• 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:
    A method for producing β-picoline using acetaldehyde and / or crotonaldehyde and formaldehyde at an elevated temperature, characterized in that, in order to increase the yield of the target product, acetaldehyde and / or crotonaldehyde and formaldehyde are reacted with the ammonium salt of an inorganic or organic acid in the liquid phase 195-260s in a closed system.
    公开号:SU1095876A3
    申请号:SU813285560
    申请日:1981-05-22
    公开日:1984-05-30
    发明作者:Динкель Рольф
    申请人:Лонца Аг (Фирма)；
    IPC主号:
    专利说明:

    with
    SP
    00
    05 The invention relates to a process for the preparation of 3-picoline, which is widely used in the chemical industry. A method of producing 3-picopin is known, which consists in reacting acetaldehyde and / or crotonic aldehyde with formaldehyde and ammonia at 400-A2U C in the presence of a catalyst consisting of silicon and aluminum. The yield of 3-picopin is 40-44%. A large amount of pyridine is formed as a by-product. However, the known method is characterized by an insufficiently high yield of the target product. The aim of the invention is to increase the yield of the target product. This goal is achieved in that according to the Method for the Production of 3-picoline, acetaldehyde and / or crotonaldehyde and formaldehyde are subjected to interaction with the ammonium salt of an inorganic or organic acid in the liquid phase at 195-260 ° C in a closed system. This allows to obtain the target product with a yield of up to 60%. Example 1. A 1130 MP 3.37-moth of an aqueous solution of diammonium hydrogenphosphate (pH 8.3) is heated in an autoclave with a capacity of 2 liters and stirred at 1500 rpm for one minute. A mixture of 114.1 g of acetaldehyde and 219.2 g of a 32.0% aqueous solution of formaldehyde (molar ratio 1: 0.90) is continuously pumped into this solution for 63 minutes. Here, the reaction pressure ranges from 38 to 40 bar. After the addition of the aldehyde mixture is completed, the reaction mass is stirred for another 10 min before and then cooled to room temperature. Finally, an amount of ZOOO mp toluene is extruded and a gas chromatographic analysis of the combined toluene extracton is carried out, and the following products are obtained with the acetaldehyde (A) or formaldehyde (F) yields used: pyridine 0.9% (A) J 3-picoline 68.0% (F), 3-ethylpyridine 15.0% (A) {2.5-lutidine 2.5% (fO 3.5-lutidine 1.4% (F) t 2-metsh-5-ethylnindin 0.6% (A). Example 2. 1130 MP A 3.38-molar aqueous solution of diammonium hydrogenphosphate (pH 8.3) is heated in a 2 l autoclave to 230 ° C and stirred at 1500 revolutions per minute. uninterrupted A mixture of 121.8 g of acetaldehyde and 208.2 g of a 32.0% aqueous solution of formaldehyde (molar ratio 1: 0.80) is pumped in for 60 minutes. At the same time, the reaction pressure varies from 33 to 35 bar After the addition of the aldehyde mixture is over, the reaction mass is further stirred for 10 minutes at 230 seconds and then cooled to room temperature. Finally, extraction is carried out by means of SOOO with ml of toluene, as well as by gas chromatography analysis of the combined toluene extracts, and the following products are obtained attitudes used for acetaldehyde (A) or formaldehyde (F) yields: pyridine 0.8% (A), 3-picoline 62.5% (F) J 3-ethylpyridine 22.6% (A) i 2,5- lutidine 3.6% (A) 3.5-lutidine 0.9% (F) 2-methy-1-5-ethylpyridine 1.9% (A). Example 3. A 1060 MP 3.37-molar solution of diammonium hydrogenphosphate (pH 8.3) is heated in a 2 l autoclave to 222 ° C. and stirred at 1200 revolutions per minute. A mixture of 108.4 g of paraldegzda, 222.4 g of a 33.2% aqueous solution of formaldehyde (molar ratio 1: 3.0) and 73.1 g of 3-picoline (homogenizing means). After the addition of the aldehyde mixture is completed, the reaction mass is further stirred for 10 minutes and then cooled to room temperature. Finally, extraction with 3100 ml of toluene is carried out, as well as gas chromatographic analysis of the combined toluene extracts, and the following products are obtained with yields based on the paraldehyde used: pyridine 0.8%} 3-picoline 55.2% (without a fraction for homogenization ); 3-ethylpyridine 10.0%} 2.5-lutidine 1.9%, 3.5-lutidine 1.4%; 2-METHYL-5-ETYL-pyridine 1.9%. Example 4. In 1140 mp 10.0 molar aqueous acetate solution
