Adams, A. published the artcileThiazoles derived from chrysean and isochrysean, HPLC of Formula: 101012-16-2, the publication is Journal of the Chemical Society (1956), 1870-7, database is CAplus.
Throughout this abstract, R is the thiazole nucleus. A solution of 25 kg. NaCN in 57 l. H2O and 1 l. aqueous NH3 (d. 0.88) was circulated through a 5′ × 6″ Pyrex tower packed with 1” Raschig rings, and treated with 15-16 kg. H2S over 6 hrs. The H2O-washed product was dried at 100° and crystallized from a mixture of 25 l. H2O, 3.15 l. HOAc and 100 g. C, giving 920 g. chrysean, 2,5-H2NSCRNH2 (I), m. 215-16° (after further crystallization from N HOAc). The mother liquor was adjusted to pH 6 with NH3, concentrated, and the crude residue H2O-washed, giving 20.7 g. isochrysean, 4,5-H2NSCRNH2 (II), m. 131-50°. Further treatment of the filtrates gave an addnl. 106.7 g. crude II. Passing a sample through an alumina column gave pure II, m. 155° (from EtOH). Treating 1 g. I in 4 cc. C5H5N with 0.55 g. AcCl at 0-5° gave 0.8 g. Ac derivative, m. 250° (decomposition) (yellow needles from 2N HOAc). Similarly, 2,5-NCRNH2 (III) (cf. C.A. 38, 36286) with BzCl gave the Bz derivative, m. 211-12° (from EtOH); this was hydrolyzed by boiling 3 hrs. with 20% aqueous NaOH and acidifying the cold solution, giving 2,5-HO2CRNHBz, m. 159°. PhCl was slowly distilled during 1 hr. from a mixture of 1 g. III, 1.4 g. o-C6H4(CO)2O (IV), and 20 cc. PhCl, fresh solvent being added as needed. The product was washed with PhCl and dried giving 5,2-o-HO2CC6H4CONHRCN (V), m. 253° (pale yellow, from MeOH), also m. 210° (decomposition) when placed in a pre-heated bath. Boiling V 1 hr. with aqueous NaOH gave 5,2-o-HO2CC6H4CONHRCO2H (VI), m. 154° (decomposition) (from dilute aqueous HCl). Boiling 1 g. VI with 15 cc. HOAc for 1 hr. gave 0.5 g. 5-o-C6H4(CO)2NR, m. 147° (from aqueous HOAc). Boiling 10 g. III and 16.5 g. powdered IV 6 hrs. in 150 cc. HOAc gave 18.4 g. 5,2-o-C6H4(CO)2NRCN (VII), m. 255-6° (orange needles, from HOAc). A stirred suspension of 50 g. VII in 825 cc. dry CHCl3 and 20 g. dry EtOH was saturated at 0-5° with dry HCl and kept at 0° for 5 days. The resulting precipitate and 2 l. H2O were heated on a steam bath 1 hr., giving 5,2-o-C6H4(CO)2NRCO2Et (VIII), m. 171° (pale yellow needles, from naphtha, b. 80-100°, and EtOH alternately) and unchanged VII. Stirring 90 cc. 100% N2H4.H2O into a suspension of 58 g. VIII in 850 cc. EtOH, filtering the solution, letting it stand overnight, removing the solid, dissolving it in 2N NaOH, acidifying the solution, removing the precipitate, neutralizing the filtrate and concentrating it, and combining the resulting solid with the solid obtained by concentrating the original reaction filtrate, gave a total of 20 g. 5,2-H2NRCONHNH2, m. 190° (from H2O, then from EtOH). When only 2 moles of N2H4 were used instead of an excess, the product was 5,2-H2NRCO2Et, m. 118° (cream-colored needles, from H2O). 5,2-o-C6H4(CO)2NRCO2Bu (IX), m. 167-9° (pale yellow needles, alternately from ligroine and EtOH) was prepared in 54% yield in the same manner as VIII and was converted to 5,2-H2NRCO2Bu, m. 81-2° (from 2N HOAc, 69% yield). Hydrolysis of 2,5-NCRNHAc with dry HCl in EtOH-CHCl3 gave 2,5-EtO2CRNHAc (X), m. 191-2° (from H2O); similarly was prepared 2,5-MeO2CRNHAc, m. 216-17° (82% yield). Heating X with 100% N2H4.H2O in EtOH 15 min. at 100°, then letting the mixture stand overnight gave 2,5-H2NHNOCRNHAc, m. 286° (decomposition) (from EtOH). Diazotizing III in the presence of freshly precipitated CuCl gave 2,5-NCRCl (XI), m. 50° (from naphtha, b. 60-80°), accompanied by 2,5-H2NOCRCl (XII), m. 189-91° (from EtOH). XI was converted into XII, m. 193°, by hydrolysis with dry HCl in CHCl3-EtOH. Boiling XI 1 hr. in 2N NaOH gave 2,5-HO2CRCl (XIII), m. 111-12°, purified by dissolving the sample in 2N NaOH, clarifying with C, and repptg. the free acid with 2N HCl. Treatment of XIII with CH2N2 gave the Me ester, m. 53° (from naphtha, b. 40-60°), which upon treatment with N2H4.H2O gave 2,5-H2NHNOCRCl, m. 197° (from EtOH). Mixing 1 g. XI with 2 cc. N2H4.H2O and letting the mixture stand 2 hrs. gave 1.12 g. 5,2-ClRC(:NH)NHNH2, m. 148° (decomposition) (pale yellow needles from EtOH), resolidifying and remelting at about 220°. Refluxing 5,2-p-AcNHC6H4SO2NHRCSNH2 1.25 hrs. with 2N NaOH gave 5,2-p-H2NC6H4SO2NHRCO2H (XIV), m. 189° (decomposition) (yellow-white, from naphtha, b. 60-80°, and EtOH). XIV in boiling H2O gave 5-p-H2NC6H4SO2NHR, which with cold, dry NaOMe in MeOH gave (5-p-H2NC6H4SO2NNaR).MeOH, decomposition by 200°. Reduction of 5,2-p-O2NC6H4SO2NHRCSNH2 with ammoniacal FeSO4 gave 5,2-p-H2NC6H4SO2NHRCSNH2, m. 219-20° (golden needles, from HOAc). Isochrysean derivatives were prepared as follows: II with AcCl in dry C5H5N at 0-5° gave 4,5-H2NSCRNHAc (XV), m. 208-10° (pale yellow needles, from 2N HOAc); XV was converted to 4,5-NCRNHAc (XVI), m. 202° (from N HOAc) either by boiling 0.75 hr. with aqueous Pb(OAc)2, or by shaking XV overnight at room temperature with a concentrated aqueous solution of Pb(NO3)2 to which 10% aqueous NaOH had been added until the precipitate redissolved. Boiling XV 1.5 hrs. with 2N NaOH and acidifying the resulting solution at 0° with 2N HCl gave 1,6-dihydro-2-methyl-6-thiazolo[4′,5′:5,4]pyrimidine, m. 266° (yellow), soluble in aqueous NaHCO3 but not in dilute acid. Warming an Me2CO suspension of XVI 45 min. with 20% aqueous H2O2 and 2N Na2CO3, Me2CO being added as required to prevent precipitation of solid, then letting the mixture stand 16 hrs., gave 4,5-H2NOCRNHAc (XVII), m. 212-13° (from H2O); ultraviolet absorption data are given. XVII was also prepared from 4,5-H2NOCRNH2 with AcCl in dry C5H5N at 0-5°. Refluxing 10 g. II, 12.5 g. VI and 150 cc. HOAc 2 hrs. and letting the mixture stand overnight gave 5,4-o-HO2CC6H4CONHRCSNH2 (XVIII), m. 243-4° (pale yellow needles, from HOAc); treatment of XVIII with alk. Pb(NO3)2 as described previously gave 5,4-o-HO2CC5H4CONHRCN (XIX), m. 224° (decomposition), hydrolyzed by 2N NaOH to 5,4-o-HO2CC6H4CONHRCONH2, m. 203° (decomposition), a white powder, resolidifying to yellow rhombohedra, m. 345-50°. Boiling XIX 2 hrs. with Ac2O gave 5,4-o-C6H4(CO)2NRCN, m. 196° (from Ac2O). A solution of 5,4-H2NRCO2Et in dry C5H5N was treated at 0° with p-AcNHC6H4SO2Cl and the crude product hydrolyzed by boiling 2 hrs. with 2N NaOH, giving 5,4-p-H2NC6H4SO2NHRCO2H, m. 184° (decomposition) on slow heating, but immediate decomposition in a bath at 160°; the compound was believed to be the hemihydrate.
Journal of the Chemical Society published new progress about 101012-16-2. 101012-16-2 belongs to thiazole, auxiliary class Thiazole,Chloride,Carboxylic acid, name is 5-Chlorothiazole-2-carboxylic acid, and the molecular formula is C4H2ClNO2S, HPLC of Formula: 101012-16-2.
Referemce:
https://pubchem.ncbi.nlm.nih.gov/compound/thiazole,
Thiazole | chemical compound | Britannica