Organic fluoronitrogens. VII. Tris(difluoroamino)-fluoromethane and related compounds

Koshar, R. J.; Husted, Donald R.; Wright, Charles D.

doi:10.1021/jo01287a031

Cited by 21 publications

(8 citation statements)

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“…Bromination with N-bromosuccinimide (NBS) followed by dehydrobromination3 has been used to make dehydroabietic acid from abietic acid. In the present investigation methyl dehydroabietate (10) was still the major product, but a fair yield of ethers was also obtained.…”

supporting

confidence: 49%

Free-radical bromination of methyl abietate by N-bromosuccinimide and solvolysis of the products

Sircar¹,

Fisher²

1970

J. Org. Chem.

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bond dipoles with approximately the same orientation are introduced at the same distance: (1) H-CH2CH2-C02H vs. C1-CH2CH2C02H, for which = 0.9 and µ = m(CC1) -m(CH) « m(CH3C1) = 1.9 D; (2) NH2CH2C02H vs. H-NH2+CH2C02H, for which = 2.2 and µ = 1.3 D. If the value of DE govering the charge-dipole interaction were the same in both pairs, the value of observed for (1) would require that the charge-dipole contribution to for (2) be 0.6 pX unit, which is 27% of the observed total Free-Radical Bromination of Methyl Abietate by N-Bromosuccinimide and Solvolysis of the Products

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supporting

confidence: 49%

Free-radical bromination of methyl abietate by N-bromosuccinimide and solvolysis of the products

Sircar¹,

Fisher²

1970

J. Org. Chem.

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“…(21) This stereospecificity was consistent with the results of others who have reported the formation of only one isomer in similar solid state fiuorinations. 10 The stereospecificity in these cases is probably dependent upon the mechanism of the fluorination and may be analogous to that observed in catalytic hydrogenations in which the catalyst surface is an important fac-(22) W. J. Middleton and C. G. Krespan, J. Org, Chem., S3, 3625 (1968). (23) E, A. Mitsch, J. Amer.…”

Section: Resultsmentioning

confidence: 66%

“…column (15% Kel-F oil on 60-80 mesh Chromosorb P) at 70°. The product was a low-boiling liquid: bp 20°( 229 mm); ir (gas) 6.20 (w) C=N; 7.45 (m); 8.05 (s) CF; 8.80 (m), 9.10 (w); 10.0 (w), 10.25 (w), 11.25 (s) and 11.70 (w) NF; 13.35 (s), 13.95µ (m); nmr (CC14) * -45.8 (s, 1, C=NF), -42.8 (s, 2, NF,), 80.2 (t, 3, / = 9.6 Hz, CF3), 109.6 (m, 2, J = 9.6 Hz, CF,C=NF), 123.9 (m, 2, J = 9.6 Hz, CF3CF2). l,l-Bis(difluoramino)heptafluorobutyl Methyl Ether (6).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of N,N,N'-trifluoroamidines

Ross¹,

Coon²,

Hill³

1970

J. Org. Chem.

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liquor from the recrystallization of 3 above was evaporated to dryness and the residual oil (745 mg), composed of methyl A6-dehydrodehydroabietate (7), methyl 7/3-methoxydehydroabietate (5), methyl 7a-methoxydehydroabietate (3), and methyl 18-methoxydehydroabietate (4) (identified 3, 4, and S by their known relative retention times) was chromatographed over alumina (25 g).Elution with 30% benzene-hexane mixture (200 ml) (Fraction 9, 10) and 40% benzene-hexane mixture (100 ml) (Fraction 11) gave methyl A6 8-dehydrodehydroabietate19 (7) as oil (120 mg) with 80% purity. Impurities are 3 and 5. Further elution with 40% benzene-hexane mixture (50 ml) (Fraction 12) gave pure 7 (26 mg): X®1°H 265 and 220 µ; Xneat 3.37 (aromatic), 5.80 (>C=0), 6.25 (>C=C<), 6.42, 6.73 (aromatic), 8.06 (C-O ester), 9.27, 12.18 (aromatic), and 14.57 (m-CH=CH) µ; nmr (cps) 428 (m, 34, aromatic protons), 394 (a pair of doublets, Jab = 9 cps, /ax = 3 cps, 1 H, C7-proton), 346 (a pair of doublets, Jab = 9 cps, /ax = 2.5 cps, 1 H, C6-proton), 220 (s, 3 H, Ci6-OCH3), 177 (t, / = 3 cps, CVproton), 166 (m, / = 7 cps, Ci8-proton), 85 (s, 3 H, Cie-protons), 75 (d, / = 7 cps, 65 (s, 3 H,.The identity was further confirmed by the relative retention time in 15% DECS column (6 X Vie in.) at 230°with the known data (methyl stearate80 as internal standard).Further elution with benzene (100 ml) (Fraction 21) and 10% ether-benzene (200 ml) (Fraction 22, 23) gave solid 3 (131 mg) mixed with 5.

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“…14,38 Whilst no difficulties were encountered in this work and, indeed, standard work-up and chromatographic purification techniques were utilised to isolate the difluoroamine products 3, appropriate precautions should be taken when handling potentially explosive materials.…”

Section: Scheme 1 Synthesis Of Perfluoroaniline Substrates 2mentioning

confidence: 99%

“…14,38 Whilst no difficulties were encountered in this work, appropriate precautions should be taken when handling potentially explosive materials.…”

Section: Synthesis Of Difluoramine Derivativesmentioning

confidence: 99%

Continuous Flow Synthesis of Difluoroamine Systems by Direct Fluorination

2013

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(2013) 'Continuous ow synthesis of diuoroamine systems by direct uorination.', Australian journal of chemistry., 66 (2). pp. 145-150. Further information on publisher's website:http://dx.doi.org/10.1071/CH12381Publisher's copyright statement: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. AbstractContinuous flow methodology for the synthesis of perfluoroaryl difluoroamine derivatives by reaction of fluorine gas with an appropriate perfluoroaniline substrate is described, further demonstrating the efficient use of flow regimes for reactions involving highly reactive and toxic reagents.

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Organic fluoronitrogens. VII. Tris(difluoroamino)-fluoromethane and related compounds

Cited by 21 publications

References 0 publications

Free-radical bromination of methyl abietate by N-bromosuccinimide and solvolysis of the products

Free-radical bromination of methyl abietate by N-bromosuccinimide and solvolysis of the products

Synthesis of N,N,N'-trifluoroamidines

Continuous Flow Synthesis of Difluoroamine Systems by Direct Fluorination

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