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2,4,6-Trimethylpyridine
2,4,6-トリメチルピリジン · s-コリジン · sym-コリジン · γ-コリジン · 2,4,6-コリジン · 2,4,6-コリジン(2,4,6-トリメチルピリジン) · 2,4,6‐トリメチルピリジン (別名2,4,6-コリジン) · 2,4,6‐トリメチルピリジン
識別子と物理属性
| CAS No. | 108-75-8 |
|---|---|
| 分子式 | C8H11N |
| 平均分子量 | 121.18 g/mol |
| 単同位体質量 | 121.08914935 g/mol |
| SMILES | Cc1cc(C)nc(C)c1 |
| InChIKey | BWZVCCNYKMEVEX-UHFFFAOYSA-N |
| PubChem CID | 7953 |
| ChEMBL | CHEMBL1209580 |
| ChEBI | CHEBI:189131 |
| EC No. | 203-613-3 |
| DTXSID | DTXSID1051561 |
| 現地名 | 2,4,6-トリメチルピリジン |
化学・物理的性質
| XLogP | 1.9 |
|---|---|
| 極性表面積 | 12.9 |
| 水素結合供与体数 | 0 |
| 水素結合受容体数 | 1 |
| 回転可能結合数 | 0 |
| 重原子数 | 9 |
| 形式電荷 | 0 |
| 複雑度 | 80.6 |
| 物質分類 | Nitrogen Compounds -> Pyridines |
| SpringerMaterials Properties | Boiling point |
| LogP（分配係数） | log Kow = 1.88 |
| 臭い | Aromatic odor |
| 密度 | 0.913 @ 20 °C/20 °C0.917 g/mL at 25 °C (lit.) |
| 香味料 | EU Flavoring substances |
| Color/Form | Colorless liquid |
| 溶解度 | Sol in methanol, ethanol, chloroform, benzene, toluene, and dil acidsmiscible with etherSol in acetoneSol in water (in g/100 ml water): 20.8 g @ 6 °C, 3.5 g @ 20 °C, 1.8 g @ 100 °C35g/リットル35g/L(20℃) |
| 引火点 | 58 °C136 °F135 °F |
| 沸点 | 170.4 °C171-172 °C (lit.) |
| Decomposition | When heated to decomposition it emits toxic vapors of /nitrogen oxides/. |
| 融点 | -44.5 °C-43 °C (lit.) |
| 蒸気圧 | 4 hPa (20 °C) |
| 屈折率 | n20/D 1.498(lit.) |
| 貯蔵条件 | Store below +30°C. |
| 外観・状態 | 液体 |
| pKa（酸解離定数） | 7.43(at 25℃) |
| 色 | 無色透明～黄色 |
| Merck | 14,9718 |
| BRN | 107283 |
| ヘンリー定数 | 1.1×100 mol/(m3Pa) at 25℃, Duchowicz et al. (2020) |
| 誘電率 | 1.9(20℃) |
| 安定性 | 安定。可燃性。強力な酸化剤とは相容れない。 |
| InChI | 1S/C8H11N/c1-6-4-7(2)9-8(3)5-6/h4-5H,1-3H3 |
| InChIKey | BWZVCCNYKMEVEX-UHFFFAOYSA-N |
| SMILES | Cc1cc(C)nc(C)c1 |
| LogP（分配係数） | 1.25 at 20℃ |
| CAS データベース | 108-75-8(CAS DataBase Reference) |
| NISTの化学物質情報 | Pyridine, 2,4,6-trimethyl-(108-75-8) |
| EPAの化学物質情報 | 2,4,6-Trimethylpyridine (108-75-8) |
化学的特性
colourless liquid
安全性と法規制
| GHS 分類 | This chemical does not meet GHS hazard criteria for 0.5% (1 of 187) of reports.DangerH226 (99.5%): Flammable liquid and vapor [Warning Flammable liquids]P210, P233, P240, P241, P242, P243, P261, P262, P264, P264+P265, P270, P271, P280, P301+P317, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P316, P317, P319, P321, P330, P332+P317, P337+P317, P361+P364, P362+P364, P370+P378, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)Aggregated GHS information provided per 187 reports by companies from 15 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies. |
|---|---|
| 規制情報 | Chemical: Pyridine, 2,4,6-trimethyl-Commission Regulation (EC) No 1565/2000 (Repealed by Com. Implementing Reg. (EU) No 872/2012)Status: Active Update: 16-02-2021 https://echa.europa.eu/registration-dossier/-/registered-dossier/32320Pyridine, 2,4,6-trimethyl-: HSNO Approval: HSR001388 Approved with controls |
| 輸送ラベル（DOT） | Flammable Liquid |
| 火災危険 | Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: |
| 健康有害性 | Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: |
| 有害性の概要 | Emergency treatment: PyridinePyridine is an irritant that causes CNS depression after ingestion of 1/2 cup or inhalation of 6-12 ppmIt can cause liver and kidney injury[HSDB] [HSDB] A skin and strong eye irritant[Alfa Aesar MSDS] See Pyridine. |
