GB1237232A – Production of cis-1,2-propenylphosphonic acid
– Google Patents
GB1237232A – Production of cis-1,2-propenylphosphonic acid
– Google Patents
Production of cis-1,2-propenylphosphonic acid
Info
Publication number
GB1237232A
GB1237232A
GB50628/68A
GB5062868A
GB1237232A
GB 1237232 A
GB1237232 A
GB 1237232A
GB 50628/68 A
GB50628/68 A
GB 50628/68A
GB 5062868 A
GB5062868 A
GB 5062868A
GB 1237232 A
GB1237232 A
GB 1237232A
Authority
GB
United Kingdom
Prior art keywords
acid
cis
diester
phosphonic acid
ester
Prior art date
1968-05-15
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
Application number
GB50628/68A
Inventor
Edward Joseph Glamkowski
George Gal
Meyer Sletzinger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck and Co Inc
Original Assignee
Merck and Co Inc
Priority date (The priority date 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 date listed.)
1968-05-15
Filing date
1968-10-24
Publication date
1971-06-30
1968-10-24
Application filed by Merck and Co Inc
filed
Critical
Merck and Co Inc
1971-06-30
Publication of GB1237232A
publication
Critical
patent/GB1237232A/en
Status
Expired
legal-status
Critical
Current
Links
Espacenet
Global Dossier
Discuss
Classifications
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
C07F9/02—Phosphorus compounds
C07F9/28—Phosphorus compounds with one or more P—C bonds
C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
C07F9/40—Esters thereof
C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
C07F9/4015—Esters of acyclic unsaturated acids
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
C07F9/02—Phosphorus compounds
C07F9/06—Phosphorus compounds without P—C bonds
C07F9/08—Esters of oxyacids of phosphorus
C07F9/141—Esters of phosphorous acids
C07F9/143—Esters of phosphorous acids with unsaturated acyclic alcohols
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
C07F9/02—Phosphorus compounds
C07F9/06—Phosphorus compounds without P—C bonds
C07F9/08—Esters of oxyacids of phosphorus
C07F9/141—Esters of phosphorous acids
C07F9/146—Esters of phosphorous acids containing P-halide groups
C—CHEMISTRY; METALLURGY
C07—ORGANIC CHEMISTRY
C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
C07F9/02—Phosphorus compounds
C07F9/28—Phosphorus compounds with one or more P—C bonds
C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
C07F9/3826—Acyclic unsaturated acids
Abstract
1,237,232. cis-1,2-propenyl phosphonic acid and intermediates therefor. MERCK & CO. Inc. 24 Oct., 1968 [15 May, 1968], No. 50628/68. Heading C2C. cis-1,2-Propenylphosphonic acid (I) is obtained by reacting phosphorus trichloride with at least two equivalents of a C 1 -C 5 alkyl, or C 2 -C 5 alkenyl alcohol or an alkalkyl alcohol, or a phenol, or with at least one equivalent of a dihydric phenol, e.g. catechol or of a C 2 -C 5 alkylene glycol in an inert organic solvent, reacting the resulting diorgano phosphorochloridite (II) with propargyl alcohol to form a 2- propynyl di-organo-phosphite (III), rearranging the latter to form the corresponding allenyl phosphonic acid diester (IV), hydrogenating the latter to form the cis-1,2-propenyl phosphonic acid diester (V) and cleaving the latter to form the free cis-1,2-propenyl phosphonic acid (I), the process being generally carried out without isolating the intermediate compounds. The 2-propynyl diorganophosphite (III) gradually rearranges on standing to form (IV) but the rearrangement is preferably effected by heating the mixture at 50-100 C. or to reflux, the heating being preferably carried out in an inert atmosphere, e.g. of N 2 or helium. The diester (IV) is then hydrogenated, preferably catalytically, in order to form the diester (V). Suitable hydrogenation catalysts are Pd/C, Pd/CaCO 3 and Raney nickel. The free olefinic acid (I) may be obtained from the cis-olefinic diester (V) by acid or base-acid hydrolysis or where appropriate by pyrolysis in the absence of a solvent. Where, however, the ester group in (IV) is aralkyl or substituted aralkyl, e.g. benzyl or chlorobenzyl, the hydrogenation step additionally serves to remove the ester groups thus yielding (I) directly. When acid is used in the ester cleavage of (V) to (I) the acid may be (I) itself or may be a strong mineral acid or an organic acid, e.g. benzene sulphonic acid or p-toluene sulphonic acid. Acidic ion exchange resins and catalytically acidic surfaces, e.g. sea sand, silica gel or acid washed alumina may also be used. When pyrolysis is used to cleave the ester it is suitably effected at 85-200 C. in the presence or absence of an acid catalyst. The reaction in the first two steps may be carried out in the presence of an acid-binding agent, e.g. a tertiary amine, or an oxide such as propylene oxide. In a modification of the process the allenylphosphonic acid diester (IV) is rearranged to form an α,#-propynylphosphonic acid diester and the latter hydrogenated to produce the cisolefinic diester (V) which is then cleaved. The cis-propenyl phosphonic acid product may be converted to the antimicrobial agent () (cis- 1,2-epoxypropyl)-phosphonic acid by oxidation with H 2 O 2 either directly or by first converting to the monobenzylamine salt prior to the oxidation. The invention also includes per se the compound di-t-butylallenyl phosphonate obtained as an intermediate in the third step of the process using the appropriate reactants.
GB50628/68A
1968-05-15
1968-10-24
Production of cis-1,2-propenylphosphonic acid
Expired
GB1237232A
(en)
Applications Claiming Priority (1)
Application Number
Priority Date
Filing Date
Title
US72944768A
1968-05-15
1968-05-15
Publications (1)
Publication Number
Publication Date
GB1237232A
true
GB1237232A
(en)
1971-06-30
Family
ID=24931069
Family Applications (1)
Application Number
Title
Priority Date
Filing Date
GB50628/68A
Expired
GB1237232A
(en)
1968-05-15
1968-10-24
Production of cis-1,2-propenylphosphonic acid
Country Status (17)
Country
Link
AT
(1)
AT300829B
(en)
BE
(1)
BE723076A
(en)
CH
(1)
CH531013A
(en)
DK
(1)
DK135996B
(en)
ES
(1)
ES359534A1
(en)
FI
(1)
FI51356C
(en)
FR
(1)
FR1590372A
(en)
GB
(1)
GB1237232A
(en)
IE
(1)
IE32524B1
(en)
IL
(1)
IL30908A0
(en)
LU
(1)
LU57189A1
(en)
MT
(1)
MTP589B
(en)
NL
(1)
NL161762C
(en)
NO
(1)
NO131032C
(en)
OA
(1)
OA02915A
(en)
SE
(1)
SE358890B
(en)
ZM
(1)
ZM14668A1
(en)
Cited By (1)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
CN108558940A
(en)
*
2018-06-01
2018-09-21
徐州诺克非医药科技有限公司
A kind of synthetic method of intermediate allene phosphonic acids
1968
1968-10-18
NL
NL6814989.A
patent/NL161762C/en
active
1968-10-21
CH
CH1570268A
patent/CH531013A/en
not_active
IP Right Cessation
1968-10-21
IE
IE1249/68A
patent/IE32524B1/en
unknown
1968-10-21
IL
IL30908A
patent/IL30908A0/en
unknown
1968-10-24
GB
GB50628/68A
patent/GB1237232A/en
not_active
Expired
1968-10-25
ES
ES359534A
patent/ES359534A1/en
not_active
Expired
1968-10-29
BE
BE723076D
patent/BE723076A/xx
unknown
1968-10-29
LU
LU57189D
patent/LU57189A1/xx
unknown
1968-10-29
NO
NO4284/68A
patent/NO131032C/no
unknown
1968-10-29
SE
SE14613/68A
patent/SE358890B/xx
unknown
1968-10-29
FI
FI683061A
patent/FI51356C/en
active
1968-10-29
DK
DK522468AA
patent/DK135996B/en
unknown
1968-10-30
FR
FR1590372D
patent/FR1590372A/fr
not_active
Expired
1968-10-30
AT
AT1056468A
patent/AT300829B/en
not_active
IP Right Cessation
1968-10-30
OA
OA53403A
patent/OA02915A/en
unknown
1968-10-30
ZM
ZM146/68A
patent/ZM14668A1/en
unknown
1968-11-26
MT
MT589A
patent/MTP589B/en
unknown
Cited By (1)
* Cited by examiner, † Cited by third party
Publication number
Priority date
Publication date
Assignee
Title
CN108558940A
(en)
*
2018-06-01
2018-09-21
徐州诺克非医药科技有限公司
A kind of synthetic method of intermediate allene phosphonic acids
Also Published As
Publication number
Publication date
MTP589B
(en)
1970-10-23
NL161762C
(en)
1980-03-17
DK135996B
(en)
1977-07-25
DK135996C
(en)
1978-01-09
SE358890B
(en)
1973-08-13
NL6814989A
(en)
1969-11-18
AT300829B
(en)
1972-08-10
ZM14668A1
(en)
1970-06-18
ES359534A1
(en)
1970-10-16
IL30908A0
(en)
1968-12-26
DE1805674B2
(en)
1973-01-04
FI51356B
(en)
1976-08-31
NL161762B
(en)
1979-10-15
NO131032B
(en)
1974-12-16
BE723076A
(en)
1969-04-29
FI51356C
(en)
1976-12-10
IE32524B1
(en)
1973-09-05
NO131032C
(en)
1975-03-25
LU57189A1
(en)
1969-05-16
OA02915A
(en)
1970-12-15
CH531013A
(en)
1972-11-30
FR1590372A
(en)
1970-04-13
DE1805674A1
(en)
1969-12-11
IE32524L
(en)
1969-11-15
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