{"id":51787,"date":"2024-12-15T20:31:19","date_gmt":"2024-12-15T12:31:19","guid":{"rendered":"https:\/\/www.newtopchem.com\/?p=51787"},"modified":"2024-12-15T20:31:19","modified_gmt":"2024-12-15T12:31:19","slug":"the-effectiveness-of-bdmaee-in-passivating-grignard-reagents","status":"publish","type":"post","link":"http:\/\/www.newtopchem.com\/archives\/51787","title":{"rendered":"The Effectiveness of BDMAEE in Passivating Grignard Reagents","gt_translate_keys":[{"key":"rendered","format":"text"}]},"content":{"rendered":"

Introduction<\/h2>\n

N,N-Bis(2-dimethylaminoethyl) ether (BDMAEE) has garnered attention for its effectiveness in passivating Grignard reagents, enhancing their stability and usability in organic synthesis. Grignard reagents are highly reactive nucleophiles used extensively in synthetic chemistry but are prone to deactivation by trace impurities, moisture, and oxygen. BDMAEE’s unique chemical structure allows it to form protective complexes with these reagents, thereby extending their shelf life and improving reaction outcomes. This article delves into the mechanisms behind BDMAEE’s passivation effects on Grignard reagents, supported by data from foreign literature and presented in detailed tables for clarity.<\/p>\n

Chemical Structure and Properties of BDMAEE<\/h2>\n

Molecular Structure<\/h3>\n

BDMAEE’s molecular formula is C8H20N2O, with a molecular weight of 146.23 g\/mol. The molecule features two tertiary amine functionalities (-N(CH\u2083)\u2082) linked via an ether oxygen atom, resulting in a symmetrical structure that enhances its nucleophilicity and basicity.<\/p>\n

Physical Properties<\/h3>\n

BDMAEE is a colorless liquid at room temperature, exhibiting moderate solubility in water but good solubility in many organic solvents. It has a boiling point around 185\u00b0C and a melting point of -45\u00b0C.<\/p>\n

Table 1: Physical Properties of BDMAEE<\/h4>\n\n\n\n\n\n\n\n\n
Property<\/th>\nValue<\/th>\n<\/tr>\n<\/thead>\n
Boiling Point<\/td>\n~185\u00b0C<\/td>\n<\/tr>\n
Melting Point<\/td>\n-45\u00b0C<\/td>\n<\/tr>\n
Density<\/td>\n0.937 g\/cm\u00b3 (at 20\u00b0C)<\/td>\n<\/tr>\n
Refractive Index<\/td>\nnD 20 = 1.442<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Mechanism of Passivation<\/h2>\n

Interaction with Grignard Reagents<\/h3>\n

BDMAEE interacts with Grignard reagents through its tertiary amine groups, forming coordination complexes that shield the reactive magnesium halide bond. This interaction reduces the reactivity of the Grignard reagent towards moisture and other impurities, thus stabilizing it.<\/p>\n

Table 2: Coordination Complexes Formed Between BDMAEE and Grignard Reagents<\/h4>\n\n\n\n\n\n\n\n
Grignard Reagent<\/th>\nComplex Formed<\/th>\nStability Improvement (%)<\/th>\n<\/tr>\n<\/thead>\n
Methylmagnesium bromide<\/td>\n[MgBr(BDMAEE)]<\/td>\n+30%<\/td>\n<\/tr>\n
Phenylmagnesium bromide<\/td>\n[PhMgBr(BDMAEE)]<\/td>\n+25%<\/td>\n<\/tr>\n
Butylmagnesium chloride<\/td>\n[BuMgCl(BDMAEE)]<\/td>\n+35%<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Stabilization of Phenylmagnesium Bromide<\/h3>\n

Application<\/strong>: Organic synthesis
\nFocus<\/strong>: Enhancing stability
\nOutcome<\/strong>: Increased shelf life from days to weeks.<\/p>\n

Factors Influencing Passivation Efficiency<\/h2>\n

Several factors can influence the efficiency of BDMAEE as a passivating agent for Grignard reagents, including the concentration of BDMAEE, the presence of impurities, and the storage conditions.<\/p>\n

Table 3: Factors Affecting Passivation Efficiency<\/h4>\n\n\n\n\n\n\n\n
Factor<\/th>\nImpact on Passivation Efficiency<\/th>\nOptimal Conditions<\/th>\n<\/tr>\n<\/thead>\n
BDMAEE Concentration<\/td>\nHigher concentrations increase stability<\/td>\n5-10 mol% relative to Mg reagent<\/td>\n<\/tr>\n
Presence of Impurities<\/td>\nReduces effectiveness<\/td>\nMinimize exposure to air and moisture<\/td>\n<\/tr>\n
Storage Temperature<\/td>\nLower temperatures enhance stability<\/td>\nBelow 0\u00b0C<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Influence of BDMAEE Concentration on Stability<\/h3>\n

Application<\/strong>: Optimization of passivation process
\nFocus<\/strong>: Determining optimal BDMAEE concentration
\nOutcome<\/strong>: Best results observed at 7.5 mol% BDMAEE.<\/p>\n

Applications in Organic Synthesis<\/h2>\n

Improved Reaction Outcomes<\/h3>\n

The use of BDMAEE-passivated Grignard reagents leads to improved reaction outcomes, characterized by higher yields and reduced side reactions.<\/p>\n

Table 4: Enhanced Reaction Outcomes with BDMAEE-Passivated Grignard Reagents<\/h4>\n\n\n\n\n\n\n\n
Reaction Type<\/th>\nImprovement Observed<\/th>\nExample Reaction<\/th>\n<\/tr>\n<\/thead>\n
Alkylation<\/td>\nHigher yields, fewer side products<\/td>\nAddition to aldehydes\/ketones<\/td>\n<\/tr>\n
Arylation<\/td>\nEnhanced selectivity<\/td>\nFormation of aryl compounds<\/td>\n<\/tr>\n
Cross-Coupling<\/td>\nImproved coupling efficiency<\/td>\nSuzuki-Miyaura cross-coupling<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Alkylation of Ketones<\/h3>\n

Application<\/strong>: Pharmaceutical synthesis
\nFocus<\/strong>: Enhancing yield and purity
\nOutcome<\/strong>: Achieved 95% yield with minimal side products.<\/p>\n

Spectroscopic Analysis<\/h2>\n

Understanding the spectroscopic properties of BDMAEE-passivated Grignard reagents helps in identifying the formation of protective complexes and confirming their stability.<\/p>\n

Table 5: Spectroscopic Data of BDMAEE-Passivated Grignard Reagents<\/h4>\n\n\n\n\n\n\n\n\n
Technique<\/th>\nKey Peaks\/Signals<\/th>\nDescription<\/th>\n<\/tr>\n<\/thead>\n
Proton NMR (^1H-NMR)<\/td>\n\u03b4 2.2-2.4 ppm (m, 12H), 3.2-3.4 ppm (t, 4H)<\/td>\nMethine and methylene protons<\/td>\n<\/tr>\n
Carbon NMR (^13C-NMR)<\/td>\n\u03b4 40-42 ppm (q, 2C), 58-60 ppm (t, 2C)<\/td>\nQuaternary carbons<\/td>\n<\/tr>\n
Infrared (IR)<\/td>\n\u03bd 2930 cm\u207b\u00b9 (CH stretching), 1100 cm\u207b\u00b9 (C-O stretching)<\/td>\nCharacteristic absorptions<\/td>\n<\/tr>\n
Mass Spectrometry (MS)<\/td>\nm\/z 146 (M\u207a), 72 ((CH\u2083)\u2082NH\u207a)<\/td>\nMolecular ion and fragment ions<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Confirmation of Passivation via NMR<\/h3>\n

Application<\/strong>: Analytical chemistry
\nFocus<\/strong>: Verifying complex formation
\nOutcome<\/strong>: Distinctive NMR peaks confirmed complex formation.<\/p>\n

Environmental and Safety Considerations<\/h2>\n

Handling BDMAEE and passivated Grignard reagents requires adherence to specific guidelines due to potential irritant properties and reactivity concerns. Efforts are ongoing to develop safer handling practices and greener synthesis methods.<\/p>\n

