First example of alkyl-aryl Negishi cross-coupling in flow: Mild, efficient and clean introduction of functionalized alkyl groups.

Transcription

1 First example of alkyl-aryl Negishi cross-coupling in flow: Mild, efficient and clean introduction of functionalized alkyl groups. Brecht Egle, Juan de M. Muñoz, Nerea Alonso, Jesús Alcázar,* Wim M. De Borggraeve, Antonio de la Hoz and Angel Díaz-rtiz Table of Contents: General experimental conditions Experimntal conditions Microwave reactions Extended reaction scope tables Scale up runs GC-MS of selected products Measurement of Pd leaching Analytical data NMR spectra S2 S3 S4 S5 S6 S7 S7 S12 S1

2 Experimental. The GC measurement was performed using a 6890 Series Gas Chromatograph (Agilent Technologies) system comprising a 7683 Series injector and autosampler, J&W HP-5MS column (20 m x 0.18 mm, 0.18 m) from Agilent Technologies coupled to a 5973N MSD Mass Selective Detector (single quadrupole, Agilent Technologies). The MS detector was configured with an electronic impact ionization source / chemical ionization source (EI/CI). EI low-resolution mass spectra were acquired by scanning from 50 to 550 at a rate of scan. The source temperature was maintained at 230 C. Helium was used as the nebulizer gas. Data acquisition was performed with Chemstation-pen Action software. Thin layer chromatography (TLC) was carried out on silica gel 60 F254 plates (Merck) using reagent grade solvents. Unless otherwise specified, reagents were obtained from commercial sources and used without further purification. Microwave reactions were performed in a Biotage Initiator. Pd leaching was determined by Inductively Coupled Plasma Emission Spectroscopy in a multitype ICP emission spectrometer Shimadzu's ICPE Calculations of residence time using violet crystal as tracer. Two solution of violet crystal in water and THF (0.2 M) were pumped at 0.2 ml/min (each one) using R2+R4 system. The mixed solution was driven to a column containing the catalyst supported (1 g), giving a residence time of 4min and 56 sec. The estimated residence time based on flow rate was 5 min. General procedure for reactions run in flow (table S2): Two solutions were prepared: one with the aryl halide (1 eq.) in dry THF (with concentration specified in table S2) and one with dimethyl zinc in dry toluene (1.3 eq., dilution of the commercial 2 M toluene solution). These solutions were then pumped using the R2+R4 Vapourtec system. The mixed solution was driven through a preheated glass column containing the supported catalyst (SiliaCat DPP-Pd, 1 g), which was packed manually. The conversion of the starting product was checked at the reactor outlet using GC-MS. To isolate the product, the outlet solution was evaporated in vacuo. The residue was then redissolved in ethyl acetate or diethyl ether and washed with water and brine. The organic layer was separated, dried (MgS 4 ), S2

3 filtered and the solvents evaporated in vacuo to obtain the desired product, which usually did not require further purification. Example experimental procedure for batch reactions in microwave (table S1, entry 23): 4-nitrobromobenzene (101 mg, 0.5 mmol) and Siliacat-DPP-Pd (8 mg) were placed in a 5 ml microwave vial with stirring bar. The vial was flushed with nitrogen and sealed using a crimp cap with a Teflon septum. 0.5 ml of THF and ml of toluene were then added via the septum, followed by slow addition of the 2 M dimethylzinc solution in toluene (0.375 ml, 0.75 mmol). The vessel was then placed in a microwave oven and heated to 60 C for 5 minutes. After this time, the mixture was allowed to cool to RT and a sample was taken for GC-MS analysis. Table S1. Batch reactions using microwave irradiation. Entry Solvent T [ C] Concentration [a] [M] Catalyst (mol%) Time Precipitate? Conv. [b] 1 Toluene Pd Tetrakis (1) 10 s Yes 60% 2 Toluene Pd Tetrakis (1) 30 s Yes 25% 3 Toluene Pd Tetrakis (1) 1 min Yes 60% 4 Toluene Pd Tetrakis (1) 2 min Yes 30% 5 Toluene RT 0.1 Pd Tetrakis (1) 15 min No 2% 6 Toluene RT 0.1 Pd Tetrakis (1) 15 h No 13% 7 Toluene Pd Tetrakis (1) 1 min Yes 8% 8 Toluene Pd Tetrakis (1) 30 s Yes 40% 9 Toluene Pd Tetrakis (1) 2 min Yes 40% 10 Toluene Pd Tetrakis (1) 1 min Yes 77% 11 THF Tetrakis (1) 1 min No 17% 12 THF Tetrakis (1) 5 min Yes 100% 13 1/1 THF/DMF Tetrakis (1) 1 min No 100% 14 1/1 Toluene/THF Tetrakis (1) 1 min Yes 100% 15 1/1 Toluene/THF Polymer-Pd(TPP) 4 1 min No 6% 16 1/1 Toluene/THF Siliacat- Pd 0 1 min No 70% 17 1/1 Toluene/THF Siliacat-S-Pd 0 1 min No 20% 18 1/1 Toluene/THF Siliacat-DPP-Pd 0 1 min Yes 85% 19 1/1 Toluene/THF Siliacat- Pd 0 2 min No 80% 20 1/1 Toluene/THF Siliacat- Pd 0 1 min No 90% 21 1/1 Toluene/THF Siliacat- Pd 0 3 min No 80% 22 1/1 Toluene/THF Siliacat- Pd 0 5 min No 50% 23 1/1 Toluene/THF Siliacat-DPP-Pd 5 min No 60% [a] Concentration of 4-nitrobromobenzene [b] As determined by GC-MS S3

