[ CAS No. 7697-29-2 ]

Name: 7697-29-2|4-Chloro-3-methylbenzoic acid|97%
Brand: Ambeed
SKU: A174705
Price: 5.0 USD
Availability: InStock
Rating: 99 (26 reviews)

{[proInfo.proName]} ,{[proInfo.pro_purity]}

Cat. No.: {[proInfo.prAm]}

DV 2D 3D

3d Animation Molecule Structure of 7697-29-2

Structure of 7697-29-2 * Storage: {[proInfo.prStorage]}

Cart0 Add to My Favorites Bulk Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 100K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 7697-29-2 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 7697-29-2 ]

SDS Specification

Alternatived Products of [ 7697-29-2 ]

Product Details of [ 7697-29-2 ]

CAS No. :	7697-29-2	MDL No. :	MFCD00045853
Formula :	C₈H₇ClO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	MRUKIIWRMSYKML-UHFFFAOYSA-N
M.W :	170.59	Pubchem ID :	282989
Synonyms :

Calculated chemistry of [ 7697-29-2 ]

Physicochemical Properties

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.12
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	1.0
Molar Refractivity :	43.38
TPSA :	37.3 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.3 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.54
Log Po/w (XLOGP3) :	2.87
Log Po/w (WLOGP) :	2.35
Log Po/w (MLOGP) :	2.52
Log Po/w (SILICOS-IT) :	2.31
Consensus Log Po/w :	2.32

Druglikeness

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

Water Solubility

Log S (ESOL) :	-3.04
Solubility :	0.154 mg/ml ; 0.000905 mol/l
Class :	Soluble
Log S (Ali) :	-3.31
Solubility :	0.083 mg/ml ; 0.000487 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.77
Solubility :	0.29 mg/ml ; 0.0017 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.2

Safety of [ 7697-29-2 ]

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 [ 7697-29-2 ]

* 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 [ 7697-29-2 ]
Downstream synthetic route of [ 7697-29-2 ]

[ 7697-29-2 ] Synthesis Path-Upstream 1~24

1
[ 7697-29-2 ]
[ 917-54-4 ]
[ 37074-39-8 ]

Reference： [1] Patent: US2010/168079, 2010, A1, . Location in patent: Page/Page column 20

2
[ 95-66-9 ]
[ 7697-29-2 ]

Reference： [1] DRP/DRBP Org.Chem.,
[2] Journal of Chemical Education, 1938, vol. 15, p. 217
[3] Journal of Organic Chemistry, 1961, vol. 26, p. 762 - 765
[4] Journal of Organic Chemistry, 1967, vol. 32, p. 134 - 136
[5] Journal of the American Chemical Society, 1959, vol. 81, p. 5641,5644

3
[ 74-11-3 ]
[ 74-88-4 ]
[ 7697-29-2 ]
[ 7499-07-2 ]
[ 58231-16-6 ]

Reference： [1] Journal of Organic Chemistry, 2005, vol. 70, # 4, p. 1501 - 1504

4
[ 103038-95-5 ]
[ 7697-29-2 ]

Reference： [1] Journal of the American Chemical Society, 1950, vol. 72, p. 4314

5
[ 101349-71-7 ]
[ 7697-29-2 ]

Reference： [1] Journal of the American Chemical Society, 1959, vol. 81, p. 5641,5644

6
[ 117890-58-1 ]
[ 7697-29-2 ]

Reference： [1] Journal of the American Chemical Society, 1959, vol. 81, p. 5641,5644

7
[ 598-30-1 ]
[ 74-11-3 ]
[ 74-88-4 ]
[ 7697-29-2 ]
[ 90269-48-0 ]
[ 7499-07-2 ]

Reference： [1] Journal of Organic Chemistry, 2005, vol. 70, # 4, p. 1501 - 1504

8
[ 38227-87-1 ]
[ 74-11-3 ]
[ 74-88-4 ]
[ 7697-29-2 ]
[ 58231-16-6 ]

Reference： [1] Journal of Organic Chemistry, 2005, vol. 70, # 4, p. 1501 - 1504

9
[ 95-68-1 ]
[ 7697-29-2 ]

Reference： [1] Journal of Organic Chemistry, 1967, vol. 32, p. 134 - 136

10
[ 84797-75-1 ]
[ 7697-29-2 ]
[ 93126-03-5 ]
[ 84658-93-5 ]

