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Trichloroacetonitrile

December 15, 2023

Trichloroacetonitrile is an organic compound with the formula CCl3CN. It is a colourless liquid, although commercial samples often are brownish. It is used commercially as a precursor to the fungicide etridiazole. It is prepared by dehydration of trichloroacetamide.[1] As a bifunctional compound, trichloroacetonitrile can react at both the trichloromethyl and the nitrile group. The electron-withdrawing effect of the trichloromethyl group activates the nitrile group for nucleophilic additions. The high reactivity makes trichloroacetonitrile a versatile reagent, but also causes its susceptibility towards hydrolysis.

Trichloroacetonitrile
Names
Preferred IUPAC name
Trichloroacetonitrile
Identifiers
  • 545-06-2 Y
3D model (JSmol)
  • Interactive image
ChemSpider
  • 13861934
ECHA InfoCard 100.008.078
  • 24900271
UNII
  • 6397DL8869 Y
  • DTXSID0021672
  • InChI=1S/C2Cl3N/c3-2(4,5)1-6
    Key: DRUIESSIVFYOMK-UHFFFAOYSA-N
  • ClC(Cl)(Cl)C#N
Properties
C2Cl3N
Molar mass 144.38 g·mol−1
Appearance colourless liquid
Density 1.44 g/mL
Melting point −42 °C (−44 °F; 231 K)
Boiling point 83 to 84 °C (181 to 183 °F; 356 to 357 K)
insoluble
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 GHS06, GHS09
NFPA 704 (fire diamond)
Health 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
4
1
0
Flash point 195 °C (383 °F; 468 K)
Safety data sheet (SDS) MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Synthesis edit

The production of trichloroacetonitrile by dehydration of trichloroacetamide was first described in 1873 by L. Bisschopinck at the Katholieke Universiteit Leuven.[2]

 

Trichloroacetonitrile can be obtained by chlorination of acetonitrile on a zinc, copper and alkaline earth metal halide-impregnated activated carbon catalyst at 200–400 °C with a 54% yield.[3]

 

The high temperatures required by this process favours the formation of byproducts, such as tetrachloromethane. In contrast, the chlorination of acetonitrile saturated with hydrogen chloride leads to pure trichloroacetonitrile even at 50–80 °C in good yields.[4]

Like other halogenated acetonitriles, trichloroacetonitrile is produced from organic substances such as algae, humic acids and proteinaceous material in the disinfecting chlorination of water from natural sources.[5][6]

Properties edit

 
Rounded bond lengths and angles of trichloroacetonitrile

Freshly-distilled trichloroacetonitrile is a colorless liquid with a pungent odor that discolours rapidly yellowish to light brown. It is sensitive towards water, acids and bases.

The bond lengths are 146.0 pm (C–C), 116.5 pm (C≡N) and 176.3 pm (C–Cl). The bond angle is 110.0° (Cl–C–Cl).[7]

Use edit

The substitution of all electronegative substituents in trichloroacetonitrile by nucleophilic attack of alkoxide anions produces orthocarbonic acid esters in high yield.

Due to the high reactivity of the chlorine atoms, trichloroacetonitrile can be used (especially in combination with triphenylphosphine) to convert allylic alcohols into the corresponding allylic chlorides.[8]

 

With carboxylic acids, acyl chlorides are obtained.[9]

Due to the mild reaction conditions, the Cl3CCN/PPh3 system is also suitable for the activation of carboxylic acids and their linkage with supported amino compounds to amides (peptides) in solid-phase syntheses.[10] From sulfonic acids, the corresponding sulfochlorides are formed analogously.[11] In an analogous manner, the activation of diphenylphosphoric acid with Cl3CCN/PPh3 and reaction with alcohols or amines proceeds to the corresponding phosphoric acid esters or amides in a gentle and efficient one-pot reaction.[12]

Also, phenolic hydroxy groups in nitrogen-containing aromatics can be converted into the chlorine compounds.[13]

 

In a Hoesch reaction, aromatic hydroxyketones are formed in the reaction of substituted phenols with trichloroacetonitrile, for example from 2-methyl phenol the 2-trichloroacyl derivative in 70% yield.[14]

 

The electron-withdrawing effect of the trichloromethyl group activates the nitrile group of trichloroacetonitrile for the attack of nucleophilic oxygen, nitrogen and sulfur compounds. For example, alcohols give O-alkyltrichloroacetimidates under basic catalysis in a direct and reversible addition,[15] which can be isolated as stable and less hydrolysis-sensitive adducts.

 

With primary and secondary amines, N-substituted trichloroacetamidines are formed in a smooth reaction with good yields, which can be purified by vacuum distillation and are obtained as colorless, malodorous liquids.[16] Reaction with ammonia and then with anhydrous hydrogen chloride gives the solid trichloroacetamidine hydrochloride, the starting compound for the fungicide etridiazole.

In academic research, trichloroacetonitrile is used as a reagent in the Overman rearrangement, converting allylic alcohols into allylic amines.[17][18][19] The reaction is based on a [3,3]-sigmatropic and diastereoselective rearrangement.

Benzyl trichloroacetimidate is easily accessible from benzyl alcohol and trichloroacetonitrile.[20] Benzyl trichloroacetimidate is useful as a benzylating reagent for sensitive alcohols under mild conditions and to preserve chirality.[21]

O-Glycosyl-trichloroacetimidates for the activation of carbohydrates edit

R. R. Schmidt and co-workers[22] have described the selective anomeric activation of O-protected hexopyranoses (glucose, galactose, mannose, glucosamine, galactosamine), hexofuranoses and pentopyranoses with trichloroacetonitrile in the presence of a base, as well as glycosylations under acid catalysis.[23][24][25]

Under kinetic control[26] with potassium carbonate as the base, β-trichloroacetimidates are formed selectively, whereas with sodium hydride, caesium carbonate or potassium hydroxide[27] and in the presence of phase-transfer catalysts[28] only α-trichloroacetimidates are obtained (thermodynamically controlled).

 

The trichloroacetimidates are reacted between −40 °C and room temperature with boron trifluoride etherate in dichloromethane with O-protected sugars. This method usually gives better results than the Koenigs–Knorr method using silver salts or the Helferich method which uses problematic mercury salts. Since an inversion occurs at the anomeric center, the reaction leads to β-O-glycosides (when using α-trichloroacetimidates). The trichloroacetimidate method often produces sterically uniform glycosides under mild reaction conditions in very good yields.

 

Thioacetic acid reacts with acetyl-protected α-galactosyl trichloroacetimidate even without additional acid catalysis to thioglycoside, from which (after cleavage of the protective groups) 1-thio-β-D-galactose is easily accessible, which is useful for the separation of racemates of amino acids.[29]

 

Trichloroacetonitrile was an important fumigant in the first half of the 20th century, but today it has become obsolete for this application.[30]

