USRE23399E - Unsaturated halogen-containing - Google Patents

Unsaturated halogen-containing Download PDF

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USRE23399E
USRE23399E US23399DE USRE23399E US RE23399 E USRE23399 E US RE23399E US 23399D E US23399D E US 23399DE US RE23399 E USRE23399 E US RE23399E
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olefinic
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/08—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to acyclic carbon atoms
    • C07C205/09—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to acyclic carbon atoms of an unsaturated carbon skeleton

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  • This invention relates to the production ,of new and useful unsaturated halogen-containing ultra-compounds, and more specifically relates to the nitration of halogen-containing olefinic compounds, and to the halo-nitro-oleflnic compounds thereby produced.
  • R1, R2, R3, R4, R5 and Rs represent hydrogen atoms, hydrocarbon radicals, or halo-substituted hydrocarbon radicals, such as alkyl, aralkyl, alkaryl, aryl, or cyclic parafiinic radicals, or their halo-substitution products, and wherein X represents a halogen atom, are subjected to the action of nitrous acid, or nitrogen oxides, under conditions hereinafter described, to produce new and useful compounds.
  • the re-. actants of the present invention therefore, areolefinic halides wherein the olefinic linkage is in the beta, gamma position with respect.
  • reactants containing not more than about 16 carbon atoms which are open chain monoolefinic halohydrocarbons containing the structural groupin I i on (halogen) C- IO: U comprise the most suitable class of olefinic halide reactants for employment in the process of the invention. It is essential that the structure and composition of the reactants employed in the process of our invention be within these limitations.
  • the unsaturated gamma carbon atom is the carbon atom of a terminal methylene group, and wherein the halogen atom is a chlorine or bromine atom, since, as we have found, excellent results are achieved therewith, i. e., relatively high yields and rates of production are obtained therewith, and the products dicates the additions made by reissue.
  • suitable alkyl radicals which R1, R2, R3, R4, R5 and He may represent are, for example, the methyl, ethyl, npropyl, isopropyl, the butyl, and the amyl radicals;
  • suitable aralkyl radicals are, for example, the benzyl, methyl benzyl, phenyl ethyl, phenyl propyl, and naphthyl methyl radicals;
  • suitable alkaryl radicals are, for example, the methyl phenyl, ethyl phenyl, propyl phenyl, methyl naphthyl and ethyl naphthyl radicals;
  • suitable aryl radicals for example, are the phenyl and naphthyl radicals; and suitable representative cycloparafiinic or cycloaliphatic hydrocarbon radicals are the cyclopentyl, methyl cyclo penty
  • halogen-substituted hydrocarbon radicals which R1, R2, R3, R4, R5 and Rs may represent are the chloromethyl, dichloromethyl, chloroethyl, bromomethyl, bromoethyl. chloropropyl, chlorobutyl, iodoethyl, fluoromethyl, chlorobenzyl, chlorophenyl, dichlorophenyl, chlorona'ohthyl, chlorocyclopentyl, bromocyclopentyl, chlorocyclohexyl, chloromethyl cyclopentyl and bromomethylcyclohexyl radicals.
  • R5, R6 and X represent the same atoms or ra icals as above described.
  • the new compounds prepared according to the process of the pre ent invention are nitrohalo-olefinic com ounds wherein the olefinic' relation to both the nitro group and the halogen atom, which nitro group and halogen atom are attached to different carbon atoms, and therefore each of the said different carbon atoms are attached to the same unsaturated tertiary carbon atom.
  • the compounds conforming in structure and composition to this definition have not been known heretoforeJ
  • the [above described! compounds of the in-' which dissociates -into nitrogen vention may be employed for a Wide variety of applications of industrial and commercial importance.
  • such compounds may be employed and are surprisingly eifective as fumigants against many harmful insects, as selective extracting agents for a variety of substances, as solvents, for example, of cellulose derivatives, in dye compositions, in the preparation of pharmarceuticals, in varnish, dope and lacquer compositions, in detergent compositions, as emulsifiers, as intermediates in the preparation of valuable derivatives and the like.
  • the new compounds 'oi lthe present invention are prepared by reacting a halogen-containing olefinic compound, as above defined, with nitrous acid or a nitrogen. oxide or mixture of oxides.
  • the preferred process contemplates performing the reaction in an aque one medium, for example, by dissolving 'or dispersing the olefinic reactant in an aqueous solution of a mineral acid, and adding thereto an aqueous solution of an alkali or alkaline earth metal nitrite.
  • the reaction between the nitrite and acid produces nitrous acid directly in the reaction mixture, which then reacts with, or
  • R1 and Rzare hydrogen atoms and X may be dissolved or dispersed in an aqueous solution of sulfuric acid.
  • aqueous solution o'fan alkali'or alkaline earth metal nitrite;
  • Thepr'eferred reaction temperature i'sfrom about to 60 C., though lower temperatures, e; 'g., 0 'C.,and'higher temperatures, 'e. g., 100C. may be used.
  • the unsaturated nitro-halo-olefinic products may be separated from the reaction mixture'by any convenient means,as for. example, by fractional distillation.
  • from-about 1 to-G .mols of methallylchloride (Z-chloromethylpropsne-l) isv dissolved or dispersed in an aqueous solution of sulfuric acid comprising from about 50 to mole of water and from about 1 to 10 mole of sulfuric acid.
  • reaction products are washed with water, mixed with about double their volume of toluene, and heated to boiling temperature.
  • the toluenean'd unreacted meth'all'yl chloride are removed by vacuum distillation and the desired products recovered'by vacuum fractional distillation.
  • the product may be further purified, for example by treatment with aqueous alkali, acidification and ether extraction.
  • nitrop'ropene-ll I "In'a'subst'antially identical manner, other haloencontaining'o'lefinic compounds or the above defined class m'aybe' treated to produce new and useful products.
  • the following compoundsma y be treated in accordance with the process of our invention [to produce unsaturated nitro compounds conforming to the above deflnition]: 2-bromomethylpropene-1; 3-chloro-2- methylbutene-l; 3-chloro-2,3-dimethyibutene-1; 3 chloro 2 methylpentene-1 3-chloro-2methylhexene-l; "3-chlcro-2Pethylbutene-l; 3-chloro- 2,3-diethylbutene-1; 3-chlo'ro-2-methyl-3-phenylbutene-l 2-iodomethy1propane-1; 2-chloromethyl-4,4-dimethylpentene-1; 2-chloromethyl- 4'-chlorobutene-1; and. their homologs, analogs, and suitableproducts, such as:
  • a nitrogen oxide such as nitrogen trioxide which may or may not be admixed with an inert gaseous diluent, may be introduced directly into the olefinic reactant, which may or may not be dissolved or dispersed in an aqueous or non-aqueous solvent.
  • a further modification is the vapor phase reaction between a vaporized olefinic reactant and a nitrogen oxide or mixture of oxides which may or may not be admixed with an inert gaseous diluent.
  • the process of the present invention may be operated batchwise, intermittently, or continuously, as is desired and convenient in any specific application. In the preferred process, or modifications thereof, super or sub-atmospheric pressures may be employed, but we have found that atmospheric pressure gives excellent results in most instances and is the preferred pressure.
  • the alkali and alkaline earth metal nitrites are generally suitable for use in the process of our invention.
  • sodium and potassium nitrites give excellent results, as do barium and strontium nitrites.
  • an insoluble precipitate may be formed, for example, when barium nitrite is used in conjunction with sulfuric acid insoluble barium sulfate is formed. However, this does not interfere with the process of our invention, and
  • the alkaline solution was acidifled, extracted with ether, and EZ-chloromethyl- B-nitropropene-l (nitromethallylchloride) ,1 the desired productL] separated therefrom.
  • the yield was about 50% based on the converted methallylchloride; omission of the alkali purification step results in a yield of about 70%.
  • Example II was repeated at four other temperatures: 0, 10, 25 and 60 C. Analogous results and substantially identical yields were obtained, but as shown in the following table, more methallyl-. chloride reacted at the higher temperatures, but a correspondingly larger residue remained after fractionation.
  • a process for the production of 1-nitro-'2- chloromethyl 4,4 dimethylpentene-z] which comprises reacting, at a temperature of. not more thanabout100 C., 2-ch1oromethy1-4,4-dimethy1- DBntene-I with a nitrogen oxide.
  • Aprocess for 'theproduction of1-nitro 2-j chloromethyl 4,4 dimethyIpentene-Z] which comprises reacting, at a temperature of not more than'about 100 0., 2chloromethyl-4,4-dimethylpentene-l in an aqueous medium with nitrous acid.

Description

Reissued Aug. 14, 1951 UNSATURATED HALOGEN-CONTAINING NITRO COMPOUNDS AND THEIR PRO- DUCTION Eduard Cornelis Kooijman and Johan overhofi,
Amsterdam,
Netherlands, assignors to Shell Development-Company, San Francisco, Calif., a
corporation of Delaw No Drawing. Original 14, 1949, Serial No. 739,948, April 7,
reissue May 8, 1951, Serial No.
plication for are No. 2,473,341, dated June 2Z5,259. In the Netherlands July. 5, 1946 (Cl. 260-644) Matter enclosed in heavy brackets I: II appears in the original patent but forms no part of this 19 Claims.
reissue specification; matter printed in italics in This invention relates to the production ,of new and useful unsaturated halogen-containing ultra-compounds, and more specifically relates to the nitration of halogen-containing olefinic compounds, and to the halo-nitro-oleflnic compounds thereby produced.
According to the process of the present invention, olefinic halogen compounds of the general formula:
wherein R1, R2, R3, R4, R5 and Rs represent hydrogen atoms, hydrocarbon radicals, or halo-substituted hydrocarbon radicals, such as alkyl, aralkyl, alkaryl, aryl, or cyclic parafiinic radicals, or their halo-substitution products, and wherein X represents a halogen atom, are subjected to the action of nitrous acid, or nitrogen oxides, under conditions hereinafter described, to produce new and useful compounds. The re-. actants of the present invention, therefore, areolefinic halides wherein the olefinic linkage is in the beta, gamma position with respect. to the halogen atom, and the beta carbon atom is an unsaturated tertiary carbon atom. In view of the diminution in the chemical reactivity of olefinic linkages caused by a multiplicity of carbon atoms, reactants containing not more than about 16 carbon atoms, which are open chain monoolefinic halohydrocarbons containing the structural groupin I i on (halogen) C- IO: U comprise the most suitable class of olefinic halide reactants for employment in the process of the invention. It is essential that the structure and composition of the reactants employed in the process of our invention be within these limitations. We prefer to employ a reactant wherein the unsaturated gamma carbon atom, as above defined, is the carbon atom of a terminal methylene group, and wherein the halogen atom is a chlorine or bromine atom, since, as we have found, excellent results are achieved therewith, i. e., relatively high yields and rates of production are obtained therewith, and the products dicates the additions made by reissue.
obtained are especially advantageous for a variety of uses. In the above structural formula, suitable alkyl radicals which R1, R2, R3, R4, R5 and He may represent are, for example, the methyl, ethyl, npropyl, isopropyl, the butyl, and the amyl radicals; suitable aralkyl radicals are, for example, the benzyl, methyl benzyl, phenyl ethyl, phenyl propyl, and naphthyl methyl radicals; suitable alkaryl radicals are, for example, the methyl phenyl, ethyl phenyl, propyl phenyl, methyl naphthyl and ethyl naphthyl radicals; suitable aryl radicals, for example, are the phenyl and naphthyl radicals; and suitable representative cycloparafiinic or cycloaliphatic hydrocarbon radicals are the cyclopentyl, methyl cyclo pentyl, dimethyl cyclopentyl, ethyl cyclopentyl, cyclohexyl, methyl cyclohexyl, polymethyl cyclohex l, and propyl cyclohexyl radicals. Representative halogen-substituted hydrocarbon radicals which R1, R2, R3, R4, R5 and Rs may represent are the chloromethyl, dichloromethyl, chloroethyl, bromomethyl, bromoethyl. chloropropyl, chlorobutyl, iodoethyl, fluoromethyl, chlorobenzyl, chlorophenyl, dichlorophenyl, chlorona'ohthyl, chlorocyclopentyl, bromocyclopentyl, chlorocyclohexyl, chloromethyl cyclopentyl and bromomethylcyclohexyl radicals.