Reference： [1] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1984, vol. 23, # 9, p. 815 - 817
[2] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1984, vol. 23, # 9, p. 815 - 817
[3] Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 1984, vol. 23, # 9, p. 815 - 817

11
[ 42044-84-8 ]
[ 7697-29-2 ]

Reference： [1] Australian Journal of Chemistry, 1973, vol. 26, p. 1337 - 1351

12
[ 15146-01-7 ]
[ 7697-29-2 ]

Reference： [1] Acta Academiae Aboensis, Series B: Mathematica et Physica, 1946, vol. 15, # 5, p. 20

13
[ 2486-70-6 ]
[ 7697-29-2 ]

Reference： [1] Justus Liebigs Annalen der Chemie, 1867, vol. 144, p. 182

14
[ 67-66-3 ]
[ 93-51-6 ]
[ 7697-29-2 ]

Reference： [1] Australian Journal of Chemistry, 1973, vol. 26, p. 1337 - 1351

15
[ 3113-71-1 ]
[ 7697-29-2 ]

Reference： [1] Justus Liebigs Annalen der Chemie, 1867, vol. 144, p. 182

16
[ 535-77-3 ]
[ 7697-29-2 ]

Reference： [1] Acta Academiae Aboensis, Series B: Mathematica et Physica, 1946, vol. 15, # 5, p. 20

17
[ 37074-39-8 ]
[ 7697-29-2 ]
[ 2845-85-4 ]

Reference： [1] Journal fuer Praktische Chemie (Leipzig), 1891, vol. <2> 43, p. 359

18
[ 19482-16-7 ]
[ 7697-29-2 ]

Reference： [1] Chemische Berichte, 1888, vol. 21, p. 1098

19
[ 89032-08-6 ]
[ 7697-37-2 ]
[ 7697-29-2 ]

Reference： [1] Bulletin de la Societe Chimique de France, 1921, vol. <4> 29, p. 290,291, 292

20
[ 337507-81-0 ]
[ 7697-37-2 ]
[ 7697-29-2 ]

Reference： [1] Chemische Berichte, 1927, vol. 60, p. 2281

21
[ 37074-39-8 ]
[ 7697-29-2 ]
[ 2845-85-4 ]

Reference： [1] Journal fuer Praktische Chemie (Leipzig), 1891, vol. <2> 43, p. 359

22
[ 7697-29-2 ]
[ 74-88-4 ]
[ 91367-05-4 ]

Yield	Reaction Conditions	Operation in experiment
93%	With caesium carbonate In N,N-dimethyl-formamide at 20 - 23℃;	EXAMPLES Preparation 1Methyl 4-chloro-3-methylbenzoateTo a solution of 4~chloro-3-methylbenzoic acid (25 g) in DMF (550 ml) under a dry atmosphere was added portion wise 50 g of caesium carbonate and then slowly, 10,95 ml of methyl iodide. Temperature rose from 20⁰C to 23 ⁰C. The reaction mixture was stirred at room temperature overnight. The mixture was cooled to 10 ⁰C and then 800 ml of an aqueous solution of NaHCO₃ (2percent) and 600 ml of ethyl acetate were successively added. The aqueous layer was separated, extracted again with 400 ml of ethyl acetate. The .bul. combined organic layers were washed successively with 2x250 ml of an aqueous solution of NaHCO₃ (2percent), then 2x250 ml of aqueous solution of NaCl (2percent), dried over Na₂SO₄ and concentrated in vacuum. The residue was purified by distillation to afford 25.31 g of a clear yellow liquid (b.p.: 78 °C/0.08 mbar). Yield: 93percentT.L.C.: Silica gel, eluents: cyclohexane-ethyl acetate 75/25

Reference： [1] Patent: WO2006/79857, 2006, A1, . Location in patent: Page/Page column 6
[2] Patent: US2010/69384, 2010, A1, . Location in patent: Page/Page column 9-10

23
[ 67-56-1 ]
[ 7697-29-2 ]
[ 91367-05-4 ]

Yield	Reaction Conditions	Operation in experiment
90.1%	for 8 h; Reflux	4-chloro-3-methyl benzoic acid 5.2 g (0.03 mol), CH₃OH 40 mLand H₂SO₄ 1 mL were refluxed for 8 h. After completion of the reaction as indicated by TLC. The solvent was evaporated under reduced pressure and the residue was dissolved in ethyl acetate 100 mL. Then the liquid was washed with saturated Na₂CO₃, waterand saturated NaCl successively. The organic layer was dried over anhydrous Na₂SO₄ and concentrated. The residue was dried to afford X13 5.1 g (90.1 percent), mp: 76-78 °C.

