|
|
| | 1,2:5,6-Bis-O-(1-methylethylidene)-D-mannitol Basic information | | Synthesis |
| Product Name: | 1,2:5,6-Bis-O-(1-methylethylidene)-D-mannitol | | Synonyms: | DIACETONE-D-MAN;1,2:5,6-ISOPROPYLIDENE-D-MANNITOL;1,2:5,6-bis-o-(1-methylethylidene)-d-mannitol;1,2:5,6-BIS-O-(1-METHYLETHYLIDENE)-D-MARNITOL;1,2-bis(2,2-dimethyl-1,3-dioxolan-4-yl)-1,2-ethanediol;1,2:5,6-Bis-O-(1-met;1,2,5,6-Di-O-isopropylidene-D-mannitol ,98%;1,2:5,6-Di-O-isopropylidene-D-maitol | | CAS: | 1707-77-3 | | MF: | C12H22O6 | | MW: | 262.3 | | EINECS: | 216-954-8 | | Product Categories: | Liver Disease Series;Chiral Reagents;Intermediates & Fine Chemicals;Pharmaceuticals;Carbohydrates;Biochemistry;Dioxanes & Dioxolanes;Dioxolanes;O-Substituted Sugars;Sugar Alcohols;Sugars;Glycon Biochem | | Mol File: | 1707-77-3.mol |  |
| | 1,2:5,6-Bis-O-(1-methylethylidene)-D-mannitol Chemical Properties |
| Melting point | 120-122 °C(lit.) | | alpha | 6 º (c=5, Chloroform) | | Boiling point | 382.0±32.0 °C(Predicted) | | density | 1.175±0.06 g/cm3(Predicted) | | refractive index | 6.5 ° (C=8, CHCl3) | | storage temp. | Keep in dark place,Sealed in dry,Room Temperature | | solubility | methanol: 100 mg/mL, clear, colorless | | form | Crystalline Powder | | pka | 12.98±0.20(Predicted) | | color | White | | Optical Rotation | [α]/D +6.0±1.0°, c = 5 in chloroform | | BRN | 83765 | | InChI | 1S/C12H22O6/c1-11(2)15-5-7(17-11)9(13)10(14)8-6-16-12(3,4)18-8/h7-10,13-14H,5-6H2,1-4H3/t7-,8-,9-,10-/m1/s1 | | InChIKey | ODYBCPSCYHAGHA-ZYUZMQFOSA-N | | SMILES | CC1(C)OC[C@@H](O1)[C@@H](O)[C@H](O)[C@H]2COC(C)(C)O2 | | CAS DataBase Reference | 1707-77-3(CAS DataBase Reference) | | NIST Chemistry Reference | D-Mannitol, 1,2:5,6-bis-o-(1-methylethylidene)-(1707-77-3) |
| | 1,2:5,6-Bis-O-(1-methylethylidene)-D-mannitol Usage And Synthesis |
| Synthesis | The unsaturated ester 20 d-mannitol (19) (20 g, 0.11 mol) was added to a stirred solution of molten zinc chloride (30 g, 0.22 mol) in dry acetone (200 mL). Stirring continued until the d-mannitol was completely dissolved (22 hours). The reaction mixture was then poured into a stirred and cooled aqueous solution of K₂CO₃ (30 g, 0.22 mol) (320 mL). The precipitate was removed by filtration and thoroughly washed with DCM (200 mL). The aqueous filtrate was evaporated to remove acetone, and the extract was extracted with DCM (3 x 200 mL). The organic washes and extract were washed with cold water (100 mL), dried with MgSO₄, evaporated to a solid residue, and recrystallized to give diacetone-D-mannitol 19A as a white needle (18.3 g, 60%). 
A solution of acetal 6a (210 mg, 0.57 mmol) in pyrrolidine (8 mL) was heated to 90°C for 48 hours. After solvent removal, the residue was purified by “rapid” column chromatography (hexane-EtOAc) to give 1,2:5,6-Bis-O-(1-methylethylidene)-D-mannitol (129 mg, 91%, 94%). | | Chemical Properties | White Solid | | Uses | Nebivolol intermediate. | | Purification Methods | Although quite soluble in H2O, it gives a purer product when crystallised from this solvent, forming needles [Baer J Am Chem Soc 67 338 1945, NMR: Curtis et al. J Chem Soc, Perkin Trans 1 1756 1977]. [Beilstein 19/11 V 589.] |
| | 1,2:5,6-Bis-O-(1-methylethylidene)-D-mannitol Preparation Products And Raw materials |
| Raw materials | D-Mannitol, 1,2:5,6-bis-O-(1-methylethylidene)-, diacetate (9CI)-->2-Methoxypropene-->Acetone-->2,2-Dimethoxypropane-->D-Mannitol | | Preparation Products | (R)-(-)-2,2-Dimethyl-1,3-dioxolane-4-methanol-->(S)-(+)-(2,2-DIMETHYL-[1,3]-DIOXOLAN-4-YL)-METHYLAMINE-->(S)-4-BENZYLOXYMETHYL-2,2-DIMETHYL-1,3-DIOXOLANE-->D-Glyceraldehyde-->(S)-4,5-ISOPROPYLIDENE-2-PENTENYLBROMIDE |
|