(R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 | 15186-48-8

• 物质功能分类: 有机原料 - 醛类化合物
• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛
• 中文别名: (R)-(+)-2,2-二甲基-1,3-二氧-4-醛基戊烷；(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛；D-甘油醛缩丙酮；R-甘油醛缩丙酮；(R)-丙酮缩甘油醛；(R)-2,2-二甲基-1,3-二氧戊环-4-甲醛；(R)-甘油醛缩丙酮
• 英文名称: 2,3-isopropylidene-glyceraldehyde
• 英文别名: (R)-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde；(4R)-2,2-dimethyl-1,3-dioxolane-4-carbaldehyde；(R)-(+)-2,2-dimethyl-1,3-dioxolane-4-carboxaldehyde；(R)-glyceraldehyde acetonide；2,3-O-isopropylideneglyceraldehyde
• CAS: 15186-48-8
• 化学式: C₆H₁₀O₃
• 分子量: 130.144
• InChiKey: YSGPYVWACGYQDJ-YFKPBYRVSA-N

物化性质

• 比旋光度：
  53.8 º (c=2, CHCl3)
• 沸点：
  139 °C (lit.)
• 密度：
  1.045 g/mL at 25 °C (lit.)
• 闪点：
  143 °F
• 溶解度：
  难溶于水

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 危险等级：
  6.1
• WGK Germany：
  3
• 海关编码：
  2932999099
• 危险类别：
  6.1
• 包装等级：
  III
• 危险性防范说明：
  P501,P273,P240,P210,P233,P243,P241,P242,P280,P370+P378,P312,P391,P303+P361+P353,P403+P235
• 危险品运输编号：
  1993
• 危险性描述：
  H303,H411,H225
• 储存条件：
  请将存放在凉爽干燥的地方，并保持密封。

SDS

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Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
Product name : (R)-(+)-2,2-Dimethyl-1,3-dioxolane-4-
carboxaldehyde
CAS-No. : 15186-48-8
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances

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Section 2. HAZARDS IDENTIFICATION
Classification of the substance or mixture
Not a hazardous substance or mixture according to Regulation (EC) No. 1272/2008.
This substance is not classified as dangerous according to Directive 67/548/EEC.
Label elements
The product does not need to be labelled in accordance with EC directives or respective national laws.
Other hazards - none

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Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Substances
Formula : C6H10O3
Molecular Weight : 130,14 g/mol

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Section 4. FIRST AID MEASURES
Description of first aid measures
General advice
Consult a physician. Show this safety data sheet to the doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.
In case of skin contact
Wash off with soap and plenty of water. Consult a physician.
In case of eye contact
Flush eyes with water as a precaution.
If swallowed
Do NOT induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with
water. Consult a physician.
Most important symptoms and effects, both acute and delayed
To the best of our knowledge, the chemical, physical, and toxicological properties have not been
thoroughly investigated.
Indication of any immediate medical attention and special treatment needed
no data available

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Section 5. FIREFIGHTING MEASURES
Extinguishing media
Suitable extinguishing media
For small (incipient) fires, use media such as "alcohol" foam, dry chemical, or carbon dioxide. For large
fires, apply water from as far as possible. Use very large quantities (flooding) of water applied as a mist or
spray; solid streams of water may be ineffective. Cool all affected containers with flooding quantities of
water.
Special hazards arising from the substance or mixture
Carbon oxides
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
Use water spray to cool unopened containers.

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Section 6. ACCIDENTAL RELEASE MEASURES
Personal precautions, protective equipment and emergency procedures
Avoid breathing vapors, mist or gas. Remove all sources of ignition. Beware of vapours accumulating to
form explosive concentrations. Vapours can accumulate in low areas.
Environmental precautions
Prevent further leakage or spillage if safe to do so. Do not let product enter drains.
Methods and materials for containment and cleaning up
Contain spillage, and then collect with an electrically protected vacuum cleaner or by wet-brushing and
place in container for disposal according to local regulations (see section 13). Keep in suitable, closed
containers for disposal.
Reference to other sections
For disposal see section 13.

