{"id":10337,"date":"2022-10-20T04:13:01","date_gmt":"2022-10-19T20:13:01","guid":{"rendered":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337"},"modified":"2022-10-20T04:13:01","modified_gmt":"2022-10-19T20:13:01","slug":"gundermann-karl-dietrichs-team-published-research-in-chemische-berichte-in-1960-cas-15366-34-4","status":"publish","type":"post","link":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337","title":{"rendered":"Gundermann, Karl Dietrich&#8217;s team published research in Chemische Berichte in 1960 | CAS: 15366-34-4"},"content":{"rendered":"<p>In 1960,Gundermann, Karl Dietrich; Thomas, Rainer published \u300aMercaptoacrylic acid derivatives. VII. The effect of thioether groups on the stabilization of 1-pyrazoline-3-carboxylic acid derivatives\u300b.Chemische Berichte published the findings.<a href=\"https:\/\/www.ambeed.com\/products\/15366-34-4.html\">Product Details of 15366-34-4<\/a> The information in the text is summarized as follows:<\/p>\n<p>cf. CA 54, 289b. 3-Alkylthio-1-pyrazoline-3-carboxylic acid esters, readily obtained from \u03b1-alkylthioacrylic acid esters and CH2N2, split off mercaptans at room temperature to yield pyrazole-3-carboxylic acid esters, but N at 50\u00b0 to give mixtures of 1-alkylthiocyclopropane-1-carboxylic acid esters and \u03b1-alkylthiocrotonic acid esters. Pyrazoline derivs, from \u03b1-alkylthioacrylonitriles and CH2N2 underwent only a stabilization reaction with the elimination of N. CH2:C(SMe)CO2Me (21.4 g.) in 200 cc. Et2O treated with CH2N2 from 25 g. H2NCON(NO)Me (I) in 200 cc. Et2O, kept overnight, filtered, evaporated in vacuo at 30\u00b0, the resulting light yellow, oily pyrazoline derivative added dropwise to a flask preheated to 90-100\u00b0, heated about 0.5 hr. on the steam bath, and fractionated gave 19.8 g. 3:1 mixture of the Me ester (II) of 1-methylthiocyclopropane-1-carboxylic acid (III) and Me \u03b1-(methylthio)crotonate (IV), b15 70-82\u00b0, n20D 1.4835. (III-IV mixture (15 g.) and 50 cc. 20% HCl refluxed about 6 hrs., evaporated in vacuo, and the residue (7.7 g.) recrystallized from 20% HCl gave III, m. 65-6\u00b0, b0.2 84-6\u00b0, Rf 0.90 (4:1:5 BuOH-glacial AcOH-H2O), colorless prisms; III with CH2N2 gave 100% pure II, b14 74\u00b0, n20D 1.4823. II treated room temperature with concentrated NH4OH and evaporated yielded the amide of III, prisms, m. 89\u00b0 (petr. ether). Crude pyrazoline derivative from CH2:C(SMe)CO2Me and CH2N2 kept 1 week at room temperature and filtered gave the Me ester of pyrazole-3-carboxylic acid (V), m. 140\u00b0 (aqueous MeOH), which was saponified to V, m. 212\u00b0. II-III mixture (3 g.) treated about 24 hrs. at room temperature with liquid NH3 gave 0.6 g. MeCH(NH2)-CH(SMe)CO2H, Rf 0.64; saponification of the nonbasic portion of the product gave 1.7 g. III. Me3CSH (45 g.) added dropwise with stirring to 60 g. CH2:CClCO2Me and 2.3 g. NaOMe at 45-50\u00b0, kept overnight, diluted with Et2O, washed, dried, and fractionated gave 68.7 g. Me3CSCH2CHClCO2Me (VI), b0.4 85-6\u00b0, b0.2 77-8\u00b0, n20D 1.4790. VI (42 g.), 26.2 g. powd. KBr, 22.2 g. Et3N, and 170 cc. HCONMe2 gave in the usual manner 22.8 g. Me2CSC(:CH2)CO2Me (VII), b12 92-3\u00b0. n20D 1.4795. VII (8.6 g.) in 70 cc. Et2O treated with CH2N2 from 10 g. I in 100 cc. Et2O, the product decomposed at 85-90\u00b0, and fractionated gave 7.0 g. oil, b12 83-5\u00b0, n20D 1.4803; the oil refluxed 1 hr. on the