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Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/lsyc20

Potassium Fluoride on Alumina: An Easy Preparation of Diazocarbonyl Compounds a

Abdelkrim Ben Alloum & Didier Villemin

a

a

I.S.M.R.A., U.R.A. 480 C.N.R.S., Laboratoire de Chimie des Composés Thioorganiques , Université de Caen , 5 avenue d'Edimbourg, F 14032, Caen Cedex, France Published online: 24 Oct 2006.

To cite this article: Abdelkrim Ben Alloum & Didier Villemin (1989) Potassium Fluoride on Alumina: An Easy Preparation of Diazocarbonyl Compounds, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 19:13-14, 2567-2571, DOI: 10.1080/00397918908052657 To link to this article: http://dx.doi.org/10.1080/00397918908052657

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SYNTHETIC COMMUNICATIONS, 19(13&14),

2567-2571 (1989)

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POTASSIUM FLUORIDE ON ALUMINA: AN EASY PREPARATION OF DIAZOCARBONYL COh4POUNDS

Abdelkrim Ben Alloum and Didier Villemin

*

I.S.M.R.A., U.R.A. 480 C.N.R.S., Laboratoire de Chimie des ComposCs Thioorganiques, Universitt de Caen, 5 avenue d'Edimbourg, F 14032 Caen Cedex, France. Abstract: A convenient synthesis of diazocarbonyl compounds from tosyl azide and carbonyl compounds with A1203-KF as solid base is reported. Diazocarbonyl compounds are versatile intermediates in the synthesis of aminoderivatives and precursors of carbenes. One of the best synthesis of this type of compounds is the diazo transfer reaction: diazo compounds can be obtained from the reaction of tosyl azide with methylene acid compounds in the presence of base(1). The principal drawback of this reaction was the formation of tosyl amide as by-product and the separation of it from diazo compound. The use of polymer supported tosyl azide (2) increase the convenience of the method but the polymer is not easily available.

*To whom correspondence should be addressed 2567 Copyright 0 1989 by k4;ircrl Ilekker. Inc

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ALLOUM AND VILLEMIN

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We reported herein a new easy, convenient and efficient method for diazo transfert base on the use of A1203-KF as solid base(3). This method has the advantage of supported reagents(4): simple work-up, an easy product isolation and mild conditions. The relatively polar tosyl amide was keep back by support A1203-KF and the less polar diazo formed was easily eluded with the organic solvent of the reactional mixture.The reaction was used with various acidic methylene carbonyl compounds(Schema I):

Schema I ;

a Z = COO Et, Y = OEt b C

(63%)

Z = CN, Y = OEt (60%) Z = PO(OE1)Z , Y = OEt (96OA)

d 2 = CO CH3, Y = OEt

(94%)

e Z = CO CH,, Y = CO CH3 f

z = co c6 H5, y = co c6 H5

(46%) (93%)

0

D

0

i (85%)

Oh

0

(88%)

9( 78%)

The combination of efficiency, convenient and cheapness makes this method competitive with procedure already described.

POTASSIUM FLUORIDE ON ALUMINA

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EXPERIMENTAL:

Tosylazide was prepared according the literature by the reaction of tosyl chloride with an aqueous solution of sodium azide(5). Potassium fluoride on alumina is prepared as follow : Potassium fluoride (209) was dissolved with water (200 ml) and mixed with neutral chromatographic alumina (30 9). The mixture was evaporated with rotary evaporator under vacuo. neral p r o c e w A mixture of methylene acid compound (7 mmol) and tosyl azide(7 mmol) was stirred in THF (10 ml ) with KF on alumina (3 g) at 0°C during 16 h. After filtration, the solid was washed with THF (2 X 5 ml) and ether (100 ml) is added to the filtrate and the organic phase was washed with an aqueous solution of potassium hydroxide (2.2.7 g of KOH in 100 ml of water). The organic phase was dried on magnesium sulfate and evaporated in vacuo. The product obtained is generally pure, if trace of tosyl amide remaining , it was removed by filtration on a small column of neutral alumina.

