Aldehydes ethyl acrylate

It has been reported that 1,1,1-trifluoroacetone trimeiizes in the presence of amines (Scheme 8) (18). Although we observed some reaction in die case of perfluoroalkyl aldehydes, ethyl acrylate and methyl vinyl ketone failed to react with 1,1,1-trifluoroacetone. Acrolein and acrylonitrile provided -10% yield of the product along with the trimer. 

The aziridine aldehyde 56 undergoes a facile Baylis-Hillman reaction with methyl or ethyl acrylate, acrylonitrile, methyl vinyl ketone, and vinyl sulfone [60]. The adducts 57 were obtained as mixtures of syn- and anfz-diastereomers. The synthetic utility of the Baylis-Hillman adducts was also investigated. With acetic anhydride in pyridine an SN2 -type substitution of the initially formed allylic acetate by an acetoxy group takes place to give product 58. Nucleophilic reactions of this product with, e. g., morpholine, thiol/Et3N, or sodium azide in DMSO resulted in an apparent displacement of the acetoxy group. Tentatively, this result may be explained by invoking the initial formation of an ionic intermediate 59, which is then followed by the reaction with the nucleophile as shown in Scheme 43. 

Ethyl acrylate Ethyl alcohol, see Ethanol Ethyl aldehyde, see Acetaldehyde 0.92 3.5 16 273... 

The asymmetric Baylis-Hillman reaction of sugar-derived aldehydes as chiral electrophiles with an activated olefin in dioxane water (1 1) proceeded with 36-86% de and in good yields of the corresponding glycosides (Eq. 10.47).104 The use of chiral /V-mcthylprolinol as a chiral base catalyst for the Baylis-Hillman reaction of aromatic aldehydes with ethyl acrylate or methyl vinyl ketone gave the adducts in good yields with moderate-to-good enantioselectivities in l,4-dioxane water (1 1, vol/vol) under ambient conditions.105... 

The Wittig-Horner (W-H) reaction is a versatile method for the synthesis of functionalized alkenes. The synthesis of 3-substituted ethyl acrylates and acrylonitriles, which are used as monomers in polymerization, were successfully carried out by the reaction of triethyl phosphonoacetate or cyanomethanephosphonate, respectively, with various aldehydes with activated Ba(OH)2 as the catalyst in the presence of dioxane solvent at 343 K (294). As was observed for other basic solid... 

Ethoxylated Dodecanol Ethoxylated Dodecyl Alcohol Ethoxylated Myristyl Alcohol Ethoxylated Nonylphenol Ethoxylated Pentadecanol Ethoxylated Pentadecyl Alcohol Ethoxylated Tetradecanol Ethoxylated Tetradecyl Alcohol Ethoxylated Tridecanol Ethoxylated Tridecyl Alcohol Ethoxytriethylene Glycol Ethoxy Triglycol Ethyl Acetate Ethylacetic Acid Ethyl Acetoacetate Ethyl Acrylate Ethyl Alcohol Ethyl Aldehyde Ethylaluminum Dichloride Ediylaluminum Sesquichloride Ethylamine Ethylbenzene Ethyl Butanoate Ethyl Butanol 2-Ethyl-1 -Butanol 2-Ethylbutyl Alcohol Ethyl Butyrate... 

Acetylated derivatives of Baylis-Hillman adducts derived from ethyl acrylate and aromatic and heteroaromatic aldehydes are synthetically accessible three-carbon fragments that readily react with phenylenediamine under the influence of base to provide l,4-benzodiazepin-2-ones in good overall yield, as depicted in Scheme 71 <2006S4205>. 

Arenediazonium o-benzenesulfonamide 89 was found to be a new and efficient reagent for the Heck-type arylation reactions of some common substrates containing C-C multiple bonds, i.e., ethyl acrylate, acrylic acid, acroleine, styrene, and cyclopentene <2006T3146>. The reactions are carried out in the presence of Pd(OAc)2 and afford arylated products, for example ethyl cinnamates, cinnamic acids, cinnamic aldehydes, and stilbenes, possessing an ( -configuration, and 1-arylcyclopentenes, in good to excellent yields (Equation 27). 

For example, coupling of complexed aldehyde 31 with ethyl acrylate gave lactone 32 with complete diastereocontrol.52 Furthermore, Lewis acid-mediated epimerisation of lactone 32 allowed for the isolation of the alternative diastereoisomer 33. Subsequent decomplexation with iodine liberated the two enantiomerically pure lactones.52... 

