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[ CAS No. 579-74-8 ] {[proInfo.proName]}

Name: 579-74-8|1-(2-Methoxyphenyl)ethanone|95%
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SKU: A194795
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3d Animation Molecule Structure of 579-74-8

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Quality Control of [ 579-74-8 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 579-74-8 ]

SDS Specification

Alternatived Products of [ 579-74-8 ]

Product Details of [ 579-74-8 ]

CAS No. :	579-74-8	MDL No. :	MFCD00008725
Formula :	C₉H₁₀O₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	DWPLEOPKBWNPQV-UHFFFAOYSA-N
M.W :	150.17	Pubchem ID :	68481
Synonyms :

Calculated chemistry of [ 579-74-8 ] Expand+

Physicochemical Properties

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.22
Num. rotatable bonds :	2
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	43.13
TPSA :	26.3 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.92 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.71
Log Po/w (XLOGP3) :	1.82
Log Po/w (WLOGP) :	1.9
Log Po/w (MLOGP) :	1.44
Log Po/w (SILICOS-IT) :	2.16
Consensus Log Po/w :	1.81

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.19
Solubility :	0.971 mg/ml ; 0.00647 mol/l
Class :	Soluble
Log S (Ali) :	-1.99
Solubility :	1.53 mg/ml ; 0.0102 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-2.84
Solubility :	0.216 mg/ml ; 0.00144 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.0

Safety of [ 579-74-8 ]

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

Application In Synthesis of [ 579-74-8 ]

* 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 [ 579-74-8 ]
Downstream synthetic route of [ 579-74-8 ]

[ 579-74-8 ] Synthesis Path-Upstream 1~9

1
[ 579-74-8 ]
[ 31949-21-0 ]

Yield	Reaction Conditions	Operation in experiment
96%	With copper(ll) bromide In chloroform; ethyl acetate at 70℃; for 8 h; Inert atmosphere; Reflux	Copper (II) bromide (2.97 g, 6.66 mmol) was placed in a twonecked round-bottomed flask fitted with a reflux condenser. EtOAc (10.0 mL) was added to it and the mixture was stirred at 70C for 5 min under nitrogen atmosphere. 1-(2-Methoxyphenyl)ethanone (6) (0.50 g, 3.33 mmol) in CHCl3 (10.0 mL) was slowly added to it and then the mixture was refluxed for 8 h. After completion of the reaction, it was cooled to room temperature, filtered through Celite® pad, and washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure. The crude was puri- fied by column chromatography (EtOAc:hexane = 1:4) to afford the pure product 7a (0.73 g, 96percent) as brown liquid. Rf = 0.43 (EtOAc/hexane = 1/4); 1 H NMR (300 MHz, CDCl3): δ 7.81 (1H, dd, J = 7.8, 1.8 Hz), 7.52 (1H, td, J = 7.8, 1.8 Hz), 7.05–6.96 (2H, m), 4.61 (2H, s), 3.94 (3H, s); 13C NMR (75 MHz, CDCl3): δ 192.3, 158.8, 134.9, 131.6, 124.9, 121.2, 111.7, 56.0, 38.0.
83%	Stage #1: at 60℃; Stage #2: at 60℃; for 0.25 h;	General procedure: The round-bottom flask containing acetophenone derivative 1, 10 (4 mmol) and PTSA (0.076 g,0.4 mmol) was heated to 60 °C to turn the reaction mixture into a paste and NBS (0.854 g, 4.8 mmol) thenadded slowly. After 15 min, the reaction mixture was cooled to room temperature and water (20 mL)added. The crude product was extracted with dichloromethane (2 x 20 mL), dried over anhydrousNa2SO4 and purified by crystallization from n-hexane–dichloromethane to give pure product. 2-Methoxyphenacyl bromide (2): Yellow solid, soluble in acetone, dichloromethane, chloroform, insolublein water; yield 83percent; m.p.: 43–45 °C; 1H-NMR (500 MHz, CDCl3) (δ, ppm): 7.78 (dd, 1H, J = 1.5,7.5 Hz, Ar–H), 7.51–7.47 (m, 1H, Ar–H), 7.02–6.96 (m, 2H, Ar–H), 4.57 (s, 2H, CH2), 3.93 (s, 3H, OCH3).This result showed consistency with the data in literature [26].
330 g	With bromine In acetonitrile at 20 - 25℃; for 4 h;	1 -(2-methoxyphenyl)ethan-1 -one 2-bromo-1 - MW: 150.17 (2-methoxyphenyl)ethan-1-one MW: 229.07 [00242] l-(2-methoxyphenyl)ethanone, 1.1, (300 g, 1.0 eq) was added to a reactor containing acetonitrile (1.2 L, 4.0 V). Br2 (319.62 g, 1.0 eq) was added by cooling the reaction to below 25°C. The reaction mixture was stirred for 4 h at 20-25 °C and sampled for IPC until the content of l-(2-methoxyphenyl)ethanone was 6.5percent. NaHSCb (600 ml, 2V) was added to quench the reaction and then stirred for an additional 0.5h at 20-25°C. Product was extracted with methyl tert-butyl ether (600 ml, 2V), three times, to yield a black oil (418 g, crude), which was purified using a column to yield 330 g of 2-bromo-l-(2-methoxyphenyl)ethan-l-one, 1.2, as an off-white solid (98percent purity).

Reference： [1] Bulletin of the Korean Chemical Society, 2017, vol. 38, # 12, p. 1481 - 1485
[2] Tetrahedron Letters, 2006, vol. 47, # 27, p. 4707 - 4710
[3] Tetrahedron Letters, 2009, vol. 50, # 6, p. 700 - 703
[4] Chemistry - A European Journal, 2011, vol. 17, # 28, p. 7953 - 7959
[5] Molecules, 2017, vol. 22, # 5,
[6] Dalton Transactions, 2008, # 6, p. 822 - 831
[7] Journal of Medicinal Chemistry, 1987, vol. 30, # 8, p. 1497 - 1502
[8] Chemical and Pharmaceutical Bulletin, 1992, vol. 40, # 5, p. 1170 - 1176
[9] Australian Journal of Chemistry, 1994, vol. 47, # 11, p. 2001 - 2012
[10] Bioorganic and Medicinal Chemistry Letters, 2002, vol. 12, # 4, p. 719 - 722
[11] Bioorganic and Medicinal Chemistry Letters, 2007, vol. 17, # 5, p. 1291 - 1295
[12] Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 4, p. 1297 - 1303
[13] Tetrahedron, 2008, vol. 64, # 22, p. 5191 - 5199
[14] Chemistry - An Asian Journal, 2010, vol. 5, # 10, p. 2258 - 2265
[15] European Journal of Medicinal Chemistry, 2012, vol. 54, p. 403 - 412
[16] Angewandte Chemie - International Edition, 2013, vol. 52, # 44, p. 11632 - 11636[17] Angew. Chem., 2013, vol. 125, # 44, p. 11846 - 11850,5
[18] Advanced Synthesis and Catalysis, 2013, vol. 355, # 18, p. 3570 - 3574
[19] Chemical Communications, 2014, vol. 50, # 51, p. 6726 - 6728
[20] Journal of Medicinal Chemistry, 2014, vol. 57, # 15, p. 6572 - 6582
[21] Journal of Materials Chemistry A, 2015, vol. 3, # 12, p. 6258 - 6264
[22] MedChemComm, 2015, vol. 6, # 6, p. 1036 - 1042
[23] European Journal of Medicinal Chemistry, 2015, vol. 104, p. 1 - 10
[24] Phosphorus, Sulfur and Silicon and the Related Elements, 2016, vol. 191, # 8, p. 1166 - 1173
[25] Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 15, p. 3669 - 3674
[26] Angewandte Chemie - International Edition, 2016, vol. 55, # 29, p. 8444 - 8447[27] Angew. Chem., 2016, vol. 128, # 29, p. 8584 - 8587,4
[28] Patent: KR101642378, 2016, B1, . Location in patent: Paragraph 0062-0066
[29] ChemMedChem, 2018, vol. 13, # 1, p. 37 - 47
[30] Patent: US2018/44459, 2018, A1, . Location in patent: Paragraph 0367
[31] Bioorganic and Medicinal Chemistry, 2018, vol. 26, # 8, p. 1986 - 1995
[32] Patent: US2018/44284, 2018, A1, . Location in patent: Paragraph 0175; 0176
[33] Organic Letters, 2018, vol. 20, # 8, p. 2257 - 2260
[34] Patent: WO2018/161008, 2018, A1, . Location in patent: Paragraph 00241-00242
[35] Chemical Communications (Cambridge, United Kingdom), 2018, vol. 54, # 86, p. 12182 - 12185

2
[ 579-74-8 ]
[ 31949-21-0 ]
[ 1121543-12-1 ]

Reference： [1] Biochemistry, 2010, vol. 49, # 36, p. 7913 - 7919

3
[ 579-74-8 ]
[ 445-82-9 ]

Reference： [1] Chemical Communications, 2000, # 14, p. 1323 - 1324

4
[ 579-74-8 ]
[ 16740-73-1 ]

Yield	Reaction Conditions	Operation in experiment
99%	With N-Bromosuccinimide; iodine In acetonitrile for 12 h; Darkness	General procedure: To a reaction tube charged with NBS (1.5 equiv, 0.3 mmol), catalyst (10 molpercent, 0.02 mmol) and CH₃CN (1.0 mL),was added para-chloroanisole 1a (0.2 mmol). After being stirred at room temperature for 12 h in dark, the reaction was quenched by saturated aq. solution of Na₂S₂O₃ (2 mL). The resulting mixture was extracted by ethyl acetate (3 5 mL). The combined organic extracts were washed by brine (10 mL), dried over Na₂SO₄ and filtered through a pad of Celite. The filtrate was concentrated under reduced pressure and the residuewas purified by flash chromatography on a silica gel column with petroleum ether/dichloromethane (5:1) as the eluent to give 4.3.1. 2-Bromo-4-chloroanisole (2a)
95%	With hydrogenchloride; N-Bromosuccinimide In water; acetone at 20℃; for 3 h;	Compound 41-2 (0492) To a solution of 41-1 (2.0 g, 13.32 mmol) in acetone (25 mL) was added NBS (2.37 g, 13.32 mmol) and 1M HCl aq. (0.13 mL, 0.13 mmol). The reaction mixture was stirred at room temperature for 3 h, and then concentrated to dryness under reduced pressure. The residue was dissolved with PE (40 mL) the resultant precipitate was filtered and dried in vacuum to afford 41-2 as a white solid (2.90 g, yield: 95percent).

Reference： [1] Tetrahedron, 2017, vol. 73, # 50, p. 7105 - 7114
[2] Tetrahedron Letters, 2006, vol. 47, # 27, p. 4707 - 4710
[3] Patent: US9138427, 2015, B2, . Location in patent: Page/Page column 312-313
[4] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1987, p. 1423 - 1428
[5] Synthesis (Germany), 2013, vol. 45, # 11, p. 1497 - 1504

5
[ 579-74-8 ]
[ 40023-74-3 ]

Yield	Reaction Conditions	Operation in experiment
72%	With ammonium hydroxide; ammonium acetate; sodium cyanoborohydride; zinc In ethanol; water at 80℃; for 36 h;	General procedure: To a saturated solution of NH4OAc in EtOH (40 mL) were added activated Zn (5 equiv), acetophenone (1 equiv), NaBCNH3(3 equiv) and 30percent aq NH3 (10 mL) respectively. The mixture wasstirred at 80 C for 36 h. The reaction mixture was cooled to rt and concentrated under reduced pressure. The residue was dissolved in CH2Cl2 and made basic using 1 M NaOH (50 mL). Theorganic phase was separated and aqua phase was extracted with (2x25 mL) CH2Cl2. The organic phases were combined and acidified with HCl (pH: 2.0). The organic layer was separated andH2O layer was extracted with CH2Cl2 (2 25 mL). The H2O layer was made basic with NaOH (pH: 10.0), The organic layer was extracted with CH2Cl2 (3 25 mL). Combined organic layers weredried over Na2SO4 and evaporation of the solvent afforded thedesired amines.

Reference： [1] Science, 2017, vol. 358, # 6361, p. 326 - 332
[2] Chemistry - A European Journal, 2014, vol. 20, # 1, p. 245 - 252
[3] Farmaco, 1991, vol. 46, # 7-8, p. 861 - 872
[4] Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 13, p. 3592 - 3602
[5] Chirality, 2018, vol. 30, # 7, p. 900 - 906
[6] Journal of the Chemical Society. Perkin Transactions 2, 2000, # 7, p. 1339 - 1347
[7] Advanced Synthesis and Catalysis, 2011, vol. 353, # 11-12, p. 2085 - 2092
[8] Molecules, 2014, vol. 19, # 12, p. 21386 - 21397
[9] Bioorganic and Medicinal Chemistry, 2016, vol. 24, # 4, p. 554 - 569
[10] Green Chemistry, 2017, vol. 19, # 2, p. 474 - 480

6
[ 67-56-1 ]
[ 579-74-8 ]
[ 149-73-5 ]
[ 27798-60-3 ]

Reference： [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1982, p. 235 - 242

7
[ 67-56-1 ]
[ 579-74-8 ]
[ 149-73-5 ]
[ 57486-68-7 ]
[ 81585-74-2 ]

Reference： [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1982, p. 235 - 242

8
[ 579-74-8 ]
[ 89368-12-7 ]

Reference： [1] Synthetic Communications, 2000, vol. 30, # 12, p. 2091 - 2098

9
[ 579-74-8 ]
[ 34589-97-4 ]

Reference： [1] Bulletin of the Korean Chemical Society, 2017, vol. 38, # 12, p. 1481 - 1485

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Ghs Precautionary Statements

Precautionary Statements-General
Code	Phrase
P101	If medical advice is needed,have product container or label at hand.
P102	Keep out of reach of children.
P103	Read label before use
Prevention
Code	Phrase
P201	Obtain special instructions before use.
P202	Do not handle until all safety precautions have been read and understood.
P210	Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P211	Do not spray on an open flame or other ignition source.
P220	Keep/Store away from clothing/combustible materials.
P221	Take any precaution to avoid mixing with combustibles
P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Ghs Hazard Statements

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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99%	With C₃₇H₂₈Cl₂N₅PRu; isopropanol; sodium hydroxide at 82℃; for 0.0166667h; Inert atmosphere;
99%	With C₁₅H₁₈BF₃; hydrogen; phosphazene base P₁-t-bu-tris(tetramethylene) In tetrahydrofuran at 75℃; for 40h;
99%	With hydrogen; anhydrous silver perchlorate; 1,1,1,3,3,3-hexamethyldisilazane potassium In toluene at 25℃; for 17h; Glovebox;
98%	With potassium-t-butoxide In isopropanol at 80℃; for 12h;
98.9%	With C₅₅H₅₄Cl₄N₂O₂PRu₂; sodium hydroxide In isopropanol at 82℃; for 0.333333h;
98%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With C₄₄H₄₄CuN₂P₂⁽¹⁺⁾*F₆P^(1-) In toluene at 25℃; for 1h; Inert atmosphere; Stage #2: With sodium hydroxide In methanol; lithium hydroxide monohydrate Inert atmosphere;	3. Typical procedure for catalytic hydrosilylation of ketones General procedure: Under nitrogen atmosphere the copper based catalyst 1 (8 7 mmg0.01 mmol), tBuOK ( 5 6 mmg0.05 mmol) and toluene (3 mL) were placed in a tube equipped with a Teflon coated magnetic stirring bar. T he mixture was stirred at 25 °C for 15 min and then polymethylhydrosiloxane (PMHS, 0.0 9 m L, 1.5 mmol mmol) was injected. After 15mins, ketone (0.5 mmol) was introduced and the mixture was stirred at 25 °C for therequired reaction time. The mixture was quenched with MeOH (1 mL) and 10%NaOH solution (3 mL), and the mixture was stirred for 4 h. T he mixture was extractedwith ethyl acetate (5 mL × 3) and the combined organic layer was washed with waterand saturated sodium chloride solution, dried over anhydrous Na2SO4. the solvent was removed under vacuum and the residue was purified by flash chromatography (silica gel) to afford the desired product. All the product alcohols were analyzed by 1H NMR, 13C NMR, or GC analysis.
97%	With methyldiethoxysilane; ferrous acetate In tetrahydrofuran at 65℃; for 24h;
97%	With manganese(I) pentacarbonyl bromide; potassium-t-butoxide; Ethane-1,2-diamine In isopropanol at 80℃; for 3h;	2.1. Representative procedure for transfer hydrogenation reaction ofacetophenone General procedure: To a solution of acetophenone (58 μL, 0.5 mmol) in 2-propanol (0.5 mL) was added a stock solution of manganese pentacarbonyl bromide (0.5 mL, 0.005 mol·L-1; 2.7 mg, 0.010 mmol, in 2 mL 2-propanol)followed, in this order, by a stock solution of ethylenediamine (0.5 mL,0.005 mol·L-1; 1.0 μL, 0.0125 mmol, in 2.5 mL 2-propanol) and tBuOK (0.5 mL, 0.010 mol·L-1; 2.4 mg, 0.020 mmol, in 2 mL 2-propanol). The reaction mixture was stirred for 3 h at 80 °C in an oil bath. The solution was then filtered through a small pad of silica (2 cm in a Pasteur pip-ette). The silica was washed with ethyl acetate. The filtrate was evaporated and the conversion was determined by 1H NMR. The crude residue was then puried by column chromatography (SiO 2 , mixture of petroleum ether/ethyl acetate or dietyl ether as eluent. Enantiomeric excesses were determined by GC analyses performedon GC-2014 (Shimadzu) 2010 apparatus equipped with Supelco beta-DEX 120 column (30 m × 0.25 mm). The determination of the absoluteconguration was done by comparison with (S)-alcohol obtained bykinetic resolution of racemic alcohols with Novozym 435 (CandidaAntarctica Lipase B) and by comparison of the retention times with the literature [32-34].
97%	With formic acid; C₁₈H₂₄ClIrN₃ In lithium hydroxide monohydrate at 80℃; for 4h; Schlenk technique; Inert atmosphere; chemoselective reaction;
95%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With Trimethyl borate; dimethylsulfide borane complex; (-)-3-amino-6,6-dimethyl-2-hydroxy-bicyclo[3.1.1]heptane In tetrahydrofuran at 20℃; Stage #2: With methanol In tetrahydrofuran
95%	With C₅₃H₄₆ClN₃P₂Ru; potassium isopropoxide; isopropanol at 82℃; for 1h;
94%	With N,N,N,N,-tetramethylethylenediamine; methyldiethoxysilane In tetrahydrofuran at 65℃; for 24h;
93%	With C₂₈H₃₆ClF₃N₂O₃RuS; potassium-t-butoxide; isopropanol at 82℃; for 12h; Inert atmosphere;
93%	With 1-hydrosilatrane; potassium-t-butoxide In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 0.5h;
93%	With isopropanol; sodium hydroxide for 3h; Inert atmosphere; Schlenk technique; Reflux;	2.3 General procedure for transfer hydrogenation of ketones catalyzed by 4 General procedure: Under nitrogen atmosphere, a mixture of ketone (2 mmol), catalyst 4 (0.008 mmol), and 2-propanol (17.6 mL) was stirred at 82°C. After 5 min, 2.4 mL of 0.1 M NaOH (0.24 mmol) solution in 2-propanol was introduced to initiate the reaction, and the reaction mixture was stirred at refluxing temperature. At the specified time, 0.1 mL of the reaction mixture was filtered through a short pad of celite to remove the complex catalyst, and immediately diluted with 0.2 mL of 2-propanol. The filtrate was used for GC analysis. After the reaction was finished, the mixture was condensed under reduced pressure and subject to flash silica gel column chromatography to afford the alcohol product (detected under 254 nm UV light or by alkaline potassium permanganate solution; eluent: petroleum ether (60-90 °C)/ethyl acetate = 10:1 or petroleum ether (30-60 °C)/dichloromethane= 1:1, v/v). The alcohol products were identified by comparison with the authentic sample through NMR and GC analyses.
92%	With potassium-t-butoxide; isopropanol at 80℃; for 12h; Inert atmosphere;
92%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With ferrous acetate; tricyclohexylphosphine In tetrahydrofuran at 65℃; Inert atmosphere; Stage #2: In tetrahydrofuran at 65℃; Inert atmosphere; Stage #3: With lithium hydroxide monohydrate; sodium hydroxide In tetrahydrofuran; methanol at 0 - 20℃; Inert atmosphere;
92%	With hydrogen In lithium hydroxide monohydrate at 20℃; for 72h; Autoclave;	2.4. General procedure for hydrogenation under hydrogen pressure General procedure: The stainless steel autoclave was charged with the previously prepared aqueous suspension of Col-Ni-CMC Nps (8 mL, from 40 mg of NiCl2·6H2O and 10 mL, from 50 mg of NiCl2·6H2O) for ketone hydrogenation. The appropriate nitro-aromatic ([substrate]/[metal] = 100) in 2 mL of MeOH, was added into the autoclave and dihydrogen was admitted to the system at constant pressure (10 to 40 bars). The mixture was stirred until the reaction was finished. Samples for gas chromatographic analysis were removed from time to time. The residue was extracted with diethyl ether (3 × 25 mL). The organic layer was dried over Na2SO4 and the solvent was removed under reduced pressure Pure products were obtained by column chromatography over silica gel using hexane/ethyl acetate as eluent.
92%	With [Re(NH{CH₂CH₂P(iPr₂)}₂)(CO)₃]Br; potassium-t-butoxide; hydrogen In toluene at 110℃; for 2h; Inert atmosphere; Glovebox; Autoclave;
90%	With trimethylamine-N-oxide; (N,N,N-trimethyl-2-(5-oxo-4,6-bis(trimethylsilyl)cyclopenta[c]pyrrol-2-(1H,3H,5H)-yl)ethanaminium) iron tricarbonyl; hydrogen In lithium hydroxide monohydrate at 85℃; for 14h; Autoclave; Inert atmosphere;
89%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With Triethoxysilane; diethylzinc(II); N,N-dimethyl-N'-(4-tert-butylphenyl)formamidine In tetrahydrofuran; hexane at 20 - 60℃; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; hexane; lithium hydroxide monohydrate at 0℃; for 1h;
88%	With C₅₆H₅₅ClN₃P₂Ru⁽¹⁺⁾*F₆P^(1-); potassium 2-methyl-2-butoxide In isopropanol at 20 - 80℃; for 1.5h; Schlenk technique; Inert atmosphere;
85%	With sodium hydroxide; ytterbium(III) tris(trifluoromethanesulfonate) In isopropanol for 0.5h; Heating;
85%	With [Ru(CH₃CN)₃(κ²-o-DPPBS)Cl] In methanol at 70℃; for 15h; Autoclave;
85%	With sodium tetrahydridoborate; lithium hydroxide monohydrate In tetrahydrofuran at 20℃; for 6h; Schlenk technique; Inert atmosphere;
81%	With potassium-t-butoxide; 1-hydrosilatrane In tetrahydrofuran; N,N-dimethyl-formamide for 0.5h; Inert atmosphere;	5. General procedure for the racemic reduction of ketones General procedure: To a 25 mL round-bottomed flask containing 5 mL N,N-dimethylformamide, were added 1-hydrosilatrane(0.263 g, 2.0 mmol), and ketone (1.0 mmol). The resulting solution was stirred for 1 minute, after which 1M tBuOK in THF (1.0 mmol, 1.0 mL) was added. Reaction mixture was allowed to stir for 30 min. Reaction was quenched with 25 mL 3M HCl, and extracted with 30 mL ethyl acetate. Organic layer was washed with brine (50 mL x 3), and dried with anhydrous sodium sulphate. After filtration, the solvent was removed under vacuum to yield product. No further steps were taken for purification.
80%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With 2.6-dimethylphenol; Triethoxysilane; diethylzinc(II) In tetrahydrofuran; hexane at 60℃; for 1h; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol; hexane; lithium hydroxide monohydrate at 0℃; for 1h;
80%	With C₂₁H₂₆ClNORu; hydrogen In methanol; lithium hydroxide monohydrate Autoclave; Heating;
80%	With C₇₀H₆₈Cl₄N₇O₂P₃Ru₂; potassium hydroxide In isopropanol at 82℃; for 2h;	2.4. Catalytic experiments General procedure: Complex 21 (the same for complexes 22-26) (1 mmol) were dissolved in 15 mL 2-propanol and acetophenone (or acetophenone derivatives) (100 mmol) and KOH (5 mmol) were added then reac- tion was refluxed at 82 °C for 2 h. The solvent was removed by ro- tary evaporator under the vacuum and washed with diethyl ether (2 ×20 ml). Oily mixture was purified with flash chromatography silica gel (petroleum ether/ethyl acetate (5:1)). The obtained oily mixture was analyzed from HPLC.
79%	With formic acid; [(dpa)(p-cymene)RuCl]Cl; anhydrous sodium formate In lithium hydroxide monohydrate at 65℃; for 24h; Inert atmosphere;
77%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With C₄₀H₃₂Cl₂N₃PRu; isopropanol at 82℃; for 0.166667h; Schlenk technique; Inert atmosphere; Stage #2: With sodium hydroxide for 3h; Schlenk technique; Inert atmosphere;
74%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With sodium tetrahydridoborate In methanol at 0 - 20℃; Inert atmosphere; Stage #2: With lithium hydroxide monohydrate
74%	With sodium tetrahydridoborate In methanol at 0 - 20℃; Inert atmosphere;
69%	With diisobutylaluminum borohydride In tetrahydrofuran at 25℃; for 1h; Inert atmosphere;
61%	With bis[chlorido(η2,η2-cycloocta-1,5-diene)rhodium(I)]; anhydrous potassium trifluoroacetate; diphenyl(methyl)phosphine; 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl-4',4',5',5'-tetramethyl-1,3,2-dioxaborolane; 4,4,5,5-tetramethyl-1,3,2-dioxaborolane In tetrahydrofuran; cyclohexane at 20℃; for 48h; regioselective reaction;
59%	With potassium-t-butoxide In 1,4-dioxane at 80℃; for 16h; Inert atmosphere; Sealed tube;
53%	With C₁₈H₃₇BrNO₄P₂Re; potassium-t-butoxide; hydrogen In toluene at 120℃; for 20h; Glovebox; Autoclave;
46%	With sodium tetrahydridoborate In methanol at 20℃;
	With tris isopropylate aluminium
18 % Spectr.	With sodium tetrahydridoborate; glacial acetic acid at 16 - 21℃; for 0.166667h;
	With sodium tetrahydridoborate In methanol for 0.75h;
	With sodium tetrahydridoborate
	With sodium tetrahydridoborate
	With sodium tetrahydridoborate In ethanol for 1.5h; Heating;
100 % Chromat.	With dodecacarbonyltri-iron; sodium isopropanolate; 5,10,15,20-tetra(pyridin-4-yl)-21H,23H-porphyrin In isopropanol at 100℃; for 7h;
97 % Chromat.	With 1H-imidazol-3-ium; sodium isopropanolate In isopropanol at 100℃; for 24h;
	With sodium tetrahydridoborate
	With methanol; sodium tetrahydridoborate
	With samarium diiodide In tetrahydrofuran
	With potassium hydroxide; di-μ-chlorobis-[(η⁶-p-cymene)chlororuthenium(II)]; (1R,2R)-3-(diphenylmethoxy)-1-methylamino-1-phenylpropan-2-ol In isopropanol at 25℃; for 4h;
99 % Chromat.	With potassium-t-butoxide; hydrogen In isopropanol at 25℃; for 8h;
	With sodium tetrahydridoborate
	With lithium isopropoxide In isopropanol at 180℃; for 0.333333h; microwave irradiation;
84 % ee	With potassium-t-butoxide; hydrogen In isopropanol at 20 - 25℃; for 24h;
	With sodium hydroxide In tetrahydrofuran; lithium hydroxide monohydrate	4.1 1-(2-Methoxyphenyl)ethanol Step 1 1-(2-Methoxyphenyl)ethanol Lithium aluminum hydride (1.52 g) was suspended in tetrahydrofuran (100 ml), 2'-methoxyacetophenone (2.76 ml) was added under ice-cooling, and the mixture was stirred for 30 min. To the reaction mixture were successively added water (1.5 ml), 15% aqueous sodium hydroxide solution (1.5 ml) and water (4.5 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give the title compound (3.05 g).
	With sodium isopropanolate; isopropanol at 100℃;
	With sodium tetrahydridoborate
	With C₄₂H₃₉ClN₂OsP₂; sodium isopropanolate In isopropanol at 82℃; for 0.0333333h; Inert atmosphere;
93 %Spectr.	With RuCl₂(NC₆H₄NHCC₅H₃NN₂C₃H(CH₃)2)(P(C₆H₅)3); potassium isopropoxide; isopropanol at 28℃; for 0.0166667h; Air;
	With [Ir(cod)(κ2-o-tBu2P-C6H4-NMe2)](+)PF6(-); isopropanol; sodium tertiary butoxide at 82℃; for 0.0833333h; Inert atmosphere;
	With sodium hydroxide; isopropanol for 0.333333h; Heating / reflux;	5 Examole 5: catalytic reduction of linear and cyclic dialkvl ketones, alkylaryl ketonesand diaryl ketones in presence of complex 8; Complex 8 (3.0 mg, 0.005 mmol) is suspended in 3 ml of 2-propanol in a 10mltailed tubes (Schlenk) and 2 ml of a 0.1M solution of NaOH in 2-propanol added.The complex is completely solubilised in a few minutes by stirring.Separately, in a 50ml tailed tubes (Schlenk), the necessary amount ofacetophenone (240 ul, 2 mmol) is dissolved in 19 ml of 2-propanol, the system isrefluxed and 1 ml of the previously prepared catalyst solution added (the addition of the complex is considered to be the starting time of the reaction). The molarratios between acetophenone/catalyst/NaOH are 2000/1/40; the reaction ismonitored at 1, 2, 5 minutes by collecting 0.5 ml of the solution and adding 4.5 mlof diethyl ether. This solution is passed through a silica column in order toeliminate the catalyst and sodium hydroxide, and finally analysed by gaschromatography. The gas chromatograph analysis data are reported in table 2.
	With [Ru(chloro)(p-cymene)(N,N'-bis[(1S)-1-benzyl-2-O-(diphenylphosphinite)ethyl]ethanediamide)] chloride; isopropanol; sodium hydroxide at 82℃; for 1h; Inert atmosphere;
	With sodium tetrahydridoborate In methanol at 20℃;
98 %Spectr.	With C₅₁H₅₃ClN₃O₂P₂Ru⁽¹⁺⁾*Cl^(1-); Cs₂CO₃; isopropanol at 83℃; for 6h; Inert atmosphere;
	With [Ru((Ph2P)2N-C6H4-2-CH(CH3)2)(η6-p-cymene)Cl]Cl; isopropanol; sodium hydroxide at 82℃; for 0.25h; Inert atmosphere;
	With [Ru{chloro(p-cymene)(N,N'-bis[(1R)-1-ethyl-2-O-(diphenylphosphinite)ethyl]ethanediamide)}]chloride; isopropanol; sodium hydroxide at 82℃; for 1h;
	With lithium aluminium hydride In tetrahydrofuran at 0℃; for 0.5h;	4.1 Example 4; (2R)-1-[1,1-Dimethyl-2-(naphthalen-2-yl)ethylamino]-3-[1-(2-methoxyphenyl)ethoxy]propan-2-ol; Step 1; 1-(2-Methoxyphenyl)ethanol Lithium aluminum hydride (1.52 g) was suspended in tetrahydrofuran (100 ml), 2'-methoxyacetophenone (2.76 ml) was added under ice-cooling, and the mixture was stirred for 30 min. To the reaction mixture were successively added water (1.5 ml), 15% aqueous sodium hydroxide solution (1.5 ml) and water (4.5 ml). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to give the title compound (3.05 g).
96 %Chromat.	With Ru(η6-cymene)(PPh2NH-C6H4-2-CH(CH3)2)Cl2; isopropanol; sodium hydroxide at 82℃; for 0.5h; Inert atmosphere;
	With C₅₈H₅₀Cl₂N₂P₄RuS₂; isopropanol; sodium hydroxide at 82℃; for 1h; Inert atmosphere;
	With sodium tetrahydridoborate In methanol at 0 - 20℃; for 2h; Inert atmosphere;
	With [Ru((PPh2)2NCH2-C4H3S)(η6-p-cymene)Cl]Cl; isopropanol; sodium hydroxide at 82℃; for 0.166667h; Inert atmosphere;
	With Candida tenuis AKR₂B₅ xylose reductase [E_.⁽¹⁾C₁₁₁₇₅]; lithium hydroxide monohydrate; NADH In ethanol at 25℃; aq. phosphate buffer; Enzymatic reaction;
97 %Chromat.	With anhydrous sodium carbonate; isopropanol at 82℃; for 8h; Inert atmosphere;
94 %Chromat.	With C₇₁H₅₆N₅P₂Ru⁽¹⁺⁾*Cl^(1-); potassium isopropoxide; isopropanol; potassium hydroxide at 82℃; for 4h; Inert atmosphere;
98 %Chromat.	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With [RuCl2(η6-benzene)tris(4-methoxyphenyl)phosphane] In isopropanol at 82℃; for 0.166667h; Inert atmosphere; Stage #2: With potassium isopropoxide In isopropanol at 82℃; for 0.5h; Inert atmosphere;
	With [RuCl(bis(2-(dimethylamino)phenyl)amide)(PPh₃)]; isopropanol; potassium hydroxide at 83℃; for 2h; Inert atmosphere;
> 99 %Chromat.	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With n-butyllithium; ferrous acetate; 1,3-bis(2,6-diisopropylphenyl)imidazolinium chloride In tetrahydrofuran; hexane at 65℃; Inert atmosphere; Stage #2: With sodium hydroxide In tetrahydrofuran; methanol; hexane; lithium hydroxide monohydrate at 20℃; for 3h; Inert atmosphere;
	With bis[dichlorido(η⁵-1,2,3,4,5-pentamethyl-cyclopentadienyl)rhodium (III)]; lithium formate; (S)-prolinehydroxamic acid In lithium hydroxide monohydrate at 24℃; for 14h; enantioselective reaction;
	With [(η⁶-p-cymene)RuCl(6,6’-dihydroxy-2,2’-bipyridine)]Cl; isopropanol; potassium hydroxide at 85℃; for 24h;
	With Ru(Ph2PNHCH2-C4H3O)(η-6-benzene)Cl2; isopropanol; potassium hydroxide at 82℃; for 0.333333h;
	With sodium tetrahydridoborate In ethanol Inert atmosphere;
	With [C₁₀H₆N₂{NHPPh₂Ru(η⁶-benzene)Cl₂}₂]; sodium hydroxide In isopropanol for 0.333333h; Reflux; Inert atmosphere;	4.3.4 General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen transfer reaction: a solution of complexes [C10H6N2{NHPPh2Ru(η6-benzene)Cl2}2], 1, [C10H6N2{PPh2NHRh(cod)Cl}2], 2 and [C10H6N2{NHPPh2Ir(η5-C5Me5)Cl2}2], 3 (0.005 mmol), NaOH (0.025 mmol) and the corresponding ketone (0.5 mmol) in degassed iso-PrOH (5 mL) were refluxed for 10 min for 1, 1 h for 2 and 3 h for 3. After this period a sample of the reaction mixture was taken off, diluted with acetone and analyzed immediately by GC. Conversions obtained are related to the residual unreacted ketone.
	With formic acid; [Cp*Rh(2,2'-dipyridylamine-κ²N1,N1')Cl]Cl; anhydrous sodium formate In lithium hydroxide monohydrate at 60℃; for 18h;
	With [(bis(5-methyl-3-phenyl-1,2,4-triazolyl)(3-methyl-5-phenyl-1,2,4-triazolyl)borate)Ru(p-cymene)Cl]; potassium hydroxide In isopropanol for 24h; Inert atmosphere; Reflux;
> 99 %Chromat.	With Triethoxysilane; C₂₇H₅₆FeN₂P₄Si In tetrahydrofuran at 100℃; for 24h; Inert atmosphere; Schlenk technique;
	With sodium tetrahydridoborate In ethanol
	With sodium tetrahydridoborate In methanol at 20℃; Schlenk technique;	Racemic: General procedure: The ketone (1mmol) was dissolved in MeOH (5cm3) in a schlenk tube, then NaBH4 (3mmol) was added slowly and the mixture was stirred at r.t. for o/n. The solvent was removed and the mixture was dissolved in DCM (10 cm3), washed with water (10cm3), filtered and solvent removed. a small amount of the residue was dilluted inEtOAc and then injected on the GC to determine the conversion.
	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With C₃₃H₅₈FeN₃PSi₂; phenylsilane In toluene at 20℃; for 4h; Inert atmosphere; Glovebox; Green chemistry; Stage #2: With sodium hydroxide In toluene for 1h; Green chemistry;
92 %Chromat.	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With (η⁶-C₆H₆)RuCl₂[μ-(PPh₂CH₂N)₂CH₂(C₁₀H₆)]RuCl₂(η⁶-C₆H₆); isopropanol for 0.166667h; Inert atmosphere; Schlenk technique; Stage #2: With potassium isopropoxide In isopropanol at 82℃; for 0.5h; Inert atmosphere; Schlenk technique;
	With [Rh((Ph₂P)₂NCH₂-C₄H₃O)(Cp*)Cl]Cl; sodium hydroxide In isopropanol at 82℃; for 10h; Schlenk technique; Inert atmosphere;
	With OsCl[PPh₂(CH₂)₄PPh₂](CNN-H); sodium isopropanolate In isopropanol for 0.0333333h; Inert atmosphere; Reflux;	19 Example 19: catalytic reduction of linear and cyclic dialkyl ketones, alkylaryl ketones and diarylketones in the presence of the osmium complex (7a) The catalyst solution was prepared in a 10 ml Schlenk by adding 5 ml of 2-propanol to the complex (7a) (1.8 mg, 0.0021 mmol). By stirring, the complex dissolves completely over a period of a few minutes. Separately, in a second Schlenk (50 ml), 200 µl of the previously prepared solution containing the catalyst and 0 4 ml of a 0.1 M NaOiPr solution in 2-propanol were added to a solution of ketone (2 mmol) in 19 ml of 2-propanol under reflux. The start of the reaction was considered to be when the complex was added. The molar ratios of ketone/catalyst/NaOiPr were 20000/1 /400. The GC analysis data are given in table 2.
	With [Ru(Cy₂PNHCH₂-C₄H₃S)(η⁶-p-cymene)Cl₂]; isopropanol; sodium hydroxide at 82℃; for 2h; Inert atmosphere; Schlenk technique;
	With [Rh(Cy₂PNHCH₂-C₄H₃O)(cod)Cl]; isopropanol; sodium hydroxide at 82℃; for 0.416667h; Inert atmosphere; Schlenk technique;	4.2. General procedure for the transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen transfer reaction: a solution of complexes [Rh(Cy2PNHCH2-C4H3O)(cod)Cl], (1),[Rh(Cy2PNHCH2-C4H3S)(cod)Cl], (2), [Ir(Cy2PNHCH2-C4H3O)(η5-C5Me5)Cl2], (3) and [Ir(Cy2PNHCH2-C4H3S)(η5-C5Me5)Cl2], (4)(0.005 mmol), NaOH (0.025 mmol) and the corresponding ketone(0.5 mmol) in degassed iso-PrOH (5 mL) were refluxed until the reactions were completed. After this period a sample of the reactionmixture was taken off, diluted with acetone and analyzed immediately by GC. Conversions obtained are related to the residual unreacted ketone.
	With [Ru((Ph₂PO)-C₇H₁₄N₂Cl)(η⁶-p-cymene)Cl₂]Cl; potassium hydroxide In isopropanol at 82℃; Inert atmosphere; Schlenk technique;	3.2 Transfer hydrogenation of ketones General procedure: Typical procedure for the catalytic hydrogen transfer reaction: a solution of the complexes [Ru((Ph2PO)-C7H14N2Cl)(η6-arene)Cl2]Cl and [Ru((Ph2PO)-C7H14N2Cl)(η6-arene)Cl2]Cl {arene: benzene 4, 5; p-cymene 6, 7} (0.005 mmol), KOH (0.025 mmol) and the corresponding ketone (0.5 mmol) in degassed 2-propanol (5 mL) was refluxed until the reactions were completed. Then, a sample of the reaction mixture was taken off, diluted with acetone and analyzed immediately by GC. The conversions are related to the residual unreacted ketone. GC analyses were performed a Shimadzu 2010 Plus Gas Chromatograph equipped with a capillary column (5 % biphenyl, 95 % dimethylsiloxane) (30 m×0.32 mm×0.25 μm). The GC parameters for transfer hydrogenation of the ketones were as follows: initial temperature, 50° C; initial time, hold min 1 min; solvent delay, 4.48 min; temperature ramp 15° C/min; final temperature, 270° C, hold min 5 min; final time, 20.67 min; injector port temperature, 200° C; detector temperature, 200° C, injection volume, 2.0 μL
98 %Spectr.	With C₃₆H₁₀₃AlO₄Si₁₄; isopropanol In neat (no solvent) at 80℃; for 24h; Glovebox; Schlenk technique;
	With sodium tetrahydridoborate In ethanol at 0 - 20℃;

