3,4-(亚甲二氧基)苯甲基硫代异氰酸酯 | 4430-47-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 中文名称: 3,4-(亚甲二氧基)苯甲基硫代异氰酸酯
• 中文别名: 3,4-(亚甲基二氧基)异硫氰酸苄；1,3-苯并二氧醇-5-基甲基异硫氰酸酯
• 英文名称: 1,3-benzodioxol-5-ylmethyl isothiocyanate
• 英文别名: 3,4-(methylenedioxy)benzyl isothiocyanate；5-(isothiocyanatomethyl)benzo[d][1,3]dioxole；5-(Isothiocyanatomethyl)-1,3-benzodioxole
• CAS: 4430-47-1
• 化学式: C₉H₇NO₂S
• mdl: MFCD00041217
• 分子量: 193.226
• InChiKey: PUJWRDBPAFJUJW-UHFFFAOYSA-N

物化性质

• 沸点：
  140 °C
• 密度：
  1.32
• 闪点：
  139-140°C/1mm
• 稳定性/保质期：
  在常温常压下保持稳定

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.222
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 危险等级：
  6.1
• 危险品标志：
  Xn
• 危险类别码：
  R20/21/22,R36/37/38
• 危险品运输编号：
  UN 2810
• 海关编码：
  2932999099
• 包装等级：
  II
• 危险类别：
  6.1
• 安全说明：
  S26,S36/37/39
• 储存条件：
  请将药品存放在避光、通风干燥的地方，并密封保存。

SDS

Name:	1 3-Benzodioxol-5-ylmethyl isothiocyanate 95%+ Material Safety Data Sheet
Synonym:
CAS:	4430-47-1

Section 1 - Chemical Product MSDS Name:1 3-Benzodioxol-5-ylmethyl isothiocyanate 95%+ Material Safety Data Sheet
Synonym:

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
4430-47-1	1,3-Benzodioxol-5-ylmethyl isothiocyan		unlisted

Hazard Symbols: XN
Risk Phrases: 20/21/22 36/37/38

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Harmful by inhalation, in contact with skin and if swallowed.
Irritating to eyes, respiratory system and skin.Moisture sensitive.
Potential Health Effects
Eye:
Causes eye irritation.
Skin:
Causes skin irritation. Harmful if absorbed through the skin.
Ingestion:
Harmful if swallowed. May cause irritation of the digestive tract.
Inhalation:
Harmful if inhaled. Causes respiratory tract irritation.
Chronic:
Not available.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Ingestion:
Get medical aid. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container.

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Section 7 - HANDLING and STORAGE
Handling:
Avoid breathing dust, vapor, mist, or gas. Avoid contact with skin and eyes.
Storage:
Keep refrigerated. (Store below 4C/39F.) Store in a tightly closed container. Store in a dry area.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 4430-47-1: Personal Protective Equipment Eyes: Not available.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Liquid
Color: Not available.
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 139 - 140 deg C @1mmHg
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density: 1.32
Molecular Formula: C9H7NO2S
Molecular Weight: 193.22

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents, moisture.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, oxides of sulfur, carbon dioxide.
Hazardous Polymerization: Not available.

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 4430-47-1 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
1,3-Benzodioxol-5-ylmethyl isothiocyanate, 95%+ - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: TOXIC LIQUID, ORGANIC, N.O.S.*
Hazard Class: 6.1
UN Number: 2810
Packing Group: III
IMO
Shipping Name: TOXIC LIQUID, ORGANIC, N.O.S.
Hazard Class: 6.1
UN Number: 2810
Packing Group: III
RID/ADR
Shipping Name: TOXIC LIQUID, ORGANIC, N.O.S.
Hazard Class: 6.1
UN Number: 2810
Packing group: III

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XN
Risk Phrases:
R 20/21/22 Harmful by inhalation, in contact with
skin and if swallowed.
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 36/37/39 Wear suitable protective clothing, gloves
and eye/face protection.
WGK (Water Danger/Protection)
CAS# 4430-47-1: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 4430-47-1 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 4430-47-1 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  3,4-(亚甲二氧基)苯甲基硫代异氰酸酯 在 氨 、 水 作用下， 以 乙酸乙酯 为溶剂， 生成 benzo[1,3]dioxol-5-ylmethyl-thiourea
  参考文献：
  名称：

