5-溴-1H-吡咯-2-羧酸甲酯 | 937-16-6

• 物质功能分类: 有机原料 - 杂环化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 中文名称: 5-溴-1H-吡咯-2-羧酸甲酯
• 英文名称: 4,5-dibromopyrrole-2-carboxylic acid methyl ester
• 英文别名: methyl 4,5-dibromo-1H-pyrrole-2-carboxylate；methyl 4,5-dibromopyrrole-2-carboxylate；O-methyl-4,5-dibromopyrrole-2-carboxylate；4,5-dibromo-pyrrole-2-carboxylic acid methyl ester；4,5-Dibrom-pyrrol-2-carbonsaeure-methylester
• CAS: 937-16-6
• 化学式: C₆H₅Br₂NO₂
• 分子量: 282.919
• InChiKey: ISQWCRSAYRXYRS-UHFFFAOYSA-N

物化性质

• 熔点：
  163-165°C
• 沸点：
  348.2±37.0 °C(Predicted)
• 密度：
  2.049±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  42.1
• 氢给体数：
  1
• 氢受体数：
  2

安全信息

• 危险等级：
  IRRITANT
• 危险品标志：
  Xi
• 海关编码：
  2933990090
• 危险性防范说明：
  P264,P280,P302+P352,P337+P313,P305+P351+P338,P362+P364,P332+P313
• 危险性描述：
  H315,H319

SDS

Material Safety Data Sheet

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Section 1. Identification of the substance
Product Name: Methyl 4,5-dibromo-1H-pyrrole-2-carboxylate
Synonyms:

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Section 2. Hazards identification
Harmful by inhalation, in contact with skin, and if swallowed.

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Section 3. Composition/information on ingredients.
Ingredient name: Methyl 4,5-dibromo-1H-pyrrole-2-carboxylate
CAS number: 937-16-6

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Section 4. First aid measures
Skin contact: Immediately wash skin with copious amounts of water for at least 15 minutes while removing
contaminated clothing and shoes. If irritation persists, seek medical attention.
Eye contact: Immediately wash skin with copious amounts of water for at least 15 minutes. Assure adequate
flushing of the eyes by separating the eyelids with fingers. If irritation persists, seek medical
attention.
Inhalation: Remove to fresh air. In severe cases or if symptoms persist, seek medical attention.
Ingestion: Wash out mouth with copious amounts of water for at least 15 minutes. Seek medical attention.

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Section 5. Fire fighting measures
In the event of a fire involving this material, alone or in combination with other materials, use dry
powder or carbon dioxide extinguishers. Protective clothing and self-contained breathing apparatus
should be worn.

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Section 6. Accidental release measures
Personal precautions: Wear suitable personal protective equipment which performs satisfactorily and meets local/state/national
standards.
Respiratory precaution: Wear approved mask/respirator
Hand precaution: Wear suitable gloves/gauntlets
Skin protection: Wear suitable protective clothing
Eye protection: Wear suitable eye protection
Methods for cleaning up: Mix with sand or similar inert absorbent material, sweep up and keep in a tightly closed container
for disposal. See section 12.
Environmental precautions: Do not allow material to enter drains or water courses.

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Section 7. Handling and storage
Handling: This product should be handled only by, or under the close supervision of, those properly qualified
in the handling and use of potentially hazardous chemicals, who should take into account the fire,
health and chemical hazard data given on this sheet.
Store in closed vessels.
Storage:

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Section 8. Exposure Controls / Personal protection
Engineering Controls: Use only in a chemical fume hood.
Personal protective equipment: Wear laboratory clothing, chemical-resistant gloves and safety goggles.
General hydiene measures: Wash thoroughly after handling. Wash contaminated clothing before reuse.

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Section 9. Physical and chemical properties
Appearance: Not specified
Boiling point: No data
No data
Melting point:
Flash point: No data
Density: No data
Molecular formula: C6H5Br2NO2
Molecular weight: 282.9

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Section 10. Stability and reactivity
Conditions to avoid: Heat, flames and sparks.
Materials to avoid: Oxidizing agents.
Possible hazardous combustion products: Carbon monoxide, nitrogen oxides, hydrogen bromide.

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Section 11. Toxicological information
No data.

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Section 12. Ecological information
No data.

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Section 13. Disposal consideration
Arrange disposal as special waste, by licensed disposal company, in consultation with local waste
disposal authority, in accordance with national and regional regulations.

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Section 14. Transportation information
Non-harzardous for air and ground transportation.

