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    • 专利摘要:

    公开号:SU1213985A3
    申请号:SU823374300
    申请日:1982-01-08
    公开日:1986-02-23
    发明作者:Динкель Рольф；Редель Хильмар；Ян Грейсон Джеймс
    申请人:Лонца Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to an improved process for the production of 3-picolin, an important intermediate in the chemical industry.
    The purpose of the invention is to discharge the output of 3-pP 1 coline
    Example 1. 1140 ml of a 3.40-molar aqueous solution of diammonium hydrogenphosphate (pH8.35) (dissociation constant at 7x1 SG) is heated in a 2 l autoclave to 230 ° C and stirred at 1500. A mixture of 117.7 g (2.67 mol of acetaldehyde-, 49, And g (0.356 mol) of hexamethylenetetramine and 200 g of water (molar ratio of acetaldehyde and formaldehyde 1: 0.78) is pumped continuously into this solution for 55 minutes. The reaction pressure ranges from 33 to 39 bar. After the NIL mixture of the educt mixture is added, the reaction mixture is stirred for another 10 min at 230 ° C and then cooled to room temperature. Then extraction of 3x100 MP of methylene chloride is carried out, and also gas chromatographic analysis is performed. dinene L) 1x extracts of large-scale methylene. The following is obtained depending on the needs of aldehyde, vypsod acetaldehyde (A) or hecromethylene tetramine (F): pyridine 1.0 g 1.0% (A 3 - PICOLIN 57.8 g. 59.4% (F) | 3 -ethylpyridine 21.8 g 22.8% (A); 2.5 - lutidine 3.8 g - 4.0% (A); H-lutidine 055 g 0.7% (F) I 2 - metsh1 5 - ztshs-- 1.4 g 1.8% (A). The aqueous phase has a pH of 9.2 after extraction.
    . Example 2, 1140 ml of a 3.40 molar aqueous solution of pugenogram phosphate ammonium (pH8., 35) (dissociation constant at 25 s - 7x10), heated in a 2 l autoclave to 230 s and stirred at 1500 vol. / min A mixture of 117.7 g (3.9 mol) of paraldehyde, 49.8 g (0.356 mol) of hexamethylenetetramine, 130 g of water and 120 g of ethanol are pumped into this solution continuously (60 g) and the alkaline molar ratio acetaldehyde with formaldehyde (150.80). At the same time, the reaction pressure ranges from j35 to 44 bar. Further, the process is carried out as in Example 1. After isolating the products, the following 1DIY5 is obtained, depending on the need of the aldehyde, the output of the paradedeck (A) or hexamethylenetetramia (F); pyrr-a12139852
    dyn 0.9 g 0.8% (A); 3-picoline 63.8 g 65.6% (F); 3-ethylpyridine 21.8 g 19.0% (A); 2.5 lutidine 3.2 g 3.4% (A) | 3.5-lutidine 6.0 0.8% (F): 2-methyl-5-ethylpyridine 2.3, 8% (A). After extraction, the pH of the aqueous phase is 9.4. Example 3. 1140 ml of a 3.40 molar aqueous solution of diammonium hydrogenphosphate (pH 8.35) (constant
    | .
    to dissociation at 25 С 7x10) is heated
    0
    They are in an autoclave with a capacity of 2 liters to 220 ° C and stirred at 1500 rpm. A mixture of 120.0 g (4.0 mol) is pumped into this solution over 59 minutes.
    i. paradehyde, 49.8 g (0.356 mol) of hexamethylenetetramine, 120 g of water and 120 g of ethanol (the calculation molar ratio of acetaldehyde to formaldehyde is 1: 0.78). At the same time, the regional pressure fluctuates between 26 and 40 bar. Further, the process scheme is the same as in example 1. The selection of products gives the following, depending on the need of aldehyde, you. the course of paraldehyde (A) or hexamethylenetetramine (F); pyridine 0.3 g; 0.3% (A) | 3-picoline 49.9, 4% (F) | 3-ethylpyridine 5.6 g 6.0% (A) | 2 ,, 5-lutidine 1.4 g 1.4% (A); 3.5-lutidine 2.0 g 2.7% (F) 2-methyl-5-α-shtsihridin 5.4 g 6.8% (A), After extraction, the pH of the aqueous phase is 9.3.
    Example 4. 1140 ml of a 3.40 molar aqueous solution of diammonium hydrogenphosphate (pH 8.35) (dissociation constant at 7x10) is heated in a 2 l autoclave to 230 ° C and stirred at 1500 rpm. A 47 ivmH mixture of 117.7 g (2.67 mol) of acetaldehyde and 162.2 g (2.13 mol) of formaldehyde dimethyl acetal (molar ratio 1: 0.80) is continuously pumped into this solution. Here, the reaction pressure ranges from 33 to 40 bar. Further, the process scheme is the same as in Example 1. The product is produced in the following way, depending on the need for aldehyde., The yield of acetaldehyde (A) or formaldehyde dimethyl acetal (P): pyridine 1.0 g 0.9% (A) ; 3-picoline 47.0 g 51.2% (F) I 3-ethylpyridine 23.4 g 24.6% (A); 2.5 lutidine 4.4 g 4.6% (A); 3.5 lutidine 0.6 g 0.8% (F); 2-Met1-t-5-ethylpyridine 3.2 g 3.9% (A).
