Generally speaking, it’s best to follow a manufacturer’s recommendations but there’s often some leeway in the specifications because the recommendations are chosen based on components readily available at the time and to allow for variances in every component.
Synology’s DS420+ uses Intel’s Celeron J4025 which was released in late 2019. Intel states that the maximum supported RAM is 8GB (ideally as a pair of 4GB modules for dual-channel performance). However, others on this forum, Reddit, YouTube and elsewhere have reported success with higher capacity modules.
Is it advisable? No. Should you do it? Sure, the risk of damage is tiny as long as the memory module is the right type and well made. Pick a module that other DS420+ owners have confirmed to work without any issues.
Having said that, a few things to consider…
Synology says that the DS420+ consumes 28.30 watts when the internal drives are being accessed (based on a stock unit populated with four WD10EFRX, aka “1TB Western Digital Red Plus”).
A WD10EFRX pulls 3.3W during read/write activity, a Celeron J4025 has a 10W TDP at full load, and 2GB of DDR4 requires about 0.75W (rule of thumb is that every 8GB of DDR4 requires 3W of power).
The WD Red Pro has a 7200RPM spindle speed so it requires more power than the Red and Red Plus models. The 6TB Red Pro pulls 7.2W during read/writes (+3.9W compared to a WD10EFRX).
Then there are also the pair of M.2 slots for optional SSDs.
16GB of DDR4 would increase the power draw by just over 21% on the 28.3W baseline reference. It’s extra load on the mainboard, power supply and cooling fans. A mainboard manufacturer would have selected components (e.g., capacitors, resistors, voltage regulators, etc.) for the intended maximum memory capacity. Likewise, Synology would have designed the DS420+ assuming a total of 6GB of DDR4.
I wouldn’t recommend upgrading the RAM immediately. It’s best to stress test the NAS for at least a few days or more just in case there’s a need to call tech support and/or get a RMA. Having an unsupported amount of RAM will complicate tracking down any stability issues (Synology says each year they receive 50+ support tickets as a result of memory upgrades).
After upgrading the RAM, run a full memory test to check for a defective memory module, compatibility, plus stability under extended high load and heat (Synology uses Memtest86 under the hood for its Synology Assistant add-on).