CN103664674A - Preparation method of multi-substituted fused ring compounds - Google Patents

Abstract

The invention belongs to the field of fine chemical industry, and relates to an improved synthesis method of multi-substituted condensed ring compounds and related chemical technologies. It is characterized in that: using N-acyl arylamine and internal alkyne as raw materials, using rhodium salt as catalyst, copper salt as oxidant, heating and reacting in an organic solvent to synthesize a series of multi-substituted condensed ring compounds. The present invention mainly provides a new method for synthesizing multi-substituted condensed ring compounds. The method has the advantages of simple method steps, easy availability of raw materials, high atom economy, and environmental friendliness. Since the multi-substituted condensed ring compound is an important skeleton structure, it is widely used in the fields of organic semiconductor materials and light-emitting materials; therefore, the present invention has great use value and social and economic benefits.

Description

A kind of preparation method of multi-substituted condensed ring compound

technical field

The invention relates to a preparation method of functional materials, especially a preparation method of multi-substituted condensed ring compounds.

Background technique

Multi-substituted fused ring compounds are an important class of skeleton structures, which are widely used in the fields of organic semiconductor materials and light-emitting materials. Regarding the synthesis of multi-substituted fused ring compounds, the following two methods are usually adopted:

(1) Cyclization of difunctional aromatic compounds with internal alkynes

D,Pérez D,Guitián E,Castedo L.J.Am.Chem.Soc.1999,121,5827.]。The substrate of this method is expensive, poor in stability, needs to be prepared in advance, and has low atom economy [see: (a) Huang W, ZhouX, Kanno K I, Takahashi T.Org.Lett.2004,6,2429; (b ) D, Pérez D, Guitián E, Castedo LJ Org. Chem. 2000, 65, 6944; (c)

D, Pérez D, Guitián E, Castedo LJ Am. Chem. Soc. 1999, 121, 5827.].

(2) Cyclization of monofunctional aromatic compounds with internal alkynes

The substrate of this method is expensive, requires multi-step synthesis, and the by-products generated are not environmentally friendly [see (a) Wu G, Rheingold AL, Feib S L, Heck R F.Organometallics1987,6,1941; (b ) Kawasaki S, Satoh T, Miura M, Nomura M.J.Org.Chem., 2003, 68, 6836; (c) Yasukawa T, Satoh T, Miura M, Nomura M.J.Am.Chem.Soc. 2002, 124, 12680 ;(d) Ueura K, Satoh T, Miura M.J.Org.Chem.2007, 72, 5362; (e) Uto T, Shimizu M, Ueura K, Tsurugi H, Satoh T, Miura M.J.Org.Chem.2008, 73, 298; (f) Fukutani T, Hirano K, Satoh T, Miura M. Org. Lett., 2009, 11, 5198.].

purpose of invention

The object of the present invention is to provide a simple, efficient, highly atom-economical and environmentally friendly synthesis method for multi-substituted condensed ring compounds.

Contents of the invention

The invention uses N-acyl arylamine and internal alkyne as raw materials, uses rhodium salt as catalyst, copper salt as oxidant, heats and reacts in an organic solvent, and synthesizes a series of multi-substituted condensed ring compounds. The synthetic route is as follows:

In the reaction of the above synthesis method, the rhodium salt catalyst used includes rhodium trichloride, rhodium acetate, dichloro(cyclopentadienyl) rhodium (III) dimer, dichloro(pentamethylcyclopentadiene base) rhodium (III) dimer and tris(triphenylphosphine) rhodium (I) chloride, and the addition amount of the rhodium salt is 1mol%-20mol% of the N-acylarylamine.

In the reaction of above-mentioned synthetic method, used copper salt oxidant comprises cuprous iodide, cuprous bromide, cuprous chloride, cuprous oxide, copper acetate, cupric acetate monohydrate, cupric chloride or cupric oxide, described The amount of copper salt added is 20mol%-400mol% of the N-acylarylamine.