    Example 5. 1140 ml of a 3.40 molar aqueous solution of hydrogenO
    0
    five
    (1.35 mol) of acetaldehyde diethyl acetal, 106.6 g (1.066 mol) of a 30% formaldehyde solution, 50.0 g of 3-picolin and 50 g of ethanol (molar content of acetaldehyde) formaldehyde 1: 0,80). In doing so, the reaction pressure ranges from 33 to 42 bar. The process is then carried out, as in Example 1, of diammonium phosphate (pH 8.35) (dissociation constant at 25 ° C, 7x1 SG) is heated in a 2 l autoclave to 230 ° C and stirred at 1500 rpm. A mixture of 117.7 g (4.0 mol) of paraldehyde and 162.2 g (2.13 mol) of formaldehyde dimethyl acetal (calculating molar ratio of acetaldehyde to the formation of products) gives 64 min to this solution. , in maldehyde 1: 0,80). In this case, the reaction is dependent on the need for aldehyde, the oning pressure fluctuates within the range of ethyl acetaldehyde diethyl acetal 33 - 40 bar. Then the process was carried out - (A) or formaldehyde (F): pyridine, as in Example 1. Separation of pro-0.5 g 0.9% (A); 3-picoline 18.9 g of ducts gives the following, depending on 15.38.3% (F) (without a fraction for homogenization — depending on the need for aldehyde, the yield of a shake); 3-ethylpyridine 11.5 g 24.6% (A); raldehyde (A) or d1-shetilacetal 2,5-lutpdine 2.2 g 4.6% (A); formaldehyde (f): pyridine 1.0 g 3.5-lutidine 0.5 g 1.4%. (f); 2-1.0% (A); 3-picoline 49.2, 6% (F); tyl-5-ethylpyridine 1.2 g 3.1% (A). 3-ethylpyridine 22,, 9% (A); 2.5-20 Example 8. 1140 ml of aqueous lutidine 4.1 g 4.3% (A); A 3.5-liter solution containing 157.4 g of sodium hydrogensulfate (dissociation constant at 25 ° С 1x103) and 85.1 g of ammonia (pH 10.8) of the heated aqueous solution are hydrogenophosphate-25. capacity 2 liters to
    230 C and stirred at 1500 rpm. B this solution is continuously pumped for 65 minutes a mixture of 117.7 g (2.67 mol) of acetaldehyde and 171.0 g (O, 25 mol)
    dyn 0.4 g 0.6% (F); 2-methyl-5-ethylpyridine 2.0 g. 2.5% (A).
    Example 6. 855 ml of a 3.40-mol mouth of diammonium (pH 8.35) (dissociation constant at 25 ° C 7x10) are heated in a 2 l autoclave to 230 ° C. And stirred at 1500 rpm,
    Formaldehyde zodimethyl acetal is continuously pumped into this solution (for 60 in a mixture of 160.0 g the calming molar ratio is
    acetaldehyde with formaldehyde 1: O, 80). At the same time, the reaction pressure (1.76 mol) of acetaldehyde dimethyl acetal, 160.0 g (0.625 mol) of a 30% aqueous formaldehyde solution and 22.5 g of 3-picoline (molar), Next, the process is carried out as
    The oscillation ranges from 43-45 bar.
    40
    dimethyl acetaldehyde with formaldehyde (1: 0.95). Here, the reaction pressure ranges from 33 to 39 bar. The process is then carried out as in Example 1. The isolation of the products gives the following, depending on the needs of the aldehyde, the yield of acetaldehyde dimethyl acetal (A) or formaldehyde (F): pyridine 0.7 g 1.1% (A); 3-picotin 40.9 g 54.9% (F) (without a fraction for homogenization); 3-ethylpyridine 7.8 g 12.7% (A); 255-lutidine 1.6 g 2.6% (A); 3.5-lutidine 0.7 g 1.2% (F); 2-methyl-5-ethylpyridine 0.3 g 0.6% (A).
    in example 1. Isolation of the products gives the following, depending on the need of aldegvd, the yield of adetaldehyde (A) or dimethyl acetal formaldehyde (F): pyridine 2.2 g 2.1% (A); 3-picoline 52.9 g 53.4% (F); 3-etylpyridine 16.8 g 17.7% (A); 2.5 lutidine 6.5 g 8.6% (A); 3.5-α-lutidine 0.8 g 1.0% (F); 2-methyl-ethylpyridine 2.9 g 3.5% (A).
    Example 9. 1140 ml of an aqueous solution containing 155.1 g of potassium dihydrogenphosphate (dissociation constant at 25 C 1x10), and
    50 85., 1 g of ammonia (pH of the solution is 10.95) is heated in an autoclave with a capacity of 2 l to 230 C is stirred at 1500 rpm. 65 min. Mixture is continuously pumped into this solution.
    Example 7, 1140 MP 3.40-molar iodine solution of diammonium hydrogen phosphate (piI8.35) (dissociation constant ng And 25 ° C 7x10), heated in a 2 l autoclave to 230 C and stirred at 1 500 vol . / min For this solution, a mixture of 160.0 g is continuously pumped over 59 minutes.
    139854
    (1.35 mol) of acetaldehyde diethyl acetal, 106.6 g (1.066 mol) of a 30% formaldehyde solution, 50.0 g of 3-picolin and 50 g of ethanol (molar content of acetaldehyde) formaldehyde 1: 0,80). In doing so, the reaction pressure ranges from 33 to 42 bar. Further, the process is carried out, as in Example 1, You 10 division of the products gives the following, depending on the needs of the aldehyde, the yield of diethyl acetal acetaldehyde (A) or formaldehyde (F): pyridine 0.5 g 0.9% (A); 3-picoline 18.9 g 15 38.3% (P) (without a fraction for homogenization); 3-ethylpyridine 11.5 g 24.6% (A); 2.5 lutpdine 2.2 g 4.6% (A); 3.5 lutidine 0.5 g 1.4%. (F); 2-me; tyl-5-ethylpyridine 1.2 g 3.1% (A). 20 Example 8. 1140 ml of an aqueous solution containing 157.4 g of a hydrodale. The process is carried out as
    The oscillation ranges from 43-45 bar.
    in example 1. Isolation of the products gives the following, depending on the need of aldegvd, the yield of adetaldehyde (A) or dimethyl acetal formaldehyde (F): pyridine 2.2 g 2.1% (A); 3-picoline 52.9 g 53.4% (F); 3-etylpyridine 16.8 g 17.7% (A); 2.5 lutidine 6.5 g 8.6% (A); 3.5-α-lutidine 0.8 g 1.0% (F); 2-methyl-ethylpyridine 2.9 g 3.5% (A).
