these compounds have been compared with those
fluorophosphines, and other similar compounds.
of phosphorus(II1) chloride, methanol, the chloro-
RECEIVEDAPRIL7, 1950
[CONTRIBl:TION
FROM THE
DEPARTMENT OF CHEMISTRY, USIVBRSITY OF
NOTRE DAME]
The Preparation and Properties of Some Thienyl Butenols'" IPORGF 'I. G i i I r T m l h
li-hen a-thienylmagnesi urn 1m i 1lit1e wa5 ;t I lowed to react with butadiene nmnoxide there was obtained a hutend ( I ) which was teiitatively assumed to be I-(ct-thieriy1)-buten-%-01-1.This assumption was based on the preparatioii by Senieniuk and Jenkins' of a series of butenols (to which was assigned the general structure of R --CH2---CH=CH-CH20H (XI) by the reaction of various Grignard reagents with butadiene monoxid?. Thev favored the reaction course AJ,
N --hfgS
+ CH,
-
CH -CH-CH,
OhfgX I
+
HLO Hi - ------+ I3 -CH=CHz --+ K--CI12--CH=CH--CH20H (S)
K---CH?-cH---CH=CH, 12 - CI-Iz-CHOH
---+
an explanation of the formation of (X) rather than the expected R-CH2-CHOH-CH=CH2. They did not exclude however, the possibility of * ' 1,A-addition" of the Grignard reagent to butadiene oxide. Evidence for assigning the general structure (X) t o this series of compounds rested solely on the identification, by physical constants of the product obtained from the reaction of 11I ethylmagnesium b romi d e with butadiene mot 1oxide as penten-2-01-1. The possibility that isomeric products3 might result from the reaction of (;rignard reagents with butadiene monoxide made it desirable to cunfirni the tentative structure assigned to (I). Confirmation was obtained in the following manner, I-(cr-Thienyl)-buten-3-ol-2 (II) and 1- (a-thienyl)-buten-3-ol-l (III)* were prepared by the reaction of a-thienylsodium with butadiene monox3s
(la) Abstracted in part from the dissertation presented to the Graduate School of the University of Notre Dame bv Ceorne T Gmitter. ilb) General 'lire Research Fellow 194fi 1949. Present ?ddress Velsicol Corporation, Chicago, Illinois. C2) Semeniuk and Jenkins, J . A n Phnrrii 4ssnc, .5cz E d , 97, 118 (1948). , 3 ) Since the conipletion of our tnvesttgation, Gaylord a n d Beckcr (J.Org. Chcm., 16, 305 (1960)) have reported the formation of 141naphthyl)-buten-3-01-2 when butadiene oxide reacted with l-naphthylmagnesium bromide Jenkins and Semeniuk,* on the other hand, report having obtained otily I-( l-naphthyl)-hiiten-2-ol-4 from the same reaction. (4) Isobutylene oxide and styrene oxide have been reported by Henry (Compl. f r n d . , 146, 21 (19907)) and Tiffeneau and Foumeati tbid., 146, 647 (1908)) t o reart %I>isobutyraldehyde and phenyluxtafdebyde, respectively, with Grignard reagents. (111) was synthesized to exclude the possibility t h a t butadiene monoxide had re rcred with a-thirnrlni3jinP.ium bromide i n d 4 m i l n r farhiori
lvr) F?, T , m R~xror;
ide arid allyliiiagnesiuni hroniide with ?-thiophene aldehyde respectively. Alttempts to synthesize (11) by 'tn alteniate route, the reaction of a-thienylmethylmagnesiuni chloride with acrolein and the Barbier modification5 of this method yielded. as the only isolable product,6 sym-di-(a-thienyljethane. A comparison of the physical constants of (It with those of IT and I11 indicated (I) is not identical with either compound, a fact which was further confirmed by the difference in melting points of the corresponding 3,3-dinitrobenzoatesa XIthough the three hutenols (I), (TI) and (111) underwent cleavage on ozonizationi indicating the presence of an olefinic linkage8 in their structures. formaldehyde (isolated as a 2,4-dinitrophenylhy-drazane J was obtained as an ozonization product only in the case of (11) and (111) but not in the case of (I) a fact indicating that the olefinic linkage in (I) is not terminally located. Failure to obtain acetaldehyde as an ozonization product of (I) was considered to exclude the possibility that (1) possessed the structure Th-CH(0H)-CH=CH---CH3 which could conceivably result if butadiene monoxide rearranged to crotonaldehyde which then underwent a normal reaction with the Grignard reagent. Dehydration of trj, (TI) and (111) yielded ail unsaturated intermediate (Ivj which, without further purification9 was converted in each case to the same maleic anhydride addition compound !V j according to the Diels-Alder method. lo If the possibility of migration of a thiophene ring from its original position on the butene chain during dehydration is excluded, then the dehydration product (IV) must be 1-(a-thienylj-butadiene-l,3,the maleic anhydride addition compound (Vi, X(m-thienyl\-14-tetrahydrophthalic anhy" I , ciride, the carlxm skeleton of (I),Th--C-&--C-C
i
l
l
1
arid the origirial butenols must differ only in the (,?) 13arhier, Compl rcnd., 148, 110
(1899).
