5,5'-双(二苯基磷)-四氟-二-1,3-苯二氧杂环 | 503538-69-0

• 物质功能分类: 化学试剂 - 有机试剂 - 膦配体
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 5,5'-双(二苯基磷)-四氟-二-1,3-苯二氧杂环
• 中文别名: R-（-）-5,5-双（二苯基膦基）-2,2,2，2-四氟-4，4-二-1,3-二氧基苯
• 英文名称: (R)-difluorphos
• 英文别名: (R)-difluorophos；R-(-)-5,5'-bis(diphenylphosphino)-2,2,2',2'-tetrafluoro-4-4'-bi-1,3-benzodioxole；(R)-(-)-5,5’-bis(diphenyl;phosphine)-2,2,2’,2’-tetrafluoro-4,4’-bi-1,3-benzodioxole；[4-(5-diphenylphosphanyl-2,2-difluoro-1,3-benzodioxol-4-yl)-2,2-difluoro-1,3-benzodioxol-5-yl]-diphenylphosphane
• CAS: 503538-69-0
• 化学式: C₃₈H₂₄F₄O₄P₂
• 分子量: 682.547
• InChiKey: HGMLTMOEYCQDDR-UHFFFAOYSA-N

物化性质

• 沸点：
  670.9±55.0 °C(Predicted)
• 稳定性/保质期：
  <p>遵照规定使用和储存，则不会分解。</p>

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  48
• 可旋转键数：
  7
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  8

安全信息

• 危险性防范说明：
  P261,P305+P351+P338
• 危险性描述：
  H302,H315,H319,H335
• 储存条件：
  密封在阴凉干燥的环境中。

SDS

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Section 1: Product Identification
R-(-)-5,5'-Bis(diphenylphosphino)-2,2,2',2'-tetrafluoro-4,4'-bi-1,3-benzodioxole, dichloromethane adduct, min.
Chemical Name:
97% (R)-DIFLUORPHOS™
CAS Registry Number: 503538-69-0
Formula: C38H24F4O4P2.xCH2Cl2
EINECS Number: none
Chemical Family: organophosphine ligand
Synonym: None

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title compound 503538-69-0 100% 2.5mg/m3 (as F) 2.5mg/m3 (as F)

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Section 3: Hazards Identification
Emergency Overview: Irritating to skin, eyes and respiratory tract. May be harmful if swallowed.
Primary Routes of Exposure: Ingestion, inhalation
Eye Contact: Irritating to eyes
Skin Contact: Causes slight to mild irritation of the skin.
Inhalation: Irritating to the nose, mucous membranes and respiratory tract.
Ingestion: May be harmful if swallowed. No information available on the physiological effects of ingestion.
Acute Health Affects: Irritating to skin, eyes and respiratory tract.
Product contains fluorine which, under certain conditions of use, decomposition or metabolism, may generate
Chronic Health Affects: fluoride ion causing nausea, vomiting, labored breathing, hypocalcaemia, deterioration of bone and tooth
structure and kidney and liver damage.
NTP: No
IARC: No
OSHA: No

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SECTION 4: First Aid Measures
Immediately flush the eyes with copious amounts of water for at least 10-15 minutes. A victim may need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area with water. Remove contaminated clothes if necessary. Seek medical assistance if
Skin Exposure:
irritation persists.
Remove the victim to fresh air. Closely monitor the victim for signs of respiratory problems, such as difficulty
Inhalation:
in breathing, coughing, wheezing, or pain. In such cases seek immediate medical assistance.
Seek medical attention immediately. Keep the victim calm. Give the victim water (only if conscious). Induce
Ingestion:
vomiting only if directed by medical personnel.

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SECTION 5: Fire Fighting Measures
Flash Point: no data
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: carbon dioxide, dry powder or foam
If this material is involved in a fire, fire fighters should be equipped with a NIOSH approved positive pressure
Special Fire Fighting Procedures:
self-contained breathing apparatus and full protective clothing.
Hazardous Combustion and If involved in a fire this material may emit toxic organic fumes.
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Spill and Leak Procedures: Small spills can be mixed with vermiculite or sodium carbonate and swept up.

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SECTION 7: Handling and Storage
Store in a tightly sealed container under an inert atmopshre of nitrogen or argon. Prolonged exposure to the
Handling and Storage:
atmosphere may lead to degradation of the product.

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SECTION 8: Exposure Controls and Personal Protection
Eye Protection: Always wear approved safety glasses when handling a chemical substance in the laboratory.
Skin Protection: Wear protective clothing and gloves.
Ventilation: Material may form a fine dust. If possible, handle the material in an efficient fume hood.
If ventilation is not available a respirator should be worn. The use of respirators requires a Respirator
Respirator:
Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: Material may form a fine dust. If possible, handle the material in an efficient fume hood.
Additional Protection: No additional protection required.

