{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-875738a3ebdc47d99b5dec0d61c0e057","dataset_id":"ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc","reaction_class":"Minisci alkylation","transformation_sha256":"0a09317f781a186188f6b0c825df18c2f47a7de22e5b56760554007b5a9d2a53","doi":"10.1021/jo9010624","dataset_source_slug":"ord-dataset-feaf1b793c6d408aaec1cac7cc3ceadc","publication_source_slug":"ord-publication-91c8bf15879e5ce2","route_slugs":["ord-875738a3ebdc47d99b5dec0d61c0e057-e931e8425800","ord-875738a3ebdc47d99b5dec0d61c0e057-a7b86e3c5c9e"],"reactant_slugs":["ord-compound-0cd18f6bf76cdbfd3d97","ord-compound-7a5ea1f0381bb40c0ab8"],"product_slugs":["ord-compound-17bfebd116d4d6775c08"],"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_117"},{"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":"FC1=CC=C(C=C1Cl)NC=2N=CN=C3C=C(OC)C(OCCCN4CCOCC4)=CC32"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"184475-35-2"}],"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 to a stirred solution of gefitinib 4d (223 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,  followed  by  dropwise  addition  of  further  H2O2 (30% in H2O; 153 μL, 1.5 mmol) over 5 min. The mixture was stirred at 60 °C for 30 min. After allowing to cool, the mixture was poured into a 0.2 M solution of NaOH which had been saturated with solid  NaCl  (30  mL)  and  EtOAc  (50  mL).  The  aqueous  and  organic  layers  were  partitioned  and  the  aqueous  layer  was  extracted  with  EtOAc  (1  x  30  mL).  The  combined  organic  layers  were  dried  (Na2SO4),  filtered  and  the  solvent  removed  under  vacuum  to  leave  a  crude  residue  (ca.  300  mg).  The  residue  was  purified  by  high-performance  liquid  chromatography  (column:  Gemini  C18;  size:  250  x  21.2 mm; eluent: 70-90% MeOH in 10 mM aqueous Et2NH or 75% MeOH in 10 mM aqueous Et2NH; run time: 25 min; detection: UV at 254 nM) to give the desired product 5f (35 mg, 93% pure, 13% yield adjusted for purity). An analytical portion of the product 5f was triturated with hot EtOAc / hexanes to  - 21 -give material for data purposes"},"outcomes":[{"reaction_time":{"value":0.5,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"FC1=CC=C(C=C1Cl)NC=2N=C(N=C3C=C(OC)C(OCCCN4CCOCC4)=CC32)C5COC5"},{"type":"CAS_NUMBER","value":"1180654-05-0"}],"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":13}}],"reaction_role":"PRODUCT"}],"analyses":{"NMR of product_1":{"type":"NMR_1H","data":{"peaks":{"string_value":"1H NMR (400 MHz; CDCl3) δ 8.01 (dd, J = 6.5, 2.7 Hz, 1H), 7.70-7.66 (m, 1H), 7.32 (br. s, 1H), 7.23 (s, 1H), 7.19 (t, J = 8.7 Hz, 1H), 7.09 (s, 1H), 5.13 (t, J = 6.3 Hz, 2H), 5.08 (dd, J = 8.5, 5.8 Hz, 2H), 4.49-4.41 (m, 1H), 4.21 (t, J = 6.6 Hz, 2H), 4.00 (s, 3H), 3.75 (t, J = 4.6 Hz,  4H),  2.60  (t,  J  =  7.0  Hz,  2H),  2.51  (br.  s,  4H),  2.17-2.20  (m,  2H);  13C  NMR  (100  MHz;  CDCl3) 162.9, 156.4, 155.5, 152.4 (d, J = 244 Hz), 147.0, 146.2, 135.7 (d, J = 5 Hz), 123.5, 121.1, 121.0 (d, J = 7  Hz),  116.8  (d,  J  =  22  Hz),  108.0,  107.2,  100.7,  76.1,  67.8,  67.0,  56.4,  55.5,  52.9,  43.0,  26.2"}}},"product_1_isolated":{"type":"WEIGHT","details":"isolated"},"MS of product_1":{"type":"MS","details":"503.18","data":{"found":{"float_value":503.18,"description":"Observed m/z"}}}}}],"provenance":{"doi":"10.1021/jo9010624"}}},"entities":[{"slug":"ord-compound-0cd18f6bf76cdbfd3d97","name":"C22H24ClFN4O3 · ORD XGALLCVXEZPNRQ-UHFFFAOYSA-N","smiles":"COc1cc2ncnc(Nc3ccc(F)c(Cl)c3)c2cc1OCCCN1CCOCC1","inchi":"InChI=1S/C22H24ClFN4O3/c1-29-20-13-19-16(12-21(20)31-8-2-5-28-6-9-30-10-7-28)22(26-14-25-19)27-15-3-4-18(24)17(23)11-15/h3-4,11-14H,2,5-10H2,1H3,(H,25,26,27)","formula":"C22H24ClFN4O3"},{"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-17bfebd116d4d6775c08","name":"C25H28ClFN4O4 · ORD FJVNPBRXSMUTPY-UHFFFAOYSA-N","smiles":"COc1cc2nc(C3COC3)nc(Nc3ccc(F)c(Cl)c3)c2cc1OCCCN1CCOCC1","inchi":"InChI=1S/C25H28ClFN4O4/c1-32-22-13-21-18(12-23(22)35-8-2-5-31-6-9-33-10-7-31)25(30-24(29-21)16-14-34-15-16)28-17-3-4-20(27)19(26)11-17/h3-4,11-13,16H,2,5-10,14-15H2,1H3,(H,28,29,30)","formula":"C25H28ClFN4O4"}],"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"]}