Reference： [1] European Journal of Medicinal Chemistry, 2015, vol. 90, p. 170 - 183

24
[ 7697-29-2 ]
[ 1044920-98-0 ]

Reference： [1] European Journal of Medicinal Chemistry, 2015, vol. 90, p. 170 - 183

[ 7697-29-2 ] Synthesis Path-Downstream 1~69

1
[ 64-17-5 ]
[ 7697-29-2 ]
ethyl 4-chloro-3-methylbenzoate [ No CAS ]

Reference： [1]Justus Liebigs Annalen der Chemie,1867,vol. 144,p. 267

2
[ 95-66-9 ]
[ 7697-29-2 ]

Reference： [1]Patent: DE767366,1940,
DRP/DRBP Org.Chem.,
[2]Journal of Chemical Education,1938,vol. 15,p. 217
[3]Journal of Organic Chemistry,1961,vol. 26,p. 762 - 765
[4]Journal of Organic Chemistry,1967,vol. 32,p. 134 - 136
[5]Journal of the American Chemical Society,1959,vol. 81,p. 5641,5644

3
[ 7697-29-2 ]
[ 21900-24-3 ]

Yield	Reaction Conditions	Operation in experiment
	With thionyl chloride;N,N-dimethyl-formamide; In dichloromethane; for 1h;Reflux;	Example EX5; (S)-2-({3'-[1-(4-Chloro-3-methyl-phenyl)-propylamino]-3,5-dimethyl-biphenyl-4-carbonyl}-amino)-propionic acid; (1) 1-(4-Chloro-3-methyl-phenyl)-propan-1-one, INT8; To a solution <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> (8.31 g, 48.7 mmol) in DCM (50 mL) was added DMF (175 muL) and thionyl chloride (35.5 mL, 487 mmol) and the resulting mixture was refluxed for 1 hour. After cooling down, the mixture was evaporated to dryness under reduced pressure and taken up in THF (50 mL). The resulting solution was cooled down to 0 C. and triethylamine (13.5 mL, 97 mmol) was added followed by N,O-dimethylhydroxylamine hydrochloride (5.7 g, 58.4 mmol) and the resulting mixture was stirred at room temperature overnight. The crude was diluted in dichloromethane and washed with 1M KHSO4, saturated aqueous sodium bicarbonate and brine, dried over sodium sulfate and concentrated. The resulting crude Weinreb amide (10.4 g, 48.7 mmol) was taken up in THF (440 mL) and cooled down to 0 C. under an argon atmosphere. EtMgBr (1N in TBME, 97 mmol) was then slowly added and the resulting mixture was stirred for 2 hours at 0 C. The reaction was then quenched with a saturated ammonium chloride solution. The THF was evaporated and the product was then extracted with EtOAc and washed with brine. The residue was purified by chromatography on silica gel (cyclohexane/EtOAc) to give INT8 as a yellow solid.1H-NMR (CDCl3): delta (ppm) 7.93 (d, 1H), 7.76 (dd, 1H), 7.55 (d, 1H), 3.01 (q, 2H), 2.39 (s, 3H) 1.06 (t, 3H).
	With thionyl chloride; for 0.5h;Reflux;	<strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> (253 mg, 1.48 mmol) was suspended in thionyl chloride (3000 mg, 30 mmol) and heated to reflux for 30 minutes. The solution was concentrated in vacuo in the presence of dichloromethane to give a residue. The residue was dissolved in 1 mL dichloromethane and added to a solution of diisopropyl ethylamine (890 mg, 6.9 mmol) and Preparation I-1A-1e (204 mg, 0.83 mmol) in 8 mL dichloromethane. The reaction was stirred for 10 minutes. The reaction was partitioned between dichloromethane and saturated, aqueous sodium bicarbonate. The organic phase as separated and then washed with saturated, aqueous sodium chloride. The organic layer was dried over sodium sulfate and concentrated in vacuo to give an oil. The oil was purified by flash chromatography using 15-100% ethyl acetate in heptane as eluent to afford the title compound as a white foam (153 mg, 46%): +ESI MS (M+H) 400.2; 1H NMR (400 MHz, CDCl3) delta ppm 7.32-7.40 (m, 2H), 7.28 (s, 1H), 7.11-7.17 (m, 1H), 5.31-5.45 (m, 1H), 3.74 (br. s., 2H), 3.42 (br. s., 2H), 2.80 (s, 2H), 2.59 (s, 2H), 2.39 (s, 3H), 1.49-1.84 (m, 4H), 1.46 (d, J=6.63 Hz, 6H).
	With oxalyl dichloride; N,N-dimethyl-formamide; In dichloromethane; at 20℃; for 0.5h;	Oxalyl chloride (2 M in DCM, 0.16 mL, 0.32 mmol) is added slowly to a mixture of <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> (27 mg, 0.16 mmol) in DCM (1 mL). DMF (1 drop) is added and the mixture is stirred 30 minutes at ambient temperature and concentrated under reduced pressure. The residue is mixed with pyridine (0.5 mL), compound 15a5 (30 mg, 0.08 mmol) is added, and the mixture is stirred at 60 C. overnight. Aqueous NaOH (10 N, 0.096 mL, 0.96 mmol) and water (0.2 mL) are added and the mixture is stirred overnight at ambient temperature, then diluted with EtOAc and washed with 1N HCl and brine. The organic phase is dried with MgSO4, filtered and concentrated under reduced pressure. Purification by preparative HPLC affords compound 2196 (Table 2).