steam bath with 2 volumes 20% aqueous NaOH and 1 volume MeOH, filtered, acidified, and the product isolated with Et2O gave 3.8 g. 1-tert-butylthiocyclopropane-1-carboxylic acid, b0.2 93-4\u00b0, n22D 1.4955. The crude product from VII and CH2N2 kept 8 days at room temperature yielded 90% Me ester of V. CH2:C(SMe)CN (8 g.) in 80 cc. Et2O treated with CH2N2 from 12 g. I, the crude product dropped at 80-90\u00b0 into a flask, and the residue fractionated yielded 6.85 g. 4:1 mixture of the nitrile of III and MeCH:C(SMe)CN, b11 67-9\u00b0, n20D 1.4900; the mixture heated 4 hrs. with a 5-fold amount 1:1 glacial AcOH-HCl, evaporated, the residue extracted with Me2CO, and the extract worked up gave 60% III. CH2:C(SCH2Ph)CN (11.5 g.) and CH2N2 from 11 g. I yielded similarly 10.53 g. 4:1 mixture of 1-benzylthio-1-cyanocyclopropane and MeCH:C(SCH2Ph)CN, b0.15 104-6\u00b0, n20D 1.5676; a 10-g. portion in 100 g. AcOH-HCl heated 7 hrs. on the steam bath and evaporated, the residue treated with Et2O and aqueous NaHCO3, and the aqueous phase acidified gave 5.55 g. 1-benzylthiocyclopropane-1-carboxylic acid, prisms, m. 132-3\u00b0 (C6H6-petr. ether). MeCH:C(SMe)CO2Me (10 g.) in 100 cc. Et2O treated with CH2N2 from 10 g. I in 100 cc. Et2O, 1 g. of the resulting crude pyrazoline ester kept at room temperature, and filtered gave 0.51 g. Me 4-methylpyrazole-3-carboxylate (VIII), m. 172\u00b0 (aqueous MeOH). Crude pyrazoline ester (12 g.) added dropwise to a flask at 110-13\u00b0 gave 5.5 g. VIII, m. 172\u00b0; the residue from the petr. ether washings gave 2.65 g. unidentified oil, b15 88-91\u00b0, n20D 1.4902, which by acid hydrolysis gave MeSH. In the experiment, the researchers used many compounds, for example, Methyl 1H-pyrazole-3-carboxylate(cas: 15366-34-4<a href=\"https:\/\/www.ambeed.com\/products\/15366-34-4.html\">Product Details of 15366-34-4<\/a>)<\/p>\n<p>Methyl 1H-pyrazole-3-carboxylate(cas: 15366-34-4) belongs to pyrazoles. The application of pyrazole derivatives in the development of anticancer agents has been thoroughly investigated and verified. Moreover, the medicinal features of a number of natural products incorporating pyrazole moiety such as pyrazofurin, pyrazofurin B, pyrazole-3(5)-carboxylic acid and 4-methylpyrazole-3(5)-carboxylic acid have been reported.<a href=\"https:\/\/www.ambeed.com\/products\/15366-34-4.html\">Product Details of 15366-34-4<\/a><\/p>\n<p>Referemce:<br \/><a href=\"https:\/\/en.wikipedia.org\/wiki\/Pyrazole\">Pyrazole &#8211; Wikipedia<\/a>,<br \/><a href=\"https:\/\/www.sciencedirect.com\/topics\/chemistry\/pyrazoles\">Pyrazoles &#8211; an overview | ScienceDirect Topics<\/a><\/p>\n","protected":false},"excerpt":{"rendered":"<p>Methyl 1H-pyrazole-3-carboxylate(cas: 15366-34-4) belongs to pyrazoles. The application of pyrazole derivatives in the development of anticancer agents has been thoroughly investigated and verified. Moreover, the medicinal features of a number of natural products incorporating pyrazole moiety such as pyrazofurin, pyrazofurin B, pyrazole-3(5)-carboxylic acid and 4-methylpyrazole-3(5)-carboxylic acid have been reported.