Preparation of N1-alkyl- and N1,N1-dialkylisoquinoline-1,3-diamines and 1-alkyl- and 1-phenylisoquinolin-3-amines from the reaction of α-cyano- o-tolunitrile with lithium amides, alkyllithiums, and phenyllithium

Article abstract of DOI:10.3987/com-99-8752

A facile, one-step synthesis of the titled compounds from the reaction of α-cyano-o-tolunitrile with LiNHR, LiNRR', RLi, or PhLi is described. A mechanism is presented in which α-cyano-o-tolunitrile is first converted quantitatively to its ketenimine carb

Full text of DOI:10.3987/com-99-8752

HETEROCYCLES, Vol. 53, No. 2, 2000, pp. 291 - 300, Received, 10th September, 1999
PREPARATION OF N1-ALKYL- AND N1,N1-DIALKYLISOQUINOLINE-1,3-
DIAMINES AND 1-ALKYL- AND 1-PHENYLISOQUINOLIN-3-AMINES
FROM THE REACTION OF α-CYANO-o-TOLUNITRILE WITH LITHIUM
AMIDES, ALKYLLITHIUMS, AND PHENYLLITHIUM
Anlai Wang, Hongming Zhang, and Edward R. Biehl8
Chemistry Department, Southern Methodist University, Dallas TX 75275
USA, Email: ebiehl@post.smu.edu
Abstract – A facile, one-step synthesis of the titled compounds from the
reaction of α-cyano-o-tolunitrile with LiNHR, LiNRR’, RLi, or PhLi is
described. A mechanism is presented in which α-cyano-o-tolunitrile is first
converted quantitatively to its ketenimine carbanion by the lithium base.
The remaining aromatic cyano group on the ketenimine carbanion then
undergoes nucleophilic attack by the lithium base to give an adduct that
subsequently cyclizes to the titled compounds. The reaction of lithiated
anilines, nitriles, methanol, and pryrrole failed, presumably due to their
inability to deprotonate α-cyano-o-tolunitrile.
Isoquinolines constitute an important class of compounds, many of which have significant
pharmacological properties.1 Accordingly, several synthetic methdologies involving classical
cyclization reactions or functionalization of a preformed isoquinoline backbone have been
reported.2 However, the application of such methods to the preparation of isoquinoline-1,3-
diamines and 1-alkyl- or 1-arylisoquinoline-3-amines is limited. One of the few reported syn-
thesis of isoquinoline-1,3-diamine involved treating the dinitrile, α-cyano-o-tolunitrile, with
ammonia at 140 oC for 24 h.3 However, the yield of the 1,3-diamine was only 47%. Treatment of
the dinitrile with sodium amide in formamide solvent did not yield isoquinoline-1,3-diamine, but
rather produced a mixture of benzylisoquinoline and azachrysene products.4 Isoquinoline-1,3-
diamine derivatives have also been prepared by the reaction of 2-methyl-4,5-dimethoxybenzo-

