Patent US3985016A successfully refreshed from Google Patents.
US4156683A
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Complexes of macrocyclic compounds
Assignee: Merck Sharp & Dohme LLC
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Filing: 1975-03-20
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Granted: 1979-05-29
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Expires: 1995-03-20
Abstract
Abstract Novel macrocyclic (monocyclic and bicyclic) compounds having nitrogen bridgehead atoms and having in the hydrocarbon bridging chains at least two additional hetero atoms selected from the group consisting of sulfur, oxygen, and nitrogen, when admixed with a compatible cation-donor compound form stable cation-containing macrocyclic complexes which, in turn, can be conveniently dissociated by addition of acid or a quaternizing agent. The novel macrocyclics are valuable for use in the same way and for the same purposes as chelating agents.
Inventors
- 👤 Jean-Marie Lehn
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 18:31
CPC Classifications
C; C07; C07D; C07D209/00; C07D209/02; C07D209/44; C07D209/48; C07C; C07C323/00; C07C323/23; C07C323/24; C07C323/25; C07C51/00; C07C51/16; C07C51/27; C07C59/00; C07C59/125; C07C59/135; C07C59/40; C07C59/58; C07C59/64; C07C59/66; C07C59/68; C07D273/00; C07F; C07F9/00; C07F9/02; C07F9/28; C07F9/50; C07F9/5027; C07F9/54; C07F9/5449
Claims Analysis
Total Claims: 46
Claim 1
Independent Claim
240 words
A cation-containing complex of macrocyclic compound selected from the group consisting of the following formula I: ##STR93## wherein R 1 and R 2 are members selected from the group consisting of hydrogen, a hydrocarbon radical having up to 12 carbon atoms, and together R 1 and R 2 form a grouping of the following formula II: ##STR94## wherein each A is a hydrocarbon radical having from 2to 8 carbon atoms; each D is a member selected from the group consisting of oxygen, sulfur, a hydrocarbon radical having up to 8 carbon atoms, and ═N--R (R being a member selected from the group consisting of hydrogen, a hydrocarbon radical having up to 12 carbon atoms, an aryl hydrocarbonsulfonyl radical having up to 12 carbon atoms, a lower alkoxycarbonyl radical, a lower alkoxycarbonylmethylene radical and a carboxymethylene radical); at least two of aid D members being hetero-substituents selected from the group consisting of oxygen, sulfur and ═N--R; and when each of R 1 and R 2 are members selected from the group consisting of hydrogen and a hydrocarbon radical, one of said two hetero-substituents is selected from the group consisting of oxygen and sulfur, the other of said two hetero-substituents is selected from the group consisting of oxygen and ═N--R; m, n and p are integers from 0 to 5; and wherein said cation is a member selected from the group consisting of a compatible metal cation and a compatible ammonium cation.
Claim 2
Dependent Claim
240 words
A cation-containing complex of macrocyclic compound selected from the group consisting of the following formula I: ##STR93## wherein R 1 and R 2 are members selected from the group consisting of hydrogen, a hydrocarbon radical having up to 12 carbon atoms, and together R 1 and R 2 form a grouping of the following formula II: ##STR94## wherein each A is a hydrocarbon radical having from 2to 8 carbon atoms; each D is a member selected from the group consisting of oxygen, sulfur, a hydrocarbon radical having up to 8 carbon atoms, and ═N--R (R being a member selected from the group consisting of hydrogen, a hydrocarbon radical having up to 12 carbon atoms, an aryl hydrocarbonsulfonyl radical having up to 12 carbon atoms, a lower alkoxycarbonyl radical, a lower alkoxycarbonylmethylene radical and a carboxymethylene radical); at least two of aid D members being hetero-substituents selected from the group consisting of oxygen, sulfur and ═N--R; and when each of R 1 and R 2 are members selected from the group consisting of hydrogen and a hydrocarbon radical, one of said two hetero-substituents is selected from the group consisting of oxygen and sulfur, the other of said two hetero-substituents is selected from the group consisting of oxygen and ═N--R; m, n and p are integers from 0 to 5; and wherein said cation is a member selected from the group consisting of a compatible metal cation and a compatible ammonium cation.
Claim 3
Dependent Claim
12 words
A cation-containing complex according to claim 1 wherein each A is ethylene.
Claim 4
Dependent Claim
48 words
A cation-containing complex of claim 1 of a macrocyclic compound of formula I wherein R 1 and R 2 are hydrogen; D is a member selected from the group consisting of sulfur and oxygen; A is ethylene; and m, n and p are integers from 0 to 3.
Claim 5
Dependent Claim
33 words
A cation-containing complex of claim 1 of a macrocyclic compound of formula I wherein each D is oxygen; each A is ethylene; and m, n and p are integers from 0 to 3.
Claim 6
Dependent Claim
39 words
A cation-containing complex of claim 1 of a macrocyclic compound of formula I wherein R 1 and R 2 together form the grouping ##STR95## each A being ethylene; and m, n and p being integers from 0 to 3.
