SPECTRAL DATA -114-
TABLE - II!_
UV/Viaible absorption spectral data of~ -oarboaJ.kox;y .ethyl tin oxinatea in methanol. - --~ Compound ::.\ max ( rllil) logE- max Figure Uumber - Oxine { CgH:6N • OH) 235 96 310 - (CH3C02CH CH ) sn(CgH60N) 255 4.81 2 2 2 2 96 315a. 3.48 334a 3.47 ---- 370 3.48 ( 370 3.21 CH3co 2mr20H2Sn0l(CgH60N) 2 245a 4.70 96 2Q5 4.82 ~ 315a 3.60 330a 3.61 375 3.76 Oontd .. I . ' \ \...... ,, ' 'I ~ ' f' ., .I \ ) ' ~ 2·0 1·0 1. Oxine. 2. Bis( ~-carbomethoxy etlwl} tin bis oxinate. 1•8 o·g a. ,t- carbomerhoxy ethyl chl_oro tin bis-ox.inate . ,..t 4. f,- carbobutoxv ethyl chl?rO tin bis- oxinate. 1'4 4) 1 '2 0'6 \) I I 3 c 0 1'0 .0 0'8 0 ' ,0 0'6 ,.. 4 0~ - 300 ' ... 220 240 ti(J. 96 UV/ v~sible spectra of oxine ~nd_,~ \"6rboalk~x.y ethvt tin. oxinates in meThanol. -115-. TABI,E - UI. ( c ont a.. ) ' •; . ~ '.,·, I,.,1,1 ·. ' . ' ~ ,.,~ ' ~ I <) '' t~i , 2.·0 1·0 1. (:.-~ carbo"inethci~V ,@.1-m~thyl eth~l C~lorb tin bi~ oxin~e . z.. f.>-,corbObutoxy ethyl.thiocvanato tin bi!' OJr.inate. ·.r o·9 1·8 3, ,&-.carbomethoxv ethyl thiocyanato tin !Jis- oxinare . 4. Bis(.~-carbomerhoxy ethyl)thiocvai!O!o tin'- oxinate. 1•5 Q-8 1·4 0•7 1: 1111·2 , • 1 o·6, .. "'c: t·o p·5 0 ..:. .! .. o·e 0·4 0 [ ,·· ., <( 0·4 ()·2 ll 4 . 0 . 2 0 1....::----1---l..-::----"--:----..__ __,.__,...... __ -L._ zzo z.w 260 280 soo 320 340 aoo· 380 400 · 420 . 440 WAV£LENSTH in· nm. •. Ffg.,97 uv / vis(ble spectra of f-.- carboalkoxy ethyl tin oxinates in meThanol. -116- TABLE- IV UV/Visible absorption spectral data of (?, -oarboalkoxy ethyl tin substituted ox:tnates in methanol. ' : '. i'· '.'f ' •)' . '(f .· :'~-- ,: l"... · 1. : 5,1- _dichloro o~ine , 2-D 1·0 t. Bis (~--carbomeTI'IOXV eThvl) tin bi_s- '5,1-dichloro oxinote: 3. ,o!>•CarbomeThOXV eThyl Cl'lloro Tin biS-5,1- dichloro o:or.inate. 4: ,o!>-c,orbobutollv eti'IVI Cl'lloro tin Dis- 5,1-dichloro oxinate . •s. ~-carb0metl10'1.y ~~methYl ethyl chtoro tin bis-5,7-dicbloro oxinate. 1·8 0·9 t·6 o-: 1·4 ~- ·~t·Z c: 0 I l 4 ..Q 1"0 ...: 0 Ill ··z ..0 DL---~~--~~--~~ ?.ZO Z40 ' 2M ?.80 320 340 360 31!0 400 4ZD 440 wave lenQth In nm. Fig.98 UV/ visible spectra of {b- corboalkoxv ethvl tin 5,1..: dichloro oxinates in meThanol. -117- T::;,;A~· B:;;:;L;:;;;;E;,_- ...n,· (Contd •• ) .. ----·------Compound Figure .Number ·------5·, 7 -di bromo oxine 245 .- 99 ---. . '325 - ( 388 3.69 ~-- CH C Oz0HzOH SnCl\ Br , CgH40N} 265 4.79 99 3 2 2 2 325 3.59 340 3.63 390 3.76 '250 99 C4HgC OzOHzCH2Sn(Br2• Ogi{40fi )3 4e75 265 4.88, -~ ::?25 ~.76 340 4.80 390 ';1:.84 265. 99 CH3oOzCH(CH3)cH2SnCl 5.07 { Br • H ON) 2 c9 4 2 340 3.96 - 390 4.04 ~ I . ':,:f .)- (:f .,~~----- ~·I 4·0 1·0 .' 1. 5-7 dibromo o~tine 2. Bis(~-carbomethoxy ethyl)1in bis- 5.7-'dibromo Ol'.inate. 0-91 3. ~- carbOmetlloxv ethvl Chloro tin bis-5,7-dibromo OKinate. "~-earb0bu1ol(vethyl tin1ris-s,7-dibromo oxinate. ().8 5. />- carbOmethoxv f.~- methyl ethyl chiOro tin bis s,7- dibromo o"inote. 0·7 ., c Ql .£l ··- 0~----~----~----L---~a&O 300 O ~~~~3~20-----~L-----36~0--.--~3~8-0----400~-----4~2~0----~----J 220 240 ' 260 .uo' 460 . WavelengTh in nm " Fig. 99 UV/ visible spectra off,.- carbo~lkoxy ~~~VI tin. 5-_7- dibromo Ol(inotes in methanoi. -118- T.tU3LE-- V UV/Visible absorption spectral data ot·~ -carbo- a.lkoxy ethyl tin phacyl-5-azo ox:tnates in methanOl - - Compound max(nm) log Figu.re ------IlBX Number "Phen.yl-5-az o oxine 240 - ,00 ( 061-!&~ Hf e00Hi;N. OR) 380 - · 4_50a - (CH oH 0H ) sn 245 100 3 co2 2 2 2 4~52 (0 H&~$N.06H 0N) 320. 4.26 ~ 0 0 2 430 . t1.49 CH co cH CH ~nCl · 260 4.52 100 3 2 2 2 c ( 06H0N a.N • o6H5 CN ) 2 340 4.37 400 4.49 ' { 0 4Hg002CH2CH 2 ) 2 sn 240 4.37 100 (06H&~sN.o~ 0N) 325· -~, 5 2 4.56 430 4.49 04HgC02CH20H2SnCl . 200 4~13 100 (06H x.r Hi • o H ON) _ 340 5 6 0 2 3~94 400 4.11 Contd •• ------1. Pherlyl- 5-0ZO O'l'.ine. · t. 6is(~-carbomethoxv. erhyl)tinbiG-Phenvl-s-azo Ol(inate . . s.p.-carbometho.~vethvt ct_hloro tin bis-phenyl- 5-ozo oxinare. 4.Bis(j!.-carbobutoxv ethyl) Tin t?is-phenvt-s-azo oxinare '5.~~ carbobutoxv: ~thyl chtoro tin bis.- phenyl-s-ozo-o"Klnote . . 6.f.,-. carbomethOXY, (:;,'._meThyl. ethyl Chlor-o tin. bis- phenyl-S-OlO oxina1e. H3 i I ~ 1·2 Q) 0 c: 1·0 ~ 0 .0 0·8 II.. 0 (I) _o 0·6· <(. 0·4 0·2 0 ~~---~------L----~------~------~-----~----~--- 220 . 260 300 340 . 380 420 460 soo . WAVELENGTH in nm. Fig.100 UV/ visible spectra of phenyl-s..:azo oxine and some ~:>- carboalkoxy ethvl tin phenvl-s- azo~oxinates in methanol. ' .~· '.· I - . . ·. ,. L..rl, p_:o-_ ·"'· .. '.' .. ·, ..., ... ;. -(; ·. ' .. • ·.r·; • -L 0 ~.... ~ .· .q .. ;.. -\ .· :;', . ' ~· ,.•., .. -119- Compound ~ max(nm) logE max Figure l'Iumber ~- -- 100 mi3co20H{CH3 )cH2~nCl 260 4.37 325 ( 0 sH5N IN • 06H50N} 2 4.55 410 4.99 5(2 1-carboxy phenyl) az o ox1ne 250 101 350a (H02c .00H4If HC 6H5I1 .