A kind of 5,6-dihydrotrihydrotriphenylene derivative and its preparation method

Abstract

The invention discloses a 5,6-dihydrobenzophenanthridines derivative and a preparation method thereof. The derivative is prepared by the palladium catalytic cyclization reaction from the precursor product diyne compound. Compared with the prior art, the preparation method is simple, has high yield, is easy to promote, and has wide application prospect in the field of chemical industry production, clinical medical, pesticide, molecule material and so on.

Description

technical field

[0001] The invention belongs to the field of chemical synthesis, and in particular relates to a preparation method of 5,6-dihydrotriphenylene derivatives. Background technique

[0002] Triphenylene compounds have four merged rings, the rings at both ends are aromatic rings, and the aza ring in the middle can be an aromatic ring or a hydrogenated aromatic ring. Triphenanthridine is an important class of heterocyclic compounds with potential biological activity and photoelectric properties, and its structural units widely exist in some natural products, drugs and functional material molecules. As an important class of alkaloids, benzophenanthridine compounds are mainly distributed in Papaveraceae and Rutaceae plants. Their broad-spectrum biological activities have attracted much attention in the fields of anticancer, bactericidal, and anti-inflammatory. For example, benzophenanthridine compounds The alkaloid limpet is widely used in the treatment of toothache,...

Examples

Embodiment 1

[0076]

[0077] Precursor synthesis:

[0078] Weigh N-(2-(phenylethynyl)phenyl)benzenesulfonamide (15mmol), 3-phenyl-2-propyn-1-alcohol (45mmol), triphenylphosphine (30mmol) in the equipped In the Shrek bottle of the constant pressure dropping funnel, anhydrous and anaerobic treatment, repeated filling and discharging of argon gas three times, adding 50mL tetrahydrofuran through constant pressure drop, stirring for 0.5h under ice-water bath, and then using the constant pressure dropping funnel dropwise Diethyl nitrogen dicarboxylate (30mmol), the addition was completed, and the reaction was carried out for 12h. After the reaction was completed, it was washed with water, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. Evaporate the solvent, separate by silica gel column chromatography (eluent: petroleum ether / ethyl acetate 30:1), and obtain the precursor diyne compound N-(3-phenylpropargyl)-N-( 2-(Phenylethynyl)phenyl)-p-toluenesulfonamide.

[00...

Embodiment 2

[0082]

[0083] For the synthesis of the precursor, refer to the synthesis method of the precursor in Example 1;

[0084] For the synthesis and purification method of the target product, refer to the synthesis and purification method of the target product in Example 1 to obtain 5,6-dihydrotrihydrotriphenylene compound (I-2) with a yield of 78%. 1 H NMR (300MHz, CDCl 3 ):δ8.31(s,1H),7.96(d,1H,J=8.7Hz),7.72~7.52(m,4H),7.41~7.34(m,5H),7.22(s,1H),7.18( d, 2H, J=8.1Hz), 6.80~6.65(m, 6H), 4.71(s, 2H), 4.34(q, 2H, J=6.9Hz), 2.02(s, 3H), 1.34(t, 3H ,J=6.9Hz); 13 CNMR (75.5MHz, CDCl 3 ): δ166.5, 143.5, 138.5, 137.9, 137.9, 136.0, 135.5, 134.6, 134.6, 133.6, 133.6, 131.9, 131.6, 130.8, 130.5, 130.2, 129.9, 129.4, 128.7, 128.2, 127 127.4, 127.3, 126.1, 125.7, 125.6, 61.1, 49.5, 21.2, 14.2ppm; FT-IR (KBr): ν3032.1, 2982.0, 1714.7, 1595.1, 1479.4, 1442.8, 1346.3, 1296.2, 11081.29, 11 893.0, 833.3, 812.0, 756.1, 706.0, 684.7cm -1 ;HRMS(APCI): calculated value C 39 h 30 ClNO 4 S[...

Embodiment 3

[0086]

[0087] For the synthesis of the precursor, refer to the synthesis method of the precursor in Example 1;

[0088] For the synthesis and purification method of the target product, refer to the synthesis and purification method of the target product in Example 1 to obtain 5,6-dihydrotrihydrotriphenylene compound (I-3) with a yield of 72%. 1 H NMR (300MHz, CDCl 3 ):7.91(s,1H),7.72~7.59(m,5H),7.44~7.37(m,3H),7.25~7.16(m,5H),6.82~6.72(m,6H),4.72(s,2H ),2.46(s,3H),2.01(s,3H); 13 C NMR (75.5MHz, CDCl 3 ): δ143.4, 138.1, 137.8, 136.4, 136.2, 136.0, 135.9, 135.3, 134.1, 133.0, 132.4, 130.9, 130.5, 130.3, 130.2, 130.1, 129.6, 129.4, 128.9, 128.7, 127. 127.6, 127.3, 126.9, 126.0, 125.7, 119.3, 109.4, 49.4, 21.4, 21.1ppm; FT-IR (KBr): ν3066.8, 2918.3, 1647.2, 1597.1, 1491.0, 1454.3, 1354.0, 1071.4.1, 16 889.2, 841.0, 771.5, 709.8, 651.9cm -1 ;HRMS(APCI): calculated value C 38 h 28 N 2 o 2 S[M+H] + , 577.1944; Found: 577.1946.