(8) Delaby (CoinP1 r e n d , 194, 1248 (1932)) reported t h a t the reaction of benzylmagnesium bromide with acrolein gave only a 6% yield of benzylvinylcarbinol ' i )Thiophene under identical conditions was not oxidized. 8) Attempts to establish the presence of an olefinic linkage in compounds (I), (11) and (111) hy catalytic hydrogenation were unsuccessful. The compounds failed to add hydrogen. (9) The tendency for a-thienyl butadienes t o polymerize was so pronounced t h a t attempts t o purify these compounds by distillation m vaczio and at temperature- as low a? 40-.50° led t o their extensive polymerization. 'IO) Dirls, Alder ani1 Priri, B o , 62, 2081 (1429).
PREPARATION OF SOME THIENYL BUTENOLS
Oct., 1950
Th-MgBr
/O\ + CHz-CH-CH=CH2
+Th-CH=CH-CHzOH (1)
/9 + CH*-CH-CH=CH2
Th--Sa
+Th-CHz-CH(OH)-CH=CH2 (11)
+ CH2=CH-CHzMgBr
Th-CHO
--f
Th
I
Sa
CHa-C(0H)CECH
----f
(11s.) a"
Th-CH(OH)-CHz-CH=CH2 (111) Th
I
CHs-C(OH)CH=CHz
(YII)
(VI)
8
ThMgBr
I! + CH,-C-CH=CH~
f
/
1 !
-HzO
---+>
4587
Th-CH=CH-CH=CH8
+CH2=C(Th)-CH=CH2 (VIII) maleic anhydride
position of the hydroxyl group and the olefinic mole) of a-bromothiophene and 20 g. (0.83 gram-atom) of magnesium in 200 ml. of anhydrous ether (cooled in an icelinkage. bath) was added with vigorous stirring, over a period of To establish the fact that no migration of the one and one-half hours, 52 g. (0.75 mole) of butadiene thiophene ring had occurred during dehydra- monoxide dissolved in an equal volume of anhydrous ether. tion a-thienylmethylethynylcarbinol(V1)was pre- After standing for seven hours under an atmosphere of dry the reaction mixture was hydrolyzed by pouring pared by the reaction of sodium acetylide with 2- nitrogen it into a mixture of ice and water made slightly acidic with acetylthiophene in liquid ammonia. Compound dilute hydrochloric acid. The aqueous portion of the (VI) was then reduced by a solution of sodium in hydrolysate was extracted with ether, the extract added to liquid ammonia to 2-( a-thienyl)-butenS-ol-2 the organic portion of the hydrolysate and the combined solutions washed first with aqueous bicarbonate, then with (VII). Confirmation of the structure of (VI11 saturated brine, and finally dried over anhydrous magnewas afforded by its alternate synthesis from a- sium sulfate. thienylinagnesium bromide and methyl vinyl keThe ether was removed by distillatioii and the residue tone. The butenol (VII) was dehydrated to an on careful fractionation under reduced pressure yielded intermediate (VIII) which, without further puri- 40 g. (2670) of ( I ) , b. p. 85-86" ( 2 nim.)," XZ5D 1.5561, fication, was converted t o a maleic addition com- dZ6r 1.117. Calcd. for CaHloOS: C, 62.34; Ii, 6.49; S, pound (IX). This addition compound (IX) on 20.77. Found: C, 61.77; H, 6.46; S, 21.42. the basis of mixed melting point and analysis, The 3,5-dinitrobenzoate of (I) was prepared in the folproved t o be isomeric with s-(a-thienyl)-A4-tet- lowing manner. To a mixture of 1.0 ml. of (I) and 3.0 Compound ml. of anhydrous pyridine was added 0.5 g. of 