Supporting information. for. The Solvent-free Michaelis-Arbuzov Rearrangement under Flow Conditions

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1 Supporting information The Solvent-free Michaelis-Arbuzov Rearrangement under Flow Conditions for Aleksandra Jasiak, * a Grażyna Mielniczak, a Krzysztof wsianik, a Marek Koprowski, a Dorota Krasowska a and Józef Drabowicz *a, b Adress: a Centre of Molecular and Macromolecular Studies, Division of rganic Chemistry, olish Academy of Sciences, Sienkiewicza 112, Łódź, oland. ajasiak@cbmm.lodz.pl; Fax: ; Tel: , b Institute of Chemistry, Health and Food Sciences, The Faculty of Mathematics and Natural Sciences, Jan Długosz University in Częstochowa, Armii Krajowej 13/15, Częstochowa , oland. draj@cbmm.lodz.pl; Fax: ; Tel.: Table of contents Technical specification of used microreactor (Tab. S1) S2 1 H, 31, 13 C NMR spectra of the obtained compounds (Fig. S1-S31) S2 ptimization of the solvent-free Arbuzov rearrangement between (1a) and (2a) (Tab. S2) S18 Conversion of (1a) against temperature under flow conditions (Fig. 32) S18 ptimization of the solvent-free Arbuzov rearrangement between (1d) and (2b) (Tab. S3) S18 Details of the conversion of (1d) against temperature under flow conditions (Fig. S33) S19 Details of the competitive reaction of phosphite (1b) with different excess of (2d) (Fig. S34) S19 S1

2 Table S1. Technical specification of used microreactor. Asia 120 Microreactor Wetter materials glass, quartz Temperature range -20 C to +250 C [a] Maximum pressure 30 bar Inside diameter of connection 0.5 mm tubing Connection tubing material TFE, FE Type of mixer Double T-mixer [a] up to 150 C. Me Me Me Figure S1: 1 H NMR (200 MHz, CDCl 3 ) of 3a. S2

3 Me Me Me Figure S2: 31 NMR (81 MHz, CDCl 3 ) of 3a. Me Me Me Figure S3: 13 C NMR (50 MHz, CDCl 3 ) of 3a. S3

4 Et Et Et Figure S4: 1 H NMR (200 MHz, CDCl 3 ) of 3b. Et Et Et Figure S5: 31 NMR (81 MHz, CDCl 3 ) of 3b. S4

5 Et Et Et Figure S6: 13 C NMR (50 MHz, CDCl 3 ) of 3b. Bn Bn Bn Figure S7: 1 H NMR (200 MHz, CDCl 3 ) of 3c. S5

6 Bn Bn Bn Figure S8: 31 NMR (81 MHz, CDCl 3 ) of 3c. Bn Bn Bn Figure S9: 13 C NMR (50 MHz, CDCl 3 ) of 3c. S6

7 Bn Bn Bn Figure S10: 13 C DET 135 NMR (50 MHz, CDCl 3 ) of 3c. Et Et Me Figure 11: 1 H NMR (200 MHz, CDCl 3 ) of 3d. S7

8 Et Et Me Figure S12: 31 NMR (81 MHz, CDCl 3 ) of 3d. Et Et Me Figure S13: 13 C NMR (50 MHz, CDCl 3 ) of 3d. S8

9 i-r i-r Me Figure S14: 1 H NMR (200 MHz, CDCl 3 ) of 3e. i-r i-r Me Figure S15: 31 NMR (81 MHz, CDCl 3 ) of 3e. S9

10 i-r i-r Me Figure S16: 13 C NMR (50 MHz, CDCl 3 ) of 3e. i-r i-r Et Figure S17: 1 H NMR (200 MHz, CDCl 3 ) of 3f. S10

11 i-r i-r Et Figure S18: 31 NMR (81 MHz, CDCl 3 ) of 3f. i-r i-r Et Figure S19: 13 C{ 1 H} NMR (125 MHz, CDCl 3 ) of 3f. S11

12 i-r i-r Et Figure S20: 13 C{ 1 H; 31 } NMR (125 MHz, CDCl 3 ) of 3f. i-r i-r n-r Figure S21: 1 H NMR (200 MHz, CDCl 3 ) of 3g. S12

13 i-r i-r n-r Figure S22: 31 NMR (81 MHz, CDCl 3 ) of 3g. i-r i-r n-r Figure S23: 13 C NMR (50 MHz, CDCl 3 ) of 3g. S13

14 i-r i-r n-bu Figure S24: 1 H NMR (200 MHz, CDCl 3 ) of 3h. i-r i-r n-bu Figure S25: 31 NMR (81 MHz, CDCl 3 ) of 3h. S14

15 i-r i-r n-bu Figure S26: 13 C{ 1 H} NMR (125 MHz, CDCl 3 ) of 3h. i-r i-r n-bu Figure S27: 13 C{ 1 H; 31 } NMR (125 MHz, CDCl 3 ) of 3h. S15

16 Et Et n-r Figure S28: 1 H NMR (200 MHz, CDCl 3 ) of 3i. Et Et n-r Figure S29: 31 NMR (81 MHz, CDCl 3 ) of 3i. S16

17 Et Et n-r Figure S30: 13 C NMR (50 MHz, CDCl 3 ) of 3i. Et Et n-r Figure S31: 13 C DET 135 NMR (50 MHz, CDCl 3 ) of 3i. S17

18 Table S2: ptimization of the solvent-free Arbuzov rearrangement between trimethylphosphite (1a) and methyl iodide (2a). Entry 2a (equiv.) t ( C) RT a (min.) Conversion b (%) a RT - residence time; b31 NMR conversion (%). Figure S32: 31 NMR (81 MHz, CDCl 3 ) details of conversion of trimethylphosphite (1a) against temperature under flow conditions. Table S3: ptimization of the solvent-free Arbuzov rearrangement between triisopropylphosphite (1d) and ethyl iodide (2b). Entry EtI (equiv.) t ( C) RT a (min.) Conversion b (%) a RT - residence time; b31 NMR conversion (%). S18

19 Figure S33: 31 NMR (81 MHz, CDCl 3 ) details of the conversion of triisopropylphosphite (1d) against temperature under flow conditions. Figure S34: 31 NMR (81 MHz, CDCl 3 ) details of the competitive reaction of phosphite (1b) with different excess of n-propyl iodide (2d). S19