CN113713858B - Alpha alkylation reaction catalyst of nitrile and preparation method thereof - Google Patents
Alpha alkylation reaction catalyst of nitrile and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for alpha alkylation reaction of nitrile and a preparation method thereof, wherein the catalyst is an asymmetric pincerlike ruthenium compound containing pyridine-benzenesulfonyl imidazoline, and the structural general formula is as follows:
，R 3 、R 4 is phenyl, R 5 Is benzenesulfonyl or benzenesulfonyl containing substituent, and the synthesis method comprises the following steps: oxidizing 2, 2-bipyridine with hydrogen peroxide, nitrifying to obtain 2, 2-bipyridine-6-carbonitrile, alcoholysis, cyclizing and sulfonylating to obtain ligand, ligand and RuCl 2 (PPh 3 ) 3 And refluxing in toluene to obtain the pyridine-phenylsulfonyl imidazoline-containing asymmetric pincerlike ruthenium compound. The pincer ruthenium compound synthesized by the invention has different electronic properties and can be well regulatedActivity in catalytic reactions.
Description
Technical Field
The invention belongs to the technical field of application of organic compounds, and particularly relates to an alpha alkylation reaction catalyst of nitrile and a preparation method thereof.
Background
The construction of C-C bonds by using alcohols as alkylating agents has become a very important method by means of hydrogen or hydrogen transfer mechanisms. In these reactions, water as the only byproduct achieves the purposes of atomic economy and environmental friendliness. To date, there have been various types of substrates by which products of alpha alkylation reactions have been obtained, including ketones, esters, indoles, and the like. Furthermore, nitriles are a very important class of building blocks in organic synthesis. Nitrile compounds can be converted very conveniently into compounds of other types of substituents, such as amides, carboxylic acid derivatives, imidazoline derivatives, oxazoline derivatives, and other types of biologically active molecules. These types of compounds have extremely important roles in organic synthesis, pharmaceutical synthesis and the like. Therefore, the alpha alkylation of nitrile compounds has attracted attention. Therefore, the development of more efficient catalysts is one of the important methods for alkylation of nitriles.
Disclosure of Invention
The invention provides a catalyst for alpha alkylation of nitrile and application thereof in the reaction, aiming at the problems in the prior art, which have the advantages of high temperature, large alkali consumption, long reaction time and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
an alpha alkylation reaction catalyst of nitrile, which is a pyridine-imidazoline asymmetric pincerlike ruthenium compound with the following structural general formula:
R 3 is C 1 -C 15 Alkyl, aryl, R 4 Is phenyl or hydrogen, R 5 Is aryl, benzenesulfonyl or benzenesulfonyl containing substituent.
The catalyst is applied to the alpha alkylation reaction of nitrile, and the alpha alkylation reaction process of nitrile is as follows: adding a catalyst, alkali, nitrile compounds and alcohol compounds into a solvent for reaction, and separating and purifying by thin layer chromatography after the reaction is finished to obtain a corresponding target product, wherein the reaction formula is as follows
The general formula of the nitrile compound is R 1 CH 2 CN, wherein R 1 Phenyl, p-methylphenyl, p-methoxyphenyl, p-chlorophenyl, thienyl; the general formula of the alcohol compound is R 2 CH 2 OH, wherein R is 2 Aryl or alkyl, wherein aryl is phenyl, p-methylphenyl, p-methoxyphenyl, p-chlorophenyl and the like, and alkyl is n-butyl, phenylpropyl; the catalyst is pyridine-imidazoline asymmetric pincerlike ruthenium compound; the alkali used is KOH, naOH, csOH, csOH.H 2 O，KO t Bu，NaO t Bu，K 2 CO 3 ，Na 2 CO 3 Or Cs 2 CO 3 The solvent is toluene, xylene, dioxane or dichloroethane, and the reaction temperature is 120-140 ℃.
Further, the molar ratio of the nitrile compound to the alcohol compound is 1:1-5, preferably 1:2.
Further, the catalyst is used in an amount of 0.5 to 2.5mol% based on the total amount of the nitrile compound and the alcohol compound.
Further, the amount of the base is 0.1 to 0.5equiv.
Further, the developing agent used for the thin layer chromatography separation is petroleum ether: ethyl acetate (v: v) =20 to 30/1.
An alpha alkylation reaction catalyst of nitrile, wherein the catalyst is pyridine-imidazoline asymmetric pincerlike ruthenium compound with the following structural general formula:
R 3 is C 1 -C 15 Alkyl, aryl, R 4 Is hydrogen, R 5 When the catalyst is aryl, the preparation method of the catalyst is as follows: the asymmetric NNN' clamp-shaped ruthenium compound containing pyridine-imidazoline is synthesized according to the following method: the preparation method comprises the steps of taking cheap 2,2 '-bipyridine as a starting material, reacting the 2,2' -bipyridine with hydrogen peroxide in trifluoroacetic acid solution to generate 2,2 '-bipyridine-1-oxide, then reacting the 2,2' -bipyridine-1-oxide with trimethylnitrile silane and benzoyl chloride in anhydrous dichloromethane for 4 days to obtain 2,2 '-bipyridine-6-carbonitrile, hydrolyzing the 2,2' -bipyridine-6-carbonitrile in alkali to obtain 2, 2-bipyridine-6-carboxylic acid, refluxing the 2, 2-bipyridine-6-carboxylic acid in thionyl chloride, steaming out thionyl chloride, adding anhydrous dichloromethane for dissolving, then dropwise adding the anhydrous dichloromethane solution of chiral amino alcohol in ice bath condition, reacting overnight at room temperature after dropwise adding, then drying the reaction solution by spin drying, continuously refluxing the thionyl chloride, steaming out thionyl chloride after refluxing, adding anhydrous dichloromethane for dissolving, dropwise adding anhydrous dichloromethane under ice bath condition, adding dropwise adding anhydrous dichloromethane solution of aromatic amine, then adding sodium hydroxide at room temperature for reaction, carrying out 10% aqueous solution of N-containing symmetric N, concentrating, and carrying out chromatography, and concentrating to obtain a non-aqueous solution after N-symmetric extraction, and carrying out N-phase separation, and carrying out overnight chromatography. NNN' clamp ligand and RuCl 2 (PPh 3 ) 3 Refluxing in toluene to precipitate purple-black solid, i.eIs an asymmetric NNN' clamp-shaped ruthenium compound.
The method comprises the following specific steps:
(1) Oxidizing 2, 2-bipyridine with hydrogen peroxide, nitrifying, and hydrolyzing to obtain 2, 2-bipyridine-6-carboxylic acid;
(2) Refluxing 2, 2-bipyridine-6-carboxylic acid in thionyl chloride, evaporating excessive thionyl chloride, dripping the thionyl chloride into an anhydrous dichloromethane solution of chiral amino alcohol in an ice bath, reacting overnight after dripping, and spin-drying to obtain an amide compound;
(3) Adding thionyl chloride into an amide compound, continuously carrying out reflux reaction, then steaming off excessive thionyl chloride, adding anhydrous dichloromethane and triethylamine, then dropwise adding aromatic amine in an ice bath, stirring overnight at room temperature, finally adding an aqueous solution of sodium hydroxide, continuously stirring overnight, extracting, drying, concentrating, and carrying out thin-layer chromatography to obtain an asymmetric pincer ligand;
(4) Asymmetric pincer ligands and RuCl 2 (PPh 3 ) 3 Reflux reaction in toluene, cooling after the reaction, directly separating out solid, washing with diethyl ether to obtain the target compound.