In the reaction of the above synthesis method, the organic solvents used include benzene, toluene, 1,4-dioxane, dimethylsulfoxide, N,N-dimethylformamide, methanol, ethanol, isopropanol, Butanol, methylene chloride, chloroform, n-butyl ether, carbon tetrachloride, ethyl acetate, petroleum ether, methyl tert-butyl ether, tetrahydrofuran, acetone, acetonitrile, the addition of the organic solvent is N - 10-100 times the weight of acyl arylamine.

In the reaction of the above synthesis method, the reaction temperature is 50-130°C.

Description of drawings

Fig. 1 is the ¹ H-NMR of compound 3a.

Fig. 2 is the ¹³ C-NMR of compound 3a.

Fig. 3 is the ¹ H-NMR of compound 3b.

Fig. 4 is the ¹³ C-NMR of compound 3b.

Fig. 5 is the ¹ H-NMR of compound 3c.

Fig. 6 is the ¹³ C-NMR of compound 3c.

Fig. 7 is the ¹ H-NMR of compound 3d.

Fig. 8 is the ¹³ C-NMR of compound 3d.

Fig. 9 is the ¹ H-NMR of compound 3e.

Fig. 10 is the ¹³ C-NMR of compound 3e.

Fig. 11 is the ¹ H-NMR of compound 3f.

Fig. 12 is the ¹³ C-NMR of compound 3f.

Fig. 13 is the ¹ H-NMR of compound 3g.

Fig. 14 is the ¹³ C-NMR of compound 3g.

Fig. 15 is the ¹ H-NMR of compound 3h.

Fig. 16 is the ¹³ C-NMR of compound 3h.

Fig. 17 is the ¹ H-NMR of compound 3i.

Fig. 18 is the ¹³ C-NMR of compound 3i.

Detailed ways

The following further describes the present invention and the manner in which the method of the present invention is carried out in conjunction with examples of implementation. These implementation examples are only for further elucidating the present invention rather than limiting the protection of the present invention thereto.

Example 1: Synthesis of N-(5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (3a)

Accurately weigh N-pivaloylanilide (44.3mg, 0.25mmol), rhodium chloride (2.6mg, 0.0125mmol), toluene (89.2mg, 0.5mmol), copper acetate (45.5mg, 0.25mmol), and Sequentially added to a 25mL Schlenk bottle, added refined ethanol (3.0mL), and placed in an oil bath at 50°C for 8h. After the reaction, the solvent was removed under reduced pressure, and petroleum ether/ethyl acetate was used as the eluent, and the silica gel column was used for separation. The yield of N-(5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide was 80%. ¹ H NMR (400MHz, CDCl ₃ )δ7.88(d, J=7.6Hz, 1H), 7.49(d, J=8.2Hz, 1H), 7.40(dd, J=7.6, 8.2Hz, 1H), 7.24 -7.14(m,11H),6.82-6.74(m,8H),6.64-6.62(m,2H),0.80(s,9H); ¹³ C NMR(100MHz,CDCl ₃ )δ177.0,142.3,141.3,140.5, ^{( 1} )3425,3337,3050,3024,1670,1601,1493,1475,1441,1382,1157,910,778,736,730,698;HRMS(ESI)Calcd for C ₃₉ H ₃₄ NO532.2640[M+H] ⁺ ,found532.2645.

Example 2: Synthesis of N-(5,6,7,8-tetrakis(4-fluorophenyl)naphthalen-1-yl)pivalamide (3b)