Reference： [1]Bulletin des Societes Chimiques Belges,1968,vol. 77,p. 273 - 285
[2]Farmaco, Edizione Scientifica,1983,vol. 28,p. 187 - 198
[3]Journal of Medicinal Chemistry,2009,vol. 52,p. 1639 - 1647
[4]Patent: US2010/168079,2010,A1 .Location in patent: Page/Page column 22
[5]Patent: US2011/111046,2011,A1 .Location in patent: Page/Page column 30
[6]Organic Letters,2017,vol. 19,p. 2746 - 2749
[7]Patent: US2008/45516,2008,A1 .Location in patent: Page/Page column 50

4
[ 15146-01-7 ]
[ 7697-29-2 ]

Reference： [1]Acta Academiae Aboensis, Series B: Mathematica et Physica,1946,vol. 15,p. 20

5
[ 19482-16-7 ]
[ 7697-29-2 ]

Reference： [1]Chemische Berichte,1888,vol. 21,p. 1098

6
[ 2486-70-6 ]
[ 7697-29-2 ]

Reference： [1]Justus Liebigs Annalen der Chemie,1867,vol. 144,p. 182

7
[ 103038-95-5 ]
[ 7697-29-2 ]

Reference： [1]Journal of the American Chemical Society,1950,vol. 72,p. 4314

8
[ 7697-29-2 ]
[ 131271-19-7 ]

Yield	Reaction Conditions	Operation in experiment
99%	With borane-THF; In tetrahydrofuran; at 20℃; for 16h;	A solution of borane in tetrahydrofuran (1M, 5.9 ml) was added dropwise to a solution of compound3-1 (1 g, 5.85 mmol) in tetrahydrofuran, and the reaction solution was stirred at room temperature for 16 h. To the reactionsolution was added methanol to quench the reaction, and concentrated under reduced pressure. The crude product waspurified by column chromatography (PE: EA = 7: 3) to give compound 4-1 (910 mg) as a pale yellow solid, purity 100%,yield 99%, MS m/z(ESI): N/A.

Reference： [1]Patent: EP3412653,2018,A1 .Location in patent: Paragraph 0251; 0252
[2]Macromolecules,2011,vol. 44,p. 512 - 520
[3]Journal of Medicinal Chemistry,1989,vol. 32,p. 1757 - 1763

9
[ 84797-75-1 ]
[ 7697-29-2 ]
[ 93126-03-5 ]
[ 84658-93-5 ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,1984,vol. 23,p. 815 - 817
[2]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,1984,vol. 23,p. 815 - 817
[3]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,1984,vol. 23,p. 815 - 817

10
[ 67-66-3 ]
[ 93-51-6 ]
[ 7697-29-2 ]

Reference： [1]Australian Journal of Chemistry,1973,vol. 26,p. 1337 - 1351

11
[ 42044-84-8 ]
[ 7697-29-2 ]

