IL36722A - Octahydro-1,2,4 methanopentalenyl-5-isocyanate and its production - Google Patents
Octahydro-1,2,4 methanopentalenyl-5-isocyanate and its productionInfo
- Publication number
- IL36722A IL36722A IL36722A IL3672267A IL36722A IL 36722 A IL36722 A IL 36722A IL 36722 A IL36722 A IL 36722A IL 3672267 A IL3672267 A IL 3672267A IL 36722 A IL36722 A IL 36722A
- Authority
- IL
- Israel
- Prior art keywords
- octahydro
- methanopentalenyl
- isocyanate
- production
- benzene
- Prior art date
Links
- 239000012948 isocyanate Substances 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 title description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polycyclic isocyanate Chemical class 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/10—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/573—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/12—Saturated polycyclic compounds
- C07C61/125—Saturated polycyclic compounds having a carboxyl group bound to a condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/12—Saturated polycyclic compounds
- C07C61/125—Saturated polycyclic compounds having a carboxyl group bound to a condensed ring system
- C07C61/135—Saturated polycyclic compounds having a carboxyl group bound to a condensed ring system having three rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Octahydro-1 , 2 , 4-methanopentalenyl-5-isocyanate and its production CIBA-G-EIGY AG C.34916 The present invention relates to a new polycyclic isocyanate, amely octahydro-1,2,4-methanopentalenyl-(5)-isocyanate having the formula I and to a process for the production thereof.
This new isocyanate is an intermediate compound in the production of the corresponding octahydro-1,2,4-methanopentalenyl-(5)-amine, which in turn has valuable therapeutic properties. The production and the utility of the said octahydro-1,2,4-methanopentalenyl-(5)-amine are described in Patent Specification No. 29191.
The compound of formula I can be produced, according to one aspect of the present invention, by thermal decomposition of Qctahydro-l,2,4-methanopentalenyl-(5)-azide in the presence of an inert organic solvent. Suitable inert organic solvents include aromatic hydrocarbons such as benzene, toluene and xylenes, and higher ethers such as dloxane.
The azide starting material can be produced either from the free octahydro-1,2,4-methanopentalenyl-(5)-carboxyllc acid, or from an alk l ester thereof, especially the methyl or ethyl ester* In the former case the free acid is first converted into the acid chloride and then this is reacted with, for example, an alkali metal azide such as sodium azide. In the latter case the alkyl ester may be converted directly into the azide by reaction with hydrazine hydrate and nitrous acid, preferably in the presence of a solvent ("According to a further aspect of the present invention , the subject octahydro-3.,2,4-methanopentalenyl-(5)-isocyanate .can also be prepared from the corresponding hydroxylarnide by heat ...rig. in the presence of a carboxylic acid anhydride such, as, acetic anhydride. The hydroxylarnide starting material may. be prepared .e.g. from the acid chloride by reaction with hydro-xylamirie hydrochloride in the presence, of an inert, organic: solvent and . an organic base such as pyridine. 1 Octahydro-1, 2, -methanopentaleriyl- ( 5) -carboxylic acid;, . f om which the chloride and alkyl esters referred to above lay be Obtained , can be prepared by the process described by H.K.Hall (J. Org. Chem. 25, A2 (i960) ) by the reaction of bi-cyclo[ 2.2.l]-hepta.-2,5-diene (2 , 5-norbornadiene), with aery-' lonitrile in the presence of copper-II acetate , followed by. Alkaline hydrolysis of the. octahydro-l,2,4-methanopentalenyl. - (5)-cyanide so formed.
The following examples illustrate the production of the ew isocyanate of formula I. All parts are given by weight . tir.less otherwise stated and all temperatures are given in degrees centigrade. . 93.6 Parts of sodium azide are dissolved in 1720 parts by volum4 o .50# aqueous acetone and the solution is cooled to 0°. 90 Parts.' .of octahydro-l,2,4-methanopentalenyl-(5)-carboxylic acid chloride are added within 5 to 10 minutes, while the reaction vessel is maintained "at a : temperature of from 0 to 2° by exterior cooling. Oh ■ completion of the addition, the whole is; stirred at ■ 0° · for another 50 minutes. The solution is then extracted, first with ;.000.p£rts by volume of ice cold, benzene, and secondly with. 300 parts by volume of ice cold benzene. The combined benzene . " extracts are then dried with finely pulverised -calcium chloride at a temperature of from 0 to 5°. The calcium chloride is filtered off to leave a solution of octahydro-l,.2,4-methanopentalenyl-(5)-. carboxylic ac I'd, a'zidc. ' ' This solution is then heated for 2 1/2 hours in a steam bath. Nitrogen is developed and the solution foams. The benzene is then, distilled off to leave the octahydro-1 , 2 , 4-methanopentalenyl- ( 5) - isocyinate v/hich boils at a temperature of from 70 to 75°/3 Torr.
