• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention includes novel alkali metal complex compounds (and processes for their preparation) which are useful, inter alia for the hydrogenation of alkali metals at room temperature or below room temperature to form hydrides or nitrides.
    公开号:SU1003758A3
    申请号:SU782617568
    申请日:1978-05-16
    公开日:1983-03-07
    发明作者:Богданович Борислав
    申请人:Штудиенгезельшафт Коле Мбх (Фирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING COMPLEX COMPOUNDS OF ALKALINE METALS The invention relates to methods for producing new complex compounds of alkali metals, which can be used as a catalyst for the preparation of hydrides or alkali metal nitrides. All currently available analytical methods do not allow to establish the structure of target products. The known disodium salt of pentane1, 3,5-tritione, which is used in the synthesis of 1,6,6a-tritiopentalena 1 and the disodium salt of 1,3,5-triketone, which is used to obtain the corresponding 1,3,5-triketone 12. Purpose the invention, cjiHTe3, of new complex compounds — catalysts, which make it possible to obtain alkali metal hydrides or nitrides at a lower temperature and atmospheric pressure. The goal is achieved by the fact that according to the method of obtaining complex compounds of alkali metals, consisting in the fact that the compound of the general) formula 1 $ - $ -V with §- $ O II II. (I (i (i (i R / i HBU i IEBR - lower alkyl, waterpad, phenyl. R - hydrogen, phenyl; 1 2. R and R, fold, give cn, cf, cn, R - hydrogen, R -., R - lower alkyl, hydrogen, phenyl g
    subjected to interaction with alkali metal in the medium of tetrahydrofuran, 1,2-dimethoxyethane or dioxane and / or tetramethylethylenediamide at -20 - + 60С.,
    The number of alkali metal atoms in alkali metal complexes produced by the proposed method largely depends on the structure of compound T-IV used in each individual case or on the type of its substituents, alkali metal, ether used, respectively, amine and the conditions under which the reaction is carried out. For example, 1,2-dithiol-3-thion (I, R, R H) reacts with lithium in tetrahydrofuran with the formation of a dilithium derivative, which is opposite under the action of 4-phenyl-1,2-dithiol-3 -thione. (l, R H, R CgHj) with lithium under the same reaction conditions, a lithium complex with seven lithium atoms in a molecule is obtained.
    The alkali metal complexes produced by the method proposed with more than two alkali metal atoms are organometallic compounds with high reactivity that are sensitive to air and moisture, and as a result, they must be prepared in a protective gas atmosphere. The alkali metal complexes produced by the process of the invention can be contained in a solution and then used in dissolved form, but they can also be used for the catalyst in solid, tricotted form.
    The proposed alkali metal complexes with several α, alkali metal volumes in a molecule can be applied either alone or in combination, for example, with transition metal compounds, to produce alkali metal hydrides, fixing molecular nitrogen, and also as catherization agents for hydrogenation.
    Example. To a solution of 3.73 g (12.0 mmol) of 2,4-diphenyl-1,6, ba-trtiapentalen (j) in 200 ml of absolute tetrahydrofuran (THF) was added 1.49 g (214 mg-at) finely ground -: lithium dioxide and the prepared mixture was stirred for 18 h at. Thereafter, the solution colored in color from deep violet to black was separated at 0 ° C by filtration from finely ground lithium which did not react. By decomposing the aliquot portion (2.0 ml) of the resulting solution with water and acidimetric determination of lithium, it was determined that 9.81 g of lithium reacted with the mole of compound (1), which corresponds to the conversion of the starting compound () to the following complex 98% . In order to isolate the lithium complex in solid form, the tetrahydrofuran solution was mixed with 500 ml of pentane with stirring and the mixture was kept for 2 hours. Then the black painted suspension was filtered at 0 ° C, the resulting precipitate was washed with pentane and dried in vacuo ( 10 mmHg) at 20 ° C to constant weight. As a result, 4.96 g (91.4%) of a complex possessing a high sensitivity to air was obtained. Calculated,%: C 55, 63; H 4, 45; S 21.19; Li 15.32,
    Cj H SjOLi o (MW 453.4). Found,%: C 55.22; H 4.65,
    0 S 21.13; Li 15.10.
    The complex injected in solid form is soluble in tetrahydrofuran, and as a result of the addition of pentane to the tetrahydrofuran solution
    again, a complex of the same composition can be besieged.
