Quantitative Acetylation of Amines by Means of Acetyl Chloride and Pyridine

Olson, Verner R.; Feldman, Harry B.

doi:10.1021/ja01289a062

Cited by 11 publications

(3 citation statements)

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“…However, Olson and Feldman (1937) (120) found the method of Smith and Bryant unsuitable for the quantitative determination of amines. Primary aromatic amines yielded widely varying results although secondary aromatic amines gave quantitative results; aliphatic amines gave very low results.…”

Section: General Macro Methodsmentioning

confidence: 99%

Determination of Reactive Hydrogen in Organic Compounds

Olleman¹

1952

Anal. Chem.

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Methods for quantitatively determining reactive hydrogen in organic compounds have been reviewed to find the most suitable procedures for estimating the reactive structural units in coal degradation products. In the past, reaction with methylmagnesium iodide or lithium aluminum hydride has been used to determine total reactive hydrogen in organic compounds with an accuracy o f 1 3 to 5%. The types of compounds which have been determined are: alcohols, phenols, enols, mercaptans, acids. amines, amides, and water. Acylation methods. including acetylation, phthaloylation, benzoylation, ETHODS for quantitatively determiningreactive hydrogen in organic compounds-Le., hydrogen attached tonitrogen. oxygen, or sulfur and exceptionally reactive carbon-hydrogen structures-have been reviewed to find the most suitable procedures for estimating the reactive oxygen-and nitrogen-containing structures in coal degradation products. The chemical literature from 1927 to 1949, inclusive, has been thoroughly searched, and some earlier and more recent references have been consulted The literature previous to 1931 was reviewed by Meyer (93).Methyl Grignard reagents and lithium aluminum hydride will react quantitatively R ith reactive hydrogen atoms in organic compounds t o form methane and hydrogen, respectively. The gaa formed in each case is a memure of the "artive hydrogen." Other reagents have been reported for the determination of active hydrogen but are generally less satisfactory.Some of the active hydrogen atoms can also be replaced b i a(-yl groups, and compounds containing such hydrogen atoms are said to contain "acylatable hydrogen" or usually "acetylatable hydrogrn." ""wylatable hydrogen" and ' acetylatable hydrogen"are not strictly correct t e i m~, inaqmuch as the hydrogen is not acylated but rather replaced by an acyl group. However, these are convenient ternis which distinctly differentiate methods which involve acylation of reactive groups from the methods I T hich determine total "active hydrogen." Different reagents and conditions cause quantitative acylation of different functional groups, and consequently the terms "acylatable hydrogen" and "acetylatahle hydrogen" have little meaning unless the reagent and conditions are specified. Pa 1 Present addreas, Verona Research Center Koppers Co , Inc , Verona,formylation, and stearylation, vary greatly among themselves and give results depending on reagents and conditions. Variations of the most common method-i.e., acetylation using acetic anhydride and pyridine at approximately 100' C.-have been used to determine primary and secondary alcohols, "unhindered" phenols, and primary and secondary amines. Other acylation reagents may be advantageous if tertiary alcohols or pyrroles must be determined or selectivity of reaction is desired. Applicability of different acylation methods for determining functional groups has been tabulated.The methods of deterniining reactive hydrogen have thus been divided into two major groups-determinations of active hydrogrn and determinations o...

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Section: General Macro Methodsmentioning

confidence: 99%

Determination of Reactive Hydrogen in Organic Compounds

Olleman¹

1952

Anal. Chem.

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“…Compounds containing these two functional groups are also routinely synthesized, and the two sources provide a variety of compounds for biological testing. While there are several methods for making amides and esters, the use of acyl chloride or acyl anhydride in a weak base like pyridine is usually employed, especially when the reactants are simple alcohols or amines [1]. Several other methods using mainly acetic anhydride with different bases and acids have been reported [2][3][4][5][6][7][8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

1-[(1S,2S)-1,2-Bis(2-hydroxyphenyl)-2-pivaloylaminoethylamino]-2,2-dimethyl-1-propanone

Lugemwa

2019

Molbank

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When 2-[(1S,2S)-1,2-diamino-2(2-hydroxyphenyl)ethyl]phenol (I) was reacted with 2 mole equivalents of trimethyl acetic (pivalic) anhydride in tetrahydrofuran at room temperature, 1-[(1S,2S)-1,2-bis(2-hydroxyphenyl)-2-pivaloylaminoethylamino]-2,2-dimethyl-1-propanone (II) was obtained quantitatively as the only product. The structure of the product was determined using 1H- and 13C-NMR. The COSY spectrum indicated that the single –NH was coupled to the single benzylic proton, –CH. The versality of the transformation could be used to generate additional compounds for use in various research areas.

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“…12 Few methods of acetylation of amines are known using ace- * For correspondence tyl chloride of which most common is the use of acetyl chloride in pyridine. 13 Acetyl chloride has also been used in combination with some fairly exotic reagents such as ZrOCl 2 •8H 2 O, 14 zinc dust 15 and thermally decomposed Ni-Fe-hydrotalcite. 16 However, owing to its aforementioned explosive nature when in contact with water and subsequent rapid hydrolysis, the use of this easily available and cost effective reagent in aqueous medium has proved elusive till date.…”

Section: Introductionmentioning

confidence: 99%

Efficient acetylation of primary amines and amino acids in environmentally benign brine solution using acetyl chloride

Basu¹,

Chakraborty²,

Sarkar

et al. 2013

J Chem Sci

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Acetyl chloride is one of the most commonly available and cheap acylating agent but its high reactivity and concomitant instability in water precludes its use to carry out acetylation in aqueous medium. The present methodology illustrates the efficient acetylation of primary amines and amino acids in brine solution by means of acetyl chloride under weakly basic condition in the presence of sodium acetate and/or triethyl amine followed by trituration with aqueous saturated bicarbonate solution. This effort represents the first efficient use of this most reactive but cheap acetylating agent to acetylate amines in excellent yields in aqueous medium. This is a potentially useful green chemical transformation where reaction takes place in environment-friendly brine solution leading to easy work-up and isolation of the amide derivatives. Mechanistic rationale of this methodology is also important.

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Quantitative Acetylation of Amines by Means of Acetyl Chloride and Pyridine

Abstract: Quantitative Acetylation of Amines 2003 2. The benzoyl and o-chlorobenzoyl esters and 3. The structure of each of the seven phenols the -naphthylurethans of the seven phenols was established by synthesis.were prepared.East Lansing, Mich.

Cited by 11 publications

References 0 publications

Determination of Reactive Hydrogen in Organic Compounds

Determination of Reactive Hydrogen in Organic Compounds

1-[(1S,2S)-1,2-Bis(2-hydroxyphenyl)-2-pivaloylaminoethylamino]-2,2-dimethyl-1-propanone

Efficient acetylation of primary amines and amino acids in environmentally benign brine solution using acetyl chloride

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