SU1310381A1 - Method for producing metal alcoholates - Google Patents

Abstract

The invention concerns derivatives of alcohols, in particular alcoholates of the general formula lMe (OR) n, where Me is a metal atom: indium, lanthanum, germanium, titanium, bismuth (III), niobium, tungsten (YI), iron (III); R is C, -C4-alkyl of normal or iso-structure, n is an integer of 3-6, which as catalysts can be used in various catalytic processes. Improving the quality and yield of 1, the dilution of the range of the obtained substances is achieved using a different solvent for the original metal salt. The process is carried out in an absolute medium from chloride or oxochloride in a disilicate ester of an aliphatic hydrocarbon or alkyl halide and an alcoholic solution of sodium alkoxide at (-20) -) (+ 20) followed by boiling, separating NaCl and distilling off the solvent. It is advisable to add an aliphatic hydrocarbon, such as hexane, to the initial alcohol solution. Output 1 70-100% versus 0% (only in isopropanol) or 76% (only in ethanol). In the case of the pre-boiling of the solutions before the reaction in the absence of inert diluents, the yield is reduced to 1. 1 hp, f-crystals, table I SL

Description

The invention relates to a method for producing metal alkoxides in catalysts and components of catalytic compositions, as well as raw materials for the production of high-purity and active oxide materials.

The aim of the invention is to increase the yield and quality of target iiyKTOB products, as well as expand their range.

The goal is achieved by introducing the corresponding metal chloride or oxochloride into an alcoholic solution of alkali-t l and sodium in the form of its suspension or solution in diethyl ether, an aliphatic hydrocarbon or alkyl halide at (-20.) - (+20) s, followed by boiling the reaction mixture.

Example 1. In a flask under argon, 2.5 g (0.11 mol) of metallic sodium are dissolved in a mixture of 50 ml of isopropyl alcohol and 50 ml of hexane Gspirt absolutized by boiling for several hours over aluminum isopropyl followed by distillation, and hexane over metallic sodium, and then over zeolite). Slight heating is used to complete the reaction. The synthesis is carried out in a round bottom flask with a stirrer, an addition funnel and a reflux condenser. The flask is placed in a cooling mixture. A current of dry argon is passed through the device. .

A suspension of 5.4 g (0.033 mol) is fresh. ferrous chloride chloride (HI) in 50 ml of absolute hexane at 0 ° C and vigorous stirring are added dropwise for 1 hour to the sodium isopropyl solution. After complete homogenization of the reaction mixture as a result of the formation of bimetallic sodium alkoxychloride and iron (III)

15

Fe (ORG-i o) rapidly increases in storage of the preparation from 90-100 0 (for 1 cyfoK) to 150 ° С (in a year),

5 The IR spectrum of this compound in the region of oscillations of the OR-group is very basic A1 (ORG-IEO) s: 2976c .; 2938 s. 2873 sr; 2620 ate; 1468 wed; 1382 1332 wed; 1165 oh; 1145 о.с;

0 1128 pp ;; 1056 ate; 1010 s .; 956 897 ate; 845 sl.pl ;; 838 sr .; 603 о.с; 555 Wed; 530 cl, pl; 485 sr .; 473 sr .; 433 wed,

The analysis data for Fe, C, and H are shown in the table.

. Example 2. To a solution of 1.8 0.08 mol) sodium in 50 ml of abs. Ethanol, cooled to -5 for 40 minutes, a solution of 6.84 g (0.02 mol) of WOC14 in 50 ml abs, diethyl ether Then another 50 ml of alcohol is added to the reaction mass (to completely dissolve the formed alcoholic water and boil it for 30 minutes. The solution obtained after centrifuging the NaCl does not contain chloride ions. After evacuating, the solution of the bodies remains crystalline

 WO (OEt), Upon recrystallization of e from abs, alcohol, 7.5 g of the substance is obtained (yield 98%), t, mp, (with rapid heating) 15-130 ° C, i.e. 130-135 ° C / JO mm (with dec,).

35 IR SpectrumJ 2975 s .; 2935 s .;

2870 s; 1460 ate, 1380 w .; 1140 avg Wed; 1095 s; 1070 e .; 922 s. 795 s; 603 e,

. Examples 3-13, Synthesis of the connection of the dineneum (l) of other derivatives is carried out analogously to examples 1 and 2.

The table shows the quantities and the active substances of chloride or oxochloride, sodium alcohol (in the calculation

20

25

40

the extraction of white curd begins with the introduction of metallic sodium), a simple precipitate of sodium chloride. The reaction mixture is stirred for another 30 minutes at reflux. The NaCl precipitate is separated by centrifugation,. Fe (ORG-CZD) .-, partially adsorbed by the precipitate, extracted with boiling hexane (3 times 20 ml each). When evacuating the combined solution, 7.2 g of red-brown liquid is formed, which in 20-30 minutes it turns into a lighter warlike substance. Output 95%, t, kip, 150 ° s (0.1 mm): t, pl.

volumes of solvents for both reagents, reaction conditions at the stage of reagent discharging (this one and further interaction in growing

50 thief (stage II), as well as the properties of the solid product and the results of its organic microorganism.

