Reaction of O,O-dialkyldithiophosphoric acids with N-alkyl-2-haloaldimines

Article abstract of DOI:10.1134/S1070363215090133

Synthetic results of reactions of O,O-dialkyldithiophosphoric acids with N-alkyl-2-haloaldimines fundamentally depend on the nature of the halogen: in the case of Cl-substituted imines the reaction afforded 2-(dialkoxythiophosphorylthio)iminium chlorides, with bromoimines bis(dialkoxythiophosphoryl) disulfide and unsubstituted iminium bromide were obtained. According to dynamic ³¹P NMR spectroscopy data the reason for this difference is the presence or absence of a free acid in the reaction medium.

Full text of DOI:10.1134/S1070363215090133

ISSN 1070-3632, Russian Journal of General Chemistry, 2015, Vol. 85, No. 9, pp. 2099–2105. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © R.A. Khairullin, M.B. Gazizov, N.G. Aksenov, Kh.R. Khayarov, 2015, published in Zhurnal Obshchei Khimii, 2015, Vol. 85, No. 9,
pp. 1520–1526.
To the 85th Anniversary of birthday of late Yu.G. Gololobov
Reaction of O,O-Dialkyldithiophosphoric Acids
with N-Alkyl-2-haloaldimines
R. A. Khairullin, M. B. Gazizov, N. G. Aksenov, and Kh. R. Khayarov
Kazan State Technological University, ul. Karla Marksa 68, Kazan, Tatarstan, 420015 Russia
e-mail: mukattisg@mail.ru
Received June 27, 2015
Abstract—Synthetic results of reactions of O,O-dialkyldithiophosphoric acids with N-alkyl-2-haloaldimines
fundamentally depend on the nature of the halogen: in the case of Cl-substituted imines the reaction afforded 2-
(dialkoxythiophosphorylthio)iminium chlorides, with bromoimines bis(dialkoxythiophosphoryl) disulfide and
unsubstituted iminium bromide were obtained. According to dynamic 31P NMR spectroscopy data the reason
for this difference is the presence or absence of a free acid in the reaction medium.
Keywords: O,O-dialkyldithiophosphoric acids, N-alkyl-2-haloaldimines, bis(dialkoxythiophosphoryl)disulfide,
unsubstituted iminium bromide, 2-(dialkoxythiophosphorylthio)iminium chloride
DOI: 10.1134/S1070363215090133
One of the basic methods for the synthesis of N,P-
containing organic compounds having diverse biolo-
gical activities and complexing properties is reactions
of P(III) and P(IV) acids with N-alkyl(aryl)aldimines
[1, 2]. The reaction of N-alkylaldimines with O,O-
dialkyldithiophosphoric acids have been initially
regarded as addition of the latter to the imine group
[3]. However, it was found later that the reaction stops
at the stage of protonation of the imine nitrogen atom
to form iminium salts [4]. In the case of chloral imines,
where the basicity of the imine nitrogen is low, their
protonation did not occur, so only the product formed
of the addition to the C=N bond [5]. In the products
obtained the chlorine atoms were inactive towards
subsequent substitution processes.
betaine 7. The reaction of dimethylphosphoric acid
with bromoimine 8, in contrast, occurred via trans-
formation of the intermediate adduct 9 into aziridinium
phosphonate 10.
Also we have previously established [9] that the
reaction of O,O-dialkyldithiophosphoric acids 11 with
N-alkyl-2-methyl-2-chloropropanimines 2 proceeded
in two stages. The first step consisted in the
protonation of the imine nitrogen atom and the
formation of the intermediate iminium salt, N-alkyl-2-
methyl-2-chloropropaniminium dialkyldithiophosphate
12, where the single chlorine atom was as labile as in
the adducts of dialkylphosphorous acid 1. In the
second stage the chlorine atom was replaced by
(dialkoxythiophosphorylthio) group to form N-alkyl-2-
(dialkoxythiophosphorylthio)-2-methylpropaniminium
chlorides 13 [9] (Scheme 1).
