催化加氢合成6-氨基-7-氟-2H-1,4-苯并口恶嗪-3(4H)-酮

6-氨基-7-氟-2H-1,4-苯并口恶嗪-3(4H)-酮(Ⅱ)是合成除草剂丙炔氟草胺的关键中间体,该文采用雷尼镍催化加氢还原7-氟-6-硝基-2H-1,4-苯并口恶嗪-3(4H)-酮(Ⅰ)高收率的制得了目标化合物Ⅱ,确定了最佳合成工艺条件:反应温度80℃,反应时间5 h,催化剂用量为原料质量的5%,氢气压力6 MPa,产品的收率95.2%,质量分数98.5%,溶剂和催化剂循环使用5次,对收率和产品质量分数无影响。产品结构经元素分析、红外光谱、核磁共振确证。     

雷尼镍催化加氢合成7-氟-2H-1,4苯并噁嗪-3(4H)-酮

研究了雷尼镍为催化剂加氢还原2-(5-氟-2-硝基苯氧基)乙酸甲酯(1)合成7-氟-2H-[1,4]苯并噁嗪-3(4H)-酮(2)的方法,使还原、合环一次完成。考察了反应温度、催化剂、氢气压力、时间、溶剂及回收的催化剂和溶剂对反应收率的影响,确定了合成工艺条件:反应温度70℃,反应时间4h,催化剂用量为原料质量的5%,氢气压力5MPa,溶剂甲醇用量为1000mL/mol1。产品的收率92.4%,含量98%,溶剂和催化剂循环使用4次,对收率无影响。产品结构经元素分析、红外光谱、核磁共振确证。     

6-氨基-7-氟-2H-1,4-苯并(噁)嗪-3(4H)-酮的高效液相色谱法测定

叙述了采用反向高效液相色谱法,以甲醇为溶剂,甲醇与水(体积比65∶35)为流动相,ODS为填料和紫外检测器分离测定6-氨基-7-氟-2H-1,4-苯并嗪-3(4H)-酮。该方法的标准偏差为0.29,变异系数为0.32%,回收率为99.85%,线性关系系数为0.9997。     

7-氟-6-胺基-2H-1,4-苯并恶嗪-3(4H)-酮的合成

由1，5-二氟-2，4-二硝基苯为原料经醚化、还原合成7-氟-6-胺基-2H-1，4-苯并恶嗪-3(4H)-酮，产率为66.3％(以1，5-二氟-2，4-二硝基苯计)，产物经IR,^1HNMR证实了结构。该化合物是合成除草剂丙炔氟草胺(Flumioxaxin)的关键中间体。     

6-氨基-7-氟-2件1，4-苯并嗯嗪-3（4H）-酮的高效液相色谱法测定

叙述了采用反向高效液相色谱法，以甲醇为溶剂，甲醇与水（体积比65：35）为流动相，ODS为填料和紫外检测器分离测定6-氨基-7-氟-2H-1，4-苯并曝嗪-3（4H）-酮。该方法的标准偏差为0．29，变异系数为0．32％，回收率为99．85％，线性关系系数为0．9997。     

2H-1,4-苯并噁嗪类化合物合成研究进展

综述了不同取代基的2H-1,4-苯并噁嗪类化合物的合成方法。可以概括为两大类,其一以邻胺基苯酚或间卤苯酚为原料,与不同的-α卤代酸或酯反应,反应中不需要催化剂,在工业生产中普遍采用;另一类是用钯作催化剂,能扩大化合物的类型,并可选择性合成光学活性物质。     

2H-1,4-苯并噁嗪衍生物的合成研究

2H-1,4-苯并噁嗪类化合物存在于许多天然产物中,具有广泛的生物活性,可用作高分子材料和农药、医药的中间体。笔者合成了5个2H-1,4-苯并噁嗪衍生物,其结构经1H NMR谱、MS谱等方法确证。其中N-[2-（2-苯基-3-氧代-2H-1,4-苯并噁嗪-6-基）乙基]乙酰胺（I）为未见文献报导的新化合物。     

