THE SYNTHESIS OF SOME 1,. 4 - DISUBSTITUTED - S-IMINOTETRAZOLINES Thesis Ior the Degree of M. S. MICHIGAN STATE UNIVERSITY Willard Jason Haak I957 Mcmcr o ' EAST LANSING, .‘ailJHIGAN . u»... who-”3mm LIBRARY Michigan State . University Mncnzm 37.6.72: rz_f::'.'::tssr\,’ EAST LANSL‘IG, MICHIGAN m1 surname. 03° 5sz 1,h-nxsvas'rmm'zm-s-n-Ismmmznmms 3y n 1111111 Jason Hank L TEESIS Bub-1““ to the College of Science and Art. of Michigan S‘ato University of Agriculture and Applied Science ll.part131 fulfillment of the requirement. for the dagroa of MASTER OF SCIEKGE Department of Chemistry 1957 ' ‘ ‘o- - n‘ .1; t J .r" r- ?‘3 ‘§‘ W ”p, :- .‘fl .4 L '« ‘ A- I} m \ ‘n A.- b ‘ hi-al‘d. ?'.cr ‘ I L'“ c“'--'Iasr.+b ”‘1‘. 1"}. I4-‘ I q pr t»... ~ It ., uT. .rv . . .‘ '1‘: LI‘(r'"~c . ‘ ‘. -41} ' _ . q, - . '. -"' 3 ~.... ,‘5 a"; .J.‘.. ‘. ‘ ;. L... ‘47:: :2 “5,4134 .I .«.0 an}. bars mnmaa a s r“ 5* g c: ,3 " . 3‘ - . a .- .v’v- ‘ '- ‘Dl ' -' 29: - v.31“. 2%.. an 153% fiflLfiEfi-tfi‘. ‘2": t “3 .. ?' (‘7‘- .‘ r. ‘1 . .fi “an - . ,. ‘. .. ‘3 . {0/7}; ACEHO‘II’LLEC’EL'EHT The writer wishes to expree. his appreciation to Doctor Robert M. Herbut for his most helpful counsel and assistance during the performance of this work. Ilinltfltfitii .OII##¢II¢ ¢¢¢t¢¢0¢ tittit 000. t! O .u .l- '. ’. THE SYLI‘ ."313 OF 8031.151 4-DISU3JI‘ITJTED— S-IELJTL; -,. mm ~. = By Willard Jason Haak Submitted to the College of Science and Arts of E1chigan State Uilvers1ty of Agriculture and .1pplled Selene. 1n partlal fulfillment of the requirements for the degree of £13311. '3? 3013' 3'23 Department of Chemistry Year 1957 ' ' ' j . f /‘.,I.’-’ f; I: -" I .f r Approved If: 049" /’/ l -’ its“: .. a. ‘+_ i. . fie! .ri u _ I d .I \ i . C. ...W .‘ :3 € ‘9‘ . ‘1 a... . . » . ‘ '.P .k‘ .. 5.. . '11 QM .r u f. .13 31.1.2 mi? ":4: aw ~21} f... I. :. .4ii':II’1-JJ: '1 m u ’1' a" ‘ .-.-.w- .1 v Le~ y—' m ~0~ 0-_ an]. Ia..- 'b"\-o- I'- , .-V II . A .a ) ';' fl ~1’r 9* .2 in.“ Q) L. /' .} 3 fl} V . . \ '. u. I \ . - — -4 \-~-‘.\ ‘y vac-v.4y—pn-u'.‘ H..- v "" 1‘) ~ \ v-wa' '1w-,--‘, *n , FILLL‘KD JASCL’ Hm}; m lmtyerk (1) has ghoum that loremonbgsyl-bomwkgq 51,-. {montnsonu has eldal action against W m n m. !t was also mm.,.aot1ve Against cute}: “may, W m m A series of new LII-dieubstltuted-fi-unetetmsouna «new»...r .- fiared for testing using the cyclahexylethyl you; 11 place of their" octyl group. The series has the fcllcwlng groups in the h-podtiom bojzyl‘ o—thorobenzyl. p—chlorobanzyl. EA—dielllcrpbongyl, :3.‘-dlch- lnrobenzyl, a—ni trobenzyl . ' p-nitrobenzyl . ' yphenylpmpyl" um I 2-phenylethy1. {the ‘5-1l3n0tetramlines were prepared by £31131“; 1: 1.42.0.1". hmlethylH-nlnetotrazole with the arelkyl helm. 1131:; the method of Sorbet. 30M!“ “4 Hardll (52} with none maximum. “- cola-Ogfinflq -—S;EH 4- RI .._.. ‘3’ ._ cycl 0-0 6311 CIIECF2W FIT-3° RX R \\H/ R g aralkyl l-(B-Cyclehexylethyl )-5~e.minotetrarole 1s a new campound prepared by the {011011113 eel-1e. of reactlons: E-Gyclohaxylethylenlne. a: “ter- nedlete, we: prepared from 3-cyclahemlproprlon1c ecld by the Schmidt rescuer. uslng hydrazeie acid (3). n at I- r H 30‘ 1~ 11- v . cycle-Gsnncfieedzuoafi «b 5213 A cyclc~c6anea20n2mz 0 Hz «b 002 3‘, 5 I -5 :I «I» \- 1 . 0‘ 3 -- ' . A . s ' . ‘ hn~~-'O”u A *6 no vp-a- 4*. I‘ v .' “t {U 7 a I: M rm :3?» h ‘ “it? Rm; rat-33mm! The amino Wm; than allouei ta react with cyABOgan bromide to fern the nonaeubstl tuted évunaaide. ‘. ' ’ , . a 1}- ; " R137}? 0 iFnr -—-’ Elia-03F #3 F1 3 cycle-G’FIICHZGEQ- ‘ '" - - 'V" f . 2h, 2.9yclohe: letfigrlcjg-mmnifie was treat-3‘3. with hydmzalc acid. and 4.5% the resulting oroduct cyclizei to l-IM—c"~‘"hexy" ‘hvl‘--~*1ne.e*ra- ‘ ‘ ’ =0..e (II/1' 1:113:3333 + 21:63 —-. 211:}; :34: 2—" II lg—rrzz #1,» 1211- 3 Q3/ Rim 111 - 1'(2"3Y°19391?1°t571)-5'flmin0tetrazole was charactertsei as the par. solid. acatyl derivative, ad infrared spectra. Characterizat1on of the l-(Q—cyclahexylethylI-h—eralkyl-S-lnlno- totrazolineo was as the hyflrochl orifie, nfienylthiourea and the Iolid free base when it could be cbtained. rand] o .. . v ! .2 . ' i 'i H - ~ ‘ v .‘ 'I‘ u.- -‘C 3 ' .4 I! . A s ' U I' O_‘ .a i I \| d . t r--v 7f ‘ " '~ ‘ Sr“ “I!“ l 1* 1“ ‘ r A‘ I A 1‘ . V l , A. l - . § ‘ a -" .- u I . .' -v. 1" "- m " I I. ‘- f A r“- -. . . Q .. (I , f 3 _. r a! V A 4: ‘. I uA'a :— ~ . ' - _ ‘ H -. ' A' I:. ' r. r- - v.1 : " . ' I n- l. I o o u h‘ "d ". .9- o O , l - . . f‘, n‘ 5 ' 1.. 4.." . q .I u .- .'. .. ‘. 4 N' .h.' 6 o ’ HA It - J o-Ll- ‘- - J I .'\ o ‘ , "‘ V.‘ ‘D O\ \ ' ' ‘-". ‘lf- 9 ' " _ ) *— 5 ' + ‘ 3 .0 H g. o 1‘ . n, A n. . . I ‘- 5‘ A l f " ‘I .- 1". t “ - v p I. '. .- . -_, . 7. H’u l!‘»‘|:'~:\,-\ "‘..—- ‘uvr l - _ " .‘I ' .. c _, . I V 0 i I ' ‘:.» 8'*0 'Vr.sfi‘ .“Ia i :n t I " | h.- r _ ‘ ' I- r . . , . n , -. r a -. 43 ' 'wc l I - r ' u 3231292 JASfiN 35a? . AVGTPEGT ervna?7“? 019*3 1. E. P. Elolnggr, E. I. Reutnor. and J. G. Petara, Abstract: of Papsrs Prosontod nt the Mootingu of tho Llorican Chonionl Society; Dallas, Tums, 72! (April 1955). G *d .. 1!. Herb“, 0. Bo'aerts. E. Hamill, J. Org. Chem. lfi, 139 (1951) vith Iodifioations. 3. E. Wilson. unpublished work. It. ‘1. Garbrooht and R. Li. Harbin, J. Org. Chem, 1;, 1003 (1953) with modifications. ‘9' .. y. In ft. n . i I 1...; v .Q I . _ .t u i. .- o ul‘ 9 U .l . 0., .l.. 3 .. _. A‘s- 9',‘ GI 11 x 17"}? 73",? '{V 3 7“" ML~vuJJAdeoooIooocoo.no.000.000.0000..oucooooo-oooo.coco-.00....a. 7.-."nrv (\‘T Ab;d£1U&&ooooooo.¢booo0.0.0-0.00.0000000.00.00.00000000900000000... 3156:35510H.000.0000000.000000000000000.COO-OIOOOOOOCIOIOOOI000...... 7' ' .u-cm‘ “EdilkbizTALOOOOOIOIIQOOOno-cooocoouoloQIIOOOOOOQOOIIOQQQC000000000. —-—. p1 Preparation of Hydrazoio Acid Solution..................... PPCParation 0f 2-0’310hoxy10thy1anin.oo0cocoo-0.000cacao-o. Preparation of 1-(2bCyclohaleathyl)-§-Anlnototrnualo...... Preparation of Aootyi Derivative of 1-(2-Gyclohoxylothyl)- E-AuinotetrazolOoc..........................o............ Preparaticn of 1.h—Ditnbatitutod—S-Ininotetrazolinou as EYdTOChloride.ooooooocoo-o.coco-000.00....ouooooooOoOoooo Benzylation of 1—(2-Cyolohexylethy1)-5—Am1notetrazolo...... Alkylation of l-Benzyl-fi-Aminotatraxolo with 2-Oyolo- hexylethyi BfOflid...0.0.0.09.co0.0000000000000-000000.000 Debenzylation of 1-(2-Cyelahexylathyl)oh—Bonzyl-S-Imino- tetrnzoline Hydrochloride................................ Praparation of Fhonylthiaureau fro- 1,3-Disubst1tutod- 5-Im1n0tetr3201130'00009-0.noo.so...coco-0000000000000... Preparation of 1.4-D1-ubaticutad-S-Ininotetrnsollno Baueio. SLI‘BiEA-EAEETQQQQOQQto...IO.COCO-QCO.QOOIOOOOOOOOOOOOOOOOOOOIIOOIO0.00000. LITinyJF-E SI'i'lm...OOOOCOOOOICOOOOOOI.DO...OOIOOOOOOOOOOCOOOOOOOOOOO 11 11 12 13 15 16 2O 22 22 26 27 .1 34 no", L 'J .auooo-asO‘lI-OIv'holvthlOIolv-IIIICUM“~; rv ‘o -. ' p . " - I nono‘ 1', ”v0, I a o I a I 9 4 a u o . s a 9 e o o I u ' ." . . . . f. '- . 4 . -1 . .. J _ a - ‘- v' I ‘ . . ., 4 “ 'V .1 . - ~ ~ g . . w 1 \ q .0):iov«-J«C|QOOOUII —w , ,‘-~. .n. .. 'V' ;.,A, ‘__ ‘J ‘ Q ! . ‘ r” . ‘ l ‘- ‘_t 'I t I , 9 ‘ I _ ’ _ - . 5 ‘ w . - l ‘6 Iii ' - ' - av " - -. '\v‘- . " .~ _‘ " "-5- -c- a“.'.'.:"a.:~ .; . ' r f _ . . _ -. _ . a ’ a l w - . . , , ...., 4,1 "vwz ,):--..—.,\ in if "‘-"""""“T «. . ' s _ . . v 4..- . - ! ¢ - . I— ; l -- — a a ‘v' ‘v ‘ ' ‘0 —.\‘ a v , oc..l..=..vgv-.|¢ aoacsoalau-udltloac " -1“! 0A r - ' . . . ' n 5" 0 r J‘. .“ J l 1 a _ .1 '4 "' . ~- . , . _. '1 Q. . l i f , 1.1 }.: I. v I .- . A- . ' ' Lou'v‘ ‘- d y- ~ ‘ “ ‘v ; ' I l‘, ‘ o o g ; a .n t- o u i v a e o o u a a u w o a a l a u 0 9 l . O I o \ A . . .. J -‘ p . ‘ .. . . , g t '- Ia . . a u. n ,. v ~, , ' ‘ , '. r" ‘.:_ s cot"' - .. “-.--*‘ ' o .1. - -' ..F. n ‘ v. ‘ - n- l l ’ _ . u u. ‘ ~ ‘1'. ,' .~~. ' M " \\. _‘ -. '.‘." v £;.. a .:v ". .c --- 'l a A .1." t ‘. .a 4 r "[ ‘..'.'-‘ l o u a o o ‘ o a '2 a I o o c o O o 9 s I o O o o O D o I v O O O O .. v V: J - C - ‘ i . ' 7' II I _ §_ ‘ .,‘.' ‘ F ‘. ~" " "' ‘ ‘_’ 'u 9 a . 1.. 1 .E .. ‘a -_ R‘ 1.. ‘ ’ . - , - ,.- ’ ' 1‘ c1. ’ . J v '»-‘- 5—1 .11 \. f. _‘ J. " .' ‘ ." ' 2'- ‘5. . . ...' .'. o: 3‘ 4 .1‘tuaatnn:o-IOO-y'leOOODOOIO‘. J.. .~'J'g. - . . u _ ' .. -‘ '3 1 ‘I ‘ - ; - -- ’fifih" ‘ "'. . '. 1-- ' . " Ll ' '0 i a- ’d.:~»~ .3; ‘1 .*_:A'.', ‘- _. L‘g l. n‘lln . - V’. .l‘ JU‘M .L- 4’ .L I‘IL l- l . “ " . t, ' A ’ :t‘ l A . ‘ 7 ; F ‘ - :01 T ,' 4 . ,-. 0.0)00090000)OcODOD'OOIs-DOO'IOIDOQ“ ..4.£-- .\. J‘; < " ‘ .. . " Q.‘ , -..‘ , .! \‘ . __‘ " .- . , I .- .~- ‘ .. ' . ' wash...» . .. .- . 1‘ ..