CN113200832B - Method for catalyzing non-tension nonpolar carbon-carbon single bond hydrogenolysis of dicarbonyl compound - Google Patents
Method for catalyzing non-tension nonpolar carbon-carbon single bond hydrogenolysis of dicarbonyl compound Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical industry, and particularly relates to a method for catalyzing the hydrogenolysis of a dicarbonyl compound non-tension nonpolar carbon-carbon single bond. In the method, under a rare earth catalytic system, a secondary alcohol (amine) compound or silane is used as a hydrogen source, and the non-tension carbon-carbon single bond of diketone and ketoester is hydrogenolyzed to form monoketone (ester). The hydrogenolysis reaction of the carbon-carbon bond of the first ketone has the advantages of good atom economy, high position selectivity and chemical selectivity, mild condition, simple and convenient operation, strong tolerance of functional groups and the like. Diketones and ketoesters are widely available and can be converted into monoketones (esters) for a wide range of applications.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for catalyzing non-tension nonpolar carbon-carbon single bond hydrogenolysis away from carbonyl by rare earth.
Background
Selective hydrogenolysis of carbon-carbon single bonds is one of the most economical and convenient ways to disassemble organic molecules. Has wide application in the fields of organic synthesis, polymers, biomass, petroleum cracking and the like (Topics in catalysis.2018,61, 183-198). Industrially, heterogeneous cracking of petroleum usually needs to be carried out under conditions of high temperature (300-450 ℃) and high pressure (100-180 atm) (Chemcat. 2012,4, 292-306). However, activation of a non-strained carbon-carbon bond by a homogeneous system is relatively not easy, and one of the C (sp) is generally required3) To a heteroatom or to two carbonyl groups, or some specific transformations which need to take place by aromatization under the action of metered metals (angelw. chem., int.ed.2012,51, 8050-; org.lett.2010,12, 2254-2257). The literature (Nature.1994,370,42-44) reports the use of HRh (PPh) with hydrogen as the hydrogen source3)4Catalytic cleavage of C (aryl) -C (CH) in chelating substrates3) A key. Recently, a method of promoting nontensile C (aryl) -C (aryl) bond cleavage by chelation of a substrate and a metal has been reported (J.Am.chem.Soc.2019,141, 18630-18640).
The above-mentioned method for hydrogenolysis of carbon-carbon bond is limited in substrate, the catalyst is more expensive, and the reaction conditions are severer. Since carbonyl groups (including alkenes) are more readily reduced than nonstrained nonpolar carbon-carbon single bonds, there have been no reports of selective hydrogenolysis of carbon-carbon single bonds of saturated and unsaturated ketones to date.
Disclosure of Invention
The invention aims to provide a method for catalyzing the non-tension nonpolar carbon-carbon single bond hydrogenolysis of dicarbonyl compounds, which has the advantages of cheap catalyst, good reaction selectivity and high product yield.
The invention provides a method for catalyzing the non-tension nonpolar carbon-carbon single bond hydrogenolysis of a dicarbonyl compound, which takes a compound shown in a formula (I) as a raw material and a diaryl methanol compound as a hydrogen source to efficiently and selectively hydrogenolyze carbon-carbon bonds of 1, 5-diketone and related similar compounds, and comprises the following specific steps:
under the protection of nitrogen, in a rare earth catalytic system, taking a compound shown as a formula (I) as a reactant, taking a diaryl methanol compound or silane as a hydrogen source, and carrying out selective hydrogenolysis on a non-tension carbon-carbon single bond far away from a carbonyl group to obtain 2 mono-ketone products (II) and (III); the reaction formula is as follows:
R4＝alkyl，aryl，alkoxyl，aryoxyl，etc；
R，R1，R2，R3＝alkyl，aryl，heteroaryl，etc
n＝0-2
the catalyst is selected from rare earth alkyl complexes, rare earth aryl complexes, rare earth amino complexes, rare earth alkoxy complexes, rare earth sulfenyl complexes, rare earth amidino complexes and the like;
the rare earth metal is selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
the solvent is selected from toluene, xylene, tetrahydrofuran and hexane;
the hydrogen source is selected from secondary alcohol (amine) compounds or silane; preferably diaryl carbinols.
In the invention, the following components are calculated according to molar ratio: the ratio of the compound of the formula (I) to the rare earth catalyst is 1/(0.005-0.30), and the ratio of the compound of the formula (I) to the hydrogen source is 0.5/(1-2.0);
the reaction temperature for hydrogenolysis of compound (I) is 0-120 deg.C, preferably 25-60 deg.C;
the reaction time of the hydrogenolysis compound (I) is 1-48 h.
The inventor provides a novel rare earth catalytic hydrogenolysis method for the nontensile nonpolar carbon-carbon single bond of dicarbonyl compounds through long-term intensive research, and reports are not found so far. By adopting the method, gram-grade carbon-carbon bond hydrogenolysis reaction can be realized to obtain a corresponding reduction product; compared with the existing process route, the invention has the following advantages:
(1) the reduction of the carbon-carbon single bond prior ketonic carbonyl is realized for the first time;
(2) the catalyst is cheap and easy to obtain, the reaction selectivity is good, and the product yield is high; in addition, functional group compatibility is good; the reaction condition is mild, and the process operation is simple and convenient;
(3) the reaction has wide application range, strong controllability and good application prospect.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The carbon-carbon bond hydrogenolysis of 1,3, 5-triphenyl-1, 5-pentanedione, the chemical structures of the reactants and products are as follows:
under the protection of nitrogen, the raw materials 1,3, 5-triphenyl-1, 5-pentanedione (0.50mmol), benzhydrol (0.55mmol) and catalyst Y [ N (SiMe)3)2]3(2 mol%) and reacting at 60 deg.C in 2mL toluene for 12h, and separating the product acetophenone and 1, 3-diphenyl-1-acetone respectively in yields of 79% and 80%.
Example 2
Under the protection of nitrogen, raw materials of 1,3, 5-triphenyl-1, 5-pentanedione (0.50mmol), triethylsilane (0.55mmol) and a catalyst Sm [ CH ]2(TMS)]3(5 mol%) and reacting at 60 deg.C in 2mL toluene for 10h, the separation yields of acetophenone and 1, 3-diphenyl-1-propanone are 80% and 83%, respectively.
Example 3
Under the protection of nitrogen, adding raw materials of 1,3, 5-triphenyl-1, 5-pentanedione (0.50mmol), diisobutylamine (1.0mmol) and catalyst Sm [ CH ]2(TMS)]3(5 mol%) and reacting at 60 deg.C in 2mL toluene for 12h, the isolation yields of acetophenone and 1, 3-diphenyl-1-propanone are 71% and 74%, respectively.
Acetophenone:1H NMR(400MHz,CDCl3)δ7.98-7.95(m,2H),7.58-7.55(m,1H),7.48-7.44(m,2H),2.61(s,3H)；
1, 3-diphenyl-1-propanone:1H NMR(400MHz,CDCl3)δ7.99-7.97(m,2H),7.59-7.56(m,1H),7.49-7.46(m,2H),7.34-7.21(m,5H),3.33(t,J＝7.7Hz,2H),3.11-3.07(m,2H)。
example 4
The hydrogenolysis of the carbon-carbon bond of 1,2,3, 5-tetraphenyl-1, 5-pentanedione, the chemical structures of the reactants and products are as follows:
under the protection of nitrogen, adding raw materials of 1,2,3, 5-tetraphenyl-1, 5-pentanedione (0.50mmol), 4-methoxyphenyl benzyl alcohol (0.50mmol) and catalyst La [ N (SiMe)3)2]3(10 mol%) and reacting at 25 deg.C in 2mL toluene for 24h, and separating the products, i.e. diphenylethanone and 1, 3-diphenyl-1-acetone, to obtain yields of 75% and 79%, respectively.
Diphenylethanone:1H NMR(400MHz,CDCl3)δ(ppm)8.05(d,J＝7.6Hz,2H),7.59(t,J＝7.2Hz,1H),7.49(t,J＝7.3Hz,2H),7.36(t,J＝7.1Hz,2H),7.29(t,J＝7.1Hz,3H),4.32(s,2H)；
1, 3-diphenyl-1-propanone:1H NMR(400MHz,CDCl3)δ7.99-7.97(m,2H),7.59-7.56(m,1H),7.49-7.46(m,2H),7.34-7.21(m,5H),3.33(t,J＝7.7Hz,2H),3.11-3.07(m,2H)。
example 5
The carbon-carbon bond hydrogenolysis of 1,3, 5-triphenyl-2-benzyl-1, 5-pentanedione, the chemical structures of the reactants and products are as follows:
under the protection of nitrogen, the raw materials of 1,3, 5-triphenyl-2-benzyl-1, 5-pentanedione (0.50mmol), phenylsilane (0.55mmol) and catalyst Y (OCHPh) are added2)3(0.5 mol%) and reacted at 60 deg.C in 2mL toluene for 48h, and the isolated yield of the product 1, 3-diphenyl-1-propanone is 58%.
