Hirono T

Ishino S

Noguthi J

Noguchi Junzo

Ishino Shohei

Hirono Tatsuo

野口 順蔵

石野 昌平

広野 達夫

Kanazawa University Repository for Academic Resources

The Science 1~eport8 of the KanazawQ University， Vol. II， No. 1， p. 75~-78， March， 1955， Studies on the Synthesis of Protein Analogus (Part V) Polymerisation of DL-alanine長By ]unzo NOGUCHI， Shohei ISHINO and Tatsuo .HIRONO (Received Odcber 30， 195'1) 75 Successively to the preceeding method， we tested the polymerisation of DL-alanine by the method of N-carbothiophenyl引 ninoacid， Polyalan加ehaving high moleculaτ weight， about 22，400， was prepared. C明I)I-点oH!j再凡民15SCO∞N悶H配o印二3耳H王;ωO叩H担也坐堅型竺目些出盟E恒空型担!担控竺型eι→C叫H凡5却S訂印H山fI+CιC刊仁Oヲパ→f円N阻JλEH1f311000h胤 at600C '-， \CH~ )n N-carbothiophenyl-DL-a.'lanine (m. p. 1380C) was prcpared as the starting rnaterial by the Lindenmann's method.1) 1n this polymerisation， the solution poJymerisation gave the better results than the block polymerisation. It was carried out at the heating of 600C fOl' 1000 hours in a sealed tube， in which the benzel1e solution contained about ten moles pyridine to the sample as in the case of polymerisation of glycineρWith the progress of the polymerisation， proteil1句likeprecipitatiol1 began to appear graduaHy. It was shaken now and again to make It unifonn. After the reaction， the polymer was isolated with centrifuge from the mother liqour anc1 thel1 washed with alcohoI al1d ether， and dried. The polymerisatiol1 rate was 70.8μof the theoretical. The al1alysis corresponded to polyalal1il1e and the clear Biuret's reactioll was observed. It is il1so1uble in water， a1cohol， be回 el1eand acetic acid， al1d sparengly soIuble in conc. alkali， and solubIe Il1 conc. hydrochloric add， the mixture of acetic acid and monochlor a;cetic acid (l : 1) and dichlora'cetic acid. The molecular weight by osmotic method and the viscocity with the Ostwald's viscocimeter were measured in the dichloracetic acid solution， and the polymerisation degree and the intrinsIc vIscocity were determined， the molecular weight M. W. = 22，400， the polymerisatiol1 degree n = 316， the il1trinsic viscocity問]=0，292.The pyrolysis of N-carbothiophel1yl-司DL-alal1ineby thermoblance showed that the decompositiol1め occuredat adout 1400C gradually， at a:bout 1500C swiftly and at 160-1700C suddenly and at last the residue came close to the poly-DL-alanine (N = 19，72が〕il1 it's nitrogen contel1t but it was di臼cultto take a value in accordance with the theoretical， al1d the polymer gave always a litle lower value. N-carbothiophenyl-DL-alanine was kept at 100 こ士 1 oC for 2 .5hours under the reduced 持Itwas published in the ]an. of the Chem. Soc. of ]apan 15， 643-645 (1954) (in Japanese) 1) A. Lindenmann， N. H. Khan， K回日ofmann，J. Am. Chem. Soc. 74 476 (1952) 2) J. Noguchi， M. Asai， S.Ishino， T. Hayakawa， Jan. of the Chem. Soc， of.Japan 75， 642 (1954). 3) J. Noguchi， Jan. of the Chem. Soc. of Japan 74， 962 (1953) Fig. 1. 76 ]. NOGUCHI， S.ISHINO and T. H，RONO pressure of 9 mm Hg and after the COllstant weight was obtained， the sample was taken out. 1 t was powder and N = 18.35μWhen it was heated 丘gainat 2500土 lOCfor・1.5hours， itwas N = 19.54，% and came close to poly一DL-alanIlein its nitrogen content. When Nー ど一DL-alaniロewas heated at 200こと lOC for about 4 hours， a part of white plate crystal sublimed and the residue was brown of the polymer. The vvhite plate crystal did not show Biuret's reaction and was found to correspond to alanine diketo.piperazine， to judge from its nitrogen 呂nalysisand its picrate. The brωown powdered polymer was hygroscopic and N = 18 The n1.onomer was heated at 150土 rC for 4 hours i.n toJuene with a sealed tube. It was dissolv吋 intoluene and then almost gelatinized. After filtration， washing with toluene and ether， the polymer was dτied. It was N二 16.48;"0.When heated at 200土1 oC fo1' 3 homs in it vvas r¥J = 17 . 81 ;7~. Vvhen heated at 180 oC fo1' 8 hom・sin toluene and then at 2500C fo1' 2 hours， itwas N = 18.14クムThe:弓e 可i7'1ere soluble in a litle soluble 1n water and showed cl告a1'Biuret's reaction. Lindenul.3'nn etc.1) showed the 1'eaction in tl前 watersolution of N-ca1'bot-este:r 』一一一一-*->consideration of the ahove rea:etion. 3;nd of the results which did not show any tracθ of thiophenol in the the formuIa of th出合 polvmerswould be as follows 中一 l NH-CH-CONCHCO (-NHCHCO-¥OH 己H:J とH3 ¥ CHs んThe formula to tI1e expe1'imental r令sultsas the following shows回n 1234567 Calc. N% 1 16.35 1'7.1 17.52 17.86 18.12 18.30 18.47 19.72 anal. N% I 16.48 一一 17.81 此 14 此 35 札 54It is na:tural that some analytical va:lues take the intermediate of the theoretical， because each polyn悶 wasnot a pm唱esubstance having吐lesame polymerisation degree. But call be c'1assified as above. After a1， in the preparation of N-carboi:吐h註一DL一alan加e，the solution polyme1'isa:tion at low temperature gave good 1'esult as in other cases. Poly-DL-alanine--N-carbothiophenyl-DL-alanine 2.25 g was dissolγed in benzene 70 cc containing pyridille 7.9 g and polymerized at 60 oC fo1' 1000 ho1.1:陪 ina sealed tube. After several some opaque fibrous precipitate separated out and after Stu必"eson the Synthesis 0/ Frotein Analogus (Fart V) 77 several houndred hours a large amount of protein-like precipitate was obtained. It was cen仕ifugedafter 1000 hours， washed wi仕1a1cohol and ether， and dried. It was white powder. Yield 0.503 g (70.8% of the theoretical). Clear Biuret's reaction was observed. N arialysis found N = 19.91μ for (C3HsON)n calc. N=19.72% Molecular weight It was measured by'仕leosmotic rnethod using Meshizuka's aparatous.めThe polymer 0.0521 g was dissolved in dichlor-acetic acid and the total volume diluted to 10 cc and measured at 30土 O.lOC.ConCentration C = 5.21g/L， Specific gravity p = 1.485 Osmotic press.π=3.89 cm=5.75x10-3 atm. Molecular weight M. W.=22，400， Polymerisation degree nキ 316Polymerisatz'・'on 0/ j¥んcarbothiothenyl一'DL-alanineat Izμ te1r.ゲerature一一(1)N-carbothiophenyl-DL-alanine 1 g was taken in a test tube and heated at 150:t 1 ocfor 2.5 hours in 9 rnm Hg vaCcum. Hygroscopic powder 0.316 g was obtained. N analysis found N = 18.35 % co-一一一Ior l l ， ‘ NHCHCONCHCO (-NHCHCO-¥OH ca1c. N = 18.30% 己H3 CH3 ¥. CH3 ) 6This sample was heated rnore at 250:l: 1 ocfor 1.5 hours. It was sornewhat hygroscopic. N analysis found N = 19.54μ for くC3HラON)ooca1c. N = 19.72% (2) N-carbothiophenyl-DL-alanine 19 was taken in a test tube and heated at 200 土 rC for 40 rninuts in 2 rnm Hg vaCc'um. Some white crystal sublirned on the wall and brown polymer W'as obtained. When the brown polyrner was washed with water， alcohol and ether， itbecame brown powder. Yield 0.2 g. Analysis of white crystal found N = 19.74μ for (C3H50N)2 ca1c. N = 19.72.% It was dissolved in water， had amrnonium picrate solution added to it. It gave yellow precipitate. Biuret's reaction was not observed. It rnust be diketopiperazine. Analysis of brown polymer fOlUld N = 18.36 % co--一一lfor NHCHCO自CHCO/-NHCHCOーヘ OH ca1c. N =18.30% 6H3 CH3 ¥. CH3 )6 (3) N-carbothiophenyl-DL-alanine 0.3 g was dissolved in toluene 10 cc and heated at 150:l: 1 ocfor 4 hours in a sealed tube. It was almost solidified in about one hour of the first reaction. It was washed with toluene and ether， and dried. N analysis found N = 16.48，% の G.Meshizuka， The Chemistry of Highpolymer 6， 305 (1949) 78 J. NOGUCHI， S.ISHINO and T. HIRONO CO-一一「for :rJmCHCOおCHCONHCHCOOH cale. N = 16.35% 己H3 己H3 とH3(4) N-carbothiophenyl-DL-alanine 1 g was dissolved in xylene 10 cc and hea，ted at 2ω:t 1 oc for 3 hours in a sealed tube. It was廿'eatedwith a:1cohol. N analysis found N = 17.81% 一一CO-for iJmICOTi-CHco--/ーNHCHCOー¥OHωc. N=17働己H3 とH3 ¥. CH3 人(5) N-carbothiophenyl-DL-alanine 2 g was dissolved in toluene 20 cc and heated at 1800C for 8 hours and then at 250 oc for 2 hours. When it was washed with a1cohol， it became white powder. N analysis fou;nd N=18.14% Z f 「co--| ‘NHCHCONCHCO~NHCHCO-\OH calc. N=18.12% 己H3 とH3 ¥ CH3 )5 

Studies on the synthesis of Protein Analogus (PartV)

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Studies on the synthesis of Protein Analogus (PartV)

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