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CAS No. :2765-11-9 MDL No. :MFCD12911660
Formula : C15H30O Boiling Point : -
Linear Structure Formula :- InChI Key :XGQJZNCFDLXSIJ-UHFFFAOYSA-N
M.W : 226.40 Pubchem ID :17697
Synonyms :

Safety of [ 2765-11-9 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P264-P280-P337+P313-P305+P351+P338-P302+P352-P332+P313-P362 UN#:N/A
Hazard Statements:H315-H319 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 2765-11-9 ]

* 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.

  • Downstream synthetic route of [ 2765-11-9 ]

[ 2765-11-9 ] Synthesis Path-Downstream   1~100

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  • [ 764-67-0 ]
  • [ 546-67-8 ]
  • [ 2765-11-9 ]
  • 3
  • [ 629-76-5 ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
100% With oxalyl dichloride; dimethyl sulfoxide; triethylamine In dichloromethane at -78℃;
90% With pyridinium chlorochromate In dichloromethane for 4h;
90.8% With mesoporous silica; 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate In dichloromethane at 20℃; Inert atmosphere;
87% With Dess-Martin periodane In dichloromethane at 20℃; for 0.75h;
87% With 1-hydroxy-3H-benz[d][1,2]iodoxole-1,3-dione In acetonitrile Reflux;
85% With Dess-Martin periodane In dichloromethane at 20℃; for 5h;
85% With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; [bis(acetoxy)iodo]benzene In dichloromethane at 20℃; for 3h;
83% Stage #1: n-pentadecyl alcohol With Chloro-oxo-acetic acid; dimethyl sulfoxide In dichloromethane at -78℃; for 0.333333h; Inert atmosphere; Stage #2: With triethylamine In dichloromethane at -78 - 20℃; for 1.25h; Inert atmosphere;
50% With ruthenium (III) chloride; sodium (meta)periodate In dichloromethane; lithium hydroxide monohydrate at 20℃; for 2h;
20% With chromium(VI) oxide In toluene for 24h; Heating;
With N-Methylmorpholine N-oxide In acetonitrile at 25℃;
With anhydrous Sodium acetate; pyridinium chlorochromate In dichloromethane
With oxalyl dichloride; dimethyl sulfoxide; triethylamine 1.) CH2Cl2, -20 deg C, 30 min, 2.) -20 deg C to r.t.; Yield given. Multistep reaction;
With diphosphorus pentoxide; dimethyl sulfoxide; triethylamine In dichloromethane at 0℃;
69 % Chromat. With polystyrene-supported 5-hydroxy-2-iodoxybenzoic acid In dichloromethane at 20℃; for 3h;
Stage #1: n-pentadecyl alcohol With diphosphorus pentoxide; dimethyl sulfoxide In dichloromethane at 0 - 20℃; for 0.75h; Stage #2: With triethylamine In dichloromethane at 0 - 20℃; for 1.5h;
With pyridinium chlorochromate
With oxalyl dichloride; dimethyl sulfoxide; triethylamine In dichloromethane at -78 - 20℃;
With pyridinium chlorochromate In dichloromethane at 0℃; for 3h;
With pivaloyl chloride; dimethyl sulfoxide; triethylamine at -78℃;
24 %Chromat. With C77H60Cl2N4O4PRu2; N-Methylmorpholine N-oxide In dichloromethane for 12h; Reflux;
Stage #1: n-pentadecyl alcohol With oxalyl dichloride; dimethyl sulfoxide In dichloromethane at -78℃; for 0.666667h; Stage #2: With triethylamine In dichloromethane at -78℃;
Stage #1: n-pentadecyl alcohol With pivaloyl chloride; dimethyl sulfoxide In dichloromethane at -78℃; Stage #2: With triethylamine In dichloromethane at -78 - 20℃;
With Dess-Martin periodane In dichloromethane at 0℃; for 0.75h; 5.1.1. General procedure for the synthesis of aldehydes 12a,b. Example: tetradecanal (12a)[67] and 77 Y.-H. Chang, B.-J. Uang, C.-M. Wu and T.-H. Yu, Synthesis 1990 (1990), p. 1033. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (5)[77] General procedure: To a solution of commercial tetradecan-1-ol (0.72 g, 3.37 mmol) in DCM (20 mL) at 0 °C Dess-Martin periodinane (DMP) (1.53 g, 3.60 mmol) was added. After completion (45 min, TLC monitoring), the reaction crude was directly purified by column chromatography (silica gel, CHCl3/n-hexane, 3:1) to afford the required aldehyde as a waxy white solid (187 mg, 98% yield). 1H NMR (CDCl3): δ 0.88 (t, 3H, CH3), 1.26-1.29 (m, 20H, 10 × CH2), 1.60-1.65 (m, 2H, CH2), 2.40-2.50 (m, 2H, CH2), 9.77 (t, 1H, H-1); MS (EI, 70 eV) m/z (%): 212.
With chromium trioxide-pyridine complex
With oxalyl dichloride; dimethyl sulfoxide; triethylamine at -78℃; for 1h; (Z)-Docosa-5-en-1,9-diyne (4) General procedure: To a solution of DMSO (0.27 mL, 3.84 mmol, 3.0 equiv) in CH2Cl2(25mL) at -78 °C was added oxalyl chloride (0.165 mL, 1.92 mmol, 1.5equiv). The resulting mixture was stirred for 15 min, then a solutionof alkynol 35(322 mg, 1.28 mmol, 1.0 equiv) in CH2Cl2(5 mL) wasadded and stirring was continued for 45 min. The reaction mixturewas then quenched with Et3N (0.8 mL, 5.76 mmol, 4.5 equiv) and saturated aq. NaHCO3(5 mL). The obtained solution was extracted withCH2Cl2(3 × 20 mL). The combined organic layers were washed withwater and brine, dried (Na2SO4) and concentrated. The crude aldehyde (307 mg) was used without purification in the next step.To a solution of pent-4-ynyltriphenylphosphonium iodide (34) (616mg, 1.35 mmol, 1.1 equiv) in THF (10 mL) under nitrogen was addedNaHMDS (1.3 mL, 1.35 mmol, 1.1 equiv, 1 M in THF) dropwise at -78°C and the mixture was stirred for 1 h. An orange coloration was observed and to this mixture was added dropwise a suspension of a predissolved solution of crude heptadec-4-ynal (307 mg, 1.23 mmol, 1equiv) in THF (10 mL). After 16 h, the reaction mixture was quenchedwith saturated aq. NH4Cl (1 mL) and concentrated. The aqueous residue was extracted with EtOAc (3 × 20 mL). The combined organic layers were washed with water and brine, dried (Na2SO4) and concentrated. The residue was purified by silica gel column chromatographywith petroleum ether as the eluent to afford (Z)-docosa-5-en-1,9-diyne (4) as a colorless oil (296.2 mg, 77% over two steps from 35).

Reference: [1]Dobbs, Adrian P.; Venturelli, Alberto; Butler, Laura A.; Parker, Robert J. [Synlett, 2005, # 4, p. 652 - 654]
[2]Mun, JiYoung; Onorato, Amber; Nichols, Frank C.; Morton, Martha D.; Saleh, Abdullah I.; Welzel, Morgan; Smith, Michael B. [Organic and Biomolecular Chemistry, 2007, vol. 5, # 23, p. 3826 - 3833]
[3]Dietz, Christopher; Clark, Robert B.; Nichols, Frank C.; Smith, Michael B. [Journal of labelled compounds and radiopharmaceuticals, 2017, vol. 60, # 6, p. 274 - 285]
[4]Sbardella, Gianluca; Castellano, Sabrina; Vicidomini, Caterina; Rotili, Dante; Nebbioso, Angela; Miceli, Marco; Altucci, Lucia; Mai, Antonello [Bioorganic and Medicinal Chemistry Letters, 2008, vol. 18, # 9, p. 2788 - 2792]
[5]Haghshenas, Pouyan; Gravel, Michel [Organic Letters, 2016, vol. 18, # 18, p. 4518 - 4521]
[6]Schlutt, Birgit; Moran, Noelia; Schieberle, Peter; Hofmann, Thomas [Journal of Agricultural and Food Chemistry, 2007, vol. 55, # 23, p. 9634 - 9645]
[7]Paul, Bishwajit; Das, Debasis; Ellington, Benjamin; Marsh, E. Neil G. [Journal of the American Chemical Society, 2013, vol. 135, # 14, p. 5234 - 5237]
[8]O'Neil, Gregory W.; Moser, Daniel J.; Volz, Erasmus O. [Tetrahedron Letters, 2009, vol. 50, # 52, p. 7355 - 7357]
[9]Genet, J. P.; Pons, D.; Juge, S. [Synthetic Communications, 1989, vol. 19, # 9-10, p. 1721 - 1726]
[10]Hamilton-Kemp, Thomas R.; Andersen, Roger A. [Phytochemistry, 1986, vol. 25, # 1, p. 241 - 243]
[11]Caroling; Rajaram; Kuriacose [Journal of the Indian Chemical Society, 1989, vol. 66, # 8-10, p. 632 - 638]
[12]Furukawa, Jun; Iwasaki, Shigeo; Okuda, Shigenobu [Tetrahedron Letters, 1983, vol. 24, # 47, p. 5257 - 5260]
[13]Enders, Dieter; Whitehouse, Darren L.; Runsink, Jan [Chemistry - A European Journal, 1995, vol. 1, # 6, p. 382 - 388]
[14]Fernandes, Rodney A.; Kumar, Pradeep [Tetrahedron Letters, 2000, vol. 41, # 52, p. 10309 - 10312]
[15]Sorg; Mengel; Jung; Rademann [Angewandte Chemie - International Edition, 2001, vol. 40, # 23, p. 4395 - 4397]
[16]Fernandes, Rodney A.; Kumar, Pradeep [Synthesis, 2003, # 1, p. 129 - 135]
[17]Murga, Juan; Garcia-Fortanet, Jorge; Carda, Miguel; Marco, J. Alberto [Journal of Organic Chemistry, 2004, vol. 69, # 21, p. 7277 - 7283]
[18]Tilley, S. David; Francis, Matthew B. [Journal of the American Chemical Society, 2006, vol. 128, # 4, p. 1080 - 1081]
[19]Venkatesan; Srinivasan [Tetrahedron Asymmetry, 2008, vol. 19, # 2, p. 209 - 215]
[20]Location in patent: scheme or table Dubey, Abhishek; Kumar, Pradeep [Tetrahedron Letters, 2009, vol. 50, # 26, p. 3425 - 3427]
[21]Location in patent: experimental part Venkatachalam; Raja; Pandiarajan; Ramesh [Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2008, vol. 71, # 3, p. 884 - 891]
[22]Location in patent: experimental part George, Shyla; Suryavanshi, Gurunath; Sudalai, Arumugam [Tetrahedron Asymmetry, 2010, vol. 21, # 5, p. 558 - 561]
[23]Location in patent: experimental part Kumar, Pradeep; Dubey, Abhishek; Puranik, Vedavati G. [Organic and Biomolecular Chemistry, 2010, vol. 8, # 22, p. 5074 - 5086]
[24]Location in patent: experimental part Milite, Ciro; Castellano, Sabrina; Benedetti, Rosaria; Tosco, Alessandra; Ciliberti, Carmen; Vicidomini, Caterina; Boully, Ludovic; Franci, Gianluigi; Altucci, Lucia; Mai, Antonello; Sbardella, Gianluca [Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 12, p. 3690 - 3701]
[25]Location in patent: body text Abdelmohsen, Usama Ramadan; Zhang, Guoliang; Philippe, Allan; Schmitz, Werner; Pimentel-Elardo, Sheila Marie; Hertlein-Amslinger, Barbara; Hentschel, Ute; Bringmann, Gerhard [Tetrahedron Letters, 2012, vol. 53, # 1, p. 23 - 29]
[26]Chandra, Naveen; Fernandes, Rodney A. [Synthesis, 2022]
  • 4
  • [ 2765-11-9 ]
  • [ 132682-21-4 ]
  • [ 143799-48-8 ]
  • [ 143799-49-9 ]
YieldReaction ConditionsOperation in experiment
With n-butyllithium Yield given. Multistep reaction. Yields of byproduct given;
Stage #1: (S)-(+)-4-(2-oxazolidonyl)-methyltriphenylphosphonyl iodide With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Stage #2: n-pentadecanal In tetrahydrofuran at -78℃; for 2.5h; Title compound not separated from byproducts;
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  • [ 6920-24-7 ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
89% With sodium periodate for 6h; Inert atmosphere;
96 % Spectr. With periodate form of Amberlite IRA 904 In dichloromethane for 3h; Heating;
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  • [ 81618-17-9 ]
  • [ 109-87-5 ]
  • [ 2765-11-9 ]
  • [ 107-31-3 ]
  • [ 1002-84-2 ]
  • [ 7132-64-1 ]
  • [ 52517-73-4 ]
YieldReaction ConditionsOperation in experiment
1: 19.6% 2: 8.8% 3: 14.1% 4: 21.3% 5: 20.3% 6: 2.2% In methanol at 90℃; for 6h; other solvents; other objects of study: energy data, velocity constant;
  • 7
  • [ 83486-16-2 ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
93% With iodine; sodium iodide
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  • [ 1120-36-1 ]
  • [ 201230-82-2 ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
97% With hydrogen; Diphenyl-4-natriumsulfonatobutyl-phosphan In methanol at 80℃; for 2h;
With hydrogen at 100℃; for 0.5h; regioselective reaction; 19 Example 19 Rh (acac) (CO)2/ [Ph (EO)16The N+the H = the C (the N (CH3)2)2]2[Xantphos- (SO3-)2] (O = p = 1, q = r = 2) / [Ph (EO)16The N+the H = the C (the N (CH3)2)2] [CH3SO3-] Under / tetradecene system of two-phase hydroformylation1-tetradecene, and the rest of the reaction conditions and procedure were the same as in Example 9. Gas chromatographic analysis showed that the conversion of 1-tetradecene was 65.6%, the chemical selectivity of the aldehyde was 84.4% aldehyde molar ratio of 18.0: 1.0 (n-aldehyde regioselectivity of 94.7%), TOF value of 1107h-1.
