CN1817825A - A kind of preparation method of polybenzene compound - Google Patents

Abstract

The invention discloses a preparation method of polybenzene compounds. It is to put 1mmol polyhalogenated aromatic hydrocarbons, 4-9mmol boric acid, 3-6mmol sodium carbonate, 1.0-2.0mol% palladium acetate in the reactor, add 3-9ml organic solvent and 3-9ml water, in Stir at 55°C-80°C for 12-18 hours, extract with ether, and spin in a solvent to obtain the product. Advantages of the present invention: 1) The mixed solution of water and N,N-dimethylformamide is selected as the reaction solvent, which combines the advantages of a single water solvent and a single organic solvent, and without ligands and any phase transfer catalysts 2) the reaction does not need the protection of any inert gas, and can be carried out well in the air; 3) the reaction is carried out under mild conditions, the operation is simple, the reaction time is short, and the reaction yield is high , the separation of the product and the reaction system can be achieved through simple ether extraction; 4) the method has good selectivity, and all halogens react to generate polyphenyl compounds.

Description

A kind of preparation method of polybenzene compound

technical field

The invention relates to a preparation method of polybenzene compounds.

Background technique

Polybenzenes are one of the most common structural components in natural products, and are widely used in materials science and biological science (Watson, M.D.; Fechtenkotter, A.; Mullen, K.Chem.Rev.2001, 101, 1267. Gary, G.W.; Winsor, P.A. Liquid Crystals and Plastic Crystals 1, John Wiley and Sons, New York (1974). Heeger, A.J.J.Phys.Chem.B 2001, 105, 8475. Yang, S.-M.; Shie , J.-J.; Fang, J.-M.; Nandy, S.K.; Chang, H.-Y.; Lu, S.-H.; Wang, G.J.Org.Chem.2002, 67, 5208.). For example, some materials based on л-conjugation are an important part in the scientific development of optoelectronic devices, some of which have been commercialized.

It has been reported in the literature that there are many ways to synthesize this class of polybenzenes (Li, S.; Wei, B.; Low, P.M.N.; Lee, H.K.; Hor, T.S.A.; Xue F.; Mak, T.C.W.J.Chem.Soc., Dalton Trans., 1997, 1289. Minato, A.; Tamao, K.; Hayashi, T.; Suzuki K.; Kumada, M. Tetrahedron Lett., 1980, 21, 845. Nakada, M.; Miura, C. ; Nishiyama, H.; Higashi, F.; Mori, T.Bull.Chem.Soc.Jpn., 1989, 62, 3122 B.), including the use of Grignard reagents. However, there are still some problems in these methods, such as some require severe reaction conditions, inconvenient operation, some reactions have poor selectivity, and the yield is very low, which limits the scope of application of this method to a certain extent. The Suzuki coupling reaction is also a classic method for preparing polyphenyl compounds, which is characterized in that polyhalogenated hydrocarbons and phenylboronic acid are used to react to generate polybenzene compounds. It is reported in the literature that this method is used to synthesize polybenzene compounds, but some highly efficient trioxide-containing ligands are often added during the reaction process. Since these ligands are sensitive to water and air, some protective measures need to be taken during the experimental operation. Practical application brings great inconvenience (Wong, K.-T.; Hung, T.S.; Lin, Y.; Wu, C.-C.; Lee, G.-H.; Peng, S.-M.; Chou, C.H.; Su, Y.O.Org.Lett.2002, 4, 513.Bo, Z.; Schlueter, A.D.J.Org.Chem.2002, 67, 5327. Garg, N.K.; Sarpong, R.; . Soc. 2002, 124, 13179. Berthiol, F.; Kondolff, I.; Doucet, H.; Santelli, M.J. Orgnomet. Chem. 2004, 689, 2786.).

Contents of the invention

The purpose of this invention is to provide a kind of preparation method of polybenzene compound.

It is the polyhalogenated aromatic hydrocarbon of 1mmol, the boric acid of 4-9mmol, the sodium carbonate of 3-6mmol, the palladium acetate of 1.0-2.0mol% in the reactor, add the water of 3-9ml organic solvent and 3-9ml, in Stir at 55°C-80°C for 12-18 hours, extract with ether, and spin dry the solvent to obtain the product.

