A New Route to Nitramines in Nonacidic Media - ACS Publications

Nitramines are a class of compound finding widespread application in ..... methods: 4-(tri-(n-butyl)silyl)morpholine (VDi) and 4-(triethylsilyl)morpho...
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Chapter 12

A New Route to Nitramines in Nonacidic Media

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R. W. Millar Defence Research Agency, Fort Halstead, Sevenoaks, Kent TN14 7BP, United Kingdom

The novel synthesis of nitramines and nitramides by nitrolysis of the corresponding N-trialkylsilyl compounds using dinitrogen pentoxide (N O ) is described. In seventeen examples the yields are generally in the range 70 to over 90%, falling below the lower figure only if alkylsilyl groups with chain lengths greater than two are employed. The reactions are characterised by their cleanliness, and the co­ -products, trialkylsilyl nitrates, are relatively stable and volatile, facilitating isolation of the nitrated products. Furthermore, these trialkylsilyl nitrates, unlike the acyl nitrates produced in conventional nitrolyses, are isolable and can be used to nitrate further substrates, thus eliminating problems of disposal of spent liquors from conventional reactions. The process is both mild and versatile, enabling nitramine functions to be introduced into a variety of molecular environments, and two notable cases are exemplified, namely N-nitroaziridines and Ν,Ν'-dinitroaminals. 2

5

Nitramines are a class of compound finding widespread application in propellant and explosive technology, and their chemistry has been reviewed (1-5). They are commonly prepared by the reaction of secondary amides with nitric acid in dehydrating media such as acetic anhydride (3), although other routes are possible, for instance by the addition of nitrate salts of secondary amines to acetic anhydride in the presence of a catalyst, e.g. chloride ion (6), by direct interaction of an amine with dinitrogen pentoxide, N2O5 (5,7), or by nitrolysis of gem-diamines with nitric acidacetic anhydride (2,3,8). More recently developed methods include the reaction of Ν,Ν-dialkylamides with nitronium tetrafluoroborate (9), the reaction of tert.butylamines with nitric acid or Ν2θ5(70), and the action of nitric acid-acetic anhydride on tert. amines with in situ oxidation of the resulting nitrosamines with peracetic acid (77). (Routes involving oxidation of isolated nitrosamines have been disregarded owing to the high toxicity of these compounds.) Many of these routes have disadvantages such as contamination of the product by nitrosamines which are awkward to remove (72), the use of reagents which are not available cheaply on an industrial scale (e.g. NO2BF4), or the production of coproducts which are difficult to dispose of, notably acyl nitrates. Further problems

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12. MILLAR

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A New Route to Nitramines in Nonacidic Media

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may arise from inaccessibility of substrates, for instance in the direct nitration of amines (7), certain categories of amine either do not form the nitramine (particularly highly basic amines), or may not be preparable in their unsubstituted form (e.g. hexahydropyrimidines - see later). Such shortcomings limit the scope and utility of existing routes for the synthesis of nitramines. The problems oudined above are exemplified in one of the most commonly used routes for nitramine synthesis, namely the reaction of secondary amides with nitric acid under dehydrating conditions (equation 1), where the cleavage of the N-acyl

N-N0 R' N-H R'

\ - O R / II

2

I

. nitramine

M

0 NOCOR"

II

2

amide (R" = alkyl) carbamate (R = alkoxy)

amine

(1)

+ acyl nitrate (R = alkyl)

M

M

[Reagents:- a) acylating agent (eg R COCI) M

b) nitrating agent, esp. pure HN0 , N0 BF " or N 0 ] 3

2

+

4

2

5

bond results in formation of the desired nitramine (I), but an acyl nitrate co-product (Π) is also formed during the reaction (termed a nitrolysis (5)). The disposal of these acyl nitrates is awkward and also poses safety problems in certain circumstances, for instance in the synthesis of H M X from D A D N (13). A further drawback of the nitrolysis of acylamines is that cleavage of N-C bonds other than the acyl linkage may occur, resulting in competing reaction pathways and hence lower yields and product contamination, and in extreme cases little of the desired product may be formed (e.g. Ν,Ν-dimethylurethane (III) yields ethyl N-methyl-N-nitrocarbamate (IV) instead of N,N-dimethylnitramine (4)). Finally, some acyl derivatives of polycyclic polyamines (e.g. the precursor of bicyclo-HMX, V) are completely inert to nitrolysis (14),

CH N-C - O C H 2

CH

3

Ο DI

HoCOC 3

N-C - O C H

5

2

0N 2

2

00

5

Ο IV

N0

/ \ N^^N / \

0N 2

COCH3

In an attempt to overcome these twin problems of controlling the direction of nitrolysis reactions and forming more easily handlable co-products, the replacement of acyl functions by other readily nitrolysable groups was considered. It was felt that these problems stemmed largely from the inertness of the nitrogen atom towards electrophilic attack as a result of the electron-withdrawing acyl function, and

In Nitration; Albright, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.

