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Quantitative determination with periodate of compounds subject to non-Malapradian oxidation Part IV. 2-ketoses
CmaOhydrnrc Research
441
Ekcvier Publishing Ccmpany,Amsterdam Prinkd in Belgium
Note
Quantitative determination with periodate of compounds non-Malapradian oxidation Part IV’. 2-Ketoses
subject to
S. ROBERT SARFATI AND PATRICIA SZAB~ Institut de Biochimie, Facuk! des Sciences,
9Z Orsay (France)
(Received October 6th, 1969)
It has long been known that, in the conditions usually employed, hex-2-uloses show fractional consumption of periodate z-g. It has been shown9 that this is due to the fact that these sugars are oxidised by two different routes to give products which behave differently towards periodate. Cleavage of a 2-ketose between C-l and C-2 leads to the formation of glyoxylic acid which is further oxidised6***‘**’ r by one equivalent of periodate, whereas cleavage between C-2 and C-3 gives glycolic acid which is practically unaffected by periodate l2 . Thus, the amount of periodate reduced by a hexulose varies between four and five molar equivalents, depending on the proportions of the sugar oxidised by each route. It has also been reported’ that three hept-2-uloses (D-gZUco-, D-manno-, and L-galacto-) are likewise oxidised by the two pathways, reducing between five and six molar equivalents of periodate; it was noted’ that less glycolic acid was formed from these sugars than from the hexuloses. To our knowledge, the periodate oxidation of octuloses has not been studied. It is evident that 2-ketoses should reduce a whole number of equivalents of periodate if oxidised in conditions where neither glyoxylic nor glycolic acids are attacked by the oxidant. It has been shown’ 3 that glyoxylic acid is not oxidised by periodate in 0.1~ sulphuric acid at 0” (“cold acid” method14); it has now been established that the same is true for glycolic acid. A number of 2-ketoses were therefore oxidised in these conditions; as would be expected, the hexuloses reduced exactly four, the heptuloses five, and the octuloses six molar equivalents of periodate (Table I). In each case, the relative importance of each of the two pathways in the oxidation of the sugar was assessed by determination of the amounts of formaldehyde, glyoxylic acid, and glycolic acid formed (Table I). It is interesting to note that no glycolic acid could be detected in the oxidation o-) and of one of mixtures of three of the five heptuloses (D- and L-gluco- and D-m the two octuloses (D-g&zero-L-gZuco-) studied. That no cleavage had occurred between C-2 and C-3 in these compounds was confirmed by the fact that, in each case, two molar equivalents of formaldehyde and one of glyoxylic acid were found amongst the reaction products (these results differ from those previously reported’ for D-gZucoand D-manno-heptuloses). None of these compounds show mutarotation; they must Curbofzyd. Res., 13 (1970).441443
442 TABLE
NOTE I
PERIODATE
OXIDATION
OF 24JLOSEs
2-Ketose
Molar IO4
D-Fructose r-Sorbose D-Tagatose D-manno-Heptulose D-ghco-Heptulose L-glum-Heptulose r_-allo-Heptulose L-galacto-Heptulose D-giycera-L-ghco-&tulose D-g]yCerO-D-gUfO-OCtUlOSe
equivalents of reduced
3.97 3.98 3.97 4.99 4.85 4.86 4.84 4.85 5.88 5.96
Formaldehyde formed
GZyoxyiic acid formed
GIycoIic acid formed
1.54 1.66 1.79 2.02 1.92 1.97 1.63 1.75 1.98 1.77
0.51 0.71
0.53 0.31 0.20 0 0 0 0.36 0.25 0 0.21
therefore be oxidised in a given conformation. that D-gZz&zu-heptulose exists in the a-pyranoid 1;it can be expected that D-manno-heptulose morphous with r_.-gluco-heptulose 2) will also ZC (D) conformations (3 and 4, respectively).
