Acrylonitrile, reaction with

Acetyloxindole, 40, 1 Aud chlorides, from acids and chloro vmylamuies, 41, 23 from cyanoacetic acid, 41, 5 from pentaacetylglucomc acid, 41, 80 Acrylamide, N benzyl, 42,16 Acrylonitrile, reaction with benzyl alcohol, 42, 16... 

The principal pathway leading to degradation of acrylonitrile in air is believed to be photooxidation, mainly by reaction with hydroxyl radicals (OH). The rate constant for acrylonitrile reaction with OH has been measured as 4.1 x 10" cm /molecule/second (Harris et al. 1981). This would correspond to an atmospheric half-life of about 5 to 50 hours. This is consistent with a value of 9 to 10 hours measured in a smog chamber (Suta 1979). 

Many inorganic and organic compounds possessing labile hydrogen atoms add acrylonitrile readily with the formation of compounds containing a cyancethyl grouping (—CH j. CH2. CN). This reaction is usually known as cyanoelhylation ... 

Acrylonitrile reacts with the sodium salt of 4.5-dimethvl-A-4-thiazoline-2-thione (73J (R4 = R5 = Me) to yield 3-(2-cyanoethyl)-4.5-dimethyl-A-4-thiazoline-2-thione (74) (R4 = R, = Me) (Scheme 35 (160). Humphlett s studies of this reaction showed that the size of the R4 substituent is a determinant factor for the S versus N ratio (161. 162). If R4 == H, 100% of the N-substituted product (74) is obtained this drops to 50% when R4 = methyl, and only the S-substituted product (75) is obtained when R4 = phenyl. The same trend is observed with various CH2 = CH-X (X = C00CH3. COCH3) reagents (149). The S/N ratio also depends on the electrophilic center for CH2 = CH-X systems thus S-reaction occurs predominantly with acrylonitrile, whereas N-substitution predominates with methvlvinvlketone (149). 

The sulfuric acid hydrolysis may be performed as a batch or continuous operation. Acrylonitrile is converted to acrylamide sulfate by treatment with a small excess of 85% sulfuric acid at 80—100°C. A hold-time of about 1 h provides complete conversion of the acrylonitrile. The reaction mixture may be hydrolyzed and the aqueous acryhc acid recovered by extraction and purified as described under the propylene oxidation process prior to esterification. Alternatively, after reaction with excess alcohol, a mixture of acryhc ester and alcohol is distilled and excess alcohol is recovered by aqueous extractive distillation. The ester in both cases is purified by distillation. 

Another type of polyol often used in the manufacture of flexible polyurethane foams contains a dispersed soHd phase of organic chemical particles (234—236). The continuous phase is one of the polyols described above for either slab or molded foam as required. The dispersed phase reacts in the polyol using an addition reaction with styrene and acrylonitrile monomers in one type or a coupling reaction with an amine such as hydrazine and isocyanate in another. The soHds content ranges from about 21% with either system to nearly 40% in the styrene—acrylonitrile system. The dispersed soHds confer increased load bearing and in the case of flexible molded foams also act as a ceU opener. 

Other reactions that show preference for the acidic N-3—H group include Mannich aminomethylation by treatment with formaldehyde and an amine (38) to yield compound (8), reaction with ethyleneimine (39) to give (9), and Michael-type additions (40) such as the one with acrylonitrile to give (10) ... 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

Cyanoethylation. One of the eadiest examples of etherification of ceUulose by an unsaturated compound through vinyl addition is the cyanoethylation of cotton (58). This base-cataly2ed reaction with acrylonitrile [107-13-1/, a Michael addition, proceeds as foUows ... 

Other modifications of the polyamines include limited addition of alkylene oxide to yield the corresponding hydroxyalkyl derivatives (225) and cyanoethylation of DETA or TETA, usuaHy by reaction with acrylonitrile [107-13-1/, to give derivatives providing longer pot Hfe and better wetting of glass (226). Also included are ketimines, made by the reaction of EDA with acetone for example. These derivatives can also be hydrogenated, as in the case of the equimolar adducts of DETA and methyl isobutyl ketone [108-10-1] or methyl isoamyl ketone [110-12-3] (221 or used as is to provide moisture cure performance. Mannich bases prepared from a phenol, formaldehyde and a polyamine are also used, such as the hardener prepared from cresol, DETA, and formaldehyde (228). Other modifications of polyamines for use as epoxy hardeners include reaction with aldehydes (229), epoxidized fatty nitriles (230), aromatic monoisocyanates (231), or propylene sulfide [1072-43-1] (232). 

