二环[2.2.1]庚烷-2,3-二羧酸二钠的合成及表征

以用量为原料质量24.33％的380～830?μm的Raney?Ni为催化剂,在常温常压条件下对二环[2.2.1]庚-5-烯-2,3-二羧酸二钠进行加氢,反应时间90?min,得到聚丙烯成核剂二环[2.2.1]庚烷-2,3-二羧酸二钠,收率达90％以上.在同样条件下,将50％(w)的再生催化剂与50％(w)的新鲜催化剂...     

PP成核剂中间体二环[2.2.1]庚-5-烯-2,3-二酸酐的合成

以环戊二烯与顺丁烯二酸酐为原料,通过Diels-Alder反应合成了聚丙烯成核剂中间体二环[2.2.1]庚-5-烯-2,3-二酸酐。通过实验确定了合成二环[2.2.1]庚-5-烯-2,3-二酸酐的优化条件为:顺丁烯二酸酐与环戊二烯摩尔比1.000∶1.050;溶剂石油醚与乙酸乙酯等体积混合,溶剂用量占进料总质量的46%;环戊二烯滴加温度控制在10～15℃,滴加30 min;升至60℃,继续反应20 min。在优化条件下,二环[2.2.1]庚-5-烯-2,3-二酸酐的收率大于95%。熔点、元素分析、红外光谱及X射线衍射分析均表明合成产物为目标产物。     

二环[2.2.1]/[2.2.2]庚烷二羧酸盐成核剂研究及应用进展

二环[2.2.1]庚烷二羧酸盐和二环[2.2.2]庚烷二羧酸盐是重要的分散型聚丙烯成核剂,HPN-68是最优秀的商业化产品。该类成核剂最大的特点是可以提高聚丙烯的结晶温度和改性PP收缩的各向同性。详细介绍了该类成核剂的结构、制备方法和在聚丙烯中的应用。     

2,3-二羧基-双环[2.2.1]2,5-庚二烯价键异构化反应的研究

以聚四苯基卟啉(P-TPP)为敏化剂,研究了2,3-二羧基-双环[2.2.1]-2,5-庚二烯(N)的光化学价键异构化反应,在0.1mol/L的碳酸钠甲醇溶剂中,在适量的P-TPP存在下,可见光照射时,N可以定量地转化为2,3-二羧基四环[2.2.1.0~(2,6).0~(3,5)]庚烷(Q),Q在聚四苯基卟啉钴络合物(Co-P-TPP)催化剂的作用下,又可定量地异构化返回N.分别研究了敏化剂和催化剂用量对反应的影响.通过反应物之间激发态能量的比较及N对P-TPP荧光的猝灭试验,证明光异构化反应是通过电子转移反应机制进行的.     

N-对甲苯磺酰基-7-氮杂-双环[2.2.1]-2,5-庚二烯-2,3-二羧酸二甲酯光敏化电子转移异构反应研究

降冰片二烯及其衍生物是分子光化学贮存太阳能反应体系中研究较多的一类模型化合物。但是,从迄今报道的研究工作来看,大部分是关于7-位为碳原子的降冰片二烯衍生物。对于7-位为杂原子的衍生物的光异构化反应以及7-位杂原子对光异构化反应的影响还未见报道。为此,我们以7-位为N原子的降冰片二烯衍生物N-对甲苯磺酰基-     

3-[4-(甲基磺酰基)-2-氯苯甲酰基]双环[3.2.1]辛烷-2,4-二酮的合成研究

标题化合物是合成稻田除草剂的中间体,以降冰片烯为原料,经二氯卡宾的加成、扩环反应和水解反应生成3-氯双环[3.2.1]-3-辛烯-2-醇;随后烯丙醇氧化制得α,β-不饱和酮;接着在氰化钾催化剂的作用下和氢氧化钠反应,得到双环[3.2.1]辛烷-2,4-二酮;最后再发生酰基化反应得到标题化合物。化合物结构用1HNMR、13CNMR表征,纯度用HPLC确定。     

季铵盐催化合成7,7-二氯双环[4.1.0]庚烷

研究了季铵盐A-1催化二氯卡宾与环己烯的加成反应,考察了不同相转移催化剂的催化活性、反应温度、催化剂用量、反应时间对产物7,7-二氯双环[4.1.0]庚烷收率的影响.在优化反应条件(即反应温度为50C,反应时间为5 h)下,以季铵盐A-1为相转移催化剂,产率可达94.0%.实验证明,季铵盐A-1的催化活性要优于其他短碳链的季铵盐和聚乙二醇,并且在分离过程中不乳化,使产物易于分离纯化.     

