US2563074A - Production of spirohydrocarbons - Google Patents

Production of spirohydrocarbons Download PDF

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US2563074A
US2563074A US763734A US76373447A US2563074A US 2563074 A US2563074 A US 2563074A US 763734 A US763734 A US 763734A US 76373447 A US76373447 A US 76373447A US 2563074 A US2563074 A US 2563074A
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spirohydrocarbon
cyclopentadiene
dihaloalkane
sodium
carbon atoms
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US763734A
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Schmerling Louis
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Universal Oil Products Co
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Universal Oil Products Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/72Spiro hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C07C1/328Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being an alkali metal atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/08Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
    • C07C13/15Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentadiene ring
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/06Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00Systems containing at least three condensed rings
    • C07C2603/93Spiro compounds
    • C07C2603/94Spiro compounds containing "free" spiro atoms

Description

Patented Aug. 7, 1951 UNITED STATES PATENT OFFICE PRODUCTION OF SPIROI -IYDROCARBON S Louis Schmerling, Riverside, I11., assignor to Universai Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application July 25, 1947,
Serial No. 763,734
7 Claims. (Cl. 260-666) where R, R, R" and R are selected from the group consisting of hydrogen and alkyl radicals, X represents a halogen and n is an integer from 1 to 5 inclusive and the unsatisfied valences of the group are combined with a member of the group consisting of hydrogen and an alkyl radical.
Another specific embodiment of this invention relates to a process for producing a spirohydrocarbon which comprises condensing an alpha, omega-dihaloalkane and a cycloalkadiene.
Yet another embodiment of this invention relates to a process for producing a spirohydrocarbon which comprises reacting an alpha, ome-ga-dihaloalkane and an addition compound of a cycloalkadiene and an alkali metal.
A further embodiment of this invention relates to a process for producing a spirohydrocarbon which comprises reacting an alpha, omega-dihalo- -dia1ky1a1kane and a sodium addition compound of a cycloalkadiene to form a diolefinic spirohydrocarbon having two quaternary carbon atoms and hydrogenating said diolefinic spirohydrocarbon to form a saturated spirohydrocarbon having two quaternary carbon atoms.
A still further embodiment of this invention relates to a process for producing a spirohydrocarbon which comprises reacting 1,5-dibromo- 3,3-dimethylpentane and disodium cyclopentadiene to form 5,5-(33-dimethylpentamethylene) 1,3-cyclopentadiene.
This invention relates to a process for preparing hydrocarbons containing conjugated double bonds and a spiro carbon atom. Such hydrocarbons which are new compositions of matter 2 are formed by the reactions indicated in the following equations:
The dihaloalkane in the above equation is 1,5-dibromo-3,3-dimethylpentane. Other suitable dihaloalkanes are those having the structure represented by R R a arm where R, R, R" and R' are selected from the group consisting of hydrogen and alkyl radicals, n is an integer from 1 to 5 inclusive, and X is halogen. The preferred compounds are those in which R, R, R" and R are hydrogen, i. e. compounds in which the halogen atoms are attached to primary carbon atoms. Foorer yields are obtained when either (or both) halogen atom is attached to a secondary carbon atom and still lower yields are obtained with compounds con taining halogen attached to a tertiary carbon atom. The preferred value of n is 2 or 3. The preferred halogen is chlorine or bromine. In dihaloallganes represented by the above formula, the unsatisfied valence bonds are combined with a member of the group consisting of hydrogen and an alkyl group. p
Dihaloalkanes preferred as starting materials in this process are indicated by the following formula:
in which each of R R R R", R and R represents a member of the group consisting of hydrogen and alkyl radicals, X represents a halogen, and the characters m and n are selected from the members of the group consisting of 0, 1, 2, and 3. The halogens generally preferred are chlorine and bromine. The characters m and n are such that their sum has a value of from 0 to 4 and preferably of 1 or 2. When m and n are zero Formula 2 is of essentially the same form as Formula 1.
