Cycloadditions of methyl dichloroacetate to electrophilic alkenes

Seven MIRC reactions of methyl dichloroacetate with alkenes containing electron-withdrawing groups were used to make 1-chlorocyclopropanecarboxylates.     

One‐Pot Substitution‐Rearrangement Reaction of 2‐Chloroglycidic Ester: Effective Protocol for the Preparation of 3‐Arylsulfenyl‐2‐keto Ester

The one‐pot substitution‐rearrangement reaction of 2‐chloroglycidic ester is reported. Treatment of 2‐chloroglycidic ester with sodium arylthiolate at room temperature results in the formation of 3‐arylsulfenyl‐2‐keto ester in excellent to good yields.     

Thiophene-2-aldehyde in the Darzens reaction

The reaction of the title compound with dichloroacetic acid esters in the presence of butyllithium gave esters of 3-thienyl-3-hydroxy-2,2-dichloropropionic acid.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan' Scientific Center of the Russian Academy of Sciences, 420083 Kazan', Russia. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1870–1873, August, 1992.     

Reaction of methyl dichloroacetate with substituted benzaldehydes under the conditions of the Darzens condensation

We have found that condensation of methyl dichloroacetate (1 with benzaldehyde, p-chloro- and p-bromobenzaldehyde in t-BuOH in the presence of t-BuOK yields methyl 3-aryl-3-chloro-2-oxopropionates (3–5). In the case of nitrobenzaldehydes the reaction products are -chloro-ketones (6, 7) and mainly methyl 2-chloro-3-aryl-2,3-epoxypropionates (8, 9). -Chloroepoxide (10) is formed in the reaction with 2,4-dichlorobenzaldehyde.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 2159–2162, September, 1992.     

二氯乙酸钠电纺纤维毡改善宫颈癌小鼠生存质量

通过溶液静电纺丝的方法,将水溶性药物二氯乙酸钠(DCA)包裹入油溶性聚乳酸(PLA)中,制备出二氯乙酸钠电纺纤维毡。 将其应用于宫颈癌的活体实验中,结果表明在为期19 d的治疗下,荷瘤小鼠的肿瘤抑制率达到94%,总体康复率达到38%。 同时,DCA电纺纤维毡还极大地抑制了宫颈癌后期复发和转移的趋势,提高了荷瘤小鼠的生存质量,是一种安全且疗效确切的抗癌给药剂型。     

Correlation of molecular and morphologic effects of thermoembolization in a swine model using mass spectrometry imaging

Hepatocellular carcinoma is a growing worldwide problem with a high mortality rate. This malignancy does not respond well to chemotherapy, and most patients present late in their disease at which time surgery is no longer an option. Over the past three decades, minimally invasive methods have evolved to treat unresectable disease and prolong survival. Intra‐arterial embolization techniques are used for large or multiple tumors but have distressingly high levels of local recurrence and can be costly to implement. A new method called thermoembolization was recently reported, which destroys target tissue by combining reactive exothermic chemistry with an extreme local change in pH and ischemia. Described herein are experiments performed using this technique in vivo in a swine model. A microcatheter was advanced under fluoroscopic guidance into a branch of the hepatic artery to deliver a targeted dose of dichloroacetyl chloride dissolved in ethiodized oil into the liver. The following day, the animals were imaged by computed tomography and euthanized. Assessing the reaction product distribution and establishing a correlation with the effects are important for understanding the effects. This presented a significant challenge, however, as the reagent used does not contain a chromophore and is not otherwise readily detectable. Mass spectrometry imaging was employed to determine spatial distribution in treated samples. Additional insights on the biology were obtained by correlating the results with histology, immunohistochemistry, and immunofluorescence. The results are encouraging and may lead to a therapy with less local recurrence and improved overall survival for patients with this disease.     

Convenient Rearrangement Reaction of 2‐Chloroglycidic Esters by PPh3: A New Synthetic Method of 3‐Chloro‐2‐keto Esters

A convenient rearrangement reaction of 2‐chloroglycidic esters is reported. Treatment of 2‐chloroglycidic esters with PPh₃ under refluxing condition results in the formation of 3‐chloro‐2‐keto esters in good to reasonable yields.