有机催化3-氨基氧化吲哚与偶氮二羧酸酯的不对称加成反应

手性3,3-双取代氧化吲哚结构单元广泛存在于具有生物活性的天然产物和具有药物活性的化合物中,尤其存在于具有光学活性的3-氨基氧化吲哚中。此外,手性3,3-双取代氧化吲哚结构单元作为有效抗疟药(NITD609)、高效焦虑和抑郁抑制剂(SSR149415)以及HIV蛋白酶抑制剂而备受关注。因此,发展合成手性3-氨基氧化吲哚的新方法具有重要意义。为了实现反应的敏感性产物N,N′-缩靛红衍生物的不对称合成,使用金鸡纳碱衍生的方酰胺作催化剂,3-氨基氧化吲哚席夫碱与偶氮二羧酸酯作模板底物,最终以70%~85%的产率和45%~88%的对映选择性获得相应产物。该反应的实验条件温和,原子经济性高。

Tungstophosphoric heteropolyacid supported onto neutral alumina: characterization and synthesis of acetals and ketals

Tungstophosphoric acid （HPW） catalyst supported on the neural alumina was studied. It was prepared by means of an equilibrium and incipient wetness impregnation technique. Solution of HPW in 50% V/V ethanol-water was used to impregnate Al2O3 at 25℃. It was found that the catalyst containing 30% PW by calcination at 500℃ showed a higher catalytic activity in the synthesis of acetals and/or ketals. In the following condition, that is, the molar ratio of aldehyde/ketone to glycol being 1：1.5, the mass fraction of the catalyst used was 0.5%, and the reaction time was 1.0 h; the yields of ketals and acetals could reach up to 60.5%-86.7%. Moreover, it could be easily recovered and reused.

手性磷酸催化非环状N,N′-缩酮的不对称合成

手性N,N′-缩酮是药物分子和生物活性化合物最重要的核心结构之一,也是有机合成中重要的催化剂或配体。因此,不对称合成N,N′-缩酮具有重要意义。通过手性磷酸、溶剂、催化剂负载量和投料比的筛选,确定了最佳的反应条件:在手性磷酸的催化下,以1,4-二氧六环作为溶剂,5-氨基异噁唑与β,γ-炔基-α-酮亚胺酯在室温下发生区域选择性的氮杂-曼尼希反应,实现异噁唑的不对称N—H烷基化,以中等至良好的收率(46%~83% yield)和较好的对映选择性(82%~92%ee)合成非环状的N,N′-缩酮。所有产物结构由^(1)H NMR,^(13)C NMR和HR-MS(ESI)确证,绝对构型通过X-射线晶体结构分析确定。

Catalytic synthesis of cyclohexanone 1,2-propanediol ketal with H_4SiW_(12)O_(40)/PAn

A new environmental friendly catalyst, H_4SiW_(12)O_(40)/PAn was prepared andidentified by means of FT-IR, XRD and TG/DTA. Cyclohexanone 1,2-propanediol ketal was synthesizedfrom cyclohexanone and 1,2-propanediol in the presence of H_4SiW_(12)O_(40)/PAn The factorsinfluencing tlie synthesis were discussed and the best conditions were found out. The optimumconditions are: molar ratio of cyclohexanone to 1,2-propanediol is 1:1.4, the quantity of catalystis equal to 1.0 percent of feed stocks, and the reaction time is 40 min. H_4SiW_(12)O_(40)/PAn is anexcellent catalyst for synthesizing cyclohexanone 1,2-propanediol ketal and its yield can reachover 96.5 percent.

