69814-56-8

Usage

Uses

Used in Pharmaceutical Industry:
2-Methylene-1,3-dioxepane is used as a building block for the construction of biodegradable pH-sensitive polymeric prodrugs. These prodrugs are designed for intracellular drug delivery, allowing for the controlled and targeted release of therapeutic agents within specific cellular environments. The use of 2-methylene-1,3-dioxepane in this context leverages its ability to form functional terpolymers, which can be tailored to respond to changes in pH, thereby enhancing the effectiveness and precision of drug delivery systems.

Upstream product

• 54237-96-6 2-Chloromethyl-1,3-dioxepane 
• 5337-72-4 2,6-dimethylcyclohexanol 
• 78-92-2 iso-butanol 
• 110-03-2 2,5-dimethyl-2,5-hexanediol 
• 110-63-4 Butane-1,4-diol 
• 97-97-2 chloroacetaldehyde dimethyl acetal 
• 57626-95-6 2-(bromomethyl)-1,3-dioxepane 
• 75-85-4 tert-Amyl alcohol 
• 1634-04-4 tert-butyl methyl ether 
• 107-21-1 ethylene glycol 
• 600-36-2 2,4-dimethyl-3-pentanol 

Downstream Products

• 628-67-1 butane-1,4-diol diacetate 
• 106842-94-8 4-acetoxybutyl benzoate 
• 116424-09-0 2-(phenylcarbamoylmethylidene)-1,3-dioxepane 
• 116424-08-9 8-phenyl-1,6-dioxa-8-azaspiro<6.3>decan-9-one 

Relevant academic research and scientific papers

Polyesters by a Radical Pathway: Rationalization of the Cyclic Ketene Acetal Efficiency

Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring-opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl-based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring-opening and ring-retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring-open under all experimental conditions. In this article we investigate the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring-opening ability of CKA monomers.

IMPLANTABLE SWELLABLE BIO-RESORBABLE POLYMER

The present invention relates to a polymer obtained from the polymerization of: (i) at least one monomer of formula (I) (CH2═CR1)CO—K (1) wherein: K represents O—Z or NH—Z, Z representing (CR2R3)m-CH3, (CH2—CH2—O)m-H, (CH2—CH2—O)m-CH3, (CH2)m-NR4R5 with m representing an integer from 1 to 30; R1, R2, R3, R4 and R5 independently represent H or a C1-C6 alkyl; (ii) at least between 0.1 and 50% mol, advantageously between 1 and 30% mol, more advantageously between 1 and 20 mol % of a cyclic monomer having a exomethylene group of formula (II) wherein: R6, R7, R8 and R9 represent independently H or a C5-C7 aryl group or R6 and R9 are absent and R7 and R8 form together with the carbon atom on which they are bonded a C5-C7 aryl group; i and j represent independently an integer chosen between 0 and 2; X represents either O or X is not present and in this latter case, CR6R7 and CR8R9 are linked via a single bond C—C and (iii) at least one bio-resorbable block copolymer cross-linker.

A short and efficient synthesis of ketene O,O-and S,S-acetals under focused microwave irradiation and solvent-free conditions

A new methodology leading to ketene O,O-and S,S-acetals is reported. The title compounds were prepared from the corresponding halogenated precursors under microwave irradiation in the absence of solvent within 5-25 minutes with excellent yields. Yields obtained under microwaves are by far the best when compared to those obtained by ultrasound or classical heating in the same conditions of time and temperature.

Process for preparing ketene acetals

The invention relates to a process for preparing ketene acetals by dehydrohalogenation of 2-haloaldehyde acetals. If the 2-haloaldehyde acetal is open chain, the dehydrohalogenation is carried out in the presence of an alkali metal hydroxide or alkaline earth metal hydroxide and a phase transfer catalyst and/or a secondary or tertiary alcohol or a secondary or tertiary diol. If the 2-haloaldehyde acetals is cyclic, the dehydrohalogenation is carried out in the presence of an alkali metal hydroxide or alkaline earth metal hydroxide and a phase transfer catalyst and with or without a secondary or tertiary alcohol or a secondary or tertiary diol, or carried out in the presence of an alkali metal hydroxide or alkaline earth metal hydroxide and a secondary or tertiary diol. The ketene acetals which can be prepared by the process of the invention serve as intermediates in organic synthesis and are suitable as monomers or comonomers in free radical polymerization for the production of biodegradable plastics.

A short and simple synthesis of ketene acetals

A novel and convenient synthesis of ketene acetals 1a-g in moderate to good yield has been achieved starting from acetonitrile by using Pinner reaction approach.

Preparation of racemic and enantiomerically pure cyclic ketene acetals

Cyclic ketene acetals have been prepared from a-haloaldehyde dimethylacetals by transacetalization and subsequent elimination in PTC without solvent conditions. No racemization has been observed when an enantiomerically pure diol has been used. Stability and storage conditions have been studies.

Purification of cyclic ketene acetals

An improved process for the purification of cyclic ketene acetals such as 2-methylene-1,3-dioxepane is provided. This process entails the purification of the cyclic ketene acetal by distillation in the presence of a solvent and an amine.

Relationship between Reaction Rates and NMR Chemical Shifts in the Reaction of Cyclic Ketene Acetals with Methanol

The reaction of cyclic ketene acetals with methanol gave the corresponding cyclic orthoacetates in fairly good yield.The linear relationship between their reaction rates and 1H or 13C NMR chemical shifts of unsaturated methylene groups was obtained from the kinetic studies.