With dicarbonyl(acetylacotonato)rhodium(I); C43H80NO17(1+)*CH3O3S(1-); hydrogen; 9,9-dimethyl-2,7-bissulfonato-4,5-bis(diphenylphosphino)xanthene-sodium salt at 100℃; for 0.5h; Autoclave; 22 Example 3Rh (acc) (C0) 2 / Xantphos- (S03Na) 2 (3) / [(N- (E0) i6Ph) (N_CH3) Mor] [CH3SO3]Synthesis of two-phase hydroformylation reaction in octene system (l = m = 2) General procedure: Under an inert atmosphere, Rh (acac) (CO) 2, Xantphos_ (SO3Na) 2 was added to the stainless steel high pressure reaction dad(S03Na) 2 (3) / Rh (acac) (C0), and the ratio of Xantphos- (N0 CH3) Mor] [CH3S03-] and 1_ (Molar ratio), [(N- (E0) 16Ph) (N-CH3) Mor] [ CH3S03 -] / Rh (acac) () 2 = 300: 1 (molar ratio), then pressurized to 5. OMPa with synthesis gas (H2 / C0 = 1: 1), reaction temperature 100 ° C, reaction time 0.5 And then rapidly cooled to room temperature, venting the synthesis gas after the opening of the reactor, the lower ionic liquid phase solidification, through the ionic liquid phase and organic phase liquid / solid two-phase separation of rhodium catalyst recovery, can also be added n-heptane extraction, The results showed that the conversion of 1-octene was 29.6%, the chemical selectivity of aldehyde was 94.5%, the molar ratio of n-aldehyde to isomer was determined by simple liquid / solid two-phase separation. The ratio was 30.0: 1.0 (96.8% of the regioselective aldehyde)
With dicarbonylacetylacetonato rhodium (I); trisulfonated triphenylphosphine trisodium salt; hydrogen; alpha cyclodextrin In water at 80℃; for 4h; regioselective reaction;
With dicarbonyl(acetylacotonato)rhodium(I); 2C21H36NO4(1+)*C39H30O7P2S2(2-); hydrogen at 100℃; for 0.5h; Autoclave; 19 Rh (acac) (CO) 2 / [(Ν- (Ε0) 4Ph) (N-C 2 H 5) Pi] 2 [(S03-) 2-12], N = 2) / 1-octeneSystem two-phase hydroformylation reaction Under an inert atmosphere, a stainless steel autoclave was charged with Rh (acac) (CO) 2, [(N_ (E0) 4Ph) (N_C2H5) Pi] 2 [(S03-) 2-12] and 1-octene, The ratio is:[(N- (E0) 4Ph) (N-C2H5) Pi] 2 [(S03-) 2_12] / Rh(acac) (CO) 2 = 1000: (acac) (CO) 2 = 5: 11 (molar ratio),Then with syngas (H /C0 = 1: 1) pressurized to 5. OMPa, the reaction temperature was 100 ° C, The reaction time 0.5 hours, Then quickly cooled to room temperature, vent togetherAfter the gas into the kettle, The system is naturally divided into two phases, the lower is the ionic liquid containing rhodium catalyst phase, the upper organic phase, but alsoAdd n-heptane extraction, after a simple two-phase separation of the organic phase containing the product aldehyde, gas chromatography analysis results: 1_ XinThe conversion of olefin was 99.2%, The selectivity of aldehyde was 74.1%, and the molar ratio of normal aldehyde to isomeric aldehyde was 1.9: 1

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  • [ 1120-36-1 ]
  • [ 201230-82-2 ]
  • [ 2765-11-9 ]
  • 2-methyl-1-tetradecanal [ No CAS ]
YieldReaction ConditionsOperation in experiment
With acetylacetonatodicarbonylrhodium(l); trisodium tris(3-sulfophenyl)phosphine; heptakis(2,6-di-O-methyl)cyclomaltoheptaose; hydrogen In water at 80℃; for 6h; stainless steel autoclave; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
With hydrogen; Aliquat 336 In 2,2,4-trimethylpentane; water at 80℃; for 21h;
With hydrogen In n-heptane; toluene at 90℃; for 20h;
With (acetylacetonato)dicarbonylrhodium (l); trisodium tris(3-sulfophenyl)phosphine; hydrogen In water at 80℃; for 6h; Inert atmosphere;
With dicarbonylacetylacetonato rhodium (I); hydrogen; trisodium triphenylphosphine‐3,3′,3″‐trisulfonate at 80℃; for 3h;
With dicarbonyl(acetylacotonato)rhodium(I); trisodium tris(3-sulfophenyl)phosphine; hydrogen; alpha cyclodextrin In water at 80℃; for 1h; chemoselective reaction;
With dicobalt octacarbonyl; C20H39P; hydrogen; sodium acetate In toluene at 110℃; for 22h; Autoclave; regioselective reaction; III-General Procedure for hydroformylation-reduction for Table 4 and 5 General procedure: Lim-10 (5-10 mol%), 2-ethylhexanoic acid (10 mol%) and KOH/EtOH (1.0 M soln.; 2.5 mol%) were loaded in to a glass liner containing a magnetic stirring bar and flushed with a continuous stream of argon. Solid Co2(CO)8 (5 mol%) was weighed promptly and added to the liner. Then, under argon protection, alkene (2.0 mmol) and solvent (5 mL) were added. The glass liner was then inserted into a stainless steel autoclave, capped and purged three times with CO and then pressurized at room temperature to 200 psi of CO and 400 psi of H2. The autoclave was heated at 110 C for 22 h and then cooled to room temperature before releasing the excess gases. The reaction mixture was then transferred to a flask using 5-10 mL of MeOH to which was added NaBH4 (1.2 equiv.) at 0 C and the consumption of the RCHO monitored by TLC. Upon completion of the reaction, the resulting mixture was acidified to PH~6 and extracted with ether (3x 50 mL). The combined organic layers were dried with anhydrous MgSO4 and the solvent was removed in vacuo to give an oil residue which was purified by flash chromatography on silica gel with hexane / EtOAc (v/v, 5:1 to 2:1) as the eluant to obtain inseparable mixture of alcohols in 53-99 % yields.
With dicarbonylacetylacetonato rhodium (I); C56H82NO40PS2(2-)*2Na(1+); hydrogen In water at 80℃; for 3h; Inert atmosphere; Autoclave; chemoselective reaction;
With acetylacetonatodicarbonylrhodium(l); C39H30O7P2S2(2-)*2C20H36O4P(1+); hydrogen at 100℃; for 0.5h; Autoclave; 17 Rh(acac)(CO)2/[Ph(OCH2CH2)16P(C2H5)3]2[(S03-)2-12](ο=p=2,n=2)/1-octene system two-phase hydroformylation reaction In an inert atmosphere, Rh (acac) (CO) 2, [Ph (OCH2CH2) 16P (C2H5) 3] 2 [(S03-) 2-12] and 1-octene were added to a stainless steel autoclave in proportions of [Ph (Acac) (CO) 2 = 5: 1 (molar ratio), 1-octyl / Rh (acac) 2 = 1000: 1 (molar ratio), Then pressurized with syngas (H2 / C0 = 1: 1) to 5.0MPa, the reaction temperature was 100 ° C, the reaction time 0.5 hours, and then quickly cooled to room temperature, venting the synthesis gas after opening the kettle, the system naturally divided into two phases, the lower Is an ionic liquid phase containing a rhodium catalyst, the upper layer is an organic phase, and n-heptane can also be added for extraction. The organic phase containing the product aldehyde is obtained through a simple two-phase separation. The gas chromatographic analysis results show that the conversion of 1-octene is 91.4%, the selectivity of aldehyde was 71.9%, the molar ratio of normal aldehyde to isomeric aldehyde was 1.8: 1, the T0F value was1314h-1.
