H. Zhao et al.
Preparation and analysis of (I)
[2H7]benzyl bromide (17.68 g, 100 mmol), NaCN (7.35 g,
150 mmol), and tetrabutylammonium bromide (0.4 g) in water
(30 mL) was then heated under reflux at 1201C for 8 h, 2-
[2H7]phenylacetonitrile (10.1 g, 80.1%) was collected from the
dark solution by steam distillation. 5-[2H7]benzyl-1H-tetrazole
(III) was obtained following the method described for II.
The crystals that formed were collected by filtration and
recrystallized from 95% ethanol in 91.3% yield. m.p.:
256–2581C. Anal. calcd. for C8HD7N4: [%] C, 57.46; H, 9.03; N,
33.51; Found: [%] C, 57.12; H, 9.24; N, 33.64; IR (KBr, cmꢀ1):
2950.3(br, m), 2861.4(m), 2775.9(m), 2701.7(m), 2596.5(m),
2271.8(m), 1801.2(br, w), 1530.0(s), 1427.6(s), 1380.7(m),
1365.5(w), 1340.8(w), 1251.8(s), 1241.3(s), 1167.6(w), 1109.0(m),
1075.6(s), 1057.6(s), 1039.1(w), 999.8(s), 900.9 (s), 820.9(m),
577.1(m), 538.0(s), 423.2(s); dC (300 MHz; CDCl3) 28.87 (Ar-CD2),
134.9 (C-3), 128.2 (C-4 and C-8), 127.9 (C-5 and C-7), 126.6 (C-6),
155.8 (C-1); m/z (-ve ion electrospray ) [M-H]ꢀ C8D7N4 required
166.23, found 166.29.
To [2H8]toluene (2.5 g, 25 mmol) in 3.5 M HNO3 (50 mL) was
added Ce(NH4)2(NO3)2 (54.8 g 100 mmol) in 3.5 M HNO3
(200 mL). After 2.5 h at 80 1C, the solution was cooled to room
temperature, extracted with chloroform (3 ꢁ 50 mL), and the
combined organic layers were washed with water until pHE7.
The orange extract was dried (MgSO4) and the solvent
removed under vacuum. The resulting red residue was distilled
to give [2H6]benzaldehyde (2.6 g, 91%). Iodine (12.57 g,
49.5 mmol) was added to a stirring solution of [2H6]benzalde-
hyde (4.56 g, 40 mmol) in aqueous ammonia (350 mL of a 28%
solution) and tetrahydrofuran (45 mL) at room temperature.
The dark solution became colorless after being stirred for 1 h,
an indication that the reaction was complete. The reaction
mixture was quenched with aqueous Na2S2O3 (50 mL of 20%
solution) and then extracted with chloroform (3 ꢁ 50 mL). The
combined organic layers were washed with water, dried
(MgSO4), and the solvent removed under vacuum to give
[2H5]benzonitrile (4.01 g, 90%), which was used without
purification. A mixture of [2H5]benzonitrile (2.16 g, 20 mmol),
NaN3 (1.43 g, 22 mmol), and NH4Cl (1.177 g, 22 mmol) in DMF
(15 mL) was heated at 1201C for 20 h then cooled and the
solvent removed under vacuum. The residue was poured into
water (20 mL) to give the crude product. 5-[2H5]Phenyl-1H-
tetrazole (I) was obtained (2.85 g, 94.7%) after recrystallization
from ethanol (95%). m.p.: 222–2251C. Anal. calcd. for C7HD5N4:
[%] C, 55.61; H, 7.33; N, 37.06; Found: [%] C, 55.42; H, 7.93; N,
36.65; IR (KBr, cmꢀ1): 3447.5(br, w), 3016.4(m), 2918.5(w),
2707.8(m), 2617.8(m), 2483.1(w), 1870.8(br, w), 1584.4(s),
1550.0(s), 1401.9(m), 1330.4(s), 1138.9(s), 1105.2(s), 1083.9(m),
1052..6(s), 984.7(s), 773.8(w), 543.6(s), 445.4(s); dC (300 MHz;
CDCl3) 123.7 (C-5), 126.4 (C-3 and C-7), 128.6(C-4 and C-6),
130.7 (C-2), 155.9 (Ar-C-1); m/z (-ve ion electrospray) [M-H]ꢀ
C7D5N4 required 150.09, found 150.22.
