h a 92% yield of 2-octanol is determined by GC. The flask is cooled to room temperature, and the reaction mixture is treated with water (4 mL) and filtered through Celite. The solvent is removed under reduced pressure and the product purified by silica gel column chromatography and distillation [10.5 g, 81% isolated yield, bp 85 °C (18 torr)]. 2-Octanol: IR (neat, absorptions in cm"1) 3400 (br); NMR (60 MHz, CDC13, values from internal Me4Si) 3.8 (m, 1 ), 1.9 (s, 1 H, OH), 1.35 (m, 10 ), 1.2 (t, 3 H), 0.9 (t, 3 H); MS (70 eV, m/e, relative intensity) 130 (M+, traces), 57 (7), 55 (16), 43 (20), 45 (100).Acknowledgment. This work was supported by the Italian C.N.R. (Progetto Finalizzato Chimica Fine e Se-condaria).
Single crystals of 10 for X-ray analysis were obtained from acetone/hexane at -10 °C after several weeks.Reaction of 1 with MejSiCl: Cp'jNb(Cl)0 (11). To a stirred dichloromethane solution of 1 (38.2 mg, 0.10 mmol) was added ClSiMe3 (10.8 mg, 0.10 mmol); the solution became yellow immediately. After the mixture was stirred for 30 min, the solvent was removed at reduced pressure. Trituration of the residue with toluene, followed by cooling of the toluene extracts at -10 °C, gave yellow crystals of Cp'2Nb(Cl)0 (52%) (11). IR (KBr, cm"1) v 3075 (w), 2922 (w), 1505 (s), 1453 (s), 1359 (m), 1220 (s), 1088 (m), 1023 (vs), 777 (m), 853 (s), 816 (vs), 617 (m);
Acrolein (C
3
H
4
O), (2‐propenal) is the simplest unsaturated aldehyde
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. The primary characteristic of acrolein is its high reactivity due to conjugation of the carbonyl group with a vinyl group. More than 80% of the refined acrolein that is produced today goes into the synthesis of methionine. Much larger quantities of crude acrolein are produced as an intermediate in the production of acrylic acid. Acrolein is a highly toxic material with extreme lacrimatory properties. Special care in handling is required because of its flammability, reactivity, and toxicity. Acrolein is highly reactive in a variety of reactions, including oxidation and reduction and in reactions with alcohols. Because of its antimicrobial activity, it has found use as an agent to control the growth of microbes in process feed lines.
An investigation of the low-temperature matrix isolation photochemistry of ferraazetines, Fe2(g-CRCHNBul 2)(CO)6 (la, R = H; lb, R = CH=CHPh) in rigid matrices is reported. Near-UV irradiation of la and lb in CO-saturated methylcyclohexane (MCH) at 298 K yields ferrapyrrolinones 2a and 2b, Fe2|g-CRCHNBulC(0)|(C0)6, and in the presence of ZerZ-butylacetylene, la and lb form ferrapyridines 3a and 3b, 2(µ-€ € = :)(€0)6.The photoinduced insertion of CO and ZerZ-butylacetylene occur at different positions in the ferraazetine metallacycle. CO insertion occurs between the Fe-N bond of the metallacycle whereas Zerz-butylacetylene insertion occurs between the Fe-C bond. At 15 or 8 K in MCH, 1:1 ZerZ-butyl acetylene/MCH, or CO matrices, the primary photoprocess for la and lb involves Fe-N bond cleavage to yield coordinatively unsaturated compounds 4a and 4b, respectively. Irradiation of 4a in a MCH matrix gives bridging CO compound 5, ß2(µ-0 0 1)(µ-0 )(0 )5, which is formed by a CO ligand swinging from the adjacent Fe center to occupy the vacant coordination site created by the Fe-N cleavage. In a 1:1 zerz-butylacetylene/ MCH matrix, irradiation of 4a at 98 K gives a Zez-r-butylacetylene adduct 6, ß2(µ-0 0 )(0 )6( 1€=0 ). When warmed to 298 K, 6 inerts the ZerZ-butylacetylene ligand to form 3a. Irradiation of 4a in a 13CO matrix at 8 K gives CO insertion product 2a with l3CO incorporation at a terminal position with no evidence of incorporation at the carbonyl of the acyl ligand. When 4b is irradiated in MCH at 15 K, compound 7, Fe2^-C(CH=NBu')CHCHPh)(CO)6, is formed. 7 derives from a ligand exchange of the C=NBu' group of the ferraazetine ring in 4b for its pendant styryl group, CH=CHPh. When irradiated at 98 K or 298 K in MCH, lb forms 7 with no detectable intermediates and the photoconversion is much faster at these temperatures than at 15 K. At 298 K 7 quantitatively re-forms lb after 2 h in the dark.
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