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124

NITRATION

therefore employment of substituents with the opposite inductive effect, i.e. electrondonating substituents, would be beneficial. With this rationale in mind, obvious candidate elements for consideration would be the group IV metalloids, and it was already known that stannylamines could be nitrolysed to yield nitramines (Nielsen, A . T., N W C China Lake, Calif., personal communication, 1988). Furthermore, publications in the mid-1980s had indicated that C-silyl compounds could be cleaved by reagents such as nitronium tetrafluoroborate to yield C-nitro compounds (15-17). However, as no reports were known of the nitrolysis of the corresponding N-silyl compounds, silylamines (VI), this therefore seemed an obvious class of compound to examine. In the subsequent discussion, the N-silyl substrates are divided into two categories - i) dialkyl and cycloalkyl silylamines, the largest category with thirteen examples, and ii) silylamides (including ureas and carbamates) with four examples. Because of their different chemistries, both in the preparation and handling of the substrates as well as their nitration chemistry, this subdivision will be maintained throughout the paper. Discussion Silylamines. The silylamines (VI) were derived from the corresponding secondary amines, formed in situ where necessary (e.g. V i m , see below). Reaction with dinitrogen pentoxide (N2O5) in halogenated solvents such as dichloromethane generated the nitramines (I) cleanly and in good to excellent yield (equation 2 and Table I). The reaction was found to be general for a range of alkyl substitutents both

N-Na "s

R'

N-H

a

\

»R

/ "

N-Si-R" ./ \ R"

nitramine

VI

amine

(2)

+

silylamine

0 NOSiR" 2

3

Vn

silyl nitrate [Reagents:- a) silylating agent (R" SiX where X is a leaving group such as halogen, dialkylamino etc) 3

b) nitrating agent, esp. N 0 , also N0 BF ] 2

5

2

4

on nitrogen (R & R') and silicon (R"), with the highest yields being obtained with trimethylsilyl derivatives (R = CH3, see Table I). The reaction is applicable to cases which have proved troublesome in the past, for instance sterically hindered nitramines such as If, and yields were in many cases improved, sometimes markedly, upon those hitherto obtained. Cyclic dinitramines (Π & Im) were likewise preparable without difficulty from the corresponding disilyl precursors. It is notable that the precursor to Im, 1,3bis(trimemylsilyl)-hexahydropyrimidine (Vim, Table I) is derived from an unstable diamine (hexahydropyrimidine, VIII) and highlights an intrinsic advantage of the novel nitration over other methods which require the use of the free amine, which may be unavailable. Furthermore, the dinitramine product (Im), which contains a

In Nitration; Albright, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.

12.

MILLAR

125

A New Route to Nitramines in Nonacidic Media

Table I: Nitrodesilylation Reactions using N O 2

1

1. Monosilylamines 1

2

4

2

2

R

3

R R N-Si(R ) R 3

R

4

R

R

s

Rn. Time (hr)

Rn. Temp. (°C)

Yield of Nitramine

2

0+2

80%

VI

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a

-(CH ) 0(CH )22

2

CH

2

3

CH

3

-(CH ) -

CH

3

CH

3

0.75

-5±2

81%

-(CH ) -

CH

3

CH

3

0.5

-7 to-1

76%

CH

3

0.75

-5±2

78%

CHa

0.75

-5±2

84%

CH

0.75

-5to0

87%

2

5

2

CH

4

CH

3

C H 2

C H

5

i-C H 4

CH

3

2

a

CH,

5

i-C H

9

4

CH

9

-(CH ) 0(CH )22

2

3

3

CH

2

3

3

t-C H 4

Oto+5

37%

+5 to +10

40%

-5 to +5

39%

0.75

0to+5

61%

1

0to+5

70%

2.25 9

6 -(CH^CKCH^-

n-C H

-(CH^CKCH^-

C H

5

C H 2

5

C H 2

5

C H 2

5

CH

3

CH

3

a

J

i-C H

k

-CH -CH(CH )-

4

9

i-C H

2

4

3

4

2

9

9

n-C H 4

9

L

5

10 min.

0±5

b

b

c

2. Disilylamines

1

(CH ) Si—Ν 3

3

Ν — Si(CH ) 3

m (CH^Si^

^Si(CH ) 3

3

l

-8to0

91%

-5 to +5

69%

d

3

Continued on next page

In Nitration; Albright, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.

NITRATION

126 Table I: Nitrodesilylation Reactions using N 0 (Contd.) 2

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3. Silylamides

Rn. Time (hr)

VI

Starting Material

Product

η

Ο Me Me-C-N^ SiMe

Ο Me Me-ONf' N0

3

\

5

Rn. Yield of Temp. Nitramine (°C)

0.75

-5

79%

0.7

0

80%

2

\

SiMe

N0

3

ο

2

ο

Ρ ^ N - P rr

Me-N^

1 n1

SiMea SiMe

N0

3

^iC^Nv γ SiMe3

Me Si 3

x

N

a

2

0

5

.

1 0 t o

-5

75%

2

^iC^NxN 0

0.75 -5 82% 2

Ο

9

3

2

2

d

2

N0

i - C H = (CH )2CHCH Larger excesses of N 0 (50 and 100% resp.) used N-Nitroaziridine not isolated - reacted further in situ (see text) Mode of addition reversed ( N 0 added to silylamine) 4

c

N - PPrr " N

0 N^ γ

Ο

b

1 1

M eMe—IjT

5

2

5

geminal dinitramine moiety which is a substructural fragment found in the R D X and H M X molecules, is preparable in a yield (69%) twice that reported in the hitherto best method (by nitro-denitrosation of the 1,3-dinitroso compound I X (18)). This hints at the potential of this reaction, and its viability is subject only to the availability of

vra

IX

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12. MILLAR

127

A New Route to Nitramines in Nonacidic Media

suitable silylated precursors; in this respect, few limitations have been encountered, one of the few groups which is incompatible with silylating agents being the nitrile group. The behaviour of one substrate, the N-trimethylsilylaziridine VIk was notable. Upon reaction with 1 mol N2O5 the N-nitroaziridine X was formed in situ in ca 80% yield, and further reaction with excess of the reagent resulted in the formation of the Ν,Ν-dinitramine-nitrate XI (equation 3), which was characterised spectroscopically,

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CH

3

\

ΟΝΟ,

•a

\

N-SiR" I

Ν-NO,

3

N 0 1 mol 2

VIk

5

N 0 excess 2

5

(3)

XI -1

the nitramine asymmetric stretching band in the i.r. being observed at 1607 c m , in line with previous findings (79). l i e formation of the N-nitroaziridine X constitutes the second reported synthesis of this class of compound (20,27) and the first by direct electrophilic substitution, although a N-nitroaziridine intermediate was postulated in earlier work on the nitration of propyleneimine by N2O5 (22). Also, the Ν,Νdinitramine-nitrate XI was contaminated with some propane-1,2-diol dinitrate (ΧΠ); such compounds are known to be decomposition products of N,N-dinitramines (Coon, C. L„ L L N L Livermore, Calif., personal communication, 1992). Therefore the behaviour of this silylamine opens the door to some novel chemistry by affording classes of compound which are only otherwise obtainable with extreme difficulty; furthermore by the ring-opening nitration yields high-energy compounds such as XI (C3H6N4O7) which possesses a similar oxygen balance to nitroglycerine. Silylamides. As mentioned above, three representative classes of acyl substrates were investigated: one amide (VIn), one carbamate (VIo) and two ureas - VIp (acyclic) and Vlq (cyclic); see Table I and equation 4. A l l gave the corresponding nitramine derivatives in good yields (75-82%), which in two cases (VIn & VIo; equations 4a & 4b) were significant improvements upon those obtained previously (27% and 53% respectively (23)). The acyclic dinitrourea (Ip) was a new compound, prepared from the known silyl precursor VIp (24), while preparation of the cyclic dinitrourea (Iq), although feasible by direct nitration of trimethyleneurea (XIII) in 87% yield (25) was nevertheless facilitated by the nitrodesilylation route by the aforementioned advantages of simplified workup and absence of contaminating by­ products (equation 4c). Conclusions Nitrodesilylations of silylamines and silylamides by N2O5 afford the corresponding N-nitro compounds, nitramines and nitramides respectively, in good to excellent yields. The reaction is of wide applicability, and several products bearing l,3-bis-(Nnitro) functions have been prepared, notably compounds Im, Ip & Iq. The success of the method with these materials is significant and augurs well for the extension to polynitramines; for instance, RDX should be available from the corresponding tris(N-trimethylsilyl) precursor (XIV), and indeed the starting materials for this synthesis have already been described in the literature (26,27). The conditions necessary to

In Nitration; Albright, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.

