Abstract
2-Iodo-3-(perfluoroalkyl)propanols are obtained in excellent yields and several-hundred-gram quantities by the controlled radical addition of commercially available n- perfluoroalkyl and perfluoroisoalkyl iodides to allyl alcohol. Their consecutive reduction with hydrazine hydrate and Raney nickel catalyst in methanol afforded the corresponding 3-(perfluoroalkyl)propanols in high yields and purity.
Key words
alkyl halides - alcohols - fluorine - reductive dehalogenation - transfer hydrogenation
References
1a
Horváth IT.
Rábai J.
Science
1994,
266:
72
1b Horváth IT, and Rábai J. inventors; US 5,463,082.
; Chem. Abstr . 1995 , 123 , 87349
2
Studer A.
Hadida S.
Ferritto R.
Kim S.-Y.
Jeger P.
Wipf P.
Curran DP.
Science
1997,
275:
823
3
Oderaotoshi Y.
Zhang Q.
Luo Z.
Curran DP.
Science
2001,
291:
1766
4
Rábai J. In
Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horváth IT.
Wiley-VCH;
Weinheim:
2004.
Chap. 9.
5a
Horváth IT.
Acc. Chem. Res.
1998,
31:
641
5b
Rábai J.
Szlávik Z.
Horváth IT. In Handbook of Green Chemistry and Technology
Clark J.
MacQuarrie D.
Blackwell Science;
Oxford:
2002.
Chap. 21.
p.502-523
5c Special issue on Fluorous Chemistry: Tetrahedron 2002 , 58 , 3823-4131.
5d
Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horváth IT.
Wiley-VCH;
Weinheim:
2004.
5e
Andrushko V.
Schwinn D.
Tzschucke CC.
Michalek F.
Horn J.
Mössner C.
Bannwarth W.
Helv. Chim. Acta
2005,
88:
936
5f
Pearson WH.
Berry DA.
Stoy P.
Jung K.-Y.
Sercel AD.
J. Org. Chem.
2005,
70:
7114
5g Special issue on Fluorous Chemistry: QSAR Comb. Sci. 2006 , 25 , 679-806.
6a
Horváth IT.
Kiss G.
Cook RA.
Bond JE.
Stevens PA.
Rábai J.
Mozeleski EJ.
J. Am. Chem. Soc.
1998,
120:
3133
6b
Szlávik Z.
Tárkányi G.
Gömöry Á.
Tarczay G.
Rábai J.
J. Fluorine Chem.
2001,
108:
7
6c
Gladysz JA.
Ponytails: Structural and Electronic Considerations , In Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horváth IT.
Wiley-VCH;
Weinheim:
2004.
Chap. 5.
7 http://www.fluorous.com.
8a
Miura T.
Hirose Y.
Ohmae M.
Inazu T.
Org. Lett.
2001,
3:
3947
8b
Mizuno M.
Goto K.
Miura T.
Matsuura T.
Inazu T.
Tetrahedron Lett.
2004,
45:
3425
8c
Goto K.
Miura T.
Mizuno M.
Tetrahedron Lett.
2005,
46:
8293
8d
Miura T.
Satoh A.
Goto K.
Murakami Y.
Imai N.
Inazu T.
Tetrahedron: Asymmetry
2005,
16:
3
8e
Vlád G.
Richter FU.
Horváth IT.
Tetrahedron Lett.
2005,
46:
8605
8f
Emnet C.
Gladysz JA.
Synthesis
2005,
1012
8g
Fustero S.
Sancho AG.
Chiva G.
Sanz-Cervera JF.
del Pozo C.
Acena JL.
J. Org. Chem.
2006,
71:
3299
8h
Zhang W.
Curran DP.
Tetrahedron
2006,
62:
11837 ; and references therein
8i
Mizuno M.
Matsumoto H.
Goto K.
Hamasaki K.
Tetrahedron Lett.
2006,
47:
8831
8j
Kojima M.
Nakamura Y.
Ishikawa T.
Takeuchi S.
Tetrahedron Lett.
2006,
47:
6309
8k
Bayardon J.
Holczknecht O.
Pozzi G.
Sinou D.
Tetrahedron: Asymmetry
2006,
17:
1568
8l
Zhang W.
Williams JP.
Lu Y.
Nagashima T.
Chu Q.
Tetrahedron Lett.
2007,
48:
563
9 FTI Catalogue (2006) lists RFn (CH2 )3 OH at $32, $35, $100, and $35 for 2 g each of n = 4, 6, 7, and 8, respectively.
From CF3 CH2 CH2 MgCl and (EtO)3 CH, see:
10a
McBee ET.
Kelley AC.
Rapkin E.
J. Am. Chem. Soc.
1950,
72:
5071
From CF3 CH2 CH2 MgCl and CO2 , see:
10b
Gavlin G.
Maguire RG.
J. Org. Chem.
1956,
21:
1342
From CF3 CH2 CH2 CO2 Et, see:
10c
Walborsky HM.
Baum M.
