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[ CAS No. 529-34-0 ]

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Chemical Structure| 529-34-0
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CAS No. :529-34-0 MDL No. :MFCD00001688
Formula : C10H10O Boiling Point : 255.8°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :146.19 g/mol Pubchem ID :10724
Synonyms :

Safety of [ 529-34-0 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P264-P270-P301+P312-P312-P330-P501 UN#:N/A
Hazard Statements:H302-H313 Packing Group:N/A
GHS Pictogram:

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  • Upstream synthesis route of [ 529-34-0 ]
  • Downstream synthetic route of [ 529-34-0 ]

[ 529-34-0 ] Synthesis Path-Upstream   1~26

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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 4, p. 1184 - 1187
[2] Patent: CN108727416, 2018, A,
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YieldReaction ConditionsOperation in experiment
81% at 15℃; for 1 h; Concentrated sulfuric acid (60 ml) was cooled to 0°C in an ice bath. A-TETRALONE (8g, 54.7 mmol) was added with stirring, then potassium nitrate (6g, 59.3 mmol, 1.08 equiv. ) dissolved in concentrated sulfuric acid (18 ml) was added dropwise via a dropping funnel, making sure that the temperature of the solution did not rise above 15°C. After addition, the solution was stirred for 1 h and then poured into crushed ice. The precipitate was filtered and washed with distilled water and then left to dry. Recrystallisation from a ETHANOL/WATER (1: 1) yielded 8 as a slightly yellow solid (8.5 g, 81percent), m. p. 104-106°C ; I. R. (FILM)/CM~L 1675,1500, 1340 ; 1H NMR (400 MHz, CDC13) 2.18-2. 25 (2H, m, CH2), 2.75 (2H, t, J 6.8, CH2), 3.10 (2H, t, J 6. 1, CH2), 7. 45 (1H, d, J 8.4, ArH), 8. 30 (1H, dd, J 2. 4, 8. 4, ArH), 8. 86 (1H, d, J 2. 4, ArH).
65% at -20℃; for 0.75 h; 7-Nitrotetralone was synthesized by nitration of commercially available 1-tetralone following the method previously described, and its spectroscopic data were consistent with those of the Literature
[16]
. Yield: 65percent.
Mp 106-108 °C (Hexane). IR: 1355, 1519, 1607, 1681, 3085. 1H NMR (CDC13): δ 2.13-2.30 (m, 2H, H3); 2.66-2.81 (m, 2H, H4); 3.10 (t, J = 6.0 Hz, 2H, H2); 7.50 (d, J = 8.4 Hz, 1H, H5); 8.30 (dd, J = 2.5 Hz, J = 8.4 Hz, 1H, H6); 8.80 (d, J = 2.5 Hz, 1H, H8).
13C NMR (CDCl3): δ 22.4 (C3); 29.6 (C4); 38.4 (C2); 122.1 (C8); 126.9 (C6); 130.2 (C5); 133.2 (C8a); 146.8 (C7); 150.9 (C4a); 195.9 (C1). MS (CI): m/z = 192.0 (MH+, 100percent), 162.1 (29).
5.2 g With sulfuric acid; nitric acid In water at 0 - 20℃; for 1.5 h; Method 17
8-Amino-1-methyl-1,3,4,5-tetrahydro-2H-1-benzazepin-2-one
5 g of alpha-tetralone are added to 18.2 ml of sulfuric acid cooled to 0° C., while maintaining the temperature <10° C.
A mixture of 1.87 ml of nitric acid at 70percent in water and of 3.65 ml of sulfuric acid is added while maintaining the temperature <10° C.
The reaction medium is stirred for 30 minutes at a temperature <10° C. and then stirred for one hour at ambient temperature.
The reaction medium is poured into ice-cold water (250 ml).
The insoluble material is filtered off under vacuum and dried, so as to give 5.2 g of 7-nitro-3,4-dihydronaphthalen-1(2H)-one in the form of a beige solid.
5.2 g With sulfuric acid; nitric acid In water at 0 - 20℃; for 1.5 h; 5 g of alpha-tetralone are added to 18.2 ml of sulfuric acid cooled to O 'C, while maintaining the temperature < l O'C. A mixture of 1 .87 ml of nitric acid at 70percent in water and of 3.65 ml of sulfuric acid is added while maintaining the temperature < l O'C. The reaction medium is stirred for 30 minutes at a temperature < l O'C and then stirred for one hour at ambient temperature. The reaction medium is poured into ice-cold water (250 ml). The insoluble material is filtered off under vacuum and dried, so as to give 5.2 g of 7-nitro- 3,4-dihydronaphthalen-1 (2H)-one in the form of a beige solid

Reference: [1] Patent: WO2004/87124, 2004, A1, . Location in patent: Page/Page column 47-48
[2] European Journal of Medicinal Chemistry, 2014, vol. 71, p. 237 - 249
[3] Tetrahedron Letters, 1994, vol. 35, # 38, p. 7061 - 7064
[4] Justus Liebigs Annalen der Chemie, 1927, vol. 451, p. 53
[5] Journal of the Chemical Society. Perkin transactions 1, 1969, vol. 10, p. 1376 - 1378
[6] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 9, p. 2649 - 2655
[7] Patent: US5216148, 1993, A,
[8] Patent: US6235789, 2001, B1,
[9] Patent: US2013/261106, 2013, A1, . Location in patent: Paragraph 0563
[10] Patent: WO2013/150036, 2013, A1, . Location in patent: Page/Page column 110
[11] Patent: US6087399, 2000, A,
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YieldReaction ConditionsOperation in experiment
16% at 0℃; for 1 h; Λ/-(5,6,7,8-Tetrahydro-2-naphthalenyl)acetamide (166). fHNO3 (8.6 mL, 144 mmol) in CH2SO4 (50 mL) was added dropwise to a stirred solution of α-tetralone (165) (20 g, 137 mmol) in CH2SO4 (300 mL) at 0 0C and the solution stirred for 1 h. The solution was poured into ice/water (2 L), stirred for 30 min, filtered and washed with water. The solid was dried and purified by chromatography, eluting with 20percent EtOAc/pet. ether, to give (i) 5-nitro-3,4-dihydro-1(2H)-naphthalenone (4.1 g, 16percent) as a white solid: 1H NMR δ 8.35 (dd, J = 7.8, 1.4 Hz, 1 H, H-6), 8.09 (dd, J = 8.0, 1.4 Hz, 1 H, H-8), 7.48 (br t, J = 7.9 Hz, 1 H, H-7), 3.22 (t, J = 6.1 Hz, 2 H, H-4), 2.74 (dd, J = 6.8, 6.4 Hz, 2 H, H-2), 2.13-2.21 (m, 2 H, H-3); and (ii) 7-nitro-3,4-dihydro-1(2H)-naphthalenone (20.1 g, 77percent) as a white solid: 1H NMR δ 8.86 (d, J = 2.5 Hz, 1 H, H-4), 8.30 (dd, J = 8.4, 2.5 Hz, 1 H, H-6), 7.46 (d, J = 8.4 Hz, 1 H, H-5), 3.09 (t, J = 6.1 Hz, 2 H, H-4), 2.74 (dd, J = 7.0, 6.2 Hz, 2 H, H-2), 2.17- 2.25 (m, 2 H, H-3).A solution of 7-nitro-3,4-dihydro-1 (2H)-naphthalenone (1.67 g, 8.7 mmol) in EtOAc/EtOH (1 :1, 150 mL), water (15 mL) and cHCI (2 mL) with Pd/C (5percent, 500 mg) was stirred vigorously under H2 (60 psi) for 16 h. The suspension was filtered through Celite, washed with EtOH (4 x 10 mL) and the organic solvent evaporated. The aqueous residue was partitioned between DCM and dilute aqueous NH3 solution and the organic fraction dried and the solvent evaporated. The residue was dissolved in dioxane (20 mL), and Ac2O (1.8 mL, 19.2 mmol) was added dropwise to the solution at 0 0C. The solution was stirred at 20 0C for 16 h, diluted with water (50 mL), and partitioned between EtOAc and dilute aqueous NH3 solution. The organic fraction was washed with water (3 \\ 20 mL), dried and the solvent evaporated to give Λ/-(5,6,7,8-tetrahydro-2-naphthalenyl)acetamide 166 (1.57 g, 95percent) as a white solid: 1H NMR δ 7.18-7.25 (m, 2 H, H-1, NH), 7.15 (dd, J = 8.2, 2.1 Hz, 1 H, H-3), 7.00 (d, J = 8.2 Hz, 1 H, H-4), 2.69-2.77 (m, 4 H, 2 x CH2), 2.15 (s, 3 H, CH3), 1.74-1.80 (m, 4 H, 2 x CH2). The procedure was repeated a number of times to give N- (5,6,7, 8-tetrahydro-2-naphthalenyl)acetamide 166 (10.21 g, 88percent overall).
Reference: [1] Journal of Medicinal Chemistry, 2008, vol. 51, # 21, p. 6853 - 6865
[2] Patent: WO2006/104406, 2006, A1, . Location in patent: Page/Page column 126
[3] Journal of the American Chemical Society, 1994, vol. 116, # 11, p. 4852 - 4857
[4] Journal of Medicinal Chemistry, 1989, vol. 32, # 9, p. 2128 - 2134
[5] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 14, p. 466
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Reference: [1] Justus Liebigs Annalen der Chemie, 1927, vol. 451, p. 53
[2] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 14, p. 466
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Reference: [1] Fortschr. Teerfarbenfabr. Verw. Industriezweige, vol. 14, p. 466
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  • [ 109-77-3 ]
  • [ 2510-03-4 ]
Reference: [1] Organic and Biomolecular Chemistry, 2012, vol. 10, # 4, p. 852 - 860
[2] European Journal of Organic Chemistry, 2006, # 16, p. 3767 - 3770
[3] Journal of Organic Chemistry, 2005, vol. 70, # 9, p. 3584 - 3591
[4] European Journal of Organic Chemistry, 2015, vol. 2015, # 19, p. 4119 - 4130
[5] Angewandte Chemie - International Edition, 2016, vol. 55, # 51, p. 15792 - 15796[6] Angew. Chem., 2016, vol. 128, # 51, p. 16024 - 16028,5
[7] Russian Chemical Bulletin, 2003, vol. 52, # 10, p. 2235 - 2240
[8] Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, 2014, vol. 69, # 5, p. 509 - 518
[9] Organic Letters, 2013, vol. 15, # 20, p. 5298 - 5301
[10] Journal of the American Chemical Society, 1945, vol. 67, p. 1050
[11] Journal of Organic Chemistry, 1966, vol. 31, p. 2784 - 2789
[12] Phosphorus, Sulfur and Silicon and the Related Elements, 1993, vol. 82, # 1-4, p. 91 - 98
[13] Journal of Medicinal Chemistry, 2005, vol. 48, # 19, p. 6066 - 6083
[14] Organic and Biomolecular Chemistry, 2006, vol. 4, # 1, p. 63 - 70
[15] Tetrahedron Letters, 2008, vol. 49, # 37, p. 5389 - 5392
[16] Advanced Synthesis and Catalysis, 2008, vol. 350, # 11-12, p. 1781 - 1784
[17] Synthetic Communications, 2011, vol. 41, # 10, p. 1410 - 1420
[18] Journal of Organic Chemistry, 2013, vol. 78, # 14, p. 7154 - 7168
[19] European Journal of Medicinal Chemistry, 2014, vol. 85, p. 450 - 457
[20] Journal of Molecular Catalysis B: Enzymatic, 2014, vol. 109, p. 170 - 177
[21] Organic Letters, 2016, vol. 18, # 3, p. 428 - 431
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Reference: [1] Tetrahedron Letters, 1985, vol. 26, # 40, p. 4955 - 4956
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  • [ 119-64-2 ]
  • [ 21032-12-2 ]
  • [ 529-33-9 ]
  • [ 529-34-0 ]
  • [ 106477-02-5 ]
Reference: [1] Tetrahedron Letters, 1996, vol. 37, # 12, p. 2063 - 2066
[2] Journal of the Chemical Society. Perkin Transactions 2, 1998, # 11, p. 2429 - 2434
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Reference: [1] Chemical and pharmaceutical bulletin, 2002, vol. 50, # 6, p. 744 - 748
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  • [ 21032-12-2 ]
Reference: [1] Journal of the American Chemical Society, 1989, vol. 111, # 1, p. 410 - 411
[2] Chemistry - A European Journal, 2016, vol. 22, # 41, p. 14567 - 14575
[3] ChemCatChem, 2018, vol. 10, # 14, p. 2962 - 2968
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Reference: [1] Chemistry Letters, 1991, # 5, p. 813 - 816
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YieldReaction ConditionsOperation in experiment
