化工社化工社 化学情報印刷レポート · 研究参考用
1,1,1,3,3,3-ヘキサメチルジシラザン
1,1,1,3,3,3-ヘキサメチルジシラザン · 1,1,1,3,3,3-ヘキサメチルプロパンジシラザン · ジ(トリメチルシリル)アミン · N-(トリメチルシリル)トリメチルシランアミン · ヘキサメチルシラザン · 1,1,1,3,3,3-ヘキサメチル-1,3-ジシラ-2-アザプロパン · イミノビス(トリメチルシラン) · ヘキサメチルジシラザン
識別子と物理属性
| CAS No. | 4039-32-1 |
|---|---|
| 分子式 | C6H19NSi2 |
| 平均分子量 | 161.39 g/mol |
| 単同位体質量 | 161.10560267 g/mol |
| SMILES | C[Si](C)(C)N[Si](C)(C)C |
| InChIKey | FFUAGWLWBBFQJT-UHFFFAOYSA-N |
| PubChem CID | 13838 |
| ChEMBL | CHEMBL3183662 |
| ChEBI | CHEBI:85068 |
| EC No. | 213-668-5 |
| DTXSID | DTXSID2025395 |
| 現地名 | 1,1,1,3,3,3-ヘキサメチルジシラザン |
化学・物理的性質
| 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 | 2 |
| 重原子数 | 9 |
| 形式電荷 | 0 |
| 複雑度 | 76.2 |
| 物質分類 | Metals -> Metalloid Compounds (Silicon)Corrosives |
| SpringerMaterials Properties | 15N nuclear magnetic resonance spectrum |
| LogP（分配係数） | log Kow = 2.62 /Estimated/ |
| 臭い | Ammonia-like odorアンモニア臭 |
| 密度 | 0.7741 g/cu cm at 25 °C0.76 @25 °C0.774 g/mL at 25 °C(lit.) |
| Viscosity | 0.90 centistokes |
| Color/Form | Colorless liquid |
| 溶解度 | Soluble in acetone, benzene, ethyl ether, heptane, perchloroethyleneInsol in water, reacts slowlyIn water, 392 mg/l @ 25 °C /Estimated/アセトン、ベンゼン、エチルエーテル、ヘプタン、ペルクロロエチレンと混和します。反応する |
| 引火点 | 48 °F (NFPA, 2010)27 °C81 °F (27 °C) closed cup14 °C (closed cup) /from table/57.2 °F |
| 沸点 | 125 °C125 °C @760 [mm Hg]125 °C (lit.) |
| 蒸気圧 | 13.8 [mmHg]13.8 mm Hg at 25 °C13.8 [mm Hg] @25 °C20 hPa (20 °C) |
| Food Contact Substances | FCS -> FDA Cumulative Estimated Daily Intake (CEDI) |
| 融点 | -78 °C |
| 蒸気密度 | 4.6 (vs air) |
| 屈折率 | n20/D 1.407(lit.) |
| 貯蔵条件 | Store below +30°C. |
| pKa（酸解離定数） | 30(at 25℃) |
| 外観・状態 | 液体 |
| 色 | 無色 |
| 比重 | 0.774 |
| 爆発限界 | 0.8-25.9%(V) |
| Merck | 14,4689 |
| BRN | 635752 |
| ヘンリー定数 | 1.1×10-1 mol/(m3Pa) at 25℃, HSDB (2015) |
| InChI | 1S/C6H19NSi2/c1-8(2,3)7-9(4,5)6/h7H,1-6H3 |
| InChIKey | FFUAGWLWBBFQJT-UHFFFAOYSA-N |
| SMILES | C[Si](C)(C)N[Si](C)(C)C |
| LogP（分配係数） | 0.23-1.19 at 20-25℃ |
| CAS データベース | 999-97-3(CAS DataBase Reference) |
| NISTの化学物質情報 | Silanamine, 1,1,1-trimethyl-N-(trimethylsilyl)-(999-97-3) |
| EPAの化学物質情報 | Hexamethyldisilazane (999-97-3) |
化学的特性
Hexamethyldisilazane, also known as HMDS, is an important organosilicon compound, a colorless and transparent liquid. It is readily hydrolyzed and gives off NH3 to produce hexamethyldisilyl ether. In the presence of a catalyst, it reacts with alcohols or phenols to produce trimethylalkoxysilane or trimethylaroxysilane. Reacts with anhydrous hydrogen chloride, releasing NH3 or NH4Cl, to produce trimethylchlorosilane.
