(S)-(+)-1-(Alpha-氨基苄基)-2-萘酚 | 219897-38-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: (S)-(+)-1-(Alpha-氨基苄基)-2-萘酚
• 中文别名: (S)-(+)-1-(氨基苯甲酰基)-2-奈酚；(S)-(+)-1-(α-氨基苄基)-2-萘酚
• 英文名称: (S)-(+)-1-(amino(phenyl)methyl)naphthalen-2-ol
• 英文别名: (S)-(+)-1-(α-aminobenzyl)-2-naphthol；(S)-1-(α-aminobenzyl)naphthalen-2-ol；(S)-1-[amino(phenyl)methyl]naphthalen-2-ol；(S)-1-(α-aminobenzyl)-2-naphthol；S(+)-1-(α-aminobenzyl)-2-napthol；(S)-1-α-aminobenzyl-2-naphthol；(S)-(+)-1-(alpha-Aminobenzyl)-2-naphthol；1-[(S)-amino(phenyl)methyl]naphthalen-2-ol
• CAS: 219897-38-8
• 化学式: C₁₇H₁₅NO
• mdl: MFCD04972351
• 分子量: 249.312
• InChiKey: PZMIGEOOGFFCNT-KRWDZBQOSA-N

物化性质

• 熔点：
  133-137 °C
• 沸点：
  451.1±30.0 °C(Predicted)
• 密度：
  1.211±0.06 g/cm3(Predicted)
• 稳定性/保质期：
  1. 遵照规定使用和储存，则不会分解。 2. 该试剂在游离胺状态下不稳定，会自动分解。通常建议以盐酸盐或酒石酸盐的形式储存和使用。

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.058
• 拓扑面积：
  46.2
• 氢给体数：
  2
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S36,S37/39
• 危险类别码：
  R36/37/38
• 海关编码：
  2922299090
• 储存条件：
  存放于4℃阴凉干燥处

SDS

Name:	(S)-(+)-1-(alpha-Aminobenzyl)-2-naphthol 98% Material Safety Data Sheet
Synonym:	(S)-Betti bas
CAS:	219897-38-8

Section 1 - Chemical Product MSDS Name:(S)-(+)-1-(alpha-Aminobenzyl)-2-naphthol 98% Material Safety Data Sheet
Synonym:(S)-Betti bas

---

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
219897-38-8	(S)-(+)-1-(alpha-Aminobenzyl)-2-naphth	98%	unlisted

Hazard Symbols: XI
Risk Phrases: 36/37/38

---

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

---

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:
Treat symptomatically and supportively.

---

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.

---

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.

---

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.

---

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# 219897-38-8: 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.

---

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Powder
Color: white to off-white
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: 133 - 137 deg C
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature: 259 deg C
Solubility in water: Insoluble.
Specific Gravity/Density:
Molecular Formula: C17H15NO
Molecular Weight: 249.31

---

Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials.
Incompatibilities with Other Materials:
Strong oxidizing agents, strong reducing agents.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported

---

Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 219897-38-8 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(S)-(+)-1-(alpha-Aminobenzyl)-2-naphthol - Not listed by ACGIH, IARC, or NTP.

---

Section 12 - ECOLOGICAL INFORMATION

---

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

---

Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
IMO
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing Group:
RID/ADR
Shipping Name: Not regulated.
Hazard Class:
UN Number:
Packing group:

---

Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XI
Risk Phrases:
R 36/37/38 Irritating to eyes, respiratory system
and skin.
Safety Phrases:
S 36 Wear suitable protective clothing.
S 37/39 Wear suitable gloves and eye/face
protection.
WGK (Water Danger/Protection)
CAS# 219897-38-8: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 219897-38-8 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 219897-38-8 is not listed on the TSCA inventory.
It is for research and development use only.

---

SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

用途

(S)-1-(α-氨基苄基)-2-萘酚[(S)-Betti碱]在有机合成中主要用于不对称催化反应中的手性配体或不对称合成中的手性辅助合成试剂。由于其对映体昂贵，(S)-Betti碱在外消旋体的拆分中更廉价且应用广泛。

外消旋Betti碱的拆分已有近一个世纪的历史，但直到1998年才再次被成功拆分[1,2]。尽管如此，使用此方法得到的手性Betti碱并未有实际应用的报道。

手性Betti碱含有1,3-氨基-羟基结构，能够与金属离子形成稳定的六元环配合物。虽然该试剂本身不是一个很好的手性配体，但其许多叔胺衍生物已被证实是非常优秀的手性配体，并用于金属催化的不对称反应。这些手性Betti碱的叔胺衍生物主要是通过直接拆分或使用手性胺进行Mannich反应制备(式1, 式2)[3~6]。

最近，有文献报道了外消旋Betti碱在丙酮溶液中高效动力学拆分的方法。作为酒石酸盐的(S)-Betti碱可以定量地从反应体系中沉淀出来，而(R)-Betti碱则被转化为相应的缩酮衍生物。这种酒石酸盐的形式不仅是一种安全的储存方式，还可以直接参与反应(式3)[7]。

该试剂与二羰基化合物发生缩合反应可方便地构建手性5~7元含氮环状结构，类似于手性苯基甘氨醇的反应，但具有以下显著优势：(1) 该试剂是一个氨基酚化合物，具有更高的反应活性；(2) 其羟基直接连接到位阻较大的萘环上，因此具有较高的立体选择性。与末端二醛发生缩合反应生成的嗪中间体既可以用于手性配体的合成(式4)[8]，也可以用于含有手性哌啶的天然产物全合成(式5)[9]。

反应信息

• 作为反应物：
  描述：

  (S)-(+)-1-(Alpha-氨基苄基)-2-萘酚 以 甲醇 为溶剂， 反应 1.0h， 生成 (1S)-2-[(1H-1,2,3-benzotriazol-1-yl)methyl]-1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazine
  参考文献：
  名称：

  Highly regioselective N-alkylation of nonracemic Betti base: a novel one-pot synthesis of chiral N-methyl-N-alkyl Betti bases

  摘要：

  A novel one-pot preparation of chiral N-methyl-N-alkyl Betti bases has been developed involving a highly regioselective N-alkylation of (S)-(+)-Betti base. The strategy involved formation-cleavage of the oxazine ring and N-methylation with BtCH(2)OH under neutral conditions. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.04.006
• 作为产物：
  描述：

  1-(α-aminobenzyl)-2-naphthol trifluoroacetate 在 sodium carbonate 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 生成 (S)-(+)-1-(Alpha-氨基苄基)-2-萘酚
  参考文献：
  名称：

  光学纯1-(α-氨基苄基)-2-萘酚的制备方法

  摘要：

  本发明提供了一种光学纯1‑(α‑氨基苄基)‑2‑萘酚（Betti Base）的制备方法。使用三氟乙酸催化合成消旋的1‑(α‑氨基苄基)‑2‑萘酚三氟乙酸盐，并利用光学纯1,1’‑联萘酚磷酸酯和光学纯1,1’‑联萘酚磷酸钠做为拆分试剂，对消旋的1‑(α‑氨基苄基)‑2‑萘酚及其三氟乙酸盐进行拆分制备光学纯1‑(α‑氨基苄基)‑2‑萘酚。该方法重复性好，拆分试剂可以重复使用，成本低，环保节能，适合光学纯1‑(α‑氨基苄基)‑2‑萘酚的大量制备。

  公开号：

  CN103102280B
• 作为试剂：
  描述：

  (S)-(+)-1-(Alpha-氨基苄基)-2-萘酚 、 (2R)-2-methyl-4-oxobutanoic acid 在 (S)-(+)-1-(Alpha-氨基苄基)-2-萘酚 作用下， 以72.9的产率得到(7aR,9R,12S)-9-methyl-10-oxo-12-phenyl-7a,8,9,10-tetrahydro-12H-naphtho[1,2-e]pyrrolo[2,1-b][1,3]oxazine
  参考文献：
  名称：

  沙库比曲的制备方法

  摘要：

  本发明揭示了一种新型降压药物LCZ696组分之一的沙库比曲(Sacubitril，AHU-377，I)的制备方法，其制备步骤包括：以手性诱导试剂(S)-1-(α-氨基苄基)-2-萘酚(S-betti Base)与2R-甲基-4-氧代-丁酸经环合、加成、脱苄基、开环、酯化及酰胺化等反应步骤制得沙库比曲(I)。该制备方法原料易得，工艺简洁，经济环保，适合工业化生产。

  公开号：

  CN104557600A

文献信息

• Chiral (thio)phosphorodiamides as excellent hydrogen bond donor catalysts in the asymmetric Michael addition of 2-hydroxy-1,4-naphthoquione to nitroolefins
  作者：Ronghua Wu、Xufang Chang、Aidang Lu、Youming Wang、Guiping Wu、Haibin Song、Zhenghong Zhou、Chuchi Tang

  DOI：10.1039/c1cc10797f

  日期：——

  A novel type of bidentate hydrogen bond donor catalysts based on (thio)phosphorodiamides catalophore has been developed for the asymmetric Michael addition of 2-hydroxy-1,4-naphthoquione to nitroolefins, affording the corresponding adducts in high yields with excellent level of enantioselectivities (97- >99% ee).

