New achiral diphosphinic ligand, complexes based on it and its manufacturing method

 

(57) Abstract:

The invention relates to novel achiral diphosphine ligands bilaterales type. Describes the new achiral diphosphinic ligand

Also describes diphosphine the transition metal complexes of the formulae IIa and IIIa.

and the method of synthesis of compounds Ia. The technical result is obtained a new connection and diphosphine complexes based on it, which can be used in catalytic processes: the aminating, cross combination, hydroformylation, hidrotsianova, hydrogenation, allylic alkylation, polymerization of olefins and other reactions leading to the formation of C-C and C-N bonds. 3 S. p. f-crystals, 2 tab.

The invention relates to novel achiral diphosphine ligands bilaterales type complexes of transition metals on the basis of these diphosphines and methods for producing diphosphines and their complexes.

Processes catalyzed diphosphine complexes of transition metals, such as amination, cross-coupling, allylic alkylation, hidrotsianova, hydroformylation, hydrogenation and others, are the object of increased interest nezavisim from the selected process and substrate used.

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

Proposed new achiral diphosphine General formula I:

where

R1=R3or R1R3- linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20alkyl, halogen; OR10where R10is hydrogen, linear or branched C1-C20alkyl, phenyl, substituted aryl; NR11R12(R11=R12or R11R12), where R11and R12- linear or branched C1-C20alkyl, aryl;

SR13where R13- linear or branched C1-C20alkyl;

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;

R6, R7, R8, R9- linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents - and branched C1-C20alkyl, phenyl, substituted aryl; NR15R16(R15=R16or R15R16), where R15and R16- linear or branched C1-C20alkyl, phenyl, substituted aryl; SR17where R17- linear or branched C1-C20alkyl; R6and R7(R8and R9) can be linked by a bridge (OR18O, where R18- 1,1'-binaphthyl; oxygen; sulfur; nitrogen);

Y=C1-C6Si;

R4, R5is hydrogen, alkyl, aryl;

X= S, N, O, P. a Variant of diphosphine General formula I is:

Proposed diphosphine the transition metal complexes of General formula II and III:

where

R1=R3or R1R3- linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20alkyl, halogen; OR10where R10is hydrogen, linear or branched C1-C20alkyl, phenyl, substituted aryl; NR11R12(R11=R12 or R11R12), where R11and R12- linear or branched C1-C20alkyl>is hydrogen; linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20alkyl, halogen;

R6, R7, R8, R9- linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20alkyl, halogen; OR14where R14is hydrogen, linear or branched C1-C20alkyl, phenyl, substituted aryl; NR15R16(R15=R16or R15R16), where R15and R16- linear or branched C1-C20alkyl, phenyl, substituted aryl; SR17where R17- linear or branched C1-C20alkyl; R6and R7(R8and R9) can be linked by a bridge (OR18O, where R18- 1,1'-binaphthyl; oxygen; sulfur; nitrogen);

Y=C1-C6Si;

R4, R5is hydrogen,alkyl,aryl;

X= S, N, O, P;

M= transition metal (including metal 3-8 groups of the periodic table);

Z= halogen; phosphine; substituted ethylene; ester; amine;uly II is:

The structure of the compound IIA is confirmed by x-ray structure analysis (PCA):

where

R1=R3or R1R3- linear or branched C1-C20alkyl; cyclic WITH3-C8alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20 alkyl, halogen; OR8where R8is hydrogen, linear or branched C1-C20alkyl, phenyl, substituted aryl; NR9R10(R9=R10or R9R10), where R9and R10- linear or branched C1-C20alkyl, aryl; SR11where R11- linear or branched C1-C20alkyl;

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;

R4, R5, R6, R7- linear or branched C1-C20alkyl; cyclic WITH3-C8 alkyl; phenyl; substituted aryl or hetaryl, where the substituents are linear or branched C1-C20alkyl, ha is aryl; NR13R14(R13=R14or R13R14), where R13and R14- linear or branched C1-C20alkyl, phenyl, substituted aryl; SR15where R15- linear or razvetvlennye1-C20alkyl; R4and R5(R6and R7) can be linked by a bridge (OR16O, where R16- 1,1'-binaphthyl; oxygen; sulfur; nitrogen);

X=S, N, O, P;

M= transition metal (including metal 3-8 groups of the periodic table);

Z= halogen; phosphine; substituted ethylene; ester; amine; acetate, including triptorelin, amide; alkoxide (n= 0-4).

Option diposting complex of General formula III is:

The structure of the compound IIIa is confirmed by x-ray method:

The method of synthesis of achiral diphosphines General formula I, including the production of intermediate delicieux salts and the subsequent treatment of the reaction mixtures (R6-9)2The PCl.

The method of synthesis of palladium complexes of the General formula II and III, which consists in heating the respective diphosphine ligands with PdCl2in tetrahydrofuran.

