GB1581359A - Substituted acetylenic compounds - Google Patents
Substituted acetylenic compounds Download PDFInfo
- Publication number
- GB1581359A GB1581359A GB22108/77A GB2210877A GB1581359A GB 1581359 A GB1581359 A GB 1581359A GB 22108/77 A GB22108/77 A GB 22108/77A GB 2210877 A GB2210877 A GB 2210877A GB 1581359 A GB1581359 A GB 1581359A
- Authority
- GB
- United Kingdom
- Prior art keywords
- general formula
- hydrogen
- compounds
- process according
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 4
- 239000000543 intermediate Substances 0.000 claims abstract description 4
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 claims description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000002140 halogenating effect Effects 0.000 claims description 7
- -1 phenylalkyl carboxylic acids Chemical class 0.000 claims description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 5
- 239000012433 hydrogen halide Substances 0.000 claims description 5
- DXYPQRPGSNUBFO-UHFFFAOYSA-N 1-bromo-3-prop-1-ynylbenzene Chemical group CC#CC1=CC=CC(Br)=C1 DXYPQRPGSNUBFO-UHFFFAOYSA-N 0.000 claims description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000003435 aroyl group Chemical group 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- QSHLXVTVXQTHBS-UHFFFAOYSA-N 1-(3-bromophenyl)propan-1-one Chemical compound CCC(=O)C1=CC=CC(Br)=C1 QSHLXVTVXQTHBS-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 abstract 1
- 230000026030 halogenation Effects 0.000 abstract 1
- 238000005658 halogenation reaction Methods 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229960005235 piperonyl butoxide Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/24—Halogenated aromatic hydrocarbons with unsaturated side chains
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The compounds of formula I, in which R<1> is H, alkyl, aralkyl or diaralkyl, R<2> is H or a halogen and R<3> is H, alkyl, aralkyl, aryl, aryloxy, benzoyl or 2-thienocarbonyl, R<2> and R<3> not being simultaneously H, are obtained by halogenation of a ketone of formula II, followed by dehydrohalogenation of the intermediate halogenated derivative of formula III by means of a strong base. The compounds of formula I are useful as intermediates for the preparation of pharmaceutically active compounds. <IMAGE>
Description
(54) SUBSTITUTED ACETYLENIC COMPOUNDS
(71) We, CHINOIN GYOGYSZER ES VEGYESZETI TERMEKEK GYARA
RT., a body corporate organised under the laws of Hungary, of 1-5 To u., Budapest
IV, Hungary, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to new substituted phenyl-acetylenes and a process for the preparation thereof. The new phenylacetylenes have the general formula I
wherein
(a) R' is alkyl of 5 or 6 carbon atoms or diaralkyl wherein the alkyl moiety has 2-6 carbon atoms;
R2 is hydrogen or halogen; and
R3 is hydrogen, alkyl having I to 6 carbon atoms, aralkyl having 1 to 6 atoms in the alkyl moiety, aryl or aryloxy or an aroyl group of the general formula ArCO, wherein Ar is phenyl or a 2-thienyl group;
with the proviso that R2 and R3 are not both hydrogen; or (b) RX is hydrogen, alkyl having 1 to 6 carbon atoms, aralkyl wherein the alkyl moiety has 1 to 6 carbon atoms, or diaralkyl wherein the alkyl moiety has 2 to 6 carbon atoms,
R2 is halogen; and
R3 is hydrogen; with the proviso that when R1 is methyl and R3 is hydrogen, R2 is not m-chloro, p-chloro, p-bromo or pfluoro.
The new compounds of the formula I can be prepared by reacting a compound of the general formula II
wherein the substituents are as defined above, with a halogenating agent, preferably with a phosphorus halide, and reacting the compounds thus obtained of the general formula III
wherein the substituents are as defined above, if desired without isolation, with a strong base.
According to an advantageous embodiment of the present invention, compounds of the general formula II are reacted with phosphorus pentachloride without any solvent or in an organic inert solvent, such as diethylether at a temperature of 20 to 1000C, preferably at the boiling point of the solvent. The reaction may be carried out in the solvent, preferably, at a temperature of 50 to 900 C.
The hydrogen halide can be split off with strong bases, preferably with alkali metal hydroxides, such as potassium hydroxide or alkali metal alcoholates, such as sodium methoxide or sodium or potassium tert.
butoxide, preferably in an organic solvent.
As an organic solvent alcohols, or aromatic hydrocarbons, preferably toluene, may be used.
Hydrogen halides are preferably split off with sodium methoxide and as a solvent preferably dimethylsulfoxide or dimethylformamide are used.
The hydrogen halide is split off preferably at 20 to 1300C, advantageously at the boiling point of the solvent employed; the preferred solvent dimethylsulfoxide boils at 70"C.
