TW388758B - Preparation of cyclic lactams - Google Patents

Description

Patent Application No. 84100496 Chinese Revised Sheet of Chinese Specification (March 88) V. Description of Invention (1)

(Please read the notes on the reverse side before filling out this page) The present invention relates to a method for preparing a cyclic internal amine by reacting an amine carboxylic acid compound of the general formula I with water:

n2 ^-(CH2) m-CORl I where R1 is -OH, -0-CH2 alkyl or -NR2R3, and R2 and R3 are each hydrogen 'CN12 alkyl or C5-8 cycloalkyl, and m is 3 Integer to 12. US 3485821 relates to the use of amino-hexanoic acid, aminohexamidine and its alkyl-substituted derivatives to borrow from 150 to 350. (: The reaction is carried out in water without catalytic conversion to caprolactam or alkyl-substituted caprolactam, which may add ammonium salts to water. However, the conversion rate to caprolactam is not higher than 90 DE-A 2535689 describes a method for preparing caprolactam by conversion of 6-aminohexanoic acid dissolved in methanol or ethanol. The solvent has an alcohol content of at least 60% by volume and the reaction system is between 170 and 200 °. C, according to DE-A 2,535,689, the higher the temperature, especially 220 ° C or higher, will cause the corresponding increase in the formation of 6-aminohexanoic acid alkyl ester, which will eventually lead to an increase in the formation of oligomers. Water content higher than 40% by volume will cause the formation of open-chain polyamines; for commercial use, the addition of 6-aminocaproic acid is considered to be a disadvantage because the aminocaproic acid needs to be converted into caprole The amidine has been completely-completely dissolved and therefore the b-aminohexanoic acid needs to be continuously added and tracked for its consumption.

Ind. Eng. Chem. Process Des. Dev. 12 (1) (1978). 9-16 (Mares et al.) Describe the conversion of 6-aminohexanoic acid to caprolactam in water and ethanol without addition Catalyst, caprolactam in water and 2 1 ° C; reaction temperature; yield is only 65%, and claimed to reach a yield of up to 98% in pure ethanol. However, the yield of 92% or higher as described by Mares et al. Is -4-this paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇χ 297 mm) Chinese specification of patent application No. 84100496 Revised page (March 88) V. Description of invention (1)

(Please read the notes on the reverse side before filling out this page) The present invention relates to a method for preparing a cyclic internal amine by reacting an amine carboxylic acid compound of the general formula I with water:

n2 ^-(CH2) m-CORl I where R1 is -OH, -0-CH2 alkyl or -NR2R3, and R2 and R3 are each hydrogen 'CN12 alkyl or C5-8 cycloalkyl, and m is 3 Integer to 12. US 3485821 relates to the use of amino-hexanoic acid, aminohexamidine and its alkyl-substituted derivatives to borrow from 150 to 350. (: The reaction is carried out in water without catalytic conversion to caprolactam or alkyl-substituted caprolactam, which may add ammonium salts to water. However, the conversion rate to caprolactam is not higher than 90 DE-A 2535689 describes a method for preparing caprolactam by conversion of 6-aminohexanoic acid dissolved in methanol or ethanol. The solvent has an alcohol content of at least 60% by volume and the reaction system is between 170 and 200 °. C, according to DE-A 2,535,689, the higher the temperature, especially 220 ° C or higher, will cause the corresponding increase in the formation of 6-aminohexanoic acid alkyl ester, which will eventually lead to an increase in the formation of oligomers. According to this document Water content higher than 40% by volume will cause the formation of open-chain polyamines; for commercial use, the addition of 6-aminocaproic acid is considered to be a disadvantage because the aminocaproic acid needs to be converted into caprole The amidine has been completely-completely dissolved and therefore the b-aminohexanoic acid needs to be continuously added and tracked for its consumption.

Ind. Eng. Chem. Process Des. Dev. 12 (1) (1978). 9-16 (Mares et al.) Describe the conversion of 6-aminohexanoic acid to caprolactam in water and ethanol without addition Catalyst, caprolactam in water and 2 1 ° C; reaction temperature; yield is only 65%, and claimed to reach a yield of up to 98% in pure ethanol. However, the yield of 92% or higher as described by Mares et al. Is -4-This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 〇χ 297 mm) No. 84100496 Chinese patent application description Book amendment hundred (December 85)

V. Description of the invention () Using heterogeneous catalyst to obtain cyclic lactam. When an amine carboxylic acid compound of the general formula I is used, the corresponding cyclic lactamamine of the general formula 11 can be obtained:

