CN105669711A - 1,4-二甲基-2,5-二-1h-双三唑均苯四酸三维铜配合物单晶与应用 - Google Patents
1,4-二甲基-2,5-二-1h-双三唑均苯四酸三维铜配合物单晶与应用 Download PDFInfo
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- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000013078 crystal Substances 0.000 title claims abstract description 21
- 150000004699 copper complex Chemical class 0.000 title claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 150000003852 triazoles Chemical class 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000005260 alpha ray Effects 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- ZHOGHWVKKXUAPI-UHFFFAOYSA-N fluorooxy(phenyl)borinic acid Chemical compound FOB(O)C1=CC=CC=C1 ZHOGHWVKKXUAPI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- QXISTPDUYKNPLU-UHFFFAOYSA-N 2-bromo-1,4-dimethylbenzene Chemical compound CC1=CC=C(C)C(Br)=C1 QXISTPDUYKNPLU-UHFFFAOYSA-N 0.000 description 4
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- NLLGFYPSWCMUIV-UHFFFAOYSA-N (3-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC(B(O)O)=C1 NLLGFYPSWCMUIV-UHFFFAOYSA-N 0.000 description 2
- OQGUQRDSLVDCRT-UHFFFAOYSA-N (4-methylsulfanylphenoxy)boronic acid Chemical compound CSC1=CC=C(OB(O)O)C=C1 OQGUQRDSLVDCRT-UHFFFAOYSA-N 0.000 description 2
- IYWWVPFEBVKLBK-UHFFFAOYSA-N 1-[2,5-dimethyl-4-(1,2,4-triazol-1-yl)phenyl]-1,2,4-triazole Chemical compound CC1=C(C=C(C(=C1)N1N=CN=C1)C)N1N=CN=C1 IYWWVPFEBVKLBK-UHFFFAOYSA-N 0.000 description 2
- NSPMIYGKQJPBQR-CVMUNTFWSA-N 1h-1,2,4-triazole Chemical class [13CH]=1[15N]=[13CH][15NH][15N]=1 NSPMIYGKQJPBQR-CVMUNTFWSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- XLGLMVCAOMQNJT-UHFFFAOYSA-N boric acid;chlorobenzene Chemical compound OB(O)O.ClC1=CC=CC=C1 XLGLMVCAOMQNJT-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QENIALCDPFDFHX-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethylbenzene Chemical compound CC1=CC(Br)=C(C)C=C1Br QENIALCDPFDFHX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- 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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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
本发明公开了1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶及其制备方法与应用,其结构:[Cu(L)0.5(H2O)(pma)0.5],其中,L?=?1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;pma?=?均苯四酸。同时还公开了单晶的制备方法。它是采用常温挥发法,即L、pma和Cu(NO3)2·6H2O在水中搅拌半小时后过滤,滤液常温挥发两周后得到适合X-射线单晶衍射的蓝色块状晶体。其中L:pma:Cu(NO3)2·6H2O的摩尔比为1:1:1。本发明进一步公开了1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶专属性用于对氟苯硼酸生成4,4ˊ-二氟联苯的催化剂方面的应用。
Description
本发明得到天津市教委创新团队(TD12-5037)的资助。
技术领域
本发明属于有机和无机合成技术领域,涉及1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶[Cu(L)0.5(H2O)(pma)0.5]的制备方法及作为催化剂方面的应用,其中,L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;pma = 均苯四酸。
背景技术
1,2,4-三唑及其衍生物兼有吡唑和咪唑的配位特点,是配位能力较强的桥连配体,目前已合成并表征了大量的单核、多核和多维化合物。这些配体能够以1,2位上的氮原子与金属离子配位形成N1,N2-桥连模式,对于4位未取代的1,2,4-三唑衍生物能通过2,4位上的氮原子形成N2,N4-桥连模式,这种N2,N4-桥连模式同金属酶中咪唑的N1,N3-桥连模式类似。对于三唑类化合物的特殊用途还表现在分子器件化的设计上,合成具有不同维数的金属配合物乃是完成器件化至关重要的一步。
本发明即是采用常温挥发法,即L、pma和Cu(NO3)2·6H2O在水中搅拌半小时后过滤,滤液常温挥发两周后得到适合X-射线单晶衍射的蓝色块状晶体,结构为[Cu(L)0.5(H2O)(pma)0.5],其中,L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;pma= 均苯四酸。该配合物还可作为对氟苯硼酸生成4,4'-二氟联苯的催化剂得以应用。
发明内容
为此本发明人提供了如下的技术方案:
一种1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物的单晶,其特征在于该单晶结构采用APEX II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线,λ = 0.71073 Å为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出单晶数据:
其结构如下:
[Cu(L)0.5(H2O)(pma)0.5],其中
L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;
pma = 均苯四酸。
本发明进一步公开了1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶的制备方法,其特征在于它是采用常温挥发法,将L、pma和Cu(NO3)2·6H2O在水中搅拌半小时后过滤,滤液常温挥发两周后得到适合X-射线单晶衍射的蓝色块状晶体;其中L:pma:Cu(NO3)2·6H2O的摩尔比为1:1:1;
1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶的结构为[Cu(L)0.5(H2O)(pma)0.5];其中L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;pma= 均苯四酸;
L pma。
本发明更进一步公开了1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶专属性对氟苯硼酸生成4,4'-二氟联苯的催化剂得以应用,实验结果显示:
(1) 实施例2中的配合物单晶专属性对氟苯硼酸生成4,4'-二氟联苯的催化剂具有较好的催化效果,催化产率达到96%;
(2)配合物单晶对3-甲氧基苯硼酸、1-萘苯硼酸、4-甲硫基苯硼酸、4-氯苯硼酸、4-吡啶苯硼酸催化效果一般甚至不反应。
本发明公开的一种1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶所具有的优点和特点在于:
(1) 反应操作简便易行。
(2) 反应收率高,所得产品的纯度高。
(3)本发明所制备的1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶,生产成本低,方法简便,适合大规模生产。在催化对氟苯硼酸生成4,4'-二氟联苯方面具有良好的催化效果。
附图说明
图1:配合物单晶的晶体结构图;
图2:配合物单晶的三维结构图;
图3:4,4'-二氟联苯的1H NMR图。
具体实施方式
下面结合实施例对本发明做进一步的说明,实施例仅为解释性的,决不意味着它以任何方式限制本发明的范围。所用原料均有市售。所有原料都是从国内外的化学试剂公司进行购买,例如1,4-二溴-2,5-二甲基苯等原料,没有经过继续提纯而是直接使用的。
实施例1
1,4-二溴-2,5-二甲基苯:1H-1,2,4-三唑:碳酸钾:氧化铜的摩尔比为2:10:30:1
在装有磁子、回流冷凝器和温度计的50 mL三口圆底烧瓶内分别加入CuO (0.0398 mg,0.5 mmol),碳酸钾 (2.0731 g, 15 mmol),1H-1,2,4-三唑(0.345 mg, 5 mmol),1,4-二溴-2,5-二甲基苯 (0.3360 g, 1 mmol),20 mL DMF。开动搅拌在100 oC,反应24小时。反应结束后,将反应液降至室温,过滤,滤液加入100 mL水,析出大量沉淀,抽滤,收集滤饼,收率60%。元素分析(C12N6H12) 理论值(%):C,59.99;H,5.03;N,34.98。实测值:C,60.02;H,5.05;N,35.05;
1,4-二溴-2,5-二甲基苯 1H-1,2,4-三唑。
本发明优选1,4-二溴-2,5-二甲基苯:1H-1,2,4-三唑:碳酸钾:氧化铜的摩尔比为2:10:30:1;反应温度80-200℃,反应时间12-120小时。采用“一锅法”,将1,4-二溴-2,5-二甲基苯和1H-1,2,4-三唑在加热条件下制备该有机化合物,1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑(L)。
实施例2
1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑(L)(0.1mmol)、均苯四酸(pma) (0.1 mmol)和Cu(NO3)2·6H2O (0.1 mmol)在水 (10 mL)中搅拌半小时后过滤,滤液常温挥发两周后得到适合X-射线单晶衍射的蓝色块状晶体。产率:40%。元素分析(C22H16CuN6O8) 理论值(%):C,47.53;H,2.90;N,15.11。实测值:C,40.56;H,2.95;N,15.18。
实施例3
晶体结构测定采用APEX II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线,λ =0.71073 Å为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出晶体结构,并经洛仑兹和极化效应修正。所有的H原子由差值傅立叶合成并经理想位置计算确定。详细的晶体测定数据:
实施例4
专属性作为催化剂的实际例子
方法:将取代对氟苯硼酸(0.82 mmol)和碳酸铯(0.01 g)溶解在3 mL DMF中,加入5 mg催化剂,室温下搅拌5小时,CH2Cl2萃取,水洗,干燥,过滤,脱溶,粗产品经石油醚/乙酸乙酯混合液(v:v = 1:1)经硅胶层析柱洗脱得到产品。
结果:得到4,4'-二氟联苯0.0756 g,计算得到的催化产率为97%。
实施例5
结论:
(1) 1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物对于催化底物4-甲硫基苯硼酸不起任何催化作用。
(2)1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物对于3-甲氧基苯硼酸、1-萘苯硼酸、4-氯苯硼酸、4-吡啶苯硼酸的催化效果一般,催化产率在2-9%之间。
(3)1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物对于催化底物4-氟苯硼酸的催化效果最好,催化产率高达97%。
在详细说明的较佳实施例之后,熟悉该项技术人士可清楚地了解,在不脱离上述申请专利范围与精神下可进行各种变化与修改,凡依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均属于本发明技术方案的范围。且本发明亦不受说明书中所举实例实施方式的限制。
Claims (3)
1.一种1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物的单晶,其特征在于该单晶结构采用APEX II CCD单晶衍射仪,使用经过石墨单色化的Mokα射线,λ = 0.71073 Å为入射辐射,以ω-2θ扫描方式收集衍射点,经过最小二乘法修正得到晶胞参数,从差值傅立叶电子密度图利用软件解出单晶数据:
其结构如下:
[Cu(L)0.5(H2O)(pma)0.5],其中
L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;
pma = 均苯四酸。
2.权利要求1所述1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶的制备方法,其特征在于它是采用常温挥发法,即L、pma和Cu(NO3)2·6H2O在水中搅拌半小时后过滤,滤液常温挥发两周后得到适合X-射线单晶衍射的蓝色块状晶体,其中L:pma:Cu(NO3)2·6H2O的摩尔比为1:1:1;
1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶的结构为[Cu(L)0.5(H2O)(pma)0.5];其中L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑;pma= 均苯四酸;
L pma。
3.权利要求1所述1,4-二甲基-2,5-二-1H-双三唑均苯四酸三维铜配合物单晶专属性对氟苯硼酸生成4,4'-二氟联苯的催化剂方面的应用。
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