CN1232819A - 丙二腈的制备方法 - Google Patents
丙二腈的制备方法 Download PDFInfo
- Publication number
- CN1232819A CN1232819A CN99104071A CN99104071A CN1232819A CN 1232819 A CN1232819 A CN 1232819A CN 99104071 A CN99104071 A CN 99104071A CN 99104071 A CN99104071 A CN 99104071A CN 1232819 A CN1232819 A CN 1232819A
- Authority
- CN
- China
- Prior art keywords
- propane dinitrile
- formula
- general formula
- cycloalkyl
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 150000002527 isonitriles Chemical class 0.000 claims abstract description 8
- 150000002825 nitriles Chemical class 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- ZRKSVHFXTRFQFL-UHFFFAOYSA-N isocyanomethane Chemical compound C[N+]#[C-] ZRKSVHFXTRFQFL-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- JJNZXLAFIPKXIG-UHFFFAOYSA-N 2-Chlorobenzylidenemalononitrile Chemical compound ClC1=CC=CC=C1C=C(C#N)C#N JJNZXLAFIPKXIG-UHFFFAOYSA-N 0.000 description 1
- PUXIXZKRDMDACV-UHFFFAOYSA-N C=CC#N.N#CCCC#N Chemical compound C=CC#N.N#CCCC#N PUXIXZKRDMDACV-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- -1 isobutyl- Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种新颖的制备丙二腈的方法,包括任意地在腈的存在下将异腈进行高温处理。
Description
本发明涉及一种新颖的制备通式Ⅰ表示的丙二腈或其衍生物的方法
式中，R1表示氢、烷基或环烷基。
丙二腈是制备极宽范围的各种活性成分(例如，药用或农业化学活性成分)的非常重要的原料和中间体(Ullmann’s Encyklopdie der technischen Chemie，第4修订增补版，Verlag Chemie Weinheim出版，第16卷，第419-423页)。
虽然已知有许多制备丙二腈的方法，但仅有一种方法在工业规模上是有重要意义的，这就是乙腈与氯化氰在700℃以上的高温的反应。
本发明的目的是，开发另一种具有潜在的工业规模应用价值的丙二腈的制造方法。
本发明的目的是用以下方法实现的。
在本发明中，将通式Ⅱ的并腈(亦即胩)
R2-NC Ⅱ
式中，R2表示氢、烷基或环烷基任意地在通式Ⅲ的腈的存在下，
R3-CN Ⅲ
式中，R3表示氢、烷基或环烷基在700℃至1000℃进行转化。
此处所述的“烷基”宜指C1-6烷基，即，甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、戊基及其异构体或己基及其异构体。优选甲基。
此处所述的“环烷基”宜指C3-6环烷基，即环丙基、环丁基、环戊基、或环己基。
最好的是，用乙腈进行甲胩的转化。
由于通式Ⅱ的异腈可异构化成相应的腈，因此，可在用通式Ⅲ的腈进行的转化过程中得到丙二腈的衍生物，其R1基团可与异腈的R2基团或腈的R3基团中的任一个对应。当然，其条件是R2和R3不同。因此，这样的转化可产生丙二腈衍生物的所有混合物。
通式Ⅱ的异腈可以是市售品，也可以是用文献(例如，Angew.Chemie,1965,77,492-504或J.Am.Chem.Soc.,1981,103,767-772)中已报道的方法合成的。
根据本发明，高温转化最好在800℃至950℃进行。
反应通常在管状反应器中进行，该反应器可任意地加以合适包裹。
转化时间一般为数秒种。
丙二腈可从反应产物中分离出来，例如用合适的溶剂进行抽提。
实施例1通过甲胩和乙腈的热分解进行丙二腈的合成和纯化
将2ml甲胩用3ml乙腈稀释后，用注射器注入将乙腈蒸馏而产生的蒸气流(用20分钟产生15g)中。将该蒸气流导入加热至870℃的石英热裂解管(长30cm，内径2.5cm)中。将反应产物收集在冷却至-50℃的冷却阱中。将冷却阱中的残留物在旋转式蒸发器中蒸发，使其浓缩，用1H-NMR测定所得反应产物(516mg)。丙二腈 18％丁二腈 1％顺式丁烯二腈和反式丁烯二腈 1％用氯仿抽提粗产物。仅丙二腈和丁二腈在该抽提液中可溶。实施例2通过甲胩和乙腈的热分解进行丙二腈的合成
将2ml甲胩用3ml乙腈稀释后，用注射器注入将乙腈蒸馏而产生的蒸气流(用20分钟产生15g)中。将该蒸气流导入加热至920℃的平衡化了的石英热裂解管(长30cm，内径2.5cm)中。将反应产物收集在冷却至-50℃的冷却阱中。
将冷却阱中的残留物在旋转式蒸发器中蒸发，使其浓缩，用1H-NMR测定所得反应产物(1400mg)。
丙二腈 40％
丁二腈 1.5％
顺式丁烯二腈和反式丁烯二腈 9％
用与实施例2相同的方法进行下述实施例，但在各实施例中所用石英管的温度有所不同。
| 实 施 例 | 温 度(℃) | 丙 烯 腈 | 丁 二 腈 | 顺式丁烯二腈和反式丁烯二腈 | 丙 二 腈 |
| 3(比较例) | 670 | 0 | 0 | 0 | |
| 4(本发明) | 770 | 1 | 0.2 | 1.1 | |
| 5(本发明) | 820 | 0.6 | 0.4 | 4 | |
| 6(本发明) | 845 | 0.8 | 1 | 12 | |
| 7(本发明) | 870 | 0.5 | 2.5 | 18 | |
| 8(本发明) | 895 | 2 | 1 | 5 | 33 |
| 9(本发明) | 920 | 10 | 1.5 | 8 | 40 |
| 10(本发明) | 945 | 33 | 1 | 17 | 35 |
| 11本发明) | 970 | 28 | 2 | 20 | 29 |
| 12(比较例) | 1070 | 0 | 0 | 0 | 0 |
Claims (3)
1．通式Ⅰ的丙二腈或其衍生物的制备方法，
式中，R1表示氢、烷基或环烷基其特征在于，将通式Ⅱ的异腈
R2-NC Ⅱ
式中，R2表示氢、烷基或环烷基任意地在通式Ⅲ的腈的存在下，
R3-CN Ⅲ
式中，R3表示氢、烷基或环烷基在700℃至1000℃进行转化。
2．如权利要求1所述的方法，其特征在于，所述通式Ⅱ的异腈是甲胩，所述通式Ⅲ的腈是乙腈。
3．如权利要求1或2所述的方法，其特征在于，转化温度是800℃至950℃。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH0665/98 | 1998-03-19 | ||
| CH66598 | 1998-03-19 | ||
| CH0665/1998 | 1998-03-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1232819A true CN1232819A (zh) | 1999-10-27 |
| CN1119323C CN1119323C (zh) | 2003-08-27 |
Family
ID=4192289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99104071A Expired - Fee Related CN1119323C (zh) | 1998-03-19 | 1999-03-18 | 丙二腈的制备方法 |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5959136A (zh) |
| EP (1) | EP0943605A3 (zh) |
| JP (1) | JPH11322699A (zh) |
| KR (1) | KR100618365B1 (zh) |
| CN (1) | CN1119323C (zh) |
| CA (1) | CA2263840C (zh) |
| CZ (1) | CZ84899A3 (zh) |
| HK (1) | HK1023108A1 (zh) |
| HU (1) | HU223518B1 (zh) |
| IL (1) | IL128844A (zh) |
| IN (1) | IN188424B (zh) |
| PL (1) | PL193541B1 (zh) |
| RU (1) | RU2225391C2 (zh) |
| SK (1) | SK34399A3 (zh) |
| TW (1) | TWI224088B (zh) |
-
1999
- 1999-03-01 IN IN250MA1999 patent/IN188424B/en unknown
- 1999-03-02 CA CA002263840A patent/CA2263840C/en not_active Expired - Fee Related
- 1999-03-04 IL IL12884499A patent/IL128844A/xx not_active IP Right Cessation
- 1999-03-10 CZ CZ99848A patent/CZ84899A3/cs unknown
- 1999-03-11 EP EP99104840A patent/EP0943605A3/de not_active Withdrawn
- 1999-03-12 KR KR1019990008314A patent/KR100618365B1/ko not_active IP Right Cessation
- 1999-03-12 SK SK343-99A patent/SK34399A3/sk unknown
- 1999-03-16 TW TW088104018A patent/TWI224088B/zh not_active IP Right Cessation
- 1999-03-16 JP JP11071055A patent/JPH11322699A/ja active Pending
- 1999-03-18 CN CN99104071A patent/CN1119323C/zh not_active Expired - Fee Related
- 1999-03-18 PL PL332064A patent/PL193541B1/pl not_active IP Right Cessation
- 1999-03-18 RU RU99105594/04A patent/RU2225391C2/ru not_active IP Right Cessation
- 1999-03-19 HU HU9900699A patent/HU223518B1/hu not_active IP Right Cessation
- 1999-03-19 US US09/272,164 patent/US5959136A/en not_active Expired - Fee Related
-
2000
- 2000-04-06 HK HK00102104A patent/HK1023108A1/xx not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IL128844A (en) | 2003-07-06 |
| HK1023108A1 (en) | 2000-09-01 |
| IN188424B (zh) | 2002-09-21 |
| CA2263840A1 (en) | 1999-09-19 |
| SK34399A3 (en) | 2000-02-14 |
| PL332064A1 (en) | 1999-09-27 |
| KR19990077832A (ko) | 1999-10-25 |
| EP0943605A3 (de) | 2000-01-19 |
| IL128844A0 (en) | 2000-01-31 |
| CN1119323C (zh) | 2003-08-27 |
| KR100618365B1 (ko) | 2006-08-30 |
| EP0943605A2 (de) | 1999-09-22 |
| TWI224088B (en) | 2004-11-21 |
| HUP9900699A1 (hu) | 2000-09-28 |
| HU9900699D0 (en) | 1999-05-28 |
| CA2263840C (en) | 2008-05-13 |
| JPH11322699A (ja) | 1999-11-24 |
| RU2225391C2 (ru) | 2004-03-10 |
| PL193541B1 (pl) | 2007-02-28 |
| HU223518B1 (hu) | 2004-08-30 |
| CZ84899A3 (cs) | 1999-10-13 |
| US5959136A (en) | 1999-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2502899B1 (de) | Synthese von alpha, omega-Dicarbonsäuren und deren Estern aus ungesättigten Fettsäurederivaten | |
| DE1182652B (de) | Verfahren zur Herstellung von Dialkylketenen | |
| US8981128B2 (en) | Process for producing compounds comprising nitrile functions | |
| CN1070634A (zh) | 无酯的醚 | |
| WO2007012387A1 (de) | Verfahren zur herstellung von nitrilen durch eliminierungsreaktionen | |
| WO2016039618A1 (en) | Bio-based crotonic acid production | |
| CN1119323C (zh) | 丙二腈的制备方法 | |
| CN106536474A (zh) | 新颖的乳酸回收方法 | |
| DE2043726A1 (de) | Verfahren zum Herstellen von Propylen ausgehend von n Butan | |
| DE2416035B2 (de) | Synthese von Chinonderivaten mit biologischer Aktivität | |
| US3359260A (en) | Purification of epsilon-caprolactams | |
| EP0189097B1 (de) | Verfahren zur Herstellung von Thiotetronsäure | |
| DE1252652B (de) | Verfahren zur Gewinnung von Adipinsäuredinitril | |
| DE1280851B (de) | Verfahren zur Herstellung von 5-Hexennitril | |
| US3065260A (en) | Process for the preparation of acrylic acid esters | |
| KR101441771B1 (ko) | 산소를 이용한 탄화수소의 산화 방법 | |
| CN104797552A (zh) | 在氧化裂解不饱和脂肪酸和衍生物之后ω-官能化酸的选择性提取 | |
| US3822300A (en) | Process for the production of alpha,beta-unsaturated carboxylic acids | |
| Nithya et al. | Dichotomous stereocontrol in Claisen-Schmidt condensations: synthesis of a propeller shaped rigid system | |
| EP1989177B1 (de) | Amidoadamantane und verfahren zu ihrer herstellung | |
| CN106631690A (zh) | 一种1‑金刚烷醇的制备方法 | |
| KR20110061590A (ko) | 카르노솔을 결정화시키는 방법 | |
| BR102018069025B1 (pt) | Processo de produção de nitrilas a partir de ácido gráxos e óleos vegetais altamente ácidos e produtos | |
| US3639436A (en) | Omega omega-dinitroalkanoic acids esters and ester-salts | |
| US2431216A (en) | Production of alkenylfurans |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030827 Termination date: 20100318 |