SU1055742A1 - Complex of alkyl(aryl)-calcium- or alkyl(aryl)-magnesium halogenide with crown ester as reactants for organic synthesis of alcohols - Google Patents

Abstract

Alkyl (aryl) calcium or alkyl (aryl) magnesium halide complexes with | crown-9 Fir of general formula 1: RMXL hee, C2H5, Sb5; M Ca; Md X 3, VG fiudi L “LJIJS as reagents for organic synthesis of alcohols. Di SP 4; ND

Description

calcium. The mixture is filtered from unreacted calcium metal and the resulting solution is poured into 16.2 g (0.045 mol) of DBC 400 ml of absolute THF saturated with nitrogen. It is heated at 60 ° C for 24 1 h. After appropriate treatment, 27.18 g (100%) of the complex was obtained, which is a white crystalline powder, soluble in THF and daFA. M.p. (different).

Found%: C 51.0; H 5.0; Ca 6.6 | i 21.5. .

 aOgt

Calculated%: C 51, b8gN 4.80; Ca 8.62; 1 20.99.

PRI me R 4 Complex dak. To 300 ml of ethereal solution, synthesized from 1.5 g of 0.062 g-atom) of magnesium and 7.1 g (0.05 mol) of methyl iodide, filtered from Henpopeaigursum metal magnesium and containing 6.65 g (mol) of methyl iodide, 600 are added ml of absolute benzene saturated with nitrogen, in which 14.4 g (0.04 mol) of DBC is dissolved. The mixture is heated by stirring for 24 hours at 30 ° C. A light yellow powder is obtained. Yield 21 g (99,: 7%) The complex pacTBOpmvi in THF and DMF. Mp-259260 ° C (decomp.).

Found% 1 s 47.4 | H 5.0 Md 4.3} ij; 25.5. . -.,: ..

 ,

Calculated% J C 47.85 H 5.13; . MD 4.62; 24x10.

Pr ı me R 5. Complex 3 18-K-6. To 300 ml of ethereal solution containing 6.65 g (0.04 mol) of iodide .. methylmagnesium, synthesized from 1.5 g (0.062). magnes and

7.1 g (0.05 mol) of methyl iodide, 1ryl 600 ml of absolute benzene saturated with nitrogen, in which 10.6 g (0.04 mol) of 1c-K-6 are dissolved. The mixture is heated with stirring ... for 24 hours at 30 C. A white fine-crystalline powder is obtained.: Yield 18.95 g (90%). The complex is soluble in THF. And in pyridine, So pl.-. 203-205 C (dec,).

Found% t C 36.0; H 6.1; MD 5.8; E 31.4 ..

C jjMgO J

Calculated% C 36.25 N 6.27; Md 5.64; J 29.49,

: Pr & M in p 6, Complex C2% Md DVK. To 250 ml of ethereal solution containing 4.9 g (0.027 mol) of ethyl iodide iodide synthesized from 1.2 g (0.05 g-atom) of magnesium and

6.2 g (0.04 mol) of ethyl iodide, add 500 ml of absolute benzene in which 9.72 tons are dissolved

(0.027 mol) DBK. The mixture is heated at 30 ° C for 24 hours. After the corresponding

of the treatment, 14.2 g (97.3%) of a light yellow powder was isolated, T. PLLZOO C. (decomp.).

Found% iC48.4; H5.0) Mg 4.2 J; 25.0.

Calculated% 1 With 48,86; H 5.36; MD 4.49; 1 23.47.

Example 12. Complex DVK. To a ml of ethereal solution containing 2.4 g (0.018 mol) of ethylmagnesium bromide synthesized from 1.2 g (0.05 g-atrm) of magnesium and 4.35 g (0.04 mol) of ethyl bromide, add 6, 48 g (0.018 mol) of DCK in 500 ml of absolute benzene. The mixture was heated for 24 hours. A white powder, soluble in pyridine, was used. Yield 8.88 g (100%). So. pl, 300®S (decomp.).

Found% t C 52.9; H 5.6 | Md 4.5; Vg 17.0.

C HflMg OgBr. .

Calculated% t With 53,48; H 5.88, MD 4.93f VG 16.19.

And p and measures 8, the Complex 18-K-6. To 300 ml of ethereal solution containing 2.7 g (0.02 gyopa} bromis: ethylmagnnn obtained from 1.2 g (0.05 g-atsvd) of magnesium and 4.35 g (0.04 mol) of ethyl bromide 500 ml of absolute benzene is poured, in which 5.3 g (0.02 mol) of 18-K-6 is dissolved. The mixture is heated at 30 ° C for 24 hours. In 4 hours, 6.18 g (78%) of white powder is obtained. soluble in THF, ether, pyridine. T.pl-177-179 C,

Found% t C 42.2; H 7.2; MD 6.0; Вг 20,5.