nitrile with LDA, followed by treatment with N,N-disubstituted cyanamides5 and by the amination
of 1-halo substituted isoquinoline-3-amines.6 However, the yields of the 1,3-diamines in the
former are very low (18-20%) and in the latter several steps are needed to prepare the requisite
haloisoquinolines from readily available starting materials.
The synthesis of 1-substituted isoquinoline-3-amines has been more actively studied, however,
the reported synthetic methods also have severe limitations. For example, Liepa7 has prepared
several 1-alkyl derivatives of N3,N3-dialkylisoquinolin-3-amines by the reaction of nitriles with
arylacetic acid tertiary amides in the presence of phosphoryl chloride. However, attempts to
prepare 1-alkyl substituted N3-alkylisoquinolin-3-amines and isoquinolin-3-amine using arylacetic
acid secondary and primary amides failed. 1-Alkylisoquinolin-3-amines have been synthesized by
the selective reduction and decarboxylation of 3-chloroisoquinoline-4-carboxylic acids.8 However,
the preparation of the requisite 4-carboxylic acids involved a four step reaction sequence, i.e.
condensation of a benzaldehyde with arylacetonitrile to give a 3(2H)-isoquinolone,9 conversion of
the isoquinolone by successive Vilsmeier-Haack10 acylation and potassium permanganate
oxidation under acidic conditions11 into an α-chlorovinylaldehyde , and oxidation of the aldehyde
with potassium permanganate under neutral conditions.8
We report herein a facile one-step synthesis of a number of different N1-substituted (3a-e), and
N1, N1-disubstituted isoquinoline-1,3-diamines (3f-j) as well as 1-substituted isoquinolin-3-amines
(3k-o). These amines were prepared by the reaction of α-cyano-o-tolunitrile (1) with the appro-
priate lithium amide (2a-j), alkyllithium (2k-n) or phenyllithium (2o) at ambient temperatures for 4
h. The individual yields are listed in Table 1. Noteworthy are the good yields of the sterically
demanding 1-tert-butyl (72 %) and 1-sec-butyl (85 %) derivatives (3n and 3m), respectively.
We also found that 1,2-ethanediamine and 1,4-butanediamine react with 1 in the presence of
excess n-BuLi to give bis-N1-(3-aminoisoquinolin-1-yl)-1,2-ethanediamine (4) and bis-N1-(3-
aminoisoquinolin-1-yl)-1,4-butanediamine (5) in high yields (eq. 1).
H2N
NH2
N
N
CN
NH-(CH ) -NH
n-BuLi
2 x
NH2(CH2)xNH2
+
eq. 1
CN
4 x = 2 (87%)
5 x = 4 (90%)

Table 1
1.GLi
NH
2
CN
2
N
CN
2. HOH/H+
G
1
3
Com-
pound
3a
G
Yield (%)
Iso-C3H7NH-
89
91
93
78
67
92
40
84
95
3b
tert-C4H9NH-
n-C4H9NH-
3c
3d
(CH3)2N(CH2)2NH
(CH3)2N(CH2)3NH
(n-C4H9)2N-
3e
3f
3g
(Iso-C3H7)2N-
(C6H5CH2)(CH3)N
pyrrolidinyl
3h
3i
3j
3k
3l
piperidinyl
CH3-
95
78
88
85
72
68
a
n-C4H9-
3m
3n
3o
3p
3q
3r
sec-C4H9-
tert-C4H9-
C6H5-
C6H5NH-
(C6H5)(CH3)N-
NCCH2-
a
a
3s
3t
(CH3)(NCCH2CH2)N
Pyrryl
a
a
3u
CH3O
a
a. not detected.
The proposed structures for 3a-o were consistent with their 1H NMR, 13C NMR and IR spectra.
For example, NMR analysis of 3a-o indicated a characteristic singlet in each spectrum that

ranged from 5.98 to 6.76 ppm (C4-H), consistent with an isoquinoline ring system.7 Moreover, the
C4-H signal for the 1-alkyl (6.58-6.60 ppm) and 1-phenyl (6.76 ppm) derivatives typically occurred
at higher fields than that of the N1-alkyl (5.96-6.60) and N1,N1-dialkyl (6.07-6.48 ppm) derivatives..
The arrangement of the 1,3-amino group was confirmed by single crystal X-Ray diffractometry of
compound (3b) from which an ORTEP drawing is shown in Figure 1.
Figure 1 ORTEP drawing of compound (3b)
The data in Table 1 show, however, that the reaction of lithiated derivatives of anilines (2p,q),
acetonitriles (2r,s), pyrrole (2t), and methanol (2u) with 1 failed, even after stirring overnight or
when they were carried in the presence of TMEDA or 12-crown-4 ether. The use of elevated
temperatures resulted in the formation of inextractable tars.
Scheme 1 depicts a likely mechanism to account for the aforementioned results. As shown, the
dinitrile (1) is initially deprotonated by the lithiated base (2) to give the ketenimine carbanion (6).
The appropriate lithium amide then adds to the free aromatic cyano group to afford the N-lithiated
amidine (G = nitrogen base) or imine (G = alkyl or phenyl) intermediate (7), which undergoes
cyclization to the N,3N3-dilithiated species (8). Upon acidic aqueous quench, 8 is converted to
product (3). In the previously reported reaction of 1 at 80 0C with sodium amide in formamide
solvent,4 the dimerized products were thought to occur by various coupling modes involving 1

