<b>The Reactions of Sulfur Atoms. III. The Insertion in Carbon-Hydrogen Bonds of Paraffinic Hydrocarbons</b>

Knight, A. R.; Strausz, O. P.; Gunning, H. E.

doi:10.1021/ja00899a001

Cited by 36 publications

(18 citation statements)

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“…The major line at 2288 A and the line of lesser intensity at 2260 A were assumed to be the only important sources of light in photolyses with the Cd/l lamps. 21 Photolysis cells were quartz cylinders with 2-mm thick plane parallel quartz windows fused on. The windows had transmittance properties similar to those of "Optosil 1.…”

Section: A Apparatusmentioning

confidence: 99%

Some Reactions of Ground-State (3P) and Electronically Excited (1D) Sulfur Atoms

Breckenridge

Taube

1970

The Journal of Chemical Physics

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Articles you may be interested inAn experimental and computational study of the reaction of ground-state sulfur atoms with carbon disulfideThe systematic behavior of (6Li,d) groundstate transitions in the 1f2p shell AIP Conf.Reactions of S (3 P) and S (1D) have been studied by utilizing carbonyl sulfide photolysis as a source of both species. It has been shown that 46%±4% of the sulfur atoms generated in the photolysis of OCS in the 2250-2650-A spectral region can react as S (3 P), but that substantial portion of the S (3]') is likely produced by deactivating collisions of OCS molecules with S(ID). Both S(1D) and S(,1') react with CS,. The rate constant ratios for these reactions relative to the reactions with OCS have been determined as ~1.9 and ~2.4X102, respectively. Efficient isotopic exchange of S(3P) with CS2 is proposed to occur by means of CS3 formation in a reaction independent of pressure above 50 torr. The reaction of S (ID) with N20 yields N2, but kinetic complexities suggest the intermediate formation of a species such as N20S. Measurement of the quenching of the N2 yield has led to the determination of the relative rates of collisional deactivation of S(ID) for several gases.

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Section: A Apparatusmentioning

confidence: 99%

Some Reactions of Ground-State (3P) and Electronically Excited (1D) Sulfur Atoms

Breckenridge

Taube

1970

The Journal of Chemical Physics

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“…Since it is known that sulfur atoms can directly insert in C-H bonds of hydrocarbons (Knight et al, 1963), then an enzymatic system capable of generating "carbene"-type sulfur could perform a thiolation the same as oxygen can perform an hydroxylation in monooxygenases. If this is in fact the mechanism of sulfur insertion, then unlike moit hydroxylations, which proceed with retention of configuration, this thiolation must proceed with inversion of configuration.…”

Section: Discussionmentioning

confidence: 99%

Stable isotope studies on the biosynthesis of lipoic acid in Escherichia coli

White¹

1980

Biochemistry

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A method has been developed for the gas chromatographic-mass spectrometric (GC-MS) identification of lipoic acid in tissue. The method consists of acid hydrolysis of the tissue to free the bound lipoic acid, methylene chloride extraction of the lipoic acid, and the subsequent chemical derivatization of the lipoic acid as methyl 6,8-bis(benzylthio)octanoate prior to GC-MS analysis. By use of this method of analysis, the incorporation of deuterium into lipoic acid by Escherichia coli growing on [methyl-2H3]acetate has been studied. The results clearly show that the lipoic acid is biosynthesized from octanoic acid with the loss of only one deuterium-containing position at C8. The deuterium incorporated at C6 of octanoic acid from the labeled acetate is retained. Since this deuterium is incorporated in the L configuration during fatty acid biosynthesis and it is known to have the D configuration in lipoic acid, it is concluded that an inversion of configuration occurs at C6 during the sulfur insertion.

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“…These plots thus indicated that reaction [4] was not occurring, but no information about the cross sections of reactions [3] and [5] could be obtained in this way, as both reactions were contributing to the gradient in each case. However, a plot of I,,/I,, vs. 16,/11, could be used, as shown in Fig.…”

Section: Cosimethyl Iodide Mixturesmentioning

confidence: 99%

Ion–molecule reactions in carbonyl sulfide – hydrocarbon mixtures

Džidić¹,

Good²,

Kebarle³

1970

Can. J. Chem.

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The major ion-molecule reactions occurring in pure COS and in mixtures of COS with methane, methyl iodide, ethane, and ethylene were investigated in a Nier-type mass spectrometer. In cases where two or more reactions could be postulated to account for the observed product ions, appearance potential data and graphical analysis were used to evaluate the contributions of the individual reactions. Phenonienological cross sections were obtained for the reactions studied and approximate rate constants were then calculated.An independent set of n2easurenlents were carried out in a high-pressure pulsed-beam mass spectrometer, in which the absol~ite rate constants for reactions occurring in COS were measured, using nitrogen as a carrier gas. The rate constants thus obtained were used to verify the validity of the rate constants calculated from the measured cross sections.

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The Reactions of Sulfur Atoms. III. The Insertion in Carbon-Hydrogen Bonds of Paraffinic Hydrocarbons

Cited by 36 publications

References 0 publications

Some Reactions of Ground-State (3P) and Electronically Excited (1D) Sulfur Atoms

Some Reactions of Ground-State (3P) and Electronically Excited (1D) Sulfur Atoms

Stable isotope studies on the biosynthesis of lipoic acid in Escherichia coli

Ion–molecule reactions in carbonyl sulfide – hydrocarbon mixtures

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