97%	With hydrogenchloride; 2,2,6,6-tetramethyl-1-piperidinyloxy free radical; Amberlite IRA 900 chlorite In dichloromethane at 20℃; for 4.5h;
97%	With 1,10-Phenanthroline; tris(2,4-pentanedionato)iron(III); potassium carbonate In toluene for 48h; Reflux; Green chemistry;
96%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; polymer-bound {NMe₃⁽¹⁺⁾*Br(OAc)2^(1-)} In dichloromethane at 40℃; for 24h;
96%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; bisacetoxybromate(I) resin In dichloromethane at 20℃; for 24h;
95%	With [(2-(benzoimidazol-2-yl)-6-(3,5-dimethylpyrazol-1-yl)pyridine)RuCl₂(PPh₃)]; potassium-t-butoxide; acetone In methanol at 56℃; for 0.333333h; Inert atmosphere;	A typical procedure for the catalytic oxidation of alcohols General procedure: The catalyst solutionwas prepared by dissolving complex 3(36.1 mg,0.05mmol) in methanol (5.0 mL).Under a nitrogen atmosphere, the mixture of an alcohol substrate (2.0 mmol) and1.0 mL of the catalyst solution (0.01mmol) in 20mL acetone was stirred at 56 Cfor 10 minutes. tBuOK(22.4mg, 0.2 mmol)was then added to initiate the reaction.At the stated time, 0.1 mL of the reaction mixture was sampled and immediately diluted with 0.5 mL acetone pre-cooled-to-0 C for GC or NMR analysis. After the reaction was complete, the reaction mixture was condensed under reduced pressure and subject to purification by flash silica gel column chromatography to afford the corresponding ketone product, which was identified by comparison with the authentic sample through NMR and GC analysis.
92%	With C₆H₄MoNO₇^(1-)*C₁₉H₄₂N⁽¹⁺⁾; oxygen In water monomer at 100℃; for 24h; Green chemistry; chemoselective reaction;	2.3. General procedure for the catalytic oxidation of alcohols toaldehydes General procedure: A mixture of alcohol (0.75 mmol), and catalyst Mo1 (13 mg,3.0 mol%) taken in 0.5 mL of water was stirred at 100 ° C under oxygenatmosphere (O2 bladder) and the stirring was continued for16-24 h as per requirement. The progress of reaction was monitoredby TLC. After completion of the reaction, ethyl acetate was added to the mixture. The aqueous phase was extracted with ethyl acetate 2-3 times. Then the combined organic extracts were driedover anhydrous sodium sulfate and the solvent was removed under reduced pressure. The crude product so obtained was purified by column chromatography using hexane-ethyl acetate as eluent. While the known products were characterized by spectroscopic techniques and compared with reported data and the new products 22b and 36b were characterized completely. The characterization detail is provided in supporting information section.
91%	With iron (ΙΙΙ) nitrate nonahydrate; oxygen; 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,2-dichloro-ethane at 60℃; for 3h; Schlenk technique; Green chemistry;
90%	With tert.-butylhydroperoxide In hexane; water monomer at 50℃; for 23.5h;
89%	With Cs₂CO₃ In toluene at 110℃; for 18h;
88%	With C₁₄H₁₄N₆O₂; oxygen; anhydrous Sodium acetate; palladium diacetate at 120℃; for 96h;
88%	With copper(II) selenite dihydrate; potassium hydroxide In toluene for 28h; Reflux;
87%	With oxygen; potassium carbonate In toluene at 110℃; for 24h; Green chemistry; chemoselective reaction;
86%	With tert.-butylhydroperoxide; Eosin In decane; acetonitrile at 25℃; for 28h; Inert atmosphere; Irradiation; Molecular sieve; Green chemistry; chemoselective reaction;	General procedure for oxidation of alcohols: General procedure: Oven dried round bottom flask was charged with Eosin Y (5 mmol) alcohol (1 mmol) and 3 equiv. of TBHP (5.5 M in decane) in dry ACN. The resulting mixture was degassed for 15 mins, followed by back filling N2, and then irradiated under Blue LED light (12W, 455 nm) at room temperature (25 oC). After reaction completion monitored through TLC, the mixture was diluted with 15 ml of 10% NaHCO3 solution, and extracted with EtOAc (3 × 20 ml). The combined organic extracts were washed with brine (20 ml), dried over Na2SO4, and concentrated on vacuo. Purification of the crude product on silica gel using EtOAc:Hexane as solvent system afforded the desired product.
85%	With calcium hypochlorite; water monomer for 0.0166667h; microwave irradiation;
85%	With phosphotungstate-Fe³⁺ dual-metal-site modulated graphitic carbon nitride In acetonitrile at 25 - 35℃; for 20h; Sealed tube; Irradiation;
80%	With Montmorillonite K₁₀; iron nitrate (III) In hexane at 60℃; for 2h;
78%	With [RuCl₂(PPh₃)₂(2-PyCH₂1,3,5-triaza-7-phosphadamantane)].Br; potassium hydroxide In water monomer for 48h; Schlenk technique; Reflux; Inert atmosphere;	General procedure for dehydrogenation of alcohols General procedure: Ruthenium complex 2 (5 mol%), KOH (15 mol%), alcohol (5 mmol) and H2O (1.0 mL) wereplaced in Schlenk tube. The reaction mixture was stirred under reflux for 48 h. After completion of thereaction, the product was extracted with dichloromethane. Then all DCM were evaporated under vacuo,the product ketones and aldehydes were isolated from crude mixture by column chromatography usinghexane/EtOAc as eluent. The formation of products was confirmed by comparing the 1H-NMR datawith literature reports.
73%	With dihydrogen peroxide; acetic acid; sodium bromide In water monomer at 60℃; for 2h; Inert atmosphere;	General Procedure for NaBr-Catalyzed Oxidation General procedure: Under nitrogen atmosphere, to a solution of substrate alcohol (0.5 mmol) in aceticacid (1.0 mL) was added a stock-solution of aqueous NaBr solution (1.94 M, 25 μL)and 30% aqueous H2O2 (50 μL, 0.5 mmol). After stirring the mixture for one hour at60 °C, additional 30% aqueous H2O2 (50 μL, 0.5 mmol) was added, and stirring wascontinued for another one hour. After cooling, the mixture was poured into a saturatedaqueous NaHCO3 solution (ca. 30 mL) with the aid of CH2Cl2, and resulting mixturewas extracted with CH2Cl2. The combined organic layers were dried over anhydrousMgSO4, filtered and concentrated in vacuo. The residue was chromatographed onsilica gel (flash column or preparative TLC) to afford the corresponding ketone.
61%	In acetonitrile at 25℃; for 15h; Schlenk technique; Inert atmosphere; Sealed tube; Irradiation;
60.7%	With tert.-butylhydroperoxide at 70℃;
58%	With ruthenium(III) trichloride hydrate; C₁₃H₁₉N₄⁽¹⁺⁾*Br^(1-) In toluene at 115℃; for 24h; Schlenk technique; Inert atmosphere;	4.3. General procedure for dehydrogenation of alcohol General procedure: RuCl3nH2O (0.5 mol %), HMTA-Bz (1 mol %), alcohol (0.25 ml)and dry toluene (1.0 ml) were placed in a Schlenk tube. The reactionmixture was stirred under open condition to nitrogen andrefluxed for 24 h. After completion of the reaction all toluene wereevaporated under vacuo, the oxidized products were isolated fromcrude mixture with the help of column chromatography using hexane/EtOAc as eluent. The formation of products was confirmed bycomparing the 1H NMR data with literature reports.
55%	With barium permanganate Irradiation;
45%	With oxygen; triethylamine In tetrahydrofuran; toluene at 45℃; for 20h;
45%	With iron (ΙΙΙ) nitrate nonahydrate; N-hydroxyphthalimide; oxygen In acetonitrile at 25℃;	3 2.2. General procedure of oxidation of secondary alcohols General procedure: Substrate (1 mmol) and the desired amounts of Fe(NO3)3·9H2Oand NHPI were added to 1.5 mL of acetonitrile in a 15 mL test tube.The solution was maintained for 20 h under an atmospheric pres-sure of O2and at 25C. After the reaction was quenched by Na2S2O3solution, 60 mg of nitrobenzene, serving as an internal standard,was added to the reaction system. The solution was centrifugedand the supernatant was diluted with diethyl ether and dried withanhydrous Na2SO4for 30 min. The products were analyzed by GC,and further confirmed by GC-MS. The isolated yield was obtainedthrough column chromatography generally performed on silica gel(200-300 mesh).
24%	With sodium tetrafluoroborate; potassium hydroxide In acetone at 100℃; for 12h; Inert atmosphere; Schlenk technique;	3.8. General procedure for catalytic Oppenauer-type oxidation General procedure: To a mixture of ruthenium complex (0.04 mmol), KOH (0.4 mmol) and NaBF 4 (0.16 mmol) were added acetone (2 mL) and a substrate (0.8 mmol), the resulting mixture was heated at reflux in argon for 12 h or 100 °C for 12 h with some inactive substrates ( Table 3 , 2o-2r ). After the reaction completed, the prod- uct was isolated by column chromatography on silica gel with dichloromethane-petroleum ether as eluents.
	With chloroform; dinitrogen tertoxide
	With potassium dichromate\|\|potassium bichromate\|\|K₂Cr₂O₇\|\|Cr₂O₇K₂; sulfuric acid
8 % Chromat.	With oxygen In benzene for 10h; Ambient temperature; Irradiation;
	With manganese(IV) oxide; molecular sieve In hexane for 12h; Heating; Yield given;
3 % Chromat.	With oxygen In benzene for 16h; Ambient temperature; Irradiation; other time, other solvent,;
	With potassium peroxodisulfate; <i>tert</i>-butyl alcohol In water monomer at 25℃; Radiolysis;
	With C₃₀H₂₆N₃OP; potassium carbonate; copper chloride (I) at 110℃; for 14h;
	With palladium diacetate; oxygen; triethylamine In tetrahydrofuran; toluene at 20℃; for 12h;
97 %Spectr.	With Br^(1-)*C₂₀H₂₇BrN₅O₂Pd⁽¹⁺⁾; oxygen; anhydrous Sodium acetate at 20 - 120℃; for 96h;
86 %Spectr.	With [Cp*Ir(6,6'-dihydroxy-2,2'-bipyridine)(H₂O)](OTf)2 In water monomer for 20h; Inert atmosphere; Reflux;
	With C₂₂H₂₈BF₂NOS; isopropanol; potassium hydroxide for 9h; Reflux;
92 %Spectr.	With Cp*Ir(6,6'-dionato-2,2'-bipyridine)(H₂O) In n-Pentane at 90℃; for 5h;
88 %Chromat.	With styrene; 2C₁₃H₈NS^(1-)C₁₂H₂₇PIr⁽³⁺⁾*CF₃O₃S^(1-); potassium-t-butoxide In toluene at 110℃; for 12h; Schlenk technique; Inert atmosphere;
	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; 6,8-di(tert-butyl)-3-[2-(1H-imidazol-4-yl)ethyl]-3,4-dihydro-2H-1,3-benzoxazine; oxygen; copper trifluoromethanesulfonate In dichloromethane at 40℃; for 28.5h;	Typical procedure for the oxidation of secondary alcohols. General procedure: A 5-mL two-necked, round-bottom flask equipped with a magnetic stirrer and an oxygen balloon was charged in succession with 0.0106 g(0.05 mmol) of Cu(OTf), 0.0078 g (0.05 mmol) of TEMPO, 0.0171 g (0.05 mmol) of benzoxazine ligand L, and 2 mL of methylene chloride. The corresponding alcohol, 1 mmol, was then added at 40°C under stirring, and oxygen from the balloon was introduced through a three-way valve. The progress of the reaction was monitored by GLC using a suitable column.
	With sodium chlorine monoxide; N-Bromosuccinimide; [(R,R)-(N,N-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminato)]manganese(III) chloride In dichloromethane; water monomer at 25℃; for 4.5h; chemoselective reaction;	Catalytic oxidation General procedure: In a typical experiment an alcohol (1 mmol), salen-Mn(III) complex (0.02 mmol), NBS (0.13 mmol), and CH2Cl2 (2 mL) was loaded into a 5 mL flask at room temperature. NaOCl (2.3 mmol) was added dropwise within 10 min and progress of the reaction was monitored by GC. Upon completion of the process the reaction mixture was treated twice with10 mL of 10% NaHSO3 solution and the organic phase was dried over anhydrous sodium sulfate and filtered off. The solvent was removed by distillation. The residue was distilled under low pressure.
	With Pd/TiO₂(at)MIL-101 at 90℃; for 24h; Inert atmosphere;
	With nickel (II) chloride In water monomer at 20℃; for 6h; Inert atmosphere; Irradiation;
	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; Trametes versicolor laccase In tert-butyl methyl ether at 30℃; for 16h; Enzymatic reaction;
	With sodium chlorine monoxide; Sodium hydrogenocarbonate; sodium bromide In water monomer at 0℃; for 0.0833333h;
	With chromium(VI) oxide
86 %Spectr.	With 2-bromoanthracene-9,10-dione; nitrobenzene In acetonitrile at 30℃; for 20h; Sealed tube; Irradiation; Inert atmosphere;
88 %Chromat.	With C₂₅H₁₆N₂O₁₀Ru₃; anhydrous sodium carbonate; acetone at 60℃; for 8h; Inert atmosphere; Schlenk technique;

Yield	Reaction Conditions	Operation in experiment
86%	Stage #1: o-hydroxyacetophenone With lithium hydroxide monohydrate In tetrahydrofuran at 20℃; for 1h; Stage #2: dimethyl sulfate In tetrahydrofuran for 60h;
86%	Stage #1: o-hydroxyacetophenone With lithium hydroxide monohydrate In tetrahydrofuran at 20℃; for 1h; Stage #2: dimethyl sulfate In tetrahydrofuran for 60h;	4.1.5. 2-Methoxyphenyl methyl ketone 14 A solution of 1-(2-hydroxy-phenyl)-ethanone 13 (35.2 mL, 300 mmol) and LiOH·H2O (24.8 g, 590 mmol) in THF (400 mL) was stirred at room temperature for 1 h, and then dimethyl sulfate (42 mL, 293 mmol) was added. After completion of the reaction (TLC, 60 h), the solvent was removed under reduced pressure. The residue was dissolved in 2 M NaOH, and the resulting solution was extracted with diethyl ether. The combined extracts were dried over anhydrous MgSO4, filtered, and concentrated under reduced pressure to afford compound 14 (38.5 g, 256.0 mmol). Yield: 86%. 1H NMR (400 MHz, CDCl3): δ 7.71-7.69 (dd, J = 7.7, 1.8 Hz, 1H), 7.44-7.40 (m, 1H), 6.97-6.92 (m, 2H), 3.86 (s, 3H), 2.58 (s, 3H). 13C NMR (100.6 MHz, CDCl3): δ 199.8, 158.9, 133.7, 130.3, 128.2, 120.5, 111.6, 55.5, 31.8. IR (KBr): 3074, 3003, 2944, 2840, 1674, 1598, 1578, 1486, 1437, 1358, 1292, 1247, 1163, 1126, 1023, 967, 805, 758, 595, 534 cm-1.
81%	With tetrabutylammomium bromide; sodium hydroxide In diethoxymethane; water at 50 - 55℃; for 4h;

Yield	Reaction Conditions	Operation in experiment
96%	Stage #1: 2-Methoxyacetophenone With potassium hydroxide In ethanol; water at 0℃; for 0.5h; Stage #2: benzaldehyde In ethanol; water for 48h;	1.1 [Step 1] Preparation of ((E)-1-(2-methoxyphenyl)-3-phenylprop-2-en-1-one 2’-Methoxyacetophenone (1.09 g, 6.60 mmol) and 10% potassium hydroxide aqueous solution (80 mL, 142mmol) were dissolved in ethanol (15mL), and stirred at 0°C for 30 min. before adding benzaldehyde (0.800 mL, 7.92mmol) dropwise, and the mixture was stirred at room temperature for about 2 days. Ethanol was removed by evaporationusing an evaporator, and the remaining mixture was extracted 4 times with ethyl acetate (30mL), after which the extractwas dried with magnesium sulfate, and the filtered solution was concentrated. The residue was purified using silica gelcolumn chromatography (silica gel 60, eluant: ethyl acetate/hexane=1:7 (v/v)) to obtain the subject compound (1.52 mg,6.36 mmol, yield: 96%) as a yellow, oil-like substance. 1H NMR (400 MHz, CDCl3): δ: 7.64 (d, J = 4.8 Hz, 1H), 7.61-7.57 (m, 3H), 7.48 (ddd, J = 15.2, 15.2, 2.0 Hz,1H), 7.41-7.35 (m, 4H), 7.05 (dd, J = 6.4, 6.4 Hz, 1H), 7.01 (d, J = 8.5 Hz, 1H), 3.91 (s, 3H).
88%	With sodium hydroxide In methanol; water for 12h; Inert atmosphere;
87%	With sodium hydroxide In water at 0 - 20℃; diastereoselective reaction;

Yield	Reaction Conditions	Operation in experiment
100%	With potassium-t-butoxide; 1-hydrosilatrane In tetrahydrofuran; N,N-dimethyl-formamide for 48h;	2 General Procedure for the Reduction of Ketones General procedure: To a 25 ml round bottom flask containing 5 ml N,N-dimethylformamide, was added 1-hydrosilatrane (0.263 g, 2.0 mmol), and ketone (1.0 mmol). The resulting solution was stirred for 1 minute, after which 1 M t-BuOK in THF (1.0 mmol, 1.0 ml) was added. Reaction mixture was allowed to stir for 30 min. Reaction was quenched with 25 ml 3 M HCl, and extracted with 30 mL ethyl acetate. Organic layer was washed with brine (50 ml×3), and dried with anhydrous sodium sulphate. After filtration, the solvent was removed under vacuum to yield product.
99%	Stage #1: 1-(2-methoxyphenyl)ethan-1-one With (dppe)2Fe(H)2*(C₇H₈)2; Na-tetrakis(ethoxy)borate In toluene at 100℃; for 2h; visible light irradiation; Inert atmosphere; Stage #2: With lithium hydroxide monohydrate; sodium hydroxide In methanol; toluene at 20℃; for 16h;
99%	With dichloro-[1-(2,3,4,5,6-pentamethylbenzyl)-3-(2-methoxyethyl)benzimidazol-2-ylidene]ruthenium (II); isopropanol; potassium hydroxide at 80℃; for 1h; Inert atmosphere;

Yield	Reaction Conditions	Operation in experiment
99%	With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; hydroxylamine; oxygen In water monomer; 1,2-dichloro-ethane at 80℃; for 6h; Autoclave;
99%	With C₅₃H₄₆ClN₃P₂Ru; potassium-t-butoxide; acetone at 56℃; for 0.0833333h;
98%	With methyl 3,5-bis((1H-1,2,4-triazol-1-yl)methyl)benzoate; oxygen; anhydrous Sodium acetate; nickel(II) bromide at 120℃; for 72h;

75%	With lithium hydroxide In tetrahydrofuran at 70℃; for 1.5h;
	With potassium hydroxide

79.6%	With sodium hydroxide In ethanol; water Heating;	4.1.2. Synthesis and spectroscopic characterization of chalcones General procedure: All syntheses were carried out in the same fashion. Each reaction was monitored by TLC for 24 h to determine when the starting materials had been consumed. All TLC analyses were run on Selecto Scientific flexible silica gel-coated plates containing a fluorescent indicator and were developed using a hexanes-ethyl acetate (4:1) solution as the eluent. The following procedure is representative of the synthesis of all chalcones (see [Chart 1] and [Chart 2] for structures): A 25-mL round-bottomed flask was charged with the appropriate derivatives of both acetophenone (3 mmol) and benzaldehyde (3 mmol), and mixed with 10 mL of 95% EtOH. The mixture was then stirred magnetically while being gently heated (in a 30 °C water bath) until both starting materials dissolved. In a separate flask, NaOH (3.5 mmol) was added to 10-mL of an ethanol-water (1:1) and the mixture was stirred magnetically until the solid dissolved. The NaOH solution was then added dropwise (using a Pasteur pipet) to the ethanolic solution of acetophenone and benzaldehyde described above. In most cases, the reaction mixture turned yellow and solidified within a few minutes. Ice water (2 mL) was added to the flask and the mixture was stirred vigorously. The solid was collected on a Hirsch funnel, washed with cold water, and air-dried overnight. The purity of the crude product was determined at this point using a combination of TLC analysis, melting point measurement, and 1H NMR spectroscopy. In case of an oily product, the reaction mixture was extracted with two 10-mL portions of CH2Cl2 and the organic phase was collected, dried over Na2SO4, and removed using a rotary evaporator. The purity of the oily product was then determined as described above. All impure products (solid or oil) were purified by column chromatography using Merck Silica gel (grade 60, 230-400 mesh) and 4:1 hexanes-ethyl acetate as eluent. In case of a solid, chromatographic separation was followed by recrystallization from either methanol or ethanol-water mixture. In all cases, the purity of the final product was checked again as described above; the spectral characteristics were found to be in good general agreement with those found in the literature.4 The organic chalcones prepared for this study were either pale-yellow solids or oils of the same color (as specified); the ferrocenyl analogs were reddish-orange solids or oils. For each of the reported compounds below, the 1H NMR data is presented as δ (multiplicity, integral ratio), and the IR data as νCO, νCC. The following % yield and physical data are for new chalcones prepared for this study. Data for other chalcones (not given below) have been reported elsewhere[4], [5] and [6] and are also available online as Supplementary data.
78%	With sodium hydroxide In ethanol; water at 20℃; for 4h;
78%	With sodium hydroxide In water at 20℃; Cooling with ice;	Synthesis of (E)-chalcones 1a-j General procedure: Into a 25 mL flask was added ethanol (1 mL), acetophenone (1 mmol) and a solution of NaOH (507 mg) in H2O (450 μL). The reaction mixture was placed in an ice bath, and benzaldehyde was slowly added (102 μL, 1 mmol). The mixture was stirred for 2 to 6 h at room temperature and then neutralized with aqueous solution of NH4Cl (5 mL), extracted with AcOEt (3 x 30 mL). The organic phase was dried over Na2SO4 and then concentrated under vacuum.
72.8%	With sodium hydroxide In methanol at 28℃; for 12h;
71%	Stage #1: 2-Methoxyacetophenone With lithium hydroxide monohydrate In ethanol at 20℃; for 0.166667h; Stage #2: benzaldehyde In ethanol at 20℃; for 2h;
71%	With lithium hydroxide monohydrate In ethanol at 20℃; for 2h;	C.1.b In a 14-mL vial, the substituted acetophenone (1.25 mmol) and lithium hydroxide monohydrate (0.251 mmol) were dissolved in ethanol (5 mL) and the mixture was stirred at room temperature (RT) for 10 min followed by addition of substituted benzaldehyde (1.272 mmol). The reaction mixture was then stirred at RT and monitored by TLC using 25% ethyl acetate/hexanes as the solvent system. The reaction was quenched after 2 hrs by pouring into 50 mL of stirring ice cold water. If the product precipitated out after quenching with cold water, it was filtered off and crystallized with hot ethanol. In some examples, a sticky mass was observed in the aqueous solution after quenching. In those cases, the product was extracted by ethyl acetate (3 x 50 mL), dried over sodium sulfate, and concentrated under vacuum. The crude product was purified by flash chromatography using ethyl acetate/hexanes as the solvent system in increasing order of polarity. (E)-l-(2-methoxyphenyl)-3-phenylprop-2-en-l-one (lb): It was obtained as yellow oil in 71% yield. *H NMR (400 MHz, DMS) δ =7.76 -7.67 (m, 2H), 7.56 - 7.46 (m, 3H), 7.44 -7.37 (m, 4H), 7.18 (d, 7 =7.9 Hz, 1H), 7.05 (td, 7 =7.5, 0.9 Hz, 1H), 3.85 (s, 3H). 13C NMR (101 MHz, DMSO) δ 192.60, 158.17, 142.97, 135.01, 133.53, 130.94, 129.98, 129.45, 129.23, 128.97, 127.41, 121.01, 112.79, 56.27. LC- MS (ESI-TOF): m/z 239.1072 ([Ci6H1402 + H]+ calcd. 239.1067). Purity 98.02% (rt 7.21 min).
70%	With carbon tetrabromide In neat (no solvent) at 60℃; for 27h;
68%	With sodium hydroxide In ethanol; water at 20℃;
64%	With iodine; triphenylphosphine In 1,4-dioxane for 11h; Reflux;	General procedure for the synthesis of compounds 3 General procedure: A mixture of PPh3 (524 mg, 2.0 mmol, 1.0 equiv), I2 (507 mg, 2.0 mmol, 1.0 equiv) and 1,4-dioxane (4 mL) was stirred at rt for 30 min. Then, compounds 1 (2.0 mmol) and 2 (2.4 mmol) were added to the mixture, and stirred for appropriate time (Tabel 2) under reflux temperuture. After completion of the reaction (TLC), DCM (20 mL) was added and the solution was washed with NaS2O3 (20 mL, 10%). Then, organic layer was washed with water (2 × 20 mL) and brine (2 × 20 mL) and was dried over anhyd. MgSO4. The organic layer was concentrated under reduced pressure and the crude product was purified by column chromatography to afford the corresponding product 3.
60%	With potassium hydroxide In ethanol; water for 12h; Heating;
52%	With lithium hydroxide monohydrate In ethanol at 20℃; for 2.25h;	Preparation of (E)-1-(2-methoxyphenyl)-3-phenylprop-2-en-1-one (8a) General procedure: To an ethanol solution of the substituted acetophenones(1.0 equiv) was added LiOHH2O (1.0 equiv). The reaction mixture was stirred for 15 min at room temperature and then treated withthe desired benzaldehyde (1.2 equiv). The mixture was stirred for2 h at room temperature. The reaction mixture was quenched withH2O (100 mL) and then diluted with EtOAc (200 mL) and washedwith H2O (2 200 mL) and brine (200 mL). The organic layer wasdried with anhydrous Na2SO4 and concentrated in vacuo. The residuewas purified by column chromatography on SiO2
33%	With sodium hydroxide at 20℃; for 48h;	2.1. Chemistry General procedure: Synthesis of methoxychalcones 5-21 was achieved byClaisen-Schmidt reaction, using protocols reported by ourgroup with minor modifications [16,17]. Appropriateacetophenone derivatives (5 mmol) and respectivebenzaldehyde derivatives (5 mmol) were solubilized inethanol (10 mL), and ethanolic solution of NaOH (1.0 mol/L,5 mL) was added dropwise to the reaction medium, whichwas submitted to magnetic stirring at room temperature.Progress of reaction was checked by thin-layerchromatography analyses. After 48 h, the reaction mediumwas poured onto crushed ice from deionized water.Precipitates were removed by filtration, washed with colddeionized water and dried at room temperature. All crudeproducts were purified over successive silica gel columns,using mixtures of hexane and ethyl acetate as mobile phase.
16%	With sodium hydroxide In ethanol for 24h; Ambient temperature;
	With sodium hydroxide; ethanol
	With sodium hydroxide In 1,4-dioxane; water
	With ethanol; sodium hydroxide at 20℃; for 3h;
	With sodium hydroxide In ethanol; water at 20℃;	General procedure for the preparation of α,β-unsaturated ketones (1b-1k). General procedure: A 50 mL round-bottomed flask was charged with the appropriate ketone (3.0 mmol), aldehyde (3.0 mmol) and 10 ml of 95% EtOH, to which a NaOH solution [3.5 mmol of NaOH in 10 mL of ethanol-water (1:1, v/v)] was added dropwise. The mixture was stirred at room temperature. In most cases, a precipitate produced after stirring for several hours. The solid was collected by filtration, washed with water and recrystallized from EtOH to get the products. In the cases that oily products were produced, the solvent of reaction mixture was removed by rotary evaporator, the residue was treated with water (20 mL) and extracted with CH2Cl2 (3×20 mL). The organic phase was dried over anhydrous Na2SO4, and solvent was removed by a rotary evaporator. The residue was purified by column chromatography with petroleum ether/ethyl acetate (15:1-5:1) as an eluent to give products.
89 %Spectr.	With A₂₆ basic resin In ethanol; toluene at 40℃; Flow reactor; chemoselective reaction;
	With potassium hydroxide In methanol; water at 0 - 20℃;
	With sodium hydroxide In methanol
	With sodium hydroxide In ethanol; water at 20℃; for 12h;	Chalcones 2a-2d were prepared following the known proceduce:[7] benzaldehyde and NaOH were added to a solution of acetophenone in EtOH at room temperature. The mixture was stirred for 12 h, neutralized with diluted HCl, and extracted with EA. The organic layer was dried over Na2SO4 and the solvents evaporated. The residue was purified by flash column chromatography to give corresponding chalcones.
	With sodium hydroxide In methanol; water at 0 - 20℃;

Yield	Reaction Conditions	Operation in experiment
96%	With copper(ll) bromide In chloroform; ethyl acetate at 70℃; for 8h; Inert atmosphere; Reflux;	2-Bromo-1-(2-Methoxyphenyl)Ethanone (7a). Copper (II) bromide (2.97 g, 6.66 mmol) was placed in a twonecked round-bottomed flask fitted with a reflux condenser. EtOAc (10.0 mL) was added to it and the mixture was stirred at 70C for 5 min under nitrogen atmosphere. 1-(2-Methoxyphenyl)ethanone (6) (0.50 g, 3.33 mmol) in CHCl3 (10.0 mL) was slowly added to it and then the mixture was refluxed for 8 h. After completion of the reaction, it was cooled to room temperature, filtered through Celite pad, and washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure. The crude was puri- fied by column chromatography (EtOAc:hexane = 1:4) to afford the pure product 7a (0.73 g, 96%) as brown liquid. Rf = 0.43 (EtOAc/hexane = 1/4); 1 H NMR (300 MHz, CDCl3): δ 7.81 (1H, dd, J = 7.8, 1.8 Hz), 7.52 (1H, td, J = 7.8, 1.8 Hz), 7.05-6.96 (2H, m), 4.61 (2H, s), 3.94 (3H, s); 13C NMR (75 MHz, CDCl3): δ 192.3, 158.8, 134.9, 131.6, 124.9, 121.2, 111.7, 56.0, 38.0.
96%	With copper(ll) bromide In chloroform; ethyl acetate for 8h; Reflux; Inert atmosphere;	{2-Bromo-1- (2-methoxyphenyl) ethanone} (Compound 7a): A two-necked round bottom flask equipped with a reflux condenser was charged with copper (II)Bromide (2.97 g, 6.66 mmol) was added and EtOAc (10.0 mL)And the mixture was stirred at 70 ° C for 5 minutes. To a solution of 1- (2-methoxyphenyl) ethanone (Compound 6) in CHCl3 (10.0 mL)(0.50 g, 3.33 mmol) was slowly added and the mixture was refluxed for 8 hours.After the reaction was completed, the reaction mixture was cooled to room temperature, filtered through a pad of Celite (R), and washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure.The crude product was purified by column chromatography (EtOAc: hexane = 1: 4)To give pure brown compound 7a (0.73 g, 96%) as a brown liquid phase.
96%	With copper(ll) bromide In chloroform; ethyl acetate for 8h; Inert atmosphere; Reflux;	2-bromo-1-(2-methoxyphenyl)ethanone(2-bromo-1-(2-methoxyphenyl)ethanone}(compound 7a) Equipped with a reflux condenserCopper (II) bromide (2.97 g, 6.66 mmol) was added to a two-neck round bottom flask,Was added, EtOAc (10.0 mL) was added, and the mixture was stirred at 70 ° C for 5 minutes.1- (2-methoxyphenyl) ethanone (Compound 6) (0.50 g, 3.33 mmol) was slowly added to CHCl 3 (10.0 mL) under nitrogen atmosphere,The mixture was refluxed for 8 hours.After completion of the reaction,After cooling to room temperature,Filtration through a Celite pad,And washed with EtOAc (20 mL).The filtrate was concentrated under reduced pressure.The crude product was purified by column chromatography (EtOAc: hexane = 1: 4) to give pure compound 7a (0.73 g, 96%) as a brown liquid phase.