and its conjugate base (6). That the strong base, sodium amide, did not completely deprotonate
1 to 6 under these conditions probably reflects the low solubility of sodium amide in formamide.
Scheme 1
C
C
NLi
Li
G-Li
N-Li
2
G-Li
N
1
C
N
-GH
G
7
6
NH
2
NLi
2
H+ / HOH
N
N
G
G
8
3
The use of strong THF-soluble bases (2a-o) and the low temperatures reaction conditions em-
ployed in this study apparently enable the conversion of 1 to 6 to occur completely before the
competing pesky coupling reactions can occur. The failure of the significantly weaker lithiated
bases (2p-u) as compared to the lithium bases (2a-o) to react with 1 under these conditions most
likely reflects their inability to convert the dinitrile (1) to its ketenimine carbanion (6).
In conclusion, a quick one-step synthesis of titled compounds from readily available starting
materials has been developed. Furthermore, the sterically demanding tert-butyl and isobutyl
groups can be added to the 1-position of the isoquinoline ring in good yields.
EXPERIMENTAL
General Data: Melting points were taken on a Mel-Temp capillary apparatus and are uncorrected
with respect to stem correction. IR spectra were recorded on a Nicolet Magna-IRTM 550 FTIR
1
13
spectrophotometer and the H and C NMR spectra were recorded on a 400 MHz Bruker
AVANCE DRX-400 Multi-nuclear NMR spectrometer; chemical shifts were referenced to TMS as
internal standard. Elemental analyses were obtained from E + R Microanalytical Laboratories,
Inc. The amines and α−cyano-o-tolunitrile, which were distilled or recrystallized before use, as

