SYNTHETIC METHOD AND APPLICATION OF 2-HYDROXYPHENYL-5-PYRAZINYL KETONE

Abstract

Disclosed is a method of synthesizing a 2-hydroxyphenyl-5-pyrazinel ketone represented by the following chemical formula (I), comprising: weighing 0.048 g of a palladium complex, 0.8413 g of chromone-3-formaldehyde and 2.5719 g of ammonium formate into a 100 mL round bottom flask, then adding 50 mL of anhydrous methanol to dissolve, heating to reflux for 36 h, then stopping the reaction, performing column chromatography with petroleum ether and dichloromethane in a volume ratio of 1:1, and then naturally volatilizing the first component to obtain a light yellow crystal, namely the 2-hydroxyphenyl-5-pyrazinel ketone, referred to as compound (I); the chemical formula of the compound (I) is as follows:

##STR00001##

an application of compound (I) as a catalyst in the reaction of benzophenone imine and trimethylsilyl nitrile showing a good catalytic performance, with a conversion rate of 69.1%.

Claims

1. A method of synthesizing a 2-hydroxyphenyl-5-pyrazinel ketone represented by a following chemical formula (I) and unit cell parameters, comprising: weighing 0.048 g of a palladium complex, 0.8413 g of chromone-3-formaldehyde and 2.5719 g of ammonium formate into a 100 mL round bottom flask, then adding 50 mL of anhydrous methanol to dissolve, heating to reflux for 36 h, then stopping the reaction, performing column chromatography with petroleum ether and dichloromethane in a volume ratio of 1:1, and then naturally volatilizing a first component to obtain a light yellow crystal, namely the 2-hydroxyphenyl-5-pyrazinel ketone, referred to as compound (I); the chemical formula of the compound (I) is as follows: ##STR00005## the unit cell parameters are as follows: collecting the diffraction data at a temperature of 273(2) K on an Oxford X-ray single crystal diffractometer using ω-θ scanning with CuKα rays 0.71073 Å, which is monochromatized by a graphite monochromator, wherein the crystal belongs to the orthorhombic system, the space group is P 21 21 21; the unit cell parameters are a=5.505 (2) Å α=90°; b=11.343(10) Å β=90°; c=14.796(13) Å γ=90°.

2. An application of compound (I) according to claim 1 as a catalyst in the reaction of benzophenone imine and trimethylsilyl nitrile, with a conversion rate of 69.1%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0014] FIG. 1 is a crystal X-ray diffraction analysis of 2-hydroxyphenyl-5-pyrazinyl ketone.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0015] 1. Preparation of Chiral Palladium Complexes

[0016] (1) Preparation of [1,4-(4R)-diisopropyl-2-oxazolinyl] benzene

[0017] In a 100 mL two-neck flask, under anhydrous and oxygen-free conditions, 1.4054 g (10.64 mmol) of anhydrous ZnCl.sub.2, 40 ml of chlorobenzene, 5.0236 g (39.2 mmol) of 1,4-dicyanobenzene, and 16.2075 g of L-valinol were added, the mixture was refluxed at high temperature for 60 h, the reaction was stopped, and the solvent was removed under reduced pressure. The residue was dissolved in water and extracted with CHCl.sub.3 (20 mL×2). The organic phase was dried with anhydrous sodium sulfate, and the solvent was removed by rotating. The crude product was subjected to column chromatography with petroleum ether/dichloromethane (4:1) to obtain a light green viscous liquid with a yield of 52%; white crystals, melting point: 48-50° C., [a].sup.5D=+111.9° (c=0.429, CHCl.sub.3); .sup.1HNMR (500 MHz, CDCl.sub.3, 27° C.), δ (ppm)=7.97 (s, 4H), 4.39-4.43 (t, 3.18 Hz, 1H), 4.09-4.15 (m, 2H), 1.85-1.86 (m, 1H), (d, J=6.24 Hz, 6H), 0.86-0.96 (d, J=6.24 Hz, 6H). .sup.13CNMR 18.13, 19.03, 32.85, 70.26, 72.76, 128.10, 128.16, 130.32, 162.82. IR: 3273, 2976, 2960, 2932, 2889, 2869, 1643, 1512, 1469, 1408, 1382, 1366, 1350, 1320, 1296, 1276, 1214, 1180, 1108, 1077, 1047, 1014, 971, 955, 900, 891, 838, 726, 698, 675, 659, 540. HRMS (EI): m/z (%): calcd for C.sub.18H.sub.24N.sub.2O.sub.2: 300.1838; found: 300.1833.

[0018] (2) Preparation of bis{[1,4-(4S)-diisopropyl-2-oxazolinylbenzene] palladium chloride} complex

[0019] In a 100 mL two-neck flask, under anhydrous and oxygen-free conditions, 1.5603 g (4.92 mmol) of palladium chloride, 1.0435 g (3.48 mmol) of 1,4-(4R)-diisopropyl-2-oxazolinylbenzene, 30 mL of chlorobenzene were added, the mixture was refluxed at high temperature for 48 h, then the reaction was stopped, and the solvent was removed under reduced pressure. The residue was dissolved in chloroform and ethanol, and the solvent was volatilized naturally to obtain a crystal with reddish-brown complex with a yield of 92%; m.p.: >200° C. [a].sup.5D=+512.8° (c 0.0564, CH.sub.3OH); .sup.1H NMR (600 MHz, CDCl.sub.3), δ ppm 8.81 (s, 8H, ArH), 4.61-4.63 (m, 4H, CH×4), 4.53 (t, J=9.6 Hz, 4H, CH×4), 4.44 (t, J=8.5 Hz, 4H, CH×4), 3.07-3.10 (m, 4H), 1.18 and 1.15 (dd, J=6.7, 7.2 Hz, 24H, CH3×4); .sup.13C NMR (150 MHz, CDCl.sub.3) ppm 166.8, 130.1(×2), 129.3, 72.0, 69.1, 30.7, 19.0, 15.6; v.sub.max (cm.sup.−1) 3487, 3049, 2957, 2929, 2872, 1642, 1609, 1572, 1509, 1480, 1464, 1416, 1379, 1331, 1288, 1246, 1178, 1141, 1123, 1099, 1045, 1018, 959, 933, 899, 854, 804, 770, 722, 693, 438; Elemental analysis for C.sub.36H.sub.48N.sub.4Cl.sub.4O.sub.4Pd.sub.2, found C 45.26%, H 5.06%, N 5.86%; requires C 45.32%, H 5.24%, N 5.48%;

[0020] 2. Preparation of 2-hydroxyphenyl-5-pyrazinyl Ketone

[0021] 0.048 g of palladium complex, 0.8413 g of chromone-3-formaldehyde and 2.5719 g of ammonium formate were weighed and put into a 100 mL round bottom flask, then 50 mL of anhydrous methanol was added to dissolve, heated to reflux for 36 h, then the reaction was stopped, the crude product was subjected to column chromatography with petroleum ether and dichloromethane in a volume ratio of 1:1, the first component was naturally volatilized to obtain the light yellow crystals. Crystal (I): yield: 52%; m.p.: 82-84° C.; FTIR (cm.sup.−1) 3408, 3044, 1621, 1602, 1574, 1465, 1432, 1416, 1335, 1299, 1242, 1219, 1191, 1178, 1149, 1115, 1035, 1001, 964, 937, 919, 895, 863, 826, 767, 751, 715, 660, 631, 586; m.p.: 132-134° C.; .sup.1H NMR (600 MHz, 298K, CDCl.sub.3 and DMSO) δ 10.6 (s, 1H, OH), 9.32 (s, 1H), 9.0 (s, 2H), 7.48-7.49 (m, 2H), 6.96-6.99 (m, 2H); .sup.13C NMR (150 MHz, 298K, CDCl.sub.3 and DMSO-d6) δ 194.2, 160.7, 158.1, 157.3, 135.3, 131.7, 131.5, 123.5, 120.0, 117.5; Anal. Calcd. for C.sub.11H.sub.8N.sub.2O.sub.2(%): C, 66.00; H, 4.03; N, 13.99. Found: C, 65.87; H, 4.38; N, 13.65; HRMS for C.sub.11H.sub.8N.sub.2O: Anal. Calcd.: 200. 0586; Found: 200.0596.

