ã«ãããªã³ã°åå¿ï¼è±: coupling reaction ï¼ã¨ã¯ã2ã¤ã®åå¦ç©è³ªãé¸æçã«çµåãããåå¿ã®ãã¨ã ç¹ã«ãããããã®ç©è³ªãæ¯è¼ç大ããªæ§é ï¼ã¦ãããï¼ãæã£ã¦ããã¨ãã«ç¨ãããããã¨ãå¤ãã ã§ããï¼ ä»åº¦ã¯ä¸å±¤é¨åãã¹ãã¤ãã§2mLåããã¼ã«ã¼ã«ã ããªããå ããã¨ããªã¬ã³ã¸-iI(赤æ©è²ã®åºä½)ãçæãã[ã¢ã¾ã«ãããªã³ ã°åå¿â¦ ã©ã³ (TMSBr) ãå ã ããã¨ã§ãã¢ãã¤ãã¼åã³éå°é¿åãªãã«ã¯ã³ãããã§é«åç¨ã«ã¯ãã¹ã«ãã ãªã³ã°ãéè¡ãã (eq. 4 Silicones for Resin Modification 1-2. é«æ ¡ã§ãææ©å®é¨ã§ã¸ã¢ã¾ã«ãããªã³ã°ã®å®é¨ãè¡ãã¾ãã canacana44.hatenablog.com æ¬æ ¡ã§è¡ã£ãå®é¨ã§ã¯ã ã¢ããªã³ å¡©é
¸å¡©ã¨ äºç¡é
¸ãããªã¦ã ã§ã¸ã¢ã¾åãã2-ãããã¼ã«ã¨ æ°´é
¸åãããªã¦ã ã®è©¦è¬ã¨ ã«ãã ãªã³ã°ããã¦ã¢ã¾ååç©ã®1-ãã§ãã«ã¢ã¾-2-ãããã¼ã«ã§å¸ãæãã¾ãã ã³ãã«ã§æç¨ åå¿æ©æ§ 1. ããã²ã³åã¢ãªã¼ã«ã®ãã©ã¸ã¦ã ã¸ã®é
¸åçä»å ã èé ã«ãããªã³ã°ï¼Sonogashira couplingï¼ èé ã«ãããªã³ã°ï¼Sonogashira couplingï¼ ãã©ã¸ã¦ã ã触åªã¨ãã¦ãããã²ã³åã¢ã«ã±ãã«ã¾ãã¯ããã²ã³åã¢ãªã¼ã«ã«é
触åªãå¡©åºãä½ç¨ãããã¢ã«ãã³æ°´ç´ ã¨ã¯ãã¹ã«ãããªã³ã°ãããåå¿ã§ããã ã¯ãã¹ã«ãããªã³ã°åå¿ã¨ã¯ã2ã¤ã®åå¦ç©è³ªãé¸æçã«çµåãããåå¿ã§ãããç¹ã«ææ©ããã²ã³åç©ã¨ ææ©éå±ååç©ã¨ã®ã¯ãã¹ã«ãããªã³ã°åå¿ã¯2000年以éæ¥éã«å©ç¨ãæ¡å¤§ããã製è¬ãã¨ã¬ã¯ãããã¯ã¹ ã®åéã§ç¨®ã
ã®ååç©åæã«å¹
åºãå©ç¨ããã¦ãã¾ãã 5) ã åå¿ã¯ã1981å¹´ã«é´æ¨ã宮浦ãã«ããå ±åãããé´æ¨ ã«ãããªã³ã°åå¿1ï¼ã¨èãããããæ¬åå¿ã¯ããã© ã¸ã¦ã 触åªã¨å¡©åºåå¨ä¸ã«ã¢ãªã¼ã«ãã©ã¤ãã¨ã¢ãªã¼ ã«ããã³é
¸ã¨ãã¯ãã¹ã«ãããªã³ã°ãããã ⦠ãããã試é¨ãªã®ã§ããã£ã¦ãããã¨ã§ããã¸ã¢ã¾ã«ãããªã³ã°ã«ã¤ãã¦ãªã®ã§ãããä¸é£ã®åå¿æ©æ§ï¼é»åã®åãã¨ããç¢å°ã¨ãï¼ãåå¿ã®ç¹å¾´ããã¤ã³ãããªãã§ããããã§ãæãã¦ãã ãããç¹ã«åå¿æ©æ§ï¼è©¦é¨ã«çµ¶å¯¾åºãï¼ã«ã¤ãã¦ã¯ã¡ ¥ç¨ã® ... ã°ã¯ã©ã¡ããåå¿ã®æ©æ§èªä½ã¯æºåæ¨-Heck ... ã¢ãªã«ã¹ãºååç©ã使ã£ãStille ã«ãããªã³ã°ããã使ãããã«ãã ãªã³ã°åå¿ã®ä¸ã¤ã§ããã(Scheme 10) 7 移éå±ãç¨ããã¢ãªã«ä½çç´ ï¼ããç´ çµåæ´»æ§åãçµãåå¿ã¨ãã¦ãæ±é»åå¤ã¨ã®è±ããç´ ã«ãã ãªã³ã°ãå ±åããã¦ãããå½ç 究室ã§ã¯ã2-ããªãã«ãªãã¡ãã«-1-ã¢ã«ã±ã³ã®çç´ âããç´ çµååæã ä¼´ãHeckåç°ååå¿ãå ±åãã¦ãã (å¼ 18) 23ã ãããçµã¦xï¼ãè±é¢ããã¨èãããã¦ãããããã® å¾ã®ç 究ã«ãã£ã¦ãç¾å¨ã§ã¯ãå¡©åºã«ããβâè±é¢ ã¨ããèãæ¹ãæåã§ãã5ï¼ã vnsåå¿ã«ãããã¢ããåå¤ã¨ãã¦ã¯ã4ï¼ã¢ã ã¸ã¢ã¾åãã¸ã¢ã¾ã«ãããªã³ã°ã¯è³é¦æã§æãé¢åãªåéã§ãããããããªä½ç³»çã«ã¾ã¨ãã¦ããã¾ããã¸ã¢ã¾åã¯ãªãäºç¡é
¸ãããªã¦ã ãä½é³ã§åå¿ãããã®ããã¸ã¢ã¾ã«ãããªã³ã°ã§ã¯ããªãNaOHã¨åå¿ãããã®ãï¼ãªã©æå³ä¸æãªåå¿ãå¤ãããã¾ãã ã¥åå¿ã¯ç³ãæ¤åºãã¾ãã ç³ãå¡©é
¸ã¨åå¿ãã¦ãã«ãã©ã¼ã«èªå°ä½ã«ãªãαãããã¼ã«ã¨åå¿ãç´«ã®è²ç´ ã®ååç©ãç®åºãããã¨ã¯ãããã®ã§ãããããªãªã¼ã¹ããã ⦠å¤å
¸çåå¿æ¡ä»¶ã§ã¯é
ã¢ã»ããªããé
¸ç´ å¦çãããã¨ã§è¡ãããå¾ã«å種å¤æ³ãéçºãããã ç¹ã«æåãªã®ã¯éå°éã®Cu(OAc)2ã使ããããªã¸ã³æº¶åªã§åå¿ãããEglintonå¤æ³ã触åªéã®CuCl-TMEDAãç¨ãã¦é
¸ç´ é°å²æ°ä¸ã§è¡ãHayå¤æ³ã®äºã¤ã åºæ¬æç® åå¿ã¾ã§é¡ã(å³2)ã1) ããã§ã¯ããã©ã¸ã¦ã ã¯ã½ã åå¿æ©æ§ ã¸ã¢ã¾ãã¦ã ååç©ã¯ãäºç¡é
¸ãããªã¦ã ãé
¸æ§æ¡ä»¶ã§å¦çãããã¨ã§çããæ´»æ§ç¨®ã¨ã¢ããªã³ã®åå¿ã§çããã çããã¸ã¢ã¾ãã¦ã å¡©ã¨é»åè±å¯è³é¦ç°ã¯ãè³é¦ææ±é»åç½®æåå¿ï¼S E Arï¼å½¢å¼ã§åå¿ â¦ ã«ãããªã³ã°åå¿ã«ã¤ãã¦. 触åªåé§ä½4ã¯1-ãããã¼ã«é¡ã®ã¿ãªãã2-ãããã¼ã«é¡ã®ä¸æååå
é
¸åçã«ãã ãªã³ã°åå¿ã«ãæå¹ã§ãããé«åçãé«ã¨ãã³ããªé¸æçã«ã©ã¯ãã³ãå¾ãã2-ãããã¼ ã«é¡ã®ä¸æååå
é
¸åçã«ãããªã³ã°åå¿ã¨ãã¦ã¯åãã¦ã®æåä¾ã§ãããååç©3ã«æ¯ ãå
±æçµåæ§ã®çµåã§ãããããã©ã³ã¹ã¡ã¿ã«åãé²è¡ããªãã§ãããå¡©åºã«ãããã¦ç´ ã®ã¢ã¼ãåé¯ä½ãå½¢æãããã¨ãçç´ ã®æ±æ ¸æ§ãä¸ãããPd-Brçµåã¸ã®ãã©ã³ã¹ã¡ã¿ã«åãé²è¡ã§ãã㠨第1ç« ã§ã¯å種ã®pHã§ã®ã«ãããªã³ã°åå¿ã®é度測å®ã«ãã,ãã®åå¿ã®æ©æ§ãæãã ã«ãã¦ã ⦠ã¢ããªã³ãã©ãã¯ãO.K. ãã®ãããªã³ã°ç¶å
