フェニルイソチオシアナート 化学特性,用途語,生産方法
外観
無色澄明の液体
溶解性
水に不溶。エタノール, エーテルに易溶。水に不溶。エタノール、エーテルに可溶。エタノール及びアセトンに溶けやすく、水にほとんど溶けない。
解説
フェニルイソチオシアナート，可燃性の無色の液体(着火温度38 ℃)．融点－21 ℃，沸点221 ℃，95 ℃(1.6 kPa)．d425"1.13．nD23"1.649．水に不溶，有機溶媒に可溶．アミノ酸と反応してフェニルチオヒダントインを生成する．アミノ酸の自動分析試薬(エドマン分解)に用いられる．催奇形性がある．
森北出版「化学辞典（第2版）
用途
フェニルイソチオシアネート (PITC、イソチオシアン酸フェニル)は、逆相高速液体クロマトグラフィーに利用される試薬である。PITCはオルトフタルアルデヒド(OPA)以下の感度で、自動化出来ない。OPAと異なり、第二級アミンを分析する事が可能である。
エドマン分解に使用されるエドマン試薬としても知られる。 リノグリリドの合成にも利用される。
製造
フェニルイソチオシアナート，種々の植物の種子油から単離されている．二硫化炭素，濃アンモニア，アニリンから生成するフェニルジチオカルバミン酸アンモニウムに硝酸鉛(Ⅱ)溶液を作用させると得られる．
毒性
LD50 87 mg/kg(マウス，経口)．
化学的特性
colourless to pale yellow liquid with a penetrating odour
使用
Phenyl isothiocyanate is the reagent of choice in automated Edman degradation systems. However, this reagent is highly toxic and for manual modification other reagents are preferred such as dimethy laminoazobenzene isothiocyanate (Chang, 1983; Wang et al, 2000) or trifluoroethyl isothiocyanate (Bartlet-Jones et al, 1994). This last reagent has the advantage of being volatile, so that the excess of reagent is easily removed by vacuum before MS analysis (Spengler, 1997). This compound was used successfully during seven successive cycles of manual cleavage coupled with MS analysis. Nevertheless, the high reactivity of such compounds seems to shows artefactual modification such as“acetylation' of the hydroxyl groups of the Ser and Thr. Allyl isothiocyanate shows better selectivity, but again this reagent is toxic and difficult to use in manual approaches (Gu & Preswich, 1997) .
定義
ChEBI: Phenyl isothiocyanate is an isothiocyanate having a phenyl group attached to the nitrogen; used for amino acid sequencing in the Edman degradation. It has a role as an allergen and a reagent.
製造方法
Synthetic procedure for phenyl isothiocyanate in 1-mol scale
Into a 2-L jacketed flask, 91.2 g of CS2 (1.2 mol) was dropwise added to a mixture of aniline (93.0 g, 1.0 mol) and K2CO3 (276.0 g, 2.0 mol) in 700 mL of water at room temperature within a period of 2.5 h. After the addition was complete, the mixture was stirred another 2 h. Then, the mixture was cooled to 0 °C, and a solution of 92.3 g of TCT (0.5 mol) in 450 mL of CH2Cl2 was dropwise added within 4 h. After the addition was complete, the mixture was stirred another 1 h to complete the conversion. The resulting mixture was basified to pH >11 with 250 mL of 6 N NaOH and yielded a clear solution. The organic layer was separated and the aqueous layer was extracted with 150 mL of CH2Cl2. The combined organic layers were dried over anhydrous Na2SO4, filtered, and the solvent of filtrate was removed via distillation under atmospheric pressure with a 25-cm Vigreux column. The residue was vacuum distilled and the desired product fraction was collected at 72–74 °C/1 mmHg. Finally, 127.0 g of colorless liquid (94%) was obtained.
生物学の機能
Phenyl isothiocyanate (PITC) is a well-established reagent in protein chemistry since its introduction in Edman degradation. PITC reacts with primary and secondary amines under alkaline conditions within 20 min. The resulting phenylthiocarbamyl (PTC) derivatives of the amino acids are stable and do not interfere with reaction by-products during chromatography. The absorption maximum is around 245 nm with a detection limit of 1 pmol.
Phenyl isothiocyanate may be employed as a derivatization reagent for high-performance liquid chromatographic (HPLC) analysis of various amphetamine derivatives in body fluids for forensic purposes.
一般的な説明
Phenyl isothiocyanate is an aromatic isothiocyanate. It participates in dehydration reactions of alcohols. It is widely used for synthesis of various biologically important heterocyclic compounds.
純化方法
It is insoluble in H2O, but soluble in Et2O and EtOH. If impure (due to formation of thiourea), then steam distil it into a receiver containing 5-10mL of N H2SO4. Separate the oil, dry over CaCl2 and distil it under vacuum. [Dains et al. Org Synth Coll Vol I 447 1941, Beilstein 12 IV 867.]
フェニルイソチオシアナート 上流と下流の製品情報
原材料
準備製品