C {4Hj gO Br

Calculated%: C 42.30; H 7.30; MD 6.12; Br 20.12.

Example 9, Complex DBK. To 1.0 g (0.025 g-atom) of calcium heated in a stream of nitrogen: with an iodine crystal, 10 ml of freshly distilled THF or diethyl ether are added, 1/3 volume of a solution of 4.26 g (0.03 mol) of methyl iodide is added in 40 ml of THF or ether. After 15-20 minutes, a slight warming up of the solution is observed; The rest of the methyl iodide solution is added to a mixture of 9 g (0.025 mol) of DCC in 500 ml of benzene. The mixture is heated at 34–40 ° C for 24 hours. The resulting fine white crystalline white powder is filtered, and washed with benzene, hexane. Dry in vacuum at room temperature (2 mm Hg). Yield 13 g (96%). T, mp (decomp).

Found%: C 46.0; H 5.1; Ca 7.4; D 24.0.

Calculated% G With 46.49; H 4.9V; Sa 7.38; i 23; 39. According to the proposed method, all previously described complexes can be performed, P p and m a p 10. Complex. DBK, To 0.48 g (0.02 g-atom) of magnesium heated in a stream of nitrogen with iodine crystal, add 3.55 g (0.025 mol) of iodistomethyl and 7.2 g (0.02 mol) of DBK in 200 ml of absolute benzene. To initiate the reaction, a catalytic amount of megyl magnesium iodine in the ester can be added. The mixture is heated at 48 hours. The formed fine precipitate is filtered, washed with benzene, hexane. Dry under vacuum at room temperature (2 mm Hg). A white powder is obtained, sometimes light yellow. Yield 10., 4 g (98.8%), T. pl., 8.2bO-2b1®C (decomp.). Found% 1 C 47.5 N 5.0 Md 4. ,, D 24.9. CjiHj gOgl Calculated,% C 47.85; H 5.13 | MD 4.625 1 24.10. According to the proposed method, all previously described can be obtained. complexes In all cases, the ratio of cyclic polyether to alkyl (aryl) calcium-alkyl (aryl) magnesium. the halide is Isl, EXAMPLE 11. To 109 g (0.2 mol 500 ml of absolute benzene saturated with nitrogen is poured in, the mixture is heated for 30 minutes at 80 ° C. Then the room temperature is dropped at room temperature with stirring 18 ml (0.02 mol) of isobutyric aldehyde solution dissolved in 100 ml of absolute benzene. The mixture is stirred in 24 h, decomposed with 5% solution of hydrochloric acid to pH 5 in a water layer, the DNA precipitate is filtered off. are washed with hexane, the aqueous layer is extracted with benzene, the benzene extracts are washed successively with a saturated solution of Ma 75 °, , On HCOj, with water and dried with anhydrous POS after distillation of the solvents, the residue is fractionated, and 9 g (51%) of secondary isoamyl alcohol are obtained, Ti.P.112 -114c, ri 1.397, 8.8 ml (49%) of isomer returned aldehyde,; Example 12, to 199 g (0.5 mop C HjMgBr 1S-K-6, 800 ml of absolute benzene is poured, filled with nitrogen, the mixture is heated for 30 minutes. Then at room temperature the stirring is dropped to 20 m (0.2 mol) of ethyl acetate dissolved in 200 MJu of absolute benzene. The mixture is stirred for 24 hours and 4 hours at SQOC., Is decomposed with a 50% chloro solution. ammonium The benzene layer is separated, washed. water, dried b / w in M 504,. Benzene is distilled off, the residue is fractionated. The yield of diethylmethyl carbinol is 9. g (45%). T, pl ipl-122 C,, 31B, P & m 13, K 158 g (0.3 mol) .СН; | Мд1ДБК 1 l of dry benzene saturated with nitrogen is poured, the mixture is kept for 30 minutes at, then at room temperature, with stirring, an equivalent amount of acetophenone, dissolved in benzene in the ratio IslO, is added dropwise. The mixture is stirred for 1 day and 2 hours at. The cooled reaction mass is first decomposed with well water, then with hydrochloric acid solution to pH 5 in the aqueous layer. The precipitate DBC filtered off, rinsed with hexane. An aqueous layer of EC: tragy with benzene; BenzolKY8 EXTENSIONS are washed successively with a saturated solution of Wcr HCO, water and dried with anhydrous MgSO |. After the solvent is distilled off, the residue is fractionated. The output of dimethylphenylcarbinol 22 g (57%), T. bip, 93-94 "with, (13 mm Hg), 532. 