{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-98133d0b8a69408ba939cadb7f0b7452","dataset_id":"ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc","reaction_class":"Minisci alkylation","transformation_sha256":"0f6ace6cf455a006d55fed6e0495e2e5a56cdecad504dd1769cedf7735f4e72d","doi":"10.1021/jo9010624","dataset_source_slug":"ord-dataset-feaf1b793c6d408aaec1cac7cc3ceadc","publication_source_slug":"ord-publication-91c8bf15879e5ce2","route_slugs":["ord-98133d0b8a69408ba939cadb7f0b7452-cb1e19c76c0b","ord-98133d0b8a69408ba939cadb7f0b7452-43729084a156"],"reactant_slugs":["ord-compound-844c99d01eaca8862f97","ord-compound-7a5ea1f0381bb40c0ab8"],"product_slugs":["ord-compound-fcc5db3006ff810bcfe8"],"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_121"},{"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":2,"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":2,"units":"MILLIMOLE"}},"reaction_role":"REACTANT"}]},"startingmat_1":{"components":[{"identifiers":[{"type":"SMILES","value":"N1=CN(C=2C=CC=CC12)C"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"1632-83-3"}],"amount":{"moles":{"value":1,"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":0.6,"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":6,"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":0.6,"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":9.4,"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;  0.31  mL,  3.0  mmol)  was  added  dropwise  over  1-2  min  to  a  stirred  solution  of  1-methylbenzimidazole  1g  (100  mg,  1.0  mmol),  concentrated  H2SO4  (107  μL,  2.0  mmol),  3-iodooxetane  (368  mg,  2.0  mmol)  and  iron(II)  sulfate  heptahydrate (80 mg, 0.3 mmol) in DMSO (10 mL) at room temperature. After 30 min a further portion of iron(II) sulfate heptahydrate (200 mg, 0.75 mmol) and H2O2 (0.31 mL, 3.0 mmol) was added, and the mixture was stirred at room temperature for 30 min. Further iron(II) sulfate heptahydrate (200 mg, 0.75 mmol)  and  H2O2 (0.31 mL, 3.0 mmol) was added and the mixture stirred at room temperature for 120 min, then heated to 60 °C and stirred for 60 min. After allowing to cool, the mixture was poured into a solution  of  NaOH  and  ice  (to  pH  >  10)  and  it  was  then  extracted  with  Et2O.  The  aqueous  layer  was  saturated  with  solid  NaCl  and  extracted  with  CHCl3.  The  combined  organic  extracts  were  dried  (MgSO4),  filtered  and  the  solvent  removed  under  vacuum  to  leave  a  crude  residue.  The  residue  was  purified  by  column  chromatography  on  silica  gel  using  EtOAc  /  MeOH  (1:0  to  4:1)  to  give  impure  product  (40  mg).  The  impure  product  was  purified  further  by  preparative  thin-layer  chromatography  using EtOAc / MeOH (19:1) as eluent to give product (25 mg). The product was purified further using preparative high-performance liquid chromatography using 0.1% aqueous formic acid / MeCN (19:1 to 9:1) as eluent to give the desired product 2g (12 mg, 6%) as a solid."},"outcomes":[{"reaction_time":{"value":3,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"N=1C=2C=CC=CC2N(C1C3COC3)C"},{"type":"CAS_NUMBER","value":"1180653-66-0"}],"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":6}}],"reaction_role":"PRODUCT"}],"analyses":{"NMR of product_1":{"type":"NMR_1H","data":{"peaks":{"string_value":"1H NMR (400 MHz; CDCl3) δ 7.80-7.78 (m, 1H), 7.31-7.29 (m, 3H), 5.21 (t, J = 5.8 Hz, 2H), 5.08 (dd, J = 8.4, 5.5 Hz, 2H), 4.63-4.55 (m, 1H), 3.65 (s, 3H); 13C NMR (100 MHz; CDCl3) δ 153.5, 142.4, 136.0, 122.9, 122.5, 119.7, 109.2, 75.0,  - 8 -75.0, 32.9, 29.7;"}}},"product_1_isolated":{"type":"WEIGHT","details":"isolated"},"MS of product_1":{"type":"MS","details":"189.1","data":{"found":{"float_value":189.1,"description":"Observed m/z"}}}}}],"provenance":{"doi":"10.1021/jo9010624"}}},"entities":[{"slug":"ord-compound-844c99d01eaca8862f97","name":"C8H8N2 · ORD FGYADSCZTQOAFK-UHFFFAOYSA-N","smiles":"Cn1cnc2ccccc21","inchi":"InChI=1S/C8H8N2/c1-10-6-9-7-4-2-3-5-8(7)10/h2-6H,1H3","formula":"C8H8N2"},{"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-fcc5db3006ff810bcfe8","name":"C11H12N2O · ORD UMZINEBODJUZMR-UHFFFAOYSA-N","smiles":"Cn1c(C2COC2)nc2ccccc21","inchi":"InChI=1S/C11H12N2O/c1-13-10-5-3-2-4-9(10)12-11(13)8-6-14-7-8/h2-5,8H,6-7H2,1H3","formula":"C11H12N2O"}],"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"]}