Catalytic synthesis of acetals and ketals with H3PW12O40/PAn

A new environmental friendly catalyst H3PW12O40/PAn was prepared and identified by means of FT-IR,XRD,and TG/DTA.The optimum conditions have been found;that is,the mass ratio of PAn to H3PW12O40 is 1：1.5,the volume of methanol is 20 mL,and the reflux reaction time is 3 h.The structural identity of Keggin units is preserved after the incorporation into polyaniline matrix.Catalytic activities of H3PW12O40/PAn in synthesizing 2-methyl-2-ethoxycarbonylmethyl-1,3-dioxolane,2,4-dimethyl-2-ethoxycarbonylmethyl-1,3-dioxolane,cyclohexanone ethylene ketal,cyclohexanone 1,2-propanediol ketal,butanone ethylene ketal,butanone 1,2-propanediol ketal,2-phenyl-1,3-dioxolane,4-methyl-2-phenyl-1,3-dioxolane,2-propyl-1,3-dioxolane,and 4-methyl-2-propyl-1,3-dioxolane were reported.It has been demon-strated that H3PW12O40/PAn is an excellent catalyst.Various factors concerned in these reactions were investigated.The optimum conditions are as follows：the molar ratio of aldehyde/ketone to glycol（r） is 1：1.5,the mass ratio of the catalyst used to the reactants is 0.6%,and the reaction time is 1.0 h.Under these conditions,the yield is as follows：2-methyl-2-ethoxycarbonylmethyl-1,3-dioxolane,69.0%;2,4-dimethyl-2-ethoxycarbonylmethyl-1,3-dioxolane,79.5%;cyclohexanone ethylene ketal,78.9%;cyclohexanone 1,2-propanediol ketal,85.3%;butanone ethylene ketal,56.9%;butanone 1,2-propanediol ketal,78.1%;2-phenyl-1,3-dioxolane,76.3%;4-methyl-2-phenyl-1,3-dioxolane,94.2%;2-propyl-1,3-dioxolane,70.7%;and 4-methyl-2-propyl-1,3-dioxolane,79.2%.

Synthesis of acetals and ketals catalyzed by tungstosilicic acid supported on active carbon

Catalytic activity of activated carbon supported tungstosilicic acidin synthesizing 2-methyl-2-ethoxycarbonylmethyl- 1,3-dioxolane, 2,4-dimethyl-2-ethoxycarbonylmethyl-1,3-dioxolane, cyclohexanone ethylene ketal, cyclohexanone 1,2-propa- nediol ketal, butanone ethylene ketal, butanone 1,2-propanediol ketal, 2-phenyl-1,3-dioxolane, 4-methyl-2-phenyl-1,3-dioxolane, 2-propyl-1,3-dioxolane, 4-methyl-2-propyl-1,3-dioxolane was reported. It has been demonstrated that activated carbon supported tungstosilicic acid is an excellent catalyst. Various factors involved in these reactions were investigated. The optimum conditions found were: molar ratio of aldehyde/ketone to glycol is 1/1.5, mass ratio of the catalyst used to the reactants is 1.0%, and reaction time is 1.0 h. Under these conditions, the yield of 2-methyl-2-ethoxycarbonylmethyl-1,3-dioxolane is 61.5%, of 2,4-dimethyl- 2-ethoxycarbonylmethyl-1,3-dioxolane is 69.1%, of cyclohexanone ethylene ketal is 74.6%, of cyclohexanone 1,2-propanediol ketal is 80.1%, of butanone ethylene ketal is 69.5%, of butanone 1,2-propanediol ketal is 78.5%, of 2-phenyl-1,3-dioxolane is 56.7%, of 4-methyl-2-phenyl-1,3-dioxolane is 86.2%, of 2-propyl-1,3-dioxolane is 87.5%, of 4-methyl-2-propyl-1,3-dioxolane is 87.9%.

Eco-friendly one-pot synthesis of acetals and ketals by heterogeneously catalyzed liquid-solid phase reaction

Twelve classes of acetals and ketals were synthesized from aldehyde/ketone and glycol using ZiSiW12O40/TiO2 as a novel eco-friendly catalyst. The physical characterizations were carried out by TG/DTA, FT-IR, XRD, and ^1H NMR spectra. The results indicated that the catalyst showed excellent catalytic activity for the condensation reactions. The yield of 12 classes of acetals and ketals reached 56.3%-96.3% under the typical reaction conditions （the molar ratio of aldehyde/ketone and glycol was 1：1.5, the quantity of catalyst was 0.5% of feed stock, the reaction time was 1.0 h, and the reaction temperature was 80-116℃）. The catalyst was easily recovered and reused to give almost the same yield of the product as that given by fresh TiSiW12O10/TiO2.

