Journal of Chemical Ecology, Vol. 16, No.

12, 1990

REPLACEMENT OF CARCINOGENIC SOLVENT HMPA

BY DMI IN INSECT SEX PHEROMONE SYNTHESIS

CHI-CHU L O l and P E I - M I N C H A O

Pesticide Chemistry Department

Taiwan Agricultural Chemicals and Toxic Substances Research Institute (TACTRI)
Taiwan. R. O. C.

(Received February 26, 1990; accepted June 1, 1990)

Abstraet--Hexamethylphosphoric triamide (HMPA) is a good solvent for

the alkylation of terminal acetylenes; however, it has been proven to be a
carcinogen towards rats and should be considered as a serious risk to man
when a large-scale synthesis is involved. Thus the search for a safe alternative
is important. The physical properties of 1,3-dimethyl-2-imidazolidinone
(DMI) are similar to DMPU (1,3-dimethyl-2-oxo-hexahydropyrimidine) and
HMPA, but the potential toxicological risk of DMI is less than DMPU and
HMPA. When used in the alkylation of terminal acetylenes, DMI is com-
parable with HMPA, thus it is a good alternative solvent to the carcinogen
HMPA in the alkylation because it provides a safer working environment than
DMPU and HMPA.

Key Words--Smaller tea tortrix, Adoxophyes fasciata, (Z)-9-tetradecenyl

acetate, (Z)- 11-tetradecenyl acetate, ( E)- 11-tetradecenyl acetate, 10-methyl-
dodecyl acetate, hexamethytphosphoric tfiamide, 1,3-dimethyl-2-oxo-hex-
ahydropyrimidine, 1,3-dimethyl-2-imidazolidinone.

INTRODUCTION

M o s t insect sex attractants h a v e at least one l o n g straight chain ( C 1 0 - - C 1 6 ) alco-

hol or acetate with a d o u b l e b o n d ( A n d o et al., 1977) and are typically prepared
by a W i t t i g reaction b e t w e e n either an aliphatic o r f u n c t i o n a l i z e d nonstabilized
t r i p h e n y l p h o s p h o n i u m y l i d e and either an aliphatic or functionalized aldehyde.
T h e y also can be p r e p a r e d f r o m an acetylenic tetrahydropyranyl ether
[ T H P - - O - - ( C H 2 ) , ~ - - C ~ C - - (CH2) n - C H 3 , T H P = tetrahydropyran-2-yl]

To whom correspondence should be addressed.