Further, in the step (2), the molar ratio of the 2, 2-dipyridine-6-carboxylic acid to the thionyl chloride is 1 (7-21), the 2, 2-dipyridine-6-carboxylic acid is subjected to reflux reaction in the thionyl chloride for 8-12h, and the molar ratio of the 2, 2-dipyridine-6-carboxylic acid to the chiral amino alcohol is 1 (1-2).
Further, the molar ratio of the amide compound to the aromatic amine in the step (3) is 1 (1-2).
Further, the amide compound in the step (3) is refluxed in thionyl chloride for 8 to 12 hours.
Further, in the step (3), the molar ratio of the amide compound to thionyl chloride is 1 (7-21), and the molar ratio of the amide compound to triethylamine and sodium hydroxide is 1:6 (8-12).
Further, dropwise adding chiral amino alcohol and aromatic amine in an ice bath, and stirring at room temperature for reaction for 8-16h.
And (3) adding an aqueous solution of sodium hydroxide, and continuing stirring and reacting for 8-12h, wherein the mass concentration of the aqueous solution of sodium hydroxide is 10%.
Further, in the step (4), an asymmetric pincer ligand and RuCl 2 (PPh 3 ) 3 The ratio of the amounts of the substances is 1 (1-2), and the reflux reaction time is 2-5 hours.
(II) a catalyst for alpha alkylation reaction of nitrile, wherein the catalyst is pyridine-imidazoline asymmetric pincerlike ruthenium compound with the following structural general formula:
R 3 、R 4 is phenyl, R 5 Is benzenesulfonyl or benzenesulfonyl containing substituent; the preparation method of the catalyst comprises the following steps: the preparation method comprises the steps of taking cheap 2,2 '-bipyridine as a starting material, reacting the 2,2' -bipyridine with hydrogen peroxide in trifluoroacetic acid solution to generate 2,2 '-bipyridine-1-oxide, then reacting the 2,2' -bipyridine-1-oxide with trimethylnitrile silane and benzoyl chloride in anhydrous dichloromethane for 2-5 days to obtain 2,2 '-bipyridine-6-carbonitrile, carrying out reflux reaction on the 2,2' -bipyridine-6-carbonitrile and sodium methoxide in anhydrous methanol to obtain bipyridine imine compounds, and continuing the bipyridine imine compounds and (1S, 2S) -1, 2-diphenylethylenediamine in anhydrous CH 2 Cl 2 The imidazoline compound containing NH is obtained after 1 to 2 days of reaction, the imidazoline compound containing NH, DMAP and p-toluenesulfonyl chloride are reacted in methylene dichloride for 3 to 7 hours, then the asymmetric pincer-shaped ligand is obtained after rotary evaporation, concentration and thin layer chromatography separation, the ligand compound and the tri (triphenylphosphine) ruthenium dichloride are subjected to reflux reaction in toluene for 3 hours, and the target compound is obtained after rapid silica gel column purification and separation.
The method comprises the following specific steps:
(1) Oxidizing 2, 2-bipyridine with hydrogen peroxide, carrying out nitrile-based reaction to obtain 2, 2-bipyridine-6-carbonitrile, and carrying out alcoholysis on the 2, 2-bipyridine-6-carbonitrile to obtain bipyridine imine compounds;
(2) The bipyridine imine compound is cyclized to obtain an imidazoline product containing NH;
(3) Sulfonylating the imidazoline cyclization product containing NH to obtain an asymmetric pincer ligand;
(4) Asymmetric pincer ligands and RuCl 2 (PPh 3 ) 3 Reflux reaction in toluene, and purifying and separating by silica gel column to obtain pyridine-phenylsulfonyl imidazoline-containing asymmetric pincerlike ruthenium compound.
Further, the preparation method of the bipyridylium imine compound in the step (1) comprises the following steps: 2, 2-dipyridine and hydrogen peroxide react overnight in trifluoroacetic acid solution to generate 2,2' -dipyridine-1-oxide, trimethylnitrile silane and benzoyl chloride react in anhydrous dichloromethane for 2-5 days to generate 2,2' -dipyridine-6-carbonitrile, and 2,2' -dipyridine-6-carbonitrile and sodium methoxide react in anhydrous methanol in a reflux way for 0.5-1 hour to obtain dipyridine imine compounds.
Further, the molar ratio of 2,2' -bipyridine-6-carbonitrile to sodium methoxide was 5:2.
Further, in the step (2), the bipyridylium imine compound and (1S, 2S) -1, 2-diphenyl ethylenediamine are refluxed in anhydrous dichloromethane for 1-2 days to obtain an imidazoline cyclization product containing NH, wherein the molar ratio of the bipyridylium imine compound to the (1S, 2S) -1, 2-diphenyl ethylenediamine is 1:1-2.
Further, the specific steps of the step (3) are as follows: adding benzenesulfonyl chloride compound and DMAP into the imidazoline cyclization product containing NH at 0 deg.C, reacting at room temperature for 3-7 hr, rotary evaporating, concentrating, and separating by thin layer chromatography to obtain asymmetric pincer ligand.
Further, the ratio of the amounts of the NH-containing imidazoline compound, DMAP, and p-toluenesulfonyl chloride compound was 1:3:2.2.
Further, the thin layer chromatography separation developing agent is PE/EA (v: v) =1/1-5.
Further, the asymmetric pincer ligand and RuCl in the step (4) 2 (PPh 3 ) 3 The ratio of the amounts of the substances is 1:1-2.
Further, the asymmetric pincer ligand and RuCl in the step (4) 2 (PPh 3 ) 3 Reflux reaction in toluene for 3h.
Further, the eluent in the purification and separation of the silica gel column in the step (4) is DCM/CH 3 OH(v:v) ＝30-70/1。
The invention has the beneficial effects that: the invention relates to an asymmetric pincer ruthenium compound-catalyzed alpha alkylation reaction of nitrile. The method uses alcohol as an alkylating reagent, generates water as a unique byproduct, accords with the ideas of atom economy and environmental friendliness, and has the advantages of catalytic amount of alkali, short reaction time, economy and the like. Meanwhile, the method provides a convenient and feasible method for synthesizing the disubstituted nitrile, and improves the application potential of the compound in the aspects of medicines and the like.
