クロロぎ酸ベンジル
クロロぎ酸ベンジル (30-35%トルエン溶液) · カルボベンゾキシクロリド · ベンジルカルボニルクロリド · クロロ炭酸ベンジル · (ベンジルオキシ)ぎ酸クロリド · Cbzクロリド · クロリド炭酸ベンジル · ベンジルオキシぎ酸クロリド
識別子と物理属性
| CAS No. | 501-53-1 |
|---|---|
| 分子式 | C8H7ClO2 |
| 平均分子量 | 170.59 g/mol |
| 単同位体質量 | 170.01345714 g/mol |
| SMILES | O=C(Cl)OCc1ccccc1 |
| InChIKey | HSDAJNMJOMSNEV-UHFFFAOYSA-N |
| PubChem CID | 10387 |
| ChEMBL | CHEMBL1581748 |
| EC No. | 207-925-0 |
| DTXSID | DTXSID9027158 |
| 現地名 | クロロぎ酸ベンジル |
化学・物理的性質
| XLogP | 3 |
|---|---|
| 極性表面積 | 26.3 |
| 水素結合供与体数 | 0 |
| 水素結合受容体数 | 2 |
| 回転可能結合数 | 3 |
| 重原子数 | 11 |
| 形式電荷 | 0 |
| 複雑度 | 130 |
| 物質分類 | Toxic Gases & Vapors -> Acid HalidesCorrosives |
| SpringerMaterials Properties | Chemical shift |
| 臭い | ACRID ODORODOR OF PHOSGENESHARP, PENETRATING ODORイライラする鋭い、貫く。 |
| 密度 | 1.22 at 68 °F (USCG, 1999) - Denser than waterwill sink1.2166 20 °C/4 °CRelative density (water = 1): 1.201.2166 @ 20°C1.212 g/mL at 20 °C |
| Viscosity | 2.57 mPa-s (cP) @ 20 °C |
| Color/Form | OILY LIQUIDCOLORLESS TO PALE YELLOW LIQUID |
| 溶解度 | SOL IN ETHER, ACETONE, BENZENESolubility in water: reactionエーテル、アセトン、ベンゼンと混和します。分解する |
| Corrosivity | Corrosive |
| 引火点 | 227 °F Vigorous decomposition occurs at these temperaturesthus these values are anomalous due to the effect of the decomp. products (benzyl chloride and CO2). (USCG, 1999)[HSDB] 80 °C176 °F OC227 °F CC80.0 °C c.c.197 °F |
| 沸点 | 306 °F at 760 mmHg (decomposes) (USCG, 1999)152 °C AT 760 MM HG152 °C @760 [mm Hg]103 °C20 mm Hg(lit.) |
| Decomposition | EMITS HIGHLY TOXIC PHOSGENE FUMES WHEN HEATED TO 100 °C.DANGEROUSWHEN HEATED TO DECOMP ... THEY EVOLVE HIGHLY TOXIC /HYDROGEN/ CHLORIDE FUMES. /CHLORIDES/>100 °C |
| 融点 | 0 °C-20 °C |
| 蒸気密度 | 1 (vs air) |
| 蒸気圧 | 1.39 psi ( 20 °C) |
| 屈折率 | n20/D 1.519(lit.) |
| 貯蔵条件 | Store at +2°C to +8°C. |
| 外観・状態 | 解決 |
| 色 | クリアー ほんのりイエロー～ほんのりピンク |
| Merck | 14,1801 |
| 安定性 | 安定。水、酸化剤と相容れない。可燃性。 |
| InChI | 1S/C8H7ClO2/c9-8(10)11-6-7-4-2-1-3-5-7/h1-5H,6H2 |
| InChIKey | HSDAJNMJOMSNEV-UHFFFAOYSA-N |
| SMILES | ClC(=O)OCc1ccccc1 |
| CAS データベース | 501-53-1(CAS DataBase Reference) |
| NISTの化学物質情報 | Benzyl chloroformate(501-53-1) |
| EPAの化学物質情報 | Carbonochloridic acid, phenylmethyl ester (501-53-1) |
化学的特性
colorless or light yellow oily liquid with rancid odor. soluble in ether, acetone, benzene and other organic solvents. It is used to protect amino groups in peptide synthesis.