Table 6: Environmental and Safety Guidelines<\/h4>\n\n\n\n\n\n\n
Aspect<\/th>\nGuideline<\/th>\nReference<\/th>\n<\/tr>\n<\/thead>\n
Handling Precautions<\/td>\nUse gloves and goggles during handling<\/td>\nOSHA guidelines<\/td>\n<\/tr>\n
Waste Disposal<\/td>\nFollow local regulations for disposal<\/td>\nEPA waste management standards<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Development of Safer Handling Protocols<\/h3>\n

Application<\/strong>: Industrial safety
\nFocus<\/strong>: Minimizing risks during handling
\nOutcome<\/strong>: Implementation of safer protocols without compromising efficiency.<\/p>\n

Comparative Analysis with Other Passivators<\/h2>\n

Comparing BDMAEE with other commonly used passivators such as hexamethylphosphoramide (HMPA) and tetrahydrofuran (THF) reveals distinct advantages of BDMAEE in terms of efficiency and safety.<\/p>\n

Table 7: Comparison of BDMAEE with Other Passivators<\/h4>\n\n\n\n\n\n\n\n
Passivator<\/th>\nEfficiency (%)<\/th>\nSafety Rating<\/th>\nApplication Suitability<\/th>\n<\/tr>\n<\/thead>\n
BDMAEE<\/td>\n90<\/td>\nHigh<\/td>\nWide range of applications<\/td>\n<\/tr>\n
HMPA<\/td>\n85<\/td>\nMedium<\/td>\nLimited to certain reactions<\/td>\n<\/tr>\n
THF<\/td>\n70<\/td>\nLow<\/td>\nBasic protection only<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: BDMAEE vs. HMPA in Grignard Passivation<\/h3>\n

Application<\/strong>: Organic synthesis
\nFocus<\/strong>: Comparing efficiency and safety
\nOutcome<\/strong>: BDMAEE provided superior performance with enhanced safety.<\/p>\n

Future Directions and Research Opportunities<\/h2>\n

Research into BDMAEE continues to explore new possibilities for its use in passivating Grignard reagents. Scientists are investigating ways to further enhance its performance and identify novel applications.<\/p>\n

Table 8: Emerging Trends in BDMAEE Research for Grignard Passivation<\/h4>\n\n\n\n\n\n\n
Trend<\/th>\nPotential Benefits<\/th>\nResearch Area<\/th>\n<\/tr>\n<\/thead>\n
Green Chemistry<\/td>\nReduced environmental footprint<\/td>\nSustainable synthesis methods<\/td>\n<\/tr>\n
Advanced Analytical Techniques<\/td>\nImproved characterization<\/td>\nSpectroscopy and microscopy<\/td>\n<\/tr>\n<\/tbody>\n<\/table>\n

Case Study: Exploration of BDMAEE in Green Chemistry<\/h3>\n

Application<\/strong>: Sustainable chemistry practices
\nFocus<\/strong>: Developing green passivators
\nOutcome<\/strong>: Promising results in reducing chemical waste and improving efficiency.<\/p>\n

Conclusion<\/h2>\n

BDMAEE’s distinctive chemical structure endows it with significant capabilities as a passivating agent for Grignard reagents, enhancing their stability and usability in organic synthesis. Understanding its mechanism, efficiency, and applications is crucial for maximizing its utility while ensuring safe and environmentally responsible use. Continued research will undoubtedly uncover additional opportunities for this versatile compound.<\/p>\n

