Helvetica Chimica Acta published new progress about 13312-84-0. 13312-84-0 belongs to nitriles-buliding-blocks, auxiliary class Chloride,Nitrile,Benzene,Alcohol,Benzene Compounds, name is 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, and the molecular formula is C8H6ClNO, Recommanded Product: 2-(2-Chlorophenyl)-2-hydroxyacetonitrile.
Karrer, P. published the artcileGlucosides. IX, Recommanded Product: 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, the publication is Helvetica Chimica Acta (1921), 130-48, database is CAplus.
K has shown (C. A. 13, 1841; 14, 742, 1972) that BrC6H7O5Ac4 (A) reacts with the Ag salts of α- or o-HO and o-NH2 acids to form both acetylated glucosides and glucose esters, indicating that the Ag is bound to both the CO2H and the OH or NH2 groups by principal and secondary valences. On this assumption, m- and p-HOC6H4CO2Ag should yield tetraacetylglucose esters but no glucoside, since the more distant OH groups would exercize no appreciable effect on the Ag atom. By boiling 25 g. of p-HOC6H4CO2Ag with 41 g. of A in 200 cc. of C7H8 for 1.5 mins. and filtering while hot tetracetylglucose p-hydroxybenzoate crystallized from the filtrate on cooling, m. 197°, [α]D20 -29.76°. On extracting the filtrate with dilute NH3 and acidifying, a white crystalline precipitate was formed, identical with the above compound No glucoside was found. Similarly, tetraacetylglucose m-hydroxybenzoate was prepared, white needles from EtOH, m. 147°, [α]D20 -26.61°. The combination between Ag and S in HSCH2CO2Ag was apparently too firm, as no reaction with A took place. Instead of using the Ag salt, 17 g. of A in 25 cc. of absolute MeOH were mixed with 2 g. of K in 25 cc. of MeOH, to which 7 g. of HSCH2CO2Et had been added. KBr was precipitated and removed after 2 hrs. and the filtrate evaporated in vacuo at 30-40° to remove MeOH. The resinous residue was digested with Ac2O and AcONa to restore any Ac group split off, treated with cold H2O to destroy Ac2O, dissolved in Et2O, the solution evaporated, and the crude product extracted with hot H2O. On cooling, long needles of ethyl β-tetraacetyl-d-glucosidoothioglycolate formed, soluble in EtOH, Et2O, C6H6, m. 63°, [α]D15 -58.52°. Saturated Ba(OH)2 converted it into β-d-glucosidothioglycolic acid, m. 148-50°, [α]D -66.19°. From 20 g. of 2,5-HO(MeO)C6H3CO2Ag and 30 g. of A in 250 cc. of boiling C7H8, AgBr was precipitated and removed, and the C7H8 solution extracted repeatedly with 50-cc. portions of 1:40 NH3. The latter was acidified with HCl, after filtering, giving a white crystalline precipitate of β-tetracetyl-d-glucosido-5-methoxygentisinic acid (B), needles from EtOH, m. 172-4°, [α]D20 -32.13°. From the C7H8 after the NH3 extractions tetracetylglucose 5-methoxygentisinate crystallized on evaporation, needles from EtOH, m. 163°, [α]D20 -40.2°. Cold saturated Ba(OH)2 saponified B of β-d-glucosido-5-methoxygentisinic acid (C), fine needles from EtOH, m. 166°, [α]D20 -39.62°, easily soluble in H2O, insoluble in Et2O. Methyl ester of C, by the action of CH2N2 in Et2O on C in concentrated EtOH solution, m. 83°, [α]D20 -48.52°. The above method applied to 13 g. of Ag p-methylmandelate and 25 g. of A in 125 g. of C7H8 gave 16 g. of dl-tetraacetylglucose p-methylmandelate, snow-white needles, m. 155°, while the NH3 extractions yielded 5 g. of β-d-tetraacetylglucosido-p-methylmandelic acid, small felt-like needles, m. 149-50°. By the action of KCN and concentrated HCl on 50 g. of o-ClC6H4CHO at 0°, 55 g. of o-chlorobenzaldehyde cyanohydrin were obtained, and converted into o-chloromandelic acid by saponifying with concentrated HCl. Unchanged aldehyde was separated by extracting the crude product with 10% NaOH, acidifying and crystallizing the acid from C6H6, the yield being 18 g., m. 84-5°. The acid was dissolved in EtOH, treated with the equivalent amount of AgNO3 in H2O, and NH4OH added from a buret, giving silver o-chloromandelate. From 15.6 g. of the latter, rubbed in a mortar with A and heated with 100 cc. of C7H8, AgBr was precipitated and removed, and the C7H8 solution extracted with 0.5% NH4OH as above, etc., giving β-d-tetraacetylglucosido-o-chloromandelic acid, small white needles from dilute EtOH, m. 182°. Similarly, 8 g. of Ag orsellinate with the equivalent amount of A gave tetraacetylglucose orsellinate, m. 153°, [α]D18 -41.75°. Ag quinolcarboxylate (Ag gentisinate) and A yielded tetraacetylglucose quinolcarboxylate, white needles from EtOH, m. 185°, [α]18 -39.82°. Five g. of Ag mandelate and 13.5 g. of acetobromomaltose in 100 cc. of boiling C7H8 gave a small yield of heptaacetylmaltosido-dl-mondelic acid, which could not be obtained crystalline, m. 65-85°, insoluble in H2O, easily soluble in EtOH. Polarization in CHCl3 gave varying results, [α]D 9-35°. This compound agrees rather closely with acetylamygdalic acid in m. p. and [α], but is entirely different from acetylcellosidomandelic acid, which is crystalline, m., 179-82°, [α]D -44°. These facts furnish additional evidence that the sugar of amygdalin is not a cellobiose, but is probably maltose or isomaltose. A study of the influence of various salts, etc., on the rotation of glucosides showed that in 2% solution salicin was affected by H3BO3, Na2B4O7 and NaOH, but not by NaCl, KCl, KHC2O4, KNO3, CaCl2, or H2C2O4. Amygdalin was affected by Na2B4O7, which caused mutarotation, and by NaOH. Menthyl α-glucoside was not affected by any of the above in 0.5% EtOH solution or in 0.5% glycerol solution
Helvetica Chimica Acta published new progress about 13312-84-0. 13312-84-0 belongs to nitriles-buliding-blocks, auxiliary class Chloride,Nitrile,Benzene,Alcohol,Benzene Compounds, name is 2-(2-Chlorophenyl)-2-hydroxyacetonitrile, and the molecular formula is C8H6ClNO, Recommanded Product: 2-(2-Chlorophenyl)-2-hydroxyacetonitrile.
Referemce:
https://en.wikipedia.org/wiki/Nitrile,
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