2-乙酰基-6,7-二甲氧基-1-亚甲基-1,2,3,4-四氢异喹啉 | 57621-04-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 中文名称: 2-乙酰基-6,7-二甲氧基-1-亚甲基-1,2,3,4-四氢异喹啉
• 英文名称: N-acetyl-6,7-dimethoxy-1-methylene-1,2,3,4-tetrahydroisoquinoline
• 英文别名: 1-(6,7-dimethoxy-1-methylene-3,4-dihydro-1H-isoquinolin-2-yl)ethanone；1-(6,7-dimethoxy-1-methylene-3,4-dihydroisoquinolin-2(1H)-yl)ethanone；2-acetyl-6,7-dimethoxy-1-methylene-1,2,3,4-tetrahydro-isoquinoline；2-Acetyl-6,7-dimethoxy-1-methylen-1,2,3,4-tetrahydro-isochinolin；2-Acetyl-6,7-dimethoxy-1-methylene-1,2,3,4-tetrahydroisoquinoline；1-(6,7-dimethoxy-1-methylidene-3,4-dihydroisoquinolin-2-yl)ethanone
• CAS: 57621-04-2
• 化学式: C₁₄H₁₇NO₃
• 分子量: 247.294
• InChiKey: JRMQVUQWPOMMAD-UHFFFAOYSA-N

物化性质

• 熔点：
  107-109 °C
• 沸点：
  390.33°C (rough estimate)
• 密度：
  1.1173 (rough estimate)
• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.357
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 安全说明：
  S24/25

SDS

Name:	2-Acetyl-6 7-Dimethoxy-1-Methylene-1 2 3 4-Tetrahydroisoquinoline Material Safety Data Sheet
Synonym:	None Known
CAS:	57621-04-2

Section 1 - Chemical Product MSDS Name:2-Acetyl-6 7-Dimethoxy-1-Methylene-1 2 3 4-Tetrahydroisoquinoline Material Safety Data Sheet
Synonym:None Known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
57621-04-2	2-Acetyl-6,7-Dimethoxy-1-Methylene-1,2	98	unlisted

Hazard Symbols: None Listed.
Risk Phrases: None Listed.

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation.
Ingestion:
May cause irritation of the digestive tract. The toxicological properties of this substance have not been fully investigated.
Inhalation:
May cause respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
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. Get medical aid.
Skin:
Get medical aid. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes.
Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. 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. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Runoff from fire control or dilution water may cause pollution.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam. Use agent most appropriate to extinguish fire.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Use with adequate ventilation. Minimize dust generation and accumulation. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing. Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Store in a tightly closed container. Store in a cool, dry, well-ventilated area away from incompatible substances.

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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# 57621-04-2: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
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: Crystals
Color: white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 107 - 109 deg C
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:
Molecular Formula: C14H17NO3
Molecular Weight: 247.1239

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
Incompatible materials, dust generation, excess heat, strong oxidants.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Nitrogen oxides, 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# 57621-04-2 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
2-Acetyl-6,7-Dimethoxy-1-Methylene-1,2,3,4-Tetrahydroisoquinoline, - 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
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
Not regulated as a hazardous material.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: Not available.
Risk Phrases:
Safety Phrases:
S 24/25 Avoid contact with skin and eyes.
WGK (Water Danger/Protection)
CAS# 57621-04-2: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 57621-04-2 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 57621-04-2 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：

  2-乙酰基-6,7-二甲氧基-1-亚甲基-1,2,3,4-四氢异喹啉 在 lithium hydroxide monohydrate 、 Ru(OAc)2((S)-BINAP) 、 水 、 氢气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 25.0~180.0 ℃ 、2.03 MPa 条件下， 反应 73.0h， 生成 猪毛菜定
  参考文献：
  名称：

  （+）-bernumidine及其非天然对映异构体的总合成

  摘要：

  通过化学酶动力学动力学拆分和钌（II）催化的对映选择性加氢完成（+）-bernumidine及其非天然对映异构体的总合成，从而高产率地提供了（R）-沙丁胺基丙基氨基甲酸酯和N-乙酰基（S）-沙丁胺碱和对映体过量。通过简单而有效的转化，获得了沙丁胺碱的两个对映异构体，并将其转化为（+）-和（-）-伯尼替丁。

  DOI：

  10.1016/j.tetlet.2018.08.046
• 作为产物：
  描述：

  N-(3,4-二甲氧基苯乙基)乙酰胺 在 吡啶 、 sodium hydroxide 、 三氯氧磷 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 5.17h， 生成 2-乙酰基-6,7-二甲氧基-1-亚甲基-1,2,3,4-四氢异喹啉
  参考文献：
  名称：

  （+）-bernumidine及其非天然对映异构体的总合成

  摘要：

  通过化学酶动力学动力学拆分和钌（II）催化的对映选择性加氢完成（+）-bernumidine及其非天然对映异构体的总合成，从而高产率地提供了（R）-沙丁胺基丙基氨基甲酸酯和N-乙酰基（S）-沙丁胺碱和对映体过量。通过简单而有效的转化，获得了沙丁胺碱的两个对映异构体，并将其转化为（+）-和（-）-伯尼替丁。

  DOI：

  10.1016/j.tetlet.2018.08.046

文献信息

• Chiral <i>C</i>₂-Symmetric Ligands with 1,4-Dioxane Backbone Derived from Tartrates:  Syntheses and Applications in Asymmetric Hydrogenation
  作者：Wenge Li、Jason P. Waldkirch、Xumu Zhang

  DOI：10.1021/jo020250t

  日期：2002.11.1

  Chiral 1,4-diphenylphosphines 5-7 as well as thioether 8 were synthesized from tartrates employing Ley's "BDA" and "Dispoke" methodologies as the key step. Rhodium(I) complexes with 5-7 are efficient catalysts for the asymmetric hydrogenation of beta-substituted enamides and MOM-protected beta-hydroxyl enamides, which furnished chiral amines or beta-amino alcohols with 94-->99% ee. These results indicated

