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Methods of preparing alpha,beta-unsaturated or alpha-halo ketones and aldehydes

A technology of unsaturated and brominated ketones, which is applied in the field of compounds for producing dehydrogenation and perfume technology, can solve the problems such as unreported enol acetate

Inactive Publication Date: 2017-07-28
INTERNATIONAL FLAVORS & FRAGRANCES
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Although copper(II) halides have been known to effect α-bromination or chlorination of ketones for more than half a century (see, e.g., Kosower, E.M. et al., J.Org.Chem. 1963, 28, 633-638; Kosower, E.M. et al., J.Org.Chem.1963,28,630-633; Kochi, J.K., J.Am.Chem.Soc.1955,77,5274-5278), but the oxidation of enol acetate by copper salts has not have been reported or used to achieve such desired chemical transformations on a commercial scale

Method used

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  • Methods of preparing alpha,beta-unsaturated or alpha-halo ketones and aldehydes
  • Methods of preparing alpha,beta-unsaturated or alpha-halo ketones and aldehydes
  • Methods of preparing alpha,beta-unsaturated or alpha-halo ketones and aldehydes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0180] Example 1. Methyl 2-(3-acetoxy-2-pentylcyclopent-2-en-1-yl)acetate (1a)

[0181]

[0182] Light brown liquid (5 mmol scale, 1.31 g, 98%). 1 H NMR (400MHz, CDCl 3)δ3.70(s, 3H), 3.07(m, 1H), 2.56(dd, J=4.4, 14.8Hz, 1H), 2.48(m, 2H), 2.14(s, 3H), 2.07-2.24(m , 3H), 1.80(m, 1H), 1.63(m, 1H), 1.42(m, 1H), 1.27(m.5H), 0.90(t, J=7.9Hz, 3H)ppm; 13 C NMR (100MHz, CDCl 3 )δ C 173.3, 168.6, 145.2, 128.3, 51.5, 39.5, 38.6, 31.7, 29.6, 27.1, 26.7, 24.4, 22.4, 20.8, 14.0ppm; FT-IR v max 1008(m), 1204(s), 1368(m), 1436(w), 1737(s), 2930(w)cm -1 ; GC-MS R t 4.79min, m / z 268[M] + , 226[M-Ac] + .

Embodiment 2

[0183] Example 2. 3-Methyl-2-pentylcyclopent-1-en-1-yl acetate (2a)

[0184]

[0185] The starting material was obtained by the organocuprate conjugate addition of 2-pentylcyclopent-2-enone (Ravid, U. and Ikan, R.J.Org.Chem. 1974, 78, 2637-2639). Pale yellow liquid (2 mmol scale, 375 mg, 86%), (3:1 isomer ratio). 1 H NMR (400MHz, CDCl 3 )δ2.70(m, 1H), 2.45(m, 2H), 2.16(s, 3H), 2.15-1.81(m, 2H), 1.51-1.22(m, 8H), 1.05(d, J=6.9Hz , 3H), 0.90 (t, J=7.0Hz, 3H) ppm; 13 C NMR (100MHz, CDCl 3 )δ C 168.8, 143.8, 130.8, 37.3, 31.7, 29.7, 29.4, 26.7, 24.4, 22.4, 20.8, 19.6, 14.0ppm; FT-IR v max 1202(s), 1180(s), 1369(w), 1756(m), 2859(w), 2929(w), 2956(w)cm -1 ; GC-MS R t 3.85min, m / z210[M] + , 168[M-Ac] + .

Embodiment 3

[0186] Example 3. 2-Pentylcyclopent-1-en 1-yl acetate (3a)

[0187]

[0188] The starting material was obtained by hydrogenation of 2-pentylcyclopent-2-enone (aldol product of cyclopentanone and valeraldehyde). Colorless liquid (2.5 mmol scale, 295 mg, 70%), (8:1 isomer ratio). 1 H NMR (400MHz, CDCl 3 )δ2.48(m, 2H), 2.31(m, 2H), 2.17(s, 3H), 2.03-1.88(m, 4H), 1.42-1.21(m, 6H), 0.90(t, J=7.1Hz , 3H)ppm. 13 C NMR (100MHz, CDCl 3 )δ C 168.9, 143.8, 126.9, 31.6, 31.1, 31.0, 26.8, 26.4, 22.5, 20.8, 19.8, 14.0ppm; FT-IR v max 1210(s), 1739(s), 2859(w), 2930(m), 2956(m)cm -1 ;GC-MSR t 3.76min, m / z 196[M] + , 154[M-Ac] + .

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Abstract

Copper (II) bromide mediated oxidation of acylated enol and use of the reaction in the synthesis of alpha,beta-unsaturated or alpha-bromo ketones or aldehydes are disclosed. A method provides an efficient and practical process for manufacturing dehydrohedione (DHH) and many other versatile alpha,beta-unsaturated or alpha-bromo ketones or aldehydes in large scales to avoid using precious metal compounds.

Description

[0001] field of invention [0002] The present invention relates to the synthesis of α,β-unsaturated or α-halogenated ketones and aldehydes, in particular by the copper(II) bromide-mediated oxidation of enol acetates, more particularly for the production of Practical methods for dehydrohedione (dehydrohedione) (DHH), a compound widely used in perfumery technology. [0003] Background of the invention [0004] α,β-Unsaturated ketones or aldehydes are important fine chemicals widely used not only in general organic synthesis such as in Michael addition and Diels-Alder reactions, etc. but also in cosmetic and personal care industries. For example, (methyldihydrojasmonate) is an important fragrance ingredient used in many commercial blends. The preparation of α,β-unsaturated ketones or aldehydes, respectively, from more readily available simple ketones and aldehydes by oxidation of the corresponding enolates is known, for example, via the Saegusa oxidation of enol silyl ethers (...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/313C07C69/738C07C45/30C07C49/597C07C49/657C07C49/687C07C49/457C07C49/697C07C49/227C07C49/327C07C49/245C07C37/06C07C39/06C07C49/80C07C49/84C07C45/61
CPCC07C37/06C07C45/002C07C45/30C07C45/61C07C67/313C07C69/738C07C49/597C07C49/657C07C49/687C07C49/457C07C49/697C07C49/227C07C49/327C07C49/245C07C39/06C07C49/603C07C49/80C07C49/84C07C45/54C07C67/00C07C2601/10C07C2601/16C07C2601/14C07C2602/08C07C69/73C07C69/145C07C69/157C07C69/757C07C49/683C07C47/353C07C45/27C07C67/317C07C2601/08
Inventor 伊恩·R·巴克森代尔詹姆斯·S·沙利阿马德奥·费尔南德斯·米兰达安娜·玛丽亚·科拉多·佩雷斯
Owner INTERNATIONAL FLAVORS & FRAGRANCES
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