-. ”Ax-h ‘1-5-"cd. :29- x .: r-s'm'r- ' . u- I... a z o 5 I o o o o o o s c a o e a o o o o o 0 u t O Q 0 O O I a I . . O o 0 o 0 o c o J o o a o o 0 I I O s a o I - "‘ ‘ . g .p 3 . g i . g g . g u o y o O O o O o v I o O o I 9 O o O O 5 o I n u s I 9 6 I O C O I I l O ‘A _._ l\. L', ...4 oooooo m 01“ mama If: '33.? I. II. III. IV. 1,u-Disubstituted-g-Iminotottaxolino Hydrochlortéoo........ Analysis of 1.h-Bisubstituxsd-S-Iminotetrazolino Hydrochlortd...iOOOOOOOOO-OIOOOOOIOO00....OOOOOOOOOIOOOOOOO. Phenylthiouroau o! 1,h—Diuubatituted-S-Ininotetrnaolinau... 1,h-DiIubutitutod-5-In1nototrasolinc Baue.................. PAGE 17 23 25 u." D ‘ I _ . . ' . \ > _' ‘- ' . w- ('v.- . f" '1’.“ . -. _ _ , 1 C O Q 0 I O u 35: 3' ‘ - .- Vv...) -' a ' I; ‘ v A ~ . . J J I .-~- — \ ' u‘J . x .. .A.’ -I « w C 4. . ‘l _ - - v p ' - . ‘ . - ' .- -‘ °.' . ’=,. .3. ~ .. ‘o . ‘ 64 .\ '5 .' . .- ~‘ .. w . . ’1' . .A.f..; 5‘ . J .. -L. .A \ " . ..~ . *q _ . , . . . au- . L- r. 4 ‘ ‘ _‘ . . , ., , ~ -:.‘.-'1n"r'«*~.. OfltuclOIloaouoIOahu-ca.Iolvanoooloooooooooogo; A. A. -_.,__.-u“ ~ . o .' .- p - a . .. 9 ' - + .9 3 4 ' ' a . . 2 .. .n . r. _. v ,. Oo-vn < _ . -.. y. , - . ~19 ( J (‘0! .". \ l \I ' 9 U s, ’5" oj-tl’ ‘ ‘ 1". . A ', ~L ~ “9 - q k d- K.’ (.4 f- '1 .- In. ' . -u A. 3 3 , . lo". :t- 4'1 —- "!1‘, L1 L t- c. ‘- 5! ,' -' 6': -, .,._ ”SW" ‘f,.,..- ,1 .. -_ fl. _::_-,! J .’ P“:- -V;:L;n ’3-11.I .UOOOOOIOOQOIOII. - ~ ‘1.L-. .- J o . ‘ . . ,3. ' I V ». . .1-.. 8 an “ ,,, c ‘ - n w": “' 3"? "s rh- n“ l ‘ ,7 a. 1 .1 z ._ . ‘I- 9"“ -... . . .u‘wfph‘v “9.“an FIGURE 1. II. III. IV. PAGE Infrared Spectra of 1-(2-Cyclohexy1athyl)-5~Amino- . tetraZOlfi from AmineOouo-oooolooo oooooo cost-ooooooooooooooi 1“ Infrared Spectra of 1-(2~Cyclchaxylethyl3-5-nmino- totrasole from Debcnzylation.................... ..... ...... 1h Infrared apectra of 1-(2-chlohexylethy1)-M—Benzy1— S-Iminotetrazoline Eydrodhloride from 1-(2-Gyclohexylethy1) .s-AnifiotetrEZOIGIOOO000000.00OQOOOOOIOOIOOIOOODQOOIOIOOQO. 20 Infrared Spectra of 1-(2-Cyclohogvlotby1)Jl-Benzyl. 5—In1notetrazolino Eyflrochlorido from l-Benzyl-fi—Inino- ‘.‘ra'°1.0000000000000COOOOQICOOOOOCOIIOOOIOOIoooooog...... 20 P -1 f v - r . a c.‘ ~ . ‘ .I- ~~ - . n. v. '4! I r r 4\ - 1 ' , -(- _ l .1 ’t n. J I I ‘ . J | . '. . 3‘ .I J J .0 VI . a" I . i - A. . 90.00Iancdocllouoicsaooo-nInsuodunuoogg.,. mt. I-u-l.-- ‘ , - a u . t .' . . ... . , o-I' '- '¢.~ A n - .. , . -- 4 ‘ \ & . ‘- . ‘. ' J.l - ' -A ‘~ a}. . .' A. ., i . - k 1. w' j .v -v .7 47,. 2. V. . . ,."._¢" , 9-2 . OOcvc. .oot.Auno..‘uvoIO#-aoopaaz.(1.a ‘.. x. ‘ 1'. "(‘a: l - .- ,' . r ' n ‘ " C . . ~~ ‘ r f, ”‘ in: - " ' and our "" 1~.' " . ~‘ . \ "‘ 7 - U" '3 "I J- n .‘ . ..~ .. _ « ' u as. . .s. . - . f ._ . ,. ‘ -~. ‘ ‘ s 0 . . ' ‘ ‘ - - : i"u‘1. " f . - I ‘1'": 5 -" ' " " ' v" .' " ’ ‘ l ‘ ' - —' . ‘ . ' ' ‘ ' ... ' ' ¢ .. .5 '1‘ L' .‘J. “1-11 "I l 'J“ On .8 ‘- ‘fhd .5 .. \O. ..2\_. ‘ ’ I. '._ ' . ‘. , II J 4 A 4" \ . ‘ .~ . .. ....'.,.'~ynrIr.(ISJ.IOIOIFOOOOOOOOQOOIOQ. .4.\.'.-'.-.: .' f k R g '1' f r ' ‘ - . ¢ 0 ‘ v - r- . . .0 W ,V .1 , ‘,6.-'. ' ‘ u' It. i ,". 1 \ I“ z" .m ' "I Q ", 3"? .31: '. _ ‘ A , .. . . .~ . . a .1 u .. _, . ' .. . . ‘ A z ‘- ,\'-‘ . . J, . a. '.-. .3, _ . .pq, ‘,:- ~ .3 ' ..‘ .. . > _. 'l - 5‘ .. .o . A- (I A ' 2 ~ 1:5 ~- n‘ ‘l A; c: 4 J ') n :. ‘o A. ..\..-' - d I. L. .. L C. "' ‘ ‘ h \v _ ’ o- _ .iu01‘109>-.1I00:0)0109u-l-100JO Idol-OIVIOIOOOIO’I u I.“ . 3 ? I .' . h I ‘ I. I. -‘l' --".ulo .~.-‘ I Recently a eeriee of1-h,dieuhetihuted-S-iminotetraxcline hydro- chloridee here been teeted in the Parke. Davie Laboratoriee (1) fbr their cidel effecte against Irichomcnae £2.32... in m. The teeting ehoeed that, of the couponflh teeted, 1-(p-chlorobeneyD-h-cctyl-5- iminotetraeoline proved to be the cost effective end ie presently being prepared for ciiucel testing. These componnde Iere eleo teeted end were ective again-t muggy; 3 25132;” end ee Mgicidce ageinet Uandide We end W gentaggaggfiel v. igterdigitelg. It we decided to prepare. e series of einilerly eutetituted 5-ininotetrezclinee es their hydrochloridee vith the n-oetyl group repleced by'e Z-qyclohexylethyl group. These eelte are preeenthy being teeted for antitrichceonal and other chemotherapeutic effecte. A new noneeubetituted flee-inetetrazole. 1-(2-cyclohexylethy1)-5- aninotetrexole wee prepared ee an intermediate for the eyneheeie e! the tetracolinee. The tetruole was characterized by infrared spectra. lelting point, and ee the ecetyl derivative.. the tetrazclinee were characterized as the tree bane. hydrochloride: and phenylthiourene. -1- F) a y ’ \ > t _ » e- .—I N ‘ . ‘‘e "4 , . V.- I . . H"I"-’I“‘ .‘-‘ ~ -! ~w vv . ~ - 1 t." " ' , L 05-. f ' v " '1‘ f l 1 .4. " ‘ " ° . 1 1 ‘ . -' 5. H . x . ‘ . “u -s\ , . _. ..e‘l‘ t_ . ' IN' w . , — .‘ t \ Ia ..P- en _ _. . . ' .. f" -‘ _ _. e 1‘“! fr ‘ w'i “ . b. i v‘.‘ . fl . g3 . . -I ~ 3 e ‘ ' I 1 . —.'. - o _e ‘. . e- “t' :“|" +“~ - - ' ‘I 1 v ‘ .‘ - ‘. f’ I‘ , ‘, ',’ ; - .r I . ‘e. r.‘ c. . A L' g. h - ‘1" I ‘ H . ‘zk- 5 ‘ l.- - x u ‘ ' -- - -' "‘ ‘t i «I \ ‘- -we- 9 ‘e‘ Lf: “n o ..I. ‘d ‘ L I.) f? I -‘ ' ‘ ‘_ n L ‘- A , y e. o ‘ .’ ‘ .e r . " . |., w- u 5'. :- . . .‘ r ' 1. _ v J x ’ f L." 1 . .5 ., {eh . . - . n ,5. , ‘ .. ' . a . J _ . . ', v ".' 3 1 ,. -. - .v ‘. > ‘3 e i 3.’ u. . A . - 2.. h -- .3. «1-3 a -. 1-4.1. .1. J , «-- . ‘n' ~ - - 1K “ ‘ P 9 ' e ‘ Pz » fl . ‘ . I ' v. .'. - ‘ " l :r‘ o! . - . .. ~v . o \ . . x _ f _x -, I. ... . ..‘ . , ‘ , L. -. . , . n ~. - . . ,u - "~. e l _ ‘ _. o . L1,... . r'. . .-_ ‘__' at A n - - " 3 er.’ ~3-Hts " " -.. a: .‘ ‘ .~ -‘ ' ‘ e ‘I'e-n.“'vW-'~ - .- pn-ve.~..v~‘p ' . . . . ~ I . w - 4. ‘ ‘ _ J . Ant. . ; I v~ V I J0 r e w» , ~. J . . A - . , .- f y Y .H ‘4 .1 ,‘ -, _ . r ’ -' u_ I. t ‘. e O a ’ .' J . . » . . w t a t‘ ' J ' '. v -.. - J :1 FL; [4 "'7 , , ..Aowp e. ~;.; .. ..1 .¢ '_'.--J,\ ~JA.. ~.o-e.~-il"u.o Lxsnm 'v .--.r I‘— .. “ r: -._._. i.,._..-,~.:.. ,fi,‘ ._-. ‘ 'U .. " ' ‘ 4‘ ' i A b e’ as 5 < 'I A V \. ' ' 4: .u”. . . ' . ’4 . N " ’ I w ' 3’ .‘ '. ' . y' " 'J . "4 ' v1: 4 u. 1 . V- ." -‘-‘ ' ”' ‘. ' r . .' , ' . .. J ' u . ~. .- - -- - u - M) t " 1 1 . in f '.' L 7“. - . ".- ' ‘ ' ' ,1 -' - 3 _. r. s *2 .' ..:.- 'r ' --.-a .' ' r f '1‘ r “, ' ' ' "- ‘ " F‘ ‘ ' , " . . 't‘ ‘t . 9. . 4. 4 y- . e p .v' o b\ . - d“- , ', *v -. ' , '. - fi. . J. , ‘_ f , u 1 ‘ A . ‘1' u V .L.-.. .» . . *. .. .. i "- J W. . If " , ;, . _, " . ‘ v '_ ,. ', .n'..'.. -‘fi l _ a \u an... . . . .' ,. _. .~ M... r.... .-. .- 4' r. n 3. . ,,_ .V - .3 . I . u > . '_ .4 ' ,3 _ ‘ "\ 1‘,“._‘ ‘7‘ :4. -b . .‘I. , . ‘_ . ‘ 1 4 II ‘ .. - -. L ‘f, L' t i. .. IQ. _.. . ~. ' .1, . . J - a. . .J» . , ‘ ‘1‘“ .1, ' I 1‘ AI - 'g": . I . - ~ - -- ~ - . v - . l- . .c . t n - , » 1 . l . . ~ 3 . 4‘e - - - ’ 1" . . e l , e “‘o p :5 _, ‘ ‘ .‘l e '(l 9.4—, ’a t . y. 5...... e.. I . . K - ....u '3 ..‘ v . 2.. , A ’f ..3“. ‘3‘." ..;....L‘..’J '1 I 7‘ . u \ b ‘ Ii 5‘ h V )7. .9. ' . I - \ a I :0 ' r'f no ’ . - o e ’ r . . ' _ . 3‘ l g ' n ~. m yo . ' . " ‘_ _ ‘ I' s:_ '. . “ ’.: ‘- _ '9 ' "' .1 M “in _ .t . . ._,-. - .“' a.’ .- 4: ’ .. 4.10573 ~ .-- 2‘ “c A- '.‘:v wk ..s.»‘ {.l "1'. “TL; I“. n d .1 I- 1 0 C ' - . - . '- 4 .1 r i -. _ ‘ q I . e - u ‘3 .. e—y .s‘ 1- -.x le «I ¥ ~e._.‘ ‘4 .‘ Pt: 4 . ~ .4 .‘ .. fl- “A . -. ..‘ 9-0 ',‘ - t . r N I. 4-; f ‘ _» ' ’. 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' “" ‘ ." i - ‘3‘ .. - vv‘ " . _ . u o)_ e 1, L.- I O R I” 111.. -!heeeyntheeie of 5-aeinotetrazoie was fir-t reporfied \y’fhiele (a) who‘prepered gnaayi ecide by interaction of eninogunnidine and nitrous acidr‘ The gunnyi oxide was heated with equeone eodin- odflbonete or coast-wooetete to firing about ring closure to fineuinotetresolet _ ETWEZ £23 835E415 m HU_HHZ Thiele end Ingle (3) reported a number of products obtained from the direoe elkylaiion of S-eninotetrezole. Hethyietion. ethyletioufiww and bellylatio: led to nixtnroe of products. both.nona end dieubetituted eninotetrazolee. The preparation of some of theee compounds was repeated by Herbet and Peroival (‘4) and it was found that the dinethyl. diethyl and "alpha” dibenxyl S-aminotetrazolee obtained 5} Thiele end Ingle were 1)Ldieubetituted-S-ininotetrazolines. Sodiun ezide end hydrasoic acid have frequently been used in the synthesis of eubetituted S-eniootetrazolee. Cyanelide (5) or dicyaodigmiée (6), which dissociates to «wide. reeofi with hydrazoio acid to give S-aminotetrazolo.a : 3234:3523} ——) iii-Tana ‘H Stolle (7) prepared 1-methyl-5-aminotetrazole by interaction of. ; S-methylthioorea with sodium acids in an ateoaphere of carbon dioxide in the preeenoe of lead carbonate. P1300} . curly-@4132 MIL. 033-3— 1312 602 \\5 By thin reaction he also prepared a number of l-ary1-5-eninotetrezolee from the corresponding N-arylthioureaa (8.9). ‘N .