CN114907279A - 一种n-氧苯丙三氮唑的合成方法 - Google Patents
一种n-氧苯丙三氮唑的合成方法 Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000012964 benzotriazole Substances 0.000 claims abstract description 33
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- DTXVEMGTMOSWBL-UHFFFAOYSA-N OC1(CC=CC=C1)C=1N=NNC1 Chemical compound OC1(CC=CC=C1)C=1N=NNC1 DTXVEMGTMOSWBL-UHFFFAOYSA-N 0.000 description 3
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- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
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- LGROKZMEHJZWDU-UHFFFAOYSA-N n-amino-n-phenylnitramide Chemical compound [O-][N+](=O)N(N)C1=CC=CC=C1 LGROKZMEHJZWDU-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- 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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Abstract
本发明公开了一种N‑氧苯丙三氮唑的合成方法。本发明以30%的双氧水为氧化剂,钨酸钠为催化剂,在相转移催化苄基三乙基氯化铵和酸性条件下,研究了苯并三氮唑氧化制N‑氧苯丙三氮唑的反应。本发明意料之外的发现较佳反应条件为钨酸钠∶苄基三乙基氯化铵∶苯并三氮唑∶30%的双氧水的物质的量比为1.6∶1.1∶50∶688,梯度升温,最后在95℃下反应6h,制得75.3%的N‑氧苯丙三氮唑。该合成方法具有操作简便、能耗小、绿色环保等优点,该产品的合成方法以及产物的定性定量对于氧化法降解苯并三氮唑产物具有重要意义,同时该产物可作为水处理剂、金属防锈剂和腐蚀抑制剂等使用,也用于医药、农药、涂料、染料以及紫外光稳定剂等多个领域。
Description
技术领域
本发明属于苯并三氮唑的制备领域,具体涉及一种N-氧苯丙三氮唑的合成方法。
背景技术
苯并三氮唑是一种重要的精细化工产品。它的用途很广,主要作为水处理剂以及金属 防锈防腐剂,润滑油添加剂,机场除霜防冻剂,抗紫外线材料稳定剂,泡沫塑料稳定剂和 抗紫外线材料的稳定剂,照相防雾剂,高分子材料稳定剂,植物生长调节剂等;它也是一种重要的有机合成中间体,在有机合成和新药合成领域备受关注,用于医药、农药及染料等多个领域。
在进行苯并三氮唑污水处理过程中,氧化产物的确定对于后续的有机物含量的确定非 常重要。现有技术表明,高效液相色谱图中得知有新的中间体产物生成,且没有进行产物 的进一步分析;另外,现有技术在进行Fenton试剂强化超声-光催化降解苯并三氮唑的研 究中也指出,降解过程中生产有色的中间体产物尚未确定。
N-氧苯丙三氮唑是苯并三氮唑上N3原子上引入氧原子,是1-羟基苯丙三氮唑的互变 异构体,也是重要的化工产品和中间体,在水溶液中稳定存在,在有机溶剂中则是以1-羟 基苯丙三氮唑形式存在,其合成方法主要是采用邻硝基氯苯法,邻氯硝基苯和过量的水合 肼反应制得。其互变异构体1-羟基苯丙三氮唑的合成的除了邻硝基氯苯法外,还有邻硝基 苯肼法,上述方法存在着高压、原料有限、水合肼回收困难等问题。
为解决这类问题,本发明以苯并三氮唑为原料,以钨酸钠和相转移催化剂苄基三乙基 氯化铵联合催化,双氧水为氧化剂得到了该化合物N-氧苯丙三氮唑(如图1所示),通过 高效液相色谱紫外联用法进行了定性,同时进行了晶体结构的测定和表征。
发明内容
为了克服现有技术中存在的不足,以及氧化法处理苯并三氮唑产物的确定,本发明提 供以苯并三氮唑为原料,以钨酸钠和相转移催化剂苄基三乙基氯化铵联合催化,双氧水为 氧化剂得到了该化合物N-氧苯丙三氮唑。
为实现上述目的,本发明公开了一种N-氧苯丙三氮唑的合成方法,具体如下:
