Day: November 22, 2022

Isonitrosoacetanilides and their condensation to form isatin derivatives was written by Sandmeyer, T.. And the article was included in Helvetica Chimica Acta in 1919.Product Details of 15540-90-6 The following contents are mentioned in the article:

Hydroxylaminesulfonic acid solution (A) was prepared by adding rapidly with stirring 627 g. NaHSO₃ to 84 g. NaNO₂ in 500 cc. H₂O containing 300 g. ice. After 1.5 hrs. a cold solution of 66 g. concentrated H₂SO₄ in 66 g. H₂O is added during the course of 2 hrs. until the solution is acid to congo paper; after 2 days the reaction is completed. Isonitrosoacetanilide (B) is prepared by boiling 3-4 hrs. under reflux 450 g. of A, adding 10 g. PhNH₂, 350 g. H₂O, 16.5 g. CCl₃CHO.H₂O and continuing the boiling for 1 hr. longer. On cooling rapidly the light yellow crystals of B sep., are filtered and washed with H₂O; they m. 175° (decomposition), are readily soluble in Et₂O or EtOH, slightly in cold H₂O or PhH; acids precipitate it unchanged from alk. solutions Isonitrosoacet-p-chloroanilide (C) is prepared by boiling under reflux for several hrs. 450 g. of A, mixing a 100-50 g. portion into a paste with 12.75 g. p-ClC₆H₄NH₂, adding the paste to the remainder of A, diluting with 300 g. H₂O and then boiling for 0.75 hr. with 16.5 g. CCl₃CHO.H₂O. The crystals of C which sep. on cooling are dissolved in dilute NaOH, dilute HCl is added nearly to neutralization and the solution filtered. C is obtained on the addition of acid as a white, crystalline precipitate which is filtered and washed with H₂O; it m. 165°, is slightly soluble in H₂O, fairly in Et₂O and readily in EtOH; yield, 14.3 g. The following derivatives were obtained in the same way from the corresponding aromatic amines and the m. p. refers to the uncrystd. reaction product: o-toluide, 121°; m-toluide, 146°; p-toluide, 162°; m-xylide, 161°; p-xylide, 151°; o-aniside, 140°; p-phenetide, 195°; methylanilide, 145°; ethylanilide, 160°; benzylanilide, 142°; o-chloroanilide, 150°; m-chloroanilide, 154°; 2,5-dichloroanilide, 163°; 3,4-dichloroanilide, 158°; 3,5-dichloroanilide, 185°; 5-chloro-2-toluide (Me = 1), 167°; 4-chloro-2-toluide, 148°; 6-chloro-3-toluide, 187°; 4-chloro-3-toluide, 134°; 2-chloro-4-toluide, 177°; 3-chloro-4-toluide, 188°; 4-chloro-2-aniside (MeO = 1), 182°; p-bromoanilide, 167°; 2,4-dibromoanilide, 215°; anthranilic acid, 208°. Isatin (D) was prepared by adding gradually with stirring 10 g. B to 50 g. of concentrated H₂SO₄ at 60° and keeping the temperature at all times below 65°; after B has been added and is in solution, the temperature, is raised to 75° for 10-5 min.; the solution is cooled and immediately diluted with 160 g. cold H₂O; the yellow-red crystals of D which sep. are filtered and washed with H₂O; these crystals show all the characteristic tests for D and m. 197°. In the same way by modifying the temperature the following isonitrosoacetanilides were converted into isatin derivatives; at 55-60° during addition and at 65-70° at completion, methyl and ethylanilides; at 60-5° and subsequently at 70-5°, o- and p- toluides and o- and p-xylides; at 80-5° and subsequently at 95°, o- and m-chloroanilides, 4-chloro-2-toluide, 4-chloro-3-toluide, 2-chloro-4-toluide, 4-chloro-2-aniside; at 90-5° subsequently 105°, 3-chloro-4-toluide, 5-chloro-2-toluide, 6-chloro-3-toluide, p-chloro-anilide, 2,5-and 3,5-dichloroanilides; at 95-100°, subsequently 110°, 3,4-dichloro-anilide, p-bromoanilide, anthranilic acid. The isatin derivatives from o-aniside, p-phenitide and 2,4-dibromoanilide could not be prepared by this reaction; a mixture of two isomers is obtained when both free o-positions are not the same, e. g., m-toluide or 3,4-dichloroanilide. The following were prepared by this reaction and the m. p. refers to the uncrystd. material; mixture of 4- and 6-methylisatins, orange-yellow, 143°; 4,7-dimethylisatin, orange-yellow, 250°; 7-chloroisatin, red-brown, 175°; mixture of 4- and 6-chloroisatins, orange-yellow, 212°; mixture of 4-chloro-7-methylisatin, orange-yellow, 4,5- and. 5,6-dichloroisatins, yellow-red 200°; 4,6-dichloroisatin, citron-yellow, 250°; 273°; 5-chloro-7-methylisatin, yellow-brown, 265°; mixture of 4-chloro-5-methyl- and 5-methyl-6-chloroisatins, red, 205°; 4-methyl-7-chloroisatin, orange-yellow, 252°; 4-chloro-7-methoxyisatin, red, 240°; isatin-7-carboxylic acid, brown-yellow, 235°. Many of the yields were quant. Application for patents has been made. This study involved multiple reactions and reactants, such as 4,7-Dimethylindoline-2,3-dione (cas: 15540-90-6Product Details of 15540-90-6).

