من در مورد شرایط حضور فرم فورانوز برای گلوکز چیزی نخونده بودم

گفتم که این تست رو از خودم درآوردم و طبیعیه که استاندارد نباشه زیاد ولی خوب میشه شرایط حضور فرم فورانوزی رو بگید؟ آخه واسه حملۀ نوکلئوفیلی اکسیژن کربن پنجم و چهارم رقابت می کنند که به دلیل ممانعت فضایی تعادل به مقدار خیلی زیادی بسوی فرم پیرانوز میره. این شرایطی که میگین شانس تشکیل فرم فورانوز رو بالا میبره چیه؟
دلیلش پدیده ایه به اسم gauche effect.
In solutions, the open-chain form of glucose (either "D-" or "L-") exists in equilibrium with several cyclic isomers, each containing a ring of carbons closed by one oxygen atom. In aqueous solution however,
more than 99% of glucose molecules, at any given time, exist as pyranose.
The open-chain form is limited to about 0.25% and
furanose exists in negligible amounts. The terms "glucose" and "D-glucose" are generally used for these cyclic forms as well. The ring arises from the open-chain form by a nucleophilic addition reaction between the aldehyde group -(C=O)H at C-1 and the hydroxyl group -OH at C-4 or C-5, yielding a hemiacetal group -C(OH)H-O-.
The reaction between C-1 and C-5 creates a molecule with a six-membered ring, called pyranose, after the cyclic ether pyran, the simplest molecule with the same carbon-oxygen ring. The (much rarer) reaction between C-1 and C-4 creates a molecule with a five-membered ring, called furanose, after the cyclic ether furan. In either case, each carbon in the ring has one hydrogen and one hydroxyl attached, except for the last carbon (C-4 or C-5) where the hydroxyl is replaced by the remainder of the open molecule (which is -(CHOH)2-H or -(CHOH)-H, respectively).
The ring-closing reaction makes carbon C-1 chiral, too, since its four bonds lead to -H, to -OH, to carbon C-2, and to the ring oxygen. These four parts of the molecule may be arranged around C-1 (the anomeric carbon) in two distinct ways, designated by the prefixes "α-" and "β-". When a glucopyranose molecule is drawn in the Haworth projection, the designation "α-" means that the hydroxyl group attached to C-1 and the -CH2OH group at C-5 lies on opposite sides of the ring's plane (a trans arrangement), while "β-" means that they are on the same side of the plane (a cis arrangement).
Therefore, the open isomer D-glucose gives rise to four distinct cyclic isomers: α-D-glucopyranose, β-D-glucopyranose, α-D-glucofuranose, and β-D-glucofuranose; which are all chiral.
GlucopyranoseThe other open-chain isomer L-glucose similarly gives rise to four distinct cyclic forms of L-glucose, each the mirror image of the corresponding D-glucose.
The rings are not planar but twisted in three dimensions. The glucopyranose ring (α or β) can assume several non-planar shapes, analogous to the "chair" and "boat" conformations of cyclohexane. Similarly, the glucofuranose ring may assume several shapes, analogous to the "envelope" conformations of cyclopentane.
The glucopyranose forms of glucose predominate in solution, and are the only forms observed in the solid state. They are crystalline colorless solids, highly soluble in water and acetic acid, poorly soluble in methanol and ethanol. They melt at 146 °C (295 °F) (α) and 150 °C (302 °F) (β), and decompose at higher temperatures into carbon and water.
Rotational isomersEach glucose isomer is subject to rotational isomerism. Within the cyclic form of glucose, rotation may occur around the O6-C6-C5-O5 torsion angle, termed the ω-angle, to form three staggered rotamer conformations called gauche-gauche (gg), gauche-trans (gt) and trans-gauche (tg). For methyl α-D-glucopyranose at equilibrium the ratio of molecules in each rotamer conformation is reported as 57:38:5 gg:gt:tg.[13] This tendency for the ω-angle to prefer to adopt a gauche conformation is attributed to the
gauche effect.
رفرنس:
1- Kirschner, Karl N.; Woods, Robert J. (2001), "Solvent interactions determine carbohydrate conformation", Proc. Natl. Acad. Sci. USA 98 (19): 10541–45
2- McMurry, John E. (1988), Organic Chemistry (2nd ed.), Brooks/Cole, p. 866, ISBN 0534079687
3- Juaristi, Eusebio; Cuevas, Gabriel (1995), The Anomeric Effect, CRC Press, pp. 9–10, ISBN 0-8493-8941-0
4- Fred W. Schenck “Glucose and Glucose-Containing Syrups” in Ullmann's Encyclopedia of Industrial Chemistry 2006, Wiley-VCH, Weinheim. doi: 10.1002/14356007.a12_457.pub2