Summary: Poly(1,4-cyclohexanedimethylene oxalate) was synthesized from oxalyl chloride and cis/trans-1,4-cyclohexandimethanol.
The polymerization kinetics of oxalyl chloride with 4,4'-isopropylidinediphenol (bisphenol A, BPA) in the presence of pyridine was studied and found that the molecular mass of the polymer was independent of reaction rate [14, 15].
The chemicals used were commercially available analytical grade reagents and used as received: oxalyl chloride, 4-dimethylaminopyridine (4-DMAP), cis/trans-1,4-cyclohexanedimethanol (CHDM) from Acros (Geel, Belgium); cadmium(II) nitrate tetrahydrate and zinc(II) nitrate hexahydrate from BDH (Poole, England); pyridine from Riedel- de Haen (Seelze, Germany); nitric acid (60% w/w), hydrochloric acid (32% w/w), and ethylenediaminetetraacetate-disodium salt (EDTA) from Scharlau (Barcelona, Spain), sodium perchlorate from Sigma-Aldrich (St.
Oxalyl chloride was obtained from Macklin Biochemical Technology Co., Ltd.
In the first step, the carboxyls of CM-[beta]-CD reacted with oxalyl chloride to form carboxymethyl chloride-[beta]-cyclodextrin through nucleophilic substitution.
In Scheme 1, oxalyl chloride (2.56 mL, 30.0 mmol) followed by one-two drops of DMF was added to a stirred suspension of 4-(1-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)vinyl)benzoic acid (413 mg, 1.19 mmol) in C[H.sub.2][Cl.sub.2] (60 mL).
In Scheme 2, oxalyl chloride (1.32 mL, 15.4 mmol) and a catalytic amount of DMF were added to a suspension of 4-(1-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl)vinyl)benzoic acid (214 mg, 0.62 mmol) in C[H.sub.2][Cl.sub.2] (40 mL).
To a stirred solution of cinnamic acid (400 mg, 2.76 mmol) in 4 mL anhydrous C[H.sub.2][Cl.sub.2] at 0[degrees]C and under argon was added 3-4 drops of anhydrous DMF followed by dropwise addition of oxalyl chloride (700 mg, 5.52 mmol, 2eq.).
Cinnamic acid dissolved in refluxing thionyl chloride with catalytic DMF was the preferred route for the synthesis of acyl chlorides destined for the synthesis of the ester, while the acyl chloride synthesized from cold oxalyl chloride in C[H.sub.2][Cl.sub.2] yielded much cleaner crude reaction mixtures and higher yields in the synthesis of the cinnamyl amide.
Aspirin was added to oxalyl chloride solution in dichloromethane followed by addition of few drops of dimethylformamide .
Aspirin, oxalyl chloride, potassium thiocyanate, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 2-toluidine, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, 3,5-dimethoxyaniline, 4-hydroxyl acetanilide, and 1-bromoalkanes were obtained from Merck.
The formation of these moieties is also reported through the formation of acyl chlorides through oxalyl chlorides
and thionyl chloride and then reaction of corresponding acyl chlorides with amine.[15, 16] The use of oxalyl chloride
or thionyl chloride results in the formation of carbon monoxide so chemical and safety measures should be maintained.