20## 
To 0.7 mL of PCl.sub.3 in 15 mL of toluene at 0.degree. C. was added 2.3 g 
of 1,1'-bi-2-naphthol and 4.1 mL of triethylamine in 20 mL of toluene. The 
mixture was stirred at room temperature. To 1.43 g of 
2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl in 15 mL of 
toluene at -20.degree. C. was added 4.5 mL of 1.77M n-butyl lithium in 
hexane. The mixture was stirred at room temperature for one hour and the 
above chlorodite solution was added. The mixture was stirred overnight and 
then filtered through celite, washed with toluene and solvent removed to 
give 4.044 g of the product as a light yellow solid. .sup.31 P {1H}(121.4 
MHz, C.sub.6 D.sub.6): 146.84, 146.74, 146.62, 146.20, 146.10, 145.76, 
145.41, 145.00, and 144.89 ppm. FABMS: Found: M+H 987.10; Calculated for 
C.sub.62 H.sub.52 O.sub.8 P.sub.2 +H: 987.32. 
EXAMPLE 63 
Hydrocyanation Using Ligand "H" 
445 mg of Ligand "H" and 0.040 g of Ni(COD).sub.2 were dissolved in 5 mL of 
tetrahydrofuran. The solvent was removed and 20 mg of ZnCl.sub.2 and 5 mL 
of 3PN were added. The mixture was treated with HCN with a nitrogen flow 
rate of 12 cc/min. The temperature bath was initially at 50.degree. C. 
After 15 minutes, the temperature controller was set at 60.degree. C. 
After 15 minute intervals, the temperature controller was set at 
70.degree., 80.degree., and 100.degree. C. After 15 minutes at the last 
temperature setting, GC analysis indicated 37.1% ADN, 5.0% MGN, and 0.9% 
ESN. 
EXAMPLE 64 
Preparation of the Ligand of Formula IV Where R.sup.14 is Triphenyl Silyl 
(Ligand "J") 
##STR21## 
Chloridite (0.34 g/1.37 mmol) derived from 2,2'-biphenol and PCl.sub.3 was 
dissolved in toluene (10 mL) and the solution was cooled to -40.degree. C. 
3,3'-Triphenylsilyl-1,1'-bi-2-naphthol (0.80 g/0.68 mmol) and 
triethylamine (0.5 mL) were dissolved in toluene (15 mL) and this solution 
was added dropwise to the cold solution. The mixture was stirred overnight 
at room temperature. The solids were filtered and the solvent was removed 
to give 0.65 g of a light yellow solid. .sup.31 P NMR (CDCl.sub.3): 
.delta. 146.23 (small peak), 136.37 (major peak) and 13 (small peak). 
EXAMPLE 65 
Hydrocyanation Using Ligand "J" 
517 mg of Ligand "J", 0.020 g of ZnCl.sub.2 and 0.040 g of Ni(COD).sub.2 
were dissolved in 5 mL of 3PN. The mixture was treated with HCN with a 
nitrogen flow rate of 30 cc/min at 70.degree. C. for one hour. GC analysis 
indicated 9.3% ADN, 0.6% MGN, and 0.1% ESN. 
EXAMPLE 66 
Preparation of the Ligand of Formula V Where R.sup.12 is H and Each 
R.sup.13 is CH.sub.3 (Ligand "K") 
##STR22## 
To 2.0 g of the chloridite derived from 2,2'-biphenol and PCl.sub.3 in 20 
mL of toluene was added 1.95 g of 2,2'-benzylidenebis(4,6-dimethylphenol) 
(prepared by the procedure of Yamada, F.; Nishiyama, T.; Yamamoto, M.; and 
Tanaka, K.; Bull. Chem. Soc. Jpn., 62, 3603 (1989)) and 2 g of 
triethylamine in 20 mL of toluene. The mixture was stirred overnight and 
refluxed for one hour. The cooled mixture was filtered through celite, 
washed with toluene and solvent removed to give 3.912 g of the desired 
product as a tan solid. .sup.31 P (.sup.1 H) (121.4 MHz, C.sub.6 D.sub.6): 
148.00 ppm. 
EXAMPLE 67 
Hydrocyanation Using Ligand "K" 
327 mg of Ligand "K" and 0.040 g of Ni(COD).sub.2 were dissolved in 5 mL of 
tetrahydrofuran. The solvent was removed and 20 mg of ZnCl.sub.2 and 5 mL 
of 3PN were added. The mixture was treated with HCN with a nitrogen flow 
rate of 30 cc/min at 70.degree. C. for one hour. GC analysis indicated 
12.9% ADN, 42.% MGN, and 0.4% ESN. 
COMATIVE EXAMPLE 68 
Preparation of Ligand "L" 
##STR23## 
Ligand "L" was prepared according to the procedure described in Example 6 
of WO 93/03839, with the exception that the weight of PCl.sub.3 listed in 
the literature procedure did not correspond to the number of moles of 
PCl.sub.3 needed, so the appropriate adjustment was made. Phosphorus 
trichloride (0.32 g; 2.3 mmol) was dissolved in toluene (10 mL) and the 
solution was cooled to 0.degree. C. S-1-1'-bi-2-naphthol (1.0 g; 3.5 mmol) 
and to 0.degree. C. S-1-1'-bi-2-naphthol (1.0 g; 3.5 mmol) and 
triethylamine (0.8 mL; 6.0 mmol) were dissolved in toluene (30 mL) and 
this solution was added dropwise to the PCl.sub.3 solution. The mixture 
was then heated to reflux for 2 hours. The solids were filtered off and 
the solvent was removed to give 0.8 g of white solid. .sup.31 P NMR 
(CDCl.sub.3): .delta. 145.4. 
COMATIVE EXAMPLE 69 
Hydrocyanation Using Ligand "L" 
384 mg of Ligand "L", 0.020 g of ZnCl.sub.2 and 0.040 g of Ni(COD).sub.2 
were dissolved in 5 mL of 3PN. The mixture was treated with HCN with a 
nitrogen flow rate of 30 cc/min at 70.degree. C. for one hour. GC analysis 
indicated 1.8% ADN, 0.8% MGN, and 0.2% ESN. 
COMATIVE EXAMPLE 70 
Hydrocyanation Using Ligand "L" 
3.84 mg of Ligand "L", 0.020 g of ZnCl.sub.2 and 0.040 g of Ni(COD).sub.2 
were dissolved in 5 mL of 3PN. The mixture was treated with HCN with a 
nitrogen flow rate of 30 cc/min at 70.degree. C. for one hour. GC analysis 
indicated 3% ADN, 1.5% MGN, and 0.3% ESN. 
COMATIVE EXAMPLE 71 
Preparation of Ligand "M" 
##STR24## 
Ligand "M" was prepared according to the procedure described in Example 1 
of WO 93/0383.9. Phosphorus trichloride (0.66 g; 4.8 mmol) was dissolved 
in toluene (15 mL) and cooled to 0.degree. C. The 
2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethoxy-1,1'-biphenyl (1.72 g; 4.8 
mmol) and triethylamine (2.7 mL; 19.2 mmol) were dissolved in toluene (25 
mL). This solution was added dropwise to the cold PCl.sub.3 solution. 
After the addition was complete, the mixture was heated to reflux for 1.5 
hrs. The mixture was then cooled to 0.degree. C., and solid 
(2R,4R)-(-)-pentanediol (0.25 g; 2.4 mmol) was added. The mixture was 
again heated to reflux for 1.5 hrs., and then stirred overnight at room 
temperature. The solids were filtered, and the toluene was removed in 
vacuo. The resulting yellow solid was dissolved in hot CH.sub.3 CN 
(approx. 10 mL) and stirred at room temperature. The resulting white solid 
was removed, washed with cold CH.sub.3 CN, and dried. 1.3 g of material 
was collected. .sup.31 P NMR (CDCl.sub.3): .delta. 146.2. 
COMATIVE EXAMPLE 72 
Hydrocyanation Using Ligand "M" 
368 mg of Ligand "M", 0.020 g of ZnCl.sub.2 and 0.040 g of Ni(COD).sub.2 
were dissolved in 5 mL of 3PN. The mixture was treated with HCN with a 
nitrogen flow rate of 30 cc/min at 70.degree. C. for one hour. GC analysis 
indicated 0.0% ADN, 0.2% MGN, and 0.0% 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.