[The new compounds of the present invention may be represented by the general formula:
' wherein R1, R2, R3, R4. R5, R6 and X represent the same atoms or ra icals as above described.-
Thus, the new compounds prepared according to the process of the pre ent invention are nitrohalo-olefinic com ounds wherein the olefinic' relation to both the nitro group and the halogen atom, which nitro group and halogen atom are attached to different carbon atoms, and therefore each of the said different carbon atoms are attached to the same unsaturated tertiary carbon atom. The compounds conforming in structure and composition to this definition have not been known heretoforeJ The [above described! compounds of the in-' which dissociates -into nitrogen vention may be employed for a Wide variety of applications of industrial and commercial importance. Thus, for example, such compounds may be employed and are surprisingly eifective as fumigants against many harmful insects, as selective extracting agents for a variety of substances, as solvents, for example, of cellulose derivatives, in dye compositions, in the preparation of pharmarceuticals, in varnish, dope and lacquer compositions, in detergent compositions, as emulsifiers, as intermediates in the preparation of valuable derivatives and the like.
As above described, the new compounds 'oi lthe present invention are prepared by reacting a halogen-containing olefinic compound, as above defined, with nitrous acid or a nitrogen. oxide or mixture of oxides. The preferred process contemplates performing the reaction in an aque one medium, for example, by dissolving 'or dispersing the olefinic reactant in an aqueous solution of a mineral acid, and adding thereto an aqueous solution of an alkali or alkaline earth metal nitrite. The reaction between the nitrite and acid produces nitrous acid directly in the reaction mixture, which then reacts with, or
oxides whiche eact with-the dissolved or dispersedolefinic compound. Various mineral acids which react with the nitritesto producenitrous acid may behemployed, sulfuric acid giving excellent results, as do phosphoric and nitric acids. The halogen acids suchas hydrochlorid however, are less suit.- able,-since they may undergo side reactions with the olei'inic reactant resulting in the formation of. undesired additive-compounds. Various modifications in the preferred process may be made, e. -g.,-the-alkali oralkaline: earth. metal nitrites maybe added to theacidified aqueous reaction mixture i-nsolidform, preferably pulverized in order -to achieve rapid reaction.
Incarrying out a preferred embodiment of the process of the invention, an olefinic compound of. thegeneral formula:
wherei'n'Ri, R2; R3, R4, R5 and Rs'representhw drogen atoms, hydrocarbon radicals orhalo-substitu'te'd hydrocarbon radicals, such as alkyl, aralkyl, 'alkaryl, 'arylor cyclic parafflnic groups, or their halo-substitution products, and wherein X represents a halogen atom, and preferably wherein R1 and Rzare hydrogen atoms and X is a chlorine or bromine atom, may be dissolved or dispersed in an aqueous solution of sulfuric acid. To this solution may be added an aqueous solution o'fan alkali'or alkaline earth metal nitrite; Thepr'eferred reaction temperature i'sfrom about to 60 C., though lower temperatures, e; 'g., 0 'C.,and'higher temperatures, 'e. g., 100C. may be used. "Temperatures of above about 100 (3., however, should be avoided, since undesirable side reactionsmay occur "at such elevated temperatures. The unsaturated nitro-halo-olefinic products may be separated from the reaction mixture'by any convenient means,as for. example, by fractional distillation. We have found, however,'that during distillation a considerable quantity of .gases may be released from the reaction mixture, especially where the nitrite additionwas performe'dat relatively low temperatures, which may interfere with the distillation process. This nitrous acidt Part of. the
60 C1, the blue color rapidly changes to green.
We have further observed, as above described, that in. the recovery'of our products by fractional distillation, there may be generated during the distillation-a considerable quantity of gas which may interfere with said distillation. This evolution/of gas is especially evident when the nitrite additionjwa's performed at relatvely low tem- .p'eratures, e. g., below about 40 C. Though we do no'twish't'o be limited by any theoretical explanation, we believe these phenomena are due at least in partto the formation of an addition product or products "between the olefin and the oxides of nitrogen, probably nitrogen trioxide, which are probably formed from the generated attached nitrogen oxidesare ,split off by the elevated temperature encountered. during the reaction or the distillation, thereby causing the color change and gas generation.
