5762-56-1

Basic information

• Product Name: TRIS(DIMETHYLAMINO)METHANE
• Synonyms: N,N,N',N',N'',N''-HEXAMETHYLMETHANETRIAMINE;N,N,N,N,N,N-HEXAMETHYLMETHANETRIAMINE;TRIS(DIMETHYLAMINO)METHANE;N,N,N',N',N'',N''-Hexamethylmethanetriamine 90%;N,N',N''-Methylidynetris(dimethylamine);Tris(dimethylamino)methane,85%;Tris(diMethylaMino)Methane, 85% 5GR;Tris(N,N-dimethylamino)methane
• CAS NO: 5762-56-1
• Molecular Formula: C₇H₁₉N₃
• Molecular Weight: 145.25
• EINECS: 227-284-0
• Product Categories: Aliphatics;Nitrogen Compounds;Organic Building Blocks;Polyamines;Building Blocks;Chemical Synthesis;Nitrogen Compounds;Organic Building Blocks
• Mol File: 5762-56-1.mol
• Article Data: 8

Chemical Properties

• Boiling Point: 42-43 °C12 mm Hg(lit.)
• Flash Point: 4 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 0.838 g/mL at 20 °C(lit.)
• Vapor Pressure: 5.24mmHg at 25°C
• Refractive Index: n20/D 1.436(lit.)
• Storage Temp.: 2-8°C
• PKA: 6.50±0.38(Predicted)
• BRN: 1901162
• CAS DataBase Reference: TRIS(DIMETHYLAMINO)METHANE(CAS DataBase Reference)
• NIST Chemistry Reference: TRIS(DIMETHYLAMINO)METHANE(5762-56-1)
• EPA Substance Registry System: TRIS(DIMETHYLAMINO)METHANE(5762-56-1)

Safety Data

• Hazard Codes: F,C
• Statements: 11-34
• Safety Statements: 16-26-36/37/39-45
• RIDADR: UN 2733 3/PG 2
• WGK Germany: 3
• F: 3-8-10-21
• HazardClass: 3.1
• PackingGroup: II
• Hazardous Substances Data: 5762-56-1(Hazardous Substances Data)

Usage

Chemical Properties

Clear colorless to slightly yellow liquid

Uses

Different sources of media describe the Uses of 5762-56-1 differently. You can refer to the following data:
1. Reagent for the introduction of the dimethylaminoethylidene group.1 General review;2 RO polymerization of lactide.3
2. N,N,N'',N'',N'''',N''''-Hexamethylmethanetriamine, can be used in the synthesis of the phosphoramidite derivative of the new nucleoside analog. It can also be used as reagent for the introduction of the dimethylaminoethylidene group.
3. Tris(dimethylamino)methane was used:to prepare the phosphoramidite derivative of the new nucleoside analogas reagent for the introduction of the dimethylaminoethylidene group in ring-opening (RO) polymerization of lactide

General Description

NMR spectra and their temperature-dependence has been reported for tris(dimethylamino)methane. Tris(dimethylamino)methane reacts with crowded α-(o-nitrophenyl) ketone to yield tetrahydroquinoline derivative.

Purification Methods

Dry it over KOH and distil it through a Vigreux column (p 11) at water pump vacuum. Store it in the absence of CO2. [Bredereck et al. Chem Ber 101 1885 1968 and Angew Chem, Int Ed Engl 5 132 1966.]

InChI:InChI=1/C7H19N3/c1-8(2)7(9(3)4)10(5)6/h7H,1-6H3/p+3

Synthetic route

butylidenetriphenylphosphorane (3728-50-5) + N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) → tris(dimethylamino)methane (5762-56-1) + butyltriphenylphosphonium chloride (13371-17-0) + <2-(Dimethylamino)-1-propylvinyl>triphenylphosphonium-chlorid (90601-14-2)

Conditions	Yield
In tetrahydrofuran; benzene for 20h;	A 75% B 90% C 67%

propylidenetriphenylphosphorane (16666-78-7) + N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) → tris(dimethylamino)methane (5762-56-1) + n-propyltriphenylphosphonium chloride (16721-43-0) + <2-(Dimethylamino)-1-ethylvinyl>triphenylphosphonium-chlorid (90601-13-1)