Detailed Description
The invention is further illustrated by the following examples:
example 1
An alpha alkylation reaction catalyst of nitrile, which is a pyridine-imidazoline asymmetric pincerlike ruthenium compound with the following structural general formula:
(1) Preparation of (S) -6- (4- (tert-butyl) -1- (p-tolyl) -4, 5-dihydro-1H-imidazol-2-yl) -2,2' -bipyridine: 2, 2-Dipyridine-6-carboxylic acid (10 mmol) was refluxed in thionyl chloride solution (5 mL) for 8h, excess thionyl chloride was removed by spin evaporation to give a pale yellow oil, which was dissolved in anhydrous dichloromethane solution, and then, dropwise added to anhydrous dichloromethane solution in which L-tertiary leucinol (11 mmol,1.29 g) and triethylamine (30 mmol,4.2 mL) were dissolved under ice bath conditions, and after completion of the dropwise addition, the reaction was carried out at room temperature overnight. After the reaction, spin-drying the reactant, adding ethyl acetate, filtering to remove insoluble matters, continuously adding thionyl chloride (5 mL) after spin-drying the filtrate, reacting for 8 hours under a reflux state, spin-evaporating to remove the excessive thionyl chloride to obtain reddish brown oily substance, dissolving the reddish brown oily substance in an anhydrous dichloromethane solution, dropwise adding the reddish brown oily substance into the anhydrous dichloromethane solution in which the p-toluidine (11 mmol,1.2 g) and the triethylamine (60 mmol,8 mL) are dissolved under the ice bath condition, stirring at room temperature overnight, adding 10% sodium hydroxide aqueous solution (35 mL) again, continuously stirring at room temperature for 8-12 hours, separating liquid after the completion, extracting the aqueous phase with dichloromethane for 3 times, and combining the organic mattersThe phases were dried with anhydrous magnesium sulfate, suction filtered, spin dried and separated by column chromatography (eluent ratio PE/ea=3/1-1/10) to give the corresponding NNN' ligand. Brown solid; yield 52%; melting point: 119-121 ℃. 1 H NMR(400MHz,CDCl 3 )δ8.57(d,J＝4.7Hz,1H), 8.33(d,J＝7.7Hz,1H),7.99(d,J＝7.7,Hz,1H),7.84(t,J＝7.7Hz,1H),7.53(ddd, J＝7.7,7.7,1.8Hz,1H),7.37(d,J＝8.0Hz,1H),7.19(ddd,J＝7.5,4.8,1.2Hz,1H),6.99(d,J＝8.0Hz,2H),6.80(d,J＝8.0Hz,2H),4.23-4.13(m,1H),4.10-4.01(m, 1H),3.71(t,J＝8.4Hz,1H),2.26(s,3H),1.03(s,9H). 13 C{ 1 H}NMR(100MHz, CDCl 3 )δ160.3,155.7,154.8,149.4,148.8,141.6,137.5,136.5,133.3,129.1,124.1, 123.7,123.5,121.4,121.3,74.2,55.6,34.3,26.0,20.8.IR(cm -1 ):2949,2860,1592, 1560,1515,1463,1432,1388,1362,1161,1144,992,821,786,750,564.HRMS (ESI-TOF)m/z:[M+H] + calcd for C 24 H 27 N 4 371.2230,found 371.2238.
(2) Preparation of (S) -6- (4- (tert-butyl) -1- (p-tolyl) -4, 5-dihydro-1H-imidazol-2-yl) -2,2' -bipyridyl triphenylphosphine ruthenium dichloride: to a 100mL Schlenk flask equipped with a stirring reflux apparatus were added (S) -6- (4- (tert-butyl) -1- (p-tolyl) -4, 5-dihydro-1H-imidazol-2-yl) -2,2' -bipyridine (0.4 mmol,148 mg), tris (triphenylphosphine) ruthenium dichloride (0.4 mmol,383 mg) and 30mL toluene, and the mixture was refluxed under nitrogen for 3 hours, after the reaction was completed, the solid was separated out by cooling, suction filtration, and washing with diethyl ether to obtain a product (170 mg). The yield thereof was found to be 53%. Purple solid, melting point:>300℃。 1 H NMR(600MHz,CDCl 3 ) δ9.55-9.45(m,1H),7.74(d,J＝7.9Hz,1H),7.63(d,J＝7.9,Hz,1H),7.48-7.37(m,7H),7.25-7.03(m,13H),6.93-6.69(m,2H),6.48(d,J＝7.9Hz,1H),4.07-3.98(m, 1H),3.97-3.90(m,1H),3.88-3.77(m,1H),2.38(s,3H),1.27(s,9H). 13 C{ 1 H}NMR (150MHz,CDCl 3 )δ160.3,157.9,138.3,136.8,134.8,133.13,133.11,131.6,131.3, 130.1,128.9,128.2,127.7,127.6,126.4,125.0,121.1,120.5,57.1,35.9,29.8,27.4,21.1. 31 P{ 1 H}NMR(162MHz,CDCl 3 )δ42.2(s,PPh 3 ).IR(cm -1 ):ν3053,2950, 2869,1739,1548,1524,1511,1490,1480,1426,1374,1363,1296,1084,833,779,749,699,685,524,510,500.HRMS(ESI-TOF)m/z:[M–2Cl - ] 2+ calcd for C 42 H 41 N 4 PRu 367.1051,found 367.1057.
example 2
An alpha alkylation reaction catalyst of nitrile, which is a pyridine-imidazoline asymmetric pincerlike ruthenium compound with the following structural general formula:
(1) Preparation of 6- ((4 s,5 s) -4, 5-diphenyl-1-tosyl-4, 5-dihydro-1H-imidazol-2-yl) -2,2' -bipyridine:
a: 2,2 '-bipyridine-6-carbonitrile (1.0 g,5.52 mmol) and sodium methoxide (120 mg,2.21 mmol) were added to a Schlenk's bottle of 50mL, followed by a reflux reaction of 20mL of anhydrous methanol for 30min, and after the completion of the reaction, glacial acetic acid was added to adjust the pH to neutral. Then spin-drying the solvent, and putting the solvent into a vacuum drying oven for drying to obtain white solid;
b: the resulting white solid and (1 s,2 s) -1, 2-diphenylethylenediamine (1.29 g,6.07 mmol) were added to a 100mL round bottom flask, then 50mL of anhydrous dichloromethane was added to reflux the reaction overnight, after the reaction was completed, the solvent was dried by spin-drying, and column chromatography was performed (PE/ea=1/1) to obtain an intermediate;
c: intermediate (376.5 mg,1.0 mmol) and DMAP (366.5 mg,3.0 mmol) were added to a 50mL schlenk flask, then 20mL dichloromethane was added, after cooling the solution to 0 ℃, p-toluenesulfonyl chloride (419.4 mg,2.2 mmol) was added, the reaction was allowed to react at room temperature for 4h, then the aqueous phase was washed with saturated aqueous ammonium chloride solution, three times with dichloromethane, the organic phase was mixed, dried over anhydrous magnesium sulfate, filtered, concentrated, and isolated by thin layer chromatography (PE/ea=1/1) to give the title compound. White solid; yield: 0.45g,91%; melting point: 181-182 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ8.75 (d,J＝4.7Hz,1H),8.56(d,J＝8.0Hz,1H),8.17(t,J＝7.7Hz,1H),8.02-7.91(m, 3H),7.55-7.46(m,5H),7.44-7.39(m,1H),7.37-7.30(m,5H),7.15-7.08(m,4H), 5,18(d,J＝4.4Hz,1H),5.15(d,J＝4.4Hz,1H),2.29(s,3H). 13 C{ 1 H}NMR(100 MHz,CDCl 3 )δ158.7,155.2,155.1,149.7,149.1,143.6,141.5,141.0,137.6,136.7, 136.4,129.7,129.13,129.07,128.98,128.3,128.0,127.6,126.6,126.4,124.6,123.8,122.3,121.5,78.6,71.7,21.5.IR(cm -1 ):3372,3269,3095,3045,1621,1583,1457, 1432,1352,1174,1096,1074,785,764,699,670,598,541.HRMS(ESI-TOF)m/z: [M+H] + calcd for C 32 H 27 N 4 O 2 S 531.1849,found 531.1854.