Claim 7
Dependent Claim
53 words
A cation-containing complex of claim 1 of a macrocyclic compound of formula I wherein R 1 and R 2 together form the grouping ##STR96## each D being a member selected from the group consisting of oxyen and sulfur; each A being ethylene; and m, n and p being integers from 0 to 3.
Claim 8
Dependent Claim
74 words
A cation-containing complex of claim 1 of a macrocyclic compound of formula I wherein R 1 and R 2 together form the grouping ##STR97## each D being a member selected from the group consisting of oxygen and ═N--R (R being a member selected from the group consisting of hydrogen and a hydrocarbon radical having up to 12 carbon atoms); each A being ethylene; and m, n and p being integers from 0 to 2.
Claim 9
Dependent Claim
42 words
A cation-containing complex of clam 1 of a compound of formula I wherein R 1 and R 2 together form the grouping ##STR98## each D is oxygen; each A is ethylene; and m, n and p are integers from 0 to 2.
Claim 10
Dependent Claim
42 words
A cation-containing complex of clam 1 of a compound of formula I wherein R 1 and R 2 together form the grouping ##STR98## each D is oxygen; each A is ethylene; and m, n and p are integers from 0 to 2.
Claim 11
Dependent Claim
14 words
A compound according to claim 1 which is the potassium thiocyanate complex of 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane.
Claim 12
Dependent Claim
14 words
A compound according to claim 1 which is the cupric chloride complex of 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane.
Claim 13
Dependent Claim
14 words
A compound according to claim 1 which is the rubidium thiocyanate complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo-[8,8,8]hexacosane
Claim 14
Dependent Claim
14 words
A compound according to claim 1 which is the barium chloride complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane.
Claim 15
Dependent Claim
14 words
A compound according to claim 1 which is the potassium hydroxide complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane.
Claim 16
Dependent Claim
14 words
A compound according to claim 1 which is the thallium formate complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane.
Claim 17
Dependent Claim
14 words
A compound according to claim 1 which is the calcium thiocyanate complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]exacosane.
Claim 18
Dependent Claim
14 words
A compound according to claim 1 which is the zinc borofluoride complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane.
Claim 19
Dependent Claim
14 words
A compound according to claim 1 which is the lead thiocyanate complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane.
Claim 20
Dependent Claim
14 words
A compound according to claim 1 which is the caesium thiocyanate complex of 4,7,10,16,19,22,27,30,33-nonoxa-1,13-diazabicyclo[11,11,11]pentatriacontane.
Claim 21
Dependent Claim
14 words
A compound according to claim 1 which is the potassium thiocyanate complex of 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8,8,5]tricosane.
Claim 22
Dependent Claim
14 words
A compound according to claim 1 which is the cobalt thiocyanate complex of 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8,8,5]tricosane.
Claim 23
Dependent Claim
15 words
A compound according to claim 1 which is the barium chloride complex of 4,7,13,16,21-pentaoxa-1,10 diazabicyclo[8,8,5]tricosane.
Claim 24
Dependent Claim
14 words
A compound according to claim 1 which is the nickel borofluoride complex of 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8,8,5]tricosane.
Claim 25
Dependent Claim
14 words
A compound according to claim 1 which is the cupric borofluoride complex of 4,7,13,16,21-pentaoxa-1,10-diazabicyclo8,8,5]tricosane.
Claim 26
Dependent Claim
14 words
A compound according to claim 1 which is the barium thiocyanate complex of 4,7,10,16,19,24,27-heptaoxa-1,13-diazabicyclo[8,8,11]nonacosane.
Claim 27
Dependent Claim
14 words
A compound according to claim 1 which is the potassium hydroxide complex of 4,7,13,18-tetraoxa-1,10-diazabicyclo[5,5,8]eicosane.
Claim 28
Dependent Claim
18 words
A compound according to claim 1 which is a cation-containing complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane wherein said cation is strontium.
Claim 29
Dependent Claim
44 words
A compound according to claim 1 which is the cation-containing complex of 4,11,17,20,25,28-hexaoxa-1,4-diazatricyclo [12,8,8,0 5 ,10 ]triaconta-5,7,9-triene with a member selected from the group consisting of LiSCN, NaSCN, KSCN, RbCl, CsCl, AgSCN, TlNO 3 , CaBr 2 , SrCl 2 and Ba(SCN) 2 .
Claim 30
Dependent Claim
44 words
A compound according to claim 1 which is the cation-containing complex of 4,11,17,24,29,32-hexaoxa-1,14-diazatetracyclo [12,12,8,0 5 ,10,18,25,23 ]tetratriaconta-5,7,9,18,20,22-hexaene with a member selected from the group consisting of LiSCN, NaSCN, KSCN, RbCl, CsCl, AgSCN, TlNO 3 , CaBr 2 , SrCl 2 and Ba(SCN) 2 .
