Houben-WeylMethods of Organic ChemistryAdditional and Supplementary Volumes to the 4th EditionEditorial Board: K.H. Büchel, J. Falbe, H. Hagemann, M. Hanack, D. Klamann, R. Kreher, H. Kropf, M. Regitz, E. Schaumann

Publication Year1985

ISBN (Print)978-3-13-125424-5

Vol. E 10 c/2

Organo-Fluorine CompoundsMethods Index II

METHODS OF

ORGANIC CHEMISTRY

METHODS OF ORGANIC CHEMISTRY

(HOUBEN-WEYL)

ADDITIONAL AND SUPPLEMENTARY VOLUMES TO THE 4TH EDITION

K.H. Büchel Leverkusen

M. Hanack Tübingen

H. Kropf Hamburg

EDITORIAL BOARD

J. Falbe Düsseldorf

D. Klamann Hamburg

M. Regitz Kaiserslautern

EDITORIAL OFFICE

H. -G. Padeken Herrenberg

H. Hagemann Leverkusen

R. Kreher Dortmund

E. Schaumann Clausthal

GEORG THIEME VERLAG· STUTTGART· NEW YORK

VOLUME E 10c / Part 2

ORGANO-FLUORINE COMPOUNDS

METHODS INDEX

Editors

B. Baasner H. Hagemann J. C. Tatlow BAYER AG, Leverkusen / Germany BAYER AG, Leverkusen / Germany Birmingham / Great Britain

GEORG THIEME VERLAG· STUTTGART· NEW YORK

This book mentions numerous commercial and proprietary trade names, registered trademarks and the like (not necessarily marked as such), patents, production and manufacturing procedures, registered designs and desig­nations. The editors and publishers wish to point out very clearly that the present legal situation in respect of these names or designations or trademarks must be carefully examined before making any commercial use of the same. Industrially produced apparatus and equipment are included to a necessarily restricted extent only and any exclusion of products not mentioned in this prospectus does not imply that any such selection of exclusion has been based on qU"llity criteria or quality considerations.

Warning! Read carefully the following: Although this reference work has been written by experts, the user must be advised that the handling of chemicals and microorganisms carries potentially life-threatening risks. For example, serious dangers could occur through quantities being incorrectly given. The authors took the utmost care that the quantities and experimental details described herein refiected the current state of the art of science when the work was published. However, the authors, editors and publishers take no responsibility as to the correctness of the content. Further, scientific knowledge is constantly changing. As new information becomes available, the user must consult it. Although the authors, publishers, and editors took great care in publishing this work, it is possible that typographical errors exist, including errors in the formulas given herein. Therefore, it is imperative that and the responsibility of every user to carefully check whether quantities, experimental details or other information given herein are correct based on the user's own understanding as a scientist. In ca ses of doubt, the user is strongly advised to seek the opinion of an expert in the field, the publishers, the editors, or the authors. When using the information described herein, the user is ultimately responsible for his or her own actions, as weIl as the actions of subordinates and assistants, and the consequences arising therefrom.

Die Deutsche Bibliothek - CI P-Einheitsaufnahme

Methoden der organischen Chemie / (Houben-Weyl). Ed. board K. H. Büchel .... Stuttgart; New York : Thieme

Additional and suppl. vol. to the 4. ed. Vol. E 10c Organo-Fluorine Compounds / Methods Index Ed. B. Baasner ... Pt. 2. - (2000)

Library of Congress Card No.: applied for

Date olpublication 09.12.99

Copyright and all related rights reserved, especially the right of copying and distribution, multiplication and reproduction, as weil as of translation. No part of this book may be reproduced by any process, whether by photostat or microfilm or any other procedure, without previous written consent by the Publisher. This also inc1udes the use of electronic media of data processing or reproduction of any kind.