安全性と法規制
| GHS 分類 | DangerH314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]P260, P264, P273, P280, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P321, P363, P391, P405, and P501 (click each P-code to see the statement)This chemical does not meet GHS hazard criteria for 0.6% (1 of 173) of reports.H314 (99.4%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation] |
|---|---|
| 規制情報 | Chemical: Carbonochloridic acid, phenylmethyl esterCarbonochloridic acid, phenylmethyl ester is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Carbonochloridic acid, phenylmethyl ester 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: 02-03-2017 https://echa.europa.eu/registration-dossier/-/registered-dossier/12078Benzyl chloroformate: Does not have an individual approval but may be used under an appropriate group standardThe 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.) |
| その他の安全情報 | Evaluation - Chemicals that are unlikely to require further regulation to manage risks to human health |
| 輸送ラベル（DOT） | Corrosive |
| 火災危険 | Special Hazards of Combustion Products: Toxic phosgene, hydrogen chloride, and benzyl chloride vapors may form.· EXCEPT FOR ACETIC ANHYDRIDE (UN1715), THAT IS FLAMMABLE, some of these materials may burn, but none ignite readily.Combustible. Gives off irritating or toxic fumes (or gases) in a fire. |
| 火災の可能性 | COMBUSTIBLE |
| 健康有害性 | Inhalation causes mucous membrane irritation. Eyes are irritated by excessive exposure to vapor. Liquid causes severe irritation of eyes and irritates skin. Ingestion causes irritation of mouth and stomach. (USCG, 1999)· CORROSIVE and/or TOXICinhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. |
| 有害性の概要 | Corrosive to skin[Quick CPC] A skin, eye, and respiratory tract irritantLacrimator[HSDB] A corrosive substance that causes lacrimation and may cause lung edema after inhalation of high concentrations[ICSC] See CHLOROFORMATES. |
| 輸送番号・ガイド（DOT） | 1739 137 |
| 反応性グループ | Acyl Halides, Sulfonyl Halides, and Chloroformates |
| EC 分類 | Symbol: C, NR: 34-50/53S: (1/2)-26-45-60-61 |
| UN 分類 | UN Hazard Class: 8UN Pack Group: I |
| Reactivity Alerts | Water-Reactive |
| 消火 | Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:Use dry powder, foam, carbon dioxide. |
| 応急処置措置 | Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention.Remove contaminated clothes. Rinse skin with plenty of water or shower.First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.Do NOT induce vomiting. Give one or two glasses of water to drink. 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.· Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. |
| 応急処置 | INHALATION: remove from exposuresupport respirationcall physician.General First Aid: |
| 安全保管 | Separated from food and feedstuffs. Dry. Well closed. |
| 暴露管理・個人防護 | · Wear positive pressure self-contained breathing apparatus (SCBA). |
| 消火手順 | EXTINGUISH WITH DRY CHEMICALS, FOAM OR CARBON DIOXIDE.If material on fire or involved in fire: Use dry chemical, dry sand, or carbon dioxide. Do not use water on material itself. If large quantities of combustibles are involved, use water in flooding quantities as spray and fog. Use water spray to knock-down vapors. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. |
| 非火災時の漏出対応 | Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]: |
| 漏出処分 | Collect leaking and spilled liquid in sealable containers as far as possible. Carefully collect remainder. Then store and dispose of according to local regulations. Personal protection: complete protective clothing including self-contained breathing apparatus. |
| Preventive Measures | If material not on fire and not involved in fire: Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. Build dikes to contain flow as necessary. Use water spray to knock-down vapors. Do not use water on material itself. Neutralize spilled material with crushed limestone, soda ash, or lime.Personnel protection: Avoid breathing vapors. Keep upwind. Wear positive pressure self-contained breathing apparatus. Avoid bodily contact with the material. Wear appropriate chemical protective gloves, boots and goggles. Do not handle broken packages unless wearing appropriate personal protective equipment Wash away any material which may have contacted the body with copious amounts of water or soap and water. If contact with the material anticipated, wear appropriate chemical protective clothing. |
