Organic Process Research & Development最新文献_第8页

IF 3.1 3区化学

Organic Process Research & Development Pub Date : 2025-02-19 DOI: 10.1021/acs.oprd.4c0052110.1021/acs.oprd.4c00521

Kelvin J. Y. Wu, Priscilla Liow and Andrew G. Myers*,

引用次数: 0

Solvent-Free Production of Triacetin from Glycerol through Complementary Mechanochemical, Biphasic, and Catalytic Approaches Using ICHeM Technology

IF 3.4 3区化学

Organic Process Research & Development Pub Date : 2025-02-19 DOI: 10.1021/acs.oprd.4c00501

Remi Nguyen, Samy Halloumi, Irene Malpartida, Christophe Len

引用次数: 0

Thermal Hazard Assessment of the Synthesis of 1,1′-Azobis-1,2,3-triazole

IF 3.4 3区化学

Organic Process Research & Development Pub Date : 2025-02-19 DOI: 10.1021/acs.oprd.4c00404

Hao Li, Jin-Xi Wu, Guang-Yuan Zhang, Ning-Ning Du, Le-Wu Zhan, Jing Hou, Bin-Dong Li

{"title":"Thermal Hazard Assessment of the Synthesis of 1,1′-Azobis-1,2,3-triazole","authors":"Hao Li, Jin-Xi Wu, Guang-Yuan Zhang, Ning-Ning Du, Le-Wu Zhan, Jing Hou, Bin-Dong Li","doi":"10.1021/acs.oprd.4c00404","DOIUrl":"https://doi.org/10.1021/acs.oprd.4c00404","url":null,"abstract":"Azo energetic compounds have attracted much attention due to their high heat of formation and high oxygen balance. However, due to a lack of safety research on this manufacturing process, industrial production cannot be carried out. 1,1′-Azobis-1,2,3-triazole was chosen as an example to identify hazardous scenarios in the synthesis of azo-energetic materials. First, the properties of the 1,1′-azobis-1,2,3-triazole synthesis experiment were studied using a reaction calorimeter (RC1). Afterward, the thermal stability of the composite materials used in the synthesis process was evaluated using accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC). DSC results showed that the heat release of the mixture was significantly reduced in all three steps. ARC experiments showed that the TD24 values of the three substances are in the range of 100.00–300.00 °C. RC1 experiments showed that the adiabatic temperature rises (ΔTad) in the whole process are 91.26 54.19, 51.49, and 4.10 K, respectively. These findings indicate that the exothermic reaction involved in the synthesis of 1,1′-azobis-1,2,3-triazole is initiated during the dosing phase and is affected by the dosing rate. The overall 1,1′-azobis-1,2,3-triazole synthesis process is a criticality class 1 of a chemical reaction. This holistic approach furnishes valuable data and insights for improving the engineering safety protocols of 1,1′-azobis-1,2,3-triazole, aimed at mitigating risks in industrial operations.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"15 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Practical Synthesis of Oxepanoprolines

IF 3.4 3区化学

Organic Process Research & Development Pub Date : 2025-02-19 DOI: 10.1021/acs.oprd.4c00521

Kelvin J. Y. Wu, Priscilla Liow, Andrew G. Myers

引用次数: 0

A Scalable Process for Synthesizing a Reactive Silicone-Acrylate Monomer

IF 3.4 3区化学

Organic Process Research & Development Pub Date : 2025-02-19 DOI: 10.1021/acs.oprd.4c00495

Souvagya Biswas, Jason S. Fisk, Michael Telgenhoff, Karin Spiers, Muhunthan Sathiosatham, Thu Vi, Matthew S. Jeletic, Jessica E. Nichols, Travis W. Scholtz

{"title":"A Scalable Process for Synthesizing a Reactive Silicone-Acrylate Monomer","authors":"Souvagya Biswas, Jason S. Fisk, Michael Telgenhoff, Karin Spiers, Muhunthan Sathiosatham, Thu Vi, Matthew S. Jeletic, Jessica E. Nichols, Travis W. Scholtz","doi":"10.1021/acs.oprd.4c00495","DOIUrl":"https://doi.org/10.1021/acs.oprd.4c00495","url":null,"abstract":"This study details the route selection, process development, and scale-up of a reactive silicone acrylate monomer, 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate. A direct hydrosilylation reaction between allyl (meth)acrylate and 1,1,1,3,5,5,5-heptamethyltrisiloxane in the presence of Karstedt’s catalyst yielded the desired monomer in 46% yield. Two other byproducts were identified: an oxy-silyl ester and a propene hydrosilylated product. Prior to scale-up, the heat release associated with the hydrosilylation reaction was measured using a combination of isothermal reaction microcalorimetry and postreaction differential scanning calorimetry (DSC). The total heat release of hydrosilylation in the observed microcalorimetry experiment was −415 J/g. DSC studies detected the decomposition of the monomer at 280 °C, thereby revealing the risk of decomposition at elevated temperatures. Finding an inhibitor to prevent unwanted free radical polymerization of the monomer during scale-up and product isolation was crucial. 4-Hydroxy TEMPO was identified as the inhibitor of choice during the scale-up and distillation steps to isolate the monomer. Overall, the process optimization described here enabled a reliable, robust, and scalable method to produce multikilogram quantities of the 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl methacrylate monomer. This approach is also expected to be suitable for other reactive silicone-acrylate-based monomers.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"15 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermal Hazard Assessment of the Synthesis of 1,1′-Azobis-1,2,3-triazole

