Synthesis of Phthalic Aldehyde and Its Diacetals

Article abstract of DOI:10.1134/S1070363219110021

Acyclic phthalaldehyde diacetal without cyclic 1,3-dihydro-1,3-dimethoxybenzo[c]furan impurity has been obtained via the reaction of 1,2-bis(dibromomethyl)benzene with trimethyl orthoformate (1:6) at 90°C in the presence of 10 mol% of ZnCl₂. Hydrolysis of phthalaldehyde diacetal has led to the formation of phthalaldehyde without HBr evolution. The reaction of phthalaldehyde with trimethyl orthoformate in the presence of trifluoroacetic acid has proceeded abnormally, with the formation of the cyclic diacetal. The acyclic diacetal has been phosphorylated by chlorophosphines and the action of PCl₃ and a P(III) acid ester in sequence.

Full text of DOI:10.1134/S1070363219110021

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 11, pp. 2178–2184. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 11, pp. 1651–1658.
Synthesis of Phthalic Aldehyde and Its Diacetals
a
a,
a
R. A. Khairullin , M. B. Gazizov *, Yu. S. Kirillina ,
a
a
a
S. Yu. Ivanova , O. D. Khairullina , and K. S. Gazizova
a
Kazan National Research Technological University, Kazan, 420015 Russia
e-mail: mukattisg@mail.ru
*
Received April 22, 2019; revised April 22, 2019; accepted April 25, 2019
Abstract—Acyclic phthalaldehyde diacetal without cyclic 1,3-dihydro-1,3-dimethoxybenzo[c]furan impurity
has been obtained via the reaction of 1,2-bis(dibromomethyl)benzene with trimethyl orthoformate (1 : 6) at 90°C
in the presence of 10 mol% of ZnCl . Hydrolysis of phthalaldehyde diacetal has led to the formation of phthal-
2
aldehyde without HBr evolution. The reaction of phthalaldehyde with trimethyl orthoformate in the presence of
trifluoroacetic acid has proceeded abnormally, with the formation of the cyclic diacetal. The acyclic diacetal has
been phosphorylated by chlorophosphines and the action of PCl and a P(III) acid ester in sequence.
3
Keywords: phthalaldehyde, phthalaldehyde diacetals, 1,3-dihydro-1,3-dimethoxybenzo[c]furan, 1,2-bis-
(dibromomethyl)benzene, phosphorylation
DOI: 10.1134/S1070363219110021
Phthalic aldehydes exhibit strong bactericide activity
and are excellent disinfectants [1]. Various formulations
basedonthemarewidelyusedinpremisesdecontamination
and sterilization of medical equipment, especially related
to endoscopy. Therefore, development of novel methods
of phthalic aldehydes synthesis from available sources is
a topical issue.
acetonitrile under ultrasonication [14], with sodium
periodate in dichloromethane, water, or acetonitrile
under ultrasonication [15], with ozone in methanol or
butyl acetate [16], or with sodium iodate in the presence
of the Ru (CO) catalyst in acetonitrile, water, or
3
12
dichloromethane [16]; 1,2-di(hydroxymethyl)benzene
with manganese dioxide in dichloromethane [17], with
The known methods of synthesis of phthalic aldehyde
are based on various reactions of 1,2-disubstituted
3 3
iron nitrate [18] or oxygen in the presence of Ru(PPh ) Cl2
invarioussolvents[19],withdipyridinesilverpermanganate
1
in benzene [20], or with dimethyl sulfoxide and oxalyl
chloride in dichloromethane [21]; 1,2-di(bromomethyl)-
benzene with di(4-methoxyphenyl) selenoxide and
potassium hydrocarbonate in acetonitrile [22].
benzenes: hydrolysis, oxidation, bis(gem-diacetate)
deprotection, and reduction. The first methods of
synthesis of phthalic aldehydes have been based on the
hydrolysis of bis(dihalomethyl)benzenes with fuming or
concentrated sulfuric acid, and their further development
consisted in the methods of neutralization of the evolving
hydrogen halide [1–6]. Hydrolysis of acyclic diacetals of
phthalic aldehydes has been performed in the presence
of sulfuric [7], formic [8], phthalic [9], acetic [8], or
hydrochloric [10] acid as well as sodium hydroxide [7, 10].
