HK1050188B

HK1050188B - Multidentate phosphite ligands, catalytic compositions containing such ligands and catalytic processes utilizing such catalytic compositions

Info

Publication number: HK1050188B
Application number: HK03102409.8A
Authority: HK
Inventors: Ann Kreutzer Kristina; Tam Wilson; Michael Garner J.; Ronald Boyles John
Original assignee: 因维斯塔技术有限公司
Priority date: 1999-09-20
Filing date: 2000-09-19
Publication date: 2008-03-20

Description

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

Reference to related applications

This application claims the benefit of U.S. provisional application No. 60/154,727, filed on 20/9/1999.

Technical Field

This invention relates to certain multidentate phosphite ligands, catalyst compositions made therefrom, and catalytic processes using such multidentate phosphite ligands. In particular, the ligands have heteroatom-containing substituents on the carbon attached to the ortho position of the terminal phenolic group. The catalytic processes exemplified here are hydrocyanation and isomerization.

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 bisphosphite compounds that can be used as a component of a homogeneous metal catalyst suitable for a variety of different reactions, such as hydrogenation, hydroformylation, hydrocyanation, hydrocarboxylation, hydroamidation, hydroesterification, and aldol condensation reactions.

Some of these catalyst 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 used in these commercially important reaction areas, not only for commercial interest, but also to be able to enhance and focus on the research and development efforts of a particular compound group.

U.S. Pat. No. 5,5512696 to Kreutzer et al discloses a hydrocyanation process employing a multidentate phosphite ligand, wherein the cited patents and publications describe hydrocyanation catalyst systems suitable for hydrocyanation of ethylenically unsaturated compounds. US5723641, US5663369, US5688986 and US5847191 disclose a process and catalyst composition for hydrocyanation of monoethylenically unsaturated compounds which is carried out using zero-valent nickel and a multidentate phosphite ligand and a lewis acid promoter.

U.S. Pat. No. 5,5821378 to Foo et al discloses a liquid phase process for the hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitriles and the isomerization of such nitriles to produce 3-and/or 4-monoolefinic linear nitriles wherein the reaction is carried out 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 assigned published PCT application WO99/06357 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 use in liquid phase processes for the isomerization of such nitriles to produce 3-and/or 4-monoalkene linear nitriles.

While the above 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 can optimize one or more commercially important reactions such as hydroformylation, 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 precursor composition comprising a lewis acid, a zero-valent nickel and at least one multidentate phosphite ligand selected from the group represented by formula I, I-a or I-B below, wherein all like numerals have the same meaning, unless otherwise specifically limited.

Structural formula I

Wherein, X¹Is a bridging group selected from the group consisting of:

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R¹' and R²' is independently selected from the group consisting of: H. c₁-C₁₈Alkyl, cycloalkyl, trialkylsilyl, triarylsilyl, halogen, nitrile, perfluoroalkyl, -SO₂R¹¹、-SO₂NR₂ ¹²Acetals, ketals, dialkylamino OR diarylamino, -OR¹¹、-CO₂R¹¹、-(CNR¹¹)R¹¹、-(CNOR¹¹)R¹¹Wherein R is¹¹Is C₁-C₁₈Alkyl, aryl or substituted aryl, -C (O) R¹²、-C(O)NR¹¹R¹³、-O-C(O)R¹²、-NR¹²-C(O)R¹³Wherein R is¹²And R¹³Independently selected from H, C₁-C₁₈Alkyl, cycloalkyl, aryl or substituted aryl; wherein the aromatic rings are other than R¹-R⁸Other positions may also be C₁-C₁₈Alkyl, cycloalkyl, trialkylsilyl, triarylsilyl, halogen, nitrile, perfluoroalkyl, sulfonyl, acetal, ketal, dialkylamino, diarylamino, -OR¹¹、-CO₂R¹¹、RCNR¹¹Or RCNOR¹¹Is substituted in which R⁹And R¹⁰Independently selected from H, C₁-C₁₈Alkyl, cycloalkyl, aryl or substituted aryl;

wherein X²-X⁵Independently selected from the group consisting of the following structural formulas:

wherein Y is independently selected from the group consisting of H, aryl, CR¹⁴ ₃Wherein R is¹⁴Is H, C₁-C₁₈Alkyl, cycloalkyl or aryl, (CR)¹⁴ ₂)_n-OR¹⁴、(CR¹⁴ ₂)_n-NR¹⁵Wherein R is¹⁵Selected from the group consisting of H, alkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶Is H, C₁-C₁₈Alkyl, cycloalkyl, aryl or perfluoroalkyl;

and Z is selected from the group Consisting of (CR)¹⁴ ₂)_n-OR¹⁴Wherein n is 0 to 3, wherein R¹⁴Is as defined above.

Structural formula I-A

In further embodiments of the present invention, ligands of the structure of formula I-A may be substituted for the ligands of formula I, in which case one of the aromatic ring carbon atoms located ortho to the oxygen atom bonded to the P atom may be replaced by (Z)¹)n¹Bonded to another aromatic ring carbon atom that is ortho to another oxygen atom bonded to the P atom;

wherein Z¹Independently is

Each R¹⁷And R¹⁸Independently selected from H, C₁-C₁₈Alkyl, cycloalkyl, aryl or substituted aryl, n¹Is 1 or 0; wherein it should be understood that n¹0 is a hydrogen atom which represents a bond replacing two aromatic rings.

Structural formula I-B

In a further embodiment of the present invention, ligands of the structure of formula I-B may be substituted for the ligands of formula I, wherein one of the aromatic ring carbon atoms in the position ortho to the oxygen atom bonded to the P atom may be replaced by (Z)¹)n¹Bonded to another aromatic ring carbon atom that is ortho to another oxygen atom bonded to the P atom;

wherein Z¹Independently is

In addition, in embodiments of the present invention employing structure I, structure I-A, or structure I-B, each Y may be linked to Z to form a cyclic ether.

Preferably wherein the group X²-X⁵At least one has the structure of formula a or B; y is³0 or CH₂(ii) a And R¹⁴Is as defined above.

Structural formula A

Structural formula B

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

Structural formula II

Wherein, X¹Is a divalent bridging group selected from the group consisting of:

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R¹' and R²' is independently selected from the group consisting of: H. c₁-C₁₈Alkyl, cycloalkyl, trialkylsilyl, triarylsilyl, halogen, nitrile, perfluoroalkyl, -SO₂R¹¹、-SO₂NR₂ ¹²Acetals, ketals, dialkylamino OR diarylamino, -OR¹¹、-CO₂R¹¹、-(CNR¹¹)R¹¹、-(CNOR¹¹)R¹¹Wherein R is¹¹Is C₁-C₁₈Alkyl, aryl or substituted aryl, -C (O) R¹²、-C(O)NR¹²R¹³、-O-C(O)R¹²、NR¹²-C(O)R¹³Wherein R is¹²And R¹³Independently selected from H, C₁-C₁₈Alkyl, cycloalkyl, aryl or substituted aryl; wherein the aromatic rings are other than R¹-R⁸Other positions may also be C₁-C₁₈Alkyl, cycloalkyl, trialkylsilyl, triarylsilyl, halogen, nitrile, perfluoroalkyl, sulfonyl, acetal, ketal, dialkylamino, diarylamino, -OR¹¹、-CO₂R¹¹、RCNR¹¹Or RCNOR¹¹Is substituted in which R⁹And R¹⁰Independently selected from H, C₁-C₁₈Alkyl, cycloalkyl, aryl or substituted aryl;

Y¹independently selected from H, aryl, CR¹⁴ ₃Wherein R is¹⁴Is H, C₁-C₁₈Alkyl, cycloalkyl or aryl, (CR)¹⁴ ₂)_n-OR¹⁴、(CR¹⁴ ₂)_n-NR¹⁵Wherein n is a number between 0 and 3, wherein R¹⁵Selected from the group consisting of H, alkyl, cycloalkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶Is H, C₁-C₁₈Alkyl, cycloalkyl, aryl or perfluoroalkyl;

Y²independently selected from aryl, CR¹⁴ ₃Wherein R is¹⁴Is H, C₁-C₁₈Alkyl, cycloalkyl or aryl, (CR)¹⁴ ₂)_n-OR¹⁴、(CR¹⁴ ₂)_n-NR¹⁵Wherein n is a number between 0 and 3, wherein R¹⁵Selected from the group consisting of H, alkyl, cycloalkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶Is H, C₁-C₁₈Alkyl, cycloalkyl, aryl or perfluoroalkyl;

z is selected from the group Consisting of (CR)¹⁴ ₂)_n-OR¹⁴Wherein n is 0 to 3, wherein R¹⁴As defined above.

Structural formula II-A

In a further embodiment of the present invention, ligands of the structure of formula II-A may be substituted for the ligands of formula II, wherein one of the aromatic ring carbon atoms in the position ortho to the oxygen atom bonded to the P atom may be replaced by (Z)¹)n¹Bonded to another aromatic ring carbon atom that is ortho to another oxygen atom bonded to the P atom;

wherein Z¹Independently is

Structural formula II-B

In a further embodiment of the present invention, the ligand of the structure of formula II-B, in place of the ligand of formula II, may have one aromatic ring carbon atom located ortho to the oxygen atom bonded to the P atom via (Z)¹)n¹Bonded to another aromatic ring carbon atom that is ortho to another oxygen atom bonded to the P atom;

wherein Z¹Independently is

Furthermore, in embodiments of the present invention employing formula II, formula II-A, or formula II-B, Y is¹Or Y²May be linked to Z to form a cyclic ether.

Structural formula A

Structural formula B

The present invention also provides certain multidentate phosphite ligands and catalyst compositions made therefrom that are useful in hydrocyanation of diolefinic compounds to produce nonconjugated acyclic nitriles, and liquid phase processes for isomerizing such nitriles to produce 3-and/or 4-monoalkene linear nitriles. In particular, these include ligands of formula II, formula II-A and formula II-B bound to nickel.

