J. Chem. Eng. Data 1906, 3 1 , 377-379
Scheme I
+
Q ! - C H 2 a
Ar-CH=CHCOp
IT
I Ether
NaOEt
+
t
m Erythro
IV Threo
a
b C
d studied extensively in the literature (5). I n some cases, both diastereomers have been isolated (6). I n the course of our study on the condensation reaction of a,P-unsaturated esters with active methylene compounds, we now report the condensation of a-phenylacetophenone with Substituted ethyl cinnamates. These condensations yielded a mixture of erythro and threo isomers of ethyl 3aryl-4,5diphenyl-5oxopentanoates, as shown in Scheme I. Slmilar to 1,2,3,5-tetraphenylpentan~ 1,5dione ( 7 ) ,the erythro configurations (IIIa-d) were assigned to the hm meMng point esters and the threo configurations (IVa-d) to the low meking esters. Experknental Section
Unless otherwise stated, IR spectra were measured with a Pye-Unlcam SP 300 spectrophotometer for solutions in CHC13, 'H NMR spectra were measured with a Brucker WP 80-SY
377
spectrometer for solutions in deuterated chloroform containing tetramethylsllane as internal standard, and MS spectra were measured with a 70704 VG analytical organic mass spectrometer. Compounds were analyzed at the M-H-W Laboratories, Phoenix, AZ. Melting points were determined with an electrothermal melting point apparatus and are uncorrected. Elemental analysis In agreement with theoretical values were obtained and submitted for review. Genera/ Procedures. I n each condensation, equimolar amounts of a-phenyiacetophenone and substituted ethyl cinnamates were added successively to a suspension of sodium ethoxide in dry e w r (150 mL). The mixture was kept at room temperature for 1-6 days and then poured into water (200 mL) and extracted with ether. The ethereal extract yielded a crude solid which after crystallization from ethanol afforded ethyl 3aryC4,5diphenyl-5-oxopentanoates, the low meiting point fraction (threo). The alkaline aqueous layer was acidified with dilute hydrochloric acid and extracted with ether and the ethereal extract was shaken with dilute sodium hydrogen carbonate solution. Evaporatlon of the ether ylelded the second diastereomer of the high melting point (erythro) of ethyl 3-aryl-43diphenyC5-oxopentanoates. The infrared spectra of these esters showed a ketonic carbonyl stretching frequency in the range of 1670-1695 cm-' in addition to an ester carbonyl stretching frequency in the range 1710-1735 cm-l. The results are shown in Table I. R.gktry No. I, 451-40-1; IIa, 20511-20-0; I I b , 6048-06-2; I I c . 1579520-7; IId, 1504-68-3; I I I a , 102697-19-8; I I I b , 102697-21-2 I I I c , 102697-23-4; I I I d , 102697-25-6; IVa, 102697-20-1; IVb, 102697-22-3; IVC, 102697-24-5; IVd, 102697-26-7.
LHerature CHed (1) Ruhemann, S. J . Chem. Soc.1910, 457. (2) . . Shandaia. M. Y.: ACKhashab. A. E.; ACArab. M. M. J . Ired Chem. s4c.1977, 2, 53. (3) Sollman, G.; EMholy, I. E. J . Chem. Soc. 1954, 1755. (4) EMholy. I.E.; Rafia, F. K.; Mtshrikey. M. M. J . &g. Chem. 1988, 31, 2167. (5) i i g k n n , E. D.; Ginsburg, D.; Pappo, R. Organic Reactbns; Wiley: New York, 1959; Vol. 10, p 179. (8) Stevenovsky, Y. N.; Vlteva, L. 2. Monatsh. Chem. 1980, 1 1 1 . 1287. (7) Baradel. A. M.; Longeray. R.; Dreux, J. BuH. SOC. &/m. Fr. 1970. 252.
Received for revlew December 27, 1985. Accepted March 11, 1988. We thank Yarmouk Unhrersity for financial support of this work through Grant 37/85.
Reaction of 2'-Hydroxychalcone Dibromides with Me,SO N. Jagannadha Reddy,'+ Sevak Ram Pawar, and Tarachand Sharma School of Studies in Chemistry, Vikram Universlty, Ujjain, India
John A. Donnelly Chemistry Department, University College, Dublin 4, Ireland
2'-Hydroxychalcone dlbromldes on treatment wHh Me,SO gave 2'-hydroxychalcone, i'hydroxy-3'- or 2'-hydroxy-5'-bromochalcone, flavone, monobromlnated flavone, 8,8-dlbromollavone, 3-bromoflavoneYand 3-, 6-, or 8-dibromof lavone. 'Current address: KSP Road, Paloncha, Khammam Dt.. AP 507 115, India.
0021-956818611731-0377$01.50/0
Several workers have used Me2S0for the oxidation and also for oxidative halogenation ( 1 , 2). I n the present communication, the action of Me2S0 on 2'41ydroxychalcone dlbromkles (1) is reported. 2'-Hydroxychalcone dlbromides (la) on heating with Me,SO for 3 h gave 3b, 2a, Sb, ab, Sc, and 8a; at room temperature the reaction products were 3b, 2a, and 6a, I d with warm Me2S0afforded 38, Qe,88, but, at room temperature, Be and 0 1986 American Chemical Society
370 Journal of Chemlcal and Engineering Data, Vol. 31, No. 3, 1986
Table I. Reaction Products of Chalcone Dibromides with Me#O compd recrystn solvent mp, OC (lit., "C) nature R 2a EtOH 88-89 (89-90) ( 4 ) yellow H 2g
EtOH
2h
EtOH
30
EtOH
H
H
CH3
OCH3 H
CH3
151-152 (151-153) (5) yellow needles C1 99 (98-99) (6)
108-109 (108) (8)
orange
R' RZ H
yellow needles H
H
yellow needles H
Br CH3
Br
formula C16H1202
NMR,d
7.6 (m, 11 H, aromatic and -CH=CH-), 13.2 (s, 1 H, -OH) C16H13C102 2.5 (a, 3 H, -CH3), 7.54 (m, 9 H, aromatic and -CH=CH-). and 13.4 ( 8 , 1 H, -OH) C1&03 2.4 (s, 3 H, -CHS), 3.85 (8, 3 H, -0CHd. and 7.7 (m. 9 H. aroma% and -CH&Hi) C16HlIBr02 7.4 (m, 10 H, aromatic and -CHNH-), 12.65 (s,1 H, -OH) C16H13Br02 2.34 (e, 3 H, -CH3), 7.7 (m, 9 H, aromatic and -CH=CH-). 13.4 ( s , l H, -OH) C16HlzBrC102 9.3 (m, 9 H, aromatic and -CH=CH-), 15.8 (a, 1 H-OH), 2.1 (s, 3 H, -CH3) C17H1&03 C,,H,,,BrCIO," 9.3 (m. 9 H. aromatic and -CH=CH-), 15.8 (a, 1 H, -OH) C16H1202 6.6 (a, 1 H, H-3), 7.4 (m,9 H, aromatic) 2.49 (8, 3 H, -CH3), 6.8 (s, 1 H, H-3), 7.8 (m, 7 H, aromatic) 2.45 (s,3 H, -CH3), 3.9 (s,3 H, -OCH3), 6.7 (a, 1 H, H-3), 7.6 (m, 7 H, aromatic) C16HllBr02 2.32 (a, 3 H, -CH3), 6.76 (s, 1 H, H-3), 7.8 (m, 7 H, aromatic) C16H1&C102 2.2 (8, 3 H, -OCH3), 6.7 (s, 1 H, H-3), 7.5 (m, 6 H, aromatic) Cl6H8BrC1O2 6.79 (a, 1 H, H-3), 7.7 (m, 7 H, aromatic) ClliH1,&02 7.6 (m, 7 H, aromatic), 8.4 (d, 1 H, H-5) CI6H$r3O2 7.7 (m, 6 H, aromatic), 8.3 (d, 1 H, H-5) CI6Hl2Br2o2 2.4 (a, 3 H, -CH3), 7.7 (m, 7 H, aromatic) C16H11Br2C102 2.5 (a, 3 H, -CH3), 7.7 (m, 6 H, aromatic) C17H1603Br 2.4 (s, 3 H, -CH3), 3.85 (8, 3 H, -OCH3),7.6 (m, 7 H, aromatic) Cl6H8Br3C1O2 8.3 (d, 1 H, H-5), 8.0 (d, 1 H, H-71, 7.5 (m, 4 H, aromatic) I ,
3f
EtOH
171-172
orange yellow needles
C1
3i 3k
EtOH EtOH
147-148 189
yellow yellow
OCH3 Br CH3 C1 Br H
6a
benzene/petroleum 99 (99) (9) ether benzene/petroleum 201-202 ether benzene/petroleum 168-169 (170) (10) ether
white needles
H
H
white crystals
H
Br CH3
6g
6h
Br CH3
H
white needles white needles
white
C1
Br CH3
8k
benzene/petroleum 181-182 (179) (11) ether benzene/petroleum 220-222 ether EtOH 235
white
C1
Br H
9b
EtOH
192-193
white
H
H
9c
EtOH
189-190
white
H
Br Br
9e
benzene/petroleum 232-233 ether benzene/petroleum 249-250 ether EtOH 136-137 (138) (12)
white needles
H
Br CH3
white needles
C1
Br CH3
white needles
OCH3 H
benzene/petroleum 231 ether
white
C1
8e 8f
9f 9h 91
Scheme I
Br
CH3
Br Br
-1
-1
J. Chem. Eng. Data 1986, 3 1 , 379-380
9e were formed (Scheme I). l e gave 88 and 9e on heating the reaction mixture and 8e, 98, and 3e at room temperature. On the other hand, 9f, 6g, 81, and 31 were obtained from l g under hot condition; 2g and 31 were formed when the same reaction was performed at room temperature. l h gave 9h, whereas, at room temperature the reaction products were 2h, 31, in addition to 6h and 9h. I n the case of 11, 81 was the only product. 11 gave 3k, 8k, 81, 91, and 61 when the reaction mixture was heated for 3 h. Authentic samples of 2a, 8b, 6a, 38, 88, 31, 61, 31, 81, and 6h were prepared by the methods reported earlier (3). Experhnental Sectlon
379
are given in Table I. Satisfactory C, H, and halogen analyses were obtained for ail the compounds. R o g W No. l a , 39729-11-8;lb, 35820-37-2;IC, 10372-55-1;Id, 22219-26-7;l e , 29976-68-9;l f , 102260-70-8; 10, 75227-44-0;lh, 22129-40-4;11, 2997670-3; 11, 43016-14-4 l k , 102260-69-5; 11, 75767-98-5;2a, 1214-47-7;2g, 16635-10-22h, 16635-13-5;3b, 121822-0;30,29976-645;3f, 10226-W 51,29978687;3k, 102260-60-6; Ba, 487-26-3;6g, 14166-166;8h, 102260-61-7;Be, 29976-76-9;81, 102260-62-8;8k, 102260-63-9;Ob, 102260-64-09c, 10226065-1;Or, 102260-66-2; 91, 102260473; gh, 72149-92-991, 102260-6W Me,SO, 67-68-5.
Llterature Clted
Melting points are uncorrected. Reaction mixtures were separated by column chromatography uslng silica gel and the purity was checked by thin-layer chromatography (TLC). R e a c t h of i'-Hydroxychalcone DlbromMs ( l a ) wlth Me,SO. (a) The chalcone dibromkle (la) in Me,SO (20 mL) was heated on a water bath for 3 h and the reaction mixture was allowed to cool to room temperature. I t was diluted with water and the precipitate was fibred off, washed with water, and dried. TLC showed six spots. By column chromatography 8b, 9c, 3b, 6a, and Sa were separated using petroleum ether, benzene, and other as eiuotropic solvents. (b) A mixture of the chalcone dibromide (la) and Me,SO (20 mL) was kept at room temperature for 5 days. I t was then worked up as described above to give 3b, 2a, and 6a. Similarly, the reactions of other chalcone dibromides (lb-1) with Me,SO were carried out and data of the reaction products
(I) Epsteln, W. W.; Sweat, F. W. Chem. Rev. 1987, 6 7 , 247. (2)Kornbium, N.; Powers, J. W.; Anderson, G. J.; Jones, W. J.; Larson, H. W.; Lhrand, 0.;Weaver, W. N. J . Am. Chem. Soc. 1957, 79, 6582. (3)Reddy, N. J.; Bokadia, M. M.; Sharma. T. C.; Donnelly, J. A. J . Org. Chem. 1981, 46, 838. (4) Feuresteln, W.; Kostanecki, St. Von. Chem. Ber. 1898, 3 7 , 715.