    .P r m ime R 2. According to the example with example 1, 1.06 g (3.36 mmol) of 2,4-diphenyl-1, 6, 6a-tri1-pentalen (G)
     was injected into the interaction with 0.57 g (82.2 mg-at) finely powdered lithium in 50 MP tetrahydrofuran at. After reacting for 5 hours, the solution was separated from not
    5 who entered into the reaction of finely powdered lithium and by hydrolysis of an excess amount of lithium it was established that 9.7 g-lithium reacted with the mole
    0 of compound (1), which corresponded to the degree of conversion (1) into the decalythium complex () 97%. In order to improve the decalitium complex as an additive compound
    5 with 1,2-dimethoxyethane, the solution was evaporated in vacuum (0.2–0.3 mm Hg) to 25 ml and at 0 ° C the residue was mixed with 20 ml of 1,2-dimethoxyethane, and a colored d black sediment. The suspension was kept for 3 hours and the precipitate was filtered off from the deeply colored solution, after which the precipitate was dried in vacuum (20 ° C, 10 mmHg) to a constant weight.
     The result was 0.82 g
    (51.5%) with high sensitivity to the action of air complex.
    Calculated,% C 53.4; H 4.70;
    0 Li 14.70.
    ., (Mv 471.5) Found,%: C 53.0; H 4.80; Li 14.67.
    By adding 40 ml
    5 1,2-dimethoxyethane to the mother liquor, it was possible to additionally select 0.27 g (17% of the theoretically calculated value) of the same complex (14.70% was calculated, 14.50% was found), so that the total yield of the obtained complex was l 1.09 or 68.5% of the theoretically calculated value. Example 3: By analogy with Example 1, 1.98 g (6.33 mmol) of 2,4-diphenyl-1, 6.6a-tritiapentalen (T) introduced interaction with 3.59 g (156 mg-at) of finely powdered sodium in 60 ml of tetrahydrofuran, after carrying out the reaction for 21 hours, the deep purple violet solution of the sodium complex was separated by filtration at 0 ° C from unreacted finely divided sodium. By decomposing an aliquot part, the solution leg was obtained with water and the acidimetric determination of sodium determined that 9.98 g of sodium at-one reacted with a mol of 2 4-diphenyl-1,6,6a-trityapentalene (1), which corresponded to an almost quantitative transformation starting compound (I) to the decanter complex (T). By adding 120 ml of 1,2-dimethoxyethane to the tetrahydrofuran solution, by analogy with that described in Example 2, the solid form was recovered in a yield of 2.30 g (57.5% of the theoretically calculated value) of the decanted E complex in the form of an additive with , 2-dimethoxyethanol and the ratio of I ;. Calculated,%: At 36.4. (m. in. 632.4). Found,%: Na 36.25. Example4. By analogy with example 1, 2.15 g (6.90 mmol) of 2,5-diphenyl b, 6a-tritiapentalen (M) was reacted with 1.25 g (179 mg-at) of finely divided lithium in 50 ml of tetrahydrofuran. stirring the reaction mixture for 16 hours at 0 ° C; the solution was colored deep purple; was separated by filtration from unreacted lithium. By hydrolysis, an aliquot of the resulting solution and the acidimetric determination of lithium showed that the compound (I) was practically quantitatively transformed into decalithium com Plex (I) (10.2 g-lithium reacted with the mole of Compound (P). As a result, 200 ml of pentane was added to the tetrahydrofuran solution with a yield of 2.84 g (90.8% of the theoretically calculated value), by analogy with the described in example 1, it was obtained in solid form, me decalithium complex in the form of a 1: 1 adduct with tetrahydrofuran, Calculated,%: Li 15.30. (MW 453.4) Found,%: Li 15.56. For chemical the characteristics of the resulting complex used, in addition to hydrolysis, deuterolysis (equation 1). Hydrolysis of the complex in solid form (in the form of an adduct with tetrahydrofuran) or in a tetrahydrofuran solution. Daval is lithium hydroxide, lithium sulfide (yield 80% calculated on the sulfur bound in the complex), and also a mixture of hydrocarbons containing 17 carbon atoms, which consists of la from isomers of 1,5-diphenyl-1,3-pentadiene and a small amount of 1,5-diphenylpentenenes (total yield of C-17 hydrocarbons is approximately 70% of the theoretically calculated value). With deuterolysis of the complex, tetradeutero-1,5-diphenyl1, 3-pentadiene and a small amount of hexadeutero-1,5-diphenylpentene were obtained. Hydrolysis and deuterolysis reactions can be considered as evidence of the structure of hydrocarbon residues (Which are in the complex. Besides decalitium The 2,5-diphenyl-1, 0,6a-tripenthenol complex is characterized by its absorption band on a UV spectrum of about 580 nm, 11000 (in the form of a 51 p molar solution in tetrahydrofuran). Example 5. By analogy with Example 1 0 , 84 g (2.84 mmol) alpha- (4-phenyl-1,2-dithiol-3-ylidene) aceto she (I, I) with the interaction with 0.51 g (73 mg-at) finely ground lithium in 60 ml of tetrahydrofuran. After stirring the reaction mixture for 18 h at 0 ° C, the deep purple color solution of the lithium complex was separated by filtering at an excess of lithium at 0 ° C. After acidimetric determination of the amount of lithium in the solution, it turned out that 10.1 g-lithium reacts with a mole of compound (T1I) to form a deJ lithium complex of compound (II). Example 6. To a solution containing 9.46 g (35.6 mmol) of 1,5-diphenylpentane-1, 5.5-trione (P /) in 450 ml of absolute tetrahydrofuran, was added 14.3 g (2.06%). mol) finely divided lithium; and the mixture was stirred at, and after stirring for about 24 hours, the solution took on a deep blue-violet color. After reacting for 40 hours, the solution was separated by filtration from an excess amount of lithium, and by hydrolysis of an aliquot part of the solution and acidimetric determination of lithium, it was determined that 10.06 g-lithium react with a mole of triketone (LV-) t which corresponds to the quantitative conversion of triketone to the decalithium complex of the compound () In order to isolate the complex in solid form, the solution was evaporated in vacuo to 200 ml, the residue was mixed with 400 ml of tetramethylethylenediamine (Me NCH-j CH NMe) and the mixture was stirred for 2 hours at. Filtration and drying of the precipitate under high vacuum to yield 8.50 g (40% of the theoretically calculated value) obtained in solid form a decapitium triketone complex () as an additive with 1 mol of tetramethylethylenediamine and 2 mol of tetrahydrofuran. Calculated,%: N, 4.70; Li 11.66. .dNaOrtstso (M.V. 595.4). Found: N: 4.72J; Li 11.48. Example 7. To a solution containing 3.61 g (13.6 mmol) of 1,5-d phenylpentane-1,3,5-trione () in 115 ml of absolute 1,2-dimethoxyethane per (,), was added 6 , 4 (0.92 g-at) finely chopped litin and the prepared mixture was stirred at. The course of the reaction was monitored by taking samples of 5.0 ml from the suspension at certain intervals. 11 grains were filtered from excess lithium, the filtrates were decomposed with water and titrated with 0.1 and. hydrochloric acid solution. After carrying out the reaction for 2.27 and 48 hours, the lithium concentrations in the solution were found to be 7.9, 9.8 and 10.3 g-at, respectively, per mole of compound (LV). This corresponded to the quantitative conversion of triketone (0) to the decalithium complex of compound (y) described in Example 6, in this example 1,2-dimethoxyethane was mixed with tetrahydrofuran as the reaction medium. Example 8. According to analogy with example 1, 2.02 g (9.9 mmol) of 6-phenylhexane-2, 4, B-trione (V) was reacted with 2.85 g (0.41 g-at) finely ground lithium in 75 ml of tetrahydrofuran. After reacting for 50 hours, the solution was separated by filtration and an excess amount of finely ground lithium and, as described in Example 1, it was determined that 5.2 g-at lithium reacts with a mole of triketone (V), which corresponds to the quantitative conversion of triketone. (V) to the pensionschite complex. In order to isolate the complex, the solution was evaporated in vacuo to 15 ml, the residue was mixed with 35 ml of tetramethylethyl diamine, and then the solution was evaporated in vacuum to 30 ml. The resulting suspension was stirred for 2 hours at which time it was filtered and the precipitate was dried under high vacuum. As a result, 2.05 g (56% of the theoretical calculated value) of the complex was obtained. Calculated,%: N 3.80 L1 9.41. S 8 6o eNaLl, o (MW 737.4). Found,%: N 3.81; Li 9.18. Example 9. By analogy with example 1, 1.05 g (5.58 mmol) 2, dimethyl-1, 6, ba-tritiapenthenene (Vj) was introduced into the interaction with 0.72 g (103 mg-at) finely ground lithium in 30 ml of tetrahydrofuran. After carrying out the reaction for 3 hours, by analogy with that described in Example 1, it was established that 4.0 g-athy react with the mole of the compound (V,) and after 5 hours of stirring the reaction mixture at a concentration of lithium in the solution remained almost constant . Accordingly, at 0 ° C, the formation of the tetralithium complex of the compound (yj) occurred in the solution. Example 10. By analogy with example 1, 0.27 g (1.3–25 mol) .. 5-Fenyl-1,2-dithiol-3-thione (UE) was reacted with 0.27 g (38 mg- a) finely ground lithium in 50 ml of tetrahydrofuran. At various times, 0.5 ml samples were taken from the suspension, the samples were filtered, ({the diltrate was mixed with water and an excess of 0.1N hydrochloric acid, followed by a reverse titration with 0.1N sodium hydroxide solution. After the reaction within 3 hours, it was found that 7.04 g of lithium react with the mole of the compound (Vil), and for the next hour the concentration of lithium in the solution remained almost constant. In accordance with this, from the blend (VII G and lithium, when in tetrahydrofuran formed hexacidal to Compound complex (ViJ). To isolate the complex in solid form, the solution was separated by filtration from excess lithium, mixed with 33 ml of tetramethylenediamine and evaporated in vacuo to 40 MP. Filtration and drying of the precipitate formed under high vacuum gave 0.38 g (66% of theoretically calculated value) of the lithium complex of the compound () in the form of its 1: 1 adduct with tetramethylethylenediamine and tetrahydrofuran. Calculated,%: N 6.27, Li 10.9. ,, S, NaOLi. (Mv. 448.2) Found,%: N 5.96; Li 11.4. Example 11. By analogy with example 1, 0.57 g (2.73 mmol) of 4-phenyl-1, 2-; Cytiol-3-thion (VI II) was reacted with 2.34 g (102 mg-at a) finely chopped sodium hydroxide in 100 ml of tetrahydrofuran. By analogy with that described in example 10,
    Reaction time, h
    monitored the progress of the reaction by sampling (15.0 mp) and acidometric determination of sodium in the samples. Reaction time:
    I
    Gat Ma I Coloring Mole (VI, I) | solution
    with the heptanate complex of the compound (USP). Example 12. By analogy with example 1, 1.50 g (8.2 mmol) of benzo 1,2-dithiol-3-thione (GC) was introduced into the reaction with 0.82 g (117 mg-at) of finely ground lithium. in 180 ml of tetrahydrofuran. After conducting the reaction for 2 h, the concentration of lithium, corresponding to b, 2 g-at Li (g-mol of benzo-1,2-dithiol-3-thione, was detected in the solution after carrying out the reaction for 24 h - 6.1 g-at Li (g-mol benzo1, 2-dityl-3-tyna). By adding 250 MP of pentane to the tetrahydr furan solution with a yield of 1.22 (50% of the theoretically calculated value), the benzoyl hexanalium complex was isolated in solid form -1,2 dithiol-3-thione as an additive compound with one molecule of tetrahydrofuran. Calculated,%: Li 14.1. (Mv 298) Found,%: Li 13.9. Example 13. Similarly With example 1, 0.74 g (4.0 mcl) of benzo-1,2-dithiol-3-thione (P) was reacted with 0.85 g (37 mg-at) finely ground sodium in 70 ml of tetrahydrofuran After the reaction was carried out for 48 hours at OC, a concentration of sodium corresponding to 4.0 g-at Ma (g-mole of benzo-1,2-dithiol-3-thione) was detected in the solution. From compound (L.) and sodium, tetrahydrofuran formed a tetranium complex of compound (IX). Example 14. To a solution containing 1.04 g (3.33 mmol) 2,4-d phenyl-1, b, ba-tritiapentalen (O in 50 ml of absolute tetrahydrofuran (THF) OC was added in pieces of potassium. The reaction mass was stirred within 48 hours at the end of the indicated time, potassium metal was separated from the solution and weighed. The potassium loss was 0.43 g, which corresponded to the interaction of 3j, 3.r-aT potassium with the compound () molar solution. again mixed with ca. lium (2.27 g) and the reaction mass of remakes for 17 h at room temperature: Natnaya temperature. by aliquotting the amount of the solution with water and by acidimetric determination of potassium it was established that the molar ratio K s (T) was 3.9: 1.0. The solution was further stirred for 93 hours in the presence of potassium, and the potassium complex was formed as a black colored precipitate. Filtration and drying of the precipitate under high vacuum to constant weight yielded 1.59 g of the complex (yield 88%). Calculated,%: K 28.9. CjiHwSbOK (mv 540.5) Found,%: K 29.8. Example 15. The use of a hexazole complex of benzo-1,2-dithiol-3-thione, obtained in accordance with example 12, as a catalyst in the hydrogenation of lithium to form lithium hydride. A solution of 2.24 mmol of benzo-1,2-dithiol-3-thionhexaly in 90 ml of tetrahydrofuran (prepared as described in Example 12) with stirring, temperature and hydrogen atmosphere (atmospheric pressure) was mixed with 1.0 g (143 mg-at) finely divided lithium, and the complete and slow absorption of hydrogen. The stirring of the reaction mixture under an atmosphere of hydrogen was continued until the absorption of hydrogen ceased, which occurred after 92 hours, with a total of 730 ml of hydrogen being absorbed by hydrating lithium precipitated after a specified time, separated from the catalyst solution and identified by IR spectroscopy. The absorbed amount of hydrogen corresponded to the conversion of 43% of the applied lithium into lithium hydride, which means that 28 mol of lithium hydride was formed per mole of catalyst. Example 16. The use of the hexa-lithium complex of benz6-1,2-dithiol 3-thione, obtained in accordance with example 12, in combination with iron trichloride (molar ratio of the lithium complex to iron trichloride 6: 1) as a catalyst in the hydrogenation of lithium with lithium hydride formation). A solution of 2.40 mmol of benz.o-1,2-dithiol-3-thionhexaly in 80 ml of tetrahydrofuran (obtained by analogy with that described in example 12) was mixed with 0.068 g (0.4 mmol) of iron trichloride ( in solid form) and the mixture was stirred for 1/2 hour. After the indicated time had elapsed, 1.0 g (143 mg-at) of finely ground lithium was added to the catalyst solution while stirring in an atmosphere of hydrogen (atmospheric pressure) uniform absorption of hydrogen. After 94 hours, the hydrogen uptake practically ceased, and a voluminous lithium hydride precipitate formed. The absorbed amount of hydrogen (1740 ml of hydrogen at 20 ° C / 760 mmHg) corresponded to a conversion of 101% of the applied lithium into lithium hydride, which means that 60 moles of lithium hydride are formed per mole of catalyst. In the experiment conducted for comparison, it was possible to show that in the same conditions, but in the absence of the benzo-1,2-dithiol-3-thione hexalitium complex, finely ground lithium hardly interacts with hydrogen, either with or without the addition of iron trichloride. . Example 17. The use of the sodium complex of 2,4-diphenyl-1,6, batritiapentalene (example 3) in combination with iron trichloride (molar ratio of the sodium complex to iron trichloride 6; 1) as a catalyst in the hydrogenation of sodium to form Sodium 1.30 g (4.15 mmol) of 2,4-diphenyl1, b, ba-tritiapenthenene (T) was dissolved in 40 ml of tetrahydrofuran. The prepared solution was mixed with 2.73 g (118.7 mg-at) of finely ground sodium and the mixture was stirred for 20 h at. After this time, the solution was separated by filtration from excess sodium, an aliquot of the solution was decomposed with water, and it was determined by means of acidimetric determination of sodium that the molar ratio of sodium to compound (T) was 9.2: 1.0. To the remaining solution containing 3.46 mmol of the sodium complex of tritiapentalen, 1.34 g (58.1 mg-at) of finely divided sodium were added under stirring in a hydrogen atmosphere, and a very slow absorption of hydrogen began (within 76 hours, 43 ml of hydrogen. I eaten; 0.094 g (0.58 mmol) of iron trichloride in 10 MP of tetrahydrofuran was added to the suspension, and the reaction mixture was again stirred in a hydrogen atmosphere at 0 ° C, and hydrogen was uniformly absorbed. n was observed after 67 hours, totally absorbed 557 ml of hydrogen at that corresponds to the conversion of approximately 80% of the sodium applied to sodium hydride (13-14 catalytic stages per mole of catalyst), Example 18. Sodium complex 2,4-diphenyl-1,6,6- in situ, in the presence of iron trichloride. As in Example 17, a combination of catalysts was used to hydrogenate sodium to form sodium hydride). A solution of 0.57 g (1.79 mmol) of 2,4 diphenyl-1, 6,6a-tritiapentalen (1) and 0.56 g (3.58 mmol) of iron trichloride in 50 ml of tetrahydrofuran was mixed with stirring under hydrogen atmosphere with 3.73 g (162 mg-at) of finely powdered sodium, and the uniform absorption of hydrogen began. At a constant temperature and a constant stirring rate until the absorption of hydrogen was completed, for a total of 62 hours, a total of 1430 ml of hydrogen was absorbed at 20 ° C and 760 mm Hg. Art., which corresponded to the conversion of 74% of the applied sodium to sodium hydride or the catalytic formation of 66 mol of sodium hydride per mole of catalyst. Example 19 Benzo-1,2-dithiol-3-thione hexalium complex (Example 12) as a catalyst for the fixation of molecular nitrogen. 