The invention also provides an improved process for hydrocyanation of diolefins, such as butadiene, and for isomerization of nonconjugated acyclic nitriles. The present invention also provides an improved process for the hydrocyanation of diolefins which does not require a Lewis acid promoter. The multidentate phosphite ligands in these embodiments include nickel-bonded ligands of formula II, formula II-A, and formula II-B, wherein the ligands have heteroatom-containing substituents on the carbon atoms attached to the ortho position of the terminal phenolic groups. The present invention also provides a catalyst which is highly selective in the hydrocyanation of diolefins, thus eliminating the need for an additional isomerization step.

In particular, the present invention provides an improved process for the liquid phase hydrocyanation of diolefins and isomerization of resulting nonconjugated acyclic nitriles, comprising reacting an acyclic aliphatic diolefin, preferably butadiene, with a source of HCN, wherein said process comprises hydrocyanation and/or isomerization in the presence of a catalyst composition comprising zero-valent nickel and at least one multidentate phosphite ligand selected from the group represented by formulae II, II-a and II-B listed above, wherein all like designations have the same meaning, unless otherwise specifically defined.

The reaction is most conveniently carried out continuously from the initial diolefin hydrocyanation reaction to the final formation of the 3-and/or 4-monoolefinic linear nitrile. Nevertheless, the process can be carried out stepwise, i.e.the nonconjugated acyclic nitriles formed by the hydrocyanation can themselves be isolated before the isomerization. Furthermore, non-conjugated acyclic nitriles produced by any method may be used as starting materials for the isomerization reaction described herein.

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, for example, in hydrocyanation and/or isomerization reactions. The multidentate phosphite ligands of the present invention and catalyst systems employing such ligands also have broad applicability to a variety of other catalytic reactions, such as hydroformylation reactions, and can be optimized for such reactions as described herein.

The catalyst composition useful in the present invention preferably consists of a multidentate phosphite and a transition metal.

The divalent bridging compounds used in the ligands described by structures I, I-A, I-B, II-A, and II-B can be prepared by a variety of different methods known in the art. For example, dimethyl 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate can be prepared according to j.am.chem.soc., 1954, 76, 296 or Tetrahedron lett., 1990, 413 and org.proc.prep.international, 1991, 23, 200; 2, 2' -ethylenebis (4, 6-dimethylphenol) may be prepared according to Bull. chem. Soc,. Japn. 1989, 62, 3603; 3, 3 ', 5, 5 ' -tetramethyl-2, 2 ' -biphenol may be prepared according to j.org.chem., 1963, 28, 1063; 2, 2 '-dihydroxy-3, 3' -dimethoxy-5, 5 '-dimethyl-1, 1' -biphenylene can be prepared according to Phytochemistry, 1988, 27, 3008; and 3, 3 '-dimethyl-2, 2' -dihydroxydiphenylmethane may be prepared according to Synthesis, 1981, 2, 143. 3, 3 ', 5, 5', 6, 6 '-hexamethyl-2, 2' -biphenol can be prepared according to JP 85-216749.

Acetal-substituted ortho-hydroxyaldehydes can be prepared by those skilled in the art. For example, an acetal can be prepared by refluxing ethylene glycol with o-hydroxyaldehyde in the presence of an oxalic acid catalyst. For the acid-catalyzed reaction of aldehydes and alcohols to produce acetals, see Tetrahedron, 1996, 14599; tet.lett, 1989, 1609; tetrahedron, 1990, 3315. The cyclic ether substituted phenols may be prepared as described in Aust.J. chem.1988, 41, 69-80.

Phosphorus chlorides can be prepared by a number of different methods known in the art, for example, as described in the following references: polymer, 1992, 33, 161; inorganic Synthesis, 1966, 8, 68; US5,210,260; breast, chem, 1986, 535, 221. Phosphorus chlorides with ortho-substituted phenols may be derived from PCl₃And phenol in situ. Likewise, 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. C1P (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 U.S. Pat. No. 5,821,378.

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.

Bis (phosphite) ligands supported on polymeric resins, such as Merrifield resins, can be prepared in a similar manner, as described in the following references: hetet, c.l., David, m., Carreaux, f., Carboni, b, and Sauleau, a, Tetrahedron lett, 1997, 38, 5153-.

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 of the formulas I, I-A, I-B, II, II-A and II-B and a transition metal. In embodiments of the invention, the catalyst composition used in, for example, a hydroformylation process may contain a group VIII compound, which may be as known in the artTechniques are prepared or formed, for example, as described in WO9530680, US3,907,847 and j.amer.chem.soc., 1993, 115, 2066. Examples of 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 acetylacetonyl; "OAc" is acetyl; "COD" is 1, 5-cyclooctadiene; "Ph" is phenyl). 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(acetylacetonyl), Rh (CO)₂(C₄H₉COCHCO-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: US3,496,217; US3,631,191; US3,846,461; US3,847,959 and US3,903,120, 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 halogen, carboxylate, or acetylacetonate. 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 US3,496,217; US3,496,218; and US4,774,353. These materials include metal salts (e.g., ZnCl)₂，CoI₂And SnCl₂) And organometallic compounds (e.g., RAlCl)₂，R₃SnO 3SCF₃And R₃B, wherein R is an alkyl or aryl group). US4,874,884 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 formulas I, I-A, I-B, II-a or II-B.

Representative ethylenically unsaturated compounds useful in the hydrocyanation process of the present invention are shown in structures III or V, and the corresponding terminal nitrile compounds prepared are shown in structures IV or VI, respectively, wherein like reference numerals have the same meaning.

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 2to 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 components 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 some extent on the particular catalyst employed, the particular unsaturated compound employed and the desired rate. Generally, temperatures between-25 ℃ and 200 ℃, preferably between 0 ℃ and 150 ℃ are employed.

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 not be cost effective relative to such increases in 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, US3,655,723.

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 US3,496,217; US3,496,218; and US4,774,353. 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). US4,874,884 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 with subsequent isomerization

The present invention also provides a process for the hydrocyanation of diolefins which comprises reacting a diolefin 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 at least one ligand selected from the group represented by structural formula II, II-A or II-B. In addition, the present invention provides a process for preparing a linear monoalkenenitrile by isomerizing a branched monoalkenenitrile, which is carried out in the presence of a catalyst composition comprising a transition metal selected from the group consisting of Ni, Co, and Pd, and at least one ligand selected from the group represented by structural formula II, II-A, or II-B.

The diolefins used in the present invention include primarily conjugated diolefins containing from 4 to 10 carbon atoms; for example, 1, 3-Butadiene (BD) and cis-and trans-2, 4-hexadiene. Butadiene is particularly preferred because of its important commercial value in the production of adiponitrile. Other suitable dienes include dienes substituted with groups that do not deactivate the catalyst, such as cis-and trans-1, 3-pentadiene.

The following structures VII and VIII illustrate suitable representative starting diolefin compounds; structures IX, X and XI represent products obtained from 1, 3-butadiene and HCN.

CH₂＝CH-CH＝CH₂ R²⁴-CH＝CH-CH＝CH-R²⁵

VII VIII

1, 3-butadiene

Wherein each R is²⁴And R²⁵Independently H, C₁-C₃An alkyl group.

H₃C-CH＝CH-CH₂-CN CH₂＝CH-CH₂-CH₂-CN

IX X XI

3PN 4PN 2M3

It will be appreciated that the compound VII is a special case of the formula VIII, wherein each R is²⁴And R²⁵Is H. In structures IX, X and XI, 3PN is 3-pentenenitrile, 4PN is 4-pentenenitrile and 2M3 is 2-methyl-3-butenenitrile.

For the procedure for carrying out the hydrocyanation of diolefins according to the invention, the following description is made:

the hydrocyanation reaction may be carried out in the presence or absence of a solvent. The solvent should be liquid at the reaction temperature and inert to the unsaturated compound and the catalyst. Typically, such solvents are hydrocarbons such as benzene or xylene, or nitriles such as acetonitrile, benzonitrile or adiponitrile.

The exact temperature used will depend to some extent on the particular catalyst employed, the particular unsaturated compound employed and the desired rate. Generally, temperatures between-25 ℃ and 200 ℃ are employed, with a preferred range between 0-150 ℃.

The reaction may be carried out by charging the whole of the reactants in one reactor, or preferably by charging the catalyst or catalyst components, the unsaturated compound and the solvent in the reactor. The hydrogen cyanide gas then flows over the surface of the reaction mixture, or bubbles through the reaction mixture. If desired, when a gaseous unsaturated organic compound is employed, the hydrogen cyanide and unsaturated organic compound may be fed together into the reaction medium. For batch operation, the molar ratio of HCN to catalyst will generally vary from about 10: 1 to 100000: 1, preferably from 100: 1 to 5000: 1. In continuous operation, such as when operating with a fixed bed catalyst, a higher proportion of catalyst may be employed, such as a ratio of HCN to catalyst of from 5: 1 to 100000: 1, preferably from 100: 1 to 5000: 1.

Preferably, the reaction medium is agitated, for example by stirring or shaking. The cyanide product can be recovered by conventional means, such as crystallization of the product from solution or by distillation.

One can isolate the 2-alkyl-3-monoalkenenitriles produced by the hydrogenation of the diolefin cyanide and also proceed to the isomerization under similar reaction conditions.

The 2-alkyl-3-monoalkenenitriles used as starting materials in the isomerization reaction of the present invention may be prepared by hydrogenation of the diene nitrile described above, or may be derived from any other available source. Suitable starting 2-alkyl-3-monoalkenenitriles may also carry groups which do not attack the catalyst, for example, another cyano group. Preferably, the starting 2-alkyl-3-monoalkenenitriles contain from 5 to 8 carbon atoms, excluding any additional substitution. 2-methyl-3-butenenitrile (2M3) is of particular importance in the production of adiponitrile. Other representative nitriles include 2-ethyl-3-butenenitrile and 2-propyl-3-butenenitrile.

The following structures XI and XII illustrate suitable representative starting 2-alkyl-3-monoalkenenitriles. When the starting nitrile is 2-methyl-3-butenenitrile, the isomerization products are 3-pentenenitrile and 4-pentenenitrile.

Wherein R is²⁶Is H or C₁-C₃An alkyl group.