‘l .\. .~:._ It" i F \e I o I v 'p. ‘ c1 . 9" A. l~-._r_ ,. .. . ..' r I, 4 I: 3' Ce .4 4e , ‘F f. v : - J - , t . ‘ ' J ‘ 1 ‘, f‘ c x u 1-“ A , . y‘. A r ’7 ~- ,- , ~ -, r3 - ‘ , ‘ m“ ‘ .. .. e .. , . ,_ _ -. L V. I I ' - a» ' ' . - ',. i -« ‘ ~’.’a s w l .1 u i'. A. . 7 ' " ~63 ”‘e‘ .. , I. I . ‘ S ‘ - ’ ~ g- ‘ . ~ V v - .’ v3 , :‘I ". .N - r. v - . .‘ '.' , ‘- ., 59‘ . . _ 1,"; .. , .- I‘w _' , :I u‘ ..i L- .' . ~ u ..w- :. -J. k ‘. fit: ' I..'...; . _',~.. It.‘ r'fi' ‘. '7“; , L»£“§ ’ r - ' I ~ .. p', ' _ ‘ 7 r ‘ ’ *v ' , I '7 , ( . , ' ‘ 7' C ' 'Y ’ n | ‘ ' v -- I . ' $. < ‘ . . L C a , , ,I . .-- . ' u 3. I ‘ . ‘ . -‘ \ ‘1 5. v.1, 'i '5 .. I. Q r" 1: ‘ 4 1 '.. ~ . - ' . , - P - ,. . ‘, ‘ $ ‘ ’ "' .; ‘ -l - - . .__ . , v . , __. I, - ‘ _= r- r.. , ,. 1' .. .. 7, . 5 I 7 ' . x. J l ‘3.J ( LV‘ .11‘4- - i‘ 1' ‘ ' ~ g . .e f 2". ' " '~.": '.~‘-- ”{va .. - . cl ! ' 4- i : c I r r l .' " '_ “:1 " ,-, ”— (mwm ‘ n‘. H ’1 +1...“ r‘ ’ i f . . ~ 0 ' ' o . t '* .- ‘ 1 v \ J . f ' . ' 4' ‘ A I, u u- . T _ a 7 . - ' ’ I ‘u' ‘ -.' ‘ ‘ , ‘ ‘.‘ f“ ‘ I Q l -I\ V II e '- - ,I .u ' _ ‘ - U -, - e“ . I '4 3 HA {LE ( x- . ‘e ‘9' p M ' ' ' ‘ - n ‘ . , m A I. , I _., -: r u - , ~ .. . .v . . ‘ ..- 3 ,. i. i . I L . :‘ .« . 7 . .u- " s - w . -‘ a . - .'.\ .1-A ' ’- a. .2 4.147 .1 t. . s. , u 5 i - f ' f ' ., .‘f ., , '4 . ,. .' ... .3 .. "grr‘? . ' ., e. .. v. . i' .. 3., . “J .J . ‘ -dniv‘ J. o I _ . . a.‘ - I ~ . .‘ . a . .. . - .-l t. e 1} -L -...‘.'a.'. _ 4 i. .3 x; , _-_" V .3 - ; 4N . pk -/ -V '- . ". ‘ ( ‘ ~. , .. “ 'r‘ q Pr,“ ‘ .- .- Q . v ‘. r . .' - L. I.“ :-. . . .-~.~. .. I. ' ' - i _' ;! . , . 1.. .. M _ I O 2 . 3 ' ’ - . 4 e .u .". . 9 ‘ ‘ - , ,- “ ’ - 7 ”1 ’.. ' V ‘ ’ . -' " , ‘ 0 " ‘ ‘ ‘ ' -' 'r. .‘ - ; .,J"‘ .. w 1'. 5-. - Us!» ‘1 ." 9‘4. .4- ' , .5” e ....'. I* J ‘- r c" 9...? . a, n ‘ J'- ‘ 7 , a o . R ‘l H o r! . u A I, ' Q- ‘ n ‘ ’f U A ' e - o , ‘ ..‘. J‘- ~ A — ,g r‘ -(. I ‘__i. ‘l .395 IJ ‘ x' 'A ' "-l L: \' 1v ‘- »’ \ n. }. .5 . -. . -5J... n- .1.:-“ e | - .. . . , f a. _ \ ' ' t J " ' ._ . ‘ ‘ " F 1" W " ‘ ‘ ~ . r ' ‘ w ' t- J-do - . ‘ .a ' I31} 3-5410 uh r-$ '4 L ' i:'_.‘, "- ‘I ‘ I . ‘ ' 3‘ .1,v 11- ' ‘V L! “f . -. 9 . I 5 Q a" I ‘ ,. -A. . ' I '2 \- 4 - c- . ' - as v u 1 A» in '..." .‘4 . ,. ' A 4 In" J a. ‘J..I v" .‘ ,. ,. I . O ‘ e I V l & a: e 1 l .0 . .r q. ._.. , 7‘ fl I, ‘. \ .. ‘ 1. ‘ , 4. . ,. . . , , . , . 4' . . 1. ~ ‘ i '. . L21 4. ". an. Lacy. '1. - ,1..- ”" r ‘~.‘J r_ 3-K £55 A.) 3 3-. "l_-J{1.’.) , . ' \ ' ,- . I - I. v ) ' . ' " ' ' ' u s -~I “ f . ‘ . v“ r‘ e . * v0 .1; . e «p v y ,u u} .c‘ v ‘e .1 I .1. ‘ ‘3 '.I. 3. ‘ " .I. “'81,"; I- v _ i A . 2". . ' i .z.‘ 4' . 'LJ' .‘3'w ‘._ -, ~ ,J‘ J v e- 1 -'. H , - '.. q ‘9 " . ." 1". . 1 t . o ' « u i a e -l'.. nhm:’( a. 5' l :g le‘ “p; .10. e . - , . .. ..— ~ k.— .. i? ‘o. ‘A I ‘ ".‘ I , .- .1 A - - . J ‘ ,_ I ' ‘ 9! I ' ‘ - fi ._ I. e r f _ I ‘J | K - A I . ~ ’ .- - ,r - "- - . e . ‘ _ e . . , . I ‘u,' .1 n " .89 t‘» . , . '30-.- ‘ ‘m'l... q"..- I ' ~. a.” ‘l’.‘ . J: ‘1 t . L} ‘ :x.‘ f” n - ‘ ’ ‘ ' I ' ~ ' - ' r v ’-r' J ”' ‘ '. I! u ., v -- ‘ r o. " J ‘o . v - \' q. n S (-.- J . ‘ -' . . ‘ ~ ~ I _ r l, .‘ P‘ I¢ 5) , , - (4..“ . - _-. 1?... a. -A . . Jm‘f "7 J ,vb 1‘. ~ ‘ .. 1- u, 7‘ . ,v“ _-..- ’ ”_. 5..“ ‘I (h “I 0-“ f o~. 4 ,. . I , , . n , I' I A M ” "-‘ ‘~ .‘ r~-. “0‘ ‘ I4 M ‘._ I", ‘ .4 p e I b u L .- ' . J' t“ " ‘ ‘ ~l , I./ - D c . , ,. ,a . ~ 7 "a W t w -v t , .- Lr‘ ’ . , ~ ' ’5‘ ‘ .e ' .(‘ r. - . 'I' .. -. “ ‘ .15 .p . ‘ v.5 - ’- - ' Sic . "- “o ‘1 - N *4 :- ‘er'ae u »‘ I. ' . . ‘ ‘a :‘ 9‘1 {1‘ L ' 3 “3' A ’ ,,.) ‘f ‘ . - u .' — ‘ — . _ 1 '11 ’* ; ~q- ’e “ - ‘1 ’ l i . o i . f“. - e . -~ , r - I‘J‘ * -.' W e ..“I ‘3 , 4* -' ’ ' ,1“- W ".-"ITc -.1 6‘34“; he ,” L proceduro thntwoliainntos thc*nso of 10nd carbonate in the presence of sodiun acids or hydrazoic acid was dovslopod by von Bruun and Keller (10). The procedure involvcs +33 {ntsrnction of nitrilos and hydruzoio acid in tbs prescnco of concentrated sulfuric acid according to the following oqudtion. ' 0.1521133 323.94 3-3—§.1;33+32 fi\\_!§/ ihe intermcé‘ into'was scanned to be a substituted carbodiimi do to which the second nolo of hydrczoio acid added. followcd by cyclizction. 333 .2—Jo Hill-+232 H . 3.. 3-0331... ——-5 1515’,” :7 R»R=C-HB‘£3—9 ‘3:- “ mug-33.2 _.; Pkg—$332 3 Vfir’ A mors.10gical explanation of this sequsncs of reactions was offered by Herbst. Robsrts and Enrvill {11) which did not as. tho {rso inins radical (38h), first pootulatod by Schmidt (12) and usod by von Brann and Keller. Borbct. gghgl. (11} ouggostcd the addition of hydrtsoio acid directly to tho cyanide 11nk8ge, followed by on acid catalytcd rearrange- nont accompanied by ths elimination of nitrOgon, similar to tho Curtius rearrangemont for acid azides. The same intcnmediato is assunod to rssnlt. After tho addition of another molecule of hydrasoic acid to the rearrangement product, the resulting guanyl aside cyclizos to the l-clkyl-S-aminotetrazole. ~u 2 r. . +3 'Q— h.‘ “w n.“ ”r n—cmHN3 -—+ 3-32.33 £3339 mks-33mg, 3 who-329833 -—-t R-HeS-NHB --’ B—g-g-Hfiz 3 sh! Garbrocht and herbnt (13) have extended the work of Hantxoch end Vagt (5) end found that the action of hydresoic acid on nonosubstituted cynnanidos led to the production of only i-eubstituted-S-ocinotetrccoles. in this method tho alkylcyonanids is allowed to react with hydrosoic acid in ether or aqueous alcohol solution. Recently several methods for the olkyletion of nonoeubstituted S-ominotctresoles have been deve10pod by Sorbet. Roberts and Horvill (11). Tho products ere:Lhmdisnbstituted-5~iminototracolinos (es mentioned before on p. 3). These methods use elkyl sulfonates. olkyl enlfctos. erelkyl and alkyl halides cs alkylating.dgents.h tith some nodifiootiono of technique (1h) theee methods were employed for the syntheses of the iminotetrezolinee in this thesis.‘ 4+- [1‘ J. o l .C. . .1 I. . _ u f. t. a I, w ...J -o .+»‘ .¢ . I 1'4 ', r. o.. . ‘- ...,‘ o + .. . A . .3 I! .1... HO .e o1 . f C ‘n a we» ... A I. . :1; .. . . . _ .t . (J .A-‘ I. n. 44 . , .t ... .v.. r s c The Bchnidt reaction (15) in which prinary aninos are moved from ‘ tho'oarbenylio acid containing one more carbon by theaotion of hydroeoio acid no need in the promotion or imagine”, 333-. mazwogaz . a-cyclohexylethyleaino (18)." One mun-mat of the Schmidt reaction is ‘ that medal-genie we need be mm. to «cram acid. gyoiomgn. proprionio acid. which was used here. satisfied this requirement. then cospared with other nethods for the preparation of prinary amines fron carbcwlic acids m as the Hofnann and Gnrtins reactions ooterai advantages of the Schmidt reaction are apparent: (l) tho'yields tron longer chain acids are usually better, and (2) only a single step is involved. Initiation and control of the reaction. ohich is exothernio, often are difficult since but results are obtained 1': the tummy. ’ *1.‘ kept between 30-6000. thud problems were solved in the precont. case by raising'the temperature of the reaction nixture to 30-35%. before beginning; addition of the bdrazoic acid solution. 'Lmbsoquontly, ' the‘tenperatnre'roee to 55-60%. where it could be maintained easily by adjusting the rate of addition “or hydrazoic me and the degree of - inner-aim: in the cooling bath. - ‘ "' ‘1' in the preparation of‘the benzene solution of hydrazoic acid by addition of concentrated snifnric acid to a water slurry of sedit- ' acids (19) covered with benzene. it nae found that by using half again as not! deter as suggested by Oarbrocht and Herbst (16) abolisono collision '- of ‘lwdrasoi‘o acid of comparable concentration sas'=obtainod.' Rho addi- . “can! enter permitted better ctirringiand the tsnporatn'ro'ioonld be noro - easily controlled. .1. 3}; n. ‘5 , u u- h A v . . , .. . _ .- I .~ I 10.. e’ , “, $1 _'...- n' to ‘ :,, "9 o .'. ... \J 1")1' T '_ n ’7‘ .. , , .. r r .‘ '3 ‘I 'u- . - s 1 l v. ... , 1 r. a - . . .' ‘. , . .‘ .> ’5 .. J. ... It A -~~ '. I ". I l .9 - ‘* ‘ ' 3 ’1’ ..‘ ‘ I ‘A~' .’ v o ‘7 . l 'u -l f . O'n' ¢ ._ . . . ‘ l-‘J - .. "' 1 -r ' w . f ..A ', . 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"v " ' ‘ ' ' h" ' ’- ’ {1‘ of .’ -‘ it v A "' O U 3-“ J» b A;-..‘..‘ 1: e -' l~'-' '~ ‘ -. -$ 4 ' -* 1. a) i...‘- -‘n ‘1 1 'h t' l a 24 . + $1.3. ‘ 4‘} “G f: V'er' it" r I) “I ‘ f 4 Hr I? - J. {' ‘ 1‘ h ‘0' ' ' ’ 1. ' M‘- .' fir ..., L h." ' " ' " 'fl 1 V‘ " ‘ " l.’ p, " .J'.» g. l. .. fl .- .I..-I-'- 2.. ... h " z ..‘s ‘ . ... ' '- T; k. ' «3-. ‘ - .1: .‘lf‘ “ :3; 52 L' .J " . ... " Br: J. I 1 £341“) ~o J 9 I o c .0. ~ ‘ ' . ¢ .