Trichloroacetyl Isocyanates Research Articles

Vibrational spectra of acetyl isocyanate and mono-, di- and trichloroacetyl isocyanates

Abstract The gas-phase infrared and liquid-phase Raman spectra of R CO NCO, where R = CH3, CH2Cl, CHCl2 and CCl3, have been recorded. For each molecule an assignment of the observed bands has been proposed in terms of the two planar conformers derived from rotation about the C N bond. The observations indicate that the cisoid conformation is the preferred one in the gas phase while substantial amounts of both cisoid and transoid conformers are present in the liquid.

ChemInform Abstract: REACTION OF ACYL ISOCYANATES WITH 3‐FORMYLCAMPHOR

AbstractBei der Umsetzung von 3‐Formylcampher (I) mit den Acylisocyanaten (II) erhält man die 3‐(N‐Acyl‐carbamoyloxy)‐methylen‐campher‐Derivate als E‐ und Z‐Isomerengemisch (III) und (IV).

Reaction of acyl isocyanates with 3-formylcamphor

Benzoyl and trichloroacetyl isocyanates react with 3-formylcamphor to form only the O-addition, products.

Reaction of acyl(aroyl) isocyanates with dimedon

The benzoyl and trichloroacetyl isocyanates react with dimedon to give the [4 + 2]-cycloadducts and the O- and C-addition products, whereas trifluoroacetyl isocyanate reacts to give the acid azomethine.

Addition of acetylacetone to acyl(aroyl) isocyanates

When reacted with acetylacetone the trichloroacetyl and trifluoroacetyl isocyanates form the O-addition products, while benzoyl isocyanate forms a mixture of the O- and C-addition products.

Reaction of acyl isocyanates with aromatic aldazines

1. Benzoyl and trichloroacetyl isocyanates react with p-dimethylaminobenzalazine and benzalazine on the type of bis-1,3-dipolar cycloaddition to give substituted triazolo[1,2-a]triazoles. 2. Trifluoroacetyl isocyanate reacts with aromatic aldazines on the type of mono-[4+2]-cycloaddition. Trichloroacetyl isocyanate reacts in a similar manner with p-methoxybenzalazine.

Reaction of acyl isocyanates with pyridine

The trichloroacetyl and trifluoroacetyl isocyanates react with pyridine to give N-(1-pyridinocarbonyl)trichloro(trifluoro)acetyl amidates, while ditrichloro(trifluoro)acetylcarbodiimides are formed in the presence of 3-phenyl-1-ethyl-3-phospholene 1-oxide, which add to the C = N bond of pyridine on the type of 1,4-cycloaddition.

Reaction of acylisocyanates with unsaturated ethers

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.

Reactions of isocyanates with azomethines

The fcenzoyl and trichloroacetyl isocyanates react with azomethines on the type of both 2 + 2-and 2 + 4-cycloaddition. The temperature, reaction time, and the electronic effects of the substituents, all exert an effect on the ratio of the isomers.

Reactions of benzoyl and trichloeoacetyl isocyanates with unsaturated ethers and sulfides

1. The benzoyl and trichloroacetyl isocyanates react with enol ethers to yield products with a linear structure. 2. Trichloroacetyl isocyanate reacts with vinyl ethyl sulfides to give the 2 + 4-cycloaddition product, and with alkene sulfides of the RSCH=CHR′ type to give produots with a linear structure. Benzoyl isocyanate does not react with alkene sulfides.

Reaction of benzoyl and trichloroacetyl isocyanates with cyclic enamines

Benzoyl isocyanate reacts with morpholinocyclohexene, morpholinocyclopentene, piperidinocyclohexene, and piperidinocyclopentene on the type of 1,4-cycloaddition, with the formation of 1,3-oxazin-4-one derivatives, while trichloroacetyl isocyanate reacts on the type of 1,2-cycloaddition, with the formation of 2-azetidinone derivatives, and only with morpholinocyclopentene does it react on the type of 1,4-cycloaddition.

Reaction of benzoyl and trichloroacetyl isocyanates with some three-membered heterocycles

1. Benzoyl isocyanate reacts with epichlorohydrin and thioepichlorohydrin to give linear isomers. 2. The benzoyl and trichloroacetyl isocyanates react with cyclohexene sulfide to give both cyclic and linear isomers. 3. Benzoyl isocyanate reacts with propylene sulfide to give both the cyclic and the linear isomer.

Benzoyl and trichloroacetyl isocyanates in cyclo-formation reactions

1. Benzoyl isocyanate reacts with acrolein and diphenylacetylene by the 1,2-cyclo-addition type. 2. Benzoyl isocyanate and trichloroacetyl isocyanate react with γ -vinylpyridine by the 1,4-cyclo-addition type, with the formation of six-membered adducts. 3. Trichloroacetyl isocyanate reacts with p-halo-substituted phenylacetylenes by the 1,4-cyclo-addition type.

Interaction of benzoyl and trichloroacetyl isocyanates with electrophilic reagents

1. Benzoyl and trichloroacetyl isocyanates react with electrophilic reagents with greater difficulty than with nucleophilic reagents. 2. Benzoyl isocyanate reacts with ethylpropionate, propargylmethyl ether, and cis-dichloroethylene according to a scheme of 1,2-cycloaddition. 3. Trichloroacetyl isocyanate interacts with propargylmethyl ether according to the type of 1,2-cy-cloaddition and according to the type of substitutional addition. 4. A dimer of benzoyl isocyanate was produced, and its structure was established.

Reaction of benzoyl and trichloroacetyl isocyanates with Schiff bases

Benzalbenzylamine and p-substituted benzalbenzylamines react with benzoyl and trichloroacetyl isocyanates by the type of 1,4-addition, with the formation of 2,6-diphenyl-3-benzyl-3,4-dihydro-2H-1-oxa-3, 5-diazin-4-one and 2-phenyl-3-benzyl-6-trichloromethyl3,4-dihydro-2H-1-oxa-3,5-diazin-4-one derivatives.

Reaction of benzoyl and trichloroacetyl isocyanates with p-benzoquinone and ?-naphthoquinone

1. Benzoyl isocyanate reacts with p-benzoquinone andα-naphthoquinone by a 1,2-addition with ring formation. 2. Trichloroacetyl isocyanate reacts with p-benzoquinone by a diene-synthesis type of reaction.