Conditions	Yield
In tetrahydrofuran; benzene for 20h;	A 75% B 90% C 72%

N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) + Triphenyl<(propylthio)methylen>phosphoran (90601-05-1) → tris(dimethylamino)methane (5762-56-1) + triphenyl-propylsulfanylmethyl-phosphonium; chloride (55064-94-3) + <2-(Dimethylamino)-1-(propylthio)vinyl>triphenylphosphonium-chlorid (90601-15-3)

Conditions	Yield
In tetrahydrofuran; benzene for 720h;	A 75% B 90% C 28%

N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) + ethylenetriphenylphosphorane (1754-88-7) → tris(dimethylamino)methane (5762-56-1) + ethyltriphenylphosphonium chloride (896-33-3) + <2-(Dimethylamino)-1-methylvinyl>triphenylphosphonium-chlorid (90601-12-0)

Conditions	Yield
In tetrahydrofuran; benzene for 20h;	A 75% B 90% C 76%

N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) + dimethyl amine (124-40-3) → tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
Stage #1: dimethyl amine With Trimethyl borate; sodium hydride In tetrahydrofuran deprotonation; complexation; cooling; Stage #2: N,N,N',N'-Tetramethylformamidinium chloride In tetrahydrofuran Addition; cooling;	84%
Stage #1: dimethyl amine With n-butyllithium In tetrahydrofuran; diethyl ether; hexane at -78 - 20℃; for 0.5h; Inert atmosphere; Stage #2: N,N,N',N'-Tetramethylformamidinium chloride In tetrahydrofuran; diethyl ether; hexane at 0 - 20℃; for 8h;	71%
With lithium
With n-butyllithium 1.) THF, hexane, 0 deg C, 30 min, 2.) RT, 18 h; Yield given. Multistep reaction;

N,N,N',N'-tetramethylformamidinium methyl sulfate (2013-91-4) + dimethyl amine (124-40-3) → tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
Stage #1: dimethyl amine With Trimethyl borate; sodium hydride In tetrahydrofuran deprotonation; complexation; cooling; Stage #2: N,N,N',N'-tetramethylformamidinium methyl sulfate In tetrahydrofuran Addition; cooling;	77%
With potassium tert-butylate

Bis(dimethylamino)acetonitrile (2214-82-6) + dimethyl amine (124-40-3) → tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
Stage #1: dimethyl amine With Trimethyl borate; sodium hydride In tetrahydrofuran deprotonation; complexation; cooling; Stage #2: Bis(dimethylamino)acetonitrile In tetrahydrofuran Substitution; cooling;	77%

N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) + Methylenetriphenylphosphorane (19493-09-5) → tris(dimethylamino)methane (5762-56-1) + methyltriphenylphosphonium chloride (1031-15-8) + <2-(dimethylamino)vinyl>triphenylphosphonium chloride (90601-11-9)

Conditions	Yield
In tetrahydrofuran; benzene for 20h;	A n/a B n/a C 75%

N,N,N',N',N'',N''-hexamethylguanidinium chloride (30388-20-6) → tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
With sodium bis(2-methoxyethoxy)aluminium dihydride In benzene at 60℃; for 1h;	55%
With Trimethyl borate; sodium hydride In tetrahydrofuran at 20℃; for 30h; Product distribution; Further Variations:; Reagents; conc./ratio; time; Reduction;

N,N,N',N',N'',N''-hexamethylguanidinium chloride (30388-20-6) + dimethyl amine (124-40-3) → tris(dimethylamino)methane (5762-56-1) + Tetrakis(dimethylamino)methan (10524-51-3)

Conditions	Yield
Stage #1: dimethyl amine With Trimethyl borate; sodium hydride In tetrahydrofuran for 0.25h; deprotonation; complexation; cooling; Stage #2: N,N,N',N',N'',N''-hexamethylguanidinium chloride In tetrahydrofuran at 20℃; for 48h; Addition; reduction;	A 50% B 11%

Bis(dimethylamino)acetonitrile (2214-82-6) + lithium dimethylamide (3585-33-9) → tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
In tetrahydrofuran; hexane

N,N,N',N'-tetramethylformamidinium methyl sulfate (2013-91-4) → tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
With sodium thioethylate In diethyl ether Heating;

tetrakis(dimethylamino)titanium (3275-24-9) + N,N-dimethyl-formamide (68-12-2, 33513-42-7) → tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
In diethyl ether

Trimethyl borate (121-43-7) + dimethyl amine (124-40-3) + tetramethylurea (632-22-4) + trichloromethyl chloroformate (503-38-8) → Tetrakis(dimethylamino)ethylen (996-70-3) + Tris(dimethylamino)methoxy-ethylen (36555-00-7) + tris(dimethylamino)methane (5762-56-1)

Conditions	Yield
Stage #1: dimethyl amine; tetramethylurea; trichloromethyl chloroformate In tetrahydrofuran at 20℃; Substitution; condensation; Stage #2: Trimethyl borate With sodium hydride In tetrahydrofuran at 20℃; for 24h; Substitution; Title compound not separated from byproducts;

sodium methylate (124-41-4) + N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) → bis(dimethylamino)methoxymethane (1186-70-5) + tris(dimethylamino)methane (5762-56-1) + N,N-dimethyl-formamide dimethyl acetal (4637-24-5)

Conditions	Yield
In tetrahydrofuran at 21℃; Title compound not separated from byproducts.;

N,N,N',N'-Tetramethylformamidinium chloride (1071-38-1) + sodium tert-pentoxide (14593-46-5) → tris(dimethylamino)methane (5762-56-1) + tert-pentoxy-bis(dimethylamino)methane (147196-94-9) + N,N-dimethylformamide di-tert-pentoxyacetal (1174130-81-4)

Conditions	Yield
In tetrahydrofuran; toluene at 20℃; for 48h; Product distribution / selectivity;

potassium tert-butylate (865-47-4) + N,N,N',N'-tetramethylformamidinium hexafluorophosphate → tris(dimethylamino)methane (5762-56-1) + tert-Butoxybis(dimethylamino)methane (5815-08-7) + N,N-dimethylformamide di-tert-butyl acetal (36805-97-7)

Conditions	Yield
In tetrahydrofuran at 50℃; for 1h;

potassium tert-butylate (865-47-4) + N,N,N',N'-tetramethylformamidinium methyl sulfate (2013-91-4) → tris(dimethylamino)methane (5762-56-1) + tert-Butoxybis(dimethylamino)methane (5815-08-7) + N,N-dimethylformamide di-tert-butyl acetal (36805-97-7)

Conditions	Yield
In tetrahydrofuran at 60℃; for 1h;

potassium tert-butylate (865-47-4) + N,N,N',N'-Tetramethylformamidinium-(p-toluolsulfonat) (3218-35-7) → tris(dimethylamino)methane (5762-56-1) + tert-Butoxybis(dimethylamino)methane (5815-08-7) + N,N-dimethylformamide di-tert-butyl acetal (36805-97-7)

Conditions	Yield
In tetrahydrofuran at 50℃; for 1h;

tris(dimethylamino)methane (5762-56-1) + 3-oxo-9-azaspiro[5.5]undec-4-ene-9-carboxylic acid benzyl ester (189333-18-4) → 8-(dimethylaminomethylene)-9-oxo-3-azaspiro[5.5]undec-10-ene-3-carboxylic acid benzyl ester (1301214-81-2)

Conditions	Yield
In toluene for 5h; Reflux;	100%
In toluene at 110℃; for 5h; Inert atmosphere;	100%
In toluene for 5h; Reflux;	100%
In toluene for 5h; Reflux;	100%
In toluene at 100℃; for 15h;	99%

tris(dimethylamino)methane (5762-56-1) + C23H34O6Si → C26H39NO6Si (85925-72-0)

Conditions	Yield
at 120℃; for 16h;	99%

5,5-diphenyldihydrofuran-2(3H)-one (7746-94-3) + tris(dimethylamino)methane (5762-56-1) → 3-Dimethylaminomethylen-5,5-diphenyl-dihydro-2(3H)-furanon (127074-68-4)

Conditions	Yield
at 100℃;	94%

tris(dimethylamino)methane (5762-56-1) + 5,6:7,8-di-O-isopropylidene-D-manno-oct-1,4-lactone (81336-67-6) → (R)-3-[1-Dimethylamino-meth-(E)-ylidene]-5-((4R,5R,4'R)-2,2,2',2'-tetramethyl-[4,4']bi[[1,3]dioxolanyl]-5-yl)-dihydro-furan-2-one