Loncrini DF.
J. Am. Chem. Soc.
1955,
77:
3637
From CF3 CO2 Et and CH3 CO2 Et, see:
10d
Raiter M.
Pereyere M.
Davies AG.
Sutcliffe R.
J. Chem. Soc., Perkin Trans. 2
1984,
1907
From CF3 CH2 OTf and malonic ester, see:
10e
Tsushima T.
Kawada K.
Ishihara S.
Uchida N.
Shiratori O.
Higaki J.
Hirata M.
Tetrahedron
1988,
44:
5375
From C3 F7 CO2 Me and CH3 OAc, see:
11a Ahlbrecht AH, and Smith S. inventors; GB 904,263.
; Chem. Abstr. 1963 , 58 , 4426
From C6 F13 I and ethyl acrylate (h ν), see:
11b
Buchanan GW.
Smits R.
Munteanu E.
J. Fluorine Chem.
2003,
123:
255
From C7 F15 I and ICH=CHI, see:
11c
Coe PL.
Millner NE.
Smith JA.
J. Chem. Soc., Perkin Trans. 1
1975,
654
12
Moore LD.
J. Chem. Eng. Data
1964,
9:
251 ; and references cited therein
13a
Brace NO.
J. Org. Chem.
1962,
27:
3033
13b Brace NO. inventors; US 3,145,222.
; Chem. Abstr. 1964 , 61 , 10589
14
Brace NO.
J. Fluorine Chem.
1999,
93:
1
15a
Brace NO.
J. Fluorine Chem.
1982,
20:
313
For the addition of (CF3 )2 CFI to allyl acetate, see:
15b Boggs J, Brandstadter SM, Chien J, Cohn M, Edwards BE, Hedrick V, Jackson A, Leman G, Ameduri B, and Kostov GK. inventors; WO 2005,074,637.
; Chem. Abstr. 2005 , 143 , 213355
16a
Metzger JO.
Mahler R.
Schmidt A.
Liebigs Ann. Org. Bioorg. Chem.
1996,
5:
693
16b
Vincent J.-M.
Rabion A.
Yachandra VK.
Fish RH.
Angew. Chem., Int. Ed. Engl.
1997,
36:
2346 ; Angew. Chem. 1997 , 109 , 2438
16c
Szlávik Z.
Tárkányi G.
Tarczay Gy.
Gömöry Á.
Rábai J.
J. Fluorine Chem.
1999,
98:
83
16d
Gambaretto G.
Conte L.
Fornasieri G.
Zarantonello C.
Tonei D.
Sassi A.
Bertani R.
J. Fluorine Chem.
2003,
121:
57
For replacement of toxic organotin hydrides and/or removal of residual tin compounds from end products, see:
17a
Baguley PA.
Walton JC.
Angew. Chem. Int. Ed.
1998,
37:
3072 ; Angew. Chem. 1998 , 110 , 3272
17b
Studer A.
Amrein S.
Synthesis
2002,
835
For an improved preparation of 3d and 4d using 1d (100 g) with the triallyl borate/Bu3 SnH protocol, see:
17c
Rábai J.
Kövesi I.
Bonto A.-M. In
Handbook of Fluorous Chemistry
Gladysz JA.
Curran DP.
Horváth IT.
Wiley-VCH;
Weinheim:
2004.
p.419-420
For the use of PtO2 /NH4 OAc, see:
18a Otsuka T, and Yamamoto S. inventors; JP 2003,146,921.
; Chem. Abstr. 2003 , 138 , 385058
For the use of Pd-C/Et3 N, see:
18b Rock M.-H, and Marhold A. inventors; DE 19,748,775.
; Chem. Abstr. 1999 , 130 , 268838
For the use of Raney Ni/KOAc, see:
18c Ukihashi K, and Hayashi T. inventors; JP 7,022,523.
; Chem. Abstr. 1970 , 73 , 98363
For the use of Raney Ni, NaOH, see:
18d Ahlbrecht AH. inventors; US 3,285,975.
; Chem. Abstr. 1967 , 66 , 46093
19 For hazards with the use of LiAlH4 /RF -amides, see: Marks BS.
Schweiker GC.
J. Am. Chem. Soc.
1958,
80:
5789
20 Ivanko, P.; Takács, F. T.; Rábai, J. Abstracts of Papers , 14th European Symposium on Fluorine Chemistry, Poznan, Poland, 2004 ; Abstract 84.
21
Lahiouhel D.
Ameduri B.
Boutevin B.
J. Fluorine Chem.
2001,
107:
81
22 Daikin Ind. Ltd. . inventors; GB 1,101,049. For an analogous synthesis of 3c with bp 88-90 °C/1.7-2.0 mbar using only 1c , 2 , and AIBN at 70-80 °C, see:
; Chem. Abstr. 1968 , 68 , 60504
23
Bálint A.-M.
Bodor A.
Gömöry Á.
Vékey K.
Szabó D.
Rábai J.
J. Fluorine Chem.
2005,
126:
1524