We have previously shown that a single chlorine
atom in the initial adducts of dialkylphosphorous acids
1 to N-alkyl-2-chloroaldimine 2 is labile, and pro-
longed keeping of the reaction mixture at room tem-
perature resulted in the formation of the products of
diverse structures [6–8]. Thus, intermediate aziridinium
salt 3 underwent isomerization of 2-chloroalkyl moiety
at P(IV) atom to give 1-chloroalkyl derivative 4. In
addition, phosphorylated ammonium salt 5 and
aziridine 6 were isolated as well as phosphonate
The reaction of O,O-dialkyldithiophosphoric acids
11 with N-alkyl-2-bromo-2-methylpropanimines 8 has
not been previously described in the literature. Based
on the fact that the primary adducts of dialkyl-
phosphorous acids 1 and 9 to chloro- (2) and bromo-
imines (8) were transformed into diverse compounds
5–7, 10, we assumed that in the case of the reactions of
imines 8 with dithio acids 11 a difference in further
2099

2100
KHAIRULLIN et al.
Scheme 1.
(R1O)2P(O)CHC(Cl)Me2
Me2C(Cl)CH
(R1O)2P(O)
_Cl
NR2
CH CMe2
N+HR2
NHR2
1
2
3
(R1O)2P(O)CHC(NHR2)Me2
(R1O)2P(O)CHCMe2
Cl
Cl N+H2R2 Cl_
4
5
(R1O) P(O)
CH CMe2
NR2
MeOP(O)CH(Cl)CMe2
2
O_
N+H2R2
6
7
NR2
CH CMe2
N+HR2
(MeO)2P(O)CHC(Br)Me2
Me2C(Br)CH
MeOP(O)
O_
NHR2
9
8
10
(R1O)2P(S)SH
N+HR2(R1O)2P(S)S_
Me2C(Cl)CH
12
11
N+HBu-t (R1O)2P(S)S_
CH NH+R2 Cl_
Me2C(Br)CH
Me2C
SP(S)(OR1)2
14
13
Scheme 2.
N+HBu-t Br_
(RO)2P(S)SH + Me2C(Br)CH
[(RO)2P(S)S]2 + Me2CHCH
NBu-t
8
16
11
15
Scheme 3.
Me2C(Br)CH NBu-t + HBr
Me2C(Br)CH N+HBu-t Br_
8
17
_
2Me2C(Br)CH N+HBu-t Br_
+ 2(RO)2P(S)SH
[(RO)2P(S)S]2 + Me2CHCHN+HBu-t Br + HBr
17
11
15
16
transformations of the intermediate iminium salt 14
might be observed.
phophate 14 occurred even at –90°C (δP = 107.7 ppm,
δN+H 13.0 ppm). At a temperature above –80°C it was
transformed into the final salt 16 and disulfide 15.
Compound 16 was a reduced starting imine salt. To
prove the existence of the stage involving reaction of
acid 11 with N-tert-butyl-2-bromo-2-methylpropani-
minium cation included in the intermediate salt 14 we
synthesized N-tert-butyl-2-bromo-2-methylpropanimi-
nium bromide 17, stable salt of this cation. It was
found that the reaction at a ratio 1 : 1 of these reagents
yielded bis(dialkoxythiophosphoryl) disulfide 15 and
N-tert-butyl-2-methylpropaniminium bromide 16
(Scheme 3).
Indeed, it was found that the major products of the
reaction between compounds 8 and 11 at a ratios of
1 : 1 and 1 : 2 were bis(dialkoxythiophosphoryl)
disulfide 15 and N-tert-butyl-2-methylpropaniminium
bromide 16. When using reagents ratio of 1 : 1 a half
of the starting imine 8 did not react, and it was
completely consumed at a ratio of 1 : 2 (Scheme 2).