Advantages of the present invention:

1) The mixture of water and organic solvent is selected as the reaction solvent, which combines the advantages of a single water solvent and a single organic solvent, and reacts without a ligand and any phase transfer catalyst, and the yield is very high;

2) The reaction does not require the protection of any inert gas, and can be carried out well in air;

3) The reaction is carried out under mild conditions, the operation is simple, the reaction time is short, the reaction yield is high, and the separation of the product and the reaction system can be achieved through simple ether extraction;

4) The method has good selectivity, and all the halogens react to generate polyphenyl compounds.

Detailed ways

The present invention adopts organic solvent and water as co-solvent, under the presence of alkali and palladium acetate, without ligand and phase transfer catalyst, without the protection of inert gas, polyhalogenated aromatic hydrocarbons and boric acid undergo coupling reactions to obtain various of polybenzenes. The basic equation for the reaction is:

The polyhalogenated aromatic hydrocarbon is X ₁ -Ph-X ₂ , and the boronic acid is R ₂ PhB(OH) ₂ , wherein, when X ₁ is I, X ₂ is 2-Br, 3-Br or 4-Br, R ₂ is H; when X ₁ is Br, X ₂ is 3-Br or 4-Br, and R ₂ is H, OMe or CF ₃ . The polyhalogenated aromatic hydrocarbon is (X ₃ ) ₃ -Ph-R ₁ , the boronic acid is R ₂ PhB(OH) ₂ , wherein X ₃ is Br, R ₁ is H or OH, and R ₂ is H, OMe or CF ₃ .

The amount of organic solvent used is 3-6ml. The organic solvent is N,N-dimethylformamide. The consumption of water is 3-6ml. The alkali is sodium carbonate, and the dosage is 4-6 mmol. The reaction temperature is 60°C-80°C, and the reaction time is 12-16 hours. The consumption of palladium acetate is 1.0-1.5% mol.

The following examples will help to understand the present invention, but are not limited to the content of the present invention:

Example 1

Weigh 1mmol of m-bromoiodobenzene, 4mmol of PhB(OH) ₂ , 3mmol of sodium carbonate, 1mol% of palladium acetate in a 25ml small flask, add 3ml of N,N-dimethylformamide and 3ml of water, Stir at 60°C for 18 hours. After the reaction, extract with 4*10ml of ether. After the solvent was spin-dried, the product was obtained with a yield of 98%. Analytical pure samples can be obtained by column separation with petroleum ether/ethyl acetate.

¹ H NMR (400MHz, CDCl ₃ , TMS): δ7.83(s, 1H), 7.68(d, 4H, J=9.2Hz), 7.61(d, 2H, J=8.4Hz), 7.54(d, 1H , J=7.4Hz), 7.68(t, 4H, J=7.6Hz), 7.68(t, 2H, J=7.5Hz).MS(EI): m/z(%): 230(100)[M ⁺ ], 202(10), 152(8), 115(12).

Example 2

Weigh 1mmol of m-dibromobenzene, 6mmol of 4-CF ₃ Ph(OH) ₂ , 4mmol of sodium carbonate, 1mol% of palladium acetate in a 25ml small flask, add 3ml of N,N-dimethylformamide and 3.5ml of water, stirred at 60°C for 12 hours. After the reaction, extract with 4*10ml of ether. After the solvent was spin-dried, the product was obtained with a yield of 95%. Analytical pure samples can be obtained by column separation with petroleum ether/ethyl acetate.

¹H NMR(500MHz，CDCl₃，TMS)：δ7.79(s，1H)，7.73(m，8H)，7.64-7.56(m，3H)；¹³C NMR(125MHz，CDCl₃)δ144.60，140.90，129.97(q，J＝32.3Hz)，129.93，127.80，127.36，126.56，126.10(q，J＝3.8Hz)，124.52(q，J＝270.3Hz)；MS(EI)：m/z(％)：366(100)[M⁺]，347(12)，296(10)，228(10)，183(8)；HRMS(EI)calcd for C₂₀H₁₂F₆，366.0838；found，366.0835；IR(KBr)v 1616，1573，1482，1410，1389，1323，1249，1173，1126，1070，1059，1023，844，796，755，737，698，601，430cm^-1.

¹ H NMR (500MHz, CDCl ₃ , TMS): δ7.79 (s, 1H), 7.73 (m, 8H), 7.64-7.56 (m, 3H); ¹³ C NMR (125MHz, CDCl ₃ ) δ144.60, 140.90, 129.97(q, J=32.3Hz), 129.93, 127.80, 127.36, 126.56, 126.10(q, J=3.8Hz), 124.52(q, J=270.3Hz); MS(EI): m/z(% ): 366(100)[M ⁺ ], 347(12), 296(10), 228(10), 183(8); HRMS(EI) calcd for C ₂₀ H ₁₂ F ₆ , 366.0838; found, 366.0835; IR(KBr)v 1616, 1573, 1482, 1410, 1389, 1323, 1249, 1173, 1126, 1070, 1059, 1023, 844, 796, 755, 737, 698, 601, ^{430cm -1} .

Example 3

Weigh 1mmol of p-dibromobenzene, 6mmol of PhB(OH) ₂ , 4mmol of sodium carbonate, and 1mol% of palladium acetate in a 25ml small flask, add 3ml of N,N-dimethylformamide and 3.5ml of water , stirred at 60 °C for 12 hours. After the reaction, extract with 4*10ml of ether. After the solvent was spin-dried, the product was obtained with a yield of 96%. Analytical pure samples can be obtained by column separation with petroleum ether/ethyl acetate.

¹H NMR(400MHz，CDCl₃，TMS)：δ7.68(s，4H)，7.68(d，4H，J＝8.0Hz)，7.46(t，4H，J＝7.6Hz)，7.36(t，2H，J＝7.4Hz).MS(EI)：m/z(％)：230(100)[M⁺]，215(8)，202(10)，152(8)，115(12).

¹ H NMR (400MHz, CDCl ₃ , TMS): δ7.68(s, 4H), 7.68(d, 4H, J=8.0Hz), 7.46(t, 4H, J=7.6Hz), 7.36(t, 2H , J=7.4Hz). MS (EI): m/z (%): 230 (100) [M ⁺ ], 215 (8), 202 (10), 152 (8), 115 (12).

Example 4

Weigh 1mmol of p-dibromobenzene, 6mmol of 4-CF ₃ PhB(OH) ₂ , 4mmol of sodium carbonate, 2mol% palladium acetate in a 25ml small flask, add 3ml of N,N-dimethylformamide and 3.5ml of water, stirred at 80°C for 18 hours. After the reaction, extract with 4*10ml of ether. After the solvent was spin-dried, the product was obtained with a yield of 95%. Analytical pure samples can be obtained by column separation with petroleum ether/ethyl acetate.

¹H NMR(400MHz，CDCl₃，TMS)：δ7.72-7.77(m，6H).MS(EI)：m/z(％)：366(100)[M⁺]，347(10)，296(8)，183(8)，158(5).

¹ H NMR (400MHz, CDCl ₃ , TMS): δ7.72-7.77 (m, 6H). MS (EI): m/z (%): 366 (100) [M ⁺ ], 347 (10), 296 (8), 183(8), 158(5).

Example 5

Weigh 1mmol of 1,3,5-tribromobenzene, 9mmol of 4-CF ₃ PhB(OH) ₂ , 6mmol of sodium carbonate, and 2mol% of palladium acetate in a 25ml small flask, add 3ml of N,N-di Methylformamide and 3.5ml of water were stirred at 60°C for 12 hours. After the reaction, extract with 4*10ml of ether. After the solvent was spin-dried, the product was obtained with a yield of 90%. Analytical pure samples can be obtained by column separation with petroleum ether/ethyl acetate.

¹ H NMR (400MHz, CDCl ₃ , TMS): δ7.82(s, 3H), 7.80(d, 6H, J=8.4Hz), 7.76(d, 6H, J=8.0Hz). ¹³ C NMR (125MHz , CDCl ₃ ) δ144.25, 141.79, 130.32 (q, J=32.4Hz), 127.94, 126.38, 126.23 (q, J=3.5Hz), 124.43 (q, J=270.4Hz).Anal.Calcd for C ₂₇ H ₁₅ F ₉ : C, 63.54; H, 2.96. Found: C, 63.59; H, 2.95.

Example 6

Weigh 1mmol of 2,4,6-tribromophenol, 9mmol of PhB(OH) ₂ , 6mmol of sodium carbonate, and 1.5mol% of palladium acetate in a 25ml small flask, add 3ml of N,N-dimethylformaldehyde Amide and 3.5 ml of water were stirred at 60°C for 14 hours. After the reaction, extract with 4*10ml of ether. After the solvent was spin-dried, the product was obtained with a yield of 97%. Analytical pure samples can be obtained by column separation with petroleum ether/ethyl acetate.

¹ H NMR (500MHz, CDCl ₃ , TMS): δ7.62(m, 6H), 7.53(s, 2H), 7.51(m, 4H), 7.42(m, 4H), 7.32(m, 1H).MS (ESI): m/z=344.9 ([M+Na] ⁺ ).

Example 7

Weigh 1mmol of 2,4,6-tribromophenol, 9mmol of 4-OCH ₃ PhB(OH) ₂ , 6mmol of sodium carbonate, and 1.5mol% of palladium acetate in a 25ml small flask, add 9ml of N,N- Dimethylformamide and 9ml of water were stirred at 55°C for 18 hours. After the reaction, extract with 4*10ml of ether. After the solvent was spin-dried, the product was obtained with a yield of 97%. Analytical pure samples can be obtained by column separation with petroleum ether/ethyl acetate.

¹ H NMR (400MHz, CDCl ₃ , TMS): δ7.53(d, 6H, J=8.8Hz), 7.42(s, 2H), 7.25(d, 4H, J=8.8Hz), 6.95(d, 2H , J=8.8Hz), 5.37 (s, 1H). MS (ESI): m/z=413.0 ([M+H] ⁺ ), 434.9 ([M+Na] ⁺ ).

Claims (9)

1. a preparation method of polyphenyl compounds is characterized in that: with the polyhalogenated aromatic hydrocarbon of 1mmol, the boric acid of 4-9mmol, the sodium carbonate of 3-6mmol, the palladium acetate of 1.0-2.0mol% in reactor, Add 3-9ml of organic solvent and 3-9ml of water, stir at 55°C-80°C for 12-18 hours, extract with ether, and spin the solvent to obtain the product. 2. The preparation method of a polyphenyl compound according to claim 1, characterized in that: the polyhalogenated aromatic hydrocarbon is X ₁ -Ph-X ₂ , and the boric acid is R ₂ PhB(OH) ₂ , wherein , when X ₁ is I, X ₂ is 2-Br, 3-Br or 4-Br, R ₂ is H; when X ₁ is Br, X ₂ is 3-Br or 4-Br, R ₂ is H , OMe or _CF3 . 3. the preparation method of a kind of polybenzene compound according to claim 1, is characterized in that: described polyhalogenated aromatic hydrocarbon is (X ₃ ) ₃ -Ph-R ₁ , boric acid is R ₂ PhB(OH) ₂ , wherein X ₃ is Br, R ₁ is H or OH, and R ₂ is H, OMe or CF ₃ . 4. The preparation method of a polybenzene compound according to claim 1: characterized in that: the amount of the organic solvent is 3-6ml. 5. the preparation method of a kind of polybenzene compound according to claim 1: it is characterized in that: described organic solvent is N, N-dimethylformamide. 6. The preparation method of a kind of polybenzene compound according to claim 1: it is characterized in that: the consumption of described water is 3-6ml. 7. the preparation method of a kind of polybenzene compound according to claim 1 is characterized in that: described alkali is that sodium carbonate consumption is 4-6mmol. 8. The preparation method of a polybenzene compound according to claim 1, characterized in that: the reaction temperature is 60°C-80°C, and the reaction time is 12-16 hours. 9. The preparation method of a polybenzene compound according to claim 1, characterized in that: the amount of palladium acetate is 1.0-1.5% mol.