    Example 9. 1140 ml of an aqueous solution containing 155.1 g of potassium dihydrogenphosphate (dissociation constant at 25 C 1x10), and
    85., 1 g of ammonia (pH of the solution is 10.95) is heated in an autoclave with a capacity of 2 liters to 230 Cu stirred at 1500 rpm. 65 min. Mixture is continuously pumped into this solution.
    out of 117.7 g (2.67 mol) of acetaldehyde and 171.0 g (2.25 mol) of formaldehyde dimethyl acetal (calculational molar ratio of acetaldehyde with formaldehyde is 1: 0.80). With this, the reaction pressure; ranges from 47 to 52 bar. Further, the process is carried out in the same way as in Example 1. The separation of products gives the following, depending on the need of the aldehyde, the yield of acetaldehyde (A) or dimethyl acetal formaldehyde (F): pyridine 1.4 g 1.3% ( BUT); 3-picoline 19.2, 3% (F) 3-ethylpyridine 31.4 g, 32.9% (A) | 2 O 5-lutidine 8.8 g, 9.3% (A-) | 3,5-lutndin 0.3 g (F7 | 2-methyl-5-ethylpyridine 16.8 g 20.8% (A).
    Example 10. 1140 ml of a 3.40 molar aqueous solution of ammonium acetate (pH 7.55) (dissociation constant at 25 ° C 1) are heated in a 2 l autoclave to 230 ° C and mixed at 1500 o b , / min. A 52 ivttiH mixture of 96.0 g (3.19 mol) of paraldehyde, 39.8 g (0.284 yul), hexamethylenetetramine, 104 g of water and 100 g of ethanol (molar ratio of acetaldehyde with formaldehyde 1: 0580). In this case, the reaction pressure fluctuates within 25-32 bar. Further, the process is carried out, as in Example 1, the isolation of the products gives the following, depending on the aldegde consumption, the yield of paraldehyde (A) or hexamethylenetetramine (F); pyridine 0.9 g 1.0% (A) 3 picolip 44.2 g 56.3% (F); 3-ethylpyridine 14 g 18.5% (A); 2.5 - lutidine 3.9 g 5.1% (A); 3.5-lutidine 0.3 g 0.6% (F); 2 methyl-5-ethylpyridine 1.8 g 2.7% (A).
    Example 11, 1140 ml of a 3.40-molar aqueous solution of diamgaprene hydroxyphosphate (pH 8.35) (dissociation constant at 25 ° C) is heated in a 2 l autoclave to 230 ° C and stirred at. 1500 rev / min A mixture of 200.0 g (1.69 mol) of acetaldehyde dietary acetaldehyde and 105.5 g (15386 mol) of formaldehyde dimethyl acetal (mol ratio of acetaldehyde with formaldehyde 1; 0.80) is continuously pumped into this solution for 55 min. At the same time, the reaction pressure ranges from 37 to 38 bar. Further, the process is carried out, as in Example 1. The volume of the products gives the following, depending on the need of the aldehyde, the yield of diethylacetal acetaldehyde
    (A) either formaldehyde dimethyl acetal (P): pyridine 0.6 g 1.0% (A); 3-picoline 21.8 g 35.7% (F) j 3-ethylpyridine 20.1 g 34.4% (A); 2.5 lutidine 4.4 g, 7.4% (A); 3,5-lutidine O, 1 g 0.3% (F); 2-methyl-4-ethylpyridine 5.3 g 10.6% (A).
    Example 12, .1140 ml of a 3.40 molar aqueous solution of hydrogenphosphate diatfeunium (pH 8.4) (dissociation constant at 25 with 7x10) is heated in an autoclave with a capacity of up to and stirred at 1500 rpm, B, V 60 minutes are continuously injected with the aid of the first pump, 237.0 g (2.0 mol) of acetaldehyde (ethyl acetate) and a second pump — a mixture of 38.8 (0.277 mol) of hexamethylenetetramine and 103 g of water (molar ratio of acetaldehyde formaldehyde 1: 085), wherein the reaction pressure ranges from 32-42 bar. Further, the process is carried out, as in Example 1, the introduction of the products gives the following. (S, depending on the needs of the aldehyde, acetaldehyde diethyl acetaldehyde (A) or hexamelo-t.elentetra of the shn (F): pyridine 0.7 g 0.9% (A) j: 3-picoline 44.2 g 57.7% (F); Z-ztilnnitsin 10.8, 6% (A); 2, 5-lutidine 2.0 g 1, 3% (A); 3,5-β-Lutidine 0.8 g - 1.3% (f): 2 - methyl-5 - ethyl pyridine 0.7 g 1.2% (A).
    Example 13, 1140 mm of an aqueous solution containing 397.1 g of dicali hydrogen phosphate (dissociation constant at 7x10) and 42.6 g of ammonia (pH of the solution is 11.8) are heated in a 2 l autoclave to 230 ° C and mixed at 1500 rpm A mixture of 117.2 g (2.66 mol) of acetaldehyde and 213.3 g (2.14 mol) of a 30.2% aqueous solution of formaldehyde is continuously pumped into this solution for 63 minutes (molar ratio 1: 0). , 81). At the same time, the reaction pressure ranges from 35 to 33 bar. After the addition of the aldehyde mixture is completed, the reaction mass is additionally stirred for 10 min at. 230 ° C and then cooled to room temperature. Next, the polar organic phase is separated, the aqueous phase is extracted with 3x100 j-in methylene chloride, the extracts are combined with the indicated organic phase and the separated phase is again
    71
    The aqueous phase is shaken with an additional 60 MP of methylene chloride. By gas chromatographic analysis of all 5 joined organic layers, the following, depending on the need of aldehyde, is obtained addetaldehyde (A) or formaldehyde (F) yield: pyridine 1.8 g 1.7% (A) 3-picoline 46.3 g 46.4 % (F); 3-ethyl pyridine 9.9 g 10.4% (A); 2.5-lutidine 4.0 g 4.2% (A)} 3.5-lutidine 2.2 g 2.9% (F); 2-methyl-5-ethylpyridine 0.8 g 1.0% (A).
    P. Example. 14. 1140 ml of an aqueous solution containing 155.1 g of potassium dihydrogenphosphate (dissociation constant at 25 ° С - 1x1 (}), and 85.1 g of ammonia (pH of the solution is 10.6) are heated in an autoclave with a capacity of 2 l to 230 ° C and stirred at 1500 rpm./minutes In this solution is continuously pumped for 65 min a mixture of 117.6 g (2.67 mol) of acetaldehyde and 213.3 g (2.17 mol) of 35% - formaldehyde solution (molar ratio 1: 0.81). At the same time, the reaction pressure ranges from 40 to 38 bar. Next. The process proceeds as in Example 13. The product is isolated according to aldehyde waste; j yield of acetaldehyde (A) or formaldehyde (F): pyridine 1.6 g 1.5% (A); 3-picoline 60.9 g 60.3% (F); 3-ethylpyridine 15.6. d. 16.4% (A); 2.5-lutidine 4.0 g 4.2% (A); 3.5-lutidine 1.1 g 1.4% (F); 2-methyl- 5-ethylpyridine 1.1 g 1.3% (A).
