4-formyl-valeronitrile | 3619-38-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-formyl-valeronitrile
• 英文别名: 4-Formyl-valeronitril；4-formylvaleronitrile；4-Methyl-5-oxopentanenitrile
• CAS: 3619-38-3
• 化学式: C₆H₉NO
• mdl: MFCD24674101
• 分子量: 111.144
• InChiKey: WZGRZLPEJDJMAI-UHFFFAOYSA-N

物化性质

• 沸点：
  92-94 °C(Press: 3 Torr)
• 密度：
  0.9865 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.666
• 拓扑面积：
  40.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-formyl-valeronitrile 在 lithium aluminium tetrahydride 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 24.5h， 生成 (1S,3S,9R,9aR)-1,3,9-trimethyl-1,3,4,6,7,8,9,9a-octahydroquinolizin-2-one
  参考文献：
  名称：

  Total Synthesis of Petrosin, Petrosin A, and Petrosin B

  摘要：

  The petrosins are a family of marine alkaloids that includes the chiral, racemic isomer petrosin (1), the meso isomer petrosin A (2), and the chiral, scalemic isomer petrosin B (3). Monte Carlo molecular mechanics calculations indicated that petrosin (1) is the most stable isomer of the group, suggesting that it might be synthesized by a route that utilizes thermodynamic control for establishing the relative configurations of the eight stereocenters. The model synthesis summarized in Scheme 1 showed that intramolecular Mannich condensation is a viable route to the quinolizidone subunit of the petrosins and that this synthesis gives isomer 5, having the relative configuration found in petrosin and petrosin A, as the kinetic product. Equilibration studies with this isomer afforded an approximate equimolar mixture of 5 and diastereomer 6, having the relative configuration found in one of the two quinolizidone milts of petrosin B. On the basis of this model study, a "stereo-uncontrolled" synthesis of petrosin was carried out, as summarized in Schemes 3-5. The key step of this synthesis is a "double-barrelled" intramolecular Mannich condensation of a diamino keto dialdehyde. This transformation provides crystalline petrosin in 23% yield, along with about 37% of a mixture of petrosin diastereomers. Although simple acid- and Lewis acid-mediated equilibrations of this mixture of diastereomers were not successful, the derived mixture of bis-butylimines undergoes equilibration upon treatment with protic acid to give a mixture that is greatly enriched in petrosin, relative to the other isomers. Crystallization of this equilibration mixture provided another 10% of petrosin, bringing the overall yield of petrosin to 33%. In the course of the equilibration studies, pure samples of petrosin A (2), petrosin B (3), and petrosin B' (7) were isolated and characterized.

  DOI：

  10.1021/jo9801768
• 作为产物：
  描述：

  2-亚甲基-4-氰基丁醛 在 palladium on activated charcoal 氢气 作用下， 以 1,4-二氧六环 为溶剂， 生成 4-formyl-valeronitrile
  参考文献：
  名称：

  Weiss,F. et al., Bulletin de la Societe Chimique de France, 1965, p. 490 - 493

  摘要：

  DOI：

文献信息

• METHOD FOR THE CONTROLLED HYDROFORMYLATION AND ISOMERIZATION OF A NITRILE/ESTER/OMEGA UNSATURATED FATTY ACID
  申请人：ARKEMA FRANCE

  公开号：US20160115120A1

  公开（公告）日：2016-04-28

  A method to synthesize a fatty nitrile/ester aldehyde comprising the following steps: 1) hydroformylation of a ω-unsaturated fatty nitrile/ester/acid substrate under particular conditions of partial pressure, temperature, reaction time, conversion rate of the ω-unsaturated fatty nitrile/ester/acid reactant, catalyst, [substrate]/[metal] molar ratio and [ligand]/[metal] molar ratio so as after the reaction to obtain: a hydroformylation product comprising at least one fatty nitrile/ester/acid aldehyde of formula: OHC—(CH 2 ) r+2 —R, and an isomerate comprising at least one fatty nitrile/ester/acid isomer with internal unsaturation in which at least 80% of the internal isomer(s) of the isomerate are formed of the ω-1 unsaturated isomer of formula CH 3 —CH═CH—(CH 2 ) r−1 —R; followed by: 2) separation and recovery of the fatty nitrile/ester/acid aldehyde and of the isomerate.

  一种合成脂肪酸腈/酯醛的方法，包括以下步骤： 1）在特定的分压、温度、反应时间、ω-不饱和脂肪酸腈/酯/酸底物的转化率、催化剂、[底物]/[金属]摩尔比和[配体]/[金属]摩尔比条件下，对ω-不饱和脂肪酸腈/酯/酸底物进行氢甲酰化反应，以便在反应后获得： a. 一个氢甲酰化产物，包括至少一种公式为 OHC—(CH2)r+2—R 的脂肪酸腈/酯/酸醛；和 b. 一个异构物，包括至少一种具有内部不饱和的脂肪酸腈/酯/酸异构体，其中至少80%的内部异构体是由公式为 CH3—CH═CH—(CH2)r−1—R 的ω-1不饱和异构体形成的；随后进行： 2）分离和回收脂肪酸腈/酯/酸醛和异构物。
• Production of alkyl 6-aminocaproate
  申请人：E. I. du Pont de Nemours and Company

  公开号：US06365770B1

  公开（公告）日：2002-04-02

  A process for making alkyl 6-aminocaproate by hydroformylating 3-pentenenitrile to produce 3-, 4-, and 5-formylvaleronitrile (FVN mixture), converting the FVN mixture to alkyl 3-, 4-, and 5-cyanovalerate by either oxidative esterification of the FVN mixture or oxidation of the FVN mixture followed by esterification; isolating alkyl 5-cyanovalerate; and hydrogenating the alkyl 5-cyanovalerate to produce alkyl 6-aminocaproate. The resulting alkyl 6-aminocaproate can be cyclized to produce caprolactam.