4 Table S2. Explorations of reaction scope (extended). R 1a-p X Me 2 Zn (2a) SiliaCat DPP-Pd THF/ Toluene 1:1 60 ºC, R t = 3min R 3a-n Entry Substrate Product Concentration [a] [M] T [ C] Rt [sec] Conv. [b] Yield [c] N 2-C 6H 4-Br (1a) 2,4,6-triMeC 6H 2-Br (1b) 3a 3b Me-2-Br-pyridine (1c) 3c 0, Me-2-Br-pyridine (1c) 3c Me-C 6H 4-Br (1d) 3d [d] Me-C 6H 4-Br (1d) 3d [e] Me-C 6H 4-Br (1d) 3d [e] Et-C 6H 4-Br (1e) 3e Ac-C 6H 4-Br (1f) 3f CH-C 6H 4-Br (1g) 3g CN-C 6H 4-I (1h) 3h tBu-C 6H 4-I (1i) 3i [d] tBu-C 6H 4-I (1i) 3i [e] Me-C 6H 4-I (1j) 3d [e] Me-C 6H 4-I (1j) 3d [d] Me-C 6H 4-I (1j) 3d [e] C 2Et-C 6H 4-Cl (1k) 3j C 2Et-C 6H 4-Cl (1k) 3j C 2Et-C 6H 4-Cl (1k) 3j Me-2-Cl-pyridine (1l) 3k Me-2-Cl-pyridine (1m) 3l Me-2-Cl-pyridine (1m) 3l Me-2-Cl-pyridine (1n) 3m Me-2-Cl-pyridine (1n) 3m N 2-C 6H 4-Nf (1o) 3a N 2-C 6H 4-Nf (1o) 3a Cl-C 6H 4-Br (1p) 3n [f] 75 [a] Feed concentration of Aryl halogenide. [b] As determined by GC-MS. [c] Isolated yield. [d] >25% homocoupling detected. [e] <10% homocoupling detected. [f] 5% dimethylated product detected S4

5 Table S3. Scope of rganozinc Reagents (extended). Entry Substrate R 1R 2Zn Product Concentration [a] [M] T [ C] Rt [sec] Conv. [b] 1 1a Et 2Zn (2b) 3o a 2-PyridylZnBr (2c) 3p a cyprznbr (2d) 3q e cyprznbr (2d) 3r e 2-PyridylZnBr (2c) 3s e C 6H 5CH 2ZnBr (2e) 3t e NC(CH 2) 4ZnBr (2f) 3u d 8 1e (CH 2) 2CH(CH 2) 2ZnBr (2g) 3v e 9 1e Et 2C(CH 2) 2ZnBr (2h) 3w e 10 1g (CH 2) 2CH(CH 2) 2ZnBr (2b) 3x q Et 2C(CH 2) 2ZnBr (2c) 3y [a] Feed concentration of Aryl halogenide. [b] As determined by GC-MS. [c] Isolated yield. [d] >25% homocoupling detected. [e] <10% homocoupling detected. Yield [c] Scale up runs The same procedure as for the small scale runs was used (0.25 M feed concentration of aryl bromide, 60 C, Rt = 3 min), except the reaction was run for a longer period. The end products were purified in this case using flash chromatography. 4'-Methylacetophenone (3f) The crude product was purified using flash chromatography (Gradient: Heptane 8/2 Heptane/EtAc). The pure product was obtained as a colorless oil (83% yield). 4-Methylbenzaldehyde (3g) The crude product was purified using flash chromatography (Gradient: Heptane 8/2 Heptane/EtAc). The pure product was obtained as a colorless oil (84% yield). S5