(CH2) m / \ HN —- CO Π Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, where m is as defined above, and particularly good lactam is where m is 4, 5, or 6, especially 5 (in the latter In this case, caprolactam was obtained). The reaction system is usually 140 to 320 in the liquid phase. (:, Preferably from 160 to 300 ° C; the pressure is usually selected from 0.5 to 25MPa, but the reaction mixture is liquid under the conditions used. The residence time is usually from 5 to 120, preferably from! 0 to 60 minutes. Advantageous Diaminoamino acid compounds are used in water or in water / solvent tear compounds in an amount of 1-50%, preferably 5.50 〇 / 〇, particularly preferably 5-25% strength weight solution 》 An example of a solvent is an alkanolase, especially a C1-4 alkanol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, a second butanol and a third butanol, a multivariate enzyme, Such as dioxalase and tetraethylene glycol, lactams such as pyrrolidine, caprolactam and alkyl-substituted lactam, especially N-C1-4 alkanol lactam, such as N-methyl Pyrrolidone, ν · methylcaprolactam, or N-ethylcaprolactam β ammonia can also be present in the reaction. Β Of course, a mixture of organic solvents can also be used. Heterogeneous catalysts that can be used are, for example, Table the acidic, qualitative or amphoteric oxides of the second, third or fourth royal family elements such as boron oxide, alumina or silica, such as diatomaceous earth, quartz or mixtures thereof, And schedules second to first

-------- P Xiang .—— (Please read the notes on the back before filling out this page) Order the printing of the A7 B7 printed by the Order of the Ministry of Economic Affairs and the Central Bureau of Quasi-Bureau Consumer Cooperatives V. Invention Description (2) The test cannot be repeated. Indeed, these high yields can only be cyclized by Mares et al. Without using a 10-strength weight solution of 6-limehexanoic acid but by continuously adding 6-aminohexanoic acid to the ethanol solution Explain the fact that you have yourself. Since caprolactam is stable under the chosen reaction conditions, it is possible to obtain high yields (92/0 and 98/0) only from the fact that the caprolactam concentration increases during the reaction. This hypothesis can be supported by US 2,535,689 (with Mares as co-inventor). Example 1 of this U.S. patent states that 6-aminocaproic acid should be avoided before the 6-aminocaproic acid is completely dissolved. For this purpose, 6-aminohexanoic acid needs to be added slowly so that no solid acid is present in the solvent, but 6-aminohexanoic acid can be immediately dispersed in a hot solvent and completely dissolved or dispersed upon heating. Since the maximum solubility of 6-aminocaproic acid in cooled and boiling ethanol (78 ° C) is only 1.3 g / l (= 0.13 o / wt), it is clearly only possible in Mares et al. Add 6-liminohexanoic acid in small amounts to obtain a pure theory; a solution containing 100/0 by weight 6-aminohexanoic acid. Otherwise, this technical step of metering at 200 ° C and 80 bar is accompanied by great difficulty and long time. In Mares et al. (Ind. Bng. Chem. Process Des. Dev.] 2 (1) (1978). 9-16), the softening of ethyl 6-aminohexanoate in caprolactam in ethanol was also studied. . And found that quantitative cyclization is only possible at low temperatures and high dilutions; according to Mares et al., Especially at 200 ° C and 10 hours reaction time can be obtained from ethyl 6-aminohexanoate only 90 〇 / 〇; Caprolactam yield. According to Mam et al., The yield can be increased to not more than 95 0/0 at 150 ° C, but the reaction time of 0 hours or longer can never be achieved for commercial use. This paper standard applies Chinese national standards (CNS) A4 specification (210X297 mm) ------- J-^; 4-pack ------ order ------ 1 line (please read the notes on the back first to write V% (This page) \ Printed A7 B7 by the Consumer Cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs V. Description of the invention (3)

Mares et al. Similarly described the conversion of ethyl 6-aminohexanoate to caprolactam in water at a temperature of 200 ° C and a reaction time of 5 hours not exceeding 62.5 〇 / 〇; in the same publication, study 6 -The conversion of amine hexamidine in water and in ethanol to caprolactam, and a yield of not more than 71 0/0 was obtained in a reaction time exceeding 70 minutes.

