Achiral p,n-bidentate ligands and method of production thereof

 

(57) Abstract:

The invention relates to new P,N-bidentate ligands of formula (I):

where a is S or NR,

where R represents a C1-C4alkyl,

R1and R2represent hydrogen, C1-C4alkyl, or R1and R2can be locked in the benzene ring,

R3and R4submit C1-C4alkyl or phenyl,

R5and R6submit C1-C4alkyl.

These compounds may be used as components of catalysts for amination reactions, cross-combination, hydroformylation, allylic alkylation, etc. 2 N. p. F.-ly, 1 table.

The invention relates to novel achiral P,N-bidentate ligands heteroaryl-aryl type, method of their production and application.

Among the ligands used to obtain complexes of transition metals, occupy a special place P,N-system. Processes catalyzed by transition metal complexes with P,N-bidentate ligands, such as amination, cross-coupling, allylic alkylation, hidrotsianova, hydroformylation, hydrogenation and kompleksow in catalytic reactions strongly depends on the selected process and substrate used.

The proposed connection is not known neither technical nor from the patent literature.

Proposed new achiral P,N-bidentate ligands heteroaryl-aryl type General formula I

where A=S, N, O.

R1, R2is hydrogen; linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20alkyl, halogen; OR11where R11is hydrogen, linear or branched C1-C20alkyl, phenyl, substituted aryl; NR12R13(R12=R13or R12R13), where R12and R13- linear or branched C1-C20alkyl, aryl; SR14where R14- linear or branched C1-C20alkyl; R1and R2can be locked in a substituted or unsubstituted aromatic ring.

R3, R4- linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20alkyl, halogen; OR15where R15is hydrogen, linear or rasvet the SUB>R17), where R16and R17- linear or branched C1-C20alkyl, phenyl, substituted aryl; SR18where R18- linear or branched C1-C20alkyl; R3and R4can be linked by a bridge (OR19O, where R19-1,1’-binaphthyl; oxygen; sulfur; nitrogen).

R5, R6- linear or branched C1-C20alkyl.

R7=R8=R9=R10or R7R8R9R10is hydrogen; linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; halogen; OR20where R20is hydrogen, linear or branched C1-C20alkyl; SO3N or the corresponding salt; NR21R22(R21=R22or R21R22), where R21and R22- linear or branched C1-C20alkyl, phenyl, substituted aryl; R9and R10can be locked in a substituted or unsubstituted aromatic ring.

Options P,N-ligands of General formula I are

The method of synthesis of achiral P,N-bidentate ligands of the General formula I, which comprises two stages: 1) the effect of BuLi in Et2O IP is S="ptx2">

The proposed scope of achiral P,N-bidentate ligands of the General formula I as components of catalysts for amination reactions, cross-combination, hydroformylation, hydrocyanide, hydrogenation, allylic alkylation, polymerization of olefins and other reactions leading to the formation of C-C and C-N bonds.

Example 1. The synthesis of compounds 1A.

To a solution of N,N-dimethyl-2-(5-methyl-3-thienyl)aniline (2 g, 0.0092 mol) in Et2O (20 ml) and cooled to -70° C in an atmosphere of argon was added a 1.6 M solution of BuLi in hexane (6.1 ml, 0.0097 mol). The reaction mixture was stirred at room temperature for 4 hours, cooled to -40° C and added to a solution of Ph2PCl (1.8 ml, 0.0099 mol) in Et2O (5 ml). The cooling was removed and left to mix for 12 hours. Then to the reaction mixture was added 10% solution of NH4Cl (20 ml), the precipitate was filtered, washed with water and hexane. The resulting substance was dried in high vacuum and purified column chromatography (silica gel 60, benzene). The solvent was removed under reduced pressure. Product: white crystalline substance. Output: 2.13 g (55%). NMR1H (CDCl3, , M. D., J/Hz): 2.44 (C., 6N, Me); 2.55 (C., 3H, Me); 6.99-7.02 (m, 1H, -CH=thiophene ring); N, 3.60. C25H24The NPS. Calculated (%): C, 74.79; H, 6.02; N, 3.49.

Example 2. Synthesis of compound IB.