Accurately weigh N-pivaloylanilide (44.3mg, 0.25mmol), rhodium acetate (1.1mg, 0.0025mmol), 1,2-di(4-fluorophenyl)acetylene (107.0mg, 0.5mmol), iodide Cuprous (47.6mg, 0.25mmol) was added to a 25mL Schlenk bottle in turn, and purified cyclohexane (3.0mL) was added, and placed in an oil bath at 100°C for 10h. After the reaction was over, the solvent was removed under reduced pressure, using petroleum ether/ethyl acetate as eluent, and silica gel column separation, N-(5,6,7,8-tetrakis(4-fluorophenyl)naphthalen-1-yl)pivalamide The yield was 63%. ¹ H NMR(400MHz, CDCl ₃ )δ7.82(d,J=6.2Hz,1H),7.48-7.43(m,2H),7.13-7.07(m,5H),6.96-6.89(m,4H), 6.68-6.65(m,2H),6.60-6.56(m,6H),0.87(s,9H); ¹³ C NMR(100MHz,CDCl ₃ )δ176.9,161.8(d, ¹ J _C–F =246.7Hz), 161.6(d, ¹ J _C–F =244.7Hz),160.7(d, ¹ J _C–F =243.9Hz),160.6(d, ¹ J _C–F =244.2Hz),140.4,138.9,138.2,137.81, ^C4 ₌ ^IR ₍ ^KBr ₎ ^_ _{_} υ(cm ^-1 )3444,3321,2956,2917,2848,1659,1604,1509,1478,1380,1224,1157,1093,1015,909,830,816,777,758,734; HRMS(ESI)Calcd for C ₃₉ H _{29 3} [NO26.20 M+Na] ⁺ ,found626.2088.

Example 3: Synthesis of N-(5,6,7,8-tetrakis(4-chlorophenyl)naphthalen-1-yl)pivalamide (3c)

Accurately weigh N-pivaloylanilide (44.3mg, 0.25mmol), dichloro(cyclopentadienyl) rhodium(III) dimer (2.4mg, 0.005mmol), 1,2-bis(4- Chlorophenyl) acetylene (123.5mg, 0.5mmol), cuprous bromide (17.9mg, 0.125mmol), and added to a 25mL Schlenk bottle in turn, added refined toluene (3.0mL), placed in 60 ° C oil Reaction in the bath for 7h. After the reaction was over, the solvent was removed under reduced pressure, and petroleum ether/ethyl acetate was used as eluent, followed by silica gel column separation, N-(5,6,7,8-tetrakis(4-chlorophenyl)naphthalen-1-yl)pivalamide The yield was 76%. ¹ H NMR (400MHz, CDCl ₃ )δ7.76(dd, J=5.0,3.7Hz,1H),7.44-7.43(m,2H),7.26-7.18(m,4H),7.07(dd,J=10.0 ,8.4Hz,4H),6.92(s,1H),6.89-6.86(m,4H),6.64(d,J=8.4Hz,2H),6.55(d,J=8.4Hz,2H),0.87(s ,9H); ¹³ C NMR (100MHz, CDCl ₃ ) δ177.0,140.1,139.7,138.7,138.2,138.0,137.7,137.6,134.1,134.0,133.5,133.4,133.0,132.3,132.2,132.0,1281.6,132.9, , 127.4, 127.3, 126.5, 126.33, 126.31, 125.7, ^39.3 , 26.9; ;HRMS(ESI) Calcd for C ₃₉ H ₂₉ NONaCl ₄ 690.0901[M+Na] ⁺ ,found 690.0890.

Example 4: Synthesis of N-(5,6,7,8-tetrakis(4-bromophenyl)naphthalen-1-yl)pivalamide (3d)

Accurately weigh N-pivaloylanilide (44.3mg, 0.25mmol), dichloro(pentamethylcyclopentadienyl) rhodium(III) dimer (3.1mg, 0.005mmol), 1,2-di (4-Bromophenyl)acetylene (168.0mg, 0.5mmol), cuprous oxide (71.6mg, 0.5mmol), and added to a 25mL Schlenk bottle in turn, added refined 1,4-dioxane ( 3.0mL), placed in an 80°C oil bath for 14h. After the reaction was over, the solvent was removed under reduced pressure, using petroleum ether/ethyl acetate as eluent, and silica gel column separation, N-(5,6,7,8-tetrakis(4-bromophenyl)naphthalen-1-yl)pivalamide The yield was 77%. ¹ HNMR(400MHz, CDCl ₃ )δ7.75(dd, J=4.4,4.4Hz,1H),7.43(d,J=4.4Hz,2H),7.39(d,J=8.2Hz,2H),7.34( d,J=8.3Hz,2H),7.04-6.98(m,8H),6.90(s,1H),6.59(d,J=8.3Hz,2H),6.49(d,J=8.2Hz,2H), 0.88(s,9H); ¹³ C NMR(100MHz,CDCl ₃ )δ177.1,140.6,139.5,138.7,138.6,138.5,138.2,137.4,134.1,134.0,133.6,132.6,132.4,132.3,131.5,130.4, 130.3,126.6,126.5,126.3,125.8,121.6,121.3,120.4,120.2,39.3,26.9; IR(KBr)υ(cm ^-1 )3438,3329,2956,2924,2854,1654,1489,1391,1101, 1071,1011,908,827,774,764,732; HRMS (ESI) Calcd for C ₃₉ H ₂₉ NONaBr ₄ 865.8880[M+Na] ⁺ ,found 865.8846.