Conditions	Yield
at 70℃; for 120h;	94%

tris(dimethylamino)methane (5762-56-1) + δ,δ-Diphenyl-δ-valerolacton (115407-73-3) → 3-Dimethylaminomethylen-6,6-diphenyl-tetrahydro-2(2H)pyranon (127074-67-3)

Conditions	Yield
at 100℃; for 6h;	93%

tris(dimethylamino)methane (5762-56-1) + (1R*,6S*,7S*,8S*)-7,8-isopropylidenedioxy-1-pentyl-3,9-dioxabicyclo<4.2.1>nonan-4-one → (1R*,6R*,7S*,8S*)-5-(dimethylaminomethylene)-7,8-isopropylidenedioxy-1-pentyl-3,9-dioxabicyclo<4.2.1>nonan-4-one

Conditions	Yield
In N,N-dimethyl-formamide at 70℃; for 1h;	91%

5-diethylcarbamoyl-5-ethyl-4-methyl-2-oxo-2,5-dihydro-furan-3-carboxylic acid ethyl ester (880815-43-0) + tris(dimethylamino)methane (5762-56-1) → 5-diethylcarbamoyl-4-((E)-2-dimethylamino-vinyl)-5-ethyl-2-oxo-2,5-dihydro-furan-3-carboxylic acid ethyl ester (880815-51-0)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 17h;	90%
In N,N-dimethyl-formamide at 20℃; for 17h; Product distribution / selectivity;	90%

(S)-5-diethylcarbamoyl-5-ethyl-4-methyl-2-oxo-2,5-dihydro-furan-3-carboxylic acid ethyl ester (880815-64-5) + tris(dimethylamino)methane (5762-56-1) → (S)-5-diethylcarbamoyl-4-((E)-2-dimethylamino-vinyl)-5-ethyl-2-oxo-2,5-dihydro-furan-3-carboxylic acid ethyl ester (880815-66-7)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 17h;	90%

tris(dimethylamino)methane (5762-56-1) + guanidine hydrogen carbonate (124-46-9, 20734-13-8, 100224-74-6, 593-85-1) + N6-(2-(4-phenylpiperazin-1-yl)-ethyl)-N6-propyl-4,5,6,7-tetrahydrobenzo[d]thiazole-2,6-diamine (477789-22-3) → 2-Amino-6-[N-propyl-(N-(4-phenylpiperazin-1-yl)-ethyl)amino]-5,6,7,8-tetrahydrobenzopyrimidine

Conditions	Yield
Stage #1: tris(dimethylamino)methane; N6-(2-(4-phenylpiperazin-1-yl)-ethyl)-N6-propyl-4,5,6,7-tetrahydrobenzo[d]thiazole-2,6-diamine In toluene at 90℃; for 4h; Stage #2: guanidine hydrogen carbonate In ethanol for 17h; heating;	88%

4,7-diaza-1,9-decadiene (61798-21-8) + tris(dimethylamino)methane (5762-56-1) → 1,3-diallyl-2-dimethylaminoimidazolidine (125815-73-8)

Conditions	Yield
In hexane for 2h; Heating;	87%

tris(dimethylamino)methane (5762-56-1) + (5S,1'S)-5-{1',2'-dihydroxy-1',2'-O-isopropylidene-ethyl}-tetrahydrofuran-2-one (128856-61-1) → (4S,5R)-2(E)-N,N-dimethylaminomethylidene-4-<5,6-O-(1-methylethylidene)>-γ-hexanolactone (128856-62-2)

Conditions	Yield
In N,N-dimethyl-formamide at 67℃;	85%

tris(dimethylamino)methane (5762-56-1) + (+/-)-trans-4-propyl-3,4,4a,5,6,7,8,8a-octahydro-2H-1,4-benzoxazin-6-one → (+/-)-trans-(E)-7-dimethylaminomethylidene-4-propyl-2,3,4,4a,5,6,8,8a-octahydro-1,4-benzoxazin-6-one

Conditions	Yield
In N,N-dimethyl-formamide at 65℃; for 16h; Condensation;	85%

4-methyl-4-phenyldihydrofuran-2(3H)-one (50598-37-3) + tris(dimethylamino)methane (5762-56-1) → 3-[1-Dimethylamino-meth-(Z)-ylidene]-4-methyl-4-phenyl-dihydro-furan-2-one (313219-82-8)

Conditions	Yield
at 70℃; for 12h; Substitution;	85%

tris(dimethylamino)methane (5762-56-1) + C11H11(2)HO2 → C11H9(2)HO2C3H7N

Conditions	Yield
at 70℃; for 12h; Substitution;	85%

tris(dimethylamino)methane (5762-56-1) → N,N,N',N'-tetramethyl-selenurea (5943-53-3)

Conditions	Yield
With selenium In xylene for 44h; Heating;	82%

2-anilino-4-(pyrrolid-2-on-1-ylmethyl)pyrimidine + tris(dimethylamino)methane (5762-56-1) → 2-anilino-4-[1-(pyrrolid-2-on-1-yl)-2-(dimethylamino)vinyl]pyrimidine (797793-43-2)

Conditions	Yield
In DMF (N,N-dimethyl-formamide) at 130℃; for 6h;	81%

tris(dimethylamino)methane (5762-56-1) + (2S,3S,2'S,5'R)-3-dimethoxymethyl-2',5'-dimethoxy-3,4,2',5'-tetrahydro-2H-2,2'-bifuranyl-5-one (1309233-72-4) → (2S,3S,2'S,5'R)-3-dimethoxymethyl-4-dimethylaminomethylene-2',5'-dimethoxy-3,4,2',5'-tetrahydro-2H-2,2'-bifuranyl-5-one (1309233-60-0)

Conditions	Yield
In toluene at 70℃; for 48h; Inert atmosphere;	81%

tris(dimethylamino)methane (5762-56-1) + (3aS,7aR)-1-Methyl-3a-(2-nitro-phenyl)-octahydro-indol-4-one (138040-08-1, 138040-09-2) → (3aRS, 6RS, 11bSR)-3-methyl-2,3,3a,4,5,6,7,11b-octahydro-1H-6,11b-methanopyrrolo<2,3-e><1>benzazocin-12-one + 3-methyl-5-(dimethylaminomethylene)-3a-(o-nitrophenyl) octahydroindol-4-one

Conditions	Yield
In tetrahydrofuran for 5h; Heating; Yields of byproduct given;	A 80% B n/a
In tetrahydrofuran for 5h; Heating; Yield given;	A 80% B n/a

tris(dimethylamino)methane (5762-56-1) + diethyl methylenebis<(ethoxymethyl)phosphinate> (130739-00-3) → C7H18NO3P + O-ethyl(ethoxymethyl)(2-dimethylamino)vinylphosphonate

Conditions	Yield
With zinc(II) chloride at 160 - 170℃; Title compound not separated from byproducts;	A n/a B 76%
With zinc(II) chloride at 160 - 170℃;	A n/a B 76%

7,8,9,10-tetrahydrocyclohepta[b]indol-6(5H)-one (7257-25-2) + tris(dimethylamino)methane (5762-56-1) → 7-[(dimethylamino)methylidene]-7,8,9,10-tetrahydrocyclohepta[b]indol-6(5H)-one (871112-20-8)

Conditions	Yield
In N,N-dimethyl-formamide at 70℃; for 3h;	76%
In DMF (N,N-dimethyl-formamide) at 70℃; for 3h;

diazoacetic acid ethyl ester (623-73-4) + tris(dimethylamino)methane (5762-56-1) → 2-Diazo-3,3-bis-dimethylamino-propionic acid ethyl ester

Conditions	Yield
at 20℃; for 0.5h;	75%

tris(dimethylamino)methane (5762-56-1) + t-butyl diazoacetate (35059-50-8) → 2-Diazo-3,3-bis-dimethylamino-propionic acid tert-butyl ester