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Section 7. HANDLING AND STORAGE
Precautions for safe handling
Avoid inhalation of vapour or mist.
Keep away from sources of ignition - No smoking.Take measures to prevent the build up of electrostatic
charge.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Containers which are
opened must be carefully resealed and kept upright to prevent leakage.
Recommended storage temperature: -20 °C
Handle and store under inert gas.
Specific end use(s)
no data available

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Section 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and
at the end of workday.
Personal protective equipment
Eye/face protection
Safety glasses with side-shields conforming to EN166 Use equipment for eye protection tested
and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
Impervious clothing., The type of protective equipment must be selected according to the
concentration and amount of the dangerous substance at the specific workplace.
Respiratory protection
Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator
with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup
to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air
respirator. Use respirators and components tested and approved under appropriate government
standards such as NIOSH (US) or CEN (EU).

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Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Information on basic physical and chemical properties
a) Appearance Form: liquid
Colour: colourless
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing no data available
point
f) Initial boiling point and 139 °C - lit.
boiling range
g) Flash point 62 °C - closed cup
h) Evaporation rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density 1,045 g/cm3 at 25 °C
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Auto-ignition no data available
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

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Section 10. STABILITY AND REACTIVITY
Reactivity
no data available
Chemical stability
no data available
Possibility of hazardous reactions
no data available
Conditions to avoid
Heat, flames and sparks.
Incompatible materials
Strong oxidizing agents
Hazardous decomposition products
Other decomposition products - no data available

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Section 11. TOXICOLOGICAL INFORMATION
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitization
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Potential health effects
Inhalation May be harmful if inhaled. May cause respiratory tract irritation.
Ingestion May be harmful if swallowed.
Skin May be harmful if absorbed through skin. May cause skin irritation.
Eyes
May cause eye irritation.
Signs and Symptoms of Exposure
To the best of our knowledge, the chemical, physical, and toxicological properties have not been
thoroughly investigated.
Additional Information
RTECS: Not available

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Section 12. ECOLOGICAL INFORMATION
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
no data available
Other adverse effects
no data available

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Section 13. DISPOSAL CONSIDERATIONS
Waste treatment methods
Product
This combustible material may be burned in a chemical incinerator equipped with an afterburner and
scrubber. Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a licensed
professional waste disposal service to dispose of this material.
Contaminated packaging
Dispose of as unused product.

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Section 14. TRANSPORT INFORMATION
UN number
ADR/RID: - IMDG: - IATA: -
UN proper shipping name
ADR/RID: Not dangerous goods
IMDG: Not dangerous goods
IATA: Not dangerous goods
Transport hazard class(es)
ADR/RID: - IMDG: - IATA: -
Packaging group
ADR/RID: - IMDG: - IATA: -
Environmental hazards
ADR/RID: no IMDG Marine Pollutant: no IATA: no
Special precautions for user
no data available

---

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SECTION 15 - REGULATORY INFORMATION
N/A

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

应用(R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛又叫R-甘油醛缩丙酮，是合成吉西他滨的中间体。盐酸吉西他滨是一种人工合成的新型二氟核苷类抗代谢抗肿瘤药，最初由美国Eli Lilly公司开发并命名为“健择”。盐酸吉西他滨能够抑制DNA的合成。

制备向洁净的反应器中依次加入220克二氯甲烷、23克双丙酮-D-甘露醇、0.23克18-冠-6-醚和0.4克TEMPO，搅拌混合均匀后缓慢降温至10℃。开始滴加质量百分数为10wt%的次氯酸钠水溶液72克，滴加过程中控制反应体系温度在15℃以下。滴加完毕后，在30℃～32℃条件下保温进行氧化反应1小时。反应结束后，静置、分层，除去水层，收集有机层用50克水洗一次，再分层除去水层。将收集的有机层与20克无水硫酸钠搅拌干燥30分钟，抽滤收集滤液。将滤液减压浓缩除去溶剂，烘后得到(R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛干品22.1克，收率97%，气相含量为99.2%。

