异长叶烯酮肟的合成及其与金属离子的配位特性

doi:10.3969/j.issn.0253-2417.2019.01.015

摘要/Abstract

摘要：

以异长叶烯酮为原料，经肟化反应合成了异长叶烯酮肟。分别采用单因素法及正交试验法考察了工艺条件对反应产率的影响，确定了最佳工艺条件为：反应时间6 h，反应温度76 ℃，以醋酸钠为催化剂，n(异长叶烯酮):n(盐酸羟胺):n(催化剂)1:1.3:0.55。在此条件下，异长叶烯酮肟的产率＞99 %。采用FT-IR、¹H NMR、GC-MS和单晶X衍射等分析手段对化合物的结构进行了表征，研究了异长叶烯酮肟对几种金属离子的络合性能，结果表明：异长叶烯酮肟与Cu²⁺的作用明显强于与Co²⁺、Cd²⁺、La³⁺、Pb²⁺、Ag⁺等金属离子的作用；异长叶烯酮肟与Cu²⁺主要是通过分子中氮原子和氧原子与Cu²⁺的配位作用进行络合。

关键词: 异长叶烯酮肟, 异长叶烯酮, 肟化反应, 金属配合物

Abstract:

Isolongifolenone oxime was prepared from isolongifolenone and hydroxylamine hydrochloride by oximation reaction. Effects of the reaction conditions on the yield of isolongifolenone oxime were investigated by single factor method and ortnogonal experiments. The optimum reaction conditions were as follows:sodium acetate as the catalyst, the molar ratio of isolongifolenone, hydroxylamine and sodium acetate 1:1.3:0.55, reaction temperature 76 ℃ and reaction time 6 h. The yield of isolongifolenone oxime reached 99.0% under the optimum reaction conditions.The structure of the isolongifolenone oxime was determined by FT-IR, ¹H NMR, GC-MS and single crystal X-ray diffraction. Complexation properties of isolongifolenone oxime on metal ions including Cu²⁺, Co²⁺, Cd²⁺, La³⁺, Pb²⁺, Ag⁺ were examined, and the results showed that isolongifolenone oxime exhibited better complexing effect to Cu²⁺ than that to other metal ions. It was also known from the FT-IR that the complexation between Cu²⁺ and isolongifolenone oxime was formed by Cu-N and Cu-O coordination bonds.

Key words: isolongifolenone oxime, isolongifolenone, oximation, metal complex

中图分类号:

TQ35

吴陈亮,王芸芸,徐徐,谷文,王石发. 异长叶烯酮肟的合成及其与金属离子的配位特性[J]. 林产化学与工业, 2019, 39(1): 101-107.

Chenliang WU,Yunyun WANG,Xu XU,Wen GU,Shifa WANG. Synthesis and Complexation Properties on Metal Ion of Isolongifolenone Oxime[J]. Chemistry and Industry of Forest Products, 2019, 39(1): 101-107.

