CN114409684A - 一种手性氨基醇锌配合物的制备及用途 - Google Patents

一种手性氨基醇锌配合物的制备及用途 Download PDF

Info

Publication number
CN114409684A
CN114409684A CN202210129958.5A CN202210129958A CN114409684A CN 114409684 A CN114409684 A CN 114409684A CN 202210129958 A CN202210129958 A CN 202210129958A CN 114409684 A CN114409684 A CN 114409684A
Authority
CN
China
Prior art keywords
complex
valinol
zinc nitrate
chiral
anhydrous methanol
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
Application number
CN202210129958.5A
Other languages
English (en)
Other versions
CN114409684B (zh
Inventor
罗梅
周伟豪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei University of Technology
Original Assignee
Hefei University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hefei University of Technology filed Critical Hefei University of Technology
Priority to CN202210129958.5A priority Critical patent/CN114409684B/zh
Publication of CN114409684A publication Critical patent/CN114409684A/zh
Application granted granted Critical
Publication of CN114409684B publication Critical patent/CN114409684B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/10—Spiro-condensed systems
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • 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
    • C07B2200/07—Optical isomers
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

一种手性L‑缬氨醇硝酸锌配合物的制备及用途,是由L‑缬氨醇和六水合硝酸锌按摩尔比为3:1在无水甲醇溶液中制备的由以下化学式(I)所示的配合物：
Figure DDA0003502061000000011
该手性L‑缬氨醇硝酸锌配合物I的合成方法，是称取1.0487g L‑缬氨醇、1.0115g六水合硝酸锌放入100mL圆底烧瓶，然后加入40mL无水甲醇作溶剂，搅拌回流48h后,热过滤，得无色滤液，静置自然挥发，7天后有无色晶体析出。该配合物(I)的用途，是作为催化剂在5‑甲氧基靛红的鲁卡特反应中，显示了较好的催化效能，其转化率达81.4％。

Description

一种手性氨基醇锌配合物的制备及用途
一、技术领域
本发明涉及一种新配合物及其用途，特别涉及一种锌配合物的制备及用途，确切地说是一种手性L-缬氨醇硝酸锌配合物的制备及用途。
二、背景技术
锌配合物是重要的催化剂和医药化工产品.其合成方法及用途见参考文献【1-3】:[1]韩佳星,刘峥,梁楚欣,et al.以吡啶-2,5-二羧酸或噻吩-2,5-二羧酸为配体的过渡金属配合物的合成、晶体结构及性质,无机化学学报,2019,35(04):605-12；[2]FREIS M,KLAPTKE T M,STIERSTORFER J,et al.Di(1H-tetrazol-5-yl)methane as Neutral Ligand inEnergetic Transition Metal Complexes[J].Inorganic chemistry,2017,56(14):7936-47；[3]AXELSON J C,GONZALEZ M I,MEIHAUS K R,et al.Synthesis andCharacterization of aTetrapodal NO44–Ligand and Its Transition MetalComplexes[J].Inorganic chemistry,2016,55(15):7527-34。
三、发明内容
本发明旨在提供含锌的配合物，所要解决的技术问题是一步合成得到目标产物。
本发明所称的锌配合物是由L-缬氨醇和六水合硝酸锌按摩尔比为3:1在无水甲醇溶液中制备的由以下化学式所示的配合物：
Figure BDA0003502060980000011
化学名称：含两分子结晶水的手性L-缬氨醇硝酸锌配合物,简称配合物(I)。
该配合物在5-甲氧基靛红的鲁卡特反应中显示了一定的催化性能，其转化率达81.4％。
本合成方法包括合成和分离,其合成方法是称取1.0487g L-缬氨醇、1.0115g六水合硝酸锌放入100mL圆底烧瓶，然后加入40mL无水甲醇作溶剂，加热搅拌回流48h后，热过滤，得无色滤液，静置自然挥发，7天后有无色晶体析出。
其合成反应如下：
Figure BDA0003502060980000021
本合成方法一步得到目标产物，工艺简单，操作方便。
该反应的反应机理可推测为三分子的手性配体L-缬氨醇化合物，在无水甲醇分子的作用下与六水合硝酸锌作用，一步形成含两分子结晶水的手性L-缬氨醇硝酸锌配合物.
四、附图说明
图1是含两分子结晶水的手性L-缬氨醇硝酸锌配合物的单晶X-衍射图。
五、具体实施方式
1.锌配合物的制备：
L-缬氨醇和六水合硝酸锌摩尔比为3:1参与反应，称取1.0487gL-缬氨醇、1.0115g六水合硝酸锌放入100mL圆底烧瓶，然后加入40mL无水甲醇作溶剂，加热搅拌回流48h，结束反应，热过滤，得无色滤液，静置自然挥发，7天后，有无色晶体析出。IR(KBr；ν,cm–1):3306,2968,1601,1522,1467,1325,1169,1030,1023,1090,881,834,825；产率:87％,m.p.:92–95℃；1H NMR(600MHz,CDCl3)1HNMR(600MHz,CDCl3,25℃),δ(ppm)＝3.67-3.71(m,1H),3.22(t,1H),2.62(s,1H),2.52(t,1H),1.64-1.66(m,1H),0.89-0.95(dd,J＝7.2Hz,6.6Hz,6H)；13C NMR(150MHz,CDCl3),δ(ppm)＝161.8,123.2,84.3,66.1,62.6,44.7,35.0,23.9；元素分析：C15H43N5O11Zn实测值为：C：33.86％；H：8.48％；N：13.45％。根据分子式计算的理论值为：C：33.65％；H：8.04％；N：13.09％；
化合物的晶体数据：
经验式 C15H43N5O11Zn
分子量 534.91
温度 293(2)K
波长
Figure BDA0003502060980000031
晶系，空间群 单斜晶系,P21 21 21
晶胞参数
Figure BDA0003502060980000032
alpha＝90°.
Figure BDA0003502060980000033
beta＝90°.
Figure BDA0003502060980000034
gamma＝90°.
体积
Figure BDA0003502060980000035
电荷密度 4,1.306Mg/m^3
吸收校正参数 0.958mm^-1
单胞内的电子数目 1144
晶体大小 0.200x0.140x0.060mm
Theta角的范围 2.618 to 24.999°
HKL的指标收集范围 -8<＝h<＝12,-14<＝k<15,-23<＝l<＝23
收集/独立衍射数据 10237/4664[R(int)＝0.0899]
theta＝30.5的数据完整度 97.1％
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 4664/10/305
精修使用的方法 1.007
衍射点的一致性因子 R1＝0.1057，wR2＝0.2590
可观察衍射的吻合因子 R1＝0.1761,wR2＝0.3214
差值傅里叶图上的最大峰顶和峰谷
Figure BDA0003502060980000041
晶体典型的键长数据：
Figure BDA0003502060980000042
Figure BDA0003502060980000051
Figure BDA0003502060980000061
晶体典型的键角数据
Figure BDA0003502060980000062
Figure BDA0003502060980000071
Figure BDA0003502060980000081
Figure BDA0003502060980000091
2.鲁卡特反应应用
目标合成的手性L-缬氨醇和六水合硝酸锌形成的配合物可作为催化剂应用于鲁卡特反应。鲁卡特反应是经典的有机反应之一。是合成喹唑啉衍生物化合物的方法之一。本实验的反应方程式：
Figure BDA0003502060980000101
称取5-甲氧基靛红0.08847g、甲酸铵0.26963g、1mmol％锌配合物I及无水甲醇5mL于25mL圆底烧瓶中，加热搅拌回流48h后，停止反应，旋转后，按石油醚：二氯甲烷1：1进行柱层分离，得晶体化合物，由核磁检测得其转化率：81.4％；1H NMR(600MHz,CDCl3),δppm10.0(s,1H),6.90-6.92(m,2H),6.85-6.87(m,3H),6.76(d,J＝8.2Hz,1H),6.55(d,J＝8.7Hz,1H),3.87(s,3H),3.73(d,J＝7.3Hz,6H)；13C NMR(150MHz,CDCl3)δppm 175.4,164.9(x2)，158.8，155.6，151.3，140.3,134.4,134.3，121.9，115.5,115.4,112.7,111.7,111.3,111.1,56.0(x2),53.0。

Claims (4)

1.一种手性L-缬氨醇硝酸锌配合物的制备及用途,其特征在于：由L-缬氨醇和六水合硝酸锌按摩尔比为3:1在无水甲醇溶液中制备的由以下化学式所示的配合物：
Figure FDA0003502060970000011
2.一种如权利要求1所述的手性L-缬氨醇硝酸锌配合物晶体I，在293(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 FDA0003502060970000012
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 21 21；晶胞参数
Figure FDA0003502060970000013
Figure FDA0003502060970000014
beta＝90°；
Figure FDA0003502060970000015
gamma＝90°。
3.一种如权利要求1所述的手性L-缬氨醇硝酸锌配合物I的合成方法，包括合成和分离，所述的合成是称取1.0487g L-缬氨醇、1.0115g六水合硝酸锌放入100mL圆底烧瓶，然后加入40mL无水甲醇作溶剂，搅拌回流48h后,热过滤，得无色滤液，静置自然挥发，7天后有无色晶体析出。
4.一种如权利要求1所述的配合物I的用途，其特征在于：其作为催化剂在5-甲氧基靛红的鲁卡特反应中，显示了较好的催化效能，转化率达81.4％。
CN202210129958.5A 2022-02-11 2022-02-11 一种手性氨基醇锌配合物的制备及用途 Active CN114409684B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210129958.5A CN114409684B (zh) 2022-02-11 2022-02-11 一种手性氨基醇锌配合物的制备及用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210129958.5A CN114409684B (zh) 2022-02-11 2022-02-11 一种手性氨基醇锌配合物的制备及用途

Publications (2)

Publication Number Publication Date
CN114409684A true CN114409684A (zh) 2022-04-29
CN114409684B CN114409684B (zh) 2023-05-26

Family

ID=81278529

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210129958.5A Active CN114409684B (zh) 2022-02-11 2022-02-11 一种手性氨基醇锌配合物的制备及用途

