Keto Ethers. IX. Propoxymethyl Alkyl (or Phenyl) Ketones<sup>1</sup>

Henze, Henry R.; Duff, Virginia B.; Matthews, Wm. H.; Melton, Joe W.; Forman, Eugene O.

doi:10.1021/ja01257a060

Cited by 24 publications

(3 citation statements)

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“…A mixture of trichlorosilane (119 g, 879 mmol) and chloromethyl n -propyl ether , (85.8 g, 790 mmol) was added dropwise at 20 °C within 1 h to a mixture of triethylamine (80.0 g, 791 mmol) and copper(I) chloride (3.80 g, 38.4 mmol) in diethyl ether (450 mL). The reaction mixture was heated under reflux for 2 h and then cooled to 20 °C, and the resulting precipitate was filtered off, washed with diethyl ether (3 × 40 mL), and discarded.…”

Section: Experimental Sectionmentioning

confidence: 99%

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of C_α- and C_γ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe₂(CH₂)_nX (R = Me, Et;n= 1, 3; X = Functional Group)

Berkefeld

Guerra²,

Bertermann

et al. 2014

Organometallics

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To understand the silicon α-effect in terms of an enhanced reactivity of the Si−OC bond of α-silanes of the formula type ROSiMe 2 CH 2 X compared to analogous γ-silanes ROSiMe 2 (CH 2 ) 3 X (R = Me, Et; X = functional group), a systematic experimental and computational study of the kinetics and mechanisms of hydrolysis of such compounds was performed. For this purpose, a series of suitable model compounds was synthesized and studied for their hydrolysis kinetics in CD 3 CN/D 2 O under basic and acidic conditions, using 1 H NMR spectroscopy as the analytical tool. To get more information about the reaction mechanisms, the experimental investigations were complemented by computational studies. These investigations demonstrated that the silicon α-effect cannot be rationalized in terms of a special single effect. The reactivities observed rather result from a summation of different components, such as electronic and steric effects, pD dependence, and hydrogen bonds between the functional group (or even protonated functional group) and the alkoxy leaving group. Therefore, the term "silicon α-effect" should not be used furthermore to explain the hydrolysis reactivity at the silicon atom of alkoxyorganylsilanes with functional groups in αor γ-position of the organyl groups (so-called αor γ-silanes).

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Section: Experimental Sectionmentioning

confidence: 99%

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of C_α- and C_γ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe₂(CH₂)_nX (R = Me, Et;n= 1, 3; X = Functional Group)

Berkefeld

Guerra²,

Bertermann

et al. 2014

Organometallics

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“…, O-Propylformocholine perchloraie.-Chloromethyl n-propyl ether, prepared from n-propanol, formaldehyde, and hydrogen chloride (Henze, Duff, Matthews, Melton, and Forman, 1942) (ii) Furfuryldimethylamine was prepared from furfural as described by Moore (1949) and 5-methylfurfuryldimethylamine from 2-methylfuran (sylvan) by the method of Holdren and Hixon (1946) …”

Section: Ketone Seriesmentioning

confidence: 99%

Studies on the Structure‐action Relationships of the Choline Group

Ing

Kordik

Williams

1952

British Journal of Pharmacology and Chemotherapy

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“…Particularly with respect to the stability of the protecting groups towards acid, this was expected to be the key step of the sequence. Because of the high reactivity towards nucleophiles and air moisture21 (neighbouring group effect), as well as the toxicity22 of the chloromethyl ether fragment, step (ii) would be directly followed by nucleophilic substitution with NaN 3 [step (iii)]. The final step (iv) should then be a preferably mild deprotection, leading to the alcohol or amine.…”

Section: Resultsmentioning

confidence: 99%

Evaluation of an Intramolecular Approach for the Synthesis of the Elusive C₅₈N₂ Heterofullerene Family

2008

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A new approach towards the synthesis of the elusive heterofullerene C 58 N 2 is presented. The synthetic strategy is based on the intramolecular 1,3-dipolar cycloaddition of a spacerlinked azide to a monoazaheterofullerene (C 59 N) core. Since this cycloaddition can theoretically result in 16 different isomeric products, the design of the spacer moiety was based on extensive molecular modelling. Two fundamental synthetic routes towards suitably functionalized C 59 N derivatives were designed and carried out. Subsequent one-pot experiments, each making use of the same conditions as had previously

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Keto Ethers. IX. Propoxymethyl Alkyl (or Phenyl) Ketones¹

Cited by 24 publications

References 0 publications

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of C_α- and C_γ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe₂(CH₂)_nX (R = Me, Et;n= 1, 3; X = Functional Group)

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of C_α- and C_γ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe₂(CH₂)_nX (R = Me, Et;n= 1, 3; X = Functional Group)

Studies on the Structure‐action Relationships of the Choline Group

Evaluation of an Intramolecular Approach for the Synthesis of the Elusive C₅₈N₂ Heterofullerene Family

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Keto Ethers. IX. Propoxymethyl Alkyl (or Phenyl) Ketones1

Cited by 24 publications

References 0 publications

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of Cα- and Cγ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe2(CH2)nX (R = Me, Et;n= 1, 3; X = Functional Group)

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of Cα- and Cγ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe2(CH2)nX (R = Me, Et;n= 1, 3; X = Functional Group)

Studies on the Structure‐action Relationships of the Choline Group

Evaluation of an Intramolecular Approach for the Synthesis of the Elusive C58N2 Heterofullerene Family

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Keto Ethers. IX. Propoxymethyl Alkyl (or Phenyl) Ketones¹

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of C_α- and C_γ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe₂(CH₂)_nX (R = Me, Et;n= 1, 3; X = Functional Group)

Silicon α-Effect: A Systematic Experimental and Computational Study of the Hydrolysis of C_α- and C_γ-Functionalized Alkoxytriorganylsilanes of the Formula Type ROSiMe₂(CH₂)_nX (R = Me, Et;n= 1, 3; X = Functional Group)

Evaluation of an Intramolecular Approach for the Synthesis of the Elusive C₅₈N₂ Heterofullerene Family