(0) 2000, Georg Thieme Verlag, Rüdigerstraße 14, D-70469 Stuttgart - Printed in Germany

Typesetting and printing: Tutte Druckerei GmbH, D-94121 Salzweg-Passau

ISBN 3-13-125424-6

Preface

Organo-fluorine compounds have become increasingly important in the last 50 years, as synthetic routes to them have been developed; very few occur naturally. Their chemical behavior covers the entire range from inertness to high reactivity and their physical properties show unique features. These characteristics have led to many specialist uses in various fields particularly as inert fluids, polymers (e. g., Teflon), elastomers, surfactants, surface treatment agents, and fire extinguishers. These prop­erties are also very important in biological and medicinal applications (e. g., the phar­maceutical Prozac and the fluoroquinolone antibiotics) and agriculture (e. g., Tri­fluralin).

Houben-Weyl Vol. E 10 Organo-Fluorine Compounds is a critical survey of the aca­demic and patent literature, organized in a systematic and structured way.

In Volume E 10a, an introduction section details the history ofthe subject (including the role played by F. Swarts), an outline ofnomenclature, physical and physicochemi­cal properties, elemental analysis, structure determination, toxicity, and applications of these extraordinarily interesting compounds. This is followed by Section A wh ich details the diverse range of fluorinating agents used to make C-F bonds, covering everything from hydrogen fluoride to high valence oxidizing metal fluorides. In Vol­urne E lOb described in detail in Section Bare methods for the synthesis of fluorinated compounds from organo-fluorine precursors (the building block approach), while in Section C are outlined general reactions and reactivity of organo-fluorides. Those familiar with the Houben-Weyl series will know that in 1962 a volume (5/3) detailing methods for the preparation of organo-fluorine compounds, written in German, was first published and it is still cited as a source ofinformation even today. Houben-Weyl Vol. E 10 Organo-Fluorine Compounds is written in the same tradition by leading experts in the field and will prove to be an invaluable tool for the student and researcher alike weIl into the next millennium.

Special thanks are due to all the authors who wrote their chapters with dedication and care and who have shown a lot of perserverance with this project. Moreover we are indebted to the editorial staff at Georg Thieme Verlag and all their technical co-workers for their support and help throughout each stage in the production of this volume.

Bernd Baasner Leverkusen

Hermann Hagemann Leverkusen

J ohn Colin Tatlow Birmingham

December 1998

Volume EIOa

Introduction

A. Fluorinating Agents

Volume EIOb/Part 1

Contents to all Volumes

B. Synthesis of Fluorinated Compounds

Volume EIOb/Part 2

B. Synthesis of Fluorinated Compounds

C. Transformations of Fluorinated Compounds

Bibliography

Author Index

Subject Index

Volume EIOc/Part 1

Methods Index

Volume EIOc/Part 2

Methods Index

Table (cont.)

Starting Material or Fragments Reaction; Product

2.10.15. To 1,3-Benzothiazole

SH

(X)Rl_~ ~NH2

SH

~ ~NH2

I

V NH, F3C

CI

F3G ()::NO, 02N

~S (X)Rl~~:>-R2

R1(X)

H

CF3 ; F

R2

4-F -C6 H4

CH 2 -Cl

I ,.1-(CF2)4~ I (Jes S=O ~ N N ~

~S F3C~:>-NR2

F3C~S Qj~ )-COOR

02N N , o

2.10.16. To Benzimidazole

F

N-CH

UNH-Go-o~3 ~I

NH2

CO-O\

VI

':?' N

F ~ I ); N

Reagent

F-o-CO-CI

CI-CHz -C(OR3 )z

r(YS ~:>-(CF2)4-CO-CI

RzN-CS-NRz

HS-CHz-COOR

Volume, Page

E8b,894

E8b,887

E8b,892

E8b,909

E8b,914f.

E8c, 248

~ C­a (1)

~ o Cl

C/J C Ü c. g ö' ? ;J;> 0-§: ö' ::l

t ::c: ~ (1) '"1 o Cl '-< Cl ~ C/l

o '"1

::c: (1)

;; '"1 (1)

::l ~

00 ....... w

Table (cont.) I~ Starting Material or Fragments Reaction; Product Reagent Volume, Page

COOR

PH2-Q-F

I H 2 E8e, 224

CC~H-CH2-Q-F Cr=N ~ N02 I }-OH ~ N I~

('1) ~

~

(JCNH2

H ö'

(XN

::s

~I I )r-X(R) ~ ::s

NH2 ~ N 0.. ('1) '"i

X(R) n ~ '"i

F F. E8e, 270 ~ a -q P-CHO

('1)

~ ::s 0..

F n F I

'11

-qCI -qCI E8e, 252 >-

Ö NH ' CI2C=N _ \ a '""Ij

CF3 '"i

CF3 ~ ('1) '"i -<

-qCI H3CS-CS-NH ~ /; I E8e, 251 f. Ig'

CF3

CXNH2 H ::r:

0

(X)R1~ Ce' ~

(X)R1-+ ~ :>-R

2(Y)

0-I~ ('1)

::s NH2 ~

':S

(X)R1 I (Y)R2

5-CO~Ar NH~COOR3 R3OOC-NCS 5/6-CF3 Ar Ar-C(OR)=NH

5-CO- NH-O--F NH~COOR H3CS - C(NH 2) = NH/Cl- COOR

5-F I--('yNO' I HOOC--(yN02

5-N0 2 I CH,-0-' I F-o-CH2-COOH

n

NH

-R R I CS 2 I

~I f~( F NH2 I }-SH F ~ N

R = H, CO-CH3

nNH-CH2-CN H Base

V N

~I I }-CN F NH2 F ~ N

2.10.17. To 2,1,3-Benzoxadithiole

D Iv~; I S03

F ~ S03H F ~ S O2

E8c,259 E8c, 283

E8c, 248

E8c,272

1 ESc,274

I E8c,260

E8c,227

I Ellb, 1081

B ~ a (t)

~ 0 (")

I~

1I >-0-0-

I~' ö' ::l

I; ~ (t) "1 0 (")

'< (")

n rJJ

0 "1

::r::

1I

00 ....... Vl

Table (cont.)

Starting Material or Fragments Reaction; Product

2.10.18. To 2,1,3-Benzoxadiazole

~N02

F~ N3

o

n~ ~ I :0

F N

2.10.19. To Pyrido[3,2-d]-1,3-oxazole

ccN-...;:: OH -0-

I Ij "\ F ~ NH-CO _

N 0 ("Y~F VJ-N~

2.10.20. To Hexahydro-( 1 ,3-oxazolo[3,4-c ]pyrimidine >

):

0 0 CF

X3

HOOC N CF3 H

o

°Y00 HNy N;(CF

3 o F3C

2.10.21. To 2,1,3-Benzothiadiazole

~NH2

F~ NH2 C _N,S

~ -- / F N

Reagent Volume, Page

E8c,782

E8a, 1099

Cl-S0 2 -NCO EI4a/2, 645

SOCl2 E8d,175

00 ....... 0'\

iO (1) ~

~ ö' ::s t:: ::s 0-(1) '"1

n ~ '"1 ~ a (1)

~ ::s 0-

n I

'Tl

:l> ö a '"0 '"1

~ (1) '"1 -< e ö' ::s

:::c: o t:: Ü (1)

::s

~ ':::..

2.10.22. To Pyrido[3,2-d]-1,3-thiazole

OH F

CCNH-co-O N-N

S~ 11

CCNH'~ F

N F a>-O N S ("Y~F ~:~

2.10.23. To Benzotriazole

F3C~N02

~CI

NH2

F41~ ~NH2

OH I

F3C'Q:N\

I "N ~ N

F _~N\N~ .. ~(4 4 ~N' )=I

H2N

P2SS

Hel

N 2H 4

Pb0 2

2.10.24. To 2,3,5,8-Tetrahydro-1H-<pyridazino[1 ,2-a]-1,2,4-triazole >

F

F~C6Hs ~F F 0

I N~ ~-iN-C6HS

C6Hs 0

N O~ ~N

/N-{O HSC6

E8b,907

E8b,872

E8d, 416f.

EI0b2 ,58

EI0b 1,653

~ 2" a (1)

~ o (")

\/1 t: cr' C. g ö' ? >-0.. g: ö' ~

t ::c: $P. (1) ""I o (")

'< (")

ff o ""I

::c: (1)

S ""I (1)

~ (1) rJl

00 ....... --.l

Table (cont.)

