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Jonah B. Eisenberg ; Kwanpyung Lee ; Xin Yuan , et al. DOI: PubMed ID:

Abstract: The hydrogenolysis or hydrodeoxygenation of a carbonyl group, where the C═O group is converted to a CH2 group, is of significant interest in a variety of fields. A challenge in electrochemically achieving hydrogenolysis of a carbonyl group with high selectivity is that electrochemical hydrogenation of a carbonyl group, which converts the C═O group to an alcohol group (CH-OH), is demonstrated not to be the initial step of hydrogenolysis. Instead, hydrogenation and hydrogenolysis occur in parallel, and they are competing reactions. This means that although both hydrogenolysis and hydrogenation require adding H atoms to the carbonyl group, they involve different intermediates formed on the electrode surface. Thus, revealing the difference in intermediates, transition states, and kinetic barriers for hydrogenolysis and hydrogenation pathways is the key to understanding and controlling hydrogenolysis/hydrogenation selectivity of carbonyl compounds. In this study, we aimed to identify features of reactant molecules that can affect their hydrogenolysis/hydrogenation selectivity on a Zn electrode that was previously shown to promote hydrogenolysis over hydrogenation. In particular, we examined the electrochemical reduction of para-substituted benzaldehyde compounds with substituent groups having different electron donating/withdrawing abilities. Our results show a strikingly systematic impact of the substituent group where a stronger electron-donating group promotes hydrogenolysis and a stronger electron-withdrawing group promotes hydrogenation. These experimental results are presented with computational results explaining the substituent effects on the thermodynamics and kinetics of electrochemical hydrogenolysis and hydrogenation pathways, which also provide critically needed information and insights into the transition states involved with these pathways.

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Product Details of [ 874-89-5 ]

CAS No. :874-89-5 MDL No. :MFCD00870633
Formula : C8H7NO Boiling Point : -
Linear Structure Formula :- InChI Key :XAASLEJRGFPHEV-UHFFFAOYSA-N
M.W : 133.15 Pubchem ID :160549
Synonyms :

Calculated chemistry of [ 874-89-5 ]      Expand+

Physicochemical Properties

Num. heavy atoms : 10
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 : 37.28
TPSA : 44.02 Ų

Pharmacokinetics

GI absorption : High
BBB permeant : Yes
P-gp substrate : No
CYP1A2 inhibitor : Yes
CYP2C19 inhibitor : No
CYP2C9 inhibitor : No
CYP2D6 inhibitor : No
CYP3A4 inhibitor : Yes
Log Kp (skin permeation) : -6.62 cm/s

Lipophilicity

Log Po/w (iLOGP) : 1.59
Log Po/w (XLOGP3) : 0.69
Log Po/w (WLOGP) : 0.9
Log Po/w (MLOGP) : 0.85
Log Po/w (SILICOS-IT) : 1.65
Consensus Log Po/w : 1.14

Druglikeness

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

Water Solubility

Log S (ESOL) : -1.48
Solubility : 4.43 mg/ml ; 0.0332 mol/l
Class : Very soluble
Log S (Ali) : -1.19
Solubility : 8.56 mg/ml ; 0.0643 mol/l
Class : Very soluble
Log S (SILICOS-IT) : -2.28
Solubility : 0.7 mg/ml ; 0.00526 mol/l
Class : Soluble

Medicinal Chemistry

PAINS : 0.0 alert
Brenk : 0.0 alert
Leadlikeness : 1.0
Synthetic accessibility : 1.3

Safety of [ 874-89-5 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302+H312+H332-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 874-89-5 ]

* 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 [ 874-89-5 ]
  • Downstream synthetic route of [ 874-89-5 ]

