Hydration with mercuric acetate and the reduction with 9-BBN-H of 2-(1-alkenyl)-4,6-dimethyl-s-triazines

Article abstract of DOI:10.1021/jo010784e

Oxymercuration-demercuration of a double bond in conjugation with the 4,6-dimethyl-s-triazin-2-yl substituent as in alkenes la,b gave anti-Markovnikov regioselectivity, which is explained by the electron-withdrawing nature of the triazinyl substituent. However, hydroboration of the conjugated alkenes with 9-BBN-H gave the corresponding alkenes 5a-c under normal workup conditions with or without oxidation. With time and without workup the hydroboration of 1b gave spectral evidence for the formation of intermediates 9-13 resulting from the migration of the 9-BBN moiety from the α-carbon to a ring nitrogen with concurrent formation of an exocyclic double bond to an α-carbon of the ring. Hydrolysis of the intermediates gave 5a-c. A possible mechanism involving successive allylic rearrangements is presented.

Full text of DOI:10.1021/jo010784e

3202
J . Org. Chem. 2002, 67, 3202-3212
Hyd r a tion w ith Mer cu r ic Aceta te a n d th e Red u ction w ith
9-BBN-H of 2-(1-Alk en yl)-4,6-d im eth yl-s-tr ia zin es
H. LeRoy Nyquist,* Edward A. Beeloo, and Lydia S. Hurlbut
Department of Chemistry, California State University, Northridge, California 91330-8262
Rachel Watson-Clark† and David E. Harwell‡
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569
leroy.nyquist@csun.edu
Received August 1, 2001
Oxymercuration-demercuration of a double bond in conjugation with the 4,6-dimethyl-s-triazin-
2-yl substituent as in alkenes 1a ,b gave anti-Markovnikov regioselectivity, which is explained by
the electron-withdrawing nature of the triazinyl substituent. However, hydroboration of the
conjugated alkenes with 9-BBN-H gave the corresponding alkanes 5a -c under normal workup
conditions with or without oxidation. With time and without workup the hydroboration of 1b gave
spectral evidence for the formation of intermediates 9-13 resulting from the migration of the 9-BBN
moiety from the R-carbon to a ring nitrogen with concurrent formation of an exocyclic double bond
to an R-carbon of the ring. Hydrolysis of the intermediates gave 5a -c. A possible mechanism
involving successive allylic rearrangements is presented.
In tr od u ction
The above triazinylalkenes, 1a -c, and 4 were synthe-
sized for the above study, and we now wish to report the
results of their reactions with mercuric acetate and
9-BBN-H. The former gave abnormal regioselectivity
with 1a ,b, and the latter reacted with 1a -c to give the
unexpected corresponding alkanes 5a -c with either
oxidative or hydrolytic workup. In addition, further in-
vestigations via 1H, 13C, and 11B NMR of the latter
reaction with no workup gave conclusive evidence of the
migration of the 9-BBN moiety from the R-carbon to a
ring nitrogen with concurrent formation of exocyclic
double bonds to the R-carbons of the ring. Similar
behavior was shown to occur in the hydroboration of 2-(1-
propenyl)pyridine.3
In a previous paper we reported that the 4,6-dimethyl-
s-triazin-2-yl substituent was electron withdrawing by
both the field effect and the resonance or conjugative
effect.1 In view of this influence, the substituent should
destabilize any intermediate or transition state which
may develop a positive charge on the adjacent R-carbon.2
Hence, it was of interest to investigate the extent to
which this behavior, as well as that of possible steric
factors, would influence the regioselectivity of the hydra-
tion of a conjugated carbon-carbon double bond by pos-
sibly forcing any developing positive charge to form on
the less, or equally, substituted â-carbon. Thus, the sub-
stituent in alkenes 1a ,b, upon oxymercuration-demercu-
ration, would enhance the formation of alcohols 2a ,b, but
in hydroboration-oxidation, it would favor alcohols 3a ,b.
Most previously reported general preparations of al-
kanes from alkenes via hydroboration have required
acidic conditions and prolonged heating,4 and trialkyl-
boranes are also reported to be stable under neutral
conditions.5 Noteworthy exceptions particularly relevant
to the present investigation are the hydrolyses under
relatively mild conditions (pH 8) of the hydroboration-
oxidation of vinyl- and propenylpyridines3 and of substi-
tuted styrenes.2a
(1) Nyquist, H. L.; Wolfe, B. J . Org. Chem. 1974, 39, 2591-2595.
(2) (a) Brown, H. C.; Sharp, R. L. J . Am. Chem. Soc. 1966, 88, 5851-
5854. (b) Brown, H. C.; Zweifel, G. J . Am. Chem. Soc. 1960, 82, 4708-
4712. (c) Traylor, T. G. Acc. Chem. Res. 1969, 2, 152-160.
(3) Brown, H. C.; Vara Prasad, J . V. N.; Zee, S.-H. J . Org. Chem.
1986, 51, 439-445.
(4) (a) Brown, H. C.; Murray, K. J . Am. Chem. Soc. 1959, 81, 4108-
4109. (b) Kabalka, G. W.; Newton, R. J ., J r.; J acobus, J . J . Org. Chem.
1979, 44, 4185-4187.
(5) J ohnson, J . R.; Snyder, H. R.; Van Campen, M. G., J r. J . Am.
Chem. Soc. 1938, 60, 115-121.
† Current address: Clorox Corp., Pleasanton, CA 94612.
‡ Current address: Department of Chemistry, University of Hawaii,
Honolulu, HI 96822-2275.
10.1021/jo010784e CCC: $22.00 © 2002 American Chemical Society
Published on Web 04/24/2002

2-(1-Alkenyl)-4,6-dimethyl-s-triazines
J . Org. Chem., Vol. 67, No. 10, 2002 3203
Ta ble 1. Resu lts of Oxym er cu r a tion -Dem er cu r a tion of
Ta ble 2. Resu lts of Hyd r obor a tion of Tr ia zin yla lk en es
Tr ia zin yla lk en es
w ith 9-BBN-H in Hexa n e
alkene
mole ratioa
% recovered 1
% 2b
yields (mol %)a,b
1a
1b
1b
1b
1:1
1:1
1:2
1:3
c
57
39d
68
78
alkene
workup
H2O2
5
2
1c
cyclooctanoned
55
29
12
1a
1b
1b
1b
1b
1c
1ch
4
62a
81a
72b
46b
23b,g
75
10a,e
0
0
0
0
H2O2
10f
10
EtOH, H2O
CD3OD, D2O
noneg
H2O2
H2O2
25
Alkene:Hg(OAc)2. b No detectable alcohol 3 by NMR. c Spectral
data indicated the possibility of a few percent. A higher temper-
ature (53 °C) did not alter the yield.
a
8
19
10g
21f
26f
13g
d
0
75
0
0
H2O2
60e
Resu lts a n d Discu ssion
Based upon GLC data. Based upon NMR data. c Recovered.
a
b
Based upon moles of 9-BBN-H. e 1° alcohol. Based upon epox-
ide yield. Products distilled from reaction. With 9-BBN-D in
hexane.
d
f
The results of the oxymercuration-demercuration of
1a ,b are given in Table 1.
g
h
The above results would support the conclusion that
the triazine ring, as a substituent, is sufficiently electron-
withdrawing to destabilize any developing charge on the
more or equally substituted R-carbon atom within the
intermediate bridged acetoxymercurinium ion.2c,6 Thus,
the normal regioselectivity is not realized. In addition,
two other factors need to be considered.
transition state species, 6a , which places a partial
positive charge on the primary â-carbon rather than the
destabilized secondary R-carbon to ultimately form the
adduct 7a . It is also reasonable that the alkane would
arise only from adduct 7a in which any carbanion
character on the R-carbon3 would be stabilized by the
s-triazinyl ring.
First, in considering the steric influence of the triazine
ring, it could direct the attacking mercuric acetate away
from the R-carbon and toward the â-carbon and hence
increase the yield of 3a ,b, or second, it could inhibit the
attack by water on the acetoxymercurinium ion at the
R-carbon and thus favor the formation of 2a ,b. The
absence of any detectable alcohols 3a ,b within the
products would indicate that the first influence is neg-
ligible, and the second influence would not appear to be
substantial in view of the fact that 3,3-dimethyl-2-butanol
is formed in 94% yield from the oxymercuration-demer-
curation of 3,3-dimethyl-1-butene in which water attacks
the carbon adjacent to the tert-butyl group.7 Thus, the
regioselectivity appears to be primarily due to the
electronic influence of the triazinyl substituent. A third
factor to be considered is that the mercuric acetate, as a
Lewis acid, may initially coordinate with the lone pair
of electrons8 on a nitrogen of the triazine ring and thereby
enhance the electron-withdrawing influence of the ring
above and beyond that which the neutral ring possesses.
The increased yield of alcohol 2b with an increase in the
mole ratio of mercuric acetate to alkene may support this
involvement of the mercuric acetate with the ring inde-
pendent of the mercuration of the double bond.
The hydroboration-oxidation with 9-BBN-H was car-
ried out on the conjugated alkenes 1a -c and on the
unconjugated alkene 4. The results are given in Table 2.
In the normal hydroboration-oxidation, alkene 1a was
the only conjugated alkene which gave evidence of the
formation of any alcohol (∼10% 2a ). On the basis of the
experimental data from the hydroboration-oxidation of
1b and the large withdrawing resonance effect of the
s-trianzinyl substituent,1 one would conclude that, in
contrast to the hydroboration-oxidation of 2-vinylpyri-
dine (R:â ≈ 1:2),3 the 9-BBN-H in this case added
predominantly to the R-carbon (R:â ≈ 6:1) to form a
When the hydroboration-oxidation was initially car-
ried out on 1b,c with an excess of the alkene, and the
normal period of time,9 a minor amount of the corre-
sponding epoxy compound was also isolated.10 Conse-
quently, subsequent reactions were carried out with
5-10% mole excess of 9-BBN-H. In view of the fact that
the triazinylalkane 5b, and not the alcohol, was the only
product isolated from the hydroboration-oxidation of 1b,
it became apparent that only a source of hydrogen, and
not an oxidizing agent, was involved in the workup. Thus,
the workup of the hydroboration of 1b with ethanol and
water in the absence of hydrogen peroxide gave isolated
5b (72 mol %). A comparable experiment with methanol-
d4 and deuterium oxide gave 5b with increased multi-
1
plicity in the H NMR for the R-methylene proton due to
the presence of deuterium which had replaced the 9-BBN
moiety on the R-carbon. This mode of addition to give the
adduct 7 was also consistent with the results of the
reaction of 9-BBN-D with 1c. There was no spectral
evidence in CDCl3 (1H and 11B NMR) for the migration
of the 9-BBN moiety along the propyl group,11 but there
was evidence in the 11B NMR spectra for the initial
association of the 9-BBN-H dimer or monomer12 with
the nitrogens of the ring (Kb for 3,5,6-trimethyl-1,2,4-
triazine: ∼7 × 10-12
)
13 as reported with amines,14 as well
(6) (a) Kitching, W. Organomet. Chem. Rev. 1968, 3, 61-133. (b)
Chatt, J . Chem. Rev. 1951, 48, 7-43. (c) Olah, G. A.; Clifford, P. R. J .