IF 3.1 3区化学

Organic Process Research & Development Pub Date : 2025-02-19 DOI: 10.1021/acs.oprd.4c0040410.1021/acs.oprd.4c00404

Hao Li, Jin-Xi Wu, Guang-Yuan Zhang, Ning-Ning Du, Le-Wu Zhan, Jing Hou* and Bin-Dong Li*,

{"title":"Thermal Hazard Assessment of the Synthesis of 1,1′-Azobis-1,2,3-triazole","authors":"Hao Li, Jin-Xi Wu, Guang-Yuan Zhang, Ning-Ning Du, Le-Wu Zhan, Jing Hou* and Bin-Dong Li*, ","doi":"10.1021/acs.oprd.4c0040410.1021/acs.oprd.4c00404","DOIUrl":"https://doi.org/10.1021/acs.oprd.4c00404https://doi.org/10.1021/acs.oprd.4c00404","url":null,"abstract":"Azo energetic compounds have attracted much attention due to their high heat of formation and high oxygen balance. However, due to a lack of safety research on this manufacturing process, industrial production cannot be carried out. 1,1′-Azobis-1,2,3-triazole was chosen as an example to identify hazardous scenarios in the synthesis of azo-energetic materials. First, the properties of the 1,1′-azobis-1,2,3-triazole synthesis experiment were studied using a reaction calorimeter (RC1). Afterward, the thermal stability of the composite materials used in the synthesis process was evaluated using accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC). DSC results showed that the heat release of the mixture was significantly reduced in all three steps. ARC experiments showed that the TD24 values of the three substances are in the range of 100.00–300.00 °C. RC1 experiments showed that the adiabatic temperature rises (ΔTad) in the whole process are 91.26 54.19, 51.49, and 4.10 K, respectively. These findings indicate that the exothermic reaction involved in the synthesis of 1,1′-azobis-1,2,3-triazole is initiated during the dosing phase and is affected by the dosing rate. The overall 1,1′-azobis-1,2,3-triazole synthesis process is a criticality class 1 of a chemical reaction. This holistic approach furnishes valuable data and insights for improving the engineering safety protocols of 1,1′-azobis-1,2,3-triazole, aimed at mitigating risks in industrial operations.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"29 3","pages":"650–662 650–662"},"PeriodicalIF":3.1,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Solvent-Free Production of Triacetin from Glycerol through Complementary Mechanochemical, Biphasic, and Catalytic Approaches Using ICHeM Technology

IF 3.1 3区化学

Organic Process Research & Development Pub Date : 2025-02-19 DOI: 10.1021/acs.oprd.4c0050110.1021/acs.oprd.4c00501

Remi Nguyen, Samy Halloumi, Irene Malpartida and Christophe Len*,

{"title":"Solvent-Free Production of Triacetin from Glycerol through Complementary Mechanochemical, Biphasic, and Catalytic Approaches Using ICHeM Technology","authors":"Remi Nguyen, Samy Halloumi, Irene Malpartida and Christophe Len*, ","doi":"10.1021/acs.oprd.4c0050110.1021/acs.oprd.4c00501","DOIUrl":"https://doi.org/10.1021/acs.oprd.4c00501https://doi.org/10.1021/acs.oprd.4c00501","url":null,"abstract":"Impact in Continuous Flow Heated Mechanochemistry (ICHeM) was utilized for the biphasic acetylation of glycerol with immiscible acetic anhydride in the presence of homogeneous acid catalysts. This innovative technology combines efficient phase dispersion with continuous flow, offering the following benefits: (i) improved mixing of the two immiscible components (liquid glycerol and highly reactive acetic anhydride); (ii) mechanochemical energy generated by bead impact in continuous flow, eliminating the need for additional heating energy; and (iii) an alternative to single- and double-screw extruders, which are ineffective with liquid reaction media. Under our optimized conditions, triacetin “t” can be obtained with a 99% yield (100% conversion and 99% selectivity) in a solvent-free biphasic continuous flow process with a residence time of 15–30 min, using efficient homogeneous Lewis acids like iron triflate II or Brönsted acids like sulfuric acid.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"29 3","pages":"769–777 769–777"},"PeriodicalIF":3.1,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Inverse Transformation of Glycine by Crystal Size Control

