US3080418A - Process for the preparation of trans, cis, trans-1, 2, 4-tricarboxy-cis-3-carboxymethylocylopentane - Google Patents

Process for the preparation of trans, cis, trans-1, 2, 4-tricarboxy-cis-3-carboxymethylocylopentane Download PDF

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Publication number
US3080418A
US3080418A US685424A US68542457A US3080418A US 3080418 A US3080418 A US 3080418A US 685424 A US685424 A US 685424A US 68542457 A US68542457 A US 68542457A US 3080418 A US3080418 A US 3080418A
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United States
Prior art keywords
tricarboxy
exo
dihydro
cis
dicyclopentadiene
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Expired - Lifetime
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US685424A
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English (en)
Inventor
Robert H Sullivan
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication date
Priority to NL231511D priority Critical patent/NL231511A/xx
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US685424A priority patent/US3080418A/en
Priority to GB17403/58A priority patent/GB823840A/en
Priority to FR1207769D priority patent/FR1207769A/fr
Priority to DEP21292A priority patent/DE1078120B/de
Application granted granted Critical
Publication of US3080418A publication Critical patent/US3080418A/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4215—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof cycloaliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof

Definitions

  • the present invention relates to a new alicyclic tetracarboxylic acid and to its dianhydride. More particularly, the present invention relates to a new geometric isomer of l,2,4-tricarboxy-3-carboxymethylcyclopentane and to the dianhydride thereof.
  • the four ring substituents of l, ,4-tricarboxy-3-carboxyrnethylcyclopentane may be arranged in a variety of ditferent configurations with respect to each other depending upon which side of the plane of the alicyclic nucleus they are situated.
  • the present invention involves the 1,2,4 tricarboxy 3 carboxymethylcyclopentane in which a pair of the ring substituents lie on one side of the alicyclic nucleus and the remaining pair lie on the opposite side. in this arrangement, it may be said that one pair of the ring substituents are trans with respect to the other pair.
  • the new acid of the present invention may be designated as trans,cis,trans-l,2,4 tricarboxy cis 3 carboxymethylcyclopentane.
  • Another, perhaps more appropriate manner of naming this compound is with the use of parenthetical arrows to indicate the relative positions of the various ring substituents.
  • the new isomer of the present invention would be l(l),2(t),4(l)-tricarboxy-3(*U-carboxymethylcyclopentane.
  • dicyclopentcnyl alcohol oxidizing or -hydroxy-S,fi-dihydroexo-dicyclopentadiene
  • dicyclopentcnyl alcohol oxidizing or -hydroxy-S,fi-dihydroexo-dicyclopentadiene
  • Dicyclopentenyl alcohol may be obtained by direct hydration of dicyclopenta diene which, in turn, is readily available in commercial quantities from the high temperature cracking of natural gas and petroleum oils as well as from coal tar.
  • the oxidation may be performed with nitric acid or other suitable oxidizing media in the presence of suitable catalysts.
  • the invention is illustrated by the following examples:
  • Example 1 A mixture of 3909 grams of 70% nitric acid and 3.0
  • the product a white solid, was washed with glacial acetic acid and dried. It was then recrystallized from additional glacial acetic acid.
  • the compound had a melting point of 136-187 C. It was identified by neutral equivalent and infrared absorption techniques as l(l),2(1 ),4(-l) tricarboxy 3Q) carboxymethylcyclopentane.
  • Example 2 Three thousand parts of 70% nitric acid was heated to 55 C. and a few grains (a pinch) of sodium nitrite was added. Then 353 parts of dicyclopentenyl alcohol was added dropwise, with stirring, over 3 hours at a rate such that the temperature of the mixture did not rise above 60 C. After being stirred for two additional hours at 55-60 C., the reaction mixture was concentrated, at reduced pressure, to a total weight of approximately 1500 parts. After the mixture stood for 2-3 days, the solids which separated were collected on a sintered glass funnel and sucked as dry as possible. The filter cake was slurried with 157 parts of acetic acid, filtered, and washed with two 50-part portions of acetic acid.
  • Example 3 A pinch of sodium nitrite was added to 3,000 grams of 70% HNO heated to 59 C, and 450 grams of 5- or 6-acetorry-dihydro-exo-dicyclopentadicnc was added dropwise over 3 hours, the temperature being maintained at 5560 C. he reaction mixture was concentrated under reduced pressure, and the product crystallized out upon standing. After slurrying in acetic acid, 19 1.5 grams ct material melting at l8l-4 C. was obtained. Upon recrystallization from boiling acetic acid, the melting point was raised to 187-8 C., and the product was i entitled as 1(l),2(1),4(J/) tricarboxy 30p) carboxymethyl yclopcntane.
  • Bicyclopenteuyl alcohol may be prepared from clicyclopentadiene with 2.125% sulfuric acid according to the technique of Bruson and Riener described in I. Am. Chem. Soc. vol. 67, pages 723-3 (1945).
  • the alcohol is used for the oxidation step rather than the dicyclopentadiene itself because the latter tends to polymerize and char in an oxidizing environment.
  • the carboxylic acid esters of dicyclopentenyl alcohol may be obtained by direct esteriiication of the alcohol or by the sulfuric acid catalyzed addition of the acid to dicyclopentadiene, as described in I. Am. Chem. Soc, vol.
  • the starting material of Example 2 may be prepared from dicyclopentadiene and acetic acid, or by direct esteriiication of dicyclopen tenyl alcohol with acetic acid.
  • the ester group does not enter into the reaction, and the new compound of the present invention may thus be prepared from dicyclopentenyl alcohol and/or from any ester thereof which is hydrolyzable to the alcohol.
  • the nature or structure of the ester group, i.e., of the acid from which the ester is prepared, is in no sense critical to the invention. For economic reasons, the esters of simple, readily-available aliphatic and aromatic acids, like acetic acid and benzoic acid, are preferred starting materials as is the dicyclopentenyl alcohol itself.
  • nitric acid having an initial concentration of about 30-75% is operable. With nitric acid below about 30% concentratiomthe reaction is too slow to be of any practical significance. Nitric acid stronger than about 75% tends to overoxidize the alcohol which leads to the formation of oxalic acid. Though oxidation with nitric acid represents the preferred procedure, other conventional oxidizing agents are operable including, for example, chromic acid and the like. I
  • a catalyst is not essential to the oxidation. It is often very advantageous, however, since the presence of a catalystwill frequently accomplish better yields at lower temperatures, and sometimes with less nitric acid than would otherwise be required.
  • Suitable catalysts include pulverized cobalt, nickel or vanadium, as well as the oxides of vanadium, tantalum, lead, manganese, cobalt, chromium, and molybdenum, etc.
  • sodium nitrite tends to promote the reaction by initiating the formation of oxides of nitrogen which tend to encourage the oxidation, as is well-known in the art. This is not a critical feature of the invention, however, inasmuch as the oxidation may be carried out in the absence of sodium nitrite as well as Without a catalyst.
  • the temperature of the reaction mass must be kept below about 75 C. This is necessary in order to prevent overoxidati'on.
  • the reaction' may be conveniently performed anywhere in the range of about 30 to 60 C. and this represents the preferred opera-ting range. Atmospheric pressure is suitable though increased pressure may facilitate the reaction in some instances.
  • 1(l),2(),4(l) tricarboxy 3(1) carboxymethylcyclopentane is a white solid melting at 136-187 C. It is soluble in water and in lower aliphatic alcohols as well as in hydrochloric and glacial ace-tic acids.
  • the dianhydride of the acid is somewhat difficult to prepare due to the presence of the methylene group be tween the carboxyl groups in the 1- and 4-positions. I have found, however, that it is possible to prepare the dianhydride by stirring the free acid with a large excess of acetyl chloride, acetic anhydride or otherdehydrating 6. agents for very long periods.
  • the preparation of the dranhydricle by this technique is illustrated by the following example:
  • Example 4 One part of l(l),2(1 ),4(l)-tricarboxy-3(N-carboxymethylcyclopentane is treated wtih 20 parts of acetyl chloride by stirring at room temperature for 3 to 5 weeks. The resulting solution is concentrated under vacuum to complete dryness. The residue is siurried in a small amount of acetyl chloride. The undissolved product is filtered off and washed with benzene.
  • the diauhydride of 1(l),2(1),4(l)-tricarboxy-3(fl-carboxymethylcyclopentane was obtained in a 39.5% yield, based on the 1 l) ,2 t) ,4 l -tricarboxy-3 (1- -carboxymethylcyclopentane. It melted at l70l72 C. The dianhydride can be converted back to the original acid by hydrolysis.
  • the tetra'butyl ester of 1(l),2(t),4(l)-tricarboxy- 3(T)-curboxymethylcyclopentane which may be formed by esterification of l(l),2(),(4(l) -tricarboxy-3(1)- carboxymethyicyclopentane with n-butanol, may be used as aplasticizer for nitrocellulose.
  • the cure may be eifected by mixing the dianhydride with the resin at moderate temperatures and thereafter'curing the mixture in a mold at elevated temperatures, usually in the neighborhood of about 200 C., for a number of hours.
  • the following example illustrates a typical epoxy cure which is effected with the dianhydride of 1(l) ,2(T) ,4(-l)-tricarboxy-3 (1) -carboxymethylcyclopentane.
  • Example 5 Twenty grams of a typical commercial epoxy resin sold by the Ciba Co. as Araldite 6020 and formed by the condensation of epiehlorohydrin with 4,4-isopropylidenediphenol is mixed with 5.68 grams of the dian'hydride of 1(l),2(1 ),4(l) -tricarboxy-3(1-)-carboxymethylcyclopentane at C. for 10 minutes to give an anhydride/epoxide ratio of 0.55/1. The dispersion was then cured in a mold at 200 C. for 24 hours to give a hard, light brown resin having a heat distortion temperature of 153 C. at 264 p.s.i. fiber stress. The resin showed a flexural strength of 7328 p.s.i. at room temperature, and a fiexural modulus of 044x10 p.s.i. at room temperature. The cured resin is useful as a molding or potting composition, etc.
  • A. process for the preparation of trans,-cis,trans- 1,2,4-t-ricarboxy-cis-3 carboxymethylcyclopcntane which comprises reacting a com-pound selected from the group consisting of (A) S-hydrox-y-S,d-dihydro-exo-dicyclopentadiene, (B) 6-hydroxy-5,6 -dihydro-exo-dicyclopentadiene, (C) the acetic acid ester of 5-hydroxy-5,6-dihydro-exo-dicyclopentadiene, (D) the acetic acid ester of 6-dihydroxy-5,6 -dihydro-exo-dicyclopentadiene, (E) the benzoic acid ester of 5 hydroXy-S,6-dihydro-exo-dicyclopentadicne and (F) the benzoic acid ester of 6- hydroxy-5,6-dihydro-exo-dicyclo

