n Bicyclo[3.3.1]nonane-2,9-dione 7-e thyleneketa l (IV). 1 ,4-Cyclohexanedione monoethyleneketal , obtained as desc r ibed in [10], was enaminated as desc r ibed in [5], and enamine (II) was Mkylated with acry leyl cMo- r ide [11]. The bicyclo[3.3 .1]nenane-2,9-dione 7-e thyleneketa l , which was i so la ted in 40% yield, has mp 65- 67 ~ ( f rom pe t ro leum ether) . I n f r a r ed spec t rum (v, cm -1, KBr) : 1720; 1740 (C=O); 1120 (COC). Found: C 63.35; IF: 6.91%. CllH1404. Calculated: C 62.90; H 6.72%. NMR spec t rum (6, ppm): 2.0-2.6 m (6 H); 2.6- 3.1 m (4 }); 3.9 s (4 H). Mass spec t rum (m/e ) : 141, 154, 182, 210 (M+).

CONCLUSIONS

Bicyclo[3.3.1]nonane-2,9-dione derivatives, containing substituents in the 7 position, were synthesized by the condensation of the morpholine enamines of 4-substituted cyclohexanones with acryloyl chloride.

LITERATURE CITED

I. V.V. Sevost'yanova, M. M. Krayushkin, and A. G. Yurehenko, Usp. Khim., 3__9_9, 1721 (1970). 2. F. I~i. Stepanov andW. D. Suchowerehow, Angew. Chem., 79_, 860 (1967). 3. K. l:~makawa, I. Jzuta, H. Oka, and R. Sakaguchi, Tetrahedron Left., 197__~4, 2187; N. Barbulesch, M.

Moraru, and D. Sokta, Rewu Roumain de Chimie, 18_, 873 (1973). 4. A. I~i. Kost and L. G. Ovseneva, Zh. Obshch. Khim., 32_~ 3983 (1962). 5. G. Stork, A. Brizzolara, II. Landesman, J. Szmuszkovicz, and R. Terrel, J. Am. Chem. Soc., 85__, 207

(1963). 6. N.F. Karpenko, O. S. Chizhov, S. S. Novikov, V. V. Sevost~yaneva, T. A. Klimova, and M. M. Krayush-

kin, Izv. Akad. Nauk SSSR, Ser. Khim., 197_._~5, 2034. 7. E.E.H. Jones and F. Sondheimer, J. Chem. Soe., 1949, 615. 8. H. ]3town and C. Gara, J. Am. Chem. Soc., 833, 2952 (1961). 9. J . A . McDonald and A. Dreiding, Helv. Claim. Acta, 5_~6, 2523 (1973).

10. M. Has lander and R. G. Lawton, Synth. Commun., 4_, 155 (1974). 11. P . W . Hiekmott and J. R. Horg reaves , Te t rahedron , 23___, 3151 (1967).

N E W M ~ T H O D F O R C O N V E R S I O N O F N - A C Y L - ~ -

A M I N O E i E T O N E S T O S U B S T I T U T E D T H I A Z O L E S

S. I . Z a v ' y a l o v , T . K. B u d k o v a , a n d M. N. L a r i o n o v a

UDC 542.91:547.789

We w e r e the f i r s t to es tabl i sh that N - a c y l - ~ -aminoke tones (Ia-h) when heated with CH3COSH and ZnC12 in e i ther dioxane or ethyl ace ta te a re conver ted in high yie lds to substi tuted th iazoles (IIa-h).

RCONHCHRICOCH3--4GHsC~ R~-T-~CH3 ZnCl~ N S

(In-- h) " \'Y" 0 h - h ) I R

R=CH3. RI~-H (in), (IIal; R:H, RI:CH~ (Ibj, (lib); R~EeHs. 111=H (Ic), (Ile); R : R I = C I - I 3 (Idj, (IId}; R :C6Hs , RI=CH~ ( Ie ) : ( I Ie ) ; R=CH3, Rl=C~Ih. (If), (IIf);

R=H, R'=(CH3hCHCH~ (Ig). (IIg); R=CH~, RI=(CH~)~CHCH2 (II~, (IIh)

The s t ruc tu re of the obtained th iazoles (IIa-h) was conf i rmed by the NMR s p e c t r a (Table 1), and also by compar i son with authentic spec imens . The convers ion of (Ia-h) to (IIa-h) apparent ly p roceeds via the i n t e r - media te s teps of adding CH3COSH to the CO group of (Ia-h)~ format ion of th ioketa ls (IIIa-h) , and the i r subse- quent cycli zation to th iazol ines (IVa-h) under the influence of ZnC12. (See scheme on following page).

