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Chemical Structure| 873-73-4 Chemical Structure| 873-73-4

Structure of 873-73-4

Chemical Structure| 873-73-4

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Gruszczyński, Marcin ; Lewandowski, Dariusz ; Kuciński, Krzysztof ; Kubicki, Maciej ; Hreczycho, Grzegorz ;

Abstract: Nickel catalysis provides opportunities to modulate reaction pathways through changes in the coordination environment, yet strategies to deliberately redirect nickel reactivity remain limited. Here we show that ligand exchange at nickel allows a single catalytic system to produce different products from the same alkyne substrates. Aminophosphine-supported nickel catalysts promote selective hydroboration in the presence of pinacolborane, which functions both as a boron source and a reaction activator. The addition of forms a distinct ligand-coordinated nickel species that suppresses hydroboration and directs the reaction toward enyne formation. Our further studies identify coordination as a key step that directs the catalytic cycle, illustrating how simple additives can influence reaction outcomes. These results offer a straightforward strategy to access divergent reactivity in nickel catalysis and provide insight into the factors controlling catalytic pathway selection.

Keywords: Alkynes ; Nickel catalysis ; Ligand effects ; Hydroboration ; Enynes

Purchased from AmBeed: ; ; ; ;

Krzysztof Kuciński ; Grzegorz Hreczycho ;

Abstract: Commercially available and inexpensive potassium bis(trimethylsilyl)amide (KHMDS) serves as an efficient transition metal-free catalyst for the catalytic sp C−H silylation of several terminal alkynes including two pharmaceuticals. Overall, the presented system allows the synthesis of various attractive silylacetylenes under mild conditions, making this approach an environmentally benign and sustainable alternative to existing synthetic solutions.

Alternative Products

Product Details of [ 873-73-4 ]

CAS No. :873-73-4
Formula : C8H5Cl
M.W : 136.58
SMILES Code : C#CC1=CC=C(Cl)C=C1
English Name :1-Chloro-4-ethynylbenzene
MDL No. :MFCD00191917
InChI Key :LFZJRTMTKGYJRS-UHFFFAOYSA-N
Pubchem ID :70118

Safety of [ 873-73-4 ]

Computational Chemistry of [ 873-73-4 ] Show Less

Physicochemical Properties

Num. heavy atoms 9
Num. arom. heavy atoms 6
Fraction Csp3 0.0
Num. rotatable bonds 0
Num. H-bond acceptors 0.0
Num. H-bond donors 0.0
Molar Refractivity 39.39
TPSA ?

Topological Polar Surface Area: Calculated from
Ertl P. et al. 2000 J. Med. Chem.

0.0 Ų

Lipophilicity

Log Po/w (iLOGP)?

iLOGP: in-house physics-based method implemented from
Daina A et al. 2014 J. Chem. Inf. Model.

2.3
Log Po/w (XLOGP3)?

XLOGP3: Atomistic and knowledge-based method calculated by
XLOGP program, version 3.2.2, courtesy of CCBG, Shanghai Institute of Organic Chemistry

3.21
Log Po/w (WLOGP)?

WLOGP: Atomistic method implemented from
Wildman SA and Crippen GM. 1999 J. Chem. Inf. Model.

2.4
Log Po/w (MLOGP)?

MLOGP: Topological method implemented from
Moriguchi I. et al. 1992 Chem. Pharm. Bull.
Moriguchi I. et al. 1994 Chem. Pharm. Bull.
Lipinski PA. et al. 2001 Adv. Drug. Deliv. Rev.

3.44
Log Po/w (SILICOS-IT)?

SILICOS-IT: Hybrid fragmental/topological method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

3.11
Consensus Log Po/w?

Consensus Log Po/w: Average of all five predictions

2.89

Water Solubility

Log S (ESOL):?

ESOL: Topological method implemented from
Delaney JS. 2004 J. Chem. Inf. Model.

-3.2
Solubility 0.0857 mg/ml ; 0.000627 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (Ali)?

Ali: Topological method implemented from
Ali J. et al. 2012 J. Chem. Inf. Model.

-2.88
Solubility 0.179 mg/ml ; 0.00131 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble
Log S (SILICOS-IT)?

SILICOS-IT: Fragmental method calculated by
FILTER-IT program, version 1.0.2, courtesy of SILICOS-IT, http://www.silicos-it.com

-3.06
Solubility 0.118 mg/ml ; 0.000861 mol/l
Class?

Solubility class: Log S scale
Insoluble < -10 < Poorly < -6 < Moderately < -4 < Soluble < -2 Very < 0 < Highly

Soluble

Pharmacokinetics

GI absorption?

Gatrointestinal absorption: according to the white of the BOILED-Egg

Low
BBB permeant?

BBB permeation: according to the yolk of the BOILED-Egg

Yes
P-gp substrate?

P-glycoprotein substrate: SVM model built on 1033 molecules (training set)
and tested on 415 molecules (test set)
10-fold CV: ACC=0.72 / AUC=0.77
External: ACC=0.88 / AUC=0.94

No
CYP1A2 inhibitor?

Cytochrome P450 1A2 inhibitor: SVM model built on 9145 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.83 / AUC=0.90
External: ACC=0.84 / AUC=0.91

Yes
CYP2C19 inhibitor?

