在复合物中可逆添加基因的化二胺联结体的化物复合物
Igor L Fedushkin1, Alexander S Nikipelov, Konstantin A Lyssenko
1G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, Tropinina str 49, 603950 Nizhny Novgorod, Russian Federation. igorfed@iomc.ras.ru
Journal of the American Chemical Society
|May 22, 2010
概括
基因可逆地增加复合体,形成新的碳-碳和碳-键. 阿尔基因消除温度取决于特定的附加物,其中一些消除在100°C以下,另一些接近200°C.
科学领域:
- 有机金属化学 有机金属化学
- 协调化学 协调化学
- 主群 化学 化学
背景情况:
- 该dpp-Bian配体与各种金属形成稳定的复合物.
- 复合物因其独特的反应性而引起人们的兴趣.
- 基环添加反应是有机合成的基础.
研究的目的:
- 为了研究-dpp-Bian复合物中可逆添加的基.
- 为了描述由此产生的有机添加物.
- 为了确定这些添加物的热稳定性和消除行为.
主要方法:
- -dpp-Bian复合物的合成.
- 复合物的与不同基因的反应.
- 使用光谱技术 (例如NMR) 进行产品的表征.
- 热分析以确定消除温度.
主要成果:
- 观察到各种基因可逆添加到复合物中.
- 在Ga-N-C碎片中形成了新的碳-碳和碳-键.
- 根据它们的热稳定性,确定了两种类型的添加物.
- 对于一些添加物来说,完全的基消除发生在100°C以下,而对于其他添加物则在200°C左右.
结论:
- -dpp-Bian系统为可逆基因功能化提供了一个多功能平台.
- 基的电子和硬质性质影响了添加物的稳定性.
- 这种反应性为控制的基释放或进一步的转化提供了潜力.
相关概念视频
02:38Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
02:34Preparation of Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
02:35Electrophilic Addition to Alkynes: Hydrohalogenation
Electrophilic addition of hydrogen halides, HX (X = Cl, Br or I) to alkenes forms alkyl halides as per Markovnikov's rule, where the hydrogen gets added to the less substituted carbon of the double bond. Hydrohalogenation of alkynes takes place in a similar manner, with the first addition of HX forming a vinyl halide and the second giving a geminal dihalide.
02:27Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
01:14Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
01:15Acid Halides to Alcohols: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert acid halides to tertiary alcohols. The reaction requires two equivalents of the Grignard reagent and proceeds via a ketone intermediate.
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...