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ピロリジン
ピロリジン · テトラヒドロ-1H-ピロール · プロラミン · テトラヒドロピロール · テトラメチレンイミン · テトラヒドロピロ-ル · ピロリジン標準品 · ピロリジン, 99%
識別子と物理属性
| CAS No. | 123-75-1 |
|---|---|
| 分子式 | C4H9N |
| 平均分子量 | 71.12 g/mol |
| 単同位体質量 | 71.07349929 g/mol |
| SMILES | C1CCNC1 |
| InChIKey | RWRDLPDLKQPQOW-UHFFFAOYSA-N |
| PubChem CID | 31268 |
| ChEMBL | CHEMBL22830 |
| ChEBI | CHEBI:33135 |
| EC No. | 204-648-7 |
| DTXSID | DTXSID3059559 |
| 現地名 | ピロリジン |
化学・物理的性質
| XLogP | 0.5 |
|---|---|
| 極性表面積 | 12 |
| 水素結合供与体数 | 1 |
| 水素結合受容体数 | 1 |
| 回転可能結合数 | 0 |
| 重原子数 | 5 |
| 形式電荷 | 0 |
| 複雑度 | 22.8 |
| 物質分類 | Nitrogen Compounds -> Amines, CyclicFlammable agents - 3rd degree |
| SpringerMaterials Properties | 15N nuclear magnetic resonance spectrum |
| LogP（分配係数） | log Kow = 0.46 at pH 130.460 |
| 臭い | Unpleasant, ammoniacal odorプロピレングリコール中0.10%。アンモニア性動物卵アミン |
| 味 | POWERFUL, AMMONIACAL TASTE |
| 食品添加物 | FLAVORING AGENT OR ADJUVANT -> FDA Substance added to food |
| 密度 | 0.8520 at 22.5 °C/4 °CRelative density (water = 1): 0.850.847-0.8530.8618 @25 °C0.852 g/mL at 25 °C (lit.) |
| 香味料 | EU Flavoring substances |
| Viscosity | 6.1472X10-3 Pa.s |
| Color/Form | Colorless to pale yellow liq |
| 溶解度 | Soluble in ethanol, ethyl etherslightly soluble in benzene, chloroformIn water, 1.0X10+6 mg/L (miscible) at 20 °C1.00E+06 mg/L @ 20 °C (exp)Solubility in water: miscibleSoluble in water, fatsSoluble (in ethanol)水: 混和性アルコール、エーテル、クロロホルム、水と混和します。 |
| Corrosivity | Corrosive |
| 融点 | -63 °C |
| 沸点 | 87-88 °C/760 mmHg (lit.) |
| 蒸気密度 | 2.45 (vs air) |
| 蒸気圧 | 128 mm Hg ( 39 °C) |
| 屈折率 | n20/D 1.443(lit.) |
| FEMA | 3523 | PYRROLIDINE |
| 引火点 | 37 °F |
| 貯蔵条件 | Store below +30°C. |
| 外観・状態 | 液体 |
| pKa（酸解離定数） | 11.27(at 25℃) |
| 色 | Colorless to Almost colorless |
| pH | 12.9 (100g/l, H2O, 20℃) |
| 爆発限界 | 1.6-10.6%(V) |
| においのタイプ | アンモニア性の |
| 由来生物 | synthetic |
| 比熱容量 | Cp(liquid): 2.2 J/(g·K), at 25℃ |
| Merck | 14,8015 |
| JECFA Number | 1609 |
| BRN | 102395 |
| ヘンリー定数 | 4.2×100 mol/(m3Pa) at 25℃, Amoore and Buttery (1978) |
| 誘電率 | 8.3000000000000007 |
| 安定性 | 安定可燃性。強酸、強酸化剤とは相容れない。 |
| InChI | 1S/C4H9N/c1-2-4-5-3-1/h5H,1-4H2 |
| InChIKey | RWRDLPDLKQPQOW-UHFFFAOYSA-N |
| SMILES | C1CCNC1 |
| LogP（分配係数） | 0.22 at 25℃ |
| 表面張力 | 30.11mN/m at 293.15K |
| CAS データベース | 123-75-1(CAS DataBase Reference) |
| NISTの化学物質情報 | Pyrrolidine(123-75-1) |
| EPAの化学物質情報 | Pyrrolidine (123-75-1) |
化学的特性
Pyrrolidine appears as a colorless to pale yellow liquid with an ammonia-like odor. It is infinitely miscible with water and conventional organic solvents such as methanol, acetone, ether, and chloroform. It acts as a lachrymator. Chemically, pyrrolidine behaves like a secondary amine in every respect. For example, it undergoes Leuckart –Wallach and Mannich reactions and is readily converted into an enamine. In the presence of a catalyst, such as platinum at 360°C or rhodium at 650°C, pyrrole is formed. In the presence of a copper catalyst, N-methylpyrrolidone is converted into N-methylpyrrolidine.
化学性质
ピロンは温度や磁場といった外部刺激によって形状が変わる特性を持っていますこの変化は可逆的であり刺激を取り除くと元の形状に戻ることが可能ですこのような特性を持つ材料は「スマート材料」とも呼ばれ多くの先進工業製品に応用されています
安全性と法規制
| GHS 分類 | DangerH225 (22%): Highly Flammable liquid and vapor [Danger Flammable liquids]P210, P233, P240, P241, P242, P243, P260, P261, P264, P264+P265, P270, P271, P280, P301+P317, P301+P330+P331, P302+P361+P354, P303+P361+P353, P304+P340, P305+P354+P338, P316, P317, P321, P330, P363, P370+P378, P403+P235, P405, and P501 (click each P-code to see the statement)Aggregated GHS information provided per 1650 reports by companies from 18 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.H225: Highly Flammable liquid and vapor [Danger Flammable liquids] |
|---|---|
| 規制情報 | Chemical: PyrrolidineRegulation (EC) No 1831/2003 (amended)Pyrrolidine is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Pyrrolidine are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)Status: Active Update: 07-10-2020 https://echa.europa.eu/registration-dossier/-/registered-dossier/5444Pyrrolidine: HSNO Approval: HSR001050 Approved with controlsThe New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.) |
| 輸送ラベル（DOT） | Flammable Liquid Corrosive |
| 火災危険 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]:· Flammable/combustible material.Highly flammable. Gives off irritating or toxic fumes (or gases) in a fire. Vapour/air mixtures are explosive. |
| 火災の可能性 | Dangerous fire hazard when exposed to heat or flame.Vapor/air mixtures are explosive. |
| 健康有害性 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]:· May cause toxic effects if inhaled or ingested. |
| 有害性の概要 | Corrosive to skin[Quick CPC] In high-dose animal studies, causes damage to the liver, kidneys, and CNS (seizures)In 6-hour inhalation studies with concentrations of 2600 ppm, no rats died. [HSDB] Corrosive to skin and eyesA respiratory tract irritantMay have effects on the nervous system[ICSC] Safe when used as a flavoring agent in food[JECFA] Causes convulsions in inhalation lethal-concentration studies of mice and oral lethal-dose studies of rats[RTECS] Causes burnsInhalation may cause corrosive injuries to upper respiratory tract and lungsHarmful by ingestion and inhalation[Alfa Aesar MSDS] |
| 輸送番号・ガイド（DOT） | 1922 132 |
| 反応性グループ | Amines, Phosphines, and Pyridines |
| UN 分類 | UN Hazard Class: 3UN Subsidiary Risks: 8UN Pack Group: II |
| Reactivity Alerts | Highly Flammable |
| Reactivity Profile | PYRROLIDINE neutralizes acids in exothermic reactions to form salts plus water. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. May generate hydrogen, a flammable gas, in combination with strong reducing agents such as hydrides. An explosion occurred when a mixture of pyrrolidine, benzaldehyde, and propionic acid was heated in an attempt to form porphyrins. |
| Chemical Dangers | Decomposes on burning. This produces toxic fumes including nitrogen oxides. The substance is a strong base. Reacts violently with oxidants. It reacts violently with acid and is corrosive. |
| 消火 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]:Use foam, powder, carbon dioxide. In case of fire: keep drums, etc., cool by spraying with water. |