Starting Material or Fragments

R1)cN I ~

N H2N H

X

N~NH2 y)l .. ;L

N NH2

2.10.25. To 9H-Purine

Reaction; Product

Nt:N F3CANJ-N~

H

R1 I R2 (X)

CO-NH 2 lOH

ceNH 2) = NH CN

X

N~N Y)l .. J- ')-CF3

N N H x y

H H CI H

OH NH 2

NH 2 NH 2

2.10.26. 6,7-Dihydro-O ,2-thiazolo[4,5-d]-1 ,2,3-triazine)

H2N_OC~, I ;,N

H2N

~ ~ CF3 --

o

CF3

Reagent

F3C-CO-NH2 (F3C-CO)20

F3C-COOH

(F3C-CO)20 F3C-COOH F3C-COOH

NaN02/NOCl

Volume, Page

E9bj2, 369 E9bj2,380

E9bj2,349 E9bj2, 340 E9bj2, 351 E9bj2,338

E8a, 767

00 ....... 00

~ (t>

~ Q. ö' ::l

~ ::l 0-(t> '"1

n .!n '"1 ~ a (t>

~ ::l 0-

n I

'Tl

> Ö a ""Cl a (t> '"1 <: ~ ö' ::l

::c: o ~ 0-(t>

::l

~ ':S

2.11. To 6/6-Heterobicycles ~ 2.11.1. To 2,J-Dihydro-4H-1-benzopyran, 2- or 4H-Pyran =-a

(l)

F

Q-CO-CH=CH-Ar WAr Itl I VI/4, 151 ~

~I 0 (')

F

OH 0

~CF3 CF3 NaH ElOb 1, 590 (/)

F3C OJCF3 = I ~ ~ OH ;,

ß CI F3C ~ ß g

o· ?

o HNl CYCOOH Hel EI0b 1, 596 > I ß I

0...

~NH g: o·

F41 ::l

ß 0 0 OH t

2.11.2. To Quinoline or lsoquinoline ::c ~ (l) ...,

UNH2

CO I Glycerin I E7a, 366f. 0 (')

F~ '<

F-(')

Iß I ß ß

~ C/)

0 ...,

eCHO CO NH 3 E7a, 596 ::c

(l)

Iß ~ I ß

~ ..., (l)

CH2 -CO-CF3 CF3 ::l (l) C/)

2.11.3. To 2,5-Dioxabicyclo[4.4.0]decane or 2,3-Dihydro-1,4-benzodioxine

I

C(j'C6F" I NBS lEIObI' 592f.

CXO~C6F" 0

OH '00 ....... \0

Table (cont.) ItJ Starting Material or Fragments Reaction; Product Reagent Volume, Page

ce O(xAr Ar - CH = CH - CH = CH - Ar VII/3b, 161 F4- F4- I ~ 0 ~ 0 CH=CH-Ar

2.11.4. To 4H-(3,1-Benzoxazine) ~ ~ ~

~

J~J(H C2H5 (H SC2)2C =O EI4a/l, 810 o'

~i-C'H5 i:j

~I ~ i:j 0..

R ?(CF3)2 h- 0 ~

R -t

OH F3C CF3 n ~ -t ~

2.11.5. 3,4-Dihydro-2H-(1,4-benzoxazine) a ~

~ i:j

IFO)~O Fe VI/4, 560 DO-CH,-COOH 0..

Ih-n I

F N02 'l1

H :l> 0 a

2.11.6. To 2H-(1,2-Benzoxaborine) 'l:I -t

~ FsC6 -BCl2 I VlAF5 I Ar-OH/Ar-C"CH I XIII/3a, 547

~ -t

I B <: ~

(X)R h- h- o' i:j

Ar

2.11.7. To 3,4-Dihydro-2H-(1,4-benzothiazine) ::r:

C(H OH F3C-CO-COOH EI4a/l, 792 0

CC1CF, $::

Ih-0"' ~ i:j

NH2 ~ N 0 H '$.