US2090603A - Condensation products of - Google Patents
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- US2090603A US2090603A US2090603DA US2090603A US 2090603 A US2090603 A US 2090603A US 2090603D A US2090603D A US 2090603DA US 2090603 A US2090603 A US 2090603A
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- condensation products
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- hydroxynaphthoic acid
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- 239000007859 condensation product Substances 0.000 title description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- PXBFMLJZNCDSMP-UHFFFAOYSA-N 2-Aminobenzamide Chemical compound NC(=O)C1=CC=CC=C1N PXBFMLJZNCDSMP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- -1 sodium-chloride-aluminium-chloride Chemical compound 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RUHKZVAPXHIWJH-UHFFFAOYSA-N 2-amino-4-methylbenzamide Chemical compound CC1=CC=C(C(N)=O)C(N)=C1 RUHKZVAPXHIWJH-UHFFFAOYSA-N 0.000 description 1
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KFLIZQDVWOYHBD-UHFFFAOYSA-N n-(2-carbamoylphenyl)naphthalene-1-carboxamide Chemical compound NC(=O)C1=CC=CC=C1NC(=O)C1=CC=CC2=CC=CC=C12 KFLIZQDVWOYHBD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
- C07D239/88—Oxygen atoms
- C07D239/91—Oxygen atoms with aryl or aralkyl radicals attached in position 2 or 3
Definitions
- the present invention relates to condensation products of 2.3-hydroxynaphthoic acid bearing in the naphthalene nucleus substituents which do' not cause solubility in water with anthranilic acid amide or its substitution products, more particularly it relates to compounds which may be represented by the following formula:
- naphthalene nucleus bears substit- I I I OH b t'tu t-- 0H su s 1 en l NH 2 substituent- 6 V HzN' HzN ooo11+ H2N ⁇ (II) p '30 o OH .
- substituentfiggl I r 35 s uents which do not cause solubility in water such as alkyl, alkoxy, halogen, the nitro group and the like
- I My new compounds of the above-identified formula are obtainable by reacting upon a substitution product of 2.3-hydroxynaphthoic acid bearing in the naphthalene nucleus at least one substituent which does not cause solubility in Water with anthranilic acid amide or a suitable nuclear substitution product thereof in the presence of a dehydrating agent.
- the process is carriedout in two steps by first 10 reacting upon the nuclear substituted 2.3-hydroxynaphthoic acid chloride with anthranilic acid amide or a substitution product thereof respectively, whereby the corresponding 2.3-hydroxynaphthoyl-anthranilic acid amide is obl5 tained, and then performing the ring closure.
- the process can be illustrated by the followingscheme:
- the ring closure from 111 to II very easily enters and can be performed, for example, by heating the substance sub III at or above its melting, point respectively, or by heating the same in 45 a suitable neutral agent, suchas glycerine, or in apotassium-sodium-acetate melt. It can already be performed at low-temperature if a condensing agent is added, for example, when working in boiling amylalcohol in the presence of go potassium acetate or when introducing the compound into a sodium-chloride-aluminium-chloride melt. Most practically the ring closure is performed by heating and dissolving the sub- 5 stance sub III in aqueous caustic alkali lye. On
- the alkali metal salt of the new compound indicated above sub II which is diflicultly soluble in excess alkali separates; it easily can be isolated, and with the aid of acids the free compound can be obtained. Or otherwise the free compound can be obtained by introducing carbon-dioxide into the hot alkaline solution whereby the free compound is precipitated.
- NHC OCs 5 yields the corresponding condensation product a by splitting off water "(see Korner; Journal fiirsteine Chemie, N. F. vol. 36, page 155) however, from this, the chemical behaviour of 'the 2.3ehydroxynaphthoyl-anthranilic acid amides could not be foreseen, it rather couldbe expected that the hydroxy group in 'o position would influence the proceeding of the reaction.
- 3 First of all it'could not be expected that the new condensation products would have thevaluable properties of the 2.3-hydroxynaphthoic acid arylamides and therefore would be important intermediate products for the manufacture ofdyestuffs of good fastness properties.
- Example 1 40 21.8 parts of 6-m.eth0xy-2.3-hydroxynaphthoic acid, parts of toluene and 11.9 parts of thionylchloride are heated at 90-100 C. with the exclusion of moisture until a clear solution has formed andthe development of hydrochloric acid has ceased.
- the solution of the 6-methoXy-2.3 hydroxynaphthoic acid chloride obtained is: added in portions while. stirring. to a warm solution.
- naphthalene nucleus bears at least I one substituent selected from the group consisting of alkyl, alkoxy, halogen and the nitro group, and wherein stands for a member selected from the group consisting of a benzene nucleus and an allgvl-, a1koxy-., halogenzene nucleus, being generally yellowish crystalline substances soluble-in alkalies and being val i uable intermediate products for the manufacture of dyestuffs.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Aug. 17, 1937 CONDENSATION PRODUCTS OF 2.3-HY- DROXYNAPHTHOIC ACID Wolfgang Winkelmiiller,
Leverkusen-Wiesdorf,
Germany, assignor to GeneralAniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application November 7,
Serial No. 48,777. In Germany November 14,
4 Claims. (c1. 200-32 The present invention relates to condensation products of 2.3-hydroxynaphthoic acid bearing in the naphthalene nucleus substituents which do' not cause solubility in water with anthranilic acid amide or its substitution products, more particularly it relates to compounds which may be represented by the following formula:
wherein the naphthalene nucleus bears substit- I I I OH b t'tu t-- 0H su s 1 en l NH 2 substituent- 6 V HzN' HzN ooo11+ H2N\ (II) p '30 o OH . substituentfiggl I r 35 s uents which do not cause solubility in water, such as alkyl, alkoxy, halogen, the nitro group and the like, and wherein I My new compounds of the above-identified formula are obtainable by reacting upon a substitution product of 2.3-hydroxynaphthoic acid bearing in the naphthalene nucleus at least one substituent which does not cause solubility in Water with anthranilic acid amide or a suitable nuclear substitution product thereof in the presence of a dehydrating agent. Advantageously the process is carriedout in two steps by first 10 reacting upon the nuclear substituted 2.3-hydroxynaphthoic acid chloride with anthranilic acid amide or a substitution product thereof respectively, whereby the corresponding 2.3-hydroxynaphthoyl-anthranilic acid amide is obl5 tained, and then performing the ring closure. The process can be illustrated by the followingscheme:
The ring closure from 111 to II very easily enters and can be performed, for example, by heating the substance sub III at or above its melting, point respectively, or by heating the same in 45 a suitable neutral agent, suchas glycerine, or in apotassium-sodium-acetate melt. It can already be performed at low-temperature if a condensing agent is added, for example, when working in boiling amylalcohol in the presence of go potassium acetate or when introducing the compound into a sodium-chloride-aluminium-chloride melt. Most practically the ring closure is performed by heating and dissolving the sub- 5 stance sub III in aqueous caustic alkali lye. On
cooling, the alkali metal salt of the new compound indicated above sub II which is diflicultly soluble in excess alkali separates; it easily can be isolated, and with the aid of acids the free compound can be obtained. Or otherwise the free compound can be obtained by introducing carbon-dioxide into the hot alkaline solution whereby the free compound is precipitated.
It has already been known that the benzoylhaving the formula:
NHC OCs 5 yields the corresponding condensation product a by splitting off water "(see Korner; Journal fiir praktische Chemie, N. F. vol. 36, page 155) however, from this, the chemical behaviour of 'the 2.3ehydroxynaphthoyl-anthranilic acid amides could not be foreseen, it rather couldbe expected that the hydroxy group in 'o position would influence the proceeding of the reaction. 3 First of all it'could not be expected that the new condensation products would have thevaluable properties of the 2.3-hydroxynaphthoic acid arylamides and therefore would be important intermediate products for the manufacture ofdyestuffs of good fastness properties.
