N-炔丙基-R-2-庚胺的合成工艺研究

以2-庚酮和甲酸铵为原料合成了2-庚胺,收率76.8%,然后经D-二苯甲酰酒石酸拆分后得到R-2-庚胺,拆分率41.4%.最后R-2-庚胺和乙炔、甲醛在碘化亚铜催化下合成N-炔丙基-R-2-庚胺,收率82.29b.并对反应可能的机理进行了探讨.     

碘代丙炔基正丁氨基甲酸酯的合成研究

以正丁胺为原料,与光气合成正丁基异氰酸酯,再与2-丙炔-1-醇反应得2-丙炔基正丁氨基甲酸酯,最后与一氯化碘反应得碘代丙炔基正丁氨基甲酸酯。研究了物料配比、反应温度及催化剂选择对反应结果的影响,产品含量达99%以上,产品总收率达93%(以2-丙炔-1-醇计,n/n),此工艺适宜于工业化。     

2-(1-羟基-3-丁炔基)-5-甲基呋喃催化重排合成2-炔丙基-3-甲基-4-羟基-2-环戊烯酮的研究

由 2 (1 羟基 3 丁炔基 ) 5 甲基呋喃催化重排合成 2 炔丙基 3 甲基 4 羟基 2 环戊烯酮 (炔丙菊醇 ) ,将传统的两步反应简化为一步反应 ,简化了工艺流程 ,缩短了反应时间 ,炔丙菊醇的产率较高 ,达到 75 .0 % ,高于文献报道的最大值 6 8.0 %。确定了反应的最佳反应条件为 :水作反应介质 ,m(催化剂 )∶m(反应物 ) =3∶10 0 ,反应时间 2 3h     

3-碘-4-苯基香豆素的简便合成

用苯酚与苯丙炔酸反应生成苯丙炔酸苯酯,在碱性条件下与碘单质发生反应,合成3-碘-4-苯基香豆素。用无机碱碳酸氢钠在硝基甲烷溶剂中合成3-碘-4-苯基香豆素时间最短,产率最高。     

2-羟基-3-丁氧基丙基淀粉的制备

以玉米淀粉为原料,丁基缩水甘油醚(BGE)为疏水化试剂,氢氧化钠作催化剂,水为溶剂,在较温和反应条件下合成了2-羟基-3-丁氧基丙基淀粉(HBPS)。考察了反应温度、反应时间、碱用量、水用量和BGE用量等因素对取代度和反应效率的影响,确定了最佳制备条件为:当n(BGE)/n〔淀粉葡萄糖单元(AGU)〕=0.615,m(H2O)∶m(AGU)=2∶1,n(NaOH)∶n(AGU)=0.5∶1,反应温度75℃和反应时间为5h,产品取代度MS=0.45,反应效率RE=73%。用IR、1HNMR、13CNMR对产物结构进行了表征。热重实验表明,疏水基团的引入可提高淀粉的耐热性能。     

(S)-1-氯-3-甲基丁基硼酸-( )-蒎烷二醇酯的合成

考察了医药中间体(S)-1-氯-3-甲基丁基硼酸-(+)-蒎烷二醇酯的合成,由异丁基硼酸经酯化,同系化反应制得,总收率87.6%。用单因素法优化了工艺条件,酯化反应:正己烷中回流反应5 h,2-甲基丙基硼酸-(+)-蒎烷二醇酯收率为98.5%;同系化反应:n〔2-甲基丙基硼酸-(+)-蒎烷二醇酯〕∶n(LDA)∶n(ZnCl2)=1∶2∶1.7,-78℃反应4 h,(S)-1-氯-3-甲基丁基硼酸-(+)-蒎烷二醇酯收率89.0%。中间体和目标产物用GC/MS、1 HNMR等方法分析,确认了其结构。     