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参考文献 18

1	崔平, 刘新华, 智丽萍, 等. 新型5-芳基-N-吡唑肟酯化合物的合成与杀菌活性[J]. 应用化学, 2008, 25 (7): 820- 824. doi: 10.3969/j.issn.1000-0518.2008.07.014
	CUI P , LIU X H , ZHI L P , et al. Synthesis and biological activity of novel 5-aryl-N-pyrazole oxime ester derivatives[J]. Chinese Journal of Applied Chemistry, 2008, 25 (7): 820- 824. doi: 10.3969/j.issn.1000-0518.2008.07.014
2	于海峰,张彦英,高金圣.肟醚类除草剂及其应用: CN101427679[P]. 2009-05-13.
	YU H F, ZHANG Y Y, GAO J S. Oxime ether-derivative herbicides and uses thereof: CN101427679[P]. 2009-05-13.
3	周爱民,崔建国,范磊,等. 3, 6-二取代甾体肟类化合物作为抗肿瘤药物:
	CN101245090A[P]. 2008-08-20. ZHOU A M, CUI J G, FAN L, et al. 3, 6-di-substituted sterides oximes compound as antineoplastic medicament: CN101245090A[P]. 2008-08-20.
4	胡仁道. 肟类除氧剂及其应用[J]. 华东电力, 2000, 28 (8): 63- 65. doi: 10.3969/j.issn.1001-9529.2000.08.026
	HU R D . Oxime Derivative Doxidantand uses thereof[J]. East China Electric Power, 2000, 28 (8): 63- 65. doi: 10.3969/j.issn.1001-9529.2000.08.026
5	唐清, 王帅, 彭静, 等. 羟肟酸类化合物的合成与应用研究进展[J]. 化工进展, 2014, (3): 703- 709.
	TANG Q , WANG S , PENG J , et al. Research progress on the synthesis and application of hydroxamic acid compounds[J]. Chemical Industry and Engineering Progress, 2014, (3): 703- 709.
6	姚秋萍, 范磊, 刘亮, 等. 某些具有孕甾烷结构肟类化合物的合成研究[J]. 化学研究与应用, 2013, 25 (2): 220- 223. doi: 10.3969/j.issn.1004-1656.2013.02.016
	YAO Q P , FAN L , LIU L , et al. Synthesis of some steriodal oximes with pregnane structure[J]. Chemical Research and Application, 2013, 25 (2): 220- 223. doi: 10.3969/j.issn.1004-1656.2013.02.016
7	AKINE S , DONG W , NABESHIMA T . Octanuclear zinc(Ⅱ) and cobalt(Ⅱ) clusters produced by cooperative tetrameric assembling of oxime chelate ligands[J]. Inorganic Chemistry, 2006, 45 (12): 4677- 4684. doi: 10.1021/ic060055n
8	AKINE S , TANIGUCHI T , DONG W , et al. Oxime-based salen-type tetradentate ligands with high stability against imine metathesis reaction[J]. Journal of Organic Chemistry, 2005, 70 (5): 1704. doi: 10.1021/jo048030y
9	AI H, SUGA N, OGITANI S, et al. Polymer/oxime ester/coumarin compound photosensitive composition: US5019482[P]. 1991-05-28.
10	武法文, 王志祥, 李磊, 等. 异长叶烯酮的绿色合成[J]. 精细化工, 2009, 26 (11): 1116- 1119. doi: 10.3321/j.issn:1003-5214.2009.11.018
	WU F W , WANG Z X , LI L , et al. Green Synthesis of Isolongifolenone[J]. Fine Chemicals, 2009, 26 (11): 1116- 1119. doi: 10.3321/j.issn:1003-5214.2009.11.018
11	WANG C , LU L , ZHANG A , et al. Repellency of selected chemicals against the bed bug (Hemiptera:Cimicidae)[J]. Journal of Economic Entomology, 2013, 106 (6): 2522- 2529. doi: 10.1603/EC13155
12	ZHANG A J, CARROLL J F, WANG S F, et al. Methods for repelling arthropods using isolongifolenone and/or isologifolenone analogs: CN101801901A[P]. 2010-08-11.
13	张华安.一种异长叶烯酮防晒驱蚊霜:
	CN103315917A[P]. 2013-09-25. ZHANG H A. Isolongifolenone sun-blocking and mosquito-repelling cream: CN103315917A[P]. 2013-09-25.
14	申利群,吴爱群,张武,等.异长叶烯酮肟醚衍生物及其制备方法和应用:
	CN106565536A[P]. 2017-04-19. SHEN L Q, WU A Q, ZHANG W, et al.Isolongifolenone oxime ether derivative, and preparation method and application thereof: CN106565536A[P]. 2017-04-19.
15	王蕊欣, 雷彩萍, 史小慧, 等. 固载化羟肟酸过渡金属配合物催化氧化乙苯的性能[J]. 功能材料, 2016, 47 (2): 2253- 2257. doi: 10.3969/j.issn.1001-9731.2016.02.049
	WANG R X , LEI C P , SHI X H , et al. Catalytic property of immobilizedsalicyl hydroxamic acid-transition metal complex in oxidation of ethylbenzene by molecular oxygen[J]. Journal of Functional Materials, 2016, 47 (2): 2253- 2257. doi: 10.3969/j.issn.1001-9731.2016.02.049
16	胡岳华, 韩海生, 田孟杰, 等. 苯甲羟肟酸铅金属有机配合物在氧化矿浮选中的作用机理及其应用[J]. 矿产保护与利用, 2018, (1): 42- 47.
	HU Y H , HAN H S , TIAN M J , et al. The application of metal-coordinated complexes in the flotation of oxide minerals and fundamental research of the adsorption mechanism[J]. Conservation and Utilization of Mineral Resources, 2018, (1): 42- 47.
17	伍娉, 何婧琳, 曹小妹, 等. 基于头孢克肟的荧光熄灭效应用于微量铬(Ⅵ)的灵敏检测[J]. 化学传感器, 2014, 34 (2): 52- 57. doi: 10.3969/j.issn.1008-2298.2014.02.007
	WU P , HE J L , CAO X M , et al. Sensitive determination of trace Cr (Ⅵ) based on cefixime fluorescence quenching effect[J]. Chemical Sensors, 2014, 34 (2): 52- 57. doi: 10.3969/j.issn.1008-2298.2014.02.007
18	彭晗, 杨丽娟, 徐徐, 等. 异长叶烯酮的绿色合成研究[J]. 林产化学与工业, 2015, 35 (3): 97- 103. doi: 10.3969/j.issn.0253-2417.2015.03.017
	PENG H , YANG L J , XU X , et al. Green synthesis of isolongifolenone[J]. Chemistry and Industry of Forest Products, 2015, 35 (3): 97- 103. doi: 10.3969/j.issn.0253-2417.2015.03.017