N. D. Zelinskii Inst i tute of Organic Chemis t ry , Academy of Sciences of the USSR, Moscow. T rans l a t ed f rom Izve~,~tiya Akademii Nauk SSSR, Ser iya Khimicheskaya, No. 6, pp. 1411-1413, June, 1976. Original a r t ic le submit ted November 24, 1975.

This material is protected by copyright registered in the name o f Plenum Publishing Corporation, 227 West 17th Street, New York, 1~: Y. 10011. No part o f this p~blication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic~ mechanical, photocopying, microfilm.~ng, recording or otherwise, without written permission o f the publisher. A copy o f this article is available from the publisher for $Z50.

1353

TABLE i. Reaction of N-Acyl- (~-aminoketones with CH~COSH and

,;~_ v,s-1321

30J" V,0--,53 I

71 IM--144 t i t )

cq 102--t~ 4! I

70 12i~--128 (0)

70 80--87 (25)

:3 I 0(~-tooI t9) i

TLC on Silu- ~ fol 7V~s 4

6 Solvent ~/

t ~ . . I Benzene" ,o~ I--acetone o,3~ (t,) t all 4:1

t,&qg0 I n 0,$9 I (22). [

i IJS0t Benze r l e 0.58 I 03) - AcOgt

1.5t")3 B e n z e n e 0.A2 (i~,) -acetone

i,c,i~o Benzene o,~o (t~) -AcOEt

I

1.50A0 n 0,29 I (20)

t,~99t 3enzene 0,c0 (rid

- acetone

i/,~33 3enzene 0,36 (2t) - AcOEt

2A6 (5800)

252 0~0oo)

29(~ 13 90s

253 (~000)

303 t2 t0f

252 (iS(0)

252 (2730)

253 {'$330)

ZnCh =

~ o

(Ia)* " 100 ] (IIa) ]

(Ib) lOO I (lib)

(Ic) 120-- t ~ I (IIc)

(Id) * too (lid)

(Ie) t20 ~ao (IIe)

(If) 6 I 120 (IIf)

(Ig) 2~ 12o (IIg)

(lh) 7 I 12o (IIh) [5]

I t

gu

NMRspec- tram (in ,~6 @ cc~) ~,

ppm N

2 3 ~ r 2.5$S (2-CH,)

/2 3~S (5-CH,) 18612187--i

[21428 (5-CtIa) t72--t73 | 7.25m (a-H ! 30, a.r.)'$ [i] 7,,qom 2na.r 2 t7 S [GHa) i3I-t32 2 22s 'CHD [S] 238 s i2-cml 2 25 g ~2 CHsl t85--t86 7'20t ~ ~Ha.r , [4] 7'75 q ~ ~Ha.r . t ' t 3 t ' (CH~ 3H~) =,22 S 5-CHa)

[ 2.$7 S :2-CH3) 12 5o .q ~CI~D IO;82d ~2CH~) (02--t03 12,021TI (CH) 12 2~ S 5-CHz) / 21~ d 'CH,) t 8 ~o s '2-H) /o:s~ d '2Ore) - - / t , o5m (CH) /2 22 s 5-CHa) t 2'25 d 'CH~) | 2:r s >'J.-CH~)

*The reaction was run in AcOEt. 1"The yields are based on (V) and (VI). $a.r. = aromatic ring. (iIf). Found: C 59.54; H 8.00; N 9.78; $ 22.59%~ CTHnNS. Calculated:c 59.60; H 7.80; N 9.93; S 22.70%. (IIg). Found: N 8.89; S 20.30%. CsHIsNS. Calculated: N 9.03; S 20.65%. (IIg) picrate. Found: C 43.76; H 4.40; N 14.81; S 8.36%. Ct~6N4OTS. Calculated: C 43.75; H 4.14; N 14.60; S 8.34%.

GKsGOSH CI-I~COSt{ (Ia-- h) . . . . . . . . RCONttCHRtC(OH)(SCOCHa)CH3 - - ~

-H..0 H~0

R CONHCtlR1C(SCOCH@~CH3 ~ RCONHCHR1C(SH)(SCOCH@CH3 (IIIa--h)

SCOCH~

-~ R ' @ C H a -CH~COSH N S ~ (IIa--h)

Y R

( I Va-- h )

In h a r m o n y w i t h t h i s s c h e m e , t h e r e a c t i o n o f (In) w i t h C t t sCOSH and Z n C l z at 20 ~ g i v e s 2 , 5 - d i m e t h y i - 5 -

a c e t y l m e r c a p t o - 2 - t h i a z o l i n e (IVa), w h i c h w h e n h e a t e d to 7 0 - 8 0 ~ c l e a v e s CHsCOSH and i s c o n v e r t e d to (IIa).

T h e s t r u c t u r e o f (IVa) i s i n a g r e e m e n t w i t h t h e d a t a o f t h e IR s p e c t r u m , w h i c h c o n t a i n s t h e b a n d o f t h e CHsCOS g r o u p at 1690 e m - i , and t h e N M R s p e c t r u m , w h i c h h a s t h e s i g n a l s o f t h e p r o t o n s o f t h r e e CH~

g r o u p s ( two s i n g l e ( s , 6 1.92 and 2 .18 p p m , and o n e t r i p l e t , 6 2 .07 , J = 1 Itz) and o n e CI t 2 g r o u p ( two d o u b l e t s

(J = 15 Hz) of q u a d r u p l e t s , 5 3.88 and 4 .33 ppm) .

T h e s t a r t i n g ( In-h) w e r e s y n t h e s i z e d by t h e D a k i n - W e s t r e a c t i o n f r o m t h e c o r r e s p o n d i n g c~-amino a c i d s and AczO [6]. C o m p o u n d s (Ib, tl) w e r e o b t a i n e d f o r t h e f i r s t t i m e by h e a t i n g o r t h o f o r m i c e s t e r w i t h t h e

h y d r o c h l o r i d e s o f ~ - a m i n o k e t o n e s (V) and (VI ) .

HC(OC~Hs)~ RCH(NH~-HC{)COCII3 - - ~ RCH(NHCHO)COCH~

R :-CH~ (V), (CHs)=,CHCIh (VI) (15, g)

As a r u l e , t h e p r e v i o u s l y d e s c r i b e d [1, 5] r e a c t i o n Of N - a c y l - a - a m i n o k e t o n e s w i t h P 2S5 g i v e s l o w e r

y i e l d s o f t h e s u b s t i t u t e d t h i a z o l e s .

1354

EXPERIMENTAL METHOD

The UV spectra were taken on a Specord UV-VIS instrument, the IR spectra were taken on a UR-10

instrument: (as KBr pellets), and the NMR spectra were taken on a DA-60-1L instrument.

3-Acetamido-2-pentanone (If). A stirred mixture of 10 g of ~-aminobutyric acid, 47 ml of pyridine,

and 46 ml ~f Ac20 was heated at I00 ~ (bath temperature) for 6 h and then vacuum-distilled. We obtained 12 g

(85%) of (I~), bp 137-138 ~ (15 ram). Found: C 58.67; H 9.09; N 10.90%. CTHI3NO 2. Calculated: C 58.80; E 9.09; N 10.78%.

3-Ar~ino-2-butanone Hydrochloride (V). A mixture of 26 g of (Id) and 260 ml of dilute HCI (i :2) was

refluxed fcr 8 h and then cooled to 20 ~ filtered, the filtrate was evaporated in vacuo to dryness and the residue

was washed with acetone. We obtained 20 g (80%) of (V) (mp 98-i03~ which was used as such to obtain (rb).

3-Fcrmamido-2-butanone (Ib). A mixture of 5.1 g of (V) m~d 50 ml of HC(OC2Hs) 3 was heated at 70-

80 ~ (bath) ]for 16 h, after which it was filtered, the filtrate was evaporated in vacuo, the residue was mixed

with 2 ml of water, 7 ml of alcohol, and 5 drops of cone. HCI, kept at 20 ~ for 21 h, again evaporated in vacuo, and the re~idue was distilled. We obtained 3.6 g (75%) of (Ib), bp 138-142 ~ (18 ram); n~ 1.4610. NMR spec-

trum (5, ppm): 1.27 d(CH3CH) ;2.12 s(CH3CO) ; 4.45 q(CH); 8.03 s(CHO). Found: C51.94; H7.89; N 12.05%. CsHgNO 2. Calculated: C 52.20; H 7.82; N 12.20%.

3-Amino-5-methyl-2-hexanone Hydrochloride (V I). A mixture of 34 g of 3-acetamido-5-methyl-2- hexanone and 340 ml of dilute IICI (i : 2) was refluxed for 8 h, after which it was evaporated in vacuo and the residue w~s washed with acetone. We obtained 20 g (60%) of (VI), mp 155-156 ~ . Found: C 50.49; H 9.91; N 8.79; Cl 21.89%. CTHi6CINO. Calculated: C 50.80; H 9.67; N 8.45; Cl 21.50%.

3-Formamido-5-methyl-2-hexanone (Ig). A mixture of 3 g of (VI) and 30 ml of HC(OC2Hs) 3 was heated

at 90-100 ~ (bath) for 9 h, after which it was evaporated in vacue and the residue was used as such to obtain (IIg). The residue was hydrolyzed as described above to isolate (Ig).

2-Phenyl-5-methylthiazole (IIc). A stirred mixture of 1.8 g of (le), 3 ml of AcSH, and 4.2 g of anhy-

drous ZnCi: 2 in 18 ml of dry dioxane was heated at 120-125 ~ (bath) for 3 h, after which it was cooled to 20 ~

t r e a t e d wi th e i t he r aqueous K2CO s or KOH so lu t ion to pH ~ 9, e x t r a c t e d wi th e the r (10 • 25 ml) , the e t h e r ex t r ac t wa~ e v a p o r a t e d and the r e s i d u e was m i x e d wi th e x c e s s d i lu te HC1 (1 : 1). T h e n e u t r a l i m p u r i t i e s w e r e r e m o v e d by e x t r a c t i o n wi th e ther , and the ac id aqueous so lu t ion was a lka l i zed wi th K2CO 3 to pH ~ 9 and then ex t r ac t ed wi th e ther . The e the r ex t r ac t was d r i e d o v e r K2CO3, f i l t e red , and evapora t ed in vacuo. D i s t i l l a - t i on of the residue gave 1.26 g (71%) of (IIc).

Compounds (IIa, b, and d-h) were synthesized in a similar manner. The physicochemical characteris- tics of (IIa.-h) are given in Table i.

2,5-I~methyl-5-acetylmercapto-2-thiazoline (IVa). A mixture of 3 g of (la), 7.5 ml of AcSH, and 10.8 g

of anhydrous ZnCI2 in 16 ml of dioxane was stirred at 20 ~ for 120 h, after which it was poured into 400 ml of

water, alkalized with K2CO 3 to pH ~ 8, and extracted with ether. The ether extract was dried over K2CO3,

filtered, a~:d evaporated at atmospheric pressure. The residue was chromatographed twice on a silica gel column, usi[ng a i0 :I benzene--AcOEt mixture for elution. We obtained 1.86 g (38%) of (IVa), n~ 1.5439,

Rf 0.46 (Silufol UV254, 4 :i benzene-acetone, detection of spots in UV light). Ultraviolet spectrum (~]cohol):

kmax 233 hm (~ 3040). Found: C 44.51; H 5.79; N 7.37; S 33.68%. CTHIINOS 2. Calculated: C 44.50; H 5.82; N 7.40; S 33.80%.

CONCLUSIONS

i. Substituted thiazoles are formed when N-acyl-(~-aminoketones are heated with thioacetic acid and ZnCI 2 in ether dioxane or ethyl acetate.

2. The reaction of acetamidoacetone with thioacetic acid and ZnCl 2 at 20 ~ leads to 2,5-dimethyl-5- acetylmercapto-2-thiazoline.

3. c~- Formamidoketones are formed when a-aminoketone hydrochlorides are heated with orthoformic ester.

1355

1 o

2. 3. 4. 5. 6.

L I T E R A T U R E C I T E D

S. Gabriel , Ber . , 43, 1283 (1910). M. Erne and H. E r l e n m e y e r , Helv. Chim. Acta, 3_~1, 652 (1948). T. Roubleff, Ann. Chem., 259,258 (1890). Yu. V. Gelly and S. A. Gusinskaya, Neftekhimiya, 11, 902 (1971).