Reference： [1]Australian Journal of Chemistry,1973,vol. 26,p. 1337 - 1351

12
[ 7697-29-2 ]
[ 445479-01-6 ]
C₁₈H₂₅ClN₂O₃ [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2007,vol. 17,p. 4419 - 4427

13
[ 7697-29-2 ]
[ 85588-36-9 ]

Reference： [1]Farmaco, Edizione Scientifica,1983,vol. 28,p. 187 - 198
[2]Angewandte Chemie - International Edition,2019,vol. 58,p. 5085 - 5089
Angew. Chem.,2019,vol. 131,p. 5139 - 5143,5

14
[ 7697-29-2 ]
[ 85588-39-2 ]

Reference： [1]Farmaco, Edizione Scientifica,1983,vol. 28,p. 187 - 198

15
[ 7697-29-2 ]
[ 85588-42-7 ]

Reference： [1]Farmaco, Edizione Scientifica,1983,vol. 28,p. 187 - 198

16
[ 7697-29-2 ]
[ 85588-45-0 ]

Reference： [1]Farmaco, Edizione Scientifica,1983,vol. 28,p. 187 - 198

17
[ 7697-29-2 ]
2-(6-chloro-3-benzoylphenyl)propionic acid [ No CAS ]

Reference： [1]Farmaco, Edizione Scientifica,1983,vol. 28,p. 187 - 198

18
[ 7697-29-2 ]
[ 117890-58-1 ]

Reference： [1]Journal of Medicinal Chemistry,1989,vol. 32,p. 1757 - 1763
[2]Macromolecules,2011,vol. 44,p. 512 - 520

19
[ 7697-29-2 ]
6-Chloro-7-(4-chloro-3-methyl-benzyl)-2-trifluoromethyl-7H-purine [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1989,vol. 32,p. 1757 - 1763

20
[ 7697-29-2 ]
[ 122488-84-0 ]

Reference： [1]Journal of Medicinal Chemistry,1989,vol. 32,p. 1757 - 1763

21
[ 7697-29-2 ]
[9-(4-Chloro-3-methyl-benzyl)-2-trifluoromethyl-9H-purin-6-yl]-dimethyl-amine [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,1989,vol. 32,p. 1757 - 1763

22
[ 3113-71-1 ]
[ 7697-29-2 ]

Reference： [1]Justus Liebigs Annalen der Chemie,1867,vol. 144,p. 182

23
[ 7697-29-2 ]
[ 106272-03-1 ]

Reference： [1]Journal of the American Chemical Society,1959,vol. 81,p. 5641,5644

24
[ 7697-29-2 ]
[ 106272-02-0 ]

Reference： [1]Journal of the American Chemical Society,1959,vol. 81,p. 5641,5644

25
[ 117890-58-1 ]
[ 7697-29-2 ]

Reference： [1]Journal of the American Chemical Society,1959,vol. 81,p. 5641,5644

26
[ 535-77-3 ]
[ 7697-29-2 ]

Reference： [1]Acta Academiae Aboensis, Series B: Mathematica et Physica,1946,vol. 15,p. 20

27
[ 7697-29-2 ]
4-Chlor-3,4'-dimethyl-benzophenon [ No CAS ]

Reference： [1]Bulletin des Societes Chimiques Belges,1968,vol. 77,p. 273 - 285

28
[ 95-68-1 ]
[ 7697-29-2 ]

Reference： [1]Journal of Organic Chemistry,1967,vol. 32,p. 134 - 136

29
[ 7697-29-2 ]
[ 75-03-6 ]
ethyl 4-chloro-3-methylbenzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
98%	With potassium carbonate; In DMF (N,N-dimethyl-formamide); at 20℃; for 18h;	Preparation 109; 4-Chloro-3-methvl-benzoic acid ethyl ester; Ethyl iodide (1.4mL, 17. 6mmol) and potassium carbonate (6g, 44mmol) were added to a solution of <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> (1.5g, 8. 8mmol) in N, N- dimethylformamide (15mL) and the mixture was stirred for 18 hours at room temperature. The reaction mixture was then diluted with water and extracted with ethyl acetate. The organic solution was dried over magnesium sulfate and concentrated in vacuo to afford the title compound in 98% yield, 1.7g. 'H NMR (400MHz, Ceci3) d : 1.40 (t, 3H), 2.42 (s, 3H), 4.36 (q, 2H), 7.38 (d, 1H), 7.78 (dd, 1H), 7.91 (d, 1H)

