Microwave catalyzed reactions of H-dimethylphosphonate with oxiranes

Article abstract of DOI:10.1080/10426500210221

Microwave catalyzed reactions of H-dimethylphosphonate with 1,2-epoxydecane, 5,6-epoxy-1-hexene, 1,2-epoxybutane and cyclohexene oxide have been found to cause oxirane ring opening, deoxygenation and hydrophosphorylation. 1,2-Epoxydecane gave three pairs

Full text of DOI:10.1080/10426500210221

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Phosphorus, Sulfur, and Silicon and the Related
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Microwave Catalyzed Reactions of H-
Dimethylphosphonate with Oxiranes
S. Munavalli a , D. K. Rohrbaugh b , F. J. Berg b , F. R. Longo a & H. D. Durst b
a Geo-Centers, Inc. , PO Box 68, Gunpowder Branch, APG, MD, 21010
b U.S. Army Edgewood Chemical Biological Center , Aberdeen Proving Ground, MD, 21010
Published online: 27 Oct 2010.
To cite this article: S. Munavalli , D. K. Rohrbaugh , F. J. Berg , F. R. Longo & H. D. Durst (2002) Microwave Catalyzed
Reactions of H-Dimethylphosphonate with Oxiranes, Phosphorus, Sulfur, and Silicon and the Related Elements, 177:1, 215-230,
DOI: 10.1080/10426500210221
To link to this article: http://dx.doi.org/10.1080/10426500210221
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Phosphorus, Sulfur and Silicon, 2002, 177:215–230
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
MICROWAVE CATALYZED REACTIONS
OF H-DIMETHYLPHOSPHONATE WITH OXIRANES
S. Munavalli,a D. K. Rohrbaugh,b F. J. Berg,b F. R. Longo,a
and H. D. Durstb
Geo-Centers, Inc., PO Box 68, Gunpowder Branch, APG,
MD 21010 a and U.S. Army Edgewood Chemical Biological
Center, Aberdeen Proving Ground, MD 21010 b
(Received July 5 2001.)
Microwave catalyzed reactions of H-dimethylphosphonate with
1,2-epoxydecane, 5,6-epoxy-1-hexene, 1,2-epoxybutane and cyclohexene
oxide have been found to cause oxirane ring opening, deoxygenation and
hydrophosphorylation. 1,2-Epoxydecane gave three pairs of isomeric
products and another arising from the loss of a two-carbon fragment,
while 5, 6-epoxy-1-hexene, cyclohexene epoxide and 1,2-epoxybutane
yielded 10, 7, and 3 compounds respectively.
Keywords: Deoxygenation; H-dimethylphosphonate; hydrophosphory-
lation; oxirane ring cleavage
INTRODUCTION
Oxiranes comprise an extremely versatile group of intermediates and
as such have attracted considerable attention.1 9 Because of their ready
availability and exceptional reactivity, the epoxides have found varied
applications in synthetic organic chemistry. The oxirane ring can be
opened under almost all conditions: electrophilic, nucleophilic, neutral,
gas-phase, thermal and free radical conditions (Figure 1).1 An excellent
review on the preparation and synthetic applications of the oxiranes
has appeared.6 Recently we investigated the free radical cleavage of
styrene oxide with trifluoromethylthiocopper and reported the forma-
tion of products arising from the C C and C O bond fission.10 How-
ever, their reaction with phosphorus compounds has found only a lim-
ited application including their routine use in the Michaelis-Becker
reaction.11,12 Tri-coordinated pentavalent phosphorus compounds or
Address correspondence to S. Munavalli, Geo-Centers, Inc., PO Box 68, Gunpowder
Branch, APG, MD 21010.
215

216
S. Munavalli et al.
FIGURE 1 Types of oxirane cleavages and reactions. (1, 2) homolytic cleav-
ages (free radical, photolytic, thermal); (3) electrophilic attack on the ring oxy-
gen; (4) nucleophilic attack on the ring carbon; (5) nucleophilic attack on the
ring hydrogen; (6) reactions with electrons and surface recactions; (7) cycload-
ditions; (8) reactions of the substituent.
in situ generated intermediates are known to react with oxiranes.11,12
Thus, phosphorus azide reacted with propylene oxide to give cyclic
oxazaphoranes as well as acyclic compounds.13 Also, highly reactive
metaphosphate intermediates have been described to open the oxirane
ring to yield isomeric 1,3,2-dioxaphospholane-2-oxide derivatives.14
The in situ generated electrical energy from microwaves has been
used to thermally catalyze chemical reactions. This type of energy trans-
fer depends on the nature and properties of the reacting molecules.15
Since the advent of commercially available microwave cookers, the
microwave thermal process is finding increasing and interesting ap-
22
plications in synthetic organic chemistry.16
The popularity of the
microwave-induced chemistry appears to rest primarily on its dramatic
reduction of the reaction time and the possibility of carrying out reac-
tions in solid phase. In fact, the latter appears to have significantly
contributed to its enhanced use. In continuation of our interest in the
28
chemistry of the oxirane cleavage reactions,10,25
the microwave cat-
alyzed oxirane ring opening in the presence of H-dimethylphosphonate
has been examined and observed to lead to unusual products. This pa-
per presents the probable mechanism of the formation of various com-
pounds and their GC-MS characterization.
RESULTS AND DISCUSSION
Recently, H-phosphonates have attracted considerable attention and
31
have found useful applications in phosphorylation reactions.29

Hydrophosphorylation
217
The presence of the readily removable hydrogen at the phospho-
rus center appears to be the genesis of its reactivity.32,33 Among
other things, H-phosphonates are known to be involved in the addi-
tion to: (i) multiple bonds,34 (ii) carbonyl group35 and (iii) in trans-
esterifications.36 Dealkylation reactions have also been recorded.35
Both P O and C O bond cleavages have been observed.37 Methyl
radicals have been stated to react with trimethylphosphite, albeit
sluggishly, to give trimethylphosphonate.38,39 What is unusual about
the reaction described here is the non-specific radical formation from
H-dimethylphosphonate. Lesser regioselectivity observed in the forma-
tion of various products has been attributed to the greater length of the
carbon-phosphorus bond as compared to the carbon-carbon bond.
Deoxygenation of organic peroxides with phosphites has been
described.40,42 Phosphoranes exhibit reducing properties.43, 44 How-
ever, epoxides are said to remain unaffected in the presence of
47
phosphites.45
It has also been stated that phosphites48 and
phosphines49 deoxygenate epoxides to furnish alkenes. There seems to
be some contradiction and uncertainty as regards the reaction of epox-
ides with phosphorus compounds. Phosphorus stabilized carbanions
yield various products on treatment with oxiranes. Thus, the formation
of alkenes, cyclopropanes and ketones has been rationalized.50 Signifi-
cant formation of ketones was observed via hydrogen migration.51 How-
ever, the reaction of styrene oxide with benzylidene trimethylphospho-
rane yielded (2-phenylethyl)ketone as the minor product and cis/trans
1,3-diphenylpropene as the major product.50 With methylenetriph-
enylphosphorane, styrene oxide furnished a ketone and triphenylphos-
phine. With strongly basic ylides, cyclic ethers were obtained.53 The
reaction of styrene oxide with ethoxycarbonyl triphenylphosphorane
gave cyclopropanoids.54,55 Cyclohexene oxide itself reacts with ylide to
yield a mixture of olefins via ring contraction.55 The reaction of oxi-
ranes with phosphines generally leads to the creation of a carbon-carbon
double bond between the two carbon atoms involved in the oxirane
ring.57,58 The oxirane ring is cleaved by phosphines in acidic media (cf.
Ref. 13, p. 119). When diphenylphosphinous azide was caused to re-
act with propenylene oxide, four compounds, two acyclic and two cyclic
oxazophospholanes, were formed.12 In the above-cited compounds, the
phenyl ring was found to have migrated from phosphorus to nitrogen.
The loss of C2H5-moiety from C2H5O-group attached to phosphorus
was noticed during the synthesis of oxaphospholanes.15 Ring contrac-
tion was observed when cyclohexene epoxide was treated with ethoxy
carbonylphosphorane,59 while the same Wittig reagent transformed
the oxirane ring into a cyclopropyl ring.59 Epoxides yield oxaphospho-
lane with metaphosphates and phosphates.13,60,61 Epoxides are formed

218
S. Munavalli et al.
FIGURE 2 Structures of compounds formed from epoxydecane and cyclohex-
ene oxide.
along with trialkylphosphates when dihydro-1,3-2-dioxaphospholanes
and dihydro-1,4,2-dioxophospholanes are heated.62,63 Free radical re-
76
actions of phosphorus compounds have been described.57,64
Microwave induced reaction of H-dimethylphosphonate (1) with 1,2-
epoxydecane (2) and cyclohexene oxide (3) has been found to yield
products arising from ring cleavage, deoxygenation and addition. Thus,
1,2-epoxydecane (2) gave three pairs of isomeric products (4–9, Figure 2)
and another compound arising from the loss of a two-carbon frag-
ment (10). While cyclohexene oxide (3) furnished seven compounds
(11–16, Figure 2). H-dimethylphosphonate (1) itself gives two com-
pounds, namely trimethylphosphonate and trimethylphosphate. There
is nothing unusual about these compounds, for they are usually
formed during the oxidation and/or free radical reactions of H-
dimethylphosphonate (1). The mass spectral breakdown of dialkylphos-
76
phonates has been described in detail.74
The formation of the isomeric pair of O-(3-decyl)-O,O-dimethyl-
phosphates (4 and 5) can be ascribed to the presence of 2,3-epoxydecane
in the starting material. This inference was supported by the GC-
MS analysis of the starting material, which indicated the presence
of isomers having the same molecular weight as 1,2-epoxydecane
(2) but different retention times on the g. c. column. O-(3-ecyl)-O,O-
dimethylphosphates (4 and 5, Figure 3) simply arise from the open-
ing of the oxirane ring to form the oxy radical intermediate, which
reacts with the phosphonyl radical, followed by hydrogen abstraction.

Hydrophosphorylation
219
FIGURE 3 Proposed mechanism of formation of compounds from 1,2-
epoxydecane (2).
Compounds 6 and 7 are isomers of O-(3-decyl)-O,O-dimethylphosphates
(4 and 5) and can be considered to have been formed from 1,2-
epoxydecane (2) via a similar process.
The third pair of isomers, namely O-3-(1-decenyl) dimethylphos-
phates (8 and 9) are formed from the same free radical intermediate that
is involved in the formation of O-(3-decyl)-O,O-dimethylphosphates
(4 and 5). In this case, instead of hydrogen abstraction, hydrogen loss
occurs to furnish the compounds in question. Finally, the formation
of dimethyl (1-octenyl)phosphonate (10), can be rationalized as having
been formed from the above mentioned free radical intermediate, which
splits off a two carbon entity to give an octyl radical. The octyl radical
in turn loses hydrogen to give compound 10. Such vinylphosphonates
81
are known.78
Figure 3.
The various processes described above are shown in

220
S. Munavalli et al.
FIGURE 4 Mechanism of formation of compounds from cyclohexene oxide.
The reaction of H-dimethylphosphonate (1) with cyclohexene oxide
(3), contrary to the latter’s reaction with stabilized phosphorane car-
banions, proceeds via free radical processes to furnish products 11–16
(Figure 2). The phosphonyl radical adds to cyclohexene, undoubtedly
formed from 3 via the deoxygenation, to give a radical intermediate
which then simply abstracts hydrogen to yield 13. The phosphonyl rad-
ical reacts with the oxy radical resulting from the oxirane ring opening
to give radical intermediate, which after hydrogen abstraction yields
O-cyclohexylphosphate (14, Figure 4). Then 14 loses a methylene moi-
ety to form O-cyclohexyl-O-methylphosphate (11). Or loses a methyl
moiety to form an oxy radical, which subsequently abstracts hydrogen
to form the compound in question. There are precedents for such a
loss of an alkyl group from an alkoxy group attached to phosphorus.15
Compounds 15 and 16 are pyrophosphate derivatives. It would be safe
to assume that compound 11 serves as the precursor for 15 and 16.
Cyclohexeyl methylphosphinate (12) results from the reaction of the
in situ formed cyclohexene and methylphosphinyl radical. The former
happens to be a product of deoxygenation, while the latter seems to
have its origin in H-dimethylphosphonate (1). The recent characteriza-
tion of a methoxylated product from the reaction of alkyl epoxide with
H-dimethylphosphonate (1) lends support to this contention.82 This
nonregioselective formation of various compounds may be attributed
to the “greater length of the carbon-phosphorus bond as compared to
the carbon-carbon bond.”15
The reaction of H-dimethylphosphonate (1) with 5,6-epoxy-1-hexene
(17) gives 8 compounds (20–25, Figure 5), excluding the two formed

Hydrophosphorylation
221
FIGURE 5 Structures of compounds derived from 5,6-exoxy-1-hexene.
from the former. For compound 20, six structures (20a–20f, Figure 6)
were considered. Based on its mass spectral fragmentation pattern,
structure 20e was assigned to this compound. Of the six structures,
20e alone can give rise to ions m/e = 59 and 45 corresponding to frag-
ments CH2CH2OCH3 and CH2OCH3 respectively. Its formation can
be rationalized on the basis of the attack by the methoxy radical on
the terminal carbon atom of the in situ formed 1,5-hexadiene (26,
Figure 6) accompanied by the C3-hydrogen migration and followed
by the loss of hydrogen to furnish the conjugated dienic derivative,
20e, Figure 6). Two hexenols (21 and 22) were characterized by their
mass spectral breakdown patterns. The mass spectrum of compound 21
shows the presence of two ions, m/e = 45 and 59, resulting from -and
-fragmentation. Compound 22 readily loses water and does not give
the above mentioned ions. The oxirane ring of 5,6- epoxy-1-hexene (17)
(Figure 5) can undergo fission to form the oxy-radical intermediates,
which abstract hydrogen to give the hexenols (21 and 22).
Hydrogen 2-(5-hexenyl) methylphosphinate (23) results from the at-
tack of the phosphinyl radical on the C2- of 1,5-hexadiene (26), which
is formed from deoxygenation of 5,6-epoxo-1-hexene (17). The last
two compounds, namely dimethyl 2-(5-hexenyl)phosphonates (24 and
25) represent a pair of stereomers resulting from the attack of the
phosponyl radical on the C2- of 1,5-hexadiene (26), followed by hydro-
gen abstraction by the resultant radical intermediate (Figure 6). Both
trimethylphosphonate and trimethylphosphate (18 and 19) are rou-
tinely formed from H-dimethylphosphonate (1) during the oxidation
reactions. Their mass spectral breakdown has been discussed.25 The
formation and properties of various phosphorus radicals, namely phos-
76
phinyl, phosphony and phosphoranyl, have been described.69,70,74
The reaction of H-dimethylphosphonate (1) with 1,2-epoxybutane
(27, Figure 7) appears to be rather simple and straightforward. It
gives only 3 compounds: (a) cis- and trans-dimethyl 1-(1-propenyl)
phosphonates (28 and 29) and (b) n-butyl 10-methylphosphinate (30).

222
S. Munavalli et al.

Hydrophosphorylation
223
FIGURE 7 Reaction products of 1,2-epoxybutane.
The formation of 28 and 29 can be ascribed to the fragmentation of
formaldehyde from the radical intermediate formed by the reaction of
the phosphonyl radical with the radical intermediate arising from epox-
ide ring opening. This radical intermediate then goes on to lose hydro-
gen to give compounds 28 and 29. The mass spectra of 28 and 29 are
very similar and have an abundant number of odd mass ions. The lat-
ter is said to be a characteristic of monoalkenes.81 The formation of 30
is straightforward. It arises via the addition of the phosphonyl radical
to the in situ formed 1-butene (31), followed by hydrogen abstraction.
Figure 8 describes the above observations and Table 3 summarizes the
mass spectral fragmentation.
FIGURE 8 Mechanism of formation of products from 1,2-epoxybutane.

224
S. Munavalli et al.
EXPERIMENTAL
Mass spectra were obtained using a Finnigan TSQ-7000 GC/MS/MS
equipped with a 30 m 0.25 mm. i.d. DB-5 capillary column (J and W
Scientific, Folsom, CA). The conditions on the TSQ-7000 were: oven tem-
perature 60–270 C at 15 C/min, injection temperature 220 , interface
temperature 250 C, source temperature 150 , electron energy 70 eV
(EI) or 200 eV (CI) and emission current 400 A (EI) or 300 A (CI)
and scan time 0.7 sec. Data was obtained in both the electron ionization
mode (range 45–450 da) and chemical ionization mode (mass range 60–
450 da). Ultrahigh purity methane was used as the CI agent gas with
a source pressure of 4 Torr. Routine GC analyses were accomplished
with a Hewlett-Packard 5890A gas chromatograph equipped with a J
and W Scientific 30 m 0.53 mm i.d. DB-5 column (J and W Scientific,
Folsom, CA). The NMR spectra (1H and 13C) were recorded in CDCl3
with TMS as the internal standard on a Varian VXR-400S spectrometer
at 100 MHz and 376 MHz respectively.
Stoichiometric amounts of the respective reagents were mixed in
glass vials, or 5 ml R. B. f lasks, vigorously shaken on a vibro-mixer
and heated in the microwave oven for a specified period. The reaction
mixture was allowed to come to ambient temperature, the cooled prod-
uct was first analyzed by gas chromatography and then subjected to
GC-MS analysis.
Reaction of Hydrogen dimethylphosphonate (1) with 1,2-
Epoxydecane (2, Figure 2): Stoichiometric amounts of hydrogen
dimethylphosphonate (1, 0.22 g, 2 mmol) and 1,2-epoxydecane (2, 0.312
g, 2 mmol) were mixed in a glass vial, stirred for a few minutes using the
vibro-mixer and then heated in a table top microwave oven at power
8 for 2 min. The reaction mixture after cooling was analyzed by gas
chromatography. Then, it was heated again for four minutes and again
analyzed by gas chromatography. When no additional peaks showed
up in the chromatogram, it was then subjected to GC-MS analysis.
Thus, a total of seven compounds; O-(3-decyl)-O,O-dimethylphosphates
(4, 5), dimethyl (1-octenyl)phosphonate (10), 2-(decyl)-O,O-dimethyl-
phosphonate (6, 7), O-3-(1-decenyl)dimethylphosphates (8, 9) exclud-
ing compounds containing only the phosphorus moieties, were charac-
terized based on their mass spectral fragmentation behavior. The mass
spectral data is given in Table I.
Reaction of H-dimethylphosphonate (1) with Cyclohexene
oxide (3, Figure 2): Stoichimetric amounts of H-dimethylphosphonate
(1, 0.22 g, 2 mmol) and cyclohexene oxide (3, 0.196 g, 2 mol) were
mixed in a glass vial, stirred for a few minutes using the vibro-
mixer and then heated in a table top microwave oven at power 8

Hydrophosphorylation
225
TABLE I Compounds Formed From Epoxydecane and Cyclohexene Oxide
1. 1,2-Epoxydecane (2): M+ = 156 (r.t = 6.24 min, 49.9%); 127 (M C2H5);
113 (M C3H7); 98 (C7H14); 96 (C6H8O); 95 (C6H7O); 85 (C6H13); 82 (C6H10);
79 (C6H7); 72 (C4H8O); 71 (C5H11, 100%); 68 (C5H8); 67 (C5H7); 58 (C6H6O);
56 (C4H8); 55 (C4H7) and 53 (C4H5).
2. 1-Decene (11, cf. Fig. 3): M+ = 140 (r.t = 3.95 min, 0.1%); 111 (C8H15); 98 (C7H14);
97 (C7H13); 85 (C6H13) (C6H12); 83 (C6H11); 70 (C6H10); 69 (C5H9); 67 (C5H7);
56 (C4H8, 100%); 55 (C4H7, 99.2%) and 53 (C4H5)
3. 3-(Decyl)dimethylphosphate (4): M+ = 266 (r.t = 11.22 min, 0.2%); 170 (M C7H12);
141(M [OP(O)(OMe) 127 (C2H8PO4); 109 [P(O)(OMe)2]; 99 (C7H15);
97 (C7H13, 100%); 85 (C6H13); 82 (C6H10); 79 (109-OCH2 and 71 (C5H11).
4. 3-(Decyl)dimethylphosphate (5): M+ = 266 (r.t = 11.4 min, 0.1%); 170 (M C7H12);
157 (M OP(OMe)2, 98% 153 [C2H4OP(O)(OMe)2]; 125 [OP(O)(OMe)2);
110 [PH(O)(OMe)2]; 99 (C7H15); 97 (C7H13); 85 (C6H13); 83 (C6H11); 79 (109-OCH2)
and 71 (C5H11, 100%).
5. 2-(Decyl)dimethylphosphonate (6): M+ = 250 (r.t = 11.96 min, 0.7%);
165 (M C6H13); 153 (M C7H13); 137 [C2H4P(O)(OMe)2]; 113 (C8H17, 100%);
109 [P(O)(OMe)2]; 99 (C7H15); 96 [H2P(O)2(OMe)]; 81 [(C6H9 or H2P(O)3]; 79 (PO3)
69 (C5H9); 57 (C4H9) and 55 (C4H7).
6. 2-(Decyl)dimethylphosphonate (7): M+ = 250 (r.t = 12.09 min, 0.4%);
165 (M C6H13); 153(M C7H13); 137 [C2H4P(O)(OMe)2]; 113 (C8H17, 100%);
109 [P(O)(OMe)2]; 99 (C7H15); 96 [H2P(O)2(OMe)] or H2P(O)3 79 (PO3) 69 (C5H9);
67 (C5H7); 57 (C4H9) and 55 (C4H7).
7. 3-(1-Decenyl)dimethylphosphate (8): M+ = 264 (r.t = 12.39 min, 0.2%);
237 (M C2H3); 207 (237-OCH2); 167(M C7H13); 139 [M C10H19 or
CH2P(O)2(OMe)]; 127 [P(OH)2(OMe)2, 100%); 109 [P(O)(OMe)2]; 99 (C7H15);
96 (C7H12); 95 [HP(O)2(OMe)]; 69 (C5H9); 67 (C5H7); 57 (C4H9) and 55 (C4H7).
8. 3-(1-Decenyl)dimethylphosphate (9): M+ = 264 (r.t = 12.48 min, 0.1%);
237 (M C2H3); 207 (237-OCH2); 167(M C7H13); 139 [M C10H19 or
CH2P(O)2(OMe)]; 127 [P(OH)2(OMe)2, 100%); 109 [P(O)(OMe)2]; 99 (C7H15);
96 (C7H12); 95 [HP(O)2(OMe)]; 69 (C5H9); 67 (C5H7); 57 (C4H9) and 55 (C4H7).
9. 3-(1-Decenyl)dimethylphosphate (10): M+ = 220 (r.t = 11.54 min, 2.4%);
123 [CH2P(O)(OMe)2]; 110 [PH(O)(OMe)2]; 109 [P(O)(OMe)2]; 125 [OP(O)(OMe)2];
110 [PH(O)(OMe)2]; 83 (C6H11, 100%); 79 [PH(O)(OMe) or PO3]; 67 (C5H7);
57 (C4H9); 55 (C4H7); and 47 (PO).
10. Cyclohexyl methylphosphate (11): M+ = 194 (r.t = 8.57 min, 1.9%); 166 (M C2H4);
151 (161-CH3); 137 (M C4H7); 127 (137-CH2); 98 (C6H10O); 97 (C6H9O, 100%);
80 (C6H8); 79 (PO3); 70 (C5H10); 69 (C5H9); 57 (C4H9) and 47 (PO).
11. Cyclohexyl hydrogen phosphinate (12): M+ = 162 (r.t = 8.77 min, 2.0%);
134 (M C2H4); 121 (M C3H5); 112 (C6H9OCH3); 97 (112-CH3); 83 (C6H11);
80 [H2P(O)(OMe) or C6H8, 100%]; 79 [(PO(H)(OMe)]; 70 (C5H10); 69 (C5H9);
57 (C4H9) and 47 (PO).
12. Cyclohexyl dimethylphosphonate (13): M+ = 192 (r.t = 9.48 min, 2.8%);
164 (M C2H4); 151 (M C3H5); 13 (151-O); 113 [P(O)CH2(OMe)2, 100%)];
95 PHO2(OMe)]; 80 [H2P(O)(OCH3)]; 79 (PO3); 67 (C5H7); 5 (C4H9);
55 (C4H7) and 47 (PO).
(Continued on next page)

226
S. Munavalli et al.
TABLE I Compounds Formed from Epoxydecane and Cyclohexene Oxide
(Continued)
13. Cyclohexyl dimethylphosphate (14): M+ = 208 (r.t = 9.39 min, 0.3%);
153 (M C4H7); 127 [P(OH)2(OMe)2, 100%)]; 109 [P(O)(OMe)2]; 95 [PHO2(OMe)];
83 (C6H11); 79 (PO3); 69 (C5H9); 57 (C4H9) and 47 (PO).
14. 1-Cyclohexyl-1,2-dimethyl-2-hydrogenpyrophosphonate (15): M+ = 272
(r.t. = 12.12 min, 2.1%); 193 [M P(O)H(OMe)]; 191 (M C6H9);
176 (191-CH3 or C6H11CH2PO3); 148 (176-C2H4); 113 (C6H10OMe); 97
(C6H9O, 100%); 81 (C6H9); 79 (C6H7); 70 (C5H10); 55 (C4H7) and 47 (PO).
15. 1-Cyclohexyl-1,2-dimethyl-2-hydrogenpyrophosphonate (16): M+ = 272
(r.t. = 12.22 min, 12.1%); 241 (M OMe); 193 [M P(O)H(OMe)];
191 (M C6H9); 176 (191-CH3 or C6H11CH2PO3); 148 (176-C2H4); 113 (C6H10OMe);
97 (C6H9O, 100%); 81 (C6H9); 79 (C6H7); 70 (C5H10) and 55 (C4H7).
for 4 min. The reaction mixture after cooling was analyzed by gas
chromatography. Then, it was heated again for four minutes and
re-analyzed by gas chromatography. When no additional peaks ap-
peared in the chromatogram, the reaction product was subjected
to GC-MS analysis. Thus, a total of six compounds: O-cyclohexyl-
O-methylphosphate (11), cyclohexyl O-methylphosphinate (12), O-
cyclohexyl)-O,O-dimethylphosphate (13, 14), and O-[(O-cyclohexyl)-
O-methyl]phosporyl-O-methylphosphonate (15, 16) excluding hydro-
gen dimethylphosphonate, trimethylphosphonate and trimethyl-
phosphate; were characterized based on their mass spectral fragmen-
tation behavior. The structure of one compound remains undetermined
as it undergoes extensive breakdown in the mass spectrometer giving
no molecular ion peak. The mass spectral data is given in Table I.
Reaction of H-dimethylphosphonate (1) with 5,6-Epoxy-1-
hexene (17, Figure 5): Stoichiometric amounts of 5,6-epoxy-1-hexene
(17, 0.19 g, 2 mmol) and H-dimethyl-phosphonate (1, 0.22 g, 2 mmol)
were mixed in a glass vial, stirred for a few minutes using the vibro-
mixer and then heated in a table top microwave oven at power 7 for
90 s; 30 s each time to a total of 3 times. The reaction mixture after
cooling was analyzed by gas chromatography. Then, it was heated again
for four minutes and reanalyzed. When no additional peaks showed
up in the chromatogram, it was then subjected to GC-MS analysis.
Based on their mass spectral fragmentation behavior, a total of eight
compounds excluding the starting materials have been characracter-
ized: (1) trimethylphosphonate (18), (2) trimethyl-phosphate (19), (3)
1-methoxy-3, 5-hexadiene (20), (4) 5-hexene-1-ol (21), (5) 5-hexene-2-ol
(22), 2-(5-hexenyl) methylphosphinate (23), and (7) 2-(5-hexenyl)
dimethylphosphonates (24–25). The mass spectral data is given in
Table II.

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227
TABLE II 5,6-Epoxy-1-hexene and H-Dimethylphosphonate
1. Hydrogen dimethylphosphonate (1): M+ = 110 (r.t. = 2.48 min, 59.9%); 109 (M H);
95 (M CH3); 93 (M OH); 80 (95-CH3, 100%); 79 (M OCH3); 65 (80-CH3);
63 (PO2); 49 (PH2O) and 47 (PO).
2. 5,6-Epoxy-1-hexene: (2): M+ = 98 (r.t. = 2.38 min, 32.4%); 97 (M H); 83 (M CH3);
79 (97-H2O) 69 (M CHO); 68 (M OCH2); 67 (M OCH3, 100%); 65 (C5H5);
57 (C4H9); 55 (M C2H3O); 54 (C4H6); 53 (C4H5) and 51 (C4H3).
3. Trimethylphosphonate (3): M+ = 124 (r.t. = 3.01 min, 0.7%); 109 (M H);
109 (M CH3); 94 (109-CH3, 100%); 79 (94-CH3); 79 (M OCH3); 65 (PH2O2);
63 (PO2); 49 (PH2O) and 47 (PO).
4. Trimethylphosphate (4): M+ = 140 (r.t. = 3.4 min, 1.3%); 110 (M OCH2, 100%);
109 (M OCH3); 95 (110-CH3, 100%); 79 [P(O)H(OCH3)]; 79 (M OCH3); 65 (PH2O2)
and 47 (PO).
5. 1-Methoxy-3,5-hexadiene (5): M+ = 112 (r.t. = 3.74 min, 0.3%); 97 (M CH3);
85 (M C2H3); 80 (M CH3OH); 71 (C3H4OCH3); 67 (C5H7, 100%); 59 (C3H7O);
57 (C4H9); 55 (C4H7); 53 (C4H5) and 45 (CH2OCH3).
6. 5-Hexenol (6): M+ = 100 (r.t. = 4.02 min, 0.1%); 99 (M H); 85 (M CH3); 84 (100-O);
69 (M CH2OH); 67 (C5H7, 100%); 59 (C3H7O); 57 (C4H9); 53 (C4H5)
and 45 (HOCH2CH2).
7. 5-Hexene-2-ol (7): M+ = 100 (r.t. = 4.38 min, 0.4%); 98 (M 2H); 85 (M CH3);
80 (98-H2O); 74 (M C2H2); 69 (C5H9); 68 (C5H8); 67 (C5H7, 100%); 61 (80-C2H5);
57 (C4H9); 55 (C4H7); 53 (C4H5) and 51 (C4H3).
8. Hydrogen-5-hexenylmethylphosphinate (8): M+ = 162 (r.t. = 7.88 min, 4.8%);
147 (M CH3); 133 (M CH2 CH3); 121 (M C3H5); 107 [C2H4P(O)H(OCH3)];
83 [M (P(O)(OCH3))]; 79 [(P(O)(OCH3)]; 77 (C6H5); 67 (C5H7); 57 (C4H9);
54 (C4H6) and 47 (PO).
9. Dimethyl 2-(5-hexenyl)phosphonate (9): M+ = 192 (not seen) (r.t. = 8.47 min, 0.1%);
163 (M C2H5); 151 (M C3H5); 137 [C2H4P(O)(OCH3)2]; 113 (137-CH2);
109 [P(O)(OCH3)2]; 95 [P(O)(OCH3)(OH)]; 79 [P(O)H(OCH3) or C6H7, 100%];
77 (C6H5); 65 (C5H5); 54 (C4H6) and 47 (PO).
10. Dimethyl 2-(5-hexenyl)phosphonate (10): M+ = 192 (r.t. = 8.60 min, 0.1%);
163 (M C2H5); 151 (M C3H5); 137 [C2H4P(O)(OCH3)2]; 113 (137-CH2);
109 [P(O)(OCH3)2]; 95 [P(O)(OCH3)(OH)]; 79 [P(O)H(OCH3) or C6H7, 100%];
77 (C6H5); 65 (C5H5); 54 (C4H6) and 47 (PO).
Reaction of H-dimethylphosphonate (1) with 1,2-Epoxybu-
tane (27, Figure 7): Stoichiometric amounts of 1,2-epoxydecane
(2, 0.14 g, 2 mmol) and H-dimethylphosphonate (1, 0.22 g, 2 mmol)
were mixed in a glass vial, stirred for a few minutes using the vibro-
mixer and then heated in a table top microwave oven at power 7
for 2 min; 30 s each time to a total of 4 times. The reaction mix-
ture after cooling was analyzed by gas chromatography. Then, it
was heated again for four minutes and reanalyzed. When no ad-
ditional peaks appeared on the chromatogram, it was then sub-
jected to GC-MS analysis. Based on their mass spectral fragmentation

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S. Munavalli et al.
TABLE III Mass Spectral Fragmentation of Compounds from
1,2-Epoxybutane
1. 1,2-Epoxybutane (2): M+ = 72 (r.t. = 162 min, 8.3%); 71 (M H); 57 (C4H9, 100%);
55 (C5H7) and 45 (C4H7).
2. Dimethyl trans-1-propenylphosphonate (3): M+ = 150 (r.t. = 3.79 min, 1.0%);
135 (M CH3); 123 (M C2H3); 121 (135-CH2); 110 [P(O)(OCH3)2];
105 (M OCH3 CH2); 96 [P(O)H(OH)(OCH3), 100%]; 91 [P(O)(OH)(C2H3)];
79 (96-OH); 65 [PH(O)(OH)]; 56 (C4H8); 5 (C4H7) and 47 (PO).
3. Dimethyl cis-1-propenylphosphonate (4): M+ = 150 (r.t. = 3.74 min, 0.3%);
135 (M CH3); 123 (M C2H3); 121 (135-CH2); 110 [P(O)(OCH3)2];
105 (M OCH3 CH2); 96 [P(O)H(OH)(OCH3), 100%]; 91 [P(O)(OH)(C2H3)];
79 (96-OH); 65 [PH(O)(OH)]; 56 (C4H8); 55 (C4H7) and 47 (PO).
4. n-Butyl methylphosphinate (5): M+ = 136 (r.t. = 5.97 min, 1.8%); 121 (M CH3);
107 (M C2H5, 100%); 79 [P(O)H(OCH3)]; 54 (C4H6); 48 [PH(O)] and 47 (PO).
behavior, a total of seven compounds: including the starting mate-
rials and two derived from H-dimethylphosphonate were characrac-
terized: (1) trimethylphosphonate (18), (2) trimtheylphosphate (19),
(3) dimethly cis-1-propenylphosphonate (28), (4) dimethly trans-1-
propenylphosphonate (29), (5) n-butyl methylphosphinate (30). The
mass spectral fragmentation data is given in Table III.
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