-Dlethvl siia7,oma1mte 13a! It was obtained from diethyl malonate, yield- 63%. Yellow liquid; Eb.: 48-50' (0.2); Eb. lit. (6) : 108" (11); IR(nujo1): 2150 (vC=N2), 1760, 1740 (vC=O ; UV (CH2C12) 251nm (log ~ = 3 . 8 6 ) . vl-3 dim0 cvanoacetate (3b! ; Obtained from ethyl cyanoacetate, yield= 60%. Orange liquid,; IR(film): 2240(vCN), 2140(vC=N2) ,172O(vC=O); NMR (CDC13) 6= 4.35(q,2H,OCH2), 1.37(t,3H,CH3). Triethvl-3 diazo phosphonoacewe (3& Obtained from triethyl phosphonoacetate , yield = 96%. Yellow liquid; Eb : 84-85(0.1); Eb. l i t . ( l l ) 103-104 (0.4); IR(film): 2140(vC=N2),1715(vC=O), 1285 (P=O).

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-

ALLOUM AND VILLEMIN

vl

3-dwo-3 one b u m a t e 1 3 u

It was prepared from ethyl acetoacetate, yield = 94%. Yellow liquid; Eb 93-95" (15); lit.(6) Eb. 83" (12); IR(film): 2 1 4 0 ( ~ C = N 2 ), 1720, 1665(vC=O); UV (CH2C12): 258 (log E= 4.0); 3NMR(CDC13): 6- 4.3(q,2H,OCH2), 2.4 (s, 3H, CH3CO) 1.3(t, 3H, C H 2 m ) . edione f3el ; Prepared from 2,4-pentanedione, yield = 46%. Yellow liquid,; Eb.: 75-73"(0.3); Eb.lit. (7) : 57" (0.1); IR(nujo1): 2130, 2260 (vC=N2),1670(vC=O). - - 0-1.3 diDhbnvl DroDane-1.3 dione 13fl; It was prepared from diphenylpropane -1,3 dione, yield= 93%. Yellow solid; Mp 108°C ; lit. (6) Mp 107°C; IR(nujo1): 2120(~C=N2), 1650, 1630(~C=O);UV( CH2C12) 257 log E= 4.37. Obtained from anthrone, yield =78%. Orange solid, Mp> 260°, lit. (8) Tdecom 280"; IR(nujo1): 2060, 21 30(~C-N2),1650(~C=O),1600(~C=C). o -1.3 i n m d i o n e (3hl; Prepared from 1,3-indandione, yield = 88%. Yellow solid; Mp 147-148";Ii.t. (9) Mp 149"; IR(nujo1): 2130(vC=N2), 165O(vC=O), 16OO(vC=C); UV (CH30H) 246 nm (log ~ ~ 4 . 6 6 ) . a70-3 7 dimbthvboxane-1.3 dione-4.6 (31) ; Obtained from Meldrum acid (12), yield- 85%. Yellow solid; Mp 94" ; Mp lit. (10): 94"; IR(film): 2180(vC=N2), 1735(~C=O). 3 dimethvl-5.5 c v c l o h e m e dione-1.3 ( 3 k Obtained from dimedone, yield 90%. Maroon solid; Mp: 106-108"; lit. (10): 108"; IR (nujol): 2140,1635, 167O(vCO).

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POTASSIUM F L U O R I D E ON ALUMINA

REFERENCES : 1.a) Regitz M., Angew. Chem. Inter. Edit., 1967,6, 733; b) Regitz M., Synthesis, 1972, 351; c) Hiinig S., Angew. Chem. Inter. Edit., 1968,1, 335. 2. Roush W.R., Feitler D. and Rebeck J. , Tetrahedron Lett., 1974, 1391.

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u,

3. Villemin D. et Racha R., Tetrahedron Lett., 1986,27, 1789, and references cited.

4. Laszlo P. editor,"Preparative Chemistry using Supported Reagents", Academic Pres , 1987, and references cited. 5.Von E. Doering W. and De Puy C.H., J . Amer. Chem. SOC., 1 9 5 3 , z , 5955. 6. a) Regitz M., Chem. Ber. , 1966,%, 3128; b) Staudinger H. and Aule A.G., Ber., 1916 ,B, 1902. 7. Hendrickson J.B. and Wolf W.A., J.Org. Chem., 1968,2,3610.

8. Regitz M. , Chem. Ber. , 1964,97, 2742. 9. Regitz M., Heck G., Chem. Ber., 1964, E, 1482. 10. Regitz M. and Stadler D., Ann. Chem. , 1965, W, 214. 11. Regitz M., Anschutz W. and Leidheger A. ,Chem. Ber. , 1968, 101 3734.

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12. Davinson D. and Bernard S.A., J . Amer. Chem. SOC.,1948, 70, 3426. (Received i n UK 20 March 1989)

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