See also edit

References edit

  1. ^ Pollak, Peter; Romeder, Gérard; Hagedorn, Ferdinand; Gelbke, Heinz-Peter. "Nitriles". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a17_363.
  2. ^ Bisschopinck, L. (1873). "Ueber die gechlorten Acetonitrile". Berichte der Deutschen Chemischen Gesellschaft. 6: 731–734. doi:10.1002/cber.187300601227.
  3. ^ US patent 2375545, R. T. Foster, "Process for the preparation of trichloroacetonitrile", issued 1945-05-08, assigned to Imperial Chemical Industries 
  4. ^ US patent 2745868, G. Käbisch, "Process for the production of trichloroacetonitrile", issued 1956-05-15, assigned to Deutsche Gold- und Silber-Scheideanstalt, formerly Roessler 
  5. ^ Guidelines for Drinking Water Quality (PDF). Recommendations. Vol. 1 (3rd ed.). Geneva: World Health Organization. 2004. ISBN 9-2415-4638-7.
  6. ^ Frank Bernsdorff (2007). Untersuchungen zur abiotischen Bildung von Acetonitril, Haloacetonitrilen und Trichlornitromethan [Investigations into abiotic formation of acetonitrile, haloacetonitriles and trichloronitromethane] (in German). GRIN. p. 5. ISBN 9783638383431.
  7. ^ Lide, David R., ed. (2010). "Structure of Free Molecules in the Gas Phase". CRC Handbook of Chemistry and Physics (90th ed.). Boca Raton, FL: CRC Press/Taylor and Francis. pp. 9–46.
  8. ^ Matveeva, E. D.; et al. (1995). "Regioselective and stereoselective substitution of hydroxyl group for halogen in allyl alcohols". Russian Journal of Organic Chemistry. 31 (8): 1121–1125.
  9. ^ Jang, D. O.; et al. (1999). "A mild and efficient procedure for the preparation of acid chlorides from carboxylic acids". Tetrahedron Letters. 40 (29): 5323–5326. doi:10.1016/S0040-4039(99)00967-3.
  10. ^ Vago, J.; Greiner, J. (2002). "A useful acylation method using trichloroacetonitrile and triphenylphosphine for solid phase organic synthesis". Tetrahedron Letters. 43 (34): 6039–6041. doi:10.1016/S0040-4039(02)01241-8.
  11. ^ Chantarasriwong, O.; et al. (2006). "A practical and efficient method for the preparation of sulfonamides utilizing Cl3CCN/PPh3". Tetrahedron Letters. 47 (42): 7489–7492. doi:10.1016/j.tetlet.2006.08.036.
  12. ^ Kasemsuknimit, A.; et al. (2011). "Efficient amidation and esterification of phosphoric acid using Cl3CCN/Ph3P". Bulletin of the Korean Chemical Society. 32 (9): 3486–3488. doi:10.5012/bkcs.2011.32.9.3486.
  13. ^ Kijrungphaiboon, W.; et al. (2006). "Cl3CCN/PPh3 and CBr4/PPh3: two efficient reagent systems for the preparation of N-heteroaromatic halides". Tetrahedron Letters. 53 (6): 674–677. doi:10.1016/j.tetlet.2011.11.123.
  14. ^ Martin, R. (2011), Aromatic Hydroxyketones: Preparation and Physical Properties. Vol. 1 Hydroxybenzophenones (in German) (3rd ed.), Springer, doi:10.1007/978-1-4020-9787-4, ISBN 978-1-4020-9787-4
  15. ^ Nef, J. U. (1895). Annalen der Chemie. 287: 274. {{cite journal}}: Missing or empty |title= (help)
  16. ^ Grivas, John C.; Taurins, Alfred (1958). "Reaction of trichloroacetonitrile with primary and secondary amines. Part I. Preparation of some trichloroacetamidines". Canadian Journal of Chemistry. 36 (5): 771–774. doi:10.1139/v58-113. ISSN 0008-4042.
