New methods to synthesize phthalaldehyde and its diacetals

Article abstract of DOI:10.1007/s11172-019-2640-y

A new synthesis of phthalaldehyde that avoided formation of HBr involved treatment of 1,2-bis(dibromomethyl)benzene with trimethyl orthoformate (1: 6, 90 °C, 10 mol.% ZnCl₂) to obtain acyclic diacetal without admixture of cyclic one (1,3-dimethoxy-1,3-dihydrobenzo-[c]furan) followed by hydrolysis to give the target dialdehyde. Phthalaldehyde reacted with CH(OMe)₃ in the presence of trifluoroacetic acid to yield exclusively cyclic diacetal. Acyclic diacetal was phosphorylated by treatment with secondary chlorophosphines and by the reaction with PCl₃ followed by treatment with P^III acid ester.

Full text of DOI:10.1007/s11172-019-2640-y

Russian Chemical Bulletin, International Edition, Vol. 68, No. 10, pp. 1878—1882, October, 2019
1878
New methods to synthesize phthalaldehyde and its diacetals
M. B. Gazizov, R. A. Khairullin, S. Yu. Ivanova, Yu. S. Kirillina, I. O. Romanenko, and N. N. Gazizova
Kazan National Research Technological University,
68 ul. K. Marx, 420015 Kazan, Russian Federation.
Fax: +7 (843) 231 9505. E-mail: mukattisg@mail.ru
A new synthesis of phthalaldehyde that avoided formation of HBr involved treatment of
1,2-bis(dibromomethyl)benzene with trimethyl orthoformate (1 : 6, 90 C, 10 mol.% ZnCl2)
to obtain acyclic diacetal without admixture of cyclic one (1,3-dimethoxy-1,3-dihydrobenzo-
[c]furan) followed by hydrolysis to give the target dialdehyde. Phthalaldehyde reacted with
CH(OMe)3 in the presence of trifluoroacetic acid to yield exclusively cyclic diacetal. Acyclic
diacetal was phosphorylated by treatment with secondary chlorophosphines and by the reaction
with PCl3 followed by treatment with PIII acid ester.
Key words: phthalaldehyde, acetals, 1,2-bis(dibromomethyl)benzene, trimethyl orthoformate,
1,3-dimethoxy-1,3-dihydrobenzo[c]furan, phosphorylation.
Phthalaldehyde (PA) (1) and its analogs exhibit pro-
oxalyl chloride in CH2Cl2;21 1,2-bis(bromomethyl)benz-
ene with bis(4-methoxyphenyl)selenoxide in the presence of
sodium hydrocarbonate in MeCN.22 Bis(gem-diacetate)
protection was cleaved by heating phthalaldehyde bis-
(diacetate) with either poly(4-vinylpyridinium) chlorate
in ethanol23 or poly(4-vinylpyridinium) hydrogen sulfate
in methanol under ultrasonic conditions;24 and by heating
bis(diacetate) with N-sulfonic acid poly(4-vinylpyridin-
ium) chloride in methanol.25 Phthalic acid and its de-
rivatives were reduced to give the corresponding aldehydes.
For instance, the reduction of phthalic acid was performed
with tert-hexyl-sec-butoxyborane in THF26 and LiAlH4,27
phthaloyl dichloride was reduced with pentacoordinated
silicon hydride;28 phthalic diamide with LiAlH4;29 dinitrile
with sodium hydridotris(dibutylamino)aluminate in THF.30
It should be underlined that hydrolysis of readily avail-
able 1,2-bis(dibromomethyl)benzene (2) is one of the
oldest1—6 but still widely used7—10 methods to synthesize
PA. However, this method suffers from numerous draw-
backs, in particular, a release of large amounts of hydrogen
bromide corroding the industry equipment, which limits
the production of PA.
In the present work, we describe a new method to
synthesize phthalaldehyde 1 from 1,2-bis(dibromomethyl)-
benzene 2 that avoids formation of HBr. The first step of
the synthesis is the reaction of tetrabromide 2 with
trimethyl orthoformate 3 to give acyclic diacetal 4.
