**1,3-Dihydroxy-5-heptylbenzene (12)**

Compound **12** was prepared as described for **10** using compound **8** (0.98 g, 4.15 mmol) and BBr3 (1 M solution in CH2Cl2, 9.5 mL, 9.5 mmol) to give compound **<sup>12</sup>** in 91% yield [30]. 1H NMR (500 MHz, CDCl3): <sup>δ</sup> 6.27 (d, 2H, aromatic, J = 2.0 Hz), 6.20 (d, 1H, aromatic, J = 2.0 Hz), 2.51 (t, 2H, CH, *J* = 7.5 Hz), 1.59 (q, 2H, CH2, J = 7.5 Hz), 1.39–1.22 (m, 14H, CH2), and 0.91 (t, 3H, CH3, J = 6.5 Hz).

#### **1,3-Dihydroxy-5-nonylbenzene (13)**

Compound **13** was prepared as described for **10** using compound **9** (0.76 g, 2.88 mmol), and BBr3 (1 M solution in CH2Cl2, 5.8 mL, 5.8 mmol) to give compound **<sup>13</sup>** in 84% yield [31]. 1H NMR (500 MHz, CDCl3): <sup>δ</sup> 6.27 (d, 2H, aromatic, J = 2.0 Hz), 6.20 (bs, 1H, aromatic), 4.72 (bs, OH), 2.51 (t, 2H, CH2, *J* = 7.5 Hz), 1.61–1.58 (m, 2H, CH2), 1.33–1.28 (m, 12H, CH2), and 0.91 (t, 3H, CH3, J = 7.0 Hz).

Syntheses of the CBG analogs of varying side chain lengths were conducted as described below and illustrated in Scheme 2.

**Scheme 2.** Synthesis of CBG analogs, **14**–**17**.

#### **Cannabigerovarin (CBGV, 14):**

To a stirred cold solution of geraniol (203 mg,1.32 mmol) in anhydrous chloroform (20 mL) was added (over a period of 20 min) a solution of 1,3-dihydroxy-5-ethylbenzene (**10**) (131 mg, 0.73 mmol) and p-toluenesulfonic acid (14 mg) in anhydrous chloroform (15 mL) at 0 ◦C and under a positive pressure of nitrogen. After stirring in the same conditions for 14 h, the reaction was quenched with saturated of NaHCO3 (5 mL). The reaction mixture was extracted with EtOAc (3 × 15 mL) and the combined organic layers were washed with water, dried (MgSO4) and evaporated. The residue was purified on silica gel column by eluting with hexane:CH2Cl2 (1:1) to give 21% yield of CBGV (**14**) [32]. 1H NMR (500 MHz, CDCl3): δ 6.26 (s, 2H, aromatic), 5.33–5.28 (m, 1H, CH), 5.14 (bs, 2H, OH), 5.08 (t, 1H, CH, J = 7.0 Hz), 3.42 (d, 2H, Ph-CH2, J = 7.0 Hz), 2.56 (t, 2H, Ph-CH2, J = 7.5 Hz), 2.18–2.0 (m, 6H), 1.84 (s, 3H, CH3), 1.70 (S, 3H, CH3), 1.63 (s, 3H, CH3), 0.95 (t, 3H, CH3, J = 7.5 Hz); HRMS calculated for C19H28O2 + H: 289.2169; the observed value was 289.2091.