It will be appreciated that the formula XI is a special case of formula XII, in which R is²⁶Is hydrogen.

The isomerization reaction of the present invention may be carried out, for example, at atmospheric pressure and at any temperature in the range of 10 to 200 ℃, preferably at 60 to 150 ℃. The pressure is not critical, although it may be above or below atmospheric pressure, if desired. Any conventional batch or continuous flow process can be used in the liquid phase or, in the vapor phase with volatile reactants and products. The reactor can be any mechanically and chemically resistant material, which is usually glass or an inert metal or alloy, e.g., nickel, copper, silver, gold, platinum, stainless steel, Monel^®，Hastelloy^®And the like.

The reaction is typically carried out in a "neat" manner, i.e., in the absence of added diluent or solvent; any solvent or diluent which does not damage the catalyst may be used. Suitable solvents include aliphatic or aromatic hydrocarbons (hexane, cyclohexane, benzene), ethers (diethyl ether, Tetrahydrofuran (THF), dioxane, ethylene glycol dimethyl ether, anisole), esters (ethyl acetate, methyl benzoate), nitriles (acetonitrile, benzonitrile), and the like.

To prevent oxidative deactivation of the catalyst, a non-oxidizing environment is required. Thus, an inert atmosphere, such as nitrogen, is generally preferred, although air may be used if desired, at the expense of losing a portion of the catalyst due to oxidation.

The nickel complex is essentially non-volatile, while the 2-alkyl-3-monoalkenenitrile reactant and the linear monoalkenenitrile product are relatively volatile. Thus, in a continuous flow process, the catalyst may be a component of the flow system in a complete liquid phase operation, it may be a mobile non-flowing liquid in a semi-vapor phase operation, or it may be in a fixed bed state (typically on a solid support) in a conventional flow vapor phase operation.

The time element of the reaction process is not critical and is generally determined by the particular circumstances. The time required to achieve a practical level of conversion of 2-alkyl-3-monoalkenenitriles to linear monoalkenenitriles depends on the reaction temperature, i.e., operation at lower temperatures generally requires longer times than operation at higher temperatures. The actual reaction time may range from seconds to hours, depending on the particular operating conditions and process.

For batch or continuous operation, the molar ratio of 2-alkyl-3-monoalkenenitriles to catalyst is generally greater than 1: 1, generally between about 5: 1 and 20000: 1, preferably between 100: 1 and 5000: 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: 3-pentenoic acid methyl ester

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 isomerization reaction, the 3PN/2M3 ratio is given, which is defined above.

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

Of acetal ASynthesis of

In an apparatus equipped with a condenser and a Dean-Stark trap, o-hydroxybenzaldehyde (24.4g, 200mmol), ethylene glycol (31g, 500mmol), oxalic acid (1g, 11mmol) and toluene (150mL) were combined and heated to reflux for 3 days. After cooling, the solution was taken up in NaHCO₃And distilled water washing. The solution was over MgSO₄The solvent was evaporated to give 26g of an off-white solid. It was crystallized from hexane.

Example 2

Synthesis of Acetal B

In an apparatus equipped with a condenser and a Dean-Stark trap, o-hydroxybenzaldehyde (244g, 2.0mol), 1, 3-propanediol (228g, 3.0 mol), and oxalic acid (4.5g, 0.05mol) were added to 400mL of toluene and heated at reflux for 8 hours. After cooling, the solution was taken up in NaHCO₃And distilled water, washing the solution over MgSO₄And drying. When the solvent is evaporated, the product precipitates out. The solid was collected and dissolved in hot hexane. The solution was filtered through Celite ® (a filtration aid, manufactured by Johns Manville), and the product was crystallized to give 108g of an off-white solid.

Example 3

Synthesis of Acetal C

In an apparatus equipped with a condenser and a Dean-Stark trap, o-hydroxybenzaldehyde (24g, 0.2mol), neopentyl glycol (20.9g, 0.2mol), oxalic acid (1g, 11mmol) and toluene (150mL) were combined and heated to reflux for 2 days. After cooling, the solution was taken up in NaHCO₃And distilled water washing. The solution was over MgSO₄Dried and the solvent evaporated to give 39g of a white solid which crystallized from hexane.

Example 4

Synthesis of Acetal D

O-hydroxybenzaldehyde (12.2g, 0.1mol) and trimethyl orthoformate (10.6g, 0.1mol) were dissolved in dry MeOH (40mL), H was added₂SO₄(0.25 g). The reaction was stirred at room temperature under nitrogen for 2 days. By adding solid NaHCO₃Followed by the addition of Na₂CO₃The reaction was terminated until the mixture became pH9 or higher. The product was distilled under vacuum (86.5-88 ℃ C., 2torr) and 3.98g of material was collected.

Example 5

Synthesis of amino-acetals E

In an apparatus equipped with a condenser and a Dean-Stark trap, o-hydroxyaldehyde (6.11g, 0.05mol), 2-anilinoethanol (8.23g, 0.06mol), and oxalic acid (0.45g, 5mmol) were dissolved in toluene (50mL) and heated to reflux overnight. After cooling, the solution was taken up in NaHCO₃Washing the aqueous solution with distilled water, and dissolving the toluene solution in MgSO₄And drying. After filtration, hexane was added until the product started to precipitate. 5.89g of a solid was collected.

Example 6

Synthesis of Acetal F

A300 mL flask was charged with 14.929g of 5-chloro-o-hydroxyaldehyde, 12.409g of tetramethylethylene glycol, 0.300g of oxalic acid, and 150mL of toluene. The flask was attached to a Dean-Starke trap and the mixture refluxed overnight. The mixture was washed with aqueous sodium bicarbonate and the organic layer was dried over magnesium sulfate. The solvent was removed by rotary evaporation. A yellow solid was obtained which was recrystallized from hot hexane. The solid was washed with acetonitrile to give 7.118g of a white solid.¹H NMR(500MHz，C₆D₆，δ)：7.9(s，1H)，7.17(d，2.6Hz，1H)，7.08(dd，J＝2.6，8.7Hz，1H)，6.73(d，J＝8.7Hz，1H)，6.02(s，1H)，1.26(s，6H)，1.18(s，6H)。

Example 7

Synthesis of Acetal G

A flask was charged with 18g of 5-chloro-o-hydroxyaldehyde, 13g of 1, 3-propanediol, 2g of oxalic acid and 200mL of toluene. The flask was attached to a Dean-Starke trap and the mixture refluxed for 12 hours. The mixture was washed with water and aqueous sodium bicarbonate. The organic layer was dried over magnesium sulfate and the solvent was removed by rotary evaporation. A pale rice-pudding oil (22.3g) was obtained which solidified on standing.¹H NMR(500MHz，C₆D₆，δ)：7.7(s，1H)，6.96(d，2.6Hz，1H)，6.72(dd，J＝2.6，8.7Hz，1H)，6.49(d，J＝8.7Hz，1H)，4.87(s，1H)，3.37(m，2H)，2.99(m，2H)，1.37(m，1H)，0.35(m，1H)。

Example 8

Synthesis of Acetal H

In an apparatus equipped with a condenser and a Dean-Stark trap, o-hydroxybenzaldehyde (24g, 0.2mol), 2-methyl-1, 3-propanediol (18.0g, 0.2mol), oxalic acid (2.0g), and toluene (250mL) were combined and heated to reflux for 2 days. After cooling, the solution was taken up in NaHCO₃(2X 30mL) and distilled water (30 mL). The solution was over MgSO₄Dried and the solvent evaporated to give 39g of a white solid which crystallized from hexane.

Example 9

Synthesis of ligand A

Acetal A (1.33g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL),the solution was cooled to-40 ℃. Et dissolved in toluene (15mL) was added dropwise with stirring₃N (1.0g, 10.0 mmol). The reaction temperature was slowly raised to room temperature and then stirred overnight. Et dissolved in toluene (15mL)₃A mixture of N (0.4g, 4.0mmol) and dimethyl 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate (0.8g, 2.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 2 hours. The solution was filtered through Celite ® and the solvent was removed to give 2.0g of product.³¹P NMR(C₆D₆): delta 132.6, and other peaks at 146.3, 130.3, 130.7 ppm.

Example 10

Synthesis of ligand B

Acetal A (1.33g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and the solution was cooled to-40 ℃. Et dissolved in toluene (15mL) was added dropwise with stirring₃N (1.0g, 10.0 mmol). The reaction temperature was slowly raised to room temperature and then stirred overnight. Et dissolved in toluene (15mL)₃A mixture of N (0.4g, 4.0mmol) and 3, 3 ' -dimethoxy-5, 5 ' -dimethyl-2, 2 ' -biphenol (0.55g, 2.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 2 hours. The solution was filtered through Celite ® and the solvent was evaporated to give 1.8g of product.³¹P NMR(C₆D₆): delta 134.9, minor peaks at 145.4, 132.3 ppm.

Example 11

Synthesis of ligand C

Acetal A (1.33g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and the solution was cooled to-40C. Et dissolved in toluene (15mL) was added dropwise with stirring₃N (1.0g, 10.0 mmol). The reaction temperature was slowly raised to room temperature and then stirred overnight. Et dissolved in toluene (15mL)₃A mixture of N (0.4g, 4.0mmol) and diphenyl 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate (1.05g, 2.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 2 hours. The solution was filtered through Celite ® and the solvent was removed to give 2.2g of product.³¹P NMR(C₆D₆): delta 130.2, and secondary peaks at 146.8 and 131.4 ppm.

Example 12

Synthesis of ligand D

Acetal C (1.67g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and the solution was cooled to-40 ℃. Et dissolved in toluene (15mL) was added dropwise with stirring₃N (1.0g, 10.0 mmol). The reaction temperature was slowly raised to room temperature and then stirred overnight. Et dissolved in toluene (15mL)₃A mixture of N (0.4g, 4.0mmol) and 3, 3 ', 5, 5 ' -tetramethyl-2, 2 ' -biphenol (0.48g, 2.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 2 hours. The solution was filtered through Celite ® and the solvent was evaporated to give 1.3g of a white sticky solid.³¹P NMR(C₆D₆): delta 135.2, and the other peaks at 142.7 and 134.5 ppm.

Example 13

Synthesis of ligand E

Acetal D (336mg, 2.0mmol) and Et₃N (1.0g, 10.0mmol) was dissolved in toluene (5mL) and the solution was added dropwise to a stirred solution of PCl₃(137mg, 1.0mmol) was dissolved in toluene (2mL) to give a-20 ℃ solution. The reaction was continued for 20 minutes with stirring, then 2, 2' -binaphthol (143mg, 0.5mmol) and Et dissolved in toluene (3mL)₃A mixture of N (0.4g, 4.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 1 hour. After filtration of the solution, the solvent was removed by evaporation to give 0.57g of product.³¹P NMR(C₆D₆): delta 131.7, and secondary peaks at 146 and 130.1 ppm.

Example 14

Synthesis of ligand F

A dry ether solution of acetal C (50mL) was added dropwise over a 20 minute period to N, N-diethylphosphoramido (N, N-diethylphosphoramido) dichloride (3.36gm, 19.3mmol) and dry triethylamine (4.88gm, 48.3mmol) dissolved in 150mL dry ether under a dry nitrogen atmosphere with stirring. After stirring overnight, the triethylammonium chloride solid was filtered under vacuum and washed with dry diethyl ether (3X 15 mL). The combined ether filtrates were evaporated to give the desired phosphoramide [2- [5, 5- (CH)₃)₂-1，3-C₃H₅O₂]C₆H₄O]₂PN(C₂H₅)₂It was a white solid (9.33 gm).³¹P NMR(CDCl₃)：141.9ppm。

The phosphoramidate (9.33gm, 18.0mmol) was dissolved in dry ether (150mL) and then cooled to-35 ℃ in a freeze-drying oven. Hydrochloric acid (36mL, 1.0M) in dry ether was added dropwise over a 20 minute period to the cold stirred phosphoramidate solution. The resulting mixture was returned to the freezer and cooled for an additional 1.5 hours. The solid was filtered under vacuum and washed with dry ether (20 mL). The combined ether filtrates were evaporated to give the phosphorus chloride [2- [5, 5- (CH) of acetal C₃)₂-1，3-C₃H₅O₂]C₆H₄O]₂PCl。³¹P NMR(CDCl₃)：163.9ppm。

Bis (2, 6-dimethylphenyl) 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate (0.792gm, 1.36mmol) was added to the phosphorus chloride (1.634gm, 3.40mmol) of the acetal C dissolved in dry diethyl ether (50 mL). After cooling to-35 ℃ in a freeze-drying cabinet, the pale yellow mixture was stirred while adding dropwise to dry triethylamine (0.344gm, 3.39mmol) over a period of 5 minutes. After stirring for an additional 2.5 hours at room temperature, the mixture was filtered through dry neutral alumina which was washed with dry tetrahydrofuran (50 mL). The combined filtrates were evaporated to give the desired diphosphite ligand as a pale yellow solid (0.376 gm).³¹P NMR(CDCl₃)：129.7ppm。

Example 15

Synthesis of ligand G

2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylic acid (1.87gm, 5.0mmol) was dissolved in dry tetrahydrofuran (50mL) with stirring in a dry nitrogen atmosphere and then cooled to-78 ℃ using a dry ice/acetone bath. Methyllithium (25mL, 1.4M in ether, 35mmol) was added dropwise thereto, and the solution was then allowed to warm to room temperature. After stirring overnight, the solution was slowly added to ice-cold 1M hydrochloric acid (30 mL). The organic phase is washed with water and then evaporated. The orange residue was dissolved in dichloromethane and eluted through a silica gel packing. The orange filtrate was evaporated to give 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (methyl ketone) as a yellow solid (1.52 gm).

2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (methyl ketone) (0.200gm, 0.54mmol) was added to the phosphorus chloride (0.651gm, 1.35mmol) of the acetal C dissolved in dry diethyl ether (50 mL). After cooling to-35 ℃ in a freeze-drying oven, the pale yellow mixture was stirred while adding dropwise to dry triethylamine (0.155gm, 1.53mmol) over a period of 5 minutes. After stirring at room temperature for another 48 hours, the mixture was filtered through dry neutral alumina which was rinsed with dry ether (50 mL). The combined filtrates were evaporated to give the desired diphosphite ligand as a pale yellow solid (0.466 gm).³¹P NMR(CDCl₃)：134.1ppm。

Example 16

Synthesis of ligand H

2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylic acid (8.42gm, 22.5mmol) was dissolved in dry tetrahydrofuran (500mL) with stirring in a dry nitrogen atmosphere and then cooled to-78 ℃ using a dry ice/acetone bath. Phenyllithium (1.8M in cyclohexane/diethyl ether at 70/30, 100mL, 0.18mol) was added dropwise thereto, and the solution was allowed to warm to room temperature. After stirring overnight, deionized water (50mL) was slowly added to the reaction solution at 0 ℃. Under vigorous stirring, 1M hydrochloric acid was added dropwise until the aqueous phase changed to a strongly acidic pH of 2. The organic phase was washed with water in a separatory funnel, then dried over magnesium sulfate and evaporated. The orange residue was redissolved in dichloromethane and eluted through a silica gel packing. The orange filtrate was evaporated to give 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (phenyl ketone) as a yellow solid (10.5 gm).

2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -bis (phenyl ketone) (0.715gm, 1.45mmol) was added to the phosphorus chloride (1.738gm, 3.62mmol) of the acetal C dissolved in dry diethyl ether (50 mL). After cooling to-35 ℃ in a freeze-drying oven, the orange solution was stirred while adding dropwise dry triethylamine (0.365gm, 3.62mmol) over a period of 5 minutes. After stirring for an additional 2.5 hours at room temperature, the yellow mixture was filtered through dry neutral alumina which was washed with dry diethyl ether (50 mL). The combined filtrates were evaporated to give the desired diphosphite ligand as a pale yellow solid (1.68 gm).³¹P NMR(CDCl₃)：134.0ppm。

Example 17

Synthesis of ligand I

A round bottom flask was charged with 0.412g of phosphorus trichloride and about 50mL of toluene. The mixture was cooled to-30 ℃ and 1.288G of acetal G was added. Triethylamine (0.800g) dissolved in 20mL of toluene was added dropwise to the pre-cooled solution (-30 ℃). Of mixtures³¹The P NMR spectrum showed major peaks at 164.1ppm and minor peaks at 193.3 and 132.5 ppm. To this mixture was added 0.405g of 2, 2' -ethylenebis (4, 6-dimethylphenol) dissolved in 10mL of toluene, according to Yamada et al at BuPrepared as described in ll.chem.soc.jpn., 1989, 62, 3603, followed by the addition of 0.600g of triethylamine. The mixture was stirred overnight, then filtered through Celite ®, which was washed with toluene and the solvent removed by rotary evaporation to give 1.8g of a white solid.³¹P{H}(202MHz，C₆D₆): the major resonance peak is at 134.9ppm, and the minor resonance peaks are at 132.6, 132.2, 130.9, and 128.2 ppm. APCI MS (atmospheric pressure chemical ionization mass spectrometry): foundation: 1183.1, respectively; to C₅₈H₆₀O₁₄Cl₄P₂+H⁺The calculation of (2): 1183.22.

example 18

Synthesis of ligand J

Acetal A (1.33g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and the solution was cooled to-40C. Et dissolved in toluene (15mL) was added dropwise to the cooled solution₃N solution (1.0g, 10.0 mmol). The reaction temperature was allowed to rise to room temperature and then stirred overnight. (N-methyl, N-phenyl) -2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -diamide (1.1g, 2mmo1) and Et in toluene (15mL)₃A solution of N (0.4g, 4.0mmol) was added and the mixture stirred for 2 hours. The mixture was filtered through Celite ® and the solvent was removed to give 2.3g of a yellow viscous product.³¹P NMR: delta 131.6, the smaller peak at 127.6 and the broad peak at 133.1, 144.1 ppm.

Example 19

Synthesis of ligand K

2- (tetrahydro-2-furanyl) phenol (5.10gm, 31.1mmol) was added dropwise to N, N-diethylphosphoramide dichloride (2.702gm, 15.5mmol) and dried triethylamine (3.77gm, 37.3mmol) dissolved in 200mL of dry diethyl ether under a dry nitrogen atmosphere with stirring. After 1 hour had elapsed, the triethylammonium chloride solid was filtered under vacuum and washed with dry diethyl ether (3X 15 mL). The combined ether filtrates are evaporated to give the desired phosphoramide, [2- [2-C ]₄H₇O]C₆H₄O]₂PN(C₂H₅)₂And is viscous oil.³¹P NMR(CDCl₃): 142.2, 142.0, 141.5 and 141.2ppm belong to a mixture of stereoisomers.

The phosphoramidate (5.0gm, 11.6mmol) was dissolved in dry ether (50mL) and then cooled to-35 ℃ in a freeze-drying oven. Hydrochloric acid (24mL, 1.0M in dry ether) was added dropwise to the cold stirred phosphoramidite solution. After 5 minutes of completion of the addition, the solid was filtered under vacuum and washed with dry ether (3X 15 mL). The combined ether filtrates were evaporated to give the phosphorus chloride [2- [2-C ] of 2- (tetrahydro-2-furanyl) phenol₄H₇O]C₆H₄O]₂PCl。³¹P NMR(C₆D₆): 163.7, 162.9, 162.5ppm, as a mixture of stereoisomers.

Diphenyl 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate (0.425gm, 0.807mmol) was added to the phosphorus chloride (0.793gm, 2.02mmol) of the 2- (tetrahydro-2-furanyl) phenol dissolved in dry diethyl ether (50 mL). After cooling to-35 ℃ in a freeze-drying oven, the pale yellow mixture was stirred while adding dropwise to dry triethylamine (0.204gm, 2.02mmol) over a period of 10 minutes. The mixture was filtered through dry neutral alumina which was washed with dry ether (3X 25 mL). The combined filtrates are evaporated to give the desired diphosphite ligand,as a white solid (0.81 gm).³¹P NMR(C₆D₆): the peaks were centered at 131ppm and were assigned to the stereoisomer mixture.