Cytochrome P450 2C19 inhibitor: SVM model built on 9272 molecules (training set)
and tested on 3000 molecules (test set)
10-fold CV: ACC=0.80 / AUC=0.86
External: ACC=0.80 / AUC=0.87

No
CYP2C9 inhibitor?

Cytochrome P450 2C9 inhibitor: SVM model built on 5940 molecules (training set)
and tested on 2075 molecules (test set)
10-fold CV: ACC=0.78 / AUC=0.85
External: ACC=0.71 / AUC=0.81

No
CYP2D6 inhibitor?

Cytochrome P450 2D6 inhibitor: SVM model built on 3664 molecules (training set)
and tested on 1068 molecules (test set)
10-fold CV: ACC=0.79 / AUC=0.85
External: ACC=0.81 / AUC=0.87

No
CYP3A4 inhibitor?

Cytochrome P450 3A4 inhibitor: SVM model built on 7518 molecules (training set)
and tested on 2579 molecules (test set)
10-fold CV: ACC=0.77 / AUC=0.85
External: ACC=0.78 / AUC=0.86

No
Log Kp (skin permeation)?

Skin permeation: QSPR model implemented from
Potts RO and Guy RH. 1992 Pharm. Res.

-4.85 cm/s

Druglikeness

Lipinski?

Lipinski (Pfizer) filter: implemented from
Lipinski CA. et al. 2001 Adv. Drug Deliv. Rev.
MW ≤ 500
MLOGP ≤ 4.15
N or O ≤ 10
NH or OH ≤ 5

0.0
Ghose?

Ghose filter: implemented from
Ghose AK. et al. 1999 J. Comb. Chem.
160 ≤ MW ≤ 480
-0.4 ≤ WLOGP ≤ 5.6
40 ≤ MR ≤ 130
20 ≤ atoms ≤ 70

None
Veber?

Veber (GSK) filter: implemented from
Veber DF. et al. 2002 J. Med. Chem.
Rotatable bonds ≤ 10
TPSA ≤ 140

0.0
Egan?

Egan (Pharmacia) filter: implemented from
Egan WJ. et al. 2000 J. Med. Chem.
WLOGP ≤ 5.88
TPSA ≤ 131.6

0.0
Muegge?

Muegge (Bayer) filter: implemented from
Muegge I. et al. 2001 J. Med. Chem.
200 ≤ MW ≤ 600
-2 ≤ XLOGP ≤ 5
TPSA ≤ 150
Num. rings ≤ 7
Num. carbon > 4
Num. heteroatoms > 1
Num. rotatable bonds ≤ 15
H-bond acc. ≤ 10
H-bond don. ≤ 5

2.0
Bioavailability Score?

Abbott Bioavailability Score: Probability of F > 10% in rat
implemented from
Martin YC. 2005 J. Med. Chem.

0.55

Medicinal Chemistry

PAINS?

Pan Assay Interference Structures: implemented from
Baell JB. & Holloway GA. 2010 J. Med. Chem.

0.0 alert
Brenk?

Structural Alert: implemented from
Brenk R. et al. 2008 ChemMedChem

1.0 alert: heavy_metal
Leadlikeness?

Leadlikeness: implemented from
Teague SJ. 1999 Angew. Chem. Int. Ed.
250 ≤ MW ≤ 350
XLOGP ≤ 3.5
Num. rotatable bonds ≤ 7

No; 1 violation:MW<1.0
Synthetic accessibility?

Synthetic accessibility score: from 1 (very easy) to 10 (very difficult)
based on 1024 fragmental contributions (FP2) modulated by size and complexity penaties,
trained on 12'782'590 molecules and tested on 40 external molecules (r2 = 0.94)

1.66

Application In Synthesis of [ 873-73-4 ]

* 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.

  • Downstream synthetic route of [ 873-73-4 ]