well as phenyllithium and the alkyllithiums (in hexanes), were purchased from Aldrich Chemical
Company. The reactions were carried out under an atmosphere of dry O -free N via balloon in
2
2
glassware that had been heated at 125 oC overnight prior to use.
General Procedure. In a flame-dried flask flushed with nitrogen, the lithium amide was prepared
by adding 6 mL of n-BuLi (15 mmol, 2.5 M in hexane) to a solution of the appropriate amine(15
o
mmol) in THF (30 mL) at 0 C. After stirring for 10 min, α-cyano-o-tolunitrile (0.71 g, 5 mmol) in
THF (15 mL) was added over 5 min. The alkyllithiums (15 mmol) and phenyllithium (1.8 mL of a
o
1.8 M soln) were added directly to the tolunitrile (1.42 g, 10 mmol) in THF (15 mL) at 0 C. The
o
stirring was continued for 10 min at 0 C, allowed to warm to rt then stirred an additional 4 h. The
reaction mixture then was quenched with sat. aq. NH Cl (30 mL), and the THF evaporated under
4
reduced pressure to give a residue that was extracted with methylene chloride (2 X 20 mL). The
combined extracts were washed with brine (2 X 20 mL), dried (Na SO ), and concentrated
2
4
(rotary evaporator). The remaining mixture was subjected to flash column chromatography (silica
gel) using a mixture of hexane/acetone (9:1) as the eluent to give a liquid or solid product. The
mp, elemental analyses and NMR spectral data of isolated compounds are given below.
N-1-Isopropylisoquinoline-1,3-diamine (3a): red oil, yield 83 %. IR (nujol) νmax 3473, 3374,
1
3054, 1707, 1623.5, 1524, 1454, 1181, 793, 740.5 cm-1. H NMR (acetone-d6) δ 1.29 (d, J = 6.8
Hz, 6 H), 4.50 (sept, J = 6.8 Hz, 1 H), 4.87 (s, 2 H), 5.96 (s, 1 H), 6.14 (s, 1 H), 6.95 (m, 1 H),
13
7.28 (m, 2 H), 7.88 (d, J = 8.4 Hz, 1 H). C NMR (acetone-d6) δ 22.4, 42.2, 87.3, 113.0, 120.2,
122.7, 124.6, 129.4, 140.9, 154.7, 155.0. Anal. Calcd for C12H15N3: C, 71.64; H, 7.46; N, 20.90.
Found: C, 71.52; H, 7.36; N. 20.97.
N1-tert-Butylisoquinoline-1,3-diamine (3b): orange solid, mp103.5-104.5 oC (EtOAc), yield 85
%. IR (KBr) νmax 3457, 3405, 3364, 2988, 1627, 1567, 1532, 1455, 1409, 1220, 793, 736 cm-1. 1H
NMR (acetone-d6) δ 1.59 (s, 9 H), 4.91 (s, 2 H), 5.81 (s, 1 H), 5.98 (s, 1 H), 6.97 (m, 1 H), 7.29 (m,
2 H), 7.83 (d, J = 8.0 Hz, 1 H). Anal. Calcd for C13H17N3: C, 72.92; H, 7.91; N, 19.12. Found: C,
72.82; H, 7.86; N. 19.18.
N1-n-Butylisoquinoline-1,3-diamine (3c): yellow crystals, mp 179-180 oC (EtOAc), yield 82 %.
IR (KBr) νmax 3477, 3374, 1683.5, 1622.5, 1178.5 cm-1. 1H NMR (acetone-d6) δ 0.98 (t, J = 7.2 Hz,
3 H), 1.47 (m, 2 H), 1.70 (m, 2 H), 3.61 (m, 2 H), 5.24 (s, 2 H), 6.60 (s, 1 H), 7.18 (t, J = 7.6 Hz, 1
H), 7.44 (s, 1 H), 7.57 (t, J = 7.6 Hz, 1 H), 8.05 (d, J = 7.6 Hz, 2 H). Anal. Calcd for C13H17N3: C,
72.92; H, 7.91; N, 19.12. Found: C, 72.80; H, 7.84; N. 19.23.

