Methyl 3,3-dimethyl acrylate

Butyl lithium Diisopropylamine Methyl 3,3-dimethyl acrylate p-Ionylidene acetaldehyde... 

Under an atmosphere of nitrogen, a solution of n-butyl lithium in hexane (321 ml, 15%) was added to a solution of diisopropylamine (48.6 g, 0.48 mole) in tetrahydrofuran (1000 ml) at -30°C and the mixture was stirred for one hour. The reaction mixture was then cooled to -72°C and methyl 3,3-dimethyl acrylate (55 g, 0.48 mole) was added to it. Stirring was continued at -65° to -75°C for 30 min. To the resulting mixture, a solution of p-ionylidene acetaldehyde (100 g, 0.458 mole, 9-trans content 80%) was added and the reaction mixture was stirred at -65° to -75°C for 1 h. The reaction mixture was then warmed to 40°C and stirred at this temperature for 3 h. Solvent was removed under vacuum and the reaction mixture was diluted with water (700 ml) and methanol (300 ml). Activated charcoal (4 g) was then added and the mixture was refluxed for 30 min. The heterogeneous mixture was filtered through hyflo and the hyflo bed was washed with methanol (300 ml) and water (150 ml). The aqueous methanolic layer was then extracted with hexanes (2 x 500 ml) and acidified with 10% sulfuric acid to pH 2.80.5. The desired product was then extracted with dichloromethane (2 x 500 ml). The combined dichloromethane layer was washed with water (2 x 300 ml) and concentrated in vacuo to afford the desired isotretinoin. Crystallization from methanol (200 ml) afforded isotretinoin (44 g) in greater than 99% HPLC purity. 

Cycloaddition of the nitrone 10a with dimethyl citraconate47 and mesaconate,47 methyl / ,/ -dimethyl acrylate,36 and mesityl oxide36 (for all of them Y = H) gives cycloadducts X. Some of the results are summarized in Table I. 

When assessing catalytic results reported for new ligands, one must bear in mind that their quality and relevance differ widely. For most new ligands only experiments with selected model test substrates carried out under standard conditions are available, and very few have already been applied to industrially relevant problems. The test substrates for alkenes used most frequently are Aceta-mido Cinnamic Acid (ACA) or its methyl ester (MAC), Methyl Acetamido Acrylate (MAA), ITaconic Acid or DiMethyl ITaconate (ITA, DMIT) and selected aryl enamides (Fig. 25.3). 

Methyl-2-butenoic (P,P-dimethyl acrylic) acid, physical properties, 5 35t... 

Omeprazole is obtained [15] by the reaction of acetyl ethyl propionate 1 with ammonia to give ethyl -3-amino-2,3-dimethyl acrylate 2. Compound 2 was converted to to 2,4-dihydroxy-3,5,6-trimethyl pyridine 3 by treatment with methyl diethylmalonate. Treatment of compound 3 with phosphorous oxychloride produced 2,4-dichloro-3,5/6-trimethyl pyridine 4. 4-Chloro-3/5,6-trimethyl pyridine 5 was obtained by treatment of compound 4 with hydrogen. On treatment of compound 5 with hydrogen peroxide and acetic acid, 4-chloro-3,5,6-trimethyl-pyridine-N-oxide 6 was produced. Treatment of compound 6 with acetic anhydride gave 4-chloro-2-hydroxymethyl-3,5-dimethyl pyridine 7 which was converted to 2-hydroxymethyl-3,5-dimethyl-4-methoxypyridine 8 by treatment with sodium methoxide. Compound 8 was treated with thionyl chloride to produce 2-chloromethyl-3,5-dimethyl-4-methoxypyridinc 9. Compound 9 interacts with 5-methoxy-2-mercaptobenzimidazole to give 5-methoxy 2-[((4-methoxy-3,5-dimethyl-2-pyridinyl)methyl)thio]-lH-bcnzimidazole 10 which is oxidized to omeprazole 11. 

Two examples of the preparation of an acid by hypochlorite oxidation of a methyl ketone are 2-acetonaphthalene — /3-naphthoie acid" and mesityl oxide - dimethyl-acrylic acid."... 

In a large number of carbene and carbenoid addition reactions to alkenes the thermodynamically less favored syn-isomers are formed 63). The finding that in the above cyclopropanation reaction the anti-isomer is the only product strongly indicates that the intermediates are organonickel species rather than carbenes or carbenoids. Introduction of alkyl groups in the 3-position of the electron-deficient alkene hampers the codimerization and favors isomerization and/or cyclodimerization of the cyclopropenes. Thus, with methyl crotylate and 3,3-diphenylcyclopropene only 16% of the corresponding vinylcyclopropane derivative has been obtained. 2,2-Dimethyl acrylate does not react at all with 3,3-dimethylcyclopropene to afford frons-chrysanthemic add methyl ester. This is in accordance with chemical expectations 69) since in most cases the tendency of alkenes to coordinate to Ni(0) decreases in the order un-, mono-< di- < tri- < tetrasubstituted olefines. 

