SU739070A1 - Method of preparing sodium lactamoaluminates - Google Patents

Abstract

To prepare sodium lactamoaluminates of the general formula (I> NaAl(OCH2CH2OCH3)xL4-x (I), where x, L and n are as defined in Patent Claim 1, an excess of lactam of the general formula LH is reacted with at least one compound from the group consisting of NaAlH4, Na3AlH6, NaAlH2 (OCH2CH2OCH3) 2 and NaAl(NH2)4 in an aromatic hydrocarbon. The molar ratio of the lactam to the hydridic hydrogen H<-> or to the (NH2) group of the aluminates listed is between 1:1 and 2:1.

Description

one

This invention relates to a process for the preparation of sodium lactamoaluminates of the general formula.

NCJ Ae, (OSI2SN,) id,

where X 0-2;

L is the residue resulting from the elimination of active hydrogen from lactam, the general formula

-N-CO10

(SIS1 „,

where n 3-11,

which are used as initiators of anionic poly-15 lactam meriation.

Alkali metal lactates are most often prepared by reacting lactam with an alkali metal alcoholate .1 or by reacting lactam c20 with an alkali metal hydroxide 2. When the alkali metal reacts with lactam, hydrogen and lactam salt form as the main product of the reaction, but at the same time a number of by-products 3,

None of these reactions can be used for the preparation of sodium lactamoaluminates. The reaction with the alcohol taMH alkali metal is used 30

for the preparation of pure alkaline salts of lactams. The reaction of alumino-alcoholic alcohols with lactam is not leaking. It is not possible to use the aneshogic reactions of lactam with an alkali metal hydroxide. In contrast to the reaction with alkali metals, the reaction of metallic aluminum with lactam also does not proceed.

A new method is proposed for the preparation of sodium lactamoaluminates of the general formula

NaAe (coch, CH och) L. Z 3 L 4 h

where X O - 2;

L is the residue obtained by the removal of active hydrogen from lactam, of the general formula

-I - CO

X /

N,) p

where n 3-11.