    Example 15. 1140 ml of an aqueous solution containing 157.4 g of sodium hydrogensulfate (dissociation constant at 25 ° С f), and 85 - 1 g of rmmiac (pH of the solution) are heated in a 2 l autoclave to 230 ° C and stirred at 1500 rpm A mixture of 117.3 g is pumped into this solution continuously for 65 minutes. (2.66 mol) of acetaldehyde and 213.3 g (2.17 mol) of a 30.5% aqueous solution of formaldehyde (molar ratio 1: 0.81). At the same time, the reaction pressure ranges from 38 to 37 bar. The process then proceeds as in Example 13. The product gives the following, depending on the sweat: the yield of acetaldehyde (A) or formaldehyde (F) depends on aldehyde: pyridine 2.0 g 1.9% (A); z-picoline. 56.7 g 56.2% (F); 3-methylpyridine
    58
    13.2 g 13.9% (A); 2.5-lutidine 4.9 g 5.2% (A), 3.5-lutidine 0.9 g 1.1% (F); 2-methyl-5-ethyl 1P1ridine 1.2g 1.5% (A).
    Example 16. 1140 ml of an aqueous solution containing 47.9 g of sodium fluoride (dissociation constant at 25 ° C -) and 85.1 g of ammonia (pH of the solution is 12.2) are heated in a 2 l autoclave to 230 ° C and stirred at 1500 rpm A mixture of 11.7.2 g (2.66 mol) of acetaldehyde and 213.3 g (2.17 mol) is continuously pumped into this solution for 67 min.
    30.5% aqueous formaldehyde solution (molar ratio 1: 0.81). At the same time, the reaction pressure ranges from 32 to 30 bar. Next, the process is carried out analogously to example 13. The separation of the products gives the following, depending on the needs of the aldehyde, the yield of acetaldehyde (A) or formaldehyde (F): pyridine 2.6 g 2 , 5% (A); 3-picoline
    43.7 g, 43.3% (F); Z-ethylpyridine. 8.9 g 9.4% (A); 2.5 lutidine 4.2g 4.4% (A); 3.5-lutidine 1.9, 5% (F); 2-methyl-5-ethylpyridine 0.9 g 1.1% (A).
    Example 17. 1140 ml of an aqueous solution containing 187.0 g of sodium acetate (dissociation constant at 25 ° C, 1.8x10, and 42.6 g of ammonia (pH 1.21) are heated in a 2 l autoclave to 230 ° C and mixed
    at 1500 vol. .. A mixture of 117.6 g (2.67 mol) of acetaldehyde and 213.3 g (2.17 mol) of 30.5% aqueous formaldehyde solution is continuously pumped into this solution for 60 min.
    (molar ratio 1: 0.81). Here, the reaction pressure ranges from 32 to 30 bar. Further ; the process is carried out analogously to example 13. The isolation of the products gives
    the next, depending on the needs of the aldehyde, is the yield of acetaldehyde (A) or formaldehyde (F): pyridine 2.5 g 2.4% (A) j 3-picoline 41.4 41.0% (F); Z-ethylpyridine
    7.0 g 7.3% (A); 2,5-lutidine. 3.8 g, 4.0% (A); 3.5 lutidine .1.9 g 2.4% (F); 2-metsh1-5-ethylpyridine 0,8, 0% - (A)
    Example 18. 1140 ml of an aqueous solution containing 200.4 g of ammonium pentaborate and 50.1 g of ammonia
    (pH of solution 10.1) is heated in an autoclave with a capacity of 2 liters to 230 ° C and mixed at 1500 rpm. This solution is continuously pumped in teggenna: 0 minutes a mixture of 109.9 g (2.49 mol) 224.1: D (2.24 molts) of 30.1% aqueous solution forms; dehydrate (molar ratio 1.) "At the same time, the reaction pressure ranges from 34-35 bar, the process carried out analogously to example 13, the production of products gives the following, B, depending on the needs of alde Idaev, the course of acetaldehyde (A.) or fmalmalde- (F); pyridine 2.1,% (L); H-picolin 54.9 g 5254% (F); H-ethylpyridine 6.9 g 7.7% (A) | 2.5 - lutidine 3.1 g (A) j 3.5-lutidn 1.2 g - 1.5% (F) J 2 metsh-5-ethyl pyrid11 1 (, 5 0.6% (A).
    Example 19, 1140 ml of B0.d; 1o: th pacTBoipa containing about 1i45l: ammonium sarb-sodium (formula P and dissapillite at 4x10), and 85.1 g of ammdac (pH of 10.3) pagreva from the mixture in container 2 l before and: lers1
    Stir at 1500 rev / min. T: this solution continuously pumps in. For 66 minutes, a mixture of 117.6 g (2.67 mol) of acetaldehyde to 213.3 g (2.17 mol) of 30.6% -11th 1 one-: th plant formaldehyde thief (molar correspondence 110,81); At the same time, the regactga onis pressure fluctuates within 38.3 bar. Next, the process is carried out analogously to example 13. The product separation gives the following aldehyde and / or acetaldegy (A) or Tegid (F) formal; pyridine 1.5 g - -.4% (A); 3 - PICOLIN 51.8 g 51.2% (“) j 3-ethylpyridine 14s5 1552% (L) i 2.5-lutidine g 4.1% (A) j 3.5 -lutidine 0.9 g one; 2% (F); 2-11-11 -5-ETYLPYRIDIN 1 ,, 1 g 13 4% (A) ..,
    Example 20, 1140 mt; water golch) solution containing about 301.3 sulphate at-tnn (dissociation constant: at 25 C 1.2x10 and 50 ga.shak (pH of solution 9.9) is heated in an autoclave
    WITH
    with a capacity of 2 liters up to 230 ° C and iieise M & waK ivjT at 1500 rpm, this is extremely pumped — for a mixture of 11756 g (2.67 mt.tg), (degca and 231.3 g (zero) of 30 e2% an aqueous solution of formaldehyde (molar ratio IjO.Of) :, The reaction pressure is 36 bar. Next, irog-esse is accomplished / -in-gat as in example 13. Vshsche.pe-- the product’s appearance gives the following; -y1tty depending on the sweat of aldehyde, acetaldehyde (A) or formaldehyde (F); pyridine 154 g 1.3% (A) °, 3 H1Icholin 57.6 g 57.5% (F ); 3-ethylpridine 15.4 g 1651% (A) I 2.5-lutidine 4.6 g 4.8% (A); S-lutidine 0.5 g 0.7% (F); 2 - meth l-b-ridin etilni- To 4 g of 1.7% (A).