2-羟基-3-丁氧基丙基淀粉的制备及性能研究

摘 要：以玉米淀粉为原料,丁基缩水甘油醚为疏水化试剂,氢氧化钠作为催化剂,水作为溶剂,在较温和反应条件下合成了2-羟基-3-丁氧基丙基淀粉(HBPS)。通过考察反应温度、反应时间、碱用量、水用量等因素对取代度和反应效率的影响,确定的最佳的制备条件为：当n(BGE):n(AGU)=0.615时,水用量m(H2O):m(AGU)=2:1、碱用量n(NaOH):n(AGU)=0.5:1、反应温度75℃和反应时间为5h,产品取代度MS=0.45,反应效率为RE=73%。使用IR、1H-NMR、13C-NMR对产物结构进行了表征,证明结构的正确。热重实验表明,疏水基团的引入可提高淀粉的耐热性能。     

一种多组分合成2-亚胺基噻唑啉衍生物的新方法

以伯胺、异硫氰酸酯和炔丙基溴为原料,在磷酸钾作用下,采用“一锅法”反应合成2-亚胺基噻唑啉衍生物。该方法具有原料易得,步骤简单,产率较高等优点,为合成2-亚胺基噻唑啉类化合物提供了一种实用的新方法。所得化合物的结构均经核磁和质谱确证。     

苯并咪唑炔丙基硫醚的合成

以２－巯基苯并咪唑和炔丙基氯为原料在碱性条件下缩合成苯并咪唑炔丙基硫醚。反应条件温和,产率６０％。     

2-溴-5-碘甲苯的合成工艺改进

以邻甲苯胺为起始原料,高碘酸钠为氧化剂,单质碘取代得2-氨基-5-碘甲苯,再经重氮化及Gattermann反应,得2-溴-5-碘甲苯,总收率66.1%(以邻甲苯胺计)。结果表明,较佳的工艺条件为:碘化过程中邻甲苯胺、高碘酸钠和碘的摩尔比为1∶0.6∶0.45,反应温度为25～30℃,反应时间3 h;在重氮化、溴代反应中,以亚硝酸钠为重氮化试剂,2-氨基-5-碘甲苯与亚硝酸钠和浓硫酸的摩尔比为1∶1∶7.5,反应温度为0～5℃,溴代反应时间为0.5 h;经精馏所得产物含量超过98%(GC法)。改进后的工艺原料易得,操作简便,适合工业化生产。     

Antifungal properties and material characteristics of PVC and wood/PVC composites doped with carbamate‐based fungicides

Antifungal properties of polyvinylchloride (PVC) and wood/PVC composites (WPVC) were studied with two different fungicides through disk diffusion and dry weight techniques against Aspergillus niger as a testing fungus. Three different types of woods, including Xylia kerrii Craib & Hutch.(XK), Hevea brasiliensis Muell.(HB), and Mangifera indica Linn.(MI), were used. The disk diffusion results revealed that the addition of 3‐iodopropinyl‐N‐butylcarbamate (IPBC) in the PVC and WPVC markedly reduced the diameter of fungi, whereas the addition of methylbenzimidazole‐2‐ylcarbamate(Carbendazim) did not. The results from IPBC samples by the dry weight technique corresponded to those by the disk diffusion method. Adding fungicides tended to slightly increase the flexural properties of PVC, whereas in the case of WPVC those properties were deteriorated by IPBC and carbendazim additions. The total color change was less when IPBC only was introduced into PVC. FTIR spectra suggested that no chemical structure changes were observed after the addition of IPBC and carbendazim. The higher surface contact angle and fungicide release values for IPBC samples could imply greater diffusibility of IPBC in PVC and WPVC matrices, accompanied by increased antifungal activity. WPVC with HB wood showed the best antifungal performance, at an optimal concentration of 10,000 ppm, when compared with XK and MI woods. POLYM. ENG. SCI., 54:1248–1259, 2014. © 2013 Society of Plastics Engineers     

高效液相色谱法对化妆品中低浓度碘丙炔醇丁基氨甲酸酯(IPBC)的检测

碘丙炔醇丁基氨甲酸酯(IPBC)在化妆品中含量极少,并对紫外线敏感,建立了一种不同的化妆品样品前处理方法,采用高效液相色谱/二极管阵列检测器(HPLC/DAD)检测.使用C18反相色谱柱(5μm,250 mm×4.6 mm),以乙腈-水为流动相进行等度洗脱,用DAD检测器扫描检测.对样品前处理条件,如前处理方法、萃取剂...     

