Buckle, F. J.; Pattison, F. L. M.; Saunders, B. C. published the artcile< Toxic fluorine compounds containing the CF link. VI. ω-Fluorocarboxylic acids and derivatives>, Category: esters-buliding-blocks, the main research area is .
AgF (34 g.), slowly added to I(CH2)4CO2Et (preparation given) with shaking and heated 20 min. at 45-50°, gives 1.5 cc. Et δ-fluorovalerate, b16 56-60°, completely nontoxic. In the preparation of 5-hydroxypentanecarboxylic acid from cyclohexanone by the method of Robinson and Smith (C.A. 31, 5351.9), the solid (m. 130°) which is formed is probably dicyclohexylidene peroxide. Br(CH2)5CO2Et (10 g.) and 11.4 g. AgF, heated 30 min. at 50°, give 27% Et 5-fluoropentanecarboxylate, b14 82-4°, LD50 4 mg./kg. Br(CH2)5CO2H (38 g.), 30 g. FCH2CH2OH, and 2.5 g. H2SO4, heated 5-6 hrs. at 120°, give 53% of the 2-fluoroethyl ester, b13 142°; with Ag2F (15 min. at room temperature and 1 hr. at 40°) it yields 2-fluoroethyl 5-fluoropentanecarboxylate, b14 103-5°, LD50 2.5 mg./kg. (CH2)6Br2 (244 g.) and 77 g. PhOH in 400 cc. H2O, treated at the b.p. with 106 cc. 30% NaOH (20 min.) and refluxed 8 hrs., give 79% 6-phenoxyhexyl bromide, b13 174-80°; with CHNa(CO2Et)2 in EtOH, it yields 51% of the Et ester, b. 155-8°/2 × 10-3 mm., of (6-phenoxyhexyl)malonic acid, m. 162-3° (decomposition); at 230°, this yields 58% 7-phenoxyheptanecarboxylic acid (I), m. 69-70°. I (5 g.) and 20 cc. HI (d. 1.7), heated 6 hrs. at 160-70°, give 70% 7-iodoheptanecarboxylic acid (II), m. 43-4°; Et ester (III), b1 114°. III (10.2 g.), treated slowly with 9.7 g. AgF, gives 0.2 g. Et 7-fluoroheptanecarboxylate, b. 191°, LD50 9 mg./kg. (in the preparation of the ester, there is formed some Et 6-heptenecarboxylate, which was transformed into the dibromide to increase the b.p.; a special apparatus is described for the purification). II (13 g.), 110 g. FCH2CH2OH, and 5.5 g. concentrated H2SO4, refluxed 6 hrs., give 62.5% of the 2-fluoroethyl ester, b0.8 122-4°; AgF gives 21% 2-fluoroethyl 7-fluoroheptanecarboxylate, b13 128-30°, fruitlike odor, L.D50 7 mg./kg. Br(CH2)9CO2H (IV) (preparation given) yields 72% of the Et ester, b10 162-4°; AgF gives 20% Et 9-fluorononanecarboxylate (V), b10 135-8°, LD50 10 mg./kg. The 2-fluoroethyl ester of IV b11 184-8°; AgF gives 17% of the 2-fluoroethyl ester of V, b12 145-9°, LD50 10 mg./kg. Et l0-bromodecanecarboxylate, b0.15 137°, 81%; Et 10-fluorodecanecarboxylate, b11 140-1°, 19%; LD50 above 100 mg./kg. 10-Bromodecanecarbonyl chloride, b10 174-5°, 83%; CH2N2 gives 98% 10-bromo-1-diazoacetyldecane (VI), yellow, m. about 30°; 12.5 g. VI in 100 cc. dioxane, treated with 30 g. 20% aqueous NH4OH and 6 cc. 10% AgNO3, gives 49% 11-bromohendecanecarboxamide (VII), m. 105°. VII (3.5 g.), 20 cc. EtOH, and 6 cc. concentrated H2SO4, refluxed 10 hrs., give 47% Et 11-bromohendecanecarboxylate, b. 127°/9 × 10-3 mm.; with AgF, this gives 12% of the II-F analog, b11 152-3°, LD50 less than 20 mg./kg. In compounds of the type F(CH2)nCO2R, it has been established that if n is odd, the compound is toxic and causes fluoroacetate-like symptoms in animals; if n is even, no such toxic properties are shown. This remarkable alternation of properties is discussed in the light of the β-oxidation theory of long-chain carboxylic acids. This theory does not, however, account for all the facts observed. The toxicity is often greatly enhanced if R = CH2CH2F, compared with R = Me or Et. This difference is less obvious when the chain is long (n = 7) and is negligible when n = 9.
Journal of the Chemical Society published new progress about Acids. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Category: esters-buliding-blocks.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics