10378-58-2

Upstream product

• 77956-17-3 1,2-diphenyl-2-trideuteriomethyl-3,3,3-trideuterio-1-propanone 
• 591-51-5 phenyllithium 
• 98-83-9 isopropenylbenzene 
• 72235-68-8 1,1,1,3,3,3-hexadeuterio-2-phenyl-2-propanol 

Downstream Products

• 79663-73-3 (α-methyl-α-neopentylbenzyl)lithium-β-d5 
• 109154-78-1 C₂₃H₁₈⁽²⁾H₅NO₃ 
• 109154-78-1 C₂₃H₁₈⁽²⁾H₅NO₃ 

Relevant academic research and scientific papers

Kinetics of hydrogen atom transfer from (η5-C 5H5)Cr(CO)3H to various olefins: Influence of olefin structure

Treating (η5-C5H5)Cr(CO)3H (1) or (η5-C5H5)Cr(CO)3D (1-d1) with an excess of olefin containing the opposite isotope generally leads to H/D exchange, althoug

Ion-Molecule Pairs in Leaving-Group-Promoted Solvolytic Elimination Reactions

Solvolysis of 1-(1-methyl-1-phenylethyl)pyridinium cation (1-P+) in 25 vol % acetonitrile in water at 60 °C provides the substitution product 2-hydroxy-2-phenylpropane (1-OH) and the elimination product 2-phenylpropene (3). The fraction of elimination is about half of that obtained with an acetate leaving group of similar basicity. The total rate of reaction is dependent on the basicity of the leaving group, 1-(1-methyl-1-(4-cyanophenyl)ethyl)pyridinium cation (1-P-CN+) reacts 1100 times faster than 1-P+ which corresponds to a Bronsted parameter of β1g = -0.93. Also the fraction of elimination is leaving-group dependent as expressed by a Bronsted parameter of β= 0.12 for the dehydronation of the ion-molecule pair by the leaving group. Addition of substituted pyridines has only a minor effect on the product ratio. The reactions are concluded to occur stepwise through a common carbocation intermediate of ion-molecule pair type. The overall kinetic deuterium isotope effects using the hexadeuteriated analogs were measured as kobsH/kobsD6 = 1.85 ± 0.10 (60 °C) with the pyridinium ion 1-P+and as kobsH/kobsD6 = 1.53 ± 0.06 (40 °C) with the 4-cyanopyridinium ion 1-P-CN+. The kinetic deuterium isotope effects on the elimination step (assuming the reaction from intermediate to alcohol is insensitive to isotopic substitution) were measured as keH/keD6 = 2.7 ± 0.2 for 1-P+ (60 °C) and 3.4 ± 0.2 for 1-P-CN+ (40 °C).

Functionalization of Alkenyl C-H Bonds with D 2 O via Pd(0)/Carboxylic Acid Catalysis

We report herein a simple catalytic method for the extensive labeling of alkenyl C-H bonds through the combination of a palladium(0) complex and a carboxylic acid in the presence of deuterium oxide. The reaction can be applied to a variety of terminal alkenes and the best results are obtained with aryl-substituted examples. This method represents a convenient approach for the preparation of extensively labeled chemicals from the cheapest and safest source of deuterium.

Solvolytic elimination reactions. Stepwise or concerted?

2-Aryl-endo-2-norbornyl trifluoroacetates 11 solvolyze to give a significant fraction of elimination product. A deuterium labeling study showed that the exo hydrogen is lost exclusively when the elimination product forms. A concerted ester pyrolysis type of mechanism is therefore ruled out. The tertiary benzylic trifluoroacetate Ph(CH3)C(CONMe2)(OCOCF3), 12, solvolyzes to give exclusively an elimination product. The β-CD3 isotope effect on rate was 1.15. There is, however, a larger isotope effect (2.5) in formation of the elimination product when Ph(CH2D)C(CONMe2)(OCOCF3) solvolyzes. The mechanism therefore has a minimum of two steps since the product-determining step and the rate-determining step have differing isotope effects. A concerted elimination mechanism is ruled out. The ortho-dimethyl-substituted cumyl trifluoroacetate 13 also solvolyzes to give an elimination product. The β-D6 isotope effect of 1.61 is in the "normal" range for a secondary isotope effect in a carbocation-forming reaction. This argues against a concerted elimination mechanism. These results contrast with the recent suggestion that cumyl systems give elimination product via a concerted elimination mechanism. The analogous tertiary benzylic systems 11-13 all give solvolytic elimination products via discrete cationic intermediates.

Photoaddition of Alkenes to N-Methyl-1,8-naphthalimide in Methanol. Evidence for the Mechanism of the Formation of the Tetracyclic Adducts.

Irradiation of N-methyl-1,8-naphthalimide (NMN) in the presence of α-methylstyrene (α-MS) or 1,1-diphenylethylene in methanol gives novel tetracyclic imides.The mechanism proposed involves photostimulated electron transfer from the alkene to 1,8-NMN and radical coupling addition of methanol to the resultant radical cation-radical anion pair at the 4-position of the aromatic ring to give an unisolable intermediate with an α,β-unsaturated carbonyl moiety.Absorption of a second photon by this chromophore gives rise to the final product.The predicted regiochemistry and stereochemistry of the reaction were established by using pentadeuterio-α-methylstyrene (16), thus providing strong evidence for the mechanism.

Photochemistry of Some Deoxybenzoins in Micellar Solutions. Cage Effects, Isotope Effects, and Magnetic Field Effects

The photolyses of 1,2-diphenyl-2-methyl-1-propanone (1) and its D-, 13C-, and alkyl-substituted derivatives 2-5 in various micellar solutions have been investigated.It was found that the extent of cage disproportionation to yield benzaldehydes 6 and α-methylstyrenes 7 is enhanced by a factor of about 10 compared to the photolyses in homogeneous organic solvents.The advantage of using micelles rather than homogeneous solutions to enhance the magnitude of magnetic isotope and magnetic field effects on cage disproportionation is demonstrated.The results are interpreted in terms of a mechanism involving the competition between hyperfine-induced intersystem crossing of a triplet radical pair (3RP) to form a singlet radical pair (1RP) and escape of 3RP from the micelle.

PHOTOCHEMISTRY OF 1,2-DIPHENYL-2,2-DIMETHYL-PROPANONE-1 IN MICELLAR SOLUTIONS. CAGE EFFECTS, ISOTOPE EFFECTS AND MAGNETIC FIELD EFFECTS.

The cage reaction resulting from photolysis of PhCOC(CH3)2Ph and PhCOC(CD3)2Ph in micellar solution is shown to be subject to substantial magnetic field and magnetic isotope effects.