Qualitative Analysis of Organosilicon Compounds and Polymers

Burkhard, Charles A.; Norton, F. J.

doi:10.1021/ac60026a019

Cited by 7 publications

(5 citation statements)

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“…H2SO4 respectively. 74 Subsequently, Gilman et al 25,71,75 and others reported the successful cleavage of aryl substituted disilanes with potassium metal, 69 sodiumpotassium alloy, 28,44,[75][76][77][78][79] potassium-graphite (C8K) [80][81] and potassium hydride to obtain silylpotassium (Scheme 18a). [82][83][84][85][86] The obtained silylpotassium 64 was further reacted with chlorosilane to form the disilane 36 (Scheme 18b).…”

Section: Silylpotassium From Disilanementioning

confidence: 99%

“…Pre-1950s studies showed that cleaved of disilanes was unsuccessfully with several reagents, such as iodine, oxygen 72 or sodium 73 in boiling xylene, aqueous or alcoholic alkali, 74 or even with concd H 2 SO 4 . 75 From the 1950s onwards, Gilman and co-workers 26,72,76 and others reported the successful cleavage of aryl-substituted disilanes to give silylpotassiums such as 64 with potassium metal, 70 sodium-potassium alloy, 29,45,[76][77][78][79][80] potassium-graphite (C 8 K), 81,82 and potassium hydride (Scheme 19a). [83][84][85][86] Triphenylsilylpotassium (64) was further reacted with chlorosilane to form 1,1,1trimethyl-2,2,2-triphenyldisilane (36) (Scheme 19b).…”

Section: Silylpotassium From Disilanesmentioning

confidence: 99%

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Preparations of Silyl Anions

Rasappan,

Pulikkottil,

Balakrishnan

et al. 2023

Synthesis

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This review is collective writing on synthetic procedures for the synthesis of different silyl nucleophiles which are valuable reagents for chemists, particularly in the field of organic synthesis and organometallic chemistry. We have described the preparations of silyl nucleophiles of lithium, sodium, potassium, rubidium, and caesium from group I metals. We have also focused on silyl anions of beryllium, magnesium, calcium, strontium, and barium from group II metals. We included synthetic procedures for silyl anions of zirconium, hafnium, cadmium, and zinc. The synthesis of group XIII silyl anions of boron and aluminium is also highlighted in this short review.

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Section: Silylpotassium From Disilanementioning

confidence: 99%

Section: Silylpotassium From Disilanesmentioning

confidence: 99%

Preparations of Silyl Anions

Rasappan,

Pulikkottil,

Balakrishnan

et al. 2023

Synthesis

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“…Weight Percent Phenyl = 118.4 -^Phenyl AdMSO typMSO ^Sample RESULTS AND DISCUSSION A number of compounds have been suggested for cleaving monovalent organic substituents attached to silicon (32)(33)(34)(35)(36)(37)(38)(39). The use of potassium hydroxide was investigated.…”

Section: )mentioning

confidence: 99%

Analysis of polysiloxanes by alkali fusion reaction gas chromatography

Schlueter¹,

Siggia²

1977

Anal. Chem.

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The technique of alkali fusion reaction gas chromatography has been applied to the determination of alkyl and aryl groups in polysiloxanes. The method involves the quantitative cleavage of ail organic substituents bonded to silicon, producing the corresponding hydrocarbons. Reactions are driven to completion, with no apparent decomposition, in less than 10 minutes by fusing the sample with potassium hydroxide in an Inert atmosphere. After concentration of the volatile products, they are separated and determined by gas chromatography. Sample losses are minimized by performing the total analysis in a single piece of apparatus. Fluids, gum rubbers, and resins are handled with equal ease. The percent relative standard deviation of the method is 1.0%; the average deviation between experimental and theoretical or check method results Is 0.5% absolute.Polysiloxanes, also referred t o as silicones or polyorganosiloxanes, are commercially important because of unique properties resulting from their dual organic-inorganic composition. The analytical chemistry of this class of polymers has been reviewed in a recent monograph by Smith ( I ) .Spectrometric techniques, such as IR and NMR, are powerful tools for the qualitative and quantitative analysis of many functional groups in t h e intact polymer. Alternatively, these organic substituents can be cleaved from the polymer to produce simple compounds that can b e determined by chemical or instrumental techniques.Alkyl and aryl substituents are readily detected by t h e above approaches, b u t quantitative analyses of these groups may be difficult with existing methodology. Instrumental techniques such as N M R (2, 3 ) , IR (4-13), and UV (14-17) spectrometry are useful for analyzing methyl and/or phenyl groups in silicone polymers, but they are generally unable t o differentiate isomers or homologues. Chemical cleavage coupled with a separation technique is a more selective approach. Several reaction-based methods have been reported for t h e quantitative determination of alkyl and aryl groups

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“…These included the use of isotope abundance ratios, the presence of ions resulting from metastable transitions, etc. Burkhard and Norton (29) applied the mass spectrometer to the qualitative analysis of organosilicon compounds and polymers. Univalent hydrocarbon radicals directly attached to silicon were connected to the related hy- drocarbon gas by heating with concentrated sulfuric acid and admitted directly to the mass spectrometer.…”

Section: Analytical Applicationsmentioning

confidence: 99%