Example 1. The synthesis of compounds Ia

To a solution of 3-bromo-2 [(is gona added 1.6 M solution of BuLi in hexane (to 19.4 ml, 0,031 mol). The reaction mixture was stirred, maintaining cooling for 1.5 h and then added a solution of Ph2PCl (6,1 ml 0,034 mol) in Et2O (10 ml). The cooling was removed and left to mix for 12 hours. Then to the reaction mixture was added 10% solution of NH4Cl (50 ml), the precipitate was filtered, washed with water and Et2O. the Obtained gray crystalline substance was dried in high vacuum and purified column chromatography (silica gel 60, benzene). The solvent was removed. Product: white crystalline substance. Output:

of 1.75 g (22 %). NMR1H (DCl3, , M. D.): 2,35 (C., 6N, Me); a 4.83 (SD, 2H, -CH2-); 6,29 (S., 2H, -CH= thiophene ring); 7,35 is 7.50 (m, 20N, -CH=, PH). NMR31R (CDCl3, , M. D.): -30,75 (C.). NMR13With (CDCl3, , M. D.,J/Hz): 15,10 (-CH3); 29,08 (t, J = 19,5) (-CH2-); 128,10, 128,18 (t, J = 3,2), 128,74 (-CH=); 131,51(D., J = 13) (=<); 132,94 (D., J = 19,9) (-CH=); 137,85 (D., J =9,0), 138,27,149,10 (D.,J = 35,8) (=<). Found (percent): C, 72,97; N, 5,18,35H30P2S2. Calculated (%): C, 72,89; N, 5,24.

Example 2. The synthesis of compounds IIA

To a solution of 3,3'-bis(diphenylphosphino)-5,5'-dimethyl-2,2'-dithienylethene Ia (0,69 g, 0,0012 mol) in tetrahydrofuran (15 ml) was added PdCl2(0.21 g, 0,0012 mol). The reaction mixture was heated under stirring for the practical stuff. Yield: 0.33 g (37%). NMR1H (DCl3, , M. D.): 2,20 (C., 6N, Me); 5,39 (ush. S., 2H, -CH2-); 6,06 (S., 2H, -CH= thiophene rings); 7,20-7,26, 7,35-7,40, 7,50-7,56 (all meters, 20N, -CH=, Ph). NMR31P (DCl3, , M. D.): 10,71 (C.). Found (Percent): C, 55,87; N, 3,91. WITH35H30P2S2dCl2. Calculated (%): C, 55,75; N, 4,01.

Example 3. The synthesis of compounds IIIA

The compound was obtained analogously to the complex IIA on the basis of: 2,2'-bis(diphenylphosphino)-5,5'-dimethyl-3,3'-dithiolane IV (1 g, 0,0018 mol), PdCl2(0.32 g, 0,0018 mol) and THF (20 ml). Product: yellow crystalline substance. Yield: 1 g (76 %). NMR1H (DCl3, , M. D.):2,20 (C., 6N, Me); 6,40 (S., 2H, -CH= thiophene ring); 7,40-7,55 (gr. m, 20N, -CH=, Ph). NMR31R (CDCl3, , M. D.): 14,25 (C.). Found (Percent): C, 55,29; N, 3,89. WITH34H28P2S2dCl2. Calculated (%): C, 55,18; N, 3,81.

Diphosphine complexes of General formulae II and III used in catalytic processes: the aminating, cross combination, hydroformylation, hidrotsianova, hydrogenation, allylic alkylation, polymerization of olefins and other reactions leading to the formation of C-C and C-N bonds. In the catalytic processes can be used not only complex, but diphosphine ligands. In this regard, the ligand (IV), the sah.

Example 4. Cross-coupling of p-bromthymol and second-butylacrylamide

The results of the quantitative analysis of the components of the reaction mixture in the cross-coupled p-bromthymol and second-butylacrylamide (4 mmol p-bromthymol, 12 mmol second-butylacrylamide, 0.04 mmol PdCl2(P-P), 20 Ml Et2O) are given in table.1.

Example 5. The amination reaction of bromine benzol with phenethylamine

The results of the quantitative analysis of the components of the reaction mixture in the reaction of bromine benzol with phenethylamine (4 mmol bromine benzol, 4.8 mmol h(MN2)CH3, 4.8 mmol NaOtBu, 0.2 mmol of Pd(dba)2, 0.4 mmol of the ligand, 50 ml of toluene, 100 C, 3 hours) are given in table.2.

Example 6. When used in the reaction of bromine benzol with phenethylamine IIIa complex obtained results similar to those shown in example 5.

1. New achiral diphosphinic ligand

2. Diphosphine the transition metal complexes of the formulae IIA and IIIa.

3. The method of synthesis of compounds Ia under item 1 which consists in the interaction of compounds Va with butyllithium with subsequent treatment of the resulting product with diphenylchlorophosphine.



 

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