在装有电动搅拌器的烧瓶中,依次加入苯并三氮唑、钨酸钠二水合物、苄基三乙基氯 化铵、稀硫酸和,搅拌溶解后,室温反应0.5-2h,缓慢加热,控制气泡产生的速度,在40~50℃反应1-3h,再将温度升至90-100℃反应3-8h,冷却,反应液倾入烧杯中放置,析出 粉末,抽滤,用少量冷水洗涤,乙醇重结晶得白色晶体,真空干燥,得N-氧苯丙三氮唑。
具体的,在装有电动搅拌器的三口烧瓶中,依次加入苯并三氮唑、钨酸钠二水合物、 苄基三乙基氯化铵、稀硫酸和,搅拌溶解后,室温反应1h,缓慢加热,控制气泡产生的速度,在40~50℃反应2h,再将温度升至95℃反应6h,冷却,反应液倾入烧杯中在冰箱 中放置过夜,析出类白色粉末,抽滤,用少量冷水洗涤,乙醇重结晶得白色晶体,真空干 燥,得N-氧苯丙三氮唑5.77g(收率75.3%),测得熔点为158-161℃;
晶体结构表征:取乙醇水溶液重结晶产物,采用挥发溶剂法得到适合单晶测试的晶体, 晶体结构分析表明,N-氧苯丙三氮唑分子N3原子上的氢与水分子的氧形成氢键,苯环、 三氮唑环、氧化的氧原子和水分子的氧在同一个平面内,然后该结构通过芳环堆积形成三 维结构;
其中,所述的苯并三氮唑的用量为5.96g,即50mmol;
其中,所述的钨酸钠二水合物的用量为0.52g,即1.6mmol;
其中,所述的苄基三乙基氯化铵的用量为0.25g,即1.1mmol;
其中,所述的稀硫酸的用量为20ml;
其中,所述的30%H2O2的用量为160ml,688mmol;
其中,反应工艺条件为钨酸钠∶苄基三乙基氯化铵∶苯并三氮唑∶30%的双氧水的物 质的量比为1.6∶1.1∶50∶688,梯度升温,最后在95℃下反应6h,得到N-氧苯并三氮唑 精制收率为75.3%。
本发明的有益效果
(1)本发明以苯并三氮唑为原料,以钨酸钠和相转移催化剂苄基三乙基氯化铵联合 催化,双氧水为氧化剂得到了N-氧苯丙三氮唑,创新了合成方法。本合成方法与现有的邻 硝基氯苯法、邻硝基苯肼法相比各个方面都有着很强优越性,回避了大量水合肼的回收和 硝基苯肼来源有限和高温高压的弊端。该方法采用绿色氧化剂双氧水氧化,不高温高压, 不使用有机溶剂、方法简单,反应条件温和,操作简便易行,成本低等绿色化学所要求的 特点。
(2)该合成工艺中的催化剂类型、反应温度、反应时间都对合成结果具很大的影响, 本发明的的反应条件为申请人意料之外的发现。
(3)本发明制备的了N-氧苯丙三氮唑可用于染料,相比于现有染料产品,具有突出的优势。
附图说明
附图1为本发明的N-氧苯丙三氮唑合成示意图。
附图2为N-氧苯丙三氮唑分子结构;
附图3为N-氧苯丙三氮唑的堆积图;
附图4为产品的HPLC和紫外吸收光谱图
具体实施方式
下面结合附图对本发明作更进一步的说明。
主要仪器与试剂:FT–IR仪(美国Nicolet公司EXUS670型);400MHz核磁共振仪(CDCl3为溶剂,TMS为内标,德国Bruker公司);APEX CCD II型单晶衍射仪(BIUKER 公司);高效液相色谱(美国Agilent科技Agilent1260);钨酸钠二水合物、苄基三乙基氯 化铵(分析纯,阿拉丁试剂有限公司);双氧水[ω(H2O2)=30.0%],苯丙三氮唑,工业 品。
实施例1 N-氧苯丙三氮唑的合成方法
在装有电动搅拌器的250mL三口烧瓶中,依次加入苯并三氮唑(5.96g,50mmol)、钨酸钠二水合物(0.52g,1.6mmol)、苄基三乙基氯化铵(0.25g,1.1mmol)、稀硫酸20ml 和30%H2O2(160ml,688mmol),搅拌溶解后,室温反应1h,缓慢加热,控制气泡产生 的速度,在40~50℃反应2h,再将温度升至95℃反应6h,冷却,反应液倾入烧杯中在 冰箱中放置过夜,析出类白色粉末,抽滤,用少量冷水洗涤,乙醇重结晶得白色晶体,真 空干燥,得N-氧苯丙三氮唑5.77g(收率75.3%),测得熔点为158-161℃(文献值:159~ 161℃)。
实施例2产品定性
采用高效液相色谱法,水相采用磷酸二氢钾2.72g,加水950ml使溶解,用磷酸调节pH值为2.5,用水定容至1000ml,过滤。将氧化产物按照文献色谱条件进行测定,利用紫 外-可见检测器(DAD检测器)于200-400nm范围内进行全波长扫描,动态地快速扫描被 测组分的紫外-可见吸收光谱图,与文献图谱进行对照,将产品进行定性。
实施例3晶体结构表征
取乙醇水溶液重结晶产物,采用挥发溶剂法得到适合单晶测试的晶体。取0.50mm× 0.30mm×0.20mm的单晶,放置在APEX CCD II型单晶衍射仪上收集衍射数据,采用 MoK射线为光源,在2.92≤θ≤27.3范围内以ω/2θ扫描方式,在室温(298.0K) 下共收集到6797个数据,其中独立衍射649个(R(int)0.062),1574个(I>2σ(I)) 可观察衍射点。全部非氢原子和氢原子采用直接法获得,偏差因子R1=0.054,ωR2=0.112, 确定该化合物为N-氧苯丙三氮唑一水合物,分子式为C6H7N3O2,单斜晶系,P21/c空间 群,a=1.03694(8)nm,b=0.95365(8)nm,c=0.71170(6)nm,α=90°,β=98.871(6)°, γ=90°,Z=4,V=6.9537(10)nm3,Dz=1.463g/cm3,μ(Mo Kα)=0.113mm-1,F(000)=320。 该发明化合物晶体学数据见表1,分子结构和堆积图分别见图2和图3。
