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Disubstitution in the Vilsmeyer-Haack Aldehyde Synthesis.

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pound in benzonitrile containing a trace of hydroquinone.
Heating is continued until the blue colour of (Ic) disappears.
The products are precipitated with methanol and recrystallized from butanol or tetrahydronaphthalene [preparation
of f4)I.
R'C-CH=CH-C
I
I35C6
I
8
-
H5C6
(3)
R = C~HSCH,m.p. 187 " c
R = C~HSCH=CH-CH, m.p. 106 " c
R = 2-Furylmethylene, m.p. 159 "C
R = Fluorenyliden, m.p. 170 "C
R = o-HO-C~HS-CH, m.p. 194 "C
320°C
Received: September loth, 1965 [Z 65/891 1El
German version: Angew. Chem. 77, 1011 (1965)
Synthesis and Reactions of N,N,N',N'-Tetramethyl-3-methoxy-l-propene-l,3-diamineand
N,N,N',N',N",N"-Hexamethyl-2-propene1,1,3-triamine
By Prof. Dr. H. Bredereck, Dr. F. Effenberger,
Dr. R. Gleiter, and cand. chem. K. A. Hirsch
Institut fur Organische Chemie
der Technischen Hochschule Stuttgart (Germany)
N, N- Dimethyl-3-dimethylaminoprop - 1-enylideneammonium
perchlorate or methyl sulfate (1) [ l , 21 react with potassium
methoxide, giving the vinylogous aminal ester 3-methoxyN, N,N',N'-tetramethyl-l-propene-l,3-diamine (2), and with
sodium dimethylamide, giving the vinylogous trisdimethylamino compound, N,N,N',N',N",N"-hexamethyl-3-propene1,1,3-triamine (3). Both products are even more reactive than
the vinylogous amidacetal, N,N-dimethyl-3,3-dimethoxypropenylamine described recently [l] and with CH-acidic
compounds gives derivatives ( 4 ) of butadiene.
(4)
Ix
(C)
P-NO2C6H4
(di
P-NOZGH~
N,N,N,N'-Tetramethyl-3-methoxy1- propene- 1,3 - diamine
(2) : 19.55 g (0.5 g-atom) of potassium is heated in 200 ml of
anhydrous benzene at 75OC and finely divided with a vibrator. When the suspension has cooled, a solution of 16.01 g
(0.5 mole) of anhydrous methanol in 400 ml of anhydrous
benzene is added with stirring during 2 h, with heating under
reflux for I/? h near the end of the reaction. 1 13.32 g (0.5 mole)
of N,N-dimethyl-3-dimethylaminopropenylideneammonium
perchlorate is added, and the whole heated for a further 2 h
under reflux, allowed to cool, and filtered from the potassium
perchlorate that separates. The benzene is distilled off in
vacuum and the residue fractionated through a short column.
of colorless liquid, b. p. 75-76 "CjlO mm.
Yield 47.5 g (60
x)
R = C~HS-C-CH~,m.p. 146 " c
(4). IL1.p.
Exarnp fes:
N,N,N',N',N",N"-Hexamethyl-3-propene-11 1,3-triamine (3) :
To a suspension of 33.5 g (0.5 mole) of sodium dimethylamide in 500 ml of anhydrous benzene is added 113.32 g
(0.5 mole) of the perchlorate ( I ) , and the mixture is heated
for 2 h under reflux and processed as described above. Yield
52.5 g (62 %) of colorless liquid, b.p. 75-76 "CjlO mm.
4-Dimethylamino-l-phenyl-l,3-butadienenitrile
(46) : 2.34 g
(0.02 mole) of benzyl cyanide, 50 ml of anhydrous petroleum
ether (b.p. 1O0-13O0C), and 31.6 g (0.02 mole) of compound
12) are heated together at 1 f0 "C for 4 h. The precipitated
oil solidifies when kept for a day in a refrigerator. Thecrystal
cake is powdered, filtered off, washed with petroleum ether
(b.p. 50-70°C) (twice with 50 ml), and dried for 24 h in
vacuum. The crude product (3.45 g) is recrystallised from ca.
300 ml of anhydrous petroleum ether (b.p. 100-130°C) in
presence of basic aluminum oxide and dried for 48 h in
vacuum. Yield 2.94 g (74 %) of yellow needles, m.p. 102OC.