- . ‘ , . . .h 'I , f" f s. u‘ . ’q a. g. dr‘, .\ - . ' j s on x ”p . _'~' .~ 3“ j ’ 4 ‘ .~. ‘ ' I 9- ‘ . x - .. .. , .115“; g. .. e; 3 . .. a ». .1 r -. ' .1 .-1-. , a .3 ‘.-.- 2‘”. I ~\ Ll ‘ | v as ~ ' ' " 7 ‘ ’ f ’4'.. :‘ ‘6 (H . ¢-,",LI?‘_ !. al:‘_“ -s- . « ‘. .... .' 3 .7 < ‘1 . A ." ;. 'c‘. ... ’ 2c) 0 .s .0.) a- ‘8 \ via-J V :e L 5 ~‘. l..- - - ‘1’“.‘5 .» - ‘ . 4 14' ‘ - - 3" ‘- qr it"‘I- a 5’ . d} A 3 - “ ‘rl‘71‘ll ‘1: 1" . . . . ., 'i . . .- 3‘ a s ; I. y t6 up,- - .- .3 ' g“ \ ‘ 1‘. 3 v - a r .+ 3 l‘ ‘ V -' .... J ‘3 ; . a J. .a' 3‘ F- .3'.‘ L. ... .. -:;'3. '~ 5' 1...- . 'e.‘ .- Q did-z:- 3 ~.-\'I "H '"t‘v a 3 ' e» r g , e g y .s ‘ I , '1 ‘ ’ _: L. ‘ . _ _ ,. . .... } 1"» ".3 . - or ’ - .x C n. ' i‘ . I *. ', ‘ . ‘ ' 1 °' : v-. r. ‘3 Q ~‘-"{' 'A i ..., '. ..., ‘ ‘-‘ an» A. -‘A‘ 2" . l‘ 2? x! t ' ’ ’4’ , b; b e: - LI IL? . Ea .' "fl, 4' :32:- - J a! . ‘_‘. t l 05.. 9 -o 7. q», I ‘ ‘. o u... -.~ -. -. u . x .' -: ‘ .5 homo: (11) u bin omoy of tho chain": of toinzoloo ho: io- cludod nun]. "that for tho props-anon of 1-oubqtitutod Mino- tetmzolel. sono of thou hav‘o boon donoribod‘iin ththiotoricol port. It mu decidod that iho hothod of Garbrocht and Horbot (13) in which o. uonombutitutod wide is ironed with hydrazoic acid would be and. Tho cpmido is prepared byilinteraction of cyahogon bromido and o pfimry «in. ‘ *" f Mei-031' d‘RHH-mg RN-CQKK Tho midi in tho- uncured to met with‘hydrozoio acid to {on o mbotitutod‘ sunny}. uido which then cyclic" to tho 5-minototrozolo. KW} -—; 33-23332 ——9 a: ~J-na2 With rooont 13pm“ of hohniquo from thin lobarotory than in no need for «panting tho cyahanido. and the hydmzoio acid is generated in tho ‘ii'oaction ”tool. fhooo Win in mouthed of preparation of tho totmolo and. tho pupal-anon bf tho aniho by tho Schmidt reaction Mo ”hood unfit-roll “no" roquirod for tho preparation of tho totanlo’ own with tho “190171.10 aid ohon non-rod with tho nothod of a. Drum om! 1.11:: (10), vhoro par-pantie: of tho nibrilo lay bo nomyi I'Io methodo- givo roasonablo yields of a product which 1: quito «oily pnrifiod.ri"‘ Biuo 1-(‘a-imlohm1othy1)-5-oi1noiotrazolo m not bun pup-at. boflro 1! rod the proporod by another method. Alkylofloh of 1M- Sqninototrozalo“) with 2-cyclohaxyletnyl bromido «3) mo 1-bonzy1- (an. 1-bonzyl-5—am1notetrmola m3: prop-area in this laboratory by tho uthod at Garbrocht and Hex-bat (13). . -5. p. I I . F-J f“ ’9. y . u o “OJ-1‘?!) ”"3 .f‘! 1- .. . - “~ 3 4391:: 1.2;! 'i‘ 0 ’04 I n ‘ I Q" - , b I. ~ thaw—-w‘osuno In 4 up...“ w 0,. 1' I11 vf‘u Ib(2-oyglqhgx;rlatru‘)aR—L'Ii’li’ tar 201 no hydrobrmida. The hydro- bromido'was converted to tho hyarochlorido can-ca?“ .w ‘13:- 5 - one 205811(oyclo) by liborauna “4&9“ Auith potasshn WW9 and. iguana; thofroo “base- wnh oonoontmted hyazfochloric ouid. -Frho ”dang-.1011“ wag than debonaylatoa by hyflmgonolyais using tho genoml toohngquos of , c a on 3101 +32 b9 23% -c Ci2053n( i" \ J. In the fir“ method tho tetrazolo ring on fox-nod fro- 241010- hoxylethylmnorn“ such o my that Vtho wm§_bopano no blur-ego: of tho ooh-non rug: 3: “museum! «that! tho thlgoqlothyl ; ...} group m odd“; oo 0-. fix oubotimt on a. pmomgjofigouy 0W. Thrown” of. tho om. coupon: hr hath 13W mom m ., ”amt. of tho .5th of tho product to WleoWkimno- "totmzolo. ‘ .- a _ . ‘ o 5 .. r. . . . .. ’5 "’I- f ‘ ‘ --4-T:-.. Inn-am mm. -..uau~-,-; and 1:. and mm Minn. 9.093%- KM.“ poo no moo-ton «towed to. shot that mo prodwopfi tho Ago ”Mo mo ,tdou'dool. who“: of tho l-(ikoyclohoxylofihpl )oS-oouoootruolo .- ' a - r ( f u‘ . .1, 1 V ‘ . g I . 1 a . _‘ ', '1 , ‘ . - p ‘3 o ‘ I : A . ‘ ’ ‘ u” v . .‘ .- .. . ,V ., “l V ‘_" -A. I . J x “‘_'n~.. ‘ . \. . ... , ‘ o . f I " y a . l E “ p -' \" a ’ ' 3‘ 3. ‘l I ' (>1 .,- '9 ”-.. . | 4‘” .' _; \l 1 w ‘gufl‘l‘ f 1-. l . ... T. r.‘ . "r y '- t ‘ 1 4o; " l u- ‘* , « ,- ‘ I 1 - .4. .. . 1’ I x .. // \N *5 . ‘ . ‘ .3 I‘ 2' ‘ ‘ ‘ -C—D ‘ ‘. .- "‘ A t ' , \ , A, 5, t \‘ ‘ . ‘-’T‘ . . -. . r‘A‘ ' ‘ , I ~ ‘ l— ,, ' ' 3 I “"‘ ‘ \ ’1' A r . 3 s A ' E 'a “a. ' _ 9 . . . .. fr _ , \ - . _ , 5 _- -\ ‘-' - _ w- _ -.-:, , ~ .3 4‘ ..- I. I - 7 . If ,- f, g. .. 32‘1_ 8,? ‘ .. r“ , . .'. l.- .« ' \ ‘3’ .u... ’ " ,-.L .-. a. ' a _.,.-....J - ‘ ‘ . .. ' ...! . a, .P 1‘ .1- .3-.- . "4 g If . ' ‘ I ’h- , I v v f ' o‘x \ ."1 .1 I" 4‘- . , u _' ‘..‘| t“ 3 u . ‘3 ~. .1 Q o ‘ - § .. -. , . .\ -x. - k .; : “ .. . I ‘ er“ '5... ' L‘ )7 "1r‘i 4 ’1"...ffi.“."‘ £..'(" '- ‘> ’ ' 3“ 'y' ‘ f" "' "' " "" 5' ‘ ' 'f ‘ . I". v ..-- (w - ~.' « w .J .. | . »‘ _ . ‘ ‘ 7- 'p, .. .-' fit ‘ . t !" '- I ,I‘ " - . .- .\" - 91'5"”. ,. g . J. 1" 1» . J 2‘. ‘ -‘ n ‘ ' ‘r r:.~ r‘ n .- . . e“ v + .. iu“-|' . -‘ ___. 1. ‘J . .1 _ .-" \- f (. r 1‘ ‘. ,.. h. .1 . . _ .. . 7‘ "i '.‘ \ -“ ‘ ‘. _.'." f I ’1 ..l' ‘ ‘>-’ " ‘ .1 x i.‘ . * \ / 1 I u. -. om na' _. ..4 9" v‘ - .- J .- + ... ~;‘ .. o, - ' . .. r... ‘_ ’ t‘ .0 " I..?} (7: o. . a I “ . V k” - z: ‘ ‘ s_l t ._ . \; 4’ ‘. f o. f x l‘ .. ._» ...- : 1F.-'io .. a": “.9, ‘A. ’ l. I.-. .Q- ‘3 -\ If n V .l 1" ‘-“a, .. 1 -.p in ( a, «1' *=-.=.'."‘..."'; (J .‘1 3' - .33 w 1.5;, 3. ’94» 'fx 3 c *3 .! Y.“ .' e, 13' -. J: ..-.t. 5-4-! I -. , '-.‘ 'o . A "I t I“ * ‘ o ‘ - ‘- _ o ‘J a 0‘ q *0. €-: " r ff 1 - —-v ~ ~ I . "I '— . no ~O' - ".' ' " x.‘ f: '< " ’-_ {\o . rv~ 1 g f -- Q ~' ~ ..<‘ ”3-- u... .usf - 3 a '3“ : 1...! .: ,u. v.'....:.32. 2-. 3- *1! d £1 - f: -.., .4 ‘ -. 't” o “ , + H 'n‘. Ar» ‘.os-h ’ -,(§ — ‘ o. s. r 3 L \'. -. . ~ I -‘ .3 . t" ' _ l" t‘~ ', . 3“. f , s 3 l‘ ' ' ‘;C~ " - . o» . 4 .- .5 - . - E _ ‘I'. J . '\. o -.. “. .. A": ..'. a1.--.¢ L, . L.u .44. . '1, 5', f‘...‘,.. O’- ‘1' ’v -.f ;) .afizufiutifi LIP2"”32? ‘cv~” 23* a an +53>ir°arr3 7&13 n :3 Béiha 3'3 :ur . . ,, . __ . v - .. H. ~.~~ " c.f"'z_-«'I-_t_rgg .-.’.. '.."\.- '1‘” 3.3,; '1 " “ r. U «u v. o t. ... n :34 "I .. ' i i.) J “v .15 03 .7; 4- .d .? Puo ‘- "5 4|} gr. . -‘ r r 1' ‘. . “- . . ‘ - ,J . .. _ . . g A 1 _, 1 '.. —. v_ 9‘ oxr _.- -~‘—f*. \ - J*r,'r0 For 0 ..w ...... . ¢-\ _ 4.3; no. .' *(3 fl: .. "'" "'2'. . .5~ . Al, 3.." ’ 11‘ ...ffi {la-"w e u 4‘ "5'... I I “be, ‘ " 3/4 HP? ‘1‘ J ' “ .. ' ~-‘.‘.'- “.1 ’ .D o 4! ' r '3 “~- "' U . "‘1'." J .. .‘ .g .0 -, .‘. 5.113 .’. 0-, ..~6-~ 3. .-.: ‘* V’ ; ~, ’;' _ r... J”, ,. Ju. ._ f . - e. , ‘r TIL; .tfi‘f ‘0 q ‘Ll t‘“ «3’ a .1. ‘3.) .a' .14) J .'..‘. 12.61;.» ' ‘- 4; .1 3 J .I. , 3 " 6 o 3 ~‘. .' 4 4'“ ..., I" C"! ‘1‘ " V . 'r‘ “ ---‘- ro‘-, 4 A .O‘ — ' ' . . - v a- ‘ - . - ~. ' . . b - , >£ . « . ‘3 . x .7. ...V v . . u. y 7‘— , ‘. 4 “5113 ah ”‘9‘ .".'J Ala .9!D-,)- - 9.--: . .x. K" ...J Y 3 ‘ .1...- 9 -u? “H.581.“ \Lfi'id 0:1 ‘9- *‘1 “(3 f'?‘ I V I _ 45 r . '5. s - 5- g V . . l‘ H‘ I P - “.- ‘ ‘_ v o ' ’p ...-.. 2-0».- ,.9 ,~,. ..I- , .fr'v- . . . ~~,IN'. a. A. w ..J' -» t. .qu a. .fi .u‘ .fiQ-n 59...‘ \9‘lvv._-u"ufli’ ' \f‘-':l¢5'-A. ‘l."\ VI .. - , Iv: "I " 7,“ . «l. a; " .‘. .“ I 0 . I I .4. ‘_. &' f;:’-_". a: ‘3’. ‘w cyclo-Céuntnauaeg— vivid? + csusonecl——-o \‘ cyan-051111 {:32 3322:— if; - golf "’ Lg‘ué.’ 5 gavo I. own“ when hydrochloride was identical with that obtained-from tho allqlation of 1-benzyl-5-aninototrazolo, doom-11ml abovo‘, no moon bylaw nootra, figures III aha IV, and fixture molting pointi.’ 111101.! ohovod. no depression. Since the some compound is for-306 roam-filo" .9: tho ago» in ohioh the two substituonto oro introduood. tho m.- hoxyiothvl nod. buzyl groups must occupy oqniuloht position: on tho totrazolo ring. This roquiro-ont in not only whoa It had R1 ”on” 1-? ' and h— pooitiono on tho 5-winototrazolo ring as in “Memo 1'; " R- -- :35 U- I B 0:631 a 2-oyolohoxy1othy1 or honzyl. Structure 1 was furthor fldbotantiatefl by the dohenzylation of tho totmoolino formod from tho olkylotion of 1-bonxyl-5—uinototnooto filth" 2-oyolohoxylothyl bromide. to give l—(2-oyoloheqlothyl)-5-uainototruolo in 71% yioli. indicating that tho 2-mlohoxy1othyl group oooupiol'tho'“ l- (or 3k)! pooition on tho ring. Sinoo only tho h- pooition io mum totho 1- paiition. substitution in any other position in tho ring would load to dittonnt products. Rearrangement during tho do‘bohtylo’tion“'f; " rothor unholy oinoo nthor mild conditions woro nood.‘ "- ‘4‘ ’ t’ .. _ . Tho;-ldz-oydohonlotwl)karolkyl-B—iminotetrazolino hydrochloride: ooro proporod by tho nothod of Horbot. Roberto and Hamill (ll)' fifth“ ooro rmt “prov-lotto in toohniqoo from thin laboratory (11:). Tho nothod -8- f. _ . P“ 3‘ ’ .‘ \‘ - t + A-.. < ‘5 ‘ a ‘ fl‘ sf ’3 ‘ _-.. l" ' I. ‘ - '0’ fl . 0‘. ., ‘ n u - w _ .... ‘.a I i -J 3 ,. " ..‘1 . . \ ['1 I y . ~ . n o - - ' v v ....