J. Org. Chem.

1980,45, 2515-2516 2515

( 2 m, 2 H, ArCHCHCN); (100MHz, CDC13/Me2SO-d6/D20)6 nitrate.' Recently, increased interest in these compounds

4.70 and 4.32 (AB q, 2 H, ArCHCHCN, J = 4.0 Hz); 13C NMR has resulted in improvements in the direct esterification2v3
(CDC13/Me2SO-d6)141.4, 132.4, 129.3, 127.8, 127.1, 126.4, 119.5, and the use of mercury(1) nitrate in the preparation from
119.3, 116.9, 114.5, 113.2, 55.23, 46.1 ppm. alkyl halide^.^
Anal. Calcd for C15H13N3:C, 76.57; H, 5.57; N, 17.86. Found: A general method for the conversion of amines into
C, 76.74; H, 5.54; N,17.73.
Tetrahydroquinoxalines 4 b - m were prepared analogously. nitrate esters was lacking until recently. In 1970-1971,
2-Cyano-3-phenylquinoxaline (5). A suspension of 1.0 g (4.3 Wudl published two preliminary communication^^^^ on the
mmol) of 4 a , 1.75 g (8.1mmol) of mercuric oxide, and 100 mL conversion of amines into nitrate esters: one involved
of absolute EtOH was stirred at reflux temperature for 1.25 h. preliminary silylation5 and the other reported four exam-
The reaction mixture was cooled and filtered through Celite. The ples of which two gave yields of only 20%. No further
filtrate was concentrated in vacuo to give a reddish brown oil which details of this work have appeared; however, Barton and
was chromatographed first on silica gel (CHC13) and then on Narang7 have shown that in the presence of excess amidine
alumina (hexanes/CHC13 1:l) to afford 630 mg (64%) of 5 as base at -78 "C, N2O4 can convert primary or secondary
colorless plates: mp 160-163 "C (lit.' mp 163 "C); 'H NMR alkyl primary amines into the corresponding alkyl nitrates
(Me2SO-d6)6 8.50-7.42 (m, Ar H). in good yield; the reaction proceeds with predominant
2-Carboxamido-3-phenylquinoxaline(6). A mixture of 7.0
g (29.8 mmol) of 4 a , 7 g (80.5 mmol) of activated MnOp,and 500 retention of configuration.
mL of toluene was stirred at 100 "C under a nitrogen atmosphere We have shown6that the conversion of primary amines
for 36 h. The reaction mixture was allowed to cool to ambient into pyridinium salts by pyryliums can be utilized as the
temperature, diluted with CHC13,and filtered through Celite. The first step in a general two-stage transformation of amino
filtrate was concentrated under reduced pressure to afford a into other functionality. The displacement of the pyri-
colorless solid which was recrystallized from aqueous EtOH: yield dinium N substituent can be carried out either by the
6.1 g (82%); mp 198-199 "C (lit." mp 198-199 "C); IR (KBr) 3360, gegen anion or by an added nucleophile. We now extend
3175,1655 cm-'; 'H NMR (CDC13/Me2SO-d6)d 8.10-7.20 (m, Ar both these procedures to give nitrate esters.
HI. Nitrate Esters by Thermolysis. 1,3,5-Triphenyl-
(8). A solution
3-Phenyl-l,2,3,4-tetrahydroquinoxalin-2-one
of 900 mg (5.3 mmol) of l,l-dicyan0-2-phenyloxirane,'~ 350 mg pent-2-ene-1,5-dione9 is converted by nitric acid into
(3.1 mmol) of o-phenylenediamine, and 10 mL of absolute EtOH 2,4,6-triphenylpyrylium nitratelo (70570 ) which reacts
was stirred a t reflux temperature under a nitrogen atmosphere readily with a series of alkyl- and benzylamines to give the
for 4 h. The reaction mixture was cooled, and the resulting corresponding 1-substituted 2,4,6-triphenylpyridinium
precipitate was collected and recrystallized from EtOH to provide nitrates (Table I); the structures of these salts are sup-
420 mg (60%) of 8 as a dark red solid: mp 196-197 "C (lit.16mp ported by their spectral features." On thermolysis of
201-203 "C); IR (KBr) 3300, 1660, 1595, 1500 cm-'; 'H NMR these salts (Table I), using triphenylpyridine where nec-
(CDC1,/MezSO-d6) 6 7.37-7.17 (m, 5 H, Ar H), 6.80-6.58 (m, 4 essary as flux, at 180-230 "C under reduced pressure, the
H,Ar H), 6.32-6.18 (m, 2 H,2 NH), 4.45 (m, 1 H, PhCHN). alkyl nitrate distilled over with purity >97 % as shown by
Anal. Calcd for C14H12N20:C, 74.99; H, 5.38; N, 12.49. Found: 'H and 13C NMR.l' The yields averaged 77% for the first
C, 74.77; H, 5.23; N, 12.35.
step and 6690 for the second step.
R e g i s t r y No. 1, 54607-00-0;&-%a,33984-96-2;trans-2a, 33984- Formation of Nitrate Esters in Solution. Although
95-1; cis-%f,73377-89-6; t r a n s - 2 f , 73377-90-9; cis-2k, 33984-92-8; mononitrates are thermally rather stable in the absence
trans-%k, 33984-91-7; 3a, 25855-20-3;3b, 71897-07-9;3c, 25187-18-2; of impurities such BS nitrites and nitric acid,' the preceding
3d, 49634-78-8;4a, 73377-91-0;4b, 73377-92-1;4c, 6-methyl deriva-
tive, 73377-93-2; 4c, 7-methyl derivative, 73378-01-5; 4d, 73378-32-2; method is clearly not suitable for large-scale work or for
4e, 73378-31-1;4 f , 73377-94-3;4g, 73377-95-4;4h, 6-methyl deriva- the preparation of high molecular weight nitrates or po-
tive, 73377-96-5;4h, 7-methyl derivative, 73378-02-6; 4i, 73378-30-0; lynitrates. Hence we sought a method in solution.
4j, 73378-29-7;4k, 73377-97-6;41,73384-19-7;4m, 6-methyl deriva- 5,6,8,9-Tetrahydro-7-phenyldibenzo[c,h]acridine (1) is a
tive, 73377-98-7; 4m, 7-methyl derivative, 73378-03-7; 5,59393-45-2;
6,73377-99-8;7,33512-02-6;8,23465-73-8; o-phenylenediamine, 95-
54-5; 3-phenyl-2-~p-tolylsulfonyl)-1,2,3,4-tetrahydroquinoxaline,
73378-00-4;4,5-dimethyl-o-phenylenediamine, 3171-45-7;4-methyl-
o-phenylenediamine,496-72-0; 4-chloro-o-phenylenediamine, 95-83-0;
4-nitro-o-phenylenediamine, 99-56-9.
S u p p l e m e n t a r y M a t e r i a l A v a i l a b l e : NMR and IR spectra
and analytical data for quinoxalines and tetrahydroquinoxalines
1,Z= N
(6 pages). Ordering information is given on any current masthead 2, Z = N'R, CF,SO;
page.
far better leaving group than 2,4,6-triphenylpyridi11e.'~We