[ 873-73-4 ] Synthesis Path-Downstream   1~10

  • 1
  • [ 873-73-4 ]
  • [ CAS Unavailable ]
  • [ 492-37-5 ]
  • [ 938-95-4 ]
  • [ 67381-50-4 ]
YieldReaction ConditionsOperation in experiment
1: 4% 2: 27% 3: 6% With potassium hydroxide; polyethylene glycol (PEG-400) In toluene at 90℃; for 24h;
  • 3
  • [ 873-73-4 ]
  • [ 122-78-1 ]
  • [ 24382-97-6 ]
YieldReaction ConditionsOperation in experiment
70% With titanium tetrachloride In dichloromethane at 20℃; for 4h;
  • 4
  • [ 873-73-4 ]
  • [ 591-50-4 ]
  • [ 5172-02-1 ]
YieldReaction ConditionsOperation in experiment
99% With (diphenylphosphin)ferrocene; gold(I) iodide; potassium carbonate In toluene at 130℃; for 24h;
99% With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 5h; Inert atmosphere;
98% With triethylamine In neat (no solvent) at 70℃; for 3.5h; A typical procedure for the Sonogashira-Hagihara cross-coupling reaction General procedure: A round-bottomed flask equipped with mechanical stirring was charged by a mixtureof phenylacetylene (1.2 mmol, 0.102 g), iodobenzene (1.0 mmol, 0.203 g), triethylamine(1 mmol, 0.101 g), and catalyst (0.007 g, 2.41 mol% Co), under solventfreeconditions at 70 °C. The progress of the reaction was monitored using TLC.After completion of the reaction (4 h), the mixture was diluted with ethyl acetate.Thereafter, the mesostructured catalyst was separated by simple filtration, washedwith EtOH (3 × 10 mL), and dried at 60 °C under vacuum overnight to remove theorganic residuals and solvents for use in the next run. The crude product was thenextracted with ethyl acetate, and the combined organic layer was dried over anhydrousNa2SO4.After solvent evaporation, the residue was purified by thin-layer chromatography using n-hexane/ethyl acetate (6:1) to afford white crystals of diphenylacetylene(0.174 g, 98% yield).
97% With potassium carbonate In ethanol at 80℃; for 6h;
93% With potassium carbonate In N,N-dimethyl-formamide at 100℃; for 6h;
92% With piperidine; 1,3-bis(5-ferrocenylisoxazoline-3-yl)benzene; tetrabutylammomium bromide; palladium diacetate In water; N,N-dimethyl-formamide at 60℃; for 3h;
92% With potassium carbonate In methanol at 60℃; for 10h; Flow reactor;
90% With 1,10-Phenanthroline; potassium carbonate In water at 100℃; for 20h; Inert atmosphere; Green chemistry;
88% With sodium tetrachloropalladate; sodium dodecyl-sulfate; sodium hydroxide In water at 20℃; for 8h;
88% With copper(l) iodide; bis(triphenylphosphine)nickel(II) chloride; potassium carbonate In water at 100℃; for 2h; Inert atmosphere;
86% With 2Na(1+)*CuC6H4(NCHC6H3OO3S)2(2-)=CuC6H4(NCHC6H3ONaO3S)2; tetrabutylammomium bromide; sodium hydroxide In water at 100℃; for 24h; Sealed tube;
85% With [2,2]bipyridinyl; caesium carbonate; iron(III) acetylacetonate In toluene at 135℃; for 42h; Inert atmosphere;
85% With potassium carbonate; chlorobenzene In ethanol for 18h; Green chemistry;
81% With potassium carbonate; triphenylphosphine In N,N-dimethyl-formamide at 100℃; for 10h; Inert atmosphere; Schlenk technique; Sealed tube; General procedure for the Sonogashira coupling of aryl halides with terminal alkynes General procedure: A Schlenk tube was charged with MCM-41-Sb,Py-CuI (122mg, 0.05mmol), triphenyphosphine (26mg, 0.10mmol), and K2CO3 (276mg, 2.0mmol). The tube was evacuated and backfilled with argon. Then, aryl halide (1.0mmol), terminal alkyne (1.2mmol) and DMF (4mL) were added under argon. The tube was sealed, and the reaction mixture was stirred at 100°C for 6-24h. The reaction mixture was cooled to room temperature, diluted with ethyl acetate (20mL), and filtered. The MCM-41-Sb,Py-CuI complex was washed with distilled water (2×5mL), DMF (2×5mL), and ethanol (2×5mL) and reused in the next run. The filtrate was washed with water, dried over MgSO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum/ethyl acetate=30:1-60:1) to provide the desired product.
80% With [bmpy]2[Pd2Cl6]; triethylamine In water at 80℃; for 4h; Inert atmosphere; Schlenk technique; 5.1 Typical procedure for a Sonogashira reaction General procedure: In an N2 atmosphere, a mixture of phenylacetylene (1.0 mmol), iodobenzene (1.0 mmol), triethylamine (2.0 mmol), palladium complex (1×10-5 mol, 1.0 mol%) and water (5.0 mL) was stirred in a Schlenk tube at 80 °C for an appropriate amount of time. Next, the tube was cooled down to room temperature, and the organic products were extracted with 10 mL of diethyl ether. To the extract, 0.1 mL of dodecane was added as an internal standard. The organic products were analyzed using the GC method. The corresponding diphenylacetylene derivatives were isolated by evaporating the solvents and purifying the crude product by column chromatography on silica gel using a hexane and diethyl ether mixture (1:0.1) as the eluent.
75% With C38H35ClCuN4P; potassium carbonate In toluene at 110 - 120℃; for 20h; Inert atmosphere; 4.5. Catalytic studies General procedure: In a round bottom flask, 8 mol% of catalyst, K2CO3 (2.0 mmol),phenylacetylene (2.5 mmol), aryl halide (2.0 mmol), and 20 mltoluene was taken. The whole solution was heated with stirring at110-120° C for 20 h under N2 atmosphere. The solutionwas cooledto room temperature and filtered to remove insoluble impurities.Filtrate was evaporated and the solid was then passed throughcolumn. The desired compound was characterized by 1H NMR and13C NMR.
74% With 1,4-diaza-bicyclo[2.2.2]octane; manganese(III) triacetate dihydrate at 70℃; Green chemistry; General procedure: General procedure: In a 25 mL reaction tube, Mn(OAc)3.2H2O(10 mol%), DABCO (2.5 equiv.) and a stirring bar were added. Then iodobenzene(1 mmol), phenyl acetylene (1 mmol) and PEG-400 were injected by syringe. The reaction tube was closed and transferred to a 70 °C oil bath for 19-24 hours. After the reaction completed, cool down the reaction mixture to room temperature. Water (2 mL) was added and the reaction mixture was extracted with ethyl acetate and then concentrated and purified by column chromatography.
