フェロセン 化学特性,用途語,生産方法
外観
黄赤色〜赤褐色, 結晶〜粉末
溶解性
エタノールにやや溶けにくく、水にほとんど溶けない。
解説
フェロセン，融点173～174 ℃，沸点249 ℃．密度1.49 g cm－3．普通の有機溶媒に可溶，水に不溶．100 ℃ 以上で昇華する．反磁性で，酸の共存下で空気酸化すると，青色のビス(η5-シクロペンタジエニル)鉄(Ⅲ)イオン [Fe(C5H5)2]＋ を生じる．ほかの芳香族化合物と同じく，求電子反応が起こりやすい．
森北出版「化学辞典（第2版）
用途
ガソリンのアンチノック剤、ロケット燃料の燃焼助剤、医薬等の合成中間体、触媒、2.危険有害性の要約
構造
二つの五員環の配置はねじれ形(図(a))とされたが，結晶中－175 ℃ では，重なり形(図(b))であり，－109 ℃ までは重なり形に近いが，上下の五員環が約9°回転した配置をとっている．室温で，ねじれ形構造をとる証拠は得られていない．ガス状態では重なり形をとる．理論的には重なり形が2.78 kJ mol－1 だけねじれ形より安定である．一方，多くのメタロセンはおもにねじれ形であり，またペンタメチル置換体の[Fe{C5(CH3)5}2]はねじれ形である．Fe
2+ のかわりにほかの金属イオンの入ったものを総称してメタロセンという．
合成法
合成法には，無水塩化鉄FeCl3と臭化シクロペンタジエニルマグネシウムとの反応，FeCl2とシクロペンタジエニルナトリウムまたはシクロペンタジエニルリチウムとを反応させる方法，ジエチルアミンのような塩基の存在下にFeCl2とシクロペンタジエンとを反応させる方法などがある．
化学的特性
Ferrocene, a metallocene, is a bright orange
salt-like crystals from alcohol. Camphor odor.
物理的性質
Orange crystals; camphor-like odor; melts at 172.5°C; vaporizes at 249°C; sublimes above 100°C; thermally stable above 500°C; insoluble in water; soluble in alcohol, ether and benzene; also soluble in dilute nitric acid and concentrated sulfuric acid forming a deep red solution that fluoresces.
使用
Ferrocene
is used as a catalyst for vulcanization, acceleration, and
polymerization, as a chemical intermediate for polymeric
compounds such as high temperature polymers, as an antiknock
additive for gasoline, as a coating for missiles and
satellites, and as a high-temperature lubricant.
定義
ferrocene: An orange-red crystallinesolid, Fe(C
5H
5)
2; m.p. 173°C. Itcan be made by adding the ioniccompound Na
+C
5H
5- (cyclopentadienylsodium, made from sodium andcyclopentadiene) to iron(III) chloride.In ferrocene, the two rings are parallel,with the iron ion sandwiched betweenthem (hence the namesandwich compound: see formula).The bonding is between pi orbitalson the rings and d-orbitals on theFe
2+ ion. The compound can undergoelectrophilic substitution on theC
5H
5rings (they have some aromatic character).It can also be oxidized to theblue ion (C
5H
5)
2Fe
+. Ferrocene is the first of a class of similar complexescalled sandwich compounds. Its systematicname is di-π-cyclopentadienyliron(II).
調製方法
Ferrocene is produced from the reaction of cyclopentadiene
with reduced iron in the presence of metal oxides. There is
also a two-stage production process in which produced iron
(II)oxide (stage 1) is reacted with cyclopentadiene.
製造方法
Dicyclopentadienyliron may be obtained in a single-step synthetic route by heating cyclopentadiene with iron or iron pentacarbonyl at 300°C:
2C
5H
5 + Fe → (C
5H
5)
2Fe
Also, it can be prepared by the reaction of iron(II) chloride with cyclopentadiene in the presence of an alkyl amine or a similar base.