(1) R. Boschan, R. T. Merrow, and R. W. van Dolah, Chem. ReG., 55,

485 (1955).
(2) C.D.Marken, C. E. Kristofferson,M. M. Rolond, A. P. Manzara,
and M.W.Barnes, Synthesis, 484 (1977).
Conversion of Primary Amines into Nitrate Esters (3) G. A. Olah, S. C. Narang, R. L. Pearson, and C. A. Cupas, Syn-
thesis. 452 (1978).
Alan R. Katritzky* and Liliana Marzorati (4) A . McKillop and M. E. Ford, Tetrahedron, 30, 2467 (1974).
(5) F. Wudl and T. B. K. Lee, J . Chem. SOC.D ,490 (1970).
School of C h e m i c a l Sciences, U n i v e r s i t y of E a s t A n g l i a , (6) F. Wudl and T. B. K. Lee, J . Am. Chem. SOC.,93, 271 (1971).
N o r w i c h , N R 4 7TJ,E n g l a n d (7) D. H.R. Barton and S. C. Narang, J . Chem. Soc., Perkin Trans.
I , 1114 (1977).
R e c e i v e d D e c e m b e r 14, 1979 (8) A. R. Katritzky, Tetrahedron Reports, in press.
(9) R. Lombard and J. P. Steohan. Bull. SOC.Chim. Fr.. 1458 (1958).
Two classical methods have been used for the prepara- (10) C. Gastaldi, Gazr. Chim. Ital., 2 , 289 (1921).
(11) See paragraph on Supplementary Material at end of paper.
tion of nitrate esters: nitric acid esterification of the ap- (12) A. R. Katritzky and S. S. Thind, J . Chem. Soc., Perkin Trans. I ,
propriate alcohol and treatment of alkyl halides with silver in press.