Country Status (1)

Country Link
CN (1) CN114409684B (zh)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718783A (zh) * 2012-07-12 2012-10-10 罗梅 一种手性化合物
CN102807577A (zh) * 2012-09-02 2012-12-05 罗梅 一种手性化合物
CN102977127A (zh) * 2012-12-19 2013-03-20 罗梅 一种手性化合物
CN103275108A (zh) * 2013-06-26 2013-09-04 罗梅 一种手性铜配合物制备及合成方法
CN105289663A (zh) * 2015-10-23 2016-02-03 同济大学 一种可磁性回收的GO/Fe3O4-CuI催化剂及其制备方法和应用
CN105777562A (zh) * 2016-04-11 2016-07-20 合肥祥晨化工有限公司 一种手性锌配合物晶体
CN107353215A (zh) * 2017-06-21 2017-11-17 合肥工业大学 一种手性s‑(+)‑2‑氨基‑1‑丁醇镍配合物晶体及用途
CN112480126A (zh) * 2020-12-11 2021-03-12 合肥工业大学 一种5-烷基喹唑啉衍生物的制备及用途

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102718783A (zh) * 2012-07-12 2012-10-10 罗梅 一种手性化合物
CN102807577A (zh) * 2012-09-02 2012-12-05 罗梅 一种手性化合物
CN102977127A (zh) * 2012-12-19 2013-03-20 罗梅 一种手性化合物
CN103275108A (zh) * 2013-06-26 2013-09-04 罗梅 一种手性铜配合物制备及合成方法
CN105289663A (zh) * 2015-10-23 2016-02-03 同济大学 一种可磁性回收的GO/Fe3O4-CuI催化剂及其制备方法和应用
CN105777562A (zh) * 2016-04-11 2016-07-20 合肥祥晨化工有限公司 一种手性锌配合物晶体
CN107353215A (zh) * 2017-06-21 2017-11-17 合肥工业大学 一种手性s‑(+)‑2‑氨基‑1‑丁醇镍配合物晶体及用途
CN112480126A (zh) * 2020-12-11 2021-03-12 合肥工业大学 一种5-烷基喹唑啉衍生物的制备及用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ABHILASH SHARMA: "A palladium-catalyzed cascade process for spirooxindole: an alternative way for the synthesis of spiro(indoline-3,2’-quinazolin)-2-ones", 《ORG. BIOMOL. CHEM》 *

Also Published As

Publication number Publication date
CN114409684B (zh) 2023-05-26

Similar Documents

Publication Publication Date Title
CN109438717B (zh) 一种金属有机框架材料及其制备方法和应用
Singh et al. Palladium (ii) complexes of N, N-diphenylacetamide based thio/selenoethers and flower shaped Pd 16 S 7 and prismatic Pd 17 Se 15 nano-particles tailored as catalysts for C–C and C–O coupling
CN111763135A (zh) 脱质子苯基桥连β-酮亚胺锂化合物在酯制备醇中的应用
Caulton et al. Synthesis and molecular structure of a mononuclear barium aryloxide-ethanolamine complex, Ba (2, 6-tert-Bu2C6H3O) 2 (HOCH2CH2NMe2) 4. cntdot. 2C7H8, exhibiting extensive hydrogen bonding
CN114409684A (zh) 一种手性氨基醇锌配合物的制备及用途
Chandler et al. Synthesis, characterization, and reactivity of lead (II) glycolate complexes
CN114621295A (zh) 一种手性噁唑啉钯配合物晶体及用途
CN112480126A (zh) 一种5-烷基喹唑啉衍生物的制备及用途
CN105566357A (zh) 一种手性l-缬氨酸铜配合物的制备及合成方法
Liu et al. Direct Synthesis of α-Methoxyphenylacetic Acid Via Tandem Catalysis from Styrene and Methanol with Co3O4/CuCo2O4 Heterostructures
CN114380765B (zh) 一种3-烯丙基洛丹宁二聚体晶体化合物的制备及用途
CN115785130A (zh) 一种铜金属配合物的制备及合成方法
GB2573886A (en) Process of preparing metal-organic framework material
CN114539325B (zh) 一种苯并三唑类钴配合物的制备及用途
CN105622646B (zh) 一种锌配合物晶体
CN113461727B (zh) 一种六苯基三硅氧环醚的合成方法及用途
CN116284064A (zh) 一种锌金属配合物
CN113563390B (zh) 双（三异丙基环戊二烯基）锶的制备方法
CA1207333A (en) Volatile cerium complexes
CN117986164A (zh) 一种四水合硫酸乙酯铜配合物晶体的制备方法
CN113461481B (zh) 一种1,1-二溴-2,2-二(氯甲基)环丙烷的制备方法
CN107827913A (zh) 含1,10‑菲啰啉状的n‑杂环卡宾铜（i）配合物及用途
CN112047982B (zh) 一种辛可宁钴钙配合物
CN115991671A (zh) 一种钴金属配合物
CN110577553B (zh) 基于六核铽簇的三维多孔配合物的合成方法和应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant