GB813460A - New esters of hyponitrous acid and their preparation - Google Patents
New esters of hyponitrous acid and their preparationInfo
- Publication number
- GB813460A GB813460A GB1351756A GB1351756A GB813460A GB 813460 A GB813460 A GB 813460A GB 1351756 A GB1351756 A GB 1351756A GB 1351756 A GB1351756 A GB 1351756A GB 813460 A GB813460 A GB 813460A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hyponitrite
- bis
- ether
- ethylene
- hal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C203/00—Esters of nitric or nitrous acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention comprises polymeric esters of hyponitrous acid wherein the organic residues contain at least one ether oxygen atom, preferably on the alpha carbon. The polymeric esters preferably contain units of the general structure -X-OCHY-ON=NO- wherein X1 may be alkenyl, alkoxyalkenyl, cycloalkenyl or arylene and Y may be hydrogen, alkyl, cycloalkyl, aryl, alkoxy, or alkoxyaryl or may form part of a ring with X1. The novel hyponitrites may be prepared by interaction between silver hyponitrite or other metal hyponitrite and a dihalide Hal-R-Hal, where R is an organic radical containing at least one ether oxygen, preferably in solution in an inert hydrocarbon solvent, for example white spirit, ethers or aromatic hydrocarbons. The reaction is controlled by external cooling of the reaction mixture usually to a temperature of - 20 DEG to 10 DEG C., preferably below - 10 DEG C. When the reaction is finished, the metal halide may be removed by filtration. The so-obtained solution of hyponitrite may be used as such in the polymerization of ethylenically unsaturated compounds, or the hyponitrite may be isolated therefrom, e.g. by evaporation of the solvent. In Example (13), silver hyponitrite and the diethyl ether of ethylene glycol are mixed at - 20 DEG C. and sym-dichloro-dimethyl ether is added slowly, the mixture being stirred at - 20 for 12 hours after which the chloride is removed by filtration. The product is poly1:2-aza : 3:5:7-oxaheptane. Polymerization of ethylenically unsaturated compounds.-Esters of hyponitrous acid (both monomeric and polymeric) wherein the organic residues contain at least one ether oxygen atom are valuable catalysts for the polymerization of ethylenically unsaturated compounds such as ethylene and vinyl acetate. The solution of hyponitrite obtained by interaction of a metal hyponitrite with a monohalide R-Hal (see Group IV (b)) or a dilahide Hal-R-Hal, where R is an organic radical containing at least one ether oxygen atom, in an inert solvent, may be used as such. The hyponitrite may be prepared in solution in the liquid monomer which is to be polymerized. In Example 34, silver hyponitrite is reacted with methyl chloromethyl ether in liquid ethylene to give bis-methoxy methyl hyponitrite; the fluid contents of the reaction vessel are discharged to a storage vessel, a flush of liquid ethylene is passed through the reaction vessel to the storage vessel, more ethylene is added and compressed to 1500 atm. and on allowing the contents of the storage vessel to warm to room temperature, polymerization of the ethylene ensues. Bis - (a ,a - di - ethoxyethyl) hyponitrite and bis-triethoxymethyl hyponitrite in ether (Examples 33 and 27) are also specified as catalysts for the polymerization of ethylene. Specification 618,168 is referred to.ALSO:The invention comprises esters of hyponitrous acid RO-N=N-OR1 wherein the organic radicals R and R1 contain at least one ether oxygen, preferably on the a -carbon atom. R and R1, and optionally the hyponitrous acid residue may form part of a ring system. The novel hyponitrites include esters of the formula (XOCHYON)2 wherein X may be alkyl, alkoxyalkyl, cycloalkyl or aryl and Y may be hydrogen, alkyl, cycloalkyl, aryl, alkoxy or alkoxyalkyl, or may form part of a ring with X; and polymeric esters containing units of the general structure -X1-OCHY-ON = N-O-wherein X1 may be alkenyl, alkoxyalkenyl, cycloalkenyl or arylene and Y is as defined above. The preferred compounds have the formula: R11-O-CH2-O-N = N-O-CH2-O-R11 wherein R11 represents ethyl, n or iso-propyl, n, iso or sec-butyl, iso-amyl, n or sec-octyl, 2 : 4 : 4 - trimethylpentan - 2 - yl, 3 : 5 : 5-trimethylhexan-1-yl, dodecyl or cyclohexyl, or stands for a difunctional group containing, for example, other or the same a -alkoxyalkyl hyponitrite groups, or a -chloroether groups. Also within the preferred class are tetrahydropyranyl and tetrahydrofuranyl hyponitrites. The new organic hyponitrites may be prepared by interaction between silver hyponitrite or other metal hyponitrite and a halide R-Hal, or Hal-R-Hal where R is as above defined, preferably in solution in an inert hydrocarbon solvent, for example white spirit, ethers or aromatic hydrocarbons. Other solvents include liquefied gases including ethylene and other polymerizable monomers. The reaction is controlled by external cooling of the reaction mixture usually to a temperature of -20 DEG C. to 10 DEG C., preferably below -10 DEG C. When the reaction is finished, the silver halide may be removed by filtration. The solution of hyponitrite obtained may be used as such, for example in the polymerization of ethylenically unsaturated compounds, or the hyponitrite may be isolated by evaporation of the solvent at low temperatures or by crystallization at low temperature. Examples describe the preparation of bis-methoxymethyl hyponitrite, bis - isobutoxymethyl hyponitrite, tetrahydropyran hyponitrite, bis - cyclohexyloxymethyl hyponitrite, tetrahydrofuran hyponitrite, bis-a - methoxybenzyl hyponitrite, bis - a - ethoxy-a - cyclohexylmethyl hyponitrite, bis - phenoxymethyl hyponitrite, poly - 1 : 2 - aza - 3 : 5 : 7 - oxaheptane, bis - chloromethoxymethyl hyponitrite, bis - (a - isobutoxyethyl) hyponitrite, bis - (a - methoxyisobutyl) hyponitrite, bis - (t - butoxymethyl) hyponitrite, bis - ethoxycarbethoxymethyl hyponitrite, bis-dodecyloxymethyl hyponitrite, bis - octan - 2 - oxymethyl hyponitrite, bis - isoamyloxymethyl hyponitrite, bis - (a ,a - diethoxyethyl) hyponitrite, bis - triethoxymethyl hyponitrite, bis - (1 : 3 - dimethylbutoxymethyl) hyponitrite, bis - (3 : 5 : 5 - trimethylhexyloxymethyl hyponitrite, bis - [(b - ethoxy) ethoxymethyl] hyponitrite. Metal hyponitrites used in the examples are those of silver, sodium barium, lead, copper, thallium, cobalt and manganese. Solvents used are white spirit, the diethyl ether of diethylene glycol, the diethyl ether of ethylene glycol, ethyl ether, petroleum ether, toluene, diethyl oxalate, liquid ethylene, and acetone, An example also describes the reaction of silver hyponitrite with ethylorthoformate in dry ether while passing in anhydrous hydrogen chloride. The Provisional Specification includes hyponitrites having the formul : <FORM:0813460/IV (b)/1> and <FORM:0813460/IV (b)/2>
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL99663D NL99663C (en) | 1956-05-02 | ||
NL102792D NL102792C (en) | 1956-05-02 | ||
BE570062D BE570062A (en) | 1956-05-02 | ||
US655478A US2913481A (en) | 1956-05-02 | 1957-04-29 | Esters of hyponitrous acid |
ES0235163A ES235163A1 (en) | 1956-05-02 | 1957-04-30 | PROCEDURE FOR OBTAINING ESTERS OF HYPONITROUS ACIDS |
FR1174746D FR1174746A (en) | 1956-05-02 | 1957-05-02 | Manufacture of hyponitrous esters |
US751135A US2961460A (en) | 1956-05-02 | 1958-07-28 | Esters |
FR772072A FR73994E (en) | 1956-05-02 | 1958-08-07 | Manufacture of hyponitrous esters |
FR7592A FR74746E (en) | 1956-05-02 | 1958-12-26 | pipe elements for transporting abrasive materials or abrasive materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2489057A GB831837A (en) | 1957-08-07 | 1957-08-07 | New esters of hyponitrous acid and their preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
GB813460A true GB813460A (en) | 1959-05-13 |
Family
ID=10218870
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1351756A Expired GB813460A (en) | 1956-05-02 | 1956-05-02 | New esters of hyponitrous acid and their preparation |
GB2489057A Expired GB831837A (en) | 1956-05-02 | 1957-08-07 | New esters of hyponitrous acid and their preparation |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB2489057A Expired GB831837A (en) | 1956-05-02 | 1957-08-07 | New esters of hyponitrous acid and their preparation |
Country Status (1)
Country | Link |
---|---|
GB (2) | GB813460A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460513A (en) * | 1982-10-25 | 1984-07-17 | Board Of Control Of Michigan Technological University | Method for preparing organic hyponitrites |
WO2012101564A3 (en) * | 2011-01-24 | 2015-08-06 | Piramal Enterprises Limited | Anti-inflammatory compounds |
CN116903427A (en) * | 2023-07-05 | 2023-10-20 | 中国科学院过程工程研究所 | Nitrate functionalized ionic liquid plasticizer and application thereof |
-
1956
- 1956-05-02 GB GB1351756A patent/GB813460A/en not_active Expired
-
1957
- 1957-08-07 GB GB2489057A patent/GB831837A/en not_active Expired
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460513A (en) * | 1982-10-25 | 1984-07-17 | Board Of Control Of Michigan Technological University | Method for preparing organic hyponitrites |
WO2012101564A3 (en) * | 2011-01-24 | 2015-08-06 | Piramal Enterprises Limited | Anti-inflammatory compounds |
CN116903427A (en) * | 2023-07-05 | 2023-10-20 | 中国科学院过程工程研究所 | Nitrate functionalized ionic liquid plasticizer and application thereof |
CN116903427B (en) * | 2023-07-05 | 2024-04-16 | 中国科学院过程工程研究所 | Nitrate functionalized ionic liquid plasticizer and application thereof |
Also Published As
Publication number | Publication date |
---|---|
GB831837A (en) | 1960-04-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4163115A (en) | Preparation of esters of poly-(tetramethylene ether) glycol | |
US3426006A (en) | Process for the production of polymers of conjugated dienes | |
US2849432A (en) | Polymerization of diolefines | |
CS249511B2 (en) | Catalytic system for conjugated diolefins' polymerization or copolymerization | |
US2967173A (en) | Polymerizable esters of acrylic and methacrylic acid and polymers thereof | |
US3045001A (en) | Polymerization process | |
GB1058159A (en) | Organosilicon polymers | |
US3903168A (en) | Stable anionic polymerization initiator | |
GB813460A (en) | New esters of hyponitrous acid and their preparation | |
JPS584053B2 (en) | HMF6 trialkyloxonium epihalohydrin | |
US3167532A (en) | Tin salts of p-vinylbenzoic acid, polymers thereof and process for preparing said salts | |
US4001191A (en) | Combustible monomers and polymers therefrom | |
US3932550A (en) | Process for production of 2,6-dimethyl-1,3,6-octatriene | |
US2327985A (en) | Acyl isothiocyanate and polymer thereof | |
EP3676312B1 (en) | Direct synthesis of glycidyl azide polymers | |
US3275598A (en) | Polymerization of oxirane monoepoxides in the presence of an organometallic compoundand an alcohol | |
US3025282A (en) | Process for polymerization of vinyl ethers | |
US4095017A (en) | Vinyl monomer polymerization or copolymerization catalyzed by organoaluminum-organophosphine-metal salt of a beta-diketone catalyst system | |
US4560779A (en) | Preparation and polymerization of oxether-1 | |
JPS5655405A (en) | Polymerization of ethylene | |
US3399149A (en) | Polymerization of oxirane monoepoxides using an organometallic compound with water as cocatalysts | |
US3069395A (en) | Halothioacyl fluorides and polymers thereof | |
CN114846033A (en) | Cyclic carbonate group-containing (methyl) acrylate monomer and polymer | |
US3900379A (en) | Hydroxyl-terminated chloroprene polymers | |
US3014075A (en) | Polymeric organoborines |