Hydrochloric Acid → HCID 14168273, compound

HRID 1052950Notes

Reaction equation

CC1C=CC(S([O:11][C@@H:12]2[CH2:25][C:24]3[C@@:15]([CH3:38])([C@@H:16]4[C@@H:21]([CH2:22][CH:23]=3)[C@@H:20]3[CH2:26][CH2:27][C@H:28]([C@@H:29]([CH2:31][CH2:32][CH2:33][CH:34]([CH3:36])[CH3:35])[CH3:30])[C@@:19]3([CH3:37])[CH2:18][CH2:17]4)[CH2:14][CH2:13]2)(=O)=O)=CC=1.[OH:39][CH2:40][CH2:41][CH2:42][C:43]#N.[OH-:45].[Na+].Cl.[CH:48]([OH:51])([CH3:50])[CH3:49]>C1(C)C=CC=CC=1.C(OCC)C>[CH3:36][CH:34]([CH2:33][CH2:32][CH2:31][C@H:29]([C@@H:28]1[C@:19]2([CH3:37])[C@H:20]([C@H:21]3[C@H:16]([CH2:17][CH2:18]2)[C@:15]2([CH3:38])[C:24]([CH2:49][C@@H:48]([O:51][CH2:43][CH2:42][CH2:41][C:40]([OH:45])=[O:39])[CH2:50][CH2:14]2)=[CH:23][CH2:22]3)[CH2:26][CH2:27]1)[CH3:30])[CH3:35].[CH3:36][CH:34]([CH2:33][CH2:32][CH2:31][C@H:29]([C@@H:28]1[C@:19]2([CH3:37])[C@H:20]([C@H:21]3[C@H:16]([CH2:17][CH2:18]2)[C@:15]2([CH3:38])[C:24]([CH2:25][C@@H:12]([O:11][CH2:41][C:40]([OH:51])=[O:39])[CH2:13][CH2:14]2)=[CH:23][CH2:22]3)[CH2:26][CH2:27]1)[CH3:30])[CH3:35]

Participants

Conditions

Temperature: 100 °C

Procedure

A solution of cholesteryl tosylate (2.8 g, 5.1 mmol) and 4-hydroxybutanenitrile (0.61 g, 7.1 mmol) in toluene was stirred at 120° C. for 24 h and then the solvent was evaporated in vacuo. The obtained crude 4-(cholest-5-en-3β-yloxy)butanenitrile was dissolved in isopropyl alcohol (30 ml), aqueous NaOH (12%; 100 ml) was added and the mixture was stirred at 100° C. for 3 days. The mixture was cooled to room temperature, aqueous hydrochloric acid (10%, 100 ml) was added and the product was taken in diethyl ether (4×30 ml). The combined extracts were dried over anhydrous MgSO4 and concentrated in vacuo. Flash chromatography of the residue on silica gel column (320 ml) in toluene-ethyl acetate (gradient: 0-40% ethyl acetate, 10 ml/min, 160 min) afforded 4-(Cholest-5-en-3β-yloxy)butanoic acid (general formula IX, where n2=3; 345 mg, 10%). 1H NMR (400 MHz, CHCl3) δ (ppm): 5.32-5.39 m, 1H (H-6); 3.55 td, J=5.90, 1.40 Hz, 2H (CH2-1′); 3.17 tt, J=11.21, 4.39 Hz, 1H (H-3); 2.49 t, J=7.01 Hz, 2H (CH2-3′); 2.36 ddd, J=13.17, 4.71, 2.08 Hz, 1H (H-4a); 2.14-2.24 m, 1H (H-4b); 1.93-2.05 m, 2H (CH2-1, H-12); 1.90 t, J=6.20 Hz, 2H (CH2-2′); 1.78-1.88 m, 3H (H-2, H-7, H-16); 1.02-1.63 m, 22H (cholesterol); 1.01 s, 3H (CH3-19); 0.92 d, J=6.57 Hz, 3H (CH3-21); 0.88 d, J=1.77 Hz, 3H (CH3-26); 0.86 d, J=1.77 Hz, 3H (CH3-27); 0.68 s, 3H (CH3-18); 13C NMR (101 MHz, CHCl3) δ (ppm): 178.28 (C-1′) 140.76 (C-5) 121.69 (C-6) 79.31 (C-3) 66.88 (C-4′) 56.77 (C-14) 56.16 (C-17) 50.18 (C-9) 42.31 (C-13) 39.78 (C-12) 39.51 (C-24) 38.98 (C-4) 37.18 (C−1) 36.86 (C-10) 36.18 (C-22) 35.78 (C-20) 31.94 (C-7) 31.88 (C-8) 31.37 (C-2′) 28.29 (C-2) 28.23 (C-16) 28.01 (C-25) 25.06 (C-3′) 24.28 (C-15) 23.83 (C-23) 22.81 (C-26) 22.55 (C-27) 21.06 (C-11) 19.36 (C-19) 18.71 (C-21) 11.86 (C-18); for C31H52O3 monoisotopic mass: calculated: 472.4. found: MS ESI m/z: 495.4 [M+Na]+. for C31H52O3 calculated: 78.76% C; 11.09% H. found: 78.80% C; 11.18% H; IR (CHCl3): 3517, 2718, 1741, 1710, 1415, 1285 (COOH); 1134, 1105, 1070, 1083, 841 (ether); 1670, 1334 (C═C); 2954, 2869, 1445, 1366 (Me); [α]D-27.2° (c 0.136; CHCl3).

Workup

customthe solvent was evaporated in vacuo
customThe obtained crude 4-(cholest-5-en-3β-yloxy)butanenitrile
temperatureThe mixture was cooled to room temperature
dry with materialThe combined extracts were dried over anhydrous MgSO4
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-10f54a95d6094019bc1608de0c537f2d
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09393200B2

Reaction notes

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