HK1050187B - Multidentate phosphite ligands, catalytic compositions containing such ligands and catalytic processes utilizing such catalytic compositions - Google Patents

Description

Multidentate phosphite ligands, catalytic compositions containing such ligands and catalytic processes using such catalytic compositions

Technical Field

This invention relates to certain multidentate phosphite ligands, catalyst compositions made therefrom, and catalytic hydrocyanation processes using such multidentate phosphite ligands. In particular, the ligands have phenyl groups with substituents attached to the ortho position of the terminal phenolic group and/or to the ortho position of the backbone.

Background of the invention

Phosphorus ligands are ubiquitous in catalysis and are used in a number of commercially important chemical conversion processes. Phosphorus ligands commonly used in catalysis include phosphines (A) and phosphites (B), as shown below. In these descriptions, R can be virtually any organic group. Monophosphine and monophosphite ligands are compounds containing a single phosphorus atom that acts as an electron donor to the metal. Bisphosphine, bisphosphite, and bis (phosphorus) ligands, generally containing two phosphorus electron donor atoms, typically form cyclic chelate structures with transition metals.

There are several industrially important catalytic processes using phosphorus ligands. For example, U.S. Pat. No. 5,910,600 to Urata et al discloses that bisphosphite compounds can be used as a component of homogeneous metal catalysts suitable for a variety of different reactions, such as hydrogenation, hydroformylation, hydrocyanation, hydrocarboxylation, hydroamidation, hydroesterification, and aldol condensation reactions.

Some of these catalytic processes are used for commercial production of polymers, solvents, plasticizers and other commodity chemicals. Thus, with a huge worldwide chemical commodity market, even small increases and improvements in the yield or selectivity of any of these commercially important reactions are highly desirable. Moreover, it would be highly desirable to find certain ligands that could be applied in these commercially important reaction areas, not only for commercial interest, but also to enable enhanced and focused research and development efforts on specific compound groups.

U.S. patent 5512696 to Kreutzer et al discloses a hydrocyanation process utilizing a multidentate phosphite ligand, wherein the referenced patents and publications describe hydrocyanation catalyst systems suitable for hydrocyanation of ethylenically unsaturated compounds. U.S. Pat. Nos. 5723641, 5663369, 5688986 and 5847191 disclose processes and catalyst compositions for hydrocyanation of monoethylenically unsaturated compounds using zero-valent nickel and multidentate phosphite ligands and Lewis acid promoters.

U.S. patent 5821378 to Foo et al discloses a liquid phase process for the hydrocyanation of diolefinic compounds to produce unconjugated acyclic nitriles and the isomerization of these nitriles to produce 3-and/or 4-monoolefinic linear nitriles in the presence of zero-valent nickel and a multidentate phosphite ligand. Other catalytic processes for olefin hydrocyanation and monoalkene nitrile isomerization are disclosed in the patents and publications cited therein. Commonly granted published PCT application WO 99/06357 discloses multidentate phosphite ligands having an alkyl ether substituent attached to the ortho carbon of a terminal phenolic group for use in liquid phase processes for the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitriles and for the isomerization of such nitriles to produce 3-and/or 4-monoalkene linear nitriles.

The use of multidentate phosphite ligands having binaphthalene and/or biphenyl bridging groups for hydroformylation reactions is disclosed in U.S. Pat. Nos. 5235113, 5874641, 5710344 and published PCT application WO 97/33854.

While the above-described catalyst systems may represent commercially viable catalysts, it would be desirable to be able to provide more efficient, higher performance catalyst precursor compositions, catalytic compositions, and catalytic processes to achieve the full commercial potential of the desired reaction. Depending on the particular reaction being carried out, the efficacy and/or performance may be achieved in any or all of speed, selectivity, efficiency or stability. It would also be desirable to be able to provide such improved catalyst systems and/or processes that optimize commercially important reactions such as hydrocyanation or isomerization. Other objects and advantages of the present invention will become more apparent to those skilled in the art after referring to the following detailed description.

Summary of The Invention

The present invention provides a hydrocyanation process comprising reacting an acyclic aliphatic monoethylenically unsaturated compound in which the olefinic double bond is not conjugated to any other olefinic group in the molecule thereof with a source of HCN in the presence of a catalyst composition comprising a lewis acid, a zero-valent nickel and at least one multidentate phosphite ligand selected from the group represented by formulas I, II or III below, wherein all like designations have the same meaning, unless otherwise specifically limited.

