CN114931976A - 一种氮乙酰氨基二苯甲酮腙的用途 - Google Patents

一种氮乙酰氨基二苯甲酮腙的用途 Download PDF

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CN114931976A
CN114931976A CN202210566341.XA CN202210566341A CN114931976A CN 114931976 A CN114931976 A CN 114931976A CN 202210566341 A CN202210566341 A CN 202210566341A CN 114931976 A CN114931976 A CN 114931976A
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crystal
hydrazone
benzophenone
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罗梅
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Hefei University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
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    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
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Abstract

一种有如下结构式及晶胞参数的晶体化合物(I)的合成方法是无水无氧条件下,称取二苯甲酮腙2.0968g及1.9990g一水合乙酸铜，放入250mL两口烧瓶中，加入100mL氯苯做溶剂，回流反应48小时后，柱层析分离，用石油醚/二氯甲烷(3/7)洗脱，将收集的第一组分点自然挥发，得单晶氮乙酰氨基二苯甲酮腙；
Figure DDA0003655235780000011
该化合物晶体(Ⅰ)的用途，是在二苯甲酮亚胺的自缩合反应作为催化剂显示了一定的催化效果，其转化率达53％。

Description

一种氮乙酰氨基二苯甲酮腙的用途
一、技术领域
本发明涉及一种化合物的用途，特别涉及一种含氮化合物的用途，确切地说是一种二苯甲酮腙的氨基保护的用途。
二、背景技术
二苯甲酮腙乙酰化产物是重要的医药中间体，其用途极为广泛。可用作抗癌试剂。其合成方法及应用已有大量文献报道【1-4】。
参考文献：
1.Cao,Sufen and Duan,Wenhu，Microwave assisted solvent-free C-H amination by silica-supported manganese dioxide,Tetrahedron Letters,57(22),2390-2394；2016.
2.Somogyi,L.,Notes on the reactions of ketone acylhydrazones under acylation conditionsSomogyi, L.Tetrahedron,41(22),5187-90；1985.
3.Suginome,Hiroshi and Uchida,Tsutomu Photoinduced transformations. 49.Monochromaticlight-induced reactions of benzophenone hydrazones and the N- acetyl derivatives in carbon tetrachloride in the presence of oxygen.Bulletinof the Chemical Society of Japan,53(11),3225-31；1980。
4.董浩，侯梅芳，酰胺类化合物合成的最新研究进展，有机化学.2017,37(02),267-283。
三、发明内容
本发明旨在为有机合成领域特别是一种氨基保护的合成方法，所要解决的技术问题是遴选相应的手性药物中间体。
(一)本发明所称的化合物是以下化学式(Ⅰ)所示的化合物：
Figure BDA0003655235760000011
其化学名称：
该化合物(Ⅰ)的合成方法是二苯甲酮腙与50mol％一水合乙酸铜在氯苯溶剂中反应，该化学反应方程式如下：
Figure BDA0003655235760000021
本化合物(I)的合成方法是称取二苯甲酮腙2.0968g及1.9990g一水合乙酸铜，放入250mL 两口烧瓶中，加入100mL氯苯做溶剂，回流反应48小时后，柱层析分离，用石油醚/二氯甲烷(3/7)洗脱，将收集的第一组分点自然挥发，得单晶氮乙酰氨基二苯甲酮腙。
该反应的反应机理可推测如下：
二苯甲酮腙在一水合乙酸铜作用下，首先，形成氮乙酰氨基二苯甲酮腙。
其作为催化剂在二苯甲酮亚胺的自缩聚过程中，转化率达53％。
四、附图说明
图1氮乙酰氨基二苯甲酮腙的单晶衍射图。
五、具体实施方式
1.氮乙酰氨基二苯甲酮腙的制备
无水无氧条件下，称取二苯甲酮腙2.0968g及1.9990g一水合乙酸铜，放入250mL两口烧瓶中，加入100mL氯苯做溶剂，回流反应48小时后，柱层析分离，用石油醚/二氯甲烷(3/7) 洗脱，将收集的第一组分点自然挥发，得单晶氮乙酰氨基二苯甲酮腙；产率20％,m.p.99-102℃；1HNMR(500MHz,CDCl3,27℃),δ(ppm)＝8.37(s,1H),7.23-7.57(m,10H),2.44(s，3H)；13CNMR(125MHz,CDCl3,27℃)172.9,150.3，137.0(x2),131.6,130.0(x2),129.9(x2),129.7, 128.4(x2),127.3,20.7；IR(KBr):3436,3181,3099,3060,1702,1671,1588,1565,1489,1456, 1402,1382,1337,1314,1297,1171,1126,1073,1022,955,782,768,697,692,667,651,629, 545.
氮化合物晶体数据如下：
Figure BDA0003655235760000022
Figure BDA0003655235760000031
晶体典型的键长数据：
Figure BDA0003655235760000032
Figure BDA0003655235760000041
晶体典型的键角数据：
Figure BDA0003655235760000042
Figure BDA0003655235760000051
二苯甲酮亚胺的自缩合反应应用；
Figure BDA0003655235760000061
称取1mmol二苯甲酮亚胺和化合物I 0.05mmol放置于25mL小烧瓶中，加入2mLDMSO, 常温下搅拌5天，取少量样品做核磁检测，转化率达:53％；1H NMR(600MHz,CDCl3,27℃)；1H NMR(400MHz,CDCl3)δ7.50–7.44(m,4H),7.43–7.36(m,6H),7.36–7.25(m, 10H)。