Bis(gem-diacetate) deprotection has been performed
via the heating of phthalic aldehyde bis(diacetate) with
poly(4-vinylpyridinium) chlorate [P(4-VPH)ClO ] in
4
ethanol [23] or poly(4-vinylpyridinium) hydrosulfate in
methanol under ultrasonication [24] or via keeping of
bis(diacetate) and N-sulfonopoly-(4-vinylpyridinium)
chloride in methanol [25].
The related oxidation processes have involved the
following substrates: o-xylene with oxygen in water
Thefollowingsubstrateshavebeensubjecttoreduction:
Восстановлению подвергали фталевые кислоты и их
производные: phthalic acid in the presence of tert-hexyl-
s-butoxyborane in tetrahydrofuran [26] or in the presence
[11] or in chloroform in the presence of 10-methyl-9-
phenyl-10-acridinium perchlorate [12]; naphthalene with
potassium metaperiodate in the presence of potassium
aquapentachlororuthenate(III) in water, dichloromethane,
or acetonitrile [13], with potassium bromate in the
presence of Ru-catalyst in dichloromethane, water, or
of LiAlH [27]; phthaloyl dichloride in the presence of
4
pentacoordinate hydrosilane [28]; phthaloyl diamide
in the presence of LiAlH [29]; and phthaloyl dinitrile
4
2
178

SYNTHESIS OF PHTHALIC ALDEHYDE AND ITS DIACETALS
2179
Scheme 1.
CHBr2
CH(OMe)2
CHBr2
+
CH(OMe)2
ZnCl2
4 CH(OMe)3 ꢀ
4(HCOOMe + MeBr)
3
2
4
OCH3
CHO
CHO
H O, HCl
H O, CF COOH
2
2
3
+
2 MeOH
+ 2 MeOH
O
'
'
OCH3
5
1
in the presence of sodium hydrotris(dibutylamino)-
aluminate in tetrahydrofuran [30].
possibility of transformation of other functional groups
under the action of a strong base (alkoxide anion).
It should be underscored that hydrolysis of readily
available 1,2-bis(dibromomethyl)benzene 2 is among
the oldest [1–6] yet used up to now [7–10] methods of
phthalic aldehyde synthesis. However, this method suffers
from several drawbacks, the major one being vigorous
evolution of hydrogen bromide corroding the equipment
and limiting the chemicals loading.
We were the first to use trialkyl orthoformates
instead of alcoholates for di(dehaloalkoxylation) of
dihalomethylarenes [40]. We have synthesized a series
of acetals of substituted benzaldehydes including
terephthalic aldehyde diacetals 6 via the interaction of
1,4-bis(dibromomethyl)benzene 7 with orthoformates 4
at 50°С during 4–5 h in the presence of 10 mol% of zinc
chloride as catalyst [41–42].
Herein we elaborated a novel method of preparation of
phthalic aldehyde 1 from 1,2-bis(dibromomethyl)benzene
The corresponding acyclic phthalic aldehyde diacetals
3 have not been described in the literature, however their
synthesis has been attempted via the interaction of phthalic
aldehyde 1 with ethanolic solution of triethyl orthoformate
(1 : 1) in the presence of aluminum chloride as catalyst
[43], via acetalization of aldehyde 1 with methanol using
2
2
avoiding the formation of HBr. First, the tetrabromide
reacted with trimethyl orthoformate to be converted
into the acyclic diacetal 3, which was transformed into
phthalic aldehyde 1 upon heating in acidified water. The
1
Н NMR study revealed that cyclic phthalic aldehyde
diacetal (1,3-dihydro-1,3-dimethoxybenzo[с]furan 5)
was initially formed at room temperature and then was
converted into the aldehyde 1 upon heating in acidic
aqueous medium (Scheme 1).
catalytic amount of TiCl or in the presence of NH3
4
or Et N [38], and via the reaction of aldehyde 1 with
3
dimethyl sulfite in methanol [44]. A mixture of acyclic
diacetal 3 and 1,3-dihydro-1,3-dialkoxybenzo[с]furan 5
has been formed in the mentioned cases.
