PREPARATION METHOD FOR CONJUGATED DIENE COMPOUND

Abstract

The current invention belongs to the technical fields of fine chemicals and related chemistry, and provides a preparation method for butadiene derivatives. Arylacetylenes and derivatives using as raw materials react in an anhydrous organic solvent in the presence of a metal catalyst and an additive, and are converted into 2,3-disubstituted-1,3-butadiene derivatives. The current invention has some beneficial characteristics such as cheap and readily available raw material, mild reaction conditions, environmentally friendly property and possibility of realizing industrialization, and obtains the 1,3-butadiene derivatives in high yields. The 1,3-butadiene derivatives synthesized by this method can be further functionalized into various compounds which have potential applications in development and research of natural products, functional materials and fine chemicals.

Claims

1. A preparation method for conjugated diene compounds, wherein arylacetylene derivatives as raw materials reacting in an anhydrous organic solvent at 20 C.80 C. in the presence of a metal catalyst and an additive for 12-24 hours, and being converted into 1,3-butadiene derivatives, with a synthetic route as follows: ##STR00010## R is selected from alkyl and aryl; a molar ratio of the arylacetylene derivative to the metal catalyst is 1:0.02 to 1:0.1; a molar ratio of the arylacetylene derivative to the additive is 1:0.1 to 1:2; and the molar concentration of the arylacetylene derivative is 0.01 mmol/mL to 2 mmol/mL.

2. The preparation method according to claim 1, wherein the anhydrous organic solvent comprises tetrahydrofuran, 1,2-dimethoxyethane, chloroform, dichloromethane, diethyl ether, dimethyl sulfoxide, carbon tetrachloride, acetone, toluene, 1,4-dioxane, N,N-dimethylformamide and hexane.

3. The preparation method according to claim 1, wherein the catalyst comprises Pd.sub.2dba.sub.3, Pd(PPh.sub.3).sub.4, Pd(PPh.sub.3).sub.2Cl.sub.2, Pd(OAc).sub.2, Pd(TFA).sub.2, PdCl.sub.2, Pd(CH.sub.3CN).sub.2Cl.sub.2 and Pd(acac).sub.2; ligands comprise PPh.sub.3, tri(p-tolyl)phosphine, tri(2-furyl)phosphine, PCy.sub.3, Ph.sub.2P.sup.tBu, P.sup.tBu.sub.3, PEt.sub.3, tri(o-tolyl)phosphine, Me.sub.2PPh and P.sup.nBu; and a molar ratio of the metal catalysts to the ligands is 1:2 to 1:4.

4. The preparation method according to claim 1, wherein the additive comprises additive 1 and additive 2; the additive 1 comprises iron powder, manganese powder, magnesium powder and zinc powder; and the additive 2 comprises toluene-p-sulfonic acid, 2,6-pyridinedicarboxylic acid, trifluoromethanesulfonic acid, trimethylacetic acid, salicylic acid, trifluoroacetic acid, methanesulfonic acid, 2-ethylhexanoic acid, m-nitrobenzoic acid and cinnamic acid.

5. The preparation method according to claim 3, wherein the additive comprises additive 1 and additive 2; the additive 1 comprises iron powder, manganese powder, magnesium powder and zinc powder; and the additive 2 comprises toluene-p-sulfonic acid, 2,6-pyridinedicarboxylic acid, trifluoromethanesulfonic acid, trimethylacetic acid, salicylic acid, trifluoroacetic acid, methanesulfonic acid, 2-ethylhexanoic acid, m-nitrobenzoic acid and cinnamic acid.

Description

DESCRIPTION OF DRAWINGS

[0018] FIG. 1 is a .sup.1H NMR of buta-1,3-diene-2,3-diyldibenzene in example 1.

[0019] FIG. 2 is a .sup.13C NMR of buta-1,3-diene-2,3-diyldibenzene in example 1.

[0020] FIG. 3 is a .sup.1H NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(methylbenzene) in example 2.

[0021] FIG. 4 is a .sup.13C NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(methylbenzene) in example 2.

[0022] FIG. 5 is a .sup.1H NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(methoxybenzene) in example 3.

[0023] FIG. 6 is a .sup.13C NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(methoxybenzene) in example 3.

[0024] FIG. 7 is a .sup.1H NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(fluorobenzene) in example 4.