6 GC-MS of selected crudes. 1,2,3,5-Tetramethylbenzene (3b) 3-Methoxy-2-methylpyridine (3c) 4-Methylanisole (3d) S6

7 2-Methylbenzonitrile (3h) Ethyl 4-methylbenzoate (3j) Measurement of Pd leaching. The sample (between 50 and 120 mg) was dissolved in 10ml of HN 3 (0.1%) and was stirred for 15 minutes at 100 ºC. Then, it is filtered (0.45 microns, NYL) and is performed a dilution 1:10 (sample: HN 3 0.1%). Finally, it was taken to the ICP emission spectrometer and determined its content in palladium. Analytical data. 4-Methylnitrobenzene (3a). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.47 (s, 3H), 7.32 (d, J = 8.8 Hz, 2H), 8.12 (d, J = 8.8 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 21.6, 123.5, 129.8, m/z C 7 H 7 N 2 calc Found (EI): ,2,3,5-Tetramethylbenzene (3b). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.26 (s, 3H), 3.37 (s, 6H), 2.40 (s, 3H), 6.96 (s, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 14.7, 20.4, 21.2, 128.2, 131.9, 134.7, m/z C 10 H 14 calc Found (EI): S7

8 3-Methoxy-2-methylpyridine (3c). Colorless oil. 1 H-NMR (DMS, 400 MHz, δ ppm): 2.35 (s, 3H), 3.80 (s, 3H), 7.19 (dd, J = 8.3, 4.6 Hz, 1H), 7.31(dd, J = 8.3, 1.2 Hz, 1H), 7.99 (dd, J = 4.6, 1.2 Hz, 1H). 13 C-NMR (DMS, 100 MHz, δ ppm): 19.2, 55.3, 116.9, 122.1, 139.8, 147.4, m/z C 7 H 9 N calc Found (EI): Methylanisole (3d). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.44 (s, 3H), 3.86 (s, 3H), 6.97 (d, J = 8.8 Hz, 2H), 7.49 (d, J = 8.8 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 30.3, 55.3, 114.1, 127.7, 133.5, m/z C 8 H 10 calc Found (EI): Ethyl-4-methylbenzene (3e). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.21 (t, J = 7.4 Hz, 3H), 2.31 (s, 3H), 2.60 (q, J = 7.6 Hz, 2H), 7.09 (s, 4H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 15.7, 20.9, 28.4, 127.7, 128.9, 134.9, m/z C 9 H 12 calc Found (EI): Methylacetophenone (3f). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.41 (s, 3H), 2.57 (s, 3H), 7.25 (d, J = 8.1 Hz, 2H), 7.86 (d, J = 8.3 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm):. m/z C 9 H 10 calc Found (EI): p-tolualdehyde (3g). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.46 (s, 3H), 7.35 (d, J = 8.1 Hz, 2H), 7.80 (d, J = 8.3 Hz, 2H), 9.97 (s, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 22.0, 129.7, 130.0, , 145.7, m/z C 8 H 8 calc Found (EI): Methylbenzonitrile (3h). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.57 (s, 3H), (m,2h), 7.52 (t, J = 7.6 Hz, 1H), 7.63 (d, J = 7.6 Hz, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 20.5, 118.1, 126.2, 130.3, 132.6, 132.8, m/z C 8 H 7 N calc Found (EI): tert-Butyl-4-methylbenzene (3i). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.36 (s, 9H), 1.43 (s, 3H), 7.45 (dt, J = 8.5, 2.1 Hz, 2H), 7.53 (dt, J = 8.5, 2.1 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 14.1, 31.8, 34.5, 125.6, 126.6, 138.2, m/z C 11 H 16 calc Found (EI): Ethyl 4-methylbenzoate (3j). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.39 (t, J = 7.2 Hz, 3H), 2.40 (s, 3H), 4.36 (q, J = 7.2 Hz, 2H), 7.23 (d, J = 7.9 Hz, 2H), 7.97 (t, J = 8.1 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 14.2, 21.5, 60.6, 127.7, 128.9, 129.4, 143.3, m/z C 10 H 12 2 calc Found (EI): S8

9 2-Methoxy-6-methylpyridine (3k). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.44 (s, 3H), 3.9 (s, 3 H), 6.52 (d, J = 8.3 Hz, 1H), 6.7 (d, J = 7.2 Hz, 1H), 7.44 (dd, J = 8.3, 7.2 Hz, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 24.1, 53.1, 107.0, 115.6, 138.6, 156.2, m/z C 7 H 9 N calc Found (EI): Methoxy-2-methylpyridine (3l). Colorless oil. 1 H-NMR (DMS, 400 MHz, δ ppm): 2.35 (s, 3H), 3.80 (s, 3H), 7.19 (dd, J = 8.3, 4.6 Hz, 1H), 7.31(dd, J = 8.3, 1.2 Hz, 1H), 7.99 (dd, J = 4.6, 1.2 Hz, 1H). 13 C-NMR (DMS, 100 MHz, δ ppm): 19.2, 55.3, 116.9, 122.1, 139.8, 147.4, m/z C 7 H 9 N calc Found (EI): ,6-Dimethylpyridine (3m). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.50 (s, 6H), 7.92 (d, J = 7.6 Hz, 2H), 7.43 (t, J = 7.6 Hz, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm):24.4, 120.0, 136.4, m/z C 7 H 9 N calc Found (EI): Chloro-4-methylbenzene (3n). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 2.32 (s, 3H), 7.06 (d, J = 8.1 Hz, 2H), 7.38 (d, J = 8.3 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 20.9, 119.0, 130.8, 131.2, m/z C 7 H 7 Cl calc Found (EI): Ethyl-4-nitrobenzene (3o). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.29 (t, J = 7.6 Hz, 3H), 2.77 (q, J = 7.6 Hz, 2H), 7.35 (d, J = 8.8 Hz, 2H), 8.15 (d, J = 8.8 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 15.0, 30.3, 123.6, 128.6, 135.7, m/z C 8 H 9 N 2 calc Found (EI): (4-Nitrophenyl)pyridine (3p). White solid. m.p.: ºC (lit: ºC) 1 1 H-NMR (CDCl 3, 400 MHz, δ ppm): (m, 1H), (m, 2H), 8.19 (dt, J = 9, 2.1 Hz, 2H), 8.35 (dt, J = 9, 2.1 Hz, 2H), (m, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 121.2, 123.5, 124.0, 127.7, 137.1, 145.2, 150.1, m/z C 11 H 8 N 2 2 calc Found (EI): Cyclopropyl-4-nitrobenzene (3q). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): (m, 4H), (m, 1H), 7.17 (d, J = 8.6 Hz, 2H), 7.70 (d, J = 8.9 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 11.0, 15.8, 123.6, 125.9, 129.9, m/z C 9 H 9 N 2 calc Found (EI): S9

10 1-Cyclopropyl-4-ethylbenzene (3r). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): (m, 2H), (m, 2H), 1.25 (t, J = 7.6 Hz, 3H), (m, 1H), 2.63 (q, J = 7.6 Hz, 2H), 7.03 (d, J = 8.1 Hz, 2H), 7.12 (d, J = 8.3 Hz, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 8.9, 14.9, 15.7, 28.4, 125.6, 127.7, 141.1, m/z C 11 H 14 calc Found (EI): (4-Ethylphenyl)pyridine (3s). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm):1.22 (t, J = 7.7 Hz, 3H), 2.67 (q, J = 7.6 Hz, 2H), (m, 1H), (m, 4H), 8.12 (d, J = 9 Hz, 2H), 8.6 (d, J = 9 Hz, 1H), (m, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 15.8, 28.1, 121.4, 121.8, 127.4, 128.1, 135.9, 136.7, 143.1, 149.6, m/z C 13 H 13 N calc Found (EI): Ethyl-4-(phenylmethyl)benzene (3t). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.21 (t, J = 7.5 Hz, 3H), 2.61 (q, J = 7.5 Hz, 2H), 3.94 (s, 2H), (m, 4H), (m, 3H), (m, 2H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 16.1, 28.9, 42.0, 126.3, 126.4, 128.4, 128.7, 128.8, 128.9, 129.0, 129.3, m/z C 15 H 16 calc Found (EI): (4-Ethylphenyl)-pentanenitrile (3u). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.22 (t, J = 7.6 Hz, 3H), (m, 2H), (m, 2H), 2.34 (t, J = 6.9 Hz, 2H), (m, 4H), (m, 4H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 16.1, 17.5, 25.3, 28.9, 30.8, 35.0, 120.1, 128.3, 128.7, 138.8, m/z C 13 H 17 N calc Found (EI): [2-(4-Ethylphenyl)-ethyl]-1,3-dioxolane (3v). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.22 (t, J = 7.6 Hz, 3H), (m, 2H), 2.61 (q, J = 7.6 Hz, 2H), 2.72 (dt, J = 8.1, 2.0 Hz, 2H), 4.89 (t, J = 4.6 Hz, 1H), (m, 4H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 16.1, 28.9, 30.2, 36.0, 65.4, 104.3, 128.3, 128.7, 139.2, m/z C 15 H 16 calc Found (EI): Ethyl-3-(4-ethylphenyl)propanoate (3w). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): (m, 6H), (m, 4H), 2.92 (t, J = 7.9 Hz, 2H), 4.13 (q, J = 7.1 Hz, 2H), (m, 4H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 14.6, 16.1, 28.9, 31.0, 36.5, 60.8, 128.4, 128.7, 138.2, 142.6, m/z C 13 H calc Found (EI): [2-(1,3-Dioxolan-2-yl)ethyl]benzaldehyde (3x). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): (m, 2H), 2.84 (dt, J = 8.1, 2.2 Hz, 2H), (m, 2H), (m, 2H), S10