3245

0098-033[/90/1200 3245506.00/0 9 1990 Plenum Publishing Corporation

 3246 Lo ANDCHAO

(Henrick, 1977) by selective reduction. These intermediates are prepared by the

alkylation of terminal acetylenes with alkyl halides. For example, (Z)-9-tetra-
decenyl acetate (Z9-TDA) and (Z)-I 1-tetradecenyl acetate (Zll-TDA) are sex
pheromones of the smaller tea tortrix Adoxophyes fasciata Walsingham (also a
serious tea pest in the northern part of Taiwan) and were generally synthesized
by a Wittig reaction (Tamaki et al., 1971).
However, the Wittig reaction is usually not as stereoselective as the alkyl-
ation route (Henrick, 1977), and our previous experiments also indicated that
the Wittig reaction can (under certain conditions) lead to a cis-trans mixture in
a 5 : 1 ratio (Lo et al., 1988). Further purification by liquid chromatography on
silica gel impregnated with 20 % silver nitrate could afford pure compound (95 %
active isomer) in low yield (less than 10%). Alkylation followed by partial
selective catalytic hydrogenation over Lindlar catalyst generally gave high yields
of the corresponding Z olefin (Henrick, 1977); therefore, the acetylenic route
was considered, but the yield and the time required for the alkylation varied
with reagents and solvent systems. For example, the classical alkylation pro-
cedure carried out in liquid ammonia gave a yield of 56.9%, with a reflux time
of 4-5 hr (Green et al., 1967), but this reaction was affected by the solubilities
of alkyl halides and metal 1-alkyn-l-ide in liquid ammonia and was not suc-
cessful with increased length of the (CH2) n chain (Warthen, 1968; Warthen and
Jacobson, 1968; Kochansky et al., 1975). The combination of HMPA with
tetrahydrofuran (THF) provided a good alternative (Schwarz and Waters, 1972;
Ando et al., 1977), and the alkylation was worked up within 30 min with a
yield of 85-92 %. However, a long-term inhalation toxicity study with rats indi-
cated that cancer emerged at levels as low as 400 ppb after eight months, and
50 ppb after 13 months, and a permissible airborne exposure limit of 0.5 ppb
was suggested (Schmutz, 1978). Consequently, HMPA must be considered as
a serious risk to man and should not be used when large-scale synthesis is con-
sidered. Thus the search for a safe substitute for HMPA is necessary.
The cyclic urea DMPU was reported to exhibit the same effects as HMPA
in oxirane opening with lithium acetylide, in a Wittig olefination, in the double
deprotonation of a nitroalkane, in the Michael addition of lithiodithiane to
cyclohexenone, and in selective generation of certain enolates (Mukhopadhyay
and Seebach, 1982). DMPU also can replace HMPA in stereoselective alkyla-
tions of chiral c~-nitro keto imine dianions (Denmark and Ares, 1988). The
possible usage of DMPU in insect sex pheromone synthesis was not reported
until 1988, and it proved to be a better solvent then HMPA in the coupling
reaction of an alkyne, or a functionalized alkyne, with an alkyl halide (Bengts-
son and Liljefors, 1988). However, DMPU is a mutagen in the Drosophila
SLRL (sex-linked recessive lethal) test (Zijlstra and Vogel, 1988), indicating a
potential toxicological risk to man.
DMI is an aprotic basic solvent, and the physical properties are similar to
REPLACEMENT OF CARCINOGENIC SOLVENT 3247

H M P A (Table 1) (Normant, 1967; Barker et al., 1979). A preliminary Salmo-

nella mutagenic test based on the revised method of Maron and A m e s (1983)
showed a negative response (You, 1988).
A comparison of the mutagenic assay system was made o f 439 references
on selected carcinogens and noncarcinogens (Brown et al., 1979). Of the com-
pounds reviewed, 19 (90%) o f the 21 carcinogens and 3 (50%) o f the six non-
carcinogens were active in the Drosophila system, whereas 37 (84%) o f the 44
carcinogens and 2 (25 %) of the eight noncarcinogens were active in the Sal-
monella system; thus, the potential carcinogenic risk of D M P U should be noted.
Furthermore, the actue toxicity (CNS toxicity) o f D M I (LDso = 2840 mg/kg,
mice) was lower than D M P U (LDs0 = 1300 mg/kg, mice) (Lien and Kumler,
1968). Thus the use o f D M I should be considered safer than the use o f D M P U
on the basis of available toxicity data (Table 1).
Seebach et al. (1982) concluded that D M P U will become generally more
useful than D M I , because a heavy precipitate was observed below ca. - 3 0 ~
from a 2 : 1 mixture o f T H F and D M I , while a 2 : 1 mixture o f T H F and D M P U
was still clear and homogeneous at - 7 8 ~ The same is noted by Mukhop-
adhyay and Seebach (1982): they found that a 1 : 2 mixture o f D M P U with T H F
was clear and homogeneous down to - 9 0 ~
However, alkylation o f an 1 - a l k y n - l - i d e ion with a primary alkyl halide