The stabilization of chloromethoxycarbene (234) was intensively studied. It is formed from diazirine (233) in a first order reaction with fi/2 = 34h at 20 C. It reacts either as a nucleophile, adding to electron poor alkenes like acrylonitrile with cyclopropanation, or as an electrophile, giving diphenylcyclopropenone with the electron rich diphenylacetylene. In the absence of reaction partners (234) decomposes to carbon monoxide and methyl chloride (78TL1931, 1935). 

Acrylic acid, -(3-benzo[f>]thienyl)-a -mercapto-reaction with iodine, 4, 764 Acrylic acid, o -cyano-y3-(2-thienyl)-ring opening, 4, 807 Acrylic acid, -formyl-in pyridazinone synthesis, 3, 46 Acrylic acid, furyl-rotamers, 4, 545 synthesis, 4, 658 Acrylic acid, 2-hydroxybenzoyl-chroman-4-one synthesis from, 3, 850 Acrylic acid, 5-(l-propynyl)-2-thienyl-methyl ester occurrence, 4, 909 Acrylonitrile... 

Imidazo[4,5-c]pyridine-2(3f7)-thione, 1-methyl-reactions with acrylonitrile, 5, 620 Imidazo[l,2-a]pyridine-2(3H)-thiones synthesis, 5, 632... 

Although hexafluoro-l,3-butadiene is better known for its [2+2] reactions, its Diels-Alder reactions, particularly with electron-deficient alkenes such as acrylonitrile and perfluoropropene, are not unknown [9] The first report of a Diels-Alder reaction is with an acetylenic dienophile Although the major product of Us reaction with phenylacetylene is its [2+2] adduct, a 3 5% yield of products of a Diels-Alder reaction is also observed [123] (equation 103)... 

The enamines derived from cyclic ketones give the normal alkylated products, although there is some evidence that unstable cycloadducts are initially formed (55b). Thus the enamine (28) derived from cyclohexanone and pyrrolidine on reaction with acrylonitrile, acrylate esters, or phenyl vinyl sulfone gave the 2-alkylated cyclohexanones (63) on hydrolysis of the intermediates (31,32,55,56). These additions are sensitive to the polarity of the solvent. Thus (28) in benzene or dioxane gave an 80% yield of the... 

The reaction of enamines with ketene (146) and sulfene (147) are presumed to proceed by a two-step process involving an iminium intermediate such as 99. In fact, reaction with all electrophilic olefins such as acrylonitrile and related reagents could be thought of as going through an iminium intermediate similar to 99. Another example is given by addition to an enamine... 

The ability of 1,2 (or l,6)-dihydropyridines to undergo a Diels-Alder reaction with dienophiles such as methyl vinyl ketone, methyl acrylate, and acrylonitrile has been utilized in the synthesis of polyfunctional isoquinuclidine as a key intermediate in the synthesis of aspidosperma- and iboga-type alkaloids (66JA3099). 

Dihydropyridines 28 behave as enamines and undergo [2 - - 2] cycloaddition reactions with dienophiles such as acrylonitrile (29) and dimethyl acetylenedicar-boxylate (32). For instance, A -alkyl-l,4-dihydropyridine 28 reacts with 29 to give... 

The Reisert compound 93, prepared from quinoline derivatives 92, gave upon reaction with dimethyl acetylenedicarboxylate the pyrroloquinoline 95. Reduction of 93 gave the tetrahydro derivative that upon reaction with dimethyl acetylenedicarboxylate afforded 96 (85JOC722). Reaction of 94 with acrylonitrile in presence of base gave pyrroloquinoline 97 (77JCS(P1)2018) (Scheme 18). 

Enamines react with acceptor-substituted alkenes (Michael acceptors) in a conjugate addition reaction for example with o ,/3-unsaturated carbonyl compounds or nitriles such as acrylonitrile 8. With respect to the acceptor-substituted alkene the reaction is similar to a Michael addition ... 

Reaction with Acrylonitrile (9) As in the preceding case, a mixture of 61 g (0.45 mole) of aluminum chloride in 300 ml of benzene is heated to 60°, and a solution of 26.6 g (0.5 mole) of acrylonitrile in 100 ml of benzene is added. Butadiene (0.9 mole) is bubbled into the stirred and heated solution over a period of 4 hours, and the reaction mixture is worked up as above. Distillation gives 3-cyclohexene-1-carbonitrile, bp 80-87°/20 mm, nj,° 1.4742, in about 85% yield. 

MMA and DMAPMA poly(MMA-co-DMAPMA) 23, obtained by radical copolymerization, can produce a photografting reaction with acrylonitrile (AN) using BP as the initiator [61]. The formation of a graft copolymer, poly[(MMA -c<7-DMAPMA)- -AN] was confirmed by FT-IR spectrophotometry. Based on ESR studies and end group analysis, the mechanism of grafting reaction is proposed as follows ... 

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