[ 874-89-5 ] Synthesis Path-Upstream   1~69

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  • [ 6068-72-0 ]
Reference: [1] Journal of the Chemical Society, 1942, p. 103,107
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  • [ 17201-43-3 ]
YieldReaction ConditionsOperation in experiment
89% With phosphorus pentoxide; potassium bromide In acetonitrile at 20℃; for 1 h; General procedure: To a mixture of alcohol (1 mmol) and KBr (1.5 mmol, 0.18 g) in acetonitrile (5 mL), P2O5 (1.5 mmol, 0.23 g) was added and the reaction was stirred at room temperature for the time specified in Table 3. After reaction completion (TLC or GC), the reaction mixture was filtered and the residue washed with ethyl acetate (3 × 8 mL). The combined organic layers were washed with water (10 mL) and dried over Na2SO4. The solvent was removed under reduced pressure to afford the corresponding product. If necessary, further purification was performed by column chromatography.
Reference: [1] Tetrahedron Letters, 2016, vol. 57, # 2, p. 168 - 171
[2] Organic Letters, 2015, vol. 17, # 15, p. 3810 - 3813
[3] Advanced Synthesis and Catalysis, 2016, vol. 358, # 11, p. 1731 - 1735
[4] Patent: US6384080, 2002, B1,
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  • [ 874-86-2 ]
Reference: [1] Tetrahedron Letters, 2014, vol. 55, # 19, p. 3045 - 3048
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  • [ 1396318-76-5 ]
  • [ 874-86-2 ]
Reference: [1] Tetrahedron Letters, 2014, vol. 55, # 19, p. 3045 - 3048
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  • [ 64-17-5 ]
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  • [ 7153-22-2 ]
YieldReaction ConditionsOperation in experiment
89% With 1H-imidazole; tert.-butylhydroperoxide; tetra-(n-butyl)ammonium iodide In water at 80℃; for 17 h; Green chemistry General procedure: To a mixture of benzyl alcohol (108 mg, 1.0 mmol) and TBHP(180 mg, 2.0 mmol) in water (3 ml), the catalyst TBAI (73.8 mg,0.2 mmol), imidazole (136 mg, 2.0 mmol), and MeOH (2 ml)were added, and the mixture was stirred at 80 °C for 8 h. Theprogress of the reaction was monitored by TLC. After completionof reaction, the reaction mixture was cooled to room temperature.Then MeOH was distilled out, and the organic productwas extracted with ethyl acetate (3 × 10 ml), repeatedly washedwith distilled water (4 × 5 ml) to remove the unreacted TBHP,dried with anhydrous sodium sulfate, and the solvent was evaporatedunder reduced pressure to afford methyl benzoate (112mg, yield 82percent).
Reference: [1] Synlett, 2018, vol. 29, # 16, p. 2208 - 2212
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  • [ 5462-71-5 ]
Reference: [1] Journal of the American Chemical Society, 2014, vol. 136, # 3, p. 1062 - 1069
  • 7
  • [ 124-38-9 ]
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  • [ 5462-71-5 ]
Reference: [1] Tetrahedron Letters, 2015, vol. 56, # 48, p. 6772 - 6776
  • 8
  • [ 619-65-8 ]
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YieldReaction ConditionsOperation in experiment
95%
Stage #1: With borane-THF; boron trifluoride diethyl etherate In tetrahydrofuran at 20 - 25℃; for 2 h;
Stage #2: With water; sodium hydrogencarbonate In ethyl acetate
