CN105985263A - 一种n,n-二取代氨基-丙二腈类化合物的合成方法 - Google Patents
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 8
- GXDKXRIMUVUELI-UHFFFAOYSA-N 2-aminopropanedinitrile Chemical class N#CC(N)C#N GXDKXRIMUVUELI-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 amino-substituted malononitrile Chemical class 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UZOFELREXGAFOI-UHFFFAOYSA-N 4-methylpiperidine Chemical compound CC1CCNCC1 UZOFELREXGAFOI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- DANBQHLZCHUINA-UHFFFAOYSA-N [SiH4].N#CC#N Chemical compound [SiH4].N#CC#N DANBQHLZCHUINA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000005936 piperidyl group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims 1
- 125000005956 isoquinolyl group Chemical group 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZEMNVPLWDUWKEG-UHFFFAOYSA-N 3,4-dihydro-1h-isoquinoline-2-carbaldehyde Chemical compound C1=CC=C2CN(C=O)CCC2=C1 ZEMNVPLWDUWKEG-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZGZUKKMFYTUYHA-HNNXBMFYSA-N (2s)-2-amino-3-(4-phenylmethoxyphenyl)propane-1-thiol Chemical group C1=CC(C[C@@H](CS)N)=CC=C1OCC1=CC=CC=C1 ZGZUKKMFYTUYHA-HNNXBMFYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
本发明涉及一种N,N-二取代氨基-丙二腈类化合物的制备方法，其反应通式如下所示
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种N,N-二取代氨基-丙二腈类化合物的的合成方法。
背景技术
N,N-二取代氨基-丙二腈类化合物是一类比较重要的合成中间体,通过氰基衍生化,可以得到许多化学合成中有用的化合物,比如α-氨基酸。也能形成亚胺中间体和碳负离子,成为合成含氮杂环的重要前体。目前针对该类化合物的合成多用亚胺盐,季胺盐,硫代亚胺盐为原料,氰化钾为氰源(Justus LiebigsAnnalen der Chemie,(4),666-9；1976；Ger.Offen.,10057055,23May 2002；Journal of Organic Chemistry,50(21),4006-14；1985；Journal of theChemical Society,Perkin Transactions 1:Organic and Bio-OrganicChemistry(1972-1999),(11),2708-10；1979),步骤繁琐,而且用了剧毒的氰化钾。我们希望用原料易得的N,N-二取代的甲酰胺、相对低毒性的三甲基氰硅烷、铜金属催化剂加热条件下一步制得N,N-二取代氨基-丙二腈。
发明内容
本发明解决的技术问题是提供一种反应过程简单且易于操作的N,N-二取代氨基-丙二腈类化合物的合成方法,以替代传统的繁琐操作方法。
本发明的技术方案为：一种N,N-二取代氨基-丙二腈类化合物的合成方法。其技术特征为：N,N-二取代的甲酰胺、三甲基氰硅烷、铜金属催化剂在加热条件下按照反应式(1)进行,得到化合物N,N-二取代氨基-丙二腈。反应通式如反应1：
其中,(1)R1、R2不在同一个环系上时,两取代基可以相同,如甲基,乙基,等烷基基团；
(2)R1、R2不在同一个环系上时,两取代基可以不同,如R1可为甲基、乙基、丙基等烷基基团；R2可为苯基、苄基等芳基基团；
(3)R1、R2在同一环系上时,R1、R2连同N原子可为二氢吲哚基、1,2,3,4-四氢异喹啉基、哌啶基、吗啡啉基、4-甲基哌啶基。
在上述方法反应中,所用的铜催化剂的选择可为三氟甲烷磺酸铜、三氟甲烷磺酸亚铜、溴化铜、溴化亚铜、氯化铜、氯化亚铜、碘化亚铜。优选三氟甲烷磺酸铜。
在上述方法反应中,所用的溶剂可为正庚烷、1.2-二氯乙烷、乙腈、正己烷、环己烷、正壬烷、甲苯、四氢呋喃、1、4-二氧六环的一种或几种。优选正庚烷。
在上述方法反应中,加热所用的温度为20-120℃。
在上述方法反应中,反应中各物质的物质的量比为：N,N-二取代的甲酰胺：三甲基氰硅烷：铜催化剂：溶剂＝1：2-5：0.05-0.20：10-100。
具体实施方式
以下通过具体实施例对本发明做进一步的说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例
以N,N-二乙基甲酰胺为原料(反应式2)
将N,N-二乙基甲酰胺(50ul,0.45mmol),加入到搅拌的正庚烷中(1mL),随后依次加入三甲基氰硅烷(126ul,0.99mmol)和三氟甲烷磺酸铜(16mg,0.045mmol)在80℃下反应五小时完成反应,在旋转蒸发仪上抽干溶剂,经柱层析得淡黄色油状液体(31.5mg,64％)。
产物检测数据如下：