Example 5: Synthesis of N-(5,6,7,8-tetra-p-tolylnaphthalen-1-yl)pivalamide (3e)

Accurately weigh N-pivaloylanilide (44.3mg, 0.25mmol), tris(triphenylphosphine) rhodium(I) chloride (10.0mg, 0.025mmol), 1,2-bis(4-tolyl)acetylene (103.2mg, 0.5mmol), copper chloride (100.9mg, 0.75mmol), and added to a 25mL Schlenk bottle in turn, added refined dimethyl sulfoxide (3.0mL), placed in an oil bath at 120°C Reaction 30h. After the reaction, the solvent was removed under reduced pressure, using petroleum ether/ethyl acetate as the eluent, and separated on a silica gel column, N-(5,6,7,8-tetra-p-tolylnaphthalen-1-yl)pivalamide (3e) The yield is 67%. ¹ H NMR (400MHz, CDCl ₃ ) δ7.88 (d, J=6.7Hz, 1H), 7.44 (d, J=8.4Hz, 1H), 7.34 (dd, J=7.8, 8.2Hz, 1H), 7.06 -6.96(m,9H),6.62-6.59(m,6H),6.49(d,J=7.9Hz,2H),2.29(s,3H),2.26(s,3H),2.09(s,3H), 2.07(s,3H),0.81(s,9H); ¹³ C NMR(100MHz,CDCl ₃ )δ177.0,141.5,139.4,139.20,139.17,137.7,137.4,137.1,136.6,135.8,134.44,134.37,134.325,13 ,133.5,131.2,131.1,131.0,129.1,128.3,127.3,127.2,125.43,125.38,124.2,39.3,26.9,21.4,21.3,21.2;IR(KBr)υ(cm ^-1 )3421,3022,2956,2923 ,2868,1670,1510,1466,1378,1157,1110,1021,817,756,744; HRMS (ESI) Calcd for C ₄₃ H ₄₁ NONa610.3086[M+Na] ⁺ ,found610.3094.

Example 6: Synthesis of N-(3-methyl-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (3f)

Accurately weigh N-pivaloyl-3-methylaniline (47.8mg, 0.25mmol), rhodium chloride (2.6mg, 0.0125mmol), toluene (89.2mg, 0.5mmol), copper acetate (45.5mg, 0.25mmol), and sequentially added to a 25mL Schlenk bottle, added refined ethanol (3.0mL), and placed in an oil bath at 70°C for 9h. After the reaction was over, the solvent was removed under reduced pressure, and petroleum ether/ethyl acetate was used as the eluent, and the silica gel column separation, the yield of N-(3-methyl-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide 79%. ¹ H NMR (400MHz, CDCl ₃ )δ7.81(s,1H),7.25–7.13(m,12H),6.81–6.73(m,8H),6.63–6.61(m,2H),2.38(s,3H ),0.80(s,9H); ¹³ C NMR(100MHz,CDCl ₃ )δ177.0,142.2,140.6,140.4,140.0,139.0,138.8,135.6,134.24,134.17,133.3,131.3,131.1,128.3,1277.6,12 126.5,126.4,125.34,125.29,125.14,125.06,124.6,124.5,123.6,39.3,26.9,21.7; IR(KBr)υ(cm ^-1 )3421,3343,2955,2923,1669,1507,1494,1457, 1441,1400,1165,1071,1027,858,757,735,698; HRMS (ESI) Calcd for C ₄₀ H ₃₅ NONa568.2616[M+Na] ⁺ ,found568.2615.