3,5-dinitrorahydrophthalic anhydride (V) . (IX) must, therefore, be 4-(a-thienyl)-A4-tetra- benzoyl chloride and the mixture then heated on a steambath for ten minutes. After cooling the reaction mixture hydrophthalic anhydride and the dehydration was poured with stirring into cold water, the resulting product (VIII) from which it was obtained, 2- precipitate allowed to settle, and the supernatant liquid decanted. The residue was washed with a few milliliters (a-thieny1)-butadiene-1,3. The principal product obtained by the reaction of 5% sodium bicarbonate solution, filtered and, on refrom absolute methanol, melted a t 74.5of a-thienylmagnesium bromide with butadiene crystallization 75O. monoxide is, therefore, 4-(a-thienyl)-buten-2-01-1, A n d . Calcd. for CljHI2X%0&: C, 51.72; H , 3.46; a conclusion in conformity with the observations S , 8.04; S, 9.19. Found: C, 62.11; H, 3.44; S , 7 . T ; of Semeniuk and Jenkins.* According to the s, 9.11. 1-(a-Thienyl) -buten-3-01-2 (11).--a-Thienylsodiuni was mechanism favored by these authors. 3 -(a-thienyl)-buten-3-01-2 (11) should be an intermediate prepared from 50 g. (2.17 gram atoms) of sodium and 118 g. (1.0 mole) of a-chlorothiophene in 600 nil. of benzene which undergoes allylic rearrangement in the for- according to the procedure of Schick and €iartough.12tL mation of (I). Compound (11), however, was To this mixture, maintained under a nitrogen atmosphere found to be stable during hydrolysis of the reac- were added, with vigorous stirring, 70 g. (1.0 mole) of tion mixture. Compound (I), therefore, must butadiene monoxide in 100 ml. of anhydrous benzene a t such a rate that the reaction mixture was held a t gentle have resulted from l,.l-addition of the Grignard reflux. Stirring was continued until it had cooled to room reagent to butadiene monoxide rather than from temperature and the mixture was then poured into ice and water. The hydrolysate was acidified with dilute hydrorearrangement of (11). chloric acid and the aqueous portion extracted with lwri-
Experimental 4-(a-Thienyl) -buten-2-01-1 (I).-To a solution of athierrylmagriesiurn bromidc prepared from 135 g. (0.83
(11) All boiling points and melting point.; unrorrecterl (12) All analyses by hficro Tecii. f.aIJorxtori?\, Skokir, l l l i ~ ~ o i s . (12a) Schick and Hartough, Tms J O U R N A L , T O , 28fj (lW3).
/c!iL. T h combined benzene eatr'ict and orgaiiic yortioii of the hydrolyzate were washed with aqueous sodium bicarbonate, brine, and fixally dried over auhydrou, magnesium sulfate. After removal of the bciizene by distillation under a nitrogen atmosphere, fractionation of the rcsidue under reduced pressure yielded 25 g. (16 zc:1 of I l l . b. p. 80-81' 12 mrn.), N'SD 1.5468, d264 1.106 J n u l . Calctl. for CsEIl~OS: C, 62.31; 11, 6 . ~ S, ; 20.7'7. Found: C, 62.08; I f , 6.56; S, 18.14. Preparation of the 3,5-dinitrobeuzoate of (11) accordiug to the method previously indicated for the 3,5-dinitrobenzoate of (1) yielded a compound which, on recrystalli?Ition from absolute methanol, melted a t 89-90'.