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Section 15. Regulatory information
No chemicals in this material are subject to the reporting requirements of SARA Title III, Section
302, or have known CAS numbers that exceed the threshold reporting levels established by SARA
Title III, Section 313.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  5-溴-1H-吡咯-2-羧酸甲酯 在 gold(III) chloride 、 水 、 sodium hydride 、 potassium carbonate 作用下， 以 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 75.0h， 生成 6,7-dibromo-3-methylene-3,4-dihydro-1H-pyrrolo[2,1-c][1,4]oxazin-1-one
  参考文献：
  名称：

  金催化的吡咯并-和吲哚-恶嗪-1-酮衍生物的形成：一些海洋天然产物的关键结构。

  摘要：

  通过金（III）催化的环化反应，将各种N-炔丙基吡咯和吲哚羧酸有效地转化为3，4-二氢吡咯并-和吲哚-恶嗪-1-酮衍生物。一些产物进行了TFA催化的双键异构化，而另一些则没有。在由Au（I）催化的醇存在下的环化反应导致级联反应后半缩醛的形成。

  DOI：

  10.3762/bjoc.11.101
• 作为产物：
  描述：

  2-吡咯甲酸甲酯 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 16.0h， 以29%的产率得到5-溴-1H-吡咯-2-羧酸甲酯
  参考文献：
  名称：

  4,5-二芳基-1H-吡咯-2-羧酸盐为康维他汀A-4 / lamellarin T杂种：合成和评估为抗有丝分裂剂和细胞毒性剂。

  摘要：

  4,5-二芳基化的1H-吡咯-2-羧酸盐3-8已分别作为有效的抗有丝分裂剂康维他汀A-4（1）和具有类似活性的海洋生物碱薄层蛋白T（2）的混合物制备。关键步骤涉及在N-PMB保护的4,5-二溴吡咯22中的C5处进行选择性的锂-卤素交换，以及衍生的锌化物质与相关的芳基碘化物的Negishi交叉偶联。然后将随后的5-芳基-4-溴吡咯与适当的芳基硼酸进行铃木-宫浦交叉偶联，得到4,5-二芳基吡咯4、6和8。TFA促进了其中N-PMB基团的去除。然后最后的化合物给出了N-未取代的同类物3、5和7。已经对化合物3-8的抗有丝分裂和细胞毒性特性进行了评估，其中的3和5是其中的两种。

  DOI：

  10.1016/j.bmc.2006.02.018

文献信息

• Selective Bromination of Pyrrole Derivatives, Carbazole and Aromatic Amines with DMSO/HBr under Mild Conditions
  作者：Cong Liu、Rongji Dai、Guowei Yao、Yulin Deng

  DOI：10.3184/174751914x14114780483352

  日期：2014.10

  Bromination of pyrrole derivatives, carbazole and aromatic amines using the DMSO/HBr system affords high yields of the corresponding bromo compounds. Temperature control used in the bromination of anilines helped to promote selective formation of mono- or di-brominated products. Simple operation, low toxicity and high selectivity make this a promising new procedure for the bromination of aromatic compounds

  使用 DMSO/HBr 系统溴化吡咯衍生物、咔唑和芳香胺可提供相应溴化合物的高产率。苯胺溴化中使用的温度控制有助于促进单溴化或二溴化产品的选择性形成。操作简单、毒性低、选择性高，使其成为一种很有前途的芳香族化合物溴化新工艺。
• HETERO-FUSED CYCLIC COMPOUND
  申请人：EISAI R&D MANAGEMENT CO., LTD.

  公开号：US20160168176A1

  公开（公告）日：2016-06-16

  A compound represented by the formula (I) or a salt thereof: wherein a ring Z is a 5 to 6-membered heteroaromatic ring having one or two heteroatoms in the ring; X 1 is a hydrogen atom, a hydroxy group, a hydroxy C 1-6 alkyl group, —B(OH) 2 , a boronate ester group, a cyclic boronate ester group, a boranyl group, a cyclic boranyl group, —BF 3 M n1 , —Sn(R 12 )(R 13 )(R 14 ), a leaving group, a carboxy group, a formyl group, or —NR 16 R 17 ; and X 2 is a hydrogen atom or —CO 2 R 18 .

  一个由化学式(I)表示的化合物或其盐：其中环Z是一个具有一个或两个杂原子的5到6元杂芳香环；X1是氢原子、羟基、羟基C1-6烷基基团、—B(OH)2、硼酸酯基团、环硼酸酯基团、硼烷基团、环硼烷基团、—BF3Mn1、—Sn(R12)(R13)(R14)、一个离去基团、一个羧基、一个甲酰基，或—NR16R17；而X2是氢原子或—CO2R18。
• Vanadate-dependent bromoperoxidases from Ascophyllum nodosum in the synthesis of brominated phenols and pyrroles
  作者：Diana Wischang、Madlen Radlow、Jens Hartung

  DOI：10.1039/c3dt51582f

  日期：——

  aqueous tert-butanol (pH 6.2) molecular bromine as reagent for electrophilic hydrocarbon bromination. Alternative compounds, such as tribromide and hypobromous acid are not sufficiently electrophilic for being directly involved in carbon–bromine bond formation. A decrease in electrophilicity from bromine via hypobromous acid to tribromide correlates in a frontier molecular orbital (FMO) analysis with

  来自褐藻Ascophyllum nodosum的溴过氧化物酶，缩写为V Br PO（An I）和V Br PO（An II），显示出41％的序列同源性，并且α-螺旋二级结构的百分比相差两倍。蛋白质单体组成V Br PO（An I）的同二聚体和V Br PO（An II）的六聚体。溴过氧化物酶II与过氧化氢和溴化物的结合强度比V Br PO（An一世）。在氧化催化中，溴过氧化物酶I和II类似地快速转移过氧化氢和溴化物，生成吗啉-4-乙磺酸（MES）缓冲的叔丁醇水溶液（pH 6.2）分子溴作为亲电烃溴化试剂。诸如三溴化物和次溴酸之类的替代化合物尚不具有足够的亲电子性，无法直接参与碳-溴键的形成。从溴到次溴酸从溴到三溴化物的亲电性下降在前沿分子轨道（FMO）分析中与烯烃的π型HOMO和σ* Br，X之间的较大能隙相关型LUMO的溴化试剂。通过这种方法，可以预测底物的反应性和在钒酸盐依赖性溴过氧化
• Vanadate(<scp>v</scp>)-dependent bromoperoxidase immobilized on magnetic beads as reusable catalyst for oxidative bromination
  作者：Diana Wischang、Jens Hartung、Thomas Hahn、Roland Ulber、Tobias Stumpf、Claudia Fecher-Trost

  DOI：10.1039/c0gc00499e

  日期：——

  Vanadate(V)-dependent bromoperoxidase I (Ascophyllum nodosum) was immobilized on magnetic micrometre-sized particles in quantitative yields, with up to 40% retention of initial bromoperoxidase (BPO) activity. The immobilized enzyme was stable with a half-life time of about 160 days. It served as reusable catalyst for bromide oxidation with H2O2 in up to 14 consecutive experiments. Reactivity that resulted

  钒酸盐（V）依赖性溴过氧化物酶I（Ascophyllum nodosum）以定量收率固定在磁性微米级颗粒上，初始溴过氧化物酶（BPO）活性的保留率高达40％。固定化酶稳定，半衰期约160天。它可以重用催化剂 溴化物 氧化作用在多达14个连续实验中使用H 2 O 2。酶促溴化物引起的反应性氧化作用 适用于 吡咯-2-羧酸甲酯转化为天然化合物（例如得自Agelas oroides的化合物）的衍生物，产品选择性高达75％。
• Direct Access to Marine Pyrrole-2-aminoimidazoles, Oroidin, and Derivatives, via New Acyl-1,2-dihydropyridin Intermediates
  作者：Cosima Schroif-Gregoire、Nathalie Travert、Anne Zaparucha、Ali Al-Mourabit

  DOI：10.1021/ol0608451

  日期：2006.7.1

  [reaction: see text] A short synthesis of the C(11)N(5) oroidin derivatives is reported. The key step of the strategy is a one-pot oxidative bromine-mediated addition of protected guanidines to the N-acyl-1,2-dihydropyridines 9a-c. The new N-acyl-1,2-dihydropyridines were prepared directly from pyridine and pyrrole-2-carbonyl chloride by reduction with borohydride reagent in one step.

  [反应：见正文]报道了C（11）N（5）麦冬蛋白衍生物的简短合成。该策略的关键步骤是将一锅氧化溴介导的受保护胍加入N-酰基-1，2-二氢吡啶9a-c。通过一步用硼氢化物还原，由吡啶和吡咯-2-羰基氯直接制得新的N-酰基-1,2-二氢吡啶。