15 g (43%) of acetophenone returned. The table shows a range of alcohols obtained under similar conditions. Studies have shown that the use of the alkyl (aryl) calcium and alkyl (aryl) magnesium halide complexes with crown ethers is a formula. (1) has significant advantages in comparison with free Grignard reagents. . Grignard free reagents are prepared and used for the synthesis of sprung-in in an environment of flammable diethyl ether or tetrahydrofuia, which means, in the form of a flammability of synthesis, of value: it narrows the area. Gripenra reagents are pruney and practically exclude them. industrial use. The synthesis of alcohols by acting on the carbonyl-containing compounds of the complexes of alkyl (aryl) calcium (magnesium) halides with crown ethers can be carried out in any hydrocarbon solvent, for example toluene, which significantly reduces the flammability. In addition, in contrast to the sabodnyk reagents. Grin ra. the reaction proceeds without much heat buildup (. it does not require cooling and is easily controlled. The free reagents are unstable and are used freshly prepared. The complexes of alkyl (aryl) calcium (magnesium) halo1 or crown ethers of formula (1) are stable can be stored without loss of activity for a long time and used in the synthesis according to MQpe needs, Interaction of free reaction of Grinra-ra with carbonyl-containing compounds, accompanied by a number of side processes (dehydration, condensation, reduction, This reduces the yield of the target product. The interaction of alkyl (aryl) calcium (magnesium) halides with crown-ethers of formula (1) with carbonyl compounds leads to the formation of alcohol with a yield of 85-95% in terms of the carbonyl reaction that s entered s compound, which is .10-40% higher than with the use of svr, bodyn {Grignard reagents. Example 14. To 158 g (0.3 mol of methylmagnesium iodide complex with DBA tide of 19F 500 ml absoluoric benzene. At room temperature, {3datbT equimolar amount of acetophenon dissolved in benzene IrlO. The mixture is stirred for 1 hour at room temperature and 2 hours. Saw dimethylphenylcarbiol 22 g and 15 g of the original acetophenone Calculated on the pro-pyropha acetone and & is 92% per year. With the use of the Grignard reagent, 1mztilphenylcarbinol and ketone is obtained with a yield of 73% (calculated on acetophenone),; PRI me R 15. K.98.7 g (mol) of the complex ethylmagnane bromide with DBC is poured 500 ml of absolute brewer with nitrogen of benzene. Stirring at room temperature is 14, J7. ml (0.2 mol) of absolute acetone, diluted in 200 m of absolute benzene. The mixture is remeshed for 1 day with a two-way tvmper atura for 2 hours at 80 ° C. ; 1.7 g of immethylt-carbinol and 3.6 ml of acetone are insoluble. The yield of dimethylethyl carbinol based on the reacted acetone is 96%. With the use of the Grignard reagent, dimethylethylcarbinol from ketone is obtained with a yield of 50%. Example 16. To 199 g (0.5 mol) of an ethyl magnesium bromide complex with 18-K-b, 500 ml of absolute benzene saturated with nitrogen is added. Then, at room temperature, 20 ml (0.2 mol) of ethyl acetate, dissolved in 200 ml of absolute benzene, are added dropwise with stirring. The mixture is stirred for 1 day — at room temperature. and 4 h at, then decompose 5: 0% solution of ammonium chloride. The benzene layer is washed with water, dried with sulphate: sodium or magnesium, Distilled vdt benzene, 9 g (98% calculated as unreacted ethyl acetate) and 11 ml of ethyl acetate are added. With the use of Grigny rat diethylmethylcarb1inol reagent from zfira, a yield of 67% is obtained. PRI me R 17. To 98.4 g (0.2 mol) of the hschagniybro: MFA complex with DBC, SOO ml of absolute benzene saturated with nitrogen is added. At room temperature, 21.8 ml (0.2 mol) of benzaldeg “and dissolved in 200 ml of absolute benzene are added dropwise. The mixture was stirred for 1 day, and the reaction mass was decomposed with hydrochloric acid to pH 5.0 in the aqueous layer. BE divided 16.3 g (99% based on the reacted benzaldegnsch) and 8.7 ml of benzaldegnd. Using the Grignard reagent, ethylphenylcarbinol from aldehyde is obtained with a yield of 78%,

Claims (2)

Alkyl (aryl) calcium or alkyl (aryl) magnesium halide complexes with (crouy-eshir of the general formula 1: dmh-b ГЗе К = СКУДЭД 'СБОДМ ^ СаОД'. X = 3, Br LP I ' (ίΤΓΐΐ as reagents for organic synthesis of alcohols. WITH one 1055742 2