1
2
0.99 0.97 1.04 0.62 0.80 1.00 0.84
It has been shown by n.m.r. studies l5 form and has the CZ (D) conformation and D-glycero-L-g&o-octulose (bomoexist as a-pyranoses in the CZ (D) and
3
It is not unexpected that preferential cleavage of the bond between C-l and C-2 should occur in structures 1-4;the truns diaxial relationship of the hydroxyl groups on C-2 and C-3 of D-manno-heptulose is known to be unfavorable for rapid glycol cleavage, and for D- and L-g&o-heptuloses and D-glycero-L-gluco-octmose it is reasonable to find that the vicinal diol having an exocyclic primary hydroxyl group should be cleaved first. On the other hand, L-allo-heptulose, which is reported to show no mutarotation, gives some glycolic acid on periodate oxidation. This heptulose most likely exists in the conformation 5 having the same steric arrangement about C-l, C-2, and C-3 as has L-gluco-heptulose. The absence of exclusive cleavage between Carbohyd. Res., 13 (1970) 441-443
NOTE
443
C-l and C-2 is probably due to the known destabilising effect of 1,3-diaxial hydroxyl groups (C-2 and C-4). The hexuloses, the fifth heptulose (L-galacro-heptulose), and the second octulose all show mutarotation. This takes pIace more rapidly than does the reaction of glycol cleavage, so that it is not possible to draw any conclusions as to the form or forms in which these sugars are oxidised. ExPERlMENTAL
Periodat;_ oxidations were carried out at 0” in 0.1~ sulphuric acid (0.6m~ in substrate and 6.6m~ in sodium periodate) as described previously’4. The 2-ketose to be oxidised was dissolved in 0.1~ sulphuric acid at 0” for 48 to 72 h before the addition of periodate, in order to allow mutarotation to go to completion. Formaldehyde was determined with chromotropic acid’ 62 glyoxylic acid with periodate13, and glycolic acid with 2,7_dihydroxynaphthalene “. No reduction of periodate by glycolic acid could be detected either in the conditions described above or when the pH of the oxidation mixture was adjusted to 5 with sodium acetate, and the solution was kept at room temperature. ACKNO\VLEDGMENTS We thank Dr. Nelson K. Richtmyer for gifts of D-gZuco-, L-gZuco-, L-allo-, and Llgaiacto-heptuloses and of D-g&zero-D-gzrlo- and D-g&zero-L-gluco-octuloses (the latter, described in the literature’*.l’ as a syrup, has now been obtained in crystalline form by Dr. Richtmyer”), and Dr. H. H. Haas for D-tagatose. REFERENCES 1 Part III: S. R. SARFATI AND P. SZAB~, Carbohyd. Res., 11 (1969) 571. 2 P. FLEURY AND J. LANGE, Compt. Rend., 195 (1932) 1395; J. Phurm. Chim., [8] 17 (1933) 409. 3 L. MALAPRADE, Bull. Sot. Chim. France, [5j 1 (1934) 833. 4 F. RAPPOPORT AND I. REIFER, Mikrochim. Acta, 2 (1937) 273. 5 Y. KHOlJVINE AND G. ARRAGON, Compt. Rend., 212 (1941) 167; Bull. Sot. Chim. France, [5J 8
(1941) 676. 6 D. B. SPRINSON AND E. CHARGAFF, J. Biol. Chem., 164 (1946) 433. 7 P. C. ARNI AND E. G. V. PERCIVAL, J. Chem. Sot., (1951) 1822. 8 L. HCXJGH, T. J. TAYLOR, G. H. S. THOMAS, AND B. M. WOODS, J. Chem. Sot., (1958) 1212. 9 P. FLEIJRY, J. E. COURTOIS, AND L. LE DIZET, Compt. Rend., 248 (1959) 235; Bull. Sot. Chim. France, (1959) 1664. 10 P. FLEURY AND G. BON-BERNATETS,J. Pharm. Chim., [8] 23 (1936) 85. 11 C. F. HUEBNER, S. R. Ahm, AND E. C. BUBL, J. Amer. Chem. Sot., 68 (1946) 1621. Y, L. HOUGH, AND A. 0. PI-~-I-ET,Chem. Ind. (London), (1959) 1126. 12 M. C13 J. P. GIRMA, M. T. ROKICKA, AND P. SZAB~), J. Chem. Sot. (C), (1969) 909. 14 P. SZAB~ AND L. SZAB~, Carbohyd. Res., 4 (1967) 206. 15 J. C. JOCHIMS,G. TAIGEL, A. SEELIGER,P. LUTZ, em H. E. DRIESEN, Tetrahedron Lett., (1967) 4363. 16 J. C. SPECK, JR., Methods Carbohyd. Chem., 1 (1962) 441. 17 S. R. SARFATIAKD P. SZAB~, Carbohyd. Res., 12 (1970) 290. 18 M. L. WOLFROM urn P. W. COOPER, J. Amer. Chem. Sot., 71 (1949) 2668. 19 J. K. N. JONESAND H. H. SEPHTON, Can. J. Chem., 38 (1960) 753. 20 N. K. RICHTMYER, personal communication. Carhohyd. Res., 13 (1970) 441-443