N1-(2’-Dimethylaminoethyl)isoquinoline-1,3-diamine (3d): oil, yield 78 %. IR (neat) νmax
3477, 3374, 1683.5, 1622.5, 1178.5 cm-1. 1H NMR (acetone-d6) δ 2.26 (s, 6 H), 2.60 (t, J = 5.6
Hz, 2 H), 3.65 (q, J = 5.6 Hz, 2 H), 4.90 (s, 2 H), 5.98 (s,1 H), 6.45 (s, 1 H), 6.98 (m, 1 H), 7.31
(m, 2 H), 7.79 (d, J = 8.0 Hz, 1 H). Anal. Calcd for C13H18N4: C, 67.80; H, 7.88; N, 24.33.
Found: C, 67.85; H, 7.93; N, 24.37.
N1- (3’-Dimethylaminopropyl)isoquinoline-1,3-diamine (3e): oil, yield 67 %. IR (neat) νmax
3357, 3086, 1685, 1569 cm-1. 1H NMR (acetone-d6) δ 1.83 (m, 2 H), 2.23 (s, 6 H), 2.43 (t, J = 5.6
Hz, 2 H), 3.65 (q, J = 5.6 Hz, 2 H), 4.97 (s, 2 H), 5.96 (s, 1 H), 6.99 (m, 1 H), 7.18 (s, 1 H), 7.29
(m, 2 H), 7.77 (d, J = 8.0 Hz, 1 H). Anal. Calcd for C14H20N4: C, 68.82; H, 8.05; N, 22.93. Found:
C, 68.81; H, 8.13; N, 22.99.
N1,N1-di-n-Butylisoquinoline-1,3-diamine (3f): tan oil, yield 86 %. IR (nujol) νmax 3405, 3061,
1614, 1557, 1264, 740, 704 cm-1. 1H NMR (acetone-d6) δ 0.88 (t, J = 7.2 Hz, 6 H), 1.31 (sext, J
= 7.2 Hz, 4 H), 1.59 (quint, J = 7.2 Hz, 4 H), 3.38 (t, J = 7.2 Hz, 4 H), 5.02 (s, 2 H), 6.28 (s, 1 H),
7.05 (t, J = 8.4 Hz, 1 H), 7.33 (t, J = 8.4 Hz, 1 H), 7.38 (d, J = 8.4, 1 H), 7.90 (d, J = 8.4 Hz, 1 H).
Anal. Calcd for C17H25N3: C, 75.28; H, 9.22; N, 15.50. Found: C, 75.34; H, 9.35; N. 15.58.
N1, N1-Diisopropylisoquinoline-1,3-diamine (3g): red oil, yield 40 %. IR (nujol) νmax 3477,
3374, 1683.5, 1622.5, 1178.5 cm-1. 1H NMR (acetone-d6) δ 1.13 (d, J = 5.6 Hz, 12 H), 3.78 (m, 2
H), 5.05 (s, 2 H), 6.48 (s, 1 H), 7.07 (t, J = 8.4 Hz,1 H), 7.35 (t, J = 8.4 Hz, 1 H), 7.40 (d, J = 8.4
Hz, 1 H), 8.19 (d, J = 8.4 Hz, 1 H). Anal. Calcd for C15H21N3: C, 74.07; H, 8.64; N, 17.28.
Found: C, 74.02: H, 8.62; N, 17.19.
N1-Benzyl-N1-methylisoquinoline-1,3-diamine (3h): yellow solid, mp 117-118 0C (EtOAc),
yield 63 %. IR (KBr) νmax 3442, 3420, 3060, 1618, 1556, 1396. 732 cm-1. 1H NMR (acetone-d6)
δ 2.95 (s, 3 H), 4.57 (s, 2 H), 5.10 (s, 2 H), 6.31 (s, 1 H), 7.01 (t, J = 5.6 Hz, 1 H), 7.33 (t, J = 5.6
Hz, 1 H), 7.36 (m, 3 H), 7.44 (m, 3 H), 7.94 (d, J = 8.4 Hz, 1 H). Anal. Calcd for C17H17N3: C,
77.54; H, 6.51; N, 15.96. Found: C, 77.75; H, 6.60; N, 15.87.
1-(Pyrrolidin-1-yl)isoquinolin-3-amine (3i): brown oil, yield 95 %. IR (nujol) νmax 3477, 3378,
3050, 1683.5, 1619.5, 1560, 1446, 738, 702 cm-1. 1H NMR (acetone-d6) δ 1.90 (m, 6 H), 3.70 (m,
4 H), 4.90 (s, 2 H), 6.07 (s, 1 H), 6.94 (m, 1 H), 7.26 (m, 2 H), 8.02 (d, J = 8.4 Hz, 1 H). Anal.
Calcd for C13H15N3: C, 73.24; H, 7.04; N, 19.72. Found: C, 73.12; H, 7.06; N. 19.78.
1-(Piperidin-1-yl)isoquinolin-3-amine (3j): yellow oil, yield 95 %. IR (nujol) νmax 3467, 3374,
1683.5, 1622.5, 1178.5 cm-1. 1H NMR (acetone-d6) δ 1.62 (m, 2 H), 1.75 (m, 4 H), 3.26 (t, J = 5.6
Hz, 4 H), 5.07, (s, 2 H), 6.30 (s, 1 H), 7.06 (t, J = 8.0 Hz, 1 H), 7.33 (t, J = 8.0 Hz, 1 H), 7.38 (d, J

= 8.0 Hz, 1 H), 7.87 (d, J = 8.0 Hz, 1 H). 13C NMR (acetone-d6), δ 24.9, 26.2, 52.7, 92.8, 115.9,
120.8, 125.1, 125.9, 129.4, 141.7, 154.1, 162.0. Anal. Calcd for C14H17N3: C, 74.01; H, 7.49; N,
18.50. Found: C, 73.86; H, 7.46; N. 18.59.
1-Methylisoquinolin-3-amine (3k): tan crystals, mp 123-125 oC, yield 78 %. IR (KBr) νmax 3387,
3374, 3050,1626, 1565, 1452, 1264.5, 741, 705 cm-1. 1NMR (acetone-d6) δ 2.74 (s, 1 H), 5.20 (s,
2 H), 6.58 (s, 1 H), 7.16 (t, J = 7.6 Hz, 1 H), 7.20 (t, J = 7.6 Hz, I H), 7.49 (d, J = 8.4 Hz, 1 H),
7.93 (d, J = 8.4 Hz, 1 H). Anal. Calcd for C10H10N2: C, 75.95; H, 6.33; N, 17.72. Found: C, 75.69;
H, 6.36; N, 17.84.
1-n-Butylisoquinolin-3-amine (3l): colorless cyrstals, mp 80.5-81.5 OC (EtOAc), yield 88 %. IR
1
(KBr) νmax 3438, 3326, 1625, 1561, 835, 743.cm-1. H NMR (acetone-d6) δ 0.97 (t, J = 7.6 Hz, 3
H), 1.48 (m, 2 H), 1.79 (m, 2 H), 3.14 (t, J = 8.0 Hz, 2 H), 5.19 (s, 2 H), 6.58 (s, 1 H), 7.17 (t, J =
8.4 Hz, 1 H), 7.40 (t, J = 8.4 Hz, 1 H), 7.50 (d, J = 8.4 Hz, 1 H), 7.99 (d, J = 8.4 Hz, 1 H). Anal.
Calcd for C13H16N2: C, 77.96; H, 8.05; N, 13.99. Found: C, 77.97; H, 8.16; N, 13.87.
1-sec-Butylisoquinolin-3-amine (3m): oil, yield 85 %. IR (neat) νmax 3367, 3358, 3067, 1622,
1592, 742 cm-1. 1H NMR (acetone-d6) δ 0.87 (t, J = 7.6 Hz, 3 H), 1.33 (d, J = 6.8 Hz, 3 H), 1.70
(m, 2 H), 3.65 (m, 2 H), 5.24 (s, 2 H), 6.60 (s, 1 H), 7.16 (t, J = 8.4 Hz, 1 H), 7.37 (t, J = 8.4 Hz,
1H), 7.52 (d, J = 8.4 Hz, 1 H), 8.05 (d, J= 8.4 Hz, 1 H). Anal. Calcd for C13H16N2: C, 75.96; H,
8.05; N, 13.99. Found: C, 77.91; H, 8.11; N, 13.92.
1-tert--Butylisoquinolin-3-amine (3n): oil, yield 72 %. IR (nujol) νmax 3476, 3367, 3051, 1624,
1557, 1201, 1149, 991, 864, 827, 748, 694 cm-1. 1H NMR (acetone-d6) δ 1.58 (s, 9 H), 5.17 (s, 2
H), 6.60 (s, 1 H), 7.16 (t, J = 8.4 Hz, 1 H), 7.37 (t, J = 8.4 Hz, I H), 7.52 (d, J = 8.4Hz, 1 H), 8.34
(d, J = 8.4 Hz, 1 H). Anal. Calcd for C13H16N2: C, 77.96; H, 8.05; N, 13.99. Found: C, 77.94; H,
8.06; N, 13.90.
1-Phenylisoquinolin-3-amine (3o): oil, yield 68 %. IR (nujol) νma 3465, 3315, 3045, 1624, 1560,
1452, 1363, 1297, 1238, 1184, 1151, 777, 745 cm-1. 1H NMR (acetone-d6) δ 5.43 (s, 2 H), 6.76
(s, 1 H), 7.11 (t, J = 8.4 Hz, 1 H), 7.49-7.56 (m, 7 H), 7.85 (d, J = 8.4 Hz, 1 H), Anal. Calcd for
C15H12N2: C, 81.79; H, 5.49; N, 12.72. Found: C, 81.94; H, 5.10; N, 12.99.
N1-2-([3-Aminoisoquinolin-1-yl]ethyl)isoquinoline-1,3-diamine (4): green solid, mp 280 oC,
decomp) (EtOAc), yield 87 %. IR (nujol) νmax 3292, 3171, 3064,1653.5, 1617, 764 cm-1. 1H NMR
(DMSO-d6) δ 4.06 (s, 4 H), 6.01 (s, 2 H), 6.88 (s, 4 H), 7.16 (t, J = 7.2 Hz, 2 H), 7.45 (d, J = 8.0
Hz, 2 H), 7.55 (t, J = 7.2 Hz, 2 H), 8.26 (d, J = 8.0 Hz, 2 H), 9.37 (s, 2H). Anal. Calcd for
C20H20N6: C, 69.75; H, 5.85; N, 24.40. Found: C, 69.85; H, 5.92; N, 24.37.