Example 7: Synthesis of N-(3-chloro-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide (3g)

Accurately weigh N-pivaloyl-3-chloroaniline (52.9mg, 0.25mmol), rhodium acetate (1.1mg, 0.0025mmol), 1,2-di(4-fluorophenyl)acetylene (107.0mg, 0.5mmol ), cuprous iodide (47.6mg, 0.25mmol), and sequentially added to a 25mL Schlenk bottle, added refined cyclohexane (3.0mL), and placed in an oil bath at 110°C for 7h. After the reaction was over, the solvent was removed under reduced pressure, and petroleum ether/ethyl acetate was used as the eluent, and the silica gel column separation, the yield of N-(3-chloro-5,6,7,8-tetraphenylnaphthalen-1-yl)pivalamide 78%. ¹ H NMR (400MHz, CDCl ₃ ) δ8.10(d, J=2.0Hz, 1H), 7.43(d, J=2.1Hz, 1H), 7.38(s, 1H), 7.24–7.13(m, 10H) ,6.82–6.78(m,6H),6.74–6.72(m,2H),6.62–6.60(m,2H),0.78(s,9H); ¹³ C NMR(100MHz,CDCl ₃ )δ177.0,141.6,141.5, 140.2,140.1,140.0,139.2,138.9,135.2,134.8,134.5,131.8,131.3,131.2,131.0,128.7,127.9,127.6,127.0,126.8,126.6,125.7,125.4,123.9,123.9,123.7,123.4,39.5, ⁽ ESI) Calcd for C ₃₉ H ₃₃ NOCl566.2251[M+H] ⁺ ,found566.2300.

Example 8: Synthesis of N-(5,6,7,8-tetraphenylnaphthalen-1-yl)acetamide (3h)

Accurately weigh N-pivaloylanilide (33.8 mg, 0.25 mmol), dichloro(cyclopentadienyl) rhodium (III) dimer (2.4 mg, 0.005 mmol), 1,2-bis(4- Chlorophenyl) acetylene (123.5mg, 0.5mmol), cuprous bromide (17.9mg, 0.125mmol), and added to a 25mL Schlenk bottle in turn, added refined toluene (3.0mL), placed in 90 ° C oil Reaction in the bath for 8h. After the reaction, the solvent was removed under reduced pressure, and petroleum ether/ethyl acetate was used as the eluent, and silica gel column separation was performed. The yield of N-(5,6,7,8-tetraphenylnaphthalen-1-yl)acetamide was 23%. ¹ H NMR(CDCl ₃ ,400MHz)δ7.94(d,J=7.4Hz,1H),7.50(d,J=8.5Hz,1H),7.38(dd,J=7.8,8.2Hz,1H),7.24 -7.17(m,10H),7.00(s,1H),6.82-6.73(m,10H),1.39(s,3H); ¹³ C NMR(CDCl ₃ ,100MHz)δ168.3,142.4,141.1,140.3,140.1, 139.8, 139.6, 139.0, 134.6, 133.9, 133.1, 131.3, 131.1, 130.7, 128.4, 127.7, 127.2, 126.7, 126.6, 126.0, 125.54, 125.45, 124.5, 123.5, 24.1.