Am. Chem. Soc. 1971, 93, 2320-2321.
(7) Brown, H. C.; Geoghegan, P. J ., J r. J . Org. Chem. 1970, 35,
1844-1850.
(8) (a) Ramachandran, L. K.; Witkop, B. Biochemistry 1964, 3,
1603-1611. (b) Dean, P. A. W. In Progress in Inorganic Chemistry;
Lippard, S. J ., Ed.; Wiley & Sons: New York, 1978; Vol. 24, pp 109-
178. (c) Wirth, T. H.; Davidson, N. J . Am. Chem. Soc. 1964, 86, 4314-
4318.
(9) Brown, H. C.; Knights, E. F.; Scouten, C. G. J . Am. Chem. Soc.
1974, 96, 7765-7770.
(10) (a) House, H. O. Modern Synthetic Reactions, 2nd ed.; Ben-
jamin: Menlo Park, CA, 1972; pp 306-310 and references therein. (b)
Bunton, C. A.; Minkoff, G. J . J . Chem. Soc. 1949, 665-670.
(11) Taniguchi, H.; Brener, L.; Brown, H. C. J . Am. Chem. Soc. 1976,
98, 7107-7108.
(12) Wang, K. K.; Brown, H. C. J . Org. Chem. 1980, 45, 5303-5306.
(13) Mason, S. F. J . Chem. Soc. 1959, 1247-1253.

3204 J . Org. Chem., Vol. 67, No. 10, 2002
Ta ble 3. NMR Ch em ica l Sh ifts fr om th e Hyd r obor a tion of 1b w ith 9-BBN-H in CDCl3
Nyquist et al.
ring CH3
a
R-CHB<
13C
R-CH2-
1H
â-CH2-
1H
γ-CH3
compd
1H
11B
13C
13C
1H
13C
1H
13H
adduct 7b
2.98 (b)
30.6 (b)
+84b
c
20.85
21.61
21.26
0.92 (t)
0.94 (t)
0.93 (t)
14.79
14.01
13.69
2.50 (s)
2.55 (s)
2.54 (s)
25.70
25.71
25.33
intermediatesd,e
alkane 5bf
2.72 (t)
2.71 (t)
41.01
40.64
1.77 (m)
1.75 (m)
a
b
d
Under argon in sealed NMR tubes. See ref 20. c Initially obscured by 9-BBN signal. Intermediates, 9b-13b, and/or 5b. e With
time the 1H NMR spectra began to show eight small signals (total area ∼ 2-3 H): two triplets (δ 0.86 and δ 4.87), a quintet (δ 2.03), a
multipet (δ 2.21), and two pairs of singlets (δ 4.04, 4.06 and δ 4.39, 4.48). The 13C NMR spectra also showed several small signals between
δ 60 and 150. Within the 11B NMR spectra the δ +84 signal decreased as the δ +59 signal increased. f Authentic sample.
Ta ble 4. Rela tive Yield s of P r od u cts fr om Rea ction
as with the nitrogen of a nitrogen-nitrogen double
Solu tion s of 9-BBN-H w ith Alk en e 1a
bond.15 Boron has also been reported to associate with
rel yields (%)
oxygen in the 1,4-addition of 9-BBN-H in CDCl3 to give
reduction of the double bond in 1-phenyl-2-alken-1-ones16
time
alkane alkene adduct
tempb (months)c
(5)
(1)
(7)
and in 4-hexen-3-one,17 as well as in the 1,2-reduction of
a number of conjugated aldehydes to the corresponding
allylic alcohols.18
alkene
solvent
1b
1b
1b
1b
1b
1b
hexaned,e
hexaneh,i
hexaneh,i
hexaneh,i
hexaned,l
rtf
56
56
55
75
rt
rt
60
rt
rt
rt
75
rt
rt
4
75g
35j
25g
22j
24k
10
9 days
1
2
2 days
2
20
7 days
4
20
1
52 h
20 days
4
43j
26k
55
50k
35
In view of the above unanticipated results and the
uncertainty of the origin of some products, such as
cyclooctanone,19 the progress of the reaction of 9-BBN-H
with 1b under argon in standard reaction apparatuses
was abandoned. Thus, all subsequent reactions, except
those for 11B NMR spectra, were carried out in degassed
solvents under argon in sealed ampules or NMR tubes.
Although abstraction of hydrogen from the glass or the
deuterium from the solvent was considered, experimental
evidence did not support either possibility. The products
arising from the reactions were examined during, and/
or after, many months (4-20) at room temperature or
at elevated temperatures (∼55 °C) for many days (25-
60) by NMR, GC-MS, and/or by quenching with deuter-
ated solvents followed by GC-MS. The following spectral
changes were observed for the reaction of 9-BBN-H with
1b in CDCl3 at room temperature. Within a few hours,
in addition to the signals from the alkene and the 9-BBN
81m
71o
85
19m
25o
i,n
CDCl3
1b-d6 CDCl3
4o
15p
3o
i,n
97o
100o,q
51
0o
0o
i,n
1b
1b
1b
1b
1b
1c
1c
CDCl3
i,n
CD2Cl2
0o
i,n
C6D6
49r
23o
d,i,n
THF-d8
37o
61s
64o
85o
40o
39s
17o
15o
THFd,l
i,n
CDCl3
CDCl3
19o
0o
i,n
a
Based upon GC-MS data before workup unless otherwise
designated. b Bath temperature, °C. c Unless otherwise designated.
Commercial 9-BBN-H solution. e Vial with septum. f Precipitate
d
g
formed. Absolute yields relative to nonane: 5b, 62%; 1b, 21%.
h
i
j
Sealed ampule. Prepared 9-BBN-H solution. Absolute yields
k
relative to nonane: 5b, 38%; 1b, 23%; 7, 46%. Absolute yields
relative to nonane: 5b, 38%; 1b, 18%; 7, 20%. l Reaction flask (Ar).
m
n
Absolute yields relative to nonane: 5b, 61%; 1b, 15%. Sealed
NMR tube. o Based upon NMR data (alkane yield also includes
intermediates 8-13). m/z 399 (7-d6 + 9-BBN-H). Absolute
yields relative to 2,4,6-tripropyl-s-triazine: 5b, 52 mol %. m/z 393
(7 + 9-BBN-H). Absolute yields relative to bibenzyl: 5b, 33 mol
%; 1b, 25 mol %.
p
q
1
moiety, the H, 13C, and 11B NMR spectra began to show
r
s
signals consistent with those of adduct 7b as shown in
1
Table 3. The broad signal at δ 2.98 within the H NMR
spectra due to the presence of boron on the R-carbon
requires some comment. A three-coordinate, but not a
four-coordinate, boron on carbon is reported not to
undergo two-bond coupling with hydrogen.21 Therefore,
this situation is either anomalous or the boron is partially
four-coordinated with a nitrogen of the ring or is still
partially associated as a dimer. The 11B NMR spectra at
δ +5922 would support an early (2 h) and an increasing
association of a boron with a nitrogen as the reaction
progressed. As the reaction continued, the signals from
7b increased and those of the alkene decreased. However,
after 3-4 days at room temperature, all of the signals
attributed to 7b had maximized and a sharp triplet at δ
2.72 (R-CH2) in the 1H NMR spectra became increasingly
evident. Thus, the signals from 7b began to decrease as
new signals consistent with those of the alkane 5b began
to appear and continue to increase over a period of
months. However, in addition to the signals attributed
to 5b, the final 1H NMR spectrum showed a total of eight
small signals (Table 3) totaling approximately two to
three protons. The final 13C NMR spectrum also gave an
increasing number (∼10) of small signals between δ 60
and 150 which a DEPT spectrum showed to be sp2
carbons. Essentially the same sequence of NMR spectra
was obtained when the reaction was carried out at 60 °C
for 8 days. Since the additional signals could not be
assigned to 7b or 5b, they were attributed to species
resulting from the rearrangement of 7b to possible
species such as 8a -c and 9a -c through 13a -c. Table 4
shows the relative yields of products from the GC-MS
analyses of the reaction solutions of 1b with 9-BBN-H
in a variety of solvents before hydrolysis. The transfor-
mation of 7b into 5b and intermediates 9b-13b appears
to proceed more rapidly in more polar solvents. Quench-
ing of the NMR solutions with water after completion of
(14) (a) Brown, H. C.; Kulkarni, S. U. Inorg. Chem. 1977, 16, 3090-
3094. (b) Brown, H. C.; Chandrasekharan, J .; Wang, K. K. J . Org.
Chem. 1983, 48, 3689-3692.
(15) Brand, U.; Hu¨nig, S.; Peters, K.; von Schnering, H. G. Chem.
Ber. 1991, 124, 1187-1190.
(16) Matsumoto, Y.; Hayashi, T. Synlett 1991, 349-350.
(17) Boldrini, G. P.; Bortolotti, M.; Tagliavini, E.; Trombini, C.;
Umani-Ronchi, A. Tetrahedron Lett. 1991, 32, 1229-1232.
(18) Krishnamurthy, S.; Brown, H. C. J . Org. Chem. 1977, 42, 1197-
1201.
(19) (a) Bulgakov, R. G.; Tishin, B. A.; Vlad, V. P.; Maistrenko, G.
Ya.; Ostakhov, S. S.; Tolstikov, G. A.; Kazakov, V. P. Khim. Vys. Energ.
1989, 23, 250-256. (b) Kulkarni, S. U.; Rao, C. G.; Patil, V. D.
Heterocycles 1982, 18, 321-326.
(20) Onak, T. Organoborane Chemistry; Academic Press: New York,
1975; p 7.
(21) (a) Onak, T. Organoborane Chemistry; Academic Press: New
York, 1975; p 9. (b) De Moor, J . E.; Van der Kelen, G. P. J . Organomet.
Chem. 1966, 6, 235-241.
1
the reaction caused all of the H NMR signals unique to
the intermediates 9b-13b to disappear and leave only
(22) No¨th, H.; Wrackmeyer, B. Chem. Ber. 1973, 106, 1145-1164.

2-(1-Alkenyl)-4,6-dimethyl-s-triazines
J . Org. Chem., Vol. 67, No. 10, 2002 3205
those signals attributable to 5b and the 9-BBN moiety,
whose broad envelope (δ 1.25-2.0) had sharpened.
Within the 13C NMR spectra the signals between δ 60
and δ 150 disappeared and the broad signals due to the
9-BBN moiety (δ 23.3 and δ 33.2) narrowed.
R-carbon (1J ) 19.5 Hz) giving evidence consistent with
the formation of 5b from the quenching of intermediates
9-13. The 9-BBN-O-CH3 (65-75% yield) from the
quenching experiments did not show any incorporation
of deuterium. Derivatization of the 9-BBN moiety at the
end of the reaction with ethanolamine24 or oxidation with
peroxide gave yields of approximately 90% of the etha-
nolamine adduct and 95% of the cis-1,5-cyclooctanediol.
Slow evaporation (14 months) of the CDCl3 of the
reaction solution from the hydroboration of 1b open to
the air gave crystals which upon crystallographic analysis
showed the presence of a 1:1 complex of boric acid and
1b together with some 5b and from which, with time,
both of the latter evaporated.25
1
(2) Low-temperature H NMR (400 MHz) enabled the
signal at δ 2.03 to be resolved into a quintet and the
signals between δ 4 and δ 5 to be resolved into a triplet
(δ 4.87) and two pairs of singlets (δ 4.04, 4.06 and δ 4.39,
4.48). The quintet and the triplet together with the small
upfield triplet (δ 0.86) are supportive of the presence of
the propylidene group of intermediates 9b and 10b.
Likewise, the presence of the two exocyclic methylene
groups and the n-propyl groups of intermediates 11b-
13b is supported respectively by the two pairs of singlets
(2J ) 0) and two large triplets (δ 0.94 and δ 2.72) and a
sextet (δ 1.77). The latter three multiple signals are also
contributed to by the n-propyl group of any alkane 5b
present. The possible presence of 5b before quenching
was indicated by a semiquantitative comparison in the
1H NMR in which the calculated areas from the ring
methyl groups of 9b-13b (relative to the areas of the
sp2 hydrogens) could account for only 55-60% of the total
area from all of the ring methyl groups. Experimentally,
the presence of 5b before quenching was also supported
by the GC-MS analyses of the reaction solutions (Table
4). The most probable sources of 5b before quenching
would arise from hydrogen abstraction from between the
intermediates (disproportionation) or from the 9-BBN
moiety.
The following experimental evidence supports the
formation of alkane 5, adduct 7, and intermediates 9-13
in the reaction of 9-BBN-H with 1a -c. Although inter-
mediate 8 is a feasible species, no experimental evidence
was found to support its existence.
(3) To further ascertain whether the methyl groups of
the ring or the allylic γ-methyl groups of 1b,c were
sources for the hydrogen that replaced the 9-BBN moiety,
the following deuterated compounds were synthesized.
Experimentally, within 6 h, the hydroboration of 1b-d6
(1) When the reaction of 1b with 9-BBN-H in CDCl3
was permitted to proceed only until the adduct 7b was
fully formed (70 h, room temperature) and then quenched
with methanol-d4, the 1H NMR gave a multiplet at δ 2.65
(R-CHD) and showed essentially a quantitative conver-
sion of 7b to 5b relative to bibenzyl as an internal
reference. However, when the reactions were permitted
to proceed for longer periods of time past the formation
of 7b before quenching, the yields of alkane 5b relative
to bibenzyl in the NMR or to nonane in GC-MS were
within 40-60% depending upon the solvent (Table 4).
These lower yields could indicate that unidentified
products were formed before quenching as a result of
disproportionation between the intermediates. Also, after
deuterium quenching, unidentified products (5-6%) con-
taining deuterium were frequently found in the GC-MS
of the products. The MS also showed an enrichment of
deuterium in the spectrum of 5b (m/z 150-155) relative
to that of 5b from nondeuterated quenches (m/z 150-
152). The 13C NMR spectrum of the 5b from the deute-
rium quench showed 13C-D coupling23 both at the
carbons of the ring methyl groups (1J ) 19.6 Hz) and the
(24) (a) Rondestvedt, C. S., J r.; Scribner, R. M.; Wulfman, C. E. J .
Org. Chem. 1955, 20, 9-12. (b) Kramer, G. W.; Brown, H. C. J . Org.
Chem. 1977, 42, 2292-2299.
(23) Friebolin, H. Basic One- and Two-Dimensional NMR Spectros-
copy, 2nd ed.; VCH Publishers: New York, 1993; pp 49-50 (translated
by J . K. Becconsall).
(25) The crystal structure will be reported elsewhere.

3206 J . Org. Chem., Vol. 67, No. 10, 2002
Nyquist et al.
Sch em e 1
coordinated with a 9-BBN moiety may be due to the
broadening of the nitrogen signal by the coupling of the
boron with the nitrogen.27
Although it was difficult to obtain a reproducible rate
for the conversion of the adduct 7b to the intermediates
9b-13b and 5b, the addition of galvinoxyl28 to the
reaction solution after 7b had formed appeared to
decrease the rate, hence indicating the possibility that
the replacement of the 9-BBN moiety by a hydrogen
proceeded via a free radical mechanism. However, this
result is suspect because a control indicated that
9-BBN-H decolorized galvinoxyl within minutes. Sup-
port for a free radical mechanism could also be concluded
from the presence within some of the final products of a
molecular ion having the mass of a coupled product (m/z
300). The ESR spectrum of the hydroboration of 1b in
C6D6 was taken at appropriate intervals after the adduct
7b had formed, but no signal was obtained either because
of the absence of free radicals or because their concentra-
tions were too low for detection.
To examine whether the behavior observed in the
triazinylalkenes 1 would be evident in comparable sys-
tems, the hydroboration with 9-BBN-H of 2-vinylpyri-
dine and trans-2-(1-propenyl)pyridine as reported by
Brown3 was carried out in sealed NMR tubes over long
periods of time. The 1H NMR spectra of the hydroboration
of the 2-vinylpyridine with 9-BBN-H (1:1) at room
temperature gave a broad singlet at δ 0.57, two sharp
triplets at δ 0.83 and δ 2.9, and an increased multiplicity
of the signals associated with the ring hydrogens after
17 days with no additional changes even with heating.
With a ratio of 1:2 (alkene:9-BBN-H) the results were
similar except for an initial broadening of the signals for
the hydrogens of the 2-vinylpyridine. These results were
consistent with the reported bonding of the 9-BBN moiety
to the â-carbon,3 but there was no evidence for the
formation of the corresponding alkane. Likewise, the
hydroboration of 2-(1-propenyl)pyridine gave no evidence
of the formation of the alkane, and 1H NMR spectral
evidence indicated that the 9-BBN moiety bonded ini-
tially to the R-carbon. In the case of a 1:1 ratio (alkene:
9-BBN-H), but not in the case of the 1:2 ratio, a new
downfield triplet in the 1H NMR spectra began to appear
after 1 day at δ 1.16 as well as a number of multiplet
signals between δ 4.5 and δ 6.3. Simultaneously, the 13C
NMR spectra began to show an increased number of
signals between δ 110 and δ 170. With the addition of
water to the NMR sample, the above signals disappeared
from the spectrum to give that of the alkane. The above
downfield triplet and the multiplet signals in the 1H
NMR, and the accompanying 13C NMR signals, would be
supportive of the migration of the 9-BBN moiety to the
nitrogen with the 1:1 ratio giving the formation of an
exocyclic double bond to the R-carbon similar to that
which formed intermediates 9 and 10 proposed for the
hydroboration of the triazinylalkenes. In the case of the
1:2 ratio presumably a second 9-BBN-H was already
coordinated with the nitrogen, thus prohibiting the
migration of the first 9-BBN moiety to the nitrogen.
However, the failure to obtain any alkane in the hy-
droboration of the alkenylpyridines would tend to pre-
clude the 9-BBN moiety as a source of the hydrogen
(93 atom % D) in CDCl3 began to show a sharp triplet
at δ 2.72 for the R-methylene group. After approximately
5 days, a broad multiplet (2J ) 2 Hz) began to appear
superimposed upon the sharp triplet. This multiplicity
at δ 2.72 continued to increase until the original broad
signal at δ 2.98 (>CHB<) had essentially disappeared
(∼15 days). No further changes in any of the signals
occurred within the following 9 months indicating the
absence of scrambling. Simultaneous with the above
changes was a significant decrease in the small signal
area for the residual protons originally remaining in the
methyl groups of the ring (δ 2.54). An approximation of
the relative areas of the superimposed sharp and broad
signals for the R-methylene group (δ 2.72) was two-thirds
(-CH2-) and one-third (-CHD-), respectively, which
would indicate a 1:1 hydrogen to deuterium migration
ratio to the R-carbon. This ratio would be unlikely to
originate only from the methyl groups of the ring (93
atom % D) even with a maximum isotope effect, and
therefore, this result is supportive of possibly another
source for the hydrogen such as the 9-BBN moiety. Also,
with time, within the 13C NMR spectra for the above
reaction of 1b-d6, a small triplet became superimposed
on the singlet for the R-methylene group (δ 41.01) giving
evidence via coupling of the presence of deuterium on the
1
R-carbon. The H and 13C NMR spectra for the reaction
of 1b-d7 with 9-BBN-H in C6D6 were also supportive of
the above conclusions. The hydroboration of 1c-d6 with
9-BBN-H in CDCl3 over a period of 10 months gave no
evidence of deuterium on the R-carbon thus ruling out
the possible involvement of the allylic hydrogens.
It is conceivable that the mechanism by which a
hydrogen is transferred intramolecularly from a ring
methyl group to the R-carbon proceeds via a series of
allylic rearrangements via an enamine tautomer, 14,
formed from 9 as shown in Scheme 1.
The 15N NMR spectrum of the reaction intermediates
from 1b (4 months) did not give evidence of a boron
coordinated with a nitrogen26 but gave only two signals
at δ 266.69 and 267.71 which did not differ significantly
from the 15N NMR spectrum of 2,4,6-trimethyl-s-triazine
alone (δ 267.23) or with 9-BBN-H present (δ 267.32).
However, the 11B NMR spectra indicated that the 9-BBN
moiety became increasingly coordinated to a nitrogen (δ
+59) throughout the reaction and was exclusively as-
sociated with a nitrogen at the end of the reaction. The
failure to observe a 15N NMR signal from a nitrogen
(27) Wrackmeyer, B. J . Magn. Reson. 1986, 66, 172-175.
(28) (a) Kabalka, G. W.; Brown, H. C.; Suzuki, A.; Honma, S.; Arase,
A.; Itoh, M. J . Am. Chem. Soc. 1970, 92, 710-712. (b) Bartlett, P. D.;
Funahashi, T. J . Am. Chem. Soc. 1962, 84, 2596-2601.
(26) Mason, J . In Multinuclear NMR; Mason, J ., Ed.; Plenum
Press: New York, 1987; pp 350-355.

2-(1-Alkenyl)-4,6-dimethyl-s-triazines
J . Org. Chem., Vol. 67, No. 10, 2002 3207
necessary to convert intermediates 7-13 into 5, unless
those intermediates had greater affinities for the hydro-
gens of the 9-BBN moiety than comparable species in the
pyridine case.
Exp er im en ta l Section
Gen er a l Meth od s. Melting points and boiling points are
uncorrected. All reactions were performed in oven-dried
glassware under an atmosphere of dried and deoxygenated
argon. 1H, 13C, 11B, and 15N NMR spectra were recorded at
200, 50, 160.5, and 50.7 MHz, respectively. Variable-temper-
ature NMR spectra were recorded at 400 MHz. Proton chemi-
cal shifts were referenced to residual solvent protons, carbon
chemical shifts were referenced to solvent, boron chemical
shifts were referenced to external BF3‚OEt2, and nitrogen
chemical shifts were referenced to external trimethyl-s-triaz-
The following controls were carried out: (a) The 1H
NMR spectra of 9-BBN-H in CDCl3 within a sealed NMR
tube at room temperature showed no changes over 70
days, and (b) 2,4,6-trimethyl-s-triazine with 9-BBN-H
in CDCl3 with bibenzyl as a reference in a sealed NMR
tube showed no change in the ratio of the signal areas
over a period of 8 months at room temperature. Addition-
ally, the hydrolysis of the final solution29 accounted for
95% of the original 9-BBN-H molarity. Thus, under the
conditions in which the hydroborations of 1 was carried
out in this study, there were no significant reactions
occurring between the 9-BBN-H and the triazine ring
or its methyl groups. However, the control studies do not
preclude the possibility that the adduct 7 may be capable
of abstracting a hydrogen, intra- or intermolecularly,
from a methyl group on the triazine ring or the 9-BBN
moiety.
Attempts at aprotic workup of the sealed and unsealed
final reaction solutions frequently gave considerable
amount of cyclooctanone, presumably due to exposure to
air and solvents that had not been degassed. The yields
of cylcooctanone exceeded the amount of excess 9-BBN-H
and, therefore, would indicate that the 9-BBN moiety
associated with intermediates 7-13, as well as unreacted
9-BBN-H, reacted with air to give cyclooctanone.19 Other
minor products evident in the GC-MS analyses and
presumably arising from the 9-BBN-H or its moiety, but
not necessarily directly involved in the conversion of
intermediates 7-13 to 5, were bicyclo[3.3.0]octane, cy-
clooctane, and cyclooctene. These products were among
those reported as products in the reaction of alkaline
AgNO3 with 9-BBN-H30 and in the oxidation of 9-BBN-H
with PCC.19b
1
ine. GLC analyses were performed with a 4 ft × /4 in. column
packed with DC 200 on Chrom-P and a TC detector. Mass
spectra were obtained with a mass spectrometer coupled with
a gas chromatograph. Elemental analyses were performed by
Desert Analytics Laboratory, Tucson, AZ. Unless otherwise
noted, materials were obtained from commercial suppliers and
used without further purification. Ether was distilled from
sodium benzophenone ketyl under argon, and final distillations
of glyme and THF were from LAH. Solvents used for the
preparation of 9-BBN-H solutions were degassed. 9-BBN-H
was either recrystallized from purified glyme12 or sublimed
(120 °C/0.04 Torr) after a forerun was taken: melting points
were within the 150-154 °C range (evacuated, sealed capil-
laries, lit.9,33 mp 152-155 °C). Solid 9-BBN-H was transferred
within an argon-filled glovebag, and the transfer of solvents,
9-BBN-H solutions, and hydroboration reaction solutions
were carried out with oven-dried, argon-flushed syringes.
Vinylpyridine was purified by distillation at reduced pressure
from calcium hydride.
2,4-Dim eth yl-6-vin yl-s-tr ia zin e (1a ). To a solution of 2a 34
(1.97 g, 12.9 mmol) in 150 mL of dry benzene was added 3 g
(0.02 mol) of phosphorus pentoxide with vigorous stirring. The
mixture was heated (50 °C) for 4 days, during which time two
portions (2 g, 1 g) (0.02 mol) of phosphorus pentoxide were
added. The mixture was filtered through Celite, and the
solution was extracted with saturated NaCl solution (3 × 1
mL). The aqueous phases were extracted with CH2Cl2 (2 × 10
mL), and the organic phases were combined, dried (MgSO4),
filtered, and evaporated to yield a liquid residue which was
distilled to afford 0.58 g (34%) of the alkene: bp 51-56 °C
(4.5 Torr) (lit.35 bp 73-75 °C (19 Torr)); IR (neat) 3025, 1630,
1530, 955 cm-1; 1H NMR (CDCl3) δ 2.52 (s, 6H), 5.78 (dd, 1H),
6.60 (dd, 1H), 6.77 (dd, 1H).
The reductions of 1b with BH3‚THF and sodium
borohydride were also examined. A large excess of
BH3‚THF with 1b at room temperature gave no evidence
of any reaction as followed by TLC, and prolonged
refluxing (28 h) led to the destruction of the triazine ring.
This may not be unexpected in view of boranes reactivity
with nitriles31 and amides.32 The reaction of 1b with
equal molar amounts of sodium borohydride gave 24%
alkane (5b) and 76% recovered 1b.
2,4-Dim eth yl-6-(1-p r op en yl)-s-tr ia zin e (1b). A solution
of 2b36 (3.16 g, 19 mmol) in 5.5 mL (58 mmol) of acetic
anhydride containing a few crystals of toluenesulfonic acid was
refluxed for 2 h and then distilled. After distillation of the
acetic acid and excess acetic anhydride, the crude alkene was
distilled to afford 2.29 g of product: bp 66-68 °C (4 Torr). The
crude alkene was dissolved in ether (15 mL) and stirred at
room temperature with saturated NaHCO3 solution (4.5 mL)
for 3 days. The phases were separated, the aqueous phase was
extracted with ether (2 × 10 mL), and the combined ether
phases were dried (MgSO4). The ether phase was evaporated
to yield a clear liquid (1.80 g), which was distilled to afford
1.60 g (56%) of 1b: bp 70-72 °C (4.0 Torr); IR (neat) 3020,
Con clu sion
The oxymercuration-demercuration of 1a ,b gave ab-
normal regioselectivity due to the electron-withdrawing
influence of the triazine ring. Hydroboration-oxidation
and hydroboration-hydrolysis of 1a -c gave the corre-
sponding alkane 5. In the absence of hydrolysis, NMR,
GC-MS, and deuterium studies showed that the 9-BBN
moiety tautomerized to a ring nitrogen to form interme-
diates 9-13 and that some alkane 5 was formed possibly
by disproportionation of the intermediates or hydrogen
abstraction from the 9-BBN moiety.
1
1650, 1530, 955 cm-1; H NMR (CDCl3) δ 1.94 (dd, J ) 8.5,
2.5 Hz, 3H), 2.53 (s, 6H), 6.35 (dq, J ) 17, 2.5 Hz, 1H), 7.38
(dq, J ) 17, 8.5 Hz, 1H); 13C NMR (CDCl3) δ 18.4, 25.5, 129.6,
142.0, 170.6, 175.8. Anal. Calcd for C8H11N3 (Mr ) 149.21):
C, 64.40; H, 7.43; N, 28.17. Found: C, 64.25; H, 7.66; N, 28.13.
2,4-Dim eth yl-d 6-6-(1-p r op en yl)-s-tr ia zin e (1b-d 6). A so-
lution of 1b (483 mg, 3.2 mmol) in D2O (5 mL) containing 6 N
(32) Brown, H. C.; Heim, P. J . Am. Chem. Soc. 1964, 86, 3566-
3567.
(33) Brown, H. C.; Liotta, R.; Kramer, G. W. J . Am. Chem. Soc. 1979,
101, 2966-2970.
(29) Brown, H. C. Organic Syntheses via Boranes; Wiley & Sons:
New York, 1975; pp 241-245.
(34) Schaefer, F. C. U.S. Patent 3,203,550, 1965; Chem. Abstr. 1965,
63, 14886g.
(30) Mehrotra, I.; Devaprabhakara, D. J . Organomet. Chem. 1974,
82, C1-C2.
(35) American Cyanamid Co. Brit. Patent 935,787, 1963; Chem.
Abstr. 1964, 60, 2987d.
(36) Nyquist, H. L.; Davenport, D. A.; Han, P. Y.; Shih, J . G.;
Speechly, T. G. J . Org. Chem. 1992, 57, 1449-1456.
(31) (a) Brown, H. C.; Subba Rao, B. C. J . Am. Chem. Soc. 1960,
82, 681-686. (b) Emele´us, H. J .; Wade, K. J . Chem. Soc. 1960, 2614-
2617.

3208 J . Org. Chem., Vol. 67, No. 10, 2002
Nyquist et al.
NaOD (2 drops) at pH 10 was permitted to stand at room
temperature under argon for 3 days during which the deute-
rium exchange was followed by 1H NMR. The solvent was
distilled under reduced pressure (3.5 Torr), and the residue
was dissolved in D2O (5.0 mL) with 1 drop of 6 N NaOD. After
3 days the solution was neutralized with acetic acid-d4 and
distilled to afford a residue which was saturated with NaCl
and extracted with ether (5 × 10 mL) and dichloromethane (2
× 10 mL). The aqueous distillate was also extracted with
dichloromethane, and the combined extracts were dried (Mg-
SO4) and evaporated to afford 534 mg (110%) of liquid residue.
The residue was eluted on neutral alumina (12 g) with 5%
ether/pentane, and selected fractions were combined and
distilled to afford 90 mg (18%) of 1b-d6: bp 66-68 °C (3 Torr);
IR (neat) 2230, 1650, 1525, 965 cm-1; 1H NMR (CDCl3) δ 1.94
(dd, 3H), 2.50 (m, 0.4H), 6.35 (dq, 1H), 7.38 (dq, 1H); 13C NMR
(CDCl3) δ 18.6, 25.7 (m), 129.8, 142.1, 170.8, 176.2.
mixture was permitted to warm to room temperature for 2 h
and then cooled to -78 °C. A solution of dry acetone (6.6 mL,
90 mmol) in ether (100 mL) was then added (25 min), and the
mixture was permitted to warm to room temperature over-
night. The mixture was cooled (0 °C), and a cold, saturated
NH4Cl solution (15 mL) was added. The ether phase was
separated and washed with NH4Cl solution (6 mL). The
aqueous phases were extracted with ether (50 mL), and the
ether phases were combined and dried (MgSO4). Evaporation
of the solvent gave 17.21 g of liquid which was distilled to
afford 7.20 g (48%) of product: bp 107-110 °C (1.9 Torr); IR
(neat) 3430, 1525, 1145 cm-1; 1H NMR (CDCl3) δ 1.31 (s, 6H),
2.60 (s, 6H), 3.00 (s, 2H), 5.10 (s, 1H); 13C NMR (CDCl3) δ 25.8,
29.6, 49.9, 70.2, 176.0, 177.0. Anal. Calcd for C9H15N3O (Mr )
181.23): C, 59.64; H, 8.34; N, 23.19. Found: C, 59.94; H, 8.55;
N, 22.78.
2,4-Dim eth yl-6-(2-m eth yl-1-p r op en yl)-s-tr ia zin e (1c).
The method for the preparation of 1b was followed. Alcohol
2c (3.04 g, 16.8 mmol) afforded 2.19 g of the crude alkene,
which after treatment with a saturated NaHCO3 solution and
workup afforded 1.98 (72%) of product: bp 128-131 °C (50
Torr); IR (neat) 3010, 1640, 1510, 850 cm-1; 1H NMR (CDCl3)
δ 1.95 (s, 3H), 2.30 (s, 3H), 2.55 (s, 6H), 6.22 (s, 1H); 13C NMR
(CDCl3) δ 20.7, 25.6, 28.4, 123.2, 153.9, 171.7, 175.4; MS m/z
(relative intensity) 163 (24), 162 (27), 148 (60), 121 (16), 81
(34), 42 (100). Anal. Calcd for C9H13N3 (Mr ) 163.21): C, 66.23;
H, 8.03; N, 25.75. Found: C, 66.12; H, 8.25; N, 25.68.
2,4-Dim eth yl-6-(2-m eth ylp r op yl)-s-tr ia zin e (5c). A 35 wt
% dispersion of KH in mineral oil (1.48 g KH, 36.8 mmol) under
argon was washed with dry benzene (5 × 5 mL) and then
covered with glyme (75 mL). To the stirred suspension at room
temperature was added (75 min) a solution of 2,4,6-trimethyl-
s-triazine (4.64 g, 37.7 mmol) in glyme (20 mL). After being
stirred for 3 h, the pumpkin-colored suspension was added (22
min) to a solution of 2-bromopropane (4.72 g, 38.3 mmol) in
75 mL of glyme at -78 °C. The reaction mixture was stirred
and warmed to room temperature overnight and then warmed
to 70 °C (1 h). The brick-red suspension was cooled to room
temperature and worked up as described above for the
preparation of 5b to afford 1.34 g of recovered 2,4,6-trimethyl-
s-triazine and 1.00 g of impure 5c (23% yield adjusted for
recovered triazine): bp 70-78 °C (2.5 Torr). A portion (653
mg) of the above product was placed on neutral alumina (l cm
× 25 cm) and eluted with 4% ether/pentane to afford, after
distillation, 450 mg of 5c: bp 76-78 °C (4.6 Torr); IR (neat)
2960, 1520 cm-1; 1H NMR (CDCl3) δ 0.88 (d, 6H), 2.20 (m, 1H),
2.53 (s, 6H), 2.61 (d, 2H); 13C (CDCl3) δ 22.3, 25.4, 28.0, 47.7,
175.7, 178.3; MS m/z (relative intensity) 165 (M+, 2), 150 (11),
2,4-Dim eth yl-d 6-6-(1-p r op en yl-1-d )-s-tr ia zin e (1b-d 7). A
solution of 2b (3.02 g, 18.1 mmol) in D2O (7.0 mL) containing
6 N NaOD (2 drops) was permitted to stand at room temper-
ature for 5 days during which the deuterium exchange was
followed by 1H NMR. The solvent was distilled under reduced
pressure (3 Torr) to afford a residue and a distillate which was
extracted with ether (3 × 10 mL), and the latter was dried
(MgSO4) and evaporated to give additional residue. The
combined residues were dissolved in D2O (6 mL), 6 N NaOD
(1 drop) was added, and the above procedure was followed.
The latter treatment with D2O was repeated twice. The final
reaction solution was worked up as described for 1b-d6 to
afford 2.15 g (68%) of solid alcohol 2b-d9: bp 99-102 °C (3.4
1
Torr); H NMR (CDCl3) δ 1.21 (d, 3H), 2.50 (m, 0.36H), 2.81
(m, 0.39H), 4.22 (m, 1H), 4.4 (br s, 0.3H). Alcohol 2b-d9 (863
mg, 4.9 mmol) was treated with acetic anhydride (3 mL)
according to the procedure for the preparation of alkene 1b to
afford 488 mg (64%) of alkene 1b-d7, whose deuterium content
of the methyl groups of the ring had decreased to 71 mol %.
Therefore, the alkene was treated with D2O (5 mL) and 6 N
NaOD (4 drops) at room temperature for 1 day and then
worked up as previously described for 1b-d6 to afford 206 mg
of crude 1b-d7. The crude 1b-d7 (156 mg) was eluted on neutral
alumina (10 g) with 5% ether/pentane, and selected fractions
were combined and distilled to afford 56 mg of 1b-d7: bp 70
°C (4 Torr); IR (neat) 2960, 2270, 1650, 1525, 895 cm-1 1H
;
NMR (CDCl3) δ 1.92 (d, 3H), 2.52 (m, 0.6H), 6.35 (dq, 0.3H),
7.36 (m, 1H); 13C NMR (C6D6) δ 18.1, 141.0, 171.0, 176.3.
2,4-Dim eth yl-6-p r op yl-s-tr ia zin e (5b). A 35 wt % disper-
sion of KH in mineral oil (1.45 g KH, 36.1 mmol) was washed
under argon with dry benzene (4 × 8 mL) and then covered
with 75 mL of glyme. To the stirred suspension at room
temperature was added (22 min) a solution of 2,4,6-trimethyl-
s-triazine (4.51 g, 36.6 mmol) in glyme (20 mL). After being
stirred for 2 days, the rust-colored suspension was added (1
h) to a solution (0 °C) of bromoethane (12.0 g, 110 mmol) in
glyme (70 mL). The reaction mixture was stirred overnight,
filtered through Celite, and evaporated to afford 5.87 g of a
dark red liquid. The liquid was dissolved in ether, extracted
with cold, saturated NH4Cl solution (3 × 2 mL), dried (MgSO4),
and evaporated to afford 4.85 g (88%) of a reddish-brown
liquid. The liquid was distilled (94-118 °C, 54 Torr) to give
2.90 g of distillate which was chromatographed on neutral
alumina (40 g) with 5% ether/pentane. Selected fractions were
combined and distilled to give 0.25 g of product: bp 102-106
°C (72 Torr) (lit37 bp 98.5-99 °C (44 Torr)); IR (neat) 2960,
1530 cm-1; 1H NMR (CDCl3) δ 0.94 (t, 3H), 1.76 (m, 2H), 2.54
(s, 6H), 2.71 (t, 2H); 13C NMR (CDCl3) δ 13.7, 21.3, 25.3, 40.6,
175.7, 178.8.
123 (49), 68 (16), 42 (100). Anal. Calcd for C9H15N3 (Mr
165.23): C, 65.42; H, 9.15; N, 25.43. Found: C, 65.41; H, 9.18;
N, 25.42.
)
2-Meth yl-d 3-1-(4,6-d im eth yl-s-tr ia zin -2-yl)-2-p r op a n ol-
3,3,3-d 3 (2c-d 6). The method for the preparation of 2c was
followed except that acetone-d6 was used. Distillation of the
product afforded a 54% yield of product. A portion (1.1 g) of
the product was eluted from alumina (11 g) with ether, and
selected cuts were distilled to afford 36 mg: bp 84-86 °C (2.8
Torr); IR (neat) 3460, 2230, 1530, 1160 cm-1; 1H NMR (CDCl3)
δ 2.56 (s, 6H), 2.92 (s, 2H), 5.06 (s, 1H); 13C NMR (CDCl3) δ
25.5, 28.5 (m), 49.7, 69.7, 175.8, 176.7. Anal. Calcd for
C9H9D6N3O (Mr ) 187.28): C, 57.72; H + 1/2D, 8.07; N, 22.44.
Found: C, 57.66; H, 7.90; N, 22.21.
2,4-Dim eth yl-6-(2-m eth yl-d 3-1-p r op en yl-3,3,3-d 3)-s-tr i-
a zin e (1c-d 6). The method for preparation of 1c was followed.
Alcohol 2c-d6 (3.08 g, 16.4 mmol) afforded 2.47 g of the crude
alkene, which after treatment with saturated NaHCO3 and
workup afforded 1.82 g (65%) of product: bp 88-89 °C (4.8
Torr); IR (neat) 2200, 1640, 1530, 880 cm-1; 1H NMR (CDCl3)
δ 2.50 (s, 6H), 6.17 (s, 1H); 13C NMR (CDCl3) δ 25.7, 123.4,
154.0, 171.9, 175.6. Anal. Calcd for C9H7D6N3 (Mr ) 169.26):
2-Meth yl-1-(4,6-dim eth yl-s-tr iazin -2-yl)-2-pr opan ol (2c).
To a stirred solution under argon of 2,4,6-trimethyl-s-triazine
(10.26 g, 83.3 mmol) in 350 mL of anhydrous ether (-78 °C)
was added n-butyllithium (2.45 M, 85.8 mmol). After the
addition was completed (30 min), the bright-yellow reaction
1
C, 63.86; H + /2D, 7.74; N, 24.83. Found: C, 63.50; H, 7.63;
N, 25.12.
2-(3-Bu ten yl)-4,6-d im eth yl-s-tr ia zin e (4). A 35 wt %
dispersion of KH in mineral oil (2.14 g KH, 53.2 mmol) under
argon was washed with dry benzene (5 × 5 mL) and then
(37) Zaitseva, E. L.; Braz, G. I.; Yakubovich, A. Ya.; Bazov, V. P.
Zh. Obshch. Khim. 1963, 33, 199-202; Chem. Abstr. 1963, 58, 13957g.

2-(1-Alkenyl)-4,6-dimethyl-s-triazines
J . Org. Chem., Vol. 67, No. 10, 2002 3209
covered with glyme (60 mL). To the stirred suspension at room
temperature was added (4 min) a solution of 2,4,6-trimethyl-
s-triazine (6.41 g, 52.0 mmol) in glyme (20 mL). After being
stirred for 1.5 h, the suspension was added to a solution (0
°C) of allyl bromide (6.32 g, 52.2 mmol) in glyme (100 mL).
The reaction mixture was stirred overnight and then worked
up as described for the preparation of 5b. Distillation of the
liquid residue afforded 2.1 g (25% yield) of crude product: bp
66-102 °C (0.30 Torr). A portion (1.13 g) of the crude product
was placed on neutral alumina (1.5 cm × 22 cm), and elution
with 10% ether/pentane gave initially the gem-diallyl prod-
uct,38 as indicated by GLC and NMR results, followed by the
monoallyl product (4): bp 78 °C (2.1 Torr); IR (neat) 3085,
1640, 1530, 905 cm-1; 1H NMR (CDCl3) δ 2.50 (m, overlapping
s, 2H), 2.54 (s, 6H), 2.83 (t, 2H), 4.92 (dt, J ) 11, 2, 0 Hz, 1H),
5.00 (dt, J ) 18, 2, 0 Hz, 1H), 5.80 (ddt, J ) 18, 11, 9 Hz, 1H);
13C NMR (CDCl3) δ 25.8, 37.9, 47.9, 116.8, 136.0, 176.0, 180.8.
