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I. the Reaction of Nitro Compounds

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I. the Reaction of Nitro Compounds Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1926 I. The er action of nitro compounds (including war gases and explosives) with organomagnesium halides; II. Study on anti-knock materials, the preparation of tetra-styryl lead Roy McCracken Iowa State College Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Organic Chemistry Commons Recommended Citation McCracken, Roy, "I. The er action of nitro compounds (including war gases and explosives) with organomagnesium halides; II. Study on anti-knock materials, the preparation of tetra-styryl lead " (1926). Retrospective Theses and Dissertations. 14247. https://lib.dr.iastate.edu/rtd/14247 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. 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Box 1346 Ann Arbor, Ml 48106-1346 II • Tin T ^ J. •Ilic Trriter vrishes to express Ixis apprsciation to r.r. :Ienr^ C-il:aan for the s"a£jgestion of these pro­ blems ar.d for his £-enero-as advice and enco-aragenent •jiven during the \vor>. A ^'4 kJ X 4 ^ •:•>"7"! T T The vrriter v;ishes to eicpress his appreciation to Ir. -.J. r.. S-v7een97 and to Lr. henr^r Gilnan for their suggestion of this problem and for uheir generous ad­ vice and encouragenient rivon curing the vvorh. S\ -r\S'^3 Ill 23.f\e Reaction of IJitrosobenzene 1 liroerinental {-"itrosolDenzerLe) 4 Preparation oT ;;iphen;"lh;;-drox;-laciLne 13 Heaction of riphenvlnvdroxjlanine 14 Table I 17 I/iscussion 19 Reaction of p-i;itroso-ciLieth.vlaniline £2 Iteaction of p-l-.itro-disieth^'-laniline 26 Table II 27 Discussion 28 ijroiaatic }Iitro Conpounds (Introduction) 29 nitrobenzene v^itli PhGn^-laagnesiun bronide 57 o-Ii'itrotoluene v;ith Phenvlmai^nssiun cronide 40 p-liitrotoluene with ?h.en;rl:aarnesiu:a Bromide 42 o-ivitrotoluene -^ith Insufficient 43 Table III 44 Z'itrobenzene, Bronobensene and llagnesiura 45 Preparation of -=henyl-a-."aphthjlaraine 48 Attempts to Prepare liitrosobenzene 51 Keaction of ^lienylacet^/leneaa^nesiun Bromide 53 Reaction of Benz^imag-nesiun Chloride 54 Experimental (Benzjrlna.^nesi'oa Chloride ) 56 Preparation of ter-Butjlraagnesiua Bromide 62 Reaction of ter-Butylmagnesium Bromide 65 17 COilTZl^TS (Cont'd) Page Reaction of iso-propylnagnesiu^i Sronide 63 sym-3ip]i€nyldi'benzylh;^'"crazine 65 iTitrooenzene v;ith 'Ctliylaagnesiuni Bronide 68 Dinetiiylaniline Ozide vrith piienylraagnesiua Broniide 71 Zth^.'l Nitrate v/ith rhenjlnagnesiiin Bronide 72 PART II Discussion — Anti-icnock Ilaterials * 74 Tetra-stjryl Lead 74 Experimental 78 Conclusions 80 TT'^ Pr,1.%>J TjT^'»/ ^ TX'oJ^ IVielana and Rosee-J.^ treated nitrosobenaene, 051151:0, V7ith. phenylnagnesiun "bronide, GgHsJ.IgBr, and obtained diphen^'l- hj'droxyl aaine, (CoIIojSI-OII. The nitrosobenzene v/as dropped into the phenylnagnesirm broraide at a temperature of -15°. Reaction: 0 0 -* 00 ^oD + 2 However in a later article the;' state that the above is the expected reaction bj conparison of tlae -I.'O group v/ith the =C=0 group but that as a rule the reaction does not stop at this stage; the R{E')K-0-;.IgZ. is reduced by a second mole of R'i%Z and the ox;-gen made available converts the into R'OLIgZ: R (R' ]uOlJgZ Tc' J.igS — R {R' )ilLTg}! H' OlsilgX The conplete reaction would then be: R-I:c -I- K'i:g~ ^ R(R')i<0]^ R(R' )irLlgX -f- R'OI.igX R{R'}iri.ig}: 4- iioH —> R(R')ini iig(oii)x R'CHgS . -f- IIOH ^ R'OH -|- Kg{OE)Z In the conplete reaction one molecule of the nitroso compound would consume two nolecules of IuiIg}C. 1. '.Vieland amd Roseeu, 3er. 45, 434-9 (1912). 2. '.Vieland and Roseeu, 3er. 4H", 1117-21 (1915). From our data the above interpretation of the reaction does not appear to "be the correct one because: (1< In this scheme -nly trro moles of r-=act v.