[ CAS No. 153775-42-9 ] {[proInfo.proName]}

Name: 153775-42-9|4-Cyano-3-nitrobenzoic acid|98%
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Quality Control of [ 153775-42-9 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

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Product Details of [ 153775-42-9 ]

CAS No. :	153775-42-9	MDL No. :	MFCD16876894
Formula :	C₈H₄N₂O₄	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	JVPRJKPSKHSUDO-UHFFFAOYSA-N
M.W :	192.13	Pubchem ID :	22168583
Synonyms :

Calculated chemistry of [ 153775-42-9 ]

Physicochemical Properties

Num. heavy atoms :	14
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	2
Num. H-bond acceptors :	5.0
Num. H-bond donors :	1.0
Molar Refractivity :	46.94
TPSA :	106.91 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	No
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.5 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.52
Log Po/w (XLOGP3) :	1.37
Log Po/w (WLOGP) :	1.16
Log Po/w (MLOGP) :	-0.05
Log Po/w (SILICOS-IT) :	-0.92
Consensus Log Po/w :	0.42

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.56

Water Solubility

Log S (ESOL) :	-2.08
Solubility :	1.6 mg/ml ; 0.00833 mol/l
Class :	Soluble
Log S (Ali) :	-3.22
Solubility :	0.116 mg/ml ; 0.000605 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-1.24
Solubility :	11.0 mg/ml ; 0.0574 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	2.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.05

Safety of [ 153775-42-9 ]

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

Application In Synthesis of [ 153775-42-9 ]

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

Upstream synthesis route of [ 153775-42-9 ]
Downstream synthetic route of [ 153775-42-9 ]

[ 153775-42-9 ] Synthesis Path-Upstream 1~4

1
[ 26830-95-5 ]
[ 153775-42-9 ]

Yield	Reaction Conditions	Operation in experiment
74.5%	With chromium(VI) oxide; periodic acid In acetonitrile at 20℃; for 16 h;	Example 17: Alternative preparation of 4-cyano-3-nitro-benzoic acid; Under an inert atmosphere, periodic acid (492 g, 2.17 mol) was dissolved in acetonitrile (7.7 1) with vigorous stirring, and then, after 15 minutes chromium(VI) oxide (25 g, 0.25 mol) and 4-methyl-2-nitro-benzonitrile (100 g, 0.62 mol) were added successively. The reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was decanted and the supernatant filtered. The filtrate was concentrated and the residue partitioned between aqueous sodium carbonate (IM) and dichloromethane. The precipitate was isolated by filtration to give 4-cyano-3-nitro-benzoic acid (150 g). The filtrate was extracted twice with dichloromethane and was then acidified by addition of aqueous hydrochloric acid (4N) to pH 1. The acidified filtrate was then extracted three times with dichloromethane. The combined organic extracts were dried over sodium sulfate and concentrated. This residue was partitioned between aqueous sodium carbonate (IM) and dichloromethane. The precipitate was isolated by filtration to give 4-cyano-3-nitro-benzoic acid (26.67 g). Total yield: 150 g + 26.67 g = 176.67 g; 74.5 percent yield.

Reference： [1] Patent: WO2008/74427, 2008, A1, . Location in patent: Page/Page column 52
[2] Patent: WO2012/59442, 2012, A2, . Location in patent: Page/Page column 88-89
[3] Journal of Medicinal Chemistry, 2018, vol. 61, # 24, p. 11250 - 11260

2
[ 96-99-1 ]
[ 153775-42-9 ]

Reference： [1] Patent: US5478820, 1995, A,

3
[ 1033997-01-1 ]
[ 153775-42-9 ]

Reference： [1] Patent: WO2008/74427, 2008, A1, . Location in patent: Page/Page column 51

4
[ 151-50-8 ]
[ 1588-83-6 ]
[ 153775-42-9 ]

Reference： [1] Patent: WO2008/74427, 2008, A1, . Location in patent: Page/Page column 50

[ 153775-42-9 ] Synthesis Path-Downstream 1~46

1
[ 96-99-1 ]
copper (I)-cyanide [ No CAS ]
[ 153775-42-9 ]

Reference： [1]Patent: US2195076,1937,

2
copper(l) cyanide [ No CAS ]
[ 96-99-1 ]
[ 153775-42-9 ]

Yield	Reaction Conditions	Operation in experiment
48%	copper(I) chloride; In quinoline; hydrogenchloride;	4-Cyano-3-nitrobenzoic acid 4-Chloro-3-nitrobenzoic acid (5.84 g, 29 mM), cuprous cyanide (5.2 g, 58 mM), cuprous chloride (0.96 g, 9.7 mM), and quinoline (6.9 ml, 58 mM) were heated under an argon atmosphere at 180 for 3.5 hours. After cooling, the mixture was dissolved in concentrated hydrochloric acid (60 ml), diluted with water (80 ml), and extracted with ethyl acetate (3*100 ml). The combined organic layers were washed with aqueous NaH2 PO4, brine, and dried over MgSO4. Crude product was purified by chromatography on silica, eluding with a mixture of dichloromethane/acetic acid (98:2), to give 4-cyano-3-nitrobenzoic acid (2.65 g, 48%). Nmr (DMSO-d6): delta8.31 (d, 1H); 8.41 (dd, 1H); 8.68 (d, 1H).

Reference： [1]Patent: US5478820,1995,A

3
[ 151-50-8 ]
[ 1588-83-6 ]
[ 153775-42-9 ]

Yield	Reaction Conditions	Operation in experiment
		Example 15: Preparation of 3-cyano-5-nitro-benzoic acid; Solution 1: 3-Amino-5-nitro-benzoic acid (10 g, 54.9 mmol) was dissolved in aqueous hydrochloric acid (concentrated) (55 ml) and diluted with water (200 ml). A solution of sodium nitrite (3.788 g, 54.90 mmol) in water (30 ml) was added at 0-5 0C.Solution 2: To a solution of copper sulfate hydrate (28.786 g, 115.29 mmol) in water (120 ml) was added a solution of potassium cyanide (27.528g, 422.73 mmol) in water (30 ml).Solution 2 was heated to 65C. The pH of Solution 1 was adjusted to 6-7 with aqueous sodium carbonate (saturated) at 0-5C. Solution 1 was added dropwise to Solution 2 at 65C. The reaction mixture was heated to reflux for 40 minutes. The reaction mixture was allowed to cool to ambient temperature and acidified with aqueous hydrochloric acid (2N). The aqueous phase was extracted three times with ethyl acetate (3x 200 ml). The combined organic extracts were washed with aqueous sodium phosphite (saturated), water, brine and concentrated to give 3-cyano-5-nitro-benzoic acid (7.2 g, 68 % yield) which was used without further purification. 1H-NMR (400 MHz, DMSOd6): 9.0 (s, IH), 8.82 (s, IH), 8.70 (s, IH) ppm.

Reference： [1]Patent: WO2008/74427,2008,A1 .Location in patent: Page/Page column 50

4
[ 26830-95-5 ]
[ 153775-42-9 ]

