THE REACTION OF UNSATURATED CARBOHYDRATES WITH CARBON MONOXIDE AND HYDROGEN: II. STRUCTURE AND STEREOCHEMISTRY OF THE ANHYDRODEOXYHEXITOLS FROM 3,4-DI-<i>O</i>-ACETYL-<scp>D</scp>-XYLAL

Rosenthal, Alex; Abson, D.

doi:10.1139/v64-272

Cited by 19 publications

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“…Soc., 48, 2933 (1926). 14, R, -OCH3; Re = H;R3-OAc was 2,4-dimethoxy-l-naphthol (2). Hydrolysis of 1 with ethanolic hydrogen chloride yielded, under the same conditions, 2,4-diethoxy-l-naphthol (3) and, furthermore, the products 2 and 3 were found to be interconvertible under the same conditions of reaction and time.…”

Section: Methodsmentioning

confidence: 88%

“…N-(2-Octyl)methylhexylketimine (2).-A solution of 2-octanone (157.5 g, 1.24 mol) and 2-aminooctane (158.9 g,1.24 mol) in toluene (1.5 1.) was refluxed overnight with a Dean-Stark trap in which water (20.2 g, 1.13 mol) was collected.…”

Section: Methodsmentioning

confidence: 99%

“…(2),161 (5).2.4-Dimethoxy-1-naphthol acetate (11) had mp 90.5-91.5°; uv max 253 m^(t 40,200), 301 (4680); ir (CHCU) 2940, 2840…”

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Alkoxyl exchange reactions of naphthalene ethers

Baldwin¹,

Basson²

1969

J. Org. Chem.

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The Journal of Organic Chemistry due to the more stable isomer 2A which seems to make up 87% of the mixture.Of the various conformations which can result from rotation about the single CN bond in ZA, the two most likely to be present in the transition state leading to reduction are shown in the diagrams below. When the tertiary hydrogen lies in the plane of the paper, the attacking hydride ion is more likely to approach the olefinic carbon from below the plane of the paper for the particular enantiomer shown. In this case, the incoming ion encounters the methyl group rather than the bulkier six-carbon chain and the amine is produced as the racemic diastereoisomer. HA second likely conformation for this enantiomer would occur when the tertiary hydrogen and the methyl group are both staggered on either side of the plane of the paper. Then the attacking hydride ion would prefer to approach from above the plane of the paper and so encounter the hydrogen atom rather than the bulkier methyl group. Consequently, the amine would be produced in the meso form when the ketimine is reduced in this conformation. /(CH2)5CH3The observation that 3 is formed as an isomeric mixture containing 627; of the racemate indicates that the first conformation is more favored than the second. Other factors, however, in addition to those described above may well be hvolved. Experimental Section N-(2-0ctyl)methylhexyketimine @).-A solution of 2-octanone (157.5 g, 1.24 mol) and 2-aminooctane (158.9 g,1.24 mol) in toluene (1.5 1.) was refluxed overnight with a Dean-Stark trap in which water (20.2 g, 1.13 mol) was collected. The solvent was evaporated and the residue distilled under nitrogen to give a small forerun of starting materials, bp 45-95' (1 mm), followed by the ketimine (190 g, 62%): bp 96-97' (52 p ) ; n*7~ 1.4414; uv max (isooctane) 245 mp (e 112); ir (liquid film) 1658 cm-l (C=N); nmr (neat) T 6.62 (m, 1, CH-N=C), 7.87 (t, 2, J = 6 He, CHz-C=N), 8.16 and 8.30 (S, 3, CHa=-N) ppm. Analysis by glpc on several different columns showed one peak. Bis( 1-methy1heptyl)amine (3).-N-(2-0ctyl)methylhexylketimine (150.0 g, 0.772 mol) was added to a stirred solution of lithium aluminum hydride (29.3 g, 0.772 mol) in tetrahydrofuran (1 1.) at room temperature under a nitrogen atmosphere. After refluxing for 24 hr, the metal complex was decomposed by treatment with aqueous base in the usual manner,8 the resulting susAnal. Calcd for ClsHaN: N, 5.85. Found: N, 5.70.During the course of our work on the photooxidation of aromatic systems* we had occasion to prepare 1,2,4 trimethoxynaphthalene. In order to do this we hydrolyzed 1,4diacetoxy-2-meth~xynaphthalene~ (1) with (1) To whom all communications should be addressed.