- .,. t. 4 - . , . . , —-- - ~ . . .". S a .v» 7...? ml. .. v.” ~ ' .. ha", ,2 3‘. fi-va . -. . . ., J. .. at. .v- "1' 3 -§ .' ‘ I" ".3 . 9. . s .i“ : J ?~' . ' u .I.‘1'." .- ' ‘ '- - . ". ‘2 . " "a. :3 “-.C- ’ ....s 9:. . . ». .. - '9' r 1 o - .‘1- . ’ ’ ‘..I t l -'. . 1' ‘ ‘ ‘ fl \. . ‘4 P ‘ 74" .I‘ . I ’2: ".‘9‘,al‘.'9 C‘tl‘ ‘ ’. ’ . ...}. - . v ' ¢ - .. . vA . . “4 - . . . ‘ ' . ' ‘ 1 _~ . - ~ 0 " ¢ " '” . J" , f - a. '. ~. . v- r . , N I '~ _ ~ . , v p. .' f . : r' . l' "V; ._- 5’ [o . .-~ - ’- 9’,’ 3 V .' f a! ififl’, ?: ‘ l.. ‘1' -.‘-).I kw . I -. ---o.. ‘- --- 0-" u. ; )3 s51 ." 'L 2. 11;; I“ F'""" g' A .-. . ‘ ... 7‘" 9‘. . ‘ . ., :7 ~ v.‘- —. ‘ :- . - 5" .01‘ ff" ' u'fl q s ” ... u ”I." .( .",» ..' “04"; I,” “‘3._, " , ‘ L; .. ' “.7 14.; 4—» s.3 .. .4 - .4 luv- -- .L. A. .“ .;" ;l.. a.) . ,..' J r1... 9 ~_. . 3 ‘ 'u- .- ‘ v .9 . “2 ‘ .17 y r .1,“ '. INN ‘ r, . p. ‘ ..‘I".'°\~ 1"‘3rtad F'H n "- or!"¢n‘ 'u'qouod ‘ '.‘l .t' ._ -\_ I ~ ,l‘r . \l;.<'-' ‘ . z . '. «I -’ .. “4L .~ ‘ -1. .L'?’ 9‘ . s. " 9- 3': g". 5 _“, .. ‘ i. h V‘ 5 - O A.- . v , ~ .t. - , § . ‘-p u ' .W - - r ‘ ‘ ' 0 ':H o ‘ 3-. (‘0 1 - Q! I"‘l -\ -. .. ‘0 -J “ v_'.-‘:.r;.__‘ ‘_ z 3 : }_ . \ogrz,“ -‘ 'L.‘ :31 4. V‘ . "1‘. . - a; t; ... .w. 5,; T ..I r':‘_]‘~ 32%., '9I . o I w r .«. . J r '0 n.1,, -a r‘ .5 o .- . ' P' :a ' D ‘ 1‘ ‘ .-o f f' + "F ‘- 3' 3"! . ‘ $.- - ‘9 l. I ‘. r 0.1- 1' {HIV .. .. . -. r‘ I; l ". . ‘ a L “A. .. .. u‘ * v’t . "fix. «3-3 3‘ (”t g”, .9. 2 ~ .1“ '4. ' .' (I .2. “—.._ no - new? .' | ‘ ... Q. Is \ /" is ’o A ‘ * ~ . 3, ,.: ".. . — *, . "" ’ q ‘ . *1": 113.. “.'."' I at! I. ‘ _’:" F19. 3‘ ' a * . 21-. - o; 9 . v ' - ' . . . ’ . "t . . .‘ 5‘ . . . .',. ... * z' ’x ‘q 9-4 - s. ..I .3 p- - ' M f - «HQ-w 6' 'd a. I 41' 11“. J " (.... - l? ' .‘A .. Ar 4 “a. to 3”. . 1." .3“. '., '- ail.’ :L- , .3 : _ ‘ u a: '-"l .I‘.’ .‘ V,“ .- J . . - .- ~ , r ‘7‘ ‘. .- ,. J . : .,.‘, ,. r- ‘.o..fi— ,' § o r ." . '...,,’ .. Q. - ,‘d l. (5 . fi . mo..‘tt.~.:~.t’t’— [.:.,,-'f £~.):‘;.:t;.; 14.. ,..- _. " g'“; 1,- .. .--... it. Ll -‘J.-_rn.. 2.791 5! :23; r (A .i ‘2‘ '13; no .‘_ , 1v ' U \ '« - “5 '2 'I. . . .- .- . . - . '. a. . - - o. r. v l. 2" ‘h -., .q a. - n .. c, p . "ogo ...._. oglf." f,- '--‘ (“f -‘ . .f“.“ a, , i'T'-1~‘OL‘.;.’i-: ~Qq‘ . ...... ‘5’? .L :1 r;i - _, :._flaJ ... f of} 3“. . ’3 ’z..3-.\°‘.r}-‘-_ -...l . _ . .. .- . \ , . m . J, . L. , .‘ _ . r. 'o ‘ . P_ . ' - .» I‘IDII "r- o' ' . ‘ - ' "" .f‘ 5" 'fi : t4 .. . o :“ »‘_’ I " Fan ~' 3;;1'4‘7'3 H ‘ . .. ' .1- .~.‘. “"9 ‘ .‘ufi‘ n. 43,-)" "ll--' ins! and ".55 ‘--'.-‘&. " L9! "-v 4- «.1. 1;}. f. ‘ ‘ " " ,1 O. Y ‘ ‘ f?" " '4 ' ~'C' o‘4‘r ~~ I " a .‘ - .-., - -.v~~ -.. ~c~ . _-«"' :‘ - r, 4' m ' . 3‘... CD?” “...{3'3 hi 3L‘.»;‘.L'."Jq '4’ 93..., 't |. -. Jo. .&~- o_ 31‘). ~ U ‘ ”wt-6‘“ ~ \"' 3--.I ‘41. . t ' ‘ . ' . .- '. f‘. . - ' ' .5 . ' - 9.. 1 -, -' .- .--'. (I r“ “ i 'J 0 '00 'v. tr yo 3" a" .‘W ’ ,.-& ‘ :' .4": n. .1: ‘(f 9.1) I...‘ 0,-I4-5'L2‘ . I , ‘._3 ‘CI' 3' I.).. f! 4 'LL v... .&"'-.:; .‘.“.‘.J_9f ._I 0.; -k'-~t ("J l_ .’ -. 1 .- ,. ._ - " P f ' .-’-. ,. . _- 3.. ~ 5‘ -. 1' -‘ . ' 4* in- . .' 11 '- 1' n ‘ ,9. .- a f 5.} {:3 L a .r 3-3?th It a. f ‘ ; J ‘1. . . :3 *.-,‘. ’.. "- .'! ... . 0?,i's1IL.Jf}-«‘-’ db ..J ; J, x ‘ Co 41.9.3. _, _ . . - i." o. 1' I, r ' i ._ . . 1- : -' :‘ur . ‘ g f; o - .r 0' go . ~' _ -.. .up‘v .x-g , LW” -" :g f--- ...; l; - ._ “9) &.L.w‘fl 3...? ..7 fiJizla -,....‘f'..'.i. .u l ' . ,3 :41 t f - r y ‘ _‘ . -‘ ' f ‘ - . p ”.t‘ _ I o. . .. - ‘4 o'- . ._ A ' ._ 4 I - 0‘. ~ . Q. -r ' -o-'r ~ , " ’ ~M~'-1 f “.- - -", ' n... " F -J‘-- " - ~ ’t‘OQ- .- -' ’ .. 91 "‘ V oun‘s l-I . . r.”- .E Q Qf n n‘o’.‘ so g-" \f" s'dlb-o. - A J -: 5‘. ‘ll""' ‘ K O ' ‘J.-- I. +' A I ‘Iq : 'IJ.’ .....- . . O . .fv'“ run. t. . r: . =-n‘~?. .: a . .. . ‘74 [1-7: r»; 2'? k .1.) .* .. L‘.’ ‘14“ ‘ -44". Ej7fid‘7w. “3.3. '16-” I“ “MIN-3 "n"? "1' 1 YJ :.~‘.‘-'1 ‘ ."'-'-‘ 3'34?!” , ,. I .. ,.’ o p ' I , o. . A . " . n. ‘.~ 9 "" -Wf\ " . ,‘ ~t r 5*} ' ~r~-. , ".\ " 7 9. . .sJ-‘na' . . o,“ 6!“.3'9‘?‘ I; ‘y . “’j‘ l' V",r'¥‘“ _‘ ,‘.\_“J ..'.l "u‘l‘ 'Jl‘» L - 5’!‘ , ‘- 1'« o i! ’5? Li a. RULI!“", Y 'J ;': It, d al-"'\'S"l1 3., involved the heating of the arelhyl halide with the l-nlhyl-S-enino- tetreeole et temperaturee o! 120-150°c. for e period or tine. ”Genelly e hOmogeneoue melt (breed. followed by'e mildly exothermic reeetion.‘ The eslt of the 1-3.dienbrtitutedofi-ieinotetrecoline oryetellired free the hot mixture and we: purified by eteee distilling the exoeee teary!” halide from the mixture. The free base wee formed and then extracted either iith other er‘beneene. The hydroehleride use formed by evapo- rating the dried ether solution, dieeolving the residual oil in eqdeoue alcohol and adding concentrated hydrochloric acid. or by treating the dried benzene eolntion with anhydroue hydrochloride. It woe found in the preparation of thie eeriee of tetreeoline hydro- chloridee that the use of a larger excess (50%) of’benzyl halide mode it eoaier to handle and dieaolve the crude tetrezoline enlte. No dielkylotion was orporont even with the large excess of halide. In the purification oomolete solution of the crude tetreeoline eelt in alcohol before etenm distillation was necessary to insure the complete removal of the elkyleting egont. All of the 16(2-oyclohexylethyl)-u~erelkyl-5-iminotetrezoline hydro- ohloridee prepared are listed in Tables I and II. The lower yield of the p-nitrobenzyl enbetituted tetreeoline hydro- chloride wee due to the dark colored impurities in the crude product which oeueed greater loeeee during purification. Longer reaction times were need for the elkyletione with 3-phenyl- propyl end 2-phenylethyl helidee beoeuee of the lover reactivity of theee reagente compared with that of the benzyl helidee. ‘ During the properetion o! the tetretoline hydrochloridee it wee found that the free tetreroline base of the 2,3—diohlorobensyl .. ‘ O ' ' ’- u a -.t. H. l...- ..h “A“ ’9“ ...}. . . y “ ,’_ "X t , 4 r " ' . N ,_ r ’ ,‘_ v- . v! ' .‘ ..' ... s“: .— . "'.t .‘, ‘ . . . . v . v - ,, . .. ¢ - r, w _ - ‘ v [V J _ .fl_ -. t‘ J 1. p . . ; ~ ' e \ ...’ . 4' a r e 0 r ‘ . J P . .1 -, . .. - u \' '- ' t . - A - A '1 . 1. ~ ' 3‘ _. ‘ _ . . . .. ve- s . _ _ _ v. . '._.- . j - £1" . -. .3, r. . p ‘ ' ‘ ‘ ' ' . f I , , . . _ - : , .. , ~ - - ..- ..f e 0 es .-P ‘ ‘ - l r \ - . p ; In ’ {N "t n. * 0.5. e . ‘ . 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' «. 4 l- -- 1,. ‘ , -. .| 4 ‘ A i g t - ‘ ‘--‘ ‘ F ' e ‘ . ‘ ‘ a u- _ e v - i. r ecu! -"\ . .; ‘ 7‘ r. ‘ .. Or - '09 4- - - Q o . V . e . .; « ... ’ -' - 5 ‘ t.- . ' , 7 . . . "‘: ‘3 ‘- Li '.I ‘ ... ’ ‘ F ’3 t ’ ‘ '7 7 " - ' ‘ ' " . ., . . ' . x "' f r ' on J .. L' :- . u‘ .. : .1 f . ‘; _; : 3 .. , , ‘r‘_ .‘ , . r a ,1 AF 1 .\.-‘_o~4 D’P M \e 7 ' ‘v k . ‘. O "F r t' P F " I" r" "‘ i" 4 ' 'i’ ’1 “ ‘ "t .3 "3 '1 " " ’ 'I' '“> a. " - I w I‘. ’ rift T’ v...“ '5‘ 'H :x'v .-- v'w |~ q. ‘0. ‘. -.-_.,‘ ‘_ ,‘_ k u ‘. -.. ..'. ¢ r- - - ... , . \ . ...'--.,' 1.. .. Aej‘: ftbl‘ .~‘ . A a A}..- . . . f. . n ,’ u-ro --.,~ on ’1 v». 5 ' 1-. 3 e I! ”F ' ’ ‘ c, ‘ ro; , .ur N ’ - - ‘9 -n , , . I‘ i\‘3e‘.l '0 «'0‘ ‘If- ”i ’ .' . ' n- .. — .x. o' L. V - ’- e a — ' .i. ‘n.' '2 fi .. ..e "( Ar'l.‘ 0. . " n; at” ‘ ‘ 4...... « rev ff .‘9‘ we ?~.. u..., u ‘ *' 1.;‘u ~”.9 94. . 1"”‘V . d . ' f ‘ t'. .. 1'“ t v' ‘ t' -, r - ' f v 0 ~\ . .' . n ‘ - 9' -~ ’ - (t f'- d. 4 9 " t , a ‘ ... -‘ ’_ f .~ . '. -.§,. ,_ ‘ r I ... r .\t 1. "3". ' L; ,3 . ‘ Y . ' .I~¢ .‘v v . peei- .A ' q. . xv A '“' , . ' e t ' 5 .~. ‘ -. “” -.. F'!¢,\' ? .. ‘ a -. , , «T - - ' «HI I -e.‘ .t u" 'm‘.‘ )‘r a r- -- -h _, ~‘-¢.-f* O \ .- .. ’ . . ' J. 4(- - ~ "" 4‘ -' #‘T ‘ ' ‘ ‘1 _ K. __'. ' .' _>;_:‘ I ‘ ,. . ‘ ’- t. 1' I ,‘ e- r ‘ vi» 1"! ' . _ v _' Apfi‘ - us 1 - . -- \ efy r- Ae' ‘ 'e _ . I . I u .' ll -:-, (m * *‘ aim: .J -. .3 «um .. .. “n. rs».- . .. -n m... .- , “3).. 9.1. J, , r w "y... - . A ) ,. S. e. ~.,. 7. u T .. f q, .. fl , ‘ .. 4 4. ,3 . .37.. , ..., r. t ' ; , . . _. . . ~ . _ .. . . - . . z .. I 5 :,.£-' ‘. ... I .}J . .e, :A- u 54 t 't -L . r ' ‘J ‘1’“ 1‘1.l‘ «I ! - A‘l-h MI .- -I -u R S ; 7"}.Aufi ' - ‘P x v I r - . ~ . .. 4 v - a -. -- - , . - -9, - .u , . -. .. . e . ,«J J . Ru... 4. '4'.’ d- t -'-‘-" "we 6*:- "*I-.- "C- 3534.0"? H .. f.. “‘ .‘ .t ' ., . '. .3» .-.' 1“ . ~,' 7‘ 37 , -. . ~. '~‘ 9- . . .‘ ~ ‘- 1".”"L1I‘fi‘ ' " r'i1( I '. ":3. '. ’ ‘3; I? 1' I. if} .f'.‘ 9 _. T.‘ - ’. “J 3 P12); 1’ 7‘- -' C’Q' '1’} thCk" ..41. ..g;.s.;_ . N ,. “ _. .5 ': ...,.... * h.: 71" (...; _,._‘.. ‘ , .',..H,., “‘3 J it! an ... ' J ., C) I "95- "‘:.2.:- {9‘1 p-t.‘ 9: 796‘": "J’H'Cz - -."- J ‘. H, “ ‘tl Jag-"glli'J-z‘g .a“.'