• 0H} ~- 475' .. 260 4.34 101 'OH3c o2cH20H 2) 2sn 38d3, (H02C @06H4 11J' : :N .06H5~! )2 4.13 420 4.21- a:.Jmall hump • J· contd•• I. (l,;j_ ' --- -· ., •, ·-) I ~= ' ..... 'l'f ~ i.\. I 1. Dithizone· 2. · Bis( ~-corbomeftloxy ethyl) tin bis- dithizonate .- 3. ~-corbomethoxv ethyl chloro tin bis- dithizonote. 4. Sis(~- corbobutox:v ethyl) tin bis- dithizonate. 5.· P..- ~arbobutoxy ethyl chloro tin bis dithizonars . . 1·8 1'6 Q) 1..) C·' 0 1·0 .D '- 0 (/) o-6 .D <( 0·4 o·z 0 220 260 300 ·340 380 420 ' 460 4 540 580 wavelength •n nm. F'!CJ.102 uv;v'tsible spectra of diJhizone and 6-corboalkoxv ethyl Tin dithizonates in methanol. \.} ) ·+ -~--- ~- '·. 2·0 1. Bis(,..carboJMthoxY sthVI) ChlorO tin dilhlZonaTI.' 2. Bls(-.·corbomattmy sttrvll thiocyonoto tin dlthizonota. 1·8 3. "-corbolltthalV ~'-JM!hvl Silly I chloro tin bls-dfthizonats. 1•6 1·4 1-2. 4) I) 1·0 c: 0 .s:. 0·8 ._ 0 Ill 0·6 .s:. 0-2 ol_~--~--~--~--~--~~~~~~~~~ 220 280 320 360 400 440 480 520 560 600 '#/~length in nm. Fig.lO~ UV/ visible specrro £. carboa!~untv ~rhyl tin dithizonates in lnffi'IOnol. -121- ~ ., . . TABLE- VI \Contd •• ) Compound ~ ma:x;(nm). log Eznox Figure l~umbar, ' ' ~ CH0C02CH,CH3)CH2SnCl 276 4.40 10?> ( 06H&'IH.NCSN JN06H5) 2 480 ------ · TABLi.!; - VII uif/Visible absorption spectral· data of ~ -carboalkoxy ethyl tin complexes of alizarin and other ligands. CompOUl_l.d ~ max(nm) :LogE: max Figure I-I umber - Alizarin 250 - 104 /oo, · 275a 06H4 / 06H..1( OH) . -~ - 'CO - 2 325a 430 - 530a ( OH C0 CH ) 3 2 C,'H2 2 2sn 262 4.45 104 /co, 3208. 3.79 (osrr4 'oo/.C6H4o2 ) 4;75 3.95 ~--- Oontd .. ·:.f ) .·r .~. :~ - ~ 1. ~lizarln 2. Bis(P.,-carbomethoxv erhyl)tin alizorinate. 3. ~- carbomethoxv·ethvl chloro tin an:z.arinate. 4. Sis (a.- corbobutoxy ethyl)tin alizorinate. 5. ~- corbobutoxy ethyl chtoro tin alizarin ate .. 1·5 1'3 Q u c 1·1 0 .Q ... o·g 0 (I) 0·7 ..0 <( 0·5 Q-3 0"1 0 - Z20 200 300 340 380 420 460 500 S4a sso 62.0 Wavelength in nm. f"iq.104 uv( visible spectra of Alizarin and ~-carboatl . -122-· .. TABLE - VII ( COn.tdi •) Compound ~roo.x(nm) log_t max Figure Nwnber I l . ~ .~ ---- ( o rr oQ.2CH CH ) s~ · 255 ·4.56 104 4 9 2 2 2 ' . ; co, . . . 320a 3~1.1 (OsH C R 0 ) · 4( . / 6 4 2 ' .co ·' ' 480 3.82 ,CH3C02CH20H2SnCl. . . . /oo, :<.c6H4, ./. OsH4o2) 250 ·4 •. 52 104 .·. - .. co ·.· ~ ·320a 3.70 .. 470 . 3.82 04H9C 020H20H2SnQ1 .. /co,. , · (CsH4...... _. co /C6H402).. . 25Q 104. 320a 460 ,. ·.·. 1,5-dipheeyl carbazone 230 ' - - . {0 6U5NH.NHCO!~JHtC 6H5 .) 290 460 565 , :. -· .. · Con.td•• ;.-, -123- TJ\BLE - VII {uontd •• / 1-nitroso~2-naphtnol 260 Cc10n6 .Ho( OH) J 370 ~- ( CH oR on ) snCl 3co2 2 2 2 260 4.49 370 4.08 (010H6U02} 580 3.57 asmll hl..lmp. The infrared sp ect:ra were recorded as_ ntl4-0l ·mulls using Beclcma.tin IR-20 >:>pectropnOtometer .equipped with KBr wjndo~s in all cases otherwise mentioned, in the range between 4000 - 300 cm-1 • The follOwing abbrevia- ti on have been used : s = strong, m = meclium, w = weak, v. • ver-J,. b =broad, sh = shoulder. Nujol has peaks at -124- 1 3000 - 2800s, 1460s, 1376m. Values_ may be in error t.5 om- • Bis (~ -carbomethoxy ethyl) tin dichloride (Fig. 1 h 3000-2840s(b), 1677s, 1455s, 1449s, 1420sh, 1407s, 1370s, 1274s, 1240s, 1230s, 1195s, 1190s,.1160sh, 1145s, 1139s, 1035s, 960s, 920m, 900w, 890w, 755s, 690s, 610s," 600sh, 570vw, 540w, 498m. ~-carbometho.x:y ethyl tiri trichloride (J?ig.' 3 h 2980-2860s(b), 1660s, l465sh, 1453s, 1402s, ~372s, 1270s, 1250sh, 1190m, 1135m, 1050m, 952s, 920sh, 900s, 750w, 700s, 600vw, 500vw, 532vw, 510w(b)., Bis( ~ -oarbobutoxy ethyl) tin dichloride (l!'ig. 4 ) 1 2960-2865s(b), 1675s, 1460s, 1402s, 1350s, 1262s, 1220s, 1130mt 1060m, 1030m, 1010sh, 990vw, 935s, 920sh, 839vw, 840w, 760s, 695s, 600w, 525m. ~ -carbobutoxy· ethyl tin trichlOride (Pig. S· )·: 2980-2850s(b), 1640s, 1445s, 1395sh, 1360s, 1270s, 1225s·, 1180w, 1120m,. 1030m, 942m, 910vw, 885m, 745m, 692m, 605vw, 590vw·, 540vw, 485w., .· ~.125.- ·.·. .· J . . . .' . ~ -:-carqome·thoxy ~ ~et_hyl ethyl tin trichloride (Fig._ '7 h 2960-2840s\b), 1640s, 1528vw, 1460a, 1440s, l400m, ·. ' ~' . 137os, l348s·,. 1280s, 1250s, l160m, ·ll40m, 1119m,. 1900W, . , ; . ' . . ' . I! . . . -970s, 912e, 850m, 795m~. 759w:, 720s, 702s, 69Bvw, 620vw, ~ ... .. 500vw. d., > "' .. 2980-2840s(bJ, 166~113; 1458s;.1400m, 1390s, 13ll5s, . I . ~ . .._, · 1334s, 1240m, 1210w, 1180s, .-1140m,_ 1112s, 1022m, 990w, 96Dlv, 720w, 622s, 512w, 50om. · . ' . . - S..;.hydrox..v quinoline ( oxine ) .( li'ig. 9 h . . ' 3200b, 3600-vw, 29so-2840s(b), 1580s, .1502a, '1470s, 1430w, 1409r:.:i, 1395eh, l38bs, i292s, ·1270s, 1242w, 1228s, 12~0s 1 1172s1 l165s, 1139m,· 1092m, 1058m, 971m, . 