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The cationic polymerization of phenyl vinyl ether (PhVE) was investigated to elucidate the reason it is much more difficult to obtain high-molecular-weight polymers of PhVE than with alkyl vinyl et...

β-Aminohydroxamic acids 6a-d are prepared in 4 steps and 30-45% overall yield from nitrones la-d by 1,3-dipolar cycloaddition with phenyl vinyl ether, N-benzylation, thermal rearrangement, and nucleophilic substitution ofthe formed phenyl ester with hydroxylamine.

1-(α-Alkoxyalkyl)benzotriazoles 1a−d add to phenyl vinyl ether to form key intermediates 4a−d, which readily undergo lithiation and subsequent trapping by a variety of electrophiles to give the expected substituted derivatives 7a−d, 9a−c, 11, 13, 15, and 18 in high yields. Subsequent hydrolysis of these compounds provides a novel high-yield acyl anion synthon approach for the synthesis of β-alkoxy ketones 8 or α‘-functionalized β-alkoxy ketones 10, 12, 14, 16, and 19 by short procedures from readily available starting materials.

Synthesis and Cation-Binding Property of Copolymers with Benzo-19-crown-6 Units via Cationic Cyclocopolymerizations of 1,2-Bis[2-(2-vinyloxyethoxy)ethoxy]-benzene with Phenyl Vinyl Ether, 4-Methoxystyrene, and 9-Vinylcarbazole

1-(α-Alkoxyalkyl)benzotriazoles 1a−d add to phenyl vinyl ether to form key intermediates 4a−d, which readily undergo lithiation and subsequent trapping by a variety of electrophiles to give the expected substituted derivatives 7a−d, 9a−c, 11, 13, 15, and 18 in high yields. Subsequent hydrolysis of these compounds provides a novel high-yield acyl anion synthon approach for the synthesis of β-alkoxy ketones 8 or α‘-functionalized β-alkoxy ketones 10, 12, 14, 16, and 19 by short procedures from readily available starting materials.

1. The trifluoroacetyl and trichloroacetyl isocyanates react with allyl vinyl and vinyl phenyl ethers to give linear adducts of general formula R1CONHCOCH=CHOR2. Benzoyl isocyanate reacts in a similar manner with allyl vinyl ether. 2. The trifluoroacetyl and trichloroacetyl isocyanates react with p-tolyl vinyl sulfide and p-bromophenyl vinyl sulfide, while benzoyl isocyanate reacts with phenyl vinyl ether, to give the corresponding substituted dihydro -1,3 -oxazin-4-ones. 3. An NMR study of the reactions of the geometric isomers of butenyl ethyl ether with trichloroacetyl isocyanate confirmed that fact that the formation of the linear isomers proceeds via intermediate 4- and 6-membered cyclic compounds.

The photocycloaddition reaction of 6-substituted phenanthridines and electron-rich olefins, such as trans-anethole and phenyl vinyl ether, is described. This reaction proceeds from the 1(π,π*) states of 6-substituted phenanthridines via the exciplex to give azocine and/or azetidine derivatives in ethanol.

2,2,2-Trimethoxy-3,3-bis(trifluormethyl)-Δ4-1,4,2λ5-oxazaphospholine 1 liefern bei der Thermolyse in Gegenwart von Phenylvinylather uber eine Nitril-ylid-Zwischenstufe zwei [3 + 2]-Cycloaddukte – 3-Phenoxy- und 4-Phenoxy-5,5-bis(trifluormethyl)-1-pyrroline (3,4). Bei Butylvinylathern als Abfangreagenzien entstehen nur noch die 4-Butoxy-5,5-bis(trifluormethyl)-1-pyrroline 4, daneben konnen 6-Butoxy-4,4-bis(trifluormethyl)-5,6-dihydro-4H-1,3-oxazine 6 isoliert werden; dies entspricht einer Konkurrenz von [3 + 2]- und [4 + 1]-Cycloreversion beim Zerfall von 1. In Anwesenheit von 1-Diathylamino-1-propin erfahrt 1 – von R = tert-Butyl abgesehen – schlieslich nur noch die [4 + 1]-Cycloeliminierung von Trimethylphosphit, die dabei freigesetzten Acylimine 5 nehmen das Inamin unter Bildung von 6 Diathylamino-5-methyl-4,4-bis(trifluormethyl)-4H-1,3-oxazinen 7 auf. On the Thermolysis of 3,3-Bis(trifluoromethyl)-Δ4-1,4,2λ5-oxazaphospholines in the Presence of Enol Ethers and 1-Diethylamino-1-propyne 2,2,2-Trimethoxy-3,3-bis(trifluoromethyl)-Δ4-1,4,2λ5-oxazaphospholines 1 on thermolysis in the presence of phenyl vinyl ether yield 3-phenoxy- and 4-phenoxy-5,5-bis(trifluoromethyl)-1-pyrrolines (3,4) via a nitrile ylide intermediate. With butyl vinyl ethers as trapping reagents only 4-butoxy-5,5-bis(trifluoromethyl)-1-pyrrolines 4 were formed, 6-butoxy-4,4-bis(trifluoromethyl)-5,6-dihydro-4H-1,3-oxazines 6 can be isolated as by-products; this corresponds to the competition of a [3 + 2]- and [4 + 1]-cycloreversion during the fragmentation of 1. In the presence of 1-diethylamino-1-propyne 1 undergoes – except in the case of R = tert-butyl – only the [4 + 1]-cycloelimination of trimethyl phosphite, the acylimines 5 thus formed add to the ynamine to yield 6-diethylamino-5-methyl-4,4-bis(trifluoromethyl)-4H-1,3-oxazines 7.