On a large-scale the hydrogen halide may be split off by subjecting the halo-olefin of general formula III to dehydrohalogenation without purification or isolation.
The phenyl-acetylene compounds of the general formula (I) can be used in the pharmaceutical industry, primarily as intermediates for the preparation of valuable pharmaceutically active phenylalkyl carboxylic acids (cf. our copending Application Serial No.
1,552,202). Hitherto the compounds of the present invention had not been prepared because of technical problems with the known synthetic routes, such as the unavailability of the starting materials. The synthesis of compounds related to those of general formula (I) by the above-described route is further illustrated in our Hungarian
Patent Application No. CI-l668 laid open under number T/15127 (equivalent to our
Spanish Patent No. 459,087).
One embodiment of our invention is illustrated in the following Example.
Example
41.6g. of m-bromo-propiophenone and 52g. of phosphorus pentachloride are heated on a water bath at 750C until evolution of hydrogen chloride ceases, i.e.
for about 20 to 25 minutes. After cooling, the reaction mixture is fractionated in vacuo.
The cut of boiling point 108---112"C at 1.5 mmHg (31g.) is dissolved in 150 ml. of anhydrous toluene, 70g. sodium tert.
butoxide are added and the mixture is heated for 7 hours under vigorous stirring.
The reaction mixture is decomposed with water, the two layers are separated and the aqueous layer is extracted with 3x 100 ml. of toluene. The toluene is distilled off after drying and the residue is fractionated in vacuo. The hot cut boiling at 11-1120C/1.5 mmHg is 1 - (3 - bromophenyl) - 2 methyl - acetylene.
nD4=1.5885.
Analysis:
Calculated: Bromine 40.98 Found: Bromine41.40"/, WHAT WE CLAIM IS:
1. Compounds of the general formula I
wherein
(a) R1 is alkyl of 5 or 6 carbon atoms or diaralkyl wherein the alkyl moiety has 2-6 carbon atoms;
R2 is hydrogen or halogen; and
R3 is hydrogen, alkyl having 1 to 6 carbon atoms, aralkyl having 1 to 6 carbon atoms in the alkyl moiety, aryl or aryloxy or an aroyl group of the general formula ArCO, wherein Ar is phenyl or a 2-thienyl group;
with the proviso that R2 and R3 are not both hydrogen; or (b) R1 is hydrogen, alkyl having 1 to 6 carbon atoms, aralkyl wherein the alkyl moiety has 1 to 6 carbon atoms, or diaralkyl wherein the alkyl moiety has 2 to 6 carbon atoms,
R2 is halogen; and
R3 is hydrogen;
with the provisos that when R1 is methyl and R3 is hydrogen, R2 is not m-chloro, pchloro, p-bromo or p-fluoro.
2. 1 - (3 - Bromophenyl) - 2 - methyl acetylene.
3. A process for the preparation of the compounds of the general formula I as defined in claim 1, which comprises reacting a compound of the general formula II.
wherein the substituents are as defined in claim 1, with a halogenating agent and reacting the corresponding compounds of the general formula III thus obtained
with a strong base.
4. A process according to claim 3 wherein said halogenating agent is a phosphorus halide.
5. A process according to claim 4 wherein said halogenating agent is phosphorus pentachloride.
6. A process according to claim 5 wherein said compound of general formula (III) is reacted with phosphorus pentachloride at 50 to 900C in the absence of a solvent.
7. A process according to claim 5 wherein said compound of general formula (III) is reacted with phosphorus pentachloride at 200 to 1000C in the presence of an organic solvent.
8. A process according to claim 7 wherein the reaction temperature is 50 to 900 C.
9. A process according to any of claims 3 to 8 wherein said strong base is an alkali metal hydroxide or alkali metal alcoholate.
10. A process according to claim 9, which
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (14)
1. Compounds of the general formula I
wherein
(a) R1 is alkyl of 5 or 6 carbon atoms or diaralkyl wherein the alkyl moiety has 2-6 carbon atoms;
R2 is hydrogen or halogen; and
R3 is hydrogen, alkyl having 1 to 6 carbon atoms, aralkyl having 1 to 6 carbon atoms in the alkyl moiety, aryl or aryloxy or an aroyl group of the general formula ArCO, wherein Ar is phenyl or a 2-thienyl group;
with the proviso that R2 and R3 are not both hydrogen; or (b) R1 is hydrogen, alkyl having 1 to 6 carbon atoms, aralkyl wherein the alkyl moiety has 1 to 6 carbon atoms, or diaralkyl wherein the alkyl moiety has 2 to 6 carbon atoms,
R2 is halogen; and
R3 is hydrogen;
with the provisos that when R1 is methyl and R3 is hydrogen, R2 is not m-chloro, pchloro, p-bromo or p-fluoro.
2. 1 - (3 - Bromophenyl) - 2 - methyl acetylene.
