1-メチル-4-ピペリドン 化学特性,用途語,生産方法
外観
微黄色～黄色の液体
用途
有機合成原料。
化学的特性
clear yellow to orange liquid
使用
1-Methyl-4-piperidone, are widely used in artificial fibre industry. They are polymerizable and used as nylon precursors. They have excellent applications as solvents and as intermediates for organic synthesis. They are used in the aqueous carrier medium and amide penetrants in inks and water soluble paints.
主な応用
N-Methyl-4-piperidone can be used as a reactant to prepare:
Spiropiperidine rings by reacting with malononitrile and electrophiles or Michael acceptors.
(3E,5E)-1-Methyl-3,5-bis(phenylmethylene)-4-piperidinone by reacting with benzaldehyde via Michael addition, followed by intramolecular O-cyclization/elimination sequential reactions.
N,N′-Dimethylbispidinone by utilizing a double Mannich condensation method.
製造方法
[JACS (1948) vol 70 p 1820] for the synthesis of 1-methyl-4-piperidone:
To a one-liter flask containing 350 ml of 20 % hydrochloric acid was added 86 g. of 1-methyl-3-carbethoxy-4-piperidone hyrdrochloride. After refluxing for one hour, the ferric chloride reagent gave no coloration. The solution was evaporated to dryness on a steam-bath at 10 mm. pressure. The solid product, heated at 100 °C for 4 hours at 0.1 mm and further dried over solid KOH for 24 hours, weighed 57.7 g, m.p. 80 - 120 °C.
Although this melting range goes above that of the pure comound 0.45 of crude material dissolved in 90 ml. of hot acetone gave 0.40 g of pure compoundd melting at 93 - 95 °C. Other samples of crude piperidone hydrochloride showed even higher melting points than the one mentioned above, yet this apperently impure material always gave good yields of sharp melting product when recrystallized.
純化方法
It is best purified by fractional distillation The hydrochloride of the hydrate (4-diol) has m 94.7-95.5o, but the anhydrous hydrochloride which crystallises from CHCl3/Et2O has m 165-168o (164-167o) and can also be obtained by sublimation at 120o/2mm. The oxime has m 130-132o (from Me2CO). The methiodide crystallises from MeOH, the crystals with 1MeOH have m 189-190o, and the solvent-free iodide has m 202-204o(dec). [Lyle et al. J Org Chem 24 342 1959, Bowden & Greeen J Chem Soc 1164 1952, Tomita Yakugaku Zasshi (J Pharm Soc Japan) 71 1053 1951, Beilstein 21 IIII/IV 3183, 21/6 V 419.]
1-メチル-4-ピペリドン 上流と下流の製品情報
原材料
準備製品
N-Methyl-3-carbomethoxy-4-piperidone hydrochloride
4-クロロ-1-メチルピペリジン
2-AMINO-6-METHYL-4,5,6,7-TETRAHYDROTHIENO[2,3-C]PYRIDINE-3-CARBONITRILE
4-ヒドロキシ-1-メチルピペリジン
5-メチル-4,5,6,7-テトラヒドロチアゾロ[5,4-c]ピリジン-2-カルボン酸塩酸塩
メブヒドロリン
2-アミノ-6-メチル-4,5,6,7-テトラヒドロチエノ-[2,3-C]ピリジン-3-カルボン酸エチル
5,6,7,8-テトラヒドロ-6-メチル-1,6-ナフチリジン-3-アミン
4-METHYLENEPIPERIDINE
4,4'-ジ(4-ピリジル)ビフェニル
5-メチル-4,5,6,7-テトラヒドロ[1,3]チアゾロ[5,4-C]ピリジン-2-アミン
4-クロロ-3-ヨードピリジン
N-Hydroxy-4-[(1,2,3,4-tetrahydro-2-methyl-5H-pyrido[4,3-b]indol-5-yl)methyl]benzamide 2,2,2-Trifluoroacetate
1-(1-メチル-4-ピペリジル)ピペラジン