N-Boc-6-氨基-3-苄基-3-氮杂双环[3.2.1]辛烷的合成

以降冰片烯-2-酰胺为原料,经霍夫曼降解、氨基保护、双键臭氧化、苄胺的还原氨化等反应合成N-Boc-6-氨基-3-苄基-3-氮杂双环[3.2.1]辛烷,通过对关键步骤的优化,总收率达到55.3％.该方法简单,操作容易且收率较高.     

5—降冰片烯—2,3—二羧酸单甲酯的合成

由双环戊二烯热解制得的环戊二烯与顺丁烯二酸酐反应得５－降冰片烯－２,３－二酸酐（ＮＡ）,再单甲酯化制得５－降冰片烯－２,３－二羧酸单甲酯（ＮＥ）,产品收率可达５．６２％,左右,纯度≥９７％。     

阿巴卡韦中间体2-杂氮双环[2,2,1]庚-5-烯-3-酮的合成

采用一步法由对甲基苯亚磺酸钠与氯化氰及1,3-环戊二烯合成目标物2-杂氮双环[2,2,1]庚-5-烯-3-酮。反应条件为:n(对甲基苯亚磺酸钠)∶n(氯化氰)∶n(1,3-环戊二烯)=0.48∶1.05∶1,反应温度控制在15℃,反应7h,反应中控制pH=5,可得纯度为95%的产品,收率由文献报道的64%提高到78%。     

The effect of bicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboxylate on the mechanical properties and crystallization behaviors of isotactic polypropylene

The mechanical and optical properties of iPP nucleated with bicyclo[2.2.1]heptenedicarboxylate salts (BCHED) have been investigated. The results showed that aluminum bicyclo[2.2.1]heptenedicarboxylate (BCHE13) is the most effective nucleating agent to improve the mechanical and optical properties. Then the effects of the BCHE13 concentration on mechanical and optical properties and crystallization behaviors were studied. The results indicated that the saturated concentration of BCHE13 is about 0.2 wt %, at which nucleated iPP showed the better comprehensive mechanical and optical properties and high crystallization peak temperature. Nonisothermal crystallization kinetics of iPP nucleated with different BCHE13 contents have been investigated by Caze method. The results indicated Avrami exponents of nucleated iPP gradually increased with the increasing of BCHE13 concentration. The results can be explained that crystallization and growth model of nucleated iPP is heterogeneous nuclei followed by more than three‐dimension spherical growth during nonisothermal crystallization, which can be proved by agglomeration of BCHE13 in melt iPP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

5-氨基-1,4-苯并二恶烷盐酸盐的合成

以2,3-二羟基苯甲酸为原料,经酚羟基烷基化保护、羧酸叠氮化、Curtius重排、水解成盐四步反应以35%的总收率合成了5-氨基-1,4-苯并二恶烷盐酸盐,其结构经1H-NMR确认。由于合理的反应溶剂选择和反应温度控制,减少了副反应的发生、简化了工艺操作、降低了分离难度、提高了收率和产品纯度,使得该路线适合于工业化生产。     

3,4-二甲基-2,5-二甲酸乙酯噻吩[2,3-b]并噻吩选择性酰肼化

以乙酰丙酮和二硫化碳为原料合成出3,4-二甲基-2,5-二甲酸乙酯噻吩,它在不同溶剂中与过量水合肼反应,得到不同的产物:在乙醇中回流24 h,以66%的产率得到单酰肼化产物3,4-二甲基-噻吩[2,3-b]并噻吩-2-甲酸乙酯-5-甲酰肼;以DMF为溶剂80℃反应得到的主要产物是3,4-二甲基-2,5-噻吩[2,3-b...     

Pyrido[2,3-d]pyrimidine-2,7-dithiol in heterocyclic synthesis: Synthesis and characterization of several new fused pyridopyrimidine heterocycles