10% With triethylamine In acetonitrile at 80℃; for 48h; Inert atmosphere;
With copper(l) iodide; triethylamine hydrochloride; triethylamine at 20℃; for 1.5h; Schlenk technique; Inert atmosphere;
85 %Chromat. With bis-triphenylphosphine-palladium(II) chloride; silver; potassium carbonate In neat (no solvent) at 20℃; for 6h; Milling;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine Inert atmosphere;
75 % With C38H35ClCuN4P; potassium carbonate In toluene at 110 - 120℃; Inert atmosphere; 4.5. Catalytic studies General procedure: In a round bottom flask, 8 mol% of catalyst, K2CO3 (2.0 mmol),phenylacetylene (2.5 mmol), aryl halide (2.0 mmol), and 20 mltoluene was taken. The whole solution was heated with stirring at110-120° C for 20 h under N2 atmosphere. The solutionwas cooledto room temperature and filtered to remove insoluble impurities.Filtrate was evaporated and the solid was then passed throughcolumn. The desired compound was characterized by 1H NMR and13C NMR.
75 % With C38H35ClCuN4P; potassium carbonate In toluene at 110 - 120℃; Inert atmosphere; 4.5. Catalytic studies General procedure: In a round bottom flask, 8 mol% of catalyst, K2CO3 (2.0 mmol),phenylacetylene (2.5 mmol), aryl halide (2.0 mmol), and 20 mltoluene was taken. The whole solution was heated with stirring at110-120° C for 20 h under N2 atmosphere. The solutionwas cooledto room temperature and filtered to remove insoluble impurities.Filtrate was evaporated and the solid was then passed throughcolumn. The desired compound was characterized by 1H NMR and13C NMR.
92 % With potassium carbonate In dimethyl sulfoxide at 90℃; Sealed tube; Inert atmosphere; General procedure for Pd(at)HKUST-1(at)Cu(II)/CMC beads catalyzed Sonogashira and decarboxylative Sonogashira coupling reactions General procedure: Ar-I (1 mmol), terminal alkyne/phenylpropiolic acid (1.2 mmol), K2CO3 (2 mmol), and a catalytic amount of PdHKUST-1Cu(II)/CMC (30 mg, 0.42 mol% Pd & 4.29 mol% Cu) were sequentially added to DMSO (2 mL) in a sealed vessel. The mixture was stirred at 90 °C for 3 h under a N2 atmosphere, as monitored by thin layer chromatography (TLC). After the completion of the reaction, ethyl acetate (EA) was added to quench the reaction and extract the product. The composite beads were then separated by filtration and thoroughly rinsed with EA and EtOH. Finally, they were dried under vacuum at 80 °C for the next run. The remaining organic filtrate was washed twice with saturated brine and dried over anhydrous Na2SO4. After removing the solvent under reduced pressure, the crude product was further purified using silica gel column chromatography. All products are known, and their 1H and 13C NMR data were found to be identical to those reported in literature.
95 % With potassium acetate In ethylene glycol at 90℃; 3.4. Catalyst Performances General procedure: Sonogashira coupling reactions of aryl halides and terminal alkynes were carried out asfollows. In a 50 mL reaction tube, a mixture of 1 mmol of aryl halides reactants, 1.2 mmol ofterminal alkynes reactants, heterogenous Pd catalysts (containing 2.3 mol of Pd),3 mmol of CH3COOK, 0.2 mL of ethylene glycol, and 5 mL of solvents was added andmagnetically stirred at 90 C (heated in an oil bath) for 1 h. The structure of the reactionproducts was confirmed with 1HNMR spectra using Brucker400-Hz NMR and mass spectrausing Agilent 6890N/5975 MSD GC/MS. The yields of the reaction were measured byGC/MS quantitative analysis based on peak-area of the coupling products and unreactedaryl halide reactant using normalization method. All the structure information was in goodagreement with our recent works [16,33,34]. The recycling experiments of Pd heterogeneouscatalysts were performed using the model coupling reaction of iodo benzene andphenyl acetylene. The catalysts were filtrated out the reaction system after each run. Thenthey were washed with ethanol and dried. Finally, they were added into the next reaction.
91 % With potassium carbonate In dimethyl sulfoxide at 80℃; Inert atmosphere;
85 % With caesium carbonate In dimethyl sulfoxide at 120℃; 2.3. Preparations General procedure: The coupling reaction was performed in a 10 mL oven-dried vial witha thick-walled screw cap. The vial was equipped with a small magneticstirrer coated with glass. The palladacycle catalyst (0.007 g, Pd 0.25 %)and Cs2CO3 (0.228 g, 0.7 mmol) were dispersed in 1.0 mL DMSO. Thearyl halide (0.5 mmol) and aryl acetylene (0.6 mmol) were added to themixture while stirring, and the reaction mixture was heated at 120 C. Asthe reaction was completed (monitored by TLC), the mixture was cooledto room temperature, and the catalyst was retrieved by a magnet. Thecrude product was separated by adding 10 mL of water and three 10 mLportions of ethyl acetate. The combined ethyl acetate extracts were driedover Na2SO4, filtered, and concentrated under a vacuum to remove thesolvent. The product was then purified using column chromatography.
86 % With copper(II) ferrite; potassium carbonate In ethanol at 80℃; Green chemistry; 2.3. Sonogashira coupling reaction General procedure: In a typical Sonogashira coupling reaction experiment, the reactantsviz., aryl halides (1 mmol), phenyl acetylenes (1.5 mmol) along withK2CO3 (2 mmol), CuFe2O4 catalyst (20 mg) were mixed in 3 mL of EtOH.The reaction mixture was constantly stirred at 80 C for 12 h. Soon afterthe reaction is completed (as tracked by TLC), the catalyst was readilyseparated using an external magnet. Ethyl acetate was used twice toextract the products and purified on a microcolumn loaded with silicagel. Then, the products were examined using 1H and 13C NMR spectralanalysis.
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 20℃; Inert atmosphere;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 80℃; for 12h;
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 55℃; for 24h; Inert atmosphere;