897m, 890w·, 865vw·, 81'56, 802vw,_ 779s, 739s, .70Qs, .632s, . 592mt 561\v, ·540~.,, 505vw. ·.· i 6, 7-dichloro oxine (Fig. ~2)' ~- 3200 (b); 3060vw, 2980-r2840s( b), 1607w, 1580w, '. ' ' ' ~ . - . - - 1568w' 1490s, 1458s, 1392s, 1375~h, 1367s, 1330s, 1270s, . .- . 1248w, 1212w,. 1199s, 1148s, _.1145~, .928s, f~65s,_ 850vw, aoo~, '?79s, 712s,.. 678m, .640s;. 6iOvw,- 670vvi •.. - ,-, ···,. ' . . I .. __ ,_ . I t~ . ' J -126-· r. 5 ,-7-dibromo oxine (E'ig. 40 ); 3200b, 2980-2840s-(b), 1610vw, 1580m, 1~95s, 1462s, 1399s, 13676, ·134.0s, 1270s, 12SQvw, 1220.s, 1212s1 l, '~- • .• ' ' .1200m, 1190s, 1139s, 1045s, :950~, 875a, 860s, 800s, 776s, ~·.':_ ¥. .-.• ,;l 740w,. 710s, 642s, 620vw • ', . ' "?h~nyl-5-a.zo oxine {Fig.4-9) 1 · ,\ '. 3400b, 298~28~e(.Q), 1600w, 15oOw(b), 1490vw, 1452s, 1400sh., 1375s, 1298a, 1245s, ll82m; .1165sh, 1130m'; 1120sh, 1080m, .1068m, 1042w, ~l009m, ~15vw, 900vw, I 340m; 822w~- 810m, 785s~ 755s_, 740vw1 715m; 700vw,. 680s, · 650vw,- 600vw; 512w • .~(2'-carboxy ~henyl)-azo-oxine (I!'1g._6o)s 3L,lq0b; 3360b 1 .1620m,·l580s, 1510sh, 1485s,, 1450s, 1420vw, 1400vw,~ 1370s, 1320vw, 1290w,- 1260-vW,- 1215vw, · ·.1170s, 1122m, 1095vw, 1Q55m, 1015s, 890w, 845s, s12w, ' . ' . . . ' 775m; 740m, 718w, 690m,· 6~0w, ·650vvi, 635vw, 540vw. ~- ,\·. i ,5-diphenyl thio ·carba.zon:e. (Di thizone). (Fi,g~·· 62 ) : •.- . . · 2.980-2840s(b), 1590m, 1495s, 1480m, 1452s, 1435s, ·1375m, ·1315m, 1250m,. 1215s,· 1170s, 1140s, 1090vw, 1065w, ~ • ' ' • • ! I 970vvT, 898w, 885m,. 822w,_ 810vw, 770m, 755s·, 740s, 705s, 6_70s,. 588m, 550vw, 530vw, 515sh, 505s., -. ~ ~127~ -, ' ' - - ' ' 3300s, 3~_60sh, 3090vw; 3050vw, 2980-2840s(b), 170!1s, 165ps, 1600s, 1560sh;' 1540sh, 1510sh, 1490s, 1450s, 1442s, 1372m7 · 134-0ni, 1285m, 1250m, ll98m; 1178m, 1147m, 1115s, 1100sh, :J.075w, 1020w, 980s-, 970sh, 930w, 900m, 875w, 810w-,790vw, 767m, .742s, 682s, 670m, 660vw, 620m, 580w1 515s, 490m. - 1,2-dipydroxy anthraquinone. (AJ.izarin) { l!1ig.7.9 h 3400s, 2980-2890s ~b), l655sh, -1630m, 1590s, 1450s, l380m; 1350sh, l3~~w7 1305sh, 1290s, 1270s, _1190s, 1160sh, llOO~v, i 050m, 1035m, l015m, 970vw, 895w, 850m; ~29m, '750s, 710s, 670vw, 605w, 615-vw, 500VY'l!t · ' \" . 1_,2,5,8- tetrahydroxy anthraquinone {C~uinalizarin) {Fig.S-6)&- 3340s, 2980:-2840s(b}, 1620s, 1590s, 1470s., 1460s,- 14'50sh, l~Ovi, 1385vi, 1330m, 12~0s(b), 1255s, 1240s, 1205w, -1170m, 1100s, l.040m, 990m, 948m, 850s, 840sh, 825vw, 815m, 790m, 770m, _7 60m,. 740m, 719m, 695m, 632m, 610w, 530vw, BlOw. :3odidum' Alizarin i:n.Qphonate (Alizarin .... S) . (Fig. sa); 3460s.~b), 2940~2SOOs . t . 1220v1., 1195w, ii50s(b),·1060~, 1038m;-1036m_, 1010s,.920rn, 90~~, S60s, 810vw, 815vw, 780w, 765vw, 755vw, 745vw, 720w, 700s, 670w,· ~ 630s, 610w, 590m,. 550vw, 525vw, 505vw. -128~ _-, 1-.tli·troso-2•naphtho~ · (:!!"'ig. 90) a 3400b, 2960-2840s(b),_ l610s·,-1600m, lo80m, 1550vw, 1515a, 1459s~ ·l~OOa,· 1370s, 1340sh, 1330m, 1317_sh, ;1305sh~ 1252s, -1210s, 1155m, ll40w, 1105vwi 10.95vw, lO'lOa,· 1045w, 1020v~, 965s, 880v;v, -850s, 800vw, 780s, 760s_; :750s, ·715m, 700VtlJ,· 688m-, 645vw,. 610vvJ, · 540vv~t 5~0vv.;r, 502~.· Bis( ~ -carbomet~oxy ethyl) chloro tin oxiuate ~:- ....·_ ·. ' , 2960-2840s( b)' 1710s, 1600w, 1580m, 1490m, 1460s, 1440sh, 1380s, -1360s, 1340sh, 1320s,· 1270m;· 1265ni, ~238w, 1~tos, 1180w, 1-1~5m, 1·120vw, 1102s, 1040m, :gaovw, ·960m, 918m, 880w, 820s, 800s_·, 780s,. '750s, '738s, 69pm-, 660vw, -630w, 620m, 5.78w, 5~'{)vl.v_, 532s. Bis( ~ -carbomethoxy ·e-thyl) tin bis-ox'inate (J!'ig•l·~··h 3180vw, 29d0-2860s(b}, 1729s·, 1610m,· 1570s,· 1490e, 1460s, 144om,- 142?vw~ 13d2s) i372s, l340w, 1320s, .1300vw, i?75s, 1240sh,. 1230sh,. 1220s, 1210s, 1195s·, 1179s, ll~9m, l115m, 1102s, 1088sh, l050m, 1038m, 1029m, lOOOvw' 980mt 960m,.950w, 910m, 900vw, 890vw, 870m, 830s, 820s, 810vw, . . . .·. 795s, ?80s, 660m, 635s, 618w, 608m, 595:n,. 575w, 5~2s, 500m. Bis (~ -~arbometh&..ty _ethyl) thioc~anato ~ixl. o~nate (.h'ig.13. )a 2960~2820s(b), 2050s, 1715s; 1610w, .1582m, 1505m, 1460s, _1385s,. 1330s, 1280s, 1225s, 1195sh '· 1150s, 1120's, .. ·~I ~129- 1049ni, 972m, 930m, 895vw-, 830~, 810m, 798s, 760s, 745a, 690m, 650vv,· 635a, 6o5vw, 565vw_, 545s, 505vw. · Pr;duct o:r reaction l'i o. 13 (page 67) r - . 2980-2840s(b),·. 2070s, i710s(b), 1_600~1510s(b), . . 1490w, 1450s, 1370s, 1~20s, 12756, 1255sh, 1240-1120s(b). ,. 1100m, 1025m,· 905m, 855vw, 8l5s, 795m, 780m, '740sh, 725.s, 685rn, G30w, 600m, 515s~.· ~ -carbomethoxy ethyl chloro tin bis-oxiu·ate <(]lig. H>)J 3100vw, 3080w, 3020vw; :2960-2840.s( b), .1'730s, 1600s, ' 1572s,· 1540vw-~ 1495s 1. '1,460s, 1429.s, 1400~h, 1390s, 1375s, 1355s,. 1322s, 1271s, 1232s, 1220s_, 1200s., ll?Om, 1140vw, 1110s, 1060vv'lt 10,50vw, .1040s, _1030s, . 995vw, 985vw, 960m, 950sh,. 