Pyridine-2(1H)-thione 1 reacted with phenyl isothiocyanate to give pyrido[2,3-d]pyrimidine derivative 3. Compound 3 reacted with halogen containing compounds 4a–d and methyl iodide in dimethylformamide/potassium hydroxide solution at room temperature to give 2,7-bisalkylthiopyrido[2,3-b]pyrimidine derivatives 5a–d and 9, respectively. Compounds 5a–d could be cyclized into thienopyrido[2,3-d]pyrimidine derivatives 6a–d by boiling with ethanolic potassium hydroxide solution. Compound 6a reacted with acetic anhydride or formic acid and gave the corresponding pyrimido[4″,5″:4′,5′]thieno[3′,2′:5,6]pyrido[2,3-d]pyrimidine derivatives 8a,b. Compound 9 reacted with hydrazine hydrate to yield pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine derivative 11 which could be reacted with nitrous acid and dimethylformamide-dimethylacetal (DMF-DMA) and gave the final isolable products corresponding to the pyrazolo[4′,3′:5,6]pyrido[2,3-d]tetrazolo-[5,1-b]pyrimidine and pyrimido[1″,2″:1′,5′]pyrazolo[4′,3′:5,6]pyrido[2,3-d]1 Abbas, A. A., Elneairy, M. A.A. and Mabkhot, Y. N. 2001. J. Chem. Res.(S), 4: 124[Crossref] , [Google Scholar] 2 Riad, B. Y., Negem, A. M., Abdou, S. E. and Daboun, H. A. 1987. Heterocycles, 26: 205[Crossref], [Web of Science ®] , [Google Scholar] 4 Gad-Elkareem, M. A.M. and Abedelhamid, A. O. 2004. Afinidad, 61(513): 427[Web of Science ®] , [Google Scholar]triazolo-[4,3-b] pyrimidine derivatives 13 and 17, respectively. Compound 11 also reacted with some β-dicarbonyl compounds such as acetylacetone (18) and ethyl acetoacetate (20) to yield the corresponding pyrimido[1″,2″:1′,5′]pyrazolo[4′,3′:5,6]pyrido[2,3-d]pyrimidine derivatives 19 and 21, respectively. Finally, compound 11 reacted with chloroacetyl chloride (22) to give the corresponding imidazo[1″′,2″′:1″,5″]pyrazolo[4″,3″:5′,6′]pyrido[3′,2′:5,6]pyrimido[2,1-c]1 Abbas, A. A., Elneairy, M. A.A. and Mabkhot, Y. N. 2001. J. Chem. Res.(S), 4: 124[Crossref] , [Google Scholar] 2 Riad, B. Y., Negem, A. M., Abdou, S. E. and Daboun, H. A. 1987. Heterocycles, 26: 205[Crossref], [Web of Science ®] , [Google Scholar] 4 Gad-Elkareem, M. A.M. and Abedelhamid, A. O. 2004. Afinidad, 61(513): 427[Web of Science ®] , [Google Scholar]triazine derivative 23.     

A Rapid and Highly Efficient Microwave-Promoted Four-Component Domino Reaction for the Synthesis of Novel Spiro[benzo[a]chromeno[2,3-c]phenazine] Derivatives Under Solvent-Free Conditions

p-Toluenesulfonic acid was applied as an efficient, non-toxic and solid acid catalyst for the one-pot, four-component condensation between 2-hydroxy-1,4-naphthoquinone, benzene-1,2-diamine, cyclic 1,3-dicarbonyl compounds and isatin or ninhydrin to afford the corresponding novel spiro[benzo[a]chromeno[2,3-c]phenazine] derivatives via a new two-step domino protocol under conventional heating and microwave irradiation. This solvent-free process produces biologically considerable heterocycles with the formation of five new bonds (two C–C, two C?N, and one C–O) and two new rings in a single operation and this effective green process provides considerable advantages such as: operational simplicity, very short reaction time, high yields, absence of any tedious process or purification, and it avoids hazardous reagents/solvents.     

四氢苯并[4,5]噻吩并[2,3-d]嘧啶含氟衍生物的合成、晶体结构及抗肿瘤活性

以环己酮、丙二腈和单质硫为起始原料,通过改良的Gewald反应合成2-氨基-3-氰基-4,5,6,7-四氢苯并[b]噻吩(Ⅰ),再与三氟乙酸、三氯氧磷反应"一锅法"直接制得4-氯-2-三氟甲基-5,6,7,8-四氢苯并[4,5]噻吩并[2,3-d]嘧啶,然后与取代苄胺反应合成13个噻吩并[2,3-d]嘧啶类含氟衍生物,收率为69%~83%。目标化合物的结构经1HNMR、IR、MS和元素分析方法进行表征。并采用X射线单晶衍射测定化合物Ⅲa的晶体结构,结果表明,该化合物晶体属单斜晶系,空间群为C2/c,a=2.695 9(4)nm,b=0.772 45(13)nm,c=1.688 5(3)nm,α=90°,β=109.320(2)°,γ=90°,V=3.318 2(9)nm3,Z=8,Dc=1.455×106g·m-3,μ=0.23 mm-1,F(000)=1 504,R1=0.057 9,wR2=0.160 4。初步的生物活性实验表明,部分化合物表现出良好的抗肿瘤活性,其中化合物Ⅲc、Ⅲf和Ⅲj对Hep G2和MCF-7细胞的抑制活性高于阳性对照样吉非替尼。