The method of producing lactamoaluminates of sodium is that the covens of the general formula LH, where L has the above meanings, are reacted in an aromatic hydrocarbon medium with one of the compounds taken from the group comprising substances of the formulas NaAeHl iIa Aea NaAe (NH2) 4H NaMH, (AXY CHjOCH U, at molar ratios of lactam and hydride hydrogen with (NH) -groups which are contained in the above sodium alumina equal to 1-Ssl, sodium lactates are obtained in one operation by slowly adding sodium or amino hydroaluminate to lactam sodium aluminate, in this case hydrogen or ammonia is released. During this process, the corresponding azacyclo-alkanes, which act as inhibitors of the polymerization of lactams, are not formed as a result of the reduction, the reduction probably does not exceed 1%. Economically, only or NaAP is used in the method according to the invention. (NH2) 4. NaAEH and- hydrides, can be dosed to the lactam in the form of a suspension, which can be prepared by direct synthesis from sodium, aluminum and hydrogen, no isolation is necessary. After reacting with lactam, filtering off unreacted aluminum and obtaining a solution of the product. In the case of using NaA6H, this hydride can be added to the solution, or the reaction can be carried out at the boiling point of the solvent, which is a mixture of aromatic hydrocarbon and ether. In this case, NaLen is extracted with a reverse stream of a vaporizable solvent. The rate of addition of this hydride depends on the amount of ether. Sodium dihydrogen bis (2-methoxyethoxo) aluminate, which is manufactured industrially, is most often added as a solution in toluene. The composition of the target product is determined by the choice of starting aluminates. When using sodium dihydride-bis (2-methoxy-ethoxo) aluminate, sodium dialactamo-bis (2-methox-ethoxo) aluminates is obtained, and when using or NaAC (NH2) 4 Na-Ag2. tetralactamino sodium. If the starting product is a ber; / t mixture of sodium dihydro bis (2-methoxyethoxo) aluminate with one of the above aluminates, then sodium lactamoaluminate of the general formula NaAe is obtained as the target product (OCH2 .. jli L where X and L have the above values The final composition (x value of the index) is determined by the molar ratio of the initial aluminates and sodium lactamoaluminates obtained from them, as is evident from the following level: XNaAei.OCH2 ,,,) l.2i-W-l4it Q№ - - NoAe OCHg CWiOCHj). Example 1 In a three-necked flask, 2 liter of volume which is equipped with a stirrer, a water-cooled reflux condenser and an addition funnel, in an inert atmosphere 565 g of 6 caprolactam (5 mol) and 300 ml of toluene are added and a solution of NaAgH is added during 3 hours with stirring, obtained by dissolving 56, 98% NaAEH (1.02 mol) in 350 ml of dimethoxyethane. After this solution was added, the addition funnel was washed with 60 ml of dimatoxyethane and the resulting solution was added to the reaction mixture. By evaporation of a part of the solvent, 877 g of a 57.5% sodium tetracaprolactamoaluminate solution are obtained. By analyzing the solution, the aluminum content was found to be 3.11%, which corresponds to 504.5 g of pure sodium tetracaprolactamoaluminate. The yield is 99.3%. After evaporation of the solvent, 609.3 g of a mixture of sodium tetracaprolactamoaluminate and an excess of caprolactam are obtained. Found,%: C 58.8 H 8.36, Ae 4.50, N 11.43; Na 3.83. S24H. APN.NaO (Mol. Weight 498,582). Calculated,%: C 57.82; H 8.09; AC 5.41; N 11., 2L; Na 4.62. EXAMPLE -2 A 250 ml flask equipped with an extraction nozzle (porous glass filter) and a water-cooled reflux condenser is introduced in an inert atmosphere with 51 g of pyrrolidone (0.6 mol), 30 ml of toluene and 30 ml of tetrahydrofur on; 5.7 g of NaAEH (0.103 mol) is applied to the extraction nozzle. The reaction mixture is heated to boiling and NaHbHd is added to it by slow extraction. After extraction of all the NaAEH. a clear, slightly yellowish solution is obtained, which, after evaporation of a part of the solvent, weighs 76.3 g and contains 52% sodium tetrapyrrolidonal aluminum. After evaporation of all the solvent, 55.8 g of a white waxy solid with a melting point of 125-135 ° C are obtained. Found,%: C51, b; H6, B1; A 4.98; N 16.0; Na 4.24. (Like, weight 386.36). Calculated,% t with 4U, / 4g Nb, 26; A 6.98 N 14.40; Na 5.95. The product yield on the introduced aluminum is 99.8%, Example 3, a 500 ml three-neck flask equipped with a stirrer, a water-cooled reflux condenser and a dropping funnel are introduced in an inert atmosphere with 98.5 g (0.5) of 12-laurolactam in 120 ml toluene. A solution of 5.4 g of 98% NaAfH (0.098 mol) in 40 ml of dimethoxyethane is added dropwise over 2 hours at the boiling point and with stirring. Upon completion of the reaction, a solution with a slightly yellowish color is obtained, which, upon evaporation of a part of the solvent, weighs 190 g and contains 43% sodium tetralaurolactamoaluminate. According to the analysis, the solution contains 1.39% aluminum, which corresponds to 81.7 g of pure sodium tetralaurolac tamoaluminate. The output of the reaction product introduced by NaAEH 99,8%. 103.1 g of a solid are obtained by evaporation of the solvent, m.p. 95 108С. Found,%: C 69.70; H 10.88; Le 2.52; N 6.82; Na 2.15. C gHggACNjNaOu (Mol. Weight, 835.427) Calculated,% C 69.02; H 10.62; AE 3.23; N 6.70; Na 2.75. Example 4. In a three-necked flask with a volume of 250 ml, equipped with an agitated and a water-cooled reflux condenser, 50.5 g of 6-caprolactam (0.447 mol) were added in 25% excess and 25 ml of toluene. To this mixture was added a suspension of 5.75 powdered NaAbN (0.104 mol (98%)) over 2 h. and 50 ml of toluene. This gives 135 g of a solution containing 38.9% sodium tetracaprolactoaluminate. According to the analysis, the solution contains 2.105% aluminum, which corresponds to 52.5 g of pure sodium tetracaprolac sodium aluminate. 100%. After evaporation of the solvent, 58.5 g of a yellow solid (tetracaprolactam sodium aluminate and an excess of 6-capro-lactam) with a point of 94-101 ° C are found.% S C 58.35; H 8.23; A6 4; 83; N 11.33; Na 4.14. C24 H gACN-NaQj (Mol. Weight 498.582) Calculated,%: C 57.82; H 8.09; de 5.41; N 11.24 Na 4.61 Example 5. A 1000 ml three-necked stake supplied with a stirrer and a water-cooled cooler gives 126 g of chi-laurolactam (0.639 mol) (20% excess) and 250 ml of benzene. With stirring, 100 ml of a suspension consisting of 10.18 g of 89% NajABHg (0.088 mol) obtained by direct synthesis from sodium aluminum and hydrogen is added to this mixture. The reaction mixture is cooled, filtered, and the precipitate is washed with 20 ml of benzene. The total yield is 461 g of a solution which contains 16.07% sodium tetralaurolactamoaluminate. After evaporation of the solvent, 94.9 g of a colorless glassy substance are obtained, mp. 103-110 C. The yield of the reaction product on the introduced aluminum is 99.8%. Found,%: C 69.89; H 10.8; le 2.52; N 6.77; Na 2.15. with. H AeN, NaO4 (Mol, weight 835, 427). Calculated,%: C 29.03; H 10.62; Le 3.23; N 6.70; Na 2.75. Example 6. In a three-neck flask with a volume of 250 4 l, equipped with a melt and reflux condenser, 68 g of J-butyrolactam (0.799 mol) were added and a suspension of 11.72 g (0.113 bottles) was added dropwise over 3 hours (98, 5% on 100 ma of toluene. 174 g of a solution containing 25% sodium tetrabutyrolactamoaluminate is obtained. After evaporation of all the solvent, 53.7 g of a white solid are obtained, mp. 125-130 ° C. The yield of the reaction product on the introduced aluminum is 99.3%. Found,% C 50.9; H 6.62; Ab 5.65; N 14.86; Na 4.82. C i5H24AEN.Naa (molo-weight 386.36). Calculated,%: C 49.77; H 6.26; AE, 6.98; N 14.50; Na 5.95. Example 7. In a three-necked flask with a volume of 6 liters, equipped with a stirrer and reflux condenser, 1709 g of 6-caprolactam (15.12 mol) and 600 ml of toluene are introduced. To this suspension is added dropwise the reaction mixture of direct synthesis of NaAeH4. in toluene. Within 3 hours, 1800 g of this mixture was added, consisting of 7.89% NaAgH (2.63 Yule), 2.1% NajAEHg (0.371 mol), 3.36% NaAEH (OCH, CH2OCH) (0.293 mell) , 2.5% aluminum (0.668 mol) and other solid impurities. After cooling, the reaction mixture is filtered and the precipitate is washed with 200 ml of toluene. 4100 g of filtrate with an aluminum content of 2.16% are obtained, which corresponds to a mixture of dissolved sodium tetracaprolactoaluminate (36.23%) and dicaprolactamis bis (2-methoxyethoxo) sodium aluminate (3, K yield of 99.5%. After evaporation of the solvent, 1805 are evaporated , 7 yellow solids. Elementary analysis,%: C 61.48; And 8.79; AE, 4.89; N 11.71; Na 4.16. Example 8. In a 6 L flask with a reflux condenser, stirrer 1832 g of 6-caprolactam (16.2 mol) and 830 MP of toluene were introduced into a two-liter dropping funnel. To this suspension, 2.5 liters of 19% g sodium di-trido (2-methoxy-ethoxo) aluminate (6.75 mol). During the reaction, the mixture heats up to 85 s. To obtain 4450 g of a clear solution containing 64.35% dicaprolactamo bis (2-methoxy-ethoxo) sodium aluminate. According to an analysis, the solution contains -, lives 4.09% aluminum, which corresponds to 2863.5 g of pure sodium dicaprolactamo bis (2-methoxyethoxo) aluminate, 89.9% &amp; 11%. After evaporation of the solvent, 3160.5 g of a kelty solid are obtained, m.p. 45-50 seconds Found,%: C 62,32; H 8.25; A 5.76; N 7.1; Na 4.90 NaO (Mol. Weight 424.452). Calculated 7%: C, 50.93; H 8.07 6, 35; N 6.59; Na 5.41. Example 9. In a 1000 ml flask with a stirrer and a reverse} 255.4 g of tt-pyrrole don (tp-butyrolactam) (3.0 mol) are introduced. To the molten d-pyrrolidone at 30 ° C and with stirring, 288.6 g of a 70% toluene solution of sodium aluminate dihydride bis (2-marks ethoxo) of sodium aluminate (0.999 mol) are added over 3 hours 530 g of a clear liquid containing 69.5% dibutyrolactamo- (2-methoxyethoxo) sodium aluminate is obtained. After evaporation of all the solvent, 453.6 g of a viscous yellowish liquid are obtained. : C, 47.68; H, 7.31; le, 5.94; N, 9.26; Na, 5.06. C. HnftABN-NaO (Mol. Weight, 368.344) B h ss, X: C, 45.65; H 7D1; 7 , 32; N 7.60; Na 6.24. P and measure 10. In a 500 MP flask with a stirrer and reflux condenser, 70 g of su-laurolac tam (0.355 mol) and 150 ml of benzene are added. To the mixture, 44.1 g of 65 are