Synthesis of 1,3,5-trioxanes: A new, simple method using a bentonitic earth as catalyst.

Camarena, R.; Cano, A.; Delgado, Francisco; Zúñiga, Niño; Álvarez, C.; García, O.

doi:10.1016/s0040-4039(00)91813-6

Cited by 20 publications

(7 citation statements)

References 8 publications

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“…Trihexyl-1,3,5-trioxane (25): From the neat aldehyde 6 and MTO at <-10°C for 2 d. The product was isolated by filtration at <0°C; mp 6-7°C 1. H NMR: d = 0.88 (t, J = 5.4 Hz,9 H), 1.33 (m, 24 H), 1.66 (m, 6 H), 4.84 (t, J = 5.1 Hz, 3 H).…”

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confidence: 99%

Synthesis of 1,3,5-Trioxanes: Catalytic Cyclotrimerization of Aldehydes

Zhu¹,

Espenson²

1998

Synthesis

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A series of 1,3,5-trioxanes derived from a single aldehyde, or from two aldehydes, were synthesized with methylrhenium trioxide as a catalyst. Cyclotrimerization of the aldehydes gave excellent yields under proper conditions, as did diethyl ketomalonate. A possible intermediate in the case of propionaldehyde was observed using 1 H NMR spectroscopy. Water inhibits both forward and reverse reactions.Practical applications abound for 1,3,5-trioxanes 1 in different fields: as constituents of a stabilizing solution in color photography, as burning regulators in fumigants for potato tuber sprouting inhibition and as the basis for many polymers and co-polymers reported in the patent literature. 2,3 Relatively few reports have dealt with the trimerization of aldehydes to form 1,3,5-trioxanes, limited to the following: acetaldehyde, propionaldehyde, isobutyraldehyde, isovaleraldehyde, and 4-tert-butylbenzaldehyde. 1,4-6 The reported methods require pretreatment of the catalyst, 1 the use of a catalyst insoluble in the nonpolar solvent, 6 or result in a reaction that gives rise to several byproducts. 4-6 Here we report a new method, based on the catalyst methylrhenium trioxide (MeReO 3 , abbreviated as MTO), that does not suffer from these limitations.We have undertaken research to describe the synthesis of 1,3,5-trioxanes from a series of aldehydes and from one keto ester (Scheme 1). dient optimization method. Each optimized structure found the R groups of the trioxanes were preferred in equatorial positions. The NMR spectra of the isolated products support the all-equatorial configuration. A single-crystal X-ray determination was carried out to confirm this point, and also to show definitively that a trimer was formed. The ORTEP diagram is displayed in the Figure. The structure is characterized by bond distances and angles that are all within the normal ranges; for example: d(O-C1) = 142.1 pm, d(C1-C2) = 150.6 pm, d(C2-C3) = 149.6 pm, Є(C2-C1-O1) = 109.4°, Ð(C3-C2-C1) = 113.1°, and Ð(O1-C1-O1b) = 109.5°.

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confidence: 99%

Synthesis of 1,3,5-Trioxanes: Catalytic Cyclotrimerization of Aldehydes

Zhu¹,

Espenson²

1998

Synthesis

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“…Many syntheses of these compounds give low yields under rather extreme conditions. A new, mild and high yielding synthesis has been developed for symmetrical 1,3,5-trioxanes which simply involves treatment of aldehydes with bentonitic earth (equation 209) 727 …”

Section: B Heterocycles With Multiple Heteroatomsmentioning

confidence: 99%

Some Synthetic Uses of Double‐Bonded Functional Groups

Hoyle

2009

Patai's Chemistry of Functional Groups

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“…The effect of the amount of ionic liquid on the reaction was studied by varying the quantity of isobutyraldehyde (10,30,40,80, 120, 180 mmol/2 mmol IL). The reactions were carried out under similar reaction conditions as described previously.…”

Section: Effect Of the Amount Of Ionic Liquidmentioning

confidence: 99%

“…1,3,5-trioxanes are used in color photography [1], burning regulators in fumigants [2], flavoring materials [3], carriers for scents, repellents, deodorants [4], and insecticides [5]. Catalysts used ___________________________ for this reaction include protonic acids [6], Keggin-type heteropolyacids [7], cation-exchange resins [8], zeolites [9], bentonitic earth [10], methylrhenium trioxide [11], trimethylsilyl chloride [12], acetyltriphenylphosphonium bromide [13] or Lewis acids such as zinc chloride [14], tantalum pentachloride [15], bismuth trichloride [16], titanium or tin tetrachlorides [17]. Liquid acid catalysts cause equipment corrosion and environmental pollution while solid acids deactivate rapidly due to the build-up of coke.…”

Section: Introductionmentioning

confidence: 99%

Cyclotrimerization of an aliphatic aldehyde catalyzed by acidic ionic liquid

Gui

Liú

Chen

et al. 2007

React Kinet Catal Lett

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Without any additional organic solvent, the cyclotrimerization of aliphatic aldehyde could be catalyzed by acidic ionic liquid. Under optimum reaction conditions (298 K, 1 h, a molar ratio of 60:1 of isobutyraldehyde to ionic liquid), the conversion rate and selectivity for cyclotrimerization of isobutyraldehyde were 93.0 and 100%, respectively. The liquid product formed a separate phase that was decanted and the solid product could be separated by extraction. The ionic liquid could be easily reused after removal of water under vacuum.

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Synthesis of 1,3,5-trioxanes: A new, simple method using a bentonitic earth as catalyst.

Cited by 20 publications

References 8 publications

Synthesis of 1,3,5-Trioxanes: Catalytic Cyclotrimerization of Aldehydes

Synthesis of 1,3,5-Trioxanes: Catalytic Cyclotrimerization of Aldehydes

Some Synthetic Uses of Double‐Bonded Functional Groups

Cyclotrimerization of an aliphatic aldehyde catalyzed by acidic ionic liquid

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