~" .5 9‘7. 7'.‘ ..-I ~ :. . t ' I ' w. o ‘ ‘ ' I‘ ‘ - ‘e ’o . y n - v 5'" . : _.‘.“'- 1‘? r“4 § ‘ " I: ll; ‘. 6‘39 1 v ~f-‘fi : $_ ‘1‘. :';.I-/.‘fi' r. .: t." . 1.59"”:- v. - . ‘; 1‘} t‘ ,, " ,f . ".. .. .:,._- ..‘4- 9‘ ,.... '. . - .‘, .3 ”MW" ' QEU.‘.T("‘,.‘.J\~-{ .‘.. :m f1'-"~-:~3 an. n‘ C- .21.;- r‘\."-‘ '-°-‘.‘.('.‘.' 9a.? r... .-f w .: '- '. .x w r. -311;.'1..{;'J-..sz..'."""".“:. 3..) 10 5'9?! 91' -.-‘.-*3“~’~'! i533 9911 .1; ‘finv’ :.~7;uiu1 Iubgtituted tetrrzcline was a 30313. Attempts to prepare the free 35363 of the other tetraxalinaa ware gain by treating the pure hyfirochlarido with potnastun hydroxiau anfl sxtracting with e$her. After drying tha ether solution. the ether was evapcratg. and the rasidual oil crystailized. The free base. were recrystallisefi from either aficluhuxnue or petruxcum other. Solid bases were obtainea for all but the 1-(3-pbanylprcpy1)-¥- (Q-oyclohexylethyl)-5—1minotetrmzaline. Faru;;&o. m?1ting painta and analyses are fauna In Table IV. ..m. N 3: ..~ ..‘ . .|‘ rv . .2. ..N'. .4- Ben: 'e ‘Solu 1 ' o y. The lethal of Germ-ea!“ and Herb" (15) ”eased mu end“. p41. flaufione of “amine to pemt «no mm. The behe‘elie eoluuoee of We“ e016. «re muted ee remove: 300 :1.“ of inter are added to 208 c. of eodhn ez1de 13 e 3 1. {leek fitted «en en eleohol theme-eta. efficient nine! and e 200 .1. droppug-Nnnel with «not mm the new: ieve1.' .11» am (herald be vested. 813 hired" sunken-e of he.“ ere. added. an. keepm the temperehre bele' 30°C. I111: en “which. 109 ll. ,0! em , mm n11.1- ere mud mpnee ever e ”2101 of one and, e theltboue. Machete: m e-deep red until the he. $10.11. deem new. flhrmg 1e cat“ for ho ham-e end the num.1._.uma ”...!“ fee eee hour mereuehdhe benzene layer “Innate“. “tog eye: . ‘ M1!- ultetea--11‘.-- ' .‘ :' -"- The «ambition of the hydreeote eeid wee de‘emnl by “Venue er ee enquoe unetenderd enema man an; mumm- manor. he ebeve procedure ghee eoluuone eente1n1n¢ mun «untreueufl of 15-113. of hydraeolo acid per 100 :1. e! eolufleu. g -"§Z§- 1Q 33:1 lgtm1am1ne I The tebhn1que deVQIOped by Wilson (22) for the prepareuoe e! e 'pr-1exary amine by the Sohm1dt reacflon from the corresponding acid wee uployed .1111 enght nod1f1cet1on as follows: 203 g. (1. 3 no1ee) of 3-cyo10he1y1propr1on1o 3614 ere dteeolved 1n 2. 2 1. of benzene 1n 9. 5 1. flaek tuna tub en 3160501 tum-m. effluent etiner. 500 m1. drappug-funnel and e reflux condeneer. ‘ 813 halted end twenty 11111111ere of omefiuted with-r19 ec1d were m deb tuning. Four hundred and “any u111111tere of e beatene me- n: hydraeoic eu1d (111.6 g. of max-Mom eo1d per mo n1.. 1.625 -11- . i . ‘ ‘ ,l ‘ f ' (I. 1 a " '9 l..' n') .5 z} ~L #_ . ‘3 J ~. . . 5 J ’ . _ | O .7 . . '_ J . . v3" .- ?.lw't f. 1 '.’.‘ _, ...: - \ ... . - . . 1.. .‘ . a I ' . I I, .‘ ‘9. ' . - - - .. .e ’2’ 1 I ‘1‘ _ 1 ~- 8: v. e" l- 4‘- ..r' I > I VI ' ' '3.‘ ‘ "I ' . ,g,‘.. ... .—. -r . ‘ ~ .‘ ‘ . .- o. " '5“ - .- .. ,, . L _.‘ Q. L .. '-_ {sf - .. 1-. - .' V " ‘e ‘ '> . \fl' "’ . *.- 1. "J . . .‘. ~e,*| . 7r:L.~-c‘:; ‘. 1.1,.“ e. . .~ 5"- ~‘ an . . .. - . ._-. e 1,: e y ' -- g.r .. ., e . r . '1} . .O\-‘ h-‘- I‘.‘ .I‘ - ~' ~ - ‘ ‘ ‘I' “ (-L .‘e‘ ’3 " " t 2' f C ‘ ll.“ :1- ~ ‘ '7‘ ‘ I ‘ .c .',..:'-"-' ‘ A l. a - -; ‘ ' ‘. .1 -.. - .1. .. . r- ... $ 7‘ _ u .1“ w. :1 v ,'. 3, E I. f . ‘\ - “r: o . 34.4.2... .. . -1 .. -. .. ’..' o ..L. '. . :_ ' , I . ‘ 1" - . If» . ‘. '\. -~ ”1" 1- ,l‘ ‘ . 1 '. . . c. . 1.»..- a e . . ». ..-! a a: .. “A" . - r ‘ ‘y e ‘16 ffd ‘ 7'. I I s! r ‘L‘ 1‘7.) ...-{11. 1w Mu. . . ' _. ' .1 . . . .t . , 5‘?“ "I ?I "- ‘4': v.1“! ’4‘” . 5"; ‘..~ . h- 0.1:. > u e ... M ‘," .1 ... . ‘ ‘» .- . ‘ K I ‘ ' ‘ ,‘ 0". . ’E’F‘. . ‘ ,. f‘ .. 7 . .. .. v ... ‘. ,. .... 7,. f a ...I .. . 3.. .'. 1.1.4.}. .‘. - 1.1:» .. F. '. L.‘ 1'}. .‘o .- "3 ~ L 1- J- .. . , " 1 3 - ' .'-”‘- $3,”; - "Tush. 41-35; .L -.I.VJ...‘I. 'f» . En .' ,. 10:3 3' .1. «~- .‘r -. 1:" ‘3- ‘ — 1 «V... a - --I u - - ‘ .5- ,r. "1'1, ."1" :3 ..J} SKQ-J'u. " 531.." "n 5 '1. ' ’ ‘r; 2‘1. r-‘r ‘ : ~ I. ,w k ‘I ,3 v . n“ r. .\ e 5-1 > 5- “ it ~~ 1 I ‘ L, _ V." 2-3 ’ it. e ‘e‘ f ...: - ' I..‘- ‘ ' U .‘ 17‘ t”, - ..e' . f" . ...,fivr’. :- ‘r‘ -’ -', 7" r.‘-.‘..'..‘.. .\ 1:. 1. J in; .m" .\.y .114...“ ' 4 ‘. f- .5 «L- ‘. 's- ' - ' " i' :3 r -q., .»- 1 ‘ {1:3 .19 4.4: .‘5 -. -. 3-. I- ‘ . ewe \. '~ .- " -'~. - .1 r -* ’ . . ‘I r. I . . ' .v- -_ 1 ',' . ““3. 5 41'1“? .x‘ -.‘.’- e“--- ’ >2 ' ea )- e ’ M P O , , . , e f. A‘.-'. .‘ 4 I 1 ' . . f .' ,u I‘ , 'L . .. 4'5 3 .4. 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I. ‘- 12.91} .1 ”I: ‘1': i A? i 3 ' ‘. . ‘ 3' Q A1 n ‘ e r ". .s-I.1t I'. v ‘l‘ o- 0 ' 3".‘I ’.L "4.", J ‘3‘..’. '. . . I ..;J -- -. I‘ '1'! . a? 4.3.2:"? in--‘f>1.?.fi 1'73 (’9 .. .g A. r. ’ -.' -‘ . '-. 'V "" ’ ’ LAVIa a.“ “no?“ e.n.: v.1 ‘ . ’ ' ¥ K fl r y . ~ ' '4 ‘1I ' . . Q- . 2" H - p . ‘- L ...I ‘ q U E ‘. ,. ' A DJ ’.."‘E ... ‘7, O 1' a J ..K‘ j - a ~ -. A 1.. C949: ‘7‘. ~.:-~ -; ’, (.."|'!',‘-‘_f'. : few, .9“ '3’ *~ *' V '- < -....." '2 nth-4h. -'v---VO'I-¢. I‘m“ 4‘0..." -. V . - u " . "v .x‘ . '\ 3o . .- a .3 ‘~ -‘ e 'I - r.» i. h . :J.‘ ' ' .3 1-! 5,: *3. :1} .t '33"! .L ,‘. ‘ .f 0.: _- ‘n. ”~‘v_. F J ‘15! gar "*""J J x . .o ’ ‘ .‘L . .. ' . .~ .. I'L- - . .. ”.1. -. 1" '\ “v : 3' '1 v- .r F" i 7- . - J a”... " ;' J. K, n .' )- Q. ”.I A. 9 .7 ' J r 5 "a it? 0 .‘. 1’. $-11 f 7.; n1 ézvicealh 9;S 52:3 ifiiifa ,1aJauwmwngs 19v”h‘w 1’22": ~...-3,>‘;I.I...-;‘..s£i If?) aw”? .1...) L .2:J1v135 aéiu Htth 539 Lin-'7: 93.0‘:I“*"‘.‘.'«“1{ 'i'fv :..‘.‘5.‘:‘.-;31:""u .0100) :11 M Iddd (baptist with tuning at Mb I. at." u:- wanna- ,tatn a mum input-stun of 6006. the uddittu at hut-W16 Idld 303$“erun Mt on. hours. mu! bu'plm «mum It, tho hydra- 1019 «M during 1- Mann-pd for n In: an. flu mun nubi- { ” Inupummwuw’mfi . .- - " ' “to! “want; the boas-m lay" to sulfuric-acid 1min. 1. pared 111 u‘ ”rr‘tua strut-Into 3.ooo.h.ooo i. 0! tab-tuft 1.’ - '" . “mm. ..w; h1WII‘-prutpttato manually-of tho ‘ ama- and ' mfi'u "alts; Tint-IMO h‘mnl’onté t 1am an» it! fictibh'lppltod mu {hi-natal. 8! ti. 92mm.» bonu‘ultwry.‘ "Rikin'thui ., 1100.100 .1. strum“; no momma» at m'nnf-mo un’ér'3tho {nu-um mm to the 5-1. mm. umlvoa “an 1; oilntor "an tho-solution...“ um u .-lttm um 50$ mum Wins «hum. m an. 1mm «sand-mu noun 1 1. dammit“ {3" Qbuiuéa; 0-0 but“! unman- ottothn an added to th distill“! mid “0116* cum 1.": upmtd.~ ‘nu‘htor mm- is gamma-«tine 'tiio’u tit): 50 n1. pu-uouu «hay-awn»:- lawns m-muud‘ mas-1.66:3! ' ”to” mbmtoi- rho ”31150! is round by dintilhttu “in; u Vim column. to as.” W b. mun» and that thwothor 1i renewed by adding 20 :11. f benzene and distilling tho Izootroplo mixture thread: the 001m. The 001m in removed for tho magnum» sud tho mo ullootod, a? who-1:500. (moment) 65 was}? my fun" “ q 1331.4821.) based on ycyclohemlethylpmpnonuhem. ' .g . ' ’ 4- p-‘q-u-u-mu- 1M .- - in WW4. . Tho uthodu described by Garbrocht and Herbst (16) for tho Inthuiu of 141kfl-5—u1notetrazolu were used in a modified for- mlvod 1n thia llbontory. an: m a: a: 03:1 ¢ g~ma 3: 31:12:34 ..i' .~; }»°. .7 seif ?"* {xeiom In. .L. .. tn't‘. .-.-- ”'2" ': » -~- -'~ “.....- 7-- .Jzi‘fs 3.! "' '.- ._;L r- .. '1. 3.9.4 7‘..- [s o- ‘.... 7.) -" .. J m ‘. 1., -‘-':‘J~HJ‘-‘9-o F “a": ~““77.--;: ~.n.5.j-' 7. 51"55- {at 7 'znwi. .' ’ i»; SILK. ...~:;l.=.. '1 uuli..a..--c 7‘... N .7 1‘; ... .I.‘ ,._> .¢ 1;:- H, "fir up .1“) Ef'.:;' .’ '3; ”: ”-4.1'1136 {’7‘fif. 01¢? a. 4 t4} 7. _ A . .. 77v ,7. - a o . ‘ -a-J ‘- .77C3 3. dani fififinm a -L vi :4}: ";—:"._f.{ ', 13.31"; - 3' .z.‘ ‘15}. 4;: ’. W: xi 14:3; ;7_J.;.'A2;?u’z-:‘Li:m “23:33:19. .2 fi 2 a: “gi 13 .fi ”_f.¢-f -,? n.1f a‘ min rt: xtav a a: Zetrfiq 32'7’71 3:: a? '” ‘*“ 33 z." :'C.v21 s; éf"u.'n avcxim; 5v 3 .va;~wn 35:17“ ':::.Z.’ ' x 242.5,". “3': ,_-" 5:. ”Ha ftfi‘nfiu‘ni 8-1 51.332221 9:3: .:.'. 1'»)th 93:55? ;;; .f.“ ,z.;'t:,...,.:-EI a: a," "-.r‘: 5.”.C‘ifi'ZLJfi‘T-Z id: “2:: 3:32:32 mi} :33 1-..: :: ...". T .1 art?“ an} .7? :,t .7 .0351..- If; “to .55: 0-2:! $215 Egg g ~~¢ 3: .f I ;, F~vf.:n: ,52'73 .2 Q m’5 2 hanggvmt 915 917~3Zi3 .n*2$y§63 aill‘fiiud :fi.a~ffi§ .33 £52? 3&03;L 0: $3335 stem nai7LICN ‘53 .32129515 9: ‘:-r:;5g;o Eu .2 I Jh-Mz Iz*~: ”7.5lratfi m 9J3 ar ng+a «1? '55,? 9.35:; air. 53‘ .13 (‘3 f)u’:f.n ..':-" ’93?" ":21 email“ 52?; ?'“-9: ; as! 6:13 Jfiiw pix}: $.17} £9.fi3?;;a a1 1: :1 téinw 41 .h=§h7;f52 Zifiii 133:0 yawn 59575 8 a »~w-u:nfi 9w: 87$291 gedjy 9&7 «wits Ta cdcjiwoq .In 93 ., 513;“, 3.353;;er £51.15; W5 .aQVCM; :31 '13:};33 my; o‘cis;?.;;JC‘-j’iz‘:c nLc'iaz-zfliadq a} 75.:3 9i: 2: E; JQITfi Y: ;L% 635 “"" “nix“ 9&5 .nxyfco xynfgz7 evzfifi': 35‘71?