912s, 870s,, 865w; 822s, 820s, 799s, ~89s, .780s, 772vw, 755m, 748s, 737s, 730sh, 660V\v, 632m, 625m, 620s, · 530s, 500s. ~-carbomethoxy ethyl thiocyanate tin bis-oxin.q.te (Jl'ig.1'7)_1 · 2960~2840s(b), 2002s, 1720s, lGOOw, 1580m, 1495.m, 1460s, 1375s, 1342vw, 1325s, 1275s, 1215s, 1175vw, 1135vw, 11Q5s, 1030m, 972w, 915vw, -890vw, 829s, 808s, 790s, 760s, .. 740:;s, 680vw, 630s, 615ah, 598vw,· 540s, 510vvf, 490m, 410Vvh -· .· ' ' -'· ' --130- - ~- . ~ -.carbomethoxy_ et!Wl tin tris-?xinate (l!~g.19): 3020vw, 29·60~2840s(b), 1720s, 1595.s, 1560s, 1tl:90a,. 1455a, 1445sh,' 1435sh~ 1420w, 1385s, 1370s, 1320s'· 1272s,. > '., 1245w; 1230m, 1205t'l~ 1170w, .1100s, ~050w, l025m, 992m, 942vw, 898vw; 880vw~ 86fivw, 850vwv, 840vw, 8l0s, 795s, 778s, ·740s, 'l26s, 6'llm, 630m-, · f310m, 560vvl, 519s, 480w, · 440w, 400w.- ~·roduct .of reaction No. 17 (page 71) (Fig. 21); · 3050\v, 2960;..2~60s( b), ·1'715s, 1590s, 1575s, 1485s, 1455s, 1410s, 1372s, 1340w, 1320m, ·1270s ~- :1215b, 1190w, 1170w, 1~135m, 1100s, 1055s, l.040,s, 1022s, 980v~, 970w, 955m, 940m, 930vi, 900m 880m, 822s, 810s, 792s,_. 782s, 778a, 750s, 740s, 660m, 638s, 630m, · 605s·, 522m. ~-carbobutoxy ethyl chloro tin bis-ox:Lnate · (J!\ig.-22) ~ -3070w, 2960-2845s(b), 1730s,-1600s; 1570s; l~OOsb, 1_492s; 1460s, 1.425s, 138'ls, 1372s, 1352s, 1320s, 1270s, 1230s; 1217s, 1197s, ·1135w, 1102s, 1098s, 1059vw,_:1049vw, _1045m, 1030m, 990vw, 980vw, 960m, 950sh, 91~m,·870m, 822s, . · S18s, 796s, 785m; 778s, 750sh, 745s, 735s, 632sh, 625sh, 620s, 535s, 505w. ~ --- D . -131-· . ~ -carbobutoxY .~1lr.byl· thiocyanate tin bis-oxinate. (Fig• 24): 2920-2820s(b), ·2020s, 1720s, 1650vw, 1600w; 1570m, 1490m, · 1460s, 1375s, .1320 s, 127~m, l225w, 1185w, 1100s, 1055w, 1040w, 975~.' 955vw, 940vw,. 88pvw, 820s, eoom, 785s, 762sh, 750s, 730s, 708sh, 670vw, 635sh, G20m, 585vw, 525s~ 510sh~· · ' . (':> -carbobutoxy etJJYl' tin tris-oxi.uate (Fig. 26) J 3040Vw, 2960-2840s{b); 1728s, 1600s, ·l575s, 1492s., 1460s, 1418vw, 1408vw,·l372s, 1320st 1270s, 1222m; 1205vw, ·1185s·, 1120m, 1100s, :lOGOm, 1028m,. 988vw ," ·952-vW, 936vw ,. ; . ' ~ . - . ~ ' ~-- 9.05vw, 852w, 819s,. 798s, 780s, 745s,· 740s, 730s, ·680s,. 64,0s, 620s, 535s, .507w:. ~ -carbometh oxy ts' -me:thyl etp;y-l· chloro tin bis-oxinate ~l!~ig_.2.8); ,, _3060vw, 2960-2860s( b), 17.22s, 1600s, 15.75s, '14_90s, 1460s, 13$0vw, 1375s, l350sh, 1320s, .. 1275s, 1238s, 12~0 sh, ,1200s, 1180vw, 1155m, 1140s, 1100 ~, 1080sh, 1050vw, 1030m, 1020vw, lOOOvi',i 980w, 905w, '890sh, 820s, 79Bs, 779s, 750s, _7.30s, .630s, · 620s·', 520s, 490vw, 470m. ' o o' • L ·o~.,o<. ,;,.d.imethyl· ~ --a.cetyl ethyl chloro t:ln bis-oxinate (Fig.3o)a 3320s(b), ·3040b, 2960-2840s(b)·, ·2780w; 2670~,· 2610vw, 1639s, 1600s,.:t..59.0s,'·1550a, 1500s, 1465s, 1422sh,·l400a,· - . - ·, , ' -· -. -:- :• .. ' '. ~ : ·.· . r , -132- 1360s, 1355sh, 1320s,. 1300s, 1270s, 1225s, 1210s, 1170vw, 1190m, 1100s; 1060m, 1050vw, '!t030vw, 1015m, lOOOm, 980w, 900w, 880s, 820s, BOOs, 788s, 758s, 710s, 620s• 595a, 570vw, 560s, 502s. l?roduot (m.p. 310°C) of preparation He. 22 (page 75) (Fig • :?>1 ) : 3060vw, 2960-2850s(b), 1600m, 1572s, 1490s, 1465s, 1430m, 1382s, 1370s, 1315s, .. l2~5sh 1 1272s, l265sh, 1230s, ll70m, l102s, 1075w, 1062m, 1035m, 975vw, 960vw, 942w, 902w, 870w, 830m, B20s, 803s, 788s, 755s, 750s, 730s, 640m, 618m, 552m, 540s, 510m. Bis{ ~- -oarbometb oxy ethyl) tin bi s-5, 7~1obJ.oro oxinate (Fig. 34) j 3100vw, 2960-·2840s(b), 1730s, 1680s, 1590m, 1550s, 1480s, 1445s, 1390m, 1372s, 1352s, 1288w, 1260m, 1245vw, 1220s, 1200sh, 1150sh, 1130w, 1120w, 1110m, llOOm, 1055s, 1044m, 1025m, 1005m, 960s, 950m, 910m, 880s, 875s, 860m, 830m, 815m,- 805m, 800m, 780s, 760sh, 752s, 745s, 715vw, 680w, 655s, 645m, 600m, 585vw, 530w 1 505w. ~ -carbomethox:y etbyl· chloro tin bis-5, 7-dichl.oro o.x:inn:te (1~1g. ~6)' 3060vvl, 2960~2840s(b),- 1732a, 1685m, 1595sh, 1550s(b), 1490s, 1460ah, 1448a, 1&95sh, 1375s1 1360sh1 1280m 1 1235a, 1200ah, 1180w, l142w1 1130ah, 1110s, 1055m, 965s, 910w, 878s, 840vw, 810m, 780m, 750s, '720vw, 690vw, 660m, 610m, 535w, 520vw, 490w. Product of the reaction illo. 25 (page 78 )'( F:ig. 37) : 3060w, 2960-2840a(b), l715s, 1680s, 1590m, l560s(b), 1480sh, 1460s, 1450a, 1380s, 1372b, 1290w, 1230m, 1190m, 1100m, 1055s, 960s, 915w, 890s, 840vw, 810a, 760s, 140m,. 665s, 650s, 605a, 555w, 522m. ~ -carbobutoxy ethyl chloro tin bis-5t7-dichloro oxina.te ( :b'ig. 38). 2940-2820s( b), 1720s, l595w, 1570s, 1485m, 1_455sh, 1440s, 1395sh, 1360s 1 1285w, 1230m, 1195m, 1140m, 1110s, 1052m, 965s, 920vw, 890s, 845V\v, 810m, 782m, 755s, 660s, 610w, 525vw, 520vw, 498~·w. I ~ ... oarbomethoxy ~ -methyl ethyl chloro tin b:l.s-5 ,'7- dichloro oxinate (:B1ig. ~9)' 3060w, 2940-2840s(b), 1720s, 1598w, 1560s, 1480s, 1460s, 1435s, '1395s, 1360s, 1290w, 1275w, l:250ah, 1230s, 1210s, 1190s, 1145s, 1105s, '1055s, 1030vw, 1010w, 989w, 9oq,s, 9~0V\v, 880s, 870s, 810s, 780s, 760s, 650s, 615vw, 598w, 540vw, 520vw. -134- Bis((S -carbomethoxy ethyl) tin bia-5 ,7-dibromo oxinate (Fig. 42 )= 3100w, 2960-2800s( b), 17:30s, 1700s, 1590w, 1550 sh, ' 1530s; 1470s, 1420s, 1400vw,·1375s, 1355s, 1350s, 1305m, 1265sh, 125.5sh, 1240s, l230m, 1200s, 11.65 sh, 1135m, 1122qa, 1100s., 1095s, 1085s, 1035s, 1028m, 1015m 1 980w, 950m, 920s, 900s, 855s, 838s, 820m, 792s, 775s1 725s, 660s, 640s, 619s, 578m; 550s 1 520m, 480m. ~ -carbomethoxy ethyl chloro tin bis-5, 7-dlbromo- . ' '.. oxinate (using .Na.Cl wtn.dO.ws) {Fig. 44h 2960-2850a(b), 1722s, 159~,1572m, 1550m, 1478m, 1448s, 1385sh, 1365e, 1280w, 1235w, 1200m, 1170w, 1135m, . ' ' 1100m, 1048m 7 942m, 910vw,_ 885sh, 875ah, 859a, 805m, 772m, 74~s, 680m, 6~s, 620vw, 600w, 586vw. ··product of reaction No .. 30, page 83 (using NaCl win~~ws) 3180m, 3040vw, 2980-287~s(b), 1720s, 1680s, .~ 1585vw, 1570s, 1540s, 1470s, 1435s, 1390sh, 1375s, l345s, 1240s, l200a{b), 1130s, 1100s, 1050s, 102Gm, 935s, 910w, 870m., 854s~ 800s, 7'78s, 735s, 675s, 6.~os, 635m, 565m; olOvw, 485w •. -135- f-carbobuto:x:y ethyl tin tris-5,7-dibromo oXina.te (Fig.46)a 3065vw, 2980-2840e( b), 1:,725s, 1590m, 1555s, 1480s, 1450s, 1390s, l365a, l280m1 1268V\v, 1240m, 1218m, 1196m, l135m, 1102s, 1047a, 942s, 910vw, 859s, aooa, 772s, 736s, 679s, 645s, 580m, 510vw. I ~~oarbomathoxy ~-methyl ethyl ohloro tin b.ls-5,7- dibromo oxi~~te (Fig.4S): 2960-2840s(b), 1730s, 1600w, 1570sh, 1505s, 1475s, 1440s, 1362s; 1290w, 1248m, 1220m, 1200m, 1180sh, 1i45s, 1105s 1 1052s, 1020VVi1 10~0vw 1 995vw, 985vw, 940s, 920vw, 865a,·810s 1 785s, 745s, 685s, 620w~ 585m, 520w, 500vw, 450w. Bis(~ -carbo~ethoxy ethyl) tin bis-phenyl 5-azo oxinate (Fig. 50): . 2940•2820s{ b), 1725a, .1,690s, 1625vw, 1595m, 1580m, 1558m; 1542m, 1515vw, 14~5m, 1450s, 1410v-.v, 1375s, 1330m, ~) ~ 1315m, 1285vw, 1251m, l~lOm, 1185w, 1152w, 1128s, 1100w, 1070w, 1042vw, 1020w, 970w, 920m, 338m, 820m, 805sh, 785sh, 769s, 740a, 685s, 650vw, 632vw 1 620vw, 550m, 520vw 1 510vw, 495vw. ~ -carbomethaxy ethyl chloro tin bis-p}).eeyl-5- azo oxinate (J:"ig. 52, ) a . 2940-2840a(b), 1720m, 1595m, 1580w, l555m 1 1490m 1 -136- 1450s, 1405w, 1390w, 1378m, 1312s, 1275vvl, 1245s,- 1200vw, 1195Vw, l185m, 1150V\v 1 1140vw, l125m, 1100s, 1080vw, 1035vw, 1020w, 975vw, 925w, 870vw 1 840m, 815~, 790m, 778VVJ, 768s, - . 738s, 685s, ffi5vvv, 645vw, 630vw, 605vw, 580vw, 550w, 530VYt, 510vw, 490m. Bis(~ -carbobutoxy ethyl) tin bis-phenyl-5-:a.zo oxinate (F.1g.54)a 3140vw, 3040vw, 2940-2840s(b), 1720s, 1680m, 1580s, 1560s, 1545s, 1490m, 1440s, 1420s, 1390s, 13lOm, 1275vw, 1250s, 1210sh, 1198s, 1149sh, 1122a, 1065m, 1040vw, 1015w, 995vw, 91.5m, 890w, 830vw, 812m, 790vw, 760s, 735s, 680s, 625vw, 542m, 520vw, 470m. (f> -ca:rbobutoxy ethyl chloro tin· bis-phenyl-5-azo oxinate {Fig. 5-6) 1 2940-2830s( b),. 1720m, 1600V\'h 1580m, 1510vw, 1490m, '1460s, 1405w, 1375m, ;L318s, 1248s, 1185m, · 1150vvv, 1125vw, 1100in, 1062vw, 1020w, tOOOvw, 980vw, 950vw, 915vw, 835m, ,910w, 780m, 750.s, 738s, 700sh, 685s, $65vw, 642vw, 552m, 530vw, 520w, 500w• .· I (/:> -carbomet,hoxy ~ -methyl ethyl chloro tin bis-phenyl- 5-aZo oxinate {Fig. '58) a 2920-2840a(b), 1715m, 1660vw, 1590m, 1575m, 1555m, -137- 1485m, 1450s, 1400w, 1370s, 1310s, 1240s, 1200V\v, 1180m, ' ll40w, l115m, 1090 a, 1060vw, lOlOm, 990vw; 9lOm, 875vw, 835s, 810m, 780m, 760s, 732a, 680e, 655VtiY, 640w, 625vw, 603vw, 560sh, 550w, 510m, 490w. Bis(~ -oarbomethoxy ethyl) tin bis-5(2'-oarboxy phenyl) a.zo~oxinate \Fig. 61) ' 1650 sh. ~400b, 29~-2840s(b), 1725a, 1690s, 1590a(b), I\ 1570s, 1500m, 1460s, 1410w, 1375s,. 1315s, 1250s, 1220m, 1190w, 1170w, 1130m, 1100s, 1060vw, 1035sh, 1020s, 970sh, · 960m, 920m, 890sh, 875ah, 862m, 840s, 785s, 765s, 740s, 710vw, OOOs, 6~9m, 620sh, 5.08s. Bis{ ~ -oarbomethoxy ethyl) tin bis-dithizonate (Fig.63): ' 3220w, 2920-2840s(b), 1735s, l~OOs, 1575s, 1495vw, 1460s, 1410w, 1380ah, 1360s, 1342m, 1310m, l265m, 1190s, 1175w, 1165m, 1150m, 1130m, 1080w, 1050w, 1005vw, 970vw, 915w, 890vw, 855w, 830vw, 760m, 75ls, 740sh, 710m, 700m, I 690m, SBOm, 615vw, 558vvl, 540s, 510sh, 500s. Bia(~ -carbomethoxy ethyl) chlorotin i:.:_.;· .. dithizona.te tt!g.65) . .lr- 3160bi 2960-2830a(b), 1705a, ~595m,.1580m, 1530m, 1462s, 146Qs, l375s, 1345s, 130~m, 1264m, 1200s, 1175w, 1250sh, 114.0m, 1120w, 1100vw, 1070vw, l030vw, lOOOvw, 970vw, 900w;, 915w, 860vw·, 830Vw, 768s, 748s, 710m, 68.0s, -138- 620m, 540m, 500s. . Bis(·(5 -oarbomethoxy ethyl) thiocyanato tin dithizon.ata (Fig. 67 ): 3220m, 2960-2840s(b)' 2010s, 1732s, 1700s, 1600m, 1530s, 1495w, 1460s, .1435m, 1380sh, 1350s., 1315s, 1265s, 1210s, 1182s, 1165m,1150 m, 1120ah, 1080w, 1045m, 1000vw,. 