Methyl trans-3- acrylates

Davis and coworkers199 found another convenient way to generate arenesulphenic acids by the thermolysis of IV-alkylidenearenesulphinamides 145. On heating 145 for 24 h at 80-115° in methyl propiolate or ethyl acrylate it afforded methyl trans-arenesulphinylacrylates 146 and ethyl arenesulphinylpropionate 147, respectively, in high yields. 

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... 

Methyl cis-3-(3- and 4-substituted benzoyl)acrylates at 1°C Methyl trans-3-(3- and 4-substituted benzoyl)-3-methylacrylates at 1°C 2.56 5 t... 

C8H15N02 3-(dimethylamino)propyl acrylate 18526-07-3 440.15 38.165 1.2 14917 C8H16 2-methyl-trans-3-heptene 692-96-6 385.15 32.917 1,2... 

C9H17N02 2- diethylamino)ethyl acrylate 2426-54-2 381.97 32.670 2 17920 C9H18 1-methyl-trans-2-ethyl cyclohexane 4923-78-8 424.85 36.041 1,2... 

The stereochemistry of the 1,3-dipolar cycloaddition of the heteroaromatic iV-imines has been investigated in some detail by using the reaction of phenanthridine N-benzoylimine with a series of activated olefins such as JV-methylmaleimide, maleic anhydride, diethyl maleate, methyl acrylate, methyl methacrylate, and methyl trans-crotonate (e.g., Eq. 30).202 The adducts from the former three have the all-cis stereochemistry. These results are rationalized in terms of secondary molecular orbital interactions. With acrylates such stereospecificity is lost, suggesting that this effect is of lesser importance in these cases (see Table II). 

A crystal structure determination of (C2H )2Pt02 reveals the expected trigonal planar (in-plane) coordination. In (cod)Nl[methyl-trans-B-(phenylsulfonyl)acrylate], the cod and olefin bonds are mutually perpendicular in a trigonal planar geometry. The... 

The addition of benzonitrile oxide to acrylic acid gave only the 4-carboxylic acid (441) (59MI41601), while addition to cis- and trans-cinnamic esters gave cis and trans diastereomeric pairs of 4-carboxylic acids (442) (Scheme 100) (59MI41600). Arbisono repeated the experiment and, when methyl c/s-cinnamate was used, in addition to the 4-carboxylic acid some 5-carboxylic acid (442) was isolated (66MI41600). The reaction of vinyl bromides with benzonitrile oxide yielded only an isoxazole and not a bromoisoxazoline (Scheme 101) (78JCR(S)192). 

Methyl acrylate [96-33-3 M 86,1, b 80 , d 0.9535, n 1.4040. Washed repeatedly with aqueous NaOH until free from inhibitors (such as hydroquinone), then washed with distd water, dried (CaCl2) and fractionally distd under reduced pressure in an all-glass apparatus. Sealed under nitrogen and stored at 0° in the dark. [Bamford and Han J Chem Soc, Faraday Trans 1 78 855 1982.]... 

Treatment of A -benzyltnfluoroacetimidoyl chloride with triethylamine in toluene at room temperature leads to in situ generation of trifluoroacetonitrile ben-zylide [4J] (equation 43), which reacts with methyl acrylate to form cycloadducts [43] (equation 44) Although the kinetic ratio of products favors the cis adduct (3 1), thermodynamic equilibration leads to an excess of the trans isomer (7 1). 

Four fluorinated acrylates are presented in Table 4 [66, 67, 68, 69] to supplement the vmyl fluoride data Perfluoroacrylic acid [70] and methyl per-fluoroaciylate [69, 70] are both reported m the literature. The cts and trans isomers of fluoroethylenes are readily distinguished by the magnitude of their couphng constants, with trans typically more than 3 times the magnitude of cis... 

The ratio of the two diastereomeric products 190 and 191 was found to depend on the reaction temperature and reaction time. The addition of acrolein or methyl vinyl ketone proceeded smoothly, but in the case of methylacrylate or acrylonitrile the reaction did not proceed under the same conditions (EtsN THF 30°C). An accompanying AMI calculation of these Q ,/3-unsaturated compounds [LUMOs for acrolein, -0.13877 for methyl vinyl ketone, -0.06805 (s-trans) for methyl acrylate, -0.01413 (s-tmns) for acrylonitrile, 0.04971] suggested the low reactivity of methyl acrylate and acrylonitrile toward the Michael reaction (99H1321). 

