胡椒环 | 274-09-9

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 芳香烃
• 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: 胡椒环
• 中文别名: 儿茶酚次甲醚；甲撑二氧基苯；1,3-苯并间二氧杂环戊烯；1,3-苯并二噁茂；1,3-苯并二氧五环；1,2-亚甲二氧基苯；1,3-苯并二恶烷；1,3-苯并二氧杂茂；1,3-苯并二恶茂；1,3-苯并恶烷
• 英文名称: Methylenedioxybenzene
• 英文别名: 1,3-Benzodioxole；benzo[d][1,3]dioxole；1,2-methylenedioxybenzene；2H-1,3-benzodioxole；MDB
• CAS: 274-09-9
• 化学式: C₇H₆O₂
• mdl: MFCD00005818
• 分子量: 122.123
• InChiKey: FTNJQNQLEGKTGD-UHFFFAOYSA-N

物化性质

• 熔点：
  -18 °C
• 沸点：
  172-173 °C(lit.)
• 密度：
  1.064 g/mL at 25 °C(lit.)
• 闪点：
  131 °F
• 溶解度：
  2克/升
• LogP：
  2.08
• 保留指数：
  1530;1531
• 稳定性/保质期：
  存在于烟气中。

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.142
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

毒理性

• 副作用

神经毒素 - 其他中枢神经系统神经毒素

Neurotoxin - Other CNS neurotoxin

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

安全信息

• TSCA：
  Yes
• 危险等级：
  3
• 危险品标志：
  Xn
• 安全说明：
  S16,S23,S24/25,S26,S36/37/39
• 危险类别码：
  R22,R10
• WGK Germany：
  3
• 海关编码：
  29329970
• 危险品运输编号：
  UN 1993 3/PG 3
• 危险类别：
  3
• RTECS号：
  DA5600000
• 包装等级：
  III
• 危险性防范说明：
  P261,P271
• 危险性描述：
  H302+H332
• 储存条件：
  本品应密封保存。

SDS

Name:	]1,3-Benzodioxole, 99% Material Safety Data Sheet
Synonym:	1,2-(Methylenedioxy)benzene; 1,3-Dioxaindane
CAS:	274-09-9

Section 1 - Chemical Product MSDS Name: ]1,3-Benzodioxole, 99% Material Safety Data Sheet
Synonym: 1,2-(Methylenedioxy)benzene; 1,3-Dioxaindane

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SECTION 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
274-09-9	1,3-Benzodioxole	99.0	205-992-0

Hazard Symbols: XN
Risk Phrases: 10 22

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SECTION 3 - HAZARDS IDENTIFICATION EMERGENCY OVERVIEW Flammable. Harmful if swallowed. Potential Health Effects
Eye:
May cause chemical conjunctivitis and corneal damage.
Skin:
May cause irritation and dermatitis. May cause cyanosis of the extremities.
Ingestion:
May cause gastrointestinal irritation with nausea, vomiting and diarrhea. Ingestion of large amounts may cause CNS depression.
Inhalation:
Aspiration may lead to pulmonary edema. Vapors may cause dizziness or suffocation. May cause burning sensation in the chest.
Chronic:
No information found.

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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. Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid immediately.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Remove contaminated clothing and shoes.
Ingestion:
If victim is conscious and alert, give 2-4 cupfuls of milk or water. Get medical aid immediately. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water.
Inhalation:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.
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. Vapors may form an explosive mixture with air. Vapors can travel to a source of ignition and flash back. Will burn if involved in a fire. Use water spray to keep fire-exposed containers cool. Containers may explode in the heat of a fire. Flammable liquid and vapor. Vapors may be heavier than air. They can spread along the ground and collect in low or confined areas.
Extinguishing Media:
For small fires, use dry chemical, carbon dioxide, water spray or alcohol-resistant foam. For large fires, use water spray, fog, or alcohol-resistant foam. Use water spray to cool fire-exposed containers. Water may be ineffective. Use agent most appropriate to extinguish fire. Do NOT use straight streams of water.

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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. Clean up spills immediately, observing precautions in the Protective Equipment section. Remove all sources of ignition. Use a spark-proof tool. A vapor suppressing foam may be used to reduce vapors.