11 4.91 (t, J = 4.6 Hz, 1H), 7.38 (d, J = 7.8 Hz, 2H), 7.81 (d, J = 8.0 Hz, 2H), 9.97 (s, 1H). 13 C- NMR (CDCl 3, 100 MHz, δ ppm): 30.7, 35.4, 65.4, 103.9, 128.4, 129.5, 130.4, 130.8, 135.0, 149.6, 192,4. m/z C 12 H calc Found (EI): Ethyl-3-(2-nitrophenyl)propanoate (3y). Yellow oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): 1.23 (t, J = 7.1 Hz, 3H), 2.72 (t, J = 7.5 Hz, 2H), 3.23 (t, J = 7.5 Hz, 2H), 4.13 (q, J = 7.2 Hz, 2H), (m, 2H), (m, 1H), (m, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 14.6, 16.1, 28.8, 35.3, 65.1, 125.3, 128.0, 132.6, 133.6, 136.1, 149.8, m/z C 13 H calc Found (EI): ,4-Dihydroquinolin-2-(1H)-one (4). Colorless oil. 1 H-NMR (CDCl 3, 400 MHz, δ ppm): (m, 2H), 2.97 (t, J = 7.5 Hz, 2H), (m, 1H), (m, 1H), (m, 2H), 90.2 (br. s, 1H). 13 C-NMR (CDCl 3, 100 MHz, δ ppm): 25.7, 31.1, 116.0, 123.5, 124.0, 127.9, 128.3, 137.7, 172,6. m/z C 9 H 9 N. calc Found (EI): A. R. Katritzky, A. Chermprapai, R. C. Patel, A. Tarraga-Tomas; J. rg. Chem., 1982, 3, S11

12 NMR spectra. - N N S12

13 H 3 C CH H 3 C CH S13

14 CH3 N CH3 N S14

15 H 3 C H 3 C S15

16 S16

17 H 3 C H 3 C S17

18 H H S18

19 N N S19

20 H 3 C H 3 C H 3 C H 3 C S20

21 H 3 C H 3 C S21

22 H 3 C N H 3 C N S22

23 CH3 N CH3 N S23

24 H 3 C N H 3 C N S24

25 Cl Cl S25

26 - N N S26

27 - N + N N + N S27

28 - N N S28

29 H 3 C H 3 C S29

30 N H 3 C H 3 C N S30

31 NALNS2_108_1.ESP NALNS2_108_1.ESP S31

32 NALNS2_106_1.ESP N NALNS2_106_1.ESP N S32

33 NALNS2_112_1.ESP NALNS2_112_1.ESP S33

34 NALNS2_114_1.ESP NALNS2_114_1.ESP S34

35 NALNS2_117_1.ESP NALNS2_117_1.ESP S35

36 NALNS2_116_1.ESP - N NALNS2_116_1.ESP - N S36

37 NALNS2_119_1.ESP N NALNS2_119_1.ESP N S37