The subsequent hydrolysis of compound 4 with diluted
HCl at elevated temperature results in phthalaldehyde 1
(Scheme 1). The 1H NMR monitoring of the reaction
course revealed that hydrolysis at room temperature ini-
tially gives cyclic phthalaldehyde diacetal, 1,3-dimethoxy-
1,3-dihydrobenzo[c]furan (5), which upon heating with
diluted hydrochloric acid provides aldehyde 1 (see Scheme 1).
nounced antibacterial activity and are high level disinfec-
tants.1 Different compositions based on PA and its de-
rivatives are used for disinfection and sterilization of
surgical instruments and devices, in particular, the complex
endoscopic surgical instruments. Therefore, the develop-
ment of new synthetic procedures to synthesize phthal-
aldehydes from available starting compounds is of great
importance. The known methods for synthesizing PA and
its analogs involve transformations of 1,2-disubstituted
benzenes via different reactions, e.g., hydrolysis, oxidation,
cleavage of bis(gem-diacetate) protective group, and reduc-
tion. Some of the first methods for the synthesis of phthal-
aldehydes were based on fuming or concentrated sulfuric
acid hydrolysis of bis(dihalomethyl)benzenes and differed
by the procedure used for neutralizing hydrogen halide
evolved.1—6 Hydrolysis of phthalaldehyde diacetals in
aqueous medium was carried out using different acids
(sulfuric,7 formic,8 phthalic,9 acetic,8 and hydrochloric10
)
and sodium hydroxide.7,10 The following compounds were
oxidized: o-xylene with either oxygen in water11 or chloro-
form in the presence of 10-methyl-9-phenyl-10-acridin-
ium perchlorate;12 naphthalene with metaperiodate in the
presence of potassium aquapentachlororuthenate(III) in
water, dichloromethane, and acetonitrile,13 with either
potassium bromate in the presence of Ru catalyst14 or
sodium periodate15 in CH2Cl2, H2O, and MeCN under
ultrasonic conditions, with ozone in methanol and butyl
acetate,16 sodium iodate in the presence of Ru3(CO)12 as
a catalyst in MeCN, H2O, and CH2Cl2;16 1,2-bis(hydr-
oxymethyl)benzene with manganese dioxide in CH2Cl2,17
with iron nitrate,18 with oxygen under catalysis with
Ru(PPh3)3Cl2 in different solvents,19 with bispyridinesilver
permanganate in benzene,20 with dimethyl sulfoxide and
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1878—1882, October, 2019.
1066-5285/19/6810-1878 © 2019 Springer Science+Business Media, Inc.

Phthalaldehyde diacetals
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 10, October, 2019
1879
Scheme 1
Transformation 5  1 was also performed as an individual
reaction to give phthalaldehyde 1 in 81% yield. Scheme 1
shows that conversion of tetrabromide 2 to phthalaldehyde 1
proceeds via intermediate phthalaldehyde diacetals 4
and 5; therefore, improvement of the methods to access
these compounds is of great importance.
One of the efficient methods towards acetals is still the
reaction of readily available organic gem-dihalides with
alkali metal alkoxides.31—37 The net result of the process
is the double dehaloalkoxylation. The similar processes
were accomplished by using mainly gem-dichlorides33—36
and, much seldom, gem-dibromides.37—39 The main dis-
advantages of this method are the necessity to prepare
alkali alkoxide and the possible transformation of the
substrate functional groups upon treatment with strong
base, i.e., alkoxide anion.
Earlier, we were the first to replace alkali metal alkox-
ides with trialkyl orthoformates to enable the double de-
haloalkoxylation of (dihalomethyl)arenes.40 Thus, we
pioneered in the synthesis of acetals of a series of function-
ally substituted benzaldehydes, for instance, by zinc
chloride-catalyzed (10 mol.%) reaction of 1,4-bis(di-
bromomethyl)benzene (4-Br2CHC6H4CHBr2) with or-
thoformates at 50 C for 4—5 h to give terephthalaldehyde
diacetals 4-(RO)2CHC6H4CH(OR)2.41—42
reacts with three-fold excess of ortho ester 3 (2 : 3 = 1 : 6)
to give the target acyclic diacetal of phthalaldehyde 4 in high
yield (see Scheme 1). Thus, we succeeded to develop the
first method to cleanly synthesize acyclic diacetal of phthal-
aldehyde 4 without admixture of its cyclic counterpart 5.
It is known that terephthalaldehyde diacetals are syn-
thesized by the reaction of the aldehyde with ortho esters
in the presence of acids.43 In the present work, we found
that the reaction of phthalaldehyde 1 with ortho ester 3
catalyzed by trifluoroacetic acid proceeds untypically to
give high yield of cyclic diacetal 5.
We also synthesized compound 5 from acyclic diacetal 4.