  17. ^ Nishikawa, T.; Asai, M.; Ohyabu, N.; Isobe, M. (1998). "Improved Conditions for Facile Overman Rearrangement". The Journal of Organic Chemistry. 63 (1): 188–192. doi:10.1021/jo9713924. PMID 11674062.
  18. ^ "Overman Rearrangement". Organic Chemistry Portal. organic-chemistry.org. Retrieved 2012-11-15.
  19. ^ Chen, Y. K.; Lurain, A. E.; Walsh, P. J. (2002). "A general, highly enantioselective method for the synthesis of D and L alpha-amino acids and allylic amines". Journal of the American Chemical Society. 124 (41): 12225–12231. doi:10.1021/ja027271p. PMID 12371863.
  20. ^ Schaefer, Fred C.; Peters, Grace A. (1961). "Base-Catalyzed Reaction of Nitriles with Alcohols. A Convenient Route to Imidates and Amidine Salts". The Journal of Organic Chemistry. 26 (2): 412–418. doi:10.1021/jo01061a034.
  21. ^ Eckenberg, E. P.; et al. (1993). "A useful application of benzyl trichloroacetimidate for the benzylation of alcohols". Tetrahedron. 49 (8): 1619–1624. doi:10.1016/S0040-4020(01)80349-5.
  22. ^ Schmidt, R. R.; Michel, J. (1980). "Einfache Synthese von α- und β-O-Glycosylimidaten. Herstellung von Glykosiden und Disacchariden" [Simple synthesis of α- and β-O-glycosylimidates. Manufacture of glycosides and disaccharides]. Angewandte Chemie. 92 (9): 763–764. Bibcode:1980AngCh..92..763S. doi:10.1002/ange.19800920933.
  23. ^ Schmidt, R. R. (1986). "Neue Methoden zur Glycosid- und Oligosaccharidsynthese – gibt es Alternativen zur Koenigs-Knorr-Methode?" [New methods for glycoside and oligosaccharide synthesis – are there alternatives to the Koenigs–Knorr method?]. Angewandte Chemie. 98 (3): 213–236. Bibcode:1986AngCh..98..213S. doi:10.1002/ange.19860980305.
  24. ^ Schmidt, R. R.; Kinzy, W. (1994). "Anomeric-oxygen activation for glycoside synthesis – the trichloroacetimidate method". Advances in Carbohydrate Chemistry and Biochemistry. 50: 21–123. doi:10.1016/S0065-2318(08)60150-X. ISBN 9780120072507. PMID 7942254.
  25. ^ Schmidt, R. R.; Jung, K.-H. (1997). "Oligosaccharide synthesis with trichloroacetimidates". In Hanessian, S. (ed.). Preparative Carbohydrate Chemistry. New York, NY: Marcel Dekker. pp. 283–312. ISBN 0-8247-9802-3.
  26. ^ Schmidt, R. R.; Michel, J. (1984). "Glycosylimidate, 12 Direkte Synthese vonO-α- undO-β-Glycosyl-imidaten". Liebigs Annalen der Chemie. 1984 (7): 1343–1357. doi:10.1002/jlac.198419840710.
  27. ^ Urban, F. J.; et al. (1990). "Synthesis of tigogenyl β-O-cellobioside heptaacetate and glycoside tetraacetate via Schmidt's trichloroacetimidate method; some new observatons [sic]". Tetrahedron Letters. 31 (31): 4421–4424. doi:10.1016/S0040-4039(00)97637-8.
  28. ^ Patil, V. J. (1996). "A simple access to trichloroacetimidates". Tetrahedron Letters. 37 (9): 1481–1484. doi:10.1016/0040-4039(96)00044-5.
  29. ^ Jegorov, A.; et al. (1994). "1-Thio-β-D-galactose as a chiral derivatization agent for the resolution of D,L-aminoacid enantiomers". Journal of Chromatography A. 673 (2): 286–290. doi:10.1016/0021-9673(94)85045-3.
  30. ^ Sax, N. M.; Lewis, R. J., eds. (1987). Hawley's Condensed Chemical Dictionary (11th ed.). New York, NY: Van Nostrand Reinhold. pp. 261, 1175.