Yield	Reaction Conditions	Operation in experiment
74.5%	With chromium(VI) oxide; periodic acid; In acetonitrile; at 20℃; for 16h;Product distribution / selectivity;	Example 17: Alternative preparation of 4-cyano-3-nitro-benzoic acid; Under an inert atmosphere, periodic acid (492 g, 2.17 mol) was dissolved in acetonitrile (7.7 1) with vigorous stirring, and then, after 15 minutes chromium(VI) oxide (25 g, 0.25 mol) and 4-methyl-2-nitro-benzonitrile (100 g, 0.62 mol) were added successively. The reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was decanted and the supernatant filtered. The filtrate was concentrated and the residue partitioned between aqueous sodium carbonate (IM) and dichloromethane. The precipitate was isolated by filtration to give 4-cyano-3-nitro-benzoic acid (150 g). The filtrate was extracted twice with dichloromethane and was then acidified by addition of aqueous hydrochloric acid (4N) to pH 1. The acidified filtrate was then extracted three times with dichloromethane. The combined organic extracts were dried over sodium sulfate and concentrated. This residue was partitioned between aqueous sodium carbonate (IM) and dichloromethane. The precipitate was isolated by filtration to give 4-cyano-3-nitro-benzoic acid (26.67 g). Total yield: 150 g + 26.67 g = 176.67 g; 74.5 % yield.
	With sodium dichromate; sulfuric acid; at 0 - 20℃; for 5h;	Example 229: 3-Chloro-benzo[b1thiophene-2-carboxylic acid [5-(4-chloro-phenyl- carbamoyl)-2-(2H-tetrazol-5-yl)phenvHamideTo a solution of 4-cyano-2-nitrotoluene (1 eq.) in 70% sulfuric acid at 0-10C sodium dichromate (1.5 eq.) was added portionwise under stirring, and stirring was continued at room temperature for 5 h. The reaction mixture was poured into crushed ice and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over Na2S04 and evaporated to dryness. The residue was dissolved in dichloromethane, treated with oxalyl chloride (4 eq.) and a catalytic amount of DMF. After stirring at room temperature for 4 h, the solvent was evaporated under vacuum, the residue re-dissolved in dichloromethane and evaporated again to dryness. The residue was dissolved in dichloromethane, treated with triethylamine (1.2 eq.) and 4-chloroaniline (1.2 eq.) and stirred at room temperature for 12 h. After evaporation of solvent under vacuum, the residue was partitioned between water and ethyl acetate. The organic layer was washed with diluted HCI and water, dried over Na2S04 and evaporated under vacuum. The residue was chromatographed over silica gel (15% ethyl acetate - hexane). The collected fractions were evaporated under vacuum to afford 0.38 eq. (38%) of 4'-chloro-4-cyano-3- nitrobenzoylaniline.This product was dissolved in MeOH and hydrogenated for 20 h in the presence of 10% platinum sulfide on carbon. After filtration of the catalyst through a Celite pad, the filtrate was concentrated under vacuum and the residue was dissolved in dry THF. 3-Chloro- thiophene-2-carbonyl chloride was added and the reaction mixture was refluxed for 14 h. The solvent was concentrated under vacuum and the residue was crystallized form ethyl acetate-hexane. The compound obtained (0.25 eq.) was dissolved in DMF and treated with sodium azide (1 eq.) and ammonium chloride (1 eq.) and the reaction mixture was stirred for 24 h at 100C. After cooling, the reaction mixture was diluted with ice cold water. The precipitated solid was collected by suction filtration, washed with water and dried to afford the title compound, mp >250C, in 12% overall yield.1 H-NMR (300 MHz, DMSO-cfe, 300K), delta ppm: 11.68 (s, 1 H, NH); 10.63 (s, 1 H, NH); 8.95 (s, 1 Ar-H); 8.21-7.44 (m, 10 Ar-H); MS: m/z = 507 [M-H]"

Reference： [1]Patent: WO2008/74427,2008,A1 .Location in patent: Page/Page column 52
[2]Patent: WO2012/59442,2012,A2 .Location in patent: Page/Page column 88-89
[3]Journal of Medicinal Chemistry,2018,vol. 61,p. 11250 - 11260

5
C₁₂H₉BrF₉N [ No CAS ]
[ 153775-42-9 ]
[ 1033996-84-7 ]

Yield	Reaction Conditions	Operation in experiment
		Similarly, as an alternative synthesis, N-[2-bromo-6-ethyl-4-(l,2,2,3,3,3-hexafluoro- l-trifluoromethyl-propyl)-phenyl]-4-cyano-3-nitro-benzamide was prepared from 4-cyano-3- nitro-benzoic acid (Example 15, 16 or 17).