Claims (1)

1.一种有如下结构式及晶胞参数的手性化合物晶体(Ⅰ)的用途，其特征在于其在二苯甲酮亚胺的自缩合反应作为催化剂显示了一定的催化效果，其转化率达53％,该手性化合物的结构式如下：
Figure FDA0003655235750000011
该手性化合物晶体(I)，在296(2)K温度下，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，
Figure FDA0003655235750000012
以ω-θ扫描方式收集衍射数据，其特征在于晶体三斜晶系,P-1,晶胞参数:
Figure FDA0003655235750000013
α＝113.018(3)°；
Figure FDA0003655235750000014
β＝95.764(3)°；
Figure FDA0003655235750000015
γ＝101.026°。
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Citations (6)

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GB1342194A (en) * 1971-04-08 1973-12-25 Chugai Pharmaceutical Co Ltd 5-substituted benzophenone hydrazone compounds and process for the production thereof
GB1380297A (en) * 1971-04-08 1975-01-15 Chugai Pharmaceutical Co Ltd 1,4,5-benzotriazocine derivatives and process for the production thereof
JPH10182625A (ja) * 1996-12-20 1998-07-07 Nippon Bayeragrochem Kk ベンゾフエノンヒドラゾン誘導体及び殺虫剤
US20050096337A1 (en) * 2003-11-05 2005-05-05 Jean Ackermann Phenyl derivatives, their manufacture and use as pharmaceutical agents
CN110256284A (zh) * 2019-06-05 2019-09-20 合肥工业大学 一种二苯甲酮肟衍生物的合成方法及用途
CN111100033A (zh) * 2019-12-25 2020-05-05 合肥工业大学 一种酰胺晶体化合物的合成方法及用途

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GB1377651A (en) * 1971-01-12 1974-12-18 Glaxo Lab Ltd Esters
US4808579A (en) * 1987-11-13 1989-02-28 American Cyanamid Company Novel monocycle β-lactam antibacterials
WO2013144228A1 (en) * 2012-03-29 2013-10-03 Basf Se Pesticidal methods using heterocyclic compounds and derivatives for combating animal pests

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1342194A (en) * 1971-04-08 1973-12-25 Chugai Pharmaceutical Co Ltd 5-substituted benzophenone hydrazone compounds and process for the production thereof
GB1380297A (en) * 1971-04-08 1975-01-15 Chugai Pharmaceutical Co Ltd 1,4,5-benzotriazocine derivatives and process for the production thereof
JPH10182625A (ja) * 1996-12-20 1998-07-07 Nippon Bayeragrochem Kk ベンゾフエノンヒドラゾン誘導体及び殺虫剤
US20050096337A1 (en) * 2003-11-05 2005-05-05 Jean Ackermann Phenyl derivatives, their manufacture and use as pharmaceutical agents
CN110256284A (zh) * 2019-06-05 2019-09-20 合肥工业大学 一种二苯甲酮肟衍生物的合成方法及用途
CN111100033A (zh) * 2019-12-25 2020-05-05 合肥工业大学 一种酰胺晶体化合物的合成方法及用途

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