Tetrahedron Lett Ugly (1980), 2443 describes the cyclization of 6-aminocaproic acid in a suspension in toluene by removing the water of reaction in the presence of alumina or silica gel. To completely desorb the extremity, the catalyst was washed with dichloromethane / methanol, and the polymer was precipitated with ether. The yield of caprolactam on alumina was 8 2% and on silica gel was 75 〇 / 〇, but the reaction time in each case was 20 hours. EP-A 271815 describes the cyclization reaction of 6-aminocaproic acid vinegar to obtain caprolactam. The ester is dissolved in an aromatic hydrocarbon and then the formed alcohol is removed simultaneously at 100 to 320 ° C for cyclization. The disadvantage is that the removal of alcohols at superatmospheric pressure and aromatic hydrocarbons is a costly removal due to its high boiling point and requires a long reaction time, such as when the reaction is performed in o-xylene (140 ° C). The reaction time is 14 hours. EP-A 376122 describes the cyclization of 6-aminohexanoate in the presence of aromatic hydrocarbons and water at 230 ° C to 350 ° C to obtain caprolactam. An object of the present invention is to provide a method for preparing cyclic lactam by reacting an amine carboxylic acid compound of the general formula with water:

H2N- (CH2) m-C0R 丨 I where R1 is -0H, -0-CM2 alkyl or -NR2 R3, and R2 and R3 are each other hydrogen * Ci-12 alkyl or C5-8 cycloalkyl 'and m is an integer from 3 to 2; this paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) -------- ^^ --- 7 Packing ------ Order- ----- Line% f .., 5 .-- (Please read the notes on the back and write this page first) ί Printed by A7 __B7___, Shellfish Consumer Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs 4) This method does not have the above disadvantages. We have found that this objective can be achieved by an improved method for the preparation of cyclic lactams using a heterogeneous catalyst in the liquid phase between the aminocarboxylic acid compound of the general formula I and water:

H2N- (CH2) m-C0R1 I where R1 is -OH, -0-CM2 alkyl or -NR2 R3, and R2 and R3 are each other hydrogen, CM2 alkyl or C5-8 cycloalkyl, and m is 3 Integer to 12. The starting material used in this novel method is an aminocarboxylic acid compound, preferably a compound of the general formula:

H2N- (CH2) ra-C0R 'I where R1 is -0H, -0-CM2 alkyl or -NR2 R3, and R2 and R3 are each other hydrogen, Ci-i2 alkyl or C5-8 cyclofluorenyl, and m is 3,4,5,6,7,8,9, 1 0-1 1 or 1 2 ° The preferred starting material is where R1 is -0H or -0-Cw alkyl such as -0-methyl, -0-ethyl, -0-n-propyl, -0-isopropyl, -0-n-butyl, -0-second butyl, -0-third butyl or -0-isobutyl, -NR2 R3 is -NH2, -NHMe, -NHBt, -NMe2 or -NBt2, and m is 5. 6-aminohexanoic acid, 6-aminohexanoic acid methyl ester, 6-aminohexanoic acid ethyl ester, 6-amino-N-methylhexamidine, 6-amino-N, N-dimethyl Hexylamine, 6-amino-N-ethylhexylamine '6-amino-N, N-diethylhexylamine and 6-aminohexylamine are particularly preferred. The starting compounds are commercially available or can be prepared according to methods such as BP 2342% and 1 n d, Bng. Chem. Process Des. Dev. 1978), 9-16. In this novel method, the aforementioned amine carboxylic acid compound and water are in the liquid phase. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm).

--------; __ ^ --- ;. Install ------ order ------ line ----- -i- · * (Please read the precautions on the back first ^ ? ^ Write this page) I Amendment to the Chinese Specification for Patent Application No. 84100496 (December 1985)

V. Description of the invention () Using heterogeneous catalyst to obtain cyclic lactam. When an amine carboxylic acid compound of the general formula I is used, the corresponding cyclic lactamamine of the general formula 11 can be obtained:

(CH2) m / \ HN —- CO Π Printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, where m is as defined above, and particularly good lactam is where m is 4, 5, or 6, especially 5 (in the latter In this case, caprolactam was obtained). The reaction system is usually 140 to 320 in the liquid phase. (:, Preferably from 160 to 300 ° C; the pressure is usually selected from 0.5 to 25MPa, but the reaction mixture is liquid under the conditions used. The residence time is usually from 5 to 120, preferably from! 0 to 60 minutes. Advantageous Diaminoamino acid compounds are used in water or in water / solvent tear compounds in an amount of 1-50%, preferably 5.50 〇 / 〇, particularly preferably 5-25% strength weight solution 》 An example of a solvent is an alkanolase, especially a C1-4 alkanol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, a second butanol and a third butanol, a multivariate enzyme, Such as dioxalase and tetraethylene glycol, lactams such as pyrrolidine, caprolactam and alkyl-substituted lactam, especially N-C1-4 alkanol lactam, such as N-methyl Pyrrolidone, ν · methylcaprolactam, or N-ethylcaprolactam β ammonia can also be present in the reaction. Β Of course, a mixture of organic solvents can also be used. Heterogeneous catalysts that can be used are, for example, Table the acidic, qualitative or amphoteric oxides of the second, third or fourth royal family elements such as boron oxide, alumina or silica, such as diatomaceous earth, quartz or mixtures thereof, And schedules second to first