[0025] FIG. 8 is a .sup.13C NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(fluorobenzene) in example 4.

[0026] FIG. 9 is a .sup.1H NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(bromobenzene) in example 5.

[0027] FIG. 10 is a .sup.13C NMR of 4,4-(buta-1,3-diene-2,3-diyl)bis(bromobenzene) in example 5.

[0028] FIG. 11 is a .sup.1H NMR of 1,1-(buta-1,3-diene-2,3-diylbis(4,1-phenylene))bis(ethan-1-one) in example 6.

[0029] FIG. 12 is a .sup.13C NMR of 1,1-(buta-1,3-diene-2,3-diylbis(4,1-phenylene))bis(ethan-1-one) in example 6.

[0030] FIG. 13 is a .sup.1H NMR of 2,2-(buta-1,3-diene-2,3-diyl)dithiophene in example 7.

[0031] FIG. 14 is a .sup.13C NMR of 2,2-(buta-1,3-diene-2,3-diyl)dithiophene in example 7.

[0032] FIG. 15 is a .sup.1HNMR of 7,8-dimethylenetetradecane in example 8.

[0033] FIG. 16 is a .sup.13C NMR of 7,8-dimethylenetetradecane in example 8.

DETAILED DESCRIPTION

[0034] The preparation method for the 1,3-butadiene derivatives in the current invention has the advantages of low cost of raw material, fewer reaction steps, mild reaction conditions, environmentally friendly property, convenient operation and high reaction yield.

[0035] The current invention is further described below in combination with the specific examples. The examples are only used for illustrating the current invention, not used for limiting the scope of the current invention. Simple replacement or improvement made to the current invention by those skilled in the art belongs to the technical solution protected by the current invention.

Example 1: Synthesis of buta-1,3-diene-2,3-diyldibenzene

[0036] In a 25 mL reactor toluene-p-sulfonic acid (0.029 g, 0.15 mmol), trimethylacetic acid (0.087 g, 0.85 mmol), zinc powder (0.033 g, 0.5 mmol) and Pd(PPh.sub.3).sub.4 (0.023 g, 0.02 mmol) are added; nitrogen is exchanged for three times; then 3 mL of anhydrous dichloromethane is added; arylacetylenes (0.051 g, 0.5 mmol) is added while stirred; and the above mixtures are stirred for 24 h at 25 C. Column chromatography separation (silica gel with 200-300 meshes; eluent, petroleum ether) is conducted to obtain 0.038 g of buta-1,3-diene-2,3-diyldibenzene with a yield of 73%.

##STR00002##

buta-1,3-diene-2,3-diyldibenzene

[0037] Clear crystal; .sup.1H NMR (CDCl.sub.3, 400 MHz) 7.38-7.40 (m, 4H), 7.19-7.27 (m, 6H), 5.53 (s, 2H), 5.30 (s, 2H); .sup.13C NMR (CDCl.sub.3, 100 MHz) 149.9, 140.2, 128.2, 127.6, 116.4 ppm; MS (D) m/z=207, 206, 191, 178, 128, 115, 91.

Example 2: Synthesis of 4,4-(buta-1,3-diene-2,3-diyl)bis(methylbenzene)

[0038] Operation is the same as that in example 1. The 1-ethynyl-4-methylbenzene reacts to produce 0.049 g of 4,4-(buta-1,3-diene-2,3-diyl)bis(methylbenzene) with a yield of 83%.

##STR00003##

4,4-(buta-1,3-diene-2,3-diyl)bis(methylbenzene)

[0039] White solid; .sup.1H NMR (CDCl.sub.3, 400 MHz) 7.28 (d, J=8.0 Hz, 4H), 7.05 (d, J=8.0 Hz, 4H), 5.50 (s, 2H), 5.26 (s, 2H), 2.28 (s, 6H); .sup.13C NMR (CDCl.sub.3, 100 MHz) 149.8, 137.4, 137.2, 128.9, 127.3, 115.4, 21.2 ppm; MS (D) m/z=235, 234, 219, 204, 128, 115, 91

Example 3: Synthesis of 4,4-(buta-1,3-diene-2,3-diyl)bis(methoxybenzene)

[0040] Operation is the same as that in example 1. The 4-methoxyl arylacetylene reacts to produce 0.060 g of 4,4-(buta-1,3-diene-2,3-diyl)bis(methoxybenzene) with a yield of 90%.

##STR00004##

4,4-(buta-1,3-diene-2,3-diyl)bis(methoxybenzene)

[0041] White solid; .sup.1H NMR (CDCl.sub.3, 400 MHz) 7.31 (d, J=8.0 Hz, 4H), 6.78 (d, J=8.0 Hz, 4H), 5.47 (s, 2H), 5.23 (s, 2H), 3.74 (s, 6H); .sup.13C NMR (CDCl.sub.3, 100 MHz) 159.1, 149.4, 132.7, 128.5, 114.3, 113.6, 55.2 ppm; MS (EI) m/z=267, 266, 251, 235, 121

Example 4: Synthesis of 4,4-(buta-1,3-diene-2,3-diyl)bis(fluorobenzene)

[0042] In a 25 mL reactor trifluoromethanesulfonic acid (0.0225 g, 0.15 mmol), trimethylacetic acid (0.087 g, 0.85 mmol), iron powder (0.028 g, 0.5 mmol), Pd.sub.2dba.sub.3 (0.092 g, 0.01 mmol) and PPh.sub.3 (0.011 g, 0.04 mmol) are added; nitrogen is exchanged for three times; then 3 mL of anhydrous acetone is added; 1-ethynyl-4-fluorobenzene (0.061 g, 0.5 mmol) is added while stirred; and the above mixtures are stirred for 24 h at 35 C. Column chromatography separation (silica gel with 200-300 meshes; eluent, petroleum ether) is conducted to obtain 0.045 g of 4,4-(buta-1,3-diene-2,3-diyl)bis(fluorobenzene) with a yield of 73%.

##STR00005##

4,4-(buta-1,3-diene-2,3-diyl)bis(fluorobenzene)

[0043] Colorless oil; .sup.1H NMR (CDCl.sub.3, 400 MHz) 7.30-7.34 (m, 4H), 6.92-6.96 (m, 4H), 5.48 (s, 2H), 5.29 (s, 2H); .sup.13C NMR (CDCl.sub.3, 100 MHz) 163.6, 161.2, 148.8, 136.0 (d, J=3.3 Hz), 129.1 (d, J=8 Hz), 116.3, 115.2, 115.0 ppm; HRMS (EI) m/z calcd. For C.sub.16H.sub.12F.sub.2: 242.0907; found: 242.0911.

Example 5: Synthesis of 4,4-(buta-1,3-diene-2,3-diyl)bis(bromobenzene)

[0044] In a 25 mL reactor trifluoromethanesulfonic acid (0.023 g, 0.15 mmol), trimethylacetic acid (0.087 g, 0.85 mmol), manganese powder (0.027 g, 0 5 mmol), Pd(PPh.sub.3).sub.2Cl.sub.2 (0.014 g, 0.02 mmol) and PPh.sub.3 (0.011 g, 0.04 mmol) are added; nitrogen is exchanged for three times; then 3 mL of anhydrous acetone is added; 1-ethynyl-4-bromobenzene (0.091 g, 0.5 mmol) is added while stirred; and the above mixtures are stirred for 24 h at 20 C. Column chromatography separation (silica gel with 200-300 meshes; eluent, petroleum ether) is conducted to obtain 0.070 g of 4,4-(buta-1,3-diene-2,3-diyl)bis(bromobenzene) with a yield of 77%.

##STR00006##

4,4-(buta-1,3-diene-2,3-diyl)bis(bromobenzene)

[0045] Yellow crystal; .sup.1H NMR (CDCl.sub.3, 400 MHz) 7.38 (d, J=8 Hz, 4H), 7.20 (d, J=8 Hz, 4H), 5.52 (s, 2H), 5.32 (s, 2H); .sup.13C NMR (CDCl.sub.3, 100 MHz) 148.4, 138.7, 131.4, 129.1, 121.8, 117.1 ppm; MS (EI) m/z=366, 364, 362, 338, 336, 334, 283, 204, 101

Example 6: Synthesis of 1,1-(buta-1,3-diene-2,3-diylbis(4,1-phenylene))bis(ethan-1-one)

