[ CAS No. 6285-05-8 ] {[proInfo.proName]}

Name: 6285-05-8|4'-Chloropropiophenone|97%
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Product Details of [ 6285-05-8 ]

CAS No. :	6285-05-8	MDL No. :	MFCD00000626
Formula :	C₉H₉ClO	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	ADCYRBXQAJXJTD-UHFFFAOYSA-N
M.W :	168.62	Pubchem ID :	22697
Synonyms :

Safety of [ 6285-05-8 ]

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

Application In Synthesis of [ 6285-05-8 ]

* 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 [ 6285-05-8 ]
Downstream synthetic route of [ 6285-05-8 ]

[ 6285-05-8 ] Synthesis Path-Upstream 1~4

1
[ 6285-05-8 ]
[ 17356-08-0 ]
[ 82632-77-7 ]

Yield	Reaction Conditions	Operation in experiment
84%	for 8 h; Heating	General procedure: Thiourea (0.04 mol) and iodine (0.02 mol)were triturated and mixed with appropriate 4-substituted propiophenone (0.02 mol), the mixture was heated on a water bathat 70 °C with occasional stirring for 8 h. The solid product was triturated and mixed with ethyl ether to remove unreacted 4-substituted phenyl propiophenone, washed with aqueous thiosulphate (5 percent) to remove excess iodine and finally with water. The crude product was dissolved in hot water, filtered toremove impurity and 2-amino-4-(4'-substituted phenyl)-5-methyl-1,3-thiazole (Scheme-II) was precipitated by additionof ammonia solution. The product was recrystallized from ethanol to give crystal of desired product [9].

Reference： [1] Asian Journal of Chemistry, 2017, vol. 29, # 12, p. 2794 - 2798
[2] Journal of the Indian Chemical Society, 1960, vol. 37, p. 427 - 428
[3] Bioorganic and Medicinal Chemistry Letters, 2001, vol. 11, # 3, p. 313 - 317

2
[ 6285-05-8 ]
[ 82632-77-7 ]

Reference： [1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1999, # 17, p. 2425 - 2428
[2] European Journal of Medicinal Chemistry, 2012, vol. 52, p. 70 - 81
[3] Journal of the Chinese Chemical Society, 2017, vol. 64, # 12, p. 1408 - 1416
[4] European Journal of Medicinal Chemistry, 2018, vol. 144, p. 179 - 200

3
[ 6285-05-8 ]
[ 31970-26-0 ]

Reference： [1] Organometallics, 2011, vol. 30, # 15, p. 4067 - 4073

4
[ 6285-05-8 ]
[ 1448902-18-8 ]

Reference： [1] Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 18, p. 5907 - 5922

[ 6285-05-8 ] Synthesis Path-Downstream 1~45

1
[ 6285-05-8 ]
[ 50-00-0 ]
[ 6091-44-7 ]
[ 3644-60-8 ]

Reference： [1]Journal of the Chemical Society,1958,p. 312,315

2
[ 6285-05-8 ]
[ 540-69-2 ]
[ 74788-46-8 ]

Reference： [1]Scientia Pharmaceutica,1953,vol. 21,p. 308,310

3
[ 6285-05-8 ]
[ 18713-58-1 ]

Reference： [1]Bulletin de la Societe Chimique de France,1959,p. 1686

4
[ 6285-05-8 ]
[ 877-37-2 ]

Yield	Reaction Conditions	Operation in experiment
98%	With bromine;hydrogen bromide; In methanol; at 20℃; for 110h;Inert atmosphere;	Step 1. 2-Bromo-<strong>[6285-05-8]4'-chloropropiophenone</strong> (1Of). 4'-Chloropropiophenone 9f(4.58 g, 0.027 mol) was dissolved in 30 mL of methanol at room temperature in a 250 mL flask equipped with a magnetic stir bar. Bromine (1.67 mL, 32.6 mmol) was added over a period of 10 min. Seven drops of 48% hydrobromic acid were added, and the reaction mixture was stirred under N2. After HO h, the solution was transferred to a separatory funnel, saturated sodium bicarbonate solution was added, and the aqueous layer was extracted with methylene chloride. The organic layer was dried (Na2SO4) and filtered. The solvent was removed under reduced pressure to give 6.60 g (98%) of 1Of as an orange oil. 1H NMR (CDCl3) delta 8.00-7.94 (d, 2H), 7.50-7.44 (d, 2H), 5.27-5.19 (q, IH), 1.92-1.89 (d, 3H).
97%	With bromine; In acetic acid; at 0 - 20℃; for 2h;	2-bromo-4'-chlorofuropiophenone (compound Ilid) 50ml of acetic acid was added dropwiselyly to 16.86g of 4'- chlorofuropiophenone and was cooled at 0C before 5. 14moi (0.1 mol) of brome was slowly added dropwiselyly. The resultant mixture was stirred at a room temperature for two hours, to which 270ml of water was added, filtered, washed with a sufficient amount of water and then dried to obtain a white solid product of 24.13g of 2-bromo-4'-chlorofuropiophenone (IIId).
87%	With hydrogen bromide; bromine; acetic acid; for 1h;	[0118] 2-Bromo-l-(4-chlorophenyl)propan-l-one: l-(4-chlorophenyl)Propan-l-one (0.2264 g, 1.34 mmol, 1.00 equiv) was dissolved in acetic acid (4mL) and 1 drop of HBr (48%) was added. Bromine (0.225 g, 0.08 mL, 1.05 equiv) was added dropwise. After 1 h the reaction was carefully quenched with aHC03 (sat. aq) and extracted with ethyl acetate (3x). The combined organic layers were washed with brine, dried over Na2S04 and concentrated under reduced pressure. The crude residue was purified via silica gel flash chromatography (25% EtO Ac/Hex) to give 0.2897 g (87%) of the title compound as an orange oil. The spectral data was identical to that reported in the literatureVI: XH NMR (500 MHz, CDC13): delta 7.99-7.94 (m, 2H), 7.49-7.40 (m, 2H), 5.25 (q, J= 6.6 Hz, 1H), 1.91 (s, 3H) ppm.

85%	With bromine; In chloroform; at 0 - 20℃; for 2h;	General procedure: To a solution of the appropriate ketone (A, 1 equiv) in chloroform, bromine (1 equiv) in chloroform was added dropwise at 0 C. The mixture was stirred at room temperature for 2 h and was washed with H2O (3 50 ml) and saturated Na2S2O3 solution (2 x 50 ml). The organic phase was dried over Na2SO4, filtered andthe solvent was removed in vacuum. The crude alpha-bromoketone (B) was recrystallized from petrolether.48
84%	With hydrogen bromide; potassium iodide; sodium nitrite; In water; acetonitrile; at 0 - 20℃; for 10h;	General procedure: In a RBF cooled in ice bath at 0 C, HBr(12 mmol, in 2 ml of water) was taken. To this a solution of NaNO2(5 mmol, in 5ml of water) was added drop wise. The reaction was stirred for 15min maintaining the temperature at 0 C and KI (5 mol %) was added. After 10 min ketone(10 mmol) was added at once. After 15 min reaction temperature was brought to room temperature slowly. Reaction was monitored by TLC (ethyl acetate: pet ether, 1:9). After completion of reaction 50 ml of CHCl3 was added and organic layer separated. Aqueous layer was extracted with 25 ml of CHCl3 and combined organic layer was washed with 10% NaHSO3 solution (2 x 20 ml) and 10% NaHCO3 solution (2 x 20 ml).The organic layer was dried over sodium sulphate and concentrated under reduced pressure. Pure product was obtained after column chromatography (silica gel, 60-120, eluentethyl acetate: pet ether).
73%	With pyridinium hydrobromide perbromide; In dichloromethane; at 20℃; for 3h;	In a 100 mL round bottom flask, PyBr3.HBr (8.3 g, 26.02 mmol, 1.10 equiv) was added to a solution of 1-(4-chlorophenyl) propan-1-one (5.0 g, 23.47 mmol, 1.00 equiv) in dichloromethane (40 mL) at room temperature. The resulting solution was stirred for 3 h at room temperature. The reaction was then quenched by the addition of water. The resulting mixture was extracted with dichloromethane (100 mL*3) and the organic layers were combined, washed with brine and dried over anhydrous sodium sulfate. The organic solvent was removed under reduced pressure and the residue was applied onto a silica gel column eluting with ethyl acetate/petroleum ether (v:v=1:5). This resulted in 5.0 g (73%) of 2-bromo-1-(4-chlorophenyl)propan-1-one as a yellow solid.
	With bromine; In diethyl ether;	(1) Bromine (5.2 ml) was added dropwise to a solution of 4-chloropropiophenone (16.8 g) in ethyl ether (170 ml) under stirring. The solvent was distilled off to give 4-chloro-alpha-bromopropiophenone.
	With bromine; In aluminium chloride; chloroform;	EXAMPLE 3 2-Bromo-<strong>[6285-05-8]4'-chloropropiophenone</strong> A solution of 15.9 g (0.1 mol) of bromine in 20 ml of chloroform is added dropwise to a solution of 16.8 g (0.1 mol) of <strong>[6285-05-8]4'-chloropropiophenone</strong> in 100 ml of chloroform, in the presence of a small amount of aluminium chloride, and the mixture is stirred overnight. After filtration and evaporation of the filtrate, the crystalline residue is washed with petroleum ether. When dry, it melts at 75 C.
	With bromine;AlCl3; In chloroform;	1. 2-Bromo-<strong>[6285-05-8]4'-chloropropiophenone</strong>. A solution of 15.9 g (0.1 mol) of bromine in 20 ml of CHCl3 is slowly added dropwise to a solution of 16.8 g (0.1 mol) of 4-chloropropiophenone in 100 ml of CHCl3, in the presence of AlCl3. The mixture is stirred overnight. After filtration through a glass plug and after evaporation of the solvent, the crystalline residue is washed with petroleum ether. The compound melts at 75 C.
	With hydrogen bromide; bromine; acetic acid;	Reference Production Example 1 To a mixture of 10.12 g of <strong>[6285-05-8]4'-chloropropiophenone</strong>, 0.1 ml of hydrobromic acid (48% aqueous solution) and 60 ml of acetic acid was added 3.1 ml of bromine at 0C under a nitrogen atmosphere, and stirred at room temperature for 1 hour. Thereafter, the reaction mixture was concentrated under reduced pressure, to obtain 14.34 g of 2-bromo-<strong>[6285-05-8]4'-chloropropiophenone</strong>. 1H-NMR(CDCl3,TMS)delta(ppm):1.90(3H,d,J=6.5Hz),5.22(1H,q, J=6.5Hz),7.46(2H,d,J=8.7Hz),7.97(2H,d,J=8.7Hz)
	With bromine; acetic acid;hydrogen bromide; In water; at 0 - 20℃; for 1h;	Reference Production Example 1 [Show Image] A mixture of 10.12 g of <strong>[6285-05-8]4'-chloropropiophenone</strong>, 0.1 ml of hydrobromic acid (48% aqueous solution) and 60 ml of acetic acid was cooled to 0C under a nitrogen atmosphere. Into the mixture, 3.1 ml of bromine was added dropwise, then, the mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure, to obtain 14.34 g of 2-bromo-<strong>[6285-05-8]4'-chloropropiophenone</strong>. 1H-NMR (CDCl3, TMS) delta (ppm) : 1.90 (2 H, d, J=6. 5 Hz), 5.22 (1 H, q, J=6.5 Hz), 7.46 (2 H, d, J=8.7 Hz), 7.97 (2 H, d, J=8.7 Hz)
	With bromine; In chloroform; at 10℃;Irradiation with a photoflood lamp; Ice-bath;	4-Chloropropiophenone (122. [5G)] was dissolved in chloroform [(500ML).] Bromine (2ml) was added and the solution irradiated with a photoflood lamp until reaction began. This was cooled to about [10C] in an ice bath and the remainder of the bromine [(35. 5ML)] was added dropwise, reacting almost immediately. After the addition, the ice bath was removed and the reaction was left to stand overnight. The reaction mixture was washed with water (2 x [200ML),] saturated sodium hydrogen carbonate and water. The organic layer was then dried [(MGS04),] and the solvent removed in vacuo to give the crude product. This was recrystallized from cyclohexane to give the product as white crystals.
	With copper(I) bromide; In chloroform; ethyl acetate; for 16h;Heating / reflux;	A chloroform solution (75 mL) of <strong>[6285-05-8]4'-chloropropiophenone</strong> (2.41 g) was added to an ethyl acetate suspension (150 mL) of copper bromide (9.48 g), and heated and stirred for 16 hours. The reaction solution was Celite filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain 2-bromo-1-(4-chlorophenyl)propan-1-one (1.52 g) as a pale yellow oil. 1H-NMR (300MHz, CDCl3); delta 1.90 (3H, d, J=6.6Hz), 5.22 (1H, q, J=6.6Hz), 7.47 (2H, d, J=8.7Hz), 7.97 (2H, d, J=8.7Hz)
	With copper(ll) bromide; In ethanol; chloroform; ethyl acetate; at 65℃; for 0.5h;	General procedure: A solution of 1-(2-chlorophenyl)ethanone (2b) (0.84 mL, 6.5 mmol) in anhydrous ethyl acetate (25 mL) and chloroform (25 mL) was treated with copper (II) bromide (4.33 g, 19.5 mmol) and ethanol (6 mL), stirred at 65 C for 0.5 h. The reaction was extracted with chloroform (40 mL). The organic extracts were washed with water (3 × 30 mL), dried (NaSO4), filtered, and concentrated in vacuo to give a colourless oil.
	With N-Bromosuccinimide; trimethylsilyl trifluoromethanesulfonate; In acetonitrile; at 40℃;	General procedure: Ketone (1 eq) and N-bromosuccinimide (NBS) (2 eq) were solved in acetonitrile and trimethylsilyl trifluoromethanesulfonate (TMS-OTf) (1 eq) was added. The reactions were stirred at T=40C until completeness, diluted with diethyl ether (2ml), washed with H2O (3×2ml), dried over Na2SO4 and concentrated under reduced pressure. This procedure provided bromoketones intermediates in 70-90% overall yield, with purities generally>90% as determined by HPLC-MS. The compounds were used without further purification.
	With hydrogen bromide; bromine; acetic acid; at 0 - 20℃; for 1h;	Reference Production Example 1 A mixture of 10.12 g of <strong>[6285-05-8]4'-chloropropiophenone</strong>, 0.1 ml of hydrobromic acid (48% aqueous solution) and 60 ml of acetic acid was cooled to 0C under a nitrogen atmosphere. 3.1 ml of bromine was added dropwise into the mixture, then, the mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was concentrated under reduced pressure to obtain 14.34 g of 2-bromo-<strong>[6285-05-8]4'-chloropropiophenone</strong>. 1H-NMR (CDCl3, TMS) delta (ppm): 1.90 (3 H, d, J=6.5 Hz), 5.22 (1 H, q, J=6.5 Hz), 7.46 (2 H, d, J=8.7 Hz), 7.97 (2 H, d, J=8.7 Hz)

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[4]European Journal of Organic Chemistry,2016,vol. 2016,p. 1982 - 1993
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[9]Journal of Organic Chemistry,2018,vol. 83,p. 15524 - 15532
[10]Patent: WO2014/47257,2014,A2 .Location in patent: Paragraph 0118
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[12]Tetrahedron Letters,2016,vol. 57,p. 4918 - 4921
[13]Synthetic Communications,2007,vol. 37,p. 87 - 90
[14]Patent: US2018/72711,2018,A1 .Location in patent: Paragraph 0453; 0454
[15]Journal of the Chemical Society. Perkin transactions I,1999,p. 2425 - 2428
[16]Journal of Organic Chemistry,1947,vol. 12,p. 617,680
[17]Zhurnal Obshchei Khimii,1949,vol. 19,p. 1324,1339
Chem.Abstr.,1950,p. 4442
[18]Journal of the American Chemical Society,1964,vol. 86,p. 684 - 687
[19]Journal fur praktische Chemie (Leipzig 1954),1963,vol. 22,p. 202 - 213
[20]Journal of Medicinal Chemistry,1987,vol. 30,p. 1497 - 1502
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[27]Patent: US4430334,1984,A
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[48]Tetrahedron,2019,vol. 75

5
[ 6285-05-8 ]
[ 56472-72-1 ]

Yield	Reaction Conditions	Operation in experiment
96.9%	With n-Butyl nitrite; In Petroleum ether; for 5h;	Operation: To 3000 liters of reactor into the 350Kg of p-chlorophenylacetone, 700Kg petroleum ether, cooled to 10 , then add 235Kg n-butyl nitrite, stirring 5h, and then cooled to 0 , holding 0.5h, , Filter, petroleum ether wash, bake Dry to obtain a solid ketoxime
81%	With chloro-trimethyl-silane; tert.-butylnitrite; In tetrahydrofuran; dichloromethane; at -20 - 20℃;Inert atmosphere;	In a flame-dried flask under argon, a solution of 4-chloropropiophenone (15 mmol) in a mixture of dry THF (3 mL) and dry DCM (3 mL) was cooled to - 20 C. Chlorotrimethylsilane (15 mmol) and tert-butyl nitrite (19.5 mmol) were added dropwise and the solution was stirred at - 20 C for 30 min and then at room temperature for 16 h. The solvent was evaporated under reduced pressure and the crude firstly purified by flash chromatography with cyclohexane/ethyl acetate (95:5) and then recrystallized in chloroform/cyclohexane (1:5) to afford compound oxime 6. White solid (m.p. 118.5-119 C), 81% yield. Chemical Formula: C9H8ClNO2. Molecular Weight: 197.62 g/mol. Rf = 0.37 (cyclohexane/ethyl acetate 9:1). 1H NMR (300 MHz, CDCl3) delta 8.89 (br s, 1H), 7.82 (dd, J1 = 8.7 Hz, J2 = 2.5 Hz, 2H), 7.38 (dd, J1 = 8.7 Hz, J2= 2.5 Hz, 2H), 2.15 (s, 3H) ppm. 13C NMR (75 MHz, CDCl3) delta 190.80, 157.08, 139.63, 134.74, 131.97, 128.71, 10.40 ppm. IR nu = 3292, 3242, 2917, 1664, 1586, 1090, 997, 900, 840, 751 cm-1; MS (ESI) m/z 195.9 [M-H]-.
	With hydrogenchloride; water; sodium nitrite; at -15℃; for 0.75h;	Experimental procedure: A CEM Discover microwave (MW) reactor was used. The reactions were followed by TLC. The reaction time was determined based on several trials in each case. Two stage synthesis: Each alpha-oximino ketone was prepared from the corresponding ketone.[27] and [28] (a) Neat: 1,2-Diaminobenzene (0.37 g, 3.4 mmol) and the oximino ketone (3.4 mmol) were mixed well by grinding. The mixture was taken in a sealed vial and subjected to MW irradiation. After the reaction was complete, the product was purified by passing through a short silica gel column (eluant, hexane/EtOAc = 9:1). (b) In PEG-400: A well ground mixture of 1,2-diaminobenzene (0.37 g, 3.4 mmol), oximino ketone (3.4 mmol) and PEG-400 was taken in a sealed vial and irradiated with MW. After the reaction was over, the product was obtained as mentioned in the previous case. (c) In AcOH: The same amounts of reactants as mentioned in the previous cases were ground with 2-3 drops of AcOH, and the mixture was subjected to the same procedure as mentioned earlier. The one-pot reaction: Sodium nitrite (0.617 g, 8.9 mmol) in 1 mL of water was taken in a 25 mL flask and cooled to -15 C. Ketone (7.5 mmol) in 1 mL of PEG-400 was added, followed by concd HCl (0.33 g) over 5 min. The mixture turned green. After the colour disappeared (about 45 min), 0.74 g (6.8 mmol) of 1,2-diaminobenzene was added. The mixture was transferred to a vial and subjected to MW irradiation (9 min). After the reaction was over, the product was added to 10 mL of water and worked up in the usual way using dichloromethane for extraction.

Reference： [1]Tetrahedron Letters,2003,vol. 44,p. 2753 - 2755
[2]Patent: CN106632131,2017,A .Location in patent: Paragraph 0041; 0043-0047; 0092
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[5]Patent: US2248035,1938,
[6]Russian Chemical Bulletin,2006,vol. 55,p. 1046 - 1051
[7]Tetrahedron Letters,2011,vol. 52,p. 544 - 547

6
[ 6285-05-8 ]
[ 70-69-9 ]

Yield	Reaction Conditions	Operation in experiment
93%	With C₄₆H₇₁Cl₃N₂Pd; ammonia; sodium t-butanolate In 1,4-dioxane at 80℃; for 2h; Inert atmosphere; Schlenk technique;
	With ammonium hydroxide; copper; copper(l) chloride at 200℃;

Reference： [1]Lombardi, Christopher; Day, Jonathan; Chandrasoma, Nalin; Mitchell, David; Rodriguez, Michael J.; Farmer, Jennifer L.; Organ, Michael G. [Organometallics, 2017, vol. 36, # 2, p. 251 - 254]
[2]Current Patent Assignee: EASTMAN KODAK CO - US2108824, 1936, A

7
[ 6285-05-8 ]
[ 91-56-5 ]
[ 43071-47-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide

Reference： [1]Buu-Hoi et al. [Journal of Organic Chemistry, 1953, vol. 18, p. 1209,1219]

8
[ 79-03-8 ]
[ 108-90-7 ]
[ 6285-05-8 ]

Yield	Reaction Conditions	Operation in experiment
96.5%	With aluminum (III) chloride; In dichloromethane; at 10 - 25℃; for 2h;	Chlorobenzene (0.1 mol), with stirring,Dichloromethane (100 mL) and anhydrous aluminum trichloride (0.12 mol)Add to the reaction vessel.Temperature 10 C,Propionyl chloride (0.11 mol) was added dropwise slowly.After the addition is completed, the temperature is raised to 25 C for 2 hr.TLC detects chlorobenzene without residue,Stop the reaction,Filtering,Collecting mother liquor,The mother liquor was successively treated with 5% citric acid (100 ml).Wash with saturated sodium bicarbonate (100 ml) and saturated brine.Dry over anhydrous sodium sulfate,Then concentrate the mother liquor,Obtained a white solid,Collecting solids,Melting point 35~37 C,The yield is 96.5 % based on chlorobenzene.The purity of HPLC was 98.9%.This solid is p-chloropropiophenone.

Reference： [1]Patent: CN108752229,2018,A .Location in patent: Paragraph 0018; 0022; 0026; 0030; 0034
[2]Chemistry Letters,2010,vol. 39,p. 929 - 931
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[4]Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences,1898,vol. 126,p. 1578
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[8]International Journal of Molecular Sciences,2019,vol. 20

9
[ 6285-05-8 ]
[ 13171-64-7 ]
[ 100791-78-4 ]

Reference： [1]Angewandte Chemie,1986,vol. 98,p. 273 - 274

10
[ 6285-05-8 ]
[ 608-68-4 ]
[ 100791-78-4 ]

Yield	Reaction Conditions	Operation in experiment
87%	With methanesulfonic acid; trimethyl orthoformate at 96℃; for 3h;
	With trimethyl orthoformate

Reference： [1]Castaldi, Graziano; Cavicchioli, Silvia; Giordano, Claudio; Uggeri, Fulvio [Journal of Organic Chemistry, 1987, vol. 52, # 14, p. 3018 - 3027]
[2]Castaldi, Graziano; Cavicchioli, Silvia; Giordano, Claudio; Uggeri, Fulvio [Angewandte Chemie, 1986, vol. 98, # 3, p. 273 - 274]

12
[ 6285-05-8 ]
[ 77-78-1 ]
[ 18713-58-1 ]
[ 79341-98-3 ]

Reference： [1]Chemische Berichte,1981,vol. 114,p. 2866 - 2883

13
[ 6285-05-8 ]
[ 74-88-4 ]
[ 18713-58-1 ]
[ 79341-98-3 ]

Reference： [1]Chemische Berichte,1981,vol. 114,p. 2866 - 2883

14
[ 6285-05-8 ]
[ 74788-46-8 ]

Reference： [1]Chirality,2018,vol. 30,p. 900 - 906
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[3]Bioorganic and Medicinal Chemistry Letters,2005,vol. 15,p. 497 - 500
[4]Patent: EP2848618,2015,A1
[5]ChemSusChem,2020,vol. 13,p. 3110 - 3114

15
[ 6285-05-8 ]
[ 95-92-1 ]
[ 169544-41-6 ]

Yield	Reaction Conditions	Operation in experiment
100%	With sodium; In ethanol; at 20℃; for 18h;	Sodium metal (0.82 g, 35.58 mmol) was added in small portion to dry ethanol (30 mL) and stirred until all the sodium had reacted. Diethyl oxalate (10) (3.62 mL, 26.69 mmol) was added, followed by dropwise addition of a solution of 4-chloropropiophenone (9) (3.00 g, 17.79 mmol) in dry ethanol (40 mL). The mixture was stirred at room temperature for 18 h and then it was slowly poured into ice and 1 N HCl was added. The resulting mixture was extracted with Et2O, dried (Na2SO4), and concentrated to afford the analytically pure product in quantitative yield as a yellowish oil: Rf = 0.23 (petroleum ether/EtOAc, 9:1); bp: 68-70 C [55-65 C/700 mmHg] [46], IR: nu = 1680, 1730, 3440; 1H NMR (CDCl3, 400 MHz) delta = 1.30 (t, 3H, J = 7.1 Hz), 1.45 (d, 3H, J = 7.1 Hz), 4.28 (q, 2H, J = 7.2 Hz), 5.00 (q, 1H, J = 7.1 Hz), 7.50 (d, 2H, J = 8.8 Hz), 7.93 (d, 2H, J = 8.8 Hz). Anal. C13H13ClO4 (C, H, N).
82%	With lithium tert-butoxide; In tetrahydrofuran; at 0 - 20℃; for 4h;Inert atmosphere;	General procedure: An oven-dried vial equipped with a stir bar was charged with a mixture of lithium tert-butoxide (0.52 g, 6.5 mmol) and diethyl oxalate (0.88 g, 6.0 mmol) in anhydrous THF (10 mL), and the mixture was then stirred at 0 oC under a nitrogen atmosphere. Ten minutes later, a solution of alkylphenones 1 (5.0 mmol) in anhydrous THF (5 mL) was added dropwise to the mixture, and the resulting mixture was allowed to stir at room temperature for 4 h. After completion of the reaction as monitored by TLC, the mixture was concentrated to remove THF giving a residual, to which were added water (10 mL), methylene chloride (15 mL) and 10% hydrochloric acid (ca. 3 mL) until pH 3-4 to make the solution partitioned into organic and aqueous layers. The aqueous layer was extracted with methylene chloride (10 mL × 2). The combined organic phase was washed with water (20 mL × 2), dried over anhydrous sodium sulfate, and concentrated to give a crude oil, which was purified by column chromatography (200-300 mesh silica gel, petroleum ether/ethyl acetate 20:1) to offer the corresponding 2.
63%		To a solution of 1.0 M LiHMDS in hexanes (13 mL, 13.0 mmol) in Et2O (15 mL) atrt., was slowly added 4?-chloropropiophenone (2.0 g, 11.9 mmol) in Et2O (5 mL). Afterstirring for 45 minutes, diethyl oxalate (2.4 mL, 17.8 mmol) was added, and the solution was stirred for16 h at rt. The precipitate was filtered, washed three times with a mixture of cold Et2O-hexanes (3:1),dissolved in EtOAc, and washed with 1M aq. HCl (1 × 20 mL). The organic phase was then washed with brine (20 mL), dried over MgSO4, filtered, and concentrated in vacuo. The resultant crude oil waspurified by flash chromatography (EtOAc-hexanes, 1:3) giving the product as a yellow oil (2.0 g, 63%).deltaH (400 MHz; CDCl3): 7.88 (dt, J = 8.9, 2.0, 2H), 7.49 (dt, J = 8.7, 2.0, 2H), 4.99 (q, J = 7.0, 1H), 4.21(q, J = 7.0, 2H), 1.44 (d, J = 7.0, 3H), 1.29 (d, J = 7.1, 3H); deltaC (100 MHz; CDCl3): 197.0, 190.4, 160.5,140.6, 133.6, 130.3, 129.4, 63.1, 51.0, 13.9, 12.8. Spectroscopic data were in good agreement with thosepreviously reported.1

		Scheme 1 shows how the condensation of a propiophenone with diethyl oxalate in the presence of a base such as lithium hexamethydilsilazide should afford, after acidification with hydrochloric acid solution, the diketoester (step a). Heating this ester with an aryl hydrazine in a solvent such as ethanol should produce the pyrazole ester along with the uncyclized imine (step b). These materials may be separated due to their solubility differences, or heated together in ethanolic hydroxide solution to cause further conversion of the imine to the pyrazole along with concomitant saponification of the ester to the carboxylic acid (step c). Subsequent conversion of the carboxylic acid to the acid chloride using thionyl chloride followed by treatment with ethyl N-aminonipecotate should afford the hydrazide ester (step d). Hydrolysis of the ester with lithium hydroxide and acidification with dilute hydrochloric acid solution should yield the hydrazide carboxylic acid (step e). Treatment of this acid with thionyl chloride followed by ammonia should afford the carboxamide (step f).
23 g		To a stirred solution of l-(4-chlorophenyl)propan-l-one (20.0 g, 119 mmol) in diisopropyl ether (150 mL) was added lithium bis(trimethylsilyl)amide (119 mL of a 1.0 M solution in THF, 119 mmol) at a temperature between 14-28 C. The resulting reaction mixture was stirred for 30 min and diethyl oxalate (21.06 mL, 154 mmol) was added to the reaction mixture at a temperature between 14-28 C. The reaction mixture was stirred further for 15 h at 25-30 C to obtain solid crude. The solid crude was filtered under nitrogen atmosphere, washed with diethyl ether and dried to give a yellow, moisture- sensitive solid which was poured in water and acidified with IN HC1 (pH = 2). The resulting mixture was extracted with ethyl acetate, washed with water and brine, dried with sodium sulphate (Na2S04) and concentrated to afford the intermediate, ethyl 4-(4-chlorophenyl)-3-methyl-2,4-dioxobutanoate. Yield: 23 g.
23 g		To a stirred solution of 1-(4-chlorophenyl)propan-1-one (20 g, 119 mmol) in diisopropyl ether (150 mL) was slowly added a solution of lithiumbis(trimethylsilyl)amide (119 mL, 119 mmol) at 14-28 C. After stirring for 30 mm, diethyl oxalate (21 .06 mL, 154 mmol) was added over 30 mm at the same temperature and the reaction mixture was stirred for 15 h at 25-30 C. The solid was filtered under nitrogen atmosphere, washed with diethyl ether and dried to give a yellow, moisturesensitive solid which was poured in water and acidified with 1 N HCI (pH = 2). The resulting mixture was extracted with ethyl acetate, washed with water and brine, dried (anhydrous Na2SO4) and concentrated to give intermediate ethyl 4-(4-chlorophenyl)-3- methyl-2,4-dioxobutanoate (23 g)
		EXAMPLE 4; PREPARATION OF 4-(4-CHLOROPHENYL)-3-METHYL-2,4-DIOXOBUTYRIC ACID ETHYL ESTER (FORMULA VIII)300 ml of methylcyclohexane was taken into a clean and dry round bottom flask under a nitrogen atmosphere followed by addition of 300 ml of lithium hexamethyldisilazamide. The mixture was cooled to 15 0C followed by addition of a mixture of 50 g of 4-chloropropiophenone and 125 ml of methylcyclohexane. The resultant reaction mixture was stirred for 3 hours followed by addition of 47.8 of diethyl oxalate. The reaction mixture was stirred for 15 hours, the separated solid was filtered, and the solid was washed with 50 ml of methylcyclohexane followed by slurrying the obtained solid in 200 ml of methylcyclohexane and filtering under a nitrogen atmosphere. The solid was dissolved in 250 ml of water, filtered and the pH of the filtrate was adjusted to 2 by the addition of 24 ml of hydrochloric acid (12N). Separated solid was filtered and the filtrate was extracted with 3x250 ml of ethyl acetate and the total organic layer was dried over anhydrous sodium sulfate (20 g) followed by distillation of the solvent completely at 65 0C under a vacuum of 700 mm Hg to afford 21.5 g of the title compound as a residue.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 62,p. 256 - 269
[2]Tetrahedron,2013,vol. 69,p. 627 - 635
[3]Patent: WO2020/103856,2020,A1 .Location in patent: Paragraph 0176
[4]Chemical Communications,2008,p. 1100 - 1102
[5]Bioorganic and Medicinal Chemistry Letters,2019,vol. 29
[6]Monatshefte fur Chemie,2008,vol. 139,p. 1091 - 1093
[7]Journal of the Chemical Society. Chemical communications,1995,p. 1549 - 1550
[8]Bioorganic and Medicinal Chemistry,2004,vol. 12,p. 393 - 404
[9]Patent: US2007/213302,2007,A1 .Location in patent: Page/Page column 11; 12; 27
[10]Bioorganic and Medicinal Chemistry Letters,2013,vol. 23,p. 2134 - 2139
[11]Patent: WO2015/155566,2015,A1 .Location in patent: Page/Page column 75
[12]Patent: WO2015/162452,2015,A1 .Location in patent: Page/Page column 69; 73
[13]Patent: WO2007/121466,2007,A2 .Location in patent: Page/Page column 20

16
[ 6285-05-8 ]
[ 2921-14-4 ]
[1-(4-Chloro-phenyl)-prop-(E)-ylideneaminooxy]-acetic acid [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1977,vol. 20,p. 1199 - 1206

17
[ 6285-05-8 ]
[ 1546-79-8 ]
1-(4-Chloro-phenyl)-4,4,4-trifluoro-2-methyl-butane-1,3-dione [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1997,vol. 40,p. 1347 - 1365

18
[ 6285-05-8 ]
[ 1678-92-8 ]
[ 103-65-1 ]
[ 93-54-9 ]
[ 1123-86-0 ]
[ 17264-02-7 ]

Reference： [1]Journal of Organic Chemistry,1998,vol. 63,p. 3266 - 3271

19
[ 6285-05-8 ]
[ 1678-92-8 ]
[ 103-65-1 ]
[ 93-54-9 ]
[ 1123-86-0 ]
[ 93-55-0 ]

Reference： [1]Journal of Organic Chemistry,1999,vol. 64,p. 3934 - 3939

20
[ 6285-05-8 ]
[ 93-54-9 ]
[ 1123-86-0 ]
[ 17264-02-7 ]
[ 93-55-0 ]

Reference： [1]Journal of Organic Chemistry,1999,vol. 64,p. 3934 - 3939

21
[ 6285-05-8 ]
[ 104408-23-3 ]
<i>N</i>-[1-(4-chloro-phenyl)-propylidene]-<i>N</i>'-(3,5-dichloro-pyridin-2-yl)-hydrazine [ No CAS ]

Reference： [1]Chemistry of Heterocyclic Compounds,2000,vol. 36,p. 931 - 943

22
[ 6285-05-8 ]
[ 73890-73-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With tetrahydrofuran; dimethylsulfide borane complex; In toluene; at 0℃;Inert atmosphere;	General procedure: ketonesBH3/SMe2(1.1 ml, 1 M) was added by syringe to a solution ofchiral polyether ligand Poly-6 (0.78 g, 0.1 mmol) in dry THF (5 ml)under nitrogen at 0C. The mixture was stirred for 1 h at 0C andthen a solution of ketone (1 mmol) in dry THF (5 ml) was addeddropwise over a period of 1 h at the same temperature and stirredfor 6 h, the reaction mixture was then quenched by dropwise addi-tion of 10% NH4Cl (5 ml). The alcohol product was isolated byextraction with ethyl acetate (10 ml × 3). The organic phase waswashed with brine, dried over anhydrous sodium sulfate. Afterconcentration by rotatory evaporation, the product was purifiedby column chromatography on silica gel (petroleum ether/ethylacetate 6:1) to afford the corresponding alcohol. The enantiomericexcesses were determined by HPLC with a chiral column (Dai-cel Chiralcel OD-H; eluent, hexane-isopropyl alcohol; UV detector,254 nm).
90%	With borane-THF; at 30℃; for 6.5h;Inert atmosphere;	General procedure: To a 25ml round-bottom flask was added 0.05mmol (0.05equiv) of chiral ligand in 5ml of THF. Under a nitrogen atmosphere and at 0C, BH3·THF (5M) (1.1mmol, 1.1equiv) was added. The mixture was stirred at 0C for 0.5h and then warmed to 30C for a further hour. The ketone (1mmol) in 2ml of THF was added slowly over a period of 0.5h under the same temperature and stirred for 6h. The reaction mixture was cooled to 0C and quenched with a 1M aqueous HCl solution (8ml), then extracted with ethyl acetate (3ml×10ml). The combined organic layer was washed twice with brine and dried with anhydrous MgSO4. The solvent was removed under reduced pressure. The residue was passed through a short silica gel column to afford a pure product before being subjected to HPLC analysis.

Reference： [1]Chirality,2015,vol. 27,p. 422 - 424
[2]Journal of Molecular Catalysis A: Chemical,2015,vol. 398,p. 407 - 412
[3]Tetrahedron Asymmetry,2015,vol. 26,p. 173 - 179
[4]Advanced Synthesis and Catalysis,2007,vol. 349,p. 1797 - 1802
[5]Journal of Organic Chemistry,2009,vol. 74,p. 4608 - 4611
[6]ACS Catalysis,2019,vol. 9,p. 5562 - 5566
[7]Organic Letters,2008,vol. 10,p. 2979 - 2982
[8]Tetrahedron Asymmetry,2002,vol. 13,p. 1681 - 1686

23
[ 6285-05-8 ]
[ 56962-09-5 ]

Yield	Reaction Conditions	Operation in experiment
93.4%	With hydroxylamine hydrochloride; sodium acetate; In 1,2-dichloro-ethane; at 25℃; for 3h;	Hydroxylamine hydrochloride (0.1 mol), with stirring,1,2-dichloroethane (150ml) and sodium acetate (0.1mol)Add to the reaction vessel,Slowly warm up to 25 C,Stir for 1hr,Add p-chloropropiophenone (0.1 mol),TLC detects the reaction,Complete reaction after 2hr,Filtering,Collecting mother liquor,The mother liquor is followed by 5wt% citric acid (100ml),Saturated sodium bicarbonate (100ml)Washed with saturated salt water,Dry over anhydrous sodium sulfate,Then concentrate the mother liquor,Obtained a white solid,Collecting solids,Melting point 61~62C,The yield was 93.4% based on p-chloropropiophenone.The purity of HPLC was 98.6%.This solid is 1-(4-chlorophenyl)-1-propanone oxime.
	With pyridine; hydroxylamine hydrochloride; In ethanol; for 3h;Heating / reflux;	EXAMPLE 162 [(4S,5R)-2-(4-tert-Butyl-2-ethoxy-phenyl)-4,5-bis-(4-chloro-phenyl)-4,5-diethyl-4,5-dihydro-imidazol-1-yl]-[4-(3-methanesulfonyl-propyl)-piperazin-1-yl]-methanone <strong>[6285-05-8]1-(4-Chlorophenyl)propan-1-one</strong> (8.4 g, 50 mmol) was combined with hydroxylamine hydrochloride (4.0 g, 58 mmol), pyridine (4.6 g, 58 mmol), and ethanol (75 mL). The mixture was refluxed for 3 h. Solvent was evaporated and the residue diluted with water and extracted into diethyl ether/hexane (1:1). The organic extracts were washed with water, brine, and dried over anhydrous magnesium sulfate. Crystallization from cold hexane gave 5.0 g of 1-(4-chlorophenyl)propan-1-one oxime.
	With hydroxylamine hydrochloride; triethylamine; In ethanol; at 10 - 35℃; for 16h;	A) 1-(4-chlorophenyl)propan-1-amine [0828] To a solution of 1-(4-chlorophenyl)propan-1-one (1.69 g) in ethanol (60 mL) were added hydroxylamine hydrochloride (1.39 g) and triethylamine (2.79 mL) at room temperature. The reaction mixture was stirred at room temperature for 16 hr, and the solvent was evaporated under reduced pressure. To the residue was added water, and the mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 1-(4-chlorophenyl)-N-hydroxypropan-1-imine. To a solution of 1-(4-chlorophenyl)-N-hydroxypropan-1-imine in tetrahydrofuran (100 mL) was added 1.1 M boranetetrahydrofuran complex/tetrahydrofuran solution (27.3 mL), and the mixture was stirred at 80C for 16 hr. To the reaction mixture was added 1 M hydrochloric acid, and the mixture was extracted with ethyl acetate. The extract was washed successively with water and saturated brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (NH, hexane/ethyl acetate) to give the title compound (520 mg). 1H NMR (300 MHz, CDCl3) delta 0.85 (3H, t, J = 7.3 Hz), 1.58-1.74 (2H, m), 3.80 (1H, t, J = 7.0 Hz), 7.21-7.40 (4H, m).

	With hydroxylamine hydrochloride; In methanol;Reflux;	200 ml of methanol, 34.06 g (0.2 mol) of p-chloropropiophenone, and 17.02 g of hydroxylamine hydrochloride were placed in a 500 ml four-necked flask.(0.24 mol), the temperature was refluxed, and the reaction was cooled. After cooling, 14.93 g (0.24 mol) of potassium hydroxide was added to neutralize to Ph=7, then methanol was recovered under reduced pressure, and then 200 ml of toluene and 100 ml of water were added, and the mixture was stirred for 30 min. After layering, the aqueous layer is separated, and the organic phase is heated to reflux to remove water, thereby obtaining (1-(p-chlorophenyl)propionyl)oxime solution.
	With hydroxylamine hydrochloride; sodium acetate; In ethanol; water; at 100℃;	General procedure: To a solution of aromatic ketones (2 mmol) in C2H5OH/H2O (v/v = 1:1) was added, hydroxylamine hydrochloride (2.2 mmol), NaOAc (3 mmol) in one portion, and the reaction mixture was stirred at 100C for 6-8 h. Upon completion of the reaction as indicated by TLC, the reaction mixture was diluted with water, extracted with ethyl acetate and dried over anhydrous Na2SO4. The solvent was removed and concentrated under reduced pressure to give oximes.

Reference： [1]Patent: CN108752229,2018,A .Location in patent: Paragraph 0019; 0023; 0027; 0031; 0035
[2]Bioorganic and Medicinal Chemistry Letters,2005,vol. 15,p. 497 - 500
[3]Journal of Organic Chemistry,2007,vol. 72,p. 204 - 208
[4]Patent: US2007/129416,2007,A1 .Location in patent: Page/Page column 62/2
[5]Organic Letters,2010,vol. 12,p. 2214 - 2217
[6]Angewandte Chemie - International Edition,2014,vol. 53,p. 13278 - 13281
[7]Patent: EP2848618,2015,A1 .Location in patent: Paragraph 0828
[8]Journal of the American Chemical Society,2017,vol. 139,p. 11702 - 11705
[9]Chemical Communications,2018,vol. 54,p. 10750 - 10753
[10]Patent: CN108558787,2018,A .Location in patent: Paragraph 0018; 0022; 0025; 0028
[11]Tetrahedron Letters,2018,vol. 59,p. 2430 - 2433

24
[ 6285-05-8 ]
[ 391-12-8 ]
C₁₈H₁₁ClF₃NO₂ [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2007,vol. 50,p. 21 - 39

25
[ 6285-05-8 ]
[ 118994-84-6 ]
[ 936331-81-6 ]

Reference： [1]Organic Letters,2007,vol. 9,p. 1875 - 1878

26
[ 6285-05-8 ]
[ 168273-06-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 5 steps 1.1: 65 percent / LDA; potassium t-butoxide / diethyl ether; tetrahydrofuran; heptane / 2.5 h / 20 °C 2.1: HCl / H₂O; CH₂Cl₂ 3.1: ethanol / 2.5 h / Heating 3.2: 89 percent / NaOH / ethanol / 2 h / Heating 4.1: 94 percent / SOCl₂ / toluene / 6 h / Heating 5.1: 11.5 g / triethylamine / CH₂Cl₂ / 2 h / 20 °C
	Multi-step reaction with 4 steps 1.1: lithium hexamethyldisilazane / Methylcyclohexane / 3 h / 20 °C 1.2: 16 h 1.3: Cooling with ice; Reflux 2.1: potassium hydroxide / ethanol / 12 h / 50 °C 3.1: thionyl chloride / toluene / 2.5 h / 110 °C 4.1: N-ethyl-N,N-diisopropylamine / chloroform / 4 h / 0 - 20 °C
	Multi-step reaction with 4 steps 1.1: lithium hexamethyldisilazane / Methylcyclohexane / 2.5 h / 15 - 25 °C / Inert atmosphere 1.2: Inert atmosphere 2.1: sulfuric acid / ethanol; lithium hydroxide monohydrate / 14 h / 79 °C / Inert atmosphere 3.1: N,N-dimethyl-formamide / toluene / 0 °C / Inert atmosphere 3.2: 4 h / 100 °C / Inert atmosphere 4.1: triethylamine / dichloromethane / 0 - 20 °C / Inert atmosphere

	Multi-step reaction with 3 steps 1.1: lithium hexamethyldisilazane / Methylcyclohexane / 3 h / 15 °C 1.2: 15 h 2.1: triethylamine / 3 h 3.1: ethanol / 8 h
	Multi-step reaction with 5 steps 1.1: lithium hexamethyldisilazane / cyclohexane; Methylcyclohexane / 3 h / 15 °C 1.2: 8 h / 15 °C 2.1: sulfuric acid / ethanol; lithium hydroxide monohydrate / 5.33 - 7.17 h / 90 °C 3.1: sulfuric acid / lithium hydroxide monohydrate / 12 h / 130 - 140 °C 4.1: potassium hydroxide; lithium hydroxide monohydrate / methanol / 3 h / 90 °C 4.2: 0.5 h / 0 - 28 °C / pH 2 5.1: Orthoboric acid / toluene / 12.83 h / 29 - 112 °C
	Multi-step reaction with 6 steps 1.1: lithium hexamethyldisilazane / cyclohexane; Methylcyclohexane / 3 h / 15 °C 1.2: 8 h / 15 °C 2.1: sulfuric acid / ethanol; lithium hydroxide monohydrate / 5.33 - 7.17 h / 90 °C 3.1: sulfuric acid / lithium hydroxide monohydrate / 12 h / 130 - 140 °C 4.1: potassium hydroxide; lithium hydroxide monohydrate / methanol / 3 h / 90 °C 4.2: 0.5 h / 0 - 28 °C / pH 2 5.1: dicyclohexyl-carbodiimide / dichloromethane / 1.17 h / 0 - 30 °C 6.1: potassium carbonate / dichloromethane / 0.5 h / 30 °C
	Multi-step reaction with 6 steps 1.1: lithium hexamethyldisilazane / cyclohexane; Methylcyclohexane / 3 h / 15 °C 1.2: 8 h / 15 °C 2.1: sulfuric acid / ethanol; lithium hydroxide monohydrate / 5.33 - 7.17 h / 90 °C 3.1: sulfuric acid / lithium hydroxide monohydrate / 12 h / 130 - 140 °C 4.1: potassium hydroxide; lithium hydroxide monohydrate / methanol / 3 h / 90 °C 4.2: 0.5 h / 0 - 28 °C / pH 2 5.1: thionyl chloride / toluene / 4 h / 30 - 110 °C 6.1: triethylamine / dichloromethane / 0.5 h / -15 - 15 °C
	Multi-step reaction with 3 steps 1.1: lithium hexamethyldisilazane / Methylcyclohexane 1.2: 17 h / 20 °C 2.1: thionyl chloride / toluene / 2 h / Reflux 3.1: N-ethyl-N,N-diisopropylamine / chloroform / 4 h / 0 - 20 °C

Reference： [1]Seltzman, Herbert H.; Carroll, F. Ivy; Burgess, Jason P.; Wyrick, Christopher D.; Burch, David F. [Journal of labelled compounds and radiopharmaceuticals, 2002, vol. 45, # 1, p. 59 - 70]
[2]Hernández-Vázquez, Eduardo; Aguayo-Ortiz, Rodrigo; Ramírez-Espinosa, Juan José; Estrada-Soto, Samuel; Hernández-Luis, Francisco [European Journal of Medicinal Chemistry, 2013, vol. 69, p. 10 - 21]
[3]Gajbhiye; More; Patil, Manoj D.; Ummanni; Kotapalli; Yogeeswari; Sriram; Masand [Medicinal Chemistry Research, 2015, vol. 24, # 7, p. 2960 - 2971]
[4]Current Patent Assignee: DR REDDY'S LABORATORIES LIMITED - WO2007/121466, 2007, A2
[5]Current Patent Assignee: DR REDDY'S LABORATORIES LIMITED - WO2007/121466, 2007, A2
[6]Current Patent Assignee: DR REDDY'S LABORATORIES LIMITED - WO2007/121466, 2007, A2
[7]Current Patent Assignee: DR REDDY'S LABORATORIES LIMITED - WO2007/121466, 2007, A2
[8]Hernández-Vázquez, Eduardo; Estrada-Soto, Samuel; Lumbreras-Zavala, Norma; Mundo-Campuzano, Martín; Chávez-Silva, Fabiola; Villalobos-Molina, Rafael; Hernández-Luis, Francisco [Chemical Papers, 2022, vol. 76, # 9, p. 5551 - 5560]

27
[ 6285-05-8 ]
[ 608-68-4 ]
[ 497-19-8 ]
2-ethyl-2-(4-chlorophenyl)-1,3-dioxolane-4(R),5(R)-dicarboxylic acid dimethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With methanesulfonic acid; trimethyl orthoformate	76 Preparation of 2-ethyl-2-(4-chlorophenyl)-1,3-dioxolane-4(R),5(R)-dicarboxylic acid dimethyl ester EXAMPLE 76 Preparation of 2-ethyl-2-(4-chlorophenyl)-1,3-dioxolane-4(R),5(R)-dicarboxylic acid dimethyl ester Methanesulfonic acid (1.03 g, 0.011 mol) was added, at 60° C., in 5 min, to a stirred solution of 1-(4-chlorophenyl)propan-1-one (25.0 g, 0.149 mol), (2R,3R)-tartaric acid dimethyl ester (62.7 g, 0.352 mol), and trimethyl orthoformate (34.6 g, 0.326 mol). The solution was heated at 96° C. and kept at this temperature for 3 h, while the volatile compounds were distilled off. The reaction mixture was cooled to room temperature, poured into a vigorously stirred 10% aqueous sodium carbonate solution (100 mL), and extracted with dichloromethane (2100 mL). The organic phases were combined together and washed with water (2250 mL) and dried over sodium sulfate, and the solvent was removed in vacuo to give an oil (55.4 g). A mixture of the oily residue, methanefulfonic acid (1.56 g, 0.016 mol) and (2R,3R)-tartaric acid dimethyl ester (116.9 g, 0.657 mol) was heated at 95° C. with stirring for 1 hour. The reaction mixture was cooled to room temperature and worked up as described in Example 74. After purification on column chromatography the desired compound was obtained. (42.8 g, 0.130 mol, 87% yield) as an oil: [α]D20 +20.6° (c 1, CHCl3); IR (neat) 1755 cm-1; 1 H NMR (300 MHz, CDCl3 -TMS) δ(ppm) 0.91 (t, 3H, J=7.4); 1.98 (q, 2H, J=7.4); 3.58 (s, 3H), 3.84 (s, 3H), 4.78 (s, 2H), 7.3-7.4 (m, 4H).

Reference： [1]Current Patent Assignee: GEFIM S.P.A. - US4810819, 1989, A

28
[ 1021934-07-5 ]
[ 6285-05-8 ]
[ 5586-88-9 ]

Yield	Reaction Conditions	Operation in experiment
1: 86% 2: 5%	With diethylzinc In dichloromethane at 20℃; for 2h;

Reference： [1]Li, Lezhen; Cai, Peijie; Guo, Qingxiang; Xue, Song [Journal of Organic Chemistry, 2008, vol. 73, # 9, p. 3516 - 3522]

29
[ 6285-05-8 ]
[ 95-92-1 ]
[ 1012314-40-7 ]

Yield	Reaction Conditions	Operation in experiment
89%		General procedure: A solution of the corresponding propiophenone (15.06 mmol) in 3 mL of anhydrous methylcyclohexane was added at room temperature to a magnetically stirred solution of lithium bis(-trimethylsilyl)amide (16.1 mmol) in anhydrous methylcyclohexane (3-5 mL). After 3 h of stirring, diethyl oxalate (16.6 mmol) was added dropwise and then left to react for 16 h. The mixture was filtered and washed with several portions of methylcyclohexane and used in the next reaction without purification.
71.9%		Methylcyclohexane(30 ml) and lithium hexamethyldisilazane (30 ml,31.7 mmol) were introduced in a round-bottom flask undernitrogen atmosphere and cooled to 15-25C. A solution of4-chloropropiophenone (A, 5.0 g, 29.65 mmol) inmethylcyclohexane (12.5 ml) was slowly added with continuousstirring for 2.5 h. To this reaction mixture, diethyloxalate (4.78 g, 32.6 mmol) was added with stirring. Thereaction progress was monitored by TLC; the solid obtainedwas filtered, washed with methylcyclohexane(30 ml) and dried under vacuum (30 min) to afford thelithium salt (Kotagiri et al., 2007) (Cream yellow solid,5.7 g, 71.9 %).

Reference： [1]European Journal of Medicinal Chemistry,2015,vol. 100,p. 106 - 118
[2]Medicinal Chemistry Research,2015,vol. 24,p. 2960 - 2971
[3]Bioorganic and Medicinal Chemistry,2009,vol. 17,p. 3080 - 3092
[4]Patent: WO2009/16241,2009,A1 .Location in patent: Page/Page column 29
[5]Patent: US2010/113546,2010,A1 .Location in patent: Page/Page column 14
[6]Chinese Journal of Chemistry,2014,vol. 32,p. 179 - 190
[7]RSC Advances,2014,vol. 4,p. 20164 - 20176

30
[ 4466-24-4 ]
[ 6285-05-8 ]
[ 1253967-16-6 ]

Yield	Reaction Conditions	Operation in experiment
94%	With 1,1'-bis(dicyclohexylphosphanyl)-3,3'-di(triphenylmethyl)ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;
84%	With 1,1',2-tris(diphenylphosphino)-3',4-di-tert-butyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;

Reference： [1]Location in patent: experimental part Mom, Sophal; Beaupérin, Matthieu; Roy, David; Royer, Sylviane; Amardeil, Régine; Cattey, Hélène; Doucet, Henri; Hierso [Inorganic Chemistry, 2011, vol. 50, # 22, p. 11592 - 11603]
[2]Roy, David; Mom, Sophal; Beauperin, Matthieu; Doucet, Henri; Hierso, Jean-Cyrille [Angewandte Chemie - International Edition, 2010, vol. 49, # 37, p. 6650 - 6654]

31
[ 1455-20-5 ]
[ 6285-05-8 ]
[ 1253967-22-4 ]

Reference： [1]Angewandte Chemie - International Edition,2010,vol. 49,p. 6650 - 6654

32
[ 6285-05-8 ]
[ 6141-58-8 ]
[ 1253967-19-9 ]

Yield	Reaction Conditions	Operation in experiment
38%	With 1,1',2-tris(diphenylphosphino)-3',4-di-tert-butyl ferrocene; tetrabutylammomium bromide; potassium acetate; palladium diacetate In N,N-dimethyl acetamide at 150℃; for 16h; Inert atmosphere;

Reference： [1]Roy, David; Mom, Sophal; Beauperin, Matthieu; Doucet, Henri; Hierso, Jean-Cyrille [Angewandte Chemie - International Edition, 2010, vol. 49, # 37, p. 6650 - 6654]

33
[ 6285-05-8 ]
[ 5446-18-4 ]
[ 95-92-1 ]
[ 158941-22-1 ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of hexamethyldisilazane (HMDS) (92.6 mL, 443 mmol) in diethyl ether (2 L) was added 15% n-butyllithium in hexane (200 mL, 443 mmol) at -20 C and stirred for 30 min. The reaction mixture was cooled to -78 C and to it was added 4-chloropropiophenone (50 g, 295 mmol) in ether (500 mL) and stirred for 45 min at -78 C. The cooling bath was removed and the reaction mixture was allowed to warm up to -20 C and stirred until the reaction mixture turned into a clear solution. The reaction mixture was cooled again to -78 C and diethyl oxalate (80.4 mL, 591 mmol) was added to it. The reaction mixture was slowly warmed up to room temperature over 4 h and stirred for additional 16 h. The yellow colored solid was filtrated and washed with ether and dried under vacuum to give 57 g of lithium salt of 4-(4-chloro-phenyl)-3-methyl-2,4-dioxo-butyric acid ethyl ester. This solid was added to a solution of <strong>[5446-18-4]2,4-dichlorophenylhydrazine hydrochloride</strong> (44.5 g, 208 mmol) in ethanol (1.2 L) and stirred at room temperature for 16 h. The precipitated solid was filtered, washed with ethanol and dried under vacuum. This solid was dissolved in acetic acid (1 L) and refluxed for 16 h. The reaction mixture was cooled and slowly poured into cold water. The separated solid was filtered, washed with water and dried to give 24 g of the pyrazole ester which was dissolved in methanol (50 mL). To this solution was added a solution of potassium hydroxide (1.6 g, 28.4 mmol) in water (10 mL) and the mixture was refluxed for 3 h. The solvent was evaporated under vacuum and the residue was poured into crushed ice and acidified with 6N HCl (pH ~2). The separated solid was filtered, washed with water and dried under vacuum to give the desired compound (4.1 g) as a solid.

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 562 - 568
[2]Tetrahedron Letters,2012,vol. 53,p. 4743 - 4746
[3]Synlett,2012,vol. 23,p. 2965 - 2968

34
[ 6285-05-8 ]
[ 31970-26-0 ]

Reference： [1]Organometallics,2011,vol. 30,p. 4067 - 4073

35
[ 6285-05-8 ]
[ 726-42-1 ]
[ 2447-95-2 ]

Yield	Reaction Conditions	Operation in experiment
96%	With [{HMn(CO)₄}3] In 1,4-dioxane at 135℃; for 24h; Sealed tube; Inert atmosphere;

Reference： [1]Kuninobu, Yoichiro; Uesugi, Tadamasa; Kawata, Atsushi; Takai, Kazuhiko [Angewandte Chemie - International Edition, 2011, vol. 50, # 44, p. 10406 - 10408]

36
[ 6285-05-8 ]
[ 158681-13-1 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 6 steps 1.1: triethylamine; methyl iodide / acetonitrile / 24 h / 20 - 45 °C / Inert atmosphere 2.1: tetrahydrofuran / 5 h / 10 - 20 °C 3.1: triethylamine / toluene / 12 h / 20 °C 4.1: toluene-4-sulfonic acid / toluene / 12 h / Reflux 5.1: oxalyl dichloride / dichloromethane; N,N-dimethyl-formamide / 2 h / 20 °C / Cooling with ice 6.1: triethylamine / dichloromethane / 1 h / 10 - 20 °C 6.2: pH 1

Reference： [1]Fang, Zheng; Yang, Zhao; Xu, Jia-Feng; Guo, Kai; Wei, Ping [Organic Preparations and Procedures International, 2012, vol. 44, # 2, p. 164 - 168]

37
[ 6285-05-8 ]
[ 2564-83-2 ]
[ 1394206-51-9 ]

Yield	Reaction Conditions	Operation in experiment
99%	With 2,6-di-tert-butyl-pyridine; 2-chloro-1,3,2-benzodioxaborole In dichloromethane at 0 - 20℃; for 3h;

Reference： [1]Li, Yi; Pouliot, Martin; Vogler, Thomas; Renaud, Philippe; Studer, Armido [Organic Letters, 2012, vol. 14, # 17, p. 4474 - 4477]

38
[ 6285-05-8 ]
[ 1448902-18-8 ]

Reference： [1]Bioorganic and Medicinal Chemistry,2013,vol. 21,p. 5907 - 5922

39
[ 925-90-6 ]
[ 122334-37-6 ]
[ 6285-05-8 ]

Yield	Reaction Conditions	Operation in experiment
77%	In diethyl ether at 0℃; for 3h;	1-(4-chlorophenyl)Propan-1-one [0117] l-(4-chlorophenyl)Propan-l-one: 4-Chloro-N-methoxy-N-methylbenzamide (0.5352 g, 2.68 mmol, 1.00 equiv) was dissolved in Et20 (10 mL) and cooled to 0 °C. Ethylmagnesium bromide (1.80 mL, 5.36 mmol, 2.00 equiv, 3M solution in Et20) was added dropwise. After stirring for 3 h the reaction was quenched with NH4C1 (sat. aq.) and the layers were separated. The aqueous layer was back extracted with Et20 (3x). The combined organic layers were washed with H20, brine, dried over Na2S04, filtered and concentrated. Purification by silica gel column chromatography using a 1 : 1 mixture of ethyl acetate in hexanes as eluant furnished the title compound (0.349 g) as a clear oil. Yield: 77%. The spectral data was identical to that reported in the literaturev: NMR (500 MHz, CDC13): δ 7.94-7.89 (m, 2H), 7.49-7.38 (m, 2H), 2.97 (q, J= 7.2 Hz, 2H), 1.22 (t, J= 7.2 Hz, 3H) ppm.

Reference： [1]Current Patent Assignee: UNIVERSITY OF PENNSYLVANIA - WO2014/47257, 2014, A2 Location in patent: Paragraph 0117

40
[ 67-56-1 ]
[ 6285-05-8 ]
[ 18713-58-1 ]

Reference： [1]Chemistry - A European Journal,2015,vol. 21,p. 3576 - 3579
[2]ACS Catalysis,2018,vol. 8,p. 6440 - 6445
[3]Organic Letters,2017,vol. 19,p. 4750 - 4753
[4]Organometallics,2018,vol. 37,p. 3353 - 3359
[5]Angewandte Chemie - International Edition,2019,vol. 58,p. 775 - 779
Angew. Chem.,2019,vol. 131,p. 785 - 789,5
[6]Journal of the Chinese Chemical Society,2019,vol. 66,p. 972 - 981

41
[ 6285-05-8 ]
[ 589-21-9 ]
5-bromo-2-(4-chlorophenyl)-3-methyl-1H-indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With Amberlite IR 120 In ethanol at 80℃; for 10h;	EXPERIMENTAL General procedure: A mixture of the carbonyl compound (5, 1.0 mmol), arylhydrazine (6, 1.2 mmol), and the solid acid (7, Amberlite, 1.5 g, obtained from Aldrich Chemical Co.) was refluxed in absolute ethanol (10 ml) for 8 h. The reaction was monitored by thin-layer chromatography(TLC), and upon completion the mixture was cooled to room temperature, the catalyst filtered off, and the product was washed thoroughly with ethylacetate (30 ml). The combined organics were washed with water, dried (Na2SO4), and concentrated in vacuo. The resulting residue was chromatographed on a silicagel column eluting with ethylacetate-hexane mixtures to obtain the purified indole (8). This was fully characterized by infrared, 400-MHz 1H NMR, high-resolution mass spectrometry, and melting point (solids).

Reference： [1]Chandrasekhar, Sosale; Mukherjee, Somnath [Synthetic Communications, 2015, vol. 45, # 8, p. 1018 - 1022]

42
[ 6285-05-8 ]
[ 5333-83-5 ]
C₁₅H₁₃ClO₃S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With potassiumhexacyanoferrate(II) trihydrate; 2,6-bis[(4,4-dimethyl)-2-oxazolin-2-yl]pyridine copper bromide; oxygen In N,N-dimethyl-formamide at 100℃; for 20h; Green chemistry;

Reference： [1]Jia, Wei-Guo; Zhang, Hui; Li, Dan-Dan; Yan, Li-Qin [RSC Advances, 2016, vol. 6, # 33, p. 27590 - 27593]

43
[ 6285-05-8 ]
[ 4996-21-8 ]
[ 87521-59-3 ]

Yield	Reaction Conditions	Operation in experiment
66%	With 1,4-diaza-bicyclo[2.2.2]octane; hydrazine hydrate; In water; at 25℃;Green chemistry;	General procedure: To a mixture of arylglyoxalmonohydrate (1 mmol), propiophenone (1 mmol) and DABCO (50 mol%) in water (10 mL) were added hydrazine hydrate (4 mmol). The suspension was stirred at 25 C until precipitation ceased (2-4 h). After completion of the reaction, the mixture was filtered and purified by recrystallization from ethanol. 3,6-Bis(4-chlorophenyl)-4-methylpyridazine (25): white crystals; 66%; mp 181 C. IR (KBr): numax = 3090, 3060, 3030, 1587, 1487, 1376, 1090, 1008, 827 cm-1. 1H NMR (300 MHz, CDCl3) delta 2.46 (s, 3H), 7.47-7.56 (m, 4H), 7.62 (d, 2H, J = 8.1), 7.72 (s, 1H), 8.09 (d, 2H, J = 8.4). C NMR (75 MHz, CDCl3) delta 20.0, 124.6, 126.0, 127.4, 127.5, 128.1, 129.1, 129.8, 130.4, 131.3, 136.2, 156.5, 159.6. Anal. found, C, 64.80; H, 3.81; N, 9.03. C17H12Cl2N2 requires C, 64.78; H, 3.84; N, 8.89.

Reference： [1]Cuihua Xuebao/Chinese Journal of Catalysis,2016,vol. 37,p. 517 - 525

44
[ 6285-05-8 ]
[ 106134-16-1 ]
3-(4-chlorophenyl)-6-(3-bromophenyl)-4-methylpyridazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
71%	With 1,4-diaza-bicyclo[2.2.2]octane; hydrazine hydrate; In water; at 25℃;Green chemistry;	General procedure: To a mixture of arylglyoxalmonohydrate (1 mmol), propiophenone (1 mmol) and DABCO (50 mol%) in water (10 mL) were added hydrazine hydrate (4 mmol). The suspension was stirred at 25 C until precipitation ceased (2-4 h). After completion of the reaction, the mixture was filtered and purified by recrystallization from ethanol. 3-(4-Chlorophenyl)-6-(3-bromophenyl)-4-methylpyridazine (28): yellow crystals; 71%; mp 132 C. IR (KBr): numax = 3091, 3056, 3011, 2971, 2932, 1567, 1487, 1376, 1091, 1001, 843 cm-1. 1H NMR (300 MHz, CDCl3) delta 2.45 (s, 3H), 7.40 (t, 1H, J = 7.8), 7.50 (d, 2H, J = 8.4), 7.57-7.67 (m, 3H), 7.72 (s, 1H), 8.07 (d, 1H, J = 7.8), 8.29 (s, 1H). C NMR (75 MHz, CDCl3) delta 20.0, 124.9, 126.3, 127.6, 129.2, 129.5, 130.8, 131.3, 131.8, 133.6, 135.2, 136.3, 138.1, 156.2, 159.8. Anal. found, C, 56.80; H, 3.38; N, 7.90. C17H12BrClN2 requires C, 56.77; H, 3.36; N, 7.79.

Reference： [1]Cuihua Xuebao/Chinese Journal of Catalysis,2016,vol. 37,p. 517 - 525

45
[ 6285-05-8 ]
[ 621-82-9 ]
1-(4-chlorophenyl)-1-oxopropan-2-yl cinnamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With di-tert-butyl peroxide; tetraethylammonium bromide In dimethyl sulfoxide at 100℃; for 12h;
76%	With copper(l) iodide; di-tert-butyl peroxide; tetraethylammonium bromide In dimethyl sulfoxide at 100℃; for 12h;	16 Example 16 General procedure: Cinnamic acid (0.5 mmol),Ketone compounds (0.5 mmol),CuI (20 mol%),TEAB (10 mol%),DTBP (3.0 equiv),DMSO (2.0 mL) was added to a 10 mL reactor,In the air environment,Heated to 100 ° C for 12 h,The reaction product was separated by column chromatography.
76%	With copper(l) iodide; di-tert-butyl peroxide; tetraethylammonium bromide In dimethyl sulfoxide at 100℃; for 12h; Industrial scale;	16 Example 16 Examples 16 to 25 were reacted as follows: Cinnamic acid (0.5 mmol), propiophenone (0.5 mmo1),CuI (20 mol%), TEAB (10 mol%), DTBP (3.0 equiv) and DMSO (2.0 mL) were added to a 10 mL reactor and heated to 100 °C for 12 h under an air atmosphere. The reaction product was separated by column chromatography.

Reference： [1]Xu, Jing-Wen; Ji, Peng-Yi; Liu, Yu-Feng; Luo, Wei-Ping; Liu, Qiang; Guo, Can-Cheng [European Journal of Organic Chemistry, 2017, vol. 2017, # 3, p. 734 - 740]
[2]Current Patent Assignee: YUANJIANG HUALONG CATALYST TECH - CN106242968, 2016, A Location in patent: Paragraph 0109; 0110; 0111; 0112; 0113-0115; 0156; 0157
[3]Current Patent Assignee: YUANJIANG HUALONG CATALYST TECH - CN106220496, 2016, A Location in patent: Paragraph 0107; 0108; 0109; 0110; 0111; 0112

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Precautionary Statements-General
Code	Phrase
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Code	Phrase
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Code	Phrase
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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

[ CAS No. 6285-05-8 ] {[proInfo.proName]}

Quality Control of [ 6285-05-8 ]

Related Doc. of [ 6285-05-8 ]

Product Details of [ 6285-05-8 ]

Safety of [ 6285-05-8 ]

Application In Synthesis of [ 6285-05-8 ]

[ 6285-05-8 ] Synthesis Path-Upstream 1~4

[ 6285-05-8 ] Synthesis Path-Downstream 1~45

Related Functional Groups of [ 6285-05-8 ]

Aryls

Chlorides

Ketones

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[ 6285-05-8 ]