441
Ekcvier Publishing Ccmpany,Amsterdam Prinkd in Belgium
Note
Quantitative determination with periodate of compounds non-Malapradian oxidation Part IV’. 2-Ketoses
subject to
S. ROBERT SARFATI AND PATRICIA SZAB~ Institut de Biochimie, Facuk! des Sciences,
9Z Orsay (France)
(Received October 6th, 1969)
It has long been known that, in the conditions usually employed, hex-2-uloses show fractional consumption of periodate z-g. It has been shown9 that this is due to the fact that these sugars are oxidised by two different routes to give products which behave differently towards periodate. Cleavage of a 2-ketose between C-l and C-2 leads to the formation of glyoxylic acid which is further oxidised6***‘**’ r by one equivalent of periodate, whereas cleavage between C-2 and C-3 gives glycolic acid which is practically unaffected by periodate l2 . Thus, the amount of periodate reduced by a hexulose varies between four and five molar equivalents, depending on the proportions of the sugar oxidised by each route. It has also been reported’ that three hept-2-uloses (D-gZUco-, D-manno-, and L-galacto-) are likewise oxidised by the two pathways, reducing between five and six molar equivalents of periodate; it was noted’ that less glycolic acid was formed from these sugars than from the hexuloses. To our knowledge, the periodate oxidation of octuloses has not been studied. It is evident that 2-ketoses should reduce a whole number of equivalents of periodate if oxidised in conditions where neither glyoxylic nor glycolic acids are attacked by the oxidant. It has been shown’ 3 that glyoxylic acid is not oxidised by periodate in 0.1~ sulphuric acid at 0” (“cold acid” method14); it has now been established that the same is true for glycolic acid. A number of 2-ketoses were therefore oxidised in these conditions; as would be expected, the hexuloses reduced exactly four, the heptuloses five, and the octuloses six molar equivalents of periodate (Table I). In each case, the relative importance of each of the two pathways in the oxidation of the sugar was assessed by determination of the amounts of formaldehyde, glyoxylic acid, and glycolic acid formed (Table I). It is interesting to note that no glycolic acid could be detected in the oxidation o-) and of one of mixtures of three of the five heptuloses (D- and L-gluco- and D-m the two octuloses (D-g&zero-L-gZuco-) studied. That no cleavage had occurred between C-2 and C-3 in these compounds was confirmed by the fact that, in each case, two molar equivalents of formaldehyde and one of glyoxylic acid were found amongst the reaction products (these results differ from those previously reported’ for D-gZucoand D-manno-heptuloses). None of these compounds show mutarotation; they must Curbofzyd. Res., 13 (1970).441443
442 TABLE
NOTE I
PERIODATE
OXIDATION
OF 24JLOSEs
2-Ketose
Molar IO4
D-Fructose r-Sorbose D-Tagatose D-manno-Heptulose D-ghco-Heptulose L-glum-Heptulose r_-allo-Heptulose L-galacto-Heptulose D-giycera-L-ghco-&tulose D-g]yCerO-D-gUfO-OCtUlOSe
equivalents of reduced
3.97 3.98 3.97 4.99 4.85 4.86 4.84 4.85 5.88 5.96
Formaldehyde formed
GZyoxyiic acid formed
GIycoIic acid formed
1.54 1.66 1.79 2.02 1.92 1.97 1.63 1.75 1.98 1.77
0.51 0.71
0.53 0.31 0.20 0 0 0 0.36 0.25 0 0.21
therefore be oxidised in a given conformation. that D-gZz&zu-heptulose exists in the a-pyranoid 1;it can be expected that D-manno-heptulose morphous with r_.-gluco-heptulose 2) will also ZC (D) conformations (3 and 4, respectively).