    PRI me R 21. 1140 ml of an aqueous solution containing, e; 223.3 g of ammonium bromide (dissociation constant at 25 ° C), and 51.1 g of ammonia (9.7 RP solution)
    1: 1H ;;;; 1; (HA at 1500 rev / min. In this plant- iop. Continuously pumped in.:; Y; a mixture of 117.6 g (2.67 mol) g T of vitaldehyde and 213 , 3 g (2.16 mol) MH:, 4% aqueous formaldehyde solution (molar ratio 1: 0.81), Pgn this reaction pressure was 40 bp, Next, the process is carried out as in Example 13 The introduction of the product gives the following: o: ций, to head, –– s; ––, most of the need for aldehyde, acetaldehyde (A) or forl: д de ida (f): pyridine 1 j 2 g 1., % (A); 3-PIKOPN1 58.6 g 58.3% (F); 3-ethyl-lyridine 10.6 g 10.5% (A);
    2.5-lutidine 3.8 g - 4.0% (A); 3.5- - mumdin 0.5 g 0.6% (f); 2- methyl- -5-ztilpyridine Oj6 g - O ,, 8% (A)
    With j; er 22, 1140 ml of water; asgvoro, content of 91 t g by droppings :. (dissociation constant
    at 25 ° С 1.2x10), and 68.1 g of ammonia: .pli of the solution 10.2) is heated in auto- 7-: .Ge. with a capacity of 2 liters up to 230 С and transfer: l ;; ; | 1: a; from at 1500 o5, / min. In this jjacTBOp, a mixture of 11 7, 6 g (2, 67 mol), ethedegy, c 1 and 213..3 g (2.16 mol) 30,;% - water solution is continuously pumped over 62 minutes formal-: (-: 1G1-schz (molar ratio IsOjBI).; JpH This reaction pressure fluctuates .uj /rc.ii in the range of 39 43 bar., Further: about 1, 1 process is absorbed in a similar way; Fri; at 13. Finishing products gives with / hedyuyutsyil depending on the consumer::; spine aldep-gda, exit and datdegida
    (A).-Gibo formaldehyde (f); pyridine 1.8 g 1.7% (A,): 3-picoline 56.4-g 56.1% (f): 3-ethylpyridine 13.8 g 14 „5% (A) :: 2.5 - lutidine g, 5.4% (A) | 3.5-lutidine 0.8 g 1.1% (F);
    2 g-; vtil-5-ethylpyridine g - 1.6% G ,,.
    Pr and -fj er 23., 1140 nl of aqueous pac J Bopa, containing 152.1 g of succinate20
    ammonium Nata (dissociation constant; Cr 25 ° C 6.4x10), and 51.1 g of ammonia (pH of the solution 10.1) are heated in a 2 liter autoclave to 230 ° C and stirred at 1500 rpm. This 5
    pacTBop is continuously pumped for 6.1 minutes. a mixture of 117.5 g (2.67 mol) of acetaldehyde and 213.3 g (2.17 mol) of a 30.6% aqueous solution of formaldehyde (molar ratio 1: 0.81). Q At the same time, the reaction pressure ranges from 36 to 36 bar. Next, the process is carried out analogously to example 13. The isolation of the products gives the following, depending on the need for aldehyde, the yield of acetaldehyde (A) or formaldehyde (F) :. pyridine 1.4 g 1.3% (A); 3-picoline 46.7 g 48.4% (F); 3-ethylpyridine 18.3 g 19.2% (A); 2.5 lutidine 6.4-g 6.7% (A); 3.5 lutidine 0.4 g 0.5% (F); 2-methyl-5-ethylpyridn 2.4 g, 3.0% (A).
    Example 24. 1140 ml of water
    solution containing 180.2 g of ammonium adipate 25 ammonium (dissociation constant at 25 ° C 3.9 x 10) and 51.1 g of ammonia (solution pH 10.1) are heated in a 2 l autoclave to 230 ° C and stirred at 1500 vol ./min. A mixture of 117.1 g (2.66 mol) of acetaldehyde and 213.3 g (2.17 mol) of a 30.6% aqueous solution of formaldehyde is continuously pumped into this solution for 59 minutes (molar ratio 1: 0, 81. At the same time, the reaction pressure ranges from 33 to 35 bar. Next, the ocyutecT- process is analogous to example 13. Completion of the products gives the following, depending on the need for aldehyde, the yield of acetaldehyde (A) or formaldehyde (F): pyridine 1, 3 g 1.2% (A); 3-picoline 56.3 g 55.7% (F); 3-ethyl-pyridine 15.4 g 16.2% (A); 2.5-lutidine 4, 6 g 4.8% (A); 3,5-lutidine 0.5 g 0.7% (F); 2-methyl-5 ethyl pyridine 1.2 g 1.5% (BUT).
