- Potassium Carboxylates by Direct Carbonylation of Potassium Alkoxides
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Reaction of the K+ alkoxide of linalool (1) in benzene with CO at 425-440 bar and 120-130 degC for 12-30 h gave the K+ salt of 2,6-dimethyl-2-vinyl-5-heptenoic acid (4a) in a ca. 25percent yield based on ca. 65percent converted alkoxide.Reaction of the + 18-crown-6> alkoxide of 1 with CO at 50-55 bar and 40 degC for 90-140 h gave a mixture containing mainly the + 18-c-6> salts of 4a (ca. 62percent) and of the homogeranic acids 3a and 6a (together ca. 27percent of the mixture) in a ca. 35percent combined yield based on 50-60percent converted alkoxide.The uncomplexed or complexed K+ alkoxide of (S)-1 gave, with ca. 85percent net retention, the K+ salt of (S)-4a.Reaction of the + 18-c-6> alkoxide of geraniol (2) with CO at 50 bar and 40 degC for 65-70 h gave myrcene (10) and geranyl formate (11) in a ca. 40-50percent yield each based on ca. 85percent converted alkoxide.Reaction of the + 18-c-6> alkoxide of 3-pentyl-1,4-pentadien-3-ol (14) at 50 bar and r.t. for 70 h gave a mixture of the + 18-c-6> salts of 2-pentyl-2-vinyl-3-butenoic acid (15a) (67percent) and the 4-pentyl-2,4-hexadienoic acids 18a and l9a (together 23percent of the mixture) in a ca. 90percent combined yield based on ca. 65percent converted alkoxide.
- Rautenstrauch, Valentin
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- Method for preparing geranyl formate through ionic liquid catalysis
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The invention discloses a method for preparing geranyl formate through ionic liquid catalysis. The preparation method comprises the following steps: carrying out esterification reaction on the ionic liquid as shown IL, carrying out esterification reaction on the geraniol, and separating after the reaction is finished to obtain the geranyl formate. In Formula IL, n is 1 or 2, Y. . Tritrifluoroacetate. Chloride, bromide, trifluoromethanesulfonate, hydrogen sulfate, bis (trifluoromethanesulfonyl) imide, and nitrate. The ionic liquid catalyst has the advantages of high efficiency, environmental friendliness, simplicity, mild reaction conditions (such as 100 °C), simplicity in separation and the like, can efficiently catalyze esterification reaction of formic acid and geraniol to prepare the geranyl formate, and has a wide industrial application prospect.
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Paragraph 0028-0049
(2021/08/25)
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- Efficient Enzymatic Preparation of Flavor Esters in Water
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A straightforward biocatalytic method for the enzymatic preparation of different flavor esters starting from primary alcohols (e.g., isoamyl, n-hexyl, geranyl, cinnamyl, 2-phenethyl, and benzyl alcohols) and naturally available ethyl esters (e.g., formate, acetate, propionate, and butyrate) was developed. The biotransformations are catalyzed by an acyltransferase from Mycobacterium smegmatis (MsAcT) and proceeded with excellent yields (80-97%) and short reaction times (30-120 min), even when high substrate concentrations (up to 0.5 M) were used. This enzymatic strategy represents an efficient alternative to the application of lipases in organic solvents and a significant improvement compared with already known methods in terms of reduced use of organic solvents, paving the way to sustainable and efficient preparation of natural flavoring agents.
- Perdomo, Igor Chiarelli,Gianolio, Stefania,Pinto, Andrea,Romano, Diego,Contente, Martina Letizia,Paradisi, Francesca,Molinari, Francesco
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p. 6517 - 6522
(2019/06/20)
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- Formyloxyacetoxyphenylmethane and 1,1-diacylals as versatile O-formylating and O-acylating reagents for alcohols
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Formyloxyacetoxyphenylmethane, symmetric 1,1-diacylals and mixed 1-pivaloxy-1-acyloxy-1-phenylmethanes have been used as moisture stable O-formylating and O-acylating reagents for primary and secondary alcohols, allylic alcohols and phenols under solvent/catalyst free conditions to afford their corresponding esters in good yield.
- Chapman, Robert S.L.,Francis, Molly,Lawrence, Ruth,Tibbetts, Joshua D.,Bull, Steven D.
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p. 6442 - 6452
(2018/10/02)
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- TiCl4/Et3N-Mediated Condensation of Acetate and Formate Esters: Direct Access to β-Alkoxy- and β-Aryloxyacrylates
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A methodology to build (E)-β-alkoxy- and (E)-β-aryloxyacrylate moieties from acetate and formate esters promoted by the TiCl4/Et3N system is presented. The reaction is compatible with a broad range of structural skeletons and elapses through an unusual condensation pathway. Taking into account the obtained results, we propose a plausible mechanism involving a bimetallic titanium intermediate for this type of transformation.
- álvarez-Calero, José María,Jorge, Zacarías D.,Massanet, Guillermo M.
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supporting information
p. 6344 - 6347
(2016/12/23)
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