项目 items		异长叶烯酮转化率/% conversion ratio of isolongifolenone	反应选择性/% reaction selectivity	产物产率/% product yield
催化剂种类 catalyst species	K₂CO₃	53.76	92.23	49.65
	C₂H₅ONa	84.62	100.00	84.62
	CH₃COONH₄	36.07	94.00	33.43
	CH₃COONa	96.79	99.61	96.41
	Al₂O₃	95.70	98.54	94.31
n(异长叶烷酮):n(催化剂)n(isolongifolenone):n(catalyst)	1:0.6	96.90	99.87	96.77
	1:0.55	100.00	99.59	99.59
	1:0.45	96.29	98.52	94.86
	1:0.3	96.66	95.03	91.85
	1:0.1	54.30	89.88	49.74
反应温度 reaction temperature	76 ℃	97.64	99.16	96.41
	65 ℃	94.11	94.11	90.92
	55 ℃	75.11	96.82	72.72
	45 ℃	58.64	99.69	58.46
	25 ℃	30.55	96.45	29.47
n(异长叶烷酮):n(盐酸羟胺)n(isolongifolenone):n(hydroxylamine hydrochloride)	1:1	86.24	95.67	82.51
	1:1.1	93.58	95.94	89.78
	1:1.2	92.96	97.32	94.59
	1:1.3	99.26	99.03	98.29
	1:1.4	98.81	97.99	96.51

序号No.	An(异长叶烯酮)/n(盐酸羟氨)n(isolongifolenone)/n(NH₂OH-HCl)	Bn(异长叶烯酮)/n(催化剂)n(isolongifolenone)/n(catalyst)	C温度/℃temperature	D时间/htime	产率/%yield
1	1:1.1	1:0.35	60	4	70.43
2	1:1.1	1:0.45	68	6	93.32
3	1:1.1	1:0.55	76	8	97.71
4	1:1.2	1:0.35	68	8	97.59
5	1:1.2	1:0.45	76	4	94.64
6	1:1.2	1:0.55	60	6	96.39
7	1:1.3	1:0.35	76	6	99.03
8	1:1.3	1:0.45	60	8	78.58
9	1:1.3	1:0.55	68	4	89.29
k₁	87.15	89.01	81.80	84.79
k₂	96.21	88.85	93.40	96.24
k₃	88.96	94.46	97.12	91.29
R	9.05	5.62	15.32	11.46