The reaction of compound 4 with PCl3 gives the corre-
sponding bis--chloro ether 6, and the subsequent hydro-
lysis of 6 provides cyclic product 5 (Scheme 2). The
1
structure of intermediate 6 was confirmed by H NMR
spectroscopy and its reaction with trimethyl phosphite to
give bisphosphonate 7 (see Scheme 2).
Scheme 2
Acyclic diacetals of phthalaldehyde of type 4 were not
obtained pure previously. However, several attempts have
been made to synthesize these compounds, for example,
by aluminum chloride-catalyzed reaction of PA 1 with
triethyl orthoformate (1 : 1) in EtOH,43 by acetalization
of aldehyde 1 with methanol using TiCl4 as a catalyst in
the presence of either NH3 or Et3N,38 and by the reaction
of aldehyde 1 with dimethyl sulfite in methanol.44 In all
the cases, mixtures of acyclic diacetal 4 and 1,3-dimeth-
oxy-1,3-dihydrobenzo[c]furan (5) were obtained.
We found that under the above conditions 1,2-bis(di-
bromomethyl)benzene (2), in contrast to 1,4-bis(dibromo-
methyl)benzene, is nearly completely unreactive towards
trialkyl orthoformate that decomposes to give alkyl formate.
However, at temperatures of 90 C and above tetrabromide 2
Diacetal 4 reacts with chlorophosphines 8a,b to give
bis(triorganylphosphine) oxides 9a,b. It is clear that this
reaction proceeds via intermediate bis--chloro ether 6
and O-methyl phosphinite 10, which react with each other
to afford compound 9 (Scheme 3).

1880
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 10, October, 2019
Gazizov et al.
Scheme 3
8—10: R = Ph (a), Et (b)
The residue was recrystallized from light petroleum to afford 1.08 g
In summary, we pioneered in the synthesis of acyclic
phthalaldehyde diacetal without admixture of cyclic one
by ZnCl2-catalyzed (10 mol.%) double didebromoalkoxyl-
ation of 1,2-bis(dibromomethyl)benzene with trimethyl
orthoformate. Hydrolysis of the synthesized acyclic di-
acetal produces phthalaldehyde. Unusual trifluoroacetic
acid-catalyzed reaction of phthalaldehyde with trimethyl
orthoformate affording cyclic acetal of PA was found.
Bisphosphorylation of acyclic diacetal of PA was per-
formed by two methods.
(81%) of phthalaldehyde (1). 1H NMR (CDCl3), : 7.60, 7.97
4
3
(both dd, 2 H each, C6H4, JH,H = 3.2 Hz, JH,H = 5.2 Hz);
10.52 (s, 2 H, CHO).
1,2-Bis(dimethoxymethyl)benzene (4). A mixture of 1,2-bis-
(dibromomethyl)benzene (2) (12.00 g, 28 mmol), trimethyl
orthoformate (3) (17.83 g, 168 mmol), and zinc chloride (0.57 g,
4.2 mmol) was heated at 90 C for 5 h. The reaction mixture was
cooled, diluted with isooctane (50 mL), and filtered. The filtrate
was concentrated in vacuo. Vacuum distillation of the residue
afforded 5.25 g (85%) of diacetal 4, colorless liquid, b.p.
65—66 C (0.3 Torr). 1H NMR (CDCl3), : 3.29 (s, 12 H, OMe);
5.67 (s, 2 H, OCHO); 7.30, 7.57 (both dd, 2 H each, C6H4,
Experimental
3
4JH,H = 3.4 Hz, JH,H = 6.4 Hz). 13C NMR (CDCl3), : 47.76
(OMe), 95.38 (CH), 121.55 (m-CHAr), 122.91 (o-CHAr),
130.49 (CAr).
Commercially available o-xylene, bromine, trimethyl orthofor-
mate, and phosphorus trichloride were used. 1,2-Bis(dibromo-
methyl)benzene (2)27 was synthesized and the solvents28 were
purified and dried as earlier described.