Received: September loth, 1965 [Z 63/889 IEI
German version: Angew. Chem. 77, 1010 (1965)
[ I ] H . Bredereck, F. Effenberger, and D . Zeyfang, Angew. Chem.
77, 219 (1965).
[2] Z . Arnold and J. Zemlicka, Coll. czechoslov. chem. Commun.
25, 1318-(1960).
Disubstitution in the Vilsmeyer-Haack
Aldehyde Synthesis [*I
By Prof. Dr. Ch. Grundmann and Judith M. Dean
Mellon Institute, Pittsburgh, Pa. (U.S.A.)
The reaction of a n aromatic system with the complex from
phosphorus oxychloride and an N-formylated secondary
amine is known as the Vilsmeyer-Haack aldehyde synthesis.
Although it belongs to the most frequently used methods for
the preparation of aromatic aldehydes, the introduction of
more than one formyl group per aromatic ring has never
been achieved [l].
32
[a1 From (2) or ( 3 ) ; [bl from (2); Icl from ( 3 ) .
Angew. Chem. internat. Edit. I Vof. 4 (1965) / No. I 1
We have, however, found it surprisingly easy to convert
N,N-dialkylanilines into dialdehydes. Thus from N,N-dimethylaniline ( I ) and 2-3 moles of the POCI3-dimethyl-
955
formamide complex [2], a mixture of 4-dimethylaminobenzaldehyde (2) and 4-dimethyIaminoisophthaldialdehyde
(3) is formed from which (3) may be isolated with 15-20 %
yield. 3,5-Dimethyl-N,N-dimethylaniline(4) is even more
easily diformylated. Under conditions which convert ( I )
exclusively to (2) [3] a mixture of about equal parts of
unchanged (4), 4-dimethylamino-2,6-dimethylbenzaldehyde
(S), and 4-dimethylamino-2,6-dimethylisophthaldialdehyde
(6) is formed. The application of more than two moles of
formylating agent results in the exclusive formation of the
dialdehyde (6) in 60-80% yield. Monoformylation of (4)
can only be achieved by adding one mole of the POC13-DMF
complex at 5 "C very slowly to a large excess (5- 10 moles)
of the amine.
[ I ] The only exception - although with a pseudp-aromatic
system - seems to be the preparation of azulene-l,3-dialdehyde
from azulene; K . Hafner and C. Bernhard, Angew. Chem. 69,
533 (1957); Liebigs Ann. Chem. 625, 108 (1959).
[21 In principle, these syntheses can be carried out as well with
N-formyl-N-methylaniline;however, the separation of the basic
aldehydes from the N-methylaniline is more difficult.
[3] Org. Syntheses, COIL Vol. IV, 331 (1963).
[4]Analogously (6), m.p. 79 "C, is obtained in 81 :/o yield.
Steam distillation of the crude product is unnecessary in this case.
Synthesis of Carboxylic Acids with
1,l-Dichloroethylene
By Dr. K. Bott
Forschungslaboratorien der Chemische Werke Huls AG.,
Marl (Germany)
The constitution of the aldehydes (3), (5), and (6) was
ascertained by NMR-spectroscopy : (5) displays, beside
signals for the C-methyl (T = 7.45) and N-methyl (T = 7.00)
groups, only one signal for the two aromatic protons (T =
3.70) and one signal (unsplit) for the aldehydic proton (T =
-0.08). The dialdehydes (3) and (6) each give two signals
for aldehydic protons (T = 0.03 and -0.20, resp. 7 = 0.10 and
-0.28); (6) gives furthermore a split signal for the C-methyl
groups (T = 7.40 and 7.20). N o indication was obtained for
the presence of the 2-dimethylaminoisophthaldialdehydesisomeric with (3) and (6). The introduction of a third formyl
group was not possible even under more rigid conditions.