The transformation of the porphyrin intermediate 4 into a chlorin can be achieved after introduction of a C — C double bond into the 15-propanoate side chain of 4 to yield 5. The cyclization of 5 with participation of the 15-acrylic ester side chain under acidic conditions gives the chlorin 6 which is then transformed in a multistep reaction sequence into chlorophyll a. The driving force of chlorin formation from the porphyrin is believed to be the relief of steric strain at the sterically overcrowded porphyrin periphery which gives the desired trans arrangement of the propanoate side chain and the methyl group in the reduced ring. The total... 

As was noted previously, Hine and Bailey (16, 17) have obtained correlation of rate data for the reaction of tra s-3-substituted acrylic acids and diphenyl-diazomethane with the Hammett equation. Bowden has reported correlation of rate data for the reaction of tra s-3-substituted acrylic acids with diphenyl-diazomethane (59) and the alkaline hydrolysis of trans-3-substituted methyl acrylates (69) with the Hammett equation. Sufficient data are available for nine sets of rate studies. The sets studied are reported in Table VIII. The results of the correlations are given in Table IX. Of the nine sets studied, seven gave... 

A similar study was done with methyl acrylate as the dienophile.28 The uncatalyzed and catalyzed TSs are shown in Figure 6.7. As with propenal, the catalyzed reaction is quite asynchronous with C(2)-C(3) bonding running ahead of C(l)-C(6) bonding. In this system, there is a shift from favoring the exo-s-cis TS in the thermal reaction to the endo-s-trans TS in the catalyzed reaction. A large component in this difference is the relative stability of the free and complexed dienophile. The free dienophile favors the s-cis conformation, whereas the BF3 complex favors the s-trans conformation. 

The complex OsH(OH)(CO)(P Pr3)2 also reacts with methyl acrylate, methyl vinyl ketone, and allyl alcohol.91 Reaction with methyl acrylate leads to OsH(OH) (COXrf-CH2=CHC02MeXP Pr3)2 containing the olefin trans to the hydride ligand. In solution, this complex releases the olefin to generate the starting complex. The thermodynamic magnitudes involved in the equilibrium have been determined in toluene-t/a by 31P 1H NMR spectroscopy. The values reported are AH° = 17.0 0.5 kcal-mor1 and AS° = 54.0 1.2 cal-K 1-mol 1. In the presence of the methyl vinyl ketone complex OsH(OH)(CO)(P Pr3)2 affords 0sH CHCHC(0) Me (CO)(P Pr3)2 and water, whereas in the presence of allyl alcohol the loss of... 

Similarly, methyl methacrylate reacts with ketones and TMSH/RuCE-SlEO to give /l-trimethylsiloxy-2,2-dimethyl methyl esters in good yields. A lactone example is shown in Eq. 292.473 Methyl acrylate, trans methyl ( )-cinnamate, and 3,4-dehydro-S-lactone react in an analogous manner, albeit in lower yields.473... 

Acrylonitrile or methyl acrylate readily inserts into allylnickel bonds (example 34, Table HI). A trans double bond is formed by loss of a proton. Insertion of acetylene followed by oxidative elimination with allyl halides gives cis double bonds (example 32, Table III). Insertion of methyl propiolate, followed by proton uptake, leads to a trans double bond (example 33, Table III). Norbomene has been shown to insert stereoselectively cis.exo into an allylnickel bond (example 35, Table III). 

Relatively polar diphosphine 8 has an elongated P-P bond, and thus exhibits unusual reactivity. The reaction of 8 with acrylonitrile or methyl acrylate proceeds at 50 °C in a chemo- and regioselective manner to afford the 1,2-addition product with the PPh2 group attached at the terminal position (Equation (64)).165 Tetrachlorodiphosphine reacts with cyclohexene to give trans-adduct presumably via an ionic pathway.166... 

