{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-47040b4dc9d846d3bba53e0f90a4fd4c","dataset_id":"ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc","reaction_class":"Minisci alkylation","transformation_sha256":"1f40ceec84a6ed1c75cadf13fbeb4802e1d16fe6cc309ec69f1b1452a0a6177e","doi":"10.1021/jo9010624","dataset_source_slug":"ord-dataset-feaf1b793c6d408aaec1cac7cc3ceadc","publication_source_slug":"ord-publication-91c8bf15879e5ce2","route_slugs":["ord-47040b4dc9d846d3bba53e0f90a4fd4c-c5a02a7fe69c","ord-47040b4dc9d846d3bba53e0f90a4fd4c-56059554b66b"],"reactant_slugs":["ord-compound-2ac0d3ea4d4960ea06af","ord-compound-7a5ea1f0381bb40c0ab8"],"product_slugs":["ord-compound-577ff53bca521dd1e7d2"],"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_132"},{"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,"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=1C=NC=2C=C(OC)C(OC)=CC2C1OC"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"881293-34-1"}],"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, 1.50 mmol) was added dropwise  to  a  stirred  solution  of  4,6,7-trimethoxyquinazoline  1i  (110  mg,  0.5  mmol),  concentrated  H2SO4 (54 μL, 1.0 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 (42 mg, 0.15 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 (42 mg, 0.15 mmol) was added, and the mixture was stirred at  60  °C  for  a  further  60  min.  Ater  allowing  to  cool,  the  mixture  was  poured  into  a  0.2  M  solution  of  NaOH  (50  mL)  and  Et2O  (30  mL).  The  aqueous  and  organic  layers  were  partitioned  and  the  aqueous  layer  was  saturated  with  solid  NaCl,  then  extracted  with  Et2O  (2  x  25  mL).  The  combined  organic   - 9 -extracts were dried (MgSO4), filtered and the solvent removed under vacuum to leave a crude oil. The oil  was  purified  by  preparative  thin-layer  chromatography  to  give  a  mixture  of  recovered  4,6,7-trimethoxyquinazoline 1i and product, followed by desired product 2i (64 mg, ca. 83% pure, 38% yield adjusted  for  purity).  An  analytical  sample  of  the  product  2i  (83%  purity)  was  purified  further  by  perparative  high-performance  liquid  chromatography  to  give  material  for  data  purposes  (column:  Gemini C6P (phenyl hexyl); size: 100 x 21.2 mm; particle size: 5 μM; eluent: 3-70% CH3CN in 10 mM aqueous  Et2NH; run time: 20 min; detection: UV at 254 nM; retention time: 7.76 min)"},"outcomes":[{"reaction_time":{"value":1.5,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"N=1C(OC)=C2C=C(OC)C(OC)=CC2=NC1C3COC3"},{"type":"CAS_NUMBER","value":"1180653-71-7"}],"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; CDCl3) δ 7.34 (s, 1H), 7.23 (s, 1H) 5.18-5.15 (m, 2H), 5.08-5.05 (m, 2H), 4.54-4.46 (m, 1H), 4.20 (d, J  =  0.8  Hz,  3H),  4.02  (m,  6H);  13C  NMR  (100  MHz;  CDCl3) δ  166.2,  163.6,  155.5,  149.5,  148.7,  109.2, 106.7, 101.4, 76.2, 56.4, 56.3, 54.2, 43.0"}}},"product_1_isolated":{"type":"WEIGHT","details":"isolated"},"MS of product_1":{"type":"MS","details":"277.6","data":{"found":{"float_value":277.6,"description":"Observed m/z"}}}}}],"provenance":{"doi":"10.1021/jo9010624"}}},"entities":[{"slug":"ord-compound-2ac0d3ea4d4960ea06af","name":"C11H12N2O3 · ORD ZRYWDTDJBHKYNL-UHFFFAOYSA-N","smiles":"COc1cc2ncnc(OC)c2cc1OC","inchi":"InChI=1S/C11H12N2O3/c1-14-9-4-7-8(5-10(9)15-2)12-6-13-11(7)16-3/h4-6H,1-3H3","formula":"C11H12N2O3"},{"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-577ff53bca521dd1e7d2","name":"C14H16N2O4 · ORD PGOPIGZGFMUHTP-UHFFFAOYSA-N","smiles":"COc1cc2nc(C3COC3)nc(OC)c2cc1OC","inchi":"InChI=1S/C14H16N2O4/c1-17-11-4-9-10(5-12(11)18-2)15-13(8-6-20-7-8)16-14(9)19-3/h4-5,8H,6-7H2,1-3H3","formula":"C14H16N2O4"}],"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"]}