The 1-phenyl 3-carboxaldehyde (148, R = H, R = Ph) underwent reaction at 20° with diethyl malonate in ether, to which one drop of piperidine was added, to give the methylenemalonate (151) (90%). Alkaline hydrolysis gave the diacid (153) (70%), which was de-carboxylated in refluxing hydrochloric acid to the jS-acrylic acid (154) (83 %). A Wittig reaction of the aldehyde (148, R = H, R = Ph) with triethyl phosphonoacetate and sodium ethoxide in DMF at 10° gave the ethyl acrylate (152, 46%), which was hydrolyzed also to the acid (154) (78%).i 9... 

Addition of carbon monoxide and hydrogen to an alkene linkage in the presence of cobalt catalysts gives aldehydes in an average yield of 50%. The reactions may be carried out in the usual hydrogenation apparatus. The poisonous properties of carbon monoxide and cobalt carbonyls call for considerable care. Compounds made by hydroformylation include cyclopentanealdehyde from cyclopentene (65%), /3-carbethoxy-propionaldehyde from ethyl acrylate (74%), and ethyl /3-formylbutyrate from ethyl crotonate (71%). 

Feringa et al. developed aqueous Michael reactions catalyzed by Yb(OTf)3 (Eq. 1) [4]. fi-keto esters and a-nitro esters could be used as Michael donors for the reaction. a,y3-Unsaturated ketones and a,/5-unsaturated aldehydes without /S-substituents were good Michael acceptors for the reaction but the reaction did not proceed with ethyl acrylate or acrylonitrile. The reported yields were excellent, though the reaction required prolonged reaction time (3-5 days). 

Carbon tetrachloride undergoes stepwise reduction at mercury in DMF containing TEABr [45]. Several groups of workers [46-52] have electrogenerated the shortlived trichloromethyl anion, which can react with acrylonitrile, ethyl acrylate, diethyl fumarate, alkyl monohalides, and a variety of aldehydes and ketones. De Angelis and coworkers [53] have used dichlorocarbene, generated via reduction of carbon tetra-... 

To a stirred solution of the aldehyde (1.0 g, 2.92 mmol) in THF (6 mL) were added DABCO (0.15 g, 1.32 mmol) and ethyl acrylate (0.8 mL, 7.28 mmol). The reaction mixture was stirred at room temperature for 24 h. The solvent was removed to give a residue which was purihed by chromatography (silica gel) eluting with hexane EtOAc (8.5 1.5) to afford 1.62 g (97%) of the ethyl acrylate as a syrup. 

Barium hydroxide [33, 34] is a strong base which has been employed not only in organic synthesis but also for other purposes. The commercially available octahydrate, l a(OI 1)2 8 11,/) is often used after transformation to the anhydrous form at 200-500 °C. Dehydrated Ba(OH)2 activated at 200°C is denoted C-200. It is known to be a heterogeneous basic catalyst in the Horner-Wadsworth-Emmons (HWE) reaction of triethyl phosphonoacetate (69) with aldehydes 70 to give the 3-substituted ethyl acrylates 71 (Scheme 5.13) [35]. The HWE reaction proceeds at 70 °C in 1,4-dioxane with a small amount of water. The yields of products 71 are usually better than those provided by typical basic catalysts such as NaOH or... 

Bakuzis has explored the use of an interesting (B-acrylate anion equivalent in his synthesis of 9 (Scheme 4.5) ° The Grignard reagent from 3-bromopropyl phenyl sulfide was condensed with acetaldehyde and the resulting alkoxide was acylated to procure 24 (70%). Oxidation of the sulfide to aldehyde 25 proceeded in 74% yield. Reaction of 25 with ethyl 3-nitropropionate followed by elimination of HNO2 from the intermediate afforded 26. The latter step, equivalent to the addition of the p-carbanion of ethyl acrylate, occurred in 38% yield. Oxidation of alcohol 26, protection of the resulting ketone, and saponification gave 17. This intermediate was then dimerized as previously described to a mixture of 9 and its meso diastereomer. 

Condensation products of aromatic aldehydes and 4-thiohydantoins react with Grignard reagents to give the colorless products 112. Compounds 113 and 114 are formed by alkylation and diazomethane addition reactions.285 These condensation products also react as dienes with acrylonitrile, ethyl acrylate, and other dienophiles giving adducts 115.286... 

The reductive coupling of ketones or aldehydes with electrophilic alkenes such as conjugated esters (Scheme 52) has been described independently by Inanaga et al. [38] and Fukuzawa et al. [123,124]. The reaction was performed in THF either in the presence of HMPA [38] or an alcohol [123,124]. The mechanistic aspects of this reaction have been discussed [ 124]. Presumably, the ketyl radical or its protonated form adds to ethyl acrylate with formation of the C-C bond. An efficient enantioselective synthesis of v-butyrolactones has been derived by using AT-methylephedrinyl acrylate or crotonate [125]. One example (synthesis of 33) is indicated in Scheme 52. 

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