-------- P Xiang .—— (Please read the precautions on the back before filling in this page) Order A7 B7 388758 Patent Application No. 84100496 Amendment Chinese Manual (March 88) V. Invention Note (6) An oxide of a metal of the six subgroups, such as titanium oxide (such as anatase or rutile), hafnium oxide, or a mixture thereof. Lanthanide and actinide oxides such as oxidized oxides, scandium oxides, scandium oxides, scandium oxides, oxides, or mixtures thereof with the above oxides can also be used. Other catalysts may be, for example, oxidized oxide, niobium oxide, iron oxide, oxide circuit, molybdenum oxide, tungsten oxide, and mixtures thereof. Mixtures of these oxides with others can also be used. The aforementioned compounds may be doped with or may contain compounds of the main groups of the Periodic Tables I and VII. Other suitable catalysts are, for example, zeolites, phosphates and heteropolyacids and acidic and ion exchangers such as Naphion (R). These compounds may, if desired, contain up to 50% by weight of copper, rhenium, zinc, manganese, iron, cobalt, nickel, ruthenium, palladium, platinum, silver or rhodium. The amount of catalyst usually depends on the step: in the batch step, the amount of catalyst is selected from 0.1 to 50 ', preferably from 1 to 30% by weight (based on the amino carboxylic acid compound of the general formula I) ); In a continuous step, the space velocity of the catalyst is selected from 0.1 to 5 kg per liter per hour (based on the aminocarboxylic compound of the general formula I). The 'in novel method' is to obtain cyclic lactam in high yield, in particular hexanolactam. Example Comparative Example 2 A solution of 6-aminohexanoic acid in water was passed into a heated reaction tube at 100 bar, the volume was 100 ml, the diameter was 9 mm and the length was 400 mm, and it was filled with * 9-this paper Standards apply to Chinese National Standards (CNS > A4 specifications (210X297)) (Please read the precautions on the back before filling out this page) Order the Ministry of Economic Affairs and the Procurement Bureau for Off-line Work and Consumer Cooperation. Printed by the Society 388758 No. 84100496 4 Lee application _ Chinese manual amendment page (March 88) V. Description of the invention (7) A7 B7 Dioxide in the form of 1.5 mm extrudate “(sharply broken) ^ The product gas leaving the reactor is in the gas phase Chromatograph and high-pressure liquid chromatography (HPLC) analysis: Aminocarboxylic acid (%) Water [%] Temperature rc] Retention time [minutes] ---- Yield [%] 10 90 220 15 --- ---- 66 10 90 220 3 0 76 Example 1 Similar to the experiment described in Example 1, the solution of aminohexanoic acid in ethanol / water was pumped through a reaction tube filled with titanium oxide extrudate.-Aminocarboxyl Acid (%) Water [%] Ethanol temperature rc] Retention time [minutes] — Yield [%] 10 40 5 0 220 15 98 10 40 5 0 220 3 0 — 90 — f (Please read the notes on the back and fill in this page again.) Ordered by the Central Standards Bureau of the Ministry of Economic Affairs, Printed by the Ordnance Industry Consumer Cooperatives. Example 2 Similar to the experiment described in Example 1, a solution of ethyl aminohexanoate in ethanol in the presence of water was pumped through. A reaction tube filled with a titanium oxide extrudate. This paper size applies to China National Standard (CNS) A4 (210X297 mm) ι A7 88 & 758 B7 V. Description of the invention (8) Ethyl aminohexanoate (〇 / 〇) water [〇 / 〇] ethanol [ 〇 / 〇] Temperature [. . ] Retention time [minutes] Conversion rate [〇 / 〇] Selectivity [〇 / 〇] Yield [〇 / 〇] 10 1.1 88.9 220 15 97 93 90 10 1.1 88.9 220 30 97 85 83 10 1.1 88.9 220 60 100 79 79 10 4, 4 85.6 220 30 97 95 92 Comparative example ---- I --- ^ pack-- (Please read the precautions on the back to write this page) In each case, 6-aminocaproic acid was used in ethanol The solution in the solution was heated to 200 ° C according to hd. Bng. Chem. Process Des. Dev. 22 (1978). 16 with different residence times. The results are shown in the table below. Residence time temperature conversion selectivity caprolactam [minutes] [. . ] [〇 / 〇] [〇 / 〇] yield (G / o) 10 200 90 80 72 15 200 87 93 80 20 200 90 90 81 30 200 90 91 82 40 200 91 88 80 did not achieve higher than 8 2 0 / 〇 yield. This paper size applies to China National Standard (CNS) Α4 specification (210X 297 mm)