4,7-Dimethylindoline-2,3-dione (cas: 15540-90-6) belongs to indole derivatives. In addition to tryptophan, indigo, and indoleacetic acid, numerous compounds obtainable from plant or animal sources contain the indole molecular structure. It is used in perfumery and in making tryptophan, an essential amino acid, and indoleacetic acid (heteroauxin), a hormone that promotes the development of roots in plant cuttings.Product Details of 15540-90-6

Referemce:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

An Antimalarial alkaloid from hydrangea. XV. Synthesis of 5-, 6-, 7-, and 8-derivatives with no identical substituents was written by Ablondi, Frank;Gordon, Samuel;Morton, John II;Williams, J. H.. And the article was included in Journal of Organic Chemistry in 1952.Application In Synthesis of 4,7-Dimethylindoline-2,3-dione The following contents are mentioned in the article:

To study the effect of substituents in the C₆H₆ ring on the antimalarial activity and chemotherapeutic index of the DL-form of the hydrangea alkaloid, a series of derivatives with 2 identical substituents in the benzene ring are synthesized by converting, according to Marvel and Hiers (C.A. 20, 193), the appropriate R₂C₆H₃NH₂ into the R₂C₆H₃NHCOCH:NOH (I) (Table F) which, on ring closure with 86% H₂SO₄, give the corresponding isatins (II) (Table G). Oxidation of II with alk. peroxide gives the disubstituted o-H₂NC₆H₄CO₂H (III) (Table H) which, on fusion with HCONH₂ (see preceding abstract), give the corresponding disubstituted 4(3H)-qainazolones (IV) (Table I). Condensation of 1-carbethoxy-2-(3-bromoacetonyl)-3-methoxypiperidine with the appropriate IV gives the disubstituted 3-[2-oxo-3-(1-carbethoxy-3-methoxy-2-piperidyl)propyl]-4(3H)-quinazolones (V) which, hydrolyzed with 6 N HCl, give the corresponding 3-[2-oxo-3 – (3-methoxy-2-piperidyl)propyl]-4(3H)-quinazolones (VI). Demethylation of VI then gives the corresponding 3-hydroxy-2-piperidyl derivatives (VII) (VIa, R = H). The IV, V, VI, and VII are listed in Table I. Cyclization of 55 g. 3,4-Me.₂C₆H₃NHCOCH:NOH with 292 cc. 96% H₂SO₄ and 29 cc. H₂O, solution of the isatin mixture in 1.2 l. H₂O and 310 cc. 10% NaOH, dropwise addition of 12 N HCl to the filtered solution until turbid, and then addition of 4-cc. portions of acid and separation of the precipitate after each addition give 12.6 g. crude 4,5-dimethylisatin. The 4th addition gives no precipitate and strong acidification of the mother liquor gives 23.3 g. 5,6-dimethylisatin. Treating 21.5 g. 4-chloroisatin 4 h. at 50° in 440 cc. AcOH with 20 cc. SO₂Cl₂ and a crystal of iodine gives 60% 4,5-dichloroisatin. In the same way 