    Example 25. 1140 ml of an aqueous solution containing 200.2 g of phthalate-50 ta of diammonium (dissociation constant at 25 ° C, 3.9x1 ()), and 51.1 g of ammonia (pH of the solution is 10.1) are heated in a 2-volume autoclave l to 230 ° C and stirred at 1500 rpm. In this 55 solution, a mixture of 117.7 g (2.67 mol) of adetaldehyde and 213.3 g is continuously pumped over 58 minutes
    thirty
    35
    40
    45
    0
    j
    five
    0 5
    0
    five
    0
    five
    (2.17 mol) of a 30.6% formaldehyde aqueous solution (molar ratio 1: 0.81). The reaction pressure was 37 bar. Further, the process is carried out analogously to example 13. The product gives the following, depending on the needs of the aldehyde, the yield of acetaldehyde (A) or formaldehyde (F): pyridine 1.4 g 1.3% ( BUT); 3-picoline
    49.0g 48.4% (F); 3-ethylpridine15.1g 15.8% (A) 2.5-lutidine. 5.4 g 5, .7% (A); 3.5-lutidine 0.5 g 0.6% (F); 2-methyl-5-ethyl 1 Pyridine
    1.7 g, 2.1% (A).
    j Example 26. 1140 ml of an aqueous solution containing 112.1 g of diammonium terephthalate (dissociation constant at 25 ° С 1) and 66.1 g of ammonia (pH of solution 10.0) are heated in a 2 l autoclave to 230 ° C and stirred at 1500 rpm, / min A mixture of 117.6. (2.68 mol) of acetaldehyde and 213.3 g (2.17 mol) of a 30.6% aqueous solution of formaldehyde is continuously pumped into this solution for 58 min. (Molar ratio 1: 0, 81). In doing so, the reaction pressure ranges from 36 to 38 bar. The process then proceeds analogously to example 13. The isolation of products gives the following, depending on the need for aldehyde, the yield of acetaldehyde (A) or formaldehyde (F): pyridine 1, 1.4% (A); 3-picoline 56.8 g 56.1% (F); 3-ethylpyridine 13.3 g 14.0% (A); 2.5 lutidine g 5.1% (A); 3.5-α-lutidine 0.6 g 0.8% (F); 2-methyl-5-ethylpyridine 1.1 g 1.4% (A).
    Example 27, 1140 m of an aqueous solution containing 403.6 nicotinate am 1oni (dissociation constant at 25 ° C, 8.1x10), and 36.1 g | ammonia (pH jpacTBOp; 9.8). Are heated in a 2-volume autoclave l to 230 C and stirred at 1500 rpm./min ... A mixture of 117.6 g (2.67 mol) of acetaldehyde and 213.3 g (2.17 mol) of 303, is continuously pumped into this solution for 60 min. 5% aqueous formaldehyde solution (molar ratio 1: 0.81). The reaction pressure was 30 bar. The process is then carried out similarly to Example 13 .: The distribution of the products gives the following, depending on the use of aldehyde j, acetaldepde yield –1 dal (A) or formaldehyde (F): pyridine 2.3 g 2.2% (A) J 3 -ncol 54.8 g 54.3% (F); 3-ethnpyr dcp 16.6 g 17j4 (A); 2, 5-percent 3.9% (A); 3.5-lutidine 0.5 g 0/7% (f) I 2-methyl-5-ethyl pyridt1 1.1 g 1.4% (A).
    Example 28 “1140 ml of aqueous pacTBopg.s containing 140.1 g of isotin-Kotin ammonium (dissociation constant at 25 ° С 1.5x10) ,, and 68.1 g (solution pH) are heated in an autoclave with a capacity of 2 l to 230 ° C and reversal at 1500 rev / min. In this solution continuously iacacinthus for 65 yush a mixture of G 7, 5 g (2, 67 mol) of acetaldehyde and 213.3 g (2.16 mol) of 30.4% formaldehyde solution (molar ciioTnci- - Sewing UOjSI). At the same time, the reaction pressure ranges from 38 to 41 bar. Next, the progress is done by way of example 13 - Vutelesh 1T Sdu; -: a goal gives the following, depending on the IVO type, the acetalde-; hida- (A) or formaldehyde (F); pi pshtin 1.9 g 1.18% (A); Z-mshkoli- 47; 7 g 47.5% (F) I 3 - ethyl pyridite | 11.7 g 12.3% (A) | 2.5 - lutsh1; t1M 4.9 g - 5.1% (A); 3.5 lutidine 0.6 g 0.8% (F); 2-methyl 5-ethyl 11iridyl 1, 3 g
    1.6% (A),
    one
    Example 29, - 1140 gtl. 3,40-s: a clear aqueous solution containing; —th hydrohephosphate diamgloich (, piI8.35 (dissociation constant at 25 С 7x10), is heated in an autoclave with an evr costyo 2 l to 180 C and perecheshivayut at 1500 rpm, B this solution is continuously nipped into a tempered 55 min mixture from 117.7 g (2.67; 40, ra-J acetaldehyde, G4., 3 g (q; 1 l; hexamethylenetetramine and 200 g water; molar ratio / 1,); At the same time, the reaction pressure varies from 33 to 39 bar, after the end of the addition of the zsgg mixture, the reaction mass of the additional mixture is crushed for 10 min at 180 ° C and then cooled; 1 to the room gel. action with
    The aqueous phase is separated (5) and the 3x100 ml of methylene chloride is extracted from the extracts of the dipo gots with indications of the organic phase and the separated s - and the aqueous phase is shaken with an additional 60 Iffl chlorostool ,, Puts of the gas chromatograph of the chesxgo;: ia liza sees 5 soad-ink orgagi
    The 5th layers get the following, the heading: - Symptoms from the need of aldeide, output of adaldehyde (A) or orormaldepad (F): S-picoline 16.3 g 23.8% (F); 3 - ethylpyridine 33.5 g 35.1% (A).
    For example, 30 ml of 3540-morno water; d; 5 solution containing hydro, e: 1 phosphate dia: .n - yunik (pH8.35)
    (constant d, isso1 iadii-at 25 C - - a h
    (xH)}, is heated in autoglass with a capacity of 2 liters to 205 ° C and stirring ™ OT three 1500 vol .. In this solution, a mixture of i-i3 117.3 g (2.66 mol) of adate is continuously pumped over 55 minutes; 1 g, 49.8 g (0.355 mol) of goksayetil tetramksh and 200 g of water (molar c (3 O: iioiLieinie 1: 0.80). With peaiainoHHoe, the pressure fluctuates between 33 and 39 bar after completing the addition of the mixture of educts 1; add additional mass: 10 minutes 205 ° C and then cool to room temperature.The resulting organic phase C) where: 1 g, extract the aqueous phase with 3x100 ml of methylene chloride, extra The acts are combined with indications of the organic phase il again divided once, about the phase of all hivathots with the complement — 1HL: and 60 M.H.x; iopHCToro of methylene, luta: gas chromatographic analysis of all 5 organic compounds: x layers get the following, depending on the need of the aldehyde,,: addetaldeh-id code (A) or formal /; er: -t11, and (;) 3 picoline, 47.3 g, 48.3% of D (0 ; 3-ethylpyridine 5.9 g 6.2% (A).