| Isolation and Evacuation | Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:Immediate precautionary measure |
| Eye Prevention | Wear face shield or eye protection in combination with breathing protection. |
| 有害作用 | Dermatotoxin - Skin burns. |
| 暴露経路 | The substance can be absorbed into the body by inhalation and by ingestion. |
| Signs and Symptoms | Cough. Shortness of breath. Sore throat. Laboured breathing.Skin burns.Watering of the eyes. Severe deep burns.Burning sensation. Abdominal pain. Shock or collapse. |
| Human Toxicity Excerpts | ... LACRIMATOR.INHALATION CAUSES MUCOUS MEMBRANE IRRITATION. EYES ARE IRRITATED BY EXCESSIVE EXPOSURE TO VAPOR. LIQ CAUSES IRRITATION OF EYES & IRRITATES SKIN. INGESTION CAUSES IRRITATION OF MOUTH & STOMACH. |
| Toxicity Data | LC50 (rat) = 590 mg/m3/4h |
| F | 19 |
| 水環境危害等級（WGK） | 3 |
| TSCA 収載状態 | TSCA listed |
| RTECS 番号 | LQ5860000 |
| 輸送番号（UN） | UN 1739 |
| 毒性 | LD50 orally in Rabbit: 3000 mg/kg |
| PRTR法 | 第一種指定化学物質 |
| 税関コード | 2915 90 70 |
| 危険文句（R） | 45-20-34-48/22-50/53-67-65-63-48/20-11-43-37-23 |
| 化審法 | (3)-1835, (3)-2885 |
| 安衛法 | 有機則 第二種有機溶剤等 |
| 消防法 | 危-4-3-III |
| 危険表示 | T,C,N,F |
| 安全措置（S） | 53-26-36/37/39-45-60-61-62-46-36/37 |
| 危険等級 | 8Aquatic Acute 1Aquatic Chronic 1Carc. 1BEye Dam. 1Skin Corr. 1BSTOT SE 3 |
| 包装等級 | I |
| 自然発火温度 | 590 °C |
| 貯蔵分類 | 6.1C - Combustible, acute toxic Cat.3toxic compounds or compounds which causing chronic effects |
| 有害物質データ | 501-53-1(Hazardous Substances Data) |
用途
用途
ペプチド合成用
用途
有機過酸化物(重合触媒)?樹脂改質剤?医薬?農薬原料 、ペプチド合成時のアミノ基ブロック剤
説明
Benzyl chloroformate, also known as benzyl chlorocarbonate or Z-chloride, is the benzyl ester of chloroformic acid. It can be also described as the chloride of the benzyloxycarbonyl (Cbz or Z) group. In its pure form it is a water-sensitive oily colorless liquid, although impure samples usually appear yellow. It possesses a characteristic pungent odor and degrades in contact with water. The compound was first prepared by Leonidas Zervas in the early 1930s who used it for the introduction of the benzyloxycarbonyl protecting group, which became the basis of the Bergmann-Zervas carboxybenzyl method of peptide synthesis he developed with Max Bergmann. This was the first successful method of controlled peptide chemical synthesis and for twenty years it was the dominant procedure used worldwide until the 1950s. To this day, benzyl chloroformate is often used for amine group protection.
使用
Benzyl chloroformate is widely used as a reactive chemical intermediate in plastic, pharmaceutical, agricultural and organic chemicals. It is useful for the introduction of carboxybenzyl (cbz) protecting group for amines such as aniline in organic synthesis. It is also involved in the synthesis of 1,2,4-oxadiazoles.
一般的な説明
Benzyl chloroformate appears as a colorless liquid with an acrid odor. Vapors irritate eyes and mucous membranes. Corrosive to metals and tissue. Long-term inhalation of low concentrations or short-term inhalation of high concentrations can result in adverse health effects.
製法・合成法
製造方法
Benzyl chloroformate is prepared in the lab by treating benzyl alcohol with phosgene:PhCH2OH + COCl2→ PhCH2OC(O)Cl + HClPhosgene is used in excess to minimise the production of the carbonate (PhCH2O)2C=O.The use of phosgene gas in the lab preparation carries a very large health hazard, and has been implicated in the chronic pulmonary disease of pioneers in the usage of the compound such as Zervas.
純化方法
The commercial material is usually better than 95% pure and may contain some toluene, benzyl alcohol, benzyl chloride and HCl. After long storage (e.g. two years at 4o, Greenstein and Winitz [The Chemistry of the Amino Acids Vol 2 p. 890, J Wiley and Sons NY, 1961] recommended that the liquid should be flushed with a stream of dry air, filtered and stored over sodium sulfate to remove CO2 and HCl which are formed by decomposition. It may further be distilled from an oil bath at a temperature below 85o because Thiel and Dent [Annalen 301 257 1898] stated that benzyloxycarbonyl chloride decarboxylates to benzyl chloride slowly at 100o and vigorously at 155o. Redistillation at higher vacuum below 85o yields material which shows no other peaks than those of benzyloxycarbonyl chloride by NMR spectroscopy. [Beilstein 6 IV 2278.] LACHRYMATORY and TOXIC.