<a href=\"https:\/\/www.ambeed.com\/products\/15366-34-4.html\">Product Details of 15366-34-4<\/a><\/p>\n","protected":false},"author":8,"featured_media":0,"comment_status":"closed","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"footnotes":""},"categories":[174,131],"tags":[128],"class_list":["post-10337","post","type-post","status-publish","format-standard","hentry","category-15366-34-4","category-pyrazoles-derivatives","tag-100-200"],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v24.9 - https:\/\/yoast.com\/wordpress\/plugins\/seo\/ -->\n<title>Gundermann, Karl Dietrich&#039;s team published research in Chemische Berichte in 1960 | CAS: 15366-34-4 | pyrazoles-derivatives<\/title>\n<meta name=\"description\" content=\"In 1960,Gundermann, Karl Dietrich; Thomas, Rainer published \u300aMercaptoacrylic acid derivatives. VII. The effect of thioether groups on the stabilization of 1-pyrazoline-3-carboxylic acid derivatives\u300b.Chemische Berichte published the findings.Product Details of 15366-34-4 The information in the text is summarized as follows:\" \/>\n<meta name=\"robots\" content=\"index, follow, max-snippet:-1, max-image-preview:large, max-video-preview:-1\" \/>\n<link rel=\"canonical\" href=\"https:\/\/www.pyrazoles-derivatives.com\/?p=10337\" \/>\n<meta property=\"og:locale\" content=\"en_US\" \/>\n<meta property=\"og:type\" content=\"article\" \/>\n<meta property=\"og:title\" content=\"Gundermann, Karl Dietrich&#039;s team published research in Chemische Berichte in 1960 | CAS: 15366-34-4 | pyrazoles-derivatives\" \/>\n<meta property=\"og:description\" content=\"In 1960,Gundermann, Karl Dietrich; Thomas, Rainer published \u300aMercaptoacrylic acid derivatives. VII. The effect of thioether groups on the stabilization of 1-pyrazoline-3-carboxylic acid derivatives\u300b.Chemische Berichte published the findings.Product Details of 15366-34-4 The information in the text is summarized as follows:\" \/>\n<meta property=\"og:url\" content=\"https:\/\/www.pyrazoles-derivatives.com\/?p=10337\" \/>\n<meta property=\"og:site_name\" content=\"pyrazoles-derivatives\" \/>\n<meta property=\"article:published_time\" content=\"2022-10-19T20:13:01+00:00\" \/>\n<meta name=\"author\" content=\"Jessica.F\" \/>\n<meta name=\"twitter:card\" content=\"summary_large_image\" \/>\n<meta name=\"twitter:label1\" content=\"Written by\" \/>\n\t<meta name=\"twitter:data1\" content=\"Jessica.F\" \/>\n\t<meta name=\"twitter:label2\" content=\"Est. reading time\" \/>\n\t<meta name=\"twitter:data2\" content=\"4 minutes\" \/>\n<script type=\"application\/ld+json\" class=\"yoast-schema-graph\">{\"@context\":\"https:\/\/schema.org\",\"@graph\":[{\"@type\":\"WebPage\",\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/?p=10337\",\"url\":\"https:\/\/www.pyrazoles-derivatives.com\/?p=10337\",\"name\":\"Gundermann, Karl Dietrich's team published research in Chemische Berichte in 1960 | CAS: 15366-34-4 | pyrazoles-derivatives\",\"isPartOf\":{\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/#website\"},\"datePublished\":\"2022-10-19T20:13:01+00:00\",\"author\":{\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/#\/schema\/person\/d9a9f27bed675392c6f363a01ffd49f1\"},\"description\":\"In 1960,Gundermann, Karl Dietrich; Thomas, Rainer published \u300aMercaptoacrylic acid derivatives. VII. The effect of thioether groups on the stabilization of 1-pyrazoline-3-carboxylic acid derivatives\u300b.Chemische Berichte published the findings.Product Details of 15366-34-4 The information in the text is summarized as