CN107337617A - 一种乙酰脲内聚体晶体化合物的合成方法及用途 - Google Patents

一种乙酰脲内聚体晶体化合物的合成方法及用途 Download PDF

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CN107337617A
CN107337617A CN201710667685.9A CN201710667685A CN107337617A CN 107337617 A CN107337617 A CN 107337617A CN 201710667685 A CN201710667685 A CN 201710667685A CN 107337617 A CN107337617 A CN 107337617A
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acetylurea
aggressiveness
crystalline compounds
synthetic method
reaction
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罗梅
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Hefei Xiangchen Chemical Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • 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
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
    • B01J31/0249—Ureas (R2N-C(=O)-NR2)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
    • C07C275/48—Y being a hydrogen or a carbon atom
    • C07C275/50—Y being a hydrogen or an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种乙酰脲内聚体化合物，其特征是由以下化学式所示的化合物：

Description

一种乙酰脲内聚体晶体化合物的合成方法及用途
一、技术领域
本发明涉及一种化合物及其制备方法，特别涉及一种含氮化合物及其制备方法，确切地说是一种乙酰脲内聚体晶体化合物的合成方法。
二、背景技术
乙酰脲化合物是重要的医药中间体，其合成方法及应用已有文献报道【1-3】：
参考文献：
1. Acetylcarbamide complexes of some lanthanide bromides and chlorides:Syntheses and structures； Alikberova, L. Yu.; Al'bov, D. V.; Bushmeleva, A.S.; Fedorova, G. A.; Kravchenko, V. V.， Russian Journal of CoordinationChemistry (2014), 40(12), 918-924.
2. New method of preparing N-​acetylurea，Kurbanova, M. M. IzvestiyaVysshikh Uchebnykh Zavedenii, Khimiya i Khimicheskaya Tekhnologiya (2004), 47(8), 165.
3. Crystallographic characterization of monoacylated ureas，Hartung,Helmut; Lux, Georg; Hennicke, Rainer; Schellenberger, Alfred，Zeitschrift fuerChemie (1973), 13(6)，234-235。
三、发明内容
本发明旨在为不对称合成领域特别是制备手性药物提供一种高效催化剂所需的化合物配体，所要解决的技术问题是遴选相应的原料并建立相应的方法合成手性催化剂配体。
（一）本发明所称的手性化合物是以下化学式(Ⅰ)所示的化合物：
其化学名称：乙酰脲内聚体。
该化合物（Ⅰ）的合成方法是间氰基苯丙烯与乙酰脲在催化剂氯化锌及无水甲醇溶液中反应，该化学反应式如下：
本乙酰脲内聚体化合物(Ⅰ)合成方法包括合成、分离和纯化，所述的合成是无水无氧条件下，称取称取0.6420g（0.005mol）氯化锌，乙酰脲1.0046g及间氰基苯丙烯1.3275g放入100mL两口烧瓶中，加入20mL无水甲醇室温搅拌使其溶解；反应48小时结束后有乙酰脲内聚体白色晶体析出。
该反应的反应机理可推测如下：乙酰脲在无水甲醇、间氰基苯丙烯及催化剂氯化锌的作用下乙酰脲发生分子内聚形成目标化合物I。
本乙酰脲内聚体化合物(Ⅰ)的制备，采用简易，高效的有机合成方法，一步合成，经X-衍射，NMR,IR及元素分析确定其结构，其作为催化剂在苯甲醛与苯甲酰胺的反应中显示了较好的催化效果，其转化率高达99%。
四、附图说明
图1是乙酰脲内聚体化合物 (I) 的单晶衍射图。
五、具体实施方式
1. 乙酰脲内聚体化合物 (I)的制备
称取0.6420g（0.005mol）氯化锌，乙酰脲1.0046g及间氰基苯丙烯1.3275g放入100mL圆底烧瓶中，加入30mL无水甲醇室温搅拌 48h后停止反应，静止后有晶体析出；将晶体用石油醚和正己烷冲洗3次，真空干燥30min，得目标产物，产率为28%，熔点232-233°C; HRMS数据C3H6N2O2，理论值：102.0429; 实测值：102.0612;元素分析数据：C：35.29%； H：5.92%；N：27.44%； 实测值：C 35.40%； H：5.69 %；N：27.65%； 1HNMR (600MHz, CDCl3, 27℃), δ(ppm) = 10.10(s, 1H), 7.70(s, 1H), 7.15(s, 1H), 2.0(s, 3H); 13C NMR (150 MHz,CDCl3) 172.4, 154.3, 24.0。红外光谱数据(KBr, cm-1)：3414, 3306, 3216,1730, 1654,1485, 1370, 1210, 1072, 1026, 919, 766, 567；
乙酰脲内聚体晶体数据如下：
经验式 C3H6N2O2
分子量 102.10
温度 100.01(10) K
波长 0.71073 Å
晶系， 空间群 单斜晶系, P21
晶胞参数 a = 6.6827(3) Å α = 90°.
b = 5.0880(2) Å β = 96.655(4)°.
c = 6.9153(3) Å γ = 90 °
体积 233.545（18）Å^3
电荷密度 2, 1.452Mg/m^3
吸收 校正参数 1.051 mm^-1
单胞内的电子数目 108.0
晶体大小 0.1 x 0.1x 0.1mm
Theta 角的范围 12.888 to 145.472
HKL的指标收集范围 -6<=h<=8, -6<k<=4，-8<l<=8
收集/独立衍射数据 758/ 628[R(int) = 0.0110]
吸收校正的方法 多层扫描
精修使用的方法 F^2 的矩阵最小二乘法
数据数目/使用限制的数目/参数数目 1326/0/111
精修使用的方法 1.045
衍射点的一致性因子 R1 = 0.0256，ωR2= 0.0647
可观察衍射的吻合因子 R1 = 0.0261, ωR2 = 0.0648
差值傅里叶图上的最大峰顶和峰谷 0.12 and -0.19 e.Å^-3
晶体典型的键长数据：
Atom Atom Length/Å Atom Atom Length/Å
C1 N1 1.319(3) C2 C3 1.498(3)
C1 N2 1.408(2) C2 N2 1.373(3)
C1 O1 1.239(3) C2 O2 1.227(3)
晶体典型的键角数据：
Atom Atom Atom Angle/˚ Atom Atom Atom Angle/˚
N1 C1 N2 118.2(2) O2 C2 C3 122.4(2)
O1 C1 N1 124.75(17) O2 C2 N2 122.7(2)
O1 C1 N2 117.1(2) C2 N2 C1 128.9(2)
N2 C2 C3 114.9(2)
，N’-（苯基亚甲基）二苯甲酰胺的制备
在25mL两口瓶中,加入0.0659g配合物I , 2mLTHF和氯苯2mL, 0.05mL苯甲醛及0.1302g苯甲酰胺,回流反应48小时后,有晶体出现：用核磁检测，转化率：>99 %;1HNMR(500MHz, CDCl3, 27℃), δ (ppm) = 9.02 (d，J=7.77Hz, 2H),7.91 (d,J=7.42Hz,4H),7.54(t，J=7.4Hz, 2H),7.47(t, J=7.7Hz, 6H), 7.37 (t,J=7.7Hz, 2H), 7.30 (t, J=7.3Hz, 1H), 7.03(t, J=7.9Hz, 1H)。

