Mass spectroscopy of organosilicon compounds. Examples of interaction of the silyl center with remote phenyl groups

Weber, William P.; Willard, Alvin K.; Boettger, Heins G.

doi:10.1021/jo00811a011

Cited by 39 publications

(14 citation statements)

References 7 publications

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“…(Pentadeuterophenyl)acetylene 12 To a mixture of methanol (50 cm 3 ) and water (5 cm 3 ) was added 1-(trimethylsilyl)-2-(pentadeuterophenyl)acetylene (4.89 g, 27.32 mmol). After adding sodium hydroxide (0.32 g, 8.19 mmol, 30 mol%), the reaction mixture was stirred at room temperature for 45 min, at which point the reaction was complete as shown by GC-MS. To the solution were added water (50 cm 3 ) and hexane (50 cm 3 ).…”

Section: -(Trimethylsilyl)-2-(pentadeuterophenyl) Acetylene 12mentioning

confidence: 99%

Time‐resolved resonance Raman study of S₁cis‐stilbene and its deuterated isotopomers

Kwok

Phillips

et al. 2003

J Raman Spectroscopy

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We present the picosecond time-resolved resonance Raman (ps-TR 3 ) spectra of the first excited singlet state (S 1 ) of cis-stilbene (d 0 /, fully deuterated cis-stilbene (d 12 ) and a,a -d 2 -cis-stilbene (d 2 ) measured in hexane at pump and probe wavelengths 267 and 630 nm, respectively. The main observation is that in the lower wavenumber region the spectra are dominated by a second-order overtone progression originating from a 229 cm −1 fundamental band for the S 1 d 0 cis-stilbene. The observed low-wavenumber modes of the excited cis-stilbene are substantially more resonantly enhanced than the modes around 1600 cm −1 .

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Section: -(Trimethylsilyl)-2-(pentadeuterophenyl) Acetylene 12mentioning

confidence: 99%

Time‐resolved resonance Raman study of S₁cis‐stilbene and its deuterated isotopomers

Kwok

Phillips

et al. 2003

J Raman Spectroscopy

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“…The trimethylsilylbenzoic acid was reduced to o-trimethylsilylbenzaldehyde (2) through its imidazolide using the method of Staab.ls Reaction of the Grignard reagent prepared from 1 with 2 yielded 2,2'-bi~-trimethylsilylbenzhydrol (3), which was purified by preparative scale t.1.c. Etherification of 3 was carried out by heating 25-50 mg of 3 with a five to sixfold excess of the desired alcohol and a small drop of concentrated DC1 in a closed vessel at 90 "C for 10-15 h.I6 After workup in the usual way the ethers were purified by preparative scale t.1.c.…”

Section: Resultsmentioning

confidence: 99%

The mass spectral fragmentation of 2,2′‐bis‐trimethylsilylbenzhydrylethers. An indication for transannular hydrogen/deuterium rearrangements and transannular elimination reactions

Akkerman

Evers

Kerkstra

1976

Org. Mass Spectrom.

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The mass spectra of the methyl-, trideuteromethyl-, ethyl-and pentadeuteroethylethers of 2,2'-bi~-trimethylsilylbenzhydrol are reported. The most significant ions arise from the [M -CH,]+ ion, formed by loss of a methyl radical from one of the trimethylsilyl groups. After ring formation by interaction of the siliconium ion centre with an aromatic nucleus, the ion loses (CH,),Si-OR (R = CH,, C,H,, CD, and C2Ds), giving ion m/e 223. The fragment (CH3),Si-0CH3 is also eliminated in the four ethers investigated from the ion [M -R]+. Attack of the siliconium ion centre in the [M -CH,]+ ion on the ether oxygen leads to the generation of the [(CH,),Si+OR] ion.

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“…H -ArCaH4. + Me2Si6H (9) f the benzene ring. Thus, the electron donating group (Y = OMe) favors the formation of e.…”

Section: ([2]+'-+ D)mentioning

confidence: 99%

A mass spectral study of 1‐(aryldimethylsilyl)‐2‐propanones and their isomeric 2‐(aryldimethylsiloxy)‐1‐propenes

TSAI¹,

Larson²,

Oliva³

1979

Org. Mass Spectrom.

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The mass spectra of a series of β‐ketosilanes, p‐YC6H4Me2SiCH2C(O)Me and their isomeric silyl enol ethers, p‐YC6H4Me2SiOC(CH3)CH2, where Y = H, Me, MeO, Cl, F and CF3, have been recorded. The fragmentation patterns for the β‐ketosilanes are very similar to those of their silyl enol ether counterparts. The seven major primary fragment ions are [MMe·]+, [MC6H4Y·]+, [MMe2SiO]+˙, [MC3H4]+˙, [MHCCCF3]+˙, [Me2SiOH]+˙ and [C3H6O]+˙ Apparently, upon electron bombardment the β‐ketosilanes must undergo rearrangement to an ion structure very similar to that of the ionized silyl enol ethers followed by unimolecular ion decompositions. Substitutions on the benzene ring show a significant effect on the formation of the ions [MMe2SiO]+˙ and [Me2SiOH]+˙, electron donating groups favoring the former and electron withdrawing groups favoring the latter. The mass spectral fragmentation pathways were identified by observing metastable peaks, metastable ion mass spectra and ion kinetic energy spectra.

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Mass spectroscopy of organosilicon compounds. Examples of interaction of the silyl center with remote phenyl groups

Abstract: The mass spectra of l-(trimethylsilyl)-3-phenylpropane and /3-(trimethylsilyl)styrene have been studied in detail. The mass spectral rearrangements observed are shown to occur by interaction of the silyl center and the phenyl ring.Mass spectroscopy is a particularly powerful analyti-

Cited by 39 publications

References 7 publications

Time‐resolved resonance Raman study of S₁cis‐stilbene and its deuterated isotopomers

Time‐resolved resonance Raman study of S₁cis‐stilbene and its deuterated isotopomers

The mass spectral fragmentation of 2,2′‐bis‐trimethylsilylbenzhydrylethers. An indication for transannular hydrogen/deuterium rearrangements and transannular elimination reactions

A mass spectral study of 1‐(aryldimethylsilyl)‐2‐propanones and their isomeric 2‐(aryldimethylsiloxy)‐1‐propenes

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Mass spectroscopy of organosilicon compounds. Examples of interaction of the silyl center with remote phenyl groups

Abstract: The mass spectra of l-(trimethylsilyl)-3-phenylpropane and /3-(trimethylsilyl)styrene have been studied in detail. The mass spectral rearrangements observed are shown to occur by interaction of the silyl center and the phenyl ring.Mass spectroscopy is a particularly powerful analyti-

Cited by 39 publications

References 7 publications

Time‐resolved resonance Raman study of S1cis‐stilbene and its deuterated isotopomers

Time‐resolved resonance Raman study of S1cis‐stilbene and its deuterated isotopomers

The mass spectral fragmentation of 2,2′‐bis‐trimethylsilylbenzhydrylethers. An indication for transannular hydrogen/deuterium rearrangements and transannular elimination reactions

A mass spectral study of 1‐(aryldimethylsilyl)‐2‐propanones and their isomeric 2‐(aryldimethylsiloxy)‐1‐propenes

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Time‐resolved resonance Raman study of S₁cis‐stilbene and its deuterated isotopomers

Time‐resolved resonance Raman study of S₁cis‐stilbene and its deuterated isotopomers