Polyaniline Supported 12-Tungstosilicic Acid as the Catalyst for Acetals and Ketals Synthesis

A novel environmental friendly catalyst, H4SiW12O40/PAn was prepared and identified by FT-IR, XRD and TG/DTA. The optimal synthetic protocol was a PAn to H4SiW12O40 mass ratio of 1 ： 1, a 20 mL of methanol and a reaction time of 2 h at reflux. It was used in catalytic synthesis of ten important ketals and acetals with a high catalytic activity. With an aldehyde/ketone to glycol molar ratio of 1 ： 1.5 and a 1 wt% catalyst loading, the yields of ketals and acetals could reach 60.0%- 93.8 % after 1 h.

H4SiW6Mo6O40-Doped Polyaniline-Synthesis, characterization and catalytic properties of acetals and ketals

A new environmental friendly catalyst, HaSiWrMo6O40/PAn was prepared and identified by means of FT-IR, XRD and TG/DTA. The optimum conditions have been found, that was, mass ratio of m（PAn）： m（HaSiW6Mo6On.） was 1：1.25, volume of methanol was 20 mL, and the reflux reaction time was 2h. The structural identity of Keggin units was preserved after the incorporation into polyaniline matrix. H4SiW6Mo6040/PAn was used as catalyst in catalytic synthesis of acetals and ketals. Effects of n（aldehyde（ketone ））： n（glycol）, catalyst dosage and reaction time on yield were investingated. Optimal conditions were： n（aldehyde（ketone））： n（glycol）=1.0： 1.5; mass fraction of catalyst to reactants, 0.5%; reaction time, 1.0 h and cyclohexane as water-stripped reagent, 15 mL. Under these conditions, yields of actels and ketals were 31.9%-91.6%.

Catalytic synthesis of acetals and ketals with H3PW6Mo6O40/TiO2

A new environmental friendly catalyst, H3PW6Mo6O40/TiO2 was prepared. The optimum conditions have been found, that is, mass ratio of m （TiO2）： m （H3PW6Mo6O40） is 1：2.0, volume of water is 30 mL, the reflux reaction time is 2 h, and activated temperature is 150 ℃. H3PW6Mo6O40/TiO2 was used as catalyst in catalytic synthesis ofacetals and ketals. Effects ofn （aldehyde（ketone））： n （glycol）, catalyst dosage and reaction time on yield were investigated. Optimal conditions were： n（aldehyde （ketone））： n （glycol）=1.0 ： 1.4; mass fraction of catalyst to reactants, 0.8%; reaction time, 1.0 h and cyclohexane as water-stripped reagent, 10 mL. Under these conditions, yields of acetals and ketals can reach 53.0% -86.9 0%

Zeolite-Catalyzed Acetalization Ⅰ. Synthesis of Some Acetals and Ketals through Reaction of Carbonyl Compounds with Ethanediol

The acetalization of a series of carbonyl compounds with ethanediolwas performed over two self-steaxned HY zeolle catalpsts' The acetal and ketaiproducts were obtained with high ytelds Espectw, the HY zeollte with highfraxnework Si/A1 ratio was proven to be suitable cataipst for the acetabotion ofunsaturated carbonyl compounds, during which the C =C double bond was notperturbed

Solventless ketalization of glycerol to solketal with acetone over the ionic liquid[P(C4H9)3C14H29][TsO]

The ketalization of glycerol with acetone was conducted over an ionic liquid[P(C4H9)3C14H29][TsO](TTPT)in a batch reactor.A scheme to obtain the purified product using TTPT as a homogeneous catalyst is proposed and a maximum solketal yield of 86%is achieved at acetone/glycerol molar ratio of 6/1,reaction time of 0.5 h,reaction temperature of 303 K,catalyst amount of 5 wt%of glycerol.TTPT was recycled and reused for ten times without obvious losses in terms of quantity and activity.Furthermore,effects of various experimental parameters(stirring speed,catalyst loadings,temperature and reactant composition)on the reaction kinetics are investigated.In terms of kinetics modeling,Kγis fitted by reactant composition at the temperature range 298 K–323 K,which was a concise strategy that showed good precision in the kinetics fitting.The activation energy for this ketalization reaction was evaluated to be 28.2 kJ·mol^-1.In addition,the kinetics of the reaction at a temperature exceeding the boiling point of acetone were also studied.We believe that all the results are important for further development of a technology for the continuous synthesis of solketal.