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
US685424A 1957-09-23 1957-09-23 Process for the preparation of trans, cis, trans-1, 2, 4-tricarboxy-cis-3-carboxymethylocylopentane Expired - Lifetime US3080418A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL231511D NL231511A (OSRAM) 1957-09-23
US685424A US3080418A (en) 1957-09-23 1957-09-23 Process for the preparation of trans, cis, trans-1, 2, 4-tricarboxy-cis-3-carboxymethylocylopentane
GB17403/58A GB823840A (en) 1957-09-23 1958-05-30 Improvements in alicyclic tetracarboxylic acids and their derivatives
FR1207769D FR1207769A (fr) 1957-09-23 1958-07-10 Nouvel acide tétracarboxylique alicyclique et son dianhydride et procédé pour leur préparation
DEP21292A DE1078120B (de) 1957-09-23 1958-09-02 Verfahren zur Herstellung von 1, 2, 4-Tricarboxy-3-carboxymethyl-cyclopentan bzw. dessen Anhydrid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US685424A US3080418A (en) 1957-09-23 1957-09-23 Process for the preparation of trans, cis, trans-1, 2, 4-tricarboxy-cis-3-carboxymethylocylopentane

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DE (1) DE1078120B (OSRAM)
FR (1) FR1207769A (OSRAM)
GB (1) GB823840A (OSRAM)
NL (1) NL231511A (OSRAM)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194816A (en) * 1961-12-18 1965-07-13 Copolymer Rubber & Chem Corp Purification of 1, 2, 3, 4-cyclopentanetet-racarboxylic acid and preparation of its anhydride
US9366906B2 (en) 2011-08-25 2016-06-14 Rolic Ag Photoreactive compounds
US9493394B2 (en) 2011-10-03 2016-11-15 Rolic Ag Photoaligning materials
US10696795B2 (en) 2015-11-11 2020-06-30 Rolic Technologies AG Photoaligning materials