With acetylacetonatodicarbonylrhodium(l); 2C19H34N3O4(1+)*C40H32O6P2S2(2-); hydrogen at 100℃; for 0.5h; Autoclave; 15 Rh(acac)(CO)2/[Ph(EO)4N+H=C(N(CH3)2)2]2[(SO3-)2-10](o=p=2,n=2)/Two-phase hydroformylation under 1-tetradecene system Add Rh(acac)(CO)2, [Ph(EO)4N+H=C(N) to a stainless steel autoclave under an inert atmosphere(CH3)2) 2]2[(SO3-)2-10] and 1-octene in the ratio: [Ph(EO)4N+H=C(N(CH3)2)2]2[(SO3 -) 2-10]/Rh(acac)(CO)2=5:1 (molar ratio), 1-octene/Rh(acac)(CO)2=1000:1 (molar ratio), then syngas (H2/)CO=1:1) Pressurization to 5.0MPa, reaction temperature 100°C, reaction time 0.5 hours, then rapidly cool to room temperature, releaseAfter the gas is formed, the system is naturally divided into two phases. The lower layer is an ionic liquid phase containing a ruthenium catalyst, and the upper layer is an organic phase.The n-heptane extraction was carried out, and the organic phase containing the product aldehyde was obtained by simple two-phase separation. The gas chromatographic analysis showed that the conversion of 1-octene was 96.8%, the selectivity of aldehyde was 69.4%, and the normal aldehyde and isomer were separated. The molar ratio of aldehyde is 1.8:1; The olefin was changed to 1-tetradecene, and the rest of the reaction conditions and procedures were the same as in Example 11. The gas chromatographic analysis showed that the conversion of 1-tetradecene was 71.2%, the selectivity of aldehyde was 75.0%, and the normal aldehyde and isomer The molar ratio of aldehyde was 1.5:1 and the TOF value was 1068 h-1.
With rhodium(III) chloride trihydrate; trisodium tris(3-sulfophenyl)phosphine; hydrogen at 85℃; for 5h; Inert atmosphere; Autoclave; Ionic liquid; chemoselective reaction;

Reference: [1]Monflier, Eric; Tilloy, Sebastien; Fremy, Georges; Castanet, Yves; Mortreux, Andre [Tetrahedron Letters, 1995, vol. 36, # 52, p. 9481 - 9484]
[2]Paganelli, Stefano; Perosa, Alvise; Selva, Maurizio [Advanced Synthesis and Catalysis, 2007, vol. 349, # 11-12, p. 1858 - 1862]
[3]Location in patent: scheme or table Zeng, Yan; Wang, Yanhua; Xu, Yicheng; Song, Ying; Zhao, Jiaqi; Jiang, Jingyang; Jin, Zilin [Cuihua Xuebao/Chinese Journal of Catalysis, 2012, vol. 33, # 2-3, p. 402 - 406]
[4]Location in patent: experimental part Ferreira, Michel; Legrand, Francois-Xavier; MacHut, Cecile; Bricout, Herve; Tilloy, Sebastien; Monflier, Eric [Dalton Transactions, 2012, vol. 41, # 28, p. 8643 - 8647]
[5]Potier, Jonathan; Menuel, Stephane; Chambrier, Marie-Heleine; Burylo, Laurence; Blach, Jean-Francois; Woisel, Patrice; Monflier, Eric; Hapiot, Frederic [ACS Catalysis, 2013, vol. 3, # 7, p. 1618 - 1621]
[6]Potier, Jonathan; Menuel, Stephane; Monflier, Eric; Hapiot, Frederic [ACS Catalysis, 2014, vol. 4, # 7, p. 2342 - 2346]
[7]Achonduh, George; Yang, Qian; Alper, Howard [Tetrahedron, 2015, vol. 71, # 8, p. 1241 - 1246]
[8]Leblond; Potier; Menuel; Bricout; Machut-Binkowski; Landy; Tilloy; Monflier; Hapiot [Catalysis science and technology, 2017, vol. 7, # 17, p. 3823 - 3830]
[9]Current Patent Assignee: QINGDAO UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN105017319, 2017, B Location in patent: Paragraph 0070-0072
[10]Current Patent Assignee: QINGDAO UNIVERSITY OF SCIENCE AND TECHNOLOGY - CN105017317, 2018, B Location in patent: Paragraph 0053; 0063; 0064; 0065
[11]Jin, Xin; Yang, Daoxing; Xu, Xinfu; Yang, Zhiqiang [Chemical Communications, 2012, vol. 48, # 72, p. 9017 - 9019,3]
  • 10
  • [ 2765-11-9 ]
  • [ 1666-13-3 ]
  • 2-(Phenylselenyl)pentadecanal [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With selenium(IV) oxide; sulfuric acid In dichloromethane Ambient temperature;
  • 11
  • [ 1002-84-2 ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
With ThxBHO-s-Bu In tetrahydrofuran at 25℃; for 96h; Yield given;
Multi-step reaction with 2 steps 1: tetrahydrofuran / 20 °C 2: Li(Et2N)3AlH; pyridine / tetrahydrofuran / 0.5 h / 0 °C
  • 12
  • [ 2765-11-9 ]
  • [ 629-76-5 ]
YieldReaction ConditionsOperation in experiment
With ruthenium trichloride; trisodium tris(3-sulfophenyl)phosphine; heptakis(2,6-di-O-methyl)cyclomaltoheptaose; hydrogen; sodium iodide In water; toluene at 80℃; for 6h;
Multi-step reaction with 2 steps 1: diethyl ether 2: 1.) RuO4*2H2O/NaIO4, 2.) LAH / 1.) CH2Cl2/H2O, 2.) Et2O
Multi-step reaction with 2 steps 1: diethyl ether 2: 1.) RuO4*2H2O/NaIO4, 2.) LAH / 1.) CH2Cl2/H2O, 2.) Et2O
  • 13
  • pentadecanoic acid 9-aza-bicyclo[3.3.1]non-9-yl ester [ No CAS ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
With pyridine; lithium-tris(diethylamino)hydridoaluminate In tetrahydrofuran at 0℃; for 0.5h;
YieldReaction ConditionsOperation in experiment
98% In chloroform at 40℃;
  • 16
  • [ 2765-11-9 ]
  • [ 667-27-6 ]
  • [ 321856-34-2 ]
YieldReaction ConditionsOperation in experiment
67% With zinc In tetrahydrofuran for 1h; Heating;
  • 19
  • [ 2765-11-9 ]
  • [ 1730-25-2 ]
  • [ 631897-61-5 ]
  • [ 791819-20-0 ]
YieldReaction ConditionsOperation in experiment
With B-chlorodiisopinocampheylborane In diethyl ether at -100℃; for 1h;
Stage #1: allylmagnesium bromide With B-chlorodiisopinocampheylborane In diethyl ether for 1h; cooling; Stage #2: n-pentadecanal In diethyl ether at -100℃; for 1h; Title compound not separated from byproducts;
  • 20
  • [ 2765-11-9 ]
  • [ 13138-33-5 ]
  • (3-pentadecylamino-propyl)-phosphonic acid [ No CAS ]
  • 21
  • [ 2765-11-9 ]
  • [ 7333-63-3 ]
  • [ 851316-89-7 ]
  • (E)-1-Bromo-nonadec-4-ene [ No CAS ]
  • 22
  • [ 2765-11-9 ]
  • [ 108-46-3 ]
  • C84H136O8 [ No CAS ]
YieldReaction ConditionsOperation in experiment
20% With hydrogenchloride In ethanol at 80℃; for 0.5h;
  • 23
  • [ 2765-11-9 ]
  • [ 1066-54-2 ]
  • [ 866946-15-8 ]
YieldReaction ConditionsOperation in experiment
99% With n-butyllithium In tetrahydrofuran at -78 - -10℃;
  • 24
  • [ 2765-11-9 ]
  • [ 1779-58-4 ]
  • [ 877212-95-8 ]
  • 25
  • [ 2765-11-9 ]
  • [ 121269-45-2 ]
  • (2R,6R,7S,9R)-2-phenyl-7,9-ditetradecyl-1-aza-4,8-dioxabicyclo[4.3.0]nonan-5-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
68% With 4 A molecular sieve In toluene for 120h; Heating;
  • 26
  • [ 201230-82-2 ]
  • [ 2765-11-9 ]
  • [ 10486-19-8 ]
  • [ 37596-36-4 ]
  • [ 73401-51-1 ]
  • [ 35518-76-4 ]
  • [ 65899-14-1 ]
  • 2-Amyldecanal [ No CAS ]
  • 2-Butylhendecanal [ No CAS ]
  • 2-Propyldodecanal [ No CAS ]
  • 2-methyl-1-tetradecanal [ No CAS ]
  • 2-Pentyl-octanal [ No CAS ]
YieldReaction ConditionsOperation in experiment
With hydrogen In toluene at 130℃; for 6 - 7h; 1 EXAMPLE 1Production of a Blend of Aldehydes of Type (I) and (II) (On the Basis of the Method According to DE 39 42 954)420 g of C12 (70%) and C14 (30%) olefin blend, 3.2 g of triphenylphosphine and 2.2 g of a toluene solution of rhodium 2-ethylhexanoate (corresponding to 125 mg of rhodium), corresponding to a rhodium:phosphorus ratio of 1:100, were introduced into a 1 I stirred autoclave. The temperature was then raised to 130° C. within one hour and hydroformylation was carried out for 6 to 7 hours at this temperature and a pressure of 26 MPa. After cooling to room temperature, the autoclave was flushed with nitrogen. The crude product was filtered (crude yield 442 g) and vacuum-fractionated using a 30 cm Vigreux column. Yield: 443.5 g (92% of theoretical) Boiling point: 130°-140° C./8 mbarGC evaluation (20 m ZB-WAX, internal diameter 0.18 μm/60-9-220° C. programmed-temperature vaporization system)
  • 27
  • [ 2765-11-9 ]
  • [ 140-88-5 ]
  • [ 502-26-1 ]
  • 28
  • [ 2765-11-9 ]
  • [ 877212-97-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1.1: aq. NaOH 1.2: 2.97 g / CH2Cl2 2.1: DIBAL-H / CH2Cl2 / 4 h / 20 °C 3.1: pyridine / CH2Cl2 / 0.17 h
  • 29
  • [ 2765-11-9 ]
  • (E)-heptadec-2-enyl taurine carbamate, sodium salt [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1.1: aq. NaOH 1.2: 2.97 g / CH2Cl2 2.1: DIBAL-H / CH2Cl2 / 4 h / 20 °C 3.1: pyridine / CH2Cl2 / 0.17 h 4.1: 0.33 g / dimethylformamide / 8 h / 20 °C
  • 30
  • [ 2765-11-9 ]
  • [ 97545-57-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: aq. NaOH 1.2: 2.97 g / CH2Cl2 2.1: DIBAL-H / CH2Cl2 / 4 h / 20 °C
  • 31
  • [ 2765-11-9 ]
  • [ 78472-08-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: 65 percent / tetrahydrofuran / 2 h / 0 °C 2: 74 percent / triphenylphosphine; diisopropyl azodicarboxylate / toluene / 24 h / 20 °C 3: 92 percent / dimethylformamide / 0.5 h / 180 °C / microwave irradiation 4: 85 percent / H2 / Pd/C / ethyl acetate / 4 h 5: 48 percent / salcomine catalyst; O2 / acetonitrile / 24 h / 20 °C
Multi-step reaction with 5 steps 1: 74 percent / DIAD; Ph3P 2: 92 percent / dimethylformamide / 0.42 h / 180 °C / microwave irradiation 3: 85 percent / H2 / Pd/C / ethyl acetate 4: 48 percent / potassium nitrosodisulfonate; aq. Na2HPO4 / acetone
  • 32
  • [ 2765-11-9 ]
  • [ 134284-28-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 65 percent / tetrahydrofuran / 2 h / 0 °C 2: 74 percent / triphenylphosphine; diisopropyl azodicarboxylate / toluene / 24 h / 20 °C 3: 92 percent / dimethylformamide / 0.5 h / 180 °C / microwave irradiation 4: 85 percent / H2 / Pd/C / ethyl acetate / 4 h