The last stage of the scheme was performed separately,
the yield of phthalic aldehyde 1 being 81%.
We found that, in contrast to 1,4-bis(dibromomethyl)-
benzene 7, 1,2-bis(dibromomethyl)benzene 2 practically
did not interact with trimethyl orthoformate under the
mentioned conditions, the latter being decomposed into
methyl formate. However, acyclic phthalic aldehyde
diacetals 3 were formed in high yield at 90°С or above
and at the threefold excess of the orthoester (ratio 1 : 6)
As seen in Scheme 1, phthalic aldehyde diacetals 3
and 5 were intermediate products, and therefore their
synthesis became an important issue. Acetals have been
successfully prepared via the interaction of available
organic gem-dihalides with alkali metals alcoholates
[31–37]: di(dehaloalkoxylation) of aryldihalomethanes or
(Scheme 2).
benzylidene halides. The interaction has involved gem-
dichlorides [33–36] and (much rarer) gem-dibromides
Hence, we elaborate a novel method of the synthesis of
[
37–39]. The major drawbacks of this approach are
acyclic phthalic aldehyde diacetal 3 free of 1,3-dihydro-
1,3-dialkoxybenzo[с]furan 5 admixture.
the need to prepare an alkali metal alcoholate and the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

2180
KHAIRULLIN et al.
Scheme 2.
CHBr2
Br HC
2
+
6CH(OMe)3
2
4
CH(OMe)2
ZnCl , 90°ɋ
CH(OMe)2
2
+ 4HCOOMe + 4MeBr + 2CH(OMe)3
3
Scheme 3.
CHO
OCH3
O
OHC
CF COOH
+
CH(OMe)3
3
OCH3
5
1
4
Scheme 4.
Cl(MeO)HC
CH(OMe)2
OCH3
O
CH(OMe)Cl
(
MeO) HC
2
2
PCl3
H O
2
ꢀ
2MeOPCl2
ꢀHCl
OCH3
3
7
5
It is known that terephthalic aldehyde diacetals 6
the reaction occurred through intermediate formation
of di-α-chloroether 7 and О-methylphosphinites 11,
the interaction of which gave diphosphine dioxides 10
(Scheme 6).
can be formed via the interaction of the aldehyde with
orthoesters 4 in the presence of acids [43]. We were the
first to find that the interaction of phthalic aldehyde 1
with orthoesters 4 in the presence of trifluoroacetic acid
as catalyst occurred abnormally to yield cyclic diacetal
In summary, we elaborated a novel method of
phthalic aldehyde synthesis avoiding evolution of
HBr, via the conversion of 1,2-bis(dibromomethyl)-
benzene into the acyclic diacetal under the action of
trimethyl orthoformate, followed by hydrolysis. A
novel method was proposed to prepare acyclic phthalic
aldehyde diacetal without cyclic one (1,3-dihydro-1,3-
dimethoxybenzo[с]furan) admixture via the interaction
of 1,2-bis(dibromomethyl)benzene with trimethyl
orthoformate (1 : 6) at 90°С in the presence of 10 mol %
5
in good yield (Scheme 3).
Compound 5 was also prepared from acyclic diacetal
3
: the interaction of the latter with PCl gave the
3
corresponding di-α-chloroether 7, hydrolysis of which
led to cyclic diacetal 5 (Scheme 4).
The structure of intermediate compound 7 was
1
confirmed by the Н NMR data and by the reaction with
trimethyl phosphite affording diphosphonate 8 (Scheme 5).
Diacetal3alsoreactedwithsecondarychlorophosphines
of ZnCl . Moreover, we developed two methods of
2
9
to yield tertiary diphosphine dioxides 10. Evidently,
synthesis of cyclic phthalic aldehyde diacetal: via the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

SYNTHESIS OF PHTHALIC ALDEHYDE AND ITS DIACETALS
2181
Scheme 5.