A NEW METHOD FOR AROMATIZAT ION OF Δ^(5(10))-STEROIDAL C_(3)-DIMETHYL KETALS

A new method for aromatization of Δ^(5(10))-steroidal C_3-dimethyl ketals with pyridinium hydrobromide perbromide (PHP.Py·HBr·Br_2) to aromatic A ring steroids in high yield (90-95%) is described.

DEPROTECTION OF ACETALS AND KETALS WITH CpTiCl_3-KI

When the mixture of CpTiCl_3-KI is used, many acetals and ketals, which are difficuitly deprotected with CpTiCl_3 alone, can be easily converted to the corresponding carbonyl compounds in high yield at 30℃ in Et_2O.

Stable Send-ketals of 3',5'-O-(Tetraisopropyldisiloxane-1,3-diyl)-2'-Ketouridine

A series of stable semi-ketals were obtained via the reactions of 3',5'-O-(tetraisopropyldisiloxane-1,3-diyl)-2'-ketouridine 1 with primary alcohols. In the addition reaction,only a single diastereomer was observed. The configuration of 3b was confirmed by X-raydiffraction.

SYNTHESIS OF A KETAL BY USING HPA AS CATALYST

The work herein reported is about a rapid and convenient synthetic method of a betal formed from ethylene glycol and cyclohexanone by using H3PW12O40(HPA)as catalyst. It has ben shown that the reaction, by using HPA as catalyst, can proceed at room temperature and have the high yield of 92% and the catalyst can be used again and again

CONVERSION OF ACETALS AND KETALS TO CARBONYL COMPOUNDS PROMOTED BY ZrCl_4-NaBH_4

In our study on the chemistry of ZrCl_4-NaBH_4,we have found that aldehydes and ketones can be regenerated from acetals and ketals at 30℃ in Et_2O in high yield The reaction mechanism was discussed.

A validated, related substance, GC method for 1,4-cyclohexanedione mono-ethylene Ketal

ABSTRACT A simple, economic, and time-efficient related substance, GC method has been developed for the analysis of 1,4-Cyclohexanedione mono- ethylene ketal(will be specified as ketal) in the presence of a potential impurity 1,4-cyclohexa- nedione bis (ethylene ketal) [will be specified as diketal]. Successful chromatographic separa- tion of the ketal from the impurity was achieved on a DBWAX ETR, 30 m x 0.32 mm x 1.0μ FT column with nitrogen as carrier gas and FID detector. The method was validated for linearity, accuracy, precision, and specificity and can be used for quality control during manufacture of ketal. A validated GC method is reported for the ketal for the first time.

分子筛HZSM-5催化合成生物基缩酮的工艺

为了制备新型生物质基甘油缩酮,开发一种以生物质基平台化学品乙酰丙酸甲酯(ML)和甘油(GLY)为原料,分子筛催化合成乙酰丙酸甘油缩酮甲酯(MLK)的绿色工艺。考察β、USY、HZSM-5型3种分子筛的催化效果,筛选出HZSM-5为适宜的催化剂。在此基础上,采用Box-Behnken实验设计考察并优化催化剂用量、反应温度和反应原料物质的量比对MLK产率的影响,同时对反应前后的催化剂进行了表征。结果表明:在ML与GLY物质的量比为4.3,反应温度为121℃,催化剂用量为1.6g的条件下,MLK产率达到92.09%。HZSM-5循环使用6次后,MLK的产率为87.89%,表明HZSM-5分子筛催化剂具有良好的催化活性和稳定性。