Examples 14-22 (comparative).

55 For comparison, the syntheses of compound (I) are given under the conditions of the prototype. The use of alcohol solutions of chlorides or oxochlorides is accompanied by

Fe (ORG-i o) rapidly increases during storage of the preparation from 90-100 0 (for 1 cyfoK) to 150 ° С (in a year),

The IR spectrum of this compound in the oscillation region of the OR group is very close to A1 (ORG-IEO) s: 2976c .; 2938 s .; 2873 sr; 2620 ate; 1468 wed; 1382s; 1332 wed; 1165 oh; 1145 о.с;

1128 sm; 1056 ate; 1010 s .; 956 s .; 897 ate; 845 sl.pl ;; 838 sr .; 603 о.с; 555 Wed; 530 cl, pl; 485 sr .; 473 sr .; 433 wed,

Data analysis for Fe, C and H are given in the table.

. Example 2. To a solution of 1.8 g of 0.08 mol) sodium in 50 ml of abs. Ethyl alcohol, cooled to -5 ° C for 40 minutes, a solution of 6.84 g (0.02 mol) of WOC14 in 50 is added dropwise from a funnel. ml abs, diethyl ether. Then another 50 ml of alcohol is added to the reaction mass (to completely dissolve the formed alcohol, and boil it for 30 minutes. The solution obtained after centrifuging the NaCl does not contain chloride ions. After evacuating the solvent, the crystalline remains

WO (OEt), When it is recrystallized from abs, alcohol, 7.5 g of substance is obtained (yield 98%), t, mp, (with rapid heating) 15-130 ° C, i.e. 130-135 ° C / JO mm (with dec,).

IR SpectrumJ 2975 s .; 2935 s .;

2870 s; 1460 ate, 1380 w .; 1140 sr .; FROM Wed; 1095 s; 1070 e .; 922 s .; 795 s; 603 e,

. Examples 3-13, The synthesis of the compound (l) of other derivatives is carried out analogously to examples 1 and 2.

The table shows the amounts of the initial substances of chloride or oxochloride, sodium alkylate (in the calculation

on input metallic sodium),

 on input metallic sodium),

volumes of solvents for both reagents, conditions for carrying out the reactions at the stage of discharging the reagents (stage 1) and further interaction in the solution (stage II), as well as the properties of the target product and the results of its organic microorganism.

Examples 14-22 (comparative).

55 For comparison, the syntheses of compound (I) are given under the conditions of the prototype. The use of alcohol solutions of chlorides or oxochlorides is accompanied by

it gives a decrease in the yield of compound I, especially in the case of the pre-boiling of the solutions (before introducing them into the reaction) in the absence of inert diluents. In the absence of the possibility of purification, the compounds (I) are contaminated by the products of hydrolysis (examples 14-16). The use of benzene as a solvent (Example 17) or an increase in temperature leads to the same results. the first stage of synthesis above 20 ° C is due to the formation of water in the reaction mixture (examples 18 and 19), as well as the products of chloride and alcoholate reduction (example 21) and, soluble in alcohol, significantly more than NaCl (examples 16). During the synthesis of compounds (I) at temperatures below -20 ° C, the solubility of NaOR (and sometimes both components) decreases sharply and, as a result, the rate of exchange reaction (Example 22).

Claims (2)