N1-2-([3-Aminoisoquinolin-1-yl]butyl)isoquinoline-1,3-diamine (5): yellow solid, mp 250-252
oC, decomp) (EtOAc) , yield 90 %. IR (KBr) νmax 3325 (br), 3194, 1645, 1569, 1091, 746 cm-1. 1H
NMR (DMSO-d6) δ 1.96 (s, 4 H), 4.25 (s, 2 H), 6.20 (s, 2 H), 6.85 (s, 4 H), 7.20 (t, J = 6.8 Hz, 2
H), 7.42 (d, J = 8.0 Hz, 2 H), 7.57 (t, J = 6.8 Hz, 2 H), 8.35 (d, J = 2 H). Anal. Calcd for C22H24N6:
C, 70.94; H, 6.49; N, 22.56. Found: C, 70.87; H, 6.44; N, 22.43.
X-Ray Single Crystal Analysis of 3b. All data shown in Table 2 were collected on a Nicolet
R3m/V diffractometer using the θ-2θ scan technique, Mo-Kα radiation (λ = 0.71073 Å), scan
speed 3.0-15 deg min-1, scan range 3.5-35.00o and a graphite monochromator. Data were
corrected for Lorentz, absorption, and polarization effects. The structures were solved by direct
methods using SHELXS-86,12 the model was refined using full-matrix least-squares methods
Table 2 X-Ray data collection and processing parameters for 3b.
formula
crystal dmns,
cm-3
C13H17N3
T (K)
228
0.20 X 0.15 X 0.10
decay, %
4.17
Space group
a (Å)
P21/c
11.086(1)
10.030(1)
11.516(2)
105.257(6)
1201.7(3)
4
Data collected
Unique reflections
R int
1363
905
b (Å
0.064
c (Å)
Parameters
R, RW
146
β
0.064, 0.082
>0.01
(Δ/σ)
V (Å)
Z-value
ρmax; ρmaxeÅ-3
0.23; - 0.25
1.77
D calc (g-cm3)
1.4190
GOF
ACKNOWLEDGMENTS
This work was supported, in part, by grants from the Welch Foundation, Houston, TX and the
Petroleum Research Corporation, administered by the American Chemical Society.

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