    Mmonium (pH 8.1) passes 25.0 g of ammonia in a gaseous form and then the mixture is heated in an autoclave with a capacity of 1 L and stirred at 1500 revolutions per minute. A mixture of 122.2 g of acetaldehyde and 208.2 g of 32.0% aqueous solution of formaldehyde (molar ratio 1: 0.80) is continuously pumped into this mixture for 58 minutes. At the same time, the reaction pressure ranges from 27 to 29 bar. After the addition of the aldehyde mixture is completed, the reaction mass is further stirred for 10 minutes at 230 ° C and then cooled to room temperature. Finally, a gas chromatographic analysis of the homogeneous reaction mixture was carried out, and the following products were obtained with yields per acetaldehyde (A) or formaldehyde (F) 0.9% pyridine (A), 44.8% 3-picoline (F), 19 , 1% 3-ethylpyridine (A); 4.0% 2.5 lutidi on (A); 0.4% 3.5-lutidine (F) 1 1.7% 2-metsh-1-5-ethylpyridine (A). Example 5. 1140 MP 3.4% molar aqueous solution of ammonium acetate (pH 7.4) is heated in an autoclave with a capacity of 2 liters to 230 ° C and stirred at 1500 revolutions per minute. A mixture of 122 is continuously pumped into this solution for 59 minutes 2 g of acetaldehyde and 208.2 g of a 32.0% formaldehyde aqueous solution (molar ratio 1: 0.80). At the same time, the reaction pressure ranges from 26 to 28 bar. After the addition of the aldehyde mixture is completed, the reaction mass is further stirred at 230 ° C for 10 minutes, then cooled to room temperature and adjusted to pH 8.1 with ammonia gas. Finally, a gas chromatographic analysis of the homogeneous reaction mixture is carried out, and the following products are obtained with yields based on acetaldehyde (A) or formaldehyde (F) used: 1.3% pyridine (A) -, 53.4% 3-picoline (F) - 14.8% 3-ethylpyridine (A) 4.1% 2.5-lutidine (A); 0.7% 3.5-lutidine (F), 1.9 5-ethylpyridine (A).
    Example 6. 1140 ml of a 3.40-molar aqueous solution of diammonium hydrogenphosphate (pH 8.35) is heated in a 2 l autoclave before and stirred at 1500 ° C 0958764
    mouths per minute, a mixture of 117.7 g of acetaldehyde, 64.0 g of trioxane and 30.0 g of 3-picoli5 (homogenizing agent) is continuously pumped into this solution for 74 minutes. The calculated molar ratio of acetaldehyde: formaldehyde is 1: 0.78. Here, the reaction pressure ranges from 32-34 bar. After
    At the end of the addition of the educt mixture, the reaction mixture is additionally stirred for 10 minutes at 230 ° C and then cooled to room temperature. Finally, the extraction is carried out by extraction with ml of methylene chloride, as well as by gas chromatography analysis of the combined methylene chloride extracts, and the following products are obtained with
    0 outputs, depending on the theoretical need for aldehyde, based on the acetaldehyde (A) or trioxane (f) used; 0.7% pyridine (A); 23.8% 3-picoline (f).
    5 (no fraction for homogenization) f 35.1% 3-ethylpyridine (A) 6.4% 2.5-lutidine (A); 0.2% 3.5-lutidine (F); 23.3% 2-methyl-5-ethylpyridine (A).
    PRI me R 7. 1140 ml of a 3.4% molar aqueous solution of diammonium hydrogenphosphate (pH 8.35) is heated in a 2 l autoclave to 230 s and stirred at 1500 revolutions per minute. Into this solution
    5 continuously pumped over
    58 min. A mixture of 117.7 g of paraldehyde, 64.0 g of trioxane, 130 g of water and 100 g of ethanol (calculated molar ratio of acetaldehyde:
    0 formaldehyde 1: 0.79). Here, the reaction pressure ranges from 32-38 bar. After the addition of the educt mixture is completed, the reaction mixture is additionally stirred for 10 minutes at 230 ° C and then cooled to room temperature. Finally, extraction is carried out by means of ZOOO with ml of methylene chloride, as well as by gas chromatography of the United States.