Structural formula I structural formula II

Structural formula III

Wherein R is¹Independently is C₁-C₁₈Primary or secondary alkyl of (a);

R²independently aryl or substituted aryl;

R³independently aryl or substituted aryl;

R⁴independently is C₁-C₁₈Primary alkyl groups of (a);

R⁵is hydrogen;

R⁶independently aryl or substituted aryl;

R⁷independently is C₁-C₁₈Primary or secondary alkyl of (a);

R⁸independently is C₁-C₁₈Primary or secondary alkyl of (a); and

R⁹independently is C₁-C₁₈Primary or secondary alkyl of (a);

wherein the aromatic ring may be substituted at other positions with alkyl, ether or ester groups or a combination of two or more thereof.

In one embodiment, wherein the ligand has the structure of formula II, R²Is a substituted aryl group.

In one embodiment, wherein the ligand has the structure of formula I, R³Is unsubstituted phenyl.

In one embodiment, wherein R is¹、R⁷And R⁹Is methyl.

In one embodiment, wherein R is¹、R⁸And R⁹Is methyl.

In one embodiment, there is an ADN distribution of at least about 97%.

The present invention also provides a multidentate phosphite ligand having the structure represented by formula I, II or III below, wherein all like designations have the same meaning, unless otherwise explicitly defined.

Structural formula I structural formula II

Structural formula III

Wherein R is¹Independently is C₁-C₁₈Primary or secondary alkyl of (a);

R²independently aryl or substituted aryl;

R³independently aryl or substituted aryl;

R⁴independently is C₁-C₁₈Primary alkyl groups of (a);

R⁵is hydrogen;

R⁶independently aryl or substituted aryl;

R⁷independently is C₁-C₁₈Primary or secondary alkyl of (a);

R⁸independently is C₁-C₁₈Primary or secondary alkane ofA group; and

R⁹independently is C₁-C₁₈Primary or secondary alkyl of (a);

wherein the aromatic ring may be substituted at other positions with alkyl, ether or ester groups or a combination of two or more thereof.

In one embodiment, wherein the ligand has the structure of formula II, R²Is a substituted aryl group.

In one embodiment, wherein the ligand has the structure of formula I, R³Is unsubstituted phenyl.

In one embodiment, wherein R is¹、R⁷And R⁹Is methyl.

In one embodiment, wherein R is¹、R⁸And R⁹Is methyl.

In one embodiment, there is an ADN distribution of at least about 97%.

Description of The Preferred Embodiment

The present invention provides certain multidentate phosphite ligands, catalyst systems modified with such ligands, and the use of such multidentate phosphite ligands in hydrocyanation reactions.

The catalyst compositions useful in the present invention preferably consist of multidentate phosphite ligands represented by structural formulae I, II and III and a transition metal.

Structural formula I structural formula II

Structural formula III

Wherein R is¹Independently is C₁-C₁₈Primary or secondary alkyl of (a);

R²independently aryl or substituted aryl;

R³independently aryl or substituted aryl;

R⁴independently is C₁-C₁₈Primary alkyl groups of (a);

R⁵is hydrogen;

R⁶independently aryl or substituted aryl;

R⁷independently is C₁-C₁₈Primary or secondary alkyl of (a);

R⁸independently is C₁-C₁₈Primary or secondary alkyl of (a); and

R⁹independently is C₁-C₁₈Primary or secondary alkyl of (a);

wherein the aromatic ring may be substituted at other positions with alkyl, ether or ester groups or a combination of two or more thereof.

The divalent bridging compounds used in the ligands of formulae I, II and III can be prepared by a variety of different methods known in the art. For example, 3, 3 ', 5, 5 ' -tetramethyl-2, 2 ' -biphenol can be prepared according to j.org.chem., 1963, 28, 1063. 3, 3 ', 5, 5', 6, 6 '-hexamethyl-2, 2' -biphenol can be prepared according to JP 85-216749. 3, 3 '-diaryl substituted 1, 1' -2-naphthols may be prepared according to J.org.chem., 1998, 63, 7536.