1.28 g (183 mg-at) of finely divided lithium was suspended in 80 ml of tetrahydrofuran and the suspension was stirred under a nitrogen atmosphere (atmospheric pressure) using a magnetic stirrer at a stirring speed of 400 rpm. During 24 hours, 18 ml of nitrogen (20s) was absorbed. After that, 0.30 g (1.63 mmol) of benone-1,2-dithiol-3-thione was added to a suspension of lithium at the same stirring speed and the same temperature under a nitrogen atmosphere, and after several hours (at that time The hexo-benzo-1,2, -dithiol-3-ti hexyl complex formed (Comparative Example 12), the azoT was absorbed significantly, more rapidly. From the time of adding benzo-1,2-dithiol-3-thione to the end of nitrogen uptake, for approximately 130 hours, 300 .. ml of nitrogen at 20 ° C was totally absorbed, which corresponded to a 41% conversion at lithium to lithium nitride. During this time, 15 mol of lithium nitride was formed per mole of the benzo-1,2-dithiol-Zgtio hexalicylate complex. Lithium nitride hydrolysis yielded 95-100% of the theoretically calculated amount of ammonia. p 20. A benzal-1,2-dithiol-3-thione hexalium complex (example 12) b combined with iron trichloride (molar ratio of lithium complex to iron trichloride -) as a catalyst for fixing molecular nitrogen. To freshly prepared. a solution of 2.15 mmol of the benzo-1,2-dithiol-3-thione hexalite complex (comparative npHbfep 12) in 60 ml of tetrahydrofuran at -40 ° C and stirring added 0.058 g (0.36 mmol) of ferric chloride (in solid mixture) and the resulting mixture was transferred for 1 hour at. Immediately after this, to the prepared solution at 0 ° C under nitrogen atmosphere (atmospheric pressure) was added with stirring 1.3 g (185 mg-at) of finely ground , lithium, and the absorption of nitrogen began. Until the cessation of nitrogen absorption, at a constant nT G-at LI
    Duration
    J Mole (X) I reaction, h
    ABOUT
    0.5
    one
    3
    6
    eight
    24 28
    Color solution
    Krasna Brown Goluba
    Bluish-Fioletova II
    Violet temperature and a constant stirring rate, for 115 hours, was absorbed by 426 ml of nitrogen at 20 ° C, which corresponded to the conversion of 58% of the applied lithium to lithium nitride or the catalytic formation of 16.5 mol of lithium nitride per mole of catalyst, or 98 mol of lithium nitride 1 gram of iron. During hydrolysis, 88% of the expected amount of ammonia was obtained. Example 21. To a solution of 0.40 g (1.28 mmol) of 2,4-di-enyl-1,6,6a-tritiyapentalen (T) in 40 ml of tetrahydrofuran was added 0.89 g of potassium-sodium alloy consisting of 80 wt.% Potassium and 20 wt.% Sodium. The prepared mixture was re-entangled for 67 h with, and the solution was colored from deep red to black-violet. Through hydrolysis of an aliquot part of the solution and acidimetric determination of alkali metals, it was found that a total of 9: g-at alkali metals react with the mole of compound (1). Using atomic adsorption spectroscopy, the atomic ratio of Na: K was determined to be 1: 2.8. Example 22. By analogy with example 10, 1.10 g (3.20 mmol) of 2,5-diphenyl-3,4-e-ylene-, 6,6a-tritiapentalen (X) is mixed with 0.64 g (92 g -at) lithium sand in 35 ml of THF at. The use of lithium, depending on the reaction time as in Example 10, was monitored by sampling (2.0 ml) and acidimetric determination of lithium in the samples. The reaction course characterizes the following.
    From (X) lithium in THF with OC, then a non-ionic complex () is formed.
    Example 23. By analogy with example 10, 0.85 g (2.88 mmol)
    I From (U) and lithium to THF, the tetralithium complex (11) then occurs.
    Pr 24. By analogy with example 10 1.03 g (4.44 mmol) Tetraltium complex (XM) is produced from (XlJ) and lithium in THF at 0 ° C. Example 25. A solution of 2.06 g (6, 62 mmol) 2,4-diphenyl-1,6, batritiapentalena (G) in 100 ml of THF and 4.58 g (0.2 g-at) of sodium sand are stirred for 70 hours, the Acidimetric determination of sodium content showed that 8.9 gms of sodium prs yagirovapo with one mole (1). The THF solution, separated from excess sodium, was evaporated under vacuum to 28 mi, and by adding dropwise 100 ml of dioxane with continuous stirring, it was treated with succession, and a black, formless precipitate fell out. It was stirred for 18 h at, then the precipitate was filtered, washed with dioxane mill and dried under vacuum (10 Torr) to constant weight. It was obtained 1.99 g sleduttsogo
    1,7-diphenyl-1,3,5-heptantrione () is mixed with 0.61 g (88 g-at) of lithium sand in 35 ml of THF, which is followed by monitoring the use of lithium depending on the reaction time:
    权利要求:
    Claims (1)
    [1]
    1-phenyl-6-methyl-1,3,5-heptantrione (XM) was mixed with 0.90 g (130 g-at) of lithium sand in 35 ml of THF at OC and, depending on the reaction time, the use of lithium complex was controlled as black is very sensitive to the air flooding. Calculated,%: Na 34.1. ScNs OaNa (MW 607) Found,%: Na 34.4. Example 26. A solution of 5.0 mmol of benzo-1,2-dithiol-3-thionhexalythion complex (example 12) in 15 ml of THF at 25 ° C was treated with 15 ml of pentamethylene diethylenetriamine (XI II), and immediately plowing a brown shapeless precipitate. It was filtered, washed successively with THF (20 ml) and ether (20 ml) and dried for 18 h at. 0.98 g of a brown amorphous powder was obtained, which contained, according to the definition of lithium and amine (Li) (CTP) a 5.8), a monoamine of triamine and a benzo-1,2-dithiol-3-thionhexalium complex. In Examples 27 and 28, the temperature range is confirmed. Example 27. In a solution of 2.0 g (6.4 mmol) of 2,4-diphenyl-1, b, ba-tritiapentalen (I) in 100 ml of absolute tetrahydrofuran (THF) to 1.5 g (216 mmol a) lithium sand and the mixture is stirred at -20 ° C for 24 hours. Thereafter, the dark purple solution is filtered from unreacted lithium sand. By decomposing the aliquot portion of the filtrate with water and acidimetric determination of lithium, it was found that 8.8 g-lithium reacted with one mole (g), corresponding to the formation of complex (1) with 9 lithium atoms. Example 28. In a solution of 1.5 g (4j8 mmol) of 2,5-diphenyl-1,6, ba-tritiapenthenene in 50 ml of absolute THF, 1.0 g (144 mmol) of lithium sand is added and the precipitate is stirred at 55- 60 ° C for 6 hours. By hydrolysis of an aliquot of the solution and acidimetric determination of lithium, it was found that 10.5 g of lithium reacted with one mole of the compound. Ii. Claims of Invention A method of producing alkali metal complex compounds, characterized in that the compound of the general formula I U C C. . / v% S- $ 0 I I U U / IU t j6. (i с с YviV Ш) Ш) R - the lowest holed, hydrogen, phenyl; - in hydrogen, phenyl, VI R, for 1 "ik, give a cn cn cn cn; R is hydrogen R is CH, -CHg, R- is lower alkyl, hydrogen, phenyl, reacts with an alkali metal in tetrahydrofur of 1,2-dimethoxyethane or dioxa / or tetramethylethylenediamide / -20 -. Sources of information that are taken into account in the examination. Chem. Comm., 466, 1969. .J. Org. Chem., 30, 1007, 1965.
    类似技术:
    公开号 | 公开日 | 专利标题
    SU1003758A3|1983-03-07|Process for producing complex compounds of alkali metals
    Alonso et al.1998|Synthesis and characterization of tetraalkylammonium thiomolybdates and thiotungstates in aqueous solution
    FRANZ et al.1961|A New Urea Synthesis. I. The Reaction of Ammonia, Carbon Monoxide, and Sulfur1
    Angelici et al.1969|Reactions of cyclopentadienyliron tricarbonyl cation with hydrazines and the azide ion
    Angelici et al.1970|Synthesis and reactions of carbamoyl carbonyl complexes of rhenium |
    Seyferth et al.1979|Photochemically induced insertion of acetylenes into μ-dithiobis |
    Brink et al.1973|Carbamoyl and alkoxycarbonyl complexes of manganese and rhenium
    US4115521A|1978-09-19|Process for the synthesis of decaborane|
    CA2086119A1|1992-10-31|Synthesis of molybdenum and tungsten complexes
    US3050361A|1962-08-21|Decaborane salts and their preparation
    US4349522A|1982-09-14|Iron, nickel and cobalt tri-osmium carbonyl hydrides and their preparation
    RU1838319C|1993-08-30|Method of vanadium-dimesitylene synthesis
    Carofiglio et al.1986|Carbon suboxide polymers
    Benn et al.1986|[MoR | 3], R= Alkyl: Alkylmolybdenum Complexes with Agostic C H⇀ Mo Bond
    Chung et al.1980|PREPARATION AND REACTIONS OF NEW DIOXYGEN BRIDGED COMPLEXES OF PALLADIUM
    AU630077B2|1992-10-22|Large scale synthesis of twelve member diazamonocyclic compounds
    Macomber1971|Reaction of propargyl alcohols with halogen donors. Novel phosphorus-oxygen heterocycle
    US4006174A|1977-02-01|Process for the preparation of uranium | chelated compounds and thorium chelated compounds
    Lindner et al.1977|Synthesis of Acyldiarylphosphane Oxides—Key Compounds in the Oxidation of Acyldiarylphosphanes with Molecular Oxygen
    Corain et al.1988|Coordination chemistry of β-ketoamides: Synthesis of copper | complexes, x-ray structure of bis-| copper | and nucleophilic behavior of the metal-β-carbonylenolate ring toward cyanogen and benzoyl cyanide
    CN108264526B|2020-05-26|O, O, N coordinated trivalent dicyclic phosphide, synthesis method and catalytic application thereof
    US4282197A|1981-08-04|Di-iron tri-osmium carbonyl hydride compound and its preparation
    Delavaux-Nicot et al.1995|[| Fe |] as a promoter for the synthesis of the 1, 2-disubstituted ferrocenyl aldehydes [| Fe |] and [| Fe {1, 2-C5H3 | CH2NMe | 2OCH CH2}]
    US4301129A|1981-11-17|Synthesis of NaBH3 CN and related compounds
    SU1057509A1|1983-11-30|Process for preparing 2,5-bismethyl-2,5-bis-|-1,4-dioxane
    同族专利:
    公开号 | 公开日
    US4301081A|1981-11-17|
    JPS6346078B2|1988-09-13|
    IT7823502D0|1978-05-17|
    DK217078A|1978-11-18|
    IT1096296B|1985-08-26|
    AT365604B|1982-02-10|
    DE2722221A1|1978-11-23|
    US4396589A|1983-08-02|
    ES469874A1|1979-01-01|
    JPS62187474A|1987-08-15|
    BE867155A|1978-09-18|
    FR2391196A1|1978-12-15|
    US4229354A|1980-10-21|
    MX149368A|1983-10-28|
    IE780986L|1978-11-17|
    JPH0130835B2|1989-06-22|
    JPH0233643B2|1990-07-30|
    JPS62174088A|1987-07-30|
    JPS53144532A|1978-12-15|
    ATA352878A|1981-06-15|
    US4370488A|1983-01-25|
    NL7805356A|1978-11-21|
    DE2722221C2|1987-09-24|
    JPS63265803A|1988-11-02|
    CH635825A5|1983-04-29|
    GB1598230A|1981-09-16|
    CA1117738A|1982-02-09|
    JPS6225650B2|1987-06-04|
    FR2391196B1|1983-11-25|
    JPS62182103A|1987-08-10|
    IE46897B1|1983-10-19|
    LU79670A1|1978-11-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3153087A|1960-12-30|1964-10-13|Pure Oil Co|Process for producing alkali metal adducts of aromatic solvent extracts of petroleum fractions, the products thereof and carbonation of the products|
    US3351631A|1963-12-02|1967-11-07|Union Oil Co|Recovery and fractionation of complex acids|
    US3617218A|1968-11-13|1971-11-02|Us Health Education & Welfare|Catalytic synthesis of metallic hydrides|
    DE2402399C3|1974-01-18|1979-11-08|Wacker-Chemie Gmbh, 8000 Muenchen|Process for the preparation of alkali acetylacetonates|
    DE2722221C2|1977-05-17|1987-09-24|Studiengesellschaft Kohle Mbh, 4330 Muelheim, De|
    DE2908928A1|1979-03-07|1980-09-18|Studiengesellschaft Kohle Mbh|METHOD FOR PRODUCING ORGANOLITHIUM COMPOUNDS IN ADDITION TO LITHIUM HYDROID|DE2722221C2|1977-05-17|1987-09-24|Studiengesellschaft Kohle Mbh, 4330 Muelheim, De|
    DE2908928A1|1979-03-07|1980-09-18|Studiengesellschaft Kohle Mbh|METHOD FOR PRODUCING ORGANOLITHIUM COMPOUNDS IN ADDITION TO LITHIUM HYDROID|
    FR2486072B1|1980-07-03|1984-01-13|Solvay|
    JPS63161142U|1987-04-09|1988-10-21|
    GB8724662D0|1987-10-21|1987-11-25|Ass Octel|Lewis base complexes of alkali metal salts|
    JPH04122505U|1991-04-23|1992-11-04|
    US5506863A|1993-08-25|1996-04-09|Motorola, Inc.|Method and apparatus for operating with a hopping control channel in a communication system|
    TW583027B|1998-10-30|2004-04-11|Shell Int Research|A method for preparing a hydrogenation catalyst system|
    JP4536931B2|1999-01-19|2010-09-01|ビーエーエスエフソシエタス・ヨーロピア|A method for the synthesis of substituted borohydride alkali metal reactants.|
    US20070148076A1|2005-02-14|2007-06-28|Yun Hang Hu|Method for producing a reversible hydrogen storage medium with high storage capacity and ultrafast kinetics|
    US7250146B2|2004-02-13|2007-07-31|The Research Foundation Of State University Of New York|Method for producing a reversible hydrogen storage medium with high storage capacity and ultrafast kinetics|
    US7537747B2|2004-06-03|2009-05-26|Gm Global Technology Operations, Inc.|Hydrogen storage mixed gas system method|
    WO2006073004A1|2005-01-06|2006-07-13|Shieldtechs, Inc.|Resin composition excellent in rust inhibition and electroconductivity, and member coated with the resin composition|
    US20090142258A1|2005-06-20|2009-06-04|University Of South Carolina|Physiochemical pathway to reversible hydrogen storage|
    US8153554B2|2006-11-15|2012-04-10|University Of South Carolina|Reversible hydrogen storage materials|
    KR102258042B1|2013-04-19|2021-05-27|알베마를 저머니 게엠베하|Stabilized lithium metal formations coated with a shell containing nitrogen, and a method for the production of same|
    WO2018217811A1|2017-05-22|2018-11-29|City Of Hope|Synthesis of etp derivatives|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DE19772722221|DE2722221C2|1977-05-17|1977-05-17|
    [返回顶部]