    Г1 р-мер 31, 1140 ml 3., 40-molten aqueous solution, containing- 14; diammonium hydrogenphosphate (рН8.35)
    at 1500 V, this solution was continuously pumped for about 55 minutes. shes from 11755 g (2,., 67 mol) of acetal; x: hydaz 49.9 g (0.356 mol) of hexameter tent blends of W and 200 g of water ( molar ratio l 0, QO) At the same time, the reaction pressure fluctuates at a limit of x 33 - 39 bar. After the addition of the mixtures of the reactants .iv t- OKiiyio is completed, the mixture is stirred for 10 minutes at 240 ° C and then cooled. to room temperature. Next, the obtained organic phase of the division Kug, - the aqueous phase is extracted
    15121
    x100 ml of methylene chloride; the extracts are combined with the indicated organic phase and the separated aqueous phase is shaken with an additional 60 ml of methylene chloride. By gas chromatographic analysis of all 5 combined organic words, the following, depending on the need of aldehyde, is obtained the yield of acetaldehyde (A) or formaldehyde (F): 3-picoline 60.3 g 60.6% (F); 3-ethylpyridine 20.5 g 21.5% (A).
    Example 32, P40 ml of a 3.40-sea water solution containing diammonium hydrogenphosphate (pH 8.35) (dissociation constant at 25 ° C 7x10) is heated in a 2 l autoclave before and stirred at 1500 rpm. A mixture of 117.4 g (2.67 mol) of acetaldehyde, 74.7 g (0.533 mol) of hexamethylene tetramine and 200 ml of water (molar ratio 1: 1.2) is continuously pumped into this solution for 55 min. pressure ranges from 33-39 bar. After the addition of the mixture of educts is completed, the reaction mass is additionally stirred for 10 minutes at 280 ° C and then cooled to room temperature. Next, the resulting organic phase is separated, the aqueous phase is extracted with 3x100 ml of methylene chloride, the extracts are combined. With this organic phase and the separated aqueous phase is shaken with an additional 60 ml of methylene chloride. By gas chromatographic analysis of all 5 connected organic layers, the following acetaldehyde yield (A) or formaldehyde (f): 3-picoline 57.3 g 38.49% (f); 3-ethylpyridine 28.8 g 30.3% (A), Example 33, 3420 ml of an aqueous solution containing 314.8 g of sodium hydrogen sulfate (dissociation constant at 1x10), 397.1 g of diammonium hydrogen phosphate (dissociation constants 25 C 7x10) and 170 g of ammonia are heated in an autoclave to 230 C and stirred at 1500 rev / min. After stirring, a solution consisting of a mixture of 117.7 g (2.94 mol) of acetaldehyde, 120.0 g (1.71 mol) of crotonaldehyde and 150.2 g (1.27 mol) of acetaldehyde diethyl acetate (educt 1) is introduced and 32.0 g (1.06 mol) of formaldehyde.
    516
    34.3 g (0.244 mol) of hexamethylenetetramine and 171 g (2.25 mol) of dimethyl acetal formaldehyde (educt 2). After completion of the addition, it is further stirred for 25 minutes at 230 ° C and cooled to room temperature. After isolation, 4.2 g of 2.18% (pyridine (A); 172.8 g of 45.8% of 3-picoline (F);
    46.4 g 22.97% ethylpiraidine (A) j. 13.8 g of 6.0% 2.5-lutidine (A); . 1.6 g 1.1% 3.5-lutidine (F); 1.8 g 0.8% 2-methyl-5-ethylpyridine (A),
    Approx. 34. 1140 ml of a 3.40-molar aqueous solution containing diammonium hydrogenphosphate (dissociation constant at 25 ° С 7x10) and 85.1 g of ammonia (pH of the solution is 10.95) are heated to 230 ° C and ne -.
    is stirred at 1500 rev / min. After stirring, a solution consisting of a mixture of 59.0 g (1.34 mol) acetaldehyde and 80.0 g (0.68 mol) diethyl acetaldetaldehyde (educt 1) and
    103.0 g (1.03 mol) of formaldehyde 30%, 17.0 g (0.12 mol) of hexamethylenetetramine and 53.0 g (0.697 mol) of formaldehyde dimethyl acetal (educt 2). After the addition is completed, the mixture is additionally stirred for 25 min. at 230 C and then cooled to room temperature. After separation, 62.9 g of 64.6% 3-α-picoline are obtained.
    Example 35. 1140 ml of a 3.40 molar aqueous solution containing diammonium hydrogen phosphate (dissociation constant at 25 C - 7x10) and 85.1 g of ammonia (pH of the solution is 10.95)
    heated in an autoclave to 230 ° C. and stirred at 1500 rev / min. After stirring, a solution consisting of a mixture of 59.0 g (1.34 mol) of acetaldehyde and 80.0 g- (1.14 mol) of crown is introduced. aldehyde (educt 1) and 106.6 g (1.065 mol) of a solution of formaldehyde 30% (educt 2). After finishing the pr50
    The rollers are additionally stirred for 25 w at 230 ° C and then cooled to room temperature. After recovery, 24.5 51.1% of 3-picoline is obtained.
    55
    Preparative release of 3-picoline.
    4624.0 g of the solution obtained according to examples from 11.9 g of pyridine, 496.2 g of 3-picoline, 118.9 g of 317 121398518
    -ethylpyridine, 32.9 g of 2,5-lutidine. Then fraction 2 is distilled from 9, 1 g of 3,5-lutidine, 53.1 g of 2-methyl-5-change of a 140 cm long column of α-etipyridine and methylene chloride type At the same time receive
    It is passed through a silver column, the parameters of which are brought in by a vacuum jacket with glass 5 ™ in the table. 2
    Raschig rings (4-4 mm). According to IR, NMR spectroscopy,
    This gives the fractions also indicated by GLC analysis of the fraction 5 containing Table 1. Lives 97.4% of 3-picoline (yield 90.9%).
