Direct determination of chlorination products of organic amines using membrane introduction mass spectrometry

Tapio Kotiaho, M. Hayward, R. Cooks

Research output: Contribution to journalArticleScientificpeer-review

38 Citations (Scopus)

Abstract

Direct analysis of organic chloramines in low concentrations in aqueous solutions is achieved by membrane introduction mass spectrometry. Tandem mass spectrometry allows structures of the chlorination products to be determined and shows that nitrogen chlorination occurs for aliphatic amines and ring chlorination for aniline. Monochlorination of aniline occurs mainly at the ortho position, while dichlorination yields 20-35% diortho and 80-65% ortho-para substitution products. Depending on the reaction conditions, the actual chlorination reagent can be chloramine, hypochlorous acid, and possibly chlorine. The high ortho chlorination yields of aniline are explained by a mechanism in which chlorination occurs first at the nitrogen atom with subsequent intramolecular rearrangement to the ortho position in analogy to rearrangement of the nitro group in N-nitro aromatic amines. Using flow injection analysis procedures, it is possible to follow in an on-line fashion reactions that yield (or remove) organic chloramines at sub parts per million levels.
Original languageEnglish
Pages (from-to)1794 - 1801
Number of pages8
JournalAnalytical Chemistry
Volume63
Issue number17
DOIs
Publication statusPublished - 1991
MoE publication typeA1 Journal article-refereed

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Chlorination
Amines
Mass spectrometry
Membranes
Chloramines
Nitrogen
Hypochlorous Acid
Chlorine
Substitution reactions
Atoms
aniline

Cite this

Kotiaho, Tapio ; Hayward, M. ; Cooks, R. / Direct determination of chlorination products of organic amines using membrane introduction mass spectrometry. In: Analytical Chemistry. 1991 ; Vol. 63, No. 17. pp. 1794 - 1801.
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abstract = "Direct analysis of organic chloramines in low concentrations in aqueous solutions is achieved by membrane introduction mass spectrometry. Tandem mass spectrometry allows structures of the chlorination products to be determined and shows that nitrogen chlorination occurs for aliphatic amines and ring chlorination for aniline. Monochlorination of aniline occurs mainly at the ortho position, while dichlorination yields 20-35{\%} diortho and 80-65{\%} ortho-para substitution products. Depending on the reaction conditions, the actual chlorination reagent can be chloramine, hypochlorous acid, and possibly chlorine. The high ortho chlorination yields of aniline are explained by a mechanism in which chlorination occurs first at the nitrogen atom with subsequent intramolecular rearrangement to the ortho position in analogy to rearrangement of the nitro group in N-nitro aromatic amines. Using flow injection analysis procedures, it is possible to follow in an on-line fashion reactions that yield (or remove) organic chloramines at sub parts per million levels.",
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Direct determination of chlorination products of organic amines using membrane introduction mass spectrometry. / Kotiaho, Tapio; Hayward, M.; Cooks, R.

In: Analytical Chemistry, Vol. 63, No. 17, 1991, p. 1794 - 1801.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Direct determination of chlorination products of organic amines using membrane introduction mass spectrometry

AU - Kotiaho, Tapio

AU - Hayward, M.

AU - Cooks, R.

PY - 1991

Y1 - 1991

N2 - Direct analysis of organic chloramines in low concentrations in aqueous solutions is achieved by membrane introduction mass spectrometry. Tandem mass spectrometry allows structures of the chlorination products to be determined and shows that nitrogen chlorination occurs for aliphatic amines and ring chlorination for aniline. Monochlorination of aniline occurs mainly at the ortho position, while dichlorination yields 20-35% diortho and 80-65% ortho-para substitution products. Depending on the reaction conditions, the actual chlorination reagent can be chloramine, hypochlorous acid, and possibly chlorine. The high ortho chlorination yields of aniline are explained by a mechanism in which chlorination occurs first at the nitrogen atom with subsequent intramolecular rearrangement to the ortho position in analogy to rearrangement of the nitro group in N-nitro aromatic amines. Using flow injection analysis procedures, it is possible to follow in an on-line fashion reactions that yield (or remove) organic chloramines at sub parts per million levels.

AB - Direct analysis of organic chloramines in low concentrations in aqueous solutions is achieved by membrane introduction mass spectrometry. Tandem mass spectrometry allows structures of the chlorination products to be determined and shows that nitrogen chlorination occurs for aliphatic amines and ring chlorination for aniline. Monochlorination of aniline occurs mainly at the ortho position, while dichlorination yields 20-35% diortho and 80-65% ortho-para substitution products. Depending on the reaction conditions, the actual chlorination reagent can be chloramine, hypochlorous acid, and possibly chlorine. The high ortho chlorination yields of aniline are explained by a mechanism in which chlorination occurs first at the nitrogen atom with subsequent intramolecular rearrangement to the ortho position in analogy to rearrangement of the nitro group in N-nitro aromatic amines. Using flow injection analysis procedures, it is possible to follow in an on-line fashion reactions that yield (or remove) organic chloramines at sub parts per million levels.

U2 - 10.1021/ac00017a025

DO - 10.1021/ac00017a025

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VL - 63

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