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[ CAS No. 84388-68-1 ]

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Chemical Structure| 84388-68-1
Chemical Structure| 84388-68-1
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Product Details of [ 84388-68-1 ]

CAS No. :84388-68-1 MDL No. :MFCD06739497
Formula : C7H4Cl2O2 Boiling Point : -
Linear Structure Formula :- InChI Key :N/A
M.W :191.01 g/mol Pubchem ID :-
Synonyms :

Safety of [ 84388-68-1 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 84388-68-1 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 84388-68-1 ]

[ 84388-68-1 ] Synthesis Path-Downstream   1~32

  • 1
  • [ 95-77-2 ]
  • [ 100-97-0 ]
  • [ 84388-68-1 ]
YieldReaction ConditionsOperation in experiment
58% With methanesulfonic acid at 105℃; for 1h; 4,5-dichloro-2-hydroxybenzaldehyde (61b). To a solution of 3,4-dichlorophenol (7.5 g, 46.3 mmol) in methane sulfonic acid (45 mL) was added hexamethylenetetramine (7.14 g, 50.9 mmol) in small portions. The mixture was slowly heated to 105 °C and kept at 105 °C for 1 h before being cooled to room temperature and poured into ice-water. The mixture was extracted with EtOAc, and the extracts were combined, washed with brine, dried over Na2SO4, and recrystallized to give a yellow solid (5.1g, 58%).
23% With methanesulfonic acid at 110℃; for 0.5h; 1.a Step a: To a stirred solution of 3,4-dichlorophenol (50.00 g, 306.75 mmol) in methanesulfonic acid (35 mL) was added hexamethyltetramine (47.50 g, 337.40 mmol) at room temperature. The reaction solution was stirred at 110 °C for 30 min. The reaction solution was allowed to cool down to room temperature and quenched with water (500 mL). The resulting solution was extracted with DCM (3 x 500 mL) and dried over anhydrous Na2SC>4. After the filtration, the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography, eluted with PE/DCM (10/1) to afford 4,5-dichloro-2- hydroxybenzaldehyde as a yellow solid (13.50 g, 23%): NMR (300 MHz, CDCh) d 10.96 (s, 1H), 9.84 (d, J= 0.7 Hz, 1H), 7.64 (s, 1H), 7.15 (s, 1H).
15% Stage #1: 3,4-dichlorophenol; hexamethylenetetramine In trifluoroacetic acid Heating / reflux; Stage #2: With sulfuric acid In water; trifluoroacetic acid at 25℃; for 4h; 2 Example 1-3; Preparation of salicylaldehydes (27a, 27b, 28b) via formylation of 4-sabstituted phenoles (duff formylation); Preparation of 4,5-dichloro-2-hydroxy-benzaldehyde (27b) General procedure. To a solution of the appropriately substituted phenol (10.0 g) in TFA (100 mL) was added HMTA (1.1 equivalent) in small portions. The reaction solution was heated at reflux overnight. After cooling, the solution was treated with 50% H2SO4 solution (40 mL) for 4 h at room temperature, and then was extracted with ether (3?100 mL). The combined ether phases were washed with 5 M HCl solution and water, and then dried over anhydrous MgSO4. After filtration, the filtrate was evaporated and purified. 2-Hydroxy-5-trifluoromethyl-benzaldehyde (27a). Following the general procedure and FCC purification with 30% ethyl acetate-hexane, 4-trifluoromethyl phenol (10.0 g, 61.7 mmol) gave 2-hydroxy-5-trifluoromethyl-benzaldehyde 27 (3.9 g, 34%) as a pink solid. Rf (20% ethyl acetate-hexane): 0.47. 1H NMR (300 MHz, CDCl3) ? 11.31 (s, 1H, OH), 9.96 (s, 1H, CHO), 7.87 (d, J=1.6 Hz, 1H, C6-H (Ph)), 7.76 (dd, J=2.0 and 8.5 Hz, 1H, C4-H (Ph)) and 7.11 (d, J=8.8 Hz, 1H, C3-H (Ph)). 13C NMR (75 MHz, CDCl3) ? 195.8, 163.8, 133.4(d), 131.0(d), 125.3, 122.1 (m), 119.8 and 118.6. 4,5-Dichloro-2-hydroxy-benzaldehyde (27b) and 5,6-dichloro-2-hydroxy-benzaldehyde (28). Following the general procedure and FCC purification with 5-10% ethyl acetate-hexane, 3,4-dichlorophenol (10.0 g, 61.1 mmol) gave 5,6-dichloro-2-hydroxy-benzaldehyde 28 (2.2 g, 19%) as a light yellow solid. Rf (40% ethyl acetate-hexane): 0.63. 1H NMR (300 MHz, CDCl3) ? 11.98 (s, 1H, OH), 10.44 (s, 1H, CHO), 7.55 (d, J=9.4 Hz, 1H, C4-H (Ph)) and 6.89 (d, J=9.3 Hz, 1H, C3-H (Ph)). 13C NMR (75 MHz, CDCl3) ? 195.4, 162.4, 137.8 (2C), 135.6, 123.8 and 118.1. From the same reaction continuous FCC purification with 10% ethyl acetate-hexane gave 4,5-dichloro-2-hydroxy-benzaldehyde 27b (1.8 g, 15%) as a light yellow solid. Rf (40% ethyl acetate-hexane): 0.47. 1H NMR (300 MHz, CDCl3) ? 10.97 (s, 1H, OH), 9.84 (s, 1H, CHO), 7.64 (s, 1H, C3-H (Ph)) and 7.15 (s, 1H, C6-H (Ph)). 13C NMR (75 MHz, CDCl3) ? 194.7, 160.0, 149.9, 141.5, 134.0, 123.6 and 119.9.
18.2 g With methanesulfonic acid at 105℃;
In methanesulfonic acid at 105℃; for 0.25h; 33.A 4,5-Dichloro-2-hydroxybenzaldehyde 3,4-Dichlorophenol (20.0 g, 0.123 mol) was added to methylsulfonic acid (120 mL) and stirred for 15 min to give a clear solution. To this solution was added slowlyhexamethylenetetramine (18.8 g, 0.134 mol) in small portions. The mixture was then heated to 105 °C and stirred for 15 min before being cooled to room temperature and poured into a mixture of ice and water (1.2 L). The mixture was extracted with DCM (200 mL *3) and the combined extracts were dried over sodium sulfate and concentrated to give the subtitle intermediate as a crude yellow solid (18.2 g, 77%).

  • 2
  • [ 1205681-42-0 ]
  • [ 84388-68-1 ]
  • [ 1205681-23-7 ]
YieldReaction ConditionsOperation in experiment
Stage #1: biphenyl-2-yl-carbamic acid 1-{2-[4-(2-amino-ethyl)-phenyl]-ethyl}-piperidin-4-yl ester; 4,5-dichloro-2-hydroxybenzaldehyde With acetic acid In ethanol for 1h; Stage #2: With sodium tris(acetoxy)borohydride In ethanol at 20℃; for 18h; Stage #3: With water In ethanol for 0.0833333h; 22 Example 22 Biphenyl-2-yl-carbamic acid 1-(2-{4-[2-(4,5-dichloro-2-hvdroxy-benzylamino)-ethyl1-phenyl)-ethvD- piperidin-4-yl ester; Biphenyl-2-yl-carbamic acid 1-{2-[4-(2-amino-ethyl)-phenyl]-ethyl}-piperidin-4-yl ester (Preparation 5, 40mg, 90μmol) was dissolved in ethanol (0.5ml) and added to a reaction vessel containing 4,5-dichloro-2- hydroxybenzaldehyde (17.2mg, 90μmol). To the reaction mixture was then added acetic acid (5.1 μl, 90μmol) and sodium sulphate (drying agent). The resulting mixture was allowed to stir for 1 hour. Sodium tri(acetoxy)borohydride (38mg, 178μmol) was then added, and the reaction allowed to stir at room temperature for 18h. The reaction was quenched with water (20μl) and stirred for 5 minutes. The solvents were removed in vacuo and the residue partitioned between dichloromethane (2ml) and saturated aqueous sodium hydrogen carbonate solution (2ml). The aqueous phase was separated and extracted with further dichloromethane (1 ml). The combined organic layers were concentrated in vacuo and the crude residue purified using an Isolute SCX-2 cartridge, eluting with methanol, followed by 1 M ammonia in methanol. The basic fractions were evaporated under reduced pressure and the residue purified by HPLC method E to afford the title compound. LCMS Method E: RT 2.27 min (100%area) ES m/z 618 [M+H]+.
