Chemistry of adamantanes and related compounds. II. 3-Substituted 4-azahomoadamantanes and endo-7-(aminomethyl)bicyclo[3.3.1]nonan-3-one from rearrangement of 1-(N,N-dichloroamino)adamantane by aluminum chloride

Kovacic, Peter; Liu, Jih-Hua; Levi, E.; Roskos, Philip D.

doi:10.1021/ja00751a036

Cited by 14 publications

(6 citation statements)

References 2 publications

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“…1.15 (s, 9), 3.22 (s, 3); mass spectrum, m/e (relative intensity) 87 (2), 74 (2), 73 (40), 59 (4), 58 (1), 57 (25), 56 (4), 55 (5), 45 (15), 44 (2), 43 (48), 42 (10), 41 (100), 40 (6), 39 (35), 31 (18). The molecular ion (m/e 88) was of the same magnitude as the background noise.…”

Section: Methodsmentioning

confidence: 99%

Nitrous acid deamination of 1,1-disubstituted aromatic hydrazines

Rosa¹,

Haberfield²

1981

J. Org. Chem.

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Section: Methodsmentioning

confidence: 99%

Nitrous acid deamination of 1,1-disubstituted aromatic hydrazines

Rosa¹,

Haberfield²

1981

J. Org. Chem.

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“…Found: C, 44.1; , 4.0; N, 5.9. (b) JV-tert-ButyI-3-methyl-2,l-benzisoxazolium Perchlorate (le). Nitromethane (20 mL) containing 3-methyl-2,l-benzisoxazole (13 g), iert-butyl alcohol (8 g) and 70% perchloric acid (16 g) was stirred at room temperature for 48 h. To the solution was added diethyl ether (200 mL), and the precipitated white solid was collected and washed with diethyl ether. Recrystallization from methanol gave lV-ferf-butyl-3-methyl-2,l-benzisoxazolium perchlorate (20 g): mp 183 °C dec; NMR (CD3CN) 8.0 (m, 3 H), 7.4 (m, 1 ), 3.0 (s, 3 H), 1.9 (s, 9 H); IR (KBr) 1625,1450,1090,760 cm-1; UV (H20) 335 TV-Methyl-3-phenyl-2,1-benzisoxazolium Fluorosulfonate (lb): 87%; mp 170 °C dec; NMR (CDaCN) 8.0 (m, 9 H), 4.5 (s, 3 H); UV (H20) 372 Anal.…”

Section: Experimental Section12mentioning

confidence: 99%

“…chemical shifts of methyl protons in 1-methyl-4-nitroimidazole ( 3.90) and 1-methyl-5-nltroimidazole ( 4.05) (ref 11). (13) Cf. chemical shifts of 1-methyl protons in 1-methylimidazole ( 3.70) and 1,2-dimethyl imidazole ( 3.52) [(a) ref 11; (b) M. R. Grimmet, Adv.…”

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confidence: 99%

Photochemistry of 2,1-benzisoxazolium (anthranilium) salts

Haley¹

1977

J. Org. Chem.

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“…

Several bridgehead azides such as 1-adamantyl (2), 3,5-dimethyl-l-adamantyl (5), 3,5,7-trimethyl-l-adamantyl (10), l-bicyclo[3.3.1]nonyl (14), and 3-homoadamantyl azide (18) were prepared in high yields from the corresponding bridgehead alcohols on treatment with sodium azide in 57% H2SO4-CHCI3. Azides 2,5, and 10 were decomposed in 95% H2SO4 to afford the rearranged products, 4-azahomoadamantan-3-ol derivatives 3, 7, 8, and 12, which were also obtained from the corresponding bridgehead alcohols on treatment with sodium azide in 95% H2SO4.

…”

mentioning

confidence: 99%

Synthesis of adamantane derivatives. 37. A convenient and efficient synthesis of 1-azidoadamantane and related bridgehead azides, and some of their reactions

Sasaki¹,

Eguchi²,

Katada³

et al. 1977

J. Org. Chem.

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Several bridgehead azides such as 1-adamantyl (Z), 3,5-dimethyl-l-adamantyl (5), 3,5,7-trimethyl-l-adamantyl (lo), l-bicyclo[3.3.l]nony1(14), and 3-homoadamantyl azide (18) were prepared in high yields from the corresponding bridgehead alcohols on treatment with sodium azide in 57% HZSOd-CHC13. Azides 2,5, and 10 were decomposed in 95% Hzs0.1 to afford the rearranged products, 4-azahomoadamantan-3-01 derivatives 3,7,8, and 12, which were also obtained from the corresponding bridgehead alcohols on treatment with sodium azide in 95% HzS04. Azides 5,10,14, and 18 were converted to the corresponding bridgehead amines 6,11,15, and 19.Organic azides are well known as a n excellent synthetic starting material, however, synthetic studies by using bridgehead azides seem to be quite limited:2 this might be due to the lack of a facile and efficient method for introduction of t h e azide group a t bridgehead positions. For example, 1-azidoadamantane (2) has been prepared previously via a direct substitution method of 1-bromoadamantane with sodium azide in dimethyl sulfoxide by us3 or via a diazo-transfer method to 1-aminoadamantane by Quast and Eckert: but the former method gives only a moderate yield of 2 and the latter method requires vigorous anhydrous conditions and longer reaction times. T h e direct substitution method was considerably improved recently by Miller5 by using zinc chloride as t h e catalyst, but t h e reaction is quite slow. This paper deals with a convenient and efficient synthesis of 2 and related bridgehead azides as well as some of their reactions. Results and DiscussionIn view df the fact that secondary and tertiary aryl carbinols can be converted t o the corresponding azides with hydrazoic acid in trichloroacetic acid6-8 and the relatively facile formation of 1-adamantylcarbenium ion under acidic conditions? we examined the reaction of 1-adamantanol(1) with in situ generated hydrazoic acid in various acid-chloroform mixtures. As shown in Table I, azide 2 was obtained in a n excellent yield by using 57% H2SO4 as the acid and 3 h as the reaction time. However, azide 2 was not stable under t h e reaction conditions and was converted slowly to a rearranged product 3, as demonstrated by t h e data of a 15-h reaction (Table I). 2 was also converted t o 3 exclusively on treatment with 95% H2S04-CHC13 (Scheme I). The rearranged product 3 was identified as 3-hydroxy-4-azatricyclo[4.3.1.13~A]undecane (4-azahomoadamantan-3-01) by comparison with an authentic ~a m p l e .~J O 3 was also obtained directly from 1 in 94% yield by using 95% H2S04-CHC13 and sodium azide (1.25-fold excess t o 1) (The Schmidt reaction). This provides a facile and efficient synthesis of 3. 'The reaction of 1 with sodium azide in other acid-CHCl3 mixtures did not give satisfactory results, as summarized in Table I. Application of this simple azide synthetic method to 1-hydroxy-3,5-dimethyladamantane (4) afforded azide 5 in 72% yield which was converted to known amine 611 on lithium aluminum hydride reduction. Azide 5 on treatment with 9...

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Chemistry of adamantanes and related compounds. II. 3-Substituted 4-azahomoadamantanes and endo-7-(aminomethyl)bicyclo[3.3.1]nonan-3-one from rearrangement of 1-(N,N-dichloroamino)adamantane by aluminum chloride

Cited by 14 publications

References 2 publications

Nitrous acid deamination of 1,1-disubstituted aromatic hydrazines

Nitrous acid deamination of 1,1-disubstituted aromatic hydrazines

Photochemistry of 2,1-benzisoxazolium (anthranilium) salts

Synthesis of adamantane derivatives. 37. A convenient and efficient synthesis of 1-azidoadamantane and related bridgehead azides, and some of their reactions

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