Symmetric olefin compound and synthesis method thereof
By catalyzing the reaction of alcohol compounds with metal catalysts, additives and bases at 160°C, the problems of limited compatibility of olefin synthesis reaction systems and difficulty in catalytic conversion of alcohol substances in the prior art are solved, and the problem of catalytic conversion of alcohol substances is achieved. The synthesis of highly efficient and green symmetrical olefin compounds has high yield and industrial application value.
Patent Information
- Application Number
- CN202410930407.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-11
- Publication Date
- 2025-01-07
AI Technical Summary
The prior art requires pre-preparation of sensitive organometallic activation reagents when synthesizing olefin compounds, resulting in limited compatibility of the reaction system, and the catalytic conversion of alcohols is difficult to achieve, and there is a lack of efficient methods to build olefins with diverse structures.
Zinc triflate as the catalyst and alcohol compounds as raw materials were used, and reacted with metal catalyst, additives and alkali in an organic solvent for 20 hours at 160°C to achieve efficient synthesis of symmetric olefin compounds.
This method is easy to operate, has high yield, wide application range, has the feasibility of industrial production, and does not require special equipment, is simple to operate, has a wide application range, high yield, and is a green and efficient synthetic method.
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Abstract
Description
[Technical field]
[0001] The invention belongs to the field of transition metal catalyzed organic synthesis, and in particular relates to a symmetrical olefin compound and a synthesis method thereof. [Background technology]
[0002] Olefins are commonly found in natural products and functional materials, and are widely used in synthetic chemistry and materials chemistry. Due to the particularity and importance of their structure, they have attracted widespread attention from chemists, and the efficient construction of carbon-carbon double bonds has also become an important research field in organic synthesis.
[0003] In the past few decades, chemists have developed many broad-spectrum chemical reactions, such as Wittig reaction, Peterson olefination, Tebbe olefination, olefin metathesis reaction and other classic reactions to synthesize olefin compounds. Among them, transition metal-catalyzed C-C coupling reaction or carbon metalation of internal alkynes also provide powerful tools for olefin construction and functionalization. However, it requires the pre-preparation of more sensitive organometallic activation reagents, such as nucleophilic reagents such as boric acid, stannane, zincate and Grignard reagent to improve the reaction efficiency, which makes the compatibility of these reaction systems have certain limitations (Chen, X.; et al. Angew. Chem. Int. Ed. 2009, 48, 5094; Cho, SH et al. Chem. Rev. 2011, 40, 5068; Godula, K.; Sames, D. Science. 2006, 312, 67). Therefore, the development of new mild and efficient methodologies to construct structurally diverse olefins remains one of the current research hotspots.
[0004] As a kind of bulk chemical widely existing in various natural products and drug molecules, alcohol compounds are widely used in the field of organic synthesis due to their richness, diversity, stability and other advantages, and are also one of the most ideal starting materials for organic synthesis. However, due to the low reactivity of alcohols, the catalytic conversion of alcohols is still difficult. Therefore, we invented a method of synthesizing symmetrical olefin compounds from alcohol compounds catalyzed by zinc trifluoromethanesulfonate. This method does not require special equipment, is simple to operate, has few additives, has high yield, has a wide range of applications, and has certain industrial application value. At present, there are no public documents and patents about the synthesis of symmetrical olefin compounds catalyzed by zinc trifluoromethanesulfonate at home and abroad. [Summary of the invention]
[0005] The object of the present invention is to provide a method for efficiently synthesizing symmetrical olefin compounds by using zinc trifluoromethanesulfonate as a catalyst and an alcohol compound as a raw material. The method has the advantages of simple operation, high yield, etc. and has certain feasibility for realizing its industrial production.
[0006] In order to achieve the above-mentioned object of the invention, the present invention proposes the following technical solutions:
[0007] A symmetrical olefin compound and a synthesis method thereof, wherein the symmetrical olefin compound I has the following general structural formula:
[0008]
[0009] The structural formula of raw material alcohol ⅠⅠ is as follows:
[0010]
[0011] The synthesis method of compound I is characterized in that alcohol compound II is used as raw material, a metal catalyst, an additive, a base, and an organic solvent are added, and an effective reaction is carried out at a temperature of 160° C. for 20 hours to obtain symmetrical olefin compound I in high yield.
[0012] Wherein R includes but is not limited to phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 4-fluorophenyl, 2-thiophene, and 1-naphthyl.
[0013] Preferably, the metal catalyst may be Zn(OAc) 2 ,Zn(OTf) 2 ,Zn(acac) 2 ,Fe(acac) 3 ,Fe(acac) 2 ,Pd(OAc) 2 The additive may be HP(O)Ph 2 , the base can be NaO t Bu,NaOMe,KO t The organic solvent may be one of Bu, and the organic solvent may be one of 1,4-dioxane, THF, Toluene, and Cyclohexane.
[0014] The synthesis method of a class of symmetrical olefin compounds provided by the present invention is a class of green and efficient synthesis route, and its advantages are: high yield of target product, simple reaction operation, and green and pollution-free.
Brief Description of the Drawings
[0015] The accompanying drawing shows a route map for preparing symmetrical olefin compounds provided by the present invention. [Specific implementation method]
[0016] The present invention provides a method for synthesizing symmetrical olefin compounds, as shown in the attached drawings: an alcohol compound is used as a raw material, 1,4-dioxane is used as a solvent, 12.5 mol% of zinc trifluoromethanesulfonate is used as a catalyst, 1.5 equivalents of diphenylphosphine is used as an additive, and 2.0 equivalents of sodium tert-butoxide is used as a base. The mixture is placed in a reaction container, heated to 160° C. under a nitrogen atmosphere, and reacted for 20 hours. After the reaction is completed, the corresponding target product is separated and purified by column chromatography to obtain the corresponding target product.
[0017] The present invention will be further described below in conjunction with specific preparation examples:
[0018] Preparation Example 1
[0019] 0.2 mmol of benzyl alcohol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160°C for 20 hours under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 98%. 1 H NMR (400 MHz, CDCl 3 ): δ7.52–7.50(m,4H),7.37–7.33(m,4H),7.27–7.22(m,4H),7.10(s,2H). 13 C NMR (100 MHz, CDCl 3 ):δ137.3,128.7,127.6,126.5.
[0020] Preparation Example 2
[0021] 0.2 mmol of 2-methylbenzyl alcohol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160° C. for 20 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 71%. 1 H NMR (400 MHz, CDCl 3 ): δ7.66–7.64(m,2H),7.30–7.23(m,8H),2.48(s,6H). 13 C NMR (100 MHz, CDCl 3 ): δ138.0,138.0,130.4,128.0,127.5,126.2,125.5,19.9.
[0022] Preparation Example 3
[0023] 0.2 mmol of 3-methylbenzyl alcohol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine oxide, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160° C. for 20 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 92%. 1 H NMR (400 MHz, CDCl 3 ): δ7.37–7.34(m,4H),7.30–7.26(m,2H),7.12–7.11(m,4H),2.41(s,6H). 13 C NMR (100 MHz, CDCl 3 ): δ138.2,137.3,128.5,128.3,127.2,126.6,21.4.
[0024] Preparation Example 4
[0025] 0.2 mmol of 4-methylbenzyl alcohol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine oxide, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160° C. for 20 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 90%. 1 H NMR (400 MHz, CDCl 3 ): δ7.43–7.40(m,4H),7.18–7.16(m,4H),7.05(s,2H),2.41(s,6H). 13 C NMR (100 MHz, CDCl 3 ): δ137.2,134.7,129.3,127.6,126.3,21.3.
[0026] Preparation Example 5
[0027] 0.2 mmol of 4-tert-butyl benzyl alcohol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine oxide, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160° C. for 20 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 94%. 1 H NMR (400 MHz, CDCl 3 ): δ7.43–7.40(m,4H),7.18–7.16(m,4H),7.05(s,2H),2.41(s,6H). 13C NMR (100 MHz, CDCl 3 ): δ150.5,134.8,127.7,126.1,125.6,34.6,31.3.
[0028] Preparation Example 6
[0029] 0.2 mmol of 4-methoxybenzyl alcohol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine oxide, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160° C. for 20 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 88%. 1 H NMR (400 MHz, CDCl 3 ): δ7.44–7.41(m,4H),6.93(s,2H),6.90–6.88(m,4H),3.83(s,6H). 13 C NMR (100 MHz, CDCl 3 ): δ159.0,130.5,127.4,126.2,114.1,55.3.
[0030] Preparation Example 7
[0031] 0.2 mmol of 4-fluorobenzyl alcohol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine oxide, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160° C. for 20 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 38%. 1 H NMR (400 MHz, CDCl 3 ): δ7.46–7.40(m,4H),7.21–6.91(m,6H). 13 C NMR (100 MHz, CDCl 3 ): δ162.3 (d, J = 247.5Hz), 133.3, 127.9 (d, J = 14.3Hz), 127.9, 115.6 (d, J = 21.6Hz). 19 F NMR (376 MHz, CDCl 3 )δ-114.08.
[0032] Preparation Example 8
[0033] 0.2 mmol of 1-naphthalene methanol, 12.5 mol% of zinc trifluoromethanesulfonate, 0.3 mmol of diphenylphosphine oxide, 0.4 mmol of sodium tert-butoxide, and 2 mL of 1,4-dioxane were added to a 25 mL tubular reactor, and heated to 160° C. for 20 h under a nitrogen atmosphere. After the reaction, the product was separated and purified by column chromatography, and the separation yield was 46%. 1 H NMR (400 MHz, CDCl 3 ):8.26–8.18(m,2H),7.92–7.76(m,8H),7.56–7.45(m,6H). 13 C NMR (100 MHz, CDCl 3 ): δ135.3,133.7,131.4,129.0,128.6,128.2,126.2,125.9,125.7,123.9,123.8.
[0034] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be based on the attached claims.
Claims
1. A symmetrical olefin compound and a method for synthesizing the same, wherein the general structural formula of the symmetrical olefin compound I is as follows: Wherein R is, but not limited to, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 4-fluorophenyl, 2-thiophene, and 1-naphthyl. The synthesis method of compound I is characterized by: Using alcohol compounds as raw materials, 12.5 mol% zinc trifluoromethanesulfonate as a catalyst, 1.5 equivalents of diphenylphosphine, 2.0 equivalents of sodium tert-butoxide, and 1,4-dioxane as a solvent, the reaction was effectively carried out at 160°C in a nitrogen environment for 20 hours to obtain symmetrical olefin compound Ⅰ in high yield.
2. The synthesis method according to claim 1, characterized in that The structural formula of the raw material alcohol compound II is as follows: Wherein R includes but is not limited to phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, 4-fluorophenyl, 2-thiophene, and 1-naphthyl.
3. The synthesis method according to claim 1, characterized in that In a nitrogen atmosphere, the catalyst is 12.5 mol%, 1,4-dioxane is the solvent; the reaction time is 20 h, and the reaction temperature is 160°C.