CN103992243B - 一种手性酰铵盐晶体的制备及用途 - Google Patents
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- -1 acyl ammonium salt Chemical class 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000009466 transformation Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- VPSSPAXIFBTOHY-ZCFIWIBFSA-N (2r)-2-amino-4-methylpentan-1-ol Chemical compound CC(C)C[C@@H](N)CO VPSSPAXIFBTOHY-ZCFIWIBFSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
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- 238000002447 crystallographic data Methods 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
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- 238000012544 monitoring process Methods 0.000 claims 1
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- 125000006850 spacer group Chemical group 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000003934 aromatic aldehydes Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- VPSSPAXIFBTOHY-LURJTMIESA-N (2s)-2-amino-4-methylpentan-1-ol Chemical compound CC(C)C[C@H](N)CO VPSSPAXIFBTOHY-LURJTMIESA-N 0.000 description 3
- 238000006842 Henry reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
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- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006987 Nef reaction Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- QDYBCIWLGJMJGO-UHFFFAOYSA-N dinitromethanone Chemical compound [O-][N+](=O)C(=O)[N+]([O-])=O QDYBCIWLGJMJGO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
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- 238000005648 named reaction Methods 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种手性酰铵盐晶体，其化学式如下：？
Description
一、技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种手性化合物及其制备方法，确切地说是一种手性酰铵盐晶体的制备及用途。
二、背景技术
手性酰铵盐是重要的催化剂和医药化工产品，其在有机合成作为一个新的课题已引起化学工作者的关注。
参考文献：
1.Quaternaryammonium(hypo)ioditecatalysisforenantioselectiveoxidativecycloetherification,UyanikMuhammet；OkamotoHiroaki；YasuiTakeshi；IshiharaKazuaki,Science.2010Jun11；328(5984):1365-6.
2.Researchprogressonchitosanquaternaryammoniumsalt,Li,Rong-chun,HuaxueShiji，2011,33(10),895-898.
3.DiastereoselectiveAziridinationofChiralElectron-DeficientOlefinswithN-Chloro-N-sodiocarbamatesCatalyzedbyChiralQuaternaryAmmoniumSalts,Murakami,Yuta；Takeda,Youhei；Minakata,Satoshi,JournalofOrganicChemistry,2011,76(15),6277-6285.
4.Synthesisofchiralspirocyclo-quaternaryammoniumsaltsfromL-prolineandtheirapplicationasphase-transfercatalystsinasymmetricalkylation,Wang,Na；Lin,Song-Wen；Yang,Qing；Sun,Qi；Li,Run-Tao,JournalofChinesePharmaceuticalSciences,2011,20(1),26-31.
5.Phosphorofluoridicacidammoniumsaltsandacids:Synthesis,NMRproperties,andapplicationasacidcatalysts,Murai,Toshiaki；Tonomura,Yusuke；Takenaka,Toru,HeteroatomChemistry,2011,22(3-4),417-425.
6.Cobalt-Mediated,EnantioselectiveSynthesisofC2andC1Dienes,Boyd,W.Christopher；Crimmin,MarkR.；Rosebrugh,LaurenE.；Schomaker,JenniferM.；Bergman,RobertG.；Toste,F.Dean,JournaloftheAmericanChemicalSociety,2010,132(46),16365-16367。
