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A kind of preparation method of inactive olefin aryl compound

A compound and olefin technology, applied in the preparation of organic compounds, chemical instruments and methods, condensation between hydrocarbons and non-hydrocarbons, etc., can solve the problem of olefin arylates that are not easy to generate a single structure, and there are no inactive olefin arylates , less research on arylation reaction, etc., to achieve the effects of reducing environmental pollution and safety hazards, good promotion prospects, and low cost

Active Publication Date: 2021-07-27
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] 1) Most of the inactive olefin substrates used in this type of reaction are chain inactive olefins, and there are very few studies on the arylation reaction of olefins in the ring, and the reactivity is extremely low (such as literature: J.Org.Chem. , 2010, 75, 95–101; Adv. Synth. Catal., 2005, 347, 1569–1575);
[0007] 2) In the arylation process of inactive olefins reported in this type of reaction, it is difficult to avoid the problem that the reaction selectivity is not easy to control, and it is difficult to generate olefin arylates with a single structure (such as literature: J.Am.Chem.Soc., 2010 , 132, 13981–13983; Chem.Sci., 2017, 8, 5181–5185);
[0008] 3) The reaction conditions of this type are relatively harsh and environmentally unfriendly, and the reaction requires the use of a large amount of environmentally unfriendly high-boiling solvents (such as DMF, 1,4-dioxane, toluene, etc.), under external heating conditions, the number of stirring Hours to tens of hours to complete
But so far, there is no work report on the use of mechanical milling technology for the solvent-free oxidation of Heck reaction to construct inactive olefin arylates

Method used

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  • A kind of preparation method of inactive olefin aryl compound

Examples

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Comparison scheme
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Embodiment 1

[0038] Example 1 Preparation of methyl 1-cyclopentene-1-carboxylate-5-phenyl

[0039] Phenylboronic acid (60.0 mg, 0.5 mmol), methyl 1-cyclopentene-1-carboxylate (63.0 mg, 0.5 mmol), and Pd(OAc) were added to a 50 mL stainless steel grinding jar 2 (11.2mg, 0.05mmol), DDQ (56.7mg, 0.25mmol), trichloroacetic acid (81.5mg, 0.5mmol), then add 2 stainless steel balls with a diameter of 12mm, tighten the grinding jar, and put it into a pendulum grinder , milled at a frequency of 20 Hz for 30 minutes. The progress of the reaction was followed by TLC (sample dissolved in ethyl acetate). After the reaction, the whole reaction mixture was poured out from the grinding tank, the stainless steel ball was taken out, and petroleum ether and ethyl acetate (volume ratio 100:1) were used as eluents, and the mixture was separated by silica gel column chromatography according to the Rf value, The obtained target fraction eluent was evaporated to remove the solvent to obtain methyl 1-phenyl-2-cy...

Embodiment 2

[0040] Example 2 Preparation of methyl 1-cyclopentene-1-carboxylate-5-phenyl

[0041] Phenylboronic acid (60.0 mg, 0.5 mmol), methyl 1-cyclopentene-1-carboxylate (15.8 mg, 0.125 mmol), and Pd(TFA) were added to a 25 mL stainless steel grinding jar 2 (16.6mg, 0.05mmol), DDQ (113.5mg, 0.5mmol), trichloroacetic acid (4.1mg, 0.025mmol), then add 1 stainless steel ball with a diameter of 14mm, tighten the grinding jar, and put it into the vibrating grinder , milled at a frequency of 20 Hz for 30 minutes. The progress of the reaction was followed by TLC (sample dissolved in ethyl acetate). After the reaction, the whole reaction mixture was poured out from the grinding tank, the stainless steel ball was taken out, and petroleum ether and ethyl acetate (volume ratio 100:1) were used as eluents, and the mixture was separated by silica gel column chromatography according to the Rf value, The obtained target fraction eluate was evaporated to remove the solvent to obtain methyl 1-phenyl...

Embodiment 3

[0042] Example 3 Preparation of methyl 1-cyclopentene-1-carboxylate-5-phenyl

[0043] Phenylboronic acid (60.0 mg, 0.5 mmol), methyl 1-cyclopentene-1-carboxylate (31.5 mg, 0.25 mmol), and Pd(OAc) were added to a 50 mL stainless steel grinding jar 2 (11.2 mg, 0.05 mmol), DDQ (113.5 mg, 0.5 mmol), acetic acid (0.6 mg, 0.01 mmol), then 4 stainless steel balls with a diameter of 6 mm were added, the grinding jar was tightened, and placed in a pendulum grinding apparatus, Grind for 30 minutes at a frequency of 10 Hz. The progress of the reaction was followed by TLC (sample dissolved in ethyl acetate). After the reaction, the whole reaction mixture was poured out from the grinding tank, the stainless steel ball was taken out, and petroleum ether and ethyl acetate (volume ratio 100:1) were used as eluents, and the mixture was separated by silica gel column chromatography according to the Rf value, The obtained target fraction eluent was evaporated to remove the solvent to obtain me...

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Abstract

The invention discloses a preparation method of an inactive olefin aryl compound. Using arylboronic acid and an inactive olefin as raw materials, under the action of a palladium catalyst, an additive and / or an oxidizing agent, the oxidation Heck reaction is carried out by mechanical grinding. After the reaction, the mixture is separated and purified to obtain the inactive olefin aryl compound; the present invention uses mechanical grinding for the first time to carry out the oxidation Heck reaction in which the inactive olefin participates, and obtains the original reaction with a good yield (49%-85%) The inactive alkene arylate that cannot be obtained or has a very low yield (0-35%) broadens the selection of alkene substrates; the reaction time is only 25-40 minutes.

Description

[0001] (1) Technical field [0002] The invention relates to a preparation method of an inactive olefin aryl compound, which is an efficient synthesis method by means of solvent-free mechanical grinding. [0003] (2) Background technology [0004] Arylated derivatives of alkenes are widely found in medicines and natural products, and are one of the important organic chemical structures. The preparation methods of such compounds are mainly Heck coupling and oxidative Heck coupling. Among them, the Heck reaction usually uses aryl halide and alkene as substrates, and it is easy to generate environmentally unfriendly halogenated waste during the reaction process. The oxidative Heck reaction has the characteristics of high atom economy and has attracted extensive attention. Usually, the oxidative Heck reaction uses active alkenes as substrates to construct arylates. Because of its low reactivity, it is difficult to realize the olefinic bond insertion process, and it is difficult t...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/343C07C69/74C07C69/757C07C69/75C07C69/618C07C2/86C07C15/44
Inventor 俞静波寿昊文苏为科
Owner ZHEJIANG UNIV OF TECH
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