3. A process for the preparation of the compounds of the general formula I as defined in claim 1, which comprises reacting a compound of the general formula II.
wherein the substituents are as defined in claim 1, with a halogenating agent and reacting the corresponding compounds of the general formula III thus obtained
with a strong base.
4. A process according to claim 3 wherein said halogenating agent is a phosphorus halide.
5. A process according to claim 4 wherein said halogenating agent is phosphorus pentachloride.
6. A process according to claim 5 wherein said compound of general formula (III) is reacted with phosphorus pentachloride at 50 to 900C in the absence of a solvent.
7. A process according to claim 5 wherein said compound of general formula (III) is reacted with phosphorus pentachloride at 200 to 1000C in the presence of an organic solvent.
8. A process according to claim 7 wherein the reaction temperature is 50 to 900 C.
9. A process according to any of claims 3 to 8 wherein said strong base is an alkali metal hydroxide or alkali metal alcoholate.
10. A process according to claim 9, which
comprises reacting said compound of the general formula (III) with sodium methoxide in the presence of dimethylsulfoxide or dimethylforamide.
I I. A process according to any of claims 3 to 10 wherein said compound of the general formula (III) is reacted with a strong base without isolation.
12. A process according to claim 3 substantially as illustrated in the Example herein.
13. Compounds according to claim 1 whenever made by the process of any of claims 3 to 12.
14. Compounds according to claim 1 wherein R1 is other than hydrogen.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU76CI00001668A HU172938B (en) | 1976-05-25 | 1976-05-25 | Process for producing substituted phenyl-acethylenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1581359A true GB1581359A (en) | 1980-12-10 |
Family
ID=10994618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB22108/77A Expired GB1581359A (en) | 1976-05-25 | 1977-05-25 | Substituted acetylenic compounds |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS52144633A (en) |
| CH (1) | CH622485A5 (en) |
| DK (1) | DK226977A (en) |
| ES (1) | ES459087A1 (en) |
| GB (1) | GB1581359A (en) |
| HU (1) | HU172938B (en) |
| NL (1) | NL7705680A (en) |
| SE (1) | SE431867B (en) |
| SU (1) | SU656499A3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665246A (en) * | 1984-03-09 | 1987-05-12 | Chem Biochem Research, Inc. | Method of producing ethynyl aromatic compounds |
| WO2005037758A1 (en) * | 2003-10-13 | 2005-04-28 | Applied Research Systems Ars Holding N.V. | Method for preparing para-phenyl alkynyl benzaldehydes |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54109952A (en) * | 1978-02-18 | 1979-08-29 | Takayuki Shioiri | 3**fluoroo4**phenylpropiophenone and its manufacture |
| JPS54128553A (en) * | 1978-03-27 | 1979-10-05 | Takayuki Shioiri | Novel 3**benzoylpropiophenone and its manufacture |
| JP2003037511A (en) * | 2001-07-26 | 2003-02-07 | Niigata Seimitsu Kk | Weak signal extraction circuit |
-
1976
- 1976-05-25 HU HU76CI00001668A patent/HU172938B/en unknown
-
1977
- 1977-05-17 SE SE7705840A patent/SE431867B/en unknown
- 1977-05-24 DK DK226977A patent/DK226977A/en not_active Application Discontinuation
- 1977-05-24 CH CH639577A patent/CH622485A5/en not_active IP Right Cessation
- 1977-05-24 NL NL7705680A patent/NL7705680A/en not_active Application Discontinuation
- 1977-05-24 SU SU772484003A patent/SU656499A3/en active
- 1977-05-24 ES ES459087A patent/ES459087A1/en not_active Expired
- 1977-05-25 JP JP5994977A patent/JPS52144633A/en active Pending
- 1977-05-25 GB GB22108/77A patent/GB1581359A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665246A (en) * | 1984-03-09 | 1987-05-12 | Chem Biochem Research, Inc. | Method of producing ethynyl aromatic compounds |
| WO2005037758A1 (en) * | 2003-10-13 | 2005-04-28 | Applied Research Systems Ars Holding N.V. | Method for preparing para-phenyl alkynyl benzaldehydes |
| US7479575B2 (en) | 2003-10-13 | 2009-01-20 | Laboratoires Serono Sa | Method for preparing para-phenyl alkynyl benzaldehydes |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7705680A (en) | 1977-11-29 |
| SE7705840L (en) | 1977-11-26 |
| CH622485A5 (en) | 1981-04-15 |
| SE431867B (en) | 1984-03-05 |
| SU656499A3 (en) | 1979-04-05 |
| HU172938B (en) | 1979-01-28 |
| JPS52144633A (en) | 1977-12-02 |
| ES459087A1 (en) | 1978-04-16 |
| DK226977A (en) | 1977-11-26 |
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| Date | Code | Title | Description |
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| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |