Isoshima, Toshizo

Nodzu, Ryuzaburo

Kyoto University Research Information Repository

TitleReactions of Ketene with Phenol, Resorcine, Phloroglucine andDimedoneAuthor(s)Nodzu, Ryuzaburo; Isoshima, ToshizoCitationBulletin of the Institute for Chemical Research, KyotoUniversity (1954), 32(3): 139-140Issue Date1954-05-31URL http://hdl.handle.net/2433/75440RightType Departmental Bulletin PaperTextversionpublisherKyoto University NOTES      Reactions of Ketene with Phenol, Resorcine, Phloroglucine                          and Dimedone                    Ryuzaburo NoDZV, Toshizo IsosHIMA*                               (Nodzu Laboratory)                            Received June 25, 1954    The reactions of ketene with phenol, resorcine, phloroglucine and dimedone have been studied.    (1) Without catalyst, ketene gave always 0-acetyl derivatives of them.    (2) With sulfuric acid, pyridine or sodium acetate as catalyst, 0-acetyl de-      Table 1. Reactions of ketene with phenol, resorcine, phloroglucine and dimedone. ___,. -------1 OHOHOH Me.  Phenols i1\/\—OH (I)/\\/\\/\ jmVI     React.II I II Iii I111/\% Catalyst Temp. Products \j\%OH HO—\/HOI                                                          OH Name(2)CI) 0 —x i  0*     Low—YieldO—80—----— 55   None---- -- -- --—---             Name —  O(mono) O(di) O(tri)  ,----------- 0*  High Yield67 , 98272         Name 0* — O(tri)0*  Na (i) Low— Yield 6829 61  1HighName O* O*(mono, di) resine0*  SaltYield — 7478 61        Name 0— resinex         Low———— H—--Yield 85  ,SOa        Name —0(di) resine resine     High —Yield .. I---------- —77  Name 0 --—----- O(tri) x  \. Low---------- Yield — 8714  II\fe. High Name —0(di) O(tri) 0*        Yield 8826  61     Name —-----------------------x—         LowYield AcONa -- —`— Name ———O*          High    Yield (44     (1) React. Temp.: Low—Cooling with ice or room temp. (solvent: ether).                       High—Warming on a steam bath (solvent:benzene).   (2) 0 : 0-acetyl derivative. 0(mono) : 0-mono-acetyl derivative. O(di) : 0-di-acetyl derivative. O(tri) : 0-tri-acetyl derivative. 0* : 0-acetyl derivative with a small amount of C-acetyl derivative, which seems            to be present although not confirmed. 3) x : No reaction.   (4) Yield (%) : Theoretical yield.    (5) Na-Salt : Treated with 20% H2SO., after the reaction. ( 139 )                             NOTES rivatives were produced.    (3) In the reactions with their sodium salts, 0-acetyl derivatives were produced, containing a small amount of C-acetyl derivatives.    Some experimental results were cited in Tables 1 and 2.           Table 2. Some physical constants of 0-acetyl derivatives obtained from                    phenol, resorcine,  phloroglucine and dimedone.                                           Physical properties0 -acetyl derivative               m.p.b.p.20                 ('C)(°C)ni) OAc 2\1111.5200 II I(60 mm.) OAc /\135-71.5328 II I(7 mm.) OAc /\130-11.5034        II -0Ac(7 mm.)                 OAc A105-7—         Ac0J LOAc me\ „..,‘„ —0Ac      me/I I128-132 1.4814                                                L15 mm.) 01-1             Reaction of Ketene with Ethyl Acetoacetate                   in the Presence of Pyridine                           Toshizo IsosiumA*                                (NodzuLaboratory)                             ReceivedJune 25, 1954    In the presence of a very small amount of pyridine, Icetene was reacted with ethyl acetoacetate above -20°C, and a reaction product rich in 0-acetyl- (II), poor in C-acetyl ethyl acetoacetate (I), was obtained.                               ( NO )

Reactions of Ketene with Phenol, Resorcine, Phloroglucine and Dimedone

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Reactions of Ketene with Phenol, Resorcine, Phloroglucine and Dimedone

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