| 反応性グループ | Amines, Phosphines, and Pyridines |
| Reactivity Profile | COLLIDINE neutralizes acids in exothermic reactions to form salts plus water. These acid-base reactions are exothermic. Incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. May generate flammable gaseous hydrogen in combination with strong reducing agents such as hydrides. |
| Air and Water Reactions | Flammable. Insoluble in water. |
| Hazard Classes and Categories | Flam. Liq. 3 (99.5%)Flammable liquids - Category 3 |
| 消火 | Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: |
| 応急処置 | Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: |
| 非火災時の漏出対応 | Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: |
| 処分方法 | SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices. |
| Isolation and Evacuation | Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: |
| Protective Action Criteria (PAC) | 1.3 [ppm]14 [ppm]85 [ppm] |
| Personal Protective Equipment (PPE) | Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: |
| 環境中動態 | TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 250(SRC), determined from a log Kow of 1.9(2) and a regression-derived equation(3), indicates that 2,4,6-trimethylpyridine is expected to have moderate mobility in soil(SRC). The pKa of 2,4,6-trimethylpyridine is 7.4(4), indicating that this compound will mainly exist in the protonated form in the environment and cations generally adsorb to organic carbon and clay more strongly than their neutral counterparts, thus attenuating soil mobility(5). Volatilization of 2,4,6-trimethylpyridine from moist soil surfaces is expected to be an important fate process(SRC) given an estimated Henry's Law constant of 8.8X10-6 atm-cu m/mole(SRC), derived from its vapor pressure, 2.0 mm Hg(6), and water solubility, 3.5X10+4 mg/l(7). However, adsorption to soil is expected to attenuate volatilization(SRC). The potential for volatilization of 2,4,6-trimethylpyridine from dry soil surfaces may exist(SRC) based upon a vapor pressure of 2.0 mm Hg(6). Under aerobic and anaerobic conditions, 2,4,6-trimethylpyridine, present at 1 mM, degraded 100% in >97 days at pH 7 using a 0.5% garden soil suspension with glucose-yeast extract (20 ppm) and a screening test(8). Within 2 weeks under aerobic conditions, 100% transformation of 2,4,6-trimethylpyridine occurred in soil previously contaminated with pyridine contaminants(9).AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 250(SRC), determined from a log Kow of 1.9(2) and a regression-derived equation(3), indicates that 2,4,6-trimethylpyridine is expected to adsorb slightly to suspended solids and sediment(SRC). However, the pKa of 2,4,6-trimethylpyridine is 7.4(4), indicating that this compound will mainly exist in the protonated form in the environment and cations generally adsorb to organic carbon and clay more strongly than their neutral counterparts(5). Volatilization from water surfaces is expected(3) based upon an estimated Henry's Law constant of 8.8X10-6 atm-cu m/mole(SRC), derived from its vapor pressure, 2.0 mm Hg(6), and water solubility, 3.5x10+4 mg/l(7). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 3.1 and 38 days, respectively(SRC). According to a classification scheme(8), an estimated BCF of 6(SRC), from its log Kow(2) and a regression-derived equation(9), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Under aerobic and anaerobic conditions, 2,4,6-trimethylpyridine, present at 1 mM, degraded 100% in >97 days at pH 7 using a 0.5% garden soil suspension with glucose-yeast extract (20 ppm) and a screening test(10).ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 2,4,6-trimethylpyridine, which has a vapor pressure of 2.0 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere(SRC). Vapor-phase 2,4,6-trimethylpyridine 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 2.3 days(SRC), calculated from its rate constant of 7.0X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). |
| 有害作用 | Neurotoxin - Other CNS neurotoxin |
| Effluent Concentrations | The concn of 2,4,6-trimethylpyridine in Australian oil shale retort water (basic fraction) was 2 mg/l(1). The concn of 2,4,6-trimethylpyridine in condensate and process retort water produced in modified in situ oil-shale retort were 70.1 and 4.0 mg/l, respectively(2). In a closed system, 2,4,6-trimethylpyridine was detected in air above 1 of 3 samples of shale oil wastewaters (detection limit of 0.4 ng per 1 ml air)(3)a concn of 8.3 ng of 2,4,6-trimethylpyridine per 1 ml of air was measured above a 1 ml sample of wastewater with a concn of <0.8 ng/ml of 2,4,6-trimethylpyridine(3). |
| Soil Adsorption/Mobility | The Koc of 2,4,6-trimethylpyridine is estimated as 250(SRC), using a log Kow of 1.9(1) and a regression-derived equation(2). According to a classification scheme(3), this estimated Koc value suggests that 2,4,6-collidine is expected to have moderate mobility in soil(SRC). The pKa of 2,4,6-trimethylpyridine is 7.4(4), indicating that this compound will partially exist in the protonated form in the environment and cations generally adsorb to organic carbon and clay more strongly than their neutral counterparts(5). |
| Natural Pollution Sources | 2,4,6-Trimethylpyridine is found in small amounts in coal tar and shale oil(1). |
| Human Toxicity Excerpts | MAJOR ACTIONS OF PYRIDINE & ITS SIMPLE ALKYL DERIV ARE...NERVOUS SYSTEM DEPRESSION... /PYRIDINE & ITS ALKYL DERIV/...PYRIDINE AND ITS DERIV CAUSE LOCAL IRRITATION ON CONTACT WITH SKIN, MUCOUS MEMBRANES AND CORNEA. /PYRIDINE & DERIVATIVES/TRANSIENT SYMPTOMS OF NAUSEA, HEADACHE, INSOMNIA, NERVOUSNESS, & LOW BACK OR ABDOMINAL DISCOMFORT WITH URINARY FREQUENCY HAVE BEEN OBSERVED IN PERSONS WITH REPEATED EXPOSURES TO PYRIDINE IN CONCN VARYING FROM 15-330 PPM. /PYRIDINE/...EXPOSURE TO...MIXT OF PYRIDINE, PICOLINE, LUTIDINE, & COLLIDINE...IN 2 MEN. BOTH HAD GI DISTURBANCES, & 1 HAD...LOSSES OF CONSCIOUSNESS...FACIAL PARALYSIS, ANISOCORIA, & ATAXIA. OTHER HAD HEADACHE... RIGHT-SIDE FACIAL PARALYSIS, & 2 DAYS LATER...PTOSIS...ANISOCORIA, & LEFT-SIDED ABDUCENS PARESIS....COLLIDINES, CAUSE SYMPTOMS RESEMBLING THOSE OBSERVED WITH PYRIDINE. THESE ARE LARGELY, NONSPECIFIC & INCL WEAKNESS, ATAXIA, DIARRHEA, & UNCONSCIOUSNESS. DELAYED DEATHS FOLLOWING SINGLE DOSE ARE UNCOMMON & SURVIVORS GENERALLY GAIN WT NORMALLY. /COLLIDINES/ |
