Solvolysis of 1-Adamantylcarbinyl and 3-Homoadamantyl Derivatives. Mechanism of the Neopentyl Cation Rearrangement<sup>1</sup>

Nordlander, J. Eric; Jindal, Satya P.; Schleyer, Paul von Ragué; Fort, Raymond C.; Harper, Jon J.; Nicholas, Robert D.

doi:10.1021/ja00971a032

Cited by 47 publications

(22 citation statements)

References 3 publications

(4 reference statements)

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“…Found: C,61.78;H,10.10;N,7.95 The amine 15 hydrochloride (25 mg, 0.14 mmol) was acetylated with acetic anhydride (0.21 g, 2.0 mmol) in pyridine (2.5 mL) at 50 "C for 2 h and the usual workup, followed by recrystallization from n-hexane-CHzCl2, afforded the acetylamino derivative 16 as colorless crystals (22 mg, 86.7%), mp 87.5-88.5 "C (lit.14 mp 85-86 "C), which the IR and NMR spectra were superimposable with an authentic sample. '4 3-Aminohomoadamantane (19). A mixture of azide 18 (90 mg, 0.47 mmol) and lithium aluminum hydride (90 mg, 2.4 mmol) in anhydrous ether (4 mL) was stirred for 15 h at room temperature.…”

Section: -Hydroxy-4-azatricyclo[43113~s]undecane (3)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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Section: -Hydroxy-4-azatricyclo[43113~s]undecane (3)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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“…However, to the best of our knowledge, there is no precedence in the literature that describes the transformation of 1‐adamantylmethyl to 3‐methyladamantane‐1‐yl. In contrast, it is well known that the homoadamantane‐1‐yl cation is readily formed from 1‐adamantylmethyl upon solvolysis . Therefore, we assumed that the [C 11 H 17 ] + fragment was homoadamantane‐1‐yl in this study.…”

Section: Resultsmentioning

confidence: 93%

Gas‐phase fragmentation of 1‐adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively ²H‐labeled guest molecules

Čablová

Rouchal

Hanulíková

et al. 2017

Rapid Comm Mass Spectrometry

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The structures of two adamantane-based fragments and the mechanisms of their formation were rationalized. Two distinct geometric arrangements for the adamantane cage inside the CB7 cavity were hypothesized to explain the differences in the fragmentation patterns for guests with minimal, moderate, and high steric hindrance. This finding brings new insight into the understanding of intrinsic behavior of the adamantane-based guests inside the CB7 cavity.

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“…For the synthetic procedure, see: Nordlander et al (1966). For the structure of a related non-polar adamantane derivate, see: Rouchal et al (2010).…”

Section: Related Literaturementioning

confidence: 99%

“…Sapphire2 diffractometer Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) T min = 0.480, T max = 1.000 5102 measured reflections 951 independent reflections 900 reflections with I > 2(I) Data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al, 2008); software used to prepare material for publication: SHELXL97. The title compound is well known and widely used in chemistry of adamantane derivates as convenient source of 1adamantylmethyl substituent (Nordlander et al, 1966). Although this compound is very easy to purify via crystallization or sublimation, it is prone to form soft thin plates.…”

Section: Oxford Diffraction Xcaliburmentioning

confidence: 99%

1-(Bromomethyl)adamantane

et al. 2011

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Solvolysis of 1-Adamantylcarbinyl and 3-Homoadamantyl Derivatives. Mechanism of the Neopentyl Cation Rearrangement¹

Cited by 47 publications

References 3 publications

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

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

Gas‐phase fragmentation of 1‐adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively ²H‐labeled guest molecules

1-(Bromomethyl)adamantane

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Solvolysis of 1-Adamantylcarbinyl and 3-Homoadamantyl Derivatives. Mechanism of the Neopentyl Cation Rearrangement1

Cited by 47 publications

References 3 publications

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

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

Gas‐phase fragmentation of 1‐adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively 2H‐labeled guest molecules

1-(Bromomethyl)adamantane

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Solvolysis of 1-Adamantylcarbinyl and 3-Homoadamantyl Derivatives. Mechanism of the Neopentyl Cation Rearrangement¹

Gas‐phase fragmentation of 1‐adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively ²H‐labeled guest molecules