72235-68-8

Upstream product

• 108-86-1 bromobenzene 
• 666-52-4 [⁽²⁾H₆]acetone 
• 591-51-5 phenyllithium 
• 77956-17-3 1,2-diphenyl-2-trideuteriomethyl-3,3,3-trideuterio-1-propanone 

Downstream Products

• 113305-58-1 (2-(4-(1,1,1,3,3,3-hexadeutero-2-propyl)phenylthio)-4-fluorophenyl)acetic acid 
• 113305-72-9 4-(1,1,1,3,3,3-hexadeutero-2-propyl)benzenesulphonyl chloride 
• 113305-57-0 4-(1,1,1,3,3,3-hexadeutero-2-propyl)thiophenol 
• 75296-07-0 C₉H₅⁽²⁾H₆⁽¹⁺⁾ 
• 10378-58-2 1,1,3,3,3-pentadeuterio-2-phenylpropene 
• 53102-26-4 2-Chloro-2-phenyl-1,1,1,3,3,3-hexadeuteropropane 
• 20201-29-0 2-phenyl<1,1,1,3,3,3-2H6>propane 

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).

Unusual Fragmentation of 1,1,2,2,3,3-Hexamethylindan. Methyl Group Equilibration and Multi-step Skeletal Rearrangements in the (1+) Ions Prior to the Formation of t-C4H9(1+) Other Fragment Ions

Based on the surprising observation of an intense C4H9(1+) (m/z 57) peak in the electron impact mass spectrum, the fragmentation of 1,1,2,2,3,3-hexamethylindan (2) was studied by mass-analysed ion kinetic energy spectrometry of its deuterium-labelled analogues.While methyl loss from ions (1+). occurs with high selectivity (92percent) from the positions 1 and 3 without any rearrangement, ions (1+) undergo complete equilibration of the five methyl groups as intact entities.Subsequent multi-step skeletal rearrangement of the (1+) ions leads to formation of tert-butyl ions and to the loss of isobutene and propene, again without concomitant hydrogen exchange.Several kinetic isotope effects and also probably a thermodynamic isotope effect associated with each of these fragmentation processes have been found and their origin is discussed.The possibility of the formation of ion-neutral complexes and is considered on the basis of the labelling and reactivity pattern.

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.

FLUORINATED TRICYCLIC NEUROLEPTICS WITH PROLONGED ACTION: DERIVATIVES AND ANALOGUES OF 2-(4-(7-FLUORO-2-ISOPROPYL-10,11-DIHYDRODIBENZOTHIEPIN-11-YL)PIPERAZINE-1-YL)ETHANOL

The preparation of 4-fluoro-2-nitrobenzonitrile (V), an intermediate in the synthesis of the title compound I, from 4-fluoro-2-nitroaniline via 5-fluoro-2-iodonitrobenzene (VII) was elaborated.Syntheses of 1,1,1,3,3,3-hexadeutero-2-propyl (XX) and 1,3,4-trideutero (XXVIII) analogues of compound I from hexadeuteroacetone, and pentadeuterobromobenzene, respectively, were carried out.Compound I was esterified with acetic anhydride, decanoic acid and 3,4,5-trimethoxybenzoyl chloride to give the esters II-IV.Acylation of compound XXX with acetyl chloride, 4-fluorophenoxyacetyl chloride and (4-fluorophenylthio)acetyl chloride and the following reduction of the amides with lithium aluminium hydride gave compounds XXXII, XXXIX, and XL.Substitution reactions of 11-chloro-7-fluoro-2-isopropyl-10,11-dihydrodibenzothiepin with the corresponding N-monosubstituted piperazines resulted in compounds XXXIII-XXXV, XXXVII, XXXVIII, XLI and XLII.Alkylation of XXX with 2-(2-chloroethyl)-1,3-dioxolane afforded compound XXXVI.Pharmacological testing of the new compounds, derivatives and analogues of the neuroleptic agent isofloxythepin (I), for discoordinating and cataleptic activities, showed especially for compounds II, XXXIV and XXXVI very intensive and long-lasting effects.The decanoate III has properties of a depot neuroleptic agent.

Conformational Dependence of Isotope Effects for Hyperconjugating Methyl Groups. Nonadditivity of NMR Isotope Shifts in Benzylic Ions

Deuterium substitution in the methyl groups induces long-range downfield shifts in 13C NMR signals of the ortho and para positions of the phenyldimethylcarbenium ion.Similar downfield isotope shifts occur in 19F signals of (p-fluorophenyl)carbenium ions upon deuteration of α-methyl groups.These NMR isotope shifts are analogous to secondary β-deuterium isotope effects on rates and equilibria and arise from hyperconjugative interactions.The effects of substituting entire CD3 groups for CH3 groups are additive, but the effects of deuterium substitution within a methyl group are not additive.The nonadditive behavior is attributed to unequal populations of the possible methyl conformation for partially deuterated methyl groups, so that each C-H(D) bond is not equally involved in hyperconjugation.This interpretation is supported by the observation of an isotope effect on the vicinal 1H-19F coupling constant in the phenylmethylfluorocarbenium ion, PhCFCH3+.

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.