Reference： [1]Patent: WO2008/74427,2008,A1 .Location in patent: Page/Page column 53

6
[ 1033997-01-1 ]
[ 153775-42-9 ]

Yield	Reaction Conditions	Operation in experiment
		4-Cyano-3-nitro-benzoic acid methyl ester (13.4 g, 61.6 mmol) was dissolved in tetrahydrofuran (74 ml) and aqueous sodium hydroxide (IM) (73.9 ml) was added. The reaction mixture was stirred at 25C for 4 hours. Then the reaction mixture was diluted with water (700 ml) and acidified with aqueous hydrochloric acid (IM). The mixture was extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. 4-Cyano-3-nitro-benzoic acid (12.0 g) was used in the next step without further purification. 1H-NMR (400 MHz, DMSO-d6): 13.00 (bs, IH), 8.79 (s, IH), 8.40 (d, IH), 8.30 (d, IH) ppm.

Reference： [1]Patent: WO2008/74427,2008,A1 .Location in patent: Page/Page column 51

7
[ 153775-42-9 ]
[ 1251424-01-7 ]

Yield	Reaction Conditions	Operation in experiment
	With oxalyl dichloride;N,N-dimethyl-formamide; In dichloromethane; at 20℃; for 1h;Reflux;	Example 1.3: 4-cyano-iV-r2,6-dibrorno-4-( 1 ,2,2,3 ,3 ,3-hexafluoro- 1 -trifluoromethylpropyl)- phenyll -3 -nitrobenzamide; To a suspension of <strong>[153775-42-9]4-cyano-3-nitrobenzoic acid</strong> (prepared as described in WO 2008/074427) (30 g, 156 mmol) in dichloromethane (150 ml) was added oxalyl chloride (15.88 ml, 187 mmol) at ambient temperature, followed by Lambda/,Lambda/-dimethylformamide ("DMF") (0.2 ml). The reaction mixture was stirred for 30 minutes at ambient temperature and then heated to reflux for 30 minutes. The reaction mixture was allowed to cool to ambient temperature, concentrated and the residue was suspended in tetrahydrofuran (150 ml). A solution of 2,6-dibromo-4-(l,2,2,3,3,3-hexafluoro-l-trifluoromethylpropyl)- phenylamine (Example 3.2) (55 g, 117.3 mmol) in a mixture of tetrahydrofuran (150 ml) and pyridine (12.57 ml, 156.4 mmol) was cooled to 00C and the solution of 4-cyano-3- nitrobenzoyl chloride was added. The reaction mixture was stirred at ambient temperature for 12 hours. Satruated aqueous sodium hydrogen carbonate (300 ml) was added and the organic phase extracted twice with ethyl acetate (2x 200 ml). The combined organic extracts were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane / ethyl acetate 4:1) to give 4-cyano-iV-[2,6- dibromo-4-(l, 2,2,3,3, 3-hexafluoro-l-trifluoromethylpropyl)phenyl]-3-nitrobenzamide (28 g, 37% yield). LC-MS (Method 2): RT = 2.24, [M-H]" = 642.
	With oxalyl dichloride; N,N-dimethyl-formamide; In dichloromethane; at 50℃; for 2h;	1.00 g (5.20 mmol) of <strong>[153775-42-9]4-cyano-3-nitrobenzoic acid</strong> was stirred in 25 mL of dichloromethane at room temperature. 0.04 mL (0.49 mmol) of DMF and 0.51 mL (5.82 mmol) of oxalyl chloride were added, and the mixture was stirred for additional 2 h at 50 C after the gas formation had stopped. After concentration, 1.02 g of raw material were obtained, which were used without further purification.

