ーノートー
239ナ ト リ ウ ム 法 融 後 ガ ス ク ロ マ ト グ ラ フ ィ ー に よ る
フ ェ ナ ン ト レ ン 中 の ジ フ ェ ニ ー レ ン ス ル ブ イ ド の 同 定
ジフェニーレンスルフィドの保持時間はフェナントレンのものに近いため，そのままでは同定に困難する ことがある。そこでジフェニーレンスルフィドをナトリウム溶融してピフェニールに変化させるとガスクロ マトグラフィーによる同定が容易になることを見出した。Identification of Diphenylenesulfide in Phenanthrene by Gaschromatography after Na fusion
Kikuo USUI*
，
Kiyoshi KIHARA * OutlineDiphenylenesulfide (DPS) has a retention time v巴ryclose to that of phenanthrene. And so we find difficulties some times to identify the contaminant in phenanthrene on gaschromatography. The authors establish巴d a new method for this purpose.
This method consists of two processes of Na fusion and gaschromatography. DPS is decomposed to biphenyl which we can identify very easily instead of DPS on gaschro. matography.
Introduction
!)
G. Schroter and his coworkers gave an evi. dence of the DPS present in phenanthrene co -mmercial by Na fusion. B. D. Blaustein and ot
21
hers referred to the desulfurization of ph巴町 田 nthreneby the same method. Itseems not so easy to find any other literatures concern -ed in this problem besides these two. Usually DPS appears at the foot of phenanthrene peak on gaschromatography (GLC). But it's some-what difficult to discriminate theDPS peak， if contain巴dsomuch as more than 1% or so.
Owing to this reason Na fusion was used here to convert DPS into biphenyl and detect its sharp peak on the chart. The reaction occurs as follows.
cc
ヌコ斗←0-0十ぬ
2S*
Department of Applied Chemistry But we should be very precarious for pro -tecting the interference by the decomposition products of phenanthrene during Na fusion. The result of investigation of this problem made us sure that biphenyl was not generated from any one of phenanthrene，
fluorene and pyrene by this process.2 Experimental process
Various kinds of phenanthrenen were zone -refined for 3 days with an elevation 'speed of 4. 4 c
冗
rand cut off into eight or nine section，
which were numbered L 2・
aー
・
.8fromthe top of zone-refining. About 10 mg of the selected section described in the next para -graph was added to0.5~O.8g metallic Na in a small test tube and heated directly over a Bunsen burner under continuous shaking until the contents were colored black soon after. The benzene extract was dehydrated with CaCb and evaporated. The residual powder
3)
was injected by the author's method in the GLC.
240 白 井 喜 久 雄 ・ 木 原 清
3
Identification of Sulfur compound in PhenanthreneOnly one pair'of charts were s巴lect巴d from
each of four companies' ph巴nanthr巴nesfor the
sake of saving spac巴. And th巴huge peal王of '
major component， phenanthrene was also cut off in every chart， but written with figures responsible for th色 lengthand width in the
middle of the peak.
① ※ 4 3 2
。
retention time (min.) Fig. 1 GLC of the desulfurization product of TZ8 Yanagimoto 5DH FID column : stainless steelO. 75m， O. 3cm PEG 20M 2% on celit巴545 Ct 150'C N2 7.5m l/min n u q o o 自 H ハ リ F D η L K 配 /ノ S 109 Q Air 0.9 l/min Att. 1 2 1 : Biphenyl*
Injection shock T: compahy， Z8: zon巴-refinedsection number from the top A : afte Na fusion B:b巴fore // 15. 5X 4 cm一
A B。
15.OX 3 ② ※ 5 4 3 2 ret巴ntiontime (min.) 1 Fig. 2 GLC of the desulfurization product of KZ6 conditions : th巴samewith Fig. 1 1: Biphenyl 16X 3臼n A B 3 2 retention time (min.) Fig.3 GLC of the desulfurization product of NZ6 conditions : the sam巴withFig. 1 except for Ct : 1200C 1 : Naphthalene 2: Biphenyl 3 : Methylbiphenyl ※ ①。
ナトリウム溶高直後ガスクロマトグラフィーによるフェナントレン中のジフェニ{レンスルフィドの同定 241 ① A B 3 2 l
。
retention tim巴 (min.) Fig. 4 GLC of the desulfurization product ofYZ6 conditions : the same with Fig.3 1: Biphenyl4
Conclusion Na fusion is a simple and convenient me-thod for the determination of DPS， one of the contaminants in phenanthren巴. But the appli-cation of this method is limitted to phenanth-rene， because of its stability against Na fusion. In every case a blank test should be tried along with the sample. Literature 1) B. D.Blaustein and others: Anal.Chem.，