8A. 4-Hydroxymethyl-benzonitrile Boron trifluoride diethyl etherate (0.85 mL, 6.8 mmol) was added to a solution of 4-cyanobenzoic acid (1.0 g, 6.8 mmol) and THF (10 mL). At room temperature, borane-tetrahydrofuran complex (1.0 M, 13.6 mL) was added to the reaction mixture drop-wise with no observed exotherm. The reaction mixture was stirred at room temperature for 2 hours and concentrated in vacuo. The resulting residue was taken up in ethyl acetate (50 mL), washed with saturated NaHCO3 and brine, dried (Na2SO4), filtered and concentrated in vacuo to give the title compound (0.900 g, 95percent yield) as a solid. 1H NMR (400 MHz, CDCl3) δ 4.65 (s, 2H), 7.38 (d, 2H), 7.53 (d, 2H).
Reference: [1] Patent: US2007/270438, 2007, A1, . Location in patent: Page/Page column 39
[2] Tetrahedron Letters, 2003, vol. 44, # 16, p. 3427 - 3428
[3] Advanced Synthesis and Catalysis, 2014, vol. 356, # 2-3, p. 308 - 312
[4] Dalton Transactions, 2016, vol. 45, # 19, p. 8265 - 8271
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YieldReaction ConditionsOperation in experiment
96.2% With potassium carbonate In water at 80℃; for 10 h; Into a 3000 mL four-necked flask, 138 g of potassium carbonate, 151.5 g of 4-chloromethylbenzonitrile, and 2300 g of water were placed.Heat to 80°C, react for 10 hours, sample for HPLC detection,It was confirmed that the hydrolysis reaction of 4-chloromethylbenzonitrile was complete. Dichloromethane extraction was performed in the hydrolysis reaction solution (800 mL each time, and extracted 3 times at room temperature).The extract was distilled to remove the extraction solvent to obtain 128 g of 4-cyanobenzyl alcohol with a purity of 96-98percent and a yield of 96.2percent.
Reference: [1] Patent: CN107556214, 2018, A, . Location in patent: Paragraph 0031; 0032; 0035; 0038; 0041; 0044; 0047
[2] Journal of the Chemical Society, 1942, p. 103,107
[3] Journal of Organic Chemistry, 2015, vol. 80, # 4, p. 2310 - 2318
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  • [ 105-07-7 ]
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YieldReaction ConditionsOperation in experiment
99% With C48H43ClN2P2Ru; ammonium formate In water; toluene at 90℃; for 3.5 h; Schlenk technique Transfer hydrogenation in a biphasic system with formate salts as hydride donor on aldehyde substrates The selected aldehyde (2.5 mmol), HCOONH4 (10 mmol, 0.63 g) and complex (e.g. 1 .25 μηιοΙ, 1 mg; S/C = 2000) are transferred into a 50 ml Schlenk tube. Then toluene (1 .2 ml) and water (5 ml) are sequentially added. The biphasic mixture is subjected to four vacuum-argon cycles under vigorous stirring and then put into an oil bath at 90°C for the desired time. The reaction is sampled by removing ~1 ml of the mixture, diethyl ether (4 ml) is added, the organic phase separated, dried over MgS04, filtered and the solvent gently removed under reduced pressure. The crude residue was dissolved with CDCI3 and analyzed by H-NMR. Alternatively, the dried organic fraction is filtered over a short silica pad and the conversion determined by GC analysis. Table 11. TH of aldehydes catalyzed by complexes 13-15 with HC02NH4 in toluene/H20 at 90°C Aldehyde Complex S/C Substrate NH4-formate Time Alcohol By- molar molar;equivalents (h) (percent) products (percentL_ 13 5000 0.5 1 ; 2 16 60 0 13 5000 0.5 1 ; 2 22 76 0 14 5000 0.5 1 ; 2 15 96 0 14 5000 0.5 1 ; 2 24 97 0 14 5000 1 .0 1 ; 2 15 86 0 14 5000 1.0 1; 2 