50% With toluene-4-sulfonic acid In toluene at 60℃; for 6 h; 2-(4-(4-chlorophenyl)-1-hydroxycyclohexyl)-3,4-dihydronaphthalen-1-(2H)-one (12.0 g, 0.0.034 mol) was charged in a reactor equipped with overhead stirrer, reflux condenser and thermo-pocket. Toluene (200 mL) was added to suspend the material and p-toluene sulfonic acid (0.3 g, 2.5 mol percent) was added to the reaction mass which was then heated to 60 °C and stirred for 6 h. Progress of reaction was monitored on TLC. After completion of reaction, reaction mass was cooled to RT and solvent was evaporated under pressure to obtain residue. To the residue, was added ethyl acetate (150 mL) and washed with sat. NaHC03 soln. and brine followed by evaporation of solvent to give crude product which was further recrystallised from methanol to afford white solid compound (5.3 g, 50 percent yield). The mother liquor obtained after re-crystallisation was subjected to GC analysis wherein both a-tetralone and 4-(4-chlorophenyl) cyclohexanone were identified to be present in approx. 1 : 1 ratio (by respective retention times and AUCs in the mother liquor) and in 50 percent yield. GC retention time: a-tetralone (XII): 17.21 min (Area percent : 46)
Reference: [1] Patent: WO2013/14486, 2013, A1, . Location in patent: Page/Page column 19
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Reference: [1] Patent: WO2013/14486, 2013, A1, . Location in patent: Page/Page column 20
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Reference: [1] Patent: WO2017/106624, 2017, A1,
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  • [ 529-34-0 ]
Reference: [1] Patent: US5492905, 1996, A,
[2] Patent: US5502048, 1996, A,
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Reference: [1] Journal of Heterocyclic Chemistry, 1983, vol. 20, # 3, p. 663 - 666
[2] Justus Liebigs Annalen der Chemie, 1927, vol. 451, p. 53
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Reference: [1] Patent: US5502048, 1996, A,
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YieldReaction ConditionsOperation in experiment
95% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Step A:
1-Tetralone oxime
To 4.6 L of water at room temperature in a 4-neck 50 L flask sitting in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol).
To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone.
Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture.
The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes.
The reaction mixture was cooled with the aid of ice packed around the flask.
When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel.
The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel.
When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water.
The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40° C. for 2 days to give 2.094 Kg (13.01 mol,95percent) of product.
1 H NMR (250 MHz,CDCl3): 1.90 (m,2H), 2.80 (t,6 Hz,2H), 2.88 (t,6 Hz,2H), 7.15-7.35 (m,3H), 7.90 (d,8 Hz,1H), 8.9 (br s,1H).
95% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Step A:
1-Tetralone oxime
To 4.6 L of water at room temperature in a 4-neck 50 L flask sitting in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol).
To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone.
Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture.
The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes.
The reaction mixture was cooled with the aid of ice packed around the flask.
When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel.
The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel.
When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water.
The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40° C. for 2 days to give 2.094 Kg (13.01 mol, 95percent) of product. 1 H NMR (250 MHz, CDCl3): 1.90 (m, 2H), 2.80 (t, 6 Hz, 2H), 2.88 (t, 6 Hz, 2H), 7.15-7.35 (m, 3H), 7.90 (d, 8 Hz, 1H), 8.9 (br s, 1H).
95% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Step A:
1-Tetralone oxime
To 4.6L of water at room temperature in a 4-neck 50 L flask sitting in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol).
To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone.
Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture.
The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes.
The reaction mixture was cooled with the aid of ice packed around the flask.
When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel.
The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel.
When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water.
The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at a40° C. for 2 days to give 2.094 Kg (13.01 mol, 95percent) of product. 1 H NMR (250 MHz, CDCl3): 1.90 (m,2 H), 2.80 (t,6 Hz,2H), 2.88 (t,6 Hz,2H), 7.15-7.35 (m,3H), 7.90 (d,8 Hz,1H), 8.9 (br s,1H).
95% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Step A
1-Tetralone oxime
To 4.6 L of water at room temperature in a 4-neck 50 L flask sitting in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol).
To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone.
Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture.
The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes.
The reaction mixture was cooled with the aid of ice packed around the flask.
When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel.
The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel.
When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water.
The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40° C. for 2 days to give 2.094 Kg (13.01 mol, 95percent) of product. 1 H NMR (250 MHz, CDCl3): 1.90 (m,2H), 2.80 (t,6 Hz,2H), 2.88 (t,6 Hz,2H), 7.15-7.35 (m,3H), 7.90 (d,8 Hz,1H), 8.9 (br s,1H).
95% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Step A
1-Tetralone oxime
To 4.6 L of water at room temperature in a 4-neck 50 L flask sitting in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol).
To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone.
Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture.
The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes.
The reaction mixture was cooled with the aid of ice packed around the flask.
When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel.
The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel.
When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water.
The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40° C. for 2 days to give 2.094 Kg (13.01 mol, 95percent) of product, 1 H NMR (250 MHz, CDCl3): 1.90 (m, 2H), 2.80 (t, 6 Hz, 2H), 2.88 (t, 6 Hz, 2H), 7.15-7.35 (m, 3H), 7.90 (d, 8 Hz, 1H), 8.9 (br s, 1H).
95% With hydroxylamine hydrochloride; sodium acetate In ethanol; water Step A
1-Tetralone oxime
To 4.6 L of water at room temperature in a 4-neck 50 L flask sitting in a steam bath apparatus equipped with an overhead stirrer, a temperature probe and reflux condenser was added 3.72 Kg (27.36 mol) of sodium acetate with stirring, followed by 1.9 Kg of hydroxylamine hydrochloride (27.36 mol).
To this slurry at room temperature, 12 L of ethanol was added followed by 1.994 Kg (13.68 mol) of 1-tetralone.
Additional ethanol (1.7 L) was used to rinse off the funnel and added to the reaction mixture.
The resulting light orange slurry was heated to 75° C. over 40 minutes and maintained at 75°-85° C. for another 75 minutes.
The reaction mixture was cooled with the aid of ice packed around the flask.
When the internal temperature reached 32° C., the reaction mixture was pumped over 15 minutes into 60 L of ice contained in a 200 L vessel.
The reaction vessel was washed with an additional 2 L of water which was added to the 200 L vessel.
When the ice melted, the mixture was filtered through a filter pad and the wet cake washed with 4 L of water.
The wet cake was suction dried for 1 hour then transferred to two trays and dried under vacuum at 40° C. for 2 days to give 2.094 Kg (13.01 mol, 95percent) of product. 1 H NMR (250 MHz, CDCl3): δ 1.90 (m, 2H), 2.80 (t, 6 Hz, 2H), 2.88 (t, 6 Hz, 2H), 7.15-7.35 (m, 3H), 7.90 (d, 8 Hz, 1H), 8.9 (br s, 1H).
75% With hydroxylamine hydrochloride In pyridine; methanol for 16 h; Heating / reflux To a solution of 3,4-dihydro-2H-naphthalen-1-one (30 g, 20.5 mmol) in 1:1 MeOH/pyridine (100 mL) was added hydroxylamine hydrochloride (1.88 g, 31 mmol) and the resulting mixture was heated at reflux for 16 h.
The solvent was evaporated to give a brown solid that was dissolved in CH2Cl2 and washed with 0.5 N HCl.
After trituation from EtOAc, 1A was obtained as a brown solid (24.8 g, 75percent). LC/MS m/z 162.0 (M+H)+.
63% With hydroxylamine hydrochloride In methanol for 2 h; Heating / reflux Preparation 17l 4,5, 6,7-Tetrahydroazepino [3,2, 1-hi] indole; 3, 4-Dihydro-2H-naphthalen-1-one oxime; Add hydroxylamine hydrochloride (71.0 g, 1.03 mol) to a solution of a-tetralone (100.0 g, 0.68 mol) in 300 mL of methanol and stir the resulting solution at reflux for 2 hours. Cool the mixture to 20-24°C and concentrate under reduced pressure. Dilute the residue with 1 L of water and extract with dichloromethane. Wash the organic layer with saturated aqueous sodium chloride, dry over sodium sulfate, filter, and concentrate under reduced pressure. Crystallize the residue from isopropanol to provide the desired compound as an off-white solid (70.0 g, 63percent). MS (FIA, m/z) CloHllNO (M++1) = 162.4.
63% With hydroxylamine hydrochloride In methanol for 2 h; Heating / reflux Preparation X 4,5,6,7-Tetrahydroazepino[3,2,1-hi]indole [0185] 3,4-Dihydro-2H-naphthalen-1-one Oxime [0186] To a solution of α-tetralone (100.0 g, 0.68 mol) in 300 mL of methanol was added hydroxylamine hydrochloride (71.0 g, 1.03 mol) and the resulting solution was stirred at reflux for 2 hours. The mixture was allowed to cool to 20-24° C. and was concentrated under reduced pressure. The resulting mixture was diluted with 1 L of water and extracted with dichloromethane. The organic layer was washed with saturated aqueous sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was crystallized from isopropanol to provide 70.0 g (63percent) of the desired compound as an off-white solid. [0187] MS (FIA, m/z) C10H11NO (M++1)=162.4. [0188] 1,3,4,5-Tetrahydrobenzo[b]azepin-2-one [0189] A 1L 3-neck round bottom flask equipped with a mechanical stirrer was charged with neat polyphosphoric acid (100 g) and the acid heated to 125° C. while being stirred under nitrogen. 3,4-Dihydro-2H-naphthalen-1-one oxime (15.0 g, 93 mmol) was added carefully to control exotherm, keeping the temperature below 175° C. Following 10 minutes of heating the mixture was cooled to 20-24° C. and the reaction quenched with ice and water to generate a precipitate. The aqueous suspension was filtered and the precipitate washed with water until the filtrate became neutral. The filtered solid was dried under vacuum to provide 12.8 g (85percent) of the desired compound as an off-white solid. [0190] MS (ES, m/z) C10H11NO (M++1)=161.9 [0191] 2,3,4,5-Tetrahydro-1H-benzo[b]azepine [0192] To a solution of 1,3,4,5-tetrahydrobenzo[b]azepin-2-one (12.9 g, 80.0 mmol) in 720 mL of tetrahydrofuran was added 80 mL of lithium aluminum hydride (1 M solution in tetrahydrofuran). The reaction mixture was stirred at reflux for 3 hours and cooled to 0° C. The reaction was quenched by the sequential addition of 3 mL of water, 3 mL of 15percent sodium hydroxide, and 9 mL of water. The mixture was filtered through Celite and the filter cake rinsed with ethyl acetate. The filtrate was concentrated under reduced pressure to provide 10.0 g (85percent) of the desired compound as an orange solid. [0193] MS (FIA, m/z) C10H13N (M++1)=148.2. [0194] 2-Oxo-3-(2,3,4,5-tetrahydro-benzo[b]azepin-1-yl)-propionic acid ethyl ester [0195] To a 0° C. suspension of 60percent sodium hydride (3.0 g, 0.12 mol) in 300 mL of dimethylformamide was added 2,3,4,5-tetrahydro-1H-benzo[b]azepine in small portions. Upon complete addition of the amine, the ice bath was removed and the reaction stirred at 20-24° C. for 40 minutes. Ethyl bromopyruvate (22.6 mL, 0.16 mol) was then added and the resulting mixture stirred at 20-24° C. for 6 hours. An additional 5 mL of ethyl bromopyruvate was added and the mixture stirred for 1 hour. The reaction was quenched by the addition of 50 mL of water followed by dilution with 1.5 L of dichloromethane. The layers were separated and the organic layer was washed with water (2.x.500 mL) and saturated aqueous sodium chloride (500 