1,2-Bis[(chloro)(methoxy)methyl]benzene (6). To PCl3
(6.04 g, 44 mmol) cooled to 5 C, a solution of diacetal 4 (2.54 g,
11 mmol) in CCl4 (5 mL) was added. The mixture was stirred at
this temperature for 1 h. Thermally unstable compound 4 was
identified without purification after removal of the solvent and
the volatiles under deep vacuum (0.05 Torr) on cooling. Yield
of crude product 4 was 2.30 g (89%). 1H NMR (CDCl3),
: 3.86 (s, 6 H, OMe); 6.92 (s, 2 H, CHCl); 7.53, 7.76 (both m,
2 H each, C6H4).
1H and 13C NMR spectra were run on Tesla BS-567A (work-
ing frequency of 100 MHz (1H)) and Avance 400WB (working
frequencies of 400.13 (1H) and 100.61 MHz (13C)) instruments
in CDCl3. The 1H and 13C chemical shifts are given in the  scale
relative to the residual proton signal (13C) and the central signal
of the carbon atom (13C) of the solvent and recalculated to Me4Si.
31P NMR spectra were recorded with an Avance 400WB (work-
ing frequency of 161.98 MHz) spectrometer, the 31P NMR
chemical shifts are given relative to 85% H3PO4 (an internal
standard).
1,3-Dimethoxy-1,3-dihydrobenzo[c]furan (5). A. To a solution
of 1,2-bis[(chloro)(methoxy)methyl]benzene (6) (2.3 g, 9.8 mmol)
in CCl4 (5 mL), water (2 mL, 110 mmol) was added at room
temperature and the mixture was stirred at this temperature for
30 min. The aqueous layer was separated, the organic one was
dried with K2CO3, and the drying agent was filtered off. Removal
of the solvent in vacuo and vacuum distillation of the residue
afforded 1.27 g (72%) of a 65 : 35 mixture of cis and trans isomers
Phthalaldehyde (1). A. A mixture of 1,2-bis(dibromomethyl)-
benzene (2) (12.00 g, 28 mmol), trimethyl orthoformate (3)
(17.83 g, 168 mmol), and zinc chloride (0.57 g, 4.2 mmol) was
heated at 90 C for 5 h. The mixture was cooled down, diluted
with isooctane (50 mL), and filtered. The filtrate was treated with
water (5 mL, 278 mmol) containing 3 drops of concentrated HCl
and the resulting mixture was heated at 80 C for 2 h with simul-
taneous removal of methanol generated upon the reaction. The
organic layer was separated and dried with MgSO4. The solvent
was removed in vacuo, and the solid residue was crystallized from
light petroleum to afford 2.97 g (79%) of phthalaldehyde (1),
m.p. 58 C (cf. Ref. 45: m.p. 56.5—58.0 C). 1H NMR (acetone-d6),
1
of compound 5, b.p. 62—63 C (0.2 Torr). H NMR (CDCl3),
: 3.32 (s, 6 H, OMe, trans isomer); 3.35 (s, 6 H, OMe, cis iso-
mer); 5.99 (s, 2 H, CHOMe, cis isomer); 6.24 (s, 2 H, CHOMe,
trans isomer); 7.37, 7.43 (both m, 2 H each, CHAr, cis and
trans isomers). 13C NMR (CDCl3), : 53.28 (OMe, trans isomer);
55.45 (OMe, cis isomer); 105.25 (OCHO, cis isomer);
106.39 (OCHO, trans isomer); 122.92, 129.47, 138.85 (C6H4,
trans isomer); 122.97, 129.36, 138.68 (C6H4, cis isomer).
B. To a mixture of phthalaldehyde (1) (1.0 g, 7.5 mmol) and
trimethyl orthoformate (3) (3.18 g, 30 mmol), 2 drops of tri-
fluoroacetic acid were added, this caused warming up of the
reaction mixture to 42 C. After 24 h, the excess of ortho ester
and other volatiles were removed in vacuo. Vacuum distillation
of the residue afforded 1.17 g (85%) of compound 5.
4
: 7.85, 8.01 (both dd, 2 H each, C6H4, JH,H = 3.2 Hz,
3JH,H = 5.2 Hz); 10.51 (s, 2 H, CHO). 13C NMR (acetone-d6),
: 130.72 (o-CHAr), 133.68 (m-CHAr), 136.65 (CCHO),
192.00 (CHO).
B. To a solution of 1,3-dimethoxy-1,3-dihydrobenzo[c]furan
(5) (1.8 g, 10 mmol) in CCl4 (10 mL), water (3 mL) and
3—4 drops of HCl were added and the mixture was refluxed with
simultaneous removal of methanol formed upon the reaction.
1,2-Bis[(dimethoxyphosphoryl)(methoxy)methyl]benzene (7).