Assessment and characterization of antifungal and antialgal performances for biocide‐enhanced linear low‐density polyethylene

In this work, four biocides were used for the purpose of growth inhibition of fungi and algae in linear low‐density polyethylene (LLDPE) specimens. Benzimidazol‐2‐yl‐carbamicacid methyl ester [carbendazim (CB)], 5‐chloro‐2‐(2,4‐dichlorophenoxy)phenol [triclosan (TS)], and 3‐iodo‐2‐propynyl N‐butylcarbamate [iodopropynyl butylcarbamate (IPBC)] were used as antifungal agents, and 2‐methylthio‐4‐ethylamino‐6‐tert‐butylamino‐triazin‐1,3,5 [terbutryn (TT)] was used as an antialgal agent. Antifungal performance was evaluated by disk diffusion and dry weight techniques, and antialgal activities were carried out by disk diffusion and chlorophyll A methods. Aspergillus niger TISTR 3245 and Chlorella vulgaris TISTR 8580 were used as the testing fungus and alga, respectively. The experimental results suggested that the wettabilities of LLDPE specimens changed with the incorporation of CB, TS, IPBC, and TT biocides without significant changes in chemical structures and mechanical properties of the LLDPE. IPBC with the recommended content of 10,000 ppm was found to give the most satisfactory growth inhibition of A. niger. Antifungal performance evaluations were dependent on the testing methods used, whereas those for antialgal activity were not. The optimum concentration of TT agent for effective killing of C. vulgaris was 750 ppm; this loading could be reduced from 750 to 250 ppm by the addition of either TS or IPBC agent. TS and IPBC could be used as antialgal promoters in the LLDPE specimens. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Partitioning of organic biocides between wood and supercritical carbon dioxide

The degree of interaction between selected organic biocides (tebuconazole, propiconazole, and IPBC) and wood under supercritical conditions was investigated using a supercritical fluid chromatograph. The biocides were carried through a sawdust column by CO₂ at various conditions. Retention times differed markedly both between the examined biocides and between physical conditions. Tebuconazole showed a higher affinity for wood than the other biocides. For all biocides, wood affinity was highest and, thus, fluid affinity lowest, at lowest pressures.     

Penetration of 3-iodo-2-propynyl butylcarbamate (IPBC) in coniferous wood pre-treated with <Emphasis Type="Italic">Physisporinus vitreus</Emphasis>

The permeability of Norway spruce wood can be reduced to 1–5% of that of green timber when dried, resulting in only slight radial penetration of chemical solutions. We investigated the penetration of the biocide 3-iodo-2-propynyl butylcarbamate, (IPBC) in Norway spruce and Scots pine sapwood when applied in a water-based coating system. Penetration of both untreated wood and specimens pretreated with the white-rot fungus Physisporinus vitreus was analyzed by the absence or presence of blue staining after incubation with Aureobasidium pullulans and Sclerophoma pithyophila. The qualitative results were compared with quantitative data obtained by chemical analysis. It was assumed a pre-treatment with Physisporinus vitreus could make the surface of the substrate more porous and improve the penetration of fluid substances. All analytical investigations of the samples were done after an outdoor weathering period of 6 months. From a practical point of view the performance of the coated substrate is more relevant after a certain aging procedure then right after the application. The chemical measured uptake of IPBC for Scots pine was similar for all samples at the surface. The penetration depth was higher for those samples with a pre-treatment with Physisporinus vitreus. The colonization pattern of the samples by blue-stain fungi depended upon the pre-treatment but did not show a clear correlation between IPBC-content and staining. The cross-section of the samples with pre-treatment was completely stained, the cross-section of the samples without pre-treatment did show a distinctive blue stain-free zone. In Norway spruce, the chemical measured uptake of IPBC was similar for all samples at the surface independent of the pre-treatment. The penetration depth was higher for those samples with a pre-treatment with Physisporinus vitreus. But a clear visible colonization by blue-stain fungi was only observed for the samples with a pre-treatment with Physisporinus vitreus. The samples without pre-treatment were locally stained across the entire cross-section. As with the Scots pine, a clear correlation between IPBC-content and blue staining was not visible, following comparison of the samples with and without pre-treatment with Physisporinus vitreus. The results suggest that not only the presence of IPBC influences colonization by A. pullulans and S. pithyophila, but also a range of other factors in wood pre-treated with P. vitreus.     