(
MeO) (O)P
Cl(MeO)HC
CH(OMe)Cl
2(MeO)3P
2
CH(OMe)
CH(OMe)
+
ꢀ
2MeCl
(
MeO) (O)P
2
7
8
Scheme 6.
CH(OMe)2
Cl(MeO)HC
CH(OMe)Cl
CH(OMe)2
+ 2R PCl
2
+ 2R2
POMe
3
9
7
11
R (O)P
2
CH(OMe)
2 MeCl
CH(OMe)
+
R (O)P
2
10
R = Et (ɚ), Ph (b).
reaction of the aldehyde with trimethyl orthoformate in
the presence of trifluoroacetic acid and via the interaction
Phthalic aldehyde (1). a. A mixture of 12.00 g
(0.028 mol) of 1,2-bis(dibromomethyl)benzene 2, 17.83 g
(0.168 mol) of trimethyl orthoformate 4, and 0.57 g
(0.0042 mol) of zinc chloride was heated at 90°C during
5 h. The reaction mass was cooled, treated with 50 mL
of isooctane, and filtered. 5 g (0.278 mol) of water and
3 drops of HCl were added to the solution, and the
obtained mixture was heated (80°С) during 2 h distilling
off the formed methanol. The organic layer was separated
of the diacetal 3 with PCl , followed by hydrolysis of
3
the di-α-chloroether intermediate; phosphorylation
of the diacetal with secondary chlorophosphines and
via sequential action of PCl and P(III) acid ester was
3
realized.
EXPERIMENTAL
1
13
and dried over MgSO . The solvent was removed, and
Н and С NMR spectra were recorded using Tesla
BS–567A(100 MHz) andAVANCE 400WB (400.13 and
1
4
the crystalline residue was recrystallized from petroleum
ether. Yield 2.97 g (79%), mp 58°С (mp 56.5–58°С [46]).
1Н NMR spectrum (acetone-d6), δ, ppm: 7.85 d. d and
8.01 d. d (4Н, С6Н4, JHH = 3.2, 5.2 Hz), 10.51 s (2Н,
31
00.61 MHz) instruments. РNMR spectra were recorded
using an AVANCE 400WB instrument (161.98 MHz)
reporting the chemical shifts of phosphorus nuclei relative
to 85% H PO .
13
CHО). С NMR spectrum (acetone-d ), δ , ppm: 130.72
3
4
6
С
(
1
2С, o-CH ), 133.68 (2C, m-CH ), 136.65 (2С, ССНО),
92.00 (2С, СНО).
Commercial o-xylene, bromine, trimethyl ortho-
formate, and phosphorus trichloride were used. 1,2-Bis-
Ar
Ar
(dibromomethyl)benzene 2 was synthesized as described
b. 3 mL of water and 3–4 drops of HCl were added
elsewhere [1]. The solvents were purified and dried via
to a solution of 1.8 g (0.01 mol) of 1,3-dihydro-1,3-
conventional procedures [45].
dimethoxybenzo[с]furan 5 in 10 mL of CCl , and the
4
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

2182
KHAIRULLIN et al.
obtained mixture was boiled distilling off the formed
methanol. The residue was dried under vacuum and
recrystallized from petroleum ether. Yield 1.08 g (81%).
After 24 h, excess of the orthoester and other volatile
compounds were removed under vacuum, and the residue
was distilled. Yield 1.17 g (85%).
