diphenylphosphoryl azide - jst
TRANSCRIPT
ãž ã ãš ã ã« ãª ã³ é ž 㢠㞠ã
å¡© å ¥ å ä¹*ã» å±± ç° ä¿ äž*
Diphenylphosphoryl Azide
Takayuki SHIOIRI*, and Shun-ichi YAMADA*
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1) T. Shioiri, K. Ninomiya, S. Yamada, J. Amer. Chem. Soc. 94 6203 (1972)
2) å¡©å ¥å ä¹,å±± ç°ä¿äž,第9å ãã ã ãèšè«äŒè¬æŒ
èŠ æšé,p.5(1971.11)é 岡
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èšè«äŒè¬æŒäºçš¿é p.17(1972.1)æ± äº¬
4) F. Cramer, M. Wintern, Chem. Ber. 94 989
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(1961)5) F.L. Scott, R.Riordan, P.D. Morton, J. Org.
Chem. 27 4255 (1962)6) ç¢ å³¶æ²» æ,æ åå2927(1971)
7) Y.S. Klausner, M. Bodanszky, Synthesis 1972
453
8) M.W. Williams, G.T. Young, J. Chem. Soc.
1963 881
9) M.W. Williams, G.T. Young, J. Chem. Soc.
1964 3701
10) å¡©å ¥åä¹,å° æ²¢å¥å¿,å±± ç°ä¿äž,第10å ãã ã ã
èšè«äŒè¬æŒèŠ æšé,p.15(1972.9)æ å¹
11) ææç« ,æŸ å°Ÿå¯¿ä¹,銬 å ŽçŸ©åœŠ,è çœè³ª æ ž é ž é µ çŽ
17 479 620 1972)
12) J. BÆÃbler, J.-K. Chang, F. Enzmann, K. Fol.-
kers, J. Med. Chem. 14 475 (1971)
13) äºæ æé,é å®æ¡å©,é å®éŽ,æº å£å¯è,æ è€æž
äž ,è¬ èª90850(1970)
14) å¡©å ¥åä¹,äº å®®éŠå,å±± ç°ä¿äž,æ æ©ã€ãª ㊠ã»ãª
ã³ååç©èšè«äŒè¬æŒ èŠæšép.79(1973.2)京
éœ15) H. Meyer, J. Mally, Monatsh. 33 393 (1912) 16) H. Wolff, Organic Reactions III 30717) äºå®®éŠå,å¡© å ¥å ä¹,å±± ç°ä¿äž,æ¥ æ¬è¬åŠäŒç¬¬93
幎äŒè¬æŒèŠ æšéII-70(1973.4)æ± äº¬
18) T. Curtius, W. Sieber, Ber. 54 1430 (1921) 19) M.I. Kabachnik, V.A. Gilyarov, Izvest. Akad.
Nauk S.S.S.R., Otdel. Khim. Nauk 1961 819; C.A. 55 27014d (1961)
20) S. Rengaraju, K.D. Berlin, Tetrahedron 27 2399 (1971)
21) ã ãšã ã°R.Breslow, Chem.Soc. Rev.1553
(1972)
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