(2) Synthesis of ruthenium compound b: the ligand compound (0.40 mmol), ruCl, was prepared under an argon atmosphere 2 (PPh 3 ) 3 (383.25 mg,0.40 mmol) was added to a 100mL Schlenk flask, then 30mL g of dry toluene was added and the mixture was refluxed for 3h under argon protection. After the reaction was completed, it was cooled, and then toluene was distilled off under reduced pressure at 70 ℃. The crude product was isolated by flash column purification on silica gel (DCM/CH 3 Oh=50/1) ruthenium compound b. A purple solid; yield: 0.20g,51%; melting point: 206-208 ℃. 1 H NMR(600 MHz,CDCl 3 )δ9.17(d,J＝5.5Hz,1H),8.56(d,J＝8.0Hz,1H),7.83(d,J＝8.0Hz, 1H),7.67(d,J＝7.8Hz,1H),7.54(d,J＝8.0Hz,2H),7.48-7.39(m,2H),7.33(d,J ＝7.5Hz,2H),7.26-7.22(m,3H),7.19-7.11(m,9H),7.07(d,J＝8.0Hz,2H),7.04-6.89(m,12H),5.17-5.09(m,2H),2.32(s,3H). 13 C{ 1 H}NMR(150MHz, CDCl 3 )δ161.8,160.4,158.2,154.6,153.9,145.6,140.2,138.5,137.2,135.5,132.9, 132.8,131.4,131.1,130.5,130.2,129.3,129.2,128.9,128.5,128.1,128.0,127.93,127.87,127.7,126.7,126.3,125.7,121.4,120.4,76.5,72.0,21.7. 31 P{ 1 H}NMR(243 MHz,CDCl 3 )δ37.0(s,PPh 3 ).IR(cm -1 ):ν3053,3029,1596,1480,1434,1365, 1301,1169,1087,772,743,694,670,662,595,520,499.HRMS(ESI-TOF)m/z:[M –2Cl - ] 2+ calcd for C 50 H 41 N 4 O 2 PRuS 447.0860,found 447.0864.
Example 3
An alpha alkylation reaction catalyst of nitrile, which is a pyridine-imidazoline asymmetric pincerlike ruthenium compound with the following structural general formula:
(1) 6- ((4S, 5S) -1- ((4-nitrophenyl) sulfonyl) -4, 5-diphenyl-4, 5-dihydro-1H-imidazol-2-yl) -2,2' -bipyridine: the procedure was as in example two, step (1) except that p-toluenesulfonyl chloride in example two, step (1) was replaced with p-nitrobenzenesulfonyl chloride (487.6 mg,2.2 mmol). White solid; yield: 0.55g,97%; melting point: 184-185 ℃. 1 H NMR(400MHz,d 6 -DMSO)δ8.73(d,J＝4.6 Hz,1H),8.53(d,J＝8.0Hz,1H),8.20(t,J＝7.7Hz,1H),8.06(d,J＝7.7Hz,1H),7.98(d,J＝8.8Hz,2H),7.83-7.72(m,2H),7.59-7.43(m,8H),7.42-7.33(m,3H), 7.30-7.23(m,2H),5.39(d,J＝3.6Hz,1H),5.29(d,J＝3.6Hz,1H). 13 C{ 1 H}NMR (100MHz,d 6 -DMSO)δ156.9,154.7,154.1,149.7,149.5,148.8,143.9,140.5,140.4, 138.7,137.0,129.3,128.9,128.5,128.4,127.9,126.2,126.1,124.6,124.5,124.2,122.5,120.5,77.5,71.0.IR(cm -1 ):3114,3096,3000,1642,1585,1581,1528,1459, 1431,1374,1348,1311,1177,1121,1091,1058,1022,859,834,780,761,738,702,654,626,585,552.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 31 H 24 N 5 O 4 S 562.1544,found 562.1547.
(2) Synthesis of ruthenium compound c: the preparation method is the same as in the second embodiment (2). A purple solid; yield: 0.19g, 47%; melting point: 206-208 ℃. 1 H NMR(600MHz,CDCl 3 )δ9.21(d,J＝4.9Hz,1H),8.48 (d,J＝8.1Hz,1H),8.01(d,J＝8.3Hz,2H),7.88-7.76(m,3H),7.68(d,J＝8.1Hz,1H),7.57-7.52(m,1H),7.51-7.48(m,2H),7.44(d,J＝8.1Hz,1H),7.29-7.24(m, 4H),7.21-7.18(m,1H),7.17-7.09(m,8H),7.01-6.87(m,11H),5.28(d,J＝11.3Hz, 2H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ161.2,160.5,158.0,154.4,154.1,151.2, 139.2,138.4,137.8,135.8,132.83,132.77,131.0,130.7,130.2,129.5,129.3,129.1,128.53,128.46,128.44,128.1,128.04,127.96,127.4,127.2,126.6,125.4,124.8, 121.4,120.4,75.7,72.2. 31 P{ 1 H}NMR(243MHz,CDCl 3 )δ36.4(s,PPh 3 ).IR(cm -1 ): ν3055,3025,1603,1528,1480,1434,1372,1346,1312,1176,1086,849,738,694,680,625,584,522,499.HRMS(ESI-TOF)m/z:[M–2Cl - ] 2+ calcd for C 49 H 38 N 5 O 4 PRuS 462.5708,found 462.5712.
Examples of applications of the above catalyst for catalyzing the alpha alkylation reaction of nitriles are as follows:
and (3) under the argon atmosphere, sequentially adding an asymmetric pincer ruthenium (II) catalyst, alkali, nitriles and alcohol into a 15mL dry Schlenk tube, adding toluene for reaction, cooling after the reaction is finished, and separating and purifying the crude product by thin layer chromatography to obtain a corresponding target product.
Example 4: catalyst a catalyzed synthesis of 2- (4-bromophenyl) -3-phenylpropane nitrile: catalyst a (0.005 mmol,1.0 mol%), KOH (0.1 mmol,0.20 equiv), p-bromophenylacetonitrile (0.5 mmol,98.02 mg), benzyl alcohol (1.0mmol,108.14 mg) and then 0.8mL toluene were sequentially added to a 15mL dry schlenk tube under argon atmosphere, the reaction mixture was reacted at 120 ℃ for 4 hours, after the reaction was completed, cooled, then dichloromethane was added to dissolve and transfer to a 100mL round bottom flask, the solvent was spun off under reduced pressure, and the crude product was purified by thin layer chromatography (PE/ea=20 to 30/1) to give the corresponding target product. White solid; yield: 29mg,20%; melting point: 80-81 ℃. 1 H NMR(400MHz,CDCl 3 ) δ7.52-7.43(m,2H),7.33-7.26(m,3H),7.14-7.06(m,4H),3.97(t,J＝7.0Hz,1H),3.18(dd,J＝13.4,7.7Hz,1H),3.09(dd,J＝13.4,6.7Hz,1H). 13 C{ 1 H}NMR(100 MHz,CDCl 3 )δ135.8,134.1,132.2,129.2,128.7,127.6,122.3,119.9,42.0,39.2.IR (cm -1 ):3054,3027,2941,2885,2242,1487,1455,1407,1073,1013,816,742,696, 568,490.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 15 H 13 BrN 286.0226,found 286.0228.
