Method for synthesizing 1,3-diiminoisoindole

Abstract

The invention discloses a synthetic method of 1, 3-di-iminoisoindoline, which comprises the

steps that: 1) raw materials, o-phthalonitrile and a catalyst are mixed, added into an alcohols
solvent in a reactor and stirred, ammonia gas is introduced, the temperature is raised to 50 to 60
DEG C, then the reaction is carried out for 4 to 6 hours at the temperature to obtain the reaction
fluid; wherein, the dosage of the catalyst is 0.01 to 10 percent of the mass of the o-phthalonitrile,
the mol ratio between the o-phthalonitrile and the solvent is 1:1 to 15, while the mol ratio
between the o-phthalonitrile and the ammonia gas is 1:0.3 to 13, the catalyst is one or the
combination of two or more than two of alkali metals and alkali metal compounds, and the alkali
metal compounds are inorganic alkali metal salt or alkali metal alkali or organic alkali metal salt;
and 2) the reaction fluid is treated with temperature reduction and filtering to obtain 1, 3-
diiminoisoindoline products. The method has the advantages of high product yield, simple
process, low cost, easy operation and less three wastes.

CN101391977A
CN Application

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Chinese
Inventor
于权
磊王
Original Assignee
河北铢峰凯美考科技有限公司
Priority date
2008-11-17

Family: CN (1)
Date App/Pub Number Status
2008-11-17 CN 200810079776
2009-03-25 CN101391977A Application

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Description

translated from Chinese

1, 3-imino-isoindoline BACKGROUND synthesis of indoline

The present invention relates to a l, 3- iso diimino isoindoline synthesis of indole.

Background technique

1, 3-imino-isoindoline (or 1,3-bis-amino-isoindoline) is an important intermediate in organic

synthesis, mainly for the synthesis of iso B and phthalocyanine-based pigments, isoindoline
primer , phthalocyanine pigment dye (brilliant blue o-carboxamide sodium benzoate), can be used
for synthesis of a porphyrazine, and l, 3, 4- thiadiazole, and a heterocyclic ring system to form a
metal complex with its ligand synthesized . L has been prepared, the method 3-imino-isoindoline
mainly of oleic acid and stearic acid as emulsifier, ammonium molybdate catalyst, phthalic
anhydride and urea was imidized, and then ammonium nitrate in the presence of a condensation
reaction to give 1,3-bis-amino-isoindoline nitrate, and finally neutralized with sodium hydroxide
to give the desired product. The above methods have low yield, complicated operation and a
large amount of wastewater, harsh conditions, waste treatment difficult issues. CN1884285A
discloses a copper phthalocyanine-type liquid-solid mixed phase reactor and a continuous
process, the reactor is by automatic feeding machine according to the set parameters input
phthalic anhydride, urea, cuprous chloride and small amount of catalyst through the liquid-solid
copper phthalocyanine mixed continuous reactor, a continuous, uninterrupted production of
copper phthalocyanine, characterized in that: liquid-solid phase segment of the reaction, the
liquid phase section using urea as a solvent, the main product is 1-imino-isoindoline and 1 , 3-
imino-isoindoline. This technique is how to improve yield, and simplify the synthesis process is
not given aspect instructive.

SUMMARY

The present invention solves the technical problem is to provide a l, 3- iso diimino isoindoline of
indole synthesis, the synthesis yield, simple process, low cost, and less waste. To solve the above
problems, the present invention adopts the technical solution as follows: A L, synthesis of 3-
imino-isoindoline, which is the aspect of synthesizing

Method comprising the following: ① From the phthalonitrile feed and catalyst mixture, adding
an alcohol in the reactor

Solvent, stirred, ammonia gas, warmed to 5 (TC~6 (TC, reacted at this temperature for 4 ~ 6
hours to obtain a reaction solution; wherein the catalyst is used in an amount phthalonitrile mass
(weight) 0.01% to 10%, molar ratio of phthalonitrile and the solvent is l: 1 ~ 15, the molar ratio
of ammonia and phthalonitrile is l: 0.3 ~ 13, the catalyst is an alkali metal and an alkali metal the
combination of compounds wherein two substances or a substance or two or more species, the
alkali metal compound is an alkali metal salt of an inorganic base or an alkali metal or organic
alkali metal salt; ② the reaction was cooled filtered to give L, 3-imino-isoindoline product.