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SECTION 9: Physical and Chemical Properties
Color and Form: White pwdr.
Molecular Weight: 682.54
Melting Point: no data
Boiling Point: no data
Vapor Pressure: no data
Specific Gravity: no data
Odor: slight odor
Solubility in Water: insoluble

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SECTION 10: Stability and Reactivity
Stability: air sensitive solid
Hazardous Polymerization: none
Conditions to Avoid: Prolonged contact with the atmosphere. Contact with strong oxidizing agents
Incompatibility: strong oxidizing agents, halogens
carbon dioxide, carbon monoxide, phosphorus pentoxide, fluorinated organics, nitrogen oxides, and organic
Decomposition Products:
fumes.

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SECTION 11: Toxicological Information
RTECS Data: No data available in the RTECS files.
Carcinogenic Effects: No data available
Mutagenic Effects: No data available
Tetratogenic Effects: No data available

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SECTION 12: Ecological Information
Ecological Information: No information available

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SECTION 13: Disposal Considerations
Disposal: Dispose of according to local, state and federal regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Non-hazardous
Hazard Class (CFR): NA
Additional Hazard Class (CFR): NA
Packaging Group (CFR): NA
UN ID Number (CFR): NA
Shipping Name (IATA): Non-hazardous
Hazard Class (IATA): NA
Additional Hazard Class (IATA): NA
Packaging Group (IATA): NA
UN ID Number (IATA): NA

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SECTION 15: Regulatory Information
TSCA: not listed on the TSCA inventory
SARA (Title 313): not reportable under SARA Title (313)
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  5,5'-双(二苯基磷)-四氟-二-1,3-苯二氧杂环 在 cesium fluoride 作用下， 以 二氯甲烷 为溶剂， 反应 49.0h， 生成
  参考文献：
  名称：

  手性双核金络合物促进对映选择性芳基-芳基偶联†

  摘要：

  在这里，我们报告的化学计量研究体现了金络合物促进的第一个高度对映选择性的芳基-芳基偶联。ee高达91％，这是金配合物具有高对映选择性的金属转移和C（sp 2）–C（sp 2）还原消除序列的第一个证明。该结果为开发对映选择性金催化的芳基-芳基偶联反应提供了基础。

  DOI：

  10.1039/c9cc07175j
• 作为产物：
  描述：

  二苯基次膦酰氯 在 三正丁胺 、 三氯硅烷 、 铜 、 magnesium 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 、 xylene 为溶剂， 反应 31.83h， 生成 5,5'-双(二苯基磷)-四氟-二-1,3-苯二氧杂环
  参考文献：
  名称：

  Difluorphos，贫电子二膦：电子和空间特征之间的良好匹配。

  摘要：

  DOI：

  10.1002/anie.200352453
• 作为试剂：
  描述：

  乙基戊-2,4-二烯酸酯 、 在 5,5'-双(二苯基磷)-四氟-二-1,3-苯二氧杂环 、 bis(η3-allyl-μ-chloropalladium(II)) 、 氟硼酸钾 、 四(3,5-二(三氟甲基)苯基)硼酸钠 、 三乙胺 、 亚磷酸二乙酯 作用下， 以 乙酸乙酯 为溶剂， 以82%的产率得到
  参考文献：
  名称：

  通过 1,5-加成和 N-1,4-加成级联立体选择性合成多取代二氢吡咯

  摘要：

  开发了一种新型立体选择性1,5-加成和N -1,4-加成级联反应，可方便地以高产率和优异的非对映选择性制备有价值的多取代二氢吡咯。还公开了一种前所未有的对映选择性方案来获取对映体富集的二氢吡咯。

  DOI：

  10.1002/chem.202401350

文献信息

• Benzimidazoles as Ligands in the Ruthenium-Catalyzed Enantioselective Bifunctional Hydrogenation of Ketones
  作者：Jeremy M. Praetorius、Ruiyao Wang、Cathleen M. Crudden

  DOI：10.1021/om900897b

  日期：2010.2.8

  ligands bound to the ruthenium center are active for the mild and chemoselective hydrogenation of ketones in the presence of alkenes. Catalysts that exist as a single diastereomer, prepared with enantiomerically pure diphosphanes, catalyze the hydrogenation of prochiral ketones with moderate levels of enantioselectivity that are significantly improved relative to catalysts existing in several conformations