To a solution of compound 6 (3.7 g, 157 mmol) (was synthesized

Phthalaldehyde diacetals
Russ. Chem. Bull., Int. Ed., Vol. 68, No. 10, October, 2019
1881
from 3.87 g of 1,2-bis(dimethoxymethyl)benzene (4)) in an-
hydrous benzene (10 mL), a solution of trimethyl phosphite
(4.1 g, 34 mmol) in anhydrous benzene (5 mL) was added under
argon. The mixture was stirred at 20 C for 1 h and heated at
60 C for 2 h. Removal of the volatiles by evacuation (0.02 Torr)
of the reaction mixture at 60 C for 1 h afforded 5.2 g (82%) of
compound 7, heavy oil. 1H NMR (CDCl3), : 3.31 (s, 6 H, OMe);
6. S. Wawzonek, R. E. Karll, J. Am. Chem. Soc., 1948, 70, 1666;
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3
3.53, 3.71 (both d, 6 H each, POMe, JH,H = 10.4 Hz); 5.12
2
(d, 2 H, CHP, JP,H = 12.8 Hz); 7.28 (dd, 2 H, m-CHAr
,
=
3JH,H = 5.2 Hz, 4JH,H = 3.6 Hz), 7.50 (d, 2 H, o-CHAr, 3JH,H
= 3.6 Hz). 13C NMR (CDCl3), : 53.11, 53.93 (OMe), 58.38
2
1
(d, POCH3, JP,C = 6.3 Hz); 75.20 (d, CH, JP,C = 166.5 Hz);
127.13, 128.29, 133.57 (C6H4). Found (%): C, 44.21; H, 6.62;
P, 15.98. C14H24O8P2. Calculated (%): C, 43.99; H, 6.33;
P, 16.20.
1,2-Bis[(diphenylphosphoryl)(methoxy)methyl]benzene (9a).
To a stirred solution of chlorodiphenylphosphine (2.5 g, 11 mmol)
in isooctane (10 mL), compound 4 (1.28 g, 5.5 mmol) was
added dropwise. Warming up of the reaction mixture to 27 C
was observed. The mixture was heated at 45—50 C for 2.5 h and
kept at room temperature for 24 h. The precipitate formed was
collected by filtration and dried to afford 2.45 g (79%) of com-
pound 9a, m.p. 183—184 C. 1H NMR (acetone-d6), : 3.46
(s, 6 H, OCH3); 6.48 (d, 2 H, CHP, 2JP,H = 10.8 Hz); 6.82, 6.90
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3
4
(both dd, 2 H each, C6H4, JH,H = 5.6 Hz, JH,H = 3.6 Hz);
7.97, 7.66 (both dd, 4 H each, o-CHAr
,
,
3JP,H = 11.0 Hz,
3JH,H = 6.0 Hz);
3JH,H = 7.2 Hz); 7.37 (t, 4 H, p-CHAr
7.48—7.59 (m, 8 H, m-CHAr). 31P NMR (CDCl3), : 31.67.
Found (%): C, 72.27; H, 5.51; P, 10.81. C34H32O4P2. Calculat-
ed (%): C, 72.08; H, 5.69; P, 10.93.
1,2-Bis[(diethylphosphoryl)(methoxy)methyl]benzene (9b).
To chlorodiethylphosphine (2.48 g, 20 mmol) cooled to 10 C,
compound 4 (2.26 g, 10 mmol) was added dropwise under stir-
ring. The resulting solid was recrystallized from isooctane to
afford 2.77 g (74%) of compound 9b, m.p. 102—104 C. 1H NMR
(CDCl3), : 0.91, 0.96, 1.29 (all t, 4 H each, CH2CH3, 3JH,H
=
= 7.6 Hz, 3JP,H = 6.8 Hz); 1.47—1.62, 1.84—1.93 (both m, 4 H
2
each, PCH2); 5.86 (d, 2 H, CHP, JP,H = 12.0 Hz); 7.29 (dd,
3
4
2 H, m-CHAr, JH,H = 5.2 Hz, JH,H = 3.6 Hz); 7.42 (dd, 2 H,
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: 53.99. Found (%): C, 57.63; H, 8.52; P, 16.48. C18H32O4P2.
Calculated (%): C, 57.75; H, 8.62; P, 16.55.
3
4
This work was financially supported by the Ministry of
Science and Higher Education of the Russian Federation
in the framework of the basic part of the state task in the
field of scientific activity (Project No. 4.5348.2017/8.9).
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Received May 13, 2019;
in revised form June 10, 2019;
accepted June 26, 2019