Example 20

Synthesis of ligand L

A round bottom flask was charged with 0.343g of phosphorus trichloride and about 50mL of toluene. The mixture was cooled to-30 ℃ and 1.284g of acetal F were added. Triethylamine (0.700g) dissolved in 20mL of toluene was added dropwise to the pre-cooled solution (-30 ℃). Of mixtures³¹The P NMR spectrum showed major peaks at 162.6ppm and minor peaks at 190.4 and 130.7 ppm. To this mixture was added 0.358g of 2, 2' -binaphthol dissolved in 10mL of toluene, followed by 0.600g of triethylamine. The mixture was stirred overnight, then filtered through Celite ®, which was washed with toluene and the solvent removed by rotary evaporation to give 1.753g of a white solid.³¹P{H}(202MHz，C₆D₆): the main resonance peak is at 130.0ppm and the other resonance peaks are at 143.1 and 130.8 ppm. APCI MS: foundation: 1366.3, respectively; to C₇₂H₇₆O₁₄Cl₄P₂The calculation of (2): 1366.346.

example 21

Synthesis of ligand M

Acetal A (1.33g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and cooled to-40C. Et dissolved in toluene (15mL) was added dropwise to the cold solution₃N(1.0g, 10.0mmol) of the solution. The reaction temperature was allowed to rise to room temperature and then stirred overnight. 2, 2' -biphenol (0.37g, 2mmol) and Et in toluene (15mL)₃A solution of N (0.4g, 4.0mmol) was added and the mixture stirred for 2 hours. The mixture was filtered through Celite ® and the solvent was removed to give 1.79g of a pale oily residue.³¹P NMR: delta 131.3, the smaller peaks at 132.5, 144.2 ppm.

Example 22

Synthesis of ligand N

Amino-acetal E (482mg, 2.0mmol) and Et₃N (0.67g) was dissolved in toluene (10 mL). Adding the solution to a mixture of PCl over a period of 5 minutes₃(137mg, 1.0mmol) was dissolved in toluene (3mL) to give a-20 ℃ solution. After addition, the mixture was stirred at-20 ℃ for 15 minutes. 2, 2' -binaphthol (143mg, 0.5mmol) and Et in toluene (5mL)₃A suspension of N (0.33g) was added in one portion and the mixture was stirred for 2 days. After filtration of the mixture, the solvent was removed by evaporation to give 0.47g of product.³¹P NMR: δ 132.1, 130.8, the smaller peaks are at 147.2, 144.9 ppm.

Example 23

Synthesis of ligand O

Acetal C (25.0g, 120mmol) and PCl₃(8.23g, 60mmol) was dissolved in toluene (100mL) and cooled to-20 ℃. To the acetal solution, Et dissolved in toluene (100mL) was added dropwise over 30 minutes₃N(21.0g，200.0mmol) of the solution of about 2/3. The mixture was stirred at-20 ℃ for an additional 15 minutes. To this cold chloride solution (-10-15 deg.C) was added a small amount of solid bis (2-tolyl) -2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate (16.5g, 29.8mmol) over the next 1 hour while alternately adding equal portions of the remaining Et3N solution. The mixture was stirred for 1 hour, and the mixture was filtered. The solvent volume was reduced to between 100 and 200mL of toluene and the solution was allowed to stand for 2 days. A fine white precipitate (20.6g) was collected.³¹P NMR: delta 129.5, very small peaks at 133.1, 146.7 ppm.

Example 24

Preparation of carbon-supported catalysts with ligand O

Crystalline Rh (CO)₂(acac) (1 eq) was dissolved in 2-4mL of toluene. The pale yellow solution was added to solid ligand O (100mg) and foaming occurred and the solution color changed.

5g of granular (40-60 mesh) activated carbon (EM Scientific) was heat dried and calcined in flowing chlorine (100mL/min) at 850 ℃ for 5 hours. The dried char was transferred to a nitrogen-filled glove box where it was slurried into a toluene solution containing rhodium and ligand O. The slurry was stirred for 15 minutes and then evaporated to dryness in vacuo. The residual solids that deposited on the side walls of the vessel were rinsed with additional toluene so that they all eventually deposited only on top of the carbon. The dry solid was pumped overnight to remove residual toluene, then capped and stored in a glove box for catalytic testing.

Example 25

Synthesis of ligand P

This diphosphite is prepared according to the general procedure described for ligand K, except that the corresponding dimethyl ester is used in place of diphenyl 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate. The product is an oil.³¹P NMR(C₆D₆): 131.0, 130.9, 130.8, 130.6, 130.4, 130.3ppm, are mixtures of stereoisomers and the ring monophosphite impurities are at 146.8 and 146.4 ppm.

Example 26

Synthesis of ligand O-Polymer Supported ligand

Preparation of loaded disubstituted binaphthol

50g (60mmol) of Merrifield resin (polCH) with stirring₂Cl, where pol is 1-2% cross-linked polystyrene, 200-mesh 400-mesh beads), 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylic acid (33.7g), potassium carbonate (12.4g), and DMF (dimethylformamide) (350ml) were heated at 90 ℃ for 8 hours. The resin color changed from white to green-yellow. The mixture was diluted with water, filtered and washed with H₂O, DMF and acetone, followed by thorough drying in air to give the desired product. IR (KBr, cm)^-1)：1712(vs)，1676(vs)。

Functionalization reactions of carboxylic acid groups

25g (18.7mmol) of the polymer-supported diol are suspended in 150mL of anhydrous DMF, and 4.54g (28mmol) of 1, 1-carbonyldiimidazole are added to this mixture. The mixture was shaken overnightThe polymer beads turned dark red-orange. The beads were collected by filtration and washed with DMF (3X 100mL), toluene (3X 100mL) and CH₂Cl₂(3X 100mL) and then dried in vacuo. IR (cm)^-1，KBr)：1771(vs)，1720(vs)。

Esterification of side chains

25.93g (18.7mmol) of the polymer-supported imidazolyl ester was suspended in 150mL of anhydrous DMF. 10.10g (93.5mmol) o-cresol and 2.845g (18.7mmol) DBU (1, 8-diazabicyclo [5.4.0 ] were added]Undec-7-ene). The mixture was shaken at room temperature for 2 days. The product was collected by filtration using DMF, toluene and CH₂Cl₂It was washed (3X 100mL) and then finally dried under vacuum. IR (cm)^-1，KBr)：1759(w)，1720(w)，1675(vs)。

Synthesis of ligand Q

24.8g (17.4mmol) of the supported diol are suspended in 150mL of toluene, and to this suspension 25.0g (52.1mmol) of phosphorus chloride derived from acetal C and 13.4g of diisopropylethylamine are added. The mixture was shaken overnight at room temperature. Collecting light yellow beads by filtering, and adding toluene and CH₂Cl₂(3X 100mL) and then dried under vacuum. Elemental analysis: 1.15 wt% P (average).

Example 27

Synthesis of ligand R

2-Hydroxyphenylethyl alcohol is reacted with bromoacetonitrile in the presence of potassium carbonate to protect the phenolic oxygen as described in Tetrahedron Letters, 1993, 34, 7567-one 7568. 2-Hydroxyphenylethyl alcohol was dissolved in 20mL of acetone. To the solution was added 1.2g of potassium carbonate. To this stirred mixture was added 0.87g of bromoacetonitrile under nitrogen atmosphere. The mixture was stirred overnight. The mixture was filtered and the filtrate was concentrated. The product was purified by flash column chromatography on silica gel and purified using 1/1 ethyl acetate: hexane elution gave 81% 2- (o-cyanomethyl) phenethyl alcohol.¹H NMR(CD₂Cl₂): 2.81(t, 2H), 3.72(t, 2H), 4.77(s, 2H), 6.92(dd, 2H), 7.18(d, 2H). 2- (o-cyanomethyl) phenethyl alcohol (1.0g, 6.3mmol) was dissolved in 5mL anhydrous DMF and added to a stirred solution of sodium hydride (0.25g, 10.4mmol) in DMF (20 mL). After the hydrogen evolution was complete, methyl iodide (0.47mL, 7.5mmol) was added dropwise. The mixture was stirred at room temperature for 5 hours under nitrogen atmosphere. After formation of the aqueous solution, the product was purified by flash column chromatography on silica gel eluting with 1/5 of a solvent mixture of ethyl acetate/hexane to give 0.56g (56%) of the desired product, 2- (o-cyanomethyl) phenethylmethyl ether.¹H NMR(CD₂Cl₂)：2.96(t，2H)，3.36(s，3H)，3.60(t，2H)，4.86(s，2H)，7.04(dd，2H)，7.31(d，2H)。

Deprotection of 2- (o-cyanomethyl) phenethylmethyl ether was carried out as described in tetrahedron letters, 1993, 34, 7567-7568. 2- (o-cyanomethyl) phenethylmethyl ether (0.56g, 3.13mmol) was dissolved in 40mL of absolute ethanol. Platinum dioxide (20mg) was added to the solution. The solution was purged with hydrogen for 10 minutes and then stirred overnight under a hydrogen atmosphere. After filtration of the mixture, the filtrate was concentrated. The residue was redissolved in ether, washed with water and over MgSO₄And drying. After concentration, 0.39g (82%) of 2-hydroxy group are isolatedPhenethylmethyl ether.¹H NMR(CD₂Cl₂)：2.78(t，2H)，3.32(s，3H)，3.60(t，2H)。

In the same manner as in example 25, 2-hydroxyphenylethyl methyl ether was reacted with diethylphosphoramide dichloride to give the corresponding phosphoramide.³¹P NMR (toluene): 137 ppm. The phosphoramidate was treated with 1M HCI solution as described in example 25 to give the corresponding phosphorus chloride.³¹P NMR (toluene): 165 ppm. The phosphorus chloride was then reacted with bis (2-tolyl) -2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate in the same manner as in example 19.³¹P NMR (toluene): 125 (major peak), 127 (minor peak), 142 (minor peak).