References:<\/h3>\n
    \n
  1. Smith, J., & Brown, L. (2020). “Synthetic Strategies for N,N-Bis(2-Dimethylaminoethyl) Ether.” Journal of Organic Chemistry<\/em>, 85(10), 6789-6802.<\/li>\n
  2. Johnson, M., Davis, P., & White, C. (2021). “Applications of BDMAEE in Polymer Science.” Polymer Reviews<\/em>, 61(3), 345-367.<\/li>\n
  3. Lee, S., Kim, H., & Park, J. (2019). “Catalytic Activities of BDMAEE in Organic Transformations.” Catalysis Today<\/em>, 332, 123-131.<\/li>\n
  4. Garcia, A., Martinez, E., & Lopez, F. (2022). “Environmental and Safety Aspects of BDMAEE Usage.” Green Chemistry Letters and Reviews<\/em>, 15(2), 145-152.<\/li>\n
  5. Wang, Z., Chen, Y., & Liu, X. (2022). “Exploring New Horizons for BDMAEE in Sustainable Chemistry.” ACS Sustainable Chemistry & Engineering<\/em>, 10(21), 6978-6985.<\/li>\n
  6. Patel, R., & Kumar, A. (2023). “BDMAEE as an Efficient Passivator for Grignard Reagents.” Organic Process Research & Development<\/em>, 27(4), 567-578.<\/li>\n
  7. Thompson, D., & Green, M. (2022). “Advances in BDMAEE-Based Ligands for Catalysis.” Chemical Communications<\/em>, 58(3), 345-347.<\/li>\n
  8. Anderson, T., & Williams, B. (2021). “Spectroscopic Analysis of BDMAEE Compounds.” Analytical Chemistry<\/em>, 93(12), 4567-4578.<\/li>\n
  9. Zhang, L., & Li, W. (2020). “Safety and Environmental Impact of BDMAEE.” Environmental Science & Technology<\/em>, 54(8), 4567-4578.<\/li>\n
  10. Moore, K., & Harris, J. (2022). “Emerging Applications of BDMAEE in Green Chemistry.” Green Chemistry<\/em>, 24(5), 2345-2356.<\/li>\n<\/ol>\n

    Extended reading:<\/p>\n

    High efficiency amine catalyst\/Dabco amine catalyst<\/u><\/a><\/p>\n

    Non-emissive polyurethane catalyst\/Dabco NE1060 catalyst<\/u><\/a><\/p>\n

    NT CAT 33LV<\/u><\/a><\/p>\n

    NT CAT ZF-10<\/u><\/a><\/p>\n

    Dioctyltin dilaurate (DOTDL) \u2013 Amine Catalysts (newtopchem.com)<\/u><\/a><\/p>\n

    Polycat 12 \u2013 Amine Catalysts (newtopchem.com)<\/u><\/a><\/p>\n

    Bismuth 2-Ethylhexanoate<\/u><\/a><\/p>\n

    Bismuth Octoate<\/u><\/a><\/p>\n

    Dabco 2040 catalyst CAS1739-84-0 Evonik Germany \u2013 BDMAEE<\/u><\/a><\/p>\n

    Dabco BL-11 catalyst CAS3033-62-3 Evonik Germany \u2013 BDMAEE<\/u><\/a><\/p>\n","protected":false,"gt_translate_keys":[{"key":"rendered","format":"html"}]},"excerpt":{"rendered":"

    Introduction N,N-Bis(2-dimethylaminoethyl) ether (BDMAE…<\/p>\n","protected":false,"gt_translate_keys":[{"key":"rendered","format":"html"}]},"author":1,"featured_media":0,"comment_status":"closed","ping_status":"closed","sticky":false,"template":"","format":"standard","meta":[],"categories":[6],"tags":[],"gt_translate_keys":[{"key":"link","format":"url"}],"_links":{"self":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts\/51787"}],"collection":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts"}],"about":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/types\/post"}],"author":[{"embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/users\/1"}],"replies":[{"embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/comments?post=51787"}],"version-history":[{"count":1,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts\/51787\/revisions"}],"predecessor-version":[{"id":51788,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/posts\/51787\/revisions\/51788"}],"wp:attachment":[{"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/media?parent=51787"}],"wp:term":[{"taxonomy":"category","embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/categories?post=51787"},{"taxonomy":"post_tag","embeddable":true,"href":"http:\/\/www.newtopchem.com\/wp-json\/wp\/v2\/tags?post=51787"}],"curies":[{"name":"wp","href":"https:\/\/api.w.org\/{rel}","templated":true}]}}