反应信息

• 作为反应物：
  描述：

  (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 在 sodium tetrahydroborate 、 sodium methylate 作用下， 反应 2.0h， 生成 (S)-2,2-Dimethyl-4-(naphthoxy)methyl-1,3-dioxolane
  参考文献：
  名称：

  Tsuda, Yoshisuke; Yoshimoto, Kimihiro; Nishikawa, Terumi, Chemical and pharmaceutical bulletin, 1981, vol. 29, # 12, p. 3593 - 3600

  摘要：

  DOI：
• 作为产物：
  描述：

  1,2;5,6-Di-O-isopropylidenmannit 在 sodium periodate 、 碳酸氢钠 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以42%的产率得到(R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛
  参考文献：
  名称：

  [EN] PROCESS FOR THE PREPARATION OF A FLUOROLACTON DERIVATIVE
  [FR] PROCÉDÉ DE PRÉPARATION D'UN DÉRIVÉ DE FLUOROLACTONE

  摘要：

  描述了一种制备公式（I）的氟内酯衍生物和其酰化衍生物的新工艺，其中R1代表一个羟基保护基团。公式（V）的酰化氟内酯，特别是R1 =苄基的苯甲酰衍生物，是合成前药化合物的重要前体，这些前药化合物具有潜力成为对丙型肝炎病毒（HCV）NS5B聚合酶具有强效抑制作用的化合物。

  公开号：

  WO2014108525A1
• 作为试剂：
  描述：

  N-甲基烯丙基胺 、 N-苄基羟胺 在 (R)-(+)-2,2-二甲基-1,3-二氧戊环-4-甲醛 作用下， 以 苯 为溶剂， 反应 24.0h， 生成 (R)-N²-benzyl-N²-hydroxy-N¹-methylpropane-1,2-diamine 、 (S)-N²-benzyl-N²-hydroxy-N¹-methylpropane-1,2-diamine
  参考文献：
  名称：

  催化束缚策略：简单的醛催化分子间烯烃氢胺化

  摘要：

  在本文中，我们描述了一种催化束缚策略，其中简单的醛预催化剂通过临时分子内、室温分子间加氢胺化反应和邻二胺的合成来实现。该催化剂允许由烯丙胺和羟胺形成混合胺醛，从而导致容易的分子内加氢胺化事件。用手性醛获得的有希望的对映选择性也突出了这种催化束缚方法在不对称催化中的潜力，并证明仅依赖临时分子内的有效对映诱导是可能的。

  DOI：

  10.1021/ja208867g

文献信息

• Total Synthesis of (−)-21-Isopentenylpaxilline
  作者：Amos B. Smith、Haifeng Cui

  DOI：10.1021/ol027575g

  日期：2003.2.1

  [structure: see text] The total synthesis of (-)-21-isopentenylpaxilline (1) has been achieved. Key elements of the synthesis include the stereocontrolled construction of the advanced eastern hemisphere (-)-5, a highly efficient union of the eastern and western fragments (-)-5 and 4, respectively, exploiting our 2-substituted indole synthesis, and a new protocol for the construction of ring C.

  [结构：见正文]已完成（-）-21-异戊烯基帕西林（1）的全合成。合成的关键元素包括先进的东半球（-）-5的立体控制结构，利用我们的2取代的吲哚合成技术分别高效合成东部和西部碎片（-）-5和4的方法，以及用于构建C环的新协议。
• Facile solid-phase ruthenium assisted azide-alkyne cycloaddition (RuAAC) utilizing the Cp∗RuCl(COD)-catalyst
  作者：Ebbe Engholm、Nicolai Stuhr-Hansen、Ola Blixt

  DOI：10.1016/j.tetlet.2017.04.095

  日期：2017.6

  The ruthenium assisted azide-alkyne cycloaddition (RuAAC) reaction is a well-established method for the generation of 1,5- and 1,4,5-substituted 1,2,3-triazoles, which we have extended to the solid-phase synthesis of 1,2,3-triazole-peptides. The 1,2,3-triazole moieties were formed upon the reaction of alkynes with a solid-phase bound secondary azide in the presence of the Cp∗RuCl(COD) catalyst at room

