Phthalylbenzoylacetic ester and its nitro and halogen derivatives were prepared through condensation of phthalic anhydride, nitrophthalic anhydride, and phthalic halide anhydride with benzoylacetic ester in a solution of acetic anhydride and triethylamine. The condensation of hemipinic acid anhydride proceeds similarly, but under more drastic conditions. Derivatives of indan-1,3-dione are also formed, with a small yield, in the reaction of nitrophthalic anhydrides with benzoylacetic ester in the presence of increased quantities of triethylamine

Oshkaya, V. P.

Rotberg, Y. T.

English

NASA Technical Reports Server

NASA TECHNICAL MEMORANDUM NASA-TM-7788519850021697 NASA TM-77885
CONDENSATION OF ANHYDRIDES OF DICARBOXYLIC ACIDS
WITH COMPOUNDS CONTAINING ACTIVE METHYLENE GROUPS.
XIX. CONDENSATION OF PHTHALIC AND SUBSTITUTED
PHTHALIC ANHYDRIDES WITH BENZOYLACETIC ESTER
YU. T. Rotberg and V. P. Oshkaya
Translation of "Kondensatsiya angidridov dikarbonovykh kislot s soyed-
ineniyami, soderzhashchimi aktivnyye metilenovyye gruppy. XIX. Konden-
satsiya ftalevogo i zameshchennykh ftalevykh angidridov s benzoiluksus-
nym efirom," Izvestiya Akademii nauk Latviyskoy SSR, No. 4, 1971,
pp. 420-4_24.
;ill i _-;Loo t
ILANGLEYRESEARCHCENTER
L.IBRARY,NASA
HAMPTON, VIRGINI#_
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
WASHINGTON, D.C. 20546 JUNE 1985
https://ntrs.nasa.gov/search.jsp?R=19850021697 2020-03-20T17:50:42+00:00Z
\STANDARO TITLE PAGE
'
]_ R.po,I No. 2. Gov.reL,m.ne A,:€.,,icn Ho. _.(Ipl,.nl's'C_lalog He.
ASA TM-77885 z
Ta,to_a _,_,a°CONDENSATION OF ANHYDRIDES O_ 5.n.po,oo,.
DICARBOXYLIC ACIDS WITH COMPOUNDS CON- June ,.1985
TAINING ACTIVE METHYLENE GROUPS. XIX. _.P_ro_a.q0,ao._,.,;,.C°_°"_
CONDENSATION OF PHTHALIC AND SUBSTITUTED _ I
7. A-_'o'(') 8. Poat'_ln e O,g_laollon Repoq! He.
Yu. T. Rotberg and
V. P. Oshkaya I0.w._u.ttN..
r 9 P.,fa,_-.QO'_o-iJ_',o-Homoo_4Ad4,gsl |1. Co..°ceoqGtlntNe.
o Kanner Asso iates NASW-4005
Redwood City, California 20546 la rr,.-_a.,o,,_a_.,;°aCo..,.,
Translation
|_. _|o,,._ Ag*.Cy No_° a,r_dA441.**
National Aeronautics and Space Adminis- I_._0,,.,,,=,:.,€,¢o_.
tration, Washington, D.C. 20546
ans±a:ion o_ Kondensatsiya angidridov dikarbonovykh kislot I
s soyedineniyami, soderzhashchimi aktivnyye metilenovyye |
gruppy. XIX. Kondensatsiya ftalevogo i zameshchennykh ftalevy_ :
angidridov s benzoiluksusnym efirom," Izvestiya Akademii nauk
Latviyskoy SSR, No. 4, 1971, pp. 420-424.
P_thalylbenzoylacetic ester and its nitro and halogen deriva-
tives were prepared through condensation of phthalic anhydride
nitrophthalic anhydride, and phthalic halide anhydride with
benzoylacetic ester in a solution of acetic anhydride and
triethylamine. The condensation of hemipinic acid'anhydride
proceeds simila£1y, but under more drastic conditions. Deri-
vatives of indan-l,3-d_one are also formed, with a small yield
in the reaction of nitrophthalic anhydrides with benzoylacetic
ester in the presence of increased quantities of triethylamine
*PHTHALIC ANHYDRIDES WITH BENZOYLACETIC ESTER
17. [°r W_,de {Sclcctca _¥ Aumor(_|) 18. Olafrlbullo. _)fot.€_o_t
Unclassified -Unlimited
"] 1 1|_. _4lCUrigy _|°eell. (of thto ,;IPo_t) 20. _°_lfll' _|°°_li0. (O_ fhl° pOg,) 21, N°_ Q_ Pewee _P.Unclassified Unclassified 9
CONDENSATION OF ANHYDRIDES OF DICARBOXYLIC ACIDS
WITH COMPOUNDS CONTAINING ACTIVE METHYLENE GROUPS.
XIX. CONDENSATION OF PHTHALIC AND SUBSTITUTED
PHTHALIC ANHYDRIDES WITH BENZOYLACETIC ESTER
Yu. T. Rotberg and V. P. Oshkaya
Latvian Order of the Red Banner of Labor
Stuchka State University
Phthalylbenzoylacetic ester and its nitro and halogen derivatives/420*
were produced through condensation of phthalic anhydride, nitrophthalic
anhydride, and phthalic halide anhydride with benzoylacetic ester in a
solution of acetic anhydride and triethylamine. The condensation of
hemipinic acid anhydride proceeds similarly, but under more drastic
conditions. Derivatives of indan-l,3-dione are also formed, with a
small yield, in the reaction of nitrophthalic anhydrides with benzoyl-
acetic ester in the presence of increased quantities of triethylamine.
Phthalic anhydride, in a solution of acetic anhydride in the pre-
sence of triethylamine, at room temperature easily condenses with
esters containing active methylene groups [i]. Interaction with malon-
ic ester forms a product of crotonic condensation of the carbonyl group
of the cyclic anhydride -- phthalylmalonic ester (I; R = H).
t
/€o0c2", /coo.H
o
I II
R----H;--NO2;--Br. R=--H; --NO:.
Also described are reactions of 3-nitro- [2], 4-nitro- [3], and
3-bromophthalic [4] anhydrides with malonic ester, leading to the
substitution in the benzene ring of a phthalylmalonic ester derivative
(I; R = -NO2, -Br). Acetoacetic ester, on the other hand, in a reaction
with phthalic anhydride yields both a product of the icondensation of
the active methylene group with the anhydride's carbonyl oxygen (II;
*Numbers _n the margin indicate pagination in the foreign text.
1
R = H) and a product in which the anhydride oxygen is replaced by a
carbon of the methylene component (III). The direction of the reaction
depends on the amount of triethylamine used in the reaction [i].
i /421
\
11I IV "'
i
R_--CI_ --Br;J.
I
While the behavior of nitrophthalic anhydrides is analogous to the
above [2, 3], with condensation of halogen-substituted phthalic anhy-
drides with acetoacetic ester it has so far proven possible to produce
only products with an indan dione structure (IV) [5], from which it is
easy to obtain the corresponding indan-l,3-dione halides with a free
methylene group.
By structure, benzoylacetic ester is close to acetoacetic ester,
so it was of interest to study its behavior in reactions with cyclic
anhydrides of dicarboxylic acids. It turned out that benzoylacetic
ester easily condenses with phthalic anhydride at room temperature,
and also with nitrophthalic anhydride and phthalic halide anhydrides,
in a solution of acetic°anhydride and triethylamine. The obtained
compounds represent white crystalline substances whose elemental
composition and IR spectroscopy data (Table i) demonstrate their
belonging to the 3-methylene phthalide series (V).
t
/COC_Hs o
V
R----H;--NO2;--CI; Br; --J.
When the concentration of triethylamine in the reaction solution
is increased, phthalylbenzoylacetic ester (V; R = H) remains virtually
the sole product of the condensation of unsubstituted phthalic anhydride
with benzoylacetic ester. Condensation of nitrophthalic anhydrides
with benzoylacetic ester in the presence of increased quantities of
triethylamine produces products of phthalide structure (V; R = -NO2)
that crystallize out of the reaction solution, but it also produces
compounds having the structure of derivatives of indan-i_3_d_One (III)
that remain in solution, i ,Theycould not be isolated in pure form, but
2
when boiled with dilute hydrochloric acid they, like the products of
the condensation of 3- and 4-nitrophthalic anhydrides with acetoacetic
ester [2, 3], produce 4-nitro- or 5-nitroindan-l,3-d±one, respectively.
T_e yields of the latter are rather small, and _his method of pro-
ducing them cannot be of preparative significance. The anhydride of
hemipinic (3,4-dimethoxyphthalic) acid, which contains an electron-donor
group in the benzene ring, reacts with benzoylacetic ester only at
high temperature in the presence of increased amounts of catalyst --
triethylamine. The product of the reaction in this case is dimethoxy-
phthalylbenzoylacetic ester (Via or VIb).
OCH3
OCH_ /coC6"s .3CO,.._co
_C /0 .M3co _coo qUs _],_c/coc_. 5
2t
CO _COOC2Hs •
Via VI6
The obtained results allow the conclusion that, despite the struc-/422
tural closeness of acetoacetic and benzoylacetic esters, the latter
have a much lesser tendency to form derivatives of indan-l:_3-dione in
reactions of condensation with phthalic anhydride and its derivatives
that occur in a solution of phthalic anhydride and triethylamine.
Experimental Part
f
Condensation of phthalic anhydride with benzoylacetic ester.
1.48 g (0.01 mole) of phthalic anhydride and 1.92 g (0.01 mole) of ben-
zoylacetic ester, under moderate heating, are dissolved in 5 g (0.05
mole) of acetic anhydride and 1 g _(0.01 mole) of triethylamine is
added at room temperature. The reaction mixture is left in a covered
flask for 24 hours, after which 20 g of ice and 5 ml of concentrated
hydrochloric acid are poured into the mixture. The precipitate forming
after a period of time is filtered out and dried. The weight is 2.8 g
(86.9%), the melting point 85-90 °. After triple crystallization from
ethanol the melting point is ii0-Ii! 0. For elemental analysis data,
see the table.
3
d
PRODUCTS OF THE CONDENSATION OF PHTHALIC AND SUBSTITUTED
PHTHALIC ANHYDRIDES WITH BENZOYLACETIC ESTER
Melt- i Element analysis
ing "_eneralI'_ve---_ed,--%-o
No. Obtained product ?°oi.nt']f°rmulal-- i....i -- "h_alo-C | [ C I H IN:| ] I ....] gen
ll0-;il1 Phthalylbenzoylacetic Jester C_H,40570.52%26 -- _
2 4-:ester(°r7-)Nitrophthalylbenzoylacetic 229--230C,0H,30,N62.523.503,98 ,/
3 5- (or 6-)Nitrophthalylbenzoylacetic 1200_20iC,0H,aO,N62.223.553.67 --:
eslter :
4- (or4 7-)Chlorophthalylbenzoyl- t79--180CI_H,_O6CI64,093.74 -- 9,62!
acetic ester
5 5- (or 6-)Chlorophthalylbenzoyl- 166--167C,gH,a05CI64.323.74 -- 9.91_
acetic ester
6 4- (or 7-)Bromophthalylbenzoylacetic 185-i87C,gH,3OsBr56_53.5i -- 19.571
ester i
• I
7 5- (or 6-)Bromophthalylbenzoylacetic 153-155C,gH,aO_Br57.003.55 --20.161
ester _
8 5- (or 6-)Iodophthalylbenzoylacetic 172--173C,gH,_OsJ51.182.70 -- 28.06
ester
9 4,5- (or 6,7-)DimethoXyphthalyl- 174--175C4,H,,O7 66,164.95 -- --
benzoylacetic ester
Element analYsis' IR spectroscopy*
calculated, %' stretch vibration frequencies, cm-_
No. C H N _al- _C=O _C=O _C=C _
o- phthal- ketone or or NO2
gen ida rin< ester arom_ttic
1 70.804,38 -- -- 1797(78) 1717(66); 1638(76); --
1679(72) 1599(46)
2 62.!3 .3.57 3.8t -- t8t2(83) t724(85); t623(68); i540(78)
• 1668(82) t599(47);
1582(45)
3 62.13 3,57 i3,81 -- 1816(84) 1712(77); 1644(79); 1537(80)
1673(81) 1599(64);
1583(48)
4 63,97 3.67 -- 9.94 1792(62) |718(57); 1629(64); --
1670(61) 1594(57);
1583(58)
5 63.97 3.67I --- 9.94 1803(72) 1711(61); 1633(67); --
1677(65) 1597(56);
1579(52)
6 56.88 3,27 -- 19.92 t788(75) t7t9(72); t635(76); --
i 673(72) 1592(66);
1576(63)
7 56.88 3.27 -- 19.92 180i(83) 1710(72); 1632(79); --
i677(76) 1600(64);
• t578(55)
8 50.92 2.92 -- 28.31 18t2(79) t704(62); t629(76); --
• 1677(81) i596(53);
1574(37)
9 65,97 4.74 -- _ 1789(88) t722(89); t632(84); --
t665(82) t598(76)
*For solids in paraffin oil, taken in IKS-14 instrument.
Condensation of substituted phthalic anhydrides with benzoylacetic
ester. 0..01 mole of 3- or 4-nitro-, 3-or 4-chloro-, 3- or 4-bromo-,
or 4-iodophthalic anhydride is_ condensed with 1.92 g (0.01 mole) of
benzoylacetic ester in a solution of 5 g (0.05 mole) of acetic anhydride
and 1 g (0.01 mole) of triethylamine, as described above. Falling out
of the reaction solution is a white precipitate that is filtered out,
washed with a small amount of acetic acid, and dried. The yield is
40-75%. It is crystallized from glacial acetic acid for purification.
The melting point and analysis data are citedlin the table.
Condensation of nitrophthalic anhydrides with benzoylacetic ester
in the presence of increased quantities of triethylamine. 3- or 4-
nitrophthalic anhydride is condensed with benzoylacetic ester using the
procedure presented above, the only difference being that 3 g (0.03 /423
mole) Of triethylamine is used. The precipitate is filtered out, and
after crystalliza%ion it turns out to be identical to that obtained
above. The filtrate is poured into a mixture of 20 g ice and 5 ml
concentrated hydrochloric acid. The precipitate thus formed is
isolated and dried.
Obtained from the product of 3-nitrophthalic anhydride is 1.05 g
of a substance that after boiling with i00 ml of water and 5 ml of
concentrated hydrochloric acid, using the procedure in [2], yields
0.32 g 4-nitroindan-l,3-dione with a melting point oF 132 ° (in [2]
the melting point is 133-135°).
Discovered %: N 7.40. C9H504N. Calculated %: N 7.33.
The condensation product of 4-nitrophthalic anhydride produces
1.9 g of a substance that after similar treatment yields a small amount
of 5-nitroindan-l,3-dione.
Discovered %: N 7.49. C9H504N. Calculated %: N 7.33.
Condensation of hemipinic acid anhydride with benzoylacetic ester.
2.08 g (0.01 mole) of hemipinic acid anhydride and 1.92 g (0.01 mole)
of benzoylacetic ester are dissolved in a heated water bath in 51 g
5
q
(0.5 mole) of acetic anhydride and 6.1 g (0.06 mole) of triethylamine
is added. Heating ±n a water bath is conducted for 30 min, after which
the solution is poured into 200 g of ice and 50 ml of concentrated
hydrochloric acid. After filtration and drying, 1.8 g (47.1%) of
material is obtained whichilafterdouble crystallization from acetic
anhydride melts at 174-175° (table).
6
d
/REFERENCES
i. Oshkaya, V. P., and G. Ya. Vanag, IzV. AN LatV. SSR, ser. khim.,
271 (1964).
2. Oshkaya, V. P., and G. Ya. Vanag, Uch. zap. LGU, Khimiya, 57, 67
(1964).
3. Oshkaya, V. P., and Yu. T. Rotberg, Izv. AN Latv. SSR, ser. khim.,
63 (1967).
4. Rotberg, Yu. T., G. Ya. Chema, V. P. Oshkaya, Izv. AN Latv. SSR,
ser. khim., 70 (1967).
5. Rotberg, Yu. T., I. D. Dervanika, V. P. Oshkaya, Izv. AN Latv. SSR,
ser. khim., 699 (1970).
7
IIliiiiiiiiiiiiiiiiiiiII
3 1176 00184 8358
Q


Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups.  Part 19:  Condensation of phthalic and substituted phthalic anhydrides with benzoylacetic ester

Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups. Part 19: Condensation of phthalic and substituted phthalic anhydrides with benzoylacetic ester

Abstract

Similar works

Full text

Available Versions

NASA Technical Reports Server