24 95 0 14 5000 0.5 1; 4 15 96 0 14 5000 0.5 1; 4 24 96 0 14 5000 1.0 1; 4 15 96 0 14 5000 1.0 1; 4 24 96 0 14 20000 2.0 2; 4 24 94 0 14 20000 2.0 2; 4 48 96 0 15 5000 0.5 1; 2 16 96 0 15 10000 2.0 1; 2 20 86 0 15 20000 2.0 1; 2 40 96 0 14 2000 0.5 1; 2 10 97 0 14 20000 2.0 2; 4 24 62 0 14 20000 2.0 2; 4 48 72 0 14 2000 0.5 2; 4 10 >99 0 14 2000 0.5 1; 2 3.5 >99 0 14 2000 0.5 1; 1.5 9 57: 83 0 58: 17 14 2000 0.5 1; 2 10 57: 71 0 58: 21 0 14 2000 0.5 1;4 10 57: 0 58: 99 14 2000 0.5 1; 2 10 97 54:10 14 5000 2.0 2; 4 16 78 0 14 5000 2.0 2; 4 24 86 0 14 5000 2.0 2; 4 48 97 0 14 5000 2.0 4; 4 16 84 0 14 5000 2.0 4; 4 24 91 0 14 5000 2.0 4; 4 48 94 0 14 10000 0.5 1;2 24 38 0 14 10000 0.5 1;2 38 49 0 With complexes 13-15 the transfer hydrogenation of aldehydes with NH4-formate is an improvement compared to using 2-propanol as hydride donor and K2C03 as base (examples 28 and 29). The use of less complex (higher S/C ratio) is possible and less by-products are formed. It is important to note that no primary amines are produced by reductive amination of the aldehyde. Interestingly, the presence of the toluene solvent as co-solvent is not entirely required, as shown in the table below. Toluene was not added to the reactions carried out on a 2.5 mmol substrate scale. Table 12. TH of aldehydes catalyzed by complex 14 with HC02NH4in H20 at 90°C Aldehyde Complex S/C Substrate NH4-formate Time Alcohol By- molar molar;equivalents (h) (percent) products (percent) 13 5000 0.5 1; 2 16 60 13 5000 0.5 1; 2 22 76 14 2000 2.5 mmol 1; 2 2 50 14 2000 2.5 mmol 1; 2 4 76 14 2000 2.5 mmol 1; 2 7 97 14 5000 2.5 mmol 1; 2 14 53 14 5000 2.5 mmol 1; 4 24 97 14 5000 2.5 mmol 2; 4 24 90 45 14 5000 0.5 1; 2 15 96 14 5000 0.5 1; 2 24 97 14 5000 1.0 1; 2 15 86 14 5000 1.0 1; 2 24 95 14 5000 0.5 1; 4 15 96 14 5000 0.5 1; 4 24 96 14 5000 1.0 1; 4 15 96 14 5000 1.0 1; 4 24 96 14 20000 2.0 2; 4 24 94 14 20000 2.0 2; 4 48 96 0 15 5000 0.5 1; 2 16 96 0 15 10000 2.0 1; 2 20 86 0 15 20000 2.0 1; 2 40 96 0 14 2000 2.5 mmol 1; 2 14 33 6 14 2000 2.5 mmol 1; 2 16 61 0 14 2000 0.5 1; 2 10 97 0 46 14 2000 2.0 2;4 11 97 0 14 10000 2.0 2;4 24 24 0 14 20000 2.0 2; 4 24 62 0 14 20000 2.0 2; 4 48 72 0 14 5000 2.0 2; 4 15 96 0 47 >99, 14 2000 0.5 2; 4 10 0 48 65[bl 14 2000 0.5 1; 2 3.5 >99 0 55 14 2000 2.0 2;4 3.5 99, 65[bl 0 14 2000 0.5 1; 1.5 9 57: 83 0 56 58: 17 14 2000 0.5 1; 2 10 57: 71 0 58: 21 14 2000 0.5 1;4 10 57: 0 0 58: 99 14 2000 0.5 1; 2 10 97 54:10 14 5000 2.0 2; 4 16 78 54:6 14 5000 2.0 2; 4 24 86 0 52 14 5000 2.0 2; 4 48 97 54:12 14 5000 2.0 4; 4 16 84 0 14 5000 2.0 4; 4 24 92 54:5 14 5000 2.0 4; 4 48 94 54:7 14 10000 0.5 1 ; 2 24 38 14 10000 0.5 1 ; 2 38 49 59 14 10000 2.0 4; 4 20 98 0 60 14 10000 2.0 2; 4 24 65 0 60 14 10000 2.0 4; 4 24 97 0 61 14 5000 2.0 4;4 20 98, 88[bl 62 14 5000 2.0 2;4 8 95 63 14 2000 2.0 4;4 9 96, 79[bl Conversion and product content were determined by GC analysis or by -NMR spectroscopy. Isolated yield. On 2.5 mmol scale, reduction of benzaldehyde 45 (0.5 molar in toluene) at S/C =2000, 90°C and 4 equivalents of 2M aqueous Na-formate gave only traces of benzylalcohol after 14 hours. Use of 4 equivalents of (NEt3H)-formate improves the yield to 50 percent in 22 hours. Use of 5 equivalents of (NEt3H)-formate on frans-cinnamaldehyde 52 gives after 18 hours 80 percent of allylic alcohol 53 and 15 percent of saturated alcohol 54. NH4-formate is preferred over the other formate reagents.
