1515-76-0

Usage

Uses

1. Used in Chemical Synthesis:
1-Acetoxy-1,3-Butadiene is used as a diene in various chemical reactions for the synthesis of different compounds. It is particularly useful in Diels-Alder reactions, which are important in the formation of cyclic compounds.
2. Used in Pharmaceutical Industry:
1-Acetoxy-1,3-Butadiene is used as a reactant in the synthesis of pharmaceutical compounds through intermolecular oxa-Pictet-Spengler cyclization, a reaction that contributes to the development of complex molecular structures.
3. Used in Polymer Industry:
1-Acetoxy-1,3-Butadiene is used as a monomer in the polymer industry for the production of various polymers with specific properties, such as rubber and plastics.
4. Used in Organic Chemistry Research:
1-Acetoxy-1,3-Butadiene is used as a reactant in organic chemistry research to study the reactivity and selectivity of different dienes and dienophiles in Diels-Alder reactions, as well as other cycloaddition reactions.
5. Used in the Synthesis of Fine Chemicals:
1-Acetoxy-1,3-Butadiene is used as a building block in the synthesis of fine chemicals, such as fragrances, dyes, and other specialty chemicals, due to its ability to participate in various cycloaddition reactions.
6. Used in the Synthesis of Chiral Compounds:
1-Acetoxy-1,3-Butadiene is used in enantioselective Diels-Alder reactions to produce chiral compounds, which are important in the pharmaceutical and agrochemical industries for their specific biological activities.

Safety Profile

Poison by inhalation. Moderatelytoxic by other routes. A skin irritant. Mutation datareported. When heated to decomposition it emits acridsmoke.

Purification Methods

The commercial sample is stabilised with 0.1% of p-tert-butylcatechol. If the material contains crotonaldehyde (by IR, used in its synthesis), it should be dissolved in Et2O, shaken with 40% aqueous sodium bisulfite, then 5% aqueous Na2CO3, water, dried (Na2SO4) and distilled several times in a vacuum through a Widmer [Helv Chim Acta 7 59 1924] (p 11) or Vigreux column (p 11) [Wicterle & Hudlicky Collect Czech Chem Commun 12 564 1947, Hagemeyer & Hull Ind Eng Chem 41 2920 1949]. [Beilstein 2 III 295.]

InChI:InChI=1/C6H8O2/c1-3-4-5-8-6(2)7/h3-5H,1H2,2H3/b5-4+

Upstream product

• 123-73-9 trans-Crotonaldehyde 
• 108-22-5 Isopropenyl acetate 
• 123-73-9 crotonaldehyde 
• 75-36-5 acetyl chloride 
• 108-24-7 acetic anhydride 
• 127-08-2 potassium acetate 
• 127-09-3 sodium acetate 
• 108-21-4 Isopropyl acetate 
• 142-71-2 copper diacetate 
• 104-15-4 toluene-4-sulfonic acid 
• 463-51-4 Ketene 
• 108-05-4 vinyl acetate 
• 64-19-7 acetic acid 
• 106-99-0 buta-1,3-diene 

Downstream Products

• 70063-66-0 1-acetoxy-5-hydroxy-9,10-dioxo-1,4,4a,9,9a,10-hexahydroanthracene 
• 73794-49-7 1-acetoxy-8-hydroxy-9,10-dioxo-1,4,4a,9,9a,10-hexahydroanthracene 
• 6956-96-3 2,3-dimethoxy-1,4-naphthoquinone 
• 167321-72-4 N,N'-(naphthalene-1,4-diyl)bis(4-chlorobenzenesulfonamide) 
• 2206-65-7 cyclohexa-1,3-diene-1-carboxylic acid 
• 73095-59-7 3-Acetoxy-4-cyclohexen-1,2-dicarbonsaeure-dimethylester 
• 73095-59-7 3-Acetoxy-4-cyclohexen-1,2-dicarbonsaeure-dimethylester 
• 4773-89-1 1,4-cyclohexadiene-1,2-dicarboxylic anhydride 
• 68659-50-7 (±)-ethyl (1R,5R,6S)-5-acetoxy-6-nitrocyclohex-3-ene-1-carboxylate 
• 68659-52-9 6-Nitro-6-methyl-3-cyclohexen-r-1-carbonsaeureethylester 
• 68659-53-0 6-Nitro-6-methyl-5-acetoxy-3-cyclohexen-r-1-carbonsaeureaethylester 
• 72167-46-5 4-Benzyloxy-3-methoxy-2'-nitrobiphenyl 
• 54637-97-7 3-<(E)-2-Acetoxyethenyl>-2.2-diphenylcyclobutanon 
• 72167-50-1 3-Acetoxy-4-acetyl-5-phenylcyclohex-1-en 

