Phenyl isocyanate, with ethyl

Phenyl isocyanate, with ethyl hydrazinecarboxylate to give 4-phenyl-1-carbethoxy-semicarbazide, 51, 122 Phenylmagnesium bromide, o-... 

Phenyl isocyanate, with ethyl hydrazine-carboxylate to give 4-phenyl-l-car-bethoxysemicarbazide,51,122 Phenylmercuric acetate, with methallyl alcohol to yield 2-methyl-3-phenyl-propionaldehyde, 51, 17 1-PHENYL-1,3-PENTADIYNE, 50, 97 1-PHENYL-1,4-PENTADIYNE. 50, 97 a-Phenylpentanal, from 2-benzyl-4,4,6-trimethyl-5,6-dihydro-l,3(4H)-... 

Phenyl isocyanate, with ethyl hydrazinecarboxylate to give 4-phenyl-... 

These herbicides contain nitrogen and respond to both FID and AFID. However, the analysis of these compounds is complicated by their thermal instability. For example, the total ion current trace obtained from the GC-MS ofamethanolic solution of monolinuron shows four peaks (Fig. 9). The formation of these peaks is illustrated in Fig. 10. This thermal decomposition appears to be general for the substituted ureas and reaction of substituted phenyl isocyanates with higher alcohols also occurs. As certain substituted alkyl phenylcarbamates are used as pesticides in their own right, inert solvents such as ethyl acetate or hexane should always be used for injection. The mass spectra of the thermal... 

A somewhat different mechanism was deduced by Baker and Bailey 4f) from their own studies of the systems phenyl isocyanate and ethyl p-aminobenzoate (benzocaine) cyclohexyl isocyanate and aniline phenyl isocyanate and aniline p-methoxyphenyl isocyanate and aniline. While Craven postulates one complex. Baker and Bailey assume two complexes of the isocyanate one with the amine, and one with the product urea. 

The rate of the triethylamine-catalyzed reaction of phenyl isocyanate with n-butanethiol depends on the solvent used and increases in the order benzene, toluene, dibutyl ether, dioxane, methyl ethyl ketone, and nitrobenzene. This solvent effect increased with the ionizing power of the solvent and was the reverse of that observed in the reaction of isocyanates with alcohol. 

The Reaction of Phenyl Isocyanate and Ethyl Isocyanate with Thiols (both Reactants at 0.1250 M) in Toluene Solution at S0° in the Presence of 0.05 M EtsN... 

Among these structures, the probability that the spectrum belongs to 6-hydroxyhexyl carbonate is higher, since the same compound is formed in the pyrolysis of poly[(1,6-hexyI-1,2-ethyl carbonate)diol 4,4 -methylenebis(phenyl isocyanate)]-co-[1,4-butandiol 4,4 -methylenebis(phenyl isocyanate)], with the pyrogram shown in Figure 11.1.6. 

Desmoras el al. (1963) described the herbicidal properties of the D-isomer of N-ethyl 2-(phenylcarbamoyloxy)propionamide, prepared by the condensation of phenyl isocyanate with N-ethyl lactamide (carbetamide, 9). 

Diphosphanylketenimines 102 are excellent 1,3-dipoles, which readily undergo regiospe-cific [3+2] cycloaddition reactions with suitable dipolarophiles, such as acetylenes, phenyl isocyanate and ethyl isothiocyanate. For example, reaction of 102 with two equivalents of acetylene derivatives form the cycloadducts 103. ... 

Analogously to ynamines and o, /3-acetylenic ketones, 4-aminobut-3-yn-2-ones react with 1,3-dipoles (68HCA443 73HCA2427 92KGS867). The reaction of 4-dimethylaminobut-3-yn-2-one with diphenylketene follows a route of [2-1-21-cycloaddition (30°C, THF, 1 h) to give 2-acetyl-3-dimethylamino-4,4-diphenyl-cyclobut-2-en-l-one (377) in 15% yield. With ethyl azidoformate (30°C, THF, 3 h), the tiiazole 378 is formed in 82% yield, whereas with phenyl isocyanate, the quinoline 379 is the product (by a [2- -4] scheme) in 70% yield (68HCA443). 

Materials and Purification. Chemicals were purchased from Aldrich chemical company and used as received unless otherwise noted 1,1,1,3,3,3-hexamethyl disilazane, ethylene glycol, triphosgene, poly(ethylene oxide) (MW = 600), poly(tetramethylene oxide) (MW = 1000), poly(caprolactonediol) (MW = 530), toluene diisocyanate (TDI), anhydrous ethanol (Barker Analyzed), L-lysine monohydride (Sigma) and methylene bis-4-phenyl isocyanate (MDI) (Kodak). Ethyl ether (Barker Analyzer), triethylamine and dimethyl acetamide were respectively dried with sodium, calcium hydride and barium oxide overnight, and then distilled. Thionyl chloride and diethylphosphite were distilled before use. 

IODONIUM CHLORIDE 1-PHENYL-2, 4-PENTANEDIONE, 51, 128 4-Phenyl-l-carbethoxysemicar-bazide, from ethyl hydra-zinecarboxylate and phenyl isocyanate, 51, 122 with potassium hydroxide to give 4-phenylurazole, 51,... 

The next study of wood modification was that reported by Baird (1969), who performed vapour-phase reactions of spruce with ethyl, n-butyl, /-butyl, allyl and phenyl isocyanate (PhNCO). Unfortunately, DMF was used as a catalyst for the reactions, which resulted in polymerization of PhNCO in the cell wall of the wood, leading to unpredictable results. No evidence was presented in support of the contention that polymerization had occurred, and since this requires an anionic catalyst initiator, this is considered unlikely. However, the presence of side reactions when DMF is used in conjunction with isocyanates has already been mentioned. Greater success was reported when butyl isocyanate was reacted with wood (presumably a consequence of the lower reactivity of this isocyanate... 