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Section: Methodsmentioning

confidence: 88%

Section: Methodsmentioning

confidence: 99%

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Alkoxyl exchange reactions of naphthalene ethers

Baldwin¹,

Basson²

1969

J. Org. Chem.

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“…needle. Conditions for paper chromatographic separations, isolation and deacetylation of 0x0 products, and measurement of infrared spectra have been described (1). T h e n.m.r.…”

Section: General Co?zsiderationsmentioning

confidence: 99%

“…The For personal use only. described previously (1). After removal of the catalyst, a portion of the sirupy product was deacetylated, and separated by paper chromatography into fractions (I) and (11).…”

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SYNTHESIS OF ANHYDRODIDEOXYHEXITOLS RELATED TO ANHYDRODEOXYHEXITOLS FROM OXO REACTION OF 3,4-DI-O-ACETYL-D-XYLAL

Rosenthal¹,

Abson²

1965

Can. J. Chem.

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2,3-Di-O-acetyl-l,5-anhydro-4,6-dideoxy-~-nrabi?~o-hexitol (VI) and 2,3-di-0-acetyl-1,s-anhydro-4,6-dideoxy-I--rylo-hexitol (VII) were prepared by reaction of ~ilethyl magnesium bromide with 3,4-di-0-acetyl-~-xylo-pyra1losyl chloride. An independent synthesis of compounds (VI) and (VII) was also achieved from the 6-0-tosyl derivatives of the 0x0 products from 3,4-di-O-acetyl-~-xylal, thus confirming that the configuration of the secondary hydroxyls of glycals is not inverted during the 0x0 reaction.Part I1 of this series ( I ) showed that application of the 0x0 reaction to 3,4-di-0-acetyl-11-xylal, followed by deacetylation, gave 1,s-anhydro-4-deoxjr-D-arabino-hexitol (I) and 1 ,5-anhydro-4-deoxy-L-xylo-hexitol (I I). The I--configuration of C-5 of (I I) was established by correlation with C-4 of 1,4-anhydro-5-deoxy-D-arabino-hexitol; the C-5 configuration of (I) must therefore be D , a s this anhydrodeoxyhexitol, on cleavage of the 0-glycol bond and reduction, formed a trio1 ether which was the mirror image of that derived from (11). The remaining asymmetric centers of (I) and (11), a t C-2 and C-3, were assuined to be unchanged in configuration from the parent polyol.Von Rudloff et al. (2) carried out the hydrogenolysis of methyl-a-D-glu~op~ranoside a t 210" t o give 1,s-anhydro-4-deoxy-hexitol along with other products. Gorin (3) subsequently sho\\red that the hexitol consisted of two 1,s-anhydro-1-deoxy-D-hexitols. On the bases of coillparative rates of lead tetracetate oxidation and con~parison of observed specific rotations with those calculated from application of the principle of opt-ical superposition, these hexitols were postulated to have structures (I) and (111) (1,;S-anhydro-4-deoxy-D-lyxo-hexitol). The compound t o which they assigned the D-nrabino configuration +19"; tris-p-nitrobenzoate, 111.p. 115-119", [a]D +59") is clearly different from our con~pound (I) ([DID -13"; tris-p-nitrobenzoate, 1n.p. 21;3", [elD -50"). We have accordingly carried out a series of reactions correlating the secondary hydroxyl configurations of (I) and (11) with those of ~-x y l a l , thereby confirming our assignments of structures (I) and (11). Bonner (1) has shown that the hemiacetal halogen of pol yacetylglycos>~l halides undergoes a et eta the tical reaction with Grignard reagent \\.hen the latter is present in sufficient-excess, and has, moreover, provided adecl~~ate experirnental proof to sho\\-that decomposition of the Grignard adduct t o the ester group does not involve rupture of asymmetric bonds, and therefore no change of configuration talres place during reaction with the Grignard reagent. lising the Grignard synthesis ure have been successful in preparing the diacetates of the two 6-deoxy analogues of (I) and (11) For personal use only.

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Sodium Tetracarbonylcobaltate

Kerr

2001

Encyclopedia of Reagents for Organic Synthesis

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THE REACTION OF UNSATURATED CARBOHYDRATES WITH CARBON MONOXIDE AND HYDROGEN: II. STRUCTURE AND STEREOCHEMISTRY OF THE ANHYDRODEOXYHEXITOLS FROM 3,4-DI-O-ACETYL-D-XYLAL

Cited by 19 publications

References 5 publications

Alkoxyl exchange reactions of naphthalene ethers

Alkoxyl exchange reactions of naphthalene ethers

SYNTHESIS OF ANHYDRODIDEOXYHEXITOLS RELATED TO ANHYDRODEOXYHEXITOLS FROM OXO REACTION OF 3,4-DI-O-ACETYL-D-XYLAL

Sodium Tetracarbonylcobaltate

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