4067-80-5

Upstream product

• 3972-26-7 2-Propanol-2-d 
• 19214-95-0 (^2-₂H)propan-2-(2H)ol 

Downstream Products

• 4019-54-9 isopropylbenzene-d1 
• 859504-83-9 4-chloro-N-[1-D]isopropylformanilide 
• 85385-44-0 4-(1-deuterio-1-methylethyl)anisole 

Relevant academic research and scientific papers

Stereodynamics of N-Ethyl-N-methyl-2-aminopropane. 1H and 13C DNMR Studies. Molecular Mechanics Calculations

N-Ethyl-N-methyl-2-aminopropane (EMAP) is one of the simplest tertiary aliphatic amines that has a chiral center at nitrogen.Racemization occurs by inversion-rotation at the pyramidal nitrogen.For each EMAP enantiomer, additional conformational interconversions occur via isolated rotation about carbon-nitrogen bonds.The 1H and 13C dynamic NMR (DNMR) spectra of EMAP and a selectively deuterated derivative decoalesce into four subspectra at 95 K.The spectrum at 95 K is best rationalized in terms of five equilibrium conformations present at concentrations high enough to be NMR-detectable including two conformations that interchange rapidly even at 95 K.A two-letter designation is used to name the various conformations.The first letter defines the orientation of the ethyl methyl group (G denotes gauche to the lone pair and to the N-methyl group; G' denotes gauche to the lone pair and to the isopropyl group; A denotes anti to the lone pair).The second letter defines the orientation of the isopropyl methine proton (G denotes gauche to the lone pair and to the N-methyl group; G' denotes gauche to the lone pair and to the ethyl group; A denotes anti to the lone pair).The major subspectrum at 95 K is assigned to a family of G'G' and GG' conformations (59percent) that interconvert rapidly at 95 K.The other three subspectra are assigned to the GG (34percent), AA (5percent), and GA (2percent) conformations.Simulations of the DNMR spectra reveal a barrier to inversion-rotation at nitrogen (ΔG(excit.) = 7.5 kcal/mol at 160 K) that is higher than the barriers for a number of observable isolated rotations about the N-CH2 and N-CH bonds (ΔG(excit.) = 4.7-6.4 kcal/mol).A 5000-point optimized energy surface computed as a function of two dihedral angles by using Allinger's MM2(87) computer program, MM2(87) energy calculations for all the optimized equilibrium conformations of EMAP, and MM2(87)-calculated isolated rotation barriers show excellent agrreement with the DNMR data.

DEUTERIUM-SUBSTITUTED OXADIAZOLES

Described are deuterated modulators of S1P1 receptors, pharmaceutical compositions thereof, and methods of use thereof.

Photochemical Reaction of 1,4-Naphthalenedicarbonitrile with Alkylbenzenes and Bibenzyls

The photochemical reaction of 1,4-naphthalenedicarbonitrile with some alkylbenzenes and bibenzyls has been examined.A unitary mechanistic picture is formulated on the basis of product study, deuteration experiments, and fluorescence and reaction quantum yield measurements.Proton transfer within the singlet radical ion pair followed by in-cage cycloaddition of the two radicals yields stereoselectively 5,11-methanodibenzo cyclooctene derivatives (8).Reaction of benzyl radicals (formed by protolysis or, for radical cations having no benzylic proton, by C-C bond cleavage) with unprotonated NDN.- leads, again stereoselectively, to 2-benzyl-1,2-dihydronaphtalenes (9).Escape of the donor radical cation and following C-H or C-C bond cleavage leads to a different product, thus, benzyl radicals are trapped by NDN to yield substitution products (11) or recombine.Benzyl cations are trapped by nucleophiles.

Mechanism of Elimination Reactions. 38. Why Is the Effect of Successive β-Alkyl Substitution on the Rates of Elimination from Quaternary Ammonium Salts Nonadditive?

Possible reasons are examined for the nonadditivity of the effect of successive β-methyl substitution on the rates of elimination reactions of quaternary ammonium salts.The temperature dependences of the deuterium isotope effects in E2 reactions of R1R2NMe2+ show that tunneling is not a significant source of nonadditivity.Neither is a change of gross mechanism or stereochemistry, for studies with C4H9CHDCHDNMe3+ and C4H9(CH3)CHCHDNMe3+ show the reactions to be very predominantly (>88percent) anti-E2 in both cases.Secondary tritium isotope effects with R1R2CHCHTNMe3+ increase, however in the order ethyl (1.108 +/- 0.002), propyl (1.150 +/- 0.015), isobutyl (1.216 +/- 0.012).This result suggests increasing rehybridization at the α-carbon in the transition state and therefore a shift toward less E1cB and more central-E2 character.Since methyl substitution is expected to favor a developing double bond, the much smaller rate-depressing effect of the second β-methyl is accounted for by such a shift in transition-state character.

GAS-PHASE THERMOLYSIS OF SULFUR COMPOUNDS. PART VI. ALLYL PROPARGYL AND ISOPROPYL PROPARGYL SULFIDES

Allyl propargyl and isopropyl propargyl sulfides were pyrolyzed in a stirred-flow system at temperatures in the range 312-402 deg C and pressures between2 and 14 torr.The allyl propargyl sulfide yielded as products a mixture of propene and allene and the corresponding propynethial and propenethial.The thioaldehydes react at room temperature to form polymers and the Diels-Alder adduct 1,3-dithia-2-ethynyl-cyclohex-5-ene.The reaction products from isopropyl propargyl sulfide were allene and thioacetone.The reaction showed first order kinetics, with the rate coefficients following the Arrhenius equations Allyl Propargyl Sulfide:k(sec-1) = 1011.22+/-0.28exp(-139 +/- 3 kJ/mol RT), Isopropyl Propargyl Sulfide: k(sec-1) = 1011.51+/-0.14exp(-155 +/- 2 kJ/mol RT).The kinetic deuterium isotope effect of 4-thia-5-deutero-5-methyl-hex-1-yne pyrolysis was studied over the temperature range 370-402 deg C.

NUCLEOPHILIC SUBSTITUTION OF α-HALO KETONES. XXI. STRUCTURE-REACTIVITY RELATIONSHIPS IN THE ACETOLYSIS OF 3-SUBSTITUTED 1-CHLORO-3-PHENYLTHIO-2-PROPANONES

The acetolyses of α-chloro ketones 1a-d have been re-investigated under standard conditions and compared with those of the corresponding isomeric substrates 2a-d.It has been shown that participation by the neighbouring phenylthio group, involving a 1-3 shift of the latter, does occur in part even in the case of 1d, while it is the only process in the case of 1e.A few structure-reactivity relationships in the two series of substrates are discussed.

DEHYDRATION OF ALCOHOLS ON ALUMINA-12

Primary kinetic isotope effects of the dehydration from the gas phase of tertiary, secondary and iso-butanol on alumina have been easured between 120 and 230 C. The deuteration on the hydroxyl group does not give rise to an isotope effect, whereas substitution of the !-proton by deuterium produces an appreciable effect. Below 200 C primary, secondary, and tertiary alcohols are dehydrated via reaction intermediates over alumina which presumably contain a certain degree of ionic contributions. With increasing temperature these ionic contributions are favored.