| Artificial Pollution Sources | 2,4,6-Trimethylpyridine's production and use as a chemical intermediate and as a dehydrohalogenation agent(1) may result in its release to the environment through various waste streams(SRC). |
| Environmental Biodegradation | AEROBIC: 2,4,6-Trimethylpyridine, present at 1 mM, degraded 100% in >97 days at pH 7 using a 0.5% garden soil suspension with glucose-yeast extract (20 ppm) and a screening test(1). Within 2 weeks, 100% transformation of 2,4,6-trimethylpyridine occurred in soil previously contaminated with pyridine contaminants(2).ANAEROBIC: 2,4,6-Trimethylpyridine, present at 1 mM, degraded 100% in >97 days at pH 7 using a 0.5% garden soil suspension with glucose-yeast extract (20 ppm) and a screening test(1). |
| Environmental Bioconcentration | An estimated BCF of 6 was calculated for 2,4,6-trimethylpyridine(SRC), using a log Kow of 1.9(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC). |
| Volatilization from Water/Soil | The Henry's Law constant for 2,4,6-trimethylpyridine is estimated as 8.8X10-6 atm-cu m/mole(SRC) derived from its vapor pressure, 2 mm Hg(1), and water solubility, 3.5X10+4 mg/l(2). This Henry's Law constant indicates that 2,4,6-trimethylpyridine is expected to volatilize from water surfaces(3). Based on this Henry's Law constant, the volatilization half-life from a model river (1 m deep, flowing 1 m/sec, wind velocity of 3 m/sec)(3) is estimated as 3.1 days(SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(3) is estimated as 38 days(SRC). 2,4,6-Trimethylpyridine's estimated Henry's Law constant indicates that volatilization from moist soil surfaces may occur(SRC). However, the pKa of 2,4,6-trimethylpyridine is 7.4(4) which suggests that volatilization from water surfaces is expected to be attenuated slightly since ions are not expected to volatilize(SRC). 2,4,6-Trimethylpyridine is expected to volatilize from dry soil surfaces(SRC) based upon its vapor pressure(1). |
| Non-Human Toxicity Excerpts | THE AMINO DERIVATIVES, THE 2- & 4-VINYL DERIVATIVES, & COLLIDINE APPEAR TO BE THE MOST POTENT PRIMARY IRRITANTS OF THE /PYRIDINE/ SERIES....RANGE-FINDING STUDIES... /TABLE:/ APPROX LD50 (G/KG) RATS ORAL 0.4IP 0.05-0.1. MICE ORAL 0.2-0.4IP 0.1-0.2. APPROX LD50 (ML/KG) GUINEA PIGS PERCUTANEOUS 1.0-2.0. WHERE RANGE IS GIVEN, ALL ANIMALS DIED AT HIGH DOSE & ALL SURVIVED AT LOWER DOSE. WHERE SINGLE FIGURE IS GIVEN, APPROX 1/2 THE ANIMALS DIED AT THAT DOSE.THREE OF THREE RATS DIED FOLLOWING EXPOSURE TO 2500 PPM FOR 2 HR. CONCENTRATED VAPOR PRODUCED BY BUBBLING AIR THROUGH COMPD AT ROOM TEMP. /FROM TABLE/ |
| Environmental Abiotic Degradation | The rate constant for the vapor-phase reaction of 2,4,6-trimethylpyridine with photochemically-produced hydroxyl radicals has been estimated as 7.0X10-12 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 2.3 hrs at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). 2,4,6-Trimethylpyridine is not expected to undergo hydrolysis in the environment due to the lack of hydrolyzable functional groups(2). 3,5-Lutidine, a structurally similar alkylated pyridine, has a weak absorption band that extends into the environmental UV spectrum(3), which suggests that direct photolysis is not likely to be an important fate process for alkylated pyridines(SRC). |