91%	With N-Bromosuccinimide at 20℃; for 2h;
91%	With N-Bromosuccinimide; toluene-4-sulfonic acid at 20℃; for 2h;
91%	With copper(ll) bromide In ethyl acetate for 3h; Reflux;
90%	With N-Bromosuccinimide; toluene-4-sulfonic acid In dichloromethane at 40℃; for 0.25h; Microwave irradiation; Green chemistry;
84%	With N-Bromosuccinimide; toluene-4-sulfonic acid
83%	Stage #1: 2-Methoxyacetophenone With toluene-4-sulfonic acid at 60℃; Stage #2: With N-Bromosuccinimide at 60℃; for 0.25h;	3.2.1. General Procedure for the Synthesis of Phenacyl Bromides 2, 11 General procedure: The round-bottom flask containing acetophenone derivative 1, 10 (4 mmol) and PTSA (0.076 g,0.4 mmol) was heated to 60 °C to turn the reaction mixture into a paste and NBS (0.854 g, 4.8 mmol) thenadded slowly. After 15 min, the reaction mixture was cooled to room temperature and water (20 mL)added. The crude product was extracted with dichloromethane (2 x 20 mL), dried over anhydrousNa2SO4 and purified by crystallization from n-hexane-dichloromethane to give pure product. 2-Methoxyphenacyl bromide (2): Yellow solid, soluble in acetone, dichloromethane, chloroform, insolublein water; yield 83%; m.p.: 43-45 °C; 1H-NMR (500 MHz, CDCl3) (δ, ppm): 7.78 (dd, 1H, J = 1.5,7.5 Hz, Ar-H), 7.51-7.47 (m, 1H, Ar-H), 7.02-6.96 (m, 2H, Ar-H), 4.57 (s, 2H, CH2), 3.93 (s, 3H, OCH3).This result showed consistency with the data in literature [26].
83%	With N-Bromosuccinimide; toluene-4-sulfonic acid In neat (no solvent) at 60℃; for 0.25h; regioselective reaction;	General procedure for the synthesis of phenacyl bromides (3a-i) General procedure: The round-bottom flask containing acetophenone derivative 2a-i (4 mmol) and PTSA (0.076 g, 0.4 mmol) was heated to 60 oC to turn the reaction mixture into a paste and then NBS (0.854 g, 4.8 mmol) was added slowly. After 15 min., the reaction mixture was cooled to room temperature and water (20 ml) was added. The crude product was extracted with dichloromethane (2 x 20 mL), dried over anhydrous Na2SO4 and puried by crystallization from hexane-dichloromethane to give pure product. 2-Methoxyphenacyl bromide (3a):[20,29] Yellow solid, soluble in acetone, dichloromethane, chloroform, insoluble in water; yield 83%; mp: 43-45 oC; 1H NMR (500 MHz, CDCl3) (δ, ppm): 7.78 (d, 1H, J = 7.5 Hz, Ar-H), 7.51-7.47 (m, 1H, Ar-H), 7.02-6.96 (m, 2H, Ar-H), 4.57 (s, 2H, CH2), 3.93 (s, 3H, OCH3).
77%	With bis(1,3-dimethyl-2-imidazolidinone) hydrotribromide In dichloromethane at 20℃; for 1h;	4.3 Typical procedure for the α-bromination of carbonyl compounds with 3a General procedure: To a solution of propiophenone (9a, 285mg, 2.15mmol) in CH2Cl2 (4mL) was added 3a (1.23g, 2.62mmol), and the mixture was stirred at 20°C for 1h. The reaction mixture was quenched with saturated NaHCO3 aqueous solution and then extracted with diethyl ether (15mL×3). The combined organic layers were washed with water (20mL×2), dried over Na2SO4 and concentrated in vacuo. The resulting crude residue was purified using silica gel column chromatography (eluent: hexane/chloroform=1:2) to afford bromide 10a (433mg, 94%) [24] as a white crystalline solid
60%	With bromine In tetrachloromethane for 0.833333h;
	With bromine In chloroform for 0.25h; Ambient temperature;
	With bromine In 1,4-dioxane; diethyl ether for 1h;
	With aluminium trichloride; bromine In diethyl ether
	With hydrogenchloride; bromine In acetic acid at 20℃;
	With bromine In diethyl ether at 20℃;
	With bromine In chloroform Heating;
	With N-Bromosuccinimide; toluene-4-sulfonic acid at 20℃; for 2h;
	With copper(ll) bromide In chloroform; ethyl acetate for 0.333333h; Reflux; Inert atmosphere;
	With toluene-4-sulfonic acid; N,N'-dibromohydantoin In methanol at 30℃; for 8h;	5.2. General procedure for the preparation of compounds 2 General procedure: To a solution of the appropriate acetophenone 1 and p-toluenesulfonic acid (15 mmol) in dry methanol (20 mL), dibromohydantoin (15 mmol), diluted in methanol (20 mL) was added dropwise and the mixture was stirred for 8 h at 30 °C. After the completion of the reaction, excess solvent was removed under reduced pressure. Ice water was added to the residue. The precipitated solid was filtered, and washed with ethanol. The resulting crude solid was directly used in the next step without purification.
	With bromine In diethyl ether Inert atmosphere;
	With copper(ll) bromide In chloroform; ethyl acetate for 8h; Reflux;
	With copper(ll) bromide In chloroform; ethyl acetate for 8h; Reflux;
	With copper(ll) bromide In chloroform; ethyl acetate at 85℃; for 3h;
	With copper(ll) bromide In tetrahydrofuran
	With tetrabutylammomium bromide In acetonitrile at 20℃;
	With copper(ll) bromide In chloroform; ethyl acetate Reflux;	Substituted 2-bromo-1-arylethanone 7a-o General procedure: Substituted 2-bromo-1-arylethanone 7a-o A solution of the appropriate ketone 3a-o (25 mmol) in hot chloroform (25 mL) was added to a preheated, stirred suspension of copper (II) bromide (50 mmol) in ethyl acetate (25 mL). The resulting reaction mixture was refluxed with vigorous stirring till completion of the reaction which detected by TLC monitoring. The reaction mixture was filtered while hot to remove copper (I) bromide then concentrated under reduced pressure. After cooling, the separated solid was filtered, washed with petroleum ether and dried to give compounds 7a-o [49] .
	With hydrogen bromide; bromine; acetic acid at 0 - 5℃;	General procedure to obtainα-bromoacetophenonederivatives General procedure: General procedure to obtainα-bromoacetophenonederivatives Acetophenone derivative (10 mmol) was solved in acetic acid(50 mL) and hydrobromic acid (0.5 mL) mixture. Bromine(10 mmol, 0.52 mL) was added dropwise to this mixture at 0-5°Ctemperatureandthemixturewasstirredfor6-7h.Afterthisperiod, the mixture was poured into ice-water, collapsed portionwas filtrated and after dryness it was crystallized from ethanol.
	With tetra-N-butylammonium tribromide In acetonitrile at 20℃; for 12h;	Step (i) General procedure: (i) The commercial available 8a-8l (4 mmol, 1.0 equiv.)was respectively dissolved in acetonitrile (50 mL), adding tetrabutylammoniumtribromide(4 mmol, 1.0 equiv.) later. The mixture was stirred overnight under roomtemperature until the solution turned light yellow or colorless. The solventwas removed in vacuo, the residue wasextracted with dichloromethane and washed with water. The organic layers werecombined and concentrated under vacuum to provide the crude products 9a-9l, which using for next step withoutany purification.
	With bromine In diethyl ether
	With bromine In toluene at 5 - 10℃; for 3h;	1 (2-phenyl-4 - (2-methoxy) phenyl imidazole for manufacturing) O- [...] (300g) is toluene (500 ml) to a solution dissolving the bromine (320g) and is adapted to hold a 5-10 °C while agitating 3 was dripped over time. Furthermore, 20 °C hereinafter water (500 ml) adding an, potassium carbonate (300g) of 1 was including neutralization with an and introduced over time. Furthermore, ethyl acetic acid (500 ml) and water (500 ml) by the addition of extracted organic layer. Saline saturated organic layer (500 ml) to 2 times cleaning and, generated α-bromo (2-methoxy) acetophenone with a biocatalyst, without isolating the ground terminal of to next reactor being. [...] benzamide with an organic layer (320g), potassium carbonate (800g) and water (600 ml) in 60 °C by mixing he stirring time 6. A reaction solution are the first using of potassium hydroxide after including neutralization with an, acetic acid ethyl (1 ℓ) extracted organic layer by the addition of. Saline saturated organic layer (1 ℓ) to 3 times cleaning and, in evaporator 150 ml was concentrating up. Hexane (1 ℓ) adding an, at room temperature to filter out generated members 150g of 2-phenyl-4 - (2-methoxy) phenyl imidazole is obtained.
	With copper(ll) bromide In dichloromethane; ethyl acetate at 60℃; Microwave irradiation; Sealed tube;
	With N-Bromosuccinimide; toluene-4-sulfonic acid In acetonitrile at 80℃; for 3.5h; Inert atmosphere;	5.A Step A. A 200 mL flask was charged with 2′-methoxyacetophenone (7.51 g, 50 mmol), N-bromosuccinimide (9.79 g, 55 mmol), p-toluenesulfonic acid (10.79 g, 55 mmol) and MeCN (100 mL) under nitrogen stream and the mixture was stirred for 3.5 hours at 80° C. The mixture was allowed to cool to room temperature and then MeCN was removed by an evaporator. CHCl3 (150 mL) and H2O (50 mL) were added to a residue and the lower layer was separated and then washed with saturated aqueous NaHCO3 (50 mL) twice and brine (50 mL). The solution was dried over anhydrous MgSO4 and filtrated. Solvents were then removed in an evaporator and the crude product as orange-brown oil (11.74 g) in >99.9% yield was obtained. This product was identified as 2-Bromo-2′-methoxyacetophenone contaminated with some dibromo compound. 1H-NMR (CDCl3), delta (ppm): 3.93 (s, 3H), 4.59 (s, 2H), 6.97 (d, J=8.4 Hz, 1H), 7.00-7.06 (m, 1H), 7.50 (ddd, J=1.8, 7.3, 8.4 Hz, 1H), 7.81 (dd, J=1.8, 7.7 Hz, 1H).
	With copper(ll) bromide In ethyl acetate for 12h; Reflux;	General procedure: In the synthesis process, different 1-(aryl/heteroaryl)ethanone(50 mmol) derivatives were brominated in the presence of copper(II) bromide (100 mmol) followed by a reaction with equimolarpyrimidine-2-carbothioamide (50 mmol). In the course of the reaction,the components were mixed in ethanol acetate for approximately1 h in room temperature and then refluxed at 77-78 Cfor 15-20 min. After cooling, the precipitate was filtered, neutralizedwith sodium acetate, and recovered from the HBr salt. Allthe synthesized compounds were purified twice by crystallizationfrom ethanol. Pyrimidine-2-carbonitrile and phosphorus pentasulfidewere mixed in dioxane for 48 h to obtain pyrimidine-2-carbothioamideas the starting material. This is the first time in theliterature that synthesis of pyrimidine thioamides has been undertakenwith this method
	With N-Bromosuccinimide; toluene-4-sulfonic acid In water; acetonitrile at 80℃; for 3.5h; Inert atmosphere;	7.A Step A. A 200 mL flask was charged with 2′-methoxyacetophenone (7.51 g, 50 mmol), N-bromosuccinimide (9.79 g, 55 mmol), p-toluenesulfonic acid (10.79 g, 55 mmol) and MeCN (100 mL) under nitrogen stream and the mixture was stirred for 3.5 hours at 80° C. The mixture was allowed to cool to room temperature and then MeCN was removed by an evaporator. CHCl3 (150 mL) and H2O (50 mL) were added to a residue and the lower layer was separated and then washed with saturated aqueous NaHCO3 (50 mL) twice and brine (50 mL). The solution was dried over anhydrous MgSO4 and filtrated. Solvents were then removed in an evaporator and the crude product as orange-brown oil (11.74 g) in >99.9% yield was obtained. This product was identified as 2-Bromo-2′-methoxyacetophenone contaminated with some dibromo compound. 1H-NMR (CDCl3), delta (ppm): 3.93 (s, 3H), 4.59 (s, 2H), 6.97 (d, J=8.4 Hz, 1H), 7.00-7.06 (m, 1H), 7.50 (ddd, J=1.8, 7.3, 8.4 Hz, 1H), 7.81 (dd, J=1.8, 7.7 Hz, 1H).
	With bromine In dichloromethane at 20℃; for 3h;
330 g	With bromine In acetonitrile at 20 - 25℃; for 4h;	5.1 [00241] Example 5.1: Preparation of 2-bromo-l-(2-methoxyphenyl)ethan-l-one (compound 1.2) 1 -(2-methoxyphenyl)ethan-1 -one 2-bromo-1 - MW: 150.17 (2-methoxyphenyl)ethan-1-one MW: 229.07 [00242] l-(2-methoxyphenyl)ethanone, 1.1, (300 g, 1.0 eq) was added to a reactor containing acetonitrile (1.2 L, 4.0 V). Br2 (319.62 g, 1.0 eq) was added by cooling the reaction to below 25°C. The reaction mixture was stirred for 4 h at 20-25 °C and sampled for IPC until the content of l-(2-methoxyphenyl)ethanone was 6.5%. NaHSCb (600 ml, 2V) was added to quench the reaction and then stirred for an additional 0.5h at 20-25°C. Product was extracted with methyl tert-butyl ether (600 ml, 2V), three times, to yield a black oil (418 g, crude), which was purified using a column to yield 330 g of 2-bromo-l-(2-methoxyphenyl)ethan-l-one, 1.2, as an off-white solid (98% purity).
	With bromine In diethyl ether at 0 - 20℃;
	With copper(ll) bromide In chloroform; ethyl acetate for 2h; Reflux;
	With copper(ll) bromide In 2-methyltetrahydrofuran at 20℃; for 24h;	General procedure for synthesis of α-haloketones(7-12) General procedure: To a solution of acetophenones 1-6 (16.65 mmol) in 2-Metetrahydrofuran(20 mL), copper(II)bromide (19.98 mmol)was added (Raghunath et al. 2015). The reaction mixturewas allowed to stir at room temperature for 24 h. Aftercompletion of the reaction (monitored by TLC), reactionmixture was filtered off. The filtrate containing the 2-bromo-1-phenylethanones 7-12 was taken to the next stepwithout isolation. However, to check the purity of theformed phenacyl bromides, two representative compounds(8 and 10) were isolated in standard procedure by evaporatingthe solvent under vacuum and confirmed by spectralanalysis (1H NMR, Mass, and HPLC). As all the derivativeswere pure by TLC, they were preceded to next step withoutpurification/isolation.
	With N-Bromosuccinimide; toluene-4-sulfonic acid In acetonitrile at 60℃; for 4h;
	With N-Bromosuccinimide; toluene-4-sulfonic acid In chloroform at 20℃; for 24h;	3.1.4 General procedure for the synthesis of b1-b5 General procedure: To a solution of acetophenone (3mmol) in CHCl3 were added p-TsOH·H2O (100mg, 0.53mmol) and N-bromosuccinimide (NBS, 214mg, 3.6mmol). The mixture was stirred at room temperature for 24h. The aqueous mixture was extracted with ether (50mL). The organic layer was dried (Na2SO4), after filtration, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (Petroleum ether and CH2Cl2, 2:1) to obtain white solid. To a solution of the white solid in DMF (50mL), NaN3 (143mg, 2.2mmol) was added. After stirred at r.t for 3h, the solid was disappeared completely. Added ascorbic acid (528mg, 3mmol) and anhydrous K2CO3 (414mg, 3mmol) into the reaction solution, stirred at r.t for 30min. Then added the intermediate 2 (680mg, 2mmol) and CuSO4·5H2O (625mg, 2.5mmol) into the reaction solution, stirred at r.t for 3h. Method as described in 4.1.2.2 (acidified to pH 5-6 and extracted with EtOAc, washed with brine solution, dried over anhydrous Na2SO4, filtered, and concentrated). The residues of b1-b5, were purified by flash column chromatography (CHCl3/Petroleum ether/mehanol=1/1, v/v) [30] (white crystal or powder, yield 36-80% for this step reaction, Scheme 1).
	With bromine In methanol
	With N-Bromosuccinimide; toluene-4-sulfonic acid In acetonitrile at 50℃; for 24h; Inert atmosphere;
	Stage #1: 2-Methoxyacetophenone With copper(I) bromide In ethyl acetate Inert atmosphere; Stage #2:
	With copper(ll) bromide In ethyl acetate for 5h; Schlenk technique; Inert atmosphere; Reflux;
	With N-Bromosuccinimide; toluene-4-sulfonic acid In water; acetonitrile Reflux;
	With copper(ll) bromide In dichloromethane; ethyl acetate at 60℃; for 0.25h; Microwave irradiation;

Yield	Reaction Conditions	Operation in experiment
99%	With N-Bromosuccinimide; iodine; In acetonitrile; for 12h;Darkness;	General procedure: To a reaction tube charged with NBS (1.5 equiv, 0.3 mmol), catalyst (10 mol%, 0.02 mmol) and CH3CN (1.0 mL),was added para-chloroanisole 1a (0.2 mmol). After being stirred at room temperature for 12 h in dark, the reaction was quenched by saturated aq. solution of Na2S2O3 (2 mL). The resulting mixture was extracted by ethyl acetate (3 5 mL). The combined organic extracts were washed by brine (10 mL), dried over Na2SO4 and filtered through a pad of Celite. The filtrate was concentrated under reduced pressure and the residuewas purified by flash chromatography on a silica gel column with petroleum ether/dichloromethane (5:1) as the eluent to give 4.3.1. 2-Bromo-4-chloroanisole (2a)
95%	With hydrogenchloride; N-Bromosuccinimide; In water; acetone; at 20℃; for 3h;	Compound 41-2 (0492) To a solution of 41-1 (2.0 g, 13.32 mmol) in acetone (25 mL) was added NBS (2.37 g, 13.32 mmol) and 1M HCl aq. (0.13 mL, 0.13 mmol). The reaction mixture was stirred at room temperature for 3 h, and then concentrated to dryness under reduced pressure. The residue was dissolved with PE (40 mL) the resultant precipitate was filtered and dried in vacuum to afford 41-2 as a white solid (2.90 g, yield: 95%).