Similarly, condensation of D-mannosamine, as well as D-mannose with methyl dimethyl[(3-bromopropen-2-yl)phosphate] [115], instead of ethyl (bromomethyl)acrylate, led to the corresponding Neu5Ac and phosphonate analogs with much higher stereoselectivity (syn/anti 20 1). 

Synonyms Benzyl trans-2,3-dimethyl acrylate Benzyl trans-2-methyl-2-butenoate Benzyl 2-methylcrotonate Benzyl trans-2-methyl... 

Synonyms 2-Butenoic acid, 2-methyl-, ethyl ester, (E)- Crotonic acid, 2-methyl-, ethyl ester, (E)- Ethyl trans-2,3-dimethyl acrylate Ethyl 2-methyl-2-butenate Ethyl (E)-2-methyl-2-butenoate... 

CAS 7785-33-3 EINECS/ELINCS 232-078-9 Synonyms 2-Butenoic acid, 2-methyl-, 3,7-dimethyl-2,6-octadienyl ester (E,E)- cis-a,p-Dimethyl acrylic acid, geraniol ester trans-3,7-Dimethyl-2,6-octadien-1-yl cis-a,p-dimethyl acrylate Geranyl trans-2-methyl-2-butenoate Tiglic acid, geraniol ester Empirical C15H24O2... 

The electron-rich ethylenes, 2,2-dimethyldioxole (46) and bis-trimethylsilyloxy-ethylene (47) are useful substitutes for vinylene carbonate in [2+ 2] cycloadditions, particularly with electron-deficient partners such as methyl-2,2-dimethyl acrylate and dimethylmaleic anhydride. Good yields of the adducts (48 and 49) are obtained, and these are easily hydrolysed to the corresponding diols. The products from additions with the acyclic olefin (47) are mixtures of stereoisomers, because of cis-trans-isomehsm of the olefin under the conditions of the cyclization. 

Adipic acid dimethyi adipate (polyesters), acrylamide (acrylonitrile co-polymers), acrylonitrile (acrylamide co-polymers), acrylic acid (acrylic polymers), buta-1,3-dlene (PS co-polymers, elastomers), butan-1,4-diol (polyesters), 2,2-bis(4-hydroxyphenyl)butan-1-ol (polyesters), 1,1-bis(4-hydroxyphenyl)cyclohexane (polyesters), 4,4 -(propane-2,2-diyl)-dlphenol known as bisphenol A (polyesters), ethyleneglycol (polyestere), formaldehyde (phenol-formaldehyde resins), isophthalic acid (PET), caprolactame and C -C,2 aminocar-boxyllc acids and their lactames (polyamides), melamine (amino-formaldehyde resins), methacryllc acid and methyl methacrylate (acrylic polymers), methylstyrene (PS and co-polymers), propyleneglycol (polyesters), sebacic acid and dimethyl sebacate (polyesters), styrene (PS and co-polymers), terephthalic acid and dimethyl terephthalate (PET), vinyl acetate (vinyl acetate co-polymers), vinyl chloride (PVC and co-polymers), vinylldenechlorlde (PVdC and co-polymers)... 

The initial stage of tetramethylene-a, -dimethyl acrylate (MB) monophase solutions polymerization was analyzed in papers [189,199], The characteristic viscosity of tetramethylene-a,o)-dimethyl acrylate q 5 centipoise. Polymerization was carried out in nonreactive oligomers with different viscosity in bis-(di-oxyethylenephthalate)-a,(D-diisobutyrate (IDF), (q 1000 centipoise) in trioxyethylene-a,(D-di-isobutyrate (TGI) (q 10 centipoise) and in full saturated analogue of tetramethylene-a, -dimethyl acrylate, tetramethylene-a,ra- di-isobutyrate (IB), (q 5 centipoise). The obtained results were compared with polymerization kinetics of methyl meta acrylate, dissolved in the same nonreactive oligomers. 

Donor substituents on the vinyl group further enhance reactivity towards electrophilic dienophiles. Equations 8.6 and 8.7 illustrate the use of such functionalized vinylpyrroles in indole synthesis[2,3]. In both of these examples, the use of acetyleneic dienophiles leads to fully aromatic products. Evidently this must occur as the result of oxidation by atmospheric oxygen. With vinylpyrrole 8.6A, adducts were also isolated from dienophiles such as methyl acrylate, dimethyl maleate, dimethyl fumarate, acrolein, acrylonitrile, maleic anhydride, W-methylmaleimide and naphthoquinone. These tetrahydroindole adducts could be aromatized with DDQ, although the overall yields were modest[3]. 

Various alkylating agents are used for the preparation of pyridazinyl alkyl sulfides. Methyl and ethyl iodides, dimethyl and diethyl sulfate, a-halo acids and esters, /3-halo acids and their derivatives, a-halo ketones, benzyl halides and substituted benzyl halides and other alkyl and heteroarylmethyl halides are most commonly used for this purpose. Another method is the addition of pyridazinethiones and pyridazinethiols to unsaturated compounds, such as 2,3(4//)-dihydropyran or 2,3(4//)-dihydrothiopyran, and to compounds with activated double bonds, such as acrylonitrile, acrylates and quinones. 