975m, 920s, 900vw, 880vv1, 860w, 830w; 805vw, 769s, 750s, 7l8m, 682s, 630sh, 610m, 555s, 540vw, 51.5s. (S -carbometho.xy ethyl. chloro tin bis-dithizo.nate (Fig. 69) a . ' 3200m, 3060w, 2980-2860s( b}, 1,720s, 1660sh, 1590s, 1560sh, l540sh, 1530s, 1480s, l455a, 1430s, 1370s, 1~36s, 1300s, 1270m, 1200s, 1170s, 1155s, 1070m, 1030vw, 1018w, 992m, 985m, 975m, 920m, 900vw, 850m, 830w,. 750s, ·ea2m, 678s, 625vw, 610m, 555vw, 540vw, 520w, 4S6vw. Bis( ~ -carbobutoxy e~hyl.) tin bis-dithizonate (Fig. 70 ) a · 3195m, 3040vw, 3000sh, 2940-2830s( b), 1712s, 1590s t 1510s, 1480s, 1450s, 1400vw, 1358m, 1350s, 1330m, 1305a, 1279w, 1260m, 1239m, 1185s; 1165s, 1152s, 1140s, 1120vw, 1000s, 1020w, 990vw, 970s, 918vw, 910w, 900m, 890vw~ 872w, 845m, 820m, 785vw, 760sh, 752s, 735s, 705m, 678s, 600vw, 620vw,· 605m, 558m, 560m, 540sh, 520m, 495s. -139- ~-oarbobutoxy ethyl chloro tin bis-dithizona~e {Fig.72): 3190mt 2960-2830s{b), 1710s, 1580s, 1503s, 1480w, 1450s, l400w, 1370s, 1335s, l292s, 1250s, 1180s, 1152m, 1130m, 111o'm, 1060m, 1010vw, 950w, 890w, 846m, 820w, 752m, 735s, 700s, 670s, 650sh, 620vw, 600m, 520s, 490e. I ~ -aarbomethoxy ~-methyl ethyl ohloro tin bis-dithizonate (Fig.74)s 3190m, 296G-2840a{b), 1705s, 1590s, 1530sh, 1495sh, 1460b, 1350s, 1310w, 1290b, '1-195s, 1135s, 1100s, 1070s, l049sh, 1020w, 990V\Vt. 980vw, 920m, 910m, 870m, 840vw, 780s, 770a, 75os; 'l30s, 715s, 6886, 622m, 585m, 5a3m, 535s, 510m. Product of reaction uo. · 46 'page gg) (Fig.'1'6) a 3200s, 3040w, 2960-2840s(b), 1600s, 1525s, 1495s, 1470s, 1405sh, 1380s, l368vw, 1340s, 1310s, 1272m, 1212s, 1i87s, ll70w, ll52vw, llOOw, 1072ui, 1025m, l010vw, lOOOm, 980vw_, 962vw, 948vw, 92om, 900w, 890w, 860m, 830w, 'l62s, -~ . 746s, 730sh, 710m, 680s 1 935m, 610m1 562s1 .548w, 530a1 520ss 505s. Bis(~ -carbomethoxy· etnyl) chloro tin diphenyl oar.bazo.nate ·(Fig. 78) ~ 3150vw, 3100-2820s(b), 1720m, 1670s, 1590m, 1542m, ··•. -14Q- 1535w, 1500w, 1450a, 1400vw, 1396m, 1362m, 1220a, 120.2- 1070b, 1020m, ·980vvJ,. 950w, 910w, 890vw, 846m, 745s, 682m, 610sh1 600m, 560vw1 515vw. Product o:t reaction .No. 48 (page 101) (Using Naci. w~~:~4:aws) . 3260m, 2980-284ba(b), .1705m, 16B0sh~ 1650s, 1600s, 1670sh, 1545w,- 1520vvv, 1490sh 1 1455s, 1400w• 1365s, 1300m,. 1245w, 1210vw, 120~1120b, 1110vw, l060w, 1010vw, 960vw, 900m, 830vw1 710w, 710s, 650vw, 600s, 570~v. Bis (~ -oarbometboxy ethyl) tin alizarinate (ffig. so)a 2960-2850s(b), 1730e, l675s, l635s, l620ah, 1585s, 1520s, 1445s, 1420sh, 1345s, 1g~5s, 12~~s, 1200s, 1182s, ll60V\v, 1142s, i1l5V\Y 1 1029m, lOlOm, 965vw, 952w, 915w, 892m, 842w, 834m, 815s, 782w, 830m,, 8l5s, 792w, 760sh, 750e, 720vw, 705s, 690m, 670vw, 655s, ·640w, 610vw, 542m, 515vw. ~ -carbometho:xy ethyl chlorotin alizarinate · (Fig.·S'2.); 1628S ~- 2960-2840s(b), 1705m, 16:41.s,"l590m, 1570sh~ 1560sh, 1545vv;, 1525s, 1450s, 1370sh, 1345s, 1300shr 1280s, 1~50b, 1210w, 1180w, 1145w, 1125vw, 1050vw, 1630vvl, 1012m, 960vl, 915vw, 8~8m, 825s, SlOsh, 790VI4•~t 7.60m, 710s, (360m, 640~, 600w, 550s. >- -141- Bis(~-oarbobutoxy e~hyl) tin aliZarinate \~ig•83): 2960-2840s(b), 1725s·, 1670sh, l660sh, l636s, 1620sh, 1585s, l570sh, 1560s, 1470sh, 1455sh, 1440a, 1420sh, 1400m, 1340s, 1295s, 1280s, l235s, 1210s, ll95w, 1180m, 1140s, 1110w, 1030w, lOlOs, 985m, 960w, 935vw, . 910w, 895m,_· 865w, 838m, 818a, 788w, 770sh, 755m, 730vw, ?lOs, 695w, 675vw, 660a, 648w, 635sh, 600m, 550s, 420m. ~ -carbobutoxy ethyl chloro tin alizarinate (Fig. 85): 2930-2820s(b), 1710m, 1640s, l625m, lp90m, 1520m, 1450s, 1375m, 1350s, 1300sh ,. 1280s, 1255s, 1225vw, 1205w, 1180w, 1148m, 1017m, 970vvl, 920vw,· 900w, 830s, 765m, 710s, 665m, 645w,". 610w, 590vw, 560s, 520vw. Product of reaction No• 53 (page 106) (Fig•87)J 3400b, 2960-2850a{b), l725s, 1665a, 1620vw, 1590vw, 1550w, 1520s, 1450s, 1385s, 1370s, l355vw, 1340s, 1285s, 1260s, 1220s, 1200sh, 1179m, l155m, 1140s, 1097m, 1030m, 970s, 940vw, 910w, 870vw, 855vw1 840w, .. 825s, 810vw, 790s, 755m, 728s, 710~v, 690vw, 660s, 630vw, 590m 1 530vwt"495w. Product of reaction l"Jo. 54 (page 106) (Fig. 89): 3460b, 2960-2840s(b), 1720b, 1680sh, 1665sh, l645s, 1590s, 1550w, 1510m, 1455s, 1435s, 1360s, 134Ds, 1290mt l260m~J 124.0.b, 1200s, 1170w,' 1130V'Nt 1100vw, 1150s, · >- l'140s, 1120vw, 1110s, 960\v, 950w' 925·s, saovw, 860s, 840vw,. 825vw,. 810vw, 790s, 760m, _7.25vvf, 706s, 682m, 655m, 630s, 610w, 595a, 550V'Il(, 535w, 520sh,. 480m. Bia( ~ -carbormtho:x:y ethyl) ~hl~ro ~tiA 1-nitroao-? naphtholate (Fi~ • 91.) '· 2940-2840s~b), l722a, 1605m, 1590s, 1560eht. 1540s, ' 1460s, 1410sht· 1380s• lMOm, 1320m, '1305m, 1245vw, 1230m, ' ' ·1210s, 1170w, l100w, 113om, 1080m, i040m, ·1010w', 995sh, 97ow,- ~lOv·1, 880vw, 800'\rw, 835s, 805w, 770m, 740m, 710w, 695vw, 665w, 630s, 600~, 585w, 530m,· 520sh, 500vw. Bis( ~ -ca.r'l?OI!fethoxy e~hyl) tin dithiocyana.te (Fig. 92.): 2900-2840a(b), 2300w, 2060s(b), 1650s(b)~ 1540vw, 1440s, 1400w, 1370s, i300sh_, 1260s_, l2~0s,. 