シクロペンタジエン 化学特性,用途語,生産方法
解説
シクロペンタジエン,無色の液体．融点－85 ℃，沸点41 ℃．d1540.8048．n20D1.4440．プロトンが引き抜かれて生成するシクロペンタジエニドイオンは，芳香族性を示す．シクロペンタジエンはディールス-アルダー反応の共役ジエンとして有機合成に広く用いられるほか，一群のシクロペンタジエニル錯体が知られている．工業的用途としては，エチレンプロピレンゴムの第三成分エチリデンノルボルネンの合成，農薬原料などがあり，またジシクロペンタジエンから誘導される化学製品が，近年，種々開発され，新しい石油化学工業分野を広げつつある．
森北出版「化学辞典（第2版）
用途
試薬
製造
シクロペンタジエン,コールタールの低沸点留分，ナフサ分解副生油中に存在する．シクロペンタジエン,室温で容易に二量化してジシクロペンタジエンとなり，これを熱分解するとシクロペンタジエンを再生するため，通常，二量体として製品化される．工業的には，ナフサ分解副生 C5 留分中に10～25％ 含まれるシクロペンタジエンを十分に反応させた後，蒸留分離し，精製してジシクロペンタジエンの製品とし，必要に応じてこれを熱分解し，シクロペンタジエンを得る．
化学的特性
1,3-Cyclopentadiene is a colorless liquid that dimerizes
easily in the presence of peroxides and trichloroacetic acid
to a colorless solid.
物理的性質
Colorless liquid with a turpentine-like odor. Odor threshold concentration is 1.9 ppm (quoted,
Amoore and Hautala, 1983).
使用
manufacture of resins; in organic synthesis as the diene in the Diels-Alder reaction producing sesquiterpenes, synthetic alkaloids, camphors.
定義
A cyclic hydrocarbon made by
cracking petroleum. The molecules have a
five-membered ring containing two carbon-
carbon double bonds and one CH
2
group. It forms the negative cyclopentadienyl
ionC
5H
5-, present in sandwich compounds,
such as ferrocene.
調製方法
This compound occurs in the C6–C8 petroleum distillation
fraction, and in coke oven light oil fractions. It is
produced by dehydrogenation of cyclopentadiene or monomerization
of its dimer.
一般的な説明
1，3-Cyclopentadiene is a colorless liquid with an irritating, terpene-like odor. Bp: 42.5°C; Flash point: 77°F. Density: 0.805 g cm-3.
反応プロフィール
1，3-Cyclopentadiene is incompatible with strong oxidizing agents. Ignites on contact with oxygen (O2) and ozone (O3). Explodes on contact with fuming nitric acid or a mixture of sulfuric acid and nitrogen tetroxide. Reacts vigorously on contact with potassium hydroxide and other strong bases. Mixtures with air are explosive. Presents a moderate explosion hazard when exposed to heat or flame. Decomposes violently at high temperature and pressure. May form explosive peroxides in storage. Undergoes a spontaneous dimerization at room temperature to give DI1，3-Cyclopentadiene (C10H12, CAS No: 77-73-6), which is a low-melting solid (melting point: 32.5°C). The reaction is strongly exothermic (Hazardous Chemicals Desk Reference, p. 360 (1987)), but occurs sufficiently slowly that 1，3-Cyclopentadiene can be said to be stable at room temperature. The dimerization accounts for the partial or complete solidification of liquid 1，3-Cyclopentadiene in storage. Polymerization occurs more rapidly and extensively at higher temperatures. When heated to 180-200°C, 1，3-Cyclopentadiene gives poly1，3-Cyclopentadiene, a white waxy solid. Stronger heating breaks down poly1，3-Cyclopentadiene and re-generates the monomeric 1，3-Cyclopentadiene as a vapor. The vapor decomposes violently at higher temperatures and pressures.
健康ハザード
Cyclopentadiene exhibited low toxicity inanimals. Inhalation produced irritation of theeyes and nose. A 3-mL amount injected subcutaneouslyinto rabbits resulted in narcosis,convulsions, and death (von Oettingen 1940).A dose of≤ 1 mL was nontoxic. Repeatedexposure to 500 ppm caused liver and kidneyinjuries in rats; but longer repeated exposuresto 250 ppm produced no such effects in testanimals (ACGIH 1986). An oral LD50 valuein rats for the dimeric form has been recordedas 820 mg/kg (Smyth 1954).
火災危険
Flammable liquid; flash point (open cup)
32°C (90°F); fire- extinguishing agent: dry
chemical, foam, or CO2; a water spray
may be used to cool the surroundings. Prolonged
exposure to air may cause peroxide
formation.
化学性质
沸点41℃の揮発性液体であるが，室温付近で容易に二量化し，沸点170℃のジシクロペンタジエン（DCPD）として存在する。
安全性プロファイル
Low toxicity by
ingestion. A dangerous fire hazard when
exposed to heat or flame; can react with
oxidizing materials. Moderate explosion
hazard in the form of gas when exposed to
heat or by chemical reaction. It decomposes
violently at hgh temperatures and pressures.
dimerization is highly exothermic.