Phosphorus chlorides can be prepared by a number of different methods known in the art, see, for example, the followingDescription in the literature: polymer, 1992, 33, 161; InorganicSynthesis, 1966, 8, 68; US5, 210, 260; breast, chem, 1986, 535, 221. For ortho-substituted phenols, phosphorus chlorides may be derived from PCl₃And phenol in situ. Phosphorus chlorides of 1-naphthol can be derived from PCl₃And 1-naphthol in the presence of a base such as triethylamine. Another process for the preparation of phosphorus chlorides involves treating an N, N-dialkyl diaryl phosphoramidate with HCl. ClP (OMe)₂It has been prepared by this method, see z. naturforsch, 1972, 27B, 1429. Phosphorus chlorides derived from substituted phenols have been prepared using methods such as those described in commonly assigned US5,821,378.

By reacting (OAr) thus obtained₂Contacting PCl, wherein Ar is a substituted aryl group, with a divalent bridging compound, for example by the method described in U.S. Pat. No. 5,235,113, gives a bidentate phosphite ligand which can be used in the process of the present invention.

The transition metal may be any transition metal capable of effecting catalytic conversion and may additionally contain labile ligands which may be displaced during the catalytic reaction or which actively participate in the catalytic conversion reaction. Any transition metal can be considered for this aspect. Preferred metals are those including group VIII of the periodic table of elements. Preferred metals for hydroformylation are rhodium, cobalt, iridium, ruthenium, palladium and platinum. Preferred metals for the hydrocyanation and/or isomerization are nickel, cobalt and palladium, nickel being particularly preferred for the hydrocyanation.

The catalyst composition of the present invention is comprised of at least one multidentate phosphite ligand based on any one of formulas I, II and III and a transition metal. In embodiments of the invention, catalyst compositions for use in, for example, hydroformylation processes may contain group VIII compounds which may be prepared or formed according to techniques known in the art, for example as described in WO 9530680, US 3,907,847 and J.Amer.chem.Soc., 1993, 115, 2066A method. Suitable group VIII metals are ruthenium, rhodium and iridium. Suitable group VIII metal compounds are hydrides, halides, organic acid salts, acetylacetonates, inorganic acid salts, oxides, carbonyl compounds and amides of these metals. Examples of suitable group VIII metal compounds are, for example, Ru₃(CO)₁₂、Ru(NO₃)₂、RuCl₃(Ph₃P)₃、Ru(acac)₃、Ir₄(CO)₁₂、IrSO₄、RhCl₃、Rh(NO₃)₃、Rh(OAc)₃、Rh₂O₃、Rh(acac)(CO)₂、[Rh(OAc)(COD)]₂、Rh₄(CO)₁₂、Rh₆(CO)₁₆、RhH(CO)(Ph₃P)₃、[RH(OAc)(CO)₂]₂And [ RhCl (COD)]₂(wherein "acac" is an acetylacetonate group; OAc "is an acetyl group; COD" is 1, 5-cyclooctadiene; and "Ph" is a phenyl group). However, it is to be noted that the group VIII metal compound is not necessarily limited to the compounds given above. The group VIII metal is preferably rhodium. Rhodium compounds containing ligands which may be replaced by multidentate phosphites are preferred rhodium sources. Examples of such preferred rhodium compounds are Rh (CO)₂(acetylacetonate), Rh (CO)₂(C₄II₉COCHCO-t-C₄H₉)、Rh₂O₃、Rh₄(CO)₁₂、Rh₆(CO)₁₆、Rh(O₂CCH₃)₂And Rh (2-ethylhexanoate). Rhodium supported on carbon may also be used in this regard.

The nickel compounds may be prepared or formed according to methods known in the art, for example, as described in the following documents: US 3,496,217; US 3,631,191; US 3,846,461; US 3,847,959 and US 3,903,120, which are incorporated herein by reference. Zero-valent nickel compounds containing ligands which may be substituted with organophosphorus ligands are a preferred source of nickel. Two such preferred zero-valent nickel compounds are Ni (COD)₂(COD is 1, 5-cyclooctadiene) and Ni { P (O-O-C)₆H₄CH₃)₃}₂(C₂H₄) All of which are known in the art. Alternatively, the divalent nickel compound may be combined with a reducing agent to serve as the nickel source in the reaction. Suitable divalent nickel compounds include those of the formula NiY₂Wherein Y is a halogen, carboxylate or acetylacetonate group. Suitable reducing agents include metal borohydrides, metal alanates, metal alkyls, Zn, Fe, Al, Na or H₂. Elemental nickel, preferably nickel powder, when combined with a halogenation catalyst, as described in U.S. Pat. No. 3,903,120, is also a suitable source of zero valent nickel.