  手性1,4-二苯基膦5-7以及硫醚8是由酒石酸盐合成的，采用Ley的“ BDA”和“ Dispoke”方法作为关键步骤。含5-7的铑（I）配合物是有效的催化剂，可用于β-取代的酰胺和MOM保护的β-羟基酰胺的不对称加氢，从而提供了94-> 99％ee的手性胺或β-氨基醇。这些结果表明，具有一般结构2的配体中的1，4-二恶烷骨架在稳定金属-配体螯合物构象中起重要作用。与具有一般结构1的类似配体相比，配体2具有更高的对映选择性。
• Homochiral NADH models in the pyrrolo[2,3-b]pyridine series bearing one or two chiral auxiliaries. Asymmetric reduction of methyl benzoylformate and N-acetyl-enamines. Influence of the magnesium salt concentration on the asymmetric induction of reductions
  作者：Corine Leroy、Vincent Levacher、Georges Dupas、Guy Quéguiner、Jean Bourguignon

  DOI：10.1016/s0957-4166(97)00436-9

  日期：1997.10

  models in the pyrrolo[2,3-b]pyridine series bearing one or two chiral auxiliaries either at the pyridine or at the pyrrole ring is described. These models were involved in the reduction of methyl benzoylformate. The reactivity of these reagents and the stereochemical outcome of reductions are discussed in relation to the nature of the chiral auxiliary at the pyrrole ring and the magnesium ions concentration

  描述了在吡啶或吡咯环上带有一个或两个手性助剂的吡咯并[2,3- b ]吡啶系列中NADH模型的合成。这些模型参与了甲基苯甲酰甲酸酯的还原。讨论了这些试剂的反应性和还原的立体化学结果，并与吡咯环上手性助剂的性质和镁离子浓度进行了讨论。试剂3在苯甲酰基甲酸酯的还原反应中显示出优异的反应活性，在几分钟内得到对映体过量（ee = 84％）的扁桃酸甲酯。最后，模型1参与了N-乙酰基-烯胺15和16的不对称还原分别是Salsolidine和Carnegine的前体。在这项研究过程中，N-乙酰基-烯胺15的还原度可降低至87％ee
• Reduction of new substrates with a NADH model reduction of N-acyl-enamines: Mechanism and scope
  作者：Corine Leroy、Georges Dupas、Jean Bourguignon、Guy Quéguiner

  DOI：10.1016/s0040-4020(01)89323-6

  日期：1994.1

  Several examples of the successful reduction of N-acyl-enamine derivatives with a NADH model in the pyrrolo[2,3-b]pyridine series are given. It is shown, that the reduction is strongly dependent on electronic and geometrical factors. It appears that in general, the success of the reduction can be related to the ability of the magnesium ions to form a complex with the acyl group and with the enamine

  给出了用吡咯并[2,3-b]吡啶系列的NADH模型成功还原N-酰基-烯胺衍生物的几个例子。结果表明，减少量很大程度上取决于电子和几何因素。通常看来，还原的成功与镁离子与酰基和烯胺官能团形成配合物的能力有关。从这一观点出发，在此讨论α-乙酰氨基丙烯酸酯衍生物中烯胺官能团的还原，并讨论烯胺亚胺平衡的影响。
• Synthesis of a new chiral bisphosphine ligand, MOCBP, and its use in rhodium(I)-catalyzed asymmetric hydrogenation of a cyclic enamide
  作者：Toshiaki Morimoto、Noriya Nakajima、Kazuo Achiwa

  DOI：10.1016/0957-4166(94)00355-f

  日期：1995.1

  A new chiral bisphosphine ligand (6) bearing a cyclobutane framework was readily prepared by using diastereoselective [2+2] cycloaddition. Its rhodium(I) complex was found to be an efficient catalyst for the asymmetric hydrogenation of a cyclic enamide, N-acetyl-1-methylene-1,2,3,4-tetrahydroisoquinoline (9), affording (R)-(−)-N-acetylsalsodine (10) in up to 80.6% ee.

  通过使用非对映选择性的[2 + 2]环加成反应，可以轻松制备带有环丁烷骨架的新手性双膦配体（6）。发现它的铑（I）络合物是环状烯酰胺N-乙酰基-1-亚甲基-1,2,3,4-四氢异喹啉（9）不对称氢化的有效催化剂，提供（R）-（- ）-最高80.6％ee的N-乙酰沙丁胺（10）。
• Synthesen in der Isochinolinreihe Halogensubstituierte 1-(?-Phenylalkyl)-1,2,3,4-tetrahydro-isochinoline als Analgetica
  作者：A. Brossi、H. Besendrof、B. Pellmont、M. Walter、O. Schinder

  DOI：10.1002/hlca.19600430603

  日期：——

  Substituted 1-methyl-3,4-dihydro-isoquinolines can easily be converted to 2-(β-acylamido-ethyl)-acetophenomes. The latter have been used as intermediates for the synthesis of various substituted 1-β-phenylethyl-2-methyl-1,2,3,4-tetrahydro-isoquinolines. Several of these compounds show interesting analgesic and spasmolytic properties, especially those containing a halogenated phenylethyl group.

  取代的1-甲基-3,4-二氢-异喹啉可以很容易地转化为2-（β-酰基酰胺基-乙基）-乙酰基。后者已用作合成各种取代的1-β-苯乙基-2-甲基-1,2,3,4-四氢-异喹啉的中间体。这些化合物中的几种显示出令人感兴趣的止痛和解痉性质，尤其是那些含有卤代苯乙基的化合物。