{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-6ae06cd6fdb442dfae1c1f5a96560381","dataset_id":"ord_dataset-feaf1b793c6d408aaec1cac7cc3ceadc","reaction_class":"Minisci alkylation","transformation_sha256":"acf4a1d7d13e6a00f49bbcc880ea3d20cd9d235b5126ad02424449431a223e79","doi":"10.1021/jo9010624","dataset_source_slug":"ord-dataset-feaf1b793c6d408aaec1cac7cc3ceadc","publication_source_slug":"ord-publication-91c8bf15879e5ce2","route_slugs":["ord-6ae06cd6fdb442dfae1c1f5a96560381-d4fb7c5cf72d","ord-6ae06cd6fdb442dfae1c1f5a96560381-7d34030f4644"],"reactant_slugs":["ord-compound-cabaa85293c4d23a00e0","ord-compound-c548c24d29328ab9f616"],"product_slugs":["ord-compound-87118402dbeefec33b60"],"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_129"},{"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":"O=C(OC(C)(C)C)N1CC(I)C1"},{"type":"CAS_NUMBER","details":"cas number from SURF _cas column","value":"254454-54-1"}],"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":50,"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-dichlorophenylamino)-6,7-dimethoxyquinoline-3-carbonitrile 4c (187 mg, 0.5 mmol), concentrated  H2SO4  (80  μL,  1.5  mmol),  1-Boc-3-(iodo)azetidine  (282  mg,  1.0  mmol)  and  iron(II)  sulfate heptahydrate (42 mg, 0.15 mmol) in DMSO (5 mL) at 50 °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 50 °C for 45 min. Further iron(II) sulfate heptahydrate (50 mg, 0.18 mmol) was then added, followed by H2O2 (153 μL,  1.5  mmol)  over  5  min.  The  mixture  was  stirred  at  50  °C  for  20  min.  After  allowing  to  cool,  the   - 20 -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 (3:2) as  eluent  to  give  the  desired  product  5e  (118  mg,  44%).  An  analytical  portion  of  the  product  5e  was  recrystallized  from  EtOAc  /  hexanes  for  data  purposes"},"outcomes":[{"reaction_time":{"value":1.1,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"N#CC=1C(=NC=2C=C(OC)C(OC)=CC2C1NC3=CC=C(Cl)C=C3Cl)C4CN(C(=O)OC(C)(C)C)C4"},{"type":"CAS_NUMBER","value":"1180654-03-8"}],"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":44}}],"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), 7.79 (s, 1H), 7.77 (s, 1H), 7.48 (s, 1H), 7.36 (s, 1H), 4.20-4.06 (m, 5H), 3.97 (s, 3H), 3.92 (s, 3H), 1.39 (s, 9H); 13C NMR (100 MHz; d6-DMSO) δ 159.3, 155.7, 153.8, 150.7, 149.2, 144.6, 136.2, 131.8, 131.4,  129.9,  129.3,  128.1,  115.7,  112.0,  108.8,  101.7,  86.0,  78.6,  56.2,  56.0,  53.5,  52.3,  33.4,  28.1"}}},"product_1_isolated":{"type":"WEIGHT","details":"isolated"},"MS of product_1":{"type":"MS","details":"529.14","data":{"found":{"float_value":529.14,"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-c548c24d29328ab9f616","name":"C8H14INO2 · ORD XPDIKRMPZNLBAC-UHFFFAOYSA-N","smiles":"CC(C)(C)OC(=O)N1CC(I)C1","inchi":"InChI=1S/C8H14INO2/c1-8(2,3)12-7(11)10-4-6(9)5-10/h6H,4-5H2,1-3H3","formula":"C8H14INO2"},{"slug":"ord-compound-87118402dbeefec33b60","name":"C26H26Cl2N4O4 · ORD QTHUSZKQIGNCRB-UHFFFAOYSA-N","smiles":"COc1cc2nc(C3CN(C(=O)OC(C)(C)C)C3)c(C#N)c(Nc3ccc(Cl)cc3Cl)c2cc1OC","inchi":"InChI=1S/C26H26Cl2N4O4/c1-26(2,3)36-25(33)32-12-14(13-32)23-17(11-29)24(30-19-7-6-15(27)8-18(19)28)16-9-21(34-4)22(35-5)10-20(16)31-23/h6-10,14H,12-13H2,1-5H3,(H,30,31)","formula":"C26H26Cl2N4O4"}],"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"]}