Photochemical hydrogen abstraction reaction for the silylimine 161 give an o-quinodimethane intermediate 162 which could be trapped with dimethyl fumarate, dimethyl maleate, trans-methyl cinnamate, methyl acrylate, acrylonitrile (equation 94)... 

DIHYDROFURAN DIVINYL ETHER METHACROLEIN 2-BUTYNE-1,4-DIOL ganna-BUTYROLACTONE cis-CROTONIC ACID trans-CROTONIC ACID METHACRYLIC ACID METHYL ACRYLATE VINYL ACETATE ACETIC ANHYDRIDE SUCCINIC ACID DIGLYCOLIC ACID MALIC ACID TARTARIC ACID n-BUTYRONITRILE ISOBUTYRONITRILE ACETONE CYANOHYDRIN... 

Preliminary results from a study of catalytic activation of the heterocoupling between arylhalides and alkenes using pony-tail-functionalized dendrimer-encapsulated Pd nanoparticles have shown promise. For example, the classic Pd-catalyzed Heck coupling between arylhalides and methacrylate yields predominately (> 97%) the trans-cinnimaldehyde product [176]. On the other hand, the C02-soluble dendrimer nanocomposite exclusively catalyzes the production of the highly unfavored 2-phenyl-acrylic acid methyl ester isomer at 5000 psi and 75 °C (Fig. 27] [177]. 

Amresco acryl-40, see Acrylamide AMS, see a-Methylstyrene n-Amyl acetate, see Amyl acetate Amyl acetic ester, see Amyl acetate Amyl acetic ether, see Amyl acetate Amylene, see 1-Pentene a-n-Amylene, see 1-Pentene p-n-Amylene, see cis-2-Pentene cis-p-Amylene, see cis-2-Pentene frans-p-Amylene, see trans-2-Venlene sec-Amyl ethanoate, see Amyl acetate Amyl ethyl ketone, see 5-Methyl-3-heptanone Amyl hydride, see Pentane Amyl methyl ketone, see 2-Heptanone n-Amyl methyl ketone, see 2-Heptanone AN, see Acrylonitrile Anaesthetic ether, see Ethyl ether Anamenth, see Trichloroethylene Anduron, see Diuron Anesthenyl, see Methylal Anesthesia ether, see Ethyl ether Anesthetic ether, see Ethyl ether Anhydrous ammonia, see Ammonia Aniline oil, see Aniline Anilinobenzene, see 4-Aminobiphenyl Anilinomethane, see Methylaniline 2-Anidine, see o-Anisidine 4-Anisidine, see p-Anisidine 2-Anisylamine, see o-Anisidine... 

The same type of addition—as shown by X-ray analysis—occurs in the cationic polymerization of alkenyl ethers R—CH=CH—OR and of 8-chlorovinyl ethers (395). However, NMR analysis showed the presence of some configurational disorder (396). The stereochemistry of acrylate polymerization, determined by the use of deuterated monomers, was found to be strongly dependent on the reaction environment and, in particular, on the solvation of the growing-chain-catalyst system at both the a and jS carbon atoms (390, 397-399). Non-solvated contact ion pairs such as those existing in the presence of lithium catalysts in toluene at low temperature, are responsible for the formation of threo isotactic sequences from cis monomers and, therefore, involve a trans addition in contrast, solvent separated ion pairs (fluorenyllithium in THF) give rise to a predominantly syndiotactic polymer. Finally, in mixed ether-hydrocarbon solvents where there are probably peripherally solvated ion pairs, a predominantly isotactic polymer with nonconstant stereochemistry in the jS position is obtained. It seems evident fiom this complexity of situations that the micro-tacticity of anionic poly(methyl methacrylate) cannot be interpreted by a simple Bernoulli distribution, as has already been discussed in Sect. III-A. 

Theoretical calculations (6-31G ) have been used to compare the energies of four possible transition states for Diels-Alder reaction of the BF3 complex of methyl acrylate with 1,3-butadiene. The results are summarized in Fig. 6.4. The endo transition state with the s-trans conformation of the dienophile is preferred to the others by about 2kcal/mol.14... 

---