added dropwise to the mixture over 2 hours. A solution of dihydrido bis (2-methoxyethoxo) aluminium sodium (0.042 mol) in benzene is obtained. The solution obtained weighs 300 g and contains 28.03% of dilaurolactamo bis (2-methoxyethoxo) apuminate sodium. After evaporation of the solvent, a solvent is obtained 98.1 g of a white crystalline substance with a point of 99–102 Ci, the yield of the reaction product on the introduced aluminum is 100%; Found,%: C 62.5; H 10.1; Ab 3, N 5,0; Na 3.32. H gAeNj NaO (Mol. Weight 592.788) Calculated,%: C 60.78; H 9.86; AC 4.55; N 4.72; Na 3.81. Example 11 A 12.2 g of 97.5% NaAe (NHj) (0.1043 mol) and 25 were introduced into a flask with a volume of 500 ml with an addition funnel and a reflux condenser closed with a tub-dryer filled with solid KOH. ml of bezol. To this mixture, add 196 ,, 5 of a 30% aqueous solution of 6-caprolactam (0.522 mol) in benzene and then heat it in a boiling water bath for 30 minutes. 196 g of a 26.5% complete solution of tetrakis (6-caprolactamo) sodium apuminate are obtained. According to the analysis, the solution contains 1.43% aluminum, which corresponds to 51.94 g of pure tetrakis (6-caprolactamo) sodium aluminate. The yield of the reaction product is 99.8%. After evaporation of the solvent, 63.8 g of a yellow solid were obtained. Mp. 94. Found,%: C 58.7; H 8.36; AE 4.41; N 11.44; Ma 3.75. C24H QAEN4Naq, (Mol. Weight 498,582). Calculated,% s fc 57,82; H 8.09; AC 5.41; N 11.24; Na 4.61. Example 12 In a 250 ml flask with a reflux condenser, closed with a tub-dryer filled with solid KOH, 6.35 g of 97.5% Kale (NH) (0.0596 mol) and 20 iktn of toluene are introduced. 70.9 g of a 50% toluene solution of 4-butyrolactam (0.417 mol) are added over 50 minutes, then the reaction mixture is heated for 45 minutes in a boiling water bath. After cooling to 20 ° C, the mixture is evacuated until a vacuum of 20 mm Hg is created. 82.1 g of a 23% solution of sodium tetrakis-4-butyrolactamoaluminate are obtained. After evaporation of the total solvent, 34.06 g of a white solid are obtained. The product yield on the introduced aluminum is 81.9%. Found,%; C 52.73; H 7.1; lez, 87; N 15, ZG Na. 3.30. .NaO. (Mol. Weight 386.36). 1a is, “: C 4U, 74; H 6.2b; AE. 6.98; N 14.50; Na 5.95. At 1/1 ep 13, into a 250 ml flask with a reflux condenser closed from the ingress of air filled with solid KOH with a dryer, 4.52 g of 95% NaAC (NH) (0.0423 mol) and 20 ml of benzene. Then, a 32.5% benzene solution of 12-laurolactam was added to this mixture over 45 minutes. The mixture was then heated for 45 minutes in a boiling water bath. After replacing the reflux condenser of the cold, a Liebig bottle of the reaction mixture was distilled off with 35 ml of benzene. 97 g of a 36.4% solution of sodium tetrakis-12-laurolactamoaluminate are obtained. After evaporation of all the solvent, 39.5 g of a glassy, colorless substance are obtained, m.p. 103-115 ° C. Sakhod reaction product on the introduced aluminum is 99.6%. Found,%: C 69.42; H 10.73; Ae2,88; N 6.72; Na 2.45. C.gHggAEN.NaO (mol. Weight 835.427). Numbered7% 5 C 69.027; H 10.62; AE 3.23; N 6.70; Na 2.75. The individuality of complex lacteyl aluminate is in sodium. The compounds obtained according to the proposed method correspond, according to the analytical definition of eshuminim, Yatri and nitrogen, to the formula NaAK (Lact) j. Unlike the sodium salts of lower lactams, which are practically insoluble in aliphatic and aromatic hydrocarbons, the complex sodium lactamoaluminates dissolve well in these solvents, the IR spectra of the complex lactamates are significantly different from those of the original lactams and correspond to the VaMaM lacquers associated with the atom . Molecular weights in all cases indicate that complex lactamoaluminates exist in the benzene solution in the form of dimers. All this testifies to the chemical individuality of complex lactamoaluminates. The best evidence is the IR spectra of these compounds. The distinctive bands of the IR spectrum of 6-caprolactam, namely the stretching vibrations of the hydrogen bond of the bound NH-group at 3412 (t) and 3215 (8 stretching vibrations of the whole amine group at 1675 (S) cm p complex and simple lactamates or not at all). are, or are shown with only very slightly (unreacted lactam or a polymer that has arisen). Distinctive bands, spectra at 2922 (S) and 1436 (S) cm are present in both the capropactam ligand and caprolactam, sodium tetracaprolactyaluminate while They produce a strong band at 2916 cm, amido group There are two broad bands at 1616 and 1577 Insoluble and free caprolactam, sodium caprolactamate in the nujol does not appear in the region above 3000 cm with any band, the amide group appears with one very intense band at 1460 CMt The weak band at 1679 cm obviously corresponds to caprolactam formed by hydrolysis. Aluminum caprolactamate also does not appear in the 3000 headline and there is no band in the high-frequency vibrations, only one broad band at 1600 cm with two arms is observed are other lakta1 s, their salts and complexes. Intensive and Significant bands of lactams and their derivatives in benzene in the range of 4000–1400 cm are shown in the table.

