缩硫醇

Then Doripenem came into the market in the July ,2005. We studied the synthesis of Doripemen.Firstly, we synthesized the chemical 2 from the starting material------o-hydroxylphenylacylamine through Reformastky reaction, alkylation, Diekmann reaction, enolization, esterification and etc. Secondly, we synthesized the chemical 3 from L — hydroxylproline through the protection of carboxyl, amidogen and hydroxyl group, reduction by NaBr, SN_2 substitution and Mitsumobu reaction.

我们以水杨酰胺为起始原料，经Reformatsky反应、烷基化、Diekmann环合、烯醇化、酯化等反应合成双环母核2；再从L-羟基脯氨酸出发，经酯化保护羧基、保护氨基、保护羟基、硼氢化还原酯得醇、Sn2取代和Mitsumobu反应等合成巯基侧链3；最后由化合物3经脱保护、水解得硫醇，和化合物2在二异丙基乙基胺的作用下缩合，最后Pd／C催化脱保护，历经16步反应最终得到产物多尼培南。

Generally speaking, the reaction types involvingα-oxoketene--acetals mainly include the regioselective addition-aromatization with organometallic reagents, conjugate addition-cyclization with nitrogen nucleophilicspecies, nucleophilic reactions ofα-carbon, acting as odorless dithiol equivalentsin thioacetalization, Michael additions and [5+1] annulation, as well as the synthetic applications based on the above reactions.

一般来说，基于α-羰基二硫缩烯酮化学的反应主要为：与金属有机试剂的选择性加成反应，与氮亲核体的共轭加成反应，α-碳原子的亲核性及相关反应，烷硫基作为硫醇的替代试剂的应用，α-羰基二硫缩烯酮在碳环、杂环化合物合成中的应用等。

In this paper, a series of 4,5-dithiacrown ether annulated 1,3-dithiole-2-thiones 8a~8d were prepared via condensing 4,5-bis-1,3-dithiole-2-thione (7) with 1,ω-dimercapto polyglycol derivatives in high dilution. The obvious template effect was found during the synthesis of 8c-8d.

在高度稀释条件下，经4，5-二溴甲基-1，3-二硫杂环戊烯-2-硫酮(7)和多缩乙二醇的1，ω-二巯基衍生物的缩合反应，方便地合成了4，5-位带二硫杂冠醚残基的2-硫代-1，3-二硫杂环戊烯的衍生物8a~8d，中间体硫杂冠醚8c~8d的合成中有明显的&模板效应&。

In this paper, a series of 4,5-dithiacrown ether annulated 1,3-dithiole-2-thiones 8a~8d were prepared via condensing 4,5-bis-1,3-dithiole-2-thione (7) with 1,ω-dimercapto polyglycol derivatives in high dilution. The obvious template effect was found during the synthesis of 8c-8d.

在高度稀释条件下，经4，5-二溴甲基-1，3-二硫杂环戊烯-2-硫酮(7)和多缩乙二醇的1，ω-二巰基衍生物的缩合反应，方便地合成了4，5-位带二硫杂冠醚残基的2-硫代-1，3-二硫杂环戊烯的衍生物8a~8d，中间体硫杂冠醚8c~8d的合成中有明显的&模板效应&。

Firstly, 3-ethylthiobutanal was prepared from crotonaldehyde reacting with ethanehiol in triethylamine with high yield. Secondly, methyl acetoacetate was converted to 6-ethylthiohept-3-en-2-one by three steps via hydrolysis, condensation with 3-ethyltio-butanal and dehydration, then 6-ethylthiohept-3-en-2-one was cycloco ndensed with dimethyl malonate by Michael addition and Claisen condensation, followed by saponification and decarboxylation to give the intermediate of 5-(2-ethylthiopropyl)-cyclohexane-1,3-dione.

首先，以巴豆醛与乙硫醇为原料，在三乙胺的催化作用下高收率制得3-乙硫基丁醛；然后从乙酰乙酸甲酯出发，通过碱水解、与3-乙硫基丁醛缩合、脱水三步反应合成6-乙硫基-3-烯-2-庚酮，接着6-乙硫基-3-烯-2-庚酮与丙二酸二甲酯通过Michael加成和Claisen缩合成环，再通过皂化和脱羧反应生成中间体5-[2-丙基]-1，3-环己二酮；再与丙酸酐反应丙酰化，最后与0-3-氯-2-丙烯基羟胺肟化，得到目标化合物烯草酮。

To synthesize the octreotide, Phe-Leu-Glu-Glu-Leu and C_(15)H_(31)-CO-Lys-Thr -Thr-Lys-Ser peptides, the strategies are as followings: Fmoc- group as protective group for α-NH_2; TBTU, DIEA and HOBt as coupling reagent; and ethanedithiol -phenol - thioanisole - H_2O - TFA ( 2.5:5:5:5:82.5 , V/V ) as cleaving solution.

采用Fmoc固相合成法，以苯并三哗四甲基脲四氟硼酸盐、二异丙基乙胺和1-羟基苯骈三氮唑为缩合剂；苯酚—乙二硫醇—苯甲硫醚—水—三氟乙酸(5：5：2.5：5：82.5，V/V)为切割试剂，合成了奥曲肽、Phe-Leu-Glu-Glu-Leu及C_(15)H_(31)-CO-Lys-Thr-Thr-Lys-Ser三种小分子多肽，并对奥曲肽的合成规模进行了放大。

The heptanal butyl mercaptal was synthesized with heptanal, sodium thiosuifate and 1bromobutane as raw materials.

以正庚醛、硫代硫酸钠和溴代正丁烷为原料，合成了正庚醛正丁硫醇缩醛。

Acetaldehyde(0\^1 mol) was treated with n propylthiol(0\^1 mol) at 35 ℃ for 20 min to yiled 72% acetaldehyde propyl mercaptal .

以 0 。1 mol乙缩醛和 0 。1 mol 正丙硫醇为原料，35℃下在四氯化碳中反应，经红外光谱，色谱，质谱，元素分析以及核磁共振谱检测，确证了产物为乙醛正丙硫醇缩醛。

The beta-thioalkoxyalcohols could be obtained in good yields by the reaction of dialkyl-substituted propargylic dithioacetals with a series of carbonyl compounds.

我们发现在铁触媒和格林那试剂的存在下，利用双烷基取代炔丙基硫缩酮和羰基化合物反应生成的beta-硫烷氧基醇，可以进行不常见的beta-氧消去反应，而得到烯炔衍生物。

In previous results, Alkyl substituted propargylic dithioacetals treating with butyl lithium then were allowed to react with carbonyl compounds to form homopropargylic alcohol with high yields and highly regioselective.

在本实验室先前的研究中发现，烷基取代炔丙基硫缩酮与正丁基锂进行开环反应后，若是与羰基化合物反应，能够以高产率、具位向选择性的生成高炔丙基醇。

On the other hand, the more important thing is because the urban housing is a kind of heterogeneity products.

另一方面，更重要的是由于城市住房是一种异质性产品。

Climate histogram is the fall that collects place measure calm value, cent serves as cross axle for a few equal interval, the area that the frequency that the value appears according to place is accumulated and becomes will be determined inside each interval, discharge the graph that rise with post, also be called histogram.

气候直方图是将所收集的降水量测定值，分为几个相等的区间作为横轴，并将各区间内所测定值依所出现的次数累积而成的面积，用柱子排起来的图形，也叫做柱状图。