Phthalic aldehyde bis(dimethyl)acetal (3).Amixture
of 12.00 g (0.028 mol) of 1,2-bis(dibromomethyl)benzene
, 17.83 g (0.168 mol) of trimethyl orthoformate 4, and
.57 g (0.0042 mol) of zinc chloride was heated at 90°C
during 5 h. The reaction mass was cooled, treated with
0 mL of isooctane, and filtered. Isooctane was removed
1,2-Benzenebis[(methoxymethyl)dimethoxyphos-
phonate] (8).Asolution of 4.1 g (0.034 mol) of trimethyl
phosphite in 5 mL of benzene was added under dry
argon stream to a solution of 3.7 g (0.157 mol) of
bis[(chloro)methoxymethyl]benzene 7 [prepared from
3.87 g of 1,2-bis(dimethoxymethyl)benzene] in 10 mL
of anhydrous benzene. The reaction mass was stirred
at 20°С during 1 h, heated at 60°С during 2 h, and kept
under vacuum (0.02 mmHg, 60°С) during 1 h. Yield 5.2 g
2
0
5
under vacuum, and the residue was distilled. Yield 5.25 g
1
(
85%), colorless liquid, bp 65–66°С (0.3 mmHg). Н
NMR spectrum (CDCl ), δ, ppm: 3.29 s (12Н, OMe),
3
1
5
.67 s (2Н, СНO ), 7.30 d. d and 7.57 d. d (4Н, С H ,
(82%), viscous liquid. Н NMR spectrum (CDCl ), δ,
2
6
4
3
13
JHH = 3.4, 6.4 Hz). С NMR spectrum (CDCl ), δ , ppm:
ppm: 3.31 s (6Н, ОМе), 3.53 d and 3.71 d (12Н, РОМе,
JНH = 10.4 Hz), 5.12 d (2H, CHP, 2JРH = 12.8 Hz),
3
С
4
1
7.76 (4С, OMe), 95.38 (2С, СН), 121.55 (2С, m-CHAr),
22.91 (2С, o-CH ), 130.49 (2С, 2C ).
7.28 d. d (2Н, m-CH , J = 5.2, 3.6 Hz), 7.50 d (2Н,
Ar
Ar
Ar НH
1
3
o-CH , J = 3.6 Hz). С NMR spectrum (CDCl ), δ ,
1
,2-Di[(chloro)methoxymethyl]benzene (7). A
Ar НH
3
С
ppm: 53.11 and 53.93 (2С, ОМе), 58.38 d (4С, РОСН ,
solution of 2.54 g (0.011 mol) of phthalic aldehyde
3
2
1
J = 6.3 Hz), 75.20 d (2С, СН, J = 166.5 Hz), 127.13,
bis(dimethyl)acetal 3 in 5 mLof СCl was added dropwise
РС
РС
4
1
6
6
28.29, and 133.57 (6С, С Н ). Found, %: С 44.21; Н
to 6.04 g (0.044 mol) of PCl at 5°C. The mixture was
6 4
3
.62; Р 15.98. С Н О Р . Calculate, %: С 43.99; Н
stirred during 1 h at that temperature. The compound was
thermally unstable and could be identified in crude form
after elimination of the solvent and volatile product under
vacuum (0.05 mmHg) on cooling. Yield 2.30 g (89%) of
14 24
8 2
.33; Р 16.20.
1,2-Benzenebis[(methoximethyl)diphenylphos-
phine oxide] (10b). 1.28 g (0.0055 mol) of compound
3 was added dropwise at stirring to a solution of 2.5 g
(0.011 mol) of diphenylchlorophosphine in 10 mL
of isooctane. The reaction mixture temperature was
increased to 27°С. The mixture was heated at 45–50°С
during 2.5 h and then left for a day at room temperature.
The crystals were filtered off and dried. Yield 2.45 g
1
crude compound 7. Н NMR spectrum (CDCl ), δ, ppm:
3
3
.86 s (6Н, ОМе), 66.92 s (2H, CHCl), 7.53 m and 7.76
m (4Н, С Н ).
6
4
1
,3-Dihydro-1,3-dimethoxybenzo[с]furan (5). a.
2
2
mL (0.11 mol) of water was added to a solution of
.3 g (0.0098 mol) of 1,2-di[(chloro)methoxymethyl]
1
benzene 7 in 5 mL of CCl at room temperature, and the
(79%), mp 183–184°С. Н NMR spectrum (acetone-d6),
4
2
mixture was stirred during 0.5 h. The aqueous layer was
separated, the organic layer was dried over K CO . The
δ, ppm: 3.46 s (6Н, ОCH ), 6.48 d (2Н, CHР, J
=
3
РH
10.8 Hz), 6.82 d. d and 6.90 d. d (4Н, С Н , J = 5.6,
2
3
6
4
HH
3
solvent was removed under vacuum, and the residue was
distilled. Yield 1.27 g (72%) of compound 5 as a 65 : 35
mixture of cis/trans-isomers, bp 62–63°С (0.2 mmHg).