References: [1]Location in patent: scheme or table Li, Pinhua; Wang, Lei; Wang, Min; You, Feng [European Journal of Organic Chemistry, 2008, # 35, p. 5946 - 5951].
[2]Wang, Yu-Mei; Tao, Mei-Xia; Mo, Kai-Ming; Chen, Xu; Zhong, Shu-Hua; Shubina, Elena S.; Ning, Guo-Hong; Li, Dan [Science China Chemistry, 2025, vol. 68, # 7, p. 2995 - 3001].
[3]Ghodsinia, Sara S. E.; Akhlaghinia, Batool; Jahanshahi, Roya [Research on Chemical Intermediates, 2021, vol. 47, # 8, p. 3217 - 3244].
[4]Li, Pin-Hua; Wang, Lei [Advanced Synthesis and Catalysis, 2006, vol. 348, # 6, p. 681 - 685].
[5]Li, Pinhua; Wang, Lei; Zhang, Lei; Wang, Guan-Wu [Advanced Synthesis and Catalysis, 2012, vol. 354, # 7, p. 1307 - 1318].
[6]Yu, Shuyan; Wu, Jingxin; He, Xinwei; Shang, Yongjia [Applied Organometallic Chemistry, 2018, vol. 32, # 3].
[7]Li, Haoran; Bao, Xiaochun; Rui, Jiacheng; Zhou, Yong; Shen, Liang; Zhang, Lianzeng; Zhu, Chenjie; Chen, Rizhi; Wu, Xiaojin [Chemical Communications, 2025, vol. 61, # 54, p. 9960 - 9963].
[8]Tang, Lin; Wu, Chaoting; Hu, Qiyan; Li, Qian; Zhang, Wu [Applied Organometallic Chemistry, 2018, vol. 32, # 1].
[9]Location in patent: experimental part Saha, Debasree; Dey, Raju; Ranu, Brindaban C. [European Journal of Organic Chemistry, 2010, # 31, p. 6067 - 6071].
[10]Wei, Ting; Zhang, Tingli; Huang, Bin; Tuo, Yuxin; Cai, Mingzhong [Applied Organometallic Chemistry, 2015, vol. 29, # 12, p. 846 - 849].
[11]Yu, Lintao; Jiang, Xiaofei; Wang, Lixia; Li, Zhengkai; Wu, Di; Zhou, Xiangge [European Journal of Organic Chemistry, 2010, # 29, p. 5560 - 5562].
[12]Location in patent: experimental part Pan, Changduo; Luo, Fang; Wang, Wenhui; Ye, Zhishi; Liu, Miaochang [Journal of Chemical Research, 2009, # 8, p. 478 - 481].
[13]Wang, Hu; Li, Li; Bai, Xing-Feng; Deng, Wen-Hui; Zheng, Zhan-Jiang; Yang, Ke-Fang; Xu, Li-Wen [Green Chemistry, 2013, vol. 15, # 9, p. 2349 - 2355].
[14]Zhao, Hong; Huang, Bin; Wu, Yichao; Cai, Mingzhong [Journal of Organometallic Chemistry, 2015, vol. 797, p. 21 - 28].
[15]Wójcik; Dziadas; Trzeciak [Journal of Organometallic Chemistry, 2022, vol. 962].
[16]Kumari, Sheela; Dhara, Ashish Kumar; Ratnam, Anand; Mawai, Kiran; Chaudhary, Virendra Kumar; Mohanty, Aurobinda; Ghosh, Kaushik [Journal of Organometallic Chemistry, 2020, vol. 928].
[17]Qi, Xinxin; Jiang, Li-Bing; Wu, Xiao-Feng [Tetrahedron Letters, 2016, vol. 57, # 15, p. 1706 - 1710].
[18]Yu, Lei; Han, Zhe; Ding, Yuanhua [Organic Process Research and Development, 2016, vol. 20, # 12, p. 2124 - 2129].
[19]Götzinger, Alissa C.; Müller, Thomas. J. J. [Organic and Biomolecular Chemistry, 2016, vol. 14, # 14, p. 3498 - 3500].
[20]Chen, Longrui; Leslie, Devonna; Coleman, Michael G.; Mack, James [Chemical Science, 2018, vol. 9, # 20, p. 4650 - 4661].
[21]Xiong, Li; Chen, Fengjuan; Wu, Yihang; Hu, Xinwei; Ruan, Zhixiong; Jiang, Huanfeng; Zeng, Wei [Organic Letters, 2022, vol. 24, # 42, p. 7856 - 7860].
[22]Kumari, Sheela; Dhara, Ashish Kumar; Ratnam, Anand; Mawai, Kiran; Chaudhary, Virendra Kumar; Mohanty, Aurobinda; Ghosh, Kaushik [Journal of Organometallic Chemistry, 2020, vol. 928].
[23]Kumari, Sheela; Dhara, Ashish Kumar; Ratnam, Anand; Mawai, Kiran; Chaudhary, Virendra Kumar; Mohanty, Aurobinda; Ghosh, Kaushik [Journal of Organometallic Chemistry, 2020, vol. 928].
[24]Huang, Yuling; Huang, Jiayi; Zhou, Yuping; Fan, Xuetao; Li, Yiqun [Carbohydrate Polymers, 2024, vol. 324].
[25]Sun, Kailang; Liu, Yonghong; Zhang, Taojun; Zhou, Jie; Chen, Jinyang; Ren, Xiaorong; Yang, Zhen; Zeng, Minfeng [Molecules, 2023, vol. 28, # 22].