Claims (4)

1.一种乙酰脲内聚体化合物，其特征是由以下化学式所示的化合物：
（Ⅰ）。
2.由权利要求1所述的乙酰脲内聚体晶体化合物（I），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CuKα (λ = 1.54184)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 P21，晶胞参数：a/Å 6.6827(3),b/Å5.0880(2) , c/Å 6.9153(3) ; α/° 90 β/° 96.655(4) , γ/° 90。
3.权利要求2所述乙酰脲内聚体晶体化合物（I）的合成方法，包括合成、分离和纯化，所述的合成是无水无氧条件下称取0.6420g（0.005mol）氯化锌，乙酰脲1.0046g及间氰基苯丙烯1.3275g放入100mL圆底烧瓶中，加入20mL无水甲醇室温搅拌使其溶解；反应48小时结束后有乙酰脲内聚体白色晶体析出。
4.权利要求2所乙酰脲内聚体晶体化合物(Ⅰ)的用途，是作为催化剂在苯甲醛与苯甲酰胺的反应，其效率达99%。
CN201710667685.9A 2017-08-07 2017-08-07 一种乙酰脲内聚体晶体化合物的合成方法及用途 Pending CN107337617A (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107698465A (zh) * 2017-11-14 2018-02-16 合肥祥晨化工有限公司 一种乙酰脲晶体化合物的合成方法

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CN106565518A (zh) * 2016-11-11 2017-04-19 合肥祥晨化工有限公司 一种酰胺晶体化合物的合成方法

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CN106565518A (zh) * 2016-11-11 2017-04-19 合肥祥晨化工有限公司 一种酰胺晶体化合物的合成方法

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CN107698465A (zh) * 2017-11-14 2018-02-16 合肥祥晨化工有限公司 一种乙酰脲晶体化合物的合成方法
CN107698465B (zh) * 2017-11-14 2019-07-05 合肥祥晨化工有限公司 一种乙酰脲晶体化合物的合成方法

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Application publication date: 20171110