  • 3
  • [ 1427594-56-6 ]
  • [ 84388-68-1 ]
  • [ 1427594-95-3 ]
YieldReaction ConditionsOperation in experiment
80.5% With sodium tris(acetoxy)borohydride; acetic acid In 1,2-dichloro-ethane at 20℃; 60 2-((4-(6-amino-5-(4-fluorophenyl)pyrimidin-4-yl)piperazin-1 -yl)methyl)-415- dichlorophenol ("60") 2-((4-(6-amino-5-(4-fluorophenyl)pyrimidin-4-yl)piperazin-1 -yl)methyl)-415- dichlorophenol ("60")A reaction mixture of 5-(4-fluoro-phenyl)-6-piperazin-1 -yl-pyrimidin-4-ylamine (400.0 mg; 1 .46 mmol; 1 .00 eq.), 4,5-dichloro-2-hydroxy-benzaldehyde (279.5 mg; 1 .46 mmol; 1 .00 eq.), Acetic acid (87.8 mg; 1 .46 mmol; 1 .00 eq.) and sodium triacetoxy borohydride (926.1 mg; 4.39 mmol; 3.00 eq.) in DCE (1 0 ml ) was stirred overnight at RT. The reaction solution was diluted with DCM and washed with brine. The organic layer was dried and concentrated, which was added 10ml of ether and stirred for 5mins. The precipitate was filtered to afford the title asd white off solid (528mg, yield 80.5%). LC-MS: (M+1 =448, obsd. = 448/450).
  • 4
  • [ 141-97-9 ]
  • [ 84388-68-1 ]
  • [ 1087738-71-3 ]
YieldReaction ConditionsOperation in experiment
92% With ziconium(IV) oxychloride octahydrate at 20℃; for 0.333333h; Milling; Green chemistry;
  • 5
  • [ 84388-68-1 ]
  • [ 105-53-3 ]
  • ethyl 6,7-dichloro-2-oxo-2H-chromene-3-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
90% With ziconium(IV) oxychloride octahydrate at 20℃; for 0.666667h; Milling; Green chemistry;
  • 6
  • [ 84388-68-1 ]
  • [ 95-54-5 ]
  • C20H12Cl4N2O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With formaldehyd EXPERIMENTAL General procedure: Modified salen ligands were synthesized by a single-step Mannich condensation between the phenylene diamine, ethylene diamine, formaldehyde and the substituted phenol. The synthesized salen compounds are shown in Scheme 1 the structures of synthetic compounds are confirmed with the spectroscopic data.
  • 7
  • [ 84388-68-1 ]
  • [ 107-15-3 ]
  • C16H12Cl4N2O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With formaldehyd EXPERIMENTAL General procedure: Modified salen ligands were synthesized by a single-step Mannich condensation between the phenylene diamine, ethylene diamine, formaldehyde and the substituted phenol. The synthesized salen compounds are shown in Scheme 1 the structures of synthetic compounds are confirmed with the spectroscopic data.