Example 9: Synthesis of N-(5,6,7,8-tetraphenylnaphthalen-1-yl)adamantane-1-carboxamide (3i)

Accurately weigh N-adamantanecarboxanilide (63.8 mg, 0.25 mmol), dichloro(pentamethylcyclopentadienyl) rhodium (III) dimer (3.1 mg, 0.005 mmol), 1,2- Bis(4-bromophenyl)acetylene (168.0mg, 0.5mmol) and cuprous oxide (71.6mg, 0.5mmol) were successively added to a 25mL Schlenk bottle, and refined 1,4-dioxane was added (3.0 mL), placed in an oil bath at 100°C for 12 h. After the reaction, the solvent was removed under reduced pressure, using petroleum ether/ethyl acetate as the eluent, and separated on a silica gel column, the yield of N-(5,6,7,8-tetraphenylnaphthalen-1-yl)adamantane-1-carboxamide 76%. ¹ H NMR (400MHz, CDCl ₃ )δ7.96(d, J=7.5Hz, 1H), 7.48(d, J=8.5Hz, 1H), 7.39(dd, J=8.2, 7.7Hz, 1H), 7.29 (s,1H),7.24–7.14(m,10H),6.81–6.74(m,8H),6.64–6.62(m,2H),1.86(s,3H),1.65–1.51(m,6H),1.39 (s,6H); ¹³ C NMR(100MHz,CDCl ₃ )δ176.5,142.3,141.4,140.5,140.4,140.0,139.5,139.0,134.4,134.2,133.5,131.31,131.29,131.1,128.6,127.1,127 , 126.5, ^125.8 , 125.5, 125.4, 125.3, 125.2, 124.5, 41.2, 38.1, 36.4, 28.1; ,1467,1441,1379,1346,1250,1220,1110,1072,910,778,734,697; HRMS (ESI) Calcd for C ₄₅ H ₃₉ NONa632.2929[M+Na] ⁺ ,found632.2921.

Claims (8)

1. A kind of preparation method of substituted condensed ring compound is characterized in that, taking N-acyl arylamine and internal alkyne as raw material, rhodium salt as catalyzer, copper salt as oxidant, heating reaction in organic solvent, synthesizes a series of Multi-substituted fused ring compounds, the reaction formula is as follows:

In the formula: R is an alkyl group or an aryl group; ^R is hydrogen, alkyl, aryl, alkoxy, ester, acyl, cyano, halogen; R ² and R ³ are alkyl, alkenyl, alkynyl, aryl. 2. preparation method according to claim 1, is characterized in that, described rhodium salt catalyst is rhodium trichloride, rhodium acetate, dichloro (cyclopentadienyl) rhodium (III) dimer, dichloro (Pentamethylcyclopentadienyl) rhodium (III) dimer, three (triphenylphosphine) rhodium chloride (I), wherein, the addition of rhodium salt is 1-20mol of N-acyl arylamine %. 3. according to the preparation method described in claim 1 or 2, it is characterized in that, described copper salt oxidizing agent is cuprous iodide, cuprous bromide, cuprous chloride, cuprous oxide, copper acetate, acetic acid monohydrate Copper, copper chloride or copper oxide, wherein the amount of copper salt added is 20mol%-400mol% of the N-acyl arylamine. 4. The preparation method according to claim 1 or 2, characterized in that, the organic solvent is benzene, toluene, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylmethane Amide, methanol, ethanol, isopropanol, n-butanol, methylene chloride, chloroform, n-butyl ether, carbon tetrachloride, ethyl acetate, petroleum ether, methyl tert-butyl ether, tetrahydrofuran, acetone, or acetonitrile One or two or more mixed solvents; the amount of the organic solvent added is 10-100 times the mass of the N-acyl arylamine. 5. preparation method according to claim 3 is characterized in that, described organic solvent is benzene, toluene, 1,4-dioxane, dimethylsulfoxide, N, N-dimethylformamide, Methanol, ethanol, isopropanol, n-butanol, methylene chloride, chloroform, n-butyl ether, carbon tetrachloride, ethyl acetate, petroleum ether, methyl tert-butyl ether, tetrahydrofuran, acetone, or acetonitrile One or more than two mixed solvents; the amount of the organic solvent added is 10-100 times the mass of the N-acyl arylamine. 6. The preparation method according to claim 1, 2 or 5, characterized in that the reaction temperature is 50-130°C. 7. The preparation method according to claim 3, characterized in that the reaction temperature is 50-130°C. 8. The preparation method according to claim 4, characterized in that the reaction temperature is 50-130°C.

Images