1, 3-diphenyl-1-propanone:1H NMR(400MHz,CDCl3)δ7.99-7.97(m,2H),7.59-7.56(m,1H),7.49-7.46(m,2H),7.34-7.21(m,5H),3.33(t,J＝7.7Hz,2H),3.11-3.07(m,2H)。
example 6
The carbon-carbon bond hydrogenolysis of 1,2, 5-triphenyl-3-cyclopropyl-1, 5-pentanedione, the chemical structures of the reactants and products are as follows:
example 7 starting materials 1,2, 5-triphenyl-3-cyclopropyl-1, 5-pentanedione (0.5mmol), benzhydrol (0.55mmol) and catalyst Lu [ CH ] were added under nitrogen2(SiMe3)]3(5 mol%) and reacting at 60 deg.C in 2mL toluene for 24h, and separating the products of diphenylethanone and 1-phenyl-3-cyclopropyl-1-acetone to obtain yields of 71% and 75%, respectively.
Example 8
Under the protection of nitrogen, adding raw materials of 1,2, 5-triphenyl-3-cyclopropyl-1, 5-pentanedione (0.5mmol), phenylsilane (1.0mmol) and catalyst Lu [ N (SiMe)3)2]3(30 mol%) and reacting at 50 deg.C in 2mL toluene for 6h, and separating the products of diphenylethanone and 1-phenyl-3-cyclopropyl-1-acetone to obtain yields of 42% and 43%, respectively.
Diphenylethanone:1H NMR(400MHz,CDCl3)δ(ppm)8.05(d,J＝7.6Hz,2H),7.59(t,J＝7.2Hz,1H),7.49(t,J＝7.3Hz,2H),7.36(t,J＝7.1Hz,2H),7.29(t,J＝7.1Hz,3H),4.32(s,2H)；
1-phenyl-3-cyclopropyl-1-propanone:1H NMR(400MHz,CDCl3)δ7.97(d,J＝7.6Hz,2H),7.54(t,J＝7.1Hz,1H),7.45(t,J＝7.4Hz,2H),3.08(t,J＝7.1Hz,2H),1.64(q,J＝7.0Hz,2H),0.81–0.74(m,1H),0.44(d,J＝7.5Hz,2H),0.07(d,J＝4.3Hz,2H)。
example 9
(E) The hydrogenolysis of the carbon-carbon bond of 1,5,6, 7-tetraphenyl-3-alkenyl-1, 7-heptanedione, the chemical structures of the reactants and the products are as follows:
under the protection of nitrogen, adding the raw material (E) -1,5,6, 7-tetraPhenyl-3-alkenyl-1, 7-heptanedione (0.5mmol), benzhydrol (0.55mmol) and catalyst Y [ N (SiMe)3)2]3(10 mol%) and reacted at 60 ℃ in 2mL of toluene for 24h, the isolation yields of the product diphenylethanone and (E) -1, 5-diphenyl-4-alkenyl-1-pentanone were 65% and 68%, respectively.
Diphenylethanone:1H NMR(400MHz,CDCl3)δ(ppm)8.05(d,J＝7.6Hz,2H),7.59(t,J＝7.2Hz,1H),7.49(t,J＝7.3Hz,2H),7.36(t,J＝7.1Hz,2H),7.29(t,J＝7.1Hz,3H),4.32(s,2H)；
(E) -1, 5-diphenyl-4-alkenyl-1-pentanone:1H NMR(400MHz,CDCl3)δ(ppm)7.98(d,J＝7.7Hz,2H),7.57(t,J＝7.3Hz,1H),7.47(t,J＝7.7Hz,2H),7.35–7.26(m,4H),7.20(t,J＝7.1Hz,1H),6.47(d,J＝15.9Hz,1H),6.34–6.26(m,1H),3.16(t,J＝7.3Hz,2H),2.67(q,J＝7.2Hz,2H)。
example 10
The carbon-carbon bond hydrogenolysis of methyl 2,3, 5-triphenyl-delta-carbonylvalerate, the chemical structures of the reactants and products are as follows:
under the protection of nitrogen, raw material 2,3, 5-triphenyl-delta-carbonyl methyl valerate (0.5mmol), diphenyl methanol (0.50mmol) and catalyst Y [ N (SiMe)3)2]3(2 mol%) and reacted at 60 deg.C in 2mL toluene for 12h, the isolated yields of methyl phenylacetate and 1, 3-diphenyl-1-propanone were 78% and 81%, respectively.