‘177 aft gnlrfffaifi 3w: c*§:v:fi 33 .Im fifl LLECV’ 'f k ?Og€1 “'3" 27.." "‘LL 3": z": Luci} 9' 4. '1'“: 19'1". :I fat-I 5.3-. 351‘? .flffh'lm' mi! zirfixovdj fiIeiv ”Si? 55%;.5 5;“ (55383TT‘ZAN) .U“f.5"34?2 LC ,iviselfcs an a: #53 .533}! 3'7.“ .3": r7 ' . :395'33- . ”1-” rs.) 5.ch 7d ' ,3) .‘3 l '5 m (...... "”“"""jf‘“’.~?:‘;-—( f-‘.:._=4;.q f‘: ‘3':j“ -.....J ..‘. ‘\_I ..‘.........'....... ...‘L.......-‘-.'..‘...a... "‘u-t‘“ " -' w--—n 0.-....“ ¢J:~d+xta 963 an? {37) SvdfiflJ Lg“ fiiaa~affiva “6 3a,: Ifiuaeb aMGK: em «J? Ewad at "ch. 2'muawna‘ " 0" 3“... -.:‘ .0 -.. he tetreoole no prepared no follows: 127 g. (l uolo) of a-eyole- hexylethyle-ine ero dioeolved in 800 :1. of 95$ ethanol in e. 3 l. fleck fitted with on alcohol thernoueter. efficient etirrer. and a 500 ll. magma. m flock not he mm. u»:- coon... 5.1.- 10%.“) in no loo-Inter both 106 3. (1 mole) of oyeno‘ea bromide. dinolvod in 200 ll. of rotor and 200 :1. of 95$ ethanol, are added dropoiee. rerty you (1 .51.) of eodim hydroxide. diuolvod in 100 .1. of «tenure added and the eolutioa otirrfe'd for en hour end o half. seventyboicht are-e (1.2 nolee) of sodiu' ';‘M. dieeelved in aha ll. of ntor. ore odded tailored W :00 .1. (1.2 min) of 1:1 hydrochloric ooid eddel. drop- Iiee. { mai- etirrinc for 5a bl! hour otter the hydrochloric do“ ie eddod. the solution ie“ Mia'm‘a- ‘reflu on o"eteei'hotb.for oi: 5...... Ibo reootion nixture ie ollond to cool elowly to no. tenperotm and then 1. ohilled in u ice-“tor both. rho preoipitoteio rum-d", no dried our ooleiu chloride and pot'ueim hydroxide in 3 room deeeioetor. i'he dried product .1: refluxed with 500 :1. of 99fiioopropyl gloomyfthe ouepen’eion cooled. filtered and dried. The yield one 89.1 3.. it?! (hand on mine). PIP 218. 5°-213.5°C. (uncorrected) ' I ' Anelyoie. Colc'd. for can a C, 55. 36; H. 8.78; l.- 35.87. Fund: ‘ C. 55-35: 3. figs! 35-30 t 'D vtivo of 1- h 10 1- 110 gram of tho tetrorole are rofluxod vith 10 ll. of ooetid: nhydride for hhlf :n‘ hour. Ton milliliters of ioopropyl eloohol had 10 II. of uter (an; ”mung“... should. be up: below 1000. until 2-,.an 1e tom. Yigorono stirring ohould be contimne throughout the prooeu. (”til ie done in tho hood boomee of the exoeoe hydroroio Mid preoent. ~0- e c- . . >- ' . ‘1 1" f ‘ t‘ u ‘ > , ‘ ... L. o . , , . . T ‘ a 1 _ \ 1 . y . 1... . 1‘ ‘ ‘ ‘ I. >1 ~‘ “C . >‘u—u \ _‘ 2.3 .\ J g 5 ‘I v. 1... - . . 1 .5 , l g‘ 1' (7*, , ’r. ' r ~ -‘ ‘ F; . l — W O ' . ' ‘ ‘ ‘ I‘ ' ' I ' I V ‘ . _ . ... .- e - v c on. ‘- -. , -... ~ . .. . _ . . . . _. . _ . I . t . . p . . . 1 , I - I o - O ‘ . I . 1 .- 0 1 . ., .. ‘- -», . .. ., ..1 ‘ ‘ w IL . . ‘ .. 1 ~ . . \_ ‘ ,A ".. . . . ' r g _ J V I -‘ . ,. . , 4 _ , «, . 1. . 3" . ) . ~ - A L '14. - . - f ,a. — '. 9 -. ‘. -. .od ... 3;; .‘ _ ." -5 ‘ I' ‘ ‘ , - ... 1 t L ‘ I. ' ‘ . . « ~ I. ' ' L’ "‘ '- ’ ‘. ‘ 1‘ p -.. 2‘ 9 \ z. - I \ ~ ‘ '. I —-' - 1 .1 9- t 1' ~ . ' . Io I . k P I . - . a . 9 9! J. I . .' - ~ .- . u . ‘v 1 ’~ ,u , . v ‘ “-a .. .I ".'I I '3. 1. .. .‘ , . . - g i ; .1 . .. ‘ é . \- . . ,. .. ‘_ ’ . -- _ v‘a‘ -. i D u . ' v- “ ‘ .' . '. .‘. - ~ ‘I , " I '1 o .... ’ ~ ' < I ' ‘ ~ Y I- ‘ ' I u 0" ’ ‘ ' -* y p o o‘ P -' J ‘ “ ' \ , 1 - f ' t '_ Q" | | I I o I - v~ ‘. v -v Q | _ _ . | .. - . . . u ' ... . . §_ o‘- ‘ 7;! -1 J. ' J. '_ k b 1’ ,2 I .- ' ' J ' . I I ’ ‘ '9 - -- "- . .F: . J.- ' .4 '-‘ .‘ ‘ I .' l‘v A r‘ Etna ‘- . ... . .. F '- . a , ~ 1 - .‘ e .- . ,. _ .. ‘ . 5“. . o , . . . ' .. , ~ 5- ‘ , ’ 1 &. i ‘3...‘. 1. ‘c . a - A _ - - - _ o 1" r v - \ - (”W I I . . ‘ 1 3 - "V ; t" 1'" " "t ' ‘3 €27 ' ~ 'r‘. ‘. I .' 1,.” ‘14; " '1': , .. ‘ , ~-~~-n,\"‘. . Q . .. n - C u . n . " ~ ’. . 1 .- . ~ ‘3 .'. ‘ J . ,-- . ...r . - .. ' .- . . K- .. - o ‘v, ._ ,1 ._ ‘ _ . - _ ' . . . - f. 'v o r 4 . w J’ ‘ l . -. .. ‘ . . ‘_ , 'v VJ .‘ . .'( ' " t r - " ‘ . 0" ’..'I ‘ . r , I _ . r as .. l 0-, o « ... . ’ - 5*, § 3* “ v . ~ . o . A . .‘ . - '. .‘..’- J .A . o - . ~ V emu » u 1; 'Ar '7‘ f‘ _' f H‘_,' :31 t l f. . ‘. r u r ‘0' a ' o u ‘ v n - , ‘ '0' .". . d ' "’ . ‘ ‘ "0 l" ”‘ ""‘ ‘ . 1‘-\ .. "W’ u I l _ . V _ | ‘ » I q . . 9 . v’l 1‘ . ~ ‘. I i a I‘ ~ 1 ~ . r '0 ', . - I ‘ , t -L . ‘: ‘. el I (-3 .~ ‘ a “ t ' . t r A ) .n_ ‘t -1 1' r 1- '- . - - ‘ ' *3 .r 7r ' ‘ - ' ' 5 t ' , '- * f. ' ' 1 . '. a m " "‘7‘ 2;“ 1‘3". 1'. ‘. -".‘. 0‘1 ”I“ k «N'-‘ g' lb ‘ g. . ‘ ' I . . J— 1 n . ‘. e ‘ or a. ’ - -r ,. t . .l l a _-.. I _ ,‘.“._ ‘,“ .... o ‘ .. . .l 1. A r. ‘ O :- ‘O- n q. o I ' . , . ‘ .. ‘. . ,A. .1 .1 . . ,- ..., _ ‘_ ... 1 ‘1... ... 1 1‘ '1 ' -;l- J -' ‘\: A. ' - -- ‘ l -' 3 n " - -'--4‘ . . 1".-cl‘.o I I. l. . .I -' o f ..p.‘.‘, ‘} ‘49 ‘l u, - a Q - 4 "I v 1 . ", J, .n g '- . 0‘ " ‘ ' 1“ * " '- ‘- ‘* ' V 7'. " ' ' “ f; ' ‘3 ‘ ". ' J J} r~ -‘ ts-‘I.’ It - . -:HA 4. ' o. ‘ ' "‘ v... ‘ “ " d ‘ '~ V'--- ' - dd n V ~ ’5' ." § . . .' .’ 4. f ‘ . 1 . ., , . 1 . ..- f“ to..- ~ 7- - , . x, o ‘ . w «- ‘I X 1 ~4_ " '5 . ‘I ‘ .-‘_ ’ ‘ .‘ . -. ‘Q' r.- " a g . ‘ V‘. ‘ .‘fgh- ”I". ~ "f 3‘ f. _| at .- 5. K a; ‘ ‘ .5 1 .‘ . ‘, I. ' ' '7‘ 4x. ‘1 A .1 . a -. ‘ L .. -'- -y' - ‘ -‘ ..<¢ I ' v 1.. o ‘o ,. 1 .‘ ., J a a. . ' ‘ .3 L .'V,." ..‘ t .- ‘. '3’? 1- .. ',.,.",’ V '. .... 1. o‘ f" .'.r1.. 1% .3 r . 1"».3.‘ rm Z-‘.' 1 fi.‘.9.".r‘:" ‘.'"w'~“\'? '4‘ "fi-" . 2.1 L Q 4 ‘ ' ._‘ LC: '; ~ l" .. 1 ‘4" ..‘ ‘I . ..\. (w ' 'c " h o "#5- l-3 J -' . ’ "‘ ‘ " ' ’ 1.‘ KY“ ..J are.; I. . a. t: " {J k 4 - I . e 5 v 7 . 9' _ 1‘. ‘ _ . a o . a, _ ‘ o 1 ‘ ‘ on X b 1 t .‘ A . ‘ '1 ... a z r l e .fi ‘ .. n. a . .- 4 ‘e" \ L ... v ' . ‘e . r “a i :‘ ‘g‘ . . .u'fin" f :e‘ ‘L‘. .4 e a .11 -.. .4 . o. -- ’ . ~ ' »-l .‘ - -- .0.» --.... .1 to uno. v Dl- - V‘- J j V ‘1 .1 I" ‘ p ~ 'I ~ —r 1 , _ ‘ , A. v w ‘ Q4 ,« ’o ' V '. V 1' ' ‘\ ‘ . .1 tn ‘ i . - I - ‘0 e- g p ' w ‘ E. J - > 1 ~ ‘) '3.- . J ‘ A ‘ ~ ‘i_ r ‘ C ' " ‘ ' } - A o o '. , 3‘93-11- J V. a ‘ f 1 . 1 -u '9. 1‘ .- 4 g- - . ' - “.4," ~-r" " P: '2 , ..fi. -' k" \. lo‘u‘3‘r‘n $0 1 . U“. 1 . o .1 ..1 .e. ..." .. Kg ~3, ‘ a . ‘ ,. 2- ‘ 1;; ,1 '.V . . ... ' - - 4‘ .. 1 - l r . z 42;, r'. .' :.=. .‘. -: ..‘2 ‘ 2 ' -‘ -~ '12:: fr 9 :; PM: ’;‘ 1:9. .. . . ‘ ‘ ‘ 5‘ u . e ,- ' . .. . _ , I. . ‘ k - . 1 u- - .' o4 ‘: ‘O ." .' '1 s II C . ..‘a ‘ .q'I' :‘O‘ Qt: .H- .4" v -. .. V 1 1‘. . - 1 J ‘. 1-" .‘ . x, Q “.4 f‘ ._ A- ' - "Czfl’ " . .. 2-. :,.‘ ‘ . 0‘ _.‘ ‘ -. .. '., .' '1 ... ”a. if. I. .. 1n." ‘,.-._ ’3 "w ‘1‘. 1 I ~-.. .......‘---¢‘. .- ...... ... .. ,,.,J-.-. _.;'_. -p--.;» ~nrA-Ifi.n-I~»o-v' j». .1; .-I-. ...-.... v . -..... . _‘ _ ..... ,. .. ‘im...-.“...-: .‘r. .: . '0: '.".' ' 1- .b-‘A . v '- f"? ‘ 39:" t’t“ wrirnr," "m4 "I .-~:,." ‘- .' . . ... mlt‘ - ..r ' ' r if f... g I) '1 V . " ....‘. , L . V 1..., I ~. 09. i t.) e 43;“. y 1‘ fl 1 ; _ ‘ I ... . ‘ . o ‘ ‘ . a» ”It - _ ‘ . ‘ , ‘n ‘ fi 1‘ p A. J A. 1 .t p f {-.o '3'; - '. . of‘ 1‘ .3 ‘1', . ‘ .--.,y fl" . 1. f‘f~[‘ - a"... 7 .z “ . fl 3 L3...) 0 .' a w 1. 3..) - "" .. . 1 3 . ‘ . “ ‘- - - w ‘.- . , Jr ~ '3 o , ~ 1- - L G 2: 41- 31- '- 4 ‘ J'- " v n V ._ '1 L f, r. I» " a b. r . > -. , ‘ " r - ~ . , 0-" 9' ' h 0’ ‘ o ' ,. bag a - _ u- - 'r 41‘ ~ P o " . I I . 4 ' ‘ ‘ ‘ " 1 ) f I ' . o -4 . ‘1 . Jon- 3 \J '9 A .4 z A lio . I. . ‘ t J‘- “ . “ , 5' ' . v ~o¢ .- u . C ‘0- )- is l 3‘ A .1 v. ‘3 U. \ ‘4 ‘ 4 \ +9. ) :3 (.V , '\ '0 L". 25‘ n 't ,1 4' x. I-"~ n1 *4 ‘1’ ... F1 'o ’9 -.’ ”-9 1".” § " ... . \w" % Transmission 20 30 MO 50 60 fl 10 80 90 ”h l 1” L 13 4 12 l_ 11 A Q J L 10 100 P 8 \m L Wavelength in microns Infrared spectrum of 1-(2-cyclohexy1ethyl)-5-amino- Figure I. tetrazole from amine. (Nujol mull) fi-e 4': \14 O 0 U1 0 Transmission on <3 .4 O 5’5 09 0 # \D O :4 1n L 13 A 11 A 10 1008::s 9 12 Wavelength in microns Infrared spectrum of 1-(2-cyclohexy1ethy1)-5—amino- .Figure II. tetrazole from debenzylation. (Nujol mull) -1H— ere edded end the solution is heated on e steam bath to remove the emu enhydride. l’he eily protect is crystallized from miohemne. H? 95.59- 96.503. (uncorrected). “We. 8818.6. for BCnH1oE;O: C, 55.67: H, 8. 07: E, 29.72. Found: 0. 