Furukawa, Kiyohisa

Oda, Ryohei

Kyoto University Research Information Repository

Title Polymerisation of Phenyl Glycide Ether andThioepichlorohydrinrAuthor(s)Furukawa, Kiyohisa; Oda, RyoheiCitation京都大学化学研究所報告 (1952), 30: 50-52Issue Date1952-09-30URL http://hdl.handle.net/2433/74453RightType Departmental Bulletin PaperTextversionpublisherKyoto University   Among these, the condensation product with  mono-t-butyl-p-cresol showed the highest  activity, which was superior to commercial  2,6-di-t-butyl15-cresol. The condensation products with  mono-t-butyl-o-cresol and  mono-t-butyl-m-cresol, respectively, showed some activities, but other products did not show high activities.    Some of the polynuclear  alkylphenols previously reported, that is con-densation products of  dimethylol-p-cresol with o-cresol (C-3), thymol (C-5), eugenol (C-6), p-hydroxyanisole  (C-7', respectively, as well as the condensa-tion product of eugenol and formaldehyde (E-2) were divided into three or four portions with different molecular weights by fractional precipitation with the aid of acetic acid and water. In the case of (C-3), (C-5), (C-6), (C-7), a portion with molecular weight of  300-503 were most effective. An anomaly was observed in the case of (E-2), that is, the monomethylolated product of eugenol,  i. e., eugenotine alcohol, m. p.  36C, was the highest in the activity.    The effects of these compounds to the stability of vitamine A were in-vestigated by G. Katui in the Laboratory of Prof. R. Takata. The results, which coincided with  our ones, will be published elsewhere.  16..  Polymerisation of Phenyl Glycide Ether  and Thioepichlorohydrinr                   Kiyohisa FURUKAWA and  Kyohei ODA                                (Oda Laboratory) A. Phenyl Glycide Ether  (P.G.E.)    1) Synthesis    P. G.  E. was prepared by the method of Boyd and Marie (J. Chem. Soc., 93, 838, (1908) ) according to the following reaction:            OH! CI CH2CH-CH2--N---n/\‘0-CH0.,                                          CH-CH N/\—/  0  0    2) Polymerisation     Exp.  Polym.  . Polym. Catalyst Mol. wt.       No. temp. CC) time (hr) (%)  (C  ryoscobic  method)  I  120-130 18 NaOH (5) 1357    2  I/  791  a (5) 1844    3  80— 90  181  n  (1) 1816     4 120-130  47)  I/ (1) 1279   5  241 KOH (5) 1531    6  I/ 14  ii(1) 1120   7  v 65  ti (1) 923    A brown, soft polymer was obtained, when the monomer was treated with molten and powdered KOH or  NaOH as catalyst in a sealed tube. It is  im-                            ( 50 )portant that the polymerisation must be carried out in the dry  state, The polymerisation may be assumed to proceed as  follows  :             0-CH2 CH  CH2 Alkali                               ).  CH-CH  -0  -CH-CH2-0  -CH -CH2,“ •  di:,  CH2  O  /\  /\  /\         I I)    3) Application    As the end group of  P.  G.  E. polymer is thought to be OH-group, we tried to prepare a non-ionic surfactant  by'reacting ethylene oxide upon the poly-mer.    The surface tension of this product was as  follows  :              1% 0.5 0.2 0.1 0.05 0.02 0.01 pure water (16'C)   dyne/cm 51.6 51.9 52.3 53.2 53.9 55.9  58.7 73.34 B. Thioepichlorohydrin (T. E. C.)    1) Synthesis  Cl-CH2-CH-C112  t.NH2CSNH2.--*CI-CH2-CH-CH2  /  /  O  0    According to the above course,  T.  E. C. was prepared by the aid of Davies' report (J. Chem. Soc., 1050, (1946) ).    2) Polymerisation    Contrary to the ordinary ethylene sulfide derivatives,  T.E.C. was not polymerized by alkali catalysts. We have succeeded in its polymerisation by adding a few drops of  112SO4 as catalyst at ordinry temperature.    The polymerisation can be considered to proceed as  follows  :  n2sot  S  CH-cH2-S-CH-cH2            /  CI-12  CR2  C112                   CI  \  CI  ix CI   When 5g. of  T.  E.  C. was warmed  with a drop of  H2SO4, polymerisation occured spontaneously and a dark brown slightly mobile resinous product was obtained.    On the other hand, gradual polymerisation at ordinary  temerature resul-ted a colourless, transparent, soft resin.    The former is soluble in  benzene and the molecular weight is about 1000 (by cryoscopic method). The latter is soluble only in CHC13 and so we cannot determine the molecular weight. Quantitative analysis of Cl of the colour-less  resin is as  follows:         Calcd.  32.72%; Found 32.68%    3) The reaction between T.  E.C. resin and aniline.                            C  51  )                                  R               Resin Aniline CIICIaReact•eact.Product                                         time.  temp.              2.7g. 11g.  20g. 21 hr. b. p. of 3.6g.  CHC13    According to the above details, light yellow and brittle resin was formed. Theoretical value of N contents calculated from the weight which increased in the product was 6.11%, and analytical value was 6.14%. From this result, it is apparent that 63% of Cl was replaced byaniline.   17. Studies  oa. Cobalt  Pdetabolism of Bacillus subtilis by  UArig  Co°            Shozo TANAKA, Yasuo SAWADA and Takuro YAMAMOTO                                (K. Kimura Laboratory)    Among many microbes,  Streptomyces griseus and Bacillus  subtilis are reported to be the good producers of vitamin B12. Microorganisms are expected that they absorb cobaltous ion from the culture media  and synthesize this vita-min. These investigations were undertaken with the intention of explaining physiological functions of vitamin B12 and other cobalt containing substances for microoranisms.  Cpm  .14  2000 8.0                                                       . count-sof                                                     acten4(  10001- b ce  • 70  BOO  •  "60 •  &00  MO  We,:9kt  of 5.0  bacter:a/  cell              400             200        1 I 1                     24  4S  72 96 120  1411           Fig. 1. Absorption of  Co" by bacillus subtilis (in  250  ml. medium).    The chemical constituents of bacillus  subtilis, grown on Waksman's media containing 2 p.  p.m. radioactive  Co60, and of the remaining media were pre-cisely analysed during the growth. Total cobalt content in the unit weight of bacterial cells was found to increase with the growth.  Co" in the 75  % alcoholic extract, however, showed the maximum  after 48 hr.  of inoculation. The amount of vitamin  B32 in bacterial cells and remaining media were also estimated by means of colorimetric determination of cyanide in  cyanoco-                           C 52 )

Polymerisation of Phenyl Glycide Ether and Thioepichlorohydrinr

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Polymerisation of Phenyl Glycide Ether and Thioepichlorohydrinr

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