traces 01 thc uuteduced acetylenic carbiuol by extractiug its ether solution with Tollens reagent, after which it was washed with brine and dried. The ether was removed by evaporation under reduced pressure and thc tion, likewise under reduced pressure, of ' \ * I l ) , h 1) fiij-ti;" 2 mni , V A ' D i r e d from
B. -To .t solution of a-thieiiyliiiagxresiurii bromide 111 400 nil. of ether prepared from 163 g (1.0 mole) of ai)rornothiophene and 24.3 g. [ i grmi atom) of nidgnesiuni were added slowly .tiid in dropbbise fashion a solution of 54.5 g. (0.79 mole) of methyl vinyl ketone in 200 ml. of
.inhydrous ether. Duririg this addition the reaction mixture was vigorously stirred and cooled. The reaction mixt u x was then hydrolyzed ant1 treated according to the procedure outlined in the preparation of ( I ) . Aftcr re9 33 moval of ether hy distillation under reduced pressure, l-ia-Thienyl) -buten-3-ol-l ,111) .---'To ,A liter of an fractionation of the reaction product under reduced prtsether solution of allylinagnesium bromide prepared from w r e yielded 7.0 g. (4.60/o) of (YII), b. y. 66-68" (2 mm.i ; f4.0 gram :ttoms) of magnesium and 145 g. (1.2 1.5438. The portions of (1'11) obtained from proceof allyl bromide according to the method of Gilman dures (A) aiid (I3) were combined and redistilled undei wly with vigorous agita- wduced pressure, 1) 1) 66-67' (2 mrii ) ; n2% 1.5430, ) of a-thiophenealdehydc d2!, 1.Oi1 ether. Throughout the i l ) i o / . Calcd. for CsHloOS: C, 632.34; H, f5 W . h , ,tdditiori of the aldchvtii the reaction mixture 'u ab cooled 2IJ.77'. Found: C, 62.50; H, 6.45; S,20.65. ni an ice-bath. Ozonization.-Three-gram samples of ( I ) , (XI) and ( I l l ) The reaction mixture M '3s then hydrolyzed and treated dissolved in 80 ml. of low-boiling ligroin were ozonized .itcording to the procedure outlined in the preparation of 'it 0' and the ozonide decomposed accordiug to the method (1) Aftel removal of ether by distillation, fractionation of n'hitmore m d Church.lY lkcomposition of the ozonides of the reaction product under rcduced pressure yielded 0 5 g . (GI?,) of IIII), h. p . 76-77" r - 0 tnln ) , )t% 15441, of (11) ,tiid (111) yielded as one of the product5 formaldehyde, isolated 3s 2,4-clinitrophenylhydrazone, m. p tElbJ 3.108. Thc identity of this compound mas further con.lncii. Calcd. for C&&S: C , ti2.34; 11, tj:Ly; S, firmed by mixed melting point with an authentic sample, the 31.77 Found: C, 61.65; H, 6.40; S, 20.95. 2,44initrophenyihydrazone of formaldehyde. No forPreparation of the 3,5-dinitrobenzo:itc of (111) accord- ination of formaldehyde 2,4-di1iitrophenylhydrazorlc YI a\ ing to the method of Marvel and Waltonil yielded a yellon observed when the ozonide of (I) was decomposed. crystalline compound, m. p. 54-55". * Dehydration of Buteno1s.--A 10-g. sample of the butenol alnul. Cdlcd. for CI,HI~N#.~~S: C, 51.72; H, 3.45; to be dehydrated was mixed with an equal weight of ans,8.04; S, Found: C, SI.58; 11, 3.67; S , 8.03; hydrous potassium acid sulfate together with a trace of s, 9.06. hydroquinone and introduced into a 50-ml. Claisen flask Z-(~~-Thienyl)-butyn-3-01-2 (VI) .