  已经开发出了一种新型的基于（硫代）磷二酰胺基阴极的双齿氢键供体催化剂，用于将2-羟基-1,4-萘并醌不对称地迈克尔加成到硝基烯烃中，从而以高收率提供相应的加合物，同时具有出色的对映选择性（ 97-> 99％ee）。
• Betti's base for crystallization-induced deracemization of substituted aldehydes: synthesis of enantiopure amorolfine and fenpropimorph
  作者：Andrea Carella、Gabriel Ramos Ferronatto、Emanuela Marotta、Andrea Mazzanti、Paolo Righi、Claudio Paolucci

  DOI：10.1039/c6ob02765b

  日期：——

  diastereoisomer transformation (CIDT) of naphthoxazines derived from racemic O-protected 2-substituted 4-hydroxybutyraldehydes and enantiopure Betti's base allows the deracemization of the starting aldehydes with ee up to 96%. As an alternative, reduction with lithium aluminum hydride of the diastereoisomerically enriched naphthoxazines leads to enantioenriched primary amines. The utility of the latter strategy

  由外消旋的O-保护的2-取代的4-羟基丁醛和对映体纯的Betti's碱衍生的萘并恶嗪的酸促进结晶诱导的非对映异构体转化（CIDT）可以使起始醛与ee的反硝化作用高达96％。或者，用氢化锂铝将非对映异构体富集的萘并恶嗪还原可得到对映体富集的伯胺。后一种方法的实用性通过将其应用于对映体富集的苯丙咪唑和ee高达99.5％的对映体纯阿莫罗芬的首次合成得到了证明。
• Phosphorylation of betti base with diethyl chlorophosphate
  作者：K. E. Metlushka、D. N. Sadkova、K. A. Nikitina、L. N. Shaimardanova、O. N. Kataeva、V. A. Alfonsov

  DOI：10.1134/s107036321603004x

  日期：2016.3

  Phosphoric acid derivatives containing chiral Betti base fragment were synthesized by reacting racemic and enantiopure N-Boc-protected 1-(α-aminobenzyl)-2-naphthols with diethyl chlorophosphate followed by deprotection.

  通过使外消旋和对映纯的N -Boc保护的1-（α-氨基苄基）-2-萘酚与氯代磷酸二乙酯反应，然后脱保护，可以合成含有手性贝蒂碱基片段的磷酸衍生物。
• Acid promoted CIDT for the deracemization of dihydrocinnamic aldehydes with Betti's base
  作者：Goffredo Rosini、Claudio Paolucci、Francesca Boschi、Emanuela Marotta、Paolo Righi、Francesco Tozzi

  DOI：10.1039/c0gc00013b

  日期：——

  Racemic α-epimerizable and unfunctionalized aldehydes have been converted into enantiomerically enriched mixtures through a sequence of (i) a conversion into the diastereoisomeric 3-substituted 1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazines by reaction with the (R)- or (S)-1-(α-aminobenzyl)-2-naphthol (Betti's base), (ii) an acid promoted crystallization-induced diastereoisomer transformation (CIDT), and (iii) a clean cleavage of the dihydro-1,3-naphthoxazinic ring of the enriched diastereoisomer, easily collected by filtration, allowing the recovery of the enantiomerically enriched aldehydes and the chiral auxiliary.

  对映体的α-可互变和未功能化的醛通过以下步骤转化为富含对映体的混合物：(i) 与(R)-或(S)-1-(α-氨基苄基)-2-萘酚（Betti碱）反应，转化为二面体异构体的3-取代1-苯基-2,3-二氢-1H-萘并[1,2-e][1,3]氧杂啉；(ii) 促酸的结晶诱导二面体异构体转化（CIDT）；(iii) 清洁地切割富集的二面体异构体的二氢-1,3-萘氧杂烯环，易于过滤收集，从而回收富含对映体的醛和手性辅助剂。
• Use of readily available chiral compounds related to the betti base in the enantioselective addition of diethylzinc to aryl aldehydes
  作者：Cosimo Cardellicchio、Giuseppe Ciccarella、Francesco Naso、Filippo Perna、Paolo Tortorella

  DOI：10.1016/s0040-4020(99)00914-x

  日期：1999.12

  complexing agents in the catalytic enantioselective addition of diethylzinc to aryl aldehydes. The use of these bases gave high ee values (up to > 99%). The highest ee values were obtained with the tertiary aminonaphthol 2. An important role was played by the solvent. The effect of the nature and the position of the substituents on the aromatic ring of the aldehyde was also investigated.

  与Betti碱1相关的手性非外消旋氨基萘家族的现有成员在将二乙基锌催化芳对醛催化对映选择性加成反应中作为络合剂进行了测试。使用这些碱可得到较高的ee值（高达> 99％）。叔氨基萘2可获得最高的ee值。溶剂起着重要作用。还研究了性质和取代基在醛的芳环上的位置的影响。