Enantioselective dehydration of butan-2-ol using zeolite Y modified with dithiane oxides

Saskia Feast, M Rafiq, H Siddiqui, Richard P.K. Wells, David J. Willock, Frank King, Colin H. Rochester, Donald Bethell, Philip C. Bulman Page, Graham J. Hutchings

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Modification of zeolite H-Y by dithiane oxides (2-R-1,3-dithiane 1-oxide; R = H, CH3, C6H5) is shown to enhance significantly its activity for the acid catalysed gas phase dehydration of butan-2-ol. The rate enhancement is observed for catalysts that are prepared by adding the dithiane oxide to the zeolite synthesis gel or by adsorption of the dithiane oxide onto commercial samples of zeolite H-Y. The origin of the rate enhancement is considered to result from a specific interaction between the dithiane oxide modifier with both the extra-framework and framework aluminium in the zeolite. Modification of zeolite H-Y with (R)-1,3-dithiane 1-oxide enhances the conversion of (S)-butan-2-ol compared to (R)-butan-2-ol in the temperature range 110-150 degrees C when the two enantiomers are reacted separately. Modification with (S)-2-phenyl-1,3-dithiane 1-oxide gives a catalyst for which (R)-butan-2-ol is the most reactive of the two enantiomers. Reaction of racemic butan-2-ol over these chirally modified H-Y zeolites demonstrates that this modification procedure makes the zeolite enantiomerically discriminating and one enantiomer preferentially reacts, although both are present in the micropores under the reaction conditions. This effect is considered to be due to enantioselective rate enhancement, since, although the rate of dehydration of both enantiomers is enhanced in the chiral environment, the dehydration rate of one enantiomer is accelerated relative to the other. It is suggested that the effect is due to preferential adsorption at the chiral active site. (C) 1997 Academic Press.

Original languageEnglish
Pages (from-to)533-542
Number of pages10
JournalJournal of Catalysis
Volume167
Issue number2
DOIs
Publication statusPublished - 15 Apr 1997

Keywords

  • asymmetric catalyst
  • hydrogenation

Cite this

Feast, S., Rafiq, M., Siddiqui, H., Wells, R. P. K., Willock, D. J., King, F., ... Hutchings, G. J. (1997). Enantioselective dehydration of butan-2-ol using zeolite Y modified with dithiane oxides. Journal of Catalysis, 167(2), 533-542. https://doi.org/10.1006/jcat.1997.1576

Enantioselective dehydration of butan-2-ol using zeolite Y modified with dithiane oxides. / Feast, Saskia; Rafiq, M ; Siddiqui, H ; Wells, Richard P.K.; Willock, David J. ; King, Frank; Rochester, Colin H. ; Bethell, Donald; Page, Philip C. Bulman; Hutchings, Graham J. .

In: Journal of Catalysis, Vol. 167, No. 2, 15.04.1997, p. 533-542.

Research output: Contribution to journalArticle

Feast, S, Rafiq, M, Siddiqui, H, Wells, RPK, Willock, DJ, King, F, Rochester, CH, Bethell, D, Page, PCB & Hutchings, GJ 1997, 'Enantioselective dehydration of butan-2-ol using zeolite Y modified with dithiane oxides' Journal of Catalysis, vol. 167, no. 2, pp. 533-542. https://doi.org/10.1006/jcat.1997.1576
Feast, Saskia ; Rafiq, M ; Siddiqui, H ; Wells, Richard P.K. ; Willock, David J. ; King, Frank ; Rochester, Colin H. ; Bethell, Donald ; Page, Philip C. Bulman ; Hutchings, Graham J. . / Enantioselective dehydration of butan-2-ol using zeolite Y modified with dithiane oxides. In: Journal of Catalysis. 1997 ; Vol. 167, No. 2. pp. 533-542.
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abstract = "Modification of zeolite H-Y by dithiane oxides (2-R-1,3-dithiane 1-oxide; R = H, CH3, C6H5) is shown to enhance significantly its activity for the acid catalysed gas phase dehydration of butan-2-ol. The rate enhancement is observed for catalysts that are prepared by adding the dithiane oxide to the zeolite synthesis gel or by adsorption of the dithiane oxide onto commercial samples of zeolite H-Y. The origin of the rate enhancement is considered to result from a specific interaction between the dithiane oxide modifier with both the extra-framework and framework aluminium in the zeolite. Modification of zeolite H-Y with (R)-1,3-dithiane 1-oxide enhances the conversion of (S)-butan-2-ol compared to (R)-butan-2-ol in the temperature range 110-150 degrees C when the two enantiomers are reacted separately. Modification with (S)-2-phenyl-1,3-dithiane 1-oxide gives a catalyst for which (R)-butan-2-ol is the most reactive of the two enantiomers. Reaction of racemic butan-2-ol over these chirally modified H-Y zeolites demonstrates that this modification procedure makes the zeolite enantiomerically discriminating and one enantiomer preferentially reacts, although both are present in the micropores under the reaction conditions. This effect is considered to be due to enantioselective rate enhancement, since, although the rate of dehydration of both enantiomers is enhanced in the chiral environment, the dehydration rate of one enantiomer is accelerated relative to the other. It is suggested that the effect is due to preferential adsorption at the chiral active site. (C) 1997 Academic Press.",
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AU - Feast, Saskia

AU - Rafiq, M

AU - Siddiqui, H

AU - Wells, Richard P.K.

AU - Willock, David J.

AU - King, Frank

AU - Rochester, Colin H.

AU - Bethell, Donald

AU - Page, Philip C. Bulman

AU - Hutchings, Graham J.

PY - 1997/4/15

Y1 - 1997/4/15

N2 - Modification of zeolite H-Y by dithiane oxides (2-R-1,3-dithiane 1-oxide; R = H, CH3, C6H5) is shown to enhance significantly its activity for the acid catalysed gas phase dehydration of butan-2-ol. The rate enhancement is observed for catalysts that are prepared by adding the dithiane oxide to the zeolite synthesis gel or by adsorption of the dithiane oxide onto commercial samples of zeolite H-Y. The origin of the rate enhancement is considered to result from a specific interaction between the dithiane oxide modifier with both the extra-framework and framework aluminium in the zeolite. Modification of zeolite H-Y with (R)-1,3-dithiane 1-oxide enhances the conversion of (S)-butan-2-ol compared to (R)-butan-2-ol in the temperature range 110-150 degrees C when the two enantiomers are reacted separately. Modification with (S)-2-phenyl-1,3-dithiane 1-oxide gives a catalyst for which (R)-butan-2-ol is the most reactive of the two enantiomers. Reaction of racemic butan-2-ol over these chirally modified H-Y zeolites demonstrates that this modification procedure makes the zeolite enantiomerically discriminating and one enantiomer preferentially reacts, although both are present in the micropores under the reaction conditions. This effect is considered to be due to enantioselective rate enhancement, since, although the rate of dehydration of both enantiomers is enhanced in the chiral environment, the dehydration rate of one enantiomer is accelerated relative to the other. It is suggested that the effect is due to preferential adsorption at the chiral active site. (C) 1997 Academic Press.

AB - Modification of zeolite H-Y by dithiane oxides (2-R-1,3-dithiane 1-oxide; R = H, CH3, C6H5) is shown to enhance significantly its activity for the acid catalysed gas phase dehydration of butan-2-ol. The rate enhancement is observed for catalysts that are prepared by adding the dithiane oxide to the zeolite synthesis gel or by adsorption of the dithiane oxide onto commercial samples of zeolite H-Y. The origin of the rate enhancement is considered to result from a specific interaction between the dithiane oxide modifier with both the extra-framework and framework aluminium in the zeolite. Modification of zeolite H-Y with (R)-1,3-dithiane 1-oxide enhances the conversion of (S)-butan-2-ol compared to (R)-butan-2-ol in the temperature range 110-150 degrees C when the two enantiomers are reacted separately. Modification with (S)-2-phenyl-1,3-dithiane 1-oxide gives a catalyst for which (R)-butan-2-ol is the most reactive of the two enantiomers. Reaction of racemic butan-2-ol over these chirally modified H-Y zeolites demonstrates that this modification procedure makes the zeolite enantiomerically discriminating and one enantiomer preferentially reacts, although both are present in the micropores under the reaction conditions. This effect is considered to be due to enantioselective rate enhancement, since, although the rate of dehydration of both enantiomers is enhanced in the chiral environment, the dehydration rate of one enantiomer is accelerated relative to the other. It is suggested that the effect is due to preferential adsorption at the chiral active site. (C) 1997 Academic Press.

KW - asymmetric catalyst

KW - hydrogenation

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DO - 10.1006/jcat.1997.1576

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VL - 167

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EP - 542

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

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ER -