0022-3263/80/1945-2515$01.00/0 0 1980 American Chemical Society

2516 J. Org. Chem., Vol. 45, No. 12, 1980 Notes
Table I. Preparation and Thermolysis of N-Substituted 2,4,6-TriphenylpyridiniumNitrates
trip henylpyridinium
nitrates b
' 9 thermolysis conditions RONO,
yield, teomp, pressure, time, yield,
N substituent % mp, "C C mm h bp, "C lit. bp,"C ( m m ) ref
n-butyl 83 202-203 250 760 3 50 115-120 130-131 (760) d
n-hexyl 85 224-227 230 15 3 68 75-80 66-70 (12) d
benzyl 70 182-184 200 20 2 85 108-110 101-104(12) d
p-methylbenzyl 90 109-112 180 10 2 73 115-118 44-49(0.015) e
p -chlorobenzyl 86 124-126 180 7 3 60 108 109 (7) e
phenyl 50 271-275
All from ethanol-ether. Satisfactory C, H, N analyses reported. Identified by IR and NMR spectra. F. L. M. *
Pattison and G . M. Brown, Can. J. Chem., 34,879 (1956). e S. D.Ross, E. R. Coburn, and M. Finkelstein, J. Org. Chem.,
33, 585 (1968).

Table 11. 20 "C for 1.5 h. The crystalline solid was filtered off and re-
5,6,8,9-Tetrahydro-7-phenyldibenzo[c,h Iacridinium crystallized from absolute EtOH.
Trifluoromethanesulfonates (2). Method B. The pyrylium trifluoromethanesulfonate (5.1g,
Preparation and Conversion to Alkyl Nitrates 0.01mol) and the amine (0.02mol) in dry (Na) Eb0 (80 mL) were
2 stirred for 12 h a t 20 "C. The precipitate (5.28g) was filtered
off and washed with EtzO (3 x 10 mL).
yield,a yield of Benzyltrimethylammonium Nitrate. Benzyltrimethyl-
N substitumt % mp, "C RONO,, % ammonium hydroxide (40% in MeOH, 11 mL, 26 mmol) and nitric
n-octyl 91b 147-148' 71 acid (1.6mL) were stirred for 15 min. Benzene was added (30
n-undecyl 92d 157-158' 72 mL) and the solvent removed at 100 "C/15 mm. The resulting
n-dodecyl 91djf 155-156 68 hygroscopic solid, mp 152-157 "C (lit.14 mp 151-160 "C),5.2 g
n-hexadecyl 92 big 160 > 90h (95%), was kept under dry dioxane.
a All compounds formed yellow prisms. From EtOH. Metathesis of N-Alkylpyridinium Trifluoromethane-
Mp 147-148 'C previously reported by Thind." sulfonates in Solution. General Procedure. 5,6,8,9-Tetra-
* Analytically pure without recrystallization. e Mp 157- hydro-7-phenyldibenzo[c,h]acridinium trifluoromethanesulfonate
158 'C, previously prepared by A. M. El-Mowafy (10mmol) and benzyltrimethylammonium nitrate (20 mmol) were
(unpublished results). Anal. Calcd f o r C,,H,,F,NO,S: heated in dry dioxane (100 mL) a t reflux for 24 h. After the
C, 70.9; H, 6.9;N, 2.1. Found: C, 70.7;H, 7.0;N, 2.1. solution was allowed to cool, water was added (80 mL) and the
Anal. Calcd for C,H,,F,NO,S: C, 72.0;H, 7.4;N, reaction mixture concentrated at 100 OC/15 mm to of its
1.9. Found: C, 71.8;H, 7.5;N, 2.0. Yield estimated
volume. After extraction with EtzO (3 X 50 mL), dry HC1 was
by NMR.
passed through the dry (MgS04)extract. After filtration, the
ethereal solution was neutralized and dried over MgS04. Evap-
prepared 1-substituted 5,6,8,9-tetrahydro-7-phenyldi- oration of the solvent gave the product pure by TLC (Table 11).
benzo[c,h]acridinium trifluoromethanesulfonates (2) from
the corresponding amines and 5,6,8,9-tetrahydro-7-
phenyldibenzo[c,h]xanthyliumtrifluoromethane~ulfonate~~ Acknowledgment. We thank Drs. R. C. Pate1 and B.
