阅读说明：本技术 一种双(1,5-环辛二烯)镍的制备方法 (Preparation method of bis (1, 5-cyclooctadiene) nickel ) 是由 张高鹏 李小安 张宇 朱大川 于 2019-11-29 设计创作，主要内容包括：本发明公开一种双(1,5-环辛二烯)镍的制备方法,包括以下步骤：(1)在无水无氧条件下,向0.5~1.0M无水二乙酰丙酮镍的四氢呋喃溶液中加入1,5-环辛二烯,降温至-78℃,然后再向其中滴加二异丁基氢化铝的有机溶液,加毕后升温至-10~25℃反应1~5h；(2)在惰性气体保护下压滤,得到双(1,5-环辛二烯)镍晶体,然后在惰性气体氛围下避光保存。本发明提供的方法制备双(1,5-环辛二烯)镍反应条件温和、便于工业化批量生产,产品纯度高,收率好。(The invention discloses a preparation method of bis (1, 5-cyclooctadiene) nickel, which comprises the following steps: (1) adding 1, 5-cyclooctadiene into 0.5-1.0M anhydrous nickel diacetylacetonate tetrahydrofuran solution under anhydrous and oxygen-free conditions, cooling to-78 ℃, then dropwise adding an organic solution of diisobutyl aluminum hydride, and heating to-10-25 ℃ for reacting for 1-5 h after the addition is finished; (2) and (3) carrying out filter pressing under the protection of inert gas to obtain bis (1, 5-cyclooctadiene) nickel crystals, and then storing the crystals in a dark place under the atmosphere of inert gas. The method for preparing the bis (1, 5-cyclooctadiene) nickel has mild reaction conditions, is convenient for industrial mass production, and has high product purity and good yield.)

1. A preparation method of bis (1, 5-cyclooctadiene) nickel is characterized by comprising the following steps: the method comprises the following steps:

(1) adding 1, 5-cyclooctadiene into 0.5-1.0M anhydrous nickel diacetylacetonate tetrahydrofuran solution under anhydrous and oxygen-free conditions, cooling to-78 ℃, then dropwise adding an organic solution of diisobutyl aluminum hydride, and heating to-10-25 ℃ for reacting for 1-5 h after the addition is finished;

(2) and (3) carrying out filter pressing under the protection of inert gas to obtain bis (1, 5-cyclooctadiene) nickel crystals, and then storing the crystals in a dark place under the atmosphere of inert gas.

2. The process for preparing bis (1, 5-cyclooctadiene) nickel according to claim 1, wherein: the molar ratio of the anhydrous nickel diacetylacetonate, the 1, 5-cyclooctadiene and the diisobutylaluminum hydride is 1 (4.3-5.5) to 2.0-4.0.

3. The process for producing bis (1, 5-cyclooctadiene) nickel according to claim 1 or 2, characterized in that: in the tetrahydrofuran solution of the anhydrous nickel diacetone, the tetrahydrofuran is subjected to dehydration treatment.

4. The process for producing bis (1, 5-cyclooctadiene) nickel according to claim 1 or 2, characterized in that: the organic solution of diisobutyl aluminum hydride is tetrahydrofuran solution of diisobutyl aluminum hydride, toluene solution of diisobutyl aluminum hydride or n-hexane solution of diisobutyl aluminum hydride.

5. The process for producing bis (1, 5-cyclooctadiene) nickel according to claim 1 or 2, characterized in that: and a sand plate filter pipe is adopted for filter pressing during filter pressing.

6. The process for producing bis (1, 5-cyclooctadiene) nickel according to claim 1 or 2, characterized in that: the inert gas is nitrogen or argon.

Technical Field

The invention belongs to the technical field of organic metal complex preparation, and particularly relates to a preparation method of bis (1, 5-cyclooctadiene) nickel.

Background

Bis (1, 5-cyclooctadiene) nickel as an organometallic complex is not only used directly as a highly efficient zero-valent nickel catalyst in many organic chemical reactions to promote or catalyze some reactions, such as: the bis (1, 5-cyclooctadiene) nickel can promote the carbon-carbon bond coupling reaction of brominated aromatic hydrocarbon to generate biphenyl under mild conditions, and can also catalyze the addition reaction of alkyne to generate bifunctional olefin derivatives. And because the 1, 5-cyclooctadiene ligand is easy to exchange and react with other ligands, the bis (1, 5-cyclooctadiene) nickel is also used as a common nickel source together with other ligands, and the bis (1, 5-cyclooctadiene) nickel is also used as a raw material for synthesizing a plurality of complex organic nickel complexes.

However, since bis (1, 5-cyclooctadiene) nickel is sensitive to light, humidity and air, is a flammable solid, and is difficult to prepare and store, few reports on effective synthesis of bis (1, 5-cyclooctadiene) nickel are made in China at present.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a preparation method of bis (1, 5-cyclooctadiene) nickel, which is simple and low in cost.

A preparation method of bis (1, 5-cyclooctadiene) nickel comprises the following steps:

(1) adding 1, 5-cyclooctadiene into 0.5-1.0M tetrahydrofuran solution of anhydrous nickel diacetone under anhydrous and oxygen-free conditions, cooling to-78 ℃, then dropwise adding organic solution of diisobutyl aluminum hydride, and heating to-10-25 ℃ after adding for reaction for 1-5 h;

(2) and (3) carrying out filter pressing under the protection of inert gas to obtain bis (1, 5-cyclooctadiene) nickel crystals, and then storing the crystals in a dark place under the atmosphere of inert gas.

Preferably, the molar ratio of the anhydrous nickel diacetylacetonate to the 1, 5-cyclooctadiene to the diisobutylaluminum hydride is 1 (4.3-5.5) to (2.0-4.0).

Preferably, in the tetrahydrofuran solution of the anhydrous nickel diacetone, the tetrahydrofuran is subjected to water removal treatment.

Preferably, the organic solution of diisobutylaluminum hydride is a tetrahydrofuran solution of diisobutylaluminum hydride, a toluene solution of diisobutylaluminum hydride, or an n-hexane solution of diisobutylaluminum hydride.

Preferably, the filter pressing is carried out by adopting a sand plate filter pipe.

Preferably, the inert gas is nitrogen or argon.

The invention has the advantages that:

the preparation method of bis (1, 5-cyclooctadiene) nickel provided by the invention has the advantages of simple method, low cost, mild reaction conditions, convenience for industrial mass production, high product purity and good yield.

Detailed Description