December 15, 2023
trichloroacetonitrile, organic, compound, with, formula, ccl3cn, colourless, liquid, although, commercial, samples, often, brownish, used, commercially, precursor, fungicide, etridiazole, prepared, dehydration, trichloroacetamide, bifunctional, compound, trich. Trichloroacetonitrile is an organic compound with the formula CCl3CN It is a colourless liquid although commercial samples often are brownish It is used commercially as a precursor to the fungicide etridiazole It is prepared by dehydration of trichloroacetamide 1 As a bifunctional compound trichloroacetonitrile can react at both the trichloromethyl and the nitrile group The electron withdrawing effect of the trichloromethyl group activates the nitrile group for nucleophilic additions The high reactivity makes trichloroacetonitrile a versatile reagent but also causes its susceptibility towards hydrolysis Trichloroacetonitrile NamesPreferred IUPAC name TrichloroacetonitrileIdentifiersCAS Number 545 06 2 Y3D model JSmol Interactive imageChemSpider 13861934ECHA InfoCard 100 008 078PubChem CID 24900271UNII 6397DL8869 YCompTox Dashboard EPA DTXSID0021672InChI InChI 1S C2Cl3N c3 2 4 5 1 6Key DRUIESSIVFYOMK UHFFFAOYSA NSMILES ClC Cl Cl C NPropertiesChemical formula C 2Cl 3NMolar mass 144 38 g mol 1Appearance colourless liquidDensity 1 44 g mLMelting point 42 C 44 F 231 K Boiling point 83 to 84 C 181 to 183 F 356 to 357 K Solubility in water insolubleHazardsOccupational safety and health OHS OSH Main hazards GHS06 GHS09NFPA 704 fire diamond 410Flash point 195 C 383 F 468 K Safety data sheet SDS MSDSExcept where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa Infobox references Contents 1 Synthesis 2 Properties 3 Use 3 1 O Glycosyl trichloroacetimidates for the activation of carbohydrates 4 See also 5 ReferencesSynthesis editThe production of trichloroacetonitrile by dehydration of trichloroacetamide was first described in 1873 by L Bisschopinck at the Katholieke Universiteit Leuven 2 nbsp Trichloroacetonitrile can be obtained by chlorination of acetonitrile on a zinc copper and alkaline earth metal halide impregnated activated carbon catalyst at 200 400 C with a 54 yield 3 nbsp The high temperatures required by this process favours the formation of byproducts such as tetrachloromethane In contrast the chlorination of acetonitrile saturated with hydrogen chloride leads to pure trichloroacetonitrile even at 50 80 C in good yields 4 Like other halogenated acetonitriles trichloroacetonitrile is produced from organic substances such as algae humic acids and proteinaceous material in the disinfecting chlorination of water from natural sources 5 6 Properties edit nbsp Rounded bond lengths and angles of trichloroacetonitrileFreshly distilled trichloroacetonitrile is a colorless liquid with a pungent odor that discolours rapidly yellowish to light brown It is sensitive towards water acids and bases The bond lengths are 146 0 pm C C 116 5 pm C N and 176 3 pm C Cl The bond angle is 110 0 Cl C Cl 7 Use editThe substitution of all electronegative substituents in trichloroacetonitrile by nucleophilic attack of alkoxide anions produces orthocarbonic acid esters in high yield Due to the high reactivity of the chlorine atoms trichloroacetonitrile can be used especially in combination with triphenylphosphine to convert allylic alcohols into the corresponding allylic chlorides 8 nbsp With carboxylic acids acyl chlorides are obtained 9 Due to the mild reaction conditions the Cl3CCN PPh3 system is also suitable for the activation of carboxylic acids and their linkage with supported amino compounds to amides peptides in solid phase syntheses 10 From sulfonic acids the corresponding sulfochlorides are formed analogously 11 In an analogous manner the activation of diphenylphosphoric acid with Cl3CCN PPh3 and reaction with alcohols or amines proceeds to the corresponding phosphoric acid esters or amides in a gentle and efficient one pot reaction 12 Also phenolic hydroxy groups in nitrogen containing aromatics can be converted into the chlorine compounds 13 nbsp In a Hoesch reaction aromatic hydroxyketones are formed in the reaction of substituted phenols with trichloroacetonitrile for example from 2 methyl phenol the 2 trichloroacyl derivative in 70 yield 14 nbsp The electron withdrawing effect of the trichloromethyl group