{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-352807a1f4c14595afeef50c6c39ae38","dataset_id":"ord_dataset-5540e162c09f4c04905ddc8ba9c931c6","reaction_class":"Copper-catalyzed hydroamination preparation","transformation_sha256":"f8359a7e36f904c23081ef69b08c14512f31651084d0f1f411318f861c76128c","doi":"10.15227/orgsyn.095.0080","dataset_source_slug":"ord-dataset-5540e162c09f4c04905ddc8ba9c931c6","publication_source_slug":"ord-publication-8e01167d3a33166e","route_slugs":["ord-352807a1f4c14595afeef50c6c39ae38-baf09891a607","ord-352807a1f4c14595afeef50c6c39ae38-38fc672fffa7"],"reactant_slugs":["ord-compound-30427a4773c302982799","ord-compound-82f8e46dee7dd5570d43"],"product_slugs":["ord-compound-c48538141f742d70e0c0"],"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":{"inputs":{"4-dimethyl-aminopyridine":{"components":[{"identifiers":[{"type":"SMILES","value":"n1ccc(N(C)C)cc1"},{"type":"NAME","value":"4-dimethyl-aminopyridine"}],"amount":{"mass":{"value":12.8,"units":"GRAM"}},"reaction_role":"REAGENT","preparations":[{"type":"NONE","details":"used as received"}],"source":{"vendor":"Sigma Aldrich"}}],"addition_order":2},"pivaloyl chloride":{"components":[{"identifiers":[{"type":"SMILES","value":"CC(C)(C)C(=O)Cl"},{"type":"NAME","value":"pivaloyl chloride"}],"amount":{"volume":{"value":12.9,"units":"MILLILITER"}},"reaction_role":"REACTANT","preparations":[{"type":"NONE","details":"used as received"}],"source":{"vendor":"Alfa Aesar"}}],"addition_order":4,"addition_speed":{"type":"DROPWISE"},"addition_duration":{"value":5,"units":"MINUTE"},"addition_device":{"type":"SYRINGE","details":"plastic 30-mL syringe"}},"dichloromethane":{"components":[{"identifiers":[{"type":"SMILES","value":"C(Cl)Cl"},{"type":"NAME","value":"dichloromethane"}],"amount":{"volume":{"value":250,"units":"MILLILITER"}},"reaction_role":"SOLVENT","preparations":[{"type":"DRIED","details":"purified by passage under argon pressure through two packed columns of neutral alumina and copper(II) oxide"}],"source":{"vendor":"J. T. Baker"}}],"addition_order":3},"N,N-dibenzylhydroxylamine":{"components":[{"identifiers":[{"type":"SMILES","value":"C1=CC=C(C=C1)CN(CC2=CC=CC=C2)O"},{"type":"NAME","value":"N,N-dibenzylhydroxylamine"}],"amount":{"mass":{"value":21.3,"units":"GRAM"}},"reaction_role":"REACTANT","is_limiting":true,"preparations":[{"type":"CUSTOM","details":"a few colored or darker crystals, which were present in trace amounts, were discarded using standard tweezers"}],"source":{"vendor":"TCI America"}}],"addition_order":1}},"setup":{"vessel":{"type":"ROUND_BOTTOM_FLASK","details":"single-necked","material":{"type":"GLASS"},"preparations":[{"type":"OVEN_DRIED"},{"type":"PURGED","details":"with nitrogen"}],"attachments":[{"type":"SEPTUM","details":"rubber"}],"volume":{"value":500,"units":"MILLILITER"}},"is_automated":false,"environment":{"type":"FUME_HOOD"}},"conditions":{"temperature":{"control":{"type":"ICE_BATH","details":"reaction started in ice bath before addition of pivaloyl \nchloride, then allowed to warm to 23 C, then stirred for additional 6 hours at \nRT (23 degC)"},"setpoint":{"value":0,"units":"CELSIUS"}},"pressure":{"control":{"type":"SLIGHT_POSITIVE","details":"sealed with rubber septum, pierced with needle connected to manifold"},"atmosphere":{"type":"NITROGEN","details":"dry nitrogen"}},"stirring":{"type":"STIR_BAR"},"conditions_are_dynamic":true,"details":"reaction started in ice bath before addition of\npivaloyl chloride, then allowed to warm to 23 C, then stirred for '\nan additional 6 hours at RT (23 degC)"},"notes":{"is_heterogeneous":true},"workups":[{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"O"},{"type":"NAME","value":"water"}],"amount":{"volume":{"value":50,"units":"MILLILITER"},"volume_includes_solutes":true}},{"identifiers":[{"type":"SMILES","value":"[NH4+].[Cl-]"},{"type":"NAME","value":"ammonium chloride"}],"amount":{"mass":{"value":19.15,"units":"GRAM"}}}]}},{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"C(Cl)Cl"},{"type":"NAME","value":"DCM"}],"amount":{"volume":{"value":50,"units":"MILLILITER"}}}]}},{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"C(Cl)Cl"},{"type":"NAME","value":"DCM"}],"amount":{"volume":{"value":50,"units":"MILLILITER"}}}]}},{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"C(Cl)Cl"},{"type":"NAME","value":"DCM"}],"amount":{"volume":{"value":50,"units":"MILLILITER"}}}]}},{"type":"EXTRACTION","details":"3 x 50 mL DCM extraction in 1 L separatory funnel","keep_phase":"organic"},{"type":"WASH","input":{"components":[{"identifiers":[{"type":"SMILES","value":"O"},{"type":"NAME","value":"water"}],"amount":{"volume":{"value":200,"units":"MILLILITER"}}}]}},{"type":"CONCENTRATION","details":"rotary evaporator (30 degC, 80 mmHg)"},{"type":"DISSOLUTION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"C(Cl)Cl"},{"type":"NAME","value":"DCM"}],"amount":{"volume":{"value":50,"units":"MILLILITER"}}}]}},{"type":"FLASH_CHROMATOGRAPHY","details":"Aluminum oxide (neutral, powder, reagent-grade) was \npurchased from J.T. Baker. The crude reaction mixture is suspended in \ndichloromethane (50 mL) and is loaded onto a column, with interior diameter of \nroughly 2 inches, packed with alumina (100 g) and wetted with hexanes. \ndichloromethane is used as the eluent, and fractions are collected in Erlenmeyer\n flasks (50 mL each). The desired product typically elutes in fractions 2 \n through 25. The fractions that contain the desired product are combined"},{"type":"CONCENTRATION","details":"rotary evaporator (30 degC, 80 mmHg)"},{"type":"DRY_IN_VACUUM"}],"outcomes":[{"reaction_time":{"value":6,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"O=C(C(C)(C)C)ON(CC1=CC=CC=C1)CC2=CC=CC=C2"},{"type":"NAME","value":"N,N-Dibenzyl-O-pivaloylhydroxylamine"}],"is_desired_product":true,"measurements":[{"analysis_key":"1H NMR","type":"IDENTITY"},{"analysis_key":"13C NMR","type":"IDENTITY"},{"analysis_key":"HRMS","type":"IDENTITY"},{"analysis_key":"thin film IR","type":"IDENTITY"},{"analysis_key":"isolated_weight","type":"YIELD","percentage":{"value":93.5,"precision":0.5}},{"analysis_key":"quantitative