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Declassified record · U.S. Department of Energy

H Division Annual Report of Research Activities (Group-4) Volume I (Organic and Biological Chemistry), Lams-815R (December 1, 1947 to December 1 1948)

Dated
Dec 1, 1947
Document type
Report
Length
115 pages
Open the original scanArchive record OSTI ID 16295675 · public domain

Document text

Machine-read from the scan, so expect some errors. Lines that couldn’t be read are left out.

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This document contains ptges Divi don Leader, Research &.dnsor Acting Did don Leader

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of Group E14 has been to write UF 3.11 raseamh work of a declassifiable nature and sutrnit it i date ly for declasrification and nibsequent pbUcation i n current scientific journals. Several reports of ffnlshed research have, therefore, never appeared in the U or W series. her of pieces of work ham bean done by the resoarch group that Hithin t h e m aelver did not justify an U,WIQS or journal pb li cation, vestigetione ere LH -mgrses, the publication of which alraitr further rcseer:iiy I)twloualy organization of +2m above mmtiowd material is necessary if th6 laboratory Director, the Association Mrector for Rosearch, the Associate concrrned are tC obtain an o ~ r a l lappreciation of the research activit:.-i :

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individual publication as I&, -US or technical journal ppers. To report on work in pmgress. To present t o the Loboratory Dtrectors, the Health Division Lador and other interested perwon8 an organized overall &ctUre of the medical end biological research ectipftfes of the Health Division. 6. To orgrniw for the research workers themselves the pact par's ing the past par two additional temporary military bam ck s have been :cin& and converted into research and electronics laboratorie~. An additional cr.e: half or a laboratory has bean obtained for the Orgsnic Section i n U-EicilYrd. P t ths beginning of 1948 the t o t a l space al1ott.d to all research s_cd Decofnber bt, 1948 the allotted spce has been increased to 7600 sq. ft, Reaaarch eqtdpment to trung about $50,000 h s been pmcurbd. several reseerch nicrorcopes, a Eeckman spectrophotometer, auto:lavr, ;:atxrk apparatus, pH meters, nicrotoaee snd accesaories, scalars and other radiac::i, Counting e qu lp nt, incubatma, centrifuges, refrigerators very important item in the ~ r o ( ; r w scf the past year hes been Th=

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logical research program for the coming year include (1) some improvement in genaral facilities (2) pctlrsmsnt of special equlpaent (3) addltioa of spca for relsan?h ara. e. Apmarameat of at hart ono additiolvll labontory for the 2. Aocunment of Spacial -pent Plans are undomay to ertabllsh a completsly neu swtion of &%e Rescurch Gboratory for the E pci fic purpase cf studyfri the effect6 of radiation on h vy molder ('proteins, nut= 3. Electslcal d if hui on amraws

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pl8nning stage or rctursllp in pogress. Undoubtedly the program is svera amb%tiousand all projects vtiill not. dwelop. 4. Synthesis of labeled in

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1, Chronic distribution a d excretiua of mericlun by the ra:. 2. Comparison of the rst L.D,% of smerfcium mci Flu- ~ hyroi dnetatmusap of 1u1as rdatei t o metaboxan of thiaurea iawd dth s 3 5 D u5. hfetabolisn of nitrogen mustard labeled with Ce 6. Metabolisn of Avertin labeled with Cue 7 . Effect o f radiation on the ~ W d dend Ma logical Methods o f dotmrminfng bericium i n bioiogfccl s p : - 9. Methode of %ag~os?g exposure of parronnel t o ameri10. Effect of firing temperature on rate of solubility of Following the blood picture -.>rough repeet penpfi6:cthe effectivemeas of ED as a hemtopictic stm:i?.&.ic:i in mice exposed to X-radiation.

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mid eamilutionr nhere practimbla, it ia proporad to bmgb a long term study of radiated prsomsl #ho hos left ala of the extendm mat- available will be undertakes to detezmine tho pracacal significance of peripheral bicad

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p Qurntitotive Study of ths Effect of Nitrogen b&- mine the relative biologicel effectc of nitrogen m s - tarda urd the pantitntdve relation to ionizing rediaUrns of Iniw FL'1 of the u i t o t ic IndaRhftel: af Llitotlc Time ox Yourn n=On aasumption that the slope of the initial drop o f mitotic index after irradiation is relatad to the mitotic time, it 5s proposed that tho mitotic time be dekrmfned In variaus actively dividing tiscrues of the mouse as a meauure of mitotic time. of the mitotic Index of various m e tissues to X-rsyr ha8 been ertablishd. It fs proposed t o detennine the runponrre to 15 Kgv, neutrons and by comparing she ewes obtained determine the r-n ratio.

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contfmous Smatml Pbmoorction. 30 t:-4 number o f perrons from other groups and other divisions hve contributed materially to the work & ~ ieamz kin Lh.3 help received from a.Gerold Tennay and o t b e r members of @Zd,51. Harriet Htwdy and Kr. Tom W t e of H-Division, Kiss Dorothy Poskcndd and other members of the Health Civision Hsmatoiogy Laboratory T.2. R3, The members of Croup H-4 wish to acknonledge spclf ~ call gthe It is also a pbauure to exprose e me cia tion -c Coi, James P, Lag 8-4 Reaearch Staff greatly by aasagrsng excellent :mung mdlcu ofSchlrmmn have served in the capacity of full researa staff m-barr and thetir contributions to the progress of *hpast, pecr n8-m

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a 60 ml. Found bottomed flask equipped with a Guard tube and standard. taper glass joints slug m d B rotating nagnet. moved a t room taper a ture under VOCU~UP, yielding pale orangs troa sodium) a0s distilled into the reactiar, flask and stirrsd .#ith the magnetic stirrer uc til solution :vas csmplete. a d a Bunsen valve scd th2 ezcess ammonia ellowed t a svaporatr. me crude product ::'as dissolved i n 25 al, sf veter and filtered through a medi u sintered glass funnel in tsa liquid - liquid exand then extracted for 1.25 hours. ng. of a reddish-brown tar, The water solution GVOS ther. neutralized w i t h 5046 EOH. and Edjusted t 3 ,DE8 with 10s NaRCOj soltaluene, decolorized ?fit3 carbon and cooled. :verb re crystallized from8 11. 3 1 Sot toluene, Stirring was mafnthined witha glass enclosed Iron of ci cot in oy l hydrochloride. AnhyC ~ u sammonia (10 ml., The filtrate wss acidified with 1,5 31. of 6 N Hcl This procedure removed 11.1 & traction ivaa contirued ;vith ethyl acetate The yield a ic xC epo duct :7aa 96.6 The crude praduct wns dissolved i n 12 nl. af hot The crystals obtained then from linseed all, then fractionally distills d and greserved In glass stopgered bottles.

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lmnary runs with pure untagzed a oo tin ic -;Yacid using 0.17 - 0.81 EM s c a l e ~ 1 1gave conversion t a the amide with arent crude yields of 114 t o 103s and nelting 2oints verylng ples were treated identically, the & purity :vas not constant i n amount or percentage b u t :7as riore a?parsnt as the scale of th8 reaction wycs lowered, Quite adequate in rai siu tba aelting point. acid (0,41 a)comparable in ;ualitp t 3 that later used i n the 1271 and 81.59 (126.5 - 128O). This indicated that the crud. n1cottd.C acid could be efficiently employed inthe synthesis of the amide.

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(Contribution of the Los Alms 3cientlfiL: Laboratory of the University o f Calif orciz,21s hlamos , New Nexicol . Tbe Synthesis of Methyl Bromide Labeled with C14. k thur Murray 111 and lath any 9. Ronzio ha the syntheses of certain organic campounds where n ethyl m a are required, nethyl iodide, now available togged with O%b either too reactive or too unstable t o be usef2l. In th& instances, the more stable methyl bromide i s indicated. tde labeled with C14ushg labeled methonal as starting n h k 9 containing 5 d of HEr - H2S4 mixture (mads by the t o 23.03 g ofaddition of 3.6 ml of concentrated H 90 4s RBr) and a glass enclosed Iron slug were attached t o fold at the point indiccted i n Fig. 1. period of gutgassinG, the flask was chilled :.lith liquid tha *Zen with liquid n it r sgen and attached t o the line. The @ a t bsyatem vias evacuatzd xi th the hi & vacuum 2nd closed Off fm vacuum manifolds. Yith Stopcock 2 clased, the m than al

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btbe purifying train bd with adoro stopcock. quantitative transfer vas tin the system waa pumped off. The transfer of known 8 of CE3Br b y this method is Guant it at ive. (99.8$). .elas of methyl bromide obtained were 94-646. The prowith liquid NZ. Any noncondensibls zas by this method vias checked for pri ty by analysis e oil bath heater was nade b y wra?ging resistance wire da crystallizing dish und xt s can trolled with a variable tlg lower yields than the m e used'which corresponds toa k"Experiments using PSr3 for the brominating agent result el - theory uith runs an the

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s a moa is a compound of great biochemical interest and also in a starting for the preparation o f a .mmber of organic compounds of pharmacolo@c in- +-e this synthesis was undertaken. )obe a s desired which utili zed this compound koamy be synthesiaed by a numbr ofme + hds b OIIllisri, Blair and Brown - 3, Am. Chem, 2ocePE, 8) Wohbr and Kern - Helv. chime ~ c t a .4, 3Cl (1925) rihthoff end Moragas - Quim. Ind, 207 (1928) 1) WVhddi and Rodzavlch - wim, Farm. Ron. 3, 20 (1934) s *t and Xrawczynald - Helv, Chim. Acta, u,1009 (1932) p Of drich either give low yields o r give complex mixtures difficult t o eeparate. nt is based on work performed unaer Sontract No. 7405-eng-36 f o r the

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wre decanted through a filter and the filtrate nas treated with carbon lpntil 811 of the barium w s precipitated as the carbonate. Frit this point The barium carbonate was filtered off and washed with dia- $$pitate should be kept until the end. of the experiment. The filtrate and r e treated with 0.6 ml, of concentrated sulfuric acid in order to hydrolyze do formud. The solution R ~ Sallowed t o evaporate slowly at a temperature of nr milliliters of eyrupy residue (2-3 h y s ) , The syrup was diluted t o 2 5 ml, ird rater and filtered in order t o remove a small amount o f barium sulphate. B then was made alkaline oi th amnonim hydroxLde ana evaporated t o dryness @mature under a gentle stream ofeir over calcium chloride The drying was completed i n a vacuum A3 the drying progressed it m s necessary tobrd The dried residue was then extracted It was necessary that the precipitate lever the liquid as often a8 it formed, 10 ml. portions o f hot propyl alcohol, a t0 afine powder during the extraction and that the solvent be allowed t o 1 filtrationr The solvent was removed from the filtrate under vacuum a t room per cent (average of eight runs) and WSt Up the brim carbonate precipitate. i n the folloving manner: b .hich mas saved, wau treated with a sllght exce8s over the calculated amount Khen t h e yields fell below 90 per cent, it was neceskte hydrochloric acid aM filtered, mount of ammonium sulphate and filter & , aoric acid, was evaporated t o dryness e: room temperature. The filtrate was then treated rith the The filtrate, already acidic from The residue was dth water, made to pH j-6 with di luce potassium kydroxide, made basic Tith am- -de, ana evaporated t o absolute awnesg. lhol as before,, thanoi, decolorizing rith Norite, evaporating t o dryness, and find3 re-crystal The f i n a l purification was carried out by dissolving the pro-

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Organic Chemistry Section si8 hydrocarbon is characterized by a high melting point I, and a brilliant Violet fluorescenos. The olompound I s pinated by a compound o r compounds whiah an part a yellow rto chrgsene and which changes the i luo re ace n ce to a green. ipagurities aannot b e removed by recrystallization from benand acetic acid. k. The method found t o be adequate for the pur ff la ation was I Chrysene was dissolved i n sym-tetrachloroethane. While b. ro lu tion it was treated successively with cono. sulfurlo i8 then dried with silica gel and concentrated. Upon cooling, 1until the acid was no longer discolor ea.

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Los Alanos Scientific Laboratory. Cas Xlamos, New Kdco & search for organic mater4els which mould serve as scintillation type ctors similar t o napthaltne (1) has resulted in ertablishing L.?e senda w t i o s of nine compounds reletive to nsptslalsne (2), both for lP21 and IF28 jbtona3tipUers. ReCry6tall i Zed and sublimed samples ofall compounds were # W d dth the exception of one sample o f commercial napthalsne for comperative at constant volume i n quertz t s ~ ttubes, the scintillations obmmed by four wtomltipliera in parallel exmounding the test tube. The @BOSS were am.. 1.8 &rsme of each material were used, packed 8s nearly as poeslble - .;.wfiSabp a Loa WBModd. $500 pulse amplifier, voltage discriminated, and rdd on 8 scale of 40% and ?egLster, The multipliers mere not refrigrrbd. A 20 rnc radium ghnnna eouxe placed ate standard dirtsnce of 71.5 Cm 'ma wed for all teats. Figures 1 and 2 show a series of integral, pulse height distributions for the conpounds inmatigated as ob s emd nith 1328s and u*Lls. it I 6 desired to call attention to the following featurest (1) Several con pds, in particular anthranilic acid, showed eaeedfng4 rtrong nuoreweme t o ultra-violrt mib ation but were wry poor as ecinUllating materials with radium gamma. (2) The -de power apply ms arranged so that the supply vol h ge Could M a d and alro the voltages to the indivlttue.1 tubes c m l d be separately adThis msde it possible t o equalize the detection seneitititrlties of the tubs and after adjuatment, to shift a l l the tubes together t o ar,y de- -'-*aaverage dynode voltage. Dynode voltage on the 1P288 was so adjusted that

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( 5 ) The stilbene, at z h ~?.Lakiasess 16 a t leart a factor of t'ares ttrr t$an a r hracana WMCI: tp 5 the b e a t material found preoiously is) (6) Although ref'rigerett-n net us&, the pulse 3eelght cumas do - '% "bt o o a ~to extrapobte back to the same m r o bias value for a l l tine compbunds. .*the cucocs for napthlene, anthracene and stilbene the zero -6 values ' oould possibly be tihe same, ar shown i n the figure, indicating that most of bfae arising f r o m the gamma radiation make enowh photon8 to be countad. fO? mot of the other uuterblu, however, there swms to be 8om indication fht not a l l beas are counted even at mro biar. The great adarntage of the ~Ulkmsis its high corneraion efficimv, i.ea, large numbbr of photon8 per bob energy loii, dich is aparent atthb lsrge pulrs heights, The flatm e of the stslbem curve at low bias leads one to hope that a mrff1cient:Y lood material may be found for which the extrapolation to zero pulrre height can Sulbane …

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