[0022] The crystal data of the compound crystal (I) is as follows:

TABLE-US-00001 Empirical formula C.sub.11H.sub.8N.sub.2O.sub.2 Molecular weight 200.19 Temperature 293 (2) K Wavelength 0.71073 Å Crystal system, space group Monoclinic system, P 21 21 21 The unit cell parameter a = 5.505 (2) Å α = 90°; b = 11.343 (10) Å β = 90°; c = 14.796 (13) Å γ = 90° Volume 923.9 (5) Å{circumflex over ( )}3 Charge density 4, 1.439 Mg/m{circumflex over ( )}3 Absorption correction parameter 0.102 mm{circumflex over ( )}−1 Number of electrons in a unit cell 416 Crystal size 0.170 × 0.140 × 0.040 mm Range of theta angle 2.753 to 25.487 HKL's indicator collection range −6 <= h < = 6, −13 < k <= 8, −16 < l <= 17 Reflections collected/unique 4688/1708 [R(int) = 0.1298] Absorption correction method Multi-layer scanning Refinement method F{circumflex over ( )}2's matrix least squares method Data/restraints/parameters 1708/0/38 Refinement method 0.998 Consistency factor of the diffraction R1 = 0.0742, ωR2 = 0.1360 points Coincidence factor of observable R1 = 0.2024, ωR2 = 0.1865 diffraction Largest diff. peak and valley 0.252 and −0.253 e .Math. A−3

[0023] Typical bond length data for crystals:

TABLE-US-00002 O (1)—C (7) 1.228 (7) O (2)—C (1) 1.356 (8) O (2)—H (2) 0.8200 N (l)—C (10) 1.305 (10) N (1)—C (11) 1.333 (11) N (2)—C (10) 1.335 (11) N (2)—C (9) 1.341 (9) C (1)—C (2) 1.394 (11) C (1)—C (6) 1.405 (10) C (2)—C (3) 1.351 (10) C (2)—H (2A) 0.9300 C (3)—C (4) 1.378 (11) C (3)—H (3) 0.9300 C (4)—C (5) 1.388 (11) C (4)—H (4) 0.9300 C (5)—C (6) 1.385 (9) C (5)—H (5) 0.9300 C (6)—C (7) 1.501 (12) C (7)—C (8) 1.482 (11) C (8)—C (9) 1.366 (9) C (8)—C (11) 1.386 (12) C (9)—H (9) 0.9300 C (10)—H (10) 0.9300 C (11)—H (11) 0.9300

[0024] Typical bond angle data of crystals:

TABLE-US-00003 C (1)—O (2)—H (2) 109.5 C (10)—N (1)—C (11) 114.1(8) C (10)—N (2)—C (9) 113.7(8) O (2)—C (1)—C (2) 117.9(8) O (2)—C (1)—C (6) 122.8(8) C (2)—C (1)—C (6) 119.3(7) C (3)—C (2)—C (1) 120.2(9) C (3)—C (2)—H (2A) 119.9 C (1)—C (2)—H (2A) 119.9 C (2)—C (3)—C (4) 121.2(10) C (2)—C (3)—H (3) 119.4 C (4)—C (3)—H (3) 119.4 C (3)—C (4)—C (5) 119.9(9) C (3)—C (4)—H (4) 120.1 C (5)—C (4)—H (4) 120.1 C (6)—C (5)—C (4) 119.7(9) C (6)—C (5)—H (5) 120.1 C (4)—C (5)—H (5) 120.1 C (5)—C (6)—C (1) 119.5(8) C (5)—C (6)—C (7) 122.0(8) C (1)—C (6)—C (7) 118.5(7) O (1)—C (7)—C (8) 118.2(8) O (1)—C (7)—C (6) 121.0(8) C (8)—C (7)—C (6) 120.8(7) C (9)—C (8)—C (11) 116.1(8) C (9)—C (8)—C (7) 124.1(8) C (11)—C (8)—C (7) 119.4(8) N (2)—C (9)—C (8) 123.1(8) N (2)—C (9)—H (9) 118.5 C (8)—C (9)—H (9) 118.5 N (1)—C (10)—N (2) 129.8(10) N (1)—C (10)—H (10) 115.1 N (2)—C (10)—H (10) 115.1 N (1)—C (11)—C (8) 123.1(8) N (1)—C (11)—H (11) 118.4 C (8)—C (11)—H (11) 118.4

[0025] Application of the condensation reaction of benzophenone imine and trimethylsilyl nitrile

##STR00004##

[0026] 1 mmol of benzophenone imine and 0.2 mL of trimethylsilyl nitrile were weighed and placed into a 25 mL small flask, 2 mL of THF and 0.1 mmol of compound (I) were added, stirred at room temperature for 5 h, a small amount of sample was taken for NMR detection. The results show that the conversion rate is 69.1%, .sup.1H NMR (600 MHz, CDCl.sub.3, 27° C.) δ 7.23-7.59 (m, 10H), 4.10 (s, 2H).