Chemical release control: Sulfonate esters from perfume and herbicide alcohols and p‐styrenesulfonyl chloride

Abstract

p‐Styrenesulfonate esters of primary and secondary perfume alcohols and phenols, including citronellol, 1‐menthol, borneol, β‐phenethyl alcohol, eugenol, p‐anisyl alcohol, cinnamyl alcohol, and geraniol, and herbicide alcohols such as 2,4‐dichloro‐ and 2,4,5‐trichlorophenoxy‐ethanols were synthesized using p‐styrenesulfonyl chloride in the presence of bases such as pyridine, triethylamine, sodium hydrogen carbonate, and sodium hydride. The hydrolytic behavior of sulfonate ester monomers and their copolymers with N‐vinyl‐2‐pyrrolidone to liberate perfume and herbicide alcohols was structure‐dependent, thereby affording chemical release control.

Controlled Release of Volatiles under Mild Reaction Conditions: From Nature to Everyday Products

“…As a result of steric hindrance, random co-polymer 72 released only about half the amount of borneol as the corresponding monomer after one week in a solution of dioxane/water (5:1). [145] Whereas esters of primary and secondary alcohols could easily be prepared, the esterification of tertiary alcohols was unsuccessful.…”

“…A series of inorganic esters of fragrance alcohols, in particular phosphates (41), sulfites (70), sulfates (71), [108] and sulfonates (72), [145][146][147] as well as borates (73), [86,148] aluminates, [149] zirconates, and titanates (74) [150] have been reported (Scheme 25). Sulfonates are readily accessible by reaction of the volatile alcohols with sulfonyl chlorides in the presence of a base.…”

Profragrances and Properfumes

“…34 Figure 13.7 indicates the extent of hydrolysis of co-polymers 32-35 determined in an aqueous solution of dioxane at 20 C after 24 h. The different amounts of alcohols released from the polymer conjugates were attributed to the possible stabilization of an intermediately formed carbocation by electron-donating groups such as the double bond in 32, or by inductive effects of secondary alkyl groups as in 33, which increase the rates of hydrolysis with respect to the nonconjugated primary alcohol-releasing polymer 34. A particular case is co-polymer 35 which readily released citronellol under the given reaction (Figure 13.7).…”

“…A particular case is co-polymer 35 which readily released citronellol under the given reaction (Figure 13.7). 34 Some additional aspects arising from the polymer structure itself are further discussed below.…”

Controlled Release of Damascone from Poly(styrene-co-maleic anhydride)-based Bioconjugates in Functional Perfumery

“…Reaction conditions allowing covalent bond cleavage and the release of the volatile biomolecule from its precursor comprise changes in temperature or pH, hydrolysis, oxidation and exposure to daylight or enzymes [9][10][11][12][13][14][15]. In addition to small molecular precursors, polymer bioconjugates have been investigated for the slow release of volatile compounds [9][10][11][16][17][18][19][20][21][22][23][24][25][26][27][28]. The ease of structural modulation of polymeric materials was expected to allow the selective influence of the properties of the delivery systems and their adaptation to the particular requirements of the formulations into which they were incorporated.…”