[26]Huang, Yuling; Lin, Dongtao; Qi, Yumei; Deng, Hanhui; Li, Yiqun [Applied Organometallic Chemistry, 2024, vol. 38, # 7].
[27]Ghahramani, Fatemeh; Mansoori, Yagoub; Esquivel, Dolores; Navarro, M. Angeles [Journal of Solid State Chemistry, 2024, vol. 336].
[28]Banda, Prashanth Goud; Kurup, Gayathri Bindu; Mucherla, Raghasudha [Journal of Organometallic Chemistry, 2024, vol. 1016].
[29]Patil, Nilam; Subramanian, Kripa; Bhanage, Bhalchandra M. [Organic and Biomolecular Chemistry, 2024, vol. 22, # 44, p. 8743 - 8748].
[30]Zhang, Haoxiang; Cui, Wentao; Jin, Xiaoyan; Yang, Yuhuan; Zhang, Xiao [Organic and Biomolecular Chemistry, 2025, vol. 23, # 10, p. 2386 - 2390].
[31]Lv, Jiaoyue; Lang, Yatao; Li, Chao-Jun; Zeng, Huiying [Chemical Communications, 2025, vol. 61, # 20, p. 4054 - 4057] Lv, Jiaoyue; Zeng, Huiying [Journal of Organic Chemistry, 2025, vol. 90, # 26, p. 9270 - 9279].
  • 5
  • [ 873-73-4 ]
  • [ 691-24-7 ]
  • [ 872420-18-3 ]
YieldReaction ConditionsOperation in experiment
95% With [Y((CH3)4C5Si(CH3)2N(phenyl))(trimethylsilylmethyl)(tetrahydrofuran)2] In toluene at 110℃; for 1h;
  • 6
  • [ 873-73-4 ]
  • [ 4016-63-1 ]
  • 2-Amino-8-(4-chloro-phenylethynyl)-9-((2R,3R,4S,5R)-3,4-dihydroxy-5-hydroxymethyl-tetrahydro-furan-2-yl)-1,9-dihydro-purin-6-one [ No CAS ]
  • 7
  • [ 873-73-4 ]
  • [ 43073-12-7 ]
  • [ 942229-71-2 ]
YieldReaction ConditionsOperation in experiment
62% Stage #1: 4-n-chlorophenylacetylene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.0833333h; Stage #2: 4,5-dimethoxy-phthalaldehyde In tetrahydrofuran; hexane at -78 - 20℃; Further stages.;
  • 8
  • [ 873-73-4 ]
  • [ 20754-24-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: ethanol / 20 h / Heating 2: 72.5 percent / PdCl2, CuCl2, Et3N / 75 h / 25 °C / 760 Torr
  • 9
  • [ 873-73-4 ]
  • [ 151978-97-1 ]
  • [ 651330-72-2 ]
YieldReaction ConditionsOperation in experiment
With triethylamine at 70℃; for 5h; 2 Example 2; N1-[2-[4-[(4-chlorophenyl)ethynyl]phenoxy]ethyl]-N4-propyl-1,4-benzenedimethanamine (Compound 2) Example 2 [/V'- [2- [4- [ (4-CHLOROPHENYL) ETHYNYL]] phenoxy] [ETHYL]-N4-PROPYL-1,] 4- benzenedimethanamine (Compound 2) Compound 2a (8.23 g, 37.4 [MMOL)] was dissolved in acetonitrile (200 mL) and Compound 2b (7.15 g, 37.4 [MMOL),] [DIISOPROPYLAZODICARBOXYLATE] (8.8 mL, 44.9 [MMOL)] and triphenylphosphine (11.77 g, 44.9 [MMOL)] were then added. After 4 hours ether (50 mL) was added and the solid was collected by filtration to give Compound 2c, which was used without further purification. Mp 180-181. [5 °C ; H] NMR [(CDCI3)] [8] 4.23 (t, 2H), 4.13 (t, 2H). Compound 2c (3.00 g, 7.63 [MMOL)] was stirred in methanol and hydrazine monohydrate (1.50 mL) was added. The mixture was heated to reflux for 3 hours then evaporated [IN VACUO.] Aqueous potassium hydroxide (5N, 150 mL) was added and the mixture was extracted with methylene chloride. The organic layer was washed with water, dried over sodium sulfate and [EVAPORATED IN VACUO] to give Compound 2d as a white solid. MS 264 [(MH+)] [; H] NMR [(CDCI3)] [8] 7.54 (d, 2H), 6.70 (d, 2H), 3.95 (t, 2H), 3.08 (t, 2H). Compound 2d (6.62 g, 25.16 [MMOL)] was dissolved in triethylamine (250 mL). Bis (acetato) bis (triphenylphosphine) palladium [(II)] (1.88 g, 10 mol%) and Compound 1d (5.16 g, 37.75 [MMOL)] were added. The resulting mixture was stirred at 70 [°C] for 5 hours and [EVAPORATED IN VACUO.] The crude solid