1
2
0.99 0.97 1.04 0.62 0.80 1.00 0.84
It has been shown by n.m.r. studies l5 form and has the CZ (D) conformation and D-glycero-L-g&o-octulose (bomoexist as a-pyranoses in the CZ (D) and
3
It is not unexpected that preferential cleavage of the bond between C-l and C-2 should occur in structures 1-4;the truns diaxial relationship of the hydroxyl groups on C-2 and C-3 of D-manno-heptulose is known to be unfavorable for rapid glycol cleavage, and for D- and L-g&o-heptuloses and D-glycero-L-gluco-octmose it is reasonable to find that the vicinal diol having an exocyclic primary hydroxyl group should be cleaved first. On the other hand, L-allo-heptulose, which is reported to show no mutarotation, gives some glycolic acid on periodate oxidation. This heptulose most likely exists in the conformation 5 having the same steric arrangement about C-l, C-2, and C-3 as has L-gluco-heptulose. The absence of exclusive cleavage between Carbohyd. Res., 13 (1970) 441-443
NOTE
443
C-l and C-2 is probably due to the known destabilising effect of 1,3-diaxial hydroxyl groups (C-2 and C-4). The hexuloses, the fifth heptulose (L-galacro-heptulose), and the second octulose all show mutarotation. This takes pIace more rapidly than does the reaction of glycol cleavage, so that it is not possible to draw any conclusions as to the form or forms in which these sugars are oxidised. ExPERlMENTAL
Periodat;_ oxidations were carried out at 0” in 0.1~ sulphuric acid (0.6m~ in substrate and 6.6m~ in sodium periodate) as described previously’4. The 2-ketose to be oxidised was dissolved in 0.1~ sulphuric acid at 0” for 48 to 72 h before the addition of periodate, in order to allow mutarotation to go to completion. Formaldehyde was determined with chromotropic acid’ 62 glyoxylic acid with periodate13, and glycolic acid with 2,7_dihydroxynaphthalene “. No reduction of periodate by glycolic acid could be detected either in the conditions described above or when the pH of the oxidation mixture was adjusted to 5 with sodium acetate, and the solution was kept at room temperature. ACKNO\VLEDGMENTS We thank Dr. Nelson K. Richtmyer for gifts of D-gZuco-, L-gZuco-, L-allo-, and Llgaiacto-heptuloses and of D-g&zero-D-gzrlo- and D-g&zero-L-gluco-octuloses (the latter, described in the literature’*.l’ as a syrup, has now been obtained in crystalline form by Dr. Richtmyer”), and Dr. H. H. Haas for D-tagatose. REFERENCES 1 Part III: S. R. SARFATI AND P. SZAB~, Carbohyd. Res., 11 (1969) 571. 2 P. FLEURY AND J. LANGE, Compt. Rend., 195 (1932) 1395; J. Phurm. Chim., [8] 17 (1933) 409. 3 L. MALAPRADE, Bull. Sot. Chim. France, [5j 1 (1934) 833. 4 F. RAPPOPORT AND I. REIFER, Mikrochim. Acta, 2 (1937) 273. 5 Y. KHOlJVINE AND G. ARRAGON, Compt. Rend., 212 (1941) 167; Bull. Sot. Chim. France, [5J 8
(1941) 676. 6 D. B. SPRINSON AND E. CHARGAFF, J. Biol. Chem., 164 (1946) 433. 7 P. C. ARNI AND E. G. V. PERCIVAL, J. Chem. Sot., (1951) 1822. 8 L. HCXJGH, T. J. TAYLOR, G. H. S. THOMAS, AND B. M. WOODS, J. Chem. Sot., (1958) 1212. 9 P. FLEIJRY, J. E. COURTOIS, AND L. LE DIZET, Compt. Rend., 248 (1959) 235; Bull. Sot. Chim. France, (1959) 1664. 10 P. FLEURY AND G. BON-BERNATETS,J. Pharm. Chim., [8] 23 (1936) 85. 11 C. F. HUEBNER, S. R. Ahm, AND E. C. BUBL, J. Amer. Chem. Sot., 68 (1946) 1621. Y, L. HOUGH, AND A. 0. PI-~-I-ET,Chem. Ind. (London), (1959) 1126. 12 M. C13 J. P. GIRMA, M. T. ROKICKA, AND P. SZAB~), J. Chem. Sot. (C), (1969) 909. 14 P. SZAB~ AND L. SZAB~, Carbohyd. Res., 4 (1967) 206. 15 J. C. JOCHIMS,G. TAIGEL, A. SEELIGER,P. LUTZ, em H. E. DRIESEN, Tetrahedron Lett., (1967) 4363. 16 J. C. SPECK, JR., Methods Carbohyd. Chem., 1 (1962) 441. 17 S. R. SARFATIAKD P. SZAB~, Carbohyd. Res., 12 (1970) 290. 18 M. L. WOLFROM urn P. W. COOPER, J. Amer. Chem. Sot., 71 (1949) 2668. 19 J. K. N. JONESAND H. H. SEPHTON, Can. J. Chem., 38 (1960) 753. 20 N. K. RICHTMYER, personal communication. Carhohyd. Res., 13 (1970) 441-443