Reference： [1]Patent: WO2005/82866,2005,A2 .Location in patent: Page/Page column 100

30
[ 7697-29-2 ]
[ 74-88-4 ]
[ 91367-05-4 ]

Yield	Reaction Conditions	Operation in experiment
93%	With caesium carbonate; In N,N-dimethyl-formamide; at 20 - 23℃;	EXAMPLES Preparation 1Methyl 4-chloro-3-methylbenzoateTo a solution of 4~chloro-3-methylbenzoic acid (25 g) in DMF (550 ml) under a dry atmosphere was added portion wise 50 g of caesium carbonate and then slowly, 10,95 ml of methyl iodide. Temperature rose from 200C to 23 0C. The reaction mixture was stirred at room temperature overnight. The mixture was cooled to 10 0C and then 800 ml of an aqueous solution of NaHCO3 (2%) and 600 ml of ethyl acetate were successively added. The aqueous layer was separated, extracted again with 400 ml of ethyl acetate. The ? combined organic layers were washed successively with 2x250 ml of an aqueous solution of NaHCO3 (2%), then 2x250 ml of aqueous solution of NaCl (2%), dried over Na2SO4 and concentrated in vacuum. The residue was purified by distillation to afford 25.31 g of a clear yellow liquid (b.p.: 78 C/0.08 mbar). Yield: 93%T.L.C.: Silica gel, eluents: cyclohexane-ethyl acetate 75/25
	With caesium carbonate; In N,N-dimethyl-formamide; at 20℃;	Add 50 g of caesium carbonate and 10.95 ml of methyl iodide dropwise to a solution of 25 g of <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> in 550 ml of dimethylformamide. Stir the reaction mixture at room temperature for 16 h, then add 800 ml of an aqueous solution of sodium bicarbonate, and extract with ethyl acetate. After decanting, extract the aqueous phase again with 400 ml of ethyl acetate. Wash the combined organic phases with 250 ml of an aqueous solution of sodium bicarbonate and then with 250 ml of an aqueous solution of sodium chloride. Dry the organic phase obtained over sodium sulphate and concentrate at reduced pressure. The desired product is purified by distillation at reduced pressure, and an oil is obtained.b.p.=78 C./0.08 mbar

Reference： [1]Patent: WO2006/79857,2006,A1 .Location in patent: Page/Page column 6
[2]Patent: US2010/69384,2010,A1 .Location in patent: Page/Page column 9-10

31
[ 79-37-8 ]
[ 7697-29-2 ]
[ 21900-24-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In dichloromethane; N,N-dimethyl-formamide;	A. 4-Chloro-3-methyl-benzoyl chloride. To a suspension of 52.55 g (0.31 mol) of <strong>[7697-29-2]4-chloro-3-methyl-benzoic acid</strong> in CH2Cl2 (1.2 L) with DMF (1 mL) at 0 C. under N2 with an outlet sparging through 2.5 N sodium hydroxide was added 29.56 mL (0.339 mol) of oxalyl chloride. The mixture was allowed to warm to room temperature over a 3 h period. The reaction mixture was concentrated and taken forward crude.

Reference： [1]Patent: US2003/69240,2003,A1

32
[ 7697-29-2 ]
[ 108-98-5 ]
3-methyl-4-phenylthiobenzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide; sodium hydroxide; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; N,N-dimethyl acetamide; nitrogen; water; benzene;	Reference Example 14 Dissolving 1.368 g of potassium hydroxide in 20 ml of N,N-dimethylacetamide in heated state, and 1.16 ml of thiophenol was added in a nitrogen stream. In succession, <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> was added, and the mixture was refluxed for 2 days under nitrogen atmosphere. After reaction, the reaction mixture was cooled, and poured into about 100 ml of ice water, and washed in 50 ml of benzene, and the water layer was separated. The benzene layer was further extracted with 50 ml of aqueous solution of 5% sodium hydroxide, and the extract and water layer were combined and the pH was adjusted to 2 to 3 with hydrochloric acid, and the precipitate was filtered, washed in water, dried, and 3-methyl-4-phenylthiobenzoic acid was obtained (1.55 g).
	With potassium hydroxide; In N,N-dimethyl acetamide;	REFERENCE EXAMPLE 7 Potassium hydroxide (1.368 g) is dissolved in N,N-dimethylacetamide (20 ml) with heating, and thereto is added thiophenol (1.16 ml) under nitrogen atmosphere. To the mixture is added <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong>, and the mixture is refluxed under nitrogen atmosphere for 2 days. After the reaction is completed, the reaction mixture is cooled and poured into ice water (about 100 ml), and the mixture is washed with benzene (50 ml) and the aqueous layer is separated. The benzene layer is further extracted with 5% aqueous sodium hydroxide solution (50 ml), and the extract is combined with the above aqueous layer and adjusted to pH 2-3 with hydrochloric acid. The resulting precipitate is separated by filtration, washed with water, and dried to give 3-methyl-4-phenylthiobenzoic acid (1.55 g).

