2
-(Perfluoroalkyl)ethanols by Thermal Alkylation of Lactams
J . Org. Chem., Vol. 61, No. 19, 1996 6515
a thick, foamy emulsion that slowly separated. GC showed
incomplete recovery had occurred. To the aqueous layer was
h, and the mixture was cooled to 25 °C. A GC sample (2.0
mL) was washed with 1% NaHCO
aqueous layer was extracted twice with HCCl
over K CO . GC results are given in Table 1B, entries 2-4,
3
solution (2.0 mL), and the
then added 1% aqueous NaHCO
extracted with toluene (1 mL), and the clear extract was
combined with the CCl layer. The mixture was dried and
3
(pH now 9), the mixture was
3
(10 d) and dried
2
3
4
individually and averaged.
diluted with acetone, and GC (“DB-5”, 15 m) was run (average
of two). See Table 2B, entry 1. After 2 h, a sample (0.4732 g)
and 1,2-DCB (0.0800 g) were similarly treated with water (2
Rea ction of P r od u ct Mixtu r e (Ta ble 4) w ith Aqu eou s
Sod iu m Bica r bon a te a n d Extr a ction in to CCl . Su bse-
4
qu en t Extr a ction of Aqu eou s la yer s w ith HCCl (Ta ble
3
3
(2 mL). To the aqueous layer
3B).7 A sample (Table 4; 7 h) was recovered from the reaction
tube by acetone rinse and evaporated. A portion (0.3739 g;
3.982% of the total reaction mixture; 0.1934 mmol of products
mL), toluene (1 mL), and HCCl
was added NaHCO (1 mL), and it was shaken with HCCl
mL). The combined extracts were used for GC. Results
average of two) are given in Table 2B, entry 2 (GC on “DB-
”, 15 m). Both runs showed substantial amounts of unknown
3
3
(1
(
5
from 1) and 1% NaHCO solution (1.00 mL) were shaken with
3
CCl (1.2 mL, 1.9 g) and formed a foamy emulsion (pH ca. 9,
4
substances, as listed. Samples after 3 h of reaction were run
on GC before and after being treated with aqueous aqueous
same as NaHCO solution). Surface active 6‚HI was probably
3
responsible for the foaming emulsion. After 5 min a cloudy
NaHCO
3
solution. Variable amounts of 3, 6, and 7 were found,
CCl layer (sample 4-5R-1; 1.8259 g) was drawn for GC (“DB-
4
as listed in Table 2B.
Rea ction of 1 a n d 2 w ith Wa ter P r esen t (m ol r a tio of
1”, 15 m col) analysis (see Table 3B). Besides 2, 3, and 7, 18.3
area % of four unknowns were observed. Lactam 2 comprised
48.70 area % of the total. The aqueous layer was shaken with
1
:2 ) 1:15.2; m ol r a t io of Wa t er :1 ) 2.25) a t 141 °C.
Isola tion of P r od u cts by Distilla tion . A heavy wall glass
reactor tube A was charged with 1 (2.4045 g, 4.930 mmol,
3
HCCl (1.00 mL; 1.49 g) for 1 min; the foamy aqueous layer
separated quickly and the lower layer (sample 4-5R-2; 1.4818
g) was drawn after 2 min. GC gave 2, 87.8 area %, 3, 4.44%,
and unknowns (six) comprised the remaining 7.3%. A second
9
8
7.2%; contained 0.57% C homologue and some polar impuri-
ties), lactam 2 (6.4467 g, 74.99 mmol, 99.5%; contained 0.10%
water impurity), and water (0.1939 g, 10.76 mmol; with the
water in 2, total wt, 0.2003 g, 11.11 mmol, 1.543 M); total
volume of reactants, 7.199 mL. After processing as above, the
reactor tube was heated in a stirred bath at 144 °C (inside
temperature was 141 °C) for 3 h. A dark reddish color
appeared as above. The reaction mixture was transferred to
a distillation flask (8.85 g, 0.9787 part, 4.825 mmol of 1
products) and volatile material distilled through a 10-in.
Vigreux column, with bad foaming at first. Fractions collected
were the following: I, bp 93-131 °C/10 mm, 5.02 g. GC gave
alcohol 3, 30.9%; 1, 0.68%; lactam 2, 46.9 mmol recovered, and
lactim 6, 0.75%. II, bp 83-101 °C/0.65 mm, 0.69 g, which was
chiefly lactam 2. Fractions I and II combined were analyzed
by GC. Lactam 2 increased to 63.3 mmol recovered, and
iminolactam 5 was 0.78%. Holdup in the column was 0.27 g.
The viscous brown residue of 2, 3, 5, and 6 HI salts was 2.44
g. The cold-trap liquid was 0.04 g. The residue of HI salts
was converted to lactam 2, alcohol 3, iminolactam 5, and
higher retention time products (probably oligomers of 5) by
extraction with HCCl
drawn after 5 min (4-5R-3; 0.6307 g). GC gave 2, 91.54 area
%; 3, 4.29%; and 7, 3.90%. A third extraction with HCCl (0.50
mL; 0.75 g) gave 4-5R-4 (0.60 g). GC gave 95.5% of 2 and
smaller amounts of 3 and 7. There was an increasing amount
3
(0.50 mL; 0.75 g) gave a cloudy layer
3
3
of 2 extracted into CHCl , and the amount of 3 remaining
diminished with each extraction. However, the extraction did
not completely recover the organic products.
7
In Table 3B the GC analysis of sample 4-5-1 is given for
reference. It is clear that the aqueous bicarbonate reaction
with this sample converted part of the unreacted lactim ether
salt 6‚HI into 3 and the new compound 7 and into the two
unknown compounds at 9.65 and 9.81 min (on the “DB-1”
column). Heating of the first extracted mixture 4-5R-1 on the
steam bath gave sample 4-5R1-1. This caused the loss of 7
and an increase in 3 and the unknown at 9.65 min, as well as
a higher boiling point unknown at 24.3 min. These results
are in accord with the expected behavior of 7 and may throw
some light on the identity of the other unknowns.
reaction with K
and HCCl (8.0 mL), as a stirred mixture in sealed tube at 66
C for 4 h. A GC sample (“DB-5” capillary column) gave 3 (2.21
2 3
CO (1.36 g, 9.86 mmol) in acetone (2.0 mL)
Rea ction of La cta m 2 w ith 1 a n d Wa ter (m ol r a tio 2:1
3
)
16.22; H
were iodoalkane 1 (0.7912 g, 1.614 mmol, 96.7% pure, GC;
.6469 M; passed down alumina to remove impurities; con-
tained 2.23% of C CH I), lactam 2 (2.2378 g, 26.187
mmol, 99.6% pure; 10.50 M), and water (0.0878 g, 4.872 mmol;
.953 M); total volume was 2.495 mL. Sealed tube A was
O:1 ) 3.02) a t 140 °C (Ta ble 2A). Materials used
2
°
mmol), 46.9 mol %, a trace of 1, recovered lactam 2 (5.24 mmol,
or 2 mols to 1 of 2:3); 5, (0.547 mmol) 11.3 mol %, and higher
0
8
F
17CH
2
2
ret time substances. HCCl
3
and acetone were distilled (up to
9
0 °C pot temp) from the filtered mixture (16.50 g), and the
1
pot liquid (4.25 g) on a “DB-1” capillary column gave 3, 45.6
mol % yield (on 1 used up); lactam 2, 5.08 mmol; and 5, 8.06
mol % on 1. Further distillation gave a mixture of 2 and 3,
bp 75-115/10 mm, 1.12 g, and a residue of 0.46 g. Isolation
of 2 and iminolactam 5 is consistent with two pathways for
conversion of lactim 6 to alcohol 3.
cooled to -196 °C, evacuated and filled with nitrogen. This
process was repeated after each sample was removed. The
tube was heated, while stirring by magnet bar in an oil bath
at 140 °C, for the times given. The reaction mixture formed
two layers at 140 °C and after 20 min remained clear
throughout the reaction period and when cooled for samples
at 25 °C. No weight loss occurred on heating at 140.0 °C.
Samples were removed by pipet into a vial and quickly
dissolved in HCCl
3
for GC. The results are given in Table 2A;
the time course of the reaction is plotted in Figure 2A, and
the least squares plot appears as Figure 2B.
Rea ction of δ-Va ler ola cta m (8) w ith 1 a n d Wa ter (m ol
r a tio 8:1 ) 14.0; w a ter :1 ) 2.10) a t 140 °C (Ta bles 8A-C).
Iodoalkane 1 (0.9038 g, 1.861 mmol, corrected, 96.7% pure by
Rea ction of Alk yla tion P r od u ct Mixtu r e of Ta ble 1A,
En tr y 8, w ith K
.989) in CCl a t 52 °C (Ta ble 1C). Sample entry no. 8 of
Table 1A (2.6882 g, 0.1503 part, 1.518 mmol of 1 products),
GC reference, 1,2-dichlorobenzene (0.1386 g), CCl (5.00 mL,
.97 g), and K CO (0.2073 g, 1.501 mmol) were stirred at 52
C under total reflux head, with a trap to the bubbler tube.
Samples (1.0 g) of the tan-colored slurry were filtered, and the
GC run was on a “DB-5”, 30 m column. The CCl solution was
2 3 2 3
CO (m ol r a tio of K CO :1 p r od u cts )
7
0
4
4
7
2
3
°
4
GC, 0.40 mL; 0.604 M; contained 2.23% of C8F17CH I), lactam
2
washed with water (1.0 mL) to give a foamy mixture and a
partial emulsion. GC results (Table 1C) for 3 are the average
of two determinations.
8 (2.60 g, 26.0 mmol, 99%), water (0.0704 g, 3.91 mmol, 0.070
mL), and 1,2-DCB (0.1500 g, GC ref) were charged to reactor
tube A. The reaction tube was cooled to -196 °C, evacuated,
and filled with nitrogen as in the tables above. This process
was repeated after each sample was removed. The tube was
heated, while stirring by magnet bar in an oil bath at 140 °C,
for the times given. The reaction mixture became homoge-
neous immediately at 140 °C and remained clear throughout
the reaction period and when cooled for samples at 25 °C. The
remaining reaction mixture, allowed to stand for 7 days,
formed long needles in the viscous mixture. GC samples were
drawn with a Pasteur pipet and weighed, and the pipet was
Rea ction of Alk yla tion P r od u ct Mixtu r e of Ta ble 1A,
En tr y 8, w ith K
2 3 2 3
CO (m ol r a tio of K CO :1 p r od u cts )
2
.00) in HCCl a n d Eth a n ol a t 68 °C (Ta ble 1B). Sample
3
entry 8 of Table 1A (9.30 g, 0.5201 part, 5.233 mmol of 1
products) was used for reaction; the sample contained 38.7%
of alcohol 3 by GC (Table 1B, entry 1). To this sample were
added ethanol (0.691 g, 10.5 mmol, 0.88 mL), HCCl
3
(5.0 mL,
(1.465
7
.46 g, 62.5 mmol), and 1,2-DCB (0.1746 g), and K CO
2
3
g, 10.61 mmol) was added while the mixture was stirred
vigorously at 25 °C. Stirring was continued at 68 °C for 7.5
rinsed with 12 drops of HCCl
3
. A “DB-5”, 30 m column was