Example 5: catalyst b catalytic synthesis of 2- (4-bromophenyl) -3-phenylpropane nitrile: catalyst b (0.005 mmol,1.0 mol%), KOH (0.1 mmol,0.2 equiv), p-bromophenylacetonitrile (0.5 mmol,98.02 mg), benzyl alcohol (1.0 mmol,108.14 mg) and then 0.8mL toluene were sequentially added to a 15mL dry schlenk tube under argon atmosphere, the reaction mixture was reacted at 120 ℃ for 4 hours, cooled after the reaction was completed, then dichloromethane was added to dissolve and transfer to a 100mL round bottom flask, the solvent was spun off under reduced pressure, and the crude product was purified by thin layer chromatography (PE/ea=20 to 30/1) to give the corresponding target product. White solid; yield: 53mg,37%; melting point: 80-81 ℃. Characterization of the compounds is described in example 4.
Example 6: catalyst c catalyzed synthesis of 2- (4-bromophenyl) -3-phenylpropane nitrile: catalyst c (0.005 mmol,1.0 mol%), KOH (0.1 mmol,0.2 equiv), p-bromophenylacetonitrile (0.5 mmol,98.02 mg), benzyl alcohol (1.0 mmol,108.14 mg) and then 0.8mL toluene were sequentially added to a 15mL dry schlenk tube under argon atmosphere, the reaction mixture was reacted at 120 ℃ for 4 hours, cooled after the reaction was completed, then dichloromethane was added to dissolve and transfer to a 100mL round bottom flask, the solvent was spun off under reduced pressure, and the crude product was purified by thin layer chromatography (PE/ea=20 to 30/1) to give the corresponding target product. White solid; yield: 53mg,37%; melting point: 80-81 ℃. Characterization of the compounds is described in example 4.
Example 7: catalyst c catalyzed synthesis of 2- (4-bromophenyl) -3-phenylpropane nitrile: catalyst c (0.0075 mmol,1.5 mol%), KOH (0.075 mmol,0.15 equiv), p-bromophenylacetonitrile (0.5 mmol,98.02 mg), benzyl alcohol (1.0 mmol,108.14 mg) and then 0.8mL toluene were added to a 15mL dry schlenk tube under argon atmosphere, the reaction mixture was reacted at 140 ℃ for 4h, after the reaction was completed, cooled, then dichloromethane was added to dissolve and transfer to a 100mL round bottom flask, the solvent was spun off under reduced pressure, and the crude product was purified by thin layer chromatography (PE/ea=20 to 30/1) to give the corresponding target product. White solid; yield: 119mg,83%; melting point: 80-81 ℃. Characterization of the compounds is described in example 4.
Example 8: synthesis of 2- (4-methoxyphenyl) -3-phenylpropionitrile: the p-bromophenylacetonitrile in example 7 was converted to the p-methyl bromideOxyphenyl acetonitrile (0.5 mmol,73.56 mg) was prepared in the same manner as in example 7.White solid.YIeld 107mg,90% MP 63-64 ℃. 1 H NMR(600MHz,CDCl 3 )δ7.33-7.22(m,3H), 7.14(dd,J＝8.0,19.7Hz,4H),6.86(d,J＝8.0Hz,2H),3.94(t,J＝8.0Hz,1H),3.80(s,3H),3.16(dd,J＝13.2,8.4Hz,1H),3.09(dd,J＝13.6,6.5Hz,1H). 13 C{ 1 H} NMR(150MHz,CDCl 3 )δ159.4,136.5,129.3,128.65,128.61,127.3,127.2,120.6, 114.4,55.3,42.3,39.0.IR(cm -1 ):3062,2971,2924,2856,2244,1616,1613,1512, 1456,1256,1179,1031,831,739,699.HRMS(ESI-TOF)m/z:[M+Na] + calcd for C 16 H 15 NNaO 260.1046,found 260.1048.
Example 9: synthesis of 2- (4- (tert-butyl) phenyl) -3-phenylpropionitrile: the procedure of example 7 was followed except that p-bromophenylacetonitrile was changed to p-t-butylphenylacetonitrile (0.5 mmol,86.63 mg). White solid. YIeld 55mg,42%. Mp 124-125 ℃. 1 H NMR(400MHz,CDCl 3 )δ7.41-7.35(m, 2H),7.34-7.26(m,3H),7.24-7.14(m,4H),3.97(dd,J＝8.6,6.4Hz,1H),3.21-3.07 (m,2H),1.32(s,9H). 13 C{ 1 H}NMR(100MHz,CDCl 3 )δ151.3,136.6,132.3,129.2, 128.7,127.3,127.1,126.0,120.5,42.3,39.5,34.6,31.3.IR(cm -1 ):3064,3060,2961, 2925,2874,2240,1728,1606,1514,1458,1362,1272,1110,1024,979,747,706,585.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 19 H 22 N 264.1747,found 264.1749.
Example 10: synthesis of 3-phenyl-2- (p-tolyl) propionitrile: the other preparation method was the same as in example 7 except that the p-bromophenylacetonitrile in example 7 was changed to p-methylphenylacetonitrile (0.5 mmol,65.59 mg). White solid. YIeld: 100mg,90%. Mp:71-73 ℃. 1 H NMR(400MHz,CDCl 3 )δ7.33-7.23(m,3H), 7.19-7.08(m,6H),3.96(dd,J＝8.4,6.4Hz,1H),3.17(dd,J＝13.7,8.4Hz,1H),3.10(dd,J＝13.7,6.4Hz,1H),2.35(s,3H). 13 C{ 1 H}NMR(100MHz,CDCl 3 )δ 138.0,136.5,132.3,129.7,129.2,128.6,127.3,120.6,42.3,39.5,21.1.IR(cm -1 ): 3055,3027,2922,2857,2240,1601,1495,1438,1027,798,736,695,572,492.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 16 H 16 N 222.1277,found 222.1278.
Example 11: synthesis of 2, 3-diphenylpropionitrile: the other preparation method was the same as in example 7 except that the p-bromophenylacetonitrile in example 7 was changed to phenylacetonitrile (0.5 mmol,58.58 mg). White solid.YIeld 99mg,95% MP 52-53 ℃. 1 H NMR(400MHz,CDCl 3 )δ7.41-7.19(m,8H),7.17-7.07(m,2H),3.98 (dd,J＝8.4,6.4Hz,1H),3.17(dd,J＝13.6,8.1Hz,1H),3.11(dd,J＝13.6,6.6Hz,1H). 13 C{ 1 H}NMR(100MHz,CDCl 3 )δ136.3,135.3,129.3,129.1,128.7,128.2, 127.5,127.4,120.4,42.2,39.8.IR(cm -1 ):3065,3032,2924,2854,2243,1599,1496, 1455,1073,1024,753,696.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 15 H 14 N 208.1121,found 208.1123.