Multi-step reaction with 4 steps 1: 74 percent / DIAD; Ph3P 2: 92 percent / dimethylformamide / 0.42 h / 180 °C / microwave irradiation 3: 85 percent / H2 / Pd/C / ethyl acetate
  • 33
  • [ 2765-11-9 ]
  • [ 791819-09-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 1.2: diethyl ether / 1 h / -100 °C 2.1: 90 percent / imidazole / dimethylformamide / 18 h / 20 °C 3.1: 9-BBN / tetrahydrofuran / 18 h / 20 °C 3.2: 82 percent / aq. NaOH; aq. H2O2 / tetrahydrofuran; methanol / 1 h / 50 °C 4.1: DMSO; (COCl)2; Et3N / CH2Cl2 / 1.25 h / -78 - 0 °C 5.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 5.2: 727 mg / diethyl ether / 1 h / -100 °C 6.1: 85 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 7.1: O3 / CH2Cl2 / -78 °C 7.2: PPh3 / CH2Cl2 / 2 h / 20 °C 8.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 8.2: 499 mg / diethyl ether / 1 h / -100 °C 9.1: 95 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 10.1: O3 / CH2Cl2 / -78 °C 10.2: PPh3 / CH2Cl2 / 2 h / 20 °C 11.1: (-)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 11.2: diethyl ether / 1 h / -100 °C 12.1: 81 percent / iPr2NEt / CH2Cl2 / 2 h / -78 °C 13.1: 86 percent / PhCH=RuCl2(PCy3)2 / CH2Cl2 / 3 h / Heating
Multi-step reaction with 13 steps 1.1: (+)-diisopinocamphenylboron chloride / diethyl ether / 1 h / -100 °C 2.1: 80 percent / imidazole / dimethylformamide / 18 h / 20 °C 3.1: 9-borabicyclo[3.3.1]nonane / tetrahydrofuran / 20 h / 20 °C 3.2: 82 percent / H2O2; NaOH / ethanol / 1 h / 50 °C 4.1: (+)-diisopinocamphenylboron chloride / diethyl ether / -100 °C 5.1: 85 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 6.1: O3 / CH2Cl2 / -78 °C 6.2: PPh3 / 3 h / 20 °C 7.1: (+)-diisopinocamphenylboron chloride / diethyl ether / 1 h / -100 °C 8.1: 95 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 9.1: O3 / CH2Cl2 / -78 °C 9.2: PPh3 / 3 h / 20 °C 10.1: (+)-diisopinocamphenylboron chloride / diethyl ether / 1 h / -100 °C 11.1: 81 percent / EtN(i-Pr)2 / CH2Cl2 / 1.5 h / -78 °C 12.1: 86 percent / PhCH=RuCl2(PCy3)2 / CH2Cl2 / 2.5 h / Heating
  • 34
  • [ 2765-11-9 ]
  • [ 631897-72-8 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 1.2: diethyl ether / 1 h / -100 °C 2.1: 90 percent / imidazole / dimethylformamide / 18 h / 20 °C 3.1: 9-BBN / tetrahydrofuran / 18 h / 20 °C 3.2: 82 percent / aq. NaOH; aq. H2O2 / tetrahydrofuran; methanol / 1 h / 50 °C 4.1: DMSO; (COCl)2; Et3N / CH2Cl2 / 1.25 h / -78 - 0 °C 5.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 5.2: 727 mg / diethyl ether / 1 h / -100 °C 6.1: 85 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 7.1: O3 / CH2Cl2 / -78 °C 7.2: PPh3 / CH2Cl2 / 2 h / 20 °C 8.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 8.2: 499 mg / diethyl ether / 1 h / -100 °C 9.1: 95 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 10.1: O3 / CH2Cl2 / -78 °C 10.2: PPh3 / CH2Cl2 / 2 h / 20 °C 11.1: (-)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 11.2: diethyl ether / 1 h / -100 °C 12.1: 86 percent / iPr2NEt / CH2Cl2 / 2 h / -78 °C 13.1: 88 percent / PhCH=RuCl2(PCy3)2 / CH2Cl2 / 3 h / Heating
  • 35
  • [ 2765-11-9 ]
  • [ 791819-32-4 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 1.2: diethyl ether / 1 h / -100 °C 2.1: 90 percent / imidazole / dimethylformamide / 18 h / 20 °C 3.1: 9-BBN / tetrahydrofuran / 18 h / 20 °C 3.2: 82 percent / aq. NaOH; aq. H2O2 / tetrahydrofuran; methanol / 1 h / 50 °C 4.1: DMSO; (COCl)2; Et3N / CH2Cl2 / 1.25 h / -78 - 0 °C 5.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 5.2: diethyl ether / 1 h / -100 °C 6.1: 84 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 7.1: O3 / CH2Cl2 / -78 °C 7.2: PPh3 / CH2Cl2 / 2 h / 20 °C 8.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 8.2: diethyl ether / 1 h / -100 °C 9.1: 87 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 10.1: O3 / CH2Cl2 / -78 °C 10.2: PPh3 / CH2Cl2 / 2 h / 20 °C 11.1: (-)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 11.2: diethyl ether / 1 h / -100 °C 12.1: 69 percent / iPr2NEt / CH2Cl2 / 2 h / -78 °C 13.1: 76 percent / ruthenium catalyst / CH2Cl2 / 3 h / Heating
  • 36
  • [ 2765-11-9 ]
  • [ 791819-29-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 1.2: diethyl ether / 1 h / -100 °C 2.1: 90 percent / imidazole / dimethylformamide / 18 h / 20 °C 3.1: 9-BBN / tetrahydrofuran / 18 h / 20 °C 3.2: 82 percent / aq. NaOH; aq. H2O2 / tetrahydrofuran; methanol / 1 h / 50 °C 4.1: DMSO; (COCl)2; Et3N / CH2Cl2 / 1.25 h / -78 - 0 °C 5.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 5.2: diethyl ether / 1 h / -100 °C 6.1: 84 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 7.1: O3 / CH2Cl2 / -78 °C 7.2: PPh3 / CH2Cl2 / 2 h / 20 °C 8.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 8.2: diethyl ether / 1 h / -100 °C 9.1: 87 percent / 2,6-lutidine / CH2Cl2 / 1 h / 20 °C 10.1: O3 / CH2Cl2 / -78 °C 10.2: PPh3 / CH2Cl2 / 2 h / 20 °C 11.1: (+)-diisopinocampheylboron chloride / diethyl ether / 1 h / cooling 11.2: diethyl ether / 1 h / -100 °C 12.1: 70 percent / iPr2NEt / CH2Cl2 / 2 h / -78 °C 13.1: 92 percent / ruthenium catalyst / CH2Cl2 / 3 h / Heating
  • 37
  • [ 2765-11-9 ]
  • [ 325829-90-1 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 9.34 g / tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; (DHQ)2-PHAL; methanesulfonamide / K3Fe(CN)6; aq. K2CO3 / 2-methyl-propan-2-ol; toluene / 24 h / 0 °C
Multi-step reaction with 2 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C
  • 38
  • [ 2765-11-9 ]
  • ethyl (2S,3R)-2,3-dihydroxyheptadecanoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1: 9.34 g / tetrahydrofuran / 12 h / Heating 2: OsO4; (DHQD)2-PHAL; methanesulfonamide / K3Fe(CN)6; aq. K2CO3 / 2-methyl-propan-2-ol; toluene
  • 39
  • [ 2765-11-9 ]
  • [ 127995-80-6 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C 11: LiAlH4 / diethyl ether / 0 - 20 °C 12: HCl / methanol / 20 °C 13: pyridine / DMAP / CH2Cl2 / 12 h / 20 °C
  • 40
  • [ 2765-11-9 ]
  • (4R,5S)-2,2-Dimethyl-5-tetradecyl-[1,3]dioxolane-4-carbaldehyde [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 5 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C
  • 41
  • [ 2765-11-9 ]
  • [ 325829-96-7 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 6 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C
  • 42
  • [ 2765-11-9 ]
  • [ 325829-94-5 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C
  • 43
  • [ 2765-11-9 ]
  • [ 325829-92-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C
  • 44
  • [ 2765-11-9 ]
  • [ 326590-16-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 11 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: 94 percent / pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C 11: 96 percent / LiAlH4 / diethyl ether / 0 - 20 °C
  • 45
  • [ 2765-11-9 ]
  • (S)-2-Amino-2-((4S,5S)-2,2-dimethyl-5-tetradecyl-[1,3]dioxolan-4-yl)-ethanol [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 11 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C 11: LiAlH4 / diethyl ether / 0 - 20 °C
  • 46
  • [ 2765-11-9 ]
  • [ 325829-98-9 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C
  • 47
  • [ 2765-11-9 ]
  • [ 325830-00-0 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 7 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C
  • 48
  • [ 2765-11-9 ]
  • 2,2-Dimethyl-propionic acid (R)-2-((4S,5S)-2,2-dimethyl-5-tetradecyl-[1,3]dioxolan-4-yl)-2-hydroxy-ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: pyridine / CH2Cl2 / 0 - 20 °C
  • 49
  • [ 2765-11-9 ]
  • [ 325830-02-2 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 8 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: 94 percent / pyridine / CH2Cl2 / 0 - 20 °C
  • 50
  • [ 2765-11-9 ]
  • [ 325830-03-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 10 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: 94 percent / pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C
  • 51
  • [ 2765-11-9 ]
  • 2,2-Dimethyl-propionic acid (S)-2-azido-2-((4S,5S)-2,2-dimethyl-5-tetradecyl-[1,3]dioxolan-4-yl)-ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 10 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C
  • 52
  • [ 2765-11-9 ]
  • 2,2-Dimethyl-propionic acid (S)-2-((4R,5S)-2,2-dimethyl-5-tetradecyl-[1,3]dioxolan-4-yl)-2-methanesulfonyloxy-ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: 94 percent / pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C
  • 53
  • [ 2765-11-9 ]
  • 2,2-Dimethyl-propionic acid (R)-2-((4R,5S)-2,2-dimethyl-5-tetradecyl-[1,3]dioxolan-4-yl)-2-methanesulfonyloxy-ethyl ester [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 9 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C
  • 54
  • [ 2765-11-9 ]
  • 3,4-di(methylcarbonyloxy)-2-methylcarboxamido-(2R,3S,4S)-octadecylacetate [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 13 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: 94 percent / pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C 11: 96 percent / LiAlH4 / diethyl ether / 0 - 20 °C 12: HCl / methanol / 20 °C 13: pyridine / DMAP / CH2Cl2 / 12 h / 20 °C
  • 55
  • [ 2765-11-9 ]