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1141988B (de) * 1960-04-28 1963-01-03 Grace W R & Co Verfahren zur Herstellung von 2, 3, 5-Tricarboxycyclopentylessigsaeure
US3242206A (en) * 1961-12-18 1966-03-22 Copolymer Rubber & Chem Corp Recycling a portion of the reaction products in an hno3 oxidation of a dicarboxy cycloalkene compound to control the oxidation rate
JP5856147B2 (ja) 2010-04-23 2016-02-09 ロリク アーゲーＲｏｌｉｃ Ａｇ 光配向材料
JP5872039B2 (ja) 2011-08-02 2016-03-01 ロリク アーゲーＲｏｌｉｃ Ａｇ 光配向性材料
JP6200424B2 (ja) 2011-10-03 2017-09-20 ロリク アーゲーＲｏｌｉｃ Ａｇ 光アライニング材料
KR20190067847A (ko) 2016-10-11 2019-06-17 롤릭 테크놀로지스 아게 광배향 공중합체 재료

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1960211A (en) * 1932-11-03 1934-05-22 Dow Chemical Co Preparation of adipic acids
US2615008A (en) * 1945-09-18 1952-10-21 Devoe & Raynolds Co Epoxide resin compositions
US2668807A (en) * 1952-04-08 1954-02-09 Devoe & Raynolds Co Epoxide compositions
US2750411A (en) * 1951-11-14 1956-06-12 Gordon S Fisher Converting alpha-pinene to mixtures of acids
US2782233A (en) * 1955-03-11 1957-02-19 Du Pont Boric tris-(fluorocarboxylic) anhydrides
US2798079A (en) * 1953-12-29 1957-07-02 Universal Oil Prod Co Condensation of aromatic hydrocarbon derivatives with carbohydrates and related materials
US2798080A (en) * 1956-05-10 1957-07-02 Eastman Kodak Co Process of manufacturing mixed anhydrides of carboxylic acids
US2806057A (en) * 1953-02-24 1957-09-10 Shell Dev Hydroxy-substituted tetrahydrophthalic acids, derivatives thereof, and method for producing the same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1960211A (en) * 1932-11-03 1934-05-22 Dow Chemical Co Preparation of adipic acids
US2615008A (en) * 1945-09-18 1952-10-21 Devoe & Raynolds Co Epoxide resin compositions
US2750411A (en) * 1951-11-14 1956-06-12 Gordon S Fisher Converting alpha-pinene to mixtures of acids
US2668807A (en) * 1952-04-08 1954-02-09 Devoe & Raynolds Co Epoxide compositions
US2806057A (en) * 1953-02-24 1957-09-10 Shell Dev Hydroxy-substituted tetrahydrophthalic acids, derivatives thereof, and method for producing the same
US2798079A (en) * 1953-12-29 1957-07-02 Universal Oil Prod Co Condensation of aromatic hydrocarbon derivatives with carbohydrates and related materials
US2782233A (en) * 1955-03-11 1957-02-19 Du Pont Boric tris-(fluorocarboxylic) anhydrides
US2798080A (en) * 1956-05-10 1957-07-02 Eastman Kodak Co Process of manufacturing mixed anhydrides of carboxylic acids

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194816A (en) * 1961-12-18 1965-07-13 Copolymer Rubber & Chem Corp Purification of 1, 2, 3, 4-cyclopentanetet-racarboxylic acid and preparation of its anhydride
US9366906B2 (en) 2011-08-25 2016-06-14 Rolic Ag Photoreactive compounds
US9493394B2 (en) 2011-10-03 2016-11-15 Rolic Ag Photoaligning materials
US10696795B2 (en) 2015-11-11 2020-06-30 Rolic Technologies AG Photoaligning materials
US11098164B2 (en) 2015-11-11 2021-08-24 Rolic Technologies AG Photoaligning materials
US11634544B2 (en) 2015-11-11 2023-04-25 Rolic Technologies AG Photoaligning materials

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DE1078120B (de) 1960-03-24
FR1207769A (fr) 1960-02-18
GB823840A (en) 1959-11-18
NL231511A (OSRAM)

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