technical field

[0001] The invention belongs to the field of chemical synthesis, and in particular relates to a preparation method of 5,6-dihydrotriphenylene derivatives. Background technique

[0002] Triphenylene compounds have four merged rings, the rings at both ends are aromatic rings, and the aza ring in the middle can be an aromatic ring or a hydrogenated aromatic ring. Triphenanthridine is an important class of heterocyclic compounds with potential biological activity and photoelectric properties, and its structural units widely exist in some natural products, drugs and functional material molecules. As an important class of alkaloids, benzophenanthridine compounds are mainly distributed in Papaveraceae and Rutaceae plants. Their broad-spectrum biological activities have attracted much attention in the fields of anticancer, bactericidal, and anti-inflammatory. For example, benzophenanthridine compounds The alkaloid limpet is widely used in the treatment of toothache,...

Examples

Embodiment 1

[0076]

[0077] Precursor synthesis:

[0078] Weigh N-(2-(phenylethynyl)phenyl)benzenesulfonamide (15mmol), 3-phenyl-2-propyn-1-alcohol (45mmol), triphenylphosphine (30mmol) in the equipped In the Shrek bottle of the constant pressure dropping funnel, anhydrous and anaerobic treatment, repeated filling and discharging of argon gas three times, adding 50mL tetrahydrofuran through constant pressure drop, stirring for 0.5h under ice-water bath, and then using the constant pressure dropping funnel dropwise Diethyl nitrogen dicarboxylate (30mmol), the addition was completed, and the reaction was carried out for 12h. After the reaction was completed, it was washed with water, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. Evaporate the solvent, separate by silica gel column chromatography (eluent: petroleum ether / ethyl acetate 30:1), and obtain the precursor diyne compound N-(3-phenylpropargyl)-N-( 2-(Phenylethynyl)phenyl)-p-toluenesulfonamide.

[00...

Embodiment 2

[0082]

[0083] For the synthesis of the precursor, refer to the synthesis method of the precursor in Example 1;

[0084] For the synthesis and purification method of the target product, refer to the synthesis and purification method of the target product in Example 1 to obtain 5,6-dihydrotrihydrotriphenylene compound (I-2) with a yield of 78%. 1 H NMR (300MHz, CDCl 3 ):δ8.31(s,1H),7.96(d,1H,J=8.7Hz),7.72~7.52(m,4H),7.41~7.34(m,5H),7.22(s,1H),7.18( d, 2H, J=8.1Hz), 6.80~6.65(m, 6H), 4.71(s, 2H), 4.34(q, 2H, J=6.9Hz), 2.02(s, 3H), 1.34(t, 3H ,J=6.9Hz); 13 CNMR (75.5MHz, CDCl 3 ): δ166.5, 143.5, 138.5, 137.9, 137.9, 136.0, 135.5, 134.6, 134.6, 133.6, 133.6, 131.9, 131.6, 130.8, 130.5, 130.2, 129.9, 129.4, 128.7, 128.2, 127 127.4, 127.3, 126.1, 125.7, 125.6, 61.1, 49.5, 21.2, 14.2ppm; FT-IR (KBr): ν3032.1, 2982.0, 1714.7, 1595.1, 1479.4, 1442.8, 1346.3, 1296.2, 11081.29, 11 893.0, 833.3, 812.0, 756.1, 706.0, 684.7cm -1 ;HRMS(APCI): calculated value C 39 h 30 ClNO 4 S[...

Embodiment 3

[0086]

[0087] For the synthesis of the precursor, refer to the synthesis method of the precursor in Example 1;

[0088] For the synthesis and purification method of the target product, refer to the synthesis and purification method of the target product in Example 1 to obtain 5,6-dihydrotrihydrotriphenylene compound (I-3) with a yield of 72%. 1 H NMR (300MHz, CDCl 3 ):7.91(s,1H),7.72~7.59(m,5H),7.44~7.37(m,3H),7.25~7.16(m,5H),6.82~6.72(m,6H),4.72(s,2H ),2.46(s,3H),2.01(s,3H); 13 C NMR (75.5MHz, CDCl 3 ): δ143.4, 138.1, 137.8, 136.4, 136.2, 136.0, 135.9, 135.3, 134.1, 133.0, 132.4, 130.9, 130.5, 130.3, 130.2, 130.1, 129.6, 129.4, 128.9, 128.7, 127. 127.6, 127.3, 126.9, 126.0, 125.7, 119.3, 109.4, 49.4, 21.4, 21.1ppm; FT-IR (KBr): ν3066.8, 2918.3, 1647.2, 1597.1, 1491.0, 1454.3, 1354.0, 1071.4.1, 16 889.2, 841.0, 771.5, 709.8, 651.9cm -1 ;HRMS(APCI): calculated value C 38 h 28 N 2 o 2 S[M+H] + , 577.1944; Found: 577.1946.

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