1
According to H and 31P NMR spectroscopy data,
the formation of the intermediate N-tert-butyl-2-
bromo-2-methylpropaniminium O,O-diisopropyldithio-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015

REACTION OF O,O-DIALKYLDITHIOPHOSPHORIC ACIDS
Table 1. 31Р NMR study of the reaction between acid 11a and imine 2b
2101
T, °С
–60
–50
–30
–20
–10
0
Time, min
2
δР of 12а, ppm
107.5
107.1
105.1
101.5
100.5
99.2
Content of 12a, %
100.00
100.00
99.94
δР of 13a, ppm
Content of 13а, %
–
0.00
0.00
23
–
54
84.5
84.6
84.6
84.6
84.9
85.0
85.2
85.3
85.4
85.4
0.06
73
99.92
0.08
88
97.73
2.27
109
130
143
182
222
310
420
91.99
8.01
10
97.6
75.94
24.06
45.12
79.67
89.25
95.66
100.00
20
95.9
54.88
20
98.8
20.33
25
98.8
10.75
25
98.7
4.34
25
–
0.00
Hence the reactions of O,O-dialkyldithiophosphoric
acids with N-alkyl-2-halo-2-methylpropanimines funda-
mentally depend on the nature of the halogen and
result in the formation of 2-(dialkoxythiophos-
phorylthio)iminium chlorides 13 at Hlg = Cl or bis-
(dialkoxythiophosphoryl)disulfide 15 and iminium
bromide 16 at Hlg = Br.
3.3% due to disulfide 15 formation. Although acid 11a
was consumed in the reaction with salt 14a, the signal
intensity in the range of 81.0–82.1 ppm increased since
the resulting disulfide 15a contained two phosphorus
atoms.
Hence, depending on the nature of the halogen
atom the position of the acid ↔ salt equilibrium is
different. In the case of chloroimine the equilibrium is
almost completely shifted to the right: the system has
no free acid 11a, and salt 12a is transformed into the
reaction product 13a as a result of the nucleophilic
substitution of the chlorine atom with dialkoxythio-
phosphorylthio group. In the case of bromoimine the
equilibrium is shifted to the left: the system has much
free acid, which is involved into reducing the cation of
the intermediate salt 14a with disulfide 15a formation.
It should also be noted that although the reaction
mixture contains a significant amount of salt 14a, the
formation of the substitution product was not found.
This is obviously due to the fact that the rate of the
reduction process exceeds significantly the rate of SN
process.
To determine the cause of the dependence of the
reaction result on the halogen nature, we applied
dynamic 31P NMR spectroscopy for studying the
reaction of acid 1a with N-tert-butyl-2-methyl-
chloropropanimine 2a. Thus, in the 31P NMR spectrum
of the reaction mixture two signals corresponding to
the phosphorus atoms of the final iminium salt 13a and
intermediate salt 12a were observed. There was an
increase in content of the reaction product 13a and a
decrease in the amount of intermediate 12a as the
temperature and the reaction time increased (Table 1).
Likewise, the reaction of acid 11a with N-tert-
butyl-2-bromo-2-methylpropanimine 8a was studied
(Table 2). Comparison of the data presented in Tables 1
and 2 shows that within 3 min after mixing the
reagents the content of salt 14a is only 12.8% unlike
chloroimine salt 12a (100%). The signal at 81.0 ppm
refers obviously to the phosphorus atom of the starting
acid, since in the 1H NMR spectrum the signal of SH at
3.5 ppm was detected. After 37 min (–85°C) the
content of salt 14a in the reaction mixture reaches a
maximum (71%) and then quite rapidly decreases to
The reducing properties of O,O-dialkyldithiophos-
phoric acids have been described in [10–14]. Thus,
they reduce azobenzene to benzidine and aniline [10–
12], sulfoxides to dialkylsulfides [13], pyridine oxide
to pyridine [14], and 4,4'-diphenoquinone to 4,4-bis-
(2,6-di-tert-butylphenol) [15 ]; in so doing acids 11 are
converted into disulfides 15. In these examples the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015

2102
KHAIRULLIN et al.
Table 2. 31Р NMR study of the reaction between acid 11a and imine 8a
Content of the reaction
products,a %
T, °С
Time, min
δР of 14a, ppm
Content of 14a, %
δР of 11а and 15a
–90
–90
–90
–85
–80
–70
–70
–60
–50
–40
–30
–15
0
3
11
107.7
107.7
107.7
107.7
107.8
107.8
107.8
107.9
108.1
108.4
108.5
108.6
108.8
12.8
58.8
70.0
71.0
68.5
52.0
51.0
36.5
24.4
13.3
11.0
7.9
81.0
81.0
81.0
81.0
81.1
81.2
81.2
81.4
81.5
81.6
81.7
81.9
82.1
87.2
38.8
27.0
25.5
28.0
46.0
47.1
62.0
75.0
86.7
89.0
92.1
96.7
31
37
44
56
63
69
79
97
104
109
123
3.3
a The total content of acid 11a and disulfide 15a based on the starting acid.
reduction of organic compounds containing unsa-
turated or semipolar bond was mentioned. In the
literature there is no information on the use of acids 11
to reduce organic halides including C–Hlg bond. It
should be noted that in our case the C–Br bond
reduction occurred not in the starting imine, but in
iminium cation regardless of the anion nature
(dithiophosphate or bromide).
respectively. As a result of electron transfer through
the six-membered ring the bromine atom is substituted
by hydrogen, i. e. a reduction occurs of iminium salt
cation to form (dialkoxythiophosphoryl)sulfenyl
bromide 18. The interaction of the latter with dithiophos-
phate anion of new intermediate salt 19 led to forma-
tion of bis(dialkoxythiophosphoryl) disulfide 15
(Scheme 4).
We believe that the conversion of imine 8 into
iminium salt 14 increases the halophilic properties of
the halogen. The thiophosphoryl sulfur atom and the
SH hydrogen are coordinated with the partially
positively charged bromine atom and the carbon atom,
After establishing the dependence of the position of
the acid ⇄ salt equilibrium on the halogen nature, we
studied the reaction of acid 11a with chlorinated imine
2a in a ratio of 2 : 1. In this case the second equivalent
of acid should be involved into a competing reduction
Scheme 4.
[(RO)2P(S)S_ Me2C(Br)CH
N+HBu-t]
(RO)2P(S)SH + Me2C(Br)CH
NBu-t
8
11
14
_δ
Me2CCH N+HBu-t (RO)2P(S)S_
1
Me2CHCH N+HBu-t (RO)2P(S)S_ + (RO)2P(S)S Br
19 18
δ
Br +
S
H
S
[(RO)2P(S)S]2 + Me2CHCH N+HBu-t Br_
15
(RO)2P
16
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015

REACTION OF O,O-DIALKYLDITHIOPHOSPHORIC ACIDS
2103
Scheme 5.
-
2(i-PrO)2P(S)SH + Me2C(Cl)CH=NBu-t
9a
(i-PrO) P(S)SMe2C(Cl)CH=N+HBu-t + (i-PrO)
2P(S)SH
11
2
4
2
_
+
Me2CHCH=NHBu-t Cl + [(RO)
2P(S)S]2
[H]
SN
20
15
_
Me
+ HBu-t
Cl
2CCH=N
SP(S)P(OPr-i)2
12a
process. To a solution in CCl4 of twofold excess of
acid 11a a solution of chloroimine 2a in the same
solvent was added, and the mixture was maintained at
room temperature for 7 days. N-tert-Butyl-2-methyl-
propaniminium chloride 20 and bis(diisopropoxy-
thiophosphoryl) disulfide 15a were isolated in
individual state; about 50% of acid 11a was consumed
in the formation of disulfide 15a. According to 1Н and
31Р NMR, the mother liquor after separation of di-
sulfide 15a contained the substitution product, N-tert-
butyl-2-(diisopropoxythiophosphorylthio)-2-methyl-
propaniminium chloride 13a, and the starting acid 11a
in 4 : 1 ratio (Scheme 5).
400.13 and 100.61 MHz, respectively, reference TMS.
31P NMR spectra were registered on spectrometers
Bruker AVANCE 400WB (161.98 MHz) and Bruker
MSL-400 (162 MHz), external reference 85% H3PO4.
Reaction of N-tert-butyl-2-methyl-2-bromopropan-
imine 8a with O,O-diisopropyldithiophosphoric
acid 11a. a. The reagents ratio 1 : 1. A solution of
1.06 g (5.13 mmol) of imine 8a in 5 mL of CCl4 was
added dropwise to a solution of 1.1 g (5.13 mmol) of
acid 11a in 5 mL of CCl4 maintaining the temperature
between 0–5°C. Then, the temperature of the reaction
mixture was raised to 20°C, the mixture was stirred for
2–3 h, and then allowed to stand at room temperature
for 24 h. The resulting crystals were filtered off to give
0.42 g (80%) of N-tert-butyl-2-methylpropaniminium
1
In general, according to H and 31P NMR spectro-
scopy, 50% of the acid 11a was consumed in reduction
of chloroimine 2a, and 40%, in the formation of 13a;
10% of the acid remained unreacted.
1
bromide 14a, mp 103–104°C. H NMR spectrum
3
(CDCl3), δ, ppm (J, Hz): 1.29 d (6H, Me2CH, JHH
7.0), 1.57 s (9H, CMe3), 3.75 d. of septets (1H, CH,
3JHH 7.0, 3JHH 8.6), 8.27 d (1H, CH=N, 3JHH 8.6), 14.34
br.s (1H, N+H). 13С NMR spectrum (CDCl3), δС, ppm:
19.24 (Me2CH), 27.77 (CMe3), 32.08 (Me2CH), 61.86
(CMe3), 180.18 (HC=N). Found, %: C 51.71; H 8.63;
N 6.85. C8H18BrN. Calculated, %: С 51.94; H 8.72; N 6.73.
In summary, as in the case of the primary
dialkylphosphorus acid adducts to N-alkyl-2-chloro-
(1) and 2-bromoimines (8) the further conversion of
iminium salts 12 and 14 depended dramatically on the
nature of the halogen: chloroiminium salts underwent
intramolecular nucleophilic substitution of chlorine
atom with dialkoxythiophosphorylthio group, while
bromoiminium salts were reduced at the C–Br bond,
and the acid was converted to bis(dialkoxythio-
phosphoryl)disulfide. The reason for this difference
lies in the presence of free acid in the reaction
medium, which is involved into the reduction of C–Br
bond of iminium salts; in the case of chloroimine there
was no free acid.
The mother liquor was evaporated in a vacuum
(0.08 mmHg), volatile products were collected in a
1
liquid nitrogen trap. According to H NMR spectrum,
the condensate from traps contained the starting
bromoimine. After removal of all the volatile products,
disulfide 15a was isolated. Yield 0.8 g (73%), mp 91°C.
1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 1.41 d and
1.43 d (24Н, Me2CH, 3JHH 6.4), 4.90 d. of septets (4H,
3
3
CHOP, JHH 6.4, JPH 12.0). 31P NMR spectrum
EXPERIMENTAL
(CDCl3): δР 81.70 ppm.
1H and 13C NMR spectra (CDCl3) were recorded on
a Bruker AVANCE 400WB spectrometer operating at
b. The reagents ratio 1 : 2. To a solution of 2.14 g
(10 mmol) of acid 11a in 15 mL of CCl4 was added
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 9 2015

2104
KHAIRULLIN et al.
dropwise a solution of 1.03 g (5 mmol) of the imine 8a
in 5 mL of CCl4 keeping the temperature between 0–5°C.
Then the temperature of the reaction mixture was
raised to room temperature and the mixture was stirred
for 3 h. On the next day the crystals formed were
filtered off. We obtained 0.4 g (78%) N-tert-butyl-2-
metilpropaniminium bromide 14a, mp 103–104°C.
From the mother liquor 1.8 g (85%) of disulfide 15a
was isolated, mp 91°C (hexane).
After removing the solvent, the residue was dissolved
in diethyl ether and cooled. The crystals were filtered
off to give 20.5 g (81%) of N-tert-butyl-2-(diiso-
propoxythiophosphorylthio)-2-methylpropaniminium
1
chloride 13a, mp 147°C. H NMR spectrum (CDCl3)
3
δ, ppm (J, Hz): 1.18 d (12H, Me2CHO, JHH 6.1), 1.52
s (9H, CMe3), 1.85 s (6Н, СMe2), 4.62 d. sept (2H,
CHOP, 3JHH 6.1, 3JPH 12.1), 8.76 s (CH=N), 14.25 br.s
(1H, N+H). 13С NMR spectrum (CDCl3), δС, ppm (J,
3
Hz): 23.91 d and 23.34 d (OCHMe2, JPC 5.0), 27.56
Reaction of N-tert-butyl-2-methyl-bromopropan-
iminium bromide 17 with O,O-diizopropyldithio-
phosforic acid 11a. To a suspension of 3.1 g (10.8 mmol)
of bromide 17 in 25 mL of CH2Cl2 was added drop-
wise 2.3 g (10.7 mmol) of acid 11a at 0–2°C. After
10 h, the reaction mixture became homogeneous. After
keeping the reaction mixture for 48 h at room
temperature the solvent was removed in a vacuum. The
solid residue was treated with hexane. Undissolved
part was filtered off, washed twice with hexane, and
dried in a vacuum to give 2.9 g of a mixture (1 : 1) of
3
2
(CMe3), 28.34 d (SCMe2, JPC 8.1), 52.09 d (CS, JPC
2
4.0), 63.57 (CMe3), 75.32 d (Me2CHO, JPC 8.1),
177.45 (СH=N+). 31Р NMR spectrum (СDCl3): δР
85.20 ppm. Found, %: С 44.89; Н 8.50; Р 8.18; S
16.88. С14H31CINO2PS2. Calculated, %: С 44.73; H
8.31; Р 8.24; S 17.05.