(5) ChCHsiungUn: Chlu-Tsudln; Chin Lung Yeh. J . Chem. Soc. (Tal@) 1887, 14 (l),9. (6) Sherma, T. c.; Pawar, S. R.; Reddy, N. J.; Donnelley, J. A. Indlen J . Chem. 1981, 208, 80. (7) Mahanthy, P.; Panda, S. P.; Sabata, B. K.; Raut, M. K. Indlen J . Chem. 1885, 3 , 121. (8) Ghlya, B. J.; Marathey, M. 0. J . Scl. Ind. Res. ( I n d h ) 1982,218, 28. (9) Mahai, H. S.; Venkataraman, K. J . Chem. Soc. 1935, 868. (IO)Fltzgerald, D. M.; OSuUhran. F. J.; Phllbln. E. M.; Wheeler, T. S. J . Chem. Soc. 1915, 860. (11)Wadodkar, P. N. IndlenJ. Chem. 1963, 1 . 183. (12)Kutumbey. K. R.; Marathey, M. Q. Chem. Ber. 1983, 9 6 , 913. Received for revlew January 28,1985. Accepted December 19,1985. We thank CSIR (New Delhi) for the award of a postdoctoral fellowshlp to N.J.R.
Reaction of Acetylenedicarboxaldehyde Bis( diethyl acetal) with Bis(azidomethyl)benzene Sultan 1. Abu-Orabi" Chemisby Department, Yarmouk University, Irbid, Jordan
Robert E. Harmon Chemistry Department, Western Michigan University, Kalamazoo, Michigan 4900 1
carboxaklehyde)tetrakis(ethyi acetals) (IIIa-c). (See Scheme Three 1,l '-[phenylenebls(methylene)]blr( trlazole-4,5-dlcarboxaldehyde) tetrakb(ethy1 acetals) (II I a - c ) were synthesized by the condensatlon of acetylenedlcarboxaldehyde bh( dkthyl acetal) wlth 1,2-, and 1,3-, and 1,4-blr( azldomethy1)benzene.
I n continuation of our previous work on the condensation reaction of l-benzyi-1H-triazoie-4,5dicarboxaidehyde with cyclic ketones to form poiymethyiene-brklged benzyl triazola tropones ( l ) , we report in the present paper details on the preparation of the three bis(azidomethyi)benzenes (I Ia-c) and on their reactions with acetylenedicarboxaklehyde bls(dlethyi acetal) to give the phenylenebis(methyiene)bis(triazoie-4,5dl0021-9568/86/1731-0379$01.50/0
I .) Experlmental Sectlon Acetyienedicarboxakhyde b&(dlethyi acetal) was prepared from acetylene gas and triethyl orthoformate by the method described by Whol(2). Melting points were determined by using a ThomasHoover Unimelt instrument and are uncut~ected.The nuclear magnetic resonance spectra were taken on a Varian A-60 spectrometer using tetramethyisilane as an internal reference, and shifts (6) are reported in ppm. Reparathwt d the Bb ( 8 z ~ f h y f(118 ) -c ~ ). ~ To a solution of 13.0 g (0.2 mol) of sodium azide in 70 mL of water and 70 mL of methanol was added 17.5 g (0.1 mol) of the bis(chloromethy1)benzene. The mixture was heated in a bomb flask at 100 O C for 2 days. The methanol was removed on a rotary evaporator at diminished pressure. The residue was 0 1986 American
Chemical Society