TABLE 1. PHYSICAL AND TOXICOLOGICAL PROPERTIES OF DMI, DMPU, AND H M P A

DMI DMPU HMPA

bp (~ 220/754 230/754 235/760

mp (~ 8.2a < -20 7.20
Density (g/ml) at 25~ 1.0519 1.0596 1.0253
Viscosity (cP) at 25~ 1.944 2.934 3.5cS (60~ t'
Dielectric constant at 25~ 37.60 36.12 30 (20~
Dipole moment (Debye) 4.09 4.23 4.31-5.37 (25~
Toxicity
Acute (mice, mg/kg) 2840 1300 NA~'
Mutagenic
Salmonella system - NA NA
Drosophila system NA + NA
Carcinogenic (rat) NA NA +

aLaboratory studies showed that DMI (>99%, Tokyo Kasei Kogyo Co., Ltd.) was crystallized in
refrigerator at -10~ and started to melt at -4~ indicating the mp should be lower than
-4~
Laboratory studies using a Brookfield digital viscometer indicated the viscosity of HMPA was 4.8
cP at 19~
~Not available.
3248 Lo ANDCHAO

usually can be carried out at temperature of 0-25~ and the yields are usually
high (Schwarz and Waters, 1972; Brattesani and Heathcock, 1973; Henrick,
1977; Bengtsson and Liljefors, 1988; Brandsma, 1988). At this temperature
range, DMI will be a clear and homogeneous solvent (Table 1) and will be a
better choice than DMPU when safety is considered.
The use of DMI as a substitute solvent for HMPA has been reported only
in the preparation of trimethylsilylsodium and trimethylsilylpotassium (Sakurai
and Kondo, 1975), in the reaction of a trialkylchlorosilane with lithium (Sakurai
and Kondo, 1976), in the preparation of homoallylic alcohol derivatives
(Mukaiyama et al., 1980), in the dehydration and dehydrohalogenation of sat-
urated and unsaturated alcohols and dienyl halides (Spangler et al., 1981), and
in Ullmann ether synthesis (Oi et al., 1988). There is no report specifically on
use of DMI in pheromone synthesis. Therefore, we report here the alternative
alkylation route in the syntheses of insect sex pheromones of Z9-TDA and Z 11-
TDA of the smaller tea tortrix, and the first use of DMI instead of DMPU and
HMPA during the organometallic reaction in the syntheses of sex pheromones.

METHODS AND MATERIALS

DMI ( > 9 9 % ) was purchased from Tokyo Kasei Kogyo Co., Ltd., and
was stored in serum-capped bottles under nitrogen over 4.~ molecular sieves.
Gas-liquid chromatography (GLC) analysis was performed on the syn-
thetic materials with an Hewlett Packard 5890 equipped with a flame ionization
detector (FID). A glass column of 3 % OV-1 on 80-100 Chromosorb W HP, 2
mm x 1.8 m was used for analysis of the synthetic intermediates with the initial
oven temperature at 160~ (1 min), then programmed to 240~ (8~ A
glass column of OV-275 on 80-100 Chromosorb W AW was used to analyze
the final synthetic pheromones; the initial oven temperature was 150~ (1 min),
then programmed to 220~ (4~ Nitrogen was used as carrier gas at the
rate of 29.9 ml/min, and air and hydrogen flows were set as recommended for
FID.
GC-MS measurements were recorded on an Hewlett-Packard 5890A GLC
combined with a 5970B mass selective detector (EI, 70 eV). Infrared data were
obtained with a Perkin Elmer 567 infrared spectrophotometer, and IH nuclear
magnetic resonance data were obtained with a Varian VXR-300 spectrometer.
14-(2- Tetrahydropyranyloxy)-3-tetradecyne (IIa) , and 14-(2- Tetrahydro-
pyranyloxy)-5-tetradecyne (lib). To a stirred solution of the co-tetrahydropyr-
anyloxy-l-alkyne (Ia, or Ib, 23 mmol) in dry solvent A (23 ml, Table 2) at 0~
under nitrogen atmosphere, n-butyllithium (n-BuLi, 1.6 M in hexane, 21.5 ml,
34.4 mmol) was added dropwise. The reaction mixture was stirred for 15 min.
The alkyl bromide (34.5 mmol) in dry solvent B (40 ml, Table 2) was added
REPLACEMENT OF CARCINOGENIC SOLVENT 3249

TABLE 2. PREPARATION OF YNYL TETRAHYDROPYRANYL ETHERS (IIa, IIb) ~

Yield (%) in 2
Solvent b hr'

