{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-28ee03ebfec6486d9771f5f5dddac929","dataset_id":"ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc","reaction_class":"Minisci alkylation","transformation_sha256":"c5db31bc9ff8f25e4f3e8de3884a5d7d8f2f6f887e50a102f53c49860c631479","doi":"10.1021/jo9010624","dataset_source_slug":"ord-dataset-feaf1b793c6d408aaec1cac7cc3ceadc","publication_source_slug":"ord-publication-91c8bf15879e5ce2","route_slugs":["ord-28ee03ebfec6486d9771f5f5dddac929-ae4c2a28c455","ord-28ee03ebfec6486d9771f5f5dddac929-2a5e4d7d1498"],"reactant_slugs":["ord-compound-cabaa85293c4d23a00e0","ord-compound-7a5ea1f0381bb40c0ab8"],"product_slugs":["ord-compound-2d094b5599e202354f56"],"selection_notes":["Only explicitly marked REACTANT inputs become graph starting points.","Only products with a positive reported numeric YIELD become graph destinations; all reported outcomes remain in raw.","One representative record per exact reactant/product structure set; other conditions are not additional transformations."],"raw":{"identifiers":[{"type":"CUSTOM","details":"rxn_id from SURF table","value":"lsf_lit_minisci_130"},{"type":"CUSTOM","details":"rxn_tech from SURF table","value":"alkylation"},{"type":"REACTION_TYPE","details":"alkylation minisci","value":"alkylation minisci"}],"inputs":{"additive_1":{"components":[{"identifiers":[{"type":"SMILES","value":"O=S(=O)(O)O"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"7664-93-9"}],"amount":{"moles":{"value":1.5,"units":"MILLIMOLE"}},"reaction_role":"REAGENT"}]},"startingmat_2":{"components":[{"identifiers":[{"type":"SMILES","value":"IC1COC1"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"26272-85-5"}],"amount":{"moles":{"value":1,"units":"MILLIMOLE"}},"reaction_role":"REACTANT"}]},"startingmat_1":{"components":[{"identifiers":[{"type":"SMILES","value":"N#CC1=CN=C2C=C(OC)C(OC)=CC2=C1NC3=CC=C(Cl)C=C3Cl"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"331662-50-1"}],"amount":{"moles":{"value":0.5,"units":"MILLIMOLE"}},"reaction_role":"REACTANT"}]},"catalyst_1":{"components":[{"identifiers":[{"type":"SMILES","value":"[Fe].O=S(=O)(O)O.O"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"7782-63-0"}],"amount":{"moles":{"value":0.3,"units":"MILLIMOLE"}},"reaction_role":"CATALYST"}]},"reagent_1":{"components":[{"identifiers":[{"type":"SMILES","value":"OO"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"7722-84-1"}],"amount":{"moles":{"value":3,"units":"MILLIMOLE"}},"reaction_role":"REAGENT"}]},"solvent_2":{"components":[{"identifiers":[{"type":"SMILES","value":"O"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"7732-18-5"}],"amount":{"volume":{"value":0.3,"units":"MILLILITER"}},"reaction_role":"SOLVENT"}]},"solvent_1":{"components":[{"identifiers":[{"type":"SMILES","value":"O=S(C)C"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"67-68-5"}],"amount":{"volume":{"value":4.7,"units":"MILLILITER"}},"reaction_role":"SOLVENT"}]}},"conditions":{"temperature":{"setpoint":{"value":60,"units":"CELSIUS"}},"pressure":{"control":{"type":"SEALED"},"atmosphere":{"type":"AIR"}}},"notes":{"procedure_details":"H2O2(30%  in  H2O;  153  μL,  1.5  mmol)  was  added  dropwise  over  5  min  to  a  stirred  solution  of  4-(2,4- - 19 -dichlorophenylamino)-6,7-dimethoxyquinoline-3-carbonitrile 4c  (187  mg,  0.5  mmol),  concentrated  H2SO4 (80 μL, 1.5 mmol), 3-iodooxetane (183 mg, 1.0 mmol) and iron(II) sulfate heptahydrate (42 mg, 0.15 mmol) in DMSO (5 mL) at 60 °C. After 1-2 min a further portion of iron(II) sulfate heptahydrate (50 mg, 0.18 mmol) was added and the mixture was stirred at 60 °C for 30 min. Further H2O2 (153 μL, 1.5  mmol)  and  iron(II)  sulfate  heptahydrate  (100  mg,  0.36  mmol)  was  added,  and  the  mixture  was  stirred  at  60  °C  for  15  min.  After  allowing  to  cool,  the  mixture  was  poured  into  a  0.1  M  solution  of  NaOH  which  had  been  saturated  with  solid  NaCl  (50  mL)  and  EtOAc  (50  mL).  The  aqueous  and  organic  layers  were  partitioned  and  the  organic  layer  was  washed  with  brine  (1  x  30  mL),  dried  (Na2SO4),  filtered  and  the  solvent  removed  under  vacuum  to  leave  a  crude  residue.  The  residue  was  purified  by  preparative  thin-layer  chromatography  using  EtOAc  /  hexanes  (7:3)  as  eluent  to  give  the  desired product 5d (86 mg, 38%). An analytical portion of the product 5d was triturated with Et2O for data purposes"},"outcomes":[{"reaction_time":{"value":0.75,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"N#CC=1C(=NC=2C=C(OC)C(OC)=CC2C1NC3=CC=C(Cl)C=C3Cl)C4COC4"},{"type":"CAS_NUMBER","value":"1180654-00-5"}],"measurements":[{"analysis_key":"MS of product_1","type":"IDENTITY"},{"analysis_key":"NMR of product_1","type":"IDENTITY"},{"analysis_key":"product_1_isolated","type":"YIELD","percentage":{"value":38}}],"reaction_role":"PRODUCT"}],"analyses":{"NMR of product_1":{"type":"NMR_1H","data":{"peaks":{"string_value":"1H NMR (400 MHz; d6-DMSO) δ 9.50 (br. s, 1H), 7.80 (s, 1H), 7.77 (t, J = 1.3 Hz, 1H), 7.47 (d, J = 1.3 Hz, 1H), 7.37 (s, 1H), 4.93 (app. t, J = 6.2 Hz, 2H), 4.85 (dd, J = 8.4, 5.6 Hz, 2H), 4.60-4.52  (m,  1H),  3.97  (s,  3H),  3.93  (s,  3H);  13C  NMR  (100  MHz;  d6-DMSO)  159.3,  153.8,  150.7,  149.2,  144.8, 136.2, 131.9, 131.4, 130.0, 129.3, 128.1, 115.7, 112.0, 108.7, 101.7, 85.8, 73.8, 56.2, 56.0, 39.6"}}},"product_1_isolated":{"type":"WEIGHT","details":"isolated"},"MS of product_1":{"type":"MS","details":"430.07","data":{"found":{"float_value":430.07,"description":"Observed m/z"}}}}}],"provenance":{"doi":"10.1021/jo9010624"}}},"entities":[{"slug":"ord-compound-cabaa85293c4d23a00e0","name":"C18H13Cl2N3O2 · ORD IUZCVUGIDCZCEQ-UHFFFAOYSA-N","smiles":"COc1cc2ncc(C#N)c(Nc3ccc(Cl)cc3Cl)c2cc1OC","inchi":"InChI=1S/C18H13Cl2N3O2/c1-24-16-6-12-15(7-17(16)25-2)22-9-10(8-21)18(12)23-14-4-3-11(19)5-13(14)20/h3-7,9H,1-2H3,(H,22,23)","formula":"C18H13Cl2N3O2"},{"slug":"ord-compound-7a5ea1f0381bb40c0ab8","name":"C3H5IO · ORD KBEIFKMKVCDETC-UHFFFAOYSA-N","smiles":"IC1COC1","inchi":"InChI=1S/C3H5IO/c4-3-1-5-2-3/h3H,1-2H2","formula":"C3H5IO"},{"slug":"ord-compound-2d094b5599e202354f56","name":"C21H17Cl2N3O3 · ORD OFKZVFIUCMJERD-UHFFFAOYSA-N","smiles":"COc1cc2nc(C3COC3)c(C#N)c(Nc3ccc(Cl)cc3Cl)c2cc1OC","inchi":"InChI=1S/C21H17Cl2N3O3/c1-27-18-6-13-17(7-19(18)28-2)26-20(11-9-29-10-11)14(8-24)21(13)25-16-4-3-12(22)5-15(16)23/h3-7,11H,9-10H2,1-2H3,(H,25,26)","formula":"C21H17Cl2N3O3"}],"dataset":{"dataset_id":"ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc","name":"Minisci dataset from Roche","description":"Minisci reactions which were extracted from the literature by Roche scientists and published in the SURF format (ChemRxiv, 2024, DOI: 10.26434/chemrxiv-2023-nfq7h)","records_in_source":130,"path":"data/fe/ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc.parquet","sha256":"ebefbe9aba687f182d4f068e94be0f7fd71d1189bdb2eff2aca6fedf4d522bf3","bytes":37643,"repository_url":"https://github.com/open-reaction-database/ord-data/blob/83f971f586f6ad18f358ae4ae99d045e94ed2066/data/fe/ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc.parquet","download_url":"https://huggingface.co/datasets/open-reaction-database/ord-data/resolve/93475c46949f9218e1dfb6624096025135db2add/data/fe/ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc.parquet"},"publication":{"slug":"ord-publication-91c8bf15879e5ce2","title":"Literature experiment — 10.1021/jo9010624","source_type":"paper","doi":"10.1021/jo9010624","url":"https://doi.org/10.1021/jo9010624","note":"Publication DOI reported by the Open Reaction Database. Experimental record data adapted under CC BY-SA 4.0; https://creativecommons.org/licenses/by-sa/4.0/"},"license":"CC-BY-SA-4.0","license_url":"https://creativecommons.org/licenses/by-sa/4.0/","attribution":"Open Reaction Database contributors and the cited original publications","changes":["Bounded selection across datasets and publications","Deduplicated exact transformations across conditions","Canonicalized molecular structures using RDKit; calculated identifiers, formulae and molecular weights","Explicitly incomplete directed branches for all recorded reactants and positively measured products","Removed submitter account and contact fields from provenance; retained scientific input and outcome fields"]}