Relevant academic research and scientific papers

1 - - 1, 3 - Alkadiene acyloxy method (by machine translation)

- 1, 3 - Alkadiene 1 - acyloxy [to] a production method of a industrially useful. (1) Represented by the formula [a] α, β - unsaturated aldehyde reaction to produce the metal alkoxide [...] process is performed, the following formula (3) is reacted with a carboxylic acid anhydride [...] step - 1, 3 - alkadiene represented by the preparation of 1 - acyloxy. (In formula (1), R1 - R3 The, each independently hydrogen, an alkyl group or the like. )[Drawing] no (by machine translation)

METHOD FOR PRODUCING 1-ACYLOXY-1,3-BUTADIENE

PROBLEM TO BE SOLVED: To provide a method for producing a 1-acyloxy-1,3-butadiene that can be performed only with a base of an industrially advantageous catalytic amount. SOLUTION: A method for producing a 1-acyloxy-1,3-butadiene represented by formula (3) includes mixing α,β-unsaturated aldehyde, carboxylic acid anhydride, and a catalytic amount of carboxylate, to heat and agitate the mixture (R1 is derived from α-position of the unsaturated aldehyde and is H, an alkyl group or the like; R2 is derived from β-position of the unsaturated aldehyde and is H, an alkyl group or the like; R3 is H, an alkyl group or the like; R4 is derived from a carboxyl residue of the carboxylic acid anhydride and is a C1-20 alkyl group). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

METHOD FOR PRODUCING 1-ACYLOXY-1,3-BUTADIENE

PROBLEM TO BE SOLVED: To provide a method for producing a 1-acyloxy-1,3-butadiene that can be performed only with a base of a catalytic amount even when a substrate has a boiling point less than 135°C. SOLUTION: A method for producing a 1-acyloxy-1,3-butadiene represented by formula (3) includes treating α,β-unsaturated aldehyde with carboxylic acid anhydride and a catalytic amount of 4-dialkylaminopyridine at a temperature less than 135°C, without requiring a base other than 4-dialkylaminopyridine (R1-R2 independently represent H, a C1-30 linear/branched alkyl; R3 is H, a C1-30 alkyl or a C2-30 alkenyl; R4 is a C1-20 alkyl; alkyl groups of R3 and R4 may be linear/branched, substituted/unsubstituted with halogen, and the alkenyl group may further contain one or more C=C bonds in the group and may be linear/branched, substituted/unsubstituted with halogen). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT

The 'Mikami'-catalyst in enantioselective diels-alder reactions of juglone-based dienophiles with different 1-oxygenated dienes: An investigation on the substitution pattern dependent regioselectivity

A mechanistic study investigating the substitution pattern depending regioselectivity of enantioselective BINOL-Ti-catalyzed Diels-Alder reactions of juglone-based dienophiles with 1-oxygenated dienes is reported. The different influences of residues both on the diene as well as on the dienophiles are investigated giving a detailed picture of their role on the regioselectivity.

The 'Mikami'-Catalyst in Enantioselective Diels-Alder Reactions of Juglone-Based Dienophiles with Different 1-Oxygenated Dienes: An Investigation on the Substitution Pattern Dependent Regioselectivity

A mechanistic study investigating the substitution pattern depending regioselectivity of enantioselective BINOL-Ti-catalyzed- Diels-Alder reactions of juglone-based dienophiles with 1-oxygenated dienes is reported. The different influences of residues both on the diene as well as on the dienophiles are investigated giving a detailed picture of their role on the regioselectivity.

Syntheses of structurally-simplified and fluorescently-labeled neovibsanin derivatives and analysis of their neurite outgrowth activity in PC12 cells

The syntheses of several neovibsanin derivatives were carried out in order to elucidate the simple structure required for displaying neurite outgrowth activity. In addition, a fluorescent probe molecule was synthesized and the analysis of its behavior in the PC12 cell line showed that the neovibsanins accumulate on the outer edge of the cell at the site of formation of prominences.