96%
Stage #1: With chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II); phenylsilane In toluene for 20 h; Reflux
Stage #2: With tetrabutyl ammonium fluoride In toluene at 20℃; for 0.5 h;
General procedure: To a solution of [CpRu(PPh3)2Cl] (1 molpercent) and solid aldehyde (1.0 mmol) in toluene (3 ml) was added PhSiH3 (1.2 mmol). The reaction mixture was stirred at reflux temperature under an air atmosphere (the reaction times are indicated in Table 4). Then, TBAF (1.0 mmol) was added and the reaction mixture was stirred at room temperature during 30 min. After evaporation, the reaction mixture was purified by silica gel column chromatography with ethyl acetate:n-hexane (1:3) to afford the corresponding alcohols.
94% With potassium diisobutyl-tert-butoxyaluminum hydride In tetrahydrofuran at 0℃; for 1 h; Inert atmosphere General procedure: A dry and argon-flushed flask, equipped with a magnetic stirring bar and a septum, was charged with dicarbonyl compound (1.0 mmol) and 10 mL THF. After cooling to 0°C, PDBBA (1.3 mmol) was added dropwise and stirred for 1h at same temperature. The reaction was stopped by the aqueous 1N HCl (10mL) and extracted with diethyl ether (2×10mL). The combined organic layers were dried over MgSO4, filtered and concentrated under reduced pressure. Purification of the residue by column chromatography on silica gel afforded the desired product.
93% With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; tris[3,5-bis(trifluoromethyl)phenyl]-borane In 1,4-dioxane at 25℃; for 12 h; Glovebox General procedure: In a glovebox, aldehydes (0.25 mmol) and the Hantzsch ester 1 (95 mg, 0.38 mmol) were added to asolution of tris[3,5-bis(trifluoromethy)phenyl]borane (9) (8.1 mg, 12.5 μmol) in 1 mL of anhydrous1,4-dioxane. The reaction mixture was stirred at 25 or 100 C for 12 h. An internal standard (biphenylor mesitylene) was added to the reaction mixture and filtrated through a cotton plug. The resultingsolution was analyzed with gas chromatography.
92% With sodium borohydrid In ethanol Step A
Preparation of 4-cyanobenzyl alcohol
To a solution of 4-cyanobenzaldehyde (1.97 g, 15.0 mmol) in 50 mL of ethanol at room temperature was added sodium borohydride (0.57 g, 15.0 mmol).
After 4 days, the solution was quenched with saturated ammonoum chloride solution, then poured into EtOAc, washed with sat, NaHCO3 soln. and brine, dried (Na2 SO4), filtered, and concentrated in vacuo to provide the product (1.82 g, 92percent yield) as a white waxy solid which was sufficiently pure for use in the next step without further purification.
85% With glucose dehydrogenase; D-glucose; Bacteroides fragilis ATCC 25285 7α-hydroxysteroid dehydrogenase; NAD In dimethyl sulfoxide at 30℃; for 25 h; aq. phosphate buffer; Enzymatic reaction General procedure: The reaction procedure was as follows: glucose (18 mg), glucose dehydrogenase (0.35 U), NAD (2 mg), 7α-hydroxysteroid dehydrogenase (1.1 U) and benzaldehyde (0.02 mmol, dissolved in 10 μL of DMSO) were mixed in 1 mL of potassium phosphate buffer (100 mM, pH 7.0). The mixture was shaken for 12 h at 30 °C, and was then extracted with methyl tert-butyl ether (800 μL). The organic extract was dried over anhydrous sodium sulfate and subjected to HPLC analysis to measure the conversion. The products were identified by comparison with authentic samples in HPLC analysis.
82% With sodium tetrahydroborate In methanol at 0℃; for 1.5 h; To a solution of 4-formyl-benzonitrile (1.51 g, 11.5 mmoL) in MeOH(15 mL)was added NaBH4 (0.51 g, 13.4 mmoL) at 0 °C. Then the mixture was stirred at this temperature for 1.5 hrs. The reaction was quenched with H20 (7.5 mL) and the resulting mixture was concentrated to remove most of the MeOH. Then the residue was poured into H20 (20 mL) and extracted with EtOAc (30 nJ*2) The combined EtOAc extracts were washed with brine (20 mL), dried over Na2SO4 and concentrated to give 4-hydroxymethyl-benzonitrile (1.26 g, yield: 82percent) as colorless oil.
81%
Stage #1: With Triethoxysilane; [cis-Fe(H)(SPh)(PMe3)4] In tetrahydrofuran at 50℃; for 2 h;
Stage #2: With methanol; sodium hydroxide In tetrahydrofuran; water at 60℃; for 24 h;
General procedure: To a 25 mL Schlenk tube containing a solution of 1 in 2 mL of THF was added an aldehyde (1.0 mmol) and (EtO)3 SiH (0.20 g, 1.2 mmol). The reaction mixture was stirred at 50–55 °C until there was no aldehyde left (monitored by TLC and GC–MS). The reaction was then quenched byMeOH (2mL) and a 10percent aqueous solution of NaOH (5 mL) with vigorous stirring at 60 °C for about 24 h.The organic product was extracted with diethyl ether (10 mL × 3), dried over anhydrous MgSO4, and concentrated under vacuum. The alcohol product was further purified using flash column chromatography (elute with 5–10percent ethyl acetate in petroleum ether). The 1H NMR and 13C NMR spectra of the alcohol products are providedin Supporting information.
10 %Chromat. With formaldehyd; tricarbonyl(η4-1,3-bis(trimethylsilyl)-4,5,6,7-tetrahydro-2H-inden-2-one)iron; water; sodium carbonate In dimethyl sulfoxide at 120℃; for 24 h; Inert atmosphere; Sealed tube General procedure: Knölker iron complex 2a (3 mol percent,12.6 mg), paraformaldehyde (300 mg, 10 mmol), and Na2CO3 (106 mg, 1 mmol,1.0 equiv) and a stirring bar were charged in a pressure tube and flushed withargon. DMSO (1.0 mL), degassed water (1.0 mL), and benzaldehyde (1 mmol)were added under an argon atmosphere to the pressure tube with a syringe.The pressure tube was placed in oil and heated at 120 C for 24 h, then cooledto room temperature. The reaction mixture was neutralized with HCl (1M) andstirred for 30 min. After extraction with EtOAc for 3 times, the combinedorganic layers were dried over MgSO4. The crude product was purified bycolumn chromatography (Heptane/EtOAc: 70:30). The reaction was cooled toroom temperature and hexadecane (100 lL) was added as a GC internalstandard.
990.0 mg With sodium tetrahydroborate In tetrahydrofuran at 20℃; for 0.25 h; Cooling with ice; Inert atmosphere Sodium borohydride (289.0 mg, 7.6 mmol) and Dowex 50 (1.4 g) were addedsuccessively to a solution of 4-cyanobenzaldehyde 27 (1.0 g, 7.6 mmol) in THF (20 mL) at icebath temperature under argon atmosphere. The reaction mixture was stirred at room temperaturefor 15 minutes and quenched with water. The layers were separated; aqueous layer was extractedwith DCM (2 × 30 mL). The combined organic layer was dried (MgSO4) and concentrated to getdesired product as a colorless solid. Yield: 990.0 mg, quant.

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  • [ 119072-55-8 ]
  • [ 18282-51-4 ]
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YieldReaction ConditionsOperation in experiment
76% With copper (II) trifluoroacetate hydrate; palladium diacetate In dimethyl sulfoxide at 130℃; for 6 h; Sealed tube; Inert atmosphere General procedure: Aryl iodide (0.7 mmol, 1 equiv), tert-butyl isocyanide (2.1 mmol, 237 μL, 3 equiv), Pd(OAc)2 (0.035 mmol, 8 mg, 5 mol percent), Cu(TFA)2*xH2O (1.4 mmol, 405 mg, 2 equiv) and DMSO (2.5 mL) were added to a 15 mL sealed tube, and stirred at 130 °C for 4-12 h under nitrogen. After completion of the reaction indicated by TLC, the mixture was extracted with Et2O (510 mL). The combined organic phases was dried over Na2SO4, and concentrated under vacuum. Then the residue was purified by column chromatography on silica gel using petroleum ether (30-60 °C)/Et2O as eluant to provide the pure target product.
Reference: [1] Tetrahedron, 2015, vol. 71, # 29, p. 4883 - 4887
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  • [ 64-17-5 ]
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YieldReaction ConditionsOperation in experiment
60 %Spectr. With C21H35BrMnN2O2P; hydrogen; potassium hydride In toluene at 100℃; for 60 h; Hydrogenation of 1 mmol of hexyl hexanoate under 20 bar at 100°C in toluene, resulted in 99percent yield of hexanol (Entry 1). Under the same conditions ethyl butyrate was hydrogenated to give 98percent yield of butanol and 91 percent yield of ethanol after 50 hours (Entry 2). When the reaction was performed at shorter reaction time (22 hours, Entry 2bis), small amounts of ethyl acetate and butyl butanoate were also formed, attributed to a transesterification reaction with the formed ethanol and butanol. Cyclohexylmethyl acetate gave 99percent yield of cyclohexylmethanol and 60percent yield of ethanol (Entry 3), and no transesterification products were observed. Hydrogenation of the secondary aliphatic ester heptan-2-yl acetate resulted in 98percent yield of heptane-2-ol and 57percent yield of ethanol (Entry 4). Ethyl 3-phenylpropanoate was smoothly hydrogenated, rendering 99percent yield of 3-phenylpropan-l-ol and 70percent yield of ethanol after 21 hours (Entry 5). Similarly, ethyl 3- phenylpropanoate gave 99percent yield of phenyknethanol and 74percent yield of butanol after 22 hours (Entry 6). In order to get full hydrogenation of benzyl benzoate longer reaction time was needed (43 hours, 99percent yield benzyl alcohol, Entry 7). Similarly, methyl benzoate gave 96percent yield of benzyl alcohol and 63 percent of methanol after 50 hours (Entry 8). ε-Caprolactone was smoothly and quantitatively hydrogenated to 1 ,6-hexanediol (99percent yield, Entry 9). The activated benzyl trifluoroacetate gave 99percent yield of benzyl alcohol and 78percent of 2,2,2- trifluoroethanol (Entry 10), and no secondary products where observed. Gratifyingly, allyl trifluoroacetate gave 97percent yield of 2,2,2-trifluoroethanol and 96percent of allyl alcohol (Entry 1 1), showing high chemoselectivity to ester hydrogenation over C=C hydrogenation. Hydrogenation of ethyl 4-isocyano-benzoate required an increase of precatalyst loading to 3percent, probably due to competing nitrile coordination, and resulted in 61 percent yield of (4-isocyanophenyl)methanol and 66percent yield of ethanol, with no hydrogenation of the nitrile group detected (Entry 12).
Reference: [1] Patent: WO2017/137984, 2017, A1, . Location in patent: Paragraph 00352-00353
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YieldReaction ConditionsOperation in experiment
61% With sodium carbonate; dimethyl sulfoxide; trifluoroacetic acid; sodium nitrite In water Example 1
p-Cyanobenzylamine (26.2 g), sodium nitrite (20.8 g), and dimethyl sulfoxide (200 ml) were mixed, and the mixture was vigorously stirred at room temperature (about 20 to 30° C.).
Trifluoroacetic acid (45.6 g) was added dropwise to the mixture over a one hour period.
After completion of addition, the mixture was further allowed to react at 100° C. for one hour.
The reaction mixture was analyzed by use of high performance liquid chromatography, to thereby obtain proportions (on the mol basis) of predominant reaction products: p-cyanobenzyl alcohol:p-cyanobenzaldehyde:p-cyanobenzoic acid=72:18:10.
Dimethyl sulfoxide was removed through distillation under vacuum, and water (300 ml) was added to the residue.
Sodium carbonate was added to the thus-formed solution, to thereby adjust pH to 8.
The resultant aqueous solution was subjected to extraction with toluene (300 ml*2).
Toluene was removed through distillation under reduced pressure, and the resultant solution was subsequently distilled under vacuum, to thereby obtain 16.2 g of p-cyanobenzyl alcohol (bp. 175-178° C./1.5 kPa) (yield 61percent).
The purity of the product was 98percent.
51% With sulfuric acid; sodium nitrite In water; toluene Example 3
p-Cyanobenzylamine (13.2 g), water (54 g), and toluene (20 g) were mixed, and the mixture was stirred with cooling with ice.
Concentrated sulfuric acid (14.7 g) was added to the mixture.
Subsequently, a 20 wt percent aqueous solution (44.9 g) of sodium nitrite was added dropwise to the mixture over one hour.
The mixture was stirred at the same temperature for four hours.
For the subsequent process, the procedure of Example 1 was repeated, to thereby obtain 6.8 g of p-cyanobenzyl alcohol (yield 51percent).
The purity of the product was 98percent.
Reference: [1] Patent: US6187945, 2001, B1,
[2] Patent: US6187945, 2001, B1,
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YieldReaction ConditionsOperation in experiment
98% With ammonia; hydrogen In methanol for 20 h; (4-Aminomethyl-phenyl)-methanol hydrochloride salt 4-Hydroxymethyl-benzonitrile (2.0 g, 15 mol) was reduced using Raney nickel (0. 5g) and hydrogen (50 psi) in MeOH: NH3 (100ml) for 20 hours. The reaction mixture was filtered through a pad of celite. The filtrate was concentrated under reduced pressure to afford (4-aminomethyl-phenyl)-methanol hydrochloride salt (2.01 g, 98percent) as a white solid of sufficient purity for use without further purification: MS (APCI+) : m/z 138.3 (M+H); H-NMR (DMSO-d6) 8 7.20 (s, 4 H), 5.04 (s, 2 H), 4.42 (s, 2 H), 3.83 (s, 1 H), 2.45 (s, 2 H).
29% With lithium aluminium tetrahydride In diethyl ether at 0℃; for 3.25 h; Reflux Example 99
N-((4-(hydroxymethyl)phenyl)methyl)-N-(1-methylpiperidin-4-yl)-2-(4-methoxyphenyl)acetamide hydrochloride (57MBT72D)
To a stirred suspension of LiAlH4 (285 mg, 7.52 mmol) in diethylether (10 mL) at 0° C. was added a solution of 4-cyanobenzyl alcohol (0.5 g, 3.76 mmol) in diethylether (5 mL) over 15 min.
The grey reaction mixture was heated to reflux for 3 h.
After cooling to r.t., the mixture was treated successively with water (1 mL), 2M NaOH (2 mL) and water (2 mL) under vigorous stirring.
The resulting white slurry was filtered and washed with CH2Cl2 (20 mL).
Extraction with additional CH2Cl2 (20 mL) and n-butanol (20 mL) and evaporation yielded an oil, which upon flash chromatography (0-15percent MeOH in CH2Cl2) gave 152 mg (29percent) of 4-(aminomethyl)benzylalcohol (57MBT52B) as a white solid. Rf=0.51 (30percent MeOH in CH2Cl2+3.5percent NH4OH).
29%
Stage #1: With lithium aluminium tetrahydride In diethyl ether at 0℃; for 3.25 h; Heating / reflux
Stage #2: With sodium hydroxide In diethyl ether; water at 20℃;
To a stirred suspension of LiAlHU (285 mg, 7.52 mmol) in diethylether (10 mL)at 0° C. was added a solution of 4-cyanobenzyl alcohol (0.5 g, 3.76 mmol) in diethylether (5 mL) over 15 min. The grey reaction mixture was heated to reflux for 3 h. After cooling to r.t, the mixture was treated successively with water (1 mL), 2M NaOH (2 mL) and water (2 mL) under vigorous stirring. The resulting white slurry was filtered and washed with CH2Cl2 (20 mL). Extraction with additional CH2Cl2 (20 mL) and n- butanol (20 mL) and evaporation yielded an oil, which upon flash chromatography (0- 15percent MeOH in CH2Cl2) gave 152 mg (29percent)of 4-(aminomethyl)benzylalcohol (57MBT52B) as a white solid. Rf=0.51 (30percent MeOH in CH2Cl2 +3.5percent NH4 OH).
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[3] Journal of Medicinal Chemistry, 2014, vol. 57, # 19, p. 8140 - 8151
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