NITRATION

128

C

H

Ν-H

|CH CO

\

N 05/CH CI • 2

N-SiR"

3

2

|CH CO

3

CH

2

N-N0

2

CH CO

3

3

VIn silylamide

amide

3 N

In nitramide

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(4a)

n

f^N—H -

N-SiR'

Ο

N 05/CH CI 2

2

3

2

Γ^Ν-ΝΟρ Ο

Ο VIo

carbamate

ίο

nitrocarbamate

N-silylcarbamate

(4b) NO,

SiR",

Η R-N

R-NL

N 05/CH CI 2

C=0

2

2

R-N.

;c=o

C=0

R'-N

R'-N

R'-N^ Yl0

SiR"

Η

3

N,N'-dinitrourea

N.N'-disilylurea

urea

XIII R = R' =-(CH ) - VIp: R = CH , R' = n-C H Vlq: R,R' = -(CH ) 2

3

3

3

2

2

3

7

Ip: R = CH , R' = n-C H Iq: R.R' = -(CH ) 3

3

2

7

3

(4c) effect the cleavage of the N-Si bond are much milder than, for instance, those required to cleave N-acyl substrates (i.e. amides) and suggest applications in those areas where cleavage of acetamides have failed to yield nitramine products, e.g. polycyclic nitramines such as bicyclo-HMX (14). SiMe

3

N>

Me Si' 3

η

XIV SiMeo

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A New Route to Nitramines in Nonacidic Media

The by-product from the nitration reaction, the volatile silyl nitrate (CH3>3SiON02 ( V u , R" = CH3, equation 2), is a nitrating agent in its own right (77) and could easily be collected by distillation and used profitably to carry out other nitrations, such as toluene to dinitrotoluene. The formation of silyl nitrates such as VII is also preferable to the acidic by-products (viz. BF3 or HBF4) which would arise from the corresponding reactions with NO2BF4. Another advantage is the non-acidic nature of the reaction medium which suggests applications involving acid-sensitive substrates hitherto precluded from study in conventional nitration media. Finally, concerning the novelty of the nitrodesilylations, although some mention has been made of the formation of N-nitroheteroaromatics by the reaction of the corresponding N-silyl compounds with NO2BF4 (77,28), the products are principally of use as transfer nitrating reagents. Furthermore, silylamines of primary amines have been shown to behave differently upon attempted nitration with oxides of nitrogen such as N2O4, undergoing deamination (29). Likewise, previous investigations of the reactions of some simple silylamines with N2O5 did not result in a general nitramine synthesis (30), although the recently reported (31,32) action of nitronium tetrafluoroborate on N-trimethylsilylamines has come close to achieving this goal. Hence the work reported here constitutes the first detailed description of nitrodesilylation by N2O5 of a comprehensive range of substrates, comprising secondary amines, amides, carbamates and ureas. Experimental Safety Note: In the reactions described herein energetic materials are produced which may be hazardous, and appropriate precautions should be taken in their preparation and handling. Also, many of the starting materials, reagents and products are toxic, corrosive or present other hazards and only suitably trained personnel should attempt the chemical transformations described here. Materials and Apparatus. The following silylamines were purchased from Aldrich Chemical Co.: 4-(trimethylsilyl)morpholine (Via), l-(trimethylsilyl)pyrrolidine (Vic), N-trimethylsilyldimethylamine (VId) and N-trimethylsilyldiethylamine (Vie); two silylamides, N-methyl-N-(trimethylsilyl)acetamide (VIn) and N-(trimethylsilyl)oxazolidin-2-one (VIo) were purchased from Fluka Chemicals. The remaining silylamines were prepared as follows:- n-alkylsilylamines derived from strong bases by direct reaction with chlorotrimethylsilane in the presence of a proton acceptor (triethylamine), either as described in the literature: l-(trimethylsilyl)piperidine (VIb) (33) and l,4-bis(trimethylsilyl)piperazine (VII) (34), or by modified literature methods: 4-(tri-(n-butyl)silyl)morpholine (VDi) and 4-(triethylsilyl)morpholine (Vii). Trimethylsilylamines derived from weaker bases, or silylamines bearing branched alkyl substituents on Si were prepared by lithiating the amine using n-butyllithium prior to reaction with the chlorosilane (35,36): N-(trimethylsilyl)di-isobutylamine (Vif), 4-(im.-butyldimethylsilyl)morpholine (VIg) and N-(triethylsilyl)diisobutylamine (VIj). l-Trimethylsilyl-2-methylaziridine (VIk) was prepared by the reaction of propyleneimine with chlorotrimethylsilane in n-pentane (37). Physical data of these materials are as follows: V l f : b.pt. 72°C/10 mm; H nmr, δ: -0.05 (s,9); 0.75 (d,12); 1.70 (sp,2); 2.45 (d,4) ppm; i.r. v (liquid film): 1468 (m), 1386 (m), 1367 (m), 1318 (w), 1260 (m), 1248 (s) cm-1; VIg: b.pt. 120-130°C/15 mm; *H nmr, δ: 0.05 (s,6); 0.90 (s,9); 2.91 (t,4), 3.55 (t,4); i.r. v (liquid film): 1471 (w), 1386 (m), 1372 (m), 1258 (s), 1159 (m), 1258 (s) cm-1; v i h : b.pt. 160163°C/9 mm; *H nmr, δ: 1.1 (m,29); 2.83 (t,4); 3.55 (t,4) ppm; i.r. v (liquid film): 1457 (w), 1374 (m), 1255 (m), 1160 (w), 1116 (s), 1080 (m) cm-1; V i i : b.pt. l

m

a

x

m

a

m

x

a

x

In Nitration; Albright, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.

NITRATION

130

155-160°C/ 47 mm; *H nmr, δ: 0.6 (m,15); 2.80 (t,4); 3.50 (t,4); i.r. v (liquid film): 1456 (w), 1371 (w), 1256 (m), 1161 (m), 1115 (s) cm-1; v i j : b.pt. 125-130°C/ 1.5 mm; l H nmr, δ: 0.8 (m,27); 1.72 (sp,2); 2.45 (d,4); i.r. v (liquid film): 1466 (m), 1385 (m), 1366 (w), 1163 (m), 1029 (s) cm-1. The remaining silylamine, l,3-bis(trimethylsilyl)hexahydropyrimidine (Vim) was prepared by the following novel procedure: hexahydropyrimidine (3.0 g) in anhydrous ether solution (150 ml), prepared as described in the literature (38), to which triethylamine (7.05 g) had been added, was treated with chlorotrimethylsilane (7.6 g) at 15 to 20°C - further anhyd. ether was added to facilitate stirring. After 20 min. at this temperature, the mixture was filtered and concentrated (Rotavapor) to give a cloudy oil which was distilled (bulb-to-bulb) to give a mobile oil (1.9 g), b.pt. 90-5°C/ 3 mm). A second batch distilled on the Spaltrohr had b.pt. 80-2°C/ 6.5 mm; l H nmr, δ: 0.05 (s,18); 1.31 (m,2); 2.97 (t,4); 3.92 (s,2) ppm; i.r. v (liquid film): 1452 (m), 1385 (m), 1365 (m), 1250 (s), 1200 (m) cm-1. NjN'-BisitrimethylsilyO-N-methyl-N'-in-propyOurea (VIp) was prepared by a modified literature procedure from η-propyl isocyanate and heptamethyldisilazane (24); l,3-bis(trimethylsilyl)-3,4,5,6-tetrahydro-2(7//)-pyrimidinone (Vlq) was prepared by silylation of the trimethyleneurea using N-trimethylsilyltrifluoroacetamide as follows:- Ν,Ν'-Trimethyleneurea (3,4,5,6-tetrahydro-2(777)-pyrimidinone) (5.80 g, 50 mmol) and N-methyl-N-(trimethylsilyl)trifluoroacetamide (24.9 g, 125 mmol) in acetonitrile (30 ml, dried over 4A molecular sieve) were heated under reflux for 18 hr under an atmosphere of dry nitrogen. The mixture was cooled and, after removal of the solvent under reduced pressure, bulb-to-bulb distillation of the residue gave a fore-run of N-methyltrifluoroacetamide, b.pt. 3 solution (3040 ml) and the organic layer separated. The aqueous layer was extracted with dichloromethane and the combined extracts were washed further with saturated sodium bicarbonate solution, dried over anhydrous MgS04 and evaporated under water-pump vacuum below 30°C. The nitramine products, Ia-lm (see Table I), were collected and characterised by m.pt., i.r. and nmr spectra; the majority were isolated as colourless solids (after trituration (ethanol) if necessary), except for lb and Ie

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A New Route to Nitramines in Nonacidic Media

which were oils. In the case of l a , the m.pt. of the product (N-nitromorpholine) was not depressed on admixture with an authentic sample, prepared from morpholine and N2O5 by the method of Emmons et al (7). In certain cases (VIg, V i i and V i m ) , larger excesses of N2O5 (100, 50 and 100% resp.) were used, and owing to the instability of nitramine Im to acid, the mode of addition of the reagents was reversed [otherwise a highly impure product was obtained]. 4-Nitromorpholine (la), m.pt. 50-51°C (lit. (7) 50-52°C); *H nmr, δ: 3.80 (s) ppm; i.r. v

m a x

(mull): 1524,1512 (-NO2 asymm.), 1315,1254 (-NO2 symm.) cm-1.

1-Nitropiperidine (lb), oil, *H nmr, δ: 1.65 (m,6), 3.85 (m,4) ppm; i.r. v (liq. fdm): 1514 (-NO2 asymm.), 1329,1279,1242 ( - N 0 symm.) cm-1. 1-nitropyrrolidine (Ic), m.pt. 55.5-56.5°C (lit. (44,7) 56°C, 58-59°C resp.); H nmr, δ: 2.00 (m,4), 3.70 (m,4) ppm; i.r. v (mull): 1500 ( - N 0 asymm.), 1307, 1280 (-NO2 symm.) cm-1. Dimethylnitramine (Id), m.pt. 54.5-55°C (lit (41) 58°C); H nmr, δ: 3.43 (m) ppm; i.r. v (mull): 1500, 1450 ( - N 0 asymm.), 1333, 1290, 1260 ( - N 0 symm.) cm-1. Diethylnitramine (Ie), oil, H nmr, δ: 1.25 (t,6), 3.80 (qr,4) ppm; i.r. v (liq. film): 1509,1470 (-NO2 asymm.), 1377,1282 (-NO2 symm.) cm-1. Di-isobutylnitramine (If), m.pt. 79-80°C (lit. (42,43) 76-77°C, 81.5-82.5°C resp.); H nmr, δ: 0.85 (d,6), 2.20 (sp,l), 3.53 (s,2) ppm; i.r. v (mull): 1526, 1492, 1462 (-NO2 asymm.), 1327,1270 ( - N 0 symm.) cm-1. 1,4-Dinitropiperazine (II), m.pt. 202°C(dec.) (lit. (43) 215°C); H nmr, δ ( Ό DMSO): 4.03 (s) ppm; i.r. v (mull): 1545 (-NO2 asymm.), 1335, 1285, 1241 (-NO2 symm.) cm-1. 1,3-Dinitrohexahydropyrimidine (Im), m.pt. 82-83°C (lit. (18) 84°C); H nmr, δ: 1.92 (m,2), 3.95 (t,4), 5.75 (s,2) ppm; i.r. v (mull): 1556, 1538 ( - N 0 asymm.), 1275 (-NO2 symm.) cm-1.

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Preparation of l-(N,N-dinitramino)propan-2-ol nitrate (XI). N-(Trimethylsilyl)propyleneimine (VIk) (2.32 g, 18.0 mmol) in dichloromethane (6 ml) was added over 12 min. at -15°C to a solution of N2O5 (2.0 g, 18.5 mmol) in the same solvent (ca 10 ml). The resulting mixture was stirred for 10 min. whilst allowing to warm to 0°C (yellow colour develops), then it was pipetted rapidly into a solution containing excess N2O5 (5.0 g, 46.3 mmol) in dichloromethane (ca 15 ml) and the mixture was monitored by HPLC (RP18 column, acetonitrile-water 60:40 volVvol. eluant, monitor at 210 nm) for disappearance of the N-nitroaziridine. After ca 90 min. at 0±5°C the N-nitroaziridine peak (shortest retention time) had reached a minimum and the peak assigned as the Ν,Ν-dinitramine (longest retention time, X ca 240 nm) had reached a maximum relative to the propane-1,2-diol dinitrate which was also present in the mixture (intermediate retention time). The mixture was worked up in the usual manner (wash with saturated sodium bicarbonate solution, dry over anhydrous MgS04 and evaporate) to give an oil (2.25 g, 62%) which comprised l-(N,N-dinitramino)propan-2-ol nitrate (XI), v (liquid film) 1647 (-ONO2 asymm.), 1607 (-N(N02)2 asymm.), 1274 (-ONO2 symm.), 1244 (-N(N02)2 symm.), 850 (-ONO2), 815 (-N(N0 )2) cm-1 j admixture with propane1,2-diol dinitrate (ΧΠ). m

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132

NITRATION

Reactions of silylamides VIn-q. The silylamide (20 mmol) was dissolved in dichloromethane (10-15 ml) and added dropwise with stirring and cooling (at -5±2°C) to a solution of N2O5 (22 mmol) in the same solvent (20-40 ml) [disilylamides VIp and Vlq were reacted with 44 mmol N2O5]. After addition was complete the mixture was stirred for the period shown at the temperature shown in Table I. The reaction mixture was then worked up as described above. N-Nitro-N-methylacetamide (In), oil, H nmr, δ: 2.68 (s,3), 3.60 (s,3) ppm, e(CCl ): 2.61 (s,3), 3.55 (s,3) ppm (lit. (23)5(CC1 ): 2.43, 3.31 ppm); i.r. v (liq. film): 1721 (CO), 1569 ( - N 0 asymm.), 1239 ( - N 0 symm.) cm-1 (H . (23) CCI4 soin.: 1720,1575 cm-1). 3-Nitro-l,3-oxazolidin-2-one(Io), m.pt. 106.5-107°C (lit. (23) 108-109.5°C); l H nmr, δ: 4.42 (s) ppm; i.r. v (mull): 1786 (CO), 1554 ( - N 0 asymm.), 1282 (-NO2 symm.) cm-1. NjN'-Dinitro-N-methyl-N^^-propyOurea (Ip), oil, H nmr, δ: 0.98 (t,3), 1.67 (m,2), 3.69 (s,3), 4.08 (t,2) ppm; i.r. v (liq. film): 1723 (CO), 1590 ( - N 0 asymm.), 1287 (-NO2 symm.) cm-1. l 3-dinitro-3,4 5 6-tetrahydro-2(7H)-pyrimidinone (N,N-Dinitro-N,N-(trimethylene)urea, Iq), m.pt. 118°C(dec.) (lit. (25) 121-122°C); *H nmr, δ: 2.35 (m,2), 4.18 (t,4) ppm; i.r. v (mull): 1753 (CO), 1571 ( - N 0 asymm.), 1266 ( - N 0 symm.) cm-1. l

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Literature Cited 1.

2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

Wright, G. F. In Methods of Formation of the Nitramino Group, its Properties and Reactions; Feuer, H., Ed.; The Chemistry of the Nitro and Nitroso Groups, Part 1 (The Chemistry of Functional Groups Series, Patai, S., Series Ed.); Interscience: New York, 1969, Ch. 9. Smith, P. A. S. Open Chain NitrogenCompounds;Benjamin: New York: 1966, Vol. 2, Ch. 15. Urbanski, T. Chemistry and Technology of Explosives; Pergamon Press: Oxford, 1967, Vol. 3. Coombes, R. G. In Nitration; Sutherland, I. O., Ed.; Comprehensive Organic Chemistry (Barton, D.; Ollis, W. D., Series Eds.); Pergamon: Oxford, 1979, Vol. 2. Fischer, J. W. In Nitro Compounds: Recent Advances in Synthesis & Chemistry ; Feuer, H.; Nielsen, A. T., Eds.; Organic Nitro Chemistry Series; VCH: New York, 1990, Ch. 3, pp 338-346. Chute, W. J.; Herring, K. G.; Tombs, L. E.; Wright, G. F. Canad. J Res. 1948, 26B, 89-103. Emmons, W. D.; Pagano, A. S.; Stevens, T. E. J Org. Chem. 1958, 23, 311-3. Chapman, F. J Chem. Soc. 1949, 1631. Andreev, S. Α.; Novik, L. Α.; Lebedeev, Β. Α.; Tselinskii, I. V.; Gidaspov, Β. V. J. Org. Chem. USSR 1978, 14(2), 221-224. Cichra, D. Α.; Adolph, H. G. J Org. Chem. 1982, 47(12), 2474-2476. Boyer, J.H.; Pillai, T. P.; Ramakrishnan, V. T. Synthesis, 1985, 677-679. Bottaro, J. C.; Schmitt, R. J.; Bedford, C. D. J. Org. Chem. 1987, 52(11), 22922294. Siele, V. I.; Warman, M.; Leccacorvi, J.; Hutchinson, R. W.; Motto, R.; Gilbert, E. E.; Benzinger, T. M.; Coburn, M. D.; Rohwer, R. K.; Davey, R. K. Propellants&Explosives 1981, 6, 67-73.

In Nitration; Albright, L., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1996.

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A New Route to Nitramines in Nonacidic Media

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14. Koppes, W. M.; Chaykovsky, M.; Adolph, H. G. J Org. Chem. 1987, 52(6), 1113-1119. 15. Schmitt, R. J.; Bottaro, J. C.; Malhotra, R.; Bedford, C. D. J Org. Chem. 1987, 52(11), 2294-2297. 16. Olah, G. Α.; Rochin, C. J. Org. Chem. 1987, 52, 701-702. 17. Olah, G. Α.; Malhotra, R.; Narang, S. C. In Nitration: Methods & Mechanisms; Feuer, H., Ed.; Organic Nitro Chemistry Series; VCH: New York, 1989, Ch. 4. 18. Willer, R. L.; Atkins, R. L. J Org. Chem. 1984, 9, 5147-5150. 19. Aerojet-General Corp.,Brit.Pat. 1126591 (6 Sept. 1963). 20. Haire, M. J.; Boswell, G. A. J Org. Chem.1977,42, 4251-4256. 21. Haire, M. J.; Harlow, R. L. J Org. Chem. 1980, 45, 2264-2265. 22. Golding, P.; Millar, R. W.; Paul, N. C.; Richards, D. H., Tetrahed. Letts. 1991, 32(37) 4985-4988. 23. White, Ε. H.; Chen, M. C.; Dolak, L. A. J Org. Chem. 1966, 31, 3038-3046. 24. Roesky, H. W.; Lucas, J. Inorg. Synth. 1986, 24, 120-121. 25. McKay, A. F.; Wright, G. F. J Am. Chem. Soc. 1948, 70, 3990-3994. 26. Bestmann, H. J.; Wölfel, G. Angew. Chem. Internat. Ed. 1984, 23, 53. 27. Morimoto, T.; Takahashi, T.; Sekiya, M. Chem. Comm. 1984(12), 794-795. 28. Glass, R. S.; Blount, J. F.; Butler, D.; Perrotta, Α.; Oliveto, E. P. Canad. J. Chem. 1972, 50, 3472-3477. 29. Wudl, F.; Lee, T. Β. K. Chem. Comm. 1970, 490-491. 30. Schultheiss, H.; Fluck, Ε. Z. Anorg. Allg. Chem. 1978, 445, 20-26. 31. Olah, G. A. In Methods for Preparing Energetic Nitro-Compounds: Nitration with Superacid Systems, Nitronium Salts and Related Complexes; Chemistry of Energetic Materials; Olah, G. Α.; Squire, D. R., Eds.; Academic Press Inc.: San Diego, 1991, Ch. 7, p.197. 32. Dave, P. R.; Forohar, F.; Axenrod, T.; Bedford, C. D.; Chaykovsky, M.; Rho, M­ -K.; Gilardi, R.; George, C. Phosphorus, Sulfur, Silicon Relat. Elem. 1994, 90(1-4), 175-184. 33. Breed, L. W.; Haggerty W. J.; Harvey, J. J Org. Chem. 1960, 25, 1804-1806. 34. Kakimoto, Μ. Α.; Oishi, Y.; Imai, Y. Makromol. Chem. Rapid Commun. 1985, 6, 557-562. 35. Rauchschwalbe, G.; Ahlbrechte, H. Synthesis 1974, 9, 663-665. 36. Sundberg, R. J.; Russell, H. F. J Org. Chem. 1973, 38, 3324-3330. 37. Scherer, O. J.; Schmidt, M. Chem. Ber. 1965, 98, 2243. 38. Titherley A. W.; Branch, G. Ε. K. J Chem. Soc. 1913, 330. 39. Birkhofer, L.; Kühlthau, H. P.; Ritter, A. Chem. Ber. 1960, 93, 2810-2813. 40. Harris, A. D.; Trebellas, J. C.; Jonassen, H. B. Inorg. Synth. 1967, 9, 83-88. 41. Lamberton, A. H. Q Rev. 1951, 5, 75-98. 42. Luk'yanov, Ο. Α.; Seregina, N. M.; Tartakovskii, V. A. Bull. Acad. Sci. USSR Chem. Ser. 1976(1) 220-221; Chem. Abs. 1976, 84, 135574. 43. Robson, J. H.; Reinhart, J. J Am. Chem. Soc. 1955, 77, 2453-2457. 44. Suri, S. C.; Chapman, R. D. Synthesis 1988, 743-745. © British Crown Copyright 1995/ DRA Farnborough Hants. U.K. Published with the permission of the Controller of Her Britannic Majesty's Stationery Office. RECEIVED January 16, 1996

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