项目 items	参数 parameter
经验分子式empirical formula	C₁₅H₂₃NO
相对分子质量formula weight	233.34
晶胞尺寸crystal size	0.11 mm×0.16 mm×0.18 mm
晶系crystal system	单斜晶monoclinic
晶体群space group	P2₁/n
晶胞参数unit cell dimensions	a=0.8913(10) nm，α=90°b=1.2369(13)nm，β=108.313(3)° c=1.3759(15) nm，γ=90°
体积volume	1.44(3) nm³
晶胞数crystal cell number(Z)	4
θ角数据收集范围θ range for data collection	2.27~28.32 °
单胞中电子的数目number of electrons in the unit cell(F(000))	516.0
计算密度calculated density(D_c)	1.081 g/cm³
全部衍射点的R值R indices (all data)	R₁= 0.0987, wR₂ = 0.2138
可观测衍射点的R值final R indices[I>2σ(I)]	R₁= 0.0651, wR₂ = 0.1857

键型 bond	键长/nm bond length
O(1)—N(1)	0.1407(2)
N(1)—C(1)	0.1284(2)
C(2)—C(3)	0.1327(2)
C(2)—C(1)	0.1442(2)
C(3)—C(4)	0.1513(3)
C(3)—C(13)	0.1520(3)
C(4)—C(5)	0.1526(3)
C(4)—C(14)	0.1538(3)
C(4)—C(10)	0.1554(3)
C(1)—C(6)	0.1505(3)
C(5)—C(6)	0.1528(3)
C(5)—C(9)	0.1535(3)
C(5)—C(8)	0.1537(3)
C(13)—C(16)	0.1514(4)
C(13)—C(12)	0.1550(4)
C(13)—C(15)	0.1555(4)
C(10)—C(11)	0.1541(5)
C(14)—C(12)	0.1523(4)
C(12)—C(11)	0.1485(5)

键型bond	键长/nmbond length
C(1)—N(1)—O(1)	112.22(15)
C(3)—C(2)—C(1)	120.16(16)
C(2)—C(3)—C(4)	123.96(16)
C(2)—C(3)—C(13)	127.06(18)
C(4)—C(3)—C(13)	108.97(15)
C(3)—C(4)—C(5)	112.80(13)
C(3)—C(4)—C(14)	100.38(17)
C(5)—C(4)—C(14)	119.33(17)
C(3)—C(4)—C(10)	103.92(16)
C(5)—C(4)—C(10)	118.29(19)
C(14)—C(4)—C(10)	99.45(19)
N(1)—C(1)—C(2)	126.23(16)
N(1)—C(1)—C(6)	116.27(16)
C(2)—C(1)—C(6)	117.49(15)
C(4)—C(5)—C(6)	107.65(16)
C(4)—C(5)—C(9)	110.04(19)
C(6)—C(5)—C(9)	108.73(17)
C(4)—C(5)—C(8)	112.55(17)
C(6)—C(5)—C(8)	109.41(18)
C(9)—C(5)—C(8)	108.4(2)
C(1)—C(6)—C(5)	112.11(17)
C(16)—C(13)—C(3)	112.8(2)
C(16)—C(13)—C(12)	115.0(2)
C(3)—C(13)—C(12)	98.57(19)
C(16)—C(13)—C(15)	109.1(3)
C(3)—C(13)—C(15)	110.3(2)
C(11)—C(10)—C(4)	103.3(2)
C(12)—C(14)—C(4)	94.6(2)
C(11)—C(12)—C(13)	111.4(3)
C(14)—C(12)—C(13)	103.1(2)
C(12)—C(11)—C(10)	103.6(2)