95; H, 7.31; N, 10.15.4-Amino-5-tert -butyl-rl'-(dimethylamino)bipheny1-3-carbonitrile (8c) was prepared from 0.17 g (0.49 mmol) of 13 in 25 mL of CH3CN by addition of 1 mL of HBF, (40% in ether).After being stirred for 45 min, the solution was treated with lu until an aqueous extract was no longer acidic. The solvent was evaporated, and the residue was several times extracted with ether. The resulting colorless material was recyrstallized from methanol and yielded 70 mg (51%) of 8c: mp 137-138 "C; MS m / z 293 (100, M' ), 278 (28), 263 (10); 'H NMR (90 MHz, CCl,) 6 1.44 (9, 9 H, tert-butyl), 2.95 (s,6 H, N(CH3),), 4.49 (s,2 H, NH,), 6.5-7.6 (m, 6 H, aromatic protons); l R (KBr) 347013390 (NH), 2900 (CH), 2205 (CN). Anal. Calcd for CIOHaN3: C, 77.78; H, 7.90; N, 14.32. Found: C, 77.61; H, 7.71; N, 14.02. Diethyl 2-[3,5-Di-tert-butyl-l-[4-(dimethylamino)-phenyl]-4-imino-2,5-cyclohexadien-1-yllmalonate ( 12). A 2.55-g (16-"01) portion of diethyl malonate was treated with 0.12 g (5.2 "01) of Na dissolved in 20 mL of EtOH. The resulting solution was added to a solution of 4c (from anodic oxidation of 0.28 g (0.86 mmol) of aniline IC) in acetonitrile. After immediate decolorization, the excess of diethylmalonate was evaporated at 100 "C (0.1 Torr). The product 12 was isolated as an oil (yield, 93%): MS m/z 482 (6, M+), 426 (13), 324 (loo), 309 (44), 173 (68); 'H NMR (90 MHz, CDC13), 6 1.13 (t, 6 H, J = 7 Hz, OCH,CH,), 1.31 (8, 18 H, tert-butyl), 2.89 ( 8 , 6 H, N(CH3),), 4.02 (4, J = 7 Hz, OCHzCH3), 4.17 (8, CH(CO0Et)z; the integration of the signals at 4.02 and 4.17 corresponds to 5 H), 6.68 (8, vinylic protons), 6.84 (q, A2Bz, J = 9 Hz, aromatic protons; the integration of the signals between 6.56 and 7.11 corresponds to 6 H), a signal for the NH proton was not found, in CeDe it was detected at 9.98 (9, broad, 1H); IR (KBr) 3400 (NH), 2960 (CH), 1760/1735 (C=O), 1565 (C=N) cm-'. Anal. Calcd for C29H42N204: C, 72.17; H, 8.77; N, 5.80. Found: C, 71.95; H, 8.61; N, 5.72. 1,5-Di-tert -butyl-3-[ 44 dimet hylamino) phenyl]-6-imino-2,4-cyclohexadiene-1-carbonitrile (13) was obtained after addition of a 7% excess of NBu4CN to the electrogenerated solution of 4c (from 0.27 g (0.83 mmol) of IC). It was recrystallized from petroleum ether (30/50), giving yellow crystals (yield, 64%): mp 98 "C dec; MS m / z 349 (1, M+), 324 (2), 293 (loo), 278 (36); 'H NMR (90 MHz, CC1$ 6 1.06 (8, 9 H, tert-butyl), 1.33 (8, 9 H, tert-butyl), 2.99 (9, 6 H, N(CH3),), 5.97 (d, 1 H, J = 2 Hz), 6.60 (d, J = 2 Hz, vinylic protons), 6.91 (9, A2B2, J = 9 Hz, aromatic protons, the integration of the signals between 6.50 and 7.50 corresponds to 5 H), 10.69 (9, broad, 1 H, NH); IR (KBr) 3390 (NH), 2890 (CH), 2225 (CN), 1585/1525 (C=N) cm-' . Anal. Calcd for C23H31N3: C, 79.04; H, 8.94; N, 12.02. Found: C, 79.25; H, 9.12; N, 12.23.Reaction of 4c with Thiophenolate Ion. To a solution of cation 4c (derived from 0.28 g (0.86 mmol) of IC) in acetonitrile were added 1 g of powdered NazCOs and 1 g (9.0 mmol) of thiophenol. From the resulting colorless solution ...
Electrophilic nitration of dibenzofuran with nitric acid by a charge-transfer mechanism occurs exclusively at the 3-position and on the other hand, substitution at the 2-position predominates in the acylation, in which a classical σ-complex mechanism is important.
Disaster and space environments are similar in that they are closed environment, with limited lifelines. Here, we examined the similarity between disaster food and space food, to explore interactive problem-solving of food support for disaster and space environments. The Japan Disaster Food Certification Standards (Japan Disaster Food Society) and the Japanese Space Food Certification Standards (Japan Aerospace Exploration Agency) requirements and certified products, which were posted on the websites as of June 16, 2021, were compared. Certified products were classified into "staple foods," "main and/ or side dishes," "milk and dairy products," "fruits," "confectionery and favorite beverages," "condiments," "dietary supplements," and "sets." Certification standards involved six items for Japan Disaster Food and eight items for Japanese Space Food. Most standards were similar. Concretely, both standards demanded room temperature storage, tough packaging and hygiene management in facilities. Both emphasized habitual food and easy eating. However, the best-by date was $6 mo for Japan Disaster Food, but $1.5 y for Japanese Space Food. In addition, Japanese Space Food required noted nutritious, food hygienic, eatable in space, cookable by specific equipment, endurable pressure by launch, and domestically produced food. There were 171 and 47 products of Japan Disaster Food and Japanese Space Food, respectively. Staple foods (pregelatinized rice, etc.) and main and/or side dishes were commonest among Japan Disaster Foods and Japanese Space Foods, respectively. It is possible to utilize of Space Food as Disaster Food, but there are some issues that must be cleared before "utilization of Disaster Food as Space Food."
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