1.
tert-Butylamine (98%, Alfa Aesar), triethylamine (99%, Fisher Chemicals), and toluene (99.9%, Fisher Chemicals, ACS grade) were used as received.
2.
Triphosgene (98%) was purchased from Alfa Aesar and used as received.
3.
The addition was carried out at such a rate that an internal temperature of 15 °C was not exceeded.
4.
The solids are suspended in the organic phase.
5.
The filtrate was concentrated to give an additional 2.35 g of di-tert-butylurea.
6.
It is imperative to wash the solids extensively with water to remove any residual Et3N·HCl, which may decrease the yield for the subsequent step.
7.
Working at 50% scale, the checkers obtained 23.1 g (76%).
8.
The product has the following physicochemical properties: White solid, mp 245-246 °C; 1H NMR pdf (300 MHz, DMSO-d6) δ: 1.18 (s, 18H), 5.45 (s, 2H); 13C NMR pdf (75 MHz, DMSO-d6) δ: 29.3, 48.8, 157.0; IR (ATR) 3349, 1633 cm-1; MS (EI+) m/z 172 (M+, 26), 157 (67), 57 (100); HRMS (EI+) m/z calcd for C9H20N2O 172.1576, found 172.1569; Anal. Calcd for C9H20N2O C, 62.75; H, 11.70; N, 16.26; Found C, 63.02; H, 11.94; N, 16.16.
9.
Diethyl ether (ACS grade) was purchased from Fisher Chemicals and dried by distillation over sodium/benzophenone under an argon atmosphere.
10.
tert-Butyl hypochlorite was prepared according to a literature procedure: Teeter, H. M.; Bell, E. W. Org. Synth. 1952, 32, 20.
11.
Solid potassium tert-butoxide (97%) was purchased from Alfa Aesar and used as received.
12.
Upon complete addition the reaction vessel does not need to be protected from light.
13.
The progress of the reaction can be monitored by 1H NMR analysis of aliquots taken directly from the reaction mixture.
14.
Anhydrous K2CO3 (ACS grade) was purchased from Fisher Chemicals and used as received.
15.
The tert-butanol generated in the reaction should be completely removed to prevent interference with the subsequent distillation.
16.
The dimensions of the distillation head are as follows. Single piece construction with inlet for vacuum/inert gas, 10/18 thermometer joint on top, 14/20 joints for distillation and collection flasks, approx. 35 mm length of condenser × 65 mm height (head).
17.
Di-tert-butyldiaziridinone is collected at 47-49 °C (7 mmHg) and stored away from light.
18.
The submitters reported a bp of di-tert-butyldiaziridinone of 60-64 °C (7 mmHg).
19.
Working at 50% scale, the checkers obtained 11.1 g (75%).
20.
The product has the following physicochemical properties: bp 47-49 °C /7 mmHg; 1H NMR pdf (300 MHz, benzene-d6) δ: 1.07 (s, 18 H); 13C NMR pdf (75 MHz, benzene-d6) δ: 27.2, 59.3, 159.3; IR (ATR) 1929, 1875, 1856 cm-1; MS (EI+) m/z 170 (M+, 5), 157 (67), 131 (15), 84 (40), 57 (100); HRMS (EI+) m/z calcd for C9H18N2O 170.1419, found 170.1420; Anal. Calcd for C9H18N2O C, 63.49; H, 10.66; N, 16.45; Found C, 63.61; H, 10.79; N, 16.17.
21.
(E)-1-Phenyl-1,3-butadiene was prepared according to a literature procedure: Grummitt, O.; Becker, E. I. Org. Synth. 1950, 30, 75; or Wittig, G.; Schoellkopf, U. Org. Synth. 1960, 40, 66. Similar results were obtained for step C using the diene prepared from either protocol.
22.
Tetrakis(triphenylphosphine)palladium (9% min. palladium) was purchased from Pressure Chemical Co. and used as received.
23.
Reaction is performed neat.
24.
The submitters added di-tert-butyl-diaziridinone via a 10-mL addition funnel. The checkers observed more consistent results using a syringe pump.
25.
Silica gel 40-63 D (60 Å) (Silicycle, Quebec City, Canada) was used.
26.
Working at 50% scale, the checkers obtained 2.86 g (95%).
27.
The product has the following physicochemical properties: 1H NMR pdf (300 MHz, benzene-d6) δ: 1.36 (s, 9 H), 1.39 (s, 9 H), 3.55 (dm, J = 8.4 Hz, 1 H), 4.05 (d, J = 1.2 Hz, 1 H), 4.86 - 4.95 (m, 2 H), 5.92 (ddd, J = 17.1, 10.2, 8.4 Hz, 1 H), 7.07-7.16 (m, 3 H), 7.27 (dm, J = 6.9 Hz, 2 H); 13C NMR pdf (75 MHz, benzene-d6) δ: 29.1, 29.2, 53.7, 53.9, 63.8, 65.5, 115.6, 126.5, 129.4, 141.8, 145.1, 159.2; IR (ATR) 1682 cm-1; MS (EI+) m/z 300 (M+, 55), 285 (100), 229 (81), 132 (60); HRMS (EI+) m/z calcd for C19H28N2O 300.2202, found 300.2191; Anal. Calcd for C19H28N2O C, 75.96; H, 9.39; N, 9.32; Found C, 76.01; H, 9.60; N, 9.31.