40422-04-6

Usage

Uses

n-Propyl-1,1-d2 Alcohol (CAS# 40422-04-6) is a useful isotopically labeled research compound.

Upstream product

• 123-62-6 propionic acid anhydride 
• 554-12-1 propanoic acid methyl ester 
• 79-03-8 propionyl chloride 
• 802294-64-0 propionic acid 
• 122-63-4 benzyl proprionate 

Downstream Products

• 40422-05-7 1-bromo-1,1-dideuteropropane 
• 25493-14-5 1-iodo<1,1-2H2>propane 
• 125640-23-5 1-(1,1-2H2)-chloropropane 

Relevant academic research and scientific papers

NITRIC OXIDE CHEMICAL IONIZATION MASS SPECTROMETRY OF ALCOHOLS.

Electron ionization of nitric oxide at 1 torr affords the nitrosonium ion, NO** plus , in high abundance. Under chemical ionization conditions, this ion undergoes a different set of ion-molecule reactions with primary, secondary, and tertiary alcohols. Reaction of NO** plus with primary and secondary alcohols affords abundant (M minus 1)** plus and (M minus 2 plus NO)** plus ions. An (M minus 3)** plus ion is generated from primary but not from secondary alcohols Secondary but not usually primary alcohol afford (M minus OH)** plus ions. Tertiary alcohols afford spectra containing a single ion corresponding to (M minus OH)** plus . Nitric oxide chemical ionization mass spectra can be used to differentiate isomeric alcohols.

FT-Raman spectra of n-propanol and selected partially 2H-labelled analogues

Fourier-transform Raman spectra of CH3CH2CH2OH and some of its selectively deuteriated analogues have been obtained. Comparisons of the Raman spectra of the protiated and partially deuteriated species, in conjunction with polarization data, has enabled improved vibrational assignments to be made for the C-H modes. As a result, confirmation of some literature assignments of stretching and bending modes and revision of other tentative assignments for large biopolymer molecules have been proposed.

Inherent asymmetry of constitutionally equivalent methyl groups in the H/D equilibration of n- and i-C3H7Fe(OH)+ complexes

Transiently formed, constitutionally identical methyl groups remain inequivalent in the course of an n-propyl?isopropyl isomerization (see scheme) operative in Fe÷-mediated dehydration of propanols. The reversibility of the β-hydrogen transfer steps is addressed by examination of the H/D equilibration in metastable complexes of Fe+ with a set of selectivity deuterated propanols by using tandem mass spectrometry.

Site-selective deuterium labeling of the tetrabutylammonium cation

Four separate selectively deuterated samples of tetrabutylammonium iodide have been prepared in which each one of the four nonequivalent alkyl carbons is separately and fully deuterated. These samples were prepared for nuclear magnetic resonance (NMR) studies of the aggregation of ion pairs in low polarity solvents.

Intermediacy of ion neutral complexes in the fragmentation of short-chain dialkyl sulfides

The main fragmentation processes after electron ionization of butyl methyl and butyl ethyl sulfides are rationalized by the intermediacy of the ion neutral complex [RSH · methylcyclopropane](+·) as demonstrated by extensive labeling and collision activation studies.

Synthesis, Structure, and Thermolysis Mechanism of S-Alkoxythiazynes

S-Alkoxy-S,S-diarylthiazynes were prepared by two methods: the alkaline hydrolysis of S,S-diaryl-N-halosulfilimines in aqueous alcohols and the reaction of S,S-diaryl-S-fluorothiazynes with sodium alkoxides. The structure of S,S-diphenyl-S-propoxythiazyne was determined by an X-ray crystallographic analysis, which showed a short SN bond length of 1.441(3) A. The thermolysis of S-alkoxythiazynes gave elimination products, which were identified as the corresponding carbonyl compounds and N-unsubstituted S,S-diarylsulfilimines. Kinetic experiments for the thermolysis of the S-alkoxy-S,S-diarylthiazynes were carried out. The first-order kinetic behavior, a large kinetic isotope effect (kHkD = 6.1 ) using S,S-diphenyl-S-[1,1-2H2]propoxythiazyne, a negative activation entropy (ΔS? = -30 J K-1mol-1), and a negative Hammett ρ-value (ρ= -0.35) on the phenyl group were obtained, suggesting that the reaction proceeds via a concerted five-membered cyclic transition state. A deviation from the ideal concerted transition state is discussed in comparison with that for sulfoxides.