Another convenient method of preparing this π-complex of iron is a twostep process in which the first step involves preparation of cyclopentadienyl Grignard reagent, such as 2,4-cyclopentadienylmagnesium bromide C5H5MgBr which may then be combined with ferric chloride to yield dicyclopentadienyl iron:
3C
5H
5MgBr + FeCl
3 → (C
5H
5)
2Fe + 3MgBrCl
Another general method of preparation involves the reaction of cyclopentadiene with sodium metal or sodium hydride in tetrahydrofuran (THF). Addition of iron(II) chloride to this solution forms the complex dicyclopentadienyliron:
2C
5H
6 + 2Na → 2C
5H
5ˉ + 2Na+ + H
2
In 3:2 molar ratio of cyclopentadiene to sodium cyclopentene is obtained along with cyclopentadienidide (C
5H
5ˉ ) anion:
3C
5H
6 + 2Na → 2C5H5¯ + 2Na+ + C
5H
8
FeCl
2 + 2C5H
6Na → (C5H5)
2Fe + 2NaCl
一般的な説明
Orange crystalline solid or orange-yellow powder. Sublimes above 212°F. Camphor odor.
空気と水の反応
Sensitive to prolonged exposure to air and may be sensitive to light. Insoluble in water.
反応プロフィール
Ferrocene reacts violently with tetranitromethane. . Contact of tetranitromethane with Ferrocene under various conditions leads to violent explosion, [Trans. Met. Chem., 1979, 4, 207-208].
危険性
Moderate fire risk. Evolves toxic products
on decomposition and heating.
健康ハザード
Dicyclopentadienyl iron causes
changes in blood parameters and hepatic
cirrhosis.
The toxicological properties of dicyclopentadienyl
iron have not been extensively
investigated. However, it has been used as a
preventive and therapeutic iron deficiency
drug, and its utilization is listed as tolerable.
火災危険
Flash point data for Ferrocene are not available. Ferrocene is probably combustible.
安全性プロファイル
Poison by
intraperitoneal and intravenous routes.
Moderately toxic by ingestion. Questionable
carcinogen with experimental tumorigenic
data. Mutation data reported. Flammable;
reacts violently with NH4ClO4. When heated
to decomposition it emits acrid smoke and
irritating fumes.
職業ばく露
Used as additive in fuel oil; antiknock
agent in gasoline fuel; used in making rubber, silicone
resins, high-temperature polymers and lubricants; interme diate for high-temperature polymers; as a smoke suppres sant and catalyst
発がん性
Ferrocene was administered by
intramuscular injection at a dose of 5175 mg/kg/2 years.
By the criterion established by the Registry of Toxic Effects
of Chemical Substances (RTECS), ferrocene was an equivocal
tumorigenic agent and tumors were most evident at the
site of multiple injections.
輸送方法
UN1325 Flammable solids, organic, n.o.s.,
Hazard Class: 4.1; Labels: 4.1-Flammable solid.
純化方法
Purify it by crystallisation from pentane or cyclohexane (also *C6H6 or MeOH can be used). It is moderately soluble in Et2O and sublimes readily above 100o. Crystallisation from EtOH gave material m 172.5-173o. [Wilkinson Org Synth Coll Vol IV 473 1963, Miller J Chem Soc 632 1952.] It has also been crystallised from methanol and sublimed in vacuo. [Saltiel et al. J Am Chem Soc 109 1209 1987, Beilstein 16 IV 1783.]
不和合性
Violent reaction with ammonium per chlorate, tetranitromethane, mercury(II) nitrate. Incompa tible with oxidizers (chlorates, nitrates, peroxides, perman ganates, perchlorates, chlorine, bromine, fluorine, etc.);
contact may cause fires or explosions. Keep away from
alkaline materials, strong bases, strong acids, oxoacids,
epoxides.
Peroxomonosulfuric acid. Decomposes @≧465 ℃.
フェロセン 上流と下流の製品情報
原材料
準備製品
[1,1'-ビス(ジ-tert-ブチルホスフィノ)フェロセン]パラジウム(II)ジクロリド
1,1'-フェロセンジカルボキシアルデヒド
1 1'-BIS(DIPHENYLPHOSPHINO)FERROCENE
1,1'-ビス(ジフェニルホスフィノ)フェロセン
1,1'-ジブチルフェロセン
1,1'-ビス(ジ-tert-ブチルホスフィノ)フェロセン
Ferrocene derivative
dibuty cebacate with ferric chloride
ブチルフェロセン
1,1'-ジメチルフェロセン
1,1'-ジアセチルフェロセン
1-ジフェニルホスフィノ-1'-(ジ-T-ブチルホスフィノ)フェロセン
1,1'-ビス(ジイソプロピルホスフィノ)フェロセン
Chlorocarbonyl ferrocene
1,1'-ジエチルフェロセン
メチルシクロペンタジエニルマンガントリカルボニル
ベンゾイルフェロセン
フェロセンボロン酸
1,1'-binaphthalene-2,2'-diyl diacetate
アセチルフェロセン