, 1T Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs

Claims (1)

Article 841. . No. 496 private scale 5 8 _ Chinese patent application scope 偬 芷 Tai Liu, patent application scope supplement 1_ A method for preparing e-caprolactam, which reacts the amino caproic acid compound of the general formula 丨 > 1 H2N- (CH2) 5-c〇r1 j where R is -OH, -0_Cl l2 alkyl, or _NR2R3, and r2 and r3 are each hydrogen, Cl-12 alkyl, or C5_8 cycloalkyl; The reaction is performed in the liquid phase using a heterogeneous catalyst, wherein the catalyst is selected from the group consisting of oxides of elements of the second, third or fourth main group of the periodic table, oxides of elements of the second to sixth order of the periodic table, phosphate Zeolite, heteropolyacid and acidic and basic ion exchange resins, and wherein the reaction is performed in a mixture of water and an organic solvent, the organic solvent is selected from alkanols and polyols. 2. According to the scope of patent application! The method of item 1, wherein the reaction is performed at 140 ° C to 320 ° C. 3. The method according to item 1 or 2 of the scope of patent application, wherein the aminocarboxylic acid compound used is selected from the group consisting of 6-aminohexanoic acid, 6-aminohexanoic acid methyl ester, 6-aminohexanoic acid ethyl ester, 6-amino_N · methylhexamidine, 6-amino_N, N-dimethylhexamidine '6_amino_N-ethylhexamidine, 6-amino-N, N -Diethylhexamidine and 6-aminohexamidine. 4. The method according to item 1 or 2 of the scope of patent application, wherein the alkanol is a C1-C4-alkanol. 5. The method according to item 1 of the scope of patent application, wherein the catalyst is selected from oxides of elements of the second, third or fourth main group of the periodic table and oxides of elements of the second to sixth order of the periodic table. This paper is in use again ® National Standard (CNS) A4 (210X297 mm) f Please read the precautions on the back before filling out this page), 1T ·· Ministry of Economic Affairs, Central Bureau of Standards and Labor, Consumer Cooperatives Neem.II I Article 841. . No. 496 private scale 5 8 _ Chinese patent application scope 偬 芷 Tai Liu, patent application scope supplement 1_ A method for preparing e-caprolactam, which reacts the amino caproic acid compound of the general formula 丨 > 1 H2N- (CH2) 5-c〇r1 j where R is -OH, -0_Cl l2 alkyl, or _NR2R3, and r2 and r3 are each hydrogen, Cl-12 alkyl, or C5_8 cycloalkyl; The reaction is performed in the liquid phase using a heterogeneous catalyst, wherein the catalyst is selected from the group consisting of oxides of elements of the second, third or fourth main group of the periodic table, oxides of elements of the second to sixth order of the periodic table, phosphate Zeolite, heteropolyacid and acidic and basic ion exchange resins, and wherein the reaction is performed in a mixture of water and an organic solvent, the organic solvent is selected from alkanols and polyols. 2. According to the scope of patent application! The method of item 1, wherein the reaction is performed at 140 ° C to 320 ° C. 3. The method according to item 1 or 2 of the scope of patent application, wherein the aminocarboxylic acid compound used is selected from the group consisting of 6-aminohexanoic acid, 6-aminohexanoic acid methyl ester, 6-aminohexanoic acid ethyl ester, 6-amino_N · methylhexamidine, 6-amino_N, N-dimethylhexamidine '6_amino_N-ethylhexamidine, 6-amino-N, N -Diethylhexamidine and 6-aminohexamidine. 4. The method according to item 1 or 2 of the scope of patent application, wherein the alkanol is a C1-C4-alkanol. 5. The method according to item 1 of the scope of patent application, wherein the catalyst is selected from oxides of elements of the second, third or fourth main group of the periodic table and oxides of elements of the second to sixth order of the periodic table. This paper is in use again ® National Standard (CNS) A4 (210X297 mm) f Please read the precautions on the back before filling out this page), 1T ·· Ministry of Economic Affairs, Central Bureau of Standards and Labor, Consumer Cooperatives印 簟 .II I A8 38S758_I 6. Application scope 6. The method according to item 5 of the application scope, wherein the catalyst is selected from the group consisting of aluminum oxide, silicon oxide, germanium oxide and oxidation. (Please read the precautions on the back before filling out this page) Customized · Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs This paper has been re-used in China National Standard (CNS) A4 (210 > < 297mm)