6-chloroisatin gives 5,6-dichloroisatin. Adding 16.2 g. NaNO₂ in small portions to 25 g. 3,5,2-Me₂(H₂N)C₆H₂NO₂ in 70 cc. 6 N HCl at 0-5° with stirring and adding the diazonium solution to 35.6 g. NaCN and 34.5 g. NiCl₂.H₂O in 230 cc. H₂O with warming on a steam bath 45 min. give 79% 3,5,2-Me₂(NC)C₆H₂NO₂, m. 125-8° which (18.7 g.), heated with 50 cc. 80% H₂SO₄ 5 h. on a steam bath and poured onto ice, gives 52% 4,6,2-Me₂(O₂N)C₆H₂CONH₂; Table F. Disubstituted α-isonitrosoacetanilides (I); Reaction time, Yield, M.p.,;R₂, (min.), %, °C.; 3,4-Di-Me, 2, 84, 179-80^a; 2,5-Di-Me, 5, 33, 151-3; 2,4-Di-Me, 8, 55, 158-9; 2,3-Di-Me, 3, 64, 131-2; 2,5-Di-Cl, 15, 22, 166-8; 3,5-Di-Br, 15, 11, 197-200; 3,4-(CH₂)_4^–, 120, 87, 147-50; (a) Decomposition Table G., Disubstituted isatins (II); Yield, M.p., R₂, Color, %, °C.; 4,5-Di-Me, red, 25, 225-6; 4,7-Di-Me, orange, 75, 260-4; 5,6-Di-Me, red, 46, 214-15; 5,7-Di-Me, orange, 91, 228-31; 6,7-Di-Me, orange, 57, 230-2; 4,5-Di-Cl, red, 60, 243-5; 4,7-Di-Cl, 99, 239-41; 5,6-Di-Cl, orange-red, 68, 264-8^a; 4,6-Di-Br, orange, 88, 254-6; 4,5-(CH₂)_4^–, orange, 32, 188-90^a; 5,6-(CH₂)_4^–, orange, 17, 176-85^a; (a) Decomposition; Table H. Disubstituted anthranilic acids; Yield, M.p.a,; R₂, %, °C.; 5,6-Di-Me, 65, 140-1; 4,6-Di-Me, 91, 160-1; 3,6-Di-Me, 58, 111-13; 4,5-Di-Me, 81, 213-14; 3,5-Di-Me, 65, 188-9; 3,4-Di-Me, 69, 184-6; 5,6-Di-Cl, 59, 165-7; 3,6-Di-Cl, 59, 148-50; 4,5-Di-Cl, 99, 208; 3,5-Di-Cl, 39, 230-1; 4,6-Di-Br, 73, 170-1; 5,6-(CH₂)_4^–, 62, 114; 4,5-(CH₂)_4^–, 86, 171-3; (a) Decomposition (VIII), m. 169-71°. Reduction of 12.9 g. VIII in 100 cc. Methyl Cellosolve 20 min. with 1 g. Pd-charcoal at 2-3 atm. H gives 91% 4,6,2-Me₂(H₂N)C₆H₂CONH₂, m. 160-1°. Adding 25 cc. SO₂Cl₂, over a period of 15 min. to 20 g. o-H₂NC₆H₄CO₂H in 500 cc. AcOH at 40°, stirring the mixture 2 h., and extracting the precipitate with 15% HCl on a steam bath give 39% 3,5,2-Cl₂(H₂N)C₆H₂CO₂H, m.230-1°. This study involved multiple reactions and reactants, such as 4,7-Dimethylindoline-2,3-dione (cas: 15540-90-6Application In Synthesis of 4,7-Dimethylindoline-2,3-dione).

4,7-Dimethylindoline-2,3-dione (cas: 15540-90-6) belongs to indole derivatives. Indole is an important structural motif of various drugs, therapeutic leads besides its prevalence in numerous natural products, agrochemicals, perfumery, and dyes.Indole was synthesized in moderate yield via an o-naphthoquinone catalyzed tandem cross-coupling of substituted aniline and benzylamine under aerobic oxidation conditions.Application In Synthesis of 4,7-Dimethylindoline-2,3-dione

Referemce:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles