Mamedov, Shamkhal; Gadzhiev, F. R.; Rzaev, A. S. published the artcile< Ethers of glycols and their derivatives. LXVII. Synthesis of alkoxymethyl ethers of ο- and p-ethylbenzyl alc>, Safety of (9Z,12Z)-Methyl octadeca-9,12-dienoate, the main research area is .
By the alk. method there were synthesized several new alkoxy derivatives of the Me ether of ο- and p-ethylbenzyl alc. and the ο- and p-monoethylbenzyl ether of ethylene glycol. To a mixture of ο- and p-ethylbenzyl alc. (16.3 g.), 21.78 g. PhNMe2, and 50 ml. dry Et2O, 24.5 g. α-chloromethyl isoamyl ether was added dropwise, and the mixture stirred and heated 4.5 hrs. at 30-40° and worked up to give 19.32 g. mixture of isopentoxymethyl ethers of ο- and p-ethylbenzyl alc. b5 141-2°, n20D 1.4828, d20 0.9392. Similarly, 9 new alkoxy ether mixtures of general formula ο- and p-EtC6H4CH2OCH2OR were obtained (R, % yield, b.p., n20D, and d20 given): Me, 58.7, b19 127-8°, 1.4972, 0.9877; Et, 60.0, b5 106-7°, 1.4920, 0.9721; iso-Pr, 52.0, b5 113-14°, 1.4857, 0.9523; Pr, 50.0, b5 123-4°, 1.4872, 0.9568; iso-Bu, 59.0, b5 129-30°, 1.4820, 0.9455; Bu, 65.6 b5 135-6°, 1.4840, 0.9483; Am, 60, b5 146-7°, 1.4833, 0.9420; n-C6H13, 66.6, b5 157-8°, 1.4806, 0.9312; and n-C7H15, 59.8, b5 167-8°, 1.4800, 0.9279. To a mixture of 34 g. ethylbenzyl alc., 50 g. acrylonitrile, and 150 ml. dry C6H6 1.5 g. MeONa was added, and the mixture stirred 5 hrs. at 40-50° and worked up to yield 94% mixture (I) of β-cyanoethyl ethers of ο- and p-ethylbenzyl alc., b1 137-8°, n20D 1.5080, d20 1.0108. To 90 g. MeOH saturated with 18 g. HCl 19 g. I was added, and the mixture heated 2 hrs. and worked up to give 48% mixture of β-carbomethoxyethyl ethers of ο- and p-ethylbenzyl alc. (II), b. 133-4°, n20D 1.4970, d20 1.0397. A mixture of 250 ml. MeOH, 13 g. NaOH, 13 ml. H2O, 15 ml. Et2O, and 15.54 g. II was kept 24 hrs., CO2 passed in, and the precipitate worked up to give 67.4% mixture of β-(ο- and p-ethylbenzoxy)propionic acids, b3 178-80°, n20D 1.5185, d20 1.0815. Ethylbenzyl alc. (50 g.) was saturated with gaseous HCHO, dry HCl passed in at 5-10°, and the mixture worked up to give 57% mixture (III) of chloromethyl ο- and p-ethylbenzyl ethers, b2 97-8°, n20D 1.5210, d20 1.0803. To PhONa from 26.5 g. PhOH and 4.6 g. Na, 18.5 g. III was added dropwise, and the mixture stirred and heated 4 hrs. at 50-60° and worked up to give 53% mixture of phenoxymethyl ethers of ο-and p-ethylbenzyl alc., b1 153-5°, n20D 1.5502, d20 1.0530. A mixture of 23.2 g. ethylbenzyl chloride, 37 g. BuOH, and 20 g. powd. NaOH was heated 8 hrs. at 80-90° and worked up to give 76.4% mixture of Bu ο- and p-ethylbenzyl ethers, b. 102-3°, n20D 1.4830, d20 0.9078. Similarly the following ethers of the general formula ο- and p-EtC6H4CH2OR were obtained (R, % yield, b.p., n20D, and d20 given): Pr, 82, b4 92-3°, 1.4910, 0.9178; iso-Bu, 60.0, b4 96-7°, 1.4862, 0.9088; iso-Am, 79.0, b4 108-9°, 1.4834, 0.8998. Am, 80.9, b4 113-14°, 1.4860, 0.9028; n-C6H13, 69.7, b4 128-9°, 1.4855, 0.9008; and n-C7H15, 73.4, b4 141-2°, 1.4850, 0.8981. A mixture of 250 g. ethylene glycol and powdered 100 g. NaOH was heated until the NaOH was dissolved, 154.5 g. ethylbenzyl chloride added dropwise, and the mixture heated with stirring 5 hrs. at 120-30° and worked up to give 52% mixture (IV) of mono ο- and p-ethylbenzyl ethers of ethylene glycol, b2 151-3°, n20D 1.5150, d20 1.0280. A mixture of 18 g. IV, 80.4 g. Ac2O, 50 ml. dry C6H6, and 2 drops H2SO4 was stirred and heated 4 hrs. at 30-40° and worked up to give 65% IV acetate, b2 126-8°, n20D 1.4985, d20 1.0391. To a mixture of 18 g. IV, 18.15 g. PhNMe2, and 50 ml. dry Et2O 18.4 g. chloromethyl Bu ether was added dropwise and the mixture stirred and heated 3 hrs. at 30-40° and worked up to give 51% mixture of ο- and p-ethylbenzyl butoxymethyl ethers of ethylene glycol, b3 157-8°, n20D 1.4809, d20 0.9684. Similarly the following ο- and p-EtC6H4CH2OCH2CH2OCH2OR were obtained (R, % yield, b.p., n20D, and d20 given): Me, 58, b12 156-7°, 1.4912, 1.0105; Et, 54.6, b3 137-9°, 1.4906, 0.9967; iso-Pr, 62.6, b3 147-8°, 1.4827, 0.9772; Pr, 55.5, b3 153-5°, 1.4847, 0.9842. Bu, 71.0, b3 162-3°, 1.4831, 0.9698; iso-Am, 62.8, b3 169-70°, 1.4812, 0.9629, Am, 62.5, b3 175-6°, 1.4821, 0.9659; n-C6H13, 67.7, b3 185-6°, 1.4807, 0.9539; and n-C7H15, 54.0, b3 192-3°, 1.4805, 0.9530.
Azerbaidzhanskii Khimicheskii Zhurnal published new progress about Ethers. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Safety of (9Z,12Z)-Methyl octadeca-9,12-dienoate.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics