Full text of DOI:10.1016/0020-1650(70)80097-6

1N0R~
NUCL. CHEM. LE77ER5
V~.
~
~.
~
1~0.
Per9am0n Pre55.
P
~
~
6~
1~1~1m
7H1080RA~E5: 7HE1R U5E 1N 7HE 5YN7HE515 0F 7H10ACE7AL5
R. H. Cra99 and J. P. N. Hu56and
7he Chem1ca1 La60rat0ry, Un1ver51ty 0f Kent at Canter6ury
(ReceWed 23 June 1970)
7h10acet~15 are w1de1y u5ed 1n 5ynthet1c 0r9an1c chem15try
6ut the1r preparat10n 1nv01ve5 the u5e 0f mercaptan5 wh1ch
nece551tate5 carefu1 hand11n9 techn14ue5.
We w15h t0 rep0rt a c0nven1ent 5ynthe515 0f th10aceta15,
1n 900d y1e1d5 and at am61ent temperature5, wh1ch enta115 the
react10n 0f an a1dehyde w1th a th1060rane (read11y 06ta1ned 6y
the 1nteract10n 0f a 60r0n ha11de and 1ead mercapt1de) 1n an
1nert 501vent 5uch a5 petr01eum 5p1r1t.
W1th the except10n 0f
6en2a1dehyde n0 react10n5 0f a1dehyde5 and th1060rane5 have
6een rep0rted. (1)
7he type5 0f react10n 5tud1ed are 5h0wn 1n e4uat10n5 1
and 2.
/H
/H
+ 3 - C ~
2(R8)58 + 3 - C~0
> ~
(1)
+
>
+
7he 60r0n-c0nta1n1n9 pr0duct5 6e1n9 1n501u61e 1n petr01eum 5p1r1t
are ea511y rem0ved 6y f11trat10n.
50me 1dea 0f the 5c0pe 0f the react10n can 6e 5een 6y the
examp1e5 91ven 1n the ta61e.
A11 c0mp0und5 have 6een
character15ed 6y ana1y515 and ~H n.m.r.
773

~4
7~080RANE5
~
7HE 5YN7HE5~ 0F 7H10ACE7AL5
V01. ~ N0. 9
7 ~
Reactant5
Pr0duct5
Y1e1d %
~F~CH(5Et)~ + (Ph80)~
CH5CH=CHCH(5Et)m + (Ph80)5
~H~CH--CHCH(5Et)~ + 8~05
45
67
59
CeF~CH0 + Ph(5Et)5
CH~CH=CHCH0 + Ph8(5Et)5
CeH5CH=CHCH0 + (Et8)58
~ CH~0CeH~CH0 + (~e8)58
P CH~0CeH~CH0 + (Et5)58
p CH50~H~CH(5Ne)5 + 8~05
56
p cH~0~H.cH(5Et)~ + ~0~
~8
A t7D1ca1 react10n wa5 a5 f0110w5:- Cr0t0na1dehyde (0.V~ 9.) and
615(ethy1th10)phen2160rane (2.2 9.) were m1xed 1n petr01eum 5p1r1t
~6.p. 60-68°, 25 m1.).
t~e ~1xture wa5 ref1uxed f0r f0ur h0ur5 t0 6r1n9 the react10n t0
c0mp1et10n. 0n c0011n9 phen7160r0x1ne (1.1 9., 98%) wa5 f11te~ed
An ex0therm1c react10n t00k p1ace and
0ff and after the rem0va1 0f the 501vent the re51due aff0rded 0n
d15t111at10n cr0t0na1deh~de d1ethy1th10aceta1 (1.2~ 9., 67%).
7he ea5e 0f the react10n can 6e attr16uted t0 the h19her
aff1n1ty 0f 60r0n f0r 0xY9en than 5u1phur.
We w15h t0 thank 5.R.C. f0r 5upp0rt.
Reference
8. E. M1kha110v and N. 5. Fed0t0v, 12ve5t.Akad.Na~k. 5.5.5.R.
0td.kh1m.Na~k0, 999, (1962).