  L = N的一系列Cl 2 Ru（diphosphane）L 2（II）配合物已经合成并表征了通过氮键与金属键合的1-烷基化苯并咪唑。对于1-甲基苯并咪唑，所得络合物以所有可能的构象异构体的统计混合物形式存在。当苯并咪唑上的取代基的大小增加到10时，可以制备出以单一非对映异构体形式存在的络合物。所有具有结合到钌中心的苯并咪唑配体的配合物在烯烃存在下对酮的轻度和化学选择性氢化均具有活性。用对映体纯的二膦制备的以单一非对映异构体形式存在的催化剂以中等对映体选择性催化前手性酮的氢化，相对于以几种构象存在的催化剂，该手性酮的氢化显着提高。
• PROCESSES FOR PREPARING JAK INHIBITORS AND RELATED INTERMEDIATE COMPOUNDS
  申请人：Zhou Jiacheng

  公开号：US20100190981A1

  公开（公告）日：2010-07-29

  The present invention is related to processes for preparing chiral substituted pyrazolyl pyrrolo[2,3-d]pyrimidines of Formula III, and related synthetic intermediate compounds. The chiral substituted pyrazolyl pyrrolo[2,3-d]pyrimidines are useful as inhibitors of the Janus Kinase family of protein tyrosine kinases (JAKs) for treatment of inflammatory diseases, myeloproliferative disorders, and other diseases.

  本发明涉及制备手性取代吡唑基吡咯并[2,3-d]嘧啶的公式III的过程，以及相关的合成中间体化合物。这些手性取代吡唑基吡咯并[2,3-d]嘧啶可用作抑制Janus激酶家族蛋白酪氨酸激酶（JAKs）的药物，用于治疗炎症性疾病、骨髓增生性疾病和其他疾病。
• Novel diphosphines, their complexes with transisition metals and their use in asymmetric synthesis
  申请人：——

  公开号：US20040260101A1

  公开（公告）日：2004-12-23

  The invention relates to novel diphosphines, in optically pure or racemic form, of formula (I): 1 in which: R 1 and R 2 are a (C 5 -C 7 )cycloalkyl group, an optionally substituted phenyl group or a 5-membered heteroaryl group; and A is (CH 2 —CH 2 ) or CF 2 . The invention further relates to the use of a compound of formula (I) as a ligand for the preparation of a metal complex useful as a chiral catalyst in asymmetric catalysis, and to the chiral metal catalysts comprising at least one ligand of formula (I).

  该发明涉及一种新型二膦化合物，其为光学纯或外消旋形式，化学式（I）如下： 其中： R1和R2为(C5-C7)环烷基，可选择取代的苯基或5-成员杂环烷基；以及 A为(CH2-CH2)或CF2。 该发明还涉及将化合物的化学式（I）用作配体，用于制备金属配合物，该金属配合物在不对称催化中作为手性催化剂有用，并且包括至少一个化学式（I）的手性金属催化剂。
• Intermolecular Palladium(0)-Catalyzed Atropo-enantioselective C–H Arylation of Heteroarenes
  作者：Qui-Hien Nguyen、Shu-Min Guo、Titouan Royal、Olivier Baudoin、Nicolai Cramer

  DOI：10.1021/jacs.9b12299

  日期：2020.2.5

  rare and challenging. An intermolecular and highly enantioselective C-H arylation of relevant heteroarenes providing an efficient access to atropisomeric (hetero)biaryls is reported. The use of a Pd(0) complex equipped with H8-BINAPO as chiral ligand enables the direct functionalization of a broad range of 1,2,3-triazoles and pyrazoles in excellent yields and selectivities of up to 97.5:2.5 er. The

  阻转异构（杂）联芳基是在配体、天然产物和生物活性分子中越来越重要的基序。通过有效的 CH 功能化方法直接构建立体轴非常罕见且具有挑战性。据报道，相关杂芳烃的分子间和高度对映选择性 CH 芳基化提供了对阻转异构（杂）二芳基的有效途径。使用配备有 H8-BINAPO 作为手性配体的 Pd(0) 配合物能够以高达 97.5:2.5 er 的优异产率和选择性直接官能化范围广泛的 1,2,3-三唑和吡唑。该方法还允许 atroposelective 双 CH 芳基化，用于构建两个具有 >99.5:0.5 er 的立体轴。
• Highly active catalysts of bisphosphine oxides for asymmetric Heck reaction
  作者：Jian Hu、Yunpeng Lu、Yongxin Li、Jianrong (Steve) Zhou

  DOI：10.1039/c3cc45233f

  日期：——

  Bisphosphine oxides formed highly active asymmetric Heck catalysts, which were applied in asymmetric synthesis of pharmacologically active azacycles. Olefin insertion proceeded via cis pathways, different from P,N-ligands.

  双膦氧化物形成高活性的不对称Heck催化剂，可用于药理活性氮杂环化合物的不对称合成。不同于P，N-配体，通过顺式途径进行烯烃插入。