1. A method for producing alcoholates of metals of the formula I or II 14 M (OR) (1) or MO (OR) n (II), where M is a metal atom selected from the group: indium, lanthanum, germanium, titanium, bismuth (III), niobium, tungsten (VI) or iron (III), R - C; | -C 4 is a normal or iso-alkyl, n is an integer from 3 to 6, including the introduction of choride or oxochloride of the corresponding metal into an alcohol solution, the corresponding sodium alkoxide while cooling the SRI, boiling the obtained reaction mixture, separating the sodium chloride precipitate and distilling off the solvent, in order to increase the yield and quality of the target products, as well as expand their range, the introduction of metal chloride or oxochloride is carried out in the form of its suspension or solution and in diethyl ether, aliphatic hydrocarbon or alkyl halide at (-20) - () C. 2. Method POP.1, which differs from the fact that an aliphatic hydrocarbon is introduced into the alcoholic alcohol solution of sodium. FeClj 5,4 0,033 Hexane NaOPr50 (eye- - lao penzi) 2 WOCL 6.8 0.02 The same NaOEt 1.8 0.08 EtOH 5050 “AXIS 6.8 0.02 Also NaOMe 1.8 0.08 MeOH 0; 40 30 50.50 4WCL 10.0 0.025 Et ... O 150 5 FeCl 5.4 0.033 EtjO 50 4.2 0.02 EtjO 100 (suspension) LaClj 4.9 0.02 HeOPTAN NeOPr- «o1, 50 (suspension) 0.11 iso-rton 50 + hex 50 0; 6P 30 -five; AO ml EtOH) NaOEt 3.5 0.15 EtOH - 10; 90 30 150 NaOBu-H 2.5 0.11 j-BuOH 5; 30 30 70 NaOPr-nv) l, 3 0.06 Mio-PrOH 50+ 0; 15 30  50 0.06 "o-PrOH30 + 10; 30 40 f heptane 20 7.2 95 KpacHO- brown, BOCKOo6p .B-BO, T.PL. 90-, t. Kip. 150 ° C / / 0.1 MM 7.5 98 Furious. Cryst., wag 130i35 c / / (Y mm 5.7 89 Besiv, Krist., Hell 130-  / 10 mm 2.1 nineteen Desc., Liq., Bk. 90 s /, 8.9 9.8 Red-brown liq., not distilled ) h 4.9 Mjo), 90 95 White fine-crystalline powder, t.rasl. 1 50 С Bessch. crista. t. 170 С (10-g different. 260 ° C) 24.17 23.96 46.31 46.39 8.92 9.02 48.54 48.42 25.04 25.26 5.00 5.26 ; 7.02 56.79 14.72 14.81 3.81 3.70 40.42 40.78 31.18 31.72 .6.08 6.61 20.25 20.31 52.60 52.40 9.9 9.83 39.20 39.33 36.81 37.01 7.08 7.20 43.31 43.97 34.02 34.19 6.91 6.65 8SeST 10.3 0.05 CCl 50 NaOMe 4.5 0.20 9GeCl, 10.3 0.05 Petro-NaOMe 4.5 0.20 MeOH 100-10; 30 90 leyn ether 50 10liC l, 9.5 0.05 Also NaOEEt 4.6 0.20 EtOH 20 -10; 30 90 .100 11liCl 9.5 0.05 HexaneNaOEt4.6 0.20 EtOH -20j 30 -90 50. 2o 12 BiCl 3, J 0.01 50 ml NaOEt 0.7 0.03 EtOH 50 20; 20 i3 NbCly 5.3 0.02 30 ml NaOEt 2.2A 0.10 EtOH 50 0; 15 40 Comparator 14 FeCl. 5, A 0.033 yoke rgona 50 15 SSC 6.8 0.02 EtOH 30 NaOEt (kip, 1 hour) WOCl 6.8 0.02 MeOH 0 NH, "benzene" -MeON 100 (kip. 1 h) MSON 100 -ten; 30 90 2.5 0.11. —PrOH 0; 60 30; 50-hect. San 30 1.84 0.08 KtOH 30 -5j 40 30 Excess — NHj current Ge (OMe) 4.7 50 Without fluid lp; -18 ° C, bk. 37.21 36.93. 23.84 24.41 6.0 6.10 / 36 mm Ge (, 5 45 Too 3.7.21 36.93 23.84. 24.41 6.01 6.10 8.0 70 Bessch. Cryst ,, t, pl. 40 s, ko 133 ° C / 5 mm Ti (OEt), 9.1 80To the same 20.95 21.20 41.21 42.10 8.95 8.76 3.4 100 5.5 90 Bessch. crisst., quickly blacken, ust. in ef. r-re Bessch. fluid, tkip, 160 С / / О, 1 mm Fe (OPr-Hio), О О 7.4 95 2.5 40 Similar- 51.52 48.42 23.11 in Example 2 Similar to example 3 (but contain I; 6% NK, Cl) 37.21 36.93. 23.84 24.41 6.0 6.10 20.95 21.20 41.2 42.10 8.93 8.76 61.05 60.75 20.71 20.93 4.15 4.36 29, -67 29.22 37.21. 37.75 7.51 7.86 25.26 4.74 5.26  17FeCL, 5.4 0.033, Benzene NaOPr- .2.5 0, l 1 eeo-RhOH O 0; 60 30 50 (eye- I50- benzene Penza) 50 18GeCl 0.3 0.05 Without ras-NaOMe tel 19TiCl4 9.5 0.05 Identical NaOEEt 4.6 0.20 EtOH 200 25; 30 90 20TiCl 9.5 0.05 No ras NaOEt 4.6 0.20 EtOH 200 0; 30 90 tel 21FeClj 5.4 0.033 Hexane NaOPr - 0.11 PrOH 10O + 25; 120 30 50 (eye- hekpeney) -san 100 22WCl 5.0, 0.01 TooNaOEt 5.2 0.06 EtOH 75 35; 60 30 75 According to chemical analysis data, the target product contains about 25% WOj (OEt) j, 1150, 980, and 880 cm, which are present along with the WO (OEt) 4 bands are impossible, since the reaction to the gas phase occurs 4.5 0.20 MeOH 100 25; 30 90 which is confirmed by the data of IR-spectroscopy: absorption bands WOjCOEt). Purification of the desired product by sublimation turns out to be disproportionate: WO (OR) (OR) g WOj (OR) j. 46.39 8.45 9.02