was slurried in methylene chloride and washed with 1 N sodium hydroxide then water. The organic layer was evaporated and the residue triturated with ether/hexane (1: 1) to give Compound 2e as a tan solid. MS 271.9 [(MH+).] Compound 2e (1.99 g, 7.32 [MMOL)] was dissolved in methylene chloride (120 mL). Compound 2f (1.32 mL, 6.66 [MMOL),] sodium [TRIACETOXYBOROHYDRIDE] (2.12 g, 9.99 [MMOL)] and acetic acid (0.40 mL) were added. The mixture was stirred for 24 hours before adding 1 N aqueous sodium hydroxide (30 mL). The organic layer was dried over sodium sulfate and concentrated. The product was purified on a silica gel column [ELUTING] with methylene chloride/methanol (19: 1) to give Compound 2g as a yellow gum. MS 465 [(MH+)] [; H] NMR (CDCI3) [8] 5.49 (s, [1H),] 4.10 (t, 2H), 3.89 (s, 2H), 3.04 (t, 2H), 1.24 (t, 6H). Compound 2g (4.96 g, 10.69 [MMOL)] was dissolved in a mixture of acetic acid and water (5: 1,60 mL). The mixture was stirred at 70 [°C] for 3 hours before being poured into ice. The solution was neutralized with 1 N sodium hydroxide to pH 7 and the product was extracted with ethyl acetate. The organic layer was evaporated and the residue was triturated in water to give Compound 2h as a tan solid. MS 390 (MH+) [; H] NMR [(CDCI3)] [8] 10.02 (s, [1 H),] 4.13 (t, 2H), 3.99 (s, 2H), 3.06 (t, 2H). Compound 2h [(0. 500] g, 1.28 [MMOL)] was dissolved in methylene chloride (50 mL). [PROPYLAMINE] (0.12 mL, 1.41 [MMOL),] sodium [TRIACETOXYBOROHYDRIDE] (0.41 g, 1.92 [MMOL)] and acetic acid (0.30 mL) were added. The mixture was stirred for 24 hours before adding 1 N aqueous sodium hydroxide (30 mL). The organic layer was concentrated and the residue was chromatographed on a silica gel column eluting with methylene [CHLORIDE/METHANOL/TRIETHYLAMINE] (9: 1: 0.05). The fractions containing the product were combined and concentrated to 50 mL and washed with 1 N aqueous sodium hydroxide (30 mL). The organic layer was dried over sodium sulfate, filtered and [EVAPORATED IN VACUO] to give Compound 2 as a yellow gum. MS 433 [; H] NMR (CDCI3) [5] 4.10 (t, 2H), 3.86 (s, 2H), 3.78 (s, 2H), 3.03 (t, 2H), 2.59 (t, 2H), 1.53 (q, 2H), 0.92 (t, 3H).
In triethylamine at 70℃; for 5h; 2 Example 2; Preparation of N1-[2-[4-[(4-chlorophenyl)ethynyl]phenoxy]ethyl]-N4-propyl-1,4-benzenedimethanamine (Compound 2) Compound 2a (8.23 g, 37.4 mmol) was dissolved in acetonitrile (200 mL) and Compound 2b (7.15 g, 37.4 mmol), diisopropylazodicarboxylate (8.8 mL, 44.9 mmol) and triphenylphosphine (11.77 g, 44.9 mmol) were then added. After 4 hours ether (50 mL) was added and the solid was collected by filtration to give Compound 2c, which was used without further purification. Mp 180-181.5° C.; 1H NMR (CDCl3) δ 4.23 (t, 2H), 4.13 (t, 2H). Compound 2c (3.00 g, 7.63 mmol) was stirred in methanol and hydrazine monohydrate (1.50 mL) was added. The mixture was heated to reflux for 3 hours then evaporated in vacuo. Aqueous potassium hydroxide (5N, 150 mL) was added and the mixture was extracted with methylene chloride. The organic layer was washed with water, dried over sodium sulfate and evaporated in vacuo to give Compound 2d as a white solid. MS 264 (MH+); 1H NMR (CDCl3) δ 7.54 (d, 2H), 6.70 (d, 2H), 3.95 (t, 2H), 3.08 (t, 2H). [0184] Compound 2d (6.62 g, 25.16 mmol) was dissolved in triethylamine (250 mL). Bis(acetato)bis(triphenylphosphine)palladium(II) (1.88 g, 10 mol %) and Compound 1d (5.16 g, 37.75 mmol) were added. The resulting mixture