and reacted them with benzyltrimethylammonium nitrate Gregory for their interest in and help with this work.
in refluxing dioxane to give the alkyl nitrates" (Table 11).
The yields in the first and second steps averaged 82% and Registry No. 2 (R = n-octyl), 73377-30-7;2 (R = n-undecyl),
7070, respectively. 2 (R = n-hexadecyl),
73377-32-9;2 (R = n-dodecyl), 73377-34-1;
73377-36-3; octyl nitrate, 629-39-0;undecyl nitrate, 73377-37-4; do-
Experimental Section decyl nitrate, 13277-59-3;hexadecyl nitrate, 24152-77-0;5,6,8,9-
tetrahydro-7-phenyldibenzo[c,h]xanthyliumtrifluoromethane-
IR and NMR spectra were measured with Perkin-Elmer 257 sulfonate, 73377-38-5; octylamine, 111-86-4; undecylamine, 7307-55-3;
and R12 instruments, respectively (Me4Sias internal standard). dodecylamine, 124-22-1; hexadecylamine, 143-27-1; 2,4,6-triphenyl-
Melting points (uncorrected) were determined on a Kofler hot- pyrylium nitrate, 73377-39-6; N-butyl-2,4,6-triphenylpyridinium
stage apparatus. nitrate, 73377-40-9;N-hexyl-2,4,6-triphenylpyridiniumnitrate,
N-Alkylpyridinium Nitrates. General Procedure. 2,4,6- 73377-41-0; N-benzyl-2,4,6-triphenylpyridinium nitrate, 73377-42-1;
Triphenylpyrylium nitrate (10mmol) dried at 20 "C/0.5mm and N-(p-methylbenzyl)-2,4,6-triphenylpyridinium nitrate, 73377-43-2;
the appropriate amine (12mmol) were stirred for 12 h in dry (Na) N-(p-chlorobenzyl)-2,4,6-triphenylpyridinium nitrate, 73377-44-3;
Ego at 20 "C.The precipitate was filtered off, washed with EGO N-phenyl-2,4,6-triphenylpyridinium nitrate, 73377-45-4; butylamine,
(3 X 10 mL), and recrystallized from EtOH-Et20 (Table I). 109-73-9;hexylamine, 111-26-2;benzylamine, 100-46-9; p-methyl-
For l-phenyl-2,4,6-triphenylpyridinium nitrate a similar pro- benzylamine, 104-84-7; p-chlorobenzylamine, 104-86-9; aniline, 62-
cedure was used except that EtOH was used as a solvent at 100 53-3;butyl nitrate, 928-45-0; hexyl nitrate, 20633-11-8; benzyl nitrate,
"Cand the product was precipitated by adding EgO after cooling. 15285-42-4; p-methylbenzyl nitrate, 13527-05-4; p-chlorobenzyl ni-
Thermolysis of Triphenylpyridinium Nitrates. The dry trate, 15313-94-7;benzyltrimethylammonium nitrate, 19876-73-4;
(20"C (0.5mm) for 4 h) N-substituted triphenylpyridinium nitrate benzyltrimethylammonium hydroxide, 100-85-6.
(3 g) was heated under the conditions shown in Table I. If the
melting point of the pyridinium salt exceeded 130 "C, 2,4,6-tri-
phenylpyridine (3 g) was used as flux. Supplementary Material Available: 'H NMR spectral data
N-Alkylpyridinium Trifluoromethanesulfonates." Me- of N-substituted 2,4,6-triphenylpyridinium nitrates and IR,'H
thod A. 5,6,8,9-Tetrahydro-7-phenyldibenzo[c,h]xanthylium NMR, and 13CNMR spectral data of alkyl and benzyl nitrates
trifluoromethanesulfonate (2.5g, 5 mmol) was stirred with the (2pages). Ordering information is given on any current masthead
amine (5mmol) in absolute EtOH (10mL) and EtzO (20mL) at page.

(13) A. R. Katritzky and S. S. Thind, J. Chem. SOC.,

Perkin Trans. 1 ,
in press. (14)H. R. Ing and R. Robinson, J . Chem. SOC.,1666 (1926).