A preferred starting material for this process is thus an alpha, omega-dihaloalkane in which a halogen atom, preferably chlorine or bromine, is combined with each of the two end carbon atoms of an alkane chain containing four or five carbon atoms. Such dihaloalkanes include 1,5- dibromo 3,3 dimethylpentane, 1,4 dibromobutane, and 1,5-dichloropentane.
Dihaloalkanes containing a quaternary carbon atom such as 1,5-dichloro-3,3-dimethylpentane and the corresponding dibromoalkane may be formed by condensing a monoolefin and a dihaloalkane in which one of the halogen atoms is attached to a tertiary carbon atom, and the other is attached to a primary carbon atom, said condensation being carried out in the presence of a Friedel-Crafts catalyst at a temperature of from about -40 to about 100 C.
Good yields of such dihaloalkanes are obtained by condensing a monoolefin such as ethylene with a dihaloalkane in which the halogens are combined with one tertiary and one non-tertiary carbon atom. Thus ethylene will condense with isoprene dihydrochloride (more exactly known as 1,3-dichloro-3-methylbutane) in the presence of aluminum chloride and other Friedel-Crafts catalysts to form 1,5-dichloro-3,3dimethylpentane.
Cyclopentadiene is a diolefin which has two hydrogen atoms that are readily replaced by sodium or by another alkali metal to form a sodium addition product of said cyclic diolefin which may be reacted with dihaloalkanes of the type described above to form a spirohydrocarbon. Thus reaction of cyclopentadiene sodium with 1,5-dibromo-3,3-dimethylpentane yields 5,5-(3,3-
The condensation of a cycloalkadiene with an alpha, omega-dihaloalkane having at least four carbon atoms per molecule may be accomplished in several ways. One method consists in adding the diene to a solution of sodium alkoxide in an alcohol such as ethyl alcohol and then adding the dihaloalkane. The addition of the diene to.
the solution of sodium alkoxide is preferably carried out at about 20 to 25 C; Reaction with 1 the dihalide may be carried out at temperatures of about l0 to +100 C., preferablyat about the reflux temperature of the reaction mixture.
Another procedure consists in adding the diene to a solution of sodium in'liquid ammonia and 1 then adding the dihalide. The reactionmay be Both 5 4 the process of this invention although the data are not introduced with the intention of limiting unduly the broad scope of the invention.
Example I The condensation of Cyclopentadiene and 1,5- dibromo-3,3-dimethylpentane was carried out as follows in a glass reactor of 500 cc. capacity. Sodium metal (5 g., 0.21 mole) was dissolved in 67 cc. of absolute alcohol (redistilled from sodium). The resulting solution was cooled to 2 C. and 7 g. (0.11 mole) of cyclopentadiene was added. A brown precipitate separated, 1,5-dibroIno-3,3-dimethylpentane (25 g., 0.10 mole) was added and the stirred mixture was heated to 60 C. A White salt precipitated. The temperature was maintained at 6070 C. for two hours, the product was then cooled, water was added and the product was steam distilled. There was obtained 9 cc. of
Cut 2 was analyzed. 88.83; H, 11.17. Found: C, 86.77; H, 10.86. Reaction of the material (a diene) with air is in-: dicated.
Cut 2 yielded a maleic anhydride adduct.
Example II Cyclopentadiene (18. g., 0.27 mole). was added to a solution of 10 g. (0.42 mole) of sodium in g. of liquid ammonia in a glass-lined reactor equipped with a, motor-driven stirrer and surrounded by a suitable cooling bath. 1,5-dibromo- 3,3-dimethylpentane (52 g., 0.20 mole) was then added dropwise with stirring during one-half hour. The blue color of the solution disappeared after about two-thirds of the dibromide had been added. The solution was stirred for an additional one-half hour, water was added, and the organic product was taken up in ether, washed,
Cut 4 crystallized when cooled to -78 C. It
yielded a maleic anhydride adduct, M. P. The adduct was analyzed. Calcd. for 0161121103; C, 73.80; H. 7.75. Found: C, 74.31; H, 7.83.
The hydrocarbon formed by the condensation of 1,5-dibrorno-3,3di1nethylpentane and cyclopentadicne had the correct boiling point and 1 composition for 5,5-(3,3-dimethylpentamethylene) -1,3-cyclopentadiene and also formed a maleic anhydride adduct having the proper carben and hydrogen content. This condensation product of an alpha, omega-dihaloalkane and a cycloalkadiene is a member of a new class of 1 hydrocarbons, namely, a conjugated diolefin containing a spiro carbon atom. Also the hydro- Calcd. for C12H18Z c,