was stirred at 70° C. for 5 hours and evaporated in vacuo. The crude solid was slurried in methylene chloride and washed with 1 N sodium hydroxide then water. The organic layer was evaporated and the residue triturated with ether/hexane (1:1) to give Compound 2e as a tan solid. MS 271.9 (MH+). Compound 2e (1.99 g, 7.32 mmol) was dissolved in methylene chloride (120 mL). Compound 2f (1.32 mL, 6.66 mmol), sodium triacetoxyborohydride (2.12 g, 9.99 mmol) and acetic acid (0.40 mL) were added. The mixture was stirred for 24 hours before adding 1N aqueous sodium hydroxide (30 mL). The organic layer was dried over sodium sulfate and concentrated. The product was purified on a silica gel column eluting with methylene chloride/methanol (19:1) to give Compound 2 g as a yellow gum. MS 465 (MH+); 1H NMR (CDCl3) δ 5.49 (s, 1H), 4.10 (t, 2H), 3.89 (s, 2H), 3.04 (t, 2H), 1.24 (t, 6H). [0185] Compound 2 g (4.96 g, 10.69 mmol) was dissolved in a mixture of acetic acid and water (5:1, 60 mL). The mixture was stirred at 70° C. for 3 hours before being poured into ice. The solution was neutralized with 1N sodium hydroxide to pH 7 and the product was extracted with ethyl acetate. The organic layer was evaporated and the residue was triturated in water to give Compound 2h as a tan solid. MS 390 (MH+); 1H NMR (CDCl3) δ 10.02 (s, 1H), 4.13 (t, 2H), 3.99 (s, 2H), 3.06 (t, 2H). Compound 2h (0.500 g, 1.28 mmol) was dissolved in methylene chloride (50 mL). Propylamine (0.12 mL, 1.41 mmol), sodium triacetoxyborohydride (0.41 g, 1.92 mmol) and acetic acid (0.30 mL) were added. The mixture was stirred for 24 hours before adding 1N aqueous sodium hydroxide (30 mL). The organic layer was concentrated and the residue was chromatographed on a silica gel column eluting with methylene chloride/methanol/triethylamine (9:1:0.05). The fractions containing the product were combined and concentrated to 50 mL and washed with 1N aqueous sodium hydroxide (30 mL). The organic layer was dried over sodium sulfate, filtered and evaporated in vacuo to give Compound 2 as a yellow gum. MS 433; 1H NMR (CDCl3) δ 4.10 (t, 2H), 3.86 (s, 2H), 3.78 (s, 2H), 3.03 (t, 2H), 2.59 (t, 2H), 1.53 (q, 2H), 0.92 (t, 3H). [C00009]
  • 10
  • [ 873-73-4 ]
  • [ 93415-79-3 ]
  • [ 7440-37-1 ]
  • [ 7681-65-4 ]
  • [ 283173-77-3 ]
YieldReaction ConditionsOperation in experiment
With triethylamine In toluene 3-Amino-2-(4-chloro-phenylethynyl)-benzoic Acid Methyl Ester 3-Amino-2-(4-chloro-phenylethynyl)-benzoic Acid Methyl Ester 2-iodo-3-nitro-benzoic acid methyl ester (0.79 g, 2.84 mmol), 1-chloro-4-ethynylbenzene (0.41 g, 2.99 mmol), palladium tetrakis(triphenylphosphine) (0.16 g, 0.14 mmol), copper (I) iodide (0.03 g, 0.14 mmol), and triethylamine (1.44 g, 14.19 mmol) were dissolved in 15 mL toluene. Argon was bubbled through the resulting solution for 15 min. The reaction was stirred under argon at 80° C. for 2 h and 20 min. The reaction mixture was then washed once with water, dried (MgSO4), and concentrated in vacuo. The orange oil was purified by flash chromatography eluding with 50 to 100% CHCl3/hexanes to yield 3-amino-2-(4-chloro-phenylethynyl)-benzoic acid methyl ester, 0.76 g (94%) as a yellow oil. 1H NMR (300 MHz, d6-DMSO) 3.84 (s,3H), 5.84 (br s, 2H), 6.97 (dd, J=8.1, 1.3 Hz, 1H), 7.05 (dd, J=7.5, 1.2 Hz, 1H), 7.17 (app t, J=7.5 Hz, 1H), 7.49 (d, J=8.7 Hz, 2H), 7.63 (d, J=8.7 Hz, 2H). MS (electrospray, MH+) 286.
 

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