Notes- ortho-Substitution Rearrangement of Benzyltrimethylammonium-benzyl-C¹⁴ Iodide

The reaction of chlorosulfonyl isocyanates with allenes and olefins

“…HC1, reflux methylbutanoic acid (32), treatment of which with aqueous ammonia led to the primary amine 24 and ultimately 25. The mechanism of formation of 11 is consistent with the initial formation of the allyl carbonium ion 7 (path a), followed successively by the 1,4-dipolar cycloaddition of 7b to a second molecule of the electrophilic dipolarophile CSI and hydrolytic cleavage to 11.14 -We recently reported the stereospecific cis addition of CSI to cis-(cis 16g) and trans-ßmethylstyrene (trans 16g) to yield 2 + 2 cycloadducts, N-chlorogulfonyl-m-(cis 17g) and -<rans-3-methyl-4phenyl-2-azetidinone (trans 17g). 6 The retention of configuration of R1--R4 in cis and trans 17g is unequivocally supported by nmr data. Thus the eclipsed cis protons in cis 17g show the expected vicinal coupling of 7.25 Hz while the ¿rans-skewed protons in trans 17g displayed vicinal coupling of 4.00 Hz.…”

“…The methylene chloride extract was evaporated in vacuo to dryness, and the residue was recrystallized from ether-hexane to give 2.4 g (32%) of 2-(1-cyclohexenyl)-2-propenamide (lOe): mp 135-137°; uv max (CH3OH), 234 µ (e 8,500); ir (KBr), 6.05 µ (C=0).…”

“…Found: C, 68.78; H, 9.58; N, 9.82. The cis-trans 8b mixture (4.5 g, 0.03 mol) gave 2.4 g (64%) of a 13% cz's-87% trans mixture of 3-ethylidene-4,4-dimethyl-2azetidinone (9b): mp 56-57°(needles from hexane); ir (KBr), 5.71 µ (0=0); nmr (CDCI3), for trans 9b, 7.65 (broad singlet, 1, NH), 6.03 (q, 1, J = 7 Hz, =CH), 1.73 (d, 3, J = 7 Hz, =CHCHs), and 1.47 (s, 6, CH3), for cis 9b, 7.65 (broad singlet, 1, NH), 5.61 (q, 1, / = 7 Hz, =CH), 1.94 (d, 3, / = 7 Hz, =CHCH3), and 1.38 (s,6,CH,).…”

“…Recently we reported that the stepwise 1,2-dipolar cycloaddition of chlorosulfonyl isocyante (CSI) to alienes [2,4-dimethyl-2,3-pentadiene (6a), 3-methyl-1,2butadiene (6d), pentamethyleneallene (6e) and 1,2-cyclononadiene (6h) ] proceeded via path a to produce initially, in the transition state, an allyl-type stabilized carbonium ion (7) leading ultimately to /3-lactams (8,9) and/or from the aqueous extract, 2-carboxamido-l,3- :oc-c=c: 10 butadienes (10). 6 The reaction between CSI and 6d produced a third product (11) which seemed to be an adduct of 2 equiv of CSI with one of 6d.5 In this paper, we (i) report on CSI addition to alienes 2-methyl-2,3pentadiene (6b), 2,3-pentadiene (6c), 1,3-diphenylpropadiene (6f), and phenylpropadiene (6g); (ii) provide experimental details of the reaction between CSI and 6a-h, with proof of structure of both /3-lactam and diene amide products; (iii) identify 11 by degradation and independent synthesis; (iv) provide experimental evidence for the stereospecific cycloaddition of CSI to cis-and ¿rcms-/3-methylstyrene (cis and trans 16g),6 and…”

Natrium‐ und kalium‐organische Verbindungen. Teil I: Eigenschaften und Reaktionsweisen [1]

“…aufgebauten Ladungen kurz. Von dem damit verbundenen hohen Energiegewinn profitiert auch die konkurrierende Sommelet-Umlagerung (96) [209,210]. Bei der gleichfalls von Stevens [21 I] untersuchten basischen Isomerisierung tertiarer Amine (97) geht die negative Ladung auf ein vorher ungeladenes Stickstoffatom iiber.…”