Conditions	Yield
at 20℃; for 20h;	74%

Upstream product

• 2214-82-6 Bis(dimethylamino)acetonitrile 
• 3585-33-9 lithium dimethylamide 
• 3728-50-5 butylidenetriphenylphosphorane 
• 1071-38-1 N,N,N',N'-Tetramethylformamidinium chloride 
• 16666-78-7 propylidenetriphenylphosphorane 
• 90601-05-1 Triphenyl<(propylthio)methylen>phosphoran 
• 14593-46-5 sodium tert-pentoxide 
• 865-47-4 potassium tert-butylate 
• 2013-91-4 N,N,N',N'-tetramethylformamidinium methyl sulfate 
• 3218-35-7 N,N,N',N'-Tetramethylformamidinium-(p-toluolsulfonat) 
• 124-41-4 sodium methylate 
• 121-43-7 Trimethyl borate 
• 124-40-3 dimethyl amine 
• 632-22-4 tetramethylurea 

Downstream Products

• 35520-41-3 trans-3-dimethylaminoacrylonitrile 
• 75374-07-1 Bis(aziridino)dimethylaminomethan 
• 124-40-3 dimethyl amine 
• 2404-04-8 NN-dimethyl di-isopropyl-phosphoramidate 
• 87594-23-8 ((E)-2-Dimethylamino-vinyl)-phosphonic acid diisopropyl ester 
• 127074-68-4 3-Dimethylaminomethylen-5,5-diphenyl-dihydro-2(3H)-furanon 
• 75374-06-0 1,3-Dimethyl-2-dimethylaminoimidazolidin 
• 5943-53-3 N,N,N',N'-tetramethylselenourea 
• 295325-91-6 2-(2-dimethylamino-6-nitrophenyl)acetaldehyde semicarbazone 
• 570386-22-0 N,N-dimethyl-N'-[4-(2-dimethylaminovinyl)-5-nitro-6-oxo-1,6-dihydropyrimidin-2-yl]formamidine 
• 20289-26-3 4-benzyloxy-1H-indole 
• 55314-16-4 (E)-3-(dimethylamino)-1-(pyridin-3-yl)prop-2-en-1-one 
• 97466-90-5 quinelorane 
• 1174130-65-4 (R)-5-biphenyl-4-ylmethyl-3-[1-dimethylaminometh-(E/Z)-ylidene]-2-oxo-pyrrolidine-1-carboxylic acid tert-butyl ester 

Relevant articles and documents

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NEW PROCESSES

The invention relates to a new process for producing NEP inhibitors or prodrugs thereof, in particular NEP inhibitors comprising a γ-amino-δ-biphenyl-α-methylalkanoic acid, or acid ester, backbone. In detail, the new processes, according to the present invention, are ultimately related to the synthesis of intermediates to prepare the above NEP inhibitors, namely compounds according to formula (1), or salt thereof, wherein R1 and R2 are, independently of each other, hydrogen or a nitrogen protecting group, and R3 is a carboxyl group or an ester group, preferably carboxyl group or alkyl ester.

Orthoamides. LII. Contributions to the synthesis of carboxylic ortho acid amides

The formamidinium salts 11a, c as well as the nitrile 12 react with sodiumhydride/dimethylamine in the presence of trimethylborate to give the ortho formic acid amide 3a. The orthoamides 6a and 16 can be prepared from the iminium salts 15 and 14, resp. by the same procedure. Treatment of the azavinylogous formamidinium salt 15 with sodiumhydride and piperidine or morpholine in the presence of trime-thylborate affords the orthoamides 6c and 6d, resp. By transamination of the azavinylogous aminalester 5a are accessible the orthoamides 6b-d. The vinylogous orthocarbonic acid derivative 17 can be obtained from the salt 14 and sodium alcoholates. The action of sodiumhydride, dimethylamine and trimethylborate on the iminium salt 18 produces a mixture of the orthocarbonic acid derivatives 7a, 8a, 9a. When the guanidinium salt 20 is treated with the same reagents the ortho-amides 3a and 10a are obtained. The reduction of the salt 20 with sodiumhydride in the presence of several activating reagents (e.g. tetrabutyl orthotitanate, aluminiumisopropylate, trimethylborate) affords the orthoamide 3a. The reduction of the iminium salts 18 and 24 does not proceed clean, giving mixtures of various orthoformic acid derivatives. The form-amidine 25 can be prepared by reduction of the salt 15 with sodiumhydride/trimethylborate with good yields. By the action of the corresponding carbanions on the guanidinium salt 20 can be obtained the carboxylic acid orthoamides 26-33. By the same procedure the orthoamides of alkyne carboxylic acids 36a-h, j-n are accessible. Wiley-VCH Verlag GmbH, 2000.