Na (CL) Ae (CL)

HaAg (CL) 2 (cel) 2

12-Laurolactam (LL)

NaAE (LL),

NaAB (LL) 2 (cel)

4-Butyrolactam (BL) 3200 (8)

I577 (s)

1379 (m)

1679 (w)

1460 (vs)

16OO (vs)

1468 (s)

1600 (s) 1440 (s)

I575 (s)

1680 (vs)

1508 (s) 1466 (s) 1439 (8)

Claims (3)

I584 (s) 1340 (m) I555 (s) 1450 (m) I555 (s) 1370 (m) I532 (sh) 1423 (m) 1700 (vs) In Nujol. . Cello 2-methoxy-e1ano The designation of intensity (vs) is very strong (t) 1. Method for preparing sodium lactamoaluminium sodium of the general formula MaD {OCH2CFij, OCH) L where X 0-2; L is the residue obtained as a result of the elimination of actinic hydrogen from lactam, of the general formula (where p. 3-11), characterized in that the total LH acts, where L has the above values, are reacted with NaAeH4, NaAAH, CaAen, ( OCH, And / or NaA6 (NH2) at a molar ratio of lactam and hydride hydrogen or -NHjf group contained in said aluminates equal to 1-8: in aromatic hydrocarbon medium 2. Method according to claim 1, characterized in that the molar ratio is Continued bands: (h) is strong, (w) is weak, dn, (sh) the shoulder of lactam and aAVI or NaAe (NH) is equal to about 4-8: 1. 3. The method according to Claim 1, characterized in that the molar ratio of lactam and MaAEN "(OSI CH OCH) is 2.05-2.1: 1, the priority according to signs 10.12.75 in the process use MaAE1C or NaAE (NH) 01.07.76. NaAeH lOCH CHg OCH.j) and / or Na, Ae are used in the process. Sources of information taken into account during the examination 1.CefeEin R., Sebenta J. Afkaishe peliymerisierung des b-caproEactams CotE. Crech. Chem, Commun. 26, 3028, 1961. 2. US patent 3674751, cl. 260/784, pub. 1972, 3 .. And, Ciaperoni and Kob., Prototti di reazione tra capro attamme e, So6io, Chem. Ond {MiEan)., 50, 772, 1968.