IF 3.1 3区化学

Organic Process Research & Development Pub Date : 2025-02-18 DOI: 10.1021/acs.oprd.4c0042210.1021/acs.oprd.4c00422

Jeongki Kang, Jongwook Park, Jinsoo Kim* and Woo-Sik Kim*,

{"title":"Inverse Transformation of Glycine by Crystal Size Control","authors":"Jeongki Kang, Jongwook Park, Jinsoo Kim* and Woo-Sik Kim*, ","doi":"10.1021/acs.oprd.4c0042210.1021/acs.oprd.4c00422","DOIUrl":"https://doi.org/10.1021/acs.oprd.4c00422https://doi.org/10.1021/acs.oprd.4c00422","url":null,"abstract":"This study proposed a method for inverse phase transformation of stable γ-glycine into metastable α-glycine by using the characteristic that solubility increases as crystal size decreases according to the Ostwald–Freundlich equation. First, we measured the change in solubility according to the particle size of glycine. The solubility of γ-glycine bulk crystals at 10 °C in water was 173 g/L, and when the crystal size decreased to about 0.9 μm, the solubility increased to about 185 g/L. This concentration was higher than the solubility of α-glycine bulk crystals, 180 g/L. Based on the above results, γ-glycine can be inverse transformed into α-glycine in aqueous solution. To demonstrate this inverse transformation, in a glycine solution, γ-glycine crystals with a size of about 2 μm were ground with glass beads for 24 h to reduce the crystal size to about 0.8 μm. And the concentration of the solution was made higher than the solubility of α-glycine bulk. α-Glycine bulk crystals (about 110 μm) were placed into this solution and grown to 170 μm. Through this, inverse phase transformation was achieved in which γ-glycine crystals were dissolved and α-glycine crystals grew. The above inverse phase transformation process was confirmed using a microscope, XRD, and ATR–FTIR.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"29 3","pages":"663–670 663–670"},"PeriodicalIF":3.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Inverse Transformation of Glycine by Crystal Size Control

IF 3.4 3区化学

Organic Process Research & Development Pub Date : 2025-02-18 DOI: 10.1021/acs.oprd.4c00422

Jeongki Kang, Jongwook Park, Jinsoo Kim, Woo-Sik Kim

{"title":"Inverse Transformation of Glycine by Crystal Size Control","authors":"Jeongki Kang, Jongwook Park, Jinsoo Kim, Woo-Sik Kim","doi":"10.1021/acs.oprd.4c00422","DOIUrl":"https://doi.org/10.1021/acs.oprd.4c00422","url":null,"abstract":"This study proposed a method for inverse phase transformation of stable γ-glycine into metastable α-glycine by using the characteristic that solubility increases as crystal size decreases according to the Ostwald–Freundlich equation. First, we measured the change in solubility according to the particle size of glycine. The solubility of γ-glycine bulk crystals at 10 °C in water was 173 g/L, and when the crystal size decreased to about 0.9 μm, the solubility increased to about 185 g/L. This concentration was higher than the solubility of α-glycine bulk crystals, 180 g/L. Based on the above results, γ-glycine can be inverse transformed into α-glycine in aqueous solution. To demonstrate this inverse transformation, in a glycine solution, γ-glycine crystals with a size of about 2 μm were ground with glass beads for 24 h to reduce the crystal size to about 0.8 μm. And the concentration of the solution was made higher than the solubility of α-glycine bulk. α-Glycine bulk crystals (about 110 μm) were placed into this solution and grown to 170 μm. Through this, inverse phase transformation was achieved in which γ-glycine crystals were dissolved and α-glycine crystals grew. The above inverse phase transformation process was confirmed using a microscope, XRD, and ATR–FTIR.","PeriodicalId":55,"journal":{"name":"Organic Process Research & Development","volume":"52 1","pages":""},"PeriodicalIF":3.4,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143452315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Nonclogging Liquid-Walled Continuous Flow Reactors

IF 3.4 3区化学

Organic Process Research & Development Pub Date : 2025-02-12 DOI: 10.1021/acs.oprd.4c00459

Alejandro Mata, Caroline de Fraipont, Céline Hervieux, Lucas Giacchetti, Oicime Hadj-Sassi, Alexandra Bogicevic, Vincent Marichez, Thomas M. Hermans

引用次数: 0