The high stereoselectivity of the tandem sequence Diels-Alder reaction/Ireland-Claisen rearrangement starting from substituted O-(E)-buta-1,3-dienyl ketene acetals and cyclic dienophiles

A new tandem reaction leads to bicyclic cyclohexene derivatives with complete control of the relative configuration of the four chiral centers formed. The high diastereoselectivity is the consequence of an endo-selective Diels-Alder reaction followed by an Ireland-Claisen rearrangement that proceeds via a boat-like transition state. Georg Thieme Verlag Stuttgart.

Competition between hetero-Diels-Alder and cheletropic addition of sulfur dioxide. Theoretical and experimental substituent effects on the relative stability of 3,6-dihydro-1,2-oxathiin-2-oxides (sultines) and 2,5- dihydrothiophene-1,1-dioxides (sulfolenes). Anomeric effects in sultine and 6-substituted derivatives

At low temperature and in the presence of CF3COOH, SO2 undergoes Diels-Alder additions with (E)-1-acetoxybutadiene (8d) giving a 1:10 mixture of diastereomeric 6-acetoxysultines (9d + 10d). The Van't Hoff plot for equilibria 8d + SO2 ? 9d + 10d led to ΔH(r) = -7.0 ± 0.3 kcal/mol, ΔS(r) = -42 ± 3 cal·mol-1·K -1. At 20 °C, 8d underwent a slow cheletropic addition with SO2 giving 2-acetoxysulfolene (11d, ΔH(r) ? -11.5 kcal/mol), the structure of which was established by single-crystal X-ray diffraction studies. (E)-Chloro (8e) and (E)-bromobutadiene (8f) did not undergo Diels- Alder additions with SO2, even in the presence of protic or Lewis acid promoters. Low yields of 2-chloro- (11e) and 2-bromosulfolene (11f) were obtained at 20 °C. The structure of 11e was confirmed by single-crystal X- ray diffraction. The potential energy hypersurfaces of the Diels-Alder and cheletropic additions of SO2 to butadiene (8a), (E)-piperilene (8b), (E)-1- methoxy- (8c), (E)-1-acetoxy- (8d), and (E)-1-chlorobutadiene (8e) were studied by ab initio quantum calculations at the MP2/631G* level. In agreement with the experiment, 6-substituted sultines 9X and 10X were less stable than the corresponding 2-substituted sulfolenes 11X for X = Me, OAc, Cl. With X = OMe, the two diastereomeric 6-methoxysultines (9c, 10c) and 2- methoxysulfolene (11c) were calculated to have similar stabilities. This is attributed to a stabilizing thermodynamic anomeric effect or gem- sulfinate/methoxy disubstitution effect in 9c, 10c. Such effects were not detected for sulfinate/acetoxy (9d, 10d) and sulfinate/chloro (9e, 10e) disubstitutions. The relative instability of 2-acetoxy- (11d) and 2- chlorosulfolene (11e) compared with their cycloaddents is attributed to repulsive interactions between the SO2 moieties and the 2-substituents. The Alder endo mode of [4 + 2] cycloaddition of SO2 is predicted to be faster than the 'anti-Alder mode' of additions for dienes 8X, X = Me, OMe, OAc, Cl. The resulting diastereomeric sultines 9X and 10X, respectively, exist as equilibria (energy barrier: ca. 5-6 kcal/mol) of two conformers 9X ? 9'X, 10X ? 10'X. In general, the conformers 9X, 10X with pseudoaxial S=O group are preferred (conformational anomeric effect of the sulfinate moiety). Repulsive interactions between pseudoaxial S=O and polar cis-6-substituents (e.g.: X = OMe, OAc) in 9X may render conformers 9'X (with the S=O and 6-X groups in pseudoequatorial positions) as stable as conformers 9X. The calculations predict the existence of conformational anomeric effects of 2-3 kcal/mol for the gem-sulfinate/methoxy (9c, 10'c) and gem-sulfinate/acetoxy disubstitution (9d, 10'd).

Synthetic routes to a constrained ring analog of didemnin B

The didemnin class of biologically active cyclodepsipeptides, isolated from a marine tunicate, has shown antitumor, antiviral, and immunosuppressive activities. Synthetic studies were undertaken to prepare a modified analog of one of the most potent congeners, didemnin B (1). The side chain of the isostatine unit was tethered into the macrocycle via a cyclohexane ring in order to provide a more rigid conformation and determine the importance of this unit in bioactive compounds. This modification created a new macrocycle core and generated a diastereomeric mixture of a constrained analog of didemnin B (2).