硝基-3-氧-3，4-二氢-2H-[1，4]苯并噁嗪-6-羧酸的合成

以4-羟基-3-硝基苯甲酸为原料,经酯化、醚化、还原合环、硝化、水解等5步反应,合成了两个未见文献报导的化合物7-硝基-3-氧-3,4-二氢-2H-[1,4]苯并噁嗪-6-羧酸和8-硝基-3-氧-3,4-二氢-2H-[1,4]苯并嗪-6-羧酸,其结构经IR、LC/MS、1HNMR和元素分析确证。     

4-(芳氨基甲酰甲基)-1,4-苯并噁嗪类化合物的合成

利用3,4-二氢-1,4-苯并噁嗪(2)和氯乙酰芳胺经N-烷基化反应合成了4-(芳氨基甲酰甲基)-1,4-苯并噁嗪类衍生物1a～1h.研究了溶剂、温度及反应时间对反应的影响,优化条件下,收率达50％～70％.用IR、1H NMR、13C NMR等对产物的结构进行了表征.     

3-甲基-7-二正丙氨基-1,4-氧氮杂萘-2-酮的合成

以间氨基酚为原料,经N 烷基化、亚硝化,制得2 亚硝基 5 二正丙氨基苯酚,其收率为91 6%。该化合物经还原、成环反应后,合成出3 甲基 7 二正丙氨基 1,4 氧氮杂萘 2 酮,其收率为80 3%。实验确定1 溴丙烷、亚硝酸钠及丙酮酸乙酯的最佳用量分别为70mL、11 5g和2mL(以15g间氨基酚为基准)。     

4-氨基-6-特丁基-3-巯基-1,2,4-三嗪-5(4H)-酮高效液相色谱定量分析方法

建立了一种采用高效液相色谱法测定4-氨基-6-特丁基-3-巯基-1,2,4-三嗪-5(4H)-酮含量的分析方法。采用C18色谱柱,以乙腈+水(体积比为2∶3)为流动相,流速为1.0 mL/min,柱温为28℃,检测波长为285 nm。方法的线性相关系数为1.0000,标准偏差为0.1389,平均回收率为99.70%。方法具有简便、快速、分离效果好、精密度和准确度高、线性相关性好的特点。     

Toxicokinetics of 2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA) in the European corn borer,Ostrinia nubilalis (Hübner)

2,4-Dihydroxy-7-methoxy-1,4-benzoxazin-3-one (DIMBOA), the major hydroxamic acid present in corn, and its tritiated derivative, were prepared synthetically for use in the determination of the toxicokinetics of this insect deterrent in the European corn borer (ECB),Ostrinia nubilalis. In growth studies with DIMBOA (0, 0.05, 0.2, and 0.5 mg/g diet), the mean time to pupation and adult emergence were significantly lengthened by an increase in concentration. Pupal and adult weights, for both female and male, decreased with an increase in concentration. Increased larval and pupal mortality occurred at the highest concentration of DIMBOA. DIMBOA, at concentrations of 0.2 and 0.5 mg/g diet, resulted in a decrease in the number of egg masses produced per female, and at 0.5 mg/g diet, in a decrease in the number of eggs per egg mass. Larvae fed from the neonate stage on a diet containing 0.2 mg [³H]- + [¹H]DIMBOA/g diet showed an increase in the content of label from fourth to fifth instar, but levels declined at pupation and emergence. A large amount of the labeled compounds was excreted by the insect in the pupal case. In dose-related studies, both uptake and excretion increased with an increase in concentration of DIMBOA (0.05, 0.2, 0.4 mg/g diet), while a body burden (concentration in the tissues/concentration in the frass) of approximately 0.25 was maintained for all concentrations. At the highest dose of DIMBOA (0.4 mg/g), the ECB increased consumption, possibly to compensate for the toxic effects of the compound. In topical application studies, elimination of the labeled compound in the frass was rapid, reaching 65% by 4 hr and 88% by 48 hr. Accumulation of label in tissues other than hemolymph was low. The results show that the ECB does possess adaptive mechanisms to deal with the effects of this host-derived compound.     

铝催化7-氯-6-氟-1,4-二氢-4-氧喹啉-3-羧酸乙酯的合成

以Al为催化剂,在微波辐射条件下,由3-氯-4-氟苯胺基甲叉丙二酸二乙酯环合制备标题化合物。通过优化实验得到最佳反应条件为:微波功率160 W、反应温度80℃、反应时间20 min,在该条件下目标物产率达94.2%。对产物进行了熔点、NMR测定,确定为目标产物。