| 応急処置措置 | Fresh air, rest. Refer for medical attention.Rinse skin with plenty of water or shower. Refer for medical attention .First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.Refer for medical attention . |
| 漏出応急措置 | · CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area. |
| 応急処置 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]:General First Aid: |
| 安全保管 | Fireproof. Separated from strong oxidants and acids. Well closed. |
| 暴露管理・個人防護 | · Wear positive pressure self-contained breathing apparatus (SCBA). |
| 消火手順 | Alcohol foam, carbon dioxide, dry chemicalIf material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Use "alcohol" foam, dry chemical or carbon dioxide. |
| 保管条件 | Bundling and sills should be provided to prevent spread of liquid accidentally escaping from storage and process vessels. |
| 清掃方法 | Remove all ignition sources. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in sand or inert absorbent and remove to safe place. Personal protection: chemical protection suit including self-contained breathing apparatus. |
| 非火災時の漏出対応 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]: |
| 処分方法 | SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational exposure or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air qualitypotential migration in soil or watereffects on animal, aquatic, and plant lifeand conformance with environmental and public health regulations. |
| 漏出処分 | Remove all ignition sources. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. Personal protection: chemical protection suit including self-contained breathing apparatus. |
| 相互作用 | Formation of n-nitrosopyrrolidine in a dog's stomach from Na nitrate & pyrrolidine. N-nitrosopyrrolidine disappeared rapidly from stomach, probably due to absorption. |
| 環境中動態 | TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 42(SRC), determined from a log Kow of 0.46(2) and a regression-derived equation(3), indicates that pyrrolidine is expected to have very high mobility in soil(SRC). The pKa of pyrrolidine is 11.31(4), indicating that this compound will primarily exist in the cation form in the environment and cations generally adsorb more strongly to soils containing organic carbon and clay than their neutral counterparts(5). Volatilization of pyrrolidine from moist soil surfaces is not expected to be an important fate process as cations do not volatilize(SRC). Pyrrolidine is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 62.7 mm Hg(6). Pyrrolidine was found to degrade anaerobically via denitrification in 7-15 days in microbial consortia from freshwater sediments, estuarine sediments and activated sludge(7).AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 42(SRC), determined from a log Kow of 0.46(2) and a regression-derived equation(3), indicates that pyrrolidine is not expected to adsorb to suspended solids and sediment(SRC). A pKa of 11.31(4) indicates pyrrolidine will exist almost entirely in the cation form at pH values of 5 to 9 and therefore volatilization from water surfaces is not expected to be an important fate process(5). According to a classification scheme(6), an estimated BCF of 3(SRC), from its log Kow(2) and a regression-derived equation(7), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Pyrrolidine was found to degrade anaerobically via denitrification in 7-15 days in microbial consortia from freshwater sediments, estuarine sediments and activated sludge(8).ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), pyrrolidine, which has a vapor pressure of 62.7 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase pyrrolidine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC)the half-life for this reaction in air is estimated to be 5 hours(SRC), calculated from its rate constant of 7.8X10-11 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Pyrrolidine does not contain chromophores that absorb at wavelengths >290 nm(4) and therefore is not expected to be susceptible to direct photolysis by sunlight(SRC). |
| 食品調査値 | Pyrrolidine was detected in 10 g samples of baked ham at 0.013 ppm(1). Pyrrolidine can be found in tilsiter, camembert, limburger, and brown bread cheeses at 19.9 mg/kg, 1 mg/kg, 0.1 mg/kg and 0.3 mg/kg, respectively(2). In coffee, pyrrolidine was detected in coffee extract and freeze dried coffee at 10 mg/kg and 11 mg/kg, respectively(3). |
| 有害作用 | Neurotoxin - Other CNS neurotoxin |
| 暴露経路 | The substance can be absorbed into the body by inhalation and by ingestion. |
| Plant Concentrations | Pyrrolidine was detected in 10 g samples of spinach and miso at 0.250 ppm and 0.020 ppm, respectively(1). Pyrrolidine can be found in spinach, red radish, and celery at 2.5 mg/kg, 38 mg/kg, and 0.4 mg/kg, respectively(2). It can also be found in maize, apple peels, beans, kale, paprika red and cornichons at 3.5 mg/kg, 1.5 mg/kg, 0.2 mg/kg, 1.6 mg/kg, 0.6 mg/kg, and 0.1 mg/kg, respectively(2). It is also found in barley, hops, and malt at 0.9 mg/kg, 1 mg/kg, and 1.5 mg/kg, respectively(2). |
| Signs and Symptoms | Burning sensation. Convulsions. Cough. Headache. Nausea. Sore throat. Vomiting.Redness. Skin burns. Pain. Blisters.Redness. Pain. Blurred vision. Severe deep burns.Convulsions. Sore throat. Vomiting. See Inhalation. |
| Effluent Concentrations | Pyrrolidine was identified in the primary effluent at a concentration of 14 ug/L from municipal wastewater treatment plants(1). |
| Soil Adsorption/Mobility | The Koc of pyrrolidine is estimated as 42(SRC), using a log Kow of 0.46(1) and a regression-derived equation(2). According to a classification scheme(3), this estimated Koc value suggests that pyrrolidine is expected to have very high mobility in soil. The pKa of pyrrolidine is 11.31(4), indicating that this compound will primarily exist in the cation form in the environment and cations generally adsorb more strongly to soils containing organic carbon and clay than their neutral counterparts(5). |
| Natural Pollution Sources | FOUND IN TOBACCO & CARROT LEAVES. PROBABLE BIOSYNTHESIS FROM ORNITHINE & PUTRESCINE.Pyrrolidine was detected in spinach(1,2) and miso(1). Pyrrolidine was also detected in red radish, celery, maize, apple peels, beans, kale, paprika red, cornichons, barley, hops, and malt(2). |
| Human Toxicity Excerpts | /SIGNS AND SYMPTOMS/ Inhalation: Burning sensation. Convulsions. Cough. Headache. Nausea. Sore throat. Vomiting. Skin: Redness. Skin burns. Pain. Blisters. Eyes: Redness. Pain. Blurred vision. Severe deep burns. Ingestion: Convulsions. Sore throat. Vomiting. (See Inhalation). |
| Fish/Seafood Concentrations | Pyrrolidine was detected in 10 g samples of cod roe at 0.006 ppm(1). |
| F | 34 |
| 水環境危害等級（WGK） | 2 |
| TSCA 収載状態 | TSCA listed |
| RTECS 番号 | UX9650000 |
| 輸送番号（UN） | UN 1922 |
| 毒性 | LD50 orally in Rabbit: 433 mg/kg |
| 税関コード | 2933 99 80 |
| 危険文句（R） | 11-22-23-34-35-20/21/22-20/22-R35-R20/21/22-R11 |
| 化審法 | (5)-103 |
| 消防法 | 危-4-1-II |
| 危険表示 | F,T,C |
| 安全措置（S） | 16-26-36/37/39-45-33-S45-S36/37/39-S26-S16 |
| 危険等級 | 3Acute Tox. 4 InhalationAcute Tox. 4 OralEye Dam. 1Flam. Liq. 2Skin Corr. 1A |
| 包装等級 | II |
| 自然発火温度 | 653 °F |
| 貯蔵分類 | 3 - Flammable liquids |
| 有害物質データ | 123-75-1(Hazardous Substances Data) |
用途
解説
C4H9N(71.12)．tetramethyleneimine．テトラヒドロピロールともいう．タバコの葉に含まれる．ピロールをヨウ化水素とリンまたはニッケル触媒を用いて水素で還元すると生成する．また4-ブロモブチルアミンを水酸化アルカリで処理するか，テトラメチレンジアミンを加熱しても生成する．特有の臭いを有する無色の液体．沸点88.5～89 ℃．d22.540.8520．n28D1.4402．水に溶けて強い塩基性を示す．エタノール，エーテル，クロロホルムに可溶．結晶性のよい塩を与える．塩化金酸塩(C4H9N·HAuCl4)は融点206 ℃(分解)．水と任意の割合でまじり，強塩基性を示す(塩基解離指数pKb＝2.7)。タバコやニンジンの葉に存在する。ピロールをニッケル触媒の存在下に水素で還元するのが最も簡便な合成法である。ピペリジンと同様に脂肪族第二アミンの性質を示す。有機合成における基礎的な原料として広く使われているが，とくにピロリジンとケトン類とを縮合させてできるエナミン(1‐ピロリジノ‐1‐シクロヘキセン)は合成化学上きわめて重要である。森北出版「化学辞典（第2版）
用途
医薬品、農薬、可塑剤、写真薬、乳化剤、腐食防止剤などの合成中間原料ならびにポリウレタン製造用触媒、エポキシ樹脂の硬化剤など
天然物の起源
Reported found in beer, bread, wheat bread, salmon caviar, fish, milk, leaves and stalks of celery, Camembert cheese, Limburger cheese, Russian cheeses, tilsit cheese, other cheeses, caviar, raw fatty fish, beer, Finnish whiskey, white wine, red wine, coffee, radish, malt, roasted peanut, sweet corn and roasted barley.
使用
Pyrrolidine is a flammable alkaline liquid that undergoes reactions typical of secondary amines. It is used to prepare pesticides and rubber accelerators and as a chemical intermediate (usually the hydrochloride form) in the pharmaceutical industry. There is relatively limited industrial exposure to this material.
一般的な説明
Pyrrolidine is a saturated heterocycliccompound having one nitrogenatom in a five-membered ring. It is a colorless to pale yellow liquid with an ammonia-like odor. It is found in certain plants andthe ring structure is present in manyalkaloids. Flash point 37°F. Density 0.85 g / cm3. Vapors heavier than air. Produces toxic oxides of nitrogen during combustion.
使用用途
ピロリジンは、有機合成の材料に広く用いられています。具体的には、ピロリジンとケトンの縮合によって、エナミン (英: enamine) を合成できます。さらにピロリジンは、強塩基性を示すため、塩基性の反応溶媒としても使用可能です。 また、ピロリジン骨格を持ついくつかの物質が医薬品に使われています。例えば、頻脈性不整脈、持続性心房細動、狭心症の治療薬に用いられているベプリジル (ベプリジル塩酸塩水和物) は、ピロリジン骨格を有します。
製法・合成法
製造方法
Pyrrolidine is formed by reduction of pyrrole. Via overall 5-endo-trig cyclizations of homoallylic tosylamides. Pyrrolidine can be produced from butanediol and ammonia, e.g., over an aluminum thorium oxide catalyst at 300°C or over a nickel catalyst at 200°C and 20 MPa under hydrogenation conditions. It can also be produced from THF and ammonia over aluminum oxide at 275-375°C.
純化方法
Dry pyrrolidine with BaO or sodium, then fractionally distil it, under N2, through a Todd column (p 11) packed with glass helices. [Beilstein 20 H 159, 20 I 36, 20 II 79, 20 III/IV 2072, 20/1 V 162.]