±æã§ã¯ãªããªãã¾ãã æ¾åºããã2åã®æ°´ç´ ã©ã¸ã«ã«ã¯ã©ã¸ã«ã«åããåå¿æ§ææ©ææ㨠çµåããåå¿æ§ææ©ææã©ããã®çµåãé»å®³ãã¾ãã ã¾ãããã³ã¾ããã³ã¯æ°´ç´ ã©ã¸ã«ã«ã¨åå¿ãå
ã®ãããããã³ï¼hq)ã« æ»ãæ§è³ªãããã¾ãã ã¹ãã£ã«ã«ãããªã³ã°åå¿ã«ãããæ´»æ§ãªè§¦åªã¯ç³»ä¸ã§å½¢æãã14é»åPdï¼0ï¼é¯ä½ã¨èãããã¦ããããã©ã¸ã¦ã ï¼0ï¼é¯ä½ãç´æ¥ãããã¯é
ä½åãå ãã¦ä½¿ç¨ãã¾ãã äºä¾¡ãã©ã¸ã¦ã 触åªã使ç¨ãããã¨ãã§ãã¾ãã ã¢ããªã³ã®åæå®é¨ã§ããããã³ã¼ã³ããã¢ããªã³ãä½ãã¾ããï¼ ä¸å±¤é¨åãã¢ããªã³ã溶ãè¾¼ãã ã¨ã¼ãã«å±¤ã§ãã ä¸å±¤é¨åã§ã®ç¢ºèªå®é¨ã¾ã§ãååã®blogã§ç´¹ä»ãã¦ããã ãããç²ã¨ã®åå¿ãO.K. ã©ã³ã«ãã ãªã³ã°å¤ã®åå¿ãªã©å¤æ°ããï¼è¡¨1 ... å¼1 æ¶æ©æ©æ§. ã©ã³ã«ãã ãªã³ã°å¤ã®éï¼pHï¼æ°´åã®å½±é¿ã調ã¹ãï¼çµå ã®å½¢æ
ã¯29Siï¼NMRã« ãã£ã¦ï¼åå¿é度ã¯çºç ããã³ã¼ã«-ããã³ãã³è»¢ä½åå¿ 203 96 Pummerer転ä½åå¿ 205 97 Rupe転ä½åå¿ 207 98 Meyer-Schuster転ä½åå¿ â¦ ã¥åå¿ã®ç¨èªè§£èª¬ - çæ°´åç©ã®æ¤åºæ³ã®1ã¤ãç³æ¶²ã«Î±-ãããã¼ã«ã¨ç¡«é
¸ãä½ç¨ããã¦èµ¤ç´«è²ã«çºè²ãããåè²åå¿ããã®åå¿ã¯ã¢ããç³ä»¥å¤ã®ãã¹ã¦ã®çæ°´åç©ã«å¯¾ãé½æ§ã§ããã ãã§ã¼ãªã³ã°åå¿ã®è¦ãæ¹ã¨åå¿å¼ã®ä½ãæ¹ãå¦ãã§è¡ãã¾ããè² ãã¼ãªã³ã°åå¿ã¯ãã¢ã«ãããã®æ¤åºåå¿ã¨ããã¾ãããå¾®å¦ã«éé¡åå¿ã¨ã¯ç°ãªãã¾ãããã®éããå®éæ°æ½å¤§å¦ã§ç¥ã£ã¦ãããªãã¨ãã¡ãªåé¡ãåºã¦ãã¾ãã®ã§ã絶対ç¥ã£ã¦ããã¦ãã ããã ãã¦ãããã¤ãã®ç 究ã°ã«ã¼ããããã¾ãã¾ãªã¯ãã¹ã«ãã ãªã³ã°åå¿ã«å¯¾ããæå¹æ§ã¨æ±ç¨æ§ãæ¤è¨ãã¦ãã¾ã1ãã ã¹ãã£ã³ã®åè£ã¨ãã¦ã¯P(t-Bu) 3 ãé¸ã°ããHeck åå¿ãæ ¹å²¸ åå¿ãé´æ¨åå¿ãèé åå¿ãªã©ã®ã¯ãã¹ã«ãããªã³ã°åå¿ã® ã«ãããªã³ã°åå¿ã«ããè²ã®å¤åã«é¢ãã質åã§ãã試é¨ç®¡å
ã§pâãããã¢ããªã³ã«æ¿ç¡«é
¸ãå ãã次ãã§äºç¡é
¸ãããªã¦ã ã§ã¸ã¢ã¾åãã¾ãã(溶液1)ãããã¦å¥ã®è©¦é¨ç®¡ã«ã¦ã2âãããã¼ã«ã«NaOHãå ãã¦æº¶ããã¾ãã(溶液2)ãæå¾ã«æº¶æ¶²1 åå¿æ©æ§. æ¦è¦ ãã©ã¸ã¦ã 触åªãç¨ããææ©ãã¦ç´ ååç©ã¨ææ©ããã²ã³ååç©ããã¯ãã¹ã«ãããªã³ã°ãããåå¿ãæ¡ä»¶ãæ¯è¼ç温åã§ããå®è½åºé¸ææ§ãé«ããæ°ãããã©ã¸ã¦ã ã«ãããªã³ã°ã®ãªãã§ã使ããããåå¿ â¦