    methylene chloride extracts, and the following products are obtained in yields, depending on the aldehyde, paraldehyde (A) used according to the theoretical need, or the trioxane used (F): 0.6%
    pyridine (A) {19.1% 3-picoline (F), 36.0% 3-ethylpyridine (A), 7.1% 2.5-lutidine (A); 0.2% 3.5-lutidine (F) 23.9% 5-ethylpyridine (A). Example 8. 1140 ml of a 3, AO-molar aqueous solution of diammonium hydrogenphosphate (pH 8.35) is heated in a 2 l autoclave before and stirred at 1600 revolutions per minute. A mixture of 64.4 g of crotonaldehyde, 239.2 g of acetaldehyde and 213.3 g of 30.3% aqueous formaldehyde solution (molar ratio of crotoaldehyde: acetaldehyde 1: 1) is continuously pumped into this solution for 60 min. the molar ratio of acetaldehyde: formaldehyde is 1: 0.79. Here, the reaction pressure ranges from 32-33 bar. After the addition of the aldehyde mixture is completed, the reaction mass is further stirred for 10 minutes at 230 ° C and then cooled to room temperature. Finally, extraction is carried out with 3-100 mp of methylene chloride, as well as by gas chromatography analysis of the combined methylene chloride extracts, and the following products are obtained with yields, depending on the theoretical need for aldehyde, based on acetaldehyde and crotonaldehyde (A) or on formaldehyde (f); t, 0% pyridine (A) 53.5% 3-picoline (F), 21.6% 3-ethylpyridine (A) i 5.9% 2.5-lutidine (A), 0.7% 3.5 -lutidine (F), 2.8% 2-methy-1-5-ethylpyridine (A). Example 9. A 1700 mp 3.41 molar diammonium hydrogenphosphate solution (pH 8.3) is heated in an autoclave with a capacity of 2 liters and stirred at 1500 revolutions per minute. Add to this solution in portions using the first pump (360 , 7 g / h) a mixture of 2214 g of acetaldehyde and 3985 g of a 30.5% aqueous solution of formaldehyde (molar ratio 1: 0.81). After 1, a second pump (1325.7 g / h) is connected, through which another 3.41 molar aqueous solution of diamonium hydrogenphosphate (pH 8.3) is added in portions. The reaction mixture then begins to be distilled through a tube attached to the lid of the autoclave to a receiving vessel heated to this temperature. After 15 minutes, both pumps are suspended, the weight of the tanks with the educt is recorded, the distillation reaction mixture is lowered into a refrigerated vessel, and then the pumps are again activated. This process is repeated every 60 minutes, so that every hour one fraction is obtained. The reaction pressure measured meanwhile ranges from 33 to 35 bar. After the end of the experiment, fractions 5-12 are processed. In each case, the organic phase and the aqueous phase are first mixed, extracted three times with 100 ml of methylene chloride, the extracts are combined with the indicated organic phase, and the aqueous phase which is again precipitated is shaken with an additional 60 ml of methylene chloride. Then, all methylene chloride extracts of fractions 5–12 are combined using an internal standard, as well as factors from the area of the curves, to be analyzed by gas chromatography. At the same time, the following products are obtained with yields, depending on the theoretical need for aldehyde to acetadehyde (A) or formaldehyde (F); 1.2% pyridine (A)} 64.1% 3-picoline (F); 21.0% 3-ethylpyridine (A); 3.5% 2.5-lutidine (A), 1.1% 3.5-lutidine (F), 1.6% 2-methyl-5-ethylpyridine (A). In tab. 1 shows the yields of the target product, depending on the process conditions. In tab. 2 gives 3-picoline yields using various ammonium salts.
    1095876
    10 Table 2
    0.6
    3.5
    7.7
    one,
    A, 1 15.2

    16.1 1.7 4.8 U, 8 10.5 4.0 1.6 14.5 5.4 6.7 3.0 19.2 4.8 1.5 16.2
    5.7
    15.8
    2.1 1, A 14.0
    5.1
    1, A 3.9
    17.4 1.6 5.1 12.3
    1, 5.3 1U, 0
    权利要求:
    Claims (1)
    [1]
    METHOD FOR PRODUCING 3-PICOLINE using acetaldehyde and / or crotonaldehyde and formaldehyde at elevated temperature, characterized in that, in order to increase the yield of the target product, acetaldehyde and / or crotonaldehyde and formaldehyde are reacted with an ammonium salt of an inorganic or organic acid in the liquid phase during 195-260 ° C in a closed system.
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US2769007A|1956-10-30|Manufacture of a pyridine homologue |
    GB534494A|1939-10-06|1941-03-07|Distillers Co Yeast Ltd|Improvements in or relating to the manufacture of heterocyclic bases|
    GB971174A|1961-08-31|1964-09-30|Distillers Co Yeast Ltd|Production of pyridine|
    GB1182705A|1966-09-21|1970-03-04|Lummus Co|Improvements in or relating to the Vapour Phase Production of Pyridine of Alkyl Pyridines|
    GB1208569A|1967-01-04|1970-10-14|Ici Ltd|Process for the production of pyridines|
    GB1188891A|1968-01-27|1970-04-22|Bp Chem Int Ltd|Picolines|
    US3846435A|1972-07-21|1974-11-05|Merck & Co Inc|Process for the production of 2-methyl-5-ethyl pyridine|FI814007L|1981-01-09|1982-07-10|Lonza Ag|FOERFARANDE FOER FRAMSTAELLNING AV 3-PIKOLIN|
    CH656879A5|1981-07-09|1986-07-31|Lonza Ag|METHOD FOR PRODUCING 3,5-DIALKYLPYRIDINE.|
    CH660733A5|1981-09-29|1987-06-15|Lonza Ag|METHOD FOR PRODUCING 3-PICOLIN.|
    JPH03111749U|1990-02-28|1991-11-15|
    AU2006283664B2|2005-08-19|2012-04-12|Houghton Technical Corp.|Methods and compositions for acid treatment of a metal surface|
    AU2012204141C1|2005-08-19|2015-10-22|Houghton Technical Corp.|Methods and compositions for acid treatment of a metal surface|
    EP2277864A1|2009-06-24|2011-01-26|Lonza Ltd.|Synthesis process for 3-methylpyridine|
    法律状态:
    优先权:
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    CH405280|1980-05-23|
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