As illustrative of a specific example of a preferred embodiment of the process of the present invention, from-about 1 to-G .mols of methallylchloride (Z-chloromethylpropsne-l) isv dissolved or dispersed in an aqueous solution of sulfuric acid comprising from about 50 to mole of water and from about 1 to 10 mole of sulfuric acid. A quantity of an. aqueous solution of sodium nitrite, comprising about 1 part of nitrite to from about 1 to 10 parts of water, preferably sufficient 'to generate an excess of nitrous acid, is slowly added, thetemperature being held to from about25' to '60 C. The reaction products are washed with water, mixed with about double their volume of toluene, and heated to boiling temperature. At the end of gas generation the toluenean'd unreacted meth'all'yl chloride are removed by vacuum distillation and the desired products recovered'by vacuum fractional distillation. If desired, the product may be further purified, for example by treatment with aqueous alkali, acidification and ether extraction. [The chief product obtained nitrop'ropene-ll] I "In'a'subst'antially identical manner, other haloencontaining'o'lefinic compounds or the above defined class m'aybe' treated to produce new and useful products. For example, the following compoundsma y be treated in accordance with the process of our invention [to produce unsaturated nitro compounds conforming to the above deflnition]: 2-bromomethylpropene-1; 3-chloro-2- methylbutene-l; 3-chloro-2,3-dimethyibutene-1; 3 chloro 2 methylpentene-1 3-chloro-2methylhexene-l; "3-chlcro-2Pethylbutene-l; 3-chloro- 2,3-diethylbutene-1; 3-chlo'ro-2-methyl-3-phenylbutene-l 2-iodomethy1propane-1; 2-chloromethyl-4,4-dimethylpentene-1; 2-chloromethyl- 4'-chlorobutene-1; and. their homologs, analogs, and suitableproducts, such as:
As above described, we prefer to carry out our process in an aqueous solution or dispersion by generating nitrous acid directly in the solution.
However, variations in the described procedure may be made without departing from the scope of our invention. For example, a nitrogen oxide such as nitrogen trioxide, which may or may not be admixed with an inert gaseous diluent, may be introduced directly into the olefinic reactant, which may or may not be dissolved or dispersed in an aqueous or non-aqueous solvent. A further modification is the vapor phase reaction between a vaporized olefinic reactant and a nitrogen oxide or mixture of oxides which may or may not be admixed with an inert gaseous diluent. The process of the present invention may be operated batchwise, intermittently, or continuously, as is desired and convenient in any specific application. In the preferred process, or modifications thereof, super or sub-atmospheric pressures may be employed, but we have found that atmospheric pressure gives excellent results in most instances and is the preferred pressure.
As above described, the alkali and alkaline earth metal nitrites are generally suitable for use in the process of our invention. For example, sodium and potassium nitrites give excellent results, as do barium and strontium nitrites. In some instances an insoluble precipitate may be formed, for example, when barium nitrite is used in conjunction with sulfuric acid insoluble barium sulfate is formed. However, this does not interfere with the process of our invention, and
may be advantageous where removal of the me-' tallic ion is desired.
The following examples further illustrate preferred embodiments of our invention, which is not to be considered as limited thereby:
EXAMPLE I To a mixture of 2'70 grams of methallyl chloride, 392 grams of sulfuric acid, and 1600 grams of water was added dropwise a solution of 520 grams of sodium nitrite in 675 grams of water. The temperature was held to about 40 C. during the nitrite addition, which required about two hours. A blue color soon appeared in the oil layer, which at the end of the reaction contained the nitrosation products, any unconverted methallyl chloride, and a minor amount of by-products. The oil layer was separated'and washed with water. The separated oil layer, weighing 380 grams, was mixed with a double quantity of toluene, and the resulting mixture heated to boiling temperature. The color rapidly changed from blue to green or greenish-yellow, with evolution of some gas, probably chiefly nitrous oxide. When gas evolution ceased, the unreacted methallyl chloride and subsequently the toluene were removed by vacuum distillation, the residue turning yellow. The yellow residue, containing the desired product and a minor amount of by-products, was subjected to fractional distillation. The fraction boiling at from 60 to C. at 10 mm. pressure was treated with a strong aqueous solution of lye, and the undissolved constituents separated therefrom by ether extraction. The alkaline solution was acidifled, extracted with ether, and EZ-chloromethyl- B-nitropropene-l (nitromethallylchloride) ,1 the desired productL] separated therefrom. The product was a pale yellow liquid with a boiling point of 62 C. at 4' mm. pressure, a refractive index n =1.4742, and a density of 1.234 at 20 C. The yield was about 50% based on the converted methallylchloride; omission of the alkali purification step results in a yield of about 70%.
