7083 Condensation of Diindeno[l,2-c:2',1'-e]pyridazine-11,12-dione (34) with Hydrazine. Diindeno[l,2-~:2',1'-e]pyridazine-11,12-dihydrazone (32). A mixture of 0.13 g (0.0045 mol) of 34 and 0.15 g (0.16 ml, 0.0045 mol) of 95% hydrazine in 30 ml of a 1O:l mixture of monoglyme and ethanol was stirred for 48 hr at room temperature and for 3 hr on a steam bath. The solution turned from dark green to orange. The reaction mixture was cooled and the solid was collected by filtration to give 0.040 g (30 %) of 32. The infrared spectrum was identical with the product 32 isolated from the condensation of 31 with hydrazine. Diindeno[l,2-c:2',1'-e]pyridazine-ll,l2-dione (34). A suspension of 0.20 g (O.ooO64mol) of 32 in 100 ml of concentrated hydrochloric acid was heated on a steam bath for 2 hr. The solid remaining was removed by filtration while the solution was still hot and the filtrate was allowed to cool to give 0.050 g (27%) of a hydrochloride salt (33) of 34. Recrystallization from chloroform removed the hydrogen chloride from the molecule and gave diketone 34, mp 306-308", as needle-like crystals. The hydrochloride salt (33) was also decomposed by heating a dry sample of it to about 200". This was carried out in a capillary tube, and the hydrogen chloride was observed with wet litmus paper. The solid turned from a dark green to a light tan a t 200" and continued heating gave mp 306-308", that of the free diketone (34). Anal. Calcd for C18H8N202: C, 76.06; H, 2.82; N, 9.86. Found: C, 75.76; H,3.03; N, 10.20. The infrared spectrum of 34 showed no >C=N- or -NHz absorption and did show a strong >C=O band at 1740 cm-'. Diindeno[l,2-c;2',1 '-elpyridazine(36). I. Preparation from 32. A mixture of 4.0 g (0.013 mol) of 32 and 5.0 g (5.1 ml, 0.15 mol) of 95% hydrazine in 100 ml of ethylene glycol was heated at 170" overnight. The solution was filtered while hot, and the product was collected and washed several times with absolute ethanol to give 3.0 g (92%) of a dark purple, highly crystalline compound, mp 285" dec.
Anal. Calcd for CI8Hl2N2: C , 84.37; H, 4.68; N, 10.93. Found: C,84.58; H,4.53; N, 11.06. The infrared spectrum showed no bands for >C=O, -NHt, or -N=N- functions. 11. Preparation from 34. A mixture of 0.075 g (0.0021 mol) of 34 and 0.67 g (0.71 ml, 0.021 mol) of 95% hydrazine in 20 ml of ethylene glycol was heated at 150' for 2 days. The solution was allowed to cool, and the solid was collected by filtration to give 0.020 g (37%) of product, mp 285" dec. The infrared spectrum was identical with that for the product when 32 was heated in hydrazine. 111. Preparation from 31. A mixture of 2.0 g (0.0070 mol) of 31 and 2.2 g (2.3 ml, 0.070 mol) of 95% hydrazine was heated at 80" for 6 hr, and the dihydrazone 32 precipitated as a copper colored crystalline solid. The solution was then heated at 150" overnight and 32 went into a solution t o give a dark brown solution. The solution was allowed to cool and the product was isolated by filtration as a brown solid in a quantitative yield, mp 285" dec. The infrared spectrum was identical with that for the product when 32 was heated in hydrazine. The condensation of 2-cyclopentene-1,4-dione(30),18 1,3-cyclopentanedione (26),19 P-tropolone (37),2012 1 or 1,3-~ycloheptanedione (38)*2 with hydrazine under the normal reaction conditions afforded no identifiable products.
(18) G . H. Rasmussen, H. 0. House, E. F. Zaweski, and C. H. DePuy, Org. Syn., 42, 36 (1962). (19) C. H. DePuy and E. F. Zaweski, J . Amer. Chem. Soc., 81, 4920 (1959). (20) J. Allan and R. Robinson, J . Chem. Soc., 376 (1926). (21) A. J. Birch, private communication, May 20, 1966. (22) B. Eistert, F. Haupter, and K. Schank, Ann., 665, 5 5 (1963).
