[ CAS No. 562-46-9 ] {[proInfo.proName]}

Name: 562-46-9|4,4-Dimethylcyclohexane-1,3-dione|97%
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Product Details of [ 562-46-9 ]

CAS No. :	562-46-9	MDL No. :	MFCD00075224
Formula :	C₈H₁₂O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	PLGPBTCNKJQJHQ-UHFFFAOYSA-N
M.W :	140.18	Pubchem ID :	136360
Synonyms :

Safety of [ 562-46-9 ]

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

Application In Synthesis of [ 562-46-9 ]

* 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.

Upstream synthesis route of [ 562-46-9 ]
Downstream synthetic route of [ 562-46-9 ]

[ 562-46-9 ] Synthesis Path-Upstream 1~11

1
[ 563-80-4 ]
[ 140-88-5 ]
[ 562-46-9 ]

Yield	Reaction Conditions	Operation in experiment
49.2%	With potassium <i>tert</i>-butylate In tetrahydrofuran at 0 - 20℃; for 0.333333 h;	Step-i: 4,4-dimethylcyclohexane- L3-dione To a 100 mL of round bottom flask, were added isopropyl methyl ketone (5.0 g, 58.05 mmol), potassium i-butoxide (13.0 g, 116.1 mmol) and THF (50 mL). The reaction mixture was cooled to 0 °C. To the same flask, ethyl acrylate (5.8 g, 58.05 mmol) was added at 0 °C. The reaction mixture was stirred at room temperature for 20 min. The reaction mixture was quenched with aqueous ammonium chloride and extracted with ethyl acetate. The solvent was separated, washed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to get crude product. The crude product was purified by column chromatography using 60-120 silica gel and 50 percent ethyl acetate in hexane to get the title compound (4.0 g, 49.2 percent). NMR (300 MHz, CDC1₃): δ 3.28 (s, 2H), 2.64 (t, 2H), 1.87 (t, 2H), 1.22 (s, 6H); LC-MS: 141.0 [M+H]⁺.
31%	Stage #1: With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.0833333 h; Stage #2: at 0 - 20℃; for 1 h;	Step-i: 4,4-dimethylcyclohexane-l,3-dione (la) To a 250 mL round bottom flask, were added 3-methyl-2-butanone (10 g, 0.1162 mol) and THF (150 mL). To the same flask, potassium feri-butoxide (36.28 g, 0.2324 mol) was added. The reaction mixture was cooled to 0 °C and stirred at 0 °C for 5 min. To the same flask, ethyl acrylate (11.62 g, 0.1162 mol) was added drop wise at 0 °C. The resulting reaction mixture was stirred at room temperature for 1 h. The reaction mixture was quenched with saturated aqueous ammonium chloride and washed with ethyl acetate. The aqueous layer was separated, acidified to pH 6.0 with 2 N hydrochloric acid and extracted with ethyl acetate. The organic layer was separated, washed with brine and dried over anhydrous sodium sulphate. The organic layer was evaporated under reduced pressure to get the crude product. The crude product was purified by column chromatography over silica gel (60-120) using 50 percent ethyl acetate in hexane as eluent to get the titled compound [5 g, 31 percent]. 1H NMR (300 MHz, CDC1₃): δ 3.28 (s, 2H), 2.64 (t, 2H), 1.87 (t, 2H), 1.22 (s, 6H); LC-MS: 141.0 [M+H]⁺.

Reference： [1] Journal of Organic Chemistry, 2001, vol. 66, # 24, p. 8000 - 8009
[2] Patent: WO2015/101928, 2015, A1, . Location in patent: Page/Page column 104; 105
[3] Patent: WO2015/83130, 2015, A1, . Location in patent: Page/Page column 30
[4] Journal of the American Chemical Society, 1968, vol. 90, p. 4085 - 4088
[5] European Journal of Organic Chemistry, 2012, # 4, p. 673 - 677

2
[ 86289-92-1 ]
[ 562-46-9 ]

Yield	Reaction Conditions	Operation in experiment
50%	With sodium methylate In diethyl ether at 5 - 20℃;	7.8 g (4.0 eq.) of sodium methoxide were suspended in 100 ml of ethyl ether and cooled to 5° C. 2,2-dimethyl-5-oxo-hexanoic acid methyl ester (7.5 g) (0.043 mole) was taken up in 25 ml of ethyl ether and added slowly to the reaction. The reaction was warmed to room temperature and stirred overnight. Cold water (100 ml) was added to the reaction and the ether layer was removed after shaking. The aqueous layer was acidified with 1N HCl and extracted with ethyl acetate. The ethyl acetate layer was dried over sodium sulfate, filtered and stripped to 5.8 g of a colorless oil. The crude product was taken up in 97.5/2.5 methylene chloride/methanol and charged on a Biotage Flash 90 cartridge (silica). The weight of the pure product which was eluted with the methylene chloride/methanol was 3.0 g ( 50percent yield). MS: (-) ES (M-H)^-139, Elemental Anal. Calcd. for: C₈H₁₂O₂=0.4 mole H₂O, C, 65.19percent; H, 8.75percent, N, 0.00percent, Found: C, 65.13percent; H, 8.20percent; N, 0.00percent, ¹H-NMR (DMSO-d₆): δ 5.09 (s, 1H); 3.31 (b,1H); 2.32 (m, 2H): 1.69 (t, 2H); 0.99 (s, 6H).

Reference： [1] Patent: US2006/14826, 2006, A1, . Location in patent: Page/Page column 14
[2] Journal of the Chemical Society, 1956, p. 4068,4071
[3] Canadian Journal of Chemistry, 1964, vol. 42, p. 212 - 222

3
[ 563-80-4 ]
[ 1663-39-4 ]
[ 562-46-9 ]

Reference： [1] Journal of Organic Chemistry, 2001, vol. 66, # 24, p. 8000 - 8009

4
[ 98-01-1 ]
[ 563-80-4 ]
[ 1663-39-4 ]
[ 562-46-9 ]

Reference： [1] Journal of Organic Chemistry, 2001, vol. 66, # 24, p. 8000 - 8009

5
[ 98-01-1 ]
[ 563-80-4 ]
[ 1663-39-4 ]
[ 562-46-9 ]

Reference： [1] Journal of Organic Chemistry, 2001, vol. 66, # 24, p. 8000 - 8009

6
[ 2938-48-9 ]
[ 562-46-9 ]

Reference： [1] Canadian Journal of Chemistry, 1964, vol. 42, p. 212 - 222

7
[ 2840-71-3 ]
[ 562-46-9 ]

Reference： [1] Canadian Journal of Chemistry, 1964, vol. 42, p. 212 - 222

8
[ 98559-84-3 ]
[ 562-46-9 ]

Reference： [1] Canadian Journal of Chemistry, 1964, vol. 42, p. 212 - 222

9
[ 4054-90-4 ]
[ 562-46-9 ]

Reference： [1] Journal of Organic Chemistry USSR (English Translation), 1966, vol. 2, p. 1771 - 1773[2] Zhurnal Organicheskoi Khimii, 1966, vol. 2, p. 1801 - 1804

10
[ 91007-14-6 ]
[ 562-46-9 ]

Reference： [1] Journal of the Indian Chemical Society, 1959, vol. 36, p. 299

11
[ 53696-42-7 ]
[ 562-46-9 ]

Reference： [1] Journal of Organic Chemistry USSR (English Translation), 1965, vol. 1, p. 1018 - 1023[2] Zhurnal Organicheskoi Khimii, 1965, vol. 1, # 6, p. 1010 - 1016

[ 562-46-9 ] Synthesis Path-Downstream 1~88

1
[ 78-83-1 ]
[ 562-46-9 ]
[ 60067-97-2 ]

Yield	Reaction Conditions	Operation in experiment
80%	With toluene-4-sulfonic acid; In benzene; at 20℃; for 15h;Dean-Stark; Reflux;	To a stirred solution of <strong>[562-46-9]4,4-dimethylcyclohexane-1,3-dione</strong> (5.00 g, 35.6 mmol) in benzene (100 mL) were added p-TsOH (355mg, 1.86 mmol) and i-BuOH (6.7 mL, 72.5 mmol) at room temperature. After reflux with Dean-Stark apparatus for 15 h, the reaction mixture was diluted with Et2O and the reaction was quenched with saturated aqueous NaHCO3. The water phase was extracted with Et2O and the combined organic extracts were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo. The residue was purifiedby flash column chromatography on silica gel (eluent: hexane/AcOEt = 3:1) to give the vinylogous ester 6(5.57 g, 80%) as a pale yellow oil. 1H NMR (300 MHz, CDCl3) delta 5.23 (1H, s), 3.58 (2H, d, J = 6.6 Hz), 2.43 (2H, t, J = 5.8 Hz), 2.17-2.15(1H, m), 1.80 (2H, t, J = 6.3 Hz), 1.15 (6H, s), 0.98 (6H, d, J = 6.6 Hz); 13C NMR (75 MHz, CDCl3) delta204.2, 175.8, 100.8, 74.4, 39.9, 34.8, 27.5, 26.0, 24.4, 18.9; IR (neat) 1655, 1611 cm-1; HRMS (EI) calcdfor C12H20O2 (M+) 196.1463, found 196.1463.

Reference： [1]Heterocycles,2016,vol. 93,p. 783 - 791
[2]Journal of the Indian Chemical Society,1959,vol. 36,p. 299

2
[ 86289-92-1 ]
[ 562-46-9 ]

Yield	Reaction Conditions	Operation in experiment
50%	With sodium methylate; In diethyl ether; at 5 - 20℃;	7.8 g (4.0 eq.) of sodium methoxide were suspended in 100 ml of ethyl ether and cooled to 5 C. 2,2-dimethyl-5-oxo-hexanoic acid methyl ester (7.5 g) (0.043 mole) was taken up in 25 ml of ethyl ether and added slowly to the reaction. The reaction was warmed to room temperature and stirred overnight. Cold water (100 ml) was added to the reaction and the ether layer was removed after shaking. The aqueous layer was acidified with 1N HCl and extracted with ethyl acetate. The ethyl acetate layer was dried over sodium sulfate, filtered and stripped to 5.8 g of a colorless oil. The crude product was taken up in 97.5/2.5 methylene chloride/methanol and charged on a Biotage Flash 90 cartridge (silica). The weight of the pure product which was eluted with the methylene chloride/methanol was 3.0 g ( 50% yield). MS: (-) ES (M-H)- 139, Elemental Anal. Calcd. for: C8H12O2=0.4 mole H2O, C, 65.19%; H, 8.75%, N, 0.00%, Found: C, 65.13%; H, 8.20%; N, 0.00%, 1H-NMR (DMSO-d6): delta 5.09 (s, 1H); 3.31 (b,1H); 2.32 (m, 2H): 1.69 (t, 2H); 0.99 (s, 6H).

Reference： [1]Patent: US2006/14826,2006,A1 .Location in patent: Page/Page column 14
[2]Journal of the Chemical Society,1956,p. 4068,4071
[3]Canadian Journal of Chemistry,1964,vol. 42,p. 212 - 222

3
[ 563-80-4 ]
[ 140-88-5 ]
[ 562-46-9 ]

Yield	Reaction Conditions	Operation in experiment
49.2%	With potassium tert-butylate; In tetrahydrofuran; at 0 - 20℃; for 0.333333h;	Step-i: 4,4-dimethylcyclohexane- L3-dione To a 100 mL of round bottom flask, were added isopropyl methyl ketone (5.0 g, 58.05 mmol), potassium i-butoxide (13.0 g, 116.1 mmol) and THF (50 mL). The reaction mixture was cooled to 0 C. To the same flask, ethyl acrylate (5.8 g, 58.05 mmol) was added at 0 C. The reaction mixture was stirred at room temperature for 20 min. The reaction mixture was quenched with aqueous ammonium chloride and extracted with ethyl acetate. The solvent was separated, washed with brine and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to get crude product. The crude product was purified by column chromatography using 60-120 silica gel and 50 % ethyl acetate in hexane to get the title compound (4.0 g, 49.2 %). NMR (300 MHz, CDC13): delta 3.28 (s, 2H), 2.64 (t, 2H), 1.87 (t, 2H), 1.22 (s, 6H); LC-MS: 141.0 [M+H]+.
31%		Step-i: 4,4-dimethylcyclohexane-l,3-dione (la) To a 250 mL round bottom flask, were added 3-methyl-2-butanone (10 g, 0.1162 mol) and THF (150 mL). To the same flask, potassium feri-butoxide (36.28 g, 0.2324 mol) was added. The reaction mixture was cooled to 0 C and stirred at 0 C for 5 min. To the same flask, ethyl acrylate (11.62 g, 0.1162 mol) was added drop wise at 0 C. The resulting reaction mixture was stirred at room temperature for 1 h. The reaction mixture was quenched with saturated aqueous ammonium chloride and washed with ethyl acetate. The aqueous layer was separated, acidified to pH 6.0 with 2 N hydrochloric acid and extracted with ethyl acetate. The organic layer was separated, washed with brine and dried over anhydrous sodium sulphate. The organic layer was evaporated under reduced pressure to get the crude product. The crude product was purified by column chromatography over silica gel (60-120) using 50 % ethyl acetate in hexane as eluent to get the titled compound [5 g, 31 %]. 1H NMR (300 MHz, CDC13): delta 3.28 (s, 2H), 2.64 (t, 2H), 1.87 (t, 2H), 1.22 (s, 6H); LC-MS: 141.0 [M+H]+.

Reference： [1]Journal of Organic Chemistry,2001,vol. 66,p. 8000 - 8009
[2]Patent: WO2015/101928,2015,A1 .Location in patent: Page/Page column 104; 105
[3]Patent: WO2015/83130,2015,A1 .Location in patent: Page/Page column 30
[4]Journal of the American Chemical Society,1968,vol. 90,p. 4085 - 4088
[5]European Journal of Organic Chemistry,2012,p. 673 - 677

4
[ 67-56-1 ]
[ 562-46-9 ]
[ 90611-61-3 ]
[ 90611-60-2 ]

Yield	Reaction Conditions	Operation in experiment
82%; 18%	With toluene-4-sulfonic acid; In benzene; for 20h;Inert atmosphere; Reflux;	4,4-Dimeth-ylcyclohexane-1,3-dione (20) (10.02 g, 71.3 mmol) and p-TsOH (136 mg, 0.71 mmol) were refluxed in benzene (50 mL) and methanol (10 mL) using a Dean-Stark trap for a 20-h period. The reaction mixture was cooled to rt and then quenched with 5% Na2CO3 (50 mL). Standard ethereal workup, followed by chromatography (elution with H/E, 3:2), provided 9.82 g (82%) of enone 39, which was homogeneous by TLC analysis (H/E, 1:1, Rf20=0.35, Rf39=0.52): 1H NMR (400 MHz) delta 1.13 (s, 6H), 1.37 (t, 3H, J=7.0 Hz), 1.81 (t, 2H, J=6.4 Hz), 2.44 (t, 2H, J=6.4 Hz), 3.90 (q, 2H, J=7.0 Hz), 5.30 (s, 1H); 13C NMR (100.6 MHz) 14.3 (q), 24.7 (q), 26.4 (q), 35.1 (t), 40.3 (s), 64.3 (t), 101.1 (d), 176.1 (s), 204.8 (s) ppm; IR (film) 2980, 2927, 2868, 1651, 1611 cm-1; MS (m/z) 268 (M+). Continued elution (H/E, 3:2) gave 2.15 g (18%) of enone 40.
	With toluene-4-sulfonic acid; In water; for 2h;Heating / reflux;	Example 19Preparation of (3S)-3-[4-(11,11-dimethyl-spiro[5.5]undec-7-en-2-ylmethoxy)-phenyl]-hex-4-ynoic acid Step 1To a solution of <strong>[562-46-9]4,4-dimethyl-cyclohexane-1,3-dione</strong> (6.0 g) in methanol (80 mL) was added para-toluenesulfonic acid monohydrate (813 mg), followed by heating the reaction mixture under reflux for 2 hours. After cooling down to room temperature, the reaction mixture was concentrated. The residue was purified by column chromatography on silica gel (hexane:ethyl acetate (volume ratio)=3:1) to give a less-polar isomer (3.7 g) and a more-polar isomer (1.1 g).Less-Polar Isomer1H-NMR (CDCl3) delta: 1.12 (6H, s), 1.81 (2H, t, J=6.3 Hz), 2.44 (2H, t, J=6.3 Hz), 3.69 (3H, s), 5.27 (1H, s).More-Polar Isomer1H-NMR (CDCl3) delta: 1.20 (6H, s), 1.83 (2H, t, J=6.7 Hz), 2.41 (2H, t, J=6.7 Hz), 3.68 (3H, s), 5.26 (1H, s).

Reference： [1]Tetrahedron,2011,vol. 67,p. 10129 - 10146
[2]Journal of Organic Chemistry,2006,vol. 71,p. 2384 - 2388
[3]Journal of the American Chemical Society,1993,vol. 115,p. 2205 - 2216
[4]Tetrahedron,2001,vol. 57,p. 217 - 225
[5]Patent: US2009/170908,2009,A1 .Location in patent: Page/Page column 44; 45

5
[ 562-46-9 ]
[ 156723-07-8 ]
[ 156723-08-9 ]

Yield	Reaction Conditions	Operation in experiment
68%	With potassium carbonate; potassium iodide; In tetrahydrofuran; water; at 20℃; for 24h;Inert atmosphere;	4,4-Dimethylcyclohexane-1,3-dione (20) (2.78 g, 19.83 mmol, Aldrich), K2CO3 (1.37 g, 9.90 mmol), bromide 19 (3.00 g, 9.90 mmol), and KI (822 mg, 4.95 mmol) were dissolved in a mixture of 3 mL of water and 1.5 mL of THF. The reaction mixture was stirred at rt for a 24-h period. The aqueous solution was first extracted with ether (2×50 mL) and the combined ethereal extracts were washed with 100 mL of saturated aqueous NaHCO3. The resulting organic phase was extracted with 5% aqueous NaOH (2×50 mL) and the resulting aqueous solutions were acidified with 10% aqueous HCl and extracted with ether (3×50 mL). The ethereal extracts were dried over anhydrous MgSO4 and concentrated. The crude residue was chromatographed (elution with H/E, 3:1) to afford 2.51 g (68%) of 21, which was homogeneous by TLC analysis (H/E, 4:1, Rf21=0.24): mp 81-83 C; 1H NMR (250 MHz) delta 1.08 (s, 6H), 1.27 (d, 6H, J=6.9 Hz), 1.75 (t, 2H, J=6.5 Hz), 2.40 (t, 2H, J=6.5 Hz), 3.46 (heptet, 1H, J=6.9 Hz), 3.49 (s, 2H), 3.73 (s, 3H), 3.79 (s, 3H), 3.84 (s, 3H), 6.66 (s, 1H); 13C NMR (62.9 MHz) 202.7 (s), 170.4 (s), 155.5 (s), 150.8 (s), 142.3 (s), 131.1 (s), 128.5 (s), 112.6 (s), 108.2 (d), 61.6 (q), 61.0 (q), 55.6 (q), 39.5 (t), 35.2 (s), 34.1 (t), 25.7 (q), 25.0 (d), 24.9 (t), 21.1 (q) ppm; IR (film) 1734, 1705, 1603 cm-1; Elemental analysis for C21H28O5. Calculated: C, 69.59%, H, 8.34%. Found: C, 69.32%, H, 8.41%.

Reference： [1]Journal of the American Chemical Society,1994,vol. 116,p. 4979 - 4980
[2]Tetrahedron,2011,vol. 67,p. 10129 - 10146

6
[ 935-04-6 ]
[ 562-46-9 ]
[ 105499-10-3 ]
3-(3,3-Dimethyl-2,6-dioxocyclohexyl)-2-methylpyrrolidine [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2001,vol. 40,p. 903 - 905

7
[ 562-46-9 ]
[ 6361-22-4 ]
9-(2-chloro-6-nitro-phenyl)-2,2,7,7-tetramethyl-3,4,6,7,9,10-hexahydro-2<i>H</i>,5<i>H</i>-acridine-1,8-dione [ No CAS ]

Reference： [1]Il Farmaco,2004,vol. 59,p. 939 - 943

8
[ 562-46-9 ]
[ 830-03-5 ]
2-acetyl-4,4-dimethyl-1,3-cyclohexanedione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69.1%	With triethylamine; 2-hydroxy-2-methylpropanenitrile; In acetonitrile; at 20℃; for 4h;Heating / reflux;	EXAMPLE 37 Preparation of 2-Acetyl-<strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> A 50-ML single neck round bottom flask was charged with 4-nitrophenyl acetate (2.03 g, 11.2 mmol), <strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> (2.10 g, 15 mmol) and acetonitrile (15 ML).Then triethylamine (2.5 g, 25 mmol) and acetone cyanohydrin (0.14 ML, 1.5 mmol) were added and the mixture was stirred for 2 hours at ambient temperature. NMR analysis of an aliquot showed that 43% of the starting acetate was still unreacted.The mixture was then refluxed for 2 hours after which time NMR analysis of an aliquot showed no starting acetate remaining. Volatiles were stripped from the reaction mixture and the residue was partitioned between diethyl ether (100 ML) and 1N hydrochloric acid (50 ML).The organic layer was washed with brine (25 ML), dried over magnesium sulfate, filtered and stripped to a brown oil (3.78 g).This oil was chromatographed on silica gel (200 g), eluding with hexanes-ethyl acetate (9:1).Concentration of the fractions containing pure product afforded the title compound as a yellow oil, 1.41 g (69.1%).1H NMR (CDCl3): delta 1.16 (s, 3), 1.30 (s, 3), 1.83 (m, 2), 2.54 (m, 1), 2.60 (s, 3), 2.69 (m, 1).

Reference： [1]Patent: US2003/232984,2003,A1 .Location in patent: Page 16

9
[ 562-46-9 ]
[ 35022-43-6 ]
4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	With triethylamine;Zinc chloride; In dichloromethane;	EXAMPLE 1-B 4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione STR35 <strong>[562-46-9]4,4-Dimethyl-1,3-cyclohexanedione</strong> [14.0 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na2 CO3 four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was chromatographed (2% AcOH/CH2 Cl2) in 5 g aliquots then reduced on rotavap under reduced pressure at 50 C. for 30 minutes to remove AcOH. This yielded an oil (40% yield). The structure was confirmed by instrumental analysis. The compounds of Embodiment C of the present invention can be prepared by the following general method. STR36 Generally, in step (1) mole amounts of the dione and substituted benzoyl chloride are used, along with a slight mole excess of triethylamine. The two reactants are combined in a solvent such as methylene chloride.

Reference： [1]Patent: US4780127,1988,A

10
[ 562-46-9 ]
[ 476415-35-7 ]

Yield	Reaction Conditions	Operation in experiment
65%	With bromine; sodium acetate; In chloroform; at 0℃; for 1h;	Step-ii: 2-bromo-4,4-dimethylcyclohexane- 1 ,3-dione To a 100 mL round bottom flask, were added 4,4-dimethylcyclo hexane- 1,3-dione (4.0 g, 28.57 mmol), sodium acetate (2.5 g, 31.0 mmol) and chloroform (50 mL). The reaction mixture was cooled to 0 C. To the same flask, bromine (1.4 mL, 28.57 mmol) in chloroform (10 mL) was added drop wise. The reaction mixture was stirred at 0 C for 1 h. The reaction mixture was poured into water to get solid. The solid was collected by filtration to get the title compound [4.0 g, 65%]. NMR (300 MHz, CDCI3): delta 3.40 (s, 1H), 2.62 (t, 2H), 1.86 (t, 2H), 1.21 (s, 6H).
	With potassium bromate; hydrogen bromide; In water;	General procedure: A mixture of cyclohexane-1,3-dione (4.90 g, 35.0 mmol), 48% hydrobromic acid (3.96 mL, 35.0 mmol), and water (70 mL) was treated dropwise with a solution of potassium bromate (1.75 g, 10.5 mmol) in warm water (75 mL). After the addition was complete, the resulting precipitate was filtrated off, washed with water and dried in vacuo to yield 2-bromo-<strong>[562-46-9]6,6-dimethylcyclohexane-1,3-dione</strong>. A mixture of the crude bromo dione, trimethylorthoformate (3.83 mL, 35.0 mmol), and methanol (70 mL) was stirred in the presence of IR120Hion-exchange resin (350 mg, pre-washed with methanol). After 4 hr the mixture was filtrated and the filtrate evaporated. The residue was purified by column chromatography with chloroform/methanol (50/1) to give 2-bromo-3-methoxy-6,6-dimethylcyclohex-2-en-1-one (7b) as a colorless crystal in 73% yield
	With bromine; In diethyl ether; at -10℃; for 0.5h;	2-bromo-4,4-dimethyl-l,3-cyclohexadione (1). To a cooled stirred suspension of 4,4-dimethyl- 1,3 -cyclohexadione (2 g, 14.3 mmol) in 75 ml of diethyl ether at -1O0C was added bromine (732 muL, 14.3 mmol) slowly by syringe. After complete addition, the solution was stirred for an additional 30 minutes, whereupon it was quenched by the addition of water. The layers were separated, and the organic layer was washed repeatedly with water, and a 1A saturated solution of sodium bicarbonate. The aqueous layers were combined and further extracted with ether several times. The combined organic fractions were dried over sodium sulfate (Na2SO4 anh.). Filtration followed by removal of the solvent under reduced pressure afforded 2.5 grams of a light yellow solid (1), which was used in the next step without further purification.

Reference： [1]Patent: WO2015/101928,2015,A1 .Location in patent: Page/Page column 104; 105
[2]Tetrahedron Letters,2014,vol. 55,p. 4146 - 4148
[3]Patent: WO2006/129318,2006,A2 .Location in patent: Page/Page column 44

11
[ 562-46-9 ]
[ 24068-46-0 ]

Yield	Reaction Conditions	Operation in experiment
62%	With ammonium acetate; In toluene; for 4h;Dean-Stark; Reflux;	Step-ii: 3-amino-6,6-dimethylcyclohex-2-enone (lb) A 50 mL round bottom flask was charged with 4,4-dimethylcyclohexane-l,3-dione (la) (3 g, 0.0214 mol), ammonium acetate (1.97 g, 0.0257 mol) and toluene (50 mL). The round bottom flask was fitted with Dean-Stark reflux condenser. The reaction mixture was stirred at reflux temperature for 4 h. The volatiles were evaporated under reduced pressure to get the residue. The residue was triturated with ethyl acetate to get the solid. The solid was collected by filtration to obtain the titled compound [1.8 g, 62 %]. FontWeight="Bold" FontSize="10" H NMR (300 MHz, DMSO-d6): delta 6.47 (brs, 2H), 4.79 (s, 1H), 2.30 (t, 2H), 1.66 (t, 2H), 0.94 (s, 6H); LC-MS: 140.2 [M+H]+.
	With ammonium acetate;	3-Amino-6,6-dimethylcyclohex-2-en-1 -one[0056] In analogy to (Baraldi, P. G.; Simoni, D.; Manfredini, S.; Synthesis 1983, (11 ) 902-903) 4,4-dimethylcyclohexane-1 ,3-dione was reacted with ammonium acetate to give the title compound as a colorless solid. Physical characteristics are as follows:Mp 153-154 -0C; 1H NMR (DMSO-D6, TMS) delta: 0.94 (s, 6H); 1.64 (t, 6.5 Hz, 2H); 2.28 (t, 6.5 Hz, 2H); 4.79 (s, 1 H) and 6.58 ppm (br s, 2H).

Reference： [1]Patent: WO2015/83130,2015,A1 .Location in patent: Page/Page column 30
[2]Patent: WO2007/23245,2007,A1 .Location in patent: Page/Page column 38
[3]ACS Combinatorial Science,2011,vol. 13,p. 427 - 435

12
[ 562-46-9 ]
[ 261763-02-4 ]
[ 22502-03-0 ]
[ 1154416-05-3 ]

Reference： [1]European Journal of Medicinal Chemistry,2009,vol. 44,p. 2052 - 2058

13
[ 562-46-9 ]
[ 4637-24-5 ]
[ 1235325-51-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	at 20℃; for 1h;Inert atmosphere;	According to Scheme 2 Step 1 : A solution of 4,4-dimethylcyclohexane-l,3-dione (157 mmol, 22 g) and of l,l-dimethoxy-N,Lambda/-dimethylmethanamine (235 mmol, 31.3 mL) was stirred at room temperature for 1 hour. After evaporation and trituration in petroleum ether, 29.2 g (150 mmol, 95%) of 2-((dimethylamino)methylene)-4,4- dimethylcyclohexane-l,3-dione were obtained as a pale orange solid.UPLC-MS: RT = 0.50 min; MS m/z ES+= 196.
39%	In acetonitrile; at 20℃;	A mixture of <strong>[562-46-9]4,4-dimethylcyclohexane-1,3-dione</strong> (4.91 g, 35.0 mmol) and DMF-DMA (8.34 g, 70.0 mmol) in MeCN (35 mL) was stirred at rt overnight. Then the reaction mixture was concentrated at reduced pressure, triturated with diethyl ether, filtered, washed with diethyl ether, and dried in vacuo to give the product (2.71 g , 39%) as a yellow solid

Reference： [1]Patent: WO2010/79238,2010,A1 .Location in patent: Page/Page column 27-28
[2]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 4493 - 4500

14
[ 1033760-83-6 ]
[ 562-46-9 ]
2-(4'-chloro-4-ethylbiphenyl-3-yl)-4,4-dimethyl-1,3-cyclohexanedione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dmap; In chloroform; toluene; at 80℃; for 4h;	Step 8Preparation of 2-(4'-chloro-4-ethylbiphen-3-yl)-4,4-dimethyl-1 ,3-cyclohexanedione. To a mixture of 4,4-dimethyl-1 ,3-cyclohexanedione (0.21 g, 1.5 mmol), 4'-chloro-4- ethylbiphen-3-yllead triacetate (1 .0 g, 1.7 mmol) and dimethylaminopyridine (0.93 g, 7.6 mmol) is added anhydrous chloroform (1 1 ml) and anhydrous toluene (2.8 ml). The reaction mixture is heated at 80 0C for 4 hours and then cooled to room temperature. The mixture is diluted with dichloromethane (50 ml) and 2M aqueous hydrochloric acid (50 ml) and filtered through diatomaceous earth. The filtrate is partitioned, the aqueous layer is extracted with dichloromethane (50 ml) and the organic extracts are combined, washed with 2M aqueous hydrochloric acid (50 ml), brine (50 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The crude product is purified by preparative reverse phase HPLC to give 2-(4'-chloro-4- ethylbiphen-3-yl)-4,4-dimethyl-1 ,3-cyclohexanedione.
	With dmap; In chloroform; toluene; at 80℃; for 4h;	Step 8 Preparation of 2-(4'-chloro-4-ethylbiphen-3-yl)-<strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong>To a mixture of <strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> (0.21 g, 1.5 mmol), 4'-chloro-4-ethylbiphen-3-yllead triacetate (1.0 g, 1.7 mmol) and dimethylaminopyridine (0.93 g, 7.6 mmol) is added anhydrous chloroform (11 ml) and anhydrous toluene (2.8 ml). The reaction mixture is heated at 80 C. for 4 hours and then cooled to room temperature. The mixture is diluted with dichloromethane (50 ml) and 2M aqueous hydrochloric acid (50 ml) and filtered through diatomaceous earth. The filtrate is partitioned, the aqueous layer is extracted with dichloromethane (50 ml) and the organic extracts are combined, washed with 2M aqueous hydrochloric acid (50 ml), brine (50 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The crude product is purified by preparative reverse phase HPLC to give 2-(4'-chloro-4-ethylbiphen-3-yl)-<strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong>.

Reference： [1]Patent: WO2011/6543,2011,A1 .Location in patent: Page/Page column 47-48
[2]Patent: US2012/190545,2012,A1 .Location in patent: Page/Page column 22-23

15
[ 1033760-96-1 ]
[ 562-46-9 ]
2-(5-bromo-2-ethylphenyl)-4,4-dimethylcyclohexane-1,3-dione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With dmap; In chloroform; toluene; at 80℃; for 2h;Inert atmosphere;	Step 5: Preparation of 2-(5-bromo-2-ethylphenyl)-4,4-dimethylcyclohexane-1 ,3-dione. To a mixture of 4,4-dimethylcyclohexane-1 ,3-dione (6.28 g, 45 mmol), 5-bromo-2- ethylphenyl lead triacetate (28 g, 49 mmol) and dimethylaminopyridine (27.4 g, 0.22 mol) under nitrogen are added anhydrous chloroform (300 ml) and toluene (75 ml). The reaction mixture is heated at 80 0C for 2 hours and then allowed to cool to room temperature overnight. 2M Aqueous hydrochloric acid (750 ml) and dichloromethane (500 ml) are added and the mixture is filtered through diatomaceous earth, washing through with more dichloromethane (250 ml). The two layers are separated and the aqueous phase is extracted with dichloromethane (500 ml). The organic layers are combined and washed with 2M aqueous hydrochloric acid (1000 ml) and then brine (1000 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by preparative normal phasechromatography to give 2-(5-bromo-2-ethylphenyl)-4,4-dimethylcyclohexane-1 ,3-dione (6.78 g).
	With dmap; In chloroform; toluene; at 80℃; for 2h;Inert atmosphere;	Step 5: Preparation of 2-(5-bromo-2-ethylphenyl)-<strong>[562-46-9]4,4-dimethylcyclohexane-1,3-dione</strong>To a mixture of <strong>[562-46-9]4,4-dimethylcyclohexane-1,3-dione</strong> (6.28 g, 45 mmol), 5-bromo-2-ethylphenyl lead triacetate (28 g, 49 mmol) and dimethylaminopyridine (27.4 g, 0.22 mol) under nitrogen are added anhydrous chloroform (300 ml) and toluene (75 ml). The reaction mixture is heated at 80 C. for 2 hours and then allowed to cool to room temperature overnight. 2M Aqueous hydrochloric acid (750 ml) and dichloromethane (500 ml) are added and the mixture is filtered through diatomaceous earth, washing through with more dichloromethane (250 ml). The two layers are separated and the aqueous phase is extracted with dichloromethane (500 ml). The organic layers are combined and washed with 2M aqueous hydrochloric acid (1000 ml) and then brine (1000 ml), dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure. The residue is purified by preparative normal phase chromatography to give 2-(5-bromo-2-ethylphenyl)-<strong>[562-46-9]4,4-dimethylcyclohexane-1,3-dione</strong> (6.78 g).

Reference： [1]Patent: WO2011/6543,2011,A1 .Location in patent: Page/Page column 50-51
[2]Patent: US2012/190545,2012,A1 .Location in patent: Page/Page column 24

16
[ 50899-05-3 ]
[ 562-46-9 ]
[ 112641-20-0 ]
[ 1282581-82-1 ]

Reference： [1]Acta Crystallographica, Section C: Crystal Structure Communications,2011,vol. 67,p. o80-o84
[2]Drug Development Research,2012,vol. 73,p. 332 - 342

17
[ 562-46-9 ]
[ 762-21-0 ]
[ 109-77-3 ]
[ 1325716-37-7 ]

Yield	Reaction Conditions	Operation in experiment
82%	With methylamine; at 80℃; for 0.5h;Neat (no solvent);	General procedure: To a mixture of cyclic 1,3-dione (7.1 mmol), diethyl acetylene dicarboxylate (7.1 mmol), and malononitrile (7.1 mmol) was added methylamine (2.1 mmol) dropwise at room temperature. The reaction mixture was thoroughly ground and heated to 80 C for 30 min. Then molten mass was allowed to cool to room temperature and the resulting mixture was poured into water and the product was extracted with a minimum amount of chloroform, dried over sodium sulfate and crystallized in 3:2 chloroform/ethyl acetate to yield pure derivative of ethyl 2-amino-3-cyano-4-(2-ethoxy-2-oxoethyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-4-carboxylate (4). Spectroscopic data for all the compounds are given below.

Reference： [1]Tetrahedron,2011,vol. 67,p. 6057 - 6064

18
[ 1821-47-2 ]
[ 505-57-7 ]
[ 562-46-9 ]
[ 1334229-74-1 ]

Yield	Reaction Conditions	Operation in experiment
79%		General procedure for asymmetric organocatalyzed addition of diketone to alpha,beta-unsaturated aldehydes. Chiral secondary amine catalyst 5 (0.02 mmol, 0.1 equiv) was added to a solution of alpha,beta-unsaturated aldehyde 4 (0.3 mmol, 1.5 equiv) in DCM (0.2 mL) at 0 C while stirring, followed by the addition of diketone 3 (0.2 mmol, 1 equiv). The reaction was stirred for 48 h at 0 C, and filtered through a short pad of silica gel. After concentration under reduced pressure, the crude product 6a was obtained and used directly in the next step.General procedure for cascade reaction. Tryptamine 7 (0.3 mmol, 1.5 equiv) was added to a solution of crude hemiacetal 6 (0.2 mmol, 1 equiv) in DCM (2 mL) in a sealed tube followed by the addition of TFA (0.2 mol, 1 equiv). The reaction mixture was heated in an oil bath at 50 C for 12 h. After cooling to room temperature, the reaction mixture was diluted with DCM (10 mL) and quenched with saturated NaHCO3 (5 mL). The organic layer was separated and washed with brine (5 mL). After drying over anhydrous Na2SO4, the solvent was evaporated under reduced pressure and the crude product was purified by column chromatography on silica gel using petroleum ether-ethyl acetate as eluents to give the desired product 8.

Reference： [1]Tetrahedron,2011,vol. 67,p. 7251 - 7257

19
[ 1550-50-1 ]
[ 562-46-9 ]
2-difluoroacetyl-4,4-dimethyl-1,3-cyclohexadione [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
73%	In dichloromethane; at 8 - 20℃; for 120h;Inert atmosphere;	A 25 mL Teflon PFA flask equipped with digital thermometer, Teflon PTFE stir bar, and N2 inlet was placed in an ice/water bath and then charged with N,N-dimethylamino-1,1,2,2-tetrafluoroethane (TFEDMA, 4.1 g, 28.5 mmol, 1.6 equiv.). Once the internal temperature reached 8 C, <strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> (2.5 g, 17.8 mmol, 1.0 equiv.) was added in small portions to the stirring TFEDMA so as to keep the temperature below 15 C. The reaction mixture was left to magnetically stir at ambient temperature for 5 days. The crude mixture was a viscous yellow oil. EtOAc (20 mL) was added, and the reaction mixture was poured over an equal volume of 10% HCl solution. The aqueous layer was back extracted with EtOAc and all organic layers were combined. The organic layer was washed with additional 10% HCl (20 mL), deionized water (2× 20 mL), dried over MgSO4, and concentrated in vacuo for 12 h to give a flaky yellow solid (4.1 g) that still contained some EtOAc. The crude product was recrystallized from a warm CH2Cl2/hexanes mixture to give a white solid (2.82 g, 73% yield). Due to lack of symmetry, the two enol isomers of this compound show up separately in NMR as a 60/40 mol% mixture:Comment1H NMR: 6.90 (t, JFH = 53.6 Hz, 1H); 2.78 (t, JHH = 6.5 Hz, 2H); 1.87 (t, JHH = 6.5 Hz, 2H); 1.18 (s, 6H). 19F NMR: -130.2 (d, JFH = 53.5 Hz, 2F).Comment1H NMR: 6.93 (t, JFH = 53.6 Hz, 1H); 2.56 (t, JHH = 6.7 Hz, 2H); 1.89 (t, JHH = 6.7 Hz, 2H); 1.36 (s, 6H). 19F NMR: -130.0 (d, JFH = 53.5 Hz, 2F). MP by DSC: 63.1 C. Anal. Calc. for C10H12F2O3: C, 55.05: H, 5.54: F, 17.41. Found: C, 54.25: H, 5.57: F, 17.95.

Reference： [1]Journal of Fluorine Chemistry,2011,vol. 132,p. 1198 - 1206

20
[ 50899-05-3 ]
[ 562-46-9 ]
[ 93118-03-7 ]
[ 1422961-71-4 ]

Reference： [1]Drug Development Research,2012,vol. 73,p. 332 - 342

21
[ 562-46-9 ]
[ 100-63-0 ]
[ 1432509-57-3 ]

Yield	Reaction Conditions	Operation in experiment
47%	With trifluoroacetic acid; at 140℃; for 0.166667h;Microwave irradiation;	Step 1. Synthesis of 3,3-dimethyl-2,3-dihydro-lH-carbazol-4(9H)-on) [formula 5-2]To a microwave vial were added phenyl hydrazine [formula 5-1] (1.0 g, 7.13 mmol), 4- 4-dimethylcyclohexan-l,3-dioncarried out in a microwave reactor at 140C for 10 minutes. Then, the reaction mixture was extracted with ethyl acetate and saturated NaHC03 aqueous solution, the organic layer was washed with brine, dried over anhydrous Na2S04, filtered and concentrated under reduced pressure. Residue was purified by column chromatography (Si02; hexane/ethylacetate, 4/1) to yield the title compound (0.72 g, 47%).
47%	With trifluoroacetic acid; at 140℃; for 0.166667h;Microwave irradiation;	To a microwave vial were added phenyl hydrazine [formula 5-1] (1.0 g, 7.13 mmol), 4-4-dimethylcyclohexan-1,3-dion (0.926 g, 8.56 mmol) and TFA (10.0 mL), and a reaction was carried out in a microwave reactor at 140 C. for 10 minutes. Then, the reaction mixture was extracted with ethyl acetate and saturated NaHCO3 aqueous solution, the organic layer was washed with brine, dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. Residue was purified by column chromatography (SiO2; hexane/ethylacetate, 4/1) to yield the title compound (0.72 g, 47%).

Reference： [1]Patent: WO2013/62344,2013,A1 .Location in patent: Page/Page column 85; 86
[2]Patent: US2014/315889,2014,A1 .Location in patent: Paragraph 0410-0412

22
[ 562-46-9 ]
[ 70577-95-6 ]
[ 109-77-3 ]
[ 1443755-17-6 ]

Yield	Reaction Conditions	Operation in experiment
92%	With methylamine; In methanol; at 60℃; for 0.5h;	General procedure: To a mixture of cyclic 1,3-diketone 1 (1.0mmol), active methylene compound 2 (1.0equiv), and methyl 2-perfluoroalkynoate (1.1equiv) was added 37% methylamine methanolic solution (0.3equiv) dropwise at room temperature. After stirring at 60C for 0.5h, the mixture was allowed to cool to room temperature and diluted with water. After extraction with a minimum amount of chloroform, the organic layer was combined and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The residue was subjected to chromatography on silica gel using petroleum ether/AcOEt (2:1) as eluent to afford product 4 and 4?.

Reference： [1]Tetrahedron,2013,vol. 69,p. 6121 - 6128

23
[ 562-46-9 ]
[ 536-74-3 ]
6,6-dimethyl-3-(1-phenylvinyloxy)-2-cyclohexenone [ No CAS ]
4,4-dimethyl-3-(1-phenylvinyloxy)-2-cyclohexenone [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
48%; 20%	With dichlorotricarbonylruthenium(II) dimer; In benzene; at 70℃; for 5h;Inert atmosphere; Sealed tube;	General procedure: Under an atmosphere of argon, 1,3-cyclohexandione (4a, 56 mg, 0.5 mmol) andphenylacetylene (2a, 102 mg, 1 mmol) were placed in a screw-cap test tube. [RuCl2(CO)3]2(12.8 mg, 0.025 mmol) and benzene (1mL) were then added. After sealing, the mixture wasstirred using a stirring bar at 70 C for 5 h. After cooling, the reaction mixture was separatedby column chromatography on silica gel (hexane:AcOEt = 60:40), which allowed theisolation of the desired product 5a (84.4 mg) in 79% yield.

Reference： [1]Synlett,2013,vol. 24,p. 2287 - 2291

24
[ 27421-51-8 ]
[ 562-46-9 ]
[ 1578269-85-8 ]

Yield	Reaction Conditions	Operation in experiment
78%	With ammonium acetate; In methanol; at 120℃; for 0.166667h;Microwave irradiation;	General procedure: One-pot three component mixture of 2 mmol appropriate 1,3-cyclic dicarbonyl compound (1,3-cyclohexanedione/<strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> or 5,5-dimethyl-1,3-cyclohexanedione),1 mmol substituted indole carboxaldehyde (1-methyl-1H-indole-2-carbaldehyde/1-methyl-1H-indole-3-carbaldehyde/5-bromo-1H-indole-3-carbaldehyde or 6-bromo-1H-indole-3-carbaldehyde)and 5 mmol ammonium acetate was filled into 10 mL-microwavepressure vial and heated under microwave irradiation (power50W, maximum temperature 120 C) for 10 min in 5 mL methanol.After the reactionwas completed, the reaction mixture was pouredinto ice-water, the obtained precipitatewas filtered and crystallizedfrom ethanolewater.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 75,p. 258 - 266

25
[ 19012-03-4 ]
[ 562-46-9 ]
[ 1578269-88-1 ]

Yield	Reaction Conditions	Operation in experiment
73%	With ammonium acetate; In methanol; at 120℃; for 0.166667h;Microwave irradiation;	General procedure: One-pot three component mixture of 2 mmol appropriate 1,3-cyclic dicarbonyl compound (1,3-cyclohexanedione/<strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> or 5,5-dimethyl-1,3-cyclohexanedione),1 mmol substituted indole carboxaldehyde (1-methyl-1H-indole-2-carbaldehyde/1-methyl-1H-indole-3-carbaldehyde/5-bromo-1H-indole-3-carbaldehyde or 6-bromo-1H-indole-3-carbaldehyde)and 5 mmol ammonium acetate was filled into 10 mL-microwavepressure vial and heated under microwave irradiation (power50W, maximum temperature 120 C) for 10 min in 5 mL methanol.After the reactionwas completed, the reaction mixture was pouredinto ice-water, the obtained precipitatewas filtered and crystallizedfrom ethanolewater.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 75,p. 258 - 266

26
[ 877-03-2 ]
[ 562-46-9 ]
[ 1578269-91-6 ]

Yield	Reaction Conditions	Operation in experiment
80%	With ammonium acetate; In methanol; at 120℃; for 0.166667h;Microwave irradiation;	General procedure: One-pot three component mixture of 2 mmol appropriate 1,3-cyclic dicarbonyl compound (1,3-cyclohexanedione/<strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> or 5,5-dimethyl-1,3-cyclohexanedione),1 mmol substituted indole carboxaldehyde (1-methyl-1H-indole-2-carbaldehyde/1-methyl-1H-indole-3-carbaldehyde/5-bromo-1H-indole-3-carbaldehyde or 6-bromo-1H-indole-3-carbaldehyde)and 5 mmol ammonium acetate was filled into 10 mL-microwavepressure vial and heated under microwave irradiation (power50W, maximum temperature 120 C) for 10 min in 5 mL methanol.After the reactionwas completed, the reaction mixture was pouredinto ice-water, the obtained precipitatewas filtered and crystallizedfrom ethanolewater.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 75,p. 258 - 266

27
[ 17826-04-9 ]
[ 562-46-9 ]
[ 1578269-94-9 ]

Yield	Reaction Conditions	Operation in experiment
84%	With ammonium acetate; In methanol; at 120℃; for 0.166667h;Microwave irradiation;	General procedure: One-pot three component mixture of 2 mmol appropriate 1,3-cyclic dicarbonyl compound (1,3-cyclohexanedione/<strong>[562-46-9]4,4-dimethyl-1,3-cyclohexanedione</strong> or 5,5-dimethyl-1,3-cyclohexanedione),1 mmol substituted indole carboxaldehyde (1-methyl-1H-indole-2-carbaldehyde/1-methyl-1H-indole-3-carbaldehyde/5-bromo-1H-indole-3-carbaldehyde or 6-bromo-1H-indole-3-carbaldehyde)and 5 mmol ammonium acetate was filled into 10 mL-microwavepressure vial and heated under microwave irradiation (power50W, maximum temperature 120 C) for 10 min in 5 mL methanol.After the reactionwas completed, the reaction mixture was pouredinto ice-water, the obtained precipitatewas filtered and crystallizedfrom ethanolewater.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 75,p. 258 - 266

28
[ 562-46-9 ]
[ 40473-50-5 ]
[ 1632130-89-2 ]

Yield	Reaction Conditions	Operation in experiment
86%	With sodium bisulfate supported on silica gel; In 1,2-dichloro-ethane; at 80℃; for 5h;	General procedure: A mixture of -diketones 1 (6 mmol), o-hydroxybenzyl alcohols 2 (2 mmol) and NaHSO4/SiO2 (2.1mmol, 1.0 g) in dichloroethane (10 mL) was stirred at 80 C for 5 h, and then the used supportedreagent was removed by filtration. The filtrate was evaporated to leave crude product, which waspurified by column chromatography (hexane/ethyl acetate) to obtain 3.

Reference： [1]Synlett,2014,vol. 25,p. 1571 - 1576

29
[ 562-46-9 ]
[ 98-16-8 ]
[ 1625672-09-4 ]

Yield	Reaction Conditions	Operation in experiment
654 mg	With ytterbium(III) triflate; In N,N-dimethyl-formamide; at 20℃;	6,6-Dimethyl-3-(3-(trifluoromethyl)phenylamino)cyclohex-2-enone A mixture of <strong>[562-46-9]4,4-dimethylcyclohexane-1,3-dione</strong> (563 mg, 4.02 mmol), 3-(trifluoromethyl)aniline (500 muL, 645 mg, 4.02 mmol), Ytterbium(III) trifluormethanesulfonate (12.5 mg, 20 mumol, 0.5 mol %) and N,N-dimethylformamide (2.5 mL) is stirred at room temperature over night. Methanol and water are added and the mixture is filtered. The precipitate is washed with water and dried under reduced pressure. Yield: 654 mg; ESI mass spectrum [M+H]+=284, Retention time HPLC: 1.18 min (Z005-001).
654 mg	With ytterbium(III) triflate; In N,N-dimethyl-formamide; at 20℃;	A mixture of 4,4-dimethylcyclohexane-l,3-dione (563 mg, 4.02 mmol), 3-(trifluoro- methyl) aniline (500 mu, 645 mg, 4.02 mmol), Ytterbium(III) trifluormethanesulfonate (12.5 mg, 20 muiotaetaomicron, 0.5 mol%) and N,N-dimethylformamide (2.5 mL) is stirred at room temperature over night. Methanol and water are added and the mixture is filtered. The precipitate is washed with water and dried under reduced pressure. Yield: 654 mg; ESI mass spectrum [M+H]+ = 284, Retention time HPLC: 1.18 min (Z005 001).

Reference： [1]Patent: US2014/249129,2014,A1 .Location in patent: Paragraph 0363-0364
[2]Patent: WO2014/135414,2014,A1 .Location in patent: Page/Page column 74

30
[ 383-62-0 ]
[ 562-46-9 ]
C₉H₁₂F₂O₂ [ No CAS ]
C₉H₁₂F₂O₂ [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2015,vol. 13,p. 3432 - 3437

31
[ 562-46-9 ]
[ 22502-03-0 ]
[ 635-93-8 ]
2-methoxyethyl 4-(5-chloro-2-hydroxyphenyl)-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8 hexahydroquinoline-3-carboxylate [ No CAS ]