EXAMPLE 2 .■ -■ ','■· A mixture of 1S.3 g (0.1 mol) of octahydro-1 , 2 , 4-m.eth--a.iopentalenyl-(5)-carboxylic acid chloride, 6.9 g (0.1 mol) of hydroxylarnine chloride and 8 g of pyridine, in 50. ml of benzene is stirred for SO minutes at 25°. Then 200ml of ice-water are added to the reaction ' mixture and the water is decanted from the oil that separates. The oil is taken up in ether and the ethereal solution is dried over sodium sulphate. The ether is removed by distillation. The oily residue is taken.-up in 150 ml of acetic anhydride and heated to the boiling point for 15 minutes. The reaction mixture is then poured into water and left to stand for 2 hour's. ' The oil that separates is taken'up i ether, the. ethereal solution is dried over sodium sulphate and the ether is removed by distillation. under. , reduced pressure. The residual oil is heated to 200° until the development of gas ceases, and then distilled. The octa- ■ hydro-l,2,4-methenopentalenyl-(5)-is0cyanate thus obtained distills at 70°/3Torr. '·
Claims (1)
1. insufficientOCRQuality
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1837566A CH472364A (en) | 1966-12-22 | 1966-12-22 | Process for the preparation of a new polycyclic amine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| IL36722A true IL36722A (en) | 1971-08-25 |
Family
ID=4432559
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL36722A IL36722A (en) | 1966-12-22 | 1967-12-21 | Octahydro-1,2,4 methanopentalenyl-5-isocyanate and its production |
| IL29191A IL29191A (en) | 1966-12-22 | 1967-12-21 | Octahydro-1,2,4-methenopentalenyl-(5)-amine and its production |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL29191A IL29191A (en) | 1966-12-22 | 1967-12-21 | Octahydro-1,2,4-methenopentalenyl-(5)-amine and its production |
Country Status (8)
| Country | Link |
|---|---|
| AT (3) | AT279582B (en) |
| BR (1) | BR6795727D0 (en) |
| CH (1) | CH495945A (en) |
| ES (1) | ES348511A1 (en) |
| GR (1) | GR37787B (en) |
| IL (2) | IL36722A (en) |
| NO (1) | NO124251B (en) |
| SE (2) | SE342033B (en) |
-
1966
- 1966-12-22 CH CH413069A patent/CH495945A/en not_active IP Right Cessation
-
1967
- 1967-12-21 AT AT02276/69A patent/AT279582B/en active
- 1967-12-21 AT AT1158767A patent/AT278743B/en not_active IP Right Cessation
- 1967-12-21 SE SE10801/70A patent/SE342033B/xx unknown
- 1967-12-21 GR GR670137787A patent/GR37787B/en unknown
- 1967-12-21 AT AT02277/69A patent/AT278745B/en not_active IP Right Cessation
- 1967-12-21 BR BR195727/67A patent/BR6795727D0/en unknown
- 1967-12-21 IL IL36722A patent/IL36722A/en unknown
- 1967-12-21 NO NO171098A patent/NO124251B/no unknown
- 1967-12-21 SE SE17579/67A patent/SE336129B/xx unknown
- 1967-12-21 IL IL29191A patent/IL29191A/en unknown
- 1967-12-21 ES ES348511A patent/ES348511A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NO124251B (en) | 1972-03-27 |
| GR37787B (en) | 1969-07-15 |
| IL29191A (en) | 1971-07-28 |
| AT278745B (en) | 1970-02-10 |
| BR6795727D0 (en) | 1973-04-26 |
| ES348511A1 (en) | 1969-03-01 |
| CH495945A (en) | 1970-09-15 |
| SE336129B (en) | 1971-06-28 |
| SE342033B (en) | 1972-01-24 |
| AT279582B (en) | 1970-03-10 |
| AT278743B (en) | 1970-02-10 |
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