Pyrrolidine hydrochloride [C4H10ClN]

Query 1. Query

Query

Results

Date

RX.PXRN=3547227

16 reactions in Reaxys

2018-06-17 16h:46m:02s (UTC)

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H N

H N Cl

H

Rx-ID: 25753224 View in Reaxys 1/16 Yield

Conditions & References General procedure for the preparation of amine hydrochloride salts 2c-2r General procedure: To a 25-mL round-bottomed flask containing ammonium chloride (0.54 g, 10 mmol) was added ethanol (3 mL) followed by the requisite amine (10 mmol). The mixture was magnetically stirred and refluxed for 2 h. The solvent was then removed by rotary evaporation affording the hydrochloride salt as a solid invariably in quantitative yield.

With hydroxylamine hydrochloride in ethanol, Time= 2h, Reflux Di Grandi, Martin J.; Bennett, Caitlin; Cagino, Kristen; Muccini, Arnold; Suraci, Corey; Saba, Shahrokh; Synthetic Communications; vol. 45; nb. 22; (2015); p. 2601 - 2607 View in Reaxys With methanol, acetyl chloride in diethyl ether, Time= 1h, T= 0 °C , Inert atmosphere Ghosh, Titli; Mukherji, Ananya; Srivastava, Hemant Kumar; Kancharla, Pavan K.; Organic and Biomolecular Chemistry; vol. 16; nb. 16; (2018); p. 2870 - 2875 View in Reaxys 5 :4N HCl/dioxane (70.5 mL) was added to a solution of pyrrolidine (20 g, 0.28 mol) in dioxane (20 ml). The reaction mixture was evaporated. The residue was recrystallized from Et2O, separated by filtration, washed with ether, and dried to give the title compound (28.5 g, 96percent) as white crystals. 1H NMR data (DMSO-d6): δ 9.40(br.s, 2H, NH+); 3.00-3.13 (m, 4H); 1.77-1.85 (m, 4H) With hydrogenchloride in 1,4-dioxane Patent; PFIZER PRODUCTS INC.; WO2007/49123; (2007); (A1) English View in Reaxys 78.A :Pyrrolidine (1.5 g, 21 mmol) was placed in a round bottom flask under N2 with stirring. THF (4 ml.) was added, followed by the drop-wise addition of 4 N HCI in dioxane (5.3 ml_, 21 mmol). Potassium thiocyanate (2.0 g, 21 mmol) was then added in one portion to the stirring solution of pyrrolidine hydrochloride. This mixture was then stirred at rt for 30 min followed by heating at 100 0C for 2 h. The reaction was then cooled to rt, MeOH (50 ml.) was added, and solids that persisted were filtered away.

Subsequent concentration of the MeOH/reaction solution yielded 3.0 g of the crude 1-pyrrolidinecarbothioamide. 1H-NMR (400 MHz, DMSO-d6) δ 8.60 (brs, 2 H), 3.07 (m, 4 H), and 1.82 (m, 4 H).

With hydrogenchloride in tetrahydrofuran, 1,4-dioxane Patent; SMITHKLINE BEECHAM CORPORATION; WO2009/32667; (2009); (A1) English View in Reaxys H N

Cl

N H

H

Cl

H

Rx-ID: 47250563 View in Reaxys 2/16 Yield

Conditions & References With C106H182Cl2N2O34Ru in water-d2, Time= 48h, T= 45 °C Kim, Cheoljae; Ondrusek, Brian A.; Chung, Hoyong; Organic Letters; vol. 20; nb. 3; (2018); p. 736 - 739 View in Reaxys H N

NH 2 Cl

H 2N

H

Rx-ID: 43640631 View in Reaxys 3/16 Yield

Conditions & References Stage 1: With [{CyPN(H)P}Co(CH2SiMe3)]-BArF 4 in toluene, Time= 24h, T= 120 °C , Schlenk technique, Sealed tube

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Stage 2: With hydrogenchloride in tetrahydrofuran Yin, Zhiwei; Zeng, Haisu; Wu, Jing; Zheng, Shengping; Zhang, Guoqi; ACS Catalysis; vol. 6; nb. 10; (2016); p. 6546 6550 View in Reaxys

H N

H N

N

Cl

Cl

Cl

H

N

Rx-ID: 41003017 View in Reaxys 4/16 Yield

Conditions & References

> 70 %

Time= 24h, Darkness Kyran, Samuel J.; Sanchez, Sergio G.; Arp, Christopher J.; Darensbourg, Donald J.; Organometallics; vol. 34; nb. 14; (2015); p. 3598 - 3602 View in Reaxys