Jap-KIingermarm reactions, 4, 301 oxidation, 4, 299 reactions, 4, 299 synthesis, 4, 362 tautomerism, 4, 38, 200 Indole, 5-amino-synthesis, 4, 341 Indole, C-amino-oxidation, 4, 299 tautomerism, 4, 298 Indole, 3-(2-aminobutyl)-as antidepressant, 4, 371 Indole, (2-aminoethyl)-synthesis, 4, 278 Indole, 3-(2-aminoethyl)-synthesis, 4, 337 Indole, aminomethyl-reactions, 4, 71 Indole, 4-aminomethyl-synthesis, 4, 150 Indole, (aminovinyl)-synthesis, 4, 286 Indole, 1-aroyl-oxidation, 4, 57 oxidative dimerization catalysis by Pd(II) salts, 4, 252 Indole, 1-aroyloxy-rearrangement, 4, 244 Indole, 2-aryl-nitration, 4, 211 nitrosation, 4, 210 synthesis, 4, 324 Indole, 3-(arylazo)-rearrangement, 4, 301 Indole, 3-(arylthio)-synthesis, 4, 368 Indole, 3-azophenyl-nitration, 4, 49 Indole, 1-benzenesulfonyl-by lithiation, 4, 238 Indole, 1-benzoyl photosensitized reactions with methyl acrylate, 4, 268 Indole, 3-benzoyl-l,2-dimethyl-reactions... 

In the case of enamines derived from aldehydes a cycloaddition to give a cyclobutane occurs (48-50). Thus the enamine (16) reacted with methyl acrylate in acetonitrile to give a 91 % yield of methyl 2-dimethylamino-3,3-dimethylcyclobutane carboxylate (56). Similarly, treatment of (16) with diethylmaleate at 170° gave a 70% yield of diethyl 4-dimethylamino-3,3-dimethyl-l,2-cyclobutanedicarboxylate (57), and 16 and acrylonitrile gave a 65% yield of 2-dimethylamino-3,3-dimethylcyclobutanecarbonitrile (58). 

The addition of ethyl acrylate to 1,2-dimethyl- -piperideine 163), l-methyl-2-ethyl-zJ -piperideine 164), and 1,2-dimethyl- -pyrrolidine 216,217) occurs, yielding both possible enamine structures (138 and 139, n=I,2). 

An interesting addition of ethyl acrylate has been reported in the case of l-methyl-2-ethylidenepyrrolidine. An unsaturated amino ketone 144 is formed, which rearranges to 1,7-dimethyloctahydroindole (145) on reduction with formic acid, as established by dehydrogenation to 1,7-dimethyl-indole (Scheme 12) 217). 

ATBN - amine terminated nitrile rubber X - Flory Huggins interaction parameter CPE - carboxylated polyethylene d - width at half height of the copolymer profile given by Kuhn statistical segment length DMAE - dimethyl amino ethanol r - interfacial tension reduction d - particle size reduction DSC - differential scanning calorimetry EMA - ethylene methyl acrylate copolymer ENR - epoxidized natural rubber EOR - ethylene olefin rubber EPDM - ethylene propylene diene monomer EPM - ethylene propylene monomer rubber EPR - ethylene propylene rubber EPR-g-SA - succinic anhydride grafted ethylene propylene rubber... 

A = Acrylonitrile B = Benzoquinone C = Naphthoquinone D = 5,8-Quinolinequinone E = Methyl vinyl ketone F = Dimethyl acetylene dicarboxylate G = Methyl acrylate ... 

The application of 3-aminopropyl phosphine (3) [41,46] as a building block for incorporation into -COOH functionalized frameworks provides an excellent example of the utility of preformed primary phosphine frameworks (Scheme 8) [46]. The reactions involved Michael addition of ferf-butyl acrylate to malonic acid dimethyl ester to produce the intermediate adduct, 2-methoxycarbonyl-pentanedioc acid 5-ferf-butyl ester 1-methyl ester, which upon treatment with trifluro-acetic acid (TFA) produced the corresponding diester acid,2-methoxy-carbonyl-pentanedioic acid 1-methyl ester, in near quantitative yield. It is remarkable to note that the reaction of NH2(CH2)3PH2 (3) with the diester acid is highly selective as the -COOH group remained unattacked whereas the reaction occurred smoothly and selectively at the -COOMe groups to pro-... 

Pyrrolidines have been prepared by 1,3-dipolar cycloaddition of N-(benzyli-dene)trimethylsilylamine/TMSOf 20 and methyl acrylate, N-methylmaleimide, or dimethyl maleate [35]. More recently, methyl trans-3-cyanociruiamate 1479 was reacted with N-benzyl-N-(trimethylsilylmethyl)aminomethyl methyl ether 1480 and trifluoroacetic acid in CH2CI2 at 0°C and 24°C to afford, via 1481, the pyrrolidine derivative 1482 in high yield and MeOSiMe3 13a [35a] (Scheme 9.20). Several... 

---