55-5933 7-93: * 29-73- .. fl, h . gt. _ 4-,. -1~_a' -' ioet.zo =3: u-l- ... i- an methode ef Herhet. Roberto end mmn (11) end Herhet (13) en. need. he preeednree vere need for the extraction of the eeiee and ’reeipttetim of the hydrochloride. Emepiee of both procedme ere given heiov. The forution e! 1-(2-eyoiohexy1ethy1)-h-I-nitrohenzy1-5-inino- tetreeeline hydrochloride viii innetrete eethod A. The tetreroiine momma-rm. ie prepared ee renown 11.! g. (.06 eoiee) of i-(R-eyeie- Wethflfifi-uinctetresole are heated vith 15.3 3. (.09 eolee) of .411th chloride at 114006. in on oil heth. rotation of e hole- me “melt is relieved by e rapid exothermic reaction after vhich the mixture eolidifieo. The hath ie kept at 1&000. for an hour end e he}! etter the exothermic reaction mbcidee. The crude product ie dieeoived in 300 ll. of boiling ethanol. Five hundred 131" iiiitere of mter ere edded end the entire eteem dietilled until the distillate ie eleer. lore veter ie edded elovly during the distillation to maintain e vole-e e! ehout 300 .1. of voter in the flock. Thirty gram of pets-ei- hydroxide ere elovly edded to the urn residue and the eoietiae etirred for tvo hcnre. One hundred end fifty eillilitere of ether ere edded efter eeoling vith ice. Stirring is continued for m: an hour. the ether leyer ie eepareted end the voter layer extracted three times vith 50 I1. P‘. 0 portione of ether. The combined other eoiutione are dried over poteeeiu -15. . . . . e e. ~ - .. , . .. . . . ’ . . ' ‘ "- r , ' _ . _ t ( ‘ -‘ .. .. . \ ‘ a .. -‘ .. i- .. e r - ,‘\ e . II n ‘ r .' .1 (I .." t I. f 1'; Fr!- e 3', r r - v .. A ' . . n 4 N I t 70‘ ’ ‘1‘ - ‘ e r .‘ -e .L J- ; —... , c. l . I. e‘ o‘- v «1‘ --- ~ ‘- 11-" -‘ 1-3 -' . J '0 e‘ . .J'. 3 \ . e . f _ .. - H I ‘ . I. ....v.’ .e-p. -.r e ‘ m .‘-‘..) e , - ~ . n4. 3 1 e -.- .. n -..- . \ e , m e a . ‘ .f I r . f ‘. e '3 '. I ' e. e . ‘ .V ‘3. re" . ,t ‘ I 0 . 3' '1! '_' . '71. .fl-_.‘;, . 5 1 ." I‘ .- . P I ‘ £ ' . a I .a a 5 .. 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(3. - ., .1! ”4’.“ J . o. ., _ . h . . _";. , ‘~ ‘w 25‘" ‘ .- "r " - ,A., .~ .23.. . xi. ..I.-..- u.~c.. r r v - ' .«- .. v -' . .. ... . ( ’0 _ , L ~ .- a. ( I; It.» . '“3 ' . ‘ I... I ) ' ". 3' .'- w - ... ; - , \ _. - . . r. . .4- ‘P‘ .. a ‘ ' £2. .. \ % Transmission % Transmission 30 ' ho L 50 60 - 70L 80~ 90- 100 ‘ilkLilJlL1‘» 2 u567891011121311+ Wavelength in microns Figure III. Infrared spectrum of 1-(2-cyc1ohexy1ethy1)-u- benzyl-S-iminotetrazoline hydrochloride from l-(2-cyclohexylethyl)-5-aminotetrazole. (NuJol mull) no . lllLllJlJll 3+5 6 78910111213114 Figure IV. Wavelength in microns Infrared spectrum of 1-(2-cyclohexylethy1)-h— benzyl-S—iminotetrazolins hydrochloride from 1- benzyl-S-aminotetrazole. (NuJol mull) ' -2o- evaporated. the residue '1. dissolved in mo .1. e: 95:: etheul and 50 ll. or enter. e nan wt of an ineoloble product 1. formed when 320.1. or ooneentretel Weldon-i0 Ania hm been added and is filtered off before the hydrochloride precipitates. the crude hydrochloride ie redieeolved by heating the euepeneio'n.‘ the hot eolution ie filtered'end chilled with en ice—veto: both. he um eo obtei'nod '1. filtered and dried. the yiell of 1-(2-oyolohew1ethwl3-3-‘bensyl-5-ininotetreeoline hydrochloride no u g. (23%). After two recrystallization of thie product tron equeoue alcohol the product'nelted is 2090-2100:; aim. ”icing pointe a: m. product and that node by the beneyletion of 2- cycloheflethyl-S—ininotetrezole showed no depreeeion. gratin ‘ at .1 - - '- 09-3 at ~. Bali. W The method of flrkhofer (21) end Percival (h) we. “on. he hydro- genolyeie or debeneylntion “done he fallout 1-(2-eyo1ehexy1‘ethy1); h-eeneyl-y-ininotetreeoline hydrochloride (3.22 p. .01 sole) 1. an- eoived 11190 .1.‘ of mania One gnu e! 55 pan-hin- on oherooei :- added and 50 p.e.i. of hydrogen is epplied to the eyete- for two bean with ehnking in e Burgeee-fPerr ice pressure hydrogemetion epperetue. The theoretical amount of hydrogen is nbeorbefl in half an hour. he catalyet ie filtered end washed with hot ethenol. Sodium carbonate (0.5 5.) ie edded and n. eolntion is concentrated. Yield of i-(2-oyolo- henletbylFS-eminotetrnsole use 1J4 g. (71%) m3 212.59-213.5°0. (anon-rooted). , . A mixture melting point of thie product and that produced ”the reaction of 2-cyclohexy1ethylamine, cyanogen bromide end hydroeoie eoid gave no depression. -21- M ~I =4 '-.'¢ . . ’— . ‘ . . I '. . . ‘ "I ' - t ...I; _ t» A r. a .4 '. . ‘ " i‘ I" re L‘i,-, I‘ 1“"‘-E 21;... I ‘. 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' -.-" ' g- 1 e ' ‘ I '1) " .1 w I“ ' ‘ ‘14-: . i. *r'fr-a, ..., 'w- ‘fic. r -. ‘ f' a ‘t ‘1 — .e. . b ' I ‘-\ T - ~ 7 ' ‘3 J'voeg- « ‘ ‘ Q ,‘. -'-~ Iv ‘ '- . . . v 1‘ 'l: 1-54—- F I yter" _ '- . , g ‘ . . I '. . . 1 . ' a '9‘ .- 6" a ... e ‘ i . ' v ‘ 0' ' - ' e v ' .‘ ‘ " . n .. A , In”.- A. .- . i ‘ eu.1»x z. gin . v I ' . ‘ \' " .3 l " ' - . ' V ' ' " "n I'""'\'r .0“ a. " .‘ev‘ " 'rl’e“ ' e ‘e l‘ . N ‘ , - 7 e. t. ‘5‘ ‘V .3 nL' a - ' , ’ g, f - Afirng “are :5 h. ‘_3_,1‘3.b.<".'.5.t-‘ {‘d-r mi. 0.3.. ”9'3 nu One gram of the ninetetraeollne modeled“ 1e mixed with 1.31 g. e! mum-me hydroflie 1n 5 ml. of water and 1 m1. of ethnol. the r} I solution 1e extmeted eueoeseively with 30 .1. end 5 e1. 6! other. The J combined ether than are dried over eodhm meow; After evaporating the ether the realm....3.qui¢1bze 1e tree tea with half its telme of 3m huu'neotMOmmte enr‘ the mixture is heated fer 1~5 minute. on a stem: be £311. The crude product. t is?! a. .eidx‘ with 5 m1. of petroleum ether and 5 m1. of 5:3; nape-633d alcohol. the pkmxylthimreae ere recrystallized I tron 75}?- leopropyl alcohol. -. 2 7" ' i It was neneseary to cool the finished product yith dry ice to cause crystallimtion in the premmtion of the nhewlthimeee den-{muted ..rm the 3-31 nylon yl and 2-phm; letilyl eubettthted tetrfieo1lnee. 3«‘* In. meme». 9! m1: e (reel of menu m Lime." tn Wing i ‘ 2 the derivattvee cf the p-nttrchenzyl mltmbeezyl ehd yphehylpropyl substituted tetrezeitaee. 3 Formal-5e. melt}. ng petite and enelfle} are given in Tellfini. 1‘4 : I . : ' i I . ‘ ' ‘ 2 2‘ E ‘ 5’" The Mnotetneoitne teeee were prepered. ee “new: I I... e! the hyfireehlortde ere trusted Itth 1 c. of poteeetue We» 5 ll. of Inter and 20 .1. of ether. The mixture 10 IM an e EItem hath until both layers no clear. 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The nomalkylation of u 1-mbsututed~5~aa1notetrasolc to give a 14-“lubcutntd-s-ininoutmtollno ha. been discussed. 1 pm! a! otmeturc for tho 1-(2-eyclobexy1athyl)-5-am1no%otmzolo has been described. ...: '- fi 0‘ - . ‘ . - ' ... . ...-(x v y") ‘ .- ‘ ‘3 :1” A“. ,_ 7 I." (V " ‘ ‘ Q * ~ - ' . r .. ,- ~ *' , w.vr" %. a“; ‘ ' ‘ ‘ 3‘ v " , r 1 fl - r’. . l ‘ ~ ‘ ‘ flux '1 . J“? .I a" . a" n "-- ..-Q -- ’4 .‘ . 'f n", . _, --V_- -_ . w. _ _ _ . , P , :1- w -- yr 9 - -.- .4 xi 1.“ . ,. u I. C —-0 t o \ I _ A 00‘ a $ - V; I I'- .‘.. H . ',‘ ... 7“ V 4.. ., _ . . . - . ‘ ..- A ‘9' u "I r ‘ ; . .- 0 ~ I . . . , _ ' o 3'. J a,“ A . -' '- .~ '_ ‘y ‘ , k r . ‘4. 3‘9“"; " ‘ ‘ .. I - J ' ‘ ' "-r ' ., ‘,. n‘ . . . l - .4 ‘ V A- ‘ . '- ' o - . 1' H’ I I P .... .1). .‘ b " A 4’ . 0 D o _ - u .A ‘ ‘ l a l . 1 .- .a ' . c \ V . .w‘ . ,,~. ‘._'_ )x} ”I '- 1- ‘. .7 ‘ ‘ "ii 7 '- : .3 , ,A, K' v I. ‘ . . ‘. f ' f If, A ‘\ .. ... v \ ...l 2...: '9 z 4 l ‘ 3' ."4:...\' “27". .,E. ”1” -ar4 :- L , ...: 0‘ :1“. up. .5 I. r h . OJ‘HO o . ’ -' 7' i ' .‘3 .: - Z ‘2; ._ . 1 .1 . . 'I": I. f - uh: . v .-J.-. ‘ 1 q ‘ ‘ . .' ~. _ ‘ .. 7, II . .f,‘.’ .“‘:‘- .31" arr-yd . ‘ ‘ f: A . . . _ ' . :1 I‘ ('3 f ..O :4 if 0- ‘ I“ V‘rI-‘ ‘ ‘l- ’ '“ ‘ -‘ 1 r I " I ‘ I} J ‘ ‘. it ‘t- ." ' u... 7‘: . -.‘I‘c I.) “1 L?;‘f.—’-’L -.& .3 ‘. Q. ‘5' 1-,.» ,1 .. .. a I .\»o'._1“!." ’8 i0 J.'O. J; «30 '3iifieab sqai r“! .’ ... 1' I ‘ V ‘ a 1 ‘ 0' -t a J 2",” -- i 'v p. 1. ' 10. n. 12. 13. 1h. 15. 16. 17. 18. 19. 21. 22. R. J. J. H. A. R. I. U. B. I. I. I. Elnlngor. I. F. Ecutaer. and J. C. Pators. fibstracts of Papers Proccntod .1 1h. fleeting: of the American Chemical society, nan”. Toma. Tu (191-11 195-3) Thin]... Ann" 213. 5“ (1332) which, and a. Inglo. 1am. 33.51. 932—2265 (1333) b u. Box-bu and n. Percival, J. Org. Charm, g3, 1:39 (1951:) autumnal A. Fan. Ann... 1‘4, 339-369 (19-01) atone. Ben, fig, 1113-25 (1923;) 8:01.10. J. prakt. Chum. 133,. 232-309 (1932) smug. J. prak‘t. one... 133, 261-300 (1900) Stella, Ber..'§fi. 1557~91 (1922) van Braun, and 3. Keller. Bar...§§, 1577 (1932) a. Earhart. c. Roberts. and x. Harvill. J. Org. Chem, ;§_. 139 (1951) smut. Bar... 51, 70:4 (13:21:) Garhrooht, and a. he. Herbst. J. Org. Chan... 3. 1313+ (1953) H. Herbst. ébutracta of fapera Presentod at tho haetinga of the Llorioan Chemical Society, Dallas. 10x30. 7% (April 1956) ggagggsna. od., Eager Adams. g3. 51.. John Wiley and Sons, Inc.. Saw York (19h6) Vol. III, p. 310 agrbrocht, and B. H. Herbst. J. Org. Chen..‘1§. 100} (1953) n. Benson. Chen. Revs..‘§;, 1 (1gh7) 19.13.15.213- nger-Jaoobeon. B X11, 3). 13 buPont. Explosive. Division Ean%mnn Kodak Reagent L. X. Btrkhofar. Ber..{15. M29 (1932) [11.93. unpubllshod work -27“ r ‘2 I." 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