  钌辅助的叠氮化物-炔烃环加成（RuAAC）反应是一种成熟的方法，用于生成1,5-和1,4,5-取代的1,2,3-三唑，我们已经扩展到固相1,2,3-三唑-肽的合成。在炔烃与固相键合的二级叠氮化物在Cp * RuCl（COD）催化剂存在下于室温下反应后，形成1,2,3-三唑部分。末端炔烃和内部炔烃都在温和条件下进行了高度区域选择性的环加成反应，从而促进了具有完整侧链保护的肽构建体从树脂中的释放。在1小时内观察到几乎定量转化为相应的1,2,3-三唑。
• [EN] PHENOTHIAZINE DERIVATIVES AND USES THEREOF<br/>[FR] DÉRIVÉS DE PHÉNOTHIAZINE ET LEURS UTILISATIONS
  申请人：CAMP4 THERAPEUTICS CORP

  公开号：WO2019195789A1

  公开（公告）日：2019-10-10

  The present invention provides phenothiazine compounds, processes for their preparation, pharmaceutical compositions comprising the compounds, and the use of the compounds or the compositions in the treatment of various diseases or conditions, for example ribosomal disorders and ribosomopathies, e.g. Diamond Blackfan anemia (DBA).

  本发明提供了吩噻嗪化合物，其制备方法，包含该化合物的药物组合物，以及在治疗各种疾病或症状中使用该化合物或组合物，例如核糖体紊乱和核糖体病，例如钻石-布莱克范贫血（DBA）。
• 一种吉西他滨中间体的高选择性的合成方法
  申请人：苏州华鑫医药科技有限公司

  公开号：CN112225767A

  公开（公告）日：2021-01-15

  本发明公开了一种吉西他滨中间体的高选择性的合成方法，具体包括如下工艺：具体包括如下工艺：Step1,T1的合成；Step2,T2的合成，将T1中滴加550kg双氧水，控制反应生成T2；Step3,T3的合成：向反应釜中加三水乙酸钠或者碳酸钠，用冰醋酸调节PH值，滴加10‑15％次氯酸钠水溶液，控制反应生成T3；Step4,T4的合成；Step5,T5的合成；Step6,T6的合成；Step7,T7的合成；Step8,T8的合成；Step9,T8构型转化；本吉西他滨中间体的高选择性的合成方法能够节省生产成本，同时还能够提高吉西他滨中间体的产率。
• Stereospecific Synthesis of 2-Deoxy-2,2-difluororibonolactone and Its Use in the Preparation of 2′-Deoxy-2′,2′-difluoro-β-D-ribofuranosyl Pyrimidine Nucleosides: The Key Role of Selective Crystallization
  作者：T. S. Chou、P. C. Heath、L. E. Patterson、L. M. Poteet、R. E. Lakin、A. H. Hunt

  DOI：10.1055/s-1992-26167

  日期：——

  A stereospecific synthesis of 2′-deoxy-2′,2′-difluorocytidine (gemcitabine), a potential anticancer agent, is described. The stereoselectivity was accomplished via two diastereoselective crystallizations, i. e. the crystallization of the key intermediate, difluororibonolactone 2a, and the crystallization of the hydrochloride salt of gemcitabine 16b from the anomeric mixture. Because of the availability of 2a in large quantities, other 2′-deoxy-2′,2′-difluoropyrimidine nucleosides such as 2′-deoxy-2′,2′-difluorouridine (19) were synthesized for structure-activity relationship studies.

  本文描述了潜在抗癌药物2′-脱氧-2′,2′-二氟胞苷（吉西他滨）的立体特异性合成。通过两次非对映选择性结晶实现了立体选择性：即关键中间体二氟乳糖内酯2a的结晶，以及从异头混合物中结晶出吉西他滨的盐酸盐16b。由于2a可以大量获得，因此合成了其他2′-脱氧-2′,2′-二氟嘧啶核苷，如2′-脱氧-2′,2′-二氟尿苷（19），用于结构-活性关系研究。