-Three grain atonis attached to a receiver cooled in a bath of Dry Ice-acetone (117.3 g.) of potassium was converted15 to potassium The flask was then heated to 80" over a period of one-half amide in 1500 ml. of liquid ammonia contained in a three- hour and kept a t 80-90' for one hour in the case of (J'II) liter three-necked flask equipped with a mechanical stirrer, or heated to 100" over one-half hour and kept a t 100-1 10 e liquid ammonia condenser, and protected from atmospheric in the cases of (11) and (111). A pressure of 2 mm. u a i iii015t~tre :md carbon dioxide by t i wcla lirnc filled drying triaintained i i i the apparatus throughout the period of heating and the nuterial collected in the receiver consisted t 01%t r . The mixture, cooled to - 50°, was then saturated II iih dry acetylene for n period of forty minutes after which of a mixture of ice and approximately 1-2 g. of :tn organic ethcr nere added I O i g. (0.85 mole) of 2-ncetylthiophenc iiibst,tnce which was imniediately separated from the ice, dried over anhydrous magnesium sulfate, and without tli~solved in 100 ml. of anhydrous ether. The reaction mixture was stirred vigorously, held a t -5U", and kept further purification* converted to the corresponding tetrasaturated with acetylene throughout the xldrtion of the hydrophthalic anhydride derivative. ketone arid for five hours thereafter. It V A S then neuDehydration of (I) mas carried out in the manner just tralized by addition of excess ammonium chloride , the described for (VII) except that pulverized potassium hymimonia removed by evaporation, and the residue hy- droxide pellets were wed inqtead of anhydrous potassium acid sulfate. iirolyzed. The aqueous portion of the acidified hydrolyti' W.IS extracted with ether and the ether extract, comj-(a-Thienyl) -Ar-tetrahydrophthalic Anhydride (V) . net! with the organic portion of the hydrolyzate wa\ A solution of 2 g. of maleic anhydride and 3 g. of I - ( a isticti with aqueous sodium bicarbonate, brim, and thienyl) -hutadiene-l,3 (IV) , obtained by the dehydration of ( 1 and dissolved in 20 i d . of anhydrous benzene, was (11 let1 over anhydrous magnesium sulfate. Removal of t I i c cther by distillation folloived by fractionation of the heated for three hours a t YO3. The product whlch c i y c i I >i(lui undcr rcduced pressurc yielded 38.8 g. (307$) of t,tlli& from thc reaction mixture on cooling, was filtered, 1 I ).If h. p 7 0 71 5" (2 mm.) ; T I ~ O D 1.5556; dZo41.1518. .tnd after four recrystdizations from A mixt ur'c of benzent itid low-t)oiling ligroin, yielded 0 17 g . of ;I. colorlesi coni.l71uI. Cnlcd. for C8€IsOS: C, 63.15; 11, 5 . 2 7 ; S, pound \.], 111. p. 101)-10lo. 31 .OX. I'ouitci: C, 02.03; H , 5.44; S, 21.33. .1nd Calcd for C121110OJS. C, 6 1 5 3 ; 11, 4 5 ,S, 2 - ( a-Thienyl) -buten-3-ol-2 (VII) .-A. Methyl-a 13.63 Found C , 61.06; 13, 4.44, S,13.80. t hwiiylethyriylcarbinol (T'I), 20 g. (0.13 mole), was reiluced by sodium in liquid ammonia according t o the it'hexi the products obtained by the dehydration of (11) inethod of Campbell and Eby.17 The crude product was and (111)were derivatized according to the same procedure, compounds were obtained whose identity with ' 13) Gilman and McClumphy, Bull soc chrm , 48, 1322 (1928) crystalline ( V j was established by absence of depression in their 14) Marvel and Walton, J OVE C h o n , 1, 88 (1942). mixed melting points with (Y) . ,16) Vaughn Vogt and Nieuuland, THIS JOZIHNAL, 56, 2120 1-(a-Thienyl) -1,4,4a,9a-tetrahydroanthraquinone and IC)%&) I-(n-Thienyl)-anthraquinone.-A mixture of 2 g. of 1,4113) I'hi. rcet\it m c c~~r!~iiioI which darhrtis rathcr rapidly on ex hoquinoue m c l 2 g. of I-(a-thienyl) -butadiene-1 ,XI O-lll < t 0 11&11t LII 1 I l T I u l i i r d i n irtrlttion of s t r ~ 1 i hcatcrl i i i i I i t c i m - ~ ~ . i tfor h two hours Thc I
-____.
'1,
~lloqulllortr 1-
Cir~i,!,cII i n < /1
)I\
lii'i
11 t n k
i
63, .!iIi
ll+i'q
I