  一锅制备 氰胺 使用分子碘从二硫代氨基甲酸酯中提取

  摘要：

  公开了一种通过使用分子碘的双脱硫策略由二硫代氨基甲酸盐合成氰胺的有效的一锅法。二硫代氨基甲酸酯，通过碘的作用异硫氰酸酯 原位，经水处理NH 3 给 硫脲。这硫脲因此生成的产物经I 2进一步氧化脱硫，从而以良好的收率得到相应的氰酰胺。环境友好性，成本效益和高产量是这一一锅法的重要属性。

  DOI：

  10.1039/b914283p
• 作为产物：
  描述：

  triethylamine (benzo[d][1,3]dioxol-5-ylmethyl)carbamodithioate 在 碳酸氢钠 、 tetrapropylammonium tribromide 作用下， 以 水 、 乙酸乙酯 为溶剂， 以86%的产率得到3,4-(亚甲二氧基)苯甲基硫代异氰酸酯
  参考文献：
  名称：

  使用环境友好的试剂四丙基三溴化铵从二硫代氨基甲酸酯盐中新颖合成一锅法合成异硫氰酸酯和氰胺。

  摘要：

  描述了在温和，有效且无毒的三溴化四铵铵存在下，由它们各自的胺合成异硫氰酸酯和氰胺的高效简单方法。试剂的高环境可接受性，成本效益和高产率是该方法的重要属性。

  DOI：

  10.17344/acsi.2017.3342

文献信息

• An automated, polymer-assisted strategy for the preparation of urea and thiourea derivatives of 15-membered azalides as potential antimalarial chemotherapeutics
  作者：Antun Hutinec、Renata Rupčić、Dinko Žiher、Kirsten S. Smith、Wilbur Milhous、William Ellis、Colin Ohrt、Zrinka Ivezić Schönfeld

  DOI：10.1016/j.bmc.2011.01.030

  日期：2011.3

  series of 15-membered azalide urea and thiourea derivatives has been synthesized and evaluated for their in vitro antimalarial activity against chloroquine-sensitive (D6), chloroquine/pyremethamine resistant (W2) and multidrug resistant (TM91C235) strains of Plasmodium falciparum. We have developed an effective automated synthetic strategy for the rapid synthesis of urea/thiourea libraries of a macrolide

  合成了一系列15元氮杂内酰胺脲和硫脲衍生物，并评估了它们对恶性疟原虫的氯喹敏感性（D6），氯喹/乙胺嘧啶抗性（W2）和多药耐药性（TM91C235）菌株的体外抗疟活性。我们已经开发出一种有效的自动化合成策略，用于大环内酯支架的尿素/硫脲库的快速合成。使用溶液相策略合成化合物，总收率为50–80％。大多数合成的化合物具有抑制作用。前三种化合物对所有三种菌株的效力比阿奇霉素高30-65倍，阿奇霉素具有抗疟疾活性。
• Chemoselective reduction of isothiocyanates to thioformamides mediated by the Schwartz reagent
  作者：Karen de la Vega-Hernández、Raffaele Senatore、Margherita Miele、Ernst Urban、Wolfgang Holzer、Vittorio Pace

  DOI：10.1039/c8ob02312c

  日期：——

  through the partial reduction of isothiocyanates with the in situ generated Schwartz reagent. The high electrophilicity of the starting materials enables the straightforward addition of the hydride ion, thus constituting a reliable and high-yielding method for obtaining variously functionalized thioformamides. Sensitive chemical groups to the reduction conditions such as nitro, ester, alkene, azo, azide and

  通过完全原位生成的Schwartz试剂将异硫氰酸酯部分还原，可以轻松地在完全化学控制下制备硫代甲酰胺。起始材料的高亲电性使氢化物离子的直接添加成为可能，从而构成了一种可靠且高产率的方法，可用于获得各种官能化的硫代甲酰胺。对还原条件敏感的化学基团，例如硝基，酯，烯烃，偶氮，叠氮化物和酮基，不会干扰该方法的化学选择性。此外，起始材料中体现的立体化学信息完全保留在最终产品中。还简要讨论了所选硫代甲酰胺模板的合成潜力。
• The thiocarbonyl ‘S’ is softer than thiolate ‘S’: A catalyst-free one-pot synthesis of isothiocyanates in water
  作者：Latonglila Jamir、Abdur Rezzak Ali、Harisadhan Ghosh、Francis A. S. Chipem、Bhisma K. Patel

  DOI：10.1039/b923336a

  日期：——

  Treatment of the preformed or the in situ generated aryl/alkyl dithiocarbamates triethylammonium salt (ArNHCSS−.Et3NH+) with methyl acrylate in an aqueous medium gave solely arylisothiocyanate (ArNCS), whereas the in situ generated aryl dithiocarbamic acid (ArNHCSS−.H+) yielded exclusively the thia-Michael adduct (ArNHCSSCH2CH2COOMe). This differential reactivity can be explained by two alternative mechanisms which is dependent both on the nature of the counter cation and on the pH of the reaction medium. Irrespective of the counter cations, the thiocarbonyl sulfur (=S) atom, having large orbital-coefficient, is softer compared to the thiol/thiolate sulfur (-SH/S−) in a dithiocarbamate salt and the former adds to the Michael acceptor by a 1,4-addition.

  在水中介质中，用甲基丙烯酸处理预制的或原位生成的芳基/烷基二硫代氨基甲酸盐三乙基铵盐（ArNHCSS−.Et3NH+）仅得到芳基异硫氰酸酯（ArNCS），而原位生成的芳基二硫代氨基甲酸（ArNHCSS−.H+）仅生成硫代迈克尔加合物（ArNHCSSCH2CH2COOMe）。这种差异性反应活性可以通过两种替代机制来解释，这取决于反荷离子的性质和反应介质的pH值。不管反荷离子如何，与二硫代氨基甲酸盐中的硫醇/硫醇盐硫（−SH/S−）相比，硫羰基硫（=S）原子具有较大的轨道系数，更为柔软，前者通过1,4-加成与迈克尔受体加合。
• A Robust, Eco‐Friendly Access to Secondary Thioamides through the Addition of Organolithium Reagents to Isothiocyanates in Cyclopentyl Methyl Ether (CPME)
  作者：Vittorio Pace、Laura Castoldi、Serena Monticelli、Sandra Safranek、Alexander Roller、Thierry Langer、Wolfgang Holzer

  DOI：10.1002/chem.201504247

  日期：2015.12.21

  The nucleophilic addition of widely available and variously functionalized organolithium reagents to isothiocyanates represents a straightforward, high‐yielding, one‐pot method to access secondary thioamides. The simple reaction conditions required and the broad scope (>50 cases examples) makes it a robust and reliable method to access both simple and complex thioamides, including enantiopure ones

  在异硫氰酸酯中亲和性广泛获得的各种官能化有机锂试剂的亲核加成反应是直接，高产率，一锅法获得仲硫代酰胺的方法。所需的简单反应条件和广泛的应用范围（> 50个案例）使其成为一种既简便又复杂的硫酰胺类（包括对映纯类）的可靠可靠的检测方法。在整个合成过程中避免使用通常在文献确定的方法中使用的有毒和难闻的硫化剂，从而使该方案在可持续性方面也具有很高的吸引力。
• Preparation of 2-Azido-1-Substituted-1 <i>H</i>-Benzo[<i>d</i>]imidazoles Using a Copper-Promoted Three-Component Reaction and Their Further Conversion into 2-Amino and 2-Triazolyl Derivatives
  作者：Tamminana Ramana、Tharmalingam Punniyamurthy

  DOI：10.1002/chem.201202215

  日期：2012.10.15

  Multicomponent reaction: 2‐Azido‐1‐substituted‐1H‐benzo[d]imidazoles were prepared using a copper‐catalyzed three‐component reaction involving 2‐bromoaniline derivatives, isothiocyanates, and sodium azide. The reaction conditions were mild and the scope was broad. The azido compounds were transformed into their 2‐amino and 2‐triazolyl derivatives using copper‐mediated reduction and cycloaddition, respectively

  多组分反应：使用2-铜苯胺衍生物，异硫氰酸盐和叠氮化钠的铜催化三组分反应制备2-叠氮基-1-取代-1 H-苯并[ d ]咪唑。反应条件温和，适用范围广。分别通过铜介导的还原和环加成将叠氮基化合物转化为它们的2-氨基和2-三唑基衍生物（参见方案）。

表征谱图