1H NMR(400MHz,CDCl3):δ4.78(S,1H),4.73(q,J＝7.2Hz,4H),1.17(t,7.2Hz,6H)；13C NMR(75MHz,CDCl3):δ110.7,46.9,44.9,12.5；MS m/z(％):137(M+,<1),111([M-25]+,25),57(100)。
以N-甲酰吗啉为原料(反应式3)
将N-甲酰吗啉(50ul,0.50mmol),加入到搅拌的正庚烷中(1mL),随后依次加入三甲基氰硅烷(141ul,1.1mmol)和三氟甲烷磺酸铜(18mg,0.050mmol)在80℃下反应五小时完成反应,在旋转蒸发仪上抽干溶剂,经柱层析得淡黄色油状液体(64.5mg,86％)
产物检测数据如下：
1H NMR(400MHz,CDCl3):δ4.65(S,1H),3.79(t,J＝3.8Hz,4H),2.72(t,4.7Hz,4H)；13C NMR(400MHz,CDCl3):δ109.6,66.2,50.1,48.5；MS m/z(％):149(M+,5),85(50),71(70),57(100)。
以1,2,3,4-四氢异喹啉-2-甲醛为原料(反应式4)
将1,2,3,4-四氢异喹啉-2-甲醛(50mg,0.31mmol),加入到搅拌的正庚烷中(1mL),随后依次加入三甲基氰硅烷(87ul,0.68mmol)和三氟甲烷磺酸铜(11mg,0.031mmol)。在80℃下反应五小时完成反应,在旋转蒸发仪上抽干溶剂,经柱层析得淡黄色油状液体(39.7mg,65％)。
产物检测数据如下：
1H NMR(400MHz,CDCl3):δ7.30-7.08(m,4H),4.87(s,1H),4.06-3.78(m,2H),3.05-2.94(m,4H)；13C NMR(75MHz,CDCl3):δ132.6,131.8,129.0,127.4,109.9,127.2,126.7,126.5,109.9,52.5,48.5,48.4,29.0；MS m/z(％):197(M+,25),171(5),104(100)。
Claims (5)
1.一种N,N-二取代氨基-丙二腈类化合物的合成方法，其特征为N,N-二取代的甲酰胺、三甲基氰硅烷、金属铜为催化剂在加热条件下按照反应式(1)进行，最终得到化合物N,N-二取代氨基-丙二腈。
其中：
(1)R1、R2不在同一个环系上时，两取代基可以相同，如甲基，乙基，等烷基基团；
(2)R1、R2不在同一个环系上时，两取代基可以不同，如R1可为甲基、乙基、丙基等烷基基团；R2可为苯基、苄基等芳基基团；
(3)R1、R2在同一环系上时，R1、R2连同N原子可为二氢吲哚基、1,2,3,4-四氢异喹啉基、哌啶基、吗啡啉基、4-甲基哌啶基。
2.根据权利要求书1所述的一种N,N-二取代氨基-丙二腈类化合物的制备方法，其特征是所用铜催化剂选自：三氟甲烷磺酸铜、三氟甲烷磺酸亚铜、溴化铜、溴化亚铜、氯化铜、氯化亚铜、碘化亚铜。
3.根据权利要求书1所述的一种N,N-二取代氨基-丙二腈类化合物的制备方法，其特征是所用的溶剂选自：正庚烷、1.2-二氯乙烷、乙腈、正己烷、环己烷、正壬烷、甲苯、四氢呋喃、1、4-二氧六环的一种或几种。
4.根据权利要求书1所述的一种N,N-二取代氨基-丙二腈的制备方法，其特征是所加热的温度为20-120℃。
5.根据权利要求书1所述的一种N,N-二取代氨基-丙二腈的制备方法，其特征是反应中各物质的物质的量比为：N,N-二取代的甲酰胺：三甲基氰硅烷：铜催化剂：溶剂＝1：2-5：0.05-0.20：10-100。
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| CN114249724A (zh) * | 2020-09-25 | 2022-03-29 | 鲁南制药集团股份有限公司 | 一种唑吡坦中间体的制备方法 |
Citations (3)
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| US3019261A (en) * | 1959-03-12 | 1962-01-30 | Du Pont | Nu-fluorinatedalkyl-amides of alkanoic acids and process of preparation |
| DE1128431B (de) * | 1960-11-16 | 1962-04-26 | Bayer Ag | Verfahren zur Herstellung basisch substituierter Malonsaeuredinitrile |
| DE10057055A1 (de) * | 2000-11-17 | 2002-05-23 | Bayer Ag | Verfahren zur Herstellung von aminosubstituierten Malonsäuredinitrilen |
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| US3019261A (en) * | 1959-03-12 | 1962-01-30 | Du Pont | Nu-fluorinatedalkyl-amides of alkanoic acids and process of preparation |
| DE1128431B (de) * | 1960-11-16 | 1962-04-26 | Bayer Ag | Verfahren zur Herstellung basisch substituierter Malonsaeuredinitrile |
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| ALBERT PADWA等: "Synthetic Application of Cyanoaminosilanes as Azomethine Ylide", 《J. ORG. CHEM.》 * |
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| CN114249724A (zh) * | 2020-09-25 | 2022-03-29 | 鲁南制药集团股份有限公司 | 一种唑吡坦中间体的制备方法 |
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