[0046] In a 25 mL reactor methanesulfonic acid (0.014 g, 0.15 mmol), trimethylacetic acid (0.087 g, 0.85 mmol), manganese powder (0.027 g, 0.5 mmol), tri(2-furyl)phosphine (0.009 g, 0.04 mmol) and Pd(OAc).sub.2 (0.005 g, 0.02 mmol) are added; nitrogen is exchanged for three times; then 3 mL of anhydrous tetrahydrofuran is added; 1-(4-ethynylphenyl)ethan-1-one (0.072 g, 0.5 mmol) is added while stirred; and the above mixtures are stirred for 24 h at 40 C. Column chromatography separation (silica gel with 200-300 meshes; eluent, petroleum ether) is conducted to obtain 0.033 g of 1,1-(buta-1,3-diene-2,3-diylbis(4,1-phenylene))bis(ethan-1-one) with a yield of 62%.

##STR00007##

1,1-(buta-1,3-diene-2,3-diylbis(4,1-phenylene))bis(ethan-1-one)

[0047] White solid; .sup.1H NMR (CDCl.sub.3, 400 MHz) 7.85 (d, J=8 Hz, 2H), 7.45 (d, J=8 Hz, 2H), 5.68 (s, 2H), 5.47 (s, 2H); .sup.13C NMR (CDCl.sub.3, 100 MHz) 197.6, 148.4, 144.3, 136.3, 128.5, 127.6, 118.5, 26.6 ppm; MS: m/z=291 [M+H.sup.+]

Example 7: Synthesis of 2,2-(buta-1,3-diene-2,3-diyl)dithiophene

[0048] In a 25 mL reactor methanesulfonic acid (0.014 g, 0.15 mmol), trifluoroacetic acid (0.097 g, 0.85 mmol), manganese powder (0.027 g, 0.5 mmol), Pd(OAc).sub.2 (0.005 g, 0.02 mmol) and tri(p-tolyl)phosphine (0.012 g, 0.04 mmol) are added; nitrogen is exchanged for three times; then 3 mL of anhydrous tetrahydrofuran is added; 2-ethynylthiophene (0.0541 g, 0.5 mmol) is added while stirred; and the above mixtures are stirred for 24 h at 50 C. Column chromatography separation (silica gel with 200-300 meshes; eluent, petroleum ether) is conducted to obtain 0.034 g of 2,2-(buta-1,3-diene-2,3-diyl)dithiophene with a yield of 62%.

##STR00008##

2,2-(buta-1,3-diene-2,3-diyl)dithiophene

[0049] Colorless oil; .sup.1H NMR (CDCl.sub.3, 400 MHz) 7.16-7.18 (m, 2H), 6.95-6.96 (m, 2H), 6.90-6.92 (in, 2H), 5.63 (s, 2H), 5.26 (s, 2H); .sup.13C NMR (CDCl.sub.3, 100 MHz) 143.6, 142.5, 127.4, 126.1, 124.9, 114.3 ppm; HRMS (EI): m/z calcd. For C.sub.12H.sub.10S.sub.2: 218.0224; found: 218.0227.

Example 8: synthesis of 7,8-dimethylenetetradecane

[0050] In a 25 mL reactor toluene-p-sulfonic acid (0.029 g, 0.15 mmol), trifluoroacetic acid (0.097 g, 0.85 mmol), Zinc powder (0.033 g, 0.5 mmol), PPh.sub.3 (0.011 g, 0.04 mmol) and Pd(acac).sub.2 (0.006 g, 0.02 mmol) are added; nitrogen is exchanged for three times; then 3 mL of anhydrous dichloromethane is added; oct-1-yne (0.055 g, 0.5 mmol) is added while stirred; and the above mixtures are stirred for 24 h at 25 C. Column chromatography separation (silica gel with 200-300 meshes; eluent, petroleum ether) is conducted to obtain 0.043 g of 7,8-dimethylenetetradecane with a yield of 77%.

##STR00009##

7,8-dimethylenetetradecane

[0051] Colorless oil; .sup.1H NMR (400 MHz, CDCl.sub.3): 5.04 (s, 2H), 4.90 (s, 2H), 2.22 (dd, J=7.2, 7.2 Hz, 4H), 1.44-1.39 (m, 4H), 1.32-1.25 (m, 12H), 0.90-0.86 (t, J=6.8 Hz, 6H) ppm. .sup.13C NMR (100 MHz, CDCl.sub.3): 148.1, 111.2, 34.3, 31.8, 29.2, 0.7, 22.7, 14.1 ppm.