follows:\",\"breadcrumb\":{\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/?p=10337#breadcrumb\"},\"inLanguage\":\"en-US\",\"potentialAction\":[{\"@type\":\"ReadAction\",\"target\":[\"https:\/\/www.pyrazoles-derivatives.com\/?p=10337\"]}]},{\"@type\":\"BreadcrumbList\",\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/?p=10337#breadcrumb\",\"itemListElement\":[{\"@type\":\"ListItem\",\"position\":1,\"name\":\"\u9996\u9875\",\"item\":\"https:\/\/www.pyrazoles-derivatives.com\/\"},{\"@type\":\"ListItem\",\"position\":2,\"name\":\"Gundermann, Karl Dietrich&#8217;s team published research in Chemische Berichte in 1960 | CAS: 15366-34-4\"}]},{\"@type\":\"WebSite\",\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/#website\",\"url\":\"https:\/\/www.pyrazoles-derivatives.com\/\",\"name\":\"pyrazoles-derivatives\",\"description\":\"Several pyrazole derivatives possess important pharmacological activities and they have been proved useful materials in drug research. Pyrazole derivatives play an important role in antitumor agents.\",\"potentialAction\":[{\"@type\":\"SearchAction\",\"target\":{\"@type\":\"EntryPoint\",\"urlTemplate\":\"https:\/\/www.pyrazoles-derivatives.com\/?s={search_term_string}\"},\"query-input\":{\"@type\":\"PropertyValueSpecification\",\"valueRequired\":true,\"valueName\":\"search_term_string\"}}],\"inLanguage\":\"en-US\"},{\"@type\":\"Person\",\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/#\/schema\/person\/d9a9f27bed675392c6f363a01ffd49f1\",\"name\":\"Jessica.F\",\"image\":{\"@type\":\"ImageObject\",\"inLanguage\":\"en-US\",\"@id\":\"https:\/\/www.pyrazoles-derivatives.com\/#\/schema\/person\/image\/\",\"url\":\"https:\/\/en.cravatar.com\/avatar\/2d1cec2a99eeaad5a5b217c9cdbfb610?s=96&d=mm&r=g\",\"contentUrl\":\"https:\/\/en.cravatar.com\/avatar\/2d1cec2a99eeaad5a5b217c9cdbfb610?s=96&d=mm&r=g\",\"caption\":\"Jessica.F\"}}]}<\/script>\n<!-- \/ Yoast SEO plugin. -->","yoast_head_json":{"title":"Gundermann, Karl Dietrich's team published research in Chemische Berichte in 1960 | CAS: 15366-34-4 | pyrazoles-derivatives","description":"In 1960,Gundermann, Karl Dietrich; Thomas, Rainer published \u300aMercaptoacrylic acid derivatives. VII. The effect of thioether groups on the stabilization of 1-pyrazoline-3-carboxylic acid derivatives\u300b.Chemische Berichte published the findings.Product Details of 15366-34-4 The information in the text is summarized as follows:","robots":{"index":"index","follow":"follow","max-snippet":"max-snippet:-1","max-image-preview":"max-image-preview:large","max-video-preview":"max-video-preview:-1"},"canonical":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337","og_locale":"en_US","og_type":"article","og_title":"Gundermann, Karl Dietrich's team published research in Chemische Berichte in 1960 | CAS: 15366-34-4 | pyrazoles-derivatives","og_description":"In 1960,Gundermann, Karl Dietrich; Thomas, Rainer published \u300aMercaptoacrylic acid derivatives. VII. The effect of thioether groups on the stabilization of 1-pyrazoline-3-carboxylic acid derivatives\u300b.Chemische Berichte published the findings.Product Details of 15366-34-4 The information in the text is summarized as follows:","og_url":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337","og_site_name":"pyrazoles-derivatives","article_published_time":"2022-10-19T20:13:01+00:00","author":"Jessica.F","twitter_card":"summary_large_image","twitter_misc":{"Written by":"Jessica.F","Est. reading time":"4 minutes"},"schema":{"@context":"https:\/\/schema.org","@graph":[{"@type":"WebPage","@id":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337","url":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337","name":"Gundermann, Karl