genation of such a conjugated cyclodiolefln containing a spiro carbon atom yields a saturated spirohydrocarbon. Some of the saturated spirohydrocarbons which may be formed by this 6 which comprises reacting an alpha, omega-d1- halo- -dimethylalkane and a sodium addition compound of a cycloalkadiene containing a methylene group attached to two double bonded process also contained two quaternary carbon 5 carbon atoms to form a diolefinic spirohydroatoms, that is, a quaternary carbon atom in addicarbon having two quaternary carbon atoms and tion to the spiro carbon atom. hydrogenating said diolefinic spirohydrocarbon to form a saturated spirohydrocarbon having two Example HI quaternary carbon atoms.
Reaction products obtained in Examples I and 3. A process for producing a spirohydrocarbon II and consisting essentially of dimethylpentawhich comprises reacting 1,5-dibromo-3,3-dlmethylenecyclopentadiene were combined and methylpentane and disodium cyclopentadiene to the resulting 10.6 cc. of liquid hydrocarbon was form 5,5-(3,3-dimethylpentamethy1ene) -1,3-cydissolved in 11 cc. of n-pentane and hydrogenated clopentadiene. at a temperature of from 50 to 75 C. in the 15 4. A process for producing a spirohydrocarbon presence of a nickel-diatomaceous earth catalyst. which comprises reacting 1,5-dibromo-3,3-di- The hydrogenation product was filtered to sepmethylpentane and disodium cyclopentadiene to arate the pentane solution from the catalyst. form 5,5-(3,3-dimethylpentamethylene)-1,3-cy- The pentane solution was then distilled and sepclopentadiene, and hydrogenating the latter arated into fractions with the following propercompound to form 8,8-dimethylspiro[4.5l-deties: cane.
A Below 2. 0 Below 175 41 g. (Pentane) 1 Determined with thermometer in liquid in test tube. 2 Slightly unstable to nitrating mixture.
Analysis of cut 4, Calcd. for 0121-122: C, 86.65; 5 5. A process for producing a spirohydrocarbon H, 13.35. Found: C, 86.79; H, 13.11. which comprises reacting 1,5-dibromo-3,3-di
Analysis of cut 3. Found: C, 85.51; H, 12.20. methylpentane and disodium cyclopentadiene in Fraction 4 consisted essentially of 8,8-diliquid ammonia to form 5,5-(3,3-dimethylpentamethylspiro[4.5l-decane which may also be remethylene)-1,3-cyclopentadiene, and hydrogenferred to as 1,1tetramethylene-4,4-dimethylcyating the latter compound to form 8,8-dimethylclohexane. spiro [4.5] -decane.
The cyclic diolefins preferred for use in this 6. A process for producing a spirohydrocarbon process are those containing a methylene group which comprises reacting 1,5-dibromo-3,3di- (that is, -CH2) attached to two doubly bonded methylpentane and disodium cyclopentadiene in carbon atoms of the diolefin. Such cyclic diole- 45 the presence of an alcohol and a sodium alkoxide fins include, for example, cyclopentadiene, 1.4- at a temperature of from about 10 to about cyclohexadiene, and the like. The hydrogen 100 0., to form 5,5-(3,3-dimethylpentamethylatoms in this particular kind of methylene group one) -1,3-cyclopentadiene and hydrogenating the are replaceable by an alkali metal such as sodium, latter compound in the presence of a nickel catpotassium, etc., and an alkali metal substituted alyst to form 8,8-dimethylspiro[4.5l-decane. cyclic diolefin is formed which is herein referred '7. 5,5-(3,3-dimethylpentamethylene) 1,3 cyto as an alkali metal addition compound of a clopentadiene. cycloalkadiene. LOUIS SCHMERLING.
I claim as my invention:
1. A process for producing a spirohydrocar- REFERENCES CITED bon which comprises condensing an alkali metal h cycloalkadlene containing a methylene group atigi z rferences are of record in t e tached to two double bonded carbon atoms and me 0 15 a dihaloalkane having the structure represented UNITED STATES PATENTS by the formula: Number Name Date R R 2,407,214 Birch et al Sept. 10, 1946 .ox OTHER REFERENCES Marvel et al.: Jour. Am. Chem. Soc., vol. 63, where R, R, R and R' are selected from the 55 3 -2 (1941) group consisting of hydrogen and alkyl radicals, Thiele! Berlchte. VOL 53-71 901)- X represents a halogen and n is an integer from Taylor 8t Jour- Chem 702 1 to 5 inclusive and the unsatisfied valences of (1941)- the group Alder et al.: Annalen, vol. 524, 164-6 (1936). Levitz et al.: Jour. Org. Chem., vol. 8, 253-255 o-(w-o (1943).
I Meyer: Synthese der Kohlenstofi-Verbendunare combined with a member of the group congen, Erste Teil, 1. Halfte, pub. by Julius Springer sisting of hydrogen and an alkyl radical. (1938) Vienna, page 379.
2. A process for producing a spirohydrocarbon 76

