Russian Chemical Bulletin, Vol. 45, No. 7, July, 1996 1781

2 AdNH2 + CH20 + ButOCI ~ [AdNCH2NHAd ] I CI

A H

K2~3 \N + -----',lD,- i N ~ (AdNH~)2CHdl C~C13 H \Ad

1 2

8

stirring to a solution oFAdNH 2 (05 g, 33 mmol) in CHCI 3 (20 mL) at 0--5 " C Then the mixture was boiled for 48 h until the characteriqic signal of HN of AdNHCI at 4.05 ppm (in CDCI3) disappealed from the I11 NMR spectrum of the sample After the separation of the precipitate and evaporation of the solvent, the residue was dissolved in CHCI 3 (5 m L ) After 2 h (at 20 °C) precipitated crystals of product 2 (I 2 rag, 2 . 1%) were separated. IH NMR (CDCl3), 8 : 1 . 6 8 (br.q, 12 H, 8-CH 2 ,ABspec tmm,Av = 30.0,2J = - 1 2 2 Hz), 1.85

(br.s, 12 H, 13-CH2), 217 (br.s, 6 H, y-CH), 7.37 (t, I H, NCHN, 3j = 129 Hz), 1031 (br.d, 2 H, HN).

ProxJuct I was isolated from the mother liquor by chroma- tography on a column with silica gel (100--160 ram, eluent CHCI3--CCI 4, I : I ) Diaziridine 1 (51 rag, 98 %) was ob- tained after two c~tal l izat ions from acetone, mp. 195 °C, Rf = 0.38 (CHCI3--CCI 4 I I). Found (%): N, 9 1 9 C?IH3zN 2, Calculated (%) N, 8 9 6 Partial MS (El, 70 eV), m/Z(Ire ~(%)): 312[MI + (518L 177[M--Adl + (6oIL 135 [Adl + (100), 42 IM-2Adl + (497) ~H NMR (CDCI3) , 8:1.56 (brs, 12 H, [~,-Ctt2), 1.59 (brq, 12 H, 8-CH 2, AB spectrum, ~,v = 21 I, 2j = - 1 2 2 Hz), 204 (bns, 6 H, -¢-CH), 255 (s, 2 H, NCH2NL 13C NMR (CDCl3): 2941 (d, -:,-C, I j = 132.2 Hz), 3676 ( t 6-C, i j = 1280 Iqz), 3955 (t, NCH2N, Ij = 173.0 I tz) ,39.66(t , [VC, I j = 1280 Ilz), 5415 (s, (x-C)

This work was f inancial ly supported by I N T A S (Gran t 94-2839) and the Russian Founda t i on for Basic Re- search (Project N o 94~03-08730).

References

I R Ohme, E. Schmirz, and P. Dolge, ChemBer, 1966, 99, 2104

2. R G Kostyanovsky, V. A Korneev, I~ 1 Chep, gn, V N Voznesensky, YtL V. Puzanov, and P~ Rademacher , Mendeleev Commun, 1996, 106.

Received April 23, 1996

ChlOrine dioxide as a novel mild oxidant of allylic alcohols

A. Is. Kutchin,* L. L. Frolova, and L V. Dreval

Institute of Chemisto', K))mi Scientific Center of the Russian Academy of Sciences, 48 ul. Pervomaiskaya, 167610 A~vktyvkar, Russian Federation.

Fax: 007 (821) 242 2264

In add i t ion to tile known me thods for oxidiz ing ell20 H allylic a l coho l s to the co r r e spond ing carbonyl corn ] pounds , t we suggest a new me thod , ox ida t ion with ch lo r ine d iox ide , wh ich has not been previously used ill Me organ ic synthesis . Being a highly react ive ox ida t ion re- ~ 1 ~ CZ) 2 is wide ly used in the paper and pulp indus- Me

1 tW tq.~r w h i t e n i n g ce l lu lose , z The m e c h a n i s m and prod- ucts of the ox ida t ion o f mode l l ignin c o m p o u n d s (sty- rene and s t i lbene der iva t ives) with ch lo r ine d ioxide have Me been s tudied in recent works. 3 J . _