H N

O H N

Cl

H

OH

Rx-ID: 41474915 View in Reaxys 5/16 Yield

Conditions & References General Decarboxylation Procedure General procedure: A magnetic stir bar, 3 mL of n-PrOH, 10 mmol of R-carvone, and 5 mmol of amino acid were charged to a pressure vessel. The vessel was heated from room temperature to 190°C over 5 min with stirring. If necessary the reaction vessel was maintained at 190°C for an additional time until the slurry became clear. The vessel was allowed to cool to below the solvent boiling point, carefully vented to release evolved CO2, and analyzed via GC-MS to verify the presence of decarboxylated imine. Ten mL of 2M HCl was then added in a one-pot fashion, and, in all cases but threonine, the reaction vessel was heated to 190°Cover 5 min with stirring and then allowed to cool. In the case of the temperature-sensitive threonine, soxhlet extraction with toluene was performed at 80°C to remove R-carvone from the reaction mixture. The aqueous reaction mixture was washed three times with 25 mL of ether, and then water solvent was distilled off from the hydrochloride salt. The hydrochloride salt was transferred to a vacuum oven and dried overnight at 150 °C and 10 Torr.

Stage 1: With (R)-Carvone in propan-1-ol, T= 0 - 190 °C , Green chemistry Stage 2: With hydrogenchloride in propan-1-ol, water, Time= 0.0833333h, T= 190 °C , Microwave irradiation, Green chemistry, Temperature Jackson, Douglas M.; Ashley, Robert L.; Brownfield, Callan B.; Morrison, Daniel R.; Morrison, Richard W.; Synthetic Communications; vol. 45; nb. 23; (2015); p. 2691 - 2700 View in Reaxys Cl

H

N

N

H N Cl

N

H

H 2N

Rx-ID: 37108152 View in Reaxys 6/16 Yield

Conditions & References

62 %Spectr. 3 : 4.4. General procedure for the reduction of dinitriles General procedure: To a 50 mL round-bottom flask, under nitrogen atmosphere, containing dinitriles 1p (500 mg, 4.2 mmol, 1.0 equiv) in 5.0 mL of toluene were added PMHS (1.0 mL, 16.8 mmol, 4.0 equiv) and Ti(Oi-Pr)4 (1.3 mL, 4.3 mmol, 1.0 equiv).

The mixture was then heated at 100°C for 24 h (the colorless solution turned into deep purple). After cooling to rt, the clear

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solution was diluted in toluene (30 mL) and hydrolyzed with aqueous 1M HCl (15 mL, 3.6 equiv) for 4 h (until the deep purple solution became yellow). The crude mixture was then concentrated under reduced pressure. The resulting solid was filtered, washed with pentane (60 mL), dissolved in chloroform and filtrate on a pad of Celite®. The filtrate was finally concentrated under reduced pressure affording the amine 3p as a hydrochloride salt.

Stage 1: With 1,1,3,3-Tetramethyldisiloxane, titanium(IV)isopropoxide in toluene, Time= 24h, T= 60 °C , Inert atmosphere Stage 2: With hydrogenchloride, water in toluene, Time= 4h, T= 20 °C , Inert atmosphere, Reagent/catalyst, Concentration, chemoselective reaction Laval, Stephane; Dayoub, Wissam; Pehlivan, Leyla; Metay, Estelle; Favre-Reguillon, Alain; Delbrayelle, Dominique; Mignani, Gerard; Lemaire, Marc; Tetrahedron; vol. 70; nb. 4; (2014); p. 975 - 983 View in Reaxys H N Cl

H

Rx-ID: 38715352 View in Reaxys 7/16 Yield

Conditions & References General “One-Pot” Procedure for the Decarboxylation of Amino Acids General procedure: General “One-Pot” Procedure for the Decarboxylation of Amino Acids [0045] A magnetic stir bar, 3 mL of n-PrOH, 10 mmol of R-Carvone, and 5 mmol of amino acid were charged to a pressure vessel. The vessel was heated from room temperature to 190° C. over 5 min with stirring. If necessary the reaction vessel was maintained at 190° C. for additional time until the slurry became clear. The vessel was allowed to cool to below the solvent boiling point, carefully vented to release evolved CO2, and 10 mL of 2M HCl was added. The vessel was heated to 190° C. over 5 min with stirring and allowed to cool.