表1
晶体结构分析表明,N-氧苯丙三氮唑分子N3原子上的氢与水分子的氧形成氢键,苯环、 三氮唑环、氧化的氧原子和水分子的氧在同一个平面内,然后该结构通过芳环堆积形成三 维结构。
本发明以苯并三氮唑为原料,以钨酸钠和相转移催化剂苄基三乙基氯化铵联合催化, 双氧水为氧化剂得到了N-氧苯丙三氮唑,创新了合成方法。本合成方法与现有的邻硝基氯 苯法、邻硝基苯肼法相比各个方面都有着很强优越性。该方法采用绿色氧化剂双氧水氧化, 不高温高压,不使用有机溶剂、方法简单,反应条件温和,操作简便易行,成本低等绿色 化学所要求的特点。
该合成工艺,催化剂类型、反应温度、反应时间都有明显的影响。本实验较佳的反应 工艺条件为钨酸钠∶苄基三乙基氯化铵∶苯并三氮唑∶30%的双氧水的物质的量比为1.6∶ 1.1∶50∶688,梯度升温,最后在95℃下反应6h,得到N-氧苯并三氮唑精制收率为75.3%。
实施例4产品的定性
从附图4中可以看出,比移值在23.491处的峰的紫外光谱扫描结果为未反应的原料 苯并三氮唑,与浙江工业大学吴成强教授指导的边康玲团队在进行超声-紫外协同强化双氧水降解苯并三氮唑的研究中报道一致。在2.861左右出现一个较大的峰的紫外光谱 扫描结果则为N-氧苯丙三氮唑,与Boyle学者团队所测得在水溶液中的紫外吸收光谱图 形一致。
实施例5产品的晶体结构
采用挥发溶剂法得到单晶,进行X射线衍射测定的表征,结果表明,确定该化合物为 N-氧苯丙三氮唑一水合物,分子式为C6H7N3O2,分子量为153.15,a=1.03694(8)nm, b=0.95365(8)nm,c=0.71170(6)nm,α=90°,β=98.871(6)°,γ=90°,属于单斜 晶系P21/c空间群。
以上所述仅是本发明的优选实施方式,应当指出:对于本技术领域的普通技术人员来 说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视 为本发明的保护范围。
Claims (5)
1.一种N-氧苯丙三氮唑的合成方法,其特征在于,具体步骤如下:在装有电动搅拌器的烧瓶中,依次加入苯并三氮唑、钨酸钠二水合物、苄基三乙基氯化铵、稀硫酸和,搅拌溶解后,室温反应0.5-2h,缓慢加热,控制气泡产生的速度,在40~50℃反应1-3h,再将温度升至90-100℃反应3-8h,冷却,反应液倾入烧杯中放置,析出粉末,抽滤,用少量冷水洗涤,乙醇重结晶得白色晶体,真空干燥,得N-氧苯丙三氮唑。
2.一种如权利要求1所示的N-氧苯丙三氮唑的合成方法,其特征在于,具体步骤如下:在装有电动搅拌器的三口烧瓶中,依次加入苯并三氮唑、钨酸钠二水合物、苄基三乙基氯化铵、稀硫酸和,搅拌溶解后,室温反应1h,缓慢加热,控制气泡产生的速度,在40~50℃反应2h,再将温度升至95℃反应6h,冷却,反应液倾入烧杯中在冰箱中放置过夜,析出类白色粉末,抽滤,用少量冷水洗涤,乙醇重结晶得白色晶体,真空干燥,得N-氧苯丙三氮唑5.77g(收率75.3%),测得熔点为158-161℃。
3.一种如权利要求1-2所述的N-氧苯丙三氮唑的合成方法制备得到的N-氧苯丙三氮唑的晶体结构表征方法:取乙醇水溶液重结晶产物,采用挥发溶剂法得到适合单晶测试的晶体,晶体结构分析表明,N-氧苯丙三氮唑分子N3原子上的氢与水分子的氧形成氢键,苯环、三氮唑环、氧化的氧原子和水分子的氧在同一个平面内,然后该结构通过芳环堆积形成三维结构。
4.如权利要求1-2所述的N-氧苯丙三氮唑的合成方法,其特征在于,
其中,所述的苯并三氮唑的用量为5.96g,即50mmol;
其中,所述的钨酸钠二水合物的用量为0.52g,即1.6mmol;
其中,所述的苄基三乙基氯化铵的用量为0.25g,即1.1mmol;
其中,所述的稀硫酸的用量为20ml;
其中,所述的30%H2O2的用量为160ml,688mmol。
5.如权利要求1-2所述的N-氧苯丙三氮唑的合成方法,其特征在于,
其中,反应工艺条件为钨酸钠∶苄基三乙基氯化铵∶苯并三氮唑∶30%的双氧水的物质的量比为1.6∶1.1∶50∶688,梯度升温,最后在95℃下反应6h,得到N-氧苯并三氮唑精制收率为75.3%。
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