安全性と法規制
| GHS 分類 | This chemical does not meet GHS hazard criteria for 5.8% (35 of 606) of reports.DangerH225 (93.7%): Highly Flammable liquid and vapor [Danger Flammable liquids]P210, P233, P240, P241, P242, P243, P260, P261, P262, P264, P270, P271, P273, P280, P301+P317, P301+P330+P331, P302+P352, P302+P361+P354, P303+P361+P353, P304+P340, P305+P354+P338, P316, P317, P321, P330, P361+P364, P363, P370+P378, P403+P235, P405, and P501 (click each P-code to see the statement)Aggregated GHS information provided per 606 reports by companies from 27 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies. |
|---|---|
| 規制情報 | Chemical: Silanamine, 1,1,1-trimethyl-N-(trimethylsilyl)-Regulation (EC) No 1935/2004 (amended)Silanamine, 1,1,1-trimethyl-N-(trimethylsilyl)- is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Silanamine, 1,1,1-trimethyl-N-(trimethylsilyl)- 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: 25-04-2023 https://echa.europa.eu/registration-dossier/-/registered-dossier/152741,1,1,3,3,3-Hexamethyldisilazane: 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.) |
| 輸送ラベル（DOT） | Flammable Liquid Corrosive |
| 火災危険 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]: |
| 火災の可能性 | Measurements of the autoignition temperatures for several series of mono-,di-, tri- and tetra-alkylsilanes showed that the ease of oxidation decrease with increasing substitution. /Hexamethylsilazane is an/ easily ignited or pyrophoric compound. |
| 健康有害性 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]: |
| 有害性の概要 | Corrosive to skin[Quick CPC] Reacts with water to release ammoniaLiquid can cause skin burns and eye damageVapors can cause respiratory tract irritation and lung damage[CSH, p. 227] A skin and eye irritant[CAMEO] |
| 反応性グループ | Reducing Agents, Strong |
| TSCA 要件 | Section 8(a) of TSCA requires manufacturers of this chemical substance to report preliminary assessment information concerned with production, exposure, and use to EPA as cited in the preamble in 51 FR 41329.Pursuant to section 8(d) of TSCA, EPA promulgated a model Health and Safety Data Reporting Rule. The section 8(d) model rule requires manufacturers, importers, and processors of listed chemical substances and mixtures to submit to EPA copies and lists of unpublished health and safety studies. Hexamethyldisilazane is included on this list. |
| Reactivity Alerts | Highly Flammable |
| Reactivity Profile | HEXAMETHYL DISILAZANE reacts with many carbonyl-containing organic compounds to generate gaseous ammonia. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Flammable gaseous hydrogen may be generated in combination with stronger reducing agents, such as hydrides. |
| Air and Water Reactions | Highly flammable. Moisture sensitive. |
| Hazard Classes and Categories | Flam. Liq. 2 (93.7%)Flammable liquids - Category 2Corrosives, Flammable agents - 3rd degree, Reactive agents - 1st degree |
| 消火 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]: |
| 応急処置 | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]: |
| 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. |
| Preventive Measures | SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place. |
| Isolation and Evacuation | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]: |
| Protective Action Criteria (PAC) | 5.8 [mg/m3]64 [mg/m3]380 [mg/m3] |
| Personal Protective Equipment (PPE) | Excerpt from ERG Guide 132 [Flammable Liquids - Corrosive]: |
| 生態毒性値 | LC50 Pimephales promelas (Fathead minnow) 167 mg/L/96 hrstaticLC50 Daphnia magna (Waterflea) 186 mg/L/48 hr /Conditions of bioassay not specified in source examined/ |
| 環境中動態 | TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 390(SRC), determined from a structure estimation method(2), indicates that hexamethyldisilazane is expected to have moderate mobility in soil(SRC). Volatilization of hexamethyldisilazane from moist soil surfaces is expected to be an important fate process(SRC) given an estimated Henry's Law constant of 8.7X10-5 atm-cu m/mole(SRC), using a fragment constant estimation method(3). The potential for volatilization of hexamethyldisilazane from dry soil surfaces may exist(SRC) based upon a vapor pressure of 13.8 mm Hg(4).AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 390(SRC), determined from a structure estimation method(2), indicates that hexamethyldisilazane may adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon an estimated Henry's Law constant of 8.7X10-5 atm-cu m/mole(SRC), developed using a fragment constant estimation method(4). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 9.9 hours and 8.9 days, respectively(SRC). The pKa of hexamethyldisilazane is 7.55(5), indicating that this compound will partially exist in cation form in the environment and cations generally adsorb more strongly to organic carbon and clay than their neutral counterparts(6). According to a classification scheme(7), an estimated BCF of 21(SRC), from an estimated log Kow of 2.6(8) and a regression-derived equation(9), suggests the potential for bioconcentration in aquatic organisms is low(SRC). Hexamethyldisilazane is expected to hydrolyze slowly in water(5,10,11), although actual rate data for this compound were not located.ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), hexamethyldisilazane, which has a vapor pressure of 13.8 mm Hg at 25 °C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase hexamethyldisilazane 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 18 days(SRC), calculated from its rate constant of 9.0X10-13 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). |
| 有害作用 | Dermatotoxin - Skin burns. |
| Soil Adsorption/Mobility | Using a structure estimation method based on molecular connectivity indices(1), the Koc for hexamethyldisilazane can be estimated to be 390(SRC). According to a classification scheme(2), this estimated Koc value suggests that hexamethyldisilazane is expected to have moderate mobility in soil. The pKa of hexamethyldisilazane is 7.55(3), indicating that this compound will partially exist exist in cation form in the environment and cations generally adsorb more strongly to organic carbon and clay than their neutral counterparts(4). |
| Human Toxicity Excerpts | /HUMAN EXPOSURE STUDIES/ During many years of production no case of skin burns has been observed although there has been skin contact with the product by accident. This may be explained by the high volatility of the substance. Skin irritation tests in animals have been conducted under occlusion. |
| Artificial Pollution Sources | Hexamethyldisilazane's production and use as a chemical intermediate, an adhesion promoter in photoresists, and a chromatographic support material(1,2) may result in its release to the environment through various waste streams(SRC). |
| Environmental Bioconcentration | An estimated BCF of 21 was calculated for hexamethyldisilazane(SRC), using an estimated log Kow of 2.6(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 hexamethyldisilazane is estimated as 8.7X10-5 atm-cu m/mole(SRC) using a fragment constant estimation method(1). This Henry's Law constant indicates that hexamethyldisilazane is expected to volatilize from water surfaces(2). 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)(2) is estimated as 9.9 hours(SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(2) is estimated as 8.9 days(SRC). Hexamethyldisilazane's Henry's Law constant indicates that volatilization from moist soil surfaces may occur(SRC). The potential for volatilization of hexamethyldisilazane from dry soil surfaces may exist(SRC) based upon a vapor pressure of 13.8 mm Hg(3). |
| Non-Human Toxicity Excerpts | /LABORATORY ANIMALS: Acute Exposure/ /In an acute oral study using mice/ ...at 300 and 450 mg/kg sedation was observed, at higher dose levels up to 1500 mg/kg: difficult breathing, ataxia and hyperexcitability followed by a "prolonged" narcosis with loss of righting reflex./LABORATORY ANIMALS: Acute Exposure/ 4 hr application /to rabbit skin/ resulted in severe erythema, moderate to severe edema and necrosis on all six rabbits. 1 hr application produced moderate erythema, minor to moderate edema and necrosis on each of six rabbits./GENOTOXICITY/ Negative with and without activation in the Escherichia coli reverse mutation assay 0-5,000 ug/plate./GENOTOXICITY/ Negative with and without activation in the Ames test using Salmonella typhimurium TA 98, TA 100, TA 1535, TA 1537, TA 1538 0-5,000 ug/plate./ALTERNATIVE IN VITRO TESTS/ The ability of two commercial in-vitro assays to predict the skin irritancy and corrosivity potential of organosilicon compounds was examined. The Skin2 1350 and CORROSITEX assays were used to evaluate skin irritancy of hexamethyldisiloxane. ...CORROSITEX classified hexamethyldisilazane as corrosive, whereas the in-vivo test indicated that it was only minimally irritating. |
| Environmental Abiotic Degradation | The rate constant for the vapor-phase reaction of hexamethyldisilazane with photochemically-produced hydroxyl radicals has been estimated as 9.0X10-13 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 18 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). One study reports that hexamethyldisilazane hydrolyzes on contact with water(2). However, other sources suggest that this substance hydrolyzes more slowly(3,4). Hydrolysis rate and half-life data for hexamethyldisilazane were not found in the literature. Hexamethyldisilazane is not expected to directly photolyze due to the lack of absorption in the environmental UV spectrum (>290 nm). |
| Probable Routes of Human Exposure | Occupational exposure to hexamethyldisilazane may occur through inhalation and dermal contact with this compound at workplaces where hexamethyldisilazane is produced or used. (SRC) |
| Environmental Fate/Exposure Summary | Hexamethyldisilazane's production and use as a chemical intermediate, an adhesion promoter in photoresists, and a chromatographic support material may result in its release to the environment through various waste streams. If released to air, a vapor pressure of 13.8 mm Hg at 25 °C indicates hexamethyldisilazane will exist solely as a vapor in the ambient atmosphere. Vapor-phase hexamethyldisilazane will be degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicalsthe half-life for this reaction in air is estimated to be 18 days. If released to soil, hexamethyldisilazane is expected to have moderate mobility based upon an estimated Koc of 390. Volatilization from moist soil surfaces is expected to be an important fate process based upon an estimated Henry's Law constant of 8.7X10-5 atm-cu m/mole. The pKa of hexamethyldisilazane is 7.55, indicating that this compound will partially exist in cation form in the environment and cations generally adsorb more strongly to organic carbon and clay than their neutral counterparts. Hexamethyldisilazane may volatilize from dry soil surfaces based upon its vapor pressure. If released into water, hexamethyldisilazane may adsorb to suspended solids and sediment based upon the estimated Koc. Volatilization from water surfaces is expected to be an important fate process based upon this compound's estimated Henry's Law constant. Estimated volatilization half-lives for a model river and model lake are 9.9 hours and 8.9 days, respectively. An estimated BCF of 21 suggests the potential for bioconcentration in aquatic organisms is low. One study reports that hexamethyldisilazane hydrolyzes on contact with water. However, other sources suggest that this substance hydrolyzes more slowly. Hydrolysis rate and half-life data for hexamethyldisilazane were not found in the literature. Occupational exposure to hexamethyldisilazane may occur through inhalation and dermal contact with this compound at workplaces where hexamethyldisilazane is produced or used. (SRC) |
| F | 21 |
| 水環境危害等級（WGK） | 2 |
| TSCA 収載状態 | TSCA listed |
| RTECS 番号 | JM9230000 |
| 輸送番号（UN） | UN 3286 3/PG 2 |
| 毒性 | LDLO i.p. in mice: 650 mg/kg (Petrarch Systems Inc. Product Information Sheets) |
| 税関コード | 2931 90 00 |
| 危険文句（R） | 11-20/21/22-34-52/53 |
| 化審法 | (2)-2044, (2)-2955, (9)-1324 |
| 消防法 | 危-4-1-II |
| 危険表示 | F,C,Xn |
| hazard_note | Flammable |
| 安全措置（S） | 16-26-36/37/39-45-61 |
| 危険等級 | 3Acute Tox. 3 DermalAcute Tox. 4 InhalationAcute Tox. 4 OralAquatic Chronic 3Flam. Liq. 2 |
| 包装等級 | II |
| 自然発火温度 | 325 °C |
| 貯蔵分類 | 3 - Flammable liquids |
| 有害物質データ | 999-97-3(Hazardous Substances Data) |
用途
解説
ヘキサメチルジシラザン，1,1,1-trimethyl-N-(trimethylsilyl)silanamine, bis(trimethylsilyl)amine．C6H19NSi2(161.40)．(CH3)3SiNHSi(CH3)3．クロロトリメチルシランとアンモニアとをエーテル中で反応させると得られる．無色の液体．沸点126 ℃．d4200.765．nD201.4071．加水分解されやすく，トリメチルシラノールを経てヘキサメチルジシロキサンになる．アルコール類，アミン，カルボン酸などの活性水素のシリル化剤に用いられる．アルカリ金属誘導体は強塩基として有機合成に使われる．
用途
クロマトグラフ支持材料の非活性化、 セミコンダクター装置製造時のシリコーンまたは酸化シリコーンのフォトレジスト圧着の推進剤
説明
Hexamethyldisilazane is a bulk organo silicon compound, being a quite useful silanizing agent. It is a reagent for the preparation of trimethylsilyl derivatives. It can also be used to dehydrate cells of biomaterials for scanning electron microscopy (SEM). Moreover, it is an adhesion promoter for photoresist in photolithography, and is also useful in the pyrolysis-gas chromatography-mass spectrometry to enhance the detectability of compounds with polar functional groups.
使用
Hexamethyldisilazane mainly used as methyl silane alkylation (such as amikacin, penicillin, cephalosporins and kinds of penicillin derivatives), hydroxyl protectants of antibiotics. It is used as surface treatment agent of diatomite, white carbon black, titanium and blond additives of photoresist in the semiconductor industry. It is used as treatment agent of tearing strength resistance. It is used as a solvent in organic synthesis and organometallic chemistry. It is used as an adhesion promoter for photoresist in photolithography. it is used for the preparation of trimethylsilyl ethers from hydroxy compounds. It is used as an alternative to critical point drying during sample preparation in electron microscopy. It is added to analyte to get silylated diagnostic products during pyrolysis in gas chromatography- mass spectrometry.
一般的な説明
Hexamethyldisilazane appears as a liquid. May be toxic by ingestion. Irritates skin and eyes. Vapors are heavier than air. May emit highly toxic nitrogen oxide fumes when heated to decomposition. Used to deactivate chromatography support materials and to promote adhesion of photoresists in the electronics industry.
製法・合成法
純化方法
A possible impurity is Me3SiCl. Wash it well with pet ether and fractionate it through a vacuum jacketed column packed with Helipac using a reflux ratio of 10:1. [Langer et al. J Org Chem 23 50 1958, Beilstein 4 IV 4014.]