Example 12:2- (4-fluorophenyl) -3-phenylpropionitrile: the other preparation method was the same as in example 7 except that the p-bromophenylacetonitrile in example 7 was changed to p-fluorophenylacetonitrile (0.5 mmol,67.57 mg). White solid.YIeld 97mg, 86% MP 85-86 ℃. 1 H NMR(600MHz,CDCl 3 )δ7.33-7.23(m,3H),7.23-7.15(m, 2H),7.13-7.06(m,2H),7.06-6.98(m,2H),3.99(t,J＝7.3Hz,1H),3.19(dd,J＝13.3,8.0Hz,1H),3.10(dd,J＝13.3,6.6Hz,1H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ 162.5(d,J F-C ＝247.3Hz),135.9,130.95(d,J F-C ＝3.0Hz),129.3,129.2,128.7, 127.5,120.2,116.0(d,J F-C ＝21.9Hz),42.2,39.0. 19 F NMR(564MHz,CDCl 3 )δ -113.52.IR(cm -1 ):2938,2888,2244,1897,1605,1509,1457,1218,1159,1078, 1017,834,816,744,701,568.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 15 H 13 FN 226.1027,found 226.1030.
Example 13:2- (4-chlorophenyl) -3-phenylpropionitrile: the other preparation method was the same as in example 7 except that p-bromophenylacetonitrile in example 7 was changed to p-chlorophenylacetone (0.5 mmol,75.80 mg). White solid.YIeld 97mg, 80%. Mp 79-80 ℃. 1 H NMR(400MHz,CDCl 3 )δ7.36-7.26(m,5H),7.20-7.13(m, 2H),7.12-7.07(m,2H),3.98(t,J＝7.3Hz,1H),3.18(dd,J＝13.6,8.0Hz,1H),3.10 (dd,J＝13.6,6.6Hz,1H). 13 C{ 1 H}NMR(100MHz,CDCl 3 )δ135.8,134.3,133.6, 129.24,129.20,128.9,128.7,127.5,120.0,42.0,39.1.IR(cm -1 ):3089,3054,2939, 2245,1605,1493,1454,1412,1094,1089,1017,828,744,701,691,569,494.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 15 H 13 ClN 242.0731,found 242.0734.
Example 14:2- (3-methoxyphenyl) -3-phenylpropionitrile: the procedure of example 7 was followed except that the p-bromophenylacetonitrile in example 7 was changed to m-methoxyphenylacetonitrile (0.5 mmol,73.56 mg). Yellow oil.YIeld 107mg,90%. 1 H NMR(600MHz,CDCl 3 )δ7.32-7.24(m,4H),7.17-7.12(m,2H), 6.85(d,J＝7.7Hz,2H),6.77(s,1H),3.96(t,J＝7.4Hz,1H),3.77(s,3H),3.21-3.15(m,1H),3.13(dd,J＝13.3,6.4Hz,1H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ160.0, 136.7,136.3,130.1,129.2,128.7,127.4,120.3,119.7,113.8,113.2,55.3,42.1,39.8.IR(cm -1 ):3086,3035,2958,2844,2246,1606,1496,1456,1267,1155,1053, 879,787,739,700.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 16 H 16 NO 238.1226, found 238.1228.
Example 15:2- (3-chlorophenyl) -3-phenylpropionitrile: the other preparation method was the same as in example 7 except that the p-bromophenylacetonitrile in example 7 was changed to m-chlorophenylacetone (0.5 mmol,75.80 mg). White solid.YIeld 97mg, 80%. Mp 61-63deg.C; 1 H NMR(600MHz,CDCl 3 )δ7.33-7.22(m,6H),7.15-7.08(m, 3H),3.96(t,J＝7.3Hz,1H),3.17(dd,J＝13.6,8.3Hz,1H),3.10(dd,J＝13.6,6.3Hz,1H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ137.1,135.8,134.9,130.3,129.2,128.8, 128.6,127.7,127.6,125.8,119.8,42.0,39.4.IR(cm -1 ):3057,2960,2932,2878,2242, 1598,1594,1500,1476,1456,1439,1194,1166,1098,1083,919,900,781,749,715,691,595,574,484.HRMS(ESI-TOF)m/z:[M+H]+calcd for C 15 H 13 ClN 242.0731,found 242.0734.
example 16: 3-phenyl-2- (o-tolyl) propionitrile: the other preparation was the same as in example 7 except that the p-bromophenylacetonitrile in example 7 was changed to o-methylphenylacetonitrile (0.5 mmol,65.59 mg). Color oil. YIeld, 22 mg,20%. 1 H NMR(600MHz,CDCl 3 )δ7.42(d,J＝6.6Hz,1H),7.33-7.26(m,3H), 7.25-7.21(m,2H),7.19-7.14(m,3H),4.14(t,J＝6.6Hz,1H),3.19-3.11(m,1H),3.10-3.03(m,1H),2.25(s,3H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ136.6,135.1, 133.7,131.0,129.2,128.7,128.3,127.7,127.4,126.9,120.7,41.0,36.6,19.1.IR (cm -1 ):3069,3034,2941,2887,2245,1068,1498,1456,1081,1052,762,751,701. HRMS(ESI-TOF)m/z:[M+H] + calcd for C 16 H 16 N 222.1277,found 222.1279.
Example 17:2- (3, 5-dimethylphenyl) -3-phenylpropionitrile: the procedure of example 7 was followed except that p-bromophenylacetonitrile was changed to 3, 5-dimethylbenzylacetonitrile (0.5 mmol,72.60 mg). Yellow oil. Yield, 113mg,96%. 1 H NMR(400MHz,CDCl 3 )δ7.35-7.22(m,3H),7.21-7.12(m,2H), 6.95(s,1H),6.89(s,2H),3.90(dd,J＝9.0,6.2Hz,1H),3.20-3.04(m,2H),2.30(s, 6H). 13 C{ 1 H}NMR(100MHz,CDCl 3 )δ138.7,136.7,135.2,129.8,129.2,128.6, 127.4,125.2,120.6,42.4,39.9,21.3.IR(cm -1 ):3035,2934,2881,2246,1610,1498, 1456,1387,1076,1042,853,754,715,701.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 17 H 18 N 236.1434,found 236.1437.
Example 18: 3-phenyl-2- (thiophen-2-yl) propionitrile: the other preparation was the same as in example 7 except that the p-bromophenylacetonitrile in example 7 was changed to 2-thiophenylacetonitrile (0.5 mmol,61.59 mg). 31 mg,29% of Colorless oil. 1 H NMR(600MHz,CDCl 3 )δ7.34-7.25(m,4H),7.19(d,J＝7.3Hz,2H), 7.00-6.97(m,1H),6.97-6.92(m,1H),4.27(t,J＝7.4Hz,1H),3.28-3.20(m,2H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ137.2,136.0,129.2,128.8,127.6,127.1,126.5, 125.7,119.5,42.3,34.9.IR(cm -1 ):3075,3034,2955,2883,2246,1608,1498,1457, 1080,1052,762,752,701,584.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 13 H 12 NS 214.0685,found 214.0684.
Example 19:3- (4-methoxyphenyl) -2-phenylpropionitrile: the p-bromophenylacetonitrile in example 7 was changed to phenylacetonitrile (0.5 mmol,58.58 mg), benzyl alcoholBy changing to p-methoxybenzyl alcohol (1.0 mmol,138.16 mg), the other preparation was as in example 7.Yellow solid.YIeld 105mg,89%. Mp 83-84 ℃. 1 H NMR(600MHz,CDCl 3 )δ7.38-7.28(m,3H),7.27-7.22(m,2H),7.05(d,J＝8.0Hz, 2H),6.82(d,J＝8.0Hz,2H),3.95(t,J＝7.1Hz,1H),3.78(s,3H),3.16-3.04(m, 2H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ158.9,135.3,130.3,129.0,128.4,128.1, 127.5,120.5,114.0,55.3,41.4,40.1.IR(cm -1 ):3082,3010,2957,2958,2834,2241, 1614,1607,1513,1466,1301,1249,1183,1177,1109,1033,838,798,770,742,705,574,522.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 16 H 16 NO 238.1226,found 238.1220.