Claim 31
Dependent Claim
29 words
A compound according to claim 1 which is the cation-containing complex of 4,11,17,22-tetraoxa-1,14-diazatricyclo[12,5,5,0 5 ,10 ]tetracosa-5,7,9-triene with a member selected from the group consisting of LiSCN, NaSCN, and KSCN.
Claim 32
Dependent Claim
14 words
A compound according to claim 1 which is the silver nitrate complex of 21,24-ditosyl-4,7,13,16-tetraoxa-1,10,21,24-tetraazabicyclo[8,8,8]hexacosane.
Claim 33
Dependent Claim
28 words
A compound according to claim 1 which is the cation-containing complex of 4,7,13,16-tetraoxa-1,10,21,24-tetraazabicyclo[8,8,8]hexacosane with a member selected from the group consisting of NaSCN, KSCN, and CdCl 2 .
Claim 34
Dependent Claim
14 words
A compound according to claim 1 which is the potassium thiocyanate complex of 21,24-dioxa-1,4,7,10,13,16-hexaazabicyclo[8,8,8]hexacosane.
Claim 35
Dependent Claim
27 words
A compound according to claim 1 which is the cation-containing complex of 21,24-dimethyl-4,7,16,19-tetraoxa-1,10,21,24-tetraazabicyclo[8,8,8]hexacosane with a member selected from the group consisting of potassium nitrate and silver nitrate.
Claim 36
Dependent Claim
15 words
A compound according to claim 1 which is the potassium nitrate complex of 13,16,21,24-tetramethyl-4,7 dioxa-1,10,13,16,21,24-hexaazabicyclo[8,8,8]hexacosane.
Claim 37
Dependent Claim
14 words
A compound according to claim 1 which is the potassium chloride complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane.
Claim 38
Dependent Claim
47 words
A macrocyclic compound according to claim 1 which is a cation-containing complex of a macrocyclic compounds wherein D is oxygen; A is ethylene; R 1 and R 2 are each a hydrocarbon radical having up to 12 carbon atoms, and m and n are the integer 1.
Claim 39
Dependent Claim
21 words
The process for the preparation of the potassium hydroxide complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane which comprises admixing 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane with potassium hydroxide in tetrahydrofuran.
Claim 40
Dependent Claim
21 words
The process for the preparation of the potassium hydroxide complex of 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane which comprises admixing 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane with potassium hydroxide in tetrahydrofuran.
Claim 41
Dependent Claim
21 words
The process for the preparation of the potassium hydroxide complex of 4,7,13,18-tetraoxa-1,10-diazabicyclo[5,5,8]eicosane which comprises admixing 4,7,13,18-tetraoxa-1,10-diazabicyclo[5,5,8]eicosane with potassium hydroxide in tetrahydrofuran.
Claim 42
Dependent Claim
21 words
The process for the preparation of the potassium hydroxide complex of 4,7,13,18-tetraoxa-1,10-diazabicyclo[5,5,8]eicosane which comprises admixing 4,7,13,18-tetraoxa-1,10-diazabicyclo[5,5,8]eicosane with potassium hydroxide in tetrahydrofuran.
Claim 43
Dependent Claim
107 words
The process which comprises treating a cation-containing complex of a compound of formula I as defined in claim 1, with a member selected from the group consisting of an acid and a quaternizing agent and, when said compound of formula I is a bicyclic compound wherein R 1 and R 2 form a grouping of formula II therein, with a per-acid, whereby said complex is dissociated and there is obtained a salt containing said cation and an acid addition or a quaternary ammonium salt, respectively, of said macrocyclic compound of formula I, claim 1, or an N-oxide salt of said bicyclic compound of formula I, claim 1.
Claim 44
Dependent Claim
36 words
The process of claim 39 wherein said cation-containing complex is treated with an acid whereby there is obtained an acid addition salt of said compound of formula I, claim 1, and a salt containing said cation.
Claim 45
Dependent Claim
38 words
The process of claim 40 wherein said cation-containing complex is treated with hydrochloric acid whereby there is obtained a hydrogen chloride acid addition salt of said compound of formula I, claim 1, and a salt of said cation.
Claim 46
Dependent Claim
75 words
A cation-containing complex of claim 1 wherein said cation is a compatible metal cation selected from the group consisting of Li + , Na + , K + , Rb + , Cs + , Mg ++ , Ca.sup. ++, Sr ++ , Ba ++ , NH 4 + , Co ++ , Ni ++ , Cu ++ , Zn ++ , Ag + , Cd ++ , Pb ++ , and Tl + .
References Cited (Backward Citations)
US3562295A
Cited
US3686225A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1982-05-28 | 1982-11-27 | 1983-05-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1986-05-28 | 1986-11-27 | 1987-05-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1990-05-28 | 1990-11-27 | 1991-05-29 | $7700.00 | Window Closed / Lapsed |