X-ray crystallography
Data collection: CrystalClear (Rigaku, 2005); cell refinement:
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku,
2005); program(s) used to solve structure: SHELXS97 (Sheldrick,
1997); program(s) used to refine structure: SHELXL97 (Sheldrick,
1997); molecular graphics: Bruker SHELXTL (Sheldrick, 1999);
Software used to prepare material for publication: Bruker
SHELXTL (Sheldrick, 1999).
Crystal data for 1
Mr = 151.19; orthorhombic; Ama2; a = 9.81(2), b = 15.26(4),
3
c = 4.544(10)A; V = 680(3)A ; Z = 4; Dcalcd = 1.476 Mg.mꢀ3
;
˚
˚
R1 = 0.0552; wR2 = 0.1281; T = 293 K; m = 0.096 mmꢀ1; S = 1.127.
Preparation and analysis of (II)
Crystal data for 2
To 1,4-[2H10] xylene (2.34 g, 20 mmol) in 3.5 M HNO3 (50 mL) was
added dropwise Ce(NH4)2(NO3)2 (44.23 g, 80 mmol) in 3.5 M
HNO3 (100 mL). After 1.5 h at 801C, workup and purification as
described for [2H6]benzaldehyde gave 4-[2H5]methylbenzalde-
hyde, which was treated by the same procedure as [2H6]ben-
zaldehyde to yield 4-[2H7]methylbenzonitrile. The nitrile was
then reacted with NaN3 and NH4Cl in DMF to give 5-[2H7]tolyl-
1H-tetrazole (II) (2.1 g, 64.2% based on [2H5]1,4-xylene). m.p.:
109–1121C. Anal. calcd. for C8HD7N4: [%] C, 57.46; H, 9.03; N,
33.51; Found: [%] C, 57.20; H, 9.33; N, 33.47; IR (KBr, cmꢀ1):
3447.4(br, w), 3023.4(w), 2933.4(w), 2830(w), 2739.2(m),
2592.2(m), 2512.7(m), 1889.5(br, w), 1591.1(s), 1563.3(m),
1405.6(s), 1363.9(s), 1255.6(w), 1189.8(w), 1136.5(s), 1084.2(m),
1056.1(s), 983.9(s), 655.6(s), 442.1(s); dC (300 MHz; CDCl3)
19.16(Ar-CD3), 120.7 (C-2), 126.3 (C-3 and C-7), 129.3(C-4 and
C-6), 141.8 (C-5), 155.5 (Ar-C-1); m/z (-ve ion electrospray ) [M-
H]ꢀ C8D7N4 required 166.23, found 166.22.
Mr = 167.23; orthorhombic; Pbcm; a = 4.5376(9), b = 17.715(4),
3
c = 9.771(2)A; V = 785.4(3)A ; Z = 4; Dcalcd = 1.414 Mg.mꢀ3
;
˚
˚
R1 = 0.0769; wR2 = 0.1555; T = 293 K; m = 0.089 mmꢀ1; S = 1.096.
Crystal data for 3
Mr = 167.23; monoclinic; P21/c; a= 8.620(13), b= 9.906(14),
3
c= 9.500(13)A; b= 91.49(3); V= 811(2)A ; Z=4; Dcalcd =1.370Mg.mꢀ3
;
˚
˚
R1 = 0.0497; wR2 = 0.1223; T= 293 K; m= 0.087 mmꢀ1; S= 0.994.
Acknowledgement
This research was supported by a Start-up Grant of Prof. Xiong
Ren-Gen from Southeast University.
Preparation and analysis of (III)
REFERENCES
To [2H8]toluene (20 g, 200 mmol) in CCl4 (350 mL) was added
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mixture was heated at 901C for 2 h then cooled and filtered.
The filtrate was concentrated to 40 mL and [2H7]benzyl bromide
(29.4 g, 82.5%) collected by filtration and dried. A mixture of
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Copyright r 2008 John Wiley & Sons, Ltd.