The stereoselectivity in the photocyclodimerization of phenyl vinyl ether (D) via electron-transfer depends strongly upon the concentration of D and the reaction temperature.

1. Under the conditions studied, in the reaction of cyclohexyl, phenyl, and butyl vinyl ethers and also of ethyl vinyl suifide with isoprene the process goes both by the diene-synthesis scheme, and also by the copolymerization of the vinyl ethers with isoprene. 2. The adducts, which are new methylcyclohexene derivatives, were prepared and characterized, New copolymers of vinyl ethers with isoprene containing up to 70 moles per cent of the vinyl ether were isolated, and also a copolymer of ethyl vinyl suifide-with isoprene containing 16 moles per cent of ethyl vinyl suifide was isolated. 3. Diene condensation with isoprene occurs most readily in the case of phenyl vinyl ether, and copolymerization with isoprene occurs most readily in the case of cyclohexyl vinyl ether.

The infrared spectra of methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, benzyl and phenyl vinyl ether and also ethyl vinyl thioether were investigated over the region of 4000-650 cm−1. The assignment of the spectrum of methyl vinyl ether has been made by the aid of the bands contours. The absorption bands of the other were discussed and the characteristic frequencies of vinyl ethers are concluded as follows. (1) three bands near 3100 cm−1…… CH stretching of vinyl group (2) 1615±5 cm−1…… C = C stretching (3) 1321±2 cm−1…… CH in-plane deformation (4) 1203±2 cm−1…… C-O stretching (5) 965±5 cm−1…… = CH- out-of-plane deformation (6) 815±5 cm−1…… = CH2 out-of-plane deformation

The molecular structure of the sole photocycloaddition product of α-naphthonitrile with phenyl vinyl ether, C19H15ON was determined by means of X-ray diffraction. The crystals are monoclinic, space group P21/c, unit-cell dimensions are a=11.563(2), b=9.826(1), c=14.324(2) A, β=113.46(1)°, Z=4. The structure was solved by the direct method, the final R value being 0,042 for 2022 non-zero reflections. The molecule has an endo-configuration, and the cyclobutane ring is puckered.

Styrene, α-ethylstyrene and phenyl vinyl ether are hydroformylated asymmetrically in the presence of chlorocarbonylbis(diphenylneomenthylphosphine)rhodium (I) as catalyst.

Irradiation of an acetonitrile solution of phenyl vinyl ether in the presence of various metal complexes[Fe(III) and Mn(II) complexes] gave two cyclodimers. Similar irradiation of 1,1-dimethylindene and 1,1-diphenylethylene afforded the corresponding cyclodimers. In these photodimerization, the metal complexes with ligands such as 2,2′-bipyridine and 1,10-phenanthroline served as catalysts for electron-transfer reaction.

Styrene, α-ethylstyrene and phenyl vinyl ether are hydroformylated asymmetrically in the presence of chlorocarbonylbis(diphenylneomenthylphosphine)rhodium (I) as catalyst.

The photocycloaddition reaction of 6-substituted phenanthridines and electron-rich olefins, such as trans-anethole and phenyl vinyl ether, is described. This reaction proceeds from the 1(π,π*) states of 6-substituted phenanthridines via the exciplex to give azocine and/or azetidine derivatives in ethanol.

The stereoselectivity in the photocyclodimerization of phenyl vinyl ether (D) via electron-transfer depends strongly upon the concentration of D and the reaction temperature.

Influence de la modification de la surface, de la purete et de sa structure de CdS sur la reactivite du semiconducteur

Irradiation of an acetonitrile solution of phenyl vinyl ether in the presence of various metal complexes[Fe(III) and Mn(II) complexes] gave two cyclodimers. Similar irradiation of 1,1-dimethylindene and 1,1-diphenylethylene afforded the corresponding cyclodimers. In these photodimerization, the metal complexes with ligands such as 2,2′-bipyridine and 1,10-phenanthroline served as catalysts for electron-transfer reaction.

The photoreactions of α-naphthonitrile with indene and phenyl vinyl ether afford 1-cyano-4,5;10,11-dibenzotricyclo[5.4.0.02,6]undeca-4,8,10-triene (I) and 1-cyano-8-phenoxy-2,3-benzobicyclo[4.2.0]octa-2,4-diene (IIa) as a single (2 + 2) cycloadduct respectively, which are shown to have an endo-configuration by the consideration of their NMR data.

Poly(ethylene terephthalate) functions as an efficient electron transfer photosensitizer in the cyclodimerization of phenyl vinyl ether.

Irradiation of phenyl vinyl ether in the presence of aromatic compounds, such as dimethyl terephthalate, methyl benzoate, or benzonitrile, gives a mixture of trans- and cis-head-to-head cyclodimers of the olefin.