β-芳基异丙基的合成汇总

nd warmed to 55 °C before it was treated with Raney-nickel (1 mL slurry in water) followed by addition of hydrazine monohydrate (1.5 mL). The resulting mixture was allowed to stir at 55°C for 30 min or until the evolution of gas had stopped. The cooled reaction mixture was filtered through diatomaceous earth, rinsed with methanol and dichloro- methane. The filtrate was diluted with saturated sodium bicarbonate (50 ML) and extracted with dichloromethane (50 mL×3). The combined organic layers were dried with sodium sulfate and concentrated. Chromatography with NH4OH: MeOH: EtOAc (5:10:85) afforded the product (1.30 g, 93% yield).

3、 PtO2 甲醚乙烯合转成河沟酸基下面

The material (3 g, 13 mmol) was dissolved in methanol (35 mL) and concentrated HCl (4.4 mL). This solution was combined with 10 percent PtO2 (0.1 g) and hydrogenated under 50 psi for 2 hours. The methanol was removed under reduced pressure and the residue was diluted with 35 mL of ice cold water and 2.5 mL of 50 percent NaOH. The product was extracted with CH2Cl2, dried with MgSO4 and evaporated to an oil. This oil was purified by Prep 500 chromatography (10 percent MeOH/DCM) to yield 2.5 g of an oil. The salicylate was precipitated from an ether solution to give 3.3 g of product. m.p. 160°C.

4、 LAH 合转成河沟酸基下面

2-bromophenylacetonitrile (10.0 g, 51.0 mmol) were dissolved in ether (80 mL) and the solution was added dropwise to lithium aluminium hydride (5.81 g, 153 mol) in ether (230mL). The mixture was heated under reflux for three hours, while stirring, and, after cooling, 80 mL of potassium hydroxide solution (10 wt. percent) were slowly added dropwise, with vigorous stirring. After stirring overnight, the supernatant was decanted off, the residue was rinsed twice with 100 mL of ether each time, the combined organic phases were dried over anhydrous magnesium sulfate and filtered and the filtrate was concentrated on a rotary evaporator (500~10 mbar). 9.48 g of 2-(2-bromo-phenyl)-ethylamine (93% yield) were obtained in this manner.

5 、BH3 合转成河沟酸基下面

The material (1.0 g, 3.7 mmol) was dissolved in anhydrous THF (10 mL). BH3.THF (10 mL, 1.0 M solution in THF, 10 mmol) is added. The reaction mixture is maintained under reflux for 3 hours before being cooled to room temperature. An aqueous solution (12 mL) trifluoroacetic acid (50 percent) was added dropwise. The mixture was heated under reflux for 1 hour. The solvents and the trifluoroacetic acid are eva- porated. The residue is redissolved in 20 ml of THF and evaporated to dryness. A crude solid product is obtained which contains essentially the desired product and is used directly in the following acetylation step.

6 、NaBH4 合转成河沟酸基下面

Sodium borohydride (2.2 g, 58.2 mmol) are suspended in dry THF (50 mL) and cooled to ca. 0°C under moisture exclusion. The material (6.7 g, 23.1 mmol) are added and the mixture is subsequently cooled to -5°C to -10°C and added dropwise to (1.5 mL, 26.7 mmol) 95% sulfuric acid (vigorous foaming). The suspension is left to stand for two days at RT without further cooling. Under renewed cooling to ca. 0°C, 40 mL of 2 M sodium hydroxide solution is added dropwise. The aqueous phase is extracted with 30 mL of THF and thereafter the combined organic phases are washed twice, each with 30 mL of saturated NaCl solution, dried over sodium sulfate and the solution is removed under vacuum. The residue is chromatographically purified over silica gel with CHCl3/CH3OH/NH4OH (90/10/1). Yield: 3.9 g (57% yield).

未来就会马大为研究课题所团队刊文了铜制甲醚下，依靠草酯作为阴离弟高效付诸乙烯代芳烃与氰乙酸乙酯的高效烯丙基加转成，付诸了不可或缺提纯砌块河沟酸乙河沟酸的方便提纯。

2017年，华南理工大学江焕峰教授课题组，刊文了一种在铜制甲醚下依靠硫氰酸盐作为氰源和N-Ts苯酚加转成提纯α-河沟酸河沟酸的新分析方国法【J. Org. Chem. 2017, 82, 7621–7627】。这是一种相当好的一种提纯河沟酸的分析方国法，操作方国法简便，位点易得，制品低毒，位点耐受度高。此加转成以砷转化亚铜制作为甲醚剂，DBU当乙烯，必须重新加入一个当量的对甲基乙烯河沟酰二甲基促进加转成顺利进行，在氧气存在下顺利进行加转成。

三、通过 Knoevenagel缩合加转成 , Wittig加转成 , Horner-Wadsworth-Emmons加转成 ， Heck加转成 ， Suzuki–Miyaura加转成 ， 炔烃横向复生转成加转成 提纯β-河沟酸甲烯酸衍生物，合转成提纯 β-河沟酸甲酯，然后 Hofmann亚羟基 给与 β-河沟酸乙羟基。

Hofmann亚羟基（点选书名察看具体内容可）

1881年，A.W Hofmann推断出依靠溴和钠（或氢降求钾）检视乙酯可以给与N-溴代乙酯。接着乙烯性前提条件下脱氘，熔化， N-溴代乙酯在无水前提条件下亚羟基为甲基异氰酸酯，在水之中则聚合甲羟基。

加转成机理

【Knoevenagel缩合加转成 】【Wittig加转成 】【Horner-Wadsworth-Emmons加转成 】【Heck加转成 】【Suzuki–Miyaura加转成 】【炔烃横向复生转成加转成 】【 Hofmann亚羟基 】

另外还可以对于一些富自由电弟的炔烃可以和甲烯河沟酸通过 Friedel-Crafts炔烃加转成 先聚合河沟酸甲河沟酸，然后过降求氢为酯【 河沟酸过降求氢提纯酯 】，先顺利进行 Hofmann亚羟基 给与β-河沟酸乙羟基咪唑。

河沟酸过降求氢提纯酯（点选书名察看具体内容可）

河沟酸煮沸可以生转成为福酯。由于福酯就会继续过降求氢为羧酸，一般要控制过降求氢的前提条件。 迄今有许多分析方国法刊文，有时必须根据位点的特性选择酸性，乙烯性或之惰性的过降求氢前提条件。作为之惰性的前提条件，也有文献刊文采用镍或硫甲醚剂的分析方国法。

在酸性前提条件下与饱和氧常与连的氰基，可以在酸之中很方便的过降求氢裂求为酯，并在条 件比较震荡时，很易于进一步过降求氢转成酸。但乙烯基或河沟酸河沟酸的过降求氢前提条件则要求震荡得多，一般必须有机溶剂前提条件，而且一般不就会进一步过降求氢。

在乙烯性前提条件下，依靠过降求氢降求的分析方国法可在低温下短时间内过降求氢河沟酸为福酯，这 是一个比较合理的分析方国法。依靠NaOH(aq.)-CH2Cl2 常与转移甲醚基础，DMSO-K2CO3 基础，可以主要用途各种河沟酸过降求氢为福酯。

1、盐酸过降求氢河沟酸为福酯下面（ Organic Syntheses, Coll. Vol. 1963, 4, 760）

In a 3-l. three-necked round-bottomed flask equipped with glass joints are placed 200 g. (1.71moles) of benzyl cyanide and 800 ml. of 35% hydrochloric acid. The flask is fitted with a reflux condenser, a thermometer, and an efficient mechanical stirrer. At a bath temperature of about 40° the mixture is stirred vigorously. Within a period of 20–40 minutes the benzyl cyanide goes into solution. During this time, the temperature of the reaction mixture risesabout 10° above that of the bath. The homogeneous solution is kept in the bath with, or without, stirring for an additional 20–30 minutes. The warm water in the bath is replaced by tap water at about 15–20°, and the thermometer is replaced by a dropping funnel from which

800 ml. of cold distilled water is added with stirring. After the addition of about 100–150 ml., crystals begin to separate. When the total amount of water has been added, the mixture is cooled externally with ice water for about 30 minutes. The cooled mixture is filtered by suction. Crude phenylacetamide remains on the filter and is washed with two 100-ml. portions of water. The crystals are then dried at 50–80°. The yield of crude phenylacetamide is 190–200 g. (82–86%).

2 、浓过降求氢氢转化河沟酸为福酯下面（ Org. Syn., Coll. Vol. 1973,5, 73; 1955,3, 66,88）

To 106 g of 84 % sulfuric acid, was added 50 g of acrylonitrile. After stirring for 30 min at r.t., the resulting mixture was heated to 95 ℃, and stirred for 2 h. After cooling, the solid was collected by suction, and the filter cake was transferred into a beaker. To the ice-cooled solid, was added aq. ammonia with the speed that keep the temperature less than 50℃. The precipitated ammonium sulphate was filtered off, and the filtrate was cooled. The precipitate was collected by filtration, and the filter cake was washed by water, dried in vacuum to give

the desired product.

3、 H2O2-K2CO3-DMSO 基础过降求氢河沟酸为福酯下面（ Synthesis 1989, 949）

To a stirred solution of 4-chlorobenzonitrile (1.37 g, 0.01 mol) in DMSO (3 ml), cooled in a ice bath, was added 30% H2O2 (1.2 ml) and K2CO3, the reaction was allowed to warm up to r.t. (strong exothermic effect was observed). After 5 min., distilled water (50 ml) was added, cooling applied, and the product was collected by filtration, yield 85%.