A B Ila IIb

THF THF 8 8
HMPA HMPA 78 88
DMI DMI 83 90
THF HMPA 78 75
THF DMI 88 75

aCompounds were purified with AgNo 3 solution, and GLC analyses and consistent spectra were
obtained for all compounds.
bco-Tetrahydropranyloxy-l-alkyne (Ia and Ib) was added in dry solvent A, and alkyl bromide was
added in dry solvent B.
CBased on 1-alkynyl tetrahydropyran-2-yl ether (Ila and IIb) starting materials.

slowly. The resulting solution was stirred for 15 min at 0~ and then stirred
for an additional 2 hr at room temperature. The reaction mixture was worked
up within 30 min by pouring into 200 ml ice water and extraction with hexane
(3 x 200 ml). The combined organic fractions were washed with water, brine,
and dried (MgSO4). The solvent was removed using a rotary evaporator to afford
the crude ynyl tetrahydropyranyl ethers (IIa, IIb) (Figure 1).
Subsequent purification by treating with 1.7% silver nitrate solution (in
ethyl alcohol) was applied to remove the unreacted terminal alkynes (Ia, Ib).
The unreacted terminal alkyne formed a white precipitate with silver nitrate,
while the yellow ynyl tetrahydropyanyl ether (IIa, IIb) remained in solution and
could be collected by filtration. The white precipitate (metal acetylide) could
explode when dry, therefore, the precipitate was treated with 65 % nitric acid
solution to recover the unreacted tetrahydropyranyl ethers (Ia, Ib). The purifi-
cation was unnecessary when the yield was higher than 90%.
1.7% AgNO3
THP--O-- (CH2) m-C=- CH ) THP--O-- (CH2) m- C~ CAg
Ia, b (precipitated)
65% HNO3
THP--O--(CH2)m--C~-CH + AgNO3
(recovered) (precipitated)

(Z)-ll-Tetradecen-l-ol (IVa), and (Z)-9-Tetradecen-l-ol (IVb). The

tetrahydropyranyl ether IIa or IIb (18.7 mmol) was converted to the correspond-
ing alcohol by treatment for 3 hr with p-toluenesulfonic acid (p-TsOH, 10.6 g)
in refiuxing methanol (300 ml) in yields of 90% for IIIa, and 92% for IIIb.
Subsequent partial hydrogenation followed, and a solution of the IIIa or
3250 Lo A N D CHAO

I. n-BuLi
2. ~H3- (CH2)n-Br
THP-O- ( CH2 ) m-C---CH THP-O-(CH2)m-C~zC-(CH2)n-CII3
la,b 80-90 % lla,b
la, re=t0 lla, m=10, n=l
Ib, m=8 llb, m=8, n=3

~-TsOH/MeOH H2/Lindlar Catalyst

9> HO-(CH2)m-C~C-(CH2)n-CH 3
90-92% 85-95%
llla,b

HO-(CH2)m~c=C~ (CH2)n-CH3 Ac20/Pyr

H H 80-85%
IV a~b

AcO- (CH2 ) m~C=C ~ ( CH2 ) n-CH3

H H
Va,b

FIG. 1. Synthesis of (Z)-11-tetradecen-l-yl acetate (Va) and (Z)-9-tetradecen-l-yl ace-

tate (Vb).

IIIb (16.8 mmol) in methanol (100 ml) was hydrogenated at room temperature
using a Lindlar catalyst (1.4 g) and quinoline (0.9 ml). When the required
amount of H2 for one double bond had been absorbed (403 ml at 760 mm), the
reaction was stopped. The catalyst was removed by filtration, the methanol was
evaporated at reduced pressure, and the residue was dissolved in ether. The
ether solution was washed with 5 % HC1, sat. aq. NaHCO3, water, and brine.
The ether solution was dried (MgSO4) and concentrated in a rotary evaporator
to give products IVa or IVb in yields of 85 % or 95 %, respectively.
(Z)-ll-Tetradecen-l-yl acetate (Va), and (Z)-9-Tetradecen-l-yl acetate
(Vb). A solution of IVa or IVb (14.8 mmol), acetic anhydride (Ac20, 14 ml),
and pyridine (Pyr, 12ml) was refluxed overnight, then poured into ice water
and neutralized with sat. aq. NaOH. The aqueous phase was extracted with
n-hexane and dried (MgSO4). The solvent was removed under vacumn, and the
residue was distilled to give colorless oily pheromone products of Va or Vb.
The physical data for these pheromones were as followed.
Va: bp 71.5-73.0~ torr (uncorrected); yield 80% (based on IVa);
purity 95%; MS(EI): m/e(%) 194 (M+'-AcOH, 8), 43(100); IR(KBr) 3008,
REPLACEMENT OF CARCINOGENIC SOLVENT 3251