Yield	Reaction Conditions	Operation in experiment
92%	With ammonia; hydrogen In water at 130℃; for 24h; Autoclave;
91%	With formic acid; C₂₆H₃₄ClIrN₄O; ammonium formate In methanol at 80℃; for 4h; Inert atmosphere; Schlenk technique;
88%	With ammonia; hydrogen In tetrahydrofuran at 120℃; for 15h;

84%	With 4-methoxy-N-(1-(naphthalen-2-yl)ethylidene)aniline; ammonium formate In methanol at 80℃; for 12h; Inert atmosphere; chemoselective reaction;
82%	With ammonium acetate; sodium cyanoborohydride In methanol for 96h; Ambient temperature;
72%	With ammonium hydroxide; ammonium acetate; sodium cyanoborohydride; zinc In ethanol; water at 80℃; for 36h;	4.2.1. General procedure for the synthesis of amines via reductive amination of acetophenones General procedure: To a saturated solution of NH4OAc in EtOH (40 mL) were added activated Zn (5 equiv), acetophenone (1 equiv), NaBCNH3(3 equiv) and 30% aq NH3 (10 mL) respectively. The mixture wasstirred at 80 C for 36 h. The reaction mixture was cooled to rt and concentrated under reduced pressure. The residue was dissolved in CH2Cl2 and made basic using 1 M NaOH (50 mL). Theorganic phase was separated and aqua phase was extracted with (2x25 mL) CH2Cl2. The organic phases were combined and acidified with HCl (pH: 2.0). The organic layer was separated andH2O layer was extracted with CH2Cl2 (2 25 mL). The H2O layer was made basic with NaOH (pH: 10.0), The organic layer was extracted with CH2Cl2 (3 25 mL). Combined organic layers weredried over Na2SO4 and evaporation of the solvent afforded thedesired amines.
57%	Stage #1: 2-Methoxyacetophenone With titanium(IV) isopropylate; ammonia In isopropyl alcohol at 20℃; Stage #2: With sodium tetrahydroborate In isopropyl alcohol at 20℃; for 2h;
	With ammonium acetate; sodium cyanoborohydride In methanol at 20℃;
	Multi-step reaction with 3 steps 1: titanium(IV) isopropylate / Isopropyl acetate / 0.5 h 2: 5%-palladium/activated carbon; hydrogen / Isopropyl acetate / 24 h / 24 °C / 11251.1 Torr 3: 5%-palladium/activated carbon; hydrogen / Isopropyl acetate / 24 h / 55 °C
	With ammonium acetate; sodium cyanoborohydride In methanol at 20℃; for 12h;	General procedure: 1-(2-methylphenyl)ethanone (0.50 mL, 3.73 mmol) and ammonium acetate (2.88 g, 37.3 mmol) were dissolved in methanol (20 mL). To the stirred solution was added slowly a solution of NaCNBH3 (0.79 g, 11.2 mmol) dissolved in methanol (15 mL) through a dropping funnel. The whole mixture was stirred at room temperature. After stirring for 12 h, solvent was removed by using rotary evaporator. The residue was dissolved in ethyl acetate and then the solution was treated with 6 N HCl solution to makethe solution to be acidic (pH = 12-13). The two layers were separated and then 6 N NaOH solutionwas added to the separated aqueous solution to make the solution to be basic (pH = 11-12). The basic aqueous solution was extracted with ethyl acetate twice and then combined organic solution was dried over anhydrous Na2SO4. Solvent was removed by using rotary evaporator to afford an intermediateamine B, 1-(2-methylphenyl)ethylamine (Ar = 2-methylphenyl, R1 = CH3, compound B in Figure 5) (0.21 g, 46% yield).
	Multi-step reaction with 2 steps 1: formic acid; formamide / 6 h / 190 °C 2: hydrogenchloride / water / 12 h / Reflux
	With ammonium acetate; sodium cyanoborohydride In methanol at 20℃; for 24h;
	With water; formamide In neat (no solvent) at 160℃;

Yield	Reaction Conditions	Operation in experiment
99%	With lithium hydroxide; hydrogen; triphenylphosphine; iridium; (8R,9R)-9-amino(9-deoxy)epicinchonin In methanol at 40℃; for 20h; optical yield given as %ee; enantioselective reaction;
99%	With hydrogen; potassium hydroxide; 9-amino-9-deoxyepicinchonine In isopropyl alcohol at 40℃; for 5h; Autoclave; optical yield given as %ee; enantioselective reaction;
99%	With bis(1,5-cyclooctadiene)diiridium(I) dichloride; (R)-N-(3-methylpyridine-2-methyl)-7-bis-(3,5-di-tert-butylphenyl)phosphino-7′-amino-1,1′-spirodihydroindane; potassium <i>tert</i>-butylate; hydrogen In ethanol at 25 - 30℃; for 0.666667h; Autoclave; optical yield given as %ee; enantioselective reaction;

Yield	Reaction Conditions	Operation in experiment
96%	With aluminum (III) chloride In dichloromethane at -5 - 25℃;
89%	With hydrogen iodide at 25℃; for 24h; Inert atmosphere;	5 Synthesis of o-hydroxyacetophenone A 2-way cock with a septum at the tip was attached to a recovery flask containing o-methoxyacetophenone (159 mg, 1.05 mmol), dried by allowing to stand overnight under reduced pressure in the presence of diphosphorus pentoxide, At atmospheric pressure. After reducing the pressure with a diaphragm pump again, hydrogen iodide gas (257 mg, 2.01 mmol) was introduced from the septum using a 50 mL syringe, and after returning to atmospheric pressure by filling with nitrogen, it was allowed to stand at 25 ° C. for 24 hours I put it. After the reaction, the mixture was reduced in pressure by a diaphragm pump to obtain a mixture of o-hydroxyacetophenone and o-methoxyacetophenone (128.6 mg). The yield was determined to be 89%: 1% of o-hydroxyacetophenone: o-methoxyacetophenone from the integral ratio of 1 H-NMR using phenanthrene as an internal standard.
85%	With 1-n-butyl-3-methylimidazolim bromide at 220℃; for 0.666667h; Inert atmosphere; Microwave irradiation;

85%	With magnesium iodide at 50℃; for 4h; Ionic liquid;
80%	With dimethyl diselenide; sodium In N,N,N,N,N,N-hexamethylphosphoric triamide for 8h; Heating;
77%	With cerium(III) chloride; sodium iodide In acetonitrile for 8h; Heating;

Yield	Reaction Conditions	Operation in experiment
92%	With silver trifluoromethanesulfonate; In water; acetic acid; at 110℃; for 6h;Schlenk technique;	General procedure: To a 25mL Schlenk tube, AuSBA-15 (6wt%, 20mg), AgOTf (0.05mmol) was added to a solution of phenylacetylene (1.0mmol) in HOAc/H2O (3.0mL, 15:1) under ambient air, the resulting mixture was stirred for 6hat 110C. It was monitored by TLC. After the reaction was completed, the solvent was removed under reduced pressure and purified of the crude product by column chromatography on silica-gel afforded the desired compound.
90%	With Perfluorooctanesulfonic acid; C8AgF17O3S*H2O; In water; at 100℃; for 8h;Darkness;	General procedure: To the mixture of phenylacetylene (1 mmol), water (3.0 mL),silver perfluorooctanesulfonate (5 mol%) and perfluorooctane sulfonateacid (2 mol%) was added. The mixture was stirred at 100 Cfor 8 h. The solution was extracted with n-hexane (diethyl ether)(3 5 mL), the combined extract was dried with anhydrous MgSO4. The rest of the solution was used for the next cycle of reaction. Theextraction solvent was removed and the crude product was separatedby column chromatography to give the pure sample.
88%	With silver tetrafluoroborate; water; In acetic acid; at 110℃; for 10h;	General procedure: To the mixture of terminal alkyne (1mmol), water (2.0 equiv), and acetic acid (2 mL), silver tetrafluoroborate (5 mol%) was added. The mixture was stirred at 110C for 10 h. Water (10 mL) was added and the solution was extracted with ethyl acetate (3×8 mL), the combined extract was dried with anhydrous MgSO4. The solvent was removed and the crude product was separated by column chromatography to give the pure sample. 4.2.9. 1-(2-Methoxyphenyl)ethanone (2i). 1H NMR (400 MHz, CDCl3): delta=7.69-7.72 (m, 1H), 7.41 (m, 1H), 6.93-6.98 (m, 2H), 3.88 (s, 3H), 2.59 (s, 3H). 13C NMR (100 MHz, CDCl3): delta=199.8, 158.9, 133.6, 130.3, 128.2, 120.5, 111.6, 55.4, 31.8. MS (EI) m/z: 150, 135, 105, 92, 77, 63.

85%	With indium(III) triflate; water; toluene-4-sulfonic acid; In 1,2-dichloro-ethane; for 0.5h;Sealed tube; Reflux;	General procedure: The reaction mixture of In(OTf)3 (11.2 mg, 2 mol %), PTSA (57.1 mg, 30 mol %), DCE (2.0 mL), alkynes 1a-1n or 1p-1t (1.0 mmol) and water (0.2 mL) in a 10 mL flask or in a 10 mL sealed tube was stirred at reflux and monitored periodically by TLC. Upon completion, DCE was removed under reduced pressure using an aspirator, and then the residue was purified by flash chromatography (PE/EA) on silica gel to afford corresponding carbonyl compounds 2a-2n or 2p-2t.
84%	With water; In methanol; at 150℃; under 8250.83 Torr; for 14h;Autoclave; Inert atmosphere; Green chemistry;	General procedure: In a 100 mL capacity of autoclave vessel a 60 mL solution of methanol and water (1:2) was added, further 1 mmol alkynes were added to this solution. The autoclave was three times purged withthe gas and then nally pressurized up to the 11 bar pressure. The reaction mixture was vigorously stirred at 150 C for continuous 14 h. After the completion of the reaction, the reactor was cooled to room temperature, and then the argon pressure was carefully released to the atmospheric pressure. Methanol from the reaction mixture is removed using rotatory evaporator. After that, the reaction mixture was transferred in a separating funnel, and it wasworked up with ethyl acetate. The organic layer was separatedand dried over Na2SO4. Afterwards, it was filtered and concentrated under reduced pressure. The resulted crude mixture waspuried by silica gel column chromatography using ethyl acetate/n-hexane as eluent, and pure keto product was isolated.
84%	With methanol; In water; at -5℃; for 0.5h;Irradiation; Green chemistry;	General procedure: To a 100 mL capacity borosilicate immersion well of UV reactor, 80 mL aqueous methanol MeOH:H2O (1:2), alkyne (1 mmol), Rh catalyst (1.5 mol%) was added, and the reaction mixture was cooled to-5 C. It was irradiated using a Hg vapor UV lamp, 125 W, 289 nm for30 min with continuous stirring. After completion of the reaction, the reaction mixture was left to warm to room temperature and then concentrated in vacuo. The residue was extracted with dichloromethaneand water, the organic phase was collected, dried with anhydrous Na2SO4, concentrated at reduced pressure, and puried by flash columnchromatography using hexane/ethyl acetate as eluent to obtain the corresponding product.The catalyst was synthesized as per the procedure reported in reference 15.
76%	With iron(III) sulfate hydrate; acetic acid; at 95℃; for 7h;Schlenk technique;	General procedure: Ferric sulfate hydrate (I, 8 mol%), glacial acetic acid (5 mL) and the alkyne (1 - 2 mmol) were introducedinto a 50 mL Schlenk tube, equipped with an air condenser, and the mixture kept under stirring at 95 C or120 C, until consumption of the substrate or no further conversion, as evidenced by TLC or GC. Uponcooling, the supernatant solution was poored into water and the residue washed twice with diethyl ether.After extraction with diethyl ether ( 2), the combined organic layers were washed with a saturated aqueoussolution of sodium bicarbonate and then water until neutrality. Alternatively, the crude from the reactions ofsubstrates featuring hydroxyl or carbonyl groups, as for 12, 15, 20 and 22, was obtained by removing aceticacid under vacuum, in order to reduce loss of material during biphasic extraction. The products were purified
99%Chromat.	With methanol; water; gold(I) chloride; at 65℃; for 3h;Green chemistry;	General procedure: In a 4 mL reaction vial equipped with a magnetic stirring bar,AuCl (5.8 mg, 0.025 mmol, 5 mol%) was added to MeOH (1 mL)under argon atmosphere. The reaction mixture was stirred for 5min, and then starting material (0.5 mmol, 1.0 equiv) and internalstandard dodecane (1.0 equiv) were added, followed bydefined amount of distilled H2O (4.0 equiv). The resulting reactionmixture was heated for 3 h, or for 24 h when needed, at65 C. After completion of the reaction, the reaction mixturewas diluted and filtered using CH2Cl2 and injected in GC foranalysis.

Yield	Reaction Conditions	Operation in experiment
82%	With dipotassium peroxodisulfate; copper(I) sulfate In water; acetonitrile at 65 - 70℃; for 3h;
77%	With pyridine; N-hydroxyphthalimide; tetrabutylammonium tetrafluoroborate; oxygen In 2,2,2-trifluoroethanol; acetonitrile at 25 - 30℃; Electrolysis;	2.2.1 Procedure for mono-oxidation General procedure: An undivided cell was equipped with a magnet stirrer, platinum plate electrode (1.0×1.0×0.3 cm3), as the working electrode and counter electrode. Substrate (0.5 mmol),nBu4NBF4 (0.5 mmol, 164.6 mg), N-hydroxyphthalimide (NHPI, 0.1 mmol, 16.3 mg), and pyridine (1.0 mmol, 82 μL)were added to MeCN/2,2,2-trifluoroethan-1-ol (TFE) (5:1,3 mL). The electrolysis was conducted in an undivided cell equipped with O2 balloon at a constant current of 5 mA at room temperature (25-30 °C). When the reaction was completed, the solvent was removed under reduced pressure and the remaining crude product was purified by column chromatography over silica gel (petroleum ether/ethyl acetate(PE/EA)=30:1-10:1) to afford the corresponding aromatic ketone product.
72%	With cerium(III) chloride In water at 25℃; for 24h; Irradiation; Green chemistry;

56%	With 2,6-dimethylpyridine; oxygen; C₃₄H₃₆NO₆⁽¹⁺⁾*ClO₄^(1-) In water; acetonitrile at 20℃; for 18h; Irradiation; Green chemistry;
50%	With oxygen; 2,6-dimethylpyridine perchlorate In acetonitrile at 20℃; for 12h; Electrolysis;
40 %Chromat.	With tert.-butylhydroperoxide; C₆₆H₆₀Fe₂N₁₂O₄⁽⁴⁺⁾4BF₄^(1-)4H₂O In water; acetonitrile at 20℃; for 6h;	Catalytic tests A Schlenk tube was charged with the substrate (0.3 mmol) andthe catalyst (4.5 lmol) dissolved in ACN (0.5 mL). The oxidanttBuOOH (0.32 mL, 70 wt% in H2O, 2.4 mmol) was slowly addedwithin 30 min, and then solution was shaken for 6 h at room temperature.0.2 mL of the solution were dissolved in 1 mL of DCM andthe yield was determined by GC
	With ketoreductase-P₃-B₀₃; oxygen; NADPH; 9‑mesityl-10-methylacridinium perchlorate In water; acetonitrile at 23℃; for 24h; Irradiation; Enzymatic reaction;

Yield	Reaction Conditions	Operation in experiment
75%	With potassium hydroxide In ethanol at 20℃;	Chalcones 3a-3d (general procedure) General procedure: Benzaldehyde1a-1c (12 mmol) and acetophenone 2a or 2b(12 mmol) were dissolved in ethanol (10 mL), and40% potassium hydroxide solution was added dropwisewhile stirring at room temperature over a period of30 min. The mixture was then stirred at room temperatureuntil the reaction was complete (4-6 h, TLCmonitoring), the solvent was removed on a rotaryevaporator under reduced pressure, the residue waspoured into ice water, and the product was filtered offand recrystallized from methanol.
60%	Stage #1: 2-Methoxyacetophenone With potassium hydroxide In ethanol at 0℃; for 0.25h; Stage #2: benzaldehyde In ethanol at 25℃; for 4h;
46%	With potassium hydroxide; water monomer In methanol for 24h;