4-DimethylaminoisopAthaldialdehyde(3) [4]:
N-Dimethylaniline (12.1 g) is added to phosphorus oxychloride (50.0 g) and D M F (81.2 g). The reaction mixture
is heated with stirring and exclusion of moisture for 16 hours
to 60-65 "C, then poured o n ice (600 g), and 33 % NaOH
(150 ml) is added at no more than 15 '. After several hours'
cooling to 0 "C, the crystalline precipitate, consisting of (2)
and (3), is filtered off, washed with water and dried in
vacuum (11.3 g). Exhaustive ether extraction of the alkaline
mother liquor followed by evaporation of the ether yields
further 3.5 g. To separate (3) from (2) the product is distilled
with steam until the distillate does not deposit any more
crystals of (2) on cooling to 0 "C. The crude dialdehyde (3)
(3.4 g) separates in crystalline form from the aqueous solution
(100 ml) remaining in the distillation flask o n cooling to
0 OC. After two recrystallizations from ligroine yellowish
felted needles of pure (3), m. p. 72 'C, are obtained. Yield:
2.4 g (14%).
Treatment of carbinols, carbinol esters, or olefins obtainable from carbinois by loss of water with I,l-dichloroethylene in 80 to 100% sulfuric acid leads to substituted
propionic acids (3) (cf. Table). The reaction, which takes
place at 0 to 15 "C, is greatly accelerated by boron trifluoride
and gives particularly good yields when carbonium ions can
easily be formed from the carbinols or olefins used.
I
Carbinol, ester, or olefin
Product ( 3 )
Norbornene
I-Adamantanol
1 -8romoadamantane
a-Methyl benzyl alcohol
exo-Norbornylacetic acid
I-Adamantanylacetic acid [ I ]
1-Adamantanylacetic acid
3-Phenylbutyric acid;
carboxylic acids of higher
molecular weight [a]
3,3-Diphenylpropionic acid
3,3-Dimethylbutyric acid [bl
3,3-Dimethylbutyric acid
3,3-Dimethylbutyric acid
Benzhydrol
t-Butyl chloride
t-Butyl alcohol
Isobutene
Yield
[%I
of 13)
72
93
86
50
20-25
71
78
79
75
[a] These acids (structure not yet clarified) are probably formed by
oligomerization of styrene.
[b] Diisobutene (dimerisation product of isobutene, principally 2,4,4trimethyl-I- and -2-pentene) and isobutyl alcohol yield only 3,3-dimethylbutyric acid.
The principle of this carboxylic acid synthesis consists in
addition of a carbonium ion ( I ) to 1,l-dichloroethylene,
giving (2), followcd by hydrolysis to the acid (3).
Bz
4-DirnethyIamino-2,6-dimethylbenzaldehyde (5) :
(31
A formylating mixture prepared from phosphorus oxychloride (15.6 g) and dimethylformamide (30.0 g) is added
dropwise, with stirring and exclusion of moisture, within
4 hours at 5-10 "C to 3,5-dimethyl-N,N-dimethylaniline
(75.5 g). After keeping the reaction mixture for 16 hours at
25-3OoC, it is decomposed with ice (300 g), made alkaline
with 33 % NaOH (75 ml) and extracted with ether. After
evaporation of the ether, excess amine (4) is distilled off
(56.6 g; b.p. 61-62'C/0.2 mm), and (5) is obtained in thick,
almost colorless plates (12.5 g, 69 %) from the residue after
one recrystallization from ligroine, m.p. 83 "C.
Received: September 15th. 1965 [Z 60/885 IE]
German version: Angew. Chem. 77, 967 (1965)
[*I This work was supported by Public Health Service Research
Grant CA 07272-02 of the National Cancer Institute, Bethesda,
Md. (U.S.A.).
956
Received: September 15th, 1965 [Z 61/887 IE]
German version: Angew. Chem. 77, 967 (1965)
[ I ] H . Stetter, M . Schwarz, and A. Hirschhorn, Chem. Ber. 92,
1630 (1959).
Formation of Carbonyl Compounds from Azines or
Hydrazones with Active Manganese Dioxide
By Priv.-Doz. Dr. G . Maier and cand. chem. U. Heep
Institut fur Organische Chemie
der Technischen Hochschule Karlsruhe (Germany)
Treatment of 2,5-diphenyl-3,4-diazanorcaradienewith active
precipitated manganese dioxide (E. Merck, Darmstadt) gives
cis-1,2-dibenzoylcycIopropane and nitrogen [I]. We have
Angew. Cheni. internat. Edit. Vol. 4 (1965) No. 11
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