The above-described prior art embodiment, the step ②, the reaction solution is preferably first
distilling off the solvent, and then cooling was filtered, the solvent was distilled off can be
recycled. The catalyst may be an inorganic alkali metal salt, an alkali metal carbonate catalyst
may be selected and an alkali metal bicarbonate, or a substance wherein the two substances or a
combination of two or more thereof. The catalyst may be an alkali metal, sodium metal or the
like can be selected. The catalyst may be alkali metal base, catalyst composition can select one or
both of potassium hydroxide and sodium hydroxide. Inorganic alkali metal salts of the above
may be used as a catalyst as potassium carbonate, sodium hydrogen carbonate, the catalyst
composition can select one or both of potassium carbonate and sodium bicarbonate. The organic
alkali metal salt may be used as a catalyst an alkali metal formates, alkali metal acetates, alkali
metal oxalates, alkali metal salts of alcohols, a catalyst can choose one of them or two substances
or substance a combination of two or more thereof. The above-mentioned organic alkali metal
salt used as a catalyst may be sodium formate, sodium acetate, sodium methoxide, sodium
oxalate, sodium ethoxide, potassium oxalate, the catalyst may choose a combination thereof
wherein the two substances or a substance or two or more substances. These solvents can be less
than an alcohol or an alcohol aqueous solution 10 carbon atoms, the solvent may be selected as
methanol, ethanol, ethylene glycol. The amount of the catalyst may range from 0.1% to 5% by
mass of phthalonitrile, the molar ratio of the above-described phthalonitrile and the solvent is 1:
9~15, the above-described molar ratio of ammonia and phthalonitrile is 1: 1 ~ 3.

The method of the present invention allows the synthesis of 1, 3-imino-isoindoline yield 107%,
purity (content) of 97.5% (HPLC). It yield, simple process, low cost, operation will be easy, and
less waste.

detailed description

Embodiment Example l: 1, synthesis of 3-imino-isoindoline comprises the steps of: ① in the

apparatus

Stirring drying apparatus with a 250ml 4-neck flask was added 68ml methanol and dried after
processing, the raw material o

Dicyanobenzene 18g (140mmo1) mixing and 0.2g sodium formate, solvent methanol was added,
with stirring, through

Ammonia gas about 6735ml (ammonia gas density at standard conditions of 0.7081g / L),
ammonia gas stream

Amount may 20~50L / h, slowly warmed to 6 (TC, Scrubber with dilute hydrochloric acid, at a
temperature trans
It should be 5.5 hours, the reaction solution obtained after the reaction. The amount ratio of the
above substances, the catalyst A

The amount of sodium phthalonitrile of 1.1% by mass, molar ratio of phthalonitrile and the
solvent is methanol

1:12, the molar ratio of ammonia and phthalonitrile is l: 2. ② The solvent was distilled off the
reaction solution A

Alcohol, cooled (to room temperature 25X :) may be filtered, and finally to give l, 3- diimino
isoindoline product

(Appearance: white crystals) 19.2 g of, 107% yield, mp measured 195.6~197.rC (and

Consistent with literature values), purity (content) of 97.8% (HPLC). ② above step was
dissolved in distilled

Methanol can be recycled agent. The present invention relates to the following experimental
equation:

<Formula> formula see original document page 6 </ formula> Example 2: 1, synthesis of 3-
imino-isoindoline comprises the following: ① From the added dried 4-neck flask equipped with
a stirring drying apparatus the ethanol 486ml, raw phthalonitrile 128g (lmol) of sodium
hydroxide 1.5g were mixed, and the solvent ethanol was added, with stirring, ammonia gas into
approximately 240.5 L, slowly warmed to 5 (TC, at this temperature molar ratio of 6 hours of
reaction, the reaction solution obtained after the reaction. the amount ratio of the above
substances, the amount of the catalyst is sodium hydroxide, the quality of the nitrile 1.1%
phthalimide, phthalonitrile and the solvent is ethanol l : 8.32, molar ratio of ammonia and
phthalonitrile is l: 10.② the solvent was distilled off the reaction solution, ethanol, cool (room
temperature to be) filtered, and finally to give l, 3- diimino isoindoline product 135.7 g, 106.1%
yield, melting point was measured 194.7~196.2.C, purity (content) of 97.1% (HPLC). ② above
step

The solvent was distilled ethanol can be recycled.

Example 3: as in Example l embodiments feeding operation, except that methanol is replaced by

ethanol 300ml, sodium formate into sodium hydroxide 1.5g, after the completion of the reaction,
distillation was filtered to give the product 19.09 g, yield 106.1%, content of 98.1% (HPLC), a
melting point was measured 194.7-196.2 ° C (literature value

Consistent).

Example 4: as in Example l embodiments feeding operation, except that methanol was replaced
by the ethylene glycol and A
Sodium methoxide, sodium replaced, after the completion of the reaction, distillation was filtered
to give the product 19.18 g, yield 106.6%, content 98%, mp 195.8~197.rC (consistent with
literature values).

Example 5: l feeding operation as in Example embodiment, except that the sodium formate 0.28
sodium metal into O.lg, after the completion of the reaction, filtration was distilled to yield
product 19.31g, yield 107.3%, purity (content) of 97.6 % (HPLC), mp 195.1~197.6. C
(consistent with literature values).

Example 6: 1, synthesis of 3-imino-isoindoline comprises the following: ① From the original

Phthalonitrile feed mixture and catalyst, alcohol solvent is added, with stirring, ammonia gas,
warmed to

55 ° C, reacted at this temperature for 4 hours to obtain a reaction solution; wherein the catalyst
is used in an amount of 3% by mass of phthalic nitrile (may also be selected from 0.01% or 5%
or 10%), phthalonitrile and the solvent

Molar ratio of i: io (can also use i: i, or i: 5, or i: 15), the molar ratio of ammonia and
phthalonitrile is i: 3 (can also use i: 0.3, or i: 6 or i: 13). The catalyst is an alkali metal and an
alkali metal compound wherein the two materials or a combination of a substance or two or more
species, the alkali metal compound is an alkali metal salt of an inorganic base or an alkali metal
or organic alkali metal salt. ② The solvent was distilled off the reaction solution, cooling was
filtered to give i, 3- diimino isoindoline product. Recycling the solvent distilled off in the above
step ②. The yield was 106% -107%, purity (content) of 97% ~97.6% (HPLC), mp 194.5~197.6.
C.

The catalyst may be an inorganic alkali metal salt, an alkali metal carbonate catalyst may be
selected and an alkali metal bicarbonate, or a substance wherein the two substances or a
combination of two or more thereof. The catalyst may be an alkali metal, sodium metal or the
like can be selected. The catalyst may be alkali metal base, catalyst composition can select one or
both of potassium hydroxide and sodium hydroxide. Inorganic alkali metal salts of the above
may be used as a catalyst as potassium carbonate, sodium hydrogen carbonate, the catalyst
composition can select one or both of potassium carbonate and sodium bicarbonate. The organic
alkali metal salt may be used as a catalyst an alkali metal formates, alkali metal acetates, alkali
metal oxalates, alkali metal salts of alcohols, a catalyst can choose one of them or two substances
or substance a combination of two or more thereof. The organic alkali metal salt used as a
catalyst may be sodium formate, sodium acetate, sodium methoxide, sodium oxalate, sodium
ethoxide, potassium oxalate, the catalyst may choose one of them was

Substance or a combination of two substances or two or more substances. For example, the
catalyst may be combinations of metallic sodium and potassium and sodium three ethanol. Also,
for example, the catalyst can be a combination of potassium hydroxide and sodium acetate.
These solvents can be less than an alcohol or an alcohol aqueous solution 10 carbon atoms, or the
solvent can be ethanol or glycol is methanol or their respective aqueous solutions.
SUMMARY foregoing embodiments of the present invention is further illustrated, but this
should not be understood that the scope of the present invention, the above subject is limited to
the above embodiments, all implemented based on the technical content of the above belong to
the scope of the present invention.