Anal. Calcd for C9H13N3 (Mr ) 163.22): C, 66.23; H, 8.03; N,
25.74. Found: C, 66.17; H, 8.22; N, 25.92.
18 h, the standard workup afforded 0.65 g of liquid residue:
1H NMR (CDCl3) δ 0.94 (t, 3H), 1.75 (m, 2H), 2.55 (s, 6H), 2.70
(t, 2H); GLC 5b 83% (0.54 g, 81 mol %), cis-1,5-cyclooctanediol
11%, 1-(4,6-dimethyl-s-triazin-2-yl)-1,2-epoxypropane 3%. Fur-
ther extraction of the ethanol phase gave additional amounts
of the diol and the epoxide: 1H NMR (CDCl3) δ 1.45 (d, J )
5.5, 0.0 Hz, 3H), 2.58 (s, 6H), 3.36 (m, J ) 5.5, 1.8 Hz, 1H),
3.62 (d, J ) 1.8, 0.0 Hz, 1H); MS m/z (relative intensity) 166
(M + 1, 8), 150 (62), 124 (15), 83 (22), 68 (34), 55 (73), 42 (100),
28 (47), 15 (16). An oxidative workup of a comparable reaction
(1.10 mmol of 1b, 1.09 mmol of 9-BBN-H) using CH2Cl2
extractions afforded 149 mg (95%) of crude diol which gave
crystals: mp 72-73 °C (lit.40 mp 73.5-74.3 °C).
A comparable hydroboration-oxidation of 1b with 9-BBN-H
in refluxing THF (17 h) gave a lower yield (50%, distilled) of
5b but no evidence of 2b or 3b.
Hyd r obor a tion -Hyd r olysis of 1b w ith 9-BBN-H. The
above general procedure9 for the hydroboration-oxidation was
followed in which 1b (658 mg, 4.41 mmol) was reacted (44 h)
with 9-BBN-H (10.2 mL, 4.90 mmol) in hexane except that
the addition of 30% H2O2 was omitted in the workup and only
absolute EtOH (1 mL) and water (3 mL) were added. The
mixture was stirred at room temperature for 1 h and saturated
with NaCl. The reaction mixture was worked up as above, and
the hexane extracts afforded 1.58 g of liquid residue. Flash
distillation of the latter afforded 694 mg of distillate. NMR
analysis: 5b, 69% (72 mol % yield); 1b, 9% (10 mol %);
cyclooctanone, 22% (25 mol %).
In a reaction comparable to the above, 1b (626 mg, 4.20
mmol) was reacted (21 h) with 9-BBN-H (9.6 mL, 4.6 mmol),
except that CD3OD (1 mL) and D2O (3 mL) were used in the
workup. Distillation of the product afforded 457 mg of distil-
late. NMR analysis: 5b, 64% (46 mol %); 1b, 11% (8 mol %);
cyclooctanone, 24% (19 mol %); 5b 1H NMR (CDCl3) δ 0.94 (t,
3H), 1.76 (m), 2.55 (s, 6.1H), 2.71 (broad m, 1.3H, triazinyl-
CHD-).
Oxym er cu r a tion -Dem er cu r a tion of 1a . The general
procedure of Brown was followed39 (caution: mercuric acetate
and mercury are highly toxic; see MSDS’s for handling and
disposal). To a stirred solution of mercuric acetate (0.72 g, 2.3
mmol) in water (2.3 mL) at room temperature was added THF
(2.5 mL) followed by 1a (0.31 g, 2.3 mmol). After 3.5 h the
yellow color had disappeared. The solution was stirred (18 h),
and then 3 M sodium hydroxide (2.3 mL) was added followed
by 0.5 M NaBH4 in 3 M NaOH (2.15 mL). After coagulation of
the mercury, the aqueous phase was saturated with NaCl, the
phases were separated, and the aqueous phase was ex-
tracted with CH2Cl2. The combined organic phases were dried
(MgSO4), the solvent was evaporated, and the liquid residue
was flash distilled: bp 80-120 °C (0.1 Torr) (lit.34 bp 89 °C
(1.5 Torr)) to give 0.20 g (57%) of 2a : IR (neat) 3360, 1530,
1
1045 cm-1; H NMR (CDCl3) δ 2.61 (s, 6H), 3.08 (t, 2H), 3.5
(bs, 1H), 4.07 (t, 2H). Its spectroscopic data was comparable
to an authentic sample used to prepare 1a .
Hyd r obor a tion s of 1b w ith 9-BBN-H in Hexa n e w ith -
ou t Oxid a tion or Hyd r olysis. The above general procedure
for the hydroboration-oxidation was followed in which 1b (462
mg, 3.09 mmol) was reacted (7 days) with 9-BBN-H (6.6 mL,
3.3 mmol) in hexane at room temperature. The volatiles and
products were distilled (100 °C (bath), 0.3 Torr) to leave a
viscous golden residue. The distillate was treated with MgSO4,
filtered, and concentrated to afford a liquid residue (209 mg).
NMR analysis: 5b, 52% (23 mol %), 1b, 23% (10 mol %),
cyclooctanone, 26% (13 mol %). The golden residue (917 mg)
remaining after the distillation was analyzed by GC-MS: 5b,
45% (88 mol %); cyclooctanone, 16%; cyclooctanol, 12%;
unidentified products, 28%; a minor amount of 7b (m/z 271).
The reaction of 1b (74 mg, 0.50 mmol) in a prepared solution
of 9-BBN-H (66 mg, 0.54 mmol) in CDCl3 (0.7 mL) was carried
out in a sealed tube at room temperature for 59 days, and then
bibenzyl (30.2 mg, 0.17 mmol) was added as a quantitative
NMR reference to indicate a 56% yield of 5b (71%, corrected
for unreacted 1b).
Hyd r obor a tion of 1b w ith 9-BBN-H in CDCl3 w ith ou t
Oxid a tion or Hyd r olysis. A solution of 1b (100 mg, 0.67
mmol) and 9-BBN-H dimer (92 mg, 0.38 mmol) in CDCl3 (1.1
mL) was prepared under argon in a sealed NMR tube. After
41 days (1H NMR analysis: 5b, 93%; 1b, 7%; cyclooctanone,
0%) the NMR tube was opened and the solvent was removed
under house vacuum to afford 293 mg (152%) of a viscous
reddish-brown liquid which was triturated with pentane (1 ×
1 mL, 2 × 0.5 mL) to afford a pentane solution and a light
orange-yellow powder (93 mg) which gave a faint green color
and a black residue upon ignition. NMR (DMSO-d6) analysis:
5b, 56%; cyclooctanone, 44%. The pentane extract was ana-
lyzed via GLC to give 79% 5b and 21% cyclooctanone. The
pentane extract was permitted to evaporate slowly over a
period of 2 months to afford crystals and a mother liquor. GC-
MS: 5b, 44%; cyclooctanone, 31%; the latter gave a 2,4-DNP,
Oxym er cu r a tion -Dem er cu r a tion of 1b. The general
procedure of Brown was followed.39 To a stirred solution of
mercuric acetate (0.95 g, 3.0 mmol) in water (2.8 mL) at room
temperature was added THF (2.8 mL) followed by 1b (0.42 g,
2.8 mmol). After 2 h the yellow color had disappeared. The
solution was stirred (42 h), and then 3 M NaOH (2.8 mL) was
added followed by 0.5 M NaBH4 in 3 M NaOH (2.8 mL). The
reaction was worked up as described for the hydration of 1a
to afford 0.43 g of product consisting of a liquid and a low
melting solid. After the mixture was homogenized by warming,
GLC analysis indicated the product composition to be 55%
alkene and 39% alcohol. Upon cooling of the product, the solid
alcohol was isolated, and its NMR spectrum was that of 2b.
GLC and NMR results gave no detectable evidence of the
isomeric alcohol. Repeating the stoichiometry of the above
reaction but with heating (53 °C) for 2 days did not signifi-
cantly change the alkene/alcohol ratio. Repeating the reaction
at room temperature for 2 days with a 2:l mole ratio of
mercuric acetate to alkene gave a product composition of 29%
1b and 68% 2b, and further increasing the ratio to 3:l gave
12% 1b and 78% 2b.
Hyd r obor a tion -Oxid a tion of 1a w ith 9-BBN-H. The
general procedure of Brown was followed.9 Neat 1a (164 mg,
1.21 mmol) was added via syringe to a refluxing solution (2.9
mL) of 9-BBN-H (1.4 mmol) in hexane under argon. After 23
h, the standard workup afforded 194 mg of liquid residue: 1H
NMR (CDCl3) δ 1.28 (t, 3H), 2.52 (s, 6H), 2.77 (q, 2H), small
signals due to the primary alcohol; GLC 5a 53% (103 mg, 62
mol %), 2a 10% (19 mg, 10 mol %), cis-1,5-cyclooctanediol and
cyclooctanone 37% (71 mg).
Hyd r obor a tion -Oxid a tion of 1b w ith 9-BBN-H. The
general procedure of Brown was followed.9 Neat 1b (664 mg,
4.45 mmol) was added via syringe to a refluxing solution (11.0
mL) of 9-BBN-H (5.28 mmol) in hexane under argon. After
(38) Osborne, D. R.; Levine, R. J . Heterocycl. Chem. 1964, 1, 128-
129.
(39) Brown, H. C.; Lynch, G. J . J . Org. Chem. 1981, 46, 531-538.
(40) Knights, E. F.; Brown, H. C. J . Am. Chem. Soc. 1968, 90, 5280-
5281.

3210 J . Org. Chem., Vol. 67, No. 10, 2002
Nyquist et al.
mp 172-173 °C (lit.41 mp 171-172 °C). The former crystals
gave a broad melting point: 70f300 °C, with gas evolution
between 125 and 140 °C. Similar crystals for X-ray diffraction
studies25 were obtained by slow evaporation (∼14 months) in
air of a solution of the above reaction contained within a
cracked NMR tube. A portion (24 mg) of the above powder was
oxidized with H2O2 by the standard procedure to afford 15 mg
of products. GLC analysis: 5b, 29%; cyclooctanone, 47%; cis-
1,5-cyclooctanediol, 24%.
for the three compounds relative to nonane as an internal
reference (100). GC-MS (compound (ratio %)) of oxidative
workup of the reaction gave the following results: nonane (100)
(some loss in workup); 5b (98); 1b (18); epoxide (14); cyclooc-
tanone (30); cyclooctanol (123); 1,5-cyclooctanediol (170).
(4) The 11B and 1H NMR (CDCl3) method is as follows. A
solution of 9-BBN-H dimer (189 mg, 0.77 mmol) in CDCl3 (3
mL) was prepared under argon in a 10 mm quartz NMR tube,
and the latter was equipped with a septum. After performing
the 11B and the 1H NMR spectra of the 9-BBN-H solution,
the alkene 1b (239 mg, 1.6 mmol), dissolved in an equal volume
of CDCl3, was added via syringe to the NMR tube, and the
latter was shaken. The solution was kept at room temperature,
and the 11B and 1H NMR spectra were taken at appropriate
intervals over a period of 9 days and then again after 29 days.
The 11B spectrum was also taken of a comparable solution in
a sealed standard NMR tube after 10 months to give the same
chemical shift (δ +59.622). Results are reported in the text and
in Table 3. Control spectra were taken on solutions of
9-BBN-H in CDCl3 with both cyclohexene and 2,4,6-trimethyl-
s-triazine.