Claims (1)

1. A PROCESS FOR PRODUCING A SPIROHYDROCARBON WHICH COMPRISES CONDENSING AN ALKALI METAL CYCLOALKADIENE CONTAINING A METHYLENE GROUP ATTACHED TO TWO DOUBLE BONDED CARBON ATOMS AND A DIHALOALKANE HAVING THE STRUCTURE REPRESENTED BY THE FORMULA:
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647081A (en) * 1951-03-23 1953-07-28 Research Corp Photochemical preparation of tropilidenes
US2716662A (en) * 1952-01-24 1955-08-30 Exxon Research Engineering Co Polycyclic dibasic acids
US2763700A (en) * 1952-10-01 1956-09-18 Du Pont Preparation of sodium derivatives of weakly acidic hydrocarbons
US2777887A (en) * 1953-11-24 1957-01-15 Du Pont Process for preparing cyclopentadienylsodium
US2818416A (en) * 1952-12-10 1957-12-31 Ethyl Corp Cyclomatic compounds
US2835712A (en) * 1955-07-11 1958-05-20 Ziegler Process for the production of calcium compounds of cyclopentadiene and its alkylated, aralkylated, and arylated derivatives
US2848506A (en) * 1954-04-29 1958-08-19 Hercules Powder Co Ltd Preparation of cyclopentadienylsodium
US2951057A (en) * 1953-07-13 1960-08-30 Exxon Research Engineering Co Cyclo-diene silane derivatives
US2953553A (en) * 1957-12-20 1960-09-20 Phillips Petroleum Co Catalytic polymerization
US2957901A (en) * 1954-04-20 1960-10-25 Pittsburgh Plate Glass Co Cyclopentadienyltrialkoxysilanes and derivatives thereof
US2974157A (en) * 1954-08-04 1961-03-07 Union Carbide Corp Cyclopentadienyl vinyl silanes and process for making same
US3067265A (en) * 1959-12-07 1962-12-04 Nat Distillers Chem Corp Dihalides from dialkali metal hydrocarbons

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2407214A (en) * 1942-07-01 1946-09-10 Anglo Iranian Oil Co Ltd Production of an aviation or motor fuel or an aviation or motor fuel constituent

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2407214A (en) * 1942-07-01 1946-09-10 Anglo Iranian Oil Co Ltd Production of an aviation or motor fuel or an aviation or motor fuel constituent

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2647081A (en) * 1951-03-23 1953-07-28 Research Corp Photochemical preparation of tropilidenes
US2716662A (en) * 1952-01-24 1955-08-30 Exxon Research Engineering Co Polycyclic dibasic acids
US2763700A (en) * 1952-10-01 1956-09-18 Du Pont Preparation of sodium derivatives of weakly acidic hydrocarbons
US2818416A (en) * 1952-12-10 1957-12-31 Ethyl Corp Cyclomatic compounds
US2951057A (en) * 1953-07-13 1960-08-30 Exxon Research Engineering Co Cyclo-diene silane derivatives
US2777887A (en) * 1953-11-24 1957-01-15 Du Pont Process for preparing cyclopentadienylsodium
US2957901A (en) * 1954-04-20 1960-10-25 Pittsburgh Plate Glass Co Cyclopentadienyltrialkoxysilanes and derivatives thereof
US2848506A (en) * 1954-04-29 1958-08-19 Hercules Powder Co Ltd Preparation of cyclopentadienylsodium
US2974157A (en) * 1954-08-04 1961-03-07 Union Carbide Corp Cyclopentadienyl vinyl silanes and process for making same
US2835712A (en) * 1955-07-11 1958-05-20 Ziegler Process for the production of calcium compounds of cyclopentadiene and its alkylated, aralkylated, and arylated derivatives
US2953553A (en) * 1957-12-20 1960-09-20 Phillips Petroleum Co Catalytic polymerization
US3067265A (en) * 1959-12-07 1962-12-04 Nat Distillers Chem Corp Dihalides from dialkali metal hydrocarbons

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