mL). The organic phase was dried over sodium sulfate, filtered and concentrated under reduced pressure at 60° C. The residual brown oil was dissolved in ethyl acetate (500 mL) and was washed 3 times with water (100 mL) and once with saturated aqueous sodium chloride, dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was subjected to silica gel chromatography, eluting with 5-10percent EtOAc/hexanes to provide 7.0 g (40percent) of the desired compound as an off white solid. [0196] MS (FID, m/z) C15H19NO3 (M+)=261.13. [0197] 4,5,6,7-Tetrahydroazepino[3,2,1-hi]indole-1-carboxylic acid ethyl ester [0198] Magnesium chloride (2.55 g, 26.8 mmol) was added to 30 mL of 2-methoxyethanol and the mixture heated to reflux. A solution of 2-oxo-3-(2,3,4,5-tetrahydro-benzo[b]azepin-1-yl)-propionic acid ethyl ester (7-0.0 g, 26.8 mmol) in 2-methoxyethanol (20 mL) was slowly added to the MgCl2 mixture over 1 hour. The resulting mixture was stirred for 6 hours at reflux, cooled to 20-24° C. and concentrated under reduced pressure. The residue was diluted with 400 mL of dichloromethane and washed with 2 N hydrochloric acid (100 mL), followed by saturated aqueous sodium bicarbonate (100 mL) and finally saturated aqueous sodium chloride (100 mL). The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. This residue was subjected to silica gel chromatography, eluting with 20percent EtOAc/Hexane. Fractions containing product were combined and concentrated under reduced pressure to provide 3.1 g (48percent) of the desired compound as a yellow oil. [0199] MS (FIA, m/z) C15H17NO2 (M++1)=244.4. [0200] 4,5,6,7-Tetrahydroazepino[3,2,1-hi]indole-1-carboxylic Acid [0201] To a solution of 4,5,6,7-tetrahydroazepino[3,2,1-hi]indole-1-carboxylic acid ethyl ester (2.0 g, 8.22 mmol) in ethanol (13 mL) and water (9 mL) was added powdered sodium hydroxide (0.71 g, 17.8 mmol) and the resulting mixture stirred at reflux for 4 hours. The reaction mixture was cooled to room temperature, diluted with water (100 mL) and washed with dichloromethane (2.x.50 mL). The layers were separated and the aqueous layer was filtered through Celite and the filtrate was acidified with concentrated hydrochloric acid. The suspension was filtered and the recovered solid washed with water and dried under reduced pressure to provide 1.59 g (90percent) of the desired compound as a white solid. [0202] MS (FIA, m/z) C13HL3NO2 (M++1)=216.3 [0203] Decarboxylation [0204] To a solution of 4,5,6,7-tetrahydroazepino[3,2,1-hi]indole-1-carboxylic acid (1.4 g, 6.5 mmol) in 7.5 mL of quinoline was added copper chromite (0.55 g, 1.77 mmol). The resulting mixture was stirred at 185° C. for 4 hours and then cooled to room temperature, diluted with dichloromethane and filtered through Celite. The filtrate was washed with 2 N hydrochloric acid (2.x.25 mL) followed by 2 N sodium hydroxide (25 mL). The organic layer was concentrated under reduced pressure and the residue subjected to silica gel chromatography, eluting with 5percent EtOAc/Hexane to provide 0.85 g (76percent) of the title compound as an orange solid. [0205] MS (EI, m/z) C12H13N (M+)=171.4
4.4 g With hydroxylamine hydrochloride; sodium acetate In methanol for 1 h; Reflux 1-tetralone (4.00 g, 27.40 mmol), sodium acetate (2.64 g, 32.20 mmol), hydroxylamine hydrochloride (2.42 g, 32.2 mmol) and methanol (12.00 mL) were stirred under reflux for 1 h, then, ethyl acetate (50.00 mL) and 2M NaOH solution (50 mL) were added and the organic phase was extracted and concentrated by reduced pressure. After this, water (40.00 mL), ethyl acetate (80.00 mL) and saturated NaCl solution (50.00 mL) were added to the resultant mixture. The organic phase was extracted, dried over MgSO4 and concentrated under reduced pressure furnishing 4.40 g (27.40 mmol) of a white solid without futher purification.

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