5160-99-6Relevant academic research and scientific papers
Catalytic Intermolecular C(sp3)-H Amination: Selective Functionalization of Tertiary C-H Bonds vs Activated Benzylic C-H Bonds
Brunard, Erwan,Boquet, Vincent,Van Elslande, Elsa,Saget, Tanguy,Dauban, Philippe
, p. 6407 - 6412 (2021/05/29)
A catalytic intermolecular amination of nonactivated tertiary C(sp3)-H bonds (BDE of 96 kcal·mol-1) is reported for substrates displaying an activated benzylic site (BDE of 85 kcal·mol-1). The tertiary C(sp3)-H bond is selectively functionalized to afford α,α,α-Trisubstituted amides in high yields. This unusual site-selectivity results from the synergistic combination of Rh2(S-Tfpttl)4, a rhodium(II) complex with a well-defined catalytic pocket, with tert-butylphenol sulfamate (TBPhsNH2), which leads to a discriminating rhodium-bound nitrene species under mild oxidative conditions. This catalytic system is very robust, and the reaction was performed on a 50 mmol scale with only 0.01 mol % of catalyst. The TBPhs group can be removed under mild conditions to afford the corresponding NH-free amines.
Process Research and Scale-Up Synthesis of 3-(4-Isobutyl-2-methylphenyl)propanal, a Safe and Uniquely Performing Perfumery Ingredient
Lovchik, Martin A.,Tse, Chi-Lam,Ellwood, Simon
, p. 2906 - 2914 (2020/12/22)
Ever since the beginning of modern perfumery, muguet (lily-of-the-valley) notes have been sought after and are now found in varying doses in practically every perfume composition, accounting for the warm, soft, and comforting facets of many fragrances. Over the past decades, Lilial and Bourgeonal have evolved to become popular and inexpensive ingredients to satisfy the high demand of such floral odors. However, the search continues for more performing ingredients, especially in this odor family. Through this effort, 3-(4-isobutyl-2-methylphenyl)propanal (Nympheal) was identified as a modern, more performing, and benign alternative to the traditional ingredients. In particular, it outperforms Lilial in a sense that it has a linden blossom, a floral aldehydic odor considered to be more natural in its character. This paper details the challenge to design an efficient synthesis for the multi-kilogram production of the fragrance ingredient Nympheal. The methyl group, strategically placed in the 2-position to ensure the biological safety of the ingredient, also introduced a level of asymmetry into the molecule resulting in regiochemical challenges to identifying potential synthetic routes. Route scouting for this initial scale-up was performed using 1-isobutyl-3-methylbenzene as a feedstock made by continuous dehydrogenation of a mixture of 3- and 5-isobutyl-1-methylcyclohex-1-ene. Different routes were explored for introduction of the propanal moiety including carbonylation, Heck reaction, and Friedel-Crafts reaction. Ultimately, 3.3 kg of Nympheal was prepared by electrophilic bromination of 1-isobutyl-3-methylbenzene, followed by reaction with magnesium and dimethylformamide to give the corresponding benzaldehyde, which was then reacted with ethyl vinyl ether by the procedure from Muller-Cunradi-Pierroh and hydrogenated to give the desired product.
MANUFACTURING METHOD OF ALKYL SUBSTITUTED AROMATIC HYDROCARBON
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Paragraph 0056-0058, (2019/01/22)
PROBLEM TO BE SOLVED: To provide a manufacturing method capable of enhancing conversion ratio of aromatic hydrocarbon of a reaction substance and manufacturing alkyl substituted aromatic hydrocarbon at high selectivity and high yield. SOLUTION: There is provided a manufacturing method of alkyl substituted aromatic hydrocarbon (X-2) including a process for alkylating an alkyl group in aromatic hydrocarbon having the alkyl group having a hydrogen atom at an α position (X-1) with alkene, in which a solid base (D) derived from a composition containing an alkali earth metal compound (A) containing one or more kind of magnesium oxide, magnesium hydroxide, magnesium carbonate, calcium oxide, calcium hydroxide, and calcium carbonate, a potassium compound (B) containing one or more kind of potassium hydroxide, and potassium carbonate, and a metal sodium (C) is used as a reaction catalyst for alkylation. SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
Reductive activation of arenes 21. Reaction of products of two-electron reduction of arenecarbonitriles by alkali metals in liquid ammonia with bromo-and dibromoalkanes
Vaganova,Panteleeva,Yuferov,Rebitva,Shteingarts
, p. 981 - 986 (2008/02/01)
Reductive alkylation of benzonitrile, ortho-, meta-, para-tolunitriles, and 1-naphthonitrile by sequential action of alkali metal and alkyl bromide in liquid ammonia results in corresponding alkylarenes and 1-alkyl-1- cyanocyclohexa-2,5-dienes. The experimental conditions for target synthesis of the specified products are found. A method of synthesis of 1-(ω- bromoalkyl)-1-cyanocyclohexa-2,5-dienes based on the interaction of two-electronic reduction products of aromatic nitriles with α,ω- dibromoalkanes Br(CH2)nBr (n = 3-5) is developed.