Reference： [1]Patent: US5420128,1995,A
[2]Patent: US4824834,1989,A

33
[ 159737-81-2 ]
[ 7697-29-2 ]
trans-O-(4-chloro-3-methylbenzoyl)-4-(4-dimethylaminomethylphenyl)-cyclohexanol [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With 1,1'-carbonyldiimidazole;	(8) trans-O-(4-chloro-3-methylbenzoyl)-4-(4-dimethylaminomethylphenyl)-cyclohexanol from trans-4-(4-dimethylaminomethylphenyl)-cyclohexanol and <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong>/N,N'-carbonyldiimidazole. White crystals. Melting point: 100-102 C.

Reference： [1]Patent: US5726205,1998,A

34
[ 1132683-03-4 ]
[ 7697-29-2 ]
[ 921211-96-3 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; HATU; In dichloromethane; for 1h;	Step 1: (S)-(2-Azidomethyl-morpholin-4-yl)-(4-chloro-3-methyl-phenyl)-methanone: 2-Azidomethyl-morpholine (prepared following the method of preparation 1 as far as step 6 immediately prior to addition of the aldehyde and triethylamine; 0.63 g), <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> (0.756 g) and triethylamine (0.897 g, 1.281 ml) were dissolved in dichloromethane (6 mL) and HATU (1.853 g) was added. The reaction mixture was stirred for Ih. The mixture was poured into water and extracted with dichloromethane thrice. The combined organic layers were washed with brine, dried and the solvents were removed to give the subtitle compound (2 g). Retention time (standard) 2.04 MS (ES+ve) 295/297 [M+H]+

Reference： [1]Patent: WO2007/11292,2007,A1 .Location in patent: Page/Page column 34

35
[ 7697-29-2 ]
[ 917-54-4 ]
[ 37074-39-8 ]

Yield	Reaction Conditions	Operation in experiment
	In tetrahydrofuran; diethyl ether; at 0 - 20℃;	Example EX2; (S)-2-({3'-[1-(4-Chloro-3-methyl-phenyl)-ethylamino]-3,5-dimethyl-biphenyl-4-carbonyl}-amino)-propionic acid; (1) 1-(4-Chloro-3-methyl-phenyl)-ethanone, INT4; To a solution <strong>[7697-29-2]4-chloro-3-methylbenzoic acid</strong> (38.4 g, 200 mmol) in THF (2 L) at 0 C. was added dropwise MeLi (500 mL, 1.6 M in ether) and the resulting mixture was stirred at room temperature for 4 hours. The mixture was then poured slowly on cooled 2N HCl (830 mL), the organic layer was separated and the aqueous layer was extracted with EtOAc (300 mL). The combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated. The residue was purified by chromatography on silica gel (cyclohexane/EtOAc) to give INT4 as a pale yellow liquid.LC/MS Method 1: MS (ESI): 169 [M+H]+, rt=1.23 min. 1H-NMR (CDCl3): delta (ppm) 7.82 (d, 1H), 7.71 (dd, 1H), 7.43 (d, 1H), 2.58 (s, 3H), 2.43 (s, 3H).

Reference： [1]Patent: US2010/168079,2010,A1 .Location in patent: Page/Page column 20

36
[ 7697-29-2 ]
[ 1301215-14-4 ]

Reference： [1]Patent: US2011/111046,2011,A1

37
[ 7697-29-2 ]
[ 1262727-25-2 ]

Reference： [1]Macromolecules,2011,vol. 44,p. 512 - 520

38
[ 7697-29-2 ]
[ 1416358-64-9 ]