Synthesis of 3-chloro-3-methyl-d3-diazirine

Abstract

solution was concentrated and distilled in a Kugelrohr apparatus (100 °C pot temperature, 30 mm) to provide 0.342 g (50%) of 2-methylcyclohexanol. Analysis by VPC (10% TCEP, 6 ft x l/a in., 110 °C) revealed no observable amounts of the cis isomer. The cis and trans isomers may also be distinguished by the NMR signal of the proton on the carbon adjacent to the oxygen. The cis isomer exhibits a multiple! at 3.7 ppm while the trans isomer exhibits a multiplet at 2.9 ppm. Again, none of the cis isomer could be detected.Acknowledgment is made to the donors of the Petroleum Research Fund, administered by the American Chemical Society, for support of this research.

Photochemistry of Crystalline Chlorodiazirines: The Influence of Conformational Disorder and Intermolecular Cl···NN Interactions on the Solid-State Reactivity of Singlet Chlorocarbenes

“…The results of solution photolyses in Table were consistent with literature reports for analogous compounds with a benzyl rather than 4-phenylbenzyl substituents and can be understood in terms of the expected carbene intermediates (Scheme ). ,− ,− In inert solvents and in the absence of trapping reagents, biphenylchlorocarbene 5a reacts with its own precursor to form azine 9a as the only observable product (Scheme , eq 1). , In contrast, halocarbenes 5b − d have migrating α-groups that undergo fast intramolecular rearrangements. Chlorocarbenes 5b , c give rise to alkenes ( Z )- 6 and ( E )- 6 by facile 1,2-H shifts (Scheme , eqs 2 and 3), ,,− and carbene 5d gives rise to 6d by an efficient 1,2-Ph migration (eq 4) 3 …”

“…Although product yields improved substantially, those of compounds 4b and 4d remained relatively modest (25 and 13%, respectively). Knowing that low yields (5−22%) have been reported for less hydrophobic benzylic diazirines using the Graham procedure, − it was of interest to carry out a side-by-side comparison of the two methods. Along with the synthesis of 4b , we decided to test the formation of 3-(1-naphthylmethyl)-3-chlorodiazirine ( 4e ) and 3-benzyl-3-chlorodiazirine ( 4f ), both of which have been previously reported (Table ).…”

“…Photoreactions in diazirine crystals proceed smoothly and are relatively clean. Aryldiazirine 4a gives only azine 9a by reaction of carbene 5a with a neighboring diazirine molecule 4,17 and (dimethylbenzyl)chlorodiazirine 4d gives the α-chlorostyrene 6d by a selective 1,2-Ph migration in the singlet state of 5d …”

Mechanism of Inactivation of Inducible Nitric Oxide Synthase by Amidines. Irreversible Enzyme Inactivation without Inactivator Modification

“…N -(3-(Aminomethyl)benzyl)acetamidine (1400W, 4). Acetimidic acid ethyl ester hydrochloride (247 mg, 2.00 mmol), prepared according to the method of Liu et al, was dissolved in 10 mL of ethanol, and then 567 mg (2.40 mmol) of 1-( N -Boc-aminomethyl)-3-(aminomethyl)benzene was added all at once. The reaction mixture was stirred at 0 °C for 3 h and then partitioned between 20 mL of diethyl ether and 20 mL of H 2 O.…”

A Remarkably Efficient Markovnikov Hydrochlorination of Olefins and Transformation of Nitriles into Imidates by Use of AcCl and an Alcohol

“…Imidates are an important class of compounds that find application in the preparation of s ‐triazines,12 1,2,4‐triazoles,13 1,2,4‐oxadiazoles,13 diazirines,14 selenoesters,15 selenoamides15 and 2‐substituted pyrimidin‐4‐(3 H )‐ones,16 and also in the conversion of pyrimidine into pyridine 17. As important as these substances are, experimentally convenient methods for their preparation are unfortunately unavailable.…”