  一种制备烷基6-氨基己酸酯的方法，包括以下步骤：通过氢甲酰化3-戊烯腈制备3-、4-和5-甲酰基戊二腈（FVN混合物），通过FVN混合物的氧化酯化或氧化后酯化将FVN混合物转化为烷基3-、4-和5-氰基戊酸酯，分离烷基5-氰基戊酸酯，将烷基5-氰基戊酸酯加氢制备烷基6-氨基己酸酯。所得的烷基6-氨基己酸酯可以环化产生己内酰胺。
• Production of 6-aminocaproic acid
  申请人：E.I. du Pont de Nemours and Company

  公开号：US06372939B1

  公开（公告）日：2002-04-16

  A process for making 6-aminocaproic acid by hydroformylating 3-pentenenitrile to produce 3-, 4-, and 5-formylvaleronitrile (FVN mixture), oxidizing the FVN mixture to produce 3-, 4-, and 5-cyanovaleric acid; hydrogenating the resulting product to produce 6-aminocaproic acid, 5-amino-4-methylvaleric acid, and 4-amino-3-ethylbutyric acid; and isolating 6-aminocaproic acid from the reaction product. The resulting 6-aminocaproic acid can be cyclized to produce caprolactam.

  一种制备6-氨基己酸的方法，包括对3-戊烯腈进行氢甲酰化反应，产生3-、4-和5-甲酰戊二腈（FVN混合物），将FVN混合物氧化以产生3-、4-和5-氰基戊酸；加氢得到产物，产生6-氨基己酸、5-氨基-4-甲基戊酸和4-氨基-3-乙基丁酸；从反应产物中分离出6-氨基己酸。所得的6-氨基己酸可环化以产生己内酰胺。
• [EN] PRODUCTION OF 6-AMINOCAPROIC ACID<br/>[FR] PRODUCTION D'ACIDE 6-AMINOCAPROIQUE
  申请人：DU PONT

  公开号：WO2002040440A1

  公开（公告）日：2002-05-23

  A process for making 6-aminocaproic acid by hydroformylating 3-pentenenitrile to produce 3-, 4-, and 5-formylvaleronitrile (FVN mixture), oxidizing the FVN mixture to produce 3-, 4-, and 5-cyanovaleric acid; hydrogenating the resulting product to produce 6-aminocaproic acid, 5-amino-4-methylvaleric acid, and 4-amino-3-ethylbutyric acid; and isolating 6-aminocaproic acid from the reaction product. The resulting 6-aminocaproic acid can be cyclized to produce caprolactam.

  一种制备6-氨基己酸的方法，包括对3-戊烯腈进行氢甲酰化反应，得到3-、4-和5-甲酰基戊腈（FVN混合物），将FVN混合物氧化得到3-、4-和5-氰基戊酸；将产物加氢得到6-氨基己酸、5-氨基-4-甲基戊酸和4-氨基-3-乙基丁酸；然后从反应产物中分离出6-氨基己酸。得到的6-氨基己酸可以环化生成己内酰胺。
• Inhibitors of aspartyl protease
  申请人：Vertex Pharmaceuticals Incorporated

  公开号：US20040127488A1

  公开（公告）日：2004-07-01

  The present invention relates to a novel class of sulfonamides which are aspartyl protease inhibitors. In one embodiment, this invention relates to a novel class of HIV aspartyl protease inhibitors characterized by specific structural and physicochemical features. This invention also relates to pharmaceutical compositions comprising these compounds. The compounds and pharmaceutical compositions of this invention are particularly well suited for inhibiting HIV-1 and HIV-2 protease activity and consequently, may be advantageously used as anti-viral agents against the HIV-1 and HIV-2 viruses. This invention also relates to methods for inhibiting the activity of HIV aspartyl protease using the compounds of this invention and methods for screening compounds for anti-HIV activity.

  本发明涉及一种新型磺酰胺类物质，其为天冬氨酸蛋白酶抑制剂。在一个实施例中，本发明涉及一种新型的HIV天冬氨酸蛋白酶抑制剂，其具有特定的结构和物理化学特征。本发明还涉及包含这些化合物的制药组合物。本发明的化合物和制药组合物特别适用于抑制HIV-1和HIV-2蛋白酶活性，因此可以作为抗HIV-1和HIV-2病毒的抗病毒制剂优势使用。本发明还涉及使用本发明的化合物抑制HIV天冬氨酸蛋白酶活性的方法以及筛选具有抗HIV活性的化合物的方法。