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NHSO2R NHSO2R NHSO2R H2O2, + H+ MeCN, OHMeOH O OH C D 40, 41 (84-92%) NHSO2R -H+ +-OMe NHSO2R O E OH 44, NHSO2R NHSO2R OMe OH OMe N OH SO2R OH 46, 47 48, (32-35%) 42, R=Me (40, 42, 44, 46, 48), R=napa-CH3C6H4 (41, 43, 45, 47, 49) B pooee cceoa, N-eoe pooe oeeao ae oepy oce ccea I II. a peyx cyax, oapye o oee poox aa opmooya. Ta, p opaoe eaa 50 H2O2 pcyc aeopa oye c xoo 44 % oc 52, a peaoo cec e pcao. Pea e 50 c H2O2, aapyea cceo Na2WO4 H3PO4, ae eoca 51 (xo 54 %). oa pepa oye oc poooe aoaa e ece pacopa aaa eaoe p oao eepaype po ae opaoa coee 51.

NH3, MeOH NHBz HO NHBz H2O2, H2O2, MeCN, OH- Me Me O Na2WO4, H3POO MeOH MeOH N Ph Me 51 (54 %) 50 52 (44%) Oo p oeo ycooc oca ao cyae ( oo peyx cyae oc oapye e ) oe e coo yeea c opae yo eo apoaecoo pa ocooc aoa copoa py C6H5CO (o cpae, apep, c CH3CO), o cae cocooc eo yceo aae aoa C(1) ocoo oa c aae eoca.

poooe aa 53 p ec oex ocex cce ae ece poy 3,1-eoca 54 (xo 5255 %).

H2OHO /Na2WO4, H3POBzCl, K2COO /MeCN, OHNH2 CH2ClMeOH NHBz N Ph 4 53 54 (5255 %) opa 55, oye aa 4 ae p opaoe ccea I II cec oo 56 57 c o xoo 60-68 %, poo e o aa opa 58 p ec oox peaeo pepaaec coy cec eec.

CHO CHO CHO H2ONH NH NH /Na2WO4, H3PO /MeCN, OH- OH OH OH OH MeOH 55 56 Bee aoa aoa aeapaa xaooy ccey pecae coco eo a, cxo c apoae, poe oo, coee xaooo ppo peca epec o pe coo ooeco aoc, cep oopo ocaoo po ca oo oec peapa, peee peoaaee pee epoo, opoo apoo. B c c pecaec eecoopa oyee xao-4-oo c 3-aee aecee, ex oea aee yoaa ece ocee.

B aece eoa cea o pao aoece eocaoa 59 c cooecy oeeao 4 15 p cae eee 3 aco. Pea poxo c xoa 7981 %.

Baoece c epec oopoa pcyc Na2WO4 H3PO4 a poooo aa 60, a poooo oya 61 e po opaoa ax-o poyo. Pea 60 c cceo II ae ece poy c xoo 53 % - N-oc (62). Coeee 61 x ycox pea c epec oopoa e cyae.

O O O H2O2, O 140oC MeCN, OH- N 4, N 3 MeOH N CHR N CHN CHO59 60, 61 (7981 %) 62 (53 %) R=H (60), R=Me (61) Be o-eo py py poox opmo-oya a poeae pea oce, aaaeec a ece N-aece, epoo, ec oe cee cepec, ee epo, a a aeoe (8) ocopoe (21) pooe napa-oya e ey pyy ae ema-ooe aeoy aece, oo o cyae oa e aoecye pocpaceo c N-aecee, o oa oaa aaooe opmo-pye epooe e a oy c, oao, peapy napa-oy (o o peyx pepo) aaoo poo aa (7,20), e e eo py pe.

2. pepae opmo-(1-e-1-ye)apao o ece H2OHapy c o-(oae)apaa eoocy poya aoepepypo ea c aece aepooe 64, oyaee c peee 3-xopeea, o ooe ocyec yee pea oce opoex poox c e cpae aopa poyo c ao ecx poox.

oepa coee 63, 64 ocyecac x ee a OH eee 1 aca pea cooecy poo 65, 66 c xoa 3638 %. Apoae 65,66 poooc ece xopopaa a oao Ac2O xopco eee (xo 8596 %).

NH2 NHCOR NHRCOCl, K2COR1 RR1 Et Ac2O KOH CH2Cl2 Et 300oC,1 R2 RR 63,64 65,66 (36-38%) 67-70 (85-96 %) R1=R2=H (63, 65, 67, 68); R1=R2=Me (64, 66, 69, 70); R=Me (67,69); R=OEt (68, 70) ece cce I II a a 67 peo opaoa ooooex eepyex cece poyo. poooe 68 ae p ec H2O2 pcyc MeCN ooao c xoo 76 % oc 71, oop yco epae xpoaopapoae a caee. ece opaao cce a 68 ae coy cec poyo.

NHCOOEt NHCOOEt H2O2, MeCN, OHMeOH Et O Et 68 71 (76 %) peee opaao cce coee 69, coepaey opmoey pyy, yeae ooaoc poea pea o cpae c ao 67 ece poyo oaaec eoca 72 (xo 77 %). B cyae pea 69 c cceo II c xoo opayec oc 73.

OH NHAc H2O2, NHAc Me Et H2O2, Na2WO4, Me Et Me Et O H3POMeCN, OHO MeOH MeOH N Me Me Me Me 73 (37 %) 69 72 (77 %) ocapooe coeee 70 p ec oex ocex cce ae eocao 74. Oeo, ae opmo-eo py cy ec ecapy aopo cae ycooc poeyoo opayeoc oca o cpae c eeco 71.

OH H2OEt Me /Na2WO4, H3PO4 Me Et O /MeCN, OHNHCOOEt MeOH N O H Me Me 70 74 (7077 %) 3. pepae opmo-(oece-1-)apao o ece H2Opocpaceoe cpoee oeceoo oa oaec o oeeoo, o ooe oa oo oee oecex cycpao ycox oce p pox pax ycox.

Aea 77, 78 oye aoece ao 75, 76 c Ac2O CH2Cl2, xo 90 %, (a 76 oye aaoo 4), ea 79, 80 oya ece a cooecye a eoxopa CH2Cl2 pcyc K2CO3 c xoa 9094%. oyee a oepa ec H2O pcyc Na2WO4 H3PO4 MeCN OH. Heaco o a cooaoo peaea aece p aoe aoa oye 3,1-eoca 81 84 c xoa 3246 %, o ec oepc cxox coee aeo e, e cyae oeex poox, oa a pe poea pea pepo a paa oe.

HO H2ONHCOR NHBzCl, K2CO3R/Na2WO4, H3POO R Ac2O /MeCN, OHN R CH2ClMeOH R75, 76 7780 8184(3246%) R1=H : 75; (77, 81) R=Me; (79, 83) R=Ph;

R1=Me: 76; (78, 82) R=Me; (80, 84) R=Ph ocapoe aao ae e oapya yceoc y opmo-aece. pooe 85, 86 oye ece EtOCOCl CH2Cl2 pcyc K2CO3 a cooecye a c xoa 9295 %.

ece cce a ocoe aeopa coee pepaac 3,1eoca-2-o 87, 88 (xo 5253 %), eoo TCX epo cyae pecppyec ae peaoo cec opoo poya apy c eocao, oeo, o ec oco peeceo 87, oao, e o coeee e yaec. Bxo x pea ae e, e cooecyx oeex coee. Ocea ccea I e oaae ec a coee 85,86.

HO EtOCOCl, H2O2, K2COO CH2ClMeCN, OHNH2 MeOH NHCOOEt N O H R R R 75,76 85,86(9295%) 87,88(5253 %) R=H (75, 85, 87), R=Me (76, 86, 88) o yeo e eo py a cpoee poyo oce.

ece oox ocee a cyoa 89 po cec eec, oop pca cpyyp acepeoepx cpo 91, 92 c o xoo % (50:50). Opayc poy, epoo, peyae aa oeyo eaoa c yx apae capoaoo eoo aoa, opayeoc epoo oca. Aaoa opaoa cyoaa 90, oyeoo epoae coee 76, e pea opaoa aex oec poyo, epoo, o cepec pa.

NHMs NHMs NHMs H2O2, O OH H+ /Na2WO4, H3PO /MeCN, OHMeOH +MeOH +MeOH MsCl, -H+ -H+ NHMs C5H5N NHMs MeO OH OH MeO 91 ecaaoo oo a, o oecee pooe ao paec e po yceoc ypoeypx ex aopo eo eee peaoococo, e paee yee oe cy o cpoe aece.

4. Ce ocee H2O2 apoox opmo-(oee-1)eoa p ye epaypx ax oapye ee pep oce ocpy peaea o-(ae-1-)eoo. Ae pooe ocex, oe o apao, ecoco ax ycox ypoeypoy aa a, o ae oooc aa peya yoaa aeoo aece e aoe a eo poecca a.

Coeee 94 o oyeo eoo oepae o-(oee-2)eoa 93 oepyo oec epec oopoa pcyc aeopa e pee poeopo py. aa pea po opaoa coo cec poyo, e oaec aay, ooo, cya ec ocoec epoaa opaoae o ece H2O2 poepoceoo, o oop o eoxooc a copoo y eoa.

eo 94 apoa ece xopopaa pcyc NaOH eoe (xo 85 %), aee oye p 95 oepy oce epec oopoa MeCN.