Qu en ch in g of Ad d u ct 7b w ith CD3OD. A solution of 1b
(97 mg, 0.65 mmol) and 9-BBN-H dimer (79 mg, 0.33 mmol)
in CDCl3 (1.0 mL) was prepared under argon in an NMR tube
with a septum cap. After the signals from the adduct 6b were
maximized and those from 1b and 5b were still small (70 h),
26 µL (0.64 mmol) of methanol-d4 was added. As a result,
within the 1H NMR spectrum the broad triplet (δ 3.0, -CHB-)
became a multiplet (δ 2.65, -CHD-) and the broad multiplet
of the 9-BBN moiety (δ 1.03-1.25, 1.45-1.83) shifted down-
field (δ 1.10-1.32, 1.51-1.85) with an accompanying change
in its profile. A solution of bibenzyl (83 mg) in CDCl3 (0.5 mL)
was injected as an internal reference to determine the yield
of 5b-d1 (104%).
Rep r esen ta tive Hyd r obor a tion Rea ction s of Alk en es
w ith 9-BBN-H for Exten d ed P er iod s of Tim e. The fol-
lowing examples are representative methods for the prepara-
tion of hydroboration reactions carried out for extended periods
of time (Tables 3 and 4). At the conclusion of the reaction the
NMR tube or ampule was opened and equipped with a septum
if quenching, or further analyses or reactions were performed.
(1) A solution of 1b (92 mg, 0.62 mmol) and 9-BBN-H dimer
(83 mg, 0.34 mmol) in CDCl3 (1.2 mL) was prepared under
argon in a sealed NMR tube and kept at room temperature.
The 1H and 13C NMR spectra were taken at appropriate
intervals over a period of approximately 50 days after which
there were essentially no changes. The results are given in
Table 3. A DEPT spectrum showed the small signals from δ
60 to 150 to be sp2 carbons. With the addition of water the
1
eight small signals in the H NMR spectra (Table 3, footnote
e) disappeared, the 9-BBN signal contracted, and the integra-
tion areas for the methyl groups of the ring and the R-meth-
ylene group increased (∼0.6-0.7H, and ∼0.2H, respectively).
Within the 13C NMR all of the peaks between δ 60 and 150
disappeared.
Repeat of the above reaction at 60 °C gave identical results
within 5 days.
A comparable run (room temperature) quenched with CH3-
OD gave a 13C NMR spectrum showing C-D coupling at δ 25.2
Eth a n ola m in e Ester of th e 9-BBN Moiety.24 A solution
of 1b (98 mg, 0.66 mmol) and 9-BBN-H dimer (95 mg, 0.39
mmol) was prepared in C6D6 (1.1 mL) under argon in a sealed
NMR tube. The 1H and 13C NMR spectra were taken at
appropriate intervals to give spectral changes comparable to
those obtained in other deuterated solvents (CDCl3, CD2Cl2,
THF-d8). After 11 months, the tube was opened, 47 µL (0.78
mmol) of ethanolamine was added, and the precipitate was
filtered, washed with hexane, and dried (1 Torr) to afford 0.13
g (91%) of the ethanolamine ester of 9-BBN with recrystalli-
zation (THF-hexane): mp 203-205 °C dec (lit.24b mp 202-
203.5 °C).
1
1
(t, J ) 19.6 Hz) and δ 40.5 (t, J ) 19.5 Hz) for ring methyl
and R-methylene carbons, respectively.
(2) To a prepared solution of 9-BBN-H dimer in degassed,
purified hexane (2.5 mL, 0.40 M) at 55 °C in a 5 mL ampule
containing a stirrer was added, under argon, a solution of 1b
(147 mg, 0.98 mmol) and nonane (130 mg, 1.02 mmol) in
purified hexane (0.5 mL). The ampule was cooled under argon,
sealed, and heated at 55 °C for 57 days after which it was
opened in an argon-filled glovebag and equipped with a
septum. Samples were withdrawn via
following.
a syringe for the
(a) GC-MS (compound, m/z (ratio %)): nonane, 128 (100);
5b, 150-152 (40); cyclooctanone, 126 (3); 1b, 148-151 (12);
7b, 271 (63); bis ether, 258 (35); 5b dimer, 300 (5).
(b) GC-MS (compound, m/z (ratio %)) of CH3OD quench:
nonane, 128 (100); 5b, 150-155 (82); cyclooctanone, 126 (3);
1b, 148-151 (7); 9-BBN-OCH3, 151-154 (62). Additional time
gave no further incorporation of deuterium.
(c) GC-MS (compound, m/z (ratio %)) of CH3OH quench:
nonane, 128 (100); 5b, 150-152 (79); 1b, 148-151 (7); 9-BBN-
OCH3, 151-154 (81).
Hyd r obor a tion of 1b w ith 9-BBN-H in THF . To a
stirred refluxing solution (2.1 mL) of 9-BBN-H (1.0 mmol) in
THF was added 1b (154 mg, 1.03 mmol). Reflux was continued
for 55 h during which GC-MS samples were taken at appropri-
ate intervals. After approximately 1 day the peak areas of 5b
(34) and 1b (26) remained constant relative to bibenzyl (186
mg, 1.02 mmol) as an internal reference (100). Comparative
quenching with CH3OD and CH3OH followed by GC-MS
showed evidence of deuterium incorporation into 5b and the
cyclooctanone.
(d) GC-MS (compound, m/z (ratio %)) of H2O quench:
nonane, 128 (100); 5b, 150-152 (67); cyclooctanone, 126 (5);
1b, 148-151 (10); bis ether, 258 (90).
Hyd r obor a tion of 1b in th e P r esen ce of Ga lvin oxyl.28
A solution of 1b (86 mg, 0.58 mmol) and 9-BBN-H dimer (70
mg, 0.29 mmol) in CDCl3 (0.8 mL) was prepared under argon
in a NMR tube with a septum cap. The reaction was followed
(e) Titration: 0.05 M in 9-BBN-H.
(f) GC-MS (compound, m/z (ratio)) of oxidative workup
(H2O2): nonane, 128 (100); 5b, 150-152 (66); 1b, 148-151 (4);
cis-diol, 116 (M-CO) (46).
1
by H and 13C NMR until the adduct 7b had maximized, and
then solutions of galvinoxyl (recrystalized) in CDCl3 were
added as follows: 31 h, 29 mg (12 mol %); 51 h, 13 mg (5 mol
%); 70 h, 27 mg (11 mol %). A plot of the logarithm of the ratio
of the area of the methyl groups of the ring of 5b to that of
the adduct versus time showed no significant change relative
to that of a control with no galvinoxyl until after approximately
90 h when the reaction rate slowed dramatically. A control
with galvinoxyl and 9-BBN-H dimer in CDCl3 at room
temperature in the dark decolorized within 1 h.
(3) To a stirred solution under argon at room temperature
of 9-BBN-H in hexane (3.3 mL, 1.6 mmol) in a conical vial
equipped with a septum was added 1b (219 mg, 1.47 mmol)
and nonane (160 mg, 1.25 mmol). The vial was kept in an
argon atmosphere, and within 1 h an unidentified precipi-
tate began to form. Following the reaction for 4 months with
GC-MS showed, with time, a decrease in 1b, an increase in
5b, a maximum for 7b at ∼4 days, and an average sum of 97
Hyd r obor a tion of 1b-d 6 w ith 9-BBN-H. A solution of 1b-
d6 (58 mg, 0.37 mmol) and 9-BBN-H dimer (50 mg, 0.20 mmol)
in CDCl3 (0.6 mL) was prepared under argon in a sealed NMR
(41) Dictionary of Organic Compounds, 5th ed.; Buckingham, J ., Ed.;
Chapman & Hall: New York, 1984; Suppl. 2, p 120. Ohtsuka, Y.; Oishi,
T. Chem. Pharm. Bull. 1983, 31, 454-465; Chem. Abstr. 1983, 99,
121863m.
1
tube. The H and 13C NMR spectra were taken at appropriate
intervals, and after 63 days the residual hydrogen content of

2-(1-Alkenyl)-4,6-dimethyl-s-triazines
J . Org. Chem., Vol. 67, No. 10, 2002 3211
the methyl groups on the ring (δ 2.55, m, J ) 2.2 Hz) had
decreased and the signal for the R-hydrogen had increased to
a sharp triplet (δ 2.72, J ) 7.5 Hz) superimposed upon a broad
triplet of triplets (3J ) 7.4, 2J ) 2.3 Hz42) with the relative
areas ∼2:1, respectively. The absolute changes in the areas of
the signals were within the integration precision.
between δ 4.0 and δ 4.8 had disappeared as well as those
signals in the 13C NMR spectrum between δ 60 and δ 160.
Hyd r obor a tion -Oxid a tion of 4 w ith 9-BBN-H. The
general procedure of Brown was followed.9 Neat 4 (904 mg,
5.54 mmol) was added via syringe to a refluxing solution (18.5
mL) of 9-BBN-H (8.88 mmol) in hexane under argon. After
18 h, the standard workup was followed except that further
hexane and ether extractions were necessary to afford 1.15 g
of liquid residue. GLC: 4-(4,6-dimethyl-s-triazin-2-yl)-1-bu-
tanol, 52% (60 mol %); recovered alkene 4, 1%; cis-1,5-
cyclooctanediol, 40%; unidentified components, 7%. The NMR
spectrum gave no evidence for 4-(4,6-dimethyl-s-triazin-2-yl)-
2-butanol. Lowering the mole ratio of 9-BBN-H to alkene from
that cited above (1.6:1.0) to a ratio of 1:1 gave a 43 mol % yield
of the primary alcohol, but raising the ratio to 2.2:l.0 did not
improve the yield (58 mol %). The product was placed on
neutral alumina (1 cm × 24 cm), and after elution with ether,
the 4-(4,6-dimethyl-s-triazin-2-yl)-1-butanol was eluted with
2% methanol/ether followed closely by the cis-1,5-cyclooc-
tanediol. Selected cuts were combined and distilled to afford
200 mg of alcohol: bp 112-124 °C (0.53 Torr); IR (neat) 3370,
Hyd r obor a tion of 1b-d 7 w ith 9-BBN-H. A solution of 1b-
d7 (32 mg, 0.21 mmol) and 9-BBN-H dimer (46 mg, 0.19 mmol)
in C6D6 (0.6 mL) was prepared under argon in a sealed NMR
1
tube. The H and 13C NMR spectra were taken at appropriate
1
intervals, and after 1 day the H NMR continued to show, for
a period of 4 months, the gradual decrease in both the weak
broad triplet at δ 3.15 (R-CHB-) and the weak multiplet at δ
2.4 (ring methyl groups) and the simultaneous increase of the
3
2
broad multiplet at δ 2.8 (R-CDH-, ∼0.8H, J ) 7.5, J ) 3.2
Hz42). The differences between the absolute changes in the
areas of the signals were within the integration precision.
ESR of Rea ction of 7b to 5b. A solution of 1b (89 mg,
0.60 mmol) and 9-BBN-H dimer (77 mg, 0.63 mmol) in C6D6
(0.9 mL) was prepared under argon in a sealed NMR tube.
After the 1H NMR spectra showed that adduct 7b had fully
formed and the signal for the R-methylene group was apparent
(∼5 days), the ESR spectrum was taken with no evidence of a
signal. The ESR spectra were repeated after 21 days and again
after 3 months with no detectable signal.
1
1525, 1035 cm-1; H NMR (CDCl3) δ 1.61 (quintet, 2H), 1.86
(quintet, 2H), 2.25 (s, 1H), 2.58 (s, 6H), 2.80 (t, 2H), 3.65 (t,
2H); 13C NMR (CDCl3) δ 24.1, 25.6, 32.2, 38.4, 62.0, 176.1,
179.0; MS m/z (relative intensity) 150 (M+ - CH2OH, 9), 136
(13), 123 (59), 42 (100), 31 (8). Anal. Calcd for C9H15N3O (Mr
) 181.24): C, 59.64; H, 8.34; N, 23.18. Found: C, 59.25; H,
8.45; N, 22.91.
Hyd r obor a tion of 2-Vin ylp yr id in e. A solution of 2-vi-
nylpyridine (60 mg, 0.57 mmol) and 9-BBN-H dimer (78 mg,
0.32 mmol) (1:1 monomer) in CDCl3 (0.8 mL) was prepared
under argon in a sealed NMR tube and permitted to stand at
room temperature. The 1H and 13C NMR spectra were taken
at appropriate intervals. Within 20 h the 1H NMR showed new
signals at δ 0.57 (b), 0.83 (t), 2.92 (t), and increased multiplicity
of the signals from the ring protons. The former three signals
of equal areas continued to increase for ∼6 days, and then the
tube was heated for 11 days at ∼55 °C until the signals for
the alkene protons disappeared, but there was no significant
changes in the remaining signals.
Hyd r obor a tion -Oxid a tion of 1c w ith 9-BBN-H. The
general procedure of Brown was followed.9 Neat 1c (725 mg,
4.44 mmol) was added via syringe to a refluxing solution (9.0
mL) of 9-BBN-H (4.5 mmol) in hexane. After 19 h, the
standard workup afforded 712 mg of liquid residue. GLC
(NMR) analyses: 5c, 78% (75 mol %); 1c-epoxide, 22% (21 mol
%); cis-1,5-cyclooctanediol (56 mol %). A portion (779 mg) of
the liquid residue from a comparable run was placed on 80 g
of neutral alumina. Elution with 10% ether/pentane afforded
161 mg of alkane 5c after distillation: bp 74 °C (4.3 Torr); IR
and NMR spectra identical to those of an authentic sample of
5c. Elution with 100% ether afforded, after distillation, 166
mg of 2-methyl-1-(4,6-dimethyl-s-triazin-2-yl)-1,2-epoxypro-
pane: bp 80-86 °C (1.2 Torr); IR (neat) 1525, 1240, 900 cm-1
;
1H NMR (CDCl3) δ 1.25 (s, 3H), 1.50 (s, 3H), 2.60 (s, 6H), 3.83
(s, 1H, no exchange with D2O); 13C NMR (CDCl3) δ 17.7, 24.9,
25.6, 62.2, 63.0, 173.5, 176.2; MS m/z (relative intensity) 179
(M+, 2), 162 (6), 138 (20), 97 (23), 69 (13) 42 (100). Anal. Calcd
for C9H13N3O (Mr ) 179.22): C, 60.32; H, 7.31; N, 23.45.
Found: C, 60.05; H, 7.33; N, 23.05.
A solution of 2-vinylpyridine (48 mg, 0.45 mmol) and
9-BBN-H dimer (118 mg, 0.48 mmol) (1:2 monomer) in CDCl3
(1.2 mL) was prepared and analyzed as above to give an initial
spectrum which had broadened signals for the hydrogens of
the 2-vinylpyridine but gave final 1H NMR spectra which were
the same as the above.
Hyd r obor a tion -Oxid a tion of 1c w ith 9-BBN-D. The
general procedure of Brown was followed.9 Neat 1c (545 mg,
3.34 mmol) was added via syringe to a refluxing solution (15
mL) of 9-BBN-D43 (0.25 M,29 3.7 mmol) in hexane under ar-
gon. After 21 h, the standard workup afforded 635 mg of liquid
residue. GLC: 5c-d1, 65% (414 mg, 75 mol %); 1c-epoxide, 25%
(26 mol %). NMR analysis gave 71% and 29%, respectively.
A portion (380 mg) of the above residue was placed on
neutral alumina (l cm × 25 cm) and eluted with 2% ether/
pentane to afford 139 mg of 5c-d1: bp 75-78 °C (4.5 Torr); IR
Hyd r obor a tion of 2-(1-p r op en yl)p yr id in e. A solution of
2-(1-propenyl)pyridine44 (103 mg, 0.86 mmol) and 9-BBN-H
dimer (113 mg, 0.46 mmol) (1:1 monomer) in CDCl3 (1.1 mL)
was prepared under argon in a sealed NMR tube and permit-
ted to stand at room temperature. The 1H and 13C NMR
spectra were taken at appropriate intervals. Within 6 h a broad
singlet (δ 0.24) and a sharp triplet (δ 0.82) appeared. The
former remained relatively constant for 62 days, but the sharp
triplet decreased with time as a new triplet (δ 1.16) increased.
Concurrently with the appearance of the new sharp downfield
triplet, small multiplet signals began to appear between δ 4.5
and 6.3, and within the 13C NMR spectra new signals appeared
between δ 110 and 170. Heating the reaction (∼67 °C) for 7
days caused the remaining alkene to react and the broad
singlet and the initial sharp triplet to disappear. No evidence
for the formation of the alkane was apparent, but the addition
of a drop of water gave rise to the alkane: 1H NMR (CDCl3) δ
0.96 (t, 3H), 1.76 (m, overlaps 9-BBN), 2.78 (t, 2H), 7.10 (m,
1H), 7.15 (d, 1H), 7.59 (dt, 1H), 8.50 (dd, 1H).
1
(neat) 2960, 1530 cm-1; H NMR (CDCl3) δ 0.90 (s, 6H), 2.55
(s, 6H), 2.61 (s, 2H). Anal. Calcd for C9H14DN3 (Mr ) 166.25):
1
C, 65.02; H + /2D, 9.09; N, 25.28. Found: C, 65.22; H, 9.11;
N, 25.11. Elution of the column with pure ether afforded
approximately 50 mg of epoxide whose spectral data were
identical to an authentic sample.
Hyd r obor a tion of 1c-d 6 w ith 9-BBN-H. A solution of 1c-
d6 (79 mg, 0.47 mmol) and 9-BBN-H dimer (62 mg, 0.25 mmol)
in CDCl3 (0.7 mL) was prepared under argon in a sealed NMR
1
tube. The H and 13C NMR spectra were taken at appropriate
intervals. After 25 days, the sharp doublet (δ 2.61, 2R-H) in
A solution of 2-(1-propenyl)pyridine (63 mg, 0.53 mmol) and
9-BBN-H dimer (132 mg, 0.54 mmol) (1:2 monomer) in CDCl3
(1.2 mL) was prepared under argon in a sealed NMR tube.
The initial NMR spectrum was identical to that of the above
(1:1) except the signals for the ring protons were broadened.
Within 5 h the broad singlet (δ 0.25) and the sharp singlet (δ
0.84) appeared and the signals for the ring protons had become
1
the H NMR spectrum showed no increased multiplicity, and
the triplet at δ 2.16 (1â-H) was broadened. After 10 months,
the NMR tube was opened and water (1 drop) was added. The
1H NMR spectrum remained unchanged except that the profile
of the 9-BBN moiety had sharpened and the small signals
(42) Gu¨nther, H. NMR Spectroscopy-An Introduction; Wiley
Sons: New York, 1980; p 51.
&
(43) Midland, M. M.; Greer, S. Synthesis 1978, 845-846.
(44) J ohnson, A. W. J . Org. Chem. 1960, 25, 2237-2238.

3212 J . Org. Chem., Vol. 67, No. 10, 2002
Nyquist et al.
sharp. The 1H NMR spectra remained as such for 78 days with
no evidence of a new triplet at δ 1.15, the small multiplets
between δ 4.5 and 6.3, or the additional signals in the 13C NMR
spectra.
University, Northridge, CA. We wish to thank Ron J .
Hekier, Donna L. Mareno, David B. Nelson, and Albert
D. Penney for their preliminary experimental work and
acknowledge the fruitful discussions with Dr. Thomas
E. Cole and Dr. F. LeRoy Lafferty, Department of
Chemistry, San Diego State University. We also wish
to thank Dr. Kenneth I. Hardcastle, Department of
Chemistry, Emory University, for his crystallographic
analyses and encouragement, Dr. Walt Niemczura,
Department of Chemistry, University of Hawaii, for
Con tr ols w ith 9-BBN-H Dim er a n d 2,4,6-Tr im eth yl-
s-tr ia zin e. (a) A solution of 2,4,6-trimethyl-s-triazine (78 mg,
0.63 mmol), 9-BBN-H dimer (86 mg, 0.35 mmol), and bibenzyl
(146 mg, 0.80 mmol) as a reference in degassed CDCl3 (1.2
1
mL) was prepared under argon in a sealed NMR tube. The H
and 13C NMR spectra were taken at appropriate intervals for
51 days with no evidence of any change at room temperature.
Hydrolysis of an aliquot of the final solution gave 95% of the
original hydride molarity. (b) A solution (3.4 mL) of 9-BBN-H
(0.68 mmol) in THF was added (0 °C) with stirring to a mixture
of 2,4,6-trimethyl-s-triazine (81 mg, 0.66 mmol) and nonane
(87 mg, 0.68 mmol) under argon in an ampule, and the latter
was sealed. After 21 days at room temperature hydrolysis29
of an aliquot of the final solution gave 90% of the original
hydride molarity, and the GC-MS of a sample quenched with
CH3OD showed no incorporation of deuterium into the 2,4,6-
trimethyl-s-triazine. A comparable study carried out at 55 °C
for 28 days gave 26% of the original hydride molarity, but no
deuterium had been incorporated into the 2,4,6-trimethyl-s-
triazine.
1
performing the variable-temperature H NMR spectra,
and Dr. J ane Strouse, Department of Chemistry, UCLA,
for performing a 15N NMR spectrum.
Su p p or tin g In for m a tion Ava ila ble: 1H spectra for com-
1
pounds 1b-d6, 1b-d7, 2b-d9, and 1c-d6; H and 13C spectra for
1
compounds 1b, 5b, 2c, 5c, 1c, 2c-d6, and 4; H, 13C, and 11B
spectra for 1b with 9-BBN-H with time and final 15N spectra;
1
1
final H and 13C spectra for 1b-d6 with 9-BBN-H, and H and
13C spectra for 2(1-propenyl)pyridine with 9-BBN-H with time.
This material is available free of charge via the Internet at
http://pubs.acs.org.
Ack n ow led gm en t. We are pleased to acknowledge
the financial support provided by the California State
J O010784E