The aqueous reaction mixture was washed three times with 25 mL of ether and water solvent distilled off from the hydrochloride salt. The hydrochloride salt was transferred to a vacuum oven and dried overnight at 150° C. and 10 Torr. The hydrochloride salt was then weighed and analyzed via IR and NMR.; 2-methylpropan-1-amine hydrochloride, δH 0.83 6H d J=4, 1.79 1H m J=8, 2.69 2H d J=8; Cδ 18.8, 26.2, 46.3 Stage 1: With (R)-Carvone in propan-1-ol, Time= 0.0833333h, T= 20 - 190 °C , p= 11251.1Torr , Sealed tube, Microwave irradiation Stage 2: With hydrogenchloride in propan-1-ol, water, Time= 0.0833333h, T= 190 °C , Microwave irradiation Patent; Morrison, Richard W.; Jackson, Douglas Michael; US2014/275569; (2014); (A1) English View in Reaxys

H N

SiH

Cl

H

N

Rx-ID: 33730635 View in Reaxys 8/16 Yield

Conditions & References Stage 1: With hydrogenchloride in diethyl ether, Time= 1h, T= 23 °C , Inert atmosphere Stage 2: With sodium hydrogencarbonate in methanol, water, Time= 2h, T= 23 °C , Inert atmosphere Cheng, Chen; Brookhart, Maurice; Journal of the American Chemical Society; vol. 134; nb. 28; (2012); p. 11304 - 11307 View in Reaxys

H H

H

(v5)

(v5) (v5)

(v5) (v5)

Cl

O P O

N

(v6)

H

Ir

(v5)

H H

H

P O N (v4) O

H Cl (v5) Ir (v4) O (v7)P O H (v5) N H H

H N Cl

H

H

Rx-ID: 23071081 View in Reaxys 9/16

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Yield

Conditions & References

85 %

Preparation of [[(COD) IR (K2-LL) LL]] (Ir-2): THF (5 mL) was added to a mixture of [[(COD) IRCL] (Ll) ] (1) [(100 MG,] 0. [110 MMOL) AND PHOSPHORAMIDITE LL] (123 mg, 0.230 mmol) at room temperature. After complete dissolution of the iridium complex, pyrrolidine (391 mg, 460 [J. L,] 5.50 mmol) was added by syringe, and the solution was strirred overnight. The color of the solution changed from orange to yellow, and a precipitate of the pyrrolidine hydrochloride was observed. The solvent was evaporated under vacuum, and the yellow residue was suspended in a mixture of 2 mL diethyl ether and 2 mL benzene. This suspension was filtered through a 0.45 [PM] nylon syringe filter. The solvent was evaporated under vacuum, and the yellow product was dissolved in 0.5 mL CH2C12 and precipitated by layering with pentane at-30°C to yield a fine yellow powder, which was dried under high vacuum overnight.

Yield: 85 percent (129 [MG). LH NMR] (400.13 MHz, [CD2CK,] 248 K) : [8-0.] 66 (dt, J= 11.8, 6.0 Hz, [1H,] [IRCH2),] 0.32 (br s, 3H, [CH3),] 0.92 (d, [J=] 6.8 Hz, 3H, [CH3),] 1. [37] (d, [J=] 6.5 Hz, 3H, CHCH3), 1.67 [(M,] [1H,] COD), 1.73 (dt, [J=] 18.6, 11.3 [HZ, 1H,] IrCH2), 1.93 [(M,] 2H, COD), 2.32 [(M,] 2H, COD), 2.45 [(M,] 2H, COD), 2.71 [(M.] 1H, COD), 2.91 [(M,] 2H, COD), 3. 28 (dd, J= 6.9 Hz, J= 7.1 Hz, [1H,] CHCH2Ir), 3.75 [(M,] 1H, CHCH3), 3.81 [(M,] 1H, COD), 4.54 [(M,] 1H, CHCH3), 4.69 [(M,] 1H, COD), 5.11 [(M,] 1H, CHCH3), 5.85 (d, J= 7.2 Hz, 1H, ArH), 6.50 (d, J= 9.5 Hz, 1H, ArH), 6.55 (t, J= 12.6 Hz, 2H, ArH), 6.92 [(M,] 4H, ArH), 6.92 (d, J= 7.0 Hz, 1H, ArH), 7.08 [(M,] 2H, ArH), 7.13 [(M,] 3H, ArH), 7.17-7.