Example 20: 2-phenyl-3- (p-tolyl) propionitrile: the procedure of example 7 was followed except that the bromobenzyl cyanide of example 7 was changed to benzyl cyanide (0.5 mmol,58.58 mg) and benzyl alcohol was changed to p-methyl benzyl alcohol (1.0 mmol,122.16 mg). White solid.YIeld 99mg,90%. Mp 53-54 ℃. 1 H NMR(400 MHz,CDCl 3 )δ7.39-7.29(m,3H),7.29-7.22(m,2H),7.09(d,J＝8.0Hz,2H),7.02 (d,J＝8.0Hz,2H),3.96(dd,J＝8.4,6.8Hz,1H),3.18-3.04(m,2H),2.32(s,3H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ137.1,135.4,133.3,129.3,129.1,129.0,128.2, 127.5,120.4,41.8,40.0,21.1.IR(cm -1 ):3068,3034,2934,2870,2243,1601,1515, 1512,1455,1108,1077,1022,912,826,782,780,739,694,575,496.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 16 H 16 N 222.1277,found 222.1279.
Example 21:3- (4-chlorophenyl) -2-phenylpropionitrile: the procedure of example 7 was followed except that the bromobenzyl cyanide of example 7 was changed to benzyl cyanide (0.5 mmol,58.58 mg) and benzyl alcohol was changed to chlorobenzyl alcohol (1.0 mmol,142.58 mg). White solid. YIeld:65mg,54%. Mp:107-108 ℃. 1 H NMR(600MHz, CDCl 3 )δ7.42-7.29(m,3H),7.27-7.21(m,4H),7.04(d,J＝7.8Hz,2H),3.98(t,J＝ 7.4Hz,1H),3.20-3.05(m,2H). 13 C{ 1 H}NMR(100MHz,CDCl 3 )δ134.8,134.6, 133.4,130.7,129.1,128.8,128.4,127.5,120.1,41.4,39.6.IR(cm -1 ):3036,2953, 2884,2246,1633,1494,1455,1411,1089,1016,843,804,787,755,697,575,498.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 15 H 13 ClN 242.0731,found 242.0734.
Example 22:3- (4-bromophenyl) -2-phenylpropionitrile: the procedure of example 7 was followed except that the p-bromophenylacetonitrile was changed to phenylacetonitrile (0.5 mmol,58.58 mg) and benzyl alcohol was changed to p-bromobenzyl alcohol (1.0 mmol,187.03 mg). White solid.YIeld 80mg,56%. Mp 106-108 ℃. 1 H NMR(600MHz, CDCl 3 )δ7.40(d,J＝8.3Hz,2H),7.38-7.31(m,3H),7.25-7.21(m,2H),6.98(d,J＝ 8.2Hz,2H),3.98(t,J＝7.3Hz,1H),3.17-3.07(m,2H). 13 C{ 1 H}NMR(150MHz, CDCl 3 )δ135.1,134.8,131.8,131.0,129.1,128.4,127.5,121.5,120.1,41.5,39.5.IR (cm -1 ):3080,3032,2965,2837,2880,2245,1738,1602,1487,1455,1406,1293, 1068,1011,841,785,755,696,654,574,495.HRMS(ESI-TOF)m/z:[M+ H] + calcd for C 15 H 13 BrN 286.0226,found 286.0228.
Example 23: 2-phenyl-3- (4- (trifluoromethyl) phenyl) propionitrile: the procedure of example 7 was followed except that the bromobenzyl cyanide of example 7 was changed to benzyl cyanide (0.5 mmol,58.58 mg) and benzyl alcohol was changed to p-trifluoromethyl benzyl alcohol (1.0 mmol, 176.14 mg). White solid.YIeld 87mg,63%. Mp 80-81 ℃. 1 H NMR(600MHz,CDCl 3 )δ7.55(d,J＝7.8Hz,2H),7.40-7.32(m,3H), 7.28-7.21(m,4H),4.03(t,J＝7.2Hz,1H),3.28-3.16(m,2H). 13 C{ 1 H}NMR(150 MHz,CDCl 3 )δ140.1,134.6,130.0,129.7,129.2,128.5,127.4,125.6(q, 3 J C-F ＝3.5 Hz),124.1(q, 1 J C-F ＝271.2Hz),119.9,41.8,39.3. 19 F NMR(564MHz,CDCl 3 )δ -62.34.IR(cm -1 ):3100,3046,2966,2244,1617,1494,1457,1421,1322,1152,1107, 1065,1018,853,820,793,749,698,654,595.HRMS(ESI-TOF)m/z:[M+ H] + calcd for C 16 H 13 F 3 N 276.0995,found 276.0993.
Example 24: 2-phenyl-3- (m-tolyl) propionitrile: the p-bromophenyl acetonitrile in example 7 was changed to benzyl cyanide (0.5 mmol,58.58 mg) and the benzyl alcohol was changed to m-methyl benzyl alcohol (1.0 mmol,122.16 mg), which was used as a catalystThe preparation method is the same as in example 7.Color oil.YIeld 107mg,97%. 1 H NMR(600MHz,CDCl 3 ) δ7.37-7.29(m,3H),7.27(d,J＝7.4Hz,2H),7.18(t,J＝7.6Hz,1H),7.07(d,J＝7.6Hz,1H),6.97-6.90(m,2H),3.98(dd,J＝8.4,6.3Hz,1H),3.14(dd,J＝13.6,8.7 Hz,1H),3.08(dd,J＝13.6,6.4Hz,1H),2.31(s,3H). 13 C{ 1 H}NMR(150MHz, CDCl 3 )δ138.3,136.3,135.5,130.0,129.1,128.5,128.2,128.1,127.5,126.2,120.5, 42.3,39.9,21.4.IR(cm -1 ):3074,3041,2953,2886,2246,1612,1498,1456,778,700, 581.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 16 H 16 N 222.1277,found 222.1278.
Example 25:3- (2-bromophenyl) -2-phenylpropionitrile: the procedure of example 7 was followed except that p-bromophenylacetonitrile was changed to phenylacetonitrile (0.5 mmol,58.58 mg), benzyl alcohol was changed to o-bromobenzyl alcohol (1.0 mmol,187.03 mg). White solid.YIeld 99mg,69%. Mp 60-61 ℃. 1 H NMR(600MHz, CDCl 3 )δ7.59(d,J＝7.8Hz,1H),7.41-7.36(m,4H),7.36-7.31(m,1H),7.28-7.22 (m,2H),7.16(t,J＝7.4Hz,1H),4.20(t,J＝7.8Hz,1H),3.30(dd,J＝13.2,5.6Hz,1H),3.25-3.18(m,1H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ135.8,135.3,133.1, 131.9,129.3,129.1,128.3,127.8,127.3,124.4,120.1,42.9,37.7.IR(cm -1 ):3085, 3051,2949,2245,1605,1568,1493,1472,1450,1286,1162,1117,1079,1028,979,756,700,659,575,503.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 15 H 13 BrN 286.0226,found 286.0225.
