报道了以磷酸盐为催化剂选择性脱去芳香性叔丁基二甲基硅醚的方法.以DMF为溶剂,室温下在0.5质量分数的Na3PO4.12H2O催化下,能顺利地脱去芳香性叔丁基二甲基硅醚得到相应的酚类化合物,而不影响其他的保护基和官能团.

A facile protocol to the chemoselective deprotection of aryl t-butyldimethylsilyl (TB-DMS) ethers using Na3 PO4?12H2 O as promoter is described .From aryl TBDMS ethers to the corresponding phenols ,the TBDMS group could be cleaved in the presence of 0 .5 equivalent of Na3 PO4?12H2 O in DMF at room temperature with good to excellent yields in the presence of other common protecting and functional groups .This is ,to our knowledge ,the first report on chemoselective deprotection of aryl TBDMS ethers using phosphates .

在101.325kPa下，用气液平衡装置测定了甲基叔丁基醚．甲醇、甲醇．二甲基亚砜、甲基叔丁基醚．二甲基亚砜和甲基叔丁基醚．甲醇．二甲基亚砜四种体系在不同气液相组成时的沸点。二元体系活度系数分别用Wilson模型和NRTL模型进行关联，用最小二乘法求出了三个二元体系模型参数并用这些参数来计算了气相组成y与泡点温度丁。由面积积分法检验二元体系相平衡数据得到很好的热力学一致性。用Wilson模型和NRTL模型参数分别对三元体系数据进行关联，计算气相组成及泡点温度，计算结果与实验数据吻合较好，表明文中所用的模型适于甲基叔丁基醚-甲醇-二甲基亚砜体系。

Vapor-liquid equilibrium data of three binary systems (MTBE-methanol, methanol-DMSO and MTBE-DMSO) and one ternary system (MTBE-methanol-DMSO) were determined at 101.325 kPa with a vapor-liquid equilibrium device. The activity coefficients of the three binary systems were correlated separately with Wilson and NRTL models, and the parameters of the activity coefficient models were calculated through the least square method. The obtained parameters were used to calculate the vapor-phase composition y and the bubble point T. The thermodynamic consistency of the three binary systems calculated by those model parameters were checked with the area test method, which shows satisfactory results. The experimental VLE data of the ternary system were correlated with the model data to construct a thermodynamic model for the ternary system, which was used to calculate its equilibrating vapor-phase composition and the bubble point. The calculation results agree well with the experimental data, which

以苯酚和邻叔丁基酚为起始原料,合成了一个新型手性二聚Salen配体5,5-亚甲基-双-[(R,R)-{N-(3-叔丁基水杨醛)-N''-(3'',5''-双-叔丁基水杨醛)}-1,2-二苯乙二胺],并运用多种谱学手段对其进行表征.在邻叔丁基酚的羟基邻位甲酰化过程中,首次运用三乙胺代替六甲基磷酰胺(HMPA)定位,取得了很好的效果.成功合成了中间体N-(2-羟基-3,5-二叔丁基苯甲醛)-(1R,2R)-1,2-二苯基乙二胺的新方法.

This paper reports the synthesis and characterization of a novel chiral dimeric Salen ligand 5,5-metheylene di-[(R,R)-{N-(3-tert-butyl salicylidine)-N''-(3'',5''-di-tert-butyl salicylidene)}-1,2-diphenyleth-ylenediamine]) which using phenol and 2-tert-butylphenol as starting materials. In the procedure of the ortho-formylation of 2-tert-butylphenol, we first employ a method which substituter triethylamine for hexamethylphosphoramide in a highly ortho regioselective formation with a good yield. Furthermore, a new method is established to synthesize N-(2-hydroxy-3,5-di-tert-butylbenzaldehyde)-(1R,2R)-1,2-diphenyl-ethylenediamine.

研究了骨髓增殖性肿瘤治疗药物TG101348的合成工艺.将2,4-二羟基-5-甲基嘧啶与三氯氧磷、氨水发生氯化、取代反应生成2-氯-4-氨基-5-甲基嘧啶(Ⅲ),而后Ⅲ与N-叔丁基-3-溴苯磺酰胺(Ⅰ)发生Buchwald偶联反应得到3-[(2-氯-5-甲基-4-嘧啶基)胺基]-N-(叔丁基)苯磺酰胺(Ⅳ),Ⅳ再与CH3OHHCl反应得到3-[(2-氯-5-甲基-4-嘧啶基)胺基]-N-(叔丁基)苯磺酰胺盐酸盐(Ⅴ),最后Ⅴ与1-(4-氨基苯氧乙基)吡咯烷(Ⅵ)发生亲核取代反应得到TG101348,HPLC测得TG101348的纯度为99.7%.

The synthetic technique of TG101348 for treating bone marrow hyperplastic tumor was studied. 2-chloro-4-amino-5-methyl-pyrimidine(Ⅲ)was prepared by chlorination and substitution reaction of 2 ,4-dihydroxy-5-meth-ylpyrimidinnel,phosphorus oxychloride and ammonium hydroxide.Ⅲreacted with 3-bromo-N-t-butyl benzenesulfon-ic amide(Ⅰ) to give 3-[( 2-chloro-5-methyl-4-pyrimidinyl ) amino ]-N-t-butyl benzenesulfonic amide(Ⅳ) by Buchwald coupling reaction.Ⅳ reacted with CH3 OH-HCl to afford 3-[(2-chloro-5-methyl-4-pyrimidinyl)amino]-N-tert-butyl benzenesuiphon amide hydrochloride(Ⅴ). TG101348 was synthesized by nucleophilic substitution re-action of the intermediate Ⅴ and Ⅵ. HPLC purity is 99 . 7%.

以2，6-二甲基吡啶、正丁基锂为初始原料，在温和的条件经一倍正丁基锂去氢后与4-甲基-2-戊酮加成得到含N，O-二齿配体化合物[2-(6-(CH3)C5H4N)CH2C(OH)(CH3)CH2CH(CH3)2]，应用1HNMR技术对其进行了结构表征。

2, 6-dimethyl pyridine, n-butyl lithium as initial raw materials. In mild conditions after double n-butyl lithium to hydrogen and 4-methyl-2-ketone addition containing N, O-bidentate ligand compounds [2-(6-(CH3)C5H4N)CH2C(OH)(CH3)CH2CH(CH3)2] ,The compound was characterized by 1H NMR technique.