申请人以7,7,8,8-四氰基奎二甲烷与D-亮氨醇在130mol％氯化锌作催化剂下，得到了一种手性化合物(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐
三、发明内容
本发明旨在提供化合物手性化合物。所要解决的技术问题是一步合成得到目标产物。
本发明所称的手性化合物是由7,7,8,8-四氰基奎二甲烷与D-亮氨醇制备的由以下化学式所示的化合物：
(I)
化学名称：(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐,简称化合物(I)。
本合成方法包括合成和分离，所述的合成用130mol％氯化锌做催化剂，7,7,8,8-四氰基奎二甲烷4.89mmol，D-亮氨醇90mmol，用50mL氯苯做溶剂，回流反应3天后，柱层析分离，用石油醚/二氯甲烷(2/8)洗脱，将收集的最后组分点自然挥发，得单晶(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐。
合成反应如下：
本合成方法一步得到目标产物，工艺简单，操作方便。
其反应机理可推测如下：
7,7,8,8-四氰基奎二甲烷由于在空气及大量路易斯酸催化剂作用下不稳定，氰基首先生成甲酸，然后与大大过量的L-亮氨醇在氯化锌作用下进行缩合反应，甲酸中的羟基与L-亮氨醇中的氨基上的氢原子，脱去1分子的氢气，形成氨基甲酸，再与过量的L-亮氨醇形成甲酸铵盐。
四、附图说明
图1是(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐的X-衍射分析图。
Henry反应是经典的有机人名反应之一。该反应是指羰基化合物通常是芳醛和有α-氢的硝基化合物之间的缩合反应,反应的结果是硝基的α-碳原子加成到羰基上,形成具有羟基、硝基的双官能团的化合物。Henry反应的产物可以方便地转化为各式各样有重要用途的化合物,如β-氨基醇、硝基烯烃、硝基酮、硝基烯酮或进行Nef反应。因此Henry反应在有机合成中是非常实用的反应之一。扩展这一反应的应用范围,合成具有更多官能团、结构上更为复杂的化合物,是一项有意义的工作。
本发明所称(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐的用途是在苯甲醛亨利反应中的用途，该化合物在苯甲醛的亨利反应中显示了良好的催化性能，其转化率达65％，e.e.％值:29.2％。
芳醛与氰化物或腈化物的加成反应为腈硅化反应。当芳醛与氰化物加成时得到芳基羟腈；当芳醛与腈化物为三甲基硅腈(TMSCN)加成时得到芳基氰醇硅醚，如下式所示:
本发明所称(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐的用途是在苯甲醛腈硅化反应中的用途，该化合物在苯甲醛的腈硅化反应中显示了较好的催化性能，其转化率达99％，ee％值达30.8％。
五、具体实施方式
在100mL两口瓶中,加入无水ZnCl270mg(0.74mmol),50mL氯苯,7,7,8,8-四氰基奎二甲烷1.0g(4.90mmol),D-亮氨醇9.3g,将混合物在高温下回流72h,停止反应,减压以除去溶剂,,将剩余物用水溶解,并用CH2Cl2(20mLx3)萃取,有机相用无水硫酸钠干燥,旋转除去溶剂,将粗产品用石油醚/二氯甲烷(3:7)柱层析,得无色油状液体,产率30％；[a]5D＝+23.8°(c＝0.25,CH2Cl2)：IR(KBr):3306,2956,2870,1746,1660,1540,1468,1385,1367,1230,1108,1070,1022,948,733；元素分析数据：C:56.12％,H:10.78％,N:10.22％；该化合物的晶体数据如下：
晶体典型的键长数据：
晶体的键角数据
六、亨利反应应用:
催化剂I(0.15mmol),苯甲醛0.10mL(0.986mmol)及硝基甲烷(0.50mL,9.255mmol)在室温下搅拌48h，柱层析分离，产率为：65％,ee％：29.2％；1HNMR(300MHz,CDCl3)7.28～7.32(m,5H,Ar-H),5.32～5.35(d,J＝9.18Hz,1H,-CH),4.38～4.56(m,2H,-CH2),3.89(br,1H,-OH).13CNMR(75MHz,CDCl3)138.30128.92(x2),128.82,125.98(x2),81.16,70.9。
七、腈硅化反应应用:
2-苯基-2-(三甲硅氧基)丙腈
0.15mmol化合物I,苯甲醛0.1mL,TMSCN0.3ml(3.3mmol),2mL二氯甲烷相继在20～30℃下加入，3天后，加入水淬灭经柱层后(石油醚/二氯甲烷：5/1)，得无色油状液体,转化率率>99％；ee％：30.8％；1HNMR(300MHz,CDCl3)7.56–7.59(m,0.9Hz,2H),7.31–7.34(m,3H),5.43(s,1H),0.16(s,9H).13CNMR(75MHz,CDCl3)136.1,128.8(x2),126.2(x2),119.1,63.5,-0.39(x3)。
Claims (2)
1.一种手性酰铵盐晶体，其特征在于是由7,7,8,8-四氰基奎二甲烷与D-亮氨醇制备的由以下化学式所示的化合物：
该手性酰铵盐晶体，其晶体结构表征参数如下：在273(2)k温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线以ω-θ扫描方式收集衍射数据，其特征在于晶体属斜方晶系,空间群C2(1)，晶胞参数：α＝90°；β＝101.955(5)°；γ＝90°。
2.(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐晶体在苯甲醛亨利反应中的用途：
(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐晶体的合成：用130mol％氯化锌做催化剂，7,7,8,8-四氰基奎二甲烷4.89mmol，D-亮氨醇90mmol，用50mL氯苯做溶剂，回流反应3天后，柱层析分离，用石油醚/二氯甲烷按体积比2/8洗脱，将收集的最后组分点自然挥发，得单晶(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐；
(R)-3-甲基-丁基-1-羟甲基氨基甲酸-(R)-3-甲基-丁基-1-羟甲基铵盐晶体催化剂0.15mmol,苯甲醛0.10mL及硝基甲烷0.50mL在室温下搅拌48h，用核磁监测，转化率：65％，e.e.％:29.2％。
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| KR20120128449A (ko) * | 2011-05-17 | 2012-11-27 | 서울대학교산학협력단 | 10-아미노데카논산 또는 그의 에스터 유도체의 제조방법 |
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