Cyanoethylation reaction

Acetyl thiadiazole also displays enhanced reactivity in both the carbonyl and the methyl groups and enters the aldol condensation, the Mannich reaction, cyanoethylation reaction, the Willgerodt... 

Vapor or Spraying Applications. Cyanoethylation. Reaction of cellulose with acrylonitrile, CH2=CHCN, a vinyl monomer, was selected for study because it is known to produce several desirable changes in the properties of cellulosic fabrics and yams. After cyanoethylation, undegraded cotton becomes more resistant to microorganism attack, heat, acid, and abrasion (3). Moisture absorption decreases and the electrical properties change. The extent of these changes varies considerably... 

This versatile and convenient reaction results in the formation of a large number of polyfunctional nitriles. The scope, limitations, and experimental procedures along with many examples of cyanoethylation reactions have been presented. ... 

Triethylamine is an effective catalyst for the cyanoethylation reaction." Thus when a solution of acetylacetone, acrylonitrile, and triethylamine in a mixture of t-butanol (45 ml.) and water (15 ml.) was allowed to stand at 25 for 2 days, y,y-diacetylpimelonitrile separated in high yield and purity. A striking solvent effect is... 

The availability and cost of 0-methoxypropionitrile should be considered since it has been produced only on a commercial scale as a chemical intermediate. Acrylonitrile reacts readily with aliphatic alcohols in the presence of strong alkaline catalysts to form a broad spectrum of compounds known as alkoxypropionitriles. These reactions, commonly known as cyanoethylation reactions, have long been of interest to organic chemists because of the ease with which the addition takes place (6). The availability of low cost acrylonitrile and methanol has now given -methoxypropionitrile an attractive price tag. Cost estimates for producing this solvent are in the range of 20 to 25 cents/lb. 

A more complicated case occurred in the addition of acrylonitrile to 2-methyl-cyclohexanone (Scheme 2.7.). This cyanoethylation reaction was studied at ambient conditions on a new chiral catalyst NaOH on d- or /-quartz... 

Cyanoethylation Reaction with acrylonitrile (ACN) Southern yellow pine 5 % sodium hydroxide in wood by empty cell process full cell loading with ACN, then heat to 70-100 C EMC 4.5 % at 30 % ACN not attacked by fungi impact strength loss None... 

Cyanoethylation Reactions (Michael-Type Additions). Most compoimds with a labile hydrogen atom can add on the double bond of acrylonitrile to form cyanoethyl groups that is, the primary products are 3-substituted propionitriles. 

Cyanoethylation. Reaction of a primary or To favor formation of the mono-substituted a secondary aromatic amine with acrylonitrile aniline, a large excess of aniline is used. 

An example of the cyanoethylation reaction is the preparation of l,l,l-/m-(2-cyanoethyl)acetone [25]. In this case, alcoholic potassium hydroxide is used as a catalyst, while benzyltrimethylammonium hydroxide is frequently used in other preparations. 

Cannizzaro reaction, 60,66-67 Claisen condensation, 17, 21-22, 74-75 Claisen rearrangement, 33, 35 Clemmensen method, 5, 8-9 Curtius reaction, 132-133 Curtius rearrangement, 108 Cyanoethylation reaction, 172... 

The last-named reaction provides an excellent method for the preparation of a-substituted glutaric acids the intermediate alkyl (aryl) -2-cyanoethyl-malonate is both hydrolysed and decarboxylated re ily by boiling with an excess of 48 per cent, hydrobromic acid solution. 

The exchange resins 6nd application in (i) the purification of water (cation-exchange resin to remove salts, followed by anion-exchange resin to remove free mineral acids and carbonic acid), (ii) removal of inorganic impurities from organic substances, (iii) in the partial separation of amino acids, and (iv) as catalysts in organic reactions (e.g., esterification. Section 111,102, and cyanoethylation. Section VI,22). 

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). 

Reaction of olefin oxides (epoxides) to produce poly(oxyalkylene) ether derivatives is the etherification of polyols of greatest commercial importance. Epoxides used include ethylene oxide, propylene oxide, and epichl orohydrin. The products of oxyalkylation have the same number of hydroxyl groups per mole as the starting polyol. Examples include the poly(oxypropylene) ethers of sorbitol (130) and lactitol (131), usually formed in the presence of an alkaline catalyst such as potassium hydroxide. Reaction of epichl orohydrin and isosorbide leads to the bisglycidyl ether (132). A polysubstituted carboxyethyl ether of mannitol has been obtained by the interaction of mannitol with acrylonitrile followed by hydrolysis of the intermediate cyanoethyl ether (133). 

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). 

A major type of reaction in this class is the cyclization of 4-amino- or 4-halo-pyrimidines carrying 5-cyanoethyl or 5-ethoxycarbonylethyl groups, which cyclize to 7-amino or 7-oxo derivatives of 5,6-dihydropyrido[2,3- f]pyrimidine, e.g. (131)->(63). The intermediates may sometimes be prepared by reaction of 4(6)-aminopyrimidines with acrylonitrile, or even via a pyrimidine ring synthesis from an amidine and a cyanoacetic ester or malononitrile derivative, e.g. (132) -> (133) (7lJOC2 85, 72BCJ1127). 

Lochte and Pitman (44) have reported the cyanoethylation of the pyrrolidine enamine of 3-methylcycIopentanone (84), the product being a mixture of C-2 and C-5 cyanoethylated ketones (85 and 86). Hunig and Salzwedel 20) have obtained a mixture of C2- and C5-acylated products from the reaction of morpholine enamine of 3-methylcyclopentanone with propionyl chloride. 

The side-chain cyanoethylation of alkyl thienyl ketones with acrylonitrile has been studied " and used for the preparation of 8-oxonitriles and S-oxoacids. Aminomethylation (Mannich reaction) of 2-acetylthiophene followed by steam distillation yielded 50% of 2-thienyl vinyl ketone, and has also been used for the synthesis of compounds of biological interest. ... 

Dimethylindole magnesium iodide reacts with chloroacetonitrile in ether to give 3-cyanomethyl-2,3-dimethylindolenine (234). Majima and Hoshino obtained 3-(2-cyanoethyl)lndole (235) by the action of -chloropropionitrile on indole magnesium iodide. The reaction was slower with -chloropropionitrilc than with chloro-aoetonitrile. 3-(3-Cyano-w-propyl)indole (236), required as an intermediate in the synthesis of 3-indolyl-y-w-butyric acid, was prepared, but not isolated, by the action of y-chloro-w-butyronitrile on indole magnesium iodide. ... 

Propose a mechanism to account for cleavage of the /3-cyanoethyl protecting group from the phosphate groups on treatment with aqueous ammonia. (Acrylonitrile, H2C=CHCN, is a by-product.) What kind of reaction is occurring ... 

In comparison with other anionics, little has been published concerning methods of analysis of ether carboxylates. Gerhardt et al. [238] investigated the analytical determination of ether carboxylic acids in reaction mixtures obtained by reaction of nonylphenol ethoxylates with sodium chloroacetate as well as by cyanoethylation by different methods. Several methods, used for other surfactants as well [239], can be used for ether carboxylates. 

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