2928, 2856, 1744(Co), 1654, 1464, 1366, 1238 (primary acetate), 1040, 720
(cis H C = C H ) ; NMR(CDC13/TMS): 0.95(t, 3H, CH3), 1.28[s, 22H, (CH2)11],
2.04(s, 3H, CH3CCOO), 4.05(t, 2H, CH2OAc), 5.30-5.36 (m, 2H, H C = C H ) .
Vb: bp 75.2-75.4~ torr (uncorrected); yield 85 % (based on IVb);
purity 94%; MS(EI): m/e(%) 194(M+-AcOH, 7), 43(100); IR(KBr) 3012,
2928, 2860, 1744(Co), 1656, 1468, 1366, 1240(primary acetate), 1040, 722
(cis H C = C H ) ; NMR(CDC13/TMS): 0.89(t, 3H, CH3), 1.30[s, 22H, (CH2)11],
2.04(s, 3H, CH3CCOO), 4.05(t, 2H, CH2OAc), 5.32-5.37(m, 2H, H C = C H ) .
Field Tests. Field testing was carried out in tea plantations in the Wenshan
Substation of the Taiwan Tea Experiment Station, from July 11 to August 8,
1989. The synthetic pheromones (0.01 mg) loaded in polyethylene tubes were
Z9-TDA, Zll-TDA, E ll-TDA, which was isomerized from Zll-TDA by
aqueous N a N Q and HNO3(Sonnet, 1974), and 10-methyldodecyl acetate
(unpublished result) in a ratio of 63 : 31 : 4 : 2 (Tamaki et al., 1979). Dispensers
were mounted at the center of the sticky wing traps.

RESULTS AND DISCUSSION

The alkylation in the DMI solvent systems was almost complete within 2
hr, and the yield was a little better than the alkylation in the HMPA system,
whereas the yield of alkylation in the THF system was very low, indicating that
alkyl bromides essentially do not react with lithium acetylide in THF. The yield
also was decreased when THF was used as a cosolvent of HMPA or DMI (Table
2); the low yield indicated that a good alkylation yield depends on the substrate
structure and solvent polarity.
The good results with DMI indicated that the preparation of sex phero-
mones by alkylation followed by hydrogenation not only gave good isomeric
purities, but also proved DMI could be a safe alternative solvent to HMPA in
insect sex pheromone synthesis, especially when large-scale synthesis was con-
sidered.
The total moth catch in the tea plantation was low unless the proportion of
each component was varied (S.N. Hsiao, 1989, unpublished results, Wenshan
Substation of the Taiwan Tea Experiment Station. In one of her field tests, she
found that the total moth catch could be increased significantly by varying the
proportion of each component to 47 : 50 : 1 : 2), indicating that the best phero-
mone formulation for the smaller tea tortrix was not established in Taiwan, and
further research on the pheromone proportion of 14 : 6 : 1 : 2 (Tamaki et al., 1979)
or other possible proportion combinations should be considered.
Our report has led to the conclusion that if a reaction could be conducted
at a temperature higher than 0~ use of DMI should be considered. We also
believe that DMI will become a more favored solvent than DMPU and HMPA
in the future.
 3252 Lo AND CHAO

Acknowledgments--This study was supported by a grant from the Chinese National Science
Council (NSC 77-0409-B086-01). Thanks are due to Miss Hsiao Suh-Neu for field tests.

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