1180vw, 1140s, 1090vw, .1075sh, 1035s, -1008m, _955s, 89D\v, 890m, soo·vw, '750s, 700s, 60~m,· 560vw, 5POs • . ~ -carbometh oX¥ ethyl -~~-: .. ;. Prod.uct o:f reaction No. 5a (page 111) 2960-284Qa(b), 2070s, l720sh, 1670s(b), 15BOb, 1460s, 1420b, 1370s,. 1340s, 1280sh, 1255s, 1210s( b), -143- 1120s, 1090sh, 1065eh, 1040s, 1005m, 910m, 855m, 800w, 750s, 690s, 645vw; 600s, 560w,' 54:0w, 520V\I'f• "Product (m.p. -110°0) of reac-tion No. 59 (page 112) (Uning Hacl wi!nd?ws; .li'ig. 94 ) 3400b1 29 60-2830a( b), l ?20s, 15'75s, 1550 s, 1450 s, 1380s, 1280m, 1220s, ll85vw, 1130s, 1020m, 960w, 920w, _cl3Bvw, 8.:10vw, 750m 1 680s; GlOm. l)roduct (m.p. 290°0) of reaction No. 59 \page 1.'\2) (Fig. 9.5): 2900-2820s(b), 1540s(b), 1460s, 1430w, 1380st 1280m, 1240m, 1115m, 915m, 775sh, 768w, 725s, 620s, 590m, 530s. The P:l'iiR (proton magnetic resonance) spectral d.ata. of several~ -ca.rboalkoxy ethyl tin coordination compounds along with those of corresponding ~-carboalkoxy ethyl tin chlorides and :few ligands taken in 0})010 against the internal standard 1.Cl-viS, are presented in the tabUlar form (!fable - VIII). The spectra were recorded on Varian :81'>11- j 390 Jpectrophotometer (oJi Bose Institute, Oalcutta)/l?erkin- Blmer R-32 spectrophotometer (at .L~egioual Jophistioatad InstrumGn.ts Centro, CDRlt LucknO\v)/lieol-Japa.n, FT .N.MR Speo·trophotometor (at Indian Institute of Chemical Biology, Calcutta). :E'ew of the spectra were aLso obtained from Indian Association for the Cultivatio.u of Science (on Varian A-60), Oalcu tta.. - ·,!_ ' )';;( -~~-(,,.,-- -- '-.d' .~-- ·f!!t'-· '·~. !, -144- _' . TA:Bf_...E - VIII . . PMR spectral data {in CD01 ), Chemical shift values, ppm ·.(down field from TMS}' ,. 3 6 Compound ·Alinhati£ nrotons Aromatic protons. c( ~'A: a _F->-OH 2 _ --OGH3/,'-0CII2 'nihers I , L UZl \ H ~ ) { H0 ) . · · Bis (~-carbomethoxy ethyl)- -1.92- 2.93 3.82 . tin d.ichlo~ide LFig(2 J. - -~-ca~bom~thoxy ethyl 1;in- · -2.27 2.9\j .. 3.97 trichloride Bis (~ -carbo butoxy_ ethyl) 1.90 _2.92 4.2{1 tin dichloride ·~ -Carbobutoxy ethyl tin 2.24 2•98 4.37 . 1.08 {-CH r trichl~ride ~Fig. 6_7 3 1.11-2.02· : '-OH2-m-I 2) · Contd •• >.Y J ~l¥'' ' f~ ~ ,. -145- TABLE- VIII (Oontd •• ) , Compound _ .. ~_1\l~i:o_b._a.tic nrotona Aromatic protons o< -CH2 ~-CH -OC%/-OCH2 Others 2 ) (Ho<) ( H~) . {H0 ------.----·------~--~------~------..--.-, . ---~· ~=carbomethoxy ~ -methyl- 2.25 3.30 4.41 1.56 (-OH) '~H3) ethyl tin trichloride a-hydroxy quinoline (oxine) 7.11-7.58 8.73 .8.11 [Fig.1o] (3,5 ,6 &7- (2-H (4-H · O.x:ine}. H ·oxine) oxine) 5 ,7-dichloro oxine L-Fig. 33:J 7.44-7.68 8.50. 8.84 (3 &6-H) {4-H) (6-H) 5,7-dibromo Oxine L~ig.4Li 7.58 ,, 7.90 8.46 8.82 (3-H) (6-H) <4-H) (2-H) 1,5-diphenyl carbazone 5.72 6.70-6.96 (-l~H) Bis( (> -carbometh oxy ethyl) 1.34 2.44 3.56 7.02-7.34 7.60 8.15 8.54 (3,5&6-H) (7-H} (4-H) (2-H) tin-bis oxinate L-Fig.1?;} Contd •• . A> ,.,jj. 0 ••. ~~y~- ·/-!'--' .. ;[~·:< ;,l,y'· "'r-.•. ,.. -146- ~A~E· ~VIII {Contd •• ) Compound Aliph_a.tic _ _]:lrotons Aromatic protons ·.:< ·-cH2 ~ -cH2 ;;ocr-r3/-00H2 others ) · ·. \Hod (H~) \H0 ----~------·--~----~~------·-.------.------~-~------.Bis (~ ..;.carbometh9XY . ethyl) 1.70.. .~.84 3.70 7.04-7.36 ji~40-7 .so 8.46 9.06. (3&6-R) {,5&7-H) · ·(~H) (2-H) t hi ocyas_at o tin oxiiiat e . . L Fig.14J . . . ~--cal:"b.Ome-Ghox.y ethyl c~loro. 1 .• 77 2.·'?2·. 3.3~ . 6.90-7.32 7~45' H.lO 8.4'7 · (3&6-i!). (7-H) (4-p:) {2-H) · ..tin-:-bi·s-ox~nate [""Fig.16J ~ ~carbomethoxy ethyl thio- 1. 47 · 2.58 . . 3.-36 6~92...:7.3(l 7·.36-7 .68 .a.i7 8.48 1.71. 2.72 3.45 '(4-H) ··(2-H) cyana.to. . .tin bis-o.xinate . •' L-Fig.1q • • p ~ · ~-carbomethoxy ethyl tin- 1.50 2.37 . 3.29 ·6.73~7.75 :7.92. '8.62 1.'J7 2.73 3.~2 a~1o 8.96 tris :·oxinate Ling. 2oJ (4~)· .(~-H) (S ~oarbobut.oxy ethyl chloro~ 1. 72 2.67 3.78 . 0.82 '6.84-7 .28 7.41 8.08 8.46 \~OH3 ) . (3,5&6-~) {7-H) . (4-H) (2-H). . tin bis-oxinate CF1g.2f/ 0.99-1.59 ' · (-OH~~2 ) ~ _ . . · 0ontd •• '~'' ·"· . -~--,...--. -~---- -'~" . .'-"-- ·1(: -:\"/ ·.-147~ -¥ ~ - TABLE -. VIII . { Oontd •• )- i- ·Compound· Alinhat·ic nrotons , Aromati_c protons {rr~~~ r--(~~ -OcH~~scu2 -- Others-- ...... ----~----~----~----·------.------5------~ ______.*" __ .______.____ ~------..----·------(S-carboblitoxy_ ethyl· 1. 46 ,:. 2. 54' 3.86 - 0.86 .· 6'.92-7 .34 7.51. 8.13. 8.46 . . (~CH ) (3,5&6~H) (7-H) {4~H) (~H) : .thi~_cy~ato -tin 0.99-1.~5 (-CH2-CH2) bis-ox:inata CFig.2§7 . ~--carbobutoxy. ethyl tm · ' 1~ 67-.2.20- 3.50- . o. 6~-0.94 .. 6.73-7.70 8e'04 ·a.73 . 1.97 '2.80 4.03 (-CH ) .8.50 8.99 . .··· t.tiia-:-oxillB.te ./:'JJig.