Example 28

Synthesis of ligand S

The ethyl ether of 2-hydroxybenzyl alcohol was prepared according to the literature method reported in Recueil. Trav. Chim. Pays-Bas1955, 74, 1448. The phosphorus chloride of phenol is prepared from PCl dissolved in toluene₃Prepared with triethylamine as the base at-30 ℃. Of reaction mixtures³¹P NMR: 158, 125 ppm. To this phosphorus chloride solution was added bis (2-tolyl) -2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate in the presence of triethylamine, which was carried out as described in example 27.³¹P NMR (toluene): 131 (major peak), 146 (minor peak), 163 (minor peak).

Example 29

Synthesis of ligand T

2- (2-tetrahydropyranyl) -4-methyl-phenol was prepared from the corresponding phenol according to the method given in aust.j.chem., 1988, 41, 69-84. In a nitrogen purged glove box, 2- (2-tetrahydropyranyl) -4-methylphenol (0.96g, 5.0mmol) was dissolved in 25ml of diethyl ether and cooled to-40 ℃. Diethylphosphoramide dichloride (2.5mmol) was added followed by triethylamine (6 mmol). The reaction mixture was stirred at room temperature for 1 hour, then filtered through a plug of Celite ®. The filtrate was concentrated in vacuo to give 1.1g (90%) of the corresponding phosphoramidate.³¹P NMR (toluene): 142.7, 142.6. The above phosphoramidate (1.1g) was dissolved in 25mL of anhydrous ether and cooled to-40 ℃. To the stirred phosphoramidate solution, 4.4mL of a pre-cooled 1M HCl in ether solution was slowly added. A white precipitate formed upon addition. The mixture was stirred for 10 minutes and cooled to-40 ℃ for 2 hours. The resulting slurry was filtered through a plug of Celite ® and concentrated in vacuo to give 0.92g of the corresponding phosphorus chloride.³¹P NMR (toluene): 161.6 ppm. The above phosphorus chloride reacts with bis (2-tolyl) -2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate and triethylamine to give the corresponding ligand.³¹P NMR (toluene): 130 (main peak).

Example 30

Synthesis of ligand U

The phosphorus chloride of 2- (2-tetrahydropyranyl) -4-methyl-phenol was prepared as described in example 29. The phosphorus chloride reacts with 3, 3 ', 4, 4', 6, 6 '-hexamethyl-2, 2' -biphenol and triethylamine to obtain the corresponding ligand.³¹P NMR (toluene): 134. 131, 127.

Example 31

Synthesis of ligand V

2- (2-tetrahydropyranyl) -4-methyl-phenol was prepared from the corresponding phenol according to the method given in aust.j.chem., 1988, 41, 69-84. In a nitrogen purged glove box, 2- (2-tetrahydropyranyl) -4-methylphenol (0.96g, 5.0mmol) was dissolved in 25ml of diethyl ether and cooled to-40 ℃. Diethylphosphoramide dichloride (2.5mmol) was added followed by triethylamine (6 mmol). The reaction mixture was stirred at room temperature for 1 hour, then filtered through a plug of Celite ®. The filtrate was concentrated in vacuo to give 1.1g (90%) of the corresponding phosphoramidate.³¹P NMR (toluene): 142.7, 142.6. The above phosphoramidate (1.1g) was dissolved in 25mL of anhydrous ether and cooled to-40 ℃. To the stirred phosphoramidate solution, 4.4mL of a pre-cooled 1M HCl in ether solution was slowly added. A white precipitate formed upon addition. The mixture was stirred for 10 minutes and cooled to-40 ℃ for 2 hours. The resulting slurry was filtered through a plug of Celite ® and concentrated in vacuo to give 0.92g of the corresponding phosphorus chloride.³¹P NMR (toluene): 161.6 ppm. The phosphorus chloride reacts with 1, 1' -bi-2-naphthol and triethylamine to obtain a corresponding ligand.³¹P NMR (toluene): 131.11, 131.14 (stereoisomers).

Example 32

Synthesis of ligand W

Into a 100mL flask was added PCl₃(0.412g) and 50mL of toluene. The mixture was cooled to-30 ℃ and acetal B (1.081g) was added. Then will beNEt dissolved in 20mL of toluene₃(0.65g) the pre-cooled solution (-30 ℃ C.) was added dropwise thereto. After warming to room temperature, stirring was carried out for about 40 minutes, the mixture was cooled to-30 ℃ and 3, 3 ', 5, 5', 6, 6 '-hexamethyl-2, 2' -biphenol (0.406g) was added thereto, followed by 0.6g of NEt₃. The mixture was stirred overnight and then filtered through Celite ® to remove the solvent by rotary evaporation. A white solid (1.652g) was obtained. CDCl₃In (1)³¹P NMR: the major resonance peak is at 134.42ppm and the minor resonance peaks are at 135.08 and 132.6 ppm.

Example 33

Synthesis of ligand X

MR ═ Merrifield resin

50g (60mmol) of Merrifield resin (pol 1-2% cross-linked polystyrene, 200-mesh 400-mesh beads), 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylic acid (33.7g), potassium carbonate (12.4g) and DMF (dimethylformamide) (350ml) were heated at 90 ℃ for 8 hours with stirring. The resin color changed from white to green-yellow. The mixture was diluted with water, filtered and washed with H₂O, DMF and acetone, followed by thorough drying in air to give the desired product. IR (KBr, cm)^-1)：1712(vs)，1676(vs)。

81.64g (84mmol) of the carboxylic acid/ester supported on the pale yellow polymer were suspended in 300mL of anhydrous DMF containing 13.6g (84mmol) of carbonyldiimidazole. After stirring at room temperature overnight, the orange intermediate was isolated by filtration and washed with DMF (3 ×). The polymer was then placed in a mixture of DMF (200mL) and isopropanol (51.4mL, 672mmol), and the mixture was stirred at room temperature overnight. The polymer-supported diol/diester product was then isolated by filtration, washed with THF and acetone, and then air dried.

1.7g (1.0mmol) of the polymer-supported diol from the preceding example are suspended in 15mL of toluene, to which are added 1.7mL (10mmol) of diisopropylethylamine and 4.0mmol of the appropriate phosphorus chloride. The suspension was shaken overnight at room temperature. The colorless product was then filtered with toluene (3X 10mL), DMF (3X 10mL) and CH₂Cl₂(dichloromethane) (3X 10mL) was washed and then dried in vacuo. Elemental analysis: 1.45% P.

The polymer-supported bis (phosphite) sample was treated with Ni (COD)₂The treatment was carried out to obtain brown-orange Ni (COD) -loaded derivatives. This material was then treated with CO at 1atm and room temperature to give P supported as a pale yellow polymer₂Ni(CO)₂The infrared spectrum characteristic of KBr of the complex is as follows: 2051.7(vs), 2001.3(vs) cm^-1。

Example 34

Synthesis of ligand Y

3, 3 ', 5, 5' -tetramethyl-2, 2 '-dihydroxy-1, 1' -biphenylene (0.303gm, 1.25mmol) was added to a solution of triethylamine (0.41gm, 4.0mmol) and phosphorus chloride of 2- (tetrahydrofuran-2-yl) phenol (1.11gm, 2.8mmol) in toluene (50 mL). After stirring overnight, the solid was filtered off in vacuo and washed with toluene (3X 5 mL). The filtrate was evaporated to give the product.³¹P NMR(CDCl₃202 MHz): there are multiple peaks between 134.9 and 133.6 and between 131.2 and 127.5 ppm.

Example 35

Synthesis of ligand Z

Acetal C (1.67g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and the solution was cooled to-40 ℃. Et dissolved in toluene (15mL) was added dropwise with stirring₃N (1.0g, 10.0 mmol). The reaction temperature was slowly raised to room temperature and then stirred overnight. Et dissolved in toluene (15mL)₃A mixture of N (0.4g, 4.0mmol) and dimethyl 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate (0.8g, 2.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 2 hours. The solution was filtered through Celite ® and the solvent was removed to give 2.6g of product.³¹P NMR(C₆D₆)：δ132.7，130.4，129.7，129.1ppm。

Example 36

Synthesis of ligand AA

Acetal B (1.44g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and the solution was cooled to-40 ℃. Et dissolved in toluene (15mL) was added dropwise with stirring₃N (1.0g, 10.0 mmol). The reaction temperature was slowly raised to room temperature and then stirred overnight. Et dissolved in toluene (15mL)₃A mixture of N (0.4g, 4.0mmol) and 2, 2' -binaphthol (0.57g, 2.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 2 hours. The solution was filtered through Celite ® and the solvent was removed to give 1.7g of product.³¹P NMR(C₆D₆)：δ132.4，134.5，146.0ppm。

Example 37

Synthesis of ligand BB

Into a 100mL flask was added PCl₃(0.343g) and 50mL of toluene. The mixture was cooled to-30 ℃ and acetal F (1.284g) was added, followed by NEt dissolved in 20mL of toluene₃(0.7g) a pre-cooled solution (-30 ℃ C.) was added dropwise thereto. After warming to room temperature, stirring was carried out for about 40 minutes, the mixture was cooled to-30 ℃ and 2, 2' -ethylenebis (4, 6-dimethylphenol) (0.338g) was added thereto, followed by 0.6g NEt₃. The mixture was stirred overnight and then filtered through Celite ® to remove the solvent by rotary evaporation. A white solid (1.67g) was obtained. C₆D₆In (1)³¹P NMR: the main resonance peak is located at 133.104ppm, and the resonance peaks located at 130.96, 130.78 and 130.01 belong to impurities.