Example 26:2, 5-diphenylvaleronitrile: the procedure of example 7 was followed except that p-bromophenylacetonitrile was changed to phenylacetonitrile (0.5 mmol,58.58 mg), benzyl alcohol was changed to 3-phenylpropanol (1.0 mmol,136.19 mg). Colorless oil. YIeld, 104mg,89%. 1 H NMR(600MHz,CDCl 3 )δ7.38-7.33 (m,2H),7.33-7.25(m,5H),7.19(t,J＝7.6Hz,1H),7.14(d,J＝7.6Hz,2H),3.77 (dd,J＝8.3,5.6Hz,1H),2.6(t,J＝7.3Hz,2H),1.99-1.73(m,4H). 13 C{ 1 H}NMR (150MHz,CDCl 3 )δ141.2,135.8,129.1,128.5,128.4,128.1,127.3,126.1,120.8, 37.3,35.3,35.1,28.6.IR(cm -1 ):3037,2947,2863,2240,1602,1496,1454,1331, 1078,1028,915,754,697,598,521.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 17 H 18 N 236.1434,found 236.1433.
Example 27: 2-phenylhexanenitrile: the procedure of example 7 was followed except that p-bromophenylacetonitrile was changed to phenylacetonitrile (0.5 mmol,58.58 mg) and benzyl alcohol was changed to n-butanol (1.0 mmol,74.12 mg). Pale yellow oil. Yield:64mg,74%. 1 H NMR(600MHz,CDCl 3 )δ7.40-7.28(m, 5H),3.76(t,J＝7.3Hz,1H),1.97-1.81(m,2H),1.53-1.31(m,4H),0.90(t,J＝7.0 Hz,3H). 13 C{ 1 H}NMR(150MHz,CDCl 3 )δ136.1,129.1,128.0,127.2,121.0,37.4, 35.7,29.2,22.1,13.8.IR(cm -1 ):3092,3065,2962,2937,2873,2245,1606,1497, 1456,1122,1094,1035,757,700.HRMS(ESI-TOF)m/z:[M+H] + calcd for C 12 H 16 N 174.1277,found 174.1274.
Claims (8)
1. An alpha alkylation reaction catalyst of nitrile, which is pyridine-benzene sulfonyl imidazoline containing asymmetric pincerlike ruthenium compound with a structural general formula as follows:
，
R 3 、R 4 is phenyl, R 5 Is benzenesulfonyl containing substituent;
the preparation method of the catalyst for the alpha alkylation reaction of the nitrile comprises the following steps:
(1) 2,2 '-dipyridine is used as a starting material, 2' -dipyridine and hydrogen peroxide react in trifluoroacetic acid solution to generate 2,2 '-dipyridine-1-oxide, then 2,2' -dipyridine-1-oxide, trimethylnitrile silane and benzoyl chloride react in anhydrous dichloromethane for 2-5 days to obtain 2,2 '-dipyridine-6-carbonitrile, and 2,2' -dipyridine-6-carbonitrile and sodium methoxide react in anhydrous methanol in a reflux way to obtain dipyridine imine compounds;
(2) Bipyridine imines continue to be summed up1S,2S) -1, 2-diphenylethylenediamine in anhydrous CH 2 Cl 2 The imidazolines containing NH are obtained after 1 to 2 days of reactionA compound;
(3) Reacting imidazoline compound containing NH, DMAP and p-toluenesulfonyl chloride compound in dichloromethane for 3-7h, then spin-evaporating, concentrating, and separating by thin layer chromatography to obtain asymmetric pincer ligand;
(4) Asymmetric pincer ligands and RuCl 2 (PPh 3 ) 3 Reflux reaction 3h in toluene, and rapid silica gel column purification and separation to obtain pyridine-phenylsulfonyl imidazoline-containing asymmetric pincerlike ruthenium compound.
2. The process for preparing a catalyst for the alpha alkylation of nitrile according to claim 1, characterized by the steps of:
(1) 2,2 '-dipyridine is used as a starting material, 2' -dipyridine and hydrogen peroxide react in trifluoroacetic acid solution to generate 2,2 '-dipyridine-1-oxide, then 2,2' -dipyridine-1-oxide, trimethylnitrile silane and benzoyl chloride react in anhydrous dichloromethane for 2-5 days to obtain 2,2 '-dipyridine-6-carbonitrile, and 2,2' -dipyridine-6-carbonitrile and sodium methoxide react in anhydrous methanol in a reflux way to obtain dipyridine imine compounds;
(2) Bipyridine imines continue to be summed up1S,2S) -1, 2-diphenylethylenediamine in anhydrous CH 2 Cl 2 Reacting for 1-2 days to obtain an imidazoline compound containing NH;
(3) Reacting imidazoline compound containing NH, DMAP and p-toluenesulfonyl chloride compound in dichloromethane for 3-7h, then spin-evaporating, concentrating, and separating by thin layer chromatography to obtain asymmetric pincer ligand;
(4) Asymmetric pincer ligands and RuCl 2 (PPh 3 ) 3 Reflux reaction 3h in toluene, and rapid silica gel column purification and separation to obtain pyridine-phenylsulfonyl imidazoline-containing asymmetric pincerlike ruthenium compound.
3. The method for producing a catalyst for alpha alkylation of nitrile according to claim 2, characterized in that: in the step (1), 2' -bipyridine-6-carbonitrile and sodium methoxide are subjected to reflux reaction in absolute methanol for 0.5-1 hour to obtain bipyridine imine compounds; the molar ratio of 2,2' -bipyridine-6-carbonitrile to sodium methoxide was 5:2.
4. The method for producing a catalyst for alpha alkylation of nitrile according to claim 2, characterized in that: the bipyridine imine compound in the step (2) and [ ]1S,2S) The molar ratio of the (E) -1, 2-diphenyl ethylenediamine is 1:1-2.
5. The method for producing a catalyst for alpha alkylation of nitrile according to claim 2, characterized in that: the specific steps of the step (3) are as follows: adding p-toluenesulfonyl chloride compound and DMAP into the imidazoline cyclization product containing NH at 0 ℃, reacting for 3-7h at room temperature, rotary evaporating, concentrating, and separating by thin layer chromatography to obtain the asymmetric pincer ligand.
6. The method for producing a catalyst for alpha alkylation of nitrile according to claim 5, characterized in that: the ratio of the mass of the imidazoline compound containing NH to the mass of the DMAP and the mass of the p-toluenesulfonyl chloride compound is 1:3:2.2, the thin layer chromatography separating developing agent is PE/EA, and the volume ratio of the PE/EA is 1/1-5.
7. The method for producing a catalyst for alpha alkylation of nitrile according to claim 2, characterized in that: the asymmetric pincer ligand and RuCl in the step (4) 2 (PPh 3 ) 3 The ratio of the amounts of the substances is 1:1-2.
8. The method for producing a catalyst for alpha alkylation of nitrile according to claim 2, characterized in that: the eluent in the purification and separation of the silica gel column in the step (4) is DCM/CH 3 OH，DCM/CH 3 The volume ratio of OH is 30-70/1.
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