Reference： [1]Synthetic Communications,2010,vol. 40,p. 2897 - 2907
[2]Patent: WO2010/127926,2010,A1 .Location in patent: Page/Page column 29-30
[3]Patent: WO2014/147021,2014,A2 .Location in patent: Page/Page column 186

8
[ 1254318-28-9 ]
[ 153775-42-9 ]
[ 1254782-12-1 ]

Yield	Reaction Conditions	Operation in experiment
90%	With bis-(2-oxo-3-oxazolidinyl)phosphoryl chloride; triethylamine; In 1,2-dichloro-ethane; at 90℃; for 6h;	1. Preparation of intermediates; Example 1.1 : Lambda/-r2-bromo-6-chloro-4-(l,2,2,3,3,3-hexafluoro-l-trifluoromethylpropyl)- phenyll-4-cyano-3-nitrobenzamide; To a suspension of 2-bromo-6-chloro-4-( 1,2,2,3, 3, 3-hexafluoro-l -trifluoromethyl- propyl)phenylamine (Example 3.3) (70 g, 165 mmol) in 1 ,2-dichloroethane (660 ml) was added triethylamine (50.09 g, 495 mmol), followed by <strong>[153775-42-9]4-cyano-3-nitrobenzoic acid</strong> (made as in WO 2008/074427) (63.4 g, 330 mmol) and bis(2-oxo-3-oxazolidinyl)phosphonic chloride ("BOP-Cl") (84 g, 330 mmol). The reaction mixture was stirred at 900C for 6 hours. The reaction was quenched by addition of aqueous hydrochloric acid (IM) (500 ml) and the phases were separated. The organic phase was washed with saturated aqueous sodium hydrogen carbonate and brine. The aqueous phase was extracted twice with 1,2-dichloroethane. The combined organic extracts were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane / ethyl acetate 7:3) to give 7V-[2-bromo-6-chloro-4-(l,2,2,3,3,3-hexafluoro-l- trifluoromethylpropyl)phenyl]-4-cyano-3-nitrobenzamide (89 g, 90% yield). 1H NMR (400 MHz, CDCl3): 8.89 (s, IH), 8.40 (d, IH), 8.12 (d, IH), 7.88 (m, 2H), 7.72 (s, IH).

Reference： [1]Patent: WO2010/127926,2010,A1 .Location in patent: Page/Page column 27

9
2,6-dichloro-3-fluoro-4-(1,2,2,2-tetrafluoro-1-trifluoromethylethyl)-phenylamine [ No CAS ]
[ 153775-42-9 ]
4-cyano-N-[2,6-dichloro-3-fluoro-4-(1,2,2,2-tetrafluoro-1-trifluoromethylethyl)phenyl]-3-nitrobenzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
91%	With pyridine; bis-(2-oxo-3-oxazolidinyl)phosphoryl chloride; In dichloromethane; for 6h;Reflux;	Example 1.2: 4-cvano-N-r2,6-dichloro-3-fluoro-4-(l,2,2,2-tetrafluoro-l-trifluoromethyl- ethvQphenyl] -3 -nitrobenzamide; To a solution of 2,6-dichloro-3-fluoro-4-(l,2,2,2-tetrafluoro-l-trifluoromethylethyl)- phenylamine (Example 3.2) (3.48 g, 10 mmol) and <strong>[153775-42-9]4-cyano-3-nitrobenzoic acid</strong> (made as in WO 2008/074427) (3.84 g, 20 mmol) in dichloromethane (40 ml) was added pyridine (4.17 ml, 30 mmol) and bis(2-oxo-3-oxazolidinyl)phosphonic chloride ("BOP-Cl") (5.09 g, 20 mmol). The reaction mixture was heated to reflux for 6 hours. The reaction mixture was cooled to ambient temperature and quenched by addition of aqueous hydrochloric acid (IN) (50 ml). The mixture was then extracted three times with dichloromethane. The combined organic extracts were washed with saturated aqueous sodium hydrogen carbonate, dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane / ethyl acetate 7:3) to give 4-cyano-Lambda/-[2,6-dichloro-3-fluoro- 4-(l,2,2,2-tetrafluoro-l-trifluoromethylethyl)phenyl]-3-nitrobenzamide (4.76 g, 91% yield). LC-MS (Method 2): RT = 2.08, [M-H]" = 520.

Reference： [1]Patent: WO2010/127926,2010,A1 .Location in patent: Page/Page column 28

10
[ 12112-67-3 ]
[ 591-87-7 ]
[ 210169-54-3 ]
[ 153775-42-9 ]
[ 1208092-27-6 ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 15559 - 15561

11
[ 1321562-65-5 ]
[ 153775-42-9 ]
[ 1321562-68-8 ]

Yield	Reaction Conditions	Operation in experiment
62%	With bis-(2-oxo-3-oxazolidinyl)phosphoryl chloride; triethylamine; In 1,2-dichloro-ethane; at 110℃;	To a suspension of 2,6-dichloro-4-[l-(4-chlorophenyl)-l,2,2,2-tetrafluoroethyl]- phenylamine (Example IV, Step 1) (1.863 g, 5.0 mmol) in 1 ,2-dichloroethane (50 ml) was added triethylamine (3.49 mL, 25 mmol), followed by <strong>[153775-42-9]4-cyano-3-nitrobenzoic acid</strong> (Prepared as described in WO 2008/074427) (1.729 g, 9.0 mmol) and bis(2-oxo-3-oxazolidinyl)- phosphonic chloride ("BOP-C1") (3.82 g, 15.0 mmol). The reaction mixture was stirred overnight at 110C. The reaction was quenched by addition of aqueous sodium hydrogen carbonate and ethyl acetate. The phases were separated. The aqueous phase was extracted twice with ethyl acetate then, the organic phase were combinated. The organic phase was washed with aqueous sodium hydrogen carbonate (saturated), water and brine. The organic phase was dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (ethyl acetate / cyclohexane 1 :5 to 1 :4) to give 4-cyano-N-{2,6- dichloro-4-[l-(4-chlorophenyl)-l,2,2,2-tetrafluoroethyl]phenyl}-3-nitrobenzamide ( 1.70 g, 62 % yield). LC-MS (Method A, Negative) RT 2.14 (544, 546, 548 M-H+).

Reference： [1]Patent: WO2011/95462,2011,A1 .Location in patent: Page/Page column 68-69

12
chloro(1,5-cyclooctadiene)iridium(I) dimer [ No CAS ]
[ 591-87-7 ]
[ 185913-97-7 ]
[ 153775-42-9 ]
(NCC₆H₃(NO₂)COO)Ir(((C₆H₅)2PC₆H₂ClOCH₃)2)(CHCHCH₂OCOCH₃) [ No CAS ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 10028 - 10030

13
[ 153775-42-9 ]
[ 106-47-8 ]
4'-chloro-4-cyano-3-nitrobenzoylaniline [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%		Example 229: 3-Chloro-benzo[b1thiophene-2-carboxylic acid [5-(4-chloro-phenyl- carbamoyl)-2-(2H-tetrazol-5-yl)phenvHamideTo a solution of 4-cyano-2-nitrotoluene (1 eq.) in 70% sulfuric acid at 0-10C sodium dichromate (1.5 eq.) was added portionwise under stirring, and stirring was continued at room temperature for 5 h. The reaction mixture was poured into crushed ice and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over Na2S04 and evaporated to dryness. The residue was dissolved in dichloromethane, treated with oxalyl chloride (4 eq.) and a catalytic amount of DMF. After stirring at room temperature for 4 h, the solvent was evaporated under vacuum, the residue re-dissolved in dichloromethane and evaporated again to dryness. The residue was dissolved in dichloromethane, treated with triethylamine (1.2 eq.) and 4-chloroaniline (1.2 eq.) and stirred at room temperature for 12 h. After evaporation of solvent under vacuum, the residue was partitioned between water and ethyl acetate. The organic layer was washed with diluted HCI and water, dried over Na2S04 and evaporated under vacuum. The residue was chromatographed over silica gel (15% ethyl acetate - hexane). The collected fractions were evaporated under vacuum to afford 0.38 eq. (38%) of 4'-chloro-4-cyano-3- nitrobenzoylaniline.This product was dissolved in MeOH and hydrogenated for 20 h in the presence of 10% platinum sulfide on carbon. After filtration of the catalyst through a Celite pad, the filtrate was concentrated under vacuum and the residue was dissolved in dry THF. 3-Chloro- thiophene-2-carbonyl chloride was added and the reaction mixture was refluxed for 14 h. The solvent was concentrated under vacuum and the residue was crystallized form ethyl acetate-hexane. The compound obtained (0.25 eq.) was dissolved in DMF and treated with sodium azide (1 eq.) and ammonium chloride (1 eq.) and the reaction mixture was stirred for 24 h at 100C. After cooling, the reaction mixture was diluted with ice cold water. The precipitated solid was collected by suction filtration, washed with water and dried to afford the title compound, mp >250C, in 12% overall yield.1 H-NMR (300 MHz, DMSO-cfe, 300K), delta ppm: 11.68 (s, 1 H, NH); 10.63 (s, 1 H, NH); 8.95 (s, 1 Ar-H); 8.21-7.44 (m, 10 Ar-H); MS: m/z = 507 [M-H]"