The t e rpeno l s myr t eno l (1) and trans-verbenol (2), whose ox ida t ion results in the fo rma t ion o f myr tena l M OH (3), m y r t e n i c acid (4), and v e r b e n o n e (5), respect ive ly , were chosen as substrates . 2

CHO COOH

--9 < Me M

3 4

Cl o 2

Me

M e m o Me

5

Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1871--1872, July, 1996

1066-5285/96/4507-1781 $1500 (O 1996 Plenum Publishing Corporation

1782 Russ ChemBul l , 1~1. 45, No. 7, July, 1996 Kutchin et aL

G L C analysis was performed on an LKhM-80 chro- matograph, argon was used as the carrier-gas, and a co lumn was filled with 5 % SKTFT-50 on Chromaton N - A W - D M C S . Peaks were identified by compar ison with known compounds , and the contents of the com- ponents were de te rmined by internal normalizat ion. IR spectra were recorded on a Specord M-80 instrument, and IH N M R spectra were recorded on a Tesla instru- ment (100 MHz),

Oxidation of I. Myrtenol I (0A5 g in 10 mL of CCI4) was oxidized by gaseous CIO? at 50 °C for 45 ra in The reaction was moni tored by TLC on Silufol UV-336 plates with hexane- -d ie thy l e ther (5 : 2) was as the eluent. Then the oxidat ion product was cooled and dried over anhydrous Na2SO 4, the solvent was distilled off, and the residue was analyzed by GLC. The degree of conversion of 1 was 6 1 % ; myrtenal 3 ( 4 1 % ) and myrtenic acid 4 (4 %) were fo~med The oxidat ion product was twice treated in a separator? funnel w i th a 3 c~ aqueous solut ion o f N a O H Neutral compound ~, were extracted with diethyl ether, The alkaline layer was treated with 10 % H?SO4 to the acidic reaction with Congo, compound 4 was extracted with diethyl ether, washed, and dried over Na2SO 4, and the solvent was evaporated. IR (KBr), v / c m - I : 3100--2500 ( C - - O H ) ; 1690 ( C = O ) ; 1630 ( R I R 2 C = C R 3 H ) ; 1280 ( C - - O L

IH N M R (CDCI3), 8 :0 ,798 (s), 1.34 (s, 6 H, CMe2); 2.455 (m, 4 H, 2 CH2); 2.78 (t, 2 H, 2 CH) ; 6.989 (m, 1 H, C H = ) ; I1,1 (b r s , I H, OH).

Oxidat ion of 2. trans-Verbenol 2, (0.4 g in 10 mL of ethanol) was oxidized by gaseous CIO? at -20 °C for 30 rain. TLC showed that the react ion ceased when the alcohol was entirely absent in the react ion mixture. According to GLC, the conversion of compound 2 was 100 %; the oxidation product consisted only of ver- benone (5).

References

I P Muller, in: The Chemistry ~ff Functional Groups Supple- ment E: The Chemistry of Ethers, Crown Ethers, tlyctroxyl Groups and their Sulphur Analogs Part /, Ed S Patat, Interscience~-Wiley. Chichester, 1980. 469--5061 H Masao, K ToshDuki, md M Takashl, S'vnth Commun, 1994. 24. 1823; J Attenburrow. A F B Cameron. J. [ I ( h l p m a n R M Evans. B A Hems. A B A Jansen. and -I Walker Y Chem So~. 1952. 1094: R Sheldon and J. Van Doom. J CataO,s~s. 1973. 31. 427

2.1 A Fumanova and [ E. His, Ftziko-khim~cheskie osnovv otbelki tsellyulocv [ Physicochemicai fbundations of Whitening c( Cellulosel, Lesnaya Prom-st ' , Moscow, 1972, 103 (in RussianL

3. C Brage, T. Enksson, and L Gierer, Hol~orschung, 1995, 49

Received May 15, 1996