Chemical ionization mass spectral analysis of pinacolyl alcohol and development of derivatization method using p-tolyl isocyanate

Murty, M. R. V. S.; Raju, N. Prasada; Prabhakar, S.; Vairamani, M.

doi:10.1039/c0ay00346h

Cited by 13 publications

(10 citation statements)

References 19 publications

(18 reference statements)

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“…A series of isomeric dialkyl alkylphosphonothiolates (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18) and dialkyl alkylphosphonothionates (19)(20)(21)(22)(23)(24)(25)(26)(27), which belong to schedule 2.B.4 of the CWC, was synthesized in-house and then analyzed by GC/MS under EI and CI conditions. The study mainly emphasizes the differentiation of phosphonothiolates and phosphonothionates (connectivity between P and S) and also the identification of the alkyl group attached to the sulfur, oxygen and phosphorus atoms.…”

Section: Discussionmentioning

confidence: 99%

“…In such a case, the presence of the [M-OR] + ion is expected in the EI spectra of dialkyl phosphonothiolates in addition to the expected [M-SR] + ion. Among the studied dialkyl alkylphosphonothiolates (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18), the [M-OR] + ion appeared only in compounds where a propyl or a butyl group was attached to sulfur (3-4, 8-10, 13-14). This reveals that the dialkyl phosphonothiolates undergo a 'thiolo-thiono' rearrangement, especially when a higher alkyl group is attached to sulfur.…”

Section: Thiono-thiolo Rearrangementmentioning

confidence: 99%

“…Of these, the MS detector has been extensively used because of its high sensitivity and versatility. Compounds of polar nature can be analyzed directly by liquid chromatography (LC)/MS or by GC/MS after derivatization . GC/MS analysis is typically performed under electron ionization (EI) or chemical ionization (CI) conditions .…”

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confidence: 99%

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Mass spectral characterization of the CWC‐related isomeric dialkyl alkylphosphonothiolates/alkylphosphonothionates under gas chromatography/mass spectrometry conditions

Karthikraj

Sridhar

Prabhakar

et al. 2013

Rapid Comm Mass Spectrometry

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The present study highlights the structural characterization of the isomeric phosphonothiolates and phosphonothionates based on their selective EI fragmentation. The assigned fragmentation pathway helps in the assignment of P-S and P-alkyl connectivity in phosphonothiolates and phosphonothionates, consequently the structure of the unknown compounds. The EI mass spectra (27 compounds) of isomeric compounds are immensely useful in the OPCW official proficiency tests and for off-site analysis.

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Section: Discussionmentioning

confidence: 99%

Section: Thiono-thiolo Rearrangementmentioning

confidence: 99%

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Mass spectral characterization of the CWC‐related isomeric dialkyl alkylphosphonothiolates/alkylphosphonothionates under gas chromatography/mass spectrometry conditions

Karthikraj

Sridhar

Prabhakar

et al. 2013

Rapid Comm Mass Spectrometry

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“…3,3-Dimethyl-1-butanol is a glass-forming material used as a chemical intermediate in organic syntheses (https://www.capotchem.com, last access: 3 June 2019). 3,3-Dimethyl-2-butanol is a potential precursor for prohibited chemical weapons such as soman, which is a nerve agent (Murty et al, 2010). It is also used in the conversion of ribose-and glucose-binding proteins into receptors for pinacolyl methylphosphonic acid (Allert et al, 2004).…”

Section: Introductionmentioning

confidence: 99%

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

et al. 2020

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Abstract. The atmospheric fate of a series of saturated alcohols (SAs) was evaluated through kinetic and reaction product studies with the main atmospheric oxidants. These SAs are alcohols that could be used as fuel additives. Rate coefficients (in cm3 molecule−1 s−1) measured at ∼298 K and atmospheric pressure (720±20 Torr) were as follows: k1 ((E)-4-methylcyclohexanol + Cl) = (3.70±0.16) ×10-10, k2 ((E)-4-methylcyclohexanol + OH) = (1.87±0.14) ×10-11, k3 ((E)-4-methylcyclohexanol + NO3) = (2.69±0.37) ×10-15, k4 (3,3-dimethyl-1-butanol + Cl) = (2.69±0.16) ×10-10, k5 (3,3-dimethyl-1-butanol + OH) = (5.33±0.16) ×10-12, k6 (3,3-dimethyl-2-butanol + Cl) = (1.21±0.07) ×10-10, and k7 (3,3-dimethyl-2-butanol + OH) = (10.50±0.25) ×10-12. The main products detected in the reaction of SAs with Cl atoms (in the absence/presence of NOx), OH radicals, and NO3 radicals were (E)-4-methylcyclohexanone for the reactions of (E)-4-methylcyclohexanol, 3,3-dimethylbutanal for the reactions of 3,3-dimethyl-1-butanol, and 3,3-dimethyl-2-butanone for the reactions of 3,3-dimethyl-2-butanol. Other products such as formaldehyde, 2,2-dimethylpropanal, and acetone have also been identified in the reactions of Cl atoms and OH radicals with 3,3-dimethyl-1-butanol and 3,3-dimethyl-2-butanol. In addition, the molar yields of the reaction products were estimated. The products detected indicate a hydrogen atom abstraction mechanism at different sites on the carbon chain of alcohol in the case of Cl reactions and a predominant site in the case of OH and NO3 reactions, confirming the predictions of structure–activity relationship (SAR) methods. Tropospheric lifetimes (τ) of these SAs have been calculated using the experimental rate coefficients. Lifetimes are in the range of 0.6–2 d for OH reactions, 7–13 d for NO3 radical reactions, and 1–3 months for Cl atoms. In coastal areas, the lifetime due to the reaction with Cl decreases to hours. The calculated global tropospheric lifetimes, and the polyfunctional compounds detected as reaction products in this work, imply that SAs could contribute to the formation of ozone and nitrated compounds at local, regional, and even global scales. Therefore, the use of saturated alcohols as additives in diesel blends should be considered with caution.

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“…Various derivatization methods have been reviewed for CWC-related chemicals by Black et al (1) The most important derivatization methods are methylation, (2) trimethylsilylation, (3) tertbutyldimethylsilylation, (4) and pentafluorobenzylation. (5) In addition to these methods, methylation in the hot GC injection port, (6) trifluoroacetylation, (7) bisheptafluorobutyrylation, (8) p-tolyl isocyanate derivatization for pinacolyl alcohol, (9) and various aliphatic thiols for the derivatization of Lewisites (10) have also been used.…”

Section: Introductionmentioning

confidence: 99%

Gas Chromatography in Screening of Chemicals Related to the Chemical Weapons Convention

Kostiainen¹

2011

Encyclopedia of Analytical Chemistry

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Various gas chromatographic methods, which are useful for the screening of Chemical Weapons Convention (CWC)‐related chemicals, are described in this section. Choice of columns, detectors, and injection techniques, crucial to the optimization of gas chromatography (GC) as a routine screening tool, are discussed. Also, various identification methods are described. The use of the retention indices (RIs) method allowing identification without the need for an authentic chemical is described in detail. RIs are used as an identification method together with electron ionization mass spectrometry (EIMS) in the on‐site analysis method established by the Organization for the Prohibition of Chemical Weapons (OPCW).

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Chemical ionization mass spectral analysis of pinacolyl alcohol and development of derivatization method using p-tolyl isocyanate

Cited by 13 publications

References 19 publications

Mass spectral characterization of the CWC‐related isomeric dialkyl alkylphosphonothiolates/alkylphosphonothionates under gas chromatography/mass spectrometry conditions

Mass spectral characterization of the CWC‐related isomeric dialkyl alkylphosphonothiolates/alkylphosphonothionates under gas chromatography/mass spectrometry conditions

Atmospheric fate of a series of saturated alcohols: kinetic and mechanistic study

Gas Chromatography in Screening of Chemicals Related to the Chemical Weapons Convention

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