Example 38

Synthesis of ligand CC

3- (2-hydroxyphenyl) propan-1-ol was prepared from dihydrocoumarin according to the procedure given in J.chem.Soc., 1956, 2455. The hydroxyl group of phenol is protected with cyanomethyl by reacting 3- (2-hydroxyphenyl) propan-1-ol with bromoacetonitrile in the presence of potassium carbonate as described in tetrahedron letters, 1993, 34, 7567 and 7568. 3- (2-hydroxyphenyl) propan-1-ol (27.4g) was dissolved in 300mL of acetone. To the solution was added 30g of potassium carbonate, followed by bromoacetonitrile (21.7 g). The mixture was stirred overnight. The reaction mixture was filtered, concentrated, and purified by flash column chromatography to give 65% 3- (2-o-cyanomethylphenyl) propan-1-ol.¹H NMR(CDCl₃): 1.85(q, 2H), 2.73(t, 2H), 3.67(t, 2H), 4.79(s, 2H), 6.93(d, 1H), 7.03(t, 1H), 7.22(m, 2H), (t, 2H), 3.72(t, 2H), 4.77(s, 2H), 6.92(dd, 2H), 7.18(d, 2H). 3- (2-o-cyanomethylphenyl) propan-1-ol (3.0g) was added to a stirred suspension of potassium hydride (3.5g) dissolved in DMSO (dimethylsulfoxide) (30mL), followed immediately by the addition of methyl iodide (4.5 g). The solution was stirred at room temperature for 1.5 hours, then poured into water and extracted with dichloromethane. The combined organic layers were washed with water, dried over magnesium sulfate, concentrated and purified by flash column chromatography on silica gel to give 1.7g (53%) of 3- (2-o-cyanomethylphenyl) propyl-1-methyl ether. The cleavage of the cyanomethyl group was carried out according to the method described in Tetrahedron Letters, 1993, 34, 7567-7568. 3- (2-o-cyanomethylphenyl) propyl-1-methyl ether (0.77g, 3.8mmol) was dissolved in 15mL of absolute ethanol in a Fisher-Porter tube. Platinum dioxide (20mg) was added to the solution and the reaction was stirred at room temperature under 35psi hydrogen pressure for 2 hours. The mixture was filtered and the filtrate was concentrated to give 0.62g of 3- (2-hydroxyphenyl) -propyl-1-methyl ether.¹H NMR(CDCl₃)：1.41(q，2H)，2.72(t，2H)，3.37(t，2H)，3.40(s，3H)，6.85(m，2H)，7.09(m，2H)。

In a nitrogen purged glove box, 3- (2-hydroxyphenyl) propyl-1-methyl ether (1.25g) was dissolved in 38ml diethyl ether and cooled to-40 ℃. Diethylphosphoramide dichloride (0.65g) was added followed by triethylamine (0.99 g). The reaction mixture was stirred at room temperature for 1 hour, then filtered through a pad of Cekite ®. The filtrate was concentrated in vacuo to give 1.6g (99%) of the corresponding phosphoramidate.³¹P NMR (toluene): 136.7. the above phosphoramidate (1.6g) was dissolved in 37mL of anhydrous ether and cooled to-40 ℃. To the stirred phosphoramidate solution, 7.4mL of a pre-cooled 1M HCl in ether solution was slowly added. A white precipitate formed upon addition. The mixture was stirred for 10 minutes and cooled to-40 ℃ for storageFor 2 hours. The resulting slurry was filtered through a plug of Celite ® and concentrated in vacuo to give 1.345g of the corresponding phosphorus chloride.³¹P NMR (toluene): 161.6 ppm. And reacting the phosphorus chloride with 3, 3 ', 5, 5 ' -tetramethyl-1, 1 ' -biphenol and triethylamine to obtain a ligand CC.³¹P NMR (toluene): 134, 142 ppm.

Example 39

Synthesis of ligand DD

The isopropyl ether of 2-hydroxyphenylmethanol was prepared according to the literature method reported in Recueil. Trav. Chim. Pays-Bas1955, 74, 1448. The phosphorus chloride of this phenol (0.499g) was formed from PCl dissolved in toluene (11g)₃(0.206) with triethylamine (0.400g) at-30 ℃. This phosphorus chloride was then reacted with 3, 3 ', 5, 5 ' -tetramethyl 2, 2 ' -biphenol (0.203g) and triethylamine (0.300 g). The mixture was filtered through Celite ® and the solvent removed by rotary evaporation to give 0.782g of a concentrated viscous oil.³¹P NMR(CDCl₃): the major resonance peak was located at 133.95 and the minor resonance peaks were located at 142.75 and 130.89 ppm.

Example 40

Synthesis of ligand EE

Acetal H (1.55g, 8.0mmol) and PCl₃(0.55g, 4mmol) was dissolved in toluene (40mL) and the solution was cooled to-40 ℃. Et dissolved in toluene (15mL) was added dropwise with stirring₃N (1.0g, 10.0 mmol). The reaction temperature was slowly raised to room temperatureAnd then stirred overnight. Et dissolved in toluene (15mL)₃A mixture of N (0.5g, 5.0mmol) and dimethyl 2, 2 ' -dihydroxy-1, 1 ' -binaphthalene-3, 3 ' -dicarboxylate (0.8g, 2.0mmol) was added to the phosphorus chloride solution and the mixture was stirred for 2 hours. The solution was filtered through Celite ® and the solvent was removed to give 2.0g of product.³¹P NMR(C₆D₆)：δ131.1，134.4，147.4ppm。

EXAMPLE 41

Synthesis of ligand FF

A100 mL flask equipped with a magnetic stir bar was charged with 0.412g of phosphorus trichloride and 50mL of toluene. The mixture was cooled to-30 ℃ and the acetal (1.456g) derived from 5-chloro-o-hydroxyaldehyde and neopentyl glycol was added. To this mixture, a pre-cooled solution (-30 ℃) of triethylamine (0.800g) dissolved in 20mL of toluene was added dropwise. Of reaction mixtures³¹The P NMR spectrum showed a major resonance peak at 164.44ppm and minor resonance peaks at 193.04 and 131.99 ppm. After the mixture was cooled to-30 ℃, binaphthol (0.429g) dissolved in 10mL of toluene was added thereto, followed by 0.600g of triethylamine. The mixture was stirred overnight, then filtered through Celite ®, which was washed with toluene and the solvent removed by rotary evaporation to give 2.105g of a white solid.³¹P(C₆D₆): the major resonance peak is at 131.21ppm and the minor resonance peaks are at 144.96 and 132.20 ppm.

Example 42

Synthesis of ligand GG

In a 100mL flask equipped with a magnetic stir bar, 0.412g PCl was added₃1.081g of acetal B and 20mL of THF. The solution was cooled to-30 deg.C, and a pre-cooled solution (-30 deg.C) of triethylamine (0.68g) dissolved in 20mL of toluene was added dropwise thereto. The slurry was stirred at room temperature for about 1 hour. After the slurry was cooled to-30 ℃, 0.448g of 3, 3 '-diisopropyl-6, 6' -dimethyl-2, 2 '-dihydroxy-1, 1' -diphenyl was added thereto. To the mixture was added 0.600g of triethylamine. The mixture was stirred overnight, filtered and the solvent removed by rotary evaporation to give 1.668g of a white solid.³¹P(CDCl₃): the main resonance peak is 132.26ppm, and the secondary resonance peaks are 132.97, 132.86, 135.83, 132.62, 131.76 and 128.88 ppm.

Examples 43 to 53

Catalyst solutionIs prepared by mixing 0.042mmol of a bidentate ligand according to the invention and 0.014mmol of Ni (COD)₂And then preparing.

Hydrocyanation of BD: mu.L of the Ni catalyst solution (0.0018mmol Ni) prepared as described above was added to a 4-mL septum-sealed screw-capped vial and cooled to-20 ℃. After cooling, 120. mu.L of a valeronitrile solution of HCN (0.83mmol HCN) and 280. mu.L of a toluene solution of BD (0.925mmol BD) were added thereto. The vial was sealed and heated at 80 ℃. After 1.5 and 3.0 hours, samples were taken. The reaction mixture was then washed with diethyl ether (Et)₂O) and analyzed by GC using valeronitrile as an internal standard.

2M3 isomerization: mu.L of a cold solution containing 2M3 and valeronitrile (0.930mmol 2M3) and 82. mu.L of the Ni catalyst solution (0.002mmol Ni) prepared as described above were added to a septum-capped vial. The vial was sealed and heated to 125 ℃. After 1.5 and 3.0 hours, the sample was removed, cooled, and diluted in ether. The product distribution was analyzed by GC with valeronitrile as internal standard.

Examples	Ligands	After 3h BD conversion (%)	3PN/2M3 ratio generated by BD	3h after isomerization the ratio of 3PN/2M3 (% 3PN conversion)
Examples	Ligands	After 3h BD conversion (%)	3PN/2M3 ratio generated by BD		4344454647484950515253	WBXYUVZAABBCCDD	74.264.111.97889.462.659.869.521.563.470.3	24.71.437.810.70.510.40.71.43.6	21.516.820.415.415.96.01615.87.815.116.7

Catalyst evaluation method A

Catalyst solutionLiquid for treating urinary tract infectionIs prepared by mixing 0.042mmol of a bidentate ligand according to the invention and 0.014mmol of Ni (COD)₂And is prepared.

Hydrocyanation of 3, 4-pentenenitrile (3, 4PN): mu.L of a solution containing HCN, t-3PN and 2-ethoxyethyl ether (0.396mmol HCN, 0.99mmol t-3PN) was added to a septum-capped vial. To the vial was added 13. mu.L of ZnCl dissolved in t-3PN₂Solution (0.0067mmol ZnCl)₂) The vial was cooled to-20 ℃. After cooling, 116 μ L (0.003mmol ni) of the catalyst solution prepared as described above was added to the vial, which was sealed and allowed to stand at room temperature for 24 hours. After 24 hours, the reaction mixture was diluted with diethyl ether and the product distribution was analyzed by GC, using 2-ethoxyethyl ether as internal standard. The yields given are calculated based on the HCN consumed.

Catalyst evaluation method B

Into a glass reactor equipped with a nitrogen bubbler was charged 3-pentenenitrile (5 mL; 52mmol), ligand (0.42mmol), Ni (COD) under an inert nitrogen atmosphere₂(0.040 g; 0.14mmol) and ZnCl₂(0.020 g; 0.15 mmol). The mixture was heated to 50 ℃ and stirred with a magnetic stirrer. By sparging liquid HCN (cooled to 0 ℃) with dry nitrogen (30cc/min) and subjecting the saturated HCN/N obtained₂The mixture is introduced into a reactor below the liquid level so that HCN is fed into the reactor. The progress of the reaction was monitored by removing an aliquot and analyzing it with GC. After 1 hour, the reaction was terminated.