Reactions of Carbonyl Compounds with Difluoramine' Kurt Baum
Contribution from Environmental Systems Division, Aerojet-General Corporation, Azusa, California 91703. Received June 27, 1968 Abstract: Ketones and aldehydes were found to react with difluoramine in sulfuric acid or oleum with replacement of carbonyl groups by two difluoramino groups. Carbonium ion precursors in the y position cyclized to give a-(difluoramino)tetrahydrofurans. One such derivative, 2,5-bis(difluoramino)-2,5-dimethyltetrahydrofuranwas treated further under more forcing conditions, to yield 2,2,5,5-tetrakis(difluoramino)hexane. Acetol gave 2,5-bis(difluoramino)-2,5-dimethyl-l,Cdioxane. Michael addition of difluoramine took place with a,P-unsaturated carbonyl compounds.
D
ifluoramine has been shown to react as a nucleophile in the presence of undergoing alkylation by carbonium ions. In the absence of catalysts, difluoramine was added reversibly to aldehydes and ketones to form a-difluoraminocarbinols. Inasmuch as the difluoramino group is capable of supporting positive charge on neighboring atoms, it appeared possible to prepare geminal bisdifluoramino compounds from carbonyl compounds in the presence of strong acids, with difluoraminocarbinols and difluoraminocarbonium ions as intermediates. (1) This work was supported by the Office of Naval Research and the Advanced Projects Research Agency. (2) W . H. Graham and J. P. Freeman, J . Am. Chem. SOC.,89, 716 (1967). (3) K. Baum, J . Org. Chem., 32, 3648 (1967). (4) J . P. Freeman, W. H.Graham, and C. 0. Parker, J. Am. Chem. SOC.,90, 121 (1968).
This result was achieved with the ketones shown in Table I. Simple ketones reacted readily with a mixture of concentrated sulfuric acid and refluxing difluoramine (bp -23"), although no reaction took place with sulfuric acid of less than 9 2 x concentration. Electronwithdrawing substituents required more forcing conditions, such as a more acidic medium (oleum) or a higher reaction temperature (attained by using a closed reactor). The sequence leading to bis(difluoramin0)alkanes was shown to be reversible; 2-octanone was recovered when 2,2-bis(difluoramino)octane was shaken with sulfuric acid for 1 hr at room temperature. Yields of bis(difluoramino)alkanes are therefore affected by any variables involved in the rates of the individual steps in the equilibria (Scheme I). In general, a high concentration of difluoramine, a solvent with a strong affinity for water, and a low solubility for the product are favor-
Baum / Difluoramine Reactions with Carbonyl Compounds
7084 Table I. gem-Bis(difluoramin0) Derivatives of Ketones ~~
Starting material
Product
CHaCCHa
~~~
BP, “C (or mp)
73
I1
0
40-41 (30 mm)
38 (0.6 mm)
36 (20 mm)
difluoramine at room temperature gave a 53 % conversion in 40 hr, and starting material was recovered. Using 20% fuming sulfuric acid, only 0.7 ml/mmol of ketone, and a threefold excess of difluoramine at its reflux temperature gave a 99.5 % yield in only 2 hr. Aldehydes were also converted to bis(difluoramino)alkanes, but more forcing conditions were required than for simple ketones. n-Propionaldehyde gave 1,lbis(difluoramino)propane, and a,d-bis(difluoramin0)propyl ether was isolated as an intermediate. Trioxane similarly was converted to bis(difluoramino)methane, which was characterized by nitrogen analysis and infrared spectra. Further characterization of bis(difluoramin0)methane was restricted by its extreme sensitivity; explosions occurred during vacuum line manipulations. The synthesis of bis(difluoramin0methyl) ether from difluoraminomethanol and sulfuric acid has been r e p ~ r t e d . ~
3
44 (7 mm)
CH3CHzCH0
KFL
NF2
I I CHBCH~CH-O-CHCHZCH, NF*
(103)
I
41 (60 mm)
ClCHzCCHa
I1
(CHzO)$
0
93 (2 mm)
CH3C(CHn)aCOzCzHj
II
0
-
CHJCH2CH
I
NF, CHZ(NFJ2
Carbonyl compounds with carbonium ion precursors in suitable positions gave difluoramino-substituted lactones, tetrahydrofurans, and dioxanes. The reactions listed in Table I1 were carried out in the presence Table 11. Cyclization Reactions
65 (0.25 mm)
CHSC(CHZ)~NOZ
11
0
NFz NOz I
CHaCCHzCHzCOOH
NFz
NOn
I
I
CH~CCHZCHZCCH~CH3CCHnCHzCCHa
11
0
I
I
NFz
NOz
Starting material
I
I1
CHaCCHzCHzCH=CHz
I1
,
NF,, CH2I CHZ
34 (8 mm)
CHn
I
CH~CCHZCHZC(NOZ)~ C H ~ C C H ~ C H Z C ( N O(42) Z)~
I
I CH3CCHzCHzCCHa
II
NF?
0
55-56 (0.5 mm)
,C,O/CHCH, CH3
0
NFz
CH,-CH2 I
CHI
I/
NOz
BP, “C (or mp)
/c. o, c= 0
0
(47)
h’F,,I
Product
able factors. The importance of reaction conditions in the case of 5,5,5-trinitro-2-pentanoneis illustrative. No reaction took place with refluxing difluoramine and concentrated sulfuric acid in 4 hr. Using 100% sulfuric acid, 4 ml/mmol of ketone, and an eightfold excess of
NF,,i
CH,-CH, I ,CCH, ‘O ‘CH,
c
I
CH,’
I
NF2, I
CHaCCHzCHzC=CHz
I1
-CH2 I
50-51 (19 mm)
CH2
c
CHI/
‘O‘
CCH, ‘CHI
50-51 (19 mm)
0
CHaCCHnCHzCCHa 0 I1
0 II
NF,,I
CH2- CH
I:NFz
35 (2.7 mm)
CH,/C‘~/C\CH,
Scheme I
?H
* OH2
CHaCCHzOH
II
0
NFi
NF2
of refluxing difluoramine, using concentrated sulfuric acid as the solvent. These reactions can be rationalized as difluoramine alkylations by the carbonium ions which result from intramolecular alkylation of carbonyl groups. In the case of levulinic acid, the same product
Journal of the American Chemical Society / 90:25 / December 4, 1968
7085 Scheme I1
0
0
0
I1
CH&CHZCHzCOH
OH
i
I
CH,CCH,CH,COH
+
OH
I
II
c-t
-H+
I +
CH3CCHZCHzCOH
CHZI
-
CHz
HNF,
(-H,O)
would be formed by the protonation of either the carboxyl or keto carbonyl groups (Scheme 11). For the olefinic starting materials in Table 11, the observed products can arise only by protonation of the olefinic bonds; initial attack on the carbonyls would give carbocyclic products.
‘c=c-
/
/ CH~CH~CCH,---+
It
0
‘c-
H’
CHZ-CHZ I t CH3C, ,COH +O I OH
0
I
,A
CHZ-
H+
Ho,c,o/c=oI
CH3\
-
CHZ
CH3-4,
F,N’
0
‘0
O\$/OH
NO,
I
-
H+
CH,$CHZCHzCCH,
--t
I
*I
I1
CH&CH,CH,CCH,
I
CH3
CH,
C/CH,CH,CCH, + II 0
I Some similar acid-catalyzed cyclization and addition reactions have been reported for reagents other than difluoramine. For example, the acetylation of levulinic acid was reported to give 4-acetoxy-4-methylbutyrolactone.5 Tetrahydrofuran derivatives were formed by the acid-catalyzed ring closure of both 4-hydroxy olefins, and 5-hydroxy olefim6 Also, y-hydr~xyaldehydes~ have been reported to give 2-alkoxytetrahydrofurans on reaction with alcohols. The reaction of acetol with alcohols gave 2,5-dialkoxy-2,5-dimethyl-l,4-dioxanes.* The reaction of 5-methyl-5-nitro-2-hexanoneis explainable on the basis of protonation of an oxygen atom of the nitro group followed by loss of nitrous acid and intramolecular alkylation of the carbonyl oxygen. This function of a nitro group as a leaving group in an alkylation reaction is novel. Primary and secondary nitroalkanes have been reported to react with acetic anhydride and Lewis acids to give alkyl acetates, but evidence was reported for an SNi mechanism involving an 0acyl intermediateeg Recent nmr studies1° have shown that primary nitroalkanes are protonated reversibly in strong acids, whereas t-nitrobutane gives the t-butyl cation. In a prolonged reaction of acetonylacetone with difluoramine in fuming sulfuric acid at room temperature, ring opening of the initially formed tetrahydrofuran de(5) J. Bredt, Ann., 256, 314 (1890); for a review of other cyclizations of levulinic acid, see R. H. Leonard, Ind. Eng. Chem., 48, 1331 (1956). (6) R. Paul and H. Normant, Compt. Rend., 216, 689 (1943); H. Normant, ibid., 226, 733 (1948); 0. Riobe, Ann. Chim., (121 4, 593 ... (1949). -, (7) B. Helferich, et al., Ber., 52, 1126 (1919). (8) M. Bergmann and A . Miekeley, ibid., 64, 802 (1931); M. Bergmann and S . Ludewig, Ann., 436, 1973 (1924). (9) P. I