  • 8
  • [ 14741-71-0 ]
  • [ 84388-68-1 ]
  • [ 1333341-00-6 ]
  • 9
  • 3-ethyl-1-isopentyl-1,3,8-triazaspiro[4.5]decane-2,4-dione hydrochloride [ No CAS ]
  • [ 84388-68-1 ]
  • 8-[(4,5-dichloro-2-hydroxyphenyl)methyl]-3-etyl-1-(3-methylbutyl)-1,3,8-triazaspiro[4.5]decane-2,4-dione hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
46.82% Stage #1: 3-ethyl-1-isopentyl-1,3,8-triazaspiro[4.5]decane-2,4-dione hydrochloride; 4,5-dichloro-2-hydroxybenzaldehyde In N,N-dimethyl-formamide at 20℃; for 0.5h; Stage #2: With sodium tris(acetoxy)borohydride In N,N-dimethyl-formamide at 20℃; for 24h; Stage #3: With hydrogenchloride In diethyl ether 8-[(4,5-dichloro-2-hydroxyphenyl)methyl]-3-etyl-1-(3-methylbutyl)-1,3,8-triazaspiro[4.5]decane-2,4-dione hydrochloride (12k) A mixture of 12n (30.3 mg, 0.10mmol, 1 equiv) and 4,5-dichloro-2-hydroxybenzaldehyde (38.2 mg, 0.20 mmol, 2 equiv) was dissolved in DMF (2 mL) and stirred at room temperature for 30 minutes before the addition of sodium triacetoxyborohydride (50.8 mg, 0.24 mmol, 2.4 equiv). The reaction stirred at room temperature under anhydrous conditions for 24 h. It was then quenched with water (1 mL) then purified by reverse phase HPLC (10% to 75% acetonitrile/water/0.05% TFA). The product was treated with 2 M HCl in diethyl either (0.1 mL) and stirred for 15 minutes before being filtered and dried to yield 66.7 mg product as a HCl salt. The solid was then dissolved in minimum amount of DCM and loaded onto an SCX column (2 g). The residual impurities were eluted with 1:1 MeOH/DCM (10 mL). The product was eluted with 2 M Ammonia/MeOH (10 mL). The ammonia eluent was then condensed yielding 30.2 mg final compound. The ammonia product was then condensed and dissolved in diethyl ether (1 mL). The product was then treated with 2M HCl in diethyl ether (0.05 mL) to make an HCl salt. The salt was filtered, yielding the final compound as an off white HCl salt (25.6 mg, 0.0532 mmol, 46.82% yield). 1H NMR (400 MHz,DMSO-d6) δ 7.42 (s, 1 H), 7.00 (s, 1 H), 3.66 (br. s., 1 H), 3.38 (q, J=7.2 Hz, 4 H), 3.09 - 3.25(m, 2 H), 2.78 (br. s., 4 H), 1.89 - 2.08 (m, 2 H), 1.69 (br. s., 2 H), 1.53 - 1.65 (m, 1 H), 1.34 -1.51 (m, 2 H), 1.07 (t, J=7.2 Hz, 3 H), 0.91 (d, J=6.6 Hz, 6 H). ES-MS m/z 443.84 (M+H).
  • 10
  • [ 84388-68-1 ]
  • tert-butyl [[2-[2-(allyloxy)-4,5-dichlorophenyl]cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 11 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: caesium carbonate / N,N-dimethyl-formamide / 80 °C / Microwave irradiation
  • 11
  • [ 84388-68-1 ]
  • tert-butyl [[2-(4,5-dichloro-2-methoxyphenyl)cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate
  • 12
  • [ 84388-68-1 ]
  • tert-butyl [[2-(4,5-dichloro-2-methoxyphenyl)cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate
  • 13
  • [ 84388-68-1 ]
  • tert-butyl [[2-[4,5-dichloro-2-(2-fluoroethoxy)phenyl]cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 12 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 1 h / 0 - 60 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate
  • 14
  • [ 84388-68-1 ]
  • tert-butyl [[2-[4,5-dichloro-2-(2-fluoroethoxy)phenyl]cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 12 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 1 h / 0 - 60 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate
  • 15
  • [ 84388-68-1 ]
  • tert-butyl [[2-[2-(allyloxy)-4,5-dichlorophenyl]cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 12 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: caesium carbonate / N,N-dimethyl-formamide / 80 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate
  • 16
  • [ 84388-68-1 ]
  • tert-butyl [[2-[2-(allyloxy)-4,5-dichlorophenyl]cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 12 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: caesium carbonate / N,N-dimethyl-formamide / 80 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate
  • 17
  • [ 84388-68-1 ]
  • (-)-[2-(4,5-dichloro-2-methoxyphenyl)cyclopropyl]-methanamine hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 10 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate 10.1: hydrogenchloride / diethyl ether / 20 °C
  • 18
  • [ 84388-68-1 ]
  • (+)-[2-(4,5-dichloro-2-methoxyphenyl)cyclopropyl]-methanamine hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 10 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate 10.1: hydrogenchloride / diethyl ether / 20 °C
  • 19
  • [ 84388-68-1 ]
  • (-)-[2-[4,5-dichloro-2-(2-fluoroethoxy)phenyl]cyclopropyl]-methanamine hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 1 h / 0 - 60 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate 13.1: hydrogenchloride / diethyl ether / 20 °C
  • 20
  • [ 84388-68-1 ]
  • (+)-[2-[4,5-dichloro-2-(2-fluoroethoxy)phenyl]cyclopropyl]-methanamine hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 1 h / 0 - 60 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate 13.1: hydrogenchloride / diethyl ether / 20 °C
  • 21
  • [ 84388-68-1 ]
  • (E)-3-(4,5-dichloro-2-methoxyphenyl)-N-methoxy-N-methylacrylamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2: dichloromethane / 20 °C
  • 22
  • [ 84388-68-1 ]
  • (-)-[2-[2-(allyloxy)-4,5-dichlorophenyl]cyclopropyl]-methanamine hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: caesium carbonate / N,N-dimethyl-formamide / 80 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate 13.1: hydrogenchloride / diethyl ether / 20 °C
  • 23
  • [ 84388-68-1 ]
  • (+)-[2-[2-(allyloxy)-4,5-dichlorophenyl]cyclopropyl]-methanamine hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: caesium carbonate / N,N-dimethyl-formamide / 80 °C / Microwave irradiation 12.1: RegisPack chiral column / ethanol; hexane / Resolution of racemate 13.1: hydrogenchloride / diethyl ether / 20 °C
  • 24
  • [ 84388-68-1 ]
  • C11H10Cl2O2 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere
  • 25
  • [ 84388-68-1 ]
  • 2-(4,5-dichloro-2-methoxyphenyl)-N-methoxy-N-methylcyclopropanecarboxamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C
  • 26
  • [ 84388-68-1 ]
  • [2-(4,5-dichloro-2-methoxyphenyl)cyclopropyl]methanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C
  • 27
  • [ 84388-68-1 ]
  • 2-[[2-(4,5-dichloro-2-methoxyphenyl)cyclopropyl]methyl]isoindoline-1,3-dione [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C
  • 28
  • [ 84388-68-1 ]
  • C11H13Cl2NO [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux
  • 29
  • [ 84388-68-1 ]
  • (rac-trans)-tert-butyl ((2-(4,5-dichloro-2-methoxyphenyl)cyclopropyl)methyl)carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C
  • 30
  • [ 84388-68-1 ]
  • C10H11Cl2NO [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere
  • 31
  • [ 84388-68-1 ]
  • tert-butyl [[2-(4,5-dichloro-2-hydroxyphenyl)cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 10 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C
  • 32
  • [ 84388-68-1 ]
  • tert-butyl [[2-[4,5-dichloro-2-(2-fluoroethoxy)phenyl]cyclopropyl]methyl]carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 11 steps 1.1: potassium carbonate / N,N-dimethyl-formamide / 20 °C 2.1: dichloromethane / 20 °C 3.1: sodium hydride / dimethyl sulfoxide / 20 °C 3.2: 20 °C 4.1: diisobutylaluminium hydride / tetrahydrofuran / -78 °C / Inert atmosphere 5.1: sodium tetrahydroborate / methanol / 0 - 20 °C 6.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 0 - 20 °C 7.1: hydrazine hydrate / ethanol / 3 h / Reflux 8.1: triethylamine / dichloromethane / 0.5 h / 20 °C 9.1: boron tribromide / dichloromethane / 3 h / -78 °C / Inert atmosphere 10.1: triethylamine / dichloromethane / 0.5 h / 20 °C 11.1: triphenylphosphine; diethylazodicarboxylate / tetrahydrofuran / 1 h / 0 - 60 °C / Microwave irradiation
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