Depending on the desired reaction, the catalyst composition of the present invention may also contain one or more lewis acid promoters, which may affect both the activity and selectivity of the catalyst system. The adjuvant may be an inorganic or organometallic compound in which at least one element is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, and tin. Specific examples include ZnBr₂，ZnI₂，ZnCl₂，ZnSO₄，CuCl₂，CuCl，Cu(O₃SCF₃)₂，CoCl₂，CoI₂，FeI₂，FeCl₃，FeCl₂，FeCl₂(THF)₂，TiCl₄(THF)₂，TiCl₄，TiCl₃，ClTi(OiPr)₃，MnCl₂，ScCl₃，AlCl₃，(C₈H₁₇)AlCl₂，(C₈H₁₇)₂AlCl, (iso-C)₄H₉)₂AlCl，Ph₂AlCl，PhAlCl₂，ReCl₅，ZrCl₄，NbCl₅，VCl₃，CrCl₂，MoCl₅，YCl₃，CdCl₂，LaCl₃，Er(O₃SCF₃)₃，Yb(O₂CCF₃)₃，SmCl₃，B(C₆H₅)₃，TaCl₅. Suitable auxiliaries are also disclosed in US 3,496,217; US3,496,218, respectively; and US 4,774,353. These materials include metal salts (e.g., ZnCl)₂，CoI₂And SnCl₂) And organometallic compounds (e.g., RAlCl)₂，R₃SnO₃SCF₃And R₃B, wherein R is an alkyl or aryl group). US 4,874,884 discloses how to select synergistic combinations of promoters to increase the catalytic activity of the catalyst system. Preferred adjuvants include CdCl₂，FeCl₂，ZnCl₂，B(C₆H₅)₃And (C)₆H₅)₃SnX, wherein X ═ CF₃SO₃，CH₃C₆H₅SO₃Or (C)₆H₅)₃BCN is adopted. The molar ratio of promoter to nickel in the reaction may be in the range of from about 1: 16 to about 50: 1.

Hydrocyanation of monoolefin compounds

The present invention provides a hydrocyanation process comprising reacting an unsaturated compound with a source of hydrogen cyanide in the presence of a catalyst composition comprising a transition metal selected from the group consisting of Ni, Co and Pd, and a lewis acid compound, and at least one ligand selected from the group consisting of those represented by structural formulae I, II or III. Representative ethylenically unsaturated compounds useful in the hydrocyanation process of the present invention are shown in structures IV or VI, and the corresponding terminal nitrile compounds produced are shown in structures V or VII, respectively, where like reference numerals have the same meaning.

Structural formula IV structural formula V

Structural formula VI structural formula VII

Wherein

R²²Is H, CN, CO₂R²³Or a perfluoroalkyl group;

y is an integer between 0 and 12;

x is an integer of 0 to 12, when R²²Is H, CO₂R²³Or perfluoroalkyl;

x is an integer of 1 to 12, when R²²When CN is present; and

R²³is C₁-C₁₂Alkyl or aryl.

The nonconjugated acyclic aliphatic monoethylenically unsaturated starting materials useful in the present invention include unsaturated organic compounds containing from 2 to about 30 carbon atoms. Suitable unsaturated compounds include unsubstituted hydrocarbons as well as hydrocarbons substituted with groups that do not attack the catalyst, such as cyano groups. Examples of such monoethylenically unsaturated compounds include ethylene, propylene, 1-butene, 2-pentene, 2-hexene, and the like; non-conjugated diolefin unsaturated compounds such as allene, substituted compounds such as 3-pentenenitrile, 4-pentenenitrile, methylpentyl-3-enoate and compounds having perfluoroalkyl substituents such as C_ZF_2z+1Wherein z is an integer up to 20. The monoethylenically unsaturated compounds may also be conjugated with an ester group, such as methylpentyl-2-enoate.

Preferred are non-conjugated linear olefins, non-conjugated linear allenitrile, non-conjugated linear alkenoic acid esters, linear alkyl-2-enoic acid esters and perfluoroalkyl ethylenes. The most preferred substrates include 3-and 4-pentenenitrile, alkyl 2-, 3-and 4-pentenoates and C_zF_2z+1CH＝CH₂(wherein z is 1 to 12).

3-pentenenitrile and 4-pentenenitrile are particularly preferred materials. In practice, when nonconjugated acyclic aliphatic monoethylenically unsaturated compounds are used in the present invention, up to about 10 weight percent of the monoethylenically unsaturated compounds may be present in the conjugated isomeric form and may themselves undergo hydrocyanation. For example, when 3-pentenenitrile is used, it may contain up to 10% by weight of 2-pentenenitrile. (for purposes herein, the term "pentenenitrile" is equivalent to "cyanobutene").

Preferred products are terminal alkanenitriles, linear dicyanoalkenes, linear aliphatic cyanates and 3- (perfluoroalkyl) propionitrile. Most preferred products are adiponitrile, alkyl 5-cyanovalerate and C_zF_2z+1CH₂CH₂CN (wherein z is 1-12).

The hydrocyanation process, for example, may be carried out by charging a reactor with the reactants, catalyst composition, and solvent, if any; preferably, however, the hydrogen cyanide is added slowly to the mixture of the other ingredients of the reaction. The hydrogen cyanide may be fed to the reaction in liquid or vapor form. Another suitable method is to add the catalyst and solvent used to the reactor and slowly add both the unsaturated compound and HCN to the reaction mixture. The molar ratio of unsaturated compound to catalyst may vary from about 10: 1 to about 2000: 1.

Preferably, the reaction medium is agitated, for example by stirring or shaking. The reaction product may be recovered by conventional means such as distillation. The reaction may be carried out in a batch mode or in a continuous mode.

The hydrocyanation reaction may be carried out in the presence or absence of a solvent. If a solvent is used, it should be liquid at the reaction temperature and pressure and inert to the unsaturated compound and the catalyst. Suitable solvents include hydrocarbons such as benzene or xylene, and nitriles such as acetonitrile or benzonitrile. In some cases, the unsaturated compound to be hydrocyanated may also be used as a solvent by itself.

The exact temperature of the reaction will depend to a certain extent on the particular catalyst employed, the particular unsaturated compound employed and the desired rate. Generally, temperatures between-25 ℃ and 200 ℃ are employed, preferably between 0 ℃ and 150 ℃.

Atmospheric pressure is sufficient to practice the present invention, and therefore pressures of about 0.05 to 10 atmospheres (50.6 to 1013kPa) are preferred. Higher pressures, up to 10000kPa or more, may be used if desired, but all of the benefits from this may be uneconomical relative to such increased operating costs.

The HCN can be introduced into the reaction as a vapor or liquid. Alternatively, cyanohydrins can be used as a source of HCN. See, for example, US 3655723.

The process of the present invention may be carried out in the presence of one or more lewis acid promoters capable of affecting both the activity and selectivity of the catalyst system. The adjuvant may be an inorganic or organometallic compound in which at least one element is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, and tin. Examples include ZnBr₂，ZnI₂，ZnCl₂，ZnSO₄，CuCl₂，CuCl，Cu(O₃SCF₃)₂，CoCl₂，CoI₂，FeI₂，FeCl₃，FeCl₂，FeCl₂(THF)₂，TiCl₄(THF)₂，TiCl₄，TiCl₃，ClTi(OiPr)₃，MnCl₂，ScCl₃，AlCl₃，(C₈H₁₇)AlCl₂，(C₈H₁₇)₂AlCl, (iso-C)₄H₉)₂AlCl，Ph₂AlCl，PhAlCl₂，ReCl₅，ZrCl₄，NbCl₅，VCl₃，CrCl₂，MoCl₅，YCl₃，CdCl₂，LaCl₃，Er(O₃SCF₃)₃，Yb(O₂CCF₃)₃，SmCl₃，B(C₆H₅)₃，TaCl₅. Suitable auxiliaries are also disclosed in US 3,496,217; US 3,496,218; and US 4,774,353. These materials include metal salts (e.g., ZnCl)₂，CoI₂And SnCl₂) And organometallic compounds (e.g., RAlCl)₂，R₃SnO₃SCF₃And R₃B, wherein R is an alkyl or aryl group). US 4,874,884 discloses how to select synergistic combinations of promoters to increase the catalytic activity of the catalyst system. Preferred adjuvants include CdCl₂，FeCl₂，ZnCl₂，B(C₆H₅)₃And (C)₆H₅)₃SnX, wherein X ═ CF₃SO₃，CH₃C₆H₅SO₃Or (C)₆H₅)₃BCN is adopted. The molar ratio of promoter to nickel in the reaction may be in the range of from about 1: 16 to about 50: 1.

The invention will now be more particularly described by the following non-limiting examples of certain embodiments, in which all parts, ratios, percentages are by weight unless otherwise indicated.

Wherever a defined term appears in the specification, the following definitions apply:

the term "hydrocarbyl" refers to a hydrocarbon molecule in which one hydrogen atom has been removed. Such molecules may contain single, double or triple bonds.

3 PN: 3-pentenenitrile

2 PN: 2-pentenenitrile

4 PN: 4-pentenenitrile

2M 3: 2-methyl-3-butenenitrile

VN: pentanitrile

ESN: ethyl succinonitrile

MGN: 2-methylglutaronitrile

5 FVN: 5-formyl valeronitrile

M3P: methyl 3-pentenoate

BD: 1, 3-butadiene

COD: 1, 5-cyclooctadiene

Et₃N: triethylamine

PCl₃: phosphorus trichloride

THF: tetrahydrofuran (THF)

One convention used to calculate some of the reaction results for hydrocyanation and isomerization reactions is shown below:

for the hydrocyanation of step 1, useful values for the percentage of Pentenenitriles (PN) and the ratio 3PN/2M3 are given. The product distribution was determined analytically by gas chromatography using valeronitrile as internal standard. Useful values for the percent of Pentenenitriles (PN) are the molar ratio of the sum of 3PN (cis and trans) and 2M3 divided by the amount of HCN. The 3PN/2M3 ratio is the ratio of cis and trans 3PN to 2M 3.

For the hydrocyanation reaction of step 2, the selectivity for Adiponitrile (ADN) is ADN/(ESN + MGN + ADN). The 3PN and 4PN conversions were calculated using 2-ethoxyethyl ether (EEE) as an internal standard. The total conversion of PN to Dinitrile (DN) based on the consumption of all the materials taken into account is calculated in moles as the sum DN/(PN + BN + DN) (BN is butenenitrile). The conversion based on HCN is obtained by dividing the total conversion of PN to DN by the ratio of HCN/PN in the starting material, i.e., (DN/starting PN)/(HCN/starting PN), in moles.

Example 1

2 '-ethoxy-1, 1' -biphenylPhenyl-2-ol was prepared by modifying the method reported in j. orgchem.1981, 46, 4988. To 50mL of acetone were added 10g of 2, 2' -biphenol and 9.4g of potassium carbonate. After stirring at room temperature for 1 hour, an iodoethane solution (9.2g dissolved in 10mL of acetone, after filtration and washing of the mixture, the solvent was removed by rotary evaporation, and the residue was separated by flash chromatography to give 5.1g of 2 '-ethoxy-1, 1' -biphenyl-2-ol as a colorless oil.¹HNMR(C₆D₆)：7.20(m，3H)，7.10(m，1H)，7.05(m，1H)，6.85(m，2H)，6.55(m，1H)，3.38(q，2H)，0.81(t，3H)。

In a nitrogen purged glove box, the above phenol (0.73g, 3.40mmol) was dissolved in 10mL of diethyl ether and cooled to-30 ℃. To this solution was added a cold (-30 ℃ C.) 1M solution of phosphorus trichloride (1.7mL), followed by dropwise addition of a 1M solution of triethylamine (4.0 mL). The solution was stirred at room temperature for 5 minutes and then kept at-30 ℃ for 2 hours. The reaction mixture was filtered through a plug of Celite * and concentrated to give 0.67g of the corresponding phosphorous oxychloride.³¹P NMR (toluene): 160.4 (78%), 126 (22%). And reacting the phosphorous chloride with 1, 1' -di-2-naphthol in the presence of triethylamine to obtain a ligand III.³¹PNMR (toluene): 131.3 (main peak), 130.2.