	With ethanol; sodium hydroxide at 25℃; for 3h; Combinatorial reaction / High throughput screening (HTS);
	With sodium hydroxide In ethanol at 25℃;
	With potassium hydroxide In ethanol at 20℃; for 48h;
	With sodium hydroxide In ethanol; water monomer at 20℃; for 5h;	General procedure for the preparation of α,β-unsaturated ketones General procedure: In a 250 mL flask, corresponding aldehyde (20 mmol),corresponding ketone (20 mmol) and ethanol (50 mL) were placed, and thesolution was stirred at room temperature. To the solution, NaOH aqueoussolution (1.5 M, 20 mL) was slowly added. The mixture was stirred for about 5 h.Crude-unsaturated ketone was obtained after filtration. Then, the crude productwas recrystallized from ethanolIn a 250 mL flask, corresponding aldehyde (20 mmol),corresponding ketone (20 mmol) and ethanol (50 mL) were placed, and thesolution was stirred at room temperature. To the solution, NaOH aqueoussolution (1.5 M, 20 mL) was slowly added. The mixture was stirred for about 5 h.Crude-unsaturated ketone was obtained after filtration. Then, the crude productwas recrystallized from ethanol.
	In ethanol; water monomer at 20℃;	General procedure for the synthesis of chalcone dienophiles 2a-d General procedure: A mixture of the corresponding acetophenone (1 equiv.) and benzaldehyde (1 equiv.) in EtOH (5 mL/1 mmol of acetophenone) was stirred at rt for 30 min. Then a solution of 50% w/w aqueous KOH (1 mL/1 mmol) was added. The reaction mixture was stirred at rt until all benzaldehyde was consumed by monitoring on TLC. Afterwards the mixture was poured into ice-water acidified with 3N HCl. In cases in which the chalcones precipitated, they were filtered, purified using column chromatography and crystallised from ethanol (yields: 85-90%).
	With sodium hydroxide In methanol at 20℃;
	With sodium hydroxide In ethanol at 0 - 20℃; for 12h;	3.2.1. General method for the synthesis of substituted 1,3-diaryl-2-propene-1-one (1-19) General procedure: 1,3-Diaryl-2-propene-1-one derivatives (1{19) were prepared according to the procedure described elsewhere inthe literature. 53 61 Equimolar quantities of substituted acetophenone (10 mmol) and substituted benzaldehyde(10 mmol) in ethanol (10 mL) were stirred at 0{5C for 30 min. Sodium hydroxide (40%, 4 mL) was thenadded dropwise. Stirring was continued for 12 h at room temperature and the reactions were stopped after TLCmonitoring. The reaction mixture was poured into crushed ice and acidied if necessary with 6 N HCl. Theprecipitated solid mass was ltered, washed with water, and crystallized from ethanol to give white, orange, oryellow products puried by column chromatography if necessary.
	With sodium hydroxide at 20℃; for 1.5h; Sealed tube; Cooling with ice;
	Stage #1: 2-Methoxyacetophenone; benzaldehyde In ethanol at 20℃; for 0.5h; Stage #2: In ethanol; water monomer at 20℃; Alkaline conditions;
	Stage #1: 2-Methoxyacetophenone With sodium hydroxide In methanol; water monomer at 0 - 20℃; for 1h; Stage #2: benzaldehyde In methanol; water monomer at 20℃;
	With sodium hydroxide In ethanol at 20℃; for 0.0833333h;

Yield	Reaction Conditions	Operation in experiment
88%	With sodium hydroxide In ethanol; water at 60℃; for 2h;
83%	With sodium hydroxide In ethanol; water at 60℃; for 2h;	Typical experimental procedure: General procedure: To a solution of acetophenone (40 mmol) and salicylaldehyde (40 mmol) in EtOH (50 mL) was added 40% NaOH (10 mL) aqueous solution dropwise and the reaction was refluxed at 60 °C for 2 h. The solution/suspension was poured onto cold H2O and the mixture neutralized with 2 M HCl until the solution was acidic. The resulting yellow precipitate was collected, washed with H2O and recrystallized from EtOH to yield a yellow solid (4.2 g, 85% yield of 3).
60%	With sodium hydroxide In ethanol at 20℃;

22 g	With sodium hydroxide In methanol; water for 96h;
	With potassium hydroxide In methanol at 20℃;
	With potassium hydroxide In ethanol at 20℃; for 24h;
	With sodium hydroxide In methanol; water at 0 - 20℃;
	With sodium hydroxide In methanol Reflux;
	With potassium hydroxide In ethanol; water at 0 - 25℃; for 48h;

[ CAS No. 579-74-8 ] {[proInfo.proName]}

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[ 579-74-8 ]

Yield	Reaction Conditions	Operation in experiment
72.4%	Stage #1: 2-Methoxyacetophenone; Glyoxilic acid at 105 - 108℃; for 3h; Stage #2: With hydrazine hydrate In water for 2h; Reflux;	General procedure for the synthesis of 6-substitutedpyridazin-3(2H)-one derivatives (1a, 1b, 1c) General procedure: The mixture of glyoxylic acid monohydrate (5.52g, 0.06mol) and appropriate acetophenone derivative (27.04g, 0.18mol) was heated at 105-108°C for 3h. At the end of the time, the reaction medium was cooled to room temperature and to added 24mL of water and 4.8mL of conc. ammonium hydroxide. Then, the mixture was extracted with dichloromethane (2×50mL), and 2.9mL (0.06mol) hydrazine hydrate was added onto the separated aqueous phase. The mixture was heated under reflux for 2h. At the end of the period, the reaction medium was cooled, the precipitate was filtered and crystallized from the appropriate solvent.
	With ammonium hydroxide; hydrazine hydrate 1) heating, 2) water, reflux; Yield given. Multistep reaction;
	With hydrazine hydrate

Yield	Reaction Conditions	Operation in experiment
88%		Sodium hydride (480mg, 20.0 mmmol) was taken in dry THF (18mL) in a 100mL round bottom flask under N2 and cooled it down to 0C. To it was added a solution of ethyl 3-(2-methoxyphenyl)-3-oxopropanoate (1.0g, 6.7mmol) in THF (2mL). The reaction mixture was stirred at rt for 30min followed by the addition of diethyl carbonate (3.2mL, 26.8mmol). The reaction mixture was then stirred at rt for 14h. Ice-cooled water was added dropwise to quench the reaction. It was extracted with EtOAc (3×75mL). The combined organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The crude was further purified by flash chromatography on silica gel (60-120 mesh) using 10% hexane-EtOAc as eluent to afford 2c as a colourless liquid (1.3g, 88%). LC-MS (ESI) m/z 223.32 [M+H+]; 97% (purity).
86%	With sodium hydride; In toluene; mineral oil;	General procedure: The substrate b-ketoesters 10 a-n were either purchased or synthesized following published procedures. Some benzoylacetates were commercially available. Ethyl 3-oxo-3-phenyl propanoate (10a) was purchased. The reaction of benzoylacetates 10 b-n was prepared as described in previous reports. 25-27 A solution of a substituted acetophenone 8 a-n (0.05 mol) dissolved in toluene (50 mL) was added dropwise to a solution containing diethyl carbonate (9) (0.10 mol) and sodium hydride (0.15 mol 60% dispersion in mineral oil). The mixture was stirred at room temperature, and then refluxed for 30 min. The mixture was poured into ice water,acidified with glacial acetic acid, and extracted with EtOAc (3x100 mL). The EtOAc extract was then dried over anhydrous MgSO4. After removal of the solvent in vacuo, the crude products were purified by silica gel column chromatography eluting with dichloromethane to afford benzoylacetates 10 b-n. All synthetic compounds were in agreement with 1H NMR, 13C NMR, IR and mass spectroscopic data.
	In tetrahydrofuran;	A. Ethyl O-methoxybenzoylacetate To a suspension of 7.7 g. (0.32 mole of oil-free sodium hydride in 200 ml. of cold (0 C.) tetrahydrofuran containing 72.6 g. (0.61 mole) of diethyl carbonate was added dropwise under a nitrogen atmosphere 44 g. (0.29 mole) of O-methoxyacetophenone in 200 ml. of tetrahydrofuran. When the addition was complete, the reaction was allowed to stir at 0 C. for 2 hours. The reaction was cooled, poured into a 10% hydrochloric acid solution and extracted with ether. The combined extracts were washed with brine and water, dried over magnesium sulfate and concentrated in vacuo, 36 g.

Yield	Reaction Conditions	Operation in experiment
99%	With (mer-[(S,S)-1,5-dimethyl-2,4-bis(4-phenyl-1,3-oxazolin-2-yl)benzene^(1-)]Ru(CO)Cl)2(ZnCl₂); hydrogen; sodium methylate; (-)-(S)-1-Anthracen-9-ylethanol In isopropyl alcohol at 40℃; for 42h; Inert atmosphere; Autoclave; optical yield given as %ee; enantioselective reaction;
97%	With dichloro(benzene)ruthenium(II) dimer; potassium <i>tert</i>-butylate; hydrogen; (R)-N,N'-((1R,2R)-cyclohexane-1,2-diyl)bis(2-((R)-tert-butyl(methyl)phosphino)benzamide) In isopropyl alcohol at 20℃; for 8h; Schlenk technique; Overall yield = 97 percent;	3.General procedu re for asymmetric hydrogenation General procedure: The [Ru(C6H6)Cl2]2(1.5 mg, 3 10-3 mmol, 1.0 mol%), (Rc,Rc,Rp,Rp)-L1 (3.5 mg, 6.610-3 mmol, 1.1 mol%) and isopropanol (1.5 mL) were added to a schlenk tube under an atmosphere of argon. After stirring at room temperature for 1.0 h, the orange-yellow solution was transferred to a stainless-steel reactor via syringe in a glovebox. Next, tBuOK (6.7 mg, 0.060 mmol, 10.0 mol%), and acetophenone (72.0 mg, 0.60 mmol, 1.0 eq) were added into the solution, and the resulting mixture was stirred under a hydrogen pressure (3.0 MPa) at room temperature for 8.0 h. The pure products were obtained by flash column chromatographic purification using petroleum and ethyl acetate as the eluent. The pure products were obtained by flash column chromatography using petroleum and ethyl acetate as the eluent. The enantiomeric excesses were measured by chiral HPLC using the Daicel chiral OD-H (4.6 mm × 250 mm, 5 μm) and REGIS (R,R)-WHELK-O1 (2.1 mm × 150 mm, 5 μm) columns and 2-propanol/hexane as the eluent. The absolute configurations of the corresponding products were determined by comparison of the results with literature reports.
1: 95.5% 2: 4.5%	With 4 A molecular sieve; (1R,2R,4S,6S)-2-(2-methoxyphenyl)-bicyclo[2.2.2]octane-2,6-diol; benzo[1,3,2]dioxaborole In tetrahydrofuran at -20℃; for 24h; Title compound not separated from byproducts.;

Yield	Reaction Conditions	Operation in experiment
95%	Stage #1: ethyl trifluoroacetate, With sodium hydride In 1,2-dimethoxyethane; mineral oil Stage #2: 2-Methoxyacetophenone In 1,2-dimethoxyethane; mineral oil at 160℃; for 0.25h; Microwave irradiation; Stage #3: With hydrogenchloride In 1,2-dimethoxyethane; water; mineral oil	5.1 Step 1. Synthesis of 4,4,4-trifluoro-1-(2-methoxyphenyl)butane-1,3-dione (C9) To a suspension of sodium hydride (60% in mineral oil, 202 mg, 8.0 mmol) in 1,2-dimethoxyethane (4 mL) was added drop-wise ethyl trifluoroacetate (954 μL, 8.0 mmol) followed by 1-(2-methoxyphenyl)ethanone (552 μL, 4.0 mmol) and the reaction was heated to 160° C. in a microwave for 15 minutes. Aqueous hydrochloric acid (1 N, 20 mL) was added and the mixture was extracted with tert-butyl methyl ether (3*10 mL). The combined organic layers were dried over sodium sulfate and concentrated in vacuo. Purification via silica gel chromatography (Gradient: 0% to 10% tert-butyl methyl ether in heptanes) afforded the title compound as a red solid. Yield: 933 mg, 3.79 mmol, 95%. GCMS m/z 246 (M+). 1H NMR (400 MHz, CDCl3) δ 3.96 (s, 3H), 6.99 (s, 1H), 7.02 (br d, J=8.5 Hz, 1H), 7.08 (ddd, J=8, 7, 1.0 Hz, 1H), 7.55 (ddd, J=8.4, 7.4, 1.8 Hz, 1H), 7.99 (dd, J=7.9, 1.9 Hz, 1H).
85%	Stage #1: 2-Methoxyacetophenone With sodium hydride In tetrahydrofuran at -5 - 0℃; for 0.5h; Inert atmosphere; Stage #2: ethyl trifluoroacetate, In tetrahydrofuran at 20℃; for 6h;	12.1 (1) in 100 ml round bottom flask is added 2 - methoxy hypnone (compound 3k) 14.9mmol, dry THF 30 ml, lowering the temperature to - 5 - 0 °C, under the protection of nitrogen addition of NaH 0.715g (29.8mmol), in this particularity stirring 30min, adding trifluoro ethyl acetate 3.175g (22.4mmol), stirring at the room temperature reaction 6h, evaporating the solvent under reduced pressure, adding ice water dilution solution, for 1 mol/L HCl solution of adjusting PH value to 6, extracted with ethyl acetate three times (10 ml × 3), recovery, combined with the organic layer, the organic layer using 5 ml water washing, and the anhydrous magnesium sulfate drying, desolvation, the concentration of the product after the drying, to obtain compound 4k (4, 4, 4 - trifluoro -1 - (2 - methoxyphenyl) - 1, 3 - Butanedione), yield 85%;
	With sodium methylate In methanol for 24h; Heating;

Yield	Reaction Conditions	Operation in experiment
85%	With sodium hydroxide In methanol; water at 20℃;	2.2. General Procedure for the Preparation of Chalcones General procedure: Sodium hydroxide solution (50 % w/v, 5.3 ml, 66.7mmol) was added to a stirred solution of the acetophenone(6.67 mmol) and aldehyde (6.67 mmol) in methanol (30 ml). The resulting mixture was stirred at room temperature and sequentially monitored by TLC until the reaction was complete. The reaction was quenched with water (30 ml) and extracted with ethyl acetate (3x30 ml). The combined organic extracts were washed with brine (50 ml), dried with anhydrous magnesium sulfate and the solvent removed invacuo. The crude product was recrystalised from ethanol
	With sodium hydroxide In ethanol for 1.5h; Ambient temperature;

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide In ethanol at 80℃;
	With potassium hydroxide In ethanol; water Heating;

Yield	Reaction Conditions	Operation in experiment
	With 3 A molecular sieve; oxygen; caesium carbonate In chloroform at 23℃; for 164h;
	With dichloro bis(acetonitrile) palladium(II); oxygen; (-)-sparteine In 1,2-dichloro-ethane at 70℃; Title compound not separated from byproducts.;
	With oxygen; caesium carbonate; (-)-sparteine In chloroform at 23℃; for 164h; Molecular sieve; optical yield given as %ee;

	With Arthrobacter atrocyaneus In N,N-dimethyl-formamide at 32℃; for 48h; Microbiological reaction;
56 % ee	Stage #1: 1-(2-methoxyphenyl)ethanol With C₂₈H₃₆ClMnN₂O₂; potassium acetate In dichloromethane; water for 0.0833333h; Stage #2: With N-Bromosuccinimide In dichloromethane; water at 20℃; for 4h; enantioselective reaction;

Yield	Reaction Conditions	Operation in experiment
94.5%	With sodium tetrahydroborate at 50℃; for 8.5h; Inert atmosphere;	17 Example 17 In a 250 ml three-necked flask, sodium borohydride (12.5 mmol) and 2-methoxyacetophenone (1.25 mol) were added. Under the protection, slowly warm up to 50 °C, stirring while dropping cyanotrimethylsilane (1.5 mol) through the dropping funnel for 0.5 hour, keeping the reaction temperature, continuing to stir the reaction for 8 hours, standing, cooling to room temperature, vacuum distillation The corresponding fractions were collected and analyzed by GC. The yield of the addition product, 2-(2-methoxyphenyl)-2-trimethylsilyloxypropionitrile, was 94.5 %.
90%	at 20℃; for 0.166667h;
59%	Stage #1: 2-Methoxyacetophenone With (R_a)-4-hydroxy-2,6-diphenyldinaphtho[1,3,2]dioxaphosphepine 4-oxide; n-butyllithium In hexane; toluene at -78℃; for 0.5h; Inert atmosphere; Stage #2: trimethylsilyl cyanide In hexane; toluene at 0℃; for 24h; Inert atmosphere;

0.25 g	With [CH₃(Ph)Si(9H-fluoren-9-yl)2]LaCl In chloroform at 25℃; for 15h;
	Stage #1: trimethylsilyl cyanide With N,N-dimethylaniline N-oxide In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 2-Methoxyacetophenone With 2,2,2-trifluoroethanol; (R,R)-N,N'-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexanediamino methylaluminium In tetrahydrofuran at -20℃; for 14h; Inert atmosphere; enantioselective reaction;
	With C₄₃H₆₁N₃Th In benzene-d6 at 80℃; for 24h; Sealed tube;