NMR","type":"PURITY","percentage":{"value":99}},{"analysis_key":"isolated_weight","type":"AMOUNT","amount":{"mass":{"value":27.75,"units":"GRAM"}}}],"isolated_color":"white","texture":{"type":"POWDER"},"reaction_role":"PRODUCT"}],"analyses":{"HRMS":{"type":"HRMS","details":"ESI-TOF","is_of_isolated_species":true,"data":{"expected":{"float_value":298.1802,"description":"Expected m/z"},"found":{"float_value":298.1794,"description":"Observed m/z"}}},"isolated_weight":{"type":"WEIGHT","details":"27.5-28.0 g recovered after workup","is_of_isolated_species":true},"13C NMR":{"type":"NMR_13C","details":"101 MHz, CDCl3","is_of_isolated_species":true,"data":{"peaks":{"string_value":"27.1, 38.4, 62.4, 127.7, 128.3, 129.6, 136.2, 176.3","description":"List of peaks"}}},"thin film IR":{"type":"IR","details":"neat film, NaCl","is_of_isolated_species":true,"data":{"peaks":{"string_value":"3064, 3031, 2973, 2932, 2906, 2872, 1751, 1496, 1479, 1456, 1273, 1116, 1029, 738, 698","description":"List of peaks [cm-1]"}}},"quantitative NMR":{"type":"NMR_1H","details":"Quantitative NMR using 1,1,2,2-tetrachloroethane (>98%, purchased from Alfa Aesar) in CDCl3","is_of_isolated_species":true},"1H NMR":{"type":"NMR_1H","details":"400 MHz, CDCl3","is_of_isolated_species":true,"data":{"peaks":{"string_value":"0.92 (s, 9H), 4.06 (s, 4H), 7.23 - 7.34 (m, 6H), 7.40 (d, J = 7.1 Hz, 4H)","description":"List of peaks"}}}}}],"provenance":{"doi":"10.15227/orgsyn.095.0080","publication_url":"http://www.orgsyn.org/demo.aspx?prep=v95p0080"}}},"entities":[{"slug":"ord-compound-30427a4773c302982799","name":"N,N-dibenzylhydroxylamine","smiles":"ON(Cc1ccccc1)Cc1ccccc1","inchi":"InChI=1S/C14H15NO/c16-15(11-13-7-3-1-4-8-13)12-14-9-5-2-6-10-14/h1-10,16H,11-12H2","formula":"C14H15NO"},{"slug":"ord-compound-82f8e46dee7dd5570d43","name":"pivaloyl chloride","smiles":"CC(C)(C)C(=O)Cl","inchi":"InChI=1S/C5H9ClO/c1-5(2,3)4(6)7/h1-3H3","formula":"C5H9ClO"},{"slug":"ord-compound-c48538141f742d70e0c0","name":"N,N-Dibenzyl-O-pivaloylhydroxylamine","smiles":"CC(C)(C)C(=O)ON(Cc1ccccc1)Cc1ccccc1","inchi":"InChI=1S/C19H23NO2/c1-19(2,3)18(21)22-20(14-16-10-6-4-7-11-16)15-17-12-8-5-9-13-17/h4-13H,14-15H2,1-3H3","formula":"C19H23NO2"}],"dataset":{"dataset_id":"ord_dataset-5540e162c09f4c04905ddc8ba9c931c6","name":"Copper-Catalyzed Enantioselective Hydroamination of Alkenes","description":"Reaction data from Org. Synth. 2018, 95, 80-96 (DOI: 10.15227/orgsyn.095.0080)","records_in_source":3,"path":"data/55/ord_dataset-5540e162c09f4c04905ddc8ba9c931c6.parquet","sha256":"7e44b014c9041d86e00bc4fb4b70b3c6b3b94c0e35634467ace02c330efcd1a4","bytes":13289,"repository_url":"https://github.com/open-reaction-database/ord-data/blob/83f971f586f6ad18f358ae4ae99d045e94ed2066/data/55/ord_dataset-5540e162c09f4c04905ddc8ba9c931c6.parquet","download_url":"https://huggingface.co/datasets/open-reaction-database/ord-data/resolve/93475c46949f9218e1dfb6624096025135db2add/data/55/ord_dataset-5540e162c09f4c04905ddc8ba9c931c6.parquet"},"publication":{"slug":"ord-publication-8e01167d3a33166e","title":"Literature experiment — 10.15227/orgsyn.095.0080","source_type":"paper","doi":"10.15227/orgsyn.095.0080","url":"https://doi.org/10.15227/orgsyn.095.0080","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"]}