Recyclable Heterogeneous Copper xide on Alumina Catalyzed Coupling of Phenols and Alcohols with Aryl halides under Ligand Free Conditions Kokkirala Swapna, a Sabbavarapu Narayana Murthy, a Mocharla Tarani Jyothi a and Yadavalli Venkata Durga Nageswar* a a rganic Chemistry Division-I, Indian Institute of Chemical Technology, Hyderabad 500607, India. Tel: +91-40-27191654, Fax: +91-40-27160512. E-mail: dryvdnageswar@gmail.com 1
Contents Representative Experimental Procedure for the Synthesis of Diaryl Ethers by Using Heterogeneous Cu on alumina as a Catalyst...3 Copies of 1 H NMR and 13 C NMR of Compounds...4 2
Representative Experimental Procedure for the Synthesis of Diaryl Ether by Using Cu on alumina as a Catalyst: To a stirred solution of iodo benzene (1a) (1.0 mmol) and phenol (2a) (1.0 mmol) in dry DMS (2.0 ml) were added Cu on alumina catalyst (13%, 120 mg) and KH (2.0 equiv) and the reaction mixture was heated at 100 0 C under nitrogen atmosphere for 18 h, The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was extracted with ethyl acetate (3x10 ml). The combined organic layers were dried with anhydrous Na 2 S 4. The solvent was evaporated under vacuum to give the crude product, which was purified by column chromatography with hexane as eluent to yield the expected product 3a (166 mg, 98%) as yellowish oil. The purity of the product was confirmed by 1 H, 13 C and Mass, IR spectroscopy. 3
Copies of 1 H NMR and 13 C NMR of Compounds 4
(entry 1, Table 2) 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 5
(entry 1, Table 2) 200 175 150 125 100 75 50 25 0 6
Me (entry 2, Table 2) 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 7
8
Me (entry 3, Table 2) 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 9
Me (entry 3, Table 2) 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 10
Me (entry 4, Table 2) 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 11
12
Me Me Me (entry 5, Table 2) 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 13
14
Me Me (entry 6, Table 2) 16 14 12 10 8 6 4 2 0-2 15
16
F (entry 7, Table 2) 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0-1 17
18
Cl (entry 8, Table 2) 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0-0.5 19
Cl (entry 8, Table 2) 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 20
F 3 C (entry 9, Table 2) 10 9 8 7 6 5 4 3 2 1 0 21
Me Me (entry 10, Table 2) 16 14 12 10 8 6 4 2 0-2 22
23
(entry 11, Table 2) 10 9 8 7 6 5 4 3 2 1 0 24
25
(entry 12, Table 2) 16 14 12 10 8 6 4 2 0-2 26
(entry 12, Table 2) 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0-10 27
(entry 13, Table 2) 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0-0.5 28
(entry 13, Table 2) 200 175 150 125 100 75 50 25 0 29
(entry 14, Table 2) 16 14 12 10 8 6 4 2 0-2 30
31
N (entry 15, Table 2) 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0-0.5 32
33
C6 H 13 (entry 16, Table 2) 14 13 12 11 10 9 8 7 6 5 4 3 2 1 0-1 34
C6 H 13 (entry 16, Table 2) 200 175 150 125 100 75 50 25 0 35
C7 H 15 (entry 17, Table 2) 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 36
C7 H 15 (entry 17, Table 2) 200 175 150 125 100 75 50 25 0 37
C8 H 17 (entry 18, Table 2) 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 38
C8 H 17 (entry 18, Table 2) 200 175 150 125 100 75 50 25 0 39
C10 H 21 (entry 19, Table 2) 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 40
C10 H 21 (entry 19, Table 2) 200 175 150 125 100 75 50 25 0 41
C12 H 25 (entry 20, Table 2) 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 42
C12 H 25 (entry 20, Table 2) 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0-10 43
C16 H 33 (entry 21, Table 2) 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 44
C16 H 33 (entry 21, Table 2) 200 175 150 125 100 75 50 25 0 45
Br (entry 8, Table 3) 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 46
Br (entry 8, Table 3) 200 175 150 125 100 75 50 25 0 47