/ . N. Gerencewc and M. Pr(~stenik, Kern. Ind. (Zagreb) , 1-3, 98 (1964); C. A., 6-3, 16326n (1965). S. I. Zav 'ya lov , N. I. Aronova, and N. N. Makhova, Study Methods and React ions of Organic Compounds [in Russian] , Vol. 22, "Khimiya" (1971), p. 9.

PHOTOCHEMICAL ADDITION OF TRIALKYLSILANE-

THIOLS AND TRIALKYLGERMANETHIOLS TO

ACETYLENIC COMPOUNDS

M. G. Voronkov, R. G. Mirskov, V. I. Rakhlin, and E. O. T s e t l i n a

UDC 541.14:542.955:547.245:547. 246:547.538.241

Prev ious ly we had descr ibed methods for the p r e p a r a t i o n of o rgany l (a lken- l -y l th io ) s i l anes , o rganyl - ( a lken - l -y l th io )ge rmanes , and e rgany l (a lken- l -y l th io ) s tannanes Rt_nM(SCHR ' = CHR") n (where M = Si, Ge, Sn; R = alkyl; R' = H, alkyl; R" = H, alkyl, a w l ) [1]. It was shown that compounds of this type, in contras t to the i r oxygen analogs, a re s table and under ord inary conditions a re incapable of t au tomer ic t r an s fo rma t io n s according to the scheme:

s

M--SCH=CH2 ~_ M--CH~.C \

H

New methods w e r e developed for the synthesis of the alkenylthio der iva t ives of the Group IVB elements , and we w e r e the f i r s t to effect the photochemical addition of t r ie thyls i lanethiol and t r ie thy lgermaneth io l to monosubst i tu ted acetylenes , including to t r ia lkyle thynyls i lanes and t r i a lky le thynylgermanes . The reac t ion p roceeds eas i ly by the genera l scheme:

hv

RC~CH -~ I-ISM (C.~H~)a --~ RCH=CItSM (C~tt~) 3 (I)--(VIII) M = Si (I), (II), (III), Ge (IV), (VIII);

R ---- (CH,),C (I), (V), C6H 5 (II), (VI), Si(CH,)~ (III), Si(C,,Hs) 3 (VII), (C2Hs)sGe (IV), (VIII)

The yield of the p roduc t s is usually c lose to quantitative. The p r o p e r t i e s of the obtained compounds ( I ) - (VIII ) a re given in Table 1. These compounds a re e i ther co lor less or yel lowish mobi le liquids with a specif ic odor. Based on the NMR spec t ra l data (Table 2), they a r e a mix tu re of the cis and t r ans i s o m e r s , with a p redominance of the la t ter . It was also es tabl i shed by this method that in the t e m p e r a t u r e range 20- 200 ~ they do not undergo the meta l lo t rop ic r e a r r a n g e m e n t s that a re cha rac t e r i s t i c for t he i r oxygen analogs [2]. The f requencies of the s t re tching v ibra t ions of the double bond in compounds ( I ) - (VIII ) a re given in Table 1.

E X P E R I M E N T A L M E T H O D

The NMR spec t r a w e r e obtained on a T e s l a BS-487C s p e c t r o m e t e r for 10-20% CC14 solutions at 20 ~ using HMDS as the in terna l standard. The accuracy of m e a s u r i n g the chemical shifts was ~0.01 ppm. The IR spec t ra w e r e taken on a UR-10 spec t ropho tomete r as a thin layer .

I rku tsk Inst i tute of Organic Chemis t ry , Siberian Branch of the Academy of Sciences of the USSR. Trans l a t ed f rom Izves t iya Akademii Nauk SSSR, Ser iya Khimicheskaya, No. 6, pp. 1413_1415, June, 1976. Original ar t ic le Submitted December i , 1975.

material is protected by copyright registered in ti, e name o f Plenum Publishing Corporation, 227 West 1 7th Street, New York, N.Y. 10011. No part ] dS publication may be reproduced, stored in a retrieval system or transmitted, in any form or by any means, electronic, mechanical, photocopying, 1 lining, recording or otherwise, without written permission o f the publisher. A copy o f this article is available from the publisher for $ 7. 50.

1356