Mechanism of Propene and Water Elimination from the Oxonium Ion CH3CH=O+CH2CH2CH3

The site-selectivity in the hydrogen transfer step(s) which result in propene and water loss from metastable oxonium ions generated as CH3CH=O+CH2CH2CH3 have been investigated by deuterium-labelling experiments.Propene elimination proceeds predominantly by transfer of a hydrogen atom from the initial propyl substituent to oxygen.However, the site-selectivity for this process is inconsistent with β-hydrogen transfer involving a four-centre transition state.The preference for apparent α- or γ-hydrogen transfer is interpreted by a mechanism in which the initial propyl cation accessible by stretching the appropriate bond in CH3CH=O+CH2CH2CH3 isomerizes unidirectionally to an isopropyl cation, which then undergoes proton abstraction from either methyl group +CH2CH2CH3 CH3CH=O---+CH2CH2CH3 +CH(CH3)2> + CH3CH=CH2>>.This mechanism involving ion-neutral complexes can be elaborated to accommodate the minor contribution of expulsion of propene containing hydrogen atoms originally located on the two-carbon chain.Water elimination resembles propene loss insofar as there is a strong preference for selecting the hydrogen atoms from the α- and γ-positions of the initial propyl group.The bulk of water loss is explicable by an extension of the mechanism for propene loss, with the result that one hydrogen atom is eventually transferred to oxygen from each of the two methyl groups in the complex +CH(CH3)2>.This site-selectivity is strikingly different from that (almost random participation of the seven hydrogen atoms of the propyl substituent) encountered in the corresponding fragmentation of the lower homologue CH2=O+CH2CH2CH3.This contrast is explained in terms of the differences in the relative energetics and associated rates of the cation rearrangement and hydrogen transfer steps.

Side-chain Effects on the Fragmentation Behaviour of Alkylthiophenes

The processes leading to the fragment ions formed from alkylthiophene molecule ions by benzylic cleavage without and with transfer of one hydrogen from the side-chain to the ring and the influence of additional methyl groups on the relative importance of these two fragmentation reactions were investigated.

Unimolecular Reactions of Isolated Organic Ions: Loss of Carbon Monoxide from the Oxonium Ion CH2=CHCH2+O=CH2 via Double Hydrogen Transfer

The reactions of the metastable oxonium ion CH2=CHCH2+O=CH2 have been investigated.This C4H7O+ species was generated by ionisation and alkyl radical loss from allyl ethyl or allyl propyl ether.CH2=CHCH2+O=CH2 is apparently ideally suited to fragmentation via simple cleavage to form the favourable products CH2=CHCH2+ and CH2O.However, at low internal energies, expulsion of a neutral species having a mass of 28 amu takes place essentially to the exclusion of CH2O loss. 2H- and 13C-labelling experiments reveal that it is carbon monoxide which is eliminated, via double hydrogen transfer between the developing products accessible to C-O bond fission.The role of ion-neutral complexes in these hydrogen transfer steps is discussed.

Unimolecular Reactions of Isolated Organic Ions: the Chemistry of the Oxonium Ions CH3CH2CH2CH2(+)O=CH2 and CH3CH2CH2CH=O(+)CH3

The reactions of the metastable oxonium ions CH3CH2CH2CH2(+)O=CH2 and CH3CH2CH2CH=O(+)CH3 are reported and discussed.Both these isomers of C5H11O(+) expel predominantly CH2O (75 - 90percent of the metastable ion current), a moderate amount of C3H6 (5-15percent), a minor amount of CH3OH (2-8percent) and a very small proportion of H2O (0.5-3percent).All these processes give rise to Gaussian metastable peaks.The kinetic energy releases associated with fragmentation of these oxonium ions are similar, but slightly larger for dissociation of CH3CH2CH2CH=O(+)CH3.The behaviour of labelled analogues confirms that the reactions of CH3CH2CH2CH2(+)O=CH2 and CH3CH2CH2CH=O(+)CH3 are closely related, but subtly different.Elimination of CH2O and C3H6 is intelligible by means of mechanisms involving CH3CH(+)CH2CH2OCH3.This open-chain cation is accessible to CH3CH2CH2CH2(+)O=CH2 by a 1,5-H shift and to CH3CH2CH2CH=O(+)CH3 by two consecutive 1,2-H shifts (or, possibly, a direct 1,3-H shift).The rates of these 1,2-, 1,3- and 1,5-H shifts are compared with one another and also with the rates of CH2O and C3H6 loss from each of the two oxonium ions.The 1,5-H shift that converts CH3CH(+)CH2CH2OCH3 formed from CH3CH2CH2CH=O(+)CH3 into CH3CH2CH2CH2(+)O=CH2 prior to CH2O elimination is essentially unidirectional.In contrast, the corresponding step converting C5H11O(+) ions generated as CH3CH2CH2CH2(+)O=CH2 into CH3CH(+)CH2CH2OCH3 competes effectively with expulsion of CH2O and C3H6.The implications of the latter finding for the degree of concert in the hydrogen transfer and carbon-carbon bond fission steps in alkene losses from oxonium ions via routes that are formally isoelectronic with the retro 'ene' pericyclic process are emphasized.