b. The reagents ratio 2 : 1. A solution of 1.31 g
(8.1 mmol) of imine 2a in 15 mL of CCl4 was added
dropwise to a solution of 3.5 g (16.3 mmol) of acid
11a in 15 mL of CCl4 at –10°C. The mixture was
allowed to stand for 7 days at room temperature. After
removing the solvent, the residue was treated with
hexane. The resulting crystals were filtered off,
washed twice with diethyl ether, and dried to yield
0.60 g (46%) of 2-methylpropaniminium chloride
1
iminium salts 16 and 17. Н NMR spectrum (CDCl3),
δ, ppm (J, Hz): N-tert-butyl-2-bromo-2-methylpro-
paniminium bromide (17), 1.73 s (9H, CMe3), 2.33 s
3
(6Н, СМе2), 8.48 d (1H, CH=N+H, JHH 16.4), 14.39
br.s (1H, N+H); N-tert-butyl-2-methylpropan-
3
1
iminium bromide (16), 1.31 d (6Н, СМе2, JНН 6.8),
20, mp 139°C. H NMR spectrum (СDCl3), δ, ppm (J,
1.59 s (9Н, СМе3), 3.75 m (1Н, Me2CH), 8.22 d.d (1Н,
Hz): 1.26 d (6H, CHMe2, 3JHH 6.8), 1.55 s (9H, CMe3),
3
3
3
3
CH=N+H, JHH 8.4, JHH 16.4), 13.59 br.s (1H, N+H).
The combined hexane filtrate was cooled to give 1.7 g
(75%) of disulfide 15a with mp 91°С (hexane).
3.77 d. sept (1Н, Me2CH, JHH 6.8, JHH 8.8), 7.89 d.d
3
3
(1H, CH=N+H, JHH 8.8, JHH 16.4), 15.8 br.s (1H,
N+H).
Reaction of N-tert-butyl-2-methyl-2-bromopro-
panimine 8a with O,O-diethyldithiophosphoric acid
11b (1 : 2). A solution of 0.99 g (5.3 mmol) of imine
8a in 5 mL of CCl4 was added dropwise to a solution
of 1.8 g (9.6 mmol) of acid 11b in 15 mL of CCl4
maintaining the temperature between 0–5°C. The
reaction mixture was kept at room temperature for
24 h. The resulting crystals were filtered off to give
0.81 g (80.1%) of N-tert-butyl-2-methylpropaniminium
bromide 16, mp 103–104°C.
Bis(diisopropoxythiophosphoryl)disulfide 15a (1.8 g)
was isolated from the cooled mother liquor.
ACKNOWLEDGMENTS
This work was supported by the Ministry of
Education and Science (Research Work no. 1629) in
the frame of the basic part of governmental contract
(no. 56/2015).
REFERENCES
Reaction of O,O-diisopropyldithiophosphoric
acid 11a with N-tert-butyl-2-methyl-2-chloropro-
panimine 2a. a. The reagents ratio 1 : 1. To a solution
of 14.1 g (87 mmol) of N-tert-butyl-2-methyl-2-chloro-
propanimine 2a in 70 mL of CCl4 with stirring was
added dropwise 18.7 g (87 mmol) of O,O-diiso-
propyldithiophosphoric acid 11a maintaining the
temperature between 0–5°C. Then, the temperature
was raised to 20°C, and the mixture was kept for 24 h.
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