Kinetics and Mechanism of the Cyanoethylation of Alcohols

Feit, Ben‐Ami; Zilkha, Albert

doi:10.1021/jo01037a031

Cited by 30 publications

(12 citation statements)

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“…In a fairly typical study of the heterogeneous reaction of methyl chloride with alkali cellulose, the relative rate constants (k2k -:k) for the 2-, 3-, and 6-position hydroxyl groups were 5, 1, and 2, respectively (8). A very similar ratio of reaction constants (p:k3:k = 4.5:1::2) was found for ethyl cellulose prepared under essentially the same conditions (19).…”

Section: Ordinary Nucleophilic Substitutionssupporting

confidence: 70%

The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose¹

Touzinsky¹

1965

J. Org. Chem.

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A carbamoethyl cellulose was prepared by the Michael addition reaction of acrylamide with cellulose in the presence of sodium hydroxide. The reaction was allowed to proceed till equilibrium conditions were approached. Nitrogen and carboxyl analyses indicated the derivatives to be 0.48 D.S. carbamoethyl and 0.30 D.S. carboxyethyl, a total of 0.78 D.S. The distribution of the substituents was studied by the hydrolysis and separation method. The procedure used to hydrolyze the cellulose also completely hydrolyzed the amide groups and gave a mixture of glucose and carboxyethyl glucoses. This mixture was separated by paper chromatography into glucose and the mono-, di-, and trisubstituted glucoses. Identities were assigned to the substituted glucoses on the basis of the molar ratio of their carboxyl content to their aldehyde content and on the basis of chromatographic comparison to carboxyethyl glucoses which were prepared by carbamoethylating suitably blocked glucoses and hydrolyzing the products. The mole fractions were measured by an alkaline hypoiodite oxidation. The Spurlin equations for the distribution of substituents in an equilibrium reaction were reduced to a cubic equation in the relative equilibrium constant, AK, in terms of the mole fractions of substituted glucoses, c.. Co(AK)-c1(AK)+c2AK-c3 = 0 This equation was solved for AK using the experimentally measured mole fractions to give the relative equilibrium constants, K:K3:K ::9:1:19.

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Section: Ordinary Nucleophilic Substitutionssupporting

confidence: 70%

The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose¹

Touzinsky¹

1965

J. Org. Chem.

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“…The conversion was increased when about 6% of cyanoethylated 1‐octadecanol was found in reaction mixture. The pseudo first‐order rate constants39, 16 for cyanoethylation of 1‐octadecanol and hexane‐1,6‐diol were 1.105 × 10 −3 (coefficient of determination R 2 = 0.67) and 6.525 × 10 −3 ( R 2 = 0.88), respectively.…”

Section: Resultsmentioning

confidence: 99%

Solvent‐free cyanoethylation of selected alcohols using amberlyst A‐21 polymer resin

Trinadh

Rajasekhar

Bhadru

et al. 2012

J of Applied Polymer Sci

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Solvent-free cyanoethylation of selected alcohols with acrylonitrile (AN) using a weakly basic polymer resin, Amberlyst A-21 (AA-21) was studied at 75 C. The conversion of primary alcohols, 1-octadecanol, hexane-1,6-diol, pentaerythritol, but-2-yne-1,4-diol, N-methyldiethanolamine, triethanolamine and diethanolamine is higher than secondary alcohols, isopropanol and glycerol in the presence of polymer resin. Of various alcohols, but-2-yne-1,4-diol gave the product in high conversion (87%) in cyanoethylation with a polymer resin/AN weight ratio of 0.04. The polymer resin showed recycling ability only in two cycles to produce cyanoethylated product from diethanolamine. In case of 1-octadecanol, hexane-1,6-diol, and N-methyldiethanolamine with AN under similar conditions, no recycling ability was observed. Thermally treated polymer resin at 75 C afforded the product in lower conversion (55%) whereas the same product was obtained in 69% when fresh polymer resin was used in cyanoethylation of 1-octadecanol. No catalytic effect was observed for polymer resin treated at 100 C. Fourier transform infrared (FTIR) spectra showed CN stretching at 2248 cm À1 for the polymer resin collected after the reaction which was caused by the AN binding on polymer resin during the reaction. As per thermogravimetric curves, 5% weight loss was observed at 201 C for recovered resin and at 161 C for polymer resin treated at 100 C. Scanning electron microscope images confirmed the AN binding on polymer beads after catalytic activity.

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“…At low NaOH concentration (<0.3 mol/l), the A.E. was low (entries 11).The concentration of the NaOH catalyst must be high enough to ionize the hydroxyl groups of inulin (pK, > 12), which subsequently react with the relatively positively charged carbon atom of acrylonitrile [9]. The cyanoethylation is reversible 181: the decyanoethylation starting with the ionization of the a-CH2 group (with recovery of inulin) is favoured at higher reaction temperatures (entry 2,10), at high concentration of NaOH (entries [12][13][14] and when the reaction is proceeded for a long time (entries [6][7][8].…”

Section: Cyanoethylation Of Inulinmentioning

confidence: 99%

Synthesis of Cyanoethyl Inulin, Aminopropyl Inulin and Carboxyethyl Inulin

et al. 1996

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Inulin was cyanoethylated by reaction with acrylonitrile in the presence of aqueous sodium hydroxide. Products with a degree of substution (ds) from 0.2 to 1.6 were prepared. The materials were analyzed using NMR spectroscopy and GPC analysis. The nitrile groups of cyanoethyl inulin were converted into amino groups by reduction with sodium borohydride in the presence of a transition metal chloride (CoCl2.6H2O). Furthermore, the nitrile groups were hydrolyzed towards carboxylates using hydrogen peroxide in alkaline medium. The polycarboxylate obtained by this means was shown to possess good calcium carbonate crystallization inhibition properties.

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Kinetics and Mechanism of the Cyanoethylation of Alcohols

Cited by 30 publications

References 0 publications

The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose¹

The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose¹

Solvent‐free cyanoethylation of selected alcohols using amberlyst A‐21 polymer resin

Synthesis of Cyanoethyl Inulin, Aminopropyl Inulin and Carboxyethyl Inulin

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Kinetics and Mechanism of the Cyanoethylation of Alcohols

Cited by 30 publications

References 0 publications

The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose1

The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose1

Solvent‐free cyanoethylation of selected alcohols using amberlyst A‐21 polymer resin

Synthesis of Cyanoethyl Inulin, Aminopropyl Inulin and Carboxyethyl Inulin

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The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose¹

The Substituent Group Distribution in a Michael Reaction. Carbamoethyl Cellulose¹