~ 27J ., 1.02-f·. 67· :(~II)' (2-H) .. (-OH2-CH2) · ·.. · . I ~-c~rbomethoxy ~-metbyl- 2.01 ·3.06 3.42 1.32 6.96-7.~1 7.58 8.24 8.62 ( -OH_) (-OH3)- .\3,5&6-:ii) (7-H) - (4-H) (2~) _ethyl c·hloro tin bie- · oxinate f:Fig. ~9J B_is{ f -:-carhomethoxy ethyl) · 1.46 · 2.50 3. 70 7.52 . 7.70 8.54 9.10 (3-H) . ( 6-II) (4-H} \2..;H) tul-bis-5,7-dichloro ox~nata CFig.'35J Oontd •• ., "'/ /,. ~~~ . '~ 't\_,1· ,\ I, } -148.;.. T.ABL~ - VIll ( Gon td. • ) l.• ... Compound' __ ..\1 iphatig_orotons . ___ .Aromatic protons ~ -OH2 .~-oH2 . -00H~-OOH Others , . 'Ho<) . (H~J · He } 2 .. Bis( ~ -carbomethoxy ethyl) 1.-34 2.41 3.57 7.39 7.83 8.45 9.02 (3-H) (6~H) . (4-H) (2~H) tin-bis 5, 7-dibromo . ' ·' ' . oxi~~te ~Fig.4~ ! ' ~~carbomethOxY ethYl 1.18 2.31 3.41 7.29-7.60 7.82-8.08 8.28-8.60 · 9e09 1.55. 2.63 3.51 chlorq-tin-bis-5;7- ... ' II ' dibromo oxinate ~Fig.45~ ~-carbobutoxy ethyl tin 1.73- 2.16- 3.82 ' o.so" . 7.54' 7.83 8.32 9.08 2.12 2.53 . · (-OH3) (3-I!) (6-H) (4-H) (2-H) tri-s-5 ,7~ibromo oxinate o. 99-1.72 ' " ' (-OH~OH2) CF1g.4Jl Oon.td •• -~-·- :;.. ).i .q·-.--'-'· , ·';_.j.,, ':Y' -~~ · .. .. -149-:' .l TABLE -.VIII· ----~~------...... -.~------....------...... ~------~------.-~~------.-.. Coninound Alinhatic protons . · Aroma-tic protons . . -- . c<--dH2 ~-OH - · -OOH3/-oOH Others 2 2 __ '_ -"'· _ -~-- ____ _ (rr_L______'-.U9__ ~---_. ~ (Hc:L . •' : ,., '· ~ _-carbomethO;fCY· -_~1::7flletbyl. 1.66 . 2.49 . . 3.37 . 1.11 7.22-7.59 7.79-8.03 . 8•23-8.57 9 .• 07. 1.-98 .. 2.82 3.46 1'.30 ·~ . ,., etby;L•c~oro tin _'~~s~5 ,7- ·. (-CH) . {-GH3) dibromo oxinate· . . , (5 -c~bometho:lo/ · e-thyl chloro· · ... - _1. 66 2.70' 3.50 '7.45 7.86 . 8~22 . 8.59 ' 9.36 . . (4-H) (2-H) t.in-bis phenyl-5-a.zo _oxinate CJP1'g.5?J . ~-ca.~b?Qutoxy_ ethyl. chloro 1.7 2 2.65 3.90 0.84 7.43 . 7.87 8.2o. s.eo 9.35 . ~ - •' - (-CH ) . ( 4-I-I) - ( 2-H) ti~-bis-phenyl-5-azo oxinate 1.20-1-.gs (-'C,'H2-0H2_) L-Fig. 57.:.7 · Bis( F -carbob11toxy ethyl.) tin. 1.'98 2.98 . 3.39 1.27 ' 6.90-7.38 ..: 7.53 .. 8.17 8~55 (-CH ) . tin bis-phanyl 5-a.zo .oxinate · · 3 1. 68 · L"1'1g •. 55 J ( -C.'H2-0H2} .·I .'y /, :''~ ,:'-f.I ·-v ,~- -150- TABLE - VIII ( Conta •• ) ---·--· •.a------·----~------·-----~--~----·~----~----~._------~------· =-· compound ______.Al~atic nrot?ns Aromatic protons o( ..._?H2 ~-OH2 -OCHz/-OOH2 others \HP Bis(~ -carbo~ethoxy 1.44 2.45 3.57 7.07-7.68 7.78 8.16 8.59 8.97 9~'30 ethyl) . . ' b"iS . . · 1.90 2.72 3.65. tin/..5(2' -carb:oxy phenyl} 9.49 ' ' azo-oxinate ~Fige51_7 Bi~( ~ -carbo~ethoXY: ethyl) 1.94 2.63 3.55 9.45 7.00-7.70 7.71-8.02 . {-NH) · tin-bis-dithizonate LFig. 64_] Oontd•• .- ,.Jlr x·; }::.· ~, r· . : ~ ' 41 ,~,/ {_ -151- ') TABLE- VIII '{Oontd •• ) coffipound Alinhatic ·protons · - .i'x~matic protons ~-CH2 -cr-r 2 -oorr:.J.:.octr2 Others (Ho<) 'HcsJ t'Hc ) ·------• • • II Bis { ~ -~arbome~hoxy .~tbyl) 1.8rt' 2.81- . ·3.65 9.15 . 6.91~7.60 7.66-8.08 (-liH~ ' chloro tin dithizonate Cf!ig.66J ... ~is(~ :-carbomethoxy 1.91 . 2.82 3.71 9e34 · 7.10-7.68 7.71-8.15 <~wr·. · ethyl )~thiocyanato tin dithizonate CFig. 68J ' Bi~( ~.-Parbo:butoxy_. ethyl) 1.83 2.54 3.83 0.76 6.71-7.51 . 7:.53-7.89 . (~CR3), tin bis-dithizo~~te 0.89-1.65 ' (-CH2-CH2) . CFig.'fiJ .4.10-4.87 ' (-NH) . ~{ ·.'y· ·~.-: y·t.- -~.: ·:yi ;. " .;_152- . - ..... 1,, ·, TABLE - VIII (Oonta.~.) ·compound . _ · . Alin~tic protons , ·.. ··Ju-_omatio protons .. · ... .:-_- o(' -on:2 ~- uu2 -o·~oF::-~l:;;...... ,...o::o:'!::'!oH::-2--~ot:-:-:h=-e-r_s_ {HoC) . {H~J · \ffo) · ------·------·--~------~------~------·------&-carbobutoxy ethyl chloro .. 2~02' 2.51 3.9.2 . o.so 6.91-2.42' ''7. .-42-,7 .86 tin-bis-dith iz onat e · (~CH ) 0.92-1.~7 CFig.Tg \-CH2-0H9.) . 6.20-6. 6'6 . (-NE} . , I . , -~ .~ ~carbomethoxy ~ -methyl~ 2.10' 2.60. 3.47 1.08' 7~02-7 .50 ,7.51:-7.89 . . . - . (-OH} (-CH3) e~hyl. chloro tin. bis~ · .. · 5.28 . '' ·. . . ,, . ··,. ' ( ~'ifH) dithizonate CF1g.75J. · :Bis ( ~ -carbom~thoxy ethyl)- · 1. 69 2.70· .3.70 6.90. 7.65 7.84· 8.23' tin alizarinate L-Fi·g. stJ . ' B:i,s ( (5 ~carbobutoxy ethyl)- · '1.-Eq 2;.66 4.13 1.0.J~-1 &:4~ 6.87 7.60 7.ao 8.19 ' ' <-cH -cH ) tin ~llzarinate ~Fig.84~ 0.842 .2 (CH3) Oon-~-d'· · Ill· ~ ... ·j . r- I 'l· r)~ ~'~..1 ·'V ·'~ ! -153- TABLE - VIII (Contd •• ) -- ...,..._ ___ _ o'ompound u-u Alinhatic grotons · _ -- .Aromatic protons o< -CR2 · ~ -CH2 -ocr(31?-ocr-r 2 ·others ___ _ {H~l. _ (H ~.. L:._~fleL-·------Bis (~· -carbomethoxy ethyl)- 1.,58 2~ 62 3. 66_ 5.85 6. 65-7.50 7 .so chloro tin diphenyl carbazonate (-HH) . . Bis{ ~ -carbomethoxy e:t;hyl) 1 .. 74 2.82 '3.76 6.58' 6. 96 ·7 .36-7. 72 7.84 8.34 chloro-tin 1-nitroso-2- naphtholate· Bis(~--~carbomethoxy ethyJ.)- 1.57 2. 73 3.7~ . ~ . ~ . 1-.21 1.98 3.30 tin -dithi ocyamte CFig.9§/ ~------~------