| 水環境危害等級（WGK） | 3 |
| TSCA 収載状態 | TSCA listed |
| RTECS 番号 | UU0970000 |
| 輸送番号（UN） | UN 1992 3/PG 3 |
| 毒性 | LD50 orally in Rabbit: 400 mg/kg |
| 税関コード | 29333999 |
| 危険文句（R） | 10-20/21/22-36/37/38 |
| 化審法 | (5)-715 |
| 消防法 | 危-4-2-III |
| 危険表示 | Xn |
| 安全措置（S） | 26-36/37-36 |
| 危険等級 | 3Acute Tox. 3 DermalAcute Tox. 4 OralAquatic Chronic 3Eye Irrit. 2Flam. Liq. 3Skin Irrit. 2STOT SE 3 |
| 包装等級 | III |
| 貯蔵分類 | 3 - Flammable liquids |
| 有害物質データ | 108-75-8(Hazardous Substances Data) |
用途
解説
コリジン，2,4,6-trimethylpyridine．C8H11N(121.18)．sym-コリジンまたはγ-コリジンともいう．骨油より分留して得られる．アセトンと尿素を塩化亜鉛の存在下で加熱して合成される．液体．沸点171～172 ℃．2,4,6-トリメチルピリジン(2,4,6-コリジン)のほかに，2,4,5-トリメチルピリジン(2,4,5-コリジン，沸点165～168 ℃)，2-メチル-4-エチルピリジン(沸点179 ℃)，および4-メチル-3-エチルピリジン(沸点195 ℃)が知られている
用途
化学中間体
用途
有機合成原料。
使用
2,4,6-Collidine is an reagent used for various synthetic preparations such as the synthesis of methylated pyridines by three-componet catalytic condensation of acetylene, acetone and ammonia.
一般的な説明
2,4,6-Trimethylpyridine is a pyridine derivative. It has a pK of 7.4. The product can react with trifluoroiodomethane in cyclopentane solution to afford 1:1 complex. This complex was investigated by NMR (Nuclear Magnetic Resonance) spectroscopy. Collidine-buffered osmium tetroxide solutions have been prepared by adding osmium tetroxide solution to it. These solutions have been used as fixative for electron microscopic studies.2,4,6-Trimethylpyridine can undergo oxidation with potassium permanganate to form 2,4,6-pyridinetricarboxylic acid.
製法・合成法
純化方法
Commercial samples may be grossly impure. Likely contaminants include 3,5-dimethylpyridine, 2,3,6-trimethylpyridine and water. Brown, Johnson and Podall [J Am Chem Soc 76 5556 1954] fractionally distilled 2,4,6-trimethylpyridine under reduced pressure through a 40cm Vigreux column (p 11) and added to 430mL of the distillate slowly, with cooling to 0o, 45g of BF3-diethyl etherate. The mixture was again distilled, and an equal volume of dry *benzene was added to the distillate. Dry HCl was passed into the solution, which was kept cold in an ice-bath, and the hydrochloride was filtered off. It was recrystallised from absolute EtOH (1.5mL/g) to m 286-287o[m 256o(sealed tube), also m 293-294o subliming slowly]. The free base was regenerated by treatment with aqueous NaOH, then extracted with *benzene, dried (MgSO4) and distilled under reduced pressure. Sisler et al. [J Am Chem Soc 75 446 1953] precipitated trimethylpyridine as its phosphate from a solution of the base in MeOH by adding 85% H3PO4, shaking and cooling. The free base was regenerated as above. Garrett and Smythe [J Chem Soc 763 1903] purified the trimethylpyridine via the HgCl2 complex. It is more soluble in cold than hot H2O [the solubility is 20.8% at 6o, 3.5% at 20o, 1.8% at 100o]. Alternatively, purify it by dissolving it in CHCl3, adding solid K2CO3 and Drierite, filtering and fractionally distilling through an 8in helix-packed column. The sulfate has m 205o, and the picrate (from hot H2O) has m 155-156o. [Frank & Meikle J Am Chem Soc 72 4184 1950, Beilstein 20 H 250, 20 I 87, 20 II 164, 20 III/IV 2810, 20/6 V 93.]