Methyl phenylacetate:1H NMR(400MHz,CDCl3)δ(ppm)7.38–7.29(m,5H),3.71(s,3H),3.66(s,2H)；13C NMR(100MHz,CDCl3)δ(ppm)172.05,134.06,129.30,128.63,127.15,52.03,41.22.
1, 3-diphenyl-1-propanone:1H NMR(400MHz,CDCl3)δ7.99-7.97(m,2H),7.59-7.56(m,1H),7.49-7.46(m,2H),7.34-7.21(m,5H),3.33(t,J＝7.7Hz,2H),3.11-3.07(m,2H)。
example 11
The exocyclic carbon-carbon bond hydrogenolysis of cyclohexanone, the chemical structures of reactants and products are as follows:
under the protection of nitrogen, raw materials of substituted cyclohexanone (0.5mmol), benzhydrol (0.50mmol) and catalyst Y [ N (SiMe) are added3)2]3(2 mol%) and reacting at 60 deg.C in 2mL toluene for 12h, and separating the products cyclohexanone and diphenylethanone to obtain yields of 78% and 80%, respectively.
Cyclohexanone:1H NMR(400MHz,CDCl3)δ(ppm)2.28(t,J＝6.5Hz,4H),1.84–1.78(m,4H),1.69–1.64(m,2H)；13C NMR(100MHz,CDCl3)δ(ppm)212.02,41.93,26.99,24.95。
example 12
The chemical structures of the reactants and products are as follows:
under the protection of nitrogen, the raw material diketone (0.50mmol), cyclohexanol (1.50mmol) and catalyst Y (C) were added5H5)3(2 mol%) and reacting at 80 deg.C in 2mL toluene for 24h, and separating the products of diphenylethanone and 1- (2-furyl) propiophenone to obtain yields of 58% and 55%, respectively.
1- (2-furyl) propiophenone: δ 7.57(dd, J ═ 1.6,0.8Hz,1H), 7.32-7.17 (m,6H),6.52(dd, J ═ 3.6,1.7Hz,1H), 3.18-3.15 (m,2H), 3.07-3.04 (m, 2H).
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered by the claims of the present invention.
Claims (3)
1. A method for carrying out catalytic hydrogenolysis on a non-tension nonpolar carbon-carbon single bond far away from a carbonyl group by using rare earth is characterized by comprising the following specific steps:
under the protection of nitrogen, in a rare earth catalytic system, taking a compound shown as a formula (I) as a reactant, taking a diaryl methanol compound or silane as a hydrogen source, and carrying out selective hydrogenolysis on a non-tension carbon-carbon single bond far away from a carbonyl group to obtain 2 mono-ketone products (II) and (III); the reaction formula is as follows:
in the compounds of the formulas (I) to (III), R is a furan ring; r2Is alkyl, aryl, heteroaryl, alkylene; r1, R3Alkyl, aryl, heteroaryl, silicon base, acyl; r4Is alkyl, aryl, alkoxy, aryloxy, heterocycle, silicon base; n = 0,1, 2;
the catalyst is selected from trialkyl rare earth complexes, triaryl rare earth complexes, triamino rare earth complexes and trialkoxy rare earth complexes;
the rare earth metal is selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu;
the solvent is selected from toluene, xylene, tetrahydrofuran and hexane.
2. The method of claim 1, wherein, in terms of mole ratios: the ratio of the compound of the formula (I) to the rare earth catalyst is 1/(0.005-0.30), and the ratio of the compound of the formula (I) to the hydrogen source is 1/(0.5-2.0).
3. The process according to claim 1, wherein the reaction temperature for hydrogenolysis of compound (I) is 0 to 120 ℃; the reaction time is 1-48 h.
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