Reference： [1]Patent: WO2012/59442,2012,A2 .Location in patent: Page/Page column 88-89

14
[ 12112-67-3 ]
[ 591-87-7 ]
[ 185913-97-7 ]
[ 153775-42-9 ]
(allyl)((Cl(MeO)(C₆H₂)PPh₂)2)Ir(O₂N(CN)(C₆H₂)COO) [ No CAS ]

Reference： [1]Chemical Communications,2012,vol. 48,p. 4692 - 4694

15
[ 153775-42-9 ]
[ 132631-86-8 ]
[ 1378870-42-8 ]

Yield	Reaction Conditions	Operation in experiment
50%	With bis-(2-oxo-3-oxazolidinyl)phosphoryl chloride; triethylamine; In dichloromethane; for 6h;Reflux;	Example 12: Preparation of 4-Cyano-N-(2-methyl-5-pentafluoroethyl-4-trifluoromethyl-2H- pyrazol-3 -yl)-3 -nitro-benzamideTo a solution of 2-methyl-5-pentafluoroethyl-4-trifluoromethyl-2H-pyrazol-3- ylamine (Example II) (5.0 g, 17.7 mmol) in dichloromethane (75 ml) was addedtriethylamine (10.72 g, 106.0 mmol). 4-Cyano-3-nitro-benzoic acid (3.73 g, 19.4 mmol, prepared according to WO2008074427) and bis(2-oxo-3-oxazolidinyl)phosphonic chloride ("BOP-C1") (13.49 g, 53.0 mmol) were added. The reaction mixture was heated to reflux for 6 hours. The reaction mixture was cooled to ambient temperature and concentrated. The residue was dissolved in dichloromethane and washed with aqueous hydrochloric acid (IN) and with aqueous sodium hydrogen carbonate (saturated). The organic extract was dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane / ethyl acetate 3 : 1) to give 4-cyano-N-(2-methyl-5- pentafluoroethyl-4-trifluoromethyl-2H-pyrazol-3-yl)-3-nitro-benzamide (4.060 mg, 50% yield). 1H-NMR (400 MHz, CDC13): 8.82 (s, 1H), 8.44 (sb, 1H), 8.31 (d, 12H), 8.06 (d, 1H), 3.82 (s, 3H) ppm

Reference： [1]Patent: WO2012/69366,2012,A1 .Location in patent: Page/Page column 98

16
(S)-((4,4’-bi-1,3-benzodioxole)-5,5’-diyl)bis(diphenylphosphine) [ No CAS ]
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
C₅₅H₃₉IrN₂O₄P₂ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2013,vol. 135,p. 4223 - 4226

17
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
(R)-segphos [ No CAS ]
[(R)-(+)-5,5'-bis(diphenylphosphino)-4,4'-bi-1,3-benzodioxole][4-cyano-3-nitrobenzenecarboxylato] [1,2,3-eta-2-propenyl Ir(III)] [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2014,vol. 136,p. 8911 - 8914

18
(R)-(+)-(4,4'-bi-1,3-benzodioxole)-5,5'-diylbis(di(3,5-dimethylphenyl)phosphine) [ No CAS ]
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
[ 1613234-46-0 ]