To a solution of N,N-dimethyl-2-(5-methyl-3-thienyl)aniline (1 g, 0.0046 mol) in Et2O (10 ml) and cooled to -70° C in an atmosphere of argon was added a 1.6 M solution of BuLi in hexane (3 ml, 0.0048 mol). The reaction mixture was stirred at room temperature for 4 hours, cooled to -40° C and added to a solution of VIt2l (0.89 g, 0.0049 mol) in Et2O (3 ml). The cooling was removed and left to mix for 12 hours. Then to the reaction mixture were added water (10 ml), the organic layer was separated, the aqueous was extracted with Et2O. the Combined organic fraction was dried over MgSO4the solvent was removed under reduced pressure. The residue was recrystallize from pentane. Product: yellow crystals. Yield: 1 g (60%). NMR 1N (C6D6, , M. D., J/Hz): 1.34 (D., N, J=11.5, But); 2.29 (D., 3H, J=1, Me); 2.53 (C., 6N, Me); 6.88-6.90 (m, 1H, -CH=thiophene ring); 6.97-7.00 (DD., 1H, J=8.1, J=1.1), 7.02-7.07 (TD, 1H), 7.24-7.29 (m, 1H), 7.39-7.42 (DD., 1H, J=7.5, J=1.8) (-CH=, AG). NMR31P (C6D6, M. D.): 14.2 (SD). Found (Percent): C, At 69.61; H, 9.02; N, 3.98. C21H32The NPS. Calculated (%): C, 69.77; H, 8.92; N, 3.87.

Example 3. The synthesis of compounds V

The compound was obtained analogously to the ora BuLi in hexane (3.8 ml, 0.006 mol), Ph2PCl (1.1 ml, 0.006 mol) and Et2O (20 ml). The resulting substance was purified column chromatography (silica gel 60, benzene:EtOAc, 4:1). Product: white crystalline substance. Yield: 1.17 g (47%). NMR1H (CDCl3, , M. D.): 2.21 (C., 6N, Me); 3.34 (C., 3H, Me); 7.11-7.16 (m, 2H), 7.20-7.54 (gr.m., 15 NM, 7.72-7.75 (m, 1H) (-CH=, AG). NMR 31P (CDCl3, , M. D.): -31.93 (C.). Found (Percent): C, 80.04; H, 6.15; N, 6.59. C29H27N2P. Calculated (%): C, 80.16; H, 6.26; N, 6.45.

The use of compounds of the formula I as ligands to obtain palladium complexes. Study of catalytic activity of palladium complexes in the reaction of allyl substitution.

To study the activity and selectivity of palladium complexes derived P,N-ligands of the formula I, as model reaction was considered the reaction of allyl substitution between 1,3-diphenylprop-2-EN-1-yl-acetate and diethylmalonate (scheme 1).

(scheme 1).

The reaction was conducted at room temperature under argon in the presence of bases: sodium hydride. Metal complex catalyst was obtained in situ by the interaction of Pd(dba)2and P,N-ligands of the formula I in the ratio of 1:1.5. As the catalyst has been used for the treatment and outputs of the reaction was determined by the method1H NMR spectroscopy. The results of catalytic transformations in the interaction of 1,3-diphenylprop-2-EN-1-yl-acetate and diethylmalonate in table 1.

Reaction conditions: 0.05 mmol of Pd(dba)2, 0.075 mmol of the ligand, 1 mmol of acetate, 2 mmol of diethylmalonate, 2 mmol of sodium hydride, 7 ml of solvent at room temperature.

Thus, complexes derived P,N-ligands of the formula I, in relation to the already known P,N-ligands exhibit new properties.

1. Achiral P,N-bidentate ligands of formula (I)

where a is S or NR, where R represents a C1-C4alkyl;

R1and R2represent hydrogen, C1-C4alkyl, or R1and R2can be locked in the benzene ring;

R3and R4submit C1-C4alkyl or phenyl;

R5and R6submit C1-C4alkyl.

2. The method of obtaining compounds of formula (I) under item 1, which consists in the fact that the compound of General formula (III)

where A, R1, R2, R5and R6are specified in paragraph 1 values

subjected to interaction with butyllithium followed about>and R4are specified in paragraph 1.



 

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