26 [(M,] 13H, ArH), 7.32 [(M,] 4H, [ARH),] 7.40 [(M,] 2H, ArH), 7.49 (t, J= 8.7 Hz, 1H, [ARH),] 7.64 (d, J= 8.6 Hz, 1H, ArH), 7.73 (d, J= 8.7 Hz, 2H, ArH), 7.83 (d, J='8. 5 Hz, 1H, ArH), 7.87 (d, J= 8.7 Hz, 1H, ArH), 7.92-8. 06 [(M,] 5H, ArH), 8.13 (d, J= 8.6 Hz, 1H, ArH); 31p NMR (161.9 MHz, [CD2C12) 6] 152.6 (d, J= 46.3 Hz, [1P),] 127.8 (d, J= 46.2 Hz, [1P)] main diastereomer (94 percent), 149.4 (d, [J=] 77.8 Hz, [1P),] 146.0 (d, J= 78. 0 Hz, [1P)] minor diastereomer (6 percent); Aliphatic region of the [13C] NMR spectrum (125.7 MHz, [CD2C12,] 248K) 8 15.2 (dd, [J=] 4.9 Hz, [J=] 5.8 Hz, IrCH2), 20.1 (s, [CH3),] 21.9 (s, [CH3),] 24.1 (s, [CH3),] 23.7 (br s, CH2-COD), 29.7 (br s, CH2-COD), 34.3 (br s, CH2-COD), 44.0 (s, [CH2-COD),] 45.7 [(M,] CH-COD), 46.2 [(M,] CH-COD), 53.9 (s, CH), 54.7 (d, J= 24.7 Hz, CH), 59.0 (br s, CH), 68.3 (d, [J=] 43.9 Hz, [CHCH2),] 69.8 (s, CH- COD), 82.6 (s, CH-COD); MS [(FAB+)] (percent): [M/Z =] 1378.1 [M+] (8), 838.2 [M+[C36H3OP02N]] (100), 730.2 [[M+-L1-CSHL2]] (69); Anal. Calc. for [CSOH7IH-N204P2] : C, 69.70 ; H, 5.19 ; N, 2.03 ; P, 4.49 ; [CL,] 0.00. Found: C, 69.55 ; H, 5.35 ; N, 2.09 ; P, 4.36, Cl <0.02.

With pyrrolidine in tetrahydrofuran, T= 20 °C Patent; YALE UNIVERSITY; WO2004/24684; (2004); (A2) English View in Reaxys

OH

H N

H N

Cl

N

Cl

HO

N

H N

Rx-ID: 4663306 View in Reaxys 10/16 Yield 75 %

Conditions & References in diethyl ether, Time= 48h, Ambient temperature Quadrelli, Paolo; Invernizzi, Anna Gamba; Falzoni, Mario; Caramella, Pierluigi; Tetrahedron; vol. 53; nb. 5; (1997); p.

1787 - 1796 View in Reaxys H N

N N

Cl

H

N

Rx-ID: 2189551 View in Reaxys 11/16 Yield

Conditions & References With hydrogenchloride, dimethylsulfide, thexylchloroborane, Yield given. Multistep reaction Jego, J. M.; Carboni, B.; Vaultier, M.; Bulletin de la Societe Chimique de France; nb. 6; (1992); p. 554 - 565 View in Reaxys

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O

N B

H N

N N

O

Cl

H

Rx-ID: 3453417 View in Reaxys 12/16 Yield

Conditions & References With boron trichloride in dichloromethane Jego, J. M.; Carboni, B.; Vaultier, M.; Bulletin de la Societe Chimique de France; nb. 6; (1992); p. 554 - 565 View in Reaxys Cl

Cl

Cl

H N

H N Cl

O

O

O

H

O

N

N

N

O

O

O

N O

Rx-ID: 1458350 View in Reaxys 13/16 Yield

Conditions & References in acetonitrile, T= 10 °C , temperature, deuterated compound, isotope effect, ΔH(excit.), ΔS(excit.), ΔG(excit.), Kinetics, Thermodynamic data Dworniczak, Miroslaw; Jarczewski, Arnold; Acta Chimica Hungarica; vol. 126; nb. 5; (1989); p. 599 - 604 View in Reaxys

HO

H N

Br B

Cl

H

OH

Rx-ID: 2028504 View in Reaxys 14/16 Yield

Conditions & References Yield given. Multistep reaction Jego, Jean Michel; Carboni, Bertrand; Vaultier, Michel; Carrie, Robert; Journal of the Chemical Society, Chemical Communications; nb. 2; (1989); p. 142 - 143 View in Reaxys

O

N B

Cl

H N

N N

B

Cl

O

Cl

H

Cl

Rx-ID: 26580633 View in Reaxys 15/16 Yield

Conditions & References in dichloromethane, to soln. of azide was added soln. of BCl3 at -78°C; mixt. was allowed to warm up to room temp. overnight, MeOH added and solvents removed; characterized as benzoyl deriv.

Jego, Jean Michel; Carboni, Bertrand; Vaultier, Michel; Carrie, Robert; Journal of the Chemical Society, Chemical Communications; nb. 2; (1989); p. 142 - 143 ; (from Gmelin) View in Reaxys

O H 2N

O NH 2

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H N Cl

resorcinol-mono-<δ-amino-butyl ether >-hydrochloride

H

HO

OH

Rx-ID: 8286652 View in Reaxys 16/16 Yield

Conditions & References p= 7Torr Wilson; Adams; Journal of the American Chemical Society; vol. 45; (1923); p. 538 View in Reaxys

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