(4-Benzylpiperazin-1-yl)(2-(isopentylamino)pyridin-3-yl)methanone (NSI-189) [C22H30N4O]

Page 1

Query Query

N

Results

Date

10 reactions in Reaxys

2018-06-06 17h:25m:31s (UTC)

O

NH

N

1. Query N

Search as: Product, As drawn, No mixtures ))

Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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2018-06-06 17:28:29


N

N

O

Cl NH

N

O N

Cl

Rx-ID: 42226858 View in Reaxys 1/10 Yield

Conditions & References Reaction Steps: 4 1: triethylamine / isopropyl alcohol / 1 h / 20 - 35 °C 2: hydrogenchloride / isopropyl alcohol / 9 h / 50 °C 3: triethylamine / acetonitrile / 3.5 h / 50 °C 4: acetonitrile / 19 h / 85 °C With hydrogenchloride, triethylamine in isopropyl alcohol, acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

O

O

N

O

NH

N

N

N

N

O

N

Cl

Rx-ID: 42226863 View in Reaxys 2/10 Yield

Conditions & References Reaction Steps: 3 1: hydrogenchloride / isopropyl alcohol / 9 h / 50 °C 2: triethylamine / acetonitrile / 3.5 h / 50 °C 3: acetonitrile / 19 h / 85 °C With hydrogenchloride, triethylamine in isopropyl alcohol, acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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H N

-1

N

HCl

O

NH

N

N

N

O

N

Cl

Rx-ID: 42226866 View in Reaxys 3/10 Yield

Conditions & References Reaction Steps: 2 1: triethylamine / acetonitrile / 3.5 h / 50 °C 2: acetonitrile / 19 h / 85 °C With triethylamine in acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

N

O

O

Cl NH

N

NH 2

N

N

N

N

Rx-ID: 42226869 View in Reaxys 4/10 Yield 7.78 g

Conditions & References 4.D : Conversion to 1E (Steps 3 and 4) D. Alternatively, to an 8.0 g sample of 3E.HCl in acetonitrile (48 mL, 6 vol) was added triethylamine (2.5 equiv) followed by benzyl chloride (1.05 equiv). The resulting suspension was heated to 50° C. when it turned into a clear solution. The reaction was monitored by HPLC and was judged complete after 3.5 hours (3.3percent of unreacted 3E.HCl). The reaction mixture was cooled to ambient temperature and the solids (TEA.HCl salt) were filtered. (0096) The filtrate was evaporated to adjust the weight of the solution to 18 g (≈1:1 acetonitrile/product by weight). To this was added isoamylamine (≈4:1 isoamylamine/acetonitrile, 10 equiv of isoamylamine) and the resulting solution was heated to 85° C. The reaction was judged complete by HPLC analysis after 19 hours (3.0percent of unreacted 2E). The reaction mixture was cooled to ambient temperature and the solvent was removed under reduced pressure to adjust weight of the solution to 22 g (1 g of solvent per gram of 1E). On cooling a wet solid was obtained and this was triturated with heptanes (6 g per gram of 1E). The suspension was stirred at ambient temperature for 16 hours and the solids were collected by filtration on a Whatman® 1 filter paper and the filter cake was washed with heptanes (20 mL), followed by water (2×20 mL). The product was dried in a vacuum oven at ambient temperature to afford 7.78 g (69percent yield over two steps) of 1E as a light brown solid. HPLC purity was >99.9percent (AUC 226 nm). in acetonitrile, Time= 19h, T= 85 °C , Temperature Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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2018-06-06 17:28:29


N

N

O

Cl NH

N

O N

OH

Rx-ID: 42226873 View in Reaxys 5/10 Yield

Conditions & References Reaction Steps: 5 1: thionyl chloride; N,N-dimethyl-formamide / 3.08 h / 65 °C 2: triethylamine / isopropyl alcohol / 1 h / 20 - 35 °C 3: hydrogenchloride / isopropyl alcohol / 9 h / 50 °C 4: triethylamine / acetonitrile / 3.5 h / 50 °C 5: acetonitrile / 19 h / 85 °C With hydrogenchloride, thionyl chloride, triethylamine, N,N-dimethyl-formamide in isopropyl alcohol, acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

N

HN

N

Cl O O

N -1

O

P HO

N

OH HO

Cl

Rx-ID: 42226860 View in Reaxys 6/10 Yield

Conditions & References Reaction Steps: 5 1: triethylamine / isopropyl alcohol / 1 h / 20 - 35 °C 2: hydrogenchloride / isopropyl alcohol / 9 h / 50 °C 3: triethylamine / acetonitrile / 3.5 h / 50 °C 4: acetonitrile / 19 h / 85 °C 5: phosphoric acid / ethanol; water / 0.5 h / 75 °C With hydrogenchloride, phosphoric acid, triethylamine in ethanol, water, isopropyl alcohol, acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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2018-06-06 17:28:29


N

O

O

HN O

N

O

N -1

P HO

N

OH HO

N

O

N

Cl

Rx-ID: 42226865 View in Reaxys 7/10 Yield

Conditions & References Reaction Steps: 4 1: hydrogenchloride / isopropyl alcohol / 9 h / 50 °C 2: triethylamine / acetonitrile / 3.5 h / 50 °C 3: acetonitrile / 19 h / 85 °C 4: phosphoric acid / ethanol; water / 0.5 h / 75 °C With hydrogenchloride, phosphoric acid, triethylamine in ethanol, water, isopropyl alcohol, acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

N

H N

-1

HCl HN O O

N

N -1

OH HO

O

N

P HO

N

Cl

Rx-ID: 42226867 View in Reaxys 8/10 Yield

Conditions & References Reaction Steps: 3 1: triethylamine / acetonitrile / 3.5 h / 50 °C 2: acetonitrile / 19 h / 85 °C 3: phosphoric acid / ethanol; water / 0.5 h / 75 °C With phosphoric acid, triethylamine in ethanol, water, acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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2018-06-06 17:28:29


N N

O

HN NH

N

O O

N -1

P HO

N

OH HO

N

Rx-ID: 42226870 View in Reaxys 9/10 Yield

Conditions & References

62 %

6 : Preparation of Phosphate Salt A. A 22 L, three-neck, round-bottom flask equipped with an addition funnel, a reflux condenser, a thermocouple, and an overhead stirrer was placed in a heating mantle. The flask was charged with ethanol (7.9 L, Pharmco lot 0802062) followed by deionized water (420 mL). Next 1E (700 g, 2.1 mol) was charged to the reactor and the resulting mixture was heated to 75° C. A 1 M solution of H3PO4 in ethanol (4.5 L, 4.5 mol, 2.1 equiv) was charged as a quick stream over a period of 30 min. The resulting mixture was stirred for 15 min and 1E.H3PO4 (0.5 g) was added as seed for recrystallization. The resulting clear solution was cooled to ambient temperature at a rate of 20° C./h. (0106) The cooled suspension was allowed to stir at ambient temperature for 11 h and filtered through a Whatman® 1 filter paper. Ethanol (2.8 L×2) was used to aid in the transfer and also to wash the filter cake. The product was dried under vacuum to a constant weight at 25° C. to obtain 1E.H3PO4 as a white solid (751 g, 62percent yield). Analysis by HPLC indicated a purity of >99.9percent (AUC 226 nm) and 1H NMR was consistent with the assigned structure. With phosphoric acid in ethanol, water, Time= 0.5h, T= 75 °C Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

N

HN

N

Cl O O

N -1

O

P HO

N

OH HO

OH

Rx-ID: 42226875 View in Reaxys 10/10 Yield

Conditions & References Reaction Steps: 6 1: thionyl chloride; N,N-dimethyl-formamide / 3.08 h / 65 °C 2: triethylamine / isopropyl alcohol / 1 h / 20 - 35 °C 3: hydrogenchloride / isopropyl alcohol / 9 h / 50 °C 4: triethylamine / acetonitrile / 3.5 h / 50 °C 5: acetonitrile / 19 h / 85 °C 6: phosphoric acid / ethanol; water / 0.5 h / 75 °C With hydrogenchloride, thionyl chloride, phosphoric acid, triethylamine, N,N-dimethyl-formamide in ethanol, water, isopropyl alcohol, acetonitrile Patent; NEURALSTEM, INC.; Venkatraman, Sripathy; Mahmood, Syed; Mobele, Bingidimi I.; Lapina, Olga; Vercoe, Kellie; Li, Ying; Salsbury, Jonathan; McLaws, Mark; (14 pag.); US9278933; (2016); (B2) English View in Reaxys

Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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Copyright © 2018 Reed Elsevier Properties SA. All rights reserved. Authorized use only. Reaxys® and the Reaxys® trademark are owned and protected by Reed Elsevier Properties SA and used under license.

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2018-06-06 17:28:29


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