activates the nitrile group of trichloroacetonitrile for the attack of nucleophilic oxygen nitrogen and sulfur compounds For example alcohols give O alkyltrichloroacetimidates under basic catalysis in a direct and reversible addition 15 which can be isolated as stable and less hydrolysis sensitive adducts nbsp With primary and secondary amines N substituted trichloroacetamidines are formed in a smooth reaction with good yields which can be purified by vacuum distillation and are obtained as colorless malodorous liquids 16 Reaction with ammonia and then with anhydrous hydrogen chloride gives the solid trichloroacetamidine hydrochloride the starting compound for the fungicide etridiazole In academic research trichloroacetonitrile is used as a reagent in the Overman rearrangement converting allylic alcohols into allylic amines 17 18 19 The reaction is based on a 3 3 sigmatropic and diastereoselective rearrangement Benzyl trichloroacetimidate is easily accessible from benzyl alcohol and trichloroacetonitrile 20 Benzyl trichloroacetimidate is useful as a benzylating reagent for sensitive alcohols under mild conditions and to preserve chirality 21 O Glycosyl trichloroacetimidates for the activation of carbohydrates edit R R Schmidt and co workers 22 have described the selective anomeric activation of O protected hexopyranoses glucose galactose mannose glucosamine galactosamine hexofuranoses and pentopyranoses with trichloroacetonitrile in the presence of a base as well as glycosylations under acid catalysis 23 24 25 Under kinetic control 26 with potassium carbonate as the base b trichloroacetimidates are formed selectively whereas with sodium hydride caesium carbonate or potassium hydroxide 27 and in the presence of phase transfer catalysts 28 only a trichloroacetimidates are obtained thermodynamically controlled nbsp The trichloroacetimidates are reacted between 40 C and room temperature with boron trifluoride etherate in dichloromethane with O protected sugars This method usually gives better results than the Koenigs Knorr method using silver salts or the Helferich method which uses problematic mercury salts Since an inversion occurs at the anomeric center the reaction leads to b O glycosides when using a trichloroacetimidates The trichloroacetimidate method often produces sterically uniform glycosides under mild reaction conditions in very good yields nbsp Thioacetic acid reacts with acetyl protected a galactosyl trichloroacetimidate even without additional acid catalysis to thioglycoside from which after cleavage of the protective groups 1 thio b D galactose is easily accessible which is useful for the separation of racemates of amino acids 29 nbsp Trichloroacetonitrile was an important fumigant in the first half of the 20th century but today it has become obsolete for this application 30 See also editAcetonitrile Trichloroacetic acid ChloralReferences edit Pollak Peter Romeder Gerard Hagedorn Ferdinand Gelbke Heinz Peter Nitriles Ullmann s Encyclopedia of Industrial Chemistry Weinheim Wiley VCH doi 10 1002 14356007 a17 363 Bisschopinck L 1873 Ueber die gechlorten Acetonitrile Berichte der Deutschen Chemischen Gesellschaft 6 731 734 doi 10 1002 cber 187300601227 US patent 2375545 R T Foster Process for the preparation of trichloroacetonitrile issued 1945 05 08 assigned to Imperial Chemical Industries US patent 2745868 G Kabisch Process for the production of trichloroacetonitrile issued 1956 05 15 assigned to Deutsche Gold und Silber Scheideanstalt formerly Roessler Guidelines for Drinking Water Quality PDF Recommendations Vol 1 3rd ed Geneva World Health Organization 2004 ISBN 9 2415 4638 7 Frank Bernsdorff 2007 Untersuchungen zur abiotischen Bildung von Acetonitril Haloacetonitrilen und Trichlornitromethan Investigations into abiotic formation of acetonitrile haloacetonitriles and trichloronitromethane in German GRIN p 5 ISBN 9783638383431 Lide David R ed 2010 Structure of Free Molecules in the Gas Phase CRC Handbook of Chemistry and Physics 90th ed Boca Raton FL CRC Press Taylor and Francis pp 9 46 Matveeva E D et al 1995 Regioselective and stereoselective substitution of hydroxyl group for halogen in allyl alcohols Russian Journal of Organic Chemistry 31 8 1121 1125 Jang D O et al 1999 A mild and efficient procedure for the preparation of acid chlorides from carboxylic acids Tetrahedron Letters 40 29 5323 5326 doi 10 1016 S0040 4039 99 00967 3 Vago J Greiner J 2002 A useful acylation method using trichloroacetonitrile and triphenylphosphine for solid phase organic synthesis Tetrahedron Letters 43 34 6039 6041 doi 10 1016 S0040 4039 02 01241 8 Chantarasriwong O et al 2006 A practical and efficient method for the preparation of sulfonamides utilizing Cl3CCN PPh3 Tetrahedron Letters 47 42 7489 7492 doi 10 1016 j tetlet 2006 08 036 Kasemsuknimit A et al 2011 Efficient amidation and esterification of phosphoric acid using Cl3CCN Ph3P Bulletin of the Korean Chemical Society 32 9 3486 3488 doi 10 5012 bkcs 2011 32 9 3486 Kijrungphaiboon W et al 2006 Cl3CCN PPh3 and CBr4 PPh3 two efficient reagent systems for the preparation of N heteroaromatic halides Tetrahedron Letters 53 6 674 677 doi 10 1016 j tetlet 2011 11 123 Martin R 2011 Aromatic Hydroxyketones Preparation and Physical Properties Vol 1 Hydroxybenzophenones in German 3rd ed Springer doi 10 1007 978 1 4020 9787 4 ISBN 978 1 4020 9787 4 Nef J U 1895 Annalen der Chemie 287 274 a href Template Cite journal html title Template Cite journal cite journal a Missing or empty title help Grivas John C Taurins Alfred 1958 Reaction of trichloroacetonitrile with primary and secondary amines Part I Preparation of some trichloroacetamidines Canadian Journal of Chemistry 36 5 771 774 doi 10 1139 v58 113 ISSN 0008 4042 Nishikawa T Asai M Ohyabu N Isobe M 1998 Improved Conditions for Facile Overman Rearrangement The Journal of Organic Chemistry 63 1 188 192 doi 10 1021 jo9713924 PMID 11674062 Overman Rearrangement Organic Chemistry Portal organic chemistry org Retrieved 2012 11 15 Chen Y K Lurain A E Walsh P J 2002 A general highly enantioselective method for the synthesis of D and L alpha amino acids and allylic amines Journal of the American Chemical Society 124 41 12225 12231 doi 10 1021 ja027271p PMID 12371863 Schaefer Fred C Peters Grace A 1961 Base Catalyzed Reaction of Nitriles with Alcohols A Convenient Route to Imidates and Amidine Salts The Journal of Organic Chemistry 26 2 412 418 doi 10 1021 jo01061a034 Eckenberg E P et al 1993 A useful application of benzyl trichloroacetimidate for the benzylation of alcohols Tetrahedron 49 8 1619 1624 doi 10 1016 S0040 4020 01 80349 5 Schmidt R R Michel J 1980 Einfache Synthese von a und b O Glycosylimidaten Herstellung von Glykosiden und Disacchariden Simple synthesis of a and b O glycosylimidates Manufacture of glycosides and disaccharides Angewandte Chemie 92 9 763 764 Bibcode 1980AngCh 92 763S doi 10 1002 ange 19800920933 Schmidt R R 1986 Neue Methoden zur Glycosid und Oligosaccharidsynthese gibt es Alternativen zur Koenigs Knorr Methode New methods for glycoside and oligosaccharide synthesis are there alternatives to the Koenigs Knorr method Angewandte Chemie 98 3 213 236 Bibcode 1986AngCh 98 213S doi 10 1002 ange 19860980305 Schmidt R R Kinzy W 1994 Anomeric oxygen activation for glycoside synthesis the trichloroacetimidate method Advances in Carbohydrate Chemistry and Biochemistry 50 21 123 doi 10 1016 S0065 2318 08 60150 X ISBN 9780120072507 PMID 7942254 Schmidt R R Jung K H 1997 Oligosaccharide synthesis with trichloroacetimidates In Hanessian S ed Preparative Carbohydrate Chemistry New York NY Marcel Dekker pp 283 312 ISBN 0 8247 9802 3 Schmidt R R Michel J 1984 Glycosylimidate 12 Direkte Synthese vonO a undO b Glycosyl imidaten Liebigs Annalen der Chemie 1984 7 1343 1357 doi 10 1002 jlac 198419840710 Urban F J et al 1990 Synthesis of tigogenyl b O cellobioside heptaacetate and glycoside tetraacetate via Schmidt s trichloroacetimidate method some new observatons sic Tetrahedron Letters 31 31 4421 4424 doi 10 1016 S0040 4039 00 97637 8 Patil V J 1996 A simple access to trichloroacetimidates Tetrahedron Letters 37 9 1481 1484 doi 10 1016 0040 4039 96 00044 5 Jegorov A et al 1994 1 Thio b D galactose as a chiral derivatization agent for the resolution of D L aminoacid enantiomers Journal of Chromatography A 673 2 286 290 doi 10 1016 0021 9673 94 85045 3 Sax N M Lewis R J eds 1987 Hawley s Condensed Chemical Dictionary 11th ed New York NY Van Nostrand Reinhold pp 261 1175 Retrieved from https en wikipedia org w index php title Trichloroacetonitrile amp oldid 1170136781, wikipedia, wiki, book, books, library,

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