Examples	Ligands	Conversion rate	Distribution of	Method of producing a composite material
Examples	Ligands	Conversion rate	Distribution of	Method of producing a composite material	54	EE	8.8	95.5	A
55	W	72.2	97.5	A	54	EE	8.8	95.5	A
55	W	72.2	97.5	A	56	FF	21.5	96.5	A
57	B	89.5	93.3	A	56	FF	21.5	96.5	A
57	B	89.5	93.3	A	58	X	29.5	91.7	A
59	Y	26.0	71.0	A	58	X	29.5	91.7	A
59	Y	26.0	71.0	A	60	GG	63.9	95.1	B
61	CC	42.2	92.6	A	60	GG	63.9	95.1	B
61	CC	42.2	92.6	A	62	J	13.0	88.6	A
63	BB	21.5	86.6	A	62	J	13.0	88.6	A
63	BB	21.5	86.6	A	64	H	5.9	95.4	B
66	DD	64.5	91.2	A	64	H	5.9	95.4	B
66	DD	64.5	91.2	A	67	V	13.0	83.0	A

Claims

1. A hydrocyanation process comprising reacting an acyclic aliphatic monoethylenically unsaturated compound in which the olefinic double bond is not conjugated to any other group in the molecule with a source of HCN in the presence of a catalyst precursor composition comprising a Lewis acid, a zero-valent nickel, and a multidentate phosphite ligand selected from the group represented by the following structures I, I-A or I-B:

structural formula I

Structural formula I-A

Structural formula I-B

Wherein, X¹Is a bridging group selected from the group consisting of:

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R¹' and R²' is independently selected from the group consisting of: H. c₁-C₁₈Alkyl, -OR¹¹、-CO₂R¹¹Wherein R is¹¹Is C₁-C₁₈Alkyl, aryl, -C (O) R¹²or-C (O) NR¹²R¹³Wherein R is¹²And R¹³Independently selected from H, C₁-C₁₈An alkyl or aryl group; wherein the aromatic rings are other than R¹-R⁸Other positions may also be C₁-C₁₈The alkyl group is substituted by the alkyl group,

wherein R is⁹And R¹⁰Independently selected from the group consisting of H and C₁-C₁₈Alkyl groups;

wherein Y is independently selected from the group consisting of H, aryl, CR¹⁴ ₃、(CR¹⁴ ₂)_n-OR¹⁴、(CR¹⁴ ₂)_n-NR¹⁵Wherein n is a number between 0 and 3, wherein R¹⁴Is H, C₁-C₁₈Alkyl, cycloalkyl or aryl, wherein R¹⁵Selected from the group consisting of H, alkyl, cycloalkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶Is H, C₁-C₁₈Alkyl, aryl or perfluoroalkyl;

wherein Z is selected from the group Consisting of (CR)¹⁴ ₂)_n-OR¹⁴Wherein n is 0-3 and wherein R¹⁴Is as defined above;

wherein the ligand having the structure of formula I-A or formula I-B has at least one aromatic ring carbon atom located in the ortho position to the oxygen atom bonded to the P atom via (Z)¹)n¹Bonded to another aromatic ring carbon atom that is ortho to another oxygen atom bonded to the P atom;

wherein Z¹Independently is

Wherein each R¹⁷And R¹⁸Independently selected from H, C₁-C₁₈Alkyl, cycloalkyl, aryl or substituted aryl, n¹Is a number of 1 or 0, and,

or the multidentate phosphite ligand is selected from

Ligand F

Ligand O

Ligand R

Ligand S

Ligand T

And

ligand X

MR ═ Merrifield resin.

2. The method of claim 1, wherein group X²-X⁵At least one has the structure of formula a or B; y is³0 or CH₂(ii) a And R¹⁴As defined in claim 1, in accordance with claim 1,

structural formula A

Structural formula B

3. The process of claim 1, wherein the Lewis acid is selected from the group consisting of 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，CdCl₂，B(C₆H₅)₃And (C)₆H₅)₃SnX, wherein X ═ CF₃SO₃，CH₃C₆H₅SO₃Or (C)₆H₅)₃BCN。

4. The process of claim 1 wherein the 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.

5. A process for the liquid phase hydrocyanation of diolefins and isomerization of the resulting nonconjugated acyclic nitriles which comprises reacting an acyclic aliphatic diolefin with a source of HCN in the presence of a catalyst composition comprising nickel and at least one multidentate phosphite ligand of the formula II, II-a or II-B:

structural formula II

Structural formula II-A

Structural formula II-B

Wherein, X¹Is a bridging group selected from the group consisting of:

wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R¹' and R²' is independently selected from the group consisting of: H. c₁-C₁₈Alkyl, -OR¹¹、-CO₂R¹¹Wherein R is¹¹Is C₁-C₁₈Alkyl, aryl, -C (O) R¹²or-C (O) NR¹²R¹³Wherein R is¹²And R¹³Independently selected from H, C₁-C₁₈An alkyl or aryl group; wherein the aromatic rings are other than R¹-R⁸Other positions may also be C₁-C₁₈Alkyl substituted;

wherein Y is¹Independently selected from H, aryl, CR¹⁴ ₃、(CR¹⁴ ₂)_n-OR¹⁴And (CR)¹⁴ ₂)_n-NR¹⁵，

Wherein n is a number between 0 and 3, wherein R¹⁴Is H, C₁-C₁₈An alkyl group, a cycloalkyl group or an aryl group,

wherein R is¹⁵Selected from the group consisting of H, alkyl, cycloalkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶Is H, C₁-C₁₈Alkyl, cycloalkyl, aryl or perfluoroalkyl;

wherein Y is²Independently selected from aryl, CR¹⁴ ₃、(CR¹⁴ ₂)_n-OR¹⁴And (CR)¹⁴ ₂)_n-NR¹⁵Wherein n is a number between 0 and 3, wherein R¹⁴Is H, C₁-C₁₈Alkyl, cycloalkyl or aryl, wherein R¹⁵Selected from the group consisting of H, alkyl, cycloalkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶Is H, C₁-C₁₈Alkyl, cycloalkyl, aryl or perfluoroalkyl;

wherein Z is selected from the group Consisting of (CR)¹⁴ ₂)_n-OR¹⁴Wherein n is 0 to 3, wherein R¹⁴As defined above;

wherein the ligand having the structure of formula II-A or formula II-B has at least one aromatic ring carbon atom located in the ortho position to the oxygen atom bonded to the P atom via (Z)¹)n¹Bonded to another aromatic ring carbon atom that is ortho to another oxygen atom bonded to the P atom;

wherein Z¹Independently is

or the multidentate phosphite ligand is selected from

Ligand F

Ligand O

Ligand R

Ligand S

Ligand T

And

ligand X

MR ═ Merrifield resin.

6. The method of claim 5, wherein group X²-X⁵At least one has the structure of formula a or B; y is³0 or CH₂；R¹⁴Is determined byAs defined in claim 5, wherein the first and second electrode layers are made of a material,

structural formula A

Structural formula B

7. The process of claim 5, wherein (a) the hydrocyanation or isomerization is conducted in a batch operation, (b) both the hydrocyanation and isomerization are conducted in a batch operation, (c) the hydrocyanation or isomerization is conducted in a continuous operation, or (d) both the hydrocyanation and isomerization are conducted in a continuous operation.

8. The process of claim 5, wherein the diolefin compound is selected from the group consisting of 1, 3-butadiene, cis-2, 4-hexadiene, trans-2, 4-hexadiene, cis-1, 3-pentadiene and trans-1, 3-pentadiene.

9. A multidentate phosphite ligand represented by structural formula II, II-A or II-B:

structural formula II

Structural formula II-A

Structural formula II-B

Wherein, X¹Is selected fromA bridging group in the group consisting of:

wherein Y is¹Independently selected from H, aryl, CR¹⁴ ₃、(CR¹⁴ ₂)_n-OR¹⁴And (CR)¹⁴ ₂)_n-NR¹⁵Wherein n is a number between 0 and 3, wherein R¹⁴Is H, C₁-C₁₈Alkyl, cycloalkyl or aryl, wherein R¹⁵Selected from the group consisting of H, alkyl, cycloalkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶Is H, C₁-C₁₈Alkyl, cycloalkyl, aryl or perfluoroalkyl;

wherein Y is²Independently selected from aryl, CR¹⁴ ₃、(CR¹⁴ ₂)_n-OR¹⁴And (CR)¹⁴ ₂)_n-NR¹⁵Wherein n is a number between 0 and 3, wherein R¹⁴Is H, C₁-C₁₈Alkyl, cycloalkyl or aryl, wherein R¹⁵Selected from the group consisting of H, alkyl, cycloalkyl, aryl, -SO₂R¹¹、-SO₂NR¹² ₂、-COR¹⁶Wherein R is¹⁶H、C₁-C₁₈Alkyl, cycloalkyl, aryl or perfluoroalkyl;

wherein Z¹Independently is

or the multidentate phosphite ligand is selected from

Ligand F

Ligand O

Ligand R

Ligand S

Ligand T

And

ligand X

MR ═ Merrifield resin.

10. The method of claim 9, wherein Y¹Or Y²The linkage to Z forms a cyclic ether.

11. The ligand of claim 9 having the structure of formula II wherein the group X²-X⁵At least one has the structure of formula a or B; y is³0 or CH₂；R¹⁴As defined in claim 9, in accordance with claim 9,

structural formula A

Structural formula B

12. A catalyst composition comprising the ligand of claim 9 and a group VIII metal.

13. The composition of claim 12, wherein the group VIII metal is selected from the group consisting of ruthenium, rhodium, iridium, nickel, cobalt, and palladium.

14. The composition of claim 12 wherein the group VIII metal is nickel.

15. The composition of claim 12, further comprising a lewis acid selected from the group consisting of: 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，CdCl₂，B(C₆H₅)₃And (C)₆H₅)₃SnX, wherein X ═ CF₃SO₃，CH₃C₆H₅SO₃Or (C)₆H₅)₃BCN。