' The' invention'is illustrated by the following examples, without being limited thereto, the parts being by weight:
1 Example, 1 40 21.8 parts of 6-m.eth0xy-2.3-hydroxynaphthoic acid, parts of toluene and 11.9 parts of thionylchloride are heated at 90-100 C. with the exclusion of moisture until a clear solution has formed andthe development of hydrochloric acid has ceased. The solution of the 6-methoXy-2.3 hydroxynaphthoic acid chloride obtained is: added in portions while. stirring. to a warm solution.
of 13.6 parts of anthranilic acid amide in 300 parts of toluene, and the reaction mixture is reflux-ed until hydrochloric acid does no longer escape. Thereby the fi-methoxy-zfi-hydroxyey naphthoyl anthranilic acid amide separates in form of a greenish yellow somewhat resinous intermediate (after recrystallizing from nitro'- benzene decomposing at 232 C.) By dissolving the reaction product in an aqueous caustic soda lye of 4% and heating the ring closure is performed and the condensation product having the following formula:
is precipitated as a greyish green. powder by in? troducing carbon dioxide:(point of decomposi tionabove300 0.). v
In an analogous manner there have beenpre pared the condensation, products from anthra nilic acid amide and 'I-rnethbxy-ZB-hjrdroxy- (and also the acetyl) anthranilic acid amide naphthoi acid (point of decomposition above 300 C.) 6-methyl-2.3-hydroxynaphthoic acid (point of decomposition above 300 C.) fi-bromo- 2.3-hydroxynaphthoic acid (point of decomposition above 300 C.), found by analysis 21.2%
of bromine, calculated 21.8% of 'bromine; 7-
chloro-2.3-hydroxynaphthoic acid (point of decomposition above 360 0.), found by analysis 8.5% of nitrogen, 11.2% of chlorine, calculated 1 8.7% of nitrogen, 11.0% of ,chlorine, Further in an analogous manner there have been prepared the condensation products from Z-amino- 4z-methoxybenzamide and 6 methoxy-2.3 hydroxynaphthoic acid (point of decomposition above 300 C.) from 4-methyl-2-aminobenzamide and 7methoxy+2.3-hydroxynaphthoic acid (point of decomposition above 300 C.).
' Example 2 Into a suspension of 23.2 parts of 8-nitro-2.3- hydroxyn'aphthoic ac'id and 13.6 parts of anthranilic acid amide inabout 250 parts of toluene there are dropped while stirring 10 parts of phosphorus trichloride dissolved in 30 parts of toluene. The reaction mass is heated to boiling, while further stirring until the development of hydrochloric acid has ceased, whereby the reaction product having the following formula:
wherein the naphthalene nucleus bears at least I one substituent selected from the group consisting of alkyl, alkoxy, halogen and the nitro group, and wherein stands for a member selected from the group consisting of a benzene nucleus and an allgvl-, a1koxy-., halogenzene nucleus, being generally yellowish crystalline substances soluble-in alkalies and being val i uable intermediate products for the manufacture of dyestuffs.
a a and nitro-substituted' ben- 2. The compound of the following formula:
being a yellowish crystalline substance soluble in alkalies and being a valuable intermediate product for the manufacture of dyestufis. 15 3. The compound of the following formula:
being a yellowish crystalline substance soluble in alkalies and being a valuable intermediate prodnot for the manufacture of dyestuffs.
4. 2.3-hydroxynaphthoic acid derivatives of the formula:
WOLFGANG WINKELMULLER.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2090603A true US2090603A (en) | 1937-08-17 |
Family
ID=3428873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2090603D Expired - Lifetime US2090603A (en) | Condensation products of |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2090603A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2439386A (en) * | 1948-04-13 | Preparation of quinazolones |
-
0
- US US2090603D patent/US2090603A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2439386A (en) * | 1948-04-13 | Preparation of quinazolones |
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