Explosive reaction with fuming nitric acid,dinitrogen tetroxide, sulfuric acid. Reaction
with nitrogen oxide + oxygen forms an
explosive product. Reaction with oxygen
forms a flame-sensitive explosive product.
Ignites on contact with oxygen + ozone.
Reacts vigorously on contact with potassium
hydroxide. Incompatible with oxides of
nitrogen, sulfuric acid. When heated to
decomposition it emits acrid smoke and
fumes.
職業ばく露
Cyclopentadiene is used as an inter-
mediate in the manufacture of resins, insecticides, fungi-
cides, and other chemicals.
環境運命予測
Biological. Cyclopentadiene may be oxidized by microbes to cyclopentanone (Dugan, 1972).
Chemical/Physical. Dimerizes to dicyclopentadiene on standing (Windholz et al., 1983).
輸送方法
UN1993 Flammable liquids, n.o.s., Hazard
Class: 3; Labels: 3-Flammable liquid, Technical Name
Required.
合成方法
ナフサ分解のC5留分として生成する。CPDは，その二量化，分解反応の容易さを利用し，DCPDとして他のC5留分と分離した後に分解されて得られる。
純化方法
Dry the diene with Mg(ClO4)2 and distil it rapidly as it dimerises readily at room temperature. It should be used immediately or stored in a Dry Ice or an ice-salt bath. HIGHLY FLAMMABLE. [Moffett Org Synth Coll Vol IV 238 1963.] Cyclopentadiene Dimer (4,7-methano-3a,4,7,7a-tetrahydroindene) has [77-73-6], M 132.3, m 33o, b 170o/atm, and d2 5 0.986; add ~0.05% of 2,6-di-tert-butyl-4-methylphenol as stabilizer. Cyclopentadiene is prepared when required by de-polymerising the technical grade dimer by heating it carefully under a fractionating column [Wilkinson Org Synth Coll Vol IV 467 1963], as described by Moffett (above reference), or by adding the dimer at a steady rate onto mineral oil heated at 240-270o (Korach et al. Org Synth 42 50 1962). [Beilstein 5 II 391.]
不和合性
Vapors may form explosive mixture with
air. Converted (dimerized) to higher-boiling dicyclopenta-
diene upon standing in air and @ 32
F/0
C; this conversion
may be violent and exothermic; this reaction is accelerated
by peroxides or trichloroacetic acid. Reacts violently with
potassium hydroxide. Violent reaction with strong oxidi-
zers; strong acids; dinitrogen tetroxide; magnesium.
Incompatible with oxidizers (chlorates, nitrates, peroxides,
permanganates, perchlorates, chlorine, bromine, fluorine,
etc.); contact may cause fires or explosions. Keep away
from alkaline materials, strong bases, strong acids, oxoa-
cids, epoxides, alkaline earth metals, nitrogen oxides. May
accumulate static electrical charges, and may cause ignition
of its vapors.
廃棄物の処理
Dissolve or mix the material
with a combustible solvent and burn in a chemical incinera-
tor equipped with an afterburner and scrubber. All federal,
state, and local environmental regulations must be
observed.
シクロペンタジエン 上流と下流の製品情報
原材料
準備製品
metallocene catalyst
(1R,1β,4β)-2-アザビシクロ[2.2.1]ヘプタ-5-エン-3-オン
titanium(zirconium)dialkyl endo-silicon cyclopentadiethyl tert-butylamine
5-エチリデン-2-ノルボルネン
フェロセン
1α,2α,4β,5,6,7β,8,8-オクタクロロ-2,3,3aα,4,7,7aα-ヘキサヒドロ-4,7-メタノ-1H-インデン
METHYL A YCLOPENTYLMANDELATE
1-Methyl-3-(a-cyclopentylmandeloyloxy)pyrrolidinehydrochloride
5-ノルボルネン-2,3-ジカルボン酸無水物
りん酸7-クロロビシクロ[3.2.0]ヘプタ-2,6-ジエン-6-イルジメチル
オラキンドクス
2-クロロ-5-(クロロメチル)ピリジン
ヘキサクロロシクロペンタジエン
N-フェニル-N'-(1,2,3-チアジアゾール-5-イル)尿素
ジシクロペンタジエン
ジチオりん酸O,O-ジメチルS-[(5-メトキシ-2-オキソ-1,3,4-チアジアゾール-3(2H)-イル)メチル]
1-メチル-1,3-シクロペンタジエン
6,7,8,9,10,10-ヘキサクロロ-1,5,5a,6,9,9a-ヘキサヒドロ-6,9-メタノ-2,4,3-ベンゾジオキサチエピン3-オキシド
1,5-ペンタンジオール
Basic Yellow 24
ジルコノセンクロリドヒドリド
シクロペンテン
シクロペンタン
ビペリデン
マロチラート
Catonic Dark Yellow 2RL
2-アザビシクロ[2.2.1]ヘプタ-5-エン-3-オン
1，2，3，4-tetrachlorocyclopentane