-ith one nole of 05115110 v/hile experinental evidence shOT/s that three noles react. (2) There is always a large anount of diphenyl produced which is not accounted for by the above scheme. (2) There should be a molar relation betvreen "Dhe anount of phenol and the amount of diphenylanine. iji in­ spection of the subsecuent data reveals that the amount of diphenjlamine is large and the araount of phenol is very small being only that v/hich results from the oxidation of the Hllgl by the air and ether under the conditions of the experiment. BlanJc runs using only the gave the same amount of phenol as the reaction mixture. from our data the reaction nay be expressed as: Q t h i- 0-0 + + IiIggCBrg The first step in the reaction is no doubt, as .Vieland and ?:oseeu^ suggest, the formation of the addition compound {C5ll5)2K-C-L!g:c which on treatment with vsrater gives .;e have duplicated their experiment and obtained the diphe- nylhydroxylam.ine, (05115)21^011, in reasonable yield. However when the dinhenylhydroxylamine was treated with phenylmag- nesiuia "bromide it consumed three ec-aivalents, the first q;j.ite prohaoly forming the sane addition product as results from nitrosooenzene and phenylmagnesium bromide, namely (C5il5)2l'-C—:.Tg3r. This compound then consumed tv/o more equivalents of phenylmagnesium "bromide before £^iving a pos- itive test*^ for excess H2%Z. The reaction mixture on being decomposed with dilute acid and worked up in the usual way, as described belov.', yielded diphenylamine [4:0.2-1], diphenyl (70.1^j) and a small amount of phenol {1.08 g.) but this amount of phenol was shown to be obtained in a blanZ-: run when diphenylh;i^droxylamine was absent. The reaction of nitrosobenzene also yielded, as 7;ieland and Roseeu report, small amounts of azobenzene. Small quan­ tities of p-phenyl diphenyl, { ooo ), not mentioned by v/ieland and Roseeu, v^ere also isolated. w'ieland and Kogl- treated p-nitrosodimethylaniline ((CH5) 0) with phenylmagnesium bromide in the hope of ob taining phenyl-p- dimethylaminophenyIhydrosylamine 05" "the product was found to consist largely of a substance regenerating on decom­ position with water, 2Lnd some (p-(CH5)2ii-^^ )2* crude product of the reaction gave with dil. HCl a canaine red color. This may hare been due to p-(CH5)2l<-^j^l«E^^ . 3. Gilman and Schulze, J. Am. Chem. Soc. 47, 2002-5 (1925). 4. V/ieland and Kogl, Ber. 553, 1798 (19221T Also p-tolyl- and ethylna^nesiua broraide reacting v/ith p- nitrosodimetiiylaniline £^ve p-p'-ainethylaainoazolDenssne. p-i:itroso-toluene, {SO), reacting in the cold with phenylmagnesiuni broaide gave the expected p-tolyl-phenjl- hydroic^laaine ) a body very similar in its properties to diphenyliiydro2jylamine. SXP2HI]fflI«TAL 52:AG2IGI< or rllTROSOBsHZSmS ATiD imiYLrilAGEESruIv: BRGIIirZ The nitrosobenzene {10.7 g., 0.1 aole) was dissolved in about 200 cc. of dry ether in a three-neclced flasi-: fitted with a reflux condenser, stirrer, dropping funnel and a tube for passing pure, dry hydrogen thru the flask. Phenylnag- nesiun broniide in ether solution vras added drop?/ise irith stirring and at the sane time hydrogen was passed thru the flask. The heat of the reaction produced a gentle refluxing of the ether at first but which was considerably less vigor­ ous after the addition of one-tenth aole of CgHsI/igSr. A brov;n precipitate appeared at first which later darkened and disappeared. After 0.1 mole of G5H5l;igBr was added the reaction mix­ ture gave no test for excess KlgZ; 0.1 mole ciore was added, stirred 6 hours and it then gave no test for excess RLIgX; 0.05 nole more was added and allowed to stand over nig'at -5- after which it still did not show an cxcess; 0.05 laole acre was added laaicing a total of approxinatelj 0.3 nole (three equivalents) after vrhich the reaction continued to sho-!7 an excess of PJigX even after 24 hours stirring.
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