Dietrich's team published research in Chemische Berichte in 1960 | CAS: 15366-34-4 | pyrazoles-derivatives","isPartOf":{"@id":"https:\/\/www.pyrazoles-derivatives.com\/#website"},"datePublished":"2022-10-19T20:13:01+00:00","author":{"@id":"https:\/\/www.pyrazoles-derivatives.com\/#\/schema\/person\/d9a9f27bed675392c6f363a01ffd49f1"},"description":"In 1960,Gundermann, Karl Dietrich; Thomas, Rainer published \u300aMercaptoacrylic acid derivatives. VII. The effect of thioether groups on the stabilization of 1-pyrazoline-3-carboxylic acid derivatives\u300b.Chemische Berichte published the findings.Product Details of 15366-34-4 The information in the text is summarized as follows:","breadcrumb":{"@id":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337#breadcrumb"},"inLanguage":"en-US","potentialAction":[{"@type":"ReadAction","target":["https:\/\/www.pyrazoles-derivatives.com\/?p=10337"]}]},{"@type":"BreadcrumbList","@id":"https:\/\/www.pyrazoles-derivatives.com\/?p=10337#breadcrumb","itemListElement":[{"@type":"ListItem","position":1,"name":"\u9996\u9875","item":"https:\/\/www.pyrazoles-derivatives.com\/"},{"@type":"ListItem","position":2,"name":"Gundermann, Karl Dietrich&#8217;s team published research in Chemische Berichte in 1960 | CAS: 15366-34-4"}]},{"@type":"WebSite","@id":"https:\/\/www.pyrazoles-derivatives.com\/#website","url":"https:\/\/www.pyrazoles-derivatives.com\/","name":"pyrazoles-derivatives","description":"Several pyrazole derivatives possess important pharmacological activities and they have been proved useful materials in drug research. Pyrazole derivatives play an important role in antitumor agents.","potentialAction":[{"@type":"SearchAction","target":{"@type":"EntryPoint","urlTemplate":"https:\/\/www.pyrazoles-derivatives.com\/?s={search_term_string}"},"query-input":{"@type":"PropertyValueSpecification","valueRequired":true,"valueName":"search_term_string"}}],"inLanguage":"en-US"},{"@type":"Person","@id":"https:\/\/www.pyrazoles-derivatives.com\/#\/schema\/person\/d9a9f27bed675392c6f363a01ffd49f1","name":"Jessica.F","image":{"@type":"ImageObject","inLanguage":"en-US","@id":"https:\/\/www.pyrazoles-derivatives.com\/#\/schema\/person\/image\/","url":"https:\/\/en.cravatar.com\/avatar\/2d1cec2a99eeaad5a5b217c9cdbfb610?s=96&d=mm&r=g","contentUrl":"https:\/\/en.cravatar.com\/avatar\/2d1cec2a99eeaad5a5b217c9cdbfb610?s=96&d=mm&r=g","caption":"Jessica.F"}}]}},"_links":{"self":[{"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=\/wp\/v2\/posts\/10337","targetHints":{"allow":["GET"]}}],"collection":[{"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=\/wp\/v2\/posts"}],"about":[{"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=\/wp\/v2\/users\/8"}],"replies":[{"embeddable":true,"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcomments&post=10337"}],"version-history":[{"count":0,"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=\/wp\/v2\/posts\/10337\/revisions"}],"wp:attachment":[{"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=%2Fwp%2Fv2%2Fmedia&parent=10337"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=%2Fwp%2Fv2%2Fcategories&post=10337"},{"taxonomy":"post_tag","embeddable":true,"href":"https:\/\/www.pyrazoles-derivatives.com\/index.php?rest_route=%2Fwp%2Fv2%2Ftags&post=10337"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}