The synthesis of 4//-pyrano[2,3-d]pyrimidines, a class of compounds important in crop protection, is presented in Scheme 91. Dichlorotriphenyl-phosphorane affords iminophosphorane 247 with ethyl 2-amino-4//-pyran-3-carboxylate (246). Phenyl isocyanate cyclizes under alkoxide migration to afford pyrano[2,3-d]pyrimidines (248) (90LA995). 

B. 4-Phenyl-l-carbethoxysemicarbazide. In a 1-1. three-necked round-bottomed flask equipped with a liquid-sealed mechanical stirrer (Note 3), a constant-pressure dropping funnel, and a reflux condenser fitted with a drying tube containing silica gel is placed a solution of 52 g. (0.5 mole) of ethyl hydrazine-carboxylate in 550 ml. of dry benzene (Note 4). The solution is cooled in an ice bath, and the stirrer is started. To the solution is added 59.7 g. (55 ml., 0.5 mole) of phenyl isocyanate (Note 5) dropwise over a period of 45 minutes. After about one-half of the isocyanate has been added, a white precipitate of the product appears, and the reaction mixture becomes progressively thicker. After addition is complete the ice bath is removed, and the mixture is stirred at room temperature for 2 hours and then is heated under reflux for 2 hours. The suspension is allowed to cool to room temperature, and 4-phenyl-1-carbethoxysemi-carbazide is isolated by suction filtration, washed with 500 ml. of benzene, and dried in a vacuum desiccator. The yield is 108 g. (97%), m.p. 151-152°. The product is not further purified before being used in the next step. It may be recrystallized from ethyl acetate to yield white crystals, m.p. 154-155°, vmax 1645, 1687, 1797, and 3300 cm.-1 (Note 6). 

Phenyl-l-carbethoxysemicarbazide, from ethyl hydrazinecarboxylate and phenyl isocyanate, 51,122 with potassium hydroxide to give... 

Isoxazoline derivatives of Cgo such as 250 (Scheme 4.40) are accessible by 1,3-dipolar cycloadditions of nitrile oxides to [6,6] double bonds of the fullerene [2, 278, 291-305]. The nitrile oxides 249 with R = methyl, ethyl, ethoxycarbonyl and anthryl are generated in situ from the corresponding nitroalkane, phenyl isocyanate and triethylamine. The isoxazoline derivative of Cgo 250 (with R = anthryl) crystallizes in black prisms out of a solvent mixture of CS2 and acetone (3 2) [292]. X-ray crystal structure analysis shows that addition of the nitrile oxide occurs on a [6,6] double bond of the fullerene framework. 

Besides removal of alkyl-based groups located at the N-2 of a pyridazin-3(27/)-one also real reactions in the side chain appeared. Pyridazinium ylides, obtained via deprotonation of iV-alkylpyridazinium salts, have been reacted with phenyl isocyanates and benzenediazonium salts <2002MI287, 1997T4411>. As discussed in Section 8.01.5.7.2 1,3-dipolar cycloaddition with ethyl acrylate and ethyl propiolate were also studied. 

Nitroalkanes are easily functionalized with a variety of acylating agents such as phenyl isocyanate, acetic anhydride, and ethyl chloroformate in the presence of a... 

To a flask containing 20 gm (0.08 mole) of methylenebis(4-phenyl isocyanate) in 150 ml of xylene is added 0.03 gm of l-ethyl-3-methyl-3-phospholine-l-oxide catalyst. The solution is refluxed for 4 hr, during which time carbon dioxide is being evolved. The xylene solvent is removed under reduced pressure to afford a nearly quantitative yield of the solid polycarbodiimide. The latter polymer was pressed at 250°C to afford a clear, crystalline, orientable film with a tenacity of about 50,000 psi, an initial modulus of 410,000 psi, and a 20 % elongation at 25°C. 

The relative reaction rates of several amines with phenyl isocyanate in ether at 0°C have been determined. Aniline is about half as reactive as ethyl-, n-propyl-, n-butylamine, and n-amylamine is between eight and ten times as reactive as ammonia [28]. 

Reaction of thienyllithium with C02 leads to thiophenecarboxylic acid. Other electrophiles which provide derivatives of carboxylic acids include ethyl chloroformate and phenyl isocyanate (Scheme 176) <790R(26)1>. 

When acrylonitrile or ethyl acrylate was used as the dipolarophile, the azomethine adducts (134) and (135) were formed no thiocarbonyl ylide addition products were isolable in refluxing toluene or xylene, although the isoindoles (136a) and (136b) derived from them were isolated. In contrast to the reactions with fumaronitrile or AT-phenylmaleimide, the azomethine adducts (134) and (135) were still present at higher reaction temperatures — almost 50% in toluene and 4-5% in xylene. Under the same reaction conditions other electron-deficient dipolarophiles like dimethyl fumarate, norbornene, dimethyl maleate, phenyl isocyanate, phenyl isothiocyanate, benzoyl isothiocyanate, p-tosyl isocyanate and diphenylcyclopropenone failed to undergo cycloaddition to thienopyrrole (13), presumably due to steric interactions (77HC(30)317). 

The ester group of ethyl 4-hydroxycoumarin-3-carboxylate (335) reacts with aniline to give the amide (336) which was also obtained by the action of phenyl isocyanate on 4-hydroxycoumarin (337) (67CJC767). 

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