{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-079d5ee961d349b3860c3cad94f9eab1","dataset_id":"ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc","reaction_class":"Minisci alkylation","transformation_sha256":"203cace9ae8bc7d13cb82dc5ff7bbb113944babebed0df5bd14e7d5d08c2f1b5","doi":"10.1021/jo9010624","dataset_source_slug":"ord-dataset-feaf1b793c6d408aaec1cac7cc3ceadc","publication_source_slug":"ord-publication-91c8bf15879e5ce2","route_slugs":["ord-079d5ee961d349b3860c3cad94f9eab1-a2a8586ecfb9","ord-079d5ee961d349b3860c3cad94f9eab1-e73c36c090b5"],"reactant_slugs":["ord-compound-7d2acc558623051e5c91","ord-compound-7a5ea1f0381bb40c0ab8"],"product_slugs":["ord-compound-850ee26a2bd36644b6ef"],"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_125"},{"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":"OC(C=1C=CN=C2C=CC(OC)=CC21)C3N4CCC(C3)C(C4)CC"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"522-66-7"}],"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":50,"units":"CELSIUS"}},"pressure":{"control":{"type":"SEALED"},"atmosphere":{"type":"AIR"}}},"notes":{"procedure_details":"H2O2 (30% in H2O; 0.15 mL, 1.5 mmol) was added dropwise over about 1 min to a stirred solution of hydroquinine (163 mg, 0.5 mmol), 3-iodooxetane (184 mg, 1.0 mmol), concentrated H2SO4 (54 μL, 1.0 mmol)  and  iron(II)  sulfate  heptahydrate  (40  mg,  0.15  mmol)  in  DMSO  (5  mL)  at  room  temperature.  After addition of the H2O2 the mixture was placed in an oil bath at 50 °C. After 2 min a further portion of iron(II) sulfate heptahydrate (40 mg, 0.15 mmol) was added and the mixture was stirred at 50 °C for 35 min. Further iron(II) sulfate heptahydrate (40 mg, 0.15 mmol) and H2O2 (30% in H2O; 0.15 mL, 1.5 mmol)  was  added  and  the  mixture  was  stirred  at  50  °C for a further 15 min then allowed to cool. The mixture was poured into a 0.2 M solution of NaOH (15 mL) and Et2O (30 mL). Saturated NaHCO3 was added to bring the pH to 10. The aqueous and organic layers were partitioned and the aqueous layer was extracted with Et2O (2 x 15 mL). The combined organic extracts were washed with brine (2 x 15 mL). The combined aqueous phases were extracted with additional Et2O (15 mL) [NB this was undertaken as some product was noted to still be in all the aqueous phase]. The combined organic extracts were dried (MgSO4),  filtered  and  the  solvent  removed  under  vacuum  to  leave  a  crude  oil  (186  mg).  The  oil  was  purified  by  preparative  high-performance  liquid  chromatography  (column:  Gemini  C18  10  μM;  size:  150 x 21.2 mm; eluent: 20-75% MeCN in 10 mM aqueous Et2NH or 35-98% MeCN in 10 mM aqueous Et2NH; run time: 17 min; flow rate: 20 mL/min; detection: UV at 254 nM) to give the desired product  - 17 -5b  collected  as  four  aliquots  (1st aliquot 12 mg, ca. 90% purity, 6% yield; 2nd aliquot 19 mg, ca. 80% purity,  8%  yield;  3rd  aliquot  17  mg,  ca.  80%  purity,  7%  yield;  4th  aliquot  12  mg,  ca.  90%  purity,  6%  yield. All yields have been adjusted for purities). Total yield = 27% (yield adjusted for purity). The 1stand 4th aliquots were purified further by preparative high-performance liquid chromatography (column: Gemini C18 10 μM; size: 150 x 21.2 mm; eluent: 55-95% MeOH in 10 mM aqueous Et2NH; run time: 20  min;  flow  rate:  20  mL/min;  detection:  UV  at 254 nM) to give material for data purposes"},"outcomes":[{"reaction_time":{"value":0.8,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"OC(C1=CC(=NC=2C=CC(OC)=CC21)C3COC3)C4N5CCC(C4)C(C5)CC"},{"type":"CAS_NUMBER","value":"1180653-96-6"}],"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":27}}],"reaction_role":"PRODUCT"}],"analyses":{"NMR of product_1":{"type":"NMR_1H","data":{"peaks":{"string_value":"1H  NMR  (400 MHz; CDCl3) δ 7.98 (d, J = 9.2 Hz, 1H), 7.62 (s, 1H), 7.34 (dd, J = 9.2, 2.6 Hz, 1H), 7.24 (d, J = 2.6 Hz, 1H), 5.55 (d, J = 3.8 Hz, 1H), 5.11-5.07 (m, 2H), 4.99 (d, J = 12.5, 6.2 Hz, 2H), 4.50-4.42 (m, 1H), 3.89 (s, 3H), 3.71 (br. s, 1H), 3.45-3.39 (m, 1H), 3.14-3.02 (m, 2H), 2.65-2.58 (m, 1H), 2.39-2.36 (m, 1H), 1.77 (br. s, 1H), 1.75-1.68 (m, 2H), 1.48-1.37 (m, 3H), 1.28-1.20 (m, 2H), 0.81 (t, J = 7.3 Hz, 3H); 13C NMR (100 MHz; CDCl3) δ 158.0, 157.7, 148.8, 144.2, 131.5, 125.6, 121.6, 116.7, 101.6, 77.1, 72.6, 59.9, 58.9, 55.9, 43.5, 42.5, 37.7, 28.5, 27.9, 25.6, 21.7, 12.2"}}},"product_1_isolated":{"type":"WEIGHT","details":"isolated"},"MS of product_1":{"type":"MS","details":"383.23","data":{"found":{"float_value":383.23,"description":"Observed m/z"}}}}}],"provenance":{"doi":"10.1021/jo9010624"}}},"entities":[{"slug":"ord-compound-7d2acc558623051e5c91","name":"C20H26N2O2 · ORD LJOQGZACKSYWCH-UHFFFAOYSA-N","smiles":"CCC1CN2CCC1CC2C(O)c1ccnc2ccc(OC)cc12","inchi":"InChI=1S/C20H26N2O2/c1-3-13-12-22-9-7-14(13)10-19(22)20(23)16-6-8-21-18-5-4-15(24-2)11-17(16)18/h4-6,8,11,13-14,19-20,23H,3,7,9-10,12H2,1-2H3","formula":"C20H26N2O2"},{"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-850ee26a2bd36644b6ef","name":"C23H30N2O3 · ORD DPRXNZZTKURJBX-UHFFFAOYSA-N","smiles":"CCC1CN2CCC1CC2C(O)c1cc(C2COC2)nc2ccc(OC)cc12","inchi":"InChI=1S/C23H30N2O3/c1-3-14-11-25-7-6-15(14)8-22(25)23(26)19-10-21(16-12-28-13-16)24-20-5-4-17(27-2)9-18(19)20/h4-5,9-10,14-16,22-23,26H,3,6-8,11-13H2,1-2H3","formula":"C23H30N2O3"}],"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"]}