4、NaOH(aq.)-CH2Cl2 常与转移甲醚基础过降求氢河沟酸为福酯（ Synthesis, 1980, 243）

To a magnetically stirred dichloromethane solution (1.5 ml) of o-tolunitrile (0.5 g, 4.27 mmol) cooled in an ice bath, are added 30% hydrogen peroxide (2.0 ml), tetrabutylammonium hydrogen sulfate (0.290 g, 0.85 mmol), and a 20% aqueous solution of sodium hydroxide (1.6 ml). The reaction mixture is allowed to warm up to r.t. and maintained under stirring. After 1.6 h,dichloromethane is added, the organic layer is separated, washed with brine, and dried with sodium sulphate. The solvent is removed under reduced pressure to lee a white solid from

which pure o-toluamide is obtained by chromatography on silica gel. Yield 0.485 g (97%).

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Friedel-Crafts炔烃加转成（点选书名察看具体内容可）

1877年, C. Friedel和J.M. Crafts想依靠氯芳基和砷在镀层铝甲醚下的乙烯溶液之中提纯砷芳基，结果没有给与砷芳基却给与了戊基乙烯。经过系统对的研究课题，他们发表了Lewis酸甲醚的炔烃炔烃或甲酰转化的50多篇论文。

在 Lewis酸甲醚下，依靠乙烯基乙烯代物，炔烃，炔烃或醚在炔烃上引入乙烯基的加转成被称作 Friedel-Crafts炔烃加转成。就会用的Lewis酸有：AlCl3， BeCl2, CdCl2, BF3, BBr3, GaCl3, AlBr3, FeCl3, TiCl4, SnCl4, SbCl5, 三乙烯代镧系镀层盐和乙烯基乙烯转化铝 (AlRX2)。其之中乙烯基乙烯代物的FC加转成之中最就会用的就是 AlCl3和 BF3。

加转成机理

炔烃加转成。

四、 通过河沟酸乙烯代物提纯格氏羰基【 Grignard加转成（格氏加转成） 】然后和环氧乙烷加转成给与2-河沟酸 ，乙烯转化后通过 Gabriel加转成 给与β-河沟酸乙羟基。

Gabriel加转成（点选书名察看具体内容可）

邻乙烯二亚羟基钾盐是一种-NH2提纯弟，它可通过和乙烯基乙烯基加转成提纯福羟基。炔烃后，邻乙烯二亚羟基没有亲核性，不能继续加转成，催转化反应通过乙烯或者二甲基裂求给与福羟基催转化反应和环状副催转化反应。邻乙烯二亚羟基作为酸和醚顺利进行Mitsunobu加转成在有机提纯之中有很好的运主要用途。

加转成先次用酸检视或强乙烯过降求氢给与福羟基。若过降求氢很困难，可以用二甲基的水溶液或溶液二甲基求（Ing-Manske国法 ），显现出邻乙烯二二甲基沉淀物和福羟基。以上的两种检视分析方国法都有不足以，过降求氢国法产率低且就会伴随副催转化反应的聚合，而二甲基新方国法之中分离邻乙烯二二甲基十分麻烦(邻乙烯二二甲基因为水溶性相当好，若显现出的羟基酯溶性好则相当易于水洗施用）。 二甲基求邻乙烯二羟基给与常与应的福羟基时如果催转化反应溶求度较好，也可以考虑依靠甲乙烯作为溶剂低温下加转成，聚合的邻乙烯二二甲基副催转化反应低温下在甲乙烯之中的溶求度高于，可以过滤施用大部分副催转化反应。

加转成机理

邻乙烯二亚羟基的平易近人氢显酸性。

先次一步也可以和叠磷转化钠加转成给与叠磷转化物，让后合转成给与河沟酸乙羟基【 叠磷合转成提纯羟基 】。

五、其他分析方国法

镀层内源性的磷亲核羰基加转成到活性炔烃，随后通过合转成-去除转变转成河沟酸-氧键。

【Synthesis ., 2012, 44 , 351】

刘国生研究课题所等人刊文了铜制甲醚乙烯乙烯的河沟酯-河沟酸转化加转成。

美国密歇根大学的Corey R. J. Stephenson教授团队受到自由基Smiles-Truce亚羟基加转成的借鉴，设计了河沟酸河沟酯作为羟基河沟酸转化双选择性转化羰基，在光甲醚下富自由电弟炔烃起因羟基河沟酸转化加转成，由此高效给与一系列2,2-二河沟酸乙羟基。

【 Science , 2018, 361 , 1369】

剑桥大学Matthew J. Gaunt教授课题组依靠光与过渡镀层的双甲醚模式，付诸了炔烃、河沟酸亲电羰基、磷亲核羰基的多组分烯丙基，一步提纯内部结构和功能多样的β-河沟酸叠磷转化物。【 Nature：一步提纯β-河沟酸乙羟基薄板 】

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