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SECTION 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Ground and bond containers when transferring material. Use spark-proof tools and explosion proof equipment. Avoid contact with eyes, skin, and clothing. Empty containers retain product residue, (liquid and/or vapor), and can be dangerous. Keep container tightly closed. Keep away from heat, sparks and flame. Avoid ingestion and inhalation. Do not pressurize, cut, weld, braze, solder, drill, grind, or expose empty containers to heat, sparks or open flames.
Storage:
Keep away from heat, sparks, and flame. Keep away from sources of ignition. Store in a cool, dry, well-ventilated area away from incompatible substances. Flammables-area.

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SECTION 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate general or local exhaust ventilation to keep airborne concentrations below the permissible exposure limits. Use process enclosure, local exhaust ventilation, or other engineering controls to control airborne levels. Use adequate general or local explosion-proof ventilation to keep airborne levels to acceptable levels. Exposure Limits CAS# 274-09-9: Personal Protective Equipment
Eyes:
Wear safety glasses and chemical goggles if splashing is possible.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use. Wear a NIOSH/MSHA or European Standard EN 149 approved full-facepiece airline respirator in the positive pressure mode with emergency escape provisions.

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SECTION 9 - PHYSICAL AND CHEMICAL PROPERTIES
Physical State: Liquid
Color: clear slightly yellow
Odor: None reported.
pH: Not available.
Vapor Pressure: 12 mmHg @ 25 C
Viscosity: Not available.
Boiling Point: 172.0 - 173.0 deg C @ 760.00m
Freezing/Melting Point: -18.00 - -0.00 deg C
Autoignition Temperature: Not available.
Flash Point: 55 deg C ( 131.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: 0.2% (25 c)
Specific Gravity/Density: 1.0640g/cm3
Molecular Formula: C7H6O2
Molecular Weight: 122.12

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SECTION 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, ignition sources, excess heat, strong oxidants.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, irritating and toxic fumes and gases, carbon dioxide.
Hazardous Polymerization: Has not been reported.

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SECTION 11 - TOXICOLOGICAL INFORMATION RTECS#: CAS# 274-09-9: DA5600000
LD50/LC50:
CAS# 274-09-9: Oral, mouse: LD50 = 1220 mg/kg; Oral, rat: LD50 = 580 mg/kg.
Carcinogenicity:
1,3-Benzodioxole - Not listed by ACGIH, IARC, or NTP.
Other:
See actual entry in RTECS for complete information.

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SECTION 12 - ECOLOGICAL INFORMATION Other No information available.

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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: FLAMMABLE LIQUID, N.O.S.
Hazard Class: 3
UN Number: 1993
Packing Group: III IMO
Shipping Name: FLAMMABLE LIQUID, N.O.S.
Hazard Class: 3.3
UN Number: 1993
Packing Group: III RID/ADR
Shipping Name: FLAMMABLE LIQUID, N.O.S.
Hazard Class: 3
UN Number: 1993
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 10 Flammable. R 22 Harmful if swallowed.
Safety Phrases:
S 9 Keep container in a well-ventilated place. S 16 Keep away from sources of ignition - No smoking. S 33 Take precautionary measures against static discharges. WGK (Water Danger/Protection) CAS# 274-09-9: No information available. Canada CAS# 274-09-9 is listed on Canada's NDSL List. CAS# 274-09-9 is not listed on Canada's Ingredient Disclosure List. US FEDERAL TSCA CAS# 274-09-9 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
MSDS Creation Date: 9/02/1997 Revision #4 Date: 3/18/2003 The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no way shall the company be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if the company has been advised of the possibility of such damages.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

胡椒环 简介

胡椒环，化学名为1,2-亚甲二氧基苯，广泛应用于低毒杀虫剂、黄连素、洋茉莉醛和芝麻酚以及抗氧化剂的制备。由于其特殊的生化活性，胡椒环及其衍生物备受关注。

外观与性状

透明无色至淡黄色液体

制备方法

1. 将440毫升DMSO、120毫升二氯甲烷和230克氢氧化钠加入到一个2升的三口烧瓶中，升温至95℃。
2. 滴加110克邻苯二酚溶解在440毫升DMSO中的溶液，控制体系温度不超过120℃，滴加时间约为3-4小时。
3. 滴完后加入90毫升二氯甲烷，并于110-115℃回流保温半小时。
4. 冷却至室温，过滤除去氯化钠。向反应液中加入400毫升水并使用油水分离器分离残余的二氯甲烷和胡椒环。
5. 分离到基本无明显油相蒸馏出来后开始蒸馏回收水，水相用适量的二氯甲烷萃取，萃取后的水相可循环套用。继续蒸馏至顶温100℃，切换为蒸馏回收DMSO，回收的DMSO也可循环利用。
6. 残余物约90克。油水分离得到有机相胡椒环129克，气相纯度为97%，收率为85.4%。

化学性质

• 沸点：172-173℃
• 相对密度：1.064（20/4℃）
• 折光率：1.5398
• 闪点：55℃
• 不溶于酸

用途

胡椒环作为有机合成中间体，主要用于黄连素的合成。此外，它也是制备奥索利酸、西诺沙星和米诺沙星等化合物的重要中间体。

生产方法

胡椒环由儿茶酚经环合而得。具体步骤如下：

1. 将儿茶酚溶于二甲基亚砜（DMSO）中。
2. 氢氧化钠溶解在剩余的二甲基亚砜中，并加入二氯甲烷，搅拌并加热回流至温度升至95℃。
3. 逐渐滴加儿茶酚溶液，保持回流温度在95-110℃。
4. 在110-115℃保温搅拌1小时后，在130℃进行水蒸气蒸馏。低沸点馏分供下批套用，收集98-110℃正馏分，静置后分出油层即得胡椒环，收率为85%。

反应信息

• 作为反应物：
  描述：

  胡椒环 在 盐酸 、 sodium hydrogen sulfate 、 氢气 、 zinc(II) oxide 、 zinc(II) chloride 作用下， 以 水 、 1,2-二氯乙烷 、 异丙醇 为溶剂， 110.0 ℃ 、689.49 kPa 条件下， 反应 8.0h， 生成 增效醚
  参考文献：
  名称：

  [EN] AN EFFICIENT PROCESS FOR PREPARATION OF ACYL DERIVATIVES OF ALKYLENEDIOXYBENZENES
  [FR] PROCÉDÉ EFFICACE POUR LA PRÉPARATION DE DÉRIVÉS ACYLE D'ALKYLÈNEDIOXYBENZÈNES

  摘要：

  本公开提供了一种制备I式化合物的过程，包括以下步骤：在溶剂存在下，将II式烷二氧基苯化合物与III式酰卤反应，其中将II式烷二氧基苯化合物与III式酰卤反应的步骤在存在两性氧化物和路易斯酸的情况下进行，以立即淬灭在反应过程中形成的H-X式化合物，从而实质性地消除任何I式和II式化合物的降解。本公开还提供了制备IVa、IVb和IVc式化合物的过程。

  公开号：

  WO2021161083A1
• 作为产物：
  描述：

  3.4-(亚甲基二氧基)苯硼酸 在 (1,5-cyclooctadiene)(methoxy)iridium(I) dimer 、 四羟基二硼 、 1,3-bis(di(4-methoxyphenyl)phosphino)propane 作用下， 以 水 、 1,2-二氯乙烷 为溶剂， 反应 0.25h， 以99%的产率得到胡椒环
  参考文献：
  名称：

  碳酸亚乙烯酯与芳基硼酸的铱催化芳基化反应合成芳基乙醛

  摘要：

  在铱/双膦催化剂和催化量的四羟基二硼存在下，碳酸亚乙烯酯与芳基硼酸的反应已实现了通过甲酰甲基与芳基之间的碳-碳键形成一步合成芳基乙醛。

  DOI：

  10.1002/anie.201906148
• 作为试剂：
  描述：

  3-methyl-2-phenyl-1-butene 在 胡椒环 、 indium(III) bromide 、 水 作用下， 以40%的产率得到1,2-二甲基丙基苯
  参考文献：
  名称：

  烯烃中的催化转移氢化和区域选择性氢-氘加成

  摘要：

  为芳香族和脂肪族 1,1-二-和三取代烯烃的氢化开发了一种独特且有价值的方法。在催化 InBr 3的存在下，容易获得的 1,3-苯并二氧杂环戊烷和存在于反应混合物中的残留 H 2 O 被用作氢气替代物，并证明是通过改变两侧的烯烃结合氘的实用来源起始氘代 1,3-苯并二恶唑或 D 2 O的来源。实验研究表明，氢化物从 1,3-苯并二恶唑转移到由 H 2 O–InBr 3加合物使烯烃质子化产生的碳阳离子中间体仍然是关键步骤。

  DOI：

  10.1021/acs.joc.3c00272

文献信息

• Cell adhesion-inhibiting antiinflammatory and immune-suppressive compounds
  申请人：Abbott Laboratories

  公开号：US20040116518A1

  公开（公告）日：2004-06-17

  The present invention relates to novel cinnamide compounds that are useful for treating inflammatory and immune diseases and cerebral vasospasm, to pharmaceutical compositions containing these compounds, and to methods of inhibiting inflammation or suppressing immune response in a mammal.

  本发明涉及新型肉桂酰胺化合物，用于治疗炎症和免疫性疾病以及脑血管痉挛，以及含有这些化合物的药物组合物，以及在哺乳动物中抑制炎症或抑制免疫反应的方法。
• Compositions for Treatment of Cystic Fibrosis and Other Chronic Diseases
  申请人：Vertex Pharmaceuticals Incorporated

  公开号：US20150231142A1

  公开（公告）日：2015-08-20

  The present invention relates to pharmaceutical compositions comprising an inhibitor of epithelial sodium channel activity in combination with at least one ABC Transporter modulator compound of Formula A, Formula B, Formula C, or Formula D. The invention also relates to pharmaceutical formulations thereof, and to methods of using such compositions in the treatment of CFTR mediated diseases, particularly cystic fibrosis using the pharmaceutical combination compositions.

  本发明涉及含有上皮钠通道活性抑制剂与至少一种ABC转运蛋白调节剂化合物（A式、B式、C式或D式）的药物组合物。该发明还涉及这些药物配方，以及使用这些组合物治疗CFTR介导的疾病，特别是囊性纤维化的方法。
• [EN] AGENTS AND METHODS FOR TREATING DYSPROLIFERATIVE DISEASES<br/>[FR] AGENTS ET MÉTHODES POUR TRAITER DES MALADIES DYSPROLIFÉRATIVES
  申请人：MEMORIAL SLOAN KETTERING CANCER CENTER

  公开号：WO2019161345A1

  公开（公告）日：2019-08-22

  Compounds are described with the general formula (I) wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, and n are defined as anywhere herein, which are useful for the treatment of cancer and other dysproliferative diseases.

  化合物的一般公式为（I），其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和n的定义如本文的任何地方所述，这些化合物对于治疗癌症和其他增生异常疾病是有用的。
• SUBSTITUTED 4-PYRIDONES AND THEIR USE AS INHIBITORS OF NEUTROPHIL ELASTASE ACTIVITY
  申请人：OOST Thorsten

  公开号：US20140057916A1

  公开（公告）日：2014-02-27

  This invention relates to substituted 4-pyridones of formula 1 and their use as inhibitors of neutrophil elastase activity, pharmaceutical compositions containing the same, and methods of using the same as agents for treatment and/or prevention of pulmonary, gastrointestinal and genitourinary diseases, inflammatory diseases of the skin and the eye and other auto-immune and allergic disorders, allograft rejection, and oncological diseases.

  这项发明涉及式1的取代4-吡啶酮及其作为中性粒细胞弹性蛋白酶活性抑制剂的用途，包含这些化合物的药物组合物，以及将其用作治疗和/或预防肺部、胃肠道和泌尿系统疾病、皮肤和眼睛的炎症性疾病以及其他自身免疫和过敏性疾病、移植物排斥反应和肿瘤性疾病的药剂的方法。
• [EN] CATHEPSIN CYSTEINE PROTEASE INHIBITORS<br/>[FR] INHIBITEURS DE PROTÉASES À CYSTÉINE DE TYPE CATHEPSINES
  申请人：MERCK SHARP & DOHME

  公开号：WO2015054038A1

  公开（公告）日：2015-04-16

  This invention relates to a novel class of compounds which are cysteine protease inhibitors, including but not limited to, inhibitors of cathepsins K, L, S and B. These compounds are useful for treating diseases in which inhibition of bone resorption is indicated, such as osteoporosis.

  这项发明涉及一类新型化合物，它们是半胱氨酸蛋白酶抑制剂，包括但不限于对卡特普辛K、L、S和B的抑制剂。这些化合物可用于治疗需要抑制骨吸收的疾病，如骨质疏松症。

表征谱图