从植物十大功劳中制取四氢小檗碱的工艺研究

研究从植物十大功劳中制取四氢小檗碱 (THB)的生产工艺。用比较法来选择盐酸小檗碱的提取工艺 ,用正交试验法选择小檗碱最佳氢化条件。从十大功劳中制取四氢小檗碱的生产工艺为 :用酸水浸渍法提取盐酸小檗碱粗品 ,粗品以硼氢化钾为还原剂 ,乙醇作为溶剂 ,用水浴加热反应 ,最佳氢化工艺条件是乙醇浓度为 70 % ,乙醇用量为粗品的 7倍量 ,硼氢化钾先用水溶解逐渐加入。实验表明 :酸水浸渍法提取盐酸小檗碱得率较高且操作简单 ;A2 B2 C3为最佳氢化工艺条件     

邻苯二甲酸二异辛酯的合成研究

以邻苯二甲酸酐和异辛醇为原料、甲苯为带水剂,分别以NaHSO4、对甲苯磺酸、阳离子交换树脂、LaCl3、LaCl3/阳离子交换树脂、LaCl3/ZSM-5、LaCl3/活性炭等为催化剂合成邻苯二甲酸二异辛酯(DEHP),经过比较,确定以自制的5％ LaCl3/ZSM-5作催化剂.通过正交实验确定最优合成条件为:邻苯二甲酸酐与异辛醇摩尔比1∶2.5、催化剂用量(以原料总质量计)5％、反应时间4h、带水剂用量(以原料总质量计)40％,在此条件下,邻苯二甲酸酐转化率达98.81％、邻苯二甲酸二异辛酯产率达96.97％,且催化剂具有较好的重复使用性.     

哌嗪合成新工艺

以乙二胺为原料气固相催化合成哌嗪和三乙烯二胺,对实验用催化剂进行制备与考察,筛选出用CaC l2改性的HZSM-5型分子筛为催化剂,确定了最佳工艺条件为:反应温度为340℃,乙二胺的质量分数为40%,进料流率为0.40 mL/m in。结果表明:合成采用CaC l2改性的HZSM-5型分子筛,以乙二胺为原料合成哌嗪的工艺路线是可行的,在最佳工艺条件下,乙二胺的转化率为95%,哌嗪的收率为65%,三乙烯二胺的收率为25%。     

2,6-二甲基哌嗪合成新工艺

以1,2-丙二胺为原料气固相催化合成2,6-二甲基哌嗪,对实验用Cu-Cr-Fe/γ-Al2O3催化剂进行制备与考察,实验所确定的最佳工艺条件为:原料液1,2-丙二胺的质量分数40%,反应温度320℃,空速490.74 h-1,结果表明:采用Cu-Cr-Fe/γ-Al2O3为催化剂,以1,2-丙二胺为原料合成2,6-二甲基哌嗪的工艺路线是可行的,在最佳工艺条件下,1,2-丙二胺的转化率为98.84%,2,6-二甲基哌嗪的收率为88.62%。     

1，6-己二醇二丙烯酸酯的合成

以1,6～己二醇、丙烯酸为原料,对甲苯磺酸与亚硫酸为催化剂,环己烷为带水剂,CuSO4／NaHSO4为复合阻聚剂,采用直接酯化法合成1,6-己二醇二丙烯酸酯。探讨了催化剂、带水剂、反应时间和温度以及酸醇比（丙烯酸／1,6-己二醇,摩尔比）对酯化反应的影响。研究结果表明,最佳的酯化反应条件为：丙烯酸／1,6-己二醇为2．5,催化剂用量（占原料总质量,％）为1．5％,带水剂用量（占原料总质量,％）为65％,反应时间为90min,反应温度为80—90℃。在此条件下,产物为无色透明油状液体,收率可达93．25％。