  • (2R,3S,4S)-2-amino-1,3,4-trihydroxyoctadecane hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 12 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: 94 percent / pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C 11: 96 percent / LiAlH4 / diethyl ether / 0 - 20 °C 12: HCl / methanol / 20 °C
  • 56
  • [ 2765-11-9 ]
  • (2S,3S,4S)-2-amino-1,3,4-trihydroxyoctadecane hydrochloride [ No CAS ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 12 steps 1: tetrahydrofuran / 12 h / Heating 2: 94 percent / OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 3: 98 percent / 2,2-DMP; PTSA / 20 °C 4: 93 percent / LiAlH4 / diethyl ether / 0 - 20 °C 5: (COCl)2; DMSO; Et3N / CH2Cl2 / -78 °C 6: NaHDMS / tetrahydrofuran / 12 h / 0 - 20 °C 7: OsO4; K3Fe(CN)6; K2CO3 / (DHQ)2-PHAL / 2-methyl-propan-2-ol; H2O / 24 h / 0 °C 8: pyridine / CH2Cl2 / 0 - 20 °C 9: pyridine / DMAP / CH2Cl2 / 60 °C 10: LiN3 / dimethylformamide / 12 h / 80 °C 11: LiAlH4 / diethyl ether / 0 - 20 °C 12: HCl / methanol / 20 °C
  • 57
  • [ 2765-11-9 ]
  • [ 143799-46-6 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 2 steps 1.1: nBuLi / tetrahydrofuran / 1 h / -78 °C 1.2: tetrahydrofuran / 2.5 h / -78 °C 2.1: 88 percent / Et3N; DMAP / CH2Cl2
Multi-step reaction with 2 steps 1: 1) BuLi 2: 92 percent / DMAP, Et3N
  • 58
  • [ 2765-11-9 ]
  • [ 214556-61-3 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1.1: nBuLi / tetrahydrofuran / 1 h / -78 °C 1.2: tetrahydrofuran / 2.5 h / -78 °C 2.1: 88 percent / Et3N; DMAP / CH2Cl2 3.1: 86 percent / Cs2CO3 / methanol / 20 °C
  • 59
  • [ 2765-11-9 ]
  • [ 21551-64-4 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 4 steps 1: 1.) n-BuLi / 1.) THF, tetramethylethylenediamine, hexane, 0 to 20 deg C; 2.) THF, RT, 1 h 2: 69 percent / Et3SiH, CF3COOH / CH2Cl2 / 4 h / Ambient temperature 3: 81 percent / O2 / salcomine / dimethylformamide / 3 h / Ambient temperature 4: 85 percent / HClO4 / CH2Cl2 / 1 h / Ambient temperature
  • 60
  • [ 2765-11-9 ]
  • [ 21551-66-6 ]
YieldReaction ConditionsOperation in experiment
Multi-step reaction with 3 steps 1: 1.) n-BuLi / 1.) THF, tetramethylethylenediamine, hexane, 0 to 20 deg C; 2.) THF, RT, 1 h 2: 69 percent / Et3SiH, CF3COOH / CH2Cl2 / 4 h / Ambient temperature 3: 81 percent / O2 / salcomine / dimethylformamide / 3 h / Ambient temperature
  • 61
  • [ 2765-11-9 ]
  • [ 1129-28-8 ]
  • methyl 3-(3-tetradecyloxiranyl)benzoate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride In thiophene; methanol; hexane; dichloromethane 22 Methyl 3-(3-tetradecyloxiranyl)benzoate EXAMPLE 22 Methyl 3-(3-tetradecyloxiranyl)benzoate Methyl 3-(bromomethyl)benzoate (0.92 g, 4.0 mmol) was dissolved in 5.0 ml of 7% aqueous methanol. Tetrahydrothiophene (0.70 ml, 8.0 mmol) was added, and the mixture was stirred at room temperature for 1 hr. The solvent was removed, the residue was washed with hexane, and the crude salt was dried under vacuum. The crude salt was suspended in 25 ml of methylene chloride with benzyltriethylammonium chloride (0.10 g) and 1-pentadecanal (0.85 g, 3.75 mmol) at 0°C. To the suspension was added 8.0 ml of 10 N sodium hydroxide at 0°C. The reaction mixture was stirred at 0°C for 5 min. and at room temperature for 20 min. then poured into ether/water. The ether layer was washed with water and saturated sodium chloride, dried over sodium sulfate, and concentrated. The crude white solid was flash chromatographed on silica gel using 100:1 then 50:1 hexane/ethyl acetate as eluent to give 0.73 g of product which was mostly trans and 0.33 g of a mixture. The trans product (0.73 g) was dissolved in 5 ml of warm hexane. Cooling at 0°C gave the product as a precipitate of white powder, m.p. 44-45°C. The lithium salt of the product was prepared as described in Example 1.
  • 62
  • [ 867-13-0 ]
  • [ 2765-11-9 ]
  • [ 404573-28-0 ]
YieldReaction ConditionsOperation in experiment
95% Stage #1: diethoxyphosphoryl-acetic acid ethyl ester With sodium hydride In tetrahydrofuran at 0℃; for 0.5h; Stage #2: n-pentadecanal In tetrahydrofuran at 0 - 20℃; Further stages.;
  • 63
  • [ 2765-11-9 ]
  • [ 105-53-3 ]
  • [ 1036939-38-4 ]
YieldReaction ConditionsOperation in experiment
86% With piperidine; 3 A molecular sieve; acetic acid In dichloromethane at 20℃; for 1h;
With piperidine; acetic acid In dichloromethane at 0 - 20℃; for 1h; Molecular sieve; 5.1.2. General procedure for the synthesis of derivatives 1-3. Example: diethyl 2-tetradecylidenemalonate (1a) General procedure: A stirred solution of the aldehyde 12a (3.98 mmol) and diethyl malonate (4.38 mmol) in anhydrous methylene chloride (3 mL) was treated with piperidine (0.08 mmol) and acetic acid (0.08 mmol) at 0 °C. After 45 min of stirring, a small amount of 3-Å molecular sieves was added. Then the reaction mixture was stirred at room temperature for another 15 min (TLC monitoring), diluted with diethyl ether (50 mL), and washed with water (10 mL) until the aqueous phase was neutral. The collected aqueous phases were extracted with diethyl ether (3 × 10 mL). The combined etheral phases were successively washed with saturated sodium hydrogen carbonate solution (3 × 10 mL) and brine (3 × 10 mL) and dried (Na2SO4). After removing the solvent, the crude was purified by column chromatography (SiO2, n-hexane/AcOEt 8:2) to obtain compound 1a as an oil, in a 83% yield.
  • 64
  • [ 2765-11-9 ]
  • [ 74181-34-3 ]
  • [ 1059573-76-0 ]
YieldReaction ConditionsOperation in experiment
59% With D-Prolin In chloroform at 20℃; for 96h; optical yield given as %ee; enantioselective reaction;
59% With D-Prolin In chloroform at 20℃; for 96h; optical yield given as %ee; enantioselective reaction;
  • 65
  • [ 2765-11-9 ]
  • [ 554-12-1 ]
  • [ 1134448-86-4 ]
YieldReaction ConditionsOperation in experiment
90% With lithium diisopropyl amide In tetrahydrofuran at -78℃;
  • 66
  • [ 2765-11-9 ]
  • [ 41795-35-1 ]
  • [ 108-24-7 ]
  • [ 1204323-01-2 ]
YieldReaction ConditionsOperation in experiment
62% Stage #1: (5-hexen-1-ylsulfonyl)-benzene With n-butyllithium In tetrahydrofuran at -78℃; for 1h; Inert atmosphere; Stage #2: n-pentadecanal In tetrahydrofuran at -78℃; for 5h; Inert atmosphere; Stage #3: acetic anhydride With dmap In tetrahydrofuran at -78 - 20℃; for 12h; Inert atmosphere;
  • 67
  • [ 112-41-4 ]
  • [ 1120-36-1 ]
  • [ 201230-82-2 ]
  • [ 2765-11-9 ]
  • [ 10486-19-8 ]
  • [ 37596-36-4 ]
  • [ 73401-51-1 ]
  • [ 35518-76-4 ]
  • [ 65899-14-1 ]
  • 2-Amyldecanal [ No CAS ]
  • 2-Butylhendecanal [ No CAS ]
  • 2-Propyldodecanal [ No CAS ]
  • 2-methyl-1-tetradecanal [ No CAS ]
  • 2-Pentyl-octanal [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 1-dodecene; 1-tetradecene at 180℃; for 1h; Stage #2: carbon monoxide With hydrogen In toluene at 130℃; for 6 - 7h; 2 EXAMPLE 2Production of a Blend of Aldehydes of Type (I) and (II) (On the Basis of the Method According to DE 43 44 064)1. 420 g of C12/C14 olefin blend (olefins of the formula A and/or B) were introduced into a 1 I stirred autoclave and heated for 1 hour to 180° C. in the presence of 0.20 g of iron pentacarbonyl. 2. Without separating the isomerization catalyst and after addition of 3.2 g of triphenylphosphine and 2.2 g of a toluene solution of rhodium 2-ethylhexanoate (corresponding 125 mg rhodium, corresponding to a rhodium:phosphorus ratio of 1:100), the resultant olefin isomer mixture was hydroformylated for 6 to 7 hours at a temperature of 130° C. and a pressure of 26 MPa. After cooling to room temperature, the autoclave was flushed with nitrogen. The crude product was filtered (crude yield 440 g) and vacuum-fractionated using a 30 cm Vigreux column. Yield: 433.2 g (89.9% of theoretical) Boiling point: 130°-140° C./8 mbarGC evaluation (20m ZB-WAX, internal diameter 0.18 μm/60-9-220° C. programmed-temperature vaporization system)
  • 68
  • [ 593-60-2 ]
  • [ 2765-11-9 ]
  • [ 131248-35-6 ]
YieldReaction ConditionsOperation in experiment
7.84 g Stage #1: Vinyl bromide With magnesium In tetrahydrofuran for 0.5h; Stage #2: n-pentadecanal In tetrahydrofuran at 0℃; for 2.33333h;
  • 69
  • [ 2033-24-1 ]
  • [ 2765-11-9 ]
  • [ 1314006-50-2 ]
YieldReaction ConditionsOperation in experiment
With piperidine; acetic acid In dichloromethane at 0 - 20℃; for 1h; Molecular sieve; 5.1.2. General procedure for the synthesis of derivatives 1-3. Example: diethyl 2-tetradecylidenemalonate (1a) General procedure: A stirred solution of the aldehyde 12a (3.98 mmol) and diethyl malonate (4.38 mmol) in anhydrous methylene chloride (3 mL) was treated with piperidine (0.08 mmol) and acetic acid (0.08 mmol) at 0 °C. After 45 min of stirring, a small amount of 3-Å molecular sieves was added. Then the reaction mixture was stirred at room temperature for another 15 min (TLC monitoring), diluted with diethyl ether (50 mL), and washed with water (10 mL) until the aqueous phase was neutral. The collected aqueous phases were extracted with diethyl ether (3 × 10 mL). The combined etheral phases were successively washed with saturated sodium hydrogen carbonate solution (3 × 10 mL) and brine (3 × 10 mL) and dried (Na2SO4). After removing the solvent, the crude was purified by column chromatography (SiO2, n-hexane/AcOEt 8:2) to obtain compound 1a as an oil, in a 83% yield.
  • 70
  • [ 2765-11-9 ]
  • [ 123-54-6 ]
  • [ 1314006-43-3 ]
YieldReaction ConditionsOperation in experiment
89% With piperidine; acetic acid In dichloromethane at 0 - 20℃; Inert atmosphere;
83% With piperidine; acetic acid In dichloromethane at 0 - 20℃; for 1h; Molecular sieve; 5.1.2. General procedure for the synthesis of derivatives 1-3. Example: diethyl 2-tetradecylidenemalonate (1a) General procedure: A stirred solution of the aldehyde 12a (3.98 mmol) and diethyl malonate (4.38 mmol) in anhydrous methylene chloride (3 mL) was treated with piperidine (0.08 mmol) and acetic acid (0.08 mmol) at 0 °C. After 45 min of stirring, a small amount of 3-Å molecular sieves was added. Then the reaction mixture was stirred at room temperature for another 15 min (TLC monitoring), diluted with diethyl ether (50 mL), and washed with water (10 mL) until the aqueous phase was neutral. The collected aqueous phases were extracted with diethyl ether (3 × 10 mL). The combined etheral phases were successively washed with saturated sodium hydrogen carbonate solution (3 × 10 mL) and brine (3 × 10 mL) and dried (Na2SO4). After removing the solvent, the crude was purified by column chromatography (SiO2, n-hexane/AcOEt 8:2) to obtain compound 1a as an oil, in a 83% yield.
  • 71
  • [ 2765-11-9 ]
  • [ 141-82-2 ]
  • [ 1351929-84-4 ]
YieldReaction ConditionsOperation in experiment
With ammonium acetate In ethanol; water Reflux; General procedure for the synthesis of rac-5a and rac-5b General procedure: 1 equiv of the corresponding aldehyde,36 1 equiv of malonic acid, and 2 equiv of ammonium acetate were suspended in EtOH/H2O (95:5). The solution was vigorously stirred under reflux overnight. The solution was then cooled down to room temperature and the precipitated solid was filtrated and recrystallized from EtOH/H2O (95:5) to get the desired products rac-5a and rac-5b as colorless crystals (17-21%).
  • 72
  • [ 2765-11-9 ]
  • [ 20989-17-7 ]
  • C23H39NO [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: n-pentadecanal; (2S)-2-phenylglycinol In tetrahydrofuran at 20℃; for 0.5h; Stage #2: With magnesium sulfate In tetrahydrofuran at 20℃; for 2h; Imines preparation General procedure: To a solution of 1-phenylglycinol (0.1 g, 0.54 mmol) in absolute THF (1 ml) at ambient temperature, 1 equiv of the corresponding aldehyde34 (0.54 mmol) was added in a dropwise manner. The mixture was stirred for 30 min at room temperature. 0.1 g of oven-dried (110 °C) MgSO4 was added and the mixture stirred for 2 h at room temperature. The suspension was directly transferred into a syringe through a syringe filter and injected into the solution containing the Reformatsky reagent.
  • 73
  • [ 2765-11-9 ]
  • [ 90965-06-3 ]
  • [ 629-74-3 ]
YieldReaction ConditionsOperation in experiment
90% With potassium carbonate In methanol at 20℃; for 18h; Inert atmosphere;
  • 74
  • [ 2765-11-9 ]
  • [ 188945-41-7 ]
  • [ 1371603-84-7 ]
YieldReaction ConditionsOperation in experiment
79% Stage #1: ethyl di-O-tolylphosphonoacetate With sodium hydride In tetrahydrofuran; mineral oil at -40 - 0℃; for 0.25h; Inert atmosphere; Stage #2: n-pentadecanal In tetrahydrofuran; mineral oil at -40℃; for 3h; Inert atmosphere; optical yield given as %de; stereoselective reaction;
  • 75
  • [ 2765-11-9 ]
  • [ 51860-45-8 ]
  • [ 41207-36-7 ]
YieldReaction ConditionsOperation in experiment
68% With phenyllithium In tetrahydrofuran at -78 - 20℃; for 1.25h; Inert atmosphere; Cooling with acetone-dry ice;
  • 76
  • [ 2765-11-9 ]
  • [ 89343-06-6 ]
  • 1-(triisopropylsilyl)heptadec-1-yn-3-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
52% Stage #1: tris-iso-propylsilyl acetylene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: n-pentadecanal In tetrahydrofuran; hexane at -78 - 20℃; for 5h; Inert atmosphere;
  • 77
  • [ 2765-11-9 ]
  • C15H22O6 [ No CAS ]
  • 3-{(3aR,4R,5R,6S,6aR)-5-{(S)-2,2-dimethyl-1,3-dioxolan-4-yl}-2,2-dimethyltetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy}octadeca-1,2-dien-4-ol [ No CAS ]
  • 3-{(3aR,4S,5R,6S,6aR)-5-{(S)-2,2-dimethyl-1,3-dioxolan-4-yl}-2,2-dimethyltetrahydro-furo[2,3-d][1,3]dioxol-6-yloxy}octadeca-1,2-dien-4-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
14 % de Stage #1: C15H22O6 With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 0.333333h; Inert atmosphere; Stage #2: n-pentadecanal In tetrahydrofuran; hexane at -78℃; for 3h; Inert atmosphere; Overall yield = 57 %; Overall yield = 2.64 g; Typical procedure for the preparation of -hydroxyallenes by addition oflithiated alkoxyallenes to aldehydes (Procedure 1): General procedure: A solution of the corresponding allene (3 equiv) in dry THF (0.7 mL/mmol) at-40 °C was treated with n-BuLi (2.5 M in hexane, 2.8 equiv). After 20 min thereaction mixture was cooled to -78 °C and a solution of the aldehyde (1 equiv) indry THF (3 mL/mmol) was added dropwise. After 3 h of stirring at -78 °C thereaction was quenched with sat. aq. NaHCO3 solution (3 mL/mmol). After warm up to rt the layers were separated, followed by extraction with ethyl acetate (2 x 3mL/mmol). The combined organic layers were dried with Na2SO4, filtered and thesolvent was removed under reduced pressure.
  • 78
  • [ 2765-11-9 ]
  • [ 13169-00-1 ]
  • 3-methoxyoctadeca-1,2-dien-4-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: Methoxyallene With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 0.333333h; Inert atmosphere; Stage #2: n-pentadecanal In tetrahydrofuran; hexane at -78℃; for 3h; Inert atmosphere; Typical procedure for the preparation of -hydroxyallenes by addition oflithiated alkoxyallenes to aldehydes (Procedure 1): General procedure: A solution of the corresponding allene (3 equiv) in dry THF (0.7 mL/mmol) at-40 °C was treated with n-BuLi (2.5 M in hexane, 2.8 equiv). After 20 min thereaction mixture was cooled to -78 °C and a solution of the aldehyde (1 equiv) indry THF (3 mL/mmol) was added dropwise. After 3 h of stirring at -78 °C thereaction was quenched with sat. aq. NaHCO3 solution (3 mL/mmol). After warm up to rt the layers were separated, followed by extraction with ethyl acetate (2 x 3mL/mmol). The combined organic layers were dried with Na2SO4, filtered and thesolvent was removed under reduced pressure.
  • 79
  • [ 2765-11-9 ]
  • [ 1195778-13-2 ]
  • [ 1643949-37-4 ]
YieldReaction ConditionsOperation in experiment
89% With sodium hydroxide In <i>tert</i>-butyl alcohol Inert atmosphere;
  • 80
  • [ 19794-97-9 ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
With Sodium orthovanadate; ethylenediaminetetraacetic acid; sphingosine-1-phosphate lyase; pyridoxal 5'-phosphate; sodium fluoride; D,L-dithiothreitol In aq. phosphate buffer at 37℃; for 1h; Enzymatic reaction; Enzyme measurements General procedure: The substrate 2-hydroxyoctadecanoyl-CoA or sphinganine-1-phosphate was incubated at 37°C with purifi ed recombinant enzyme, tissue homogenate, or cell lysate in baked Pyrex 5 ml glass tubes. Reaction mixtures for activity measurement consisted of 50 mM Tris-HCl (pH 7.5), 0.8 mM MgCl 2 ,20 M TPP, 6.6 M BSA, and 40 M 2-hydroxyoctadecanoyl-CoA for HACL1 ( 6 ); and 0.1 M K-phosphate buffer(pH 7.5), 25 mM NaF, 0.1 mM Na-orthovanadate, 0.25 mM pyridoxal-phosphate, 1 mM DTT, 1 mM EDTA, 0.1% (v/v)Triton X-100, and 40 M sphinganine-1-phosphate forSGPL1 ( 8 ). Reactions for tissue homogenates and celllysates were halted after 5 min (HACL1) or 60 min (SGPL1) by adding 1 vol of methanol (see below).
  • 81
  • [ 2765-11-9 ]
  • [ 141-82-2 ]
  • 2-pentadecylidenemalonic acid [ No CAS ]
YieldReaction ConditionsOperation in experiment
78% With piperidine; acetic acid In dichloromethane at 0 - 20℃; Inert atmosphere;
  • 82
  • [ 2765-11-9 ]
  • ((6R)-2,2-dimethyl-6-vinyl-1,3-dioxan-4-yl)diphenylphosphine oxide [ No CAS ]
  • (R)-3-hydroxyicos-1-en-5-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% Stage #1: ((6R)-2,2-dimethyl-6-vinyl-1,3-dioxan-4-yl)diphenylphosphine oxide With lithium diisopropyl amide In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: n-pentadecanal In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Inert atmosphere; Stage #3: With potassium <i>tert</i>-butylate In tetrahydrofuran; hexane for 1h; Inert atmosphere;
  • 83
  • [ 2765-11-9 ]
  • C20H23O5P [ No CAS ]
  • (R)-3-hydroxyicos-1-en-5-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
83% Stage #1: C20H23O5P With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: n-pentadecanal In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Inert atmosphere; Further stages;
  • 84
  • [ 108-31-6 ]
  • [ 2765-11-9 ]
  • [ 56-81-5 ]
  • C22H38O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: n-pentadecanal; glycerol With toluene-4-sulfonic acid In water at 120℃; for 9h; Inert atmosphere; Stage #2: maleic anhydride With sodium formate at 120℃; for 2h; Inert atmosphere; 9 Example 9 Equipped with electric mixer, trap, condenser,Neck round bottom flask, a nitrogen inlet tube was added glycerol 7.37g (0.080mol), n-pentadecyl aldehyde by: glycerol = 1: 4 (molar ratio) was added n-pentadecyl aldehyde 4.53g (0.020mol), in accordance with the n-pentadecyl aldehyde 1.5% by mass of the catalyst was added 0.07 g of p-toluenesulfonic acid, in accordance with the n-pentadecyl aldehyde: water = 1: 2 (mass ratio) was added 9.06 g of water, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction was cooled to 9 hours at room temperature, the resulting reaction solution was extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated in vacuo to give the product pentadecyl glycerol acetal after 5.47 g, as measured by gas chromatographic purity of the product was 92.1%, yield 84.0%, measured by mass spectrometry the molecular weight of 300. It said acetalization reaction equation is as follows: Take the above reaction of the resulting aldehyde diglycidyl pentadecyl product 4.80g (0.016mol) was added into a reactor equipped with a stirrer motor, trap, condenser, nitrogen inlet three-necked round-bottomed flask, n-pentadecyl according aldolase glycerin: = maleic anhydride: 1.8 (molar ratio) of maleic anhydride was added 2.82g (0.029mol), in accordance with maleic anhydride 5.0% by mass of sodium formate was added 0.14 g of catalyst, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction 5 hours after cooling to room temperature. 25.20g was added at a concentration of 20wt.% Aqueous solution of potassium sulfite, the reaction temperature was raised to 100 deg.] C for 2 hours to give the product n-pentadecyl aldehyde diglycidyl sulfosuccinate monoesters dipotassium salt. It was determined that the esterification was 80.2%, 90.6% rate of sulfonated anionic active matter content of 66.1% The reaction equation for the chemical reaction is as follows: 1) esterification reaction equation:
  • 85
  • [ 108-31-6 ]
  • [ 2765-11-9 ]
  • [ 56-81-5 ]
  • C22H38O6 [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: n-pentadecanal; glycerol With toluene-4-sulfonic acid In water at 120℃; for 9h; Inert atmosphere; Stage #2: maleic anhydride With sodium formate at 120℃; for 2h; Inert atmosphere; 9 Example 9 Equipped with electric mixer, trap, condenser,Neck round bottom flask, a nitrogen inlet tube was added glycerol 7.37g (0.080mol), n-pentadecyl aldehyde by: glycerol = 1: 4 (molar ratio) was added n-pentadecyl aldehyde 4.53g (0.020mol), in accordance with the n-pentadecyl aldehyde 1.5% by mass of the catalyst was added 0.07 g of p-toluenesulfonic acid, in accordance with the n-pentadecyl aldehyde: water = 1: 2 (mass ratio) was added 9.06 g of water, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction was cooled to 9 hours at room temperature, the resulting reaction solution was extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated in vacuo to give the product pentadecyl glycerol acetal after 5.47 g, as measured by gas chromatographic purity of the product was 92.1%, yield 84.0%, measured by mass spectrometry the molecular weight of 300. It said acetalization reaction equation is as follows: Take the above reaction of the resulting aldehyde diglycidyl pentadecyl product 4.80g (0.016mol) was added into a reactor equipped with a stirrer motor, trap, condenser, nitrogen inlet three-necked round-bottomed flask, n-pentadecyl according aldolase glycerin: = maleic anhydride: 1.8 (molar ratio) of maleic anhydride was added 2.82g (0.029mol), in accordance with maleic anhydride 5.0% by mass of sodium formate was added 0.14 g of catalyst, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction 5 hours after cooling to room temperature. 25.20g was added at a concentration of 20wt.% Aqueous solution of potassium sulfite, the reaction temperature was raised to 100 deg.] C for 2 hours to give the product n-pentadecyl aldehyde diglycidyl sulfosuccinate monoesters dipotassium salt. It was determined that the esterification was 80.2%, 90.6% rate of sulfonated anionic active matter content of 66.1% The reaction equation for the chemical reaction is as follows: 1) esterification reaction equation:
  • 86
  • [ 108-31-6 ]
  • [ 2765-11-9 ]
  • [ 56-81-5 ]
  • C22H38O9S(2-)*2K(1+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: n-pentadecanal; glycerol With toluene-4-sulfonic acid In water at 120℃; for 9h; Inert atmosphere; Stage #2: maleic anhydride With sodium formate at 120℃; for 2h; Inert atmosphere; Stage #3: With potassium sulfite In water at 100℃; for 2h; 9 Example 9 Equipped with electric mixer, trap, condenser,Neck round bottom flask, a nitrogen inlet tube was added glycerol 7.37g (0.080mol), n-pentadecyl aldehyde by: glycerol = 1: 4 (molar ratio) was added n-pentadecyl aldehyde 4.53g (0.020mol), in accordance with the n-pentadecyl aldehyde 1.5% by mass of the catalyst was added 0.07 g of p-toluenesulfonic acid, in accordance with the n-pentadecyl aldehyde: water = 1: 2 (mass ratio) was added 9.06 g of water, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction was cooled to 9 hours at room temperature, the resulting reaction solution was extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated in vacuo to give the product pentadecyl glycerol acetal after 5.47 g, as measured by gas chromatographic purity of the product was 92.1%, yield 84.0%, measured by mass spectrometry the molecular weight of 300. It said acetalization reaction equation is as follows: Take the above reaction of the resulting aldehyde diglycidyl pentadecyl product 4.80g (0.016mol) was added into a reactor equipped with a stirrer motor, trap, condenser, nitrogen inlet three-necked round-bottomed flask, n-pentadecyl according aldolase glycerin: = maleic anhydride: 1.8 (molar ratio) of maleic anhydride was added 2.82g (0.029mol), in accordance with maleic anhydride 5.0% by mass of sodium formate was added 0.14 g of catalyst, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction 5 hours after cooling to room temperature. 25.20g was added at a concentration of 20wt.% Aqueous solution of potassium sulfite, the reaction temperature was raised to 100 deg.] C for 2 hours to give the product n-pentadecyl aldehyde diglycidyl sulfosuccinate monoesters dipotassium salt. It was determined that the esterification was 80.2%, 90.6% rate of sulfonated anionic active matter content of 66.1% The reaction equation for the chemical reaction is as follows: 1) esterification reaction equation: 2) sulfonation reaction equation:
  • 87
  • [ 108-31-6 ]
  • [ 2765-11-9 ]
  • [ 56-81-5 ]
  • C22H38O9S(2-)*2K(1+) [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: n-pentadecanal; glycerol With toluene-4-sulfonic acid In water at 120℃; for 9h; Inert atmosphere; Stage #2: maleic anhydride With sodium formate at 120℃; for 2h; Inert atmosphere; Stage #3: With potassium sulfite In water at 100℃; for 2h; 9 Example 9 Equipped with electric mixer, trap, condenser,Neck round bottom flask, a nitrogen inlet tube was added glycerol 7.37g (0.080mol), n-pentadecyl aldehyde by: glycerol = 1: 4 (molar ratio) was added n-pentadecyl aldehyde 4.53g (0.020mol), in accordance with the n-pentadecyl aldehyde 1.5% by mass of the catalyst was added 0.07 g of p-toluenesulfonic acid, in accordance with the n-pentadecyl aldehyde: water = 1: 2 (mass ratio) was added 9.06 g of water, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction was cooled to 9 hours at room temperature, the resulting reaction solution was extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated in vacuo to give the product pentadecyl glycerol acetal after 5.47 g, as measured by gas chromatographic purity of the product was 92.1%, yield 84.0%, measured by mass spectrometry the molecular weight of 300. It said acetalization reaction equation is as follows: Take the above reaction of the resulting aldehyde diglycidyl pentadecyl product 4.80g (0.016mol) was added into a reactor equipped with a stirrer motor, trap, condenser, nitrogen inlet three-necked round-bottomed flask, n-pentadecyl according aldolase glycerin: = maleic anhydride: 1.8 (molar ratio) of maleic anhydride was added 2.82g (0.029mol), in accordance with maleic anhydride 5.0% by mass of sodium formate was added 0.14 g of catalyst, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction 5 hours after cooling to room temperature. 25.20g was added at a concentration of 20wt.% Aqueous solution of potassium sulfite, the reaction temperature was raised to 100 deg.] C for 2 hours to give the product n-pentadecyl aldehyde diglycidyl sulfosuccinate monoesters dipotassium salt. It was determined that the esterification was 80.2%, 90.6% rate of sulfonated anionic active matter content of 66.1% The reaction equation for the chemical reaction is as follows: 1) esterification reaction equation: 2) sulfonation reaction equation:
  • 88
  • [ 2765-11-9 ]
  • [ 56-81-5 ]
  • C18H36O3 [ No CAS ]
  • C18H36O3 [ No CAS ]
YieldReaction ConditionsOperation in experiment
With toluene-4-sulfonic acid In water at 120℃; for 9h; Inert atmosphere; Overall yield = 84.0 %; Overall yield = 5.47 g; 9 Example 9 Equipped with electric mixer, trap, condenser,Neck round bottom flask, a nitrogen inlet tube was added glycerol 7.37g (0.080mol), n-pentadecyl aldehyde by: glycerol = 1: 4 (molar ratio) was added n-pentadecyl aldehyde 4.53g (0.020mol), in accordance with the n-pentadecyl aldehyde 1.5% by mass of the catalyst was added 0.07 g of p-toluenesulfonic acid, in accordance with the n-pentadecyl aldehyde: water = 1: 2 (mass ratio) was added 9.06 g of water, under nitrogen atmosphere, was heated to 120 deg.] C with stirring, the reaction was cooled to 9 hours at room temperature, the resulting reaction solution was extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and concentrated in vacuo to give the product pentadecyl glycerol acetal after 5.47 g, as measured by gas chromatographic purity of the product was 92.1%, yield 84.0%, measured by mass spectrometry the molecular weight of 300. It said acetalization reaction equation is as follows:
  • 89
  • [ 2765-11-9 ]
  • (S)-tert-butyl (1-((benzyloxy)methoxy)-3-oxopropan-2-yl)carbamate [ No CAS ]
  • tert-butyl ((2S)-1-((benzyloxy)methoxy)-3-hydroxy-4-oxooctadecan-2-yl)carbamate [ No CAS ]
  • tert-butyl ((2S)-1-((benzyloxy)methoxy)-3-hydroxy-4-oxooctadecan-2-yl)carbamate [ No CAS ]
YieldReaction ConditionsOperation in experiment
With C6H10N3(1+)*BF4(1-); N-ethyl-N,N-diisopropylamine In toluene at 70℃; for 4h; Schlenk technique; Inert atmosphere; Optical yield = 66.667 %de;
  • 90
  • [ 2765-11-9 ]
  • [ 127382-65-4 ]
  • (3R,4S)-1,3--butyl(dimethyl)silyl]oxy}-4-hydroxyoctadecan-2-one [ No CAS ]
  • 1,3--butyl(dimethyl)silyl]oxy}-4-hydroxyoctadecan-2-one [ No CAS ]
  • -2-tridecyl-2-heptadecenal [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 84.615 % de 2: 22% With 1,3-bis(3,5-bis(trifluoro-ethyl)phenyl)thiourea; O-(tert-butyldimethylsilyloxy)-L-threonine In toluene at 20℃; for 48h; Green chemistry; Overall yield = 65 %;
  • 91
  • [ 2765-11-9 ]
  • [ 127382-65-4 ]
  • (3R,4S)-1,3--butyl(dimethyl)silyl]oxy}-4-hydroxyoctadecan-2-one [ No CAS ]
  • -2-tridecyl-2-heptadecenal [ No CAS ]
YieldReaction ConditionsOperation in experiment
1: 55% 2: 19% With methyl (Z)-2-cyano-2-(hydroxyimino)acetate; O-(tert-butyldimethylsilyloxy)-L-threonine In water at 20℃; for 24h; Green chemistry; diastereoselective reaction; (3R,4S)-1,3-Bis[(tert-butyl(dimethyl)silyl]oxy}-4-hydroxyoctadecan-2-one (9) To a mixture of O-(tert-butyldimethylsiloxy)-L-threonine (5g; 11 mg, 0.044 mmol, 10 mol%), (Z)-methyl 2-cyano-2-(hydroxyimino)acetate (6a; 5.63 mg, 0.044 mmol, 10 mol%) and TBS protected 1,3-dihydroxypropan-2-one 8 (280 mg, 0.88 mmol, 2.0 equiv) were added pentadecanal (7; 100 mg, 0.44 mmol, 1.0 equiv) and H2O (8 μL, 0.044 mmol). The mixture was stirred at r.t. for 24 h. Reaction progress was monitored by NMR analysis of the crude. After completion of the reaction, the product was directly purified by flash column chromatography (PE/EtOAc, 15:1 to 10:1) to afford the pure compound 9 (132 mg, 55%) as a colorless oil; dr (syn/anti) = 19:1; [α]D20 +3.1 (c = 1.0, CHCl3); Rf = 0.41 (PE/EtOAc, 10:1).
  • 92
  • [ 2765-11-9 ]
  • [ 105-34-0 ]
  • methyl 2-amino-5-tridecylthiophene-3-carboxylate [ No CAS ]
YieldReaction ConditionsOperation in experiment
89% With sulfur; triethylamine for 12h; Reflux; Inert atmosphere; 5.1.2.1. General procedure for the synthesis of 2-amino-5-alkylthiophene-3-carboxylate derivatives 3 as shown in Table 1 General procedure: A solution of aliphatic carbonyl compound 1 (2 mmol), activatednitrile (2 mol), elemental sulfur (2 mmol) and triethylamine(2 mmol) in MeOH (15 ml) was heated at reflux temperature for12 h under argon atmosphere. The MeOH was evaporated underreduced pressure and the residue was extracted with dichloromethane(3 50ml). The combined organic phases were washedwith a saturated solution of NaHCO3, dried over magnesium sulfateand the solvent was evaporated under reduced pressure. Purificationby column chromatography (silica, eluent CH2Cl2) afforded 3 asan off-white solid or a semi-solid.
  • 93
  • [ 623-73-4 ]
  • [ 2765-11-9 ]
  • [ 112548-17-1 ]
YieldReaction ConditionsOperation in experiment
89.6% Stage #1: diazoacetic acid ethyl ester With tin(II) chloride dihdyrate In dichloromethane for 0.25h; Inert atmosphere; Stage #2: n-pentadecanal In dichloromethane at 20℃; for 6h; Inert atmosphere;
  • 94
  • [ 2765-11-9 ]
  • [ 627-82-7 ]
  • C36H70O5 [ No CAS ]
YieldReaction ConditionsOperation in experiment
86.08% With p-ethylbenzenesulfonic acid In water at 140℃; for 15h; Inert atmosphere; Green chemistry; 9 Example 9 In a three-necked round-bottomed flask equipped with an electric stirrer, a water separator, a condenser, and a nitrogen inlet tube, 33.23 g of diglycerin was added, followed by n-pentadeca:Diglycerol = 1: 10 was added 4.53g n-pentadecylenide, according to n-pentadecenal: ethylbenzene sulfonic acid = 1: 0.12 ethylbenzene sulfonic acid catalyst 0.45g, according to n-pentadecyl:Water = 1: 40, 14.40 g of water was added, and the temperature was raised to 140 ° C. with stirring under a nitrogen atmosphere. After the reaction was carried out for 15 hours, the mixture was cooled to room temperature and the resulting reaction solution was extracted with ethyl acetate.Washed with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, concentrated in vacuo to give diglycerol diacetal product 5.01g, the yield was 86.08%.
  • 95
  • [ 1120-36-1 ]
  • [ 2765-11-9 ]
YieldReaction ConditionsOperation in experiment
With 3C38H72NO16(1+)*C18H12O9PS3(3-); Rh(CO)<SUB>2</SUB>acac at 20 - 95℃; for 0.5h; Inert atmosphere; 18 Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3-)2-12](o=p=2,n=2)/1-octene system under twoPhase hydroformylation Add Rh(acac)(CO)2, [(N-(EO)4Ph)Py]2 [(SO3-)2-12] and 1-octene to a stainless steel autoclave under an inert atmosphere, the ratio Is: [(N-(EO)4Ph)Py]2[(SO3-)2-12]/Rh(acac)(CO)2=5:1Erby), 1-octene / Rh (acac) (CO) 2 = 1000:1 (molar ratio), and then pressurized with syngas (H2 / CO = 1:1) to5.0MPa, reaction temperature 100 ° C, reaction time 0.5 hours, then rapidly cooled to room temperature, vent the synthesis gas, then open the kettle, systemNaturally divided into two phases, the lower layer is an ionic liquid phase containing a ruthenium catalyst, the upper layer is an organic phase, and n-heptane extraction can also be added.The organic phase containing the product aldehyde was obtained by simple two-phase separation. The gas chromatographic analysis showed that the conversion of 1-octene was98.4%, the selectivity of aldehyde is 72.8%, the molar ratio of normal aldehyde to isomeric aldehyde is 1.8:1, and the TOF value is 1433h-1.; The olefin was changed to 1-tetradecene, and the remaining reaction conditions and steps were the same as those in Example 14. The gas chromatographic analysis results were: 1-tenThe conversion of tetraene is 48.7%, the selectivity of aldehyde is 75.3%, the molar ratio of normal aldehyde to isomer is 1.5:1, and the TOF value is733h-1.
  • 96
  • [ 2765-11-9 ]
  • [ 107-19-7 ]
  • (Sa)-octadeca-2,3-dien-1-ol [ No CAS ]
YieldReaction ConditionsOperation in experiment
67% With (R)-α,α-diphenylprolinol; copper(ll) bromide In 1,4-dioxane at 130℃; for 12h; Schlenk technique; Inert atmosphere; (Sa)-Octadeca-2,3-dien-1-ol (4) To a flame-dried Schlenk tubewith a Teflon plug were added sequentially CuBr2 (132 mg, 0.59mmol), (R)-α,α-diphenylprolinol (750 mg, 2.96 mmol), propargylicalcohol (255 μL, 248 mg, 4.42 mmol), pentadecanal (1.0 g,4.42 mmol) and dioxane (14 mL) under nitrogen atmosphere.The Schlenk tube was then sealed and the reaction mixture was placed in a preheated oil bath at 130 °C for 12 h. After cooling to r.t., the resulting brown mixture was diluted with ether (30 mL)and washed with an aqueous solution of hydrochloric acid (3 M,20 mL). The organic layer was separated and the aqueous layerthen extracted with ether (20 mL). The organic phases were collected,washed with saturated NaCl solution, dried over magnesium sulfate and concentrated to dryness to give a residue,which was purified by flash chromatography on silica gel(EtOAc/petroleum ether 1:8) to give the allenol 4 (530 mg, 67%yield). 1H NMR (CDCl3, 300 MHz): δ = 5.4-5.2 (m, 2 H, H2 andH4), 4.11 (dd, J = 5.4, 3.3, 2 H, H1), 2.02 (ddt, J = 9.9, 6.9, 3.6 Hz,2 H, H5), 1.53 (br s, 1 H, OH), 1.45-1.2 (m, 24 H, H6-H17), 0.95-0.8 (m, 3 H, H18). 13C NMR (CDCl3, 75 MHz): δ = 203.1 (C3), 94.3(C4), 91.9 (C2), 60.9 (C1), 32.0 (C5), 29.8, 29.6, 29.5, 29.3, 29.2,28.8, 22.8 (C6-C17), 14.3 (C18). HRMS: m/z [M+H]+ calcd forC18H35O: 267.2688; found: 267.2688. [α]D25= +44.3 (c 0.51,CHCl3). 98% ee [SFC conditions: Chiralcel IA-3 column, CO2 toCO2-MeOH 95:5, 2.0 mL/min, λ = 210 nm, tR = 6.6 (minor), 6.9(major) min].
  • 97
  • [ 2765-11-9 ]
  • (R)-(+)-1,2-epoxypentadecane [ No CAS ]
YieldReaction ConditionsOperation in experiment
79% Stage #1: n-pentadecanal With (2R,5S)-2-tert-butyl 3,5-dimethylimidazolidin-4-one trifluoroacetic acid salt; 2,2,3,4,5,6-hexachloro-cyclohexa-2,4-dien-1-one In tetrahydrofuran at 20℃; Stage #2: With sodium tetrahydroborate In tetrahydrofuran; ethanol at 0 - 20℃; Stage #3: With potassium hydroxide In tetrahydrofuran; ethanol; water at 20℃; 3.2.1. General Procedure for the Synthesis of Chiral Epoxides 2a-d, 10 General procedure: To a solution of (2R,5S)-2-(tert-butyl)-3,5-dimethylimidazolidin-4-one triuoroacetate (57 mg,0.20 mmol) in THF (0.5 mL), 2,3,4,5,6,6-hexachlorocyclohexa-2,4-dien-1-one (331 mg, 1.10 mmol) wasadded and the solution was stirred for 5 min, before the aldehyde (1.00 mmol) was added. The reaction mixture was stirred for 30 min at room temperature and was cooled to 0 °C, before EtOH (0.6 mL) andNaBH4 (121 mg, 3.20 mmol) were added. After 10 min, the medium was warmed to room temperaturefor 5 min, before a freshly prepared solution of aqueous KOH (1.70 g KOH diluted in 2.7 mL water) andEtOH (1.3 mL) were added and the resulting mixture was stirred vigorously for 30 min. Then, water(1 x 20 mL) was added to the mixture before it was extracted with Et2O (3 x 10 mL), washed withbrine (1 x 20 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. Purificationof the resulting residue by silica gel chromatography (petroleum ether 40-60 °C/diethyl ether, 9:1 or 8:2) aorded the title compounds.
  • 98
  • [ 2765-11-9 ]
  • 2,2-d<SUB>2</SUB>-pentadecanal [ No CAS ]
YieldReaction ConditionsOperation in experiment
81% With water-d2; triethylamine at 100℃; for 1h; Inert atmosphere; 3.2.9. 2,2-d2-Pentadecanal (5) To a flame-dried round-bottom ask under argon atmosphere, pentadecanal (226 mg, 1.00 mmol),D2O (1 mL) and triethylamine (0.01 mL, 0.10 mmol) were added and the mixture was left stirring in an oil bath at 100 °C for 1 h. Then, the mixture was allowed to warm to room temperature and after the addition of an aqueous solution of 1 N HCl, it was extracted with Et2O (2 x 10 mL). The organic layers were washed successively with an aqueous solution of 10% NaHCO3 (10 mL) and brine (10 mL) andthen collected, dried over Na2SO4 and concentrated in vacuo. The aldehyde was immediately used forthe next step without further purification. Colorless oil, 185 mg, yield 81%; Rf value (pet. ether:diethylether = 9:1) 0.37; 1H-NMR (CDCl3) δ 9.59 (s, 1H, CHO), 1.46-1.06 (m, 24H, 12 x CH2), 0.75 (t, J = 6.2 Hz,3H, CH3); 13C-NMR (CDCl3) δ 201.9, 43.6-42.1 (m, CD2) 31.7, 29.5, 29.4, 29.3, 29.2, 28.9, 22.5, 21.7, 13.8.
  • 99
  • [ 2765-11-9 ]
  • C27H32O2P(1+)*Br(1-) [ No CAS ]
  • 2-(henicos-6-en-1-yl)-1,3-dioxolane [ No CAS ]
YieldReaction ConditionsOperation in experiment
87% Stage #1: C27H32O2P(1+)*Br(1-) With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone at 80℃; for 0.5h; Stage #2: With n-butyllithium In tetrahydrofuran; hexane at -5 - -1℃; for 2h; Inert atmosphere; Stage #3: n-pentadecanal In cyclohexane at 25℃; for 0.25h;
  • 100
  • [ 2765-11-9 ]
  • [ 4301-14-8 ]
  • C17H32O [ No CAS ]
YieldReaction ConditionsOperation in experiment
91% In tetrahydrofuran at 0 - 20℃; for 1.5h; Further stages;
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