EXAMPLE II Example I was repeated at four other temperatures: 0, 10, 25 and 60 C. Analogous results and substantially identical yields were obtained, but as shown in the following table, more methallyl-. chloride reacted at the higher temperatures, but a correspondingly larger residue remained after fractionation.
Reaction Unconvcrtcd Residue Tempera- Methallylafter Fracture Chloride tionation G. Grams Grams 0 140 15 10 1-50 20 25 50 1 40 90 60 60 75 G5 EXAMPLE W methyl-3-nitropropene-1] which comprises reacting, at a temperature of not more than about 100 C., methallyl-chloride with nitrous acid.
3. The process [for the production of 2-ch1oro 7 methyI Smitropropene-ljl" which comprises reacting; at atemperature of not more than about 100 C., methallyl-chloride in an aqueous-medium with nitrous acid.
4-. The'process [for theproduction of 2-'ch1oromethyl-3-nitropropene-l1 which comprises reacting, at a temperature of not more than about 100 -C., methallyl-chloridein an aqueous medium with nitrous acid which is generated within the aqueous medium.
55 A process [for the production of 1-nitro-'2- chloromethyl 4,4 dimethylpentene-z] which comprises reacting, at a temperature of. not more thanabout100 C., 2-ch1oromethy1-4,4-dimethy1- DBntene-I with a nitrogen oxide.
6. Aprocess [for 'theproduction of1-nitro 2-j chloromethyl 4,4 dimethyIpentene-Z] which comprises reacting, at a temperature of not more than'about 100 0., 2chloromethyl-4,4-dimethylpentene-l in an aqueous medium with nitrous acid.
7. [1 nitro 2- chloromethyl 4,4-dimethyipentene-ZJ 8. A process [for-the production of l-nitro-Z- chloromethyl e-chiorobutene-fl which comprises reacting, at a temperature of not more than about 100 0., Z-chloromethyl-A-ch1or'obu= tene lwith anitrogen' oxide.
9. A-processlffor the production of 1-nitro-2- chloromethyl 4-=ch1orobutene21 which com= prises reacting, at a temperature of not more than about 100 C., 2-ehloromethyii -chlorobu tene-l in an aqueous medium with nitrous'acid.
10. [1 nitro 2 chlorcmethyl 4-ch1orobutens-2.]
11. [A 3 -'ch1oro- Z-aikylidene-l-nitroa1kane containingfrom 4 to 16 carbon atoms] 12. A process [for the production of 3-ch1oro- 2'-a.1ky1idene-l-nitroalkanes] which comprises reacting, at a temperature of not more than about (halogen)Oy -CN Or 14. A process for the production of monoolefinic-mononitroha1ohydrocarbons which com- :prises reacting at a temperature of not more than about 100 C. a mono-olefinic halohydrocarbon having from 4 to 16 carbon atoms to the molecule and which contains the structural grouping OH (haJogen)C- (I): C with a, nitrogen oxide.
15. The mcno-olefinic mononitrohalohydnocarbon produced by "the process defined in claim 2.
16. The mono-olefinic mononitrohalohydrocarb-on produced by the process defined in claim 5.
17. The mono-olefimc mononitrohalohydrocarbon produced by the process defined in claim 9.
18. The mono-olefim'c mononitrohalohydrocarbon prodnced'by the process defined in claim 12. 19. The mono-olefinzc mononitrohalohydrocar bon produced by the process defined in claz'mlsl.
EDUARD CORNELIS KOOIJMAN. JOHAN OVERHOFF.
REFERENCES CITED The'follo-wing references'are of record in the file of this patent or the original patent:
Science News Letter. March 22,1947, page 188.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2770657A (en) * 1953-02-11 1956-11-13 Du Pont Nitrogen dioxide compounds of 1, 3-dichloro-2-butene, and compositions containing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2770657A (en) * 1953-02-11 1956-11-13 Du Pont Nitrogen dioxide compounds of 1, 3-dichloro-2-butene, and compositions containing the same

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