3.6 Hz), 7.97 d. d and 7.66 d. d (8Н, o-CH , J
=
Ar
РH
11.0, JHH = 7.2 Hz), 7.37 t (4Н, p-CH , J = 6.0 Hz),
Ar HH
31
7.48–7.59 m (8Н, m-CH ). Р NMR spectrum (CDCl ):
Ar
3
1
Н NMR spectrum (CDCl ), δ, ppm: 3.32 s (6Н, ОМе,
δP 31.67 ppm. Found, %: С 72.27; Н 5.51; Р 10.81.
С Н О Р . Calculated, %: С 72.08; Н 5.69; Р 10.93.
3
trans), 3.35 s (6Н, ОМе, cis), 5.99 s (2Н, СНОМе, cis),
3
4
32
4 2
6
.24 s (2Н, СНОМе, trans), 7.37 m and 7.43 m (4Н,
1
,2-Benzenebis[(methoxymethyl)diethylphosphine
13
CH ). С NMR spectrum (CDCl ), δ , ppm: 53.28 (2С,
ОМе, trans), 55.45 (2С, ОМе, cis), 105.25 (2С, СНО2,
cis), 106.39 (2С, СНО , trans), 122.92, 129.47, and
1
Ar
3
С
oxide (10a). 2.26 g (0.01 mol) of compound 3 was
added dropwise at stirring and cooling (10°С) to 2.48 g
(0.02 mol) of diethylchlorophosphine. The obtained
crystalline mass was recrystallized from isooctane.
2
38.85 (6Н, С Н , trans), 122.97, 129.36, and 138.68
6 4
(6Н, С Н , cis).
1
6
4
Yield 2.77 g (74%), mp 102–104°С. Н NMR spectrum
b. 2 drops of trifluoroacetic acid were added to a
(CDCl ), δ, ppm: 0.91 t, 0.96 t, 1.29 t, and 1.33 t (12Н,
3
CH CH , J = 7.6, 3JPH = 6.8 Hz), 1.47–1.62 m and
mixture of 1.0 g (0.0075 mol) of phthalic aldehyde 4
and 3.18 g (0.03 mol) of trimethyl orthoformate 6. The
reaction mixture temperature was increased to 42°С.
2
3
HH
2
1.84–1.93 m (8Н, РСН ), 5.86 d (2Н, CHР, J = 12.0
2
РH
Hz), 7.29 d. d (2Н, m-CH , J = 5.2, 3.6 Hz), 7.42
Ar HH
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 11 2019

SYNTHESIS OF PHTHALIC ALDEHYDE AND ITS DIACETALS
2183
3
31
d. d (2Н, o-CH , J = 5.2, JHH = 3.6 Hz). Р NMR
and Eftekhari, T., RSC Adv., 2015, vol. 5, p. 101013.
Ar
РH
spectrum (CDCl ): δ 53.99 ppm. Found, %: С 57.63; Н
https://doi.org/10.1039/C5RA18179H
3
Р
8
8
.52; Р 16.48. С Н О Р . Calculated, %: С 57.75; Н
.62; Р 16.55.
16. Reintjens, R.W.E., Broxterman, Q.B., Kotthaus, M., and
Poechlauer, P., WO Patent 2007/134847, 2006.
1
8
32
4 2
1
1
1
2
2
2
7. Endo, K., Takahashi, H., and Aihara, M., Heterocycles,
996, vol. 42, p. 589.
https://doi.org/10.3987/COM-95-S48
8. Namboodiri, V.V., Polshettiwar, V., and Varma, R.S.,
Tetrahedron Lett., 2007, vol. 48, p. 8839.
https://doi.org/10.1016/J.tetlet.2007.10.068
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vol. 1, p. 713.
https://doi.org/10.1021/ol990117w
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FUNDING
1
This study was financially supported by the Ministry of
Education and Science of Russian Federation in the scope of
the basic part of the State Task (project no. 4.5348.2017/8.9).
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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