Reference： [1]Journal of the American Chemical Society,2014,vol. 136,p. 8911 - 8914

19
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
[ 76144-87-1 ]
[ 1346158-92-6 ]

Reference： [1]Journal of the American Chemical Society,2014,vol. 136,p. 8911 - 8914

20
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
[ 99646-28-3 ]
[ 1613234-48-2 ]

Reference： [1]Journal of the American Chemical Society,2014,vol. 136,p. 8911 - 8914

21
[ 153775-42-9 ]
4-cyano-3-nitro-N-(5-phenyl-1,3,4-thiadiazol-2-yl)benzamide [ No CAS ]

Reference： [1]Patent: WO2014/147021,2014,A2

22
[ 153775-42-9 ]
3-amino-4-cyano-N-(5-phenyl-1,3,4-thiadiazol-2-yl)benzamide [ No CAS ]

Reference： [1]Patent: WO2014/147021,2014,A2

23
[ 153775-42-9 ]
3-[(chloroacetyl)amino]-4-cyano-N-(5-phenyl-1,3,4-thiadiazol-2-yl)benzamide [ No CAS ]

Reference： [1]Patent: WO2014/147021,2014,A2

24
[ 153775-42-9 ]
4-cyano-3-[(4-methylpiperazin-1-yl)acetyl]amino}-N-(5-phenyl-1,3,4-thiadiazol-2-yl)benzamide [ No CAS ]

Reference： [1]Patent: WO2014/147021,2014,A2

25
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
[ 76144-87-1 ]
C₅₅H₃₈IrN₂O₄P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

26
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
[ 76144-87-1 ]
C₅₅H₃₈IrN₂O₄P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

27
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
(R)-segphos [ No CAS ]
C₄₉H₃₄IrN₂O₈P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

28
(S)-((4,4’-bi-1,3-benzodioxole)-5,5’-diyl)bis(diphenylphosphine) [ No CAS ]
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
C₄₉H₃₄IrN₂O₈P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

29
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
(+)-(R)-[2,3,2',3'-tetrahydro-5,5'-bi(1,4-benzodioxin)-6,6'-diyl]bis(diphenylphosphane) [ No CAS ]
C₅₁H₃₈IrN₂O₈P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

30
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
[ 503538-68-9 ]
C₅₁H₃₈IrN₂O₈P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

31
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
(R)-(+)-5,5’-dichloro-2,2’-bis(diphenylphosphino)-6,6’-dimethoxy-1,1’-biphenyl [ No CAS ]
C₄₉H₃₆Cl₂IrN₂O₆P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

32
[ 185913-98-8 ]
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
C₄₉H₃₆Cl₂IrN₂O₆P₂ [ No CAS ]

Reference： [1]Chemical Science,2015,vol. 6,p. 6747 - 6753

33
(S)-5,5 ′-bis[di(3,5-xylyl)phosphino]-4,4 ′-bi-1,3-benzodioxole [ No CAS ]
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
C₄₉H₃₅IrN₂O₈P₂ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2016,vol. 138,p. 3655 - 3658

34
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
[ 99646-28-3 ]
[ 1613234-48-2 ]

Reference： [1]Chemistry - A European Journal,2017,vol. 23,p. 2557 - 2559

35
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
(S)-(-)-(6,6’-dimethoxybiphenyl-2,2’-diyl)bis(diphenylphosphine) [ No CAS ]
C₄₉H₃₉ClIrN₂O₆P₂ [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2018,vol. 57,p. 1390 - 1393
Angew. Chem.,2018,vol. 130,p. 1404 - 1407,4

36
[ 185913-98-8 ]
[ 12112-67-3 ]
[ 591-87-7 ]
[ 153775-42-9 ]
C₄₉H₃₆Cl₂IrN₂O₆P₂ [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2018,vol. 140,p. 9392 - 9395

37
[ 153775-42-9 ]
[ 89939-36-6 ]