    ,, , Table 1
    Frak- Pressure, Point Kolichest- The result of the distillation of qi Torr. boil, g
    Nin,
    ° С
    1700 To 81 3555.0. Mostly chloride
    methylene
    214 to 60 771.3 Mainly pyridine bases
    3178.0 Balance
    .Table 2
    Fraction-Pressure, Point Kolichest- The result of the distillation of qi Torr boiling, g
    neither
    ° С
    78 To 73 61.8 Doubles shoulder straps 78 73-77 463.0 Main shoulder straps 78 77-97 167.7. Last episode
    7 5 3 Contents of the cooling trap
    20.0 Balance
    p: edactor E. Egorova
    Compiled by M. Borin
    Tehred M. Gargel KoppeKTopiB. Tit
    Order 789/63 Circulation 379 Subscription of the USSR State Committee
    Inventions and discoveries 113035, Moscow, 1-35, Raushsk nab. d. 4/5
    Branch PPP Patent, Uzhgorod, y. Project, 4
    权利要求:
    Claims (4)
    [1]
    1. METHOD FOR PRODUCING 3-PICOLINE using acetaldehyde, formaldehyde and ammonia in the presence of a catalyst upon heating, which is based on the fact that, in order to increase the yield of 3-picoline, the initial product 1, consisting of acetaldehyde and / or acetaldehyde acetals , and / or crotonaldehyde, are reacted with starting material 2 consisting of formaldehyde. and / or formaldehyde acetals and / or hexamethylenetetramine in water at 180-280 ° C in a closed vessel in the presence of ammonia and / or ammonium ions and diammonium hydrogen phosphate, sodium hydrogen sulfate, potassium dihydrogen phosphate, ammonium ammonium acetate, dipotassium hydrogen phosphate are used as catalyst ammonium isonicotinate, sodium fluoride, sodium acetate, ammonium pentaborate, ammonium carbonate, sulfate ammo 1 Nia, ammonium bromide, ammonium propionate, ammonium succinate · adipate, ammonium diammoniyftalat, diammoniytereftalat, nicotinate ammonium koto- 'rye at 20 ° C are dissociation constant 10 6 - 10 ~ 1 < .
    [2]
    2. The method of pop. 1, characterized in that they add β-acetaldehyde per se and / or in the form of its acetals or in the form of paraldehyde and formaldehyde per se and / or in the form of its acetals or in the form of urotropin at a molar ratio of 1-0, 55 to
    1-1.2.
    [3]
    3. The method according to PP. 1 and 2, which is different in that the heating is carried out at 205-240 C.
    [4]
    4. The method according to PP. 1-3, t l and characterized in that the salts are used in an aqueous solution at a concentration of 0.3-10 mol / L.
    Priority by feature.
    01/09/81. - The interaction of the starting product 1, consisting of acetaldehyde and / or protonaldehyde, with the starting product 2, consisting of formaldehyde at a ratio of 1-0.55- * -1-1.2, in water at 180-280 ° C in a closed vessel in the presence of ammonia and / or ammonium ions as kata. lyser use salts of inorganic or organic acids, which at 20 ° C have a dissociation constant of 10 * - 10 ’
    03/12/81. - the interaction of acetaldehyde acetals with formaldehyde acetals and the use of acid salts with a concentration of 0.3-10 mol / l.
    SU ,, .. 1213985
    1 1213
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    同族专利:
    公开号 | 公开日
    AR229800A1|1983-11-30|
    ES8300705A1|1982-11-01|
    GR74775B|1984-07-12|
    BG36933A3|1985-02-15|
    EP0056496B1|1984-06-27|
    NO159268B|1988-09-05|
    US4482717A|1984-11-13|
    IN154978B|1984-12-22|
    US4481361A|1984-11-06|
    IE812959L|1982-07-09|
    MX157219A|1988-11-04|
    YU482A|1984-10-31|
    RO82034A|1983-06-01|
    NO820048L|1982-07-12|
    RO82034B|1983-05-30|
    TR21423A|1984-05-31|
    IL64687A|1985-01-31|
    DK5782A|1982-07-10|
    CS230589B2|1984-08-13|
    AU550454B2|1986-03-20|
    DE3164475D1|1984-08-02|
    FI814007L|1982-07-10|
    ES508585A0|1982-11-01|
    DD208978A5|1984-04-18|
    HU186022B|1985-05-28|
    IE52431B1|1987-10-28|
    IL64687D0|1982-03-31|
    EP0056496A1|1982-07-28|
    NO159268C|1988-12-14|
    AU7875881A|1982-07-15|
    BR8200094A|1982-11-03|
    CA1161845A|1984-02-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    GB1208569A|1967-01-04|1970-10-14|Ici Ltd|Process for the production of pyridines|
    US3846435A|1972-07-21|1974-11-05|Merck & Co Inc|Process for the production of 2-methyl-5-ethyl pyridine|
    EP0040698B1|1980-05-23|1983-12-28|Lonza Ag|Process for the preparation of 3-picoline|
    FI77025C|1981-03-18|1989-01-10|Lonza Ag|FOERFARANDE FOER FRAMSTAELLNING AV 3-PIKOLIN.|CH660733A5|1981-09-29|1987-06-15|Lonza Ag|METHOD FOR PRODUCING 3-PICOLIN.|
    NL8403616A|1984-11-28|1986-06-16|Stamicarbon|PROCESS FOR THE PREPARATION OF A BASIC LITHIUM PHOSPHATE CATALYST FOR THE ISOMERIZATION OF OXENE OXIDES.|
    US4701530A|1985-11-12|1987-10-20|The Dow Chemical Company|Two-stage process for making trimethyl pyridine|
    EP2277864A1|2009-06-24|2011-01-26|Lonza Ltd.|Synthesis process for 3-methylpyridine|
    CN101979380B|2010-10-18|2012-05-30|浙江新和成股份有限公司|Method for synthesizing 3-methylpyridine|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    CH10481|1981-01-09|
    CH168581|1981-03-12|
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