Friedel-Crafts Alkylation of Substituted Benzenes by Allyldichlorosilane

Lee, Bong Woo; Yoo, Bok Ryul; Kim, Sunil; Jung, Il Nam

doi:10.1021/om00016a038

Cited by 21 publications

(17 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since the allylsilylated products obtained from the allylsilylation of alkenes still have a double bond at the terminus, a continuous polyallylsilylation of alkenes with allylsilanes was expected to give polyallylsilylation products. The reaction of 4-alkyl-5-silyl-1-pentenes 3b-d, prepared by the allylsilylation of terminal alkenes 2a-c, with 1.2 molar equiv of allylsilanes 1a,b in the presence of anhydrous aluminum chloride and trimethylchlorosilane activator [10][11][12] in organic solvents or neat at 40 o C gave as the major products the unusual allylsilylation products, 2-alkyl-8,8-dimethyl-4-(trimethylsilylmethyl)-8-silanon-1-enes 4a'-d', in addition to polymeric materials. Compounds 4a'-d' are different from the previously reported allylsilylation products, [13][14][15][16] and have a double bond on the carbon with the R 1 group but not on the carbon with R 2 (eq 6).…”

Section: -(Trimethylsilyl)-1-pentenementioning

confidence: 99%

“…10,11 The reactivity of allylsilanes increased as the number of chlorine atoms on the silicon increased, but decreased as the number of methyl groups increased. 12 Surprisingly, allyltrimethylsilane did not give the alkylation product but instead dimerized to give 6,6-dimethyl-4-(trimethylsilylmethyl)-6-silahept-1-ene.…”

Section: Introductionmentioning

confidence: 99%

“…During the alkylation studies using allylsilanes in the presence of aluminum chloride as catalyst, we compared the relative reactivities of allylsilane compounds in the synthesis of 3-aryl-1,1-dichlorosilabutanes. 10,11 The reactivity of allylsilanes increased as the number of chlorine atoms on the silicon increased, but decreased as the number of methyl groups increased.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Jung¹,

Yoo²

1999

Synlett

Self Cite

View full text Add to dashboard Cite

The reactions of allylsilanes with unsaturated hydrocarbons such as alkenes and alkynes in the presence of Lewis acid catalyst give regio-and stereospecific trans-allylsilylated products in good yields. In the allylsilylations of terminal alkenes and alkynes, the silyl group adds to the terminal carbon and the allyl group adds to the inner carbon of the multiple bonds. Reaction with cyclic olefins gives allylsilylated products having the silyl and allyl groups in trans positions. In allylsilylations with the stereohomogeneous (Z)crotyltrimethylsilane, an allylic inversion is observed indicating a stepwise allylsilylation process. The reaction of conjugated dienes with allylsilanes gives [3+2] annulation products having the silyl and the vinyl groups in trans positions on the ring. Allylsilylation of 5-(trimethylsilyl)-1-pentenes gives unusual allylsilylated products through an intramolecular 1,5-hydride rearrangement reaction in the normal allylsilylated products. All results are consistent with the involvement of silylenium ions in the allylsilylations. 1 Introduction 2 Allylsilylation of Alkenes 2.1 Linear Alkenes 2.2 Cyclic Alkenes 2.3 5-(Trimethylsilyl)-1-pentene 3 Allylsilylation and Intramolecular Cyclization of Diallylsilanes 4 Allylsilylation and [3+2] Cycloaddition of Conjugated Dienes 4.1 Linear Conjugated Dienes 4.2 Cyclic Conjugated Dienes 5 Allylsilylation of Alkynes 5.1 Terminal Alkynes 5.2

show abstract

Section: -(Trimethylsilyl)-1-pentenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Jung¹,

Yoo²

1999

Synlett

Self Cite

View full text Add to dashboard Cite

show abstract

“…Nametkin et al first reported that the reaction of substituted benzenes with alkenylsilanes such as allylsilanes and vinylsilanes afforded mono- and bis(silylethyl)benzene derivatives . We also reported detailed information on the Friedel−Crafts type alkylation of substituted benzenes with allyldichlorosilane, including relative reaction rates and product isomer distribution . In an extension of this study, the polyalkylation of benzene with allylchlorosilanes was attempted but trialkylated products were the most highly alkylated compounds obtained, perhaps because of steric hindrance due to the bulky silyl-containing isopropyl groups .…”

Section: Introductionmentioning

confidence: 81%

Syntheses and Structures of Silyl-Group-Containing Hexaalkylated Benzenes

et al. 1997

Self Cite

View full text Add to dashboard Cite

Friedel−Crafts alkylation of vinyldichloromethylsilane to benzene in the presence of aluminum chloride catalyst at room temperature gave hexakis((dichloromethylsilyl)ethyl)benzene (1) in 56% yield, along with small amounts of less alkylated products. 1 was easily converted to the corresponding compounds, C6(CH2CH2SiMeR2)6; (5 (R = OCH3), 6 (R = H), 7 (R = CH3), 8 (R = vinyl), 9 (R = allyl), 10 (R = ethynyl), and 11 (R = benzyl)) by reaction with the appropriate nucleophilic reagents. The molecular structures of hexakis((methylsilylethyl)benzene (6) and the solvent adducts of hexakis((trimethylsilyl)ethyl)benzene (7·2CH2Cl2) and hexakis((dibenzylmethylsilyl)ethyl)benzene (11·2CHCl3) have been determined by X-ray diffraction studies. Each dichloromethane and chloroform molecule formed C−H···aryl hydrogen bonds, one above and one below, to the ring centroid. The distances between the carbon and the ring centroid were 3.469 and 3.466 Å for CH2Cl2 and CHCl3, respectively.

show abstract

“…However, it is difficult to obtain anthracenylchlorosilanes having reactive chlorine atoms on the silicon by this method because of the strong reactivity of organometallic reagents toward the coupling reaction. 7 We have previously reported the Friedel-Crafts alkylations of simple ring compounds such as benzene derivatives, [8][9][10][11] ferrocene, 12 and biphenyl 7 with organosilicon compounds such as allylchlorosilanes, vinylchlorosilanes, and (ω-chloroalkyl)chlorosilanes in the presence of Lewis acid catalysts to give (phenylalkyl)chlorosilanes with Si-Cl bonds. 13 However, the reaction of poly-annulated anthracene with vinylchlorosilanes in the presence of Lewis acid catalyst was not successful because of the deactivation of catalyst by complexation with anthracene ring.…”

Section: Introductionmentioning

confidence: 99%

Friedel-Crafts Type alkylation of 1,2,3,4,5,6,7,8,-Octahydroanthracene with Vinylchlorosilanes:Synthesis of Mono,Bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8,-Octahydroanthracenes

Kong¹,

Lee²,

Yoo³

et al. 2002

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

Friedel-Crafts alkylation reaction of an isomeric mixture of 1,2,3,4,5,6,7,8-(2) and 1,2,3,4,5,6,7,8-octahydrophenanthrene (2') with excess vinylchlorosilanes such as vinyl(methyl)dichlorosilane (1a) and vinyltrichlorosilane (1b) in the presence of aluminum chloride catalyst at 80 o C gives only one dialkylated products, 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthrenes [(Cl 2 XSiCH 2 CH 2 ) 2 C 14 H 16 : X = Me (4a), Cl (4b)] in good yields, but 9,10-bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydrophenanthrenes are not obtained. However, monoalkylation of 2 with 1 affords a mixture of both isomeric compounds, 9-[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8-octahydroanthracenes 3 and -phenanthrenes 3'. The yield of product 3' is always higher than that of 3. When a mixture of 3 and 3' is alkylated again with 1, only product 4 without phenanthrene type compounds is obtained, indicating that the isomerizations between 2 and 2', or 3 and 3' occur under the alkylation condition. The alkylation with dimethylvinylchlorosilane or trimethylvinylsilane did not proceed. The structure of 4a is determined by X-ray single crystal diffraction analysis.

show abstract

Friedel-Crafts Alkylation of Substituted Benzenes by Allyldichlorosilane

Cited by 21 publications

References 0 publications

Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Lewis Acid-Catalyzed Regio- and Stereoselective Allylsilation of Simple Unsaturated Hydrocarbons

Syntheses and Structures of Silyl-Group-Containing Hexaalkylated Benzenes

Friedel-Crafts Type alkylation of 1,2,3,4,5,6,7,8,-Octahydroanthracene with Vinylchlorosilanes:Synthesis of Mono,Bis[2-(chlorosilyl)ethyl]-1,2,3,4,5,6,7,8,-Octahydroanthracenes

Contact Info

Product

Resources

About