OCOOEt OMe OH OCOOEt (33 %) OH H2O2, EtOCOCl, NaOH MeCN, OHMeOH C6HOH OMe (85 %) (24 %) OCOOEt Pea poxo eooc, poy ec xpoaopapoae a caee. Oco poyo (33 %) oaac eo p 96, opayc, oeo, p epe eoc-oa pacope epo opayc oc. Oapyeo ae aeoe oeco (%) poya ypoeypoo epeapoa, opayeoc, o, peyae aa aoa copoa poeyooo ocpaa a apo ao py c papo cxoo c O-C=O oopee axao oey MeOH.

Aepoae eoa ece ycycoo apa poooc xopoope pcyc HClO4 p oao eepaype. Pea, oe o peyeo cya, poxo eooao, a a epoaao opayc O-aea (xo 47 %) apyec aee o pe-pacy ae aece o peaea, pepaac eo (29 %). oa aaooo apoa aooo aaoa pea N,Nae-2-(oee-1-)ay ae p oe eepayp.

Me O OH OAc OAc Ac2O, HClOCHCl94 98 (47 %) 99 (29 %) p oce H2O2 pcyc MeCN, pepaac p o c 101.

xoo 45 % poy oce-epeapoa OH OAc OMe H2O2, MeCN, OHMeOH OAc 98 101 (45 %) Ocee aaox ycox eoa 99 e po opaoa ax-o poyo. Bepoo, o pocxo -a epoaeopoo eopy a oy c.

eooe poooe 102 opmo-(oe-1-e)eoa, oyeoe p ec eoxopa a coeee 94 pcyc oaa, ae p oce yaao cceo aece eceoo poya cp 103 c xoo 47 %. epeapoae ao cyae e pocxo.

OBz OH OBz OMe H2O2, MeCN, OHBzCl, K2COMeOH OH 94 102 (80 %) 103 (47%) oyex peyao o, o cyae poox eoa, ecocox cy coeo cpoe a, caa epx epeao pocxo c axao oey pacope. Opaoae p o ooo acepeoepa (apep, 101, 103) yaae a cxpooe oe ey poeae papa c C(1)-O aa yeoa.

5. Ocee opmo-(oae-1-)ao aypao coo Haypaa coa ec oee ec peaeo o cpae c cooa a paee ccea I II, acoc, o pe ee oe cooc, o oe a poeae aex pepae epx poyo. Pea pooac oaee a 50 % epec oopoa pacopy aeaa 92 % ypao coe, eepaypa peaoo cec oepaac a ypoe 40C. ee pea pa a 15 77, oaae y peaoy cocooc p ec opaao cce. o oapyeo, o ao cyae cxoe a cya pea ooc, aece ecex eex poyo oye eoco 104, 105 (xo 5962 %).

O NHAc O NHAc H2OCOOH R R (CH2)n - 15, (CH2)n HCOOH 104, 105 (5962 %) 104 (n=3, R=Me); 105 (n=4, R=H) Oeo, o epoaao ec ae pocxo ocpoae cxooo aea aypao coo, oc aee pacpaec (ca cpea) c opaoae ooopaa o, epepypoaeoc 2apoaao-1. ec pep, oa eo aoo cpoe eca eo occ cooecye eoco ye p ec copoa oyxa.

6. Ocee N-ae-2-(oee-1-)ao eocpao ClOeocpa (MO) pecae coo ocpy ae, ecy, oe o cce I II, epax ycox. Opaoa coee 7,8 MO aeoe po opaoa eocao 10, 11 c xoa 9495 %.

Me Me HO O O R O 7,CH3COCHN CH 10, oc xopa ec poeo ocy peaeo, ece oopoo a aea paee e yaoc, c c e o poeeo pooe ocee. ece 1 aea ClO2 aeope a a 7 po opaoa cec,-eoa 107 poxopa eocaa 106 (xo 34 32 % cooeceo), aaoc aeoe ocoee peaoo cec. poy paee oooo xpoaopae a caee.

NHAc HO ClOO CH3CN O N CHHCl 106 (32%) 107 (34%) 7. pepae opmo-(oae-2-)apao o ece H2OB epaype yaoc oapy pep oce acoa ceo o-(ae-2-)ao, ex aec ae aece c oceye ae. Ha pepe aeao a o yeo ece epec oopoa a o-(oae-2-)a. Pea Nae-2-(oee-2-)aa 108 c H2O2 pcyc opaaa a p ocopo co ycyco coe po opaoa cec cepeooepx oco 109, 110 coooe 63 : 37.

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