Example 2

2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (diphenyl ether) was prepared according to the literature method reported in J.org.chem.1998, 63, 7536. To a 250mL two-necked Schlenk flask with reflux condenser, under nitrogen, was added 3, 3 ' -bis (dihydroxyborane) -2, 2 ' -dimethoxy-1, 1 ' -binaphthyl (2.250g, 5.60mmol), Pd (PPh)₂)₄(0.360g，0.42mmol)、Ba(OH)₂(5.25g，30.6mmol), 4-bromo-diphenyl ether (4.47g, 17.9mmol), 1, 4-dioxane (36mL) and H₂O (12 mL). The reaction mixture was refluxed for 24 hours. Upon cooling to room temperature, the mixture was quenched with CH₂Cl₂Diluted (150mL) and washed with 1N HCl (2X 75mL) and brine (2X 75 mL). The solution was over MgSO₄Drying the mixture. Removal of the solvent gave a brown oil which was dried over CH₂CL₂Diluted (125mL) and cooled to-40 ℃. After 10 minutes, BBr was added slowly₃(3mL), the reaction mixture was stirred at room temperature overnight. The resulting reddish brown solution was cooled to 0 ℃ and H was carefully added₂O (300 mL). Separating the organic layer, followed by H₂It was washed with O (2X 300mL), 1N HCl (300mL) and brine (300 mL). The resulting solution was over MgSO₄Dried and concentrated. The resulting red oil was chromatographed on silica to give 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (diphenyl ether) as a white crystalline solid (0.80g, 23%).¹HNMR(C₆D₆)：7.80(s，2H)，7.64(d，J＝8.2Hz，2H)，7.53(d，J＝8.7Hz，4H)，7.22(d，J＝8.3Hz，2H)，7.12(m，4H)7.05-6.96(m，14H)，5.03(s，2H)。

A cold (-35 ℃ C.) anhydrous solution of 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (diphenyl ether) (0.405g, 0.65mmol) in diethyl ether (20mL) was added to phosphorus chloride of 5, 6, 7, 8-tetrahydro-1-naphthol (0.588g, 1.63mmol) dissolved in diethyl ether (10mL) under nitrogen. To the above mixture was added triethylamine (0.23mL, 1.63mmol) dropwise while maintaining this temperature, and a white precipitate formed. After stirring at room temperature for 3 hours, the reaction mixture was filtered through a plug composed of basic alumina and Celite *. The filtrate was evaporated to give the desired diphosphite as a white powder (0.537g, 65%).³¹P{¹H}NMR(202.4MHz，C₆D₆)：132.75ppm。

Example 3

A cold (-35 ℃ C.) anhydrous diethyl ether solution (5mL) of 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (diphenyl) (0.050g, 0.08mmol) was added to a solution of phosphorus chloride (0.076g, 0.21mmol) of 5, 6, 7, 8-tetrahydro-1-naphthol dissolved in diethyl ether (5mL) under nitrogen. While maintaining this temperature, triethylamine (0.03mL, 0.21mmol) was added dropwise to the above mixture, forming a white precipitate. After stirring at room temperature for 3 hours, the reaction mixture was filtered through a plug composed of basic alumina and Celite *. The filtrate was evaporated to give the desired diphosphite as a white powder (0.043g, 58%).³¹P{¹H}NMR(202.4MHz，C₆D₆): 127.83, 132.14, 132.60 (main peaks), 133.66, 141.51, 143.99 ppm.

Hydrocyanation reaction result of ligand of example 2

Preparation of the catalyst: the catalyst solution was prepared by dissolving 0.0039g of Ni (COD) in 0.320ml of toluene₂(0.014mmol) was added to 0.062g of the ligand of example 2 (0.049mmol) dissolved in 0.200mL of toluene.

Hydrocyanation of 3,4 pentenenitrile (3, 4 PN): mu.L of the above catalyst solution (0.0031mmol Ni) and 13. mu.L of ZnCl dissolved in 3PN₂Solution (0.0067 mmolZnCl)₂) Into a vial fitted with a septum cap. The vial was cooled to-20 deg.C and 125. mu.L of a solution containing HCN, t-3PN, and 2-ethoxyethyl ether (0.396mmol of HCN, 0.99mmol of t-3PN) was added. The vial was sealed and allowed to stand at room temperature for 24 hours. The reaction mixture was diluted with ether and the product distribution was analyzed by GC using 2-ethoxyethyl ether as internal standard. Analysis indicated that 22.7% of the starting pentenenitrile had been converted to dinitrile product (62.8% yield, based on HCN). Straight chainSelectivity to ADN isomer was 97.4%.

Hydrocyanation reaction result of ligand of example 3

Preparation of the catalyst: the catalyst solution was prepared by dissolving 0.0039g of Ni (C0D) in 0.320ml of toluene₂(0.014mmol) was added to 0.025g of the ligand of example 3 (0.020mmol) dissolved in 0.200mL of toluene.

Hydrocyanation of 3,4 pentenenitrile (3, 4 PN): mu.L of the above catalyst solution (0.0031mmol Ni) and 13. mu.L of ZnCl dissolved in 3PN₂Solution (0.0067 mmolZnCl)₂) Into a vial fitted with a septum cap. The vial was cooled to-20 deg.C and 125. mu.L of a solution containing HCN, t-3PN, and 2-ethoxyethyl ether (0.396mmol of HCN, 0.99mmol of t-3PN) was added. The vial was sealed and allowed to stand at room temperature for 24 hours. The reaction mixture was diluted with ether and the product distribution was analyzed by GC using 2-ethoxyethyl ether as internal standard. Analysis indicated that 9.2% of the starting pentenenitrile had been converted to dinitrile product (25.4% yield, based on HCN). The selectivity of the linear ADN isomer was 97.5%.

Example #	Step 2 conversion	Step 2 distribution
			1	10.4	94.6
2	22.7	97.4
			3	9.2	97.5

Claims (11)

1. A hydrocyanation process comprising reacting an acyclic aliphatic monoethylenically unsaturated compound in which the olefinic double bond is not conjugated to any other olefinic group in the molecule thereof with a source of HCN in the presence of a catalyst composition comprising a lewis acid, a zero-valent nickel and at least one multidentate phosphite ligand represented by the following structure III, wherein all like designations have the same meaning, with the further proviso that:

structural formula III

Wherein R is⁵Is hydrogen;

R⁶independently aryl or substituted aryl; and

wherein the aromatic ring may be substituted at other positions with alkyl, ether or ester groups or a combination of two or more thereof.

2. The method of claim 1, wherein R⁶Is 2-ethoxyphenyl.

3. The process of claim 1, wherein the starting ethylenically unsaturated compound is selected from the group consisting of 3-pentenenitrile, 4-pentenenitrile; alkyl 2-, 3-and 4-pentenoates and C_zF_2z+1CH＝CH₂Wherein z is an integer between 1 and 12.

4. The process of claim 3, wherein the starting ethylenically unsaturated compound is 3-pentenenitrile or 4-pentenenitrile.

5. The process of claim 1 which is carried out at a temperature of from-25 ℃ to 200 ℃ and a pressure of from 50.6 to 1013 kPa.

6. The process of claim 5 which is carried out at atmospheric pressure and at a temperature of from 0 ℃ to 150 ℃.

7. The process of claim 1 wherein the lewis acid is selected from the group consisting of inorganic or organometallic compounds in which the cation is selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper, zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium, rhenium, and tin.

8. The method of claim 1Process wherein the lewis acid is selected from ZnBr₂，ZnI₂，ZnCl₂，ZnSO₄，CuCl₂，CuCl，Cu(O₃SCF₃)₂，CoCl₂，CoI₂，FeI₂，FeCl₃，FeCl₂(THF)₂，TiCl₄(THF)₂，TiCl₄，TiCl₃，ClTi(OiPr)₃，MnCl₂，ScCl₃，AlCl₃，(C₈H₁₇)AlCl₂，(C₈H₁₇)₂AlCl, (iso-C)₄H₉)₂AlCl，Ph₂AlCl，PhAlCl₂，ReCl₅，ZrCl₄，NbCl₅，VCl₃，CrCl₂，MoCl₅，YCl₃，CdCl₂，LaCl₃，Er(O₃SCF₃)₃，Yb(O₂CCF₃)₃，SmCl₃，TaCl₅，B(C₆H₅)₃And (C)₆H₅)₃SnX, wherein X ═ CF₃SO₃，CH₃C₆H₅SO₃Or (C)₆H₅)₃BCN。

9. The process of claim 1, having an adiponitrile distribution of at least about 97%.

10. A multidentate phosphite ligand represented by structural formula III:

structural formula III

Wherein R is⁵Is hydrogen;

R⁶independently aryl or substituted aryl; and

wherein the aromatic ring may be substituted at other positions with alkyl, ether or ester groups or a combination of two or more thereof.

11. The ligand of claim 10, wherein R⁶Is 2-ethoxyphenyl.